JP2002212788A - Aluminum material and aluminum alloy material having gray-colored combined coating film, and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aluminum material and an aluminum alloy material having a warm gray-colored combined anodized coating film and organic films of low saturation which can have a product-colored variation without receiving the variation of the coloring of a base and the variation of the thickness of the coating film, and to provide a production method therefor. SOLUTION: An anodized coating film is deposited on an aluminum material or an aluminum alloy material, and is colored into black to bronze by an electrolytic pigmentation method. After that, electrodeposition coating is performed by using a brown translucent coating material containing a 0.15 to 0.5 wt.% white pigment having a particle size of 0.1 to <0.5 μm, a 0.01 to 0.3 wt.% black pigment having a particle size of 0.01 to 0.5 μm and a 0.01 to 0.3 wt.% pigment having a particle size of 0.01 to 0.5 μm and a peak of light reflectance in the wavelength of 570 to 700 nm. In this way, the aluminum material or aluminum alloy material having a warm gray-colored combined coating of low saturation can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum material and an aluminum alloy material having a gray color composite film and a method for producing the same, and more particularly, to an aluminum material and an aluminum alloy material having corrosion resistance, weather resistance and decorativeness. The present invention relates to an electrodeposition coating method and an electrodeposition coating product for producing an anodized coating composite film having a low-saturation warm gray color by electrolytic coloring and electrodeposition coating without impairment.

[0002]

2. Description of the Related Art Methods for coloring aluminum materials and aluminum alloy materials include an alloy coloring method, an electrolytic coloring method, a secondary electrolytic coloring method, a tertiary electrolytic coloring method, a dyeing method and a coating method. In general, a secondary electrolytic coloring method is used from the viewpoints of performance, cost, and stability in production. However, coloring by the secondary electrolytic coloring method is limited to coloring from yellowish to brownish colors such as amber color, bronze color, and black color, and it is difficult to develop a low saturation gray color. However, in recent years, there has been an increasing demand for calm gray-colored products in relation to building materials or exteriors, and it is desired to develop gray-colored products that are low in cost and have good performance in terms of corrosion resistance and weather resistance. I was

[0003] As a gray coloring method for aluminum materials and aluminum alloy materials, an alloy coloring method for forming a gray color in the process of forming an anodic oxide film by giving a coloring factor to the alloy composition, and controlling the structure of the anodic oxide film. Electrolytic coloring method to produce a gray color by performing a tertiary electrolytic coloring method, dyeing method, electrostatic coating method, powder coating method, etc., in which an electrolytic step is further performed between the anodic oxide film forming step and the electrolytic coloring step with a metal salt. However, all of these methods have many limitations in terms of cost, manufacturing stability, and performance, and cannot be a popular method.

In recent years, as a method of coloring a gray-based color which is low in cost and has good performance in terms of corrosion resistance and weather resistance, etc., a gray-based coloring method by opaque colored electrodeposition coating, and a base color and semi-transparent by secondary electrolytic coloring. A gray-based coloring method has been developed in combination with a colored electrodeposition coating. In the former case of coloring by opaque colored electrodeposition coating, although the color stability is high, the color of the electrodeposition coating itself is fixed, and in order to change the color, the paint itself must be changed, and versatility It is a technique with few.

On the other hand, the latter method using a combination of an undercoating color by secondary electrolytic coloring and translucent colored electrodeposition coating is disclosed in, for example, Japanese Patent No. 2938781. 0.0 μm of 10 μm white pigment
A method of forming a bluish-gray composite film by combining a white film with an electrodeposition paint containing 1 wt% to 0.5 wt% is disclosed. Also, JP-A-11-106
No. 994 discloses that an anodized film having an L ^* value of 30 or more contains a white pigment of 0.7 to 1.2 wt% and a black pigment of 0.03 to 0.08 wt% based on the resin solid content. A method of obtaining an achromatic gray by applying an electrodeposition coating using a translucent gray paint is disclosed.

However, the coloring method based on the combination of the base color by the secondary electrolytic coloring and the translucent colored electrodeposition coating has the following problems: (1) The degree of coloring or the degree of coloring caused by the variation in the conditions during the secondary electrolytic coloring of the base. Variation of color tone (2) Variations in the transparency and color tone of the coating film due to variations in the film thickness and pigment concentration of the semi-transparent colored electrodeposition coating film occur, and the synergistic effects of these changes the color of the composite coating surface. It can be said that this is a coloring method that is very difficult to control in terms of color stability, because the variation greatly increases.

In the above-mentioned Japanese Patent No. 2938781 and Japanese Patent Application Laid-Open No. H11-106994, when the background is black or dark bronze, the color tone is fixed to a blue-based cold color system, and the color tone is determined by the present invention. It cannot be a warm gray color. Furthermore, even with such a coloring method using a combination of the base color and the translucent colored electrodeposition coating by secondary electrolytic coloring, if the coating film is scratched, the same as the case of gray coloring by opaque colored electrodeposition coating In addition, even if the scratches have a small area, an anodized film base having a completely different color tone appears, and the scratches are more conspicuous than general composite film products.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems in the anodic oxidation coating composite coating of aluminum and aluminum alloy materials, and is expected to occur during actual production. It is hardly affected by the variation in the color of the base and the variation in the thickness of the coating film, and it is possible to have a variation in the product color. It is an object of the present invention to provide an aluminum material and an aluminum alloy material having a color anodized coating composite film and a method for producing the same.

[0009]

According to the present invention, there is provided, in accordance with the present invention, an anodic oxide film colored in black to bronze, and a film having a particle size of from 0,0 to 0,0. 0.15 to less than 0.5 μm of white pigment
wt% to 0.5wt%, and the particle size is 0.01μ
0.01 to 0.3 wt% of black pigment of m to 0.5 μm
Using a translucent brown paint containing 0.01% to 0.3% by weight of a pigment having a particle size of 0.01 μm to 0.5 μm and a peak of light reflectance at a wavelength of 570 nm to 700 nm. An aluminum material or an aluminum alloy material having a low-saturation warm color gray composite film composed of the generated brownish translucent coating film is provided. According to a preferred embodiment, the colored anodic oxide film has a color difference from the composite film surface color of ΔE ^* ab of 8 or less and a chroma difference of ΔC of 4 or less.

Further, according to the present invention, an anodic oxide film is formed on an aluminum material or an aluminum alloy material, and is colored black to bronze by an electrolytic coloring method. 0.15 wt% to 0.5 wt% of a white pigment having a particle size of less than 5 μm, and 0.01 wt% to a black pigment having a particle size of 0.01 μm to 0.5 μm.
0.3 wt%, and the particle size is 0.01 μm to 0.1 μm.
Low chroma, characterized by applying an electrodeposition coating using a brownish translucent paint containing 0.01 wt% to 0.3 wt% of a pigment having a peak of light reflectance at a wavelength of 570 nm to 700 nm at 5 μm. The present invention provides a method for producing an aluminum material or an aluminum alloy material having a warm gray composite film. In a preferred embodiment, the color difference between the anodized film colored by the electrolytic coloring method and the surface color of the composite film is ΔE
^* Adjusted so that ab is 8 or less and the saturation difference is 4 or less in ΔC.

The low-saturation warm-colored gray color referred to in this specification is an L ^* a ^* b ^* color system (CIE 1976).
The L ^* value indicating the lightness in (JIS Z8729) is 33.
A ^* value and b ^* value indicating saturation (a red value indicates a positive a ^* value, a green direction indicates a negative a ^* value, b
^{* When the} value is positive, the color tone in the yellow direction, and when the value is negative, the color tone in the blue direction is 0 to 3 inclusive. Also, as used herein, black to bronze refers to a density having an L ^* value of 22 to 50.

Further, the color difference ΔE as referred to in this specification
^*ab (CIE 1976) (JIS Z8729) and
Is the colorimetric value of the electrolytically colored anodized film.
And, further subjected to electrodeposition coating according to the production method of the present invention
The colorimetric value of the surface color of the composite film is L^*a^*b^*Color system (CIE
 1976) (JIS Z8729),
It is represented by the following equation. That is, it is electrolytically colored
The colorimetric value of the anodized film₁, A₁, B₁, Composite coating
The colorimetric value of the surface color is L_Two, A_Two, B_TwoThen, the color difference ΔE^*ab = [(L₁-L_Two)^Two+ (A₁-A_Two)^Two+
(B₁-B_Two)^Two]^1/2 Saturation difference ΔC = [(a₁-A_Two)^Two+ (B₁-B_Two)^Two]^1/2 Is represented by However, the saturation difference is generally used.
"CIE 1976" or "JIS Z87
29 ”^*ab = (a₁ ^Two+ B₁ ^Two)^1/2
− (A _Two ^Two+ B_Two ^Two)^1/2Then the difference in hue appears as a numerical value
Therefore, in this specification, the saturation difference is represented by ΔC = [(a₁−
a_Two)^Two+ (B₁-B_Two)^Two]^1/2Shall be expressed as

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have adjusted an anodized film colored in black to bronze and a brown translucent film formed thereon. In combination with the applied coating, it is possible to obtain a low-saturation warm gray anodized coating composite coating,
In the case of such a combination, there is almost no influence of the coloring degree and the color tone of the electrolytic coloring which may occur in production, and by changing the coloring degree of the electrolytic coloring, it is possible to have a color variation as a product. I found something. When a brownish translucent coating film is formed on the black-bronze-colored anodic oxide film of the base, the color difference between the colored anodic oxide film and the composite film surface color is ΔE ^* ab of 8 in particular. It was also found that when the difference in saturation was ΔC of 4 or less, even if the coating film was scratched, it became less noticeable. Further, such a translucent brown coating film has a particle size of 0.15 wt% to 0.5 wt% of a white pigment having a particle size of 0.1 μm or more and less than 0.5 μm, and a particle size of 0.05 wt% or less.
Black pigment of 1 μm to 0.5 μm is added in an amount of 0.01 wt% to 0.3%.
By using a translucent brownish paint containing 0.01 wt% to 0.3 wt% of a pigment having a light reflectance peak at a wavelength of 570 nm to 700 nm having a particle size of 0.01 μm to 0.5 μm and a wavelength of 0.01 μm to 0.5 μm. They have found that a film can be formed, and have completed the present invention.

Hereinafter, the method of the present invention will be described in detail. First, a method for forming an anodic oxide film on an aluminum material and an aluminum alloy material, and a treatment method for coloring the anodic oxide film to a black to bronze color are described above. Except for using a paint containing the specific pigment described above, it can be carried out by a generally known method. That is, in the step of forming the anodized film, an inorganic or organic acid such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, or a mixed acid thereof can be used for the electrolytic solution. In the electrolytic solution, an aluminum material or an aluminum alloy material is used as an anode, and a DC current, a pulse current, an AC / DC superimposed current, an AC current, or the like is applied to the electrolytic solution to form a 6 μm to 3 μm
A 0 μm porous anodic oxide film is formed.

Next, for coloring the base of the anodic oxide film, various coloring methods such as a secondary electrolytic coloring method, a tertiary electrolytic coloring method, an electrolytic coloring method, an alloy coloring method, and a dyeing method can be applied. In consideration of production stability and the like, a general secondary electrolytic coloring method is preferably effective. In this secondary electrolytic coloring method, in an electrolytic coloring solution containing a metal salt such as a nickel salt, a tin salt, and a cobalt salt, various organic acids, and a sulfur compound, an aluminum material on which the above-described anodized film is formed or The aluminum alloy material is colored black to bronze by applying an alternating current, a direct current, an AC / DC superimposed current, a pulse current, or the like.

Thereafter, the electrodeposition paint as described above, that is, containing 0.15 wt% to 0.5 wt% of a white pigment having a particle size of 0.1 μm or more and less than 0.5 μm, and further having a particle size of 0.01 μm 0.01 wt% of 0.5 μm black pigment
0.3 wt%, and the particle size is 0.01 μm to 0.1 μm.
Using a translucent brown-colored paint containing 0.01 wt% to 0.3 wt% of a pigment having a light reflectance peak at a wavelength of 570 nm to 700 nm at 5 μm, a semi-transparent electrodeposition coating on the above-mentioned colored anodic oxide film By forming the film with a thickness of 5 μm to 30 μm, a low-color warm gray color is developed.

In the present invention, the base electrodeposition paint used for the brownish translucent paint is particularly a type of paint capable of being electrodeposited on an anodic oxide film on an aluminum material or an aluminum alloy material. Without being limited, a general acrylic melamine resin, an epoxy ester resin type, a polyester resin type, a fluororesin type, etc., a transparent or translucent glossy paint or matte paint can be used. .

A white pigment (one or more of titanium dioxide, lead white, zinc white, zirconium oxide and the like) adjusted to have a particle size of 0.1 μm or more and less than 0.5 μm is added to the base paint in an amount of 0.1 to 0.2 μm. 15 wt% to 0.5 wt%, particle size 0.0
Black pigment of 1 μm to 0.5 μm is added in an amount of 0.01 wt% to 0.3%.
wt%, and 0.01 wt% to 0.3 wt% of a pigment having a particle size of 0.01 μm to 0.5 μm and a peak of light reflectance at a wavelength of 570 nm to 700 nm is added to prepare a brownish translucent paint. To use.

When a white pigment having a particle size of 0.5 μm or more is used, sedimentation due to agglomeration of the pigment easily occurs and it is difficult to maintain the stability of the liquid. Must be adjusted to less than 0.5 μm. For the same reason, the black pigment and the pigment having a light reflectance peak at a wavelength of 570 nm to 700 nm are also 0.5 μm
It is necessary to adjust the following. The particle size of the white pigment,
It is desirable to adjust the thickness to preferably 0.2 μm to 0.4 μm.

Further, the concentration of the white pigment is set to the lower limit of 0.1%.
When the amount is less than 5 wt%, the coating film concealing property becomes extremely low, and the influence of the color of the colored anodic oxide film, which is the base, appears strongly. Occurs as When trying to obtain the above-mentioned effect at such a low concentration, in order to ensure its concealing properties, it is necessary to form an extreme coating film thickness,
Problems also arise with respect to the stability of the coating, and also the economics. In this case, the toning pigment described below (in the present specification,
In order to secure the concealing property by using a black pigment and a pigment having a light reflectance peak at a wavelength of 570 nm to 700 nm), a toning pigment must be added more than necessary, and the L ^* required in the present invention is required ^. A low-saturation warm color gray color having a value of 33 or more is not obtained. On the other hand, if it exceeds the upper limit of 0.5 wt%, the weather resistance of the coating film tends to be slightly inferior, and furthermore, the concealing property becomes too high and becomes close to an opaque coating film. Even if is extremely changed, it is impossible to cause a change in color development as a composite film, and it becomes impossible to obtain a color variation as a product.
In the present invention, in consideration of the above, the white pigment concentration is set to 0.1.
15 wt% to 0.5 wt%, preferably 0.18 wt%
% To 0.3 wt%.

The toning pigment has a particle size of 0.01 μm.
0.01 to 0.3 wt% of black pigment of m to 0.5 μm
Further, a pigment having a particle size of 0.01 μm to 0.5 μm and a peak of light reflectance at a wavelength of 570 nm to 700 nm is added in an amount of 0.01 wt% to 0.3 wt%. In the present invention, as a toning pigment, if it is a black pigment, for example, carbon black, iron black, or the like, and a wavelength of 570 nm to 7
As a pigment having a light reflectance peak at 00 nm,
For example, yellow pigments such as yellow iron oxide, zinc yellow and isoindolenone, and red pigments such as lead red, red iron oxide, quinacridone and other inorganic pigments, and organic pigments may be used alone or in combination of two or more. Can be used.

When the concentration of the toning pigment is lower than the lower limit, the coloring by the pigment is hardly perceived or does not appear in the measurement result, so that the effect of the addition is significantly reduced. On the other hand, when the value exceeds the upper limit, the coloring by the toning pigment is strong and the lightness is too low to be black, or a specific color is emphasized, and the saturation is too high to be grayish. The texture differs from the color. In the present invention, in consideration of the above, the concentration of the black pigment having a particle size to be added of 0.01 μm to 0.5 μm is set to 0.01%.
wt% to 0.3 wt%, preferably 0.02 wt% to
Adjusted to 0.1 wt%, and the particle size is 0.01 μm ~
The concentration of the pigment having a light reflectance peak at a wavelength of 570 nm to 700 nm at 0.5 μm is adjusted to 0.01 wt% to 0.3 wt%.
wt%, preferably 0.02 wt% to 0.2 wt%.

[0023] By combining the electrodeposition paint adjusted to be translucent brown as described above with an anodic oxide film colored black to bronze, the influence of the degree of coloration and the color tone variation of the electrolytic coloring which may occur in production. However, it is possible to obtain a low-saturation, warm gray-colored anodic oxide composite film capable of having a variety of colors as a product by extremely changing the degree of electrolytic coloring.

[0024]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited to the following Examples.

Example 1 An aluminum extruded material A-6063S, which had been degreased, etched, and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode, and was placed between an aluminum cathode provided as a counter electrode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Melamine-based electrodeposition containing 0.02 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm and 0.04 wt% of a red pigment (a red iron oxide) having a particle size of 0.3 μm The anode was immersed in the coating material to form an anode, and a DC voltage of 170 V was applied for 120 seconds to form a 13 μm coating on the surface. After that, bake and dry at 185 ° C for 30 minutes,
A gray-colored composite film with low chroma was obtained.

The results of measuring the color of this sample with a color difference meter CR-200 manufactured by Minolta Co., Ltd. are described below. Product surface color: L ^* value = 34.9, a ^* value = 0.5, b ^* value = 1.3 Base color: L ^* value = 29.2, a ^* value = 2.8, b ^* value =
3.6 As for the product surface color, both the a ^* value and the b ^* value were between 0 and 3, and it was a low-saturation warm gray color. At this time, the color difference between the product surface color and the base color is ΔE ^* ab = 6.5, and the chroma difference is ΔC = 3.3. Has become.

Example 2 An aluminum extruded material A-6063S, which was degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 7 minutes to obtain a dark bronze colored film having an L ^* value of about 33. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Melamine-based electrodeposition containing 0.02 wt% of a yellow pigment (yellow iron oxide) having a particle diameter of 0.3 μm and 0.03 wt% of a red pigment (agar red) having a particle diameter of 0.3 μm. The anode was immersed in the coating material to form an anode, and a DC voltage of 170 V was applied for 120 seconds to form a 13 μm coating on the surface. After that, bake and dry at 185 ° C for 30 minutes,
A warm-colored gray-colored composite film was obtained.

The results of measuring the color of this sample with a colorimeter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 35.0, a ^* value = 0.5, b ^* value = 1.4 Base color: L ^* value = 33.1, a ^* value = 3.9, b ^* value =
6.7 The colorimetric values of the samples were almost the same as those in Example 1, and it was found that even if there was some variation that could occur during production in the electrolytic coloring of the base, the surface color of the product was hardly affected. At this time, the color difference between the product surface color and the base color was ΔE ^* ab = 6.6, and the chroma difference was ΔC = 6.3. It became easier.

Example 3 An aluminum extruded material A-6063S, which had been degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Melamine-based electrodeposition containing 0.02 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm and 0.04 wt% of a red pigment (a red iron oxide) having a particle size of 0.3 μm It was immersed in a paint to form an anode, and a DC voltage of 190 V was supplied for 120 seconds to form a 17 µm coating on the surface. After that, bake and dry at 185 ° C for 30 minutes,
A warm-colored gray-colored composite film was obtained.

The results of measuring the color of this sample with a color difference meter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 35.2, a ^* value = 0.6, b ^* value = 1.4 Base color: L ^* value = 29.1, a ^* value = 2.7, b ^* value =
The colorimetric values of the 3.5 samples were almost the same as in Example 1, and it can be seen that even if there is a possible variation in the coating film thickness during production, the surface color of the product is hardly affected. At this time, the color difference between the product surface color and the base color is ΔE ^* a
b = 6.8 and the saturation difference was ΔC = 3.0, making it less noticeable even when the underlying colored oxide film was exposed due to the coating film flaw.

Example 4 An aluminum extruded material A-6063S, which had been degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 6 V was applied for 6 minutes to obtain a bronze colored film having an L ^* value of about 50. Next, a resin solid content of 9% and a particle size of 0.
0.2 wt% of a 3 μm white pigment (titanium dioxide) and 0.1 wt% of a black pigment (carbon black) having a particle size of 0.05 μm.
In an acrylic melamine-based electrodeposition coating material containing 0.04 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm and 0.03 wt% of a red pigment having a particle size of 0.3 μm. The anode was immersed and a DC voltage of 170 V was applied to 12
Electric current was applied for 0 seconds to form a 13 μm coating on the surface.
Thereafter, baking and drying were performed at 185 ° C. for 30 minutes to obtain a low-chroma gray composite coloring film.

The results of measuring the color of this sample with a colorimeter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 38.5, a ^* value = 1.9, b ^* value = 2.9 Base color: L ^* value = 49.7, a ^* value = 3.5, b ^* value = 1
5.1 Due to the semi-transparent electrodeposition coating, by changing the degree of coloring of the base material extremely, the saturation becomes slightly higher, but the absolute values of a ^* value and b ^* value are both between 0 and 3. The color became warm gray, and the brightness increased, resulting in a color tone that could be clearly recognized as a color variation different from that of Example 1 as a product. At this time, the color difference between the product surface color and the base color is ΔE ^*
ab = 16.7, the saturation difference was ΔC = 12.3, and when the colored oxide film on the base was exposed due to a scratch on the coating film, it became more conspicuous.

Example 5 An aluminum extruded material A-6063S, which had been degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 12 minutes to obtain a black colored film having an L ^* value of about 22. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Melamine-based electrodeposition containing 0.02 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm and 0.04 wt% of a red pigment (a red iron oxide) having a particle size of 0.3 μm The anode was immersed in the coating material to form an anode, and a DC voltage of 170 V was applied for 120 seconds to form a 13 μm coating on the surface. After that, bake and dry at 185 ° C for 30 minutes,
A gray-colored composite film with low chroma was obtained.

The results of measuring the color of this sample with a colorimeter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 34.6, a ^* value = 0.4, b ^* value = 1.1 Base color: L ^* value = 22.2, a ^* value = 0.1, b ^* value =
The colorimetric values of the 0.2 samples are almost the same as in Example 1, and it can be seen that even when the electrolytic coloring of the base is colored to black, the surface color of the product is hardly affected. At this time, the color difference between the product surface color and the base color is ΔE ^* ab = 1.
2.4, the chroma difference was ΔC = 0.9, and when the underlying colored oxide film was exposed due to a scratch on the coating film, it became slightly noticeable.

Example 6 An aluminum extruded material A-6063S, which had been degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Melamine-based electrodeposition containing 0.05 wt%, 0.04 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm, and 0.03 wt% of a red pigment (bengala) having a particle size of 0.3 μm The anode was immersed in the coating material to form an anode, and a DC voltage of 170 V was applied for 120 seconds to form a 13 μm coating on the surface. After that, bake and dry at 185 ° C for 30 minutes,
A low-saturation warm gray-colored composite coating was obtained.

The results of measuring the color of this sample with a color difference meter CR-200 manufactured by Minolta Co., Ltd. are described below. Product surface color: L ^* value = 33.2, a ^* value = 0.7, b ^* value = 2.1 Base color: L ^* value = 28.8, a ^* value = 2.7, b ^* value =
3.5 As for the product surface color, both the a ^* value and the b ^* value were between 0 and 3, and the color became a low-saturation warm gray color. At this time, the color difference between the product surface color and the base color is ΔE ^* ab = 5.0, and the chroma difference is ΔC = 2.4. Has become.

COMPARATIVE EXAMPLE 1 Aluminum extruded material A-6063S, which had been degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.05 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Melamine-based electrodeposition containing 0.02 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm and 0.04 wt% of a red pigment (a red iron oxide) having a particle size of 0.3 μm The anode was immersed in the coating material to form an anode, and a DC voltage of 170 V was applied for 120 seconds to form a 13 μm coating on the surface. Thereafter, baking and drying were performed at 185 ° C. for 30 minutes.

The results of measuring the color of this sample with a colorimeter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 27.1, a ^* value = 2.0, b ^* value = 3.8 Base color: L ^* value = 28.9, a ^* value = 2.7, b ^* value =
3.5 Since the concentration of the white pigment in the electrodeposition coating is lower than the range specified in the present invention, the hiding power of the coating is low, and the deep bronze and brown electrodeposition coatings, which are the base colors, are synergized, The color became deeper and more brownish, but not gray.

Comparative Example 2 An aluminum extruded material A-6063S, which had been degreased, etched, and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
In an acrylic melamine-based electrodeposition paint containing 2 wt%, 0.04 wt% of a yellow pigment (yellow iron oxide) having a particle size of 0.3 μm, and 0.03 wt% of a red pigment (bengala) having a particle size of 0.3 μm. To a positive electrode, and apply a DC voltage of 170 V to 12
Electric current was applied for 0 seconds to form a 13 μm coating on the surface.
Thereafter, baking and drying were performed at 185 ° C. for 30 minutes.

The results of measuring the color of this sample with a color difference meter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 23.7, a ^* value = 0.6, b ^* value = 0.8 Base color: L ^* value = 28.9, a ^* value = 2.6, b ^* value =
3.5 Since the concentration of the black pigment in the electrodeposition paint is higher than the range specified in the present invention, both the a ^* value and the b ^* value are almost 0, but almost black, and cannot be said to be gray. It became a color tone.

Comparative Example 3 An aluminum extruded material A-6063S, which had been degreased, etched and smut-removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode, and was placed between an aluminum cathode provided as a counter electrode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Is immersed in an acrylic melamine-based electrodeposition paint containing 0.01% by weight of a blue pigment (phthalocyanine blue) having a wavelength of 470 nm with a light reflectance peak of 0.02% by weight, a particle size of 0.3 μm and an anode. , 170 V DC voltage was applied for 120 seconds to form a 13 μm coating on the surface. Thereafter, baking and drying were performed at 185 ° C. for 30 minutes.

The results of measuring the color of this sample with a color difference meter CR-200 manufactured by Minolta Co., Ltd. are described below. Product surface color: L ^* value = 35.2, a ^* value = -1.0, b ^*
Value = -6.2 Base color: L ^* value = 29.0, a ^* value = 2.7, b ^* value =
3.4 Since the toning pigment added to the electrodeposition paint is a blue pigment (phthalocyanine blue) having a light reflectance peak at a wavelength of 470 nm, the bluish color becomes strong and a low chroma gray color is obtained. Did not become. At this time, the color difference between the product surface color and the base color is ΔE ^* ab = 12.0, and the saturation difference is ΔC =
10.3, when the underlying oxide film was exposed due to the coating film flaw, it became very noticeable.

Comparative Example 4 An aluminum extruded material A-6063S, which was degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface. Next, this is washed with water, and further, nickel sulfate 50 is added.
g / L, 10 g / L boric acid in an electrolytic coloring solution
An AC voltage of 8 V was applied for 8 minutes to obtain a dark bronze colored film having an L ^* value of about 29. Next, 0.2 wt% of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle size of 0.3 μm was used.
%, Black pigment with a particle size of 0.05 μm (carbon black)
Was immersed in an acrylic melamine-based electrodeposition paint containing 0.02% by weight of the same as an anode, and a direct current voltage of 170 V was supplied for 120 seconds to form a 13 μm coating film on the surface. Thereafter, baking and drying were performed at 185 ° C. for 30 minutes to obtain a low-chroma gray composite coloring film.

The results of measuring the color of this sample with a color difference meter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 34.4, a ^* value = 0.1, b ^* value = -2.0 Base color: L ^* value = 29.0, a ^* value = 2.7, b ^* value =
3.6 Since the toning pigment was not added to the electrodeposition paint, the b ^* value was a negative value (blue direction) although the saturation was low,
The color was not the warm gray color obtained in the present invention, but was a cool gray color.

Comparative Example 5 An aluminum extruded material A-6063S, which had been degreased, etched and smut removed by a conventional method, was immersed in a 17 W / V% sulfuric acid aqueous solution to form an anode, and was placed between an aluminum cathode provided as a counter electrode. 30 at a current density of ² A / dm ²
An electric current was applied for a minute to form an anodic oxide film of about 10 μm on the surface, and a silver film having an L ^* value of about 86 was obtained. Next, 0.2% by weight of a white pigment (titanium dioxide) having a resin solid content of 9% and a particle diameter of 0.3 μm, 0.02% by weight of a black pigment (carbon black) having a particle diameter of 0.05 μm, and a particle diameter of 0% 0.3 μm
0.04 wt% of yellow pigment (yellow iron oxide) with a particle size of 0.3
immersion in an acrylic melamine-based electrodeposition paint containing 0.03 wt% of red pigment
A DC voltage of 0 V is applied for 120 seconds, and 13 μm
Was formed. Thereafter, baking and drying were performed at 185 ° C. for 30 minutes.

The results of measuring the color of this sample with a colorimeter CR-200 manufactured by Minolta Co., Ltd. are shown below. Product surface color: L ^* value = 44.5, a ^* value = 3.1, b ^* value = 6.9 Base color: L ^* value = 86.2, a ^* value = −0.1, b ^* value =
0.2 It is possible to increase the variation of product colors by using a silver film as the underlayer, but the color tone of the composite film is a brownish color tone of the film itself, not a low-saturation gray . At this time, the color difference between the product surface color and the base color is ΔE ^* ab = 42.5, the chroma difference is ΔC = 7.4, and when the base oxide film is exposed due to the coating film flaw,
It became very noticeable.

Table 1 shows the processing conditions and results of Examples 1 to 6, and Table 2 shows the processing conditions and results of Comparative Examples 1 to 5.

[Table 1]

[0048]

[Table 2]

[0049]

As described above, according to the method of the present invention,
The combination of the black-bronze-colored anodized film and the brown-semi-transparent coated film formed on it forms a low-saturation, warm-colored, gray-colored anodized paint composite film. can get. In the case of such a combination, there is almost no influence of the coloring degree and the color tone of the electrolytic coloring which may occur in production, and by changing the coloring degree of the electrolytic coloring, it is possible to have a color variation as a product. There is an effect that there is. The color difference between the colored anodized film and the surface of the composite film is ΔE ^* ab of 8
In the case where the difference is less than or equal to 4 and the difference in chroma is 4 or less, an advantage is obtained in that even if the coating film is scratched, the scratches become less noticeable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C25D 11/22 306 C25D 11/22 306A 13/00 13/00 P 13/20 13/20 A F term ( Reference) 4D075 BB67X BB89Y DB07 EA43 EB16 EB22 EB33 EB35 EC11 EC53 EC54

Claims (4)

[Claims] An anodic oxide film colored black to bronze, and a film having a particle size of 0.1
0.15 wt% of white pigment of not less than μm and less than 0.5 μm
0.5 wt% and particle size 0.01 μm
It contains 0.01 to 0.3 wt% of a 0.5 μm black pigment, and has a particle size of 0.01 to 0.5 μm and a wavelength of 5 μm.
A low-saturation film comprising a brownish translucent coating film produced using a brownish translucent paint containing 0.01 wt% to 0.3 wt% of a pigment having a light reflectance peak at 70 nm to 700 nm. An aluminum material or an aluminum alloy material having a warm gray composite film. 2. The colored anodized film according to claim 1, wherein the color difference from the surface color of the composite film is not more than 8 in ΔE ^* ab and the difference in saturation is not more than 4 in ΔC. An aluminum material or an aluminum alloy material as described above. 3. An anodized film is formed on an aluminum material or an aluminum alloy material and is colored black to bronze by an electrolytic coloring method.
As described above, 0.15 wt% or less of the white pigment having a size of less than 0.5 μm
0.5 wt%, and the particle size is 0.01 μm to 0.1 μm.
It contains 0.01 to 0.3 wt% of a 5 μm black pigment, and has a particle size of 0.01 to 0.5 μm and a wavelength of 57 μm.
Low-color warm color system characterized by applying an electrodeposition coating using a brownish translucent paint containing 0.01 wt% to 0.3 wt% of a pigment having a light reflectance peak at 0 nm to 700 nm. A method for producing an aluminum material or an aluminum alloy material having a gray composite coating. 4. The anodic oxide film colored by the electrolytic coloring method is characterized in that the color difference from the surface color of the composite film is ΔE ^* ab of 8 or less and the chroma difference is ΔC of 4 or less. The method according to claim 3.