JP2002212788A - Aluminum material and aluminum alloy material having gray-colored combined coating film, and production method therefor - Google Patents
Aluminum material and aluminum alloy material having gray-colored combined coating film, and production method thereforInfo
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- JP2002212788A JP2002212788A JP2001013138A JP2001013138A JP2002212788A JP 2002212788 A JP2002212788 A JP 2002212788A JP 2001013138 A JP2001013138 A JP 2001013138A JP 2001013138 A JP2001013138 A JP 2001013138A JP 2002212788 A JP2002212788 A JP 2002212788A
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、グレー系色複合皮
膜を有するアルミニウム材及びアルミニウム合金材並び
にその製造方法に関し、さらに詳しくは、アルミニウム
材及びアルミニウム合金材に、耐食性、耐候性、装飾性
を損なうことなく、電解着色と電着塗装により低彩度の
暖色系グレー色を有する陽極酸化塗装複合皮膜を生成さ
せる電着塗装方法及び電着塗装物に関するものである。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】[0002]
【従来の技術】アルミニウム材及びアルミニウム合金材
の着色方法には、合金発色法、電解発色法、二次電解着
色法、三次電解着色法、染色法、塗装法等があるが、耐
食性や耐候性等の性能面やコスト面、さらには製造上の
安定性等の問題から、一般的には二次電解着色法が使用
されている。しかしながら、二次電解着色法による着色
はアンバー色、ブロンズ色、ブラック色等の黄味系統か
ら茶系統の発色に限られ、低彩度のグレー系色の発色は
困難である。ところが、近年では、建材あるいはエクス
テリア関係において、落ち着いたグレー系色の商品の要
望が高まってきており、低コストかつ耐食性や耐候性等
の性能面も良好なグレー系色の商品の開発が望まれてい
た。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】アルミニウム材及びアルミニウム合金材の
グレー系着色法としては、合金組成に発色因子を持たせ
ることにより陽極酸化皮膜生成過程でグレー系に発色さ
せる合金発色法や、陽極酸化皮膜の構造を制御してグレ
ーに発色させる電解発色法、また陽極酸化皮膜生成工程
と金属塩による電解着色工程の間にさらに電解工程を行
なう三次電解着色法、染色法、静電塗装法、粉体塗装法
等が挙げられるが、これらの手法はいずれもコスト面や
製造上の安定性や性能面での制約が多く、ポピュラーな
手法にはなり得ていない。[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.
【0004】近年、低コストかつ耐食性や耐候性等の性
能面も良好なグレー系色の着色法として、不透明有色電
着塗装によるグレー系色着色法、及び二次電解着色によ
る下地色と半透明有色電着塗装との組み合わせによるグ
レー系色着色法が開発されている。前者の不透明有色電
着塗装による着色は、色の安定性は高いものの、電着塗
料そのものの色が固定されてしまい、色替えを行なうに
は塗料そのものを変更しなくてはならず、汎用性の少な
い手法である。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.
【0005】一方、後者の二次電解着色による下地色と
半透明有色電着塗装の組み合わせによる手法は、例えば
特許第2938781号公報には、黒色陽極酸化皮膜の
下地と、粒径0.5μm〜10μmの白色顔料を0.0
1wt%〜0.5wt%含有する電着塗料による白色塗
膜の組み合わせにより、青系グレー色の複合皮膜を形成
する方法が開示されている。また、特開平11−106
994号公報には、L*値=30以上の陽極酸化皮膜上
に、樹脂固形分に対して0.7〜1.2wt%の白色顔
料と0.03〜0.08wt%の黒色顔料を含有する半
透明の灰色塗料を用いて電着塗装を施すことで、無彩色
グレーを得る方法が開示されている。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.
【0006】しかしながら、この様な二次電解着色によ
る下地色と半透明有色電着塗装の組み合わせによる着色
方法では、 (1)下地の二次電解着色時における諸条件のバラツキ
に起因する着色度あるいは色調のバラツキ (2)半透明有色電着塗膜の膜厚や顔料濃度のバラツキ
に起因する塗膜の透明感や色調のバラツキ が発生し、それらが相乗しあうことで複合皮膜の表面色
がさらに大きくバラツキを生じる為、色の安定性という
面では非常に管理が困難な着色法であるといえる。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.
【0007】また、上記特許第2938781号公報及
び特開平11−106994号公報においては、下地が
ブラック色や濃ブロンズ色の場合、色調が青系の寒色系
に固定されてしまい、本発明で求める暖色系グレー色と
はなりえない。さらに、この様な二次電解着色による下
地色と半透明有色電着塗装の組み合わせによる着色方法
であっても、塗膜にキズが付いた場合、不透明有色電着
塗装によるグレー着色の場合と同様に、仮にそのキズが
微小面積であっても全く異なる色調の陽極酸化皮膜下地
が現われ、一般の複合皮膜商品よりもキズが目立ち易く
なるという欠点がある。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】[0008]
【発明が解決しようとする課題】本発明は、アルミニウ
ム材及びアルミニウム合金材の陽極酸化塗装複合皮膜に
おける前述したような従来の問題を解決すべくなされた
ものであり、実際の製造時に生じると予想される程度の
下地の着色のバラツキや塗膜厚のバラツキではほとんど
影響を受けず、かつ製品色のバリエーションを持つこと
が可能であり、さらには塗膜キズが目立ち難い低彩度の
暖色系グレー色の陽極酸化塗装複合皮膜を有するアルミ
ニウム材及びアルミニウム合金材並びにその製造方法を
提供することを目的としている。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】[0009]
【課題を解決するための手段】前記目的を達成するため
に、本発明によれば、ブラック〜ブロンズ色に着色した
陽極酸化皮膜と、該陽極酸化皮膜上に成膜され、粒径が
0.1μm以上、0.5μm未満の白色顔料を0.15
wt%〜0.5wt%含有し、さらに粒径が0.01μ
m〜0.5μmの黒顔料を0.01wt%〜0.3wt
%含有し、さらに粒径が0.01μm〜0.5μmで波
長570nm〜700nmに光線反射率のピークを有す
る顔料を0.01wt%〜0.3wt%含有する茶褐色
系の半透明塗料を用いて生成された茶褐色系の半透明塗
膜とからなる低彩度の暖色系グレー色複合皮膜を有する
ことを特徴とするアルミニウム材又はアルミニウム合金
材が提供される。好適な態様によれば、着色した陽極酸
化皮膜は、複合皮膜表面色との色差がΔE*abで8以
下で、かつ彩度の差がΔCで4以下である。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.
【0010】さらに本発明によれば、アルミニウム材又
はアルミニウム合金材に、陽極酸化皮膜を形成させ、電
解着色法によりブラック〜ブロンズ色に着色し、しかる
後、粒径が0.1μm以上、0.5μm未満の白色顔料
を0.15wt%〜0.5wt%含有し、さらに粒径が
0.01μm〜0.5μmの黒顔料を0.01wt%〜
0.3wt%含有し、さらに粒径が0.01μm〜0.
5μmで波長570nm〜700nmに光線反射率のピ
ークを有する顔料を0.01wt%〜0.3wt%含有
する茶褐色系の半透明塗料を用いて電着塗装を施すこと
を特徴とする、低彩度の暖色系グレー色複合皮膜を有す
るアルミニウム材又はアルミニウム合金材の製造方法が
提供される。好適な態様においては、電解着色法により
着色した陽極酸化皮膜と複合皮膜表面色との色差がΔE
*abで8以下で、かつ彩度の差がΔCで4以下となる
ように調整される。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.
【0011】本明細書で言うところの低彩度の暖色系グ
レー色とは、L*a*b*表色系(CIE 1976)
(JIS Z8729)の内の明度を示すL*値が33
以上であり、また彩度を示すa*値、b*値(a*値がプ
ラスの場合は赤味方向、マイナスの場合は緑味方向、b
*値がプラスの場合は黄味方向、マイナスの場合は青味
方向の色調)がそれぞれ0以上、3以下の色調のものを
言う。また、本明細書で言うところのブラック〜ブロン
ズ色とは、22〜50のL*値を有する濃さを指す。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.
【0012】さらに、本明細書でいうところの色差ΔE
*ab(CIE 1976)(JIS Z8729)及
び彩度差ΔCは、電解着色された陽極酸化皮膜の測色値
と、さらに本発明の製造方法に従って電着塗装を施した
複合皮膜の表面色の測色値をL*a*b*表色系(CIE
1976)(JIS Z8729)で表わしたとき、
以下の式で表わすものとする。すなわち、電解着色され
た陽極酸化皮膜の測色値をL1、a1、b1、複合皮膜の
表面色の測色値をL2、a2、b2とすると、 色差ΔE*ab=[(L1−L2)2+(a1−a2)2+
(b1−b2)2]1/2 彩度差ΔC=[(a1−a2)2+(b1−b2)2]1/2 で表わされる。但し、彩度差については、一般的に用い
られる「CIE 1976」あるいは「JIS Z87
29」で定めるところのΔC*ab=(a1 2+b1 2)1/2
−(a 2 2+b2 2)1/2では色相の違いが数値として現わ
れないため、本明細書では彩度差をΔC=[(a1−
a2)2+(b1−b2)2]1/2として表わすものとする。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 LTwo, ATwo, BTwoThen, the color difference ΔE*ab = [(L1-LTwo)Two+ (A1-ATwo)Two+
(B1-BTwo)Two]1/2 Saturation difference ΔC = [(a1-ATwo)Two+ (B1-BTwo)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+ BTwo Two)1/2Then the difference in hue appears as a numerical value
Therefore, in this specification, the saturation difference is represented by ΔC = [(a1−
aTwo)Two+ (B1-BTwo)Two]1/2Shall be expressed as
【0013】[0013]
【発明の実施の形態】本発明者らは、前記した課題を解
決すべく鋭意研究の結果、ブラック〜ブロンズ色に着色
された陽極酸化皮膜と、その上に成膜された茶褐色半透
明に調整された塗膜との組合わせによって、低彩度の暖
色系グレー色の陽極酸化塗装複合皮膜が得られること、
このような組合わせの場合、生産上起こり得る電解着色
の着色度や色調のバラツキの影響をほとんど受けず、し
かも電解着色の着色度を変化させることで商品として色
のバリエーションをもつことが可能であることを見出し
た。また、下地のブラック〜ブロンズ色に着色された陽
極酸化皮膜上に茶褐色半透明の塗膜が成膜されている場
合、特に着色陽極酸化皮膜の複合皮膜表面色との色差が
ΔE*abで8以下で、かつ彩度の差がΔCで4以下で
ある場合には、塗膜にキズが付いても目立ち難くなると
いうことも見出した。さらに、このような茶褐色半透明
の塗膜は、粒径が0.1μm以上、0.5μm未満の白
色顔料を0.15wt%〜0.5wt%、粒径が0.0
1μm〜0.5μmの黒顔料を0.01wt%〜0.3
wt%、さらに粒径が0.01μm〜0.5μmで波長
570nm〜700nmに光線反射率のピークを有する
顔料を0.01wt%〜0.3wt%含有する茶褐色系
の半透明塗料を用いることによって成膜できることを見
出し、本発明を完成するに至ったものである。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.
【0014】以下、本発明の方法について詳しく説明す
ると、まず、アルミニウム材及びアルミニウム合金材に
陽極酸化皮膜を形成させる方法、さらにその陽極酸化皮
膜をブラック〜ブロンズ色に着色する処理方法について
は、前記した特定の顔料を含有する塗料を用いることを
除けば、一般的な既知の方法により実施できる。すなわ
ち、陽極酸化皮膜を形成させる工程においては、その電
解液に硫酸、燐酸、クロム酸、蓚酸等の無機酸や有機
酸、あるいはそれらの混酸を使用することができる。そ
の電解液中において、アルミニウム材又はアルミニウム
合金材を陽極とし、直流電流、パルス電流、交直重畳電
流、あるいは交流電流等を通電することで、6μm〜3
0μmのポーラスな陽極酸化皮膜を形成させる。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.
【0015】次に、陽極酸化皮膜下地の着色において
は、二次電解着色法、三次電解着色法、電解発色法、合
金発色法、染色法等、多岐にわたる着色法が適用できる
が、経済性や生産の安定性等を考慮すると、好ましくは
一般的な二次電解着色法が有効である。この二次電解着
色法においては、ニッケル塩、スズ塩、コバルト塩、等
の金属塩や各種有機酸、硫黄化合物等を含む電解着色液
中で、前述の陽極酸化皮膜を形成させたアルミニウム材
又はアルミニウム合金材に交流電流、直流電流、交直重
畳電流、パルス電流等を通電することでブラック〜ブロ
ンズ色に着色を行なう。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.
【0016】しかる後、前述したような電着塗料、すな
わち粒径が0.1μm以上、0.5μm未満の白色顔料
を0.15wt%〜0.5wt%含有し、さらに粒径が
0.01μm〜0.5μmの黒顔料を0.01wt%〜
0.3wt%含有し、さらに粒径が0.01μm〜0.
5μmで波長570nm〜700nmに光線反射率のピ
ークを有する顔料を0.01wt%〜0.3wt%含有
する茶褐色系の半透明塗料を用い、前述の着色陽極酸化
皮膜上に半透明の電着塗膜を5μm〜30μm形成する
ことで、低彩度の暖色系グレー色に発色させる。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.
【0017】本発明において、この茶褐色系の半透明塗
料に使用されるベースとなる電着塗料は、アルミニウム
材及びアルミニウム合金材上の陽極酸化皮膜上に電着塗
装できるタイプの塗料であれば特に限定されることはな
く、一般的なアクリルメラミン樹脂をはじめ、エポキシ
エステル樹脂系、ポリエステル樹脂系、フッ素樹脂系等
の、透明系あるいは半透明系の艶有り塗料もしくは艶消
し塗料を用いることができる。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. .
【0018】このベース塗料中に、粒径0.1μm以
上、0.5μm未満に調整された白色顔料(二酸化チタ
ン、鉛白、亜鉛華、酸化ジルコニウム等の1種又は2種
以上)を0.15wt%〜0.5wt%、粒径が0.0
1μm〜0.5μmの黒顔料を0.01wt%〜0.3
wt%、さらに粒径が0.01μm〜0.5μmで波長
570nm〜700nmに光線反射率のピークを有する
顔料を0.01wt%〜0.3wt%添加して茶褐色系
の半透明塗料に調製して使用する。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.
【0019】ここで白色顔料は、粒径が0.5μm以上
のものを使用した場合、顔料分の凝集による沈降が発生
し易く、液の安定性を保つことが難しくなるため、顔料
の粒径を0.5μm未満に調整する必要がある。同様の
理由から、黒顔料及び波長570nm〜700nmに光
線反射率のピークを有する顔料についても、0.5μm
以下に調整する必要がある。なお、白色顔料の粒径は、
好ましくは0.2μm〜0.4μmに調整することが望
ましい。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.
【0020】また、白色顔料の濃度が、下限値の0.1
5wt%を下回った場合、塗膜隠蔽性が極端に低くな
り、下地である着色陽極酸化皮膜の色の影響が強く現わ
れてしまい、電解着色の着色度や色調のバラツキがその
まま複合皮膜色のバラツキとして生じる。このような低
濃度で前述の効果を得ようとした場合、その隠蔽性を確
保する為に、極端な塗膜厚を形成させなくてはならず、
塗膜の安定性、さらには経済性でも問題が生じる。また
この場合、後述する調色用顔料(本明細書においては、
黒顔料及び波長570nm〜700nmに光線反射率の
ピークを有する顔料の意)で隠蔽性を確保しようとする
と、調色用顔料を必要以上に添加しなくてはならず、本
発明で求めるL*値が33以上の低彩度暖色系グレー色
とはならない。一方、上限値0.5wt%を超えた場
合、塗膜の耐候性がやや劣る傾向にあり、さらには、隠
蔽性が高くなりすぎて不透明塗膜に近くなるため、下地
の電解着色の着色度を極端に変化させても複合皮膜とし
ての発色に変化を生じさせることができなくなり、商品
として色のバリエーションを得ることができなくなる。
本発明では、以上のことを考慮し、白色顔料濃度は0.
15wt%〜0.5wt%に、好ましくは0.18wt
%〜0.3wt%に調整する。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%.
【0021】調色用顔料については、粒径が0.01μ
m〜0.5μmの黒顔料を0.01wt%〜0.3wt
%添加し、さらに粒径が0.01μm〜0.5μmで波
長570nm〜700nmに光線反射率のピークを有す
る顔料を0.01wt%〜0.3wt%添加する。本発
明においては、調色用顔料として、黒顔料であれば例え
ばカーボンブラックや鉄黒等、また波長570nm〜7
00nmに光線反射率のピークを有する顔料としては、
例えば黄顔料であれば黄酸化鉄、亜鉛黄、イソインドレ
ノン等、赤顔料であれば鉛丹、ベンガラ、キナクリドン
等の無機系顔料、有機系顔料を、それぞれ単独であるい
は2種以上を混合して用いることができる。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.
【0022】また、調色用顔料の濃度は、前記下限値を
下回った場合、その顔料による発色がほとんど感知でき
ない、あるいは測定結果に現われず、添加の効果が著し
く低くなる。一方、前記上限値を超えた場合、その調色
用顔料による発色が強く、明度が低くなりすぎてブラッ
ク色になったり、あるいは特定の色味が強調され、彩度
が高くなりすぎてグレー系色とは質感を異にするように
なる。本発明では、以上のことを考慮し、添加する粒径
が0.01μm〜0.5μmの黒顔料の濃度を0.01
wt%〜0.3wt%、好ましくは0.02wt%〜
0.1wt%に調整し、さらに粒径が0.01μm〜
0.5μmで波長570nm〜700nmに光線反射率
のピークを有する顔料の濃度を0.01wt%〜0.3
wt%、好ましくは0.02wt%〜0.2wt%に調
整する。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】上述のように茶褐色半透明に調整された電
着塗料を、ブラック〜ブロンズ色に着色された陽極酸化
皮膜と組み合わせることで、生産上起こり得る電解着色
の着色度や色調のバラツキの影響をほとんど受けず、し
かしながら電解着色の着色度を極端に変化させることで
商品として色のバリエーションをもつことが可能な、低
彩度の暖色系グレー色の陽極酸化塗装複合皮膜を得るこ
とができる。[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】[0024]
【実施例】以下、実施例及び比較例を示して本発明につ
いてさらに具体的に説明するが、本発明が下記実施例に
限定されるものでないことはもとよりである。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.
【0025】実施例1 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%、粒径が0.3μmの黄顔料(黄酸化
鉄)を0.04wt%、粒径が0.3μmの赤顔料(ベ
ンガラ)を0.03wt%含有するアクリルメラミン系
電着塗料中に浸漬して陽極とし、170Vの直流電圧を
120秒通電し、その表面に13μmの塗膜を形成させ
た。その後、185℃で30分焼き付け乾燥を行ない、
低彩度のグレー発色複合皮膜が得られた。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.
【0026】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=34.9、a*値=0.5、b*値
=1.3 下地色:L*値=29.2、a*値=2.8、b*値=
3.6 製品表面色はa*値、b*値が共に0〜3の間にあり、低
彩度の暖色系グレー色となった。また、このときの製品
表面色と下地色との色差はΔE*ab=6.5、彩度差
はΔC=3.3となり、塗膜キズにより下地の着色酸化
皮膜が露出した場合でも目立ち難くなっている。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.
【0027】実施例2 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を7分通電し、L*値=約33の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%、粒径が0.3μmの黄顔料(黄酸化
鉄)を0.04wt%、粒径が0.3μmの赤顔料(ベ
ンガラ)を0.03wt%含有するアクリルメラミン系
電着塗料中に浸漬して陽極とし、170Vの直流電圧を
120秒通電し、その表面に13μmの塗膜を形成させ
た。その後、185℃で30分焼き付け乾燥を行ない、
暖色系のグレー発色複合皮膜が得られた。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.
【0028】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=35.0、a*値=0.5、b*値
=1.4 下地色:L*値=33.1、a*値=3.9、b*値=
6.7 サンプルの測色値は実施例1とほとんど同じとなり、下
地の電解着色において製造上起こり得る多少のバラツキ
が生じても製品の表面色にはほとんど影響を与えないこ
とがわかる。また、このときの製品表面色と下地色との
色差はΔE*ab=6.6、彩度差はΔC=6.3とな
り、塗膜キズにより下地の着色酸化皮膜が露出した場合
に若干目立ち易くなった。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.
【0029】実施例3 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%、粒径が0.3μmの黄顔料(黄酸化
鉄)を0.04wt%、粒径が0.3μmの赤顔料(ベ
ンガラ)を0.03wt%含有するアクリルメラミン系
電着塗料中に浸漬して陽極とし、190Vの直流電圧を
120秒通電し、その表面に17μmの塗膜を形成させ
た。その後、185℃で30分焼き付け乾燥を行ない、
暖色系のグレー発色複合皮膜が得られた。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.
【0030】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=35.2、a*値=0.6、b*値
=1.4 下地色:L*値=29.1、a*値=2.7、b*値=
3.5 サンプルの測色値は実施例1とほとんど同じとなり、塗
膜厚において製造上起こり得るバラツキが生じても製品
の表面色にはほとんど影響を与えないことがわかる。ま
た、このときの製品表面色と下地色との色差はΔE*a
b=6.8、彩度差はΔC=3.0となり、塗膜キズに
より下地の着色酸化皮膜が露出した場合でも目立ち難く
なっている。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.
【0031】実施例4 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
6Vの交流電圧を6分通電し、L*値=約50のブロン
ズの着色皮膜を得た。次に、樹脂固形分9%、粒径0.
3μmの白色顔料(二酸化チタン)を0.2wt%、粒
径が0.05μmの黒顔料(カーボンブラック)を0.
02wt%、粒径が0.3μmの黄顔料(黄酸化鉄)を
0.04wt%、粒径が0.3μmの赤顔料(ベンガ
ラ)を0.03wt%含有するアクリルメラミン系電着
塗料中に浸漬して陽極とし、170Vの直流電圧を12
0秒通電し、その表面に13μmの塗膜を形成させた。
その後、185℃で30分焼き付け乾燥を行ない、低彩
度のグレー発色複合皮膜が得られた。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.
【0032】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=38.5、a*値=1.9、b*値
=2.9 下地色:L*値=49.7、a*値=3.5、b*値=1
5.1 半透明電着塗膜の為、下地の着色度を極端に変えること
により、彩度がやや高くなるが、a*値、b*値の絶対値
が共に0〜3の間にある暖色系のグレー色となり、また
明度が上がることで実施例1と比較し商品としてあきら
かに違う色のバリエーションとして認識できる色調とな
った。このときの製品表面色と下地色との色差はΔE*
ab=16.7、彩度差はΔC=12.3となり、塗膜
キズにより下地の着色酸化皮膜が露出した場合、目立ち
易くなった。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.
【0033】実施例5 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を12分通電し、L*値=約22のブラ
ックの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%、粒径が0.3μmの黄顔料(黄酸化
鉄)を0.04wt%、粒径が0.3μmの赤顔料(ベ
ンガラ)を0.03wt%含有するアクリルメラミン系
電着塗料中に浸漬して陽極とし、170Vの直流電圧を
120秒通電し、その表面に13μmの塗膜を形成させ
た。その後、185℃で30分焼き付け乾燥を行ない、
低彩度のグレー発色複合皮膜が得られた。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.
【0034】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=34.6、a*値=0.4、b*値
=1.1 下地色:L*値=22.2、a*値=0.1、b*値=
0.2 サンプルの測色値は実施例1とほとんど同じとなり、下
地の電解着色がブラック色まで着色された場合でも製品
の表面色にはほとんど影響を与えないことがわかる。こ
のときの製品表面色と下地色との色差はΔE*ab=1
2.4、彩度差はΔC=0.9となり、塗膜キズにより
下地の着色酸化皮膜が露出した場合、若干目立ち易くな
った。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.
【0035】実施例6 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.05wt%、粒径が0.3μmの黄顔料(黄酸化
鉄)を0.04wt%、粒径が0.3μmの赤顔料(ベ
ンガラ)を0.03wt%含有するアクリルメラミン系
電着塗料中に浸漬して陽極とし、170Vの直流電圧を
120秒通電し、その表面に13μmの塗膜を形成させ
た。その後、185℃で30分焼き付け乾燥を行ない、
低彩度の暖色系グレー発色複合皮膜が得られた。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.
【0036】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=33.2、a*値=0.7、b*値
=2.1 下地色:L*値=28.8、a*値=2.7、b*値=
3.5 製品表面色はa*値、b*値が共に0〜3の間にあり、低
彩度の暖色系グレー色となった。また、このときの製品
表面色と下地色との色差はΔE*ab=5.0、彩度差
はΔC=2.4となり、塗膜キズにより下地の着色酸化
皮膜が露出した場合でも目立ち難くなっている。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.
【0037】比較例1 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.05wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%、粒径が0.3μmの黄顔料(黄酸化
鉄)を0.04wt%、粒径が0.3μmの赤顔料(ベ
ンガラ)を0.03wt%含有するアクリルメラミン系
電着塗料中に浸漬して陽極とし、170Vの直流電圧を
120秒通電し、その表面に13μmの塗膜を形成させ
た。その後、185℃で30分焼き付け乾燥を行なっ
た。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.
【0038】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=27.1、a*値=2.0、b*値
=3.8 下地色:L*値=28.9、a*値=2.7、b*値=
3.5 電着塗料中の白色顔料の濃度が本発明で規定する範囲よ
りも低いため、塗膜の隠蔽力が低く、下地色である濃ブ
ロンズ色と褐色の電着塗膜が相乗され、さらに濃く褐色
感が強い色調となり、グレー色とはならなかった。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.
【0039】比較例2 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を2wt%、粒径が0.3μmの黄顔料(黄酸化鉄)を
0.04wt%、粒径が0.3μmの赤顔料(ベンガ
ラ)を0.03wt%含有するアクリルメラミン系電着
塗料中に浸漬して陽極とし、170Vの直流電圧を12
0秒通電し、その表面に13μmの塗膜を形成させた。
その後、185℃で30分焼き付け乾燥を行なった。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.
【0040】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=23.7、a*値=0.6、b*値
=0.8 下地色:L*値=28.9、a*値=2.6、b*値=
3.5 電着塗料中の黒顔料の濃度が本発明で規定する範囲より
も高いため、a*値、b*値が共にほぼ0に近いが、ほと
んどブラック色となり、グレー色とは言えない色調とな
った。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.
【0041】比較例3 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%、粒径が0.3μmで光線反射率のピ
ークが波長470nmに存在する青顔料(フタロシアニ
ンブルー)を0.01wt%含有するアクリルメラミン
系電着塗料中に浸漬して陽極とし、170Vの直流電圧
を120秒通電し、その表面に13μmの塗膜を形成さ
せた。その後、185℃で30分焼き付け乾燥を行なっ
た。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.
【0042】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=35.2、a*値=−1.0、b*
値=−6.2 下地色:L*値=29.0、a*値=2.7、b*値=
3.4 電着塗料中に添加した調色用顔料が、光線反射率のピー
クが波長470nmに存在する青顔料(フタロシアニン
ブルー)であるため、青味が強い色調となり、低彩度の
グレー色とはならなかった。このときの製品表面色と下
地色との色差はΔE*ab=12.0、彩度差はΔC=
10.3となり、塗膜キズにより下地の酸化皮膜が露出
した場合、非常に目立ち易くなった。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.
【0043】比較例4 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させた。次いでこれを水洗し、さらに硫酸ニッケル50
g/L、ホウ酸10g/Lを溶解した電解着色液中で1
8Vの交流電圧を8分通電し、L*値=約29の濃ブロ
ンズの着色皮膜を得た。次に、樹脂固形分9%、粒径
0.3μmの白色顔料(二酸化チタン)を0.2wt
%、粒径が0.05μmの黒顔料(カーボンブラック)
を0.02wt%含有するアクリルメラミン系電着塗料
中に浸漬して陽極とし、170Vの直流電圧を120秒
通電し、その表面に13μmの塗膜を形成させた。その
後、185℃で30分焼き付け乾燥を行ない、低彩度の
グレー発色複合皮膜が得られた。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.
【0044】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=34.4、a*値=0.1、b*値
=−2.0 下地色:L*値=29.0、a*値=2.7、b*値=
3.6 電着塗料中に調色用顔料が添加されていないため、低彩
度ではあるがb*値がマイナス値(青味方向)であり、
本発明で求めるところの暖色系グレー色とはならず、寒
色系のグレー色となった。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.
【0045】比較例5 常法により脱脂、エッチング、スマット除去されたアル
ミニウム押出材A−6063Sを17W/V%硫酸水溶
液中に浸漬して陽極とし、対極として設けられたアルミ
ニウム陰極との間に1.2A/dm2の電流密度で30
分通電し、その表面に約10μmの陽極酸化皮膜を形成
させ、L*値=約86のシルバー皮膜を得た。次に、樹
脂固形分9%、粒径0.3μmの白色顔料(二酸化チタ
ン)を0.2wt%、粒径が0.05μmの黒顔料(カ
ーボンブラック)を0.02wt%、粒径が0.3μm
の黄顔料(黄酸化鉄)を0.04wt%、粒径が0.3
μmの赤顔料(ベンガラ)を0.03wt%含有するア
クリルメラミン系電着塗料中に浸漬して陽極とし、17
0Vの直流電圧を120秒通電し、その表面に13μm
の塗膜を形成させた。その後、185℃で30分焼き付
け乾燥を行なった。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.
【0046】このサンプルをミノルタ(株)製色彩色差
計CR-200で測色した結果を以下に記す。 製品表面色:L*値=44.5、a*値=3.1、b*値
=6.9 下地色:L*値=86.2、a*値=−0.1、b*値=
0.2 下地をシルバー皮膜とすることで製品色のバリエーショ
ンを増やすことは可能となるが、複合皮膜の色調は塗膜
そのものの茶褐色系の色調となり、低彩度のグレーには
なっていなかった。このときの製品表面色と下地色との
色差はΔE*ab=42.5、彩度差はΔC=7.4と
なり、塗膜キズにより下地の酸化皮膜が露出した場合、
非常に目立ち易くなった。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.
【0047】前記実施例1〜6の処理条件及び結果を表
1に、また、比較例1〜5の処理条件及び結果を表2に
まとめて示す。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.
【表1】 [Table 1]
【0048】[0048]
【表2】 [Table 2]
【0049】[0049]
【発明の効果】以上のように、本発明の方法によれば、
ブラック〜ブロンズ色に着色された陽極酸化皮膜と、そ
の上に成膜された茶褐色半透明に調整された塗膜との組
合わせによって、低彩度の暖色系グレー色の陽極酸化塗
装複合皮膜が得られる。このような組合わせの場合、生
産上起こり得る電解着色の着色度や色調のバラツキの影
響をほとんど受けず、しかも電解着色の着色度を変化さ
せることで商品として色のバリエーションをもつことが
可能である、という効果が得られる。また、着色した陽
極酸化皮膜の複合皮膜表面色との色差がΔE*abで8
以下で、かつ彩度の差がΔCで4以下である場合、塗膜
にキズが付いても、キズが目立ち難くなるという利点が
得られる。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.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C25D 11/22 306 C25D 11/22 306A 13/00 13/00 P 13/20 13/20 A Fターム(参考) 4D075 BB67X BB89Y DB07 EA43 EB16 EB22 EB33 EB35 EC11 EC53 EC54 ──────────────────────────────────────────────────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)
化皮膜と、該陽極酸化皮膜上に成膜され、粒径が0.1
μm以上、0.5μm未満の白色顔料を0.15wt%
〜0.5wt%含有し、さらに粒径が0.01μm〜
0.5μmの黒顔料を0.01wt%〜0.3wt%含
有し、さらに粒径が0.01μm〜0.5μmで波長5
70nm〜700nmに光線反射率のピークを有する顔
料を0.01wt%〜0.3wt%含有する茶褐色系の
半透明塗料を用いて生成された茶褐色系の半透明塗膜と
からなる低彩度の暖色系グレー色複合皮膜を有すること
を特徴とするアルミニウム材又はアルミニウム合金材。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.
表面色との色差がΔE*abで8以下で、かつ彩度の差
がΔCで4以下であることを特徴とする請求項1に記載
のアルミニウム材又はアルミニウム合金材。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.
に、陽極酸化皮膜を形成させ、電解着色法によりブラッ
ク〜ブロンズ色に着色し、しかる後、粒径が0.1μm
以上、0.5μm未満の白色顔料を0.15wt%〜
0.5wt%含有し、さらに粒径が0.01μm〜0.
5μmの黒顔料を0.01wt%〜0.3wt%含有
し、さらに粒径が0.01μm〜0.5μmで波長57
0nm〜700nmに光線反射率のピークを有する顔料
を0.01wt%〜0.3wt%含有する茶褐色系の半
透明塗料を用いて電着塗装を施すことを特徴とする、低
彩度の暖色系グレー色複合皮膜を有するアルミニウム材
又はアルミニウム合金材の製造方法。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.
皮膜は、複合皮膜表面色との色差がΔE*abで8以下
で、かつ彩度の差がΔCで4以下であることを特徴とす
る請求項3に記載の製造方法。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.
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JP2017057506A (en) * | 2011-09-29 | 2017-03-23 | 電化皮膜工業株式会社 | Colored aluminum product or colored aluminum alloy product |
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US6930840B2 (en) * | 2002-03-22 | 2005-08-16 | Fujinon Corporation | Mechanism element for optical devices |
US7478547B2 (en) | 2003-03-06 | 2009-01-20 | Kabushiki Kaisha Toshiba | Drum washing machine |
JP2010031330A (en) * | 2008-07-30 | 2010-02-12 | Fujisash Co | Surface treatment method for aluminum material and surface-treated aluminum material |
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JP2013082994A (en) * | 2011-09-29 | 2013-05-09 | Denka Himaku Inc | Method for manufacturing colored aluminum product or colored aluminum alloy product, pigment composition for coloration, and colored aluminum product or colored aluminum alloy product |
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CN114867796A (en) * | 2019-12-19 | 2022-08-05 | 巴斯夫涂料有限公司 | Electrodeposition coating composition containing lampblack pigment |
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