JP2937963B2 - Colored aluminum or aluminum alloy - Google Patents
Colored aluminum or aluminum alloyInfo
- Publication number
- JP2937963B2 JP2937963B2 JP26822997A JP26822997A JP2937963B2 JP 2937963 B2 JP2937963 B2 JP 2937963B2 JP 26822997 A JP26822997 A JP 26822997A JP 26822997 A JP26822997 A JP 26822997A JP 2937963 B2 JP2937963 B2 JP 2937963B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- oxide film
- pigment
- colored
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- Application Of Or Painting With Fluid Materials (AREA)
- Printing Plates And Materials Therefor (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、アルミニウム又はアル
ミニウム合金(以下、アルミニウムと称する)の着色体
に関し、さらに詳しくは、アルミニウムの陽極酸化皮膜
の細孔深くに有機顔料やカーボンブラックを析着させ
て、堅牢で鮮やかな着色酸化皮膜を形成する技術に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored body of aluminum or an aluminum alloy (hereinafter referred to as "aluminum"), and more particularly, to an organic pigment or carbon black deposited deep in pores of an anodized aluminum film. And a technique for forming a robust and vivid colored oxide film.
【0002】[0002]
【従来の技術】従来、アルミニウム陽極酸化皮膜の着色
方法としては、各種金属塩の浴を用いての電解着色法を
中心に、無機化合物の浴あるいは有機染料の浴を用いて
の浸漬着色法等、多くの方法が知られている。しかしな
がら、電解着色法では所望の色を容易に得がたく、色の
種類が限定され、また染色法では着色操作は可能ではあ
るが、得られる着色酸化皮膜の耐久性が低いなど、従来
の技術において、建築外装材等に要求される諸耐久性も
満たすような仕様の鮮やかな原色性の着色酸化皮膜を得
ることは、非常に困難とされている。2. Description of the Related Art Conventionally, as a method for coloring an anodized aluminum film, an electrolytic coloring method using a bath of various metal salts, an immersion coloring method using a bath of an inorganic compound or a bath of an organic dye, and the like have been known. Many methods are known. However, in the electrolytic coloring method, it is difficult to obtain a desired color easily, the kind of color is limited, and in the coloring method, although coloring operation is possible, the obtained colored oxide film has low durability such as low durability. It is very difficult to obtain a vivid primary color colored oxide film having specifications satisfying various durability required for building exterior materials and the like.
【0003】このような問題を解決するための一つの方
策として、特公昭52−5010号公報及び特公昭51
−35177号公報には、アルミニウムをリン酸水溶液
中で陽極酸化し、これを水性有機顔料微分散体浴中に浸
漬処理またはさらに通電処理することにより着色する方
法が提案されている。ところで、上記各公報には顔料粒
子のサイズが約1μ(1000nm)前後、好ましくは
0.5μ(500nm)以下の顔料微分散体を用いると
記載されている。また、現在市販されているものは平均
粒子径が200〜300nm位である顔料水分散体であ
る。一方、これを適用する陽極酸化皮膜は、一般に細孔
径が50nm以下位である。したがって、殆どの顔料粒
子が細孔径より大きいため、アルミニウムの着色におい
て、顔料は陽極酸化皮膜の細孔口及び皮膜表面に層状に
吸着積層した形で着色する。そのため、着色・封孔体の
摩擦堅牢性が低く、また顔料の脱離が生じ易いという問
題があり、さらに、上記各公報に記載されているような
樹脂被覆なくしては堅牢な着色体にできないという欠点
がある。As one measure for solving such a problem, Japanese Patent Publication No. 52-5010 and Japanese Patent Publication No.
JP-A-35177 proposes a method of anodizing aluminum in a phosphoric acid aqueous solution and coloring the aluminum by immersion or further energization in an aqueous organic pigment fine dispersion bath. Incidentally, each of the above publications describes that a pigment fine dispersion having a pigment particle size of about 1 μ (1000 nm), preferably 0.5 μ (500 nm) or less is used. Currently commercially available pigment aqueous dispersions having an average particle diameter of about 200 to 300 nm. On the other hand, the anodic oxide film to which this is applied generally has a pore diameter of about 50 nm or less. Therefore, since most of the pigment particles are larger than the pore diameter, in coloring aluminum, the pigment is colored in the form of layered adsorption and lamination on the pore openings of the anodized film and on the film surface. Therefore, there is a problem that the friction / fastness of the coloring / sealing body is low, and there is a problem that detachment of the pigment is apt to occur, and further, it is impossible to form a robust coloring body without resin coating as described in each of the above publications There is a disadvantage that.
【0004】[0004]
【発明が解決しようとする課題】したがって、本発明の
目的は、前記したような従来技術の問題を解決し、アル
ミニウムの多孔質陽極酸化皮膜の細孔深くに顔料を析着
・充填させ、建築外装材等に要求される諸耐久性を満た
すと共に、変・褪色もなく、堅牢で色鮮やかな所望の色
相の着色酸化皮膜を有するアルミニウム着色体を提供す
ることにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to deposit and fill a pigment deep into the pores of a porous anodic oxide film of aluminum. It is an object of the present invention to provide an aluminum colored body having a colored oxide film of a desired hue that is robust and has a vivid color without discoloration or fading, while satisfying various durability required for an exterior material and the like.
【0005】[0005]
【課題を解決するための手段】本発明によれば、前記目
的を達成するために、アルミニウムに形成された細孔径
50〜200nmの多孔質陽極酸化皮膜の細孔の開口部
から孔底にかけて粒子径3〜150nmの有機顔料又は
カーボンブラックが析着されてなる着色酸化皮膜を有す
るアルミニウム着色体が提供される。このようなアルミ
ニウム着色体は、本発明によれば、第一の方法として、
アルミニウムを鉱酸又は有機酸の1種又は2種以上の酸
水溶液中で高電圧で陽極酸化し、該アルミニウムの表面
に通常の50nm以下程度の細孔径より大きい細孔径の
多孔質陽極酸化皮膜を形成させた後、該皮膜の細孔中に
3〜150nmの大きさに微細化した有機顔料又はカー
ボンブラックの水分散体中から電気泳動法によって有機
顔料又はカーボンブラックを泳動・析出させる方法によ
り得られる。さらに第二の方法として、アルミニウムを
鉱酸又は有機酸の1種又は2種以上の酸水溶液中で陽極
酸化し、該アルミニウムの表面に多孔質陽極酸化皮膜を
形成させた後、リン酸、硫酸、蓚酸、スルファミン酸の
1種又は2種以上の酸水溶液に浸漬する処理、又は浸漬
と交流電解を一定サイクルで繰り返す処理により、上記
多孔質陽極酸化皮膜の細孔の拡大処理を行い、細孔径を
50〜200nmとした後、該皮膜の細孔中に3〜15
0nmの大きさに微細化した有機顔料又はカーボンブラ
ックの水分散体中から電気泳動法によって有機顔料又は
カーボンブラックを泳動・析出させる方法によって得ら
れる。According to the present invention, in order to achieve the above object, particles are formed from the opening of the pores of a porous anodic oxide film having a pore diameter of 50 to 200 nm formed on aluminum to the bottom of the pores. An aluminum colored body having a colored oxide film formed by depositing an organic pigment or carbon black having a diameter of 3 to 150 nm is provided. According to the present invention, such an aluminum colored body is, as a first method,
Anodizing aluminum at a high voltage in an aqueous solution of one or more acids of a mineral acid or an organic acid, and forming a porous anodic oxide film having a pore diameter larger than a normal pore diameter of about 50 nm or less on the surface of the aluminum. After formation, the organic pigment or carbon black is obtained by electrophoresis from an aqueous dispersion of an organic pigment or carbon black finely divided to a size of 3 to 150 nm in the pores of the coating. Can be Further, as a second method, aluminum is anodized in an aqueous solution of one or more acids of a mineral acid or an organic acid to form a porous anodized film on the surface of the aluminum, and then phosphoric acid, sulfuric acid, or the like. By performing a treatment of immersing in one or two or more acid aqueous solutions of oxalic acid and sulfamic acid, or a treatment of repeating the immersion and AC electrolysis in a constant cycle, the porous anodic oxide film is subjected to a pore enlargement treatment, and the pore diameter is increased. Is set to 50 to 200 nm, and 3 to 15
It can be obtained by a method in which an organic pigment or carbon black is electrophoresed and precipitated by electrophoresis from an aqueous dispersion of an organic pigment or carbon black fined to a size of 0 nm.
【0006】[0006]
【発明の作用及び態様】本発明者らは、耐光性、耐侯
性、耐熱性等の諸特性に優れ、顔料の離脱もなく、堅牢
で色鮮やかなアルミニウムの着色酸化皮膜を得るために
は、顔料が多孔質陽極酸化皮膜の細孔内に出来るだけ深
く析着されることが必要であると考え、顔料粒子の微細
化及び水分散化、顔料を析出・充填できる陽極酸化皮膜
細孔の生成調整(細孔径拡大処理)、及び該細孔奥深く
にまで顔料を析着する方法等の研究を進め、本発明の着
色体を得るに至ったものである。すなわち、本発明によ
れば、3〜150nmの大きさに微細化した有機顔料又
はカーボンブラックの水分散体を用いること、アルミニ
ウム表面に通常の細孔径より大きい細孔径を有する陽極
酸化皮膜を形成させること、及び該皮膜の細孔中に電気
泳動法によって上記有機顔料又はカーボンブラックを泳
動・析出させることによって、前記のような優れた性質
を有するアルミニウム着色酸化皮膜を得るものである。
ここで、上記のように通常の細孔径より大きい細孔径を
有する陽極酸化皮膜を形成させる方法は、第一の方法に
おいては、アルミニウムを鉱酸又は有機酸の1種又は2
種以上の酸水溶液中で高電圧で陽極酸化処理することに
より行われ、一方、第二の方法においては、アルミニウ
ムの表面に多孔質陽極酸化皮膜を形成させた後、リン
酸、硫酸、蓚酸、スルファミン酸の1種又は2種以上の
酸水溶液に浸漬する処理又は浸漬と交流電解を一定サイ
クルで繰り返す処理により、上記多孔質陽極酸化皮膜の
細孔を拡大処理することによって行われる。なお、陽極
酸化皮膜の細孔径の拡大は、その強度等の特性上問題と
ならない程度に止めるべきである。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have found that in order to obtain a robust and vivid aluminum colored oxide film having excellent properties such as light resistance, weather resistance and heat resistance, no detachment of the pigment, and Considering that it is necessary for the pigment to be deposited as deeply as possible into the pores of the porous anodic oxide film, the pigment particles are made finer and dispersed in water, and the anodic oxide film pores that can deposit and fill the pigment are formed. Researches on the adjustment (pore diameter enlargement treatment) and the method of depositing the pigment deep into the pores have been advanced, and the colored body of the present invention has been obtained. That is, according to the present invention, an aqueous dispersion of an organic pigment or carbon black finely divided to a size of 3 to 150 nm is used, and an anodic oxide film having a pore size larger than a normal pore size is formed on the aluminum surface. And the above-mentioned organic pigment or carbon black is electrophoresed and deposited in the pores of the film by electrophoresis to obtain an aluminum-colored oxide film having the above-mentioned excellent properties.
Here, as described above, the method of forming an anodic oxide film having a pore diameter larger than the ordinary pore diameter is as follows. In the first method, aluminum is converted into one or more of a mineral acid or an organic acid.
It is performed by performing anodizing treatment at a high voltage in an aqueous solution of at least one kind of acid, while in the second method, after forming a porous anodized film on the surface of aluminum, phosphoric acid, sulfuric acid, oxalic acid, It is performed by expanding the pores of the porous anodic oxide film by a process of dipping in one or more kinds of aqueous solutions of sulfamic acid or a process of repeating dipping and alternating current electrolysis in a fixed cycle. It should be noted that the expansion of the pore diameter of the anodic oxide film should be stopped to such an extent that there is no problem in properties such as strength.
【0007】以下、本発明について詳細に説明する。ま
ず、着色剤として使用する高級有機顔料は、近年進歩著
しい顔料で、着色性及び耐光性、耐候性、耐熱性、耐溶
剤性等の耐久性に優れた高品位の顔料である。この部類
に属するものには、縮合アゾ系顔料、フタロシアニン系
顔料、及びペリレン系、ペリノン系、キナクリドン系、
チオインジゴ系、ジオキサジン系、イソインドリノン
系、イソインドリン系、キノフタロン系、金属錯体系等
の縮合多環顔料等がある。これらの顔料粒子は、一般
に、10〜500nmの大きさの一次粒子が集合して凝
集体を形成しており、この凝集体を元の一次粒子の大き
さにまで分散させることは非常にむつかしい。さらに、
これらの顔料は表面の極性が小さく、水を始めとする極
性溶媒中に安定な状態で分散させることは特に難しい。
また、これらの顔料の一次粒子の大きさは、通常の方法
で得られるアルミニウム陽極酸化皮膜の細孔径と同等以
上かもしくはそれよりもはるかに大きい。したがって、
これら顔料粒子の微細化と分散化を行う必要がある。Hereinafter, the present invention will be described in detail. First, a high-grade organic pigment used as a coloring agent is a pigment which has been remarkably advanced in recent years, and is a high-grade pigment excellent in durability such as coloring property, light resistance, weather resistance, heat resistance and solvent resistance. Condensed azo-based pigments, phthalocyanine-based pigments, and perylene-based, perinone-based, quinacridone-based pigments,
Condensed polycyclic pigments such as thioindigo, dioxazine, isoindolinone, isoindoline, quinophthalone, metal complex and the like. In these pigment particles, generally, primary particles having a size of 10 to 500 nm are aggregated to form an aggregate, and it is very difficult to disperse the aggregate to the size of the original primary particles. further,
These pigments have a small surface polarity, and it is particularly difficult to disperse them in a stable state in a polar solvent such as water.
The size of the primary particles of these pigments is equal to or larger than the pore size of the aluminum anodic oxide film obtained by a usual method, or much larger. Therefore,
It is necessary to refine and disperse these pigment particles.
【0008】顔料粒子の微細化と分散化については、分
散剤として陰イオン性の高分子活性剤、例えば、ナフタ
レンスルホン酸のホルマリン縮合物、ポリスチレンスル
ホン酸塩、ポリアクリル酸塩などを用いてサンドミルで
分散させると、安定な水分散体が得られることがわかっ
た。また、サンドミルで分散させる前に、前もって顔料
にプラズマ処理などの表面処理を施しておくと、より優
れた水分散体が得られる。さらに、これらの高級有機顔
料は濃硫酸に溶解するものが大部分であるので、それら
の顔料については、一度濃硫酸に溶解し、それを水中に
加えて、より微細な顔料粒子として析出させる方法も併
用出来る。このような方法によって、粒子径が3〜15
0nm、好ましくは3〜100nmの顔料の安定な水分
散体を調整する。[0008] The pigment particles are made finer and dispersed by using an anionic polymer activator such as a formalin condensate of naphthalene sulfonic acid, polystyrene sulfonic acid salt or polyacrylic acid salt as a dispersing agent. It was found that a stable aqueous dispersion could be obtained by dispersing in water. Further, if the pigment is previously subjected to a surface treatment such as a plasma treatment before being dispersed by a sand mill, a more excellent aqueous dispersion can be obtained. Furthermore, since most of these higher organic pigments dissolve in concentrated sulfuric acid, these pigments are dissolved in concentrated sulfuric acid once, added to water, and precipitated as finer pigment particles. Can also be used together. By such a method, the particle diameter is 3 to 15
A stable aqueous dispersion of the pigment of 0 nm, preferably 3 to 100 nm, is prepared.
【0009】次に、顔料を析着出来る細孔径を有するア
ルミニウム陽極酸化皮膜としては、50〜200nm、
好ましくは50〜150nmの細孔径を有する陽極酸化
皮膜であることが必要である。陽極酸化処理浴として
は、鉱酸又は有機酸、例えば硫酸、リン酸、蓚酸、マロ
ン酸、マレイン酸の1種又は2種以上の酸水溶液を用い
ることが出来、好ましくは蓚酸水溶液を主体とした浴が
望ましい。本発明の第一の方法においては、アルミニウ
ムを前記鉱酸又は有機酸の1種又は2種以上の酸水溶液
中で約130V以上の高電圧で陽極酸化し、該アルミニ
ウムの表面に通常の細孔径より大きい多孔質陽極酸化皮
膜を形成させる。前記したように、通常の陽極酸化処理
によつて得られる陽極酸化皮膜の細孔径は50nm以下
であるため、該細孔内に前記顔料を析着することは、顔
料の平均粒子径の大小にもよるが、一般に困難であるの
に対し、概してDC150V〜200Vの高電圧で陽極
酸化した場合、通常120nm以上の細孔径を有する陽
極酸化皮膜が得られるので、該細孔内に前記顔料の殆ど
を析着出来る。すなわち、陽極酸化処理の電圧が上記電
圧よりも低い場合、顔料の析着に十分な大きさの細孔が
得られにくいので好ましくなく、一方、200Vを越え
ると陽極酸化皮膜の強度等の物性に悪影響を及ぼすので
好ましくない。Next, as an aluminum anodic oxide film having a pore diameter capable of depositing a pigment, 50 to 200 nm,
Preferably, it is necessary to have an anodized film having a pore diameter of 50 to 150 nm. As the anodizing bath, a mineral acid or an organic acid such as sulfuric acid, phosphoric acid, oxalic acid, malonic acid, one or two or more acid aqueous solutions of maleic acid can be used, and preferably an oxalic acid aqueous solution is mainly used. Bath is desirable. In the first method of the present invention, aluminum is anodized at a high voltage of about 130 V or more in an aqueous solution of one or more of the above-mentioned mineral acids or organic acids, and a normal pore size is formed on the surface of the aluminum. Form a larger porous anodic oxide film. As described above, since the pore diameter of the anodic oxide film obtained by the ordinary anodic oxidation treatment is 50 nm or less, the deposition of the pigment in the pores depends on the average particle diameter of the pigment. Although it is generally difficult, when anodizing is generally performed at a high voltage of 150 to 200 V DC, an anodic oxide film having a pore diameter of 120 nm or more is obtained. Can be deposited. That is, if the voltage of the anodic oxidation treatment is lower than the above-mentioned voltage, it is difficult to obtain pores large enough for the deposition of the pigment, which is not preferable. It is not preferable because it has an adverse effect.
【0010】本発明の第二の方法では、まずアルミニウ
ムを前記鉱酸又は有機酸の1種又は2種以上の酸水溶液
中で陽極酸化し、該アルミニウムの表面に多孔質陽極酸
化皮膜を形成させる。電解条件としては、35V以上、
好ましくは50〜160Vの高電圧電解により、セルサ
イズ及び細孔径の大きな陽極酸化皮膜を得る。次いで、
リン酸、硫酸、蓚酸、スルファミン酸の1種又は2種以
上の酸水溶液、好ましくはリン酸3〜10W/V%の水
溶液に浸漬して皮膜細孔の拡大処理を行い、最終的には
50〜200nm、好ましくは50〜150nmの細孔
に調整して、本発明の着色に適する陽極酸化皮膜を得
る。また、皮膜細孔の拡大処理の時間を短縮するため
に、リン酸3〜10W/V%の水溶液中で、浸漬と交流
電解の処理を交互に短時間間隔で繰り返すことにより、
該皮膜細孔の拡大処理を比較的短時間に行うことが出来
る。In the second method of the present invention, aluminum is first anodized in an aqueous solution of one or more of the above-mentioned mineral acids or organic acids to form a porous anodized film on the surface of the aluminum. . As the electrolysis conditions, 35 V or more,
An anodic oxide film having a large cell size and a large pore diameter is obtained by high-voltage electrolysis of preferably 50 to 160 V. Then
The film pores are expanded by immersing in one or more aqueous acid solutions of phosphoric acid, sulfuric acid, oxalic acid, and sulfamic acid, preferably in an aqueous solution of 3 to 10 W / V% phosphoric acid. The anodic oxide film suitable for coloring of the present invention is obtained by adjusting the pore size to 200 nm, preferably 50 nm to 150 nm. Further, in order to shorten the time required for the process of expanding the pores of the film, the immersion and alternating current electrolysis are alternately repeated at short intervals in an aqueous solution of phosphoric acid of 3 to 10 W / V%.
The process of expanding the film pores can be performed in a relatively short time.
【0011】着色処理においては、高級有機顔料又はカ
ーボンブラックの水分散体中で上記陽極酸化皮膜を有す
るアルミニウム材を陽極とする電気泳動処理により、皮
膜細孔の深部にまで分散顔料が誘導析出され、鮮やかな
着色皮膜を得ることが出来る。電気泳動法としては、直
流電圧を低電圧より高電圧へ一定の昇圧速度で所望の色
になるまで走査する直流電圧走査法、及び定電圧で所望
の色になるまでの時間を電解する直流定電圧法等により
着色処理を行う。なお、このようにして得られたアルミ
ニウム着色体には、さらに必要に応じて封孔処理やクリ
ヤー塗装を施すことが出来る。In the coloring treatment, the dispersed pigment is induced and deposited to the deep part of the pores of the film by electrophoresis in an aqueous dispersion of a high-quality organic pigment or carbon black using the aluminum material having the anodic oxide film as an anode. And a vivid colored film can be obtained. As the electrophoresis method, a DC voltage scanning method in which a DC voltage is scanned from a low voltage to a high voltage at a constant step-up speed until a desired color is obtained, and a DC voltage scanning method in which the time until the desired color is obtained at a constant voltage is performed. A coloring process is performed by a voltage method or the like. The aluminum colored body thus obtained can be subjected to a sealing treatment or a clear coating, if necessary.
【0012】[0012]
【発明の効果】本発明の方法により着色された酸化皮膜
中の着色顔料は、図1に示すEPMAによる線分析のカ
ーボン線から分かるように、酸化皮膜細孔の最深部にま
で析着されている。そのため、着色体の顔料が摩擦等に
より容易に脱離することがなく、堅牢で耐久性に優れた
鮮やかな着色皮膜を得ることが出来る。また、顔料を選
択することにより、赤、黒、青等の種々の所望の色に着
色出来、アルミニウムの多色化のニーズに十分に応える
ことが出来る。従来、顔料を用いたアルミニウムの着色
法は実用化されていないが、本発明はそれを可能とする
ものであり、実用上極めて大きな価値を有するものと言
える。The coloring pigment in the oxide film colored by the method of the present invention is deposited on the deepest portion of the oxide film pores, as can be seen from the carbon wire obtained by the line analysis by EPMA shown in FIG. I have. For this reason, the pigment of the colored body does not easily come off due to friction or the like, and it is possible to obtain a strong and durable bright colored film. In addition, by selecting a pigment, it can be colored in various desired colors such as red, black, and blue, and can sufficiently meet the needs for multicolor aluminum. Conventionally, a method of coloring aluminum using a pigment has not been put to practical use, but the present invention makes it possible and can be said to be of great value in practical use.
【0013】[0013]
【実施例】以下、実施例を示して本発明について具体的
に説明する。 実施例 1 工業用純アルミニウム板(JIS A1050P−H2
4,大きさ50×20mm)を常法に従って前処理した
後、30℃、5%蓚酸浴中、DC160Vで定電圧電解
を5分間行って、皮膜厚さ10μmの陽極酸化皮膜を形
成させた。次いで、該アルミニウム板を陽極として、2
5℃の10%カーボンブラック水分散体浴中でDC60
Vで電気泳動処理を1分間行い、黒色に鮮やかに着色し
たアルミニウム陽極酸化皮膜を生成させた。なお、陰極
としては同じ大きさの炭素電極を用いた。得られた着色
酸化皮膜は、堅牢で耐久性にも優れていた。なお、カー
ボンブラック水分散体は、ポリアクリル酸ソーダを分散
剤としてカーボンブラツク100gに対して固形分量で
5g添加した水1L溶液をサンドミルで5時間分散させ
たもので、その平均粒子径は60nmである。The present invention will be specifically described below with reference to examples. Example 1 Industrial pure aluminum plate (JIS A1050P-H2)
4, 50 × 20 mm) was pretreated according to a conventional method, and then subjected to constant voltage electrolysis at 30 ° C. in a 5% oxalic acid bath at 160 V DC for 5 minutes to form an anodized film having a film thickness of 10 μm. Then, using the aluminum plate as an anode, 2
DC 60 in a 10% carbon black aqueous dispersion bath at 5 ° C.
The electrophoresis treatment was carried out for 1 minute at V to produce an aluminum anodic oxide film that was brightly colored black. The same size carbon electrode was used as the cathode. The obtained colored oxide film was robust and excellent in durability. The aqueous carbon black dispersion was obtained by dispersing a 1 L solution of water in which 5 g of a solid content was added to 100 g of carbon black using sodium polyacrylate as a dispersant for 5 hours with a sand mill, and the average particle diameter was 60 nm. is there.
【0014】実施例 2 前記工業用純アルミニウム板を常法に従って前処理した
後、20℃、0.3%蓚酸浴中、DC150Vで定電圧
電解を6分間行って、皮膜厚さ10μmの陽極酸化皮膜
を形成させた。次いで、このアルミニウム板を5%リン
酸溶液中に0〜300分間浸漬して、皮膜孔径の拡大処
理を行った。その後、このアルミニウム板を陽極とし
て、前記実施例1で用いた25℃の10%カーボンブラ
ック水分散体浴中で電気泳動処理を行い、黒色に着色し
たアルミニウム陽極酸化皮膜を生成させた。なお、陰極
としては同じ大きさの炭素電極を用いた。結果を表1に
示す。また、上記皮膜孔径拡大浸漬処理を100分行っ
た場合の着色酸化皮膜中のカーボンのEPMAによる線
分析図を図1に示す。Example 2 After pretreatment of the industrial pure aluminum plate according to a conventional method, constant voltage electrolysis was performed for 6 minutes at 20 ° C. in a 0.3% oxalic acid bath at DC 150 V for anodizing with a film thickness of 10 μm. A film was formed. Next, this aluminum plate was immersed in a 5% phosphoric acid solution for 0 to 300 minutes to perform a process of enlarging the film pore diameter. Thereafter, the aluminum plate was used as an anode to perform an electrophoresis treatment in the aqueous 10% carbon black dispersion bath at 25 ° C. used in Example 1 to form an aluminum anodic oxide film colored black. The same size carbon electrode was used as the cathode. Table 1 shows the results. In addition, FIG. 1 shows a line analysis diagram of carbon in the colored oxide film by EPMA when the above-mentioned coating pore diameter dip treatment was performed for 100 minutes.
【0015】[0015]
【表1】 [Table 1]
【0016】実施例 3 アルミニウム合金63S板を常法に従って前処理した
後、20℃の0.3%蓚酸浴中、DC150Vで6分
間、定電圧電解を行って、皮膜厚さ10μmの陽極酸化
皮膜を形成させた後、30℃の5%リン酸水溶液中に1
20分間浸漬して、皮膜孔径の拡大処理を行った。次い
で、これを25℃の10%ジオキサジンバイオレット水
分散体1L浴中で、該アルミニウム板を陽極として、8
0Vの定電圧で電気泳動処理して、紫色に着色した皮膜
を得た。ジオキサジンバイオレットの水分散体は、ジオ
キサジンバイオレット100gに1%ポリスチレンスル
ホン酸ソーダ水溶液を加えて全量1Lとし、これをサン
ドミルを用いて10時間分散させたもので、ジオキサジ
ンバイオレツトの平均粒子径は55nmである。Example 3 After pretreatment of an aluminum alloy 63S plate in accordance with a conventional method, constant voltage electrolysis was performed in a 0.3% oxalic acid bath at 20 ° C. for 6 minutes at 150 V DC to obtain an anodic oxide film having a film thickness of 10 μm. Is formed and then placed in a 5% phosphoric acid aqueous solution at 30 ° C.
The film was immersed for 20 minutes to perform a process of enlarging the film pore diameter. Next, this was placed in a 1 L bath of an aqueous dispersion of 10% dioxazine violet at 25 ° C., using the aluminum plate as an anode, for 8 hours.
Electrophoresis was performed at a constant voltage of 0 V to obtain a purple-colored film. The aqueous dispersion of dioxazine violet is obtained by adding a 1% aqueous solution of sodium polystyrene sulfonate to 100 g of dioxazine violet to make a total volume of 1 L, and dispersing the mixture for 10 hours using a sand mill. Is 55 nm.
【0017】実施例 4 アルミニウム合金63S板を常法に従って前処理した
後、実施例2と同様の方法で陽極酸化皮膜の形成及び孔
径の拡大処理を行った。次いで、30℃の50g/Lの
銅フタロシアニンブルーの水分散体中で、該アルミニウ
ム板を陽極として、DC80Vの電圧で電気泳動処理し
て、青色に着色した陽極酸化皮膜を得た。陰極は炭素電
極とし、電気泳動時間は2分であった。なお、顔料の水
分散体は、銅フタロシアニンブルー50gを98%の硫
酸600mLに溶解し、攪拌しながら、これを0.5%
のポリアクリル酸ソーダ水溶液5Lに加えてフタロシア
ニン粒子を析出させ、硫酸根がなくなるまで水洗した
後、水酸化ナトリウムでpH9に調整し、全量が1Lに
なるように0.5%アクリル酸ソーダ水溶液を加え、次
いで、これをサンドミルにかけて分散させ、粒子径50
nmの銅フタロシアニンブルーの水分散体を得た。Example 4 After pretreatment of an aluminum alloy 63S plate according to a conventional method, formation of an anodic oxide film and enlargement of the hole diameter were performed in the same manner as in Example 2. Next, in an aqueous dispersion of 50 g / L copper phthalocyanine blue at 30 ° C., the aluminum plate was used as an anode and subjected to electrophoresis at a voltage of DC 80 V to obtain an anodized film colored blue. The cathode was a carbon electrode, and the electrophoresis time was 2 minutes. The aqueous dispersion of the pigment was prepared by dissolving 50 g of copper phthalocyanine blue in 600 mL of 98% sulfuric acid, and stirring it with 0.5%.
Was added to 5 L of aqueous sodium polyacrylate solution to precipitate phthalocyanine particles, washed with water until the sulfate group disappeared, adjusted to pH 9 with sodium hydroxide, and added with 0.5% aqueous sodium acrylate solution so that the total amount became 1 L. Then, the mixture is dispersed in a sand mill to obtain a particle diameter of 50.
An aqueous dispersion of copper phthalocyanine blue having a thickness of nm was obtained.
【0018】実施例 5 アルミニウム合金63S板を常法に従って前処理した
後、20℃の0.3%蓚酸浴中、DC150Vで6分
間、定電圧電解を行って、皮膜厚さ10μmの陽極酸化
皮膜を形成させた後、25℃の8%リン酸水溶液中でA
C8V電解1分とAC0Vで2分の繰返し処理を30分
間行い、皮膜細孔の拡大処理を行った。次いで、実施例
4の方法で作成した30℃の50g/Lの銅フタロシア
ニンブルーの水分散体中で、該アルミニウム板を陽極と
し、陰極を炭素として、DC80Vの定電圧で2分間電
気泳動処理して、青色に着色した陽極酸化皮膜を得た。Example 5 An aluminum oxide 63S plate was pretreated according to a conventional method, and then subjected to constant voltage electrolysis in a 0.3% oxalic acid bath at 20 ° C. for 6 minutes at 150 V DC to form an anodic oxide film having a film thickness of 10 μm. Is formed, and A is added in an aqueous 8% phosphoric acid solution at 25 ° C.
A repetitive treatment of C8V electrolysis for 1 minute and AC0V for 2 minutes was performed for 30 minutes to perform a process of enlarging film pores. Next, in an aqueous dispersion of 50 g / L copper phthalocyanine blue at 30 ° C. prepared by the method of Example 4, the aluminum plate was used as an anode, and the cathode was made of carbon, followed by electrophoresis at a constant voltage of 80 V DC for 2 minutes. Thus, a blue-colored anodized film was obtained.
【0019】実施例 6 アルミニウム合金63S板を、実施例4の銅フタロシア
ニンブルーの代わりにキナクリドンレッド50g/Lを
用いて、実施例4と全く同様に処理して赤色の陽極酸化
皮膜を得た。キナクリドンレッド水分散体の平均粒子径
は70nmであった。Example 6 A red anodic oxide film was obtained by treating an aluminum alloy 63S plate in exactly the same manner as in Example 4 except that 50 g / L of quinacridone red was used instead of the copper phthalocyanine blue of Example 4. The average particle size of the aqueous quinacridone red dispersion was 70 nm.
【0020】実施例 7 アルミニウム合金63S板を、実施例4の銅フタロシア
ニンブルーの代わりに高塩素化銅フタロシアニングリー
ンを、また分散剤のポリアクリル酸ソーダの代わりにナ
フタレンスルホン酸ナトリウムホルマリン縮合物を用い
て、実施例4と全く同様に処理して緑色の陽極酸化皮膜
を得た。Example 7 An aluminum alloy 63S plate was used instead of copper phthalocyanine blue of Example 4, and a highly chlorinated copper phthalocyanine green was used. In place of sodium polyacrylate as a dispersant, sodium naphthalene sulfonate formalin condensate was used. In the same manner as in Example 4, a green anodic oxide film was obtained.
【図1】実施例2で得られた着色酸化皮膜中のカーボン
のEPMAによる線分析図である。FIG. 1 is a line analysis diagram of carbon in a colored oxide film obtained in Example 2 by EPMA.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6,DB名) C25D 11/20 - 11/22 302 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) C25D 11/20-11/22 302
Claims (1)
成された細孔径50〜200nmの多孔質陽極酸化皮膜
の細孔の開口部から孔底にかけて粒子径3〜150nm
の有機顔料又はカーボンブラックが析着されてなる着色
酸化皮膜を有するアルミニウム又はアルミニウム合金の
着色体。1. A particle diameter of 3 to 150 nm from the opening to the bottom of a pore of a porous anodic oxide film having a pore diameter of 50 to 200 nm formed on aluminum or an aluminum alloy.
Aluminum or aluminum alloy having a colored oxide film formed by depositing an organic pigment or carbon black.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26822997A JP2937963B2 (en) | 1997-09-16 | 1997-09-16 | Colored aluminum or aluminum alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26822997A JP2937963B2 (en) | 1997-09-16 | 1997-09-16 | Colored aluminum or aluminum alloy |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3276490A Division JP2759897B2 (en) | 1991-09-30 | 1991-09-30 | Method for producing colored body of aluminum or aluminum alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH10121293A JPH10121293A (en) | 1998-05-12 |
JP2937963B2 true JP2937963B2 (en) | 1999-08-23 |
Family
ID=17455712
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JP (1) | JP2937963B2 (en) |
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JP6093523B2 (en) * | 2011-09-29 | 2017-03-08 | 電化皮膜工業株式会社 | Method for producing colored aluminum product or colored aluminum alloy product |
US20160362808A1 (en) * | 2014-02-28 | 2016-12-15 | Sakura Color Products Corporation | Colored shaped aluminum article and method for manufacturing same |
JP6306897B2 (en) * | 2014-02-28 | 2018-04-04 | 株式会社サクラクレパス | Colored aluminum molded body and method for producing the same |
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1997
- 1997-09-16 JP JP26822997A patent/JP2937963B2/en not_active Expired - Fee Related
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