JPH07243092A - Method for coloring aluminum or aluminum alloy - Google Patents
Method for coloring aluminum or aluminum alloyInfo
- Publication number
- JPH07243092A JPH07243092A JP5501794A JP5501794A JPH07243092A JP H07243092 A JPH07243092 A JP H07243092A JP 5501794 A JP5501794 A JP 5501794A JP 5501794 A JP5501794 A JP 5501794A JP H07243092 A JPH07243092 A JP H07243092A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- aluminum
- coloring
- bath
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Abstract
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、アルミニウムと総称する）の着色
方法に関し、さらに詳しくは、アルミニウムの多孔質陽
極酸化皮膜の細孔中に電気泳動法によって有機顔料又は
カーボンブラックを析出・充填させ、着色する方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coloring aluminum or an aluminum alloy (hereinafter collectively referred to as "aluminum"), and more specifically, an organic pigment in the pores of a porous anodic oxide film of aluminum by an electrophoretic method. Alternatively, the present invention relates to a method of depositing / filling carbon black and coloring.
【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、各種金属塩を含有する浴中での交流電解
による電解着色法を中心に、各種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、電解着色法ではブロンズ色等の茶色系以外の着色は
容易でなく、色の種類が限定されるという難点があり、
一方、染料による染色では各種の色への着色は容易であ
るが、光等に対する耐久性が低いという難点がある。こ
のような問題を解決するための方策として、微細粒顔料
の水分散体中で電気泳動法により多孔質陽極酸化皮膜を
着色する方法が種々提案されており、本出願人も、アル
ミニウムの表面に通常の細孔径より大きい細孔を有する
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・析出させて充填し、
着色する方法を既に提案している（特開平５−９３２９
６号公報参照）。2. Description of the Related Art Conventionally, as a method for coloring an aluminum anodic oxide film, mainly an electrolytic coloring method by AC electrolysis in a bath containing various metal salts, a dipping coloring method using a bath of various dyes, etc. Many methods are known. However, in the electrolytic coloring method, it is not easy to color a color other than brown, such as a bronze color, and there is a drawback that the type of color is limited.
On the other hand, in dyeing with a dye, coloring to various colors is easy, but there is a drawback that durability against light or the like is low. As a measure for solving such a problem, various methods of coloring a porous anodic oxide film by an electrophoretic method in an aqueous dispersion of fine particle pigments have been proposed, and the applicant of the present invention also applied the method to the surface of aluminum. After forming a porous anodic oxide film having pores larger than the usual pore size, electricity is removed from an aqueous dispersion of an organic pigment or carbon black finely sized to 3 to 150 nm in the pores of the film. An organic pigment or carbon black is electrophoresed and deposited by the electrophoretic method, and then filled.
A method for coloring has already been proposed (JP-A-5-9329).
No. 6 publication).
【０００３】[0003]
【発明が解決しようとする課題】上記特開平５−９３２
９６号公報に記載の着色方法によれば、顔料の選択に応
じて赤、黒、青等の種々の所望の色に着色でき、また、
例えば直流定電圧電解法を用い、所望の色の濃さに応じ
た電圧を印加することにより、これに応じた広い範囲で
色の濃淡をコントロールすることが可能である。しかし
ながら、皮膜の着色状態は顔料分散体の条件により、色
むらの発生が見られたり、顔料が皮膜表面に異常析出し
濃い着色皮膜が得られないという欠点がある。すなわ
ち、顔料分散体が必要以上の電気電導性を持つと、顔料
の泳動に無関係な電流が多く流れる。この電流により、
皮膜細孔内では水の電気分解などの陽極反応が激しく起
こり、着色皮膜の細孔内又は皮膜近傍のｐＨは低下す
る。この変化が激しいため、顔料の表面電位の低下、凝
集、析出が皮膜細孔内で不均一に起こり、または皮膜表
面に析出しやすくなるため、色むら、皮膜表面での顔料
の異常析出が見られる。また、皮膜の着色状態は、顔料
分散体の他の条件によっても色むらの発生が見られる。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
According to the coloring method described in Japanese Patent Publication No. 96, it is possible to color various desired colors such as red, black, and blue according to the selection of the pigment.
For example, by using a direct current constant voltage electrolysis method and applying a voltage according to a desired color strength, it is possible to control the lightness and shade of the color in a wide range corresponding to this. However, depending on the conditions of the pigment dispersion, the coloring state of the film has the drawbacks that uneven coloring is observed and the pigment is abnormally deposited on the surface of the film so that a dark colored film cannot be obtained. That is, when the pigment dispersion has an electric conductivity that is higher than necessary, a large amount of current flows unrelated to the migration of the pigment. With this current,
Anodic reactions such as electrolysis of water occur violently in the pores of the coating, and the pH in the pores of the colored coating or in the vicinity of the coating is lowered. This change is so severe that the surface potential of the pigment decreases, agglomerates and deposits unevenly within the pores of the coating, or easily deposits on the coating surface, resulting in uneven color and abnormal pigment deposition on the coating surface. To be Further, in the coloring state of the film, the occurrence of color unevenness can be seen depending on other conditions of the pigment dispersion.
【０００４】従って、本発明の基本的な目的は、微細顔
料をアルミニウムの多孔質陽極酸化皮膜に電気泳動法に
よって析出・充填させ着色する方法において、色むらの
発生や皮膜表面に顔料が凝集（ゲル化）し異常析出する
のを防止することにある。さらに本発明の目的は、多孔
質陽極酸化皮膜表面への顔料の異常析出や色むらの発生
もなく、所望の色相及び濃淡に広い範囲でコントロール
可能なアルミニウムの着色方法を提供することにある。
本発明の他の目的は、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・退色もなく、
堅牢で色鮮やかな所望の色相の着色酸化皮膜を作製でき
るアルミニウムの着色方法を提供することにある。Therefore, the basic object of the present invention is to deposit and fill a fine pigment in a porous anodic oxide coating of aluminum by an electrophoretic method to color the pigment, thereby causing uneven coloring and agglomeration of the pigment on the coating surface ( This is to prevent gelation) and abnormal precipitation. A further object of the present invention is to provide a method for coloring aluminum in which a desired hue and shade can be controlled in a wide range without causing abnormal precipitation of pigments or uneven coloring on the surface of the porous anodic oxide film.
Another object of the present invention is to deposit and fill a pigment deep in the pores of a porous anodic oxide coating of aluminum to satisfy various durability required for building exterior materials and the like, without discoloration or fading,
An object of the present invention is to provide a method for coloring aluminum, which is capable of forming a colored oxide film having a desired hue that is robust and vivid.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明によれば、多孔質陽極酸化皮膜を形成したア
ルミニウム又はアルミニウム合金を、顔料濃度１０ｇ／
ｌ当り１０００μＳ／ｃｍ以下の比電導度に調整した有
機顔料又はカーボンブラックの顔料分散体の浴中で電気
泳動処理し、多孔質陽極酸化皮膜の細孔深部にまで有機
顔料又はカーボンブラックを析出・充填させ着色するこ
とを特徴とするアルミニウム又はアルミニウム合金の着
色方法が提供される。好適な態様によれば、上記顔料分
散体としては、粒子径３〜１５０ｎｍの有機顔料又はカ
ーボンブラックの顔料分散体が用いられ、また該顔料分
散体の浴の条件としては、顔料濃度は５０ｇ／ｌ以下、
好ましくは１０〜４０ｇ／ｌ、浴の温度は２５℃以下、
好ましくは１５〜２５℃、浴のｐＨは１０以下、好まし
くは８．５〜９．５が望ましい。In order to achieve the above object, according to the present invention, aluminum or aluminum alloy having a porous anodic oxide film formed thereon has a pigment concentration of 10 g /
Electrophoresis is performed in a bath of a pigment dispersion of an organic pigment or carbon black adjusted to a specific electric conductivity of 1000 μS / cm or less per liter, and the organic pigment or carbon black is deposited even in deep pores of the porous anodized film. There is provided a method for coloring aluminum or an aluminum alloy, which comprises filling and coloring. According to a preferred embodiment, as the pigment dispersion, an organic pigment having a particle diameter of 3 to 150 nm or a pigment dispersion of carbon black is used, and the condition of the pigment dispersion bath is that the pigment concentration is 50 g / l or less,
Preferably 10 to 40 g / l, the temperature of the bath is 25 ° C or lower,
The temperature of the bath is preferably 15 to 25 ° C., and the pH of the bath is 10 or less, preferably 8.5 to 9.5.
【０００６】[0006]
【発明の作用及び態様】前記したように、微細顔料を電
気泳動法によって多孔質陽極酸化皮膜の細孔内に析出・
充填させる着色方法においては、顔料分散体の条件によ
り、皮膜の着色状態には色むらの発生や皮膜表面への顔
料の異常析出がみられる。すなわち、微細顔料の電気泳
動法による着色方法においては、電圧の印加により顔料
が多孔質陽極酸化皮膜の細孔内に泳動されるが、顔料分
散体が必要以上の電導性を持つと、電圧の印加によって
顔料の泳動に無関係な電流が多く流れる。この電気泳動
に関係のない電流により、皮膜細孔内では水の電気分解
などの陽極反応が必要以上に起こり、着色皮膜の細孔内
又は皮膜近傍のｐＨを急激に低下させるため、顔料が皮
膜細孔内に不均一に析出したり、皮膜表面に凝集（ゲル
化）、析出し易くなる。そこで、本発明では、顔料の泳
動に作用しない電流が殆ど流れないように顔料分散体の
浴の比電導度を顔料濃度１０ｇ／ｌ当り１０００μＳ／
ｃｍ以下に調整して電気泳動を行うものであり、それに
よって上記のような必要以上な陽極反応や皮膜近傍での
ｐＨの急激な低下が抑制され、顔料の凝集を防止でき
る。従って、色むらや皮膜表面への顔料の異常析出の発
生もなく、広い電圧範囲で所望の濃淡の着色皮膜に着色
が可能となり、耐光性、耐候性、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
の着色皮膜を得ることができる。As described above, the fine pigment is deposited in the pores of the porous anodic oxide film by the electrophoretic method.
In the coloring method of filling, depending on the condition of the pigment dispersion, uneven coloring occurs in the colored state of the film and abnormal deposition of the pigment on the surface of the film. That is, in the method of coloring the fine pigment by the electrophoretic method, the pigment is migrated into the pores of the porous anodic oxide film by the application of a voltage. Due to the application, a large amount of current that is unrelated to the migration of the pigment flows. Due to this electric current not related to electrophoresis, anodic reactions such as electrolysis of water occur in the pores of the film more than necessary, and the pH in the pores of the colored film or in the vicinity of the film sharply decreases. It is likely to be deposited nonuniformly in the pores, or to be agglomerated (gelled) on the surface of the coating to be deposited. Therefore, in the present invention, the specific conductivity of the bath of the pigment dispersion is set to 1000 μS / g per 10 g / l of the pigment concentration so that an electric current that does not affect the migration of the pigment hardly flows.
The electrophoresis is performed by adjusting the thickness to be equal to or less than 10 cm, whereby the excessive anodic reaction and the sharp decrease in pH in the vicinity of the film as described above are suppressed, and the aggregation of the pigment can be prevented. Therefore, it is possible to color a desired tint colored film in a wide voltage range without causing color unevenness or abnormal deposition of the pigment on the film surface, and it is excellent in various properties such as light resistance, weather resistance, and heat resistance. It is possible to obtain a robust and colorful colored film of aluminum without separation.
【０００７】本発明によるアルミニウムの着色方法にお
いて、基本的な着色条件は、顔料分散体の浴を顔料濃度
１０ｇ／ｌ当り１０００μＳ／ｃｍ以下の比電導度に調
整することである。顔料分散体の比電導度が１０００μ
Ｓ／ｃｍを越えると、前記したように顔料の泳動に関係
のない電流が流れ易くなり、陽極反応、具体的には、水
の電気分解などが起こり、色むらや顔料の表面析出が生
じ易くなるので好ましくない。顔料分散体は、有機顔料
又はカーボンブラックの顔料分散体を、分散剤として陰
イオン性の高分子活性剤、たとえばナフタリンスルホン
酸のホルマリン縮合物、ポリスチレンスルホン酸塩、ポ
リアクリル酸塩及びこれらの共重合体等を用いて作製す
る。この時、分散剤の量や各種添加剤の添加を調整し、
顔料分散体の比電導度があまり高くならないようにす
る。この顔料分散体は、通常、着色に供する時、希釈や
ｐＨ調整が行なわれるが、そのときの比電導度が前記の
ように分散体中の顔料濃度１０ｇ／ｌ当り１０００μＳ
／ｃｍ以下であるようにする。In the method for coloring aluminum according to the present invention, the basic coloring condition is to adjust the bath of the pigment dispersion to a specific electric conductivity of 1000 μS / cm or less per 10 g / l of the pigment concentration. The specific conductivity of the pigment dispersion is 1000μ
If it exceeds S / cm, an electric current unrelated to the migration of the pigment easily flows as described above, and an anodic reaction, specifically, electrolysis of water or the like occurs, and color unevenness or pigment deposition on the surface easily occurs. Therefore, it is not preferable. The pigment dispersion comprises an organic pigment or a pigment dispersion of carbon black as an anionic polymer activator as a dispersant, such as a formalin condensate of naphthalene sulfonic acid, a polystyrene sulfonate, a polyacrylate and a mixture thereof. It is prepared using a polymer or the like. At this time, adjust the amount of dispersant and the addition of various additives,
Make sure that the specific conductivity of the pigment dispersion does not become too high. This pigment dispersion is usually diluted or pH-adjusted when it is subjected to coloring, and the specific conductivity at that time is 1000 μS per 10 g / l of the pigment concentration in the dispersion as described above.
/ Cm or less.
【０００８】また、顔料分散体は、顔料濃度が５０ｇ／
ｌ以下、好ましくは１０〜４０ｇ／ｌ、ｐＨが１０以
下、好ましくは８．５〜９．５の範囲が望ましい。この
ような範囲に調整された顔料分散体中で、アルミニウム
陽極酸化皮膜を陽極として、電気泳動法で着色すると、
色むらの発生もなく、また顔料の皮膜表面への異常析出
が高い泳動電圧でも起こらない為、広い電圧範囲で着色
が可能となり、また濃淡の制御された着色が可能とな
る。浴中の顔料濃度が５０ｇ／ｌを越えて高くなると、
顔料濃度が大きいために顔料が凝集し易くなり、皮膜表
面に析出し易くなり、逆に顔料濃度が１０ｇ／ｌ未満で
あると、顔料が少ないために色を濃くすることが難し
く、いずれの場合も十分な着色を行うことができなくな
るので好ましくない。また、浴のｐＨが８．５未満で
は、ｐＨが低く、顔料の表面電位が低くなり、凝集し易
く、皮膜表面に析出し易くなるので好ましくない。一
方、ｐＨが１０を越えるとアルカリ性が強く、細孔内に
析出した顔料が再び溶け、分散してしまうために、色が
薄くなってしまい色むらを発生するので好ましくない。The pigment dispersion has a pigment concentration of 50 g /
1 or less, preferably 10 to 40 g / l, and a pH of 10 or less, preferably 8.5 to 9.5. In the pigment dispersion adjusted to such a range, when the aluminum anodic oxide film is used as an anode and is colored by an electrophoretic method,
Since no color unevenness occurs and abnormal deposition of the pigment on the film surface does not occur even at a high electrophoretic voltage, coloring is possible in a wide voltage range, and coloring with controlled shade is possible. If the pigment concentration in the bath becomes higher than 50 g / l,
Since the pigment concentration is high, the pigment easily aggregates and easily deposits on the coating surface. On the contrary, when the pigment concentration is less than 10 g / l, it is difficult to darken the color due to the small amount of pigment. Is not preferable because sufficient coloring cannot be performed. On the other hand, if the pH of the bath is less than 8.5, the pH is low, the surface potential of the pigment is low, the pigment easily aggregates, and the pigment easily deposits on the coating surface, which is not preferable. On the other hand, if the pH exceeds 10, the alkalinity is strong and the pigment deposited in the pores is dissolved and dispersed again, resulting in a lighter color and uneven color.
【０００９】顔料分散体の作製には、顔料として高級有
機顔料やカーボンブラック、分散剤として陰イオン性の
高分子活性剤、たとえばナフタリ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
酸塩及びこれらの共重合体を用いるが、この時、分散剤
の溶解や分散の安定剤として、アルカリや種々の添加剤
が加えられる。また着色に供する際にもｐＨの調整等で
薬品が加えられる。上記高級有機顔料は、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、１
０〜５００ｎｍの大きさの一次粒子が集合して凝集体を
形成しており、この凝集体を粒子径３〜１５０ｎｍの大
きさにまで分散させることが好ましい。これら顔料粒子
の微細化と分散化は、前記特開平５−９３２９６号公報
に記載のように、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、ポリアクリル酸塩又は
これらの共重合体などを用いてサンドミルで分散させて
安定な水分散体を得る方法、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
ておき、より優れた水分散体を得る方法、あるいはさら
に、濃硫酸等に溶解する顔料については、一度濃硫酸等
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などを単独で又は併用して採用する
ことが出来る。To prepare a pigment dispersion, a higher organic pigment or carbon black is used as a pigment, and an anionic polymer activator is used as a dispersant, for example, a formalin condensate of naphthalene sulfonic acid, a polystyrene sulfonate, or a polyacrylate. Also, these copolymers are used, but at this time, an alkali and various additives are added as a stabilizer for the dissolution or dispersion of the dispersant. Also, when it is used for coloring, a chemical is added to adjust the pH. The above high-grade organic pigments are pigments that have made remarkable progress in recent years, and are high-quality pigments that are excellent in durability such as colorability, light resistance, weather resistance, heat resistance, and solvent resistance. Those belonging to this category include condensed azo pigments, phthalocyanine pigments, and perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments,
Examples include condensed polycyclic pigments such as isoindoline type, quinophthalone type, and metal complex type. These pigment particles generally have 1
Primary particles having a size of 0 to 500 nm are aggregated to form an aggregate, and it is preferable to disperse the aggregate to a particle size of 3 to 150 nm. As described in JP-A-5-93296, the pigment particles are finely divided and dispersed by using an anionic polymer activator as a dispersant, for example, a formalin condensate of naphthalene sulfonic acid or a polystyrene sulfonic acid. A method of obtaining a stable aqueous dispersion by dispersing with a sand mill using a salt, a polyacrylic acid salt or a copolymer thereof, a pigment is subjected to a surface treatment such as plasma treatment before the dispersion with a sand mill. , A method of obtaining a better aqueous dispersion, or, for pigments that dissolve in concentrated sulfuric acid, etc., a method of once dissolving it in concentrated sulfuric acid, etc., adding it to water, and precipitating it as finer pigment particles, etc. They can be used alone or in combination.
【００１０】上記のような有機顔料やカーボンブラック
を析出・充填させる多孔質陽極酸化皮膜としては、通常
の陽極酸化皮膜のポア径よりも大きな細孔、例えば５０
〜２００ｎｍ（５００〜２０００Å）程度の細孔を持つ
多孔質陽極酸化皮膜が望ましい。このような大きな細孔
を有する多孔質陽極酸化皮膜は、従来公知の種々の方法
により作成可能である。また、本出願人により既に特開
平５−９３２９６号公報で提案されている陽極酸化皮膜
の作成方法を好適に用いることができ、その方法は大別
して以下の二つの方法からなる。 （１）アルミニウムを鉱酸又は有機酸、例えば硫酸、リ
ン酸、シュウ酸、マロン酸、マレイン酸等の１種又は２
種以上の酸水溶液中で高電圧（例えば、ＤＣ１５０〜２
００Ｖ）で陽極酸化し、該アルミニウムの表面に通常の
ポア径より大きい細孔を持つ多孔質陽極酸化皮膜を形成
させる方法、及び（２）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、シュウ酸、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
化皮膜の細孔の孔径拡大処理を行う方法。The porous anodic oxide film for depositing / filling the organic pigment or carbon black as described above has pores larger than the pore size of a normal anodic oxide film, for example, 50.
A porous anodized film having pores of about 200 nm (500 to 2000 Å) is desirable. The porous anodic oxide film having such large pores can be prepared by various conventionally known methods. Further, the method of forming an anodic oxide film already proposed by the present applicant in Japanese Patent Application Laid-Open No. 5-93296 can be suitably used, and the method is roughly classified into the following two methods. (1) Aluminum is used as a mineral acid or an organic acid such as sulfuric acid, phosphoric acid, oxalic acid, malonic acid, maleic acid, etc.
High voltage (eg DC 150-2
00V) to form a porous anodic oxide film having pores larger than the normal pore size on the surface of the aluminum, and (2) one or more of mineral acid or organic acid. After anodizing in an acid aqueous solution of to form a porous anodized film on the surface of the aluminum,
One or two of phosphoric acid, sulfuric acid, oxalic acid, sulfamic acid
A method of enlarging the pore size of the pores of the porous anodic oxide coating by a treatment of dipping in an aqueous acid solution of one or more kinds or a treatment of repeating dipping and alternating current electrolysis in a constant cycle.
【００１１】着色処理においては、有機顔料やカーボン
ブラック等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泳動析着され、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
処理を行うことができる。In the coloring treatment, an electrophoretic treatment using an aluminum material having the above anodic oxide coating as an anode in an aqueous dispersion of an organic pigment or carbon black or the like is carried out, whereby the dispersed pigment is electrophoretically deposited even deep in the pores of the coating. As a result, a bright colored film can be obtained. The electrophoresis method includes a DC voltage scanning method in which a DC voltage is scanned from a low voltage to a high voltage at a constant boosting rate until a desired color is obtained, and a DC voltage scanning method in which a constant voltage is electrolyzed for a time until a desired color is obtained. Coloring treatment can be performed by a voltage method or the like.
【００１２】電気泳動処理の条件は、陽極酸化の条件、
使用する顔料分散体及び所望の色濃度等に応じて適宜設
定することができる。例えば直流定電圧電解法で電気泳
動を行う場合、泳動電圧が高くなるにしたがい皮膜は濃
く着色され、泳動電圧が高くなり過ぎると顔料の皮膜表
面への異常析出が始まるが、顔料濃度が高くなると異常
析出する電圧が高くなるため、良好な状態で濃く着色さ
れた皮膜が得られる。一方、低い電圧では、顔料濃度が
高いと色むらの発生がみられる。そのため、例えば陽極
酸化電圧が１３０Ｖの場合、顔料濃度に応じて一般に１
１０〜１４０Ｖの範囲に設定することが望ましい。ま
た、泳動電圧が低い場合、浴温度が高くなるにしたがっ
て皮膜は濃く着色されるが、高電圧では大きな差はみら
れない。しかし、高電圧では、浴温度が高いと顔料の皮
膜表面への異常析出が起こり易くなる。従って、浴温度
は２５℃以下、好ましくは１５〜２５℃の範囲が望まし
い。このような電気泳動処理条件で着色処理を行うこと
により、色むらのない良好な着色が可能となり、また顔
料の皮膜表面への異常析出を起こさないで皮膜の濃淡が
広い電圧範囲で制御できる。なお、このようにして得ら
れたアルミニウムの着色皮膜には、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。The conditions of the electrophoretic treatment are the conditions of anodic oxidation,
It can be set appropriately according to the pigment dispersion used, the desired color density, and the like. For example, in the case of performing electrophoresis by the direct current constant voltage electrolysis method, the film is colored deeply as the migration voltage becomes high, and when the migration voltage becomes too high, abnormal deposition of the pigment on the film surface starts, but when the pigment concentration becomes high. Since the voltage for abnormal deposition increases, a darkly colored film can be obtained in a good state. On the other hand, at a low voltage, color unevenness occurs when the pigment concentration is high. Therefore, for example, when the anodic oxidation voltage is 130 V, it is generally 1 depending on the pigment concentration.
It is desirable to set in the range of 10 to 140V. Further, when the migration voltage is low, the coating is deeply colored as the bath temperature increases, but no significant difference is observed at high voltage. However, at high voltage, when the bath temperature is high, abnormal deposition of the pigment on the coating surface is likely to occur. Therefore, the bath temperature is preferably 25 ° C. or lower, preferably 15 to 25 ° C. By performing the coloring treatment under such an electrophoretic treatment condition, good coloring without color unevenness is possible, and the density of the coating can be controlled in a wide voltage range without causing abnormal deposition of the pigment on the coating surface. The colored coating of aluminum thus obtained may be subjected to sealing treatment or clear coating, if necessary.
【００１３】[0013]
【実施例】以下、実施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。The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to the following examples.
【００１４】実施例１ 工業用純アルミ材Ａ１１００材を常法に従って前処理し
た後、２０℃の０．３％シュウ酸浴中で１５０Ｖ定電圧
電解を行った。次いで３０℃の５％リン酸溶液中に６０
分浸漬し、最後にホウ酸中性浴中で１１０Ｖで電解を行
い、皮膜厚１３μｍの陽極酸化皮膜を得た。その後、該
アルミ材を陽極として、ｐＨが９．０、比電導度が４０
００μＳ／ｃｍとした２５℃の濃度５０ｇ／ｌのカーボ
ンブラック水分散体中で、１３０Ｖで電気泳動処理を１
分間行い、鮮やかに着色された均一な黒色皮膜を得た。
なお、顔料の水分散体は、ポリアクリル酸ソーダを用い
て分散して調製し、その顔料粒径は６０ｎｍであった。Example 1 Industrial pure aluminum material A1100 material was pretreated by a conventional method, and then 150V constant voltage electrolysis was carried out in a 0.3% oxalic acid bath at 20 ° C. 60% in 5% phosphoric acid solution at 30 ° C.
It was dipped for a minute, and finally electrolyzed at 110 V in a neutral boric acid bath to obtain an anodized film having a film thickness of 13 μm. Then, using the aluminum material as an anode, the pH was 9.0 and the specific electric conductivity was 40.
Electrophoresis treatment was carried out at 130 V in an aqueous dispersion of carbon black having a concentration of 50 μg / l at 25 ° C. and 00 μS / cm.
It was performed for a minute to obtain a brightly colored uniform black film.
An aqueous dispersion of the pigment was prepared by dispersing it with sodium polyacrylate, and the pigment particle size was 60 nm.
【００１５】比較例１ 実施例１と同じ条件で形成した陽極酸化皮膜を用い、同
じく実施例１で用いたカーボンブラック水分散体を蒸留
水で希釈して１０ｇ／ｌの濃度とし、これに水酸化ナト
リウム及び炭酸水素ナトリウムにてｐＨを９．０、比電
導度を４０００μＳ／ｃｍに調整した２５℃の顔料分散
体中で、１３０Ｖで１分間着色処理した。得られた着色
皮膜は色むらとなり、実施例１で得られた着色皮膜より
うすい着色となった。Comparative Example 1 Using the anodic oxide film formed under the same conditions as in Example 1, the carbon black aqueous dispersion used in Example 1 was diluted with distilled water to a concentration of 10 g / l, and water was added to this. Coloring treatment was carried out at 130 V for 1 minute in a pigment dispersion at 25 ° C., the pH of which was adjusted to 9.0 with sodium oxide and sodium hydrogen carbonate, and the specific electric conductivity thereof was adjusted to 4000 μS / cm. The obtained colored film became uneven in color and was lighter in color than the colored film obtained in Example 1.
【００１６】実施例２及び比較例２ 実施例１と同じ条件で形成した陽極酸化皮膜を、ポリア
クリル酸ソーダを分散剤に用いて、ｐＨを９．５、比電
導度が１２００μＳ／ｃｍとした２０ｇ／ｌの濃度の銅
フタロシアニンブルー水分散体中で、温度を表１に示す
１５〜３５℃の範囲の種々の温度に設定して電気泳動処
理し、着色した。泳動電圧は１２５Ｖとし、電気泳動処
理を１分間行った。なお、顔料の水分散体は、ポリアク
リル酸ソーダを用いて分散して調製し、その顔料粒径は
４０ｎｍであった。その結果を表１に示す。また、比較
例２として、同じ顔料濃度の銅フタロシアニンブルー水
分散体にマレイン酸ソーダ及び水酸化ナトリウムを加
え、ｐＨを９．５、比電導度を４０００μＳ／ｃｍとし
た分散体で泳動着色した結果も併せて示す。Example 2 and Comparative Example 2 The anodic oxide film formed under the same conditions as in Example 1 was adjusted to pH 9.5 and specific electric conductivity 1200 μS / cm by using sodium polyacrylate as a dispersant. In a copper phthalocyanine blue water dispersion having a concentration of 20 g / l, the temperature was set to various temperatures within the range of 15 to 35 ° C. shown in Table 1 and the sample was subjected to electrophoresis treatment and colored. The electrophoretic voltage was 125 V, and the electrophoretic treatment was performed for 1 minute. An aqueous dispersion of the pigment was prepared by dispersing it with sodium polyacrylate, and the pigment particle size was 40 nm. Table 1 shows the results. As Comparative Example 2, sodium phthalate and sodium hydroxide were added to an aqueous dispersion of copper phthalocyanine blue having the same pigment concentration, and electrophoretic coloring was performed using a dispersion having a pH of 9.5 and a specific conductivity of 4000 μS / cm. Is also shown.
【００１７】[0017]
【表１】 表１に示す結果から明らかなように、比較例２のように
浴中の顔料濃度１０ｇ／ｌ当り４０００μＳ／ｃｍの高
い比電導度で電気泳動処理を行った場合、いずれの浴温
度においても色むらを生じ、特に高い浴温度においては
陽極酸化皮膜表面に顔料が異常析出したが、本発明に従
って浴中の顔料濃度１０ｇ／ｌ当り６００μＳ／ｃｍの
比電導度で電気泳動処理を行った場合、広い浴温度範囲
で、色むらや顔料の表面析出もなく、多孔質陽極酸化皮
膜の細孔内に顔料が析出・充填され、着色堅牢性に優れ
た色鮮やかな着色皮膜が得られた。但し、浴温度が３０
℃以上になると、色むらや顔料の表面析出が観察され
た。従って、浴温度は２５℃以下、特に１５〜２５℃の
範囲が好ましい。[Table 1] As is clear from the results shown in Table 1, when the electrophoretic treatment was carried out at a high specific conductivity of 4000 μS / cm per 10 g / l of the pigment concentration in the bath as in Comparative Example 2, the color was obtained at any bath temperature. The unevenness occurred, and the pigment was abnormally deposited on the surface of the anodic oxide film at a particularly high bath temperature. However, when the electrophoretic treatment was performed according to the present invention at a specific conductivity of 600 μS / cm per 10 g / l of the pigment concentration in the bath, Within a wide bath temperature range, the pigment was deposited and filled in the pores of the porous anodic oxide coating without color irregularity or surface deposition of the pigment, and a bright colored coating with excellent coloring fastness was obtained. However, the bath temperature is 30
At temperatures above ℃, color unevenness and surface precipitation of pigments were observed. Therefore, the bath temperature is preferably 25 ° C or lower, and particularly preferably in the range of 15 to 25 ° C.
【００１８】実施例３及び比較例３ 実施例１と同じ条件で形成した陽極酸化皮膜を用い、ポ
リスチレンスルホン酸ソーダを用いて分散した表２に示
す顔料濃度５〜１００ｇ／ｌの範囲の種々の濃度の銅フ
タロシアニングリーンの水分散体中で、泳動電圧１２５
Ｖで１分間電気泳動処理し、着色を行った。なお、この
ときのｐＨは９．０であり、顔料粒径は４０ｎｍであっ
た。このときの顔料分散体の比電導度と着色結果を表２
に示す。また、比較例３として、顔料濃度を５ｇ／ｌ一
定にし、比電導度を実施例３と同じように調整して着色
した場合の着色状態も併せて示す。Example 3 and Comparative Example 3 Using the anodic oxide film formed under the same conditions as in Example 1, dispersed with sodium polystyrene sulfonate, various pigment concentrations shown in Table 2 were in the range of 5 to 100 g / l. In an aqueous dispersion of copper phthalocyanine green of high concentration, a migration voltage of 125
Electrophoresis was carried out for 1 minute with V for coloring. At this time, the pH was 9.0 and the pigment particle size was 40 nm. Table 2 shows the specific electric conductivity and the coloring result of the pigment dispersion at this time.
Shown in In addition, as Comparative Example 3, the coloring state when the pigment concentration is fixed at 5 g / l and the specific electric conductivity is adjusted in the same manner as in Example 3 for coloring is also shown.
【００１９】[0019]
【表２】 表２に示す結果から、電気泳動浴中の顔料濃度が低すぎ
ると顔料の表面析出が観察され、逆に高すぎると色むら
が観察された。従って、顔料濃度は１０〜５０ｇ／ｌ、
特に１０〜４０ｇ／ｌが望ましい。[Table 2] From the results shown in Table 2, when the pigment concentration in the electrophoresis bath was too low, surface precipitation of the pigment was observed, and conversely, when it was too high, color unevenness was observed. Therefore, the pigment concentration is 10 to 50 g / l,
Particularly, 10 to 40 g / l is desirable.
【００２０】実施例４及び比較例４ 実施例１と同じ条件で形成した陽極酸化皮膜を用い、ナ
フタレンスルホン酸ナトリウムホルマリン縮合物を分散
剤とした１０ｇ／ｌの濃度のキナクリドンレッドの分散
体中で、表３に示すようにｐＨを変え、１２０Ｖで１分
間電気泳動処理し、着色を行った。なお、浴温は２０
℃、顔料粒径は７０ｎｍであった。ｐＨ８．５〜１０．
０では均一な赤色着色皮膜が得られたが、ｐＨ１１で
は、淡赤色で色むらとなり、ｐＨ１２では着色しなかっ
た。また、比較例４として、ｐＨ１０以下の浴をｐＨ１
２の浴の比電導度（３０００μＳ／ｃｍ）と同じに四ホ
ウ酸ナトリウムを用いて調整し着色したところ、うすい
色むらの着色となった。結果を表３に示す。Example 4 and Comparative Example 4 Using the anodic oxide film formed under the same conditions as in Example 1, in a dispersion of quinacridone red at a concentration of 10 g / l using sodium naphthalenesulfonate formalin condensate as a dispersant. As shown in Table 3, pH was changed, and electrophoresis was performed at 120 V for 1 minute to perform coloring. The bath temperature is 20
C., the particle size of the pigment was 70 nm. pH 8.5-10.
At 0, a uniform red colored film was obtained, but at pH 11, it became light red and uneven in color, and at pH 12, it was not colored. In addition, as Comparative Example 4, a bath having a pH of 10 or less was adjusted to pH 1
When adjusted by using sodium tetraborate in the same manner as the specific electric conductivity (3000 μS / cm) of the bath No. 2 and colored, it became light and uneven coloring. The results are shown in Table 3.
【００２１】[0021]
【表３】 [Table 3]
【００２２】[0022]
【発明の効果】以上のように、本発明のアルミニウムの
着色方法によれば、顔料の泳動に無関係な電流が殆んど
流れないように顔料分散体の浴の比電導度を顔料濃度１
０ｇ／ｌ当り１０００μＳ／ｃｍ以下に調整して電気泳
動を行うものであるため、前記したような陽極反応の生
起や皮膜近傍でのｐＨの急激な低下が抑制され、顔料の
異常な凝集を防止でき、従って、色むらや皮膜表面への
顔料の異常析出のない着色を行うことができる。また、
広い電圧範囲で所望の濃淡の着色皮膜に着色が可能とな
り、しかも顔料は皮膜細孔の深部にまで析出・充填され
ているため、耐光性、耐候性、耐熱性等の諸特性に優
れ、顔料の離脱もなく、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も十分に応えることが
できる。As described above, according to the method for coloring aluminum of the present invention, the specific electric conductivity of the bath of the pigment dispersion is adjusted so that a current irrelevant to the migration of the pigment hardly flows.
Since the electrophoresis is performed by adjusting the concentration to 1000 μS / cm or less per 0 g / l, the occurrence of the anodic reaction and the sharp drop in pH near the film as described above are suppressed, and abnormal pigment aggregation is prevented. Therefore, it is possible to perform coloring without uneven color or abnormal deposition of the pigment on the surface of the film. Also,
It is possible to color a desired tint colored film over a wide voltage range, and since the pigment is deposited and filled deep into the pores of the film, it has excellent properties such as light resistance, weather resistance, and heat resistance. It is possible to obtain a bright and colored film which is robust and has excellent durability without separation. Also, by selecting a pigment, it can be colored in various desired colors such as red, black, and blue.
It can fully meet the needs for multi-colored aluminum.
Claims (5)
ウム又はアルミニウム合金を、顔料濃度１０ｇ／ｌ当り
１０００μＳ／ｃｍ以下の比電導度に調整した有機顔料
又はカーボンブラックの顔料分散体の浴中で電気泳動処
理し、多孔質陽極酸化皮膜の細孔深部にまで有機顔料又
はカーボンブラックを析出・充填させ着色することを特
徴とするアルミニウム又はアルミニウム合金の着色方
法。1. An aluminum or aluminum alloy on which a porous anodic oxide film is formed is adjusted to have a specific electric conductivity of 1000 μS / cm or less per 10 g / l of pigment concentration in a bath of a pigment dispersion of an organic pigment or carbon black. A method for coloring aluminum or an aluminum alloy, which comprises performing an electrophoretic treatment and depositing and filling an organic pigment or carbon black even in deep pores of a porous anodic oxide coating to color.
ーボンブラックの顔料分散体を用いることを特徴とする
請求項１に記載の着色方法。2. The coloring method according to claim 1, wherein an organic pigment or a carbon black pigment dispersion having a particle diameter of 3 to 150 nm is used.
ｇ／ｌ以下、好ましくは１０〜４０ｇ／ｌであることを
特徴とする請求項１又は２に記載の着色方法。3. The pigment concentration in the bath of the pigment dispersion is 50.
g / l or less, preferably 10 to 40 g / l, the coloring method according to claim 1 or 2.
℃であることを特徴とする請求項１乃至３のいずれか一
項に記載の着色方法。4. The temperature of the pigment dispersion bath is 15 to 25.
4. The coloring method according to any one of claims 1 to 3, wherein the coloring method is C.
好ましくは８．５〜９．５であることを特徴とする請求
項１乃至４のいずれか一項に記載の着色方法。5. The pH of the pigment dispersion bath is 10 or less,
The coloring method according to any one of claims 1 to 4, wherein the coloring method is preferably 8.5 to 9.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6055017A JP2995711B2 (en) | 1994-03-01 | 1994-03-01 | Method of coloring aluminum or aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6055017A JP2995711B2 (en) | 1994-03-01 | 1994-03-01 | Method of coloring aluminum or aluminum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07243092A true JPH07243092A (en) | 1995-09-19 |
| JP2995711B2 JP2995711B2 (en) | 1999-12-27 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6055017A Expired - Fee Related JP2995711B2 (en) | 1994-03-01 | 1994-03-01 | Method of coloring aluminum or aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2995711B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006269425A (en) * | 2005-03-21 | 2006-10-05 | Samsung Sdi Co Ltd | Secondary battery and its manufacturing method |
| JP2007009333A (en) * | 2006-10-23 | 2007-01-18 | Shinshu Univ | Plated structure and method of manufacturing the same |
| WO2013010289A1 (en) * | 2011-07-15 | 2013-01-24 | Chan Tu Cheng | Filling decoration method for surface of workpiece |
| KR20130035246A (en) * | 2011-09-29 | 2013-04-08 | 덴카 히마쿠 고교 가부시키가이샤 | Method for manufacturing colored aluminum product or colored aluminum alloy product, pigment composition for coloration, and colored aluminum product or colored aluminum alloy product |
| WO2013075267A1 (en) * | 2011-11-25 | 2013-05-30 | Chan Tu Cheng | Workpiece surface color treatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495840A (en) * | 1972-05-11 | 1974-01-19 | ||
| JPH0593296A (en) * | 1991-09-30 | 1993-04-16 | Yoshida Kogyo Kk <Ykk> | Colored aluminum or aluminum alloy and its coloring method |
-
1994
- 1994-03-01 JP JP6055017A patent/JP2995711B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495840A (en) * | 1972-05-11 | 1974-01-19 | ||
| JPH0593296A (en) * | 1991-09-30 | 1993-04-16 | Yoshida Kogyo Kk <Ykk> | Colored aluminum or aluminum alloy and its coloring method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006269425A (en) * | 2005-03-21 | 2006-10-05 | Samsung Sdi Co Ltd | Secondary battery and its manufacturing method |
| JP2007009333A (en) * | 2006-10-23 | 2007-01-18 | Shinshu Univ | Plated structure and method of manufacturing the same |
| JP4599565B2 (en) * | 2006-10-23 | 2010-12-15 | 国立大学法人信州大学 | Electrolytic plating method and electrolytic plating solution |
| WO2013010289A1 (en) * | 2011-07-15 | 2013-01-24 | Chan Tu Cheng | Filling decoration method for surface of workpiece |
| CN103717789A (en) * | 2011-07-15 | 2014-04-09 | 明通企业股份有限公司 | Filling decoration method for surface of workpiece |
| KR20130035246A (en) * | 2011-09-29 | 2013-04-08 | 덴카 히마쿠 고교 가부시키가이샤 | Method for manufacturing colored aluminum product or colored aluminum alloy product, pigment composition for coloration, and colored aluminum product or colored aluminum alloy product |
| WO2013075267A1 (en) * | 2011-11-25 | 2013-05-30 | Chan Tu Cheng | Workpiece surface color treatment method |
| CN103917698A (en) * | 2011-11-25 | 2014-07-09 | 詹涂城 | Workpiece surface color treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2995711B2 (en) | 1999-12-27 |
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