JPS5846558B2 - Method for forming colored patterns on aluminum or aluminum alloy - Google Patents
Method for forming colored patterns on aluminum or aluminum alloyInfo
- Publication number
- JPS5846558B2 JPS5846558B2 JP14414179A JP14414179A JPS5846558B2 JP S5846558 B2 JPS5846558 B2 JP S5846558B2 JP 14414179 A JP14414179 A JP 14414179A JP 14414179 A JP14414179 A JP 14414179A JP S5846558 B2 JPS5846558 B2 JP S5846558B2
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- JP
- Japan
- Prior art keywords
- sodium
- phosphate
- potassium
- carbonate
- aluminum
- 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
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- Electrochemical Coating By Surface Reaction (AREA)
Description
【発明の詳細な説明】
本発明はアルミニウムまたはアルミニウム合金(以下ア
ルミニウムという)の被処理物表面に電気化学的に鮮明
な着色筋目模様を形成させる方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for electrochemically forming a clear colored streak pattern on the surface of an aluminum or aluminum alloy (hereinafter referred to as aluminum) workpiece.
従来アルミニウム表面に筋目模様を形成させる電気化学
的方法として特開昭52−60244が知られている。JP-A-52-60244 is known as an electrochemical method for forming a streak pattern on an aluminum surface.
該技術は被処理物を各種ナトリウム塩の少なくとも一種
を添加した浴、あるいは前記浴に各種バリヤー型皮膜物
質のいずれか一種を加えた浴中で交流電解し、その表面
に模様付けを行う方法に関する。This technique relates to a method of subjecting a workpiece to alternating current electrolysis in a bath to which at least one of various sodium salts has been added, or a bath to which one of various barrier-type coating materials has been added, and patterning the surface thereof. .
しかしながら、該方法により被処理体に模様を形成して
から常法により前記被処理体に陽極酸化被膜を形威し、
その後金属塩を添加した無機着色浴中で交流電解し、前
記模様に着色処理を施すと、得られる着色模様は非常に
不鮮明に表われるという欠点がある。However, after forming a pattern on the object to be treated by this method, forming an anodic oxide film on the object by a conventional method,
If the pattern is then subjected to alternating current electrolysis in an inorganic coloring bath to which metal salts have been added and the pattern is colored, the resulting colored pattern has the disadvantage that it appears very indistinctly.
この理由は次のように推測される。The reason for this is assumed to be as follows.
■ 該方法により得られる着色模様は、表面粗さ、すな
わち、表面のマットな部分と平滑な部分の呈する光沢の
違いを利用するものであるため、見る方向により模様の
輪郭が不明瞭となる。(2) The colored pattern obtained by this method makes use of the surface roughness, that is, the difference in gloss exhibited by matte and smooth parts of the surface, so the outline of the pattern becomes unclear depending on the viewing direction.
■ 該方法により得られる着色模様の色彩は2色のみで
あり、かつ類似した色彩であるため、模様の輪郭が不鮮
明に視覚される。(2) The colored pattern obtained by this method has only two colors, and since the colors are similar, the outline of the pattern appears unclear.
また、該方法によるとアルミニウム素地面または得られ
たバリヤ型皮膜面が各種ナトリウム塩の作用により、い
わゆる軽く食刻された状態であるため、着色模様が硬い
線として視覚され、自然木の木目模様とかけ離れたもの
であった。In addition, according to this method, the aluminum base surface or the obtained barrier type film surface is in a so-called lightly etched state due to the action of various sodium salts, so the colored pattern is perceived as hard lines, and the grain pattern of natural wood is visible. It was a far cry from that.
そこでより一層自然木の感じを与える柔かな線をもった
筋目模様が要望されていた。Therefore, there was a demand for a vein pattern with soft lines that would give an even more natural wood feel.
本発明は前記問題点にかんがみ、なされたものであり、
第1の目的は模様部を強く食刻し、はっきりした筋目模
様を形成することである。The present invention has been made in view of the above problems, and
The first purpose is to strongly etch the pattern to form a clear streak pattern.
第2の目的は筋目模様形成工程と着色皮膜工程の間に模
様調整工程を設けて、着色皮膜を形成した時、模様の中
央部、端部および非模様部の色彩がそれぞれ異なる濃淡
3色模様の装飾効果にすぐれた着色筋目模様を得ること
である。The second purpose is to provide a pattern adjustment process between the streak pattern forming process and the colored film process, so that when the colored film is formed, a three-color pattern with different shading and light colors in the center, edges, and non-patterned parts of the pattern is created. To obtain a colored streak pattern with excellent decorative effect.
さらに、第3の目的は、柔かでかつ滑らかな、いわゆる
自然木の筋目模様に近似した着色模様を得ることである
。Furthermore, the third objective is to obtain a colored pattern that is soft and smooth and approximates the so-called vein pattern of natural wood.
前記目的は本発明の以下に述べる方法によって達成され
る。The above object is achieved by the method of the invention described below.
すなわち、本発明はアルミニウム表面に常法により陽極
酸化皮膜を形成し、続いて無機酸または有機酸のアルカ
リ金属塩もしくはアルカリ土類金属塩の一種または二種
以上を含む電解液中で交流電解し、引続き同一液中で直
流陰極電解して凹凸のある筋目模様を付けた後、無機酸
または有機酸のアルカリ金属塩もしくはアルカリ土類金
属塩を含むpH6〜11の水溶液中で交流電解し、しか
る後着色皮膜を形成させることを特徴とするアルミニウ
ムの着色模様形成方法である。That is, in the present invention, an anodic oxide film is formed on an aluminum surface by a conventional method, and then AC electrolysis is performed in an electrolytic solution containing one or more types of alkali metal salts or alkaline earth metal salts of inorganic acids or organic acids. Then, after applying direct current cathodic electrolysis in the same solution to form an uneven streak pattern, alternating current electrolysis is carried out in an aqueous solution with a pH of 6 to 11 containing an alkali metal salt or alkaline earth metal salt of an inorganic or organic acid. This is a method for forming a colored pattern on aluminum, which is characterized by forming a post-colored film.
本発明の方法では前記筋目模様付は工程における交流電
解を省略して直流陰極電解を行って模様付けすることも
できる。In the method of the present invention, the streak pattern can also be created by omitting the AC electrolysis in the process and performing DC cathode electrolysis.
本発明に使用される電解液の無機酸または有機酸のアル
カリ金属塩としては、リン酸カルシウム、リン酸カリウ
ム、ピロリン酸カリウム、メタリン酸カリウム、リン酸
ナトリウム、メタリン酸ナトリウム、次亜リン酸ナトリ
ウム、ピロリン酸ナトリウム、環リン酸ナトリウム、リ
ン酸三ナトリウム、リン酸水素アンモニウムナトリウム
、リン酸リチウム等がありまた、アルカリ土類金属塩と
しては、リン酸亜鉛、リン酸水素カルシウム、リン酸カ
ルシウム、リン酸マグネシウムアンモニウム、炭酸ナト
リウム、炭酸カリウム、炭酸カルシウム、クロム酸ナト
リウム、クロム酸カリウム、メタホウ酸ナトリウム、ク
エン酸ナトリウム、酒石酸ナトリウム、フタル酸ナトリ
ウム、マレイン酸ナトリウム等がある。Examples of the alkali metal salts of inorganic or organic acids in the electrolyte used in the present invention include calcium phosphate, potassium phosphate, potassium pyrophosphate, potassium metaphosphate, sodium phosphate, sodium metaphosphate, sodium hypophosphite, and pyrroline. Examples of alkaline earth metal salts include zinc phosphate, calcium hydrogen phosphate, calcium phosphate, and magnesium ammonium phosphate. , sodium carbonate, potassium carbonate, calcium carbonate, sodium chromate, potassium chromate, sodium metaborate, sodium citrate, sodium tartrate, sodium phthalate, sodium maleate, and the like.
これらの薬品は一種類のみでもよく、また二種類以上混
合してもよい。These chemicals may be used alone or in combination of two or more.
さらに、前記電解液の電気伝導度、液の安定化、液のp
Hを適当な状態に保つため、添加剤として硫酸、亜リン
酸、クロム酸、硝酸、けい酸、酢酸、クエン酸、グルコ
ン酸、シュウ酸、スルファミン酸、酒石酸などの無機酸
または有機酸の一種または二種以上を添加するのが好ま
しい。Furthermore, the electrical conductivity of the electrolyte, the stabilization of the solution, the p of the solution,
To maintain H in an appropriate state, an inorganic or organic acid such as sulfuric acid, phosphorous acid, chromic acid, nitric acid, silicic acid, acetic acid, citric acid, gluconic acid, oxalic acid, sulfamic acid, or tartaric acid is used as an additive. Alternatively, it is preferable to add two or more kinds.
また、前記筋目模様付は工程後に行う、模様調整のため
の無機酸または有機酸のアルカリ土類金としでは炭酸ナ
トリウム、炭酸水素ナトリウム、リン酸三ナトリウム、
リン酸水素ナトリウム、ピロリン酸ナトリウム、メタホ
ウ酸ナトリウム、硫酸水素ナトリウム、シュウ酸ナトリ
ウム、フッ化ナトリウム、グルコン酸ナトリウム、水酸
化ナトリウム、クエン酸ナトリウム、硫酸ナトリウム、
酢酸ナトリウム、酒石酸ナトリウム、ケイ酸ナトリウム
、スルファミン酸ナトリウム、フッ化カリウム、硫酸カ
リウム、ケイ酸カリウム、酒石酸カリウム、ピロリン酸
カリウム、酢酸カリウム、炭酸カリウム等がありこれら
の一種類または二種類以上が用いられる。In addition, the above-mentioned streak patterning is carried out after the process, and examples of alkaline earth metals of inorganic or organic acids for pattern adjustment include sodium carbonate, sodium hydrogen carbonate, trisodium phosphate,
Sodium hydrogen phosphate, sodium pyrophosphate, sodium metaborate, sodium hydrogen sulfate, sodium oxalate, sodium fluoride, sodium gluconate, sodium hydroxide, sodium citrate, sodium sulfate,
Sodium acetate, sodium tartrate, sodium silicate, sodium sulfamate, potassium fluoride, potassium sulfate, potassium silicate, potassium tartrate, potassium pyrophosphate, potassium acetate, potassium carbonate, etc., and one or more of these are used. It will be done.
本発明方法を実施するには、まずアルミニウム表面に常
法によって脱脂、エツチング、中和等の前処理を施し、
ついで前記無機酸または有機酸あるいは、これらの混酸
からなる電解液中で電解処理することにより、アルミニ
ウム表面に陽極酸化皮膜を形成し水洗後に次の筋目模様
形成工程に移る。To carry out the method of the present invention, first, the aluminum surface is pretreated by conventional methods such as degreasing, etching, and neutralization.
Next, an anodic oxide film is formed on the aluminum surface by electrolytic treatment in an electrolytic solution made of the inorganic acid, organic acid, or a mixed acid thereof, and after washing with water, the next step of forming a streak pattern is performed.
すなわち、無機酸または有機酸のアルカリ金属塩もしく
はアルカリ土類金属塩の一種または二種以上を含む電解
液中に添加剤として無機酸または有機酸の一種または二
種以上を加え、pH調整して、前記アルミニウムを前記
電解液中に浸漬し、対極にステンレス、またはカーボン
を用い、次の処理条件で交流電解を行い、アルミニウム
表面に局部的なピッティングを発生させる。That is, one or more types of inorganic acids or organic acids are added as additives to an electrolytic solution containing one or more types of alkali metal salts or alkaline earth metal salts of inorganic acids or organic acids, and the pH is adjusted. The aluminum is immersed in the electrolytic solution, and using stainless steel or carbon as a counter electrode, alternating current electrolysis is performed under the following processing conditions to generate local pitting on the aluminum surface.
(I) 電流密度 0.1〜2.OA/d〆好ましく
は0.3〜1.OA/di
(n) 無機・有機酸塩の濃度 0.1〜50 g/
13好ましくは 1.0〜10 g/It
(III) 電解液のp)T 1〜11、好ましく
は2〜5(I%’) 電解液の温度範囲 10〜50
℃、好ましくは20〜35℃
(V)処理時間 0.5〜10分、好ましくは1〜5分
この交流電解は、前工程で得られた陽極酸化皮膜上に筋
目模様の基点を形成するための工程であり、その模様形
態の目的に応じて、液温、pH1印加電圧、電流密度、
濃度、組成等の各要因の相関関係により最適条件を選択
する。(I) Current density 0.1-2. OA/d〆Preferably 0.3-1. OA/di (n) Concentration of inorganic/organic acid salts 0.1-50 g/
13 Preferably 1.0-10 g/It (III) p)T of electrolyte 1-11, preferably 2-5 (I%') Temperature range of electrolyte 10-50
°C, preferably 20 to 35 °C (V) Treatment time 0.5 to 10 minutes, preferably 1 to 5 minutes This AC electrolysis is used to form the base points of the streak pattern on the anodic oxide film obtained in the previous step. The process is based on the liquid temperature, pH1 applied voltage, current density,
Optimum conditions are selected based on the correlation of each factor such as concentration and composition.
たとえば、処理時間の長短により、または電流密度の高
底により単位面積当りの筋目模様の量を調節することが
できる。For example, the amount of streaks per unit area can be adjusted by lengthening or shortening the processing time or by changing the current density.
すなわち、電解処理時間が長いほど、また電流密度が高
いほど筋目模様が多く表出し、相互の間隔が狭くなる。That is, the longer the electrolytic treatment time and the higher the current density, the more streaks appear and the mutual spacing becomes narrower.
また、アルミニウムの全面溶解を抑え、かつその溶出を
防ぐためpHを2〜5に保つのが好ましい0
交流電解の印加電圧を高くすると前記陽極酸化皮膜のバ
リヤ一層が成長し、後の着色工程において、非模様部に
鮮明な着色がなされない場合があるので低電圧15〜3
5Vで処理することが好ましい。In addition, in order to suppress the total dissolution of aluminum and prevent its elution, it is preferable to keep the pH at 2 to 5.0 When the applied voltage of AC electrolysis is increased, a layer of the barrier layer of the anodic oxide film grows, and in the subsequent coloring process. , because the non-patterned areas may not be clearly colored, use a low voltage of 15 to 3.
It is preferable to process at 5V.
つぎに同浴中で電源を切替え、前記アルミニウムを陰極
として、直流もしくはこれと同等の効果をもつ電流波形
により直流陰極電解する。Next, in the same bath, the power source is switched, and direct current cathodic electrolysis is carried out using direct current or a current waveform having an equivalent effect, using the aluminum as a cathode.
この場合、電流密度は0.5〜3.OA/drrl”好
ましくは1、0〜1.5 A/ dm2、処理時間は5
〜20分、好ましくは5〜15分の条件で実施さぁこれ
によって局部的に破壊された陽極酸化皮膜のピッティン
グ部を基点としで、アルミニウムの陽極酸化皮膜および
素地面がえぐり取られるように食刻され、時間の経過と
ともに食刻が成長して筋目模様が形成される。In this case, the current density is 0.5 to 3. OA/drrl” preferably 1.0 to 1.5 A/dm2, processing time is 5
Carry out the process for ~20 minutes, preferably 5 to 15 minutes. Starting from the pitting area of the locally destroyed anodic oxide film, the aluminum anodized film and base surface are gouged out. The etches grow over time, forming a streaked pattern.
上記のように模様形成工程においては、交流電解に続い
て同じ電解液中でアルミニウムを陰極に接続し、直流電
解するのであるが、この場合交流電解を省略して、常法
によりアルミニウム表面に陽極酸化皮膜を形成した後、
前記電解液中で陰極直流電解しても模様が形成できる。As mentioned above, in the pattern forming process, following AC electrolysis, aluminum is connected to the cathode in the same electrolytic solution and DC electrolysis is performed. After forming an oxide film,
A pattern can also be formed by cathodic direct current electrolysis in the electrolytic solution.
ただこの場合は模様選択条件、すなわち電解操作条件を
幅広くとることができないので交流電解を省略しない方
が有利である。However, in this case, it is not possible to have a wide range of pattern selection conditions, that is, electrolysis operation conditions, so it is advantageous not to omit AC electrolysis.
次に模様調整工程に移る。Next, move on to the pattern adjustment process.
この模様調整工程は本発明の特徴部を形成する工程であ
る。This pattern adjustment process is a process for forming the characteristic parts of the present invention.
この工程は、前記筋目模様形成後のアルミニウムを無機
酸または、有機酸のアルカリ金属塩もしくはアルカリ土
類金属塩を含む水溶液中でpHを6〜11、好ましくは
、6.5〜9に保ち、次の条件で交流電解を行うもので
ある。In this step, the aluminum after the streak pattern is formed is kept at a pH of 6 to 11, preferably 6.5 to 9, in an aqueous solution containing an inorganic acid or an alkali metal salt or alkaline earth metal salt of an organic acid. AC electrolysis is performed under the following conditions.
(I) 電流密度
0.1〜IOA/dm2、好ましくは0.5〜1.OA
/di
(II) 無機、有機酸塩の濃度
10〜120g/11好ましくは30〜80g/1
(I)電解液の温度範囲
20〜60℃、好ましくは20〜300C(IV)
処理時間
1〜15分、好ましくは5〜10分
この時、pHを前記範囲以外に調整すると後の着色酸化
皮膜形成工程後に非模様部が着色されない。(I) Current density 0.1 to IOA/dm2, preferably 0.5 to 1. OA
/di (II) Concentration of inorganic or organic acid salt 10 to 120 g/11, preferably 30 to 80 g/1 (I) Temperature range of electrolyte solution 20 to 60°C, preferably 20 to 300°C (IV)
Processing time: 1 to 15 minutes, preferably 5 to 10 minutes At this time, if the pH is adjusted outside the above range, the non-patterned areas will not be colored after the colored oxide film forming step.
すなわち、白木調模様として表出するので好ましくない
。That is, it appears as a plain wood-like pattern, which is not preferable.
この処理工程によって、後の着色酸化皮膜形成工程で、
アルミニウムに着色皮膜を形成した時得られる着色筋目
模様の中央部と端部との間にはっきり区別できる色調の
差が生じ、かつ該模様部と非模様部との間にもはっきり
と区別できる色調の差が生じ、濃淡3色の非常に鮮明で
きれいな着色筋目模様を得ることができる。Through this treatment step, in the subsequent colored oxide film formation step,
When a colored film is formed on aluminum, there is a clearly distinguishable difference in color tone between the center and the edges of the colored streak pattern, and there is also a clearly distinguishable color tone between the patterned area and the non-patterned area. A very clear and beautiful colored streak pattern in three shades of light and shade can be obtained.
この処理工程を行なうとなぜ得られる着色筋目模様が3
色に表出するか明らかでないが、恐らく前記模様調整工
程を行う事により、後の2次陽極酸化皮膜を形成した時
、最初に形成した陽極酸化皮膜と、模様形成工程でその
一部を食刻された陽極酸化皮膜および食刻されたアルミ
素地面に形成された2次陽極酸化皮膜との間の皮膜の活
性度合に差が生じ、その差が後の着色処理後に各々の皮
膜面に着色に関与する薬品や金属の析出度に差が生じ、
その差が模様の濃淡差としてアルミニウム表面に表出す
るものと推考される。Why does this processing step result in a colored streak pattern of 3?
It is not clear whether it will show up in the color, but perhaps by performing the pattern adjustment process, when the secondary anodic oxide film is formed later, the initially formed anodic oxide film and a part of it will be eroded during the pattern forming process. There is a difference in the activity level of the film between the etched anodic oxide film and the secondary anodic oxide film formed on the etched aluminum base surface, and this difference causes the surface of each film to be colored after the subsequent coloring process. Differences occur in the degree of precipitation of chemicals and metals involved in
It is assumed that this difference appears on the aluminum surface as a difference in the shade of the pattern.
また、このような模様調整工程を行うと模様食刻部に電
流が集中して食刻度が増す事と、模様周辺の陽極酸化皮
膜が電解液による軽いエツチング作用により溶出する事
により以後の着色皮膜形成後に、着色筋目模様の輪郭が
はっきりとかつ柔らかい線として表出する。In addition, when such a pattern adjustment process is performed, the current concentrates on the etched part of the pattern, increasing the degree of etching, and the anodic oxide film around the pattern is eluted by the light etching action of the electrolyte, which prevents the subsequent colored film from forming. After formation, the outline of the colored streak pattern appears as clear and soft lines.
最後に前記アルミニウムを水洗し、以下の着色酸化皮膜
形成を実施する。Finally, the aluminum is washed with water, and the following colored oxide film formation is performed.
1)無機酸または有機酸あるいはこれらの混酸からなる
電解液中で陽極酸化処理し2次陽極酸化皮膜を形成した
後、無機金属塩を含む電解液中で交流電解または直流陰
極電解して着色化膜を形威させる。1) After anodic oxidation treatment in an electrolytic solution consisting of an inorganic acid, an organic acid, or a mixed acid thereof to form a secondary anodic oxide film, coloring is performed by alternating current electrolysis or direct current cathodic electrolysis in an electrolytic solution containing an inorganic metal salt. Gives shape to the membrane.
2)有機酸を含む電解液中で2次陽極酸化皮膜の生成と
着色を同時に行う。2) Generation and coloring of a secondary anodic oxide film are performed simultaneously in an electrolytic solution containing an organic acid.
以上の各工程を経過する本発明方法によれば、次のよう
な効果が得られる。According to the method of the present invention that passes through each of the above steps, the following effects can be obtained.
■)着色筋目模様の中央部と端部との間にはっきり区別
できる色調の差が生じ、かつ模様部と非模様部との間に
もはっきりと区別できる色調の差が生じる。(2) A clearly distinguishable difference in color tone occurs between the center and end portions of the colored streak pattern, and a clearly distinguishable difference in color tone also occurs between the patterned portion and the non-patterned portion.
したがって濃淡3色の装飾効果の豊かな模様が表出でき
る。Therefore, a pattern with a rich decorative effect of three shades of light and shade can be expressed.
2)着色筋目模様は立体感にあふれ、その輪郭が非常に
鮮明である。2) The colored streak pattern has a three-dimensional effect and its outline is very clear.
3)着色筋目模様が非常に滑らかで、柔かな線として視
覚され、自然木に近似した模様である。3) The colored vein pattern is very smooth and can be seen as soft lines, resembling that of natural wood.
4)アルミニウムの非模様部が鮮明に着色される。4) Non-patterned areas of aluminum are clearly colored.
以下本発明の実施例と比較例をあげて、さらに本発明を
説明する。The present invention will be further explained below by giving Examples and Comparative Examples of the present invention.
実施例 1
アルミニウム合金A6063S材を公知の方法により脱
脂、エツチング、中和後硫酸180.9/lの電解液中
で液温20℃、電流密度1.OA/drr?の条件下に
35分間直流電解し前記被処理剤に陽極酸化皮膜を9〜
10μ生成した後、メタリン酸ナトリウム5 g/l!
水溶液を亜リン酸でpH2に調整し浴温25℃に保ち、
対極にステンレスを用い、電流密度0.5A/dm2、
交流印加電圧30Vで2分間処理した後、電源を直流に
切替え、被処理物を陰極とし同一液中で電流密度1.0
A/drrFで10分間電解処理し、陽極酸化皮膜を部
分的に食刻した凹状の筋目模様を得た。Example 1 Aluminum alloy A6063S material was degreased, etched, and neutralized by a known method, and then heated in an electrolytic solution containing 180.9/l of sulfuric acid at a liquid temperature of 20°C and a current density of 1. OA/drr? Direct current electrolysis was carried out for 35 minutes under the conditions of
After producing 10 μ, sodium metaphosphate 5 g/l!
Adjust the aqueous solution to pH 2 with phosphorous acid and keep the bath temperature at 25°C.
Using stainless steel as the counter electrode, current density 0.5A/dm2,
After processing for 2 minutes with an AC applied voltage of 30 V, the power source was switched to DC, and the object to be treated was used as a cathode, and the current density was 1.0 in the same solution.
Electrolytic treatment was performed with A/drrF for 10 minutes to obtain a concave streak pattern in which the anodic oxide film was partially etched.
つぎに、この筋調整のために、グルコン酸ナトリウム4
0 j!/l!溶液(pH6,8、液温30℃)中で電
流密度1、 OA/ dm2.7分間の条件下に交流電
解したところ、鮮明な筋目模様となった。Next, for this muscle adjustment, sodium gluconate 4
0 j! /l! When alternating current electrolysis was carried out in a solution (pH 6.8, liquid temperature 30° C.) under the conditions of a current density of 1 and OA/dm of 2.7 minutes, a clear streak pattern was obtained.
これをその後筋部に耐食性をもたせるため、硫酸i s
o g/ l N電流密度1.OA/dm、液温20
℃で5分間直流電解を行なって陽極酸化皮膜を形威し、
続いて硫酸40 g/ll、硫酸第一すゾ40 g/1
3.チオ硫酸アンモニウム1.0i/ll、ホルマリン
(37%水溶液) 409//lを含む電解液中で液温
20℃、電圧16Vの条件で3分間電解着色したところ
、濃淡の差のある黄金色の美しい筋目模様が得られた。After this, in order to give corrosion resistance to the muscle part, sulfuric acid is
o g/l N current density 1. OA/dm, liquid temperature 20
Perform direct current electrolysis at ℃ for 5 minutes to shape the anodic oxide film,
Subsequently, sulfuric acid 40 g/1, di-sulfuric acid 40 g/1
3. When electrolytically colored in an electrolytic solution containing 1.0 i/l of ammonium thiosulfate and 409//l of formalin (37% aqueous solution) at a temperature of 20°C and a voltage of 16 V for 3 minutes, a beautiful golden yellow with different shades was obtained. A streak pattern was obtained.
実施例 2
アルミニウム合金A6063S材を公知の方法により、
脱脂、エツチング、中和後、硫酸1809/lの電解液
中で液温20℃、電流密度1.0A/cldの条件下に
35分間陽極酸化皮膜処理をした後、メタリン酸カリウ
ムlog7i水溶液を亜リン酸でpH3に調整し、浴温
30℃に保ち、対極にステンレスを用い、0.5A/d
rri”で交流印加、電圧30Vで3分処理した後、電
流を直流に切替え被処理物を陰極として、1.5A/a
rr?で10分間電解処理し、陽極酸化皮膜を部分的に
食刻した凹状の筋目模様を得た。Example 2 Aluminum alloy A6063S material was prepared by a known method.
After degreasing, etching, and neutralization, anodic oxide film treatment was performed for 35 minutes in an electrolytic solution containing 1809/l of sulfuric acid at a temperature of 20°C and a current density of 1.0 A/cld. Adjust the pH to 3 with phosphoric acid, keep the bath temperature at 30℃, use stainless steel as the counter electrode, and apply 0.5A/d.
After processing for 3 minutes at a voltage of 30 V with alternating current applied with "rri", the current was switched to direct current and the treated object was used as a cathode, and the current was 1.5 A/a.
rr? Electrolytic treatment was carried out for 10 minutes to obtain a concave streak pattern in which the anodic oxide film was partially etched.
これを酢酸ナトリウム30 g/l溶液(pH11、液
温25℃)中で10分間、筋調整のため交流電解したと
ころ、鮮明な筋目模様となった。When this was subjected to alternating current electrolysis in a 30 g/l sodium acetate solution (pH 11, liquid temperature 25° C.) for 10 minutes to adjust the streaks, a clear streak pattern was obtained.
その後筋部に耐食性をもたせるため、硫酸18(Bi’
/#、電解密度1. OA / dm2で10分間電解
処理を行ない、陽極酸化皮膜を形成した後、ホウ酸30
g/l、Ni50430fJ/11からなる電解液中で
液温26℃、電圧16Vの条件で3分間電解着色したと
ころ、背景が淡く筋部が濃い濃淡の差がある調和のとれ
たブロンズ色のきれいな模様入りのアルミニウム形材が
得られた。Afterwards, in order to provide corrosion resistance to the muscle, sulfuric acid 18 (Bi'
/#, electrolytic density 1. After electrolytic treatment was performed for 10 minutes at OA/dm2 to form an anodic oxide film, boric acid 30
When electrolytically colored in an electrolytic solution consisting of Ni50430fJ/11 at a temperature of 26°C and a voltage of 16V for 3 minutes, the result was a beautiful, harmonious bronze color with a light background and dark streaks. A patterned aluminum profile was obtained.
実施例 3
アルミニウム合金A6063S材を公知の方法により、
脱脂、エツチング、中和後、硫酸180g//lの電解
液中で液温20℃、電流密度1.OA/dm2の条件下
に35分間陽極酸化皮膜処理をした後、ピロリン酸ナト
リウム4j9/11. グルコン酸2g#水溶液を亜リ
ン酸でpH2,0に調整し、液温35℃に保ち、対極に
ステンレスを用い017A/amで2分間、30Vで交
流印加した後、電源を直流に切替え被処理を陰極として
1°OA/dm2で15分間電解処理を行ない陽極酸化
皮膜を部分的に食刻した筋目模様を得た。Example 3 Aluminum alloy A6063S material was prepared by a known method.
After degreasing, etching, and neutralization, electrolysis was performed in an electrolytic solution containing 180 g//l of sulfuric acid at a liquid temperature of 20°C and a current density of 1. After anodizing for 35 minutes under OA/dm2 conditions, sodium pyrophosphate 4j9/11. Adjust 2 g of gluconic acid #aqueous solution to pH 2.0 with phosphorous acid, keep the liquid temperature at 35°C, apply AC at 30V for 2 minutes at 017A/am using stainless steel as the counter electrode, then switch the power supply to DC and apply it to the treated object. Electrolytic treatment was carried out for 15 minutes at 1° OA/dm2 using as a cathode to obtain a streak pattern in which the anodic oxide film was partially etched.
これをクエン酸ナトリウム30 g/l (pH8,8
、液温25℃)液中で電流密度1.OA/drJで10
分間交流電解して筋調整を行なった。This was added to 30 g/l of sodium citrate (pH 8.8
, liquid temperature 25°C) current density 1. 10 in OA/drJ
Muscle adjustment was performed by alternating current electrolysis for a minute.
その後硫酸tso、9/A中で電流密度1. OA /
dm2のもとに5分間直流電解処理し、引続き陽極酸
化皮膜を形成した後、ホウ酸309/l、HiSO43
0g/l!からなる26℃の液中で16Vの電圧下に電
解着色したところ、濃淡の差があるブロンズ色のきれい
な模様入りのアルミニウム形材が得られた。Then in sulfuric acid tso, 9/A with a current density of 1. OA/
After performing direct current electrolysis treatment under dm2 for 5 minutes and subsequently forming an anodic oxide film, boric acid 309/l, HiSO43
0g/l! When electrolytically colored at a voltage of 16 V in a solution at 26° C., an aluminum profile with a beautiful pattern of bronze color with different shading was obtained.
実施例 4
アルミニウム合金A6063S材を公知の方法により脱
脂、エツチング、中和後、硫酸1809/lの電解液中
で液温20℃、電流密度1.OA/diの条件下に35
分間陽極酸化皮膜処理をした後、メタリン酸ナトリウム
8j!/1.水溶液を暉リン酸でpH2に調整し浴温3
0℃に保ち、対極にステンレスを用い、1.OA/dr
r?で交流印加電圧30Vで1分間電解処理した後、電
源を直流に切替え、被処理物を陰極として1.OA/
dJで10分間電解処理を行い、陽極酸化皮膜を部分的
に食刻した筋目模様を得た。Example 4 After degreasing, etching, and neutralizing aluminum alloy A6063S material by a known method, it was heated in an electrolytic solution of 1809/l sulfuric acid at a liquid temperature of 20°C and a current density of 1. 35 under OA/di conditions
After being anodized for a minute, sodium metaphosphate 8j! /1. Adjust the aqueous solution to pH 2 with phosphoric acid and bath temperature 3.
Maintain at 0°C, use stainless steel as the counter electrode, 1. OA/dr
r? After performing electrolytic treatment for 1 minute at an AC applied voltage of 30 V, the power source was switched to DC, and the object to be treated was used as a cathode. OA/
Electrolytic treatment was performed for 10 minutes using dJ to obtain a streak pattern in which the anodic oxide film was partially etched.
これをグルコン酸ナトリウム80g/ !l (pH6
,8、液温30℃)液中で電流密度1.OA/drr?
で7分間交流電解すると鮮明な筋目模様となった。80g of this sodium gluconate! l (pH6
, 8, liquid temperature 30°C) current density 1. OA/drr?
After 7 minutes of alternating current electrolysis, a clear streak pattern was obtained.
その筋部に耐食性をもたせるため、スルホサリチル酸1
00g/lと硫酸5 g/lの水溶液浴中で40Vの電
圧下に10分間直流電解したところ、美しい自然発色皮
膜をもつ模様入りアルミニウム形材が得られた。In order to provide corrosion resistance to the muscle, sulfosalicylic acid 1
When subjected to direct current electrolysis for 10 minutes at a voltage of 40 V in an aqueous solution bath of 00 g/l and 5 g/l of sulfuric acid, a patterned aluminum profile with a beautiful naturally colored film was obtained.
実施例 5
アルミニウム合金A6063R材を公知の方法により脱
脂、エツチング、中和後、硫酸180g/13中で液温
20°C1電流密度1.OA/dイの条件下で35分間
陽極酸化皮膜処理をした後、メタリン酸ナトリウム5g
/11を亜リン酸でpH2に調整し、液温25℃に保ち
対極にステンレスを用い、前記合金を陰極として電圧5
0V、電流密度0.8 A / dm2で10分間直流
電解処理を行い、陽極酸化皮膜を部分的に食刻した筋目
模様を得た。Example 5 Aluminum alloy A6063R material was degreased, etched, and neutralized by a known method, and then heated in 180 g/13 sulfuric acid at a liquid temperature of 20° C. and a current density of 1. After anodizing for 35 minutes under OA/di conditions, 5g of sodium metaphosphate
/11 was adjusted to pH 2 with phosphorous acid, the liquid temperature was kept at 25°C, stainless steel was used as a counter electrode, and a voltage of 5 was applied using the alloy as a cathode.
Direct current electrolysis treatment was performed at 0 V and a current density of 0.8 A/dm2 for 10 minutes to obtain a streak pattern in which the anodic oxide film was partially etched.
これをグルコン酸ナトリウム40g/1(pH6,8、
液温25℃)液中で電圧30V下に電流密度0.6 A
/ drr?で10分間交流電解すると鮮明な筋目模様
となった。Sodium gluconate 40g/1 (pH 6,8,
Current density 0.6 A under voltage 30 V in liquid (liquid temperature 25°C)
/ drr? After 10 minutes of alternating current electrolysis, a clear streak pattern was obtained.
その後硫酸ニッケル309/13.ホウ酸30g/13
を含む20℃の電解液中で12V、3分間交流電解着色
処理を行ったところ模様部と非模様部がきれいなブロン
ズ色に着色されたアルミニウム形材が得られた。Then nickel sulfate 309/13. Boric acid 30g/13
When an alternating current electrolytic coloring treatment was carried out at 12 V for 3 minutes in an electrolytic solution at 20° C. containing 10% of aluminum, an aluminum profile was obtained in which the patterned and non-patterned portions were colored in a beautiful bronze color.
比較例 1
アルミニウム合金A6063Sを実施例1と同様の方法
によって陽極酸化皮膜処理し、ついでメタリン酸ナトリ
ウム水溶液中で交流電解し、さらに直流電解処理して陽
極酸化皮膜を部分的に食刻した凹状の筋目模様を得た。Comparative Example 1 Aluminum alloy A6063S was treated with an anodized film in the same manner as in Example 1, then subjected to AC electrolysis in an aqueous sodium metaphosphate solution, and further subjected to DC electrolysis treatment to form a concave shape with the anodic oxide film partially etched. A streak pattern was obtained.
つぎに、筋調整のための交流電解を省略し、以後、実施
例1と同じ陽極酸化皮膜処理と電解着色を行なったとこ
ろ、筋目模様部は硬い線として視覚され、非模様部との
区別が鮮明でない着色模様のアルミニウム形材が得られ
た。Next, when the AC electrolysis for streak adjustment was omitted and the same anodic oxidation film treatment and electrolytic coloring as in Example 1 were performed, the streak pattern area was visible as a hard line, and it was difficult to distinguish it from the non-pattern area. An aluminum profile with an indistinct colored pattern was obtained.
比較例 2
アルミニウム合金A6063Sを実施例2と同様の方法
によって陽極酸化皮膜処理し、ついでメタリン酸カリウ
ム水浴液甲で交流電解し、さらに直流電解処理して陽極
酸化皮膜を部分的に食刻した凹状の筋目模様を得た。Comparative Example 2 Aluminum alloy A6063S was anodized by the same method as in Example 2, then AC electrolyzed in a potassium metaphosphate water bath, and then DC electrolyzed to form a concave shape in which the anodic oxide film was partially etched. A streak pattern was obtained.
つぎにこれを炭酸ナトリウム31/11(pH12、液
温20℃)溶液中で電流密度1.OA/d♂の条件下に
8分間交流電解して筋調整を行なったところ、鮮明な筋
模様が表れた。Next, this was placed in a sodium carbonate 31/11 (pH 12, liquid temperature 20°C) solution at a current density of 1. When the stripes were adjusted by alternating current electrolysis for 8 minutes under OA/d♂ conditions, a clear stripe pattern appeared.
その後筋部に耐食性をもたせるための陽極酸化皮膜形成
と電解着色処理を実施例2の方法で行なった結果、筋部
だけが着色さへ非模様部の着色が不鮮明な模様入りアル
ミニウム形材が得られた。Thereafter, an anodic oxide film was formed and electrolytically colored in order to impart corrosion resistance to the striations using the method of Example 2. As a result, a patterned aluminum profile was obtained in which only the striations were colored and the non-patterned areas were not clearly colored. It was done.
Claims (1)
により陽極酸化皮膜を形成し、続いてリン酸カルシウム
、リン酸カリウム、ピロリン酸カリウム、メタリン酸カ
リウム、リン酸ナトリウム、メタリン酸ナトリウム、次
亜リン酸ナトリウム、ピロリン酸ナトリウム、類リン酸
ナトリウム、リン酸三ナトリウム、リン酸水素アンモニ
ウムナトリウム、リン酸リチウム、リン酸亜鉛、リン酸
水素カルシウム、リン酸カルシウム、リン酸マグネシウ
ムアンモニウム、炭酸ナトリウム、炭酸カリウム、炭酸
カルシウム、クロム酸ナトリウム、クロム酸カリウム、
メタホウ酸ナトリウム、クエン酸ナトリウム、酒石酸ナ
トリウム、フタル酸ナトリウム、マレイン酸ナトリウム
の一種または二種以上を含む電解液中で交流電解し、引
続き同一液中で直流陰極電解して凹凸のある筋目模様を
付けた後、炭酸ナトリウム、炭酸水素ナトリウム、リン
酸三ナトリウム、リン酸水素ナトリウム、ピロリン酸ナ
トリウム、メタホウ酸ナトリウム、硫酸水素ナトリウム
、シュウ酸ナトリウム、フッ化ナトリウム、グルコン酸
ナトリウム、水酸化ナトリウム、クエン酸ナトリウム、
硫酸ナトリウム、酢酸ナトリウム、酒石酸ナトリウム、
ケイ酸ナトリウム、スルファミン酸ナトリウム、フッ化
カリウム、硫酸カリウム、ケイ酸カリウム、酒石酸カリ
ウム、ピロリン酸カリウム、酢酸カリウム、炭酸カリウ
ムの一種以上を含むpH6〜11の水溶液中で交流電解
し、しかる後着色皮膜を形成させることを特徴とするア
ルミニウムまたはアルミニウム合金の着色模様形成方法
。 2 アルミニウムまたはアルミニウム合金の表面に常法
により陽極酸化皮膜を形威し、続いてリン酸カルシウム
、リン酸カリウム、ピロリン酸カリウム、メタリン酸カ
リウム、リン酸ナトリウム、メタリン酸ナトリウム、次
亜リン酸ナトリウム、ピロリン酸ナトリウム、類リン酸
ナトリウム、リン酸三ナトリウム、リン酸水素アンモニ
ウムナトリウム、リン酸リチウム、リン酸亜鉛、リン酸
水素カルシウム、リン酸カルシウム、リン酸マグネシウ
ムアンモニウム、炭酸ナトリウム、炭酸カリウム、炭酸
カルシウム、クロム酸ナトリウム、クロム酸カリウム、
メタホウ酸ナトリウム、クエン酸ナトリウム、酒石酸ナ
トリウム、フタル酸ナトリウム、マレイン酸ナトリウム
の一種または二種以上を含む電解液中で直流陰極電解し
て凹凸のある筋目模様を付けた後、炭酸ナトリウム、炭
酸水素ナトリウム、リン酸三ナトリウム、リン酸水素ナ
トリウム、ピロリン酸ナトリウム、メタホウ酸ナトリウ
ム、硫酸水素ナトリウム、シュウ酸ナトリウム、フッ化
ナトリウム、グルコン酸ナトリウム、水酸化ナトリウム
、クエン酸ナトリウム、硫酸ナトリウム、酢酸ナトリウ
ム、酒石酸ナトリウム、ケイ酸ナトリウム、スルファミ
ン酸ナトリウム、フッ化カリウム、硫酸カリウム、ケイ
酸カリウム、酒石酸カリウム、ピロリン酸カリウム、酢
酸カリウム、炭酸カリウムの一種以上を含むpH6〜1
1の水溶液中で交流電解し、しかる後着色皮膜を形成さ
せることを特徴とするアルミニウムまたはアルミニウム
合金の着色模様形成方法。[Claims] 1. An anodic oxide film is formed on the surface of aluminum or aluminum alloy by a conventional method, and then calcium phosphate, potassium phosphate, potassium pyrophosphate, potassium metaphosphate, sodium phosphate, sodium metaphosphate, hypochlorite, etc. Sodium phosphate, sodium pyrophosphate, sodium phosphate, trisodium phosphate, sodium ammonium hydrogen phosphate, lithium phosphate, zinc phosphate, calcium hydrogen phosphate, calcium phosphate, ammonium magnesium phosphate, sodium carbonate, potassium carbonate, Calcium carbonate, sodium chromate, potassium chromate,
AC electrolysis is performed in an electrolytic solution containing one or more of sodium metaborate, sodium citrate, sodium tartrate, sodium phthalate, and sodium maleate, followed by direct current cathodic electrolysis in the same solution to create an uneven streak pattern. After applying, sodium carbonate, sodium hydrogen carbonate, trisodium phosphate, sodium hydrogen phosphate, sodium pyrophosphate, sodium metaborate, sodium hydrogen sulfate, sodium oxalate, sodium fluoride, sodium gluconate, sodium hydroxide, citric acid. acid sodium,
Sodium sulfate, sodium acetate, sodium tartrate,
AC electrolysis in an aqueous solution with a pH of 6 to 11 containing one or more of sodium silicate, sodium sulfamate, potassium fluoride, potassium sulfate, potassium silicate, potassium tartrate, potassium pyrophosphate, potassium acetate, and potassium carbonate, followed by coloring. A method for forming a colored pattern on aluminum or aluminum alloy, the method comprising forming a film. 2 Form an anodized film on the surface of aluminum or aluminum alloy by a conventional method, and then apply calcium phosphate, potassium phosphate, potassium pyrophosphate, potassium metaphosphate, sodium phosphate, sodium metaphosphate, sodium hypophosphite, pyrroline. Sodium acid, sodium phosphate, trisodium phosphate, sodium ammonium hydrogen phosphate, lithium phosphate, zinc phosphate, calcium hydrogen phosphate, calcium phosphate, ammonium magnesium phosphate, sodium carbonate, potassium carbonate, calcium carbonate, chromic acid sodium, potassium chromate,
After applying DC cathode electrolysis in an electrolytic solution containing one or more of sodium metaborate, sodium citrate, sodium tartrate, sodium phthalate, and sodium maleate to create an uneven streak pattern, sodium carbonate and hydrogen carbonate are added. Sodium, trisodium phosphate, sodium hydrogen phosphate, sodium pyrophosphate, sodium metaborate, sodium hydrogen sulfate, sodium oxalate, sodium fluoride, sodium gluconate, sodium hydroxide, sodium citrate, sodium sulfate, sodium acetate, pH 6-1 containing one or more of sodium tartrate, sodium silicate, sodium sulfamate, potassium fluoride, potassium sulfate, potassium silicate, potassium tartrate, potassium pyrophosphate, potassium acetate, and potassium carbonate.
1. A method for forming a colored pattern on aluminum or an aluminum alloy, which comprises carrying out alternating current electrolysis in an aqueous solution according to item 1, and then forming a colored film.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14414179A JPS5846558B2 (en) | 1979-11-07 | 1979-11-07 | Method for forming colored patterns on aluminum or aluminum alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14414179A JPS5846558B2 (en) | 1979-11-07 | 1979-11-07 | Method for forming colored patterns on aluminum or aluminum alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5669391A JPS5669391A (en) | 1981-06-10 |
JPS5846558B2 true JPS5846558B2 (en) | 1983-10-17 |
Family
ID=15355171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14414179A Expired JPS5846558B2 (en) | 1979-11-07 | 1979-11-07 | Method for forming colored patterns on aluminum or aluminum alloy |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5846558B2 (en) |
-
1979
- 1979-11-07 JP JP14414179A patent/JPS5846558B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5669391A (en) | 1981-06-10 |
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