JPH01205092A - Electrolytic coloring method for aluminum or aluminum alloy - Google Patents
Electrolytic coloring method for aluminum or aluminum alloyInfo
- Publication number
- JPH01205092A JPH01205092A JP2849088A JP2849088A JPH01205092A JP H01205092 A JPH01205092 A JP H01205092A JP 2849088 A JP2849088 A JP 2849088A JP 2849088 A JP2849088 A JP 2849088A JP H01205092 A JPH01205092 A JP H01205092A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- coloring
- electrolytic coloring
- electrolytic
- waveform
- 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
- 238000004040 coloring Methods 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 18
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 7
- 239000000243 solution Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101100342332 Mus musculus Klf16 gene Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Shaping Metal By Deep-Drawing, Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアルミニウムまたはアルミニウム合金（以下単
に「アルミニウム」という。）の電解着色方法に関し、
詳しくは陽極酸化処理を施したアルミニウムを電解着色
するにあたって、まず正電圧波形の電圧を印加して予備
処理し、次いで特定の波形の電圧を印加して電解着色処
理することによって、アルミニウム表面に均一かつ美麗
な着色を効率よく施すことのできる方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for electrolytically coloring aluminum or aluminum alloy (hereinafter simply referred to as "aluminum").
In detail, when electrolytically coloring aluminum that has been anodized, a voltage with a positive voltage waveform is first applied for pretreatment, and then a voltage with a specific waveform is applied to electrolytically color the aluminum surface. The present invention also relates to a method that can efficiently apply beautiful coloring.
〔従来技術および発明が解決しようとする課題〕従来か
らアルミニウムを電解着色するにあたって、付き廻り性
や着色速度を改善するために様々な方法が提案されてい
る。例えば着色の付き廻り性を改善するために、電解液
に様々な工夫をする方法（特公昭６０−１１１１９号公
報）、電解着色の際に加える電圧の昇圧あるいは印加の
仕方に工夫をする方法（特公昭５４−２３６６’ ３号
公報（米国特許第４０７０２５５号明細書）、特公昭５
Ｂ−４６５５７号公報、特開昭５９−１４５７９８号公
報、特公昭４９−３４２８７号公報、特公昭５２−４９
４０８号公報、特公昭５７−２７９５３号公報、特公昭
５３−４５０３号公報）、あるいは電解着色に先立って
特定の直流陽極電解を行う方法（特公昭５４−１３８５
９号公報、特公昭５４−２５８９８号公報（米国特許第
４０２１３１５号明細書）、特公昭５４−２３６６４号
公報、特公昭５Ｂ−５２０３７号公報（米国特許第４３
１６７８０号明細書）、特公昭５８−３９２３７号公報
）などがある。また、電解着色の着色速度を向上させる
ために、電解液に工夫を 。[Prior Art and Problems to be Solved by the Invention] Various methods have been proposed to improve coverage and coloring speed when electrolytically coloring aluminum. For example, in order to improve the coverage of coloring, there are methods for making various improvements to the electrolyte (Japanese Patent Publication No. 11119/1983), methods for increasing the voltage applied during electrolytic coloring, or improving the way the voltage is applied ( Japanese Patent Publication No. 54-2366' 3 (U.S. Patent No. 4070255), Japanese Patent Publication No. 54-2366'
B-46557, JP 59-145798, JP 49-34287, JP 52-49
408, Japanese Patent Publication No. 57-27953, Japanese Patent Publication No. 53-4503), or a method of carrying out a specific DC anodic electrolysis prior to electrolytic coloring (Japanese Patent Publication No. 54-1385).
9, Japanese Patent Publication No. 54-25898 (U.S. Patent No. 4021315), Japanese Patent Publication No. 54-23664, Japanese Patent Publication No. 5B-52037 (U.S. Patent No. 43)
16780) and Japanese Patent Publication No. 58-39237). In addition, in order to improve the coloring speed of electrolytic coloring, we made improvements to the electrolyte.
する方法（特公昭６０−１１１１９号公報、特公昭５４
−２３６６３号公報）あるいは対極板に工夫をする方法
（特公昭６０−１３４４０号公報）などがある。method (Japanese Patent Publication No. 11119/1983,
23663) or a method of modifying the return electrode (Japanese Patent Publication No. 60-13440).
しかし、一般に電解着色法、特に交流電解着色法におい
ては、上述したような工夫では着色の際に、付き廻り性
と着色速度のいずれか一方は改善されるが、他方は充分
に改善されず、むしろ低下する傾向を示す。However, in general, in the electrolytic coloring method, and in particular in the AC electrolytic coloring method, the above-mentioned devices improve one of the coverage and coloring speed, but the other is not sufficiently improved. Rather, it shows a decreasing trend.
特に、交流を抵抗やサイリスク制御して着色する方法（
特公昭５３−４５０３号公報、特公昭４９−３４２８７
号公報−１特公昭５７−２７９５３号公報）は、バリヤ
ー層の調整工程を行わないため、充分な着色効果を発現
できないという問題がある。さらに、予めバリヤー層を
調整し、しかる後に正のパルス電圧を印加した直流電流
によって電解着色処理を行う特公昭５８−５２０３７号
公報（米国特許第４３１６７８０号明細書）に開示され
た方法は、電流の制御が掻めて煩雑となるとともに設備
費がかさみ、経済的に不利である。In particular, methods for coloring alternating current by controlling resistance and cyrisk (
Special Publication No. 53-4503, Special Publication No. 49-34287
No. 1 (Japanese Patent Publication No. 57-27953) has the problem that a sufficient coloring effect cannot be achieved because the barrier layer adjustment step is not performed. Furthermore, the method disclosed in Japanese Patent Publication No. 58-52037 (U.S. Pat. No. 4,316,780), in which the barrier layer is adjusted in advance and then subjected to electrolytic coloring treatment using a direct current to which a positive pulse voltage is applied, The control becomes difficult and complicated, and the equipment cost increases, which is economically disadvantageous.
そこで本発明者は上述の従来技術の欠点を克服し、付き
廻り性と着色速度の両者を同時に向上させることのでき
る方法を開発すべく鋭意研究を重ねた。Therefore, the present inventor has conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method that can simultaneously improve coverage and coloring speed.
その結果、陽極酸化処理を施したアルミニウムを、正電
圧波形の電圧を印加して予備処理し、しかる後に特定の
非対称波形の電圧を印加して電解着色処理することによ
って、目的を達成しうろことを見出した。本発明はかか
る知見に基いて完成したものである。As a result, the objective can be achieved by pre-treating the anodized aluminum by applying a positive voltage waveform and then electrolytically coloring the anodized aluminum by applying a specific asymmetric voltage waveform. I found out. The present invention was completed based on this knowledge.
すなわち本発明は、陽極酸化処理を施したアルミニウム
またはアルミニウム合金を、金属塩を含有する電解着色
液中で電解着色するにあたり、前記電解着色液中あるい
は前記電解着色液と同等の電気伝導性を有する電解液中
で実質的に正電圧波形の電圧を印加して予備処理し、し
かる後に前記電解着色液中で正の電圧と負の電圧の印加
時間の比率が１：１〜３になるように制御された波形の
電圧を１秒間に１〜２５回の割合で印加して電解着色す
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
金の電解着色方法を提供するものである。That is, in electrolytically coloring anodized aluminum or aluminum alloy in an electrolytic coloring solution containing a metal salt, the present invention provides an electrolytic coloring solution that has electrical conductivity equivalent to that of the electrolytic coloring solution or the electrolytic coloring solution. Pretreatment is performed by applying a voltage with a substantially positive voltage waveform in the electrolytic solution, and then the ratio of the application time of the positive voltage to the negative voltage in the electrolytic coloring solution is 1:1 to 3. The present invention provides a method for electrolytically coloring aluminum or an aluminum alloy, characterized in that electrolytically coloring is performed by applying a voltage with a controlled waveform at a rate of 1 to 25 times per second.
本発明の方法に用いるアルミニウムは、その表面に陽極
酸化処理を施したものである。ここで行う陽極酸化処理
は従来から広く行われている方法でよ（、通常はアルミ
ニウムの表面を脱脂洗浄し、これを陽極として、またア
ルミニウム、グラファイト等を陰極として用い、硫酸、
シュウ酸、スルファミン酸などの酸性電解液中で直流通
電することにより行う。The aluminum used in the method of the present invention has its surface subjected to anodic oxidation treatment. The anodizing treatment performed here is a method that has been widely used in the past (usually, the surface of aluminum is degreased and cleaned, and this is used as an anode, and aluminum, graphite, etc. are used as a cathode, and sulfuric acid,
This is carried out by applying direct current in an acidic electrolyte such as oxalic acid or sulfamic acid.
本発明の方法では、上述の如く陽極酸化処理を施したア
ルミニウムを、電解着色処理するに先立って予備処理し
ておくことが必要である。予備処理を行う電解液は、後
続の電解着色処理で用いる電解着色液と必ずしも同じで
ある必要はなく、この電解着色液と同等の電気伝導性を
有する電解液であれば特に制限はない。しかしながら、
電解着色液中で予備処理すれば、同一電解浴にて予備処
理から電解着色処理までを連続して操作できるため、工
程が簡略化し工業的に有利である。In the method of the present invention, it is necessary to pre-treat aluminum that has been anodized as described above before electrolytically coloring it. The electrolytic solution used in the preliminary treatment does not necessarily have to be the same as the electrolytic coloring solution used in the subsequent electrolytic coloring treatment, and is not particularly limited as long as it has the same electrical conductivity as this electrolytic coloring solution. however,
If the pretreatment is performed in an electrolytic coloring solution, the steps from pretreatment to electrolytic coloring can be carried out continuously in the same electrolytic bath, which simplifies the process and is industrially advantageous.
一般に、陽極酸化処理によって形成されるバリヤー層を
改質する場合、改質したバリヤー層が厚ければ厚い程、
陽極酸化時に形成したバリヤー層の電気的な抵抗が均一
化し、均一な電解着色が可能であるが、あまり厚すぎる
と電解着色時にピッティングが発生するという問題があ
る。Generally, when modifying a barrier layer formed by anodizing, the thicker the modified barrier layer, the more
The electrical resistance of the barrier layer formed during anodization becomes uniform and uniform electrolytic coloring is possible, but if it is too thick, there is a problem that pitting will occur during electrolytic coloring.
しかし、本発明の方法では予備処理後に行う電解着色処
理の段階で用いる電圧波形に工夫を施しているため、予
備処理によるバリヤー層の改質の程度はあまり問題にな
らない。すなわち、改質したバリヤー層が多少薄くても
、電解着色の付き廻り性は充分確保でき、また逆にやや
厚くなりすぎてもピンティングが発生するおそれはない
。However, in the method of the present invention, the voltage waveform used in the electrolytic coloring step performed after the pretreatment is devised, so the degree of modification of the barrier layer by the pretreatment does not matter much. That is, even if the modified barrier layer is somewhat thin, sufficient coverage of electrolytic coloring can be ensured, and conversely, even if it becomes slightly too thick, there is no risk of pinting occurring.
このような理由から、本発明の方法の予備処理では印加
する電圧は、実質的に正電圧波形を示すものであれば特
に制限はなく、直流の正波、三相を含む半波整流、同全
波整流等で充分である。また、実質的に正電圧波形とは
、用いる電圧波形の一周期に亘るすべてにおいて正電圧
を示す波形のみならず、若干の負電圧部分（例えば負電
圧／正電圧＝０〜０．５）を有する波形をも含むもので
ある。ここで負電圧部分を有する波形の電圧を印加させ
ることにより、正電圧を高くすることができ、バリヤー
層の改質効果が高められる。またこの予備処理では、後
続の電解着色工程で用いる波形の正負を逆にした波形を
用いることもできるが、このような電圧波形を用いるこ
とは設備上便宜的な方法となる。For this reason, the voltage to be applied in the pretreatment of the method of the present invention is not particularly limited as long as it exhibits a substantially positive voltage waveform; Full wave rectification etc. is sufficient. In addition, a substantially positive voltage waveform refers not only to a waveform that shows positive voltage throughout one period of the voltage waveform used, but also to a waveform that shows a certain negative voltage portion (for example, negative voltage/positive voltage = 0 to 0.5). This also includes waveforms with By applying a waveform voltage having a negative voltage portion here, the positive voltage can be increased, and the effect of modifying the barrier layer is enhanced. Further, in this preliminary treatment, a waveform with the polarity reversed from that used in the subsequent electrolytic coloring process can be used, but using such a voltage waveform is a convenient method in terms of equipment.
この予備処理の際の通電時間、印加すべき正電圧の大き
さ、その昇圧速度等については特に制限はなく、状況に
応じて適宜定めればよい。予備処理時間は、各種状況に
よって異なり、一義的に定めることはできないが、通常
は昇圧に要する時間を含めて５秒〜３分間、好ましくは
１０秒〜１．５分間である。また電流密度は、正の平均
値電流で０、Ｏ１〜２Ａ／ｄｍ２、好ましくは０．０１
〜ＩＡ ／ ｄ ｍ ”である。There are no particular restrictions on the energization time, the magnitude of the positive voltage to be applied, the boosting speed, etc. during this preliminary treatment, and they may be determined as appropriate depending on the situation. Although the pretreatment time varies depending on various situations and cannot be unambiguously determined, it is usually 5 seconds to 3 minutes, including the time required for pressure increase, and preferably 10 seconds to 1.5 minutes. In addition, the current density is 0, O1 to 2A/dm2 at a positive average value current, preferably 0.01
~IA/dm''.
上記予備処理を行うことなく、直接に電解着色処理を行
うと、電解液の種類によっては付き廻り性が充分でなく
均一な着色が得られないかあるいは着色されにくいとい
う問題がある。また着色を早めるために着色時に高電圧
を印加するとピッティングが発生するおそれがある。。If the electrolytic coloring treatment is directly performed without performing the above pretreatment, there is a problem that depending on the type of electrolyte, the permeability is insufficient and uniform coloring cannot be obtained or coloring is difficult. Moreover, if a high voltage is applied during coloring to accelerate coloring, pitting may occur. .
本発明の方法では、上記予備処理を電解着色液または他
の予備処理用電解液中で行った後、電解着色液中で引き
続いて電解着色処理を行う。In the method of the present invention, after the above pretreatment is performed in an electrolytic coloring solution or other pretreatment electrolyte, an electrolytic coloring treatment is performed in an electrolytic coloring solution.
ここで行う電解着色処理は、基本的には交流電解着色処
理であるが、印加電圧として正電圧が負電圧より小さい
波形の電圧を用いることが必要である。The electrolytic coloring treatment performed here is basically an AC electrolytic coloring treatment, but it is necessary to use a voltage with a waveform in which the positive voltage is smaller than the negative voltage as the applied voltage.
ここで使用できる波形は不完全整流法や電流反転整流（
Ｄｕｔｙ）法で得られるものである。不完全整流法の場
合は例えば三相交流の一相を逆転させて整流することに
よって得られる。また電流反転整流法では正と負のパル
ス数を１：１〜３にすることによって得られる。いずれ
にしても、正電圧と負電圧の印加時間の比率を正電圧：
負電圧＝１：１〜３の範囲に設定するとともに、このよ
うに制御された波形の電圧を１秒間に１〜２５回、好ま
しくは５〜２０回の割合で印加することが必要である。The waveforms that can be used here are incomplete rectification method and current reversal rectification method (
This is obtained by the Duty) method. In the case of the incomplete rectification method, for example, one phase of a three-phase alternating current is reversed and rectified. In the current reversal rectification method, the ratio of positive and negative pulses is 1:1 to 3. In any case, the ratio of the application time of positive voltage and negative voltage to positive voltage:
It is necessary to set the negative voltage in the range of 1:1 to 3, and to apply the voltage with the waveform controlled in this way at a rate of 1 to 25 times, preferably 5 to 20 times per second.
なお、これらの電圧電源としては三相交流電圧を好適な
ものとして挙げることができる。Note that a three-phase AC voltage can be cited as a suitable voltage source for these voltage sources.
またこれらの波形によって電解着色するにあたって、正
負の電流密度の比率は、特に制限はないが、一般には正
の電流密度：負の電流密度＝１：２〜６、好ましくは１
：３〜５になるように通電する。またこのときの正の電
流密度は好ましくは０．０１〜０．５Ａ／ｄｒｒｆ、特
に好ましくは０．０２〜０．３Ａ／ｄボであり、負の電
流密度は好ましくは０．０５〜ＬＡ／ｄｒｒｒ、特に好
ましくは０．１〜０．６Ａ／ｄボである。In addition, when performing electrolytic coloring using these waveforms, the ratio of positive and negative current densities is not particularly limited, but generally positive current density: negative current density = 1:2 to 6, preferably 1.
: Electrify so that the voltage becomes 3 to 5. Further, the positive current density at this time is preferably 0.01 to 0.5 A/drrf, particularly preferably 0.02 to 0.3 A/dbo, and the negative current density is preferably 0.05 to LA/drrf. drrr, particularly preferably 0.1 to 0.6 A/dbo.
電解時間は必要とする色調によって異なるが、−船釣に
は、１０秒〜３０分、好ましくは３０秒〜２０分である
。The electrolysis time varies depending on the desired color tone, but for boat fishing it is 10 seconds to 30 minutes, preferably 30 seconds to 20 minutes.
本発明の方法に用いる電解着色液には目的に応じて様々
な金属塩が含有されている。この金属塩の具体例をあげ
れば、ニッケル、コバルト、銅。The electrolytic coloring solution used in the method of the present invention contains various metal salts depending on the purpose. Specific examples of these metal salts are nickel, cobalt, and copper.
セレン、鉄、モリブデン、スズなどの金属の硫酸塩、硝
酸塩、リン酸塩、塩酸塩、シュウ酸塩、酢酸塩、酒石酸
塩などがある。These include sulfates, nitrates, phosphates, hydrochlorides, oxalates, acetates, and tartrates of metals such as selenium, iron, molybdenum, and tin.
電解着色処理に際しての条件、例えば印加すべき電圧の
大きさ２通電時間、液温などについては適宜選定すれば
よい。しかし、本発明の方法にょれば、従来の交流電解
着色よりも高電圧（負電圧）で着色処理ができるので、
着色速度も速く比較的短時間で電解着色を行うことがで
きる。Conditions for the electrolytic coloring treatment, such as the magnitude of the voltage to be applied, the current application time, and the liquid temperature, may be appropriately selected. However, according to the method of the present invention, coloring can be performed at a higher voltage (negative voltage) than the conventional AC electrolytic coloring.
The coloring speed is fast and electrolytic coloring can be done in a relatively short time.
本発明の方法によれば、予備処理を行ってアルミニウム
表面の陽極酸化皮膜のバリヤー層をある程度改質すると
ともに、電解着色工程で特定の波形を用いるため、電解
着色を高電圧で行ってもピッティング等を起こすことな
く、着色が速やかにしかも付き廻り性よく進行し、短時
間で均一かつ美麗な電解着色皮膜が形成される。According to the method of the present invention, the barrier layer of the anodic oxide film on the aluminum surface is modified to some extent by pre-treatment, and a specific waveform is used in the electrolytic coloring process, so even if electrolytic coloring is performed at high voltage, it will not smudge. Coloring progresses quickly and with good coverage without causing any staining, etc., and a uniform and beautiful electrolytically colored film is formed in a short time.
［実施例］ 次に本発明を実施例によりさらに詳しく説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
実施例１
アルミニウム材としてＡ・６０６３−ＴＳ材（１５０Ｘ
７０Ｘ２ｍｍ）を使用し、常法に従って、脱脂、エッチ
ラグ、中和処理を行った後、硫酸浴を用いて直流電解し
、無色の陽極酸化皮膜を形成した。Example 1 A 6063-TS material (150X
After degreasing, etch lag, and neutralizing according to conventional methods, direct current electrolysis was performed using a sulfuric acid bath to form a colorless anodic oxide film.
次に、Ｎ ｉ Ｓ Ｏａ・６Ｈ２０を９０ ｇ／１．お
よびＨ，ＢＯ，を４０ｇ／ｌ含有しｐ Ｈ５，０の電解
着色液を用い、温度３０°Ｃの条件で６相半波整流０．
２Ａ／ｄｎ（で３０秒間予備処理を行い、次いで正のパ
ルス３．負のパルス６の電流反転整流波を用い、正の電
流密度０．０４Ａ／ｄポ、正の電圧７．５■、負の電流
密度０．１５Ａ／ｄボ、負の電圧１３Ｖの条件で３分間
電解着色を行った。その結果、得られた着色膜は濃ブロ
ンズ色であった。Next, 90 g/1. Using an electrolytic coloring solution containing 40 g/l of H, BO, and pH 5.0, six-phase half-wave rectification at a temperature of 30° C.
2A/dn (pretreatment for 30 seconds, then using a current reversal rectified wave of positive pulse 3 and negative pulse 6, positive current density 0.04A/d, positive voltage 7.5μ, negative Electrolytic coloring was carried out for 3 minutes under the conditions of a current density of 0.15 A/d and a negative voltage of 13 V. As a result, the colored film obtained was a deep bronze color.
実施例２
アルミニウム材としてＡ・１１００・ＨＩ３材（１５０
Ｘ７０Ｘ２世）を使用し、常法に従って、脱脂、エッチ
ラグ、中和処理を行った後、硫酸浴を用いて直流電解し
、無色の陽極酸化皮膜を形成した。Example 2 A・1100・HI3 material (150
X70
次に、ＣｏＳＯ４・６Ｈ２０を５０ ｇ＃！およびＨ，
ＢＯ，を３０ ｇ＃金含有ｐＨ４，５の電解着色液を用
い、温度３５°Ｃの条件で正のパルス１２゜負のパルス
４の電流反転整流波を用い、正の電流密度０．２Ａ／ｄ
イ、負の電流密度０．ＯＩＡ／ｄボで２０秒間予備処理
を行った。次いで正のパルス４、負のパルス１２の電流
反転整流波を用い、正の電流密度０．０４Ａ／ｄボ、正
の電圧７■、負の電流密度０．２Ａ／ｄｒｄ、負の電圧
１４Ｖの条件で６分間電解着色を行った。その結果、得
られた着色膜は黒色であった。Next, add 50 g of CoSO4 6H20! and H,
Using 30 g of BO, a gold-containing electrolytic coloring solution with a pH of 4.5 and a temperature of 35°C, using a current reversal rectified wave with a positive pulse of 12° and a negative pulse of 4, a positive current density of 0.2 A/ d
A, negative current density 0. Pretreatment was performed for 20 seconds with OIA/dbo. Next, using a current inversion rectified wave of positive pulse 4 and negative pulse 12, a positive current density of 0.04 A/d, a positive voltage of 7 cm, a negative current density of 0.2 A/drd, and a negative voltage of 14 V were applied. Electrolytic coloring was carried out for 6 minutes under these conditions. As a result, the colored film obtained was black.
第１図は、実施例１の電解着色処理で使用した電流反転
整流波の波形を示す。FIG. 1 shows the waveform of the current reversal rectified wave used in the electrolytic coloring process of Example 1.
Claims (3)
ニウム合金を、金属塩を含有する電解着色液中で電解着
色するにあたり、前記電解着色液中あるいは前記電解着
色液と同等の電気伝導性を有する電解液中で実質的に正
電圧波形の電圧を印加して予備処理し、しかる後に前記
電解着色液中で正の電圧と負の電圧の印加時間の比率が
１：１〜３になるように制御された波形の電圧を１秒間
に１〜２５回の割合で印加して電解着色することを特徴
とするアルミニウムまたはアルミニウム合金の電解着色
方法。(1) When anodized aluminum or aluminum alloy is electrolytically colored in an electrolytic coloring solution containing a metal salt, an electrolytic solution having electrical conductivity equivalent to that of the electrolytic coloring solution or the electrolytic coloring solution. A voltage having a substantially positive voltage waveform is applied therein for pretreatment, and then the ratio of the application time of the positive voltage to the negative voltage is controlled to be 1:1 to 3 in the electrolytic coloring solution. 1. A method for electrolytically coloring aluminum or an aluminum alloy, the method comprising electrolytically coloring aluminum or aluminum alloy by applying a waveform voltage at a rate of 1 to 25 times per second.
３に制御された波形の電圧を、正と負の電流密度の比率
が１：２〜６になるように通電して電解着色することを
特徴とする請求項１記載の電解着色方法。(2) The ratio of the application time of positive voltage and negative voltage is 1:1 or more
2. The electrolytic coloring method according to claim 1, wherein the electrolytic coloring is carried out by applying a voltage having a waveform controlled to 3:3 so that the ratio of positive to negative current densities is 1:2 to 6.
３になるように制御された波形の電圧が、三相交流電圧
を制御したものである請求項１記載の電解着色方法。(3) The ratio of the application time of positive voltage and negative voltage is 1:1 or more
2. The electrolytic coloring method according to claim 1, wherein the voltage of the waveform controlled to be 3 is a controlled three-phase AC voltage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63028490A JP2659545B2 (en) | 1988-02-09 | 1988-02-09 | Electrolytic coloring method of aluminum or aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63028490A JP2659545B2 (en) | 1988-02-09 | 1988-02-09 | Electrolytic coloring method of aluminum or aluminum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01205092A true JPH01205092A (en) | 1989-08-17 |
| JP2659545B2 JP2659545B2 (en) | 1997-09-30 |
Family
ID=12250105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63028490A Expired - Lifetime JP2659545B2 (en) | 1988-02-09 | 1988-02-09 | Electrolytic coloring method of aluminum or aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2659545B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101622375B1 (en) | 2014-11-03 | 2016-05-19 | (주)구수중전기 | Electrochromic System of the Aluminum Material using a Crossflow Asymmetry Power Source and Controlling Method for the Same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5249408A (en) * | 1975-10-17 | 1977-04-20 | Citizen Watch Co Ltd | Motor for electronic watch |
| JPS5522558A (en) * | 1978-08-04 | 1980-02-18 | Mazda Motor Corp | Moving device of driver cabin seat in cab-over type vehicle |
| JPS5852037A (en) * | 1981-09-21 | 1983-03-28 | セテツク・コ−ポレ−シヨン | Box structure |
-
1988
- 1988-02-09 JP JP63028490A patent/JP2659545B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5249408A (en) * | 1975-10-17 | 1977-04-20 | Citizen Watch Co Ltd | Motor for electronic watch |
| JPS5522558A (en) * | 1978-08-04 | 1980-02-18 | Mazda Motor Corp | Moving device of driver cabin seat in cab-over type vehicle |
| JPS5852037A (en) * | 1981-09-21 | 1983-03-28 | セテツク・コ−ポレ−シヨン | Box structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2659545B2 (en) | 1997-09-30 |
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