JPS6261120B2 - - Google Patents
Info
- Publication number
- JPS6261120B2 JPS6261120B2 JP15459484A JP15459484A JPS6261120B2 JP S6261120 B2 JPS6261120 B2 JP S6261120B2 JP 15459484 A JP15459484 A JP 15459484A JP 15459484 A JP15459484 A JP 15459484A JP S6261120 B2 JPS6261120 B2 JP S6261120B2
- Authority
- JP
- Japan
- Prior art keywords
- bath
- acid
- electrolytic coloring
- film
- 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
Links
- 238000004040 coloring Methods 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000838 Al alloy Inorganic materials 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 239000010407 anodic oxide Substances 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 235000019646 color tone Nutrition 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910017888 Cu—P Inorganic materials 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
（産業上の利用分野）
本発明は、アルミニウム及びアルミニウム合金
の陽極酸化皮膜の電解着色浴組成に関するもので
ある。
（従来の技術）
アルミニウム及びアルミニウム合金の陽極酸化
皮膜とは、アルミニウム及びアルミニウム合金の
表面に硫酸電解法などの方法を用いて陽極酸化処
理を行なつて得た酸化皮膜（以下単に皮膜）をい
う。
従来の電解着色浴において、赤から赤紫色系統
の色調を得るものとしては、硫酸銅を主成分とす
る浴がある（例えば特公昭38―1715号）。しかし
硫酸銅浴では、灰色味のある赤から赤紫色系統の
着色しか得られず、鮮明な色調を得ることはでき
ない。又硫酸銅浴で電解着色した皮膜は、ニツケ
ル塩、スズ塩等による電解着色皮膜と比較する
と、耐食性に劣ることが知られている。しかもい
わゆる「つきまわり」性が悪く、工業的生産性に
劣るという欠陥も有している。
一方電解着色浴としてピロリン酸銅を含有する
例が既に知られている（例えば特開昭57−140895
号）。しかしその構成ではピロリン酸銅の沈澱が
生じ易い等、浴安定性が悪く、安定した電解着色
を行えない。又ピロリン酸銅を溶解させるために
EDTA、エチレンジアミン等の錯化剤が必要とな
り、浴がコスト高になるのを避けることができな
い。
（発明が解決しようとする問題点）
上記従来の構成では、鮮明な着色が得られず、
しかも形成される皮膜に充分な耐食性が得られな
いという問題点を有している。又色のつきまわり
性が悪く、工業的生産性に劣つている。一方ピロ
リン酸銅を含む電解着色浴は既に提案されている
が、その構成では浴安定性が悪く安定した電解着
色が行えないという問題点を有している。又錯化
剤が不可欠であるため、コスト高になるという問
題もある。
本発明は、上記問題点を解決しようとするもの
である。
（問題点を解決するための手段）
本発明は、ピロリン酸銅を主成分とし、硫酸ニ
ツケル、硫酸マグネシウム、硫酸亜鉛の金属塩の
いずれか或はそれらの組合せからなる添加剤を含
み、硫酸、ピロリン酸、リン酸等の無機酸又はシ
ユウ酸、酒石酸、クエン酸等の有機酸のいずれか
或はそれらの組合せからなるPH調整剤を含み、PH
調整剤によつてPHが２以下に調整されていること
を特徴とするアルミニウム及びアルミニウム合金
の陽極酸化皮膜の電解着色浴組成である。
（手段の説明）
本発明による電解着色浴組成の特色の一つは、
従来にない色調が得られることであり、それは、
原色に近い鮮明な、赤、朱、深紅、赤紫、紫等で
ある。又得られる皮膜は耐食性に優れている。更
に電解着色の際の色のつきまわり性が良好で、工
業的生産性に優れている。
本発明によつて、原色に近い鮮明な色調が得ら
れること及び、耐食性に優れた皮膜がえられる理
由は次の通りである。電解着色浴中の主成分であ
るピロリン酸銅（Cu2P2O7）は、それ自体で不溶
性錯化合物を形成する。分子中の一つの銅原子は
イオン結合で、残りの銅原子は強固な錯体配位の
結合を成している（入門キレート化学：上野景平
著、221頁、南江堂）。即ちCu++［Cu―P2O7］--
の構造をもち、かつこれらの銅原子間には、
Cu（イオン結合）Cu（配位結合）
の平衡が保たれている。従つて例えば本発明によ
る電解着色浴組成を２次電解着色浴に採用した場
合には、電解着色によつて皮膜の孔中に析出する
銅の形態は、約半分が金属銅或は酸化銅である
が、残りはピロリン酸と結合した状態のままとな
る。それは得られた着色皮膜の成分を分析した結
果（表１）、多量のリンを検出したことから明ら
かである。なお表１は、後述する実施例２のNo.１
とNo.２の方法で得られた着色皮膜の成分の分析結
果を示している。
(Industrial Application Field) The present invention relates to an electrolytic coloring bath composition for anodic oxidation films of aluminum and aluminum alloys. (Prior art) The anodized film of aluminum and aluminum alloy refers to an oxide film (hereinafter simply referred to as film) obtained by anodizing the surface of aluminum and aluminum alloy using a method such as sulfuric acid electrolysis. . Among conventional electrolytic coloring baths, there is a bath containing copper sulfate as a main component (for example, Japanese Patent Publication No. 38-1715) for obtaining color tones ranging from red to reddish-purple. However, in a copper sulfate bath, only a grayish red to reddish-purple coloration can be obtained, and a clear color tone cannot be obtained. Furthermore, it is known that a film electrolytically colored in a copper sulfate bath has inferior corrosion resistance compared to a film electrolytically colored with nickel salt, tin salt, or the like. Moreover, it also has the disadvantage of poor "throwing" properties and poor industrial productivity. On the other hand, examples of electrolytic coloring baths containing copper pyrophosphate are already known (e.g., JP-A-57-140895
issue). However, with this configuration, the bath stability is poor, such as easy precipitation of copper pyrophosphate, and stable electrolytic coloring cannot be performed. Also, to dissolve copper pyrophosphate
A complexing agent such as EDTA or ethylenediamine is required, which inevitably increases the cost of the bath. (Problems to be solved by the invention) With the above conventional configuration, clear coloring cannot be obtained;
Moreover, there is a problem in that the film formed does not have sufficient corrosion resistance. In addition, the color spread is poor and the industrial productivity is poor. On the other hand, an electrolytic coloring bath containing copper pyrophosphate has already been proposed, but this configuration has a problem in that the bath stability is poor and stable electrolytic coloring cannot be performed. Furthermore, since a complexing agent is essential, there is also the problem of high cost. The present invention attempts to solve the above problems. (Means for Solving the Problems) The present invention contains copper pyrophosphate as a main component, contains an additive consisting of any one of metal salts of nickel sulfate, magnesium sulfate, zinc sulfate, or a combination thereof, and contains sulfuric acid, Contains a PH adjuster consisting of inorganic acids such as pyrophosphoric acid and phosphoric acid, or organic acids such as oxalic acid, tartaric acid, and citric acid, or a combination thereof.
This is an electrolytic coloring bath composition for anodic oxidation films of aluminum and aluminum alloys, characterized in that the pH is adjusted to 2 or less using a regulator. (Description of Means) One of the features of the electrolytic coloring bath composition according to the present invention is:
It is possible to obtain an unprecedented color tone, which is,
Vivid colors close to primary colors, such as red, vermilion, crimson, magenta, and violet. Furthermore, the resulting film has excellent corrosion resistance. Furthermore, it has good color coverage during electrolytic coloring and is excellent in industrial productivity. The reason why the present invention allows a clear color tone close to the primary color and a film with excellent corrosion resistance to be obtained is as follows. Copper pyrophosphate (Cu 2 P 2 O 7 ), which is the main component in the electrolytic coloring bath, forms an insoluble complex compound by itself. One copper atom in the molecule forms an ionic bond, and the remaining copper atoms form strong complex coordination bonds (Introductory Chelate Chemistry: Keihei Ueno, p. 221, Nankodo). That is, Cu ++ [Cu―P 2 O 7 ] --
It has a structure of , and an equilibrium of Cu (ionic bonds) and Cu (coordination bonds) is maintained between these copper atoms. Therefore, for example, when the electrolytic coloring bath composition according to the present invention is adopted as a secondary electrolytic coloring bath, about half of the copper deposited in the pores of the film due to electrolytic coloring is in the form of metallic copper or copper oxide. However, the rest remains bound to pyrophosphate. This is clear from the fact that a large amount of phosphorus was detected as a result of analyzing the components of the obtained colored film (Table 1). Table 1 shows No. 1 of Example 2, which will be described later.
and shows the analysis results of the components of the colored film obtained by method No. 2.
【表】
このように本発明による電解着色浴組成を用い
た場合には、ピロリン酸と結合した状態のままの
銅が多く存在することから、ピロリン酸銅に代え
て硫酸銅を用いた従来の電解着色浴組成の場合に
比べて、形成された皮膜の電触性は半減すること
になる。表２にキヤス試験の結果を示す。表２で
明らかなように、本発明による電解着色浴組成と
した２次電解着色浴を用いて着色処理した皮膜の
耐食性は、従来の硫酸銅浴のものに比べて良好で
あつた。[Table] As described above, when using the electrolytic coloring bath composition according to the present invention, there is a large amount of copper still bound to pyrophosphate. Compared to the case of electrolytic coloring bath composition, the electrocontact properties of the formed film are reduced by half. Table 2 shows the results of the Cass test. As is clear from Table 2, the corrosion resistance of the coatings colored using the secondary electrolytic coloring bath having the electrolytic coloring bath composition according to the present invention was better than that of the conventional copper sulfate bath.
【表】
なお表２は次のような条件のもとでの試験結果
である。アルミニウム合金としてA6063S―T5材
（大きさ；75×150mm）を用い、硫酸浴で陽極酸化
処理を行ない、９μｍの厚さの皮膜を得た後、カ
ーボンを一方の極とし、下記のそれぞれの浴中で
電解着色した。上記浴としては、本発明による電
解着色浴（実施例１（後述）と同様）、硫酸銅浴
（硫酸銅30ｇ／、硫酸マグネシウム30ｇ／及
び硫酸10ｇ／からなる浴）、ニツケル塩浴（硫
酸ニツケル30ｇ／、ホウ酸30ｇ／からなる
浴）を用いた。各々交流電圧15Vを４分間通電し
て得られた着色皮膜に、純水中で煮沸封孔操作を
30分間行なつた後、JISH8681によるキヤス耐食
試験をそれぞれ８時間、16時間、24時間実施し
た。
上述したように本発明による電解着色浴組成を
用いた場合には、ピロリン酸と結合した状態のま
まの銅が皮膜中に多く存在する。このピロリン酸
銅は［Cu―P2O7］--で示される陰性基を有して
おり、これが色調に多大の影響を与える。なぜな
らば、特公昭38−1715号に記載されているよう
に、SeO3 --、TeO3 --、MnO4 --のような酸素酸
塩を持つ金属塩は、電解着色によつて皮膜中に析
出するが、これらと同様に［Cu―P2O7］--も皮
膜中に析出するからである。これは先に示したよ
うに、皮膜成分中に多量のリンが含まれているこ
とからも明らかである。
このことから本発明による電解着色組成を採用
して得られる皮膜の色調は、従来の硫酸銅浴の場
合と根本的に異なり、赤から赤紫系統の鮮明な色
調となる。
なおピロリン酸銅の濃度が１ｇ／以下では淡
色しかえられず、又10ｇ／以上では浴が過飽和
となる場合がある。従つてピロリン酸銅の濃度は
１〜10ｇ／が良く、好ましくは１〜５ｇ／で
ある。硫酸ニツケル、硫酸マグネシウム、硫酸亜
鉛の金属塩のいずれか或はそれらの組合せからな
る添加剤は、銅と共に電解着色時に皮膜の孔中に
は析出しない。この添加剤は着色時に発生するガ
スの均一化と微細化を行ない、従つて着色ムラの
防止、皮膜破壊の抑制に不可欠である。添加剤の
濃度は10ｇ／以下では効果が少なく、50ｇ／
以上では金属塩によつては孔中に析出が生じ、色
調が不透明となる。従つて添加剤は10〜50ｇ／
が好ましい。
又硫酸、ピロリン酸、リン酸等の無機酸又はシ
ユウ酸、酒石酸、クエン酸等の有機酸のいずれか
或はそれらの組合せからなるPH調整剤によつて、
浴のPHを２以下とするのは、ピロリン酸銅がPH２
以上では溶解しないので、その沈澱を防ぐためで
ある。第２の理由は、浴組成分及びPHの安定性を
確保するためである。ピロリン酸銅を電解着色浴
組成分とした場合に、従来の構成（例えば特開昭
57−140895号）では浴組成中に錯化剤を加えてピ
ロリン酸銅の沈澱を防止し、しかもそのためにPH
を４〜６程度に維持する必要がある。しかしその
構成では浴組成分の種類が増大し、又工業的生産
においては、陽極酸化処理後の水洗水を電解着色
浴に持込むことが避けられないが、そのことによ
つて陽極酸化処理用の酸が電解着色浴中に蓄積
し、電解着色浴のPHは抵下する。その結果容易に
着色変化が生じることになる。これに対し本発明
によれば、錯化剤を使用する必要がなく、又工業
的生産においては、前述の理由により電解着色浴
のPHは低下するが、PHが２以下であれば全く安定
しているので、着色変化が生じ難く浴管理が容易
になる。又PHを２以下とすれば、液伝導度が高く
なつて、つきまわり性が良くなる。更に浴の老化
を防止する働きもある。このようにPHを調整する
ために用いる無機酸及び有機酸は、ピロリン酸銅
の溶解を促進する働きと浴を安定する働きを有す
るばかりでなく、色のつきまわり性を良くする効
果も有している。
（実施例）
実施例 １
アルミニウム合金としてA6063S―T5材を用
い、通常の硫酸浴で陽極酸化処理を行ない、９μ
ｍの皮膜を得た。次にカーボンを一方の極として
硫酸10ｇ／、ピロリン酸銅1.5ｇ／、硫酸ニ
ツケル20ｇ／からなる電解着色浴中で、交流電
圧15Vを４分間通電した。その結果、鮮明な深紅
色の着色皮膜を得た。
実施例 ２
アルミニウム合金としてA1100P―H24材を用
い、通常の硫酸浴で陽極酸化処理を行ない、12μ
ｍの皮膜を得た。次にカーボンを一方の極とし、
表３に示す種々の電解着色浴中で、交流電圧18V
を２分間通電した。この結果、表中に示したよう
な色調の皮膜を得た。[Table] Table 2 shows the test results under the following conditions. Using A6063S-T5 material (size: 75 x 150 mm) as the aluminum alloy, anodize it in a sulfuric acid bath to obtain a 9 μm thick film, then use carbon as one electrode and apply the following baths. It was electrolytically colored inside. The above baths include an electrolytic coloring bath according to the present invention (same as in Example 1 (described later)), a copper sulfate bath (a bath consisting of 30 g of copper sulfate, 30 g of magnesium sulfate, and 10 g of sulfuric acid), and a nickel salt bath (a bath of nickel sulfate). (30 g/bath) was used. The colored films obtained by applying an AC voltage of 15V for 4 minutes were boiled and sealed in pure water.
After 30 minutes, a cast corrosion resistance test according to JISH8681 was conducted for 8 hours, 16 hours, and 24 hours, respectively. As described above, when the electrolytic coloring bath composition according to the present invention is used, a large amount of copper remains bonded to pyrophosphoric acid in the film. This copper pyrophosphate has a negative group represented by [Cu—P 2 O 7 ] -- , which has a great effect on the color tone. This is because, as described in Japanese Patent Publication No. 38-1715, metal salts with oxyacids such as SeO 3 -- , TeO 3 -- , and MnO 4 -- can be dissolved in the film by electrolytic coloring. This is because, like these, [Cu—P 2 O 7 ] -- also precipitates in the film. This is clear from the fact that the film components contain a large amount of phosphorus, as shown above. Therefore, the color tone of the film obtained by employing the electrolytic coloring composition according to the present invention is fundamentally different from that of the conventional copper sulfate bath, and has a clear color tone ranging from red to reddish-purple. Note that if the concentration of copper pyrophosphate is less than 1 g/g, only a pale color will be obtained, and if the concentration is more than 10 g/p, the bath may become supersaturated. Therefore, the concentration of copper pyrophosphate is preferably 1 to 10 g/, preferably 1 to 5 g/. The additive consisting of a metal salt of nickel sulfate, magnesium sulfate, zinc sulfate, or a combination thereof does not precipitate into the pores of the film during electrolytic coloring together with copper. This additive homogenizes and refines the gas generated during coloring, and is therefore essential for preventing uneven coloring and suppressing film destruction. If the concentration of the additive is less than 10g/, it will have little effect;
Above this, some metal salts may precipitate in the pores, making the color opaque. Therefore, the amount of additive is 10-50g/
is preferred. Also, by using a PH regulator consisting of inorganic acids such as sulfuric acid, pyrophosphoric acid, phosphoric acid, or organic acids such as oxalic acid, tartaric acid, citric acid, or a combination thereof,
Copper pyrophosphate keeps the pH of the bath below 2.
This is to prevent precipitation since it will not dissolve at this temperature. The second reason is to ensure stability of bath composition and pH. When copper pyrophosphate is used as an electrolytic coloring bath composition, conventional compositions (for example,
No. 57-140895), a complexing agent was added to the bath composition to prevent precipitation of copper pyrophosphate, and to do so, the PH
It is necessary to maintain the value at around 4 to 6. However, this configuration increases the variety of bath compositions, and in industrial production, it is unavoidable to bring the washing water after anodizing treatment into the electrolytic coloring bath, which makes it difficult to use for anodizing treatment. of acid accumulates in the electrolytic coloring bath, and the pH of the electrolytic coloring bath decreases. As a result, color changes easily occur. On the other hand, according to the present invention, there is no need to use a complexing agent, and in industrial production, the pH of the electrolytic coloring bath decreases due to the above-mentioned reasons, but if the pH is 2 or less, it is completely stable. Therefore, color change is less likely to occur and bath management becomes easier. Furthermore, if the pH is set to 2 or less, the liquid conductivity will be high and the throwing power will be improved. It also has the effect of preventing the aging of the bath. The inorganic acids and organic acids used to adjust the pH in this way not only have the function of promoting the dissolution of copper pyrophosphate and the function of stabilizing the bath, but also have the effect of improving color spread. ing. (Example) Example 1 A6063S-T5 material was used as the aluminum alloy, anodized in a normal sulfuric acid bath, and 9μ
A film of m was obtained. Next, an AC voltage of 15 V was applied for 4 minutes in an electrolytic coloring bath consisting of 10 g of sulfuric acid, 1.5 g of copper pyrophosphate, and 20 g of nickel sulfate, using carbon as one electrode. As a result, a clear deep red colored film was obtained. Example 2 A1100P-H24 material was used as the aluminum alloy, anodized in a normal sulfuric acid bath, and 12μ
A film of m was obtained. Next, use carbon as one pole,
In various electrolytic coloring baths shown in Table 3, an AC voltage of 18 V
was energized for 2 minutes. As a result, a film having the color tone shown in the table was obtained.
【表】
（発明の効果）
ピロリン酸銅を主成分とし、硫酸ニツケル、硫
酸マグネシウム、硫酸亜鉛の金属塩のいずれか或
はそれらの組合せからなる添加剤を含み、硫酸、
ピロリン酸、リン酸等の無機酸又はシユウ酸、酒
石酸、クエン酸等の有機酸のいずれか或はそれら
の組合せからなるPH調整剤を含み、PH調整剤によ
つてPHが２以下に調整されているので；
(a) 製品の電解着色皮膜に鮮明な着色が得られる
ばかりでなく、形成される皮膜に充分な耐食性
が得られる。
(b) 電解着色時において色のつきまわり性が良い
ことから、均質な着色が行なえ、工業的生産に
優れている。
(c) 浴安定性が良く、浴管理が容易である。又安
定した電解着色が行える。
(d) 錯化剤が不要であるため、浴の低コスト化が
図れる。[Table] (Effects of the invention) The main component is copper pyrophosphate, contains an additive consisting of metal salts of nickel sulfate, magnesium sulfate, zinc sulfate, or a combination thereof, and contains sulfuric acid,
Contains a PH adjuster consisting of either an inorganic acid such as pyrophosphoric acid or phosphoric acid, or an organic acid such as oxalic acid, tartaric acid, or citric acid, or a combination thereof, and the pH is adjusted to 2 or less by the PH adjuster. (a) Not only can the electrolytically colored film of the product be clearly colored, but also sufficient corrosion resistance can be obtained in the formed film. (b) Since the color spread is good during electrolytic coloring, uniform coloring can be achieved and it is excellent for industrial production. (c) Good bath stability and easy bath management. Moreover, stable electrolytic coloring can be performed. (d) Since no complexing agent is required, the cost of the bath can be reduced.
Claims (1)
硫酸マグネシウム、硫酸亜鉛の金属塩のいずれか
或はそれらの組合せからなる添加剤を含み、硫
酸、ピロリン酸、リン酸等の無機酸又はシユウ
酸、酒石酸、クエン酸等の有機酸のいずれか或は
それらの組合せからなるPH調整剤を含み、PH調整
剤によつてPHが２以下に調整されていることを特
徴とするアルミニウム及びアルミニウム合金の陽
極酸化皮膜の電解着色浴組成。 ２ 上記ピロリン酸銅の濃度が１〜10ｇ／であ
る特許請求の範囲第１項記載のアルミニウム及び
アルミニウム合金の陽極酸化皮膜の電解着色浴組
成。 ３ 上記添加剤の濃度が10〜50ｇ／である特許
請求の範囲第１項記載のアルミニウム及びアルミ
ニウム合金の陽極酸化皮膜の電解着色浴組成。[Claims] 1. Copper pyrophosphate as the main component, nickel sulfate,
Contains an additive consisting of either a metal salt of magnesium sulfate or zinc sulfate, or a combination thereof, and either an inorganic acid such as sulfuric acid, pyrophosphoric acid, or phosphoric acid, or an organic acid such as oxalic acid, tartaric acid, or citric acid. An electrolytic coloring bath composition for anodic oxidation films of aluminum and aluminum alloys, characterized in that it contains a PH adjuster consisting of a combination thereof, and the PH is adjusted to 2 or less by the PH adjuster. 2. The electrolytic coloring bath composition for anodic oxidation films of aluminum and aluminum alloys according to claim 1, wherein the concentration of the copper pyrophosphate is 1 to 10 g/. 3. The electrolytic coloring bath composition for anodic oxide films of aluminum and aluminum alloys according to claim 1, wherein the concentration of the additive is 10 to 50 g/.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15459484A JPS6134198A (en) | 1984-07-24 | 1984-07-24 | Electrolytic coloring bath composition for anodic oxidation film of aluminum and its alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15459484A JPS6134198A (en) | 1984-07-24 | 1984-07-24 | Electrolytic coloring bath composition for anodic oxidation film of aluminum and its alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6134198A JPS6134198A (en) | 1986-02-18 |
| JPS6261120B2 true JPS6261120B2 (en) | 1987-12-19 |
Family
ID=15587596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15459484A Granted JPS6134198A (en) | 1984-07-24 | 1984-07-24 | Electrolytic coloring bath composition for anodic oxidation film of aluminum and its alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6134198A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63210295A (en) * | 1987-02-25 | 1988-08-31 | Fujita Shoji Kk | Coloring treatment of aluminum or aluminum alloy for developing pastel color |
-
1984
- 1984-07-24 JP JP15459484A patent/JPS6134198A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6134198A (en) | 1986-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4606796A (en) | Colored, anodized aluminum-base article and method of preparing same | |
| US4070255A (en) | Process for electrolytically coloring aluminum and aluminum alloys | |
| JPS6261120B2 (en) | ||
| JPS60110895A (en) | Electrolytic coloring method of aluminum and aluminum alloy | |
| JPS60197897A (en) | Formation of opaque white anodized film of aluminum or aluminum alloy | |
| JPS644598B2 (en) | ||
| JPS5925039B2 (en) | Method for forming a colored anodic oxide film with improved durability on aluminum or aluminum alloys | |
| JPH01139798A (en) | Surface treating agent for aluminum-based metal having oxide film | |
| JPS5948879B2 (en) | Aluminum electrolytic coloring method | |
| JPS63223199A (en) | Method for electrolytically-coloring aluminum material | |
| JPH02194195A (en) | Anodic oxidation of titanium and titanium alloy | |
| SU411164A1 (en) | ||
| JPS5956594A (en) | Method for coloring aluminum | |
| JPS5858440B2 (en) | aluminum material | |
| JPS5830398B2 (en) | Electrolytic coloring bath composition of aluminum anodic oxide film | |
| JPS5928636B2 (en) | Method of forming a colored protective film on the surface of aluminum materials | |
| JPS58161796A (en) | Method for coloring anodic oxide film of aluminum or aluminum alloy | |
| JPS6233318B2 (en) | ||
| JPH0480396A (en) | Method of coloring anodically oxidized coating on aluminum | |
| JPS5855593A (en) | Multi-color electrolytic coloration of aluminum of aluminum alloy | |
| JPS61204395A (en) | Colored aluminum material | |
| JPH0450400B2 (en) | ||
| JPS5913095A (en) | Electrolytic pigmentation method of aluminum or aluminum alloy | |
| JPS6020478B2 (en) | Aluminum surface treatment method | |
| JPH0454760B2 (en) |