JPS6360290A - Blackening solution for aluminum or its alloy - Google Patents
Blackening solution for aluminum or its alloyInfo
- Publication number
- JPS6360290A JPS6360290A JP20385886A JP20385886A JPS6360290A JP S6360290 A JPS6360290 A JP S6360290A JP 20385886 A JP20385886 A JP 20385886A JP 20385886 A JP20385886 A JP 20385886A JP S6360290 A JPS6360290 A JP S6360290A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- soln
- aluminum
- zinc
- treatment
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 22
- 229910052782 aluminium Inorganic materials 0.000 title claims description 22
- 229910045601 alloy Inorganic materials 0.000 title abstract 2
- 239000000956 alloy Substances 0.000 title 1
- 238000011282 treatment Methods 0.000 claims abstract description 44
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001439 antimony ion Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 20
- 239000011701 zinc Substances 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 15
- 229910052725 zinc Inorganic materials 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 229910052787 antimony Inorganic materials 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000007747 plating Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- -1 aluminum alloys Chemical compound 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 235000019646 color tone Nutrition 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Chemical Treatment Of Metals (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に黒色
の着色被膜を形成する処理液に関するものであり、さら
に詳しく述べるならば、家!製品部品、光学機器部品、
電子機器部品等として使用されるアルミニウムまたはア
ルミニウム合金に化学置換法により黒色被膜を形成させ
るために用いられる処理液に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a treatment solution for forming a black colored film on aluminum or an aluminum alloy. product parts, optical equipment parts,
The present invention relates to a treatment liquid used to form a black film on aluminum or aluminum alloys used as electronic device parts by chemical substitution.
アルミニウム(アルミニウム合金を含む、以下同じ)の
表面に、化学置換亜鉛メッキ法を利用して黒色化亜鉛め
っき被膜を形成する方法として、特公昭44−8338
号公報は、第1段処理として化学置換亜鉛メッキを施し
次いで第2段処理としてモリブデン酸塩および弗化物を
含む弱酸性加熱水溶液浸漬法を開示している。Japanese Patent Publication No. 44-8338 describes a method of forming a blackened galvanized film on the surface of aluminum (including aluminum alloys, the same shall apply hereinafter) using a chemical displacement galvanizing method.
The publication discloses a method in which chemical displacement zinc plating is performed as a first stage treatment, followed by immersion in a weakly acidic heated aqueous solution containing a molybdate and a fluoride as a second stage treatment.
さらに、上記特公昭44−8338号公報の方法により
得られる黒色化被膜の外観を改善しまた排水処理を容易
にする方法として、特公昭55−51030号公報の方
法は、カルシウムイオン、亜鉛イオン、亜硝酸イオン、
ケイ酸イオンを含んだ、−9〜12の処理液にアルミニ
ウムを浸漬する方法全提案している。この方法による処
理液の温度は80℃ないし沸騰点であり、浸漬時間は1
0ないし40分であると説明されている。処理液の温度
が80℃未満となると、着色速度が低下する念めこの方
法では80℃以上を処理温度としている。Furthermore, as a method for improving the appearance of the blackened coating obtained by the method of Japanese Patent Publication No. 44-8338 and facilitating wastewater treatment, the method of Japanese Patent Publication No. 55-51030 discloses calcium ions, zinc ions, nitrite ion,
All methods are proposed in which aluminum is immersed in a -9 to 12 treatment solution containing silicate ions. The temperature of the treatment liquid in this method is 80℃ or boiling point, and the immersion time is 1
It is explained that the duration is 0 to 40 minutes. In this method, the processing temperature is set at 80°C or higher, in order to prevent the rate of coloring from decreasing if the temperature of the processing liquid is lower than 80°C.
又亜鉛置換法によらない黒色化法としては、硫酸、クロ
ム酸ナトリウム、塩酸、過マンガン酸カリウム、表面活
性剤全含む水溶gを加熱して被処理アルミニウムを浸漬
する方法がある。As a blackening method that does not rely on the zinc substitution method, there is a method in which aluminum to be treated is immersed in an aqueous solution containing sulfuric acid, sodium chromate, hydrochloric acid, potassium permanganate, and a surfactant by heating.
上述のように、従来のアルミニウム黒色化処理は高温長
時間で所望の着色効果をも念らすものであった。このた
め、加熱エネルギの消耗が大きくまた処理液が作業者に
触れ***合の危険性が高くなるなどの問題があった。As mentioned above, conventional aluminum blackening treatments require high temperatures and long periods of time to achieve the desired coloring effect. Therefore, there were problems such as a large consumption of heating energy and an increased risk of the processing liquid coming into contact with the operator.
さらに、従来のアルミニウム黒色化処理は2段処理であ
った。Furthermore, conventional aluminum blackening treatment is a two-stage treatment.
したがりて、従来の処理液と同等以上の仕上げ外観を有
する被膜を一段処理で従来のものと同等以上の被膜形成
速度で形成できる低温アルミニウム黒色化処理液の出現
が切望されていた。Therefore, there has been a strong desire for a low-temperature aluminum blackening treatment solution that can form a film having a finished appearance equal to or better than that of conventional treatment solutions in a single step at a film formation rate equal to or higher than that of conventional treatment solutions.
c問題点を解決するための手段および作用〕本発明は以
上の問題点を解決するために成されたものであって、ア
ルミニウムを亜鉛およびアンチモンを含むアルカリ水溶
液に浸漬することによって、低温でアルミニウム表面に
黒色被膜を形成させることができるアルミニウム用置換
型黒色化処理液を提供せんとするものである。(c) Means and operation for solving the problems] The present invention has been made to solve the above problems, and is made by immersing aluminum in an alkaline aqueous solution containing zinc and antimony. It is an object of the present invention to provide a substitution type blackening treatment liquid for aluminum that can form a black film on the surface.
しかして、本発明に係る処理液は、亜鉛イオン111/
1以上とアンチモンイオン0.05〜5g/ノを含み且
つpHが12以上であることを特徴とする。本発明に係
る処理液に浸漬されたアルミニウムの表面では、まずア
ルカリ性水溶液中でのアルミニウムの溶解が開始し、次
いで処理液に溶解しているZnとsbのイオンが還元さ
れそしてアルミニウムの表面に共析する。この結果、黒
色外観を有する被膜が形成される。かかる被膜形成は低
温(20〜45℃)で進行する。Therefore, the treatment liquid according to the present invention has zinc ion 111/
1 or more and antimony ion 0.05 to 5 g/no, and has a pH of 12 or more. On the surface of aluminum immersed in the treatment solution according to the present invention, dissolution of aluminum in the alkaline aqueous solution first begins, and then Zn and sb ions dissolved in the treatment solution are reduced and co-exist on the surface of aluminum. analyze. As a result, a coating having a black appearance is formed. Such film formation proceeds at low temperatures (20 to 45°C).
以下、本発明に係る処理液の組成全詳しく説明する。Hereinafter, the entire composition of the treatment liquid according to the present invention will be explained in detail.
亜鉛を処理液に含ませるためには、酸化亜鉛、炭酸亜鉛
、水酸化亜鉛、硝酸亜鉛等を液中に添加。In order to include zinc in the treatment solution, zinc oxide, zinc carbonate, zinc hydroxide, zinc nitrate, etc. are added to the solution.
溶解させる。これらの他に硫酸亜鉛、塩化亜鉛等も使用
することができる。要は亜鉛イオンを水溶液中に存在さ
せる方法を採用すればよい。処理液中の亜鉛の濃度は1
1/1以上、特に4〜20I/!の範囲が好ましい。亜
鉛濃度が1g/lよりも低いときは亜鉛めっき被膜が形
成されない。亜鉛濃度の上限は特に制限がなく、溶解限
度まで亜鉛を水溶液中釦添加してもよい。その限度は後
述の声調節を行なっても309/lよりも多く亜鉛弁を
溶解させることは困難である。即ち、30E/1が一般
に亜鉛の溶解限度となる。Dissolve. In addition to these, zinc sulfate, zinc chloride, etc. can also be used. In short, a method may be adopted in which zinc ions are present in an aqueous solution. The concentration of zinc in the treatment solution is 1
1/1 or more, especially 4-20I/! A range of is preferred. When the zinc concentration is lower than 1 g/l, no galvanized film is formed. There is no particular upper limit to the zinc concentration, and zinc may be added to the aqueous solution up to the solubility limit. This limit makes it difficult to dissolve more than 309/l of zinc valve even if the voice adjustment described below is performed. That is, 30E/1 is generally the solubility limit for zinc.
アンチモンを含ませるための方法としては、三酸祐4ン
チモン、酒石酸アンチモニルカリウム、酒石酸アンチモ
ニルナトリウム等の化合物を添加、溶解する方法が好ま
しいが、これらに限らず要はアンチモンイオンを水溶液
中に存在させる方法全採用すればよい。処理液中のアン
チモンの濃度は0.05〜5g/lの範囲である。アン
チモンの濃度が0.051/lよすも低いと、メッキ枝
膜は亜鉛めっき被膜とほぼ同色となり、黒色被膜が形成
されない。一方アンチモン濃度が5 Elllを越える
と被膜の密着性が低下するので好ましくない。Preferred methods for incorporating antimony include adding and dissolving compounds such as antimony triate, antimonyl potassium tartrate, and antimonyl sodium tartrate, but are not limited to these methods. All methods of making it exist should be adopted. The concentration of antimony in the treatment solution ranges from 0.05 to 5 g/l. If the antimony concentration is as low as 0.051/l, the plated branch film will have almost the same color as the galvanized film, and no black film will be formed. On the other hand, if the antimony concentration exceeds 5 Ells, the adhesion of the coating decreases, which is not preferable.
より好ましいアンチモンの濃度は0.2〜2 E/1で
ある。A more preferable concentration of antimony is 0.2 to 2 E/1.
次表に亜鉛とアンチモンの濃度を変化させて被膜の形成
と特性を調査した実験結果を示し、これらの好ましい濃
度比について説明する。この実験では、アルミニウム(
規格52S)を脱脂、水洗。The following table shows the results of an experiment in which film formation and properties were investigated by varying the concentrations of zinc and antimony, and the preferred ratio of these concentrations will be explained. In this experiment, aluminum (
Standard 52S) is degreased and washed with water.
酸洗、水洗後、25℃、−14の水溶液に2分浸漬し、
その後水洗し乾燥した。亜鉛とアンチモンは、それぞれ
、酸化亜鉛および三酸柾4ンチモンとして添加した。After pickling and water washing, immerse in a -14 aqueous solution at 25°C for 2 minutes,
It was then washed with water and dried. Zinc and antimony were added as zinc oxide and antimony trioxide, respectively.
以下余B 表 1 備考二表中の符号の意味は次のとおりである。The rest B below Table 1 Note: The meanings of the symbols in Table 2 are as follows.
Q 黒色度強い
× 灰黒色
表の結果より、亜鉛イオン/アンチモンイオンJi[i
t比f)E 1 / 2 (Znイ、tyai=1.P
/l : Sbイオン濃度=21713 )未満となる
か、あるいは亜鉛イオン/アンチモンイオン重量比が3
00/1(Znイオン濃度=15.9/):Sbイオン
濃度=0.05g/l)を越えると、被膜の黒色度が低
下することが分かる。亜鉛イオン/アンチモンイオン重
量比の範囲を2/1〜100/1とするとさらに黒色度
が高まる。Q Strong blackness
t ratio f) E 1/2 (Zn i, tyai=1.P
/l: Sb ion concentration = 21713) or the zinc ion/antimony ion weight ratio is 3.
It can be seen that when the ratio exceeds 00/1 (Zn ion concentration = 15.9/): Sb ion concentration = 0.05 g/l), the blackness of the coating decreases. When the weight ratio of zinc ions/antimony ions is in the range of 2/1 to 100/1, the degree of blackness is further increased.
本発明の処理液の−は12以上である。pHが12未満
であるとアルミのエツチングが弱くなるので黒色被膜生
成が不充分となる。処理液のpHが13以上であると、
さらにエツチング力が増すので短時間で黒色被膜を生成
させることができる。- of the treatment liquid of the present invention is 12 or more. If the pH is less than 12, the etching of aluminum becomes weak, resulting in insufficient formation of a black film. When the pH of the treatment liquid is 13 or more,
Furthermore, since the etching power is increased, a black film can be formed in a short time.
亜鉛添加溶解用化合物は酸性、中性もしくは弱アルカリ
性であるので、PHを調整し亜鉛化合物を溶解させるた
めにアルカリ化合物の添加が必要になる。Since the zinc-added dissolving compound is acidic, neutral or weakly alkaline, it is necessary to add an alkaline compound to adjust the pH and dissolve the zinc compound.
かかるアルカリ化合物としては、水酸化ナトリウム又は
水酸化カリウムが入手し易いために好ましく、これらの
他に炭酸ナトリウム又は第三リン酸ナトリウム等も使用
することができる。As such an alkali compound, sodium hydroxide or potassium hydroxide is preferred because it is easily available, and in addition to these, sodium carbonate, trisodium phosphate, etc. can also be used.
上記した処理液で黒色化処理を行なうには、特公昭44
−8338号公報もしくは特公昭55−51030号公
報等に記載されている公知の方法によりアルミニウムを
充分に清浄化しかつ酸化被膜を除去した後に、上記処理
液にアルミニウムを浸漬する。To perform blackening treatment with the above-mentioned treatment liquid,
After sufficiently cleaning the aluminum and removing the oxide film by a known method described in Japanese Patent Publication No. 8338 or Japanese Patent Publication No. 55-51030, the aluminum is immersed in the above treatment liquid.
浸漬温度が余り低いと黒色被膜生成に時間がかかり、一
方浸漬温度が余り高いと生成された被膜の密着性が悪く
、1九作業上危険であるので、それを考慮すると20〜
45℃で行なうのが適当である。浸漬時間は処理液の温
度、組成、被処理物の材質に応じて変化させるが一般的
には1〜3分である。If the dipping temperature is too low, it will take a long time to form a black film, while if the dipping temperature is too high, the resulting film will have poor adhesion, which can be dangerous for work.
It is appropriate to carry out the reaction at 45°C. The immersion time varies depending on the temperature and composition of the treatment liquid and the material of the object to be treated, but is generally 1 to 3 minutes.
上記処理液に浸漬後は水洗と乾燥を行なうことにより黒
色化したアルミニウム物品が得られる。After immersion in the treatment solution, a blackened aluminum article is obtained by washing with water and drying.
本発明の黒色化処理を一層改良し、工業的に望ましい表
面処理法とするために次のような処理液成分調整を行な
うことができる。In order to further improve the blackening treatment of the present invention and make it an industrially desirable surface treatment method, the following treatment liquid components can be adjusted.
メッキ処理液からの亜鉛の還元析出速度を適度に抑制し
て被膜の密着性を改良するためにメッキ処理液に、好ま
しくは5〜15!//lの硝酸塩を加える。硝酸塩とし
ては硝酸ナトリウム、硝酸カリウム又はメッキ液の亜鉛
分を上記濃度に維持する範囲内で硝酸亜鉛等が使用でき
る。硝酸塩と同様の目的で、例えば亜硝酸ナトリウムな
どの亜硝酸塩を、好ましくは0.5〜5j!/1.加え
ることもできる。In order to moderately suppress the rate of reduction and precipitation of zinc from the plating solution and improve the adhesion of the film, the plating solution should preferably contain 5 to 15%! Add //l nitrate. As the nitrate, sodium nitrate, potassium nitrate, or zinc nitrate may be used within a range that maintains the zinc content of the plating solution at the above concentration. For the same purpose as nitrates, nitrites such as sodium nitrite, preferably 0.5 to 5j! /1. You can also add
同一処理液に′liT液を補充せず処理回数が増大する
と処理液の老化が加速される。かかる処理液の老化を抑
制するために処理液に、例えばクエン酸ナトリウム、酒
石酸ナトリウム等のオキシカルゲン酸塩又はEDTAの
ナトリウム塩又はカリウム塩等のキレート剤を1〜51
/l加えることもできる。If the same processing solution is not replenished with the 'liT solution and the number of processing increases, the aging of the processing solution will be accelerated. In order to suppress aging of the processing solution, a chelating agent such as an oxycargenate salt such as sodium citrate or sodium tartrate or a sodium salt or potassium salt of EDTA is added to the processing solution.
/l can also be added.
又、本発明のメッキ処理液でアルミニウムに形成される
被膜の密着性を高めるために界面活性剤を例えば0.0
5〜11/l加えることもできる。Furthermore, in order to improve the adhesion of the film formed on aluminum with the plating solution of the present invention, a surfactant of, for example, 0.0
It is also possible to add 5 to 11/l.
界面活性剤は特定の種類に限定されないが、低発泡性の
点で非イオン界面活性剤が好着しい。Although the surfactant is not limited to a particular type, nonionic surfactants are preferred from the viewpoint of low foaming properties.
本発明によると、密着性が充分あシかっ充分従来被膜と
色調の面で競合できる落ち付いた均−黒色波gXヲ低温
で形成することができる。このため、省エネルギになる
し、作業上の危険性も少なくまた色調が安定した一定の
製品を工業的に量産できるようKなった。According to the present invention, it is possible to form a uniform black wave gX with sufficiently strong adhesion and a uniform black color that can compete with conventional coatings in terms of color tone at a low temperature. This saves energy, reduces the risk of work, and makes it possible to industrially mass-produce products with stable color tones.
又、処理液は一液タイブであるため、2段処理〈比較し
工程を短縮することができた。Furthermore, since the treatment liquid is a one-component type, the process can be shortened compared to a two-stage treatment.
以下、実施例を挙げさらに本発明を説明する。Hereinafter, the present invention will be further explained with reference to Examples.
処理材ニアルミニウム板 材質 2Sアルミニウム合
金板 材質 528
処理工程
1)アルカリ清浄 パーコクリーナーN372(日本パ
ーカライジング■’B) IU/1.60℃、1分ス
プレー
2)水洗
3)酸洗 10%HC1、常温、15秒浸漬4)
水洗
5)置換メッキ処理 25℃で実施例1の場合2分、実
施例2の場合3分浸漬
表2 メッキ処理液
6)水洗
7)乾燥 約80℃、5分
比較例として、特公昭44−8338号公報記載の黒色
化処理(ただし、Mo fit機含有処理液の温度は4
0℃とした)を行なった。Treatment material Nialuminum plate Material 2S aluminum alloy plate Material 528 Treatment process 1) Alkaline cleaning Perco Cleaner N372 (Nippon Parkerizing ■'B) IU/1.60℃, 1 minute spray 2) Water washing 3) Pickling 10% HC1, room temperature , 15 seconds immersion 4)
Washing with water 5) Displacement plating treatment Immersion at 25°C for 2 minutes in the case of Example 1 and 3 minutes in the case of Example 2 Table 2 Plating treatment solution 6) Washing with water 7) Drying Approximately 80°C, 5 minutes As a comparative example, Blackening treatment described in No. 8338 (however, the temperature of the treatment liquid contained in the Mo fit machine is 4
0°C).
比較例
処理材 実施例と同じ
処理工程
1)アルカリ清浄 実施例と同じ
2)水洗 実施例と同じ
3)酸洗 実施例と同じ
4)水洗 実施例と同じ
5)ZnIt換メッキ
メツキ 3
アルミニウム板(材質28)i比較例1の処理液に、ア
ルミニウム合金板(材質52S)を比較例2の処理液に
、夫々35℃で25秒間浸漬した。Comparative example treated material Same treatment steps as the example 1) Alkaline cleaning Same as the example 2) Water washing Same as the example 3) Pickling Same as the example 4) Water washing Same as the example 5) ZnIt replacement plating 3 Aluminum plate (Material) 28) i An aluminum alloy plate (material 52S) was immersed in the treatment solution of Comparative Example 1 and the treatment solution of Comparative Example 2 at 35° C. for 25 seconds.
6)水洗
7)黒色処理
(NH4)6MO,024−4H20151/13NH
4F 49/1水
残
上記処理液(40℃)の中に8分間浸漬した(tVj公
昭44−8338号公報の例1参照)。6) Washing with water 7) Black treatment (NH4) 6MO, 024-4H20151/13NH
4F 49/1 Wednesday
The remainder was immersed in the above treatment solution (40° C.) for 8 minutes (see Example 1 of tVj Publication No. 44-8338).
8)水洗 実施例と同じ
9)乾燥 実施例と同じ
試験方法
1)外観 O・・・均一で落ち付いた黒色Δ・・・黒色
比だし色ムラあり
2)密着性被膜を乾いた布切れで強く擦ったときの被膜
の除去性を調べた。8) Washing with water Same as the example 9) Drying Same test method as the example 1) Appearance 0... Uniform and calm black Δ... Black color unevenness 2) Adhesive coating with a dry cloth The removability of the film when rubbed strongly was investigated.
○・・・全く被膜が除去されない Δ・・・多少被膜が除去される 表 4○...The film is not removed at all. Δ... Some coating is removed Table 4
Claims (1)
5〜5g/lを含み且つpHが12以上であることを特
徴とするアルミニウム又はアルミニウム合金の黒色化処
理液。 2、前記水溶液中の亜鉛イオン/アンチモンイオン重量
比が1/2〜300/1の範囲にあることを特徴とする
特許請求の範囲第1項記載のアルミニウム又はアルミニ
ウム合金の黒色化処理液。[Claims] 1. Zinc ion 1 g/l or more and antimony ion 0.0
5 to 5 g/l and a pH of 12 or more. 2. The blackening treatment solution for aluminum or aluminum alloy according to claim 1, wherein the weight ratio of zinc ions/antimony ions in the aqueous solution is in the range of 1/2 to 300/1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20385886A JPS6360290A (en) | 1986-09-01 | 1986-09-01 | Blackening solution for aluminum or its alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20385886A JPS6360290A (en) | 1986-09-01 | 1986-09-01 | Blackening solution for aluminum or its alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6360290A true JPS6360290A (en) | 1988-03-16 |
JPH0527709B2 JPH0527709B2 (en) | 1993-04-22 |
Family
ID=16480859
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20385886A Granted JPS6360290A (en) | 1986-09-01 | 1986-09-01 | Blackening solution for aluminum or its alloy |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6360290A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6092495A (en) * | 1983-09-28 | 1985-05-24 | メタル ゲゼルシャフト アクチェン ゲゼルシャフト | Zinc electroplating of steel |
-
1986
- 1986-09-01 JP JP20385886A patent/JPS6360290A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6092495A (en) * | 1983-09-28 | 1985-05-24 | メタル ゲゼルシャフト アクチェン ゲゼルシャフト | Zinc electroplating of steel |
Also Published As
Publication number | Publication date |
---|---|
JPH0527709B2 (en) | 1993-04-22 |
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