JPH02270994A - Post-treatment of zinc or zinc alloy plated steel sheet with superior coatability, corrosion resistance and resistance to leaving of fingerprint - Google Patents
Post-treatment of zinc or zinc alloy plated steel sheet with superior coatability, corrosion resistance and resistance to leaving of fingerprintInfo
- Publication number
- JPH02270994A JPH02270994A JP9019389A JP9019389A JPH02270994A JP H02270994 A JPH02270994 A JP H02270994A JP 9019389 A JP9019389 A JP 9019389A JP 9019389 A JP9019389 A JP 9019389A JP H02270994 A JPH02270994 A JP H02270994A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- steel sheet
- treatment
- resistance
- corrosion resistance
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 43
- 239000010959 steel Substances 0.000 title claims abstract description 43
- 238000005260 corrosion Methods 0.000 title claims abstract description 33
- 230000007797 corrosion Effects 0.000 title claims abstract description 33
- 229910001297 Zn alloy Inorganic materials 0.000 title abstract description 22
- 229910052725 zinc Inorganic materials 0.000 title abstract description 20
- 239000011701 zinc Substances 0.000 title description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 27
- -1 4^2^- Chemical class 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 238000004532 chromating Methods 0.000 abstract 3
- 239000011651 chromium Substances 0.000 description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 229910052804 chromium Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 208000008454 Hyperhidrosis Diseases 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010064127 Solar lentigo Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
この発明は、耐食性、耐指紋性および塗装性に優れた亜
鉛または亜鉛合金めっき鋼板の後処理方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for post-treatment of zinc or zinc alloy coated steel sheets having excellent corrosion resistance, anti-fingerprint properties and paintability.
亜鉛または亜鉛合金めっき鋼板には、通常、耐食性や塗
装性の向上を目的としてクロメート処理が施される。ク
ロメート処理の方法としては、スプレーあるいは浸漬に
よってめっき表面と処理液とを反応させてクロメート皮
膜を形成させる反応型クロメート処理方法、処理液成分
の造膜作用によってクロメート皮膜を形成させる塗布型
クロメート処理方法、そして、電気化学的に皮膜を形成
させる電解クロメート処理方法が知られている。Zinc or zinc alloy coated steel sheets are usually subjected to chromate treatment for the purpose of improving corrosion resistance and paintability. Chromate treatment methods include a reactive chromate treatment method in which a chromate film is formed by reacting the plating surface with a treatment solution by spraying or dipping, and a coating-type chromate treatment method in which a chromate film is formed by the film-forming action of treatment solution components. , and an electrolytic chromate treatment method in which a film is formed electrochemically is known.
反応型クロメート処理および塗布型クロメート処理の何
れの方法も、ライン速度等のライン操業条件を変更する
と、クロメート皮膜量のコントロールが困難となり、し
かも、生成するクロメート皮膜の性能は、乾燥条件等に
よって刻−刻変化するために安定性に欠けるといった問
題を有していた。In both reactive chromate treatment and application-type chromate treatment, it is difficult to control the amount of chromate film when line operating conditions such as line speed are changed, and the performance of the chromate film formed is affected by drying conditions and other factors. - It had the problem of lack of stability because it changes from time to time.
電解クロメート処理方法は、主成分となるＣｒ”および
Ｓｏ、”、 Ｆ−等の陰イオンを添加したものからなる
水溶液中で、めっき鋼板を陰極として電解することによ
って、クロメート皮膜を形成させるもので、これを開示
した刊行物として、特公昭４７−４４４１７号、特公昭
４８−４３０１９号等の公報がある。これらの処理方法
は、めっき鋼板の種類によってクロム付着量が左右され
ず、電気量によってクロム付着量を容易に制御でき、且
つ、処理ムラが出にくい等の利点を有する。しかし、最
近、亜鉛または亜鉛合金めっき鋼板に要求される耐食性
の水準が以前に比べて大幅に高くなっているために、形
成されるクロメート皮膜の水準は今ひとつ不十分であっ
た。しかも、めっき表面を素手で扱うために指紋がめつ
き表面に付着しやすく、外観上好ましくなかった。The electrolytic chromate treatment method forms a chromate film by electrolyzing a plated steel sheet as a cathode in an aqueous solution containing Cr as the main component and anions such as So, F-, etc. , Publications disclosing this include Japanese Patent Publications No. 47-44417 and Japanese Patent Publication No. 43019-1974. These treatment methods have the advantage that the amount of chromium deposited is not affected by the type of plated steel sheet, the amount of chromium deposited can be easily controlled by the amount of electricity, and treatment unevenness is less likely to occur. However, recently, the level of corrosion resistance required for zinc or zinc alloy coated steel sheets has become much higher than before, so the level of the chromate film formed has been insufficient. Moreover, since the plated surface is handled with bare hands, fingerprints tend to adhere to the plated surface, which is unfavorable in terms of appearance.
また、Ｃｒ”を主成分とする処理液中に、シリカを添加
し電解クロメート処理する方法を開示した刊行物として
、特公昭６１−５．１８８０号、特開昭６２−１０７０
９６号、特開昭６２−２７８２９７号、特開昭６２−２
７８２９８号等の公報がある。特公昭６１−５４８８０
号公報には、シリカとしてカチオン型コロイダルシリカ
を含む溶液中で３０ク一ロン／ｄ１１！以上の電気量で
電解処理し、亜鉛系めっき表面にＣｒとＳｉとを含むク
ロメート皮膜を形成する方法が開示されている。特開昭
６２−１０７０９６号公報には、シリカの他にＮｏ、−
を添加し、さらにＣＳ”／Ｃｒ２＋の比を１７５０から
１７３の範囲内に維持した処理液で電解処理する方法が
開示されている。In addition, publications disclosing a method for electrolytic chromate treatment by adding silica to a treatment solution containing Cr as a main component include Japanese Patent Publication No. 5.1880/1980 and Japanese Patent Application Laid-open No. 1070/1983.
No. 96, JP-A-62-278297, JP-A-62-2
There are publications such as No. 78298. Special Public Service No. 61-54880
The publication describes that in a solution containing cationic colloidal silica as silica, 30 coulombs/d11! A method is disclosed in which a chromate film containing Cr and Si is formed on a zinc-based plating surface by electrolytic treatment using the above amount of electricity. JP-A-62-107096 discloses that in addition to silica, No.
A method is disclosed in which electrolytic treatment is carried out using a treatment solution in which the CS''/Cr2+ ratio is maintained within the range of 1750 to 173.
特開昭６２−２７８２９８号には、クロメート処理液中
にシリカの外にぶつ化物を添加し、電解処理する方法が
開示されている。JP-A No. 62-278298 discloses a method in which a fluoride is added in addition to silica to a chromate treatment solution and electrolytic treatment is carried out.
しかし、これらの方法によって生成されるシリカを含む
クロメート皮膜は、耐食性が優れる場合は塗装性が劣り
、塗装性が優れる場合は耐食性が劣る。However, when the chromate film containing silica produced by these methods has excellent corrosion resistance, it has poor paintability, and when it has excellent paintability, it has poor corrosion resistance.
さらに、特開昭６２−２７８２９７号には、Ｃｒ６°を
主成分とする処理液の中にシリカとケイ酸塩とを含をし
、さらに、Ｚ ｎ ＋ Ｎ ＋ ＋ Ｃｏ ｒ Ａｊ
＋ Ｍ ｇ ＋ Ｓ ｎ ＋ Ｐ ｂ ＋ Ｍ ｎイオ
ンの１種または２種以上を含有する組成からなるクロメ
ート浴で亜鉛または亜鉛合金めっき鋼板を陰極電解し、
クロメート皮膜を形成させた後、直ちに陽極電解処理す
る方法が開示されている。この電解処理方法によって生
成するクロメート皮膜は、陰極処理によってのみ生成す
るクロメート皮膜より皮膜量が著しく多く、塩水噴霧等
の耐食性に対して良好である。これは、陽極電解処理に
よって素地の亜鉛および亜鉛合金めっき皮膜が溶解し、
その部分に素地金属の酸化物を含んだ新しいクロメート
皮膜が析出し、シーリング作用をしているためと考えら
れる。しかしながら、塗装性は殆んど改善されなかった
。Furthermore, in JP-A No. 62-278297, silica and silicate are contained in a treatment liquid mainly composed of 6° Cr, and Z n + N + + Cor Aj
+ M g + S n + P b + M n A zinc or zinc alloy plated steel sheet is cathodically electrolyzed in a chromate bath having a composition containing one or more of the following ions,
A method is disclosed in which a chromate film is formed and then immediately subjected to anodic electrolysis treatment. The chromate film produced by this electrolytic treatment method has a significantly larger amount of film than the chromate film produced only by cathodic treatment, and has good corrosion resistance against salt spray and the like. This is because the zinc and zinc alloy plating film on the base material is dissolved by anodic electrolytic treatment.
It is thought that this is because a new chromate film containing oxide of the base metal is deposited in that area and has a sealing effect. However, the paintability was hardly improved.
このように、公知技術は、いずれも耐食性と塗装性とを
同時に満足させるものではなかった。As described above, none of the known techniques satisfies both corrosion resistance and paintability at the same time.
従って、この発明は、下記の問題点を解決することをそ
の目的とする。Therefore, an object of the present invention is to solve the following problems.
（１） クロメート処理皮膜を工業的に安定して亜鉛
または亜鉛めっき表面に形成させる。(1) Form a chromate-treated film industrially and stably on zinc or zinc-plated surfaces.
（２） 亜鉛または亜鉛合金めっき鋼板に要求される
耐食性を改善する。(2) Improve the corrosion resistance required for zinc or zinc alloy coated steel sheets.
（３） めっき表面に指紋が付着しないこと。(3) Fingerprints should not adhere to the plating surface.
（４） 亜鉛または亜鉛合金めっきｗ４板に要求され
る塗装性を改善すること。(4) To improve the paintability required for zinc or zinc alloy plated W4 sheets.
発明者らは、上述した問題点を解決するために、亜鉛ま
たは亜鉛合金めっき鋼板のクロメート皮膜とクロメート
処理方法を種々検討した６その結果、クロメート処理液
中に、Ｃｒ”、Ｃｒ” 、Ｚｎ” およびＮｉ２＋また
はＣｏ２＋の陽イオンと、ＳＯａ ’−、ＨＯｊ−、Ｃ
Ｉ−の陰イオンと、ＳｉＯ□とを含有した浴で、上記イ
オンの量をある範囲内に限定して後処理することにより
、耐食性、耐指紋性および塗装性に優れた亜鉛または亜
鉛合金めっきｔＩＡ仮を得られることを知見した。この
発明は上述の知見に基いてなされたものであり、Ｃｒ”
、 （：ｒ３’、 Ｚｎ”およびＮｉ２＋またはＣｏ２
＋の陽イオンと、ＳＯａ”−、Ｃ１−、ＨＯｊ−の１種
または２種以上の陰イオンと、シリカゾルとを主成分と
して含有し、全Ｃｒに対するＣＳ’の重量比が０．０５
〜０．２５の範囲内、Ｚｎ２＋の重量比がＯ０旧〜０．
５０の範囲内、Ｎｉ”°またはＧｏ２＋の重量比が０．
０５〜０．８０の範囲内であり、シリカの重量比が０．
３〜３゜０の範囲内であるクロメート処理液中にて、亜
鉛または亜鉛合金めっき鋼板を陰極電解処理することに
特徴を有するものである。このような処理を行なうこと
により、亜鉛または亜鉛合金めっき表面上に、金属と複
合酸化物からなるクロメート皮膜が形成される。このク
ロメート皮膜の金属層が、ＮｉまたはＣｏ、およびＣｒ
からなり、全金属量が５〜１０００■／ｎｆであり、さ
らに、その」二層には、Ｃｒ、 ＮｉまたはＣｏ、シリ
カ、およびＺｎからなる複合酸化物が形成しており、前
記複合酸化物は、クロム酸化物がクロム換算で５〜１０
０■／ボ、Ｓｉ酸化物が５ｉｔｆＡ算で５〜２００ｍｇ
／ｒｒｆ、Ｎ１またはＣｏ酸化物力＜ＮｉまたはＣｏ換
算で２〜５０Ｉ１ｇ／ｒＩ′ｆ、さらに、微量のＺｎを
含有することにより、耐食性、耐指紋性および塗装性に
優れた亜鉛または亜鉛合金めっき鋼板が捉供される。In order to solve the above-mentioned problems, the inventors investigated various chromate coatings and chromate treatment methods for zinc or zinc alloy coated steel sheets6. As a result, Cr'', Cr'', and Zn'' and Ni2+ or Co2+ cations, SOa'-, HOj-, C
Zinc or zinc alloy plating with excellent corrosion resistance, fingerprint resistance, and paintability is achieved by post-processing in a bath containing I- anions and SiO□, with the amount of the above ions limited within a certain range. It was found that tIA provisional can be obtained. This invention was made based on the above-mentioned knowledge, and Cr"
, (:r3', Zn'' and Ni2+ or Co2
Contains a + cation, one or more anions of SOa''-, C1-, HOj-, and silica sol as main components, and the weight ratio of CS' to total Cr is 0.05.
~0.25, the weight ratio of Zn2+ is O0 old ~0.25.
Within the range of 50, the weight ratio of Ni”° or Go2+ is 0.
0.05 to 0.80, and the weight ratio of silica is 0.05 to 0.80.
This method is characterized in that zinc or zinc alloy coated steel sheets are subjected to cathodic electrolytic treatment in a chromate treatment solution having a temperature within the range of 3 to 3 degrees. By performing such treatment, a chromate film made of metal and a composite oxide is formed on the zinc or zinc alloy plating surface. The metal layer of this chromate film is made of Ni or Co, and Cr.
The total metal content is 5 to 1000 μ/nf, and further, a composite oxide consisting of Cr, Ni or Co, silica, and Zn is formed in the two layers, and the composite oxide The chromium oxide is 5 to 10 in terms of chromium.
0 ■/bo, Si oxide is 5 to 200 mg calculated by 5 itfA
/rrf, N1 or Co oxide force < 2 to 50 I1g/rI'f in terms of Ni or Co, and zinc or zinc alloy coated steel sheet with excellent corrosion resistance, fingerprint resistance and paintability by containing a trace amount of Zn. is captured and provided.
本発明における亜鉛または亜鉛合金めっき鋼板とは、電
気亜鉛めっき鋼板、Ｚｎ−Ｆｅ、 Ｚｎ−Ｘｌその他の
電気亜鉛合金めっき鋼板、溶融亜鉛めっき鋼板および加
熱亜鉛合金めっき鋼板等を意味する（以下ｒＺｎめっき
鋼板Ｊという）。In the present invention, the term "zinc or zinc alloy coated steel sheet" refers to electrogalvanized steel sheet, Zn-Fe, Zn-Xl or other electrolytic zinc alloy coated steel sheet, hot-dip galvanized steel sheet, heated zinc alloy coated steel sheet, etc. (hereinafter referred to as rZn-plated steel sheet). (referred to as steel plate J).
クロメート皮膜の金属Ｎｉまたは金属Ｃｏ、および、金
属Ｃｒの全金属量が５ｍｇ／ｒｒ？未満では、耐食性が
不十分となって上記目的（２）を達成できない。一方、
前記全金属量が１０００■／ポを超えても性能の向上は
望めず、これ以上析出させても経済的に好ましくない。Is the total metal amount of metal Ni or metal Co and metal Cr in the chromate film 5 mg/rr? If it is less than that, the corrosion resistance will be insufficient and the above objective (2) cannot be achieved. on the other hand,
Even if the total amount of metal exceeds 1000 μ/Po, no improvement in performance can be expected, and further precipitation is not economically preferable.
従って、金属層を形成する金属Ｎｉまたは金属Ｃｏ、お
よび、金属Ｃｒの全付着量を、５〜１０００■／ｎ（の
範囲に限定した。Therefore, the total amount of deposited metal Ni or metal Co and metal Cr forming the metal layer was limited to a range of 5 to 1000 .mu./n.
クロメート皮膜の複合酸化物を形成するＣｒ酸化物とＳ
ｉ酸化物の量が各々５ＩＩ１ｇ／ｎ（未満では、耐食性
と塗装性が不十分で上記目的（２）、 （４）を達成で
きない、また、クロメート皮膜の複合酸化物中のＮｉま
たはＣｏ酸化物の量が２■／イ未満では、耐食性と耐指
紋性が不十分で上記目的（２）、 （３）を達成できな
い。一方、前記複合酸化物中のＣｒ酸化物の量が１００
ｍｇ／ｎｆを超えるか、または、ＮｉまたはＣｏ酸化物
の量が５０■／ポを超えると、塗装性が劣って上記目的
（４）を達成できない。また、前記複合酸化物中のＳｉ
酸化物の量が２００■／イを超えると、耐食性が不十分
となり上記目的（２）を達成できない。Cr oxide and S forming the composite oxide of chromate film
If the amount of each oxide is less than 5II1 g/n, the corrosion resistance and paintability will be insufficient and the above objectives (2) and (4) cannot be achieved. If the amount of Cr oxide is less than 2 / I, the corrosion resistance and fingerprint resistance will be insufficient and the above objectives (2) and (3) cannot be achieved. On the other hand, if the amount of Cr oxide in the composite oxide is 100
If it exceeds mg/nf, or if the amount of Ni or Co oxide exceeds 50 μg/nf, the paintability will be poor and the above objective (4) cannot be achieved. Moreover, Si in the composite oxide
If the amount of oxide exceeds 200 .mu./i, the corrosion resistance will be insufficient and the above objective (2) cannot be achieved.
以上説明したように、本発明の目的を達成するためには
、ＮｉまたはＣｏと、Ｃｒの金属層によって耐食性を向
上せしめ、そして、Ｃｒ、 Ｓｉ、 ＮｉまたはＣＯと
Ｚｎの複合酸化物組成の組み合わせによって、耐食性、
塗装性および耐指紋性を向上せしめている。As explained above, in order to achieve the object of the present invention, corrosion resistance is improved by a metal layer of Ni or Co and Cr, and a combination of a composite oxide composition of Cr, Si, Ni or CO and Zn is used. Corrosion resistance,
Improves paintability and fingerprint resistance.
従って、上記皮膜組成は必須である。Therefore, the above coating composition is essential.
次に、本発明の処理方法について述べる。Next, the processing method of the present invention will be described.
本発明におけるクロメート処理液中のＣｒ”としては、
無水クロム酸、重クロム酸アンモニウムおよび重クロム
酸のアルカリ金属塩類の１種または２種以上を任意に適
用できる。 Ｃｒ２＋の濃度は３〜１５ｇ／ｌが適当で
ある。 Ｃｒ２＋の濃度が３ ｇ／１未満では、皮膜を
長期間にわたって均一にすることが困難であり、上記目
的（１）を達成できない、また、Ｃｒ２＋の濃度が７５
ｇ／ｌを超えると、めっき表面の亜鉛が溶出し易（な
り、クロメート処理液中の濃度バランスが崩れ、上記目
的（２）、 （４）を安定して達成できない。Cr” in the chromate treatment solution in the present invention is as follows:
One or more of chromic anhydride, ammonium dichromate, and alkali metal salts of dichromate can be optionally applied. The appropriate concentration of Cr2+ is 3 to 15 g/l. If the concentration of Cr2+ is less than 3 g/1, it is difficult to make the film uniform over a long period of time, and the above objective (1) cannot be achieved.
If it exceeds g/l, zinc on the plating surface is likely to be eluted (the concentration balance in the chromate treatment solution will be disrupted, making it impossible to stably achieve the above objectives (2) and (4)).
さらに、全Ｃｒに対するＣｒ３’の重量比を、０．０５
〜０．２５の範囲内に限定した。その理由は、Ｃｒ３＋
の重量比が０．０５未満では、白錆発生防止効果は良好
であるが、塩水噴霧初期にめっき表面に微小の黒点が発
生する。一方、Ｃｒ２＋の重量比が０．２５を超えると
白錆が発生し易くなり、上記目的（２）を達成できない
、 Ｃｒ”は、硫酸塩、硝酸塩、フッ化物等によって添
加できるが、これらの塩に限定されるものでなく 、Ｃ
ｒ”をメタノール等で還元して使用してもよい。Furthermore, the weight ratio of Cr3' to total Cr was set to 0.05.
-0.25. The reason is Cr3+
When the weight ratio is less than 0.05, the white rust prevention effect is good, but minute black spots are generated on the plating surface at the initial stage of salt water spraying. On the other hand, if the weight ratio of Cr2+ exceeds 0.25, white rust is likely to occur and the above objective (2) cannot be achieved. Not limited to, C
r'' may be used after being reduced with methanol or the like.
本発明のＮｉ２＋またはＣｏ２＋においては、硫酸塩。In Ni2+ or Co2+ of the present invention, sulfate.
塩化物、炭酸塩、硝酸塩の１種または２種以上を任意に
適用できる。Ｎｉ！＋またはＣｏ”°の濃度は、全Ｃｒ
に対しての重量比で０．０５〜０．８０が適当である。One or more of chlorides, carbonates, and nitrates can be optionally applied. Ni! + or Co”° concentration is total Cr
A weight ratio of 0.05 to 0.80 is appropriate.
Ｎｉ２＋またはＣｏ２＋の濃度が重量比で０．０５未満
では、皮膜中に金属Ｎ！またはＣｏが析出せず、上記目
的（２）。If the concentration of Ni2+ or Co2+ is less than 0.05 in terms of weight ratio, metal N! will be present in the film. Or Co is not precipitated, and the above objective (2) is achieved.
（４）を達成できないと同時にクロメート皮膜中のＮｉ
またはＣｏ酸化物量が目標値に達せず、上記目的（２）
。(4) cannot be achieved and at the same time Ni in the chromate film
Or the amount of Co oxide does not reach the target value, and the above purpose (2)
.
（３）を達成できない、また、Ｎｉ２＋またはＣｏ２＋
″の濃度が重量比で０．８を超えると、クロメート皮膜
中のＮｉまたはＣｏ酸化物量が増大して、上記目的（４
）を達成できない。(3) cannot be achieved, or Ni2+ or Co2+
If the concentration of `` exceeds 0.8 in terms of weight ratio, the amount of Ni or Co oxide in the chromate film increases, and the above objective (4) is achieved.
) cannot be achieved.
クロメート処理液中のＺｎ”イオンを、全Ｃｒに対して
重量比で０．０１〜０．５０の範囲内に限定した。この
理由は不明であるが、Ｚｎ”イオンの重量比をこの範囲
に維持すると、複合酸化物中のＮｉまたはＣ。The weight ratio of Zn" ions in the chromate treatment solution was limited to a range of 0.01 to 0.50 relative to the total Cr. The reason for this is unknown, but the weight ratio of Zn" ions was limited to this range. If maintained, Ni or C in the composite oxide.
酸化物が少なくても、耐指紋性および耐食性が良好とな
り、塗装性を劣化させることがない。Even if the oxide content is small, fingerprint resistance and corrosion resistance will be good, and paintability will not deteriorate.
本発明のシリカとしては、無水ケイ酸を２０〜４０％含
有したコロイダルシリカを使用する。市販されているも
のとしては、例えば、日産化学工業■製のスノーテック
ス−０、あるいは、スノーテックス−ＯＬ等が該当する
。シリカの濃度は１０〜１５０ ｇ／ｌが適当である。As the silica of the present invention, colloidal silica containing 20 to 40% of silicic anhydride is used. Commercially available products include, for example, Snowtex-0 and Snowtex-OL manufactured by Nissan Chemical Industries, Ltd. A suitable concentration of silica is 10 to 150 g/l.
この濃度範囲を外れると、クロメート皮膜中のＳｔ量が
目標値を逸脱し、上記目的（２）、 （４）を達成でき
ない。If the concentration falls outside this range, the amount of St in the chromate film will deviate from the target value, making it impossible to achieve the above objectives (2) and (4).
その他の、処理液中の３０４”−、（Ｊ−、Ｎ（ｈ−の
陰イオンは、Ｃｒ ” ’ 、 ）ｉ ｉ １ ＊また
はＣｏ”、 Ｚｎ２＋の陽イオンを最初に添加する際に
同時に入るものであるが、クロメート皮膜の品質に影響
し、少なすぎても多すぎても、上記目的（１） 、、
（２） 、 （３） 、 （４）を達成できない。Other anions of 304"-, (J-, N(h-) in the treatment solution are added simultaneously when cations of Cr"', )i i 1 * or Co" and Zn2+ are added for the first time. However, if it is too little or too much, it will affect the quality of the chromate film, and the above purpose (1).
(2), (3), and (4) cannot be achieved.
好ましくは、全クロム量に対して、重量比で０．１〜２
．０の範囲である。Preferably, the weight ratio is 0.1 to 2 with respect to the total amount of chromium.
．． It is in the range of 0.
陰極電解処理の電流密度は、５〜４０Ａ／ｄｍ２＋の範
囲内が好ましい、電流密度が５＾／ｄ＊″未満では、金
属層が均一な皮膜として生成せず外観上好ましくない、
一方、４０Ａ／ｄａ” を超えると、複合酸化物中のＣ
ｒ、ＮｔまたはＣｏ量が少なすぎ、十分な耐食性が得ら
れない。The current density of the cathodic electrolytic treatment is preferably within the range of 5 to 40 A/dm2+. If the current density is less than 5^/d*'', the metal layer will not be formed as a uniform film, which is unfavorable in terms of appearance.
On the other hand, if it exceeds 40 A/da, C in the composite oxide
The amount of r, Nt or Co is too small and sufficient corrosion resistance cannot be obtained.
陰極電解処理の処理時間は、ＮｉまたはＣｏ、 Ｃｒ。The treatment time for cathodic electrolysis treatment is Ni, Co, or Cr.
Ｓｉの付着量を所望の範囲にするためにコントロールさ
れる０本発明においては、処理液の各成分の濃度および
電流密度を好ましい条件に固定しておき、処理時間を変
えることによって所望の付着量に制御する方法を採るこ
とも可能であり、または、処理時間を固定しておき、電
流密度を変えることによって付着量を制御することも可
能である。In the present invention, the concentration and current density of each component of the processing solution are fixed to preferred conditions, and the desired amount of Si adhesion is controlled by changing the treatment time. Alternatively, it is also possible to control the amount of adhesion by fixing the treatment time and changing the current density.
本発明により陰極電解処理されたＺｎめっき鋼板は、水
洗乾燥されたままの状態で、耐食性鋼板として使用され
る場合もあり、または、塗装下地用鋼板として使用され
る場合もある。さらに、本発明の方法により形成された
皮膜には、必要に応じて、さらに、−ｔａに行なわれて
いるクロメート水溶液または存機復合水溶液による後処
理の適用も可能である。The Zn-plated steel sheet subjected to the cathodic electrolytic treatment according to the present invention may be used as a corrosion-resistant steel sheet after washing and drying, or may be used as a steel sheet for painting base. Furthermore, the film formed by the method of the present invention can be further subjected to post-treatment with an aqueous chromate solution or an aqueous condensation solution, which is carried out in -ta, if necessary.
次に、この発明の実施例について説明する。 Next, embodiments of the invention will be described.
実施例１
公知の方法によってめっきした付着量２０ｇ／ｒｔ（の
電気亜鉛めっき鋼板に、以下の条件に従って陰極電解処
理を施し、次いで、水洗後乾燥させて、本発明鋼板１を
得た０本発明鋼板ＩのＮｉ＋Ｃｏ’＋Ｃｒ＋Ｓ＋の付着
量、耐食性、耐１旨紋性、塗装性を調べた結果を第１表
に示す。Example 1 An electrogalvanized steel sheet with a coating weight of 20 g/rt (plated by a known method) was subjected to cathodic electrolytic treatment according to the following conditions, and then washed with water and dried to obtain steel sheet 1 of the present invention. Table 1 shows the results of examining the adhesion amount of Ni+Co'+Cr+S+, corrosion resistance, scratch resistance, and paintability of steel plate I.
処理液組成
Ｃｒ” ： １０．５ ｇ ／ ｌ （ＮａｔＣｒＪ
、・２１１！Ｏを使用）Ｃｒ” ： ２．１ ｇ／
１（４０χＣｒｔ（ＳＯａ）ｓを使用）Ｚｎ”°：
１．１ ８ ／ Ｎ （ＺｎＳＯ４・７ＨｚＯを使用）
Ｎｉ” ： ３．４ ｇ ／ １２ （ＮｉＳＯｔ
・６］１□０を使用）Ｓ：Ｏｔ ： １０．Ｏｇ
／ ｌ （スノーテックス−〇 を使用 ）ＳＯ
ａ”−： １３．０ ｇ ／ １陰極電解条件
電流密度： ＩＯＡ／ｄａ！
処理時間： ０．９ｓｅｃ
実施例２
公知の方法によってめっきした付着量２０ ｇ ／ ｎ
ｌの電気亜鉛めっき鋼板に、以下の条件に従って陰極電
解処理を施し、次いで、水洗後乾燥させて、本発明鋼板
２を得た。本発明鋼板２のＮｉ、Ｃｏ、Ｃｒ’、Ｓｉの
付着量、耐食性、耐指紋性、塗装性を調べた結果を第１
表に示す。Treatment liquid composition Cr”: 10.5 g/l (NatCrJ
,・211! Cr”: 2.1 g/
1 (using 40χCrt(SOa)s) Zn”°:
1.1 8/N (using ZnSO4・7HzO)
Ni”: 3.4 g/12 (NiSOt
・6] Use 1□0) S:Ot: 10. Og
/ l (using Snowtex-〇) SO
a”-: 13.0 g/1 Cathodic electrolysis conditions Current density: IOA/da! Processing time: 0.9 sec Example 2 Coating amount 20 g/n plated by a known method
An electrogalvanized steel sheet of No. 1 was subjected to cathodic electrolysis treatment according to the following conditions, and then washed with water and dried to obtain steel sheet 2 of the present invention. The results of investigating the adhesion amount of Ni, Co, Cr', and Si, corrosion resistance, fingerprint resistance, and paintability of the steel plate 2 of the present invention are as follows.
Shown in the table.
処理液組成
Ｃｒ” ： １１．３ ｇ ／ ｐ、 ＜Ｎａｚｃｒ
ｔｏｑ ・ｕｔｏを使用）Ｃｒ’°： １．３ ｇ
／ Ｑ （４０ＸＣｒｔ（ＳＯａ）３を使用）Ｚｎ”
： ０．５ ｇ ／ ｌ−（５Ｚｎ０ ・２ＣＯｚ
ｌＨｚＯを使用）ｌｉｔ” ： ３．４ ｇ ／
ｌ （ＮｉＳＯａ・６Ｈ，Ｏを使用）ＳｉＯｇ ：
１．Ｏｇ ／ １． （スハテフクス−ＯＬ
を使用）ＳＯａ”−： ９．３ ｇ ／ １
陰極電解条件
電流密度： ２０Ａ／ｄｍ”
処理時間： ０．６ｓｅｃ
実施例３
公知の方法によってめっきした付着量２０ｇ／ｎｆの電
気亜鉛−ニッケル合金めっき鋼板に、以下の条件に従っ
て陰極電解処理を施し、次いで、水洗後乾燥させて、本
発明鋼板３を得た０本発明鋼板３のＮｉ、Ｃｏ＋Ｃｒ、
Ｓｔ の付着量、耐食性、耐指紋性。Treatment liquid composition Cr”: 11.3 g/p, <Nazcr
toq ・Uto) Cr'°: 1.3 g
/ Q (Using 40XCrt(SOa)3) Zn”
: 0.5 g/l-(5Zn0・2COz
1HzO) lit”: 3.4 g/
l (Using NiSOa・6H,O) SiOg:
1. Og / 1. (Suhatefukus-OL
SOa"-: 9.3 g/1 Cathode electrolysis conditions Current density: 20 A/dm" Processing time: 0.6 sec Example 3 Electrolytic zinc-nickel alloy plating with a coating weight of 20 g/nf plated by a known method The steel plate was subjected to cathodic electrolytic treatment according to the following conditions, and then washed with water and dried to obtain the steel plate 3 of the present invention.
Amount of St attached, corrosion resistance, fingerprint resistance.
塗装性を調べた結果を第１表に示す。Table 1 shows the results of examining the paintability.
処理液組成
Ｃｒ” ： ７．Ｏｇ ／ ｌ （ＮａｔＣｒｉｔ
・２ＨｔＯを使用）Ｃｒ” ： ０．９ ｇ／１ｃｒ
（Ｎ（ｈ）ｓ・９ＨｚＯを使用）Ｚｎ” ： ０．４
ｇ ／ ｌ （Ｚｎ（Ｎｏｗ）ｚ Ｈ６）１ｔＯを
使用）Ｃｏ” ： ３．Ｏｇ ／ ｌ （Ｃｏ（Ｎｏ
ｗ）ｚ ・６ＨｔＯを使用）Ｓｉｏｔ ： ４．
Ｏｇ ／ １ ＜、ｕ−ｔフクス ＯＬ を（
受用 ）ＮＯ，−： １０．２ ｇ ／ ｆｆｉ
陰極電解条件
電流密度： ＩＯＡ／ｄａ＋”
処理時間： ０．６ｓｅｃ
比較例１
公知の方法によってめっきした付着１１２０ｇ／ｒｒｌ
の電気亜鉛めっき鋼板に、以下の条件に従って陰極電解
処理を施し、次いで、乾燥させて、比較鋼板１を得た。Treatment liquid composition Cr”: 7.Og/l (NatCrit
・Using 2HtO) Cr”: 0.9 g/1cr
(Using N(h)s・9HzO) Zn”: 0.4
g/l (Using Zn(Now)z H6)1tO) Co”: 3.Og/l (Co(No
w) z ・Using 6HtO) Siot: 4.
Og / 1 <, ut Fuchs OL (
Acceptance) NO, -: 10.2 g/ffi
Cathodic electrolysis conditions Current density: IOA/da+" Processing time: 0.6 sec Comparative example 1 Deposition 1120 g/rrl plated by a known method
An electrogalvanized steel sheet was subjected to cathodic electrolytic treatment according to the following conditions, and then dried to obtain Comparative Steel Sheet 1.
比較鋼°板ＩのＮｉ、Ｇｏ、Ｃｒ、Ｓｉ の付着量。Amounts of Ni, Go, Cr, and Si deposited on comparative steel plate I.
耐食性２耐Ｉ旨紋性、塗装性を調べた結果を第１表に示
す。Corrosion Resistance 2 Resistance I The results of examining the marking properties and paintability are shown in Table 1.
処理液組成
Ｃｒ” ： ２３．４ ｇ ／ ｌ （Ｃｒｙ、を使
用）ＳＯａト： ０．２ｇ ／ ｌ （Ｎａｚｓｏａ
を使用）陰極電解条件
電流密度ｉ ２０Ａ／ｄｍ”
処理時間： １．２ｓｅｃ
比較例２
公知の方法によってめっきした付着１２０ｇ／ｎｆの電
気亜鉛めっき鋼板に、以下の条件に従って陰極電解処理
を施し、次いで、乾燥させて、比較鋼板２を得た。比較
鋼板２ （７）Ｎｉ、 Ｃｏ、 Ｃｒ、 Ｓｉの付着量
、耐食性、耐指紋性、塗装性を調べた結果を第１表に示
す。Processing liquid composition Cr": 23.4 g/l (using Cry) SOa: 0.2 g/l (Nazsoa)
(using) cathodic electrolytic conditions current density i 20 A/dm" treatment time: 1.2 sec Comparative Example 2 An electrolytic galvanized steel sheet with an adhesion of 120 g/nf plated by a known method was subjected to cathodic electrolytic treatment according to the following conditions, and then , and dried to obtain Comparative Steel Plate 2. Comparative Steel Plate 2 (7) Table 1 shows the results of examining the adhesion amount of Ni, Co, Cr, and Si, corrosion resistance, fingerprint resistance, and paintability.
処理液組成
Ｃｒ” ： ２３．４ ｇ ／ Ｉｌ （Ｃｒｙｓを使
用）Ｓ：Ｏｔ ： Ｉｏ、Ｏｇ ／ ｌ （
スノー？フクスＯをイ吏用 ）Ｆ −： １．５ ｇ
／ ｊ！ （ＮａｚＳｉＦａを使用）陰極電解条件
電流密度： ２０Ａ／ｄａ”
処理時間： ０．６ｓｅｃ
比較例３
公知の方法によってめっきした付着量２０ｇ／ｎｆの電
気亜鉛めっき鋼板に、以下の条件に従って陰極電解処理
を施し、次いで、水洗後乾燥させて、比較鋼板３を得た
。比較鋼板３のＮ ｒ ＋ Ｃｒ ＋ Ｓ ｔの付着量
、耐食性、耐指紋性、塗装性を調べた結果を第１表に示
す。Treatment liquid composition Cr”: 23.4 g/Il (using Crys) S:Ot: Io, Og/l (
snow? For Fukusu O) F-: 1.5 g
/ j! (Using NazSiFa) Cathodic electrolytic conditions Current density: 20 A/da'' Treatment time: 0.6 sec Comparative example 3 An electrolytic galvanized steel sheet with a coating weight of 20 g/nf plated by a known method was subjected to cathodic electrolytic treatment according to the following conditions. The coating was then washed with water and dried to obtain comparative steel plate 3. Table 1 shows the results of examining the amount of N r + Cr + S t adhesion, corrosion resistance, fingerprint resistance, and paintability of comparative steel plate 3. .
処理液組成
Ｃｒ” ： １０．５ ｇ ／ ｌ ＜ＮａｚＣｒｔＯ
６−２ＨｚＯを使用）Ｎｉ” ： ３．４ ｇ ／
１ （ＮｉＳＯｎ ・６ＨｉＯを使用）Ｓｉｎｇ ：
１０．０ ｇ ／ ｌ （Ｘ／−？フクス
Ｏをイ吏用 ）ＳＯａ！″： ５−５ ｇ ／ ｌ
（ＮｉＳＯｎ ・６８！Ｏを使用）陰極電解条件
電流密度： １５Ａ／ｄｍ”
処理時間： １．２ｓｅｃ
〔耐食性試験〕
耐食性試験は、以下の方法に従って行った。Treatment liquid composition Cr”: 10.5 g/l <NazCrtO
6-2HzO) Ni”: 3.4 g/
1 (Using NiSOn/6HiO) Sing:
10.0 g/l (X/-? Fuchs
O for official) SOa! ″: 5-5 g/l
(Using NiSOn 68!O) Cathode electrolysis conditions: Current density: 15 A/dm'' Treatment time: 1.2 sec [Corrosion resistance test] The corrosion resistance test was conducted according to the following method.
ＪＩＳ−Ｚ−２３７１に規定された、塩水噴霧試験を１
６８時間行い、白錆の発生面積を測定し、鋼板の全面積
に封子る白錆の発生面積をパーセントで示し、さらに、
黒点が発生するまでの時間を調査した。1 salt spray test specified in JIS-Z-2371
The test was carried out for 68 hours, the area of white rust generation was measured, and the area of white rust that was sealed over the entire area of the steel plate was expressed as a percentage.
The time taken for sunspots to appear was investigated.
クロメート処理した鋼板を汗の出た手で触り、指紋の付
着状態を観察し、その付着状態を肉眼で判定した。The chromate-treated steel plate was touched with sweaty hands, the state of fingerprint adhesion was observed, and the state of adhesion was determined with the naked eye.
〔塗装性］
塗装性は、市販のアルキルトメラミン系の白色塗料を約
３０−塗装し、塗膜にｌｓｍ間隔の基盤目を１．００個
入れ、この後、エリクセン試験機によって７−押し出し
、押し出し部をセロテープによって剥離し、塗膜の剥離
状態によって評価した。[Paintability] Paintability was determined by applying approximately 30cm of commercially available alkyl melamine-based white paint, placing 1.00 base holes with lsm spacing in the coating film, and then extruding 7cm using an Erichsen tester. The extruded portion was peeled off using cellophane tape, and the peeled state of the coating film was evaluated.
第１表から明らかなように、本発明鋼板は、比較鋼板と
異なり、耐食性、耐指紋性および塗装性に優れているこ
とがわかる。特に、本発明鋼板においては、塩水噴霧に
よって黒点の発生が認められず、従来にない良好な耐食
性が得られた。As is clear from Table 1, the steel sheets of the present invention are superior in corrosion resistance, fingerprint resistance, and paintability, unlike the comparative steel sheets. In particular, in the steel sheet of the present invention, no black spots were observed due to salt spray, and better corrosion resistance than ever before was obtained.
以上説明したように、この発明によれば、耐食性、耐指
紋性および塗装性に優れた亜鉛または亜鉛合金めっき鋼
板が得られるきわめて有用な効果がもたらされる。As explained above, the present invention brings about the extremely useful effect of providing a zinc or zinc alloy plated steel sheet with excellent corrosion resistance, anti-fingerprint properties, and paintability.
Claims (1)
Ｎｉ＾２＾＋またはＣｏ＾２＾＋の陽イオンと、ＳＯ＿
４＾２＾−、Ｃｌ＾−、ＮＯ＿３＾−の１種または２種
以上の陰イオンと、シリカゾルとを主成分として含有し
、全Ｃｒに対するＣｒ＾３＾＋の重量比が０．０５〜０
．２５の範囲内、Ｚｎ＾２＾＋の重量比が０．０１〜０
．５０の範囲内、Ｎｉ＾２＾＋またはＣｏ＾２＾＋の重
量比が０．０５〜０．８０の範囲内であり、シリカの重
量比が０．３〜３．０の範囲内であるクロメート処理液
中にて、亜鉛または亜鉛合金めっき鋼板を陰極電解処理
することを特徴とする、耐食性、耐指紋性および塗装性
に優れた亜鉛または亜鉛合金めっき鋼板の後処理方法。1 Cr^6^+, Cr^3^+, Zn^2^+ and Ni^2^+ or Co^2^+ cations and SO_
Contains one or more anions such as 4^2^-, Cl^-, and NO_3^- and silica sol as main components, and the weight ratio of Cr^3^+ to total Cr is 0.05~ 0
．． Within the range of 25, the weight ratio of Zn^2^+ is 0.01 to 0
．． 50, the weight ratio of Ni^2^+ or Co^2^+ is within the range of 0.05 to 0.80, and the weight ratio of silica is within the range of 0.3 to 3.0. A method for post-treatment of zinc- or zinc-alloy-plated steel sheets having excellent corrosion resistance, fingerprint resistance, and paintability, the method comprising cathodic electrolytically treating the zinc- or zinc-alloy-plated steel sheets in a chromate treatment solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1090193A JP2808649B2 (en) | 1989-04-10 | 1989-04-10 | Post-processing method of zinc or zinc alloy coated steel sheet with excellent corrosion resistance, fingerprint resistance and paintability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1090193A JP2808649B2 (en) | 1989-04-10 | 1989-04-10 | Post-processing method of zinc or zinc alloy coated steel sheet with excellent corrosion resistance, fingerprint resistance and paintability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02270994A true JPH02270994A (en) | 1990-11-06 |
| JP2808649B2 JP2808649B2 (en) | 1998-10-08 |
Family
ID=13991646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1090193A Expired - Fee Related JP2808649B2 (en) | 1989-04-10 | 1989-04-10 | Post-processing method of zinc or zinc alloy coated steel sheet with excellent corrosion resistance, fingerprint resistance and paintability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2808649B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04304397A (en) * | 1991-03-29 | 1992-10-27 | Nkk Corp | Chromate treated zinc plated steel sheet excellent in corrosion resistance, finger print resistance and production thereof |
-
1989
- 1989-04-10 JP JP1090193A patent/JP2808649B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04304397A (en) * | 1991-03-29 | 1992-10-27 | Nkk Corp | Chromate treated zinc plated steel sheet excellent in corrosion resistance, finger print resistance and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2808649B2 (en) | 1998-10-08 |
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