JPH0288799A - Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production - Google Patents
Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its productionInfo
- Publication number
- JPH0288799A JPH0288799A JP23830988A JP23830988A JPH0288799A JP H0288799 A JPH0288799 A JP H0288799A JP 23830988 A JP23830988 A JP 23830988A JP 23830988 A JP23830988 A JP 23830988A JP H0288799 A JPH0288799 A JP H0288799A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- steel sheet
- oxide
- corrosion resistance
- 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 38
- 239000010959 steel Substances 0.000 title claims abstract description 38
- 239000011701 zinc Substances 0.000 title claims abstract description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 230000007797 corrosion Effects 0.000 title claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011248 coating agent Substances 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 title abstract description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000007747 plating Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 25
- 229910052804 chromium Inorganic materials 0.000 abstract description 15
- 229910052759 nickel Inorganic materials 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 101100342332 Mus musculus Klf16 gene Proteins 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 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
- 241000080590 Niso Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 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
- 239000010953 base metal Substances 0.000 description 1
- 125000002091 cationic group Chemical group 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
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (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、塗装性および耐指紋性に優れた亜
鉛または亜鉛合金めっき鋼板およびその製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a zinc or zinc alloy coated steel sheet having excellent corrosion resistance, paintability and fingerprint resistance, and a method for manufacturing the same.
［従来の技術］
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−１〜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でている。[Prior Art] 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 in which a chromate film is formed by the film-forming action of the treatment solution components. A chromate treatment method and an electrolytic chromate treatment method in which a film is formed electrochemically are known.
［発明が解決しようとする課題］
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、刻−開度化す
るために安定性に欠けるといった問題を有していた。[Problems to be Solved by the Invention] In both the reactive chromate treatment and the coating-type chromate treatment, it is difficult to control the amount of chromate film when line operating conditions such as line speed are changed, and moreover, the amount of chromate film formed is The performance of this method had a problem of lack of stability due to the increase in the degree of carving.
電解クロメート処理方法は、主成分となるＣｒＧ＋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４７−４４４．１７号、特
公昭４８−４３０：１９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 CrG+ as the main component and anions such as So, "-, F-, etc. , Publications disclosing this include Japanese Patent Publication No. 47-444.17 and Japanese Patent Publication No. 430:19-1973.These treatment methods do not affect the amount of chromium deposited depending on the type of plated steel sheet. , the amount of chromium deposited can be easily controlled by the amount of electricity, and it has the advantage of being less likely to cause uneven treatment.However, recently, the level of corrosion resistance required for zinc or zinc alloy coated steel sheets has increased significantly compared to before. As a result, the level of the chromate film formed was insufficient.Furthermore, since the plated surface was handled with bare hands, fingerprints were likely to adhere to the plated surface, which was 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６１−５４−８８０号、特開昭６２−１０７
０９６号、特開昭６２−２７８２９７号、特開昭６２−
２７８２９８号等の公報がある。特公昭６１−５４８８
０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／ｄｒｒｒ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Ｎｏ３
−を添加し、さらにＣｒ３”／ Ｃｒ’＋の比を１７５
０から１／３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. 61-54-880 and Japanese Patent Application Laid-open No. 62-107.
No. 096, JP-A-62-278297, JP-A-62-
There are publications such as No. 278298. Tokuko Sho 61-5488
Publication No. 0 describes a method of forming a chromate film containing Cr and Si on a zinc-based plating surface by electrolytically treating the material in a solution containing cationic colloidal silica as silica with an amount of electricity of 30 corons/drrr or more. Disclosed. JP-A-62-107096 discloses that in addition to silica, No. 3
- was added, and the ratio of Cr3''/Cr'+ was further increased to 175.
A method of electrolytic treatment using a treatment solution maintained within the range of 0 to 1/3 is disclosed.
特開昭６２−２７８２９８号には、クロメート処理液中
にシリカの外にふっ化物を添加し、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 fluoride is added in addition to silica to a chromate treatment solution for electrolytic treatment.
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、Ｃｒ’＋を
主成分とする処理液の中にシリカとケイ酸塩とを含有し
、さらに、Ｚｎ、 Ｎｉ、 Ｇｏ、 Ａ Ｑ 。Furthermore, in JP-A No. 62-278297, a treatment solution containing Cr'+ as a main component contains silica and silicate, and further contains Zn, Ni, Go, and AQ.
Ｍｇ、Ｓｎ、Ｐｂ、Ｍｎ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。A method is to cathodically electrolyze a zinc or zinc alloy plated steel sheet in a chromate bath containing one or more of Mg, Sn, Pb, and Mn ions to form a chromate film, and then immediately perform anodic electrolysis treatment. Disclosed.
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。The chromate film produced by this electrolytic treatment method is
The amount of film is significantly larger than that of the chromate film produced only by cathodic treatment, and it has good corrosion resistance against salt spray and the like. This is thought to be because the zinc and zinc alloy plating film on the base material is dissolved by the anodic electrolytic treatment, and a new chromate film containing oxides of the base metal is deposited in that area, which 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、この発明の目的は、
（１）クロメート皮膜を工業的に安定して亜鉛または亜
鉛合金めっき表面に形成でき、
（２）亜鉛または亜鉛めっき鋼板に要求される耐食性を
有し、
（３）めっき表面に指紋が付着せず、そして、（４）亜
鉛または亜鉛合金めっき鋼板に要求される塗装性を有す
る、亜鉛または亜鉛合金めっき鋼板およびその製造方法
を提供することにある。Therefore, the objects of the present invention are as follows: (1) A chromate film can be industrially stably formed on a zinc or zinc alloy plated surface, (2) It has the corrosion resistance required for zinc or galvanized steel sheets, and (3) The object of the present invention is to provide a zinc- or zinc-alloy-plated steel sheet and a method for manufacturing the same, which prevents fingerprints from adhering to the plating surface and (4) has the paintability required of a zinc- or zinc-alloy-plated steel sheet.
［課題を解決するための手段］
この発明は、５から７５ ｇ／ｆｌのＣｒ”、Ｎｉ／Ｃ
ｒの重量比が０．０５から０．８になるＮｉ２＋および
１０から１５０ｇ／ｌ のシリカを含有し、さらに、Ｓ
Ｏ２”−、ＣＱ−、Ｎｏ、−、Ｆ−のうちの少なくとも
１種を０．０５から８０ ｇＩＱ含有するクロメート処
理液中で、亜鉛または亜鉛合金めっき鋼板を陰極電解処
理して、亜鉛または亜鉛合金めっき層上にクロメート皮
膜が形成され、前記クロメート皮膜は、前記めっき層上
に形成された金属層と、前記金属層上に形成された酸化
物層からなり、前記金属層は、５から１０００ｍｇ／ｍ
２の金属Ｎ］および３から１００■／♂の金属Ｃｒがら
なり、前記酸化物層は、主としてＣｒ換算で５から１０
０■／ｍのＣｒ酸化物、Ｎ」換算で３から５０ｍｇ／ｍ
２のＮｉ酸化物およびＳｉ換算で５から５００ｍｇ／ｍ
２のＳｉ酸化物からなる複合酸化物であり、且つ、前記
複合酸化物の一部が球状の突起をなしている、耐食性、
塗装性および耐指紋性に優れた亜鉛または亜鉛合金めっ
き鋼板を製造することに特徴を有するものである。[Means for Solving the Problems] This invention provides 5 to 75 g/fl of Cr, Ni/C.
containing Ni2+ and 10 to 150 g/l silica with a weight ratio of r from 0.05 to 0.8;
A zinc or zinc alloy plated steel sheet is cathodic electrolytically treated in a chromate treatment solution containing 0.05 to 80 gIQ of at least one of O2''-, CQ-, No, -, and F- to form zinc or zinc. A chromate film is formed on the alloy plating layer, the chromate film consists of a metal layer formed on the plating layer, and an oxide layer formed on the metal layer, and the metal layer has a weight of 5 to 1000 mg. /m
2 metal N] and 3 to 100 ■/♂ metal Cr, and the oxide layer mainly consists of 5 to 10
0■/m of Cr oxide, 3 to 50 mg/m in terms of N
2 Ni oxide and Si equivalent 5 to 500 mg/m
Corrosion resistance, which is a composite oxide consisting of Si oxide of No. 2, and a part of the composite oxide forms a spherical protrusion;
This method is characterized by producing a zinc or zinc alloy coated steel sheet with excellent paintability and fingerprint resistance.
次に、この発明を図面を参照しながら説明する。Next, the present invention will be explained with reference to the drawings.
この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−Ｎｉ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そ
の加熱亜鉛合金めっき鋼板等を意味する。The zinc or zinc alloy coated steel sheet in this invention is
It refers to electrogalvanized steel sheets, Zn-Fe, Zn-Ni and other electrozinc alloy-plated steel sheets, hot-dip galvanized steel sheets, hot zinc alloy-plated steel sheets, and the like.
第１図はこの発明のめっき鋼板の表面の１”ＥＭ写真、
第２図は断面を模式的に示す説明図である。Figure 1 is a 1" EM photograph of the surface of the plated steel sheet of this invention.
FIG. 2 is an explanatory diagram schematically showing a cross section.
第２図中の１は酸化物−層、２は金属層、３はＺｎめっ
き層である。In FIG. 2, 1 is an oxide layer, 2 is a metal layer, and 3 is a Zn plating layer.
第１図および第２図に示す球状の突起６が、クロメート
皮膜中のＣｒ、Ｓｉ、Ｎｉ、Ｚｎの複合酸化物の一部が
なす球状の突起である。The spherical protrusion 6 shown in FIGS. 1 and 2 is a spherical protrusion formed by a part of the composite oxide of Cr, Si, Ni, and Zn in the chromate film.
クロメート皮膜の金属層を形成する金属Ｎｉおよび金属
Ｃｒの付着量が各々５■／ｍ未満、３ｍｇ／ｍ２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、金属Ｎｉおよび金属Ｃｒの付着量が各々１
０００ ｍｇ／ｒｒ？、 １００ ｍｇ／ｎ？を超えて
も性能の向上は望めず、経済的にも好ましくない。従っ
て、金属層を形成する金属Ｎｉおよび金属Ｃｒの付着量
を、５から１０００ｍｇ／ｍ２および３から１００■／
ｒｒｉｌの範囲に限定した。If the deposited amounts of metallic Ni and metallic Cr forming the metal layer of the chromate film are less than 5 .mu./m and less than 3 mg/m.sup.2, respectively, the corrosion resistance will be insufficient and the above objective (2) cannot be achieved. On the other hand, the adhesion amount of metal Ni and metal Cr is 1
000 mg/rr? , 100 mg/n? Even if it exceeds 100%, no improvement in performance can be expected and it is not economically preferable. Therefore, the amount of deposited metal Ni and Cr forming the metal layer should be adjusted to 5 to 1000 mg/m2 and 3 to 100 mg/m2.
limited to the range of rril.
第２図に示すように、複合酸化物皮膜の一部がシリカ４
（ＳｉＯ２）の周囲５にＣｒイオン（Ｃｒ”Ｃｒ”）
、Ｎｉイオン（Ｎｉ２＋）、Ｚｎイオン（ｚｎ２＋）を
配位しながら球状になることによって析出応力を緩和し
、密着性の良い、厚いクロメート皮膜の形成が可能とな
った。一方、皮膜が球状の突起６をなしていることによ
って、塗料との密着性がアンカー効果によって良好とな
った。As shown in Figure 2, a part of the composite oxide film is made of silica 4
Cr ions (Cr"Cr") around (SiO2) 5
By coordinating , Ni ions (Ni2+), and Zn ions (zn2+) into a spherical shape, the precipitation stress is alleviated, making it possible to form a thick chromate film with good adhesion. On the other hand, since the film formed the spherical protrusions 6, the adhesion with the paint was improved due to the anchor effect.
上記クロメート皮膜の酸化物層中のＣｒ酸化物がＣｒ換
算で、および、Ｓｉ酸化物がＳｉ換算で、各々５■／ポ
未満では、耐食性および塗装性が不十分となって、上記
目的（２） 、 （４）が達成できない。If the Cr oxide and the Si oxide in the oxide layer of the chromate film are less than 5 cm/po in terms of Cr and Si in terms of Si, respectively, corrosion resistance and paintability will be insufficient, and the above objective (2) ), (4) cannot be achieved.
クロメート皮膜の酸化物層中のＮｉ酸化物がＮｉ換算で
３ｍｇ／ｍ２未満では、耐食性および耐指紋性が不十分
となって、上記目的（２）、（３）が達成できない。一
方、上記クロメ−Ｉ・皮膜の酸化物中のＣｒ酸化物がＣ
ｒ換算で、および、Ｎｉ酸化物がＮｉ換算で、各々１０
０ｍｇ／ｒｒＦ、 ５０ｍｇ／ｒｒｆを超えると、塗装
性が劣って、上記目的（４）が達成できない。If the Ni oxide in the oxide layer of the chromate film is less than 3 mg/m2 in terms of Ni, the corrosion resistance and fingerprint resistance will be insufficient, and the above objects (2) and (3) cannot be achieved. On the other hand, the Cr oxide in the oxide of the chrome-I film is
10 in terms of r and Ni oxide in terms of Ni.
If it exceeds 0 mg/rrF or 50 mg/rrf, the paintability will be poor and the above objective (4) cannot be achieved.
クロメート皮膜の酸化物層中のＳｉ酸化物がＳｉ換算で
５００ｍｇ／ｍ２を超えると、耐食性が不十分となって
、上記目的（２）が達成できない。従って、クロメート
皮膜の酸化物層中のＣｒ酸化物をＣｒ換算で５から１０
０■／ ｒｒＦ 、 Ｎ ｉ酸化物をＮｉ換算で３から
５０ｍｇ／ｍ２、そして、Ｓｉ酸化物をＳｉ換算で５か
ら５００■／ポの範囲に各々限定した。When the amount of Si oxide in the oxide layer of the chromate film exceeds 500 mg/m2 in terms of Si, corrosion resistance becomes insufficient and the above objective (2) cannot be achieved. Therefore, the Cr oxide in the oxide layer of the chromate film is 5 to 10% in terms of Cr.
The amount of Ni oxide was limited to 3 to 50 mg/m2 in terms of Ni, and the amount of Si oxide was limited to 5 to 500 mg/m2 in terms of Si.
以上説明したように、この発明の目的を達成するために
は、ＮｉおよびＣｒの金属層によって耐食性を向上せし
め、そして、Ｃｒ、Ｓｉ、およびＮｉの複合酸化物組成
の組み合わせと球状の突起によって、耐食性、塗装性お
よび耐指紋性を向上せしめている。なお、複合酸化物中
のＺｎは性能上殆んど影響しないが、少ない方が良い。As explained above, in order to achieve the object of the present invention, the corrosion resistance is improved by the metal layer of Ni and Cr, and the combination of the composite oxide composition of Cr, Si, and Ni and the spherical protrusions Improves corrosion resistance, paintability, and fingerprint resistance. Note that Zn in the composite oxide has almost no effect on performance, but the smaller the amount, the better.
次に、この発明の亜鉛または亜鉛合金めっき鋼板の製造
方法について説明する。Next, a method for producing a zinc or zinc alloy coated steel sheet according to the present invention will be explained.
この発明において使用するクロメート処理液は、５から
７５ ｇ／ｌのＣｒ６” 、 Ｎ ｉ／ Ｃｒの重量比
が０．０５から０．８になるＮｉ２＋および１０から１
５０ ｇＩＱ のシリカを含有し、さらに、ＳＯ４２
−、Ｃｌ−、Ｆ−のうちの少なくとも１種を０．０５か
ら８０ｇ／ｌ 含有する。The chromate treatment solution used in this invention contains 5 to 75 g/l of Cr6'', Ni2+ with a Ni/Cr weight ratio of 0.05 to 0.8, and 10 to 1
Contains 50 gIQ of silica and additionally contains SO42
-, Cl-, and F- at 0.05 to 80 g/l.
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少なくと
も１種を用いる。Ｃ＋・６＋の濃度が５ｇ／ｌ未満では
、クロメ−１へ皮膜を長期間に亘って均一に形成するこ
とができず、上記目的（１）を達成することができない
。一方、７５ ｇＩＱ を超えると、めっき表面の亜
鉛が溶出してクロメート処理液中のＣｒ” の濃度バラ
ンスが崩れて、上記目的（２） 、 （４）が達成でき
ない。従って、この発明においては、クロメート処理液
中のＣｒ’“の濃度を５から７５ｇ／ｌ の範囲に限定
した。As Cr''', at least one of chromic anhydride, ammonium dichromate, and alkali metal salts of dichromate is used.If the concentration of C+. It cannot be formed uniformly over the area, and the above objective (1) cannot be achieved. On the other hand, if it exceeds 75 gIQ, the zinc on the plating surface will dissolve and the concentration balance of Cr in the chromate treatment solution will become unbalanced. It collapses, and objectives (2) and (4) above cannot be achieved. Therefore, in this invention, the concentration of Cr' in the chromate treatment solution is limited to a range of 5 to 75 g/l.
Ｎｉ２＋として１よ、ＮｉＳ Ｏ４，ＮｉＣＯ２，Ｎｉ
ＣＯ３のうちの少なくとも１種を用いる。Ｎ１２”の濃
度は重量比で０．０５から０．８の範囲が適当である。1 as Ni2+, NiS O4, NiCO2, Ni
At least one type of CO3 is used. The concentration of N12'' is suitably in the range of 0.05 to 0.8 in terms of weight ratio.
Ｎｉ２＋の濃度が重量比で０．０５未満では、皮膜中に
金属Ｎ１が析出せず、上記目的（２）、（４）が達成で
きないと同時に、クロメート皮膜中のＮｉ酸化物量が目
標値に達せず、上記目的（２）、 （３）が達成できな
い。一方、０．８ を超えると、クロメート皮膜中のＮ
ｉ酸化物量が増大して、」二記目的（４）が達成できな
い。従って、Ｎ１２＋の濃度は重量比で０．０５から０
．８の範囲に限定した。If the concentration of Ni2+ is less than 0.05 by weight, metal N1 will not precipitate in the film, and the above objectives (2) and (4) cannot be achieved, and at the same time, the amount of Ni oxide in the chromate film will not reach the target value. Therefore, objectives (2) and (3) above cannot be achieved. On the other hand, if it exceeds 0.8, N in the chromate film
The amount of i oxide increases, and the second objective (4) cannot be achieved. Therefore, the concentration of N12+ is from 0.05 to 0 by weight.
．． It was limited to a range of 8.
シリカとしては、無水ケイ酸を２０から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、８産化学工業（株）製のスノーテックス−０，ス
ノーテックス−ＯＬ等がある。シリカの濃度が１０ ｇ
ＩＱ 未満では、クロメート皮膜中にシリカが十分に
析出しないので、」二記目的（２）、（３）が達成でき
ない。一方、１５０ｇ／ｌを超えると、クロメート皮膜
中のシリカの含有量が増加して、クロメート皮膜が粗雑
になって、上記目的（２）、（４）が達成できない。従
って、この発明においては、クロメート処理液中のシリ
カの濃度を１０から１５０ｇ／Ω の範囲に限定した。As the silica, colloidal silica containing 20 to 40% of silicic anhydride is used. Commercially available products include Snowtex-0 and Snowtex-OL manufactured by Yassan Kagaku Kogyo Co., Ltd. Concentration of silica is 10 g
If it is less than IQ, silica will not be sufficiently precipitated in the chromate film, and objectives (2) and (3) of "2" cannot be achieved. On the other hand, if it exceeds 150 g/l, the silica content in the chromate film will increase and the chromate film will become coarse, making it impossible to achieve the above objectives (2) and (4). Therefore, in this invention, the concentration of silica in the chromate treatment solution is limited to a range of 10 to 150 g/Ω.
ＳＯ２”−、ＣＱ−、Ｎｏ、−、Ｆ−の陰イオンは、ク
ロメート皮膜の均一性に影響を及ぼし、上記範囲に維持
することによって、上記目的（１）から（４）が達成さ
れる。従って、この発明においては、」二記陰イオンの
濃度を０．０５からＢｏｇ／ｌの範囲に限定した。The anions SO2''-, CQ-, No, -, and F- influence the uniformity of the chromate film, and by maintaining them within the above range, the above objectives (1) to (4) are achieved. Therefore, in this invention, the concentration of the anion is limited to a range of 0.05 to Bog/l.
陰極電解処理の電流密度は、５から４０Ａ／ｄｒＪの範
囲が良い。５Ａ／ｄｒｙｌ’未満では、金属層が均一に
形成されず、クロメート皮膜量が増大して外観上好まし
くなく、一方、４０Ａ／ｄｒｒｉを超えると、クロメー
ト皮膜中の複合酸化物中のＣｒ、Ｎｉ量が少なすぎて、
十分な耐食性が得られないからである。The current density for cathodic electrolytic treatment is preferably in the range of 5 to 40 A/drJ. If it is less than 5 A/dryl', the metal layer will not be formed uniformly and the amount of chromate film will increase, which is unfavorable in terms of appearance. On the other hand, if it exceeds 40 A/dryl', the amount of Cr and Ni in the composite oxide in the chromate film will There are too few
This is because sufficient corrosion resistance cannot be obtained.
陰極電解処理時間をコントロールすることによって、Ｎ
ｉ、Ｃｒ、Ｓｉの付着量を所望の値に維持することがで
きる。この発明においては、クロメート処理液の各成分
濃度および電流密度を好ましい条件に固定しておき、前
記処理時間をコントロールすることによって、前記付着
量を所望の値に維持することも可能であり、また、前記
処理時間を固定し、電流密度をコントロールすることに
よって、前記付着量を所望の値に維持することも可能で
ある。By controlling the cathodic electrolysis treatment time, N
The deposited amounts of i, Cr, and Si can be maintained at desired values. In the present invention, it is also possible to maintain the amount of adhesion at a desired value by fixing the concentration of each component and current density of the chromate treatment solution to preferable conditions and controlling the treatment time. It is also possible to maintain the deposition amount at a desired value by fixing the treatment time and controlling the current density.
この発明によって陰極電解処理された亜鉛または亜鉛合
金めっき鋼板は、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、塗装用下地鋼
板として使用される場合もある。さらに、この発明の方
法によって形成されたクロメート皮膜には、必要に応じ
てさらに一般に行われているクロメート水溶液または有
機複合水溶液による後処理の適用も可能である。A zinc or zinc alloy coated steel sheet that has been cathodically electrolytically treated according to the present invention may be used as a corrosion-resistant steel sheet after washing and drying, or may be used as a base steel sheet for painting. Furthermore, the chromate film formed by the method of the present invention can be subjected to a commonly used post-treatment with a chromate aqueous solution or an organic composite aqueous solution, if necessary.
［実施例コ 次に、この発明の実施例について説明する。[Example code] 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／ボの電気
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
。本発明鋼板１の、Ｎｉ、 Ｃｒ。Example 1 An electrogalvanized steel sheet with a coating weight of 20 g/bo was coated by a known method and 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. Ni and Cr of the steel plate 1 of the present invention.
Ｓｉの付着量、耐食性、耐指紋性、塗装性の結果を第１
表に示す。The results of Si adhesion amount, corrosion resistance, fingerprint resistance, and paintability were evaluated first.
Shown in the table.
処理液組成
Ｃｒ” ： １０．５ｇ／ｌ（Ｎａ２Ｃｒ２０７・２Ｈ
２０）、Ｎｉ” ： ３．４ ｇＩＱ（ＮｉＳＯ，・６
Ｈ２０）、ＳｘＯ，： １０．０ ｇ／ Ｑ （ス／
７ ツクＸ−０）、Ｓ０４” ：５−５ｇ／ｌＣＮ
ｘＳＯ１・６Ｈ２０）。Treatment liquid composition Cr”: 10.5g/l (Na2Cr207・2H
20), Ni”: 3.4 gIQ(NiSO,・6
H20), SxO,: 10.0 g/Q (S/
7 TsukuX-0), S04”: 5-5g/lCN
xSO1・6H20).
陰極電解条件 電流密度：１５Ａ／ｄｍ、 処理時間：１．２ｓｅｃ。Cathode electrolysis conditions Current density: 15A/dm, Processing time: 1.2 seconds.
実施例２
公知の方法によってめっきした付着量２０ｇ／Ｍの電気
亜鉛−鉄合金めっき鋼板に、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
２を得た。本発明鋼板２の、Ｎｉ、 Ｃｒ、 Ｓｊの付
着量、耐食性、耐指紋性、塗装性の結果を第１表に示す
。Example 2 An electrolytic zinc-iron alloy plated steel sheet with a coating weight of 20 g/M was plated by a known method and 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. Table 1 shows the results of the adhesion amounts of Ni, Cr, and Sj, corrosion resistance, fingerprint resistance, and paintability of the steel sheet 2 of the present invention.
処理液組成
Ｃｒ”’ ： ２１．Ｏｇ／ｌ（Ｎａ２Ｃｒ２０７・２
Ｈ２０）Ｎｉ” ： ３．７ ｇ／Ｄ （ＮｉＣ１１２
・６Ｈ２０）Ｓ ］、 ０２ ： １０ 、 Ｏｇ ／
Ｑ （入／−チックＸ−０Ｌ）Ｃｎ ： ４．５
ｇ／ｌＣＮｉｃｎｚ ・６Ｈ２０）。Treatment liquid composition Cr"': 21.Og/l (Na2Cr207.2
H20) Ni”: 3.7 g/D (NiC112
・6H20)S], 02: 10, Og/
Q (in/-tic X-0L) Cn: 4.5
g/lCNicnz 6H20).
陰極電解条件 電流密度：２０Ａ／ｄボ、 処理時間： １．８ ｓｅｃ。Cathode electrolysis conditions Current density: 20A/dbo, Processing time: 1.8 sec.
比較例１
公知の方法によってめっきした付着量２０ｇ／ポの電気
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。比較鋼
板１の、Ｃｒの付着量、耐食性、耐指紋性塗装性の結果
を第１表に合わせて示す。Comparative Example 1 An electrogalvanized steel sheet with a coating weight of 20 g/Po was coated by a known method and subjected to cathodic electrolytic treatment according to the following conditions, and then dried to obtain Comparative Steel Sheet 1. Table 1 shows the results of Cr adhesion, corrosion resistance, fingerprint resistance, and paintability of Comparative Steel Sheet 1.
処理液組成
ＣｒＧ＋： ２３．４ｇＩＱ （ＣｒＯ２）、ＳＯ２”
：０．２ ｇＩＱ （Ｎａ２Ｓｏ、、）。Treatment liquid composition CrG+: 23.4gIQ (CrO2), SO2"
:0.2 gIQ (Na2So, ).
陰極電解条件 電流密度：２０Ａ／ｄｒｒｆ、 処理時間： １．２ ｓｅｃ。Cathode electrolysis conditions Current density: 20A/drrf, Processing time: 1.2 sec.
比較例２
公知の方法によってめっきした付着量２０ｇ／イの電気
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の、Ｃｒ、 Ｓｊの付着量、耐食性、耐指紋性塗装
性の結果を第１表に合わせて示す。Comparative Example 2 An electrolytic galvanized steel sheet with a coating weight of 20 g/i plated by a known method was subjected to cathodic electrolysis treatment according to the following conditions, and then dried to obtain Comparative Steel Sheet 2. Table 1 shows the results of Cr and Sj adhesion, corrosion resistance, fingerprint resistance, and paintability of Comparative Steel Sheet 2.
処理液組成
Ｃｒ” ：２３．４ｇＩＱ（ＣｒＯ２）、５ｉｎ２：
ｌｏ、ｏｇ／ｌ（スノーテックス−Ｏ）、Ｆ ：１
．５ ｇＩＱ（Ｎａ２ＳｊＦ６）陰極電解条件
電流密度：２ＯＡ／ｄｒｒｆ、
処理時間： ０．６ ｓｅｃ口
＝１６
目を１００個入れ、この後、エリクセン試験機によって
７１１ＮＩ＋押し出し、押出し部をセロテープによって
剥離させ、塗膜の剥離状態によって評価した。Processing liquid composition Cr": 23.4gIQ (CrO2), 5in2:
lo, og/l (Snowtex-O), F:1
．． 5 gIQ (Na2SjF6) cathode electrolysis conditions Current density: 2OA/drrf, Processing time: 0.6 sec Port = 16 Insert 100 pieces, then extrude with 711NI+ using an Erichsen tester, peel off the extruded part with cellophane tape, and apply. Evaluation was made based on the peeling state of the film.
耐食性試験は、以下の方法に従って行った。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１６８時間行い、白錆の発生面積を測定し、鋼板の全
面積に対する白錆の発生面積をパーセントで示すことに
よって行った。A salt water spray test specified in JIS-Z-2371 was conducted for 168 hours, the area where white rust occurred was measured, and the area where white rust occurred was expressed as a percentage of the total area of the steel plate.
耐指紋性試験は、クロメート処理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
定することにより行った。The fingerprint resistance test was conducted by touching the chromate-treated steel plate with sweaty hands, observing the state of fingerprint adhesion, and judging the state of adhesion with the naked eye.
塗装性は、市販のアルキッドメラミン系の白色塗料を約
３０μｍ塗装し、塗膜に１ｍ間隔の基盤第１表から明ら
かなように、本発明ｆａ板は、比較鋼板と異なり、耐食
性、塗装性および耐指紋性共に優れていることがわかる
。特に本発明鋼板に指紋の付着は殆んどみられず、従来
にない耐指紋性を示した。Paintability was determined by applying approximately 30 μm of commercially available alkyd melamine-based white paint to the base plate at 1 m intervals. It can be seen that both fingerprint resistance is excellent. In particular, almost no fingerprints were observed on the steel sheet of the present invention, demonstrating unprecedented fingerprint resistance.
［発明の効果］
以上説明したように、この発明によれば、耐食性、塗装
性および耐指紋性に優れた亜鉛または亜鉛合金めっき鋼
板を製造することができるといったきわめて有用な効果
がもたらされる。[Effects of the Invention] As explained above, the present invention brings about extremely useful effects such as being able to produce a zinc or zinc alloy coated steel sheet with excellent corrosion resistance, paintability, and fingerprint resistance.
第１図はこの発明のめっき綱板の表面のＴＥＭ写真、第
２図は断面を模式的に示す説明図である。
図面において、
１・・・酸化物層、
２ 金属層、
３ ・Ｚｎめっき層、
４ ・シリカ、
５・・シリカの周囲、
６・・・球状の突起。FIG. 1 is a TEM photograph of the surface of the plated steel sheet of the present invention, and FIG. 2 is an explanatory diagram schematically showing a cross section. In the drawings, 1... Oxide layer, 2 Metal layer, 3 Zn plating layer, 4 Silica, 5 Surroundings of silica, 6 Spherical protrusion.
Claims (1)
形成され、前記クロメート皮膜は、前記めっき層上に形
成された金属層と、前記金属層上に形成された酸化物層
からなり、前記金属層は、５から１０００ｍｇ／ｍ＾２
の金属Ｎｉおよび３から１００ｍｇ／ｍ＾２の金属Ｃｒ
からなり、前記酸化物層は、主としてＣｒ換算で５から
１００ｍｇ／ｍ＾２のＣｒ酸化物、Ｎｉ換算で３から５
０ｍｇ／ｍ＾２のＮｉ酸化物およびＳｉ換算で５から５
００ｍｇ／ｍ＾２のＳｉ酸化物からなる複合酸化物であ
り、且つ、前記複合酸化物の一部が球状の突起をなして
いることを特徴とする、耐食性、塗装性および耐指紋性
に優れた亜鉛または亜鉛合金めっき鋼板。 ２ ５から７５ｇ／ｌのＣｒ＾６＾＋、Ｎｉ／Ｃｒの重
量比が０．０５から０．８になるＮｉ＾２＾＋および１
０から１５０ｇ／ｌのシリカを含有し、さらに、ＳＯ＿
４＾２＾−、Ｃｌ＾−、ＮＯ＿３＾−、Ｆ＾−のうちの
少なくとも１種を０．０５から８０ｇ／ｌ含有するクロ
メート処理液中で、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、塗装性およ
び耐指紋性に優れた亜鉛または亜鉛合金めっき鋼板の製
造方法。[Claims] 1. A chromate film is formed on a zinc or zinc alloy plating layer, and the chromate film is composed of a metal layer formed on the plating layer and an oxide layer formed on the metal layer. and the metal layer has a content of 5 to 1000 mg/m^2
of metallic Ni and 3 to 100 mg/m^2 of metallic Cr
The oxide layer mainly contains 5 to 100 mg/m^2 of Cr oxide in terms of Cr and 3 to 5 mg/m in terms of Ni.
0mg/m^2 of Ni oxide and 5 to 5 in terms of Si
00mg/m^2 of Si oxide, and a part of the composite oxide has spherical protrusions, and has excellent corrosion resistance, paintability, and fingerprint resistance. Zinc or zinc alloy coated steel sheet. 2 5 to 75 g/l of Cr^6^+, Ni^2^+ with a Ni/Cr weight ratio of 0.05 to 0.8 and 1
Contains 0 to 150 g/l silica and additionally SO_
A zinc or zinc alloy plated steel sheet is cathodic electrolytically treated in a chromate treatment solution containing 0.05 to 80 g/l of at least one of 4^2^-, Cl^-, NO_3^-, and F^-. A method for producing a zinc or zinc alloy coated steel sheet having excellent corrosion resistance, paintability and fingerprint resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23830988A JPH0288799A (en) | 1988-09-22 | 1988-09-22 | Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23830988A JPH0288799A (en) | 1988-09-22 | 1988-09-22 | Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0288799A true JPH0288799A (en) | 1990-03-28 |
| JPH0543799B2 JPH0543799B2 (en) | 1993-07-02 |
Family
ID=17028292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23830988A Granted JPH0288799A (en) | 1988-09-22 | 1988-09-22 | Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0288799A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04116193A (en) * | 1990-09-05 | 1992-04-16 | Nkk Corp | Multilayered electrolytic chromate treated steel plate having excellent corrosion resistance and weldability |
| 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 |
| JP2002322566A (en) * | 2001-04-23 | 2002-11-08 | Nippon Steel Corp | Grain oriented silicon steel sheet having excellent adhesion to tension impartable insulation film and production method therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59100291A (en) * | 1982-11-30 | 1984-06-09 | Nippon Kokan Kk <Nkk> | Production of electrolytically chromate treated steel sheet having excellent adhesion to secondary painting |
| JPS62278297A (en) * | 1986-05-24 | 1987-12-03 | Nippon Steel Corp | Method for chromating metal-surface-treated steel sheet |
| JPS62278298A (en) * | 1985-08-28 | 1987-12-03 | Kawasaki Steel Corp | Chromated zn or zn alloy plated steel sheet and its production |
| JPS6347400A (en) * | 1986-08-15 | 1988-02-29 | Nippon Steel Corp | Method for chromating metal |
-
1988
- 1988-09-22 JP JP23830988A patent/JPH0288799A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59100291A (en) * | 1982-11-30 | 1984-06-09 | Nippon Kokan Kk <Nkk> | Production of electrolytically chromate treated steel sheet having excellent adhesion to secondary painting |
| JPS62278298A (en) * | 1985-08-28 | 1987-12-03 | Kawasaki Steel Corp | Chromated zn or zn alloy plated steel sheet and its production |
| JPS62278297A (en) * | 1986-05-24 | 1987-12-03 | Nippon Steel Corp | Method for chromating metal-surface-treated steel sheet |
| JPS6347400A (en) * | 1986-08-15 | 1988-02-29 | Nippon Steel Corp | Method for chromating metal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04116193A (en) * | 1990-09-05 | 1992-04-16 | Nkk Corp | Multilayered electrolytic chromate treated steel plate having excellent corrosion resistance and weldability |
| 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 |
| JP2002322566A (en) * | 2001-04-23 | 2002-11-08 | Nippon Steel Corp | Grain oriented silicon steel sheet having excellent adhesion to tension impartable insulation film and production method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0543799B2 (en) | 1993-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6096140A (en) | Treating solution and treating method for forming protective coating films on metals | |
| US4407900A (en) | Electroplated corrosion resistant steels and method for manufacturing same | |
| JP3987633B2 (en) | Metal protective film forming treatment agent and forming method | |
| JP4845951B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin | |
| JP3078015B2 (en) | Method of treating metal surface of article and treatment solution used in this method | |
| JPH0288799A (en) | Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production | |
| JPS5928638B2 (en) | Method of forming a colored protective film on the surface of magnesium material | |
| JPS6210292A (en) | Manufacture of colored galvanized steel sheet | |
| JP4179527B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin | |
| JP2808649B2 (en) | Post-processing method of zinc or zinc alloy coated steel sheet with excellent corrosion resistance, fingerprint resistance and paintability | |
| JPS6213590A (en) | Surface-treated steel sheet having excellent coating property, adhesion after coating and corrosion resistance and its production | |
| JPH0456798A (en) | Production of chromated galvanized steel sheet excellent in resistance to corrosion and fingerprinting, coating suitability and surface color tone | |
| JP2712924B2 (en) | Zinc-nickel-chromium alloy electroplated steel sheet with excellent corrosion resistance, plating adhesion, chemical conversion treatment and coating film adhesion | |
| JPH04246193A (en) | Galvanized metal material excellent in resistance to heat and corrosion | |
| JPH01255690A (en) | Zinc or zinc alloy plated steel sheet having superior corrosion resistance, coatability and resistance to leaving of fingerprint and production thereof | |
| JPH01290797A (en) | Composite electroplated steel sheet having superior corrosion resistance | |
| JP2569993B2 (en) | Method for producing chromate-treated galvanized steel sheet with excellent corrosion resistance, fingerprint resistance and paintability | |
| JP2636589B2 (en) | Zinc-nickel-chromium alloy electroplated steel sheet with excellent corrosion resistance, plating adhesion and chemical conversion treatment | |
| JPS58210193A (en) | Iron-zinc alloy electroplated steel plate having excellent phosphatability | |
| JPH03202497A (en) | Production of steel sheet galvanized or plated with zinc alloy which is excellent in corrosion resistance, fingerprint resistance, coating property and surface color tone | |
| JP3241170B2 (en) | Pretreatment method for cationic electrodeposition coating of aluminum-based metal materials | |
| JPH02104695A (en) | Black surface-treated steel material and production thereof | |
| JPS6075584A (en) | Method for modifying surface of zinc alloy plated steel sheet | |
| JPH0472077A (en) | Improvement of low-temperature chipping resistance of plated steel sheet | |
| JPS58224194A (en) | Surface treated steel sheet having excellent secondary adhesion of painted film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080702 Year of fee payment: 15 |
|
| LAPS | Cancellation because of no payment of annual fees |