JPS62278297A - Method for chromating metal-surface-treated steel sheet - Google Patents
Method for chromating metal-surface-treated steel sheetInfo
- Publication number
- JPS62278297A JPS62278297A JP11839386A JP11839386A JPS62278297A JP S62278297 A JPS62278297 A JP S62278297A JP 11839386 A JP11839386 A JP 11839386A JP 11839386 A JP11839386 A JP 11839386A JP S62278297 A JPS62278297 A JP S62278297A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- chromate
- treatment
- plated steel
- film
- 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 54
- 239000010959 steel Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 25
- 238000004532 chromating Methods 0.000 title 1
- 150000002500 ions Chemical class 0.000 claims abstract description 81
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 16
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims description 65
- 239000011701 zinc Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims 3
- 238000002407 reforming Methods 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 4
- 229910052745 lead Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 48
- 239000011248 coating agent Substances 0.000 description 43
- 230000007797 corrosion Effects 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 26
- 230000000694 effects Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 239000011651 chromium Substances 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- -1 Cr6+ ion Chemical class 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（産業上の利用分野）
本発明は、亜鉛及び亜鉛合金メッキ鋼板、アルミ及びア
ルミ合金メッキ鋼板、鉛及び鉛合金メッキ鋼板の表面に
、耐食性、塗装性能、特にカチオン電着塗装に対する塗
装適合性にすぐれた、陰極電解被膜及び陽極電解被膜か
らなる、複合クロメート被膜を形成させる、表面処理鋼
板のクロメート処理法に関するものである。[Detailed Description of the Invention] 3. Detailed Description of the Invention (Field of Industrial Application) The present invention provides corrosion resistance on the surface of zinc and zinc alloy plated steel sheets, aluminum and aluminum alloy plated steel sheets, lead and lead alloy plated steel sheets. This invention relates to a method for chromate treatment of a surface-treated steel sheet, which forms a composite chromate coating consisting of a cathodic electrolytic coating and an anodic electrolytic coating, which has excellent coating performance, particularly compatibility with cationic electrodeposition coating.
（従来の技術）
亜鉛メッキ鋼板の電解クロメート処理技術としては、特
公昭４７−４４４１７ （Ｃｒ０３−Ｈ２ＳＯ４処理液
で陰極電解処理する方法）、特開昭６０−Ｌ Ｌ Ｏ８
９６（ＣｒＯ３−８ｉＯ２処理液で陰極電解処理する方
法）で開示されているが、これらは総て、陰極電解処理
により、亜鉛メッキ鋼板の表面にクロメート皮膜を形成
させる方法である。一般に、これら陰極電解皮膜は、塗
装性能は良好であるが。(Prior art) Techniques for electrolytic chromate treatment of galvanized steel sheets include Japanese Patent Publication No. 47-44417 (method of cathodic electrolytic treatment using Cr03-H2SO4 treatment solution) and Japanese Patent Publication No. 60-1989-L L O8.
No. 96 (method of cathodic electrolytic treatment using CrO3-8iO2 treatment solution), all of which are methods for forming a chromate film on the surface of a galvanized steel sheet by cathodic electrolytic treatment. Generally, these cathode electrolytic coatings have good coating performance.
耐食性が不十分であるといわれている。It is said that corrosion resistance is insufficient.
（発明の解決しようとする問題点）
従って、これらの陰極電解皮膜は、皮膜形成量（主にク
ロム付着量）を多くすることにより耐食性を補っている
。しかし、クロメート皮膜は皮膜形成量が多くなると着
色し、被処理材の外観を損なわれ、又、更に塗装性能が
低下するという欠点があるだめ、外観、＃Ｆ食性、塗装
性能共に優れた皮膜の形成が困難であった。又、これら
陰極電解法では、亜鉛メッキ鋼板等を連続して処理する
と、Ｚｎ イオンが処理液中に蓄積し、耐食性が著
しく低下する等の問題を有していた。(Problems to be Solved by the Invention) Therefore, these cathode electrolytic coatings compensate for corrosion resistance by increasing the amount of film formed (mainly the amount of chromium deposited). However, chromate coatings have the drawback of becoming colored when the amount of coating increases, impairing the appearance of the treated material, and further reducing coating performance. It was difficult to form. In addition, these cathodic electrolytic methods have had the problem that when galvanized steel sheets and the like are continuously treated, Zn ions accumulate in the treatment solution, resulting in a significant decrease in corrosion resistance.
次に、陽極電解処理であるが、亜鉛メッキ鋼板を陽極電
解処理しても、クロメート皮膜の形成は可能であるが、
得られる皮膜は耐食性、塗装性能に乏しく、又、陽極電
解処理では、ファラデーの法則に従い被処理材の亜鉛等
のメッキ金属が溶解し、その含有量がばらつく等、処理
液が不安定となり、工業的に安定な処理が困難である。Next, regarding anodic electrolytic treatment, it is possible to form a chromate film even if galvanized steel sheets are subjected to anodic electrolytic treatment.
The resulting film has poor corrosion resistance and coating performance, and in anodic electrolytic treatment, zinc and other plated metals of the treated material dissolve according to Faraday's law, making the treatment solution unstable due to variations in its content, etc. It is difficult to perform stable treatment.
また、クロメート浴にＣｏ金属等のカチオンを添加して
、塗布又は浸漬処理する方法等が提案されているが、ク
ロメート被膜中に安定して金属イオンを含有せしめ、ク
ロメート被膜の電気的特性を向上せしめる方法等は開発
されていない。In addition, a method has been proposed in which cations such as Co metal are added to a chromate bath and applied or dipped, but this method stably contains metal ions in the chromate film and improves the electrical properties of the chromate film. No method has been developed to prevent this.
本発明は、従来のクロメート被膜、特に陰極電解クロメ
ート処理技術の欠点を改善して、クロメート被膜の均一
性、耐食性、カチオン電着塗装に対する塗装適合性等を
中心とした塗装性能にすぐれたクロメート被膜を、工業
的に安定して、亜鉛及び亜鉛合金メッキ、アルミ及びア
ルミ合金メッキ、鉛及び鉛合金メッキ表面に工業的に安
定して形成させる事を目的とする。The present invention improves the shortcomings of conventional chromate coatings, especially cathodic electrolytic chromate treatment technology, and provides a chromate coating with excellent coating performance, including uniformity, corrosion resistance, and suitability for cationic electrodeposition coating. The purpose is to form this on the surface of zinc and zinc alloy plating, aluminum and aluminum alloy plating, lead and lead alloy plating in an industrially stable manner.
（問題点の解決手段）
亜鉛及び亜鉛合金メッキなどの表面処理方法について、
種々検討を行なった結果、下記の如きカチオンを含有す
るクロメート浴を用いて、陰極電解処理後、直ちに陽極
電解処理する複合電解処理により、これら表面処理メッ
キ鋼板をクロメート処理する方法、即ち、
（１） Ｃｒ６＋イオンにＰＯ４”−イオンと弗素化
合物の１棟または２種これにＺｎイオン、Ｎｉイオン、
ｃ。(Means for solving problems) Regarding surface treatment methods such as zinc and zinc alloy plating,
As a result of various studies, we have found a method of chromate treatment of these surface-treated plated steel sheets by a composite electrolytic treatment in which cathodic electrolytic treatment is immediately followed by anodic electrolytic treatment using a chromate bath containing the following cations, namely (1) ) One or two types of Cr6+ ion, PO4''- ion and fluorine compound, and Zn ion, Ni ion,
c.
イオン、Ａｌイオン、ｒＡｇイオン、Ｓｎイオン、Ａｌ
ｎイオン、ｐｂイオンの１棟又は２種以上を含有する組
成からなるクロメート浴中で、亜鉛及び亜鉛合金メッキ
鋼板、アルミ及びアルミ合金メッキ鋼板、鉛及び鉛合金
メッキ鋼板を陰極電解処理し、クロメート被膜を形成さ
せた後直ちに陽極電解処理して陽極電解改質被膜を設け
る表面処理鋼板のクロメート処理法、
（２） Ｃｒ’＋ イオンに７リカとケイ酸塩の１種
または２種これにＺｎイオン、Ｎｉイオン、Ｃｏイオン
、成イオン、Ａｌフイオン、Ｓｎイオン、Ａｌｎイオン
、ｐｂイオン、０１種又は２種以上を含有する組成から
なるクロメート浴中で、亜鉛及び亜鉛合金メッキ鋼板、
アルミ及びアルミ合金メッキ鋼板、鉛及び鉛合金メッキ
鋼板を陰極電解処理し、クロメート被膜を形成させだ後
直ちに陽極電解処理して陽極電解改質被膜を設ける表面
処理鋼板のクロメート処理法
（３） Ｃｒ’＋イオンにＰＯ４３−イオンと弗素化
合物の１十重まだは２千重、シリカとケイ酸塩の１種ま
たは２種これに、Ｚｎイオン、Ｎｉイオン、Ｃｏイオン
、Ａ２イオン、Ａｌ？イオン、Ｓｎイオン、Ａｌｎイオ
ン、ｐｂイオンの１種又は２種以上を含有するクロメー
ト浴中で、亜鉛及び亜鉛合金メッキ鋼板、アルミ及びア
ルミ合金メッキ鋼板、鉛及び鉛合金メッキ鋼板を陰極電
解処理し、クロメート被膜を形成させた後直ちに陽極電
解処理して陽極改質被膜を設ける表面処理鋼板のクロメ
ート処理法
を見出した。ion, Al ion, rAg ion, Sn ion, Al
Zinc and zinc alloy plated steel sheets, aluminum and aluminum alloy plated steel sheets, lead and lead alloy plated steel sheets are cathodic electrolytically treated in a chromate bath containing one or more of n ions and pb ions to remove chromate. Chromate treatment method for surface-treated steel sheets in which anodic electrolytic treatment is performed immediately after coating is formed to form an anodic electrolytic modified coating, (2) Cr'+ ion, 7 Lika and one or two types of silicate, and Zn. ion, Ni ion, Co ion, formation ion, Al ion, Sn ion, Aln ion, PB ion, zinc and zinc alloy plated steel sheet in a chromate bath having a composition containing 01 type or two or more types.
Chromate treatment method for surface-treated steel sheets in which aluminum and aluminum alloy plated steel sheets, lead and lead alloy plated steel sheets are cathodic electrolytically treated to form a chromate film, and then immediately anodic electrolytically treated to form an anodic electrolytically modified film (3) Cr '+ ions, PO43- ions, 10 to 2,000 fluorine compounds, one or two types of silica and silicate, Zn ions, Ni ions, Co ions, A2 ions, Al? Zinc and zinc alloy plated steel sheets, aluminum and aluminum alloy plated steel sheets, lead and lead alloy plated steel sheets are cathodic electrolytically treated in a chromate bath containing one or more of ion, Sn ion, Aln ion, and PB ion. discovered a method for chromate treatment of surface-treated steel sheets in which a chromate film is formed and then immediately subjected to an anodic electrolytic treatment to form an anodic modification film.
すなわち、本発明の処理方法の適用により、陰極電解処
理により金属イオンを含有するクロメート被膜を形成さ
せた後、直ちに陽極電解処理によって、クロメート被膜
が改質され難溶性の被膜が形成されるとともに、内部に
金属カチオンが含有されるクロメート被膜が形成される
。That is, by applying the treatment method of the present invention, after forming a chromate film containing metal ions by cathodic electrolysis treatment, the chromate film is immediately modified by anodic electrolysis treatment to form a poorly soluble film, and A chromate film containing metal cations is formed.
その結果として、耐食性、塗装性能、特にクロメート被
膜中に含有される金属の効果によって、カチオン電着塗
装においてクロメート被膜が、従来のクロメート被膜に
比して、陽極としての作用効果を有するため、その塗装
適合性が極めて向上する効果が得られる。As a result, due to corrosion resistance, coating performance, and especially the effects of the metals contained in the chromate coating, the chromate coating has a greater effect as an anode than conventional chromate coatings in cationic electrodeposition coating. The effect of greatly improving coating compatibility can be obtained.
（作用） 以下、本発明について詳細に説明する。(effect) The present invention will be explained in detail below.
本発明におけるクロメート浴には。In the chromate bath in the present invention.
■ Ｃｒ イオン、Ｐｏ４３−イオン及び／又は弗素
化合物、及びこれにＺｎイオン、Ｎｉイオン、Ｃ○イオ
ン、Ａｌイオン、Ａｌｐイオン、Ｓｎイオン、Ａｌｎイ
オン、Ｐｂイオンの１種又は２種以上を含むクロメート
浴。■ Cr ions, Po43- ions and/or fluorine compounds, and chromates containing one or more of Zn ions, Ni ions, C○ ions, Al ions, Alp ions, Sn ions, Aln ions, and Pb ions. bath.
■ Ｃｒ’＋イオン、シリカ及び／ケイ酸塩、及びこれ
にＺｎイオン、Ｎｉイオン、ＣＯイオン、成イオン、Ａ
ｌ？イオン、Ｓｎイオン、Ａｌｎイオン、ｐｂイオンの
１種又は２種以上を含むクロメート浴。■ Cr'+ ion, silica and/or silicate, and Zn ion, Ni ion, CO ion, formation ion, A
l? A chromate bath containing one or more of Sn ions, Aln ions, and PB ions.
■ Ｃｒ’＋イオン、ＰＯ４３−イオン及び／又は弗素
化合物、シリカ及び／又はケイ酸塩及びこれにＺｎイオ
ン、Ｎｉイオン、ＣＯイオン、Ａｌイオン、Ａｌｆイオ
ン、Ｓｎイオン、Ａｌｎイオン、ｐｂイオンの１種又は
２種以上を含むクロメート浴を使用する。■ Cr'+ ion, PO43- ion and/or fluorine compound, silica and/or silicate, and one of Zn ion, Ni ion, CO ion, Al ion, Alf ion, Sn ion, Aln ion, pb ion A chromate bath containing one or more species is used.
これらの浴は、同一浴で陰極電解、及び陽極電解を行な
うことができ、又それぞれ異なる組成の処理浴で陰極電
解および陽極電解処理することも。With these baths, cathodic electrolysis and anodic electrolysis can be performed in the same bath, or cathodic electrolysis and anodic electrolysis can be performed in treatment baths with different compositions.
できる。can.
クロメート浴中のＣｒ’＋イオンは、クロム酸、重クロ
ム酸及びこれらのアルカリ金属塩類、アンモニウム塩類
の１種又は２種以上の混合物が任意に適用でき、その濃
度がＣｒ’＋とじて５〜７０ ｆ／Ｌ、（好ましくは７
．５〜５０ ｆ、’ｚ ）の範囲がよい。For the Cr'+ ions in the chromate bath, one or a mixture of two or more of chromic acid, dichromic acid, their alkali metal salts, and ammonium salts can be applied as desired, and the concentration thereof is 5 to 5% as Cr'+. 70 f/L, (preferably 7
．． A range of 5 to 50 f,'z) is preferable.
この場合５ ？／を未満の濃度では、本発明の処理を施
しても、耐食性能の向上効果が小さく、また７ ０ ｙ
／ｌをこえる濃度では効果が飽和するとともに、処理時
のクロメート浴持出し量が多くなりすぎ、またフユーム
、ミスト等による作業環境の問題等好ましくない。5 in this case? If the concentration is less than /, even if the treatment of the present invention is applied, the effect of improving corrosion resistance is small;
If the concentration exceeds /l, the effect will be saturated, the amount of chromate bath taken out during treatment will be too large, and fumes, mist, etc. will cause problems in the working environment, which is not preferable.
ＰＯ４３−イオンとしては、リン酸、リン酸のアルカリ
金属塩類、及びリン酸アンモニウム等、又、弗素化合物
としては、弗化水素酸、ケイ弗化水素酸、ホウ弗化水素
酸、チタン弗化水素酸ジルコン弗化水素酸、又はこれら
の塩類１等の、１種又は２種以上の混合物が任意に適用
でき、その濃度を、ＰＯ４３−イオンと弗素化合物の合
計としてｌ〜ｘｏｏｒ／ｚ の範囲にすることにより、
一層好ましい結果が得られる。Examples of PO43- ions include phosphoric acid, alkali metal salts of phosphoric acid, ammonium phosphate, etc., and examples of fluorine compounds include hydrofluoric acid, hydrofluorosilicic acid, hydrofluoroboric acid, and titanium hydrogen fluoride. One type or a mixture of two or more types of acid zirconate hydrofluoric acid or salts 1 thereof can be optionally applied, and the concentration thereof is in the range of 1 to xoor/z as the sum of PO43- ions and fluorine compounds. By doing so,
More favorable results are obtained.
これらの濃度が、１２／を未満では、クロメート浴の電
導塵或いは金属イオンの処理浴への溶解度が小さくなり
すぎ、本発明の目的とするクロメート被膜の性能向上効
果が得られない場合がある。If these concentrations are less than 12/1, the solubility of the conductive dust or metal ions in the chromate bath becomes too low, and the performance improvement effect of the chromate film, which is the objective of the present invention, may not be achieved.
また、その濃度が１００ ｔ／ｌをこえると、処理浴に
よってクロメート被膜が水洗或いは乾燥されるまでの間
に、部分的に溶解されるためか、外観に不均一なむらを
発生するため好ましくない。Furthermore, if the concentration exceeds 100 t/l, it is undesirable because the chromate film will be partially dissolved before it is washed with water or dried in the treatment bath, resulting in uneven appearance. .
シリカ及び／又はケイ酸塩は、コロイダルシリカを形成
するために処理液に加えられるものであり、アニオン型
コロイダルシリカ、カチオン型コロイダルシリカ、及び
アルカリ金属のケイ酸塩の１種又は２種以上の混合物が
任意に適用でき、濃度をＳｉＯ□として、１〜１００
？／ｌの範囲にすることにより、一層好ましい結果が得
られる。Silica and/or silicate are added to the treatment solution to form colloidal silica, and include one or more of anionic colloidal silica, cationic colloidal silica, and alkali metal silicate. Mixtures can be applied arbitrarily, with concentrations ranging from 1 to 100 as SiO□.
? More preferable results can be obtained by setting the amount within the range of /l.
すなわち、１１μ未満では本発明の目的とする耐食性能
及び塗装性能向上の効果が小さく、また１ ００ ｆ／
Ｌをこえる場合には、性能向上効果が飽和するとともに
、クロメート浴の電導塵が低下し、クロメート被膜量生
成のための電気量が増加する等の欠点を生じるため好ま
しくない。That is, if it is less than 11μ, the effect of improving corrosion resistance and coating performance, which is the objective of the present invention, will be small, and if it is less than 100 f/
If it exceeds L, the performance improvement effect will be saturated, and the electrically conductive dust in the chromate bath will decrease, resulting in disadvantages such as an increase in the amount of electricity required to generate the amount of chromate film, which is not preferable.
また、金属イオンは、上記クロメート浴に金属粉末、ク
ロム酸塩、リン酸塩、弗化物、炭酸塩、水酸化物等の形
態で添加される。Further, metal ions are added to the chromate bath in the form of metal powder, chromate, phosphate, fluoride, carbonate, hydroxide, and the like.
而して、その添加量は０．５〜５０？／ｌの範囲にする
ことにより、−１脅好ましい結果が得られる。So, the amount added is 0.5 to 50? By setting it in the range of /l, a favorable result of −1 threat can be obtained.
ｏ、ｓｙ／を未満の添加量では、陰極電解処理によるク
ロメート被膜形成時に、クロメート被膜中に含有され、
耐食性を向上せしめるとともに、クロメート被膜に電導
性を付与して、カチオン電着塗装時に陽極としての作用
効果を増大せしめるだめの効果が少なく、また５ ｏ
ｙ／ｌをこえる添加量ではこれらの効果が飽和するとと
もに、クロメート被膜の加工性が劣化し、加工部の耐食
性が劣化するなどの欠点を生じるので好ましくない。If the amount added is less than o, sy/, it will be contained in the chromate film when forming the chromate film by cathodic electrolysis treatment,
In addition to improving corrosion resistance, it imparts electrical conductivity to the chromate film, which increases its effectiveness as an anode during cationic electrodeposition coating.
Addition amounts exceeding y/l are not preferred because these effects are saturated, and the workability of the chromate film deteriorates, resulting in disadvantages such as deterioration of the corrosion resistance of processed parts.
浴中のｐＨは、６以下、好ましくは４以下である、ｐＨ
が６以上では、処理浴中に沈澱等が生じ易くなり、電解
処理時にこれら沈澱物、浮遊物によって被処理材に対し
てアークスポット等が発生し、耐食性及び外観劣化の原
因となるので好ましくない。The pH in the bath is below 6, preferably below 4, pH
If it is 6 or more, it is undesirable because precipitates are likely to form in the treatment bath, and during electrolytic treatment, arc spots etc. are generated on the treated material due to these precipitates and suspended matter, causing deterioration of corrosion resistance and appearance. .
処理敵のｐＨｋコントロールするためには、硫酸硝酸、
水酸化アンモニウム、アルカリ金属水酸化物、及びアル
カリ金属炭酸化合物等から任意に選んで、処理液に加え
ることができる。又、本発明の陰極電解処理時の濫元反
応により生成するｃ ｒ３＋イオンを、予め、Ｃｒ３＋
の水酸化物、及び炭酸化合物として、或いは、Ｃｒ６
＋ とアルコール類、澱粉類、及びタンニン酸等の有機
化合物との酸化還元反応生成物として、処理液に加えて
もよい。In order to control the pHk of the processing enemy, sulfuric acid, nitric acid,
Any one selected from ammonium hydroxide, alkali metal hydroxides, alkali metal carbonate compounds, etc. can be added to the treatment liquid. Further, the cr3+ ions generated by the explosion reaction during the cathodic electrolytic treatment of the present invention are preliminarily treated with Cr3+
as hydroxide and carbonate compounds, or as Cr6
+ may be added to the treatment liquid as a redox reaction product between alcohols, starches, and organic compounds such as tannic acid.
次に、本発明における陰極電解処理は、亜鉛及び亜鉛合
金メッキ鋼板、アルミ及びアルミ合金メッキ鋼板、鉛及
び鉛合金メッキ鋼板ケ陰極として、その表面に金属イオ
ンを含有してなるクロメート被膜を形成するだめに行な
われ、被膜生成量の調整は、電流密度及び電解時間によ
り行なわれる。Next, the cathodic electrolytic treatment in the present invention forms a chromate film containing metal ions on the surface of zinc and zinc alloy plated steel sheets, aluminum and aluminum alloy plated steel sheets, and lead and lead alloy plated steel sheets as a cathode. The amount of film produced is controlled by the current density and electrolysis time.
この陰極電解処理の電流密度、及び電解時間は特定する
ものではないが、電流密度を３〜５０Ａ／ ｄ ｍ”
の範囲に、１〜５秒の゛電解時間で被膜生成量を調整す
るのが好ましい。The current density and electrolysis time of this cathodic electrolytic treatment are not specified, but the current density is 3 to 50 A/dm"
It is preferable to adjust the amount of film produced within the range of 1 to 5 seconds with an electrolysis time of 1 to 5 seconds.
この陰極電解処理に続いて行なわれる陽極電解処理であ
るが、これは、前記の陰極電解被膜が形成された亜鉛メ
ッキ鋼板等の被処理材を、陽極として陽極電解被膜を形
成させるとともに、陰極電解被膜を改質、難溶性化する
ために行なわれるものである。この陽極電解処理は、電
流密度が１〜５０Ａ／ｄｒｒ？、好ましくは５−４０
Ａ／ｄｔｒ？、クーロン量が０．１−３０クーロン／ｄ
ｙｒ？、好ましくは１〜２０クーロン／ａｉの範囲で行
なわれる。The anodic electrolytic treatment is performed following this cathodic electrolytic treatment, and in this process, the material to be treated, such as a galvanized steel plate on which the cathodic electrolytic coating has been formed, is used as an anode to form an anodic electrolytic coating, and the cathodic electrolytic coating is This is done to modify the coating and make it less soluble. This anodic electrolytic treatment has a current density of 1 to 50 A/drr? , preferably 5-40
A/dtr? , the amount of coulombs is 0.1-30 coulombs/d
yr? , preferably in the range of 1 to 20 coulombs/ai.
電流密度がｌ Ａ ／ ｄ−未満では、この被膜改質効
果が得られず、被膜があまり難溶性化せず、また耐食性
向上効果も得られない。また５０Ａ／ｄｍ’をこえる電
流密度では、陰極処理による形成被膜の部分的な被膜溶
解が生じ、耐食性が劣化する現象を生じるので好ましく
ない。If the current density is less than 1 A / d-, this coating modification effect cannot be obtained, the coating will not become very insoluble, and the corrosion resistance improvement effect will not be obtained. Further, a current density exceeding 50 A/dm' is not preferable because it causes partial dissolution of the film formed by cathodic treatment, resulting in a phenomenon of deterioration of corrosion resistance.
クーロン量が０．１クーロン／ａｒｒ？より少ない時は
、本発明の目的とする被膜性能の向上効果が得られず、
また３０クーロン／ｄｙｒ？をこえる時には、被膜性能
向上効果が飽和すると共に、前記と同様にクロメート被
膜の部分的溶解により耐食性が劣化するので好ましくな
い。Is the amount of coulombs 0.1 coulombs/arr? When the amount is less, the effect of improving the film performance which is the objective of the present invention cannot be obtained,
30 coulombs/dyr again? If it exceeds this, the effect of improving coating performance will be saturated, and the corrosion resistance will deteriorate due to partial dissolution of the chromate coating, which is not preferable.
処理液の温度としては、常温〜７０′Ｃである。The temperature of the treatment liquid is from room temperature to 70'C.
７０’Ｃより高くしても、形成される皮膜の特性に変化
はないが、不経済になるので、工業的ては７０°Ｃが限
度である。Even if the temperature is higher than 70'C, there is no change in the properties of the film formed, but it becomes uneconomical, so 70°C is the industrial limit.
本発明により、電解処理（陰極電解後、陽極電解処理）
された亜鉛メッキ鋼板等の処理材は、水洗したのち乾燥
して、防食用又は塗装下地として適用されるが、水洗せ
ずにスキイジーロールを通した後、乾燥して適用するこ
ともできる。又、必要に応じては、一般に行われている
、クロメート水溶液、及び防食性水溶性有機化合物によ
る、後処理もできる。According to the present invention, electrolytic treatment (after cathodic electrolysis, anodic electrolytic treatment)
The treated materials, such as galvanized steel sheets, are washed with water and then dried and applied for corrosion protection or as a base for painting, but they can also be applied after being passed through a squeegee roll and dried without being washed. Further, if necessary, post-treatment with a chromate aqueous solution and an anticorrosive water-soluble organic compound can also be carried out, which is generally performed.
尚、本発明の方法によって、処理される金属表面処理鋼
板は、電気メツキ法、溶融メッキ法、真空蒸着法等によ
り製造された以下の如き鋼板に適用される。例えば、
■ 亜鉛及び亜鉛合金メッキ鋼板とは、Ｚｎ及びＺｎに
０．５％以下の成を含有するメッキ鋼板、これらに少量
のｓｂ或いはＰｂ、Ｃｄ等の不可避的不純物全含有する
メッキ鋼板、Ｚｎに、ＡＡを（３〜６０係）含有し、こ
れにＳｉ 、 Ｍｙ、ミソシュメタルの１種以上又は２
種以上を２チ以下含有する合金メッキ鋼板、ＺｎにＮｉ
、Ｃｏの１種又は２種以上を（５〜２５チ）含有する合
金メッキ鋼板、これに５ｉ０２ 、 Ｃｒ の１種又
は２種以上を１０チ以下含有する合金メッキ鋼板、Ｚｎ
にＦｅを（８〜９０％）含有する合金メッキ鋼板
■ アルミ及びアルミ合金メッキ鋼板とは、Ａｌと不可
避高不純物からなるアルミメッキ鋼板、Ａｌに（１〜１
５％）の８１と不可避的不純物からなるアルミ合金メッ
キ鋼板、Ａｌに（１〜１５チの８１と３％以下のＭ？を
含有する合金メッキ鋼板■ 鉛及び鉛合金メッキ鋼板と
は、ｐｂと不可避的不純物からなるｐｂメッキ鋼板、ｐ
ｂに（１〜３０％）のＳｎと不可避的不純物からなる合
金メッキ鋼板、Ｐｂに（１〜３０％）のＳｎと５％以下
のｓｂ。The metal surface-treated steel sheet treated by the method of the present invention can be applied to the following steel sheets manufactured by electroplating, hot-dip plating, vacuum evaporation, or the like. For example, ■ Zinc and zinc alloy plated steel sheets include plated steel sheets containing Zn and 0.5% or less of Zn, plated steel sheets containing a small amount of sb or all unavoidable impurities such as Pb and Cd, and zinc and zinc alloy plated steel sheets. Contains AA (3 to 60 parts), and one or more of Si, My, and Misosmetal, or two
Alloy plated steel sheet containing 2 or more species, Zn and Ni
, an alloy-plated steel sheet containing one or more types of Co (5 to 25 inches), an alloy-plated steel sheet containing one or more types of 5i02, Cr, or less than 10 inches, Zn
Alloy-plated steel sheet containing (8 to 90%) Fe in
5%) of 81 and unavoidable impurities; Alloy-plated steel sheet containing (1 to 15%) of 81 and 3% or less of M?■ Lead and lead alloy plated steel sheets are PB plated steel sheet consisting of unavoidable impurities, p
Alloy-plated steel plate consisting of (1-30%) Sn and unavoidable impurities in b, and Pb (1-30%) Sn and 5% or less sb.
Ｚｎ、Ｃｄの１種又は２種以上、不可避的不純物からな
る合金メッキ鋼板
等を含む。It includes alloy-plated steel sheets made of one or more of Zn, Cd, and unavoidable impurities.
（実施例） 以下に本発明の実施例と比較例を示す。(Example) Examples and comparative examples of the present invention are shown below.
（実施例）
鋼板ストリップを通常表面処理鋼板の製造工程において
施される前処理を施して製造された表面処理鋼板に対し
て、第１表に示す、本発明の処理浴及び処理条件を用い
て、クロメート処理を施した。尚、クロメート処理は、
第１表記載の処理後水洗して、ロール絞りを行ない雰囲
気温度１５０℃で５秒間、加熱乾燥処理を行なった。ま
た、これら処理材の性能評価結果を第２表に、比較材の
性能評価結果と併せ示す。(Example) Using the treatment bath and treatment conditions of the present invention shown in Table 1, a surface-treated steel sheet manufactured by subjecting a steel sheet strip to pretreatment that is normally applied in the manufacturing process of surface-treated steel sheets. , chromate treatment was applied. In addition, chromate treatment is
After the treatments listed in Table 1, the samples were washed with water, squeezed with a roll, and then heated and dried at an ambient temperature of 150° C. for 5 seconds. Further, the performance evaluation results of these treated materials are shown in Table 2 together with the performance evaluation results of the comparative materials.
尚、本発明の処理材と比較材の性能比較については、第
１表及び第２表に記載の同一表面処理鋼板同志について
、本発明のクロメート処理法と比較例のクロメート処理
法の各々の性能を相対的に評価した。Regarding the performance comparison between the treated material of the present invention and the comparative material, the performance of the chromate treatment method of the present invention and the chromate treatment method of the comparative example for the same surface-treated steel sheets listed in Tables 1 and 2 is compared. were evaluated relatively.
尚、評価試験法及び評価基準は以下の方法に拠った。The evaluation test method and evaluation criteria were based on the following methods.
■耐食性
ＪＩＳ−Ｚ−２３７１に準拠した塩水噴霧試験法により
、特定時間後の発錆状態（白隋及びメッキ層の部分的溶
解による黒点の両方）を観察し、以下の評価基準で評価
した。(2) Corrosion Resistance The state of rust (both white spots and black spots due to partial dissolution of the plating layer) after a specific time was observed using the salt spray test method in accordance with JIS-Z-2371, and evaluated using the following evaluation criteria.
◎・・・・・発錆１％未満
Ｏ・・・・・ Ｉ １チ超〜５％未満
Δ・・・・・ ｌ ５％超〜１５％未満Ｘ・・・・・
＃ １５％超〜
■塗装性能
市販のメラミンアルキッド系白色塗料を２５μ厚さ塗装
してその性能を評価した。◎・・・・Rusting less than 1% O・・・・ I More than 1 inch to less than 5% Δ・・・・ l More than 5% to less than 15%
#More than 15%~ ■Painting Performance A commercially available melamine alkyd white paint was applied to a thickness of 25μ and its performance was evaluated.
■−１
塗膜に１ｍｍ間隔の基盤目を１００マ、ス切ったのち、
エリクセン試’Ｊｄで７ｗＲ押し出し、セロファンテー
プで剥離試験を行い、塗膜の剥離の程度を肉眼で判定し
、イＱ、○、Δ、×の４段階で評価。◎が最良である。■-1 After cutting 100 base lines at 1mm intervals on the coating film,
Extrude at 7wR with Erichsen's Jd, perform a peeling test with cellophane tape, judge the degree of peeling of the coating film with the naked eye, and evaluate it in 4 grades: A, Q, ○, Δ, and ×. ◎ is the best.
■−２デュポン衝修試験
デュポン衝撃試４験機を用い、重さ５ｏ０２の重錘を５
０α高さから落下して、塗膜面に衝撃を加え、塗膜の剥
離程度を肉眼で判定し、◎、○、Δ、×の４段階で評４
曲、◎が最良である。■-2 DuPont impact test Using a DuPont impact tester 4, a weight of 5o02 was
After falling from a height of 0α, impact is applied to the coating surface, and the degree of peeling of the coating film is judged with the naked eye.
The song ◎ is the best.
■−３塗装後耐食性
メッキ表面まで達するスクラッチ疵を入れ、塩水噴霧試
験２４０時間後の塗膜のフクレ巾の観察により評価を行
なった。(3) Corrosion resistance after coating Scratches reaching the plating surface were made, and evaluation was made by observing the blistering width of the coating film after 240 hours of salt spray test.
◎・・・・・スクラッチ部からの平均フクレ巾２朧以下
○００００．スクラッチ部からの平均フクレ巾２゜超〜
４ＩＩＩ１１以下
Δ１１１．．スクラッチ部からの平均フクレ巾４１雨超
〜７調以下
Ｘ・・・・・スクラッチ部からの平均フクレ巾７１超
■カチオン電着性能
２００ｖで３分間の塗装条件で、塗装処理を施し、
■−１−１塗膜量
クロメート処理を施さない表面処理鋼板に対する付着量
とクロメート処理後の付着量を測定して、その付着性を
評価した、すなわち、無処理材の付着量を１とした場合
のクロメート処理材の付着量が、各々
◎・・・・・０．９５以上の塗膜厚（付着量）○・・・
・・０．９５未満〜０．８５以上の塗膜厚△・・・・・
０．８５未満〜０．７０以上の塗膜厚×・・・・・０．
７０未満の塗膜厚
■−２カチオン電着塗装後の耐食性
上記の電着塗装後１８０°Ｃで２０分間焼付は塗装後に
、メッキ面に達するスクラッチ疵を入れ、塩水噴霧試、
＠ ２４０時間後に、セロテープ剥離を行ない、その塗
膜剥離中によってその耐食性を評価した。◎・・・Average blister width from scratch area 2 hazy or less ○0000. Average bulge width from scratch area exceeds 2°
4III11 or less Δ111. ．． Average width of blisters from the scratch area: 41+ to 7 or less 1-1 Coating Amount The adhesion was measured by measuring the amount of adhesion on a surface-treated steel sheet without chromate treatment and the amount of adhesion after chromate treatment, that is, when the amount of adhesion on the untreated material was set as 1. The coating thickness (amount of adhesion) of the chromate treated material is ◎...0.95 or more ○...
・・Coating film thickness of less than 0.95 to 0.85 or more △・・・・
Coating film thickness of less than 0.85 to 0.70 or more×・・・0.
Coating film thickness less than 70 ■-2 Corrosion resistance after cationic electrodeposition coating After the above electrodeposition coating, bake at 180°C for 20 minutes, make scratches that reach the plated surface, salt water spray test,
After 240 hours, cellophane tape was removed, and the corrosion resistance was evaluated while the coating was being removed.
（＠・・・・・スクラッチ部及びその他部分からの剥離
が少なく、塗装後耐食性極めて良好
○・・・・・スクラッチ部からの剥離は比較的大きいが
、その他部分からの剥離は少なく、塗装後耐食性比較的
良好
Δ・・・・・スクラッチ部からの剥離及びその他平面部
からの剥離が可成り大きく、塗装
後付食性可成り劣る。(@... There is little peeling from the scratch area and other parts, and the corrosion resistance after painting is extremely good.○... The peeling from the scratch area is relatively large, but there is little peeling from other parts, and after painting Corrosion resistance relatively good Δ...Peeling from scratch areas and other flat areas is quite large, and corrosion resistance after painting is quite poor.
×・・・・・スクラッチ部及びその他平面部とも塗膜剥
離大きく、塗装後耐食性著しく劣
る。×...The paint film peeled off significantly in the scratched area and other flat areas, and the corrosion resistance after painting was significantly inferior.
（発明の効果）
これらの結果から判然とする様に、本発明のクロメート
処理被膜はすぐれた性能を有する、即ち、本発明の方法
によるクロメート被膜は、金属物を含有する被膜で形成
されるため、耐食性能を確保するだめのクロメート被膜
量が増加した場合でも、カチオン電着性能が損なわれる
事がなく、耐食性、カチオン電着性能等多機能な高性能
処理が可能である。(Effects of the Invention) As is clear from these results, the chromate-treated film of the present invention has excellent performance. That is, the chromate film produced by the method of the present invention is formed from a film containing a metal substance. Even if the amount of chromate film required to ensure corrosion resistance is increased, the cationic electrodeposition performance is not impaired, and multifunctional high-performance processing such as corrosion resistance and cationic electrodeposition performance is possible.
Claims (3)
弗素化合物の１種または２種、これにＺｎイオン、Ｎｉ
イオン、Ｃｏイオン、Ａｌイオン、Ｍｇイオン、Ｓｎイ
オン、Ｍｎイオン、Ｐｂイオンの１種又は２種以上を含
有する組成からなるクロメート浴中で、亜鉛及び亜鉛合
金メッキ鋼板、アルミ及びアルミ合金メッキ鋼板、鉛及
び鉛合金メッキ鋼板を陰極電解処理し、クロメート被膜
を形成させた後直ちに陽極電解処理して陽極電解改質被
膜を設ける事を特徴とする表面処理鋼板のクロメート処
理法、(1) Cr^6^+ ion, PO_4^3^- ion and one or two kinds of fluorine compounds, and Zn ion, Ni
ion, Co ion, Al ion, Mg ion, Sn ion, Mn ion, and Pb ion, in a chromate bath having a composition containing one or more of the following: , a chromate treatment method for a surface-treated steel sheet, characterized in that a lead and lead alloy plated steel sheet is subjected to cathodic electrolysis treatment to form a chromate film, and then immediately subjected to anodic electrolysis treatment to form an anodic electrolytic modification film;
たは２種、これにＺｎイオン、Ｎｉイオン、Ｃｏイオン
、Ａｌイオン、Ｍｇイオン、Ｓｎイオン、ｐｂイオン、
Ｍｎイオンの１種又は２種以上を含有する組成からなる
クロメート浴中で、亜鉛及び亜鉛合金メッキ鋼板、アル
ミ及びアルミ合金メッキ鋼板、鉛及び鉛合金メッキ鋼板
を陰極電解処理し、クロメート被膜を形成させた後直ち
に陽極電解処理して陽極電解改質被膜を設ける事を特徴
とする表面処理鋼板のクロメート処理法(2) Cr^6^+ ion, silica, one or two kinds of silicate, Zn ion, Ni ion, Co ion, Al ion, Mg ion, Sn ion, pb ion,
In a chromate bath containing one or more types of Mn ions, zinc and zinc alloy plated steel sheets, aluminum and aluminum alloy plated steel sheets, lead and lead alloy plated steel sheets are subjected to cathodic electrolysis treatment to form a chromate film. A chromate treatment method for a surface-treated steel sheet, which is characterized by immediately applying an anodic electrolytic treatment to provide an anodic electrolytic reforming film.
と弗素化合物の１種または２種、シリカとケイ酸塩の１
種または２種、これに、Ｚｎイオン、Ｎｉイオン、Ｃｏ
イオン、Ａｌイオン、Ｍｇイオン、Ｓｎイオン、Ｍｎイ
オン、Ｐｂイオンの１種又は２種以上を含有するクロメ
ート浴中で、亜鉛及び亜鉛合金メッキ鋼板、アルミ及び
アルミ合金メッキ鋼板、鉛及び鉛合金メッキ鋼板を陰極
電解処理し、クロメート被膜を形成させた後直ちに陽極
電解処理して陽極改質被膜を設ける事を特徴とする表面
処理鋼板のクロメート処理法(3) Cr^6^+ ion, PO_4^3^- ion and one or two fluorine compounds, and one of silica and silicate.
species or two species, including Zn ions, Ni ions, Co
Zinc and zinc alloy plated steel sheets, aluminum and aluminum alloy plated steel sheets, lead and lead alloy plated in a chromate bath containing one or more of the following: ion, Al ion, Mg ion, Sn ion, Mn ion, Pb ion. A chromate treatment method for a surface-treated steel sheet, characterized in that the steel sheet is subjected to cathodic electrolysis treatment to form a chromate film, and then immediately subjected to anodic electrolysis treatment to form an anodic modification film.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11839386A JPS62278297A (en) | 1986-05-24 | 1986-05-24 | Method for chromating metal-surface-treated steel sheet |
| AU72517/87A AU574609B2 (en) | 1986-05-12 | 1987-05-05 | Chromate treatment of metal coated steel sheet |
| DE8787106797T DE3772117D1 (en) | 1986-05-12 | 1987-05-11 | CHROMATE TREATMENT OF A METAL COATED STEEL SHEET. |
| EP87106797A EP0250792B1 (en) | 1986-05-12 | 1987-05-11 | A chromate treatment of a metal coated steel sheet |
| ES87106797T ES2023378B3 (en) | 1986-05-12 | 1987-05-11 | CHROME TREATMENT OF METAL COATED STEEL SHEET. |
| CA000537100A CA1318635C (en) | 1986-05-24 | 1987-05-12 | Chromate treatment of a metal coated steel sheet |
| US07/049,502 US4784731A (en) | 1986-05-12 | 1987-05-12 | Chromate treatment of a metal coated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11839386A JPS62278297A (en) | 1986-05-24 | 1986-05-24 | Method for chromating metal-surface-treated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62278297A true JPS62278297A (en) | 1987-12-03 |
| JPH0214436B2 JPH0214436B2 (en) | 1990-04-09 |
Family
ID=14735568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11839386A Granted JPS62278297A (en) | 1986-05-12 | 1986-05-24 | Method for chromating metal-surface-treated steel sheet |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS62278297A (en) |
| CA (1) | CA1318635C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63250497A (en) * | 1987-04-06 | 1988-10-18 | Nisshin Steel Co Ltd | Post-treatment of alloyed hot dipped steel sheet |
| JPH0288799A (en) * | 1988-09-22 | 1990-03-28 | Nkk Corp | Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production |
| 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 |
| KR100554146B1 (en) * | 2001-11-14 | 2006-02-20 | 주식회사 포스코 | Chromate treatment method for the zinc plated steel |
-
1986
- 1986-05-24 JP JP11839386A patent/JPS62278297A/en active Granted
-
1987
- 1987-05-12 CA CA000537100A patent/CA1318635C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63250497A (en) * | 1987-04-06 | 1988-10-18 | Nisshin Steel Co Ltd | Post-treatment of alloyed hot dipped steel sheet |
| JPH0288799A (en) * | 1988-09-22 | 1990-03-28 | Nkk Corp | Zinc or zinc alloy-plated steel sheet having excellent corrosion resistance, coating property, and fingerprinting resistance and its production |
| JPH0543799B2 (en) * | 1988-09-22 | 1993-07-02 | Nippon Kokan Kk | |
| 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 |
| KR100554146B1 (en) * | 2001-11-14 | 2006-02-20 | 주식회사 포스코 | Chromate treatment method for the zinc plated steel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0214436B2 (en) | 1990-04-09 |
| CA1318635C (en) | 1993-06-01 |
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