JPH02118099A - Electrolytic chromating bath for metal plated steel sheet - Google Patents
Electrolytic chromating bath for metal plated steel sheetInfo
- Publication number
- JPH02118099A JPH02118099A JP26825188A JP26825188A JPH02118099A JP H02118099 A JPH02118099 A JP H02118099A JP 26825188 A JP26825188 A JP 26825188A JP 26825188 A JP26825188 A JP 26825188A JP H02118099 A JPH02118099 A JP H02118099A
- Authority
- JP
- Japan
- Prior art keywords
- plated steel
- steel sheet
- bath
- corrosion resistance
- steel sheets
- 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 46
- 239000010959 steel Substances 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title abstract description 11
- 239000002184 metal Substances 0.000 title abstract description 11
- 238000004532 chromating Methods 0.000 title abstract 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 29
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000005260 corrosion Methods 0.000 abstract description 27
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000007921 spray Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 3
- 229910003899 H2ZrF6 Inorganic materials 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 230000007935 neutral effect Effects 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000011701 zinc Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008397 galvanized steel Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- 229910000680 Aluminized steel Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 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
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 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
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000002087 whitening effect Effects 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)
- Chemical Treatment Of Metals (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）
本発明は、亜鉛または亜鈴系合金メッキ鋼板、アルミま
たはアルミ系合金メッキ鋼板などのような金属メッキ鋼
板に、耐食性と塗装性にすぐれた白色外観性の電解クロ
メート皮膜を形成する金属メッキ鋼板用電解クロメート
（処理）浴に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention provides a method for applying white color with excellent corrosion resistance and paintability to metal-plated steel sheets such as zinc or tin alloy-plated steel sheets, aluminum or aluminum-based alloy-plated steel sheets, etc. This invention relates to an electrolytic chromate (treatment) bath for metal-plated steel sheets that forms an electrolytic chromate film with good appearance.
（従来技術及び発明が解決しようとする課題）電解クロ
メート皮膜は、塗料との密着性を維持して耐食性を向Ｅ
せしめる皮膜として、多くの種類の金属メッキ鋼板に施
されている。例えば特公昭４７−４４４１７号公報は「
無水クロム酸１５〜１３０ご／ｌ、硫１浚０．０５〜０
、５ ｇ／ Ｑを含む１容液中で、亜鉛メッキ鋼板を
陰極′Ｋｉ解処卵処理ことによって耐食性と塗装後の二
次密着性にすぐれた亜鉛メッキ鋼板の製造法」をμｓ供
するものであるが、今日のように厳しい環境の中で耐食
性は不充分であり、淡黄色外観を呈する。このように淡
杭色を呈した電解クロメート処理鋼板は、外観上の問題
から、商品的価値を著しく損なう問題があった。(Prior art and problems to be solved by the invention) The electrolytic chromate film maintains adhesion with paint and improves corrosion resistance.
It is applied to many types of metal-plated steel sheets as a protective coating. For example, Japanese Patent Publication No. 47-44417 states “
Chromic anhydride 15-130/l, sulfur 1/l 0.05-0
, a method for producing galvanized steel sheets with excellent corrosion resistance and secondary adhesion after painting by subjecting galvanized steel sheets to cathodic ``Ki-dissolving egg treatment'' in 1 volume solution containing 5 g/Q. However, in today's harsh environments, its corrosion resistance is insufficient and it exhibits a pale yellow appearance. The electrolytic chromate-treated steel sheet exhibiting such a pale yellow color has a problem in its appearance, which significantly impairs its commercial value.
一般に陰極電解皮膜は、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
理材の外観を損ない更に塗装性能を低下するという欠点
があるため、外ｗ！。In general, cathode electrolytic coatings compensate for corrosion resistance by increasing the amount of film formed (mainly the amount of chromium deposited). but,
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. .
耐食性、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、金属メッキ鋼板を連続し
て処理すると、７ ｎ２ ＋イオンが処理液中に蓄積し
、耐食性を著しく低下する等の問題を有している。It was difficult to form a film with excellent corrosion resistance and coating performance. Furthermore, these cathodic electrolytic methods have a problem in that when metal-plated steel sheets are continuously treated, 7 n2 + ions accumulate in the treatment solution, significantly reducing corrosion resistance.
さらに耐食性と塗装性能と外観性を改善する方法に、特
開昭６２−２６３９９７号公報の［クロメート浴で金属
メッキ鋼板を陰極電解処理し続いて陽極電解処理するク
ロメート皮膜の改質方法」がある。この方法は使用初期
のクロメート浴では所要目的の性質を満足するクロメー
ト皮膜の金属メッキ鋼板が得られるが、長期使用してい
る間に陽極電解処理ではファラデーの法則に従ってメッ
キ金属を溶解して該浴組成が変化し安定した性質を保有
するクロメート皮膜が得られない問題があった・
また、クロメート浴にＣＯ金金属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
ロメート皮膜中に安定して金属イオンを含有せしめ、ク
ロメート皮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。Furthermore, a method for improving corrosion resistance, coating performance, and appearance is disclosed in Japanese Patent Application Laid-open No. 62-263997, entitled ``A method for modifying a chromate film in which a metal-plated steel sheet is cathodic electrolytically treated in a chromate bath, followed by anodic electrolytically treated.'' . In this method, a metal-plated steel sheet with a chromate film that satisfies the desired properties can be obtained in the initial chromate bath, but during long-term use, the anodic electrolytic treatment dissolves the plated metal according to Faraday's law and the bath There was a problem that a chromate film with stable properties could not be obtained due to changes in composition.Also, methods have been proposed in which CO gold metal cations are added to a chromate bath and applied or immersed. No method has been developed for stably incorporating metal ions into a chromate film to improve the electrical properties of the chromate film.
（課題を解決するための手段）
本発明は上記のような従来の電解クロメート処理法の欠
点を改善してクロメート皮膜の均一性。(Means for Solving the Problems) The present invention improves the above-mentioned drawbacks of the conventional electrolytic chromate treatment method and improves the uniformity of the chromate film.
耐食性、白色外観性、塗’１ｖｌｉ着性にすぐれたクロ
メート皮膜が工業的に安定して、亜鉛または亜鉛系合金
メッキ鋼板、アルミまたはアルミ系合金メッキ鋼板など
の金属メッキ鋼板表面に形成できる電解クロメート（処
理）浴を提供することを目的としたものである。その要
旨はＣｒｙ、：１０〜６０ ｇ ／ Ｑ Ｉ５１０２
： ｌ 〜２０ ｇ ／ Ｑ ＋ Ｈ２Ｚ ｒ Ｆ ｓ
：０．５〜１０ｇハ’ ＊ Ｈｚ Ｓ ０４ ： Ｏ
−１〜２ｇ／１２：Ｆ−イオン：０．１〜３ ｇＩＱ
からなる組成でかつＰＨを２．０〜３．２に調整した
金属メッキ鋼板用電解クロメート浴である。An electrolytic chromate that can form an industrially stable chromate film with excellent corrosion resistance, white appearance, and paint adhesion on the surface of metal-plated steel sheets such as zinc or zinc-based alloy-plated steel sheets, aluminum or aluminum-based alloy-plated steel sheets. The purpose is to provide a (processing) bath. The gist is Cry: 10-60 g/Q I5102
: l~20g/Q+H2ZrFs
: 0.5~10g *Hz S 04 : O
-1~2g/12:F-ion: 0.1~3 gIQ
This is an electrolytic chromate bath for metal-plated steel sheets having a composition consisting of the following and having a pH adjusted to 2.0 to 3.2.
（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.
洛中のＣｒＯ３濃度は、第１図で示すように。The CrO3 concentration in Rakuchu is as shown in Figure 1.
１０〜６０ｇＩＱが必要である。ＣｒＯ，ａ度が１０ｇ
／Ｑ未満では形成される皮膜の耐食性が不充分であり、
また６０ｇ／Ｑを越える濃度では皮膜の効果が飽和する
と共に外観が淡黄色に帯び易い。５ｉｎ２は皮膜の耐食
性と塗料密着性を高める成分とじてコロイダルシリカか
ら供給され、第２図で示すように、Ｉｇ・７０未満では
その効果が本発明の目的から小さく、また２０ｇ１を越
える濃度ではそれらの効能が飽和に達すると共に浴の電
導度を低下し。10-60g IQ is required. CrO, a degree is 10g
If it is less than /Q, the corrosion resistance of the formed film is insufficient,
Further, at a concentration exceeding 60 g/Q, the effect of the film becomes saturated and the appearance tends to take on a pale yellow tinge. 5in2 is supplied from colloidal silica as a component that improves the corrosion resistance and paint adhesion of the film, and as shown in Figure 2, its effect is small for the purpose of the present invention at Ig. The conductivity of the bath decreases as its efficacy reaches saturation.
皮膜生成に必要な電気量を増加する問題がある、したが
って１本発明においてＳｉＯ，ｆｉ度は１〜２ Ｑ ｇ
ＩＱに限定した。Ｈｔ Ｚ ｒ Ｆ 、は皮膜に耐食性
と外観白色度を付与するために添加するもので、第３図
で示すように０．５ｇ／Ｑ未満の濃度では添加効果が小
さく、１０ｇ／Ｑ を越える濃度では外観白色度を低
下する。Ｈ２ＳＯ４の添加は第４図で示すように皮膜の
耐食性を向上させると共に、Ｐ）ｔを制御し、沈澱物の
発生を抑制して浴の安定性を維持するために添加するも
のであって、０．１ｇ／Ｑ未満ではその効果が小さく、
また２ ｇ／ Ｑを越える濃度では電解処理される鋼板
のメッキ金属が溶解し金属メッキ鋼板自体の耐食性を劣
化する。There is a problem of increasing the amount of electricity required for film formation, therefore, in the present invention, the SiO, fi degree is 1 to 2 Q g
Limited to IQ. Ht Z r F is added to impart corrosion resistance and appearance whiteness to the film.As shown in Figure 3, the effect of addition is small at concentrations below 0.5 g/Q, and at concentrations exceeding 10 g/Q. In this case, the appearance whiteness is reduced. As shown in Figure 4, H2SO4 is added to improve the corrosion resistance of the coating, control P)t, suppress the generation of precipitates, and maintain bath stability. If it is less than 0.1g/Q, the effect is small;
In addition, if the concentration exceeds 2 g/Q, the plated metal of the steel plate to be electrolytically treated will dissolve and the corrosion resistance of the metal plated steel plate itself will deteriorate.
Ｆ−イオンは第５図で示すように、皮膜の均一性や耐食
性を付与するために添加するもので、０．１ｇ／Ｑ未満
ではその効果が小さい、また３ｇＩＱを越えろ濃度では
それらの効果が飽和すると共に。As shown in Figure 5, F- ions are added to impart uniformity and corrosion resistance to the film, and their effects are small at concentrations below 0.1 g/Q, and their effects are diminished at concentrations above 3 g/Q. Along with saturation.
皮膜の外ｖ１白色度を減じ淡黄色化する。このような理
由から本発明においてはＦ＋イオンの、５度を０．１〜
３．０ｇ／Ｑに限定した。また浴の円１は第６図で示す
ように耐食性を外観白色度から ２．０〜３．２とする
。 ｐＨが２．０未満では皮膜の外観白色度を減じて淡
黄色化を呈し、耐食性、塗装性を劣、化し、Ｚｎ、Ａｌ
ｌ、Ｐｂなどのメッキ金属の溶解速度を大きくして金属
メッキ鋼板がもつ耐食性を減じる傾向にある。また３、
２を越えるＰｌ＋は浴の安定性が著しく低下し、皮膜の
耐食性を劣化する傾向にある。図中、白色度（Ｗ’）は
ｊＩｓ Ｋ−７１０５に準拠して刺激値Ｘ、Ｙ、Ｚを測
定し、次式により求めた値である。The outer v1 whiteness of the film is reduced and it becomes pale yellow. For this reason, in the present invention, the 5 degree of F+ ion is set to 0.1~
It was limited to 3.0g/Q. Further, as shown in FIG. 6, the bath circle 1 has a corrosion resistance of 2.0 to 3.2 based on the external whiteness. If the pH is less than 2.0, the external whiteness of the film will decrease and it will become pale yellow, resulting in poor corrosion resistance and paintability, and
There is a tendency to increase the dissolution rate of plated metals such as L and Pb and reduce the corrosion resistance of metal plated steel sheets. Also 3,
If Pl+ exceeds 2, the stability of the bath decreases significantly and the corrosion resistance of the coating tends to deteriorate. In the figure, the whiteness (W') is a value obtained by measuring the stimulation values X, Y, and Z according to JIs K-7105 and using the following formula.
Ｗ’ ＝４（０，８４７Ｚ）−：３Ｖ
上記のような浴組成とＰＨで構成された電解クロメート
浴中で、金属メッキ鋼板を陰極にして陰極電解処理する
８
尚、本発明のクロメート処理浴によって、処理される金
属表面処理鋼板は、電気メッキ法、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Ａ１２を含有するメッキ鋼板。W' = 4 (0,847Z) -: 3V In an electrolytic chromate bath having the bath composition and pH as described above, cathodic electrolysis treatment is performed using a metal plated steel plate as a cathode.8 Note that the chromate treatment bath of the present invention The metal surface-treated steel sheet treated by this method is applied to the following steel sheets manufactured by electroplating, hot-dip plating, vacuum evaporation, etc. For example, (1) Zinc and zinc alloy plated steel sheet is a plated steel sheet containing Zn and 0.5% or less of A12 in Zn.
これらに少量のｓｂ或いはＰｂ、Ｃｄ等の不可避的不純
物を含有するメッキ鋼板、ＺｎにＡＱを（３〜６０％）
含有し、これにＳｉ、Ｍｇ、 ミツシュメタルの１種
以上又は２種以上を２％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％）
含有する合金メッキ鋼板、これにＳｉＣ，、Ｃｒの１種
又は２種以上を１０％以ト含有する合金メッキ鋼板、Ｚ
ｎにＦ ｔｒを（８〜９０％）含有する合金メッキ鋼板
（２〕 アルミ及びアルミ合金メッキ鋼板とは。These include plated steel sheets containing a small amount of unavoidable impurities such as sb, Pb, and Cd, and AQ (3 to 60%) to Zn.
alloy-plated steel sheet containing 2% or less of one or more or two or more of Si, Mg, and Mitsushi metal;
Zn with one or more of Ni and Co (5-25%)
Alloy plated steel plate containing 10% or more of one or more of SiC, Cr, Z
Alloy-plated steel sheet containing F tr (8-90%) in n (2) What is aluminum and aluminum alloy-plated steel sheet?
ＡＭと不可避的不純物からなるアルミメッキｔｉ板、Ａ
Ｑに（１〜１５％）のＳｌと不可避的不純物からなるア
ルミ合金メッキ鋼板、ＡＱに（１〜１５％のＳｌと３％
以下のＭｇを含有する合金メッキ鋼１反
（■ 釦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、ｐｂ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、 Ｚｎ、Ｃｄ
（１） １種又は２種以り二、不ｉｉｆ避的不純物か
らなる合金メッキ鋼板
等が挙げられる。Aluminized Ti plate consisting of AM and inevitable impurities, A
Q is an aluminum alloy plated steel sheet consisting of (1~15%) Sl and unavoidable impurities, AQ is (1~15% Sl and 3%
Alloy-plated steel sheets containing the following Mg (■ Buttons and lead alloy-plated steel sheets are PB-plated steel sheets consisting of PB and inevitable impurities; Gold-plated steel plate, Pb with (1-30%) Sn and 5% or less Sb, Zn, Cd
(1) Examples include alloy plated steel sheets containing one or more of two or more unavoidable impurities.
又本発明の陰極電解処理時の還元反応により生成するＣ
ｒ”イオンと予めＯｒ１′の水酸化物、戻、贅化物或い
はＣｒ”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。さらにまた’＋？ｔ Ｆｉｌクロメート浴中に
少量のこれらのメッキ金Ｌ〕（が溶出してくるが、これ
らのメッキ金属イオンを予め酸化物、水酸化物、硫酸塩
、炭酸塩等の形て添加してもよい。In addition, C generated by the reduction reaction during the cathodic electrolytic treatment of the present invention
It may be added to the treatment solution in advance as a redox reaction product between r'' ion and Or1' hydroxide, reconstituted or refined product, or Cr'' and an organic compound such as alcohol, starch, or tannic acid. Yet another '+? A small amount of these plated gold L]( will be eluted into the tFil chromate bath, but these plated metal ions may be added in advance in the form of oxides, hydroxides, sulfates, carbonates, etc.) .
次に本発明の実施例について説明する。Next, examples of the present invention will be described.
各種メッキ鋼板に対して本発明の処理浴で電解クロメー
ト処理を施した。その時の処理条件と、得られたクロメ
ート処理鋼板の性能及びその比１１々例をそれぞれ第１
表に示す。Various plated steel plates were subjected to electrolytic chromate treatment using the treatment bath of the present invention. The treatment conditions at that time, the performance of the obtained chromate-treated steel sheets, and 11 examples of their ratios are shown in the first section.
Shown in the table.
実施例１及びその比較例１は被処理材が電気亜鉛メッキ
鋼板で本発明の処理材の性能は外観塩水噴霧耐食性、塗
装性、塗装後嗣食性等調査項目すべての点ですぐれた性
能を示した。実施例２及びその比較例２は被処理材が溶
融亜鉛メッキ鋼板、実施例３及びその比較例３は被処理
材が合金化溶融亜鉛メンキ鋼板、実施例４及びその比較
例４の被処理材は＋８融アルミメッキ鋼板、実施例５及
びその比較例５の被処理材は溶融ターンメッキ鋼板。In Example 1 and Comparative Example 1, the materials to be treated were electrogalvanized steel sheets, and the treated materials of the present invention showed excellent performance in all the investigated items such as appearance salt spray corrosion resistance, paintability, and corrosion resistance after painting. . In Example 2 and Comparative Example 2, the material to be treated is a hot-dip galvanized steel sheet, in Example 3 and Comparative Example 3, the material to be treated is an alloyed hot-dip galvanized steel sheet, and in Example 4 and Comparative Example 4, the material to be treated is The material to be treated in Example 5 and its comparative example 5 was a +8 fusion aluminized steel plate, and the material to be treated was a fusion turn-plated steel plate.
実施例６及びその比較例６は電気鉛メッキ鋼板をそれぞ
れ用いてクロメート処理を行い１本発明の処理浴でクロ
メート処理を行ったものは比較例に比へて良好な性能が
得られている。In Example 6 and Comparative Example 6, electrolytic lead-plated steel plates were subjected to chromate treatment, and those subjected to chromate treatment using the treatment bath of the present invention obtained better performance than the comparative example.
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.
ｍ外観
クロメート処理後のメッキ表面を肉眼ＩＬＮにより次の
基準で評価した。(m) Appearance The plated surface after chromate treatment was evaluated by naked eye ILN according to the following criteria.
Ｏ黄着色、処理ムラなし
Ｏわずかに黄着色又は処理ムラあす
Δ 黄着色又は処理ムラが明瞭
× 黄着色又は処理ムラが顕著
（２）耐食性
ＪＩＳ −Ｚ −２３７１に準拠した塩水噴霧試験法に
より。O No yellow coloration or uneven treatment O Slight yellow coloration or uneven treatment Tomorrow Δ Yellow coloration or uneven treatment is clear × Yellow coloration or uneven treatment is noticeable (2) Corrosion resistance According to the salt spray test method based on JIS-Z-2371.
特定時間後の発錆状態（白錆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。The state of rust (both white rust and black spots due to partial dissolution of the plating layer) after a specific time was observed and evaluated using the following evaluation criteria.
＠・・・・・発錆１％未満
Ｏ・・・・・ 〃 １％超〜５％未満
△・・・・・ ５％超〜１５％未満
×・・・・・ １５％超〜
（３）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。@・・・・Rust less than 1% O・・・・ More than 1% to less than 5% △・・・・・・ More than 5% to less than 15%×・・・・・・ More than 15% (3 ) Coating Performance A commercially available melamine alkyd white paint was coated to a thickness of 25μ and its performance was evaluated.
？！！！膜に１ｍ間隔の基盤目を１００マス切ったのち
、エリクセン試験機で７ｍ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、
◎１０１Δ、Ｘの４段階で評価。? ! ! ! After cutting 100 base grids at 1 m intervals on the film, extrude it 7 m using an Erichsen tester, perform a peel test with cellophane tape, and visually judge the degree of peeling of the paint film.
◎Evaluated in 4 stages: 101Δ, X.
Ｏが最良である。O is the best.
（３）−２デユポン衝撃試験
デュポン衝撃試験機を用い１重さ５００ｇの重錘を５０
ＣＩ１１高さから落下して、塗膜面に？＃撃を加え、塗
膜の剥離程度を肉眼で判定し、◎１０１Δ。(3)-2 Dupont impact test Using a Dupont impact tester, one weight of 500g was
Falling from a height of CI11 and landing on the paint surface? #A blow was applied and the degree of peeling of the coating film was judged with the naked eye: ◎101Δ.
Ｘの４段階で評価、Ｏが最良である。Evaluation on a four-point scale of X, with O being the best.
（３）−３塗装後嗣食性
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)-3 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２ＩＩＷ
１１以下
Ｏ・・・・・スクラッチ部からの平均フクレＩ４］２ｍ
超〜４ｍ以下
Δ・・・・・スクラッチ部からの平均フクレ巾４ＩＩＩ
Ｉ超〜７ｍ以下
×・・・・・スクラッチ部からの平均フクレ巾７［Ｉ１
１超（発明の効果）
本発明の金属メッキ鋼板用電解クロメート浴によって処
理された電気亜鉛メッキ鋼板、溶融亜鉛メッキ鋼板１合
金化溶融亜鉛メッキ鋼板、溶融アルミメッキ鋼板、溶融
ターンメッキ鋼板、電気鉛メッキ鋼板は何れも外観、塩
水噴霧耐食性、塗装性、塗装後の耐食性等信れも従来の
ものより優れた結果が得られた。◎・・・Average blister width from scratch part 2IIW
11 or less O...Average blistering from scratch area I4] 2m
Super~4m or less Δ...Average blister width from scratch area 4III
More than I~7m or less×・・・Average blister width from scratch area 7 [I1
More than 1 (Effects of the invention) Electrolytic galvanized steel sheets, hot-dip galvanized steel sheets 1 Alloyed hot-dip galvanized steel sheets, hot-dip aluminized steel sheets, hot-dip turn-plated steel sheets, electrolytic lead treated with the electrolytic chromate bath for metal-plated steel sheets of the present invention All of the plated steel plates showed better results than conventional ones in terms of appearance, salt spray corrosion resistance, paintability, and corrosion resistance after painting.
第１図〜第５図はクロメート処理浴で各添加薬剤の濃度
とクロメ−１〜皮膜の耐食性（塩水噴霧状１ｊＩ）、表
面の白色度の関係を示す線図である。第１図はＣｒｙ、
濃度と白色化、第２図はＳｉＯ，４度、第３図はＨＺ
Ｚ ｒ Ｆｂ ６度、第４図はＨ，Ｓｏ、、第５図はＦ
−イオン濃度、第６図はＩ〕１（の影響についてそれぞ
れ示した。
ＳＳＴ （）２Ｈ）臼錆完生工（Ｚ）
白色度（ｗ）
ＳＳＴ（７２Ｈ）臼錆光生率（Ｚ）
白色ｆｆｉ（ｗ’）
ＳＳＴ （７２Ｈ）白錆完生率（Ｚ）FIGS. 1 to 5 are diagrams showing the relationship between the concentration of each additive agent, the corrosion resistance of the chromate-1 coating (salt spray type 1jI), and the whiteness of the surface in a chromate treatment bath. Figure 1 shows Cry,
Concentration and whitening, Figure 2 is SiO, 4 degrees, Figure 3 is HZ
Z r Fb 6 degrees, Figure 4 is H, So, Figure 5 is F
-Ion concentration, Figure 6 shows the influence of I〕1 (SST ()2H) Mill rust photogenicity (Z) Whiteness (w) SST (72H) Mill rust photogenicity (Z) White ffi (w') SST (72H) White rust completion rate (Z)
Claims (1)
ｇ／ｌ、Ｈ＿２ＺｒＦ＿６：０．５〜１０ｇ／ｌ、Ｈ＿
２ＳＯ＿４：０．１〜２ｇ／ｌ、Ｆ＾−イオン：０．１
〜３ｇ／ｌからなる成分の溶液で、ＰＨが２．０〜３．
２に調整したことを特徴とする金属メッキ鋼板用電解ク
ロメート浴。CrO_3: 10-60g/l, SiO_2: 1-20
g/l, H_2ZrF_6:0.5-10g/l, H_
2SO_4: 0.1-2g/l, F^-ion: 0.1
A solution of components consisting of ~3 g/l with a pH of 2.0-3.
An electrolytic chromate bath for metal-plated steel sheets, characterized in that the bath is adjusted to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26825188A JPH02118099A (en) | 1988-10-26 | 1988-10-26 | Electrolytic chromating bath for metal plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26825188A JPH02118099A (en) | 1988-10-26 | 1988-10-26 | Electrolytic chromating bath for metal plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02118099A true JPH02118099A (en) | 1990-05-02 |
| JPH0561358B2 JPH0561358B2 (en) | 1993-09-06 |
Family
ID=17455985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26825188A Granted JPH02118099A (en) | 1988-10-26 | 1988-10-26 | Electrolytic chromating bath for metal plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02118099A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145797A (en) * | 1988-11-28 | 1990-06-05 | Nippon Steel Corp | Electrolytically chromating treatment of steel sheet having metallic surface to be treated |
| US5259937A (en) * | 1991-12-27 | 1993-11-09 | Nihon Parkerizing Co. Ltd. | Process for forming colorless chromate coating film on bright aluminum wheel |
-
1988
- 1988-10-26 JP JP26825188A patent/JPH02118099A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145797A (en) * | 1988-11-28 | 1990-06-05 | Nippon Steel Corp | Electrolytically chromating treatment of steel sheet having metallic surface to be treated |
| US5259937A (en) * | 1991-12-27 | 1993-11-09 | Nihon Parkerizing Co. Ltd. | Process for forming colorless chromate coating film on bright aluminum wheel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0561358B2 (en) | 1993-09-06 |
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