JPS6347400A - Method for chromating metal - Google Patents
Method for chromating metalInfo
- Publication number
- JPS6347400A JPS6347400A JP19042886A JP19042886A JPS6347400A JP S6347400 A JPS6347400 A JP S6347400A JP 19042886 A JP19042886 A JP 19042886A JP 19042886 A JP19042886 A JP 19042886A JP S6347400 A JPS6347400 A JP S6347400A
- Authority
- JP
- Japan
- Prior art keywords
- chromic anhydride
- ions
- moles
- corrosion resistance
- chromate
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 11
- 238000004532 chromating Methods 0.000 title abstract 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 88
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000084 colloidal system Substances 0.000 claims abstract description 22
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 claims abstract 2
- 238000011282 treatment Methods 0.000 claims description 36
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 33
- 238000005260 corrosion Methods 0.000 abstract description 32
- 230000007797 corrosion Effects 0.000 abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 19
- 150000001450 anions Chemical class 0.000 abstract description 13
- 150000001768 cations Chemical class 0.000 abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 29
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 239000008119 colloidal silica Substances 0.000 description 16
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 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 10
- 238000007747 plating Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- -1 chlorine ions Chemical class 0.000 description 7
- 239000010960 cold rolled steel Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000005029 tin-free steel Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- 229910003267 Ni-Co Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910003262 Ni‐Co Inorganic materials 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000283153 Cetacea Species 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は金属の表面処理法に関するものであり、特に金
属の耐食性及び塗料密着性に優れた皮膜をうるクロメー
ト処理法である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for treating the surface of metals, and in particular, a chromate treatment method for producing a film having excellent corrosion resistance and paint adhesion on metals.
ここでいう金属とは鉄、亜鉛、スズ、アルミニウム、ク
ロム、ニッケル、銅およびこれらの合金、あるいはこれ
らに各種のめっきを施こしたものを対象とするが、特に
のがき口板あるいは各種めっきｒＩ仮（合金めっき柵板
を含む）に通用した場合、きわめて短時間の処理で優れ
た・耐蝕性及び塗料密着性を与えることが出来るもので
ある。The metals mentioned here include iron, zinc, tin, aluminum, chromium, nickel, copper, and alloys of these, or those coated with various types of plating, but in particular metals such as plated plates or plated with various types of plating. If it is applied to temporary materials (including alloy plated fence boards), it can provide excellent corrosion resistance and paint adhesion in an extremely short treatment time.
（従来の技術〕
現在、鋼板の最外層にクロメート皮膜をもつ、いわゆる
ティン・フリー・スチールが広く市販され、一般に表面
色調が美しく、また、塗装下地鋼板として優れた特性を
有しているため、缶用その他の用途に広く使用されてい
る。(Prior art) At present, so-called tin-free steel, which has a chromate film on the outermost layer of the steel sheet, is widely available on the market, and generally has a beautiful surface color tone and has excellent properties as a base steel sheet for painting. Widely used for cans and other purposes.
一方、亜鉛めっき鋼板やＺｎ−Ｎｉ系、Ｚｎ−Ｆｅ系、
Ｚｎ−Ｎｉ−Ｃｏ系、Ｚｎ−Ｍｎ系、Ｚｎ−Ｃｏ系等を
はじめとする各種合金めっき鋼板が製造され、家電、自
動車用鋼板、建材などに多量に使用されている。特に家
電や建材については、多くの場合クロメート処理されて
使用されている。On the other hand, galvanized steel sheets, Zn-Ni series, Zn-Fe series,
Various alloy plated steel sheets including Zn-Ni-Co, Zn-Mn, Zn-Co, etc. are manufactured and are used in large quantities in home appliances, automobile steel sheets, building materials, and the like. In particular, home appliances and building materials are often treated with chromate.
これらＺｎ系めっき鋼板のクロメート処理も、すでに公
知のものが多く、種々のクロメート処理法が開発され、
プロパー化されている。Many of these chromate treatments for Zn-based plated steel sheets are already known, and various chromate treatment methods have been developed.
Properized.
例えばクロム酸を主成分とし、他に硫酸（特公昭３９−
７４６１号公報）、リン酸（特公昭３０−３５１４号、
特公昭３５−８９１７号公報、特公昭３６−９５５９号
公報、特公昭３６−９５６０号公報）、ホウ酸（米国特
許第２７３３１９９号、第２７８０５９２号）、ハロゲ
ン（ＣＡ−１Ｆ−）（特公昭３９−１４３６３号公報）
等の各種陰イオンを添加した浴を用いて、鋼板を陰極電
解処理することが行なわれてきた。For example, chromic acid is the main component, and sulfuric acid
7461), phosphoric acid (Japanese Patent Publication No. 30-3514,
Japanese Patent Publication No. 35-8917, Japanese Patent Publication No. 36-9559, Japanese Patent Publication No. 36-9560), boric acid (U.S. Patent No. 2733199, No. 2780592), halogen (CA-1F-) -14363 Publication)
Cathode electrolytic treatment of steel sheets has been carried out using baths containing various anions such as .
しかるに、一般にティン・フリー・スチールは、耐錆性
に関しては未だしの感があり、また、低温焼付型塗料（
たとえばメラミン系塗料）に対する密着性も不十分であ
る。However, in general, tin-free steel is lacking in rust resistance, and low-temperature baking paints (
For example, adhesion to melamine-based paints is also insufficient.
更に、製造工程においても脱脂、酸洗などの一連の前処
理を行ない、その後所定の表面処理を施こすので、多く
の工程が必要となり設備費が大きくなって、製造コスト
もみがき板に比べかなり高くなる欠点がある。Furthermore, in the manufacturing process, a series of pre-treatments such as degreasing and pickling are performed, and then a specified surface treatment is applied, so many steps are required and equipment costs are high, making the manufacturing cost considerably lower than that of polished boards. It has the disadvantage of being expensive.
一方、亜鉛めっき鋼板（合金めっき鋼板を含む）は、耐
食性と塗料密着性を同時にあわせもつクロメート処理は
、きわめてまれであり＠無といっても過言ではない、そ
の多くは、耐食性に優れたものは塗料密着性に劣り、逆
に塗料密着性に優れたものは耐食性に劣る。On the other hand, galvanized steel sheets (including alloy-plated steel sheets) are extremely rarely treated with chromate, which provides both corrosion resistance and paint adhesion. has poor paint adhesion, and conversely, those with excellent paint adhesion have poor corrosion resistance.
本発明は、上記従来の技術の欠点を解決する金属の耐食
性及び塗料密着性に優れた皮膜を有するクロメート処理
法を提供することを目的とするものである。The object of the present invention is to provide a chromate treatment method that solves the drawbacks of the above-mentioned conventional techniques and provides a film with excellent metal corrosion resistance and paint adhesion.
すなわち本発明は、クロム酸浴にカチオンとしてＣｕ、
Ｚｎ、Ｎｉ、Ｃｄ、Ｐｂ、、Ｍｎ５Ｆｅ。That is, the present invention provides Cu as a cation in a chromic acid bath.
Zn, Ni, Cd, Pb, Mn5Fe.
ＣＯのイオンを、１種あるいは２種以上とＦ−１ＣＺ−
１ＳＯ４−、ＰＯ４−一のイオンを１種あるいは２種以
上含有せしめ、かつ、ＳｉＯ□、Ｃｎ、０３、ＦｅｚＯ
ｚ、ＦｅｚＯａ、ＭｇＯ、ＺｎＯ，、Ａ７！２０３、Ｔ
ｉ Ｏｚ、ＳｎＯ□のコロイド（ゾル）を１種あるい
は２種以上含有せしめ、しかも無水クロム酸とカチオン
とアニオン及びコロイドの囲者が、特定の割合になるよ
うに調整した処理液中で、金属を陰極として電解処理す
ることにより、金属上に掻く短時間のうちに皮膜をつく
り、耐食性および塗料密着性をいちじるしく向上させる
ことにより、商品価値を著しく高めるものである。F-1CZ- with one or more CO ions
Contains one or more ions of 1SO4-, PO4-, and SiO□, Cn, 03, FezO
z, FezOa, MgO, ZnO,, A7!203, T
In a processing solution containing one or more types of colloids (sols) of iOz, SnO By electrolytically treating the metal with the metal as a cathode, a film is formed on the metal within a short period of time, significantly improving corrosion resistance and paint adhesion, thereby significantly increasing commercial value.
先ず耐食性、塗装性に関しては、前述した従来公知の特
公昭３９−７４６１号、特公昭３０−３５１４号、特公
昭３５−８９１７号、特公昭３６−９５５９号、特公昭
３６−９５６０号、特公昭３９−１４３６３号クロメー
ト処理法によれば、処理時間を長（する等して耐食性の
良い皮膜を作ると、塗装性は悪くなり、塗装性を良くす
れば、反対に耐食性が悪くなる欠点がある。これに対し
て、本発明の方法によるクロメート皮膜は、前述したよ
うに優れた耐食性と、優れた塗装性を同時に満足するこ
とが出来るものである。First of all, regarding corrosion resistance and paintability, the conventionally known Japanese Patent Publication No. 39-7461, Japanese Patent Publication No. 30-3514, Japanese Patent Publication No. 35-8917, Japanese Patent Publication No. 36-9559, Japanese Patent Publication No. 36-9560, Japanese Patent Publication No. According to the chromate treatment method No. 39-14363, if a film with good corrosion resistance is created by increasing the treatment time, the paintability will deteriorate, and if paintability is improved, the corrosion resistance will deteriorate. On the other hand, the chromate film produced by the method of the present invention can satisfy both excellent corrosion resistance and excellent paintability as described above.
この優れた特性は、無水クロム酸浴に上記カチオンのみ
を含有せしめた場合、あるいは上記アニオンのみを含有
せしめた場合、あるいはコロイドのみを含有せしめた場
合には得られないもので、囲者の相乗効果によるもので
ある。This excellent property cannot be obtained when the chromic anhydride bath contains only the above cations, only the above anions, or only colloids; This is due to the effect.
この際の無水クロム酸、カチオン、アニオン、コロイド
、の間には、次の関係がなければならないことを見い出
した。It has been found that the following relationship must exist among chromic anhydride, cation, anion, and colloid in this case.
かつ、
かつ、
かつ、
上記の条件を同時に満足する処理浴中で、金属を陰極で
電解処理した場合、住成される皮膜は耐食性、塗装密着
性がいちじるしく向上することを確ｔ＝ Ｌ’た。And, and, and, it was confirmed that when a metal is electrolytically treated with a cathode in a treatment bath that satisfies the above conditions at the same time, the corrosion resistance and paint adhesion of the resulting film are significantly improved. .
第１図、第２図、第３図は上記（１）、（２）、（３）
をかえた場合、第４図、第５図は上記（１）、（２）、
（３）を固定し、無水クロム酸の濃度をかえた場合の本
発明の処理による鋼板の耐食性、塗料密着性の影響を調
べたものである。Figures 1, 2, and 3 are shown in (1), (2), and (3) above.
4 and 5 are the above (1), (2),
The effects of the treatment of the present invention on the corrosion resistance and paint adhesion of steel plates were investigated when (3) was fixed and the concentration of chromic anhydride was varied.
すなわち、第１図の曲＆’１ｌ（ａ）は無水クロム酸５
０ ｇ ／ １に、炭酸コバルトを０．４４〜４４ｇ／
ｌ含有せしめ
）容重している無水クロム酸のモル数
とし、さらに塩素イオンを０．０１８〜１．８ｇ／ｌ含
有せしめ
とし、さらにコロイダルシリカＳ１０！を種々加え
含有せしめたコロイダルシリカ（Ｓｉｎ、）のモル数を
かえた場合の耐食性の変化を示したものである。In other words, the song &'1l(a) in Figure 1 is composed of chromic anhydride 5
0 g/1, and 0.44 to 44 g/1 of cobalt carbonate.
1) The number of moles of chromic anhydride is the same as the volume, and 0.018 to 1.8 g/l of chlorine ion is added, and colloidal silica S10! This figure shows the change in corrosion resistance when the number of moles of colloidal silica (Sin) containing various amounts is changed.
曲線（ｂ）は無水クロム酸５０ ｇ／Ｉ！、に、＃ｌ酸
コバルトを０．４４〜４４ ｇ／ｌ含有せしめ、とし、
さらに塩素イオンを０−０．０１８ｇ／ｘ含有せしめ
）漂している舗［７にクロム酸のモル数とし、さらにコ
ロイダルシリカ（Ｓｉｎ２）を種々加え、
含有せしめたコロイダルシリカ（Ｓ ｉ ＯＪのモル数
溶解している鯨クロム酸のモル数
をかえた場合の耐食性の変化を示したものである。Curve (b) shows 50 g/I of chromic anhydride! , containing 0.44 to 44 g/l of cobalt #l acid,
In addition, the number of moles of chromic acid is set to 7, and various colloidal silica (Sin2) is added to the colloidal silica (moles of Si OJ) containing 0 to 0.018 g/x of chlorine ions. This figure shows the change in corrosion resistance when the number of moles of dissolved whale chromic acid is changed.
更に曲ｂｉｃｃ）は、無水クロＬｆｌ！ ５０ ｇ／
Ｊ ニ、炭酸コバルトを０．４４〜４４ ｇ／ｌ含有せ
しめ、とし、さらに塩素イオンを１．８ｇ／１以上含有
せしめ
含有せしめた塩素イオンのダラムイオン数溶解している
無水クロム酸のモノｐ
を０．１超とし、さらにコロイダルシリカを種々加え
含有せしめたコロイダルシリカ（Ｓｉｎりのモル数をか
えた場合の耐食性の変化を示したものである。Furthermore, the song BICC) is anhydrous black Lfl! 50g/
J D. Contains 0.44 to 44 g/l of cobalt carbonate, and further contains 1.8 g/l or more of chlorine ions.Number of dulam ions of chlorine ions dissolved in monop of chromic anhydride. The graph shows the change in corrosion resistance when the number of moles of colloidal silica (Sin) was changed, and the number of moles of colloidal silica was set to exceed 0.1, and various colloidal silicas were added.
次に第２図の曲！ （ａ）、（ｂ）、（Ｃ）は無水クロ
ムＭ ５０ ｇ ／ １に、炭酸コバルトをｏ−０，４
４ｇ／Ｉｌ含有せしめ
とし、第１図と同じように
及びＯ１■超にそれぞれａ各値に対し
溶解しているＷロム酸のモル数
を示したものである。Next is the song in Figure 2! (a), (b), and (C) are chromium anhydride M 50 g/1 and cobalt carbonate o-0.4
As shown in Figure 1, the number of moles of W romic acid dissolved for each value of a is shown in the same manner as in Figure 1 and in excess of O1.
次に第３図の曲線（ａ）、（ｂ）、（Ｃ）は、無水クロ
ム酸５０ ｇ／Ｍに、炭酸コハル１を４−１ｇ／１以上
含有せしめ
とし、第１図と同じように
及び０．１１にそれぞれ改各値に対し
しかして第１図、第２図、第３図から明らかなように、
耐食性については
）容質している鯨クロム酸のモ月、蔓交溶解している無
水クロム酸のモノ１汐
含有せしめたコロイダルシリカ（Ｓ ｉ Ｏｘ）のモル
数７容罫している無水クロム酸のモル数
を特定の割合にしたとき、初めて優れた特性を示し、こ
の特性は無水クロム酸浴に、Ｃ０４゛イオンのみを、あ
るいは塩素イオンのみを、あるいはコロイダルシリカ（
Ｓｉｎｇ）のみを加えた場合よりもはるかに優れたもの
で、これはアニオン（塩素イオン）とカチオン（Ｃｏ０
′″イオン）及びコロイダルシリカ（Ｓｉｆｔ）の相乗
効果によるものである。Next, curves (a), (b), and (C) in Fig. 3 are obtained in the same manner as in Fig. 1, when 50 g/M of chromic acid anhydride contains 4-1 g/1 or more of Kohar 1 carbonate. and 0.11, respectively. However, as is clear from Figures 1, 2, and 3,
As for corrosion resistance) 7 molar volumes of colloidal silica (S i Ox) containing 1 mole of whale chromic acid and 1 mole of dissolved chromic acid anhydride. Excellent properties are shown for the first time when the number of moles of acid is set to a specific ratio, and this property is demonstrated by adding only C04 ions, only chlorine ions, or colloidal silica (
This is much better than adding only anion (chloride ion) and cation (Co0
This is due to the synergistic effect of colloidal silica (Sift) and colloidal silica (Sift).
次に第４図に
溶解している無水クロム酸のモル数
含有せしめたコロイダルシリカのモノｐを第１図、第２
図、第３図と同様に、種々かえた場合の塗料密着性の変
化を示したものである。Next, the colloidal silica monop containing the number of moles of chromic anhydride dissolved in Figure 4 is shown in Figures 1 and 2.
Similarly to FIG. 3, it shows changes in paint adhesion when various changes were made.
第４図、第５図、第６図の曲線（ａ） ′、（ｂ）′、
（Ｃ）′は第１図、第２図、第３図（ａ）、（ｂ）、（
ｃ）と同条件である。Curves (a)', (b)' in Figures 4, 5, and 6,
(C)' are Fig. 1, Fig. 2, Fig. 3 (a), (b), (
The conditions are the same as c).
第４図、第５図、第６図から明らかなように、塗料密着
性については
）蕩了している無水クロム酸のモ／Ｌ１次で
）窯している琳クロム酸のモル数
でかつ
溶解している無水クロム酸のモル数
のとき優れた特性を示す。As is clear from Figures 4, 5, and 6, paint adhesion depends on the number of moles of chromic acid in the kiln and the number of moles of chromic acid in the kiln. It exhibits excellent properties when the number of moles of chromic anhydride dissolved.
次に、第７図、第８図に溶解している無水クロム酸のモ
ル数を種々かえ、それに応して熔解しているｊ吟とクロ
ム酸のモル数
７容罫している無水クロム酸のモル数
（容騨している；腹にクロム酸のモル数になるようにＧ
ｏ ”イオン、塩素イオン、コロイダルシリカを含有
せしめた場合の耐食性及び塗料密着性を示す。Next, the number of moles of chromic anhydride dissolved in Figures 7 and 8 was varied, and the number of moles of dissolved chromic acid and chromic acid in a 7-volume box was adjusted accordingly. The number of moles of G
Shows corrosion resistance and paint adhesion when containing o'' ions, chloride ions, and colloidal silica.
第７図、第８図から明らかなように、無水クロム酸の１
度は０．０５モル／ｐ〜５モル／ｌが過当である。As is clear from Figures 7 and 8, 1 of chromic anhydride
A suitable degree is 0.05 mol/p to 5 mol/l.
なお、第１図、第２図、第３図、第４図、第５図、第６
図は金属イオンとしてＣＯ゛イオンを、アニオンとして
Ｃｌ−イオンを、コロイド（ゾル）としてコロイダルシ
リカ（Ｓｉ０２）を含有せしめた場合について示したが
、コロイダルシリカを含めて、他のコロイドを含有せし
めた場合に、最高の耐食性、塗料密着性が得られる
含有せしめたＣＯ°１イオンのダラムイオン数）藝騨し
ている無水クロム酸のモノ１次かどのようなものである
か
）容質している無水クロム酸のモル数
第１表及び第２表である。In addition, Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6
The figure shows the case in which CO' ions are contained as metal ions, Cl- ions as anions, and colloidal silica (Si02) as a colloid (sol), but other colloids including colloidal silica are contained. In this case, the highest corrosion resistance and paint adhesion can be obtained (the number of Durham ions in the CO° 1 ion contained). Tables 1 and 2 show the number of moles of chromic anhydride present.
すなわち、第１表及び第２表は無水クロム酸５０ ｇｅ
ｌにそれぞれＳ ｉ Ｏｔ 、 Ｃｎｚｏ＊ −Ｆ’３
ｘＯｓ−ＦｅコｏａＳＭｇＯ−、Ｚｎ０ｔ、Ａｌ２Ｏ３
、ＴｌＯ！、ＳｎＯ，のコロイド（ゾル）をとなるよう
に含有せしめ、かつ
）容質している無水クロム酸のモノｐ
となるように含有せしめＣｏ”イオンの？】度をかえた
処理浴中で、電気亜鉛めっき鋼板を陰極電解処理した場
合の皮膜特性を示す。That is, Tables 1 and 2 show that 50 ge of chromic anhydride
S i Ot and Cnzo* −F'3 for l, respectively.
xOs-FeCoaSMgO-, Zn0t, Al2O3
, TlO! , SnO, and colloids (sols) of chromic anhydride contained in the solution, and colloids (sols) of chromic anhydride held therein. This figure shows the film characteristics when an electrolytic galvanized steel sheet is subjected to cathodic electrolytic treatment.
電解条件は、電流密度２０Ａ／ｄｍ”、電解時間１秒、
浴温４５℃である。The electrolysis conditions were: current density 20A/dm'', electrolysis time 1 second,
The bath temperature was 45°C.
第１表はＣＯ゛°イオン濃度と耐食性の関係を（以下余
白、次頁へつづく）
第１表
第１表の耐食性は、ＪＩＳ−Ｚ−２３７１規格に準拠し
た塩水噴霧試験により（食塩水、・壱度５％、槽内温度
３５℃、噴霧圧力２０Ｐｓｊ） ２４０時間後の発錆状
況を肉眼で、■、Ｏ１△、×の４段階で評価し、◎が最
良である。Table 1 shows the relationship between CO゛° ion concentration and corrosion resistance (see the margin below, continued on the next page).・Ability: 5%, temperature inside the tank: 35°C, spray pressure: 20Psj) The state of rust after 240 hours was evaluated with the naked eye on a 4-level scale of ■, O1△, and ×, with ◎ being the best.
第２表の塗料はメラミン系（焼付温度１２０℃）、アク
リル系（焼付温度１８０℃）の焼付塗料を使用し、塗料
密着評価法はＪＩｓ−５４００によす描画、ゴバン目エ
リクセン、衝撃、２Ｔ折曲の各試験を行ない、これらの
綜合評価によって判定した。評価は◎、○、△、×の４
段階判定で行ない◎が最良である。The paints in Table 2 are melamine-based (baking temperature: 120°C) and acrylic-based (baking temperature: 180°C) baking paints, and the paint adhesion evaluation method is JIs-5400 drawing, Goban Eriksen, impact, and 2T. Each bending test was conducted and judgment was made based on the comprehensive evaluation of these tests. Rating: ◎, ○, △, ×
Perform the evaluation in stages, with ◎ being the best.
第２表はＣｏ−イオン濃度と塗料密着性の関係（以下余
白、次頁へつづく）
第２表
なお、塩素イオンにかえてＦ−イオンあるいは５Ｏ４−
−イオン、ＰＯ，−−−イオンを含有せしめた場合も、
全く同様な結果が得られた。Table 2 shows the relationship between Co- ion concentration and paint adhesion (the following margins are continued on the next page).
- ion, PO, --- ion also contained,
Exactly similar results were obtained.
また、Ｃｏ ”イオンのかわりにＣｕ ”、Ｚｎ４＋、
Ｎ１３９、Ｃｄ ”、Ｐ ｂ ” 、Ｍ ｎ ”、Ｆ
ｅ ”イオンを含有せしめた場合も、全く同様な結果が
得られた。Also, instead of Co “ion”, Cu”, Zn4+,
N139, Cd ”, P b ”, M n ”, F
Exactly the same results were obtained when e'' ions were included.
第１図〜第８図及び第１表、第２表から明らかなごとく
、耐食性及び塗料密着性の両者を満足する無水クロム酸
濃度は、０．０５モル／ｌ〜５モル／ｌ、
熔解している無水クロム酸のモル数
溶解している無水クロム酸のモル数
であることが判る。As is clear from Figures 1 to 8 and Tables 1 and 2, the concentration of chromic anhydride that satisfies both corrosion resistance and paint adhesion is 0.05 mol/l to 5 mol/l. It can be seen that the number of moles of chromic anhydride in the solution is the number of moles of chromic anhydride dissolved in it.
アニオンとして臭素イオン、ヨウ素イオンなどを含有せ
しめて実施したが、全く効果はなかった。Although attempts were made to include bromide ions, iodine ions, etc. as anions, there was no effect at all.
この際、無水クロム酸と無水クロム酸、クロム酸塩、垂
クロム酸塩により含有せしめることができ、この場合ク
ロム酸塩、重クロム酸塩は無水クロム酸に換算して０．
０５〜５モル／１含有せしめればよい。At this time, chromic anhydride, chromic acid anhydride, chromate, and dichromate can be contained. In this case, the chromate and dichromate are 0.00% in terms of chromic anhydride.
The content may be 05 to 5 mol/1.
また、カチオンは炭酸塩、酸化物、水酸化物あるいは有
機金属等の形で添加すればよい。また、アニオンも無ｉ
酸としての他金属塩あるいは有機物等の形で添加しても
よい。Further, the cation may be added in the form of carbonate, oxide, hydroxide, organic metal, or the like. Also, there are no anions.
In addition to being an acid, it may be added in the form of a metal salt or an organic substance.
しかし、いずれの場合でも添加して解離したカチオン、
アニオンが、上記比を満足するように含有せしめなけれ
ばならない点に注意を要する。However, in any case, the added and dissociated cation,
Care must be taken that the anion must be contained so as to satisfy the above ratio.
ここで、コロイド（ゾル）を添加すると、クロメート皮
膜の性能がさらに改善されるのは次の理由による。The reason why the addition of colloid (sol) further improves the performance of the chromate film is as follows.
すなわち、本発明におけるように、重金属イオンとコロ
イドが共存すると、重金属イオンがコロイドに吸着し、
コロイドはイオン化する。従って、電解するとコロイド
もクロメート皮膜中に容易に共析し、従来公知の皮膜と
は、まったく異なるコロイドが皮膜中に存在するクロメ
ート皮膜が形成される。このようにコロイドとクロメー
トが共存した構造の皮膜の形成によって、さらに優れた
性能が得られる。That is, when heavy metal ions and colloid coexist as in the present invention, the heavy metal ions are adsorbed to the colloid,
Colloids become ionized. Therefore, when electrolyzed, colloids are easily eutectoid in the chromate film, and a chromate film is formed in which colloids are present in the film, which is completely different from conventionally known films. By forming a film with a structure in which colloid and chromate coexist in this way, even better performance can be obtained.
本発明の処理法における電解処理条件は、使用浴温２０
〜８０℃が効果的であり、電流密度は０．５〜１２０
Ａ ／ｄｌｌ”、電気量はＩＣ／ｄ＋ｗ”以上で、処理
時間は０．１秒以上でよい。電気量が多くなるにつれ、
耐食性はさらに向上するが、塗料密着性はかわらない。The electrolytic treatment conditions in the treatment method of the present invention include a bath temperature of 20
~80℃ is effective, current density is 0.5~120
A/dll'', the amount of electricity may be IC/d+w'' or more, and the processing time may be 0.1 seconds or more. As the amount of electricity increases,
Corrosion resistance is further improved, but paint adhesion remains the same.
通常のめっき用原板は、冷間圧延後焼鈍及び調質圧延し
たものが用いられるが、その表面にある酸化皮膜は、め
っきの密着性を悪くするので、通常脱脂、酸洗されてめ
っきされる。しかるに本発明の処理法によれば、通常の
めっき原板に脱脂、酸洗の前処理をせずに直接適用する
ことができる。Normally, the original plate for plating is cold-rolled, then annealed and temper-rolled, but the oxide film on its surface impairs the adhesion of the plating, so it is usually degreased and pickled before plating. . However, according to the treatment method of the present invention, it can be directly applied to ordinary plating plates without pretreatment such as degreasing and pickling.
すなわち、公知のクロメート処理では、ローモ板を使用
しても前処理が十分行なわれないと、皮膜が均一に生成
されず、また、密着性の悪いものとなるが、本発明の処
理においては耐食性、塗料密着性共に優れた皮膜が生成
される。In other words, in the known chromate treatment, even if a Romo plate is used, if the pretreatment is not performed sufficiently, the film will not be formed uniformly and the adhesion will be poor, but in the treatment of the present invention, the corrosion resistance , a film with excellent paint adhesion is produced.
前処理を行なわないで、めっき原板に本発明の処理を施
こすに際しては、■いきなり陰極電解処理する。■同じ
処理浴で最初デイツプし、その後陰極電解処理する。■
同じ処理浴で最初陽極電解処理し、その後陰極電解処理
するなどの方法があるが、いずれにおいてもきわめて優
れた性能が得られる。When applying the treatment of the present invention to a plating original plate without pretreatment, (1) immediately cathodic electrolytic treatment is performed. ■First dip in the same treatment bath, then cathodic electrolysis treatment. ■
There are methods such as first carrying out anodic electrolysis treatment and then cathodic electrolysis treatment in the same treatment bath, but extremely excellent performance can be obtained with either method.
また、上述したように高速処理が可能なこと、前処理が
省略出来、処理装置がきわめてコンパクトですむことな
ど、多くの優れた点を有する。Furthermore, as mentioned above, it has many advantages, such as high-speed processing, the ability to omit pre-processing, and the ability to use an extremely compact processing device.
また、処理する鋼板は冷延鋼板、Ｚｎめっき鋼板あるい
はＺｎ−Ｎｉ系、Ｚｎ−Ｎｉ−Ｃｏ系、Ｚｎ−Ｆｅ系合
金めっき鋼板あるいはＳｎめっき網板など、いずれの素
材においても、容易にクロメート皮膜を形成することが
できる。In addition, the chromate film can be easily formed on any of the steel sheets to be treated, such as cold-rolled steel sheets, Zn-plated steel sheets, Zn-Ni-based, Zn-Ni-Co-based, Zn-Fe-based alloy-plated steel sheets, or Sn-plated mesh sheets. can be formed.
以下本発明の実施例を比較例と共に示す。Examples of the present invention will be shown below along with comparative examples.
〈実施例１〉 冷延鋼板を次の条件で陰極電解処理した。<Example 1> A cold-rolled steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ Ｏｓ ５０ ｇ ／ ＩＣｏ ＣＯ３
５ｇ ／ Ｅ
ＨＣｌ Ｏ，２ｇ／β
コロイダルシリカ（Ｓ ｉ Ｏｚ） １ ｇ ／β含
存せしめたＣｏ１４イオンのグラムイオン数熔解してい
る無水クロム酸のモル数
）欝している無水クロム酸のモル数
電解条件 電流密度 ２０Ａ／ｄｒａ”電解時間
１秒
浴 温 ４５ ℃
〈実施例２〉
冷延鋼板を次の条件で陰極電解処理した。Cn Os 50 g / ICo CO3
5 g / E HCl O, 2 g / β Colloidal silica (S i Oz) 1 g / β Number of grams of Co14 ions included Number of moles of dissolved chromic anhydride) Moles of condensed chromic anhydride Electrolysis conditions Current density 20A/dra” Electrolysis time
1 second bath temperature 45°C <Example 2> A cold rolled steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
ＣｎＯｓ ６０ｇ／ｌ
ＺｎＣＯ５５ｇ／ｊ！
ＮＩＧＯ２５ｇ ／ Ｉ
ＨＦ ０．４ｇ／ｊ！
コロイダルシリカ（Ｓ Ｉ Ｏり １．５ｇ ／ Ｉ
ｌ）漂している無水クロム酸のモル数
・含何せしめたＦ−イオンのグラムイオン数電解条件
電流密度 ４０Ａ／ｃｌ＋ａ”電解時間 ０．
５秒
浴 温 ４５ ℃
〈実施例３〉
冷延鋼板を次の条件で陰極電解処理した。CnOs 60g/l ZnCO55g/j! NIGO25g/IHF 0.4g/j! Colloidal silica (SIO 1.5g/I
l) Number of moles of floating chromic acid anhydride/gram ion number of F- ions contained Electrolytic conditions
Current density 40A/cl+a” Electrolysis time 0.
5 seconds bath temperature 45°C <Example 3> A cold rolled steel plate was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ Ｏｘ ８０ ｇ ／ ＩＮ ｉ ＣＯ
ｓ １０ ｇ ／ ｌＨＣｌ ０．
２ｇ／Ｉ
Ａ１富０コゾル ０．１ｇ／ｌ
）鏝している無水クロム酸のモル数
電解条件 電流密度 ６０Ａ／ｄ＋ｍ”電解時間
０．２秒
浴 温 ４５ ℃
〈実施例４〉
Ｚｎめっき鋼板を次の条件で陰極電解処理した。Cn Ox 80 g/IN i CO
s 10 g/lHCl 0.
2g/I A1 rich 0 cosol 0.1g/l) Number of moles of chromic anhydride being troweled Electrolysis conditions Current density 60A/d+m" Electrolysis time
0.2 seconds bath temperature 45°C <Example 4> A Zn-plated steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ Ｏｓ ４０ ｇ ／ ｊＩＣｏ Ｃ
Ｏ３５ｇ ／ １ｔ
ＨｚＳ ０４ ０．５ｇ ／ ｊ１ＭｇＯゾル
０．５ｇ／Ｉ
Ｔ ｉ Ｏ，ゾル ０．５ｇ／ｌ熔解している無
水クロム酸のモノｐ
熔解している無水クロム酸のモノル
ミ解条件 電流密度 ８０Ａ／ｄＩＩ＋”電解時間
０．２秒
浴 温 ５０ ℃
〈実施例５）
Ｚｎ−Ｎｌ系合金めっき鋼板を次の条件で陰極電解処理
した。CnOs 40g/jICoC
O35g/1t HzS 04 0.5g/j1MgO sol 0.5g/I T i O, sol 0.5g/l Monop of dissolved chromic anhydride Monoluminization conditions of dissolved chromic anhydride Current density 80A /dII+'' Electrolysis time: 0.2 seconds Bath temperature: 50°C (Example 5) A Zn-Nl alloy plated steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ ０３ １００ ｇ ／ ＩＣｕ ＣＯｓ
１０ ｇ ／ ｌＨ３ＰＯ４１，Ｏｇ／Ｉ
Ｃｎ、Ｏ，ゾル １．５ｇ１ｌ
熔解している琳クロム酸のモル数
溶解している無水クロム酸のモル数
電解条件 電流密度 １００ Ａ ／ｄａ”電解時
間 ０．１秒
浴 温 ５５ ℃
（実施例６〉
Ｚｎ−Ｎｉ−Ｃｏ系合金めっき鋼板を次の条件で陰極電
解処理した。Cn 03 100 g/ICu COs
10 g/lH3PO41,Og/I Cn, O, sol 1.5g1l Number of moles of dissolved chromic acid Number of moles of dissolved chromic acid anhydride Electrolytic conditions Current density 100 A/da" Electrolysis time 0.1 Second bath temperature: 55°C (Example 6) A Zn-Ni-Co alloy plated steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ Ｏｚ ５ ０ ｇ ／
ＩＰ ｂ ＣＯｚ ５ ｇ
／ １ｌ−１０ｎ ０．２ｇ／Ｉ
Ｉ！ＺｎＱ、ゾル １．０ｇ／ｊ！
ＴｔＭ条件 電流密度 ４０Ａ／ｄｍ’電解時間
０．４秒
浴 温 ４５ ℃
〈実施例７〉
Ｚｎ−Ｆｅ系合金めっき鋼板を次の条件で、陰１２ｊ電
解処理した。Cn Oz 50 g /
IP b COz 5 g
/ 1l-10n 0.2g/I
I! ZnQ, Sol 1.0g/j! TtM conditions Current density 40A/dm' Electrolysis time
0.4 seconds bath temperature 45°C <Example 7> A Zn-Fe alloy plated steel sheet was subjected to negative 12J electrolytic treatment under the following conditions.
ＣｎＯ３５０ｇ／Ｉ
Ｆ ｅ ＣＯｓ ５ ｇ ／ ｊ！ＨＣｌ
Ｏ，２ｇ／ＩＦｅｚＱコゾル
１ ｇ／ｌ
熔解している無水クロム酸のモル数
電解条件 電流密度 ２ＯＡ／ｄｍ”電解時間
１秒
浴 温 ５ ｏ ℃
く比較例１＞
冷延綱板を次の条件で陰極電解処理した。CnO350g/IFeCOs 5g/j! HCl
O, 2g/IFezQ cosol
1 g/l Number of moles of melted chromic anhydride Electrolytic conditions Current density 2OA/dm Electrolysis time
Comparative Example 1> A cold-rolled steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ Ｏｓ ５０ ｇ ／ ＩＨｔ５０４
０．２ｇ／ｌ
電解条件 電流密度 ４０Ａ／ｄｍ”電解時間
２秒
浴 ／ＩＡ６ ０ ℃
く比較例２）
市販のティンフリースチールの無塗油のものく比較例３
〉
Ｚｎめっき鋼板を次の条件で陰極電解処理した。CnOs 50g/IHt504
0.2g/l Electrolysis conditions Current density 40A/dm” Electrolysis time
2 seconds bath /IA6 0℃ Comparative Example 2) Commercially available tin-free steel without oil coating Comparative Example 3
> A Zn-plated steel sheet was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ０． ５０ｇ／ｆ
１１□Ｓ０． ０．３ｇ／ｌ
電解条件 電流密度 ６０Ａ／ｄｍ”電解時間
２秒
浴 １ ５５ ℃
く比較例４〉
Ｚｎ−Ｎｉ系合金めっきＰ４仮を次の条件で陰極電解処
理した。Cn0. 50g/f 11□S0. 0.3g/l Electrolysis conditions Current density 60A/dm” Electrolysis time
Comparative Example 4 Zn-Ni alloy plating P4 temporary was subjected to cathodic electrolysis treatment under the following conditions.
Ｃｎ Ｏｙ ５０ ｇ ／ Ｉ！Ｈ２Ｓ（
１０，２５ｇ／１２
電解条件 電流密度 ５０ Ａ ／ ｄｍ”電解時
間 ２秒
浴 温 ６０ ℃
第３表に各実施例及び比較例の塩水噴霧試験による耐食
性を示し、第４表に塗料密着性を示す。Cn Oy 50 g/I! H2S(
10.25g/12 Electrolysis conditions: Current density: 50 A/dm Electrolysis time: 2 seconds Bath temperature: 60°C Table 3 shows the corrosion resistance of each example and comparative example by salt spray test, and Table 4 shows the paint adhesion. .
（以下余白、次頁へつづく） 第３表（１） 第３表（２） 第３表（３） 第４表（１） 第４表（２） 塗月密着性ＬＫ験法及び評価法は表と同し。(Margin below, continued on next page) Table 3 (1) Table 3 (2) Table 3 (3) Table 4 (1) Table 4 (2) The coating adhesion LK test method and evaluation method are the same as in the table.
第３表から明らかなように、冷延鋼板に本発明を実施し
た場合、耐食性は５ＳＴ４８ｈではまったく変化なく、
７２ｈでわずかに（０，０１％以下）赤錆が発生した程
度であるが、公知のクロメート浴で処理した場合〈比較
例１〉あるいは市販されているＴＦＳ （比較例２〉で
は、５ＳＴＳｈ後でかなり赤錆が発生しく１０％以上）
、２４ｈでは５０％以上発生した。As is clear from Table 3, when the present invention is applied to cold-rolled steel sheets, the corrosion resistance does not change at all in 5ST48h.
Only a small amount (less than 0.01%) of red rust occurred after 72 hours, but when treated with a known chromate bath (Comparative Example 1) or commercially available TFS (Comparative Example 2), there was considerable rust after 5STSh. Red rust occurs (more than 10%)
, 50% or more occurred in 24 hours.
また、電気亜鉛めっき鋼板に本発明を実施した場合、耐
食性は５ＳＴ１４４ｈで白錆が０．５％はど発生したの
に対し、公知のクロメート浴で処理した場合〈比較例３
ンでは、５ＳＴ７２ｈ後で、すでに白錆が２〜３％発生
した。In addition, when the present invention was applied to an electrogalvanized steel sheet, the corrosion resistance was 5ST144h and 0.5% white rust occurred, whereas when treated with a known chromate bath <Comparative Example 3
In the case of 5ST, 2 to 3% white rust had already occurred after 72 hours.
また、各種合金めっき鋼板に本発明を実施した場合、耐
食性は５ＳＴ１０００ｈでも発錆は情無であるのに対し
、公知のクロメート浴で処理した場合〈比較例４〉では
、５ＳＴ４００ｈ時点で、すてに白錆が５０％前後発生
していた。Furthermore, when the present invention is applied to various alloy-plated steel sheets, the corrosion resistance is poor even after 5ST 1000h, whereas when treated with a known chromate bath (Comparative Example 4), the corrosion resistance is poor even after 5ST 400h. Approximately 50% of the parts had white rust.
一方塗料密着性は本発明を実施した場合、ｓｐＣ，電気
Ｚｎめっき、各種合金めっきなど素材のいかんにかかわ
らず、また、塗料のいかんにかかわらず、きわめて優れ
た塗料密着性を示すが、公知のクロメート処理を実施し
た場合、高温焼付型塗料の場合は、まあまあの塗料密着
性を示すが、低温焼付型塗料の場合は塗膜はほぼ全面剥
離する。On the other hand, when the present invention is implemented, extremely excellent paint adhesion is exhibited regardless of the material used, such as spC, electrolytic Zn plating, or various alloy plating, and regardless of the paint used. When chromate treatment is performed, high-temperature baking paints exhibit fair paint adhesion, but low-temperature baking paints cause the paint film to peel off almost entirely.
従来、公知のクロメート処理には、耐食性と塗料密着性
を同時に十分満足するものは存在しなかった。これに対
し無水クロム酸、特殊なアニオン、カチオン及びコロイ
ド（ゾル）を本発明の比率で混合した浴で処理すると、
上記囲者の相乗効果と共析によって、きわめて優れた耐
食性と塗料密着性とが同時に得られる優れた皮膜が形成
され、本発明を適用することにより、その経済的効果は
きわめて大なるものである。Hitherto, there has been no known chromate treatment that satisfies both corrosion resistance and paint adhesion. On the other hand, when treated with a bath containing chromic anhydride, special anions, cations, and colloids (sols) in the proportions of the present invention,
Due to the synergistic effect and eutectoid of the above-mentioned enclosures, an excellent film is formed that provides extremely excellent corrosion resistance and paint adhesion at the same time, and by applying the present invention, the economic effect is extremely large. .
第１（ｆｆｌ〜第３図は無水クロム酸浴中のカチオン、
アニオン、コロイドの耐食性に与える影響を調査した図
表、第４図〜第６図は無水クロム酸浴中のカチオン、ア
ニオン、コロイドの塗料密着性に与える影響を調査した
図表、第７図〜第８図はカチオン、アニオン、コロイド
の共存した浴での無水クロム酸の耐食性及び塗料密着性
に与える影Ｃを調査した図表である。1st (ffl~Figure 3 shows cations in chromic anhydride bath,
Figures 4 to 6 are graphs investigating the effects of anions and colloids on corrosion resistance. The figure is a chart that investigates the influence of chromic anhydride on corrosion resistance and paint adhesion in a bath in which cations, anions, and colloids coexist.
Claims (1)
、無水クロム酸に換算して、０．０５モル／ｌ〜５モル
／ｌ含む浴にＣｕ、Ｎｉ、Ｚｎ、Ｆｅ、Ｃｄ、Ｐｂ、Ｍ
ｎ、Ｃｏのイオンを１種または２種以上含有せしめ、さ
らにＣｌ＾−、Ｆ＾−、ＳＯ＿４＾−＾−、ＰＯ＿４＾
−＾−＾−イオンを、１種または２種以上含有せしめ、
さらにＳｉＯ＿２、Ｃｎ＿２Ｏ＿３、Ｆｅ＿２Ｏ＿３、
Ｆｅ＿３Ｏ＿４、ＭｇＯ、ＺｎＯ＿２、Ａｌ＿２Ｏ＿３
、のコロイド（ゾル）の１種あるいは２種以上含有せし
め、かつ、 熔解しているクロム以外の金属イオンのグラムイオン数
＝０．００５〜０．５ 無水クロム酸又はクロム酸塩若しくは重クロム酸塩を無
水クロム酸に換算したモル数 かつ、 溶解しているＣｌ＾−、Ｆ＾−、ＳＯ＿４＾−＾−、Ｐ
Ｏ＿４＾−＾−＾−イオンのグラムイオン数 ＝０．００１〜０．１ 無水クロム酸又はクロム酸塩若しくは重クロム酸塩を無
水クロム酸に換算したモル数 かつ、 溶解しているＳｉＯ＿２、Ｃｎ＿２Ｏ＿３、Ｆｅ＿２Ｏ
＿３、Ｆｅ＿３Ｏ＿４、ＭｇＯ、ＺｎＯ＿２、Ａｌ＿２
Ｏ＿３のコロイド（ゾル）のモル数＝０．００１〜０．
８ 無水クロム酸又はクロム酸塩若しくは重クロム酸塩を無
水クロム酸に換算したモル数 とした浴で、金属を陰極として電解処理することを特徴
とする金属のクロメート処理法。[Claims] Cu, Ni, Zn, Fe, Cd, Pb, M
Contains one or more types of n, Co ions, and further contains Cl^-, F^-, SO_4^-^-, PO_4^
Containing one or more types of -^-^- ions,
Furthermore, SiO_2, Cn_2O_3, Fe_2O_3,
Fe_3O_4, MgO, ZnO_2, Al_2O_3
contains one or more types of colloids (sols), and number of dissolved metal ions other than chromium in grams of ions = 0.005 to 0.5 chromic anhydride, chromate, or dichromic acid Number of moles of salt converted to chromic anhydride and dissolved Cl^-, F^-, SO_4^-^-, P
Number of gram ions of O_4^-^-^- ions = 0.001 to 0.1 Number of moles of chromic anhydride, chromate, or dichromate converted to chromic anhydride, and dissolved SiO_2, Cn_2O_3 , Fe_2O
_3, Fe_3O_4, MgO, ZnO_2, Al_2
Number of moles of colloid (sol) of O_3 = 0.001 to 0.
8. A method for chromate treatment of metals, which is characterized by electrolytically treating the metal in a bath containing chromic anhydride, chromate, or dichromate in the number of moles calculated in terms of chromic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19042886A JPH0672316B2 (en) | 1986-08-15 | 1986-08-15 | Metal chromating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19042886A JPH0672316B2 (en) | 1986-08-15 | 1986-08-15 | Metal chromating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6347400A true JPS6347400A (en) | 1988-02-29 |
| JPH0672316B2 JPH0672316B2 (en) | 1994-09-14 |
Family
ID=16257964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19042886A Expired - Lifetime JPH0672316B2 (en) | 1986-08-15 | 1986-08-15 | Metal chromating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672316B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1986
- 1986-08-15 JP JP19042886A patent/JPH0672316B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672316B2 (en) | 1994-09-14 |
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