JPS6350484A - After-treating bath for improving corrosion resistance of metal plated steel sheet - Google Patents
After-treating bath for improving corrosion resistance of metal plated steel sheetInfo
- Publication number
- JPS6350484A JPS6350484A JP19372786A JP19372786A JPS6350484A JP S6350484 A JPS6350484 A JP S6350484A JP 19372786 A JP19372786 A JP 19372786A JP 19372786 A JP19372786 A JP 19372786A JP S6350484 A JPS6350484 A JP S6350484A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- plated steel
- post
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 22
- 239000010959 steel Substances 0.000 title claims abstract description 22
- 238000005260 corrosion Methods 0.000 title claims abstract description 18
- 230000007797 corrosion Effects 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title abstract description 9
- 239000002184 metal Substances 0.000 title abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000009931 harmful effect Effects 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- 150000003841 chloride salts Chemical class 0.000 abstract description 2
- 150000004673 fluoride salts Chemical class 0.000 abstract description 2
- 150000004679 hydroxides Chemical class 0.000 abstract description 2
- 150000002823 nitrates Chemical class 0.000 abstract description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 2
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 3
- 238000004532 chromating Methods 0.000 abstract 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 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 2
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、金属メッキ鋼板の耐食性に優れた後処理浴に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a post-treatment bath that has excellent corrosion resistance for metal-plated steel sheets.
（従来の技術）
従来から亜鉛又は亜鉛系合金メッキ鋼板の耐白錆性向上
処理として、クロム酸を中心とした後処理が採用されて
いる。こｎは、メッキ金属の亜鉛が大気中に暴露される
と、空気中の酸素、炭酸ガス、水分等と反応して、白錆
（ｗｈｉｔｅ ｒｕｓｔ）という特有の錆を形成して耐
食性を劣化するのを防止する為に採用される。このクロ
ム酸を中心とした後処理が一般的なのは、クロムの優れ
た後処理効果によるもので、過去、この元素中心以外に
、優れた後処理浴が見出せなかったこともあって、現在
でも、後処理浴としての主流にある。(Prior Art) As a treatment for improving the white rust resistance of zinc or zinc-based alloy plated steel sheets, post-treatment using chromic acid has been employed. When zinc plated metal is exposed to the atmosphere, it reacts with oxygen, carbon dioxide, moisture, etc. in the air, forming a unique type of rust called white rust, which deteriorates its corrosion resistance. It is adopted to prevent The reason why chromium-based post-treatment is common is due to the excellent post-treatment effect of chromium.In the past, no excellent post-treatment bath other than this element was found, and even now, It is mainstream as a post-treatment bath.
（発明が解決しようとする問題点）
然し、クロムは、６価クロムが食品衛生公害上、特に注
意すべき有害な元素であり、身体に接触することも、注
意される金属である。そこで、過去、クロムの有害性を
避ける為に、数多くのノンクロメート後処理浴が研究さ
れたが、なかなかクロムの優れた耐食性に匹敵する後処
理浴が開発できなかった。(Problems to be Solved by the Invention) However, hexavalent chromium is a harmful element that should be especially careful in terms of food hygiene pollution, and chromium is a metal that should be careful not to come into contact with the body. Therefore, in the past, many non-chromate post-treatment baths have been studied in order to avoid the harmful effects of chromium, but it has been difficult to develop a post-treatment bath that rivals the excellent corrosion resistance of chromium.
（問題点を解決するための手段）
本発明者はこうしたクロムを使用した場合の有害性を鑑
み、他の元素、Ｔｉ、 Ｚｒ、 Ｂａ、 Ｍｇ等の効果
を鋭意研究した結果、クロムの耐食性向上効果に劣らな
い後処理浴全開発した。即ち、本発明の要旨とするとこ
ろは、Ｔｉ、 Ｚｒ、 Ｍｇ、Ｂａ、 Ｓｒ、 Ｗ、
Ｎｉ、 Ｃｏ、 Ｖ、Ｃａ、 Ｍｏ、 Ｃｕ、 Ａｌ、
Ｓｎ％Ｂｅ、 Ｍｎ イオンの一種又は二種以上を珪
酸ゾルを含む水溶液に混合したものを、金属メッキ鋼板
の耐食性を改善する後処理浴である。(Means for Solving the Problems) In view of the harmful effects of using chromium, the present inventor conducted intensive research on the effects of other elements such as Ti, Zr, Ba, Mg, etc., and as a result, improved the corrosion resistance of chromium. We have developed a complete post-treatment bath that is no less effective. That is, the gist of the present invention is that Ti, Zr, Mg, Ba, Sr, W,
Ni, Co, V, Ca, Mo, Cu, Al,
This is a post-treatment bath for improving the corrosion resistance of metal-plated steel sheets, in which one or more of Sn%Be and Mn ions are mixed into an aqueous solution containing silicic acid sol.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
（作 用）
珪酸ゾｋ ｋ含む水溶液に、Ｔｉ１Ｚｒ、 Ｍｇ、 Ｅ
ａ。(Function) In an aqueous solution containing silicate, Ti1Zr, Mg, E
a.
Ｓｒ、 ＷｌＮｉ、 Ｃｏ、■、Ｃａ、 Ｍｏ、 Ｃｕ
、 Ａｌ、 Ｓｎ。Sr, WlNi, Co, ■, Ca, Mo, Cu
, Al, Sn.
Ｂｅ、 Ｍｎイオンを添加した後処理浴で、金属メッキ
鋼板を処理すると、−段と耐食性が改善される。特に、
Ｔｉ、Ｚｒ 、 Ｍｇ、 Ｂａ 等に、その効果が顕
著に見られ、Ｚｒの場合を説明すると、Ｚｒを添加した
珪酸ゾルを含む水溶液で、金属メッキ鋼板を処理すると
、珪酸ゾル被膜中に水に難溶なＺｒ（ＯＨ）、被膜が形
成され、このＺｒ（ＯＨ）４被膜が、ｐＨＯ〜１４の環
境で極めて安定な為に、珪酸ゾル等の腐食環境に接触し
た場合の溶出が抑えられ、従って結果として、耐食性が
改善される。こうした効果は、Ｔｉ、 Ｍｇの場合にも
顕著で、微量添加高複合耐食性向上効果と思われる。When a metal-plated steel sheet is treated with a post-treatment bath containing Be and Mn ions, its corrosion resistance is significantly improved. especially,
This effect is noticeable for Ti, Zr, Mg, Ba, etc. In the case of Zr, when a metal plated steel sheet is treated with an aqueous solution containing silicate sol added with Zr, water is absorbed into the silicate sol coating. A poorly soluble Zr(OH) film is formed, and this Zr(OH)4 film is extremely stable in an environment with a pH of ~14, so elution is suppressed when it comes into contact with a corrosive environment such as silicate sol. Corrosion resistance is therefore improved as a result. Such an effect is also remarkable in the case of Ti and Mg, and is thought to be due to the high composite corrosion resistance improvement effect when added in small amounts.
第１図は、珪酸ゾル（ＳｉＣ２）４０ｇ／ｌの水溶液に
、Ｋ２Ｚｒｌ；’６５ ｇ／Ｌ又ハに２ＴｉＦ６ ｓ
ｇ／ ｌ ｋ含む後処理浴に溶融亜鉛メッキ鋼板を浸漬
して、リンガロールで付着量調整し、Ｔｉ、 Ｚｒ付着
量１、４ ｍ９／ｌｒ？片面塗布して、熱風乾燥した製
品の塩水噴霧試験を行い、そΩ結果を、横軸に塩水噴霧
時間、縦軸に白錆発生面積（イ）に整理して示したもの
である。Δ印かに２ＺｒＦ６． ｘ印かに２ＴｉＦ’６
添加のもので、○印は、Ｃｒｙ３１５ ｇ／ ｌの同様
後処理毎で、同様、Ｏｒ付着量１０ｒｎ９／ｍ”・片面
塗布したサンプルを、比較材として示したものである。Figure 1 shows that 40 g/l of silicate sol (SiC2) was added with K2Zrl;
A hot-dip galvanized steel plate was immersed in a post-treatment bath containing g/lk, and the adhesion amount was adjusted with a Ringer roll to give a Ti, Zr adhesion amount of 1.4 m9/lr? A product coated on one side and dried with hot air was subjected to a salt spray test, and the results are shown organized as salt water spray time on the horizontal axis and white rust occurrence area (A) on the vertical axis. Δ mark crab2ZrF6. x mark crab 2TiF'6
In the case of additives, the circle mark indicates a sample that was similarly post-treated with Cry315 g/l and coated on one side with an Or coating amount of 10rn9/m'' as a comparative material.
本発明浴のＴｉ又はＺｒｉ添加した珪酸ゾル水溶液で処
理した製品は極めて耐食性が優れていることが判る。It can be seen that the products treated with the Ti or Zri-added silicic acid sol aqueous solution of the bath of the present invention have extremely excellent corrosion resistance.
ここで、本発明浴は、金属イオン又は珪酸ゾル溶液濃度
を特に規定しない。一般には、金属イオン濃度の高い程
、珪酸ゾル濃度の高い程、耐食性は優れる。又、珪酸ゾ
ルには、塗料、密着性向上効果もある。Here, in the bath of the present invention, the metal ion or silicate sol solution concentration is not particularly defined. Generally, the higher the metal ion concentration and the higher the silicate sol concentration, the better the corrosion resistance. In addition, silicic acid sol also has the effect of improving adhesion to paints.
金属イオンの元素源は、これらの元素一種又は二種以上
を含む可溶性の酸化物、水酸化物、炭酸塩、硫酸塩、硝
酸塩、塩化物、弗化物、カリウム塩、ナトリウム塩、ア
ンモニウム塩等の無機化合物である。Elemental sources of metal ions include soluble oxides, hydroxides, carbonates, sulfates, nitrates, chlorides, fluorides, potassium salts, sodium salts, ammonium salts, etc. containing one or more of these elements. It is an inorganic compound.
又、浴処理の温度は常温でも良く、４０〜６０℃に加熱
された処理浴でも良い。Further, the temperature of the bath treatment may be normal temperature or a treatment bath heated to 40 to 60°C.
金属イオンの付着量調整方法は、浸漬又はスプレー後、
リンガ−ロール、エアナイフ等で調整され、ロールコー
タ−１静電塗布方法の場合は、各々従来の調整方法が踏
襲される。The method for adjusting the amount of metal ions adhered to is after dipping or spraying.
Adjustments are made using ringer rolls, air knives, etc., and in the case of the roll coater 1 electrostatic coating method, conventional adjustment methods are followed.
この発明における処理対象とする鋼板は、溶融亜鉛メッ
キ鋼板を中心に述べたが、溶融亜鉛メッキ鋼板、溶融亜
鉛系合金メッキ鋼板、溶融アルミメッキ鋼板等の溶融メ
ッキ鋼板、及び電気亜鉛メッキ鋼板、亜鉛系合金電気メ
ツキ鋼板等の電気メツキ鋼板、それらの金属、合金類に
よる被履全した各種金属メッキ鋼板で、そのメッキ手段
を問わない。The steel sheets to be treated in this invention have mainly been described as hot-dip galvanized steel sheets, but include hot-dip galvanized steel sheets, hot-dip galvanized steel sheets, hot-dip aluminized steel sheets, etc., electrogalvanized steel sheets, zinc-coated steel sheets, etc. Electroplated steel sheets such as alloy electroplated steel sheets, and various metal-plated steel sheets that have been completely coated with those metals and alloys, regardless of the plating method used.
上記のような本発明により、従来のクロム酸の後処理浴
に劣らない、クロムを用いない一段と優れた耐食性全有
する金属メッキ鋼板が得られる。According to the present invention as described above, it is possible to obtain a metal-plated steel sheet that does not use chromium and has even better corrosion resistance than conventional chromic acid post-treatment baths.
（爽 施 例） 以下、本発明の実施例を述べる。(Example of refreshing) Examples of the present invention will be described below.
表に示す処理浴と処理条件で、各穏亜鉛メッキ鋼板及び
アルミメッキ鋼板を処理し、水洗することなく、リンガ
−ロール絞沙ヲ行って、熱風乾燥することにより、各種
製品を得た。Various products were obtained by treating mildly galvanized steel sheets and aluminium-plated steel sheets using the treatment baths and treatment conditions shown in the table, applying ring roll sanding without washing with water, and drying with hot air.
珪酸ゾルとして、水ガラス系水溶液を使用した０
得られた製品は、性能評価として、耐食性試験を施した
。耐食性試験は、平板部の塩水噴霧試験を７２時間行い
、白錆発生面積＠）全測定したＯ
性能評価した結果を表に示す。A water glass-based aqueous solution was used as the silicic acid sol.The resulting product was subjected to a corrosion resistance test for performance evaluation. For the corrosion resistance test, a salt water spray test was conducted on the flat plate portion for 72 hours, and the white rust occurrence area @) was completely measured and the performance was evaluated.The results are shown in the table.
（発明の効果）
表に示す如く、本発明の処理浴によって処理された鋼板
は、比較例に比し、優れた耐食性を示す。(Effects of the Invention) As shown in the table, the steel plate treated with the treatment bath of the present invention exhibits superior corrosion resistance compared to the comparative example.
第１図は本発明処理浴を用いた製品と従来から使用され
ている浴を用いた製品の白錆発生面積を示す図である。
第１図FIG. 1 is a diagram showing the white rust occurrence area of a product using the treatment bath of the present invention and a product using a conventionally used bath. Figure 1
Claims (1)
Ｃａ、Ｍｏ、Ｃｕ、Ａｌ、Ｓｎ、Ｂｅ、Ｍｎイオンの一
種又は二種以上を珪酸ゾルを含む水溶液に混合したこと
を特徴とする金属メッキ鋼板の耐食性を改善する後処理
浴。Ti, Zr, Mg, Ba, Sr, W, Ni, Co, V,
A post-treatment bath for improving the corrosion resistance of metal-plated steel sheets, characterized in that one or more of Ca, Mo, Cu, Al, Sn, Be, and Mn ions are mixed into an aqueous solution containing silicic acid sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19372786A JPS6350484A (en) | 1986-08-19 | 1986-08-19 | After-treating bath for improving corrosion resistance of metal plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19372786A JPS6350484A (en) | 1986-08-19 | 1986-08-19 | After-treating bath for improving corrosion resistance of metal plated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6350484A true JPS6350484A (en) | 1988-03-03 |
Family
ID=16312796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19372786A Pending JPS6350484A (en) | 1986-08-19 | 1986-08-19 | After-treating bath for improving corrosion resistance of metal plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6350484A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011184769A (en) * | 2010-03-10 | 2011-09-22 | Murata:Kk | Chemical conversion liquid, method for producing the same and method for forming chemical conversion coating film |
-
1986
- 1986-08-19 JP JP19372786A patent/JPS6350484A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011184769A (en) * | 2010-03-10 | 2011-09-22 | Murata:Kk | Chemical conversion liquid, method for producing the same and method for forming chemical conversion coating film |
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