JPH01104783A - Production of surface treated steel sheet having superior resistance to corrosion and leaving of fingerprint - Google Patents
Production of surface treated steel sheet having superior resistance to corrosion and leaving of fingerprintInfo
- Publication number
- JPH01104783A JPH01104783A JP26987987A JP26987987A JPH01104783A JP H01104783 A JPH01104783 A JP H01104783A JP 26987987 A JP26987987 A JP 26987987A JP 26987987 A JP26987987 A JP 26987987A JP H01104783 A JPH01104783 A JP H01104783A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- fingerprint
- corrosion
- soln
- treated steel
- 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 28
- 239000010959 steel Substances 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title claims abstract description 15
- 230000007797 corrosion Effects 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 7
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 4
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 125000005595 acetylacetonate group Chemical group 0.000 abstract 2
- 229910018137 Al-Zn Inorganic materials 0.000 abstract 1
- 229910018573 Al—Zn Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- -1 impropoxide Chemical compound 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 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、耐食性、耐指紋性に優れ、しかも衛生的にも
安全である表面処理鋼板の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a surface-treated steel sheet that has excellent corrosion resistance and anti-fingerprint properties, and is also hygienically safe.
（従来技術）
亜鉛めっき、アルミニウムめっきあるいは亜鉛−アルミ
ニウム合金めっき鋼板は、従来より種々の用途に使用さ
れている。これらのめっき鋼板は、耐食性向上のため、
製造の際に通常後処理を施しているが、この後処理とし
ては、従来、クロメート処理が主に行なわれている。(Prior Art) Galvanized, aluminum plated or zinc-aluminum alloy plated steel sheets have been used for various purposes. These plated steel sheets are used to improve corrosion resistance.
Post-treatment is usually performed during manufacturing, and conventionally, chromate treatment has been mainly performed as this post-treatment.
（発明が解決しようとする問題点）
しかし、クーロメート皮膜は、使用環境が湿潤環境であ
ると、り・ロムイオンが溶出してくるため、食品関連の
用途に使用するものにクロメート処理を施すことは、衛
生上問題があった。特にクロメート処理は、耐食性向上
のために、クロメート皮膜のＣｒ付着量を２０〜４０
ｍｇ／ｍ”以上にすると、クロムイオン溶出が多くなり
、皮膜も黄褐色に着色して、外観を損なうものであった
。また、クロメート皮膜は、指紋が付着すると、付着部
分が変色し、その部分の耐食性が低下してしまうもので
あった。(Problem to be solved by the invention) However, if the couromate film is used in a humid environment, lithium and chromium ions will elute, so chromate treatment cannot be applied to products used in food-related applications. , there were hygiene problems. In particular, chromate treatment reduces the amount of Cr attached to the chromate film by 20 to 40 to improve corrosion resistance.
mg/m" or more, chromium ion elution increases, and the film is also colored yellowish-brown, impairing its appearance. In addition, when fingerprints adhere to the chromate film, the attached part changes color, and The corrosion resistance of the parts deteriorated.
このため、クロメート処理のように処理が簡単で、上記
のような問題のない表面処理鋼板の得られる方法が一必
要であった。For this reason, there was a need for a method such as chromate treatment that is easy to process and that can produce a surface-treated steel sheet free from the problems described above.
（問題、αを解決するための手段）
本発明は、Ｓｉ、 Ｔｉ、 Ｚｒ、Ａｌ、Ｗ、 Ｃｅ、
Ｓｎ、 Ｙのアルコキシドもしくはアセチルアセトネ
ート塩の１種または２種以上を０．００５重皿％以上含
有するアルコール溶液を亜鉛、アルミニウムまたは亜鉛
−アルミニウム合金めっき鋼板に塗布して、２００〜５
００℃に加熱し、溶液中に含まれる金属の酸化物皮膜を
鋼板表面に形成することにより衛生上安全で、耐食性、
耐指紋性に優れた表面処理鋼板を製造できるようにした
。(Means for solving the problem α) The present invention provides Si, Ti, Zr, Al, W, Ce,
An alcoholic solution containing 0.005% or more of Sn, Y alkoxide or acetylacetonate salt is applied to a zinc, aluminum or zinc-aluminum alloy plated steel sheet,
By heating to 00℃ and forming an oxide film of the metal contained in the solution on the surface of the steel plate, it is hygienically safe, corrosion resistant,
It has become possible to manufacture surface-treated steel sheets with excellent fingerprint resistance.
Ｓ；％ Ｔｊｓ Ｚｒ、＾ｌ、 ＷｌＣｅＳＳｎｘ Ｙ
のアルコキシドもしくはアセチルアセトネート塩は、加
水分解して金属水酸化物となり、これを加熱すると、脱
水縮合して、金属酸化物となる。従って、鋼板に塗布し
て加熱すれば、表面に金属酸化物皮膜を形成することが
できる。S;% Tjs Zr, ^l, WlCeSSnx Y
The alkoxide or acetylacetonate salt of is hydrolyzed to become a metal hydroxide, and when this is heated, it undergoes dehydration condensation to become a metal oxide. Therefore, by applying it to a steel plate and heating it, a metal oxide film can be formed on the surface.
上記元素のアルコキシドとしては、メトキシド、エトキ
シド、インプロポキシド、ｎ−ブトキシドを使用すれば
よく、また、アセチルアセトネート塩としては、ジルコ
ニウムアセチルアセトネート、アルミニウムアセチルア
セトネート、チタンアセチルアセトネート、イツトリア
７セチルアセトネートなどを使用すればよい。As the alkoxide of the above element, methoxide, ethoxide, impropoxide, n-butoxide may be used, and as the acetylacetonate salt, zirconium acetylacetonate, aluminum acetylacetonate, titanium acetylacetonate, ittria 7 Cetyl acetonate or the like may be used.
溶液中には、アルコキシドや７セチル７セトネート塩の
加水分解を促進するため、陵や塩基を触媒として添加す
ることも可能である。In order to promote the hydrolysis of alkoxides and 7-cetyl 7-cetonate salts, it is also possible to add a base or a base to the solution as a catalyst.
溶液を希釈するアルコールには、特に制限はないが、メ
タ／−ル、エタノール、インプロパノール、ブタノール
なと低級アルコールが好ましい。The alcohol used to dilute the solution is not particularly limited, but lower alcohols such as methanol, ethanol, impropanol, and butanol are preferred.
溶液の鋼板への塗布は、浸漬引き上げ法、スプレー法、
スピン法、ロールコート法など公知方法によればよい。The solution can be applied to the steel plate using the dipping method, spray method,
A known method such as a spin method or a roll coating method may be used.
鋼板への塗布後の溶液加熱温度を２００〜５００℃にし
たのは、２００℃未満であると、アルコキシドやアセチ
ルアセトネート塩の脱水縮合が完全に進行しないため、
完全な金属酸化物のポリマー皮膜にならず、５００℃を
越えると、アルコールが急激に蒸発して、ピンホールが
発生するからである。The reason why the solution heating temperature after application to the steel plate was set at 200 to 500°C is because if the temperature is less than 200°C, the dehydration condensation of alkoxides and acetylacetonate salts will not proceed completely.
This is because, if the temperature exceeds 500° C., the alcohol will evaporate rapidly and pinholes will occur without forming a complete metal oxide polymer film.
塗布量は、乾燥後の皮ｉ厚が０．０５μｍ以上、好まし
くけ０．０５〜０．６μ論、−前約には０．１μｍにな
るようにする。０．０５μｍ未満であると、耐食性、耐
指紋性が劣り、０．６μ鎗より厚くすると、可撓性が低
下し、クラックや剥離が生じ易くなる。The amount of application is such that the skin thickness after drying is 0.05 μm or more, preferably 0.05 to 0.6 μm, and preferably 0.1 μm. If it is less than 0.05 μm, corrosion resistance and fingerprint resistance will be poor, and if it is thicker than 0.6 μm, flexibility will decrease and cracks and peeling will easily occur.
（実施例）
板厚０．４１１１ｍの蒸着または電気亜鉛めっき鋼板、
溶融亜鉛−アルミニウム合金めっき鋼板および溶融また
は電気アルミニウムめっき鋼板を７七トンで１５分間超
音波脱脂した後、表１の左側に示す組成の金属アルコキ
シドおよび／＊たはアセチルアセトネート金属塩のアル
コール溶液に浸漬し、３ＩＩＩＩｌ／秒の一定速度で引
上げ、均一に塗布した。(Example) Vapor deposited or electrogalvanized steel sheet with a thickness of 0.4111 m,
After ultrasonic degreasing of hot-dip zinc-aluminum alloy coated steel sheets and hot-dip or electro-aluminum coated steel sheets at 77 tons for 15 minutes, an alcohol solution of metal alkoxide and/or acetylacetonate metal salt having the composition shown on the left side of Table 1 was prepared. The coating was applied uniformly by dipping it in water and pulling it up at a constant speed of 3IIIl/sec.
そして、塗布後これらの鋼板を３００℃の電気炉・ 中
に２分間入れ、膜厚的０．１μｍの酸化物皮膜を形成し
た。After coating, these steel plates were placed in an electric furnace at 300° C. for 2 minutes to form an oxide film with a thickness of 0.1 μm.
一方、比較材として、前記めっき鋼板にクロメート処理
（Ｃｒ付′；４量１５−２７ ｍｇ／ｍ２）を施したも
のを作成した。On the other hand, as a comparative material, the above plated steel sheet was subjected to chromate treatment (Cr added; 4 amount: 15-27 mg/m2).
表１の右側にこれらの表面処理鋼板の耐食性、加熱後耐
食性、耐指紋性および耐久性を示す。The right side of Table 1 shows the corrosion resistance, corrosion resistance after heating, fingerprint resistance, and durability of these surface-treated steel sheets.
なお、試験は、次のようにして行った６（１）耐食性
ＪＩＳ、 Ｚ ２３７１による塩水噴霧試験を２４０時
間実施し、白錆発生率（％）を評価した。In the test, a salt spray test according to 6(1) Corrosion Resistance JIS, Z 2371 was carried out for 240 hours, and the white rust occurrence rate (%) was evaluated.
（２）加熱後耐食性
電気炉中にて５００℃で１時間加熱し、その後上記塩水
噴霧試験を同時間実施した。(2) Corrosion resistance after heating The sample was heated at 500° C. for 1 hour in an electric furnace, and then the salt water spray test described above was conducted for the same period of time.
（３）耐指紋性
人工指紋液をゴム栓に付着させ、ＩＫｇ／＋ａ”の圧力
で試験片に一定時間押し付け、指紋の付着状態を次の基
準で評価した。(3) Fingerprint resistance An artificial fingerprint liquid was applied to a rubber stopper and pressed against a test piece for a certain period of time at a pressure of IKg/+a'', and the state of fingerprint adhesion was evaluated according to the following criteria.
○ 指紋跡が全く目立たない
Δ 指紋跡がわずかに目立つ
× 指紋跡が目立つ
（４）耐久性
試験片を３年問屋外暴露し、表面の変色程度を次の基準
で評価した。○ Fingerprint marks are not noticeable at all Δ Fingerprint marks are slightly noticeable × Fingerprint marks are noticeable (4) Durability test pieces were exposed outdoors for 3 years, and the degree of surface discoloration was evaluated using the following criteria.
○ 変色が全くない Δ わずかに変色 Ｘ 着しく変色 （発明の効果） 以上のごとく、本発明の方法は、Ｓ１％Ｔｉ５Ｚｒ。○ No discoloration at all Δ Slight discoloration X Discolored (Effect of the invention) As described above, the method of the present invention uses S1%Ti5Zr.
Ａｌ、Ｗ、 Ｃｅ５Ｓｎ、 Ｙのアルコキシドもしくは
アセチルアセトネート塩を添加したアルコール溶液をめ
っき鋼板に塗布して、加熱するだけであるので、処理は
簡単である。また、得られた表面処理銅板は、ｉｔ食性
、耐指紋性に優れ、しかもクロムを含有しないので、衛
生的にも安全である。The treatment is simple, as it only involves applying an alcohol solution containing an alkoxide or acetylacetonate salt of Al, W, Ce5Sn, or Y to a plated steel plate and heating it. Furthermore, the obtained surface-treated copper plate has excellent corrosion resistance and anti-fingerprint properties, and is hygienically safe since it does not contain chromium.
Claims (1)
キシドもしくはアセチルアセトネート塩の１種または２
種以上を０．００５重量％以上含有するアルコール溶液
を亜鉛、アルミニウムまたは亜鉛−アルミニウム合金め
っき鋼板に塗布して、２００〜５００℃に加熱し、溶液
中に含まれる金属の酸化物皮膜を鋼板表面に形成するこ
とを特徴とする耐食性、耐指紋性に優れた表面処理鋼板
の製造方法。One or two alkoxides or acetylacetonate salts of Si, Ti, Zr, Al, W, Ce, Sn, Y
An alcoholic solution containing 0.005% by weight or more of metal or more is applied to a zinc, aluminum or zinc-aluminum alloy coated steel sheet and heated to 200 to 500°C to form an oxide film of the metal contained in the solution on the surface of the steel sheet. A method for producing a surface-treated steel sheet with excellent corrosion resistance and fingerprint resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26987987A JPH01104783A (en) | 1987-07-23 | 1987-10-26 | Production of surface treated steel sheet having superior resistance to corrosion and leaving of fingerprint |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-184393 | 1987-07-23 | ||
| JP18439387 | 1987-07-23 | ||
| JP26987987A JPH01104783A (en) | 1987-07-23 | 1987-10-26 | Production of surface treated steel sheet having superior resistance to corrosion and leaving of fingerprint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01104783A true JPH01104783A (en) | 1989-04-21 |
Family
ID=26502474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26987987A Pending JPH01104783A (en) | 1987-07-23 | 1987-10-26 | Production of surface treated steel sheet having superior resistance to corrosion and leaving of fingerprint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01104783A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006519308A (en) * | 2003-02-25 | 2006-08-24 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for coating a metal surface with a polymer-rich composition |
-
1987
- 1987-10-26 JP JP26987987A patent/JPH01104783A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006519308A (en) * | 2003-02-25 | 2006-08-24 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for coating a metal surface with a polymer-rich composition |
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