JP2007297646A - Method for manufacturing electrogalvanized steel sheet - Google Patents
Method for manufacturing electrogalvanized steel sheet Download PDFInfo
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- JP2007297646A JP2007297646A JP2006079068A JP2006079068A JP2007297646A JP 2007297646 A JP2007297646 A JP 2007297646A JP 2006079068 A JP2006079068 A JP 2006079068A JP 2006079068 A JP2006079068 A JP 2006079068A JP 2007297646 A JP2007297646 A JP 2007297646A
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- electrogalvanized steel
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 37
- 239000010959 steel Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title abstract description 20
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 21
- -1 2-benzothiazolylthio group Chemical group 0.000 claims abstract description 17
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 238000007747 plating Methods 0.000 abstract description 20
- 238000011282 treatment Methods 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、白色度の高い電気亜鉛めっき鋼板の製造方法に関するものである。 The present invention relates to a method for producing an electrogalvanized steel sheet having high whiteness.
電気亜鉛めっき鋼板は家電製品、自動車、建材等の広範な用途で使用されている。中でも、近年、無塗装で使用される家電用途向け各種化成処理電気亜鉛めっき鋼板の需要が増大しており、重要な用途分野となっている。この用途では無塗装で使用されるために表面外観に優れることが要求される。優れた表面外観の条件としては、ムラ等の表面欠陥が無いことに加え、白色度が高いことが要求され、各種化成処理後の外観は化成処理前の亜鉛めっきの外観に大きく左右されるため、白色度が高い電気亜鉛めっき鋼板を得ることが求められてきている。
上記を受けて、めっき鋼板の白色度を向上させる方法として、めっき浴に無機イオンを添加する方法がある（例えば、特許文献１）。
また、別の方法として、めっき浴中に有機物を添加する方法がある。特許文献２では、グリシン、アスパラギン酸、カルボン酸基を２つ以上有するカルボン酸またはその塩の群から選択された１種又は２種をめっき浴中に添加する方法が開示されている。特許文献３では、電気亜鉛めっき浴添加剤として、ナフテン酸の金属塩、アニリン誘導体、低級アルカノイル化合物、及び有機過酸化物よりなる群から選択される少なくとも１種が開示されている。
また、特許文献４では、可溶性のイオウ含有有機化合物を含有する酸性浴中で陰極電解し、引き続き、りん酸亜鉛処理する方法が開示されている。
In response to the above, there is a method of adding inorganic ions to the plating bath as a method of improving the whiteness of the plated steel sheet (for example, Patent Document 1).
Another method is to add an organic substance to the plating bath. Patent Document 2 discloses a method in which one or two selected from the group of glycine, aspartic acid, a carboxylic acid having two or more carboxylic acid groups, or a salt thereof is added to the plating bath. Patent Document 3 discloses at least one selected from the group consisting of a metal salt of naphthenic acid, an aniline derivative, a lower alkanoyl compound, and an organic peroxide as an electrogalvanizing bath additive.
Patent Document 4 discloses a method of cathodic electrolysis in an acidic bath containing a soluble sulfur-containing organic compound, followed by zinc phosphate treatment.
しかしながら、上記特許文献には以下の問題点がある。
特許文献１においては、めっき浴に無機物を添加する方法であるため、めっき皮膜中に無機物が共析し、共析によりめっき皮膜の耐食性が劣化したり外観が急激に変化して光沢化してしまう。
特許文献２および３では、白色度の上昇に伴い光沢度が上昇したり、めっき電流効率の低下により製造コストアップを招くなどの問題がある。
特許文献４では、めっきの光沢度を上昇させ、緻密で平滑なりん酸亜鉛皮膜を形成させてりん酸亜鉛処理後のL値を高くするための技術である。即ち、りん酸亜鉛処理による白色度の低下が8未満と小さいことに特徴がある。しかし、めっき後の外観については、光沢度は上昇するが、白色度を上昇させる効果はない。
このように、従来の方法では、いずれもめっきの白色度の上昇効果が不十分である。また、白色度を上昇させることはできても耐食性低下、光沢化等の他の特性が大きく変化してしまう、あるいは電流効率が大きく低下してしまうといった問題がある。
However, the above patent document has the following problems.
In patent document 1, since it is the method of adding an inorganic substance to a plating bath, an inorganic substance co-deposits in a plating film, and the corrosion resistance of the plating film deteriorates due to the eutectoid or the appearance rapidly changes to become glossy. .
In Patent Documents 2 and 3, there is a problem that the glossiness increases with an increase in whiteness and a manufacturing cost increases due to a decrease in plating current efficiency.
In patent document 4, it is the technique for raising the glossiness of metal plating, forming a precise | minute and smooth zinc phosphate film, and raising the L value after a zinc phosphate process. That is, the reduction in whiteness due to the zinc phosphate treatment is as small as less than 8. However, with regard to the appearance after plating, the glossiness increases, but there is no effect of increasing the whiteness.
As described above, any of the conventional methods is insufficient in increasing the whiteness of the plating. In addition, even if the whiteness can be increased, other characteristics such as a decrease in corrosion resistance and glossing are greatly changed, or the current efficiency is greatly decreased.
本発明は、上記の事情に鑑み、他の特性が大きく変化することなく、また、電流効率が大きく低下することなく、高い白色度を有する電気亜鉛めっき鋼板を製造する方法を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a method for producing an electrogalvanized steel sheet having high whiteness without greatly changing other characteristics and without greatly reducing current efficiency. And
本発明者らが高い白色度を有する電気亜鉛めっき鋼板の製造方法を開発する為、研究を重ねた結果、2-ベンゾチアゾリルチオ基を持つ有機化合物の１種又は２種以上を合計で0.01〜3ppm含有する電気亜鉛めっき浴中で鋼板を陰極電解処理することにより、耐食性低下及び光沢化を生じさせずに高い白色度を有する電気亜鉛めっき鋼板が製造できることを見出した。
本発明は、このような知見に基づきなされたもので、その特徴は以下のとおりである。
［１］2-ベンゾチアゾリルチオ基を持つ有機化合物の１種又は２種以上を合計で0.01〜3ppm含有する電気亜鉛めっき浴中で鋼板を陰極電解処理することを特徴とする電気亜鉛めっき鋼板の製造方法。
［２］前記［１］において、前記2-ベンゾチアゾリルチオ基を持つ有機化合物が2-メルカプトベンゾチアゾール又はその塩であることを特徴とする電気亜鉛めっき鋼板の製造方法。
In order to develop a method for producing an electrogalvanized steel sheet having high whiteness by the present inventors, as a result of repeated research, one or more organic compounds having a 2-benzothiazolylthio group were combined in a total amount of 0.01. It has been found that an electrogalvanized steel sheet having high whiteness can be produced by subjecting the steel sheet to cathodic electrolysis in an electrogalvanizing bath containing ˜3 ppm without causing deterioration in corrosion resistance and brightening.
The present invention has been made based on such findings, and the features thereof are as follows.
[1] An electrogalvanized steel sheet characterized by cathodic electrolytic treatment of a steel sheet in an electrogalvanizing bath containing a total of 0.01 to 3 ppm of one or more organic compounds having a 2-benzothiazolylthio group Manufacturing method.
[2] The method for producing an electrogalvanized steel sheet according to [1], wherein the organic compound having a 2-benzothiazolylthio group is 2-mercaptobenzothiazole or a salt thereof.
本発明によれば、白色度の高い電気亜鉛めっき鋼板が得られる。また、電気亜鉛めっき処理後にクロメート又はクロメートフリー型の各種化成処理（塗布型、反応型、電解型）や、更にその上に樹脂被覆処理等を実施した鋼板についても同様の効果は得られ、表面外観に優れた化成処理電気亜鉛めっき鋼板が得られることになる。 According to the present invention, an electrogalvanized steel sheet having high whiteness can be obtained. In addition, the same effects can be obtained with various chemical treatments (coating type, reaction type, electrolytic type) of chromate or chromate-free type after electrogalvanizing treatment, and further steel coating with resin coating treatment on it. A chemical conversion electrogalvanized steel sheet having an excellent appearance can be obtained.
本発明は、2-ベンゾチアゾリルチオ基を持つ有機化合物の１種又は２種以上を合計で0.01〜3ppm含有する電気亜鉛めっき浴中で鋼板を陰極電解処理することを特徴とする。これにより、耐食性低下及び光沢化を生じさせずに高い白色度を有する電気亜鉛めっき鋼板が得られる。また、更に、2-ベンゾチアゾリルチオ基を持つ有機化合物として、2-メルカプトベンゾチアゾール又はその塩を使用することで、より一層高い白色化効果が得られることになる。
まず、本発明の完成に至った経緯について説明する。2-ベンゾチアゾリルチオ基を持つ有機化合物を含有しない電気亜鉛めっき浴を使用した場合と2-ベンゾチアゾリルチオ基を持つ有機化合物を含有する電気亜鉛めっき浴を使用した場合について、亜鉛めっき結晶を走査型電子顕微鏡で観察した。その結果、2-ベンゾチアゾリルチオ基を持つ有機化合物を含有する電気亜鉛めっき浴を使用した場合の方が亜鉛めっき結晶の凹凸の深さがやや小さくなる傾向があることがわかった。
これを基に、メカニズムについて考察した結果、メカニズムは以下の様に推定される。すなわち、2-ベンゾチアゾリルチオ基を持つ有機化合物は、電解時に亜鉛めっき表面に吸着し、亜鉛めっきの結晶成長を阻害し、また２次結晶の発生を促進する。これにより、亜鉛の結晶形態を変化させ、亜鉛めっき結晶の凹凸の深さが小さくなる。このために、凹凸の深い部分での光の吸収が少なく、拡散反射光が増加し、外観上明るく見える（白色度が向上する）と考えられる。
以上より、本発明においては、電気亜鉛めっき浴中に、2-ベンゾチアゾリルチオ基を持つ有機化合物の１種又は２種以上を含有することとする。また、電気亜鉛めっき浴中に添加する前記有機化合物の合計濃度が0.01ppm未満では、白色度の上昇効果が不十分となる。一方、3ppmを超えると、表面が極端に平滑化して金属光沢のある外観となってしまい、白色度が逆に低下してしまう。また、濃度が0.5ppmを超えると、電流効率が低下するため、上限は0.5ppm以下が望ましい。よって、2-ベンゾチアゾリルチオ基は、１種又は２種以上を合計で0.01〜3ppm、望ましくは0.5ppm以下、電気亜鉛めっき浴中に含有することとする。
The present invention is characterized by cathodic electrolytic treatment of a steel sheet in an electrogalvanizing bath containing a total of 0.01 to 3 ppm of one or more organic compounds having a 2-benzothiazolylthio group. As a result, an electrogalvanized steel sheet having high whiteness without causing deterioration of corrosion resistance and glossing can be obtained. Furthermore, when 2-mercaptobenzothiazole or a salt thereof is used as the organic compound having a 2-benzothiazolylthio group, an even higher whitening effect can be obtained.
First, the background to the completion of the present invention will be described. Zinc-plated crystals when using an electrogalvanizing bath that does not contain an organic compound with a 2-benzothiazolylthio group and when using an electrogalvanizing bath that contains an organic compound with a 2-benzothiazolylthio group Were observed with a scanning electron microscope. As a result, it was found that when the electrogalvanizing bath containing an organic compound having a 2-benzothiazolylthio group was used, the concavo-convex depth of the galvanized crystal tended to be somewhat smaller.
As a result of considering the mechanism based on this, the mechanism is estimated as follows. That is, an organic compound having a 2-benzothiazolylthio group is adsorbed on the surface of the zinc plating during electrolysis, inhibits the crystal growth of the zinc plating, and promotes the generation of secondary crystals. Thereby, the crystal form of zinc is changed, and the depth of the unevenness of the galvanized crystal is reduced. For this reason, it is considered that there is little light absorption in a deep uneven portion, diffuse reflection light increases, and the appearance looks bright (whiteness is improved).
From the above, in the present invention, the electrogalvanizing bath contains one or more organic compounds having a 2-benzothiazolylthio group. Further, when the total concentration of the organic compounds added to the electrogalvanizing bath is less than 0.01 ppm, the whiteness increasing effect is insufficient. On the other hand, if it exceeds 3 ppm, the surface becomes extremely smooth and has a metallic luster appearance, and the whiteness is decreased. Further, if the concentration exceeds 0.5 ppm, the current efficiency decreases, so the upper limit is preferably 0.5 ppm or less. Accordingly, the 2-benzothiazolylthio group contains one or more kinds in a total amount of 0.01 to 3 ppm, preferably 0.5 ppm or less in the electrogalvanizing bath.
以上は本発明の最も重要な要件である。次に、上記特徴に基づき、本発明を詳細に説明する。
電気亜鉛めっき鋼板の製造においては、通常、電気亜鉛めっき処理を行う前の処理として、鋼板表面を清浄化するための脱脂処理および水洗、さらには、鋼板表面を活性化するための酸洗処理および水洗が施され、これらの前処理に引き続いて電気亜鉛めっきを実施する。
脱脂処理および水洗方法は特に限定しない。通常の方法を用いることができる。
酸洗処理においては、硫酸、塩酸、硝酸、及びこれらの混合物等各種の酸が使用できる。中でも、硫酸、塩酸あるいはこれらの混合が望ましい。酸の濃度は特に規定しないが、酸化皮膜の除去能力、過酸洗による肌荒れ防止等を考慮すると、1〜20％程度が望ましい。また、酸洗処理液には、消泡剤・酸洗促進剤・酸洗抑制剤等を含有しても良い。
The above are the most important requirements of the present invention. Next, the present invention will be described in detail based on the above features.
In the production of an electrogalvanized steel sheet, normally, as a process before performing the electrogalvanizing process, a degreasing process and water washing for cleaning the steel sheet surface, and further a pickling process for activating the steel sheet surface and Washing with water is performed, and electrogalvanization is performed following these pretreatments.
The degreasing treatment and the water washing method are not particularly limited. Conventional methods can be used.
In the pickling treatment, various acids such as sulfuric acid, hydrochloric acid, nitric acid, and mixtures thereof can be used. Of these, sulfuric acid, hydrochloric acid, or a mixture thereof is desirable. The concentration of the acid is not particularly specified, but is preferably about 1 to 20% in consideration of the ability to remove the oxide film, prevention of rough skin by peracid washing, and the like. The pickling treatment liquid may contain an antifoaming agent, a pickling accelerator, a pickling inhibitor, and the like.
次いで、電気亜鉛めっき浴中で鋼板を陰極電解処理する。この時、電気亜鉛めっき浴中には、前述の通り、以下に示す2-ベンゾチアゾリルチオ基を持つ有機化合物の１種又は２種以上を合計で0.01〜3ppm含有することとする。 The steel sheet is then subjected to cathodic electrolysis in an electrogalvanizing bath. At this time, as described above, the electrogalvanizing bath contains a total of 0.01 to 3 ppm of one or more organic compounds having a 2-benzothiazolylthio group shown below.
電気亜鉛めっきの浴条件及び電解条件については、電気めっき浴中に前記有機化合物を前記濃度範囲で含有することを除き、特に限定されない。例えば、電気めっき浴としては硫酸浴、塩酸浴あるいは両者の混合などが適用できる。また、電気めっき浴中にはZnイオンの他、添加剤あるいは不純物として硫酸ナトリウム、硫酸カリウム等の伝導度補助剤、Fe、Ni、Pb、Sn、Co等の金属イオン等を含有しても良い。電気めっき浴条件についても特に限定しないが、例えば、浴温を30〜70℃、pHを0.5〜4.5、相対流速を0〜4.0m/secとすれば良い。電解電流密度についても特に限定しないが、例えば、10〜150A/dm2とすれば良い。電気亜鉛めっきの付着量についても特に限定しないが、通常5〜40g/m2程度である。 The electrogalvanizing bath conditions and electrolysis conditions are not particularly limited except that the organic compound is contained in the concentration range in the electroplating bath. For example, as the electroplating bath, a sulfuric acid bath, a hydrochloric acid bath, or a mixture of both can be applied. In addition to Zn ions, the electroplating bath may contain additives or impurities as conductivity aids such as sodium sulfate and potassium sulfate, metal ions such as Fe, Ni, Pb, Sn, and Co. . The electroplating bath conditions are not particularly limited. For example, the bath temperature may be 30 to 70 ° C., the pH may be 0.5 to 4.5, and the relative flow rate may be 0 to 4.0 m / sec. The electrolytic current density is not particularly limited, but may be, for example, 10 to 150 A / dm 2 . Not limited particularly also the adhesion amount of electro-galvanized, it is usually 5 to 40 g / m 2 approximately.
2-ベンゾチアゾリルチオ基を持つ有機化合物としては、特に、以下に示す２-メルカプトベンゾチアゾール又はその塩を使用することで白色度を更に効果的に上昇させることができるため、好ましい。２-メルカプトベンゾチアゾールの塩としては、Na塩、K塩、Zn塩及びCu塩などが例示できる。 As the organic compound having a 2-benzothiazolylthio group, it is particularly preferable to use 2-mercaptobenzothiazole or a salt thereof shown below, since the whiteness can be further effectively increased. Examples of the salt of 2-mercaptobenzothiazole include Na salt, K salt, Zn salt and Cu salt.
電気亜鉛めっき処理後、必要により、耐食性、耐疵付き性、加工性等の各種性能の更なる向上を目的として、クロメート又はクロメートフリー型の各種化成処理（塗布型、反応型、電解型）、更には、その上に樹脂被覆処理等を実施することができる。なお、これらの処理を施した鋼板についても、本発明の効果は得られることはいうまでもない。特に、これらの処理を施した化成処理鋼板の外観は、無塗装で使用される場合、電気亜鉛めっき後（化成処理前）の外観に大きく左右される。ゆえに、本発明の方法により製造した電気亜鉛めっき鋼板を使用することにより、高い白色度を有する化成処理鋼板の製造が可能となる。 After electrogalvanizing treatment, various chemical treatments (coating type, reaction type, electrolytic type) of chromate or chromate-free type, if necessary, for the purpose of further improving various performances such as corrosion resistance, scratch resistance, and workability. Furthermore, a resin coating process etc. can be implemented on it. In addition, it cannot be overemphasized that the effect of this invention is acquired also about the steel plate which performed these processes. In particular, the appearance of the chemical conversion treated steel sheet subjected to these treatments greatly depends on the appearance after electrogalvanizing (before chemical conversion treatment) when used without coating. Therefore, by using the electrogalvanized steel sheet produced by the method of the present invention, it is possible to produce a chemical conversion treated steel sheet having high whiteness.
めっき原板として冷延鋼板を使用し、これをアルカリで電解脱脂し、水洗した後、酸洗処理を実施した。なお、アルカリでの電解脱脂は、10％NaOH、70℃×10秒間、鋼板を陰極とした電解の条件で、酸洗は10％H2SO4の溶液を用いて25℃、10秒浸漬の条件で行った。引き続き、水洗した後、以下の条件で、かつ、表１および化３に示す有機化合物の種類および濃度で、鋼板を陰極として電気亜鉛めっき処理を実施した。なお、一部のものについては、電気めっき浴中に有機化合物を添加せずにめっきを実施した。
＜電気亜鉛めっき条件＞
・めっき浴：Zn2+イオン1.5mol/l含有する硫酸酸性浴（pH2.0、温度50℃）
・相対流速：1.5m/sec
・電流密度：100A/dm2
・めっき付着量：20g/m2
・電極（陽極）：酸化イリジウム電極
以上より得られた電気亜鉛めっき鋼板について、以下の測定方法および評価基準に基づき、白色度評価としての明度（L値）と、光沢度を測定した。得られた結果を表１に併せて示す。
＜L値測定方法および評価基準＞
めっき表面の明度をJIS Z 8722に記載の方法により測定し、下記基準により評価した。
◎：85≦L値
○：82≦L値＜85
×：78≦L値＜82
＜光沢度測定方法＞
JIS Z 8741に記載の方法により測定し、下記基準により評価した。測定角度は20°とした。
○：2≦光沢度＜4
△：4≦光沢度＜6
×：6≦光沢度
A cold-rolled steel sheet was used as the plating original sheet, and this was electrolytically degreased with alkali, washed with water, and then pickled. In addition, electrolytic degreasing with an alkali is 10% NaOH, 70 ° C. × 10 seconds under conditions of electrolysis using a steel plate as a cathode, and pickling is performed by using a 10% H 2 SO 4 solution at 25 ° C. for 10 seconds. Performed under conditions. Subsequently, after rinsing with water, electrogalvanizing treatment was carried out using the steel sheet as a cathode under the following conditions and with the types and concentrations of organic compounds shown in Table 1 and Chemical Formula 3. In some cases, plating was performed without adding an organic compound in the electroplating bath.
<Electrogalvanizing conditions>
・ Plating bath: Acidic sulfuric acid bath containing 1.5 mol / l Zn 2+ ions (pH 2.0, temperature 50 ° C)
・ Relative flow velocity: 1.5m / sec
・ Current density: 100A / dm 2
・ Plating adhesion amount: 20g / m 2
-Electrode (anode): With respect to the electrogalvanized steel sheet obtained from the iridium oxide electrode or more, the brightness (L value) and glossiness as whiteness evaluation were measured based on the following measurement method and evaluation criteria. The obtained results are also shown in Table 1.
<L value measurement method and evaluation criteria>
The brightness of the plating surface was measured by the method described in JIS Z 8722 and evaluated according to the following criteria.
◎: 85 ≦ L value ○: 82 ≦ L value <85
×: 78 ≦ L value <82
<Glossiness measurement method>
It was measured by the method described in JIS Z 8741 and evaluated according to the following criteria. The measurement angle was 20 °.
○: 2 ≦ Glossiness <4
Δ: 4 ≦ Glossiness <6
×: 6 ≦ Glossiness
表１より、本発明例においては、電流効率が高く、めっき外観を示すＬ値が82以上と高い。すなわち、白色度が高いことがわかる。また、光沢度の大幅な上昇も見られていない。特に、2-メルカプトベンゾチアゾール又はその塩を用いた本発明例では、Ｌ値がより優れていることがわかる。
一方、電気めっき浴中に含有する有機化合物の濃度が本発明範囲未満では、L値の向上効果が見られていない。また、本発明範囲を超えると、電流効率が低く、Ｌ値および光沢度が劣っている。また、従来技術である比較例９、１０は電流効率が高く、光沢度にも優れているが、Ｌ値が劣っている。そのため、無塗装で使用される用途等では不適である。
From Table 1, in the example of this invention, current efficiency is high and L value which shows a plating external appearance is as high as 82 or more. That is, it can be seen that the whiteness is high. In addition, there is no significant increase in glossiness. In particular, it can be seen that the L value is more excellent in the inventive examples using 2-mercaptobenzothiazole or a salt thereof.
On the other hand, when the concentration of the organic compound contained in the electroplating bath is less than the range of the present invention, the effect of improving the L value is not observed. Moreover, if it exceeds the range of the present invention, the current efficiency is low, and the L value and glossiness are inferior. Further, Comparative Examples 9 and 10, which are conventional techniques, have high current efficiency and excellent glossiness, but the L value is inferior. Therefore, it is unsuitable for applications that are used without painting.
本発明の電気亜鉛めっき鋼板は表面外観に優れ、無塗装で問題なく使用される。そのため家電製品、自動車、建材等の広範な用途での使用が可能となる。 The electrogalvanized steel sheet of the present invention has an excellent surface appearance and can be used without any problem without being painted. Therefore, it can be used in a wide range of applications such as home appliances, automobiles, and building materials.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012193419A (en) * | 2011-03-17 | 2012-10-11 | Jfe Steel Corp | Method for producing chemical conversion steel plate |
| CN102747396A (en) * | 2012-06-28 | 2012-10-24 | 贵州钢绳股份有限公司 | Technology for electrogalvanizing of specially-shaped steel wire |
| WO2013051268A1 (en) * | 2011-10-04 | 2013-04-11 | Ｊｆｅスチール株式会社 | Production method for zinc-electroplated steel sheet |
| WO2013051269A1 (en) * | 2011-10-04 | 2013-04-11 | Ｊｆｅスチール株式会社 | Production method for zinc-electroplated steel sheets |
| JP2013185190A (en) * | 2012-03-07 | 2013-09-19 | Jfe Steel Corp | Method for manufacturing electrogalvanized steel sheet |
| JP2013194259A (en) * | 2012-03-16 | 2013-09-30 | Jfe Steel Corp | Method for producing electrogalvanized steel sheet |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331457A (en) * | 1994-06-02 | 1995-12-19 | Sumitomo Metal Ind Ltd | Zinc phosphate treating plated metallic sheet bright in color tone and its production |
| JPH081858A (en) * | 1994-06-16 | 1996-01-09 | Sumitomo Metal Ind Ltd | Surface-treated steel sheet having excellent workability |
| JP2001234391A (en) * | 1999-03-15 | 2001-08-31 | Kobe Steel Ltd | Zn-Mg ELECTROPLATED METALLIC SHEET AND ITS MANUFACTURING METHOD |
| JP2001254195A (en) * | 2000-03-13 | 2001-09-18 | Nippon Steel Corp | Highly corrosion-resistant composite electroplated steel sheet and its manufacturing method |
| JP2003073882A (en) * | 2001-08-31 | 2003-03-12 | Nippon Hyomen Kagaku Kk | Alkaline galvannealing bath and galvannealing method |
| JP2003183875A (en) * | 2001-10-02 | 2003-07-03 | Shipley Co Llc | Plating bath and method for depositing metal layer on substrate |
| JP2004068153A (en) * | 2002-07-23 | 2004-03-04 | Nippon Hyomen Kagaku Kk | Galvanizing method with zincate bath |
-
2006
- 2006-03-22 JP JP2006079068A patent/JP4862445B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331457A (en) * | 1994-06-02 | 1995-12-19 | Sumitomo Metal Ind Ltd | Zinc phosphate treating plated metallic sheet bright in color tone and its production |
| JPH081858A (en) * | 1994-06-16 | 1996-01-09 | Sumitomo Metal Ind Ltd | Surface-treated steel sheet having excellent workability |
| JP2001234391A (en) * | 1999-03-15 | 2001-08-31 | Kobe Steel Ltd | Zn-Mg ELECTROPLATED METALLIC SHEET AND ITS MANUFACTURING METHOD |
| JP2001254195A (en) * | 2000-03-13 | 2001-09-18 | Nippon Steel Corp | Highly corrosion-resistant composite electroplated steel sheet and its manufacturing method |
| JP2003073882A (en) * | 2001-08-31 | 2003-03-12 | Nippon Hyomen Kagaku Kk | Alkaline galvannealing bath and galvannealing method |
| JP2003183875A (en) * | 2001-10-02 | 2003-07-03 | Shipley Co Llc | Plating bath and method for depositing metal layer on substrate |
| JP2004068153A (en) * | 2002-07-23 | 2004-03-04 | Nippon Hyomen Kagaku Kk | Galvanizing method with zincate bath |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012193419A (en) * | 2011-03-17 | 2012-10-11 | Jfe Steel Corp | Method for producing chemical conversion steel plate |
| CN103842559A (en) * | 2011-10-04 | 2014-06-04 | 杰富意钢铁株式会社 | Production method for zinc-electroplated steel sheets |
| WO2013051268A1 (en) * | 2011-10-04 | 2013-04-11 | Ｊｆｅスチール株式会社 | Production method for zinc-electroplated steel sheet |
| WO2013051269A1 (en) * | 2011-10-04 | 2013-04-11 | Ｊｆｅスチール株式会社 | Production method for zinc-electroplated steel sheets |
| JP2013079421A (en) * | 2011-10-04 | 2013-05-02 | Jfe Steel Corp | Production method for zinc-electroplated steel sheet |
| JP2013079422A (en) * | 2011-10-04 | 2013-05-02 | Jfe Steel Corp | Production method for zinc-electroplated steel sheet |
| CN103842558A (en) * | 2011-10-04 | 2014-06-04 | 杰富意钢铁株式会社 | Production method for zinc-electroplated steel sheet |
| TWI461575B (en) * | 2011-10-04 | 2014-11-21 | Jfe Steel Corp | Method of manufacturing electrogalvanized steel sheets |
| TWI465612B (en) * | 2011-10-04 | 2014-12-21 | Jfe Steel Corp | Method of manufacturing electrogalvanized steel sheets |
| KR20160113312A (en) | 2011-10-04 | 2016-09-28 | 제이에프이 스틸 가부시키가이샤 | Method for manufacturing electrogalvanized steel sheet |
| CN103842559B (en) * | 2011-10-04 | 2016-11-09 | 杰富意钢铁株式会社 | The manufacture method of plated steel sheet |
| JP2013185190A (en) * | 2012-03-07 | 2013-09-19 | Jfe Steel Corp | Method for manufacturing electrogalvanized steel sheet |
| JP2013194259A (en) * | 2012-03-16 | 2013-09-30 | Jfe Steel Corp | Method for producing electrogalvanized steel sheet |
| CN102747396A (en) * | 2012-06-28 | 2012-10-24 | 贵州钢绳股份有限公司 | Technology for electrogalvanizing of specially-shaped steel wire |
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