JP6950656B2 - Black steel plate - Google Patents
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- JP6950656B2 JP6950656B2 JP2018187331A JP2018187331A JP6950656B2 JP 6950656 B2 JP6950656 B2 JP 6950656B2 JP 2018187331 A JP2018187331 A JP 2018187331A JP 2018187331 A JP2018187331 A JP 2018187331A JP 6950656 B2 JP6950656 B2 JP 6950656B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 104
- 239000010959 steel Substances 0.000 title claims description 104
- 239000010960 cold rolled steel Substances 0.000 claims description 9
- 239000011701 zinc Substances 0.000 description 24
- 238000011282 treatment Methods 0.000 description 14
- 239000003929 acidic solution Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- -1 nitrate ions Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Description
本発明は、黒色鋼板及びその製造方法に関する。 The present invention relates to a black steel sheet and a method for producing the same.
黒色鋼板は、装飾性に優れていることから、パーソナルコンピュータ、複写機などの事務機器、空調機器などの家庭電化機器、自動車部品、及び内装建材などに広く用いられている。従来、黒色鋼板としては、ＮｉやＭｇを含有するめっきを施した鋼板や、カーボンブラックを含有する皮膜が形成された鋼板が一般的である。 Since black steel sheets are excellent in decorativeness, they are widely used in office equipment such as personal computers and copiers, household electrical equipment such as air conditioning equipment, automobile parts, and interior building materials. Conventionally, as a black steel sheet, a steel sheet plated with Ni or Mg or a steel sheet having a film containing carbon black is generally used.
特許文献１には、「Ｚｎ−Ｎｉめっき鋼板と、該Ｚｎ−Ｎｉめっき鋼板の表面に形成される黒色化処理層と、該黒色化処理層の外側に形成される有機樹脂層とを備える、黒色化鋼板であって、前記黒色化処理層に含まれる、金属ニッケル、酸化ニッケル、及び、酸化亜鉛の質量％を、それぞれ、Ａ％、Ｂ％、及び、Ｃ％とするとともに、前記黒色化処理層の表面をＰ１、該Ｐ１から０．１μｍ内側の前記黒色化処理層部位をＰ２とするとき、前記Ｐ１では、（Ａ＋Ｂ）／（Ａ＋Ｂ＋Ｃ）≧０．０１であるとともに、前記Ｐ２では、（Ａ＋Ｂ）／（Ａ＋Ｂ＋Ｃ）≦０．１５であることを特徴とする、黒色化鋼板」が開示されている。 Patent Document 1 includes "a Zn-Ni plated steel sheet, a blackening-treated layer formed on the surface of the Zn-Ni plated steel sheet, and an organic resin layer formed on the outside of the blackening-treated layer. The mass% of metallic nickel, nickel oxide, and zinc oxide contained in the blackened steel sheet in the blackened steel sheet is A%, B%, and C%, respectively, and the blackening is performed. When the surface of the treated layer is P1 and the blackened treatment layer portion 0.1 μm inside the P1 is P2, (A + B) / (A + B + C) ≥ 0.01 in the P1 and P2. A blackened steel sheet characterized by (A + B) / (A + B + C) ≦ 0.15 ”is disclosed.
特許文献２には、「Ｍｇの含有量が０.１〜４８.０質量％であり、Ａｌの含有量が１.０質量％未満である溶融Ｍｇ含有Ｚｎめっき層を有し、 前記溶融Ｍｇ含有Ｚｎめっき層は黒色酸化物を含有しており、前記溶融Ｍｇ含有Ｚｎめっき層の表面の明度は、Ｌ*値で４０未満である、黒色めっき鋼板」が開示されている。 Patent Document 2 states that "a molten Mg-containing Zn-plated layer having an Mg content of 0.1 to 48.0% by mass and an Al content of less than 1.0% by mass is provided, and the molten Mg is described. The black-plated steel sheet in which the contained Zn-plated layer contains a black oxide and the surface brightness of the molten Mg-containing Zn-plated layer is less than 40 in L * value is disclosed.
特許文献３には、「鋼板の少なくとも片面に形成された亜鉛系めっき層と、該亜鉛系めっき層上に形成されたクロムを含有しない化成皮膜と、該化成皮膜上に形成された単一有機塗膜とを具え、該単一有機塗膜は、カーボンブラックを12質量％超え、50質量％以下含有し、膜厚が0.3〜2μmであることを特徴とする黒色塗装鋼板」が開示されている。 Patent Document 3 states that "a zinc-based plating layer formed on at least one side of a steel plate, a chromium-free chemical conversion film formed on the zinc-based plating layer, and a single organic film formed on the chemical conversion film. A black-coated steel plate comprising a coating film, wherein the single organic coating film contains more than 12% by mass and 50% by mass or less of carbon black and has a film thickness of 0.3 to 2 μm. There is.
特許文献１では、黒色鋼板の黒色度は、黒色化処理層における金属ニッケル、酸化ニッケル、及び酸化亜鉛の割合に依存する。また、特許文献２では、黒色鋼板の黒色度は、溶融Ｍｇ含有Ｚｎめっき層が水蒸気に接触することにより生成する酸素欠乏型の酸化物量に依存する。特許文献３の方法によれば、黒色鋼板の黒色度は、単一有機塗膜におけるカーボンブラックの色に依存する。そのため、これらの方法では黒色度の細かい調整が困難であり、これに起因してＬ値（白色度）が高くなる場合がある。よって、黒色外観には改善の余地がある。 In Patent Document 1, the blackness of the black steel sheet depends on the ratio of metallic nickel, nickel oxide, and zinc oxide in the blackening treatment layer. Further, in Patent Document 2, the blackness of the black steel sheet depends on the amount of oxygen-deficient oxide generated when the molten Mg-containing Zn plating layer comes into contact with water vapor. According to the method of Patent Document 3, the blackness of the black steel sheet depends on the color of carbon black in the single organic coating film. Therefore, it is difficult to finely adjust the blackness with these methods, and the L value (whiteness) may increase due to this. Therefore, there is room for improvement in the black appearance.
本発明は、上記課題に鑑み、優れた黒色外観を有する黒色鋼板を提供することを目的とする。また、本発明は、優れた黒色外観を有する黒色鋼板を得ることが可能な黒色鋼板の製造方法を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a black steel sheet having an excellent black appearance. Another object of the present invention is to provide a method for producing a black steel sheet capable of obtaining a black steel sheet having an excellent black appearance.
本発明者らは、上記課題を解決すべく検討したところ、鋼板の少なくとも片面上に酸化物層を形成し、該酸化物層におけるＺｎとＳの含有量を最適化することにより、優れた黒色外観を有する黒色鋼板が得られることを知見した。 As a result of studies to solve the above problems, the present inventors have formed an oxide layer on at least one surface of the steel sheet, and optimized the content of Zn and S in the oxide layer to obtain an excellent black color. It was found that a black steel sheet having an appearance can be obtained.
本発明は、上記知見に基づき、その要旨構成は以下のとおりである。
（１）鋼板の少なくとも片面に酸化物層を有し、該酸化物層は、Ｚｎを３００ｍｇ／ｍ2以上含有し、Ｓを１０ｍｇ／ｍ2以上含有する黒色鋼板。
Based on the above findings, the present invention has the following gist structure.
(1) A black steel sheet having an oxide layer on at least one side of the steel sheet, and the oxide layer contains Zn of 300 mg / m 2 or more and S of 10 mg / m 2 or more.
（２）前記酸化物層の平均厚さが１００ｎｍ以上である、上記（１）に記載の黒色鋼板。 (2) The black steel sheet according to (1) above, wherein the oxide layer has an average thickness of 100 nm or more.
（３）前記酸化物層の表面におけるＬ値が２０以下である、上記（１）または（２）に記載の黒色鋼板。 (3) The black steel sheet according to (1) or (2) above, wherein the L value on the surface of the oxide layer is 20 or less.
（４）前記鋼板は、冷延鋼板、熱延鋼板、またはめっき鋼板である、上記（１）〜（３）のいずれか一つに記載の黒色鋼板。 (4) The black steel sheet according to any one of (1) to (3) above, wherein the steel sheet is a cold-rolled steel sheet, a hot-rolled steel sheet, or a plated steel sheet.
（５）硫酸イオンを０．０５ｍｏｌ／ｌ以上、亜鉛イオンを０．０５ｍｏｌ／ｌ以上、及び硝酸イオンを０．０１ｍｏｌ／ｌ以上含有する酸性溶液中において、鋼板を陰極とする、電解処理を行って、該鋼板の少なくとも片面に酸化物層を形成する黒色鋼板の製造方法。 (5) Electrolysis is performed using a steel plate as a cathode in an acidic solution containing 0.05 mol / l or more of sulfate ions, 0.05 mol / l or more of zinc ions, and 0.01 mol / l or more of nitrate ions. A method for producing a black steel plate having an oxide layer formed on at least one surface of the steel plate.
（６）前記電解処理を行う際の電流密度を１Ａ／ｄｍ2以上２０Ａ／ｄｍ2以下とする、上記（５）に記載の黒色鋼板の製造方法。 (6) The method for producing a black steel sheet according to (5) above, wherein the current density at the time of performing the electrolytic treatment is 1 A / dm 2 or more and 20 A / dm 2 or less.
（７）前記酸性溶液のｐＨを２以上５以下とする、上記（５）または（６）に記載の黒色鋼板の製造方法。 (7) The method for producing a black steel sheet according to (5) or (6) above, wherein the pH of the acidic solution is 2 or more and 5 or less.
（８）前記酸化物層の平均厚さを１００ｎｍ以上とする、上記（５）〜（７）のいずれか一つに記載の黒色鋼板の製造方法。 (8) The method for producing a black steel sheet according to any one of (5) to (7) above, wherein the average thickness of the oxide layer is 100 nm or more.
（９）前記酸化物層の表面におけるＬ値を２０以下とする、上記（５）〜（８）のいずれか一つに記載の黒色鋼板の製造方法。 (9) The method for producing a black steel sheet according to any one of (5) to (8) above, wherein the L value on the surface of the oxide layer is 20 or less.
（１０）前記鋼板を冷延鋼板、熱延鋼板、またはめっき鋼板とする、上記（５）〜（９）のいずれか一つに記載の黒色鋼板の製造方法。 (10) The method for producing a black steel sheet according to any one of (5) to (9) above, wherein the steel sheet is a cold-rolled steel sheet, a hot-rolled steel sheet, or a plated steel sheet.
本発明によれば、優れた黒色外観を有する黒色鋼板を得ることができる。 According to the present invention, a black steel sheet having an excellent black appearance can be obtained.
以下、本発明の構成と限定理由を説明する。 Hereinafter, the configuration of the present invention and the reasons for limitation will be described.
（黒色鋼板）
本発明の黒色鋼板は、鋼板と、該鋼板の少なくとも片面に形成された酸化物層を有する。以下、黒色鋼板の各構成要素の詳細について説明する。
(Black steel plate)
The black steel sheet of the present invention has a steel sheet and an oxide layer formed on at least one side of the steel sheet. Hereinafter, details of each component of the black steel sheet will be described.
［鋼板］
本発明の鋼板は、特に限定されず、例えば冷延鋼板、熱延鋼板、またはめっき鋼板が挙げられる。めっき鋼板としては、Ｚｎ系めっき鋼板やＡｌ系めっき鋼板などが挙げられる。Ｚｎ系めっき鋼板としては、一般的な電気亜鉛めっき鋼板（ＥＧ）、溶融亜鉛めっき鋼板（ＧＩ）、合金化溶融亜鉛めっき鋼板（ＧＡ）、Ｚｎ−Ｎｉめっき鋼板、Ｚｎ−Ａｌめっき鋼板、Ｚｎ−Ｍｇめっき鋼板、Ｚｎ−Ａｌ−Ｍｇめっき鋼板、蒸着Ｚｎめっき鋼板などが挙げられる。Ａｌ系めっき鋼板としては、Ａｌ−Ｓｉめっき鋼板、Ａｌ−Ｍｇ−Ｓｉめっき鋼板などが挙げられる。
[Steel plate]
The steel sheet of the present invention is not particularly limited, and examples thereof include cold-rolled steel sheets, hot-rolled steel sheets, and plated steel sheets. Examples of the plated steel sheet include a Zn-based plated steel sheet and an Al-based plated steel sheet. As Zn-based plated steel sheets, general electrogalvanized steel sheets (EG), hot-dip galvanized steel sheets (GI), alloyed hot-dip galvanized steel sheets (GA), Zn-Ni plated steel sheets, Zn-Al plated steel sheets, Zn- Examples thereof include Mg-plated steel sheets, Zn-Al-Mg-plated steel sheets, and vapor-deposited Zn-plated steel sheets. Examples of the Al-based plated steel sheet include an Al-Si plated steel sheet and an Al-Mg-Si plated steel sheet.
［酸化物層］
本発明の酸化物層は、酸化物層におけるＺｎの含有量が３００ｍｇ／ｍ2以上であり、Ｓの含有量が１０ｍｇ／ｍ2以上であることが重要である。これにより、優れた黒色外観を有する黒色鋼板が得られる。この理由は、定かではないが、以下のように考えられる。すなわち、図１Ａ，Ｂを参照して、酸化物層におけるＺｎおよびＳの含有量を上述した範囲とすることにより、酸化物層の表面に深い凹凸構造が形成される。すると、図１Ｃに示すように、この深い凹凸構造による入射光の多重反射による光の減衰に起因して、外部に放出される光の量が抑制され、優れた黒色外観が得られる。具体的には、酸化物層の表面におけるＬ値を２０以下にすることができる。なお、本明細書における「Ｌ値」とは、分光色彩計（日本電色工業株式会社製のＳＤ７０００）を用いて、酸化物層の表面における色調をＳＣＥ（正反射光除去）モードで測定した値を意味する。
[Oxide layer]
It is important that the oxide layer of the present invention has a Zn content of 300 mg / m 2 or more and an S content of 10 mg / m 2 or more in the oxide layer. As a result, a black steel sheet having an excellent black appearance can be obtained. The reason for this is not clear, but it is thought to be as follows. That is, by referring to FIGS. 1A and 1B and setting the contents of Zn and S in the oxide layer within the above-mentioned range, a deep uneven structure is formed on the surface of the oxide layer. Then, as shown in FIG. 1C, the amount of light emitted to the outside is suppressed due to the attenuation of the light due to the multiple reflection of the incident light due to this deep uneven structure, and an excellent black appearance can be obtained. Specifically, the L value on the surface of the oxide layer can be 20 or less. The "L value" in the present specification means that the color tone on the surface of the oxide layer was measured in the SCE (specular reflection light removal) mode using a spectrocolorimeter (SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.). Means a value.
より優れた黒色外観を得るために、酸化物層におけるＺｎの含有量は１１００ｍｇ／ｍ2以上とすることが好ましく、Ｓの含有量は１００ｍｇ／ｍ2以上とすることが好ましい。これによりＬ値を１０未満にできる。また、鋼板と酸化物層との密着性を向上させる観点から、酸化物層におけるＺｎの含有量は５０００ｍｇ／ｍ2以下とすることが好ましく、Ｓの含有量は２００ｍｇ／ｍ2以下とすることが好ましい。 In order to obtain a more excellent black appearance, the Zn content in the oxide layer is preferably 1100 mg / m 2 or more, and the S content is preferably 100 mg / m 2 or more. As a result, the L value can be set to less than 10. Further, from the viewpoint of improving the adhesion between the steel sheet and the oxide layer, the Zn content in the oxide layer is preferably 5000 mg / m 2 or less, and the S content is 200 mg / m 2 or less. Is preferable.
本願明細書における「Ｚｎの含有量」および「Ｓの含有量」は、以下の定義に従う。すなわち、重クロム酸アンモニウム２質量％＋アンモニア水１４質量％の溶液において、酸化物層を溶解した溶液を、ＩＣＰ発光分析装置を用いて分析することにより、酸化物層におけるＺｎおよびＳの含有量を算出する。 The "Zn content" and "S content" in the specification of the present application follow the following definitions. That is, the content of Zn and S in the oxide layer was analyzed by using an ICP emission spectrometer to analyze the solution in which the oxide layer was dissolved in a solution of 2% by mass of ammonium dichromate + 14% by mass of aqueous ammonia. Is calculated.
黒色外観をさらに向上させる観点から、酸化物層の平均厚さは１００ｎｍ以上であることが好ましい。また、基板と酸化物層との密着性を向上させる観点から、酸化物層の平均厚さは４００ｎｍ以下であることが好ましい。 From the viewpoint of further improving the black appearance, the average thickness of the oxide layer is preferably 100 nm or more. Further, from the viewpoint of improving the adhesion between the substrate and the oxide layer, the average thickness of the oxide layer is preferably 400 nm or less.
本願明細書における「酸化物層の平均厚さ」は、以下の定義に従う。すなわち、酸化物層における酸素強度を蛍光Ｘ線により測定し、得られた酸素強度から、厚さが既知のシリコン酸化膜を形成したシリコンウェーハの値を基準として、酸化物層の厚さをシリコン酸化膜の厚さに換算する。同様の測定を酸化物層の表面の３箇所以上において行い、これらの平均値を酸化物層の平均厚さとする。 The "average thickness of the oxide layer" in the specification of the present application follows the following definition. That is, the oxygen intensity in the oxide layer is measured by fluorescent X-ray fluorescence, and the thickness of the oxide layer is determined from the obtained oxygen intensity based on the value of the silicon wafer on which the silicon oxide film having a known thickness is formed. Converted to the thickness of the oxide film. Similar measurements are made at three or more locations on the surface of the oxide layer, and the average value of these is taken as the average thickness of the oxide layer.
本発明の黒色鋼板は、必要に応じて、酸化物層の表面に無機系皮膜、有機系皮膜、又はこれらの複合皮膜を有していてもよい。なお、これらの皮膜を有する黒色鋼板も、本発明の効果を奏することはいうまでもない。 The black steel sheet of the present invention may have an inorganic film, an organic film, or a composite film thereof on the surface of the oxide layer, if necessary. Needless to say, the black steel sheet having these films also exerts the effect of the present invention.
（黒色鋼板の製造方法）
次に、本発明による黒色鋼板の製造方法について説明する。
(Manufacturing method of black steel sheet)
Next, a method for manufacturing a black steel sheet according to the present invention will be described.
［鋼板の準備］
まず、上述した冷延鋼板や熱延鋼板やめっき鋼板などの鋼板を準備する。なお、冷延鋼板やめっき鋼板の製造方法については、特に限定されず、一般的な方法を用いることができる。
[Preparation of steel plate]
First, steel sheets such as the above-mentioned cold-rolled steel sheet, hot-rolled steel sheet, and plated steel sheet are prepared. The method for producing the cold-rolled steel sheet or the plated steel sheet is not particularly limited, and a general method can be used.
［酸化物層の形成］
次に、本発明では、硫酸イオンを０．０５ｍｏｌ／ｌ以上、亜鉛イオンを０．０５ｍｏｌ／ｌ以上、及び硝酸イオンを０．０１ｍｏｌ／ｌ以上含有する酸性溶液中において、鋼板を陰極とする、電解処理を行うことが重要である。これにより、鋼板の少なくとも片面に、Ｚｎの含有量が３００ｍｇ／ｍ2以上であり、Ｓの含有量が１０ｍｇ／ｍ2以上となる酸化物層が形成される。
[Formation of oxide layer]
Next, in the present invention, the steel plate is used as a cathode in an acidic solution containing 0.05 mol / l or more of sulfate ions, 0.05 mol / l or more of zinc ions, and 0.01 mol / l or more of nitrate ions. It is important to perform electrolytic treatment. As a result, an oxide layer having a Zn content of 300 mg / m 2 or more and an S content of 10 mg / m 2 or more is formed on at least one surface of the steel sheet.
酸化物層の形成メカニズムは、定かではないが、以下のように考えられる。上述した電解処理を行うと、鋼板（陰極）側では、水素イオンの還元による水素の発生と硝酸イオンの還元によって、鋼板の少なくとも片面におけるｐＨが急激に上昇する。この時、鋼板の少なくとも片面付近の酸性溶液中に硫酸イオンと亜鉛イオンが存在するので、鋼板の少なくとも片面において、Ｚｎ、Ｏ、Ｓが化合物として沈殿析出し、ＺｎおよびＳを含有する酸化物層が形成される。 The mechanism of formation of the oxide layer is not clear, but it is considered as follows. When the above-mentioned electrolysis treatment is performed, on the steel plate (cathode) side, the pH on at least one side of the steel plate sharply rises due to the generation of hydrogen by the reduction of hydrogen ions and the reduction of nitrate ions. At this time, since sulfate ion and zinc ion are present in the acidic solution near at least one side of the steel plate, Zn, O, and S are precipitated as compounds on at least one side of the steel plate, and the oxide layer containing Zn and S. Is formed.
このような形成メカニズムの観点から、酸性溶液中の硫酸イオンは０．０５ｍｏｌ／ｌ以上、亜鉛イオンは０．０５ｍｏｌ／ｌ以上、及び硝酸イオンは０．０１ｍｏｌ／ｌ以上とする。硫酸イオンおよび亜鉛イオンがそれぞれ０．０５ｍｏｌ／ｌ未満の場合、鋼板の少なくとも片面におけるｐＨが急激に上昇した時に、ＺｎイオンおよびＳイオンの供給不足となる。また、硝酸イオンが０．０１ｍｏｌ／ｌ未満の場合、電解処理を行った時のｐＨの上昇が不十分となる。これらに起因して、酸化物層におけるＺｎの含有量が３００ｍｇ／ｍ2未満となり、Ｓの含有量が１０ｍｇ／ｍ2未満となるので、優れた黒色外観が得られない。なお、本発明では、鋼板を陰極とする電解処理を行うので、鋼板として亜鉛系めっき鋼板を用いる場合でも、亜鉛系めっき中のＺｎが酸性溶液に溶解することはほぼないと考えられる。 From the viewpoint of such a formation mechanism, the sulfate ion in the acidic solution is 0.05 mol / l or more, the zinc ion is 0.05 mol / l or more, and the nitrate ion is 0.01 mol / l or more. When the sulfate ion and the zinc ion are less than 0.05 mol / l, respectively, the supply of Zn ion and S ion becomes insufficient when the pH on at least one side of the steel sheet rises sharply. Further, when the nitrate ion is less than 0.01 mol / l, the increase in pH at the time of performing the electrolytic treatment becomes insufficient. Due to these, the Zn content in the oxide layer is less than 300 mg / m 2 , and the S content is less than 10 mg / m 2 , so that an excellent black appearance cannot be obtained. In the present invention, since the electrolytic treatment is performed using the steel sheet as the cathode, it is considered that Zn in the zinc-based plating is hardly dissolved in the acidic solution even when the zinc-based plated steel sheet is used as the steel sheet.
製造コストの観点から、酸性溶液中の硫酸イオンは１．５ｍｏｌ／ｌ以下とすることが好ましく、亜鉛イオンは１．５ｍｏｌ／ｌ以下とすることが好ましく、硝酸イオンは１．５ｍｏｌ／ｌ以下とすることが好ましい。 From the viewpoint of production cost, the sulfate ion in the acidic solution is preferably 1.5 mol / l or less, the zinc ion is preferably 1.5 mol / l or less, and the nitrate ion is 1.5 mol / l or less. It is preferable to do so.
電解処理を行う際の電流密度は、１Ａ／ｄｍ2以上２０Ａ／ｄｍ2以下とすることが好ましい。１Ａ／ｄｍ2以上であれば、鋼板（陰極）の少なくとも片面におけるｐＨの上昇がより促進されるので、より優れた黒色外観が得られるからである。２０Ａ／ｄｍ2以下であれば、酸化物層が急激に形成されるおそれがないので、酸化物層の表面においてムラ（外観不均一）が生じるおそれがないからである。なお、電流密度は、５Ａ／ｄｍ2以上とすることがより好ましい。 The current density during the electrolytic treatment is preferably 1 A / dm 2 or more and 20 A / dm 2 or less. This is because when it is 1 A / dm 2 or more, the increase in pH on at least one side of the steel sheet (cathode) is further promoted, so that a better black appearance can be obtained. When it is 20 A / dm 2 or less, there is no possibility that the oxide layer is rapidly formed, so that there is no possibility that unevenness (non-uniform appearance) occurs on the surface of the oxide layer. The current density is more preferably 5 A / dm 2 or more.
酸性溶液のｐＨは２以上５以下とすることが好ましい。ｐＨが２以上であれば、上述した還元がより促進されるので、より優れた黒色外観が得られるからである。ｐＨが５以下であれば、鋼板の表面にＺｎイオンが析出するおそれがないので、スラッジが発生するおそれもないからである。 The pH of the acidic solution is preferably 2 or more and 5 or less. This is because when the pH is 2 or more, the above-mentioned reduction is further promoted, so that a better black appearance can be obtained. This is because when the pH is 5 or less, there is no possibility that Zn ions are deposited on the surface of the steel sheet, so that sludge is not generated.
電解処理の時間は０．１秒以上２００ｓ以下とすることが好ましい。０．１秒以上であれば、酸化物層の平均厚さを１００ｎｍ以上にすることができるので、優れた黒色外観が得られるからである。２００ｓ以下であれば、酸化物層の平均厚さを４００ｎｍ以下にすることができるので、鋼板と酸化物層との密着性を劣化させることがないからである。 The time of the electrolysis treatment is preferably 0.1 seconds or more and 200 s or less. This is because the average thickness of the oxide layer can be 100 nm or more in 0.1 seconds or more, so that an excellent black appearance can be obtained. This is because if it is 200 s or less, the average thickness of the oxide layer can be 400 nm or less, so that the adhesion between the steel sheet and the oxide layer is not deteriorated.
なお、黒色度の調整は、酸化物層の平均厚さを変化させることにより行うことが好ましい。ただし、酸化物層の平均厚さを一定にしつつ、黒色度を高めたい場合には、電流密度を上昇させることが好ましい。 The blackness is preferably adjusted by changing the average thickness of the oxide layer. However, if it is desired to increase the blackness while keeping the average thickness of the oxide layer constant, it is preferable to increase the current density.
電解処理中の酸性溶液の温度は、２０℃以上８０℃以下とすることが好ましい。２０℃以上であれば、酸化物層の形成速度が低下するおそれがなく、生産性を確保できるからである。８０℃以下であれば、酸性溶液が蒸発するのを抑制することができるので、溶液管理が容易になるからである。 The temperature of the acidic solution during the electrolytic treatment is preferably 20 ° C. or higher and 80 ° C. or lower. This is because if the temperature is 20 ° C. or higher, the formation rate of the oxide layer does not decrease and the productivity can be ensured. This is because if the temperature is 80 ° C. or lower, evaporation of the acidic solution can be suppressed, so that solution management becomes easy.
なお、酸性溶液の残部は、水および不可避的不純物であり、例えば水に不純物が含まれることによりＮ、Ｂ、Ｆ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ａｌ、Ｍｎ、Ｃｕなどが不可避的に取り込まれても、本発明の効果を奏することはいうまでもない。 The balance of the acidic solution is water and unavoidable impurities. For example, N, B, F, Na, K, Mg, Ca, Al, Mn, Cu and the like are inevitably taken in by the inclusion of impurities in water. Needless to say, the effect of the present invention is exhibited.
［水洗および乾燥］
電解処理の後、黒色鋼板を水洗することが好ましく、必要に応じて、水洗後に乾燥を行ってもよい。なお、水洗および乾燥の方法は、特に限定されず、一般的な方法を用いることができる。
[Washing and drying]
It is preferable to wash the black steel sheet with water after the electrolytic treatment, and if necessary, drying may be performed after washing with water. The method of washing with water and drying is not particularly limited, and a general method can be used.
また、電解処理の後、必要に応じて、酸化物層の表面に無機系皮膜、有機系皮膜、又はこれらの複合皮膜を形成してもよい。これらの皮膜は、ロールコーター法、浸漬法、スプレー塗装など任意の方法により形成することができる。なお、これらの処理を施した黒色鋼板も、本発明の効果を奏することはいうまでもない。 Further, after the electrolytic treatment, an inorganic film, an organic film, or a composite film thereof may be formed on the surface of the oxide layer, if necessary. These films can be formed by any method such as a roll coater method, a dipping method, and a spray coating method. Needless to say, the black steel sheet subjected to these treatments also exerts the effect of the present invention.
以下、実施例に従って、本発明をより具体的に説明するが、本発明は下記の実施例によって制限されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
（実施例１）
板厚：０．６ｍｍのＡｌキルド冷延鋼板を準備し、表１に示す酸性溶液中において、当該冷延鋼板を陰極とする、表１に示す条件下で電解処理を行って、その後、水洗および乾燥を行って、黒色鋼板を得た。その後、以下の方法で黒色鋼板から採取した各試験片に対して、以下の評価を行った。
(Example 1)
An Al-killed cold-rolled steel sheet having a plate thickness of 0.6 mm is prepared, electrolyzed in the acidic solution shown in Table 1 under the conditions shown in Table 1 with the cold-rolled steel sheet as a cathode, and then washed with water. And drying was performed to obtain a black steel plate. Then, the following evaluations were performed on each test piece collected from the black steel sheet by the following method.
＜酸化物層の平均厚さ＞
蛍光Ｘ線分析装置の測定ステージ上に直径４８ｍｍの円形に打抜いた試験片をセットし、酸化物層からＯ−Ｋα線を検出した。また、試料ステージ上には、試験片と一緒に、適当な大きさに劈開した膜厚：９６ｎｍ、５４ｎｍ及び２４ｎｍのシリコン酸化膜をそれぞれ形成したシリコンウェーハをセットし、これらのシリコン酸化膜からもＯ−Ｋα線を検出した。これらのデータを用いて、酸化物層の厚さとＯ−Ｋα線の強度との検量線を作成し、試験片における酸化物層の厚さをシリコン酸化膜換算での酸化物層の厚さとして算出した。そして、同様の測定を３箇所にて行い、これらの平均値を酸化物層の平均厚さとした。評価結果を表１に示す。なお、測定時の管球の電圧を３０ｋＶとし、電流を１００ｍＡとし、分光結晶をＴＡＰに設定した。また、Ｏ−Ｋα線の測定に際しては、そのピーク位置に加えてバックグラウンド位置での強度も測定し、Ｏ−Ｋα線の正味の強度を算出した。ピーク位置およびバックグラウンド位置での積分時間はそれぞれ２０秒とした。
<Average thickness of oxide layer>
A circularly punched test piece having a diameter of 48 mm was set on the measurement stage of the fluorescent X-ray analyzer, and OKα rays were detected from the oxide layer. Further, on the sample stage, a silicon wafer having silicon oxide films of 96 nm, 54 nm, and 24 nm formed on the sample stage, which are cleaved to an appropriate size, is set together with the test piece, and these silicon oxide films are also used. OKα rays were detected. Using these data, a calibration curve was created between the thickness of the oxide layer and the intensity of the OKα ray, and the thickness of the oxide layer in the test piece was used as the thickness of the oxide layer in terms of silicon oxide film. Calculated. Then, the same measurement was performed at three points, and the average value of these was taken as the average thickness of the oxide layer. The evaluation results are shown in Table 1. The voltage of the tube at the time of measurement was set to 30 kV, the current was set to 100 mA, and the spectroscopic crystal was set to TAP. In addition, when measuring the OKα ray, the intensity at the background position was measured in addition to the peak position, and the net intensity of the OKα ray was calculated. The integration time at the peak position and the background position was set to 20 seconds, respectively.
＜酸化物層の表面におけるＬ値＞
黒色度の指標として、酸化物層の表面におけるＬ値を測定した。すなわち、分光色彩計（日本電色工業株式会社製のＳＤ７０００）を用いて、５０ｍｍ×５０ｍｍに切り出した試験片の酸化物層の表面における色調をＳＣＥ（正反射光除去）モードで測定した。評価結果を表１に示す。
<L value on the surface of the oxide layer>
As an index of blackness, the L value on the surface of the oxide layer was measured. That is, using a spectrocolorimeter (SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the color tone on the surface of the oxide layer of the test piece cut out to 50 mm × 50 mm was measured in the SCE (specular reflection light removal) mode. The evaluation results are shown in Table 1.
＜酸化物層の組成分析＞
重クロム酸アンモニウム２質量％＋アンモニア水１４質量％の溶液を用いて、試験片のうち酸化物層のみを溶解した。そして、溶解した溶液を、ＩＣＰ発光分析装置を用いて分析することで、酸化物層におけるＺｎおよびＳの含有量を算出した。評価結果を表１に示す。なお、表１に示す結果は、ＺｎおよびＳの含有量を試験片の主面の面積（５０ｍｍ×５０ｍｍ）で除した値である。
<Composition analysis of oxide layer>
Only the oxide layer of the test pieces was dissolved using a solution of 2% by mass of ammonium dichromate + 14% by mass of aqueous ammonia. Then, the dissolved solution was analyzed using an ICP emission spectrometer to calculate the contents of Zn and S in the oxide layer. The evaluation results are shown in Table 1. The results shown in Table 1 are values obtained by dividing the Zn and S contents by the area of the main surface of the test piece (50 mm × 50 mm).
＜密着性試験＞
３０ｍｍ×１００ｍｍに切り出した試験片の評価面を外側に向け、先端が２．０Ｒで９０°の金型を用いて曲げ加工を加えた後にセロハンテープ（登録商標）を貼り付けて引き離した後、色調変化の認められないものを「○」、黒色度がわずかに低下したものを「△」、酸化物層が剥離し、金属光沢が見られたものを「×」として、密着性を評価した。評価結果を表１に示す。
<Adhesion test>
After bending the test piece cut into 30 mm x 100 mm with the evaluation surface facing outward and using a mold with a tip of 2.0 R and 90 °, a cellophane tape (registered trademark) is attached and separated. Adhesion was evaluated as "○" when no color change was observed, "△" when the blackness was slightly reduced, and "×" when the oxide layer was peeled off and metallic luster was observed. .. The evaluation results are shown in Table 1.
（実施例２）
板厚：０．６ｍｍのＡｌキルド冷延鋼板に対して、表３に示すめっき種にてめっき処理を行って、めっき鋼板を準備した。引き続き、表２に示す酸性溶液中において、当該めっき鋼板を陰極とする、表２に示す条件下で電解処理を行って、その後、水洗および乾燥を行って、黒色鋼板を得た。その後、実施例１と同様の評価を行った。評価結果を表２に示す。
(Example 2)
An Al-killed cold-rolled steel sheet having a plate thickness of 0.6 mm was plated with the plating types shown in Table 3 to prepare a plated steel sheet. Subsequently, in the acidic solution shown in Table 2, electrolytic treatment was carried out under the conditions shown in Table 2 using the plated steel sheet as a cathode, and then water washing and drying were carried out to obtain a black steel sheet. Then, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.
本発明によれば、優れた黒色外観を有する黒色鋼板を得ることができる。 According to the present invention, a black steel sheet having an excellent black appearance can be obtained.
Claims (3)
The black steel sheet according to claim 1 or 2 , wherein the steel sheet is a cold-rolled steel sheet, a hot-rolled steel sheet, or a plated steel sheet.
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