JP2021059779A - Electrogalvanized steel sheet and method for producing electrogalvanized steel sheet - Google Patents
Electrogalvanized steel sheet and method for producing electrogalvanized steel sheet Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 74
- 239000010959 steel Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000010419 fine particle Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 24
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims 1
- 239000004020 conductor Substances 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 239000002932 luster Substances 0.000 description 24
- 238000007747 plating Methods 0.000 description 20
- 238000005422 blasting Methods 0.000 description 17
- 238000011282 treatment Methods 0.000 description 16
- 238000005259 measurement Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 210000002287 horizontal cell Anatomy 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本発明は、コンダクターロール圧下による金属光沢を大きく低減させた美麗な外観を有する電気亜鉛めっき鋼板および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 an electrogalvanized steel sheet and a method for producing an electrogalvanized steel sheet having a beautiful appearance in which metallic luster due to conductor roll reduction is greatly reduced.
電気亜鉛めっき鋼板は、家電製品、自動車、建材などの広範な用途で使用されている。中でも、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においては、表面外観に優れることが要求される。各種化成処理後の外観は化成処理前の亜鉛めっき外観に大きく左右されるため、化成処理前の外観が重要である。電気亜鉛めっき鋼板においては亜鉛結晶の微細な凹凸による拡散反射により、金属光沢の少ない白色美麗な外観を有することが知られている。 Electrogalvanized steel sheets are used in a wide range of applications such as home appliances, automobiles, and building materials. Above all, various chemical conversion-treated electrogalvanized steel sheets for home appliances used without painting are required to have excellent surface appearance. Since the appearance after various chemical conversion treatments is greatly affected by the appearance of zinc plating before the chemical conversion treatment, the appearance before the chemical conversion treatment is important. It is known that an electrogalvanized steel sheet has a beautiful white appearance with little metallic luster due to diffuse reflection due to fine irregularities of zinc crystals.
電気亜鉛めっき鋼板は、冷延鋼板を亜鉛イオンを含有する電解液中で陰極電解処理することによって得られる。電気めっき装置としては、電解槽の形式によって、縦型、水平型、ラジアル型の３種類が知られている。いずれの装置においてもめっき槽内に鋼板と相対して対極を配し、コンダクターロールを通して鋼板に通電している。 The electrogalvanized steel sheet is obtained by cathodic electrolysis treatment of a cold-rolled steel sheet in an electrolytic solution containing zinc ions. Three types of electroplating devices are known, vertical type, horizontal type, and radial type, depending on the type of electrolytic cell. In each of the devices, a counter electrode is arranged in the plating tank so as to face the steel sheet, and the steel sheet is energized through a conductor roll.
ここで、電気めっき後にコンダクターロールと接する側において、亜鉛めっき結晶がコンダクターロールに押し潰されることで亜鉛結晶の平滑な箇所ができ、金属光沢を発する部分が散在する外観を呈し、表面外観を損なう及びめっき後の外観に表裏差が生じるという問題があった。図１に水平型セルを示すが、電気めっき後に５ｂのコンダクターロールに接触することで、平滑部が形成される。 Here, on the side in contact with the conductor roll after electroplating, the zinc-plated crystal is crushed by the conductor roll to form a smooth portion of the zinc crystal, which gives an appearance in which metallic luster is scattered and impairs the surface appearance. In addition, there is a problem that the appearance after plating has a difference between the front and back sides. A horizontal cell is shown in FIG. 1, and a smooth portion is formed by contacting the conductor roll of 5b after electroplating.
このようなめっき面の表裏差の解消および外観を改善する方法として、コンダクターロールやバックアップロールの配置、圧下力、硬度を調整する技術が検討され、特許文献１には、複数配置されたコンダクターロールとバックアップロールの上下配置を交互に替える技術が、特許文献２には、コンダクターロールの圧下力を低減し、バックアップロールの硬度を制御する技術が開示されている。
As a method for eliminating the difference between the front and back surfaces of the plated surface and improving the appearance, a technique for adjusting the arrangement, rolling force, and hardness of conductor rolls and backup rolls has been studied, and Patent Document 1 describes a plurality of conductor rolls arranged.
特許文献３には、溶融亜鉛めっき鋼板の表面に個体微粒子を投射し、表面に微細な凹凸を付与してめっき表面光沢を調整して電気亜鉛めっき鋼板と同様な外観を得る技術が開示されている。
特許文献１の技術では、めっき面外観の表裏差を軽減することはできても、両面に押しつぶされた跡は残るために、金属光沢を誘発する外観は変わらない。そのため、無塗装で使用される場合、良好な外観を得られないという問題があった。 Although the technique of Patent Document 1 can reduce the difference between the front and back surfaces of the plated surface, the appearance that induces metallic luster does not change because crushed marks remain on both sides. Therefore, when it is used without painting, there is a problem that a good appearance cannot be obtained.
特許文献２の技術では、金属光沢部の軽減はできるが、金属光沢を有する部分が散在する外観を解消するには至らないという課題があった。
The technique of
特許文献３の技術では、金属光沢部の軽減はできるが、めっき面表裏の光沢度の差を十分に少なくすることは出来なかった。
With the technique of
本発明は、かかる事情を鑑みてなされたものであって、コンダクターロール圧下で形成される金属光沢度を大きく低減して、表裏の光沢度差を低減し、表裏共に美麗な表面外観を有する電気亜鉛めっき鋼板および電気亜鉛めっき鋼板の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances. Electricity having a beautiful surface appearance on both the front and back sides by greatly reducing the metallic luster formed under conductor roll pressure and reducing the difference in glossiness between the front and back surfaces. It is an object of the present invention to provide a method for manufacturing a galvanized steel sheet and an electrogalvanized steel sheet.
本発明者らは、前記課題を解決すべく、電気亜鉛めっき鋼板特有の美麗な外観を維持しながらコンダクターロール圧下による金属光沢部を光沢のない状態に変化させる方法について鋭意研究を重ねた。その結果、電気亜鉛めっき鋼板表面に平均粒径６〜１５０μｍの特定形状の微粒子を混合した液体を噴射することにより、金属光沢部のない外観が得られ、表裏の光沢度差が最小となる電気亜鉛めっき鋼板を製造できることが明らかになった。ここで、表裏の光沢度差が最小となる電気亜鉛めっき鋼板とは、表裏の光沢度差が５以下であることを意味する。表裏の光沢度差が５以下であれば、肉眼での光沢度差は認識困難である。更に、電気亜鉛めっき面の光沢度Ｇｓ（６０°）が１５以下であれば、光沢が無いと認識できる。 In order to solve the above problems, the present inventors have conducted extensive research on a method of changing the metallic luster portion under conductor roll reduction to a dull state while maintaining the beautiful appearance peculiar to the electrogalvanized steel sheet. As a result, by injecting a liquid mixed with fine particles having a specific shape having an average particle size of 6 to 150 μm onto the surface of an electrogalvanized steel sheet, an appearance without metallic luster is obtained, and the difference in gloss between the front and back surfaces is minimized. It has become clear that galvanized steel sheets can be manufactured. Here, the electrogalvanized steel sheet having the minimum gloss difference between the front and back means that the gloss difference between the front and back is 5 or less. If the difference in glossiness between the front and back surfaces is 5 or less, it is difficult to recognize the difference in glossiness with the naked eye. Further, if the glossiness Gs (60 °) of the electrogalvanized surface is 15 or less, it can be recognized that there is no glossiness.
また、電気亜鉛めっき鋼板には表面の白色度が高いことが要求される場合がある。亜鉛めっき鋼板表面の白色度は明度で評価される場合が多いが、明度指数Ｌが６５以上であれば白色度が高いと評価される。 Further, the electrogalvanized steel sheet may be required to have a high whiteness on the surface. The whiteness of the surface of a galvanized steel sheet is often evaluated by the lightness, but if the lightness index L is 65 or more, the whiteness is evaluated to be high.
上記より、表裏面の光沢度Ｇｓ（６０°）が１５以下であり、表裏面の光沢度差が５以下であり、表裏面の明度Ｌが６５以上である電気亜鉛めっき鋼板は、表裏共に美麗な表面外観を有する電気亜鉛めっき鋼板と評価される。 From the above, the galvanized steel sheet having a glossiness Gs (60 °) on the front and back surfaces of 15 or less, a glossiness difference of 5 or less on the front and back surfaces, and a brightness L of 65 or more on the front and back surfaces is beautiful on both the front and back surfaces. It is evaluated as an electrogalvanized steel sheet with a smooth surface appearance.
また、表裏面の三次元粗さパラメータのスキューネス（Ｓｓｋ）を０．３０以下とすることにより、細かな谷状の形状が多く付与され、電気亜鉛めっき鋼板の金属光沢部を十分に除去できる。 Further, by setting the skewness (Ssk) of the three-dimensional roughness parameter of the front and back surfaces to 0.30 or less, many fine valley-shaped shapes are imparted, and the metallic luster portion of the electrogalvanized steel sheet can be sufficiently removed.
本発明はこのような知見に基づきなされたもので、その要旨は以下の通りである。
［１］電気亜鉛めっき鋼板の、少なくとも電気亜鉛めっき時に通電ロールと接しためっき鋼板の表面に、平均粒径が６〜１５０μｍであり、平均円形度０．９０以下である微粒子を混合した液体を噴射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］前記微粒子の平均粒径が４０μｍ以上であることを特徴とする［１］に記載の電気亜鉛めっき鋼板の製造方法。
［３］電気亜鉛めっき鋼板の、少なくとも電気亜鉛めっき時に通電ロールと接しためっき鋼板の表面に前記微粒子を混合した液体を噴射して、電気亜鉛めっき時に通電ロールと接した面の光沢度Ｇｓ（６０°）を１５以下にすることを特徴とする［１］〜［２］のいずれかに記載の電気亜鉛めっき鋼板の製造方法。
［４］前記微粒子を混合した液体を噴射した後の電気亜鉛めっき鋼板の表裏面の光沢度差が５以下であることを特徴とする［３］に記載の電気亜鉛めっき鋼板の製造方法。
［５］前記微粒子を混合した液体を電気亜鉛めっき鋼板の表裏面に噴射することを特徴とする［１］〜［４］のいずれかに記載の電気亜鉛めっき鋼板の製造方法。
［６］表裏面の光沢度Ｇｓ（６０°）が１５以下であり、表裏面の光沢度差が５以下であり、表裏面の明度Ｌが６５以上であることを特徴とする電気亜鉛めっき鋼板。
［７］表裏面の三次元粗さパラメータのスキューネス（Ｓｓｋ）が０．３０以下であることを特徴とする［６］に記載の電気亜鉛めっき鋼板。
The present invention has been made based on such findings, and the gist thereof is as follows.
[1] A liquid in which fine particles having an average particle size of 6 to 150 μm and an average circularity of 0.90 or less are mixed on the surface of an electrogalvanized steel sheet that is in contact with an energizing roll at least during electrogalvanizing. A method for manufacturing an electrogalvanized steel sheet, which comprises injecting.
[2] The method for producing an electrogalvanized steel sheet according to [1], wherein the average particle size of the fine particles is 40 μm or more.
[3] Gs (glossiness Gs) of the surface of the electrogalvanized steel sheet in contact with the energizing roll at least during electrogalvanizing by injecting a liquid mixed with the fine particles onto the surface of the plated steel sheet in contact with the energizing roll. The method for producing an electrogalvanized steel sheet according to any one of [1] to [2], wherein 60 °) is set to 15 or less.
[4] The method for producing an electrogalvanized steel sheet according to [3], wherein the difference in glossiness between the front and back surfaces of the electrogalvanized steel sheet after injecting a liquid mixed with the fine particles is 5 or less.
[5] The method for producing an electrogalvanized steel sheet according to any one of [1] to [4], wherein a liquid mixed with the fine particles is sprayed onto the front and back surfaces of the galvanized steel sheet.
[6] An electrogalvanized steel sheet characterized in that the glossiness Gs (60 °) of the front and back surfaces is 15 or less, the glossiness difference between the front and back surfaces is 5 or less, and the brightness L of the front and back surfaces is 65 or more. ..
[7] The electrogalvanized steel sheet according to [6], wherein the skewness (Ssk) of the three-dimensional roughness parameters on the front and back surfaces is 0.30 or less.
本発明により、コンダクターロール圧下による金属光沢部を低減し、外観の良好な電気亜鉛めっき鋼板を得ることができる。 According to the present invention, it is possible to reduce the metallic luster due to the reduction of the conductor roll and obtain an electrogalvanized steel sheet having a good appearance.
本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。 An embodiment of the present invention will be described. The present invention is not limited to the following embodiments.
先ず、電気亜鉛めっき工程について説明する。電気亜鉛めっきの処理条件は特に限定されず、適宜好ましい条件を採用すればよい。めっき浴中に亜鉛イオンが存在する状態で、鋼板を陰極として電解し、その後水洗を行う。なお、必要に応じて、その後、乾燥を行ってもよい。なお、水洗、乾燥の方法は特に限定されず、一般的な方法を採用可能である。めっき浴種は特に限定されるものではなく、硫酸浴、塩化物浴、ジンケート浴などを用いることができる。 First, the electrogalvanization process will be described. The treatment conditions for electrogalvanization are not particularly limited, and preferable conditions may be appropriately adopted. In the presence of zinc ions in the plating bath, electrolysis is performed using the steel sheet as a cathode, and then washing with water is performed. If necessary, drying may be performed thereafter. The method of washing with water and drying is not particularly limited, and a general method can be adopted. The type of plating bath is not particularly limited, and a sulfuric acid bath, a chloride bath, a zincate bath and the like can be used.
ここで、亜鉛めっきが施される鋼板の鋼種は特に限定されるものではなく、低炭素鋼、極低炭素鋼、ＩＦ鋼、各種合金元素を添加した高張力鋼板等の種々の鋼板を用いることができる。また、前記鋼板は、熱延鋼板、冷延鋼板のいずれも用いることができる。鋼板の厚さは特に限定されないが、家電、自動車車体、建材等の用途に用いる観点から、０．４〜５．０ｍｍが好ましい。 Here, the steel type of the steel sheet to be galvanized is not particularly limited, and various steel sheets such as low carbon steel, ultra-low carbon steel, IF steel, and high-strength steel sheet to which various alloying elements are added are used. Can be done. Further, as the steel plate, either a hot-rolled steel plate or a cold-rolled steel plate can be used. The thickness of the steel sheet is not particularly limited, but is preferably 0.4 to 5.0 mm from the viewpoint of being used for home appliances, automobile bodies, building materials, and the like.
次に、微粒子を混合した液体を噴射する工程について説明する。前記噴射に用いる粒子サイズは平均粒径６〜１５０μｍである必要がある。ここで、平均粒径とは、メディアン径Ｄ５０のことである。「メディアン径Ｄ５０」とは、累積質量５０％径、すなわち、粒子群をある粒子径から２つに分けたとき、大きい側の粒子群の積算粒子量と、小さい側の粒子群の積算粒子量が等量となる径のことで、ＪＩＳＲ６００１における「累積高さ５０％点の粒子径」を示す。尚、メディアン径Ｄ５０の測定では、粒子径として体積球相当径を採用する。平均粒径が６μｍ未満であると表面に十分な凹凸形状を付与することができないため、平滑な金属光沢部の解消に至らない。一方、平均粒径が１５０μｍを越えると、表面全体に均一に微粒子があたらず、局所的に金属光沢部の残存する箇所が見られる。また、新たに付与される凹凸形状が大きくなり、電気亜鉛めっき鋼板と大きく異なる、ザラザラ感のある表面外観に変化してしまう。 Next, a step of injecting a liquid mixed with fine particles will be described. The particle size used for the injection needs to have an average particle size of 6 to 150 μm. Here, the average particle size is a median diameter D 50 . "Median diameter D 50 " means the cumulative mass diameter of 50%, that is, when the particle group is divided into two from a certain particle size, the integrated particle amount of the larger particle group and the integrated particle of the smaller particle group. It is a diameter at which the amounts are equal, and indicates the "particle size at a cumulative height of 50% point" in JIS R6001. In the measurement of the median diameter D 50, the diameter equivalent to a volume sphere is adopted as the particle diameter. If the average particle size is less than 6 μm, it is not possible to impart a sufficient uneven shape to the surface, so that a smooth metallic luster portion cannot be eliminated. On the other hand, when the average particle size exceeds 150 μm, the fine particles are not uniformly applied to the entire surface, and a portion where the metallic luster portion remains locally can be seen. In addition, the newly added uneven shape becomes large, and the surface appearance changes to a rough surface, which is significantly different from the electrogalvanized steel sheet.
更に、前記平均粒径は４０μｍ以上であることがより好ましい。４０μｍ未満では得られる電気亜鉛めっき鋼板表面のＬ値がブラスト処理を行わない場合と比べて大きく低下するためである。 Further, the average particle size is more preferably 40 μm or more. This is because if the thickness is less than 40 μm, the L value of the obtained galvanized steel sheet surface is significantly reduced as compared with the case where the blast treatment is not performed.
噴射する粒子は平均円形度が０．９０以下である微粒子（以下、本件発明微粒子と称する。）を用いることが必要である。ここで、円形度とは、粒子表面の凹凸度合いを表すもので、Ｗａｄｅｌｌの円形度のことを示しており、下記式で求められる。 It is necessary to use fine particles having an average circularity of 0.90 or less (hereinafter referred to as the fine particles of the present invention) as the particles to be jetted. Here, the circularity represents the degree of unevenness on the particle surface, and indicates the circularity of Waddell, which is calculated by the following formula.
円形度＝投影面積の等しい円の周長／粒子の周長
ここで、「投影面積の等しい円の周長」とは、ある粒子を真上から観察したとき、下の平面に映った粒子の影の面積を求め、この面積に等しい円の輪郭の長さである。「粒子の周長」とは、粒子を真上から観察したとき、下の平面に映った粒子の影の輪郭の長さである。粒子表面の凹凸度合いが小さいほど、円形度は１に近くなる。
Circularity = Perimeter of circles with equal projected area / Perimeter of particles Here, "perimeter of circles with equal projected area" means that when a certain particle is observed from directly above, it is reflected in the plane below. The area of the shadow is calculated, and it is the length of the contour of the circle equal to this area. The "perimeter of a particle" is the length of the outline of the shadow of the particle reflected on the lower plane when the particle is observed from directly above. The smaller the degree of unevenness on the particle surface, the closer the circularity is to 1.
平均円形度が０．９０を超えると、得られる電気亜鉛めっき鋼板の光沢度が高くなり、電気亜鉛めっき鋼板特有の外観が失われるため不適である。外観の観点からの平均円形度の下限は無いが、製造コストの点で平均円形度が０．７０以上０．９０以下の粒子が好ましい。 If the average circularity exceeds 0.90, the glossiness of the obtained electrogalvanized steel sheet becomes high, and the appearance peculiar to the electrogalvanized steel sheet is lost, which is unsuitable. Although there is no lower limit of the average circularity from the viewpoint of appearance, particles having an average circularity of 0.70 or more and 0.90 or less are preferable in terms of manufacturing cost.
本件発明微粒子を用いた場合、電気亜鉛めっきの金属光沢部以外の場所に近い、光沢感の低い外観を全面にわたって得ることができる。一方、本件発明微粒子以外の形状の粒子を用いた場合、本件発明微粒子を用いた場合に比べて全体的に光沢度は高くなる。このメカニズムは明らかでは無いが、本件発明微粒子は、一般にブラスト処理等で使用される球形ではなく、表面が凹凸を有するため、本件発明微粒子を用いた場合、表層に細かい鋭角な凹凸形状が付与され、光が正反射しにくいのに対し、本件発明微粒子以外の形状の粒子を用いた場合、表層に細かい鋭角な凹凸形状が付与されないため、その底面部では光が正反射され易いためと考えられる。 When the fine particles of the present invention are used, it is possible to obtain an appearance having a low glossiness, which is close to a place other than the metallic luster portion of electrogalvanization. On the other hand, when particles having a shape other than the fine particles of the present invention are used, the glossiness is higher as a whole as compared with the case of using the fine particles of the present invention. Although this mechanism is not clear, the fine particles of the present invention are not spherical, which is generally used in blasting and the like, and have irregularities on the surface. Therefore, when the fine particles of the present invention are used, a fine and sharp uneven shape is imparted to the surface layer. It is considered that, while light is difficult to specularly reflect, when particles having a shape other than the fine particles of the present invention are used, fine sharp uneven shapes are not imparted to the surface layer, so that light is easily specularly reflected on the bottom surface. ..
本件発明は、少なくとも電気亜鉛めっき時に通電ロールと接しためっき鋼板の表面に平均粒径が６〜１５０μｍであり、平均円形度が０．９０以下である微粒子を混合した液体を噴射することが必要である。電気亜鉛めっき時に通電ロールと接しためっき鋼板の表面のみに上記微粒子を混合した液体を噴射することによって、噴射しない亜鉛めっき面の光沢度や白色度との間に明確な差が発生して好ましくないと判断される場合は、めっき鋼板の両面に微粒子を混合した液体を噴射しても構わない。その場合は、めっき鋼板の両面に同時に噴射してもよいし、別々に噴射しても構わない。表裏で噴射条件を違えても構わない。 In the present invention, it is necessary to inject a liquid mixed with fine particles having an average particle size of 6 to 150 μm and an average circularity of 0.90 or less onto the surface of a plated steel sheet in contact with an energizing roll at least during electrogalvanization. Is. By injecting a liquid mixed with the above fine particles only on the surface of the plated steel sheet in contact with the energizing roll during electrogalvanizing, a clear difference is generated between the glossiness and whiteness of the non-injected galvanized surface, which is preferable. If it is determined that the case is not present, a liquid mixed with fine particles may be sprayed on both sides of the plated steel sheet. In that case, both sides of the plated steel sheet may be sprayed at the same time, or they may be sprayed separately. The injection conditions may be different on the front and back.
本件発明微粒子の材質としては、ステンレス、アルミナ、ジルコニア、樹脂、ガラスのうち１種類または２種類以上であることが望ましい。 The material of the fine particles of the present invention is preferably one or more of stainless steel, alumina, zirconia, resin, and glass.
ブラスト処理方法には、遠心力ブラスターで、粒子を照射するショットブラスト、圧縮エアを用いて粒子を照射するサンドブラストなどが広く知られている。ショットブラストは、比較的粒径が大きく、質量が重い粒子でブラストすることが可能ではあるが、質量の小さい粒子は、空気抵抗によって粒子の速度が低下してしまい、ブラストすることができない。一方、サンドブラスト処理は、圧縮エアによって照射するため、質量の小さい粒子を照射することが可能である。しかし、放射状に粒子が放射状に噴射するため、板幅方向の均一性を保持するためには、ノズルを左右にスキャンさせ、オーバーラップする箇所を作る等が必要で、処理速度が極端に遅くなる。また、粒子が衝突する際の、めっき層へのダーメージも大きくなる。 Widely known blasting methods include shot blasting, in which particles are irradiated with a centrifugal blaster, and sandblasting, in which particles are irradiated using compressed air. Shot blasting can be performed with particles having a relatively large particle size and a heavy mass, but particles having a small mass cannot be blasted because the velocity of the particles decreases due to air resistance. On the other hand, since the sandblasting treatment irradiates with compressed air, it is possible to irradiate particles having a small mass. However, since the particles are ejected radially, it is necessary to scan the nozzles to the left and right to create overlapping points in order to maintain uniformity in the plate width direction, and the processing speed becomes extremely slow. .. In addition, the damage to the plating layer when the particles collide is also increased.
本件発明では、本件発明微粒子を混合した液体を電気亜鉛めっき鋼板表面に噴射する方法を用いる（以下、この方法をウェットブラストと称する。）。前記噴射は噴射ノズルを用いて行うことが望ましい。ウェットブラストはノズル形状を比較的自由に設計できるため、幅広ノズルを用いることができる。この方法を用いることで、板幅方向の均一性を保持することができ、更には、電気亜鉛めっき層の損傷を最小限に抑制することも可能である。 In the present invention, a method of injecting a liquid mixed with the fine particles of the present invention onto the surface of an electrogalvanized steel sheet is used (hereinafter, this method is referred to as wet blasting). It is desirable that the injection is performed using an injection nozzle. Since the nozzle shape can be designed relatively freely in wet blasting, a wide nozzle can be used. By using this method, the uniformity in the plate width direction can be maintained, and further, damage to the electrogalvanized layer can be minimized.
電気亜鉛めっき鋼板のめっき皮膜の厚さは一般的に約１〜１０μｍ（めっき付着量として約５〜６０ｇ／ｍ２）程度の薄膜厚であり、微粒子を液体と混合しないでめっき鋼板に噴射すると、めっき層が微粒子の衝突エネルギーで加熱されて軟化し、めっき層が損傷する場合がある。ウェットブラストでは、めっき層が加熱されても液体で冷却され、めっき層が損傷しにくいため、本件発明ではウェットブラストを適用する。 The thickness of the plating film of an electrogalvanized steel sheet is generally about 1 to 10 μm (about 5 to 60 g / m 2 as the amount of plating adhesion), and when fine particles are sprayed onto the plated steel sheet without mixing with liquid. , The plating layer may be heated and softened by the collision energy of the fine particles, and the plating layer may be damaged. In wet blasting, even if the plating layer is heated, it is cooled by a liquid and the plating layer is not easily damaged. Therefore, wet blasting is applied in the present invention.
ウェットブラスト処理は、例えばマコー(株)製ウェットブラスト装置を用いて処理することができる。ウェットブラスト処理に用いる粒子は、ステンレス、アルミナ、ジルコニア、樹脂、ガラスのうち１種類または２種類以上であることが望ましい。比較的硬い粒子のほうが、表面形状を制御するのに有効であり、耐摩耗性に優れる粒子のほうが循環して使用する際の粒子寿命の観点で有効である。 The wet blasting treatment can be performed using, for example, a wet blasting apparatus manufactured by Macau Corporation. The particles used in the wet blasting treatment are preferably one or more of stainless steel, alumina, zirconia, resin, and glass. Relatively hard particles are more effective in controlling the surface shape, and particles having excellent wear resistance are more effective in terms of particle life when circulated and used.
ウェットブラスト処理時の圧縮エア圧は０．０５〜１．０ＭＰａが望ましい。０．０５ＭＰａ未満では、粒子が有するエネルギーが不十分で、十分に圧縮応力を導入できないことがある。１．０ＭＰａを超えると、装置が摩耗し易くなる。処理時の投射距離は３〜５００ｍｍが望ましい。３ｍｍ未満であると、鋼板とノズルが接触してしまう可能性がある。また、５００ｍｍより長いと、十分に表面形状を制御できないことがある。処理角度は、表面に対して３０〜９０°の範囲であることが望ましい。９０°が最も効率的に表面形状を制御できるが、何らかの理由で傾きを持っても構わない。３０°を下回ると、表面形状の制御性が低下する。処理速度、処理回数は、所望される表面形状によって適宜決定すれば良い。 The compressed air pressure during the wet blast treatment is preferably 0.05 to 1.0 MPa. If it is less than 0.05 MPa, the energy of the particles is insufficient, and it may not be possible to sufficiently introduce compressive stress. If it exceeds 1.0 MPa, the device is likely to be worn. The projection distance during processing is preferably 3 to 500 mm. If it is less than 3 mm, the steel plate and the nozzle may come into contact with each other. Further, if it is longer than 500 mm, the surface shape may not be sufficiently controlled. The processing angle is preferably in the range of 30 to 90 ° with respect to the surface. 90 ° is the most efficient way to control the surface shape, but it may be tilted for some reason. If it is less than 30 °, the controllability of the surface shape is lowered. The treatment speed and the number of treatments may be appropriately determined depending on the desired surface shape.
ウェットブラスト処理液中の微粒子濃度は５質量％以上が好ましい。 The concentration of fine particles in the wet blasting solution is preferably 5% by mass or more.
ウェットブラスト処理後の鋼板は、ブラストした粒子が残存しないように、水洗し、乾燥する。水洗方法や乾燥方法は限定されず、適宜必要な方法を用いればよい。ブラストした粒子が残存すると腐食の拠点になる可能性があるため、十分に洗浄して除去することが好ましい。 The steel sheet after the wet blasting treatment is washed with water and dried so that the blasted particles do not remain. The washing method and the drying method are not limited, and a necessary method may be used as appropriate. If the blasted particles remain, they may become a base of corrosion, so it is preferable to thoroughly wash and remove them.
また、本発明による電気亜鉛めっき鋼板は、三次元粗さパラメータのスキューネス（Ｓｓｋ）が０．３０以下であることが好ましい。
ここで、亜鉛めっき表面のスキューネス（Ｓｓｋ）とは、三次元粗さパラメータのことであり、ＪＩＳ Ｂ０６０１（２００１）に規定されたＲｓｋを三次元に拡張したものである。Ｓｓｋ＝０のときは、表面高さ分布が表面高さの平均線に対して対称であり、Ｓｓｋ＜０のときは、表面高さ分布が平均面に対して上（表面側）に偏っていることを示す。
Further, the electrogalvanized steel sheet according to the present invention preferably has a skewness (Ssk) of 0.30 or less as a three-dimensional roughness parameter.
Here, the skewness (Ssk) of the galvanized surface is a three-dimensional roughness parameter, which is a three-dimensional extension of Rsk defined in JIS B0601 (2001). When Ssk = 0, the surface height distribution is symmetric with respect to the average line of surface height, and when Ssk <0, the surface height distribution is biased upward (surface side) with respect to the average surface. Indicates that you are.
三次元粗さパラメータのスキューネス（Ｓｓｋ）が０．３０を超えると、ウェットブラスト処理後の鋼鈑において、ブラスト粒子が衝突しなかった箇所には急峻な山状の形状が残り、他の箇所は平坦な形状となる。このような場合、電気亜鉛めっき鋼板の金属光沢部を十分に除去できないおそれがある。三次元粗さパラメータのスキューネス（Ｓｓｋ）が０．３０以下の場合は、細かな谷状の形状が多く付与され、電気亜鉛めっき鋼板の金属光沢部を十分に除去できる。 When the skewness (Ssk) of the three-dimensional roughness parameter exceeds 0.30, a steep mountain-shaped shape remains in the part where the blast particles did not collide in the steel plate after the wet blasting treatment, and the other parts are in the shape of a steep mountain. It has a flat shape. In such a case, the metallic luster portion of the electrogalvanized steel sheet may not be sufficiently removed. When the skewness (Ssk) of the three-dimensional roughness parameter is 0.30 or less, many fine valley-shaped shapes are imparted, and the metallic luster portion of the electrogalvanized steel sheet can be sufficiently removed.
ここで、三次元粗さパラメータのスキューネス（Ｓｓｋ）を０．３０以下とするためには、電気亜鉛めっき鋼板の表面に、平均粒径が１５０μｍ以下であり、平均円形度が０．９０以下である粒子をブラストすることが肝要である。ブラスト粒子の平均粒径を１５０μｍ以下に制限することで、ブラスト粒子が衝突しなかった隙間箇所が急峻な山状の形状となり、他の箇所が平坦な形状となることを抑制できる。また、平均円形度が小さいと、ブラスト粒子が衝突した箇所においても細かな谷状の形状を付与できる。 Here, in order to set the skewness (Ssk) of the three-dimensional roughness parameter to 0.30 or less, the average particle size is 150 μm or less and the average circularity is 0.90 or less on the surface of the galvanized steel sheet. It is essential to blast a particle. By limiting the average particle size of the blast particles to 150 μm or less, it is possible to prevent the gaps where the blast particles did not collide from having a steep mountain-like shape and the other parts from becoming a flat shape. Further, if the average circularity is small, a fine valley-like shape can be imparted even at a location where the blast particles collide.
前記Ｓｓｋを測定する方法は、特に限定はされないが、電子線三次元走査電子顕微鏡（３Ｄ−ＳＥＭ）を用いて亜鉛めっき表面の三次元表面形状を測定し、測定した三次元表面形状のデータのゆがみを除去することによって算出されることが好ましい。ここで、前記測定した三次元表面形状データのゆがみとは、前記３Ｄ−ＳＥＭの測定原理上、本来の三次元形状に重畳する二次式で表される放物線状の歪みのことである。そのため、本発明では、測定した三次元表面形状測定データに対し、最小二乗法で当てはめた二次曲面を測定データから差し引く二次元曲面回帰処理を施すことが好ましい。 The method for measuring Sk is not particularly limited, but the three-dimensional surface shape of the zinc-plated surface is measured using an electron beam three-dimensional scanning electron microscope (3D-SEM), and the measured three-dimensional surface shape data is obtained. It is preferably calculated by removing the distortion. Here, the distortion of the measured three-dimensional surface shape data is a parabolic distortion represented by a quadratic equation superimposed on the original three-dimensional shape in the measurement principle of the 3D-SEM. Therefore, in the present invention, it is preferable to perform a two-dimensional curved surface regression process on the measured three-dimensional surface shape measurement data by subtracting the quadric surface applied by the least squares method from the measured data.
なお、前記のようにして二次元曲面回帰処理を施して求めた粗さ曲面データは、めっき原板のマクロな凹凸の上に微細なめっき結晶の形状が重畳したものであるが、めっき原板のマクロな凹凸はめっき後の色調への寄与は小さい。そのため、本発明では、前記のようにして二次元曲面回帰処理を施して求めた粗さ曲面データに対し、さらにハイパスフィルター処理を施すことで得られる、微細なめっき結晶形状のみを抽出したデータから、前記Ｓｓｋを算出する。前記ハイパスフィルター処理のカットオフ波長λｃは、１０μｍである。 The roughness curved surface data obtained by performing the two-dimensional curved surface regression processing as described above is obtained by superimposing the shape of fine plating crystals on the macro unevenness of the plating original plate, but the macro of the plating original plate. The unevenness contributes little to the color tone after plating. Therefore, in the present invention, the roughness curved surface data obtained by performing the two-dimensional curved surface regression processing as described above is further subjected to the high-pass filter processing, and only the fine plating crystal shape is extracted from the data. , The Ssk is calculated. The cutoff wavelength λc of the high-pass filter processing is 10 μm.
ブラスト処理後の鋼板は、必要に応じて、めっき表面に無機系皮膜、有機系皮膜、又はこれらの複合皮膜を有してもよい。 The blasted steel sheet may have an inorganic film, an organic film, or a composite film thereof on the plated surface, if necessary.
本発明を実施例により更に詳細に説明する。なお、本発明は以下の実施例に限定されない。 The present invention will be described in more detail by way of examples. The present invention is not limited to the following examples.
素材鋼板として、板厚０．６ｍｍの冷延鋼板を下地とする、めっき付着量が片面あたり２０ｇ／ｍ２の電気亜鉛めっき鋼板を用いた。本実施例においては、コンダクターロールが接触し、金属光沢部の見られる面をＣＤＲ面、コンダクターロールが接触していない側の面を非ＣＤＲ面とする。供試材を２３０ｍｍ×３５０ｍｍサイズにせん断し、ウェットブラスト処理を施した。両面の光沢度差を観察するため、両面ウェットブラスト処理を施した。粒子の材質はアルミナ、ステンレスの本件発明微粒子及び本件発明外微粒子とし、幅広ガンを用いて処理した。使用した微粒子の形状は、下記手法により測定した。 As the material steel sheet, an electrogalvanized steel sheet having a plating adhesion amount of 20 g / m 2 per side, which was based on a cold-rolled steel sheet having a plate thickness of 0.6 mm, was used. In this embodiment, the surface on which the conductor rolls are in contact and where the metallic luster is visible is the CDR surface, and the surface on the side where the conductor rolls are not in contact is the non-CDR surface. The test material was sheared to a size of 230 mm × 350 mm and wet blasted. Both sides were wet blasted to observe the difference in glossiness on both sides. The material of the particles was alumina, stainless steel fine particles of the present invention and fine particles of non-invention, and the particles were treated with a wide gun. The shape of the fine particles used was measured by the following method.
微粒子を走査型電子顕微鏡（ＳＥＭ）にて撮影し、粒子１００個を無作為に選択した。 Fine particles were photographed with a scanning electron microscope (SEM) and 100 particles were randomly selected.
選択した粒子それぞれについて面積と周長とを画像解析ソフト（Ｉｍａｇｅ Ｐｒｏ Ｐｌｕｓ）を用いて求め、下記式に従って円形度を算出し、その平均値を各微粒子の平均円形度とした。 The area and perimeter of each of the selected particles were determined using image analysis software (Image Pro Plus), the circularity was calculated according to the following formula, and the average value was taken as the average circularity of each fine particle.
円形度＝投影面積の等しい円の周長（μｍ）／粒子の周長（μｍ）
詳細条件を表１に示す。処理後の供試材を水洗・乾燥した。
Circularity = circumference of circles with equal projected area (μm) / circumference of particles (μm)
The detailed conditions are shown in Table 1. The treated test material was washed with water and dried.
以上のようにして得られた試験片について、以下の評価を行った。得られた結果を、表２に示す。
（１）金属光沢部の有無
試験片を目視で観察し、金属光沢部の有無を調査した。
○：金属光沢部なし
×：局所的に金属光沢部あり
（２）光沢度の測定
各試験片について、日本電色製のＰＧ−１Ｍを用いて測定した。測定角度は６０°とした。
光沢度は表裏ともに測定し、表裏差を算出した。
（３）Ｌ値の測定
各試験片について、コニカミノルタ製分光色彩計ＣＭ−２６００ｄを用い、ＳＣＥ（正反射光除去）モードで測定した。
（４）三次元表面形状測定
各試験片について、エリオニクス社製の電子線三次元粗さ解析装置（ＥＲＡ−８８００ＦＥ）を用いて、加速電圧５ｋＶ、測定領域６０μｍ×４５μｍ、測定間隔０．１μｍの条件で測定を行い、スプラインハイパスフィルター処理のカットオフ波長を１０μｍとしてスキューネス（Ｓｓｋ）を算出した。
The test pieces obtained as described above were evaluated as follows. The results obtained are shown in Table 2.
(1) Presence or absence of metallic luster The test piece was visually observed to investigate the presence or absence of metallic luster.
◯: No metallic luster ×: Locally metallic luster (2) Measurement of glossiness Each test piece was measured using PG-1M manufactured by Nippon Denshoku. The measurement angle was 60 °.
The glossiness was measured on both the front and back sides, and the difference between the front and back sides was calculated.
(3) Measurement of L value Each test piece was measured in SCE (specular reflection light removal) mode using a Konica Minolta spectrocolorimeter CM-2600d.
(4) Three-dimensional surface shape measurement For each test piece, an electron beam three-dimensional roughness analyzer (ERA-8800FE) manufactured by Elionix Inc. was used to accelerate the voltage at 5 kV, the measurement area at 60 μm × 45 μm, and the measurement interval at 0.1 μm. The measurement was performed under the conditions, and the skewness (Ssk) was calculated with the cutoff wavelength of the spline high-pass filter treatment set to 10 μm.
表２に示したように、本発明によれば、ウェットブラスト後の通電ロールと接しためっき面（ＣＤＲ面）の光沢度は１５以下であり、表裏面の光沢度差は５以下であり、かつ、金属光沢部も認められなかった。更に、本発明によれば、ウェットブラスト後のＬ値は表裏共に白色度が高いと判定される６５以上であった。また、表裏面のスキューネス（Ｓｓｋ）はいずれも０．３０以下であった。 As shown in Table 2, according to the present invention, the glossiness of the plated surface (CDR surface) in contact with the energizing roll after wet blasting is 15 or less, and the glossiness difference between the front and back surfaces is 5 or less. Moreover, no metallic luster was observed. Further, according to the present invention, the L value after wet blasting was 65 or more, which is judged to have high whiteness on both the front and back sides. The skewness (Ssk) on the front and back surfaces was 0.30 or less.
一方、ブラストに使用した粒子の平均円形度が０．９０を超える比較例では光沢度が低下せず、いずれも１５を超えている。また、表裏面のスキューネス（Ｓｓｋ）はいずれも０．３０超であった。 On the other hand, in the comparative example in which the average circularity of the particles used for blasting exceeds 0.90, the glossiness does not decrease, and all of them exceed 15. The skewness (Ssk) on the front and back surfaces was more than 0.30.
なお、ウェットブラスト処理を行う条件（平均円形度、平均粒径）の変化により、Ｌ値を低い領域から高い領域まで制御できていることも確認した。 It was also confirmed that the L value could be controlled from a low region to a high region by changing the conditions for performing the wet blast treatment (average circularity, average particle size).
本発明によれば、コンダクターロール圧下で形成される金属光沢度を大きく低減して、表裏の光沢度差を最小とし、表裏共に美麗な表面外観を有する電気亜鉛めっき鋼板および電気亜鉛めっき鋼板の製造方法を提供することが出来る。 According to the present invention, the production of an electrogalvanized steel sheet and an electrogalvanized steel sheet having a beautiful surface appearance on both the front and back sides by greatly reducing the metallic luster formed under the pressure of a conductor roll to minimize the difference in glossiness between the front and back surfaces. A method can be provided.
１ めっきセル
２ 対極
３ めっき液
４ 鋼帯
５ａ、５ｂ コンダクターロール
６ バックアップロール
７ ダムロール
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0474887A (en) * | 1990-07-13 | 1992-03-10 | Nkk Corp | Production of electrogalvanized steel sheet having excellent appearance |
| JP2003306759A (en) * | 2002-04-18 | 2003-10-31 | Jfe Steel Kk | Method of producing galvanized steel sheet excellent in press formability |
| CN1809650A (en) * | 2003-04-23 | 2006-07-26 | 住友金属工业株式会社 | Hot press-formed article and method for its manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0474887A (en) * | 1990-07-13 | 1992-03-10 | Nkk Corp | Production of electrogalvanized steel sheet having excellent appearance |
| JP2003306759A (en) * | 2002-04-18 | 2003-10-31 | Jfe Steel Kk | Method of producing galvanized steel sheet excellent in press formability |
| CN1809650A (en) * | 2003-04-23 | 2006-07-26 | 住友金属工业株式会社 | Hot press-formed article and method for its manufacture |
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