JP4742629B2 - Quality judgment method for resin-coated hot-dip galvanized steel sheet - Google Patents
Quality judgment method for resin-coated hot-dip galvanized steel sheet Download PDFInfo
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Description
本発明は、家電、建材等の用途分野に使用される化成処理溶融亜鉛めっき鋼板の品質判定方法、より具体的には外観品質の判定方法に関する。 The present invention relates to a method for determining the quality of a chemical conversion galvanized steel sheet used in application fields such as home appliances and building materials, and more specifically to a method for determining the appearance quality.
家電、建材等の用途分野には、従来から亜鉛系めっき鋼板またはアルミニウム系めっき鋼板の表面に、耐食性（耐白錆性、耐赤錆性）を向上させる目的でクロム酸、重クロム酸またはその塩類を主成分とする処理液で処理した、所謂、クロメート処理鋼板が幅広く用いられている。クロメート処理は耐食性の改善効果に優れ、比較的簡便に行える経済的な処理である。 In application fields such as home appliances and building materials, chromic acid, dichromic acid or its salts have been used for the purpose of improving corrosion resistance (white rust resistance, red rust resistance) on the surface of galvanized steel sheets or aluminum-based galvanized steel sheets. A so-called chromate-treated steel sheet treated with a treatment liquid containing as a main component is widely used. Chromate treatment is an economical treatment that has an excellent effect of improving corrosion resistance and can be performed relatively easily.
クロメート処理は公害規制物質である６価Ｃｒを使用するものであるが、工業的には密閉系で行われるため、６価Ｃｒが処理工程で自然界に放出されることはない。また、製品においても有機皮膜シーリングなどの工夫によって、クロメート皮膜中からの６価Ｃｒ溶出は殆ど無視できるレベルまで抑制されている。したがって、実際にはクロメート処理によって環境や人体が汚染される危険性は極めて低い。しかしながら、最近の地球環境問題から、６価Ｃｒを含めた重金属の使用を自主的に削減する動きや、廃棄製品のシュレッダーダストを投棄した場合にも環境を汚染しないよう、製品中の重金属の量を規制しようとする動きが強まっている。 The chromate treatment uses hexavalent Cr, which is a pollution-controlling substance. However, since it is industrially performed in a closed system, hexavalent Cr is not released to nature in the treatment process. Also, in products, the elution of hexavalent Cr from the chromate film is suppressed to a level that can be almost ignored by means such as organic film sealing. Therefore, the risk of contamination of the environment and human body due to the chromate treatment is actually very low. However, due to recent global environmental problems, the amount of heavy metals contained in products is not to pollute the environment when voluntarily reducing the use of heavy metals, including hexavalent Cr, or when the shredder dust of discarded products is dumped. There is a growing movement to regulate this.
このような背景から、亜鉛系めっき鋼板の耐食性の向上、特に、亜鉛めっきの白錆の発生を抑制するため、クロメート処理に依存しない化成処理技術、所謂、クロメートフリー化成処理技術が注目されている。この種の技術としては、例えば、無機化合物、有機化合物、有機高分子材料、あるいは、これらを組み合わせた溶液を用い、浸漬、塗布、電解処理などの方法によって薄膜を生成させる方法などが知られている（例えば、特許文献１等参照。）。
従来用いられてきたクロメート処理では、その皮膜厚さは極薄く、数ｎｍ〜数十ｎｍの膜厚で十分な耐食性を発現する。一方、クロメートフリー化成処理では、その皮膜厚みは数μｍ程度のものもあり、溶融亜鉛めっき鋼板のように表面が平滑で光沢のあるめっき上にこのような厚さの皮膜を成膜すると、干渉色により外観品質が著しく悪化する。 In the chromate treatment conventionally used, the film thickness is extremely thin, and sufficient corrosion resistance is expressed with a film thickness of several nanometers to several tens of nanometers. On the other hand, in the chromate-free chemical conversion treatment, the film thickness is about several μm, and if a film with such a thickness is formed on a plating with a smooth surface and gloss like a hot-dip galvanized steel sheet, interference will occur. The appearance quality is significantly deteriorated by the color.
従来、このような干渉色による外観品質の劣化程度を適切に評価、判定できる手法が存在しないため、干渉色による外観品質の劣化を効果的に防止できなかった。 Conventionally, since there is no method that can appropriately evaluate and determine the degree of deterioration in appearance quality due to such interference colors, it has been impossible to effectively prevent deterioration in appearance quality due to interference colors.
本発明はこのような実情に鑑みてなされたものであり、その目的は、干渉色の抑制を適切に判定できる化成処理溶融亜鉛めっき鋼板の品質判定方法を提供することにある。 This invention is made | formed in view of such a situation, The objective is to provide the quality determination method of the chemical conversion treatment hot dip galvanized steel plate which can determine appropriately suppression of interference color.
上記課題を解決する本発明の手段は、膜厚が０．０８〜２．０μｍの樹脂塗膜を形成した樹脂被覆溶融亜鉛めっき鋼板において、表面粗さが、算術平均粗さＲａで０．４μｍ以上であることをもって干渉色が抑制されていると判定することを特徴とする樹脂被覆溶融亜鉛めっき鋼板の品質判定方法である。 The means of the present invention for solving the above problems is that a resin-coated hot-dip galvanized steel sheet having a resin film thickness of 0.08 to 2.0 μm has a surface roughness of 0.4 μm in terms of arithmetic average roughness Ra. It is the quality determination method of the resin-coated hot-dip galvanized steel sheet characterized by determining that the interference color is suppressed as described above.
ここで、算出平均粗さＲａは、ＪＩＳ Ｂ０６０１−１９９４で規定されるものであり、評価長さ：４ｍｍ、カットオフ値：０．８ｍｍで測定、算出した。 Here, the calculated average roughness Ra is defined by JIS B0601-1994, and measured and calculated at an evaluation length of 4 mm and a cutoff value of 0.8 mm.
本発明によれば、化成処理溶融亜鉛めっき鋼板の干渉色による外観品質の悪化程度を適切に評価、判定することができる。本発明法を利用することで、耐食性その他の品質特性を損なうことなく干渉色による外観品質の劣化が抑制された化成処理溶融亜鉛めっき鋼板を製造できる。 ADVANTAGE OF THE INVENTION According to this invention, the deterioration degree of the external appearance quality by the interference color of a chemical conversion treatment hot dip galvanized steel plate can be evaluated and determined appropriately. By using the method of the present invention, it is possible to produce a chemically treated hot-dip galvanized steel sheet in which deterioration of appearance quality due to interference colors is suppressed without impairing corrosion resistance and other quality characteristics.
以下、本発明の詳細とその限定理由について説明する。 The details of the present invention and the reasons for limitation will be described below.
溶融めっき法による亜鉛めっき鋼板には、溶融亜鉛めっき後めっき皮膜を冷却凝固させたものと、溶融亜鉛めっき後めっき皮膜を加熱して合金化処理したものがある。本明細書では、溶融亜鉛めっき後めっき皮膜を冷却凝固させたものを溶融亜鉛めっき鋼板と記載し、めっき皮膜を加熱して合金化処理したものを合金化溶融亜鉛めっき鋼板と記載することで両者を区別する。化成処理溶融亜鉛めっき鋼板とは、めっき表面に化成処理皮膜が形成された溶融亜鉛めっき鋼板のことである。 There are two types of galvanized steel sheets obtained by the hot dipping method: one obtained by cooling and solidifying a plated film after hot dip galvanizing, and one obtained by heating the plated film after hot dip galvanizing and alloying. In this specification, what is obtained by cooling and solidifying the coating film after hot dip galvanizing is described as a hot dip galvanized steel sheet, and what is obtained by alloying treatment by heating the plating film is referred to as an alloyed hot dip galvanized steel sheet. To distinguish. The chemical conversion treated galvanized steel sheet is a hot dip galvanized steel sheet in which a chemical conversion film is formed on the plating surface.
合金化溶融亜鉛めっき鋼板では、めっき皮膜表面に合金化処理によって生成した微細な凹凸が存在する。これに対して、溶融亜鉛めっき鋼板では、めっき皮膜は溶融状態の亜鉛が凝固して形成されるため表面が平滑である。溶融亜鉛めっき鋼板では、めっき皮膜が凝固する際にスパングルと称する華模様が生成するが、スパングルを微細化したミニマムスパングルは、表面の平滑度がより優れる。 In an alloyed hot-dip galvanized steel sheet, fine irregularities generated by alloying treatment exist on the surface of the plating film. On the other hand, in the hot dip galvanized steel sheet, the plating film is formed by solidification of molten zinc, so that the surface is smooth. In the hot dip galvanized steel sheet, a splendid pattern called spangle is generated when the plating film is solidified, but the minimum spangle with the spangle refined has a more excellent surface smoothness.
化成処理溶融亜鉛めっき鋼板における干渉色は、めっき表面と化成処理皮膜表面で正反射する成分が干渉することによって生じる。溶融亜鉛めっき鋼板では、めっき表面が平滑であることから、干渉色による外観品質の悪化が特に顕著に発生する。 The interference color in the chemical conversion-treated galvanized steel sheet is caused by interference between components that are regularly reflected on the plating surface and the chemical conversion coating surface. In the hot dip galvanized steel sheet, since the plating surface is smooth, the deterioration of the appearance quality due to the interference color is particularly noticeable.
本発明者らは、ミニマムスパングル溶融亜鉛めっき鋼板のクロムフリー化成処理皮膜の干渉色に影響を与える因子について種々検討した。その結果、皮膜厚さが０．０８〜２．０μｍの範囲で干渉色の発生が認められた。皮膜厚さが０．０８μｍ未満または２．０μｍ超では、干渉色の発生は殆ど無くなった。一方、表面粗さを、算術平均粗さＲａで評価することで、干渉色が抑制されているか否かを適切に評価、判定できることが明らかになった。本発明はこの知見に基づくものである。 The present inventors have studied various factors affecting the interference color of the chromium-free chemical conversion coating on the minimum spangled galvanized steel sheet. As a result, the generation of interference colors was observed when the film thickness was in the range of 0.08 to 2.0 μm. When the film thickness was less than 0.08 μm or more than 2.0 μm, the generation of interference color almost disappeared. On the other hand, it has been clarified that by evaluating the surface roughness with the arithmetic average roughness Ra, it is possible to appropriately evaluate and determine whether or not the interference color is suppressed. The present invention is based on this finding.
そして、本発明では、化成処理溶融亜鉛めっき鋼板表面粗さが、算術平均粗さＲａで０．４μｍ以上であることをもって干渉色が抑制されていると判定する。これは、算術平均粗さＲａが０．４μｍ以上であると、干渉色が発生しても極軽微であり、干渉色が抑制されていると判断できるためである。 And in this invention, it determines with the interference color being suppressed by having the surface roughness of chemical conversion treatment galvanized steel plate being 0.4 micrometer or more by arithmetic mean roughness Ra. This is because, when the arithmetic average roughness Ra is 0.4 μm or more, it can be determined that the interference color is extremely small even if the interference color is generated and the interference color is suppressed.
化成処理皮膜の膜厚が０．０８〜２．０μｍの範囲内にあると干渉色が発生しやすい。したがって、本発明は、膜厚が０．０８〜２．０μｍの範囲内にある化成処理溶融亜鉛めっき鋼板について干渉色の抑制有無を判定する方法として好適である。 If the film thickness of the chemical conversion coating is in the range of 0.08 to 2.0 μm, interference colors are likely to occur. Therefore, this invention is suitable as a method of determining the presence or absence of interference color suppression for a chemically treated hot-dip galvanized steel sheet having a thickness in the range of 0.08 to 2.0 μm.
前記したように、クロメートフリー皮膜を有する溶融亜鉛めっき鋼板で干渉色が問題になっている。したがって、本発明は、クロメートフリー皮膜を有する溶融亜鉛めっき鋼板の干渉色の抑制有無を判定する方法として好適である。 As described above, interference color has become a problem in hot-dip galvanized steel sheets having chromate-free coatings. Therefore, the present invention is suitable as a method for determining the presence or absence of interference color suppression of a hot-dip galvanized steel sheet having a chromate-free coating.
以上、クロメートフリー皮膜を有する溶融亜鉛めっき鋼板について説明したが、本発明はこれに限定されない。ベースとなるめっき鋼板は、めっき皮膜が溶融金属の凝固によって形成される溶融めっき鋼板を対象とする。このようなめっき鋼板としては、溶融亜鉛系めっき鋼板（Ｚｎめっき鋼板（めっき後合金化処理されていないもの）、所謂５％Ａｌ−Ｚｎ合金めっき鋼板、所謂５５％Ａｌ−Ｚｎ合金めっき鋼板等）、アルミめっき鋼板等が例示される。 The hot dip galvanized steel sheet having a chromate-free coating has been described above, but the present invention is not limited to this. The base plated steel sheet is a hot-dip plated steel sheet in which the plating film is formed by solidification of the molten metal. Examples of such plated steel sheets include hot dip galvanized steel sheets (Zn plated steel sheets (those that have not been alloyed after plating), so-called 5% Al—Zn alloy plated steel sheets, so-called 55% Al—Zn alloy plated steel sheets). Examples thereof include an aluminum-plated steel plate.
処理原板として、付着量：片面あたり６０ｇ／ｍ２のミニマムスパングルでブライト調圧を行った溶融亜鉛めっき鋼板を準備した。化成処理用組成物として、水分散性のエマルジョン樹脂、または水溶性樹脂を準備した。処理原板を湯洗、乾燥させた後、その表面に準備した水分散性樹脂、または水溶性樹脂をバーコーターで塗布し、インダクションヒータを用いて、板温が室温から３秒間で１００〜１４０℃になるように加熱乾燥させた。表面粗度の調整は、エマルジョン樹脂の粒径を変化させること、および乾燥温度の調整によっておこなった。本実験では、エマルジョン樹脂の粒径が大きいほど、また乾燥温度が低いほど、算術平均粗さＲａは大きくなる。このようにして作成した樹脂被覆溶融亜鉛めっき鋼板の算術平均粗さＲａと外観の関係を表１に示す。外観の評価は、著しい干渉色が認められる試料は×、干渉色が抑制されて軽度な試料は△、干渉色が抑制されて極軽微な試料は○とした。 A hot-dip galvanized steel sheet that was brightly regulated with a minimum spangle of 60 g / m 2 of adhesion amount per side was prepared as a processing original plate. A water-dispersible emulsion resin or a water-soluble resin was prepared as a chemical conversion treatment composition. After the treated original plate is washed with hot water and dried, the prepared water-dispersible resin or water-soluble resin is applied to the surface with a bar coater, and the plate temperature is 100 to 140 ° C. for 3 seconds from room temperature using an induction heater. And dried by heating. The surface roughness was adjusted by changing the particle size of the emulsion resin and adjusting the drying temperature. In this experiment, the arithmetic average roughness Ra increases as the particle size of the emulsion resin increases and the drying temperature decreases. Table 1 shows the relationship between the arithmetic average roughness Ra and the appearance of the resin-coated hot-dip galvanized steel sheet thus prepared. The appearance was evaluated as “x” for a sample in which a remarkable interference color was recognized, “Δ” for a mild sample in which the interference color was suppressed, and “◯” in a sample with a very light interference color.
算術平均粗さＲａが０．４μｍ未満は干渉色の評価が×、０．４μｍ以上０．７μｍ未満は干渉色の評価が△、０．７μｍ以上で干渉色の評価が○である。このことから、算術平均粗さＲａによって干渉色の抑制程度が適切に評価できること、また算術平均粗さＲａで０．４μｍ以上であると干渉色が抑制されていると判定できることが判る。 When the arithmetic average roughness Ra is less than 0.4 μm, the interference color is evaluated as x. When the arithmetic average roughness Ra is less than 0.4 μm and less than 0.7 μm, the evaluation of the interference color is Δ, and when it is 0.7 μm or more, the evaluation of the interference color is ○. From this, it can be seen that the suppression degree of the interference color can be appropriately evaluated by the arithmetic average roughness Ra, and that the interference color can be determined to be suppressed when the arithmetic average roughness Ra is 0.4 μm or more.
前述の例は、有機樹脂のみを含有する処理液を用いて皮膜を形成した例であるが、本発明は、無機成分が添加された処理液を用いて皮膜を形成した場合も同様の効果が奏される。 The above example is an example in which a film is formed using a treatment liquid containing only an organic resin, but the present invention has the same effect when a film is formed using a treatment liquid to which an inorganic component is added. Played.
本発明法を利用することで、耐食性その他の品質特性を損なうことなく干渉色による外観品質の劣化が抑制された化成処理溶融亜鉛めっき鋼板を製造できる。 By using the method of the present invention, it is possible to produce a chemically treated hot-dip galvanized steel sheet in which deterioration of appearance quality due to interference colors is suppressed without impairing corrosion resistance and other quality characteristics.
本発明は、家電、建材等の用途分野に使用される化成処理溶融亜鉛めっき鋼板の干渉色の抑制を判定する方法として利用することができる。 INDUSTRIAL APPLICATION This invention can be utilized as a method of determining suppression of the interference color of the chemical conversion treatment hot-dip galvanized steel plate used for application fields, such as household appliances and building materials.
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