JP2006299299A - Clear-lacquer-coated stainless steel sheet superior in designability, and manufacturing method therefor - Google Patents

Clear-lacquer-coated stainless steel sheet superior in designability, and manufacturing method therefor Download PDF

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JP2006299299A
JP2006299299A JP2005118479A JP2005118479A JP2006299299A JP 2006299299 A JP2006299299 A JP 2006299299A JP 2005118479 A JP2005118479 A JP 2005118479A JP 2005118479 A JP2005118479 A JP 2005118479A JP 2006299299 A JP2006299299 A JP 2006299299A
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stainless steel
clear
steel sheet
steel plate
coated stainless
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JP4606929B2 (en
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Masuhiro Fukaya
益啓 深谷
Naoto Ono
直人 小野
Haruki Ariyoshi
春樹 有吉
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Nippon Steel Stainless Steel Corp
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Nippon Steel and Sumikin Stainless Steel Corp
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Priority to TW099137242A priority patent/TWI370847B/en
Priority to TW95112989A priority patent/TWI354029B/en
Priority to MYPI20061697 priority patent/MY141238A/en
Priority to CN200680001695A priority patent/CN100585006C/en
Priority to AU2006237998A priority patent/AU2006237998B2/en
Priority to PCT/JP2006/307902 priority patent/WO2006112376A1/en
Priority to NZ555633A priority patent/NZ555633A/en
Priority to KR20077014730A priority patent/KR101018487B1/en
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C22/68Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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    • C23C2222/00Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20Use of solutions containing silanes

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a clear-lacquer-coated stainless steel sheet superior in whiteness and designability, and to provide a manufacturing method therefor. <P>SOLUTION: The clear-lacquer-coated stainless steel sheet superior in whiteness is a ferritic stainless steel sheet containing 0.2-0.8 mass% Si; has a surface oxide film containing Cr, Si, Al and Fe so that the atomic concentration ratio (Cr+Si+Al)/Fe can be 0.6 or more, in a region between the surface and a 50 Å deep plane therefrom; has a chemical conversion coating has a coating film, which is formed by using a chemical agent prepared from one or two compounds of an aminosilane-based compound and an epoxysilane-based compound, and has a coating mass of 2 to 20 mg/m<SP>2</SP>(in terms of SiO<SB>2</SB>measured with X-ray fluorescent analysis); and has the coating film with a thickness of 1 to 10 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ステンレス鋼が有する金属素材特有の優れた意匠性に優れ、塗装時に黄色に着色されない家電、建材、自動車等の部品に利用されるクリヤ塗装ステンレス鋼板に関するものである。   The present invention relates to a clear-coated stainless steel sheet that is excellent in the excellent design characteristics unique to a metal material possessed by stainless steel and is used in parts such as home appliances, building materials, and automobiles that are not colored yellow during coating.

ステンレス鋼は優れた耐食性、意匠性を有することから家電、厨房、自動車、建材分野において裸状態で使用されてきた。最近では、ステンレス鋼板の金属光沢等優れた意匠性を生かしながら、さらに耐汚染性、耐食性等の機能を付加したクリヤ塗装ステンレス鋼板の家電分野での適用が増えてきている。   Stainless steel has been used barely in the fields of home appliances, kitchens, automobiles, and building materials because it has excellent corrosion resistance and design properties. Recently, application of the clear-coated stainless steel sheet to which functions such as contamination resistance and corrosion resistance have been added while taking advantage of the excellent design such as the metallic luster of the stainless steel sheet has been increasing.

これらのクリヤ塗装ステンレス鋼板は意匠性から、無色のクリヤ塗装の他、顔料等により着色されたクリヤ塗装やパール調やメタリック調の顔料を添加したクリヤ塗装鋼板も適用されるようになってきた。しかしながら、これらの顔料の添加はクリヤ皮膜の透明感を低下させ、ステンレス鋼特有の金属光沢を持つ質感を低下させる。   These clear-coated stainless steel sheets have been designed to be applied in addition to colorless clear coating, clear-coated steel sheets to which pigment-colored clear coating or pearl-like or metallic-like pigments are added. However, the addition of these pigments lowers the transparency of the clear film and lowers the texture with the metallic luster unique to stainless steel.

一方、無色のクリヤ塗装ステンレス鋼板では、下地処理のクロメート処理により黄色味を帯び、意匠性を損なうと共に、見る角度によっては黒っぽく見えるとの問題がある。これらの問題に対して、特許文献1や特許文献2ではクロメート皮膜におよぼす処理液組成や塗布量を検討したり、特許文献3ではリン酸やシリカによる下地ステンレス鋼板の外観性、塗膜の耐汚染性と耐焼つき性の改善について検討がなされてきた。   On the other hand, a colorless clear-coated stainless steel sheet has a problem that it becomes yellowish due to the chromate treatment of the base treatment, impairs the design, and looks black depending on the viewing angle. To deal with these problems, Patent Document 1 and Patent Document 2 examine the composition of the treatment solution and the amount of coating applied to the chromate film, and Patent Document 3 describes the appearance of the underlying stainless steel plate with phosphoric acid and silica, and the resistance of the coating film. Studies have been made on improving the contamination and seizure resistance.

特開平5−106057号公報JP-A-5-106057 特開平11−269660号公報JP-A-11-269660 特開平8−281864号公報JP-A-8-281864 特開昭56−259号公報JP-A-56-259 特開昭62−156253号公報JP 62-156253 A 特開平11−254585号公報Japanese Patent Laid-Open No. 11-254585

上記のようなクロメート処理方法の改善のみでは、白色度に優れ、かつ透明度の高いクリヤ塗装ステンレス鋼板を得ることができない。本発明は、化成処理条件、素材表面の特性および塗装条件を検討し、白色度に優れたクリヤ塗装ステンレス鋼板およびその製造方法を提供することを課題とする。   Only by improving the chromate treatment method as described above, a clear coated stainless steel sheet having excellent whiteness and high transparency cannot be obtained. It is an object of the present invention to provide a clear-coated stainless steel sheet excellent in whiteness and a method for producing the same by examining chemical treatment conditions, material surface characteristics, and coating conditions.

本発明者らの検討の結果、無色のクリヤ塗装ステンレス鋼板の黄色味着色(黄変)については、クロメート処理に起因するほか、クリヤ塗膜の焼付け時にステンレス鋼板表面にテンパーカラー着色が発生し、このテンパーカラー着色も黄変の原因となっていることが判明した。そして、化成処理をクロメート処理からノンクロメート処理に変更するとともに化成処理皮膜の厚さを最適化し、さらにクリヤ塗装ステンレス鋼板に適用するステンレス鋼板として耐テンパーカラー性に優れたステンレス鋼板を用いることにより、クリヤ塗装時の黄変防止を実現できることが明らかになった。   As a result of the examination by the inventors, the yellowish coloring (yellowing) of the colorless clear-coated stainless steel sheet is caused by chromate treatment, and temper color coloring occurs on the surface of the stainless steel sheet when the clear coating film is baked. It has been found that this temper color coloring also causes yellowing. And by changing the chemical conversion treatment from chromate treatment to non-chromate treatment and optimizing the thickness of the chemical conversion treatment film, and using a stainless steel plate with excellent temper color resistance as a stainless steel plate applied to a clear coated stainless steel plate, It became clear that yellowing prevention at the time of clear painting can be realized.

ステンレス鋼板のテンパーカラーは、Si、Alを増加したステンレス鋼板を光輝焼鈍して鋼板表面にSiO2、Al23を含む酸化皮膜を形成することにより抑制できることが知られている。すなわち、SiまたはAl含有量の増加に伴ってSi,Alが濃化した酸化皮膜が形成されやすくなり、耐テンパーカラー性が向上する。このようなステンレス鋼として高Si鋼(特許文献4、5)および高Al鋼(特許文献5)等が知られている。また、フェライト系ステンレス鋼板表面のAlあるいはSiを4.5〜6原子%に規制した耐熱透明塗装ステンレス鋼板として、特許文献6が知られている。 It is known that the temper color of a stainless steel plate can be suppressed by bright annealing a stainless steel plate with increased Si and Al to form an oxide film containing SiO 2 and Al 2 O 3 on the surface of the steel plate. That is, as the Si or Al content increases, an oxide film enriched with Si and Al is easily formed, and the temper color resistance is improved. As such stainless steel, high Si steel (Patent Documents 4 and 5), high Al steel (Patent Document 5) and the like are known. Patent Document 6 is known as a heat-resistant transparent coated stainless steel plate in which Al or Si on the surface of a ferritic stainless steel plate is regulated to 4.5 to 6 atomic%.

本発明者らは、前記課題を解決する手段を鋭意検討した結果、上記のとおり、化成処理条件、素材表面の特性および塗装条件を検討し、白色度に優れたフェライト系ステンレス鋼板を用いたクリヤ塗装ステンレス鋼板およびその製造方法を確立した。   As a result of intensive studies on the means for solving the above problems, the present inventors have studied the chemical conversion treatment conditions, the material surface characteristics, and the coating conditions, as described above, and used a ferrite stainless steel sheet having excellent whiteness. A painted stainless steel sheet and its manufacturing method were established.

本発明の要旨とするところは下記の通リである。
(1)ステンレス鋼板が質量%でSi:0.2〜0.8%を含有するフェライト系ステンレス鋼板であり、該鋼板はその表面から50Åまでの深さにおけるCr,Si,Al,Fe原子濃度比(Cr+Si+Al)/Feが0.6以上の表面酸化皮膜を有し、塗膜の化成処理剤がアミノシラン系、エポキシシラン系の1種類または2種類よりなり、該化成処理剤の付着量が2〜20mg/m2(蛍光X線にてSiO2量を測定)であり、クリヤ塗料厚さが1〜10μmの塗膜を有することを特徴とする白色度に優れるクリヤ塗装ステンレス鋼板。
(2)前記ステンレス鋼板はさらに質量%でAl:0.005〜0.15%を含有することを特徴とする請求項1に記載の白色度に優れるクリヤ塗装ステンレス鋼板。
(3)前記ステンレス鋼板はさらに質量%でNb:0.1〜0.7%を含有することを特徴とする請求項1又は2に記載の白色度に優れるクリヤ塗装ステンレス鋼板。
(4)最終光輝焼鈍の温度T1(℃)および焼鈍雰囲気の露点T2(℃)が1式および2式を満足する条件で行なうことを特徴とする(1)乃至(3)のいずれかに記載の白色度に優れたクリヤ塗装ステンレス鋼板素材の製造方法。
750≦T1≦5×T2+1200 ……1式
−70≦T2≦−30 ……2式
(5)冷間圧延したフェライト系ステンレス鋼板を、表面研磨した後に最終光輝焼鈍を施すことを特徴とする(4)に記載の白色度に優れるクリヤ塗装ステンレス鋼板素材の製造方法。
The gist of the present invention is as follows.
(1) A ferritic stainless steel sheet in which the stainless steel sheet contains Si: 0.2 to 0.8% by mass%, and the steel sheet has Cr, Si, Al, and Fe atomic concentrations at a depth of up to 50% from the surface. It has a surface oxide film with a ratio (Cr + Si + Al) / Fe of 0.6 or more, and the chemical conversion treatment agent for the coating film is composed of one or two types of aminosilane type and epoxysilane type, and the amount of the chemical conversion treatment agent is 2 A clear-coated stainless steel sheet having excellent whiteness, which is ˜20 mg / m 2 (the amount of SiO 2 is measured by fluorescent X-rays) and has a clear coating thickness of 1 to 10 μm.
(2) The clear coated stainless steel sheet having excellent whiteness according to claim 1, wherein the stainless steel sheet further contains Al: 0.005 to 0.15% by mass.
(3) The clear-coated stainless steel plate having excellent whiteness according to claim 1 or 2, wherein the stainless steel plate further contains Nb: 0.1 to 0.7% by mass.
(4) The temperature of the final bright annealing T1 (° C.) and the dew point T2 (° C.) of the annealing atmosphere are performed under the conditions satisfying the first and second formulas, according to any one of (1) to (3) Of clear-coated stainless steel sheet material with excellent whiteness.
750 ≦ T1 ≦ 5 × T2 + 1200 (1) −70 ≦ T2 ≦ −30 (2) (5) The surface of a cold-rolled ferritic stainless steel plate is subjected to final bright annealing after surface polishing ( The method for producing a clear-coated stainless steel sheet material having excellent whiteness as described in 4).

クリヤ塗装ステンレス鋼板の意匠性と色調の関係を検討した本発明によれば、b*(色度、黄/青の程度、JIS Z 8729)が0から2の範囲であり、白色度に優れたクリヤ塗装鋼板を製造することが可能となる。一般のクリヤ塗装ステンレス鋼板ではb*が4から6程度と黄色っぽく、見る角度によっては暗い色調に見える。一方、本発明のクリヤ塗装ステンレス鋼板は、白っぽく、かつ見る方向により暗い色調には見えない。   According to the present invention in which the relationship between the design and color tone of the clear coated stainless steel sheet was examined, b * (chromaticity, yellow / blue degree, JIS Z 8729) was in the range of 0 to 2, and the whiteness was excellent. It becomes possible to manufacture clear coated steel sheets. In general clear-coated stainless steel sheet, b * is yellowish, about 4 to 6, and looks dark depending on the viewing angle. On the other hand, the clear-coated stainless steel sheet of the present invention is whitish and does not appear in a dark color tone depending on the viewing direction.

本発明者らは、クリヤ塗装ステンレス鋼板の意匠性における前処理と素材表面の特性を研究した結果、白色度に優れるクリヤ塗装ステンレス鋼板を得るには以下の2点が重要であることを見出した。まず第1に、前処理としての化成処理剤にクロメート処理剤ではなく、アミノシラン系、エポキシシラン系化成処理剤を用いるとともに、該化成処理剤の付着量を最適範囲とすることである。第2に、ステンレス鋼板素材として、表面にCr,Si、Alの成分を富化させ、塗装焼付け時にテンパーカラー着色による素材の変色を防ぐことである。なお、無色のクリヤ塗料については、ポリエステル樹脂系、アクリル樹脂系、アクリルウレタン樹脂系、エポキシ変性ポリエステル樹脂系等のいずれでも良い。   As a result of studying the pretreatment in the design of the clear coated stainless steel sheet and the characteristics of the material surface, the present inventors have found that the following two points are important for obtaining a clear coated stainless steel sheet having excellent whiteness. . First of all, an aminosilane-based or epoxysilane-based chemical conversion treatment agent is used as a chemical conversion treatment agent as a pretreatment instead of a chromate treatment agent, and the adhesion amount of the chemical conversion treatment agent is set to an optimum range. Second, as a stainless steel plate material, the surface is enriched with Cr, Si, and Al components to prevent discoloration of the material due to temper color coloring during paint baking. The colorless clear paint may be any of polyester resin, acrylic resin, acrylic urethane resin, epoxy-modified polyester resin, and the like.

本発明のクリヤ化成処理について説明する。   The clear chemical conversion treatment of the present invention will be described.

本発明のクリヤ化成処理剤は、アミノシラン系、エポキシシラン系の1種類又は2種類よりなる。アミノシラン系とエポキシシラン系を選択した理由は、これらを用いると付着性が良好であり、またクロメート処理剤を用いた場合と比較して黄色着色を防止できるからである。化成処理剤の付着量が2〜20mg/m2(蛍光X線にてSiO2量を測定)になるように処理し、ステンレス鋼板素材の表面温度(MT)が60〜140℃で焼付け乾燥される。 The clear chemical conversion treatment agent of the present invention comprises one or two types of aminosilane type and epoxysilane type. The reason for selecting the aminosilane type and the epoxysilane type is that when these are used, the adhesion is good and yellow coloring can be prevented as compared with the case where the chromate treatment agent is used. It is processed so that the amount of chemical conversion treatment is 2 to 20 mg / m 2 (measured by the amount of SiO 2 by fluorescent X-ray), and the surface temperature (MT) of the stainless steel plate is baked and dried at 60 to 140 ° C. The

図1に日本パーカライジング社のE−206(アミノシラン系)を100℃で付着量が2mg/m2から50mg/m2付着量まで変化させ、2μmのアクリルウレタン樹脂系クリヤ塗料をロールコートし、焼付け温度を200℃で塗装したクリヤ塗装ステンレス鋼板の色調の変化を調査した。クリヤ塗装に用いるステンレス鋼板素材としては、表面から50Åまでの深さにおける原子濃度比(Cr+Si+Al)/Fe(後述)が0.6以上のSUS430/光輝焼鈍材を用いることにより、テンパーカラー着色起因の黄変を極力少なくしている。図1の縦軸(Δb*)は、横軸に示すように化成処理剤の付着量を変化させ、クリヤ塗料を焼付け塗装させたときのb*(1)から鋼板素材のb*(2)を引いたものである。即ち、Δb*=b*(1)−b*(2)である。 Fig. 1 rolls E-206 (aminosilane) from Nihon Parkerizing Co., Ltd. at 100 ° C., changing the adhesion amount from 2 mg / m 2 to 50 mg / m 2 and applying a 2 μm acrylic urethane resin clear paint. The change in the color tone of the clear coated stainless steel sheet coated at 200 ° C. was investigated. As a stainless steel plate material used for clear coating, an SUS430 / bright annealed material having an atomic concentration ratio (Cr + Si + Al) / Fe (described later) of 0.6 or more at a depth from the surface to 50 mm is used, resulting in temper color coloring. Yellowing is minimized. The vertical axis (Δb *) in FIG. 1 shows the b * (2) of the steel plate material from b * (1) when the coating amount of the chemical conversion treatment agent is changed and the clear coating is baked as shown on the horizontal axis. Is subtracted. That is, Δb * = b * (1) −b * (2).

その結果、図1に示すように、化成処理剤の付着量が20mg/m2を超えるとクリヤ塗装ステンレス鋼の光沢が低下するとともに、若干黄色味を帯びる。付着量が20mg/m2以下では、Δb*が0.3以下となり、化成処理による色調の変化は少ない。一方、化成処理2mg/m2未満では、皮膜が不均一になりクリヤ塗膜とステンレス鋼の密着性が低下する。このため、本発明において化成処理剤の付着量を2〜20mg/m2とした。なお、化成処理剤の付着量については、クリヤ塗装ステンレス鋼板表面について蛍光X線にてSiO2量を測定することによって定量することかできる。 As a result, as shown in FIG. 1, when the adhesion amount of the chemical conversion treatment agent exceeds 20 mg / m 2 , the gloss of the clear coated stainless steel is lowered and slightly yellowish. When the adhesion amount is 20 mg / m 2 or less, Δb * is 0.3 or less, and the change in color tone due to the chemical conversion treatment is small. On the other hand, when the chemical conversion treatment is less than 2 mg / m 2 , the coating becomes non-uniform, and the adhesion between the clear coating and the stainless steel decreases. Therefore, the deposition amount of the chemical conversion treatment agent in the present invention was 2 to 20 mg / m 2. Note that the deposition amount of the chemical conversion treatment agent can either be determined by measuring the amount of SiO 2 by a fluorescent X-ray for clear coated stainless steel surface.

クリヤ塗膜厚さは、1μmから10μm以下の範囲である。これは、1μm以下では安定的な色調を得ることが難しく、10μm以上では1コートでの製造が難しくなり、塗膜コストも高くなるためである。好ましくは2μmから5μmの範囲である。   The clear coating thickness is in the range of 1 μm to 10 μm. This is because it is difficult to obtain a stable color tone at 1 μm or less, and it becomes difficult to produce one coat at 10 μm or more, and the coating cost increases. Preferably, it is in the range of 2 μm to 5 μm.

次に 本発明のクリヤ塗装ステンレス鋼板の素材について述べる。   Next, the material of the clear coated stainless steel sheet of the present invention will be described.

本発明においては、表面から50Åまでの深さにおけるCr,Si,Al,Fe原子濃度比(Cr+Si+Al)/Feが0.6以上の表面酸化皮膜を有する鋼板を用いることにより、塗装焼付け時におけるテンパーカラー着色を防止して黄変を防止することを特徴とする。Siを0.2質量%以上含有するフェライト系ステンレス鋼板を用い、この鋼板に所定の温度と雰囲気で光輝焼鈍を行うことにより、鋼板表面の原子濃度比を上記好適範囲とすることができる。   In the present invention, by using a steel plate having a surface oxide film having a Cr, Si, Al, Fe atomic concentration ratio (Cr + Si + Al) / Fe of 0.6 or more at a depth of 50 mm from the surface, a temper during coating baking is used. It is characterized by preventing coloration and preventing yellowing. By using a ferritic stainless steel plate containing 0.2% by mass or more of Si and subjecting this steel plate to bright annealing at a predetermined temperature and atmosphere, the atomic concentration ratio on the surface of the steel plate can be made within the above preferred range.

クリヤ塗装ステンレス鋼板のステンレス鋼は、質量%でSi:0.2〜0.8%を含有するフェライト系ステンレス鋼板である。フェライト系ステンレス鋼中の元素の拡散速度はオーステナイト系に比較して速いので、皮膜中へCrやSiを濃化させやすい。そこで、本発明はフェライト系ステンレス鋼板に限定した。特にAlやSiを含有する特殊な鋼種(Cr−Al鋼やCr−Si鋼)では比較的容易であり、特許文献4および5に記載されている。しかしながら、本発明のフェライト系ステンレス鋼すなわちSi:0.2〜0.8%を含有する鋼においては、次に述べるCr、Si、Alを皮膜中に濃化するための技術が必須となる。   The stainless steel of the clear coated stainless steel plate is a ferritic stainless steel plate containing Si: 0.2 to 0.8% by mass. Since the diffusion rate of elements in ferritic stainless steel is faster than that of austenite, Cr and Si are easily concentrated in the film. Therefore, the present invention is limited to ferritic stainless steel sheets. In particular, special steel types (Cr—Al steel and Cr—Si steel) containing Al and Si are relatively easy and are described in Patent Documents 4 and 5. However, in the ferritic stainless steel of the present invention, that is, a steel containing Si: 0.2 to 0.8%, a technique for concentrating Cr, Si, and Al described below is essential.

本発明においては、ステンレス鋼板表面にSiが濃化した表面酸化皮膜を形成するため、Siは0.2%以上含有することが必須であり、この場合、Siは鋼の溶製時の脱酸元素として使用されるものも含まれる。Siの上限の0.8%は本願発明が汎用的なフェライト系ステンレス鋼であることを特に示すものである。これ以上Siを含有すると、汎用的なフェライト系ステンレス鋼、たとえばSUS430あるいはNb添加のSUS430J1Lの成分範囲を超えてしまう。すなわち、0.8%超のSi添加は固溶硬化作用のため、加工性を劣化させ汎用的な用途に適さない。   In the present invention, in order to form a surface oxide film in which Si is concentrated on the surface of the stainless steel plate, it is essential that Si is contained in an amount of 0.2% or more. In this case, Si is deoxidized during melting of steel. Those used as elements are also included. The upper limit of 0.8% of Si particularly indicates that the present invention is a general-purpose ferritic stainless steel. If Si is further contained, the component range of general-purpose ferritic stainless steel, for example, SUS430 or Nb-added SUS430J1L is exceeded. That is, addition of Si exceeding 0.8% is not suitable for general-purpose use because it degrades workability due to the solid solution hardening action.

本発明においては、0.005%以上、0.15%以下の微量のAlを含有することが望ましい。AlはSiと同様に、以下に述べるように、光輝焼鈍皮膜中に濃化することにより、クリヤ塗膜焼付け時のb*増加を抑制する効果を有するからである。Alは,脱酸元素として0.005%以上添加される。多量Al添加は加工性を劣化させる。よって,Alは,0.005〜0.15%が望ましい。   In the present invention, it is desirable to contain a trace amount of Al of 0.005% or more and 0.15% or less. This is because Al, like Si, has the effect of suppressing an increase in b * during baking of the clear coating film by being concentrated in the bright annealed coating as described below. Al is added in an amount of 0.005% or more as a deoxidizing element. Addition of a large amount of Al deteriorates workability. Therefore, Al is preferably 0.005 to 0.15%.

本発明においては、フェライト系ステンレス鋼板の基本成分であるCrの含有量は16.0〜20.0質量%の範囲とすることができる。さらに、白色度に優れるクリヤステンレス鋼板とするためには、Cr含有量はできるだけ多い方がよい。光輝焼鈍時の皮膜中へのCrの濃化を促進する作用があるからである。さらに本発明においては、Nbを0.1〜0.7%含有することが望ましい。Nbの酸化物はCr酸化物よりも熱力学的に安定であり、Crと同様の作用を有すると考えられるからである。   In the present invention, the content of Cr, which is a basic component of a ferritic stainless steel sheet, can be in the range of 16.0 to 20.0 mass%. Furthermore, in order to obtain a clear stainless steel plate having excellent whiteness, the Cr content should be as high as possible. This is because it has the effect of promoting the concentration of Cr in the film during bright annealing. Furthermore, in this invention, it is desirable to contain 0.1-0.7% of Nb. This is because the oxide of Nb is thermodynamically more stable than Cr oxide and is considered to have the same action as Cr.

次に、Si:0.2〜0.8%を含有するフェライト系ステンレス鋼において、表面酸化皮膜中にCr、Si、Alを濃化するための技術について説明する。   Next, a technique for concentrating Cr, Si, and Al in the surface oxide film in ferritic stainless steel containing Si: 0.2 to 0.8% will be described.

フェライト系ステンレス鋼であるSUS430の冷延焼鈍後、No.4研磨仕上げした材料を光輝焼鈍し、光輝焼鈍の温度と雰囲気を変化させることによって酸化皮膜中のCr,Si,Al,Feの割合を変化させた。原子濃度比(Cr+Si+Al)/Feを0.15〜3.5の範囲で調整した材料に、化成処理としてアミノシラン系化成処理剤を付着量が10mg/m2となるように塗布し、100℃で焼付け乾燥をした後、2μmのアクリルウレタン樹脂系クリヤ塗料をロールコートした。図2に示すものは、クリヤ塗料塗布後の焼付け温度を224℃とし、原子濃度比(Cr+Si+Al)/FeとΔb*との関係を示したものである。焼付け後と基準材(クリヤ塗装ステンレス鋼板素材)とのb*の差であるΔb*により評価した。図2から明らかなように、原子濃度比(Cr+Si+Al)/Feを0.6以上に調整した材料では、塗装・焼付けによる色調の変化が少なく、Δb*が1未満で変色が少ない。 After cold rolling annealing of SUS430, which is a ferritic stainless steel, no. 4. The polished material was bright annealed, and the ratio of Cr, Si, Al, and Fe in the oxide film was changed by changing the temperature and atmosphere of the bright anneal. An aminosilane-based chemical conversion treatment agent is applied as a chemical conversion treatment to a material in which the atomic concentration ratio (Cr + Si + Al) / Fe is adjusted in the range of 0.15 to 3.5 so that the amount of adhesion is 10 mg / m 2. After baking and drying, a 2 μm acrylic urethane resin-based clear paint was roll-coated. FIG. 2 shows the relationship between the atomic concentration ratio (Cr + Si + Al) / Fe and Δb * when the baking temperature after applying the clear paint is 224 ° C. Evaluation was performed by Δb *, which is a difference in b * between the baking and the reference material (clear coated stainless steel plate material). As is clear from FIG. 2, a material in which the atomic concentration ratio (Cr + Si + Al) / Fe is adjusted to 0.6 or more has little color tone change due to painting and baking, and Δb * is less than 1 and there is little color change.

次に、原子濃度比(Cr+Si+Al)/Feを0.6以上に調整した材料と原子濃度比(Cr+Si+Al)/Feを0.6未満に調整した材料を準備し、焼付け温度を150℃から250℃まで変化させて、色調の変化を見た。焼付け温度の相違及び品種の相違以外については上記図2の場合と同様である。図3において、○と△の材料については原子濃度比(Cr+Si+Al)/Feを3程度としている。●と▲については、原子濃度比(Cr+Si+Al)/Feをそれぞれ0.4程度、0.2程度としている。その結果、図3に示すように光輝焼鈍により(Cr+Si+Al)/Feを0.6以上に調整した材料では、塗装・焼付けによる色調の変化が少ない。一方、研磨仕上げ後、光輝焼鈍しない材料や本発明の範囲外の光輝焼鈍条件で処理し、原子濃度比(Cr+Si+Al)/Feを0.6未満に調整した材料は、塗装・焼付け時の黄色っぽい変色が大きく、特に焼付け温度が200℃以上の高い場合で顕著である。   Next, a material in which the atomic concentration ratio (Cr + Si + Al) / Fe is adjusted to 0.6 or more and a material in which the atomic concentration ratio (Cr + Si + Al) / Fe is adjusted to less than 0.6 are prepared, and the baking temperature is 150 ° C. to 250 ° C. Until I saw the change in color. Except for the difference in baking temperature and the difference in variety, the same as in the case of FIG. In FIG. 3, the atomic concentration ratio (Cr + Si + Al) / Fe is about 3 for the materials of ◯ and Δ. For ● and ▲, the atomic concentration ratio (Cr + Si + Al) / Fe is about 0.4 and 0.2, respectively. As a result, as shown in FIG. 3, in the material in which (Cr + Si + Al) / Fe is adjusted to 0.6 or more by bright annealing, the change in color tone due to painting and baking is small. On the other hand, after polishing finish, materials that are not brightly annealed or processed under bright annealing conditions outside the scope of the present invention and whose atomic concentration ratio (Cr + Si + Al) / Fe is adjusted to less than 0.6 are yellowish during coating and baking. Discoloration is large, especially when the baking temperature is as high as 200 ° C. or higher.

なお、本発明においては、表面酸化皮膜中の成分はAES(オージェ電子分光分析法)により分析し、酸素濃度が最も高い点での原子濃度比(Cr+Si+Al)/Feとした。本発明においては、(Cr+Si+Al)/Feを0.6以上に制御し、CrやSiの濃化した表面酸化皮膜とすることが極めて重要である。この場合、表面酸化皮膜の外層にSiが濃化し、Alはバルク近傍の内層に濃化する。この理由は、光輝焼鈍条件が、Crにとっては還元される条件、Si、Alにとっては酸化される条件となるとともに、SiO2よりもAl23の方が解離圧が低いからである。また、表面酸化皮膜の測定方法によっては、(Cr+Si+Al)/Feの適正範囲が異なってくることも考えられるが、必要な表面酸化皮膜構造は上記のとおりで同じある。 In the present invention, the components in the surface oxide film were analyzed by AES (Auger electron spectroscopy), and the atomic concentration ratio (Cr + Si + Al) / Fe at the highest oxygen concentration was obtained. In the present invention, it is extremely important to control the (Cr + Si + Al) / Fe to be 0.6 or more to obtain a surface oxide film enriched with Cr or Si. In this case, Si is concentrated in the outer layer of the surface oxide film, and Al is concentrated in the inner layer near the bulk. The reason for this is that the bright annealing condition is a reducing condition for Cr and an oxidizing condition for Si and Al, and Al 2 O 3 has a lower dissociation pressure than SiO 2 . Further, depending on the method of measuring the surface oxide film, the appropriate range of (Cr + Si + Al) / Fe may be different, but the necessary surface oxide film structure is the same as described above.

冷延焼鈍材、研磨仕上げ材の表面酸化皮膜中の原子濃度比(Cr+Si+Al)/Feは0.2程度である。そこで、本発明者らは、ステンレス鋼板に光輝焼鈍を施し、表面から50Åまでの深さにおけるCr,Si,Al,Feの原子濃度比(Cr+Si+Al)/Feが0.6以上となる酸化皮膜を形成させる光輝焼鈍条件を検討した。   The atomic concentration ratio (Cr + Si + Al) / Fe in the surface oxide film of the cold-rolled annealed material and the polished finish is about 0.2. Therefore, the present inventors performed bright annealing on the stainless steel plate, and formed an oxide film in which the atomic concentration ratio of Cr, Si, Al, Fe (Cr + Si + Al) / Fe is 0.6 or more at a depth of 50 mm from the surface. The bright annealing conditions to be formed were examined.

光輝焼鈍は一般に水素と窒素をH2:N2=(1〜9):1範囲の割合で混合した還元性雰囲気の中で行うが、その際焼鈍温度T1(℃)と雰囲気露点T2(℃)の組み合わせによって焼鈍後の酸化皮膜中の成分が変化する。 Bright annealing is generally performed in a reducing atmosphere in which hydrogen and nitrogen are mixed in a ratio of H 2 : N 2 = (1 to 9): 1. At that time, the annealing temperature T1 (° C.) and the atmospheric dew point T 2 (° C. ) Changes the components in the oxide film after annealing.

冷間圧延したSUS430J1LおよびSUS430鋼板に対して、冷間圧延焼鈍あるいはNo.4仕上げ(JIS G 0203 No.5349)相当の機械研磨を施し、種々の焼鈍温度T1(℃)と雰囲気露点T2(℃)で光輝焼鈍した結果を図4に示す。焼鈍温度T1を横軸に、雰囲気露点T2を縦軸にとり、それぞれの表面から50Åまでの深さにおける(Cr+Si+Al)/Fe原子濃度比が安定して0.6以上となる範囲は、
750≦T1≦5・T2+1200 ……1式
−70≦T2≦−30 ……2式
である。
For cold-rolled SUS430J1L and SUS430 steel plates, cold rolling annealing or no. FIG. 4 shows the results of bright annealing at various annealing temperatures T1 (° C.) and atmospheric dew points T2 (° C.) after mechanical polishing equivalent to 4 finishing (JIS G 0203 No. 5349). The range in which the annealing temperature T1 is on the horizontal axis and the atmospheric dew point T2 is on the vertical axis, and the (Cr + Si + Al) / Fe atomic concentration ratio at a depth of 50 mm from each surface is stably 0.6 or more,
750 ≦ T1 ≦ 5 · T2 + 1200 Equation 1 −70 ≦ T2 ≦ −30 Equation 2

1式、2式の範囲では、Crは還元される条件となる一方、Si,Alは酸化される条件となるため、有効成分(Si,Al)の皮膜中への選択酸化による濃化が効果的に行われる。光輝焼鈍の温度T1(℃)が750℃未満の場合は、Crを中心とした有効元素(Si,Al)の拡散移動が遅くなって十分な原子濃度比の酸化皮膜とならない。また温度T1(℃)が(5×T2+1200)℃を超える場合は、1式の範囲よりもさらに還元側の条件となるため、SiやAlの選択酸化が抑制され、十分な原子濃度比の酸化皮膜とならない。したがって、光輝焼鈍温度T1(℃)は、露点との関係から決まる1式の範囲が良い。好ましくは800℃以上、1000℃以下が良い。さらに好ましくは、800℃以上、900℃以下である。   In the range of Formulas 1 and 2, Cr is a condition for reduction, while Si and Al are conditions for oxidation. Therefore, concentration by selective oxidation of active ingredients (Si, Al) into the film is effective. Done. When the bright annealing temperature T1 (° C.) is lower than 750 ° C., the diffusion movement of effective elements (Si, Al) centering on Cr is slowed down, and an oxide film having a sufficient atomic concentration ratio is not obtained. Further, when the temperature T1 (° C.) exceeds (5 × T2 +1200) ° C., the condition is on the reduction side further than the range of the formula 1, so that selective oxidation of Si and Al is suppressed and oxidation with a sufficient atomic concentration ratio is achieved. It does not become a film. Therefore, the bright annealing temperature T1 (° C.) is preferably in the range of one set determined from the relationship with the dew point. Preferably 800 degreeC or more and 1000 degrees C or less are good. More preferably, it is 800 degreeC or more and 900 degrees C or less.

光輝焼鈍の露点T2(℃)は、−30℃を超えるとFeの酸化が激しくなり、表面の酸化皮膜へのFeの濃化が避けられず、テンパーカラーにより変色するのでクリヤ塗装ステンレス鋼板の素材として好ましくない。また、−70℃未満のガス露点は工業的に非常に難しい。従って、光輝焼鈍の露点は2式の範囲が良い。好ましくは、−60℃以上−35℃未満が良い。   The bright annealing dew point T2 (° C) exceeds -30 ° C, and the oxidation of Fe becomes intense. Concentration of Fe on the oxide film on the surface is inevitable, and the color changes due to the temper color. It is not preferable. Moreover, a gas dew point of less than -70 ° C is very difficult industrially. Accordingly, the dew point of bright annealing is preferably in the range of the two formulas. Preferably, -60 degreeC or more and less than -35 degreeC are good.

特許文献5に記載のものは、Si濃度0.3%においてテンパーカラー着色が少ないとしているものの、同文献におけるSi濃度0.3%の実施例はテンパーカラー着色評点3(黄色)であり、これでは白色度に優れたクリヤ塗装ステンレス鋼板とすることはできない。本発明においては、酸化皮膜中の原子濃度比(Cr+Si+Al)/Feを0.6以上と明確に規定し、この原子濃度比を実現することのできる製造条件を明確にすることにより、Si濃度0.8%以下の低Si濃度であっても白色度の優れたクリヤ塗装ステンレス鋼板とすることを可能とした。   Although the thing of patent document 5 says that there is little temper color coloring in Si density | concentration 0.3%, the Example of Si density | concentration 0.3% in the same literature is temper color coloring grade 3 (yellow). Therefore, it is not possible to obtain a clear coated stainless steel sheet having excellent whiteness. In the present invention, the atomic concentration ratio (Cr + Si + Al) / Fe in the oxide film is clearly defined as 0.6 or more, and the manufacturing conditions capable of realizing this atomic concentration ratio are clarified, whereby the Si concentration is reduced to 0. Even with a low Si concentration of 8% or less, it was possible to obtain a clear coated stainless steel plate with excellent whiteness.

研磨目によりステンレス独特の表面模様をつけた研磨仕上げ材が、意匠性が重視される部材として重宝されている。しかしながら、表面研磨を施したステンレス鋼の表面皮膜にはCr,Si,Alの濃化が非常に少ないので、クリヤ塗膜をつける時に黄変し、白色度に優れた高意匠性のクリヤ塗膜ステンレス鋼板を得ることはできない。そこで表面皮膜中にCr,Si,Alを濃化させるため光輝焼鈍を施す必要があるが、通常の軟化焼鈍を施したフェライト系ステンレス鋼板を表面研磨した後に光輝焼鈍を施すと、製造プロセスが煩雑になりコストアップの要因となる。そこで、本発明においては、冷間圧延したフェライト系ステンレス鋼板を、表面研磨した後に最終光輝焼鈍を施すことが望ましい。冷間圧延−表面研磨−光輝焼鈍の製造プロセスによって、材質造り込みのための軟質化焼鈍と表面皮膜中へのCr,Si,Alの濃化(高(Cr+Si+Al)/Fe)が1回の光輝焼鈍により同時に実施できる。特に本発明のフェライト系ステンレス鋼板においては、軟質化温度と表面皮膜中へのCr,Si,Alの濃化温度を合致するために、Nbの含有量によって再結晶温度を制御・調整することも可能である。また、オーステナイト系ステンレス鋼板の場合には、固溶化焼鈍は通常1000℃以上であるため、表面皮膜中へCr,Si,Alが濃化する温度とは一致しない。したがって、冷間圧延―研磨の後、固溶化焼鈍と酸化皮膜形成のための光輝焼鈍の2回の焼鈍を付与する必要がある。   Polishing finishes with a surface pattern peculiar to stainless steel by polishing eyes are useful as members that emphasize design. However, the surface coating of stainless steel that has undergone surface polishing has very little concentration of Cr, Si, and Al, so it turns yellow when applying a clear coating, and a highly designed clear coating with excellent whiteness Stainless steel sheets cannot be obtained. Therefore, it is necessary to perform bright annealing in order to concentrate Cr, Si, and Al in the surface film. However, if bright annealing is performed after surface polishing of a ferritic stainless steel sheet that has been subjected to normal softening annealing, the manufacturing process is complicated. This increases the cost. Therefore, in the present invention, it is desirable to subject the cold-rolled ferritic stainless steel sheet to the final bright annealing after surface polishing. Brightening of softening annealing for material preparation and concentration of Cr, Si, Al in the surface film (high (Cr + Si + Al) / Fe) by one manufacturing process of cold rolling-surface polishing-bright annealing It can be performed simultaneously by annealing. In particular, in the ferritic stainless steel sheet of the present invention, the recrystallization temperature may be controlled and adjusted by the Nb content in order to match the softening temperature with the concentration temperature of Cr, Si, Al in the surface film. Is possible. Further, in the case of an austenitic stainless steel sheet, since the solution annealing is usually 1000 ° C. or higher, it does not coincide with the temperature at which Cr, Si, Al is concentrated in the surface film. Therefore, after the cold rolling-polishing, it is necessary to provide two annealing steps, ie, solution annealing and bright annealing for forming an oxide film.

表1に、本発明の実施例および比較例を示す。フェライト系ステンレス鋼板の表面仕上げを、No.4(細かい目の研磨仕上げ)、HL(ヘアラインの研磨仕上げ)、および2B(酸洗後軽く圧延した肌)の3種類とした。これらフェライト系ステンレス鋼板を表1の条件で光輝焼鈍を施した。なお、2B仕上げのフェライト系ステンレス鋼板は、冷間圧延後に焼鈍を施した製造プロセスであるのに対し、その他の表面仕上げのものは、冷間圧延後の焼鈍はなされていないので、光輝焼鈍によって軟質化も同時に実施されるものである。   Table 1 shows examples and comparative examples of the present invention. The surface finish of ferritic stainless steel sheet is No. There were three types: 4 (polishing finish for fine eyes), HL (polishing finish for hairline), and 2B (skin that was lightly rolled after pickling). These ferritic stainless steel plates were brightly annealed under the conditions shown in Table 1. The ferritic stainless steel sheet with 2B finish is a manufacturing process that has been annealed after cold rolling, while other surface finishes have not been annealed after cold rolling. Softening is also performed at the same time.

Figure 2006299299
Figure 2006299299

光輝焼鈍後の各々のフェライト系ステンレス鋼板について表面から50Åまでの深さにおける酸化皮膜中のCr,Si,Al,Feの原子濃度比をAES(オージェ電子分光分析法)により測定し、原子濃度比(Cr+Si+Al)/Feを求めた。   For each ferritic stainless steel sheet after bright annealing, the atomic concentration ratio of Cr, Si, Al, Fe in the oxide film at a depth of 50 mm from the surface was measured by AES (Auger Electron Spectroscopy), and the atomic concentration ratio (Cr + Si + Al) / Fe was determined.

光輝焼鈍後の各々のフェライト系ステンレス鋼板に対し、化成処理として日本パーカライジング社の化成処理剤(E−206)についてアミノシラン系のものとエポキシシラン系のものを用い、その付着量を2mg/m2から50mg/m2の範囲で変化させた。比較として化成処理剤にクロメート処理を施した。その後、アクリルウレタン樹脂系のクリヤ皮膜を1〜10μmを焼付け温度220℃で処理した。 For each ferritic stainless steel sheet after bright annealing, an aminosilane-based and epoxysilane-based chemical conversion treatment agent (E-206) manufactured by Nippon Parkerizing Co., Ltd. was used as the chemical conversion treatment, and the adhesion amount was 2 mg / m 2. To 50 mg / m 2 . As a comparison, the chemical conversion treatment agent was chromated. Thereafter, the acrylic urethane resin-based clear film was treated at a baking temperature of 220 ° C. for 1 to 10 μm.

クリヤ塗装後の色調は、b*(JIS Z8729)で測定し、変色の程度を評価した。   The color tone after clear coating was measured by b * (JIS Z8729), and the degree of discoloration was evaluated.

本発明例では、フェライト系ステンレス鋼板表面の酸化皮膜中の原子濃度比が0.6以上で、アミノシラン系、エポキシシラン系の1種類又は2種類よりなる化成処理を、付着量が2〜20mg/m2にすることにより、b*が2以下の白色度に優れたクリヤ塗装鋼板を得ることができるのに対して、比較例ではb*が2を超える黄色みを帯びたクリヤ塗装鋼板となり、見る角度によっては黒っぽい色調に見える。 In the present invention example, a chemical conversion treatment having an atomic concentration ratio in the oxide film on the surface of the ferritic stainless steel sheet of 0.6 or more and consisting of one or two types of aminosilane type and epoxysilane type, the adhesion amount is 2 to 20 mg / By making m 2 , a clear coated steel sheet having excellent b * with a b * of 2 or less can be obtained, whereas in a comparative example, a clear coated steel sheet with a b * exceeding 2 is obtained, Depending on the viewing angle, it looks dark.

比較例20では、ステンレス鋼板のSiの成分が下限を外れたため、酸化皮膜中の(Cr+Si+Al)/Feが下限を外れ、b*が2以上で白色度に劣る。比較例21〜25は光輝焼鈍条件の温度T1および露点T2の一方が上下限を外れたため、酸化皮膜中の(Cr+Si+Al)/Feが下限を外れ、b*が2以上で白色度に劣る。特に比較例25は、ステンレス鋼板の素材のテンパーカラーが明瞭に観察されたので(Cr+Si+Al)/Feを測定していない。比較例26〜32は、素材の(Cr+Si+Al)/Feは0.6以上だが、化成処理剤の条件が本発明範囲を外れている。比較例26は化成処理剤の付着量が下限を外れ、密着性不良である。比較例27は化成処理剤の付着量が上限を外れ、比較例28は化成処理剤がクロメート剤であり本発明のノンクロメート系の処理剤ではないことより、b*が2以上で白色度に劣る。比較例29および31はクリヤ塗料厚さが下限を外れており、色調が不安定である。比較例30および32はクリヤ塗料厚さが上限外れており、製造困難である。   In Comparative Example 20, since the Si component of the stainless steel plate deviated from the lower limit, (Cr + Si + Al) / Fe in the oxide film deviated from the lower limit, and b * was 2 or more, resulting in poor whiteness. In Comparative Examples 21 to 25, one of the temperature T1 and the dew point T2 under the bright annealing condition deviated from the upper and lower limits, so (Cr + Si + Al) / Fe in the oxide film deviated from the lower limit, and b * was 2 or more, resulting in poor whiteness. In particular, Comparative Example 25 did not measure (Cr + Si + Al) / Fe because the temper color of the stainless steel plate material was clearly observed. In Comparative Examples 26 to 32, the material (Cr + Si + Al) / Fe is 0.6 or more, but the conditions of the chemical conversion treatment agent are out of the scope of the present invention. In Comparative Example 26, the adhesion amount of the chemical conversion treatment agent deviated from the lower limit, resulting in poor adhesion. In Comparative Example 27, the adhesion amount of the chemical conversion treatment agent deviated from the upper limit, and in Comparative Example 28, the chemical conversion treatment agent was a chromate agent and not the non-chromate treatment agent of the present invention. Inferior. In Comparative Examples 29 and 31, the clear paint thickness is outside the lower limit, and the color tone is unstable. In Comparative Examples 30 and 32, the clear paint thickness is outside the upper limit, and it is difficult to manufacture.

化成処理付着量とクリヤ塗装ステンレス鋼板の変色Δb*の関係を示す図である。It is a figure which shows the relationship between a chemical conversion treatment adhesion amount and discoloration (DELTA) b * of a clear coating stainless steel plate. 表面から50Åまでの深さにおける酸化皮膜中のCr,Si,Al,Feの原子濃度比(Cr+Si+Al)/Feと224℃焼付けによるクリヤ塗装ステンレス鋼板の変色Δb*の関係を示す図である。It is a figure which shows the relationship of the discoloration (DELTA) b * of the clear coating stainless steel plate by 224 degreeC baking, and atomic concentration ratio (Cr + Si + Al) / Fe of Cr, Si, Al, and Fe in the oxide film in the depth from the surface to 50 mm. 研磨仕上げステンレス鋼板と研磨後本発明範囲の光輝焼鈍を施した鋼板の焼付け温度とクリヤ塗装ステンレス鋼板の変色Δb*の関係を示す図である。It is a figure which shows the relationship between the baking temperature of a polished finish stainless steel plate and the steel plate which gave the bright annealing of the range of this invention after grinding | polishing, and discoloration (DELTA) b * of a clear coating stainless steel plate. 光輝焼鈍の焼鈍温度T1(℃)、露点T2(℃)と表面から50Åまでの深さにおける酸化皮膜中のCr,Si,Al,Feの原子濃度比(Cr+Si+Al)/Feの関係を示す図である。It is the figure which shows the relationship of the atomic concentration ratio (Cr + Si + Al) / Fe of Cr, Si, Al, and Fe in the oxide film in the depth from the surface to the annealing temperature T1 (° C.) and dew point T 2 (° C.) of bright annealing. is there.

Claims (5)

ステンレス鋼板が質量%でSi:0.2〜0.8%を含有するフェライト系ステンレス鋼板であり、該鋼板はその表面から50Åまでの深さにおけるCr,Si,Al,Fe原子濃度比(Cr+Si+Al)/Feが0.6以上の表面酸化皮膜を有し、
塗膜の化成処理剤がアミノシラン系、エポキシシラン系の1種類または2種類よりなり、該化成処理剤の付着量が2〜20mg/m2(蛍光X線にてSiO2量を測定)であり、クリヤ塗料厚さが1〜10μmの塗膜を有することを特徴とする白色度に優れるクリヤ塗装ステンレス鋼板。
The stainless steel plate is a ferritic stainless steel plate containing Si: 0.2 to 0.8% by mass%, and the steel plate has a Cr, Si, Al, Fe atomic concentration ratio (Cr + Si + Al at a depth of 50 mm from the surface thereof. ) / Fe has a surface oxide film of 0.6 or more,
The chemical conversion treatment agent of the coating film is composed of one or two types of aminosilane type and epoxysilane type, and the adhesion amount of the chemical conversion treatment agent is 2 to 20 mg / m 2 (the amount of SiO 2 is measured by fluorescent X-ray). A clear-coated stainless steel sheet excellent in whiteness, characterized in that it has a coating with a clear paint thickness of 1 to 10 μm.
前記ステンレス鋼板はさらに質量%でAl:0.005〜0.15%を含有することを特徴とする請求項1に記載の白色度に優れるクリヤ塗装ステンレス鋼板。   The clear coated stainless steel sheet having excellent whiteness according to claim 1, wherein the stainless steel sheet further contains Al: 0.005 to 0.15% by mass. 前記ステンレス鋼板はさらに質量%でNb:0.1〜0.7%を含有することを特徴とする請求項1又は2に記載の白色度に優れるクリヤ塗装ステンレス鋼板。   The said stainless steel plate contains Nb: 0.1-0.7% further by the mass%, The clear coated stainless steel plate excellent in the whiteness of Claim 1 or 2 characterized by the above-mentioned. 最終光輝焼鈍の温度T1(℃)および焼鈍雰囲気の露点T2(℃)が1式および2式を満足する条件で行なうことを特徴とする請求項1乃至3のいずれかに記載の白色度に優れるクリヤ塗装ステンレス鋼板素材の製造方法。
750≦T1≦5×T2+1200 ……1式
−70≦T2≦−30 ……2式
The whiteness according to any one of claims 1 to 3, wherein the final bright annealing temperature T1 (° C) and the dew point T2 (° C) of the annealing atmosphere are satisfied under the conditions of the first and second formulas. Manufacturing method of clear coated stainless steel sheet material.
750 ≦ T1 ≦ 5 × T2 + 1200 Equation 1 −70 ≦ T2 ≦ −30 Equation 2
冷間圧延したフェライト系ステンレス鋼板を、表面研磨した後に最終光輝焼鈍を施すことを特徴とする請求項4に記載の白色度に優れるクリヤ塗装ステンレス鋼板素材の製造方法。   The method for producing a clear coated stainless steel sheet material having excellent whiteness according to claim 4, wherein the bright bright annealing is performed after surface polishing of the cold rolled ferritic stainless steel sheet.
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JPH0985880A (en) * 1995-09-25 1997-03-31 Nkk Corp Clear coating stainless steel sheet
JP2002105605A (en) * 2000-07-25 2002-04-10 Kawasaki Steel Corp Ferritic stainless steel sheet having excellent cold workability and high temperature mechanical property, and its production method
JP2004122409A (en) * 2002-09-30 2004-04-22 Sumitomo Metal Ind Ltd Clear coating stainless steel sheet

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JP2008231551A (en) * 2007-03-23 2008-10-02 Nisshin Steel Co Ltd Stainless steel product excellent in temper coloring resistance and method for manufacturing the same
JP2009256786A (en) * 2008-03-25 2009-11-05 Nisshin Steel Co Ltd Heat resistant non-adhesive clear coated stainless steel sheet free from the generation of tamper color
JP2010229488A (en) * 2009-03-27 2010-10-14 Nisshin Steel Co Ltd Method for manufacturing polish-finished material of ferritic-stainless steel
JPWO2016039429A1 (en) * 2014-09-10 2017-07-06 新日鐵住金株式会社 Austenitic stainless steel sheet that is difficult to diffuse and bond

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CN101098988A (en) 2008-01-02
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WO2006112376A1 (en) 2006-10-26
AU2006237998B2 (en) 2009-06-11
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CN100585006C (en) 2010-01-27
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KR101018487B1 (en) 2011-03-03
TW200702453A (en) 2007-01-16

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