JP2002275541A - Method for manufacturing stainless steel sheet - Google Patents
Method for manufacturing stainless steel sheetInfo
- Publication number
- JP2002275541A JP2002275541A JP2001071820A JP2001071820A JP2002275541A JP 2002275541 A JP2002275541 A JP 2002275541A JP 2001071820 A JP2001071820 A JP 2001071820A JP 2001071820 A JP2001071820 A JP 2001071820A JP 2002275541 A JP2002275541 A JP 2002275541A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- steel sheet
- pickling
- gas
- steel plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Heat Treatment Of Sheet Steel (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、表面に塗装、メ
ッキ、ハンダなどの表面処理が施されるステンレス鋼板
やフォトエッチング加工されるステンレス鋼板の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a stainless steel sheet whose surface is subjected to surface treatment such as painting, plating, soldering and the like, and a stainless steel sheet which is subjected to photo-etching.
【０００２】[0002]
【従来の技術】ステンレス鋼は、耐食性や機械的特性に
優れることから、建材、外装材、厨房用品、精密電子部
品などに利用される。また、耐食性の向上や意匠性およ
び機能性などを付与するために、ステンレス鋼板の表面
に塗装、メッキおよびハンダなどの表面処理が施される
こともある。このような表面処理が施される場合は、ス
テンレス鋼板の表面と、塗料、メッキ、ハンダなどの被
覆物質との密着性に優れることが要求される。2. Description of the Related Art Stainless steel is used for building materials, exterior materials, kitchenware, precision electronic parts, etc. because of its excellent corrosion resistance and mechanical properties. Further, the surface of the stainless steel plate may be subjected to a surface treatment such as painting, plating and soldering in order to improve corrosion resistance and impart design and functionality. When such a surface treatment is performed, it is required that the surface of the stainless steel sheet has excellent adhesion to coating materials such as paint, plating, and solder.
【０００３】また、精密な電子部品は、フォトエッチン
グ加工により製造されることが多く、この場合は、ステ
ンレス鋼板の表面と、フォトレジストとの密着性に優れ
ることが要求される。フォトエッチング加工とは、金属
の腐食現象を利用した加工技術であり、各種の精密電子
部品やプリント配線板、シャドウマスク、ＩＣリードフ
レームなどの微細な加工を行う方法として欠かせない加
工法である。このフォトエッチング加工は、例えば、次
のようにして行われる。In addition, precision electronic components are often manufactured by photoetching, and in this case, it is required that the surface of the stainless steel plate and the photoresist have excellent adhesion. Photoetching is a processing technique that utilizes the corrosion phenomenon of metal, and is an indispensable processing method for performing fine processing of various precision electronic components, printed wiring boards, shadow masks, IC lead frames, and the like. . This photo-etching is performed, for example, as follows.
【０００４】冷間圧延により製造されたステンレス鋼板
などの被加工鋼板（以下、単に鋼板と表す）に、前処理
（一般的には、アルカリ脱脂、酸洗、水洗および乾燥）
を施した後、その表面にフォトレジスト膜を被覆する。
次に、フォトレジスト膜の上に露光用原版を重ねた後、
紫外線を照射する。その後、これを現像液で処理する
と、紫外線が照射されなかった部分のフォトレジスト膜
が溶けて除去され、その部分の鋼板が露出して、鋼板の
表面に露光用原版と同じパターンが形成される。[0004] Pre-treatment (generally, alkali degreasing, pickling, water washing and drying) is applied to a steel sheet to be processed (hereinafter simply referred to as a steel sheet) such as a stainless steel sheet manufactured by cold rolling.
After that, the surface is coated with a photoresist film.
Next, after overlaying the exposure master on the photoresist film,
Irradiate with ultraviolet light. After that, when this is treated with a developing solution, the photoresist film in the portion not irradiated with the ultraviolet rays is melted and removed, and the steel plate in that portion is exposed, and the same pattern as the original plate for exposure is formed on the surface of the steel plate. .
【０００５】所定のパターンが形成された鋼板に、塩化
第二鉄溶液などのエッチング液をスプレーして、鋼板の
露出した部分を溶解する。その後、フォトレジスト膜を
剥離すると、露光用原版と同じパターンにエッチングさ
れた製品が得られる。An exposed portion of the steel sheet is dissolved by spraying an etching solution such as a ferric chloride solution on the steel sheet on which a predetermined pattern is formed. Thereafter, when the photoresist film is removed, a product etched in the same pattern as the original plate for exposure is obtained.
【０００６】上記の工程において、フォトエッチング加
工の前工程で実施されるアルカリ脱脂は、鋼板の表面に
付着した圧延油やその他の汚染物質を除去するための処
理である。次いで実施される酸洗は、鋼板の表面に残留
したアルカリ分を中和し、かつ酸化皮膜を溶解して鋼板
の表面を活性化させることによって、鋼板の表面と有機
樹脂との密着性を高めることを目的としている。酸洗液
には、塩酸、硫酸、硝酸および弗酸の１種または２種以
上を含む水溶液が用いられることが多い。[0006] In the above process, the alkaline degreasing performed before the photoetching process is a process for removing rolling oil and other contaminants adhering to the surface of the steel sheet. Next, pickling is carried out to neutralize the alkali remaining on the surface of the steel sheet and dissolve the oxide film to activate the surface of the steel sheet, thereby increasing the adhesion between the steel sheet surface and the organic resin. It is intended to be. For the pickling solution, an aqueous solution containing one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid is often used.
【０００７】前記のフォトレジストは、例えば、カゼイ
ンあるいはアクリル樹脂系の感光性の有機樹脂である。
このフォトレジスト膜を鋼板の表面に被覆するには、鋼
板を液体状のフォトレジストに浸漬した後に乾燥する方
法と、予めフィルム状に成形されたフォトレジストを鋼
板の表面に張付ける方法とがある。The photoresist is, for example, casein or an acrylic resin-based photosensitive organic resin.
In order to coat the photoresist film on the surface of the steel plate, there are a method of dipping the steel plate in a liquid photoresist and then drying the same, and a method of attaching a photoresist formed in a film shape in advance to the surface of the steel plate. .
【０００８】ところで、ステンレス鋼板は、溶解および
鋳造後に熱間圧延された熱延鋼板を脱スケールした後、
冷間圧延と焼きなましとを繰返して行うことにより製造
される。工業的な焼きなましとして、光輝焼きなましが
採用されることが多い。[0008] Incidentally, the stainless steel sheet is obtained by descaling a hot-rolled steel sheet which has been hot-rolled after melting and casting.
It is manufactured by repeatedly performing cold rolling and annealing. Bright annealing is often employed as industrial annealing.
【０００９】光輝焼きなましは、無酸化雰囲気中で焼き
なまし処理を行う方法であり、酸化スケールが生成しな
いため、酸洗脱スケールの工程を省略することができ
る。また、冷間圧延によりステンレス鋼板の表面に生じ
た光沢を、そのまま製品肌とすることができるという利
点がある。Bright annealing is a method in which annealing is performed in a non-oxidizing atmosphere, and since no oxide scale is generated, the step of pickling and descaling can be omitted. Further, there is an advantage that the gloss generated on the surface of the stainless steel plate by cold rolling can be used as the product surface as it is.
【００１０】ところが、光輝焼きなましが施されたステ
ンレス鋼板の表面には、Ｆｅ系酸化物、Ｃｒ酸化物およ
び結晶質または非晶質のＳｉＯ２ などを主成分とする
酸化皮膜が形成される。この酸化皮膜は、ステンレス鋼
板の耐食性を維持するために有効である。しかし、酸化
皮膜を構成する酸化物は、水や有機被覆物との親和性が
悪く、ステンレス鋼板の表面のヌレ性を悪化させる原因
となる。However, on the surface of the brightly annealed stainless steel sheet, an oxide film mainly composed of Fe-based oxide, Cr oxide and crystalline or amorphous SiO 2 is formed. This oxide film is effective for maintaining the corrosion resistance of the stainless steel sheet. However, the oxide constituting the oxide film has a poor affinity for water and an organic coating, and causes deterioration of the wettability of the surface of the stainless steel sheet.
【００１１】このようなヌレ性の悪い酸化皮膜が表面に
形成されたステンレス鋼板を、塗装鋼板の母材として使
用すると、十分な塗膜密着性が得られず、塗装鋼板の成
形加工時や使用中に、塗膜の亀裂や剥離などが発生しや
すい。この現象は、ステンレス鋼板の表面にメッキやハ
ンダが施される場合にも生じる。When a stainless steel sheet having such an oxide film having poor wettability formed on the surface is used as a base material of a coated steel sheet, sufficient adhesion of the coating film cannot be obtained, and the coated steel sheet is formed and used. During the coating, cracks and peeling of the coating film easily occur. This phenomenon also occurs when the surface of the stainless steel plate is plated or soldered.
【００１２】また、表面のヌレ性に劣るステンレス鋼板
をフォトエッチング加工する場合、前処理工程でアルカ
リ脱脂を行っても十分に脱脂されないばかりか、その後
に酸洗を行った際に、酸洗液を弾いてしまい前処理の効
果が得られない。さらに、酸化皮膜が残存した状態でフ
ォトレジスト膜を被覆しても、フォトレジストは前記の
ように有機被覆物であるため、十分な密着性を得ること
ができない。When a stainless steel sheet having poor surface wetting properties is subjected to photoetching, not only is it not sufficiently degreased even if alkali degreasing is performed in the pretreatment step, but also if pickling is performed thereafter, the pickling solution is removed. And the effect of pre-processing cannot be obtained. Further, even if the photoresist film is coated with the oxide film remaining, sufficient adhesion cannot be obtained because the photoresist is an organic coating as described above.
【００１３】このように、フォトレジスト膜が十分に密
着していないステンレス鋼板をフォトエッチング加工す
ると、エッチング中にステンレス鋼板とフォトレジスト
膜の界面にエッチング液が浸透する。そのため、予期し
ない腐食溶解が進行して製品形状を著しく損ねたり、最
悪の場合は、現像工程あるいはフォトエッチング工程で
フォトレジスト膜が剥離するという問題が生じる。As described above, when a stainless steel plate on which the photoresist film is not sufficiently adhered is photo-etched, the etching solution permeates the interface between the stainless steel plate and the photoresist film during the etching. As a result, unexpected corrosion and dissolution progresses to significantly impair the product shape, and in the worst case, there arises a problem that the photoresist film is peeled off in the developing step or the photo etching step.
【００１４】ステンレス鋼板の表面を、物理的に粗くす
ることによって塗膜との密着性を向上させる方法が、例
えば、特開平９−１４１３０３号公報、および特開平９
−２５６１９９号公報に提案されている。A method for improving the adhesion to a coating film by physically roughening the surface of a stainless steel plate is disclosed in, for example, Japanese Patent Application Laid-Open Nos.
-256199.
【００１５】特開平９−１４１３０３号公報に提案され
た方法は、ステンレス鋼板を表面粗度の粗いロールで仕
上げ圧延して、ステンレス鋼板の表面に凹凸を付与する
方法である。また、特開平９−２５６１９９号公報に提
案された方法は、フェライト系ステンレス鋼板を塩化第
二鉄中で交番電解して、フェライト系ステンレス鋼板の
表面にピットを隙間なく形成させる方法である。The method proposed in Japanese Patent Application Laid-Open No. 9-141303 is a method in which a stainless steel plate is finish-rolled with a roll having a rough surface to provide irregularities on the surface of the stainless steel plate. The method proposed in Japanese Patent Application Laid-Open No. 9-256199 is a method in which a ferrite stainless steel sheet is alternately electrolyzed in ferric chloride to form pits on the surface of the ferrite stainless steel sheet without gaps.
【００１６】しかし、これらの２つの方法を、フォトエ
ッチング加工用のステンレス鋼板に採用した場合、ステ
ンレス鋼板の表面粗さを粗くしすぎると、ステンレス鋼
板とフォトレジスト膜の界面との間に隙間が生じやすく
なり、フォトエッチング加工したときにエッチング液が
隙間に浸透しやすくなる。このようにしてフォトエッチ
ング加工された製品は、エッチング端面の直線性が乱れ
たり、あるいは正確な寸法の製品が得られないおそれが
ある。However, when these two methods are applied to a stainless steel plate for photo-etching, if the surface roughness of the stainless steel plate is too coarse, a gap is formed between the stainless steel plate and the interface between the photoresist film. This tends to occur, and the etching liquid easily penetrates into the gap when performing photoetching. In the photo-etched product, the linearity of the etched end face may be disturbed, or a product having accurate dimensions may not be obtained.
【００１７】ステンレス鋼板と塗膜との密着性を向上さ
せる別の方法として、化学的に表面皮膜を溶解して活性
な素地を露出させる方法、あるいはシランカップリング
やクロメートなどの化成処理を施す方法が知られてい
る。例えば、特開平６−２３５１００号公報には、フェ
ライト系ステンレス鋼板を、露点が−３５〜−４５℃の
雰囲気中で光輝焼きなましを行った後に、硝酸溶液中で
陽極電解する方法が提案されている。As another method for improving the adhesion between the stainless steel plate and the coating film, a method of chemically dissolving a surface film to expose an active substrate, or a method of performing a chemical conversion treatment such as silane coupling or chromate. It has been known. For example, JP-A-6-235100 proposes a method in which a ferritic stainless steel sheet is brightly annealed in an atmosphere having a dew point of -35 to -45 ° C, and then anodically electrolyzed in a nitric acid solution. .
【００１８】しかし、このように化学的に表面を溶解す
る方法や化成処理を施す方法は、塗装用のステンレス鋼
板に対しては有効であるが、過剰に表面を溶解すると、
ステンレス鋼板本来の光沢を損う。したがって、最終的
にフォトレジストを除去して使用されるフォトエッチン
グ加工用のステンレス鋼板に、これらの方法を採用する
のは製品の外観上好ましくない。However, such a method of chemically dissolving the surface and a method of performing a chemical conversion treatment are effective for a stainless steel plate for coating, but when the surface is excessively dissolved,
Impairs the original gloss of stainless steel plates. Therefore, it is not preferable in terms of the appearance of a product to employ these methods for a stainless steel plate for photo-etching, which is used after finally removing the photoresist.
【００１９】また、フォトエッチング加工されたステン
レス鋼板は、フォトレジストを被覆した状態で成形加工
されることがなく、被覆されたフォトレジストを最終工
程で除去する必要がある。そのため、密着性が強すぎる
と除去されなかったり残滓が残ったりするので、塗装鋼
板のような永続的かつ強固な樹脂密着性を形成する際に
有効な化成処理は適さない。Further, the stainless steel plate subjected to the photo-etching process is not formed in a state where the photo-resist is coated, and the coated photo-resist needs to be removed in the final step. Therefore, if the adhesion is too strong, it will not be removed or a residue will remain. Therefore, a chemical conversion treatment that is effective in forming a permanent and strong resin adhesion such as a coated steel sheet is not suitable.
【００２０】さらに化成処理を施した場合は、フォトレ
ジストで所定のパターンが形成されたステンレス鋼板
の、金属が露出した部分に化成処理皮膜が存在するため
に、フォトエッチング加工するときの腐食溶解の進行が
阻害されることになる。Further, when a chemical conversion treatment is performed, since a chemical conversion coating is present on a portion of the stainless steel plate on which a predetermined pattern is formed with a photoresist and where the metal is exposed, corrosion and dissolution during photoetching are performed. Progression will be hindered.
【００２１】フォトエッチング加工される鋼板のフォト
レジストとの密着性を改善する方法が、特開昭５５−１
２２８７６号公報、特開平８−２２５９６０号公報およ
び特開２０００−４５０８０号公報に提案されている。A method for improving the adhesion of a steel plate to be subjected to photoetching to a photoresist is disclosed in
No. 22,876, Japanese Patent Application Laid-Open No. 8-225960 and Japanese Patent Application Laid-Open No. 2000-45080.
【００２２】特開昭５５−１２２８７６号公報に提案さ
れた方法は、クロム酸と硫酸の混合水溶液あるいはアル
カリ性酸化液（水酸化ナトリウムと硝酸ナトリウムの混
合水溶液等）を用いて表面に酸化皮膜を形成させ、フォ
トレジストと鋼材との密着性を改善する方法である。し
かし、この方法では、特に光輝焼きなましが施されて酸
化皮膜が存在している場合は、逆にフォトレジスト密着
性を阻害することになる。The method proposed in Japanese Patent Application Laid-Open No. 55-122876 discloses a method of forming an oxide film on the surface using a mixed aqueous solution of chromic acid and sulfuric acid or an alkaline oxidizing solution (a mixed aqueous solution of sodium hydroxide and sodium nitrate). This is a method of improving the adhesion between the photoresist and the steel material. However, according to this method, especially when bright annealing is performed and an oxide film is present, the adhesiveness of the photoresist is adversely affected.
【００２３】特開平８−２２５９６０号公報に提案され
た方法は、フォトレジスト塗布前に、１０〜３０％燐酸
溶液あるいは１０〜３０％燐酸と０．２〜１０％硝酸と
の混合溶液で酸洗して酸化被膜を除去する方法である。
また、特開２０００−４５０８０号公報に提案された方
法は、フォトレジスト塗布前に、０．５〜１％未満の弗
酸と２〜４％未満の硝酸とを含む液温が２０〜３５℃の
水溶液に２０〜６０秒浸漬して酸化被膜を除去する方法
である。しかし、これらの方法では、鋼板に生じるスケ
ールの厚さが厚い場合には、短時間でスケールを除去す
ることができない。The method proposed in Japanese Patent Application Laid-Open No. 8-225960 discloses a method of pickling with a 10 to 30% phosphoric acid solution or a mixed solution of 10 to 30% phosphoric acid and 0.2 to 10% nitric acid before applying a photoresist. To remove the oxide film.
In addition, the method proposed in Japanese Patent Application Laid-Open No. 2000-45080 discloses that the temperature of a solution containing 0.5 to less than 1% of hydrofluoric acid and 2 to less than 4% of nitric acid before coating a photoresist is 20 to 35 ° C. This is a method in which the oxide film is removed by immersion in an aqueous solution for 20 to 60 seconds. However, these methods cannot remove the scale in a short time when the scale generated on the steel sheet is thick.
【００２４】[0024]
【発明が解決しようとする課題】この発明の課題は、ヌ
レ性に優れるステンレス鋼板を、表面の光沢を損なうこ
となく製造することのできるステンレス鋼板の製造方法
を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a stainless steel sheet which can produce a stainless steel sheet having excellent wettability without impairing the surface gloss.
【００２５】[0025]
【課題を解決するための手段】この発明の要旨は、次の
ステンレス鋼板の製造方法にある。The gist of the present invention resides in the following method for manufacturing a stainless steel plate.
【００２６】冷間圧延されたステンレス鋼板に、露点が
−４０℃より低く、かつ下記（１）式で表される水素ガ
スの比率Ａが７５％を超える水素ガスと窒素ガスの混合
ガスの雰囲気中で光輝焼なましを施し、その後、塩酸、
硫酸、硝酸および弗酸の１種または２種以上を合計で１
〜１０重量％含む水溶液で酸洗することを特徴とするス
テンレス鋼板の製造方法。An atmosphere of a mixed gas of hydrogen gas and nitrogen gas having a dew point lower than -40 ° C. and a ratio A of hydrogen gas represented by the following formula (1) exceeding 75% on a cold-rolled stainless steel plate: In the bright annealing in, then, hydrochloric acid,
One or more of sulfuric acid, nitric acid and hydrofluoric acid in a total of 1
Pickling with an aqueous solution containing from 10 to 10% by weight.
【００２７】 Ａ＝１００・Ｈ２／（Ｈ２＋Ｎ２）・・・（１） ここでＨ２ ：雰囲気ガス中の水素ガスの濃度（容量
％）、 Ｎ２ ：雰囲気ガス中の窒素ガスの濃度（容量％）。A = 100 · H 2 / (H 2 + N 2 ) (1) where H 2 : concentration of hydrogen gas in the atmosphere gas (volume%), N 2 : nitrogen gas in the atmosphere gas Concentration (% by volume).
【００２８】ステンレス鋼板がフォトエッチング加工用
の場合は、フォトエッチング処理の前処理工程における
酸洗時に本発明で規定する条件の酸洗を行う。When the stainless steel plate is used for photoetching, pickling under the conditions specified in the present invention is performed at the time of pickling in the pretreatment step of the photoetching process.
【００２９】本発明のステンレス鋼板の製造方法は、冷
間圧延されたステンレス鋼板に、まず、露点が−４０℃
より低く、かつ前記（１）式で表される水素ガスの比率
Ａが７５％を超える水素ガスと窒素ガスの混合ガスの雰
囲気中で光輝焼なましを施す。この光輝焼きなましによ
って、ステンレス鋼板の表面に生成する酸化皮膜の厚さ
を薄くすることができる。In the method for producing a stainless steel sheet according to the present invention, a cold rolled stainless steel sheet is first subjected to a dew point of -40 ° C.
Bright annealing is performed in an atmosphere of a mixed gas of hydrogen gas and nitrogen gas, which is lower and the ratio A of the hydrogen gas represented by the formula (1) exceeds 75%. By this bright annealing, the thickness of the oxide film formed on the surface of the stainless steel plate can be reduced.
【００３０】その後、塩酸、硫酸、硝酸、弗酸の１種ま
たは２種以上を合計で１〜１０重量％含む水溶液で酸洗
を行う。前記の光輝焼きなましによって生成された酸化
被膜の厚さは薄いので、このような弱酸による酸洗によ
っても容易に除去されて、ステンレス鋼板の表面は、極
めて良好なヌレ性を示す。また、表面の光沢も失われな
い。Thereafter, pickling is carried out with an aqueous solution containing 1 to 10% by weight in total of one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid. Since the thickness of the oxide film formed by the bright annealing is thin, the oxide film is easily removed even by pickling with such a weak acid, and the surface of the stainless steel sheet exhibits extremely good wetting properties. Also, the gloss of the surface is not lost.
【００３１】[0031]
【発明の実施の形態】（１）光輝焼きなまし 厚い酸化皮膜が形成されたステンレス鋼板を、フォトエ
ッチング処理の前処理で行われる酸洗のように、弱酸で
短時間に酸洗する方法では、酸化皮膜を除去しきれな
い。一方、強酸で長時間の酸洗を行うことは、生産性が
低下するとともに、表面の光沢を損い、品質上好ましく
ない。したがって、光輝焼きなましでステンレス鋼板の
表面に形成される酸化皮膜は、できるだけ薄いことが望
ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Bright Annealing In a method in which a stainless steel sheet on which a thick oxide film is formed is pickled in a short time with a weak acid, such as pickling performed in a pretreatment of a photoetching process, oxidation is performed. The film cannot be completely removed. On the other hand, performing acid pickling for a long time with a strong acid not only reduces the productivity but also impairs the surface gloss, which is not preferable in terms of quality. Therefore, it is desirable that the oxide film formed on the surface of the stainless steel plate by bright annealing is as thin as possible.
【００３２】ステンレス鋼板の表面に形成される酸化皮
膜は、光輝焼きなましにおける露点と雰囲気ガスの組成
が大きく影響している。The oxide film formed on the surface of the stainless steel sheet is greatly influenced by the dew point and bright gas composition in bright annealing.
【００３３】光輝焼きなましにおける露点は、−４０℃
より低くする。発明者の検討では、露点が高くなると、
雰囲気中の水分濃度が増加してステンレス鋼板の表面の
酸化が促進され、酸化皮膜の厚さが厚くなる。特に露点
が−４０℃以上では、ステンレス鋼板に厚い酸化皮膜が
形成される。一方、露点が−４０℃より低いと、ステン
レス鋼板の表面に形成される酸化被膜の厚さが薄くなる
（後述する図１参照）。そのため、フォトエッチング処
理の前処理で行われる酸洗のような軽度の酸洗によって
も、容易に表面ヌレ性が改善される。露点を−４０℃よ
り低くする方法は、水分量が少なく純度の高い雰囲気ガ
スを使用するとともに、水分の進入経路を遮断する。ま
た、ステンレス鋼板の表面に付着して持込まれる水分を
抑制するため、焼きなまし炉に入る前のステンレス鋼板
の表面に、１００℃以上の熱風を吹き付けて乾燥させる
方法が効果的である。また、焼きなまし炉の密閉性を高
めておくことも重要である。The dew point in bright annealing is -40 ° C.
Lower. According to the inventors' examination, when the dew point increases,
Oxidation of the surface of the stainless steel sheet is promoted by increasing the moisture concentration in the atmosphere, and the thickness of the oxide film is increased. In particular, when the dew point is −40 ° C. or higher, a thick oxide film is formed on the stainless steel plate. On the other hand, when the dew point is lower than −40 ° C., the thickness of the oxide film formed on the surface of the stainless steel sheet becomes thin (see FIG. 1 described later). Therefore, the surface wetness can be easily improved even by light pickling such as pickling performed in the pre-treatment of the photo-etching treatment. The method of setting the dew point to be lower than −40 ° C. uses an atmosphere gas having a small amount of water and a high purity, and shuts off a water entry path. Further, in order to suppress moisture adhering to the surface of the stainless steel plate, a method of blowing hot air of 100 ° C. or more onto the surface of the stainless steel plate before entering the annealing furnace to dry the surface is effective. It is also important to improve the tightness of the annealing furnace.
【００３４】雰囲気ガスは、下記の（１）式で表される
水素ガスの比率Ａが、７５％を超える水素ガスと窒素ガ
スの混合ガスとする。The atmosphere gas is a mixed gas of hydrogen gas and nitrogen gas in which the ratio A of hydrogen gas represented by the following formula (1) exceeds 75%.
【００３５】 Ａ＝１００・Ｈ２／（Ｈ２＋Ｎ２）・・・（１） 上記（１）式において、Ｈ２は雰囲気ガス中の水素ガス
の濃度（容量％）、Ｎ ２は雰囲気ガス中の窒素ガスの濃
度（容量％）を表す。A = 100 · H2/ (H2+ N2(1) In the above equation (1), H2Is hydrogen gas in the atmosphere gas
Concentration (% by volume), N 2Is the concentration of nitrogen gas in the atmosphere gas
Degree (% by volume).
【００３６】水素ガスのような還元性ガスの雰囲気中で
焼きなまし処理を行うと、表面に酸化物が生成されるの
が抑制され、薄い酸化皮膜が形成される。水素ガスの比
率Ａが低下するにつれて酸化皮膜は厚くなり、水素ガス
の比率Ａが７５％以下になると、エッチング処理の前処
理のような軽度の酸洗では除去しきれないような厚い酸
化皮膜となる。したがって本発明では、上記（１）式で
表される水素ガスの比率Ａを７５％超と規定した。なお
前記の混合ガスとしては、アンモニア分解ガスのみでは
不十分でであるので、上記（１）式を満足するように水
素ガスを加えるか、または水素ガスと窒素ガスとを流量
比率を調整して用いればよい。このときにはできるだけ
純度の高いガスを用いるのがよい。When annealing is performed in an atmosphere of a reducing gas such as hydrogen gas, the formation of oxides on the surface is suppressed, and a thin oxide film is formed. As the ratio A of hydrogen gas decreases, the oxide film becomes thicker. When the ratio A of hydrogen gas becomes 75% or less, a thick oxide film which cannot be completely removed by light pickling such as pretreatment of an etching process. Become. Therefore, in the present invention, the ratio A of the hydrogen gas represented by the above formula (1) is specified to be more than 75%. As the above mixed gas, ammonia decomposition gas alone is not sufficient, so that hydrogen gas is added or the flow ratio of hydrogen gas and nitrogen gas is adjusted so as to satisfy the above equation (1). It may be used. At this time, it is preferable to use a gas having a purity as high as possible.
【００３７】温度は、鋼種および必要とする機械的性質
によって決定すれば良い。保持時間は、１０〜２００秒
程度とすれば十分である。このような条件による光輝焼
きなましは、最終の冷間圧延後に行い、連続炉で行うこ
とができる。The temperature may be determined according to the type of steel and the required mechanical properties. A holding time of about 10 to 200 seconds is sufficient. Bright annealing under such conditions is performed after the final cold rolling, and can be performed in a continuous furnace.
【００３８】（２）酸洗 酸洗に用いる液は、塩酸、硫酸、硝酸および弗酸の１種
または２種以上を合計で１〜１０重量％含む水溶液とす
る。(2) Pickling The solution used for pickling is an aqueous solution containing 1 to 10% by weight in total of one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid.
【００３９】前記の条件による光輝焼きなましが施され
たステンレス鋼板は、本質的に酸化皮膜が薄いので、軽
度の酸洗によって酸化皮膜を除去することができる。こ
こでいう軽度の酸洗とは、ステンレス鋼板の表面の光沢
を損わない程度の酸洗をさし、塩酸、硫酸、硝酸および
弗酸の単体またはこれらの２種類以上を混合したもの
を、１〜１０重量％含む水溶液である。前記の酸が１重
量％未満では、酸化被膜の除去に時間がかかり、１０重
量％を超えると、ステンレス鋼板の表面の光沢が消失す
る。なお、水溶液の温度は、室温〜５０℃程度の範囲と
し、酸洗時間は３０秒以上で光沢を損なわない程度の時
間とすればよい。Since the stainless steel sheet subjected to bright annealing under the above-described conditions has an essentially thin oxide film, the oxide film can be removed by light pickling. Mild pickling, as used herein, refers to pickling that does not impair the gloss of the surface of the stainless steel sheet, and uses hydrochloric acid, sulfuric acid, nitric acid, and a mixture of two or more of these acids, It is an aqueous solution containing 1 to 10% by weight. When the acid is less than 1% by weight, it takes time to remove the oxide film, and when it exceeds 10% by weight, the surface gloss of the stainless steel plate is lost. The temperature of the aqueous solution may be in the range of room temperature to about 50 ° C., and the pickling time may be 30 seconds or longer, so long as the gloss is not impaired.
【００４０】この酸洗は、ステンレス鋼板に光輝焼きな
ましを施した直後、または光輝焼きなまし後調質圧延を
行った後に、ステンレス鋼板を前記の水溶液中に浸漬す
る方法、またはステンレス鋼板の表面に前記の水溶液を
スプレーノズルから噴霧する方法により行う。The pickling may be performed by immersing the stainless steel sheet in the aqueous solution immediately after bright annealing of the stainless steel sheet, or after temper rolling after bright annealing, or by applying the above-described method to the surface of the stainless steel sheet. The method is performed by spraying an aqueous solution from a spray nozzle.
【００４１】また、ステンレス鋼板がフォトエッチング
用の場合は、フォトエッチング処理の前に、アルカリ脱
脂、酸洗、水洗および乾燥の前処理が行われるので、ア
ルカリ脱脂の後の酸洗と兼ねて行ってもよい。When the stainless steel plate is used for photoetching, pretreatments such as alkali degreasing, pickling, water washing and drying are performed before the photoetching treatment, so that the stainless steel plate is also used for pickling after alkali degreasing. You may.
【００４２】本発明の方法により製造されるステンレス
鋼板は、表面を粗面化したり特別な化成処理を施すこと
なく、良好な表面のヌレ性を得ることができる。そのた
め、フォトエッチング加工用に用いれば、フォトレジス
トとの密着性に優れ、また、フォトエッチング加工の最
終工程で容易にフォトレジストを除去することができ
る。そのため、除去後にフォトレジストの残滓が付着す
ることのない表面が良好な製品を得ることができる。The stainless steel sheet produced by the method of the present invention can obtain a good surface wetting property without roughening the surface or performing a special chemical conversion treatment. Therefore, when used for photo-etching, the adhesiveness with the photoresist is excellent, and the photoresist can be easily removed in the final step of the photo-etching. Therefore, it is possible to obtain a product having a good surface on which no photoresist residue adheres after removal.
【００４３】なお、本発明法により製造されるステンレ
ス鋼板は、本質的に表面ヌレ性が優れるためフォトレジ
ストに対してだけではなく、塗装あるいはメッキ、ハン
ダを施すような用途に対しても十分な密着性を発揮する
ことができる。The stainless steel sheet produced by the method of the present invention is essentially excellent in surface wetting properties, and is therefore not only sufficient for photoresists but also for applications such as painting, plating and soldering. Adhesion can be exhibited.
【００４４】[0044]
【実施例】＜実施例１＞冷間圧延された板厚０．２ｍｍ
のＳＵＳ４３０のステンレス鋼板を、露点および水素ガ
スの比率Ａ（１００・Ｈ２／（Ｈ２＋Ｎ２））を変化さ
せた連続加熱炉の中で、昇温時間３０秒、温度８３０
℃、保持時間１０秒、２００℃まで３０秒で冷却した後
大気中で放冷、の条件で光輝焼きなましを行った。この
ステンレス鋼板を、７０℃の１０％苛性ソーダ溶液中に
２分間浸漬するアルカリ脱脂を行った後、室温の８％塩
酸の水溶液に０〜５分間浸漬する酸洗を行い、その後、
水洗および乾燥を行った。このステンレス鋼板の表面の
ヌレ性を評価するために、光輝焼きなましのままおよび
酸洗後の接触角を測定した。<Example 1> Cold rolled sheet thickness 0.2 mm
SUS430 stainless steel plate in a continuous heating furnace in which the dew point and the ratio of hydrogen gas A (100 · H 2 / (H 2 + N 2 )) were changed, the temperature rising time was 30 seconds, and the temperature was 830.
Bright annealing was performed under the conditions of cooling at a temperature of 10 ° C., a holding time of 10 seconds, and cooling to 200 ° C. for 30 seconds and then cooling in the air. This stainless steel plate is subjected to alkaline degreasing by dipping in a 10% caustic soda solution at 70 ° C. for 2 minutes, and then is pickled by dipping in an aqueous solution of 8% hydrochloric acid at room temperature for 0 to 5 minutes.
Washing and drying were performed. In order to evaluate the wettability of the surface of this stainless steel sheet, the contact angles were measured with bright annealing and after pickling.
【００４５】なお、接触角は、ステンレス鋼板の表面に
純水を滴下し、このときのステンレス鋼板の表面と液滴
の接線がなす角度を測定したものである。この接触角が
小さいほど表面ヌレ性が良好であり、接触角がおおむね
３０度以下であれば表面ヌレ性が極めて良好であると評
価される。The contact angle is obtained by measuring the angle between the surface of the stainless steel plate and the tangent of the droplet at the time when pure water is dropped on the surface of the stainless steel plate. The smaller the contact angle is, the better the surface wetting property is. If the contact angle is about 30 degrees or less, it is evaluated that the surface wetting property is extremely good.
【００４６】図１は、水素ガスの比率を７７％の一定と
して、露点を−２０〜−４９℃まで変えて光輝焼きなま
しを行ったときの、光輝焼きなましのままの場合と１分
間の酸洗後の場合の、露点と接触角との関係を示す図で
ある。同図から次のことがわかる。 光輝焼きなましのままの場合、および１分間の酸洗後
の場合のいずれも、露点が低くなるに従い接触角が小さ
くなる。 光輝焼きなましのままの場合に比べて、１分間の酸洗
後の場合の方が接触角の低下の程度が大きい。 １分間の酸洗後の場合では、露点が−４０℃より低い
と接触角がほぼ３０度以下になる。FIG. 1 shows a case where bright annealing is performed while the dew point is changed to -20 to -49 ° C. while the ratio of hydrogen gas is kept constant at 77%. FIG. 4 is a diagram illustrating a relationship between a dew point and a contact angle in the case of FIG. The following can be seen from FIG. In both cases of bright annealing and after one minute of pickling, the contact angle decreases as the dew point decreases. The degree of decrease in the contact angle is larger after pickling for one minute than in the case of bright annealing. After one minute of pickling, if the dew point is lower than −40 ° C., the contact angle becomes approximately 30 degrees or less.
【００４７】図２は、露点を−４３℃の一定として、水
素ガスの比率を０〜１００％まで変えて光輝焼きなまし
を行ったときの、光輝焼きなましのままの場合と１分間
の酸洗後の場合の、水素ガスの比率と接触角との関係を
示す図である。同図から次のことがわかる。 光輝焼きなましのままの場合、および１分間の酸洗後
の場合のいずれも、水素ガスの比率が高くなるに従い接
触角が小さくなる。 光輝焼きなましのままの状態に比べて、１分間の酸洗
後の場合の方が接触角の低下の程度が大きい。 １分間の酸洗後の場合では、水素ガスの比率が７５％
を超えると、接触角がほぼ３０度以下になる。FIG. 2 shows bright anneal performed when the dew point is kept constant at -43 ° C. and the hydrogen gas ratio is changed from 0 to 100%. FIG. 6 is a diagram showing a relationship between a ratio of hydrogen gas and a contact angle in the case. The following can be seen from FIG. In both cases of bright annealing and after 1 minute of pickling, the contact angle decreases as the ratio of hydrogen gas increases. The degree of reduction in the contact angle is greater after pickling for one minute than in the state of bright annealing. After one minute of pickling, the ratio of hydrogen gas is 75%
Is larger than the above, the contact angle becomes approximately 30 degrees or less.
【００４８】図３は、水素ガスの比率７７％とし、露点
を−２０℃および−４３℃として光輝焼きなましを行っ
た後、酸洗時間を変化させて酸洗したときの、酸洗時間
と接触角との関係を示す図である。同図から次のことが
わかる。 露点が−２０℃の場合、および−４３℃の場合のいず
れも、酸洗時間が長くなると接触角は小さくなる。 露点が−４３℃の場合は、露点が−２０℃の場合に比
べて、短い酸洗時間の範囲で接触角が低下する。 露点が−４３℃の場合は、１分の酸洗時間で接触角が
ほぼ３０度以下になるが、露点が−２０℃の場合は、接
触角が３０度を下回るまでに少なくとも３分の酸洗時間
を必要とする。FIG. 3 shows the contact between the pickling time and the pickling time when bright annealing was performed with the hydrogen gas ratio being 77% and the dew points at -20 ° C. and −43 ° C., and then the pickling time was changed. It is a figure showing the relation with a corner. The following can be seen from FIG. In both the case where the dew point is −20 ° C. and the case where the dew point is −43 ° C., as the pickling time becomes longer, the contact angle becomes smaller. When the dew point is −43 ° C., the contact angle is reduced in a shorter pickling time range than when the dew point is −20 ° C. When the dew point is -43 ° C, the contact angle becomes approximately 30 degrees or less in one minute of pickling time, but when the dew point is -20 ° C, the contact angle becomes at least 3 minutes before the contact angle falls below 30 degrees. Requires washing time.
【００４９】＜実施例２＞冷間圧延された板厚０．２ｍ
ｍのＳＵＳ４３０のステンレス鋼板、および板厚０．１
ｍｍのＳＵＳ３０４のステンレス鋼板に、条件を種々変
えて光輝焼きなましを施し、その後、７０℃の１０％苛
性ソーダ溶液中に１分間浸漬するアルカリ脱脂を行った
後、２５℃の水溶液に１分間浸漬する酸洗を行った。そ
の後、水洗および乾燥を行った後、接触角を調査した。
光輝焼きなましの条件、酸洗の条件および接触角を表１
に示す。なお、接触角は、実施例１に示す方法と同様の
方法により求めた。<Example 2> Cold rolled sheet thickness 0.2 m
SUS430 stainless steel plate with a thickness of 0.1 m
mm SUS304 stainless steel plate is subjected to bright annealing under various conditions, then alkali degreased by immersion in 70% 10% caustic soda solution for 1 minute, and then acid immersed in 25 ° C aqueous solution for 1 minute Washing was performed. Then, after washing and drying, the contact angle was examined.
Table 1 shows the conditions of bright annealing, pickling conditions and contact angles.
Shown in Note that the contact angle was determined by the same method as the method shown in Example 1.
【００５０】[0050]
【表１】 次に、このステンレス鋼板の両面に、アクリル樹脂系フ
ォトレジストを厚さ１０μｍで塗布し、幅０．１ｍｍ、
長さ５ｍｍのスリット状のパターンを形成した。その
後、比重１．４８ｇ／ｃｍ３ 、温度６０℃の塩化第二
鉄溶液を両面に噴霧してスプレーエッチング加工を行
い、エッチング加工性およびレジスト除去後の外観を調
査した。結果を表１に併せて示す。[Table 1] Next, on both sides of this stainless steel plate, an acrylic resin-based photoresist was applied in a thickness of 10 μm, and a width of 0.1 mm was applied.
A slit-shaped pattern having a length of 5 mm was formed. Thereafter, a ferric chloride solution having a specific gravity of 1.48 g / cm 3 and a temperature of 60 ° C. was sprayed on both surfaces to perform spray etching, and the etching processability and the appearance after removing the resist were examined. The results are shown in Table 1.
【００５１】エッチング加工性は、フォトレジストの剥
離がなく、良好な形状に加工できたものを○、ステンレ
ス鋼板とフォトレジストとの界面に、エッチング液が浸
透しエッチング端面の直線性が悪いものを△、エッチン
グ加工の途中にフォトレジストが剥離したものを×とし
た。The etching processability was evaluated as follows: those which were processed into a good shape without peeling of the photoresist were evaluated as good, and those whose etching solution permeated the interface between the stainless steel plate and the photoresist and had poor linearity of the etched end face were evaluated. Δ, the one in which the photoresist was peeled off during the etching process was evaluated as ×.
【００５２】また、レジスト除去後の外観は、フォトレ
ジストを除去した後の表面に着色が認められなかったも
のをＡ、光輝焼きなましの際のテンパーカラーによる着
色が認められものをＢ、表面の光沢が消失したものをＣ
とした。The appearance after the removal of the resist was A when no color was observed on the surface from which the photoresist was removed, B when color was observed by the temper color during bright annealing, and B when the surface was glossy. C that disappeared
And
【００５３】同表から次のことがわかる。光輝焼きなま
しの条件および酸洗の条件が、本発明で規定する条件を
満足するＮｏ．１〜Ｎｏ．１４の本発明例は、いずれも
酸洗後の接触角が３０度以下の良好な表面ヌレ性を示
し、エッチング加工性およびレジスト除去後の外観も良
好であった。The following can be seen from the table. The bright annealing condition and the pickling condition satisfy the conditions specified in the present invention. 1 to No. All of the 14 examples of the present invention exhibited good surface wetting properties with a contact angle of 30 ° or less after pickling, and also had good etching workability and appearance after removing the resist.
【００５４】これに対して、光輝焼きなましにおける露
点とＨ２ガスの比率のいずれか一方または両方が本発明
で規定する条件を外れるＮｏ．１５〜Ｎｏ．２４の比較
例は、いずれも接触角が３０度を超えて表面ヌレ性に劣
り、またエッチング加工性も悪かった。特に露点が−２
０℃のＮｏ．１５とＮｏ．２４、およびＨ２ガスの比率
が０％（窒素ガス１００％）のＮｏ．１８の比較例は、
エッチング加工性が特に悪く、また、レジスト除去後の
外観では、光輝焼きなましの際のテンパーカラーによる
着色が認められた。On the other hand, one or both of the ratio of the dew point and the H 2 gas in the bright annealing deviated from the conditions specified in the present invention. 15-No. In all of the comparative examples 24, the contact angle exceeded 30 degrees, the surface wetting property was poor, and the etching workability was poor. Especially the dew point is -2
No. of 0 ° C. 15 and no. No. 24 and No. 2 in which the ratio of H 2 gas was 0% (nitrogen gas 100%). Comparative Example 18
The etching processability was particularly poor, and in the appearance after removal of the resist, coloring by a temper color during bright annealing was recognized.
【００５５】酸洗における酸の濃度が本発明に規定する
条件を超えるＮｏ．２５〜Ｎｏ．２８の比較例では、接
触角が３０度以下でエッチング加工性も良好であった
が、レジスト除去後の外観は、酸洗時に表面皮膜が過剰
に溶解したため表面の光沢が消失した。In the case of No. 3 in which the concentration of the acid in the pickling exceeds the condition specified in the present invention. 25-No. In Comparative Example No. 28, although the contact angle was 30 ° or less and the etching processability was good, the appearance after removing the resist lost the gloss of the surface because the surface film was excessively dissolved at the time of pickling.
【００５６】[0056]
【発明の効果】この発明の方法によれば、ヌレ性に優れ
たステンレス鋼板を表面の光沢を損なうことなく製造す
ることができる。また、フォトエッチング加工用のステ
ンレス鋼板に採用すれば、エッチング加工性および表面
の光沢に優れたステンレス鋼板を、工程を増やすことな
く製造することができる。According to the method of the present invention, a stainless steel sheet having excellent wettability can be manufactured without impairing the surface gloss. In addition, if the stainless steel plate is used for a photo-etching process, a stainless steel plate having excellent etching processability and surface gloss can be manufactured without increasing the number of steps.
【図１】板厚０．２ｍｍのＳＵＳ４３０のステンレス鋼
板を、水素ガスの比率を７７％の一定として、露点を−
２０〜−４９℃まで変えて光輝焼きなましを行ったとき
の、光輝焼きなましのままの場合と１分間の酸洗後の場
合の、露点と接触角との関係を示す図である。FIG. 1 shows a stainless steel sheet of SUS430 having a thickness of 0.2 mm with a hydrogen gas ratio of 77% and a dew point of −
It is a figure which shows the relationship between a dew point and a contact angle in the case of bright annealing as it is, when performing bright annealing by changing from 20 to -49 degreeC, and in the case of pickling for 1 minute.
【図２】板厚０．２ｍｍのＳＵＳ４３０のステンレス鋼
板を、露点を−４３℃の一定として、水素ガスの比率を
０〜１００％まで変えて光輝焼きなましを行ったとき
の、光輝焼きなましのままの場合と１分間の酸洗後の場
合の、水素ガスの比率と接触角との関係を示す図であ
る。FIG. 2 shows a bright anneal of a SUS430 stainless steel plate having a thickness of 0.2 mm when the bright annealing is performed while the dew point is kept constant at −43 ° C. and the hydrogen gas ratio is changed from 0 to 100%. It is a figure which shows the relationship between the ratio of a hydrogen gas, and the contact angle in the case and the case after 1 minute pickling.
【図３】板厚０．２ｍｍのＳＵＳ４３０のステンレス鋼
板を、水素ガスの比率７７％とし、露点を−２０℃およ
び−４３℃として光輝焼きなましを行った後、酸洗時間
を変化させて酸洗したときの、酸洗時間と接触角との関
係を示す図である。[FIG. 3] A SUS430 stainless steel plate having a thickness of 0.2 mm is subjected to bright annealing at a hydrogen gas ratio of 77% with dew points of −20 ° C. and −43 ° C., and then pickling by changing the pickling time. FIG. 4 is a diagram showing a relationship between the pickling time and the contact angle when the cleaning is performed.
Claims (2)
−４０℃より低く、かつ下記（１）式で表される水素ガ
スの比率Ａが７５％を超える水素ガスと窒素ガスとの混
合ガスの雰囲気中で光輝焼なましを施し、その後、塩
酸、硫酸、硝酸および弗酸の１種または２種以上を合計
で１〜１０重量％含む水溶液で酸洗することを特徴とす
るステンレス鋼板の製造方法。 Ａ＝１００・Ｈ２／（Ｈ２＋Ｎ２）・・・（１） ここでＨ２ ：雰囲気ガス中の水素ガスの濃度（容量
％） Ｎ２ ：雰囲気ガス中の窒素ガスの濃度（容量％）1. A mixture of hydrogen gas and nitrogen gas having a dew point lower than -40 ° C. and a ratio A of hydrogen gas represented by the following formula (1) exceeding 75% is added to a cold-rolled stainless steel plate. A stainless steel sheet characterized by being subjected to bright annealing in a gas atmosphere, and then pickling with an aqueous solution containing 1 to 10% by weight in total of one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid. Manufacturing method. A = 100 · H 2 / (H 2 + N 2 ) (1) where H 2 : concentration of hydrogen gas in the atmosphere gas (volume%) N 2 : concentration of nitrogen gas in the atmosphere gas (volume%) )
−４０℃より低く、かつ下記（１）式で表される水素ガ
スの比率Ａが７５％を超える水素ガスと窒素ガスとの混
合ガスの雰囲気中で光輝焼なましを施し、その後、フォ
トエッチング処理の前処理工程における酸洗時に、塩
酸、硫酸、硝酸および弗酸の１種または２種類以上を合
計で１〜１０重量％含む水溶液で酸洗することを特徴と
するフォトエッチング加工用ステンレス鋼板の製造方
法。 Ａ＝１００・Ｈ２／（Ｈ２＋Ｎ２）・・・（１） ここでＨ２ ：雰囲気ガス中の水素ガスの濃度（容量
％） Ｎ２ ：雰囲気ガス中の窒素ガスの濃度（容量％）2. A mixture of hydrogen gas and nitrogen gas having a dew point lower than -40.degree. C. and a ratio A of hydrogen gas represented by the following formula (1) exceeding 75% in a cold-rolled stainless steel sheet. Bright annealing is performed in a gas atmosphere, and then one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid are contained in a total amount of 1 to 10% by weight at the time of pickling in a pretreatment step of a photoetching treatment. A method for producing a stainless steel plate for photoetching, comprising pickling with an aqueous solution. A = 100 · H 2 / (H 2 + N 2 ) (1) where H 2 : concentration of hydrogen gas in the atmosphere gas (volume%) N 2 : concentration of nitrogen gas in the atmosphere gas (volume%) )
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|---|---|---|---|
| JP2001071820A JP3861612B2 (en) | 2001-03-14 | 2001-03-14 | Stainless steel sheet manufacturing method |
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|---|---|---|---|
| JP2001071820A JP3861612B2 (en) | 2001-03-14 | 2001-03-14 | Stainless steel sheet manufacturing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432296C (en) * | 2003-08-15 | 2008-11-12 | 东南大学 | Solution for removing oxide layer on surface of annealed stainless steel |
| KR20150024945A (en) | 2012-09-04 | 2015-03-09 | 신닛테츠스미킨 카부시키카이샤 | Stainless steel sheet and method for producing same |
| JP2021154335A (en) * | 2020-03-26 | 2021-10-07 | 日本製鉄株式会社 | Clad |
-
2001
- 2001-03-14 JP JP2001071820A patent/JP3861612B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432296C (en) * | 2003-08-15 | 2008-11-12 | 东南大学 | Solution for removing oxide layer on surface of annealed stainless steel |
| KR20150024945A (en) | 2012-09-04 | 2015-03-09 | 신닛테츠스미킨 카부시키카이샤 | Stainless steel sheet and method for producing same |
| JP2021154335A (en) * | 2020-03-26 | 2021-10-07 | 日本製鉄株式会社 | Clad |
| JP7440756B2 (en) | 2020-03-26 | 2024-02-29 | 日本製鉄株式会社 | cladding |
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