JP2004307951A - Roughened steel sheet - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、有機高分子樹脂被覆との密着性を高めた普通鋼または特殊鋼の粗面化鋼板であって、特に鋼板表面を選択的にエッチングして得られる粗面化鋼板に関する。
【０００２】
【従来の技術】
一般に鋼板素材の表面には、防錆や塗膜密着性の観点からめっきを施すことが多いが、用途によってはめっき層を介さずに直接鋼板素地の上に塗料や接着剤を塗布する必要が生じることがある。
【０００３】
近年では接着剤の性能向上もあり、各種構造物を製作する際に、接着剤により鋼板同士あるいは鋼板と異種材料を接合する工法が多用されるようになってきた。このような接着工法には、溶接歪みがない，シール性が向上する，軽量化が図れる，作業性が向上するなどの利点があり、例えば、工業用計算機や各種制御盤等の重要機器を収容する筐体，鉄道車両用ドア，屋根・エクステリア等の建材，エレベーター用壁パネル，ダクト，システムキッチンなど、広範な用途に利用されている。また、３次元データをもとに鋼板を所定形状に打ち抜き、積層、接着して「積層部品」や「積層金型」が製作されている。
【０００４】
鋼板と異種材料を接着する用途として、例えば自動車のオートマチック・トランスミッションの構成部品であるフリクションプレートが挙げられる。これはコア材（鋼板）の表面に摩擦材（例えば、繊維基材に充填材や樹脂結合材などを含浸させて加熱硬化させた複合体）を貼り付けたものであり、トランスミッション内の湿式クラッチ板を構成するものである。また、免震構造の建築物を支える積層ゴムアイソレーターが挙げられる。これは、天然ゴムと鋼板を積層、接着したものであり、建築物と地面の間に介在して免震機構を担う。
【０００５】
鋼板素地は一般に有機高分子樹脂等の塗膜や接着剤との密着性があまり良好ではない。このため、鋼板素地に直接塗料や接着剤を塗布した場合、曲げ加工や絞り加工で塗膜が剥離したり、接着剤を介して接合された材料が外部応力によって剥離したりする問題が生じやすい。そこで、前処理として、鋼板表面の粗面化が行われることがある。その代表的手段として、ブラスト処理およびダルロール圧延が挙げられる。
【０００６】
ブラスト処理は、シュートやグリッドなどの研磨粒子を高圧の空気で送り出して粗面化すべき鋼板の表面に衝突させ、その衝突によって鋼板表面を削り取って凹凸形状にする粗面化手段である。しかし、削り取られた鋼粉の処理により連続生産性が低下し、また特に薄ゲージ鋼板の場合は板が反り返る等の形状不良が生じやすい。さらに研磨粒子の種類や空気圧等の条件によって表面粗さが変動しやすいという欠点もある。
【０００７】
ダルロール圧延は、圧延ロール表面に形成した凹凸形状を鋼板表面に転写する粗面化手段であり、表面粗さの制御はある程度可能である。しかし、有機高分子樹脂皮膜との密着性を大幅に向上させるような粗面化は困難である。
【０００８】
一方、ステンレス鋼を対象とした粗面化技術として、電解粗面化方法が開発されている。例えば、下記特許文献１には、硝酸または硝酸を主成分とする水溶液中でステンレス鋼の陽極電解または陽極電解＋陰極電解を行う粗面化方法が開示されている。また特許文献２には、塩化第二鉄水溶液中でステンレス鋼板を交番電解することによりアンカー効果の高い特異な形状のピットを高密度に形成する方法が開示されている。これらはいずれも、ステンレス鋼が不動態皮膜を形成し易いという性質を利用したものである。すなわち、ステンレス鋼は本来、腐食形態が孔食状になりやすいため、この性質を巧みに利用すればアンカー効果の高い粗面化表面が比較的容易に作れる。
【０００９】
これに対し、ステンレス鋼ではない普通鋼や特殊鋼を電解やエッチングによって粗面化することは必ずしも容易でない。これらの鋼種はＣｒ含有量が低く、孔食よりも全面溶解の傾向が強いため、本来的にピットを高密度に形成させることが難しい。このため、電解やエッチングで工業的にアンカー効果の高い粗面化鋼板を製造するには多大なコストを要する。
【００１０】
【特許文献１】特開平６−１３６６００号公報
【特許文献２】特開平１０−２５９４９９号公報
【００１１】
【発明が解決しようとする課題】
本発明は、ステンレス鋼ではない普通鋼や特殊鋼の鋼板においても、接着剤や塗料との密着性に優れた粗面化鋼板であって、一般的な鋼板製造設備を利用して低コストで生産性よく製造できる粗面化鋼板を提供することを目的とする。
【００１２】
【課題を解決するための手段】
発明者らは種々研究を重ねた結果、塩酸などの電解質水溶液中においてＦｅよりも電位的に「貴」になるＮｉによって鋼板表面の大部分をマスキングすると、電解質水溶液中で鋼板素地の露出部を選択的にエッチングすることが可能になり、ステンレス鋼ではない普通鋼や特殊鋼の表面にも樹脂被覆との密着性に優れた複雑形状の粗面化表面が形成できることを見出した。そのようなＮｉによるマスキングは、ピンホール状のめっき欠陥が多数散在するような薄いＮｉめっき、すなわち「不完全なＮｉめっき」を施すことによって実現できる。エッチングは塩酸浸漬が好適に利用できる。また、予めダルロール圧延により粗面化した鋼板を素材に用いると一層効果的である。本発明はこれらの知見に基づいて完成したものである。
【００１３】
すなわち、上記目的は、鋼板表面にＮｉめっき被覆部と鋼素地露出部が混在しており、電解質水溶液中で前記鋼素地露出部が優先的にエッチングされた表面凹凸を有する、圧延方向の中心線平均粗さＲａが０．３〜２．０μｍの粗面化鋼板によって達成される。ダルロール圧延材を素材に用いた粗面化鋼板としては、ダルロール圧延による表面凹凸と、前記鋼素地露出部が電解質水溶液中で優先的にエッチングされた表面凹凸を併せ持つものが提供される。
特に、上記鋼素地露出部が、鋼板の圧延方向と板厚方向を含む断面において、圧延方向１ｍｍ当たり平均１５〜１００箇所の割合で存在するものが提供される。
「電解質水溶液」は電解質が溶けた水溶液である。
【００１４】
また、鋼板表面にピンホール状欠陥が散在するＮｉめっき層を形成した後、電解質水溶液中、例えば塩酸水溶液中で、鋼板素地を前記ピンホール状欠陥部において優先的に溶解させて表面凹凸を形成した、圧延方向の中心線平均粗さＲａが０．３〜２．０μｍの粗面化鋼板が提供される。そのＮｉめっきを施す鋼板にはダルロール圧延材を用いることができる。
ここでいう「ピンホール状欠陥」は、Ｎｉめっき層を厚さ方向に貫通する孔あるいは隙間であり、電解質水溶液中において鋼素地表面と水溶液との間でイオンの授受ができる部分を意味する。必ずしも表面から鋼素地露出部が観察されるような欠陥である必要はない。
【００１５】
以上の粗面化鋼板において、特に鋼板がＣｒ：３．５質量％以下，Ｎｉ：５．０質量％以下，およびＭｏ：１．０質量％以下の鋼種であるものが提供される。
【００１６】
また、Ｃｒ：３．５質量％以下，Ｎｉ：５．０質量％以下，Ｍｏ：１．０質量％以下の鋼種の鋼板に片面当たり０．０５〜１．０ｇ／ｍ２のＮｉめっきを施した後、この鋼板を塩酸濃度５０〜１５０ｇ／Ｌ（リットル），温度６０〜９５℃の塩酸水溶液に合計２５〜３００秒浸漬することによって得られる、圧延方向の中心線平均粗さＲａが０．３〜２．０μｍの粗面化鋼板が提供される。特に、そのＮｉめっきを施す鋼板にダルロール圧延材を用いたものが提供される。
【００１７】
さらに、これらの粗面化鋼板であって、特に、表面に有機高分子樹脂系接着剤を塗布して使用されるものが提供される。
【００１８】
【発明の実施の形態】
本発明は、基本的に電解質水溶液中で溶解し得る種々の鋼種に適用できるが、特にＣｒ含有量が３．５質量％以下（０％を含む），Ｎｉ含有量が５．０質量％以下（０％を含む），かつＭｏ含有量が１．０質量％以下（０％を含む）の鋼種、すなわち、普通鋼や一般的な特殊鋼に適用することが望ましい。これらはステンレス鋼のように強固な不動態皮膜を形成せず、全面溶解の傾向が強いため、粗面化を電解質水溶液中で行うことが本来困難な鋼種である。
【００１９】
具体的には、例えば以下のような鋼種に適用することができる。
ｉ） 質量％で、Ｃ：０．３２〜０．３８％，Ｓｉ：０．１５〜０．３５％，Ｍｎ：０．６０〜０．９０％，Ｐ：０．０３０％以下，Ｓ：０．０３５％以下，残部Ｆｅおよび不可避的不純物。
ｉｉ） 質量％で、Ｃ：０．５２〜０．５８％，Ｓｉ：０．１５〜０．３５％，Ｍｎ：０．６０〜０．９０％，Ｐ：０．０３０％以下，Ｓ：０．０３５％以下，残部Ｆｅおよび不可避的不純物。
ｉｉｉ） 質量％で、Ｃ：０．１７〜０．２０％，Ｓｉ：０．０４％以下，Ｍｎ：０．６０〜０．９０％，Ｐ：０．０３０％以下，Ｓ：０．０２５％以下，残部Ｆｅおよび不可避的不純物。
ｉｖ） 質量％で、Ｃ：０．１０〜０．１５％，Ｓｉ：０．０４％以下，Ｍｎ：０．３０〜０．５０％，Ｐ：０．０２５％以下，Ｓ：０．０２５％以下，残部Ｆｅおよび不可避的不純物。
【００２０】
図１（ａ）は、質量％で、Ｃ：０．１１％，Ｓｉ：０．０１％，Ｍｎ：０．３１％，Ｐ：０．０１８％，Ｓ：０．００８％を含有し残部がＦｅおよび不可避的不純物からなる鋼の冷延焼鈍鋼板（板厚１．０ｍｍ）に、約６％のダルロール圧延を施した後の表面について、圧延方向に測定した粗さ曲線（ＪＩＳ Ｂ ０６０１）の例である。
【００２１】
図１（ｂ）は、そのダルロール圧延材を用いて製造した本発明の粗面化鋼板について、圧延方向に測定した粗さ曲線の例である。この粗面化鋼板は以下の手順で得たものである。すなわち、上記ダルロール圧延材に、硫酸ニッケル２４０ｇ／Ｌ，塩化ニッケル５０ｇ／Ｌ，ホウ酸３５ｇ／Ｌを含むｐＨ＝４．１，６０℃の水溶液中で電流密度５Ａ／ｄｍ２にて電気Ｎｉめっきを施した。その際、通電時間を調整してＮｉめっき付着量を０．５ｇ／ｍ２とした。次いで、これを塩酸濃度１００ｇ／Ｌ，温度９０℃の塩酸水溶液に６０秒浸漬してエッチングして、粗面化した。
【００２２】
これらの図からわかるように、粗面化エッチングの前後で中心線平均粗さＲａの値そのものにはあまり大きな変化はないものの、エッチング後には、ピッチが細かい割に山と谷の高さ変化が大きい凹凸が形成されている。このような急峻かつ細かい凹凸からなる複雑形状の粗面化表面は、後述のように、樹脂被覆との密着性を顕著に向上させるのである。この例ではダルロール圧延材を素材に用いているので、ダルロール圧延による表面凹凸と、エッチングによる表面凹凸が重畳した粗面化形態を呈している。
【００２３】
本発明に係る粗面化表面は、大部分がＮｉめっきに覆われているが、細かい凹部を形成している箇所には鋼板素地の露出が認められる。すなわち、鋼板表面にはＮｉめっき被覆部と鋼素地露出部が混在している。その鋼素地露出部は周囲のＮｉめっき被覆部よりも優先的にエッチングされており、その結果、複雑形状の粗面化表面が形成されている。
【００２４】
種々検討の結果、このような粗面化表面においては、鋼板の圧延方向と板厚方向を含む断面において、圧延方向１ｍｍ当たり平均１５〜１００箇所の鋼素地露出部（凹部）が存在するとき、有機高分子樹脂系接着剤との密着性が特に優れたものとなることがわかった。図１（ｂ）の例では、圧延方向１ｍｍ当たり平均約３２箇所の鋼素地露出部が存在する。
【００２５】
本発明の粗面化鋼板は以下のような方法で製造することができる。
まず、鋼板表面にＮｉめっきを施す。その際、ピンホール状欠陥が多数散在するようなＮｉめっき層を形成することが重要である。後述するように、ピンホール状欠陥の部分はエッチングによって凹部となる。したがって、エッチング後に鋼素地露出部（凹部）が鋼板断面の圧延方向１ｍｍ当たり平均１５〜１００箇所の割合で生成するのに必要な数だけピンホール状欠陥が散在したＮｉめっき層を形成することが望ましい。ピンホール状欠陥の生成数をコントロールするには、鋼板表面が完全にＮｉめっき層で覆われるまでの段階でめっき時間を調整すればよい。その段階では、めっき付着量の増加とともにピンホール状欠陥の数が減少するので、めっき付着量によってピンホール状欠陥の生成数をコントロールすることも有効である。電気めっきの場合、鋼板片面当たり０．０５〜１．０ｇ／ｍ２のＮｉめっき付着量とすれば良好な結果が得られることが明らかになった。
【００２６】
Ｎｉめっきは、電気めっき法，無電解めっき法の何れでもよいが、生産性の観点から電気めっき法によるのが好ましい。電気めっき法ではＷａｔｔ浴，Ｗｏｏｄ浴など、公知の電解浴が使用できる。Ｗａｔｔ浴を用いた電気めっき条件の一例として、硫酸ニッケル２４０ｇ／Ｌ，塩化ニッケル５０ｇ／Ｌ，ホウ酸３５ｇ／Ｌを含み、ｐＨ＝３．８〜４．５，浴温４０〜６５℃の電解液中で電流密度２〜１０Ａ／ｄｍ２で実施する方法が挙げられる。
【００２７】
次に、鋼板を電解質水溶液中でエッチングする。このとき、Ｎｉめっき層のピンホール状欠陥部を通して鋼板素地を優先的に溶解させるのである。そのメカニズムは以下のように考えられる。すなわち、金属の化学溶解速度の序列は一般に電気化学列で示されている。電気化学列とは１気圧の水素で飽和した白金黒で作られた標準水素電極の電位を基準として、各金属をその標準電極電位の順に並べたものである。この標準電極電位が低いほど「卑」あるいはイオン化傾向が大きく、標準電極電位が高いほど「貴」あるいはイオン化傾向が小さい。つまり、標準電極電位により金属の基本的な腐食傾向がわかる。ここで、Ｆｅ、Ｎｉの金属対を考えると、標準電極電位は、
Ｆｅ２＋＋２ｅ−＝Ｆｅ ； −０．４４Ｖ
Ｎｉ２＋＋２ｅ−＝Ｎｉ ； −０．２５Ｖ
２Ｈ＋＋２ｅ−＝Ｈ２ ； ０．００Ｖ
である。塩酸，硝酸，硫酸等の水溶液中においても（不動態皮膜を形成するような特殊な状況を除き）この序列は変わらず、ＮｉよりＦｅの方が溶解（腐食）しやすい。これらの液中でＦｅとＮｉが接触しているとき、Ｎｉがカソード極となって水素発生反応が起こり、他方のＦｅがアノード極となって鉄の溶解反応が起こる。
【００２８】
鋼板表面をピンホール状欠陥の散在したＮｉめっき層で被覆し、これを電解質水溶液（例えば塩酸）中に浸漬すると、ピンホール欠陥部分において鋼板素地のＦｅが優先的に溶解して、孔食状の凹部が形成される。前述のようにＮｉめっき付着量を鋼板片面当たり０．０５〜１．０ｇ／ｍ２の範囲に調整してピンホール状欠陥の分散状態を適正化したとき、鋼板表面に孔食状の凹部を多数形成することができ、樹脂被覆に対して優れたアンカー効果を呈する複雑形状の粗面化表面が得られる。Ｎｉめっき付着量が０．０５ｇ／ｍ２未満では鋼素地露出部で全面溶解の傾向が大きくなり、アンカー効果の高い粗面化が難しい。逆に１．０ｇ／ｍ２を超えるとピンホール状欠陥の数が少なくなり、孔食状の凹部が多数形成された複雑形状の粗面化は達成し難い。
【００２９】
Ｆｅとの金属対を考えた場合、Ｎｉと同様にＦｅの溶解反応を生じさせる金属種は多くある。溶解環境にもよるが、例を挙げるとＡｕ，Ｐｔ，Ａｇ，Ｈｇ，Ｃｕ，Ｐｂ，Ｓｎ，Ｃｏ，Ｃｄなどである。ここで、現実的な前提条件として、ｉ） 工業的に安価に鋼板へのめっきが可能なこと、ｉｉ） めっき廃液が水質汚濁の原因にならないこと、を考慮すると、めっき金属としてはＣｕ，Ｎｉ，Ｓｎやこれらの合金に限定される。しかしながら、ＣｕやＳｎの単独めっき、あるいはＣｕ，Ｓｎ，Ｎｉのうち２種以上からなる合金めっきについて検討したが、樹脂被覆との密着性を顕著に改善する複雑形状の凹凸表面を実現することは難しいことがわかった。
【００３０】
エッチングの方法として、塩酸，硫酸，硝酸などの無機酸水溶液に浸漬する方法が採用できる。特に塩酸によるエッチングは鉄鋼メーカーの連続酸洗ラインが利用できるというメリットがある。例として、塩酸濃度５０〜１５０ｇ／Ｌ，温度６０〜９５℃の塩酸水溶液に２５〜３００秒浸漬する方法が好適である。この場合、浸漬回数は１回でもよいが、複数回に分けて浸漬してもよい。浸漬時間の合計が２５〜３００秒の範囲になるようにすればよい。
【００３１】
以上の処理により、圧延方向に測定した中心線平均粗さＲａ（ＪＩＳ Ｂ ０６０１）が０．３〜２．０μｍの粗面化鋼板を得る。Ｒａ値がこの範囲にあるとき、被覆層（特に有機高分子樹脂系接着剤）との密着性向上効果と製造コストのバランスが非常に良好である。また、圧延方向に測定した最大高さＲｙ（ＪＩＳ Ｂ ０６０１）が２．５〜１５．０μｍであることが望ましい。ただし、本発明の粗面化鋼板は、多数の細かい孔食状の凹部で構成される特異な凹凸形態を特徴とするものであり、単にＲａあるいはＲｙの値が上記の範囲にあるだけで被覆層に対する優れたアンカー効果が得られるわけではない。
【００３２】
本発明では、Ｎｉめっきを施す前の鋼板素材としてダルロール圧延材を使用すると一層効果がある。この場合、図１（ｂ）に示したように、ダルロール圧延による凹凸とエッチングによる凹凸の重畳した粗面化表面が得られ、樹脂被覆との密着性能は向上する。ダルロール圧延率は概ね１〜１０％程度が良く、ダルロール圧延後の表面粗さは圧延方向に測定した中心線平均粗さＲａが０．３〜２．０μｍ程度、最大高さＲｙが２．５〜１５．０μｍ程度に調整すれば良い。特に、Ｒａは０．５〜２．０μｍ、Ｒｙは３．０〜１５．０μｍに調整するのが一層好ましい。
【００３３】
【実施例】
素材鋼板として、質量％で、Ｃ：０．１８％，Ｓｉ：０．０１％，Ｍｎ：０．６３％，Ｐ：０．０１８％，Ｓ：０．００３％を含有し残部がＦｅおよび不可避的不純物からなる鋼の冷延焼鈍鋼帯（板厚０．９ｍｍ）を用いた。この鋼帯の一部には約５％のダルロール圧延を施した。めっき原板として、ダルロール圧延を施さない冷延焼鈍材、およびダルロール圧延材の２種類を用意した。それぞれめっき前の表面粗さは以下のとおりである。
〔冷延焼鈍材〕 Ｒａ：０．３μｍ，Ｒｙ：２．２μｍ
〔ダルロール圧延材〕 Ｒａ：０．６μｍ，Ｒｙ：３．８μｍ
【００３４】
これら２本の鋼帯を脱脂した後、片面電気Ｎｉめっきを施した。めっき浴として硫酸ニッケル２４０ｇ／Ｌ，塩化ニッケル５０ｇ／Ｌ，ホウ酸３５ｇ／Ｌを含み、ｐＨ＝４．１，液温６０℃のＷａｔｔ浴を用い、電流密度５Ａ／ｄｍ２として、通電時間を調整することによりＮｉめっき付着量が０．０３ｇ／ｍ２，０．０８ｇ／ｍ２，０．５ｇ／ｍ２，０．９ｇ／ｍ２，２．０ｇ／ｍ２の５水準のＮｉめっき鋼帯を作製した。これらの鋼帯からエッチング用鋼板を切り出し、塩酸濃度１００ｇ／Ｌ，温度９０℃の塩酸水溶液に６０秒浸漬することによりエッチングを行った。
表１に、各鋼板のＮｉめっき付着量，塩酸浸漬後の表面粗さＲａ，Ｒｙの値を示す。表面粗さはＮｉめっきを施した面について圧延方向に測定した値である。
【００３５】
【表１】
各鋼板Ａ〜Ｊについて複数のサンプルを切り出し、Ｎｉめっきを施してエッチングした面に有機高分子樹脂系接着剤（田岡化学工業（株）製「テクノダインＡＨ」）を平均厚さが１０μｍとなるようにほぼ均一に塗布し、以下の２通りの条件で焼付硬化処理を行った。
〔焼付条件１〕 ８０℃×６０分
〔焼付条件２〕 １００℃×６５分
ここで、温度は雰囲気（大気）の温度を意味する。
【００３７】
焼付硬化処理後の一部のサンプルは沸騰水中に１時間浸漬した。
各サンプルから曲げ試験片を切り出し、接着剤被覆面が外側になるように３．５Ｒ−９０°Ｖ曲げ試験を行い、「セロハンテープ剥離試験」を実施した。
セロハンテープ剥離試験は、ＪＩＳ Ｚ １５２２で定めるセロハン粘着テープを曲げ加工部の外周部に貼付した後、剥ぎ取って、接着剤皮膜の剥離状況を観察し、以下の基準で密着性を評価した。○以上が密着性「良好」と判断される。
〔密着性評価基準〕
◎：剥離は認められない
○：点状の剥離が認められる
△：線状に連なった剥離が認められる
×：全面剥離またはそれに近い著しい剥離が認められる
結果を表２に示す。
【００３８】
【表２】
表１，２から判るように、ダルロール圧延の有無にかかわらず、Ｎｉめっき付着量が０．０５〜１．０ｇ／ｍ２の本発明例のものは接着剤との良好な密着性が得られた。特にダルロール圧延材では、焼付条件２の場合、沸騰浸漬後においても非常に優れた密着性（◎評価）が維持されるものが得られた（鋼板Ｇ，Ｈ）。
【００４０】
これに対し、ダルロール圧延なしの場合、Ｎｉめっき付着量が０．０５ｇ／ｍ２未満の鋼板Ａおよび１．０ｇ／ｍ２を超える鋼板Ｅは、いずれも全てのサンプルで接着剤との良好な密着性が得られなかった。
また、ダルロール圧延材の場合、Ｎｉめっき付着量が０．０５ｇ／ｍ２未満の鋼板Ａは焼付条件１の沸騰浸漬後において良好な接着剤密着性が維持されなかった。Ｎｉめっき付着量が１．０ｇ／ｍ２を超える鋼板Ｊでは全てのサンプルで良好な接着剤密着性は得られなかった。
【００４１】
【発明の効果】
以上のように、本発明では電解粗面化が難しい普通鋼や特殊鋼において、意図的に形成したピンホール状欠陥の多いＮｉめっき層を巧みに利用することで、特異な凹凸形態を有するエッチング表面の形成を可能にした。この粗面化鋼板は特に有機高分子樹脂皮膜との密着性が従来のダルロール仕上材などに比べ顕著に向上した。しかも、その製造は、一般的な鋼板製造ラインを利用して比較的簡単に実施することができる。したがって、本発明は、鋼板表面への各種樹脂コーティングの適用性を高め、特に接着接合の用途においては接合力の向上をもたらすものである。
【図面の簡単な説明】
【図１】（ａ）はダルロール圧延後の鋼板表面を圧延方向に測定した粗さ曲線の例であり、（ｂ）は（ａ）の鋼板表面にＮｉめっきおよび塩酸浸漬処理を施して得た本発明に係る粗面化鋼板の表面を圧延方向に測定した粗さ曲線の例である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a roughened steel sheet of ordinary steel or special steel having improved adhesion to an organic polymer resin coating, and more particularly to a roughened steel sheet obtained by selectively etching the surface of a steel sheet.
[0002]
[Prior art]
Generally, the surface of a steel sheet material is often plated from the viewpoint of rust prevention and coating film adhesion, but depending on the application, it is necessary to apply a paint or adhesive directly on the steel sheet base without using a plating layer. May occur.
[0003]
In recent years, there has been an improvement in the performance of adhesives, and when manufacturing various structures, a method of joining steel sheets to each other or to a steel sheet and a dissimilar material using an adhesive has come to be used frequently. Such a bonding method has advantages such as no welding distortion, improved sealability, reduced weight, and improved workability. For example, it accommodates important equipment such as industrial computers and various control panels. It is used for a wide range of applications, such as housings that can be used, doors for railway vehicles, building materials such as roofs and exteriors, wall panels for elevators, ducts, and system kitchens. Further, “laminated parts” and “laminated dies” are manufactured by punching a steel sheet into a predetermined shape based on three-dimensional data, laminating and bonding.
[0004]
As an application for bonding a steel sheet and a dissimilar material, for example, there is a friction plate which is a component of an automatic transmission of an automobile. This is a friction material (for example, a composite obtained by impregnating a fibrous base material with a filler or a resin binder and heating and curing) on the surface of a core material (steel plate). It constitutes a plate. Another example is a laminated rubber isolator that supports buildings with seismic isolation structures. This is made by laminating and bonding natural rubber and steel plate, and acts as a seismic isolation mechanism between the building and the ground.
[0005]
Generally, a steel sheet base material has not very good adhesion to a coating film such as an organic polymer resin or an adhesive. For this reason, when a paint or an adhesive is applied directly to a steel sheet substrate, a problem that the coating film is peeled off by bending or drawing or that the material joined via the adhesive is peeled off by external stress is likely to occur. . Therefore, the surface of the steel sheet may be roughened as a pretreatment. Typical means include blasting and dull roll rolling.
[0006]
Blasting is a roughening means in which abrasive particles such as chutes and grids are sent out with high-pressure air to collide with the surface of a steel sheet to be roughened, and the collision causes the steel sheet surface to be shaved to form an uneven shape. However, the processing of the scraped steel powder reduces continuous productivity, and particularly in the case of a thin gauge steel sheet, a shape defect such as warping of the sheet is likely to occur. Another drawback is that the surface roughness tends to fluctuate depending on the type of abrasive particles, air pressure and other conditions.
[0007]
Dull roll rolling is a roughening means for transferring the unevenness formed on the surface of the rolling roll to the surface of the steel sheet, and the surface roughness can be controlled to some extent. However, it is difficult to roughen the surface to greatly improve the adhesion to the organic polymer resin film.
[0008]
On the other hand, as a surface roughening technique for stainless steel, an electrolytic surface roughening method has been developed. For example, Patent Document 1 listed below discloses a surface roughening method in which anodic electrolysis or anodic electrolysis + cathodic electrolysis of stainless steel is performed in nitric acid or an aqueous solution containing nitric acid as a main component. Patent Literature 2 discloses a method in which a stainless steel plate is alternately electrolyzed in an aqueous ferric chloride solution to form pits having a unique shape with a high anchor effect at a high density. These all utilize the property that stainless steel easily forms a passive film. That is, since the corrosion form of stainless steel is apt to be pitting in nature, a rough surface having a high anchor effect can be relatively easily formed by using this property skillfully.
[0009]
On the other hand, it is not always easy to roughen ordinary steel or special steel other than stainless steel by electrolysis or etching. Since these steel types have a low Cr content and are more likely to dissolve over the entire surface than pitting corrosion, it is inherently difficult to form pits with high density. For this reason, large costs are required to industrially produce a roughened steel sheet having a high anchor effect by electrolysis or etching.
[0010]
[Patent Document 1] JP-A-6-136600 [Patent Document 2] JP-A-10-259499
[Problems to be solved by the invention]
The present invention is a roughened steel sheet having excellent adhesiveness with adhesives and paints, even at a steel sheet of ordinary steel or special steel other than stainless steel. It is an object to provide a roughened steel sheet that can be manufactured with high productivity.
[0012]
[Means for Solving the Problems]
As a result of various studies, the inventors have found that in an aqueous electrolyte solution such as hydrochloric acid, most of the steel sheet surface is masked with Ni, which is more noble than Fe, so that the exposed portion of the steel sheet base is exposed in the aqueous electrolyte solution. It has been found that etching can be selectively performed, and a rough surface having a complicated shape with excellent adhesion to a resin coating can be formed on the surface of ordinary steel or special steel other than stainless steel. Such Ni masking can be realized by performing thin Ni plating in which a large number of pinhole-shaped plating defects are scattered, that is, “incomplete Ni plating”. Hydrochloric acid immersion can be suitably used for etching. Further, it is more effective to use a steel sheet which has been roughened in advance by dull roll rolling as a material. The present invention has been completed based on these findings.
[0013]
That is, the above-mentioned object is to provide a center line in the rolling direction in which a Ni-plated coating portion and a steel base exposed portion are mixed on the surface of a steel sheet, and the steel base exposed portion has surface irregularities preferentially etched in an aqueous electrolyte solution. This is achieved by a roughened steel sheet having an average roughness Ra of 0.3 to 2.0 μm. As a roughened steel sheet using a dull roll material as a raw material, a steel sheet having both surface irregularities by dull roll rolling and surface irregularities in which the exposed portion of the steel substrate is preferentially etched in an aqueous electrolyte solution is provided.
In particular, there is provided a steel base exposed portion having an average of 15 to 100 portions per 1 mm in the rolling direction in a cross section including the rolling direction and the thickness direction of the steel sheet.
“Electrolyte aqueous solution” is an aqueous solution in which an electrolyte is dissolved.
[0014]
Further, after forming a Ni plating layer in which pinhole-shaped defects are scattered on the surface of the steel sheet, the steel sheet substrate is preferentially dissolved in the aqueous solution of an electrolyte, for example, an aqueous hydrochloric acid solution at the pinhole-shaped defect to form surface irregularities. Thus, a roughened steel sheet having a center line average roughness Ra in the rolling direction of 0.3 to 2.0 μm is provided. A roll rolled material can be used for the steel plate to be Ni-plated.
The “pinhole-shaped defect” here is a hole or a gap penetrating the Ni plating layer in the thickness direction, and means a portion in the electrolyte aqueous solution where ions can be exchanged between the steel substrate surface and the aqueous solution. The defect does not necessarily have to be such that the exposed portion of the steel base is observed from the surface.
[0015]
Among the above roughened steel sheets, there is provided a steel sheet whose steel type is Cr: 3.5% by mass or less, Ni: 5.0% by mass or less, and Mo: 1.0% by mass or less.
[0016]
Further, a steel sheet of steel type of Cr: 3.5% by mass or less, Ni: 5.0% by mass or less, and Mo: 1.0% by mass or less is subjected to Ni plating of 0.05 to 1.0 g / m 2 per one surface. After this, the steel sheet is immersed in a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 50 to 150 g / L (liter) and a temperature of 60 to 95 ° C. for a total of 25 to 300 seconds. A 3-2.0 μm roughened steel sheet is provided. In particular, there is provided a steel sheet to be subjected to Ni plating using a roll rolled material.
[0017]
Further, there is provided a roughened steel sheet which is used by applying an organic polymer resin-based adhesive to the surface thereof.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention can be basically applied to various steel types that can be dissolved in an aqueous electrolyte solution. In particular, the Cr content is 3.5% by mass or less (including 0%), and the Ni content is 5.0% by mass or less. It is desirable to apply the present invention to a steel type having a Mo content of 1.0% by mass or less (including 0%), that is, ordinary steel or general special steel. Since these do not form a strong passive film like stainless steel and have a strong tendency to dissolve over the entire surface, they are inherently difficult to roughen in an aqueous electrolyte solution.
[0019]
Specifically, for example, it can be applied to the following steel types.
i) In mass%, C: 0.32 to 0.38%, Si: 0.15 to 0.35%, Mn: 0.60 to 0.90%, P: 0.030% or less, S: 0 0.035% or less, balance Fe and inevitable impurities.
ii) In mass%, C: 0.52 to 0.58%, Si: 0.15 to 0.35%, Mn: 0.60 to 0.90%, P: 0.030% or less, S: 0 0.035% or less, balance Fe and inevitable impurities.
iii) In mass%, C: 0.17 to 0.20%, Si: 0.04% or less, Mn: 0.60 to 0.90%, P: 0.030% or less, S: 0.025% Hereinafter, the balance is Fe and inevitable impurities.
iv) In mass%, C: 0.10 to 0.15%, Si: 0.04% or less, Mn: 0.30 to 0.50%, P: 0.025% or less, S: 0.025% Hereinafter, the balance is Fe and inevitable impurities.
[0020]
FIG. 1A shows, by mass%, C: 0.11%, Si: 0.01%, Mn: 0.31%, P: 0.018%, S: 0.008%, and the balance is The surface of a cold-rolled annealed steel sheet (sheet thickness: 1.0 mm) composed of Fe and unavoidable impurities was subjected to about 6% dull roll rolling, and the surface was measured for a roughness curve (JIS B 0601) measured in the rolling direction. It is an example.
[0021]
FIG. 1B is an example of a roughness curve measured in the rolling direction of the roughened steel sheet of the present invention manufactured using the rolled roll material. This roughened steel sheet was obtained by the following procedure. That is, the Ni rolled material is subjected to electric Ni plating at a current density of 5 A / dm 2 in an aqueous solution containing 240 g / L of nickel sulfate, 50 g / L of nickel chloride, and 35 g / L of boric acid at a pH of 4.1 and 60 ° C. Was given. At that time, the energization time was adjusted to make the Ni plating adhesion amount 0.5 g / m 2 . Next, this was immersed in a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 100 g / L and a temperature of 90 ° C. for 60 seconds to be etched and roughened.
[0022]
As can be seen from these figures, the value of the center line average roughness Ra itself does not change so much before and after the surface roughening etching, but after the etching, the height change of the peaks and valleys changes despite the fine pitch. Large irregularities are formed. Such a rough surface having a complicated shape composed of steep and fine irregularities significantly improves the adhesion to the resin coating as described later. In this example, since a roll-rolled material is used as a material, a roughened surface in which surface irregularities due to dull roll rolling and surface irregularities due to etching are superimposed is exhibited.
[0023]
Most of the roughened surface according to the present invention is covered with Ni plating, but at the places where fine recesses are formed, exposure of the steel sheet base is observed. That is, the Ni-plated coated portion and the exposed portion of the steel base are mixed on the surface of the steel plate. The exposed portion of the steel base is etched preferentially over the surrounding Ni plating coating portion, and as a result, a rough surface having a complicated shape is formed.
[0024]
As a result of various studies, in such a roughened surface, in a cross section including the rolling direction and the thickness direction of the steel sheet, when an average of 15 to 100 steel base exposed portions (recesses) exist per 1 mm in the rolling direction, It was found that the adhesiveness with the organic polymer resin-based adhesive was particularly excellent. In the example of FIG. 1B, there are an average of about 32 exposed portions of the steel base per 1 mm in the rolling direction.
[0025]
The roughened steel sheet of the present invention can be manufactured by the following method.
First, Ni plating is applied to the steel sheet surface. At that time, it is important to form a Ni plating layer in which many pinhole-shaped defects are scattered. As will be described later, the portion of the pinhole-like defect becomes a concave portion by etching. Therefore, it is possible to form a Ni plating layer in which pinhole-like defects are scattered by the number necessary to generate the exposed portions (concave portions) of the steel base after etching at an average rate of 15 to 100 locations per 1 mm in the rolling direction of the cross section of the steel sheet. desirable. In order to control the number of generated pinhole defects, the plating time may be adjusted until the steel sheet surface is completely covered with the Ni plating layer. At that stage, the number of pinhole-like defects decreases with an increase in the amount of plating, so it is also effective to control the number of pinhole-like defects generated by the amount of plating. In the case of electroplating, it was clear that good results could be obtained if the Ni plating adhesion amount was 0.05 to 1.0 g / m 2 per one surface of the steel sheet.
[0026]
Ni plating may be performed by either an electroplating method or an electroless plating method, but is preferably performed by an electroplating method from the viewpoint of productivity. In the electroplating method, a known electrolytic bath such as a Watt bath or a Wood bath can be used. As an example of electroplating conditions using a Watt bath, electrolysis containing 240 g / L of nickel sulfate, 50 g / L of nickel chloride, and 35 g / L of boric acid, and having a pH of 3.8 to 4.5 and a bath temperature of 40 to 65 ° C. A method in which the current density is 2 to 10 A / dm 2 in a liquid may be used.
[0027]
Next, the steel sheet is etched in an aqueous electrolyte solution. At this time, the steel sheet base is preferentially melted through the pinhole-shaped defect portion of the Ni plating layer. The mechanism is considered as follows. That is, the order of the chemical dissolution rate of the metal is generally represented by the electrochemical sequence. The electrochemical column is obtained by arranging each metal in the order of the standard electrode potential with reference to the potential of a standard hydrogen electrode made of platinum black saturated with 1 atm of hydrogen. The lower the standard electrode potential, the more “base” or ionization tendency, and the higher the standard electrode potential, the “noble” or ionization tendency. That is, the basic corrosion tendency of the metal can be understood from the standard electrode potential. Here, considering the metal pair of Fe and Ni, the standard electrode potential is
Fe 2+ + 2e − = Fe; −0.44 V
Ni 2+ + 2e − = Ni; −0.25V
2H + + 2e - = H 2 ; 0.00V
It is. This order does not change even in an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid or the like (except for a special situation where a passive film is formed), and Fe is more easily dissolved (corroded) than Ni. When Fe and Ni are in contact with each other in these liquids, Ni becomes a cathode electrode and a hydrogen generation reaction occurs, and the other Fe becomes an anode electrode and a dissolution reaction of iron occurs.
[0028]
When the steel sheet surface is covered with a Ni plating layer having pinhole-like defects scattered therein and immersed in an aqueous electrolyte solution (for example, hydrochloric acid), Fe of the steel sheet base material is preferentially dissolved in the pinhole defect portions, and pitting corrosion is caused. Is formed. As described above, when the amount of Ni plating is adjusted to the range of 0.05 to 1.0 g / m 2 per one side of the steel sheet to optimize the dispersion state of the pinhole-like defects, a pit-like concave portion is formed on the steel sheet surface. A large number of layers can be formed, and a complex-shaped roughened surface exhibiting an excellent anchor effect on the resin coating can be obtained. If the amount of Ni plating adhered is less than 0.05 g / m 2 , the tendency of the entire surface to be melted at the exposed portion of the steel substrate increases, and it is difficult to roughen the surface with high anchor effect. Conversely, if it exceeds 1.0 g / m 2 , the number of pinhole-like defects decreases, and it is difficult to achieve a rough surface of a complicated shape in which many pit-like concave portions are formed.
[0029]
When a metal pair with Fe is considered, there are many metal species that cause a dissolution reaction of Fe similarly to Ni. Although it depends on the dissolution environment, examples include Au, Pt, Ag, Hg, Cu, Pb, Sn, Co, and Cd. Here, considering as practical prerequisites that i) plating on a steel plate can be performed industrially at low cost and ii) that the plating waste liquid does not cause water pollution, the plating metal is Cu, Ni , Sn and their alloys. However, a single plating of Cu or Sn or an alloy plating composed of two or more of Cu, Sn, and Ni has been studied. However, it is impossible to realize a complex-shaped uneven surface that remarkably improves the adhesion to a resin coating. I found it difficult.
[0030]
As an etching method, a method of dipping in an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid, and nitric acid can be employed. Particularly, etching with hydrochloric acid has an advantage that a continuous pickling line of a steel maker can be used. As an example, a method of immersing in a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 50 to 150 g / L and a temperature of 60 to 95 ° C. for 25 to 300 seconds is suitable. In this case, the number of times of immersion may be one, but the immersion may be divided into a plurality of times. The total immersion time may be in the range of 25 to 300 seconds.
[0031]
By the above processing, a roughened steel sheet having a center line average roughness Ra (JIS B 0601) measured in the rolling direction of 0.3 to 2.0 μm is obtained. When the Ra value is in this range, the balance between the effect of improving the adhesion to the coating layer (particularly the organic polymer resin-based adhesive) and the manufacturing cost is very good. Further, the maximum height Ry (JIS B 0601) measured in the rolling direction is desirably 2.5 to 15.0 μm. However, the surface-roughened steel sheet of the present invention is characterized by a peculiar uneven shape composed of a large number of fine pit-like recesses, and the steel sheet is coated only when the value of Ra or Ry is in the above range. It does not result in a good anchoring effect for the layer.
[0032]
In the present invention, it is more effective to use a roll-rolled material as a steel sheet material before Ni plating. In this case, as shown in FIG. 1 (b), a roughened surface in which the unevenness by dull roll rolling and the unevenness by etching are overlapped is obtained, and the adhesion performance with the resin coating is improved. The dull roll rolling ratio is preferably about 1 to 10%, and the surface roughness after dull roll rolling is such that the center line average roughness Ra measured in the rolling direction is about 0.3 to 2.0 μm, and the maximum height Ry is 2.5. It may be adjusted to about 15.0 μm. In particular, it is more preferable to adjust Ra to 0.5 to 2.0 μm and Ry to 3.0 to 15.0 μm.
[0033]
【Example】
As a material steel sheet, it contains C: 0.18%, Si: 0.01%, Mn: 0.63%, P: 0.018%, S: 0.003% by mass%, and the balance is Fe and inevitable. A cold-rolled annealed steel strip (sheet thickness: 0.9 mm) made of steel containing impurities was used. A part of this steel strip was subjected to about 5% dull roll rolling. Two types of cold rolled and annealed dull rolls and dull rolls were prepared as plating base plates. The surface roughness before plating is as follows.
[Cold rolled annealing material] Ra: 0.3 μm, Ry: 2.2 μm
[Rolled rolled material] Ra: 0.6 μm, Ry: 3.8 μm
[0034]
After these two steel strips were degreased, single-sided electric Ni plating was performed. Nickel sulfate 240 g / L as a plating bath, nickel chloride 50 g / L, containing boric acid 35g / L, pH = 4.1, using a Watt bath at a liquid temperature of 60 ° C., as a current density of 5A / dm 2, the energization time Ni plating steel with five levels of Ni plating adhesion amount of 0.03 g / m 2 , 0.08 g / m 2 , 0.5 g / m 2 , 0.9 g / m 2 , 2.0 g / m 2 by adjusting A belt was made. A steel sheet for etching was cut out from these steel strips and etched by immersing in a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 100 g / L and a temperature of 90 ° C. for 60 seconds.
Table 1 shows the values of the Ni plating adhesion amount and the surface roughness Ra and Ry after immersion in hydrochloric acid of each steel sheet. The surface roughness is a value measured in the rolling direction on the Ni-plated surface.
[0035]
[Table 1]
A plurality of samples were cut out from each of the steel plates A to J, and an organic polymer resin-based adhesive (“Technodine AH” manufactured by Taoka Chemical Industry Co., Ltd.) was applied to the surface etched and plated with Ni to have an average thickness of 10 μm. The coating was applied almost uniformly as described above, and a bake hardening treatment was performed under the following two conditions.
[Baking condition 1] 80 ° C. × 60 minutes [Baking condition 2] 100 ° C. × 65 minutes Here, the temperature means the temperature of the atmosphere (atmosphere).
[0037]
Some of the samples after the bake hardening treatment were immersed in boiling water for 1 hour.
A bending test piece was cut out from each sample, a 3.5R-90 ° V bending test was performed so that the adhesive-coated surface was on the outside, and a “cellophane tape peeling test” was performed.
In the cellophane tape peeling test, a cellophane adhesive tape specified in JIS Z 1522 was applied to the outer peripheral portion of the bent portion, and then peeled off, the peeling state of the adhesive film was observed, and the adhesion was evaluated according to the following criteria. ○ The above is judged to be “good” in adhesion.
(Adhesion evaluation criteria)
：: No peeling was observed. 点: Point-like peeling was observed. △: Linear continuous peeling was observed. X: Total peeling or significant peeling similar thereto was observed.
[0038]
[Table 2]
As can be seen from Tables 1 and 2, regardless of the presence or absence of dull roll rolling, those of the examples of the present invention having a Ni plating adhesion amount of 0.05 to 1.0 g / m 2 can obtain good adhesion to the adhesive. Was. In particular, in the case of the dull rolled material, in the case of the baking condition 2, a material having extremely excellent adhesion (evaluation of ◎) was obtained even after boiling immersion (steel plates G and H).
[0040]
In contrast, when no dull roll rolling steel sheet E which Ni coating weight is more than the steel sheet A and 1.0 g / m 2 of less than 0.05 g / m 2 are both good with the adhesive in all samples Adhesion was not obtained.
Further, in the case of the rolled rolled material, the steel sheet A having a Ni plating adhesion amount of less than 0.05 g / m 2 did not maintain good adhesiveness after boil-immersion under the baking condition 1. In the case of the steel sheet J having the Ni plating adhesion amount exceeding 1.0 g / m 2 , good adhesiveness was not obtained in all the samples.
[0041]
【The invention's effect】
As described above, in the present invention, in the ordinary steel and the special steel in which the electrolytic surface roughening is difficult, the Ni plating layer having many pinhole-like defects formed intentionally is used to perform the etching having the peculiar irregularities. The formation of the surface was made possible. This roughened steel sheet has remarkably improved adhesiveness particularly to an organic polymer resin film as compared with a conventional dull roll finishing material. Moreover, the production can be performed relatively easily using a general steel sheet production line. Therefore, the present invention enhances the applicability of various resin coatings to the surface of a steel sheet, and particularly improves the bonding strength in the application of adhesive bonding.
[Brief description of the drawings]
FIG. 1A is an example of a roughness curve obtained by measuring the surface of a steel sheet after dull roll rolling in the rolling direction, and FIG. 1B is obtained by subjecting the steel sheet surface of FIG. It is an example of the roughness curve which measured the surface of the roughened steel sheet concerning this invention in the rolling direction.
Claims (8)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7092173B2 (en) * | 2003-04-10 | 2006-08-15 | Sony Corporation | Objective lens drive device, optical pickup device, and disk drive device |
| JP2011007250A (en) * | 2009-06-25 | 2011-01-13 | Mazda Motor Corp | Joining structure of metallic plate material |
| JP2014126034A (en) * | 2012-12-27 | 2014-07-07 | Yanmar Co Ltd | Package storage type engine generator |
| JP2017196874A (en) * | 2016-04-28 | 2017-11-02 | サスティナブル・テクノロジー株式会社 | Surface protection structure for substrate and surface protection method for substrate |
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2003
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7092173B2 (en) * | 2003-04-10 | 2006-08-15 | Sony Corporation | Objective lens drive device, optical pickup device, and disk drive device |
| JP2011007250A (en) * | 2009-06-25 | 2011-01-13 | Mazda Motor Corp | Joining structure of metallic plate material |
| JP2014126034A (en) * | 2012-12-27 | 2014-07-07 | Yanmar Co Ltd | Package storage type engine generator |
| JP2017196874A (en) * | 2016-04-28 | 2017-11-02 | サスティナブル・テクノロジー株式会社 | Surface protection structure for substrate and surface protection method for substrate |
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