JP4495543B2 - Hot water soluble resin coated stainless steel sheet - Google Patents
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本発明は、温水洗浄によって樹脂皮膜を容易に除去できる樹脂被覆ステンレス鋼板に関する。 The present invention relates to a resin-coated stainless steel sheet that can easily remove a resin film by washing with warm water.
ステンレス鋼板の美麗な外観を活用する用途では、加工時に鋼板表面の疵付きを防止するため、塩化ビニル等の保護フィルムをステンレス鋼板に貼り付け、加工後にステンレス鋼板から保護フィルムを剥離する方法が採用されている。保護フィルムの貼付け，剥離は作業工数を増加させることになるので、加工後の鋼板表面から容易に除去できる有機樹脂皮膜が検討されている。 In applications that utilize the beautiful appearance of stainless steel sheets, a method of attaching a protective film such as vinyl chloride to the stainless steel sheet and preventing the protective film from being peeled off after processing is used to prevent the surface of the steel sheet from becoming wrinkled. Has been. Since sticking and peeling of the protective film increases the number of work steps, an organic resin film that can be easily removed from the steel sheet surface after processing has been studied.
有機樹脂皮膜としてアルカリ可溶型の皮膜を形成すると、所定形状に成形されたステンレス鋼板をアルカリ洗浄することにより有機樹脂皮膜を溶解除去できる。アルカリ可溶型有機樹脂皮膜としては、たとえば鹸化度：90％以上，ガラス転移温度：50〜70℃，数平均分子量：50,000〜100,000の水溶性カルボキシル基変性ポリビニルアルコールと水溶性潤滑剤を含む皮膜（特許文献１），酸価：40〜90，イソシアネート換算ウレタン結合含有量：12〜20質量％，弾性率（100℃）：1,000〜60,000Ｎ／ｃｍ2，流動開始温度：75〜170℃のカルボキシル基含有ウレタン樹脂皮膜（特許文献２）等がある。
アルカリ可溶型の有機樹脂皮膜は、アルカリ洗浄によって容易に除去できるため、従来の保護フィルムを使用する場合と比較して工程負荷が軽減される。しかし、アルカリ洗浄のために専用設備が必要で、アルカリ洗浄後の水洗工程も必要になる。しかも、アルカリ洗浄液の取扱いに注意を要し、洗浄廃液の処理にかかる負担も余儀なくされる。
アルカリ洗浄に代えて温水洗浄で有機樹脂皮膜を除去できると、設備，処理等にかかる負担から加工メーカが解放され、美麗な外観を活かしたステンレス鋼板の各種用途への一層の展開が図られる。
Since the alkali-soluble organic resin film can be easily removed by alkali cleaning, the process load is reduced as compared with the case of using a conventional protective film. However, dedicated equipment is required for alkali cleaning, and a water washing step after alkali cleaning is also required. In addition, care must be taken in handling the alkaline cleaning liquid, and the burden on the processing of the cleaning waste liquid is unavoidable.
If the organic resin film can be removed by hot water cleaning instead of alkali cleaning, processing manufacturers are freed from the burden of equipment and processing, and further development of various applications for stainless steel sheets that take advantage of the beautiful appearance is achieved.
本発明は、ステンレス鋼板表面に対する有機樹脂皮膜の密着性，有機樹脂種に応じた温水への溶解度について種々調査・検討した結果、親水化処理したステンレス鋼板表面に鹸化度の高いポリビニルアルコール皮膜を形成することにより、高温多湿化で膨潤することなく、しかも温水洗浄で容易に除去できる有機樹脂皮膜を鋼板表面に設けた樹脂被覆ステンレス鋼板を提供することを目的とする。 As a result of various investigations and examinations on the adhesion of an organic resin film to the surface of a stainless steel plate and the solubility in warm water according to the type of organic resin, a polyvinyl alcohol film having a high degree of saponification is formed on the surface of a hydrophilic stainless steel plate. Accordingly, an object of the present invention is to provide a resin-coated stainless steel sheet provided with an organic resin film on the steel sheet surface that does not swell due to high temperature and humidity and can be easily removed by washing with warm water.
本発明の温水可溶型樹脂被覆ステンレス鋼板は、鋼板表面から深さ：１０ｎｍまでの表層域におけるＣｒ2Ｏ3に対するＣｒ(ＯＨ)3・ｎＨ2ＯとのＣｒ2p3/2ピーク強度比が０.５〜２.８に調整されたステンレス鋼板を基材とし、鹸化度：90モル％以上のポリビニルアルコール皮膜が設けられていることを特徴とする。
皮膜樹脂としては、重合度：３００〜３０００のポリビニルアルコールが好ましい。
ポリビニルアルコール皮膜に潤滑剤を含ませると、加工時の滑りが改善され鋼板表面の疵付きが防止される。潤滑剤としては、ポリエチレン樹脂粉末及びポリエチレン樹脂の粒子表面にフッ素樹脂微粉末が結合したポリエチレン-フッ素樹脂粉末を複合した潤滑剤が好適である。
The hot water-soluble resin-coated stainless steel plate of the present invention has a Cr2p 3/2 peak intensity ratio of Cr (OH) 3 .nH 2 O to Cr 2 O 3 in the surface layer region from the steel plate surface to a depth of 10 nm is 0. A stainless steel plate adjusted to 0.5 to 2.8 is used as a base material, and a polyvinyl alcohol film having a saponification degree of 90 mol% or more is provided.
As the coating resin, polyvinyl alcohol having a polymerization degree of 300 to 3000 is preferable.
When a lubricant is included in the polyvinyl alcohol film, slippage during processing is improved, and wrinkling of the steel sheet surface is prevented. As the lubricant, a polyethylene resin powder and a lubricant in which a polyethylene-fluororesin powder in which a fluororesin fine powder is bonded to the surface of polyethylene resin particles are combined are suitable.
除去容易な有機樹脂皮膜としては、アルカリ可溶型以外に水可溶型が考えられるが、水に可溶な有機樹脂皮膜では高温多湿環境に曝されると膨潤し、樹脂被覆ステンレス鋼板が相互にブロッキングする虞がある。実用的な有機樹脂皮膜とするためには、水に溶けることなく温水のみに可能な特性を付与する必要がある。本発明では、水に不溶で温水に可溶とする観点からポリビニルアルコールを皮膜の主樹脂に選択し、ＯＨ基含有量の指標である鹸化度を９０モル％以上に調整することによって水に不溶で温水に可溶な有機樹脂皮膜に改質している。 As an organic resin film that can be easily removed, a water-soluble type can be considered in addition to an alkali-soluble type, but a water-soluble organic resin film swells when exposed to a high-temperature and high-humidity environment, and the resin-coated stainless steel sheets are mutually There is a risk of blocking. In order to obtain a practical organic resin film, it is necessary to impart characteristics that are possible only to warm water without dissolving in water. In the present invention, polyvinyl alcohol is selected as the main resin of the film from the viewpoint of being insoluble in water and soluble in warm water, and insoluble in water by adjusting the degree of saponification, which is an index of OH group content, to 90 mol% or more. The organic resin film is soluble in hot water.
鹸化度が温水可溶性に及ぼす影響は、次のように説明できる。鹸化度が高いことは、ポリビニルアルコールのＯＨ基含有量が多いことを意味する。鹸化度：９０モル％以上では多量のＯＨ基があるため、隣接するＯＨ基間で水素結合が生じ、水分子による水和作用が阻害されるため常温の水に不溶となる。他方、温水環境下では分子の運動エネルギーが大きくなってＯＨ基間の水素結合が切れやすくなり、フリーなＯＨ基が水分子と水和反応する結果、有機樹脂皮膜が温水に溶解する。 The influence of the degree of saponification on hot water solubility can be explained as follows. A high degree of saponification means that the OH group content of polyvinyl alcohol is high. When the degree of saponification is 90 mol% or more, a large amount of OH groups are present, so that hydrogen bonds are formed between adjacent OH groups and the hydration action by water molecules is inhibited, so that it becomes insoluble in water at room temperature. On the other hand, in a warm water environment, the kinetic energy of the molecules increases and the hydrogen bonds between the OH groups are easily broken. As a result of the free OH groups hydrating with water molecules, the organic resin film dissolves in the warm water.
皮膜の主樹脂であるポリビニルアルコールは、樹脂被覆ステンレス鋼板の加工性を改善するため重合度：３００〜３０００のポリビニルアルコールが好ましい。重合度の増加に従い皮膜強度が向上し、加工時にカジリ疵等の欠陥が生じがたいポリビニルアルコール皮膜となる。重合度が皮膜強度，加工性に及ぼす影響は、重合度：３００以上で顕著になる。しかし、３０００を超える重合度のポリビニルアルコールでは、樹脂の結晶性が高くなって脆化し、却ってカジリ疵が加工時に発生しやすくなる。 The polyvinyl alcohol which is the main resin of the film is preferably polyvinyl alcohol having a polymerization degree of 300 to 3000 in order to improve the workability of the resin-coated stainless steel plate. As the degree of polymerization increases, the film strength is improved, and a polyvinyl alcohol film in which defects such as galling are difficult to occur during processing. The influence of the degree of polymerization on the film strength and workability becomes significant when the degree of polymerization is 300 or more. However, in the case of polyvinyl alcohol having a polymerization degree exceeding 3000, the crystallinity of the resin becomes high and becomes brittle, and on the contrary, galling is likely to occur during processing.
ステンレス鋼板表面に対するポリビニルアルコール皮膜の密着性は、鋼板表面を親水化処理することにより改善される。
アクリル樹脂やウレタン樹脂では、導入したＯＨ基がステンレス鋼板表面のＯＨ基と反応して有機樹脂皮膜の密着性を高める。他方、ポリビニルアルコールはＯＨ基が相互に接近しやすい分子構造であり、分子間でＯＨ基が相互に水素結合すると分子中のＯＨ基がステンレス鋼板表面に配向せず、ポリビニルアルコール皮膜の密着性が低下する。
The adhesion of the polyvinyl alcohol film to the stainless steel plate surface is improved by hydrophilizing the steel plate surface.
In acrylic resin and urethane resin, the introduced OH group reacts with the OH group on the surface of the stainless steel plate to enhance the adhesion of the organic resin film. On the other hand, polyvinyl alcohol has a molecular structure in which OH groups are easy to approach each other. When OH groups are hydrogen bonded to each other between molecules, the OH groups in the molecules are not oriented on the surface of the stainless steel plate, and the adhesion of the polyvinyl alcohol film is improved. descend.
密着性向上に必要な量のＯＨ基をステンレス鋼板／有機樹脂皮膜の界面に確保するため、ステンレス鋼板表面を親水化処理することにより酸化皮膜のクロム酸化物をクロム水酸化物に変えている。親水化処理で鋼板表面に多量のＯＨ基を存在させると、ポリビニルアルコール中のＯＨ基が鋼板表面に優先配向されて鋼板表面のＯＨ基と反応するため、ポリビニルアルコール皮膜の密着性が向上する。 In order to secure an amount of OH groups necessary for improving adhesion at the stainless steel plate / organic resin film interface, the chromium oxide of the oxide film is changed to chromium hydroxide by hydrophilizing the surface of the stainless steel plate. When a large amount of OH groups are present on the steel sheet surface by the hydrophilization treatment, the OH groups in the polyvinyl alcohol are preferentially oriented on the steel sheet surface and react with the OH groups on the steel sheet surface, thereby improving the adhesion of the polyvinyl alcohol film.
ステンレス鋼板表面は、リン酸及び／又はリン酸化合物と硝酸とを含む混酸水溶液で洗浄することにより親水化処理される。リン酸（リン酸化合物），硝酸の混酸水溶液に代え、塩酸，水酸化ナトリウム，水酸化カリウム等の水溶液も親水化処理液として使用可能である。
親水化処理で鋼板表面から深さ：１０ｎｍまでの表層域をＣｒ2Ｏ3に対するＣｒ(ＯＨ)3・ｎＨ2ＯのＣｒ2p3/2ピーク強度比が０.５〜２.８となるように改質すると、後述の実施例にもみられるように密着性に優れたポリビニルアルコール皮膜を形成できる。他方、０.５未満のピーク強度比では鋼板表面が十分に親水化されず、ポリビニルアルコール皮膜の密着性が不足しがちになる。逆に２.８を超えるピーク強度では、ステンレス鋼板表面が部分的にエッチング過剰となり、ステンレス鋼板本来の美麗な外観が損なわれる。
The surface of the stainless steel plate is hydrophilized by washing with a mixed acid aqueous solution containing phosphoric acid and / or a phosphoric acid compound and nitric acid. Instead of a mixed acid aqueous solution of phosphoric acid (phosphoric acid compound) and nitric acid, an aqueous solution of hydrochloric acid, sodium hydroxide, potassium hydroxide or the like can also be used as a hydrophilic treatment solution.
In the surface layer region from the steel sheet surface to a depth of 10 nm by the hydrophilization treatment, the Cr2p 3/2 peak intensity ratio of Cr (OH) 3 .nH 2 O to Cr 2 O 3 is 0.5 to 2.8. When modified, a polyvinyl alcohol film excellent in adhesion can be formed as seen in Examples described later. On the other hand, when the peak intensity ratio is less than 0.5, the steel sheet surface is not sufficiently hydrophilized, and the adhesion of the polyvinyl alcohol film tends to be insufficient. Conversely, at a peak intensity exceeding 2.8, the surface of the stainless steel plate is partially over-etched, and the original beautiful appearance of the stainless steel plate is impaired.
ポリビニルアルコール皮膜に潤滑剤を分散させると、樹脂被覆ステンレス鋼板の加工時に金型に接する素材の滑りが改善され、樹脂被覆ステンレス鋼板の加工性が向上する。潤滑剤としては、常用のフッ素樹脂粉末やポリエチレン，ポリプロピレン等のポリオレフィン樹脂粉末、ＡＢＳ，ポリスチレン等のスチレン系樹脂粉末、塩化ビニル，塩化ビニリデン等のハロゲン樹脂粉末等を使用可能であるが、ポリエチレン樹脂及びポリエチレン-フッ素樹脂粉末を樹脂塗料に複合分散させることが好適である。ポリエチレン-フッ素樹脂粉末は、ポリエチレン樹脂の粒子表面にフッ素樹脂微粉末を結合させた複合粒子であり、加熱・軟化したポリエチレン樹脂粒子にフッ素樹脂微粉末を接触・吸着させることにより製造される。 When the lubricant is dispersed in the polyvinyl alcohol film, the slip of the material in contact with the mold during the processing of the resin-coated stainless steel plate is improved, and the workability of the resin-coated stainless steel plate is improved. As the lubricant, conventional fluororesin powder, polyolefin resin powder such as polyethylene and polypropylene, styrene resin powder such as ABS and polystyrene, and halogen resin powder such as vinyl chloride and vinylidene chloride can be used. In addition, it is preferable that the polyethylene-fluororesin powder is compositely dispersed in the resin paint. The polyethylene-fluororesin powder is a composite particle in which a fluororesin fine powder is bonded to the surface of a polyethylene resin particle, and is produced by contacting and adsorbing the fluororesin fine powder to a heated and softened polyethylene resin particle.
ポリエチレン樹脂，ポリエチレン-フッ素樹脂粉末を複合添加した樹脂塗料で成膜した有機樹脂皮膜は、以下の理由で優れた潤滑性を示す。
ポリエチレン-フッ素樹脂粒子は、粒子表面に結合したフッ素樹脂微粉末によって耐熱性が付与され、ポリエチレン樹脂粉末に比較して若干比重が大きくなっているものの、比重が大きく液中で安定分散しない従来のフッ素樹脂粒子単独に比較して水溶液中の分散安定性も向上している。
An organic resin film formed with a resin coating in which polyethylene resin and polyethylene-fluorine resin powder are added in combination exhibits excellent lubricity for the following reasons.
Polyethylene-fluorine resin particles are given heat resistance by the fluororesin fine powder bonded to the particle surface, and the specific gravity is slightly higher than that of polyethylene resin powder, but the specific gravity is large and stable dispersion in liquid is not possible. The dispersion stability in the aqueous solution is also improved as compared with the fluororesin particles alone.
ポリエチレン樹脂粒子，ポリエチレン−フッ素樹脂粒子を配合した樹脂塗料を下地金属板に塗布した状態では、ウエットな樹脂塗膜にポリエチレン樹脂粒子，ポリエチレン-フッ素樹脂粒子が懸濁する。乾燥・焼成時の昇温過程で、樹脂塗料から水分が蒸発し、樹脂塗膜の膜厚が減少するに伴い、樹脂塗膜の表面からポリエチレン樹脂粒子，ポリエチレン-フッ素樹脂粒子が突出する。
樹脂塗膜の乾燥・焼成時に１００〜２００℃の範囲に板温が通常設定されており、ポリエチレン樹脂は種類，分子量によって異なるものの融点が１００〜１３０℃の範囲にある。乾燥・焼成時の加熱温度がポリエチレン樹脂粒子の融点を超えると、樹脂塗膜から突出しているポリエチレン樹脂粒子がリフローし、ブリードしたポリエチレン樹脂で樹脂塗膜の表面が覆われる。他方、ポリエチレン-フッ素樹脂粒子は、ポリエチレン樹脂の粒子表面にフッ素樹脂微粉末が結合して耐熱性が高くなっているので、ポリエチレン樹脂粒子の融点を超える高温状態でもブリードすることなく初期の粒形状を維持する。
In a state where a resin coating containing polyethylene resin particles and polyethylene-fluorine resin particles is applied to the base metal plate, the polyethylene resin particles and the polyethylene-fluorine resin particles are suspended in the wet resin coating film. In the temperature rising process during drying and baking, moisture evaporates from the resin paint, and as the film thickness of the resin coating film decreases, polyethylene resin particles and polyethylene-fluororesin particles protrude from the surface of the resin coating film.
The plate temperature is usually set in the range of 100 to 200 ° C. when the resin coating is dried and baked, and the polyethylene resin has a melting point in the range of 100 to 130 ° C. although it varies depending on the type and molecular weight. When the heating temperature during drying / firing exceeds the melting point of the polyethylene resin particles, the polyethylene resin particles protruding from the resin coating film reflow, and the surface of the resin coating film is covered with the bleed polyethylene resin. On the other hand, since the polyethylene-fluorine resin particles have high heat resistance due to the fluororesin fine powder bonded to the polyethylene resin particle surface, the initial particle shape does not bleed even at high temperatures exceeding the melting point of the polyethylene resin particles. To maintain.
樹脂塗膜からポリエチレン-フッ素樹脂粒子が突出し、樹脂塗膜の表面一部又は全部がブリードしたポリエチレン樹脂で覆われているため、塗装金属板の潤滑性，加工性が大幅に改善される。潤滑性，加工性の改善は、ポリエチレン−フッ素樹脂粒子，ブリードしたポリエチレン樹脂によって樹脂塗膜の表面におけるポリエチレン濃度が高くなることに加え、樹脂塗膜から突出するポリエチレン-フッ素樹脂粒子がプレス加工時にコロの機能を呈することに起因すると推察される。ポリエチレン-フッ素樹脂粒子の一部は加工変形の進行に応じて一部圧潰されるが、圧潰されたポリエチレン-フッ素樹脂粒子がポリエチレン樹脂の供給源となり、プレス加工時に高面圧がかかったときでも優れた潤滑作用を期待できる。 Since the polyethylene-fluororesin particles protrude from the resin coating and the surface of the resin coating is partially or entirely covered with the bleed polyethylene resin, the lubricity and workability of the coated metal plate are greatly improved. The improvement of lubricity and workability is due to the fact that polyethylene-fluorine resin particles and bleed polyethylene resin increase the polyethylene concentration on the surface of the resin coating, and the polyethylene-fluororesin particles protruding from the resin coating It is inferred to be due to the function of the roller. Part of the polyethylene-fluororesin particles is crushed as the processing deformation progresses, but the crushed polyethylene-fluororesin particles are the source of polyethylene resin, even when high surface pressure is applied during press processing. Excellent lubrication can be expected.
板厚：０.８ｍｍのSUS304ステンレス鋼板２Ｂ仕上げ材を塗装原板に使用した。ｐＨ１２.５，液温：６０℃のアルカリ脱脂液に５秒浸漬することにより脱脂，洗浄した後、リン酸：１２ｇ／ｌ，硝酸：２ｇ／ｌの混酸水溶液（液温：６０℃）に浸漬し、水洗，乾燥することによりステンレス鋼板を親水化処理した。混酸水溶液への浸漬時間によって、ステンレス鋼板表面の改質状況を制御した。親水化の程度は、鋼板表面から深さ：１０ｎｍまでの表層域をXPS分析し、Ｃｒ2Ｏ3に対するＣｒ(ＯＨ)3・ｎＨ2ＯのＣｒ2p3/2ピーク強度比で定量化した。なお、親水化処理していないステンレス鋼板表面のＣｒ2p3/2ピーク強度比は０.２であった。 Plate thickness: 0.8 mm SUS304 stainless steel plate 2B finishing material was used as the coating original plate. After degreasing and washing by immersing in alkaline degreasing solution at pH 12.5, liquid temperature: 60 ° C. for 5 seconds, immersed in mixed acid aqueous solution (liquid temperature: 60 ° C.) of phosphoric acid: 12 g / l, nitric acid: 2 g / l The stainless steel plate was hydrophilized by washing with water and drying. The modification state of the stainless steel plate surface was controlled by the immersion time in the mixed acid aqueous solution. The degree of hydrophilization was quantified by XPS analysis of the surface layer region from the steel sheet surface to a depth of 10 nm and Cr2p 3/2 peak intensity ratio of Cr (OH) 3 .nH 2 O to Cr 2 O 3 . The Cr2p 3/2 peak intensity ratio on the surface of the stainless steel plate not subjected to hydrophilic treatment was 0.2.
親水化処理後のステンレス鋼板表面にポリビニルアルコール水溶液をバーコータで塗布し、到達板温：１００℃で加熱・乾燥することによりポリビニルアルコール皮膜を形成した。
ステンレス鋼板の親水化表面，樹脂塗料の主成分であるポリビニルアルコールの鹸化度，重合度と共に形成されたポリビニルアルコール皮膜の膜厚を表１に示す。
A polyvinyl alcohol aqueous solution was applied to the surface of the stainless steel plate after the hydrophilization treatment with a bar coater, and heated and dried at a reaching plate temperature of 100 ° C. to form a polyvinyl alcohol film.
Table 1 shows the film thickness of the polyvinyl alcohol film formed along with the hydrophilic surface of the stainless steel plate, the degree of saponification and polymerization of polyvinyl alcohol, which is the main component of the resin coating.
得られた各樹脂被覆ステンレス鋼板から試験片を切り出し、次の試験に供した。
〔ブロッキング試験〕
有機樹脂皮膜が相互に対向する状態で複数枚の試験片（サイズ：５０ｍｍ×５０ｍｍ）を重ね合わせて梱包し、４０℃，９５％RHの雰囲気に２４時間保管した後、開梱した。そして、試験片を個々に分離することによりブロッキングの発生状況を調査した。ブロッキングなく当初の塗膜表面が維持されていた試験片を○，ブロッキング起因の表面欠陥が塗膜面に発生した試験片を×として耐ブロッキング性を評価した。
〔温水溶解試験〕
８０℃の温水に試験片を浸漬し、浸漬時間の経過に伴う有機樹脂皮膜の溶解状況を調査した。有機樹脂皮膜の溶解除去に要した時間が１分以下を◎，１〜２分を○，２〜５分を△，５分以上を×として温水に対する溶解性を評価した。
A test piece was cut out from each obtained resin-coated stainless steel plate and subjected to the next test.
[Blocking test]
A plurality of test pieces (size: 50 mm × 50 mm) were overlaid and packed with the organic resin films facing each other, stored in an atmosphere of 40 ° C. and 95% RH for 24 hours, and then unpacked. Then, the occurrence of blocking was investigated by separating the test pieces individually. The blocking resistance was evaluated by setting the test piece in which the original coating film surface was maintained without blocking as ◯ and the test piece in which the surface defect due to blocking occurred on the coating surface as x.
[Warm water dissolution test]
The test piece was immersed in warm water of 80 ° C., and the state of dissolution of the organic resin film with the passage of the immersion time was investigated. The time required for dissolution and removal of the organic resin film was evaluated as solubility in warm water with ◎ for 1 minute or less, ○ for 1-2 minutes, Δ for 2 to 5 minutes, and × for 5 minutes or more.
〔潤滑試験〕
サイズ：３０ｍｍ×２５０ｍｍの試験片を用いてドロービード試験（金型のビード高さ：４ｍｍ，加圧力：３.０ｋＮ）し、金型摺動時の引抜き力を測定した。引抜き力が１.０ｋＮ以下を◎，１.０〜１.５ｋＮを○，１.５〜２.０ｋＮを△，２.０ｋＮ以上を×として潤滑性を評価した。
〔カジリ試験〕
同様に試験片をドロービード試験した後、金型が摺動した部分の有機樹脂皮膜の残存率を調査した。皮膜残存率が８０面積％以上を◎，６０〜８０面積％を○，４０〜６０面積％を△，６０面積％未満を×として耐カジリ性を評価した。
[Lubrication test]
A draw bead test (die bead height: 4 mm, pressure: 3.0 kN) was performed using a test piece of size: 30 mm × 250 mm, and the pulling force at the time of die sliding was measured. Lubricity was evaluated with a pulling force of 1.0 kN or less as ◎, 1.0 to 1.5 kN as ○, 1.5 to 2.0 kN as Δ, and 2.0 kN or more as x.
[Caulking test]
Similarly, after the test piece was subjected to a draw bead test, the remaining rate of the organic resin film in the portion where the mold slid was investigated. The galling resistance was evaluated with a film residual ratio of 80 area% or more as ◎, 60 to 80 area% as ○, 40 to 60 area% as Δ, and less than 60 area% as ×.
表２の調査結果にみられるように、本発明例No.１〜１３の樹脂被覆ステンレス鋼板は、耐ブロッキング性，有機樹脂皮膜の温水溶解性，皮膜密着性の何れも良好であった。ポリビニルアルコールの重合度を３００〜３０００の範囲に維持したNo.１〜１１では、過酷な加工条件下でも潤滑性が良好でポリビニルアルコール皮膜にカジリ疵等の欠陥が発生しなかった。重合度が３００未満のポリビニルアルコール皮膜（No.１２）や３０００を超えるポリビニルアルコール皮膜（No.１３）を設けた樹脂被覆ステンレス鋼板は、潤滑性，耐カジリ性に若干劣るものの、親水化処理していないステンレス鋼板を原板に用いた樹脂被覆ステンレス鋼板No.１６に比較すると格段に加工性に優れていた。 As seen in the investigation results in Table 2, the resin-coated stainless steel plates of Invention Examples Nos. 1 to 13 were all good in blocking resistance, hot water solubility of the organic resin film, and film adhesion. In Nos. 1 to 11 in which the polymerization degree of polyvinyl alcohol was maintained in the range of 300 to 3000, lubricity was good even under severe processing conditions, and defects such as galling were not generated in the polyvinyl alcohol film. The resin-coated stainless steel sheet provided with a polyvinyl alcohol film (No. 12) having a degree of polymerization of less than 300 or a polyvinyl alcohol film (No. 13) having a polymerization degree exceeding 3000 is slightly inferior in lubricity and galling resistance, but is hydrophilized. Compared to the resin-coated stainless steel plate No. 16 using an unstained stainless steel plate as the original plate, the workability was markedly superior.
他方、鋼板表面の親水化が不十分な比較例No.１４の樹脂被覆ステンレス鋼板では、親水化処理していないステンレス鋼板No.１６と同様にポリビニルアルコール皮膜の密着力が不足するため加工時にカジリ疵が発生し、皮膜損傷に起因して潤滑性も低下した。鹸化度が９０モル％に達しないポリビニルアルコールから成膜された有機樹脂皮膜No.１５では、ブロッキングが発生し、スタックして保管する際に塗膜面の劣化が避けられなかった。また、アクリル樹脂塗膜で被覆したステンレス鋼板No.１７，ウレタン樹脂塗膜で被覆したステンレス鋼板No.１８は、加工後にステンレス鋼板から樹脂塗膜を除去する際にアルカリ洗浄が必要とし、温水洗浄では樹脂塗膜を溶解除去できなかった。 On the other hand, in the resin-coated stainless steel plate of Comparative Example No. 14 in which the surface of the steel plate is insufficiently hydrophilic, the adhesion of the polyvinyl alcohol film is insufficient as in the case of the stainless steel plate No. 16 that has not been hydrophilized. Wrinkles occurred and the lubricity decreased due to film damage. In the organic resin film No. 15 formed from polyvinyl alcohol whose saponification degree did not reach 90 mol%, blocking occurred, and deterioration of the coating film surface was unavoidable when stacked and stored. Also, stainless steel plate No. 17 coated with acrylic resin coating and stainless steel plate No. 18 coated with urethane resin coating require alkaline cleaning when removing the resin coating from the stainless steel plate after processing. Then, the resin coating film could not be dissolved and removed.
また、前掲条件下のドロービード試験後に有機樹脂皮膜の残存率を計測し、Ｃｒ2p3/2ピーク強度比で表されるステンレス鋼板の親水化度との関係を調査した。図１の調査結果にみられるように、Ｃｒ2p3/2ピーク強度比が０.５〜２.８の範囲に維持されているステンレス鋼板では良好な皮膜密着性を示していたが、０.５に達しないＣｒ2p3/2ピーク強度比では不十分な親水化処理のため有機樹脂皮膜の密着性に劣っていた。皮膜密着性はＣｒ2p3/2ピーク強度比が大きくなるほど改善されたが、２.８を超えるＣｒ2p3/2ピーク強度比ではステンレス鋼板表面に肌荒れが目立つようになった。 Further, the residual ratio of the organic resin film was measured after the draw bead test under the above-described conditions, and the relationship with the degree of hydrophilicity of the stainless steel plate represented by the Cr2p 3/2 peak intensity ratio was investigated. As can be seen from the results of the investigation in FIG. 1, the stainless steel sheet in which the Cr2p 3/2 peak intensity ratio was maintained in the range of 0.5 to 2.8 showed good film adhesion. When the Cr2p 3/2 peak intensity ratio did not reach the range, the adhesion of the organic resin film was inferior due to insufficient hydrophilic treatment. The film adhesion was improved as the Cr2p 3/2 peak intensity ratio was increased. However, when the Cr2p 3/2 peak intensity ratio exceeded 2.8, the surface roughness of the stainless steel sheet became conspicuous.
更に、鹸化度を種々代えたポリビニルアルコール皮膜で被覆した樹脂被覆ステンレス鋼板を２０℃の常温水及び８０℃の温水に浸漬し、ポリビニルアルコール皮膜が溶解除去されるまでの時間を計測した。その結果、鹸化度：９０モル％以上のポリビニルアルコール皮膜は、常温水にほとんど溶解しなかったが、温水浸漬した場合には１分以内でほぼ完全に溶解除去した。温水に対するポリビニルアルコール皮膜の溶解は、鹸化度が高くなるほど短時間に完了する傾向にあった（図２）。他方、９０モル％に達しない鹸化度では、常温水にも溶解するため高温多湿環境に曝されると皮膜が膨潤し、樹脂皮膜が相互にブロッキングする虞がある。 Further, a resin-coated stainless steel plate coated with polyvinyl alcohol films having various saponification degrees was immersed in normal temperature water at 20 ° C. and warm water at 80 ° C., and the time until the polyvinyl alcohol film was dissolved and removed was measured. As a result, the polyvinyl alcohol film having a saponification degree of 90 mol% or more was hardly dissolved in room temperature water, but was almost completely dissolved and removed within 1 minute when immersed in warm water. The dissolution of the polyvinyl alcohol film in warm water tended to be completed in a shorter time as the degree of saponification increased (FIG. 2). On the other hand, when the degree of saponification does not reach 90 mol%, it dissolves in room temperature water, so that the film swells when exposed to a high temperature and high humidity environment, and the resin film may block each other.
表１の試験No.３，４，６，８，９のポリビニルアルコール水溶液に、ポリエチレン樹脂：フッ素樹脂の重量比が９：１となる割合でポリエチレン樹脂粉末，ポリエチレン-フッ素樹脂粉末を添加した塗料（表３）を用意した。 Paint obtained by adding polyethylene resin powder and polyethylene-fluorine resin powder to the polyvinyl alcohol aqueous solution of Test Nos. 3, 4, 6, 8, and 9 in Table 1 at a weight ratio of polyethylene resin: fluorine resin of 9: 1 (Table 3) was prepared.
親水化処理したステンレス鋼板に塗料を塗布し、実施例１と同じ条件下でポリビニルアルコール皮膜を形成した。
得られた各樹脂被覆ステンレス鋼板の物性を実施例１と同じ条件で調査した。表４の調査結果にみられるように、耐ブロッキング性，ポリビニルアルコール皮膜の温水溶解性，密着性を劣化させることなく、潤滑性，耐カジリ性が改善されていた。すなわち、ポリエチレン-フッ素樹脂粉末，ポリエチレン樹脂の複合添加により、温水にのみ溶解するポリビニルアルコール皮膜の特性を維持しながら加工性が改善された樹脂被覆ステンレス鋼板が得られることが判る。
A paint was applied to the hydrophilic stainless steel plate, and a polyvinyl alcohol film was formed under the same conditions as in Example 1.
The physical properties of the obtained resin-coated stainless steel sheets were investigated under the same conditions as in Example 1. As seen in the investigation results in Table 4, the lubricity and galling resistance were improved without deteriorating the blocking resistance, the hot water solubility of the polyvinyl alcohol film, and the adhesion. That is, it can be seen that a resin-coated stainless steel sheet having improved workability while maintaining the properties of a polyvinyl alcohol film that dissolves only in warm water can be obtained by the combined addition of polyethylene-fluorine resin powder and polyethylene resin.
以上に説明したように、親水化処理したステンレス鋼表面に鹸化度の高いポリビニルアルコール皮膜を形成することにより、加工時の潤滑性が確保され、所定形状に加工された後では温水洗浄によって容易に皮膜を溶解除去できる樹脂被覆ステンレス鋼板が得られる。しかも、切板をスタックした保管時等の際にブロッキング現象が生じ難く、皮膜の潤滑機能，ひいては樹脂被覆ステンレス鋼板の加工性が良好に保たれる。温水洗浄による皮膜の溶解除去が可能なことは、加工メーカ側の負担を大幅に軽減し、美麗な表面肌を活用する用途に適したステンレス鋼板として重宝される。 As explained above, by forming a polyvinyl alcohol film having a high degree of saponification on the surface of a stainless steel that has been subjected to hydrophilic treatment, lubricity during processing is ensured, and after being processed into a predetermined shape, it can be easily washed with warm water. A resin-coated stainless steel sheet capable of dissolving and removing the film is obtained. In addition, the blocking phenomenon is unlikely to occur during storage such as when the cut plates are stacked, and the lubrication function of the coating and, in turn, the workability of the resin-coated stainless steel plate are kept good. The ability to dissolve and remove the film by washing with hot water greatly reduces the burden on the processing manufacturer, and is useful as a stainless steel sheet suitable for applications that use beautiful surface skin.
Claims (3)
鹸化度：９０モル％以上であり、重合度が３００〜３０００であり、かつＯＨ基が無変性であるポリビニルアルコール皮膜が設けられていることを特徴とする温水可溶型樹脂被覆ステンレス鋼板。 Is measured XPS analysis, the depth from the surface of the steel sheet is: 10 nm to Cr2p 3/2 peak intensity ratio of the Cr (OH) 3 · nH 2 O with respect to Cr 2 O 3 in the surface region of 0.5-2 The base material is a stainless steel plate adjusted to .8,
A hot water-soluble resin-coated stainless steel sheet provided with a polyvinyl alcohol film having a saponification degree of 90 mol% or more , a polymerization degree of 300 to 3000, and an OH group unmodified .
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| JPH11269661A (en) * | 1998-03-24 | 1999-10-05 | Nisshin Steel Co Ltd | Production of structure made of stainless steel excellent in rusting resistance |
| JP2000169753A (en) * | 1998-12-04 | 2000-06-20 | Nippon Paint Co Ltd | Alkalide-film type aqueous lubricating composition and forming of lubricating film |
| JP2002337266A (en) * | 2001-05-22 | 2002-11-27 | Nisshin Steel Co Ltd | Coated steel sheet having excellent galling resistance and coating film adhesive properties, and coating composition |
| JP2004501252A (en) * | 2000-06-22 | 2004-01-15 | ポーハング アイアン アンド スティール シーオー．，エルティディ． | Method for producing aqueous urethane resin composition |
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| JPH11269661A (en) * | 1998-03-24 | 1999-10-05 | Nisshin Steel Co Ltd | Production of structure made of stainless steel excellent in rusting resistance |
| JP2000169753A (en) * | 1998-12-04 | 2000-06-20 | Nippon Paint Co Ltd | Alkalide-film type aqueous lubricating composition and forming of lubricating film |
| JP2004501252A (en) * | 2000-06-22 | 2004-01-15 | ポーハング アイアン アンド スティール シーオー．，エルティディ． | Method for producing aqueous urethane resin composition |
| JP2002337266A (en) * | 2001-05-22 | 2002-11-27 | Nisshin Steel Co Ltd | Coated steel sheet having excellent galling resistance and coating film adhesive properties, and coating composition |
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