JP5428906B2 - Tin-plated steel sheet with excellent paint performance - Google Patents

Tin-plated steel sheet with excellent paint performance Download PDF

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JP5428906B2
JP5428906B2 JP2010022526A JP2010022526A JP5428906B2 JP 5428906 B2 JP5428906 B2 JP 5428906B2 JP 2010022526 A JP2010022526 A JP 2010022526A JP 2010022526 A JP2010022526 A JP 2010022526A JP 5428906 B2 JP5428906 B2 JP 5428906B2
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retort
plated steel
steel sheet
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JP2010202975A (en
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茂 平野
浩 西田
和成 長谷川
利明 ▲高▼宮
正之 太田
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Nippon Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

本発明は、果実や魚肉等の食缶として使用され、特に、缶内面側において塗装して用いる場合に、優れた塗料密着性、レトルト塗料密着性および塗装後耐食性を発揮するスズめっき鋼板に関するものである。   The present invention relates to a tin-plated steel sheet that is used as a food can for fruits, fish, etc., and particularly exhibits excellent paint adhesion, retort paint adhesion, and post-coating corrosion resistance when used on the inner surface of the can. It is.

食缶用の鋼板は、一般にブリキと称されているスズめっき鋼板が用いられている。このスズめっき鋼板は、以下の方法によって製造されている。即ち、調質圧延された鋼板に、スズを電気めっきした後、リフロー処理とも呼ばれる溶融溶錫処理（スズの融点を超える温度まで加熱、溶融した後、急冷する処理）により、地鉄界面近傍のスズを合金化させると共にブリキ独特の鏡面光沢の外観を得た後、重クロム酸処理液中での電解処理によりクロメート皮膜が付与され、最後に、目的に応じた種類の油が塗油される。   As a steel plate for cans, a tin-plated steel plate generally referred to as tinplate is used. This tin-plated steel sheet is manufactured by the following method. In other words, after electroplating tin on a temper-rolled steel sheet, the molten tin treatment (heating to a temperature exceeding the melting point of tin, melting and then rapidly cooling), also called reflow treatment, is performed near the interface After tin is alloyed and tinplate has a specular gloss appearance, a chromate film is applied by electrolytic treatment in a dichromic acid treatment solution, and finally, the type of oil suitable for the purpose is applied. .

このスズめっき鋼板は製缶メーカーや食缶メーカーで、以下の工程で缶詰が製造されている。即ち、スズめっき鋼板を必要に応じて塗装した後に、剪段、溶接して円筒形の缶胴部が作製される。缶胴部の片方に底蓋を取付けた缶に充填機で果実や魚肉あるいはルーやソースなど様々な食料を詰め、蓋が取付けられる。その後、場合によっては１００℃を超えるレトルト処理（加熱殺菌処理）が施され、缶詰として出荷されている。   This tin-plated steel sheet is made by a can manufacturer or a food can manufacturer, and cans are manufactured in the following process. That is, a tin-plated steel sheet is coated as necessary, and then pruned and welded to produce a cylindrical can body. A can with a bottom lid attached to one side of the can body can be filled with various foods such as fruit, fish, roux and sauce with a filling machine, and the lid can be attached. Then, depending on the case, the retort process (heat sterilization process) exceeding 100 degreeC is given, and it is shipped as a can.

特開平７−１１４８３号公報Japanese Patent Laid-Open No. 7-11483 特開昭５４−１４２１３５号公報JP 54-142135 A 特開昭６１−１０４０９９号JP-A-61-1040099 特開２００２−１２９８５号JP 2002-12985

これまで、缶内面用には、８ｇ／ｍ２以上のスズを厚目付けしたスズめっき鋼板を無塗装で使用されてきたが、近年、スズ地金の高騰から、コストダウンの為に、スズめっき量の低下が志向され、その低スズめっき鋼板に塗装を施すことで、従来と同等の耐食性や内容物の保存性を確保するようになってきた。また、消費者から、より一層の品質、性能向上が求められてきている。 Up to now, tin-plated steel sheets with a tin weight of 8 g / m 2 or more have been used without coating for the inner surface of tins. However, in recent years, tin plating has been used to reduce costs due to soaring tin bullion. The reduction of the amount is aimed at, and by applying the coating to the low tin-plated steel sheet, the same corrosion resistance and the preservation of the contents as in the past have been secured. In addition, further quality and performance improvements have been demanded by consumers.

従って、塗装に用いられるスズめっき鋼板には、レトルト時の塗料密着性や塗装後耐食性が求められるが、特に湿潤環境下での経時によるスズ酸化膜の成長によって、スズめっき鋼板の黄変化やレトルト時の塗料密着性や塗装後耐食性の劣化も防止する技術が求められるようになった。   Accordingly, tin-plated steel sheets used for painting are required to have paint adhesion during retort and post-coating corrosion resistance. There is now a need for technology to prevent deterioration of paint adhesion and corrosion resistance after painting.

上記の課題に対して、例えば、「湿潤下での経時塗料密着性に優れたスズめっき鋼板の製造法」（特許文献１を参照）が提案されているが、「前処理工程，スズめっき工程，リフロー工程，アルカリ性の炭酸塩を含む水溶液での清浄化処理工程，硫酸またはフッ化物を含むクロム酸浴での後処理工程を順次行うスズめっき鋼板の製造法において、前記後処理工程後に、さらに８０℃以上で０．３秒〜１０秒間、スズめっき鋼板を洗浄する洗浄工程を付加してなる」工程である。このため、一般的なスズめっき鋼板の製造工程には無いアルカリ性の炭酸塩を含む水溶液での清浄化処理工程や後処理工程後の洗浄工程が必要になり、新たな設備投資が必要で経済的には不利益である。また、本製造法によって得られたスズめっき鋼板の湿潤環境下での経時後の経時後の塗料密着性、レトルト塗料密着性および塗装後耐食性は十分ではない。   In response to the above problems, for example, “a method for producing a tin-plated steel sheet excellent in paint adhesion under wet conditions” (see Patent Document 1) has been proposed. , A reflow step, a cleaning treatment step with an aqueous solution containing an alkaline carbonate, and a post-treatment step in a chromic acid bath containing sulfuric acid or fluoride. It is a process formed by adding a cleaning step of cleaning the tin-plated steel sheet at 80 ° C. or higher for 0.3 seconds to 10 seconds. For this reason, a cleaning process with an aqueous solution containing an alkaline carbonate and a cleaning process after the post-treatment process, which are not included in the general tin-plated steel plate production process, are required, and new equipment investment is necessary and economical. Is disadvantageous. In addition, the tin-plated steel sheet obtained by the present production method is not sufficient in paint adhesion, retort paint adhesion and post-coating corrosion resistance after aging in a wet environment.

また、例えば、スズめっき鋼板の酸化錫を斜方晶のＳｎＯにする提案（特許文献２を参照）があるが、この方法でも十分な密着性を確保することはできなかった。   Further, for example, there is a proposal (see Patent Document 2) that tin oxide of the tin-plated steel sheet is orthorhombic SnO, but even this method could not secure sufficient adhesion.

更に、特許文献３では、リフロー処理で生成した酸化スズ（ＩＩ）をアルカリ塩の溶液中で陰極電解して還元除去した後、同液で陽極処理して表面に酸化スズ（ＩＶ）を生成させて塗料密着性を確保する技術が提案されている。確かに、該提案技術では、レトルト処理をしない場合の塗料密着性の向上は期待されるものの、レトルト塗料密着性には触れられていない。後述する本願発明の知見Ａにあるように、良好なレトルト塗料密着性を有する溶融溶錫処理で生成した酸化スズを還元除去する為、レトルト塗料密着性は確保できない上、通常のブリキ製造ラインには無い、アルカリ塩中での電解処理工程が必要であり、新たな設備投資を要し経済的には不利益である。   Further, in Patent Document 3, tin oxide (II) produced by reflow treatment is subjected to cathodic electrolysis in an alkaline salt solution and reduced and removed, and then anodized with the same solution to produce tin oxide (IV) on the surface. Thus, techniques for ensuring paint adhesion have been proposed. Certainly, in the proposed technique, improvement in paint adhesion without retort treatment is expected, but retort paint adhesion is not touched. As shown in Knowledge A of the present invention to be described later, in order to reduce and remove tin oxide produced by molten molten tin treatment having good retort paint adhesion, retort paint adhesion cannot be ensured and a normal tin production line is used. There is no need for an electrolytic treatment process in an alkali salt, which requires a new equipment investment and is economically disadvantageous.

一方、金属スズめっき層上に付与するクロメート皮膜を金属クロムとクロム水和酸化物から構成する事で密着性向上させる技術（特許文献４）が提案されている。確かに、該提案技術では、レトルト処理をしない場合の塗料密着性の向上は期待されるものの、レトルト塗料密着性には触れられていない。また、クエン酸等の有機酸が含まれている酸性の内容物中でのイオン化傾向は、スズ＞鉄＞金属クロムの順序になる為、金属クロムの存在により、スズの溶出速度が、金属クロムが存在しない場合に比べて、著しく促進される。更に、スズが溶出し終わると、金属クロムの影響で鉄が板厚方向に急速に溶解し穿孔腐食が進行し、缶の寿命が著しく低下し、実用上はその使用に大きな制約がある。   On the other hand, the technique (patent document 4) which improves adhesiveness by comprising the chromate film | membrane provided on a metal tin plating layer from a metal chromium and chromium hydrated oxide is proposed. Certainly, in the proposed technique, improvement in paint adhesion without retort treatment is expected, but retort paint adhesion is not touched. In addition, since the ionization tendency in acidic contents containing organic acids such as citric acid is in the order of tin> iron> metal chromium, the elution rate of tin is reduced due to the presence of metal chromium. This is significantly promoted compared to the case where no is present. Further, when tin is completely eluted, iron is rapidly dissolved in the thickness direction due to the effect of metallic chromium, and piercing corrosion progresses, the life of the can is remarkably reduced, and its use is greatly restricted in practical use.

そこで、本発明は、このような問題に鑑みてなされたもので、果実や魚肉等の食缶として使用され、特に、缶内面側において塗装して用いる場合に、優れた塗料密着性、レトルト塗料密着性および塗装後耐食性を発揮するスズめっき鋼板を提供することを目的とする。   Therefore, the present invention has been made in view of such problems, and is used as a food can for fruits, fish meat, and the like, and particularly excellent paint adhesion and retort paint when used on the inner surface side of the can. An object is to provide a tin-plated steel sheet that exhibits adhesion and corrosion resistance after painting.

本発明者らは、前述の課題に対応する為、重クロム酸処理液中での電解クロメート処理を行っていないスズめっき鋼板と電解クロメート処理を施したスズめっき鋼板を作製し、湿潤環境下での経時後のレトルト塗料密着性を詳細に調査、検討した。その結果、電解クロメート処理を行っていないスズめっき鋼板は、経時前には良好なレトルト塗料密着性を有するが、湿潤環境下での経時後のレトルト塗料密着性は大幅に劣化する知見（知見Ａ）を得た。更に、過度なクロメート皮膜を均一に施す電解クロメート処理を行うと、経時前のレトルト塗料密着性がやや劣化する（知見Ｂ）ものの、湿潤環境下での経時後のレトルト塗料密着性は、電解クロメート処理を行っていないスズめっき鋼板で認められた大幅な劣化は認められず、劣化の程度は電界クロメート処理を行っていないものよりも小さくなる知見（知見Ｃ）を得た。   In order to respond to the above-mentioned problems, the present inventors produced a tin-plated steel sheet that was not subjected to electrolytic chromate treatment in a dichromic acid treatment solution and a tin-plated steel sheet that was subjected to electrolytic chromate treatment, in a wet environment. The adhesion of the retort paint after aging was investigated and examined in detail. As a result, the tin-plated steel sheet that has not been subjected to electrolytic chromate treatment has good retort paint adhesion before aging, but the knowledge that retort paint adhesion after aging in a humid environment deteriorates significantly (Knowledge A) ) Furthermore, when the electrolytic chromate treatment is applied to uniformly apply an excessive chromate film, the adhesion of the retort paint before aging is slightly deteriorated (knowledge B), but the adhesion of the retort paint after aging in a humid environment is The significant deterioration observed in the tin-plated steel sheet not subjected to the treatment was not recognized, and a knowledge (knowledge C) was obtained in which the degree of deterioration was smaller than that in the case where the electric field chromate treatment was not performed.

知見Ａのメカニズムは明確ではないが、溶融溶錫処理でスズめっき鋼板表面に生成した酸化スズが良好なレトルト塗料密着性を有しているものの、湿潤環境下の経時によって、その酸化スズが水蒸気を吸収し、変性、劣化し、レトルト塗料密着性の大幅な劣化に至ったものと考えられる。   Although the mechanism of Knowledge A is not clear, although tin oxide formed on the surface of the tin-plated steel sheet by melted tin treatment has good adhesion to the retort paint, the tin oxide becomes water vapor over time in a wet environment. This is considered to have absorbed, modified and deteriorated, and led to significant deterioration of adhesion to the retort paint.

知見Ｂおよび知見Ｃについては、クロメート皮膜自体のレトルト塗料密着性は低いものの、湿潤環境下の経時による酸化スズの変性、劣化を防止する効果がある為、経時前後で大幅な劣化が認められなかったものと推定される。   Regarding knowledge B and knowledge C, although the retort paint adhesion of the chromate film itself is low, it has the effect of preventing the modification and deterioration of tin oxide over time in a humid environment, so no significant deterioration is observed before and after aging. Estimated.

本発明者らは、以上の知見Ａ、Ｂ、Ｃに基き、適量のクロメート皮膜を不均一にする、即ち、分散させることにより、優れたレトルト塗料密着性を有する酸化スズの湿潤環境下の経時劣化を防止すると共に十分なレトルト塗料密着性を発揮し、しかも、塗装缶用鋼板として必要とされる経時後の塗料密着性や塗装後耐食性も兼備したスズめっき鋼板の発明を完成するに至った。   Based on the above findings A, B, and C, the present inventors made an appropriate amount of chromate film non-uniform, that is, dispersed, thereby allowing tin oxide having excellent retort paint adhesion over time in a wet environment. We have completed the invention of a tin-plated steel sheet that prevents deterioration and exhibits sufficient adhesion to retort paint, and also combines paint adhesion and corrosion resistance after painting, which are required for steel sheets for paint cans. .

即ち、本発明は、
（１）缶内面に使用される鋼板片面にめっき量が１．２ｇ／ｍ２以上のスズめっきを施し、溶融溶錫処理によりその一部を鋼板と合金化させた後に、溶融溶錫処理により生成された酸化スズ（ＩＩ）を除去することなく、金属クロム換算で２〜２０ｍｇ／ｍ２のクロメート皮膜を２０〜８０％の面積率で分散被覆させた事を特徴とする経時後の塗料密着性、レトルト塗料密着性および塗装後耐食性に優れたスズめっき鋼板、
を提供できる。 That is, the present invention
(1) After applying tin plating with a plating amount of 1.2 g / m 2 or more on one side of the steel plate used for the inner surface of the can, and partly alloying it with the steel plate by molten tin treatment, Paint adhesion after aging characterized in that a chromate film of 2 to 20 mg / m 2 in terms of metallic chromium is dispersed and coated at an area ratio of 20 to 80% without removing the produced tin oxide (II) , Tin-plated steel sheet with excellent retort paint adhesion and post-coating corrosion resistance ,
It can provide.

本発明により製造されるスズめっき鋼板は、優れた密着性および塗装後耐食性を有する。   The tin-plated steel sheet produced according to the present invention has excellent adhesion and post-coating corrosion resistance.

以下に本発明について詳細に説明する。   The present invention is described in detail below.

本発明に使用されるめっき原板の製造法、材質などは特に規制されるものではなく、通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。このめっき原板に、スズめっきを行う際、通常、めっき原板表面を清浄化するため前処理として脱脂、酸洗が行われるが、それらの方法は特に規制するものでは無く、例えば、１０質量％苛性ソーダ中で脱脂した後、５質量％硫酸溶液中で電解酸洗を行えばよい。   The manufacturing method, material, etc. of the plating base plate used in the present invention are not particularly restricted, and the processes such as hot rolling, pickling, cold rolling, annealing, temper rolling, etc. from the normal steel slab manufacturing process. It is manufactured after. When performing tin plating on this plating base plate, degreasing and pickling are usually performed as pretreatments to clean the plating base plate surface, but these methods are not particularly restricted, for example, 10% by weight caustic soda After degreasing, electrolytic pickling may be performed in a 5% by mass sulfuric acid solution.

脱脂、酸洗に引続き、電気的にスズめっきが行われる。電気スズめっきの方法についても特に規制しない。フェロスタン浴等の公知のスズめっき浴を使用すればよい。好ましくは、２０〜４０ｇ／Ｌのスズイオンを含む３０〜４５℃、ｐＨ０．７〜１程度のフェノールスルホン酸溶液中で、電流密度１Ａ／ｄｍ２〜５Ａ／ｄｍ２の条件でスズめっきすると良い。スズをめっきする目的は、耐食性の確保である。スズは高耐食として知られているが、有機酸中では鉄に対して犠牲防食する事が知られており、これらの効果により食品保存用途として缶内面に使用されている。スズのめっき量が１．２ｇ／ｍ２以上でこれらの効果が発現し、優れた塗装後耐食性が確保され始める。スズめっき量の増加に伴い、耐食性の向上効果も増加するが、６ｇ／ｍ２を超えると、その向上効果が飽和する。従って、スズめっき量は１．２ｇ／ｍ２以上にする必要があり、６ｇ／ｍ２以下にすることが好ましい。 Subsequent to degreasing and pickling, tin plating is performed electrically. There are no particular restrictions on the method of electrotin plating. A known tin plating bath such as a ferrostan bath may be used. Preferably, tin plating may be performed in a phenolsulfonic acid solution containing 20 to 40 g / L of tin ions at 30 to 45 ° C. and a pH of about 0.7 to 1 under a current density of 1 A / dm 2 to 5 A / dm 2 . The purpose of plating tin is to ensure corrosion resistance. Tin is known for its high corrosion resistance, but it is known to be sacrificial and anticorrosive against iron in organic acids, and due to these effects, it is used on the inner surface of cans for food preservation purposes. These effects are manifested when the tin plating amount is 1.2 g / m 2 or more, and excellent post-coating corrosion resistance begins to be ensured. As the amount of tin plating increases, the effect of improving corrosion resistance also increases. However, when the amount exceeds 6 g / m 2 , the improvement effect is saturated. Therefore, the tin plating amount needs to be 1.2 g / m 2 or more, and preferably 6 g / m 2 or less.

上記のスズめっき層が付与された後に、スズめっき層の一部を合金化する為に溶融溶錫処理が施される。溶融溶錫処理についても特に規制するものではなく、例えば、通電加熱によってスズの融点以上に昇温し、温水中で冷却すれば良い。好ましくは、通電加熱によって、１０〜３０℃／秒の昇温速度でスズの融点まで加熱し、直ちに、８０〜９０℃の温水中に浸漬して冷却する。溶融溶錫処理を行う目的は、耐食性に優れたスズ−鉄合金層の形成による耐食性の向上である。スズを一旦溶融することにより、スズは下地の鉄と容易に合金化し、非常に均一な合金層を形成する為、上層のスズ層に欠陥が存在しても、その下層に耐食性に優れたスズ−鉄合金層が存在する事で、より一層、スズめっき鋼板の耐食性は向上する。合金化させるスズ量（合金化率）は、特に規制しない。本発明においては、スズめっき量が１．２ｇ／ｍ２〜６ｇ／ｍ２であることから、概ね０．３〜１．５ｇ／ｍ２程度となる。余り多くのスズが合金化すると、加工性の優れない合金層が製缶加工中で損傷し、腐食の起点になる場合もあるので、用途に応じて合金量を制御する必要がある。好ましい合金化率は、１５〜２５％である。なお、合金化させたスズ量の定量方法としては、例えば、ＡＳＴＭのＡ６３０に規定されている電解剥離による方法がある。また、合金化させるスズ量の制御は上述したように通電加熱で行う事が好ましく、好ましい加熱条件としては、上述した１０〜３０℃／秒の昇温速度である。 After the above tin plating layer is applied, a molten tin treatment is performed in order to alloy a part of the tin plating layer. There is no particular restriction on the molten tin treatment. For example, the temperature may be raised above the melting point of tin by energization heating and cooled in warm water. Preferably, it is heated to a melting point of tin by a heating rate of 10 to 30 ° C./second by energization heating, and immediately immersed in warm water of 80 to 90 ° C. for cooling. The purpose of the molten tin treatment is to improve corrosion resistance by forming a tin-iron alloy layer having excellent corrosion resistance. Once the tin is melted, it is easily alloyed with the underlying iron to form a very uniform alloy layer, so even if there is a defect in the upper tin layer, it has excellent corrosion resistance in the lower layer. -The presence of the iron alloy layer further improves the corrosion resistance of the tin-plated steel sheet. The amount of tin to be alloyed (alloying rate) is not particularly restricted. In the present invention, since the tin plating amount is 1.2g / m 2 ~6g / m 2 , the generally 0.3 to 1.5 g / m 2 approximately. If too much tin is alloyed, an alloy layer with poor workability may be damaged during canning and may become a starting point of corrosion. Therefore, the amount of alloy must be controlled depending on the application. A preferable alloying rate is 15 to 25%. As a method for determining the amount of tin alloyed, for example, there is a method by electrolytic stripping defined in ASTM A630. The amount of tin to be alloyed is preferably controlled by energization heating as described above, and a preferable heating condition is the above-described temperature increase rate of 10 to 30 ° C./second.

溶融溶錫処理に引き続き、クロメート処理が行われる。このクロメート処理によって、本発明の本質とする分散被覆させたクロメート皮膜が形成される。クロメート皮膜は、前述の如く、湿潤環境下での経時後のレトルト塗料密着性の大幅な劣化の抑制である。この抑制効果は、クロメート皮膜が金属クロム換算で２ｍｇ／ｍ２以上付与されると発揮され始め、２０ｍｇ／ｍ２を超えると経時前のレトルト塗料密着性が劣化する。従って、クロメート皮膜量は、金属クロム換算で２〜２０ｍｇ／ｍ２にする必要がある。更に、クロメート皮膜がスズ表面を覆っている面積率が２０％を下回ると、湿潤環境下での経時後のレトルト塗料密着性が大幅に劣化する為、クロメート皮膜の面積率は２０％以上にする必要がある。一方、クロメート皮膜の面積率が８０％を超えると、経時前のレトルト塗料密着性が劣化する為、クロメート皮膜の面積率は８０％以下にする必要がある。なお、本発明における「クロメート皮膜の面積率」とは、クロメート処理前におけるスズめっきの表面積全体に対するクロメート処理後のクロメート皮膜の表面積の割合を意味する。クロメート皮膜の面積率は、ＥＰＭＡ（エレクトロンマイクロプローブ分析法）で測定する事が出来る。例えば、電子ビーム径を１０μｍにし、縦１００点、横５０点のエリアでクロムの強度を面分析することにより、クロメート皮膜の面積率を測定する事が出来る。このような観点から、クロメート皮膜の面積率は、０．５ｍｍ２の面内で測定されることが好ましい。ＥＰＭＡの装置としては市販の分析装置を使用すれば良い。 Following the molten tin treatment, a chromate treatment is performed. By this chromate treatment, a dispersion-coated chromate film as the essence of the present invention is formed. As described above, the chromate film suppresses the significant deterioration of the adhesion of the retort paint after aging in a humid environment. This suppression effect starts to be exerted when the chromate film is applied in an amount of 2 mg / m 2 or more in terms of metallic chromium, and when it exceeds 20 mg / m 2 , the retort paint adhesion before aging deteriorates. Therefore, the chromate film amount needs to be 2 to 20 mg / m 2 in terms of metal chromium. Furthermore, if the area ratio of the chromate film covering the tin surface is less than 20%, the adhesion of the retort paint after aging in a wet environment is significantly deteriorated, so the area ratio of the chromate film should be 20% or more. There is a need. On the other hand, if the area ratio of the chromate film exceeds 80%, the adhesiveness of the retort paint before aging deteriorates, so the area ratio of the chromate film needs to be 80% or less. The “area ratio of the chromate film” in the present invention means the ratio of the surface area of the chromate film after the chromate treatment to the entire surface area of the tin plating before the chromate treatment. The area ratio of the chromate film can be measured by EPMA (electron microprobe analysis). For example, the area ratio of the chromate film can be measured by making the electron beam diameter 10 μm and analyzing the strength of chromium in an area of 100 points in length and 50 points in width. From such a viewpoint, the area ratio of the chromate film is preferably measured in a plane of 0.5 mm 2 . A commercially available analyzer may be used as the EPMA apparatus.

上記のクロメート皮膜を付与する方法は、通常のブリキの製造では使用される金属クロムが析出しない重クロム酸ソーダ液中での電解処理でクロメート処理を行えば良い。一般に電気めっきでは、低電流密度では電析物の核発生より核成長が生じやすく、比較的高電流密度では、その逆に核成長より核発生が生じやすくなり被覆性が向上する傾向があるが、クロメート処理でも、この知見が適用できる。例えば、低電流密度でクロメート処理を行えば、分散被覆しやすくなる。また、高電流密度電解処理の前に、低電解処理を行う複合電解を行えば、一旦、分散発生した核が高電流密度電解でも成長し易くなることから高生産性を確保する事も可能である。いずれにしても、重クロム酸ソーダ液中での電解処理で電解条件を適度に設定することにより、クロメート皮膜を分散被覆させる事ができる。   As a method for applying the chromate film, the chromate treatment may be performed by electrolytic treatment in a sodium dichromate solution in which metal chromium used in normal tin production is not deposited. In general, in electroplating, nucleation is more likely to occur than nucleation of deposits at a low current density, and at a relatively high current density, conversely, nucleation is more likely to occur than nucleation and coverage tends to be improved. This knowledge can also be applied to chromate treatment. For example, if the chromate treatment is performed at a low current density, dispersion coating is facilitated. In addition, if composite electrolysis that performs low electrolysis treatment is performed before high current density electrolysis, it is possible to ensure high productivity because dispersed nuclei are likely to grow even in high current density electrolysis. is there. In any case, the chromate film can be dispersedly coated by appropriately setting the electrolysis conditions by electrolytic treatment in a sodium dichromate solution.

好ましいクロメート処理条件は、４０℃の４０ｇ／Ｌの重クロム酸溶液で０．１〜０．３Ａ／ｄｍ２の電流密度で０．１〜１秒電解し、その後、同一の溶液で１〜５Ａ／ｄｍ２の電流密度で０．１〜１秒電解するものである。即ち、重クロム酸溶液を用いて電解電流を変えた２段階の電解処理を行うことで、クロメート皮膜を２０〜８０％の面積率で分散被覆することができる。 Preferred chromate treatment conditions include electrolysis for 0.1 to 1 second at a current density of 0.1 to 0.3 A / dm 2 with a 40 g / L dichromic acid solution at 40 ° C., and then 1 to 5 A with the same solution. Electrolysis is performed at a current density of / dm 2 for 0.1 to 1 second. That is, the chromate film can be dispersedly coated at an area ratio of 20 to 80% by performing a two-stage electrolytic treatment using a dichromic acid solution and changing the electrolytic current.

以下に本発明の実施例及び比較例について述べ、その結果を表１に示す。   Examples of the present invention and comparative examples are described below, and the results are shown in Table 1.

冷間圧延後、焼鈍、調圧された板厚０．２０ｍｍのめっき原板に、スズイオン：２５ｇ／Ｌを含むフェロスタン浴でスズめっきを行った後、最高到達温度２４５℃で溶融溶錫処理を行い、８０℃の温水中で冷却して、スズめっき量の約２０％を合金化した。引続き８０ｇ／Ｌの重クロム酸ソーダ溶液中で、０.１Ａ／ｄｍ２と１Ａ／ｄｍ２で０．１〜０．４秒間カソード電解処理し試料を作製した。また、金属クロムの影響を示す為、特許文献４記載のクロム酸−硫酸浴中を用い、６０℃、１８Ａ／ｄｍ２、３０Ｃ／ｄｍ２でカソード電解処理した試料も作製した。前記処理材にエポキシフェノール塗料を８ｇ／ｍ２塗布し、２０４℃で１０分間加熱した後、室温まで冷却した。さらに、８時間以上室温で保管したのち、塗装面を缶内面となるようにφ２００ｍｍのＥＮＤ（缶エンド）を成型した。 After cold rolling, an annealed and regulated plated original plate with a thickness of 0.20 mm is subjected to tin plating in a ferrostan bath containing tin ions: 25 g / L, and then subjected to molten tin treatment at a maximum temperature of 245 ° C. About 20% of the tin plating amount was alloyed by cooling in warm water at 80 ° C. Continue with dichromate soda solution in 80 g / L, to prepare a 0.1 A / dm 2 and at 1A / dm 2 0.1 to 0.4 seconds cathodic electrolysis treatment and sample. Moreover, in order to show the influence of metallic chromium, a sample subjected to cathode electrolytic treatment at 60 ° C., 18 A / dm 2 and 30 C / dm 2 using a chromic acid-sulfuric acid bath described in Patent Document 4 was also produced. 8 g / m 2 of an epoxy phenol paint was applied to the treatment material, heated at 204 ° C. for 10 minutes, and then cooled to room temperature. Furthermore, after storing at room temperature for 8 hours or more, END (can end) of φ200 mm was molded so that the painted surface becomes the inner surface of the can.

成型されたＥＮＤを下記（Ａ）〜（Ｄ）の項目について特性を評価した。   The characteristics of the molded END were evaluated for the following items (A) to (D).

（Ａ）塗料密着性
成形したＥＮＤに２ｍｍ間隔で地鉄に達する１００マスの碁盤目を入れ、テープ剥離を行い塗膜の残存面積により、１０段階（塗膜剥離無しを１０点、１００％剥離したものを０点）の密着性評価を行った。密着性９点（塗膜の残存面積９０％）以上を合格とした。 (A) Paint adhesion Adhesiveness of 100 squares reaching the iron core at intervals of 2 mm is put into the molded END, and the tape is peeled off to make 10 steps (10 points for no coating peeling, 100% peeling). The adhesion evaluation was 0). Adhesion of 9 points (remaining area of the coating film 90%) or more was regarded as acceptable.

（Ｂ）レトルト塗料密着性
成型したＥＮＤを４種の水溶液に浸漬して１２０℃で９０分のレトルト処理を行い、レトルト終了後、直ちに水洗、乾燥後、２ｍｍ間隔で地鉄に達する１００マスの碁盤目を入れ、テープ剥離を行い塗膜の残存面積により、１０段階（塗膜剥離無しを１０点、１００％剥離したものを０点）の密着性評価を行った。４種の浸漬液での試験で、全て密着性７点以上を合格とした。 (B) Retort paint adhesion Adhesion of the molded END in 4 types of aqueous solution and retort treatment at 120 ° C for 90 minutes. A cross-cut was made and the tape was peeled off, and the adhesion evaluation was performed in 10 stages (10 points for no peeling of the coating film, 0 points for 100% peeling). In the test with four kinds of immersion liquids, all of the adhesion points of 7 or more were regarded as acceptable.

浸漬液は以下の（ａ）〜（ｄ）の水溶液の４種とした。
（ａ）３質量％酢酸＋２質量％塩化ナトリウム
（ｂ）１．１質量％乳酸
（ｃ）２質量％クエン酸＋０．４質量％アスコルビン酸
（ｄ）０．０５６質量％システイン塩酸塩＋０．４質量％リン酸２水素カリウム＋０．８１質量％リン酸ナトリウム The immersion liquid was four types of the following aqueous solutions (a) to (d).
(A) 3% by mass acetic acid + 2% by mass sodium chloride (b) 1.1% by mass lactic acid (c) 2% by mass citric acid + 0.4% by mass ascorbic acid (d) 0.056% by mass cysteine hydrochloride + 0.4 Mass% potassium dihydrogen phosphate + 0.81 mass% sodium phosphate

（Ｃ）経時後レトルト塗料密着性
作成したスズめっき鋼板を、５０℃で湿度９０％ＲＨの条件で防錆紙に梱包し、同条件で７日間貯蔵したのち、前記（Ｂ）の評価を行った。 (C) Retort paint adhesion after aging The prepared tin-plated steel sheet was packed in rust-proof paper at 50 ° C. and humidity of 90% RH, stored for 7 days under the same conditions, and then evaluated (B). It was.

（Ｄ）塗膜下耐食性
成形したＥＮＤに地鉄に達する深さのクロスカットを入れ、１．５％クエン酸−１．５％塩化ナトリウム混合液からなる試験液に、４５℃、７２時間浸漬し、洗浄、乾燥後、テープ剥離を行い、クロスカット部の塗膜下腐食状況と平板部の腐食状況を４段階（◎：塗膜下腐食が認められない、○：実用上問題無い程度の僅かな塗膜下腐食が認められる、△：微小な腐食下腐食と平板部に僅かな腐食が認められる、×：激しい腐食塗膜下腐食と平板部に腐食が認められる）で判断して評価した。◎、○を合格とした。 (D) Corrosion resistance under the coating film A cross cut with a depth reaching the base iron is put into the molded END, and immersed in a test solution composed of a 1.5% citric acid-1.5% sodium chloride mixed solution at 45 ° C. for 72 hours. After cleaning and drying, the tape is peeled off, and the corrosion condition under the coating film in the crosscut part and the corrosion condition in the flat plate part are classified into four stages (◎: No corrosion under the coating film is recognized, ○: No problem in practical use) Slight under-coating corrosion is observed, Δ: Corrosion under micro-corrosion and slight corrosion is observed on flat plate part, X: Vigorous corrosive under-coating corrosion and corrosion on flat plate part are recognized) did. ◎ and ○ were accepted.

（Ｅ）実缶試験
成形したＥＮＤの塗膜に硬度４Ｈ鉛筆で疵をつけ、全塗装されているφ２００×１１０ｍｍの缶体に、パイナップルとシロップを詰め、該ＥＮＤを巻き締め、３８℃で３ヶ月間貯蔵後、該ＥＮＤの塗膜疵部の穿孔腐食を４段階（◎：殆ど穿孔腐食が認められない、○：板厚の１０〜３０％程度の穿孔腐食が認められる、△：板厚の３０％以上の穿孔腐食が認められる、×：完全に貫通し液漏れが認められる）で判断して評価した。◎、○を合格とした。 (E) Actual can test A molded END coating film is glazed with a pencil of 4H hardness, pineapple and syrup are packed into a fully coated can body of φ200 × 110 mm, and the END is wound and tightened at 38 ° C. After storage for months, the END coating has a four-stage piercing corrosion (◎: almost no piercing corrosion is observed, ○: piercing corrosion about 10 to 30% of the plate thickness is observed, △: plate thickness 30% or more of perforation corrosion was observed, x: completely penetrated and liquid leakage was observed). ◎ and ○ were accepted.

Figure 0005428906
Figure 0005428906

上記表１に示すように、実施例１〜９については、（Ａ）塗料密着性、（Ｂ）レトルト塗料密着性、（Ｃ）経時後レトルト塗料密着性、（Ｄ）塗膜下耐食性、（Ｅ）実缶試験結果のいずれについても良好な結果が得られた。一方、スズめっき量が本発明の範囲よりも少ない比較例１については、塗膜下耐食性が劣っていた。また、クロメート皮膜の付着量が本発明の範囲よりも少ない比較例２については、（Ｃ）経時後のレトルト塗料密着性が劣っていた。また、クロメート皮膜の付着量が本発明の範囲よりも多い比較例３については、（Ｂ）レトルト塗料密着性が劣っていた。また、クロメート皮膜の面積率が本発明の範囲よりも小さい比較例４については、（Ｃ）経時後のレトルト塗料密着性に劣る結果となった。さらに、クロメート皮膜の面積率が本発明の範囲よりも大きい比較例５については、（Ｂ）レトルト塗料密着性に劣る結果となった。金属クロムが析出した比較例６は急速に穿孔腐食が進行する結果となった。   As shown in Table 1 above, for Examples 1 to 9, (A) paint adhesion, (B) retort paint adhesion, (C) post-time retort paint adhesion, (D) corrosion resistance under coating film, ( E) Good results were obtained for any of the actual can test results. On the other hand, in Comparative Example 1 in which the tin plating amount is smaller than the range of the present invention, the corrosion resistance under the coating film was inferior. Moreover, about the comparative example 2 with the adhesion amount of a chromate film | membrane being less than the range of this invention, (C) Retort paint adhesion after time passed was inferior. Moreover, about the comparative example 3 with much adhesion amount of a chromate film | membrane than the range of this invention, (B) retort paint adhesion was inferior. Moreover, about the comparative example 4 whose area ratio of a chromate film | membrane is smaller than the range of this invention, it became a result inferior to the retort paint adhesiveness after (C) time-lapse | temporal. Furthermore, about the comparative example 5 whose area ratio of a chromate film | membrane is larger than the range of this invention, it became a result inferior to (B) retort paint adhesion. In Comparative Example 6 in which metallic chromium was deposited, the result of rapid piercing corrosion progressed.

以上、本発明の好適な実施形態について説明したが、本発明はかかる例に限定されないことは言うまでもない。当業者であれば、特許請求の範囲に記載された範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。

As mentioned above, although preferred embodiment of this invention was described, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

Claims (1)

缶内面に使用される鋼板片面にめっき量が１．２ｇ／ｍ２以上のスズめっきを施し、溶融溶錫処理によりその一部を鋼板と合金化させた後に、前記溶融溶錫処理により生成された酸化スズ（ＩＩ）を除去することなく、金属クロム換算で２〜２０ｍｇ／ｍ２のクロメート皮膜を２０〜８０％の面積率で分散被覆させたことを特徴とする、スズめっき鋼板。
The steel plate used on the inner surface of the can is tin plated with a plating amount of 1.2 g / m 2 or more, and a part thereof is alloyed with the steel plate by molten tin treatment, and then produced by the molten tin treatment. A tin-plated steel sheet obtained by dispersing and coating a 2-20 mg / m 2 chromate film in an area ratio of 20 to 80% in terms of metallic chromium without removing tin (II) oxide .
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