JP2000008189A - Plated steel sheet excellent in corrosion resistance after working, film adhesion and printing appearance and its production - Google Patents
Plated steel sheet excellent in corrosion resistance after working, film adhesion and printing appearance and its productionInfo
- Publication number
- JP2000008189A JP2000008189A JP10175974A JP17597498A JP2000008189A JP 2000008189 A JP2000008189 A JP 2000008189A JP 10175974 A JP10175974 A JP 10175974A JP 17597498 A JP17597498 A JP 17597498A JP 2000008189 A JP2000008189 A JP 2000008189A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- chromium
- plated steel
- film adhesion
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は印刷外観、耐食性、
樹脂密着性に優れた、容器用めっき鋼板およびその製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to printing appearance, corrosion resistance,
The present invention relates to a plated steel sheet for containers having excellent resin adhesion and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、金属飲料缶として、鋼板の両面に
熱可塑性樹脂フィルムをラミネートし、深絞り加工で成
形された缶が使用されている。上記ラミネート鋼板用の
原板としては、加工後のフィルム密着性が優れている点
で、鋼板表面にクロムめっき層とクロム水和酸化物層を
有するティンフリー鋼板が使用されている。2. Description of the Related Art In recent years, metal beverage cans formed by laminating a thermoplastic resin film on both sides of a steel plate and forming by deep drawing are used. As an original sheet for the laminated steel sheet, a tin-free steel sheet having a chromium plating layer and a chromium hydrated oxide layer on the surface of the steel sheet is used because of excellent film adhesion after processing.
【０００３】[0003]
【発明が解決しようとする課題】近年、金属飲料缶の印
刷外観に対する要求が高まり、今まで以上の印刷仕上が
り性が要望されている。金属飲料缶の印刷外観を高める
ためには、印刷後の外観が優れるラミネート鋼板を開発
する必要がある。そこで、本発明の目的は、加工後の耐
食性、フィルム密着性および印刷外観に優れた安価なラ
ミネート鋼板およびその原板を提供することである。In recent years, there has been an increasing demand for the printed appearance of metal beverage cans, and there has been a demand for higher print finishability. In order to enhance the printed appearance of metal beverage cans, it is necessary to develop a laminated steel sheet having an excellent printed appearance. Accordingly, an object of the present invention is to provide an inexpensive laminated steel sheet excellent in corrosion resistance after processing, film adhesion, and printed appearance, and an original sheet thereof.
【０００４】[0004]
【課題を解決するための手段】本発明は、 １）鋼板の両面に、鋼板側から３０〜３００ｍｇ／ｍ2
のクロムめっき層、１０００超〜３０００ｍｇ／ｍ2 の
錫めっき層、５〜１００ｍｇ／ｍ2 のクロムめっき層、
５〜３０ｍｇ／ｍ2 のクロム水和酸化物層を有すること
を特徴とする、加工後の耐食性、フィルム密着性および
印刷外観に優れためっき鋼板。 ２）鋼板にクロムめっきを施し、引き続き錫めっきを行
うに際し、錫めっき浴中で限界電流密度以上で電解を行
いクロム水和酸化物を除去した後、通常の電流密度で電
解し錫めっき層を形成させて上記１）記載のめっき鋼板
とする、加工後の耐食性、フィルム密着性および印刷外
観に優れためっき鋼板の製造方法。The present invention provides: 1) 30-300 mg / m 2 from both sides of a steel sheet from the steel sheet side.
Chrome plating layer, 1000 a tin-plated layer of ultra ~3000mg / m 2, chrome plating layer of 5 to 100 mg / m 2,
A plated steel sheet having a chromium hydrated oxide layer of 5 to 30 mg / m 2 and excellent in corrosion resistance after processing, film adhesion and printed appearance. 2) When chromium plating is applied to the steel sheet and then tin plating is performed, electrolysis is performed at a current higher than the limit current density in a tin plating bath to remove chromium hydrated oxide, and then electrolysis is performed at a normal current density to form a tin plating layer. A method for producing a plated steel sheet having excellent corrosion resistance after processing, film adhesion, and printed appearance, which is formed into the plated steel sheet according to the above 1).
【０００５】[0005]
【発明の実施の形態】以下、本発明の内容について詳細
に説明する。図１は本発明のラミネート用鋼板の一実施
例を模式的に示す図である。本発明者らは、めっき金属
の種類や厚み、めっき層の加工性等を種々検討し、製缶
後の耐食性、フィルム密着性および印刷外観に優れたラ
ミネート鋼板用めっき鋼板として、鋼板の両面に鋼板側
からクロムめっき層（Ａ）、錫めっき層（Ｂ）、クロム
めっき層（Ｃ）およびクロム水和酸化物層（Ｄ）を有す
る錫めっき鋼板を新たに見出したものである。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the contents of the present invention will be described in detail. FIG. 1 is a view schematically showing one embodiment of the steel sheet for lamination of the present invention. The present inventors have studied various types and thicknesses of plated metal, workability of a plated layer, and the like, and as a plated steel sheet for a laminated steel sheet excellent in corrosion resistance after film making, film adhesion and printed appearance, on both sides of the steel sheet. A tin-plated steel sheet having a chromium plating layer (A), a tin plating layer (B), a chromium plating layer (C) and a chromium hydrated oxide layer (D) has been newly found from the steel sheet side.
【０００６】クロムめっき層（Ａ）は、３０〜３００ｍ
ｇ／ｍ2 のめっき量が施されるが、４０〜２００ｍｇ／
ｍ2 が望ましい。ラミネ−トおよび製缶加工後の熱処理
時に錫と地鉄の合金化を抑制するためには３０ｍｇ／ｍ
2 以上のめっき量が必要であるが、製缶加工時の加工密
着性の点から、３００ｍｇ／ｍ2 以下にする必要があ
る。また、クロムめっき層に、クロムめっき浴中に含ま
れる不可避的な不純物を含んでも本発明の効果に変化は
ない。The chrome plating layer (A) has a thickness of 30 to 300 m.
g / m 2 , but 40-200 mg / m 2
m 2 is desirable. In order to suppress the alloying of tin and ground iron during heat treatment after lamination and can making, 30 mg / m
Although a plating amount of 2 or more is required, it is required to be 300 mg / m 2 or less from the viewpoint of processing adhesion during can-making. Further, even if the chromium plating layer contains unavoidable impurities contained in the chromium plating bath, the effect of the present invention is not changed.
【０００７】錫めっき層（Ｂ）は、１０００超〜３００
０ｍｇ／ｍ2 のめっき量が施されるが、１５００〜２０
００ｍｇ／ｍ2 が望ましい。缶内面の耐食性および缶外
面の印刷外観を確保するためには、製缶加工後の缶壁部
の地鉄露出率を抑制する必要があり、１０００ｍｇ／ｍ
2 超の錫めっきが必要である。ただし、多過ぎても効果
が飽和し経済的でないため、３０００ｍｇ／ｍ2 以下が
妥当である。また、錫めっき層に、錫めっき浴中に含ま
れる不可避的な不純物を含んでも本発明の効果に変化は
ない。The tin plating layer (B) has a thickness of more than 1000 to 300
A plating amount of 0 mg / m 2 is applied.
00 mg / m 2 is desirable. In order to ensure the corrosion resistance of the inner surface of the can and the appearance of printing on the outer surface of the can, it is necessary to suppress the exposure rate of the ground iron on the can wall after the can-making process, and 1000 mg / m2.
More than 2 tin platings are required. However, if the amount is too large, the effect is saturated and it is not economical, so 3000 mg / m 2 or less is appropriate. Further, even if the tin plating layer contains unavoidable impurities contained in the tin plating bath, the effect of the present invention is not changed.
【０００８】クロムめっき層（Ｃ）は、５〜１００ｍｇ
／ｍ2 のめっき量が施されるが、１０〜４０ｍｇ／ｍ2
が望ましい。フィルム密着性を得るためには、５ｍｇ／
ｍ2以上のめっきが必要であるが、製缶加工時の加工密
着性の点から１００ｍｇ／ｍ 2 以下にする必要がある。
また、クロムめっき層に、電解クロム酸処理浴中に含ま
れる不可避的な不純物を含んでも本発明の効果に変化は
ない。Chromium plating layer (C) is 5 to 100 mg
/ MTwoPlating amount of 10 to 40 mg / mTwo
Is desirable. To obtain film adhesion, 5 mg /
mTwoAlthough the above plating is necessary, the processing density during
100mg / m from the point of adhesion TwoIt must be:
Also included in the electrolytic chromic acid treatment bath in the chromium plating layer
Changes in the effect of the present invention even if unavoidable impurities
Absent.
【０００９】クロム水和酸化物層（Ｄ）は、クロム換算
で５〜３０ｍｇ／ｍ2 のめっき量が施される。フィルム
密着性を得るためには、５ｍｇ／ｍ2 以上のめっきが必
要であるが、製缶加工時の加工密着性およびめっき外観
の点から３０ｍｇ／ｍ2 以下にする必要がある。また、
クロム水和酸化物層に、電解クロム酸処理浴中に含まれ
る不可避的な不純物を含んでも本発明の効果に変化はな
い。The chromium hydrated oxide layer (D) is provided with a plating amount of 5 to 30 mg / m 2 in terms of chromium. In order to obtain film adhesion, plating of 5 mg / m 2 or more is necessary, but from the viewpoint of processing adhesion and plating appearance at the time of can making, it is required to be 30 mg / m 2 or less. Also,
Even if the chromium hydrated oxide layer contains unavoidable impurities contained in the electrolytic chromic acid treatment bath, the effect of the present invention is not changed.
【００１０】また、上記のめっき鋼板を製造する上で、
鋼板にクロムめっきを施し、引き続き錫めっきを行った
場合、錫めっきの表面外観およびめっき密着性が著しく
劣る問題がある。本発明者らは、錫めっきの表面外観お
よび密着性が劣化する原因として、クロムめっき時に生
成するクロム水和酸化物に着目し、各種検討を重ねた結
果、錫めっき浴中でまず限界電流密度以上で短時間の電
解を行い、クロム水和酸化物を除去した後、通常の電流
密度で電解することにより、表面外観とめっき密着性に
優れた錫めっきが得られることを新たに見出した。クロ
ム水和酸化物を除去するためには、錫の析出電流効率を
下げて水素ガス発生を増やすことで、鋼板表面のｐＨを
７以上にする必要があり、そのためには該めっき浴中で
限界電流密度以上で電解を行う必要がある。鋼板界面を
アルカリ性にすることで、クロム水和酸化物が容易に溶
解あるいは／および剥離し、クロムめっきの表面が活性
化され、密着性に優れた錫めっきが可能になると考えら
れる。限界電流密度は、錫めっき浴中のＳｎ2+イオン濃
度と鋼板とめっき浴の相対流速により決定されるため、
一概には言えないが、一般に工業的に用いられる錫めっ
き鋼板の製造方法では、１０〜１００Ａ／ｄｍ2 であ
る。また、クロム水和酸化物層を除去するための通電量
としては、少なすぎるとクロム水和酸化物層が十分に除
去できず、多過ぎるとめっき外観が劣化するため１〜１
５クーロン／ｄｍ2 が望ましい。錫めっき後に光沢を付
与するためのリフロー処理を施しても本発明の効果には
なんら変化はない。[0010] In producing the above-mentioned plated steel sheet,
When chromium plating is applied to a steel sheet and then tin plating is applied, there is a problem that the surface appearance and plating adhesion of the tin plating are extremely poor. The present inventors have focused on chromium hydrated oxide generated during chromium plating as a cause of deterioration of the surface appearance and adhesion of tin plating, and as a result of repeated examinations, as a result, firstly the critical current density in the tin plating bath As described above, it was newly found that by performing electrolysis for a short time to remove chromium hydrated oxide and then performing electrolysis at a normal current density, tin plating excellent in surface appearance and plating adhesion was obtained. In order to remove chromium hydrated oxide, it is necessary to lower the pH of the steel sheet surface to 7 or more by lowering the current efficiency of depositing tin and increasing the generation of hydrogen gas. It is necessary to perform electrolysis at a current density or higher. It is considered that by making the steel sheet interface alkaline, the chromium hydrate oxide easily dissolves and / or peels off, the surface of the chromium plating is activated, and tin plating with excellent adhesion is enabled. The critical current density is determined by the Sn 2+ ion concentration in the tin plating bath and the relative flow rate between the steel plate and the plating bath,
Although it cannot be said unconditionally, it is 10 to 100 A / dm 2 in the method of manufacturing a tin-plated steel sheet generally used industrially. On the other hand, when the amount of electricity for removing the hydrated chromium oxide layer is too small, the chromium hydrated oxide layer cannot be sufficiently removed.
5 coulombs / dm 2 is desirable. Even if a reflow treatment for imparting gloss is performed after tin plating, the effect of the present invention does not change at all.
【００１１】また、錫めっき後電解クロム酸処理の前
に、硫酸等のｐＨ４以下の酸洗溶液中にて浸漬あるいは
／および電解処理を行うことが、フィルム密着性の点か
ら望ましい。It is preferable to perform immersion or / and electrolytic treatment in a pickling solution having a pH of 4 or less such as sulfuric acid after tin plating and before electrolytic chromic acid treatment from the viewpoint of film adhesion.
【００１２】本発明で使用する熱可塑性フィルムとして
は、食品衛生性、耐食性、加工性等の性能から、ポリエ
チレン、ポリプロピレン、ポリアミド、ポリエステル、
ポリカーボネイト、ポリエーテルスルホン、アイオノマ
ー等の熱可塑性樹脂の１種または２種以上から構成され
る樹脂を用いる。樹脂の厚みとしては特に制限するもの
ではないが、５〜５０μｍが好ましい。厚みが５μｍ未
満では、鋼板への積層作業が著しく低下するとともに十
分な加工耐食性が得にくくなり、一方５０超では、製缶
分野で広く用られているエポキシ系樹脂塗料と比較した
時、経済的な点で望ましくない。As the thermoplastic film used in the present invention, polyethylene, polypropylene, polyamide, polyester,
A resin composed of one or more thermoplastic resins such as polycarbonate, polyether sulfone, and ionomer is used. The thickness of the resin is not particularly limited, but is preferably 5 to 50 μm. When the thickness is less than 5 μm, laminating work on a steel sheet is remarkably reduced, and it is difficult to obtain sufficient work corrosion resistance. On the other hand, when the thickness is more than 50, it is economical when compared with an epoxy resin paint widely used in the field of cans. Is not desirable.
【００１３】上述の樹脂について、いくつか以下に補足
説明する。本発明でのポリエステル樹脂とは、ジカルボ
ン酸とジオールの縮重合で得られる線状熱可塑性ポリエ
ステルであり、ポリエチレンテレフタレートで代表され
るものである。ジカルボン酸成分としては、テレフタル
酸、イソフタル酸、フタル酸、アジピン酸、セバチン
酸、アゼライン酸、２，６−ナフタレンジカルボン酸、
デカンジカルボン酸、ドデカンジカルボン酸、シクロヘ
キサンジカルボン酸などの単独または混合物であり、ジ
オール成分としては、エチレングリコール、ブタンジオ
ール、デカンジオール、ヘキサンジオール、シクロヘキ
サンジオール、ネオペンチルグリコールなどの単独また
は混合物である。２種以上のジカルボン酸成分やジオー
ル成分による共重合体や、ジエチレングリコール、トリ
エチレングリコールなどの他のモノマ−やポリマ−との
共重合体であっても良い。Some of the above resins will be supplementarily described below. The polyester resin in the present invention is a linear thermoplastic polyester obtained by condensation polymerization of a dicarboxylic acid and a diol, and is represented by polyethylene terephthalate. As the dicarboxylic acid component, terephthalic acid, isophthalic acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, 2,6-naphthalenedicarboxylic acid,
It is a single or mixture of decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid and the like, and the diol component is a single or mixture of ethylene glycol, butanediol, decanediol, hexanediol, cyclohexanediol, neopentyl glycol and the like. It may be a copolymer of two or more dicarboxylic acid components or diol components, or a copolymer with another monomer or polymer such as diethylene glycol or triethylene glycol.
【００１４】ポリアミド樹脂は、ナイロン６，ナイロン
７，ナイロン１１，ナイロン６６，ナイロン６１０，ナ
イロン６１２，ポリｍ−フェニレンイソフタルアミドな
どの単独または混合物である。The polyamide resin is a single or a mixture of nylon 6, nylon 7, nylon 11, nylon 66, nylon 610, nylon 612, and polym-phenylene isophthalamide.
【００１５】アイオノマー樹脂は、α−オレフィンと不
飽和カルボン酸との共重合体を金属イオンで分子鎖間を
架橋した樹脂であり、α−オレフィン成分としてはエチ
レン、プロピレン、ブテン、ペンテンなどの単独または
混合物であり、不飽和カルボン酸としてはアクリル酸、
メタクリル酸などの単独または混合物であり、金属イオ
ン成分としては、銀、錫、ニッケル、ナトリウムなどの
単独または混合物である。The ionomer resin is a resin in which a copolymer of an α-olefin and an unsaturated carboxylic acid is cross-linked between molecular chains with metal ions, and the α-olefin component is a homopolymer such as ethylene, propylene, butene and pentene. Or a mixture, wherein the unsaturated carboxylic acid is acrylic acid,
It is a single or a mixture of methacrylic acid and the like, and the metal ion component is a single or a mixture of silver, tin, nickel, sodium and the like.
【００１６】さらに、本発明で使用される樹脂は、可塑
剤・酸化防止熱安定剤・無機粒子・顔料・有機滑剤など
の添加物を配合してもかまわない。また、樹脂は、溶融
状、フィルム状いずれの形態でも差し支えなく特に規制
するものではない。溶融状ではＴダイ法等により鋼板に
積層し、フィルム状ではフィルム自体を熱接着するか、
熱硬化型接着剤を塗布して鋼板に積層される。また、本
発明で使用する鋼板は、特に限定するものではないが、
加工性の点で低炭素鋼や極低炭素鋼が望ましい。Further, the resin used in the present invention may contain additives such as a plasticizer, an antioxidant heat stabilizer, inorganic particles, a pigment and an organic lubricant. Further, the resin may be in any of a molten state and a film state and is not particularly limited. In the molten state, it is laminated on a steel plate by the T-die method or the like.
A thermosetting adhesive is applied and laminated on a steel plate. Further, the steel sheet used in the present invention is not particularly limited,
From the viewpoint of workability, low carbon steel and ultra low carbon steel are desirable.
【００１７】[0017]
【実施例】以下に本発明の実施例と比較例を述べる。板
厚０．２６ｍｍの冷延鋼板を５％ＮａＯＨ溶液中で電解
脱脂、１０％Ｈ2 ＳＯ4 溶液中への浸漬で酸洗後、下記
の条件でめっきを行った。めっき工程は（１）クロムめ
っき、（２）錫めっき、（３）電解クロム酸処理工程の
順に行い、各工程の間および（３）終了後に水洗を行っ
た。特に、（２）と（３）の工程間では、短時間の水洗
後、金属錫表面が再び酸化しない様に速やかに処理を行
う必要がある。EXAMPLES Examples of the present invention and comparative examples will be described below. A cold rolled steel sheet having a thickness of 0.26 mm was electrolytically degreased in a 5% NaOH solution, pickled by immersion in a 10% H 2 SO 4 solution, and then plated under the following conditions. The plating step was performed in the order of (1) chromium plating, (2) tin plating, and (3) electrolytic chromic acid treatment step, and water washing was performed between each step and after completion of (3). In particular, between the steps (2) and (3), it is necessary to quickly perform treatment after washing with water for a short time so that the metal tin surface is not oxidized again.
【００１８】（１）クロムめっき 無水クロム酸と硫酸および不可避的な不純物を含むクロ
ムめっき浴を用い、該めっき浴中で鋼板を陰極として電
解し、クロムめっきを行った。 （２）錫めっき 錫イオン、フェノ−ルスルフォン酸、ＥＮＳＡ，ＥＮ等
の光沢添加剤および不可避的な不純物を含む錫めっき浴
を用い、該めっき浴中で鋼板を陰極として電解し、Ｓｎ
めっきを行った。 （３）電解クロム酸処理 無水クロム酸と硫酸および不可避的な不純物を含むクロ
ムめっき浴を用い、該めっき浴中で鋼板を陰極として電
解し、金属クロムと水和酸化クロムをめっきした。(1) Chromium Plating A chromium plating bath containing chromic anhydride, sulfuric acid and unavoidable impurities was used, and a chromium plating was carried out in the plating bath by using a steel sheet as a cathode. (2) Tin plating Using a tin plating bath containing a brightening additive such as tin ion, phenolsulfonic acid, ENSA, EN and unavoidable impurities, electrolyzing a steel sheet as a cathode in the plating bath,
Plating was performed. (3) Electrolytic chromic acid treatment Using a chromium plating bath containing chromic anhydride, sulfuric acid and unavoidable impurities, electrolysis was performed using a steel sheet as a cathode in the plating bath, and chromium metal and hydrated chromium oxide were plated.
【００１９】上記の工程より得られた鋼板を２３０℃に
加熱し、両面に着色顔料を含まない２５μｍのＰＥＴフ
ィルムを熱融着で接着した後、絞り比２．８の深絞り加
工を行い、缶内面の耐食性、缶外面の印刷外観およびフ
ィルムの密着性を評価した結果を表１に示す。実施例１
〜６はいずれも、加工後の耐食性（鉄溶出量が１ｐｐｍ
以下）、フィルム密着性（フィルムの剥離無し）および
印刷外観（白色塗装後のＬ値が７０以上）に優れ、ラミ
ネート用鋼板として好適である。The steel sheet obtained from the above process is heated to 230 ° C., and a 25 μm PET film containing no coloring pigment is bonded on both sides by heat fusion, and then subjected to deep drawing at a drawing ratio of 2.8. Table 1 shows the results of evaluating the corrosion resistance of the inner surface of the can, the printed appearance of the outer surface of the can, and the adhesiveness of the film. Example 1
No. to No. 6 are corrosion resistance after processing (iron elution amount is 1 ppm
Excellent in film adhesion (no peeling of the film) and printed appearance (L value after white coating is 70 or more), and is suitable as a steel sheet for lamination.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表１中の特性評価は次の方法により行っ
た。 （１）フィルム密着性 表１の鋼板に着色顔料を含まない熱可塑性フィルムをラ
ミネートした後、薄肉化深絞り加工で絞り比２．８の深
絞り缶に加工した。フィルムの密着性は、加工した缶の
フランジ部にフィルムの剥離が有るか否かで評価した。
表中の○は剥離が無いもの、×は剥離が見られたもので
ある。 （２）耐食性 前記（１）と同様の条件で製缶加工後、缶胴の中央部を
５ｃｍ角に切り出し、５℃で硬球による落下デントを行
い、フィルムに微細なクラックを与えた。その試験片を
１．５％のクエン酸と１．５％の食塩を含む３８℃に保
持した水溶液１００ｍｌに１週間浸漬後、溶出した鉄の
量を化学分析で定量した。表中の◎は溶出した鉄の量が
０．１ｐｐｍ以下、○は０．１ｐｐｍ超１ｐｐｍ以下、
△は１ｐｐｍ超である。 （３）印刷外観 前記（１）と同様の条件で製缶加工後、缶の外面に白色
塗料を３μｍ厚で塗布し焼き付けた後、缶胴の中央部を
切り出した。島津製分光測色計ＵＶ−２１００Ｓを用
い、Ｃ光源・視野角１０°の条件で拡散反射光の測色を
行い、Ｌａｂ表色系のＬ値を指標とし、印刷外観を評価
した。表中の◎はＬ値が７５以上、○はＬ値が７０以上
７５未満、×はＬ値が７０未満である。The characteristics in Table 1 were evaluated by the following methods. (1) Film adhesion After laminating a thermoplastic film containing no coloring pigment on the steel sheet shown in Table 1, it was processed into a deep drawn can having a drawing ratio of 2.8 by thinning deep drawing. The adhesion of the film was evaluated based on whether or not the film was peeled off at the flange portion of the processed can.
In the table, ○ indicates no peeling, and X indicates that peeling was observed. (2) Corrosion resistance After the can-making process under the same conditions as in (1) above, the center of the can body was cut into 5 cm squares, and a drop dent was performed with a hard ball at 5 ° C. to give fine cracks to the film. The test piece was immersed in 100 ml of an aqueous solution containing 1.5% citric acid and 1.5% sodium chloride and maintained at 38 ° C. for one week, and the amount of eluted iron was quantified by chemical analysis. In the table, ◎ indicates that the amount of eluted iron was 0.1 ppm or less,
Δ is more than 1 ppm. (3) Printing Appearance After can-making under the same conditions as in (1) above, a white paint was applied to the outer surface of the can at a thickness of 3 μm and baked, and then the center of the can body was cut out. Using a spectral colorimeter UV-2100S manufactured by Shimadzu, colorimetry of diffuse reflected light was performed under the conditions of a C light source and a viewing angle of 10 °, and the print appearance was evaluated using the L value of the Lab color system as an index. In the table, ◎ indicates an L value of 75 or more, O indicates an L value of 70 or more and less than 75, and X indicates an L value of less than 70.
【００２２】[0022]
【発明の効果】本発明により始めて、加工後の耐食性、
フィルム密着性および印刷外観に優れたラミネート鋼板
が得られる。これにより、印刷時の顔料低減による缶コ
ストの低減が可能になること等の優れた効果が得られ
る。According to the present invention, for the first time, corrosion resistance after processing,
A laminated steel sheet excellent in film adhesion and printed appearance can be obtained. As a result, an excellent effect such as a reduction in can cost due to a reduction in pigment at the time of printing is obtained.
【図１】本発明のめっき鋼板の断面図である。FIG. 1 is a sectional view of a plated steel sheet according to the present invention.
１ 鋼板 ２ クロムめっき層 ３ 錫めっき層 ４ クロムめっき層 ５ クロム水和酸化物層 DESCRIPTION OF SYMBOLS 1 Steel plate 2 Chromium plating layer 3 Tin plating layer 4 Chromium plating layer 5 Chromium hydrate oxide layer
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F100 AA22D AA28C AB03A AB13B BA05 BA06 BA13 EH71B EH71C EH712 EJ611 JB02 JK06 YY00B YY00C YY00D 4K024 AA02 AA07 AB03 BA03 BB23 BC01 CA08 DA03 DA04 DB04 GA04 GA12 GA16 4K044 AA02 AB02 BA02 BA10 BA15 BB06 BC02 BC04 BC09 CA18 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA22D AA28C AB03A AB13B BA05 BA06 BA13 EH71B EH71C EH712 EJ611 JB02 JK06 YY00B YY00C YY00D 4K024 AA02 AA07 AB03 BA03 BB23 BC01 CA08 DA03 BA04 BA04 GA04 GA04 GA04 GA04 BC02 BC04 BC09 CA18
Claims (2)
ｍｇ／ｍ2 のクロムめっき層、１０００超〜３０００ｍ
ｇ／ｍ2 の錫めっき層、５〜１００ｍｇ／ｍ2 のクロム
めっき層、クロム換算で５〜３０ｍｇ／ｍ2 のクロム水
和酸化物層を有することを特徴とする、加工後の耐食
性、フィルム密着性および印刷外観に優れためっき鋼
板。1. A steel sheet having a thickness of 30 to 300 from both sides of the steel sheet.
mg / m 2 chrome plating layer, more than 1000 to 3000 m
g / m 2 tin plating layer, 5 to 100 mg / m 2 chromium plating layer, and 5 to 30 mg / m 2 chromium hydrated oxide layer in terms of chrome, corrosion resistance after processing, film Plated steel sheet with excellent adhesion and printed appearance.
めっきを行うに際し、錫めっき浴中でまず限界電流密度
以上で電解を行いクロム水和酸化物を除去した後、通常
の電流密度で電解し錫めっき層を形成させて請求項１に
記載のめっき鋼板とすることを特徴とする、加工後の耐
食性、フィルム密着性および印刷外観に優れためっき鋼
板の製造方法。2. A steel sheet is subjected to chromium plating and subsequently to tin plating. First, in a tin plating bath, electrolysis is performed at a current higher than the limit current density to remove chromium hydrated oxide, and then electrolysis is performed at a normal current density. A method for producing a plated steel sheet having excellent corrosion resistance, film adhesion, and printed appearance after processing, wherein a plated steel sheet according to claim 1 is formed by forming a tin plating layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10175974A JP2000008189A (en) | 1998-06-23 | 1998-06-23 | Plated steel sheet excellent in corrosion resistance after working, film adhesion and printing appearance and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10175974A JP2000008189A (en) | 1998-06-23 | 1998-06-23 | Plated steel sheet excellent in corrosion resistance after working, film adhesion and printing appearance and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000008189A true JP2000008189A (en) | 2000-01-11 |
Family
ID=16005512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10175974A Withdrawn JP2000008189A (en) | 1998-06-23 | 1998-06-23 | Plated steel sheet excellent in corrosion resistance after working, film adhesion and printing appearance and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000008189A (en) |
-
1998
- 1998-06-23 JP JP10175974A patent/JP2000008189A/en not_active Withdrawn
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