JPH06101092A - Chromium-plated steel sheet for laminating polyester and method for producing the same - Google Patents
Chromium-plated steel sheet for laminating polyester and method for producing the sameInfo
- Publication number
- JPH06101092A JPH06101092A JP25497692A JP25497692A JPH06101092A JP H06101092 A JPH06101092 A JP H06101092A JP 25497692 A JP25497692 A JP 25497692A JP 25497692 A JP25497692 A JP 25497692A JP H06101092 A JPH06101092 A JP H06101092A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- steel sheet
- plated steel
- layer
- polyester
- 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.)
- Withdrawn
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】
【目的】 本発明は、製缶用のポリエステル積層用クロ
ムめっき鋼板とポリエステル樹脂との密着性を大幅に向
上させることを目的とする。
【構成】 （１）鋼板表面の少なくとも片面に下層に金
属クロム層、上層にカルボン酸含有クロム酸化物層を形
成したことを特徴とするポリエステル積層用クロムめっ
き鋼板。
（２）鋼板表面の少なくとも片面に下層に金属クロム
層、上層にカルボン酸含有クロム酸化物層を生成したク
ロムめっき鋼板の製造に際して、クロムめっき浴中又
は、クロム酸化物処理浴中へカルボン酸を０．１〜１０
ｇ／ｌ添加し、鋼板を陰極として、電解処理することを
特徴とする、ポリエステル積層用クロムめっき鋼板の製
造方法。(57) [Summary] [Object] An object of the present invention is to significantly improve the adhesion between a polyester resin and a chromium-plated steel sheet for polyester lamination for can manufacturing. [Structure] (1) A chromium-plated steel sheet for laminating polyester, wherein a metal chromium layer is formed as a lower layer and a carboxylic acid-containing chromium oxide layer is formed as an upper layer on at least one surface of the steel sheet. (2) When producing a chromium-plated steel sheet in which a metal chromium layer is formed as a lower layer and a carboxylic acid-containing chromium oxide layer is formed as an upper layer on at least one surface of the steel sheet, carboxylic acid is added to a chromium plating bath or a chromium oxide treatment bath. 0.1-10
A method for producing a chromium-plated steel sheet for polyester lamination, which comprises adding g / l and electrolytically treating the steel sheet as a cathode.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製缶用鋼板としてのポ
リエステル積層用クロム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 a chromium-plated steel sheet for polyester lamination as a steel sheet for can making and a method for producing the same.
【０００２】[0002]
【従来の技術】缶容器は２ピース缶と３ピース缶に大別
され、内容物の特性に応じて両者は使い分けされてい
る。しかし近年においては、製缶コスト、蓋の巻締め易
さ、缶体の美観等に優れる２ピース缶の生産量増加が著
しい。従来、２ピース缶のほとんどは絞りしごき缶、い
わゆるＤＩ缶といわれるものであり、鋼板素材としては
錫めっき鋼板が用いられてきた。しかし、最近になって
特開平１−２５８８２２号公報、特開平２−２６９６４
７号公報、特開平２−２６３５２３号公報等に見られる
ような、絞り再絞り法による２ピース缶製造技術が開発
された。この一連の製缶技術では、ＤＩ缶のようなしご
き加工を施さず、絞り加工のみで缶成形するために、缶
外面とダイスとの擦過がＤＩ缶ほど激しくなく、たとえ
ば特公平２−５８０９４号公報に見られるようなポリエ
ステル樹脂フィルム被覆金属板をその素材として使用す
ることができる。ポリエステル樹脂としては、実用的に
はポリエチレンテレフタレートが用いられることが多
い。2. Description of the Related Art Can containers are roughly classified into two-piece cans and three-piece cans, and both can be used properly according to the characteristics of the contents. However, in recent years, the production amount of two-piece cans, which are excellent in can manufacturing cost, easiness of winding the lid, and aesthetics of the can body, has remarkably increased. Conventionally, most of the two-piece cans are so-called squeezed and ironed cans, so-called DI cans, and tin-plated steel plates have been used as the steel plate material. However, recently, JP-A-1-258822 and JP-A-2-26964 have been proposed.
A two-piece can manufacturing technique has been developed by the squeezing and redrawing method as seen in Japanese Unexamined Patent Application Publication No. 7-27, Japanese Unexamined Patent Publication No. 2-263523, and the like. In this series of can making technology, since the can is formed only by drawing without performing the ironing process like the DI can, the friction between the outer surface of the can and the die is not as severe as that of the DI can. For example, Japanese Patent Publication No. 2-58094. A polyester resin film-coated metal plate as found in the publication can be used as the material. Practically, polyethylene terephthalate is often used as the polyester resin.
【０００３】このようなポリエステル樹脂フィルム被覆
金属板を用いた絞り再絞り缶では、該金属板での樹脂フ
ィルムと金属板（電解クロム酸処理鋼板等）との密着性
が十分でないため、たとえば特開平１−２４９３３１号
公報に見られるようにフィルムと金属板との密着面に接
着剤を塗布する等の工夫がなされる。In a drawn and redrawn can using such a polyester resin film-coated metal plate, the adhesion between the resin film on the metal plate and the metal plate (electrolytic chromic acid-treated steel plate, etc.) is not sufficient, and therefore, for example, As can be seen in Japanese Patent Laid-Open No. 1-249331, a device such as applying an adhesive to the contact surface between the film and the metal plate is made.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、この場
合には接着剤塗布によるコスト増加が避けられず、実用
面では不利となる。本発明は、このようなポリエステル
樹脂被覆金属板でのフィルム密着性を有利に改善するク
ロムめっき鋼板とその製造方法を提供することを目的と
する。However, in this case, the cost increase due to the application of the adhesive is unavoidable, which is disadvantageous in practical use. An object of the present invention is to provide a chrome-plated steel sheet that advantageously improves the film adhesion on such a polyester resin-coated metal sheet and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
に本発明は、 （１）鋼板表面の少なくとも片面に下層に金属クロム
層、上層にカルボン酸含有クロム酸化物層を生成したこ
とを特徴とするポリエステル積層用クロムめっき鋼板。 （２）前項のめっき鋼板表面にポリエステル層を有する
ことを特徴とするクロムめっき鋼板。 （３）鋼板表面の少なくとも片面に下層に金属クロム
層、上層にクロム酸化物層を有するクロムめっき鋼板の
製造に際し、クロムめっき浴中又は、クロム酸化物処理
浴中へカルボン酸を０．１〜１０ｇ／ｌ添加し、鋼板を
陰極として電解処理することを特徴とする、ポリエステ
ル積層用クロムめっき鋼板の製造方法である。To achieve the above object, the present invention is characterized in that (1) a metal chromium layer is formed as a lower layer and a carboxylic acid-containing chromium oxide layer is formed as an upper layer on at least one surface of a steel sheet surface. Chromium-plated steel sheet for polyester lamination. (2) A chrome-plated steel sheet having a polyester layer on the surface of the plated steel sheet according to the preceding paragraph. (3) When producing a chromium-plated steel sheet having a metal chromium layer as a lower layer and a chromium oxide layer as an upper layer on at least one surface of the steel sheet, 0.1 to 0.1% of carboxylic acid is added to the chromium plating bath or the chromium oxide treatment bath. It is a method for producing a chromium-plated steel sheet for polyester lamination, which comprises adding 10 g / l and electrolytically treating the steel sheet as a cathode.
【０００６】以下、本発明を詳細に説明する。周知のよ
うに缶用のクロムめっき鋼板は塗膜の密着性に優れてい
る。これは、クロムめっき鋼板の最表層のクロム酸化物
と塗膜の間に水素結合が形成されることによると言われ
ている。ポリエステル樹脂フィルム被覆の場合も同様と
考えられる。水素結合は共有結合のような強固な結合で
はなく、水のような極性分子が結合界面に浸透してくる
と結合力が弱まる傾向にある。The present invention will be described in detail below. As is well known, chrome-plated steel sheets for cans have excellent coating film adhesion. It is said that this is due to the formation of hydrogen bonds between the chromium oxide on the outermost layer of the chrome-plated steel sheet and the coating film. The same applies to the case of polyester resin film coating. The hydrogen bond is not a strong bond like a covalent bond, but the bonding force tends to be weakened when a polar molecule such as water permeates the bonding interface.
【０００７】そこで、本発明者らはポリエステル樹脂と
クロムめっき鋼板最表層との間で結合力の強固な共有結
合を形成する方法について研究した結果、新たに形成方
法を見出し本発明に至った。すなわち、クロムめっき鋼
板の最表層クロム酸化物中にカルボン酸を共析させると
該鋼板に積層したポリエステル樹脂との密着力が飛躍的
に向上することを見出した。これは、ポリエステル樹脂
分子の末端の水酸基−ＯＨとカルボン酸のカルボキシル
基−ＣＯＯＨとがエステル化反応を起こして強固な結合
を形成するためと考えられる。すなわち、 ＲＣＯＯＨ（カルボン酸）＋Ｒ′ＯＨ（ポリエステル）
→ＲＣＯＯＲ′＋Ｈ2 Ｏ 但し、ＲおよびＲ′は炭化物水酸基 なる反応により、クロムめっき鋼板の最表層のクロム酸
化物中に共析したカルボン酸とポリエステル樹脂とが共
有結合による強固な結合を形成して、クロムめっき鋼板
とポリエステル樹脂フィルムとの密着力が飛躍的に向上
するものと推測される。Therefore, as a result of researching a method for forming a covalent bond having a strong bonding force between the polyester resin and the outermost surface layer of the chrome-plated steel sheet, the present inventors have found a new forming method and arrived at the present invention. That is, it has been found that when carboxylic acid is co-deposited in the chromium oxide on the outermost surface of the chromium-plated steel sheet, the adhesion with the polyester resin laminated on the steel sheet is dramatically improved. It is considered that this is because the hydroxyl group -OH at the terminal of the polyester resin molecule and the carboxyl group -COOH of the carboxylic acid cause an esterification reaction to form a strong bond. That is, RCOOH (carboxylic acid) + R'OH (polyester)
→ RCOOR '+ H 2 O However, R and R'become a strong hydroxyl bond by covalent bond between the carboxylic acid and the polyester resin co-deposited in the chromium oxide in the outermost layer of the chromium-plated steel sheet due to the reaction of a carbide hydroxyl group. It is speculated that the adhesion between the chrome-plated steel sheet and the polyester resin film will be dramatically improved.
【０００８】カルボン酸としては、モノカルボン酸、ジ
カルボン酸、あるいは鎖式カルボン酸、芳香族カルボン
酸等広範囲なものが可能であるが、クロムめっき浴中へ
の溶解性の点から、低位の鎖式モノカルボン酸、たとえ
ば蟻酸、酢酸、プロピオン酸、酪酸、吉草酸等が使用し
やすい。As the carboxylic acid, a wide range of monocarboxylic acids, dicarboxylic acids, chain carboxylic acids, aromatic carboxylic acids and the like can be used, but from the viewpoint of solubility in the chromium plating bath, the lower chain Formula monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid and the like are easy to use.
【０００９】クロムめっき鋼板の最表層のクロム酸化物
層へのカルボン酸の共析は、ＸＰＳ（X-ray Photo-elec
tron Spectroscopy)によるＣ元素の分析により確認でき
る。試料の表面汚染の原因であるＣ−Ｈ結合のＣの結合
エネルギーは２８５eVであるのに対し、ＣＯＯＨ結合の
Ｃのそれは２８９eVであり、両者は区別できる。Ｃの結
合エネルギーが２８５eVのピーク強度をＰ（Ｃ）、２８
９eVのピーク強度をＰ（Ｃｒ）とすると、Ｐ（Ｃ）／Ｐ
（Ｃｒ）が０．０１〜１であると密着力向上効果が認め
られる。０．０１未満では、カルボン酸量が不足して共
有結合の形成が不十分であり、１超ではカルボン酸量が
多すぎてクロム酸化物層の本来の構造が破壊されるもの
と考えられる。The eutectoid of carboxylic acid on the outermost chromium oxide layer of the chromium-plated steel sheet is obtained by XPS (X-ray Photo-elec
It can be confirmed by analysis of C element by tron spectroscopy. The C—H bond C, which causes the surface contamination of the sample, has a binding energy of 285 eV, whereas the COOH bond C has a binding energy of 289 eV, which are distinguishable from each other. The peak intensity at which the binding energy of C is 285 eV is P (C), 28
If the peak intensity of 9 eV is P (Cr), P (C) / P
When (Cr) is 0.01 to 1, the effect of improving the adhesion is recognized. When it is less than 0.01, it is considered that the amount of carboxylic acid is insufficient and covalent bond formation is insufficient, and when it is more than 1, the amount of carboxylic acid is too large and the original structure of the chromium oxide layer is destroyed.
【００１０】周知のようにクロムめっき方法には１ステ
ップ法と２ステップ法とがある。１ステップ法は金属ク
ロムとクロム酸化物生成を同時に行ない、２ステップ法
は第１ステップ目で金属クロム生成、第２ステップ目で
クロム酸化物生成を行なうものであるが、本発明のクロ
ム酸化物中へのクロム酸共析には、１ステップ法ではク
ロムめっき処理、２ステップ法では第２ステップ目の処
理が重要となる。該処理浴中へのカルボン酸添加量は、
電解条件によっても異なるが、概ね０．１〜１０ｇ／ｌ
程度が適当である。０．１ｇ／ｌ未満では、効果が不十
分であり、１０ｇ／ｌ超では、クロム酸化物層の構造が
破壊される。As is well known, the chromium plating method includes a one-step method and a two-step method. The one-step method simultaneously produces metallic chromium and chromium oxide, and the two-step method produces metallic chromium in the first step and chromium oxide in the second step. For chromic acid co-deposition in the inside, the chromium plating treatment in the one-step method and the second step treatment in the two-step method are important. The amount of carboxylic acid added to the treatment bath is
Although it depends on the electrolysis conditions, it is generally 0.1-10 g / l
The degree is appropriate. If it is less than 0.1 g / l, the effect is insufficient, and if it exceeds 10 g / l, the structure of the chromium oxide layer is destroyed.
【００１１】本発明におけるクロムめっき鋼板の金属ク
ロム量、クロム酸化物量は特に規定するものではない
が、通常缶用材料として用いられているクロムめっき鋼
板と同等でよい。すなわち、金属クロムは５０〜２００
mg／ｍ2 、クロム酸化物はクロム量として５〜３０mg／
ｍ2 程度が適当である。尚、下限値未満では、耐食性が
不十分であり、上限値超では、効果が飽和し、コストア
ップが著しい。The amount of metallic chromium and the amount of chromium oxide of the chrome-plated steel sheet according to the present invention are not particularly specified, but may be the same as those of the chrome-plated steel sheet that is usually used as a can material. That is, metallic chromium is 50 to 200
mg / m 2 , chromium oxide is 5-30 mg /
m 2 is suitable. If it is less than the lower limit, the corrosion resistance is insufficient, and if it exceeds the upper limit, the effect is saturated and the cost is significantly increased.
【００１２】[0012]
【実施例】次に本発明の実施例を挙げる。アルミキルド
鋼で、板厚０．２６mm、テンパー度Ｔ−５Ｃ、表面粗度
０．２５μｍのめっき原板を常法により脱脂、酸洗して
クロムめっきを施した。クロムめっき浴は、 ＣｒＯ3 ２００ｇ／ｌ（リットル） ＮＦ4 Ｆ ４ｇ／ｌ カルボン酸 ０〜１０ｇ／ｌ で、浴温４０℃、電流密度５０Ａ／dm2 で金属クロム析
出量が約１００mg／ｍ2になるように通電時間を調整し
た。作成したクロムめっき鋼板の最表層のクロム酸化物
中のカルボン酸濃度をＸＰＳにより分析し、Ｐ（Ｃ）／
Ｐ（Ｃｒ）で評価した。EXAMPLES Next, examples of the present invention will be described. An aluminum killed steel plate having a plate thickness of 0.26 mm, a temper degree of T-5C and a surface roughness of 0.25 μm was degreased and pickled by a conventional method and then plated with chromium. The chromium plating bath was CrO 3 200 g / l (liter) NF 4 F 4 g / l carboxylic acid 0 to 10 g / l, the bath temperature was 40 ° C., the current density was 50 A / dm 2 , and the amount of metal chromium deposited was about 100 mg / m 2. The energization time was adjusted so that The concentration of carboxylic acid in the chromium oxide in the outermost layer of the prepared chromium-plated steel sheet was analyzed by XPS, and P (C) /
It was evaluated by P (Cr).
【００１３】クロムめっき鋼板とポリエステル樹脂フィ
ルムとの密着性は以下の方法で評価した。クロムめっき
鋼板を電気炉で２４０℃に加熱し、炉からすばやく取り
出してゴムロール（径２００mm）により厚み２０μｍの
ポリエステルフィルム（予熱温度２００℃）と熱ラミネ
ートし、ロール引出し後０．３秒で表面温度１５０℃に
水冷した。その後、該フィルム面を外面にして絞り比２
で絞り加工を施し缶を成形し、その缶胴部にカッターナ
イフで素地に達する疵（幅０．０５mm）を入れ、１３０
℃×３０分のレトルト処理を行ない、疵部におけるフィ
ルム剥離幅を測定し、密着性の指標とした（剥離幅が大
きいほど密着性は劣る。）。結果を表１に示す。The adhesion between the chrome-plated steel sheet and the polyester resin film was evaluated by the following method. A chrome-plated steel sheet is heated to 240 ° C in an electric furnace, quickly taken out of the furnace, and thermally laminated with a 20 μm thick polyester film (preheating temperature 200 ° C) using a rubber roll (diameter 200 mm), and the surface temperature is 0.3 seconds after the roll is pulled out. It was water-cooled to 150 ° C. After that, with the film surface as the outer surface, the drawing ratio is 2
Squeeze the can to form a can, and put a flaw (width 0.05 mm) that reaches the base with a cutter knife in the body of the can.
The retort treatment was performed at 30 ° C. for 30 minutes, and the film peeling width at the scratched portion was measured and used as an index of the adhesiveness (the larger the peeling width, the poorer the adhesiveness). The results are shown in Table 1.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【発明の効果】上記実施例からも明らかのように、本発
明によれば、製缶用のポリエステル積層用クロムめっき
鋼板とポリエステル樹脂との密着性を大幅に向上させる
ことができ、工業的に顕著な効果を奏することができ
る。As is apparent from the above examples, according to the present invention, it is possible to greatly improve the adhesiveness between the chrome-plated steel sheet for polyester lamination for can manufacturing and the polyester resin. A remarkable effect can be produced.
Claims (3)
クロム層、上層にカルボン酸含有クロム酸化物層を生成
したことを特徴とするポリエステル積層用クロムめっき
鋼板。1. A chromium-plated steel sheet for laminating polyester, wherein a metal chromium layer is formed as a lower layer and a carboxylic acid-containing chromium oxide layer is formed as an upper layer on at least one surface of the steel sheet.
ル層を有することを特徴とするクロムめっき鋼板。2. A chromium-plated steel sheet having a polyester layer on the surface of the plated steel sheet according to claim 1.
クロム層、上層にカルボン酸含有クロム酸化物層を生成
したクロムめっき鋼板の製造に際し、クロムめっき浴中
又は、クロム酸化物処理浴中へカルボン酸を０．１〜１
０ｇ／ｌ添加し、鋼板を陰極として、電解処理すること
を特徴とする、ポリエステル積層用クロムめっき鋼板の
製造方法。3. In the production of a chromium-plated steel sheet in which a metal chromium layer is formed as a lower layer and a carboxylic acid-containing chromium oxide layer is formed as an upper layer on at least one surface of the steel sheet, carbon is introduced into a chromium plating bath or a chromium oxide treatment bath. 0.1 to 1 acid
A method for producing a chromium-plated steel sheet for polyester lamination, which comprises adding 0 g / l and electrolytically treating the steel sheet as a cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25497692A JPH06101092A (en) | 1992-09-24 | 1992-09-24 | Chromium-plated steel sheet for laminating polyester and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25497692A JPH06101092A (en) | 1992-09-24 | 1992-09-24 | Chromium-plated steel sheet for laminating polyester and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06101092A true JPH06101092A (en) | 1994-04-12 |
Family
ID=17272488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25497692A Withdrawn JPH06101092A (en) | 1992-09-24 | 1992-09-24 | Chromium-plated steel sheet for laminating polyester and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06101092A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997016582A1 (en) * | 1995-11-02 | 1997-05-09 | Toyo Kohan Co., Ltd. | Process for producing laminated steel sheet, laminated steel sheet, and surface-treated steel sheet used therefor |
-
1992
- 1992-09-24 JP JP25497692A patent/JPH06101092A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997016582A1 (en) * | 1995-11-02 | 1997-05-09 | Toyo Kohan Co., Ltd. | Process for producing laminated steel sheet, laminated steel sheet, and surface-treated steel sheet used therefor |
| US6280852B1 (en) | 1995-11-02 | 2001-08-28 | Toyo Kohan Co., Ltd. | Process for producing laminated steel sheet, laminated steel sheet, and surface-treated steel sheet used therefor |
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Legal Events
| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19991130 |