JP5093797B2 - Steel plate for containers with excellent can processability - Google Patents

Steel plate for containers with excellent can processability Download PDF

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JP5093797B2
JP5093797B2 JP2007062237A JP2007062237A JP5093797B2 JP 5093797 B2 JP5093797 B2 JP 5093797B2 JP 2007062237 A JP2007062237 A JP 2007062237A JP 2007062237 A JP2007062237 A JP 2007062237A JP 5093797 B2 JP5093797 B2 JP 5093797B2
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JP2007284789A (en
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茂 平野
浩 西田
光 立木
博一 横矢
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Nippon Steel Corp
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本発明は、製缶加工用素材として、特に、絞りしごき加工、溶接性、耐食性、塗料密着性、フィルム密着性に優れた容器用鋼板に関するものである。   The present invention relates to a steel plate for containers excellent in drawing ironing, weldability, corrosion resistance, paint adhesion, and film adhesion, in particular, as a can-making material.

飲料や食品に用いられる金属容器は、2ピース缶と3ピース缶に大別される。DI缶に代表される2ピース缶は、絞りしごき加工が行われた後、缶内面側に塗装が、缶外面側には塗装及び印刷が行われる。3ピース缶は、缶内面に相当する面に塗装が、缶外面側に相当する面に印刷が行われた後、缶胴部の溶接が行われる。   Metal containers used for beverages and foods are roughly classified into two-piece cans and three-piece cans. A two-piece can represented by a DI can is squeezed and ironed, then painted on the inner surface of the can and painted and printed on the outer surface of the can. The three-piece can is coated on the surface corresponding to the inner surface of the can and printed on the surface corresponding to the outer surface of the can, and then the can body is welded.

何れの缶種においても、製缶前後に塗装工程が不可欠な工程である。塗装には、溶剤系もしくは水系の塗料が使用され、その後、焼付けが行われるが、この塗装工程において、塗料に起因する廃棄物(廃溶剤等)が産業廃棄物として排出され、排ガス(主に炭酸ガス)が大気に放出されている。近年、地球環境保全を目的とし、これら産業廃棄物や排ガスを低減しようとする取組みが行われている。この中で、塗装に代わるものとしてフィルムをラミネートする技術が注目され、急速に広まってきた。   In any type of can, a coating process is indispensable before and after canning. Solvent-based or water-based paints are used for painting, followed by baking. In this painting process, waste (such as waste solvents) resulting from the paint is discharged as industrial waste, and exhaust gas (mainly Carbon dioxide) is released to the atmosphere. In recent years, efforts have been made to reduce these industrial waste and exhaust gas for the purpose of protecting the global environment. Among these, the technique of laminating films as an alternative to painting has attracted attention and has spread rapidly.

これまでに、2ピース缶においては、フィルムをラミネートし製缶する缶の製造方法やこれに関連する発明が多数提供されている。例えば、特許第1571783号公報(特許文献1)「絞りしごき罐の製造方法」、特許第1670957号公報(特許文献2)「絞りしごき罐」、特開平2−263523号公報(特許文献3)「薄肉化深絞り缶の製造方法」、特許第1601937号公報(特許文献4)「絞りしごき罐用被覆鋼板」が挙げられる。   So far, in the two-piece can, there have been provided a large number of methods for producing a can in which a film is laminated and made, and related inventions. For example, Japanese Patent No. 1571783 (Patent Document 1) “Manufacturing Method of Squeezed Ironing Bowl”, Japanese Patent No. 1670957 (Patent Document 2) “Squeezed Ironing Bowl”, Japanese Patent Laid-Open No. 2-263523 (Patent Document 3) “ A method for producing a thinned deep-drawn can ”, Japanese Patent No. 1601937 (Patent Document 4)“ Coated steel sheet for drawn irons ”.

また、3ピース缶においては、特開平3−236954号公報(特許文献5)「スリーピース缶用フィルム積層鋼帯およびその製造方法」、特開平5−124648号公報(特許文献6)「缶外面に多層有機皮膜を有するスリーピース缶用」、特開平5−111979号公報(特許文献7)「ストライプ状の多層有機皮膜を有すスリーピース缶用鋼板」、特開平5−147181号公報(特許文献8)「3ピース缶ストライプラミネート鋼板の製造方法」が挙げられる。   In addition, in a three-piece can, Japanese Patent Laid-Open No. 3-236955 (Patent Document 5) “Three-piece Can Film Laminated Steel Band and its Manufacturing Method”, Japanese Patent Laid-Open No. 5-124648 (Patent Document 6) “On the outer surface of the can "Three-piece cans having a multilayer organic coating", JP-A-5-111979 (Patent Document 7) "Three-piece can steel plates having a striped multilayer organic coating", JP-A-5-147181 (Patent Document 8) “Production method of three-piece can striped laminated steel sheet”.

一方、ラミネートフィルムの下地に用いられる鋼板には、多くの場合、電解クロメート処理を施したクロメート皮膜が用いられている。クロメート被膜は、2層構造を有し、金属Cr層の上層に水和酸化Cr層が存在している。従って、ラミネートフィルム(接着剤付きのフィルムであれば接着層)はクロメート皮膜の水和酸化Cr層を介して鋼板との密着性を確保している。この密着発現の機構について、詳細は明らかにされていないが、水和酸化Crの水酸基とラミネートフィルムのカルボニル基あるいはエステル基などの官能基との水素結合であると言われている。
特許第1571783号公報 特許第1670957号公報 特開平2−263523号公報 特許第1601937号公報 特開平3−236954号公報 特開平5−124648号公報 特開平5−111979号公報 特開平5−147181号公報
On the other hand, in many cases, a chromate film subjected to electrolytic chromate treatment is used for a steel sheet used as a base of a laminate film. The chromate film has a two-layer structure, and a hydrated Cr oxide layer is present on the metal Cr layer. Therefore, the laminate film (adhesive layer in the case of a film with an adhesive) ensures adhesion to the steel sheet through the hydrated Cr oxide layer of the chromate film. Although the details of the mechanism of this adhesion development are not clarified, it is said to be a hydrogen bond between a hydroxyl group of hydrated Cr oxide and a functional group such as a carbonyl group or an ester group of a laminate film.
Japanese Patent No. 1571783 Japanese Patent No. 1670957 JP-A-2-263523 Japanese Patent No. 1601937 Japanese Patent Laid-Open No. 3-236554 JP-A-5-124648 JP-A-5-111979 JP-A-5-147181

上記の発明は、確かに、地球環境の保全を大きく前進せしめる効果が得られるが、その一方で、近年、飲料容器市場では、PETボトル、瓶、紙等の素材とのコスト並びに品質競争が激化しており、上記のラミネート容器用鋼板に対しても、従来技術である塗装用途に対して、優れた密着性、耐食性を確保した上で、より優れた製缶加工性、特に、フィルム密着性、加工フィルム密着性、耐食性などが求められるようになった。   Although the above-mentioned invention certainly has the effect of greatly advancing the conservation of the global environment, on the other hand, in the beverage container market, cost and quality competition with materials such as PET bottles, bottles and paper have intensified in recent years. In addition, for the above-mentioned steel sheet for laminated containers, it is possible to achieve superior can-making processability, especially film adhesion, while ensuring excellent adhesion and corrosion resistance for the conventional coating application. , Processed film adhesion, corrosion resistance, etc. have come to be required.

本発明者等は、クロメート皮膜に代わる新たな被膜としてZr皮膜の活用を鋭意検討した結果、Zr皮膜あるいはZr皮膜にリン酸皮膜やフェノール樹脂皮膜を複合されたZr皮膜が塗装あるいはラミネートフィルムと非常に強力な共有結合を形成し、従来のクロメート被膜以上の優れた製缶加工性が得られることを知見し本発明に至ったものである。   As a result of diligent research on the use of the Zr film as a new film that replaces the chromate film, the present inventors have found that the Zr film or a Zr film obtained by combining a Zr film with a phosphate film or a phenol resin film is painted or laminated. The present inventors have found that a strong covalent bond is formed, and that excellent can processability can be obtained over the conventional chromate film.

すなわち、本発明は、
(1)少なくとも鋼板片面に、金属Zr量で1〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。
That is, the present invention
(1) a composite in at least the steel sheet one side, the metal Zr amount 1-500 mg / m 2 of Zr, the phenolic resin of 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the amount of P The steel plate for containers which was excellent in the can-making process characteristic which gave the coated film | membrane by the cathodic electrolysis process .

(2)少なくとも鋼板片面に、Niを金属Niとして10〜1000mg/m2 、Snを金属Snとして80〜6000mg/m2 の1種以上を含む表面処理層を有し、その上に金属Zr量で1〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 (2) at least on the steel sheet one side, Ni and the 10 to 1000 mg / m 2, Sn has a surface treatment layer containing one or more 80~6000mg / m 2 as metallic Sn as metal Ni, metal Zr content thereon can manufacturing in the 1-500 mg / m 2 of Zr, a film that combines phenolic resin 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the P content was applied by cathodic electrolysis treatment Steel plate for containers with excellent processing characteristics.

(3)少なくとも鋼板片面に、Niを金属Niとして10〜1000mg/m2 、Snを金属Snとして80〜6000mg/m2 の1種以上を含む表面処理層を有し、その上に金属Zr量で20〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 (3) at least on the steel sheet one side, Ni and the 10 to 1000 mg / m 2, Sn has a surface treatment layer containing one or more 80~6000mg / m 2 as metallic Sn as metal Ni, metal Zr content thereon can manufacturing in the 20 to 500 mg / m 2 of Zr, a film that combines phenolic resin 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the P content was applied by cathodic electrolysis treatment Steel plate for containers with excellent processing characteristics.

)少なくとも鋼板片面に、金属Zr量で20〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 (4) the composite to at least the steel sheet one side, the metal Zr amount 20 to 500 mg / m 2 of Zr, the phenolic resin of 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the amount of P The steel plate for containers which was excellent in the can-making process characteristic which gave the coated film | membrane by the cathodic electrolysis process .

以上述べたように、本発明により製造された製缶加工性に優れたラミネート容器用鋼板は、優れた絞りしごき加工、溶接性、耐食性、塗料密着性、フィルム密着性を有することが明らかになった。   As described above, it is clear that the steel sheet for laminate containers manufactured by the present invention and excellent in can-making process has excellent drawing ironing, weldability, corrosion resistance, paint adhesion, and film adhesion. It was.

以下に、本発明の作用である製缶加工性に優れた容器用鋼板について詳細に説明する。本発明で用いられる原板は特に規制されるものではなく、通常、容器材料として使用される鋼板を用いる。この原板の製造法、材質なども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、酸先、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。この原板にNi、Snの1種以上を含む表面処理層が付与されるが、付与する方法については特に規制するものでは無い。例えば、電気めっき法や真空蒸着法やスパッタリング法などの公知技術を用いれば良く、拡散層を付与するための加熱処理を組み合わせても良い。また、NiはFe−Ni合金めっきを行っても本発明の本質は不変である。   Below, the steel plate for containers excellent in can manufacturing process which is an effect | action of this invention is demonstrated in detail. The original plate used in the present invention is not particularly restricted, and usually a steel plate used as a container material is used. There are no particular restrictions on the manufacturing method and material of the original plate, and the original plate is manufactured through steps such as hot rolling, acid tip, cold rolling, annealing, temper rolling, etc. from a normal slab manufacturing process. A surface treatment layer containing one or more of Ni and Sn is applied to the original plate, but the method of applying is not particularly restricted. For example, a known technique such as an electroplating method, a vacuum evaporation method, or a sputtering method may be used, and a heat treatment for providing a diffusion layer may be combined. Further, even if Ni is plated with Fe—Ni alloy, the essence of the present invention is not changed.

こうして付与されたNi、Snの1種以上を含む表面処理層において、Niは金属Niとして10〜1000mg/m2 、Snは金属Snとして80〜6000mg/m2 に規制される。Snは優れた加工性、溶接性を発揮する。この効果が発現するのは、金属Snとして80mg/m2 以上必要である。十分な溶接性を確保するためには200mg/m2 以上、十分な加工性を確保するためには、1000mg/m2 以上付与する事が望ましい。 In the surface treatment layer containing one or more of Ni and Sn applied in this way, Ni is regulated to 10 to 1000 mg / m 2 as metal Ni and Sn is regulated to 80 to 6000 mg / m 2 as metal Sn. Sn exhibits excellent workability and weldability. This effect is required to be 80 mg / m 2 or more as metal Sn. In order to ensure sufficient weldability, it is desirable to apply 200 mg / m 2 or more, and in order to ensure sufficient workability, it is desirable to apply 1000 mg / m 2 or more.

Sn付着量の増加に伴い、Snの優れた加工性、溶接性の向上効果は増加するが、6000mg/m2 以上ではその向上効果が飽和するため経済的に不利である。従って、Snの付着量は金属Snとして6000mg/m2 以下にする必要がある。また、Snめっき後にリフロー処理を行うことによりSn合金層が形成され耐食性がより一層向上する。 As the Sn adhesion amount increases, the improvement effect of excellent workability and weldability of Sn increases, but if it is 6000 mg / m 2 or more, the improvement effect is saturated, which is economically disadvantageous. Therefore, the amount of Sn deposited needs to be 6000 mg / m 2 or less as metallic Sn. Further, by performing a reflow treatment after Sn plating, an Sn alloy layer is formed, and the corrosion resistance is further improved.

Niは塗料密着性、フィルム密着性、耐食性、溶接性にその効果を発揮し、その為には、金属Niとして、10mg/m2 以上のNiが必要である。Niの付着量の増加に伴い、Niの優れたフィルム密着性、耐食性、溶接性の向上効果は増加するが、1000mg/m2 以上ではその向上効果が飽和するため経済的に不利である。従って、Niの付着量は金属Niとして10mg/m2 以上、1000mg/m2 以下に規制される。 Ni exerts its effects on paint adhesion, film adhesion, corrosion resistance, and weldability. For this purpose, Ni of 10 mg / m 2 or more is necessary as metal Ni. With an increase in the amount of Ni deposited, the improvement effect of excellent film adhesion, corrosion resistance and weldability of Ni increases. However, if it is 1000 mg / m 2 or more, the improvement effect is saturated, which is economically disadvantageous. Therefore, the adhesion amount of Ni is regulated to 10 mg / m 2 or more and 1000 mg / m 2 or less as metal Ni.

これらのNi、Snの1種以上を含む表面処理層の上層に、本発明の本質とする処である、Zr皮膜、リン酸皮膜、フェノール樹脂皮膜が付与される。これらの皮膜を付与する方法は、Zrイオン、リン酸イオン、低分子のフェノール樹脂を溶解させた酸性溶液に鋼板を浸漬する方法や陰極電解処理により行う方法があるが、浸漬処理では、下地をエッチングして各種の皮膜が形成される為、付着が不均一になり、また、処理時間も長くなる為、工業生産的には不利である。   A Zr film, a phosphoric acid film, and a phenol resin film, which are the essence of the present invention, are applied to the upper layer of the surface treatment layer containing one or more of these Ni and Sn. Methods for applying these films include a method of immersing a steel plate in an acidic solution in which Zr ions, phosphate ions, and low molecular weight phenolic resins are dissolved, and a method of performing cathodic electrolysis. Since various films are formed by etching, the adhesion becomes non-uniform, and the processing time becomes longer, which is disadvantageous for industrial production.

一方、陰極電解処理では、強制的な電荷移動および鋼板界面での水素発生による表面清浄化とpH上昇による付着促進効果も相俟って、均一な皮膜が数秒から数十秒程度の短時間処理が可能である事から、工業的には極めて有利である。従って、本発明のZr皮膜、リン酸皮膜、フェノール樹脂皮膜の付与には陰極電解処理が望ましい。また、浸漬処理や陰極電解処理に使用する酸性溶液中にタンニン酸を添加すると、タンニン酸がFeと結合し、表面にタンニン酸Feの皮膜を形成し耐錆性や密着性を向上させる効果がある事から、用途に依ってはタンニン酸を添加した溶液中で処理しても良い。   On the other hand, in the cathode electrolysis treatment, a uniform film can be treated for a short time of several seconds to several tens of seconds, combined with forced charge transfer, surface cleaning by hydrogen generation at the steel plate interface, and adhesion promotion effect by pH increase. Therefore, it is extremely advantageous industrially. Accordingly, cathodic electrolysis is desirable for the application of the Zr film, phosphoric acid film, and phenol resin film of the present invention. In addition, when tannic acid is added to an acidic solution used for immersion treatment or cathodic electrolysis, tannic acid is combined with Fe, and a film of Fe tannic acid is formed on the surface, thereby improving rust resistance and adhesion. Therefore, depending on the application, the treatment may be performed in a solution to which tannic acid is added.

Zr皮膜は単独に使用しても優れた実用特性を有しているが、リン酸皮膜、フェノール樹脂皮膜は単独に使用してもある程度の効果は認められるのみで、十分な実用性能が有していない。しかし、リン酸皮膜とフェノール樹脂皮膜を複合した皮膜では優れた実用性能を発揮する。また、Zr皮膜にリン酸皮膜あるいはフェノール皮膜の1種以上複合するとより一層優れた実用性能が発揮される。   The Zr film has excellent practical characteristics even when used alone, but the phosphoric acid film and the phenol resin film have sufficient practical performance with only a certain degree of effect even when used alone. Not. However, a film in which a phosphate film and a phenol resin film are combined exhibits excellent practical performance. In addition, when the Zr film is combined with one or more of a phosphoric acid film or a phenol film, a further excellent practical performance is exhibited.

Zr皮膜の役割は、耐食性と密着性、特に加工密着性の確保である。Zr皮膜は、酸化Zr、水酸化Zr、フッ化Zr、リン酸Zr等のZr化合物あるいはこれらの複合皮膜から構成されるが、これらのZr化合物は優れた耐食性と密着性を有している。従って、Zr皮膜が金属Zr量で1mg/m2 以上になると、耐食性や密着性が向上し始めるが、実用上、安定した問題ないレベルの耐食性と密着性を確保するには、金属Zr量で20mg/m2 以上にする事が好ましい。 The role of the Zr film is to ensure corrosion resistance and adhesion, particularly processing adhesion. The Zr coating is composed of a Zr compound such as Zr oxide, hydroxide Zr, Zr fluoride, Zr phosphate, or a composite coating thereof, and these Zr compounds have excellent corrosion resistance and adhesion. Therefore, when the Zr film has a metal Zr amount of 1 mg / m 2 or more, the corrosion resistance and adhesion start to improve. However, in order to ensure a stable and practical level of corrosion resistance and adhesion, 20 mg / m 2 or more is preferable.

更に、Zr皮膜量が増加すると耐食性、密着性の向上効果も増加するが、Zr皮膜量が金属Zr量で500mg/m2 を超えると、Zr皮膜が厚くなり過ぎZr皮膜自体の密着性が劣化すると共に電気抵抗が上昇し溶接性が劣化する。従って、Zr皮膜付着量は金属Zr量で1〜500mg/m2 にする必要がある。 Furthermore, when the amount of Zr film increases, the effect of improving corrosion resistance and adhesion also increases, but when the amount of Zr film exceeds 500 mg / m 2 in terms of metal Zr, the Zr film becomes too thick and the adhesion of the Zr film itself deteriorates. In addition, the electrical resistance increases and the weldability deteriorates. Therefore, the Zr film adhesion amount needs to be 1 to 500 mg / m 2 in terms of metal Zr amount.

リン酸皮膜の役割は、耐食性と密着性、特に加工密着性の確保である。リン酸皮膜は、下地と反応して形成されるリン酸Fe、リン酸Sn、リン酸Niやリン酸Zrやリン酸−フェノール樹脂皮膜等の皮膜あるいはこれらの複合皮膜から構成されるが、これらのリン酸皮膜は優れた耐食性と密着性を有している。従って、リン酸皮膜が増加すると、耐食性や密着性が向上し始め、P量で、0.1mg/m2 以上になると、実用上、問題ないレベルの耐食性と密着性が確保される。 The role of the phosphoric acid film is to ensure corrosion resistance and adhesion, particularly processing adhesion. The phosphate film is composed of a film such as Fe phosphate, Sn phosphate, Ni phosphate, Zr phosphate, phosphate-phenol resin film or a composite film of these formed by reacting with the base. The phosphoric acid film has excellent corrosion resistance and adhesion. Therefore, when the phosphoric acid film increases, the corrosion resistance and adhesion begin to improve, and when the P amount is 0.1 mg / m 2 or more, a practically satisfactory level of corrosion resistance and adhesion are secured.

更に、リン酸皮膜量が増加すると耐食性、密着性の向上効果も増加するが、リン酸皮膜量がP量で100mg/m2 を超えると、リン酸皮膜が厚くなり過ぎリン酸皮膜自体の密着性が劣化すると共に電気抵抗が上昇し溶接性が劣化する。従って、リン酸皮膜付着量はP量で0.1〜100mg/m2 にする必要がある。 Furthermore, when the amount of phosphoric acid film increases, the effect of improving corrosion resistance and adhesion also increases. However, when the amount of phosphoric acid film exceeds 100 mg / m 2 in terms of P amount, the phosphoric acid film becomes too thick and adhesion of the phosphoric acid film itself is increased. As a result, the electrical resistance increases and the weldability deteriorates. Therefore, it is necessary that the phosphoric acid film adhesion amount is 0.1 to 100 mg / m 2 in terms of P amount.

フェノール樹脂皮膜の役割は密着性、特に加工密着性の確保である。フェノール樹脂自体が有機物であることから塗料やラミネートフィルムと非常に優れた密着性を有している。表面処理層が大きく変形するような加工を受ける場合、表面処理層自体がその加工により凝集破壊され、密着性が劣化する場合があるが、フェノール樹脂は、Zr皮膜やリン酸皮膜の加工密着性を著しく向上せしめる効果を有している。従って、フェノール樹脂皮膜が増加すると密着性が向上し始め、C量で、0.1mg/m2 以上になると、実用上、問題ないレベルの密着性が確保される。 The role of the phenolic resin film is to ensure adhesion, particularly processing adhesion. Since the phenol resin itself is an organic substance, it has excellent adhesion to paints and laminate films. When the surface treatment layer undergoes processing that greatly deforms, the surface treatment layer itself may be coherently broken due to the processing, and adhesion may deteriorate. However, phenolic resins are processed adhesion of Zr film and phosphate film. Has the effect of remarkably improving. Therefore, when the phenol resin film increases, the adhesiveness starts to improve. When the C amount is 0.1 mg / m 2 or more, a practically satisfactory level of adhesiveness is secured.

更に、フェノール樹脂皮膜量が増加すると密着性の向上効果も増加するが、フェノール樹脂皮膜量がC量で100mg/m2 を超えると、電気抵抗が上昇し溶接性が劣化する。従って、リン酸皮膜付着量はC量で0.1〜100mg/m2 にする必要がある。 Furthermore, when the amount of the phenol resin film increases, the effect of improving the adhesion also increases. However, when the amount of the phenol resin film exceeds 100 mg / m 2 in terms of the C amount, the electrical resistance increases and the weldability deteriorates. Therefore, it is necessary that the phosphoric acid film adhesion amount is 0.1 to 100 mg / m 2 in terms of C amount.

以下に、本発明の実施例及び比較例についてに述べ、その結果を表1に示す。
以下の処理法は(0)〜()の方法を用いて板厚0.17〜0.23mmの鋼板上に表面処理層を付与した。
(処理法0)冷間圧延後、焼鈍、調圧された原板に脱脂、酸洗を施した鋼板を作製した。
Hereinafter, Examples and Comparative Examples of the present invention will be described, and the results are shown in Table 1.
In the following treatment method, a surface treatment layer was applied on a steel plate having a thickness of 0.17 to 0.23 mm using the methods (0) to ( 3 ).
(Treatment method 0) After cold rolling, a steel sheet was prepared by degreasing and pickling the annealed and pressure-adjusted original sheet.

(処理法)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、ワット浴を用いてNiめっきを施し、Niめっき鋼板を作製した。
(処理法)冷間圧延後、焼鈍、調圧された原板に脱脂、酸洗後、フェロスタン浴を用いてSnをめっきし、その後、リフロー処理を行い、Sn合金層を有するSnめっき鋼板を作製した。
(Treatment method 1 ) After cold rolling, the annealed and regulated original sheet was degreased, pickled, and then Ni-plated using a Watt bath to prepare a Ni-plated steel sheet.
(Treatment method 2 ) After cold rolling, annealed and pressure-controlled original sheet is degreased, pickled, plated with Sn using a ferrostan bath, and then subjected to reflow treatment to obtain a Sn-plated steel sheet having a Sn alloy layer Produced.

(処理法)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、硫酸−塩酸浴を用いてSn−Ni合金めっきを施し、Ni、Snめっき鋼板を作製した。 (Treatment method 3 ) After cold rolling, the annealed and regulated original plate was degreased, pickled, and then subjected to Sn-Ni alloy plating using a sulfuric acid-hydrochloric acid bath to prepare Ni and Sn plated steel plates.

上記の処理により表面処理層を付与した後、以下の処理法()〜()でZr皮膜、リン酸皮膜、フェノール樹脂皮膜を付与した。
(処理法)フッ化Zrを溶解させた処理液に上記鋼板を浸漬し、陰極電解後、乾燥し、Zr皮膜を付与した。
(処理法)フッ化Zr、リン酸、フェノール樹脂を溶解させた処理液に、上記鋼板を浸漬し、陰極電解後、乾燥し、Zr皮膜、リン酸皮膜、フェノール樹脂皮膜を付与した。
After the surface treatment layer was applied by the above treatment, a Zr film, a phosphoric acid film, and a phenol resin film were applied by the following treatment methods ( 4 ) to ( 6 ).
(Treatment method 4 ) The steel sheet was immersed in a treatment solution in which Zr fluoride was dissolved, and after cathodic electrolysis, it was dried to give a Zr film.
(Treatment method 5 ) The steel sheet was immersed in a treatment solution in which Zr fluoride, phosphoric acid, and a phenol resin were dissolved, and after cathodic electrolysis, dried to give a Zr film, a phosphate film, and a phenol resin film.

(処理法)リン酸、フェノール樹脂を溶解させた処理液に、上記鋼板を浸漬し、陰極電解後、乾燥し、リン酸皮膜、フェノール樹脂皮膜を付与した。 (Treatment method 6 ) The steel sheet was immersed in a treatment solution in which phosphoric acid and a phenol resin were dissolved, and after cathodic electrolysis, it was dried to give a phosphoric acid film and a phenol resin film.

上記の処理を行った試験材について、以下に示す(A)〜(F)の各項目についての性能評価を行った。
(A)加工性
試験材の両面に厚さ20umのPETフィルムを200℃でラミネートし、絞り加工としごき加工による製缶加工を段階的に行い、成型を4段階(◎:非常に良い、○:良い、△:疵が認められる、×:破断し加工不能)で評価した。
About the test material which performed said process, the performance evaluation about each item of (A)-(F) shown below was performed.
(A) PET film having a thickness of 20 μm is laminated at 200 ° C. on both sides of the workability test material, canned processing by drawing and ironing is performed in stages, and molding is performed in four stages (◎: very good, ○ : Good, Δ: wrinkles were observed, x: fractured and unworkable).

(B)溶接性
ワイヤーシーム溶接機を用いて、溶接ワイヤースピード80m/minの条件で、電流を変更して試験材を溶接し、十分な溶接強度が得られる最小電流値とチリ及び溶接スパッタなどの溶接欠陥が目立ち始める最大電流値からなる適正電流範囲の広さおよび溶接欠陥の発生状況かから総合的に判断して、4段階(◎:非常に良い、○:良い、△:劣る、×:溶接不能)で溶接性を評価した。
(B) Using a weldable wire seam welder, the current is changed under the conditions of a welding wire speed of 80 m / min, the test material is welded, and the minimum current value that provides sufficient welding strength, dust and welding spatter, etc. 4 steps (◎: very good, ○: good, △: inferior, ×) comprehensively judged from the wide range of the appropriate current range consisting of the maximum current value at which the welding defect starts to become noticeable and the occurrence state of the welding defect : Weldability was evaluated).

(C)フィルム密着性
試験材の両面に厚さ20umのPETフィルムを200℃でラミネートし、絞りしごき加工を行い、缶体を作製し、125℃、30minのレトルト処理を行い、缶内外面のフィルムの剥離状況を、4段階(◎:全く剥離無し、○:実用上問題無い程度の極僅かな剥離有り、△:僅かな剥離有り、×:大部分で剥離)で評価した。
(C) Laminate a PET film having a thickness of 20 μm on both surfaces of the film adhesion test material at 200 ° C., squeeze and iron it to produce a can body, perform a retort treatment at 125 ° C. for 30 minutes, The peeling state of the film was evaluated in four stages (◎: no peeling at all, ○: very slight peeling with no practical problem, Δ: slight peeling, ×: peeling at most).

(D)塗料密着性
試験材にエポキシ−フェノール樹脂を塗布し、200℃、30minで焼付けた後、1mm間隔で地鉄に達する深さのゴメン目を入れ、テープで剥離し、剥離状況を4段階(◎:全く剥離無し、○:実用上問題無い程度の極僅かな剥離有り、△:僅かな剥離有り、×:大部分で剥離)で評価した。
(D) An epoxy-phenol resin is applied to the paint adhesion test material, baked at 200 ° C. for 30 minutes, and then cut off at a depth of 1 mm to reach the iron core, and peeled off with tape. Evaluation was made at the stage ((: no peeling at all, ○: slight peeling at a practical level, Δ: slight peeling, ×: peeling at most).

(E)耐食性
試験材にエポキシ−フェノール樹脂を塗布し、200℃、30minで焼付けた後、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%食塩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。
(E) After applying an epoxy-phenolic resin to the corrosion resistance test material and baking at 200 ° C. for 30 minutes, put a crosscut at a depth reaching the base iron, and mix 1.5% citric acid-1.5% salt In a test solution consisting of: 45 ° C for 72 hours, washed, dried, and then peeled off from the tape. There are 4 levels of cross-cut corrosion under the coating and flat corrosion (◎: under-corrosion corrosion) Not recognized, ○: Slight under-coating corrosion to the extent that there is no practical problem is observed, Δ: Corrosion under micro-corrosion and slight corrosion is observed in the flat plate part, ×: Severe corrosive under-coating corrosion and flat plate The corrosion was recognized in the part) and evaluated.

(F)耐錆性
試験材を乾湿繰返し(湿度90%、2hr←→湿度40%、2hr)の雰囲気中に2ヶ月間放置し、錆の発生状況を4段階(◎:全く発錆無し、○:実用上問題無い程度の極僅かな発錆有り、△:僅かな発錆有り、×:大部分で発錆)で評価した。
(F) The rust resistance test material is left in an atmosphere of repeated drying and wetting (humidity 90%, 2 hr ← → humidity 40%, 2 hr) for 2 months, and the rust generation status is divided into 4 levels (◎: no rusting, (Circle): There was very slight rusting to the extent that there is no problem in practical use, (triangle | delta): There was slight rusting, and x: Rust was mostly evaluated.

Figure 0005093797
表1に示すように、No.1〜は本発明例であり、No.8〜9は比較例である。比較例No.はZr付着量が低く、しかもリン酸皮膜、フェノール樹脂皮膜もないことから、加工性、溶接性、フィルム密着性、塗料密着性、耐食性および耐錆性のいずれも悪い。また、比較例No.は鋼板にNi層を形成しているが、そのNi量が低く、かつリン酸皮膜およびフェノール樹脂皮膜の付着量がいずれも低いために、加工性が劣り、かつ溶接性、フィルム密着性、塗料密着性、耐食性および耐錆性のいずれも悪い。
これに対して、本発明例であるNo.1〜はいずれも本発明の条件を満たしていることから、加工性、溶接性、フィルム密着性、塗料密着性、耐食性および耐錆性のいずれも優れていることが分かる。
Figure 0005093797
As shown in Table 1, no. 1-7 is an example of the present invention, No. 8 to 9 are comparative examples. Comparative Example No. Since No. 8 has a low Zr adhesion amount and no phosphoric acid film or phenol resin film, all of workability, weldability, film adhesion, paint adhesion, corrosion resistance and rust resistance are poor. Comparative Example No. No. 9 has a Ni layer formed on the steel sheet, but its Ni amount is low, and since both the phosphoric acid film and the phenolic resin film are low in adhesion, workability is inferior, and weldability, film adhesion, Paint adhesion, corrosion resistance and rust resistance are all poor.
On the other hand, No. which is an example of the invention. Both 1-7 from that meets the conditions of the present invention, workability, weldability, film adhesion property, coating adhesion, that is none of the corrosion resistance and rust resistance superior seen.

Claims (4)

少なくとも鋼板片面に、金属Zr量で1〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 At least on the steel sheet one side of 1-500 mg / m 2 of metal Zr content Zr, the composite was coating the phenolic resin of 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the amount of P Steel plate for containers with excellent can-making characteristics imparted by cathodic electrolysis . 少なくとも鋼板片面に、Niを金属Niとして10〜1000mg/m2 、Snを金属Snとして80〜6000mg/m2 の1種以上を含む表面処理層を有し、その上に金属Zr量で1〜500mg/m2 のZr、P量で12〜100mg/m2のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 At least on the steel sheet one side, Ni and the 10 to 1000 mg / m 2, Sn has a surface treatment layer containing one or more 80~6000mg / m 2 as metallic Sn as metal Ni,. 1 to a metal Zr content thereon 500 mg / m 2 of Zr, the can-processing characteristics of the film obtained by combining a phenolic resin of 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the P content imparted by cathodic electrolysis treatment Excellent steel plate for containers. 少なくとも鋼板片面に、Niを金属Niとして10〜1000mg/m2 、Snを金属Snとして80〜6000mg/m2 の1種以上を含む表面処理層を有し、その上に金属Zr量で20〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 At least on the steel sheet one side, Ni and having a surface treatment layer containing one or more 80~6000mg / m 2 of 10 to 1000 mg / m 2, Sn as Sn metal as metal Ni,. 20 to a metal Zr content thereon 500 mg / m 2 of Zr, the can-processing characteristics of the film obtained by combining a phenolic resin of 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the P content imparted by cathodic electrolysis treatment Excellent steel plate for containers. 少なくとも鋼板片面に、金属Zr量で20〜500mg/m2 のZr、P量で12〜100mg/m2 のリン酸およびC量で0.1〜100mg/m2 のフェノール樹脂を複合した皮膜を陰極電解処理により付与した製缶加工特性に優れた容器用鋼板。 At least on the steel sheet one side of 20 to 500 mg / m 2 of metal Zr content Zr, the composite was coating the phenolic resin of 0.1-100 mg / m 2 with phosphoric acid and the C content of 12 -100 mg / m 2 in the amount of P Steel plate for containers with excellent can-making characteristics imparted by cathodic electrolysis .
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