JP4626518B2 - Surface-treated metal plate and manufacturing method thereof, resin-coated metal plate, metal can and can lid - Google Patents
Surface-treated metal plate and manufacturing method thereof, resin-coated metal plate, metal can and can lid Download PDFInfo
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Description
本発明は、主に缶などの容器に加工して用いられる金属板、特にプラスチックフィルムなどの樹脂との密着性(以後、樹脂密着性と呼ぶ)に優れる表面処理金属板およびその製造方法、ならびにこの表面処理金属板に有機樹脂が被覆された樹脂被覆金属板、それを用いた金属缶および缶蓋に関する。 The present invention is a metal plate that is mainly processed into a container such as a can, and in particular, a surface-treated metal plate excellent in adhesion to a resin such as a plastic film (hereinafter referred to as resin adhesion), and a method for producing the same, and The present invention relates to a resin-coated metal plate in which an organic resin is coated on the surface-treated metal plate, a metal can using the same, and a can lid.
飲料缶、食品缶、ペール缶や18リットル缶などの各種金属缶には、錫めっき鋼板やティンフリー鋼板と呼ばれる電解クロム酸処理鋼板などの金属板が用いられている。なかでも、ティンフリー鋼板は、6価クロムを含む浴中で鋼板を電解処理することにより製造され、塗料などとの優れた樹脂密着性を有していることに特長がある。 Various metal cans such as beverage cans, food cans, pail cans and 18 liter cans use metal plates such as electrolytic chromic acid treated steel plates called tin-plated steel plates or tin-free steel plates. Among these, tin-free steel plates are manufactured by electrolytic treatment of steel plates in a bath containing hexavalent chromium, and are characterized by excellent resin adhesion to paints and the like.
近年、環境に対する意識の高まりから、世界的に6価クロムの使用が規制される方向に向かっており、製造に6価クロム浴を用いるティンフリー鋼板に対しても代替材が求められている。クロムを用いないティンフリー鋼板の代替材として、例えば特許文献1には、タングステン酸溶液中で電解処理が施された容器用鋼板が開示されている。また、特許文献2には、表面にリン酸塩層が形成された容器用表面処理鋼板が開示されている。さらに、特許文献3には、Sn、Niの１種以上を含む表面処理層を有し、その上にタンニン酸または酢酸の１種以上およびTiまたはZrまたはそれらの化合物の１種以上を含んだフェノール構造を有する樹脂皮膜を施す容器用鋼板が提案されている。 In recent years, with the increasing awareness of the environment, the use of hexavalent chromium has been restricted worldwide, and alternative materials are also required for tin-free steel sheets that use a hexavalent chromium bath for production. As an alternative to tin-free steel plates that do not use chromium, for example, Patent Document 1 discloses a steel plate for containers that has been subjected to electrolytic treatment in a tungstic acid solution. Patent Document 2 discloses a surface-treated steel sheet for containers having a phosphate layer formed on the surface. Furthermore, Patent Document 3 has a surface treatment layer containing at least one of Sn and Ni, and further includes at least one of tannic acid or acetic acid and at least one of Ti or Zr or a compound thereof. A steel plate for a container to which a resin film having a phenol structure is applied has been proposed.
一方、各種金属缶は、従来より、ティンフリー鋼板などの金属板に塗装を施した後に、缶体に加工して製造されていたが、近年、製造に伴う廃棄物の抑制のために、塗装に代わってプラスチックフィルムなどの樹脂をラミネートしたラミネート金属板(樹脂被覆金属板)を缶体に加工する方法が多用されるようになっている。このラミネート金属板には、樹脂と金属板が強く密着していることが必要であり、特に飲料缶や食品缶として用いられるラミネート金属板には、内容物の充填後にレトルト殺菌工程を経る場合があるため、高温の湿潤環境でも樹脂が剥離することのない強い樹脂密着性が要求される。
しかしながら、特許文献1に記載のタングステン酸溶液中で電解処理が施された容器用鋼板、特許文献2に記載の表面にリン酸塩層が形成された容器用表面処理鋼板を用いたラミネート鋼板、および特許文献3に記載のフェノール構造を有する樹脂皮膜を施す容器用鋼板では、いずれもレトルト殺菌工程における樹脂密着性が不十分である。 However, a steel plate for containers subjected to electrolytic treatment in the tungstic acid solution described in Patent Document 1, a laminated steel plate using a surface-treated steel sheet for containers in which a phosphate layer is formed on the surface described in Patent Document 2, In both the steel sheet for containers to which the resin film having a phenol structure described in Patent Document 3 is applied, the resin adhesion in the retort sterilization process is insufficient.
本発明は、クロムを用いず、樹脂密着性に優れ、ティンフリー鋼板の代替材となり得る表面処理金属板およびその製造方法、ならびにこの表面処理金属板に有機樹脂が被覆された樹脂被覆金属板、それを用いた金属缶および缶蓋を提供することを目的とする。 The present invention provides a surface-treated metal plate that does not use chromium, has excellent resin adhesion, and can be used as a substitute for a tin-free steel plate, and a method for producing the same, and a resin-coated metal plate obtained by coating the surface-treated metal plate with an organic resin, An object is to provide a metal can and a can lid using the same.
本発明者らは、クロムを用いず、樹脂密着性に優れる表面処理金属板について鋭意研究を重ねた結果、表面にTiおよびOを含む皮膜を形成し、その皮膜上にさらに有機皮膜を形成することにより極めて優れた樹脂密着性が得られることを見出した。 As a result of intensive research on a surface-treated metal plate excellent in resin adhesion without using chromium, the present inventors formed a film containing Ti and O on the surface, and further formed an organic film on the film It was found that extremely excellent resin adhesion can be obtained.
本発明は、このような知見に基づきなされたもので、金属板の少なくとも片面に、TiおよびOを含む皮膜を有し、前記皮膜上にクエン酸、酒石酸、グリコール酸、乳酸、グリセリン酸、マンデル酸の中から選ばれた少なくとも1種の酸を塗布した後、乾燥することにより形成された有機皮膜を有することを特徴とする表面処理金属板を提供する。 The present invention has been made based on such knowledge, and has a film containing Ti and O on at least one surface of a metal plate, and citric acid, tartaric acid, glycolic acid, lactic acid, glyceric acid, mandel on the film. There is provided a surface-treated metal sheet characterized by having an organic film formed by applying at least one acid selected from acids and drying it .
本発明の表面処理金属板では、TiおよびOを含む皮膜のTi量が3〜200mg/m2であることが好ましい。 In the surface-treated metal plate of the present invention, it is preferable that the Ti content of the coating containing Ti and O is 3 to 200 mg / m 2 .
本発明は、また、本発明の表面処理金属板の有機皮膜上に、有機樹脂が被覆されている樹脂被覆金属板、それを用いた金属缶および缶蓋を提供する。 The present invention also provides a resin-coated metal plate in which an organic resin is coated on the organic film of the surface-treated metal plate of the present invention, a metal can and a can lid using the same.
本発明の表面処理鋼板は、例えば、フルオロチタン酸イオンを含む水溶液中で金属板を陰極電解処理してTiおよびOを含む皮膜を形成後、クエン酸、酒石酸、グリコール酸、乳酸、グリセリン酸、マンデル酸の中から選ばれた少なくとも1種の酸を塗布し、乾燥して有機皮膜を形成する方法により製造可能である。 The surface-treated steel sheet of the present invention is, for example, after cathodic electrolytic treatment of a metal plate in an aqueous solution containing fluorotitanate ions to form a film containing Ti and O, citric acid, tartaric acid, glycolic acid, lactic acid, glyceric acid, It can be produced by a method in which at least one acid selected from mandelic acid is applied and dried to form an organic film.
本発明により、クロムを用いず、樹脂密着性に優れる表面処理金属板を製造できるようになった。本発明の表面処理金属板は、これまでのティンフリー鋼板の代替材として問題なく、有機樹脂を被覆して樹脂被覆金属板とし、金属缶や缶蓋に加工しても、樹脂の剥離が全く起こらず加工できる。 According to the present invention, it is possible to produce a surface-treated metal plate that is excellent in resin adhesion without using chromium. The surface-treated metal plate of the present invention has no problem as an alternative to the conventional tin-free steel plate, and is coated with an organic resin to form a resin-coated metal plate. Can be processed without happening.
1)表面処理金属板
本発明の表面処理金属板では、金属板の少なくとも片面に、TiおよびOを含む皮膜が形成され、さらにこの皮膜上に有機皮膜が形成されている。
1) Surface-treated metal plate In the surface-treated metal plate of the present invention, a film containing Ti and O is formed on at least one surface of the metal plate, and an organic film is further formed on this film.
金属板としては、一般的な缶用の鋼板、アルミニウム板、アルミニウム合金板などを用いることができる。 As the metal plate, a general steel plate for cans, an aluminum plate, an aluminum alloy plate, or the like can be used.
金属板表面に形成されたTiおよびOを含む皮膜は、下地金属板と強固に結合し、金属板に耐食性を付与するとともに、その上に形成された有機皮膜との相乗効果で樹脂密着性を向上させる。 The film containing Ti and O formed on the surface of the metal plate is firmly bonded to the base metal plate to give the metal plate corrosion resistance, and also provides resin adhesion due to the synergistic effect with the organic film formed on it. Improve.
TiおよびOを含む皮膜のTi量は、片面あたり、3mg/m2未満だと樹脂との密着性改善の効果が不十分であり、200mg/m2を超えると更なる密着性の向上が望めず、コスト高となるので、3〜200mg/m2であることが好ましい。なお、皮膜のTi量の測定は、蛍光X線による表面分析により行うことができる。また、O量については、特に規定しないが、XPSによる表面分析でその存在を確認することができる。 If the amount of Ti in the coating containing Ti and O is less than 3 mg / m 2 per side, the effect of improving adhesion with the resin is insufficient, and if it exceeds 200 mg / m 2 , further improvement in adhesion can be expected. However, since it becomes expensive, it is preferable that it is 3-200 mg / m < 2 >. In addition, the measurement of the Ti amount of the film can be performed by surface analysis using fluorescent X-rays. The amount of O is not particularly defined, but its presence can be confirmed by surface analysis using XPS.
TiおよびOを含む皮膜の形成方法としては、フルオロチタン酸イオンを含む水溶液中で金属板を陰極電解処理または浸漬処理する方法、またはフルオロチタン酸イオンおよびフッ素塩を含む水溶液中で金属板を陰極電解処理または浸漬処理する方法等が好適である。フルオロチタン酸イオンを与える化合物としては、フッ化チタン酸、フッ化チタン酸アンモニウム、フッ化チタン酸カリウムなどを用いることができる。フッ素塩としては、フッ化ナトリウム、フッ化カリウム、フッ化銀、フッ化錫などを用いることができる。特に、フッ化チタン酸カリウム水溶液中で、さらにはフッ化チタン酸カリウムおよびフッ化ナトリウムを含む水溶液中で、金属板を陰極電解処理する方法は、効率良く均質な皮膜を形成することが可能であり好適である。なお、陰極電解処理する方法での電流密度および電解時間、ならびに浸漬処理での浸漬時間は、必要なTi量に応じて適宜決定すればよい。 As a method for forming a film containing Ti and O, a method in which a metal plate is subjected to cathodic electrolytic treatment or immersion treatment in an aqueous solution containing fluorotitanate ions, or a metal plate is made into a cathode in an aqueous solution containing fluorotitanate ions and a fluorine salt. A method of electrolytic treatment or immersion treatment is suitable. As the compound that gives fluorotitanate ions, fluorinated titanate, ammonium fluoride titanate, potassium fluoride titanate, and the like can be used. As the fluorine salt, sodium fluoride, potassium fluoride, silver fluoride, tin fluoride, or the like can be used. In particular, the method of cathodic electrolysis of a metal plate in an aqueous solution of potassium fluorinated titanate and further in an aqueous solution containing potassium fluorinated titanate and sodium fluoride can form a uniform film efficiently. It is preferable. In addition, what is necessary is just to determine suitably the current density and electrolysis time in the method of cathodic electrolysis treatment, and the immersion time in immersion treatment according to required Ti amount.
TiおよびOを含む皮膜の形成方法の一例を次に挙げる。金属板にアルカリ脱脂および酸洗を施し、陰極電解処理もしくは浸漬処理を行う。処理液としては、フルオロチタン酸イオンを、Tiにして0.1〜10g/L(L:リットル)、またはさらにフッ素塩を、Fにして0.05〜5g/L含み、温度20〜70℃の水溶液を用いる。陰極電解処理条件の場合は電解時間を0.5〜10sec、電流密度1〜100A/dm2、浸漬処理の場合は浸漬時間1〜10secで行う。その後、水洗し、常温の冷風で乾燥する。その結果、Ti量が3〜200mg/m2のTiおよびOを含有する皮膜を有する表面処理金属板を得られる。 An example of a method for forming a film containing Ti and O is given below. The metal plate is subjected to alkali degreasing and pickling, and subjected to cathodic electrolysis treatment or immersion treatment. As the treatment liquid, an aqueous solution containing 0.1 to 10 g / L (L: liter) of fluorotitanate ion or Ti, further containing 0.05 to 5 g / L of fluorine salt and having a temperature of 20 to 70 ° C. is used. . In the case of cathodic electrolytic treatment conditions, the electrolysis time is 0.5 to 10 seconds and the current density is 1 to 100 A / dm 2. In the case of immersion treatment, the immersion time is 1 to 10 seconds. Then, it is washed with water and dried with cold air at room temperature. As a result, a surface-treated metal plate having a film containing Ti and O with a Ti content of 3 to 200 mg / m 2 can be obtained.
TiおよびOを含む皮膜上に形成される有機皮膜も、その後に被覆するプラスチックフィルムなどとの樹脂密着性に寄与する。有機皮膜を構成する有機物としては、例えばアルコール類、フェノール類、エーテル類、アルデヒド類、ケトン類、カルボン酸類、アミン類等のうち、常温で固体の不揮発性物質が好ましく、このような有機物からなる有機皮膜を形成させることが好ましい。中でも有機酸が好適であり、特にヒドロキシ酸が好適である。ヒドロキシ酸とは、1分子中にカルボキシル基とアルコール性水酸基とを持つ有機化合物の総称であり、本発明では、クエン酸、酒石酸、グリコール酸、乳酸、グリセリン酸、マンデル酸などの中から選ばれた少なくとも1種の酸を用いることができる。この有機皮膜の形成方法としては、上記の有機物を水または有機溶剤に溶解し、溶液として金属板上に塗布した後、乾燥する方法が好適である。塗布方法としては、各種公知のコーティング法を用いることができる。乾燥時間短縮のために、必要に応じて金属板を加熱する工程を設けてもよい。なお、乾燥によって皮膜を形成した後は、水洗工程を経ることによって金属上に残存した過剰な有機物を除去することが好ましい。この場合、特に強力な水洗である必要はなく、水槽に浸漬、あるいは水スプレー程度で十分である。水洗後は、再度乾燥し、実用に供することができる。 An organic film formed on a film containing Ti and O also contributes to resin adhesion with a plastic film or the like to be coated thereafter. The organic substance constituting the organic film is preferably a non-volatile substance that is solid at room temperature among alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids, amines, and the like, and is made of such an organic substance. It is preferable to form an organic film. Of these, organic acids are preferred, and hydroxy acid is particularly preferred. Hydroxy acid is a general term for organic compounds having a carboxyl group and an alcoholic hydroxyl group in one molecule. In the present invention, hydroxy acid is selected from citric acid, tartaric acid, glycolic acid, lactic acid, glyceric acid, mandelic acid, and the like. At least one acid can be used. As a method for forming this organic film, a method in which the above organic substance is dissolved in water or an organic solvent, applied as a solution on a metal plate, and then dried is preferable. As a coating method, various known coating methods can be used. In order to shorten the drying time, a step of heating the metal plate may be provided as necessary. In addition, after forming a film | membrane by drying, it is preferable to remove the excess organic substance which remain | survived on the metal by passing through a water washing process. In this case, it is not necessary to perform particularly strong water washing, and it is sufficient to immerse in a water tank or water spray. After washing with water, it can be dried again and put to practical use.
有機皮膜の付着量は、0.1mg/m2未満だと樹脂密着性の改善効果が不十分であり、50mg/m2を超えると有機皮膜中で凝集破壊が生じ、かえって樹脂密着性が低下する恐れがあるので、0.1〜50mg/m2であることが好ましい。なお、有機皮膜の付着量の測定は、皮膜を水または適当な有機溶媒で溶解し、燃焼して発生した気体の組成をガスクロマトグラフィーで分析することにより行うことができる。 If the adhesion amount of the organic film is less than 0.1 mg / m 2 , the effect of improving the resin adhesion is insufficient, and if it exceeds 50 mg / m 2 , cohesive failure occurs in the organic film, resulting in a decrease in resin adhesion. Since there exists a possibility, it is preferable that it is 0.1-50 mg / m < 2 >. The amount of the organic film deposited can be measured by dissolving the film with water or an appropriate organic solvent and analyzing the composition of the gas generated by combustion by gas chromatography.
2)樹脂被覆金属板(ラミネート金属板)
本発明の表面処理金属板の有機皮膜上に、有機樹脂を被覆して樹脂被覆金属板とすることができる。上述したように、本発明の表面処理金属板は樹脂密着性に優れているため、この樹脂被覆金属板は優れた耐食性と加工性を有する。
2) Resin-coated metal plate (laminated metal plate)
The organic film of the surface-treated metal plate of the present invention can be coated with an organic resin to form a resin-coated metal plate. As described above, since the surface-treated metal plate of the present invention is excellent in resin adhesion, the resin-coated metal plate has excellent corrosion resistance and workability.
本発明の表面処理金属板に被覆する有機樹脂としては、特に限定はなく、各種熱可塑性樹脂や熱硬化性樹脂を挙げることができる。例えば、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン-酢酸ビニル共重合体、エチレン-アクリルエステル共重合体、アイオノンマー等のオレフィン系樹脂フィルム、またはポリブチレンテレフタラート等のポリエステルフィルム、もしくはナイロン6、ナイロン6,6、ナイロン11、ナイロン12等のポリアミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム等の熱可塑性樹脂フィルムの未延伸または二軸延伸したものであってもよい。積層の際に接着剤を用いる場合は、ウレタン系接着剤、エポキシ系接着剤、酸変性オレフィン樹脂系接着剤、コポリアミド系接着剤、コポリエステル系接着剤(厚さ:0.1〜5.0μm)等が好ましく用いられる。さらに熱硬化性塗料を、厚み0.05〜2μmの範囲で表面処理金属板側、あるいはフィルム側に塗布し、これを接着剤としてもよい。 There is no limitation in particular as organic resin coat | covered on the surface treatment metal plate of this invention, Various thermoplastic resins and thermosetting resins can be mentioned. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyester film such as polybutylene terephthalate, or nylon 6 It may be a non-stretched or biaxially stretched thermoplastic resin film such as a polyamide film such as nylon 6,6, nylon 11, or nylon 12, a polyvinyl chloride film, or a polyvinylidene chloride film. When using an adhesive during lamination, urethane adhesive, epoxy adhesive, acid-modified olefin resin adhesive, copolyamide adhesive, copolyester adhesive (thickness: 0.1 to 5.0 μm), etc. Is preferably used. Furthermore, a thermosetting paint may be applied to the surface-treated metal plate side or film side in a thickness range of 0.05 to 2 μm, and this may be used as an adhesive.
さらに、フェノールエポキシ、アミノ-エポキシ等の変性エポキシ塗料、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-酢酸ビニル共重合体けん化物、塩化ビニル-酢酸ビニル-無水マレイン酸共重合体、エポキシ変性-、エポキシアミノ変性-、エポキシフェノール変性-ビニル塗料または変性ビニル塗料、アクリル塗料、スチレン-ブタジェン系共重合体等の合成ゴム系塗料等の熱可塑性または熱硬化性塗料の単独または2種以上の組合わせであってもよい。 Furthermore, modified epoxy paint such as phenol epoxy, amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, epoxy-modified- , Epoxyamino-modified, Epoxyphenol-modified Vinyl paint or Modified vinyl paint, Acrylic paint, Synthetic rubber paint such as styrene-butadiene copolymer, etc. It may be a combination.
本発明において、有機樹脂被覆層の厚みは3〜50μm、特に5〜40μmの範囲にあることが望ましい。厚みが上記範囲を下回ると耐食性が不十分となり、厚みが上記範囲を上回ると加工性の点で問題を生じやすい。 In the present invention, the thickness of the organic resin coating layer is desirably 3 to 50 μm, particularly 5 to 40 μm. When the thickness is below the above range, the corrosion resistance becomes insufficient, and when the thickness is above the above range, problems are likely to occur in terms of workability.
本発明において、表面処理金属板への有機樹脂被覆層の形成は任意の手段で行うことができ、例えば、押出コート法、キャストフィルム熱接着法、二軸延伸フィルム熱接着法等により行うことができる。押出コート法の場合、表面処理金属板の上に有機樹脂を溶融状態で押出コートして、熱接着させることにより製造することができる。すなわち、有機樹脂を押出機で溶融混練した後、T-ダイから薄膜状に押し出し、押し出された溶融樹脂膜を表面処理金属板と共に一対のラミネートロール間に通して冷却下に押圧一体化させ、次いで急冷する。多層の有機樹脂被覆層を押出コートする場合には、表層樹脂用の押出機および下層樹脂用の押出機を使用し、各押出機からの樹脂流を多重多層ダイ内で合流させ、以後は単層樹脂の場合と同様に押出コートを行えばよい。また、一対のラミネートロール間に垂直に表面処理金属板を通し、その両側に溶融樹脂ウエッブを供給することにより、前記表面処理金属板両面に有機樹脂被覆層を形成させることができる。 In the present invention, the formation of the organic resin coating layer on the surface-treated metal plate can be performed by any means, for example, by an extrusion coating method, a cast film thermal bonding method, a biaxially stretched film thermal bonding method, or the like. it can. In the case of the extrusion coating method, it can be produced by extrusion coating an organic resin in a molten state on a surface-treated metal plate and thermally bonding it. That is, after melt-kneading the organic resin with an extruder, it is extruded from the T-die into a thin film, and the extruded molten resin film is passed through a pair of laminating rolls with a surface-treated metal plate to be pressed and integrated under cooling, Then quench rapidly. When extrusion coating a multilayer organic resin coating layer, an extruder for the surface layer resin and an extruder for the lower layer resin are used, and the resin flow from each extruder is merged in a multi-layer die, and thereafter Extrusion coating may be performed as in the case of the layer resin. Moreover, an organic resin coating layer can be formed on both surfaces of the surface-treated metal plate by passing a surface-treated metal plate vertically between a pair of laminate rolls and supplying a molten resin web to both sides thereof.
3)金属缶および缶蓋
本発明の金属缶は、前述した樹脂被覆金属板から形成されている限り、任意の製缶法によるものでよい。この金属缶は、側面継ぎ目を有するスリーピース缶であることもできるが、一般にシームレス缶(ツーピース缶)であることが好ましい。このシームレス缶は、表面処理金属板の有機樹脂の被覆面が缶内面側となるように、絞り・再絞り加工、絞り・再絞りによる曲げ伸ばし加工(ストレッチ加工)、絞り・再絞りによる曲げ伸ばし・しごき加工、あるいは絞り・しごき加工等の従来公知の手段に付すことによって製造される。
3) Metal can and can lid As long as the metal can of the present invention is formed from the above-mentioned resin-coated metal plate, any can-making method may be used. The metal can can be a three-piece can having a side seam, but is generally preferably a seamless can (two-piece can). This seamless can is drawn and redrawn, bent and stretched by drawing and redrawing (stretching), and stretched and drawn by drawing and redrawing so that the surface of the surface-treated metal plate coated with the organic resin faces the inner surface of the can. -It is manufactured by attaching to a conventionally known means such as ironing or drawing / ironing.
また、本発明の缶蓋は、上述した樹脂被覆金属板から形成されている限り、従来公知の任意の製蓋法によるものでよい。一般には、ステイ・オン・タブタイプのイージーオープン缶蓋やフルオープンタイプのイージーオープン缶蓋に適用することができる。 The can lid of the present invention may be formed by any conventionally known lid-making method as long as it is formed from the above-described resin-coated metal plate. In general, the present invention can be applied to a stay-on-tab type easy open can lid and a full open type easy open can lid.
上述したところは、この発明の実施形態の一例を示したに過ぎず、請求の範囲内において種々の変更を加えることができる。 The above description is merely an example of an embodiment of the present invention, and various modifications can be made within the scope of the claims.
金属板として、
A:板厚0.20mm、調質度T-4の低炭素冷延鋼板
B:板厚0.20mm、調質度T-2の極低炭素冷延鋼板
C:板厚0.28mmのJIS5021H18アルミニウム板
を使用し、アルカリ脱脂、酸洗を施した後、表1に示す組成の処理液中で、同じく表1に示す条件で陰極電解処理または浸漬処理を行い、水洗、乾燥してTiおよびOを含有する皮膜を金属板の両面に形成した。陰極電解処理の際は、陽極には酸化イリジウム被覆したチタンを用いた。続いて、表1に示す組成の有機処理液をロールコーターを用いて金属板上に塗布し、80℃の電気炉中で20sec間乾燥した後、水洗して有機皮膜を金属板の両面に形成し、表面処理金属板No.1〜11を作製した。ここで、表面処理金属板No.5では、電解処理ではなく浸漬処理によりTiとOを含む皮膜が金属板の両面に形成されている。
As a metal plate,
A: Low carbon cold-rolled steel sheet with a thickness of 0.20mm and tempering grade T-4
B: Ultra low carbon cold-rolled steel sheet with a thickness of 0.20mm and tempering grade T-2
C: Using a JIS5021H18 aluminum plate with a thickness of 0.28 mm, after performing alkaline degreasing and pickling, in the treatment liquid with the composition shown in Table 1, perform cathodic electrolysis treatment or immersion treatment under the same conditions as shown in Table 1. The film containing Ti and O was formed on both surfaces of the metal plate by washing with water and drying. In the cathode electrolysis treatment, iridium oxide-coated titanium was used for the anode. Subsequently, an organic treatment liquid having the composition shown in Table 1 was applied onto a metal plate using a roll coater, dried in an electric furnace at 80 ° C. for 20 seconds, and then washed with water to form an organic film on both surfaces of the metal plate. Thus, surface-treated metal plates No. 1 to 11 were produced. Here, in the surface-treated metal plate No. 5, films containing Ti and O are formed on both surfaces of the metal plate by dipping treatment instead of electrolytic treatment.
比較のため、金属板Aを用い、表2に示す条件で電解処理を行い、一部の金属板には、その後、表2に示す組成の浸漬処理液に1sec間浸漬して、表面処理金属板No.12〜14を作製した。いずれの金属板にも有機皮膜を形成するための処理は行われていない。ここで、表面処理金属板No.12では、陰極電解処理によりW含有皮膜が、表面処理金属板No.13では、陽極電解処理後、リン酸マグネシウム水溶液に浸漬処理を行ってMg含有皮膜が、形成されている。また、表面処理金属板No.14では、陰極電解処理によりNi含有皮膜が形成された後、浸漬処理によりTi含有フェノール樹脂皮膜が形成されている。 For comparison, electrolytic treatment was performed using the metal plate A under the conditions shown in Table 2, and a portion of the metal plate was then immersed in an immersion treatment liquid having the composition shown in Table 2 for 1 second to obtain a surface-treated metal. Plate No. 12-14 were produced. No treatment for forming an organic film on any metal plate is performed. Here, in the surface-treated metal plate No. 12, the W-containing film is obtained by cathodic electrolysis, and in the surface-treated metal plate No. 13, after the anodic electrolytic treatment, the magnesium-containing film is immersed in an aqueous magnesium phosphate solution. Is formed. Further, in the surface-treated metal plate No. 14, after the Ni-containing film is formed by the cathodic electrolysis treatment, the Ti-containing phenol resin film is formed by the immersion treatment.
表面処理金属板No.1〜11の皮膜のTi量、No.12の皮膜のW量、No.13の皮膜のMg量、No.14の皮膜のNi、Ti量の測定は、それぞれ予め付着量を湿式分析して求めた検量板との比較による蛍光Ｘ線分析により行った。なお、Oは、XPSによる表面分析でその存在を確認した。また、表面処理金属板No.1〜11の有機皮膜の付着量の測定を、水またはエタノールに皮膜を溶解し、燃焼して発生した気体の組成をガスクロマトグラフィー分析することにより行った。皮膜のTi量、W量、Mg量、Ni量、有機皮膜の付着量を、表1、2に示す。 Surface treatment metal plate No.1 to 11 coating Ti amount, No.12 coating W amount, No.13 coating Mg amount, No.14 coating Ni amount, Ti amount measurement are pre-adhered respectively. The amount was measured by fluorescent X-ray analysis by comparison with a calibration plate obtained by wet analysis. The presence of O was confirmed by XPS surface analysis. Moreover, the adhesion amount of the organic film of the surface treatment metal plates No. 1 to 11 was measured by dissolving the film in water or ethanol and analyzing the composition of the gas generated by combustion by gas chromatography. Tables 1 and 2 show the Ti amount, W amount, Mg amount, Ni amount, and organic film adhesion amount of the film.
これらの表面処理金属板No.1〜14の両面に、厚さ25μm、共重合比12mol%のイソフタル酸共重合ポリエチレンテレフタラートフィルム(有機樹脂被覆層)をラミネートして、ラミネート金属板(樹脂被覆金属板)No.1〜14を作製した。ラミネートは、245℃に加熱した金属板とフィルムを一対のゴムロールで挟んでフィルムを金属板に融着させ、ゴムロール通過後1sec以内に水冷して行った。このとき、金属板の送り速度は40m/min、ゴムロールのニップ長は17mmであった。ここで、ニップ長とは、ゴムロールと金属板が接する部分の搬送方向の長さのことである。そして、作製したラミネート金属板No.1〜14について、次の樹脂密着性の評価を行った。 Laminated metal plates (resin coating) were laminated on both surfaces of these surface-treated metal plates No. 1 to 14 with an isophthalic acid copolymerized polyethylene terephthalate film (organic resin coating layer) having a thickness of 25 μm and a copolymerization ratio of 12 mol%. Metal plates No. 1 to 14 were prepared. Lamination was performed by sandwiching a metal plate heated to 245 ° C. and a film between a pair of rubber rolls, fusing the film to the metal plate, and cooling with water within 1 second after passing through the rubber roll. At this time, the feed speed of the metal plate was 40 m / min, and the nip length of the rubber roll was 17 mm. Here, the nip length is the length in the conveyance direction of the portion where the rubber roll and the metal plate are in contact. And about the produced laminated metal plate No. 1-14, the following resin adhesiveness evaluation was performed.
樹脂密着性評価：
温度130℃、相対湿度100%のレトルト雰囲気における180°ピール試験により樹脂密着性の評価を行った。180°ピール試験とは、図1の(a)に示すようなフィルム2を残して金属板1の一部3を切リ取った試験片(サイズ：30mm×100mm)を用い、図1の(b)に示すように、試験片の一端に重り4(100g)を付けてフィルム2側に180°折り返して30min間放置して行うフィルム剥離試験のことである。そして、図1の(c)に示す剥離長5を測定し、次のように樹脂密着性を評価し、◎または○であれば樹脂密着性が良好であるとした。
◎：剥離長が15mm未満
○：剥離長が15mm 以上20mm未満
△：剥離長が20mm以上50mm未満
×：剥離長が50mm以上
樹脂密着性の評価結果を表3に示す。本発明例であるラミネート金属板No.1〜9は、いずれも極めて良好な樹脂密着性を示している。これに対し、比較例であるラミネート金属板No.12〜14は、いずれも樹脂密着性に劣っている。
Resin adhesion evaluation:
Resin adhesion was evaluated by a 180 ° peel test in a retort atmosphere at a temperature of 130 ° C. and a relative humidity of 100%. The 180 ° peel test is a test piece (size: 30 mm × 100 mm) obtained by cutting off a part 3 of the metal plate 1 while leaving the film 2 as shown in FIG. As shown in b), this is a film peeling test performed by attaching a weight 4 (100 g) to one end of the test piece, turning it 180 ° to the film 2 side, and allowing it to stand for 30 minutes. Then, the peel length 5 shown in (c) of FIG. 1 was measured, and the resin adhesion was evaluated as follows.
A: Peeling length is less than 15 mm B: Peeling length is 15 mm or more and less than 20 mm Δ: Peeling length is 20 mm or more and less than 50 mm ×: Peeling length is 50 mm or more Table 3 shows the evaluation results of resin adhesion. Laminated metal plates No. 1 to 9 which are examples of the present invention all show extremely good resin adhesion. To this, laminated metal sheet No.12~14 is a comparative example are all inferior to the resin adhesion.
実施例1で作製したラミネート金属板No.1、3〜6、14を用いて、表4に示す条件で製缶加工を行い、缶胴の開口端をネックイン、フランジ加工して金属シームレス缶No.1〜6を作製した。また、同じラミネート金属板を用いて、209径のSOT蓋を作製し、スコア加工部内外面をエポキシフェノール系塗料で補修した。 Using the laminated metal plates No.1, 3-6, and 14 produced in Example 1, the can is processed under the conditions shown in Table 4, and the opening end of the can body is necked in and flanged to form a metal seamless can No. 1-6 were produced. In addition, using the same laminated metal plate, a 209-diameter SOT lid was prepared, and the inner and outer surfaces of the score processed part were repaired with an epoxy phenol-based paint.
作製した金属缶No.1〜6および蓋について、製缶後のフィルムの剥離や穴あきなどの異常の有無を目視で調査した。また、金属缶に50℃でコーヒー飲料を充填した後、蓋を2重巻締めし、125℃で25min間のレトルト処理を行い、37℃で6ヶ月放置後開缶して、缶内面側の腐食やフィルム異常を目視で調査した。 The produced metal cans Nos. 1 to 6 and the lids were visually inspected for abnormalities such as peeling of the film after the can making and perforation. After filling a metal can with a coffee drink at 50 ° C, double-wrap the lid, perform a retort treatment at 125 ° C for 25 min, leave it at 37 ° C for 6 months, and then open the can. Corrosion and film abnormalities were examined visually.
結果を表5に示す。本発明であるラミネート金属板を用いた金属缶No.1〜5には、製缶後および内容物充填後、金属缶および蓋を調べたが、いずれにおいてもフィルムの異常は確認できなかった。 The results are shown in Table 5. For metal cans Nos. 1 to 5 using the laminated metal plate according to the present invention, the metal can and the lid were examined after making the can and filling the contents, but in any case, no abnormality of the film could be confirmed.
一方、本発明でないラミネート金属板を用いた金属缶No.6では、製缶後にフィルム異常や、内容物充填後にフィルム異常(剥離)と腐食が確認された。 On the other hand, in metal can No. 6 using a laminated metal plate not according to the present invention, film abnormality after can making, film abnormality (peeling) and corrosion after filling contents were confirmed.
1 金属板
2 フィルム
3 金属板の切リ取った部位
4 重り
5 剥離長
1 Metal plate
2 film
3 Parts cut out of a metal plate
4 weights
5 Peel length
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| JP5827789B2 (en) * | 2010-03-26 | 2015-12-02 | 東洋鋼鈑株式会社 | Resin-coated Al plate for squeezed iron cans with excellent luster and method for producing squeezed iron cans |
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| JP2003213459A (en) * | 2002-01-28 | 2003-07-30 | Nisshin Steel Co Ltd | Surface treated steel sheet having excellent corrosion resistance and spot weldability and production method therefor |
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| JP2004143578A (en) * | 2002-08-27 | 2004-05-20 | Kansai Paint Co Ltd | Precoated aluminum plate |
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