JP2017150092A - Surface treatment liquid, production method of surface treatment aluminum plate using surface treatment liquid and surface treatment aluminum plate - Google Patents
Surface treatment liquid, production method of surface treatment aluminum plate using surface treatment liquid and surface treatment aluminum plate Download PDFInfo
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- JP2017150092A JP2017150092A JP2017115988A JP2017115988A JP2017150092A JP 2017150092 A JP2017150092 A JP 2017150092A JP 2017115988 A JP2017115988 A JP 2017115988A JP 2017115988 A JP2017115988 A JP 2017115988A JP 2017150092 A JP2017150092 A JP 2017150092A
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- aluminum plate
- acid
- surface treatment
- zirconium
- titanium
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 61
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- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 8
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- MYYUWUVATCWCES-UHFFFAOYSA-L potassium;oxalate;titanium(4+);dihydrate Chemical compound O.O.[K+].[Ti+4].[O-]C(=O)C([O-])=O MYYUWUVATCWCES-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、表面処理液及び該表面処理液を用いた表面処理アルミニウム板の製造方法並びに表面処理アルミニウム板に関するものであり、より詳細には、有機樹脂被覆の密着性に優れ、製缶材料として優れた耐食性及び加工密着性を発現可能な表面処理アルミニウム板及びその製造方法並びに上記表面処理アルミニウム板を形成可能な表面処理液に関する。 The present invention relates to a surface treatment liquid, a method for producing a surface-treated aluminum plate using the surface treatment liquid, and a surface-treated aluminum plate. More specifically, the present invention has excellent adhesion with an organic resin coating and can be used as a can-making material. The present invention relates to a surface-treated aluminum plate capable of exhibiting excellent corrosion resistance and work adhesion, a method for producing the same, and a surface treatment liquid capable of forming the surface-treated aluminum plate.
アルミニウム等の金属素材を有機樹脂で被覆した有機樹脂被覆金属板は、製缶材料として古くから知られており、この積層体を絞り加工或いは絞り・しごき加工に付して、飲料等を充填するためのシームレス缶とし、或いはこれをプレス成形してイージイオープンエンド等の缶蓋とすることもよく知られている。 An organic resin-coated metal plate obtained by coating a metal material such as aluminum with an organic resin has long been known as a can-making material, and this laminate is subjected to drawing processing or drawing / ironing processing to fill beverages and the like. It is also well known to make a seamless can for this purpose, or press-mold it to make a can lid such as an easy open end.
このような有機樹脂被覆金属板において、アルミニウム板と有機樹脂被覆との密着性或いはアルミニウム板の耐食性が不十分であるため、アルミニウム板の表面を無機或いは有機の表面処理剤で処理を行うことが行われている。例えばリン酸クロメート系表面処理材があり、皮膜単独の耐食性に優れ、かつ、各種有機樹脂を塗装した際の密着性にも優れていることから広く使用されている。これらクロメート処理は、最終製品中に６価クロムが残存しないタイプであるものの、処理液中に有害物質である６価クロムを含んでいることや、また廃棄後においてクロムの土壌環境中への溶出の可能性が懸念されることなどから、クロムを含有しないノンクロム系の表面処理が望まれている。 In such an organic resin-coated metal plate, since the adhesion between the aluminum plate and the organic resin coating or the corrosion resistance of the aluminum plate is insufficient, the surface of the aluminum plate can be treated with an inorganic or organic surface treatment agent. Has been done. For example, there is a phosphate chromate-based surface treatment material, which is widely used because it is excellent in corrosion resistance of the coating alone and also in adhesion when various organic resins are coated. Although these chromate treatments are of a type in which hexavalent chromium does not remain in the final product, the treatment liquid contains hexavalent chromium, which is a harmful substance, and elution of chromium into the soil environment after disposal Therefore, a non-chromium-based surface treatment not containing chromium is desired.
製缶材料におけるノンクロム系の表面処理も種々提案されており、アルミニウム合金系金属板のノンクロム表面処理として、例えば、ジルコニウム、チタン、またはこれらの化合物と、リン酸塩およびフッ化物を含有し、約ｐＨ１．０〜４．０の酸性処理液を用い、アルミニウム含有金属材料の表面上にジルコニウム及び／又はチタンの酸化物を主成分とする化成皮膜 （特許文献１）や、カーボンを主成分とする有機化合物とリン化合物とジルコニウムあるいはチタン化合物を含む有機−無機複合被膜を形成する方法（特許文献２）、或いは本出願人により、アルミニウム板にも鋼板にも適用でき、容器用としても利用できるノンクロム処理としてＺｒ，Ｏ，Ｆを主成分とし、リン酸イオンを含有しないことを特徴とする表面処理金属材料が提案されている（特許文献３）。 Various non-chromium-based surface treatments for can-making materials have also been proposed. As the non-chromium surface treatment for aluminum alloy metal plates, for example, zirconium, titanium, or a compound thereof, and phosphate and fluoride are contained. Using an acidic treatment solution having a pH of 1.0 to 4.0, a chemical conversion film (Patent Document 1) mainly containing an oxide of zirconium and / or titanium on the surface of an aluminum-containing metal material, or mainly containing carbon. A method of forming an organic-inorganic composite coating containing an organic compound, a phosphorus compound and zirconium or a titanium compound (Patent Document 2), or by the present applicant, it can be applied to both aluminum plates and steel plates, and can be used for containers. Surface-treated metal material characterized by containing Zr, O, and F as main components and not containing phosphate ions Has been proposed (Patent Document 3).
しかしながら、上述した化成処理皮膜では、有機樹脂被覆を形成し、プレコート材料として缶体或いは缶蓋の製造に用いた場合には、有機樹脂被覆の密着性や耐食性を得ることができなかった。またカーボンを主成分とする有機化合物とリン化合物とジルコニウム化合物或いはチタン化合物を含む有機−無機複合被膜を形成する方法では、ある程度密着性は向上するが、耐食性や耐衝撃性（耐デント性）が十分でなかった。更にＺｒ，Ｏ，Ｆを主成分とし、リン酸イオンを含有しない表面処理材料は有機樹脂被覆の密着性に優れ、優れた耐食性を発現し得るものであるが、電解処理によるものであるため、化成処理により、有機樹脂被覆の密着性、耐食性及び耐衝撃性に優れていると共に経済性及び生産性にも優れた表面処理金属材料を提供することが望まれている。 However, when the above-mentioned chemical conversion coating is formed with an organic resin coating and used as a precoat material in the production of a can or a can lid, the adhesion and corrosion resistance of the organic resin coating cannot be obtained. Further, in the method of forming an organic-inorganic composite film containing an organic compound containing carbon as a main component, a phosphorus compound, a zirconium compound, or a titanium compound, adhesion is improved to some extent, but corrosion resistance and impact resistance (dent resistance) are improved. It was not enough. Furthermore, the surface treatment material containing Zr, O, F as a main component and not containing phosphate ions is excellent in the adhesion of the organic resin coating and can exhibit excellent corrosion resistance, but is due to electrolytic treatment, It is desired to provide a surface-treated metal material that is excellent in adhesion, corrosion resistance, and impact resistance of an organic resin coating, as well as economical efficiency and productivity by chemical conversion treatment.
従って本発明の目的は、有機樹脂被覆の密着性に優れ、製缶材料として優れた耐食性及び耐衝撃性（耐デント性）を発現可能な表面処理アルミニウム板及びその製造方法を提供することである。
本発明の他の目的は、上記表面処理アルミニウム板を形成可能な表面処理液を提供することである。
Accordingly, an object of the present invention is to provide a surface-treated aluminum plate that is excellent in adhesion of an organic resin coating and that can exhibit excellent corrosion resistance and impact resistance (dent resistance) as a can-making material, and a method for producing the same. .
Another object of the present invention is to provide a surface treatment liquid capable of forming the surface-treated aluminum plate.
本発明によれば、アルミニウム板を化成処理により表面処理するための表面処理液であって、水分散性のポリエステル樹脂とポリカルボン酸、フッ素イオン、及びジルコニウムイオン又はチタンイオンを含有し、前記ポリカルボン酸がポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、ポリイタコン酸、アクリル酸―メタクリル酸コポリマーから選ばれる少なくても一種であって、前記ポリエステル樹脂が１００００ｐｐｍ未満、前記ジルコニウムイオン又はチタンイオンが５０００ｐｐｍ未満の量で含有され、前記ポリカルボン酸の量がジルコニウムイオン／又はチタンイオンの含有量よりも少ないことを特徴とする表面処理液が提供される。 According to the present invention, there is provided a surface treatment liquid for surface treatment of an aluminum plate by chemical conversion treatment, comprising a water-dispersible polyester resin, polycarboxylic acid, fluorine ions, and zirconium ions or titanium ions, The carboxylic acid is at least one selected from polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, acrylic acid-methacrylic acid copolymer, the polyester resin is less than 10,000 ppm, and the zirconium ion or titanium ion is less than 5000 ppm. And the amount of the polycarboxylic acid is less than the content of zirconium ions / or titanium ions.
本発明によればまた、ｐＨ１．５乃至４．０、温度３５乃至７０℃に調整された上記表面処理液を用いて、２乃至２０秒間の浸漬処理又はスプレー処理によりアルミニウム板に化成処理皮膜を形成することを特徴とする表面処理アルミニウム板の製造方法が提供される。
本発明の表面処理アルミニウム板の製造方法においては、前記化成処理皮膜における炭素量Ｃと、ジルコニウム又はチタン量Ｍの比Ｃ／Ｍが、４０未満であることが好適である。
本発明によれば更に、前記表面処理液を用いて形成された化成処理皮膜を有する表面処理アルミニウム板であって、該化成処理皮膜における炭素量Ｃと、ジルコニウム又はチタン量Ｍの比Ｃ／Ｍが、４０未満であることを特徴とする表面処理アルミニウム板が提供される。
According to the present invention, a chemical conversion coating is applied to an aluminum plate by immersion treatment or spray treatment for 2 to 20 seconds using the surface treatment liquid adjusted to pH 1.5 to 4.0 and temperature 35 to 70 ° C. A method for producing a surface-treated aluminum plate is provided.
In the method for producing a surface-treated aluminum plate of the present invention, it is preferable that the ratio C / M of the carbon content C and the zirconium or titanium content M in the chemical conversion coating is less than 40.
According to the present invention, there is further provided a surface-treated aluminum plate having a chemical conversion treatment film formed using the surface treatment liquid, wherein the ratio C / M of carbon amount C and zirconium or titanium amount M in the chemical conversion treatment film. Is less than 40. A surface-treated aluminum plate is provided.
本発明の表面処理アルミニウム板は、優れた耐食性及び有機樹脂被覆の密着性を有し、この表面処理アルミニウム板に有機樹脂を被覆して成る有機樹脂被覆表面処理アルミニウム板は、絞りしごき加工等の過酷な加工に賦された場合にも耐食性及び加工密着性に優れており、従来より製缶材料に使用されていたリン酸クロメート処理と比べても格段に優れた耐食性及び加工密着性を有しており、缶体或いは缶蓋用の製缶材料として好適に用いることができる。
また有機樹脂被覆としてポリエステルフィルムを用いたプレコート材料とする場合にも、表面処理膜とポリエステルフィルムとの間にプライマー等の塗装層を介在させる必要がなく、生産性及び経済性に優れている。
更に本発明の表面処理アルミニウム板の製造に用いられる表面処理液は、水分散性のポリエステル樹脂及びポリカルボン酸を用いることにより、ジルコニウム化合物又はチタン化合物と共にポリエステル樹脂を表面処理膜に一様に存在させることができると共に、ポリカルボン酸がジルコニウムイオン又はチタンイオンと金属キレート錯体を形成することによって、優れた耐食性及び加工密着性を得ることが可能になる。
The surface-treated aluminum plate of the present invention has excellent corrosion resistance and adhesion of an organic resin coating, and the organic resin-coated surface-treated aluminum plate formed by coating the surface-treated aluminum plate with an organic resin is used for squeezing and ironing. It has excellent corrosion resistance and work adhesion even when subjected to harsh processing, and has much better corrosion resistance and work adhesion than the phosphoric acid chromate treatment conventionally used in canning materials. And can be suitably used as a can-making material for can bodies or can lids.
In addition, when a pre-coating material using a polyester film as the organic resin coating is used, it is not necessary to interpose a coating layer such as a primer between the surface treatment film and the polyester film, which is excellent in productivity and economy.
Furthermore, the surface treatment liquid used for the production of the surface-treated aluminum plate of the present invention uses a water-dispersible polyester resin and a polycarboxylic acid so that the polyester resin is uniformly present in the surface treatment film together with the zirconium compound or the titanium compound. In addition, when the polycarboxylic acid forms a metal chelate complex with zirconium ions or titanium ions, it is possible to obtain excellent corrosion resistance and work adhesion.
本発明の表面処理アルミニウム板は、アルミニウム板の少なくとも一方の表面に、ポリエステル樹脂、ポリカルボン酸、及びジルコニウム化合物又はチタン化合物を含有する化成処理皮膜が形成されて成ることを特徴とするものである。
従来よりジルコニウム化合物又はチタン化合物を含有する無機表面処理膜は知られているが、本発明の表面処理アルミニウム板における化成処理皮膜は、これらの無機物質に加えてポリエステル樹脂及びポリカルボン酸が存在することにより、従来の無機表面処理膜に比して顕著に耐食性及び加工密着性が向上することがわかった。
すなわち、本発明の表面処理アルミニウム板における化成処理皮膜は、アルミニウム板側にジルコニウム化合物又はチタン化合物が位置し、このジルコニウム化合物又はチタン化合物によってポリエステル樹脂が基板に固定され、有機樹脂被覆が施される際等の熱処理によって、ポリエステル樹脂が化成処理皮膜表面を均一に覆うことによって耐食性を発現するとともに、次いで施される有機樹脂被覆との密着性が顕著に向上される。またアルミニウムイオン、ジルコニウムイオン又はチタンイオンと、ポリカルボン酸が金属キレート錯体となって存在し、この金属キレート錯体によっても金属と有機物の密着性が向上するため、上記ポリエステル樹脂による密着性の向上と相俟って、顕著に耐食性及び加工密着性を向上させることが可能になる。
The surface-treated aluminum plate of the present invention is characterized in that a chemical conversion film containing a polyester resin, a polycarboxylic acid, and a zirconium compound or a titanium compound is formed on at least one surface of the aluminum plate. .
Conventionally, an inorganic surface treatment film containing a zirconium compound or a titanium compound has been known, but the chemical conversion treatment film in the surface-treated aluminum plate of the present invention contains a polyester resin and a polycarboxylic acid in addition to these inorganic substances. As a result, it was found that the corrosion resistance and the processing adhesion were remarkably improved as compared with the conventional inorganic surface treatment film.
That is, in the chemical conversion coating on the surface-treated aluminum plate of the present invention, the zirconium compound or titanium compound is located on the aluminum plate side, and the polyester resin is fixed to the substrate by the zirconium compound or titanium compound, and the organic resin coating is applied. When the polyester resin uniformly covers the surface of the chemical conversion treatment film by the heat treatment such as the occasion, the corrosion resistance is exhibited and the adhesion with the organic resin coating to be applied subsequently is remarkably improved. In addition, aluminum ion, zirconium ion or titanium ion and polycarboxylic acid are present as a metal chelate complex, and this metal chelate complex also improves the adhesion between the metal and the organic matter. Together, it becomes possible to significantly improve the corrosion resistance and the work adhesion.
本発明のこのような優れた効果は、後述する実施例の結果からも明らかである。すなわち、表面処理液に水分散型ポリエステル樹脂及びポリカルボン酸の両方が含有されていない場合（比較例２）は勿論、ポリカルボン酸のみが含有されていない場合（比較例１）においても満足する耐食性が得られていないのに対して、本発明の表面処理アルミニウム板では、耐食性及び加工密着性共に満足する結果が得られている（実施例１〜６）。 Such excellent effects of the present invention are also apparent from the results of Examples described later. That is, the case where both the water-dispersed polyester resin and the polycarboxylic acid are not contained in the surface treatment liquid (Comparative Example 2) is satisfied as well as the case where only the polycarboxylic acid is not contained (Comparative Example 1). Whereas the corrosion resistance is not obtained, in the surface-treated aluminum plate of the present invention, results satisfying both the corrosion resistance and the work adhesion are obtained (Examples 1 to 6).
本発明の表面処理アルミニウム板においては、化成処理膜中のポリエステル樹脂及びポリカルボン酸に由来する炭素量Ｃ（ｍｇ／ｍ２）と、ジルコニウム化合物又はチタン化合物に由来するジルコニウム又はチタン量Ｍ（ｍｇ／ｍ２）の比で表わされる有機／無機比（Ｃ／Ｍ）が１乃至４０の範囲、好適には５乃至３０の範囲にあることが特徴である。
Ｃ／Ｍが上記範囲にある表面処理アルミニウム板は、表面処理に際してジルコニウムイオン又はチタンイオンが適切に析出して、ポリエステル樹脂及びポリカルボン酸と共に良好な化成処理皮膜が形成されており、上述した優れた耐食性及び加工密着性を備えた表面処理アルミニウム板を確実に得ることが可能になるが、上記範囲よりもＣ／Ｍの値が小さいと耐食性が劣るようになる。一方、上記範囲よりもＣ／Ｍの値が大きいと、表面処理に要する時間が長くなり、生産性に劣る。
また、析出皮膜量としては特に制限されるものではないが、上記炭素量Ｃが５ｍｇ／ｍ２乃至１０００ｍｇ／ｍ２、特に５０ｍｇ／ｍ２乃至５００ｍｇ／ｍ２の範囲にあることが好まく、またジルコニウム又はチタン量Ｍが、１ｍｇ／ｍ２乃至２００ｍｇ／ｍ２、特に２ｍｇ／ｍ２乃至１００ｍｇ／ｍ２の範囲にあることが好ましい。上述した範囲よりも少ない場合には、アルミニウム板の被覆が十分に行われず耐食性が劣るようになり、一方、上述した範囲よりも多い場合は、皮膜量の増加に応じた性能向上の効果が得られないため、生産性に劣る。
尚、化成処理皮膜中の炭素量（Ｃ）及びジルコニウム又はチタン量（Ｍ）は、市販の蛍光Ｘ線分析装置によって膜厚を定量することができる。この場合、予め炭素及びジルコニウム又はチタンについて重量膜厚が既知の複数のサンプルからこれらの重量膜厚とＸ線強度の関係を示す検量線を作成しておき、試料を用いて測定したＸ線強度を、検量線に基づき重量膜厚に換算する。
In the surface-treated aluminum plate of the present invention, the amount of carbon C (mg / m 2 ) derived from the polyester resin and polycarboxylic acid in the chemical conversion film and the amount of zirconium or titanium M (mg from the zirconium compound or titanium compound) The organic / inorganic ratio (C / M) expressed by the ratio of / m 2 ) is in the range of 1 to 40, preferably 5 to 30.
In the surface-treated aluminum plate having C / M in the above range, zirconium ions or titanium ions are appropriately deposited during the surface treatment, and a good chemical conversion treatment film is formed together with the polyester resin and the polycarboxylic acid. It is possible to reliably obtain a surface-treated aluminum plate having corrosion resistance and work adhesion, but if the C / M value is smaller than the above range, the corrosion resistance will be inferior. On the other hand, when the value of C / M is larger than the above range, the time required for the surface treatment becomes long and the productivity is inferior.
Further, the amount of the deposited film is not particularly limited, but the carbon amount C is preferably in the range of 5 mg / m 2 to 1000 mg / m 2 , particularly 50 mg / m 2 to 500 mg / m 2 , Further, it is preferable that the amount M of zirconium or titanium is in the range of 1 mg / m 2 to 200 mg / m 2 , particularly 2 mg / m 2 to 100 mg / m 2 . When the amount is less than the above range, the aluminum plate is not sufficiently coated and the corrosion resistance becomes inferior. On the other hand, when the amount is more than the above range, the effect of improving the performance according to the increase in the coating amount is obtained. It is inferior in productivity.
The amount of carbon (C) and the amount of zirconium or titanium (M) in the chemical conversion coating can be quantified with a commercially available fluorescent X-ray analyzer. In this case, a calibration curve indicating the relationship between the weight film thickness and the X-ray intensity is prepared in advance from a plurality of samples with known weight film thicknesses for carbon and zirconium or titanium, and the X-ray intensity measured using the sample. Is converted into a weight film thickness based on a calibration curve.
また本発明の有機樹脂被覆表面処理アルミニウムにおいては、上記表面処理アルミニウム板の化成処理皮膜上に有機樹脂被覆を形成してなるものであるが、本発明においては、表面処理アルミニウム板及び有機樹脂被覆の密着性に優れているため、化成処理皮膜に直接、すなわちプライマー等を施すことなく、有機樹脂被覆を形成することができる。
図１は、本発明の有機樹脂被覆表面処理アルミニウム板の一例の断面構造を示す図であり、アルミニウム板２の両面に化成処理皮膜３，３が形成されており、この化成処理皮膜３，３の上に直接有機樹脂被覆４，４が形成されている。
Moreover, the organic resin-coated surface-treated aluminum of the present invention is formed by forming an organic resin coating on the chemical conversion film of the above-mentioned surface-treated aluminum plate. Therefore, the organic resin coating can be formed directly on the chemical conversion film, that is, without applying a primer or the like.
FIG. 1 is a diagram showing a cross-sectional structure of an example of an organic resin-coated surface-treated aluminum plate of the present invention. Chemical conversion coatings 3 and 3 are formed on both surfaces of an aluminum plate 2. The organic resin coatings 4 and 4 are formed directly on the top.
（表面処理液）
本発明の表面処理アルミニウム板の表面処理に用いる表面処理液としては、水分散性のポリエステル樹脂と、ポリカルボン酸、フッ素イオン、ジルコニウムイオン又はチタンイオンを含有することを特徴とする水溶液から成るものである。
すなわち、本発明においては、上述したとおり、表面処理液中にポリエステル樹脂が分散体の形態で存在し、このポリエステル樹脂分散体が、化成処理皮膜中のジルコニウム化合物又はチタン化合物と共に一様にアルミニウム板表面に存在し、またポリカルボン酸は、カルボキシル基の存在により密着性を向上できると共に、ジルコニウムイオン又はチタンイオンと金属キレート錯体を形成することにより、有機樹脂被覆との密着性及び耐食性に優れた化成処理皮膜を提供することが可能になる。
更にポリカルボン酸が含有されていることにより、表面処理に際して過剰なジルコニウム化合物又はチタン化合物の析出が抑制できる。
また本発明の表面処理液においては、ポリエステル樹脂が５００乃至１００００ｐｐｍ、特に１０００乃至５０００ｐｐｍ、ポリカルボン酸が５乃至２０００ｐｐｍ、特に１００乃至１０００ｐｐｍ、ジルコニウムイオン又はチタンイオンが５乃至５０００ｐｐｍ、特に５乃至４０００ｐｐｍ、特に５０乃至１０００ｐｐｍの量で含有されていることが好適である。後述する表面処理の条件等と共に、表面処理液中の各成分が上記範囲にあることにより、化成処理皮膜におけるＣ／Ｍの値が上述した範囲にあり、上述した優れた化成処理皮膜を形成できるが、上記範囲よりも各成分の含有量が少ない場合には、満足する耐食性及び密着性を得ることができず、その一方、上記範囲よりも各成分が多いと、処理液の安定性が劣るようになるおそれがあると共に、更なる耐食性等の向上も得られず、経済性も低下する。
(Surface treatment liquid)
The surface treatment liquid used for the surface treatment of the surface-treated aluminum plate of the present invention comprises a water-dispersible polyester resin and an aqueous solution containing polycarboxylic acid, fluorine ions, zirconium ions or titanium ions. It is.
That is, in the present invention, as described above, the polyester resin is present in the form of a dispersion in the surface treatment liquid, and this polyester resin dispersion is uniformly aluminum plate together with the zirconium compound or titanium compound in the chemical conversion coating. Polycarboxylic acid exists on the surface, and the adhesion can be improved by the presence of a carboxyl group, and by forming a metal chelate complex with zirconium ion or titanium ion, it has excellent adhesion and corrosion resistance with an organic resin coating. It becomes possible to provide a chemical conversion film.
Furthermore, by containing polycarboxylic acid, precipitation of an excessive zirconium compound or titanium compound can be suppressed during the surface treatment.
In the surface treatment liquid of the present invention, the polyester resin is 500 to 10,000 ppm, particularly 1000 to 5000 ppm, the polycarboxylic acid is 5 to 2000 ppm, particularly 100 to 1000 ppm, the zirconium ion or the titanium ion is 5 to 5000 ppm, particularly 5 to 4000 ppm, It is particularly preferable that it is contained in an amount of 50 to 1000 ppm. When the components in the surface treatment liquid are in the above range together with the conditions for the surface treatment to be described later, the C / M value in the chemical conversion treatment film is in the above range, and the above excellent chemical conversion treatment film can be formed. However, when the content of each component is less than the above range, satisfactory corrosion resistance and adhesion cannot be obtained, and on the other hand, when there are more components than the above range, the stability of the treatment liquid is poor. In addition to the possibility of further improvement in corrosion resistance, etc., the economy is also lowered.
本発明の表面処理液に用いる水分散性ポリエステル樹脂としては、親水基を成分として含むポリエステル樹脂を挙げることができる。これらの親水基成分は、ポリエステル分散体表面に物理吸着していても良いし、好ましくはポリステル樹脂骨格中に化学的に共重合されていても良い。
親水基としては、水酸基、アミノ基、カルボキシル基、スルホン酸基、又はこれらの誘導体や金属塩、エーテル等であり、これらを分子内に含むことにより水に分散可能な状態で存在する。
親水性基を含むモノマーとしては、具体的にはポリエチレングリコール，ポリプロピレングリコール，グリセリン，ポリグリセリン等の水酸基含有ポリエーテルモノマー、５−スルホイソフタル酸，４−スルホナフタレン−２，７−ジカルボン酸，５（４−スルホフェノキシ）イソフタル酸等のスルホン酸含有モノマーの金属塩又はアンモニウム塩等を挙げることができる。
また親水性基を有するビニル系モノマーをポリエステル樹脂にグラフト重合させたものでもよく、親水性基を有するビニル系モノマーとしては、カルボキシル基、水酸基、スルホン酸基、アミド基等を含むもの、親水性基に変化させることができる基としては酸無水物基、グリシジル基、クロル基等を含むものを挙げることができる。
本発明においては、水分散性ポリエステル樹脂としては、親水基としてスルホン酸基を有するものを好適に用いることができる。
Examples of the water-dispersible polyester resin used in the surface treatment liquid of the present invention include a polyester resin containing a hydrophilic group as a component. These hydrophilic group components may be physically adsorbed on the surface of the polyester dispersion, or may be chemically copolymerized preferably in the polyester resin skeleton.
The hydrophilic group is a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a derivative or metal salt thereof, ether, or the like, and exists in a state dispersible in water by including these in the molecule.
Specific examples of the monomer containing a hydrophilic group include a hydroxyl group-containing polyether monomer such as polyethylene glycol, polypropylene glycol, glycerin and polyglycerin, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 Examples thereof include metal salts or ammonium salts of sulfonic acid-containing monomers such as (4-sulfophenoxy) isophthalic acid.
Also, a vinyl monomer having a hydrophilic group may be graft-polymerized to a polyester resin. Examples of the vinyl monomer having a hydrophilic group include those containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, etc. Examples of the group that can be changed into a group include an acid anhydride group, a glycidyl group, a chloro group, and the like.
In the present invention, as the water dispersible polyester resin, those having a sulfonic acid group as a hydrophilic group can be suitably used.
また、前記親水性基を含むモノマーと組み合わせて、水分散性ポリエステル樹脂を形成するその他のモノマー成分としては、一般的なポリエステルに用いられるモノマーであれば特に限定されるものではないが、例えば多価カルボン酸として例えばフタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸等の芳香族多価カルボン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸，シクロヘキサンジカルボン酸、ダイマー酸等の脂肪族多価カルボン酸が挙げられる。グリコール成分としては、例えばエチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、ネオペンチルグリコール、１，６ーヘキサンジオールなどが挙げられる。
また、これら水分散性ポリエステル樹脂のガラス転移温度は、−４０℃〜１４０℃が好ましく、２０℃乃至１２０℃がより好ましい。また、水分散性ポリエステル樹脂の数平均分子量は１０００乃至１０万が好ましく、３０００乃至８万がより好ましい。
In addition, the other monomer component that forms the water-dispersible polyester resin in combination with the monomer containing the hydrophilic group is not particularly limited as long as it is a monomer used for general polyester, for example, many Examples of polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, and dimer acid. Carboxylic acid is mentioned. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, and the like.
Further, the glass transition temperature of these water-dispersible polyester resins is preferably -40 ° C to 140 ° C, more preferably 20 ° C to 120 ° C. The number average molecular weight of the water-dispersible polyester resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.
本発明の表面処理液に用いるポリカルボン酸としては、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、ポリイタコン酸、アクリル酸−メタクリル酸コポリマー等のカルボキシル基を有するモノマーの単独重合体又は共重合体、及びその部分中和物を挙げることができ、特に、ポリアクリル酸、ポリメタクリル酸を好適に用いることができる。 As the polycarboxylic acid used in the surface treatment liquid of the present invention, a homopolymer or copolymer of a monomer having a carboxyl group such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, acrylic acid-methacrylic acid copolymer, And partially neutralized products thereof, in particular, polyacrylic acid and polymethacrylic acid can be preferably used.
表面処理液に、ジルコニウムイオン又はチタンイオンを供給可能なジルコニウム化合物又はチタン化合物としては、これに限定されないが、ヘキサフルオロジルコニウム酸、ヘキサフルオロジルコニウムカリウム（ＫＺｒＦ６）やヘキサフルオロジルコニウムアンモニウム（（ＮＨ４）２ＺｒＦ６）、炭酸ジルコニウムアンモニウム溶液（（ＮＨ４）２ＺｒＯ（ＣＯ３）２）、オキシ硝酸ジルコニウムＺｒＯ（ＮＯ３）２、オキシ酢酸ジルコニウム（ＺｒＯ（ＣＨ３ＣＯＯ）２）等、或いはチタンフッ化カリウム（Ｋ２ＴｉＦ６）、チタンフッ化アンモニウム（（ＮＨ４）２ＴｉＦ６）、チタンフッ化ソーダ（Ｎａ２ＴｉＦ６）、シュウ酸チタンカリウム２水和物（Ｋ２ＴｉＯ（Ｃ２Ｏ４）２・２Ｈ２Ｏ）、塩化チタン（ＩＩＩ）溶液（ＴｉＣｌ３）、塩化チタン（ＩＶ）溶液（ＴｉＣｌ４）等を挙げることができる。
尚、本発明の表面処理液においては、フッ素イオンを含有することにより、アルミニウムが溶解し、ジルコニウム化合物又はチタン化合物を適切に析出させることができる。従って上記のうちフッ素イオンを供給可能な化合物以外を用いる場合は、フッ素化合物としてフッ化ナトリウム（ＮａＦ）、フッ化カリウム（ＫＦ）、フッ化アンモニウム（ＮＨ４Ｆ）等を組み合わせて用いることもできる。
Zirconium compounds or titanium compounds that can supply zirconium ions or titanium ions to the surface treatment liquid are not limited to these, but include hexafluorozirconic acid, hexafluorozirconium potassium (KZrF 6 ), and hexafluorozirconium ammonium ((NH 4 ) 2 ZrF 6 ), zirconium carbonate ammonium solution ((NH 4 ) 2 ZrO (CO 3 ) 2 ), zirconium oxynitrate ZrO (NO 3 ) 2 , zirconium oxyacetate (ZrO (CH 3 COO) 2 ), etc., or titanium fluoride Potassium fluoride (K 2 TiF 6 ), ammonium titanium fluoride ((NH 4 ) 2 TiF 6 ), sodium titanium fluoride (Na 2 TiF 6 ), potassium titanium oxalate dihydrate (K 2 TiO (C 2 O 4 ) 2 · 2H 2 O) Titanium (III) chloride solution (TiCl 3), titanium (IV) chloride solution can be mentioned (TiCl 4) or the like.
In addition, in the surface treatment liquid of this invention, by containing a fluorine ion, aluminum melt | dissolves and a zirconium compound or a titanium compound can be precipitated appropriately. Therefore, in the case where a compound other than the compound capable of supplying fluorine ions is used, sodium fluoride (NaF), potassium fluoride (KF), ammonium fluoride (NH 4 F) or the like can be used in combination as the fluorine compound. .
本発明の表面処理液においては、ポリエステル樹脂を分散させるための界面活性剤や、或いは酸化剤等を配合する必要は特になく、水、或いは水と少量の有機溶媒から成る水性媒体に、水分散型ポリエステル樹脂、ジルコニウム化合物又はチタン化合物を、上述した濃度でポリエステル樹脂、及びジルコニウムイオン又はチタンイオンが存在するように、配合することにより調製することができる。
尚、表面処理液中にフッ素イオンを存在させる場合には、フッ素イオンが５乃至４０００ｐｐｍの範囲にあることが望ましい。上記範囲よりもフッ素イオン濃度が低いと、フッ素イオンのエッチング効果を得ることができず、一方上記範囲よりもフッ素イオン濃度が高いと析出効率をかえって阻害するおそれがある。
In the surface treatment liquid of the present invention, it is not particularly necessary to add a surfactant or an oxidizing agent for dispersing the polyester resin, and the water dispersion is carried out in water or an aqueous medium composed of water and a small amount of an organic solvent. Can be prepared by blending a polyester resin, a zirconium compound or a titanium compound so that the polyester resin and zirconium ions or titanium ions are present at the concentrations described above.
In the case where fluorine ions are present in the surface treatment liquid, the fluorine ions are preferably in the range of 5 to 4000 ppm. When the fluorine ion concentration is lower than the above range, the fluorine ion etching effect cannot be obtained. On the other hand, when the fluorine ion concentration is higher than the above range, the deposition efficiency may be hindered.
（表面処理方法）
本発明の表面処理液を用いたアルミニウム板の表面処理方法は、上述した水分散性ポリエステル樹脂、ポリカルボン酸、及びジルコニウム化合物又はチタン化合物を水性媒体に配合し、ポリエステル樹脂が５００乃至１００００ｐｐｍ、ポリカルボン酸が５乃至２０００ｐｐｍ、ジルコニウムイオン又はチタンイオンが５乃至５０００ｐｐｍの量となるように調製された表面処理液を用い、浸漬処理或いはスプレー処理、ロールコーターによる処理によって行うことができる。
表面処理液のｐＨは、１．５乃至４．０の範囲にあることが好ましく、必要に応じて硝酸又はアンモニアを添加して調整する。上記範囲よりもｐＨが低いと十分な皮膜を得ることができず、一方上記範囲よりもｐＨが大きいと、処理液の安定性に劣るようになる。
また表面処理液の温度は、特に限定されないが、３５乃至７０℃の範囲にあることが、安定して被膜を形成する上で望ましい。
表面処理液への浸漬に先立って、アルミニウム板は、常法により、脱脂、水洗、必要に応じて、エッチング処理、水洗、更に酸洗、水洗の前処理を行う。次いで、上記ｐＨ及び温度範囲に調整された表面処理液に２乃至２０秒間浸漬、或いはスプレー処理した後、水洗し、乾燥することによって、化成処理被膜が形成された表面処理アルミニウム板を得ることができる。
尚、アルミニウム板は、従来製缶材料に用いられていたアルミニウム板を全て使用することができ、アルミニウム合金板の他、純アルミニウム板であってもよく、またその厚みはこれに限定されないが、１００乃至５００μｍの範囲にあるものを好適に使用することができる。
また、表面処理の方法によっては、基板のアルミニウムが溶解することもあり、化成皮膜にアルミニウム化合物が含有する場合がある。
(Surface treatment method)
The surface treatment method for an aluminum plate using the surface treatment liquid of the present invention comprises mixing the above-mentioned water-dispersible polyester resin, polycarboxylic acid, and zirconium compound or titanium compound in an aqueous medium, the polyester resin being 500 to 10,000 ppm, A surface treatment solution prepared so that the amount of carboxylic acid is 5 to 2000 ppm and the amount of zirconium ions or titanium ions is 5 to 5000 ppm can be used by immersion treatment, spray treatment, or treatment with a roll coater.
The pH of the surface treatment solution is preferably in the range of 1.5 to 4.0, and is adjusted by adding nitric acid or ammonia as necessary. If the pH is lower than the above range, a sufficient film cannot be obtained. On the other hand, if the pH is higher than the above range, the stability of the treatment liquid becomes poor.
The temperature of the surface treatment liquid is not particularly limited, but is preferably in the range of 35 to 70 ° C. in order to stably form a film.
Prior to the immersion in the surface treatment solution, the aluminum plate is subjected to pretreatments such as degreasing, water washing, and if necessary, etching treatment, water washing, further acid pickling, and water washing in a conventional manner. Subsequently, after being immersed or sprayed in a surface treatment solution adjusted to the above pH and temperature range for 2 to 20 seconds, washed with water and dried to obtain a surface-treated aluminum plate on which a chemical conversion film has been formed. it can.
In addition, the aluminum plate can use all the aluminum plates conventionally used for can-made materials, and may be a pure aluminum plate other than an aluminum alloy plate, and the thickness is not limited to this, Those in the range of 100 to 500 μm can be preferably used.
Further, depending on the surface treatment method, the aluminum of the substrate may be dissolved, and the chemical conversion film may contain an aluminum compound.
（有機樹脂被覆表面処理アルミニウム板）
本発明の有機樹脂被覆表面処理アルミニウム板は、上記表面処理アルミニウム板の化成処理皮膜上に有機樹脂から成る層を被覆して成るものであり、上述した表面処理アルミニウム板を用いることから、有機樹脂被覆の密着性、特に加工密着性に優れており、このため優れた耐食性、耐デント性を有している。
本発明の有機樹脂被覆表面処理アルミニウム板において、化成処理皮膜上に設ける有機樹脂としては、特に限定はなく、熱可塑性樹脂から成るフィルム、或いは熱硬化性乃至熱可塑性樹脂から成る塗膜を挙げることができる。
(Organic resin-coated surface-treated aluminum plate)
The organic resin-coated surface-treated aluminum plate of the present invention is formed by coating a layer made of an organic resin on the chemical conversion film of the surface-treated aluminum plate. Since the above-mentioned surface-treated aluminum plate is used, the organic resin It has excellent coating adhesion, particularly processing adhesion, and therefore has excellent corrosion resistance and dent resistance.
In the organic resin-coated surface-treated aluminum plate of the present invention, the organic resin provided on the chemical conversion coating is not particularly limited, and examples thereof include a film made of a thermoplastic resin or a coating film made of a thermosetting or thermoplastic resin. Can do.
フィルム形成可能な熱可塑性樹脂としては、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、アイオノマー等のオレフィン系樹脂フィルム、またはポリエチレンテレフタレ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を挙げることができ、かかる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。
更に塗膜形成可能な塗料としては、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、ポリエステル系塗料、スチレン−ブタジェン系共重合体等の合成ゴム系塗料等を挙げることができ、これらの２種以上の組合わせであってもよい。
Examples of the thermoplastic resin capable of forming a film include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyethylene terephthalate. Polyester film, polyamide film such as nylon 6, nylon 6,6, nylon 11, nylon 12, etc., polyvinyl chloride film, polyvinylidene chloride film, etc. can be mentioned. Unstretched or biaxially stretched of such a thermoplastic resin film It may be what you did.
Further, paints capable of forming a coating include modified epoxy paints such as phenol epoxy and amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-anhydrous maleic anhydride. Examples include acid copolymers, epoxy-modified, epoxy-amino-modified, epoxy-phenol-modified vinyl paints or modified vinyl paints, acrylic paints, polyester paints, and styrene-butadiene copolymers. It may be a combination of two or more of these.
これらの中でも、製缶材料としてポリエステル樹脂フィルムから成る被覆が最も好適に用いられる。
ポリエステル樹脂としては、ホモポリエチレンテレフタレートも勿論使用可能であるが、フィルムの到達し得る最高結晶化度を下げることが耐衝撃性や加工性の点で望ましく、この目的のためにポリエステル中にエチレンテレフタレート以外の共重合エステル単位を導入するのがよい。エチレンテレフタレート単位を主体とし、他のエステル単位の少量を含む共重合ポリエステル樹脂を用いることが特に好ましい。
一般に共重合ポリエステル中の二塩基酸成分の７０モル％以上、特に７５モル％以上がテレフタル酸成分から成り、ジオール成分の７０モル％以上、特に７５モル％以上がエチレングリコールから成り、二塩基酸成分の１乃至３０モル％、特に５乃至２５モル％がテレフタル酸以外の二塩基酸成分から成ることが好ましい。
テレフタル酸以外の二塩基酸としては、イソフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸：シクロヘキサンジカルボン酸等の脂環族ジカルボン酸：コハク酸、アジピン酸、セバチン酸、ドデカンジオン酸等の脂肪族ジカルボン酸：の１種又は２種以上の組合せが挙げられ、エチレングリコールまたはブチレングリコール以外のジオール成分としては、プロピレングリコール、ジエチレングリコール、１，６−ヘキシレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加物等の１種又は２種以上が挙げられる。
Among these, a coating made of a polyester resin film is most preferably used as a can-making material.
Of course, homopolyethylene terephthalate can be used as the polyester resin, but it is desirable in terms of impact resistance and workability to lower the maximum crystallinity that the film can reach. For this purpose, ethylene terephthalate is contained in the polyester. It is preferable to introduce copolymer ester units other than the above. It is particularly preferable to use a copolymerized polyester resin mainly composed of ethylene terephthalate units and containing a small amount of other ester units.
In general, 70 mol% or more, particularly 75 mol% or more of the dibasic acid component in the copolyester is composed of a terephthalic acid component, and 70 mol% or more, particularly 75 mol% or more of the diol component is composed of ethylene glycol. It is preferable that 1 to 30 mol%, particularly 5 to 25 mol% of the components are composed of a dibasic acid component other than terephthalic acid.
Dibasic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid: alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid: succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc. Or a combination of two or more of the aliphatic dicarboxylic acids: As the diol component other than ethylene glycol or butylene glycol, propylene glycol, diethylene glycol, 1,6-hexylene glycol, cyclohexane dimethanol, bisphenol A 1 type, or 2 or more types, such as an ethylene oxide adduct.
また、このポリエステル樹脂は、成形時の溶融流動特性を改善するために、三官能以上の多塩基酸及び多価アルコールから成る群より選択された少なくとも１種の分岐乃至架橋成分を含有することができる。これらの分岐乃至架橋成分は、３．０モル％以下、好適には０．０５乃至３．０モル％の範囲にあるのがよい。
三官能以上の多塩基酸及び多価アルコールとしては、トリメリット酸、ピロメリット酸、ヘミメリット酸、１，１，２，２−エタンテトラカルボン酸、１，１，２−エタントリカルボン酸、１，３，５−ペンタントリカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸、ビフェニル−３，４，３’，４’−テトラカルボン酸等の多塩基酸や、ペンタエリスリトール、グリセロール、トリメチロールプロパン、１，２，６−ヘキサントリオール、ソルビトール、１，１，４，４−テトラキス（ヒドロキシメチル）シクロヘキサン等の多価アルコールが挙げられる。
In addition, the polyester resin may contain at least one branching or crosslinking component selected from the group consisting of trifunctional or higher polybasic acids and polyhydric alcohols in order to improve the melt flow characteristics during molding. it can. These branching or crosslinking components should be in the range of 3.0 mol% or less, preferably 0.05 to 3.0 mol%.
Examples of the trifunctional or higher polybasic acid and polyhydric alcohol include trimellitic acid, pyromellitic acid, hemimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1 , 3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polybasic acids such as biphenyl-3,4,3 ′, 4′-tetracarboxylic acid, pentaerythritol, glycerol, Examples include polyhydric alcohols such as trimethylolpropane, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane.
ホモポリエステル樹脂或いは共重合ポリエステル樹脂は、フィルム形成範囲の分子量を有するべきであり、溶媒として、フェノール／テトラクロロエタン混合溶媒を用いて測定した固有粘度〔η〕は０．５乃至１．５、特に０．６乃至１．５の範囲にあるのがよい。
本発明の有機樹脂被覆に用いるポリエステル樹脂層は、単層の樹脂層であってもよく、また同時押出などによる多層の樹脂層であってもよい。多層のポリエステル樹脂層を用いると、下地層、すなわち表面処理アルミニウム板側に接着性に優れた組成のポリエステル樹脂を選択し、表層に耐内容物性、すなわち耐抽出性やフレーバー成分の非吸着性に優れた組成のポリエステル樹脂を選択できるので有利である。
上記ポリエステル樹脂層には、それ自体公知の樹脂用配合剤、例えば非晶質シリカ等のアンチブロッキング剤、無機フィラー、各種帯電防止剤、滑剤、酸化防止剤、紫外線吸収剤等を公知の処方に従って配合することができる。
本発明において、有機樹脂被覆がポリエステル樹脂等の熱可塑性樹脂から成る被覆である場合の厚みは、一般に３乃至５０μｍの範囲にあることが望ましく、有機樹脂被覆が塗膜である場合には、０．５乃至２０ｇ／ｍ２の塗工量であることが望ましい。有機樹脂被覆の厚みが、上記範囲よりも小さいと耐食性が不十分となり、一方上記範囲よりも大きいと加工性の点で問題を生じやすい。
The homopolyester resin or copolymer polyester resin should have a molecular weight in the film forming range, and the intrinsic viscosity [η] measured using a phenol / tetrachloroethane mixed solvent as the solvent is 0.5 to 1.5, especially It may be in the range of 0.6 to 1.5.
The polyester resin layer used for the organic resin coating of the present invention may be a single resin layer or a multilayer resin layer formed by coextrusion or the like. When a multilayer polyester resin layer is used, a polyester resin having a composition with excellent adhesiveness is selected for the base layer, that is, the surface-treated aluminum plate, and the surface layer has content resistance, that is, extraction resistance and non-adsorption of flavor components. This is advantageous because a polyester resin having an excellent composition can be selected.
In the polyester resin layer, known compounding agents for resins, for example, antiblocking agents such as amorphous silica, inorganic fillers, various antistatic agents, lubricants, antioxidants, ultraviolet absorbers, etc., according to known formulations Can be blended.
In the present invention, the thickness when the organic resin coating is a coating made of a thermoplastic resin such as a polyester resin is generally desirably in the range of 3 to 50 μm, and when the organic resin coating is a coating film, the thickness is 0. The coating amount is desirably 5 to 20 g / m 2 . If the thickness of the organic resin coating is smaller than the above range, the corrosion resistance becomes insufficient. On the other hand, if the thickness is larger than the above range, a problem is likely to occur in terms of workability.
（有機樹脂被覆表面処理アルミニウム板の製造）
本発明において、表面処理アルミニウム板への有機樹被覆の形成は任意の手段で行うことができ、例えば、ポリエステル樹脂被覆の場合では、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、熱硬化性塗料による被覆等の場合には、ロールコート法、スプレー法等、従来公知の方法で塗工できる。
また前述した通り、本発明においては、表面処理アルミニウム板の有機樹脂被覆の密着性に優れていることから、化成処理膜と有機樹脂被覆、特にポリエステル樹脂から成る被覆との間に、接着用プライマー等の塗膜を設ける必要はないが、勿論設けることを除外するものではなく、密着性と耐食性とに優れた従来公知のフェノールエポキシ系塗料等のプライマー塗料を用いることもでき、表面処理アルミニウム板或いはポリエステルフィルムの何れに予め設けてもよい。
(Manufacture of organic resin-coated surface-treated aluminum plate)
In the present invention, formation of the organic resin coating on the surface-treated aluminum plate can be performed by any means. For example, in the case of polyester resin coating, extrusion coating, cast film thermal bonding, biaxially stretched film thermal bonding. In the case of coating with a thermosetting paint, it can be applied by a conventionally known method such as a roll coating method or a spray method.
In addition, as described above, in the present invention, since the adhesion of the organic resin coating of the surface-treated aluminum plate is excellent, the primer for adhesion between the chemical conversion treatment film and the organic resin coating, particularly a coating made of a polyester resin. It is not necessary to provide a coating film such as, but of course, it does not exclude the provision of a primer paint such as a conventionally known phenol epoxy paint excellent in adhesion and corrosion resistance. Or you may provide in any of polyester films beforehand.
（缶体）
本発明の缶体は、前述した有機樹脂被覆表面処理アルミニウム板から形成されている限り、従来公知の任意の製缶法により成形することができ、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、有機樹脂被覆表面処理アルミニウム板の有機樹脂被覆面が少なくとも缶内面側となるように、絞り・再しぼり加工、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・しごき加工或いは絞り・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。
(Can body)
As long as the can body of the present invention is formed from the aforementioned organic resin-coated surface-treated aluminum plate, it can be formed by any conventionally known can-making method, and can also be a three-piece can having a side seam. In general, a seamless can (two-piece can) is preferable. This seamless can is drawn and re-squeezed, bent and stretched by drawing and redrawing (stretching), and drawn and redrawn so that the organic resin-coated surface of the organic resin-coated surface-treated aluminum plate is at least the inside of the can. It is manufactured by attaching to a conventionally known means such as bending / stretching or ironing by drawing or drawing / ironing.
（缶蓋）
本発明の缶蓋は、前述した有機樹脂被覆表面処理アルミニウム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り成形することができ、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。
(Can lid)
The can lid of the present invention can be formed by any conventionally known lid-making method as long as it is formed from the above-mentioned organic resin-coated surface-treated aluminum plate, and is generally a stay-on-tab type easy open. It can be applied to a can lid or a full open type easy open can lid.
本発明を次の実施例により更に説明するが、本発明は次の例により何らかの制限を受けるものではない。実施例および比較例で使用した供試板の試験方法について述べる。 The present invention is further illustrated by the following examples, but the invention is not limited in any way by the following examples. The test method of the test plate used in the examples and comparative examples will be described.
（炭素量）
化成処理皮膜中のポリエステル樹脂及びポリカルボン酸に由来する炭素原子の量は、蛍光Ｘ線分析装置を用いて測定した。測定に用いた検量線は、濃度が既知の水分散型ポリエステル及びポリカルボン酸含有水溶液を、清浄なアルミニウム合金上に塗装焼き付けして炭素量が既知の標準板を作製し、これらの蛍光Ｘ線強度と測定炭素量との相関から測定した。
(Carbon content)
The amount of carbon atoms derived from the polyester resin and the polycarboxylic acid in the chemical conversion film was measured using a fluorescent X-ray analyzer. The calibration curve used for the measurement was a standard plate with a known carbon content obtained by painting and baking a water-dispersed polyester and polycarboxylic acid-containing aqueous solution having a known concentration on a clean aluminum alloy. It was measured from the correlation between strength and measured carbon content.
（ジルコニウムまたはチタン量）
化成処理皮膜中のジルコニウム化合物又はチタン化合物に由来するジルコニウム又はチタン量は、蛍光Ｘ線分析装置を用いて測定した。検量線は、皮膜量が既知のジルコニウム又はチタン析出標準板を用意し、これらの蛍光Ｘ線強度と皮膜量の相関から測定した。
(Zirconium or titanium content)
The amount of zirconium or titanium derived from the zirconium compound or titanium compound in the chemical conversion coating was measured using a fluorescent X-ray analyzer. The calibration curve was measured from the correlation between the fluorescent X-ray intensity and the coating amount by preparing a zirconium or titanium deposition standard plate with a known coating amount.
（有機／無機比の算出方法）
化成処理皮膜中の、ポリエステル樹脂及びポリカルボン酸に由来する炭素量と、ジルコニウム化合物又はチタン化合物に由来するジルコニウム又はチタン量の比で表わされる有機／無機比の算出については、蛍光Ｘ線分析により得られた皮膜量を、以下の式を用いて計算することで得た。
有機／無機比＝Ｃ／Ｍ （−）
Ｃ：化成処理皮膜中の炭素量（ｍｇ／ｍ２）
Ｍ：化成処理皮膜中のジルコニウム又はチタン量（ｍｇ／ｍ２）
(Calculation method of organic / inorganic ratio)
Regarding the calculation of the organic / inorganic ratio represented by the ratio of the amount of carbon derived from the polyester resin and the polycarboxylic acid and the amount of zirconium or titanium derived from the zirconium compound or titanium compound in the chemical conversion coating film, by fluorescent X-ray analysis The obtained coating amount was obtained by calculating using the following formula.
Organic / inorganic ratio = C / M (-)
C: Carbon amount in the chemical conversion coating (mg / m 2 )
M: amount of zirconium or titanium in the chemical conversion coating (mg / m 2 )
（蛍光Ｘ線分析装置の測定条件）
使用機器： 理学電機製 ＺＳＸ１００ｅ
測定条件： 測定対象 Ｚｒ−Ｋα線、Ｃ−Ｋα線
測定径 ２０ｍｍ
Ｘ線出力 ５０ｋＶ−７０ｍＡ
測定時間 ２０秒（Ｚｒ）、１００秒（Ｃ）
(Measurement conditions of X-ray fluorescence analyzer)
Equipment used: ZSX100e manufactured by Rigaku Corporation
Measurement conditions: Measurement object Zr-Kα ray, C-Kα ray
Measurement diameter 20mm
X-ray output 50kV-70mA
Measurement time 20 seconds (Zr), 100 seconds (C)
（金属キレート錯体の確認方法）
表面処理アルミニウム板の化成皮膜中の金属キレート錯体の確認は、フーリエ変換赤外分光光度計で測定した。金属イオンと複合化することにより、カルボン酸はカルボン酸塩へと転換する。一般に、カルボン酸の特性吸収帯は、９２０〜９７０ｃｍ−１付近、１７００〜１７１０ｃｍ−１付近、２５００〜３２００ｃｍ−１付近の波長にあることが知られている。また、カルボン酸塩の特性吸収帯は、１４８０〜１６３０ｃｍ−１付近の波長にあることが知られており、これらピークのシフトを確認することで金属キレート錯体を確認した。
(Metal chelate complex confirmation method)
Confirmation of the metal chelate complex in the chemical conversion film of the surface-treated aluminum plate was measured with a Fourier transform infrared spectrophotometer. By complexing with a metal ion, the carboxylic acid is converted to a carboxylate. In general, the characteristic absorption band of the carboxylic acid, 920～970Cm around -1, 1700～1710Cm around -1, it is known that a wavelength of around 2500～3200Cm -1. Moreover, it is known that the characteristic absorption band of a carboxylate salt exists in the wavelength of 1480-1630 cm < -1 > vicinity, The metal chelate complex was confirmed by confirming the shift of these peaks.
（フーリエ変換赤外分光光度計の測定条件）
使用機器：Ｄｉｇｉｌａｂ社製 ＦＴＳ７０００ｓｅｒｉｅｓ
測定方法：ゲルマニウムプリズムを用いた一回反射法
測定波長領域：４０００〜７００ｃｍ−１
(Measurement conditions of Fourier transform infrared spectrophotometer)
Equipment used: Digilab FTS7000series
Measurement method: single reflection method using germanium prism Measurement wavelength region: 4000 to 700 cm −1
（耐食試験）
作製した表面処理アルミニウム板の耐食性能は、塩化物イオンを含有する酸性水溶液に浸漬し、性状の変化を経時で観察することで行った。アルミ供試板の耐食性が不足している場合、露出部の金属基板が溶解し、腐食により金属化合物が発生するので、これらに由来する白錆を確認することで評価した。
試験に用いたモデル水溶液は、食塩を１０００ｐｐｍとし、これにクエン酸を加えてｐＨが３．０となるよう調整したものを用いた。また、試験時の保管温度は３７℃で行った。
耐食性 可 ：経時２週間の時点で、白錆の発生なし
耐食性 不可 ：経時２週間の時点で、白錆の発生あり
(Corrosion resistance test)
The corrosion resistance of the produced surface-treated aluminum plate was measured by immersing it in an acidic aqueous solution containing chloride ions and observing changes in properties over time. When the corrosion resistance of the aluminum test plate was insufficient, the exposed metal substrate was dissolved and a metal compound was generated due to corrosion. Therefore, the evaluation was made by confirming white rust derived therefrom.
The model aqueous solution used for the test was adjusted to a pH of 3.0 by adding sodium chloride to 1000 ppm and adding citric acid thereto. The storage temperature during the test was 37 ° C.
Corrosion resistance Yes: No white rust occurs at 2 weeks of age Corrosion resistance No: White rust occurs at 2 weeks of age
（加工密着性評価）
作製した缶体の缶側壁部の缶底から高さ４５ｍｍ〜９５ｍｍの部分を幅１５ｍｍで短冊状に切り出し、短冊状の先端から３５ｍｍ位置（缶底からの高さ８０ｍｍの位置に相当）に缶外面側素地に達する傷を入れた。予め入れた傷を起点として折り曲げを繰り返すことにより金属片のみを切断し、樹脂フィルムだけで繋がっている部分を作った後、この部分を内面側になるようにし、ピール試験機を用いて１８０度剥離試験を２３℃下、引張速度５ｍｍ／ｍｉｎで行って密着強度を測定した。
評価結果は
加工後密着力 ○：密着強度が、１．０Ｎ／１５ｍｍ以上
加工後密着力 ×：密着強度が、１．０Ｎ／１５ｍｍ以下
で示した。
(Processing adhesion evaluation)
Cut out the 45mm to 95mm height portion from the bottom of the can side wall of the can body into a strip shape with a width of 15mm, and place it at the 35mm position from the strip tip (equivalent to a position of 80mm height from the bottom) Scratches reaching the outer side substrate were made. By cutting the metal piece only by repeating bending with the scratches made in advance as the starting point, and making a part connected only by the resin film, this part is made to be the inner surface side, and 180 degrees using a peel tester A peel test was performed at 23 ° C. and a tensile speed of 5 mm / min to measure the adhesion strength.
The evaluation result is
Adhesion strength after processing ○: Adhesion strength is 1.0 N / 15 mm or more
Adhesion strength after processing ×: Adhesion strength is 1.0 N / 15 mm or less.
（実施例１）
アルミニウム合金板（３００４材）を準備し、日本ペイント社製の脱脂剤「サーフクリーナーＥＣ３７１」（商品名）の２％水溶液中（５０℃）に、６秒間浸漬して脱脂処理を行った。脱脂処理後、水洗してから、日本ペイント社製のエッチング剤「サーフクリーナー４２０Ｎ−２」（商品名）の２％水溶液中（５０℃）に、６秒間浸漬してアルカリエッチング処理を行った。エッチング処理後、水洗してから、２％硫酸水溶液中（５０℃）に６秒間浸漬して酸洗浄を行った。
酸洗浄後、水洗してから、水分散型ポリエステル樹脂（東洋紡績社製ポリエステル「バイロナ−ルＭＤ２０００」）、ポリカルボン酸（東亜合成社製ポリアクリル酸「ジュリマー１０ＬＨＰ」）、及びジルコニウム化合物（アルドリッチ社製ヘキサフルオロジルコニウム酸）を、それぞれポリエステルが５０００ｐｐｍ、ポリアクリル酸が１００ｐｐｍ、ジルコニウムイオンが２００ｐｐｍとなるように配合し、必要に応じて硝酸或いはアンモニアを添加してｐＨを１．８に調整し、その後６秒間の浸漬処理することで化成処理皮膜を形成した。更に水洗した後、２１０℃×１８０秒の条件で乾燥させ、表面処理アルミニウム板を得た。
Example 1
An aluminum alloy plate (3004 material) was prepared, and degreased by immersing in a 2% aqueous solution (50 ° C.) of a degreasing agent “Surf Cleaner EC371” (trade name) manufactured by Nippon Paint Co., Ltd. for 6 seconds. After degreasing, the substrate was washed with water and then immersed in a 2% aqueous solution (50 ° C.) of an etching agent “Surf Cleaner 420N-2” (trade name) manufactured by Nippon Paint Co., Ltd. for 6 seconds to perform an alkali etching treatment. After the etching treatment, the substrate was washed with water and then immersed in a 2% aqueous sulfuric acid solution (50 ° C.) for 6 seconds for acid cleaning.
After acid washing and water washing, water-dispersed polyester resin (polyester “Vylonal MD2000” manufactured by Toyobo Co., Ltd.), polycarboxylic acid (polyacrylic acid “Jurimer 10LHP” manufactured by Toagosei Co., Ltd.), and zirconium compound (Aldrich) Hexafluorozirconic acid) is blended so that the polyester is 5000 ppm, the polyacrylic acid is 100 ppm, and the zirconium ions are 200 ppm. If necessary, the pH is adjusted to 1.8 by adding nitric acid or ammonia. Then, a chemical conversion treatment film was formed by immersion treatment for 6 seconds. After further washing with water, it was dried at 210 ° C. for 180 seconds to obtain a surface-treated aluminum plate.
作製した表面処理アルミニウム板を、予め板温度２５０℃に加熱しておき、アルミニウム板の両面にイソフタル酸１５ｍｏｌ％共重合のポリエチレンテレフタレートフィルム（フィルム厚み：１６μｍ）を、ラミネートロールを介して熱圧着した後、直ちに水冷することにより、有機樹脂被覆表面処理アルミニウム板を得た。
得られた有機樹脂被覆アルミニウム板の両面に、パラフィンワックスを静電塗油した後、直径１５６ｍｍの円形に打ち抜き、浅絞りカップを作成した。次いで、この浅絞りカップを、再絞り−しごき加工及びドーミング成形を行い、続いて開口端縁部のトリミング加工を行うことにより、缶体を得た。缶体の諸特性は以下の通りであった。
缶体径：６６ｍｍ
缶体高さ：１６８ｍｍ
元板厚に対する缶側壁部の平均板厚減少率：６０％
The prepared surface-treated aluminum plate was previously heated to a plate temperature of 250 ° C., and a polyethylene terephthalate film (film thickness: 16 μm) copolymerized with 15 mol% isophthalic acid was thermocompression bonded to both surfaces of the aluminum plate via a laminate roll. Thereafter, it was immediately cooled with water to obtain an organic resin-coated surface-treated aluminum plate.
After paraffin wax was electrostatically applied to both surfaces of the obtained organic resin-coated aluminum plate, it was punched out into a circle having a diameter of 156 mm to produce a shallow drawn cup. Next, this shallow drawn cup was subjected to redrawing-ironing processing and doming forming, followed by trimming of the opening edge portion to obtain a can body. Various characteristics of the can body were as follows.
Can body diameter: 66 mm
Can height: 168mm
Average thickness reduction rate of can side wall relative to original thickness: 60%
（実施例２）
実施例１において、処理液のジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 2)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions in the treatment liquid was 500 ppm.
（実施例３）
実施例１において、処理液のポリエステル量を処理液のジルコニウムイオン量を１０００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 3)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can are obtained in the same manner as in Example 1 except that the amount of polyester in the treatment liquid is 1000 ppm in the amount of zirconium ions in the treatment liquid. It was.
（実施例４）
実施例１において、処理液のポリエステル量を２５００ｐｐｍ、ポリアクリル酸量を２００ｐｐｍ、ジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
Example 4
In Example 1, the surface-treated aluminum plate and the organic resin-coated surface-treated aluminum plate were the same as in Example 1 except that the amount of polyester in the treatment liquid was 2500 ppm, the amount of polyacrylic acid was 200 ppm, and the amount of zirconium ions was 500 ppm. A can body was obtained.
（実施例５）
実施例１において、処理液のポリアクリル酸量を８００ｐｐｍ、ジルコニウムイオン量を１０００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 5)
In Example 1, the surface-treated aluminum plate, the organic resin-coated surface-treated aluminum plate, and the can were prepared in the same manner as in Example 1 except that the amount of polyacrylic acid in the treatment liquid was 800 ppm and the amount of zirconium ions was 1000 ppm. Obtained.
（実施例６）
実施例１において、ポリアクリル酸量を８００ｐｐｍ、ジルコニウムイオン量を４０００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Example 6)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of polyacrylic acid was 800 ppm and the amount of zirconium ions was 4000 ppm.
（比較例１）
実施例１において、処理液のポリアクリル酸を除き、ジルコニウムイオン量を５００ｐｐｍとする以外は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Comparative Example 1)
In Example 1, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that the amount of zirconium ions was changed to 500 ppm except for polyacrylic acid in the treatment liquid. It was.
（比較例２）
実施例２において、処理液のポリエステルとポリアクリル酸を除く以外は実施例２と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
(Comparative Example 2)
In Example 2, a surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 2 except that the polyester and polyacrylic acid in the treatment liquid were removed.
（比較例３）
市販のリン酸クロメート処理膜を用いる他は実施例１と同様の方法で、表面処理アルミニウム板、有機樹脂被覆表面処理アルミニウム板、及び缶体を得た。
実施例および比較例の試験評価結果を、表１に示した。
(Comparative Example 3)
A surface-treated aluminum plate, an organic resin-coated surface-treated aluminum plate, and a can were obtained in the same manner as in Example 1 except that a commercially available phosphoric acid chromate-treated film was used.
The test evaluation results of Examples and Comparative Examples are shown in Table 1.
表１から、本発明の表面処理アルミニウム板の耐食性は、実施例１〜６に示した領域、すなわち有機／無機比が１．０以上において、特に耐食性が優れている。また、得られた皮膜の加工後密着性は、缶材として使用されるリン酸クロメート処理と比べて大きく、有機樹脂被覆表面処理アルミニウム板として加工性に優れている。以上の理由から、厳しい加工と金属基板保護が要求される缶体および缶蓋として、実用上極めて有用であると言える。 From Table 1, the corrosion resistance of the surface-treated aluminum plate of the present invention is particularly excellent in the region shown in Examples 1 to 6, that is, the organic / inorganic ratio is 1.0 or more. Moreover, the adhesion after processing of the obtained film is larger than that of the phosphoric acid chromate treatment used as a can material, and the organic resin-coated surface-treated aluminum plate is excellent in workability. For the above reasons, it can be said that it is extremely useful in practice as a can body and a can lid that require strict processing and metal substrate protection.
本発明の表面処理アルミニウム板は、優れた耐食性及び有機樹脂被覆の密着性を有し、この表面処理アルミニウム板に有機樹脂を被覆して成る有機樹脂被覆表面処理アルミニウム板は、過酷な加工に賦された場合にも加工密着性に優れており、絞りしごき缶等の過酷な加工により成形される缶体、或いはリベット加工やスコア加工等が施されるイージーオープン蓋等の缶蓋に有効に利用できる。
また耐食性にも優れていることから、腐食性の強い内容物に使用される缶体或いは缶蓋用の製缶材料として好適に用いることができる。
The surface-treated aluminum plate of the present invention has excellent corrosion resistance and adhesion of an organic resin coating. The organic resin-coated surface-treated aluminum plate obtained by coating the surface-treated aluminum plate with an organic resin is suitable for severe processing. Even when it is applied, it has excellent processing adhesion and can be used effectively for cans formed by severe processing such as squeezing and ironing cans, or can lids such as easy open lids that are subjected to rivet processing and score processing, etc. it can.
Moreover, since it is excellent also in corrosion resistance, it can be used suitably as a can-making material for can bodies or can lids used for highly corrosive contents.
１：有機樹脂被覆表面処理アルミニウム板、２：アルミニウム合金材料、３：化成処理皮膜、４：有機樹脂被覆材料 1: Organic resin-coated surface-treated aluminum plate, 2: Aluminum alloy material, 3: Chemical conversion coating, 4: Organic resin coating material
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| JP2001303267A (en) * | 2000-04-20 | 2001-10-31 | Nippon Paint Co Ltd | Non-chromium rust-preventive treating agent for aluminum, rust preventive treating method and aluminum product subjected to rust preventive treatment |
| JP2002060699A (en) * | 2000-08-21 | 2002-02-26 | Nippon Parkerizing Co Ltd | Agent and process for treating substrate |
| JP2008297595A (en) * | 2007-05-31 | 2008-12-11 | Nippon Paint Co Ltd | Substrate treating method for can |
| WO2008149787A1 (en) * | 2007-05-31 | 2008-12-11 | Toyo Seikan Kaisha, Ltd. | Resin-coated metal sheet and formed object made therefrom |
| JP2009079252A (en) * | 2007-09-26 | 2009-04-16 | Furukawa Sky Kk | Non-chromium type aluminum alloy plate chemical-converted material, and its coated material |
| JP2009132952A (en) * | 2007-11-29 | 2009-06-18 | Jfe Steel Corp | SURFACE-TREATED, HOT-DIP Zn-Al-BASED ALLOY PLATED STEEL SHEET |
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| JP4901116B2 (en) * | 2004-03-04 | 2012-03-21 | 新日本製鐵株式会社 | Surface-treated metal plate |
| JP4668063B2 (en) * | 2005-12-28 | 2011-04-13 | 古河スカイ株式会社 | Resin-coated aluminum plate and method for producing the same |
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| JP2001303267A (en) * | 2000-04-20 | 2001-10-31 | Nippon Paint Co Ltd | Non-chromium rust-preventive treating agent for aluminum, rust preventive treating method and aluminum product subjected to rust preventive treatment |
| JP2002060699A (en) * | 2000-08-21 | 2002-02-26 | Nippon Parkerizing Co Ltd | Agent and process for treating substrate |
| JP2008297595A (en) * | 2007-05-31 | 2008-12-11 | Nippon Paint Co Ltd | Substrate treating method for can |
| WO2008149787A1 (en) * | 2007-05-31 | 2008-12-11 | Toyo Seikan Kaisha, Ltd. | Resin-coated metal sheet and formed object made therefrom |
| JP2009079252A (en) * | 2007-09-26 | 2009-04-16 | Furukawa Sky Kk | Non-chromium type aluminum alloy plate chemical-converted material, and its coated material |
| JP2009132952A (en) * | 2007-11-29 | 2009-06-18 | Jfe Steel Corp | SURFACE-TREATED, HOT-DIP Zn-Al-BASED ALLOY PLATED STEEL SHEET |
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