JPH10317162A - Surface treatment bath for aluminum type metal, surface treatment, surface treated aluminum product, and surface treated aluminum can - Google Patents
Surface treatment bath for aluminum type metal, surface treatment, surface treated aluminum product, and surface treated aluminum canInfo
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- JPH10317162A JPH10317162A JP12971897A JP12971897A JPH10317162A JP H10317162 A JPH10317162 A JP H10317162A JP 12971897 A JP12971897 A JP 12971897A JP 12971897 A JP12971897 A JP 12971897A JP H10317162 A JPH10317162 A JP H10317162A
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- aluminum
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- surface treatment
- treatment bath
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Abstract
Description
【０００１】[0001]
【発明の属する分野】本発明はアルミニウム系金属表面
処理浴、表面処理方法および表面処理されたアルミニウ
ム製品、アルミニウム缶、特に、薄膜で均一性の高い皮
膜を形成し、外観、防食性、塗膜密着性の良好な保護被
覆を提供するアルミニウム系金属表面処理浴、表面処理
方法および表面処理されたアルミニウム製品、アルミニ
ウム缶に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum-based metal surface treatment bath, a surface treatment method and a surface-treated aluminum product, an aluminum can, and in particular, to form a thin and highly uniform film, to provide an appearance, an anticorrosion, and a coating The present invention relates to an aluminum-based metal surface treatment bath, a surface treatment method, a surface-treated aluminum product, and an aluminum can that provide a protective coating having good adhesion.
【０００２】[0002]
【従来の技術】従来、アルミニウム及びそれらの合金の
表面処理方法は、クロメート処理又はアルマイト処理等
が行われていた。しかしながら、クロメート処理は、環
境汚染並びに人体に対する毒性、排水処理スラッジの廃
棄が困難等の欠点があり、一方、アルマイト処理は多大
な設備を要し電力の消費は多く経済的でない等の欠点は
あった。2. Description of the Related Art Conventionally, as a surface treatment method for aluminum and their alloys, a chromate treatment or an alumite treatment has been performed. However, chromate treatment has drawbacks such as environmental pollution, toxicity to the human body, and difficulty in disposing of wastewater treatment sludge.On the other hand, alumite treatment requires a large amount of equipment, consumes much power, and is not economical. Was.
【０００３】そこで、上記の欠点を解消するために、種
々のノンクロメート処理方法が提案されている。例え
ば、特公昭５６−３３４６８号公報の「金属表面用コー
チング溶液」には、ジルコニウム又はチタンあるいはこ
れらの混合物と、ホスフェート（すなわち、リン酸塩）
及びフッ化物を含有し、かつ約１．５〜約４．０の範囲
内のｐＨを有する酸性の水性コーチング溶液が提案され
ている。[0003] In order to solve the above-mentioned disadvantages, various non-chromate treatment methods have been proposed. For example, “Coating solution for metal surface” in JP-B-56-33468 includes zirconium or titanium or a mixture thereof, and a phosphate (that is, a phosphate).
And an acidic aqueous coating solution containing a fluoride and a pH in the range of about 1.5 to about 4.0.
【０００４】また、特公昭５７−３９３１４号公報の
「アルミニウムの表面処理方法」には、チタン塩又はジ
ルコニウム塩の１種又は２種以上の濃度を金属換算で
０．０１〜１０ｇ／ｌ、過酸化水素濃度を０．００５〜
５ｇ／ｌとし、これにリン酸又は縮合リン酸の１種又は
２種以上を含有するリン酸換算で０．０５〜２０ｇ／ｌ
の濃度とし、これらの重量比率を１〜１０：０．１〜１
０：１．５〜３０の範囲で含有する酸性水溶液で処理す
るアルミニウム及びその合金の表面処理法が提案されて
いる。Japanese Patent Publication No. 57-39314 discloses a "method for surface treatment of aluminum". One or more concentrations of a titanium salt or a zirconium salt are 0.01 to 10 g / l in terms of metal. Hydrogen oxide concentration 0.005 to
5 g / l, and 0.05 to 20 g / l in terms of phosphoric acid containing one or more of phosphoric acid and condensed phosphoric acid.
And their weight ratios are 1 to 10: 0.1 to 1
A surface treatment method for aluminum and its alloys, which is treated with an acidic aqueous solution containing 0: 1.5 to 30, has been proposed.
【０００５】この上述の特公昭５６−３３４６８号公報
の「金属表面用コーチング溶液」や特公昭５７−３９３
１４号公報の「アルミニウムの表面処理方法」は、例え
ばアルミニウムまたはアルミニウム合金からなる飲料用
アルミニウム容器の表面に、保護皮膜を被覆する時に用
いることができる。The above-mentioned “Coating solution for metal surface” disclosed in JP-B-56-33468 and JP-B-57-393.
No. 14, "Surface treatment method for aluminum" can be used, for example, when a surface of a beverage aluminum container made of aluminum or an aluminum alloy is coated with a protective film.
【０００６】通常、アルミニウムまたはアルミニウム合
金からなる飲料用アルミニウム容器は、ドローイング・
アンド・アイアニングという成形操作（以下、ＤＩ加工
という）によって製造される。この成形操作時には金属
表面に潤滑油が適用され、また得られた容器には、特に
その内壁にアルミニウム粉末（スマット）が付着してい
るため、一般に化成処理等の前に、上記潤滑油またはス
マットを金属表面から除去し、清浄化してから、化成処
理または塗装によって容器の金属表面を保護する。[0006] Usually, aluminum containers for beverages made of aluminum or aluminum alloy are made of drawing or aluminum.
It is manufactured by a molding operation called AND ironing (hereinafter referred to as DI processing). During this molding operation, lubricating oil is applied to the metal surface, and the resulting container has aluminum powder (smut) adhered to its inner wall, in particular. Is removed from the metal surface and cleaned, and then the metal surface of the container is protected by chemical conversion or painting.
【０００７】近年では、コスト低減のため、缶蓋の外径
が２０６（６．０ｃｍ）から２０４（約５．７ｃｍ）、
更には２０２（約５．４ｃｍ）と縮径されつつある。そ
れに対応するためには、容器の上部の径も縮径しなけれ
ばならず、塗装後の缶の上部絞り加工（ネッキング加
工）がきびしくなりつつある。この縮径缶ではより高い
塗膜密着性が要求される。In recent years, the outer diameter of the can lid has been reduced from 206 (6.0 cm) to 204 (about 5.7 cm) to reduce costs.
Further, the diameter is being reduced to 202 (about 5.4 cm). In order to cope with this, the diameter of the upper portion of the container must be reduced, and the upper drawing process (necking process) of the painted can is becoming severe. In this reduced diameter can, higher coating film adhesion is required.
【０００８】[0008]
【発明が解決しようとする課題】従来の上記特公昭５７
−３９３１４号公報の「アルミニウムの表面処理方法」
に用いる表面処理浴には、金属表面に形成された酸化皮
膜を金属表面から除去する薬剤が添加されていないため
に、酸化皮膜の上に化成皮膜を形成することとなる。か
かる場合、化成皮膜は不均一となるため、沸水性やレト
ルト性等の耐食性を満足させようとすれば、化成皮膜の
膜厚を厚くする必要がある。しかしながら、化成皮膜の
膜厚を厚くすると、ネッキング加工時の塗膜と金属表面
との密着性、すなわち塗膜密着性が不十分となる。一
方、塗膜密着性を満足させようとすると、化成皮膜の膜
厚を薄くしなければならず、化成皮膜が不均一であるた
め、上記耐食性が不十分となる。Problems to be Solved by the Invention
-39314, "Surface treatment method for aluminum"
Since the surface treatment bath used for the above does not contain an agent for removing the oxide film formed on the metal surface from the metal surface, a chemical conversion film is formed on the oxide film. In such a case, since the chemical conversion film becomes non-uniform, it is necessary to increase the thickness of the chemical conversion film in order to satisfy corrosion resistance such as boiling water and retort properties. However, when the thickness of the chemical conversion coating is increased, the adhesion between the coating and the metal surface during necking, that is, the coating adhesion, becomes insufficient. On the other hand, if the adhesion of the coating film is to be satisfied, the chemical conversion film must be made thinner, and the corrosion resistance becomes insufficient because the chemical conversion film is non-uniform.
【０００９】一方、上記特公昭５６−３３４６８号公報
の「金属表面用コーチング溶液」に含まれるフッ化物
は、金属表面に形成された酸化皮膜をエッチングし、表
面より酸化皮膜を離脱させることができるが、離脱した
酸化皮膜に含有された酸素を取り込む薬剤がないため
に、再度金属表面が酸化されてしまう。このため、上記
同様、酸化皮膜の上に化成皮膜を形成することとなり、
化成皮膜は不均一となる。化成皮膜の均一性が不十分な
状態で、耐食性を満足させようとすれば、化成皮膜の膜
厚が厚くなり、塗膜密着性が不十分となる。一方、塗膜
密着性を満足させようとすると、化成皮膜の膜厚を薄く
する必要があり、化成皮膜が不均一な状態なため、上記
耐食性が不十分となる。On the other hand, the fluoride contained in the "coating solution for metal surface" disclosed in JP-B-56-33468 can etch an oxide film formed on a metal surface and release the oxide film from the surface. However, the metal surface is oxidized again because there is no agent for taking in oxygen contained in the detached oxide film. Therefore, as described above, a chemical conversion film is formed on the oxide film,
The conversion coating becomes non-uniform. If the corrosion resistance is to be satisfied in a state where the uniformity of the chemical conversion film is insufficient, the thickness of the chemical conversion film is increased, and the adhesiveness of the coating film becomes insufficient. On the other hand, in order to satisfy the coating film adhesion, it is necessary to reduce the thickness of the chemical conversion coating, and the chemical conversion coating is in an uneven state, so that the above-mentioned corrosion resistance becomes insufficient.
【００１０】すなわち、従来の表面処理方法等では、縮
径缶に対して、耐食性と塗膜密着性を両立させることは
困難であった。That is, it is difficult to achieve both corrosion resistance and coating film adhesion to a reduced diameter can by a conventional surface treatment method or the like.
【００１１】本発明は上記従来の課題に鑑みたものであ
り、その目的は、薄膜で均一性の高い皮膜を形成し、外
観、防食性、塗膜密着性の良好な保護皮膜を形成するア
ルミニウム系金属表面処理浴、表面処理方法、表面処理
されたアルミニウム製品、および表面処理アルミニウム
缶を提供することである。The present invention has been made in view of the above-mentioned conventional problems, and has as its object to form an aluminum film which forms a thin film with high uniformity and which forms a protective film having good appearance, corrosion resistance and coating adhesion. An object of the present invention is to provide a base metal surface treatment bath, a surface treatment method, a surface-treated aluminum product, and a surface-treated aluminum can.
【００１２】[0012]
【課題を解決するための手段】前述した目的を達成する
ために、本発明のアルミニウム系金属の表面処理浴は、
リン酸又はその塩の少なくとも１種をリン酸換算で２０
〜８０ｐｐｍと、ジルコニウム塩の少なくとも１種をジ
ルコニウム換算で２０〜８０ｐｐｍと、有効フッ化物を
フッ素換算で少なくとも１ｐｐｍと、亜リン酸又はその
塩の少なくとも１種を亜リン酸換算で５０〜２００ｐｐ
ｍと、硝酸又はその塩の少なくとも１種を硝酸換算で１
５０〜３５０ｐｐｍと、を含有し、ｐＨが２．６〜３．
１である。In order to achieve the above-mentioned object, an aluminum-based metal surface treatment bath of the present invention comprises:
At least one phosphoric acid or a salt thereof is converted to phosphoric acid in an amount of 20
-80 ppm, at least one kind of zirconium salt is 20-80 ppm in terms of zirconium, effective fluoride is at least 1 ppm in terms of fluorine, and at least one of phosphorous acid or a salt thereof is 50-200 pp in terms of phosphorous acid.
m and at least one of nitric acid or a salt thereof in terms of nitric acid
50 to 350 ppm, and the pH is 2.6 to 3.
It is one.
【００１３】本発明のアルミニウム系金属の表面処理浴
によって、金属表面に化成皮膜を被覆する（すなわち、
表面処理を行う）場合、本発明の表面処理浴に含まれる
フッ化物が、金属表面に形成された酸化皮膜をエッチン
グし、表面より酸化皮膜を離脱させる。また、本発明の
表面処理浴に含まれる亜リン酸又はその塩は、反応促進
剤として作用する。すなわち、これらは還元剤として働
き、金属表目面の酸化を極力防止することができると考
えられる。更に、処理浴中のジルコニム塩と、フッ化物
と、リン酸と、亜リン酸とによって、複塩が形成され、
これによって金属表面に強固な皮膜を形成する。The metal surface is coated with a conversion coating by the aluminum-based metal surface treatment bath of the present invention (ie,
In the case of performing a surface treatment), the fluoride contained in the surface treatment bath of the present invention etches the oxide film formed on the metal surface and releases the oxide film from the surface. Further, phosphorous acid or a salt thereof contained in the surface treatment bath of the present invention acts as a reaction accelerator. That is, it is considered that these act as reducing agents and can prevent oxidation of the metal surface as much as possible. Further, a double salt is formed by the zirconium salt, the fluoride, the phosphoric acid, and the phosphorous acid in the treatment bath,
This forms a strong film on the metal surface.
【００１４】また、処理浴は、通常電気伝導度（以下
「ＥＣ」という）を測定することで、自動管理される。
このＥＣは、一般に±０．０５ｍｓ／ｃｍ程度の変動幅
を許容範囲として自動管理される。しかしながら、処理
浴のＥＣが低い場合に、上記ＥＣの変動幅を許容する
と、処理浴組成の変動が大きくなってしまい、処理浴の
管理が困難となる。そこで、本発明の表面処理浴では、
処理浴のＥＣの値を引き上げる作用を有する硝酸又はそ
の塩を処理浴中に含有することとし、上記ＥＣの変動幅
を許容範囲としても、リン酸濃度、ジルコニウム濃度お
よびｐＨの変動を許容範囲に治める自動管理を可能とし
た。The treatment bath is usually automatically controlled by measuring electric conductivity (hereinafter referred to as "EC").
This EC is generally automatically controlled with a fluctuation range of about ± 0.05 ms / cm as an allowable range. However, when the EC of the treatment bath is low, if the fluctuation range of the EC is allowed, the composition of the treatment bath greatly fluctuates, and it becomes difficult to manage the treatment bath. Therefore, in the surface treatment bath of the present invention,
The treatment bath contains nitric acid or a salt thereof having an action of raising the EC value of the treatment bath, and even if the fluctuation range of the EC is within the allowable range, the fluctuation of the phosphoric acid concentration, the zirconium concentration and the pH is within the allowable range. Automatic management to control is enabled.
【００１５】[0015]
【発明の実施の形態】本発明のアルミニウム系金属表面
処理浴は、リン酸又はその塩の少なくとも１種をリン酸
換算で２０〜８０ｐｐｍと、ジルコニウム塩の少なくと
も１種をジルコニウム換算で２０〜８０ｐｐｍと、有効
フッ化物をフッ素換算で少なくとも１ｐｐｍと、亜リン
酸（Ｈ2ＰＨ2Ｏ2）又はその塩の少なくとも１種を亜リ
ン酸換算で５０〜２００ｐｐｍと、硝酸又はその塩の少
なくとも１種を硝酸換算で１５０〜３５０ｐｐｍと、を
含有し、ｐＨが２．６〜３．１である。BEST MODE FOR CARRYING OUT THE INVENTION The aluminum-based metal surface treatment bath of the present invention comprises 20 to 80 ppm of at least one phosphoric acid or a salt thereof in terms of phosphoric acid and 20 to 80 ppm of at least one zirconium salt in terms of zirconium. At least 1 ppm of effective fluoride in terms of fluorine, at least one of phosphorous acid (H 2 PH 2 O 2 ) or a salt thereof in an amount of 50 to 200 ppm in terms of phosphorous acid, and at least one of nitric acid or a salt thereof In the range of 150 to 350 ppm in terms of nitric acid, and the pH is 2.6 to 3.1.
【００１６】ここで、リン酸、リン酸塩としては、例え
ば、Ｈ3ＰＯ4 、(ＮＨ4）Ｈ2ＰＯ4、ＮａＨ2ＰＯ4、Ｋ
Ｈ2ＰＯ4等のリン酸アルカリ金属塩、リン酸カルシウ
ム、リン酸マグネシウム等のリン酸アルカリ土類金属塩
等が挙げられる。Here, as the phosphoric acid and the phosphate, for example, H 3 PO 4 , (NH 4 ) H 2 PO 4 , NaH 2 PO 4 , K
Examples thereof include alkali metal phosphates such as H 2 PO 4 and the like, and alkaline earth metal phosphates such as calcium phosphate and magnesium phosphate.
【００１７】ジルコニウム塩としては、例えばジルコニ
ウムフッ化水素酸（Ｈ2ＺｒＦ6）及びフルオロジルコニ
ウム酸のリチウム、ナトリウム、カリウム、アンモニウ
ム塩（Ｌｉ2ＺｒＦ6、Ｎａ2ＺｒＦ6、Ｋ2ＺｒＦ6、(Ｎ
Ｈ4)2ＺｒＦ6）、硫酸ジルコニウム（Ｚｒ(ＳＯ4)2）、
硫酸ジルコニル（ＺｒＯ(ＳＯ4））、硝酸ジルコニウム
（Ｚｒ(ＮＯ3)4）、硝酸ジルコニル（ＺｒＯ(Ｎ
Ｏ3)2）、酢酸ジルコニウム、フッ化ジルコニウム（Ｚ
ｒＦ4）等を挙げることができる。フッ化物としては、
例えば、フッ化水素酸（ＨＦ）、フッ化アンモニウム
（ＮＨ4Ｆ）、フッ化水素アンモニウム（ＮＨ4 Ｈ
Ｆ2 ）、フッ化ナトリウム（ＮａＦ）、フッ化水素ナト
リウム（ＮａＨＦ2）等が挙げられる。Examples of the zirconium salt include lithium, sodium, potassium and ammonium salts of zirconium hydrofluoric acid (H 2 ZrF 6 ) and fluorozirconic acid (Li 2 ZrF 6 , Na 2 ZrF 6 , K 2 ZrF 6 , ( N
H 4 ) 2 ZrF 6 ), zirconium sulfate (Zr (SO 4 ) 2 ),
Zirconyl sulfate (ZrO (SO 4 )), zirconium nitrate (Zr (NO 3 ) 4 ), zirconyl nitrate (ZrO (N
O 3 ) 2 ), zirconium acetate, zirconium fluoride (Z
rF 4 ). As fluoride,
For example, hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium hydrogen fluoride (NH 4 H)
F 2 ), sodium fluoride (NaF), sodium hydrogen fluoride (NaHF 2 ), and the like.
【００１８】亜リン酸、亜リン酸塩としては、例えばＨ
2 ＰＨＯ3 、（ＮＨ4)2ＰＨＯ3や、Ｎａ2ＰＨＯ3、Ｋ2
ＰＨＯ3等のアルカリ金属塩、ＣａＰＨＯ3、ＭｇＰＨＯ
3等のアルカリ土類金属塩等が挙げられる。Examples of phosphorous acid and phosphite include H
2 PHO 3 , (NH 4 ) 2 PHO 3 , Na 2 PHO 3 , K 2
Alkali metal salts such as PHO 3 , CaPHO 3 , MgPHO
And alkaline earth metal salts such as 3.
【００１９】硝酸、硝酸塩としては、例えばＨＮＯ3、
ＮＨ4ＮＯ3 や、ＮａＮＯ3、ＫＮＯ3等のアルカリ金属
塩、Ｃａ(ＮＯ3)2、Ｍｇ(ＮＯ3)2等のアルカリ度類金属
塩等が挙げられる。As nitric acid and nitrate, for example, HNO 3 ,
Examples thereof include alkali metal salts such as NH 4 NO 3 , NaNO 3 and KNO 3 , and alkali metal salts such as Ca (NO 3 ) 2 and Mg (NO 3 ) 2 .
【００２０】また、ｐＨは２．６〜３．１に調整される
が、これは配合されるリン酸、ジルコニウム塩、フッ化
水素、亜リン酸、硝酸の適当な塩で添加することが可能
である。The pH is adjusted to 2.6 to 3.1, which can be added with a suitable salt of phosphoric acid, zirconium salt, hydrogen fluoride, phosphorous acid, and nitric acid. It is.
【００２１】なお、本発明のアルミニウム系金属の表面
処理浴は、濃縮物を適量の水によって使用範囲内の濃度
に希釈することによって得られる。The aluminum-based metal surface treatment bath of the present invention can be obtained by diluting the concentrate with an appropriate amount of water to a concentration within the range of use.
【００２２】リン酸又はその塩の少なくとも１種が、本
実施形態の処理浴中に、リン酸換算で２０〜８０ｐｐ
ｍ、好ましくは３０〜５０ｐｐｍ含まれている。リン酸
又はその塩の少なくとも１種が、処理浴中にリン酸換算
で２０ｐｐｍ未満の場合には、耐沸水黒変性が低下し、
一方リン酸等が多い場合には、塗膜の密着性が低下する
ため、リン酸換算で８０ｐｐｍ以内が好ましい。At least one kind of phosphoric acid or a salt thereof is contained in the treatment bath of this embodiment in an amount of 20 to 80 pp in terms of phosphoric acid.
m, preferably 30 to 50 ppm. When at least one of phosphoric acid or a salt thereof is less than 20 ppm in terms of phosphoric acid in the treatment bath, blackening resistance to boiling water decreases,
On the other hand, when the amount of phosphoric acid or the like is large, the adhesion of the coating film is reduced.
【００２３】ジルコニウム塩の少なくとも１種は、本実
施形態の処理浴中に、金属換算で２０〜８０ｐｐｍ、好
ましくは３０〜５０ｐｐｍ含まれている。ジルコニウム
塩の少なくとも１種が、処理浴中に金属換算で２０ｐｐ
ｍ未満の場合には、ほとんど化成皮膜が形成されない。
一方処理浴中にジルコニウム塩等を多く添加しても効果
が上がらないため、金属換算で８０ｐｐｍ以内が好まし
い。At least one zirconium salt is contained in the treatment bath of the present embodiment in an amount of 20 to 80 ppm, preferably 30 to 50 ppm in terms of metal. At least one zirconium salt is contained in the treatment bath in an amount of 20 pp in terms of metal.
If it is less than m, a chemical conversion film is hardly formed.
On the other hand, even if a large amount of zirconium salt or the like is added to the treatment bath, the effect is not improved.
【００２４】有効フッ化物は、本実施形態の処理浴中
に、フッ素換算で少なくとも１ｐｐｍ、好ましくは３〜
５０ｐｐｍ含まれる。有効フッ化物が、本実施形態の処
理浴中に、フッ素換算で１ｐｐｍ未満の場合には、アル
ミニウム系金属の表面のエッチングがほとんど起こらな
いため、アルミニウム系金属（アルミニウム、アルミニ
ウム合金等を含む）の表面と皮膜の密着性が低下する。
一方、フッ化物の含有量が多いと、被膜の生成速度より
もエッチングの速度の方が早いために被膜の形成が困難
となるだけでなく、耐沸水黒変性、塗膜との密着性が低
下するので、フッ素換算で５０ｐｐｍ以内が好ましい。The effective fluoride is present in the treatment bath of the present embodiment in an amount of at least 1 ppm, preferably from 3 to 3 ppm in terms of fluorine.
50 ppm is contained. If the effective fluoride is less than 1 ppm in terms of fluorine in the treatment bath of the present embodiment, the etching of the surface of the aluminum-based metal hardly occurs, so that the aluminum-based metal (including aluminum, aluminum alloy, etc.) The adhesion between the surface and the film decreases.
On the other hand, when the content of fluoride is large, not only the formation rate of the coating is difficult because the etching rate is faster than the formation rate of the coating, but also the blackening resistance to boiling water and the adhesion to the coating are reduced. Therefore, the content is preferably within 50 ppm in terms of fluorine.
【００２５】ここで、有効フッ化物とは、処理浴中でフ
ッ素イオンを遊離するフッ化物をいい、この処理浴中の
遊離のフッ素イオン（Ｆ-）を、以下「有効フッ素イオ
ン」という。この有効フッ素イオンの濃度は、フッ素イ
オン電極を有するメーターで処理浴などを測定すること
によって求められる。有効フッ素イオンは、アルミニウ
ム表面の酸化膜をエッチングする他に、処理浴中のジル
コニウム・ホスフェートの沈殿生成を制止するか又は防
ぐ働きがある。更に、アルミニウム表面処理中に処理浴
に溶け出したアルミニウムを錯体として処理浴中に溶解
させ、表面処理のプロセスにおける悪影響を制止又は予
防する働きもある。Here, the effective fluoride means a fluoride that releases fluorine ions in the treatment bath, and the free fluoride ions (F − ) in the treatment bath are hereinafter referred to as “effective fluorine ions”. The concentration of this effective fluorine ion can be determined by measuring the treatment bath or the like with a meter having a fluorine ion electrode. Effective fluorine ions, besides etching the oxide film on the aluminum surface, also serve to control or prevent precipitation of zirconium phosphate in the treatment bath. Furthermore, it also has the function of dissolving aluminum dissolved in the treatment bath during the aluminum surface treatment as a complex in the treatment bath to control or prevent adverse effects in the surface treatment process.
【００２６】亜リン酸又はその塩の少なくとも１種は、
本実施形態の処理浴中に、亜リン酸換算で、５０〜２０
０ｐｐｍ、好ましくは８０〜１００ｐｐｍ含まれる。亜
リン酸又はその塩の少なくとも１種が、本実施形態の処
理浴中に、亜リン酸換算で５０ｐｐｍ未満の場合には、
化成被膜の均一性が不十分となり、一方処理浴中の亜リ
ン酸の濃度が高いと、塗膜密着性が低下し、また不溶解
物（「スラッジ」という）が発生しやすくなるので、亜
リン酸換算で２００ｐｐｍ以内が好ましい。At least one of phosphorous acid or a salt thereof is
In the treatment bath of this embodiment, 50 to 20 in terms of phosphorous acid
0 ppm, preferably 80 to 100 ppm. When at least one of phosphorous acid or a salt thereof is less than 50 ppm in terms of phosphorous acid in the treatment bath of the present embodiment,
If the conversion coating film has insufficient uniformity and the concentration of phosphorous acid in the treatment bath is high, the adhesion of the coating film will be reduced and insolubles ("sludge") will be easily generated. It is preferably within 200 ppm in terms of phosphoric acid.
【００２７】硝酸又はその塩の少なくとも１種は、本実
施形態の処理浴中に、硝酸換算で１５０〜３５０ｐｐ
ｍ、好ましくは２００〜２５０ｐｐｍ含まれる。硝酸又
はその塩の少なくとも１種が、本実施形態の処理浴中に
硝酸換算で１５０ｐｐｍ未満の場合には、処理浴組成の
変動が大きくなる。一方、処理浴中の硝酸濃度が高い
と、廃水処理に負荷がかかる（窒素規制）ので、硝酸換
算で３５０ｐｐｍ以内が好ましい。At least one kind of nitric acid or a salt thereof is added to the treatment bath of the present embodiment in an amount of 150 to 350 pp in terms of nitric acid.
m, preferably 200 to 250 ppm. When at least one of nitric acid and its salt is less than 150 ppm in terms of nitric acid in the treatment bath of the present embodiment, the composition of the treatment bath greatly fluctuates. On the other hand, if the concentration of nitric acid in the treatment bath is high, a load is imposed on wastewater treatment (nitrogen regulation).
【００２８】本実施形態の処理浴のｐＨは、２．６〜
３．１、好ましくは２．８〜２．９ある。処理浴のｐＨ
が２．６未満の場合には、エッチング過剰となり、被膜
の生成が困難となるだけでなく、耐沸水黒変性、塗膜密
着性が低下する。一方処理浴のｐＨが３．１を越える
と、処理浴が白濁し、スラッジが発生しやすくなる。ま
た、被膜もほとんど生成しないため、耐沸水黒変性が低
下する。The pH of the treatment bath of the present embodiment is from 2.6 to
3.1, preferably 2.8 to 2.9. PH of treatment bath
If the ratio is less than 2.6, etching becomes excessive and not only the formation of a coating film becomes difficult, but also the blackening resistance to boiling water and the adhesion of the coating film decrease. On the other hand, when the pH of the treatment bath exceeds 3.1, the treatment bath becomes cloudy and sludge is easily generated. Further, since almost no film is formed, the blackening resistance to boiling water is reduced.
【００２９】本発明のアルミニウム系金属の表面処理浴
に供される対象素材は、アルミニウム及び／又はアルミ
ニウム合金である。このアルミニウム及び／又はアルミ
ニウム合金としては、例えばアルミニウム、アルミニウ
ム−銅、アルミニウム−亜鉛、アルミニウム−マンガ
ン、アルミニウム−マグネシウム、アルミニウム−マグ
ネシウム−ケイ素、アルミニウム−亜鉛−マグネシウム
等が挙げられる。更に、対象素材の形状は、板状、棒
状、線、管でもよく、飲料缶などに適用することができ
る。The target material provided in the aluminum-based metal surface treatment bath of the present invention is aluminum and / or an aluminum alloy. Examples of the aluminum and / or aluminum alloy include aluminum, aluminum-copper, aluminum-zinc, aluminum-manganese, aluminum-magnesium, aluminum-magnesium-silicon, and aluminum-zinc-magnesium. Further, the shape of the target material may be a plate shape, a bar shape, a line, a tube, and can be applied to a beverage can or the like.
【００３０】本実施形態のアルミニウム系金属表面処理
方法（以下「処理方法」）の処理温度は、室温〜６０
℃、好ましくは３０〜５０℃である。処理温度が室温
（例えば２５℃）未満の場合には、被膜生成速度が遅い
ため、高濃度仕様となり経済的に不利である。一方、処
理温度が６０℃を超える場合には、処理浴が白濁し、ス
ラッジが発生しやすくなる。また、温度維持に多大なエ
ネルギーを必要とするため、経済的に不利である。The treatment temperature of the aluminum-based metal surface treatment method (hereinafter referred to as "treatment method") of the present embodiment is from room temperature to 60.
° C, preferably 30 to 50 ° C. If the treatment temperature is lower than room temperature (for example, 25 ° C.), the film formation rate is low, and the concentration is high, which is economically disadvantageous. On the other hand, when the processing temperature exceeds 60 ° C., the processing bath becomes cloudy and sludge is easily generated. Further, a large amount of energy is required for maintaining the temperature, which is economically disadvantageous.
【００３１】本実施形態の処理方法の処理時間は、処理
組成物、処理温度と処理方法によって異なるが、一般的
には５〜６０秒であり、本実施形態の処理方法として
は、上記処理浴中にアルミニウム製品等を浸漬してもよ
いし、また上記処理浴をアルミニウム製品等に噴霧又は
塗布等の公知の方法で処理してもよい。The processing time of the processing method of the present embodiment varies depending on the processing composition, the processing temperature and the processing method, but generally ranges from 5 to 60 seconds. An aluminum product or the like may be immersed therein, or the treatment bath may be treated by a known method such as spraying or coating on the aluminum product or the like.
【００３２】更に、請求項に記載以外の本発明の好まし
い他の実施態様を以下に示す。Further, other preferred embodiments of the present invention other than those described in the claims are shown below.
【００３３】１．アルミニウム系金属の表面処理浴は、
リン酸又はその塩の少なくとも１種をリン酸換算で３０
〜５０ｐｐｍと、ジルコニウム塩の少なくとも１種をＺ
ｒ換算で３０〜５０ｐｐｍと、有効フッ化物をフッ素換
算で３〜５０ｐｐｍと、亜リン酸又はその塩の少なくと
も１種を亜リン酸換算で８０〜１００ｐｐｍと、硝酸ま
たはその塩の少なくとも１種を硝酸換算で２００〜２５
０ｐｐｍと、を含有し、ｐＨが２．８〜２．９である。1. Aluminum-based metal surface treatment baths
Phosphoric acid or at least one of its salts is converted to phosphoric acid by 30
And at least one zirconium salt with Z
30 to 50 ppm in terms of r, 3 to 50 ppm of effective fluoride in terms of fluorine, 80 to 100 ppm in terms of phosphorous acid of at least one kind of phosphorous acid or a salt thereof, and at least one kind of nitric acid or a salt thereof. 200 to 25 in terms of nitric acid
0 ppm, and the pH is 2.8 to 2.9.
【００３４】２．アルミニウム系金属表面処理方法の処
理温度は、室温〜６０℃である。2. The treatment temperature of the aluminum-based metal surface treatment method is from room temperature to 60 ° C.
【００３５】[0035]
【実施例】次に、実施例及び比較例を挙げて、本発明を
具体的に説明する。Next, the present invention will be described in detail with reference to examples and comparative examples.
【００３６】実施例１〜１１及び比較例１〜６ （１）被処理物：３００４合金のアルミニウム板をＤＩ
加工して得られた、潤滑油とスマットの付着したフタな
し容器を用いた。 Examples 1 to 11 and Comparative Examples 1 to 6 (1) Object to be treated: A 3004 alloy aluminum plate was treated with DI
A lidless container to which lubricating oil and smut adhered was used.
【００３７】（２）洗浄剤：日本ペイント（株）社製酸
性洗浄剤「サーフクリーナーＮＨＣ２５０」を使用し
た。(2) Detergent: An acidic detergent "Surf Cleaner NHC250" manufactured by Nippon Paint Co., Ltd. was used.
【００３８】（３）処理条件：上記容器を上記洗浄剤
で、７５℃で６０秒間スプレー処理し、潤滑油とスマッ
トを除去した後、水道水を１５秒間スプレー水洗後、表
１に示す処理浴の処理液をスプレーした。次いで水道水
で１５秒間、脱イオン水で５秒間スプレー水洗し、その
後２００℃で２分間乾燥した。(3) Treatment conditions: The above-mentioned container was spray-treated with the above-mentioned cleaning agent at 75 ° C. for 60 seconds to remove lubricating oil and smut, followed by spray-washing with tap water for 15 seconds, and a treatment bath shown in Table 1. Was sprayed. Then, it was spray-washed with tap water for 15 seconds and deionized water for 5 seconds, and then dried at 200 ° C. for 2 minutes.
【００３９】（４）洗浄性評価：以下の項目について試
験した。その結果を表２に示す。(4) Evaluation of detergency: The following items were tested. Table 2 shows the results.
【００４０】（ａ）耐沸水黒変性：処理されたＤＩ加工
容器（以下「処理缶」という）から切り出したボトム部
を１００℃の沸騰した水道水に３０分間浸漬し、黒変の
程度を観察した。黒変の程度に応じて以下の５段階評価
した。(A) Blackening resistance to boiling water: A bottom part cut out from a treated DI processing container (hereinafter referred to as a “processing can”) is immersed in boiling tap water at 100 ° C. for 30 minutes, and the degree of blackening is observed. did. The following five grades were evaluated according to the degree of blackening.
【００４１】 ◎ ： 全く黒変なし ○ ： 僅かに黒変 △ ： 軽く黒変 × ： かなり黒変 ××： 完全に黒変 （ｂ）耐レトルト性：圧力釜内で水道水を加圧して１２
５℃にした蒸気部に処理缶を３０分間設置し、白化の程
度を観察した。白化の程度に応じて以下の５段階評価し
た。◎: No blackening at all ○: Slight blackening Δ: Slightly blackening ×: Pretty blackening XX: Completely blackening (b) Retort resistance: 12% by pressurizing tap water in pressure cooker
The treatment can was placed in the steam section at 5 ° C. for 30 minutes, and the degree of whitening was observed. The following five levels were evaluated according to the degree of whitening.
【００４２】 ◎ ： 全く白化なし ○ ： 僅かに白化 △ ： 軽く白化 × ： かなり白化 ××： 完全に白化 （ｃ）塗膜密着性：処理缶の外面に、水性ホワイト塗料
を塗布し、更にその上にクリヤー塗料（エポキシ変性ア
クリル系クリヤー塗料）を塗布して、焼き付け乾燥して
試験片とした。塗膜密着性の評価は、折り曲げ（ウェッ
ジベンディング法）により行った。この塗膜密着性の評
価方法は、図１に示すように、先端の０ｍｍφから３°
の傾斜で折り曲げ、この先端から８０ｍｍにおいて４ｍ
ｍφになる（図２参照）ように折り曲げた後、図３に示
すように、折曲げ部にテープを貼ってから、テープを剥
離させ（図３の白抜き矢印方向に剥離させ）、テープを
剥離させた際に先端からの塗膜の剥離長さ（ｍｍ）によ
って評価する方法である。なお、塗膜の剥離長さが短い
ほど塗膜密着性が良好であることを示す。◎: no whitening ○: slight whitening △: light whitening ×: considerable whitening ××: complete whitening (c) Coating adhesion: A water-based white paint was applied to the outer surface of the treated can, and A clear paint (epoxy-modified acrylic clear paint) was applied thereon, baked and dried to obtain test pieces. Evaluation of coating film adhesion was performed by bending (wedge bending method). As shown in FIG. 1, the evaluation method of the coating film adhesion is 3 ° from 0 mmφ at the tip.
4m at 80mm from this tip
After bending so as to have a diameter of mφ (see FIG. 2), as shown in FIG. 3, a tape is stuck to the bent portion, and then the tape is peeled off (peeled in the direction of the white arrow in FIG. 3). This is a method of evaluating the peeling length (mm) of the coating film from the tip when peeled. The shorter the peel length of the coating film, the better the coating film adhesion.
【００４３】表２、評価結果を示す。Table 2 shows the evaluation results.
【００４４】[0044]
【表１】 [Table 1]
【表２】 実施例１２、１３及び比較例７ 実施例１に示す処理浴に準じて、硝酸濃度を１５０ｐｐ
ｍ（実施例１２）、３００ｐｐｍ（実施例１３）、０ｐ
ｐｍ（比較例７）に変えて、電気伝導度（ＥＣ）の許容
変動幅を±０．０５ｍｓ／ｃｍとして自動管理したとき
の処理浴のＺｒ濃度、ＰＯ4濃度及びｐＨの変動を評価
した。結果を表３に示す。[Table 2] Examples 12 and 13 and Comparative Example 7 According to the treatment bath shown in Example 1, the nitric acid concentration was 150 pp.
m (Example 12), 300 ppm (Example 13), 0 p
pm (Comparative Example 7), and the fluctuation of the Zr concentration, PO 4 concentration and pH of the treatment bath when the allowable fluctuation width of the electric conductivity (EC) was automatically controlled as ± 0.05 ms / cm was evaluated. Table 3 shows the results.
【００４５】[0045]
【表３】 これらの結果から、本発明のアルミニウム系金属の表面
処理浴、表面処理方法によれば、薄膜で均一性の高い皮
膜を形成し、得られるアルミニウム製品、アルミニウム
缶は、外観、防食性、塗膜密着性ともに従来のものに比
べ向上し、処理浴組成の変動も非常に少ないことが判明
した。[Table 3] From these results, according to the aluminum-based metal surface treatment bath and the surface treatment method of the present invention, a thin and highly uniform film is formed, and the obtained aluminum product and aluminum can have an appearance, corrosion resistance, It was found that the adhesion was improved as compared with the conventional one, and that the variation in the composition of the treatment bath was very small.
【００４６】[0046]
【発明の効果】以上のように、本発明に係るアルミニウ
ム系金属の表面処理用浴、表面処理方法によれば、薄膜
で均一性が高い皮膜を形成できるので、得られるアルミ
ニウム製品、アルミニウム缶は加工密着性が従来より、
格段に優れ、かつ耐沸水黒変性や耐レトルト性にも優れ
る。As described above, according to the aluminum-based metal surface treatment bath and the surface treatment method of the present invention, a thin and highly uniform film can be formed. Processing adhesion is better than before
It is remarkably excellent and has excellent resistance to boiling water blackening and retort resistance.
【図１】 塗膜密着性の評価に用いる試験片の折り曲げ
状態を示す斜視図である。FIG. 1 is a perspective view showing a bent state of a test piece used for evaluation of coating film adhesion.
【図２】 図１に示す折り曲げられた試験片を背面から
見た斜視図である。FIG. 2 is a perspective view of the bent test piece shown in FIG. 1 as viewed from the back.
【図３】 塗膜密着性の試験方法を説明する図である。FIG. 3 is a diagram illustrating a method for testing coating film adhesion.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池田 哲 東京都品川区南品川４丁目１番15号 日本 ペイント株式会社東京事業所内 (72)発明者 神村 雅之 東京都品川区南品川４丁目１番15号 日本 ペイント株式会社東京事業所内 (72)発明者 園村 一夫 東京都品川区南品川４丁目１番15号 日本 ペイント株式会社東京事業所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsu Ikeda 4-1-1-15 Minamishinagawa, Shinagawa-ku, Tokyo Japan Paint Co., Ltd. Tokyo Office (72) Inventor Masayuki Kamimura 4-1-1 Minamishinagawa, Shinagawa-ku, Tokyo No. 15 Nippon Paint Co., Ltd. Tokyo Office (72) Inventor Kazuo Sonomura 4-1-1, Minamishinagawa, Shinagawa-ku, Tokyo Nippon Paint Co., Ltd. Tokyo Office
Claims (5)
ン酸換算で２０〜８０ｐｐｍと、 ジルコニウム塩の少なくとも１種をジルコニウム換算で
２０〜８０ｐｐｍと、 有効フッ化物をフッ素換算で少なくとも１ｐｐｍと、 亜リン酸又はその塩の少なくとも１種を亜リン酸換算で
５０〜２００ｐｐｍと、 硝酸又はその塩の少なくとも
１種を硝酸換算で１５０〜３５０ｐｐｍと、 を含有し、ｐＨが２．６〜３．１であることを特徴とす
るアルミニウム系金属の表面処理浴。(1) at least one kind of phosphoric acid or a salt thereof is 20 to 80 ppm in terms of phosphoric acid, at least one kind of zirconium salt is 20 to 80 ppm in terms of zirconium, and effective fluoride is at least 1 ppm in terms of fluorine. At least one of phosphorous acid or a salt thereof is 50 to 200 ppm in terms of phosphorous acid; and at least one of nitric acid or a salt thereof is in a range of 150 to 350 ppm in terms of nitric acid, and has a pH of 2.6 to 3. A surface treatment bath for an aluminum-based metal, which is 1.
ニウム系金属製品に接触させることを特徴とするアルミ
ニウム系金属の表面処理方法。2. A method for surface-treating an aluminum-based metal, comprising bringing the surface-treatment bath according to claim 1 into contact with an aluminum-based metal product.
度、ジルコニウム濃度およびｐＨ管理を浴の電気伝導度
の測定により自動管理するに際し、前記表面処理浴中に
含有されている１５０〜３５０ｐｐｍの硝酸又はその塩
の少なくとも１種によって、前記電気伝導度の許容変動
幅における前記リン酸濃度、ジルコニウム濃度およびｐ
Ｈの変動幅を縮小させて自動管理を容易にすることを特
徴とするアルミニウム系金属の表面処理方法。3. The method for automatically controlling the concentration of phosphoric acid, the concentration of zirconium, and the pH of the surface treatment bath according to claim 1 by measuring the electric conductivity of the bath, wherein the concentration of the phosphoric acid is 150 to 150%. The phosphoric acid concentration, the zirconium concentration and p
A surface treatment method for an aluminum-based metal, characterized in that the fluctuation range of H is reduced to facilitate automatic management.
せることにより得られる表面処理されたアルミニウム製
品。4. A surface-treated aluminum product obtained by contacting the surface treatment bath according to claim 1.
せることにより得られる表面処理されたアルミニウム
缶。5. A surface-treated aluminum can obtained by contacting the surface treatment bath according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12971897A JP3502235B2 (en) | 1997-05-20 | 1997-05-20 | Aluminum-based metal surface treatment bath, surface treatment method, surface-treated aluminum product, and surface-treated aluminum can |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12971897A JP3502235B2 (en) | 1997-05-20 | 1997-05-20 | Aluminum-based metal surface treatment bath, surface treatment method, surface-treated aluminum product, and surface-treated aluminum can |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10317162A true JPH10317162A (en) | 1998-12-02 |
| JP3502235B2 JP3502235B2 (en) | 2004-03-02 |
Family
ID=15016495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12971897A Expired - Lifetime JP3502235B2 (en) | 1997-05-20 | 1997-05-20 | Aluminum-based metal surface treatment bath, surface treatment method, surface-treated aluminum product, and surface-treated aluminum can |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3502235B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007113097A (en) * | 2005-10-24 | 2007-05-10 | Showa Aluminum Kan Kk | Method for manufacturing aluminum can, and aluminum can manufactured with the method |
| JP2012107309A (en) * | 2010-10-18 | 2012-06-07 | Kobe Steel Ltd | Aluminum alloy sheet, joined body using the same, and automobile member |
| JP2016211012A (en) * | 2015-04-28 | 2016-12-15 | 株式会社神戸製鋼所 | Aluminum alloy sheet for packaging container |
-
1997
- 1997-05-20 JP JP12971897A patent/JP3502235B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007113097A (en) * | 2005-10-24 | 2007-05-10 | Showa Aluminum Kan Kk | Method for manufacturing aluminum can, and aluminum can manufactured with the method |
| JP2012107309A (en) * | 2010-10-18 | 2012-06-07 | Kobe Steel Ltd | Aluminum alloy sheet, joined body using the same, and automobile member |
| JP2014198911A (en) * | 2010-10-18 | 2014-10-23 | 株式会社神戸製鋼所 | Aluminum alloy sheet, joined body using the same, and automotive member |
| JP2016211012A (en) * | 2015-04-28 | 2016-12-15 | 株式会社神戸製鋼所 | Aluminum alloy sheet for packaging container |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3502235B2 (en) | 2004-03-02 |
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