JP3623015B2 - Surface treatment liquid for aluminum-containing metal material and surface treatment method - Google Patents
Surface treatment liquid for aluminum-containing metal material and surface treatment method Download PDFInfo
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- JP3623015B2 JP3623015B2 JP16624395A JP16624395A JP3623015B2 JP 3623015 B2 JP3623015 B2 JP 3623015B2 JP 16624395 A JP16624395 A JP 16624395A JP 16624395 A JP16624395 A JP 16624395A JP 3623015 B2 JP3623015 B2 JP 3623015B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
Description
【０００１】
【産業上の利用分野】
本発明はアルミニウム含有金属材料、即ちアルミニウム材料およびアルミニウム合金材料表面に優れた耐食性と塗膜密着性を付与するための新規なアルミニウム含有金属材料用表面処理組成物、表面処理液および表面処理方法に関するものである。本発明は、アルミニウム合金製のコイル、シート材の表面処理に特に効果的に適用される。
【０００２】
【従来の技術】
アルミニウム含有金属材料用表面処理液はクロメートタイプとノンクロメートタイプとに大別できる。クロメートタイプ処理液の代表的なものとしては、クロム酸クロメート化成処理液とりん酸クロメート化成処理液とを挙げることができる。
クロム酸クロメート化成処理液は、１９５０年頃に実用化され、現在も熱交換器用フィン材、および航空機材料などに広く使用されている。このクロム酸クロメート化成処理液は、クロム酸と、反応促進剤として作用するフッ化物とを主成分として含有するものであって、金属材料表面上に若干量の６価クロムを含有する化成皮膜を形成する。
【０００３】
りん酸クロメート化成処理液は、米国特許第２４３８８７７号公報に開示された発明によるものであり、この化成処理液はクロム酸、りん酸およびフッ化水素酸を主成分として含有するもので、金属材料表面上に水和したりん酸クロムを主成分とする化成皮膜を形成する。この化成皮膜には６価クロムが含有されていないので、この処理液は飲料缶のボディー材および蓋材の塗装下地処理などの用途に現在も広く使用されている。しかし、前記クロメートタイプ表面処理液中には、有害な６価クロムが含有されているので、環境上の問題より６価クロムを含有しない処理液の使用が望まれている。
【０００４】
クロムを含有しないノンクロメートタイプ表面処理液の代表的な発明としては、特開昭５２−１３１９３７号公報に開示の方法が挙げられる。この処理液はジルコニウムまたはチタン、あるいはこれらの混合物と、ホスフェートおよびフッ化物とを含有し、且つ約１．５〜４．０のｐＨを有する、酸性の水性コーティング溶液である。この表面処理液を用いて金属材料表面上に処理を施すと、金属表面上にジルコニウムあるいはチタンの酸化物を主成分とする化成皮膜が形成される。このノンクロメートタイプ表面処理液は、６価クロムを含有しないという利点を有しており、現在アルミニウムＤＩ缶の表面処理等に広く用いられているが、クロメートタイプ表面処理液に比べると、反応性が低いために皮膜を形成させるまでの処理時間が長く、また、形成された皮膜の耐食性および塗膜密着性が、クロメート皮膜よりも劣るという欠点がある。また近年、生産性の向上に伴うラインスピードの高速化が進んでおり、表面処理時間の短縮化が大きな課題となっているのである。
【０００５】
前記表面処理時間の短縮化を目的とした発明としては、特開平１−２４６３７０号公報に開示の処理方法が知られている。この方法は、アルミニウム含有金属材料にアルカリ脱脂剤による表面洗浄を施し、次にこの洗浄表面にジルコニウムイオン０．０１〜０．５ｇ／リットル、りん酸イオン０．０１〜０．５ｇ／リットルおよび有効フッ素イオン０．００１〜０．０５ｇ／リットル、あるいは更にバナジウムイオン０．０１〜１ｇ／リットルを含有し、且つ１．５〜４．０のｐＨを有する酸性水溶液を用いて表面処理するものであるが、この方法をアルミニウムＤＩ缶に用いた際には、得られる皮膜が十分な耐黒変性を有していない場合がある。
【０００６】
また、他のノンクロメート処理方法として、特公昭５７−３９３１４号公報に、チタン塩またはジルコニウム塩の１種または２種以上と、過酸化水素と、りん酸または縮合りん酸の１種または２種以上とを含む酸性溶液により、アルミニウム含有金属表面を処理する処理方法が開示されている。しかし、この処理液は不安定であり、且つ表面皮膜形成のための反応性も不満足であり、かつ上記公報には、処理時間、処理温度、処理操作についての具体的な記載も開示されていない。
【０００７】
このような理由により、短時間処理が要求されるアルミニウム含有金属材料のコイルおよびシート材の表面処理ラインにおいて、現状ではノンクロメートタイプの表面処理液はほとんど使用されていないのである。
従って現在までのところ、処理液中に６価クロムを含有せず、短時間処理が可能で、且つ耐食性および塗膜密着性に優れる皮膜を形成することができるアルミニウム含有金属材料用表面処理組成物、表面処理液、および表面処理方法は確立されていないのである。
【０００８】
【発明が解決しようとする課題】
本発明は、従来技術の抱える上記問題点を解決するためのものであり、具体的にはアルミニウム含有金属材料表面に優れた耐食性と塗膜密着性を有する皮膜を短時間で形成することが可能なアルミニウム含有金属材料用表面処理組成物、表面処理液および表面処理方法を提供しようとするものである。
【０００９】
【課題を解決するための手段】
本発明者らは、従来技術の抱える前記問題点を解決するための手段について鋭意検討を行った。その結果、特定量のりん酸イオンと、チタン化合物と、フッ化物と、特定組成の促進剤とを含有する表面処理組成物を用いることにより優れた耐食性および塗膜密着性を有する皮膜を、短時間内に、アルミニウム含有金属材料表面に形成し得ることを新たに見い出し、本発明を完成するに至った。
【００１０】
本発明に係るアルミニウム含有金属材料用表面処理組成物は、０．０１〜５重量部のりん酸イオンと、チタン原子に換算して０．０１〜２重量部のチタン化合物と、フッ素原子に換算して０．０１〜１２重量部のフッ化物と、０．０１〜２重量部の、硝酸、過マンガン酸、及びこれらの水溶性塩、並びに水溶性有機過酸化物から選ばれた少なくとも１種からなる促進剤とを含むことを特徴とするものである。
【００１２】
また、本発明のアルミニウム含有金属材料用表面処理液は、前記本発明のアルミニウム含有金属材料用表面処理組成物から調製されたものであって、０．０１〜５ｇ／リットルのりん酸イオンと、チタン原子に換算して０．０１〜２ｇ／リットルのチタン化合物と、フッ素原子に換算して０．０１〜１２ｇ／リットルのフッ化物と、０．０１〜２ｇ／リットルの、硝酸、過マンガン酸、及びこれらの水溶性塩並びに水溶性有機過酸化物から選ばれた少なくとも１種からなる促進剤とを含み、かつ１．０〜４．５のpHを有することを特徴とするものである。
【００１３】
また、本発明のアルミニウム含有金属材料の表面処理方法は、前記の処理組成物から調製され、かつ１．０〜４．５のpHを有する表面処理液を、室温〜８０℃の温度において、アルミニウム含有金属材料の表面に、接触させ、その後、前記金属材料の表面処理液付着表面を水洗し、加熱乾燥して化成皮膜を形成することを特徴とするものである。前記表面処理液による前記アルミニウム含有金属材料表面の接触処理時間は４〜１２秒間であることが好ましい。また、この化成皮膜は、チタン原子に換算して３〜５０mg／ｍ2 の重量であることが好ましい。
【００１４】
【作用】
次に、本発明の構成について詳細に説明する。
本発明の処理組成物は、りん酸イオンとチタン化合物とフッ化物と特定促進剤を必須成分として含有する水性溶液であって、通常酸性を示すものである。特に、本発明の処理組成物において、特定促進剤が使用されていることが好ましい。このような特定促進剤を用いた場合、処理液の反応性、形成された皮膜の耐食性および塗膜密着性を著しく向上させることができる。
【００１５】
本発明のアルミニウム含有金属材料表面処理用処理組成物において、りん酸イオン、チタン化合物、フッ化物および促進剤は、下記重量比で配合されている。りん酸イオン０．０１〜５重量部；チタン化合物（チタン原子に換算して）０．０１〜２重量部；フッ化物（フッ素原子に換算して）０．０１〜１２重量部；促進剤０．０１〜２重量部。
各成分の配合重量比が上記のように特定される理由は、後述の表面処理液の組成に関する説明において順次明確にする。
【００１６】
本発明の組成物および表面処理液にりん酸イオンを含有させるために、オルトりん酸（Ｈ３ ＰＯ４ ）またはその塩、あるいはピロりん酸（Ｈ４ Ｐ２ Ｏ７ ）、トリポリりん酸（Ｈ５ Ｐ３ Ｏ１０）などの縮合りん酸またはその塩の一種或いは二種以上を配合することができる。このようなりん酸化合物の種類に限定はない。本発明の処理組成物から得られる表面処理液においてりん酸イオンの含有量は０．０１〜５ｇ／リットルの範囲内にあることが好ましく、より好ましくは０．０５〜５ｇ／リットル、さらに好ましくは０．３〜２ｇ／リットルの範囲内である。りん酸イオンの含有濃度が０．０１ｇ／リットル未満でも皮膜は形成されるが、優れた耐食性、塗膜密着性は得られない。また、５ｇ／リットルを超えて多量に配合すると、良好な皮膜は形成されるが、その効果は飽和し処理液のコストが高くなり経済的に無駄になる。
【００１７】
本発明の組成物および表面処理液にチタン化合物を含有させるには、チタンの硫酸塩、オキシ硫酸塩、フッ化物等を使用することができ、その種類に限定はない。表面処理液におけるチタン化合物の含有量は、チタン原子に換算して０．０１〜２ｇ／リットルの範囲内にあり、好ましくは０．０１〜２ｇ／リットル、さらに好ましくは０．１〜１ｇ／リットルの範囲である。チタンの含有量が０．０１ｇ／リットル未満では、短時間で皮膜を十分に形成することが困難になる。また、それを２ｇ／リットルを超えて多量に配合しても、良好な皮膜は形成されるが、その効果は飽和し、処理液のコストが高くなり経済的に無駄になる。
【００１８】
本発明の組成物および表面処理液にフッ化物を含有させるには、フッ化水素酸（ＨＦ）、チタンフッ化水素酸（Ｈ２ ＴｉＦ６ ）、ケイフッ化水素酸（Ｈ２ ＳｉＦ６ ）およびジルコニウムフッ化水素酸（Ｈ２ ＺｒＦ６ ）などのフッ素含有酸、並びにこれらの酸の塩を使用することができるが、その種類に限定はない。表面処理液中のフッ化物の含有量は、フッ素原子に換算して０．０１〜１２ｇ／リットルの範囲内にあり、０．０５〜５ｇ／リットルであることが好ましく、０．１〜２ｇ／リットルの範囲内にあることがより好ましい。
【００１９】
但し、この含有量は、素材から溶出したアルミニウムイオンをフッ化アルミニウムとして液中で安定化させる為に必要なフッ素の量を包含するものであり、このフッ化アルミニウムは皮膜形成反応に対し、殆ど影響を及ぼさない。例えば、表面処理液中のアルミニウム濃度が０．１ｇ／リットルの場合、安定に存在させるのに必要なフッ素濃度は約０．２ｇ／リットルである。そして、このフッ化アルミニウムを生成させる為に必要なフッ素量を除いた場合、皮膜形成に好適なフッ化物の含有量としてはフッ素原子に換算し０．０１〜５ｇ／リットルの範囲内にあり、好ましくは０．１〜３ｇ／リットルの範囲内である。フッ素の含有量が０．０１ｇ／リットル未満では、反応性が不十分になり皮膜が十分に形成されない。また、それが１２ｇ／リットルを超えると、エッチング量が増加し外観にムラを生じるため好ましくなく、且つ廃水処理も困難となる。
【００２０】
本発明の組成物および表面処理液に含まれる促進剤は、皮膜形成を促進するものであって、硝酸（ＨＮＯ3）、過マンガン酸（ＨＭｎＯ4）及びこれらの水溶性塩、並びに水溶性有機過酸化物から選ばれた少なくとも１種からなるものであり、必要により、上記促進剤に、例えば、タングステン酸（Ｈ2 ＷＯ4 ）及びモリブデン酸（ＨＭｏＯ3 ）とそれらの塩、亜硝酸（ＨＮＯ2 ）、次亜塩素酸（ＨＣｌＯ）、亜塩素酸（ＨＣｌＯ2 ）、塩素酸（ＨＣｌＯ3 ）、臭素酸（ＨＢｒＯ3 ）、ヨウ素酸（ＨＩＯ3 ）、過塩素酸（ＨＣｌＯ4 ）、過臭素酸（ＨＢｒＯ4 ）、過ヨウ素酸（ＨＩＯ4 ）、オルト過ヨウ素酸（Ｈ5 ＩＯ6 ））およびそれらの塩、ペルオキソ酸（例えばペルオキソ一硫酸（Ｈ2 ＳＯ5 ）、ペルオキソ二硫酸（Ｈ2 Ｓ2 Ｏ8 ）、ペルオキソ一リン酸（Ｈ3 ＰＯ5 ）、ペルオキソ二リン酸（Ｈ4 Ｐ2 Ｏ8 ）、ペルオキソ一炭酸（Ｈ2 ＣＯ4 ）、ペルオキソ二炭酸（Ｈ2 Ｃ2 Ｏ6 ）、およびペルオキソホウ酸（ＨＢＯ3 ・１／２Ｈ2 Ｏ，ＨＢＯ4 ・Ｈ2 Ｏ，ＨＢＯ5 ・Ｈ2 Ｏ）など）およびそれらの塩、高原子価金属イオン（例えば４価セリウム（Ｃｅ4+）、３価鉄（Ｆｅ3+）、および４価錫（Ｓｎ4+）など）、過酸化水素（Ｈ2 Ｏ2 ）、並びに水溶性有機過酸化物などを併用することができる。
【００２１】
本発明に併用し得る亜硝酸塩としては、水溶性の化合物であれば特に限定されるものではないが、亜硝酸のナトリウム塩（ＮａＮＯ2 ）、およびカリウム塩（ＫＮＯ2 ）などを使用することが好ましい。硝酸塩としては、水溶性の化合物であれば特に限定するものではないが、硝酸のナトリウム塩（ＮａＮＯ3 ）、およびカリウム塩（ＫＮＯ3 ）などを使用することが好ましい。
【００２２】
本発明に併用し得るタングステン酸塩としては、水溶性の化合物であれば特に限定されるものではないが、タングステン酸のナトリウム塩（Ｎａ2 ＷＯ4 ）、およびカリウム塩（Ｋ2 ＷＯ4 ）などを使用することが好ましい。
【００２３】
本発明に併用し得るモリブデン酸塩としては、水溶性の化合物であれば特に限定されるものではないが、モリブデン酸のナトリウム塩（Ｎａ2 ＭｏＯ4 ）、およびアンモニウム塩（（ＮＨ4 ）6 Ｍｏ7 Ｏ24）などを使用することが好ましい。
【００２４】
過マンガン酸塩としては、水溶性の化合物であれば特に限定されるものではないが、過マンガン酸のナトリウム塩（ＮａＭｎＯ４ ）、およびカリウム塩（ＫＭｎＯ４ ）などを使用することが好ましい。
【００２５】
水溶性有機過酸化物としては、例えばｔｅｒｔ−ブチルヒドロパーオキサイド（（ＣＨ３ ）３ Ｃ−Ｏ−ＯＨ）、ｔｅｒｔ−ヘキシルヒドロパーオキサイド（ＣＨ３ ＣＨ２ （ＣＨ３ ）２ Ｃ−Ｏ−ＯＨ）又はジ−ｔｅｒｔ−ブチルパーオキサイド（（ＣＨ３ ）３ Ｃ−Ｏ−Ｏ−Ｃ（ＣＨ３ ）３ ）などが好ましく用いられる。
【００２６】
本発明の組成物、表面処理液および表面処理方法において、促進剤は金属材料表面上におけるチタン皮膜の生成速度を促進し、且つ優れた耐食性および塗膜密着性を有する皮膜を形成させる働きがある。表面処理液中の促進剤の濃度としては０．０１〜２ｇ／リットルの範囲内にあることが必要であり、好ましくは０．１〜１ｇ／リットルである。促進剤の濃度が０．０１ｇ／リットル未満では皮膜形成反応の促進効果が認められない。一方、それが２ｇ／リットルを超える量を含有させてもその効果は飽和してしまうので、それ以上の添加は、コストの上昇と経済的無駄を助長するだけである。
【００２７】
本発明の表面処理液は、処理組成物から調製されるが、そのｐＨは、１．０〜４．５の範囲内に調整されなければならない。ｐＨが１．０未満では、処理液による金属材料表面に対するエッチングが過多となり皮膜が形成されにくい。また、ｐＨが４．５を超えると、耐食性および塗膜密着性に優れた皮膜の形成が困難となる。より好ましいｐＨの範囲は１．３〜３．０である。本発明の表面処理液のｐＨは、硝酸、硫酸およびフッ化水素酸などの酸、並びに水酸化ナトリウム、炭酸ナトリウムおよび水酸化アンモニウムなどのアルカリを使用し調整することができる。
【００２８】
なお、本発明において金属材料がアルミニウムと、銅およびマンガンなどとの合金からなる場合、表面処理液中に溶出した合金成分の銅やマンガンなどの金属イオンにより処理液の安定性が著しく低下することがある。このような場合には、これらの合金成分金属をキレートするために、金属封鎖剤としてグルコン酸、ヘプトグルコン酸、蓚酸、酒石酸およびエチレンジアミンテトラ酢酸などの有機酸またはこれらのアルカリ金属塩を添加してもよい。
【００２９】
次に、本発明の表面処理方法について説明する。
本発明の表面処理液は、好ましい例として次に示す工程でアルミニウム含有金属材料の表面に適用される。
本発明の処理方法においては、前記表面処理液を温度室温〜８０℃、好ましくは３５〜７０℃において接触時間０．５〜１２０秒、好ましくは１〜６０秒の条件下でアルミニウム含有金属材料の表面に接触させる。処理時間が０．５秒未満では十分に反応せず、耐食性、塗膜密着性に優れた皮膜は形成されないことがある。一方、処理時間が１２０秒を超えても、得られる皮膜の性能は飽和し、その向上は認められなくなることがある。本発明の処理方法において、表面処理液によるアルミニウム含有金属材料表面の接触処理時間は４〜１２秒間で十分である。
【００３１】
本発明では金属材料表面と、表面処理液との接触方式は特に限定はしていないが、スプレー法を用いた方が良好な皮膜が形成されやすい。なお、処理方式が浸漬法ではスプレー法と異なり、金属材料表面への反応性が低下したり、エッチングが不均一になったりすることがあるが、その場合は処理時間を延長すればよい。
【００３２】
本発明方法により、アルミニウム含有金属材料表面上に形成させる皮膜の付着量は、チタンに換算して３〜５０ｍｇ／ｍ２ であることが好ましく、より好ましくは５〜３０ｍｇ／ｍ２ である。表面皮膜量（チタンに換算）が３ｍｇ／ｍ２ 未満では、得られる皮膜の耐食性が不十分になることがあり、また、それが５０ｍｇ／ｍ２ を超えると得られる皮膜の塗膜密着性が不十分になることがある。
【００３３】
本発明方法により表面処理されるアルミニウム含有金属材料は、アルミニウムからなる材料およびアルミニウム合金よりなる金属を包含し、アルミニウム合金は、例えばＡｌ−Ｃｕ，Ａｌ−Ｍｎ，Ａｌ−Ｍｇ，Ａｌ−ＳｉおよびＡｌ−Ｚｎなどの合金を包含する。また、本発明方法に用いられるアルミニウム含有金属材料には、その形状、寸法などに制限はなく、例えば板材および各種成形品などを包含する。
【００３４】
【実施例】
以下に、実施例を比較例とともに挙げ、本発明の処理組成物、表面処理液および表面処理方法をより具体的に説明する。
【００３５】
実施例１〜５、比較例１〜５
実施例１〜５および比較例１〜５の各々において下記の処理操作を行った。
〔供試材〕
アルミニウム−マグネシウム合金板（ＪＩＳ ５１８２）を使用した。
寸法：３００mm×２００mm、板厚０．２５mm
〔処理条件〕
下記工程<1>→<2>→<3>→<4>→<5>→<6>の順序で行い、化成処理板を作製した。
<1> 脱脂（６０℃、１０秒、スプレー処理）
市販のアルカリ性脱脂剤（登録商標ファインクリーナー４３７７Ｋ、日本パーカライジング株式会社製）の２％水溶液を用いた。
<2> 水洗（常温、１０秒、スプレー処理）
【００３６】
<3> 化成処理（スプレー処理）
実施例１〜５および比較例１〜５の表面処理液（化成処理液）に用いられた成分物質を表１に示す。また表２および表３に示される組成および処理条件において、脱脂<1>水洗<2>された金属材料に表面処理（化成処理）を施した。比較例６および比較例７の表面処理条件（化成処理条件）については別に示す。なお、実施例１、実施例４、および比較例２においてチタン化合物およびフッ化物を添加するために、両成分を包含する４０％チタンフッ化水素酸を用いた。また、実施例１、実施例２において、促進剤およびpH調整剤の両方を兼用する６７．５％硝酸を用いた。
【００３７】
<4> 水洗（常温、１０秒、スプレー処理）
<5> 脱イオン水洗（常温、５秒、スプレー処理）
<6> 加熱乾燥（８０℃、３分、熱風オーブン）
上記脱脂、水洗、脱イオン水洗および化成処理には、小型のスプレー装置を用いた。この小型スプレー装置は、アルミニウム合金のコイルの実用連続表面処理ラインにおいて用いられているスプレー処理と同様のスプレー条件になるように設計されているものである。
【００３８】
得られた処理材料の反応性（皮膜付着量）、耐食性、塗膜密着性について下記方法によりテストを行った。
（１）反応性
蛍光Ｘ線分析装置（理学電機工業株式会社製、ＲＩＸ１０００）を用いて、化成処理板のＴｉまたはＺｒ付着量（ｍｇ／ｍ２ ）を測定した。
【００３９】
（２）耐食性
耐食性の評価には、ＪＩＳ−Ｚ−２３７１に準拠した塩水噴霧試験を用いた。塩水噴霧１５０時間後の化成処理板の腐食発生状態を目視で評価した。
評価基準は、以下の通りである。
◎：腐食面積率１０％未満
○：腐食面積率１０％以上、５０％未満
△：腐食面積率５０％以上、９０％未満
×：腐食面積率９０％以上
【００４０】
（３）塗膜密着性
表面処理されたアルミニウム−マグネシウム合金板の表面にエポキシフェノール系の缶蓋用塗料を塗膜厚８μｍの厚さで塗装し、２２０℃で３分間焼付け、２つの塗装面にポリアミド系のフィルムを挟んで２００℃で２分間熱圧着した。次に、この熱圧着板を幅１０ｍｍ×長さ１２０ｍｍの短冊状に切断し、試験片とした。そして、Ｔピール試験法により試験片をポリアミド系フィルムから剥離し、その際の剥離強度により１次密着性を評価した。また、耐水後の密着性を評価するため、上記試験片を脱イオン沸騰水中に６０分間浸漬し、上記Ｔピール試験法による剥離強度を測定し、その結果から２次密着性を評価した。
この剥離強度の値が大きいほど塗膜密着性が優れていることを意味し、１次密着性では剥離強度が７．０ ｋｇｆ／１０ｍｍ幅以上、また、２次密着性の場合には５．０ ｋｇｆ／１０ｍｍ幅以上であれば、実用上十分な性能である。
上記テスト結果を表２、表３に示す。
【００４１】
【表１】
比較例６
実施例１と同様の処理を行った。但し、化成処理工程▲３▼において表面処理液として、市販のジルコニウム系化成処理剤（商標アロジン４０４０、日本パーカライジング株式会社製）の２％水溶液を用いた。この処理液を用いて、温度４０℃、時間３０秒の条件で前記アルミニウム−マグネシウム合金板にスプレー処理を施した。テスト結果を表３に示す。
【００４３】
比較例７
実施例１と同様の処理操作を行った。但し、化成処理液として、市販のジルコニウム系化成処理剤（商標アロジン４０４０、日本パーカライジング株式会社製）の２％水溶液を用いた。そして、この液を温度４０℃、時間５秒の条件で前記アルミニウム−マグネシウム合金板にスプレー処理した。テスト結果を表３に示す。
【００４４】
【表２】
【表３】
【発明の効果】
上記の説明から明らかなように、本発明に係る処理組成物、表面処理液および表面処理方法をアルミニウム含有金属材料に適用することにより、塗装または成形前の金属材料表面に優れた耐食性と塗膜密着性を有する皮膜を短時間で形成させることが可能となった。
また、本発明の処理組成物を用いた表面処理液および表面処理方法を、アルミニウム含有金属コイル、又はシート材に適用すれば、その材料表面に優れた耐食性と塗膜密着性とを短時間で付与することができ、また製造ラインの高速化および処理設備のコンパクト化（省スペース）も可能となる。
従って、本発明のアルミニウム含有金属材料用表面処理組成物、表面処理液および表面処理方法は、実用上極めて有用なものである。[0001]
[Industrial application fields]
The present invention relates to a novel surface treatment composition for aluminum-containing metal materials, a surface treatment liquid and a surface treatment method for imparting excellent corrosion resistance and coating film adhesion to the surfaces of aluminum-containing metal materials, that is, aluminum materials and aluminum alloy materials. Is. The present invention is particularly effectively applied to the surface treatment of aluminum alloy coils and sheet materials.
[0002]
[Prior art]
Surface treatment solutions for aluminum-containing metal materials can be broadly classified into chromate type and non-chromate type. Typical examples of the chromate type treatment liquid include chromic acid chromate chemical conversion liquid and phosphoric acid chromate chemical conversion liquid.
The chromate chromate chemical conversion treatment solution was put into practical use around 1950, and is still widely used for fin materials for heat exchangers and aircraft materials. This chromate chromate chemical conversion treatment liquid contains chromic acid and a fluoride acting as a reaction accelerator as main components, and a chemical film containing a slight amount of hexavalent chromium is formed on the surface of the metal material. Form.
[0003]
The phosphoric acid chromate chemical conversion treatment solution is in accordance with the invention disclosed in US Pat. No. 2,438,877, and this chemical conversion treatment solution contains chromic acid, phosphoric acid and hydrofluoric acid as main components. A chemical conversion film composed mainly of hydrated chromium phosphate is formed on the surface. Since this chemical film does not contain hexavalent chromium, this treatment liquid is still widely used for applications such as body treatment of beverage cans and coating base treatment of lid materials. However, since the chromate type surface treatment liquid contains harmful hexavalent chromium, it is desired to use a treatment liquid that does not contain hexavalent chromium due to environmental problems.
[0004]
As a typical invention of a non-chromate type surface treatment solution containing no chromium, there is a method disclosed in Japanese Patent Application Laid-Open No. 52-131937. The treatment liquid is an acidic aqueous coating solution containing zirconium or titanium, or a mixture thereof, phosphate and fluoride, and having a pH of about 1.5 to 4.0. When the surface treatment solution is used to treat the surface of the metal material, a chemical conversion film mainly composed of zirconium or titanium oxide is formed on the metal surface. This non-chromate type surface treatment solution has the advantage that it does not contain hexavalent chromium, and is currently widely used for the surface treatment of aluminum DI cans, but it is more reactive than the chromate type surface treatment solution. Therefore, the treatment time until the film is formed is long, and the corrosion resistance and film adhesion of the formed film are inferior to those of the chromate film. In recent years, the line speed has been increased along with the improvement of productivity, and shortening of the surface treatment time has become a major issue.
[0005]
As an invention aimed at shortening the surface treatment time, a treatment method disclosed in JP-A-1-246370 is known. In this method, an aluminum-containing metal material is subjected to surface cleaning with an alkaline degreasing agent, and then, on this cleaned surface, zirconium ions 0.01 to 0.5 g / liter, phosphate ions 0.01 to 0.5 g / liter and effective Surface treatment is performed using an acidic aqueous solution containing 0.001 to 0.05 g / liter of fluorine ions or 0.01 to 1 g / liter of vanadium ions and having a pH of 1.5 to 4.0. However, when this method is used for an aluminum DI can, the resulting film may not have sufficient blackening resistance.
[0006]
As another nonchromate treatment method, Japanese Patent Publication No. 57-39314 discloses one or more of titanium salt or zirconium salt, hydrogen peroxide, and one or two of phosphoric acid or condensed phosphoric acid. A treatment method for treating an aluminum-containing metal surface with an acidic solution containing the above is disclosed. However, this treatment liquid is unstable, and the reactivity for forming the surface film is unsatisfactory, and the above publication does not disclose any specific description about the treatment time, treatment temperature, and treatment operation. .
[0007]
For these reasons, non-chromate type surface treatment liquids are rarely used at present in coil and sheet surface treatment lines for aluminum-containing metal materials that require short-time treatment.
Therefore, to date, a surface treatment composition for aluminum-containing metal materials that does not contain hexavalent chromium in the treatment liquid, can be treated for a short time, and can form a film having excellent corrosion resistance and coating film adhesion. The surface treatment liquid and the surface treatment method have not been established.
[0008]
[Problems to be solved by the invention]
The present invention is for solving the above-mentioned problems of the prior art, and specifically, it is possible to form a film having excellent corrosion resistance and coating film adhesion on the surface of an aluminum-containing metal material in a short time. An object of the present invention is to provide a surface treatment composition for an aluminum-containing metal material, a surface treatment liquid and a surface treatment method.
[0009]
[Means for Solving the Problems]
The present inventors diligently studied a means for solving the above-described problems of the prior art. As a result, by using a surface treatment composition containing a specific amount of phosphate ion, a titanium compound, a fluoride, and an accelerator having a specific composition, a film having excellent corrosion resistance and coating film adhesion can be shortened. It was newly found that it can be formed on the surface of the aluminum-containing metal material within the time, and the present invention has been completed.
[0010]
The surface treatment composition for an aluminum-containing metal material according to the present invention is 0.01 to 5 parts by weight of a phosphate ion, 0.01 to 2 parts by weight of a titanium compound in terms of titanium atoms, and a fluorine atom. At least one selected from 0.01 to 12 parts by weight of fluoride, 0.01 to 2 parts by weight of nitric acid, permanganic acid, water-soluble salts thereof, and water-soluble organic peroxides And an accelerator comprising:
[0012]
Further, the surface treatment liquid for aluminum-containing metal material of the present invention is prepared from the surface treatment composition for aluminum-containing metal material of the present invention, and 0.01 to 5 g / liter of phosphate ions, 0.01-2 g / liter of titanium compound in terms of titanium atom, 0.01-12 g / liter of fluoride in terms of fluorine atom, 0.01-2 g / liter of nitric acid, permanganic acid And at least one accelerator selected from water-soluble salts and water-soluble organic peroxides, and has a pH of 1.0 to 4.5.
[0013]
Moreover, the surface treatment method of the aluminum-containing metal material of the present invention is a method for treating a surface treatment solution prepared from the treatment composition and having a pH of 1.0 to 4.5 at a temperature of room temperature to 80 ° C. The surface of the metal material is brought into contact with the surface, and then the surface of the metal material to which the surface treatment liquid is attached is washed with water and dried by heating to form a chemical conversion film. The contact treatment time of the surface of the aluminum-containing metal material with the surface treatment liquid is preferably 4 to 12 seconds. Moreover, it is preferable that this chemical conversion film is the weight of 3-50 mg / m < 2 > converted into a titanium atom.
[0014]
[Action]
Next, the configuration of the present invention will be described in detail.
The treatment composition of the present invention is an aqueous solution containing phosphate ions, a titanium compound, a fluoride, and a specific accelerator as essential components, and usually exhibits acidity. In particular, it is preferable that a specific accelerator is used in the treatment composition of the present invention. When such a specific accelerator is used, the reactivity of the treatment liquid, the corrosion resistance of the formed film, and the coating film adhesion can be remarkably improved.
[0015]
In the treatment composition for surface treatment of an aluminum-containing metal material of the present invention, phosphate ions, titanium compounds, fluorides and accelerators are blended in the following weight ratio. 0.01-5 parts by weight of phosphate ion; 0.01-2 parts by weight of titanium compound (converted to titanium atom); 0.01-12 parts by weight of fluoride (converted to fluorine atom); accelerator 0 .01-2 parts by weight.
The reason why the blending weight ratio of each component is specified as described above will be clarified sequentially in the description regarding the composition of the surface treatment liquid described later.
[0016]
In order to contain phosphate ions in the composition and surface treatment solution of the present invention, orthophosphoric acid (H 3 PO 4 ) or a salt thereof, pyrophosphoric acid (H 4 P 2 O 7 ), tripolyphosphoric acid (H One kind or two or more kinds of condensed phosphoric acid such as 5 P 3 O 10 ) or a salt thereof can be blended. There is no limitation on the type of such phosphoric acid compound. In the surface treatment liquid obtained from the treatment composition of the present invention, the content of phosphate ions is preferably in the range of 0.01 to 5 g / liter, more preferably 0.05 to 5 g / liter, and still more preferably. It is in the range of 0.3-2 g / liter. Even if the phosphate ion concentration is less than 0.01 g / liter, a film is formed, but excellent corrosion resistance and coating film adhesion cannot be obtained. Moreover, when it mix | blends in large quantities exceeding 5 g / liter, although a favorable film | membrane will be formed, the effect will be saturated and the cost of a process liquid will become high and it will be economically useless.
[0017]
In order to contain the titanium compound in the composition and the surface treatment liquid of the present invention, titanium sulfate, oxysulfate, fluoride, and the like can be used, and the type is not limited. The content of the titanium compound in the surface treatment liquid is in the range of 0.01 to 2 g / liter in terms of titanium atoms, preferably 0.01 to 2 g / liter, more preferably 0.1 to 1 g / liter. Range. If the titanium content is less than 0.01 g / liter, it is difficult to sufficiently form a film in a short time. Moreover, even if it is blended in a large amount exceeding 2 g / liter, a good film is formed, but the effect is saturated, the cost of the treatment liquid is increased, and it is economically wasteful.
[0018]
In order to make the composition and the surface treatment liquid of the present invention contain fluoride, hydrofluoric acid (HF), titanium hydrofluoric acid (H 2 TiF 6 ), silicohydrofluoric acid (H 2 SiF 6 ), and zirconium fluoride are used. Fluorine-containing acids such as hydrofluoric acid (H 2 ZrF 6 ) and salts of these acids can be used, but the type is not limited. The content of fluoride in the surface treatment liquid is in the range of 0.01 to 12 g / liter in terms of fluorine atoms, preferably 0.05 to 5 g / liter, and 0.1 to 2 g / liter. More preferably in the range of liters.
[0019]
However, this content includes the amount of fluorine necessary to stabilize aluminum ions eluted from the raw material in the solution as aluminum fluoride. Has no effect. For example, when the aluminum concentration in the surface treatment solution is 0.1 g / liter, the fluorine concentration necessary for stable presence is about 0.2 g / liter. And when the amount of fluorine necessary for producing this aluminum fluoride is removed, the content of fluoride suitable for film formation is in the range of 0.01 to 5 g / liter in terms of fluorine atoms, Preferably it is in the range of 0.1 to 3 g / liter. When the fluorine content is less than 0.01 g / liter, the reactivity is insufficient and a film is not sufficiently formed. On the other hand, if it exceeds 12 g / liter, the etching amount increases and the appearance becomes uneven, which is not preferable, and wastewater treatment becomes difficult.
[0020]
The accelerator contained in the composition and the surface treatment liquid of the present invention promotes film formation, and includes nitric acid (HNO 3 ), permanganic acid (HMnO 4 ) and water-soluble salts thereof, and water-soluble organic compounds. It is composed of at least one selected from peroxides, and if necessary, for example, tungstic acid (H 2 WO 4 ), molybdic acid (HMoO 3 ) and their salts, nitrous acid (HNO) 2 ), hypochlorous acid (HClO), chlorous acid (HClO 2 ), chloric acid (HClO 3 ), bromic acid (HBrO 3 ), iodic acid (HIO 3 ), perchloric acid (HClO 4 ), perbromine Acids (HBrO 4 ), periodic acid (HIO 4 ), orthoperiodic acid (H 5 IO 6 )) and their salts, peroxoacids (eg peroxomonosulfuric acid (H 2 SO 5 ), peroxodisulfuric acid (H 2) S 2 O 8), Ruokiso monophosphate (H 3 PO 5), peroxo diphosphate (H 4 P 2 O 8) , peroxomonosulfuric carbonate (H 2 CO 4), peroxo dicarbonate (H 2 C 2 O 6) , and peroxoborate (HBO 3 · 1 / 2H 2 O, HBO 4 · H 2 O, HBO 5 · H 2 O) , etc.) and their salts, high valent metal ion (e.g., tetravalent cerium (Ce 4+), 3 ferric (Fe 3+ ) and tetravalent tin (Sn 4+ )), hydrogen peroxide (H 2 O 2 ), water-soluble organic peroxide, and the like can be used in combination.
[0021]
The nitrite that can be used in the present invention is not particularly limited as long as it is a water-soluble compound, but sodium nitrite (NaNO 2 ), potassium salt (KNO 2 ), and the like may be used. preferable. The nitrate is not particularly limited as long as it is a water-soluble compound, but it is preferable to use a sodium salt of nitric acid (NaNO 3 ), a potassium salt (KNO 3 ), or the like.
[0022]
The tungstate that can be used in the present invention is not particularly limited as long as it is a water-soluble compound, but a sodium salt of tungstic acid (Na 2 WO 4 ), a potassium salt (K 2 WO 4 ), and the like. Is preferably used.
[0023]
The molybdate that can be used in the present invention is not particularly limited as long as it is a water-soluble compound, but sodium molybdate (Na 2 MoO 4 ) and ammonium salt ((NH 4 ) 6 Mo 7 O 24 ) or the like is preferably used.
[0024]
The permanganate is not particularly limited as long as it is a water-soluble compound, but it is preferable to use a sodium salt of permanganate (NaMnO 4 ), a potassium salt (KMnO 4 ), or the like.
[0025]
Examples of the water-soluble organic peroxide include tert-butyl hydroperoxide ((CH 3 ) 3 C—O—OH) and tert-hexyl hydroperoxide (CH 3 CH 2 (CH 3 ) 2 C—O—OH). ) Or di-tert-butyl peroxide ((CH 3 ) 3 C—O—O—C (CH 3 ) 3 ) or the like is preferably used.
[0026]
In the composition, surface treatment liquid and surface treatment method of the present invention, the accelerator has a function of accelerating the formation rate of the titanium film on the surface of the metal material and forming a film having excellent corrosion resistance and coating film adhesion. . The concentration of the accelerator in the surface treatment liquid needs to be in the range of 0.01 to 2 g / liter, preferably 0.1 to 1 g / liter. When the concentration of the accelerator is less than 0.01 g / liter, the effect of promoting the film formation reaction is not recognized. On the other hand, even if it contains an amount exceeding 2 g / liter, the effect is saturated, so addition beyond that only promotes an increase in cost and economic waste.
[0027]
The surface treatment liquid of the present invention is prepared from the treatment composition, but its pH must be adjusted within the range of 1.0 to 4.5. When the pH is less than 1.0, the surface of the metal material is excessively etched by the treatment liquid and a film is not easily formed. Moreover, when pH exceeds 4.5, formation of the film | membrane excellent in corrosion resistance and coating-film adhesiveness will become difficult. A more preferable pH range is 1.3 to 3.0. The pH of the surface treatment liquid of the present invention can be adjusted by using acids such as nitric acid, sulfuric acid and hydrofluoric acid, and alkalis such as sodium hydroxide, sodium carbonate and ammonium hydroxide.
[0028]
In the present invention, when the metal material is made of an alloy of aluminum, copper, manganese, etc., the stability of the treatment liquid is significantly reduced by the metal ions of the alloy components, such as copper and manganese, eluted in the surface treatment liquid. There is. In such a case, an organic acid such as gluconic acid, heptogluconic acid, succinic acid, tartaric acid and ethylenediaminetetraacetic acid or an alkali metal salt thereof may be added as a sequestering agent to chelate these alloy component metals. Good.
[0029]
Next, the surface treatment method of the present invention will be described.
As a preferred example, the surface treatment liquid of the present invention is applied to the surface of an aluminum-containing metal material in the following steps.
In the treatment method of the present invention, the surface treatment solution is used at a temperature of room temperature to 80 ° C., preferably 35 to 70 ° C., and a contact time of 0.5 to 120 seconds, preferably 1 to 60 seconds. Touch the surface. When the treatment time is less than 0.5 seconds, it does not react sufficiently, and a film excellent in corrosion resistance and coating film adhesion may not be formed. On the other hand, even when the treatment time exceeds 120 seconds, the performance of the obtained film is saturated and the improvement may not be recognized. In the treatment method of the present invention, 4 to 12 seconds is sufficient for the contact treatment time of the surface of the aluminum-containing metal material with the surface treatment liquid.
[0031]
In the present invention, the contact method between the surface of the metal material and the surface treatment liquid is not particularly limited, but a better film is more easily formed by using the spray method. Note that, unlike the spray method, the immersion method may be less reactive to the surface of the metal material or may have uneven etching. In that case, the treatment time may be extended.
[0032]
It is preferable that the adhesion amount of the film | membrane formed on the aluminum containing metal material surface by this invention method is 3-50 mg / m < 2 > in conversion to titanium, More preferably, it is 5-30 mg / m < 2 >. If the surface coating amount (in terms of titanium) is less than 3 mg / m 2 , the resulting coating may have insufficient corrosion resistance, and if it exceeds 50 mg / m 2 , the coating film adhesion of the resulting coating may be insufficient. It may be insufficient.
[0033]
The aluminum-containing metal material surface-treated by the method of the present invention includes a material composed of aluminum and a metal composed of an aluminum alloy. Examples of the aluminum alloy include Al—Cu, Al—Mn, Al—Mg, Al—Si, and Al. Includes alloys such as Zn. Moreover, there is no restriction | limiting in the shape, a dimension, etc. in the aluminum containing metal material used for this invention method, For example, a board | plate material and various molded articles etc. are included.
[0034]
【Example】
Hereinafter, examples will be given together with comparative examples, and the treatment composition, surface treatment liquid and surface treatment method of the present invention will be described more specifically.
[0035]
Examples 1-5, Comparative Examples 1-5
In each of Examples 1 to 5 and Comparative Examples 1 to 5, the following processing operations were performed.
[Sample material]
An aluminum-magnesium alloy plate (JIS 5182) was used.
Dimensions: 300mm x 200mm, plate thickness 0.25mm
[Processing conditions]
The following steps <1> → <2> → <3> → <4> → <5> → <6> were performed in this order to produce a chemical conversion treatment plate.
<1> Degreasing (60 ° C, 10 seconds, spray treatment)
A 2% aqueous solution of a commercially available alkaline degreasing agent (registered trademark Fine Cleaner 4377K, manufactured by Nippon Parkerizing Co., Ltd.) was used.
<2> Washing with water (normal temperature, 10 seconds, spray treatment)
[0036]
<3> Chemical conversion treatment (spray treatment)
Table 1 shows component substances used in the surface treatment liquids (chemical conversion liquids) of Examples 1 to 5 and Comparative Examples 1 to 5. Moreover, the surface treatment (chemical conversion treatment) was performed on the degreased <1> water-washed <2> metal material under the compositions and treatment conditions shown in Tables 2 and 3. The surface treatment conditions (chemical conversion treatment conditions) of Comparative Example 6 and Comparative Example 7 will be shown separately. In addition, in order to add a titanium compound and a fluoride in Example 1, Example 4, and Comparative Example 2, 40% titanium hydrofluoric acid including both components was used. Further, in Example 1 and Example 2, 67.5% nitric acid, which is both an accelerator and a pH adjuster, was used.
[0037]
<4> Washing with water (normal temperature, 10 seconds, spray treatment)
<5> Deionized water washing (normal temperature, 5 seconds, spray treatment)
<6> Heat drying (80 ° C, 3 minutes, hot air oven)
A small spray device was used for the degreasing, water washing, deionized water washing and chemical conversion treatment. This small spray device is designed to have the same spray conditions as the spray treatment used in a practical continuous surface treatment line for coils of aluminum alloy.
[0038]
Tests were performed on the reactivity (film adhesion amount), corrosion resistance, and coating film adhesion of the obtained treatment materials by the following methods.
(1) Ti or Zr adhesion amount (mg / m 2 ) of the chemical conversion treatment plate was measured using a reactive fluorescent X-ray analyzer (RIX1000, manufactured by Rigaku Corporation).
[0039]
(2) Corrosion resistance The salt spray test based on JIS-Z-2371 was used for evaluation of corrosion resistance. The state of corrosion occurrence of the chemical conversion treatment plate after 150 hours of salt spray was visually evaluated.
The evaluation criteria are as follows.
◎: Corrosion area ratio less than 10% ○: Corrosion area ratio 10% or more, less than 50% △: Corrosion area ratio 50% or more, less than 90% ×: Corrosion area ratio 90% or more
(3) Coating surface adhesion Surface-treated aluminum-magnesium alloy plate was coated with an epoxyphenol-based can lid coating with a thickness of 8 μm and baked at 220 ° C. for 3 minutes. The film was thermocompression bonded at 200 ° C. for 2 minutes with a polyamide film interposed therebetween. Next, this thermocompression bonding plate was cut into a strip shape having a width of 10 mm and a length of 120 mm to obtain a test piece. And the test piece was peeled from the polyamide-type film by the T peel test method, and primary adhesiveness was evaluated by the peeling strength in that case. Moreover, in order to evaluate the adhesiveness after water resistance, the said test piece was immersed in deionized boiling water for 60 minutes, the peeling strength by the said T peel test method was measured, and the secondary adhesiveness was evaluated from the result.
The larger the value of the peel strength, the better the coating film adhesion. In the case of primary adhesion, the peel strength is 7.0 kgf / 10 mm width or more, and in the case of secondary adhesion, 5. If it is 0 kgf / 10 mm width or more, it is a practically sufficient performance.
The test results are shown in Tables 2 and 3.
[0041]
[Table 1]
Comparative Example 6
The same processing as in Example 1 was performed. However, in the chemical conversion treatment step (3), a 2% aqueous solution of a commercially available zirconium-based chemical conversion treatment agent (trade name Allodin 4040, manufactured by Nihon Parkerizing Co., Ltd.) was used. Using this treatment solution, the aluminum-magnesium alloy plate was sprayed under conditions of a temperature of 40 ° C. and a time of 30 seconds. Table 3 shows the test results.
[0043]
Comparative Example 7
The same processing operation as in Example 1 was performed. However, as the chemical conversion treatment solution, a 2% aqueous solution of a commercially available zirconium chemical conversion treatment agent (trademark Allodin 4040, manufactured by Nippon Parkerizing Co., Ltd.) was used. Then, this solution was sprayed onto the aluminum-magnesium alloy plate under the conditions of a temperature of 40 ° C. and a time of 5 seconds. Table 3 shows the test results.
[0044]
[Table 2]
[Table 3]
【The invention's effect】
As is clear from the above description, by applying the treatment composition, the surface treatment liquid and the surface treatment method according to the present invention to an aluminum-containing metal material, excellent corrosion resistance and coating film on the surface of the metal material before coating or forming It became possible to form a film having adhesiveness in a short time.
Moreover, if the surface treatment liquid and the surface treatment method using the treatment composition of the present invention are applied to an aluminum-containing metal coil or sheet material, excellent corrosion resistance and coating film adhesion can be achieved on the material surface in a short time. In addition, it is possible to increase the production line speed and the processing equipment to be compact (space saving).
Therefore, the surface treatment composition for aluminum-containing metal material, the surface treatment liquid and the surface treatment method of the present invention are extremely useful in practice.
Claims (5)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16624395A JP3623015B2 (en) | 1995-06-30 | 1995-06-30 | Surface treatment liquid for aluminum-containing metal material and surface treatment method |
| EP96924286A EP0837954A4 (en) | 1995-06-30 | 1996-06-25 | Composition and process for treating the surface of aluminiferous metals |
| AU64781/96A AU708280B2 (en) | 1995-06-30 | 1996-06-25 | Composition and process for treating the surface of aluminiferous metals |
| PCT/US1996/010683 WO1997002369A1 (en) | 1995-06-30 | 1996-06-25 | Composition and process for treating the surface of aluminiferous metals |
| NZ312858A NZ312858A (en) | 1995-06-30 | 1996-06-25 | Composition and process for treating the surface of aluminiferous metals |
| US08/983,599 US6193815B1 (en) | 1995-06-30 | 1996-06-25 | Composition and process for treating the surface of aluminiferous metals |
| CA 2225757 CA2225757A1 (en) | 1995-06-30 | 1996-06-25 | Composition and process for treating the surface of aluminiferous metals |
| BR9609331A BR9609331A (en) | 1995-06-30 | 1996-06-25 | Aqueous liquid composition and process for treating an aluminum metallic surface |
| MXPA/A/1997/010210A MXPA97010210A (en) | 1995-06-30 | 1997-12-16 | Composition and process for treating metal surface aluminife |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16624395A JP3623015B2 (en) | 1995-06-30 | 1995-06-30 | Surface treatment liquid for aluminum-containing metal material and surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0920984A JPH0920984A (en) | 1997-01-21 |
| JP3623015B2 true JP3623015B2 (en) | 2005-02-23 |
Family
ID=15827772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16624395A Expired - Fee Related JP3623015B2 (en) | 1995-06-30 | 1995-06-30 | Surface treatment liquid for aluminum-containing metal material and surface treatment method |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0837954A4 (en) |
| JP (1) | JP3623015B2 (en) |
| AU (1) | AU708280B2 (en) |
| BR (1) | BR9609331A (en) |
| CA (1) | CA2225757A1 (en) |
| NZ (1) | NZ312858A (en) |
| WO (1) | WO1997002369A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200693B1 (en) | 1997-05-22 | 2001-03-13 | Henkel Corporation | Water-based liquid treatment for aluminum and its alloys |
| ZA984335B (en) * | 1997-05-22 | 1998-11-30 | Henkel Corp | Waster-based liquid treatment for aluminum and its alloys |
| AU757539B2 (en) | 1997-08-21 | 2003-02-27 | Henkel Kommanditgesellschaft Auf Aktien | Process for coating and/or touching up coatings on metal surfaces |
| US6074464A (en) * | 1998-02-03 | 2000-06-13 | Sermatech International, Inc. | Phosphate bonded aluminum coatings |
| CA2332620A1 (en) * | 1998-05-20 | 1999-11-25 | Henkel Corporation | Composition and process for treating surfaces of light metals and their alloys |
| US6485580B1 (en) | 1998-05-20 | 2002-11-26 | Henkel Corporation | Composition and process for treating surfaces or light metals and their alloys |
| JP4408474B2 (en) * | 1999-01-25 | 2010-02-03 | トピー工業株式会社 | Aluminum alloy substrate coating method and wheel |
| US6679952B2 (en) * | 1999-02-12 | 2004-01-20 | Topy Industries, Limited | Method of coating aluminum and aluminum alloy substrates and coated articles |
| DE19933189A1 (en) * | 1999-07-15 | 2001-01-18 | Henkel Kgaa | Process for the protection against corrosion or aftertreatment of metal surfaces |
| DE60127793T2 (en) * | 2000-11-07 | 2007-12-27 | Nisshin Steel Co., Ltd. | Chemically processed steel sheet with excellent corrosion resistance |
| US7147934B2 (en) | 2000-11-07 | 2006-12-12 | Nisshin Steel Co., Ltd. | Chemically processed steel sheet excellent in corrosion resistance |
| JP4562897B2 (en) * | 2000-11-20 | 2010-10-13 | 三菱アルミニウム株式会社 | Fin material for heat exchanger having non-chromate reaction type underlayer and heat exchanger provided with the same |
| US7077895B2 (en) | 2001-10-30 | 2006-07-18 | Kansai Paint Co., Ltd. | Coating compound for forming titanium oxide film, method for forming titanium oxide film and metal susbstrate coated with titanium oxide film |
| US6887320B2 (en) * | 2002-02-11 | 2005-05-03 | United Technologies Corporation | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
| US6692583B2 (en) * | 2002-02-14 | 2004-02-17 | Jon Bengston | Magnesium conversion coating composition and method of using same |
| US6749694B2 (en) | 2002-04-29 | 2004-06-15 | Ppg Industries Ohio, Inc. | Conversion coatings including alkaline earth metal fluoride complexes |
| US7402214B2 (en) | 2002-04-29 | 2008-07-22 | Ppg Industries Ohio, Inc. | Conversion coatings including alkaline earth metal fluoride complexes |
| DE10358590A1 (en) | 2003-12-12 | 2005-07-07 | Newfrey Llc, Newark | Process for the pretreatment of surfaces of welded parts of aluminum or its alloys and corresponding welded parts |
| JP5215043B2 (en) * | 2008-06-02 | 2013-06-19 | 日本パーカライジング株式会社 | Metal surface treatment liquid and surface treatment method |
| JP2012017524A (en) * | 2010-06-09 | 2012-01-26 | Nippon Paint Co Ltd | Inorganic chromium-free metal surface treatment agent |
| JP6553936B2 (en) * | 2015-04-28 | 2019-07-31 | 株式会社神戸製鋼所 | Method for producing aluminum alloy sheet for packaging container |
| CN105862020A (en) * | 2016-05-31 | 2016-08-17 | 无锡伊佩克科技有限公司 | Steel surface fluoroferrite conversion plating solution and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH273704A (en) * | 1940-09-07 | 1951-02-28 | Parker Ste Continentale | Process for coating aluminum. |
| JPS5173938A (en) * | 1974-12-25 | 1976-06-26 | Nippon Packaging Kk | Aruminiumuoyobi sonogokinnohyomenshoriho |
| JPS5424232A (en) * | 1977-07-26 | 1979-02-23 | Nippon Packaging Kk | Surface treating method of aluminum |
| FR2417537A1 (en) * | 1978-02-21 | 1979-09-14 | Parker Ste Continentale | COMPOSITION BASED ON HAFNIUM TO INHIBIT CORROSION OF METALS |
| DE2905535A1 (en) * | 1979-02-14 | 1980-09-04 | Metallgesellschaft Ag | METHOD FOR SURFACE TREATMENT OF METALS |
| AU4751885A (en) * | 1984-10-09 | 1986-04-17 | Parker Chemical Company | Treating extruded aluminium metal surfaces |
| JPH0364484A (en) * | 1989-08-01 | 1991-03-19 | Nippon Paint Co Ltd | Surface treating agent and treating bath for aluminum or aluminum alloy |
| GB2259920A (en) * | 1991-09-10 | 1993-03-31 | Gibson Chem Ltd | Surface conversion coating solution based on molybdenum and phosphate compounds |
| US5143562A (en) * | 1991-11-01 | 1992-09-01 | Henkel Corporation | Broadly applicable phosphate conversion coating composition and process |
| JPH0748677A (en) * | 1993-07-05 | 1995-02-21 | Nippon Parkerizing Co Ltd | Aluminum di can and common surface treatment solution and process for tin di can |
| US5449415A (en) * | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
| US5427632A (en) * | 1993-07-30 | 1995-06-27 | Henkel Corporation | Composition and process for treating metals |
| DE4401566A1 (en) * | 1994-01-20 | 1995-07-27 | Henkel Kgaa | Process for the common pretreatment of steel, galvanized steel, magnesium and aluminum before joining with rubber |
| JP3315529B2 (en) * | 1994-06-03 | 2002-08-19 | 日本パーカライジング株式会社 | Composition for surface treatment of aluminum-containing metal material and surface treatment method |
-
1995
- 1995-06-30 JP JP16624395A patent/JP3623015B2/en not_active Expired - Fee Related
-
1996
- 1996-06-25 WO PCT/US1996/010683 patent/WO1997002369A1/en not_active Application Discontinuation
- 1996-06-25 AU AU64781/96A patent/AU708280B2/en not_active Ceased
- 1996-06-25 CA CA 2225757 patent/CA2225757A1/en not_active Abandoned
- 1996-06-25 NZ NZ312858A patent/NZ312858A/en unknown
- 1996-06-25 BR BR9609331A patent/BR9609331A/en not_active Application Discontinuation
- 1996-06-25 EP EP96924286A patent/EP0837954A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| CA2225757A1 (en) | 1997-01-23 |
| WO1997002369A1 (en) | 1997-01-23 |
| EP0837954A4 (en) | 1998-10-28 |
| JPH0920984A (en) | 1997-01-21 |
| NZ312858A (en) | 1999-11-29 |
| AU708280B2 (en) | 1999-07-29 |
| AU6478196A (en) | 1997-02-05 |
| EP0837954A1 (en) | 1998-04-29 |
| MX9710210A (en) | 1998-03-29 |
| BR9609331A (en) | 1999-05-25 |
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