JPH03243781A - Chemical conversion treating solution for aluminum and aluminum alloy - Google Patents
Chemical conversion treating solution for aluminum and aluminum alloyInfo
- Publication number
- JPH03243781A JPH03243781A JP4016890A JP4016890A JPH03243781A JP H03243781 A JPH03243781 A JP H03243781A JP 4016890 A JP4016890 A JP 4016890A JP 4016890 A JP4016890 A JP 4016890A JP H03243781 A JPH03243781 A JP H03243781A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- aluminum
- ions
- treatment liquid
- conversion treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000126 substance Substances 0.000 title claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 52
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229940104869 fluorosilicate Drugs 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims description 80
- 239000007788 liquid Substances 0.000 claims description 39
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 229910001430 chromium ion Inorganic materials 0.000 claims description 4
- 229940085991 phosphate ion Drugs 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 27
- 239000003973 paint Substances 0.000 abstract description 25
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical class C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 9
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 8
- 229960002050 hydrofluoric acid Drugs 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007739 conversion coating Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 210000003298 dental enamel Anatomy 0.000 description 5
- 210000003746 feather Anatomy 0.000 description 5
- -1 fluorine ions Chemical class 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
〔産業上の利用分野〕
本発明はアルミニウムおよびアルミニウム合金を塗装す
る前に、該表面に優れた耐食性と塗料密着性を付与する
新規なアルミニウムおよびアルミニウム合金の化成処理
液に関し、例えば、飲料缶の蓋材すなわち缶エンド材等
の表面に効果的に適用されるものである。
〔従来の技術〕
アルミニウムおよびアルミニウム合金の化成処理液とし
てはクロメートタイプとノンクロメートタイプに大別で
きる。クロメートタイプの代表的なものとしては、クロ
ム酸クロメート処理とりん酸クロメート処理とがあり、
クロム酸クロメート処理は１９５０年頃に実用化され現
在も熱交換器のフィン材などに広く使用されている。化
成処理液はクロムＩＩ（Ｃｒｙ３）とフッ化水素酸（Ｈ
Ｆ）が主成分でさらに促進剤が添加されているものであ
りで、若干６価クロムを含有する皮膜を形成する。
りん酸クロメート化成処理は米国特許第２．４３８．８
７７号明細書に開示されており、化成処理液はクロム［
１（Ｃｒｙ）、りん酸（■３ＰＯ４〉、フッ化水素酸（
ＨＦ）からなり、形成される皮膜は水和したりん酸り０
ム（ＣｒＰＯ４・４Ｈ２０）を主成分とするものである
。この皮膜は６価クロムを含有しないことから、飲料用
節および蓋材の塗装下地処理として現在も広く使用され
ている。
以上説明したクロメートタイプの処理液とは別にノンク
ロメートタイプのものが開発されており、その代表的な
発明として特開昭５２−１３１９３７号公報に開示され
たものが挙げられる。この開示された処理液は、ジルコ
ニウムまたはチタンあるいはこれらの混合物、ホスフェ
ートおよびフッ化物を含有し、且つ、０口が約１．０〜
４．０の酸性の水性コーティング溶液である。この開示
された化成処理液を用いて処理を行うとアルミニウム表
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
する化成皮膜を形成する。しかしながら、ノンクロメー
トタイプの処理液は６価クロムを含有しないという利点
を有するもののクロメートタイプに比べると耐食性およ
び塗料密着性が劣るという欠点を有しているのである。
一方、アルミニウム合金の板またはコイルは、塗装され
飲料用筒の蓋材すなわち缶エンド材として広く使用され
ているが、耐食性および塗料密着性向上のために化成処
理がなされており、国内では殆んどの場合にりん酸クロ
メート処理が採用されでいる。これに対してノンクロメ
ートタイプの化成処理はりん酸クロメート処理に比べ塗
料密着性が劣るために米国で一部採用されているにすぎ
ないのが現状である。缶エンド材用のりん酸りＤメート
化成処理の場合は一般的に、りん酸イオン１０．０〜４
０．０’ｊ／１．６（ｉｉクロム２．０〜４．０９／１
およびフッ素イオン０．７〜１．５ｇ／ｌを含有する処
理液で処理されている。また、缶エンド材の塗装には現
在、塩化ビニル系の塗料が主に使用されている。すなわ
ち、缶エンドはアルミニウム合金のコイルあるいは板材
をりん酸クロメート処理し、塩化ビニル系の塗料を塗布
して、その後成型という工程により生産されている。
（発明が解決しようとする課題）
前記従来例で処理されたアルミニウム合金またはコイル
を用いて成形された缶エンドと、ジュースやビールなど
が充填された缶本体により飲料用筒が形成さた飲料用筒
は、その充填物によりバック後に相当過酷な条件で殺菌
処理されるのである。
この殺菌工程において、水蒸気は塗膜を透過し、透過し
た水蒸気はその後塗膜と化成皮膜との界面で凝縮し、こ
れにより塗膜の密着力が低下するといった問題が発生し
やすいのである。実際に、缶エンドの一部がイージーオ
ー＝ブン方式で開缶された時に、開孔部に塗膜剥離によ
る欠陥（エナメルフェザ−〉を生じることがあるので、
この対応として塗料密着性の向上は従来例において解決
しなければならない重要な課題である。
〔課題を解決するための手段〕
前記従来例の課題を解決する具体的手段として本発明は
、りん酸イオン５．０〜４０．０ｇ／ｌ、６価クロムイ
オン１．０〜４．０ｇ／Ｉｔおよびフッ素イオン０．１
〜２．０ｇ／ｌ、フルオロケイ酸イオンを４．０〜１５
゜Ｏｇ／ｌもしくはフルオロホウ酸イオンを０．５〜３
．０ｇ／ｌを含有し、ＤＨを１．０〜３．０にしたこと
を特徴とするアルミニウムおよびアルミニウム合金用化
成処理液を提供するものであり、該化成処理液によって
アルミニウムあるいはアルミニウム合金表面に優れた耐
食性を付与し、且つ塗料密着性の非常に優れた化成皮膜
を形成することができるのである。
つまり、アルミニウムおよびアルミニウム合金を塗装す
る前に、その表面に優れた耐食性と塗料密着性とを付与
する化成処理液を提供しようとするものである。
〔組成および処理工程の説明）
本発明の化成処理液はフッ素錯体イオン、りん酸イオン
、６価クロム、フッ素イオンを必須成分として含む酸性
処理液に関するものである。
フッ素錯体イオンはフルオロケイ酸イオンとフルオロホ
ウ酸イオンから選択される。フッ素錯体イオンの含有に
はフルオロケイ酸、フルオロホウ酸およびこの可溶性塩
から任意に選んで使用できる。フルオロケイ酸イオンの
場合には４．０〜１５．０ｇ／ｊ！の範囲が好ましく、
４．０９／１未満では良好な塗料密着性が得られない。
逆に１５゜ＯｆＪ／１を超えるとエツチングが多くなり
皮膜が充分に形成されない。フルオロホウ酸イオンの場
合には０．５〜５．０ｇ／ｌの範囲が好ましく、０．５
ｆＪ１１未満の場合には良好な塗料密着性が得られない
。逆に５．０ｇ／ｌを超えると廃水処理性が悪くなり経
済上の問題がある。
りん酸イオンを含有させるにはりん１（Ｈ３ＰＯ４）を
使用することが好ましい。りん酸の含有量は５゜０〜４
０．０ｇ／ｌの範囲が好ましく、５．０ｇ／１未満では
形成される皮膜にりん酸クロムが少なくなり塗料密着性
が低下する。４０．０ｇ／ｌを超えても良好な皮膜は形
成されるが、処理液のコストが高くなり経済的に問題が
ある。
６価クロムを含有させるにはりＯム１ｍ（ＣｒＯ２）を
使用することが好ましい。このクロム酸の含有量は１．
０〜４．０ｇ／ｌの範囲が好ましく１ｇ／１未満では化
成皮膜が充分に形成されないため耐食性が劣る。４．０
ｇ／ｌを超えると処理液の廃水処理性が悪くなり、環境
上及び経済上の問題がある。
フッ素イオンは化成皮膜の皮膜成長速度を左右する重要
成分である。フッ素イオンを含有させるにはフッ化水素
酸（ＨＦ）、フッ化ナトリウム（ＮａＦ）、フッ化カリ
ウム（ＫＦ）などを使用することができる。
化成液中のフッ素イオン濃度は以下の如く規定した。イ
オン電極〈フッ素Ｆ−１２５、比較ｌ５−３０５ＤＰ東
亜電波工業■製〉およびイオンメーター（ＩＮ−４０８
東亜電波工業■製）を用い、クロム酸５ｇ／ｌ、リンｌ
１１５ｇ／ｉにフッ化水素酸を一定量ＵＮ、ｔ４ｆ０．
１９／１．１９／１．１０’Ｊ／１ ）を加え、リン酸
あるいは水酸化ナトリウムでｐＨを２．０に調整した液
を基準液（フッ素イオン濃度は添加したフッ化水素酸の
全フッ素量と規定〉とし校正した。そして、化成液の０
口をリン酸あるいは水酸化ナトリウムで２．０に調整後
、フッ素イオンメーターで測定し、その測定値をフッ素
イオン濃度とした。
このフッ素イオンの濃度は０．１〜２．０ｇ／ｌの範囲
が好ましく、０．１ＳＦ／ｊ！未満では成長速度が遅す
ぎ、充分な化成皮膜を得るには長時間処理を行わなけれ
ばならず生産性が劣るという問題がある。逆に２．０ｇ
／ｌを超えると成長速度が速くなり、皮ＩＩ ｆｆｌが
多くなって、不透明な外観になるという問題がある。し
たがって、濃度は０．１〜２．０９／ｌの範囲が好まし
く、特に０．４〜１．（１／ｊ！の範囲が好ましい。
化成処理液のｐＨは１．０〜３．０の範囲に制御される
が、ｐＨの調整にはりん酸、硝酸、塩酸などの酸または
水酸化ナトリウム、水酸化アンモニウムなどから任意に
選んで用いることができる。
ｐＨが１．０未満ではエツチングが多くなって皮膜が形
成され難くなり、逆にｐＨが３．０を超えるとエツチン
グが弱くなり均一な皮膜が形成できなくなる。
次に本発明の化成処理液による処理工程について説明す
る。本発明の化成処理液は現在広く使用されているりん
酸クロメート処理液の代替として用することが可能であ
る。アルミニウムおよびアルミニウム合金の表面に本発
明の化成処理液により化成処理を施す場合に先ず表面の
清浄化が必要であり、そのための洗浄方法としては酸系
、アルカリ系または溶剤系の洗浄液による処理またはこ
れらの組み合せの処理のいずれでもよい。また、必要あ
ればアルミニウムおよびアルミニウム合金の表面を洗浄
後さらに酸あるいはアルカリによりエツチングしてもよ
い。本発明液による処理方法は浸漬、スプレー処理のい
ずれでもよく、処理温度と処理時間は形成する化成皮膜
量を左右する因子となる。処理液の温度は室温〜７０℃
の範囲が可能であり、好ましくは３５〜５５℃の範囲で
あり、また、処理時間は１〜９０秒の範囲が好ましい。
化成皮膜量はりん酸クロメート皮膜と同様にクロム付着
量で評価する。クロム付着量は５〜５０ｑ／ｉの範囲が
好ましく、要求される耐食性の度合により調整する。ク
ロム付′！！組のコントロールは上記処理温度と処理時
間を適宜調整することにより可能である。
本発明の化成処理液より形成される化成皮膜はりん酸ク
ロメート処理において形成される皮膜と同等であり、化
成皮膜は主に水和したりん酸クロム（ＣｒＰＯ４−４８
２０）からなる。
〔実施例〕
以下に本発明の化成処理液に関し、いくつかの実施例を
挙げ、その有用性を比較例と対比して表１に示す。
素材には、アルミニウムーマグネシウム合金（ＪＩＳ
Ａ３０８２ ）を使用した。このアルミニウム合金の脱
脂および化成処理には小型スプレー装置を使用した。こ
の小型スプレー装置は、現在、アルミニウム合金のコイ
ルの化成処理において使用されている連続化成処理ライ
ンにおいてスプレー処理された場合と同様のスプレー条
件になるよう設計されている。化成処理されたアルミニ
ウム合金板に缶エンド用塗料（塩化ビニル系）を塗膜厚
１２〜１４μ扉に塗装し、２００℃で１０分間焼付けを
行い試験板とした。また、化成皮膜のクロム付Ｍ畿は蛍
光Ｘ線分析装置（理学電機工業製３０７０Ｅ型〉を用い
測定した。
耐食性の評価には塩水噴霧試験を行った。塩水噴霧試験
は、ＪＩＳ ２−２３７１に準拠し塗装後の試験板の塗
膜クロスカット部のフクレ発生までの時間で表記した。
したがって、時間が長いほど耐食性は優れる。噴霧時間
が２０００時間以上であれば良好である。塗料密着性は
塗装後の試験板を５×１５０ｍ＋の短冊状に切断し、ボ
リアくド系のフィルムで熱圧着し試片とし、これを脱イ
オン導水に３時間浸漬後１８０度ビール試験法により剥
離し、その際のビール強度より評価した。したがって、
ビール強度が大きいほど塗料密着性は優れる。−般に３
、０ ｋＱｆ１５ ｍ幅であれば良好である。また、
エナメルフェザ−の評価には、軽金属学会第７３回状期
大会講演概要（Ｄ４９）に記載のアルコア法に準拠し行
った。評価は剥離後の最大塗膜残存幅で行った。したが
って、塗膜残存幅が小さい番よどエナメルフェザ−に優
れる。一般に残存幅が０．５Ｍ以下であれば良好である
。
実施例１
アルミニウム合金を市販の強アルカリ性脱脂剤（登録商
標ファインクリーナー４４１８、日本バー力ライジング
株式会社製）の４％加熱水溶液（７０℃〉を用いて洗浄
し、次いで水洗して表面を清浄にした後、化成処理液１
を５０℃に加温して５秒間スプレー処理し次いで水道水
で水洗し、さらに３０００．０００ΩＣＸ１Ｘ上の脱イ
オン水で１０秒問スプレーした後、７０℃の熱風乾燥炉
内で５分間乾燥した。乾燥後、前記の条件で塗装を行い
耐食性、塗料密着性、エナメルフェザ−を評価した。
化成処理液１
４０％フルオロケイ酸（Ｈ３ｉＦ６）
１ Ｂ、８９／１ （ＳｉＦ６τ ７．４９＃り７５
％りんＩｌ！（０３Ｐ０４）
２１ 、 ３ ｇ／ｌ （ＰＯ４３° １５．５ｇ
＃！ ）クロム酸（ＣｒＯ２＞
５．８９／１ （Ｃｒ ３．Ｏｇ／ｌ ）２０
％フン化水素ｉ！１（ＨＦ）
３、０ｇ／ｌ （Ｆ −０，６ｇ／ｌ ）０日２．０
（水酸化アンモニウムで調整）実施例２
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液２を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液２
４０％フルオロケイ酸（Ｈ２ＳｉＦ ６）１ ２ 、
５ ｇ／ｌ （５ｉＦａγ ４．９ｆＪ／１ ）７
５％りん酸（Ｈ３Ｐ０４〉
２１ 、 ３ ｇ／ｊ （Ｐ、０４３− １５．５Ｓ
Ｆ／Ｊ！ ）クロム酸＜ ｃｒｏ３＞
６◆
５．８９／１ （Ｃｒ ３．０ｇ／ｌ！ ）２
０％フッ化水素ＩＩＩ（ＨＦ）
３、０ｇ／ｌ （Ｆ −０，６ｇ／ｌ ）ｐＨ２，０（
水酸化アンモニウムで調整）実施例３
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液３を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液３
４０％フルオロケイ酸（Ｈ３ｉＦ６）
１８、 ８ ｇ／ｌ （５ｉＦｓｔ７．４９／１
）７５％りん酸（８３ＰＧ４）
２１ 、３９／Ｉｔ （ＰＯ４３−１５，５９／ｊ ）
クロムＷｉ（ＣｒＯ３）
２．９９／ｊ！ （Ｃｒ １．５９／ｌ ）２
０％フッ化水素１（ＨＦ）
３、０ｇ／ｌ （Ｆ ０．６ｇ／ｌ ）ｐＨ１，
５（塩酸で調整）
実施例４
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液４を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液４
４０％フルオロケイ酸（８２ＳＩＦ ｓ ）１８、８ｇ
／ｌ （ＳｉＦ６γ７．４９／１ ）７５％りん１ｌｌ
（Ｈ３Ｐ０４）
２１、３９／Ｉｔ （ＰＯ４］−１５，５ｇ／Ｊ！
）クロム酸（ＣｒＯ３）
５、８ｇ／１（Ｃｒ ３．Ｏｇ／ｌ ）２０％フッ化
水素酸（ＨＦ）
５．０’；Ｊ／ｌ （Ｆ １．Ｏｇ／ｌンｐＨ２，
０（水酸化ナトリウムで調整〉実施例５
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液５を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液５
フルオロホウ酸塩（ＮａＢＦ４）
１ 、 ０９／ｌ （ＢＦ４− ０．８９／Ｉ ）
７５％りんＭ （８３ＰＯ４）
２１．３ｇ／ｌ （ＰＯ４３−１ｓ、ｓｇ、／１ ）
クロム酸（ＣｒＯ３）
５．８ｇ／ｌ （Ｃｒ ３．Ｏ’Ｊ／ｌ ）２
０％フッ化水素酸（ＨＦ）
３、０ｇ／ｌ （Ｆ −０，６ｇ／ｌ ）０口２．０（
水酸化アンモニウムで調整）実施例６
実施例１と周一条件でアルミニウム合金を清浄後、化成
処理液６を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液６
フルオロホウ酸塩（ＮａＢｒ４ ）
２．０９／１ （ＢＦ４− １．６９／ｌ ）７５
％りん酸（Ｈ３ＰＯ４）
２１ 、３９／１ （ＰＯ４’−１５，５９／ｊ！
）り０ムＩＩ （ＣｒＯ３）
５．８ｇ／ｌ （Ｃｒ ３．Ｏｇ／ｌ ）２０
％フッ化水馬１（ＨＦ）
３．０９／１ （Ｆ Ｏ，６９／１ ）ｐＨ
２，５（水酸化アンモニウムで調整）実施例７
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液１を４０℃に加温して１０秒間スプレー処理した
。処理後、実施例１と同一条件で水洗、乾燥、塗装し、
性能を評価した。
実施例８
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液１を５０℃に加温して１０秒間スプレー処理した
。処理後、実施例１と同一条件で水洗、乾燥、塗装し、
性能を評価した。
比較例１
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液７を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液７
４０％フルオロケイＩ！（ｔｌ ＳＩＦ ６ ）６．
３９／Ｉ （５ｉＦ６ｒ ２．５９／ｌ ）７５％
りん酸（８３ＰＯ４）
２１ 、 ３ｇ／Ｊ！（ＰＯ４３−１５，５９／１
）クロム酸（Ｃｒ０３）
５．８ｆｌ／Ｉ （Ｃｒ ３．Ｏｇ／ｌ ）２
０％フッ化水素酸（ＨＦ）
３．０ｇ／ｌ （Ｆ −０，６ｇ／ｌ）０口２．０（水
酸化アンモニウムで調整）比較例２
実施例１と同一条件でアルミニウム合金を清浄後、化成
処理液８を５０℃に加温して５秒間スプレー処理した。
処理後、実施例１と同一条件で水洗、乾燥、塗装し、性
能を評価した。
化成処理液８
４０％フルオＯケイ酸（Ｈ２ＳｉＦ ６）４０、０ｇ／
ｌ （５ｉＦｓγ１５．８９／ｊ！ ”）７５％りん酸
（Ｈ３Ｐ０４）
２１、３ｇ／ｌ （ＰＯ４３−１５，５ｇ＃ ）クロ
ム酸（ＣｒＯ３）
５、８ｙ／ｊ！ （Ｃｒ ３．Ｏｇ／ｌ ）２０％０
％フッ素酸（ＨＦ）
３、０ｇ／Ｊ （Ｆ −０，６９／ｌ ）０口２．０
（水酸化アンモニウムで調整）比較例３
実施例１と同一条件でアルミニウム合金を清浄後、市販
のりん酸クロメート剤（登録商標アルクロムに７０２、
日本バー力ライジング株式会社製）の５％水溶液を５０
℃に加温して５秒間スプレー処理した。処理後、実施例
１と同一条件で水洗、乾燥、塗装し、性能を評価した。
比較例４
実施例１と同一条件でアルミニウム合金を清浄後、市販
のノンクロメート剤（登録商標パルコートに３７６１、
日本バー力ライジング株式会社製）の２％水溶液を５０
℃に加温して３０秒間スプレー処理した。処理後、実施
例１と同一条件で水洗、乾燥、塗装し、性能を評価した
。
表１ 評価試験結果
注）傘Ｚ「付着量を示す。
表１に示したように、本発明の化成処理液を用いること
により、優れた耐食性、塗料密着性が得られ、エナメル
フェザ−にも優れることが理解できる。[Industrial Application Field] The present invention relates to a novel chemical conversion treatment solution for aluminum and aluminum alloys that imparts excellent corrosion resistance and paint adhesion to the surfaces of aluminum and aluminum alloys before painting them. It can be effectively applied to the surface of lid materials, ie, can end materials, etc. [Prior Art] Chemical conversion treatment solutions for aluminum and aluminum alloys can be broadly classified into chromate type and non-chromate type. Typical chromate types include chromate chromate treatment and chromate phosphoric acid treatment.
Chromate chromate treatment was put into practical use around 1950 and is still widely used for fin materials of heat exchangers. The chemical conversion treatment liquid consists of chromium II (Cry3) and hydrofluoric acid (H
F) is the main component and an accelerator is further added, forming a film containing a slight amount of hexavalent chromium. Phosphate chromate chemical conversion treatment is based on U.S. Patent No. 2.438.8
It is disclosed in the specification of No. 77, and the chemical conversion treatment liquid is chromium [
1 (Cry), phosphoric acid (■3PO4>, hydrofluoric acid (
HF), and the film formed is made of hydrated phosphoric acid.
The main component is CrPO4.4H20. Since this film does not contain hexavalent chromium, it is still widely used as a coating base treatment for beverage closures and lid materials. In addition to the chromate-type processing liquids described above, non-chromate-type processing liquids have been developed, and a typical invention is one disclosed in Japanese Patent Laid-Open No. 131937/1983. The disclosed treatment liquid contains zirconium or titanium or mixtures thereof, phosphate and fluoride, and has a
4.0 acidic aqueous coating solution. When the disclosed chemical conversion treatment liquid is used for treatment, a chemical conversion film containing zirconium or titanium oxide as a main component is formed on the aluminum surface. However, although non-chromate type treatment liquids have the advantage of not containing hexavalent chromium, they have the disadvantage of inferior corrosion resistance and paint adhesion compared to chromate type treatment liquids. On the other hand, aluminum alloy plates or coils are painted and widely used as can end materials for beverage cylinders, but they are chemically treated to improve corrosion resistance and paint adhesion, and are rarely used in Japan. Phosphoric chromate treatment is used in all cases. On the other hand, non-chromate type chemical conversion treatments have inferior paint adhesion compared to phosphoric acid chromate treatments, and are currently only partially used in the United States. In the case of phosphate D-mate chemical conversion treatment for can end materials, the phosphate ion is generally 10.0 to 4.
0.0'j/1.6 (ii chromium 2.0~4.09/1
and a treatment liquid containing 0.7 to 1.5 g/l of fluorine ions. Furthermore, vinyl chloride-based paints are currently mainly used for painting can end materials. That is, can ends are produced by a process of treating aluminum alloy coils or plates with phosphoric acid chromate, coating them with vinyl chloride paint, and then molding them. (Problems to be Solved by the Invention) A beverage tube in which a beverage cylinder is formed by a can end formed using aluminum alloy or coil treated in the conventional example and a can body filled with juice, beer, etc. The cylinder is sterilized under extremely harsh conditions after being packed with the filling. In this sterilization process, water vapor permeates through the paint film, and the permeated water vapor then condenses at the interface between the paint film and the chemical conversion film, which tends to cause problems such as reduced adhesion of the paint film. In fact, when some can ends are opened using the easy oven method, defects (enamel feathers) may occur at the opening due to paint peeling off.
In response to this, improving paint adhesion is an important issue that must be solved in the conventional example. [Means for Solving the Problems] As a specific means for solving the problems of the conventional example, the present invention provides phosphate ions of 5.0 to 40.0 g/l and hexavalent chromium ions of 1.0 to 4.0 g/l. It and fluorine ion 0.1
~2.0g/l, 4.0-15 fluorosilicate ions
°Og/l or 0.5 to 3 fluoroborate ions
．． 0 g/l and a DH of 1.0 to 3.0, the chemical conversion treatment solution can improve the surface of aluminum or aluminum alloys. It is possible to form a chemical conversion film that provides excellent corrosion resistance and has excellent paint adhesion. That is, the present invention aims to provide a chemical conversion treatment solution that imparts excellent corrosion resistance and paint adhesion to the surfaces of aluminum and aluminum alloys before painting them. [Description of Composition and Treatment Steps] The chemical conversion treatment liquid of the present invention relates to an acidic treatment liquid containing fluorine complex ions, phosphate ions, hexavalent chromium, and fluorine ions as essential components. The fluorine complex ions are selected from fluorosilicate ions and fluoroborate ions. For containing fluorine complex ions, any one selected from fluorosilicic acid, fluoroboric acid, and soluble salts thereof can be used. In the case of fluorosilicic acid ions, it is 4.0 to 15.0 g/j! It is preferable that the range of
If it is less than 4.09/1, good paint adhesion cannot be obtained. On the other hand, if it exceeds 15°OfJ/1, etching will increase and a film will not be formed sufficiently. In the case of fluoroborate ion, the range is preferably 0.5 to 5.0 g/l, and 0.5
If fJ is less than 11, good paint adhesion cannot be obtained. On the other hand, if it exceeds 5.0 g/l, the wastewater treatment properties will deteriorate and there will be economic problems. It is preferable to use phosphorus 1 (H3PO4) to contain phosphate ions. The content of phosphoric acid is 5°0-4
A range of 0.0 g/l is preferable, and if it is less than 5.0 g/l, the formed film will contain less chromium phosphate and paint adhesion will deteriorate. Even if it exceeds 40.0 g/l, a good film can be formed, but the cost of the treatment liquid increases, causing an economical problem. It is preferable to use 1m (CrO2) to contain hexavalent chromium. The content of this chromic acid is 1.
The range of 0 to 4.0 g/l is preferable, and if it is less than 1 g/l, the chemical conversion film will not be sufficiently formed, resulting in poor corrosion resistance. 4.0
If it exceeds g/l, the wastewater treatment properties of the treatment liquid deteriorate, resulting in environmental and economic problems. Fluorine ions are important components that affect the growth rate of chemical conversion coatings. Hydrofluoric acid (HF), sodium fluoride (NaF), potassium fluoride (KF), etc. can be used to contain fluorine ions. The fluorine ion concentration in the chemical solution was defined as follows. Ion electrode (Fluorine F-125, comparative l5-305DP manufactured by Toa Denpa Kogyo ■) and ion meter (IN-408)
(manufactured by Toa Denpa Kogyo ■), chromic acid 5g/l, phosphorus l
Add a certain amount of hydrofluoric acid to 115g/i UN, t4f0.
19/1.19/1.10'J/1) and adjusted the pH to 2.0 with phosphoric acid or sodium hydroxide. The amount and specifications were calibrated.Then, the 0 of the chemical solution was
After adjusting the concentration to 2.0 with phosphoric acid or sodium hydroxide, it was measured with a fluoride ion meter, and the measured value was taken as the fluoride ion concentration. The concentration of this fluorine ion is preferably in the range of 0.1 to 2.0 g/l, and 0.1 SF/j! If it is less than that, the growth rate is too slow and a long treatment time is required to obtain a sufficient chemical conversion film, resulting in poor productivity. On the other hand, 2.0g
If it exceeds /l, there is a problem that the growth rate becomes faster and skin II ffl increases, resulting in an opaque appearance. Therefore, the concentration is preferably in the range of 0.1-2.09/l, particularly 0.4-1. (The range of 1/j! is preferable. The pH of the chemical conversion treatment liquid is controlled within the range of 1.0 to 3.0. To adjust the pH, use an acid such as phosphoric acid, nitric acid, or hydrochloric acid, or sodium hydroxide, It can be arbitrarily selected from ammonium hydroxide, etc. If the pH is less than 1.0, etching will increase and it will be difficult to form a film, and if the pH exceeds 3.0, etching will be weak and a uniform film will be formed. will no longer be formed. Next, the treatment process using the chemical conversion treatment liquid of the present invention will be explained. The chemical conversion treatment liquid of the present invention can be used as a substitute for the phosphoric acid chromate treatment liquid that is currently widely used. Aluminum When carrying out chemical conversion treatment on the surface of an aluminum alloy using the chemical conversion treatment solution of the present invention, it is first necessary to clean the surface, and cleaning methods for this purpose include treatment with an acid-based, alkaline-based or solvent-based cleaning solution, or treatment with an acid-based, alkaline-based or solvent-based cleaning solution, or Any combination of treatments may be used.Also, if necessary, the surfaces of aluminum and aluminum alloys may be etched with acid or alkali after cleaning.The treatment method with the solution of the present invention may be either immersion or spray treatment; Temperature and treatment time are factors that affect the amount of chemical conversion coating formed.The temperature of the treatment solution is room temperature to 70℃.
The temperature is preferably in the range of 35 to 55°C, and the treatment time is preferably in the range of 1 to 90 seconds. The amount of chemical conversion coating is evaluated by the amount of chromium deposited in the same way as the phosphoric acid chromate coating. The amount of chromium deposited is preferably in the range of 5 to 50 q/i, and is adjusted depending on the required degree of corrosion resistance. Comes with chrome! ! The combination can be controlled by appropriately adjusting the above-mentioned processing temperature and processing time. The chemical conversion coating formed from the chemical conversion treatment solution of the present invention is equivalent to the coating formed in phosphoric acid chromate treatment, and the chemical conversion coating mainly consists of hydrated chromium phosphate (CrPO4-48
20). [Examples] Several Examples regarding the chemical conversion treatment liquid of the present invention are listed below, and Table 1 shows the usefulness thereof in comparison with Comparative Examples. The material is aluminum-magnesium alloy (JIS
A3082) was used. A small spray device was used for degreasing and chemical conversion treatment of this aluminum alloy. This small spray device is designed to provide spray conditions similar to those in continuous chemical conversion treatment lines currently used in the chemical conversion treatment of aluminum alloy coils. A can end paint (vinyl chloride type) was applied to the door of a chemical conversion treated aluminum alloy plate with a film thickness of 12 to 14 μm, and the test plate was baked at 200° C. for 10 minutes. In addition, the chromium-attached M ridge of the chemical conversion coating was measured using a fluorescent X-ray analyzer (Model 3070E, manufactured by Rigaku Denki Kogyo).A salt spray test was conducted to evaluate corrosion resistance.The salt spray test conforms to JIS 2-2371. Based on this, the time until blistering occurs at the cross-cut part of the paint film on the test plate after painting is expressed as the time. Therefore, the longer the time, the better the corrosion resistance.If the spray time is 2000 hours or more, it is good.Paint adhesion is The coated test plate was cut into strips of 5 x 150 m+ and heat-pressed with a boria-based film to make test pieces. After immersing this in deionized water for 3 hours, it was peeled off using the beer test method at 180 degrees. It was evaluated based on the beer strength at the time.
The higher the beer strength, the better the paint adhesion. -generally 3
, 0 kQf15 m width is good. Also,
The enamel feather was evaluated in accordance with the Alcoa method described in the 73rd Annual Conference of the Japan Society of Light Metals (D49). Evaluation was performed based on the maximum remaining width of the coating film after peeling. Therefore, the smaller the residual width of the coating film, the better the enamel feather. Generally, it is good if the remaining width is 0.5M or less. Example 1 An aluminum alloy was cleaned using a 4% heated aqueous solution (70°C) of a commercially available strong alkaline degreaser (registered trademark Fine Cleaner 4418, manufactured by Nihon Bariki Rising Co., Ltd.), and then washed with water to clean the surface. After that, chemical conversion treatment liquid 1
was heated to 50° C., sprayed for 5 seconds, washed with tap water, further sprayed with deionized water above 3000.000Ω CX1X for 10 seconds, and dried in a hot air drying oven at 70° C. for 5 minutes. After drying, it was painted under the above conditions and its corrosion resistance, paint adhesion, and enamel feather were evaluated. Chemical conversion treatment solution 1 40% fluorosilicic acid (H3iF6) 1 B, 89/1 (SiF6τ 7.49 #75
%phosphorus! (03P04) 21, 3 g/l (PO43° 15.5g
#! ) Chromic acid (CrO2>5.89/1 (Cr 3.Og/l)20
% hydrogen fluoride i! 1 (HF) 3.0 g/l (F -0.6 g/l) 0 days 2.0
(Adjusted with ammonium hydroxide) Example 2 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 2 was heated to 50° C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Chemical conversion treatment liquid 2 40% fluorosilicic acid (H2SiF 6) 1 2,
5 g/l (5iFaγ 4.9fJ/1)7
5% phosphoric acid (H3P04> 21, 3 g/j (P, 043-15.5S
F/J! ) Chromic acid <cro3> 6◆ 5.89/1 (Cr 3.0g/l!)2
0% hydrogen fluoride III (HF) 3.0 g/l (F -0.6 g/l) pH 2.0 (
Adjustment with ammonium hydroxide) Example 3 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 3 was heated to 50° C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Chemical conversion treatment liquid 3 40% fluorosilicic acid (H3iF6) 18.8 g/l (5iFst7.49/1
) 75% phosphoric acid (83PG4) 21, 39/It (PO43-15,59/j)
Chromium Wi (CrO3) 2.99/j! (Cr 1.59/l)2
0% hydrogen fluoride 1 (HF) 3, 0g/l (F 0.6g/l) pH 1,
5 (adjusted with hydrochloric acid) Example 4 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 4 was heated to 50° C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Chemical conversion treatment liquid 4 40% fluorosilicic acid (82SIFs) 18.8g
/l (SiF6γ7.49/1) 75% phosphorus 1ll
(H3P04) 21,39/It (PO4]-15,5g/J!
) Chromic acid (CrO3) 5.8g/1 (Cr 3.Og/l) 20% Hydrofluoric acid (HF) 5.0'; J/l (F 1.Og/l pH2,
0 (adjusted with sodium hydroxide) Example 5 After cleaning the aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 5 was heated to 50°C and sprayed for 5 seconds. After treatment, the same as in Example 1 The performance was evaluated by washing with water, drying, and painting under the following conditions.Chemical treatment liquid 5 Fluoroborate (NaBF4) 1,09/l (BF4-0.89/I)
75% phosphorus M (83PO4) 21.3g/l (PO43-1s,sg,/1)
Chromic acid (CrO3) 5.8g/l (Cr 3.O'J/l)2
0% Hydrofluoric acid (HF) 3.0 g/l (F -0.6 g/l) 0 mouth 2.0 (
Adjustment with ammonium hydroxide) Example 6 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 6 was heated to 50° C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Chemical conversion treatment liquid 6 Fluoroborate (NaBr4) 2.09/1 (BF4- 1.69/l) 75
% phosphoric acid (H3PO4) 21, 39/1 (PO4'-15,59/j!
) Rim II (CrO3) 5.8g/l (Cr 3.Og/l)20
% Fluoride water horse 1 (HF) 3.09/1 (FO, 69/1) pH
2,5 (Adjusted with ammonium hydroxide) Example 7 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 1 was heated to 40° C. and sprayed for 10 seconds. After treatment, it was washed with water, dried, and painted under the same conditions as Example 1.
Performance was evaluated. Example 8 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 1 was heated to 50° C. and sprayed for 10 seconds. After treatment, it was washed with water, dried, and painted under the same conditions as Example 1.
Performance was evaluated. Comparative Example 1 After cleaning an aluminum alloy under the same conditions as in Example 1, chemical conversion treatment liquid 7 was heated to 50° C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Chemical conversion treatment liquid 7 40% fluorosilicone I! (tl SIF 6)6.
39/I (5iF6r 2.59/l) 75%
Phosphoric acid (83PO4) 21, 3g/J! (PO43-15, 59/1
) Chromic acid (Cr03) 5.8fl/I (Cr 3.Og/l)2
0% hydrofluoric acid (HF) 3.0 g/l (F -0.6 g/l) 0 mouth 2.0 (adjusted with ammonium hydroxide) Comparative Example 2 After cleaning the aluminum alloy under the same conditions as Example 1 The chemical conversion treatment liquid 8 was heated to 50° C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Chemical conversion treatment liquid 8 40% fluorosilicic acid (H2SiF 6) 40.0g/
l (5iFsγ15.89/j!”) 75% phosphoric acid (H3P04) 21,3g/l (PO43-15,5g#) Chromic acid (CrO3) 5,8y/j! (Cr 3.Og/l)20 %0
% Fluoric acid (HF) 3.0g/J (F -0.69/l) 0 mouths 2.0
(Adjusted with ammonium hydroxide) Comparative Example 3 After cleaning the aluminum alloy under the same conditions as in Example 1, a commercially available phosphoric acid chromate agent (registered trademark Alchrom 702,
50% aqueous solution of Nippon Bar Riki Rising Co., Ltd.)
It was heated to 0.degree. C. and sprayed for 5 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Comparative Example 4 After cleaning the aluminum alloy under the same conditions as in Example 1, a commercially available non-chromate agent (registered trademark Palcoat 3761,
50% aqueous solution of Nippon Bar Riki Rising Co., Ltd.)
It was heated to 0.degree. C. and sprayed for 30 seconds. After the treatment, it was washed with water, dried, and painted under the same conditions as in Example 1, and its performance was evaluated. Table 1 Evaluation test results (Note) Shows the amount of coating on Umbrella Z. As shown in Table 1, by using the chemical conversion treatment liquid of the present invention, excellent corrosion resistance and paint adhesion can be obtained, and it can also be applied to enamel feathers. I can understand that it is excellent.
以上説明したように本発明に係るアルミニウムおよびア
ルミニウム合金用化成処理液は、りん酸イオン５．０〜
４０．０ｇ／ｌ、６価クロムイオン１．０〜４．０ｇ／
Ｉｌおよびフッ素イオン０１〜２．０９／１、フルオロ
ケイ酸イオンを４６０〜１５−０ｇ／ｊ！もしくはフル
オロホウ酸イオンを０．５〜３．０ｇ／ｌを含有し、０
口を１゜０〜３．０にしたものであって、特にフルオロ
ケイ酸もしくはフルオロホウ酸を配合させることにより
、塗装前のアルミニウムおよびアルミニウム合金の表面
に優れた耐食性と塗料密着性を有する化成皮膜が形成で
きるという優れた効果を奏する。
平成３年２月４日
平成２年特許願第４０１６８号
２、発明の名称
アルミニウム及びアルミニウム合金用化成処理液３、補
正をする者
事件との関係 特許出願人
名 称 日本パーカライジング株式会社４、代理人
住 所 東京都港区南青山−丁目１番１号発明の詳細
な説明の欄
７、補正の内容
（ヨ）本願明細書中、第６頁、第１９行目の「０５〜５
．０ｇ／Ｉ」を「０．５〜３．０ｇ／ｌ」と訂正する。
（２）同書中、第７頁、第１行目のｒ５．ｏｇ／ｌ」を
ｒ３．Ｏｇ／ＩＪと訂正する。
（３） 同書中、同頁、第１２行目の「量は」と「１
．０〜４．０ｇ／Ｉ」との間に「６価クロムイオンとし
て」を挿入する。
以上As explained above, the chemical conversion treatment liquid for aluminum and aluminum alloys according to the present invention has a phosphate ion concentration of 5.0 to
40.0g/l, hexavalent chromium ion 1.0-4.0g/
Il and fluorine ions 01-2.09/1, fluorosilicate ions 460-15-0 g/j! Or it contains 0.5 to 3.0 g/l of fluoroborate ion, and 0.
A chemical conversion film with a diameter of 1°0 to 3.0, which has excellent corrosion resistance and paint adhesion on the surface of aluminum and aluminum alloys before painting, especially by incorporating fluorosilicic acid or fluoroboric acid. It has the excellent effect of forming February 4, 1991 1990 Patent Application No. 40168 2 Name of the invention Chemical conversion treatment liquid for aluminum and aluminum alloys 3 Relationship to the case of the person making the amendment Patent applicant name Nippon Parkerizing Co., Ltd. 4 Agent Address: 1-1 Minami Aoyama-chome, Minato-ku, Tokyo Column 7 of the detailed description of the invention, Contents of the amendment (Y) "05-5" on page 6, line 19 of the specification of the present application
．． 0g/I" is corrected to "0.5-3.0g/l". (2) In the same book, page 7, line 1, r5. og/l” to r3. Correct it as Og/IJ. (3) In the same book, on the same page, line 12, “quantity is” and “1
．． 0 to 4.0 g/I" and "as a hexavalent chromium ion" is inserted. that's all
Claims (1)
ムイオン１．０〜４．０ｇ／ｌおよびフッ素イオン０．
１〜２．０ｇ／ｌ、フルオロケイ酸イオンを４．０〜１
５．０ｇ／ｌもしくはフルオロホウ酸イオンを０．５〜
３．０ｇ／ｌを含有し、ｐＨを１．０〜３．０にしたこ
とを特徴とするアルミニウムおよびアルミニウム合金用
化成処理液。(1) Phosphate ion 5.0 to 40.0 g/l, hexavalent chromium ion 1.0 to 4.0 g/l, and fluorine ion 0.
1-2.0 g/l, 4.0-1 fluorosilicate ion
5.0g/l or 0.5 to fluoroborate ion
A chemical conversion treatment liquid for aluminum and aluminum alloys containing 3.0 g/l and having a pH of 1.0 to 3.0.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2040168A JPH07100872B2 (en) | 1990-02-21 | 1990-02-21 | Chemical conversion treatment liquid for aluminum and aluminum alloys |
| EP91904950A EP0516700B1 (en) | 1990-02-21 | 1991-02-13 | Conversion treatment method and composition for aluminum and aluminum alloys |
| DE69103139T DE69103139T2 (en) | 1990-02-21 | 1991-02-13 | METHOD AND COMPOSITIONS FOR THE CONVERSION TREATMENT OF ALUMINUM AND ALUMINUM ALLOYS. |
| PCT/US1991/000965 WO1991013186A1 (en) | 1990-02-21 | 1991-02-13 | Conversion treatment method and composition for aluminum and aluminum alloys |
| BR919106049A BR9106049A (en) | 1990-02-21 | 1991-02-13 | WATER CONVERSION COATING SOLUTION, AND, PROCESS TO TREAT AN ALUMINUM SURFACE OR AN ALUMINUM ALLOY |
| US07/923,889 US5451271A (en) | 1990-02-21 | 1991-02-13 | Conversion treatment method and composition for aluminum and aluminum alloys |
| AU73370/91A AU642478B2 (en) | 1990-02-21 | 1991-02-13 | Conversion treatment method and composition for aluminum and aluminum alloys |
| CA 2072592 CA2072592A1 (en) | 1990-02-21 | 1991-02-13 | Conversion treatment method and composition for aluminum and aluminum alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2040168A JPH07100872B2 (en) | 1990-02-21 | 1990-02-21 | Chemical conversion treatment liquid for aluminum and aluminum alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03243781A true JPH03243781A (en) | 1991-10-30 |
| JPH07100872B2 JPH07100872B2 (en) | 1995-11-01 |
Family
ID=12573238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2040168A Expired - Lifetime JPH07100872B2 (en) | 1990-02-21 | 1990-02-21 | Chemical conversion treatment liquid for aluminum and aluminum alloys |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07100872B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2495967C1 (en) * | 2012-07-03 | 2013-10-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие "Уралавиаспецтехнология" | Method of electrolyte-plasma grinding parts made from titanium alloys |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62177182A (en) * | 1986-01-30 | 1987-08-04 | Sumitomo Light Metal Ind Ltd | Chromating method |
-
1990
- 1990-02-21 JP JP2040168A patent/JPH07100872B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62177182A (en) * | 1986-01-30 | 1987-08-04 | Sumitomo Light Metal Ind Ltd | Chromating method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2495967C1 (en) * | 2012-07-03 | 2013-10-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие "Уралавиаспецтехнология" | Method of electrolyte-plasma grinding parts made from titanium alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07100872B2 (en) | 1995-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3964936A (en) | Coating solution for metal surfaces | |
| US4921552A (en) | Composition and method for non-chromate coating of aluminum | |
| EP1433875B1 (en) | Chemical conversion coating agent and surface-treated metal | |
| US5328525A (en) | Method and composition for treatment of metals | |
| US5393354A (en) | Iridescent chromium coatings and method | |
| US5304257A (en) | Trivalent chromium conversion coatings for aluminum | |
| US5641542A (en) | Chromium-free aluminum treatment | |
| US5451271A (en) | Conversion treatment method and composition for aluminum and aluminum alloys | |
| JPH04293789A (en) | Method of coating steel with innoxious, inorganic and corrosion-resistant coating | |
| JPS6022067B2 (en) | Method for forming film on metal surface | |
| JPH07310189A (en) | Surface treating composition for aluminum containing metallic material and surface treatment | |
| US4595424A (en) | Method of forming phosphate coating on zinc | |
| EP0411606B1 (en) | Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method | |
| US6030710A (en) | Copolymer primer for aluminum alloy food and beverage containers | |
| JPH08176841A (en) | Surface treating composition for aluminum-containing metallic material excellent in sludge controlling property and treatment of surface | |
| JPS5841352B2 (en) | Coating treatment liquid for metal surfaces | |
| US5358623A (en) | Corrosion resistant anodized aluminum | |
| EP0516700B1 (en) | Conversion treatment method and composition for aluminum and aluminum alloys | |
| JPH03243781A (en) | Chemical conversion treating solution for aluminum and aluminum alloy | |
| GB871606A (en) | Improvements relating to the production of phosphate coatings on metallic surfaces | |
| US5961809A (en) | Chromium-free process for improving paint adhesion after thin-layer anodization | |
| JPH03243782A (en) | Chemical conversion treating solution for aluminum and aluminum alloy | |
| US6200693B1 (en) | Water-based liquid treatment for aluminum and its alloys | |
| JPH01208477A (en) | Surface treating agent and treating bath for aluminum or alloy thereof | |
| JP3930640B2 (en) | Surface treatment solution for light metal or light alloy materials |