CA2166482A1 - Composition and process for treating tinplate and aluminum - Google Patents
Composition and process for treating tinplate and aluminumInfo
- Publication number
- CA2166482A1 CA2166482A1 CA002166482A CA2166482A CA2166482A1 CA 2166482 A1 CA2166482 A1 CA 2166482A1 CA 002166482 A CA002166482 A CA 002166482A CA 2166482 A CA2166482 A CA 2166482A CA 2166482 A1 CA2166482 A1 CA 2166482A1
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- Prior art keywords
- ppm
- cans
- component
- aluminum
- aqueous liquid
- Prior art date
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Classifications
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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
- C23C22/34—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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A bath for the treatment of DI cans that contains phosphate ions, at least one of zirconium and titanium, oxidizing agent at no more than 500 ppm, and fluorides at no more than 2,000 ppm as fluorine, and that has a pH of 2.0 to 4.0 is useful for treating the surface of both aluminum and tinplate cans prior to the painting/printing thereof.
Description
wo g5/02077 ~ ~ ~6A%~ PCT/US94/07298 .
Description COMPOSITION AND PROCESS FOR TREATING TINPLATE AND ALUMINUM
Technical Field The invention relates to a novel co,npositio", usually called a "bath" here-inafter for brevity, and process that can be used to treat the surface of both alum-inum Dl cans and li,1plale Dl cans and that impart an excellent corrosion resist-5 ance and paint adherence to the surface of these cans prior to painting and/orp, i"lir~g them. "Aluminum Dl cans" and "til ~pldle Dl cans" refer to cans fabricated by the drawing and ironing, also called draw-ironing, of aluminum sheet and tin-plated steel sheet respectively.
Background Art Aluminum Dl cans and linpldle Dl cans have her~lorore been treated with separaLe special purpose surface treatment baths. Baths for treating the surfaceof aluminum Dl cans are exemplified by the bath taught in Japanese Laid Open [Kokai or Unexamined] Patent Application Number Sho 52-131937 [131,937/
1977]. The surface treatment bath taught therein is an acidic aqueous coating solution that has a pH of a~ roxi" ~ately 1.0 to 4.0 and that COI ,lains phosphate, fluoride, and zirconium and/or titanium. Tr~at" ,enl with this conversion treaLn ,e, ll bath results in the r("",alion of a highly paint-adherent, highly corrosion-resistant conversion film on the aluminum surface. The main components of this film are phosphate salt and zirconium oxide or titanium oxide.
Baths for treating the surface of tinplate Dl cans are exemplified by the bath taught in Japanese Laid Open Patent Application Number Hei 1-100281 [100,281/1989]. This invention co",,urises a conversion film-forming bath for the treatment of metal surfaces. The bath in this case has a pH of 2 to 6 and con-tains 1 to 50 g/L of phosphale ions, 0.2 to 20.0 g/L of oxyacid ions, 0.01 to 5.0 9/L of tin ions, and 0.01 to 5.0 g/L of condensed phospl ~dle ions. Treatment with this conversion treatment bath results in the formation of a highly corrosion-re-sistant film on the surface of tinplate Dl cans. The main component of this filmis tin phosphate.
A device known as a washer is generally used to treat the surface of Dl WO 95/02077 ~16~ PCT/US94/07298 cans. The formed Dl cans are continuously treated with a degreasing composi-tion and a conversion coating composition while turned upside down. Washers currently in use most often execute the following 6 processes: preliminary de-greasing, degreasing, water wash, surface treatment, water wash, and a wash 5 with de-ionizedwater.
In order to conduct surface l,edl",ent using such a washer, it has been necessary to select a surface treatment bath adapted to the type of Dl cans to be treated. In other words, a Iredl",enl bath in accor~l~nce with, for example, the invention in Japanese Laid Open Patent Application Number Sho 52-131937 10 would be used as the surface l,eal"~enl bath for aluminum Dl cans, while a treat-ment bath in accordance with, for example, Japanese Laid Open Patent Applica-tion Number Hei 1-100281 would be used as the treatment bath for tinplate Dl cans.
Disclosure of the Invention Problems to Be Solved by the lnvention Accompanying recent increases in the diversity of Dl cans fabrication, there has been increasing opportunity to collect aluminum Dl cans and tinplate Dl cans into respective lots of some size and treat these in a single washer in an alternating sequence. However, a high-quality film with good corrosion resist-20 ance is not produced when the l,eal",enl bath in acc~,dance with Japanese LaidOpen Patent Application Number Sho 52-131937 is also applied to tinplate Dl cans. On the other hand, a conversion film is not formed when the lrealmenl bath of Japdl ,ese Laid Open Patent Appli~lion Number Hei 1-100281 is also ap-plied to aluminum Dl cans; this results in a poor corrosion resislance and a poor 25 paint film adherence. As a result, each time the treatment subslrale changes,it has been necess~y to discard the treatment bath, clean the l~eal~ent cham-ber itself, and install a freshly prepared treatment bath that cGrtespGI ,cls to the type of substrate.
In view of the circumstances described above, this invention takes as its 30 object the provision of a multipurpose treatment bath and treatment process wherein a single treatment bath can be used to lay down a highly corrosion-re-sistant, highly paint-adherent film on the surface of both aluminum Dl cans and ~1~6~8~
tinplate Dl cans.
Summary of the Invention The applica"ls have discovered that eluted metal ions, i.e., aluminum ions or tin ions, have a negative effect on film formation on the surface of a subsll ale which is not of the same metal. This is a major reason why a high-quality film is not rolllled when the conventional treatment baths are also applied to suL,sl,ale dirrt:r~nl ~rom the one for which they were desiyned. The applicants further form-ulated the following working hypotheses which were useful in solving the prob-lems with the prior art as outlined above.
o (1) With the conventional l,~cl",e,)l baths, a film based on zirconium oxide or titanium oxide is formed on the surface of aluminum Dl cans, while a tin oxide-based film is formed on the surface of tinplate Dl cans.
Description COMPOSITION AND PROCESS FOR TREATING TINPLATE AND ALUMINUM
Technical Field The invention relates to a novel co,npositio", usually called a "bath" here-inafter for brevity, and process that can be used to treat the surface of both alum-inum Dl cans and li,1plale Dl cans and that impart an excellent corrosion resist-5 ance and paint adherence to the surface of these cans prior to painting and/orp, i"lir~g them. "Aluminum Dl cans" and "til ~pldle Dl cans" refer to cans fabricated by the drawing and ironing, also called draw-ironing, of aluminum sheet and tin-plated steel sheet respectively.
Background Art Aluminum Dl cans and linpldle Dl cans have her~lorore been treated with separaLe special purpose surface treatment baths. Baths for treating the surfaceof aluminum Dl cans are exemplified by the bath taught in Japanese Laid Open [Kokai or Unexamined] Patent Application Number Sho 52-131937 [131,937/
1977]. The surface treatment bath taught therein is an acidic aqueous coating solution that has a pH of a~ roxi" ~ately 1.0 to 4.0 and that COI ,lains phosphate, fluoride, and zirconium and/or titanium. Tr~at" ,enl with this conversion treaLn ,e, ll bath results in the r("",alion of a highly paint-adherent, highly corrosion-resistant conversion film on the aluminum surface. The main components of this film are phosphate salt and zirconium oxide or titanium oxide.
Baths for treating the surface of tinplate Dl cans are exemplified by the bath taught in Japanese Laid Open Patent Application Number Hei 1-100281 [100,281/1989]. This invention co",,urises a conversion film-forming bath for the treatment of metal surfaces. The bath in this case has a pH of 2 to 6 and con-tains 1 to 50 g/L of phosphale ions, 0.2 to 20.0 g/L of oxyacid ions, 0.01 to 5.0 9/L of tin ions, and 0.01 to 5.0 g/L of condensed phospl ~dle ions. Treatment with this conversion treatment bath results in the formation of a highly corrosion-re-sistant film on the surface of tinplate Dl cans. The main component of this filmis tin phosphate.
A device known as a washer is generally used to treat the surface of Dl WO 95/02077 ~16~ PCT/US94/07298 cans. The formed Dl cans are continuously treated with a degreasing composi-tion and a conversion coating composition while turned upside down. Washers currently in use most often execute the following 6 processes: preliminary de-greasing, degreasing, water wash, surface treatment, water wash, and a wash 5 with de-ionizedwater.
In order to conduct surface l,edl",ent using such a washer, it has been necessary to select a surface treatment bath adapted to the type of Dl cans to be treated. In other words, a Iredl",enl bath in accor~l~nce with, for example, the invention in Japanese Laid Open Patent Application Number Sho 52-131937 10 would be used as the surface l,eal"~enl bath for aluminum Dl cans, while a treat-ment bath in accordance with, for example, Japanese Laid Open Patent Applica-tion Number Hei 1-100281 would be used as the treatment bath for tinplate Dl cans.
Disclosure of the Invention Problems to Be Solved by the lnvention Accompanying recent increases in the diversity of Dl cans fabrication, there has been increasing opportunity to collect aluminum Dl cans and tinplate Dl cans into respective lots of some size and treat these in a single washer in an alternating sequence. However, a high-quality film with good corrosion resist-20 ance is not produced when the l,eal",enl bath in acc~,dance with Japanese LaidOpen Patent Application Number Sho 52-131937 is also applied to tinplate Dl cans. On the other hand, a conversion film is not formed when the lrealmenl bath of Japdl ,ese Laid Open Patent Appli~lion Number Hei 1-100281 is also ap-plied to aluminum Dl cans; this results in a poor corrosion resislance and a poor 25 paint film adherence. As a result, each time the treatment subslrale changes,it has been necess~y to discard the treatment bath, clean the l~eal~ent cham-ber itself, and install a freshly prepared treatment bath that cGrtespGI ,cls to the type of substrate.
In view of the circumstances described above, this invention takes as its 30 object the provision of a multipurpose treatment bath and treatment process wherein a single treatment bath can be used to lay down a highly corrosion-re-sistant, highly paint-adherent film on the surface of both aluminum Dl cans and ~1~6~8~
tinplate Dl cans.
Summary of the Invention The applica"ls have discovered that eluted metal ions, i.e., aluminum ions or tin ions, have a negative effect on film formation on the surface of a subsll ale which is not of the same metal. This is a major reason why a high-quality film is not rolllled when the conventional treatment baths are also applied to suL,sl,ale dirrt:r~nl ~rom the one for which they were desiyned. The applicants further form-ulated the following working hypotheses which were useful in solving the prob-lems with the prior art as outlined above.
o (1) With the conventional l,~cl",e,)l baths, a film based on zirconium oxide or titanium oxide is formed on the surface of aluminum Dl cans, while a tin oxide-based film is formed on the surface of tinplate Dl cans.
(2) Etching of the metal sub:jlr~le is necessary in order to form the films not-ed under (1), and this is most readily ac h ~vcd by adjustment of the treat-ment bath pH to 2.0 to 4Ø At a pH below 2.0, film formation is impaired due to an excessive etch, while it becomes difficult to produce a highly co" osio, I-resislanl film at a pH in excess of 4Ø Ther~rore, the pH should be controlled to 2.0 to 4Ø
(3) Tin ions (Sn2~, Sn4') elute from the surface of tinplate Dl cans under the 2 0 COndi~iGI IS noted in item (2). When an aluminum can is then treated, the divalent tin ions that have eluted into the treatment bath tend to be re-duced to tin metal at the aluminum surface; this prevents the formation of a high~uality film on the aluminum surface. As a result, an oxidizing ag-ent is prt:r~rably added to the l~dtll ~enl bath in order to rapidly oxi~i~e thetinl ions in the t~eat~enl bath to the tetravalent state and thereby achieve their stable presence in the bath.
(4) Aluminum ions elute from the aluminum surface under the conditions not-ed in item (2), and these aluminum ions dest~hi~ any zirconium or titani-um compounds present in the bath. To counter this, fluoride or hydro-3 O fluoric acid pr~r~:r~bly is added to the treatment bath in order to stabilize the p~sence of aluminum in the treatment bath by forming fluoride com-plexes with the aluminum ions.
WO 95/02077 ~ PCT/US94/07298 .
WO 95/02077 ~ PCT/US94/07298 .
(5) While the oxidi~ g agent accelerates the fo""alion of zirconium oxide or titanium oxide on an aluminum surface, it tends to inhibit the formation of a prute~ /e codling including tin p hospllale on a tin surface. Since more than 500 parts per million by weight (hereinafter usually abbreviated s "ppm") of oxidizing agent will usually prevent film formation, the appropri-ate upper limit on the oxicli~i"g agent is 500 ppm. Fxcessive levels of hy-drofluoric acid or fluoride result in an excessive etch, which degrades the appearance, and a suitable upper limit on this additive is 2,000 ppm as fluorine.
Accordingly, a composilion according to the invention for the treatment of Dl cans contains phosphate ion and at least 1 selection from zirconium com-pounds and titanium compounds and has a pH of 2.0 to 4.0, contains oxidizing agent at no more than 500 ppm and at least 1 selection from simple and complex fluorides and their corresponding acids in a total amount that is no more than 2,000 ppm stoichiometric equivalent as fluorine. More prererably, a composition according to the invention consists essenlially of water, the other ingredients not-ed above, and, if desired, the optional ingredient(s) noted below, and still more pr~rerably co, Isisls only of these ingredients plus any necess~ry counterions to provide electrical neutrality to the co,l,posilion and possible impurities in the de-sired ingredients.
Another embodiment of the invention is a process for treating the surface of aluminum Dl cans and tinplate Dl cans, said process being characterized by ccl lla.Aing the cleaned surface of aluminum Dl cans or tinplate Dl cans with the treatment bath described above.
Description of Pleferled Embodiments The oxidi~i"g agent in a cor, IpOSiliOn accorli. ,9 to the invention is exempli-fied by h~ oge, l peroxide, chlorates, nitrites, tungsl~es, molybdates, and the like, and thus is not narrowly restricted in scope. However, hyd~ogen peroxide is ~refe~ I ed. Since the oxidizing agent functions to stabilize the tin ion eluted 3 O from the Dl cans, its optimal conlenl is a function of the amount of tin elution. An oxi.li~ing agent content in the range of 20 to 500 ppm is preferred for eluted tin cc:, Icenlrdliol ,s on the level of 50 ppm, while the range of 40 to 200 ppm for the wo 95,02077 2~ PCT/US94/07298 oxidi~i"g agent is particularly prererl ed under most conditions of operation of a process according to this invention. These numerical values apply specifically to hydluell peroxide; for other oxidizing agents the values should be adjusted a~.pr~p, i~lely to provide the same oxidizing power as does the stated amounts of hydrogen peroxide. Ordinarily, the value for other oxidizing agents may be computed with sufficient accuracy for the p-" ~ oses of the invention by noting the number of electrons involved in the reduction reaction of the particular oxidizing agent used and adjusting the amount of oxidi~i"g agent to provide removal of thesame number of electrons from the oxidized subsl~le as does the specified amounts of h~/dluyell peruxide. Alternatively, the oxidizing power may be mea-sured by con,pa, in~ the electrical pole"lial of an inert electrode such as a platin-um electrode that is immersed in the composition, and ~',usting the amount of other oxidizing agents so that the same electrical potential is produced in the lledlll~enl Gomposition according to the invention as with the specified amountsof hydlogen peroxide.
~1 organic acid that can readily form complexes with dissolved tin ions, aluminum ions, or both, for example, gluconic acid or oxalic acid, may be added on a supple",e"la~y basis in the event of a major decline in treatment bath stabi-lity due to metal ions, for example, iron or tin ions eluting from tinplate Dl cans, aluminum eluting from aluminum Dl cans, and the like.
The l, ~at" ,enl bath must contain at least 1 sele~lion from simple and com-plex fluorides and their corresponding acids. The fluoride COI ,lenl ,~,rererably is derived from hydrofluoric acid (HF) or a salt thereof such as sodium fluoride (NaF), or through the use of nuO ilconic acid (H2ZrF6) or fluotitanic acid (H2TiF6) or their salts. The oplilll21 fluoride conl~nl is determined as a function of the con-ce"I,alion of aluminum that elutes from the aluminum Dl cans. For example, 100 ppm alunninum prerer~bly requires approxi",~lely 200 ppm fluorine. The fluoride content preferably falls in the range of 10 to 2,000 ppm as fluorine and more prererdbly, with i"cr~asing pr~fere~ ,ce in the order given, falls in the range of 20 to 900, 40 to 500, 60 to 200, or 90 to 165, ppm as fluorine. When the fluoride conlenl falls below 10 ppm as fluorine, the treatment bath becomes poorly react-ive with ~he surface of aluminum Dl cans and an acceptable film is not usually WO 95/02077 ~ - PCT/US94/07298 2~C~
produced.
The other components used in the invention treatment bath correspond to those used in conventional treatment baths. Thus, phosphoric acid (H3P04), sodium pl ,osphdle (Na3PO4), and the like can be used to supply the phosphate ion in the treatment bath. Although less prerer, ed, condensed pl ,osphoric acids such as py, op hospl ,o, ic acid (H4P207) and tripolyphosphoric acid (H5P30,0) and their salts can also be used. While the phospl ,ate ion COI ,lenl is not narrowly re-stricted, values in the range of 10 to 500 ppm are preferred and values in the range of 20 to 90 ppm are more prere"ed. In determining these values, the stoi-chior"~:l, ic equivalent as phosphale of all phospl)Gric acid(s) and anions formed by ionization thereof is considered to be phosphate.
The source of the zirconium and titanium cor,)pounds for the treatment bath is not narrowly restricted in scope, and the oxides, hydroxides, fluorides,and the like of zirconium and titanium can all be used, as can fluo~ir~o"ic and flu-otitanic acids and their salts, these acids and their salts being prefer,ed. Theconlenl of zirconium or titanium compound is preferably 10 to 200 ppm as Zr or Ti and more prerer~bly, with in~;teasing prererel1ce in the order given, 10 to 150, 20 to 100, or 25 to 90, ppm as Zr or Ti.
The pH of the t,~lment bath can be adjusted through the use of an acid such as phosphoric acid, nitric acid, hydrochloric acid, or hydrofluoric acid, or through the use of an alkali such as sodium hy, lo,dde, sodium carbonate, or am-monium hydroxide. The pH of the treatment bath normally should be from 2.0 to 4.0, while the range of 2.5 to 3.3 is prerer,ed.
The leclmi4ue for conlac~ g the surface l,e~l"~ent bath with aluminum Dl cans or tinplate Dl cans is exemplified by immersion, spraying, and the like as generally known in the art, with spraying being the p~efe"ed technique. The tem-perature of the treatment bath should usually be 20 to 65C and is prererably 25 to 65, more preferably 30 to 60, or still more preferably 30 to 35, C. The l,edl",e"l time usually is from 2 to 120 seconds, ~,ererably from 2 to 60secotlds, and particularly pr~rerdbly from 15to60 seconds. A tlt:dtlllenl time below 2 sec-onds does not usually produce an ~de~u~te r~c;lion, thereby esse"lially preclud-ing the formation of a highly corrosion-resistant film, while the improvement in wo 95,02077 2 1 6 ~4 ~2 PCT/US94/07298 performance diminishes at treatment times in excess of 60 seconds.
The L,eat",e, ll bath of the present invention is preferably used as part of the following process steps:
(1 ) cleaning of the Dl cans surface, prererably by degreasing;
5 (2) water wash;
(3) filrrl-ro""alion t~:dLmelll, using a cGn,posilion according to the invention;
(4) water wash;
(5) wash with deionized water; and (6) drying.
Examples The usefulness of the surface treatment bath of the present invention is illustrated below through a comparison of several working examples with com-parative examples. In these examples and cor"parison examples, any unspeci-fied material in a treatment bath co,nposition is water.
15General ~ondilio"s for Examples and Comparison Examples The aluminum Dl cans The aluminum Dl cans were fabricated by the draw-ironing of aluminum sheet. They were cleaned using the hot ~gueo-ls solution of an acidic deg, easer(PalklinTM 400, from Nihon Parke,i~ing Corn~any, Ltd., Tokyo) and then subject-20 ed to surFace l,edl",enl.
The tinplate Dl cans The lil ,,.,lale Dl cans were rabricale.l by the draw-ironing of tin-plated steel sheet. They were claaned using a hot ~ueo~ ~s solution of a weakly alkaline de-y,easer (IFinecleanerTM 4361A, from Nihon Parkerizing Co~npa~)y, Ltd., Tokyo) 25 and then subjected to surface treatment.
Corrosion resisla,)ce The co"osion resistance of the aluminum Dl cans was evaluated by im-,ner~i"g tlhe treated cans in boiling water for 30 minutes and then evaluating the degree of blackening (the a6sel,ce of blackening is prerel,ed). The corrosion re-30 sistance of the tinplate Dl cans was evaluated using the iron exposure value("IEV") measured in accordal ,ce with United States Patent Number 4,332,646.
A lower IFV is indicative of a better co" usion resisldnce, and values at or below wo 95/02077 ~6 ~ 4~ ~ PCT/US94/07298 150 are generally considered excellent.
Paint adherence The paint adherence was evaluated on the basis of the peel sL, e, IlJth as follows: An epoxy-urea can paint was applied on the surface of the treated can 5 to yield a paint film thickness of 5 to 7 micrometers. After baking for 4 minutes at 215 C, a 5 x 150 mm strip was cut from the can. A test specimen was pre-pared by hot-press bonding the strip with polyamide film, and the test specimen was peeled in a 180 peel test to provide the peel strength value. Higher peel ,gti, values are indicative of a better paint adhesion, and values of at least 10 1.5 kilograms-force ("kgf")/5 mm of width are generally considered excellent.
Example 1 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of treatments: spraying for 30 seconds with surface l~edl",e, It bath 1 heated to 40 C, then washing with tap water, spraying with de-15 ionized water (having a specific r~:sislance of at least 3 megaohm-cm) for 10 sec-onds, and finally drying for 3 minutes in a forced convection drying oven at 180 C. The corrosion resistance and adherence of the resulting Dl cans were then measured.
Surface treatment bath 1 75 % ,chos~ l,oric acid (H3PO4): 69 ppm (Po43-: 50 ppm) 20 % fluo~ir~nic acid (H2ZrF6): 500 ppm (zr4t 44 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-': 95 ppm') 30 % h~,clrogen peroxide (H2O2): 166 ppm (H2O2 50 ppm) pH 3.0 (adjusted with ~q~leous ~r"",~nia) Example 2 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of treatments: spraying for 15 seconds with surface Ll~dtlllel ll bath 2 heated to 30 C, then a water wash, wash with de-ionized wat-er, and drying as in Exa",~lc 1. The corrosion resistance and adherence of the 1The total fluoride in this and all the other cGr"posilions containing both simple and complex fluoride ions is the total from both sources.
~B&~
WO 9~/02077 PCT/US94/07298 .
resulting Dl cans were subsequently measured.
Surface treal",ellt bath 2 75 % phosphoric acid (H3P04): 69 ppm (PO43-: 50 ppm) 20 % fluo~irco"ic acid (H2ZrF6): 1000 ppm (Zr4~: 88 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-: 150 ppm) 30 % hydrogen peroxide (H2O2): 166 ppm (H2O2: 50 ppm) pH 3.3 (adjusted with aqueous atn,nonia) Example 3 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected o to the following sequence of treatments: spraying for 15 seconds with surface Il edl",enl bath 3 heated to 35 C then a water wash wash with deionized water and drying as in Exal ~ c 1. The corrosion resislance and adherence of the re-sulting Dl cans were subsequently measured.
~urface treatment bath 3 75 % phospi ,oric acid (H3PO4): 69 ppm (Po43-: 50 ppm) 20 % fluotitanic acid (H2TiFB): 500 ppm (Ti4~ 29 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-: 110 ppm) 30 % hydrogen peroxide (H2O2): 664 ppm (H2O2: 200 ppm) pH 2.5 (adjusted with ~queo~ls a~mG~Iia) FY:~rnple 4 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of treatments: spraying for 30 seconds with surface l,~dt",ent bath 4 heated to 40 C then a water wash wash with deionized water and drying as in Example 1. The co,tosion lesislance and adherence of the re-sulting Dl cans were sl Ihse~uently measured.
Surface treatment bath 4 75 % phosphoric acid (H3PO4): 138 ppm (PO4~: 100 ppm) 20 % fluotitanic acid (H2TiF6): 500 ppm (Tj4t 29 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-: 1 10 ppm) 30 % hydrogen peroxide (H2O2): 166 ppm (H2O2 50 ppm) pH 3.5 (adjusted with aqueous an,r"onia) Example 5 As discussed above, a critical issue for multipurpose treatment baths is the film performance when metal ions different from the substrate metal have entered the bath by a preceding elution from Dl cans. In this example, 500 ppm 5 of tin ions was introduced into surface treatment bath 1 and the resulting surface treatment bath, heated to 60 C, was used for a 30-second spray treatment.
Washing and drying were then carried out as in Example 1.
Example 6 100 ppm of aluminum ions were introduGed into surface treatment bath 1 o and the resulting surface l,e~t"~enl bath, heated to 30 C, was used for a 30-sec-ond spray t,edl",e, ll. Washing and drying were then carried out as in Example 1.
Example 7 50 ppm of tin ions were introduced into surface treatment bath 2 and the 15 resulting surface treatment bath, heated to 60 C, was used for a 30-sec~nd spray treatment. Washing and drying were then carried out as in Example 1.
Example 8 100 ppm of aluminum ions were introduced into surface ll eaLmenl bath 2 and the resulting surface treatment bath, heated to 30 C, was used for a 2 0 30-second spray treatment. Washing and drying were then carried out as in Ex-ample 1, and the corrosion resistance and adherence of the resulting Dl cans were measured.
Comparative Example 1 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected 25 to the following sequence of treatments: spraying for 30 seconds with surfacell ealmenl bath S heated to 30 C, then a water wash, wash with deionized water,and drying as in Example 1. The corrosion resistance and adherence of the re-sulting Dl cans were subsequently measured.
Surface treatment bath 5 75 % phosphoric acid (H3P04): 69 ppm (P043~ 50 ppm) 20 % fluo~irc~"ic acid (H2ZrF6): 500 ppm (Zr4~ 44 ppm) wo 95,02077 ~ 4 ~ PCT/US94/07298 20 % hydrofluoric acid (HF): 210 ppm (total F: 95 ppm)pH 3.0 (adjusted with aqueous ammonia) Comparative Example 2 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were sl lhjected 5 to the following sequence of treatments: spraying for 30 seconds with surface lreal",ent bath 6 heated to 30 C then a water wash wash with deionized water and drying as in Exan,~ 1. The corrosion resistance and adherence of the re-sulting Dl cans were subsequently measured.
Surface I,edl,nel,t bath 6 o 75 % pl ,osphoric acid (H3P04): 69 ppm (P04~: 50 ppm) 20 % hydrofluoric acid (HF): 210 ppm (F- 40 ppm) pH 3.0 (adjusted with aqueous ammonia) Comparative Example 3 50 ppm of tin ions were introduced into surface treatment bath 5 and the resulting surface treatment bath heated to 30 C was used for a 30-second spray treaImenL Washing and drying were then carried out as in Example 1 and the co" osion r~sistance and a-ll ,ere"ce of the resulting Dl cans were measured.
Co")pal alive Example 4 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of Ir~al~"e"Ls; heating a co",n,er~ ial surface treaI",el1I
bath intended for application to aluminum Dl cans (AlodineTM 404 from Nihon Parkerizing Company Ltd. Tokyo) to 30 C and spraying with this for 30 sec-onds then a water wash wash with deionized water and drying as in Example 1. The cor,osio" r~sisIal ,ce and a.ll ,er~"ce of the resulting Dl cans were subse-quently measured.
Cor"paré,Iive Example 5 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the foliowing sequence of tredImenIs; heaIi"g a cor~ er~ ial surface treatment bath intended for application to tinplate Dl cans (PalfosTM K3482 from Nihon Parkerizing Co""~al1y Ltd. Tokyo) to 30 C and spraying with this for 30 seG
onds then a water wash wash with deionized water and drying as in Example W0 95/02077 ~ .a~ PCT/US94107298 1. The co" uSiOI ~ resisldl ,ce and adherence of the resulting Dl cans were subse-quently measured.
The results of all the measurements noted above are shown in Table 1 on the following page.
5 Benefits of the Invention The treatment bath in accordance with the present invention produces a titanium oxide-containing or zirconium oxide-containing film on the surface of aluminum Dl cans and prod~ ~Ges a tin oxide-containing film on the surface of tin-plate Dl cans. This multipurpose applicability to different types of substrates is 10 made possible by the presence in the treatment bath of both an oxidizing agent and hydrofluoric acid and/or fluoride and by the stipulation of specir,c upper limits for them. A process according to the invention provides cans, prior to painting and/or ,c ri, llil 19 them, with an excellen~ co" osion resi~lance and paint adherence through a low-temperature treatment.
WO 9~/02077 PCT/US94/07298 ~6~8~
Table I
Cor,~sion Ræsisl~nce Paint Film Adher~.. ce (K~r/5m." of Width) Aluminum Tin- Alum- Tinplate (Blacheni"~) plateinum (IE~
Example 1 no 100 5.0 3.5 blackening Example 2 no 100 5.0 3.5 blackening Example 3 no 100 5.0 3.5 blackening Example 4 no 100 5.0 3.5 blackening Example 5 no 100 5.0 3.5 blackening Example 6 no 100 5.0 3.5 blackening Example 7 no 100 5.0 3.5 blackening Example 8 no 100 5.0 3.5 blackening Compar~tive ",oder;lte 200 2.5 1.5 Example 1 blackening Compar~tive blackening over 300 1.0 1.0 Example 2 entire surface Co."pa.. aliie blackening over 180 1.0 1.0 Example 3 entire surface Compar~lhre no blackening 300 5.0 1.0 Cxan ~le 4 Comparative blackening over 100 1.0 3.5 Exdl~ le 5 entire surface
Accordingly, a composilion according to the invention for the treatment of Dl cans contains phosphate ion and at least 1 selection from zirconium com-pounds and titanium compounds and has a pH of 2.0 to 4.0, contains oxidizing agent at no more than 500 ppm and at least 1 selection from simple and complex fluorides and their corresponding acids in a total amount that is no more than 2,000 ppm stoichiometric equivalent as fluorine. More prererably, a composition according to the invention consists essenlially of water, the other ingredients not-ed above, and, if desired, the optional ingredient(s) noted below, and still more pr~rerably co, Isisls only of these ingredients plus any necess~ry counterions to provide electrical neutrality to the co,l,posilion and possible impurities in the de-sired ingredients.
Another embodiment of the invention is a process for treating the surface of aluminum Dl cans and tinplate Dl cans, said process being characterized by ccl lla.Aing the cleaned surface of aluminum Dl cans or tinplate Dl cans with the treatment bath described above.
Description of Pleferled Embodiments The oxidi~i"g agent in a cor, IpOSiliOn accorli. ,9 to the invention is exempli-fied by h~ oge, l peroxide, chlorates, nitrites, tungsl~es, molybdates, and the like, and thus is not narrowly restricted in scope. However, hyd~ogen peroxide is ~refe~ I ed. Since the oxidizing agent functions to stabilize the tin ion eluted 3 O from the Dl cans, its optimal conlenl is a function of the amount of tin elution. An oxi.li~ing agent content in the range of 20 to 500 ppm is preferred for eluted tin cc:, Icenlrdliol ,s on the level of 50 ppm, while the range of 40 to 200 ppm for the wo 95,02077 2~ PCT/US94/07298 oxidi~i"g agent is particularly prererl ed under most conditions of operation of a process according to this invention. These numerical values apply specifically to hydluell peroxide; for other oxidizing agents the values should be adjusted a~.pr~p, i~lely to provide the same oxidizing power as does the stated amounts of hydrogen peroxide. Ordinarily, the value for other oxidizing agents may be computed with sufficient accuracy for the p-" ~ oses of the invention by noting the number of electrons involved in the reduction reaction of the particular oxidizing agent used and adjusting the amount of oxidi~i"g agent to provide removal of thesame number of electrons from the oxidized subsl~le as does the specified amounts of h~/dluyell peruxide. Alternatively, the oxidizing power may be mea-sured by con,pa, in~ the electrical pole"lial of an inert electrode such as a platin-um electrode that is immersed in the composition, and ~',usting the amount of other oxidizing agents so that the same electrical potential is produced in the lledlll~enl Gomposition according to the invention as with the specified amountsof hydlogen peroxide.
~1 organic acid that can readily form complexes with dissolved tin ions, aluminum ions, or both, for example, gluconic acid or oxalic acid, may be added on a supple",e"la~y basis in the event of a major decline in treatment bath stabi-lity due to metal ions, for example, iron or tin ions eluting from tinplate Dl cans, aluminum eluting from aluminum Dl cans, and the like.
The l, ~at" ,enl bath must contain at least 1 sele~lion from simple and com-plex fluorides and their corresponding acids. The fluoride COI ,lenl ,~,rererably is derived from hydrofluoric acid (HF) or a salt thereof such as sodium fluoride (NaF), or through the use of nuO ilconic acid (H2ZrF6) or fluotitanic acid (H2TiF6) or their salts. The oplilll21 fluoride conl~nl is determined as a function of the con-ce"I,alion of aluminum that elutes from the aluminum Dl cans. For example, 100 ppm alunninum prerer~bly requires approxi",~lely 200 ppm fluorine. The fluoride content preferably falls in the range of 10 to 2,000 ppm as fluorine and more prererdbly, with i"cr~asing pr~fere~ ,ce in the order given, falls in the range of 20 to 900, 40 to 500, 60 to 200, or 90 to 165, ppm as fluorine. When the fluoride conlenl falls below 10 ppm as fluorine, the treatment bath becomes poorly react-ive with ~he surface of aluminum Dl cans and an acceptable film is not usually WO 95/02077 ~ - PCT/US94/07298 2~C~
produced.
The other components used in the invention treatment bath correspond to those used in conventional treatment baths. Thus, phosphoric acid (H3P04), sodium pl ,osphdle (Na3PO4), and the like can be used to supply the phosphate ion in the treatment bath. Although less prerer, ed, condensed pl ,osphoric acids such as py, op hospl ,o, ic acid (H4P207) and tripolyphosphoric acid (H5P30,0) and their salts can also be used. While the phospl ,ate ion COI ,lenl is not narrowly re-stricted, values in the range of 10 to 500 ppm are preferred and values in the range of 20 to 90 ppm are more prere"ed. In determining these values, the stoi-chior"~:l, ic equivalent as phosphale of all phospl)Gric acid(s) and anions formed by ionization thereof is considered to be phosphate.
The source of the zirconium and titanium cor,)pounds for the treatment bath is not narrowly restricted in scope, and the oxides, hydroxides, fluorides,and the like of zirconium and titanium can all be used, as can fluo~ir~o"ic and flu-otitanic acids and their salts, these acids and their salts being prefer,ed. Theconlenl of zirconium or titanium compound is preferably 10 to 200 ppm as Zr or Ti and more prerer~bly, with in~;teasing prererel1ce in the order given, 10 to 150, 20 to 100, or 25 to 90, ppm as Zr or Ti.
The pH of the t,~lment bath can be adjusted through the use of an acid such as phosphoric acid, nitric acid, hydrochloric acid, or hydrofluoric acid, or through the use of an alkali such as sodium hy, lo,dde, sodium carbonate, or am-monium hydroxide. The pH of the treatment bath normally should be from 2.0 to 4.0, while the range of 2.5 to 3.3 is prerer,ed.
The leclmi4ue for conlac~ g the surface l,e~l"~ent bath with aluminum Dl cans or tinplate Dl cans is exemplified by immersion, spraying, and the like as generally known in the art, with spraying being the p~efe"ed technique. The tem-perature of the treatment bath should usually be 20 to 65C and is prererably 25 to 65, more preferably 30 to 60, or still more preferably 30 to 35, C. The l,edl",e"l time usually is from 2 to 120 seconds, ~,ererably from 2 to 60secotlds, and particularly pr~rerdbly from 15to60 seconds. A tlt:dtlllenl time below 2 sec-onds does not usually produce an ~de~u~te r~c;lion, thereby esse"lially preclud-ing the formation of a highly corrosion-resistant film, while the improvement in wo 95,02077 2 1 6 ~4 ~2 PCT/US94/07298 performance diminishes at treatment times in excess of 60 seconds.
The L,eat",e, ll bath of the present invention is preferably used as part of the following process steps:
(1 ) cleaning of the Dl cans surface, prererably by degreasing;
5 (2) water wash;
(3) filrrl-ro""alion t~:dLmelll, using a cGn,posilion according to the invention;
(4) water wash;
(5) wash with deionized water; and (6) drying.
Examples The usefulness of the surface treatment bath of the present invention is illustrated below through a comparison of several working examples with com-parative examples. In these examples and cor"parison examples, any unspeci-fied material in a treatment bath co,nposition is water.
15General ~ondilio"s for Examples and Comparison Examples The aluminum Dl cans The aluminum Dl cans were fabricated by the draw-ironing of aluminum sheet. They were cleaned using the hot ~gueo-ls solution of an acidic deg, easer(PalklinTM 400, from Nihon Parke,i~ing Corn~any, Ltd., Tokyo) and then subject-20 ed to surFace l,edl",enl.
The tinplate Dl cans The lil ,,.,lale Dl cans were rabricale.l by the draw-ironing of tin-plated steel sheet. They were claaned using a hot ~ueo~ ~s solution of a weakly alkaline de-y,easer (IFinecleanerTM 4361A, from Nihon Parkerizing Co~npa~)y, Ltd., Tokyo) 25 and then subjected to surface treatment.
Corrosion resisla,)ce The co"osion resistance of the aluminum Dl cans was evaluated by im-,ner~i"g tlhe treated cans in boiling water for 30 minutes and then evaluating the degree of blackening (the a6sel,ce of blackening is prerel,ed). The corrosion re-30 sistance of the tinplate Dl cans was evaluated using the iron exposure value("IEV") measured in accordal ,ce with United States Patent Number 4,332,646.
A lower IFV is indicative of a better co" usion resisldnce, and values at or below wo 95/02077 ~6 ~ 4~ ~ PCT/US94/07298 150 are generally considered excellent.
Paint adherence The paint adherence was evaluated on the basis of the peel sL, e, IlJth as follows: An epoxy-urea can paint was applied on the surface of the treated can 5 to yield a paint film thickness of 5 to 7 micrometers. After baking for 4 minutes at 215 C, a 5 x 150 mm strip was cut from the can. A test specimen was pre-pared by hot-press bonding the strip with polyamide film, and the test specimen was peeled in a 180 peel test to provide the peel strength value. Higher peel ,gti, values are indicative of a better paint adhesion, and values of at least 10 1.5 kilograms-force ("kgf")/5 mm of width are generally considered excellent.
Example 1 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of treatments: spraying for 30 seconds with surface l~edl",e, It bath 1 heated to 40 C, then washing with tap water, spraying with de-15 ionized water (having a specific r~:sislance of at least 3 megaohm-cm) for 10 sec-onds, and finally drying for 3 minutes in a forced convection drying oven at 180 C. The corrosion resistance and adherence of the resulting Dl cans were then measured.
Surface treatment bath 1 75 % ,chos~ l,oric acid (H3PO4): 69 ppm (Po43-: 50 ppm) 20 % fluo~ir~nic acid (H2ZrF6): 500 ppm (zr4t 44 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-': 95 ppm') 30 % h~,clrogen peroxide (H2O2): 166 ppm (H2O2 50 ppm) pH 3.0 (adjusted with ~q~leous ~r"",~nia) Example 2 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of treatments: spraying for 15 seconds with surface Ll~dtlllel ll bath 2 heated to 30 C, then a water wash, wash with de-ionized wat-er, and drying as in Exa",~lc 1. The corrosion resistance and adherence of the 1The total fluoride in this and all the other cGr"posilions containing both simple and complex fluoride ions is the total from both sources.
~B&~
WO 9~/02077 PCT/US94/07298 .
resulting Dl cans were subsequently measured.
Surface treal",ellt bath 2 75 % phosphoric acid (H3P04): 69 ppm (PO43-: 50 ppm) 20 % fluo~irco"ic acid (H2ZrF6): 1000 ppm (Zr4~: 88 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-: 150 ppm) 30 % hydrogen peroxide (H2O2): 166 ppm (H2O2: 50 ppm) pH 3.3 (adjusted with aqueous atn,nonia) Example 3 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected o to the following sequence of treatments: spraying for 15 seconds with surface Il edl",enl bath 3 heated to 35 C then a water wash wash with deionized water and drying as in Exal ~ c 1. The corrosion resislance and adherence of the re-sulting Dl cans were subsequently measured.
~urface treatment bath 3 75 % phospi ,oric acid (H3PO4): 69 ppm (Po43-: 50 ppm) 20 % fluotitanic acid (H2TiFB): 500 ppm (Ti4~ 29 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-: 110 ppm) 30 % hydrogen peroxide (H2O2): 664 ppm (H2O2: 200 ppm) pH 2.5 (adjusted with ~queo~ls a~mG~Iia) FY:~rnple 4 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of treatments: spraying for 30 seconds with surface l,~dt",ent bath 4 heated to 40 C then a water wash wash with deionized water and drying as in Example 1. The co,tosion lesislance and adherence of the re-sulting Dl cans were sl Ihse~uently measured.
Surface treatment bath 4 75 % phosphoric acid (H3PO4): 138 ppm (PO4~: 100 ppm) 20 % fluotitanic acid (H2TiF6): 500 ppm (Tj4t 29 ppm) 20 % hydrofluoric acid (HF): 210 ppm (total F-: 1 10 ppm) 30 % hydrogen peroxide (H2O2): 166 ppm (H2O2 50 ppm) pH 3.5 (adjusted with aqueous an,r"onia) Example 5 As discussed above, a critical issue for multipurpose treatment baths is the film performance when metal ions different from the substrate metal have entered the bath by a preceding elution from Dl cans. In this example, 500 ppm 5 of tin ions was introduced into surface treatment bath 1 and the resulting surface treatment bath, heated to 60 C, was used for a 30-second spray treatment.
Washing and drying were then carried out as in Example 1.
Example 6 100 ppm of aluminum ions were introduGed into surface treatment bath 1 o and the resulting surface l,e~t"~enl bath, heated to 30 C, was used for a 30-sec-ond spray t,edl",e, ll. Washing and drying were then carried out as in Example 1.
Example 7 50 ppm of tin ions were introduced into surface treatment bath 2 and the 15 resulting surface treatment bath, heated to 60 C, was used for a 30-sec~nd spray treatment. Washing and drying were then carried out as in Example 1.
Example 8 100 ppm of aluminum ions were introduced into surface ll eaLmenl bath 2 and the resulting surface treatment bath, heated to 30 C, was used for a 2 0 30-second spray treatment. Washing and drying were then carried out as in Ex-ample 1, and the corrosion resistance and adherence of the resulting Dl cans were measured.
Comparative Example 1 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected 25 to the following sequence of treatments: spraying for 30 seconds with surfacell ealmenl bath S heated to 30 C, then a water wash, wash with deionized water,and drying as in Example 1. The corrosion resistance and adherence of the re-sulting Dl cans were subsequently measured.
Surface treatment bath 5 75 % phosphoric acid (H3P04): 69 ppm (P043~ 50 ppm) 20 % fluo~irc~"ic acid (H2ZrF6): 500 ppm (Zr4~ 44 ppm) wo 95,02077 ~ 4 ~ PCT/US94/07298 20 % hydrofluoric acid (HF): 210 ppm (total F: 95 ppm)pH 3.0 (adjusted with aqueous ammonia) Comparative Example 2 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were sl lhjected 5 to the following sequence of treatments: spraying for 30 seconds with surface lreal",ent bath 6 heated to 30 C then a water wash wash with deionized water and drying as in Exan,~ 1. The corrosion resistance and adherence of the re-sulting Dl cans were subsequently measured.
Surface I,edl,nel,t bath 6 o 75 % pl ,osphoric acid (H3P04): 69 ppm (P04~: 50 ppm) 20 % hydrofluoric acid (HF): 210 ppm (F- 40 ppm) pH 3.0 (adjusted with aqueous ammonia) Comparative Example 3 50 ppm of tin ions were introduced into surface treatment bath 5 and the resulting surface treatment bath heated to 30 C was used for a 30-second spray treaImenL Washing and drying were then carried out as in Example 1 and the co" osion r~sistance and a-ll ,ere"ce of the resulting Dl cans were measured.
Co")pal alive Example 4 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the following sequence of Ir~al~"e"Ls; heating a co",n,er~ ial surface treaI",el1I
bath intended for application to aluminum Dl cans (AlodineTM 404 from Nihon Parkerizing Company Ltd. Tokyo) to 30 C and spraying with this for 30 sec-onds then a water wash wash with deionized water and drying as in Example 1. The cor,osio" r~sisIal ,ce and a.ll ,er~"ce of the resulting Dl cans were subse-quently measured.
Cor"paré,Iive Example 5 Cleaned aluminum Dl cans and cleaned tinplate Dl cans were subjected to the foliowing sequence of tredImenIs; heaIi"g a cor~ er~ ial surface treatment bath intended for application to tinplate Dl cans (PalfosTM K3482 from Nihon Parkerizing Co""~al1y Ltd. Tokyo) to 30 C and spraying with this for 30 seG
onds then a water wash wash with deionized water and drying as in Example W0 95/02077 ~ .a~ PCT/US94107298 1. The co" uSiOI ~ resisldl ,ce and adherence of the resulting Dl cans were subse-quently measured.
The results of all the measurements noted above are shown in Table 1 on the following page.
5 Benefits of the Invention The treatment bath in accordance with the present invention produces a titanium oxide-containing or zirconium oxide-containing film on the surface of aluminum Dl cans and prod~ ~Ges a tin oxide-containing film on the surface of tin-plate Dl cans. This multipurpose applicability to different types of substrates is 10 made possible by the presence in the treatment bath of both an oxidizing agent and hydrofluoric acid and/or fluoride and by the stipulation of specir,c upper limits for them. A process according to the invention provides cans, prior to painting and/or ,c ri, llil 19 them, with an excellen~ co" osion resi~lance and paint adherence through a low-temperature treatment.
WO 9~/02077 PCT/US94/07298 ~6~8~
Table I
Cor,~sion Ræsisl~nce Paint Film Adher~.. ce (K~r/5m." of Width) Aluminum Tin- Alum- Tinplate (Blacheni"~) plateinum (IE~
Example 1 no 100 5.0 3.5 blackening Example 2 no 100 5.0 3.5 blackening Example 3 no 100 5.0 3.5 blackening Example 4 no 100 5.0 3.5 blackening Example 5 no 100 5.0 3.5 blackening Example 6 no 100 5.0 3.5 blackening Example 7 no 100 5.0 3.5 blackening Example 8 no 100 5.0 3.5 blackening Compar~tive ",oder;lte 200 2.5 1.5 Example 1 blackening Compar~tive blackening over 300 1.0 1.0 Example 2 entire surface Co."pa.. aliie blackening over 180 1.0 1.0 Example 3 entire surface Compar~lhre no blackening 300 5.0 1.0 Cxan ~le 4 Comparative blackening over 100 1.0 3.5 Exdl~ le 5 entire surface
Claims (10)
1. An aqueous liquid composition suitable for treating both aluminum and tinplate surfaces to form a protective coating thereon, said aqueous liquid compo-sition having a pH of 2.0 to 4.0 and consisting essentially of water and:
(A) at least one dissolved zirconium or titanium compound in an amount stoi-chiometrically equivalent to at least 10 ppm of the total of zirconium and titanium;
(B) an amount of dissolved oxidizing agent that has oxidizing power equiva-lent to that of a concentration of from 20 to 500 ppm of hydrogen peroxide;
(C) from 10 to 2000 ppm stoichiometric equivalent as F- of a dissolved com-ponent selected from the group consisting of fluorine-containing anions and their corresponding acids; and (D) at least 10 ppm of dissolved phosphate anions; and, optionally, one of more of:
(E) a component of organic acid that can form complex ions with dissolved tin or aluminum ions or both;
(F) dissolved aluminum ions; and (G) dissolved tin ions.
(A) at least one dissolved zirconium or titanium compound in an amount stoi-chiometrically equivalent to at least 10 ppm of the total of zirconium and titanium;
(B) an amount of dissolved oxidizing agent that has oxidizing power equiva-lent to that of a concentration of from 20 to 500 ppm of hydrogen peroxide;
(C) from 10 to 2000 ppm stoichiometric equivalent as F- of a dissolved com-ponent selected from the group consisting of fluorine-containing anions and their corresponding acids; and (D) at least 10 ppm of dissolved phosphate anions; and, optionally, one of more of:
(E) a component of organic acid that can form complex ions with dissolved tin or aluminum ions or both;
(F) dissolved aluminum ions; and (G) dissolved tin ions.
2. An aqueous liquid composition according to claim 1, wherein the concen-tration of component (A) is from 10 to 200 ppm stoichiometric equivalent as the total of zirconium and titanium, the concentration of component (B) is such as to be equivalent in oxidizing power to from 40 to 200 ppm of hydrogen peroxide, the concentration of component (C) is from 20 to 900 ppm as F-, and the concen-tration of component (D) is from 10 to 500 ppm as phosphate.
3. An aqueous liquid composition according to claim 2, wherein the concen-tration of component (A) is from 10 to 150 ppm stoichiometric equivalent as the total of zirconium and titanium, the concentration of component (C) is from 40 to 500 ppm as F-, and the concentration of component (D) is from 20 to 90 ppm as phosphate.
4. An aqueous liquid composition according to claim 3, wherein the con-centration of component (A) is from 20 to 100 ppm stoichiometric equivalent as the total of zirconium and titanium and the concentration of component (C) is from 60 to 200 ppm as F-.
5. An aqueous liquid composition according to claim 4, wherein the con-centration of component (A) is from 25 to 90 ppm stoichiometric equivalent as the total of zirconium and titanium and the concentration of component (C) is from 90 to 165 ppm as F-.
6. An aqueous liquid composition according to any one of claims 1 - 5, wherein component (A) is selected from the group consisting of fluozirconic and fluotitanic acids and salts thereof and the pH is from 2.5 to 3.3.
7. A process of treating tinplate or aluminum cans by contacting the sur-faces of the cans with a composition according to claim 6.
8. A process according to claim 7, where the time of contacting the cans is from 2 to 120 seconds and the aqueous liquid composition is maintained at a temperature between 20 and 65 °C during contacting.
9. A process of treating tinplate or aluminum cans by contacting the sur-faces of the cans with a composition a according to any one of claims 1 - 5.
10. A process according to claim 9, where the time of contacting the cans is from 2 to 120 seconds and the aqueous liquid composition is maintained at a temperature between 20 and 65 °C during contacting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5/165601 | 1993-07-05 | ||
| JP5165601A JPH0748677A (en) | 1993-07-05 | 1993-07-05 | Aluminum di can and common surface treatment solution and process for tin di can |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2166482A1 true CA2166482A1 (en) | 1995-01-19 |
Family
ID=15815457
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002166482A Abandoned CA2166482A1 (en) | 1993-07-05 | 1994-07-05 | Composition and process for treating tinplate and aluminum |
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| Country | Link |
|---|---|
| EP (1) | EP0726968B1 (en) |
| JP (1) | JPH0748677A (en) |
| AT (1) | ATE186755T1 (en) |
| AU (1) | AU682706B2 (en) |
| CA (1) | CA2166482A1 (en) |
| DE (1) | DE69421716T2 (en) |
| ES (1) | ES2140546T3 (en) |
| WO (1) | WO1995002077A1 (en) |
| ZA (1) | ZA944822B (en) |
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| JP3349851B2 (en) * | 1994-12-22 | 2002-11-25 | 日本パーカライジング株式会社 | Surface treatment composition for aluminum-containing metal material excellent in sludge suppression property and surface treatment method |
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| JP2828409B2 (en) * | 1994-03-24 | 1998-11-25 | 日本パーカライジング株式会社 | Surface treatment composition for aluminum-containing metal material and surface treatment method |
| US6193815B1 (en) | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
| JP3623015B2 (en) * | 1995-06-30 | 2005-02-23 | 日本パーカライジング株式会社 | Surface treatment liquid for aluminum-containing metal material and surface treatment method |
| US6432603B1 (en) * | 1998-11-27 | 2002-08-13 | Canon Kabushiki Kaisha | Process for producing electrophotographic photosensitive member |
| DE19921842A1 (en) | 1999-05-11 | 2000-11-16 | Metallgesellschaft Ag | Pretreatment of aluminum surfaces with chrome-free solutions |
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| JP4778769B2 (en) * | 2005-10-24 | 2011-09-21 | 昭和アルミニウム缶株式会社 | Aluminum can manufacturing method and aluminum can manufactured by the method |
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| JP4276689B2 (en) * | 2006-12-20 | 2009-06-10 | 日本ペイント株式会社 | Cationic electrodeposition coating method and metal substrate coated with cationic electrodeposition |
| TWI391530B (en) * | 2007-04-04 | 2013-04-01 | Nippon Steel Corp | A plated steel sheet for use in a tank and a method for manufacturing the same |
| DE102007037903A1 (en) * | 2007-08-10 | 2009-02-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for cleaning surfaces and use of the process |
| CN101784700B (en) | 2007-08-23 | 2012-10-24 | 新日本制铁株式会社 | Environmentally friendly steel sheet for container material, process for producing the same, and environmentally friendly laminated steel sheet for container material and precoated steel sheet for container material each produced from that steel shee |
| MY160955A (en) | 2010-04-06 | 2017-03-31 | Nippon Steel Corp | Process for producing environmentally-friendly steel sheet for container material |
| JP6295832B2 (en) * | 2014-05-28 | 2018-03-20 | 株式会社ブリヂストン | Aluminum-rubber composite and method for producing the same |
| EP4276219A1 (en) * | 2022-05-09 | 2023-11-15 | Atotech Deutschland GmbH & Co. KG | Process for wet-chemical formation of a stable tin oxide layer for printed circuit boards (pcbs) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1098253A (en) * | 1976-04-05 | 1981-03-31 | Timm L. Kelly | Zirconium/titanium coating solution for aluminum surfaces |
| JPS5424232A (en) * | 1977-07-26 | 1979-02-23 | Nippon Packaging Kk | Surface treating method of aluminum |
| JPS5468734A (en) * | 1977-11-11 | 1979-06-02 | Nippon Packaging Kk | Surface treatment of tin plated steel plate and can |
| FR2417537A1 (en) * | 1978-02-21 | 1979-09-14 | Parker Ste Continentale | COMPOSITION BASED ON HAFNIUM TO INHIBIT CORROSION OF METALS |
| DE3236247A1 (en) * | 1982-09-30 | 1984-04-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR SURFACE TREATMENT OF ALUMINUM |
| US4470853A (en) * | 1983-10-03 | 1984-09-11 | Coral Chemical Company | Coating compositions and method for the treatment of metal surfaces |
| AU4751885A (en) * | 1984-10-09 | 1986-04-17 | Parker Chemical Company | Treating extruded aluminium metal surfaces |
| CA1333043C (en) * | 1988-02-15 | 1994-11-15 | Nippon Paint Co., Ltd. | Surface treatment chemical and bath for aluminium and its alloy |
| US4992116A (en) * | 1989-04-21 | 1991-02-12 | Henkel Corporation | Method and composition for coating aluminum |
| US5139586A (en) * | 1991-02-11 | 1992-08-18 | Coral International, Inc. | Coating composition and method for the treatment of formed metal surfaces |
| US5143562A (en) * | 1991-11-01 | 1992-09-01 | Henkel Corporation | Broadly applicable phosphate conversion coating composition and process |
-
1993
- 1993-07-05 JP JP5165601A patent/JPH0748677A/en active Pending
-
1994
- 1994-07-04 ZA ZA944822A patent/ZA944822B/en unknown
- 1994-07-05 AU AU72521/94A patent/AU682706B2/en not_active Ceased
- 1994-07-05 AT AT94922040T patent/ATE186755T1/en not_active IP Right Cessation
- 1994-07-05 ES ES94922040T patent/ES2140546T3/en not_active Expired - Lifetime
- 1994-07-05 CA CA002166482A patent/CA2166482A1/en not_active Abandoned
- 1994-07-05 WO PCT/US1994/007298 patent/WO1995002077A1/en active IP Right Grant
- 1994-07-05 EP EP94922040A patent/EP0726968B1/en not_active Expired - Lifetime
- 1994-07-05 DE DE69421716T patent/DE69421716T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69421716D1 (en) | 1999-12-23 |
| ZA944822B (en) | 1995-02-22 |
| EP0726968B1 (en) | 1999-11-17 |
| WO1995002077A1 (en) | 1995-01-19 |
| ES2140546T3 (en) | 2000-03-01 |
| DE69421716T2 (en) | 2000-06-29 |
| EP0726968A1 (en) | 1996-08-21 |
| EP0726968A4 (en) | 1996-05-24 |
| AU682706B2 (en) | 1997-10-16 |
| AU7252194A (en) | 1995-02-06 |
| JPH0748677A (en) | 1995-02-21 |
| ATE186755T1 (en) | 1999-12-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |