CA2232998A1 - Composition and process for surface treatment of aluminum and its alloys - Google Patents
Composition and process for surface treatment of aluminum and its alloys Download PDFInfo
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- CA2232998A1 CA2232998A1 CA002232998A CA2232998A CA2232998A1 CA 2232998 A1 CA2232998 A1 CA 2232998A1 CA 002232998 A CA002232998 A CA 002232998A CA 2232998 A CA2232998 A CA 2232998A CA 2232998 A1 CA2232998 A1 CA 2232998A1
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- phosphoric acid
- surface treatment
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
-
- 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
- C23C22/07—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 phosphates
- C23C22/23—Condensed phosphates
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/76—Applying the liquid by spraying
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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)
- Paints Or Removers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
An aqueous liquid surface treatment composition having a pH value not more than 6.5 and containing phosphoric acid ions, condensed phosphoric acid ions, an oxidizing agent, and a water-soluble polymer consisting, except for end groups, of polymer units expressed by formula (I), in a weight ratio of 0.1 to 30 : 0.1 to 10 : 0.1 to 10 : 0.1 to 20 respectively, when brought into contact with an aluminiferous metal surface, rapidly forms on the surface a conversion coating that has good corrosion resistance and adhesion to subsequently applied organic coatings such as paint and is less easily damaged by mechanical stresses than prior art conversion coatings.
Description
CA 02232998 1998-03-2~
W O 97/13887 PCT~US96/16132 Description - - -COMPOSITION AND PROCESS FOR SURFACE TREATMENT OF ALUMINUM
Technical Field The present invention relates to a novel composition and method for the surface l,t:~l",ent of aluminum and its alloys, such as aluminum-manganese al-loys, aluminum-magnesium alloys,, and aluminum-silicon alloys, that contain at least 45 % by weight of aluminurn, all of these being jointly hereinafter briefly designated as "aluminiferous metals", in which the surface of an aluminiferous metal is provided with better corrosion resistance and adhesion to paint or syn-thetic resin film before said surface is painted or is laminated to a synthetic resin film. One field in which the present invention may be particularly effectively ap-~0 plied is the surface treatment of aluminiferous coils.Background Art ChromdLe treatments are presently being used for the most part in the in-dustrial surface treatment of alurninum coils. Typical examples of chromate treatments include chrul "ic acid chromate conversion treatments and phosphoric acid chromate conversion ll~:al,llenl~. Chromic acid chromate conversion treat-ment solutions were put to practical use around 1950 and are still widely used for fin members and the like in heat exchangers. This chemical conversion treat-ment solution consists primarily of chromic acid (CrO3) and hydrofluoric acid (HF), with a promoter added, and forms a film containing some hexavalent 20 chromium. Phosphoric acid chromate conversion treatment solutions are based on the invention in US Patent 2,438,877 from 1945. This chemical conversion treatment solution contains chromic acid (CrO3), phosphoric acid (H3PO4), and hydrofluoric acid (HF). The film that is formed consists primarily of hydrated chromium phosphate (CrPO4-4H2O). Since the film does not contain hexavalent 25 chromium, it is widely used at present for the paint undercoating treatment of beverage can bodies, particularly drawn and ironed aluminum cans and lids.
However, in the interests of environmental protection, a need has arisen for sur-face ll~:dllnent solutions which contain no chromium. In recent years, the paint-CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 ing or lamination following such surface treatment has been followed by an in-creasingly wide range of shaping processes with the need for increasingly strin-gent levels of processing but films made from inorganic systems such as chro-mate suffer from problems; e.g.~ the film is broken when bent sharply prevent-s ing adequate pe~ rur" ,ance from being re~li7ed and the like. There is thus strong demand for the development of a technique for forming a flexible film with better corrosion resi:jldl ~ce and/or adl1esion in articles of manufacture that are shaped after the conversion coating is formed.
Treatment solutions or methods intended to provide the surface of alumin-iferous metals with cor,usion resistance and paint adhesion using a water-solu-ble resin have been proposed in Japanese Laid-~)pen Patent Applications 61-91369 1-172406 1-177379 1-177380 2-608 2-609 and others. In these conventional l, ~aL" ,ent methods the metal surface is treated with a solution con-taining a derivative of a polyhydric phenol compound. Problems in these con-ventional methods however are that it is difficult to form a sufficiently stable film in a short period of time on the surface of aluminiferous metal ",aterials and adequate corrosion resistance cannot be obtained.
n;SclQsure of the Invention Problems to Be Solved by the Invention The present invention is intended to remedy the aforementioned draw-backs of the conventional technology and more specifically is intended to offer a novel CGI I Iposilion and method for surface treating aluminiferous rnetals which allow the surface of an aluminiferous metal to be provided in a short period of time with better corrosion resistance and paint or laminated film adhesion without the use of chromium and which also allow a film with better workability to be formed.
~ummary of the Invention It has been found that an aqueous liquid surface treatment composition containing phosphoric acid ions condensed phosphoric acid ions an oxidizer and a water-soluble polymer with a specific structure and that has a pH within a specific range forms a film with better corrosion It::SiSldl ~ce and paint or lamin-CA 02232998 l998-03-2~
- W O 97/13887 PCTrUS96/16132 ated film adhesion, as well as better workability, when a surface of an alun~inifer-~ ~
ous metal is brought into contact with such a surface treatment composition.
More particularly, a composition according to the invention for the surface treatment of an aluminiferous metal comprises, preferably consists essentially 5 of, or more preferably consists of, water and:
(A) a component of ions of orthophosphoric acid;
(B) a component of ions of condensed phosphoric acid(s);
(C) a component of oxidizing agent; and (D) a component of molecules of water-soluble polymer and/or oligomers conforming, except for end groups, to the following general formula (I):
-- OH
~ CH2 X~--C---X2 ( I ) ~y2 OH
in which each of X' and x2 independently of each other and independently from one unit of the polymer, said unit being defned as repr~senled by a ll lodiricdliol~
25 of formula (I) above in which the square brackets and the subscript n are omit-ted, to another unit of the polymer represents a hydrogen atom, a C1 to Cs alkylgroup, or a C, to C5 hydroxyalkyl group; each of Y' and y2 independently of one ~ another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which co,)rOr",s to one of the fcll~wi"g general formulas (Il) 30 and (Ill):
CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 - C H 2--N ( ~ C H 2--N--R ( I I I
in which each of R', R2, R3, R4, and R5 in each of general formulas (Il) and (Ill) independently represents a C, to C,0 alkyl group or a C1 to C10 hydroxyalkyl group; one moiety "Z" may be identical to or may differ from any other moiety "Z" in the polymer molecule, so long as each "Z" con-forms to one of the general formulas (Il) and (Ill); and n repr~:sellls a posi-tive integer, which may be the same as or different from the value of n for any other polymer molecule; in addition, in component (D) as a whole:
the average value for the number of Z moieties sl ~hstitl ~3d on each phen-yl ring in the polymer molecule', which may be referred to hereinafter as "the average value for Z moiety substitution", is from 0.2 to 1.0; the av-~s erage value of n, which may be referred to hereinafter as "the average degree of polymerization", is from 2 to 50, and, bec~ e it is an average, need not be an integer;
and, optionally, one or both of the following cornponents:
(E) a component of aluminum sequestering agent that is not part of any of the previously recited components; and (F) a component of antifoam agent that is not part of any of the previously re-cited components, and in the composition as a whole, the aforementioned phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble poly-mer (D) are present in a weight ratio (A):(B):(C):(D) of 0.1 to 30: 0.1 to 10: 0.1 1For example, if a polymer with an average degree of poly"leri~dlion of 10, which COI lldil IS 20 benzene rings, has only 10 of these 20 benzene rings each s~ Ihstihlted with one group Z, the mean group Z sllhstitlltion rate of the polymer is:
~(1 x 10) + (0 x 10')}/20 = 0.5 CA 02232998 l998-03-2~
- W O 97/13887 PCTrUS96/16132 to 10: 0.1 to 20. A composition according to the invention may be immediately suitable for use as such in treating aluminiferous metal, in which instance it is called a working composition, or it may be suitable for diluting with additional- water to form a working cornrosition, in which instance it is called a concentrate composition. Some compositions are suitable for both purposes.
A process for the surface treatment of an aluminiferous metal according to the present invention is charac:terized by the fact that an aqueous surface treatment solution which contains the dror~ e~ llioned surface ll ~dll I ~el ,L compo-sition pe, l~i";"g to the present invention and which has a pH value no more than 10 6.5 is brought into contact with the surface of an aluminiferous metal, prer~rdbly for a total of 1 to 60 seconds, and lthe surface which has thus contacted prefer-ably is then rinsed with water, andl then is dried and preferably heated.
Detailed Description of the Invention. Including Preferred Fmbodiments Orthophosphoric acid, having the chemical formula H3PO4 and herein usually desiyl Idl~3d simply as "phosphoric acid" unless the co, ll~xL requires differ-entiating it from other phosphoric acids, and any water soluble salt or acid salt of orthophosphoric acid that does not act adversely to the objects of the in-vention may be used as a source of component (A) of a composition according to the invention as defined above, and any such salt is to be under~luod, for the 20 purpose of the preferences i"dicz~lt d below, as contributing its full 6h -hiolll~llic equivalent as orthophosphate ions (i.e., PO4~3) to the conce~ dlion thereof in any composition according to the invention, irrespective of the actual degree of ionization that may prevail in the composition. The phosphoric acid ions contentranges from 0.1 to 30 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 25 to 20 weight parts of water-soluble polymer (D) in the aforementioned ratio. A
phosphoric acid ions content of less than 0.1 weight part in the aforementioned blend ratio often results in inadequate reactivity between the surface treatmentsolution and the surface of the metal substrate being coated, as well as in an inadequately formed film. More than 30 weight parts in this ratio does not harm 30 rc""~dLion of a favorable conversion coating but is uneconomical bec~llse of the higher cost of the treatment solution and lack of any ofFsetting benefit compared CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 with compositions containing somewhat less of this component. ~
Similarly, one or two or more types selected from among pyrophosphoric acid, tripolyphosphoric acid and tetrapolyphosphoric acid, and the salts of all of these acids, can be used to provide the condensed phosphoric acid ions in a water-based composition of this invention, but the invention is not lirnited to the use of these materials. Any water soluble source of any phos,uhale anions that CGI lldill at least two atoms of phosphorus each may be used, and is to be under-stood for the purposes of the preferences below as supplying its full stoichio-metric equivalent as condensed phosphate anions to the composition used ac-0 cording to the invention, irrespective of the actual degree of ionization that exists in the composition. For example, pyrophosphoric acid ~H4P2~17), sodium pyro-phosphate (Na4P2O7) and like compounds can be used to provide pyrophosphate ions. In a surface treatment composition according to the present invention, thecontent of the condensed phosphoric acid ions component (B) ranges from 0.1 to 10 weight parts, and preferably 0.5 to 3.0 weight parts, per 0.1 to 20 weightparts of water-soluble polymer (D). A condensed phosphoric acid ions content of less than 0.1 weight part in the aforementioned ratio normally results in a sur-face treatment solution with weak etching action, preventing a film from being adequateiy forrned. A content of more than 10 weight parts usually results in a surface treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
In a surface treatment composition acco~ Ig to the pr~sel ll invention, the oxidizing agent preferably comprises, more preferably consists essentially of, or still more preferably consists of one or more sl ~hst~nces selecttsd from the group consi~ g of hydrogen peroxide, chlorates, and nitrites; the use of hydrogen per-oxide is most preferred. The content of oxidizing agent component (C) in the aforementioned ratio for the surface treatment composition according to the present invention ranges from 0.1 to 10 weight parts, and preferably 2 to 5 weight parts, per 0.1 to 20 weight parts of water-soluble polymer COI "pone"l (D).
so An oxidizing agent co, ll~lll of less than 0.1 weight part usually results in a treat-ment solution with weak etching action, preventing an adequate film from being CA 02232998 l998-03-2~
W O 97/13887 PCTrUS96/16132 formed. More than 10 weight parts usually results in a treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
The water-soluble polymem~sed in the present invention is a water-sol-uble polymer (a term intended herein to include oligomers) that has an average 5 degree of polymeri~lion of 2 to 5al, or preferably of 2 to 20, and that contains, ~ preferably consists essentially of, Ol more pr~r~l dbly consists of (except for end groups) polymer units as described above in connection with general formula (I).When the alkyl or hydroxyalkyl groups represented by X1 and x2 in general formula (I) have 6 or more carbon atoms, the resulting polymer becon ,esbulky, usually causing steric hindrance and preventing a compact film with good corrosion reslstance from being obtained.
When the average value for Z substitutions is less than 0.2, the resulting polymer normally has poor water solubility, and the resulting surface treatment composition stability is usually inadequate. When the average value for Z moietysl Ihstitlltion is more than 1.0, and thus contains a substantial fraction of benzene rings s~ Ihstitl Ited by two or more Z ç roups, the polymer usually has such a high water solubility that a composition containing it as component (D) has great difficulty in forming a satisfactorily protective surface film.
The alkyl or hydroxyalkyl groups expressed by R', R2, R3, R4, and R5 in general formulas (Il) and (Ill) have 1 to 10 carbon atoms. A number of carbon atoms of 11 or more usually results in a polymer molecule that is too bulky, leading to a film with poor density and insuffcient corrosion resistance.
In a surface treatment composition according to the present invention, the content of the water-soluble polymer component (D), in terms of the aforemen-2s tioned ratios to other components, is 0.1 to 20 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 to 30 weight parts of phosphoric acid ions (A). When this ratio is less than 0.1 weight parlt, it is diffcult to form a film on the surface of aluminiferous metals with the surface treatment composition, whereas more than 20 weight parts in this ratio is uneconomical bec~use of the higher cost of the re-sulting surface treatment and laclc of any s~hst~ntial improvement over the results achieved with a composition according to the invention containing 20 or CA 02232998 l998-03-2~
W O 97/13887 PCTrUS96/16132 fewer parts in this ratio. - -Although not narrowly limited, the pH of a working surface llt:dllllel)l com-position according to the present invention is preferably no more than 6.5, and even more preferably is between 2.0 and 6.5. When the pH of the surface treat-5 ment composition is higher than 6.5, the polymer of forrnula (I) in the resultingsurface treatment composition tends to precipitate, impairing the treatment com-position stability and its use life. When the pH is lower than 2.0, tl-e etching ac-tion of the surFace l~t:almenl composition on the surface of the metal material is very strong, making it difficult to form a surFace film. The pH of the surface treat-10 ment composition can be ~justed using an acid such as phosphoric acid, nitricacid, and hydrochloric acid, or an alkali such as sodium hydroxide, sodium car-bonate, and ammonium h~/-lr~xide. Hydrofluoric acid may be used to adjust the pH when wastewater disposal is not a problem.
In a surface treatment method according to the present invention, the 15 aforementioned surface treatment solution preferably has a pH of 2.0 to 6.5 and contains from 1 to 30 grams per liter (hereinafter usually abbreviated as "g/l") of phosphoric acid ions, from 0.1 to 10 9/l of condensed phos,c I ,oric acid ions, from 0.1 to 10 g/l of oxidizing agent, and from 0.1 to 20 gA of water-soluble polymercomponent (D) as described above. When the conce"l,dlion of phosphoric acid 20 ions in a surface treatment composition according to the invention is lower than 0.1 g/l, a surface film is usually inadequately formed, whereas more than 30 g/lis uneconomical bec~se of higher costs. When the conce"l,dliG" of the con-densed phosphoric acid ions is lower than 0.1 g/l, the etching action of the result-ing surface treatment composition is usually too weak, and a suRace film is in-25 adequately formed, whereas more than 10 9/l results in a surface L~ ~l" ,el ,t com-position with etcl~ ;a properties that are so strong that the film-forming reaction is hindered. When the oxidizing agent concentration is lower than 0.1 g/l, the etching action of the resulting surface treatment composition is weak, usually preventing the formation of an adequate film, whereas more than 10 g/l results in a surface treatment composition with etching action that is too high, which hinders the film-forming reaction. When the conce"lldlion of the water-soluble -CA 02232998 1998-03-2~
W O 97/13887 PCT~US96/16132 polymer component (D) is lower than 0.1 g/l, the resulting surface treatment~
composition usually has inadequal:e film formability, whereas more than 20 g/l is economically disadvantageous because of higher costs.
When aluminum ions that have eluted from the aluminiferous metal be-5 come mixed with the surface treatment composition, the water-soluble polymer (D) and the metal ions sometimes fomm a conl,~lex and produce precipitation. In such instances, an aluminum sequestering agent should be added to the surface treatment composition. Examples of useful aluminum sequestering agents in-clude, but are not limited to, ethylene dian ,i"e tetra-acetic acid, 1 ,2-cyclohexane-.0 diamine tetra-acetic acid, triethanolamine, gluconic acid, heptogluconic acid, ox-alic acid, tartaric acid, malic acid, and organophosphonic acids. When the use of hydrofluoric acid poses no problems for wastewater treatment, it may be used as a sequestering agent.
In a ll l~:lhod of the present invention, a working surface Ll~::dl",ent compo-15 sition as described above is brought into conl~;l, preferably for a total of 1 to 60seconds and independently prert:r~bly at a temperature within a range from 30 to 65 oc, with a surface of an aluminiferous metal. The film formed on the sur-face of the metal material is then preferably rinsed with water, and thereafter preferably is heated and dried. Contact between the aluminiferous metal and a 20 working composition may be established by any convenient method, among which immersion of the substrate in a bath of the working composition and spraying the working composition on the metal are most cG",mon. A contact time of less than 1 second usually results in inadequate formation of a cor,usion-resislanl film, whereas a contact time of more than 60 seconds yields no greater25 benefits and thus leads to less operational efficiency.
When a spray treatment is used, the surface treatment composition some-times foams and thus causes problems in the film that is formed. Although the presence or absence of foaming and the extent of such foaming depends largely on the spraying equipment and conditions, a defoaming agent should be added 30 to the surface l,~ "ent composition when foaming is not suitably avoided by modification of the spraying equipmlent and conditions. The type of defoaming CA 02232998 l998-03-2~
agent, the amount used, and so forth are not narrowly limited, but the adhesion-between the resulting film and the paint or laminated film should not be compro-mised.
The film formed on the surface of the aluminiferous metal in a process ac-cording to the invention is believed to be a film of an organic-inorganic composite consisting primarily of phosphates and water-soluble polymer (resin) (D). The metal substrate is etched by the ions of the phosphoric acid and condensed phosphoric acid, at which time the pH becomes elevated in some areas at the interface, resulting in the prec;~.iLdLion of phosphates on the surface. The amino groups (included in the groups Z) of the water-soluble polymer (D) have chelat-ing action, and are believed to form a type of coordination con~poun~ with the re-generated surface of the metal sul.~ le produced by the etching. Although the organic-inorganic composite film is h~sic~lly formed as a result of the two afore-mentioned actions, the additional presence of the condensed phosphoric acid ions in the surface treatment composition appears to allow some water-soluble polymer-metal coordination compound(s) to be more readily formed, thereby al-lowing a stable organic-inorganic complex film to be formed on the metal surfacewithin a wide pH range.
After a coating film has been formed in a process according to the inven-tion, the film can be and preferably is heated to allow the polymer from compon-ent (D) of the working composition according to the invention that was used, andthat was incorporated into the coating film formed on the surface, to undergo fur-ther polymeri~dlion on the surface. At least one minute at 200 ~C (in the normalambient natural atmosphere) is sufficient for the heating conditions.
A preferred expanded treatment process step sequence, using a surface treatment composition according to the present invention, is outlined below.
(1) Surface cleaning/degreasing (any acidic, alkaline, or solvent type);
W O 97/13887 PCT~US96/16132 Description - - -COMPOSITION AND PROCESS FOR SURFACE TREATMENT OF ALUMINUM
Technical Field The present invention relates to a novel composition and method for the surface l,t:~l",ent of aluminum and its alloys, such as aluminum-manganese al-loys, aluminum-magnesium alloys,, and aluminum-silicon alloys, that contain at least 45 % by weight of aluminurn, all of these being jointly hereinafter briefly designated as "aluminiferous metals", in which the surface of an aluminiferous metal is provided with better corrosion resistance and adhesion to paint or syn-thetic resin film before said surface is painted or is laminated to a synthetic resin film. One field in which the present invention may be particularly effectively ap-~0 plied is the surface treatment of aluminiferous coils.Background Art ChromdLe treatments are presently being used for the most part in the in-dustrial surface treatment of alurninum coils. Typical examples of chromate treatments include chrul "ic acid chromate conversion treatments and phosphoric acid chromate conversion ll~:al,llenl~. Chromic acid chromate conversion treat-ment solutions were put to practical use around 1950 and are still widely used for fin members and the like in heat exchangers. This chemical conversion treat-ment solution consists primarily of chromic acid (CrO3) and hydrofluoric acid (HF), with a promoter added, and forms a film containing some hexavalent 20 chromium. Phosphoric acid chromate conversion treatment solutions are based on the invention in US Patent 2,438,877 from 1945. This chemical conversion treatment solution contains chromic acid (CrO3), phosphoric acid (H3PO4), and hydrofluoric acid (HF). The film that is formed consists primarily of hydrated chromium phosphate (CrPO4-4H2O). Since the film does not contain hexavalent 25 chromium, it is widely used at present for the paint undercoating treatment of beverage can bodies, particularly drawn and ironed aluminum cans and lids.
However, in the interests of environmental protection, a need has arisen for sur-face ll~:dllnent solutions which contain no chromium. In recent years, the paint-CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 ing or lamination following such surface treatment has been followed by an in-creasingly wide range of shaping processes with the need for increasingly strin-gent levels of processing but films made from inorganic systems such as chro-mate suffer from problems; e.g.~ the film is broken when bent sharply prevent-s ing adequate pe~ rur" ,ance from being re~li7ed and the like. There is thus strong demand for the development of a technique for forming a flexible film with better corrosion resi:jldl ~ce and/or adl1esion in articles of manufacture that are shaped after the conversion coating is formed.
Treatment solutions or methods intended to provide the surface of alumin-iferous metals with cor,usion resistance and paint adhesion using a water-solu-ble resin have been proposed in Japanese Laid-~)pen Patent Applications 61-91369 1-172406 1-177379 1-177380 2-608 2-609 and others. In these conventional l, ~aL" ,ent methods the metal surface is treated with a solution con-taining a derivative of a polyhydric phenol compound. Problems in these con-ventional methods however are that it is difficult to form a sufficiently stable film in a short period of time on the surface of aluminiferous metal ",aterials and adequate corrosion resistance cannot be obtained.
n;SclQsure of the Invention Problems to Be Solved by the Invention The present invention is intended to remedy the aforementioned draw-backs of the conventional technology and more specifically is intended to offer a novel CGI I Iposilion and method for surface treating aluminiferous rnetals which allow the surface of an aluminiferous metal to be provided in a short period of time with better corrosion resistance and paint or laminated film adhesion without the use of chromium and which also allow a film with better workability to be formed.
~ummary of the Invention It has been found that an aqueous liquid surface treatment composition containing phosphoric acid ions condensed phosphoric acid ions an oxidizer and a water-soluble polymer with a specific structure and that has a pH within a specific range forms a film with better corrosion It::SiSldl ~ce and paint or lamin-CA 02232998 l998-03-2~
- W O 97/13887 PCTrUS96/16132 ated film adhesion, as well as better workability, when a surface of an alun~inifer-~ ~
ous metal is brought into contact with such a surface treatment composition.
More particularly, a composition according to the invention for the surface treatment of an aluminiferous metal comprises, preferably consists essentially 5 of, or more preferably consists of, water and:
(A) a component of ions of orthophosphoric acid;
(B) a component of ions of condensed phosphoric acid(s);
(C) a component of oxidizing agent; and (D) a component of molecules of water-soluble polymer and/or oligomers conforming, except for end groups, to the following general formula (I):
-- OH
~ CH2 X~--C---X2 ( I ) ~y2 OH
in which each of X' and x2 independently of each other and independently from one unit of the polymer, said unit being defned as repr~senled by a ll lodiricdliol~
25 of formula (I) above in which the square brackets and the subscript n are omit-ted, to another unit of the polymer represents a hydrogen atom, a C1 to Cs alkylgroup, or a C, to C5 hydroxyalkyl group; each of Y' and y2 independently of one ~ another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which co,)rOr",s to one of the fcll~wi"g general formulas (Il) 30 and (Ill):
CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 - C H 2--N ( ~ C H 2--N--R ( I I I
in which each of R', R2, R3, R4, and R5 in each of general formulas (Il) and (Ill) independently represents a C, to C,0 alkyl group or a C1 to C10 hydroxyalkyl group; one moiety "Z" may be identical to or may differ from any other moiety "Z" in the polymer molecule, so long as each "Z" con-forms to one of the general formulas (Il) and (Ill); and n repr~:sellls a posi-tive integer, which may be the same as or different from the value of n for any other polymer molecule; in addition, in component (D) as a whole:
the average value for the number of Z moieties sl ~hstitl ~3d on each phen-yl ring in the polymer molecule', which may be referred to hereinafter as "the average value for Z moiety substitution", is from 0.2 to 1.0; the av-~s erage value of n, which may be referred to hereinafter as "the average degree of polymerization", is from 2 to 50, and, bec~ e it is an average, need not be an integer;
and, optionally, one or both of the following cornponents:
(E) a component of aluminum sequestering agent that is not part of any of the previously recited components; and (F) a component of antifoam agent that is not part of any of the previously re-cited components, and in the composition as a whole, the aforementioned phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble poly-mer (D) are present in a weight ratio (A):(B):(C):(D) of 0.1 to 30: 0.1 to 10: 0.1 1For example, if a polymer with an average degree of poly"leri~dlion of 10, which COI lldil IS 20 benzene rings, has only 10 of these 20 benzene rings each s~ Ihstihlted with one group Z, the mean group Z sllhstitlltion rate of the polymer is:
~(1 x 10) + (0 x 10')}/20 = 0.5 CA 02232998 l998-03-2~
- W O 97/13887 PCTrUS96/16132 to 10: 0.1 to 20. A composition according to the invention may be immediately suitable for use as such in treating aluminiferous metal, in which instance it is called a working composition, or it may be suitable for diluting with additional- water to form a working cornrosition, in which instance it is called a concentrate composition. Some compositions are suitable for both purposes.
A process for the surface treatment of an aluminiferous metal according to the present invention is charac:terized by the fact that an aqueous surface treatment solution which contains the dror~ e~ llioned surface ll ~dll I ~el ,L compo-sition pe, l~i";"g to the present invention and which has a pH value no more than 10 6.5 is brought into contact with the surface of an aluminiferous metal, prer~rdbly for a total of 1 to 60 seconds, and lthe surface which has thus contacted prefer-ably is then rinsed with water, andl then is dried and preferably heated.
Detailed Description of the Invention. Including Preferred Fmbodiments Orthophosphoric acid, having the chemical formula H3PO4 and herein usually desiyl Idl~3d simply as "phosphoric acid" unless the co, ll~xL requires differ-entiating it from other phosphoric acids, and any water soluble salt or acid salt of orthophosphoric acid that does not act adversely to the objects of the in-vention may be used as a source of component (A) of a composition according to the invention as defined above, and any such salt is to be under~luod, for the 20 purpose of the preferences i"dicz~lt d below, as contributing its full 6h -hiolll~llic equivalent as orthophosphate ions (i.e., PO4~3) to the conce~ dlion thereof in any composition according to the invention, irrespective of the actual degree of ionization that may prevail in the composition. The phosphoric acid ions contentranges from 0.1 to 30 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 25 to 20 weight parts of water-soluble polymer (D) in the aforementioned ratio. A
phosphoric acid ions content of less than 0.1 weight part in the aforementioned blend ratio often results in inadequate reactivity between the surface treatmentsolution and the surface of the metal substrate being coated, as well as in an inadequately formed film. More than 30 weight parts in this ratio does not harm 30 rc""~dLion of a favorable conversion coating but is uneconomical bec~llse of the higher cost of the treatment solution and lack of any ofFsetting benefit compared CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 with compositions containing somewhat less of this component. ~
Similarly, one or two or more types selected from among pyrophosphoric acid, tripolyphosphoric acid and tetrapolyphosphoric acid, and the salts of all of these acids, can be used to provide the condensed phosphoric acid ions in a water-based composition of this invention, but the invention is not lirnited to the use of these materials. Any water soluble source of any phos,uhale anions that CGI lldill at least two atoms of phosphorus each may be used, and is to be under-stood for the purposes of the preferences below as supplying its full stoichio-metric equivalent as condensed phosphate anions to the composition used ac-0 cording to the invention, irrespective of the actual degree of ionization that exists in the composition. For example, pyrophosphoric acid ~H4P2~17), sodium pyro-phosphate (Na4P2O7) and like compounds can be used to provide pyrophosphate ions. In a surface treatment composition according to the present invention, thecontent of the condensed phosphoric acid ions component (B) ranges from 0.1 to 10 weight parts, and preferably 0.5 to 3.0 weight parts, per 0.1 to 20 weightparts of water-soluble polymer (D). A condensed phosphoric acid ions content of less than 0.1 weight part in the aforementioned ratio normally results in a sur-face treatment solution with weak etching action, preventing a film from being adequateiy forrned. A content of more than 10 weight parts usually results in a surface treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
In a surface treatment composition acco~ Ig to the pr~sel ll invention, the oxidizing agent preferably comprises, more preferably consists essentially of, or still more preferably consists of one or more sl ~hst~nces selecttsd from the group consi~ g of hydrogen peroxide, chlorates, and nitrites; the use of hydrogen per-oxide is most preferred. The content of oxidizing agent component (C) in the aforementioned ratio for the surface treatment composition according to the present invention ranges from 0.1 to 10 weight parts, and preferably 2 to 5 weight parts, per 0.1 to 20 weight parts of water-soluble polymer COI "pone"l (D).
so An oxidizing agent co, ll~lll of less than 0.1 weight part usually results in a treat-ment solution with weak etching action, preventing an adequate film from being CA 02232998 l998-03-2~
W O 97/13887 PCTrUS96/16132 formed. More than 10 weight parts usually results in a treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
The water-soluble polymem~sed in the present invention is a water-sol-uble polymer (a term intended herein to include oligomers) that has an average 5 degree of polymeri~lion of 2 to 5al, or preferably of 2 to 20, and that contains, ~ preferably consists essentially of, Ol more pr~r~l dbly consists of (except for end groups) polymer units as described above in connection with general formula (I).When the alkyl or hydroxyalkyl groups represented by X1 and x2 in general formula (I) have 6 or more carbon atoms, the resulting polymer becon ,esbulky, usually causing steric hindrance and preventing a compact film with good corrosion reslstance from being obtained.
When the average value for Z substitutions is less than 0.2, the resulting polymer normally has poor water solubility, and the resulting surface treatment composition stability is usually inadequate. When the average value for Z moietysl Ihstitlltion is more than 1.0, and thus contains a substantial fraction of benzene rings s~ Ihstitl Ited by two or more Z ç roups, the polymer usually has such a high water solubility that a composition containing it as component (D) has great difficulty in forming a satisfactorily protective surface film.
The alkyl or hydroxyalkyl groups expressed by R', R2, R3, R4, and R5 in general formulas (Il) and (Ill) have 1 to 10 carbon atoms. A number of carbon atoms of 11 or more usually results in a polymer molecule that is too bulky, leading to a film with poor density and insuffcient corrosion resistance.
In a surface treatment composition according to the present invention, the content of the water-soluble polymer component (D), in terms of the aforemen-2s tioned ratios to other components, is 0.1 to 20 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 to 30 weight parts of phosphoric acid ions (A). When this ratio is less than 0.1 weight parlt, it is diffcult to form a film on the surface of aluminiferous metals with the surface treatment composition, whereas more than 20 weight parts in this ratio is uneconomical bec~use of the higher cost of the re-sulting surface treatment and laclc of any s~hst~ntial improvement over the results achieved with a composition according to the invention containing 20 or CA 02232998 l998-03-2~
W O 97/13887 PCTrUS96/16132 fewer parts in this ratio. - -Although not narrowly limited, the pH of a working surface llt:dllllel)l com-position according to the present invention is preferably no more than 6.5, and even more preferably is between 2.0 and 6.5. When the pH of the surface treat-5 ment composition is higher than 6.5, the polymer of forrnula (I) in the resultingsurface treatment composition tends to precipitate, impairing the treatment com-position stability and its use life. When the pH is lower than 2.0, tl-e etching ac-tion of the surFace l~t:almenl composition on the surface of the metal material is very strong, making it difficult to form a surFace film. The pH of the surface treat-10 ment composition can be ~justed using an acid such as phosphoric acid, nitricacid, and hydrochloric acid, or an alkali such as sodium hydroxide, sodium car-bonate, and ammonium h~/-lr~xide. Hydrofluoric acid may be used to adjust the pH when wastewater disposal is not a problem.
In a surface treatment method according to the present invention, the 15 aforementioned surface treatment solution preferably has a pH of 2.0 to 6.5 and contains from 1 to 30 grams per liter (hereinafter usually abbreviated as "g/l") of phosphoric acid ions, from 0.1 to 10 9/l of condensed phos,c I ,oric acid ions, from 0.1 to 10 g/l of oxidizing agent, and from 0.1 to 20 gA of water-soluble polymercomponent (D) as described above. When the conce"l,dlion of phosphoric acid 20 ions in a surface treatment composition according to the invention is lower than 0.1 g/l, a surface film is usually inadequately formed, whereas more than 30 g/lis uneconomical bec~se of higher costs. When the conce"l,dliG" of the con-densed phosphoric acid ions is lower than 0.1 g/l, the etching action of the result-ing surface treatment composition is usually too weak, and a suRace film is in-25 adequately formed, whereas more than 10 9/l results in a surface L~ ~l" ,el ,t com-position with etcl~ ;a properties that are so strong that the film-forming reaction is hindered. When the oxidizing agent concentration is lower than 0.1 g/l, the etching action of the resulting surface treatment composition is weak, usually preventing the formation of an adequate film, whereas more than 10 g/l results in a surface treatment composition with etching action that is too high, which hinders the film-forming reaction. When the conce"lldlion of the water-soluble -CA 02232998 1998-03-2~
W O 97/13887 PCT~US96/16132 polymer component (D) is lower than 0.1 g/l, the resulting surface treatment~
composition usually has inadequal:e film formability, whereas more than 20 g/l is economically disadvantageous because of higher costs.
When aluminum ions that have eluted from the aluminiferous metal be-5 come mixed with the surface treatment composition, the water-soluble polymer (D) and the metal ions sometimes fomm a conl,~lex and produce precipitation. In such instances, an aluminum sequestering agent should be added to the surface treatment composition. Examples of useful aluminum sequestering agents in-clude, but are not limited to, ethylene dian ,i"e tetra-acetic acid, 1 ,2-cyclohexane-.0 diamine tetra-acetic acid, triethanolamine, gluconic acid, heptogluconic acid, ox-alic acid, tartaric acid, malic acid, and organophosphonic acids. When the use of hydrofluoric acid poses no problems for wastewater treatment, it may be used as a sequestering agent.
In a ll l~:lhod of the present invention, a working surface Ll~::dl",ent compo-15 sition as described above is brought into conl~;l, preferably for a total of 1 to 60seconds and independently prert:r~bly at a temperature within a range from 30 to 65 oc, with a surface of an aluminiferous metal. The film formed on the sur-face of the metal material is then preferably rinsed with water, and thereafter preferably is heated and dried. Contact between the aluminiferous metal and a 20 working composition may be established by any convenient method, among which immersion of the substrate in a bath of the working composition and spraying the working composition on the metal are most cG",mon. A contact time of less than 1 second usually results in inadequate formation of a cor,usion-resislanl film, whereas a contact time of more than 60 seconds yields no greater25 benefits and thus leads to less operational efficiency.
When a spray treatment is used, the surface treatment composition some-times foams and thus causes problems in the film that is formed. Although the presence or absence of foaming and the extent of such foaming depends largely on the spraying equipment and conditions, a defoaming agent should be added 30 to the surface l,~ "ent composition when foaming is not suitably avoided by modification of the spraying equipmlent and conditions. The type of defoaming CA 02232998 l998-03-2~
agent, the amount used, and so forth are not narrowly limited, but the adhesion-between the resulting film and the paint or laminated film should not be compro-mised.
The film formed on the surface of the aluminiferous metal in a process ac-cording to the invention is believed to be a film of an organic-inorganic composite consisting primarily of phosphates and water-soluble polymer (resin) (D). The metal substrate is etched by the ions of the phosphoric acid and condensed phosphoric acid, at which time the pH becomes elevated in some areas at the interface, resulting in the prec;~.iLdLion of phosphates on the surface. The amino groups (included in the groups Z) of the water-soluble polymer (D) have chelat-ing action, and are believed to form a type of coordination con~poun~ with the re-generated surface of the metal sul.~ le produced by the etching. Although the organic-inorganic composite film is h~sic~lly formed as a result of the two afore-mentioned actions, the additional presence of the condensed phosphoric acid ions in the surface treatment composition appears to allow some water-soluble polymer-metal coordination compound(s) to be more readily formed, thereby al-lowing a stable organic-inorganic complex film to be formed on the metal surfacewithin a wide pH range.
After a coating film has been formed in a process according to the inven-tion, the film can be and preferably is heated to allow the polymer from compon-ent (D) of the working composition according to the invention that was used, andthat was incorporated into the coating film formed on the surface, to undergo fur-ther polymeri~dlion on the surface. At least one minute at 200 ~C (in the normalambient natural atmosphere) is sufficient for the heating conditions.
A preferred expanded treatment process step sequence, using a surface treatment composition according to the present invention, is outlined below.
(1) Surface cleaning/degreasing (any acidic, alkaline, or solvent type);
(2) Rinsing with water;
(3) Surface treatment (by method of the present invention);
(4) Riosing with water;
(5) Deionized water rinsing;
CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 (6) Heating and drylng; - -(7) Painting or film lamination.
Before the method of the present invention is implemented, the surface of the metal ",dlt :l ial is preferably c;leaned so that it is degreased of oil such as 5 rolling oil or the like remaining on the surface of the aluminiferous metal that is being treated. No particular restrictions are imposed on the type of degreasing agent or the degreasing method used in this step. The degreased material is then preferably rinsed with water. The rinsing is intended to remove the de-greasing composition from the surface; therefore, any rinsing method may be .0 used, provided that the degreasing composition is removed from the surface.
The sur~ace l,t:aLment of the methud according to the present invention is then implemented. The surface of the aluminiferous metal being treated is the prefer-ably further rinsed with water. This rinsing is intended to remove the surface treatment composition, so any rins;ing method may be used, provided that the 15 unreacted surface treatment composition is removed from the surface. The heating and drying are intended to dry offthe rinsing water, with no narrow re-strictions imposed on the method, drying temperature, drying time, or the like, although hot air drying or the like is generally useful for industrial purposes. The surface of the aluminiferous metal that has been surFace treated is then paintedor la" ,i"~led with film. The coali"g ~ormed by a method according to the present invention has good adhesion to paint or laminated films. Since the coating formed by means of the present invention is also flexible, it also has excellentperformance after processing such as folding or drawing.
The aluminiferous metals used in the method according to the present in-26 vention include forms such as sheets, bars, tubes, wires, and the like. No re-sL, i~;tiGns whatever are imposed on the dimensions and configuration of the met-al, although the method according to the present invention is especially effective when used on aluminiferous metal coils.
The present invention is described in further detail below with reference 30 to specific working and comparison examples.
CA 02232998 l998-03-2~
Examples and Comparison Examples Methods of Evaluation (1 ) Corrosion Resist~nce The cor,osiol1 resistance of aluminum materials (resistance to darkening 5 from boiling water) was evaluated by the following test: Treated aluminum ob-jects were bent into the shape of a U around a round bar with a diameter of 1 millimeter (hereinafter usually abbreviated as "mm"); these were immersed for 30 minutes in boiling tap water; and the degree of discoloration (darkening) in the bent parts was visually ~ssessed. No darkening was rated as "O", partial .0 darkening was rated as "A", and total darkening was rated as "x".
(2) Paint Adhesion Paint adhesion was tested in the following manner: Polyvinyl chloride paint for cans was painted to a thickness of between 5 and 10 micrometres (hereinafter usually abbreviated as "~um") on the surface of treated aluminum, fol-lowed by 1 minute of baking at 260 oC; the samples were cut into rectangles 5 x 150 mm; the painted surfaces were thermally bonded via a polyamide film to form test pieces; the bonded surfaces were separated by the 180 degree peel test method; and the peel strength was evaluated at that time. The greater the peel strength, the better the paint adhesion. In general, a peel strength of 4.020 kilograms-force (hereil1~rler usually abbreviated as "kgf') or more per 5 mm of width is considered excellent for practical purposes.
(3) Wastewater Disposability Used surface treatment composition waste was diluted twenty-fold with water, and the concentration of hexavalent chromium in the thus formed compo-25 sition was measured. For the purposes of environmental protection, no chromi- um should be detected.
F~rnple 1 An aluminum-magnesium alloy sheet (alloy according to Japanese Indus-trial Standard, hereinafter usually abbreviated as "JIS", A5182) was degreased so by spraying with a 2 % aqueous solution of an alkaline degreaser (trade name:
CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 FlNECLEANER~g) 4377K, by Nihon Parkerizing) for 5 seconds at 60 oc, and was then rinsed clean with water. The sheet was then sprayed for 3 seconds at 60 oc with Surface Treatment Composition 1 having the ingredients noted below, with the balance being water; it was then rinsed with tap water, then sprayed and 5 washed for 10 seconds with deionized water having a specific resistivity of atleast 3,000,000 ohm-centimeters, and was then dried for 2 minutes in a hot air drying furnace at 80 oc.
Surface Treatment Composition 1 75 % Phosphoric acid (i.e., H3P04) : 10.0 g/l (PO43~: 7.2 g/l) Sodium pyrophosphate (i.e., Na4P~!O7 1 0H2O) : 3.0 g/l (P2O74-: 1.2 g/l) 31 % Hydrogen peroxide in water : 10.0 g/l (H2O2: 3.1 9/l) Polymer (1) - solids part : 2.0 g/l pH 4.0 (Adjusted with sodium hydroxide) Water Soluble Polymer (1 ) was according to general formula (I) when: the average value of n = 5; each of X1 and x2 represents a hydrogen atom; each of y1 and y2 represents a -CH2N(CH3)~ moiety or hydrogen atom; and the average Z moiety substitution number = 0.50 Fxample 2 Aluminum alloy materials were degreased and rinsed clean in the same 20 manner as in Example 1, and they were then treated by immersion for 10 sec-onds at 40 oC using Surface Trealment Composition 2 having the ingredients shown below, with the balance be!ing water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
Surface Treatment Composition 2 2!i 75 % Phosphoric acid (i.e., H3PO4) : 10.0 g/l (PO43~: 7.2 g/l) Sodium pyrophosphate (i.e., Na4P,!O7-10H2O) : 3.0 g/l (P2O74-: 1.2 g/l) 31 % Hydrogen peroxide in water : 15.0 g/l (H2O2: 4.6 g/l) Polymer (2) - solids part : 0.4 g/l pH 3.0 (Adjusted with sodiurn carbonate) 30 Water soluble polymer (2) was according to general formula (I) when: the CA 02232998 1998-03-2~
W O 97/13887 PCTrUS96116132 average value of n = 5; each of X' and x2 = a -C2H5 moiety; each of y1 and y2- -= a -CH2N(CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.25.
FY~PIe 3 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 1 second at 65 oc using Surface Treatment Composition 3 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
~o Surface Treatment Composition 3 75 % Phosphoric acid (i.e., H3PO4) : 20.0 9/l (PO43~: 14.4 g/l) Sodium pyrophosphate (i.e., Na4P2O7-1 OH2O) : 6.0 g/l (P2O74-: 2.4 g/l) 31 % Hydrogen Peroxide in water : 15.0 9/l (H2O2: 4-6 g/l) Polymer (3) - solids part : 8.0 9/
~s pH 4.0 (Adjusted with sodium hydroxide) Water soluble polymer (3) was according to general formula (I) when: the aver-age value of n = 15; each of X' and X2 = a -C2H5 moiety; each of Y' and y2 = a -CH2N(CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z
moiety substitution = 1Ø
20 Fy:3rnple 4 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Exalnple 1, were then spray treated for 30 seconds at 40 oc using Surface Treatment Composition 4 conldil ~ing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
Surface Treatment Composition 4 75 % Phosphoricacid (i.e., H3PO4) : 20.0g/l (PO43-: 14.4g/l) Sodium tripolyphosphate (i.e., Na~jP30,0) : 1.2 g/l (P3O,04~: 0.8 g/l) 43 % Sodium chlorate in water : 10.0 g/l (NaClO3: 4.3 9/l) Polymer(4) -solids part : 1.0 g/l CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 pH 4.0 (Adjusted with aqueous ammonia~
Water soluble polymer (4) was according to general formula (I) when: the average value of n = 15; each of X' and X2 represents a hydrogen atom; each of Y' and y2 represents a -CH2N(CIH2OH)2 moiety or a hydrogen atom; and the 5 average value for Z moiety substihltion = 0.50 Fxample 5 Aluminum alloy sheets wer~ degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 5 seconds at 50 oc using Surface Treatment Composition 5 containing the ingredients shown below, with 10 the balance being water, then rinsed and dried under the same conditions as in Example 1.
Surface Treatment Composition 5 75 % Phosphoric acid (i.e., H3PO4) : 20.0 g/l (PO43- 14.4 g/l) Pyrophosphoric acid (i-e-, H4P2O~) : 1.0 9/l (P2O74-: 0.98 g/l) 31 % Hydrogen Peroxide in water : 5.0 g/l (H2O2: 1-6 g/l) Polymer (5) - solids part : 1.0 g/l pH 3.5 (Adjusted with aqueous ammonia) Water soluble polymer (5) was according to general formula (I) when: the average value of n = 20; each of Xl and x2 = a hydrogen atom; each of Y' and y2 = a -CH2N(CH2CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0. 75.
Comparative Example 1 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, and they were then spray treated for 5 seconds at 50 ~C using Surface Treatment Composition C1 having the ingredients set forth be-low, with the balance being water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
Surface Treatment Composition C1--with no condensed phosphoric acid ions or oxidizing agent 75 % Phosphoric acid (i.e., H3PO4) : 20.0 g/l (PO43~: 14.4 g/l) CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 Polymer(6) - solids part : 1.0 g/l pH 3.5 (Adjusted with aqueous ammonia) Water soluble polymer (6) was according to general formula (I) when: the average value of n = 10; each of X1 and X2= a hydrogen atom; each of Y' and y2 = a -CH2N(CH2CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.75.
~omparative Example 2 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 2 seconds at 50 oc using ~0 a 5 % aqueous solution of a commercially available phosphoric acid chromatetype of chemical conversion composition (tradename: ALCHROME~) K 702, by Nihon Parkerizing). The treatment was followed by rinsing and drying under the same conditions as in Example 1.
Comparative Example 3 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 10 seconds at 50 oc using a 6 % aqueous solution of a commercially available zirconium phosphate type of chemical conversion composition (tradename. AEROSILTM 404, by Nihon Par-kerizing). The treatment was followed by rinsing and drying under the same con-ditions as in Example 1.
Table 1 shows the results obtained in the evaluations of the above noted Examples 1 through 5 and Comparative Examples 1 through 3.
CA 02232998 l998-03-2~
W O 97/13887 PCTrUS96/16132 Table 1 CorrosionPaint AdhesionWast~ater ResistanceaPeel Strength,Disros~bilibr kgf/5 mm) (crt6 g/l) Example 1 0 4.0 none detected Example 2 O 4.0 none detected Example3 0 4.0 nonedetected Example4 0 4.0 nonedetected Example 5 0 4.0 none detected Comparative x 1.5 none detected Example 1 Comparative x 4.0 0.2 ~x~,3le 2 Comparative x 1.5 none detected Example 3 It is appa,~nL from the results in Table 1 that Examples 1 through 5 which used a method according to the present invention had better corrosion resist-ance, adhesion, and wastewater alisposability.
In Comparative Example 1, the surface treatment composition contained 5. no condensed phosphoric acid ions or oxidizing agent, resulting in a film with in-adequate corrosion resistance and paint adhesion. In Comparative Examples 2 and 3, convel lliGnal surface treatment compositions were used, resulting in films with low corrosion resistance. In Comparative Example 2, the wastewater con-tained hexavalent chromium, while in Comparative Example 3, the paint adhe-~o sion was poor.Benefits of the Invention It is apparent from the aforelmentioned description that the surface treat-ment composition and method according to the present invention allow a chem-ical conversion film with better corrosion resistance and paint adhesion to be 15 formed on the surfaces of aluminiferous metals before they are painted. The surface treatment composition and method according to the present invention are non-chromium and non-fluorine types, and have the exceptional merit of al-leviating the burden of wastewater disposal.
CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 (6) Heating and drylng; - -(7) Painting or film lamination.
Before the method of the present invention is implemented, the surface of the metal ",dlt :l ial is preferably c;leaned so that it is degreased of oil such as 5 rolling oil or the like remaining on the surface of the aluminiferous metal that is being treated. No particular restrictions are imposed on the type of degreasing agent or the degreasing method used in this step. The degreased material is then preferably rinsed with water. The rinsing is intended to remove the de-greasing composition from the surface; therefore, any rinsing method may be .0 used, provided that the degreasing composition is removed from the surface.
The sur~ace l,t:aLment of the methud according to the present invention is then implemented. The surface of the aluminiferous metal being treated is the prefer-ably further rinsed with water. This rinsing is intended to remove the surface treatment composition, so any rins;ing method may be used, provided that the 15 unreacted surface treatment composition is removed from the surface. The heating and drying are intended to dry offthe rinsing water, with no narrow re-strictions imposed on the method, drying temperature, drying time, or the like, although hot air drying or the like is generally useful for industrial purposes. The surface of the aluminiferous metal that has been surFace treated is then paintedor la" ,i"~led with film. The coali"g ~ormed by a method according to the present invention has good adhesion to paint or laminated films. Since the coating formed by means of the present invention is also flexible, it also has excellentperformance after processing such as folding or drawing.
The aluminiferous metals used in the method according to the present in-26 vention include forms such as sheets, bars, tubes, wires, and the like. No re-sL, i~;tiGns whatever are imposed on the dimensions and configuration of the met-al, although the method according to the present invention is especially effective when used on aluminiferous metal coils.
The present invention is described in further detail below with reference 30 to specific working and comparison examples.
CA 02232998 l998-03-2~
Examples and Comparison Examples Methods of Evaluation (1 ) Corrosion Resist~nce The cor,osiol1 resistance of aluminum materials (resistance to darkening 5 from boiling water) was evaluated by the following test: Treated aluminum ob-jects were bent into the shape of a U around a round bar with a diameter of 1 millimeter (hereinafter usually abbreviated as "mm"); these were immersed for 30 minutes in boiling tap water; and the degree of discoloration (darkening) in the bent parts was visually ~ssessed. No darkening was rated as "O", partial .0 darkening was rated as "A", and total darkening was rated as "x".
(2) Paint Adhesion Paint adhesion was tested in the following manner: Polyvinyl chloride paint for cans was painted to a thickness of between 5 and 10 micrometres (hereinafter usually abbreviated as "~um") on the surface of treated aluminum, fol-lowed by 1 minute of baking at 260 oC; the samples were cut into rectangles 5 x 150 mm; the painted surfaces were thermally bonded via a polyamide film to form test pieces; the bonded surfaces were separated by the 180 degree peel test method; and the peel strength was evaluated at that time. The greater the peel strength, the better the paint adhesion. In general, a peel strength of 4.020 kilograms-force (hereil1~rler usually abbreviated as "kgf') or more per 5 mm of width is considered excellent for practical purposes.
(3) Wastewater Disposability Used surface treatment composition waste was diluted twenty-fold with water, and the concentration of hexavalent chromium in the thus formed compo-25 sition was measured. For the purposes of environmental protection, no chromi- um should be detected.
F~rnple 1 An aluminum-magnesium alloy sheet (alloy according to Japanese Indus-trial Standard, hereinafter usually abbreviated as "JIS", A5182) was degreased so by spraying with a 2 % aqueous solution of an alkaline degreaser (trade name:
CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 FlNECLEANER~g) 4377K, by Nihon Parkerizing) for 5 seconds at 60 oc, and was then rinsed clean with water. The sheet was then sprayed for 3 seconds at 60 oc with Surface Treatment Composition 1 having the ingredients noted below, with the balance being water; it was then rinsed with tap water, then sprayed and 5 washed for 10 seconds with deionized water having a specific resistivity of atleast 3,000,000 ohm-centimeters, and was then dried for 2 minutes in a hot air drying furnace at 80 oc.
Surface Treatment Composition 1 75 % Phosphoric acid (i.e., H3P04) : 10.0 g/l (PO43~: 7.2 g/l) Sodium pyrophosphate (i.e., Na4P~!O7 1 0H2O) : 3.0 g/l (P2O74-: 1.2 g/l) 31 % Hydrogen peroxide in water : 10.0 g/l (H2O2: 3.1 9/l) Polymer (1) - solids part : 2.0 g/l pH 4.0 (Adjusted with sodium hydroxide) Water Soluble Polymer (1 ) was according to general formula (I) when: the average value of n = 5; each of X1 and x2 represents a hydrogen atom; each of y1 and y2 represents a -CH2N(CH3)~ moiety or hydrogen atom; and the average Z moiety substitution number = 0.50 Fxample 2 Aluminum alloy materials were degreased and rinsed clean in the same 20 manner as in Example 1, and they were then treated by immersion for 10 sec-onds at 40 oC using Surface Trealment Composition 2 having the ingredients shown below, with the balance be!ing water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
Surface Treatment Composition 2 2!i 75 % Phosphoric acid (i.e., H3PO4) : 10.0 g/l (PO43~: 7.2 g/l) Sodium pyrophosphate (i.e., Na4P,!O7-10H2O) : 3.0 g/l (P2O74-: 1.2 g/l) 31 % Hydrogen peroxide in water : 15.0 g/l (H2O2: 4.6 g/l) Polymer (2) - solids part : 0.4 g/l pH 3.0 (Adjusted with sodiurn carbonate) 30 Water soluble polymer (2) was according to general formula (I) when: the CA 02232998 1998-03-2~
W O 97/13887 PCTrUS96116132 average value of n = 5; each of X' and x2 = a -C2H5 moiety; each of y1 and y2- -= a -CH2N(CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.25.
FY~PIe 3 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 1 second at 65 oc using Surface Treatment Composition 3 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
~o Surface Treatment Composition 3 75 % Phosphoric acid (i.e., H3PO4) : 20.0 9/l (PO43~: 14.4 g/l) Sodium pyrophosphate (i.e., Na4P2O7-1 OH2O) : 6.0 g/l (P2O74-: 2.4 g/l) 31 % Hydrogen Peroxide in water : 15.0 9/l (H2O2: 4-6 g/l) Polymer (3) - solids part : 8.0 9/
~s pH 4.0 (Adjusted with sodium hydroxide) Water soluble polymer (3) was according to general formula (I) when: the aver-age value of n = 15; each of X' and X2 = a -C2H5 moiety; each of Y' and y2 = a -CH2N(CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z
moiety substitution = 1Ø
20 Fy:3rnple 4 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Exalnple 1, were then spray treated for 30 seconds at 40 oc using Surface Treatment Composition 4 conldil ~ing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
Surface Treatment Composition 4 75 % Phosphoricacid (i.e., H3PO4) : 20.0g/l (PO43-: 14.4g/l) Sodium tripolyphosphate (i.e., Na~jP30,0) : 1.2 g/l (P3O,04~: 0.8 g/l) 43 % Sodium chlorate in water : 10.0 g/l (NaClO3: 4.3 9/l) Polymer(4) -solids part : 1.0 g/l CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 pH 4.0 (Adjusted with aqueous ammonia~
Water soluble polymer (4) was according to general formula (I) when: the average value of n = 15; each of X' and X2 represents a hydrogen atom; each of Y' and y2 represents a -CH2N(CIH2OH)2 moiety or a hydrogen atom; and the 5 average value for Z moiety substihltion = 0.50 Fxample 5 Aluminum alloy sheets wer~ degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 5 seconds at 50 oc using Surface Treatment Composition 5 containing the ingredients shown below, with 10 the balance being water, then rinsed and dried under the same conditions as in Example 1.
Surface Treatment Composition 5 75 % Phosphoric acid (i.e., H3PO4) : 20.0 g/l (PO43- 14.4 g/l) Pyrophosphoric acid (i-e-, H4P2O~) : 1.0 9/l (P2O74-: 0.98 g/l) 31 % Hydrogen Peroxide in water : 5.0 g/l (H2O2: 1-6 g/l) Polymer (5) - solids part : 1.0 g/l pH 3.5 (Adjusted with aqueous ammonia) Water soluble polymer (5) was according to general formula (I) when: the average value of n = 20; each of Xl and x2 = a hydrogen atom; each of Y' and y2 = a -CH2N(CH2CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0. 75.
Comparative Example 1 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, and they were then spray treated for 5 seconds at 50 ~C using Surface Treatment Composition C1 having the ingredients set forth be-low, with the balance being water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
Surface Treatment Composition C1--with no condensed phosphoric acid ions or oxidizing agent 75 % Phosphoric acid (i.e., H3PO4) : 20.0 g/l (PO43~: 14.4 g/l) CA 02232998 l998-03-2~
W O 97/13887 PCT~US96/16132 Polymer(6) - solids part : 1.0 g/l pH 3.5 (Adjusted with aqueous ammonia) Water soluble polymer (6) was according to general formula (I) when: the average value of n = 10; each of X1 and X2= a hydrogen atom; each of Y' and y2 = a -CH2N(CH2CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.75.
~omparative Example 2 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 2 seconds at 50 oc using ~0 a 5 % aqueous solution of a commercially available phosphoric acid chromatetype of chemical conversion composition (tradename: ALCHROME~) K 702, by Nihon Parkerizing). The treatment was followed by rinsing and drying under the same conditions as in Example 1.
Comparative Example 3 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 10 seconds at 50 oc using a 6 % aqueous solution of a commercially available zirconium phosphate type of chemical conversion composition (tradename. AEROSILTM 404, by Nihon Par-kerizing). The treatment was followed by rinsing and drying under the same con-ditions as in Example 1.
Table 1 shows the results obtained in the evaluations of the above noted Examples 1 through 5 and Comparative Examples 1 through 3.
CA 02232998 l998-03-2~
W O 97/13887 PCTrUS96/16132 Table 1 CorrosionPaint AdhesionWast~ater ResistanceaPeel Strength,Disros~bilibr kgf/5 mm) (crt6 g/l) Example 1 0 4.0 none detected Example 2 O 4.0 none detected Example3 0 4.0 nonedetected Example4 0 4.0 nonedetected Example 5 0 4.0 none detected Comparative x 1.5 none detected Example 1 Comparative x 4.0 0.2 ~x~,3le 2 Comparative x 1.5 none detected Example 3 It is appa,~nL from the results in Table 1 that Examples 1 through 5 which used a method according to the present invention had better corrosion resist-ance, adhesion, and wastewater alisposability.
In Comparative Example 1, the surface treatment composition contained 5. no condensed phosphoric acid ions or oxidizing agent, resulting in a film with in-adequate corrosion resistance and paint adhesion. In Comparative Examples 2 and 3, convel lliGnal surface treatment compositions were used, resulting in films with low corrosion resistance. In Comparative Example 2, the wastewater con-tained hexavalent chromium, while in Comparative Example 3, the paint adhe-~o sion was poor.Benefits of the Invention It is apparent from the aforelmentioned description that the surface treat-ment composition and method according to the present invention allow a chem-ical conversion film with better corrosion resistance and paint adhesion to be 15 formed on the surfaces of aluminiferous metals before they are painted. The surface treatment composition and method according to the present invention are non-chromium and non-fluorine types, and have the exceptional merit of al-leviating the burden of wastewater disposal.
Claims (9)
1. A liquid composition of matter suitable for use as such, after dilution with water, or both as such and after dilution with water for the surface treatment of aluminiferous metals, said composition comprising water and:
(A) a component of ions of orthophosphoric acid;
(B) a component of ions of condensed phosphoric acid(s);
(C) a component of oxidizing agent; and (D) a component of molecules of water-soluble polymers, oligomers, or both polymers and oligomers, each of said molecules conforming, except for end groups, to the following general formula (I):
in which each of X1 and X2 independently of each other and independently from one unit of the molecule, said unit being defined as represented by a modification of formula (I) above in which the square brackets and the subscript n are omitted, to another unit of the molecule represents a hydrogen atom, a C1 to C5 alkyl group, or a C1 to C5 hydroxyalkyl group; each of Y1 and Y2 independently of one another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which conforms to one of the following general formulas (II) and (III):
in which each of R1, R2, R3, R4, and R5 in each of general formulas (II) and (III) independently represents a C1 to C10 alkyl group or a C1 to C10 hydroxyalkyl group; one moiety "Z" may be identical to or may differ from any other moiety "Z" in the same or another molecule, so long as each "Z"
moiety conforms to one of the general formulas (II) and (III); and n represents a positive integer, which may be the same as or different from the value of n for any other molecule in component (D); and in component (D) as a whole: the average value for the number of Z moieties substituted on each phenyl ring in the polymer molecule, which may be referred to hereinafter as "the average value for Z moiety substitution", is from 0.2 to 1.0; the average value of n, which may be referred to hereinafter as "the average degree of polymerization", is from 2 to 50, and, because it is an average, need not be an integer, in said composition as a whole, the aforementioned phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble polymer (D) being present in a weight ratio (A):(B):(C):(D) of 0.1 to 30: 0.1 to 10: 0.1 to 10: 0.1 to 20.
(A) a component of ions of orthophosphoric acid;
(B) a component of ions of condensed phosphoric acid(s);
(C) a component of oxidizing agent; and (D) a component of molecules of water-soluble polymers, oligomers, or both polymers and oligomers, each of said molecules conforming, except for end groups, to the following general formula (I):
in which each of X1 and X2 independently of each other and independently from one unit of the molecule, said unit being defined as represented by a modification of formula (I) above in which the square brackets and the subscript n are omitted, to another unit of the molecule represents a hydrogen atom, a C1 to C5 alkyl group, or a C1 to C5 hydroxyalkyl group; each of Y1 and Y2 independently of one another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which conforms to one of the following general formulas (II) and (III):
in which each of R1, R2, R3, R4, and R5 in each of general formulas (II) and (III) independently represents a C1 to C10 alkyl group or a C1 to C10 hydroxyalkyl group; one moiety "Z" may be identical to or may differ from any other moiety "Z" in the same or another molecule, so long as each "Z"
moiety conforms to one of the general formulas (II) and (III); and n represents a positive integer, which may be the same as or different from the value of n for any other molecule in component (D); and in component (D) as a whole: the average value for the number of Z moieties substituted on each phenyl ring in the polymer molecule, which may be referred to hereinafter as "the average value for Z moiety substitution", is from 0.2 to 1.0; the average value of n, which may be referred to hereinafter as "the average degree of polymerization", is from 2 to 50, and, because it is an average, need not be an integer, in said composition as a whole, the aforementioned phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble polymer (D) being present in a weight ratio (A):(B):(C):(D) of 0.1 to 30: 0.1 to 10: 0.1 to 10: 0.1 to 20.
2. A composition as defined in claim 1, wherein the oxidizing agent component includes at least one material selected from the group consisting of hydrogen peroxide, chlorates, and nitrites.
3. A composition as defined in claim 2, wherein phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble polymer (D) are present in a weight ratio (A):(B):(C):(D) of 0.5 to 5: 0.5 to 3.0: 2 to 5: 0.5 to 5.
4. A composition as defined in claim 1, wherein phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble polymer (D) are present in a weight ratio (A):(B):(C):(D) of 0.5 to 5: 0.5 to 3.0: 2 to 5 : 0.5 to 5.
5. A method for the treatment of an aluminiferous metal surface, comprisinga step of bringing the aluminiferous metal surface into contact with an aqueous liquid surface treatment composition which contains a composition as defined in any of claims 1 through 4 and has a pH value not more than 6.5.
6. A method according to claim 5, wherein the contact between the aluminiferous metal surface and the aqueous liquid surface treatment composition is maintained for a time from 1 to 60 seconds at a temperature from 35 to 65°C, and the surface which has thus been brought into contact is rinsed with water after discontinuance of the contact and is subsequently dried.
7. A method according to claim 6, wherein the dried surface formed has been or is subsequently heated to a temperature of at least 200 °C for a time of at least 1 minute in the ambient atmosphere.
8. A method according to claim 6 or 7, wherein the surface treatment composition has a pH from 2.0 to 6.5 and comprises:
from 1 to 30 g/l of component (A);
from 0.1 to 10 g/l of component (B);
from 0.1 to 10 g/l of component (C); and from 0.1 to 20 g/l of component (D).
from 1 to 30 g/l of component (A);
from 0.1 to 10 g/l of component (B);
from 0.1 to 10 g/l of component (C); and from 0.1 to 20 g/l of component (D).
9. A method according to claim 5, wherein the surface treatment composition has a pH from 2.0 to 6.5 and comprises:
from 1 to 30 g/l of component (A);
from 0.1 to 10 g/l of component (B);
from 0.1 to 10 g/l of component (C); and from 0.1 to 20 g/l of component (D).
from 1 to 30 g/l of component (A);
from 0.1 to 10 g/l of component (B);
from 0.1 to 10 g/l of component (C); and from 0.1 to 20 g/l of component (D).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26550195A JP3544761B2 (en) | 1995-10-13 | 1995-10-13 | Surface treatment composition for aluminum-containing metal material and surface treatment method |
| JP7/265501 | 1995-10-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2232998A1 true CA2232998A1 (en) | 1997-04-17 |
Family
ID=17418054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002232998A Abandoned CA2232998A1 (en) | 1995-10-13 | 1996-10-15 | Composition and process for surface treatment of aluminum and its alloys |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0859871A4 (en) |
| JP (1) | JP3544761B2 (en) |
| KR (1) | KR970021375A (en) |
| CN (1) | CN1081663C (en) |
| AR (1) | AR003859A1 (en) |
| AU (1) | AU709612B2 (en) |
| BR (1) | BR9611045A (en) |
| CA (1) | CA2232998A1 (en) |
| NZ (1) | NZ319963A (en) |
| TW (1) | TW375659B (en) |
| WO (1) | WO1997013887A1 (en) |
| ZA (1) | ZA968625B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101782A (en) * | 1996-06-13 | 1998-01-06 | Nippon Paint Co Ltd | Metallic surface treating agent, treatment and surface treated metallic material |
| JPH1046101A (en) * | 1996-08-01 | 1998-02-17 | Nippon Parkerizing Co Ltd | Coated metallic material prepared by forming undercoat for film lamination on the surface of metallic material and its production |
| JP3898302B2 (en) * | 1997-10-03 | 2007-03-28 | 日本パーカライジング株式会社 | Surface treatment agent composition for metal material and treatment method |
| EP1221497A3 (en) * | 1998-06-19 | 2003-12-03 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
| CA2336186A1 (en) * | 1998-06-19 | 1999-12-23 | Raymond J. Colbert | Method for inhibiting stains on aluminum product surfaces |
| JP4550956B2 (en) * | 1999-08-10 | 2010-09-22 | 新日本製鐵株式会社 | Painted metal plate with excellent anticorrosion paint and corrosion resistance |
| MX2017013713A (en) | 2015-05-01 | 2018-03-02 | Novelis Inc | Continuous coil pretreatment process. |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714752A (en) * | 1986-07-26 | 1987-12-22 | Detrex Corporation | 2,2-bis (4 hydroxyphenyl) alkyl poly derivatives for use in after-treatment of conversion coated metals |
| US4963596A (en) * | 1987-12-04 | 1990-10-16 | Henkel Corporation | Treatment and after-treatment of metal with carbohydrate-modified polyphenol compounds |
| JPH03207766A (en) * | 1990-01-10 | 1991-09-11 | Nippon Parkerizing Co Ltd | Surface treatment of tin di can |
| CA2085489C (en) * | 1990-06-19 | 2000-12-12 | Tomoyuki Aoki | Liquid composition and process for treating aluminum or tin cans to impart corrosion resistance and mobility thereto |
| JPH04187782A (en) * | 1990-11-21 | 1992-07-06 | Nippon Parkerizing Co Ltd | Surface treating solution for di can made of tin plate |
| US5427632A (en) * | 1993-07-30 | 1995-06-27 | Henkel Corporation | Composition and process for treating metals |
| JP2771110B2 (en) * | 1994-04-15 | 1998-07-02 | 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 |
| JP3587590B2 (en) * | 1995-07-21 | 2004-11-10 | 日本パーカライジング株式会社 | Aqueous composition for tinplate DI can surface treatment and surface treatment method |
-
1995
- 1995-10-13 JP JP26550195A patent/JP3544761B2/en not_active Expired - Fee Related
-
1996
- 1996-10-09 KR KR1019960044679A patent/KR970021375A/en active IP Right Grant
- 1996-10-11 AR ARP960104707A patent/AR003859A1/en unknown
- 1996-10-11 CN CN96112741A patent/CN1081663C/en not_active Expired - Fee Related
- 1996-10-11 TW TW085112427A patent/TW375659B/en active
- 1996-10-11 ZA ZA9608625A patent/ZA968625B/en unknown
- 1996-10-15 NZ NZ319963A patent/NZ319963A/en unknown
- 1996-10-15 EP EP96934123A patent/EP0859871A4/en not_active Withdrawn
- 1996-10-15 CA CA002232998A patent/CA2232998A1/en not_active Abandoned
- 1996-10-15 AU AU72616/96A patent/AU709612B2/en not_active Ceased
- 1996-10-15 WO PCT/US1996/016132 patent/WO1997013887A1/en not_active Application Discontinuation
- 1996-10-15 BR BR9611045A patent/BR9611045A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| TW375659B (en) | 1999-12-01 |
| AU709612B2 (en) | 1999-09-02 |
| BR9611045A (en) | 1999-07-06 |
| EP0859871A1 (en) | 1998-08-26 |
| AR003859A1 (en) | 1998-09-09 |
| AU7261696A (en) | 1997-04-30 |
| KR970021375A (en) | 1997-05-28 |
| WO1997013887A1 (en) | 1997-04-17 |
| CN1081663C (en) | 2002-03-27 |
| NZ319963A (en) | 1999-07-29 |
| EP0859871A4 (en) | 2001-04-18 |
| JP3544761B2 (en) | 2004-07-21 |
| JPH09111466A (en) | 1997-04-28 |
| CN1154390A (en) | 1997-07-16 |
| MX9802196A (en) | 1998-08-30 |
| ZA968625B (en) | 1997-08-14 |
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