WO1995033869A1 - Composition et procede de traitement de la surface de metaux alumineux - Google Patents

Composition et procede de traitement de la surface de metaux alumineux Download PDF

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Publication number
WO1995033869A1
WO1995033869A1 PCT/US1995/006710 US9506710W WO9533869A1 WO 1995033869 A1 WO1995033869 A1 WO 1995033869A1 US 9506710 W US9506710 W US 9506710W WO 9533869 A1 WO9533869 A1 WO 9533869A1
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Prior art keywords
seconds
water
spraying
phosphate
composition according
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PCT/US1995/006710
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English (en)
Inventor
Yasuo Iino
Masahiro Motozawa
Toshihiro Ikeda
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Henkel Corporation
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Publication date
Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to AU26525/95A priority Critical patent/AU2652595A/en
Priority to US08/750,261 priority patent/US5904784A/en
Publication of WO1995033869A1 publication Critical patent/WO1995033869A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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

Definitions

  • This invention relates to a liquid composition, which may be either a work ⁇ ing composition suitable for direct use in treating metal (and if so may also be called a “bath” herein below even if not used by immersion) or a concentrate composition suitable for diluting with water and/or mixing with one or more other concentrate compositions to form a working composition, and to a method for treating the surface of aluminiferous metals, which are defined for this purpose to be aluminum and its alloys that contain at least 45 % by weight of aluminum.
  • this invention relates to a composition and/or method, for treating the surface of aluminiferous metals, that imparts thereto an excellent re ⁇ sistance to blackening by boiling water, an excellent paint adherence, and an ex ⁇ cellent lubricity, and which are therefore useful, for example, for creating surface conditions that are highly adapted for aluminum can fabrication.
  • These con ⁇ version coating treatments may be broadly classified into chromate treatments, which produce chromium phosphate coatings, and non-chromate treatments, which usually contain zirconium compounds such as fluozirconic acid and salts thereof and produce composite films of zirconium oxide, zirconium phosphate,, and the like.
  • conversion-coated aluminum cans are generally subjected to a thorough rinse in a washer and drying in a water-draining oven, and, upon exiting the oven, are transported to a printing or painting process.
  • the cans Upon reaching the print- ing or painting process, the cans, which during previous process steps are typ ⁇ ically running in about five to thirty lines, are passed through a single filer to form a single line for transfer to a special-purpose conveyor.
  • Can transport is imped ⁇ ed at this point by the contact occurring between the cans and guides and be ⁇ tween individual cans.
  • Japanese Patent Application Laid Open [Kokai or Unexam- ined] Number Sho 64-85292 [85,292/1989] teaches a method for imparting lu ⁇ bricity to aluminum cans and thereby raising the can transport efficiency.
  • a water-soluble organophosphate ester, water-soluble derivative of a saturated fatty acid, or the like is sprayed onto the can surface between the final deionized water rinse in the can washer line and the draining-drying process. This spraying serves to form a lubricating organic film on the can surface.
  • Japanese Patent Application Laid Open [Kokai or Unexamined] Number Hei 5-239434 [239,434/1993] describes a method for forming a highly lubricating organic-inorganic composite coating.
  • the aluminiferous metal substrate is sprayed with or immersed in an acidic aqueous solution (pH adjusted to 2 to 5) that contains metal ions (Fe, Zr, Sn, Al, and/or Ce) and/or water-soluble or- ganophosphate esters or water-soluble derivatives of a saturated fatty acid.
  • metal ions Fe, Zr, Sn, Al, and/or Ce
  • the present invention seeks to solve the problems described above for the related art.
  • the present invention introduces a novel sur ⁇ face-treatment composition and/or method that is able to form a very corrosion- resistant, strongly paint-adherent, and highly lubricating conversion coating on the surface of aluminiferous metals.
  • a composition according to the present invention which may be either a working composition directly suitable for treating the surface of aluminiferous metals or a concentrate for making a working composition by dilution with water and/or mixing with other concentrates, comprises, preferably consists essentially of, or more preferably consists of, water and: (A) phosphate ions;
  • (C) a component selected from simple and complex fluoride anions, in an amount such that the ratio by weight of the stoichiometric equivalent as total fluorine to the weight of phosphate ions in the composition is from 0.01 to 200; and (D) a component selected from polyamides that include moieties selected from the group consisting of tertiary amino moieties and polyoxyalkylene moieties, in an amount such that the ratio by weight of the polyamides to the weight of phosphate ions in the composition is from 0.01 to 200.
  • a bath according to the present invention for treating the surface of aluminiferous metals is an aqueous solution, with a pH value in the range from
  • 1.8 to 4.0 which comprises, preferably consists essentially of, or more preferably consists of water and:
  • a method according to the present invention for treating a surface of aluminiferous metals characteristically comprises the formation of a conversion coating on a surface of aluminiferous metal by contacting the metal surface with a surface-treatment bath according to the invention as described above, in order to form thereon a layer including material incorporated from the surface- treat ⁇ ment bath and, optionally but preferably, thereafter rinsing with water and drying by heating.
  • Figure 1 (A) is a top view showing cans to be tested for coefficient of fric ⁇ tion in place on a tiltable plate in testing apparatus.
  • Figures 1(B) and 1 (C) are front and side views respectively of the same apparatus, with cans in place there ⁇ on, as is shown in Figure 1(A). ⁇ o Description of Preferred Embodiments.
  • Aluminiferous metals which may be subjected to the present invention en ⁇ compass aluminum and aluminum alloys, wherein said aluminum alloys encom ⁇ pass aluminum/manganese alloys, aluminum/magnesium alloys, aluminum/cop ⁇ per alloys, and the like.
  • the shape and dimensions of the aluminiferous metal is are not critical; for example, sheet, tubing, wire, and the like, may all be treated.
  • a concentrate composition according to the present invention is a water- based mixture — and preferably an aqueous solution — containing the neces ⁇ sary ingredients already described above.
  • the total solids concentration in such as concentrate composition is not critical, but in general preferably does not ex- 0 ceed 10 weight % and more preferably is 0.01 to 1 weight %.
  • the phosphate ions source can be, for example, phosphoric acid (H 3 P0 4 ), sodium phosphate (Na 3 P0 4 ), ammonium phosphate ((NH 4 ) 3 P0 4 ), and/or the like.
  • the phosphate ions concentration preferably ranges from 0.01 to 1.0 g/L and particularly preferably ranges from 0.02 to 0.40 g/L.
  • the reactivity, with a surface 5 of aluminiferous metal, of a bath otherwise according to the invention but with phosphate ions concentrations below 0.01 g/L generally is inadequate, so that an acceptable coating will not be produced. Since no additional improvements in film-forming capacity are obtained at phosphate ions concentrations beyond 1.0 g L, the corresponding increase in the cost of the treatment bath is econom- o ically unjustified.
  • the water-soluble zirconium compounds and water-soluble titanium com ⁇ pounds can be selected, for example, from oxides such as zirconium oxide and titanium oxide, hydroxides such as zirconium hydroxide and titanium hydroxide, fluorides such as zirconium fluoride and titanium fluoride, and nitrates such as zirconium nitrate and titanium nitrate; however, other water-soluble compounds of zirconium and titanium may be used.
  • the concentration of this component 5 preferably ranges from 0.01 to 0.5 g/L, measured as the stoichiometric equiva ⁇ lent as zirconium and/or titanium metal, and particularly preferably ranges from 0.02 to 0.08 g/L as metal.
  • the film-forming capacity of the surface-treatment bath is usually inadequate at concentrations below 0.01 g/L.
  • no additional improvements in film-forming capacity are normally obtained at con- o centrations beyond 2.0 g/L, and the corresponding increase in the cost of the treatment bath is therefore economically unjustified.
  • the fluoride component can be obtained from acids such as hydrofluoric acid (HF), fluozirconic acid (H j ZrF e ), fluotitanic acid (H 2 TiF 6 ), and the like, and from the salts of these acids (for example, ammonium salts, sodium salts, and s the like), but no specific limitations apply to the particular fluoride selected.
  • acids such as hydrofluoric acid (HF), fluozirconic acid (H j ZrF e ), fluotitanic acid (H 2 TiF 6 ), and the like, and from the salts of these acids (for example, ammonium salts, sodium salts, and s the like), but no specific limitations apply to the particular fluoride selected.
  • the fluoride concentration in the surface-treatment bath preferably ranges from 0.03 to 1.0 g/L, measured as o its stoichiometric equivalent as fluorine, and particularly preferably ranges from 0.03 to 0.6 g/L as fluorine.
  • the poor reactivity occurring at concentrations below 0.03 g/L generally prevents the formation of an acceptable coating.
  • concentrations above 1 g/L are undesirable due to the deteri ⁇ oration in appearance that results from the greater degree of etching of the alum- 5 iniferous metal surface.
  • the most optimal fluoride concentration is determined by the concentration of aluminum that elutes from the metal and will therefore vary as a function of this aluminum concentration. This is due to the fact that the fluoride is required at least in part for the purpose of stabilizing, as aluminum fluoride, the aluminum eluted into the treatment bath. For example, approximate- ly 0.2 g/L of fluorine is required per 0.1 g/L of eluted aluminum.
  • One type of amino-functional water-soluble polyamides used by the pres ⁇ ent invention is exemplified by condensation polyamides from dicarboxylic acid molecules (e.g., adipic acid, sebacic acid, etc.) and diamine molecules that con ⁇ tain a tertiary amino group in their main chains, such as N-(aminoethyl)pipera- zine, bis[N-(aminopropyl)piperazine], and the like, and by copolyamides of the preceding with lactams, including lactams that contain a pendant tertiary amino group, e.g., alpha-dimethylamino-epsilon-caprolactam.
  • dicarboxylic acid molecules e.g., adipic acid, sebacic acid, etc.
  • diamine molecules that con ⁇ tain a tertiary amino group in their main chains, such as N-(aminoethyl
  • a second type of polyamides whose main chains contain polyoxyalkylene moieties, are exemplified by polyamides from dicarboxylic acid molecules (e.g., adipic acid, sebacic acid, etc.) and diamine molecules obtained from polyoxyeth ⁇ ylene with a molecular weight of approximately 200 to 4,000, optionally also in- eluding diamines such as hexamethylenediamine, and by copolyamides of the preceding with lactams.
  • dicarboxylic acid molecules e.g., adipic acid, sebacic acid, etc.
  • diamine molecules obtained from polyoxyeth ⁇ ylene with a molecular weight of approximately 200 to 4,000
  • polyoxyethylene moieties are preferred over those derived from higher molecular weight epoxides than ethylene oxide.
  • the surface-treatment bath concentration of water-soluble polyamide mol ⁇ ecules preferably ranges from 0.01 to 2.0 g/L and particularly preferably ranges from 0.05 to 0.5 g/L.
  • the pH of a surface-treatment bath according to the present invention should be from 1.8 to 4.0.
  • the stronger etching that occurs at pH values below 1.8 makes it difficult for a coating to form, while the formation of highly corrosion- resistant coatings is hindered at pH values in excess of 4.0.
  • the pH of the surface-treatment bath can be adjusted through the use of acid, e.g., phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid, and the like, or alkali, e.g., sodium hydroxide, sodium carbonate, ammonium hydrox ⁇ ide, and the like.
  • an at least difunctional organic acid such as gluconic acid, oxalic acid, etc. and/or other known chelating agent(s) may advantageously be added to a bath according to this invention, in order to chelate this destabilizing component.
  • treatment preferably uses the following conditions: (i) when the surface-treatment bath is applied to the aluminiferous metal sur ⁇ face by spraying, preferred conditions are contact for 15 to 40 seconds at temperatures of 25 °C to 50 °C, followed by water rinsing; (ii) when the metal workpiece is immersed in the surface-treatment bath, pre ⁇ ferred conditions are immersion for 15 to 60 seconds at 25 °C to 50 °C, followed by water rinsing.
  • 25°C to 50°C is the preferred range for the treatment temperature using a surface-treatment bath according to the present invention.
  • Low reactivity at temperatures below 25 °C can lead to failure to form a high quality coating.
  • Most zirconium compounds in the treatment bath according to this invention become unstable at temperatures above 50 °C, which leads to their partial precipitation and can lead to loss of treatment bath stability.
  • appropriate treatment times in the case of surface-treatment Alternative Preferred Process #1 are 15 to 50 seconds. Sufficient reaction does not reliably occur and a strongly corro ⁇ sion-resistant coating may therefore not be produced at treatment times below 15 seconds. Additional increases in performance become uncertain at treatment times in excess of 50 seconds.
  • a particularly preferred treatment time range for surface-treatment Alternative Preferred Process #1 above is 20 to 30 seconds.
  • Preferred treatment times for surface-treatment Alternative Preferred Pro ⁇ Waits 2 and 3 above are 3 to 30 seconds. Sufficient reaction does not reliably occur and a strongly corrosion-resistant coating may therefore not be produced at treatment times below 3 seconds. Additional increases in performance be ⁇ come uncertain at treatment times in excess of 30 seconds.
  • a range of 5 to 15 seconds is the particularly preferred treatment time range for surface-treatment Alternative Processes #2 and #3 above.
  • the known non-chromium conversion coatings for aluminum can be used as the phosphate conversion coating in the two-reactive-treatment sequences of Processes 2 and 3 above. These are specifically exemplified by the conver ⁇ sion coatings described in Japanese Patent Publication Numbers Sho 52-131937 [131,937/1977], Sho 58-30344 [30,344/1983], and Sho 57-39314 [39,314/1982].
  • the conversion treatment bath does not contain a component (e.g., S0 4 ions) that is detrimental to the effects of the present invention
  • treatment with a bath according to the present invention can be executed immediately after con ⁇ version treatment without an intervening water rinse, as in Alternative Preferred Process 2 above.
  • treatment with a bath according to the present invention is preferably carried out following a water rinse after conversion coating.
  • the aluminum Dl cans that were surface treated as described beiow were fabricated by Dl-processing of aluminum sheet and then cleaned with a hot aque- ous solution of PALKLIN® 500 acidic degreaser, commercially supplied by Nihon Parkerizing Company, Ltd. _ Evaluation methods
  • Corrosion resistance of the aluminum Dl cans was examined by evaluating the extent of blackening after immersion of the treated can in boiling water for 30 minutes. Absence of blackening is the desired result.
  • Lubricity was evaluated based on the following test using the sliding tester depicted in Figures 1(A), (B), and (C). Three of the surface-treated aluminum Dl sample cans were placed on the horizontally positioned tiltable plate 1 in the sliding tester. Two of the cans, designated as 2a, were loaded with their bottom ends facing to the front. The remaining single can, designated as 2b, was loaded with its open end facing to the front. The tiltable plate 1 was then tilted at a constant rate of 3° of angle per sec ⁇ ond by the action of the motor 3. The coefficient of static friction was calculated from the angle of inclination, determined from the time required until at least one can fell off.
  • Paint adherence In order to evaluate the paint adherence, the surface of the treated can was coated with an epoxy-urea can paint to a paint film thick ⁇ ness of 5 to 7 micrometers, then baked for 4 minutes at 215 °C. Cellophane tape-peel testing was then carried out on a cross scribed in the evaluation sur ⁇ face using a knife cutter to determine primary adherence. The sample cans were subsequently immersed for 60 minutes in a boiling test solution with the composi- tion given below, after which cellophane tape-peel testing was again carried out to determine secondary adherence. The adherence was evaluated as the pres ⁇ ence/absence of paint film peeling.
  • Test solution 5 g/L of sodium chloride 5 g/L of citric acid
  • Example 1 The surfaces of cleaned aluminum Dl cans were subjected to the following treatment steps in the sequence given: spraying for 20 seconds with ALODINE® 404 zirconium phosphate based conversion coating bath for aluminum Dl can ap ⁇ plications heated to 35 °C (commercially supplied by Nihon Parkerizing Com ⁇ pany, Ltd.); spraying for 10 seconds with Surface-treatment Bath 1 having the composition shown below and heated to 35 °C; rinsing with tap water; spraying for 10 seconds with deionized water with a specific resistivity of at least 3,000,000 ohm-cm; and drying for 2 minutes at 200 °C in a hot-air drying oven. The corrosion resistance and paint adherence of the resulting Dl can were then evaluated.
  • Water-soluble polyamide #1 was a terpol- ymer of adipic acid, N-(aminoethyl)piperazine, and caprolactam.
  • Example 2 Cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 25 seconds with the same surface-treatment as was used in the first step in Example 1 ; immersion for 15 seconds in Surface- treatment Bath 2 having the composition shown below and heated to 30 °C; a water rinse and 10-second spray with de-ionized water as in Example 1 ; and drying for 2 minutes at 200 °C in a hot-air drying oven. The corrosion resistance and paint adherence of the resulting Dl cans were then evaluated.
  • Surface-treatment Bath 2
  • Example 3 The cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 20 seconds with the same surface-treatment as was used in the first step in Example 1 ; spraying for 5 seconds with Surface- treatment Bath (3) having the composition shown below and heated to 45 °C; and a water rinse, de-ionized water rinse, and drying as in Example 1. The cor ⁇ rosion resistance and paint adherence of the resulting Dl cans were then evalu ⁇ ated.
  • Water-soluble polyamide #2 is a terpolymer of adipic acid; an amine terminated polyoxyethylene with the general formula H 2 N-(C 2 H 4 0) n -NH 2 , where n represents a positive integer with a value such that the polyoxyethylene block represented by (C 2 H 4 0) n has a molecular weight in the range from about 200 to 4,000; and caprolactam.
  • the cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 20 seconds with the same surface-treatment as was used in the first step in Example 1 ; immersion for 30 seconds in Surface- treatment Bath 4 having the composition shown below and heated to 50 °C; and a water rinse, deionized water rinse, and drying as in Example 1. The corrosion resistance and paint adherence of the resulting Dl cans were then evaluated.
  • Surface-treatment Bath 4
  • Example 5 The cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 20 seconds with the same surface-treatment as in the first step of Example 1 ; spraying for 8 seconds with Surface-treatment Bath 5 having the composition shown below and heated to 35 °C; and a water rinse, deionized water rinse, and drying as in Example 1. The corrosion resist ⁇ ance and paint adherence of the resulting Dl cans were then evaluated.
  • Surface-treatment Bath (5 s 75 % phosphoric acid (H 3 P0 4 ) 138 ppm (P0 4 : lOOppm)
  • Water-soluble polyamide #3 was a block terpolymer of blocks of (i) polycaproiactam, (ii) a copolymer of adipic acid and N-(aminoethyl)piperazine, and (iii) a copolymer of adipic acid and an amine ter ⁇ minated polyoxyethylene with the general formula H 2 N-(C 2 H 4 0) n -NH 2) where n represents a positive integer with a value such that the polyoxyethylene block s represented by (C 2 H 4 0) n has a molecular weight in the range from about 200 to 4,000.
  • Example 6 The cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 30 seconds with PALCOAT® 3753 surface- o treatment, for aluminum Dl cans, commercially supplied by Nihon Parkerizing Company, Ltd. and heated to 50 °C; rinsing with water; spraying for 15 seconds with Surface-treatment Bath 6 having the composition shown below and heated to 35 °C; and a water rinse, deionized water rinse, and drying as in Example 1. The corrosion resistance and paint adherence of the resulting Dl cans were then 5 evaluated.
  • the cleaned aluminum Dl cans were sprayed for 30 seconds with Sur ⁇ face-treatment Bath 7 having the composition shown below and heated to 25 °C, followed by a water rinse, de-ionized water rinse, and drying as in Example 1. The corrosion resistance and paint adherence of the resulting Dl cans were then evaluated.
  • the cleaned aluminum Dl cans were immersed for 35 seconds in Surface- treatment Bath 8 having the composition shown below and heated to 40 °C, fol ⁇ lowed by a water rinse, deionized water rinse, and drying as in Example 1.
  • the corrosion resistance and paint adherence of the resulting Dl cans were then eval- uated.
  • Comparative Example 1 The cleaned aluminum Dl cans were sprayed for 25 seconds with the same surface-treatment as in the first step of Example 1 , followed by a water rinse, deionized water rinse, and drying as in Example 1. The corrosion resist ⁇ ance and paint adherence of the resulting Dl cans were then evaluated. Comparative Example 2 The cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 20 seconds with the same surface-treatment as in the first step of Example 1 ; spraying for 10 seconds with Surface-treatment Bath 9 having the composition shown below and heated to 35 °C; and a water rinse, deionized water rinse, and drying as in Example 1. The corrosion - resistance and paint adherence of the resulting Dl cans were then evaluated.
  • Example 3 The cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 25 seconds with the same surface-treatment as in the first step of Example 1 ; spraying for 20 seconds with Surface-treatment Bath 10 having the composition shown below and heated to 35 °C; and a water rinse, deionized water rinse, and drying as in Example 1. The corrosion resist- ance and paint adherence of the resulting Dl cans were then evaluated.
  • Comparative Example 4 The cleaned aluminum Dl cans were subjected to the following treatments in the sequence given: spraying for 25 seconds with the same surface-treatment as in the first step of Example 1 ; spraying for 15 seconds with Surface-treatment Bath 11 having the composition shown below and heated to 35 °C; and a water rinse, deionized water rinse, and drying as in Example 1. The corrosion reresist- ance and paint adherence of the resulting Dl cans were then evaluated.
  • the balance of the Bath was water.
  • Example 1 The test results from Examples 1 to 8 and Comparative Examples 1 to 5 are reported in Table 1.
  • the surfaces of aluminiferous metal were treated with a surface-treatment bath according to the present invention by the surface-treatment method according to the present invention.
  • the corre- sponding results in Table 1 make clear, an excellent corrosion resistance, excel ⁇ lent paint adherence, and excellent lubricity were obtained in all cases.
  • a poor lubrication performance in particular was obtained for the products in Comparative Examples 1 to 5, which used surface-treatment baths outside the scope of the invention.
  • Application of the surface-treatment bath ac- cording to the present invention to aluminum Dl cans provides the surface of Table 1
  • RtBbBW "Resistance to Blackening by Boiling Water” and was reported on the following scale: x: entire surface blackened
  • aluminum Dl cans with an excellent corrosion resistance and lubricity prior to the painting or printing thereof. This makes possible the highly desirable effect of supporting an acceleration of the manufacturing line.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un traitement de surfaces de métaux alumineux avec une composition liquide aqueuse, dont le pH est compris entre 1,8 et 4, comprenant: a) 0,01 à 1 g/l d'ions phosphate, b) 0,01 à 0,5 g/l de composés de zircone et de titane hydrosolubles mesurés en équivalent st÷chiométrique total de ces métaux, c) 0,01 à 2 g/l d'anions fluorure simples et/ou complexes mesurés en tant que fluor, et d) 0,01 à 2 g/l de polyamides hydrosolubles qui contiennent au moins une fraction tertiaire amino ou polyoxyalkylène. Ce traitement forme, sur une telle surface métallique, une couche de conversion hautement résistante à la corrosion, fortement adhésive pour les peintures, et à faible frottement.
PCT/US1995/006710 1994-06-03 1995-06-02 Composition et procede de traitement de la surface de metaux alumineux WO1995033869A1 (fr)

Priority Applications (2)

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AU26525/95A AU2652595A (en) 1994-06-03 1995-06-02 Composition and method for treating the surface of aluminiferous metals
US08/750,261 US5904784A (en) 1994-06-03 1995-06-02 Composition and method for treating the surface of aluminiferous metals

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JP6/122,603 1994-06-03
JP12260394A JP3315529B2 (ja) 1994-06-03 1994-06-03 アルミニウム含有金属材料の表面処理用組成物及び表面処理方法

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Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812933A2 (fr) * 1996-06-13 1997-12-17 Nippon Paint Co., Ltd. Méthode de traitement de surfaces métalliques et produit obtenu
EP0837954A1 (fr) * 1995-06-30 1998-04-29 Henkel Corporation Compositions et procede pour traiter la surface de metaux alumineux
WO1998026109A1 (fr) * 1996-12-11 1998-06-18 Henkel Kommanditgesellschaft Auf Aktien Traitement de surfaces en aluminium
EP1037719A1 (fr) * 1997-10-14 2000-09-27 Henkel Corporation Composition et procede de traitement polyvalent de surfaces metalliques
WO2000068458A1 (fr) * 1999-05-11 2000-11-16 Chemetall Gmbh Traitement prealable de surfaces d'aluminium a l'aide de solutions exemptes de chrome
US6168868B1 (en) 1999-05-11 2001-01-02 Ppg Industries Ohio, Inc. Process for applying a lead-free coating to untreated metal substrates via electrodeposition
US6193815B1 (en) 1995-06-30 2001-02-27 Henkel Corporation Composition and process for treating the surface of aluminiferous metals
US6217674B1 (en) 1999-05-11 2001-04-17 Ppg Industries Ohio, Inc. Compositions and process for treating metal substrates
US6312812B1 (en) 1998-12-01 2001-11-06 Ppg Industries Ohio, Inc. Coated metal substrates and methods for preparing and inhibiting corrosion of the same
US6802913B1 (en) 1997-10-14 2004-10-12 Henkel Kommanditgesellschaft Aut Aktien Composition and process for multi-purpose treatment of metal surfaces
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CN103240295A (zh) * 2012-02-07 2013-08-14 马尔和赫兰股份有限公司 用于对圆柱体进行表面加工的设备和方法
US8652270B2 (en) 2007-09-28 2014-02-18 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
WO2014137796A1 (fr) 2013-03-06 2014-09-12 Ppg Industries Ohio, Inc. Procédés de traitement d'un substrat métallique ferreux
WO2014150050A1 (fr) 2013-03-15 2014-09-25 Ppg Industries Ohio, Inc. Compositions de prétraitement et procédés de revêtement d'une électrode de batterie
WO2014150020A1 (fr) 2013-03-15 2014-09-25 Ppg Industries Ohio, Inc. Procédé de préparation et de traitement d'un substrat d'acier
WO2014164105A1 (fr) 2013-03-11 2014-10-09 Ppg Industries Ohio, Inc. Revêtements qui présentent un aspect tri-couche, procédés de revêtement et substrats associés
US9428410B2 (en) 2007-09-28 2016-08-30 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
WO2017066168A1 (fr) 2015-10-12 2017-04-20 Ppg Industries Ohio, Inc. Procédés de dépôt électrolytique de compositions de prétraitement
WO2017079421A1 (fr) 2015-11-04 2017-05-11 Ppg Industries Ohio, Inc. Compositions de prétraitement et procédés de traitement d'un substrat
WO2018031996A1 (fr) 2016-08-12 2018-02-15 Ppg Industries Ohio, Inc. Composition de prétraitement
WO2018032010A1 (fr) 2016-08-12 2018-02-15 Prc-Desoto International, Inc. Systèmes et procédés de traitement d'un substrat métallique par prétraitement de film mince et composition d'étanchéité
WO2018039462A1 (fr) 2016-08-24 2018-03-01 Ppg Industries Ohio, Inc. Composition alcaline destiné au traitement de substrats métalliques
EP3293287A1 (fr) 2012-08-29 2018-03-14 PPG Industries Ohio, Inc. Compositions de prétraitement de zirconium contenant du molybdène, procédés associés de traitement de substrats métalliques et substrats métalliques revêtus associés
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
WO2019243973A2 (fr) 2018-06-22 2019-12-26 Ppg Industries Ohio, Inc. Procédé d'amélioration de la résistance à la corrosion d'un substrat métallique
WO2020214592A1 (fr) 2019-04-16 2020-10-22 Ppg Industries Ohio, Inc. Systèmes et procédés de maintien de bains de prétraitement
WO2021071574A1 (fr) 2019-10-10 2021-04-15 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat
WO2022187847A1 (fr) 2021-03-05 2022-09-09 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat
WO2022197357A1 (fr) 2021-03-19 2022-09-22 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat
WO2023015060A1 (fr) 2021-08-03 2023-02-09 Ppg Industries Ohio, Inc. Systèmes et procédé de traitement d'un substrat
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6432603B1 (en) * 1998-11-27 2002-08-13 Canon Kabushiki Kaisha Process for producing electrophotographic photosensitive member
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2487381A1 (fr) * 1980-07-23 1982-01-29 Produits Ind Cie Fse Solution acide aqueuse, son utilisation pour le traitement des surfaces de metaux a base d'aluminium, et concentre pour la preparer
DE3236247A1 (de) * 1982-09-30 1984-04-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur oberflaechenbehandlung von aluminium
US5139586A (en) * 1991-02-11 1992-08-18 Coral International, Inc. Coating composition and method for the treatment of formed metal surfaces
US5421913A (en) * 1989-08-01 1995-06-06 Nippon Paint Co., Ltd. Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2487381A1 (fr) * 1980-07-23 1982-01-29 Produits Ind Cie Fse Solution acide aqueuse, son utilisation pour le traitement des surfaces de metaux a base d'aluminium, et concentre pour la preparer
DE3236247A1 (de) * 1982-09-30 1984-04-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur oberflaechenbehandlung von aluminium
US5421913A (en) * 1989-08-01 1995-06-06 Nippon Paint Co., Ltd. Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method
US5139586A (en) * 1991-02-11 1992-08-18 Coral International, Inc. Coating composition and method for the treatment of formed metal surfaces
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals

Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6193815B1 (en) 1995-06-30 2001-02-27 Henkel Corporation Composition and process for treating the surface of aluminiferous metals
EP0837954A1 (fr) * 1995-06-30 1998-04-29 Henkel Corporation Compositions et procede pour traiter la surface de metaux alumineux
EP0837954A4 (fr) * 1995-06-30 1998-10-28 Henkel Corp Compositions et procede pour traiter la surface de metaux alumineux
EP0812933A3 (fr) * 1996-06-13 1998-08-19 Nippon Paint Co., Ltd. Méthode de traitement de surfaces métalliques et produit obtenu
US6013377A (en) * 1996-06-13 2000-01-11 Nippon Paint Co., Ltd. Surface-treated metal material and metal surface treatment method
EP0812933A2 (fr) * 1996-06-13 1997-12-17 Nippon Paint Co., Ltd. Méthode de traitement de surfaces métalliques et produit obtenu
WO1998026109A1 (fr) * 1996-12-11 1998-06-18 Henkel Kommanditgesellschaft Auf Aktien Traitement de surfaces en aluminium
EP1037719A1 (fr) * 1997-10-14 2000-09-27 Henkel Corporation Composition et procede de traitement polyvalent de surfaces metalliques
US6802913B1 (en) 1997-10-14 2004-10-12 Henkel Kommanditgesellschaft Aut Aktien Composition and process for multi-purpose treatment of metal surfaces
EP1037719A4 (fr) * 1997-10-14 2001-01-03 Henkel Corp Composition et procede de traitement polyvalent de surfaces metalliques
US6312812B1 (en) 1998-12-01 2001-11-06 Ppg Industries Ohio, Inc. Coated metal substrates and methods for preparing and inhibiting corrosion of the same
US6562148B1 (en) 1999-05-11 2003-05-13 Chemetall Gmbh Pretreatment of aluminum surfaces with chrome-free solutions
US6168868B1 (en) 1999-05-11 2001-01-02 Ppg Industries Ohio, Inc. Process for applying a lead-free coating to untreated metal substrates via electrodeposition
US6217674B1 (en) 1999-05-11 2001-04-17 Ppg Industries Ohio, Inc. Compositions and process for treating metal substrates
WO2000068458A1 (fr) * 1999-05-11 2000-11-16 Chemetall Gmbh Traitement prealable de surfaces d'aluminium a l'aide de solutions exemptes de chrome
WO2007019144A1 (fr) * 2005-08-03 2007-02-15 Ppg Industries Ohio, Inc. Revêtements de boîtes de conserve, procédés destinés au revêtement d’une boîte de conserve et boîtes de conserve ainsi revêtues
US7475786B2 (en) 2005-08-03 2009-01-13 Ppg Industries Ohio, Inc. Can coatings, methods for coating can and cans coated thereby
US8652270B2 (en) 2007-09-28 2014-02-18 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
US9428410B2 (en) 2007-09-28 2016-08-30 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
WO2013033372A1 (fr) 2011-09-02 2013-03-07 Ppg Industries Ohio, Inc. Procédé de phosphatation au zinc en deux étapes
WO2013052195A2 (fr) 2011-09-30 2013-04-11 Ppg Industries Ohio, Inc. Compositions de prétraitement à rhéologie modifié et méthodes d'utilisation associées
WO2013049004A1 (fr) 2011-09-30 2013-04-04 Ppg Industries Ohio, Inc. Agents nettoyants acides pour substrats métalliques et procédés associés pour nettoyage et revêtement de substrats métalliques
US9051475B2 (en) 2011-09-30 2015-06-09 Ppg Industries Ohio, Inc. Rheology modified pretreatment compositions and associated methods of use
WO2013089903A1 (fr) 2011-12-13 2013-06-20 Ppg Industries Ohio, Inc. Post-rinçage à base de résine permettant un meilleur pouvoir de dépôt uniforme des compositions de revêtement électrodéposables sur des substrats métalliques prétraités
CN103240295A (zh) * 2012-02-07 2013-08-14 马尔和赫兰股份有限公司 用于对圆柱体进行表面加工的设备和方法
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
EP3293287A1 (fr) 2012-08-29 2018-03-14 PPG Industries Ohio, Inc. Compositions de prétraitement de zirconium contenant du molybdène, procédés associés de traitement de substrats métalliques et substrats métalliques revêtus associés
WO2014137796A1 (fr) 2013-03-06 2014-09-12 Ppg Industries Ohio, Inc. Procédés de traitement d'un substrat métallique ferreux
WO2014164105A1 (fr) 2013-03-11 2014-10-09 Ppg Industries Ohio, Inc. Revêtements qui présentent un aspect tri-couche, procédés de revêtement et substrats associés
WO2014150020A1 (fr) 2013-03-15 2014-09-25 Ppg Industries Ohio, Inc. Procédé de préparation et de traitement d'un substrat d'acier
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
US9303167B2 (en) 2013-03-15 2016-04-05 Ppg Industries Ohio, Inc. Method for preparing and treating a steel substrate
WO2014150050A1 (fr) 2013-03-15 2014-09-25 Ppg Industries Ohio, Inc. Compositions de prétraitement et procédés de revêtement d'une électrode de batterie
WO2017066168A1 (fr) 2015-10-12 2017-04-20 Ppg Industries Ohio, Inc. Procédés de dépôt électrolytique de compositions de prétraitement
US11591707B2 (en) 2015-10-12 2023-02-28 Ppg Industries Ohio, Inc. Methods for electrolytically depositing pretreatment compositions
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
WO2017079421A1 (fr) 2015-11-04 2017-05-11 Ppg Industries Ohio, Inc. Compositions de prétraitement et procédés de traitement d'un substrat
US10113070B2 (en) 2015-11-04 2018-10-30 Ppg Industries Ohio, Inc. Pretreatment compositions and methods of treating a substrate
WO2018031996A1 (fr) 2016-08-12 2018-02-15 Ppg Industries Ohio, Inc. Composition de prétraitement
WO2018032010A1 (fr) 2016-08-12 2018-02-15 Prc-Desoto International, Inc. Systèmes et procédés de traitement d'un substrat métallique par prétraitement de film mince et composition d'étanchéité
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
WO2018039462A1 (fr) 2016-08-24 2018-03-01 Ppg Industries Ohio, Inc. Composition alcaline destiné au traitement de substrats métalliques
WO2019243973A2 (fr) 2018-06-22 2019-12-26 Ppg Industries Ohio, Inc. Procédé d'amélioration de la résistance à la corrosion d'un substrat métallique
US11566330B2 (en) 2019-04-16 2023-01-31 Ppg Industries Ohio, Inc. Systems and methods for maintaining pretreatment baths
WO2020214592A1 (fr) 2019-04-16 2020-10-22 Ppg Industries Ohio, Inc. Systèmes et procédés de maintien de bains de prétraitement
WO2021071574A1 (fr) 2019-10-10 2021-04-15 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat
WO2022187847A1 (fr) 2021-03-05 2022-09-09 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat
WO2022197357A1 (fr) 2021-03-19 2022-09-22 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat
WO2023015060A1 (fr) 2021-08-03 2023-02-09 Ppg Industries Ohio, Inc. Systèmes et procédé de traitement d'un substrat
WO2023102284A1 (fr) 2021-12-03 2023-06-08 Ppg Industries Ohio, Inc. Systèmes et procédés de traitement d'un substrat

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ZA954578B (en) 1996-01-25
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JPH07331276A (ja) 1995-12-19

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