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WO1999002758A1 - Bain et procede de traitement aqueux pour surfaces aluminiferes - Google Patents

Bain et procede de traitement aqueux pour surfaces aluminiferes Download PDF

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Publication number
WO1999002758A1
WO1999002758A1 PCT/US1998/013590 US9813590W WO9902758A1 WO 1999002758 A1 WO1999002758 A1 WO 1999002758A1 US 9813590 W US9813590 W US 9813590W WO 9902758 A1 WO9902758 A1 WO 9902758A1
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WO
WIPO (PCT)
Prior art keywords
substrate
surface treatment
aluminiferous
water
aqueous
Prior art date
Application number
PCT/US1998/013590
Other languages
English (en)
Inventor
Masayuki Yoshida
Akio Shimizu
Kenchiro Oshita
Original Assignee
Henkel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US09/462,704 priority Critical patent/US6369149B1/en
Application filed by Henkel Corporation filed Critical Henkel Corporation
Publication of WO1999002758A1 publication Critical patent/WO1999002758A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates

Definitions

  • This invention relates to a novel surface treatment liquid composition , usually for brevity called hereinafter a "bath”, even though it may be applied to surfaces by other methods than immersion, that imparts an excellent corrosion resistance and paint
  • aluminiferous surfaces i.e., a surface of pure aluminum or of any aluminum alloy that contains at least 50 atomic percent of aluminum
  • the invention also relates to a process for treating the surface of aluminiferous materials using this novel surface treatment bath.
  • the o present invention can be applied with particularly good results to the surface treatment of drawn-and-ironed, alternatively called “draw-ironed” and hereinafter usually abbreviated as "Dl", aluminum cans.
  • the present invention relates most specifically and most preferably to a novel aqueous surface treatment bath (1) that imparts an excellent corrosion resistance and paint adherence to the surfaces of 5 aluminum Dl cans prior to the painting or printing of the can surfaces and (2) that also supplies the excellent slidability required for the smooth conveyor transport of the cans (hereinafter abbreviated simply as slidability).
  • the invention additionally relates to a process for treating the surface of aluminiferous materials using the described surface treatment bath.
  • Dl cans are already known as a type of two piece can.
  • a Dl can is fabricated by a drawing process and an ensuing ironing process.
  • Tin-plated steel and aluminum alloy are used as the metal stock for Dl cans based on their excellent workabilities.
  • Draw- ironed aluminum alloy cans are in wide use at the present time for beer and carbonated 5 beverages.
  • Conversion treatment is a process in which a coating is formed on a surface by chemical reactions that occur, without any need for imposition of electric current from an outside source, when the workpiece and a treatment bath are brought into contact. This process is also known as “chemical conversion coating” and “conversion coating”.
  • Phosphate-chromate conversion treatments employ conversion treatment baths that contain hexavalent chromium and are thus a burden on wastewater treatment and are undesirable from an environmental standpoint.
  • the surface treatment coatings produced by zirconium system conversion treatments suffer from problems, vide infra, with regard to corrosion resistance (particularly resistance to retort whitening), adherence (particularly in the case of a neck- in with its high degree of working), and slidability.
  • the outer wall is typically printed with any of various designs adapted to the fill that will be introduced later and the inner wall is painted with a paint that will improve the corrosion resistance.
  • both the inner and outer walls are overcoated with paint or ink and only the outer surface of the bottom of the can is typically left unpainted.
  • the sterilization conditions vary as a function of the particular fill.
  • the sterilization methodologies include sterilization by immersing the can in hot water at 65 to 90 °C and more severe, higher temperature sterilization methods in which the can is exposed to an atmosphere at 115 to 130 °C (generally a retort treatment).
  • retort treatment is carried out when the fill is cafe au lait or tea.
  • the bottom of a Dl aluminum alloy can is basically left unpainted.
  • the coating produced by the surface treatment exhibits a poor corrosion resistance, the aluminum will become oxidized (corroded) in this region during the sterilization processes under discussion and a discolored appearance will be produced.
  • a black discoloration is typically produced by immersion in hot water
  • a white discoloration is typically produced by retort treatment.
  • Aluminum oxide is white in its native form, but in the case of immersion in hot water the growing oxide takes up, for example, the hardness components in the water and takes on a black color. These phenomena are generally known as "whitening” and “blackening”.
  • the surface treatment coatings produced by the heretofore known phosphate-chromate conversion treatments and zirconium system conversion treatments are prone to undergo whitening during retort treatment, and the bottom is often painted in commercial applications to counter this problem.
  • a type of primer known as a size coat or sizing may be applied prior to printing when a retort treatment will be carried out.
  • No surface treatment coating is known at the present time that exhibits a high corrosion resistance and that, in the absence of a size coat, can prevent a loss of ink adherence during retort treatment.
  • Another problem area in the can fabrication process is the frequent transport upsets that can occur during the conveyor transport of cans. These upsets occur when a can tips over sideways and are due to the poor slidability of the can surface caused by a high friction coefficient of the outer can surface.
  • Can conveyability is a particularly critical issue for transport to the printer. This creates a requirement in the can fabrication process for a reduction in the coefficient of static friction of the cans without any associated impairment in the adherence of the paint or ink that will be applied to the can.s
  • An example of methods for improving the slidability is the invention disclosed in Japanese Patent Application Laid Open (Kokai or Unexamined) Number Sho 64-85292 (85,292/ 1989).
  • This invention relates to a surface treatment agent for metal cans that contains water-soluble organic substance selected from phosphate esters, alcohols, monovalent and polyvalent fatty acids, fatty acid derivatives, and mixtures of the preceding.
  • water-soluble organic substance selected from phosphate esters, alcohols, monovalent and polyvalent fatty acids, fatty acid derivatives, and mixtures of the preceding.
  • Another method directed to improving the slidability is the invention disclosed in Japanese Patent Application Laid Open (Kokai or Unexamined) Number Hei 5-239434 (239,434/1993). This method, which uses phosphate ester, again produces an increase in the slidability, but again also does not produce improvements in the corrosion resistance or paint adherence.
  • the lid is rolled on and the can is sealed.
  • the desire to economize on lid stock has resulted in the use of lid diameters that are smaller than the diameter of the can body.
  • the constriction or reduction in the diameter of the can body is known as the "neck-in”.
  • the diameter of the 350 milliliter (hereinafter usually abbreviated as "mL") can body primarily used for beer, etc. is denoted as "211" for (2 + 11/16) inches, while the lid diameter is (2 + 6/16) inches or "206".
  • the lid end of the can body is necked in from 211 to 206.
  • the object of the present invention is to solve the problems described above for the prior art. More specifically, the object of the present invention is to provide a surface treatment bath and surface treatment process that can form on aluminiferous stock a surface treatment coating that (a) exhibits a high corrosion resistance during high-temperature sterilization (retorting) and does not whiten the surface of the workpiece during high-temperature sterilization, (b) renders a size coating (primer coating) unnecessary, (c) has a slidability that provides an excellent can conveyability during the can fabrication process, and (d) has an excellent adherence even when subjected to neck-in working. DESCRIPTION OF THE INVENTION, INCLUDING PREFERRED EMBODIMENTS
  • an aqueous surface treatment bath for aluminiferous materials that characteristically has a pH from 2.5 to 4.5 and contains at least 0.1 gram of phosphate ions per liter of total treatment bath, this concentration unit of grams of any particular constituent per liter of total treatment bath being hereinafter usually abbreviated as "g/L", from 0.1 to 3 g/L of condensed phosphate ions, from 0.1 to 0.5 g/L of free hydrofluoric acid, and at least 0.1 g/L of water-soluble polymer molecules that, except for short end groups as generally known in the art, conform to general formula (I) below:
  • n is the degree of polymerization and has an integral value or each molecule, the average value of n for all of the molecules present being from 2 to 50 and not necessarily integral
  • Another embodiment of the invention is a process for treating the surface of aluminiferous materials that is characterized by the formation of a coating on the surface of an aluminiferous material by dipping said surface for at least 5 seconds in, or by intermittently spraying said surface for a total treatment time of at least 5 seconds with, an above-described surface treatment bath according to the invention that is maintained during its contact with the aluminiferous surface being treated at a temperature of at least 35 °C, subsequently rinsing with water, and then drying by heating at at least one temperature from 160 to 240 °C, the coating formed containing carbon in an amount of from 3 to 40 milligrams of carbon per square meter of the coating formed, this unit of surface mass increase per unit area during the coating process being hereinafter usually abbreviated as "mg/m 2 " and being applicable to other materials as well as to carbon, the coating formed also containing phosphorus in an amount from 0.5 to 10 mg/m 2 .
  • Orthophosphoric acid i.e., H 3 PO 4
  • sodium phosphate i.e., Na 3 PO 4
  • other sufficiently water-soluble salts can be used to furnish phosphate ions to a treatment bath according to the invention.
  • the phosphate ions content must be at least 0.1 g/L and is preferably from 0.3 to 3 g/L and more preferably is from 0.4 to 2.2 g/L. At below 0.1 g/L the reactivity is poor and an acceptable coating will not usually be formed as a result. While good-quality coatings are formed at above 3 g/L, such concentrations are uneco- nomical due to the corresponding high cost of the treatment bath.
  • the condensed phosphate ions consist of at least one selection from the pyrophosphate ions, tripolyphosphate ions, tetrapolyphosphate ions, and the like conforming to the general chemical formula P x O (3x+1) (x+2 " , where "x" represents a positive integer that is at least 2.
  • the condensed phosphate ions can be supplied using either acid or salt.
  • pyrophosphoric acid H 4 P 2 O 7
  • sodium pyrophosphate Na 4 P 2 O 7
  • the condensed phosphate ions concentration must be from 0.1 to 3 g/L and is preferably from 0.3 to 1.5 g/L and more preferably is from 0.4 to 1.2 g/L. Concentrations below 0.1 g/L result in a weak etch and failure usually to form an acceptable coating. Concentrations in excess of 3 g/L result in an overly strong etch and inhibition of the coating-forming reactions.
  • the free hydrofluoric acid i.e., HF
  • hydrofluoric acid could simply be called hydrofluoric acid, but the "free” is added in order to exclude F ⁇ ions bonded by complex coordinate bonds to metal ions such as aluminum ions.
  • Metal ions, such as aluminum ions, will be introduced when an aqueous surface treatment bath according to the present invention is used on a repetitive basis.
  • the free hydrofluoric acid content must be from 0.1 to 0.5 g/L and is preferably from 0.1 to 0.3 g/L. Concentrations below 0.1 g/L result in a weak etch and failure to form an acceptable coating. Concentrations in excess of 0.5 g/L result in an overly strong etch and inhibition of the coating-forming reactions.
  • n denotes the average degree of polymerization of the water-soluble polymer molecules with formula (I) and must have a value from 2 to 50 and preferably has a value from 4 to 45.
  • a value below 2 results in an excessively low molecular weight and hence in an inability to improve the corrosion resistance. Values in excess of 50 result in a decline in the stability of the aqueous bath and thus create the risk of problems appearing during actual applications.
  • X is hydrogen or a group Y with formula (II).
  • Y moieties must be present in the polymer molecules, and the molar ratio of the Y moieties to the moles of aromatic rings in the polymer should be from 0.2:1.0 to 1.0: 1.0.
  • a ratio below 0.2:1.0 gives a sparingly water- soluble polymer, which will cause problems with treatment bath stability. At the other extreme, at a ratio in excess of 1.0 the water solubility becomes too high and an acceptable coating will not be formed.
  • the molar ratio as defined above is preferably from 0.3 to 0.7.
  • the R 1 and R 2 moieties in Y are independently selected from C, to C 3 alkyl and C, to C 3 hydroxyalkyl moieties.
  • the R 1 and R 2 moieties become too bulky, resulting in a coarse coating and hence in a diminished corrosion resistance, when they contain more than 3 carbon atoms.
  • the water-soluble polymer with formula (I) can be prepared by the usual methods. For example, this polymer can be prepared by the polycondensation of phenol and formaldehyde and then introduction of the functional group X using formaldehyde and amine. Formalin is typically used as the formaldehyde.
  • An aqueous surface treatment bath according to the present invention must contain at least 0.1 g/L of the water-soluble polymer, measured as polymer solids only, and preferably contains from 0.2 to 5 g/L and more preferably from 0.5 to 4 g/L, measured in the same way.
  • a concentration below 0.1 g/L makes it extremely difficult to induce stable coating formation on the surface of the workpiece.
  • the high cost of the treatment bath can become an economic problem.
  • the pH of the treatment bath should be from 2.5 to 4.5 and is preferably from 2.8 to 4.5.
  • a pH below 2.5 results in an overly strong etch and scanty coating formation.
  • the polymer has a pronounced tendency to precipitate, which results in a shortened bath life.
  • the pH can be adjusted using an acid such as phosphoric acid, nitric acid, or hydrochloric acid, or a base such as sodium hydroxide, sodium carbonate, or ammonium hydroxide.
  • Problems can be produced by treatment bath foaming when a spray treatment is carried out. The appearance of foaming is strongly dependent on the equipment conditions, but, when changing the equipment conditions does not lead to sufficient improvement, a defoamer may be added to the treatment bath.
  • Aluminum stock and aluminum alloy stock are examples of aluminiferous materials to which the aqueous surface treatment bath according to the present invention may be applied.
  • the aluminum alloy preferably contains at least 80 weight percent of alumin- um and more preferably at least 90 weight percent of aluminum; examples of the alloying component are copper, silicon, magnesium, and manganese.
  • Specific examples of the alloy are aluminum/manganese alloys of the Japanese Industrial Standard (hereinafter usually abbreviated as "JIS") A3000 system and aluminum/magnesium alloys of the JIS A5000 system.
  • the shape of the aluminiferous material is not critical and can be exemp- lified by plate, sheet, coil, and can.
  • aluminum Dl can is the most preferred aluminiferous material for application of the aqueous surface treatment bath according to the present invention.
  • the treatment bath according to the present invention can be applied, for example, according to the following process, which is provided as a preferred example.
  • Surface cleaning degreasing (can be carried out using acid, alkali, or solvent)
  • Water rinse
  • Treatment temperature 35 to 65 °C treatment method: dipping or spraying treatment time: 5 to 30 seconds
  • a surface treatment bath according to the present invention should be used heated to at least 35 °C and preferably at 35 to 65 °C.
  • the reactivity is usually inadequate below 35 °C, preventing the formation of good-quality coatings. While good-quality coatings are formed above 65 °C, the high energy costs for heating associated with such temperatures are economically undesirable.
  • the dipping treatment time should normally be at least 5 seconds and preferably from 5 to 30 seconds. The reaction is usually inadequate in less than 5 seconds, preventing the formation of a coating with an excellent corrosion resistance. Treatment times in excess of 30 seconds provide no additional increase in performance.
  • the bath should be sprayed intermittently, with a preferred interval of from 1 to 5 seconds between periods of spraying.
  • the total time of spraying during treatment, when spraying is the means of establishing contact normally should be at least 5 seconds and is preferably from 7 to 30 seconds.
  • the reaction will usually be inadequate in less than 5 seconds, preventing the formation of a coating with an excellent corrosion resistance.
  • treatment times in excess of 30 seconds provide no additional increase in performance.
  • a workpiece After being contacted with the bath, a workpiece preferably is rinsed with water and then with deionized water, and then independently preferably is heated to at least one elevated temperature in a range from 160 to 240 °C, for a sufficient time to dry the workpiece if it is not already dry when heating is begun.
  • This heating and, optionally, drying is believed to cause an increase in the molecular weight of the water-soluble polymer (oligomer) adhering on the surface, and, whatever the actual chemical reason, results in the development of a more satisfactory corrosion resistance.
  • This increase in corrosion resistance will not usually adequately develop at drying temperatures below 160 °C, while temperatures in excess of 240 °C will in many cases cause a reduction in the strength of the metal substrate and therefore are undesirable.
  • the increase in corrosion resistance requires a certain amount of time at the elevated temperature; this time independently preferably is at least, with increasing preference in the order given, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0 minutes and independently, primarily for reasons of economy, preferably is not more than, with increasing preference in the order given, 30, 20, 10, 5.0, 4.0, 3.0, or 2.5 minutes.
  • heating and drying are accomplished simultaneously by beginning drying as soon as practically possible after the last rinsing operation, or at least while the surface that has been treated is still wet.
  • the added-on mass (hereinafter usually abbreviated as "add-on") of the coating formed per unit area of the surface of the aluminiferous material preferably includes from 3 to 40 "mg/m 2 of carbon and from 0.5 to 10 mg/m 2 of phosphorus.
  • a satisfactory corrosion resistance is not usually obtained when the carbon add-on falls below 3 mg/m 2 or the phosphorus add-on falls below 0.5 mg/m 2 .
  • interference coloration which compromises the appearance, will often appear on the treated surface when the carbon add-on exceeds 40 mg/m 2 or when the phosphorus add-on exceeds 10 mg/m 2 .
  • the preferred carbon add-on is from 5 to 35 mg/m 2 and the preferred phosphorus add-on is from 0.5 to 8 mg/m 2 .
  • Aqueous surface treatment baths according to the present invention and processes for treating the surface of aluminiferous materials using this bath will be explained hereinbelow through a variety of working examples. The efficacy of these working examples will become clear through comparison with the comparative examples. The compositions of the aqueous surface treatment bath and the conditions of the surface treatment process are explained individually in each example and comparative example.
  • a commercial cleaner PALKLIN® 500 from Nihon Parkerizing Co. Ltd.
  • the coating add-ons to the treated aluminum alloy surface were quantitatively measured.
  • the carbon add-on was determined using a commercial surface carbon analyzer.
  • the sample size was 32 square centimeters, and the measurement conditions were set at 500 °C for 5 minutes.
  • the phosphorus add-on was determined using a commercial x-ray fluorescence analyzer. The sample size in this case was 3 centimeters in diameter.
  • the corrosion resistance was evaluated through both the resistance to blackening and the resistance to retort whitening.
  • To evaluate the resistance to blackening the treated but unpainted can was dipped in boiling tapwater for 30 minutes, after which the change in appearance was evaluated. No blackening was scored as + +, partial blackening was scored as +, and blackening over the entire surface was scored as *.
  • To evaluate the resistance to retort whitening the treated but unpainted can was retorted at 121 °C for 30 minutes, after which the change in appearance was evaluated. No whit- ening was scored as + +, partial whitening was scored as +, and whitening over the entire surface was scored as x.
  • the treated can lacking a size coating, was printed with a commercial ink for outer can surfaces.
  • the can was then retorted at 121 °C for 30 minutes, after which the ink adherence was evaluated by peeling with adhesive tape. No delamination was scored as + +, partial delamination was scored as +, and complete delamination was scored as *.
  • the treated can was painted with a commercial exterior surface white paint to give a thickness of 10 micrometres ( hereinafter usually abbreviated as " ⁇ m").
  • ⁇ m 10 micrometres
  • the can was then necked-in to 202 using a commercial necking machine, after which the adherence in the neck region was evaluated. No paint film delamination was scored as + +, partial delamination was scored as +, and complete delamination was scored as *.
  • Example 2 The aqueous surface treatment bath described below was used for the treatment.
  • Example 3 The aqueous surface treatment bath described below was used for the treatment. The add-ons for the resulting coating are also reported below.
  • Aqueous surface treatment bath 3 phosphate ions (added as 75 % H 3 PO 4 in water) 1.0 g/L pyrophosphate ions (added as Na 4 P 2 O 7 ) 1.0 g/L free hydrofluoric acid (HF) 0.2 g/L aluminum (Al) was added dissolved in hydrofluoric acid (HF) (Al 0.2 g/L, HF 0.44 g/L) water-soluble polymer solids 0.5 g/L pH 3.5 (adjusted with sodium hydroxide) Water-soluble polymer 3 n 10
  • Example 4 The aqueous surface treatment bath described below was used for the treatment. The add-ons for the resulting coating are also reported below.
  • Example 5 The aqueous surface treatment bath described below was used for the treatment. The add-ons for the resulting coating are also reported below.
  • Comparative Example 1 The aqueous surface treatment bath described below was used for the treatment. The add-ons for the resulting coating are also reported below.
  • Aqueous surface treatment bath 6 phosphate ions (added as 75 % H 3 PO 4 in water) 0.5 g/L free hydrofluoric acid (as HF) 0.3 g/L water-soluble polymer solids 1.0 g/L
  • Aqueous surface treatment bath described below was used for the treatment.
  • the add-ons for the resulting coating are also reported below.
  • Comparative Example 3 Treatment was carried out in this instance using a 3 % aqueous solution of a commercial phosphate-chromate surface treatment bath concentrate (ALODINE® 401 from Nihon Parkerizing Co., Ltd.). The add-ons for the resulting coating are reported below.
  • Table 1 reports the results from the performance evaluation tests carried out on the coatings produced in Examples 1 to 5 and Comparative Examples 1 to 4.
  • Examples 1 to 5 employed aqueous surface treatment baths according to the present invention and surface treatment processes using this bath, and, as demonstrated by the results in Table 1 , the coatings produced in Examples 1 to 5 gave excellent values for all the properties considered (corrosion resistance, adherence, and slidability). In contrast to this, the coatings produced in Comparative Examples 1 to 4 gave poorer values for almost all of the properties considered (corrosion resistance, adherence, and slidability), and each one of the Comparison Examples gave at least one value that was very much poorer than that achieved with the examples according to the invention. Good-quality coatings were not produced in Comparative Examples 1 and 2; Comparative Example 3 used a commercial phosphate-chromate agent; and Comparative Example 4 used a commercial zirconium system agent. BENEFITS OF THE INVENTION
  • a coating with an excellent corrosion resistance (particularly resistance to retort whitening), excellent paint adherence, and excellent slidability can be formed on the surface of aluminiferous materials through the use of the surface treatment bath for aluminiferous materials according to the present invention and the surface treatment process using said bath.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Cette invention se rapporte à un bain de traitement surfacique aqueux possédant un pH compris entre 2,5 et 4,5 et contenant au moins 0,1g/L d'ions orthophosphate, de 0,1 à 3 g/L d'ions phosphate condensés, de 0,1 à 0,5 g/L d'acide hydrofluorique libre, et au moins 0,1 g/L de molécules d'un polymère soluble dans l'eau qui, à l'exception des groupes terminaux courts bien connus, est représenté par la formule (I), dans laquelle n est le degré de polymérisation et possède une valeur entière pour chaque molécule, la valeur moyenne de n pour toutes les molécules présentes étant comprise entre 2 et 50 et n'étant pas obligatoirement entière, X est un atome d'hydrogène ou une fraction Y représentée par la formule générale (II), dans laquelle R1 et R2 sont chacun une fraction alkyle ou une fraction hydroxy-alkyle possédant de 1 à 3 atomes de carbone, le rapport du nombre total de fractions Y au nombre total de noyaux aromatiques étant compris entre 0,2/1,0 et 1,0/1,0. Ce bain sert à la fabrication de revêtements offrant une excellente résistance à la corrosion (notamment une résistance au blanchiment en autoclave), un excellent coefficient de glissement et une excellente adhérence de la peinture sur des matières aluminifères.
PCT/US1998/013590 1997-07-11 1998-07-09 Bain et procede de traitement aqueux pour surfaces aluminiferes WO1999002758A1 (fr)

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US09/462,704 US6369149B1 (en) 1997-07-11 1998-07-08 Aqueous treatment process and bath for aluminiferous surfaces

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JPH9-202,525 1997-07-11
JP20252597A JPH1135880A (ja) 1997-07-11 1997-07-11 アルミニウム系材料用水性表面処理液およびそれを用いる表面処理方法

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JP5111701B2 (ja) * 2001-09-11 2013-01-09 日本ペイント株式会社 アルミニウムまたはアルミニウム合金の表面処理方法
JP5311266B2 (ja) * 2005-09-09 2013-10-09 東洋製罐株式会社 耐食性、密着性に優れる樹脂被覆シームレスアルミニウム缶
EP1932944B1 (fr) 2005-09-09 2020-01-08 Toyo Seikan Kaisha, Ltd. Boite metallique en aluminium sans soudure enduite de resine et couvercle en alliage d'aluminium enduit de resine
JP4915068B2 (ja) * 2005-09-09 2012-04-11 東洋製罐株式会社 耐食性、密着性に優れるアルミニウム合金缶蓋及びその製造方法
US8871351B2 (en) * 2006-02-09 2014-10-28 Toyo Seikan Kaisha, Ltd. Easy-open end

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4178400A (en) * 1976-12-30 1979-12-11 Amchem Products, Inc. Autodeposited coatings
US4347172A (en) * 1971-03-10 1982-08-31 Amchem Products, Inc. Process and composition for coating metals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347172A (en) * 1971-03-10 1982-08-31 Amchem Products, Inc. Process and composition for coating metals
US4178400A (en) * 1976-12-30 1979-12-11 Amchem Products, Inc. Autodeposited coatings

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