WO2000024948A1 - Composition et procede de traitement de surfaces metalliques - Google Patents

Composition et procede de traitement de surfaces metalliques Download PDF

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Publication number
WO2000024948A1
WO2000024948A1 PCT/US1999/023982 US9923982W WO0024948A1 WO 2000024948 A1 WO2000024948 A1 WO 2000024948A1 US 9923982 W US9923982 W US 9923982W WO 0024948 A1 WO0024948 A1 WO 0024948A1
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Prior art keywords
component
bath
treatment
aqueous liquid
alloys
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PCT/US1999/023982
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English (en)
Inventor
Kazuya Nakada
Motoki Kawaguchi
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Henkel Corporation
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Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to US09/830,736 priority Critical patent/US6361833B1/en
Priority to BR9914970-2A priority patent/BR9914970A/pt
Priority to AU20202/00A priority patent/AU2020200A/en
Priority to CA002349376A priority patent/CA2349376A1/fr
Priority to EP99963840A priority patent/EP1171648A1/fr
Publication of WO2000024948A1 publication Critical patent/WO2000024948A1/fr

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Classifications

    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds

Definitions

  • This invention relates to a novel aqueous liquid composition, which is usually hereinafter called a "bath” for brevity, without any implication thereby that it must be used by immersion only, and to a process for treating a metal surface.
  • the composition and process can provide the surfaces of various metals, especially aluminum, aluminum alloys, magnesium, magnesium alloys, and galvanized steel sheet, with an excellent corrosion resistance and excellent paint adherence.
  • the baths used to treat aluminum and aluminum alloy surfaces can be broadly classified into chromate-type baths and non-chromate-type baths. Chromic acid chro- mate conversion baths and phosphoric acid chromate conversion baths are typical examples of the chromate-type treatment baths.
  • Chromic acid chromate conversion baths first reached practical application in about 1950 and even now are widely used for the surface treatment of automotive heat exchangers, aluminum wheels, building materials, and aerospace materials.
  • the main components in chromic acid chromate conversion baths are chromic acid and a fluoride reaction accelerator. This type of bath produces a conversion coating containing moderate amounts of hexavalent chromium on the metal surface.
  • Phosphoric acid chromate conversion baths originated with the invention disclosed in United States Patent No. 2,438,877.
  • the main components in phosphoric acid chromate conversion baths are chromic acid, phosphoric acid, and hydrofluoric acid.
  • a conversion coating whose main component is hydrated chromium phosphate is formed by this type of bath on the metal surface. Since the resulting conversion coating does not contain hexavalent chromium, this type of bath is in wide use at the present time as an underpaint treatment for the body stock and lid stock of beverage cans.
  • the treatment bath disclosed in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Sho 52-131937 (131 ,937/1977) is an invention typical of the chromium-free non-chromate-type surface treatment baths.
  • This non-chromate-type surface treatment bath offers the advantage of not containing hexavalent chromium and for this reason is widely used at present for treating aluminum drawn-and-ironed, hereinafter usually abbreviated as "Dl", can surfaces.
  • Dl aluminum drawn-and-ironed
  • the treatment method disclosed in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Sho 57-41376 (41 ,376/1982) comprises treating the surface of aluminum, magnesium, or an alloy thereof with an aqueous solution containing at least one selection from titanium salts and zirconium salts, at least one selection from imida- zole derivatives, and an oxidizer selected from nitric acid, hydrogen peroxide, and potassium permanganate. While the corrosion resistance of the coatings produced by this treatment bath would have been considered acceptable 15 years ago, this level of corrosion resistance is not unequivocally satisfactory at the present time.
  • Japanese Laid Open (Kokai or Unexamined) Patent Application Number Sho 56- 136978 (136,978/1981) teaches a conversion bath that characteristically comprises an aqueous solution containing a vanadium compound and at least one compound selected from the group consisting of titanium salts, zirconium salts, and zinc salts.
  • the conversion coating formed by this treatment bath cannot be expected to have a corrosion resistance better than or even as good as that of a chromate film in the case of challenge by long-term anticorrosion testing.
  • This treatment process comprises a phosphate treatment followed by a silicate treatment and then execution of a silicone treatment after the silicate treatment.
  • the phosphate treatment coating by itself provides a low level of corrosion resistance and paint adherence when used as an underpaint treatment for magnesium and magnesium alloy surfaces.
  • This treatment method also requires a multistage treatment process, uses high treatment temperatures, and requires long treatment times.
  • the known phosphate-based surface treatment methods for magnesium and its alloys include methods that employ treatment baths based on zinc phosphate, iron phosphate, calcium phosphate, or zirconium phosphate. However, these methods are not believed to have consistently provided a corrosion resistance that is satisfactory at a practical level.
  • a manganese phosphate treatment is disclosed in category 7 of JIS H-8651. This treatment bath is not acceptable from a practical standpoint because it contains chromium, requires high treatment temperatures of 80 °C to 90 °C, and requires long treatment times of 30 to 60 minutes.
  • Non-chromate-type technology is found in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 9-228062 (228,062/1997), which teaches a surface treatment process that uses an aqueous solution that contains at least one organometal compound selected from metal alkoxides, metal acetylaceton- ates, and metal carboxylates and at least one film-formation stabilizer or film-formation auxiliary selected from acids, bases, their salts, and organic compounds containing the hydroxyl group, carboxyl group, or amino group.
  • This aqueous solution is applied to magnesium stock at from 0 to 50 °C.
  • the conversion coating formed by this treatment bath cannot be expected to have a corrosion resistance better than or even as good as that of a chromate film in the case of challenge by long-term anticorrosion testing.
  • Chromate treatments and zinc phosphate treatments are the treatment processes generally applied to galvanized materials.
  • the chromate treatments provide an excellent coating performance, but the corresponding treatment baths contain toxic chromium and hence raise issues with regard to the working environment and effluent discharge.
  • the zinc phosphate treatments in some cases are unable to provide an acceptable corrosion resistance.
  • Patent Application Number Hei 1 -104783 discloses a process for producing surface-treated steel sheet.
  • steel sheet plated with zinc, aluminum, or a zinc-aluminum alloy is coated with an alcohol solution containing at least one selection from the alkoxides and acetylacetonates of Si, Ti, Zr, Al, W, Ce, Sn, and Y.
  • An oxide of the metal present in the solution is then formed on the surface of the steel sheet by heating to 200 to 500 °C after application of the bath.
  • This preparative method suffers from issues with the working environment and energy costs, because it must use a flammable alcohol and requires fairly high temperatures for coating formation.
  • a major object of the present invention is to provide a non-polluting composition and process for treating surfaces of at least one of aluminum and its alloys, magnesium and its alloys, and steel coated with zinc and its alloys that can impart thereto an excellent corrosion resistance and excellent paint adherence.
  • highly corrosion-resistant, highly paint-adherent conversion coatings can be formed on metal surfaces by the use of a special surface treatment composition that contains in suitable proportions at least one metal acetylacetonate selected from the group consisting of AI(C 5 H 7 O 2 ) 3 , V(C 5 H 7 O 2 ) 3 , VO(C 5 H 7 O 2 ) 2 , Zn(C 5 H 7 O 2 ) 2 , and Zr(C 5 H 7 O 2 ) 4 , and at least one compound selected from water-soluble inorganic titanium compounds and water-soluble inorganic zirconium compounds.
  • a special surface treatment composition that contains in suitable proportions at least one metal acetylacetonate selected from the group consisting of AI(C 5 H 7 O 2 ) 3 , V(C 5 H 7 O 2 ) 3 , VO(C 5 H 7 O 2 ) 2 , Zn(C 5 H 7 O 2 ) 2 , and Zr(C 5 H 7 O 2 ) 4
  • a composition according to the present invention for treating metal surfaces comprises, preferably consists essentially of, or more preferably consists of, water and the following components:
  • (B) a component of at least one compound selected from water-soluble inorganic titanium compounds and water-soluble inorganic zirconium compounds, components (A) and (B) being present at a weight ratio of (A) to (B) that is from 1 : 5,000 to 5,000 : 1.
  • a bath according to the present invention for treating metal surfaces preferably, independently for each preference: has a pH from 2.0 to 7.0; contains from 0.01 to 50 grams of component (A) as described above per liter of bath, this unit of concentration being freely applied hereinafter to any constituent of the bath and being usually abbreviated as "g/l"; and contains from 0.01 to 50 g/l of component (B) as described above.
  • a process according to the present invention for treating metal surfaces preferably forms on said metal surface an organic-inorganic composite conversion coating at a coating weight of 5 to 2,000 milligrams of coating per square meter of the surface coated, this unit of coating weight being hereinafter usually abbreviated as "mg/m 2 ", by bringing the above-described bath for treating metal surfaces into contact with aluminum or an alloy thereof, magnesium or an alloy thereof, or zinc or an alloy thereof.
  • An important feature of the present invention is the formation of an organic- inorganic composite coating. It is believed that the corrosion resistance of the resulting conversion coating in particular is improved through the formation of this organic- inorganic composite coating.
  • the water-soluble inorganic titanium compound and/or water-soluble inorganic zirconium compound which is an essential component in the surface treatment composi- tion of the present invention, can be one or more selections, for example, from the sul- fates, oxysulfates, nitrates, phosphates, chlorides, ammonium salts, and fluorides of titanium and zirconium.
  • this component is a water-soluble inorganic compound, its specific type is not critical. However, at least for economy, at least one of fluorotitanic and fluorozirconic acids and the salts of both of these acids are preferred.
  • the water-soluble inorganic titanium and/or zirconium compound(s) are believed to precipitate on the surface of the metal workpiece as, for example, the oxide, phosphate, or fluoride of Ti or Zr and thus to form a framework or skeletal element of the organic-inorganic composite coating that is produced with the simultaneously precipitating metal acetylacetonate.
  • the presence of the Ti and/or Zr also improves the barrier performance (interception capability) of the coating with respect to corrosive environments and as a result makes possible the formation of a coating that has a corrosion resistance and paint adherence superior to the use of only the metal acetylacetonate.
  • the metal acetylacetonate : water-soluble inorganic compound concentration ratio preferably is at least, with increasing preference in the order given, 1.00:100, 1.00:50, 1.00:10, 1.00:7.0, 1.00:5.0, 1.00:3.0, 1.00:2.0, or 1.00:1.40 and independently preferably is not more than, with increasing preference in the order given, 400:1.00, 100:1.00, 10:1.00, 7.0:1.00, 5.0:1.00, or 2.5:1.00.
  • the organic-inorganic composite coating formed when this weight ratio is below 1 :5000 will have a poor corrosion resistance, while production of the organic-inorganic composite coating itself becomes difficult at above 5000:1.
  • a bath according to the present invention for treating metal surfaces essentially employs water and the hereinabove described surface treatment composition.
  • This bath contains the metal acetylacetonate preferably at from 0.01 to 50 g/l and more preferably at from 0.1 , or still more preferably, 1.0, to 20 g/l. While a conversion coating will be formed at a metal acetylacetonate content below 0.01 g/l, such a coating will usually have a poor corrosion resistance and paint adherence. Good quality conversion coatings are still formed at above 50 g/l, but since no additional increment in performance is obtained above 50 g/l, such concentrations are uneconomical due to the additional cost of the bath.
  • the content of water-soluble inorganic titanium compound(s) and/or water- soluble inorganic zirconium compound(s) is preferably from 0.01 to 50 g/l and more preferably from 0.05, or still more preferably 0.5, to 10 g/l. While a conversion coating will be formed at a content below 0.01 g/l, such a coating will usually have a poor corrosion resistance. Good quality conversion coatings are still formed at above 50 g/l, but since no additional improvement in performance is obtained above 50 g/l, such s concentrations are uneconomical due to the additional cost of the bath.
  • the pH of a surface treatment bath according to the present invention must be within the range from 2.0 to 7.0 and preferably is within the range from 3.0 to 6.0.
  • a pH below 2.0 hinders precipitation of the metal acetylacetonate on the metal surface and can cause irregularities or unevenness in appearance due to excessive etching of the o metal surface.
  • Formation of a highly corrosion-resistant conversion coating is strongly impaired at a pH above 7.0, and a pH above 7.0 can also cause problems with bath stability due to a pronounced tendency for the metal ions present in the bath to form a precipitate at such pH values.
  • the pH of the surface treatment bath of the present invention can be adjusted into the desired range through the use of an acid such s as nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, or fluorosilicic acid, or a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, or ammonium hydroxide.
  • an acid such as nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, or fluorosilicic acid
  • a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, or ammonium hydroxide.
  • the stability of the treatment bath can be strongly impaired during execution of the surface treatment of the present invention by elution into the bath of metal ions, e.g., o aluminum, magnesium, or zinc ions, from the metal workpiece.
  • metal ions e.g., o aluminum, magnesium, or zinc ions
  • an organic acid or alkali metal salt thereof may be added to the bath as a sequestering agent in order to chelate the metal ions.
  • Organic acids used for this purpose can be exemplified by gluconic acid, heptogluconic acid, oxalic acid, tartaric acid, organophosphonic acids, and ethylenediaminetetraacetic acid. 5
  • An oxidizing agent can also be used in order to accelerate formation of the conversion coating of the present invention.
  • This oxidizing agent can be exemplified by hydrogen peroxide, tungstic acid and its salts, molybdic acid and its salts, permanganic acid and its salts, and water-soluble organoperoxides such as tert-butyl hydroperoxide ((CH 3 ) 3 C-O-OH).
  • the mass per unit area, usually called "coating weight”, of the organic-inorganic composite conversion coating formed by the hereinabove described process is preferably from 5 to 2,000 mg/m 2 and more preferably is from 50, or still more preferably 140, to 500 mg/m 2 .
  • the corrosion resistance and paint adherence may be inadequate at a coating weight below 5 mg/m 2 . While an excellent corrosion resistance is obtained
  • Coating weights above 2,000 mg/m 2 are also undesirable because they can cause a conspicuous unevenness in coating appearance and tend to impair the paint adherence.
  • metal components Al, V, Zn, Zr, Ti
  • their chemical characteristics in the coating itself for example, their bonding status, oxidation state, extent of polymerization or increase in molecular weight, and the like, are not critical.
  • Highly corrosion-resistant, highly paint-adherent conversion coatings can be formed by bringing the surface treatment bath of the invention into contact with aluminum or an alloy thereof, magnesium or an alloy thereof, or zinc or an alloy thereof. This process for treating the surface of various types of metals will be explained in greater detail in the following.
  • the surface treatment bath of the invention is used in a preferred embodiment as part of the following process operations: (1 ) Surface cleaning/degreasing (this can be acidic, neutral, alkaline, or solvent cleaning/degreasing)
  • the surface treatment bath of the present invention is preferably brought into contact with the metal surface for 1 to 600 seconds at 10, or more preferably 35, to 80 °C.
  • the reactivity between the treatment bath and metal surface usually will be inadequate at contact temperatures below 10 °C, and inadequate reactivity will prevent the formation of good quality conversion coatings.
  • a conversion coating is still formed at contact temperatures above 80 °C, but the correspondingly increased energy costs create undesirable economics for such temperatures.
  • the extent of reaction will usually be inadequate at a treatment time below 1 second, preventing the formation of a highly corrosion-resistant conversion coating. At the other end of this range, no additional improvements are seen in the corrosion resistance and paint adherence of the conversion coating at times in excess of 600 seconds.
  • a surface treatment composition bath according to the invention can be advantageously applied to pure aluminum and aluminum alloys that contain at least 50 % by weight of aluminum.
  • the applicable aluminum alloys encompass both multicomponent alloys, e.g., Al-Cu, Al-Mn, Al-Si, Al-Mg, Al-Mg-Si, and Al-Zn-Mg, and metals on which Al plating or Al alloy plating has been executed, for example, Al-plated steel sheet.
  • the surface treatment composition and bath according to the invention can also be advantageously applied to pure magnesium and magnesium alloys that contain at least 50 % by weight of magnesium.
  • Applicable magnesium alloys encompass multi- component alloys such as Mg-AI-Zn, Mg-Zn, and Mg-AI-Zn-Mn, and the magnesium or alloys can be plated on other metals.
  • Zinc and zinc alloys to which the invention can be advantageously applied include in particular metals on which Zn plating has been executed, including hot-dip zinc-plated steel sheet, galvannealed hot-dip zinc-plated steel sheet, Al/Zn alloy-plated steel sheet
  • the surface of the workpiece may be in any condition as long as a metal as described above is present at least at a portion of the surface.
  • the surface can be cold rolled or plated as such, or can have been subjected to a treatment such as shot blasting, roughening with acid or alkali, or activation.
  • sample substrate materials were used in these examples: AL-Mn alloy sheets according to Japanese Industrial Standard ("JIS") 3004, with dimensions of 150 millimeters (hereinafter usually abbreviated as "mm") x 70 mm x 0.2 mm thick; Die-cast sheets with dimensions of 150 mm x 100 mm x 1 mm thick of AZ91 D magnesium alloy as specified by JIS H2222; and Galvannealed hot-dip zinc-plated steel sheets with dimensions of 150 mm x 70 mm x 0.8 mm thick.
  • JIS Japanese Industrial Standard
  • mm 150 millimeters
  • Die-cast sheets with dimensions of 150 mm x 100 mm x 1 mm thick of AZ91 D magnesium alloy as specified by JIS H2222
  • Galvannealed hot-dip zinc-plated steel sheets with dimensions of 150 mm x 70 mm x 0.8 mm thick.
  • the surface-treated samples were prepared by treatment according to the following operations in the sequence (1 ) - (2) - (3) - (4) - (5) - (6).
  • Ambient temperature means temperature as normally maintained in buildings for human comfort, i.e., about 18 - 23 °C.
  • the metal acetylacetonates used are listed below in Table 1
  • the water-soluble titanium compounds used are listed below in Table 2
  • the water-soluble zirconium compounds used are listed below in Table 3
  • the reagents used to adjust the pH of the surface treatment baths are listed below in Table 4, in each instance together with the identifying symbols used for them in later tables.
  • Comparative Example 1 used a metal acetylacetonate as the only component of the treatment bath in order to provide a comparative example testing the formation of a coating of the metal acetylacetonate alone.
  • Comparative Example 2 used a water-soluble titanium compound as the only component of the treatment bath in order to provide a comparative example testing the formation of a coating of the inorganic titanium compound alone.
  • Comparative Example 3 employed a treatment bath comprising both the water-soluble inorganic titanium compound and the water-soluble inorganic zirconium compound in order to provide a comparative example testing the formation of an inorganic composite coating constituted of titanium and zirconium but lacking the metal acetylacetonate.
  • Comparative Example 4 was directed to the formation of coatings with very low coating weights.
  • Comparative Example 5 a 2 % solution in water of a commercial zirconium phosphate surface treatment agent (ALODINE® 4040 from Nihon Parkerizing Co., Ltd.) was used to carry out surface treatment. This solution was applied to the above-de- scribed Al alloy sheet by spraying for 60 seconds at 50 °C, after which the corrosion resistance and paint adherence were evaluated.
  • AODINE® 4040 from Nihon Parkerizing Co., Ltd.
  • Comparative Example 6 an aqueous solution of a commercial phosphoric acid chromate surface treatment agent (mixed aqueous solution of 4 % of ALCHROM® K702SL and 0.3 % of ALCHROM® K702AC, both from Nihon Parkerizing Co., Ltd.) was used to carry out surface treatment. This solution was applied to the above-described Al alloy sheet by spraying for 20 seconds at 50 °C, after which the corrosion resistance and paint adherence were evaluated. Table 5 - Part A
  • Comparative Example 7 a 7 % solution in water of a commercial chromic acid chromate surface treatment agent (ALCHROM® 713M from Nihon Parkerizing Co., Ltd.) was used to carry out surface treatment. This solution was applied to the above-described Al alloy sheet, Mg alloy sheet, and Zn-plated steel sheet by dipping for 60 sec- onds at 40 °C, after which the corrosion resistance and paint adherence were evaluated.
  • a treatment bath based on MIL-M-3171 C TYPE III, with a main component of sodium bichromate
  • Coating Weight The coating weight of the entire organic-inorganic composite coating was measured using either a fluorescence x-ray analyzer or stripping by dipping for 5 minutes at 90 °C in 5 weight % aqueous chromic acid solution.
  • Corrosion Resistance The corrosion resistance was evaluated using the salt spray test described in JIS Z-2371. The extent of corrosion development on the surface- treated sheet was evaluated visually after the salt spray test and reported on the following scale:
  • Paint Adherence Paint adherence testing was carried out on the Al alloy sheet, Mg alloy sheet, and Zn-plated steel sheet samples after surface treatment under the conditions of Examples 1 to 5 and Comparative Examples 1 to 9.
  • the surface of the sample was coated to a dry film thickness of 10 micrometres (hereinafter usually abbreviated as " ⁇ m") with an epoxy resin paint from Kansai Paint Co., Ltd. and the sample was then baked for 10 minutes at 200 °C.
  • a grid of 100 squares (width 2 mm) was subsequently introduced in the center of the painted sheet using a cutter, after which the sample was dipped for 60 minutes in boiling deionized water. After this boiling water challenge, the painted sheet was air-dried and then subjected to a peeling test with cellophane tape. The paint adherence was evaluated on the basis of the number of grid squares that were not peeled off.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

Une composition de traitement de surfaces métalliques contenant, en un rapport pondéral de 1:5000 à 5000:1, au moins un acétylacétonate métallique choisi dans le groupe contenant Al(C5H7O2)3, V(C5H7O2)3, VO(C5H7O2)2, Zn(C5H7O2)2, et Zr(C5H7O2)4, ainsi qu'au moins un composé choisi entre des composés de titane organiques hydrosolubles et des composés de zirconium organiques hydrosolubles, fournit une composition de type non chromate conférant une excellente résistance à la corrosion et une excellente adhérence des peintures à des surfaces de métaux, en particulier l'aluminium et ses alliages, le magnésium et ses alliages, le zinc et ses alliages.
PCT/US1999/023982 1998-10-28 1999-10-27 Composition et procede de traitement de surfaces metalliques WO2000024948A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US09/830,736 US6361833B1 (en) 1998-10-28 1999-10-27 Composition and process for treating metal surfaces
BR9914970-2A BR9914970A (pt) 1998-10-28 1999-10-27 Composição lìquida aquosa para o tratamento deuma superfìcie de metal e processo paraproporcionar um revestimento redutor decorrosão sobre uma superfìcie
AU20202/00A AU2020200A (en) 1998-10-28 1999-10-27 Composition and process for treating metal surfaces
CA002349376A CA2349376A1 (fr) 1998-10-28 1999-10-27 Composition et procede de traitement de surfaces metalliques
EP99963840A EP1171648A1 (fr) 1998-10-28 1999-10-27 Composition et procede de traitement de surfaces metalliques

Applications Claiming Priority (4)

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JP30766598 1998-10-28
JP10/307665 1998-10-28
JP29196799A JP3992173B2 (ja) 1998-10-28 1999-10-14 金属表面処理用組成物及び表面処理液ならびに表面処理方法
JP11/291967 1999-10-16

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001086016A2 (fr) * 2000-05-11 2001-11-15 Henkel Corporation Agent de traitement de surface metallique
US6730414B2 (en) * 2000-11-07 2004-05-04 Nisshin Steel Co., Ltd. Chemically processed steel sheet excellent in corrosion resistance
WO2006108655A1 (fr) * 2005-04-14 2006-10-19 Chemetall Gmbh Procede de formation d'une couche de conversion sans chromate, bien visible, pour magnesium et alliages de magnesium
US7147934B2 (en) 2000-11-07 2006-12-12 Nisshin Steel Co., Ltd. Chemically processed steel sheet excellent in corrosion resistance
US9879345B2 (en) 2012-03-09 2018-01-30 Nippon Paint Surf Chemicals Co., Ltd. Chemical conversion agent and chemical conversion coating film
US10005912B2 (en) 2010-06-09 2018-06-26 Chemetall Gmbh Inorganic chromium-free metal surface treatment agent
US10138559B2 (en) 2013-04-03 2018-11-27 Nippon Paint Surf Chemicals Co., Ltd. Chemical conversion agent and metal surface treatment method

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI268965B (en) 2001-06-15 2006-12-21 Nihon Parkerizing Treating solution for surface treatment of metal and surface treatment method
TW567242B (en) 2002-03-05 2003-12-21 Nihon Parkerizing Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment
JP4242827B2 (ja) 2004-12-08 2009-03-25 日本パーカライジング株式会社 金属の表面処理用組成物、表面処理用処理液、表面処理方法、及び表面処理金属材料
JP4510079B2 (ja) * 2005-03-16 2010-07-21 日本パーカライジング株式会社 表面処理金属材料
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JP2000199077A (ja) 2000-07-18
AU2020200A (en) 2000-05-15
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KR20000029286A (ko) 2000-05-25
EP1171648A1 (fr) 2002-01-16
JP3992173B2 (ja) 2007-10-17

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