WO2003052005A1 - Produit servant a former un appret d'adherence sur des surfaces metalliques et procede de traitement - Google Patents

Produit servant a former un appret d'adherence sur des surfaces metalliques et procede de traitement Download PDF

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Publication number
WO2003052005A1
WO2003052005A1 PCT/EP2002/013923 EP0213923W WO03052005A1 WO 2003052005 A1 WO2003052005 A1 WO 2003052005A1 EP 0213923 W EP0213923 W EP 0213923W WO 03052005 A1 WO03052005 A1 WO 03052005A1
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groups
metal
group
polymer
producing
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PCT/EP2002/013923
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German (de)
English (en)
Inventor
Kazuya Tanaka
Shimizu Akio
Ryoji Morita
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Henkel Kommanditgesellschaft Auf Aktien
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Priority claimed from JP2001382635A external-priority patent/JP2003138382A/ja
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU2002361029A priority Critical patent/AU2002361029A1/en
Publication of WO2003052005A1 publication Critical patent/WO2003052005A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C09D161/14—Modified phenol-aldehyde condensates
    • 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
    • C09D5/002—Priming 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the invention relates to a means for producing an adhesive primer on metal surfaces, by means of which the adhesive strength between metal materials and foils or lacquer layers applied thereon, and the corrosion resistance and solvent resistance of metal materials to which foils or lacquer layers are applied, is improved. More particularly, the invention relates to the invention a means of producing an adhesive primer on metal surfaces, which gives metal materials such as aluminum, magnesium, copper, steel and alloys of these metals an excellent adhesive strength in the sense that applied foils are subjected to stressful shaping processes such as deep drawing, ironing (English: "wall ironing") The agent also gives the shaped articles an extremely excellent resistance to corrosion and solvents. The invention also relates to an agent for producing an adhesive base on metal surfaces, which can significantly improve the adhesion of paint layers. The invention also relates to a corresponding treatment method in which this agent is used.
  • Metal materials such as aluminum, magnesium, copper, steel and alloys of these metals, after having gone through various manufacturing processes, are mostly painted and used in automobiles, electrical household appliances, as building materials or for the manufacture of beverage cans.
  • Solvent-based or water-based resin-based paints are generally used for painting.
  • the functionality of these lacquers is then expressed in the form of layers of lacquer which are produced by applying the lacquers to the metal materials and then drying them with the addition of heat.
  • Powder coatings are also used in the fields of automobile construction and building materials. For painting, these are applied using spray guns.
  • Industrial waste (paint residues and solvents) accumulates in large quantities during painting. Also be volatile organic solvents and carbon dioxide are released into the atmosphere due to the baking of the paints at high temperatures. The generation of the lacquer layers is also associated with a high time requirement.
  • JP-A 10-46101 discloses a coated metal material, the surface of which is coated by means of an aqueous composition containing certain phenol compounds and also phosphoric acid compounds and organic silicon compounds, and a process for producing this coated metal material.
  • JP-A 11-140691 discloses a surface treatment method, a surface-hardened steel sheet and a steel sheet coated with a thermoplastic resin, for which the surface-treated steel sheet is used.
  • the technique disclosed here provides for chromating using a hexavalent chromium-containing agent and then, as a surface treatment to improve the adhesive strength, a silane treatment using a silane coupling reagent.
  • Metal materials that have been surface-treated according to these known techniques can be formed after the application of polyester films by deep drawing, stretch drawing and ironing.
  • the durability and corrosion resistance (when immersed in salt water) of objects that were sterilized after being deformed by pressurized water vapor are considered good. Nevertheless, the fatigue strength and, under severe conditions, corrosion and solvent resistance are insufficient. So far, no technique is known with which, using coated metal materials which have been treated with a surface treatment agent without hexavalent chromium, excellent adhesive strength, corrosion resistance and solvent resistance are achieved.
  • the object of the invention is therefore to remedy the shortcomings of the prior art and in particular to provide a means for producing an adhesive primer on metal surfaces, by means of which the adhesive strength between metal material and foils or lacquer layers and the corrosion resistance and solvent resistance of metal materials with foils or films applied thereon Paint coats can be improved.
  • Another object of the invention is to provide a treatment method in which this agent is used.
  • the inventors have found that by treating the surface of metal materials with a surface treatment agent which, at a pH in a range from 1.5 to 6.0, an aminated phenolic polymer and certain metal compounds or an aminated phenolic polymer, an acrylic polymer and contains defined metal compounds, the surface treatment being carried out according to a defined method, between the metal material and after the treatment of the films applied thereon there is an excellent adhesive strength between the layers, and at the same time excellent corrosion resistance and solvent resistance are achieved.
  • the inventors have found that the treatment according to the aforementioned, defined method between the metal material and the lacquer layers applied to it gives excellent adhesive strength and, at the same time, excellent corrosion resistance and solvent resistance are achieved.
  • the present invention is based on these findings.
  • the invention thus provides 1 a means for producing an adhesive primer on metal surfaces, which is characterized in that it is an aminated phenol polymer and at least one metal compound selected from Ti, Zr, Hf, Mo, W, Se, Ce, Fe, Cu, Zn and trivalent Cr, and the pH of the agent is in a range of 1.5 to 6.0.
  • the aminated phenol polymer improves the adhesion between the metal surface and the film during the formation of the coating, which is why even stressful forming processes can be met.
  • the aforementioned metal compounds cause a dense coating due to the crosslinking between the aminated phenolic polymer and metal during the formation of the coating, and thus lead to excellent resistance to corrosion and solvents.
  • the pH of the agent for treating metal surfaces according to the invention is in the range from 1.5 to 6.0, which means that the agent is in a stable state.
  • Aminated phenol polymers having a structure according to the following general formula (I) are preferably used as the aminated phenol polymer for use in agents according to the invention for treating metal surfaces.
  • X1 independently represents a hydrogen atom or the group Z1 according to the following general formula (II)
  • R 1 and R 2 independently of one another represent hydrogen atoms, C - O - alkyl groups or Y1 represents a hydrogen atom, a hydroxyl group, a C1-5 alkyl group, a C1-5 hydroxyalkyl group, a C1-12 aryl group or benzyl group or a structure according to the following general formula (III)
  • R3 and R4 independently of one another represent hydrogen atoms, C1-10 alkyl groups or C1-10 hydroxyalkyl groups
  • X 2 in the structural units indicated by formula (I) independently represents a hydrogen atom or the group Z 2 according to the following general formula (IV):
  • R 5 and R 6 independently of one another represent hydrogen atoms, C 1-10 -
  • Alkyl groups or C 1-10 hydroxyalkyl groups
  • Y2 stands for a hydrogen atom or, in the case of Y2 present at a position adjacent to Y1, for condensed benzene rings including the bonds between Y1 and
  • n stands for integers
  • substitution rate for groups Z 1 and Z 2 is based on 1
  • Agents for treating metal surfaces according to the invention can contain acrylic polymer (s) as a further component.
  • the combination with acrylic polymers can further improve the adhesive strength between metal material and foils or lacquer layers, as well as corrosion and solvent resistance.
  • the ratio of aminated phenol polymer to acrylic polymer, calculated as a solid, is preferably 100/1 to 1/20.
  • the acrylic polymer preferably contains at least one monomer unit which is selected from the following structures (V) and (VI). - (CH 2 -CHCOR 7 ) - (V)
  • R 7 and R 8 represent hydroxyl groups, amide groups or d. 5 - hydroxyalkyl groups.
  • the invention further provides a treatment method which is characterized in that a metal surface is brought into contact with the above-mentioned agent for treating metal surfaces and then dried without rinsing at a temperature in a range from 80 to 300 ° C.
  • the layer weight of the aminated phenol polymer or the joint layer weight of aminated phenol polymer and acrylic polymer after drying in the coating produced by the above-mentioned process is preferably 1 to 100 mg / m 2 and the layer weight of Ti, Zr, Hf, Mo, W , Se, Ce, Fe, Cu, Zn and trivalent Cr selected metal compound or metal compounds, calculated as metal, preferably at 1 to 100 mg / m 2 .
  • metal materials for use in metals coated according to the invention.
  • the shape of the materials is not subject to any restrictions. However, since foils are applied, sheets are preferably used. The sheets can be available as individual sheets or as strips ("coils").
  • R 1 , F ⁇ in the general formula (II) independently of one another represent hydrogen atoms, C 1 -C 10 -alkyl groups or O O - hydroxyalkyl groups. If the carbon number of the alkoxy or hydroxyalkyl groups is 11 and more, areas with micropores and therefore no dense coatings form, which leads to reduced corrosion resistance. In addition, the adhesive strength of the films would suffer, since the hydrophobicity increases due to the long alkyl chains.
  • Y 1 represents n of the general formula (I), as already stated above
  • Hydrogen atom a hydroxyl group, a C 1-5 alkyl group, a C 1 . 5 -
  • Hydroxyalkyl group a C ⁇ . 12 aryl group or benzyl group, a structure according to the general formula (III) or for fused benzene rings which result together with Y 2 or together with bonds between Y 1 and Y 2 .
  • Hydroxyalkyl groups with a carbon number of 6 and higher or of aryl or
  • the common substitution rate of the groups Z 1 and Z 2 introduced into the aminated phenolic polymers is, as already explained above, 0.2 to 1.0 groups per benzene ring.
  • the joint rate of substitution of the groups Z 1 + Z 2 is 1.0 if Y 1 is not a group according to formula (III), or that the common substitution rate of the groups Z 1 + Z 2 is 0.5 if Y 1 is a group according to formula (III).
  • the common substitution rate of the groups Z 1 + Z 2 is obtained by dividing the total number of groups Z 1 + Z 2 in the polymer by the total number of benzene rings in the general formula (I) and the benzene rings in the formula (III). With a common substitution rate of the groups Z 1 + Z 2 below 0.2, the adhesive strength between the aminated phenol polymer and the metal surface is insufficient, which disadvantageously promotes detachment of the foils during processing. With a common substitution rate of the groups Z 1 + Z 2 above 1.0, the polarity becomes too strong, which favors the penetration of water and thus leads to poor corrosion resistance.
  • aminated phenol polymers contained in surface treatment agents according to the invention can be prepared by customary processes, for example by polycondensation of phenol compounds, naphthol compounds or bisphenols (for example bisphenol A, bisphenol F) with formamide and subsequent introduction of the functional groups X 1 and X 2 using formaldehyde and amine , Formaldehyde is usually used in the form of formalin.
  • acids such as organic acids, inorganic acids or complex fluorides can be added.
  • Examples include acetic acid, citric acid, lactic acid, malic acid, succinic acid, Adipic acid, sulfuric acid, nitric acid, silica, fluorosilicic acid, hydrofluoric acid, phosphoric acid, fluorozirconic acid and fluorotitanic acid.
  • the molecular weight of the aminated phenolic polymers is not particularly restricted. Those with a molecular weight of about 1000 to 1,000,000 have proven suitable.
  • Surface treatment agents according to the invention further contain at least one metal compound which is selected from compounds of Ti, Zr, Hf, Mo, W, Se, Ce, Fe, Cu, Zn and trivalent Cr. These are necessary in order to improve the corrosion resistance of the metal materials with the foil or lacquer layer applied to them.
  • the metal connections include Metal oxides, hydroxides, complex compounds and salts of organic and inorganic acids are available.
  • the following metal compounds can be used in the invention: fluorozirconic acid, ammonium zirconium fluoride, zirconium acetate, zirconium nitrate, zirconium sulphate, zirconium ammonium carbonate, fluorotitanic acid, ammonium titanium fluoride, titanyl sulphate, titanium lactate, diisopropoxytitanium bisacetylacetate, ammonium vanadium acetylacetate, vanadium meta methane acetate, ammonium vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid, vanadium acetic acid , Cerium sulfate, cerium fluoride, selenium dioxide, selenium sulfide, sodium selenate, nickel
  • Molybdatophosphoric acid ammonium salt molybdatophosphoric acid sodium salt, ammonium tungstate, sodium tungstate, tungsten hexacarbonyl, 12-tungstophosphoric acid, tungstophosphoric acid ammonium salt, tungstophosphoric acid sodium salt, tungstate silicate, iron ammonium nitrate, iron ammonium nitrate, iron ammonium nitrate, iron ammonium nitrate, iron ammonium sulfate, iron ammonium sulfate, , Iron fluoride, iron (II) lactate, iron (III) nitrate, zinc acetate, zinc acetylacetate, zinc carbonate, zinc citrate, zinc fluoride, fluorosilicic acid-zinc salt, zinc lactate, zinc nitrate, chromium sulfate, chromium nitrate, chromium fluoride, chromium oxalate and chromium acetate.
  • Water is predominantly used as the solvent in the surface treatment agents according to the invention, and the water can be combined with organic solvents, for example alcohols, to adjust the liquid properties, for example to reduce the surface tension or to adjust the drying behavior at low temperatures.
  • the pH of surface treatment agents according to the invention must be in a range from 1.5 to 6.0 are, since at a pH value below 1.5 technical difficulties, especially corrosion of the systems, are foreseeable, while at a pH value above 6.0 the aminated phenolic polymers are precipitated and are therefore no longer stable in the solution.
  • Organic and inorganic acids can be used to adjust the pH. Examples include acetic acid, citric acid, lactic acid, malic acid, succinic acid, adipic acid, sulfuric acid, nitric acid, silica, fluorosilicic acid, hydrofluoric acid and phosphoric acid.
  • the acrylic polymers used to further improve the adhesive strength between the layers, the corrosion and solvent resistance in the surface treatment agents can be selected from a wide range of acrylic-based polymers and are not subject to any particular restrictions in this regard. However, those acrylic polymers are preferably used which contain at least one monomer unit according to the general formulas (V) and (VI) in their structure.
  • Suitable are, for example, acrylic homopolymers in which the structural units according to the general formula (V) each have an identical radical R 7 , or acrylic copolymers in which the structural units according to the general formula (V) each have two or more different radicals R 7 , and methacrylic homopolymers , in which the structural units according to the general formula (VI) each have an identical radical R 8 , or methacrylic copolymers in which the structural units according to the general formula (VI) each have two or more different radicals R 8 .
  • mixtures consisting of two or more of these homopolymers or copolymers, and also copolymers which in their structure predominantly have at least one monomer unit selected from those of the general formulas (V) and (VI) in combination with other vinyl monomer units have used.
  • the radicals R 7 and R 8 are hydroxyalkyl groups
  • the carbon number of the alkyl chains is preferably in a range from 1 to 5, but in particular 1 or 2.
  • the molecular weight (middle of number!) Of the acrylic polymers is suitably about 5000 to 1,000,000, but preferably 10,000 to 200,000.
  • the method according to the invention for the treatment of metal surfaces is discussed below. Before the surfaces of the metal materials used as substrates for the application of foils are brought into contact with surface treatment agents according to the invention, they have to be cleaned. This means that corrosion protection and rolling oils, which are often applied to their surfaces in metal materials used in industry, must be removed. The method used for this is not subject to any particular restrictions. Degreasing with solvents, with alkalis and with acids are mentioned as examples. After degreasing, the surfaces must be rinsed to remove any remaining degreasing agent by exchanging them with water.
  • the treatment process thus belongs to the group of processes in which drying follows continuously after application (“no-rinse process”).
  • the application process is not subject to any particular restrictions. Examples of such processes are roller application processes, spray processes, dipping processes and
  • the temperature of the surface treatment agent is not particularly limited and is usually in a range from 10 to 40 ° C., but preferably in a range from 15 to 25 ° C.
  • the solvent namely water
  • the aminated phenolic polymers are rendered insoluble and a crosslinking reaction is effected with the metal compounds.
  • the drying temperature lies in a range from 80 to 300 ° C, but preferably in a range of 100 to 250 C C. At a drying temperature below 80 ° C, the corrosion resistance as a result of water entry (due to high contents of the GruDDen Z 1 and Z 2 according to the general formulas [II] and [IV]).
  • the content of the aminated phenol polymer or the common content of the aminated phenol polymer and acrylic polymer in the dried coating must be 1 to 100 mg / m 2 as the layer weight after drying. If this characteristic value is below 1 mg / m 2 , the performance with regard to the adhesive strength during processing after the application of foils remains inadequate, while layer weights over 100 mg / m 2 are not useful from an economic point of view due to the further increase in performance.
  • the layer weight of the metal compound or metal compounds selected from compounds of Ti, Zr, Hf, Mo, W, Se, Ce, Fe, Cu, Zn and trivalent Cr must be 1 to 100 mg / m 2 , calculated as the basis weight of the applied metal , since corrosion resistance and solvent resistance are impaired with a layer weight below 1 mg / m 2 and embrittlement of the dry layer occurs with a layer weight above 100 mg / m 2 , which leads to poor adhesive strength during processing.
  • Foils are applied to the metal materials on which a dry.coating surface treatment agent according to the invention has been produced.
  • the foils used for this purpose can have a wide variety of functionalities, such as adhesiveness, effectiveness as a gas barrier, electrical conductivity and formability.
  • films are available. Examples of films that can be applied include, without being restricted, films made of polyester, polyvinyl terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl alcohol, polyamide, polyvinyl acetate and copolymers of the substances mentioned. These can, to give them functionality, conductive fillers, colorants and the like. ⁇ . Be added.
  • Examples of methods for applying the foils to the metal materials are direct gluing of foils softened by heating (heat lamination), gluing using adhesive primers (dry lamination) and extrusion by extrusion of molten resins Called slot tools.
  • the invention can also be used, for example, to produce adhesive primers for lacquer layers.
  • the paints that can be used for painting are not subject to any particular restrictions, for example Acrylic resin-epoxy water-based paints and solvent-based PVC paints can be used. .
  • Aluminum alloy sheet (JIS A3004, 0.26 mm thick) was sprayed with a 2% aqueous solution of Fine Cleaner 4377K (alkaline degreasing agent from Nihon Parkerizing) for 10 seconds at 50 ° C. and then rinsed with water. To evaporate water from the sheet surface, the sheet was dried at 80 ° C for 1 minute.
  • Fine Cleaner 4377K alkaline degreasing agent from Nihon Parkerizing
  • the constituents of the surface treatment agents used in the exemplary and comparative examples are mentioned below. Deionized water and acidifying or alkalizing agents were used to prepare the surface treatment agents.
  • Aminated phenol polymer II (see below) 10 g / l
  • Aminated phenol polymer II aminated phenol polymer according to the general formula
  • Aminated phenol polymer III (see below) 10 g / l -.
  • Aminated phenol polymer IM aminated phenol polymer according to the general formula
  • Formula (III) in which R 3 and R 4 are CH 3 and X 2 in the structural units of the formula (I) are each independently a hydrogen atom or the group Z 2 -CH 2 -N (CH 2 CH 2 OH) 2 ,
  • Y 2 is a hydrogen atom, substitution rate for the groups Z 1 + Z 2 : 0.7,
  • Acrylic polymer I (see below) 5 g / l pH 4.0 (adjusted with ammonia water)
  • Acrylic polymer I acrylic polymer consisting of monomer units according to the general
  • Acrylic polymer II (see below) 5 g / l pH 4.0 (adjusted with ammonia water)
  • Acrylic polymer II copolymer consisting of monomer units A according to the general
  • Acrylic polymer III (see below) 16 g / l
  • Acrylic polymer III acrylic polymer consisting of monomer units according to the general
  • Formula (V), in the formula R 7 is a hydroxyl group, molecular weight: 10,000 ⁇
  • the surface treatment agents prepared as described above were applied to the surfaces of the surface using a roller application machine with a wet weight of 5 g / m 2
  • coated metal sheets were produced with predetermined layer weights.
  • 16 ⁇ m thick polyester film was applied directly to the metal materials coated by surface treatment as above for 5 seconds at 250 ° C. (temperature of the incoming metal sheets: 180 ° C.) with a surface pressure of 50 kg / cm 2 (“heat lamination”).
  • the coated metal sheets with a film applied thereon were subjected to a drawing and ironing test, in which the first step was to use 100 mm diameter cups from the metal sheet cut into round disks of 160 mm diameter, then in a second step by intermediate drawing cups of 75 mm and finally by a third Pulling test specimens made with a diameter of 65 mm.
  • the ironing rate factor with which the Wall thickness is reduced
  • the initial adhesive strength was evaluated according to the following criteria:
  • the molded cans were subjected to a sterilization test under heated, compressed water vapor.
  • the sterilization was carried out for 1 hour at 125 ° C in a commercially available sterilization device.
  • the aluminum alloy sheets were selected to test the corrosion resistance, since a comparison in the case of different metal materials has no meaningfulness.
  • the DWI cans were filled with a model juice consisting of citric acid monohydrate, sodium chloride and fully demineralized water in a ratio of 5 to 5 to 990 (parts by weight) and stored at 60 ° C. for 120 hours. The appearance of the inside of the can was then examined with the naked eye.
  • the molded sample cans were immersed in a 20% aqueous solution of ethanol at 60 ° C for 120 hours, after which the appearance of the films was examined. 1 no change in appearance
  • the surface treatment agents, treatment conditions and the layer weights of the coatings produced on the metal materials used in working examples 1 to 12 and comparative examples 1 to 3 are summarized in table 1 and in table 2 the results of the individual tests.
  • the results in Table 2 show an excellent initial and endurance strength as well as an excellent corrosion and solvent resistance for the exemplary embodiments 1 to 12.
  • the comparative examples comparative example 1: only using the aminated phenol polymer without the metal compound required in the invention, comparative example 2: using orthophosphoric acid and organic silicon compound without a metal compound, comparative example 3: using polyacrylic acid instead of the aminated phenolic polymer with the addition of a trivalent chromium compound) satisfy all requirements (initial and endurance strength as well as corrosion and solvent resistance).
  • coated metal materials were produced by a treatment carried out in the same way, to which acrylic resin-epoxy resin-water-based paint and PVC (solvent-based) paint were applied in the roller application process. Subsequent drying with the addition of heat (temperature of the incoming sheets 250 ° C.) gave test pieces. The thickness of the lacquer layers, measured with an electromagnetic layer thickness measuring device, was 10 ⁇ m in each case.
  • test pieces (Cr layer weight 20 mg / m) were degreased for 10 seconds with 2% aqueous solution of Fine Cleaner 4377K (alkaline degreasing agent from Nihon Parkerizing) at 50 ° C., rinsed with water to clean the surfaces, followed by continuous treatment with AM-K702 (agent for phosphoric acid / chromate conversion treatment by Nihon Parkerizing, 5 seconds Spray at 50 ° C), remove unreacted conversion treatment agent by rinsing with water and drying for 1 minute at 80 ° C.
  • Fine Cleaner 4377K alkaline degreasing agent from Nihon Parkerizing
  • test pieces were subjected to the tests described above for performance evaluation, the results are summarized in Table 3.
  • results in Table 3 show that surface treatment agents according to the invention have outstanding performances even when used as a primer for lacquer layers.
  • the crosslinking of the functional groups contained in the aminated phenolic polymers brings about corrosion and solvent resistance on account of the improved barrier properties.
  • the remaining hydroxyl groups also lead to firm adhesion to the metal surfaces. This enables an improvement in the adhesive strength of foils or lacquer layers applied to the surfaces.
  • the corrosion protection caused by the metal connections results in excellent corrosion resistance of the materials after the metal materials have been formed, if they are exposed to corrosive environments.
  • Combinations with acrylic polymers also make another one It is possible to increase the performance in terms of adhesive strength between the layers and in terms of corrosion and solvent resistance.
  • metal materials with foils or lacquer layers applied thereon are obtained which show good adhesion between the layers and offer excellent initial and long-term strength.
  • these metal materials with foils or lacquer layers applied to them are characterized by excellent resistance to corrosion and solvents.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Mechanical Engineering (AREA)
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  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un produit servant à former un apprêt d'adhérence sur des surfaces métalliques ainsi qu'un procédé de traitement de surfaces métalliques consistant à utiliser ce produit, par l'intermédiaire duquel l'adhérence entre un matériau métallique et des pellicules appliquées sur ce matériau ainsi que la résistance à la corrosion et aux solvants de matériaux métalliques, recouverts de pellicules, sont améliorées et une meilleure adhérence des couches de vernis est obtenue. Ce produit de traitement de surfaces contient, à une valeur pH comprise entre 1,5 et 6, un polymère phénolique aminé et au moins un composé métallique, sélectionné parmi Ti, Zr, Hf, Mo, W, Se, Ce, Fe, Cu, Zn et Cr trivalent. Cette invention concerne également un procédé de traitement, consistant à mettre en contact des surfaces métalliques avec ce produit de traitement de surfaces puis à effectuer une étape de séchage à une température comprise entre 80 et 300 °C, aucune étape de rinçage n'étant effectuée après l'entrée en contact avec ledit produit de traitement de surfaces.
PCT/EP2002/013923 2001-12-17 2002-12-09 Produit servant a former un appret d'adherence sur des surfaces metalliques et procede de traitement WO2003052005A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002361029A AU2002361029A1 (en) 2001-12-17 2002-12-09 Agent for producing a primer on metallic surfaces and method for treatment

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP01/382635 2001-12-17
JP2001382635A JP2003138382A (ja) 2000-12-26 2001-12-17 接着下地用の金属表面処理薬剤及び処理方法

Publications (1)

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WO2003052005A1 true WO2003052005A1 (fr) 2003-06-26

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7780771B2 (en) 2005-12-05 2010-08-24 Rohm And Haas Electronic Materials Llc Metallization of dielectrics
CN107073873A (zh) * 2014-05-28 2017-08-18 凯密特尔有限责任公司 夹层结构的制造方法、由此制造的夹层结构及其用途
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511404A (en) * 1982-11-02 1985-04-16 Itt Industries, Inc. Compositions for inhibiting corrosion of metal surfaces
EP0168870A1 (fr) * 1984-06-15 1986-01-22 BASF Aktiengesellschaft Procédé de préparation d'un liant convenant pour un revêtement et son application
WO1998005804A1 (fr) * 1996-08-01 1998-02-12 Henkel Corporation Surfaces metalliques pelliculees de resine phenolique-formaldehyde et procede correspondant
EP1120478A2 (fr) * 2000-01-28 2001-08-01 Henkel Corporation Compositions et procédés de phosphatation au zinc sans rinçage
WO2001064356A1 (fr) * 2000-02-28 2001-09-07 Henkel Kommanditgesellschaft Auf Aktien Feuille de metal avec resistance a la corrosion superieure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511404A (en) * 1982-11-02 1985-04-16 Itt Industries, Inc. Compositions for inhibiting corrosion of metal surfaces
EP0168870A1 (fr) * 1984-06-15 1986-01-22 BASF Aktiengesellschaft Procédé de préparation d'un liant convenant pour un revêtement et son application
WO1998005804A1 (fr) * 1996-08-01 1998-02-12 Henkel Corporation Surfaces metalliques pelliculees de resine phenolique-formaldehyde et procede correspondant
JPH1046101A (ja) * 1996-08-01 1998-02-17 Nippon Parkerizing Co Ltd 金属材料の表面にフィルムラミネート用下地皮膜を形成させた被覆金属材料、およびその製造方法
EP1120478A2 (fr) * 2000-01-28 2001-08-01 Henkel Corporation Compositions et procédés de phosphatation au zinc sans rinçage
WO2001064356A1 (fr) * 2000-02-28 2001-09-07 Henkel Kommanditgesellschaft Auf Aktien Feuille de metal avec resistance a la corrosion superieure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7780771B2 (en) 2005-12-05 2010-08-24 Rohm And Haas Electronic Materials Llc Metallization of dielectrics
CN107073873A (zh) * 2014-05-28 2017-08-18 凯密特尔有限责任公司 夹层结构的制造方法、由此制造的夹层结构及其用途
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

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