EP3426822B1 - Fluoride-free zirconium-based metal pre-treatment for passivation - Google Patents
Fluoride-free zirconium-based metal pre-treatment for passivation Download PDFInfo
- Publication number
- EP3426822B1 EP3426822B1 EP17701835.5A EP17701835A EP3426822B1 EP 3426822 B1 EP3426822 B1 EP 3426822B1 EP 17701835 A EP17701835 A EP 17701835A EP 3426822 B1 EP3426822 B1 EP 3426822B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zirconium
- less
- corrosion agent
- particularly preferably
- water
- Prior art date
- Legal status (The legal status 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 status listed.)
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims description 40
- 229910052726 zirconium Inorganic materials 0.000 title claims description 40
- 229910052751 metal Inorganic materials 0.000 title claims description 24
- 239000002184 metal Substances 0.000 title claims description 24
- 238000002161 passivation Methods 0.000 title description 12
- 238000002203 pretreatment Methods 0.000 title description 2
- 238000005260 corrosion Methods 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 64
- 239000000758 substrate Substances 0.000 claims description 38
- -1 polycyclic hydrocarbon Chemical class 0.000 claims description 35
- 229930195733 hydrocarbon Natural products 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
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- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
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- 239000002253 acid Substances 0.000 claims description 9
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 9
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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
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D28/00—Shaping by press-cutting; Perforating
-
- 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
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
Definitions
- the present invention relates to a method for the anticorrosive pretreatment of metal substrates using zirconium-based aqueous corrosion protection agents.
- the anti-corrosive effect of the zirconium-based agent is based on the presence of polycyclic hydrocarbons, which have at least one fused benzene ring with in each case at least two nucleus-substituted hydroxyl groups in the ortho position to one another.
- the aqueous corrosion protection agent can be essentially free both of passivating chromium-containing compounds and of fluoride-containing compounds that pickle the metal substrate.
- the pretreatment by drying is particularly advantageous.
- the method according to the invention is particularly suitable for the pretreatment of metal strip, with excellent corrosion protection results being achieved on surfaces of aluminum or steel.
- the invention additionally comprises a method for producing coated can ends from aluminum strip using the aforementioned zirconium-based corrosion protection agent.
- an aqueous concentrate for providing the ready-to-use corrosion protection agents is included.
- the conversion treatment of metallic surfaces to provide a coating that protects against corrosion and is based on aqueous compositions containing water-soluble compounds of the element zirconium is a technical field that is extensively described in the patent literature.
- various variants of such a metal pretreatment are known, which either aim at the composition of the agents causing the conversion or use further wet chemical treatment steps in the immediate context of the conversion treatment.
- the EP 1 455 002 A1 suggests that the proportion of fluorides in the passivating coating caused by wet-chemical conversion using water-soluble fluoro compounds of the element zirconium should not exceed a certain proportion and, at the same time, suggests drying at an elevated temperature and rinsing with an alkaline solution as suitable post-treatments, in order to bring about a considerable reduction in the fluoride content.
- the suitability of the anti-corrosive agent by drying to provide a good paint adhesion primer on aluminum substrates and thus being suitable for the production of beverage cans is desirable here.
- the anti-corrosion agent to be applied in such a process is also largely free of compounds that release fluoride which are problematic in terms of environmental hygiene.
- This range of tasks is achieved by a method for the anticorrosive pretreatment of a metallic substrate, in which the surface of the metallic substrate is brought into contact with an aqueous corrosion protection agent which contains at least one water-soluble compound (A) of the element zirconium, the agent additionally at least one polycyclic Contains hydrocarbon (B) which has at least one fused benzene ring each with at least two nucleus-substituted hydroxyl groups in ortho-position to one another, and wherein the molar ratio of zirconium to the total fluoride content in the homogeneous aqueous phase of the anti-corrosion agent is greater than 1.
- a compound (A) of the element zirconium is water-soluble in the context of the present invention if it has a solubility of at least 0.1 g of the compound at 20 ° C. in deionized water, which has a specific conductivity of less than 11 ⁇ Scm ⁇ 1 on the element zirconium per kilogram of the aqueous solution thus produced.
- the method according to the invention ensures that, as a result of a pickling attack on the metallic substrate, passivation of the metallic substrate occurs mediated by a surface covering based on poorly soluble compounds of the element zirconium and the polycyclic hydrocarbon.
- Metallic substrates pretreated according to the invention which thus have a corresponding surface coverage, are also ideally suited to impart an excellent paint primer to subsequent primers containing film-forming organic resins; for this purpose, the aqueous corrosion protection agent can additionally contain organic polymers without the passivation being adversely affected.
- the polycyclic hydrocarbon (B) has a low solubility in water, so that it is necessary for adequate surface coverage in the respective application process
- the necessary dissolved amount of polycyclic hydrocarbon (B) is ideally still just dissolved in the aqueous corrosion protection agent.
- processes according to the invention are preferred in which the polycyclic hydrocarbon (B) at 20 ° C in deionized water with a specific conductivity of less than 1 ⁇ Scm -1 has a solubility of less than 5 g, particularly preferably less than 1 g per Has kilograms of the aqueous solution produced thereby
- a low solubility of the polycyclic hydrocarbon (B) is particularly advantageous when applying the anti-corrosion agent in the drying process (so-called "dry-in-place process”), in which even small amounts of the active components of the anti-corrosion agent for a passivating surface covering of the metallic to be protected Substrates can be sufficient.
- solubility in water is to be understood with respect to the compound (B) so that above the solubility limits mentioned at a shear rate of 100 s -1 result in dispersions or emulsions with an average particle diameter (D50 value) calculated from cumulative particle diameter distribution curves determined by dynamic light scattering methods of more than 50 nm.
- D50 value average particle diameter
- the polycyclic hydrocarbon (B) contains at least two fused benzene rings each with at least two nucleus-substituted hydroxyl groups in the ortho position to one another, the benzene rings each being bridged to one another by fusing to an acyclic hydrocarbon system, the acyclic hydrocarbon system preferably at least has an oxo group or hydroxyl group.
- Such polycyclic hydrocarbons (B) are familiar to the person skilled in the art, for example in the form of hematoxylin and its oxidation product hematein and in the form of alizarin.
- polycyclic hydrocarbons (B) which build on the anthraquinone basic structure.
- those polycyclic hydrocarbons (B) are preferred in the process according to the invention which are selected from the group of anthraquinones with at least two hydroxyl groups in the ortho-position to one another, particularly preferably selected from the group consisting of 1,2-dihydroxyanthraquinone, 3 , 4-dihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,5-trihydroxyanthraquinone, 1,2,6-trihydroxyanthraquinone, 1,2,7 Trihydroxyanthraquinone, 1,2,8-trihydroxyanthraquinone, 1,2,3-tri
- the ratio of water-soluble compounds (A) of the element zirconium to polycyclic hydrocarbons (B) should be in a certain range for optimal passivation of the surfaces of the metallic substrates pretreated in the process according to the invention.
- the weight ratio of water-soluble compounds (A) of the zirconium element based on the zirconium element to polycyclic hydrocarbons (B) in the corrosion protection agent of the process according to the invention is preferably less than 0.2, particularly preferably less than 0.1, but preferably greater than 0.02 is.
- Preferred amounts of the polycyclic hydrocarbons (B) in the anti-corrosion agent of the process according to the invention are in the range from 5-250 mg / kg.
- the anti-corrosive agent which is used in the process according to the invention is preferably adjusted to be acidic for an increased solubility of the water-soluble compounds (A) of the element zirconium and an acidic effect on the metal substrate.
- the pH of the corrosion protection agent is less than 2.0, particularly preferably less than 1.6, but preferably greater than 0.5, particularly preferably greater than 1.0.
- the method according to the invention is characterized in that a high rate of pickling removal, ie a high rate of metal dissolution during the bringing into contact with the corrosion protection agent, is not necessary for adequate surface passivation. Consequently, in particularly advantageous embodiments of the invention, the corrosion protection agent can be formulated largely free of environmentally harmful fluorides or fluoride-releasing compounds which are usually used to increase the pickling rate, in particular on aluminum substrates.
- the molar ratio of zirconium to the total fluoride content in the homogeneous aqueous phase of the anti-corrosion agent is greater than 1, preferably greater than 2, particularly preferably greater than 4.
- the total fluoride content is in a TISAB buffered aliquot of the anti-corrosion agent determined with a fluoride-sensitive electrode at 20 ° C (TISAB: "Total lonic Strength Adjustment Buffer"), the volume-based mixing ratio of buffer to the aliquot of the corrosion protection agent being 1: 1.
- the TISAB buffer is prepared by dissolving 58 g of NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and setting a pH value of 5.3 using 5 N NaOH and making up to a total volume of 1000 ml again with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ).
- the source of the water-soluble compound (A) of the element zirconium is not also a source of fluoride ions and is preferably selected from zirconyl nitrate, zirconium acetate and / or ammonium zirconium carbonate, particularly preferably from zirconyl nitrate.
- the preferred amount of the water-soluble compound (A) in the corrosion protection agent of the process according to the invention is at least 40 mg / kg, particularly preferably at least 200 mg / kg, in particular at least 400 mg / kg, but preferably not more than 4000 mg / kg, based on the amount of the element zirconium.
- the total fluoride content in the aqueous phase of the corrosion protection agent is less than 50 mg / kg, preferably less than 10 mg / kg, particularly preferably less than 1 mg / kg, based on the corrosion protection agent.
- the corrosion protection agent does not have to contain anions which form sparingly soluble salts such as phosphates in order to form a passivating coating.
- the corrosion protection agent therefore contains less than 0.2% by weight, particularly preferably less than 0.1% by weight, of dissolved phosphates, calculated as PO 4 .
- the method according to the invention is outstandingly suitable for providing a paint primer on metallic substrates, in particular by drying a wet film of the corrosion protection agent.
- This suitability means that the presence of organic polymers that improve paint adhesion in the aqueous corrosion protection agent does not have a negative effect on the passivation.
- the corrosion protection agent therefore contains at least 0.1% by weight, particularly preferably at least 0.2% by weight, of organic compounds (C) each based on the aqueous corrosion protection agent, which have a molar mass above 5,000 g / mol. In the present case, the molar mass can be determined directly in the anticorrosion agent at 20 ° C.
- the organic compounds (C) preferably contain at least partially functional groups selected from hydroxyl groups, carboxyl groups, phosphate groups, phosphonate groups and amino groups.
- the sum of the acid number and hydroxyl number is at least 100 milligrams of KOH per gram, particularly preferably at least 200 milligrams of KOH per gram of the organic compounds (C), but preferably not more than 600 milligrams of KOH per gram of the organic compounds (C) .
- the acid number is a measured variable to be determined experimentally, which is a measure of the number of free acid groups in the polymer or in a polymer mixture.
- the acid number is determined by dissolving a weighed amount of the polymer or the polymer mixture in a solvent mixture of methanol and distilled water in a volume ratio of 3: 1 and then potentiometrically titrating it with 0.05 mol / l KOH in methanol.
- the potentiometric measurement is carried out with a combination electrode (LL-Solvotrode® from Metrohm; reference electrolyte: 0.4 mol / l tetraethylammonium bromide in ethylene glycol).
- the acid number corresponds to the added amount of KOH in milligrams per gram of polymer or polymer mixture at the turning point of the potentiometric titration curve.
- the hydroxyl number can be determined experimentally by potentiometric titration as a measure of the number of free hydroxyl groups in the polymer or in a polymer mixture.
- a weighed amount of the polymer or the polymer mixture in a reaction solution of 0.1 mol / l phthalic anhydride in pyridine is heated at 130 ° C for 45 minutes and first with 1.5 times the volume of the reaction solution of pyridine and then with the 1, 5 times the volume of the reaction solution of deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) was added.
- the amount of phthalic acid released is titrated in this mixture using 1 M potassium hydroxide solution.
- the potentiometric measurement is carried out with a combination electrode (LL-Solvotrode® from Metrohm; reference electrolyte: 0.4 mol / l tetraethylammonium bromide in ethylene glycol).
- the hydroxyl number corresponds to the added amount of KOH in milligrams per gram of polymer or polymer mixture at the turning point of the potentiometric titration curve.
- those aqueous corrosion inhibitors are preferred according to the invention which contain, as organic compounds (C), copolymers or copolymer mixtures of alkenes and vinyl alcohol, particularly preferably ethene and vinyl alcohol, which particularly preferably have a hydroxyl number im Range from 200 to 500 milligrams of KOH per gram of the copolymer or the copolymer mixture.
- the proportion of these copolymers or copolymer mixture is preferably at least 0.1% by weight, particularly preferably at least 0.2% by weight, but preferably does not exceed 5% by weight, particularly preferably not 2% by weight, in each case based on the aqueous corrosion protection agents.
- the corrosion protection agent contains less than 0.1% by weight, particularly preferably less than 0.01% by weight, of particulate inorganic constituents which, in the case of ultrafiltration, have an exclusion limit of 50 kD Retentate to be retained.
- the aqueous corrosion protection agent can be formulated essentially free of toxic heavy metals.
- the aqueous corrosion protection agent therefore contains less than 50 mg / kg, preferably less than 10 mg / kg, particularly preferably less than 10 mg / kg, of compounds of the element chromium, and in a further preferred embodiment less than 50 mg / kg kg, preferably less than 10 mg / kg, particularly preferably less than 1 mg / kg, of compounds of the elements chromium, nickel and cobalt.
- the metallic substrates pretreated in the process according to the invention should have a sufficient solution pressure in the aqueous anti-corrosive agent under the usual process engineering conditions with respect to acids and atmospheric oxygen, and thus corrode at least to such an extent that a conversion of the natural or thin oxide layer specifically adjusted by means of wet-chemical cleaning on the respective Metal substrate is set in motion, which is completed by the deposition of elements and compounds of the active components of the anti-corrosion agent.
- the pretreatment of those metallic substrates is preferred according to the invention, which in an oxygen-saturated potassium hydrogen phthalate buffer (0.05 mol / L, pH 4.01, 20 ° C, 0.21 bar oxygen partial pressure in the atmosphere) has a corrosion potential of less as +0.2 V (SHE).
- the metallic substrates are selected from zinc and / or aluminum and their alloys, particularly preferably from aluminum and its alloys.
- alloys are formed from metal substrates which contain the respective metal element in a proportion of at least 50 at%.
- the anti-corrosion agent can be brought into contact with the metal substrate by means of conventional methods known to those skilled in the art of surface treatment.
- a preferred type of application according to the invention is the setting of a defined wet film on the surface of a preferably flat metal substrate, for example in the roller application process or by spraying and wiping it on, and drying it, so that reproducible and always sufficient quantities of the active components of the corrosion protection agent on the Metal substrate remain.
- a wet chemical treatment is any treatment of the substrate with a water-containing agent which does not only serve to remove active components contained in a wet film from a previous treatment step from the surface of the metal substrate.
- the wet film of the corrosion protection agent remains on the metal substrate in such a film thickness that, after drying, a layer of zirconium of more than 5 mg / m 2 , preferably more than 10 mg / m 2 , but preferably less than 150 mg / m 2 , particularly preferably less than 50 mg / m 2 .
- a special embodiment of the method according to the invention therefore serves to produce coated can ends from aluminum strip, for their production in a first step on aluminum strip such a wet film of an aqueous corrosion protection agent containing at least one water-soluble compound (A) of the element zirconium and at least one polycyclic hydrocarbon (B) , which has at least one fused benzene ring with at least two nucleus-substituted hydroxyl groups in ortho position to one another, is applied, which, after drying, realizes a layer of zirconium of more than 5 mg / m 2 , whereupon, after drying, the cover material is punched out of the tape and Can end is reshaped.
- A water-soluble compound
- B polycyclic hydrocarbon
- an organic coating is applied by means of a primer containing at least one curable film-forming organic resin, which in turn preferably has functional groups capable of condensation selected from phosphonic acid, phosphoric acid, oxirane, amino, hydroxyl and / or has carboxyl groups, preferably applied according to the invention and cured.
- a primer is understood to mean an agent for the first coating of the metal substrates pretreated according to the invention with the corrosion protection agent with an organic material which as such necessarily contains at least one curable film-forming organic resin.
- layer thicknesses in the range of 0.5 - 50 ⁇ m are usually implemented.
- the corrosion protection agents already described in more detail in the context of the general method for the anticorrosive pretreatment of a metallic substrate are preferably to be used.
- the primer contains a curable film-forming organic resin which is selected from a copolymer or a copolymer mixture of at least one aliphatic and acyclic alkene with at least one ⁇ , ⁇ unsaturated carboxylic acid in water-dispersed form, the acid number being of the copolymer or the copolymer mixture is preferably at least 20 mg KOH / g, but preferably not more than 200 mg KOH / g and the acid groups of the copolymer or the copolymer mixture in water-dispersed form is preferably at least 20%, but preferably not more than 60% neutralized exist.
- a curable film-forming organic resin which is selected from a copolymer or a copolymer mixture of at least one aliphatic and acyclic alkene with at least one ⁇ , ⁇ unsaturated carboxylic acid in water-dispersed form, the acid number being of the copolymer or the copolymer mixture is preferably at least 20 mg KOH /
- the curable film-forming organic resin of the primer is preferably selected from an acrylate dispersion obtainable as a reaction product of a polymer having terminal or pendant ethylenically unsaturated groups, which preferably has a number average molecular weight in the range of 3000-50,000 g / mol, with a mixture of ethylenic Monomers containing unsaturated groups include those with carboxyl groups such as, for example, (meth) acrylic acid, itaconic acid and crotonic acid.
- the preparation of such dispersions is in the US 2015/0218407 A1 described in detail in paragraphs [0048] - [0049].
- the primers for the first coating of the pretreated aluminum strip for the production of can lids are preferably largely free of organic compounds that have a diphenylmethane structural unit and particularly preferably contain less than 0.1% by weight of diphenylmethane structural units, calculated as C 15 H 14 and based on the total amount of compounds with a boiling point of more than 150 ° C at 1 bar (0.1 MPa).
- the present invention comprises a concentrate of the above-described corrosion protection agent, the concentrate having a pH in the range from 0.5 to 2.0 and based on at least 1% by weight of a water-soluble compound (A) of the element zirconium on the element zirconium and at least 0.01% by weight of polycyclic hydrocarbons (B) with at least two fused benzene rings each with at least contains two ring-substituted hydroxyl groups in the ortho position to one another, the benzene rings being bridged to one another by annulation to an acyclic hydrocarbon system, the acyclic hydrocarbon system preferably having at least one oxo group or hydroxyl group.
- A water-soluble compound
- B polycyclic hydrocarbons
- the concentrate optionally contains at least 1% by weight, preferably at least 2% by weight, but preferably not more than 20% by weight, particularly preferably not more than 10% by weight, of organic compounds (C) selected are made from copolymers or copolymer mixtures of alkenes and vinyl alcohol, preferably of ethene and vinyl alcohol, which in turn preferably each have a hydroxyl number in the range from 200 to 500 milligrams of KOH per gram of the copolymer or the copolymer mixture.
- organic compounds (C) selected are made from copolymers or copolymer mixtures of alkenes and vinyl alcohol, preferably of ethene and vinyl alcohol, which in turn preferably each have a hydroxyl number in the range from 200 to 500 milligrams of KOH per gram of the copolymer or the copolymer mixture.
- the water-soluble compound (A) of the element zirconium is preferably selected from zirconyl nitrate.
- the polycyclic hydrocarbon (B) selected from 1,2-hydroxyanthraquinone is also preferred in the concentrate according to the invention.
- the corrosion protection agent for use in a method according to the invention can be produced by diluting the concentrate by a factor of 5-20.
- the effectiveness of the pretreatment according to the invention to form a potential paint primer can be achieved after a small amount (approx. 1 ml) of an acidic aqueous pretreatment solution according to the invention (pH 1.5) containing 15 g / kg Zr in the form of zirconyl nitrate and 500 mg / kg alizarin on aluminum sheet (AI 3008; 0.2 mm thickness) and subsequent drying at 30 ° C in comparison to a treatment with a solution that does not contain the alizarin.
- an acidic aqueous pretreatment solution according to the invention pH 1.5
- an acidic aqueous pretreatment solution according to the invention pH 1.5
- the treatment according to the invention provides an iridescent coating that cannot be wiped off
- the rather white coating based solely on the zirconyl nitrate-containing solution is easy to remove with a cloth.
- Table 1 lists the various pretreatments and primer coatings that were tested in this regard.
- the pretreatment was carried out on alkaline (Bonderite® C-AK 1803 from Henkel AG & Co.KGaA, 15 g / L, 60 ° C, 10 s) cleaned and rinsed with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) aluminum sheets (AI 3006) was carried out with a thickness of 0.2 mm and a wet film of the pretreatment solution of approx. 4-6 ml / m 2 was applied and dried at 80 ° C. so that the zirconium layer was 12 mg / m 2 in each case.
- the organic primer was applied with a doctor blade and dried and cured at 249 ° C.
- PMT Peak Metal Temperature
- the pretreatment according to the invention in particular for the coating based on the acrylate-based primer, provides excellent paint adhesion values compared to a conventional fluorozirconate-based pretreatment, while for a coating based on the epoxy-based primer at least equally good results both in terms of paint adhesion as well as in terms of "blushing".
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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur korrosionsschützenden Vorbehandlung von Metallsubstraten unter Verwendung Zirkonium-basierter wässriger Korrosionsschutzmittel. Die korrosionsschützende Wirkung des Zirkonium-basierten Mittels beruht dabei auf der Anwesenheit polyzyklischer Kohlenwasserstoffe, die mindestens einen anellierten Benzenring mit jeweils mindestens zwei kernsubstituierten Hydroxylgruppen in ortho-Stellung zueinander aufweisen. Das wässrige Korrosionsschutzmittel kann dabei im Wesentlichen frei sowohl von passivierenden Chrom-haltigen Verbindungen als auch von das Metallsubstrat beizenden Fluorid-haltigen Verbindungen sein. Erfindungsgemäß ist die Vorbehandlung durch Auftrocknen (Dry-in-Place Verfahren) besonders vorteilhaft. Dementsprechend eignet sich das erfindungsgemäße Verfahren insbesondere für die Vorbehandlung von Metallband, wobei hervorragende Korrosionsschutzergebnisse auf Oberflächen von Aluminium oder Stahl erzielt werden. Die Erfindung umfasst zusätzlich ein Verfahren zur Herstellung beschichteter Dosendeckel aus Aluminiumband unter Verwendung des zuvor genannten Zirkonium-basierten Korrosionsschutzmittels. In einem weiteren Aspekt wird ein wässriges Konzentrat zur Bereitstellung der anwendungsfertigen Korrosionsschutzmittel umfasst.The present invention relates to a method for the anticorrosive pretreatment of metal substrates using zirconium-based aqueous corrosion protection agents. The anti-corrosive effect of the zirconium-based agent is based on the presence of polycyclic hydrocarbons, which have at least one fused benzene ring with in each case at least two nucleus-substituted hydroxyl groups in the ortho position to one another. The aqueous corrosion protection agent can be essentially free both of passivating chromium-containing compounds and of fluoride-containing compounds that pickle the metal substrate. According to the invention, the pretreatment by drying (dry-in-place method) is particularly advantageous. Accordingly, the method according to the invention is particularly suitable for the pretreatment of metal strip, with excellent corrosion protection results being achieved on surfaces of aluminum or steel. The invention additionally comprises a method for producing coated can ends from aluminum strip using the aforementioned zirconium-based corrosion protection agent. In a further aspect, an aqueous concentrate for providing the ready-to-use corrosion protection agents is included.
Die Konversionsbehandlung metallischer Oberflächen zur Bereitstellung eines vor Korrosion schützenden Überzuges auf Basis wässriger Zusammensetzungen enthaltend wasserlösliche Verbindungen des Elements Zirkonium ist ein in der Patentliteratur extensiv beschriebenes technisches Gebiet. Zur Verbesserung der Eigenschaftsprofils derartiger Konversionsbehandlungen hinsichtlich Korrosionsschutz und Vermittlung einer hinreichenden Lackhaftung sind vielfältige Varianten einer solchen Metallvorbehandlung bekannt, die entweder auf die Zusammensetzung der die Konversion bewirkenden Agentien abzielen oder auf im unmittelbaren Kontext der Konversionsbehandlung weitere nasschemische Behandlungsschritte zurückgreifen.The conversion treatment of metallic surfaces to provide a coating that protects against corrosion and is based on aqueous compositions containing water-soluble compounds of the element zirconium is a technical field that is extensively described in the patent literature. In order to improve the profile of properties of such conversion treatments with regard to corrosion protection and to provide adequate paint adhesion, various variants of such a metal pretreatment are known, which either aim at the composition of the agents causing the conversion or use further wet chemical treatment steps in the immediate context of the conversion treatment.
In diesem Zusammenhang sind auch verschiedene Verfahrensvarianten zur Bereitstellung der passivierenden Beschichtung prinzipiell bekannt, wobei das Auftrocknen derselben nach Aufbringen eines definierten Nassfilms stets eine Vorbehandlung in möglichst wenigen Schritten ermöglicht und diesbezüglich in verfahrenstechnischer Sicht eine herausragende Stellung einnimmt.
Grundsätzlich ist die Applikation wässriger Korrosionsschutzmittel durch Auftrocknen eines Nassfilms vollkommen etabliert und in der Praxis umgesetzt. Der
Basically, the application of aqueous corrosion protection agents by drying a wet film is completely established and implemented in practice. Of the
Es besteht demnach weiterhin ein Bedarf darin, ein verfahrenstechnisch hinsichtlich der Anzahl an notwendigen Verfahrensschritten möglichst effizientes Verfahren für die korrosionsschützende Vorbehandlung metallischer Substrate bereitzustellen, bei dem auf die passivierende Wirkung von Verbindungen des Elements Zirkonium abgestellt wird. Von besonderer Bedeutung ist dabei, ein solches Korrosionsschutzmittel bereitzustellen, dass bereits durch Auftragen und Auftrocknen ("Dry-in-Place" Verfahren) hervorragende Ergebnisse erzielt. Hervorragende Ergebnisse sind dann erreicht, wenn die Applikation im Dry-in-Place Verfahren Beschichtungen ergibt, die zusätzlich zu ihrer temporär vor Korrosion schützenden Wirkung im Zusammenspiel mit nachfolgend aufgebrachten Primer-Beschichtungen auf Basis filmbildender organischer Harze einen hervorragenden Schutz gegenüber korrosiver Enthaftung entfalten. Insbesondere die Eignung des Korrosionsschutzmittels durch Auftrocknen einen guten Lackhaftgrund auf Aluminiumsubstraten zu vermitteln und somit für die Herstellung von Getränkedosen in Frage zu kommen, ist vorliegend wünschenswert. Vorteilhafterweise ist das in einem deratigen Verfahren aufzutragende Korrosionsschutzmittel zudem weitgehend frei von umwelthygienisch problematischen Fluorid-freisetzenden Verbindungen.Accordingly, there is still a need to provide a process for the anti-corrosion pretreatment of metallic substrates that is as efficient as possible in terms of the number of process steps required, in which the passivating effect of compounds of the element zirconium is used. It is of particular importance here to provide such a corrosion protection agent that already achieves excellent results by applying and drying ("dry-in-place" method). Excellent results are achieved when the application in the dry-in-place process produces coatings which, in addition to their temporary protection against corrosion, in combination with subsequently applied primer coatings based on film-forming organic resins, provide excellent protection against corrosive delamination. In particular, the suitability of the anti-corrosive agent by drying to provide a good paint adhesion primer on aluminum substrates and thus being suitable for the production of beverage cans is desirable here. Advantageously, the anti-corrosion agent to be applied in such a process is also largely free of compounds that release fluoride which are problematic in terms of environmental hygiene.
Dieses Aufgabenspektrum wird gelöst durch ein Verfahren zur korrosionsschützenden Vorbehandlung eines metallischen Substrats, bei dem die Oberfläche des metallischen Substrats mit einem wässrigen Korrosionsschutzmittel in Kontakt gebracht wird, das mindestens eine wasserlösliche Verbindung (A) des Elements Zirkonium enthält, wobei das Mittel zusätzlich mindestens einen polyzyklischen Kohlenwasserstoff (B) enthält, der mindestens einen anellierten Benzenring mit jeweils mindestens zwei kernsubstituierten Hydroxylgruppen in ortho-Stellung zueinander aufweist, und wobei das molare Verhältnis von Zirkonium zum Gesamtfluorid-Gehalt in der homogenen wässrigen Phase des Korrosionsschutzmittels größer als 1 ist.This range of tasks is achieved by a method for the anticorrosive pretreatment of a metallic substrate, in which the surface of the metallic substrate is brought into contact with an aqueous corrosion protection agent which contains at least one water-soluble compound (A) of the element zirconium, the agent additionally at least one polycyclic Contains hydrocarbon (B) which has at least one fused benzene ring each with at least two nucleus-substituted hydroxyl groups in ortho-position to one another, and wherein the molar ratio of zirconium to the total fluoride content in the homogeneous aqueous phase of the anti-corrosion agent is greater than 1.
Eine Verbindung (A) des Elements Zirkonium ist im Rahmen der vorliegenden Erfindung wasserlöslich, wenn selbige bei 20°C in entionisierten Wasser, das eine spezifische Leitfähigkeit von weniger als 11µScm-1 aufweist, eine Löslichkeit von zumindest 0,1 g der Verbindung bezogen als auf das Element Zirkonium pro Kilogramm der dadurch hergestellten wässrigen Lösung aufweist.A compound (A) of the element zirconium is water-soluble in the context of the present invention if it has a solubility of at least 0.1 g of the compound at 20 ° C. in deionized water, which has a specific conductivity of less than 11 μScm −1 on the element zirconium per kilogram of the aqueous solution thus produced.
Im erfindungsgemäßen Verfahren ist gewährleistet, dass in Folge eines Beizangriffes auf das metallische Substrat eine Passivierung des metallischen Substrats vermittelt durch eine Oberflächenbelegung auf Basis schwerlöslicher Verbindungen des Elements Zirkon und des polyzyklischen Kohlenwasserstoffs eintritt. Erfindungsgemäß vorbehandelte metallische Substrate, die damit eine entsprechende Oberflächenbelegung aufweisen, sind darüber hinaus bestens geeignet einen hervorragenden Lackhaftgrund zu nachfolgenden Primern enthaltend filmbildende organische Harze zu vermitteln, hierzu kann das wässrige Korrosionsschutzmittel zusätzlich organische Polymere enthalten, ohne dass die Passivierung nachteilig beeinflusst wird. Für eine gute Passivierung, auf die sich auch die Anwesenheit von die Lackhaftung verbessernden organischen Polymeren nicht negativ auswirkt, ist es insbesondere vorteilhaft, wenn der polyzyklische Kohlenwasserstoff (B) eine geringe Löslichkeit in Wasser aufweist, so dass die für eine hinreichend Oberflächenbelegung im jeweiligen Applikationsverfahren notwendige gelöste Menge an polyzyklischen Kohlenwasserstoffs (B) idealerweise gerade noch im wässrigen Korrosionsschutzmittel gelöst vorliegt. In diesem Zusammenhang sind erfindungsgemäße Verfahren bevorzugt, in denen der polyzyklische Kohlenwasserstoff (B) bei 20°C in entionisierten Wasser mit einer spezifischen Leitfähigkeit von weniger als 1 µScm-1 eine Löslichkeit von weniger als 5 g, besonders bevorzugt von weniger als 1 g pro Kilogramm der dadurch hergestellten wässrigen Lösung aufweist. Eine derart geringe Löslichkeit des polyzyklischen Kohlenwasserstoffs (B) ist insbesondere bei Applikation des Korrosionsschutzmittels im Auftrocknungsverfahren (sogenanntes "Dry-in-Place Verfahren") von Vorteil, in der bereits geringe Mengen der Aktivkomponenten des Korrosionsschutzmittels für eine passivierend wirkende Oberflächenbelegung des zu schützenden metallischen Substrates ausreichend sein können. Der Begriff der Löslichkeit in Wasser ist bezüglich der Verbindung (B) so zu verstehen, dass oberhalb der genannten Löslichkeitsgrenzen bei einer Schergeschwindigkeit von 100 s-1 Dispersionen oder Emulsionen mit einem mittleren Partikeldurchmesser (D50-Wert) berechnet aus kumulativen Partikeldurchmesserverteilungskurven bestimmt mittels dynamischer Lichtstreumethoden von mehr als 50 nm resultieren.The method according to the invention ensures that, as a result of a pickling attack on the metallic substrate, passivation of the metallic substrate occurs mediated by a surface covering based on poorly soluble compounds of the element zirconium and the polycyclic hydrocarbon. Metallic substrates pretreated according to the invention, which thus have a corresponding surface coverage, are also ideally suited to impart an excellent paint primer to subsequent primers containing film-forming organic resins; for this purpose, the aqueous corrosion protection agent can additionally contain organic polymers without the passivation being adversely affected. For good passivation, on which the presence of organic polymers that improve paint adhesion does not have a negative effect, it is particularly advantageous if the polycyclic hydrocarbon (B) has a low solubility in water, so that it is necessary for adequate surface coverage in the respective application process The necessary dissolved amount of polycyclic hydrocarbon (B) is ideally still just dissolved in the aqueous corrosion protection agent. In this context, processes according to the invention are preferred in which the polycyclic hydrocarbon (B) at 20 ° C in deionized water with a specific conductivity of less than 1 μScm -1 has a solubility of less than 5 g, particularly preferably less than 1 g per Has kilograms of the aqueous solution produced thereby Such a low solubility of the polycyclic hydrocarbon (B) is particularly advantageous when applying the anti-corrosion agent in the drying process (so-called "dry-in-place process"), in which even small amounts of the active components of the anti-corrosion agent for a passivating surface covering of the metallic to be protected Substrates can be sufficient. The term solubility in water is to be understood with respect to the compound (B) so that above the solubility limits mentioned at a shear rate of 100 s -1 result in dispersions or emulsions with an average particle diameter (D50 value) calculated from cumulative particle diameter distribution curves determined by dynamic light scattering methods of more than 50 nm.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens enthält der polyzyklische Kohlenwasserstoff (B) mindestens zwei anellierte Benzenringe mit jeweils mindestens zwei kernsubstituierten Hydroxylgruppen in ortho-Stellung zueinander, wobei die Benzenringe jeweils durch Anellierung an ein acyclisches Kohlenwasserstoffsystem miteinander verbrückt vorliegen, wobei das acyclische Kohlenwasserstoffsystem vorzugsweise mindestens eine Oxo-Gruppe oder Hydroxyl-Gruppe aufweist. Derartige polyzyklische Kohlenwasserstoffe (B) sind dem Fachmann beispielsweise in Form des Hämatoxylins und dessen Oxidationsprodukts Hämatein sowie in Form des Alizarins geläufig.In a preferred embodiment of the process according to the invention, the polycyclic hydrocarbon (B) contains at least two fused benzene rings each with at least two nucleus-substituted hydroxyl groups in the ortho position to one another, the benzene rings each being bridged to one another by fusing to an acyclic hydrocarbon system, the acyclic hydrocarbon system preferably at least has an oxo group or hydroxyl group. Such polycyclic hydrocarbons (B) are familiar to the person skilled in the art, for example in the form of hematoxylin and its oxidation product hematein and in the form of alizarin.
Eine besonders homogene Oberflächenbelegung auf Basis des Elements Zirkonium und damit auch Passivierung gelingt, wenn die erfindungsgemäße Vorbehandlung in Anwesenheit von polyzyklischen Kohlenwasserstoffen (B) erfolgt, die auf dem Anthrachinon-Grundgerüst aufbauen. Dem folgend sind solche polyzyklischen Kohlenwasserstoffe (B) in erfindungsgemäßen Verfahren bevorzugt, die aus der Gruppe der mit mindestens zwei Hydroxyl-Gruppen in ortho-Stellung zueinander kernsubstituierten Anthrachinonen ausgewählt sind, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus 1,2-Dihydroxyanthrachinon, 3,4-Dihydroxyanthrachinon, 1,2,3-Trihydroxyanthrachinon, 1,2,4-Trihydroxyanthrachinon, 1,2,3-Trihydroxyanthrachinon, 1,2,5-Trihydroxyanthrachinon, 1,2,6-Trihydroxyanthrachinon, 1,2,7-Trihydroxyanthrachinon, 1,2,8-Trihydroxyanthrachinon, 1,2,3-Trihydroxyanthrachinon, 1,3,4-Trihydroxyanthrachinon, 1,4,5-Trihydroxyanthrachinon, 1,6,7-Trihydroxyanthrachinon, 1,2,5,8-Tetrahydroxyanthrachinon, 1,2,5,8-Tetrahydroxyanthrachinon 1,4,5,8-Tetrahydroxyanthrachinon, 1,2,3,4-Tetrahydroxyanthrachinon, insbesondere bevorzugt ist der polyzyklische Kohlenwasserstoff (B) ausgewählt aus 1,2-Hydroxyanthrachinon.A particularly homogeneous surface covering based on the element zirconium and thus also passivation is achieved if the pretreatment according to the invention takes place in the presence of polycyclic hydrocarbons (B) which build on the anthraquinone basic structure. Accordingly, those polycyclic hydrocarbons (B) are preferred in the process according to the invention which are selected from the group of anthraquinones with at least two hydroxyl groups in the ortho-position to one another, particularly preferably selected from the group consisting of 1,2-dihydroxyanthraquinone, 3 , 4-dihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,2,5-trihydroxyanthraquinone, 1,2,6-trihydroxyanthraquinone, 1,2,7 Trihydroxyanthraquinone, 1,2,8-trihydroxyanthraquinone, 1,2,3-trihydroxyanthraquinone, 1,3,4-trihydroxyanthraquinone, 1,4,5-trihydroxyanthraquinone, 1,6,7-trihydroxyanthraquinone, 1,2,5,8 -Tetrahydroxyanthraquinone, 1,2,5,8-tetrahydroxyanthraquinone 1,4,5,8-tetrahydroxyanthraquinone, 1,2,3,4-tetrahydroxyanthraquinone, the polycyclic hydrocarbon (B) selected from 1,2-hydroxyanthraquinone is particularly preferred.
Weiterhin sollte das Verhältnis von wasserlöslichen Verbindungen (A) des Elements Zirkonium zu polyzyklischen Kohlenwasserstoffen (B) für eine optimale Passivierung der Oberflächen der im erfindungsgemäßen Verfahren vorbehandelten metallischen Substrate in einem bestimmten Bereich liegen. Vorzugsweise ist das Gewichtsverhältnis von wasserlöslichen Verbindungen (A) des Elements Zirkonium bezogen auf das Element Zirkonium zu polyzyklischen Kohlenwasserstoffen (B) im Korrosionsschutzmittel des erfindungsgemäßen Verfahrens kleiner als 0,2, besonders bevorzugt kleiner als 0,1, jedoch bevorzugt größer als 0,02 ist.Furthermore, the ratio of water-soluble compounds (A) of the element zirconium to polycyclic hydrocarbons (B) should be in a certain range for optimal passivation of the surfaces of the metallic substrates pretreated in the process according to the invention. The weight ratio of water-soluble compounds (A) of the zirconium element based on the zirconium element to polycyclic hydrocarbons (B) in the corrosion protection agent of the process according to the invention is preferably less than 0.2, particularly preferably less than 0.1, but preferably greater than 0.02 is.
Bevorzugte Mengen der polyzyklischen Kohlenwasserstoffe (B) im Korrosionsschutzmittel des erfindungsgemäßen Verfahrens liegen im Bereich von 5 - 250 mg/kg.Preferred amounts of the polycyclic hydrocarbons (B) in the anti-corrosion agent of the process according to the invention are in the range from 5-250 mg / kg.
Das Korrosionsschutzmittel, das in erfindungsgemäßen Verfahren eingesetzt wird, ist für eine erhöhte Löslichkeit der wasserlöslichen Verbindungen (A) des Elements Zirkonium und eine das Metallsubstrat beizende Wirkung vorzugsweise sauer eingestellt. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist der pH-Wert des Korrosionsschutzmittels kleiner als 2,0, besonders bevorzugt kleiner als 1,6, jedoch vorzugsweise größer als 0,5, besonders bevorzugt größer als 1,0.The anti-corrosive agent which is used in the process according to the invention is preferably adjusted to be acidic for an increased solubility of the water-soluble compounds (A) of the element zirconium and an acidic effect on the metal substrate. In a preferred embodiment of the method according to the invention, the pH of the corrosion protection agent is less than 2.0, particularly preferably less than 1.6, but preferably greater than 0.5, particularly preferably greater than 1.0.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, dass ein hoher Beizabtrag also eine hohe Metallauflösungsrate während des In-Kontakt-Bringens mit dem Korrosionsschutzmittel für eine hinreichende Oberflächenpassivierung nicht notwendig ist. Konsequenterweise kann das Korrosionsschutzmittel in besonders vorteilhaften Ausführungsformen der Erfindung weitgehend frei von umwelthygienisch bedenklichen Fluoriden oder Fluorid-freisetzenden Verbindungen formuliert sein, die üblicherweise zur Erhöhung der Beizrate, insbesondere auf Aluminiumsubstraten, eingesetzt werden.The method according to the invention is characterized in that a high rate of pickling removal, ie a high rate of metal dissolution during the bringing into contact with the corrosion protection agent, is not necessary for adequate surface passivation. Consequently, in particularly advantageous embodiments of the invention, the corrosion protection agent can be formulated largely free of environmentally harmful fluorides or fluoride-releasing compounds which are usually used to increase the pickling rate, in particular on aluminum substrates.
Dementsprechend ist im erfindungsgemäßen Verfahren das molare Verhältnis von Zirkonium zum Gesamtfluorid-Gehalt in der homogenen wässrigen Phase des Korrosionsschutzmittels größer als 1, vorzugsweise größer als 2, besonders bevorzugt größer als 4. Der Gesamtfluorid-Gehalt wird dabei in einem TISAB gepufferten aliquoten Teil des Korrosionsschutzmittels mit einer Fluoridsensitiven Elektrode bei 20 °C bestimmt (TISAB: "Total lonic Strength Adjustment Buffer"), wobei das volumenbezogene Mischungsverhältnis von Puffer zum aliquoten Teil des Korrosionsschutzmittels 1 : 1 ist. Der TISAB Puffer wird hergestellt durch Auflösung von 58 g NaCI, 1 g Natriumcitrat und 50 ml Eisessig in 500 ml entionisiertem Wasser (κ < 1µScm-1) und Einstellen eines pH-Wertes von 5,3 mittels 5 N NaOH sowie Auffüllen auf ein Gesamtvolumen von 1000 ml wiederum mit entionisiertem Wasser (κ < 1µScm-1).Accordingly, in the process according to the invention, the molar ratio of zirconium to the total fluoride content in the homogeneous aqueous phase of the anti-corrosion agent is greater than 1, preferably greater than 2, particularly preferably greater than 4. The total fluoride content is in a TISAB buffered aliquot of the anti-corrosion agent determined with a fluoride-sensitive electrode at 20 ° C (TISAB: "Total lonic Strength Adjustment Buffer"), the volume-based mixing ratio of buffer to the aliquot of the corrosion protection agent being 1: 1. The TISAB buffer is prepared by dissolving 58 g of NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water (κ <1 μScm -1 ) and setting a pH value of 5.3 using 5 N NaOH and making up to a total volume of 1000 ml again with deionized water (κ <1µScm -1 ).
Weitergehend ist in diesem Zusammenhang erfindungsgemäß bevorzugt, dass die Quelle der wasserlöslichen Verbindung (A) des Elements Zirkonium nicht auch eine Quelle für Fluorid-Ionen darstellt und vorzugsweise ausgewählt ist aus Zirkonylnitrat, Zirkoniumacetat und/oder Ammoniumzirkoniumcarbonat, besonders bevorzugt aus Zirkonylnitrat.Furthermore, in this context it is preferred according to the invention that the source of the water-soluble compound (A) of the element zirconium is not also a source of fluoride ions and is preferably selected from zirconyl nitrate, zirconium acetate and / or ammonium zirconium carbonate, particularly preferably from zirconyl nitrate.
Die bevorzugte Menge der wasserlöslichen Verbindung (A) im Korrosionsschutzmittel des erfindungsgemäßen Verfahrens beträgt mindestens 40 mg/kg, besonders bevorzugt mindestens 200 mg/kg, insbesondere zumindest 400 mg/kg, jedoch vorzugsweise nicht mehr als 4000 mg/kg jeweils bezogen auf die Menge des Elements Zirkonium.The preferred amount of the water-soluble compound (A) in the corrosion protection agent of the process according to the invention is at least 40 mg / kg, particularly preferably at least 200 mg / kg, in particular at least 400 mg / kg, but preferably not more than 4000 mg / kg, based on the amount of the element zirconium.
In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist der Gesamtfluorid-Gehalt in der wässrigen Phase des Korrosionsschutzmittels kleiner als 50 mg/kg, vorzugsweise kleiner als 10 mg/kg, besonders bevorzugt kleiner als 1 mg/kg jeweils bezogen auf das Korrosionsschutzmittel.In a particularly preferred embodiment of the method according to the invention, the total fluoride content in the aqueous phase of the corrosion protection agent is less than 50 mg / kg, preferably less than 10 mg / kg, particularly preferably less than 1 mg / kg, based on the corrosion protection agent.
Ein weiterer Vorteil der vorliegenden Erfindung in ökologischer Hinsicht besteht auch darin, dass das Korrosionsschutzmittel keine schwerlöslichen Salze bildenden Anionen wie Phosphate enthalten muss, um eine passivierende Beschichtung auszubilden. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens sind im Korrosionsschutzmittel daher weniger als 0,2 Gew.-%, besonders bevorzugt weniger als 0,1 Gew.-%, an gelösten Phosphaten berechnet als PO4 enthalten.Another advantage of the present invention from an ecological point of view is that the corrosion protection agent does not have to contain anions which form sparingly soluble salts such as phosphates in order to form a passivating coating. In a preferred embodiment of the method according to the invention, the corrosion protection agent therefore contains less than 0.2% by weight, particularly preferably less than 0.1% by weight, of dissolved phosphates, calculated as PO 4 .
Das erfindungsgemäße Verfahren ist hervorragend geeignet, um auf metallischen Substraten einen Lackhaftgrund, insbesondere durch Auftrocknen eines Nassfilms des Korrosionsschutzmittels, bereitzustellen. Diese Eignung beinhaltet, dass sich die Anwesenheit lackhaftungsverbessernder organischer Polymere im wässrigen Korrosionsschutzmittel nicht negativ auf die Passivierung auswirkt. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens, in der organische Polymere zur weitergehenden Verbesserung der Lackhaftung eingesetzt werden, sind im Korrosionsschutzmittel daher mindestens 0,1 Gew.-%, besonders bevorzugt mindestens 0,2 Gew.-%, an organischen Verbindungen (C) jeweils bezogen auf das wässrige Korrosionsschutzmittel enthalten, die eine Molmasse oberhalb von 5.000 g/mol aufweisen. Die Molmasse kann vorliegend direkt im Korrosionsschutzmittel bei 20 °C mittels Gelpermeationschromatographie unter Verwendung eines konzentrationsabhängigem Detektor bestimmt werden, wobei auf gegen Pullalan-Standards kalibrierte Molmassenverteilungskurven zurückzugreifen ist. Die organischen Verbindungen (C) enthalten vorzugsweise zumindest teilweise funktionelle Gruppen ausgewählt aus Hydroxyl-Gruppen, Carboxyl-Gruppen, Phosphat-Gruppen, Phosphonat-Gruppen und Amino-Gruppen. In einer besonders bevorzugten Ausführungsform beträgt die Summe aus Säurezahl und Hydroxylzahl mindestens 100 Milligramm KOH pro Gramm, besonders bevorzugt mindestens 200 Milligramm KOH pro Gramm der organischen Verbindungen (C), jedoch vorzugsweise nicht mehr als 600 Milligramm KOH pro Gramm der organischen Verbindungen (C).The method according to the invention is outstandingly suitable for providing a paint primer on metallic substrates, in particular by drying a wet film of the corrosion protection agent. This suitability means that the presence of organic polymers that improve paint adhesion in the aqueous corrosion protection agent does not have a negative effect on the passivation. In a preferred embodiment of the process according to the invention, in which organic polymers are used to further improve paint adhesion, the corrosion protection agent therefore contains at least 0.1% by weight, particularly preferably at least 0.2% by weight, of organic compounds (C) each based on the aqueous corrosion protection agent, which have a molar mass above 5,000 g / mol. In the present case, the molar mass can be determined directly in the anticorrosion agent at 20 ° C. by means of gel permeation chromatography using a concentration-dependent detector, using molar mass distribution curves calibrated against Pullalan standards. The organic compounds (C) preferably contain at least partially functional groups selected from hydroxyl groups, carboxyl groups, phosphate groups, phosphonate groups and amino groups. In a particularly preferred embodiment, the sum of the acid number and hydroxyl number is at least 100 milligrams of KOH per gram, particularly preferably at least 200 milligrams of KOH per gram of the organic compounds (C), but preferably not more than 600 milligrams of KOH per gram of the organic compounds (C) .
Die Säurezahl ist erfindungsgemäß eine experimentell zu bestimmende Messgröße, die ein Maß für die Anzahl der freien Säuregruppen im Polymer oder in einer Polymerenmischung ist. Die Säurezahl wird bestimmt, indem eine eingewogene Menge des Polymers oder der Polymerenmischung in einem Lösemittelgemisch aus Methanol und destilliertem Wasser im Volumenverhältnis 3 : 1 gelöst und anschließend mit 0,05 mol/l KOH in Methanol potentiometrisch titriert wird. Die potentiometrische Messung erfolgt mit einer Einstabmesskette (LL-Solvotrode® der Fa. Metrohm; Bezugselektrolyt: 0,4 mol/l Tetraethylammoniumbromid in Ethylenglykol). Die Säurezahl entspricht dabei der hinzugesetzten Menge an KOH in Milligramm pro Gramm Polymer bzw. Polymerenmischung im Wendepunkt der potentiometrischen Titrationskurve.According to the invention, the acid number is a measured variable to be determined experimentally, which is a measure of the number of free acid groups in the polymer or in a polymer mixture. The acid number is determined by dissolving a weighed amount of the polymer or the polymer mixture in a solvent mixture of methanol and distilled water in a volume ratio of 3: 1 and then potentiometrically titrating it with 0.05 mol / l KOH in methanol. The potentiometric measurement is carried out with a combination electrode (LL-Solvotrode® from Metrohm; reference electrolyte: 0.4 mol / l tetraethylammonium bromide in ethylene glycol). The acid number corresponds to the added amount of KOH in milligrams per gram of polymer or polymer mixture at the turning point of the potentiometric titration curve.
Analog gilt erfindungsgemäß, dass die Hydroxylzahl als Maß für die Anzahl an freien Hydroxylgruppen im Polymer oder in einer Polymerenmischung experimentell durch potentiometrische Titration bestimmt werden kann. Hierfür wird eine eingewogene Menge des Polymers oder der Polymerenmischung in einer Reaktionslösung von 0,1 mol/l Phthalsäureanhydrid in Pyridin bei 130 °C für 45 Minuten erwärmt und zunächst mit dem 1,5 fachen Volumen der Reaktionslösung an Pyridin und anschließend mit dem 1,5 fachen Volumen der Reaktionslösung an entionisiertem Wasser (κ < 1 µScm-1) versetzt. Die freigesetzte Menge an Phthalsäure wird in diesem Gemisch mittels 1 M Kalilauge titriert. Die potentiometrische Messung erfolgt mit einer Einstabmesskette (LL-Solvotrode® der Fa. Metrohm; Bezugselektrolyt: 0,4 mol/l Tetraethylammoniumbromid in Ethylenglykol). Die Hydroxylzahl entspricht dabei der hinzugesetzten Menge an KOH in Milligramm pro Gramm Polymer bzw. Polymerenmischung im Wendepunkt der potentiometrischen Titrationskurve.Analogously, according to the invention, the hydroxyl number can be determined experimentally by potentiometric titration as a measure of the number of free hydroxyl groups in the polymer or in a polymer mixture. For this purpose, a weighed amount of the polymer or the polymer mixture in a reaction solution of 0.1 mol / l phthalic anhydride in pyridine is heated at 130 ° C for 45 minutes and first with 1.5 times the volume of the reaction solution of pyridine and then with the 1, 5 times the volume of the reaction solution of deionized water (κ <1 µScm -1 ) was added. The amount of phthalic acid released is titrated in this mixture using 1 M potassium hydroxide solution. The potentiometric measurement is carried out with a combination electrode (LL-Solvotrode® from Metrohm; reference electrolyte: 0.4 mol / l tetraethylammonium bromide in ethylene glycol). The hydroxyl number corresponds to the added amount of KOH in milligrams per gram of polymer or polymer mixture at the turning point of the potentiometric titration curve.
Insbesondere für die Vorbehandlung von Aluminium im Dry-in-Place Verfahren sind erfindungsgemäß solche wässrigen Korrosionsschutzmittel bevorzugt, die als organische Verbindungen (C) Copolymere oder Copolymerenmischungen von Alkenen und Vinylalkohol, besonders bevorzugt von Ethen und Vinylalkohol, enthalten, die insbesondere bevorzugt eine Hydroxylzahl im Bereich von 200 bis 500 Milligramm KOH pro Gramm des Copoylmers bzw. der Copolymerenmischung aufweisen. Der Anteil dieser Copolymere oder Copolymerenmischung beträgt vorzugsweise mindestens 0,1 Gew.-%, besonders bevorzugt mindestens 0,2 Gew.-%, übersteigt jedoch vorzugsweise nicht 5 Gew.-%, besonders bevorzugt nicht 2 Gew.-% jeweils bezogen auf das wässrige Korrosionsschutzmittel.Particularly for the pretreatment of aluminum in the dry-in-place process, those aqueous corrosion inhibitors are preferred according to the invention which contain, as organic compounds (C), copolymers or copolymer mixtures of alkenes and vinyl alcohol, particularly preferably ethene and vinyl alcohol, which particularly preferably have a hydroxyl number im Range from 200 to 500 milligrams of KOH per gram of the copolymer or the copolymer mixture. The proportion of these copolymers or copolymer mixture is preferably at least 0.1% by weight, particularly preferably at least 0.2% by weight, but preferably does not exceed 5% by weight, particularly preferably not 2% by weight, in each case based on the aqueous corrosion protection agents.
Die Anwesenheit von partikulären Bestandteilen, beispielsweise Korrosionsschutzpigmenten, im Korrosionsschutzmittel bringt für eine weitergehende Passivierung keine signifikanten Vorteile und ist für die Ausbildung homogener dünner Überzüge im erfindungsgemäßen Verfahren eher nachteilig. Entsprechend sind erfindungsgemäße Verfahren bevorzugt, in denen im Korrosionsschutzmittel weniger als 0,1 Gew.-%, besonders bevorzugt weniger als 0,01 Gew.-%, an partikulären anorganischen Bestandteilen enthalten sind, die bei einer Ultrafiltration mit einer Ausschlussgrenze von 50 kD im Retentat zurückgehalten werden.The presence of particulate constituents, for example anti-corrosive pigments, in the anti-corrosive agent brings no significant advantages for further passivation and is rather disadvantageous for the formation of homogeneous thin coatings in the process according to the invention. Correspondingly, processes according to the invention are preferred in which the corrosion protection agent contains less than 0.1% by weight, particularly preferably less than 0.01% by weight, of particulate inorganic constituents which, in the case of ultrafiltration, have an exclusion limit of 50 kD Retentate to be retained.
Ein weiterer Vorteil der vorliegenden Erfindung besteht darin, dass das wässrige Korrosionsschutzmittel im Wesentlichen frei von toxischen Schwermetallen formuliert sein kann. In einer bevorzugten Ausführungsform enthält das wässrige Korrosionsschutzmittel daher weniger als 50 mg/kg, vorzugsweise weniger als 10 mg/kg, besonders bevorzugt weniger als 10 mg/kg, an Verbindungen des Elements Chrom, und in einer weiteren bevorzugten Ausführungsform weniger als 50 mg/kg, vorzugsweise weniger als 10 mg/kg, besonders bevorzugt weniger als 1 mg/kg, an Verbindungen der Elemente Chrom, Nickel und Cobalt.Another advantage of the present invention is that the aqueous corrosion protection agent can be formulated essentially free of toxic heavy metals. In a preferred embodiment, the aqueous corrosion protection agent therefore contains less than 50 mg / kg, preferably less than 10 mg / kg, particularly preferably less than 10 mg / kg, of compounds of the element chromium, and in a further preferred embodiment less than 50 mg / kg kg, preferably less than 10 mg / kg, particularly preferably less than 1 mg / kg, of compounds of the elements chromium, nickel and cobalt.
Die im erfindungsgemäßen Verfahren vorbehandelten metallischen Substrate sollten im wässrigen Korrosionsschutzmittel unter den verfahrenstechnisch üblichen Bedingungen gegenüber Säuren und Luftsauerstoff einen hinreichenden Lösungsdruck aufweisen, und damit zumindest in einem solchem Umfang korrodieren, dass eine Konversion der natürlichen oder mittels nasschemischer Reinigung spezifisch eingestellten dünnen Oxidschicht auf dem jeweiligen Metallsubstrat in Gang gesetzt wird, die durch die Abscheidung von Elementen und Verbindungen der Aktivkomponenten des Korrosionsschutzmittels vollendet wird.The metallic substrates pretreated in the process according to the invention should have a sufficient solution pressure in the aqueous anti-corrosive agent under the usual process engineering conditions with respect to acids and atmospheric oxygen, and thus corrode at least to such an extent that a conversion of the natural or thin oxide layer specifically adjusted by means of wet-chemical cleaning on the respective Metal substrate is set in motion, which is completed by the deposition of elements and compounds of the active components of the anti-corrosion agent.
Daher ist die Vorbehandlung von solchen metallischen Substraten erfindungsgemäß bevorzugt, die in einem mit Sauerstoff gesättigten Kaliumhydrogenphthalat-Puffer (0,05 mol/L, pH 4,01, 20 °C, 0,21 bar Sauerstoffpartialdruck in der Atmosphäre) ein Korrosionspotential von weniger als +0,2 V (SHE) aufweisen.Therefore, the pretreatment of those metallic substrates is preferred according to the invention, which in an oxygen-saturated potassium hydrogen phthalate buffer (0.05 mol / L, pH 4.01, 20 ° C, 0.21 bar oxygen partial pressure in the atmosphere) has a corrosion potential of less as +0.2 V (SHE).
In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens sind die metallischen Substrate ausgewählt aus Zink und/oder Aluminium sowie deren Legierungen, besonders bevorzugt aus Aluminium und seinen Legierungen. Legierungen werden dabei im Rahmen der vorliegenden Erfindung von solchen Metallsubstraten gebildet, die das jeweilige Metallelement mit einen Anteil von mindestens 50 At.-% enthalten. Gerade auf Substraten des Metalls Aluminium kann im erfindungsgemäßen Verfahren eine besonders effektive und homogene Passivierung des Aluminiumwerkstoffes beobachtet werden, die nahezu unabhängig von der Applikationsart eintritt und üblicherweise derart vollzogen ist, dass eine hervorragende Haftung zu nachträglich aufgebrachten Primern enthaltend mindestens ein aushärtbares filmbildendes organisches Harz resultiert, insbesondere dann wenn das filmbildende Harz zur Kondensation befähigte funktionelle Gruppen ausgewählt aus Phosphonsäure-, Phosphorsäure-, Oxiran-, Amino-, Hydroxyl- und/oder Carboxylgruppen aufweist.In a particular embodiment of the method according to the invention, the metallic substrates are selected from zinc and / or aluminum and their alloys, particularly preferably from aluminum and its alloys. In the context of the present invention, alloys are formed from metal substrates which contain the respective metal element in a proportion of at least 50 at%. In the process according to the invention, particularly effective and homogeneous passivation of the aluminum material can be observed, especially on substrates made of the metal aluminum, which occurs almost independently of the type of application and is usually carried out in such a way that excellent adhesion to subsequently applied primers containing at least one curable film-forming organic resin results , especially when the film-forming resin has functional groups capable of condensation selected from among phosphonic acid, phosphoric acid, oxirane, amino, hydroxyl and / or carboxyl groups.
Das Korrosionsschutzmittel kann mittels üblicher dem Fachmann der Oberflächenbehandlung bekannter Methoden mit dem Metallsubstrat in Kontakt gebracht werden. Eine erfindungsgemäß bevorzugte Applikationsart ist jedoch die Einstellung eines definierten Nassfilms auf der Oberfläche eines vorzugsweise flächig ausgebildeten Metallsubstrates, bspw. im Walzenauftragsverfahren oder durch Aufsprühen und Abwischen, und Auftrocknen desselben, so dass reproduzierbare und für eine Passivierung stets ausreichende Mengen der Aktivkomponenten des Korrosionsschutzmittels auf dem Metallsubstrat verbleiben.The anti-corrosion agent can be brought into contact with the metal substrate by means of conventional methods known to those skilled in the art of surface treatment. A preferred type of application according to the invention, however, is the setting of a defined wet film on the surface of a preferably flat metal substrate, for example in the roller application process or by spraying and wiping it on, and drying it, so that reproducible and always sufficient quantities of the active components of the corrosion protection agent on the Metal substrate remain.
Insofern ist ein solches Verfahren erfindungsgemäß bevorzugt, bei dem nach dem In-Kontakt-Bringen des metallischen Substrats mit dem wässrigen Korrosionsschutzmittel ein Nassfilm des Korrosionsschutzmittels auf der Oberfläche des metallischen Substrats verbleibt, der vor einem nachfolgenden Spülschritt oder einer nachfolgenden nasschemischen Behandlung, vorzugsweise durch Wärmezufuhr, getrocknet wird (sogenanntes "Dry-in-Place" Verfahren). Die Trocknung kann mit allen technischen Mitteln erfolgen, die im Resultat bewirken, dass die flüssigen Bestandteile des Nassfilms mit einem Siedepunkt bei 1 bar (1 bar = 0,1 MPa) von nicht mehr als 150 °C in die umgebende Atmosphäre übergehen. Die Trocknung kann daher alternativ zur Wärmezufuhr, auch durch Überleiten eines trockenen Luftstromes erfolgen. Eine nasschemische Behandlung ist im Rahmen der vorliegenden Erfindung jedwede Behandlung des Substrats mit einem Wasser enthaltenden Mittel, die nicht allein dazu dient, in einem Nassfilm enthaltende Aktivkomponenten eines vorausgegangenen Behandlungsschrittes von der Oberfläche des Metallsubstrates zu entfernen.In this respect, such a method is preferred according to the invention in which, after the metallic substrate has been brought into contact with the aqueous corrosion protection agent, a wet film of the corrosion protection agent remains on the surface of the metallic substrate, which is preferably applied before a subsequent rinsing step or a subsequent wet chemical treatment by supplying heat, is dried (so-called "dry-in-place" method). Drying can be carried out with all technical means that have the effect that the liquid components of the wet film with a boiling point at 1 bar (1 bar = 0.1 MPa) of no more than 150 ° C pass into the surrounding atmosphere. As an alternative to the supply of heat, drying can therefore also be carried out by passing a dry air stream over it. In the context of the present invention, a wet chemical treatment is any treatment of the substrate with a water-containing agent which does not only serve to remove active components contained in a wet film from a previous treatment step from the surface of the metal substrate.
Weiterhin ist für eine hinreichende Passivierung, insbesondere auf den Substraten Zink und/oder Aluminium sowie deren Legierungen, erfindungsgemäß zu bevorzugen, dass der Nassfilm des Korrosionsschutzmittels in einer solchen Filmdicke auf dem Metallsubstrat verbleibt, dass nach dem Trocknen eine Schichtauflage an Zirkonium von mehr als 5 mg/m2, vorzugsweise mehr als 10 mg/m2, jedoch vorzugsweise von weniger als 150 mg/m2, besonders bevorzugt von weniger als 50 mg/m2 resultiert.Furthermore, for sufficient passivation, in particular on the substrates zinc and / or aluminum and their alloys, it is preferable according to the invention that the wet film of the corrosion protection agent remains on the metal substrate in such a film thickness that, after drying, a layer of zirconium of more than 5 mg / m 2 , preferably more than 10 mg / m 2 , but preferably less than 150 mg / m 2 , particularly preferably less than 50 mg / m 2 .
Die besondere Eignung des erfindungsgemäßen Verfahrens für Aluminium und seine Legierungen im Zusammenspiel mit der bevorzugten Applikation des Korrosionsschutzmittels durch Auftragen und unmittelbar nachfolgendem Eintrocknen macht das erfindungsgemäße Verfahren speziell für die Bereitstellung von vorbehandeltem Aluminiumband attraktiv. Eine besondere Ausgestaltung des erfindungsgemäßen Verfahrens dient daher der Herstellung beschichteter Dosendeckel aus Aluminiumband, wobei zu deren Herstellung in einem ersten Schritt auf Aluminiumband ein solcher Nassfilm eines wässrigen Korrosionsschutzmittels enthaltend mindestens eine wasserlösliche Verbindung (A) des Elements Zirkonium und mindestens einen polyzyklischen Kohlenwasserstoff (B), der mindestens einen anellierten Benzenring mit jeweils mindestens zwei kernsubstituierten Hydroxylgruppen in ortho-Stellung zueinander aufweist, aufgebracht wird, der nach Trocknung eine Schichtauflage an Zirkonium von mehr als 5 mg/m2 realisiert, woraufhin nach Trocknung das Deckelmaterial aus dem Band ausgestanzt und zum Dosendeckel umgeformt wird. Der Trocknung nachfolgend, jedoch vorzugsweise vor der Umformung zum Deckelmaterial wird eine organische Beschichtung mittels Primer enthaltend mindestens ein aushärtbares filmbildendes organisches Harz, das wiederum bevorzugt zur Kondensation befähigte funktionelle Gruppen ausgewählt aus Phosphonsäure-, Phosphorsäure-, Oxiran-, Amino-, Hydroxyl- und/oder Carboxylgruppen aufweist, erfindungsgemäß bevorzugt aufgebracht und ausgehärtet. Als Primer wird vorliegend ein Mittel zur Erstbeschichtung der erfindungsgemäß mit dem Korrosionsschutzmittel vorbehandelten Metallsubstrate mit einem organischen Material verstanden, das als solches notwendigerweise mindestens ein aushärtbares filmbildendes organisches Harz enthält. Im Zuge der Erstbeschichtung mit dem Primer werden üblicherweise Schichtdicken im Bereich von 0,5 - 50 µm realisiert.The particular suitability of the method according to the invention for aluminum and its alloys in conjunction with the preferred application of the corrosion protection agent by application and immediately subsequent drying makes the method according to the invention especially attractive for the provision of pretreated aluminum strip. A special embodiment of the method according to the invention therefore serves to produce coated can ends from aluminum strip, for their production in a first step on aluminum strip such a wet film of an aqueous corrosion protection agent containing at least one water-soluble compound (A) of the element zirconium and at least one polycyclic hydrocarbon (B) , which has at least one fused benzene ring with at least two nucleus-substituted hydroxyl groups in ortho position to one another, is applied, which, after drying, realizes a layer of zirconium of more than 5 mg / m 2 , whereupon, after drying, the cover material is punched out of the tape and Can end is reshaped. Subsequent to drying, but preferably before reshaping to form the lid material, an organic coating is applied by means of a primer containing at least one curable film-forming organic resin, which in turn preferably has functional groups capable of condensation selected from phosphonic acid, phosphoric acid, oxirane, amino, hydroxyl and / or has carboxyl groups, preferably applied according to the invention and cured. In the present case, a primer is understood to mean an agent for the first coating of the metal substrates pretreated according to the invention with the corrosion protection agent with an organic material which as such necessarily contains at least one curable film-forming organic resin. In the course of the initial coating with the primer, layer thicknesses in the range of 0.5 - 50 µm are usually implemented.
Für das erfindungsgemäße Verfahren zur Herstellung beschichteter Dosendeckel aus Aluminiumband sind analog die bereits im Kontext des allgemeinen Verfahrens zur korrosionsschützenden Vorbehandlung eines metallischen Substrats näher beschriebenen Korrosionsschutzmittel vorzugsweise einzusetzen.For the method according to the invention for producing coated can ends from aluminum strip, the corrosion protection agents already described in more detail in the context of the general method for the anticorrosive pretreatment of a metallic substrate are preferably to be used.
In einem bevorzugten erfindungsgemäßen Verfahren zur Herstellung beschichteter Dosendeckel aus Aluminiumband enthält der Primer ein aushärtbares filmbildendes organisches Harz, das ausgewählt ist aus einem Copolymer oder einer Copolymerenmischung mindestens eines aliphatischen und acyclischen Alkens mit mindestens einer α,β ungesättigten Carbonsäure in wasserdispergierter Form, wobei die Säurezahl des Copolymers oder der Copolymerenmischung vorzugsweise mindestens 20 mg KOH / g, jedoch vorzugsweise nicht mehr als 200 mg KOH / g beträgt und die Säuregruppen des Copolymers oder der Copolymerenmischung in wasserdispergierter Form vorzugsweise zumindest zu 20%, jedoch vorzugsweise nicht mehr als zu 60% neutralisiert vorliegen.In a preferred method according to the invention for producing coated can lids from aluminum strip, the primer contains a curable film-forming organic resin which is selected from a copolymer or a copolymer mixture of at least one aliphatic and acyclic alkene with at least one α, β unsaturated carboxylic acid in water-dispersed form, the acid number being of the copolymer or the copolymer mixture is preferably at least 20 mg KOH / g, but preferably not more than 200 mg KOH / g and the acid groups of the copolymer or the copolymer mixture in water-dispersed form is preferably at least 20%, but preferably not more than 60% neutralized exist.
Alternativ ist das aushärtbare filmbildende organische Harz des Primers bevorzugt ausgewählt aus einer Acrylat-Dispersion erhältlich als Reaktionsprodukt eines terminale oder seitenständige ethylenisch ungesättigte Gruppen aufweisenden Polymers, das vorzugsweise eine zahlenmittlere Molmasse im Bereich von 3000-50.000 g/mol aufweist, mit einer Mischung von ethylenisch ungesättigten Gruppen aufweisenden Monomeren umfassend solche mit Carboxyl-Gruppen wie beispielsweise (Meth)acrylsäure, Itaconsäure und Crotonsäure. Die Herstellung derartiger Dispersionen ist in der
Aufgrund der ausgesprochen guten Lackhaftung, die durch eine erfindungsgemäße Vorbehandlung auf Basis der zuvor beschriebenen Korrosionsschutzmittel erzielt wird, kann auf spezielle häufig Epoxid-basierte Primer verzichtet werden, die im Verpackungsbereich geringe Mengen an Hormongiften, beispielsweise Bisphenol A, an das bevorratete Lebensmittel abgeben können und daher vorzugsweise nicht zur Anwendung kommen sollten. Entsprechend sind die Primer zur Erstbeschichtung des vorbehandelten Aluminiumbands zur Herstellung von Dosendeckeln vorzugsweise weitestgehend frei von organischen Verbindungen, die eine Diphenylmethan-Struktureinheit aufweisen und enthalten besonders bevorzugt weniger als 0,1 Gew.-% an Diphenylmethan-Struktureinheiten berechnet als C15H14 und bezogen auf die Gesamtmenge der Verbindungen mit einem Siedepunkt von mehr als 150 °C bei 1 bar (0,1 MPa).Due to the extremely good paint adhesion that is achieved by a pretreatment according to the invention on the basis of the corrosion protection agents described above, special often epoxy-based primers can be dispensed with, which can release small amounts of hormone poisons, for example bisphenol A, to the stored food in the packaging area should therefore preferably not be used. Accordingly, the primers for the first coating of the pretreated aluminum strip for the production of can lids are preferably largely free of organic compounds that have a diphenylmethane structural unit and particularly preferably contain less than 0.1% by weight of diphenylmethane structural units, calculated as C 15 H 14 and based on the total amount of compounds with a boiling point of more than 150 ° C at 1 bar (0.1 MPa).
In einem weiteren Aspekt umfasst die vorliegende Erfindung ein Konzentrat des zuvor beschriebenen Korrosionsschutzmittels, wobei das Konzentrat einen pH-Wert im Bereich von 0,5 bis 2,0 aufweist und mindestens 1 Gew.-% einer wasserlöslichen Verbindung (A) des Elements Zirkonium bezogen auf das Element Zirkonium sowie mindestens 0,01 Gew.-% an polyzyklischen Kohlenwasserstoffen (B) mit mindestens zwei anellierten Benzenringen mit jeweils mindestens zwei kernsubstituierten Hydroxylgruppen in ortho-Stellung zueinander enthält, wobei die Benzenringe jeweils durch Anellierung an ein acyclisches Kohlenwasserstoffsystem miteinander verbrückt vorliegen, wobei das acyclische Kohlenwasserstoffsystem vorzugsweise mindestens eine Oxo-Gruppe oder Hydroxyl-Gruppe aufweist.In a further aspect, the present invention comprises a concentrate of the above-described corrosion protection agent, the concentrate having a pH in the range from 0.5 to 2.0 and based on at least 1% by weight of a water-soluble compound (A) of the element zirconium on the element zirconium and at least 0.01% by weight of polycyclic hydrocarbons (B) with at least two fused benzene rings each with at least contains two ring-substituted hydroxyl groups in the ortho position to one another, the benzene rings being bridged to one another by annulation to an acyclic hydrocarbon system, the acyclic hydrocarbon system preferably having at least one oxo group or hydroxyl group.
Für das erfindungsgemäße Konzentrat sind naturgemäß dieselben Anteile an wasserlöslichen Verbindungen (A) des Elements Zirkonium und polyzyklischen Kohlenwasserstoffen (B) relativ zueinander bevorzugt wie für das daraus bereitgestellte Korrosionsschutzmittel im erfindungsgemäßen Verfahren.The same proportions of water-soluble compounds (A) of the element zirconium and polycyclic hydrocarbons (B) relative to one another are naturally preferred for the concentrate according to the invention as for the corrosion protection agent provided therefrom in the process according to the invention.
Optional enthält das Konzentrat mindestens 1 Gew.-%, vorzugsweise mindestens 2 Gew.-%, jedoch vorzugsweise nicht mehr als 20 Gew.-%, besonders bevorzugt nicht mehr als 10 Gew.-%, an organischen Verbindungen (C), die ausgewählt sind aus Copolymeren oder Copolymerenmischungen von Alkenen und Vinylalkohol, vorzugsweise von Ethen und Vinylalkohol, die wiederum jeweils bevorzugt eine Hydroxylzahl im Bereich von 200 bis 500 Milligramm KOH pro Gramm des Copoylmers bzw. der Copolymerenmischung aufweisen.The concentrate optionally contains at least 1% by weight, preferably at least 2% by weight, but preferably not more than 20% by weight, particularly preferably not more than 10% by weight, of organic compounds (C) selected are made from copolymers or copolymer mixtures of alkenes and vinyl alcohol, preferably of ethene and vinyl alcohol, which in turn preferably each have a hydroxyl number in the range from 200 to 500 milligrams of KOH per gram of the copolymer or the copolymer mixture.
Vorzugsweise ist im erfindungsgemäßen Konzentrat die wasserlösliche Verbindung (A) des Elements Zirkonium ausgewählt aus Zirkonylnitrat.In the concentrate according to the invention, the water-soluble compound (A) of the element zirconium is preferably selected from zirconyl nitrate.
Weiterhin bevorzugt ist im erfindungsgemäßen Konzentrat der polyzyklische Kohlenwasserstoff (B) ausgewählt aus 1,2-Hydroxyanthrachinon.The polycyclic hydrocarbon (B) selected from 1,2-hydroxyanthraquinone is also preferred in the concentrate according to the invention.
Das Korrosionsschutzmittel zur Anwendung in einem erfindungsgemäßen Verfahren kann durch Verdünnen des Konzentrates um den Faktor 5-20 hergestellt werden.The corrosion protection agent for use in a method according to the invention can be produced by diluting the concentrate by a factor of 5-20.
Insoweit zuvor für das Korrosionsschutzmittel in den beschriebenen erfindungsgemäßen Verfahren herausgestellt ist, dass selbiges bestimmte Komponenten für die Gewährleistung einer hinreichenden Passivierung nicht oberhalb vorgegebener Mengen enthalten soll, gilt dies sinngemäß auch für das erfindungsgemäße Konzentrat, wobei die jeweiligen Obergrenzen im erfindungsgemäßen Konzentrat um den Faktor 5 höher liegen als für das Korrosionsschutzmittel im erfindungsgemäßen Verfahren.Insofar as it was previously pointed out for the corrosion protection agent in the described method according to the invention that it should not contain certain components to ensure adequate passivation above specified amounts, this also applies accordingly to the concentrate according to the invention, the respective upper limits in the concentrate according to the invention by a factor of 5 are higher than for the corrosion protection agent in the method according to the invention.
Die Effektivität der erfindungsgemäßen Vorbehandlung einen potentiellen Lackhaftgrund auszubilden kann nach Aufträufeln einer geringen Menge (ca. 1 ml) einer erfindungsgemäßen sauren wässrigen Vorbehandlungslösung (pH-Wert 1,5) enthaltend 15 g/kg Zr in Form von Zirkonylnitrat sowie 500 mg/kg Alizarin auf Aluminiumblech (AI 3008; 0,2 mm Dicke) und nachfolgendem Eintrocknen bei 30 °C im Vergleich zu einer Behandlung mit einer Lösung, die das Alizarin nicht enthält, nachgewiesen werden. Während die erfindungsgemäße Behandlung einen nicht abwischbaren irisierenden Überzug liefert, ist der eher weiße Überzug basierend allein auf der Zirkonylnitrat-haltigen Lösung mit einem Tuch leicht zu entfernen.The effectiveness of the pretreatment according to the invention to form a potential paint primer can be achieved after a small amount (approx. 1 ml) of an acidic aqueous pretreatment solution according to the invention (pH 1.5) containing 15 g / kg Zr in the form of zirconyl nitrate and 500 mg / kg alizarin on aluminum sheet (AI 3008; 0.2 mm thickness) and subsequent drying at 30 ° C in comparison to a treatment with a solution that does not contain the alizarin. While the treatment according to the invention provides an iridescent coating that cannot be wiped off, the rather white coating based solely on the zirconyl nitrate-containing solution is easy to remove with a cloth.
Für die Darlegung der Eignung der erfindungsgemäßen Vorbehandlung einen guten Lackhaftgrund bereitzustellen wurden verschiedene Beschichtungssysteme für Dosendeckel aufgebracht und die Lackhaftung, insbesondere Lackablösungen, das sogenannte "Feathering", sowie Verfärbungen, das sogenannte "Blushing", nach Auslagerung unter Sterilisationsbedingungen, denen eine Beschichtung, eines Werkstoffes, die zur Bevorratung von Lebensmitteln geeignet sein will und daher in direktem Kontakt mit Lebensmitteln steht, üblicherweise standhalten muss, bewertet.To demonstrate the suitability of the pretreatment according to the invention to provide a good paint primer, various coating systems for can lids were applied and paint adhesion, in particular paint detachment, the so-called "feathering", and discoloration, the so-called "blushing", after storage under sterilization conditions, which a coating, one Material that wants to be suitable for storing food and is therefore in direct contact with food, usually has to withstand, assessed.
In Tabelle 1 sind die verschiedenen Vorbehandlungen und Primerbeschichtungen aufgeführt, die diesbezüglich getestet wurden. Die Vorbehandlung erfolgte auf alkalisch (Bonderite® C-AK 1803 der Fa. Henkel AG & Co.KGaA, 15 g/L, 60°C, 10 s) gereinigten und mit entionisiertem Wasser (κ < 1µScm-1) gespülten Aluminiumfeinblechen (AI 3006) mit einer Stärke von 0,2 mm durchgeführt und hierfür ein Nassfilm der Vorbehandlungslösung von ca. 4-6 ml/m2 aufgebracht und bei 80 °C getrocknet, so dass die Schichtauflage an Zirkon jeweils 12 mg/m2 betrug. Der organische Primer wurde unmittelbar nach dem Trockenschritt aufgerakelt und bei 249 °C PMT (Peak Metal Temperature) eingetrocknet und ausgehärtet, wobei eine Trockenfilmauflage an Primer von ca. 12 g/m2 eingestellt wurde.Table 1 lists the various pretreatments and primer coatings that were tested in this regard. The pretreatment was carried out on alkaline (Bonderite® C-AK 1803 from Henkel AG & Co.KGaA, 15 g / L, 60 ° C, 10 s) cleaned and rinsed with deionized water (κ <1 μScm -1 ) aluminum sheets (AI 3006) was carried out with a thickness of 0.2 mm and a wet film of the pretreatment solution of approx. 4-6 ml / m 2 was applied and dried at 80 ° C. so that the zirconium layer was 12 mg / m 2 in each case. Immediately after the drying step, the organic primer was applied with a doctor blade and dried and cured at 249 ° C. PMT (Peak Metal Temperature), a dry film coverage of approx. 12 g / m 2 being set on the primer.
Die Auslagerung der derart beschichteten Aluminiumbleche unter Sterilisationsbedingungen erfolgte bei 121°C mit Leitungswasser oder in Leitungswasser enthaltend 2 Gew.-%ige Zitronensäure für jeweils 30 Minuten im Autoklaven. Eine Beurteilung der Lackenthaftung am Gitterschnitt nach DIN EN ISO 2409 und des "Blushing", also dem Auftreten von weißlichen Verfärbungen, wurde sodann vorgenommen. Die Ergebnisse sind in Tab. 2 zusammengefasst.
Es zeigt sich, dass die erfindungsgemäße Vorbehandlung insbesondere für die Beschichtung auf Basis des Acrylat-basierten Primer im Vergleich zu einer konventionellen Fluorozirkonat-basierten Vorbehandlung hervorragende Lackhaftungswerte liefert, während für eine Beschichtung auf Basis des Epoxid-basierten Primers zumindest gleich gute Ergebnisse sowohl hinsichtlich Lackhaftung als auch hinsichtlich "Blushing" resultieren.
Claims (15)
- A method for the anti-corrosion pretreatment of a metal substrate, in which method the surface of the metal substrate is brought into contact with an aqueous anti-corrosion agent which contains at least one water-soluble compound (A) of the element zirconium and at least one polycyclic hydrocarbon (B) which comprises at least one anellated benzene ring having in each case at least two hydroxyl groups substituted in the ring in the ortho position relative to one another, characterized in that the molar ratio of zirconium to the total fluoride content in the homogenous aqueous phase of the anti-corrosion agent is greater than 1.
- The method according to claim 1, characterized in that the polycyclic hydrocarbon (B) has a solubility of less than 5 g/kg, preferably less than 1 g/kg, at 20 °C in deionized water having a specific conductance of less than 1 µScm-1.
- The method according to one or both of the preceding claims, characterized in that the polycyclic hydrocarbon (B) comprises at least two anellated benzene rings each having at least two hydroxyl groups substituted in the ring in the ortho position relative to one another, the benzene rings being bridged in each case by being anellated on an acyclic hydrocarbon system, the acyclic hydrocarbon system preferably comprising at least one oxo group or hydroxyl group.
- The method according to one or more of the preceding claims, characterized in that the polycyclic hydrocarbon (B) is selected from the group of the anthraquinones which are substituted in the ring by at least two hydroxyl groups in the ortho position relative to one another, preferably 1,2-hydroxyanthraquinone.
- The method according to one or more of the preceding claims, characterized in that the source of the water-soluble compound (A) of the element zirconium is not additionally a source of fluoride ions, and is preferably selected from zirconyl nitrate, zirconium acetate and/or ammonium zirconium carbonate, particularly preferably zirconyl nitrate.
- The method according to one or more of the preceding claims, characterized in that the total fluoride content in the aqueous phase of the anti-corrosion agent is less than 50 mg/kg, preferably less than 10 mg/kg, particularly preferably less than 1 mg/kg.
- The method according to one or more of the preceding claims, characterized in that the weight ratio of water-soluble compounds (A) of the element zirconium, based on the element zirconium, to polycyclic hydrocarbon (B) is less than 0.2, preferably less than 0.1, but preferably greater than 0.02.
- The method according to one or more of the preceding claims, characterized in that the pH of the anti-corrosion agent is less than 2.0, particularly preferably less than 1.6, but preferably greater than 0.5, particularly preferably greater than 1.0.
- The method according to one or more of the preceding claims, characterized in that at least 0.1 wt.%, preferably at least 0.2 wt.%, of organic compounds (C), based in each case on the aqueous anti-corrosion agent, are additionally contained in the anti-corrosion agent, which compounds have a molar mass of above 5,000 g/mol and preferably comprise at least in part functional groups selected from hydroxyl groups, carboxyl groups, phosphate groups, phosphonate groups and amino groups, the sum of the acid number and hydroxyl number preferably being at least 100 milligrams KOH per gram, but preferably no greater than 600 milligrams KOH per gram, of the organic compounds (C).
- The method according to claim 9, characterized in that the organic compounds (C) are selected from copolymers or copolymer mixtures of alkenes, preferably ethene, and vinyl alcohol, which preferably have a hydroxyl number in the range of from 200 to 500 milligrams KOH per gram of copolymer or copolymer mixture, the proportion of these copolymers or copolymer mixtures preferably not exceeding 5 wt.%, particularly preferably not exceeding 2 wt.%, based in each case on the aqueous anti-corrosion agent.
- The method according to one or more of the preceding claims, characterized in that the metal substrates are selected from zinc and/or aluminum, preferably aluminum.
- The method according to one or more of the preceding claims, characterized in that, after the metal substrate has been brought into contact with the aqueous anti-corrosion agent, a wet film remains on the surface of the metal substrate and is dried, preferably by supplying heat, before a subsequent rinsing step or subsequent wet-chemical treatment.
- The method according to claim 12, characterized in that the wet film remains with a film thickness which produces, after drying, a coating layer of zirconium of greater than 5 mg/m2, preferably greater than 10 mg/m2, but preferably less than 150 mg/m2, particularly preferably less than 50 mg/m2.
- A method for producing coated can lids from strip aluminum, wherein, in a first step, a coating layer of zirconium of greater than 5 mg/m2 is first applied to strip aluminum according to the method from claim 13 and a primer is then optionally applied and cured, whereupon the lid material is punched out of the strip and shaped into can lids.
- A concentrate of an anti-corrosion agent according to claim 1, wherein the concentrate has a pH in the range of from 0.5 to 2.0 and contains at least 1 wt.% of a water-soluble compound of the element zirconium, based on the element zirconium, and at least 0.01 wt.% of polycyclic hydrocarbons that have at least two anellated benzene rings having in each case at least two hydroxyl groups substituted in the ring in the ortho position relative to one another, wherein the benzene rings are bridged in each case by being anellated on an acyclic hydrocarbon system, wherein the acyclic hydrocarbon system preferably comprises at least one oxo group or hydroxyl group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016203771.4A DE102016203771A1 (en) | 2016-03-08 | 2016-03-08 | Fluoride-free zirconium-based metal pretreatment for passivation |
| PCT/EP2017/051291 WO2017153075A1 (en) | 2016-03-08 | 2017-01-23 | Fluoride-free zirconium-based metal pre-treatment for passivation |
Publications (2)
| Publication Number | Publication Date |
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| EP3426822A1 EP3426822A1 (en) | 2019-01-16 |
| EP3426822B1 true EP3426822B1 (en) | 2020-10-21 |
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| EP17701835.5A Active EP3426822B1 (en) | 2016-03-08 | 2017-01-23 | Fluoride-free zirconium-based metal pre-treatment for passivation |
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| Country | Link |
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| US (1) | US11142827B2 (en) |
| EP (1) | EP3426822B1 (en) |
| JP (1) | JP7049259B2 (en) |
| KR (1) | KR20180118680A (en) |
| CN (1) | CN108699699B (en) |
| AU (1) | AU2017229193B2 (en) |
| BR (1) | BR112018016295B1 (en) |
| CA (1) | CA3015541A1 (en) |
| DE (1) | DE102016203771A1 (en) |
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| WO (1) | WO2017153075A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9914916A (en) * | 1998-10-30 | 2001-07-10 | Henkel Corp | Composition of aqueous liquid matter, and process to form a colored conversion coating on a metal surface |
| DE19923118A1 (en) * | 1999-05-19 | 2000-11-23 | Henkel Kgaa | Polymerizable composition for the anticorrosion coating of metallic substrates contains an organic titanium, silicon or zirconium compound |
| DE19933186A1 (en) | 1999-07-15 | 2001-01-18 | Henkel Kgaa | Process for applying no-rinse products to running metal belts |
| US6893687B2 (en) * | 2000-09-25 | 2005-05-17 | Chemetall Gmbh | Method for coating metallic surfaces |
| DE10146446B4 (en) * | 2000-09-25 | 2006-05-18 | Chemetall Gmbh | Coating metal strip for use in automobile, aircraft or aerospace industry, including formation of flexible, adherent lacquer layer using aqueous dispersion of UV-crosslinkable resin, wax and corrosion inhibitor |
| US20040054044A1 (en) * | 2000-10-11 | 2004-03-18 | Klaus Bittner | Method for coating metallic surfaces with an aqueous composition, the aqueos composition and use of the coated substrates |
| JP4652592B2 (en) | 2001-03-15 | 2011-03-16 | 日本ペイント株式会社 | Metal surface treatment agent |
| DE10164671A1 (en) * | 2001-12-27 | 2003-07-10 | Basf Ag | Derivatives of polymers for metal treatment |
| JP4526807B2 (en) | 2002-12-24 | 2010-08-18 | 日本ペイント株式会社 | Pre-painting method |
| CA2512591C (en) * | 2003-01-10 | 2011-11-01 | William E. Fristad | A coating composition |
| US7063735B2 (en) * | 2003-01-10 | 2006-06-20 | Henkel Kommanditgesellschaft Auf Aktien | Coating composition |
| ES2748850T3 (en) * | 2009-07-02 | 2020-03-18 | Henkel Ag & Co Kgaa | Chromium and fluorine free chemical conversion metal surface treatment solution, metal surface treatment method, and metal surface coating method |
| US10233349B2 (en) | 2014-02-04 | 2019-03-19 | Ppg Industries Ohio, Inc. | Acrylic aqueous dispersions for container coatings |
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2016
- 2016-03-08 DE DE102016203771.4A patent/DE102016203771A1/en not_active Withdrawn
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- 2017-01-23 AU AU2017229193A patent/AU2017229193B2/en active Active
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- 2017-01-23 WO PCT/EP2017/051291 patent/WO2017153075A1/en active Application Filing
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- 2017-01-23 ES ES17701835T patent/ES2831777T3/en active Active
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| US11142827B2 (en) | 2021-10-12 |
| CA3015541A1 (en) | 2017-09-14 |
| BR112018016295A2 (en) | 2018-12-26 |
| WO2017153075A1 (en) | 2017-09-14 |
| BR112018016295B1 (en) | 2023-03-07 |
| AU2017229193B2 (en) | 2022-10-27 |
| JP2019513892A (en) | 2019-05-30 |
| ES2831777T3 (en) | 2021-06-09 |
| DE102016203771A1 (en) | 2017-09-14 |
| AU2017229193A1 (en) | 2018-09-06 |
| CN108699699B (en) | 2021-07-20 |
| JP7049259B2 (en) | 2022-04-06 |
| US20190010610A1 (en) | 2019-01-10 |
| KR20180118680A (en) | 2018-10-31 |
| EP3426822A1 (en) | 2019-01-16 |
| CN108699699A (en) | 2018-10-23 |
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