WO2005116294A1 - Farbige konversionsschichten auf metalloberflächen - Google Patents
Farbige konversionsschichten auf metalloberflächen Download PDFInfo
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- WO2005116294A1 WO2005116294A1 PCT/EP2005/000769 EP2005000769W WO2005116294A1 WO 2005116294 A1 WO2005116294 A1 WO 2005116294A1 EP 2005000769 W EP2005000769 W EP 2005000769W WO 2005116294 A1 WO2005116294 A1 WO 2005116294A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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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
- C23C22/73—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 characterised by the process
- C23C22/77—Controlling or regulating of the coating process
Definitions
- the invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium or their alloys. It describes chrome-free conversion processes for such metal surfaces, i. H. chemical treatment processes that lead to the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated.
- the chrome-free coating is colored so that a simple visual check can be used to determine whether an adequate conversion layer has been formed.
- the task of this conversion layer is to reduce the tendency of the metal surface to corrode and to produce good adhesion between the metal surface and an organic coating applied to the conversion layer, such as, for example, a varnish or an adhesive.
- US-A-5 129 967 discloses treatment baths for a no-rinse treatment (referred to there as “dried in place conversion coating") containing aluminum
- EP-B-8 942 discloses treatment solutions containing, preferably for aluminum cans
- US-A-4 992 116 describes treatment baths for the conversion treatment of aluminum with pH values between about 2.5 and 5, which contain at least three components:
- WO 92/07973 teaches a chromium-free treatment process for aluminum, which as essential components in acidic aqueous solution 0.01 to about 18 wt .-% ⁇ ZrFg and 0.01 to about 10 wt .-% of a 3- (NC ⁇ . 4th alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer used.
- Optional components are 0.05-10% by weight of dispersed SiO 2, 0.06-0.6% by weight of a solubilizer for the polymer and
- the polymer mentioned falls under the group of the "reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl group-containing amines" which can be used in the context of the present invention.
- WO 00/71626 discloses a chromium-free corrosion protection agent containing water and a.) 0.5 to 100 g / l hexafluoro anions of titanium (IV), silicon (IV) and / or zircon (IV) b.) 0 to 100 g / l Phosphoric acid c.) 0 to 100 g / l of one or more compounds of cobalt, nickel, vanadium, iron, manganese, molybdenum or tungsten, d.) 0.5 to 30% by weight of at least one water-soluble or water-dispersible film-forming organic polymer or copolymer (based on active substance), e.) 0.1 to 10% by weight of an organophosphonic acid f.) if necessary, other auxiliaries and additives.
- WO 94/25640 discloses a method for producing blue-colored conversion layers on zinc / aluminum alloys.
- the metal surfaces are brought into contact with a treatment solution which has a pH between 3.5 and 6 and which has 0.2 to 3.0% by weight of molybdenum and a fluoride content of 0.1 to 2.0%. -% having.
- Molybdenum can be used as molybdate, as phosphomolybdic acid, as molybdenum chloride and the like.
- Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoric acids such as fluorotitanic acid or fluorozirconic acid.
- WO 00/26437 goes the way of coloring the conversion layer using an organic dye (alizerin dye).
- the conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to other inorganic oxides, hydroxides or carbonates or their reaction products with the fluoric acids.
- a poly-4-hydroxystyrene (polyvinylphenol) substituted with amino groups can be present as the organic polymer.
- FR 2 461 764 proposes chemical oxidation of the aluminum surface with organic nitro compounds in alkaline solution. After this oxidation, the layers can be colored with an organic dye.
- a similar two-stage process is proposed by WO 01/71060.
- This document describes a multi-layer coating consisting of a conversion layer applied to a metal (e.g. is available electrochemically and has pores) and a colored layer located on this conversion layer. The second colored layer can be obtained by contact with a solution containing at least one alkoxysilane compound and a dye, followed by subsequent polymerization and / or crosslinking of the alkoxysilane compound.
- the methods cited above for producing chromium-free colored conversion layers on metals such as aluminum can be divided into two groups.
- colored transition metal compounds such as molybdates or polymolybdates or organic dyes are incorporated into the conversion layer.
- a conversion layer is produced in a conventional manner and the organic dyes are applied to the conversion layer already formed in a second step.
- the conversion treatment taking place in the presence of an organic polymer which on the one hand enhances the corrosion protection effect and the paint adhesion of the conversion layer and on the other hand carries coloring substituents, so that the presence of this polymer on the metal surface contributes can be recognized by the eye.
- EP 504 520 proposes for this purpose to covalently bind dye residues to the organic polymers used for this purpose, so that the concentration of the polymers in the circulating water can easily be determined by absorption or fluorescence measurement.
- This document discloses a number of organic dye residues as well as monomers that can be reacted and polymerized with one another to obtain polymers with coloring groups.
- these polymers can contain one or more of the following monomers: acrylic acid, acrylamide, sulfomethylacrylamide, vinyl acetate, methacrylic acid or acrylonitrile.
- the object of the present invention is to provide means and methods for producing chromium-free conversion layers on metal surfaces, conversion layers being produced in a single step which appear colored to the human eye or fluoresce visibly. None of the actual Conversion active substances independent dye are used, since otherwise it cannot be guaranteed that the intensity of the coloring or the fluorescence correlates with the thickness of the conversion layer.
- a chromium-free treatment solution for producing colored or fluorescent corrosion protection layers on metal surfaces which a) phosphoric acid and / or at least one fluoric acid of one or more elements from group B, Si, Ti, Zr and Hf or in each case their anions and at least b) contains an organic polymer, the organic polymer being able to bind to the metal surface via oxygen and / or nitrogen atoms, characterized in that the organic polymer carries covalently bonded groups which appear colored to the human eye or which, when exposed to UV light, are used for the fluorescent human eye recognizable.
- the treatment solution is free of chromium, i.e. contains no intentionally added chromium compounds. Traces of chromium cannot, however, be excluded as impurities, for example as a result of detachment from container material. Furthermore, it preferably also contains no heavy metal ions other than those listed as components a). This reduces the demands on the treatment of waste water.
- the treatment solution should not contain more than 3 g / l phosphoric acid and more than 0.3 g / l zinc and / or manganese ions at the same time. This prevents zinc and / or manganese phosphate crystals from depositing on the metal surface. This would correspond to a more or less complete layer-forming phosphating, which is undesirable in the context of the present invention.
- a preferred treatment solution is characterized in that it a) 0.02 to 20 g / l phosphoric acid and / or at least one fluoro acid of one or more elements from group B, Si, Ti, Zr and Hf or their respective anions and b) 0, Contains 1 to 200 g / l of the organic polymer. If the treatment solution contains phosphoric acid, its minimum concentration is preferably at least 1 g / l, in particular at least 5 g / l. 15 g / l is usually sufficient as the upper limit of the concentration.
- the treatment solution contains as component a) a fluoric acid of boron, for example tetrafluoroboric acid, its concentration is preferably selected such that the treatment solution is at least 0.01 g / l, preferably at least 0.02 g / l, and up to 5 g / l , preferably up to 1 g / l and in particular up to 0.5 g / l boron (calculated as an element).
- a fluoric acid of boron for example tetrafluoroboric acid
- the concentration is preferably chosen such that the treatment solution is at least 0.02 g / l, preferably at least 0.5 g / l, and up to 10 g / l, preferably up to contains up to 5 g / l and in particular up to 1 g / l hafnium.
- Treatment solutions which contain, as component a), fluoro acids of Si, Ti and / or Zr are particularly preferred.
- a treatment solution is preferably used which contains a total of at least 0.01 g / l, preferably at least 0.025 g / l, and up to 10 g / l, preferably up to 1 g / l, in particular up to 0.5 g / l Ti and / or Zr and / or Si ions and at least such an amount of fluoride that the atomic ratio Ti to F and / or Zr to F and / or Si to F is in the range from 1: 1 to 1: 6.
- the Ti, Zr and / or Si ions mentioned can be used completely in the form of hexafluoro complexes such as, for example, hexafluoro acids or their salts which are water-soluble in the concentration range mentioned, such as sodium salts. In this case, the atomic ratio is 1: 6.
- complex compounds can also be used, in each of which less than six fluoride ions are connected to the central elements Ti, Zr or Si. These can form automatically in the treatment solution if both hexafluoro complexes of at least one of the central elements Ti, Zr or Si and at least one further compound of one of these central elements are added to it.
- the treatment solution may contain hexafluorozirconate ions as well as (preferably colloidal) silica (SiO 2 ) or its reaction products. Unreacted silica can be suspended in the treatment solution.
- a treatment solution can also be obtained by using hydrofluoric acid or its (optionally acidic) salts together with those compounds of Ti, Zr and / or Si which can form fluorocomplexes with them. Examples are the nitrates, carbonates, hydroxides and / or already mentioned Oxides.
- the central metal It is preferred to use a total of such an amount of Ti, Zr and / or Si as the central metal and such an amount of fluoride that the atomic ratio of central metal to fluoride is less than or equal to 1: 2, in particular less than or equal to 1: 3.
- the atomic ratio can also be less than 1 to 6 if the treatment solution contains more fluoride, for example in the form of hydrofluoric acid or its salts, than is required stoichiometrically to form the hexafluoro complexes of the central metals Ti, Zr and / or Si.
- the atomic ratio can be as small as 1 to 12 or 1:18 or even lower if an appropriate excess of fluoride is used, ie two or three times or even more than that which is necessary for the complete formation of the hexafluoro complexes.
- Treatment solutions which contain fluoric acids of Ti and / or Zr are particularly preferred. It can be particularly favorable for the corrosion protection effect if the treatment solution contains both fluoric acids of Ti and of Zr.
- the molar ratio of Ti to Zr can be in the range from 10: 1 to 1:10, in particular in the range from 2: 1 to 1: 2.
- the pH value of the treatment solution should not be significantly below a value of 1, since lower pH values lead to an increasingly stronger pickling attack on the metal surface.
- the pH is preferably not less than 2 and in particular not less than 2.5. At pH values above 6, the conversion layer is no longer formed to the desired extent. It is preferable to work at pH values which are not higher than 4 and in particular not higher than 3.5.
- the essential components a) and possibly also b) mentioned are all protolytes, that is to say molecules or ions which can react with the release or absorption of protons in the sense of an acid-base reaction. It is therefore obvious to the person skilled in the art that these components undergo such reactions with one another and with the solvent water until the corresponding chemical equilibria have been reached.
- the pH values mentioned which are in the acidic range, are preferably set by introducing the phosphoric acid and / or complex fluoric acids in the form of the free acids.
- the concentration of the organic polymer b) in the treatment solution is preferably in the range between 0.1 and 200 g / l.
- the particularly preferred minimum concentration with increasing preference is: at least 1 g / l, at least 5 g / l, at least 10 g / l, at least 15 g / l.
- the upper limit of the concentration can be selected: 150 g / l, 100 g / l, 70 g / l.
- the proportion by weight of the covalently bonded groups which appear colored to the human eye or which fluoresce recognizable to the human eye when irradiated with UV light is at least 0.1, preferably at least 0.5, of the total weight of the organic polymer and in particular at least 1% by weight and up to 20, preferably up to 15 and in particular up to 10% by weight.
- the organic polymer b) can be selected from different groups.
- the organic polymer is preferably selected from epoxy resins, aminoplast resins, phenol-aldehyde resins, polymers bearing carboxylic acid groups, polymeric alcohols, esterification products of polymeric alcohols with polymers bearing carboxylic acid groups, polymers bearing amino groups, homo- or copolymers of vinylpyrrolidone and from polymers with phosphinic acid -, Phosphonic acid or phosphoric acid ester groups.
- poly-4-vinylphenol compounds are chosen in particular as polymers bearing amino groups. Examples of such poly-4-vinylphenol compounds, without a covalently bound coloring group, can be found in WO 00/26437 cited at the outset and the literature cited therein, in particular US Pat. No. 5,281,282. Furthermore, the organic polymers b) can be selected from their polymer backbone from:
- polyvinyl alcohol or water-soluble or water-dispersible partial esters thereof f) polymers or copolymers of unsaturated mono- or dicarboxylic acids or their amides, g) esters from the polymers of groups e) and f), h) polymers or copolymers of vinylpyrrolidone, i ) Polymers of the diglycidyl ether of bisphenol A, k) copolymers of alkylenephosphonic or alkylenephosphinic acids and one or more unsaturated carboxylic acids.
- a “partial ester” is understood to mean that only a part of the alcohol groups is esterified, the ester formation taking place with non-polymeric carboxylic acids.
- the ester formation can take place with monobasic carboxylic acids having 1 to 4 carbon atoms.
- the polymers or copolymers of group f) can be selected, for example, from homo- or copolymers of acrylic acid and / or methacrylic acid, the acid groups of which can be partially replaced by amide groups or esterified with alcohols, in particular with simple alcohols having 1 to 4 carbon atoms.
- Specific examples are homo- or copolymers of or with methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and glycerol propoxitria acrylate. These specific examples are known for example from WO 95/14117.
- the polymers of group f) can also be selected from those which contain maleic acid monomers. A specific example of this is a maleic acid-methyl vinyl ether copolymer.
- Polymers of group e) generally contain free alcohol groups, those of group f) contain free carboxylic acid groups. These two polymers can therefore not only be used in a mixture with one another, but in a form in which ester formation has at least partially occurred between the alcohol groups of the polymer e) and the carboxylic acid groups of the polymer f). This is explained in more detail in WO 94/12570. The teaching described there can also be used in the context of the present invention.
- the treatment solution can also contain polymers of group h). Such polymers and their use in treatment solutions for conversion treatment are described in more detail in DE-A-100 05 113 and DE-A-101 31 723.
- the additional polymers can be selected from those of group i), as is described in more detail in US Pat. No. 5,356,690.
- organic polymers b) are preferred which, with regard to their polymeric backbone, are selected from polymers or copolymers of acrylate and / or methacrylate monomers, maleic anhydride which can be wholly or partly hydrolyzed (in particular methyl vinyl ether / maleic anhydride copolymers) and acrylate or methacrylate monomers, which are terminated with phosphate groups. Specific examples of this are mentioned in the experimental section.
- the covalently bonded groups in the organic polymer b) which appear colored to the human eye or which fluoresce visibly for the human eye when irradiated with UV light are preferably selected from Tuloidin Blue (CAS No. 92-31-9) and Made of neutral red (CAS No. 553-24-2).
- the average molecular weight of the organic polymers a) is preferably at least 10,000 daltons.
- the upper limit of the molecular weight is not critical as long as the polymer is soluble or dispersible in the preferably acidic treatment solution in the desired concentration range.
- the upper limit of the molar mass can be 50,000,000, in particular 20,000,000 and particularly preferably 10,000,000 Daltons.
- An upper limit of 5,000,000 daltons can also be sufficient.
- the average molecular weight is preferably greater than 50,000 daltons and in particular greater than 100,000 daltons.
- the average molecular weights can be determined, for example, by gel permeation chromatography using a polyethylene glycol standard.
- organic polymer b a copolymer of i) acrylic acid and / or methacrylic acid with ii) acrylate and / or methacrylate monomers terminated with phosphate groups is preferred, the copolymer containing covalently bound molecules of toluidine blue or neutral red.
- An exemplary production of this polymer is described in working example 3, another example in working example 10.
- These polymers are examples of polymers which have both carboxylate and phosphonic acid groups or phosphoric acid ester groups. Because of her particularly high affinity for metal surfaces, these polymers with different polar adhesion groups are particularly preferred.
- Such particularly preferred copolymers can also be obtained, for example, by reacting acrylic acid and / or methacrylic acid with other unsaturated phosphonic acids, phosphinic acids or phosphoric acid esters.
- vinylphosphonic acid can be used as the unsaturated monomer with a phosphonic acid group.
- the applicant was unable to find any prior art document in which the particularly preferred copolymer of i) acrylic acid and / or methacrylic acid terminated with ii) acrylate and / or methacrylate monomers with phosphate groups, which contains covalently bound molecules of tuloidin blue or neutral red , is described. Therefore, this copolymer itself also forms an object of the present invention.
- the statements made above apply.
- the statements made above regarding the mass fraction of the dye groups in the total mass of the polymer also apply.
- the weight ratio between the monomers i) and the monomers ii) is preferably in the range from 10: 1 to 1:10, in particular from 5: 1 to 1: 5 and particularly preferably in the range from 3: 1 to 1: 1.
- Another polymer preferred for the treatment solution according to the invention is a methyl vinyl ether-maleic anhydride copolymer to which molecules of toluidine blue or neutral red are covalently bound and whose anhydride groups are at least partially, preferably at least 90% hydrolyzed.
- the molar ratio of the monomeric methyl vinyl ether and maleic anhydride is preferably in the range from 10: 1 to 1:10, in particular from 5: 1 to 1: 5, particularly preferably from 1: 2 to 2: 1.
- the molar ratio can be essentially 1: 1 be.
- the aqueous treatment solution can contain, as further component c), a total of 1 to 2,000 mg / l of one or more chelating complexing agents which do not fall under the definition of the organic polymers of group b).
- the chelating complexing agent c) is preferably non-polymeric and is preferably selected from molecules with 2 or more phosphonic acid groups, in particular from geminal diphosphonic acids, and phosphonocarboxylic acids and their anions in each case. (As explained above, depending on the pH value, the corresponding acid-base balance between acid form and Set the salt form of the complexing agent, regardless of the form in which it was introduced into the solution or the concentrate.)
- Such complexing agents are those which can also be used according to DE-A-103 39 165. Reference is hereby made to this reference.
- the properties of the conversion layer obtained can be further improved if the treatment solution (regardless of whether component c) is also present or not) as additional component d) at least one inorganic compound in particle form with an average particle diameter, measured with a Scanning electron microscope, in the range from 0.005 to 0.2 ⁇ m in diameter.
- the inorganic compound in particle form is preferably present in the aqueous bath solution in a content of 0.1 to 80 g / l, particularly preferably in a range from 0.2 to 25 g / l, very particularly preferably from 0.5 to 10 g / l, in particular from 1 to 4 g / l.
- the ratio of the contents of organic polymer b) to contents of inorganic compounds in particle form in the aqueous bath solution can vary within wide ranges, in particular it can be ⁇ 3.8: 1. This ratio is preferably in a range from 0.05: 1 to 3.5: 1, particularly preferably in a range from 0.18: 1 to 2.5: 1.
- a finely divided powder, a dispersion or a suspension such as e.g. a carbonate, an oxide, a silicate or a sulfate, in particular colloidal or amorphous particles.
- Particularly preferred as an inorganic compound in particle form are particles based on at least one compound of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc and / or zirconium, in particular particles based on aluminum oxide, barium sulfate, cerium dioxide, rare earth - Mixed oxide, silicon dioxide, silicate, titanium oxide, yttrium oxide, zinc oxide and / or zirconium oxide.
- the at least one inorganic compound is preferably in particle form in particles with an average particle size in the range from 6 nm to 150 nm, particularly preferably in the range from 7 to 120 nm, very particularly preferably in the range from 8 to 90 nm, even more preferably in Range from 8 to 60 nm to 25 nm. It is preferred that larger particles have a more platelet-like or elongated grain shape.
- particles of the compound in particle form those with higher or high electrical conductivity, in particular those of oxides, phosphates, Phosphides or sulfides of aluminum, iron or molybdenum, in particular aluminum phosphide or, iron oxide, iron phosphide, at least one molybdenum compound such as molybdenum sulfide, graphite and / or carbon black, these particles then also being able to have such an average particle size that they may be obtained from the invention protruding layer slightly more.
- the present invention relates to a method for producing colored or fluorescent corrosion protection layers on metal surfaces, characterized in that the metal surfaces are in contact with a treatment solution according to one or more of claims 1 for a period in the range from 0.5 to 10 minutes brings to 8, which has a temperature in the range of 20 to 80 ° C.
- the metal surface can be brought into contact with the treatment solution by methods customary in the art, such as dipping, spraying, a combination of spraying and dipping, rolling, etc.
- the metal surfaces are preferably rinsed with water, in particular with demineralized water, and then dried using customary methods.
- the contact time is preferably at least 1 minute, in particular at least 2 minutes. A contact time of up to 7 minutes, for example up to 5 minutes, is usually sufficient.
- a “no-rinse” treatment ie application (roller application, spray application with squeezing) without rinsing is also possible.
- the temperature of the treatment solution is preferably at least 30 ° C., for example 35 ° C. Usually it is not necessary that the temperature of the treatment solution exceeds an upper limit of 60 ° C, in particular 50 ° C.
- the metal surfaces which can be treated with the method according to the invention are preferably selected from surfaces of aluminum and aluminum alloys, magnesium and magnesium alloys, titanium and titanium alloys, zinc and zinc alloys, galvanized or alloy galvanized steel.
- the metal surfaces can be surfaces of the metals mentioned or their alloys as such, but also surfaces of a substrate such as steel which is coated with the metals mentioned or their alloys. Examples of the latter are electrolytically galvanized or hot-dip galvanized steel, aluminized steel, or coated steels such as Galvalume ® or Galfan ® , which have a coating of zinc / aluminum alloys.
- the invention relates to a metal part, the surface of which has a colored or fluorescent corrosion protection layer, as can be obtained by the method according to the invention.
- the metal part can have the colored or fluorescent corrosion protection layer, which can be obtained with the method according to the invention, as the only or outermost coating.
- the method according to the invention generally serves as a pretreatment for a further coating, for example a coating with a lacquer or also with an adhesive, if the treated metal parts are to be bonded to one another or to other substrates.
- the metal part according to the invention can have a varnish as the outermost layer or can be glued to a further metal part according to the invention or also to another substrate.
- the treatment step according to the invention is generally part of a treatment sequence, as is customary in the case of conversion treatment of the metal surfaces mentioned before a subsequent coating or adhesive bonding.
- a sequence of procedures usually begins with cleaning / degreasing of the metal surfaces, for which an alkaline cleaner can be used, for example.
- This is followed by one or more rinsing steps with water.
- This can be followed by an acidic treatment step to remove superficial oxides that are not removed during alkaline cleaning.
- This step is also referred to as "deoxidizing" or "pickling” and is used in particular on surfaces of aluminum and its alloys.
- an intermediate rinse with water and preferably an additional rinse with demineralized water this is followed by the treatment step according to the invention with the treatment solution according to the invention. Then you can rinse again with water.
- the method can also be carried out as a "no-rinse” method, ie rinsing with water after the treatment step according to the invention can also be dispensed with
- a colored or fluorescent, corrosion-protected metal surface which has good adhesion to a subsequently applied layer based on organic polymers, for example a paint or an adhesive.
- This surface generally contains 1 to 70 mg titanium and / or zirconium per m 2 , in particular 3 to 30 mg / m 2 , if the fluoro acids of these metals have been used as component a). These values can be measured using standard surface analysis methods, for example with X-ray fluorescence methods.
- the process according to the invention therefore provides metal surfaces which have good corrosion protection and good paint adhesion, as the person skilled in the art knows as a result of the technically very advantageous chromating processes which are undesirable for ecological and health reasons.
- the person skilled in the art immediately sees whether an adequate conversion layer has formed during the treatment, as is usual with chromating.
- the process according to the invention thus has the technical advantage over the production of colorless conversion layers that the result of the treatment is immediately visually recognizable without the need for special surface analysis.
- 3g neutral red (CAS No. 553-24-2) are dissolved in 50ml water and mixed with 200ml pyridine. While cooling with ice, 1.1 g of methacrylic acid chloride are added dropwise to the solution and the mixture is stirred at 40 ° C. for one hour and 3 hours. The solvent is distilled off in vacuo. 3.7 g of the crude product were obtained.
- toluidine blue monomer 13.8 g of acrylic acid and 6 g of methacrylate monomer terminated with phosphate groups (Sipomer PAM100, from Rhodia) are dissolved in 300 ml of water and oxygen is removed at 30 ° C. for 30 minutes by introducing nitrogen.
- the polymerization is then started by adding 0.1 g of V-44 (initiator).
- the solution is stirred for 24 hours at 50 ° C., started with a further 0.1 g of V-44 and polymerized for a further 24 hours.
- start again with 0.1g V-50 (initiator) raise the reaction temperature to 80 ° C and stir for a further 4 hours.
- the colored polymer solution is dialyzed for 48 hours (dialysis tube with an exclusion limit of 10,000 daltons).
- the colored polymer solution is dialyzed for 48 hours (with dialysis tubing).
- toluidine blue 0.1 g of toluidine blue are dissolved in 300 ml of a water / ice mixture.
- M w 216000 g / mol
- the solution is heated to 80 ° C for 2 hours.
- the solution was dialyzed for 48 hours (dialysis tube with an exclusion limit of 10,000 daltons). After dialysis, 400 ml of a 0.31% colored solution were obtained.
- the solution is heated to 80 ° C for 2 hours.
- the solution was dialyzed for 48 hours (dialysis tube with an exclusion limit of 10,000 daltons).
- Example 7 Reaction of toluidine blue with methyl vinyl ether-maleic anhydride copolymers
- Example 8 Reaction of toluidine blue with methyl vinyl ether-maleic anhydride copolymers
- toluidine blue 0.4 g of toluidine blue are dissolved in 380 ml of a water / ice mixture.
- M w 1080000 g / mol
- the solution is heated to 80 ° C for 2 hours.
- the solution was dialyzed for 48 hours (dialysis tube with an exclusion limit of 10,000 daltons). After dialysis, 400 ml of a 2.24% colored solution were obtained.
- 0.2 g neutral red monomer, 13.8 g acrylic acid and 6 g methacrylate monomer, terminated with phosphate groups (Sipomer PAM100, Rhodia) are dissolved in 550 ml water and freed of oxygen by introducing nitrogen at 50 ° C. for 30 min.
- the polymerization is then started by adding 0.1 g of V-44 (initiator).
- the solution is stirred for 24 hours at 50 C C, started from there further with 0.1 g of V-44 and polymerized for another 24 hours.
- start again with 0.1g V-50 (initiator) raise the reaction temperature to 80 ° C and stir for a further 4 hours.
- Rinse city water, room temperature, 1 minute
- Rinse Demineralized water, room temperature, 1 minute.
- the sheets were dried at 60 ° C. in a forced air oven and then painted with a commercially available powder coating.
- a practical paint adhesion test was then carried out: The test sheets were cross-cut, stored in boiling demineralized water for 2 hours and then at room temperature for one hour. Then an adhesive tape was stuck over the cross-cut area and peeled off again. The amount of paint removed from the sample plate was assessed and characterized by cross-cut marks: Gt 0: no paint loss, Gt 5: extensive paint loss.
- the paint infiltration was checked after the salt spray test.
- compositions of the treatment solutions and treatment results are shown below.
- Example 11 Composition of a 100 g aqueous treatment solution: H2TiF6 0.1 g polymer (Example 6) 2.55 g
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- composition of a 100 g aqueous treatment solution Composition of a 100 g aqueous treatment solution:
- the treatment solutions contained 1% by weight of H 2 TiF 6 and the amount of polymer mentioned in Table 1. Temperature: 35 ° C. Treatment duration, pH of the treatment solution and tests: see Table 1; Test results: Tables 2 and 3
- Paint BASF standard, white powder paint, Ral 9010 curing: 20 minutes, 360 ° C paint thickness: See Tables 2 and 3.
- Table 2 Test results on selected sheets (see Table 1): Salt spray test according to DIN 50021 SS
- Table 3 Test results on selected trays (see Table 1): Cooking test in demineralized water, 2 hours at 100 ° C
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- Metallurgy (AREA)
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- Chemical Treatment Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05707023A EP1751327A1 (de) | 2004-05-07 | 2005-01-27 | Farbige konversionsschichten auf metalloberflächen |
US11/593,690 US20070095435A1 (en) | 2004-05-07 | 2006-11-07 | Colored conversion layers on metallic substrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004022565.6 | 2004-05-07 | ||
DE102004022565A DE102004022565A1 (de) | 2004-05-07 | 2004-05-07 | Farbige Konversionsschichten auf Metalloberflächen |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/593,690 Continuation US20070095435A1 (en) | 2004-05-07 | 2006-11-07 | Colored conversion layers on metallic substrates |
Publications (1)
Publication Number | Publication Date |
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WO2005116294A1 true WO2005116294A1 (de) | 2005-12-08 |
Family
ID=34960495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2005/000769 WO2005116294A1 (de) | 2004-05-07 | 2005-01-27 | Farbige konversionsschichten auf metalloberflächen |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070095435A1 (de) |
EP (1) | EP1751327A1 (de) |
CN (1) | CN1950543A (de) |
DE (1) | DE102004022565A1 (de) |
WO (1) | WO2005116294A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007005943A1 (de) | 2007-02-01 | 2008-08-07 | Henkel Ag & Co. Kgaa | Metall-Vorbehandlung mit lumineszierenden Pigmenten |
WO2021233714A1 (en) * | 2020-05-19 | 2021-11-25 | Rhodia Operations | Metal surface treatment |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2867199B1 (fr) * | 2004-03-03 | 2006-06-23 | Ppg Ind France | Procede pour l'obtention d'un substrat mettalique comportant un revetement protecteur |
US7351295B2 (en) * | 2006-03-23 | 2008-04-01 | Pp6 Industries Ohio, Inc. | Cleaning and polishing rusted iron-containing surfaces |
US9347134B2 (en) | 2010-06-04 | 2016-05-24 | Prc-Desoto International, Inc. | Corrosion resistant metallate compositions |
US8496762B2 (en) * | 2011-02-04 | 2013-07-30 | Roberto Zoboli | Aluminum treatment compositions |
DE102012103159A1 (de) | 2012-04-12 | 2013-10-17 | Osram Opto Semiconductors Gmbh | Strahlung emittierendes Bauelement, transparentes Material und Füllstoffpartikel sowie deren Herstellungsverfahren |
WO2016048608A1 (en) * | 2014-09-24 | 2016-03-31 | Momentive Performance Materials Inc. | Conversion coating compostion comprising a dye and a method for coating a metal surface with said conversion coating composition |
CN104988478A (zh) * | 2015-07-11 | 2015-10-21 | 合肥正浩机械科技有限公司 | 一种凝胶状薄膜金属表面处理剂及其制备方法 |
CN104988482A (zh) * | 2015-07-11 | 2015-10-21 | 合肥正浩机械科技有限公司 | 一种多酸金属表面处理剂及其制备方法 |
CN105063594A (zh) * | 2015-08-14 | 2015-11-18 | 霍春月 | 一种抗氧化抗腐蚀镀锌板专用表面处理剂及其制备方法 |
CN109312469A (zh) * | 2016-06-22 | 2019-02-05 | 凯密特尔有限责任公司 | 包含钢、镀锌钢、铝、镁和/或锌镁合金的金属表面的防腐蚀预处理的改进方法 |
KR102472747B1 (ko) | 2016-08-23 | 2022-11-30 | 헨켈 아게 운트 코. 카게아아 | 디- 또는 폴리아민과 α,β-불포화 카르복실산 유도체의 반응 생성물로서 수득될 수 있는 접착 촉진제의 금속 표면 처리를 위한 용도 |
EP3659715A1 (de) * | 2018-11-27 | 2020-06-03 | Rhodia Operations | Metalloberflächenbehandlung |
EP3670613B1 (de) * | 2018-12-20 | 2021-10-06 | Goodrich Actuation Systems Limited | Korrosionsschutzbeschichtungsverfahren |
CN111363459A (zh) * | 2020-04-15 | 2020-07-03 | 上海达克罗涂复工业有限公司 | 一种锌铝涂料及其制备方法和应用 |
CN114959672A (zh) * | 2022-06-30 | 2022-08-30 | 联宝(合肥)电子科技有限公司 | 钝化液、铝材表面处理工艺及铝材 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0504520A2 (de) * | 1991-03-20 | 1992-09-23 | Nalco Chemical Company | Überwachung eines in einem Wasser-Kühlsystem zirkulierenden Behandlungsmittels |
US5294265A (en) * | 1992-04-02 | 1994-03-15 | Ppg Industries, Inc. | Non-chrome passivation for metal substrates |
US5516696A (en) * | 1994-09-13 | 1996-05-14 | Bulk Chemicals, Inc. | Method and composition for indicating the presence of chrome-free pretreatments on metal surfaces by fluorescence |
WO2000026437A1 (en) * | 1998-10-30 | 2000-05-11 | Henkel Corporation | Visible chromium- and phosphorus-free conversion coating for aluminum and its alloys |
WO2001025347A1 (en) * | 1999-10-01 | 2001-04-12 | Ppg Industries Ohio, Inc. | Coating with optical taggent |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5129967A (en) * | 1988-05-03 | 1992-07-14 | Betz Laboratories, Inc. | Composition and method for non-chromate coating of aluminum |
US4992116A (en) * | 1989-04-21 | 1991-02-12 | Henkel Corporation | Method and composition for coating aluminum |
US5281282A (en) * | 1992-04-01 | 1994-01-25 | Henkel Corporation | Composition and process for treating metal |
US5356490A (en) * | 1992-04-01 | 1994-10-18 | Henkel Corporation | Composition and process for treating metal |
DE10005113A1 (de) * | 2000-02-07 | 2001-08-09 | Henkel Kgaa | Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen |
DE10131723A1 (de) * | 2001-06-30 | 2003-01-16 | Henkel Kgaa | Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen |
US7063735B2 (en) * | 2003-01-10 | 2006-06-20 | Henkel Kommanditgesellschaft Auf Aktien | Coating composition |
DE10339165A1 (de) * | 2003-08-26 | 2005-03-24 | Henkel Kgaa | Farbige Konversionsschichten auf Metalloberflächen |
-
2004
- 2004-05-07 DE DE102004022565A patent/DE102004022565A1/de not_active Withdrawn
-
2005
- 2005-01-27 CN CNA2005800143837A patent/CN1950543A/zh active Pending
- 2005-01-27 EP EP05707023A patent/EP1751327A1/de not_active Withdrawn
- 2005-01-27 WO PCT/EP2005/000769 patent/WO2005116294A1/de not_active Application Discontinuation
-
2006
- 2006-11-07 US US11/593,690 patent/US20070095435A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0504520A2 (de) * | 1991-03-20 | 1992-09-23 | Nalco Chemical Company | Überwachung eines in einem Wasser-Kühlsystem zirkulierenden Behandlungsmittels |
US5294265A (en) * | 1992-04-02 | 1994-03-15 | Ppg Industries, Inc. | Non-chrome passivation for metal substrates |
US5516696A (en) * | 1994-09-13 | 1996-05-14 | Bulk Chemicals, Inc. | Method and composition for indicating the presence of chrome-free pretreatments on metal surfaces by fluorescence |
WO2000026437A1 (en) * | 1998-10-30 | 2000-05-11 | Henkel Corporation | Visible chromium- and phosphorus-free conversion coating for aluminum and its alloys |
WO2001025347A1 (en) * | 1999-10-01 | 2001-04-12 | Ppg Industries Ohio, Inc. | Coating with optical taggent |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007005943A1 (de) | 2007-02-01 | 2008-08-07 | Henkel Ag & Co. Kgaa | Metall-Vorbehandlung mit lumineszierenden Pigmenten |
WO2021233714A1 (en) * | 2020-05-19 | 2021-11-25 | Rhodia Operations | Metal surface treatment |
US20230340306A1 (en) * | 2020-05-19 | 2023-10-26 | Rhodia Operations | Metal surface treatment |
Also Published As
Publication number | Publication date |
---|---|
DE102004022565A1 (de) | 2005-12-22 |
CN1950543A (zh) | 2007-04-18 |
US20070095435A1 (en) | 2007-05-03 |
EP1751327A1 (de) | 2007-02-14 |
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