WO2017186931A1 - Verfahren zur korrosionsschützenden behandlung einer metallischen oberfläche mit vermindertem beizabtrag - Google Patents

Verfahren zur korrosionsschützenden behandlung einer metallischen oberfläche mit vermindertem beizabtrag Download PDF

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Publication number
WO2017186931A1
WO2017186931A1 PCT/EP2017/060229 EP2017060229W WO2017186931A1 WO 2017186931 A1 WO2017186931 A1 WO 2017186931A1 EP 2017060229 W EP2017060229 W EP 2017060229W WO 2017186931 A1 WO2017186931 A1 WO 2017186931A1
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Prior art keywords
composition
compound
formula
range
diol
Prior art date
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Ceased
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PCT/EP2017/060229
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German (de)
English (en)
French (fr)
Inventor
Anna Verena MOHR
Michael DRÖGE
Daniel SCHATZ
Marc RITTMEYER
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Chemetall GmbH
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Chemetall GmbH
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Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Priority to US16/097,169 priority Critical patent/US20220119650A9/en
Priority to EP17723944.9A priority patent/EP3448938A1/de
Priority to CN201780024292.4A priority patent/CN109071973A/zh
Priority to JP2018556915A priority patent/JP7034090B2/ja
Priority to KR1020187030704A priority patent/KR102373768B1/ko
Priority to MX2018013229A priority patent/MX2018013229A/es
Priority to RU2018141059A priority patent/RU2754070C2/ru
Priority to BR112018071503-4A priority patent/BR112018071503A2/pt
Publication of WO2017186931A1 publication Critical patent/WO2017186931A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/12Wash primers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19Iron or steel
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10Homopolymers or copolymers of methacrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/60Chemical 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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62Treatment of iron or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20Other heavy metals
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22Light metals
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20Use of solutions containing silanes

Definitions

  • the invention relates to a method for corrosion-protective treatment of a metallic surface and to an aqueous composition for reducing pickling in the corrosion-protective treatment of metallic surfaces.
  • the acidic or alkaline pH initially serves to remove oxide films and impurities from the metallic surface.
  • the oxidative proton attack on the metallic surface itself causes the metal cations necessary for the formation of the conversion coating to be dissolved out of it (so-called anodic metal dissolution).
  • the object of the invention was therefore to avoid the disadvantages of the prior art and a method for corrosion-protective treatment of a To provide metallic surfaces with reduced pickling and a composition for reducing pickling in the anti-corrosive treatment of metallic surfaces.
  • This object is achieved by a method according to claim 1, a composition according to claim 20, a concentrate according to claim 21 and a use according to claim 22.
  • Advantageous embodiments are each described in the dependent claims.
  • the surface is contacted successively with the following aqueous compositions: i) an alkaline or acidic cleaner composition,
  • compositions comprising a (meth) acrylate and / or epoxide-based KTL, wherein at least one of the compositions i) to v) at least one compound of the formula I.
  • R 1 is O- (CH 2 ) x Z- (CH 2 ) y-OR 2 (I), and wherein R 1 and R 2 are each independently H or an HO- (CH 2 ) W group with w> 2 , x and y are each independently 1 to 4, and Z is an S atom or a CC triple bond.
  • an "aqueous composition” is to be understood as meaning that, for the most part, ie more than 50% by weight, as the solvent / dispersant, water is contained Composition of a solution, more preferably a solution containing only water as a solvent.
  • That the metallic surface is successively contacted with the aqueous compositions i) to vi) does not exclude that it is brought into contact with one or more further compositions before and / or after this sequence. Also, it is not excluded that the metallic surface between the contacting with the different compositions i) to vi) is brought into contact with one or more further compositions.
  • the at least one compound of formula I acts as a physical corrosion inhibitor which is adsorbed by van der Waals forces on the metallic surface, forming a monomolecular, homogeneous, densely packed layer thereon. By means of said layer, the metallic surface is physically shielded from a proton or hydroxide ion attack and thus the pickling of the surface is prevented or at least reduced.
  • the detergent composition i) contains at least one compound of the formula I.
  • the concentration of the at least one compound of the formula I in the detergent composition i) is preferably in the range from 6 to 625 mg / l, particularly preferably in the range from 31 to 313 mg / l (calculated as 2-butin-1, 4-diol ).
  • the first rinsing composition ii), the second rinsing composition iii) and / or the third rinsing composition v) comprises at least one compound of the formula I.
  • the use of the at least one compound of formula I in one or more of the rinse compositions has the advantage of reducing the formation of flash rust on steel and / or galvanized steel.
  • the concentration of the at least one compound of the formula I is in the first rinsing composition ii), in the second rinsing composition iii) and in the third rinsing composition v) preferably in the range of 1 to 100 mg / l, particularly preferably in the range of 6 to 60 mg / l (calculated as 2-butyne-1, 4-diol).
  • the conversion composition iv) comprises at least one compound of the formula I.
  • concentration of the at least one compound of the formula I in the conversion composition iv) is in the range from 1 to 100 mg / l, preferably in the range from 3 to 100 mg / l and more preferably in the range 30 to 100 mg / l (calculated as 2-butyne-1,4-diol).
  • the metallic surface is contacted between contacting with the first rinse composition ii) or optionally the second rinse composition iii) and the conversion composition iv) with an aqueous pickle composition vii) and then with a fourth rinse composition viii).
  • the pickling composition vii) preferably contains at least one compound selected from the group consisting of phosphonates, condensed phosphates and citrate and / or at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, more preferably it contains at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, most preferably it contains sulfuric acid.
  • the pickling composition vii) contains at least one compound of the formula I.
  • the concentration of the at least one compound of the formula I in the mordant composition vii) is in the range from 31 to 620 mg / l, preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1, 4-diol).
  • the use of the at least one compound of the formula I in the pickling composition has the advantage of particularly effectively reducing pickling.
  • the detergent composition is i) alkaline, more preferably has a pH of 9.5 or greater.
  • the first rinsing composition ii), the second rinsing composition iii) and the third rinsing composition v) preferably have a pH in the range from 2 to 10, more preferably in the range from 3 to 10.
  • the first rinse composition is preferably weakly acidic, slightly alkaline or neutral. Particularly preferably, it has a pH in the range from 6 to 9.
  • the second rinse composition is preferably weakly alkaline or neutral. Most preferably, it has a pH in the range of 7 to 9.
  • the third rinse composition preferably has a pH in the range of 4 to 9, more preferably it is slightly acidic, slightly alkaline or neutral. Most preferably, it has a pH in the range of 6 to 8.
  • the conversion composition iv) is a passivating composition containing a titanium, zirconium and / or hafnium compound.
  • the passivating composition iv) is substantially free of manganese.
  • essentially manganese-free is meant that less than 10 mg / l of manganese is contained in the four pass composition.
  • the titanium, zirconium and / or hafnium compound is preferably the corresponding hexafluoro complex, most preferably hexafluorozirconate.
  • the passivating composition iv) preferably contains copper ions and / or a compound which releases copper ions and / or zinc ions and / or a compound which liberates zinc ions.
  • the passivating composition iv) preferably contains an organoalkoxysilane and / or a hydrolysis and / or a condensation product thereof.
  • the organoalkoxysilane preferably has at least one amino group. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
  • the passivating composition may also contain a polymer and / or copolymer.
  • the at least one compound of the formula I is a mixture of a compound of the formula I in which R 1 and R 2 are both H, and a compound of the formula I in which R 1 and R 2 are each independently one HO- (CH 2 ) w group with w> 2.
  • the at least one compound of formula IR 1 and R 2 are both H or an HO- (CH 2 ) 2 group, the sum of x and y is 2 to 5 and Z is a CC triple bond.
  • the at least one compound of the formula I is 2-butyne-1,4-diol and / or 2-butyne-1,4-diol bis (2-hydroxyethyl ether).
  • the at least one compound of the formula I is particularly preferably a mixture of 2-butyne-1,4-diol and 2-butyne-1,4-diol bis (2-hydroxyethyl ether), the mixing ratio based on wt Range of 0.5: 1 to 2: 1, preferably in the range of 0.75: 1 to 1, 75: 1 and particularly preferably in the range 1: 1 to 1, 5: 1.
  • the metallic surface treated with the method according to the invention is preferably the surface of a metal strip or a metallic component, for example a body.
  • the metallic surface may include bare steel, electrolytically galvanized and / or hot-dip galvanized steel, aluminum and / or an aluminum alloy.
  • the metallic surface in addition to bare steel and / or galvanized steel, the metallic surface also contains aluminum or an aluminum alloy (so-called multimetal capability).
  • the process according to the invention has proved to be advantageous in the case of acrylate- and / or epoxide-based cathodic electrocoating paint (EPC) in terms of improved paint adhesion and improved corrosion protection.
  • EPC cathodic electrocoating paint
  • a topcoat is optionally applied to the KTL-coated metallic surface.
  • the present invention further relates to an aqueous composition for reducing pickling in the anti-corrosive treatment of metallic surfaces, which contains at least one compound of the formula I as described above.
  • aqueous composition according to the invention in addition, it relates to a concentrate from which the aqueous composition according to the invention can be obtained by dilution with a suitable solvent and / or dispersion medium, preferably with water, and optionally adjusting the pH.
  • the dilution factor is preferably in the range from 1:10 to 1: 10,000, more preferably in the range from 1:50 to 1: 200.
  • the present invention also relates to the use of the metallic surface treated by the method according to the invention.
  • the present invention is to be illustrated by the following - not to be limited - embodiments.
  • the system is brought out of equilibrium by applying an external potential.
  • the cathodic substream represents the cathodic reaction. At pH values of 4 or higher, oxygen reduction is dominant here.
  • the anodic substream must be set equal to the anodic reaction or the metal oxidation. From this, partial current density-potential curves can be derived:
  • anodic and cathodic partial currents are equal in magnitude at a potential. This point is the resting potential. From the above equations for the cathodic and anodic substream, it is finally possible to determine the corrosion potential E kor r and the corrosion current density Ikon, from which conclusions can be drawn about the corrosion behavior of the sample.
  • E k0 rr describes the rest potential.
  • Ikon- corresponds to the cathodic and anodic partial current density, which are the same at the resting potential.
  • the respective partial flows are plotted as a straight line.
  • the logarithm of the currents is plotted against the potential, which results in straight lines.
  • the corrosion potential E kor r and the corrosion current density Ikon- can be read on the basis of the intersection of the logarithmic partial flows. The evaluation is carried out in the linear part of the curve.
  • Beizenabtrag indicates by what percentage of the weight loss of the metal by the addition of an inhibitor is reduced.
  • a defined test sheet is dipped in the appropriate test solution.
  • the mass loss on the surface is determined gravimetrically before and after each.
  • test panels were first cleaned with petroleum benzine. The residual carbon content after purification was less than 10 mg / m 2 .
  • the mass of each 105 x 190 mm sized and cleaned hot dip galvanized steel test plate was determined on the analytical balance. Immediately following the determination of the mass, the test panels were each hung in a 3 liter beaker with an appropriate test solution. It was stirred with a 40 mm magnetic stir bar. The stirring speed was 400 rpm at the bottom of the beaker. After 3 minutes, the test panels were each removed from the solution, rinsed with distilled water and dried with compressed air. Subsequently, the mass of each test sheet was again determined with the analytical balance.
  • the inhibition value indicates by what percentage the attack on the workpiece by the inhibitor (s) can be reduced. The higher this inhibition value compared to the non-inhibited solution A, the greater the corrosion-protecting properties within the pretreatment process.
  • the reduction of the material loss is necessary in order to remove as little as possible of the galvanizing within the process and to reduce associated zinc phosphate sludge in the corresponding cleaner zones of a pretreatment plant.
  • Blank steel (CRS) test panels were sprayed in sequence with each other for 180 seconds and 45 ° C. with a strong alkaline multi-metal cleaner, city water (first rinse composition) for 30 seconds, and deionized water (second rinse composition) for 20 seconds , They were then treated for 120 s at 30 ° C (conversion composition A ', see below) or 40 ° C (conversion composition B' and C, see below) with a conversion composition (see Table 3) and then for 20 s with VE Water (third rinse composition) sprayed. Finally, the test panels were dried with compressed air, coated with an acrylate-based KTL and subjected to crosshatch, stone chip and NSS tests.
  • the conversion composition A ' is an acidic aqueous solution of 0.2 g / l zirconium, 0.1 g / l each of zinc and manganese, 0.3 g / l of total fluoride and 30 mg / l of free fluoride at pH 5 ; 2.
  • the conversion composition B ' is an acidic aqueous solution of 0.1 g / L zirconium, 0.4 g / L zinc, 0.1 g / L total fluoride, 2 mg / L copper and 30 mg / L free Fluoride at pH 4.9, which additionally contains 3.1 mg / l but-2-yn-1,4-diol and 2.5 mg / l 2-butyne-1,4-diol bis (2-hydroxyethyl ether) ,
  • the conversion composition C is an acidic aqueous solution of 0.1 g / l zirconium, 0.4 g / l zinc, 0.1 g / l total fluoride, 5 mg / l Copper and 30 mg / l free fluoride at pH 4.9, which additionally contains 31 mg / l but-2-yn-1,4-diol and 25 mg / l 2-butyne-1,4-diol-bis (2- hydroxyethyl ether).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
PCT/EP2017/060229 2016-04-29 2017-04-28 Verfahren zur korrosionsschützenden behandlung einer metallischen oberfläche mit vermindertem beizabtrag Ceased WO2017186931A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US16/097,169 US20220119650A9 (en) 2016-04-29 2017-04-28 Method for anti-corrosion treatment of a metal surface with reduced pickling material
EP17723944.9A EP3448938A1 (de) 2016-04-29 2017-04-28 Verfahren zur korrosionsschützenden behandlung einer metallischen oberfläche mit vermindertem beizabtrag
CN201780024292.4A CN109071973A (zh) 2016-04-29 2017-04-28 具有减少的酸洗材料的金属表面防腐蚀处理方法
JP2018556915A JP7034090B2 (ja) 2016-04-29 2017-04-28 材料の腐食除去が低減される金属表面の防食処理のための方法
KR1020187030704A KR102373768B1 (ko) 2016-04-29 2017-04-28 재료의 피클링이 감소된 금속 표면의 부식방지 처리 방법
MX2018013229A MX2018013229A (es) 2016-04-29 2017-04-28 Proceso para el tratamiento anticorrosion de una superficie metalica con remocion corrosiva reducida de material.
RU2018141059A RU2754070C2 (ru) 2016-04-29 2017-04-28 Способ антикоррозионной обработки металлической поверхности с уменьшенным травлением материала
BR112018071503-4A BR112018071503A2 (pt) 2016-04-29 2017-04-28 processo para tratamento anticorrosivo de uma superfície metálica, composição aquosa, concentrado, e, uso da superfície metálica

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