EP3011074A1 - Procédé à plusieurs étapes pour le laquage par électro-immersion - Google Patents

Procédé à plusieurs étapes pour le laquage par électro-immersion

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Publication number
EP3011074A1
EP3011074A1 EP14725124.3A EP14725124A EP3011074A1 EP 3011074 A1 EP3011074 A1 EP 3011074A1 EP 14725124 A EP14725124 A EP 14725124A EP 3011074 A1 EP3011074 A1 EP 3011074A1
Authority
EP
European Patent Office
Prior art keywords
less
ppm
reaction rinse
conversion treatment
aqueous composition
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.)
Granted
Application number
EP14725124.3A
Other languages
German (de)
English (en)
Other versions
EP3011074B1 (fr
Inventor
Nils BONGARTZ
Kirsten Agnes LILL
Ralf POSNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP14725124.3A priority Critical patent/EP3011074B1/fr
Publication of EP3011074A1 publication Critical patent/EP3011074A1/fr
Application granted granted Critical
Publication of EP3011074B1 publication Critical patent/EP3011074B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the present invention is a multi-stage process for corrosion-protective coating of metallic components, in which a conversion treatment is followed by a reaction rinse, before a
  • Electrocoating of the component is performed.
  • the conversion treatment initially involves the deposition of an inorganic thin layer containing the elements Zr and / or Ti.
  • the metallic component is then aftertreated with a reaction rinse containing a surface-active substance and subsequently electrocoated.
  • Electrocoating is a process that has been practiced for decades. From an economic point of view and due to ecological concerns, the automotive industry is endeavoring to replace the technically established conversion treatment by means of zinc phosphating by a resource-sparing and preferably equivalent pretreatment. In contrast to zinc phosphating, alternative concepts for conversion treatment often provide amorphous coatings with layer thicknesses in the nanometer range, in order to meet the desire for a less extensive pretreatment process.
  • WO 07/065645 discloses such a resource-conserving process for the anticorrosive coating of metallic substrates such as steel and galvanized steel comprising the process steps of the conversion treatment and subsequent dip-coating, wherein between the
  • Conversion treatment and electrocoating optionally a rinsing and / or drying step takes place.
  • a "wet-on-wet" process is preferred in which a drying step is omitted, and thus with a
  • Electrocoating as a high electrical resistance that
  • Coating behavior of electrocoating is referred to as
  • EP 1 455 002 A1 discloses in a related context a
  • Post-treatment steps are proposed to reduce the proportion of water-soluble fluorides in the conversion layer and thus to improve the corrosion protection after electrocoating. As more effective
  • an intermediate sink may also be effected before the electrodeposition coating and after the conversion treatment, it being possible to use aqueous solutions containing water-soluble compounds of the elements Co, Ni, Sn, Cu, Ti and Zr or water-soluble or water-dispersible organic polymers.
  • the object is to optimize the known process sequence of corrosion-protective pretreatment and subsequent electrocoating in such a way that on the one hand realizes savings in the coating material in the electrodeposition coating and on the other hand components with complex geometries can be satisfactorily electrocoated.
  • This object is achieved by a multi-stage method for
  • “Surface-active substances” in the context of the present invention are organic compounds composed of a hydrophilic and at least a lipophilic molecular constituent or a lipophilic and at least one hydrophilic molecular constituent, wherein the molecular weight of the
  • Electroating in the context of the present invention is each brought about by applying an external voltage source to the metallic component
  • a "rinsing step" in the sense of the present invention refers to a process that is intended solely for the immediate purpose of active components
  • active components in this context are constituents contained in a liquid phase which cause an analytically detectable coating of the metal surfaces of the component with elemental constituents of the active components.
  • a "drying step” in the context of the present invention refers to a process in which the surfaces of the metallic component having a wet film are to be dried with the aid of technical measures.
  • the layer coating of zirconium and / or titanium can be determined directly after the conversion treatment by means of X-ray fluorescence analysis method (RFA) after rinsing with deionized water ( ⁇ ⁇ ⁇ 1 ) and subsequent drying of the component.
  • RFA X-ray fluorescence analysis method
  • Electrodeposition coating with constant wringing a smaller layer thickness of the dipping paint or at a constant immersion coating thickness improved Umgriffs . Accordingly, a comparatively resource-saving operation is ensured in the electrocoating and the
  • the proportion of surface-active substances in the reaction rinse is preferably at least 20 ppm, more preferably at least 50 ppm. If these preferred minimum levels of surfactants are undercut, there will be a significant decrease in wrap-around with otherwise identical electrocoating parameters that is no longer acceptable for certain complex geometry applications and components. Above 1 wt .-% of surface-active substances, a further improvement of Umgriffs regularly not observed, so that for reasons of economy preferably not more than 1 wt .-% of surface-active substances in the reaction rinse of the inventive method are included.
  • ppm stands for "parts per million” and in the context of the present invention refers to the mass of the respective composition so that 1 ppm corresponds to a proportion of 1 mg of the respective substance per kilogram of the respective composition.
  • the surface-active substances in the reaction rinse of the process according to the invention can be selected from anionic surfactants, cationic surfactants,
  • nonionic surfactants zwitterionic surfactants and nonionic surfactants, wherein the use of nonionic surfactants is preferred in the reaction rinse, inter alia, because of their good compatibility with the bath constituents of the electrodeposition coating. Compatibility here is to be understood as the absence of precipitates in the dip-coating bath.
  • Electrocoating is to be considered, as the lugging of
  • nonionic surfactants are components of
  • HLB value hydrophilic-lipophilic balance
  • the HLB value is used for the quantitative classification of nonionic surfactants according to their internal molecular structure, with a breakdown of the nonionic surfactant into a lipophilic and a hydrophilic group.
  • the HLB value according to The present invention is calculated according to the following formula and can assume values of zero to 20 on the arbitrary scale:
  • Mi molar mass of the lypophilic group of nonionic surfactant
  • nonionic surfactants are preferred in the reaction rinse of the process according to the invention for further improving the encasing of the dip coating, which are selected from alkoxylated alkyl alcohols, alkoxylated fatty amines and / or alkylpolyglycosides, particularly preferably from alkoxylated alkyl alcohols and / or alkoxylated fatty amines, particularly preferably from alkoxylated alkyl alcohols.
  • the alkoxylated alkyl alcohols and / or alkoxylated fatty amines are preferably end-capped, particularly preferably having an alkyl group which in turn preferably has not more than 8 carbon atoms, more preferably not more than 4 carbon atoms.
  • alkoxylated alkyl alcohols and / or alkoxylated fatty amines as nonionic surfactants in the reaction rinse of the process according to the invention which are ethoxylated and / or propoxylated, the number of alkylene oxide units preferably not being greater than 20, particularly preferably not greater than 16. but more preferably at least 4, more preferably at least 8.
  • those alkoxylated alkyl alcohols and / or alkoxylated fatty amines are preferred as nonionic surfactants in the reaction rinse of the process according to the invention whose alkyl group is saturated and preferably unbranched, the number of carbon atoms in the alkyl group preferably not being smaller than 6, more preferably not less than 10, but preferably not greater than 24, more preferably not greater than 20.
  • alkoxylated alkyl alcohols and / or alkoxylated fatty amines are those alkoxylated alkyl alcohols and / or alkoxylated fatty amines, in particular the alkoxylated alkyl alcohols, whose lipophilic alkyl group comprises at least 10 carbon atoms, more preferably at least 12 carbon atoms, wherein the longest carbon chain in the alkyl group of at least 8th
  • Carbon atoms and an HLB value is realized in the range of 12 to 16 realized.
  • the pH is preferably not below 4, more preferably not below 6, in order to minimize the pickling attack on the coating produced in the conversion treatment by an acid reaction rinse.
  • Reaction rinses preferably have no pH above 12, more preferably above 10.
  • the pH in a preferred embodiment of the process according to the invention is to be adjusted to neutral (pH 7) to alkaline, the pH again preferably not being above 12, more preferably not above 1 , particularly preferably should not be above 10, but preferably at least 7, more preferably at least 8.
  • the adjustment of the alkaline pH causes in the presence of nonionic surfactants a significant improvement of the Umgriffs in subsequent electrocoating, especially if between the conversion treatment and reaction rinse no rinsing step, more preferably neither a rinsing step nor a drying step.
  • the adjustment of the pH of the reaction rinse is preferably carried out via a
  • Buffer system making the entry of components of acidic aqueous
  • composition from the conversion treatment in the Nach Hughese does not lead to a shift in the pH outside the optimal range.
  • the method according to the invention therefore, after the conversion treatment and before the reaction rinse on a be dispensed with additional rinsing step.
  • the use of a buffer system also facilitates the bath control, since a re-dosing of the pH-stabilizing substances has to be done only moderately and occasionally.
  • the method according to the invention contains
  • a preferred buffer system is a carbonate-bicarbonate buffer system (for example Na 2 C0 3 / NaHC0 3 ).
  • the “pH” in the present invention refers to the negative decadic logarithm of the activity of the hydronium ions at 25 ° C.
  • the positive influence of the reaction rinse on the immersion of the dipping paint is weakened by the additional presence of layer-forming active components and sometimes fails completely. This applies in particular to those active components which are capable of forming thin amorphous phosphate layers.
  • reaction sink less than 1 g / kg, more preferably less than 0, 1 g / kg, most preferably less than 0.01 g / kg dissolved in water phosphates calculated as P0. 4
  • the layer-forming active components which cause worsening of the wraparound also include water-soluble compounds of certain metal elements, which usually cause a conversion of the metal surface.
  • the aqueous composition of the reaction rinse less than 20 ppm, more preferably less than 10 ppm, more preferably less than 1 ppm of water-soluble compounds of elements of subgroups HIB, IVB, VIB and / or the element vanadium based on the respective Contains element, wherein preferably less than 20 ppm of these water-soluble compounds are contained in total based on said elements.
  • silanes which are present in the reaction rinse of the process according to the invention preferably in an amount of less than 0.005 g / l, more preferably less than 0.002 g / l, particularly preferably less than 0.001 g / l are calculated based on the corresponding silanols.
  • Silanes in the context of this invention include silanes, silanols, siloxanes,
  • reaction products are in particular condensation and hydrolysis products in the aqueous medium to understand.
  • the process according to the invention can be the presence of such layer-forming active components in the reaction rinse, which cause the deposition of a metallic phase upon contact with the metallic component.
  • the aqueous composition of the reaction solution is less than 50 ppm, preferably less than 10 ppm, more preferably less than 5 ppm of water-soluble compounds of the elements Co, Ni, Cu and / or Sn contains on the respective element, wherein preferably less than 50 ppm in total of these water-soluble compounds are contained based on said elements.
  • compositions containing fluoro acids of the elements zirconium and / or titanium and their salts and hydrolysis products are
  • the reaction rinse for such processes according to the invention in which a phosphate layer is produced in the conversion treatment, produces a substantially lower effect with regard to the improvement of the encapsulation in the subsequent electrodeposition coating.
  • the acidic aqueous composition for the conversion treatment does not produce a phosphate layer with a layer coverage of at least 0.2 g / m 2, based on P0 4, on the metallic component.
  • the acidic aqueous composition should be any suitable for the conversion treatment.
  • Conversion treatment preferably less than 1 g / kg in total, especially preferably a total of less than 0.1 g / kg of phosphates dissolved in water, calculated as P0 4 .
  • Conversion layer formation based on the elements zirconium and / or titanium is added can affect the application of the spray process adversely affect the effectiveness of the method according to the invention. It is therefore preferred that the acidic conversion conversion composition in such processes according to the invention in which the conversion treatment is effected by spraying has a total of less than 50 ppm, more preferably less than 10 ppm, most preferably less than 1 ppm of copper dissolved in water. Contains ions.
  • the molar ratio of the total proportion of water-soluble compounds of zirconium and / or titanium based on the respective elements zirconium and titanium to the total content of water-soluble compounds of the elements Co, Ni, Cu and / or Sn based on the respective elements Co, Ni, Cu and / or Sn in the conversion bath is preferably not less than 0.6, more preferably not less than 1.0.
  • the presence in the reaction rinse can be disadvantageous for the process according to the invention. Accordingly, preference is given to those processes in which the introduction of silanes into the reaction rinse is largely prevented.
  • This can be done, for example, by the acidic composition not being a silane-based composition in the conversion treatment.
  • the acidic composition in the conversion treatment contains a total of less than 0.005 g / l, more preferably less than 0.002 g / l, particularly preferably less than 0.001 g / l of silanes calculated on the basis of the corresponding silanols.
  • the type of application of both the acidic aqueous composition in the conversion treatment and the reaction rinse is freely selectable under conventional application methods.
  • the aqueous compositions of the method according to the invention can be brought into contact with the metallic component either by spraying or by immersion.
  • a rinsing and / or drying step can be intermediately interposed between the reaction rinse and the subsequent electrocoating.
  • the advantage of the method according to the invention is that contained in the reaction rinse in a preferred embodiment according to the invention
  • Nonionic surfactants exert no adverse effect on the electrodeposition coating, so that can be dispensed with an intermediate rinsing step to remove the surface-active substances in adhering to the component wet film before electrocoating.
  • an intermediate rinsing step to remove the surface-active substances in adhering to the component wet film before electrocoating.
  • the metallic component can therefore be electrocoated after the reaction rinse without intervening rinsing step.
  • Drying step - can be performed.
  • the corrosion-protected coated metallic component in the method according to the invention is preferably selected from aluminum, zinc, iron, steel and / or galvanized steel.
  • the method according to the invention is particularly suitable for improving the encircling of an immersion paint on surfaces of steel and / or galvanized steel.
  • the bath is filled with service water, 3% Ridoline® 1574 and 0.3% Ridosol® 1270 (each Henkel AG & Co. KGaA) added and the pH adjusted to pH 1 1 by slow addition of a phosphate solution.
  • Treatment time 120 seconds
  • Treatment time 30-60 seconds
  • Treatment time 30-60 seconds
  • Separation voltage was set within 15 seconds by means of a corresponding potential ramp. The determination of
  • Coating layer thickness was carried out after curing of the dip coating for 25 min at 180 ° C by means of a coating thickness gauge (DUALSCOPE® FMP40, Helmut Fischer GmbH).
  • a coating thickness gauge DUALSCOPE® FMP40, Helmut Fischer GmbH.
  • Reference sheet pair only the treatment steps 1 -3, 5 and 6 passes.
  • the changes in dip paint thickness and wrap around refer to the corresponding values of the reference plate pair.
  • Electrocoating bath brought and switched as a cathode.
  • a stainless steel anode was arranged in parallel at a distance of 10 cm, the cathode to anode area ratio being 5: 1.
  • the conversion bath contained 270 ppm H 2 ZrF 6 , 60 ppm ZrO (NO 2) 2 and 300 ppm HNO 3 .
  • the pH was adjusted to pH 4.5 by addition of aqueous ammoniacal solution.
  • the conversion treatment was carried out at 40 ° C bath temperature for 60 seconds by spraying at a pressure of 1 bar.
  • reaction rinse was carried out with a solution of 750 ppm 2,4,7,9-tetramethyl-5-decyne-4,7-diol in demineralized water for 60 seconds at 20 ° C by immersion.
  • reaction rinse was carried out with 200 ppm of butyl end-capped 4- to 5-tuply ethoxylated octanol (C8, 4-5 EO, butyl, HLB value 14) in deionized water for 60 seconds at 20 ° C. by immersion.
  • reaction rinse was carried out with a solution of 20 ppm of butyl end-capped 10-times ethoxylated C12-C18 fatty alcohols (C12-C18, 10 EO, butyl, HLB value 13.3-15) in demineralized water for 60 seconds at 20.degree by spraying at an injection pressure of 1 bar.
  • C12-C18, 10 EO, butyl, HLB value 13.3-15 ethoxylated C12-C18 fatty alcohols
  • the reaction rinse was carried out for 60 seconds at 20 ° C. by spraying at an injection pressure of 1 bar with a solution of 100 ppm of butyl end-capped 10-times ethoxylated C12-C18 fatty alcohols (C12-C18, 10 EO, butyl, HLB value 13, 3-15) and 5 wt .-% of a buffer system consisting of 0.2 mol / L Na 2 C0 3 and 0.2 mol / L NaHCOs in deionized water (pH 9.7).
  • reaction rinse was carried out for 60 seconds at 20 ° C. by spraying at an injection pressure of 1 bar with a solution of 100 ppm of butyl end-capped 10-times ethoxylated C12-C18 fatty alcohols (C12-C18, 10 EO, butyl, HLB value 13, 3-15) at a pH of 7.8.
  • the conversion bath contained 340 ppm H 2 ZrF 6 , 15 ppm Cu (NO 2) 2 and 4 ppm HF.
  • the pH was adjusted to pH 4.0 by addition of aqueous ammoniacal solution.
  • the conversion treatment was carried out at 20 ° C bath temperature for
  • reaction rinse was carried out with a solution of 1000 ppm of butyl end-capped 10-times ethoxylated C12-C18 fatty alcohols (C12-C18, 10EO, butyl, HLB value 13.3-15) in demineralized water for 120 seconds at 20 ° C by immersion.
  • reaction sink effected with a solution of 67 ppm butyl-sealed end group 10-tuply ethoxylated C12-C18 fatty alcohols (C12-C18, 10 EO, butyl; HLB value from 13.3 to 15) and 27 ppm H 2 ZrF 6 in VE - Water for 60 seconds at 20 ° C by spraying at an injection pressure of 1 bar.
  • Comparative Example CB1 To prepare a Eisenphosphatierirri a bath was filled with deionized water, 2 wt .-% Duridine 7760 (Henkel AG & Co. KGaA) was added, the pH adjusted by slow addition of sodium hydroxide solution to pH 4.5. The sheet was then sprayed from the bath at a temperature of 50 ° C for 1 10 seconds at an injection pressure of 1 bar with the iron phosphating solution. The layer weight of iron phosphate was 0.5 g / m 2 determined as P0. 4
  • reaction rinse was carried out with a solution of 1000 ppm of butyl end-capped 10-times ethoxylated C12-C18 fatty alcohols (C12-C18, 10 EO, butyl, HLB value 13.3-15) in deionised water for 60 seconds at 20.degree by immersion.
  • Table 1 summarizes the values for the electrodeposition paint thickness and the throw-over for the exemplary embodiments described above.
  • example B7 shows that the additional presence of
  • the absolute values were measured on the outer sides of the plate pairs facing the anode (in each case averaged over 5 layer thickness measurements). The respective absolute value corresponds to the longest visible extent of the dip coating on the insides of the plate pair

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Un objet de la présente invention est un procédé à plusieurs étapes pour le revêtement de protection contre la corrosion d'éléments métalliques, dans lequel un traitement de conversion est suivi d'un rinçage de réaction, avant qu'un laquage par électro-immersion de l'élément ne soit réalisé. Le traitement de conversion comporte d'abord le dépôt d'une couche mince inorganique contenant les éléments Zr et/ou Ti. L'élément métallique est ensuite post-traité par un rinçage de réaction contenant une substance tensio-active et ensuite laqué par électro-immersion.
EP14725124.3A 2013-06-20 2014-05-16 Procédé à plusieurs étapes pour un revêtement électrophorétique Active EP3011074B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14725124.3A EP3011074B1 (fr) 2013-06-20 2014-05-16 Procédé à plusieurs étapes pour un revêtement électrophorétique

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13173055 2013-06-20
EP14725124.3A EP3011074B1 (fr) 2013-06-20 2014-05-16 Procédé à plusieurs étapes pour un revêtement électrophorétique
PCT/EP2014/060063 WO2014202294A1 (fr) 2013-06-20 2014-05-16 Procédé à plusieurs étapes pour le laquage par électro-immersion

Publications (2)

Publication Number Publication Date
EP3011074A1 true EP3011074A1 (fr) 2016-04-27
EP3011074B1 EP3011074B1 (fr) 2017-07-05

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Country Status (8)

Country Link
US (1) US9382628B2 (fr)
EP (1) EP3011074B1 (fr)
JP (1) JP6465871B2 (fr)
KR (1) KR102278974B1 (fr)
CN (1) CN105324517B (fr)
BR (1) BR112015031240A2 (fr)
ES (1) ES2642271T3 (fr)
WO (1) WO2014202294A1 (fr)

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EP3502311A1 (fr) * 2017-12-20 2019-06-26 Henkel AG & Co. KGaA Procédé de prétraitement de nettoyage et de protection anticorrosion de composants métalliques

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Also Published As

Publication number Publication date
KR102278974B1 (ko) 2021-07-16
JP2016527391A (ja) 2016-09-08
ES2642271T3 (es) 2017-11-16
US20160102405A1 (en) 2016-04-14
BR112015031240A2 (pt) 2017-07-25
EP3011074B1 (fr) 2017-07-05
WO2014202294A1 (fr) 2014-12-24
CN105324517A (zh) 2016-02-10
US9382628B2 (en) 2016-07-05
JP6465871B2 (ja) 2019-02-06
KR20160022309A (ko) 2016-02-29
CN105324517B (zh) 2017-10-27

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