EP3449040B1 - Zusammensetzung zur verminderung des beizabtrags beim beizen von metallischen oberflächen enthaltend blanken und/oder verzinkten stahl - Google Patents

Zusammensetzung zur verminderung des beizabtrags beim beizen von metallischen oberflächen enthaltend blanken und/oder verzinkten stahl Download PDF

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Publication number
EP3449040B1
EP3449040B1 EP17721118.2A EP17721118A EP3449040B1 EP 3449040 B1 EP3449040 B1 EP 3449040B1 EP 17721118 A EP17721118 A EP 17721118A EP 3449040 B1 EP3449040 B1 EP 3449040B1
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EP
European Patent Office
Prior art keywords
pickling
composition
formula
range
diol
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Active
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EP17721118.2A
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German (de)
English (en)
French (fr)
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EP3449040A1 (de
Inventor
Anna Verena MOHR
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Chemetall GmbH
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Chemetall GmbH
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Priority to PL17721118T priority Critical patent/PL3449040T3/pl
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/081—Iron or steel solutions containing H2SO4
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors

Definitions

  • the invention relates to an aqueous composition for reducing the pickling removal when pickling metallic surfaces containing bright and / or galvanized steel and a method for pickling a corresponding metallic surface with reduced pickling removal.
  • Atmospheric corrosion or during heat treatment e.g. heat development during forming or welding
  • heat treatment e.g. heat development during forming or welding
  • pickling refers to the dissolution of these oxide layers in mineral acid solutions in order to achieve a clean metallic surface for further processing.
  • This essentially serves to remove oxide films from rust - FeO, Fe 2 O 3 , Fe 3 O 4 and iron oxide hydrates - or zinc oxide from the surface, which in turn increases the adhesive strength and uniformity of subsequent coatings, in particular a conversion coating, on the surface.
  • the atomic hydrogen (H ⁇ ) which develops in accordance with equation (4) is preferably absorbed on iron, penetrates into the crystal lattice and combines there to form hydrogen molecules (H 2 ).
  • the pressures generated by the hydrogen gas deteriorate the mechanical properties of the metal.
  • This embrittlement is irreversible and can lead to cracks or pickling bubbles.
  • the decisive factor for the extent of embrittlement is the amount of hydrogen developed during pickling removal.
  • the metallic surface Due to excessive pickling removal and, above all, the cracks and pickling bubbles formed due to the pickling hydrogen embrittlement, the metallic surface receives an uneven morphology, which is transferred to subsequent coatings to the extent that they also have a certain unevenness. This in turn leads to a reduction in the adhesive strength of the coatings and in the corrosion protection they produce.
  • alkali metal alkoxylates or thiodiglycolate alkoxylates which act as pickling inhibitors, i.e. reduce the pickling removal.
  • N, N'-diethylthiourea and mixtures of N, N'-di (o-tolyl) thiourea, N, N'-dibutylthiourea and hexamethylenetetraamine give satisfactory results due to an inhibition value of 96 percent each.
  • N, N'-diethylthiourea is increasingly undesirable since this is very questionable from a toxicological and environmental point of view.
  • Each of the pamphlets FR 1 475 895 A , US 2009/032057 A1 , FR 2 158 664 A5 , US 3,310,497 A. , DE 25 07 059 A1 , DE 10 2015 005521 A1 each discloses an aqueous composition for reducing the pickling removal when pickling steel surfaces and / or galvanized steel surfaces containing an acid, such as sulfuric acid, hydrochloric acid or phosphoric acid, and 2-butyne-1,4-diol as a corrosion inhibitor.
  • an acid such as sulfuric acid, hydrochloric acid or phosphoric acid
  • 2-butyne-1,4-diol as a corrosion inhibitor.
  • the object of the invention was therefore to provide a composition for reducing the removal of pickling when pickling metallic surfaces containing bright and / or galvanized steel, and a method for pickling a corresponding metallic surface with reduced pickling removal, which completely with a subsequent pickling Conversion treatment is compatible and less toxicologically harmful and less harmful to the environment.
  • the reduced pickling removal should preferably increase the service life of a corresponding pickling bath.
  • composition according to claim 1 a concentrate according to claim 7, a method according to claim 8 and a use according to claim 15.
  • Advantageous embodiments are described in the dependent claims.
  • the aqueous composition according to the invention for reducing the removal of pickling when pickling metallic surfaces containing bright and / or galvanized steel contains a mixture of a compound of the formula I.
  • an "aqueous composition” is to be understood to mean one which for the most part, i.e. contains more than 50% by weight of water as a solvent / dispersant.
  • the aqueous composition is preferably a solution, more preferably a solution which contains only water as a solvent.
  • the “galvanized steel” can be either electrolytically galvanized or hot-dip galvanized steel.
  • Compounds of the formula I act as physical corrosion inhibitors which are adsorbed on the metallic surface by Van der Waals forces, as a result of which a monomolecular, homogeneous, densely packed layer is formed thereon. Said layer physically shields the metallic surface from a proton attack at least partially and thus prevents or at least reduces the pickling removal of the surface.
  • the aqueous composition according to the invention is essentially free of N, N'-diethylthiourea, N, N'-di (o-tolyl) thiourea, N, N'-dibutylthiourea and hexamethylenetetraamine.
  • Essentially free means that the aforementioned compounds have not been added to the composition at will, so that they are at most impurities in the starting materials used.
  • the total content of these compounds in the composition according to the invention is preferably below 5 mg / l, more preferably below 1 mg / l.
  • the mixing ratio, based on% by weight, of the compound of the formula I in which R 1 and R 2 are both H and the compound of the formula I in which R 1 and R 2 are each independently an HO- (CH 2 ) w Group with w ⁇ 2 is preferably in the range from 0.5: 1 to 2: 1, particularly preferably in the range from 0.75: 1 to 1.75: 1 and very particularly preferably in the range from 1: 1 to 1.5: 1 (calculated as 2-butyne-1,4-diol and 2-butyne-1,4-diol-bis (2-hydroxyethyl ether)).
  • the sum of x and y in each of the two compounds of the formula I is preferably 2 to 5.
  • the aqueous composition contains a mixture of 2-butyne-1,4-diol and 2-butyne-1,4-diol-bis (2-hydroxyethyl ether).
  • the mixing ratio based on% by weight is again preferably in the range from 0.5: 1 to 2: 1, particularly preferably in the range from 0.75: 1 to 1.75: 1 and very particularly preferably in the range 1: 1 up to 1.5: 1.
  • the composition additionally contains at least one compound of the formula II R 1 O- (CH 2 ) x -S- (CH 2 ) y -OR 2 (II), wherein R 1 and R 2 are each independently H or a HO- (CH 2 ) w group with w ⁇ 2, and x and y are each independently 1 to 4.
  • the at least one compound of the formula II is preferably HO-CH 2 -S-CH 2 .
  • the aqueous composition according to the invention can be obtained from the concentrate according to the invention by dilution with a suitable solvent and / or dispersion medium, preferably with water, and if necessary adjusting the pH.
  • the dilution factor is preferably in the range from 1:23 to 1: 225.
  • the dilution factor when adding the concentrate to the rinsing solution in step iii) is preferably in the range from 1: 225 to 1: 2250.
  • an alkaline cleaning solution is preferably used, particularly preferably with a pH of 9.5 or more.
  • the pickling composition ii) 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, particularly preferably it contains at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, very particularly preferably contains sulfuric acid.
  • the pH of the rinsing composition in step iii) is preferably strongly acidic, neutral or slightly alkaline, particularly preferably it is in the range from 2 to 8.
  • the pickling composition in step ii) is a composition according to the invention as described above.
  • the total concentration of the mixture of the two compounds of the formula I in the pickling composition is preferably in the range from 31 to 620 mg / l, particularly preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1,4-diol) .
  • the use of the mixture of the two compounds of the formula I in the pickling composition has the advantage of reducing the pickling removal particularly effectively.
  • the rinsing composition in step iii) is a composition according to the invention as described above.
  • the total concentration of the mixture of the two compounds of the formula I in the rinsing composition is preferably in the range from 3 to 62 mg / l, particularly preferably in the range from 3 to 31 mg / l (calculated as 2-butyne-1,4-diol) . Even during the rinsing of the previously pickled metallic surface, mineral acid is still present from the liquid film adhering to the surface, so that the pickling attack continues, albeit in a weakened form. As a result, flash rust is formed.
  • the use of the mixture of the two compounds of formula I in the rinsing composition has the advantage of reducing this rust formation.
  • the pickling composition in step ii) and the rinsing composition in step iii) are each a composition according to the invention as described above.
  • the mixture of the two compounds of the formula I in the pickling composition and that in the rinsing composition can be the same or a different mixture.
  • the total concentration of the mixture of the two compounds of the formula I in the pickling composition is again preferably in the range from 31 to 620 mg / l, particularly preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1,4-diol ) and in the rinsing composition preferably in the range from 3 to 62 mg / l, particularly preferably in the range from 3 to 31 mg / l (calculated as 2-butyne-1,4-diol).
  • the metallic surface containing bright and / or galvanized steel pickled with the method according to the invention is preferably the surface of a metallic component / workpiece, for example a steel tube, of wires or screws (piece goods).
  • the metallic surface pickled with the method according to the invention is therefore used in the area of parts treatment.
  • the pickled and rinsed metallic surface is preferably first conversion-treated.
  • For the conversion treatment there is preferably one acidic aqueous composition for use, which contains zinc phosphate, manganese phosphate and optionally nickel ions (so-called zinc phosphating).
  • a thin film coating can also be carried out by means of an acidic aqueous composition which contains a titanium, zirconium and / or hafnium compound and optionally copper ions and / or a compound which releases copper ions, optionally a polymer and / or copolymer and optionally a Organoalkoxysilan and / or a hydrolysis and / or a condensation product thereof.
  • an acidic aqueous composition which contains a titanium, zirconium and / or hafnium compound and optionally copper ions and / or a compound which releases copper ions, optionally a polymer and / or copolymer and optionally a Organoalkoxysilan and / or a hydrolysis and / or a condensation product thereof.
  • a base lacquer which is preferably a KTL (cathodic electro-dipping lacquer), particularly preferably a (meth) acrylate or epoxy-based KTL, is preferably applied first, and then a top lacquer is applied.
  • KTL cathodic electro-dipping lacquer
  • a top lacquer is applied.
  • a lubricant containing salts, polymers and / or soaps is applied to the pickled and rinsed metallic surface.
  • Aqueous pickling solutions A to F were prepared, each containing 20% by weight H 2 SO 4 , 50 g / L Fe 2+ and optionally one or two pickling inhibitors.
  • Test sheets made of CRS were weighed before treatment with one of the pickling solutions.
  • pickling inhibitors of pickling solutions B and C to be avoided from a toxicological and environmental point of view each had an excellent inhibitory value of 96%.
  • the inhibitory values of the individual inhibitors but-2-in-1,4-diol (pickling solution D) and 2-butyne-1,4-diol-bis (2-hydroxyethyl ether) (pickling solution E) remained clear at 85% and 92%, respectively back there.
  • the inhibitory value of the mixture according to the invention of the two last-mentioned pickling inhibitors (pickling solution F) was surprisingly high at 97% and even exceeded that of the aforementioned pickling inhibitors.
  • the sheets were then zinc-phosphated.
  • the pickling solutions B and F were added to the phosphating bath in increasing amounts.
  • the look of the sheets was evaluated.
  • the layer weights in g / m 2 calculated from P 2 O 5 were determined by means of XRF.
  • the mixture according to the invention not only reduces the pickling removal, but also does not lead to any disturbances in the layer formation in a subsequent phosphating step, for example due to the carryover of the pickling solution.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • ing And Chemical Polishing (AREA)
EP17721118.2A 2016-04-29 2017-04-28 Zusammensetzung zur verminderung des beizabtrags beim beizen von metallischen oberflächen enthaltend blanken und/oder verzinkten stahl Active EP3449040B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL17721118T PL3449040T3 (pl) 2016-04-29 2017-04-28 Kompozycja do zmniejszania ubytku wskutek trawienia podczas trawienia powierzchni metalowych zawierających stal niepowlekaną i/lub ocynkowaną

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016207429 2016-04-29
PCT/EP2017/060227 WO2017186929A1 (de) 2016-04-29 2017-04-28 Zusammensetzung zur verminderung des beizabtrags beim beizen von metallischen oberflächen enthaltend blanken und/oder verzinkten stahl

Publications (2)

Publication Number Publication Date
EP3449040A1 EP3449040A1 (de) 2019-03-06
EP3449040B1 true EP3449040B1 (de) 2020-03-18

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EP17721118.2A Active EP3449040B1 (de) 2016-04-29 2017-04-28 Zusammensetzung zur verminderung des beizabtrags beim beizen von metallischen oberflächen enthaltend blanken und/oder verzinkten stahl

Country Status (12)

Country Link
US (1) US11124884B2 (enExample)
EP (1) EP3449040B1 (enExample)
JP (1) JP6968825B2 (enExample)
KR (1) KR102369545B1 (enExample)
CN (1) CN109072454B (enExample)
DE (1) DE102017207232A1 (enExample)
ES (1) ES2795655T3 (enExample)
MX (1) MX385665B (enExample)
PL (1) PL3449040T3 (enExample)
RU (1) RU2747720C2 (enExample)
WO (1) WO2017186929A1 (enExample)
ZA (1) ZA201807922B (enExample)

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WO2019028400A1 (en) 2017-08-03 2019-02-07 Ecolab Usa Inc. THIOL ADDITION PRODUCTS FOR INHIBITING CORROSION
EP3724371A1 (de) 2017-12-12 2020-10-21 Chemetall GmbH Borsäurefreie zusammensetzung zur entfernung von kryolithhaltigen ablagerungen

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RU2747720C2 (ru) 2021-05-13
KR102369545B1 (ko) 2022-03-03
RU2018140856A3 (enExample) 2020-06-25
JP2019515133A (ja) 2019-06-06
EP3449040A1 (de) 2019-03-06
ES2795655T3 (es) 2020-11-24
WO2017186929A1 (de) 2017-11-02
CN109072454B (zh) 2021-03-05
US11124884B2 (en) 2021-09-21
PL3449040T3 (pl) 2020-08-24
RU2018140856A (ru) 2020-05-29
JP6968825B2 (ja) 2021-11-17
DE102017207232A1 (de) 2017-11-02
ZA201807922B (en) 2020-02-26
MX2018013233A (es) 2019-02-13
KR20190003514A (ko) 2019-01-09
US20190112717A1 (en) 2019-04-18
MX385665B (es) 2025-03-18
BR112018071497A2 (pt) 2019-02-19

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