EP3947773A1 - Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit - Google Patents

Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit

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Publication number
EP3947773A1
EP3947773A1 EP20732490.6A EP20732490A EP3947773A1 EP 3947773 A1 EP3947773 A1 EP 3947773A1 EP 20732490 A EP20732490 A EP 20732490A EP 3947773 A1 EP3947773 A1 EP 3947773A1
Authority
EP
European Patent Office
Prior art keywords
acrylic acid
meth
weight
mol
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20732490.6A
Other languages
German (de)
English (en)
Inventor
Andre SCHAUS
Dominic WEIL
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.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
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 Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP3947773A1 publication Critical patent/EP3947773A1/fr
Pending legal-status Critical Current

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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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4415—Copolymers wherein one of the monomers is based on an epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • 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
    • 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
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a water-based, alkaline cleaner concentrate and a corresponding cleaner for metallic surfaces with reduced pickling removal, which does not require the use of phosphates, and a method for the anti-corrosion treatment of metallic surfaces, which includes a corresponding cleaning step, a metallic surface, obtainable by said process, as well as its use in the field of the metalworking industries.
  • Phosphate-containing cleaning products have long been used as standard products in industrial metal cleaning because of their degreasing-accelerating effect.
  • phosphates also have the advantage of acting as complexing agents for interfering ions such as magnesium or calcium.
  • aqueous cleaning systems and conversion solutions are used, which have a pH value in the clearly acidic or alkaline range.
  • Silicate compounds such as potassium and sodium silicate as well as potash and soda waterglass, however, tend to precipitate at a pH value of less than 11 and thus their activity to lose, and can also lead to encrustation of the cleaning baths or to subsequently difficult to remove and visually disturbing drying on the metal surfaces to be treated. For this reason they are nowadays only reluctantly used as pickling inhibitors in alkaline cleaning systems. Boron compounds such as boric acid, sodium or potassium borate are now used as a replacement for silicate compounds, especially for aluminum and galvanized steels.
  • organosilane-based thin-film systems such as Oxsilan ® (Chemetall GmbH, Germany) are moving more into focus. These act like zinc phosphating as an aqueous conversion system, but have clear advantages especially with regard to more sustainable products, ecological thinking and raw material bans, e.g. of nickel or phosphate.
  • aqueous cleaners not only have to be highly compatible with well-known conversion processes such as trication phosphating, but also with nickel-free zinc phosphating and, above all, with the aforementioned thin-film systems, which means that the metal surface must be optimally prepared for any type of conversion treatment. No.
  • 9,567,552 B2 describes a phosphate-free cleaner in which long-chain polyacrylates are used as corrosion inhibitors.
  • the cleaner is suitable for the treatment of aluminum / aluminum alloys, but not for multi-metal systems such as are common in the automotive industry.
  • the compatibility of the cleaner with a subsequent organosilane-based thin film coating or a trication phosphate is not shown.
  • the object of the present invention was therefore to provide a water-based cleaner concentrate and a corresponding water-based cleaner for metallic surfaces, which on the one hand manages without the use of phosphates and still combines a balanced pickling attack with good cleaning performance, and on the other hand the metal surface optimally for each Type of conversion treatment prepared.
  • a water-based, alkaline cleaner concentrate for the production of a cleaner for metallic surfaces, which a) at least one (meth) acrylic acid homopolymer with a weight average molar mass in the range from 3,000 to 19,000 g / mol and
  • b) contains at least one (meth) acrylic acid copolymer with a weight average molar mass in the range from 50,000 to 100,000 g / mol, the at least one (meth) acrylic acid copolymer being at least one copolymer of (meth) acrylic acid and at least one monomer which has a vinyl group and at least two acid groups selected from the group consisting of carboxylic acid groups and sulfonic acid groups.
  • the polymers of components a) and b) are used in the present case as a phosphate substitute in the cleaning concentrate according to the invention described. It has surprisingly been found that none of the polymers alone can achieve the performance of a phosphate-containing standard cleaner. Rather, comparable results can only be achieved with a polymer mixture of components a) and b).
  • the polymers of component a) are rather short-chain (meth) acrylic acid homopolymers which combine an inhibition of the pickling attack with an average cleaning effect.
  • the polymers of component b) are special long-chain (meth) acrylic acid copolymers and, due to their highly complexing properties and the associated strong pickling attack, act as cleaning enhancers, with their cleaning performance corresponding to the phosphates used as standard.
  • the weight-average molar mass of the polymers of components a) and b) was always determined in the present case by means of GPC (gel permeation chromatography) with aqueous eluents. The columns were calibrated using polystyrene sulfonates with a narrow molar weight distribution. Definitions:
  • water-based is to be understood as meaning that a corresponding composition, which can contain both dissolved and dispersed components, for example a cleaning concentrate or cleaner, consists of at least 50% by weight, preferably at least 55% by weight, of water.
  • the terms “detergent” and “detergent composition” are used synonymously here.
  • the cleaner or the cleaner composition can in particular be a cleaner solution.
  • (meth) acrylic acid always means methacrylic acid, acrylic acid or both.
  • deprotonated form i.e. the conjugate base of methacrylic acid or acrylic acid, should also always be included.
  • a “(meth) acrylic acid homopolymer” can be a polymer that contains only methacrylic acid, only acrylic acid or both methacrylic acid and acrylic acid as monomer units - but has no further monomer units.
  • a “meth (acrylic) acid copolymer” This can only contain methacrylic acid, only acrylic acid or both methacrylic acid and acrylic acid as monomer units - but also always has other monomer units that are not methacrylic acid or acrylic acid.
  • the at least one monomer which has a vinyl group and at least two acid groups all deprotonated forms of the corresponding acid groups should also be included.
  • the at least one (meth) acrylic acid homopolymer of component a) of the cleaner concentrate according to the invention preferably comprises at least one acrylic acid homopolymer.
  • (Meth) acrylic acid homopolymer of component a) at least one (meth) acrylic acid homopolymer with a weight average molar mass in the range from 5,000 to 15,000 g / mol, particularly preferably from 6,000 to 12,000 g / mol and very particularly preferably from 7,000 to 9,000 g / mol - calculated as polyacrylic acid.
  • the at least one (meth) acrylic acid homopolymer of component a) is at least one acrylic acid homopolymer with a weight-average molecular weight in the range from 5,000 to 15,000 g / mol, particularly preferably from 6,000 to 12,000 g / mol and very particularly preferably from 7,000 up to 9,000 g / mol - calculated as polyacrylic acid.
  • the at least one (meth) acrylic acid homopolymer of component a) is added to the cleaning concentrate preferably as a salt, more preferably as an alkali metal salt and particularly preferably as a sodium salt.
  • the sodium salt in particular, is advantageous due to the resulting alkalinity of the cleaning concentrate.
  • Particularly suitable polyacrylic acid for example, having a weight average molecular weight of about 8,000 g / mol (available as Sokalan ® PA 30 CL from BASF SE, Germany)
  • the at least one (meth) acrylic acid copolymer of component b) of the cleaning concentrate according to the invention is at least one, preferably linear, copolymer of (meth) acrylic acid and at least one monomer which has a vinyl group and at least two acid groups selected from the group consisting of carboxylic acid groups and Has sulfonic acid groups.
  • the (meth) acrylic acid units on the one hand and the monomer units with the at least two acid groups on the other hand are preferably arranged in an alternating sequence.
  • Corresponding block copolymers and statistical copolymers are also suitable in principle.
  • the at least one (meth) acrylic acid copolymer preferably does not contain any other monomer units, in particular no vinyl acetate or vinyl alcohol units, and in particular no vinyl acetate units.
  • the (meth) acrylic acid units make up preferably 35 to 65 mol%, particularly preferably 40 to 50 mol% and very particularly preferably 45 to 55 mol% of the at least one (meth) acrylic acid copolymer of component b), while the monomer units with the at least two acid groups make up preferably 65 to 35 mol%, particularly preferably 60 to 40 mol% and very particularly preferably 55 to 45 mol% of the at least one (meth) acrylic acid copolymer of component b), the aforementioned mol% Preferably add% to each 100.
  • the at least one (meth) acrylic acid copolymer of component b) comprises at least one - preferably alternating - copolymer of (meth) acrylic acid and at least one, preferably exactly one, monomer containing a vinyl group and at least two, preferably has exactly two carboxylic acid groups.
  • the at least one monomer which has a vinyl group and at least two carboxylic acid groups is preferably selected from the group consisting of vinyl dicarboxylic acids, in particular consisting of maleic acid and fumaric acid, more preferably maleic acid.
  • maleic acid is mentioned here, maleic anhydride or a mixture of maleic acid and maleic anhydride should also be included. In particular, however, it is maleic acid, which is formed from maleic anhydride by hydrolysis in an aqueous medium.
  • the at least one (meth) acrylic acid copolymer of component b) comprises at least one - preferably alternating - copolymer of (meth) acrylic acid and at least one, preferably exactly one, monomer that has a vinyl group and at least two, preferably has exactly two sulfonic acid groups.
  • the monomer which has a vinyl group and at least two sulfonic acid groups is preferably selected from the group consisting of vinyl disulfonic acids.
  • the at least one (meth) acrylic acid copolymer of component b) is at least one (meth) acrylic acid copolymer with a weight average molecular weight in the range from 55,000 to 90,000 g / mol, particularly preferably from 60,000 to 80,000 g / mol and very particularly preferred from 65,000 to 75,000 g / mol - calculated as poly (acrylic acid e-maleic acid).
  • the at least one (meth) acrylic acid copolymer of component b) comprises at least one - preferably alternating - copolymer of (meth) acrylic acid and at least one, preferably exactly one, monomer which has a vinyl group and at least two, preferably exactly two carboxylic acid groups has, with a weight-average molecular weight in the range from 55,000 to 90,000 g / mol, particularly preferably from 60,000 to 80,000 g / mol and very particularly preferably from 65,000 to 75,000 g / mol - calculated as poly (acrylic acid-a / f-maleic acid).
  • the at least one (meth) acrylic acid comopolymer of component b) is added to the cleaning concentrate preferably as a salt, more preferably as an alkali metal salt and particularly preferably as a sodium salt.
  • the sodium salt in particular, is advantageous due to the resulting alkalinity of the cleaning concentrate.
  • poly (acrylic acid-a / f-maleic acid) with a weight-average molar mass of approx. 70,000 g / mol available as Sokalan® CP 5 from BASF SE, Germany) is very particularly suitable.
  • the inventive polymer mixture of components a) and b) for example, the combination of polyacrylic acid with a weight-average molar mass of approx. 8,000 g / mol (available as Sokalan® PA 30 CL from BASF SE, Germany) and poly (acrylic acid-a / f-maleic acid) with a weight average molar mass of approx. 70,000 g / mol (available as Sokalan® CP 5 from BASF SE, Germany) is particularly suitable.
  • the at least one (meth) acrylic acid homopolymer of component a) is preferably in a concentration of at least 1.0% by weight, particularly preferably at least 1.5% by weight and very particularly preferably at least 1.7% by weight , but preferably of at most 2.5% by weight, more preferably of at most 2.0% by weight - calculated as polyacrylic acid and based on the total cleaner concentrate - before, while the at least one (meth) acrylic acid copolymer of component b) in a concentration of at least 0.5% by weight, particularly preferably of at least 0.7% by weight and very particularly preferably of at least 0.9% by weight, but preferably of at most 1.5% by weight - calculated as poly (acrylic acid-a / f-maleic acid) and based on the total cleaning concentrate.
  • the at least one (meth) acrylic acid homopolymer of component a) and the at least one (meth) acrylic acid homopolymer of component b) in the cleaning concentrate according to the invention are preferably in a weight ratio in the range from 1.0: 1 to 2.5: 1, more preferably 1 , 3: 1 to 2.0: 1, particularly preferably from 1.5: 1 to 1.9: 1 and very particularly preferably from 1.7: 1 to 1.8: 1 - calculated as polyacrylic acid: poly (acrylic acid- a / f-maleic acid) - before.
  • the performance - good cleaning performance with a balanced pickling attack - of the cleaning agent obtainable from the cleaning concentrate according to the invention can be brought even closer to the performance of a phosphate-containing standard cleaning agent or even exceed it.
  • the cleaning concentrate according to the invention is preferably phosphate-free, i. by definition, no phosphates were added to it during manufacture. However, it is possible, albeit undesirable, for the raw materials used to have low levels of phosphate contamination and the cleaning concentrate therefore also contains a small amount of phosphate. More preferably, however, the cleaning concentrate contains less than 100 ppm, more preferably less than 10 ppm, particularly preferably less than 1 ppm and very particularly preferably less than 0.1 ppm of phosphate.
  • the cleaning concentrate is preferably free of silicate compounds, i. that no silicate compounds were added to it during manufacture. It is possible, however, that the raw materials used have a low level of silicate contamination and the cleaning concentrate therefore also contains a small amount of silicate compounds. More preferably, however, the cleaner concentrate contains less than 100 ppm, more preferably less than 10 ppm, particularly preferably less than 1 ppm and very particularly preferably less than 0.1 ppm of silicate compounds.
  • silicate compounds tend to precipitate at a pH value of less than 11 and thus lose their activity as pickling inhibitors. They can also lead to encrustation of the cleaning baths or to optically disruptive drying on the metal surfaces to be treated.
  • the cleaning concentrate according to the invention preferably additionally contains at least one water-soluble boron compound c), which is preferably selected from the group consisting of boric acid and alkali metal borates, in particular consisting of boric acid, sodium borate and potassium borate.
  • at least one water-soluble boron compound c which is preferably selected from the group consisting of boric acid and alkali metal borates, in particular consisting of boric acid, sodium borate and potassium borate.
  • galvanized steels can in particular be hot-dip galvanized or electrolytically galvanized steels or steels that are coated with a zinc-magnesium alloy.
  • the galvanized steels can also be pre-phosphated.
  • aluminum alloys should always be included.
  • the at least one water-soluble boron compound c) is preferably in a concentration of at least 7.5% by weight, more preferably at least 10.0% by weight, more preferably at least 10.5% by weight, particularly preferably at least 12.5% by weight and very particularly preferably at least 14.0% by weight, but preferably at most 25.0% by weight, more preferably at most 20.0% by weight, particularly preferably at most 17 , 0% by weight and very particularly preferably not more than 16.0% by weight - calculated as boric acid and based on the total cleaning concentrate - before.
  • the multimetal capability of the corresponding cleaner can be further improved - especially when diluted 1:50 from the concentrate - while the upper limits are based on the pH-dependent solubility of the water-soluble ones Result in boron compounds.
  • the cleaning concentrate according to the invention is alkaline, ie it has a pH of greater than 7. Its pH is preferably in the range from 9.5 to 14.0, particularly preferably from 10.5 to 14.0 and very particularly preferably from 11.5 to 14.0.
  • the alkalinity can be adjusted, for example, by adding an appropriate amount of sodium or potassium hydroxide and / or sodium or potassium carbonate to the cleaning composition according to the invention.
  • the cleaning concentrate preferably also contains at least one salt which, together with its conjugate acid formed in situ, forms a buffer system and ensures a stable pH value for the concentrate according to the invention and the cleaning agent obtainable therefrom, primarily by counteracting a carbon dioxide entry from the ambient air Lowering the pH value takes effect.
  • the at least one salt is preferably sodium carbonate, sodium hydrogen carbonate, potassium carbonate and / or potassium hydrogen carbonate.
  • the at least one salt is preferably in a concentration of at least 5% by weight, more preferably at least 7% by weight and particularly preferably in the range from 8 to 12% by weight - calculated as potassium carbonate and based on the total cleaning concentrate - in front.
  • the cleaning composition preferably also has at least one complexing agent that can complex interfering foreign ions, in particular Ca, Mg and Zn cations, and thus keep them in solution so that they do not have a negative effect on the overall process, i.e. Do not pollute the baths in the form of crusts and thus lead to increased cleaning effort and do not reduce the performance of the system through reaction with cleaning agents.
  • the at least one complexing agent preferably comprises gluconate, which was added to the cleaning composition, preferably as sodium and / or potassium gluconate.
  • the at least one complexing agent is preferably in a concentration of at least 1.0% by weight, more preferably at least 2.0% by weight and particularly preferably in the range from 2.5 to 3.5% by weight - calculated as sodium gluconate and based on the total cleaner concentrate.
  • the cleaning concentrate according to the invention contains the following components: a) at least 1, 0 wt .-%, calculated as polyacrylic acid, one
  • the present invention also relates to a water-based, alkaline cleaner for metallic surfaces, which a) at least one (meth) acrylic acid homopolymer with a weight-average molar mass in the range from 3,000 to 19,000 g / mol,
  • h) contains at least one surfactant, the at least one (meth) acrylic acid copolymer being at least one copolymer of (meth) acrylic acid and at least one monomer which has a vinyl group and at least two acid groups selected from the group consisting of carboxylic acid groups and sulfonic acid groups , and in the case that it is a fresh cleaner, the component a) in a concentration of at most 0.65 g / l, preferably in the range from 0.1 to 0.50 g / l - calculated as polyacrylic acid - and component b) in a concentration of at most 0.35 g / l, preferably in the range from 0.05 to 0.30 g / l - calculated as poly (acrylic acid-a / f-maleic acid) - is present.
  • the at least one (meth) acrylic acid copolymer being at least one copolymer of (meth) acrylic acid and at least one monomer which has a vinyl group and at least two acid groups selected from
  • a “fresh cleaner” is understood to mean one that has not yet been brought into contact with a metallic surface. In contact with a metallic surface, ions are released from it and oils and fats are removed from it, which accumulate in the cleaning bath. One then speaks of bath aging. This reduces the pickling attack of the cleaner, which makes it possible to use component a) in a concentration of up to 1.0 g / l and component b) in a concentration of up to 0.55 g / l and nevertheless none To obtain excessive pickling removal.
  • the cleaner according to the invention can be obtained from the cleaner concentrate according to the invention by
  • the dilution factor in step 1) is particularly preferably in the range from 1:40 to 1:60 and very particularly preferably from 1:45 to 1:55.
  • the concentration of the at least one surfactant in step 2) is particularly preferably in the range of 0.4 to 5 g / l and very particularly preferably from 0.5 to 3.5 g / l - based on the cleaner.
  • the at least one surfactant serves to remove any organic contamination such as mineral oils and fats within the cleaning process, and must therefore necessarily be added to the diluted concentrate.
  • the at least one surfactant is in particular at least one nonionic, anionic and / or cationic surfactant.
  • Alkylphenol alkoxylates in particular alkylphenol ethoxylates, with C6 to C14 alkyl chains and a degree of alkoxylation of 5 to 30 mol per mol of phenol,
  • Alkyl polyglucosides which have an alkyl chain length of C8 to C22, preferably C10 to C18 and contain 1 to 20, preferably 1 to 5 glucoside units,
  • alkoxylated C8 to C22 alcohols such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol alkoxylates, it being possible for the alkoxylation to take place with ethylene oxide, propylene oxide, butylene oxide and / or a mixture of these as a block copolymer or a random copolymer.
  • the alcohols preferably have 8 to 18 carbon atoms; the degree of alkoxylation is usually between 2 to 50 mol, preferably 3 to 20 mol, of at least one of the alkylene oxides mentioned per mole of alcohol.
  • the alkylene oxide head group can furthermore contain the following so-called end group closures as a modification: benzyl, methyl and / or t-butyl closure.
  • anionic surfactants are mainly used:
  • alkyl ether sulfates with alkyl chain lengths of 8 to 22, preferably 10 to 18, carbon atoms and - Linear C8 to C20 alkylbenzenesulfonates or alkanesulfonates and soaps, such as sodium or potassium salts of C8 to C24 carboxylic acids.
  • Cationic surfactants used are, depending on the application, in particular:
  • the at least one surfactant is at least one nonionic surfactant.
  • anionic surfactants have too high a tendency to foam, whereas cationic surfactants often attach to the metallic surface and can thus create problems within the conversion layer deposition.
  • Nonionic surfactants do not have these disadvantages.
  • a pH value suitable for use in a multimetal pretreatment system (“ready-to-use” pH) is achieved even without setting the pH value, so that at least one acid or Base must be added.
  • the cleaner of the invention is preferably phosphate-free, i. no phosphates were added to it. However, it is possible - albeit undesirable - for the raw materials used to have low levels of phosphate contamination and the cleaning concentrate and the cleaning agent made from it therefore also contain a small amount of phosphate. A small amount of phosphate in the cleaner can also be caused by detachment from the cleaned metallic surfaces, especially if the surfaces are pre-phosphated. More preferably, however, the cleaner contains less than 200 ppm, particularly preferably less than 20 ppm and very particularly preferably less than 2 ppm of phosphate.
  • the cleaner is preferably free from silicate compounds, ie no silicate compounds were added to it during manufacture. However, it is possible that the raw materials used have low levels of silicate contamination and the cleaner therefore also contains a small amount of silicate compounds. More preferably, however, the cleaner contains less than 100 ppm, more preferably less than 10 ppm, particularly preferably less than 1 ppm and very particularly preferably less than 0.1 ppm of silicate compounds.
  • the cleaner according to the invention preferably additionally contains at least one water-soluble boron compound c), which is preferably selected from the group consisting of boric acid and alkali metal borates, in particular consisting of boric acid, sodium borate and potassium borate.
  • the at least one water-soluble boron compound c) is preferably in a concentration of at least 0.15% by weight, more preferably at least 0.20% by weight, more preferably at least 0.21% by weight, particularly preferably at least 0.25% by weight and very particularly preferably at least 0.28% by weight, but preferably at most 0.50% by weight, more preferably at most 0.40% by weight, particularly preferably at most 0 , 34% by weight and very particularly preferably at most 0.32% by weight - calculated as boric acid and based on the total cleaning concentrate.
  • the multi-metal capability of the cleaner can be further improved, while the upper limits are increased by the pH-dependent solubility of the water-soluble boron compounds in the corresponding concentrate - especially with a 1:50 dilution of the Cleaner from the concentrate - result.
  • the present invention also relates to a method for the anti-corrosion treatment of a metallic surface, in which the surface is brought into contact successively with the following compositions: i) at least one water-based, alkaline cleaner for metallic surfaces, which a) at least one (meth) acrylic acid homopolymer with a weight average molecular weight in the range from 3,000 to 19,000 g / mol, b) at least one (meth) acrylic acid copolymer with a weight average molecular weight in the range of 50,000 to 100,000 g / mol and h) contains at least one surfactant, the at least one (meth) acrylic acid copolymer being at least one copolymer of (meth) acrylic acid and at least one monomer which has a vinyl group and at least two acid groups selected from Group consisting of carboxylic acid groups and sulfonic acid groups, and in the event that it is a fresh cleaner, component a) in a concentration of at most 0.65 g / l, preferably in the range
  • the fact that the metallic surface is brought into contact one after the other with the compositions i) to vi) should not exclude that it is before, after or in between with at least one further, preferably water-based composition, for example an activation composition or a passivation composition - as below in the phosphating process - or brought into contact with another rinsing composition or that it is subsequently subjected to at least one drying process - for example in a drying oven - or provided with further layers of paint such as filler, topcoat and clearcoat (automotive paintwork).
  • the method according to the invention is characterized in that it manages without the use of a phosphate-containing cleaning composition, and it nevertheless leads to corrosion protection and paint adhesion results which are comparable to those obtained when using a phosphate-containing cleaning composition.
  • the metallic surface is optimally prepared for any type of conversion treatment.
  • the acidic conversion composition in step iv) can be not only one for trication phosphating but also one for nickel-free zinc phosphating, one for applying an organosilane-based thin film coating or a passivation composition.
  • the at least one cleaner in step i) preferably additionally contains at least one water-soluble boron compound c), which is preferably selected from the group consisting of boric acid and alkali metal borates, in particular consisting of boric acid, sodium borate and potassium borate.
  • at least one water-soluble boron compound c which is preferably selected from the group consisting of boric acid and alkali metal borates, in particular consisting of boric acid, sodium borate and potassium borate.
  • the metallic surface therefore preferably comprises at least one sensitive material selected from the group consisting of aluminum, galvanized steels and pre-phosphated steels.
  • the metallic surface therefore preferably comprises at least two metallic materials selected from the group consisting of steel, aluminum, galvanized steels and pre-phosphated steels, in particular selected from the group consisting of aluminum, galvanized steels and pre-phosphated steels.
  • the metallic surface further preferably comprises both aluminum and at least one galvanized and / or pre-phosphated steel, particularly preferably both aluminum as well as at least one galvanized and at least one pre-phosphated steel.
  • the acidic conversion composition in step iv) is a composition for nickel-free zinc phosphating which, in addition to zinc ions and manganese ions, also contains phosphate ions and to which no nickel ions have been added.
  • the metallic surface is usually also brought into contact with an aqueous activation composition, which is preferably particles, before step iv) contains zinc and / or titanium phosphate crystals. This facilitates the deposition of a phosphate crystal layer in step iv).
  • the metallic surface can also be brought into contact with an aqueous passivation composition.
  • Said passivation composition preferably contains at least one titanium, zirconium and / or hafnium compound, in particular at least one fluorocomplex of the elements mentioned, and more preferably also at least one organosilane - including its hydrolysis and condensation products.
  • the acidic conversion composition in step iv) is a composition for applying an organosilane-based thin film system which, in addition to at least one organosilane - including its hydrolysis and condensation products - optionally also at least one titanium, zirconium and / or Contains hafnium compound.
  • the cleaning composition according to the invention in combination with an organosilane-based thin film system even leads to better corrosion protection results than a Standard cleaner containing phosphate, especially if the cleaner composition is phosphate-free.
  • the at least one inventive cleaner in step i) and accordingly also the inventive cleaner concentrate are therefore preferably phosphate-free, particularly when an organosilane-based thin-film system is subsequently applied.
  • the acidic conversion composition in step iv) is a passivation composition which, in addition to at least one titanium, zirconium and / or hafnium compound, in particular at least one fluorocomplex of the elements mentioned, optionally also at least one organol silane - its hydrolysis and condensation products included - contains.
  • the present invention also relates to a metallic surface treated to protect against corrosion, which can be obtained with the method according to the invention, and its use in the field of metalworking industries in which conversion processes are used for pretreatment, in particular in the field of the automotive, automotive supplier or general industry.
  • the pickling rate indicates the weight loss of the bare metal during a cleaning step.
  • a defined standard sheet of aluminum quality AA6014 with the dimensions 105 x 190 mm (Gardobond® test sheet, Chemetall GmbH, Germany) is immersed in the solution to be tested - here the corresponding cleaning solution.
  • the mass loss is then determined gravimetrically using an analytical balance. It was limited to aluminum surfaces, as these are the most sensitive to pickling.
  • test panels were first pre-degreased with petroleum spirit in order to remove any kind of organic contamination. In this way, the direct attack of the test solution on the base substrate itself can be assessed and compared.
  • test sheet The mass of the respective pre-degreased test sheet was determined on an analytical balance. Immediately thereafter, the test sheet was immersed for 10 min at 55 ° C. in a 3 l beaker which contained the corresponding test solution. A 40 mm magnetic stirrer bar at the bottom of the beaker was used to stir at a speed of 500 rpm.
  • test panel was removed from the test solution, rinsed with fully demineralized (DI) water and dried with compressed air. The weight loss was then determined on the analytical balance.
  • DI fully demineralized
  • the minimum cleaning time indicates the minimum duration of a cleaning step that is required to clean a standard sheet of steel quality 1 .0312 with the dimensions 105 x 190 mm (test sheet) under constant conditions of organic To rid impurities.
  • the quality of the cleaning must reach a certain minimum value, which is determined on the basis of the percentage of water wetting of the metal surface.
  • the focus here is exclusively on steel surfaces, as these are usually the most difficult surfaces to degrease.
  • Test panels were used which had a constant oil layer (1.7 +/- 0.2 g / m 2 ). This served to compare the results.
  • test panel was immersed for 1 min at 55 ° C. in a 3 l beaker which contained the appropriate cleaning solution.
  • a 40 mm magnetic stirrer bar at the bottom of the beaker was used to stir at a speed of 500 rpm.
  • the test panel was then rinsed with lifting movements (approx. 15 strokes) in the immersed sink, the panel always being pulled completely out of the rinsing water and held vertically for assessment after 10 s (to rule out false wetting).
  • the minimum cleaning time is reached when the water wetting of the surface is at least 95%, i.e. there is a closed film of water. If this condition is not met, the test panel is immersed in the cleaning solution for a further minute as described above and then rinsed in the immersion sink. This is repeated until the condition is met.
  • a standard cleaning concentrate (VB1) with a pH value of 12.9 was initially used as a reference, which, in addition to deionized water, contained the following components:
  • a standard cleaning concentrate containing phosphate (VB7) with a pH value greater than 11.5 was used as a reference, which, in addition to deionized water, contained the following components:
  • cleaner concentrates were then diluted by a factor of 1:50 (corresponding to 20 g concentrate for 1.0 l cleaner) with deionized water and mixed with 2 g / l of an ethylene / propylene oxide fatty alcohol, i.e. a nonionic surfactant, added.
  • the test results show that the cleaning performance (see MRZ) can be greatly improved by adding a polymer - polyacrylic acid or poly (acrylic acid-a / f-maleic acid) (VB2 to VB6 and B1 vs. VB1).
  • a polymer - polyacrylic acid or poly (acrylic acid-a / f-maleic acid) (VB2 to VB6 and B1 vs. VB1).
  • the aggressiveness of the medium increases Aluminum increased (see pickling removal). It can be seen that with polyacrylic acid, with increasing chain length, ie molar mass of the Influence of the addition of polymer in relation to pickling attack and MRZ increases (VB2 to VB4).
  • the pickling attack with the cleaning agent solution (B1) according to the invention is somewhat higher compared to a cleaning agent containing phosphate (VB7).
  • a cleaning solution based on only one polymer with a lower polymer concentration (VB8) values are also obtained on aluminum (AA6014) which are acceptable for a running process, which proves the multi-metal capability of the cleaning solution according to the invention.
  • Tab. 3 shows that with the cleaning solution (B1) according to the invention the minimum cleaning time (MRZ), i.e. the cleaning performance is better, especially in comparison to a phosphate-containing cleaner (VB7) but also to a cleaning solution based on only one polymer with a lower polymer concentration (VB8) on each of the substrates used in a multimetal process.
  • MRZ minimum cleaning time
  • the borate concentration was also varied in order to determine the optimum with regard to the pickling attacks within a multimetal process.
  • the metal sheets used for this purpose were each pre-degreased with an aqueous surfactant solution.
  • the pickling attack on aluminum is at a concentration of 14.5 and 16.5% by weight boric acid in the concentrate - i.e. from 0.29 or 0.33% by weight at a dilution of 1:50 in the cleaning solution - in the desired low range.
  • all tested substrates - including aluminum - can be optimally treated as a composite.
  • the compatibility of the cleaning solution (B1) according to the invention with known conversion treatments was checked on the basis of an organosilane-based thin-film coating and a trication phosphating.
  • the corresponding polymers were added to the two conversion baths (B2 and B3) in larger quantities than usual in the process - as they can get into a conversion bath through a carryover of cleaning medium through components.
  • the substrates used in the automotive industry were cold-rolled steel (CRS), hot-dipped-galvanized steel (HDG) and aluminum (AA6014) in one
  • the layer weights obtained show that the two polymers show no influence at all on zinc phosphate activation (cf. Tab. 6) and only slight effects on trication phosphate (cf. Tab. 7) (B4 and B5 vs. VB10), which occur during the ongoing process Adjustment of the phosphating parameters are compensated can.
  • the SEM images of the surface structure of the trication conversion layer show no abnormalities.
  • the cleaning steps 1.) and 2.) were carried out with the aid of the phosphate-free cleaning solution B1 according to the invention at a dilution of 1:50 from the concentrate and with 2 g / l of an ethylene / propylene oxide fatty alcohol.
  • two phosphate-containing standard cleaners (VB11 and VB12) were also tested.
  • An organosilane-based thin film system (Chemetall, Germany) was used for the conversion in step 4.).
  • step 6 the treated sheets were tested for corrosion and paint adhesion by means of a cyclical corrosion test (VDA 621-415) that is customary in the automotive industry.
  • inventive phosphate-free cleaning solution B1 in combination with an organosilane-based conversion system significantly improves both the corrosion behavior and the paint adhesion properties of the surface compared to a standard cleaning agent containing phosphate (VB11 and VB12).
  • Table 8 a standard cleaning agent containing phosphate

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Abstract

La présente invention concerne un concentrat aqueux, alcalin d'agent de nettoyage pour la préparation d'un agent de nettoyage pour des surfaces métalliques qui contient a) au moins un homopolymère de l'acide (méth)acrylique présentant une masse molaire moyenne en poids dans la plage de 3000 à 19.000 g/mole ainsi que b) au moins un copolymère d'acide (méth)acrylique présentant une masse molaire moyenne en poids dans la plage de 50.000 à 100.000 g/mole, ledit au moins un copolymère de l'acide (méth)acrylique étant au moins un copolymère linéaire d'acide (méth)acrylique et au moins un monomère qui présente un groupe vinyle et au moins deux groupes acides choisis dans le groupe constitué par les groupes d'acide carboxylique et les groupes d'acide sulfonique, ainsi qu'un agent de nettoyage correspondant pour des surfaces métalliques à enlèvement par décapage réduit, qui est obtenu sans utiliser de phosphates. En outre, l'invention concerne un procédé pour le traitement de protection contre la corrosion de surfaces métalliques, qui comprend une étape de nettoyage correspondante, une surface métallique pouvant être obtenue par ledit procédé, ainsi que leur utilisation dans le domaine des industries métallurgiques.
EP20732490.6A 2019-04-04 2020-03-20 Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit Pending EP3947773A1 (fr)

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Families Citing this family (4)

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JP2025540919A (ja) 2022-11-04 2025-12-17 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング アルカリ性組成物、及び亜鉛－マグネシウム表面の洗浄方法
EP4689227A2 (fr) 2023-04-04 2026-02-11 Chemetall GmbH Composition de nettoyage et procédé de nettoyage de surfaces métalliques pour empêcher la corrosion d'un bain de rinçage
WO2024256447A1 (fr) 2023-06-13 2024-12-19 Chemetall Gmbh Composition comprenant un polymère à base de lysine destinée à être utilisée dans le prétraitement chimique de substrats métalliques
WO2026020360A1 (fr) * 2024-07-24 2026-01-29 Henkel Ag & Co. Kgaa Composition dégraissante et procédé de traitement d'une surface métallique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19938640A1 (de) * 1999-08-14 2001-02-15 Henkel Kgaa Verhinderung von Ablagerungen
US20110021410A1 (en) * 2009-07-27 2011-01-27 Ecolab Usa Inc. Novel formulation of a ware washing solid controlling hardness
JP2018193464A (ja) * 2017-05-17 2018-12-06 株式会社Adeka アルカリ洗浄剤組成物及びその洗浄方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2831564B2 (ja) * 1994-03-18 1998-12-02 日本ペイント株式会社 アルカリ脱脂洗浄液
JP2938840B2 (ja) * 1997-02-04 1999-08-25 花王株式会社 鋼板用アルカリ洗浄剤組成物
PT1111037E (pt) * 1999-12-17 2003-07-31 Unilever Nv Utilizacao de composicoes para maquinas de lavar louca
EP1111037B1 (fr) * 1999-12-17 2003-03-26 Unilever Plc Utilisation d'une composition lave-vaiselle
EP1444318B1 (fr) * 2001-11-14 2009-07-01 The Procter & Gamble Company Composition pour lave-vaisselle automatique sous forme de dose unitaire comprenant un polymere anti-tartre
MXPA05001956A (es) * 2002-08-20 2005-04-28 Procter & Gamble Composicion detergente en gel liquido para el lavado automatico de platos y utensilios que comprende un disolvente anhidro.
US20040149311A1 (en) * 2002-11-15 2004-08-05 The Procter & Gamble Company Method for cleaning cookware and tableware with film-forming liquid dishwashing compositions, and compositions therefore
JP2006002229A (ja) * 2004-06-18 2006-01-05 Nippon Parkerizing Co Ltd アルミニウム又はアルミニウム合金用洗浄剤及び洗浄方法
PL2333042T3 (pl) * 2009-12-10 2015-12-31 Procter & Gamble Produkt do automatycznych zmywarek do mycia naczyń i jego wykorzystanie
PL2361964T3 (pl) * 2010-02-25 2013-05-31 Procter & Gamble Kompozycja detergentu
US8691018B2 (en) 2010-08-27 2014-04-08 Ecolab Usa Inc. High molecular weight polyacrylates for aluminum protection in warewash applications
WO2013142458A1 (fr) * 2012-03-23 2013-09-26 Ecolab Usa Inc. Terpolymère contenant des monomères acides maléiques, acétate de vinyle et acrylate d'alkyle pour la protection de l'aluminium
CN104781400A (zh) * 2012-11-05 2015-07-15 丹尼斯科美国公司 包含嗜热菌蛋白酶变体的组合物和方法
JP2016506442A (ja) * 2012-12-20 2016-03-03 ザ プロクター アンド ギャンブルカンパニー ケイ酸塩でコーティングされた漂白剤を含む洗剤組成物
US10154771B2 (en) * 2013-02-04 2018-12-18 The Procter & Gamble Company Cleaning system for a low temperature fill-and-dump dishwashing machine
JP6232246B2 (ja) * 2013-09-26 2017-11-15 シーバイエス株式会社 自動食器洗浄機用洗浄剤組成物およびその使用方法
US9139799B1 (en) * 2014-07-11 2015-09-22 Diversey, Inc. Scale-inhibition compositions and methods of making and using the same
US20220119650A9 (en) * 2016-04-29 2022-04-21 Chemetall Gmbh Method for anti-corrosion treatment of a metal surface with reduced pickling material
DE102017208802A1 (de) * 2016-05-25 2017-11-30 Chemetall Gmbh Verfahren zur korrosionsschützenden Phosphatierung einer metallischen Oberfläche mit vermindertem Beizabtrag
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
JP2018039938A (ja) * 2016-09-09 2018-03-15 株式会社Adeka 液体洗浄剤組成物
US20210171865A1 (en) * 2018-07-19 2021-06-10 Lonza, Llc Detergent Composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19938640A1 (de) * 1999-08-14 2001-02-15 Henkel Kgaa Verhinderung von Ablagerungen
US20110021410A1 (en) * 2009-07-27 2011-01-27 Ecolab Usa Inc. Novel formulation of a ware washing solid controlling hardness
JP2018193464A (ja) * 2017-05-17 2018-12-06 株式会社Adeka アルカリ洗浄剤組成物及びその洗浄方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2020200838A1 *

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US20220162760A1 (en) 2022-05-26
WO2020200838A1 (fr) 2020-10-08
JP2022527547A (ja) 2022-06-02
US12460304B2 (en) 2025-11-04
CN113646467A (zh) 2021-11-12
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