EP3898860A1 - Agent de revêtement de formage, feuillard d'acier revêtu de cet agent et son utilisation dans la fabrication de pièces par formage - Google Patents

Agent de revêtement de formage, feuillard d'acier revêtu de cet agent et son utilisation dans la fabrication de pièces par formage

Info

Publication number
EP3898860A1
EP3898860A1 EP19812823.3A EP19812823A EP3898860A1 EP 3898860 A1 EP3898860 A1 EP 3898860A1 EP 19812823 A EP19812823 A EP 19812823A EP 3898860 A1 EP3898860 A1 EP 3898860A1
Authority
EP
European Patent Office
Prior art keywords
forming
component
forming coating
coating composition
particularly preferably
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
EP19812823.3A
Other languages
German (de)
English (en)
Inventor
Michael Wolpers
Sophie ILGAS
Sophie Cornen-Schaeuble
Frank Stahnke
Stefan Schwarz
Jessica BRINKBAEUMER
Hans Clodt
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
ThyssenKrupp Steel Europe AG
Original Assignee
Henkel AG and Co KGaA
ThyssenKrupp Steel Europe AG
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, ThyssenKrupp Steel Europe AG filed Critical Henkel AG and Co KGaA
Publication of EP3898860A1 publication Critical patent/EP3898860A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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

  • Forming coating agent strip steel coated with this agent and its use in the production of components by forming
  • the present invention relates to a water-based metal-forming coating suitable for steel strip comprising an aliphatic organosulfonic acid, a partially hydrolyzable organosilane, which has an amino function, and an alkanolamine.
  • the forming coating agent which can be applied to form a layer in the drying process, low sliding friction is achieved on galvanized steel strip with excellent compatibility in bonding and wet-chemical metal pretreatment in the manufacturing steps following the forming.
  • the invention therefore also includes strip steel, which is provided on one or both sides with a metallic zinc or aluminum coating and with a coating based on the metal-forming agent, and a method in which the coated steel strip is formed to produce a component, and that from the formed part coated steel strip manufactured component.
  • the manufacturer supplies electrolytically galvanized or hot-dip coated steel strip with a metallic coating in the form of quasi-continuous strip (rolls, slit strip) or in the form of strip sections (plates) and temporarily protects it from corrosion for transport to the customer and therefore surface-treated and, for example, chemically passivated or phosphated and, if necessary, additionally oiled.
  • the delivered galvanized or hot-dip coated steel strip is unwound and cut off at the customer's and the flat product is formed to produce more complex semi-finished products and components.
  • the forming process at the customer uses process energy, wears out the forming tools used there, requires high precision and causes abrasion from the metallic coating, which has a negative effect on the surface quality of the formed component, particularly when forming by deep drawing. For this reason, the surface treatment of steel strip provided with a metallic coating regularly also includes conditioning which gives the strip or strip sections delivered improved forming properties.
  • forming coating agents can be applied at the factory during the strip production which either alone or in cooperation with the surface treatment brought about for temporary protection against corrosion have a positive influence on the forming behavior. So in the prior art for electrolytically galvanized steel strip by a
  • Prephosphating and oiling the strip facilitates the forming and at the same time achieves a high surface quality of the strip formed into the component, since the abrasion of zinc material and its mechanical incorporation into the surface of the strip during deep drawing is largely prevented due to the phosphating.
  • the concept of pre-phosphating galvanized steel strip can only be transferred to the hot-dip galvanized and alloy-galvanized steel strip obtained by hot-dip coating because of the high uniformity in the nature of the phosphating required for the forming.
  • the application of thin coatings of zinc sulfates should be emphasized and more recent developments, such as the application of inorganic sulfate-based coatings described in WO 2015/197430 from aqueous alkaline solutions of the respective water-soluble alkali metal salts
  • the electrolytically galvanized or hot-dip coated strip steel is given both temporary corrosion protection and sufficient forming properties and also enables subsequent pre-treatment of the formed components to protect them against corrosion by means of conventional wet-chemical processes such as zinc phosphating.
  • strip sheets which are formed into semi-finished products, are often joined together by gluing and welding for the production of more complex components, for example automobile bodies.
  • the strip steel surfaces equipped or coated with the forming coating agent are only suitable to a limited extent in order to build up sufficient adhesion to adhesives and sealants or to enable welding.
  • This task profile in the forming of coated strip steel provided with a metallic zinc or aluminum coating surprisingly does justice to coatings which comprise an organosulfonic acid, an amino- or epoxy-functionalized organosilane and an alkanolamine are available.
  • the present invention therefore relates to a
  • Forming coating agent for steel strip one or both sides with a metallic
  • Zinc or aluminum coating is provided, containing
  • organosilanes (B) each of which has at least one hydrolyzable substituent which is split off on hydrolysis as alcohol, which has a boiling point below 100 ° C. at an atmospheric pressure of 1 bar, and on the respective silicon atom carry one to three non-hydrolyzable substituents which have at least one primary amino group and / or epoxy group, the total number of substituents on the respective silicon atoms of the organosilanes (A) being four, and
  • a forming coating composition according to the invention after drying on strip steel, provides excellent forming properties with low metal abrasion. At the same time, the dried coating does not have to be cleaned before the formed workpiece is glued or welded, and good adhesion values are nevertheless achieved, in particular when it is glued or sealed with conventional industrial adhesives and sealants.
  • the forming coating agent is due to the salt character After drying, essential components of the agent are perfectly compatible with the wet chemical process steps for corrosion-protective metal treatment that usually follow the forming.
  • component (A) essential for the good forming properties are the aliphatic organosulfonic acids according to component (A), for example 1-octanesulfonic acid, 1-heptanesulfonic acid, 1-hexanesulfonic acid, 1 -pentanesulfonic acid, 1-butanesulfonic acid, 1-propanesulfonic acid, 1-ethanesulfonic acid, methanesulfonic acid and methylenedisulfonic acid in the metal-forming coating composition according to the invention are preferably selected from organosulfonic acids with no more than 3 carbon atoms, with particularly good metal-forming and compatibility with subsequent wet chemical process steps for corrosion-protective metal treatment with metal-coating agents based on the commercially readily available methanesulfonic acid, so that this organosulfonic acid as component (A ) is particularly preferred.
  • organosulfonic acids according to component (A ) for example 1-octanesulfonic acid, 1-heptanesul
  • the organosilanes according to component (B) impart good adhesion to the conventional adhesives and sealants used in industry in the coating dried on the flat product, but without significantly reducing the good forming properties.
  • the organosilanes according to component (B) have a non-hydrolyzable substituent which in turn is functionalized with an amino group or epoxy group.
  • an organosilane according to component (B) has a non-hydrolyzable substituent if the substituent has a carbon atom covalently bonded to the silicon atom and thus the structural unit Si-C, whereas an organosilane with at least one hydrolyzable substituent has the Has structural unit Si-OC. It is known to the person skilled in the art that the organosilanes according to component (B) undergo hydrolysis and condensation reactions in water and are therefore at least partly also in the form of their silanols / siloxanes.
  • organosilanes according to component (B) which have a primary amino group in the non-hydrolyzable substituent and are again preferably selected from aminosilanes with the general structural formula (I ):
  • Preferred representatives of such organosilanes (B) according to the structural formula (I) are selected from the group consisting of 3- (diethylenetriamino) propyltrimethoxysilane, 3- (ethylenediamino) propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-
  • the relative ratio is in a certain range.
  • the relative proportion of organosulfonic acids according to component (A) should not become too low and the molar ratio of compounds of component (A) to compounds of component (B) is therefore preferably at least 1.0, particularly preferably at least 1.0. 5, particularly preferably at least 2.00.
  • the relative proportion for the desired adhesive finish of a dried coating of the metal-forming coating composition should not fall below a certain threshold value and the molar ratio of compounds of component (A) to compounds of component (B) is therefore preferably less than 4.0, particularly preferably less than 3.5, particularly preferably less than 3.0.
  • the alkanolamines according to component (C) contained in the metal-forming coating composition according to the invention are necessary for the formation of neutral salt in the dried coating and thus for compatibility with the wet-chemical process steps following the metal-forming for corrosion-protective metal treatment, which are usually carried out using water-based compositions, for example alkaline cleaning / degreasing and acid zinc phosphating.
  • the neutral salt formation facilitates the detachment of the dried coating in the respective water-based treatment baths and thus increases the efficiency of the corrosion-protecting metal treatment.
  • alkanolamines as salt formers, in comparison to alkalis such as sodium hydroxide solution, has an advantageous effect on the adhesion after the bonding / sealing, that is to say when the process of cleaning the adhesive and sealing points is not intended.
  • the metal coating composition contains alkanolamines according to (C) which are aliphatic, particularly preferably aliphatic and acyclic and particularly preferably have no more than 6 carbon atoms.
  • Preferred representatives of the alkanolamines of component (C) of the metal coating composition are selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine, preferably from the group consisting of monoethanolamine diethanolamine, diethanolamine , particularly preferably from monoethanolamine.
  • the proportion of alkanolamines of component (C) in the metal coating composition is adapted to the proportion of organosulfonic acids according to component (A) in such a way that a substantial proportion of the organosulfonic acids are neutralized as the alkanolammonium salt, since the neutral salt formation that occurs when a wet film of the metal coating composition dries out , which creates compatibility with the wet chemical water-based metal pretreatment steps following the forming process due to the then easy removal of the dried coating from the metal substrate.
  • the molar ratio of compounds of component (A) to compounds of component (C) is therefore less than 1.5, preferably less than 1.2, and, for the setting of an alkalinity, particularly preferably less than 1, 0.
  • the water-based metal-forming agent is preferably made alkaline in order to keep the pickling removal when contacting and drying of the metal-coating agent with the aluminum and / or zinc coating as low as possible. Accordingly, it is advantageous if the metal-forming coating composition according to the invention has a pH which is preferably greater than 7, particularly preferably greater than 8, very particularly preferably greater than 8.5, but preferably not greater than 11, particularly preferably not greater than 10.
  • a pH-regulating compound can be added to the metal-forming coating agent which is not a component (A), (B) or (C) and which in turn is preferably selected from ammonia or organic acids.
  • organic acids which at the same time have complexing properties
  • organic acids which have the desired complexing properties organic phosphonic acids, a-hydroxycarboxylic acids and / or dicarboxylic acids each with no more than 10 carbon atoms, in particular 1-hydroxyethane (1, 1-diphosphonic acid),
  • Diethylenetriaminepenta methylenephosphonic acid
  • ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid
  • Nitrilotriacetic acid citric acid, tartaric acid and / or gluconic acid.
  • the water-based forming coating composition according to the present invention contains the active components at least in such an amount that is sufficient to be able to be applied in customary application methods for flat products such as steel strip in a layer layer sufficient for the forming and for the provision of a concentrate of the forming coating composition at best up to an amount in which the stability of the concentrate is still present until the application solution is prepared.
  • the proportion by weight of compounds of component (A) in the ready-to-use forming coating composition is at least 0.1% by weight, preferably at least 0.3% by weight, particularly preferably is at least 0.5% by weight, but preferably not more than 2% by weight, particularly preferably not more than 1% by weight, in each case calculated as the amount of S and based on the composition.
  • a proportion by weight of compounds of component (B) which is at least 0.05% by weight, preferably at least 0.1% by weight, particularly preferably at least 0.2% by weight, but preferably not more than 1 % By weight, particularly preferably not more than 0.8% by weight, in each case calculated as the amount of Si and based on the average.
  • the proportion by weight of compounds of component (A) is at least 2% by weight, preferably at least 3% by weight, particularly preferably at least 4% by weight, but preferably not more than 8% by weight, particularly preferably not more than 7% by weight, in each case calculated as the amount of S and based on the average.
  • a proportion by weight of compounds of component (B) which is at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 4% by weight, but preferably not more than 10% by weight preferably not more than 8% by weight, calculated in each case as the amount of Si and based on the average.
  • a metal-forming coating composition is still water-based if the proportion by weight of water is at least 40% by weight.
  • a metal-forming coating composition is considered water-based both as a ready-to-use solution and as a concentrate if the proportion by weight of water is at least 40% by weight, with the proportion by weight of water usually being at least 80% by weight for the ready-to-use solution.
  • the coating of the steel strip does not have to produce a corrosion-protective conversion of the metal surface, in the course of which a passive layer is formed on the basis of inorganic salts which are sparingly soluble in water. Accordingly, it is advantageous if the forming coating agent for providing the coated steel strip according to the invention in each case less than 10 mg / kg, particularly preferably in each case less than 1 mg / kg, based on the respective element and the forming coating agent, of water-soluble compounds containing elements of groups IB, III B - VIII B of the periodic table contains.
  • forming coating compositions for the provision of the coated steel strip according to the invention preferably contain less than 1 g / kg, particularly preferably less than 0.1 g / kg, particularly preferably less than 0.01 g / kg of water-soluble phosphates.
  • particulate organic or inorganic constituents which can usually be used to improve sliding friction, such as waxes or molybdenum sulfide, can and should be dispensed with entirely in accordance with the invention for the bondability of the formed strip steel, so that the form-coating composition according to the invention is preferably less than 1 g / kg , preferably less than 0.1 g / kg of particulate constituent.
  • the particulate component of a metal forming coating is the proportion of solids that remains after drying the retentate by ultrafiltration of a defined partial volume of the forming coating composition with a nominal exclusion limit of 10 kD (NMWC, Nominal Molecular Weight Cut Off). The ultrafiltration is carried out with the addition of deionized water (K ⁇ 1 pScnr 1 ) until a conductivity below 10 pScnr 1 is measured in the filtrate.
  • Form coating compositions according to the invention are therefore preferably translucent, the translucency at 20 ° C. and a wavelength of 860 nm being determined in the scattered light method by means of DIN ISO 7027 as the haze value (NTU) and a haze value below 50 indicating a translucent form coating agent.
  • the present invention relates to strip steel which is provided on one or both sides with a metallic zinc or aluminum coating, the coating having on at least one side a coating which comprises silanols / siloxanes and ammonium salts of aliphatic organosulfonic acids, a layer coating on Sulfur is realized, which is in the range of at least 3 mg / m 2 , preferably at least 4 mg / m 2 and at most 40 mg / m 2 , preferably at most 24 mg / m 2 .
  • Strip steel coated in this way fulfills the requirement profile for a forming process and can be deep-drawn with very little metal abrasion, so that material surfaces of the deep-drawn workpiece and the deep-drawing tools are protected.
  • the term “strip steel” encompasses hot strip and cold thin sheet. Due to the salt character of essential components of the coating, the strip steel coated according to the invention is very well compatible with the processes for corrosion-protective metal treatment regularly used by its customers and can, for example, easily carry out alkaline cleaning and subsequent phosphating or chromium-free conversion treatment, especially based on elements containing fluoride-containing acidic compositions of groups IVB - VIB of the periodic table, without sacrificing performance.
  • silanol / siloxane are hydrolysis and condensation products of hydrolyzable organosilanes which, in a preferred embodiment, have both hydrolyzable and non-hydrolyzable substituents, at least one non-hydrolyzable substituent having a primary amino or epoxy group . While a silanol has the structural unit Si-OH, a siloxane is characterized by the structural unit Si-O-Si.
  • the molar ratio of sulfur to silicon in the coating comprising silanols / siloxanes and ammonium salts of aliphatic organosulfonic acids is preferably at least 1.0, particularly preferably at least 1.5, particularly preferably at least 2.0, but preferably less than 4.0 , particularly preferably less than 3.5, particularly preferably less than 3.0.
  • coatings are produced which, on the one hand, as such allow bonding with adhesives and sealants customary in parts production and thereby provide good adhesion, and on the other hand it is guaranteed that the proportion of silanols / siloxanes for imparting adhesion does not exceed values for which the good deep-drawing properties on the strip steel can no longer be maintained.
  • the layer coating for a sufficiently low sliding friction during deep drawing is at least 3, preferably at least 4 mg of sulfur per m 2 . If the strip steel coated for forming is to be fed to a corrosion-protective conversion treatment in subsequent production stages, it is preferred that the layer support is not greater than 40, preferably a maximum of 24, sulfur per m 2 .
  • the layer of sulfur and silicon on the steel strip coated with a metallic zinc or aluminum coating can be determined by means of X-ray fluorescence analysis (XRF).
  • the metallic coating is composed of at least 50 at.% Of the respective element and preferably in a layered coating determined according to DIN EN 10346: 2015 of at least 20 g / m 2 , particularly preferably of at least 40 g / m 2 is applied, magnesium, iron and / or silicon being particularly suitable as alloy components of the metallic coating.
  • Such types of steel strip are preferably electrolytically galvanized steel strip and hot-dip coated steel strip, which in turn is preferably coated with aluminum-silicon (AS), aluminum-zinc (AZ), zinc (Z), zinc-iron (ZF), zinc-aluminum (ZA) and Zinc-Magnesium (ZM) are equipped.
  • particularly suitable strip steels provided with metallic coatings - and therefore particularly relevant and therefore preferred for the process according to the invention - are electrolytically galvanized or hot-dip coated strip steel with an io Proportion of at least 50 at% of zinc in the metallic coating, particularly preferably a coating selected from zinc (Z), zinc-iron (ZF), zinc-aluminum (ZA) or zinc-magnesium (ZM).
  • Strip steel according to the second aspect of the present invention is preferably obtainable in a process in which, on the bare surface of at least one side of the strip steel, which is provided with a metallic zinc or aluminum coating, a wet film of a water-based forming coating composition according to the first aspect of the present Invention is applied and dried, including all of the embodiments of the metal-forming coating described within the scope of the present invention.
  • the surface of the strip steel is considered to be “bare” if, in an alternative, it originates directly from the production stage of applying the metallic coating, that is to say the electrolytic galvanizing or hot-dip coating of the strip steel, the production stage also coming from the application of the metallic coating a subsequent skin pass or cold rolling and / or stretching or stretch bending of the steel strip provided with the metallic coating.
  • Dressing or cold re-rolling serves on the one hand to harden and on the other hand to emboss a surface texture for a matt optical impression of the metal surface.
  • Dressing or cold re-rolling is often carried out using mildly alkaline cleaners and then ends with a sink to remove detergent components and metal debris adhering to the material surface.
  • the surface is "bare” immediately after a cleaning step, in particular to remove a previously applied oil layer.
  • the aqueous forming coating composition is applied by applying a defined amount or by applying an excess amount to the continuous steel strip. Coating is carried out by means of spraying / squeezing devices, roller coating devices, coaters, but possibly also by other methods, such as, for example, rotary coating. Many parameters can be varied in these methods.
  • the rolls are layered at a belt speed of 30 to 120 m / min. Then relative roller speeds are usually used, which move very generously in the range from 50% to 150% of the belt speed. In the case of a coater application, there are also the speeds of the immersion rollers, which form the composition Transfer the feed trough to the application or squeeze roll via a defined gap.
  • the gap setting is defined directly via forces, which can vary greatly depending on the manufacturer of the coater.
  • the forming coating agent is evenly distributed on the surface. The wet film is then promptly converted into a dry film.
  • the contact time of the liquid before drying is only a few tenths of a second up to a maximum of 15 seconds before the “generation” of the dry film begins by removing the water in the dryer.
  • This drying is preferably carried out by heating the steel strip to a peak temperature (so-called PMT or “peak metal temperature”) of at least 40 ° C., particularly preferably of at least 60 ° C., but not above 250 ° C., preferably not more brought about as 150 ° C, particularly preferably not more than 120 ° C. Drying can be additionally supported and accelerated by applying an air flow.
  • the coated steel strip according to the second aspect of the present invention can additionally be provided with an oil coating in order to reduce the susceptibility to corrosion and the formation of corrosion products during transport and storage, in particular in rolled-up form. Oiling often also has a positive effect on the forming behavior of the steel strip in downstream production stages.
  • the oil layer should be selected so that it can be removed with mild cleaners that do not attack the surface, for example in the course of a corrosion-protective metal treatment.
  • a forming process is also detected using the strip steel coated according to the second aspect of this invention.
  • the invention thus also relates to a method for producing a component or semi-finished product by shaping, comprising or consisting of at least the following method steps:
  • Forming coating agent is coated
  • step (B) inserting the steel sheet or the steel plate from step (A) into a shaping tool, and (C) shaping the steel sheet or the steel plate in order to obtain the component or semi-finished product,
  • the method is characterized in that the shaping in step (C) is carried out by means of a stamp or by means of at least one fluid, for example water.
  • step (C) takes place at a temperature of 5 to 100 ° C.
  • the component can be glued better than existing systems, in particular with crash-relevant adhesives, which are used in the field of automotive manufacturing for the bonding of structural components that are particularly capable of absorbing and dissipating impact energy in the event of a crash,
  • the component can be laser welded (soldered), or better, advantageously, without any oiling or coating or oxide layer.
  • Another embodiment relates to the method, characterized in that the steel sheet or steel plate provided in step (A) does not have to be subjected to a previous cleaning step.
  • the cleaning step serves exclusively to remove impurities, in particular particles, the metal-forming coating composition according to the invention is not affected by this and in particular is not removed.
  • a forming process is included in which coated strip steel according to the second aspect of the present invention is additionally oiled and then deep-drawn.
  • Deep drawing is a special embodiment of a forming process and includes the tensile pressure forming of a flat product into an open on one side
  • the coated steel strip after For this purpose, the first aspect of the present invention is preferably cut before deep-drawing, but after an optional oiling, and preferably cuts selected from blanks, sheets, plates or boards are produced.
  • the forming process by deep drawing in the context of the second aspect of the present invention thus takes place with a molding tool by pressing and preferably in such a way that the molding tool is pressed on the side of the strip steel which has the coating.
  • the invention also relates to a component produced by shaping in accordance with the second aspect of the present invention or a component consisting of at least one steel strip blank shaped in accordance with the second aspect of the present invention, which is preferably selected from automobile body parts, heat exchangers, white goods , Profiles, pipes, cans, tanks or tubs.
  • these components can be fed directly to the customary wet-chemical process steps for corrosion-protecting metal treatment, including cleaning, conversion layer formation and optionally painting, in particular cathodic electrocoating.
  • the sheet metal sections coated in this way were then measured in the strip pull test.
  • the coated sheet metal sections were clamped between two flat metal jaws and, under constant force in the clamping direction, moved a defined distance out of the clamping by the metal jaws and the force required for this was measured as a function of time.
  • the strip tensile test was repeated at the same point in the sheet section under the same conditions and carried out a total of ten times.
  • the coefficient of friction for all coatings was approximately 0.1, which indicates sufficient formability during deep drawing.
  • the formulation E3 after gluing with the industrial adhesives listed in Table 2 as a dried coating on the sheet metal sections showed the highest values under tensile shear stress in accordance with DIN EN 1465: 2009, whereas the formulation CE1 was not adequately bondable mediated with significantly falling values in the tensile shear stress.
  • the phosphatability (cleaning with Bonderite ® C-AK 11566-1 while diving at 60 ° C for 3 minutes; phosphating with Bonderite ® M-ZN 2798 at 50 ° C for 3 minutes; rinsing with Bonderite ® M-PT 54 NC at 40 ° C for 1 minute each from Henkel AG & Co. KGaA) was given in all cases and opaque, homogeneous zinc phosphate coatings were obtained.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
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  • Chemical Treatment Of Metals (AREA)

Abstract

La présente invention concerne un agent de revêtement de formage à base d'eau adapté à un feuillard d'acier comprenant un acide organosulfonique aliphatique, un organosilane partiellement hydrolysable présentant une fonction amino et une alcanolamine. Avec l'agent de revêtement de formage qui peut être appliqué par couches lors du procédé de séchage, un faible frottement de glissement sur le feuillard d'acier galvanisé peut être obtenu avec en même temps une excellente compatibilité dans le collage et le prétraitement de métal chimique par voie humide lors des étapes de fabrication suivant le formage. L'invention comprend également un feuillard d'acier qui est muni sur une ou deux faces d'un revêtement métallique en zinc ou en aluminium et d'un revêtement à base de l'agent de revêtement de formage, et un procédé dans lequel le feuillard d'acier revêtu est mis en forme pour fabriquer une pièce et la pièce fabriquée à partir du feuillard d'acier revêtu et mise en forme.
EP19812823.3A 2018-12-19 2019-12-05 Agent de revêtement de formage, feuillard d'acier revêtu de cet agent et son utilisation dans la fabrication de pièces par formage Pending EP3898860A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18214073 2018-12-19
PCT/EP2019/083795 WO2020126518A1 (fr) 2018-12-19 2019-12-05 Agent de revêtement de formage, feuillard d'acier revêtu de cet agent et son utilisation dans la fabrication de pièces par formage

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EP3898860A1 true EP3898860A1 (fr) 2021-10-27

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EP19812823.3A Pending EP3898860A1 (fr) 2018-12-19 2019-12-05 Agent de revêtement de formage, feuillard d'acier revêtu de cet agent et son utilisation dans la fabrication de pièces par formage

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Publication number Priority date Publication date Assignee Title
DE102023110139A1 (de) 2023-04-21 2024-10-24 Thyssenkrupp Steel Europe Ag Stahlblech mit doppelschichtigem temporärem Korrosionsschutz für optimierte Lackierung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2864552B1 (fr) 2003-12-24 2006-07-21 Usinor Traitement de surface par hydroxysulfate
DE102013215440A1 (de) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Metallvorbehandlung mit sauren wasserhaltigen Zusammensetzungen umfassend Silane
RU2692361C2 (ru) 2014-06-27 2019-06-24 Хенкель Аг Унд Ко. Кгаа Твердый смазочный материал для оцинкованной стали

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