EP2665846A1 - Mehrstufige vorbehandlung von weissblech vor einer lackierung - Google Patents
Mehrstufige vorbehandlung von weissblech vor einer lackierungInfo
- Publication number
- EP2665846A1 EP2665846A1 EP11801688.0A EP11801688A EP2665846A1 EP 2665846 A1 EP2665846 A1 EP 2665846A1 EP 11801688 A EP11801688 A EP 11801688A EP 2665846 A1 EP2665846 A1 EP 2665846A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tinplate
- water
- process step
- aqueous composition
- acidic aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005028 tinplate Substances 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 title claims abstract description 10
- 239000004922 lacquer Substances 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 81
- 239000003792 electrolyte Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 230000002378 acidificating effect Effects 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 230000010287 polarization Effects 0.000 claims description 20
- 238000002161 passivation Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 150000001282 organosilanes Chemical class 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal salts Chemical class 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 25
- 235000013305 food Nutrition 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 102000004169 proteins and genes Human genes 0.000 abstract description 5
- 108090000623 proteins and genes Proteins 0.000 abstract description 5
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 5
- 235000013361 beverage Nutrition 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002987 primer (paints) Substances 0.000 abstract 2
- 238000002845 discoloration Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003973 paint Substances 0.000 description 7
- 150000004760 silicates Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004532 chromating Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000014613 canned/preserved soup Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013332 fish product Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 229910001134 stannide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
- B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
Definitions
- the present invention relates to a two-stage process for corrosion protection
- tinplate in which a corrosion-protective lacquer base is applied in one step, which causes black discoloration of the metallically shiny surface of the pretreated upon contact of provided with a topcoat inventively treated tinplate with liquids that release or contain sulfur compounds, and protein-containing foods Tinplate can be effectively suppressed.
- the tinplate is anodically polarized in an electrolyte containing at least one inert water-soluble salt and then brought into contact with an acidic aqueous composition containing water-soluble inorganic compounds of the elements Zr, Ti, Hf and / or Si.
- Tinplate pretreated according to the invention can be used in particular for the production of
- food-safe packaging such as beverage or food cans are used.
- Tinplate strip is considered in the food industry as a suitable material for the production of packaging units for holding liquids or preserved foods, since tinplate due to the electrochemically noble tin layer even over a prolonged period only small amounts of potentially harmful tin salts in contact with the tin surface Delivers food product. Tinplate strip is therefore an important
- tinplate for can production, which is already provided with an organic topcoat, in order to further minimize the entry of iron salts, which can enter the product if the protective tin layer is damaged and negatively affect the taste of the food.
- lacquered tinplate strip it is necessary to pretreat the tin surface, on the one hand to ensure the adhesion of the paint on the metal surface and on the other hand to build up an additional protection against corrosive infiltration of the paint.
- a suitable pretreatment is the still widespread in the prior art chromating the tin surface by contacting bring the tinplate with an acid chromium salts containing aqueous
- pretreatments of tinplate are known, which include the electrochemical modification of the tin surface and subsequent passivation.
- the aim of this pretreatment methods described in the prior art is in addition to the provision of a suitable Lackhaft groundes to protect against corrosion, in particular the guarantee of color fidelity of pretreated and painted tinplate products in contact with food, the
- the GB 479,746 already describes the problem of discoloration of the inner surfaces of containers made of tinplate, which are in contact with proteinaceous foods, and proposes the
- Tin plate in an ammoniacal electrolyte to impart an anodic current that makes the tin surface insensitive to discoloration by sulfur-containing compounds.
- the anodically oxidized tinplates according to GB 479,746 are then provided with an organic topcoat.
- No. 3,491,001 describes a process for the passivation of tinplates, in which, after an anodic pretreatment in an alkaline electrolyte, a cathodic treatment of the tinplate in an alkaline chromate-containing electrolyte follows.
- An electrolytic process chain as described in US Pat. No. 3,491,001, protects the tin surface against corrosion and before
- the electrolytic chromium-containing passivation also serves as a primer for subsequently applied organic topcoats.
- the object of the present invention is, in particular, tinplate products for the production of food packaging with the lowest possible pickling loss of tin
- pretreatment that excellent adhesion of organic topcoats on the tinplate is guaranteed at the same time permanent resistance of the pretreated and painted tin surfaces against discoloration by sulfidic compounds, based on the state of the art as effective as possible passivation of the tin surface is to be established for this purpose.
- This object is achieved in a process for the pretreatment of tinplate prior to painting with an organic topcoat, in which, in a first step, an anodic polarization takes place in an aqueous electrolyte containing at least one inert water-soluble salt and then in a second step a passivation by Contacting the tinplate with an acidic aqueous composition containing water-soluble inorganic compounds of the elements Zr, Ti, Hf and / or Si.
- Salts which are constituents of the electrolyte in the process according to the invention are considered to be water-soluble in the context of the present invention if their solubility in water at a temperature of 20 ° C. is at least 50 g / l, based on the particular salt.
- inert water-soluble salts are water-soluble salts which do not participate in the electrode processes (tinplate, cathode) in aqueous solution, ie do not participate in heterogeneous electron transfer reactions, and which serve exclusively for current transport.
- Suitable inert water-soluble salts are, for example, carbonates, phosphates, sulfates, nitrates and hydroxides of the alkali metals, which are equally preferred as constituents of the electrolyte in the process according to the invention, whereas halides can also be used, but are less suitable because of their corrosivity to metal surfaces.
- Inert salts are preferably contained in the electrolyte of the first process step in such an amount that the specific conductivity of the electrolyte is at least 1 mScm.
- the anodic polarization in the first step of the method according to the invention is preferably carried out at a current density of at least 0.005 A / dm 2 , more preferably at least 0.1 A / dm 2 , but preferably not more than 6 A / dm 2 , more preferably not more than 4 A / dm 2 .
- Oxidation stages + II and + IV to convert into an oxide layer the majority of
- Tin (IV) oxide / hydroxide consists.
- anodic current densities above 6 A / dm 2 in the context of the present invention are disadvantageous, since at these current densities due to the semiconducting properties of the tin oxide layer, a large portion of the amount of electricity is applied for the evolution of oxygen.
- this oxygen evolution necessitates a strong reduction of the pH in front of the tinplate surface, resulting in increased corrosive removal of the tin oxide layer and, on the other hand, inhomogeneous oxide layers with local defects, which represent a less suitable primer for organic topcoats, due to the intensive evolution of gas bubbles.
- the duration of the anodic polarization in the process according to the invention is preferably at least 0.2 seconds, more preferably at least one second, since at lower
- the tin surface is mainly capacitively reloaded without a sufficient Faraday current flows, which is able to chemically modify the tin surface.
- a polarization time of more than 300 seconds, even at low current densities, does not improve the properties of the oxide covering layer as a coating adhesion base. Rather, with increasing polarization time, the amorphousness of the oxide layer seems to increase due to a constant repassivation of the surface, so that in processes with long-lasting polarization the
- Lacquer adhesion to the pretreated and passivated tinplate thus deteriorated.
- the type of anodic polarization can be chosen freely in the first step of the method according to the invention and, for example, can be potentiostatic, potentiodynamic, galvanostatic or galvanodynamic. However, because of the easier processability, the galvanostatic embossing of a current is preferred.
- a galvanostatic process step is
- the method according to the invention is carried out in a potentiostatic or potentiodynamic manner in the first step, then the generally preferred current densities are to be regarded in each case as time-averaged current densities.
- the implementation of a pulse method in which anodic current or voltage pulses are impressed is suitable in the first step of the method according to the invention, wherein the single pulse preferably lasts at least 0.2 seconds and the total anodic polarization time, that is summed over all anodic pulses, preferably Does not exceed 300 seconds.
- bringing the electrolyte into contact with the tinplate for anodic polarization is preferably carried out by complete immersion of the tinplate in the tinplate
- the electrolyte may additionally contain at least one organic dicarboxylic acid having not more than 6 carbon atoms and / or its water-soluble metal salt, which is preferably selected from succinic acid,
- Dicarboxylic acids to the electrolyte causes the tinplate surface in the process according to the invention is given an increased resistance to discoloration in contact with proteinaceous foods.
- the proportion of organic dicarboxylic acids in the electrolyte of the process of the invention is preferably in the range of 0.01 to 2 wt .-%.
- the electrolyte may additionally comprise at least one water-soluble silicate of the composition M 2 O nSiO 2 in the first step of the process according to the invention, where M is an alkali metal ion or quaternary ammonium ion and n is a natural Number is between 0.8 and 7.
- water-soluble silicates are compounds of the general empirical formula M 2 O.sub.SiO 2 with M as the alkali metal ion or quaternary ammonium ion and n as the natural number between 0.8 and 7, which at a pH of 8 and a temperature of 20 ° C have a solubility of at least 1 g / l based on Si0 2 .
- the alkali metal ions M of the water-soluble silicates are preferably selected from Li, Na and K.
- quaternary ammonium ions with aliphatic radicals, each having not more than 10 carbon atoms, are equally preferred in electrolytes of the process according to the invention.
- Suitable water-soluble silicates are in particular the so-called water glasses, which are produced by melting Si0 2 with the respective oxide M 2 0. Preference is given to those water glasses whose proportion of Si0 2 in the range of 20-40 wt .-% is. There are such Water glasses are particularly preferred, the molar ratio of Si0 2 : M 2 0 in the range of 2 to 5, in particular in the range of 3 to 4.
- the presence of at least one water-soluble silicate in the electrolyte of the process according to the invention causes a thin silicate layer to be produced on the tinplate during the anodic polarization, which in combination with the subsequent passivation based on water-soluble compounds of the elements Zr, Ti, Hf and / or Si provides an improved primer for organic topcoats.
- a thin silicate layer to be produced on the tinplate during the anodic polarization, which in combination with the subsequent passivation based on water-soluble compounds of the elements Zr, Ti, Hf and / or Si provides an improved primer for organic topcoats.
- the in this electrolyte anodically polarized and subsequently passivated tinplate on contact with sulfur-containing compounds no significant blackening and the metallic luster of the coated tinplate surface is almost completely preserved over a longer period.
- the proportion of water-soluble silicates in the electrolyte is preferably at least 0.1% by weight, more preferably at least 1% by weight, more preferably at least 2% by weight, but preferably less than 30% by weight. %, more preferably less than 20 wt .-% in each case based on the proportion of Si0 second Below a proportion of 0.1 wt .-% based on Si0 2 in the electrolyte, the layer support based on the element silicon, which can be deposited at anodic polarization on the tinplate surfaces is too low to an additional positive effect on the adhesion of the subsequently applied organic paint systems on the inventively treated tinplate exercise.
- Drying steps are required before the organic topcoat can be applied to the pretreated tinplate.
- the pH of the electrolyte is preferably in the range of 2 to 13, more preferably in the range of 3 to 12.
- the tin layer of the tinplates is corroded.
- the preferred pH is in the range from 8 to 13, particularly preferably in the range from 10 to 12.
- electrolytes having a pH below 8 the water solubility of the silicates in the electrolyte decreases sharply and is increased Si0 2 precipitated
- the electrolyte additionally contains at least one water-soluble silicate in the first step of the process according to the invention
- at least one organosilane is contained, which as such brings about improved silicatization of the tinplate surfaces and moreover has suitable functionality in the art non-hydrolysable organic Rest improves the adhesion to organic paint systems. It is the addition of such
- Organosilanes are preferred to the electrolyte having at least one hydrolyzable substituent, which is cleaved on hydrolysis as an alcohol having a boiling point below 100 ° C, and containing at least one non-hydrolyzable substituent, said non-hydrolyzable substituent preferably at least partially has primary amino functions.
- the organosilane is selected from compounds of the following general structural formula (I):
- n and n are each independently integers between 1 and 4 and y is an integer between 0 and 4.
- the proportion of organosilanes in the electrolyte of the first process step containing water-soluble silicates is preferably in the range of 0.01 to 5 wt .-%.
- such electrolytes may additionally be supplemented with water-soluble aluminum salts containing no halides, preferably in an amount of at least 0.001% by weight, however
- the second step of the process according to the invention follows, with or without the intervening water rinse and / or drying step, directly on the anodic pretreatment of the first process step.
- the acidic aqueous composition in the second step of the passivation preferably contains such water-soluble inorganic compounds of the elements Zr, Ti, Hf and / or Si, particularly preferably those compounds of the elements Zr, Ti and / or Si, in particular those compounds of the elements Zr and / or Ti, which are selected from the respective fluorocomplex salts,
- the acidic aqueous composition in the second step comprises at least one water-soluble inorganic compound of the element titanium, which is preferably selected from the respective fluorocomplex salts, fluoro acids and / or salts of the fluoro acids of titanium.
- the proportion of the water-soluble inorganic compounds of the elements Zr, Ti, Hf and / or Si in the acidic aqueous composition of the passivation in the second step of the process according to the invention is preferably at least 0.001 wt .-%, more preferably at least
- the acidic aqueous composition of the passivation in the second process step contains phosphate ions, preferably with a fraction of the acidic aqueous composition of at least 0.01% by weight, particularly preferably at least 0.1% by weight, but preferably not more than 3% by weight, based on PO 4 .
- the acidic aqueous composition for passivating the anodically pretreated tinplate in the second process step may comprise water-soluble and / or water-dispersible organic polymers, such as, for example, polyacrylates, polyisocyanates, polyepoxides, polyalkylamines,
- polyalkyleneimine or amino-substituted polyvinylphenol derivatives included are included. If the electrolyte additionally contains amino-functionalized organosilanes in the anodic pretreatment of the tinplate, preference is given to those water-soluble and / or water-dispersible organic polymers which can be further crosslinked under condensation reactions, ie polyisocyanates, polyepoxides and / or mixtures thereof.
- the total proportion of water-soluble and water-dispersible organic polymers in the acidic aqueous composition of the passivation in the second process step in a process according to the invention is preferably in the range from 0.05 to 10% by weight, more preferably in the range from 2 to 5% by weight ,
- the pH of the acidic aqueous composition which is brought into contact with the anodically pretreated tinplate according to the invention is preferably in the range from 2.5 to 5.5.
- Composition preferably takes place in the so-called "dry-in-place" process, in which a wet film of the acidic aqueous composition is applied to the tinplate surface, which is dried immediately after application should be treated.
- inventive method applied in the so-called coil coating process In this case, running metal strip is continuously coated.
- the acidic aqueous composition can be applied by different methods which are familiar in the prior art. For example, applicator rolls can be used to directly adjust the desired wet film thickness. Alternatively, the metal tape may be immersed in the acidic aqueous composition or sprayed with the acidic aqueous composition, after which the desired wet film thickness is adjusted by means of squeeze rolls.
- the coated tinplate is set to the required
- the second step of the process according to the invention is preferably by contacting with the acidic aqueous composition layer deposits of at least 0.3 mg / m 2 , more preferably at least 2 mg / m 2 , but not more than 30 mg / m 2 , more preferably not more than 20 mg / m 2 based on the respective elements Zr, Ti, Hf and / or Si to realize.
- the layer support can be reduced and is preferably at least 0.3 mg / m 2 but not more than 20 mg / m 2, without the present invention treated tin surface their good
- tinplate strip Insofar as only tinplate strip is treated according to the invention, which originates directly from the electrolytic production process for tin-plated strip material and which has not been oiled for transport purposes or for later forming, cleaning of the tinplate surface prior to carrying out the method according to the invention is not required. However, if the tinplate strip has already been stored and in particular wetted with anticorrosion or forming oils, then a cleaning step for removing organic soiling and salt residues is necessary in most cases before the tinplate can be anodically pretreated according to the invention. Surfactant cleaners known in the art can be used for this purpose.
- the invention relates to the use of tinplate treated in the method according to the invention for the production of packaging, in particular cans, for
- purified tinplate (tin coating 2.8 g / m 2 ) was first pretreated electrolytically, then rinsed with distilled water and then applied a wet film of a passivating agent by means of Chemcoater ® and dried at 50 ° C for 1 min.
- the corresponding test series are listed in Table 1.
- the whitewares treated in this manner were immersed in a potassium sulfide solution (5 g / LK 2 S + 5 g / L NaOH in water) at 90 ° C. for half a minute without topcoat, rinsed with water and dried.
- a potassium sulfide solution (5 g / LK 2 S + 5 g / L NaOH in water) at 90 ° C. for half a minute without topcoat, rinsed with water and dried.
- Coating layer of titanium 3 mg / m 2 measured by X-ray fluorescence analysis (Axio Advanced, Fa. Panalytical) corresponds in addition to about 2 mg / m 2 coating zirconium
- Chromating (0.12% by weight CrO 3 );
- Coating chromium 3 mg / m 2 measured by X-ray fluorescence analysis (Axio Advanced, Fa. Panalytical)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102011002837A DE102011002837A1 (de) | 2011-01-18 | 2011-01-18 | Mehrstufige Vorbehandlung von Weißblech vor einer Lackierung |
PCT/EP2011/072769 WO2012097927A1 (de) | 2011-01-18 | 2011-12-14 | Mehrstufige vorbehandlung von weissblech vor einer lackierung |
Publications (2)
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EP2665846A1 true EP2665846A1 (de) | 2013-11-27 |
EP2665846B1 EP2665846B1 (de) | 2015-06-17 |
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EP11801688.0A Active EP2665846B1 (de) | 2011-01-18 | 2011-12-14 | Mehrstufige vorbehandlung von weissblech vor einer lackierung |
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Country | Link |
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US (1) | US10011915B2 (de) |
EP (1) | EP2665846B1 (de) |
JP (1) | JP6061864B2 (de) |
CN (1) | CN103429795B (de) |
DE (1) | DE102011002837A1 (de) |
ES (1) | ES2547091T3 (de) |
RS (1) | RS54307B1 (de) |
WO (1) | WO2012097927A1 (de) |
Families Citing this family (8)
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DE102012000414B4 (de) * | 2012-01-12 | 2014-03-20 | Thyssenkrupp Rasselstein Gmbh | Verfahren zur Passivierung von Weißblech, sowie verzinntes Stahlband oder -blech |
DK2728041T3 (en) * | 2012-10-30 | 2017-03-20 | Hydro Aluminium Rolled Prod | Coated aluminum strip and method of manufacture |
JP6094693B2 (ja) * | 2014-01-24 | 2017-03-15 | Jfeスチール株式会社 | 容器用鋼板およびその製造方法 |
DE102017117080A1 (de) * | 2017-07-28 | 2019-01-31 | Thyssenkrupp Ag | Stahlblech mit einer Konversionsschicht, Verfahren zur Herstellung eines konversionsbeschichteten Stahlblechs und Behandlungsmittel zur Applizierung einer Konversionsschicht auf einem Stahlblech |
MY195277A (en) * | 2017-08-25 | 2023-01-12 | Jfe Steel Corp | Steel Sheet for Container and Production Method Therefor |
CA3162200C (en) | 2019-12-20 | 2024-04-16 | Jan Paul Penning | Method for manufacturing laminated tinplate, a laminated tinplate produced thereby and use thereof |
US20230220579A1 (en) * | 2020-03-13 | 2023-07-13 | Tata Steel Ijmuiden B.V. | Method for passivating a tinplate strip and apparatus for producing said passivated tinplate strip |
CN115247263A (zh) * | 2022-06-20 | 2022-10-28 | 上海兴赛尔表面材料有限公司 | 一种镀锡板用环保型钝化组合物及其制备方法和应用 |
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- 2011-12-14 ES ES11801688.0T patent/ES2547091T3/es active Active
- 2011-12-14 RS RS20150593A patent/RS54307B1/en unknown
- 2011-12-14 EP EP11801688.0A patent/EP2665846B1/de active Active
- 2011-12-14 CN CN201180069111.2A patent/CN103429795B/zh active Active
- 2011-12-14 WO PCT/EP2011/072769 patent/WO2012097927A1/de active Application Filing
- 2011-12-14 JP JP2013549743A patent/JP6061864B2/ja active Active
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Also Published As
Publication number | Publication date |
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JP6061864B2 (ja) | 2017-01-18 |
JP2014503038A (ja) | 2014-02-06 |
WO2012097927A1 (de) | 2012-07-26 |
US20130299379A1 (en) | 2013-11-14 |
US10011915B2 (en) | 2018-07-03 |
DE102011002837A1 (de) | 2012-07-19 |
ES2547091T3 (es) | 2015-10-01 |
RS54307B1 (en) | 2016-02-29 |
CN103429795A (zh) | 2013-12-04 |
EP2665846B1 (de) | 2015-06-17 |
CN103429795B (zh) | 2016-04-20 |
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