EP2208809B9 - Zusammensetzung zur Beschichtung eines metallischen Substrates - Google Patents
Zusammensetzung zur Beschichtung eines metallischen Substrates Download PDFInfo
- Publication number
- EP2208809B9 EP2208809B9 EP20100159057 EP10159057A EP2208809B9 EP 2208809 B9 EP2208809 B9 EP 2208809B9 EP 20100159057 EP20100159057 EP 20100159057 EP 10159057 A EP10159057 A EP 10159057A EP 2208809 B9 EP2208809 B9 EP 2208809B9
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- EP
- European Patent Office
- Prior art keywords
- weight
- coating composition
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- composition according
- dry coating
- 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.)
- Expired - Lifetime
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 72
- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 82
- 239000011248 coating agent Substances 0.000 claims description 66
- 238000000576 coating method Methods 0.000 claims description 66
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 229920000573 polyethylene Polymers 0.000 claims description 20
- -1 acetylene glycol Chemical compound 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 238000010981 drying operation Methods 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000003666 anti-fingerprint Effects 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 235000013869 carnauba wax Nutrition 0.000 claims description 2
- 239000004203 carnauba wax Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims 1
- 229910002065 alloy metal Inorganic materials 0.000 claims 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 14
- 239000011734 sodium Substances 0.000 abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052913 potassium silicate Inorganic materials 0.000 abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011591 potassium Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- 239000004115 Sodium Silicate Substances 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 10
- 229920001983 poloxamer Polymers 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000007888 film coating Substances 0.000 description 8
- 238000009501 film coating Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005238 degreasing Methods 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 238000005461 lubrication Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000004111 Potassium silicate Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000013074 reference sample Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241001080024 Telles Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920013808 TRITON DF-16 Polymers 0.000 description 1
- 241000282485 Vulpes vulpes Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical class CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a metal substrate coating composition based on an aqueous solution of lithium silicate.
- the present invention also relates to methods of applying this composition to said metal substrate and to the various uses of this coating composition.
- the coating composition is intended to be applied to a steel substrate having a free outer surface consisting of a metal layer of zinc or zinc-based alloy.
- said metal layer may have been deposited on said steel substrate electrolytically or by hot dipping.
- the metal surface treatment is subject to multiple constraints of a technical, economic and environmental nature.
- Sheet metal coils are produced by steelmakers using very fast processes, with line speeds ranging from a few m / min up to 250 m / min.
- the surface treatment technologies must accommodate these line speed constraints.
- Technical difficulties can then arise if one wishes to maintain a good chemical reactivity between the substrate and the treatment products, but also in terms of film formation, if one wishes to obtain a good tension and a good homogeneity of the deposits. of movie.
- Anti-corrosion treatment technologies usually use chromium-based products (hexavalent or trivalent) that are applied in one or more layers. However, these products are harmful to the environment and need to be replaced by non-environmental treatment products.
- on-line operating constraints also require products that are on the one hand mono-component (that is to say that do not require the preparation of a mixture of several products prior to industrial implementation) and which are, on the other hand, stable over time (that is to say, with a lifespan of more than 3 weeks to accommodate the productions made by campaign).
- the present invention relates to a composition that meets the requirements and constraints mentioned above.
- the coating composition is intended to be applied to a metal substrate.
- the wet film thus obtained is then dried and gives rise to a dry coating film.
- the coating composition preferably contains 5 to 30% by weight of lithium siticate (s), more preferably 5 to 20% by weight of lithium silicate (s), even more preferentially 8 to 15% by weight of silicate (s). ) of lithium.
- this coating composition may be prepared in the form of a concentrate in which the percentage of lithium silicate (s) may be up to about 40% by weight, or in the form of a powder in which the percentage of silicate (s) lithium can reach up to about 80% by weight.
- the present invention also relates to the dry coating film obtainable from the application method (described below) of the coating composition on a metal substrate.
- This dry film of coating is characterized in that it comprises at least 40% by weight of dry matter lithium sillcate (s), preferably between 60% and 99.9% by weight relative to the total weight of dry film coating.
- tensioning agent means an additive whose function is to lower and control the liquid surface energy of the composition (or surface tension).
- Surface energy is the energy required to bring the molecules of the liquid interior of the composition to its surface. The lower the surface energy of the composition, the greater the wettability of the surface of the metal substrate. Wettability is the ability for said substrate to receive a liquid allowing it to spread over the largest possible area.
- the surface energy of the composition is preferably adjusted to obtain good wettability of the surface to be coated under high line speed conditions before the product is frozen upon entering the drying zone.
- the coating composition contains between 0.01 and 1% by weight of a tensioning agent, preferably about 0.1% by weight of a tensioning agent.
- the tensioning agent may be added separately or on the occasion of the incorporation of another component containing such an agent, for example a dispersion or an emulsion of a polymer.
- voltage agent may be mentioned copolymers of polypropylene glycol and polyéthytèneglycol (such as Pluronic ® PE 3100 manufactured by BASF), silicone resins (such as ® BYK348, manufactured by BYK ), acetylenic glycols (such as Dyno1604 ® manufactured by Air Products), anionic and nonionic mixtures (such as Dapro W95 HS ® , marketed by Elementis), quaternary ammoniums (such as Cycloquart ® , manufactured by Clariant ), modified polyethoxylated alcohols (such as Triton ® DF16, manufactured by Union Carbide), and compatible mixtures thereof.
- copolymers of polypropylene glycol and polyéthytèneglycol such as Pluronic ® PE 3100 manufactured by BASF
- silicone resins such as ® BYK348, manufactured by BYK
- acetylenic glycols such as Dyno1604 ® manufactured by Air Products
- the tensioning agent can be added to the composition according to the present invention in the form of an aqueous solution, a dispersion or an emulsion in water, with or without a co-solvent.
- the water used in the coating composition according to the present invention is first subjected to a deionization process such that the conductivity of this water is approximately less than 20 ⁇ S / cm.
- the pH of the coating composition will be an alkaline pH of between 11 and 13, more preferably between 11 and 12.
- the coating composition may further contain a polymer whose function is to lower the glass transition temperature of the dry coating film.
- the presence of said polymer imparts elasticity and flexibility properties to the dry film of coating thus obtained. Said polymer then makes it possible to reduce or eliminate the appearance of cracks in the dry coating film, during a subsequent mechanical deformation of the metal substrate.
- acrylic polymers or copolymers such as Polysol M-19 ® (manufactured by SHOWA Highpolymer Co. Ltd.) or Rhodopas D-20 40 ® (manufactured by Rhodia), polyurethanes, alkyds, epoxy esters, as well as their compatible mixtures.
- said polymer can be added to the composition according to the present invention in the form of a dispersion or an emulsion in water or of an aqueous solution, in a proportion which advantageously allows to reach up to 60 % by weight of the dry coating film.
- said polymer can at the same time provide the composition with the previously mentioned tensioning agent.
- the coating composition contains an additive for increasing the hydrophobicity of the dry film coating, in a proportion that achieves up to 50% by weight of the dry film coating, preferably up to 25% by weight dry film coating.
- This additive is a silane, preferably chosen from di- or trimethoxysilanes, or functionalized di- or triethoxysilanes, and mixtures thereof.
- the organic functionality can be vinyl, amine or oxyrane (epoxy) type.
- the silane is chosen from epoxy-functional silanes such as beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 4- (trimethoxysilyl) 1,2-butane-epoxide or gamma-glycidoxypropyltrimethoxysilane.
- the silane may also act as a binder, a stabilizer for the coating composition, and may increase the corrosion resistance of the dry coating film.
- silanes can be used independently or in combination in prehydrolysed form or not.
- silane may also be associated addition of titanate or zirconate to enhance the crosslinking of the binder system depending on the characteristics required of the coating.
- the increase in the hydrophobicity of the dry film coating can be observed visually, especially during cyclic corrosion tests (DIN 50017KTW), by the formation of droplets of condensed water vapor (from the electrolyte) less spread only in the case of a coating whose binder is only composed of silicate.
- the introduction of the silane into the coating composition leads to the decrease of the permeability and / or porosity of the dry film coating to the electrolyte, thereby conferring its hydrophobicity.
- the hydrophobicity of the dry coating film obtained by introducing the silane into the coating composition allows a lower dry film thickness to be applied for the same corrosion resistance result.
- the coating composition may furthermore contain an additive making it possible to reduce the free surface alkalinity of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight. dry film coating.
- This additive is preferably a cerium (Ce) salt, a Lanthanum salt (La), a molybdenum salt (Mo), molybdic acid, paratoluene sulphonic acid, and their salts, or a polyol such as glycerol, as well as their mixtures.
- the coating composition may furthermore contain an additive making it possible to increase the anticorrosion properties of the dry coating film, in a proportion which advantageously makes it possible to attain up to 25% by weight of the film dry coating.
- This additive is preferably a mineral binder such as a titanate or a zirconate, and mixtures thereof.
- the coating composition may further contain a lubricating agent.
- a lubricating agent such as polytetrafluoroethylene, polyethylene, polyethylene glycol or natural organic polymers such as carnauba wax or paraffins, and mixtures thereof.
- the lubricant is added to the coating composition in a proportion which advantageously makes it possible to attain up to 15% by weight of the dry coating film, preferably between 1.5 and 15% by weight of the dry coating film, more preferably between 3 and 15% by weight of the dry coating film, more preferably between 5 and 15% by weight of the dry coating film.
- the lubricant may require a stabilizer to avoid phase separation in the coating composition.
- organophilic clays natural or synthetic
- silica derivatives cellulose derivatives
- xanthan gum or associative thickeners of polyurethane or acrylic type, and mixtures thereof.
- the stabilizer is added to the coating composition according to the present invention in a proportion which achieves between about 0.1 and 5% by weight of the dry coating film.
- the coating composition may additionally be added with an antifoam agent chosen in a manner compatible with the other constituents of the coating composition and the optimal amount of which is determined according to the conventional experiments of routines known to those skilled in the art.
- said composition may be substantially free of organic solvent.
- organic solvents have been found, in practice, to be incompatible with sodium and / or potassium and / or lithium silicates, the main constituents of the coating composition.
- the present invention also relates to a method of coating a metal substrate which comprises applying the previously described coating composition to the surface of said substrate.
- the application of the coating composition described above is carried out during an operation which consists in depositing a wet film of said composition, of suitable low thickness, followed by a drying operation of said composition.
- metal substrate thus coated, giving rise to a dry coating film of said substrate.
- the wet film thickness of the coating composition deposited on the metal substrate is between 0.3 and 39 ⁇ m, preferably between 0.3 and 30 ⁇ m and the wet film is applied at a rate of 0.6 at 40 g / m 2 , preferably from 0.6 to 24 g / m 2 .
- the method which is the subject of the present invention can be carried out online, after the metal coating step of zinc or zinc-based alloy of the steel substrate, or on a recovery line such as on a pre-lacquering line (" coil-coating ").
- the operation of depositing the wet film of the coating composition on the metal substrate can advantageously be carried out by spraying, spraying followed by a spinning operation, by soaking followed by spinning operation or by means of a coating system composed of at least one roller.
- the spinning operation makes it possible to control the thickness of the wet film deposited on the metal substrate.
- This spinning operation can be advantageously carried out using a set of spinning rolls.
- the drying operation of the metal substrate coated with the wet film is carried out by heating the metal substrate or the wet film so as to bring the latter to a temperature of between room temperature and room temperature. ° C.
- the heating operation can be performed directly by induction, or indirectly by convection or infrared. Convection heating generally requires a longer drying time than induction heating or infrared heating.
- This drying operation is advantageously carried out by heating the metal substrate or the wet film so as to bring the latter preferably to a temperature of at least about 35 ° C for a period of at least 2 seconds if heating is used. convection and for a maximum of 10 seconds, preferably 5 seconds, more preferably 1 to 2 seconds, if using induction heating or infrared heating.
- the drying operation is carried out in order to obtain a dry film thickness of coating of between 0.05 and 0.80 ⁇ m, preferably between 0.05 and 0.60 ⁇ m and so as to obtain a weight of layer of dry film coating between 0.1 g / m 2 and 1.3 g / m 2 , preferably between 0.2 g / m 2 and 1.2 g / m 2 , more preferably between 0.2 and 0.5 g / m 2 .
- the wet film deposition and drying operations are carried out between zinc or zinc alloy metal coating operations of the steel substrate and final winding.
- the present invention also relates to the various uses of the coating composition object of the present invention.
- the coating composition can be used as a corrosion protection layer of metal sheets when it is applied to said sheets.
- said composition can be used as an anti-corrosion protection layer for metal sheets to be temporarily stored.
- a layer of dry coating film according to the present invention when it has been applied to a metal substrate and then dried at 240 ° C., completely resists said soak baths. degreasing.
- said layer of dry coating film is partially solubilized by the degreasing baths and when it has been dried at 50 ° C., it is completely solubilized by the degreasing baths. .
- the coating composition can be used as a lubricating layer when it further contains a lubricant and is applied to metal sheets for shaping, particularly for folding, bending and stamping said metal sheets.
- the coating composition may be used as an anti-fingerprint agent.
- metal sheets coated with the coating composition object of the present invention can be handled as is, without fingerprints remaining subsequently printed on said metal sheets.
- the coating composition may be applied to metal substrate parts to be welded.
- said substrates thus coated retain their weldability property and the welding operations can be done directly.
- the coating composition may require the addition of conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.
- conductive pigments such as iron phosphide, ammonium silicate, nickel, tungsten, zinc (pure or alloyed) and carbon, as well as their mixtures.
- Lubricated coating composition (B) % mass Sodium silicate 10.8 Polytetrafluoroethylene (PTFE) 0.7 Polyethylene (PE) 1.3 Acrylic polymer 1.1 Water 86.1 Composition of lubricated dry coating film (B) % mass Sodium silicate 78 Acrylic polymer 8 PTFE and PE 14
- the test consists of subjecting the metal substrate sample to a friction over a length of about 50 mm (see FIG. figure 1 ).
- the samples have a size of 50 mm x 200 mm and are processed on both sides.
- a lateral force (F L ) is imposed on the sample and it is subjected to a constant speed pull of 20 mm / min.
- the tensile force F T is measured after a friction distance of 50 mm.
- the measurement temperature is 21 ⁇ 2 ° C.
- the coating dry film layer weights deposited on the metal substrate samples are between 1 and 1.2 g / m 2 .
- the reference sample is an electrogalvanised sheet (7.5 ⁇ m on each side) on which a layer of ANTICORRIT 4107 S ® oil (manufacturer FUCHS) has been applied at a height of 2.5 g / m 2 on each face .
- This oil is widely used in the automotive industry as a lubricant for sheet metal for stamping.
- the coefficients of friction of the dry film-coated samples of composition according to the present invention (B1) to (86) are lower than the coefficient of friction of the reference sample. This indicates that lubrication of the dry film-coated samples of the present invention (B1) to (B6) is better than that of the reference sample.
- Sample hot-dip galvanized steel (10 ⁇ m) Sample of hot-dip galvanized steel (10 ⁇ m) coated with a dry coating film according to composition (A) with a coating weight of: 0.3 g / m 2 0.6 g / m 2 0.9g / m 2 1.2 g / m 2 Humidotherm test (duration 15 cycles) performed according to DIN 50017 White rust on 100% of the surface (after 5 cycles only) Change in appearance: White rust on 70% of the surface No appearance changes No appearance changes No appearance changes No appearance changes Salt spray test (48 hours duration) according to ISO 9227 White rust on 100% of the surface (after 24 hours only) White rust on 60% of the surface White rust on 20% of the surface White rust on less than 5% of the surface No appearance changes
- Test DIN 50017KTW (20 cycles) Hot-dip galvanized steel substrate (10 ⁇ m) coated with a dry coating film according to composition (A) or (E) with a coating weight of: 0.2 g / m 2 0.5 g / m 2 0.65 g / m 2 Formulation (A) Change in appearance: white rust on 90% of the surface Change in appearance: white rust on 50% of the surface Very slight change in appearance: white rust on 15% of the surface Formulation (E) Very slight change in appearance: white rust on 20% of the surface No change in appearance No change in appearance No change in appearance No change in appearance No change in appearance
- composition comprising the silane is more effective against corrosion than the silane-free composition.
- introduction of silane thus makes it possible to reduce the weight of the layer while maintaining the same anticorrosion properties.
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Claims (23)
- Beschichtungszusammensetzung für Metallsubstrat, eine freie Außenschicht aufweisend, die von einer Zinkschicht oder einer Schicht einer Legierung auf Zinkbasis gebildet wird, dadurch gekennzeichnet, dass sie umfasst (Gew.-%):- Lithiumsilikat(e), eingebracht in Form wässriger Lösung 3% - 35%- Tensid 0,01% - 1%- ein Silan in einem Anteil, der erlaubt, bis zu 50 Gew.-% der trockenen Beschichtungsschicht zu erreichen,- Wasser qsp 100%,wobei die Zusammensetzung einen pH zwischen 11 und 13 inklusive, in vorteilhafter Weise zwischen 11 und 12 hat.
- Beschichtungszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass sie umfasst (Gew.-%):- 5 bis 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, in noch bevorzugter Weise 8 bis 15 Gew.-% Lithiumsilikat(e) und/oder- zirka 0,1 Gew.-% eines Tensids.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das Lithiumsilikat in der Zusammensetzung in Form einer wässrigen Lithiumsilikatlösung verwendet wird mit folgender Gewichtszusammensetzung:- - SiO2 15% - 40%- - Li2O 1% - 10%- - Wasser qsp 100%.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Tensid ausgewählt ist aus einem Polypropylenglykol- und Polyethylenglykolcopolymer, einem Harz auf Silikonbasis, einem Azetylenglykol, einem anionischen und nicht ionischen Gemisch, einem quaternären Ammonium, einem modifizierten Polyethoxylalkohol und einem ihrer kompatiblen Gemische.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie weiterhin ein Polymer umfasst, dessen Funktion in der Absenkung der Glasübergangstemperatur der trockenen Beschichtungsschicht besteht, insbesondere ein Acrylpolymer oder -copolymer, ein Polyurethan, ein Alkyd, einen Epoxyester oder eines ihrer kompatiblen Gemische, wobei das Polymer in vorteilhafter Weise zu der Zusammensetzung in Form einer Dispersion oder einer Emulsion in Wasser oder einer wässrigen Lösung hinzugefügt wird.
- Beschichtungszusammensetzung nach Anspruch 5, dadurch gekennzeichnet, dass das Polymer der Zusammensetzung in einem Anteil hinzugefügt wird, der es erlaubt, bis zu 60 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie weiterhin einen Hilfsstoff umfasst, der erlaubt, die freie Oberflächenalkalinität der trockenen Beschichtungsschicht zu verringern, insbesondere ein Ceriumsalz, ein Lanthansalz, ein Molybdänsalz, Molybdänsäure, p-Toluolsulfonsäure oder ein Polyol sowie ihre Gemische, in einem Anteil, der erlaubt, bis zu 25 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie weiterhin einen Hilfsstoff umfasst, der erlaubt, die korrosionshemmenden Eigenschaften der trockenen Beschichtungsschicht zu steigern, insbesondere ein Titanat oder ein Zirconat sowie ihre Gemische, in einem Anteil, der erlaubt, bis zu 25 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass sie weiterhin ein Schmiermittel enthält, insbesondere Polytetrafluorethylen, Polyethylen, Polyethylenglycol, Carnaubawachs oder Paraffin sowie ihre Gemische, wobei das Schmiermittel zu der Beschichtungszusammensetzung in einem Anteil hinzugefügt wird, der erlaubt, bis zu 15 Gew.-% der trockenen Beschichtungsschicht, vorzugsweise zwischen 1,5 und 15 Gew.-% der trockenen Beschichtungsschicht, in noch bevorzugter Weise zwischen 3 und 15 Gew.-% der trockenen Beschichtungsschicht, in noch mehr bevorzugter Weise zwischen 5 und 15 Gew.-% der trockenen Beschichtungsschicht zu erreichen.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass sie weiterhin ein Antischaummittel umfasst.
- Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 10, durch einen Oberflächenspannungswert zwischen 20 mN.m-1 und 50 mN.m-1 inklusive, vorzugsweise zwischen 22 mN.m-1 und 45 mN.m-1, in noch bevorzugter Weise zwischen 22 mN.m-1 und 40 mN.m-1 gekennzeichnet.
- Metallsubstrat, welches mit Hilfe einer Zusammensetzung nach einem der Ansprüche 1 bis 11 beschichtet wird.
- Auftragsverfahren auf Metallsubstrat, das eine freie Außenschicht aufweist, die von einer Metallschicht auf Zinkbasis oder auf Basis einer Legierung auf Zinkbasis gebildet wird, einer Zusammensetzung nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass es einen Arbeitsgang umfasst, der darin besteht, eine feuchte Schicht der Zusammensetzung in geeigneter geringer Stärke aufzubringen, gefolgt von einem Arbeitsgang der Trocknung des derart beschichteten Metallsubstrats, wodurch eine trockene Beschichtungsschicht des Substrats gebildet wird.
- Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass die Schicht der Beschichtungszusammensetzung in Form einer feuchten Schicht einer Stärke zwischen 0,3 µm und 39 µm inklusive, vorzugsweise zwischen 0,3 und 30 µm inklusive aufgebracht wird.
- Verfahren nach einem der Ansprüche 13 und 14, dadurch gekennzeichnet, dass die Schicht der Beschichtungszusammensetzung in Form einer feuchten Schicht aufgebracht wird, die in einer Menge von 0,6 g/m2 bis 40 g/m2, vorzugsweise von 0,6 bis 24 g/m2 aufgetragen wird.
- Verfahren nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, dass der Arbeitsgang des Aufbringens der feuchten Schicht ausgeführt wird:- durch Zerstäuben; oder- durch Aufsprühen, gefolgt von einem Arbeitsgang des Abquetschens der aufgebrachten feuchten Schicht, um die Steuerung ihrer Stärke zu erlauben, wobei der Arbeitsgang des Abquetschens in vorteilhafter Weise mit Hilfe von einem Satz Abquetschwalzen durchgeführt wird; oder- durch Eintauchen, gefolgt von einem Arbeitsgang des Abquetschens, um die Stärke der aufgebrachten feuchten Schicht zu steuern, wobei der Arbeitsgang des Abquetschens in vorteilhafter Weise mit Hilfe von einem Satz Abquetschwalzen durchgeführt wird; oder- mittels eines Beschichtungssystems, das sich aus mindestens einer Walze zusammensetzt.
- Verfahren nach einem der Ansprüche 13 bis 16, dadurch gekennzeichnet, dass der Arbeitsgang des Trocknens durch Erhitzen des Metallsubstrats oder der feuchten Schicht erfolgt in der Art, dass diese Letzteren auf eine Temperatur zwischen der Raumtemperatur und 240°C inklusive gebracht werden, der Arbeitsgang des Trocknens in vorteilhafter Weise durch Erhitzen des Metallsubstrats oder der feuchten Schicht erfolgt in der Art, dass diese Letzteren vorzugsweise auf eine Temperatur von mindestens zirka 35°C gebracht werden während einer Dauer von mindestens 2 Sekunden bei Verwendung einer Konvektionsheizung und während einer maximalen Dauer von 10 Sekunden, vorzugsweise von 5 Sekunden, in noch bevorzugter Weise von 1 bis 2 Sekunden bei Verwendung einer Induktions- oder Infrarotheizung.
- Verfahren nach einem der Ansprüche 13 bis 17, dadurch gekennzeichnet, dass der Arbeitsgang des Trocknens durchgeführt wird, um eine Endstärke der trockenen Beschichtungsschicht zwischen 0,05 µm und 0,80 µm inklusive, vorzugsweise zwischen 0,05 und 0,60 µm zu erhalten.
- Verfahren nach einem der Ansprüche 13 bis 18, dadurch gekennzeichnet, dass der Arbeitsgang des Trocknens durchgeführt wird, um ein Schichtgewicht der trockenen Beschichtungsschicht zwischen 0,1 g/m2 und 1,3 g/m2 inklusive, vorzugsweise zwischen 0,2 g/m2 und 1,2 g/m2, in noch bevorzugter Weise zwischen 0,2 und 0,5 g/m2 zu erhalten.
- Verfahren nach einem der Ansprüche 13 bis 19, dadurch gekennzeichnet, dass die Arbeitsgänge des Aufbringens der feuchten Schicht und des Trocknens zwischen den Arbeitsgängen der metallischen Beschichtung mit Zink oder einer Legierung auf Zinkbasis des Metallsubstrats und dem abschließenden Aufwickeln durchgeführt werden.
- Verfahren nach einem der Ansprüche 13 bis 20, dadurch gekennzeichnet, dass die trockene Beschichtungsschicht mindestens 40 Gew.-% Trockenmaterial Lithiumsilikat(e), vorzugsweise zwischen 60 Gew.-% und 99,9 Gew.-% im Verhältnis zum Gesamtgewicht der trockenen Beschichtungsschicht umfasst.
- Verwendung einer Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 11:- für den Rostschutz von Metallblechen;- als Mittel gegen Fingerabdrücke, wenn sie auf Metallbleche aufgetragen wird;- für das Beschichten von Metallsubstratteilen, die zum Schweißen bestimmt sind, was in vorteilhafter Weise ein direktes Schweißen der Metallsubstratteile erlaubt, sobald sie mit der Beschichtungszusammensetzung beschichtet sind.
- Verwendung einer Beschichtungszusammensetzung nach Anspruch 9 als Schmierschicht, wenn sie auf Metallbleche im Hinblick auf ihre Formung, insbesondere im Hinblick auf Biegen, Walzen und Pressen der Metallbleche, aufgetragen wird.
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FR0203353A FR2837218B1 (fr) | 2002-03-18 | 2002-03-18 | Composition de revetement de substrat metallique |
EP20030727594 EP1485519B1 (de) | 2002-03-18 | 2003-03-18 | Zusammensetzung und verfahren zur beschichtung von metallsubstraten |
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Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2837218B1 (fr) * | 2002-03-18 | 2005-02-18 | Dacral Sa | Composition de revetement de substrat metallique |
US20060263613A1 (en) * | 2005-05-20 | 2006-11-23 | General Electric Company | Temperature dependent transparent optical coatings for high temperature absorption |
US8124113B2 (en) * | 2005-09-06 | 2012-02-28 | Hamilton Sundstrand Space Systems International, Inc. | Hydrophilic coating |
JP2009514694A (ja) * | 2005-10-21 | 2009-04-09 | アグフア−ゲヴエルト | 改竄防止id証書の作製方法 |
KR100858995B1 (ko) * | 2007-11-23 | 2008-09-18 | 씨캠 주식회사 | 송전시설의 부식방지 및 전력손실을 방지하는 기능을 보유한 기능성도료 조성물 |
KR101168628B1 (ko) † | 2008-01-24 | 2012-07-30 | 유껜 고교 가부시기가이샤 | 내식성 도포막을 갖는 부재, 그 제조 방법 및 그것을 제조하기 위한 도료 조성물 |
EP2154111A1 (de) * | 2008-07-10 | 2010-02-17 | Cognis IP Management GmbH | Wasserlösliche Silikate und deren Verwendung |
GB2466270A (en) | 2008-12-19 | 2010-06-23 | 3M Innovative Properties Co | Composition for providing stain release or stain repellency to stone substrates |
CN201383872Y (zh) * | 2009-01-19 | 2010-01-13 | 歌尔声学股份有限公司 | 电容式麦克风的隔离片 |
US8067486B1 (en) | 2009-01-26 | 2011-11-29 | The Sherwin-Williams Company | Low VOC water-based epoxy coatings |
EP2451880B1 (de) | 2009-07-07 | 2014-04-16 | Ak Steel Properties, Inc. | Polymerbeschichtetes metallisches substrat und verfahren zu dessen herstellung |
EP2633099B1 (de) * | 2010-10-27 | 2019-07-03 | Chemetall GmbH | Wässerige zusammensetzung zur vorbehandlung einer metallischen oberfläche vor einer weiteren beschichtung oder zur behandlung jener oberfläche |
DE102011111757A1 (de) * | 2011-08-24 | 2013-02-28 | Coventya Gmbh | Versiegelungsmittel sowie dessen Verwendung und versiegeltes metallisches Substrat |
ITFI20130039A1 (it) * | 2013-03-01 | 2014-09-02 | Colorobbia Italiana Spa | Composizioni a base di vetro polimerico per coating vetroso. |
EP2971230B1 (de) * | 2013-03-16 | 2021-11-10 | PRC-Desoto International, Inc. | Korrosionshemmende sol-gel-zusammensetzungen |
JP7036508B2 (ja) | 2016-03-18 | 2022-03-15 | スリーエム イノベイティブ プロパティズ カンパニー | 金属表面をコーティングするための双性イオン性ポリマー含有組成物、方法、及び物品 |
FR3096051B1 (fr) * | 2019-05-17 | 2021-06-04 | Nof Metal Coatings Europe | Composition de revetement deshydratee, sous forme solide, son procede d’obtention et son procede de rehydratation |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3565675A (en) * | 1966-10-05 | 1971-02-23 | Philadelphia Quartz Co | Coatings from lithium silicate |
US3884863A (en) * | 1970-11-27 | 1975-05-20 | Exxon Research Engineering Co | Zinc enriched lithium silicate-latex coating composition |
JPS5276236A (en) * | 1975-12-22 | 1977-06-27 | Toyo Kohan Co Ltd | Process for treating steel sheet to be worked |
US4169916A (en) | 1975-12-22 | 1979-10-02 | Toyo Kohan Co., Ltd. | Steel sheets and method of treating steel sheets |
DE3064550D1 (en) * | 1979-01-22 | 1983-09-22 | Ball Corp | A solution for imparting tarnish resistance on aluminium surfaces and method for applying it |
CS231073B1 (cs) * | 1982-06-11 | 1984-09-17 | Karel Barton | Přípravek pro úpravu povrchu zinku, hliníku a slitin na jejich bázi před nanášením organických povlaků |
JPH0639568B2 (ja) * | 1985-04-24 | 1994-05-25 | 東レ・ダウコーニング・シリコーン株式会社 | シリコ−ン水性エマルジヨン組成物の製造方法 |
JPS62127366A (ja) * | 1985-11-26 | 1987-06-09 | Kansai Paint Co Ltd | 無機質亜鉛末塗料 |
JPS62235477A (ja) * | 1986-04-03 | 1987-10-15 | Showa Alum Corp | アルミニウムの親水性皮膜形成剤 |
JPS6372887A (ja) * | 1986-09-12 | 1988-04-02 | Nisshin Steel Co Ltd | 耐食性、耐加工性に優れた溶融めつき鋼板の製造方法 |
US5350791A (en) * | 1992-07-02 | 1994-09-27 | Henkel Corporation | Hydrophilicizing treatment for metal objects |
US5412011A (en) * | 1993-10-15 | 1995-05-02 | Betz Laboratories, Inc. | Composition and process for coating metals |
US5854190A (en) * | 1997-01-16 | 1998-12-29 | Dalco Industries, Ltd. | Water-based flushing for paints and other coatings |
JPH10130687A (ja) * | 1996-10-30 | 1998-05-19 | Kawasaki Steel Corp | 熱間加工用潤滑剤組成物 |
US5908501A (en) * | 1998-01-27 | 1999-06-01 | Pucillo; Patric M. | Composition and a method for preventing dustfall from material |
DE19814605A1 (de) * | 1998-04-01 | 1999-10-07 | Kunz Gmbh | Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen |
WO2002085541A2 (en) * | 2001-04-20 | 2002-10-31 | Savin Roland R | Silicate coating compositions |
FR2837218B1 (fr) * | 2002-03-18 | 2005-02-18 | Dacral Sa | Composition de revetement de substrat metallique |
-
2002
- 2002-03-18 FR FR0203353A patent/FR2837218B1/fr not_active Expired - Fee Related
-
2003
- 2003-03-18 US US10/508,347 patent/US7232479B2/en not_active Expired - Lifetime
- 2003-03-18 EP EP20100159057 patent/EP2208809B9/de not_active Expired - Lifetime
- 2003-03-18 WO PCT/FR2003/000863 patent/WO2003078683A2/fr not_active Application Discontinuation
- 2003-03-18 ES ES10159057T patent/ES2423317T3/es not_active Expired - Lifetime
- 2003-03-18 AU AU2003233381A patent/AU2003233381A1/en not_active Abandoned
- 2003-03-18 EP EP20030727594 patent/EP1485519B1/de not_active Expired - Lifetime
- 2003-03-18 CA CA 2479060 patent/CA2479060C/fr not_active Expired - Lifetime
- 2003-03-18 AT AT03727594T patent/ATE468424T1/de not_active IP Right Cessation
- 2003-03-18 ES ES03727594T patent/ES2343244T3/es not_active Expired - Lifetime
- 2003-03-18 BR BR0308562A patent/BR0308562A/pt not_active Application Discontinuation
- 2003-03-18 DE DE60332605T patent/DE60332605D1/de not_active Expired - Lifetime
- 2003-03-18 MX MXPA04009082A patent/MXPA04009082A/es active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
WO2003078683A9 (fr) | 2004-07-15 |
EP2208809A1 (de) | 2010-07-21 |
CA2479060C (fr) | 2011-05-24 |
FR2837218B1 (fr) | 2005-02-18 |
EP1485519A2 (de) | 2004-12-15 |
DE60332605D1 (de) | 2010-07-01 |
AU2003233381A1 (en) | 2003-09-29 |
WO2003078683A3 (fr) | 2004-06-03 |
ATE468424T1 (de) | 2010-06-15 |
US7232479B2 (en) | 2007-06-19 |
AU2003233381A8 (en) | 2003-09-29 |
BR0308562A (pt) | 2005-01-04 |
EP2208809B1 (de) | 2013-06-12 |
US20060086281A1 (en) | 2006-04-27 |
WO2003078683A2 (fr) | 2003-09-25 |
FR2837218A1 (fr) | 2003-09-19 |
ES2423317T3 (es) | 2013-09-19 |
EP1485519B1 (de) | 2010-05-19 |
MXPA04009082A (es) | 2004-12-06 |
ES2343244T3 (es) | 2010-07-27 |
CA2479060A1 (fr) | 2003-09-25 |
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