EP2084252A1 - Ultradünne hydrophobe und oleophobe schicht, herstellungsverfahren dafür und verwendung in der uhrmacherei als epilam - Google Patents
Ultradünne hydrophobe und oleophobe schicht, herstellungsverfahren dafür und verwendung in der uhrmacherei als epilamInfo
- Publication number
- EP2084252A1 EP2084252A1 EP07816284A EP07816284A EP2084252A1 EP 2084252 A1 EP2084252 A1 EP 2084252A1 EP 07816284 A EP07816284 A EP 07816284A EP 07816284 A EP07816284 A EP 07816284A EP 2084252 A1 EP2084252 A1 EP 2084252A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ultra
- layer according
- thin layer
- gold
- nickel
- 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
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000001338 self-assembly Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 27
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052737 gold Inorganic materials 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 CF 3 Inorganic materials 0.000 claims description 16
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 239000010979 ruby Substances 0.000 claims description 11
- 229910001750 ruby Inorganic materials 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000572 ellipsometry Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- NRAPFTXDAUHVJY-UHFFFAOYSA-N n-[2-(3,4-dihydroxyphenyl)ethyl]-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide Chemical compound OC1=CC=C(CCNC(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1O NRAPFTXDAUHVJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003586 protic polar solvent Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910001369 Brass Inorganic materials 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- OVKMDTVKFLNYRN-UHFFFAOYSA-N [Cd].[Cu].[Au] Chemical compound [Cd].[Cu].[Au] OVKMDTVKFLNYRN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010951 brass Substances 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002048 anodisation reaction Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 230000007480 spreading Effects 0.000 description 8
- 238000003892 spreading Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- IIYCFYBNWUGFSA-RGMNGODLSA-N (2s)-2-amino-3-(3,4-dihydroxyphenyl)propanoic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 IIYCFYBNWUGFSA-RGMNGODLSA-N 0.000 description 2
- JZRCRCFPVAXHHQ-UHFFFAOYSA-N 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanoic acid Chemical compound OC(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JZRCRCFPVAXHHQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229960004624 perflexane Drugs 0.000 description 2
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- ROKKQKVMKURKER-UHFFFAOYSA-O 1-(2-aminoethyl)pyridin-1-ium-3,4-diol Chemical compound NCC[N+]1=CC=C(O)C(O)=C1 ROKKQKVMKURKER-UHFFFAOYSA-O 0.000 description 1
- QDHWEQVVRFFGKU-UHFFFAOYSA-N 12-hydroxydodecyl dihydrogen phosphate Chemical class OCCCCCCCCCCCCOP(O)(O)=O QDHWEQVVRFFGKU-UHFFFAOYSA-N 0.000 description 1
- FBRIJIUAKOFHGK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10-heptadecafluoroundecanamide Chemical compound FC(C(C(C(C(C(C(C(C(C(=O)N)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)C FBRIJIUAKOFHGK-UHFFFAOYSA-N 0.000 description 1
- ZDKUZKWBJPGAMA-UHFFFAOYSA-N 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide Chemical compound NC(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZDKUZKWBJPGAMA-UHFFFAOYSA-N 0.000 description 1
- GAWRYVJRKWPEFX-UHFFFAOYSA-N 4-(2-aminoethyl)-5-nitrobenzene-1,2-diol Chemical compound NCCC1=CC(O)=C(O)C=C1[N+]([O-])=O GAWRYVJRKWPEFX-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000776457 FCB group Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000971 Silver steel Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N dopa Chemical compound OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000001516 effect on protein Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PNUKLZJGBUJWBU-UHFFFAOYSA-O n-(6,7-dihydroxy-1,1-dimethyl-3,4-dihydro-2h-quinolin-1-ium-3-yl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide Chemical compound OC1=C(O)C=C2[N+](C)(C)CC(NC(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)CC2=C1 PNUKLZJGBUJWBU-UHFFFAOYSA-O 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/68—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/20—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
- C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
- C10M105/60—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom
- C10M105/62—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/70—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen as ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/08—Aldehydes; Ketones
- C10M2207/085—Aldehydes; Ketones used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
- C10M2215/0425—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/0806—Amides used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/2203—Heterocyclic nitrogen compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- 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]
- Y10T428/31511—Of epoxy ether
-
- 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]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- 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
-
- 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]
- Y10T428/31725—Of polyamide
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a new ultra-thin hydrophobic and oleophobic layer formed by self-assembly on a solid substrate surface of catechol foot compounds, a process for preparing this ultra-thin layer and the use thereof as an epilame.
- the proper functioning of a watch movement depends, among other things, on its lubrication.
- the durability of the lubricant depends in particular on its maintenance in the operating zone: every watchmaker, however, has noticed that a drop of lubricant spreads rapidly over a clean part.
- the deposition of an epilame layer generally in the form of a hydrophobic and oleophobic invisible molecular layer, avoids the spreading of the lubricant and its components.
- the spreading of a liquid depends on the interaction forces between the liquid, the surface and the surrounding air (see JC Berg, “Wettability", Marcel Dekker, New York, 1993 and AW Adamson, “Physical Chemistry of Surfaces”. “, Wiley).
- the parameter that characterizes the interaction forces between a liquid and the air is the surface tension, ⁇ LV .
- a surface energy ⁇ sv is similarly defined between a solid and the surrounding air and a parameter ⁇ L s between the solid and the liquid.
- the Young equation also shows that if the surface tension of the liquid is lower than the surface energy, the contact angle is zero and the liquid wets the surface. This is what happens for a lubricant deposited on a clean metal surface: in In fact, a lubricant has a surface tension of 35-40 mN / m, whereas a common metal surface has a higher surface energy.
- the surface energy depends on several factors (JP Renaud and P. Dinichert, 1956, “Surface states and spreading of clockwork oils", Bulletin SSC III page 681): the chemical composition and the crystallographic structure of the solid, and in particular of its surface, the geometrical characteristics of the surface and its roughness (and thus the defects and / or the polishing state), the presence of molecules adsorbed physically or chemically bonded to the surface, which can easily mask the solid and significantly change its surface energy.
- this contact angle is about 30 °, whereas it is about 110 ° for a -CH 3 functional group (eg C 12 H 25 SH ) and about 118 ° for a -CF 3 functional group (eg, C 10 F 17 H 4 SH).
- a -CH 3 functional group eg C 12 H 25 SH
- a -CF 3 functional group eg, C 10 F 17 H 4 SH
- the deposition of the compound on the substrate is carried out by soaking it in a solution of perfluorinated solvent loaded with polymer.
- the solvent used is generally tetradecafluorohexane (CeFi 4 ) which, once volatilized, is a greenhouse gas since it remains stable for 3200 years in the air and has a greenhouse potential of 7400 equ. CO 2 . It is an object of the invention to provide compounds useful as an epilame which can be attached to a solid substrate surface without the use of environmentally toxic fluorinated solvents.
- the invention indeed proposes a novel ultra-thin hydrophobic and oleophobic layer formed by self-assembly on a solid substrate surface of catechol foot compounds, and a process for preparing this ultra-thin layer which uses a non-fluorinated solvent which is environmentally friendly.
- the environment for example a mixture of water and 2-propanol.
- This ultra-thin layer is firmly fixed to the surface of the solid substrate.
- This ultra-thin layer has satisfactory properties for use as epilame, particularly a contact angle in advance with water and a spread of a drop of oil, quite comparable to those of the layer obtained from the reference product Fixodrop FK-BS.
- the invention thus makes an important contribution to the ecological preparation of epilames.
- the catechol foot compounds have the general formula
- A represents a group of formula
- Z represents C or N +
- X represents CH or CL
- L being an electron-withdrawing group chosen from F, Cl, Br, I, CF 3 , NO 2 and N (CH 3 ) S + ,
- Y represents H or CH 3 , or Y forms with X a heterocycle of 5 or 6 atoms
- T represents NH, NH-CO, NH-CO-NH or NH 2 + U " , ⁇ " being a soluble anion, such as by example F “, Cl”, Br ⁇ , I, OH “, NO 3", HSO 4 ", SO 4 2 ', CO 3 2-", HCO 3 "or SCN", and
- Group B represents a linear aliphatic alkyl group C x -C 20 substituted partially or completely by F.
- Group A is used in particular to allow attachment of compounds to the surface of the solid substrate with the catechol group and solubilizing the amphiphilic molecule in the AB soaking solution.
- Group B gives the ultra-thin layer its hydrophobic and oleophobic properties.
- the group B is a linear aliphatic group perfluorinated in its terminal part, for example of formula (CH 2 ) n - (CF 2 ) m CF 3 in which n is 1 to 5, in particular 1 to 3 and m is 4 to 11, especially 5 to 9.
- Interesting groups A are those selected from one of the following groups:
- a particularly preferred compound is N- (3,4-dihydroxyphenethyl) -4,4,5,6,6,7,7,8,8,9,9,10,10,11,11,11,11. heptadécafluoroundécanamide
- the compounds of formulas AB can be obtained from known compounds using techniques and reactions well known to the organic chemist.
- N- (3,4-dihydroxyphenethyl) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide may be obtained by reacting 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl ester and 3-hydroxy-tyrosine acid hydrochloric acid solution in DMF in the presence of N-methylmorpholine.
- the solid substrate on the surface of which the self-assembly is made may be any solid substrate involved in the operation of a mechanical movement, in particular consisting of a material selected from among gold, silver, silver steel, including 20AP steel, aluminum, brass, bronze, cuproberyllium, titanium dioxide, ruby, sapphire, silicon, nickel and nickel-phosphorus, as well as other surfaces metal, such as iron, chromium, tantalum, yttrium, silicon, germanium, copper, platinum, and metal or ceramic oxides, such as zirconia and niobium (niobium oxide), list not being limiting.
- the substrate may also be a substrate in one of these materials or another whose surface has been coated or coated, for example by a galvanic deposition of gold, gold-copper-cadmium and gold, nickel, rhodium, tin-nickel, or anodized, as in the case of aluminum alloy or titanium parts, or modified by a surface treatment such as oxidation, carburization or nitriding.
- the thickness of the ultra-thin layer measured in ellipsometry is generally 0.5 to 10 nm, a higher value which will be retained for the definition of ultrathin, preferably 1 to 4 nm.
- the contact angle in advance with the water must generally be at least 100 °.
- the ultra-thin layer of formula A-B remains functional as epilame after two watch washes.
- the invention also relates to a timepiece characterized in that it comprises an ultra-thin layer as defined above.
- the invention also relates to a process for preparing the ultra-thin layer defined above, characterized in that it comprises immersing the substrate in a solution of the compound of formula AB, for example in water, or a mixture of water and protic solvent such as, for example, 2-propanol.
- This process does not use a fluorinated solvent and is therefore respectful of the environment.
- SuSoS2 (0.052 mmol) 33 mg was dissolved in 35 ml of 2-propanol in a graduated 100 ml flask and shaken until completely dissolved. Ultrapure water was added to the mark and shaken vigorously, which increased the temperature of the solution. After returning the solution to room temperature, a few drops of water were added to adjust the volume to 100 ml. The solution was sonicated for 10 seconds to degas it and allow complete mixing of water and 2-propanol.
- Samples of gold, polished steel, aluminum, titanium oxide and rubies were cleaned in a UV / ozone chamber for 30 minutes and immersed overnight in the SuSoS2 solution. The samples were then immersed in 2-propanol for 10 seconds, rinsed with 2-propanol and dried with a stream of nitrogen. In the case of steel, the surfaces were lightly polished with a wipe soaked in 2-propanol, rinsed with additional 2-propanol and dried with nitrogen flow.
- VASE Variable Angle
- Titanium and Titanium Oxide Surfaces ", Langmuir 18 (9): 3537-3548, as follows: Surface wettability was determined by measuring the angles of contact in advance and recoil on a sessile (water) drop (Contact Angle Measuring System, G2 / G40 2.05-D, Kruss GmbH, Hamburg, Germany); the experiment was conducted automatically by increasing and decreasing the size of the drop at a rate of 15 ml per minute; 480 values were measured for the advance contact angle and 240 for the recoil contact angle, at 3 different locations for each sample); the data collected was analyzed by the tangents 2 method (Drop-Shape Analysis program adjustment routine in Version DSA 1.80.0.2 for
- the different substrates used are:
- Table 1 Thickness measured by ellipsometry and advance contact angles with water
- XPS X-ray photoelectron spectroscopy
- An ultra-thin layer of SuSoS2 is coated with substrates of gold, polished steel and ruby as described in Example 2.
- the surface appearance is excellent and no markings can be distinguished due to the deposit .
- Fixodrop FK-BS An ultra-thin layer of Fixodrop FK-BS is coated with gold, polished steel and ruby substrates as specified by the manufacturer by dipping the substrates in a solution of tetradecafluorohexane.
- the thickness of this layer measured by ellipsometry on gold is 0.7 nm for SuSoS2 and 1.7 nm for Fixodrop.
- the contact angles with water, hexadecane, diodomethane and ethylene glycol are acceptable for use as epilam, and comparable with those measured for Fixodrop.
- SuSoS2 For gold, steel and ruby, the layer formed with SuSoS2 shows a dispersive character only, as expected for a molecule of this type.
- the surface energy seems to vary with the material, but is in any case below 20 mJ / m 2 .
- the weakest energy (and therefore a priori the best holding) is obtained for steel, followed by ruby and gold. 3) Measurement of spreading lubricants
- the spreading of the lubricants on a surface is characterized by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after the drop has been deposited and after 20 minutes.
- the spread corresponds to the relative variation of the average diameter after 20 minutes.
- a good performance of a lubricant corresponds to a spread of 2% or less. Spreading greater than 10% is noticeable in the eye and is not acceptable.
- the oils used for the tests are a watch oil “941" (house Moebius and Fils, mixture of alkyl-aryl-monooleate and two C 3.0 -C 13 di-esters, viscosity of 110 cSt at 20 0 C, surface tension of 32.8 mN / m) and a test oil CESNIII (Swiss Laboratory for Watchmaking Research, silicone oil, surface tension of 23.1 mN / m, "Watchmaking Switzerland” No 43, 7.11.1974).
- the spread is in all cases less than 1%, and is comparable to that measured for the Fixodrop, as shown by the table below.
- the contact angle obtained on the ultra-thin layers made with the SuSoS2 molecule is greater than 100 °, the surface energy is less than 20 mJ m -2 , and the spread is less than
- the properties of the SuSoS2 ultra-thin layer are at least as good as those obtained with the commercial product Fixodrop, and the solvent used for the dipping is environmentally friendly.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07816284.9A EP2084252B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20060405504 EP1927648A1 (de) | 2006-12-01 | 2006-12-01 | Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame |
PCT/CH2007/000601 WO2008064510A1 (fr) | 2006-12-01 | 2007-11-29 | Couche ultra-mince hydrophobe et oleophobe, procede de fabrication et utilisation en horlogerie comme epilame |
EP07816284.9A EP2084252B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2084252A1 true EP2084252A1 (de) | 2009-08-05 |
EP2084252B1 EP2084252B1 (de) | 2017-03-29 |
Family
ID=38031431
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20060405504 Withdrawn EP1927648A1 (de) | 2006-12-01 | 2006-12-01 | Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame |
EP07816284.9A Active EP2084252B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
EP07816285.6A Active EP2084253B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20060405504 Withdrawn EP1927648A1 (de) | 2006-12-01 | 2006-12-01 | Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07816285.6A Active EP2084253B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
Country Status (5)
Country | Link |
---|---|
US (2) | US20100075138A1 (de) |
EP (3) | EP1927648A1 (de) |
JP (1) | JP5385788B2 (de) |
CN (1) | CN101611124B (de) |
WO (2) | WO2008064510A1 (de) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8951630B2 (en) | 2006-12-01 | 2015-02-10 | Rolex S.A. | Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame and in mechanical engineering as a barrier film |
EP1927648A1 (de) * | 2006-12-01 | 2008-06-04 | Rolex Sa | Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame |
WO2012085130A1 (fr) * | 2010-12-23 | 2012-06-28 | Rolex Sa | Composition pour augmenter la lipophobicite d'un composant horloger |
DE102011088232A1 (de) * | 2011-12-12 | 2013-06-13 | Aktiebolaget Skf | Lagerkäfig und Lagerkäfigsegment |
FR2990433A1 (fr) * | 2012-05-10 | 2013-11-15 | Surfactis Technologies | Compositions catanioniques de recouvrement de surface par des molecules phosphoniques et amines |
CH708539B1 (de) * | 2012-07-10 | 2017-03-31 | Swatch Group Res & Dev Ltd | Mittel für die Oberflächenschmierung eines Gegenstands. |
EP2865737A1 (de) * | 2013-10-28 | 2015-04-29 | The Swatch Group Research and Development Ltd. | Edelprodukt aus Epilam |
CN107974680A (zh) * | 2016-10-21 | 2018-05-01 | 苏州汉力新材料有限公司 | 一种铝基底表面制备超疏油表面的方法 |
EP3315214B1 (de) | 2016-10-25 | 2020-07-15 | The Swatch Group Research and Development Ltd | Verfahren zur epilamisierung eines elements einer uhr oder eines schmuckstücks |
EP3398978B1 (de) * | 2017-05-05 | 2020-03-11 | The Swatch Group Research and Development Ltd | Epilamisierungsmittel und epilamisierungsverfahren, bei dem dieses epilamisierungsmittel verwendet wird |
EP4075205A1 (de) * | 2021-04-16 | 2022-10-19 | ETA SA Manufacture Horlogère Suisse | Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD238812C2 (de) * | 1985-06-27 | 1989-05-03 | Ruhla Uhren Veb K | Verfahren zur herstellung von schmier-, gleit- und antisreadschichten auf lager- und gleitelementen von uhren |
JP3583168B2 (ja) * | 1994-08-03 | 2004-10-27 | 株式会社ネオス | 含フッ素ベンズアセタール誘導体 |
US20030087338A1 (en) * | 2001-07-20 | 2003-05-08 | Messersmith Phillip B. | Adhesive DOPA-containing polymers and related methods of use |
US7858679B2 (en) * | 2001-07-20 | 2010-12-28 | Northwestern University | Polymeric compositions and related methods of use |
US8815793B2 (en) * | 2001-07-20 | 2014-08-26 | Northwestern University | Polymeric compositions and related methods of use |
US7618937B2 (en) * | 2001-07-20 | 2009-11-17 | Northwestern University | Peptidomimetic polymers for antifouling surfaces |
DE10163892A1 (de) * | 2001-12-27 | 2003-07-17 | Basf Ag | Derivate von Polymeren für die Metallbehandlung |
JP2006291266A (ja) * | 2005-04-08 | 2006-10-26 | Daikin Ind Ltd | フッ素化合物の気相表面処理法 |
WO2007022645A1 (en) * | 2005-08-24 | 2007-03-01 | Eth Zurich | Catechol functionalized polymers and method for preparing them |
WO2008019352A1 (en) * | 2006-08-04 | 2008-02-14 | Nerites Corporation | Biomimetic compounds and synthetic methods therefor |
EP2097119A4 (de) * | 2006-11-21 | 2012-10-17 | Abbott Lab | Verwendung eines terpolymers von tetrafluorethylen, hexafluorpropylen und vinylidenfluorid in medikamentenbeschichtungen |
EP1927648A1 (de) * | 2006-12-01 | 2008-06-04 | Rolex Sa | Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame |
EP1927649A1 (de) * | 2006-12-01 | 2008-06-04 | SurfaceSolutions GmbH | Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren sowie deren mechanische Anwendung als Sperrschicht |
-
2006
- 2006-12-01 EP EP20060405504 patent/EP1927648A1/de not_active Withdrawn
-
2007
- 2007-11-29 JP JP2009538570A patent/JP5385788B2/ja not_active Expired - Fee Related
- 2007-11-29 EP EP07816284.9A patent/EP2084252B1/de active Active
- 2007-11-29 CN CN2007800439661A patent/CN101611124B/zh not_active Expired - Fee Related
- 2007-11-29 WO PCT/CH2007/000601 patent/WO2008064510A1/fr active Application Filing
- 2007-11-29 US US12/516,865 patent/US20100075138A1/en not_active Abandoned
- 2007-11-29 EP EP07816285.6A patent/EP2084253B1/de active Active
- 2007-11-29 US US12/516,231 patent/US20100068553A1/en not_active Abandoned
- 2007-11-29 WO PCT/CH2007/000602 patent/WO2008064511A1/fr active Application Filing
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2008064510A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN101611124A (zh) | 2009-12-23 |
EP2084253A1 (de) | 2009-08-05 |
US20100068553A1 (en) | 2010-03-18 |
WO2008064510A1 (fr) | 2008-06-05 |
WO2008064511A1 (fr) | 2008-06-05 |
EP1927648A1 (de) | 2008-06-04 |
EP2084253B1 (de) | 2017-03-29 |
JP5385788B2 (ja) | 2014-01-08 |
EP2084252B1 (de) | 2017-03-29 |
US20100075138A1 (en) | 2010-03-25 |
JP2010511099A (ja) | 2010-04-08 |
CN101611124B (zh) | 2013-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2084252B1 (de) | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame | |
US8951630B2 (en) | Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame and in mechanical engineering as a barrier film | |
EP2102319B1 (de) | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht | |
EP2655577B1 (de) | Zusammensetzung zur erhöhung der lipophobie einer komponente zur uhrherstellung | |
EP2846931B1 (de) | Abdeckung von oberflächen zur uhrenherstellung unter verwendung kationischer zusammensetzungen mit phosphonischen molekülen und aminen | |
EP1051408A1 (de) | Fluorochemische benzotriazole | |
EP3290451B1 (de) | Substrat, das eine mit epilamisierungsmittel beschichtete oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats | |
JP6470815B2 (ja) | 時計または宝飾品の要素のエピラム化方法 | |
EP2655523B1 (de) | Lipophobe und hydrophobe zusammensetzung enthaltend komponenten mit einer diphosphon- und thiol-gruppe | |
US20140308513A1 (en) | Noble metal protective film and method of forming the same | |
CA2962057C (fr) | Traitement de surface de substrats metalliques | |
EP3420037A1 (de) | Zusammensetzungen mit in fluoriniertem lösungsmittel aufgelösten bisphosphonischen verbindungen und verwendung davon zur abdeckung der oberfläche eines teils | |
EP3192854B1 (de) | Artikel, dessen oberfläche mit einem kopplungsmittel mit oleophoben und/oder hydrophoben eigenschaften behandelt wurde | |
JP4723161B2 (ja) | 多芳香環化合物による紫外線耐性自己組織化単分子膜 | |
EP3192853B1 (de) | Oberflächenbehandlungsverfahren zum erzeugen einer oleophoben und/oder hydrophoben beschichtung | |
JPH0569878B2 (de) | ||
RU2141496C1 (ru) | Полимерная защитная композиция "полизам" | |
EP4394020A1 (de) | Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats | |
EP4394021A1 (de) | Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats | |
CH720411A2 (fr) | Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20090507 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20130424 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602007050414 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: C10M0133060000 Ipc: C10M0105200000 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C10M 105/62 20060101ALI20160804BHEP Ipc: C10M 105/70 20060101ALI20160804BHEP Ipc: C10M 105/20 20060101AFI20160804BHEP Ipc: C10M 105/68 20060101ALI20160804BHEP Ipc: C10M 105/54 20060101ALI20160804BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20161007 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 879765 Country of ref document: AT Kind code of ref document: T Effective date: 20170415 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602007050414 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: MOINAS AND SAVOYE SARL, CH |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170630 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20170329 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 879765 Country of ref document: AT Kind code of ref document: T Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170629 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170731 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170729 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602007050414 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20180103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171129 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20171130 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20071129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170329 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20201130 Year of fee payment: 14 Ref country code: GB Payment date: 20201118 Year of fee payment: 14 Ref country code: DE Payment date: 20201109 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602007050414 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20211129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211129 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220601 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211130 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230528 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20231201 Year of fee payment: 17 |