EP2102319B1 - Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht - Google Patents

Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht Download PDF

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EP2102319B1
EP2102319B1 EP07816286.4A EP07816286A EP2102319B1 EP 2102319 B1 EP2102319 B1 EP 2102319B1 EP 07816286 A EP07816286 A EP 07816286A EP 2102319 B1 EP2102319 B1 EP 2102319B1
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Prior art keywords
ultra
thin layer
gold
water
nickel
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EP2102319A1 (de
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Samuele Tosatti
Stefan Zürcher
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SUSOS AG
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SUSOS AG
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    • 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
    • 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
    • C10M105/68—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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
    • C10M2211/0425—Alcohols; Ethers; 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • C10M2211/063—Perfluorinated compounds 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
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1023—Ureas; Semicarbazides; Allophanates 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
    • 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
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

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 a barrier film.
  • antimigration film or antimouillage film which will be called "epilame” in the rest of the exposition by analogy with the watchmaking world.
  • the proper functioning of a mechanical movement depends inter alia on its lubrication.
  • the durability of the lubricant depends in particular on its maintenance in the operating zone: however, 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 (cf. 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 between a solid and the surrounding air and a parameter ⁇ LS between the solid and the liquid is similarly defined.
  • Young's 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 with a lubricant deposited on a clean metal surface: in fact, a lubricant has a surface tension of 35-40 mN / m, whereas a current metal surface has a higher surface energy.
  • the coating of the components on the substrate is carried out by soaking it in a solution of perfluorinated solvent loaded with polymer.
  • the solvent used is generally tetradecafluorohexane (C 6 F 14 ) which, once volatilized, is a greenhouse gas since it remains stable for 3200 years in the air and has a greenhouse potential of 7'400 equiv. . CO 2 .
  • the object of the invention is to propose compounds which can be used as epilame and which can be attached to a solid substrate surface without the use of environmentally toxic fluorinated solvents.
  • the invention indeed proposes a new ultra-thin hydrophobic and oleophobic layer formed by self-assembly on a solid substrate surface of catechol foot compounds, and a method for preparing this ultra-thin layer which uses a respectful non-fluorinated solvent. from the environment, for example a mixture of water and 2-propanol. Thanks to the catechol foot of the compounds used, this ultra-thin layer is firmly attached to the solid substrate surface. This ultra-thin layer has satisfactory properties for use as an epilame, in particular a contact angle in advance with water and a spreading of a drop, quite comparable to that of the layer obtained from the product. Fixodrop FK-BS reference product.
  • the invention thus makes an important contribution to the ecological preparation of epilames.
  • the group A serves in particular to allow the attachment of the compounds to the solid substrate surface thanks to the group catechol and the solubilization of the amphiphilic molecule AB in the dipping solution.
  • Group B gives the ultra-thin layer its hydrophobic and oleophobic properties.
  • group B is a linear aliphatic group perfluorinated in its terminal part, for example of formula (CH 2 ) n - (CF 2 ) m CF 3 wherein n is 1 to 5, especially 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) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11- 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 hydrochloric acid dissolved in DMF in the presence of N-methylmorpholine.
  • 3- (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamido) -6,7-dihydroxy-1,1 dimethyl-1,2,3,4-tétrahydroquinolinium can be prepared from ANACAT and 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl by methods analogous to those described by Y.Bethuel. K. Gademann, J. Org. Chem 2005, 70, 6258 .
  • 1- (2- (4,4,5,5,6,6,7,7,8,8,9,9,10,10,10,11,11,11-heptadecafluoroundecanamido) ethyl) -3,4- dihydroxypyridinium may also be prepared by methods analogous to those mentioned above, from 1- (2-aminoethyl) -3,4-dihydroxypyridinium and 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl .
  • N- (3,4-dihydroxyphenethyl) -3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10,10-heptadecafluorodecan-1-aminium can also be prepared by methods analogous to those mentioned above, from 3-hydroxy-tyrosine hydrochloric acid and 1,1,1,2,2,3,3,4,4,5,5 , 6,6,7,7,8,8-heptadecafluoro-10-iododecane.
  • N- (4,5-dihydroxy-2-nitrophenethyl) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide (SuSoS6) can also be prepared by methods analogous to those mentioned above, from 4- (2-aminoethyl) -5-nitrobenzene-1,2-diol and 2H, 2H, 3H, 3H-perfluoro-undecanoic -acid-N-succinimidyl.
  • the solid substrate on the surface of which the self-assembly is made can 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, aluminum, brass, bronze, cuproberyllium, titanium dioxide, ruby, sapphire, as well as other metallic surfaces, such as iron, chromium, tantalum, yttrium, silicon, germanium, copper, platinum, nickel, and nickel-phosphorus, and metal or ceramic oxides, such as zirconia, or niobia (niobium oxide), this 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 treated by anodizing, as in the case of coins aluminum alloy or titanium, or modified by a surface treatment such as oxidation, carburization or nitriding.
  • the thickness of the ultra-thin layer measured in ellipsometry is 0.5 to 10 nm, which value is higher for the definition of ultra-thin, 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 washes.
  • the invention also relates to a mechanical part 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 additional 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.
  • X-ray photoelectron spectroscopy (XPS) analysis shows that SuSoS2 molecules are present on all surfaces by the detection of N and F elements.
  • 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 for gold and ruby: the layer is invisible and no mark is visible 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.
  • 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 has a priori the best hold) is obtained for steel, followed by ruby and gold.
  • 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" (Moebius and Fils house, mixture of alkyl-aryl-monooleate and two C 10 -C 13 di-esters, viscosity of 110 cSt at 20 ° C, surface tension 32.8 mN / m) and a test oil CESNIII ( Swiss Laboratory of Horological Research, silicone oil, surface tension of 23.1 mN / m, "The Swiss watchmaker” No 43, 7.11.1974 ).
  • 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 1%.
  • the layers are resistant to ruby washes, but less well on gold and steel.
  • the properties of the ultra-thin layer SuSoS2 are equivalent to those obtained with the commercial product Fixodrop.

Claims (11)

  1. Ultradünne Schicht, deren mittels Ellipsometrie gemessene Dicke zwischen 0,5 und 10 nm beträgt, hydrophob und oleophob, gebildet durch Selbstassemblierung auf einer festen Substratoberfläche aus Verbindungen der allgemeinen Formel

            A-B

    in welcher A eine Gruppe der Formel
    Figure imgb0015
     darstellt,
    in welcher Z für C oder N+ steht,
    X für C-H oder C-L steht, wobei L eine Elektronen anziehende Gruppe ist, gewählt aus F, Cl, Br, I, CF3, NO2 und N (CH3) 3 +,
    Y für H oder CH3 steht, wobei Y mit X einen Heterozyklus von 5 oder 6 Atomen bildet,
    T für NH, CO, NH-CO, NH-CO-NH oder NH2 +U steht, wobei U- gewählt ist aus F-, Cl-, Br-, I-, OH-, NO3 -, HSO4 -, SO4 2-, CO3 2-, HCO3 - oder SCN-, und
    B für eine lineare, aliphatische Alkylgruppe C1-C20 steht, teilweise oder vollständig substituiert durch F.
  2. Ultradünne Schicht gemäß Anspruch 1, dadurch gekennzeichnet, dass B eine lineare, aliphatische Alkylgruppe ist, die in ihrem Endabschnitt perfluoriert ist mit der Formel

            (CH2)n-(CF2)mCF3

    wobei n zwischen 1 und 5 liegt, und m zwischen 4 und 11.
  3. Ultradünne Schicht gemäß Anspruch 2, dadurch gekennzeichnet, dass n zwischen 1 und 3 liegt und m zwischen 5 und 9.
  4. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass A gewählt ist aus einer der folgenden Gruppein :
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
  5. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass sie erhalten wird ausgehend von N-(3,4-Dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoroundecanamid.
  6. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das feste Substrat zusammengesetzt ist aus einem Material gewählt aus Gold, Silber, Stahl, Aluminium, Messing, Bronze, Kupfer-Beryllium, Titandioxid, Rubin, Saphir, Silizium, Nickel und Nickel-Phosphor, sowie anderen metallischen Oberflächen, wie Eisen, Chrom, Tantal, Yttrium, Germanium, Kupfer, Platin und metallischen oder keramischen Oxiden, wie Zirkonoxid oder Nioboxid, oder Polymeren, wie Polyethylenen, Polystyrolen, Polyamiden, Polydimethylsiloxanen, Polyvinylchloriden, Epoxyharzen, oder auch ein Substrat aus einem dieser Materialien, dessen Oberfläche beschichtet oder überzogen worden ist, beispielsweise mit einer galvanischen Abscheidung von Gold, Gold-Kupfer-Cadmium und Gold, Nickel, Rhodium, Zinn-Nickel, oder anodisiert, wie im Falle von Teilen aus Aluminium- oder Titan-Legierungen, oder modifiziert durch eine Oberflächenbehandlung, wie Oxidation, Karburierung oder Nitrierung.
  7. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Vorwärts-Kontaktwinkel mit Wasser mindestens 100° beträgt.
  8. Mechanisches Teil, dadurch gekennzeichnet, dass es eine ultradünne Schicht gemäß einem der vorangehenden Ansprüche umfasst.
  9. Verfahren zur Herstellung einer ultradünnen Schicht gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es das Eintauchen des Substrats in eine Lösung der Zusammensetzung mit der Formel A-B in Wasser oder ein Wassergemisch und einer protischen Lösung umfasst.
  10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, dass die protische Lösung 2-Propanol ist.
  11. Verwendung einer ultradünnen Schicht gemäß einem der Ansprüche 1 bis 7 als Sperrschicht.
EP07816286.4A 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht Not-in-force EP2102319B1 (de)

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EP07816286.4A EP2102319B1 (de) 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht

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EP20060405505 EP1927649A1 (de) 2006-12-01 2006-12-01 Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren sowie deren mechanische Anwendung als Sperrschicht
EP07816286.4A EP2102319B1 (de) 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht
PCT/CH2007/000603 WO2008064512A1 (fr) 2006-12-01 2007-11-29 Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere

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EP2102319A1 EP2102319A1 (de) 2009-09-23
EP2102319B1 true EP2102319B1 (de) 2017-03-29

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EP07816286.4A Not-in-force EP2102319B1 (de) 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren sowie deren mechanische anwendung als sperrschicht

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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
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Also Published As

Publication number Publication date
EP1927649A1 (de) 2008-06-04
EP2102319A1 (de) 2009-09-23
WO2008064513A1 (fr) 2008-06-05
US20100098926A1 (en) 2010-04-22
WO2008064512A1 (fr) 2008-06-05

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