EP2084253B1 - Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame - Google Patents

Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame Download PDF

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EP2084253B1
EP2084253B1 EP07816285.6A EP07816285A EP2084253B1 EP 2084253 B1 EP2084253 B1 EP 2084253B1 EP 07816285 A EP07816285 A EP 07816285A EP 2084253 B1 EP2084253 B1 EP 2084253B1
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ultra
thin layer
gold
formula
water
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EP2084253A1 (de
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Samuele Tosatti
Stefan Zürcher
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Rolex SA
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Rolex SA
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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 (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.
  • 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 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 (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 7400 equivalents. CO 2 .
  • the object of the invention is to propose compounds that can be used as epilame and that can be attached to a solid substrate surface.
  • 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, by for example a mixture of water and 2-propanol. Thanks to the catechol foot of the compounds used, this ultra-thin layer is firmly fixed to the surface of the solid substrate. This ultra-thin layer has satisfactory properties for use as an 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 group A serves in particular to allow the attachment of the compounds to the surface of the solid substrate through the catechol group and the solubilization of the amphiphilic molecule A-B in the dipping solution.
  • Group B gives the ultra-thin layer its hydrophobic and oleophobic properties.
  • Interesting groups A are those selected from one of the following groups:
  • the compounds of formulas A-B can be obtained from known compounds using techniques and reactions well known to the organic chemist.
  • 1- (3,4-dihydroxyphenethyl) -3-octadecylurea can be obtained by reacting octadecylisocyanate and 3-hydroxy-tyramine hydrochloric acid in solution in DMF in the presence of N-methyl-morpholine.
  • 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, 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 metallic or ceramic oxides, such as zirconia and niobium (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 parts made of 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 will be 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 contact angle in advance with the water must generally be at least 100 °.
  • epilame a film whose contact angle may be substantially less than 100 °, for example between 90 and 100 °, but still prevents spreading, which remains less than 2%.
  • 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, or a mixture of an aprotic solvent and a solvent protic such as 2-propanol.
  • 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, or a mixture of an aprotic solvent and a solvent protic such as 2-propanol.
  • Octadecylisocyanate (668 mg, 2.26 mmol) was dripped into a solution of 3-hydroxy-tyramine hydrochloric acid (428 mg, 2.26 mmol) and N-methyl-morpholine (372 ⁇ l). ) in DMF (5 ml). The mixture was stirred under a nitrogen atmosphere for 6 hours. Water (50 ml) was added and the white precipitate formed was filtered and washed with water (10 ml) and acetone (10 ml). Recrystallization from acetone (160 ml) at -20 ° C gave 870 mg of white powder.
  • the gold, polished steel, aluminum, titania and ruby samples were cleaned in a UV / ozone chamber for 30 minutes and immersed overnight in the SuSoS1 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 slightly polished with a wipe impregnated with 2-propanol, rinsed with additional 2-propanol and dried with a stream of nitrogen (see Table 1A below). Or
  • X-ray photoelectron spectroscopy (XPS) analysis shows that SuSoS1 molecules are present on all surfaces by the detection of N elements.
  • An ultra-thin layer of SuSoS1 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 1.0 nm for SuSoS1 and 1.7 nm for Fixodrop.
  • 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 oil used for the tests is 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 of 32.8 mN / m).
  • the spread obtained is compared on surfaces of steel, ruby, aluminum, titanium dioxide, and gold coated with the SuSoS1 molecule, as well as a gold surface coated with the commercial product Fixodrop FK -BS of the Moebius and Son house as indicated by the manufacturer.
  • the spread is in all cases less than 2%, and is comparable to that measured for the Fixodrop, as shown in the table below.
  • the contact angle obtained on the ultra-thin layers made with the molecule SuSoS1 is greater than 100 °, the surface energy is less than 20 mJ m -2 , and the spread is less than 2%.
  • the layers are resistant to ruby, aluminum and titanium dioxide washings, but less well to gold and steel.
  • the properties of the ultra-thin layer SuSoS1 are at least as good as those obtained with the commercial product Fixodrop.

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  • 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)

Claims (10)

  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 imgb0012
     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, nicht substituierte Alkylgruppe C1-C20 steht.
  2. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass A gewählt ist aus einer der folgenden Gruppen:
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
  3. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, gekennzeichnet durch eine Verbindung der folgenden Formel:
    Figure imgb0016
  4. 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.
  5. Ultradünne Schicht gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Vorwärts-Kontaktwinkel mit Wasser mindestens 100° beträgt.
  6. Uhr, dadurch gekennzeichnet, dass sie eine ultradünne Schicht gemäß einem der vorangehenden Ansprüche umfasst.
  7. Verfahren zur Herstellung einer ultradünnen Schicht gemäß einem der Ansprüche 1 bis 5, 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.
  8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass die protische Lösung 2-Propanol ist.
  9. Verfahren zur Herstellung einer ultradünnen Schicht gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es das Eintauchen des Substrats in eine Lösung der Zusammensetzung mit der Formel A-B in ein Gemisch aus aprotischem Lösungsmittel und protischem Lösungsmittel umfasst.
  10. Verwendung einer ultradünnen Schicht gemäß einem der Ansprüche 1 bis 5 als Epilame.
EP07816285.6A 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame Active EP2084253B1 (de)

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EP07816285.6A EP2084253B1 (de) 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame

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EP20060405504 EP1927648A1 (de) 2006-12-01 2006-12-01 Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame
PCT/CH2007/000602 WO2008064511A1 (fr) 2006-12-01 2007-11-29 Couche ultra-mince hydrophobe et oleophobe, procede de fabrication et utilisation en horlogerie comme epilame
EP07816285.6A EP2084253B1 (de) 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame

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EP2084253A1 EP2084253A1 (de) 2009-08-05
EP2084253B1 true EP2084253B1 (de) 2017-03-29

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EP20060405504 Withdrawn EP1927648A1 (de) 2006-12-01 2006-12-01 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
EP07816284.9A Active EP2084252B1 (de) 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame

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US (2) US20100068553A1 (de)
EP (3) EP1927648A1 (de)
JP (1) JP5385788B2 (de)
CN (1) CN101611124B (de)
WO (2) WO2008064510A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1927648A1 (de) * 2006-12-01 2008-06-04 Rolex Sa Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame
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
CN103476908B (zh) * 2010-12-23 2015-12-16 劳力士有限公司 用于增加钟表制造元件的疏油性的组合物
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)

* Cited by examiner, † Cited by third party
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
US7858679B2 (en) * 2001-07-20 2010-12-28 Northwestern University Polymeric compositions and related methods of use
US20030087338A1 (en) * 2001-07-20 2003-05-08 Messersmith Phillip B. Adhesive DOPA-containing polymers and related methods of use
US7618937B2 (en) * 2001-07-20 2009-11-17 Northwestern University Peptidomimetic polymers for antifouling surfaces
US8815793B2 (en) * 2001-07-20 2014-08-26 Northwestern University Polymeric compositions and related methods of use
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
EP1927649A1 (de) * 2006-12-01 2008-06-04 SurfaceSolutions GmbH Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren sowie deren mechanische Anwendung als Sperrschicht
EP1927648A1 (de) * 2006-12-01 2008-06-04 Rolex Sa Hydrophobe und oleophobe ultradünne Schicht, Herstellungsverfahren und Anwendung beim Uhrenbau als Epilame

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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Publication number Publication date
US20100068553A1 (en) 2010-03-18
CN101611124B (zh) 2013-11-06
EP2084253A1 (de) 2009-08-05
EP1927648A1 (de) 2008-06-04
JP2010511099A (ja) 2010-04-08
CN101611124A (zh) 2009-12-23
EP2084252A1 (de) 2009-08-05
WO2008064511A1 (fr) 2008-06-05
JP5385788B2 (ja) 2014-01-08
WO2008064510A1 (fr) 2008-06-05
US20100075138A1 (en) 2010-03-25
EP2084252B1 (de) 2017-03-29

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