EP2084252B1 - 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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EP2084252B1
EP2084252B1 EP07816284.9A EP07816284A EP2084252B1 EP 2084252 B1 EP2084252 B1 EP 2084252B1 EP 07816284 A EP07816284 A EP 07816284A EP 2084252 B1 EP2084252 B1 EP 2084252B1
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ultra
thin layer
gold
water
nickel
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French (fr)
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EP2084252A1 (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 states that ⁇ SV - LS - ⁇ LV ⁇ cos ⁇ , where ⁇ is the contact angle of the drop of liquid with respect to the surface.
  • 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 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 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 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.
  • 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 (SuSoS2).
  • 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.
  • 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 (SuSoS 3) 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 .
  • 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, 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 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 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.
  • 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 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.
  • 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.
  • 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 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 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 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.

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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 (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 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 Gruppen:
    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. Uhr, dadurch gekennzeichnet, dass sie 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 Epilame.
EP07816284.9A 2006-12-01 2007-11-29 Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame Active EP2084252B1 (de)

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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
EP07816284.9A EP2084252B1 (de) 2006-12-01 2007-11-29 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

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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
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
WO2014009059A1 (en) * 2012-07-10 2014-01-16 The Swatch Group Research And Development Ltd Surface lubrication of an article
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

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EP2084253B1 (de) 2017-03-29
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JP2010511099A (ja) 2010-04-08
US20100075138A1 (en) 2010-03-25
JP5385788B2 (ja) 2014-01-08
EP2084253A1 (de) 2009-08-05
CN101611124A (zh) 2009-12-23
US20100068553A1 (en) 2010-03-18
WO2008064511A1 (fr) 2008-06-05
CN101611124B (zh) 2013-11-06
WO2008064510A1 (fr) 2008-06-05

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