EP1927648A1 - 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 PDFInfo
- Publication number
- EP1927648A1 EP1927648A1 EP20060405504 EP06405504A EP1927648A1 EP 1927648 A1 EP1927648 A1 EP 1927648A1 EP 20060405504 EP20060405504 EP 20060405504 EP 06405504 A EP06405504 A EP 06405504A EP 1927648 A1 EP1927648 A1 EP 1927648A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ultra
- layer according
- gold
- water
- thin layer
- 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.)
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- 0 Oc(cc[n+](CCN*=O)c1)c1O Chemical compound Oc(cc[n+](CCN*=O)c1)c1O 0.000 description 2
- HQLZFBUAULNEGP-UHFFFAOYSA-N CCCC(CC)N Chemical compound CCCC(CC)N HQLZFBUAULNEGP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C10M105/68—Amides; Imides
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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
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/20—Aldehydes; Ketones
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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
- C10M105/50—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
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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
- C10M105/58—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
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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
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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
- 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
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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
- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/0806—Amides used as base material
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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
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 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 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 (SuSoS2).
- the compounds of formulas A-B 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 got by doing reacting 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl ester and 3-hydroxy-tyrosine hydrochloric acid in solution in DMF in the presence of N-methylmorpholine; 1- (3,4-dihydroxyphenethyl) -3-octadecylurea by reacting octadecylisocyanate and 3-hydroxy-tyramine hydrochloric acid in solution in DMF in the presence of N-methyl-morpholine.
- 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. Orch. 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 may also be prepared by methods analogous to those mentioned above, starting with 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 chosen from gold, steel, in particular 20AP steel, aluminum, brass, cuproberyllium, titanium dioxide, ruby, sapphire, silicon, nickel and nickel-phosphorus, as well as other metal surfaces, such as iron, chromium, tantalum, yttrium, copper, platinum, and metal or ceramic oxides, such as zirconia and 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 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 generally from 0.5 to 10 nm, preferably from 1 to 4 nm.
- the angle of contact in advance with the water is at least 100 °.
- the ultra-thin layer 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 method 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 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 for degassing and allowing complete mixing of water and 2-propanol.
- the samples of gold, polished steel, aluminum, titanium oxide and ruby were cleaned in a UV / ozone chamber for 30 minutes and immersed overnight in the SuSoS1 or SuSoS2 solution.
- the samples were then immersed in 2-propanol for 10 seconds, rinsed with 2-propanol and dried with a stream of nitrogen.
- 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 the SuSoS1 and SuSoS2 molecules are present on all surfaces by the detection of N and F elements (for the SuSoS2 molecule).
- Example 5 Comparison of ultra-thin layers formed by self-assembly of SuSoS2 and Fixodrop FK-BS on surfaces of gold, polished steel and ruby.
- 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 0.66 ⁇ 0.01 nm for SuSoS2 and 1.70 ⁇ 0.04 nm for Fixodrop.
- the contact angles in advance with water, hexadecane, diodomethane and ethylene glycol were measured by dynamic contact angle measurement or direction finding according to a technique similar to that used in Example 4.
- SuSoS2 For gold, steel and ruby, the layer formed with SuSoS2 shows a dispersive character only, as expected for a molecule of this type. 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)
Priority Applications (10)
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 |
EP07816285.6A EP2084253B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
US12/516,231 US20100068553A1 (en) | 2006-12-01 | 2007-11-29 | Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame |
CN2007800439661A CN101611124B (zh) | 2006-12-01 | 2007-11-29 | 疏水且疏油的超薄涂层、其制造方法及其作为基膜在钟表制造业中的应用 |
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 |
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 |
JP2009538570A JP5385788B2 (ja) | 2006-12-01 | 2007-11-29 | 疎水性かつ疎油性の超薄膜、その製造法および時計製造におけるエピラムとしての使用 |
EP07816284.9A EP2084252B1 (de) | 2006-12-01 | 2007-11-29 | Hydrophobe und oleophobe ultradünne schicht, herstellungsverfahren und anwendung beim uhrenbau als epilame |
US12/516,865 US20100075138A1 (en) | 2006-12-01 | 2007-11-29 | Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame |
US13/323,773 US8951630B2 (en) | 2006-12-01 | 2011-12-12 | Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame and in mechanical engineering as a barrier film |
Applications Claiming Priority (1)
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 |
Publications (1)
Publication Number | Publication Date |
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EP1927648A1 true EP1927648A1 (de) | 2008-06-04 |
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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 |
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 |
Family Applications After (2)
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 |
EP07816284.9A Active EP2084252B1 (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) | US20100068553A1 (de) |
EP (3) | EP1927648A1 (de) |
JP (1) | JP5385788B2 (de) |
CN (1) | CN101611124B (de) |
WO (2) | WO2008064510A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014009059A1 (en) * | 2012-07-10 | 2014-01-16 | The Swatch Group Research And Development Ltd | Surface lubrication of an article |
EP2865738A1 (de) * | 2013-10-28 | 2015-04-29 | The Swatch Group Research and Development Ltd. | Epilamisiertes Edelprodukt |
EP3315214A1 (de) | 2016-10-25 | 2018-05-02 | The Swatch Group Research and Development Ltd | Verfahren zur epilamisierung eines elements einer uhr oder eines schmuckstücks |
EP4075205A1 (de) * | 2021-04-16 | 2022-10-19 | ETA SA Manufacture Horlogère Suisse | Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder |
Families Citing this family (7)
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 |
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 |
EP3398978B1 (de) * | 2017-05-05 | 2020-03-11 | The Swatch Group Research and Development Ltd | Epilamisierungsmittel und epilamisierungsverfahren, bei dem dieses epilamisierungsmittel verwendet wird |
Citations (1)
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DD238812A1 (de) * | 1985-06-27 | 1986-09-03 | Ruhla Uhren Veb K | Verfahren zur herstellung eines schmier-, gleitmittels und antispreads fuer lager- und gleitelemente |
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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 |
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 |
WO2003008376A2 (en) * | 2001-07-20 | 2003-01-30 | Northwestern University | 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 |
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 |
JP4941845B2 (ja) * | 2005-08-24 | 2012-05-30 | イーティーエイチ・チューリッヒ | 表面改質のために有用なカテコール等価分子の製造方法 |
JP5597836B2 (ja) * | 2006-08-04 | 2014-10-01 | ケンジー ナッシュ コーポレイション | バイオミメティック化合物およびその合成方法 |
WO2008064058A2 (en) * | 2006-11-21 | 2008-05-29 | Abbott Laboratories | Use of a terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride in drug eluting coatings |
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 |
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2006
- 2006-12-01 EP EP20060405504 patent/EP1927648A1/de not_active Withdrawn
-
2007
- 2007-11-29 US US12/516,231 patent/US20100068553A1/en not_active Abandoned
- 2007-11-29 US US12/516,865 patent/US20100075138A1/en not_active Abandoned
- 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 JP JP2009538570A patent/JP5385788B2/ja not_active Expired - Fee Related
- 2007-11-29 WO PCT/CH2007/000602 patent/WO2008064511A1/fr active Application Filing
- 2007-11-29 EP EP07816285.6A patent/EP2084253B1/de active Active
- 2007-11-29 EP EP07816284.9A patent/EP2084252B1/de active Active
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014009059A1 (en) * | 2012-07-10 | 2014-01-16 | The Swatch Group Research And Development Ltd | Surface lubrication of an article |
CN104603247A (zh) * | 2012-07-10 | 2015-05-06 | 斯沃奇集团研究和开发有限公司 | 制品的表面润滑 |
EP2865738A1 (de) * | 2013-10-28 | 2015-04-29 | The Swatch Group Research and Development Ltd. | Epilamisiertes Edelprodukt |
EP2865737A1 (de) * | 2013-10-28 | 2015-04-29 | The Swatch Group Research and Development Ltd. | Edelprodukt aus Epilam |
EP3315214A1 (de) | 2016-10-25 | 2018-05-02 | The Swatch Group Research and Development Ltd | Verfahren zur epilamisierung eines elements einer uhr oder eines schmuckstücks |
EP4075205A1 (de) * | 2021-04-16 | 2022-10-19 | ETA SA Manufacture Horlogère Suisse | Verfahren zur herstellung einer uhrentriebfeder und durch dieses verfahren erhaltene uhrentriebfeder |
Also Published As
Publication number | Publication date |
---|---|
WO2008064511A1 (fr) | 2008-06-05 |
JP5385788B2 (ja) | 2014-01-08 |
EP2084253B1 (de) | 2017-03-29 |
EP2084252A1 (de) | 2009-08-05 |
EP2084253A1 (de) | 2009-08-05 |
EP2084252B1 (de) | 2017-03-29 |
CN101611124B (zh) | 2013-11-06 |
US20100068553A1 (en) | 2010-03-18 |
WO2008064510A1 (fr) | 2008-06-05 |
CN101611124A (zh) | 2009-12-23 |
JP2010511099A (ja) | 2010-04-08 |
US20100075138A1 (en) | 2010-03-25 |
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