EP2102319A1 - Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere - Google Patents
Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriereInfo
- Publication number
- EP2102319A1 EP2102319A1 EP07816286A EP07816286A EP2102319A1 EP 2102319 A1 EP2102319 A1 EP 2102319A1 EP 07816286 A EP07816286 A EP 07816286A EP 07816286 A EP07816286 A EP 07816286A EP 2102319 A1 EP2102319 A1 EP 2102319A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ultra
- layer according
- thin layer
- gold
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C10M105/70—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen as ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
- C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
- C10M105/60—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom
- C10M105/62—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/68—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
- C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
- C10M2211/0425—Alcohols; Ethers; Aldehydes; Ketones used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/06—Perfluorinated compounds
- C10M2211/063—Perfluorinated compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
- C10M2215/0425—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/0806—Amides used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/10—Amides of carbonic or haloformic acids
- C10M2215/102—Ureas; Semicarbazides; Allophanates
- C10M2215/1023—Ureas; Semicarbazides; Allophanates used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/2203—Heterocyclic nitrogen compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Definitions
- the present invention relates to a novel hydrophobic and oleophobic ultra-thin layer formed by self-assembly on a solid substrate surface of catechol foot compounds, a process for preparing this ultra-thin layer and the use thereof as a barrier film, film antimigration or antimouillage film, which will be called "epilame" in the rest of the presentation by analogy with the watchmaking world.
- the proper functioning of a mechanical movement depends, among other things, on its lubrication.
- the durability of the lubricant depends in particular on its maintenance in the operating zone: however, a drop of lubricant spreads rapidly over a clean part.
- the deposition of an epilame layer generally in the form of a hydrophobic and oleophobic invisible molecular layer, avoids the spreading of the lubricant and its components.
- the spreading of a liquid depends on the interaction forces between the liquid, the surface and the surrounding air (see JC Berg, “Wettability", Marcel Dekker, New York, 1993 and AW Adamson, “Physical Chemistry of Surfaces”. “, Wiley).
- the parameter that characterizes the interaction forces between a liquid and the air is the surface tension, ⁇ LV .
- a surface energy ⁇ S v between a solid and the surrounding air and a parameter ⁇ L s between the solid and the liquid are similarly defined.
- Young's equation also shows that if the surface tension of the liquid is lower than the surface energy, the contact angle is zero and the liquid wets the surface. This is what happens with a lubricant deposited on a clean metal surface: in fact, a lubricant has a surface tension of 35-40 mN / m, whereas a current metal surface has a higher surface energy.
- the coating of the components on the substrate is carried out by soaking it in a solution of perfluorinated solvent loaded with polymer.
- the solvent used is generally tetradecafluorohexane (C 6 Fi 4 ) which, once volatilized, is a greenhouse gas since it remains stable for 3200 years in the air and has a greenhouse potential of 7M00 equ. CO 2 .
- 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 an environmentally friendly non-fluorinated solvent, for example a mixture of water and 2- propanol. Thanks to the catechol foot of the compounds used, this ultra-thin layer is firmly attached to the solid substrate surface. This ultra-thin layer has satisfactory properties for use as an epilame, in particular a contact angle in advance with water and a spreading of a drop, quite comparable to that of the layer obtained from the product. Fixodrop FK-BS reference product.
- the invention thus makes an important contribution to the ecological preparation of epilames.
- the catechol foot compounds have the general formula
- A-B wherein A represents a group of formula
- Z represents C or N +
- X represents CH or CL
- L being an electron-withdrawing group chosen from F, Cl, Br, I, CF 3 , NO 2 and
- Y represents H or CH 3 , or Y forms with X a heterocycle of 5 or 6 atoms,
- T represents NH, NH-CO, NH-CO-NH or NH 2 + U “ , U “ being a soluble anion, such as for example F “ , Cl “ , Br “ , I, OH “ , NO 3 “ , HSO 4 “ , SO 4 2” , CO 3 2 “ , HCO 3 “ or SCN “ , and
- B represents a C 1 -C 20 aliphatic linear alkyl group partially or completely substituted with F.
- the group A serves in particular to allow the attachment of the compounds to the solid substrate surface thanks to the group catechol and the solubilization of the amphiphilic molecule AB in the dipping solution.
- Group B gives the ultra-thin layer its hydrophobic and oleophobic properties.
- group B is a linear aliphatic group perfluoroalkyl in its terminal part, for example of formula (CH 2 ) n - (CF 2 ) m CF 3 in which n is 1 to 5, in particular 1 to 3, and m is 4 to 11, especially 5 to 9.
- Interesting groups A are those selected from one of the following groups:
- a particularly preferred compound is N- (3,4-dihydroxyphenethyl) -4,4,5,6,6,7,7,8,8,9,9,10,10,11,11,11,11. heptadécafluoroundécanamide
- the compounds of formulas AB can be obtained from known compounds using techniques and reactions well known to the organic chemist.
- N- (3,4-dihydroxyphenethyl) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide may be obtained by reacting 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl ester and 3-hydroxy-tyrosine hydrochloric acid in solution in DMF in the presence of N-methylmorpholine.
- the solid substrate on the surface of which the self-assembly is made can be any solid substrate involved in the operation of a mechanical movement, in particular consisting of a material selected from among gold, silver, silver steel, aluminum, brass, bronze, cuproberyllium, titanium dioxide, ruby, sapphire, as well as other metallic surfaces, such as iron, chromium, tantalum, yttrium, silicon, germanium, copper, platinum, nickel, and nickel-phosphorus, and metal or ceramic oxides, such as zirconia, or niobia (niobium oxide), this list not being limiting.
- the substrate may also be a substrate in one of these materials or another whose surface has been covered or coated, for example by an electroplating of gold, gold-copper-cadmium and gold, nickel, rhodium, one of tin-nickel, or treated by anodization, as in the case of parts 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 0.5 to 10 nm, a higher value that will be used for the definition of ultra-thin, preferably 1 to 4 nm.
- the contact angle in advance with the water must generally be at least 100 °.
- the ultra-thin layer of formula A-B remains functional as epilame after two washes.
- the invention also relates to a mechanical part characterized in that it comprises an ultra-thin layer as defined above.
- the invention also relates to a process for preparing the ultra-thin layer defined above, characterized in that it comprises immersing the substrate in a solution of the compound of formula AB, for example in water, or a mixture of water and protic solvent such as, for example, 2-propanol.
- This process does not use a fluorinated solvent and is therefore respectful of the environment.
- SuSoS2 (0.052 mmol) 33 mg was dissolved in 35 ml of 2-propanol in a graduated 100 ml flask and shaken until completely dissolved. Ultrapure water was added to the mark and shaken vigorously, which increased the temperature of the solution. After returning the solution to room temperature, a few drops of water were added to adjust the volume to 100 ml. The solution was sonicated for 10 seconds to degas it and allow complete mixing of water and 2-propanol.
- VASE Variable Angle Spectroscopic Ellipsometry
- the different substrates used are:
- Table 1 Thickness measured by ellipsometry and advance contact angles with water
- An ultra-thin layer of SuSoS2 is coated with substrates of gold, polished steel and ruby as described in Example 2.
- the surface appearance is excellent for gold and ruby: the layer is invisible and no mark is visible due to the deposit.
- Fixodrop FK-BS An ultra-thin layer of Fixodrop FK-BS is coated with gold, polished steel and ruby substrates as specified by the manufacturer by dipping the substrates in a solution of tetradecafluorohexane.
- the thickness of this layer measured by ellipsometry on gold is 0.7 nm for SuSoS2 and 1.7 nm for Fixodrop.
- SuSoS2 shows a dispersive character only, as expected for a molecule of this type.
- the surface energy seems to vary with the material, but is in any case below 20 mJ / m 2 .
- the weakest energy (and therefore has a priori the best hold) is obtained for steel, followed by ruby and gold.
- the spreading of the lubricants on a surface is characterized by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after the drop has been deposited and after 20 minutes.
- the spread corresponds to the relative variation of the average diameter after 20 minutes.
- a good performance of a lubricant corresponds to a spread of 2% or less. Spreading greater than 10% is noticeable to the eye and is not acceptable.
- the oils used for the tests are a watch oil “941" (house Moebius and Fils, mixture of alkyl-aryl-monooleate and two C 10 -C 18 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 spread is in all cases less than 1%, and is comparable to that measured for the Fixodrop, as shown by the table below.
- the contact angle obtained on the ultra-thin layers made with the SuSoS2 molecule is greater than 100 °, the surface energy is less than 20 mJ m -2 , and the spread is less than
- the layers are resistant to ruby washes, but less well on gold and steel.
- the properties of the ultra-thin layer SuSoS2 are equivalent to those obtained with the commercial product Fixodrop.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07816286.4A EP2102319B1 (fr) | 2006-12-01 | 2007-11-29 | Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20060405505 EP1927649A1 (fr) | 2006-12-01 | 2006-12-01 | Couche ultra-mnce hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
EP07816286.4A EP2102319B1 (fr) | 2006-12-01 | 2007-11-29 | Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
PCT/CH2007/000603 WO2008064512A1 (fr) | 2006-12-01 | 2007-11-29 | Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2102319A1 true EP2102319A1 (fr) | 2009-09-23 |
EP2102319B1 EP2102319B1 (fr) | 2017-03-29 |
Family
ID=38137733
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20060405505 Withdrawn EP1927649A1 (fr) | 2006-12-01 | 2006-12-01 | Couche ultra-mnce hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
EP07816286.4A Not-in-force EP2102319B1 (fr) | 2006-12-01 | 2007-11-29 | Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20060405505 Withdrawn EP1927649A1 (fr) | 2006-12-01 | 2006-12-01 | Couche ultra-mnce hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere |
Country Status (3)
Country | Link |
---|---|
US (1) | US20100098926A1 (fr) |
EP (2) | EP1927649A1 (fr) |
WO (2) | WO2008064512A1 (fr) |
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 (fr) * | 2006-12-01 | 2008-06-04 | Rolex Sa | Couche ultra-mince hydrophobe et oléophobe, procédé de fabrication et utilisation en horlogerie comme épilame |
EP2655577B1 (fr) * | 2010-12-23 | 2014-04-23 | Rolex S.A. | Composition pour augmenter la lipophobicite d'un composant horloger |
CH708539B1 (en) * | 2012-07-10 | 2017-03-31 | Swatch Group Res & Dev Ltd | Agent for the surface lubrication of an object. |
EP3070152B1 (fr) * | 2015-03-18 | 2018-02-28 | The Swatch Group Research and Development Ltd. | Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat |
EP3398978B1 (fr) * | 2017-05-05 | 2020-03-11 | The Swatch Group Research and Development Ltd | Agent d'épilamage et procédé d'épilamage utilisant un tel agent d'épilamage |
EP3627237B1 (fr) * | 2018-09-20 | 2022-04-06 | ETA SA Manufacture Horlogère Suisse | Composant en materiau micro-usinable pour resonateur à haut facteur de qualité |
Family Cites Families (1)
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 |
-
2006
- 2006-12-01 EP EP20060405505 patent/EP1927649A1/fr not_active Withdrawn
-
2007
- 2007-11-29 WO PCT/CH2007/000603 patent/WO2008064512A1/fr active Application Filing
- 2007-11-29 WO PCT/CH2007/000604 patent/WO2008064513A1/fr active Application Filing
- 2007-11-29 EP EP07816286.4A patent/EP2102319B1/fr not_active Not-in-force
- 2007-11-29 US US12/517,121 patent/US20100098926A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2008064512A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1927649A1 (fr) | 2008-06-04 |
WO2008064513A1 (fr) | 2008-06-05 |
EP2102319B1 (fr) | 2017-03-29 |
US20100098926A1 (en) | 2010-04-22 |
WO2008064512A1 (fr) | 2008-06-05 |
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