Patent Grant
8951630
The present invention relates to a novel ultra-thin hydrophobic and oleophobic layer, formed by self-assembly on a solid substrate surface, of compounds based on catechol, a method of preparing this ultra-thin layer and the use thereof as an epilame in watchmaking, and more generally in mechanical engineering, as a barrier film, an anti-migration film or an anti-wetting film, which will be referred to in the disclosure below as an “epilame” by analogy with the watchmaking sector.
The proper functioning of a watch or mechanical movement depends among other things on its lubrication. The durability of the lubricant depends particularly on its being maintained in the functioning area; however, a drop of lubricant rapidly spreads on a clean part, as observed by all watchmakers. The deposition of a layer of epilame, generally in the form of an invisible hydrophobic and oleophobic molecular layer, enables the spread of the lubricant and its components to be avoided.
The spread of a liquid depends on the forces of interaction between the liquid, the surface and the surrounding air (cf. J. C. Berg, “Wettability”, Marcel Dekker, New York, 1993 and A. W. Adamson, “Physical Chemistry of Surfaces”, Wiley). The parameter that characterises the forces of interaction between a liquid and air is the surface tension, γLV. Similarly, a surface energy γSV is defined between a solid and the surrounding air and a parameter γLS between the solid and the liquid. For a drop of liquid in equilibrium on a surface, Young's equation stipulates that γSV−γLS=γLV·cos θ, where θ is the contact angle of the drop of liquid in relation to the surface. 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 for a lubricant deposited on a clean metallic surface, since a lubricant has a surface tension of 35-40 mN/m whereas a common metallic surface has a higher surface energy.
The surface energy depends on several factors (J. P. Renaud and P. Dinichert, 1956, “Etats de surface et étalement des huiles d′ horlogerie”, Bulletin SSC III page 681):
The surface energy is often determined by the last atomic or molecular layer. The chemical nature of the solid is of little importance in relation to the state of its surface and the contamination covering it. On a clean metallic surface free from organic contamination, the advancing contact angle with a drop of water is less than 10°. With a molecule forming self-assembled monomolecular layers (SAM: Self-Assembled Monolayers) having an —OH functional group (e.g. HOC11H22SH), this contact angle is about 30°, whereas it is about 110° for a —CH3 functional group (e.g. C12H25SH) and about 118° for a —CF3 functional group (e.g. C10F17H4SH).
The manufacturing techniques used in mechanical engineering, especially watchmaking up to the 1930s left a surface state that minimised the spread of lubricants by means of the presence of a film that lowered the surface energy (M. Osowiecki, 1957, “Un nouvel épilame résistant aux lavages”, Bulletin SSC III, page 735). This film disappeared with the improvements made to washing techniques, causing more or less rapid spread of the lubricants. In 1930, P. Woog of the Compagnie Francaise de Raffinage developed an anti-migration product based on stearic acid, which he called “epilame”. This was used in various branches of industry until the end of the 1960s. The name remained, and refers in watchmaking to any product used to guarantee that lubricants are retained on a surface.
The deposition of a compound on a functional surface in order to reduce surface energy and to control wettability and adhesion is a fairly widespread process. However, its application as a barrier film or anti-migration film is limited to watchmaking (M. Massin, “Epilames et lubrifiants associés a haute stabilité: propriétés, technologie d′ application et résultats en horlogerie”, Actes du congrès de Chronométrie Franco-Allemand, page 85, 1970, and “Conception de la lubrification en micromécanique: réalisations nouvelles par préparation des surfaces associées à des fluides silicones”, Actes du congrés des Sociétés Allemande et Francaise de Chronométrie, page 95, 1971), the space industry (M. Marchetti, “Aspects globaux et locaux de la mise en oeuvre de la lubrication fluide en ambiance spatiale”, doctoral thesis, INSA, Lyon, 2000) and electronics. Common to the first two sectors is the difficulty in replacing a used or exhausted lubricant.
Products based on stearic acid diluted in toluene were used in watchmaking until the 1970s (M. Osowiecki, see reference above, and P. Ducommun, 1956, “Les huiles d′ horlogerie synthtéiques”, J. Suisse Horl. Bij. 9-10, 117). Research undertaken in the late 1960s led to two important developments. On the one hand, a silicone-based product was developed (P. Massin, see references above) but met with only limited success. On the other hand, fluorinated polymer-based products were introduced during the 1970s and are still in use today.
Currently, the great majority of epilames available on the market, such as Fixodrop FK-BS from Moebius or the Fluorad product range (FC-722 and others) from 3M, consist of a fluorinated polymer dissolved in a perfluorinated solvent.
The deposition or coating of the compound or component on the substrate takes place by dipping the latter in a solution of perfluorinated solvent loaded with polymer. The solvent used is generally tetradecafluorohexane (C6F14) which, once volatilised, is a greenhouse gas since it remains stable in air for 3200 years and has a global warming potential of 7400 CO2 equivalents.
Another object of the invention is to propose compounds which can be used as an epilame and are capable of being fixed to a solid substrate surface.
Another object of the invention is to propose compounds which can be used as an epilame and are capable of being fixed to a solid substrate surface without the use of environmentally toxic fluorinated solvents.
These objects are achieved by the respective features of the present invention.
The invention proposes a novel ultra-thin hydrophobic and oleophobic layer, formed by self-assembly on a solid substrate surface, of compounds based on catechol and a method of preparing this ultra-thin layer which uses a non-fluorinated solvent, such as an environmentally friendly non-fluorinated solvent, e.g. a mixture of water and 2-propanol. Owing to the catechol base 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 an advancing contact angle with water and a spread of a drop, such as a drop of oil, entirely comparable with those of the layer obtained from the commercial reference product, Fixodrop FK-BS.
In some aspects, the invention thus makes an important contribution to the eco-friendly preparation of epilames.
In particular embodiments of the present invention, the catechol-based compounds have the general formula
A-B
in which
B represents an unsubstituted C1-C20 linear aliphatic alkyl group, or a C1-C20 linear aliphatic alkyl group partially or completely substituted with F.
The group A is used particularly to enable the attachment of the compounds to the surface of the solid substrate owing to the catechol group and the solubilisation of the amphiphilic molecule A-B in the dipping solution.
The group B provides the ultra-thin layer with its hydrophobic and oleophobic properties.
In embodiments where group B has partial or complete substitution with F, the group B is preferably a linear aliphatic alkyl group perfluorinated in its terminal section, e.g. with the formula
(CH2)n—(CF2)mCF3
in which n is 1 to 5, particularly 1 to 3, and m is 4 to 11, particularly 5 to 9.
Groups A of interest are those selected from one of the following groups:
A particularly useful compound, for example, in embodiments where the group B has partial or complete substitution with F, is N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide
(SuSoS2).
The compounds of formulae A-B can be obtained from known compounds using techniques and reactions well known to the organic chemist.
For example, 1-(3,4-dihydroxyphenethyl)-3-octadecylurea
(SuSoS1) can be obtained by reacting octadecyl isocyanate and 3-hydroxytyramine hydrochloride in solution in DMF in the presence of N-methylmorpholine.
For example, N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide can be obtained by reacting N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoate and 3-hydroxytyrosine hydrochloride in solution in DMF in the presence of N-methylmorpho line.
(SuSoS 3) can be prepared from ANACAT and N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoic acid by processes similar to those described by Y. Bethuel, K. Gademann, J. Org. Chem. 2005, 70, 6258; Zürcher, S.; Wäckerlin, D.; Bethuel, Y.; Malisova, B.; Textor, M.; Tosatti, S.; Gademann, K. Journal of the American Chemical Society 2006, 128, 1064-1065.
(SuSoS4) can also be prepared by processes similar to those mentioned above, from 1-(2-aminoethyl)-3,4-dihdyroxypyridinium and from N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoic acid.
(SuSoS5) can also be prepared by processes similar to those mentioned above from 3-hydroxytyrosine hydrochloride and 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-iodo-decane.
(SuSoS6) can also be prepared by processes similar to those mentioned above from 4-(2-aminoethyl)-5-nitro-benzene-1,2-diol and N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoic acid.
The solid substrate on the surface of which the self-assembly takes place may be any solid substrate involved in the functioning of a mechanical movement, particularly composed of a material selected from gold, silver, steel, for example, 20AP steel, aluminium, brass, bronze, copper-beryllium, titanium dioxide, ruby, sapphire, in some embodiments, silicon, nickel and nickel phosphorus, as well as other metallic surfaces such as iron, chromium, tantalum, yttrium, silicon, germanium, copper, platinum, in some embodiments, nickel and nickel-phosphorus, and metal oxides or ceramics, such as zirconia and/or niobia (niobium oxide), this list being non-limitative. It is also possible to use as the substrate polymers such as polyethylenes, polystyrenes, polyamides, polydimethyl-siloxanes, polyvinyl chlorides or epoxy resins, this list also being non-limitative. The substrate may also be a substrate made of one of these materials or another, the surface of which has been covered or coated, for example by an electroplating of gold, of gold-copper-cadmium and of gold, of nickel, of rhodium, of tin-nickel, or treated by anodising, as in the case of parts made of aluminium alloy or titanium alloy, or modified by a surface treatment such as oxidation, carburisation or nitriding.
The thickness of the ultra-thin layer, measured by ellipsometry, is generally 0.5 to 10 nm, the upper value that will be used for the definition of ultra-thin, preferably 1 to 4 nm.
In order to be considered or effective as an epilame, i.e. satisfactorily to prevent the spread of oil, the advancing contact angle with water must generally be at least 100°. Also, a film having a contact angle that may be significantly less than 100°, for example from 90 to 100°, but which nevertheless prevents spread, which remains lower than 2%, will also be considered as an epilame.
The ultra-thin layer of formula A-B preferably remains effective as an epilame after two washing operations.
The invention also relates to a watchmaking or to a mechanical part characterised in that it comprises an ultra-thin layer as defined above.
The invention also relates to a method of preparing the ultra-thin layer defined above, characterised in that it comprises the immersion of the substrate in a solution of the compound of formula A-B, 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 protic solvent such as 2-propanol. This method, in embodiments where it does not use any fluorinated solvent, is therefore environmentally friendly.
The invention will be better understood with the aid of the following examples, which are illustrative in nature and non-restrictive.
Octadecyl isocyanate (668 mg, 2.26 mmol) was added dropwise to a solution of 3-hydroxytyramine hydrochloride (428 mg, 2.26 mmol) and N-methylmorpholine (372 μl) in DMF (5 ml). The mixture was stirred under a nitrogen atmosphere for 6 hours. Water (50 ml) was added and the white precipitate that formed was filtered and washed with water (10 ml) and acetone (10 ml). Recrystallisation from acetone (160 ml) at −20° C. gave 870 mg of white powder.
Molecular weight: 448.68%
% by weight: C, 72.28; H, 10.78; N, 6.24; O, 10.70
without H: C, 84.375; N, 6.25; O, 9.373
1H NMR (DMSO-d6, 300 MHz, 300 K, ppm): 8.72 (s, 1H OH), 8.62 (s, 1H OH), 6.7-6.5 (m, 3H dopamine), 5.82 (t, 1H NH), 5.68 (t, 1H NH), 3.12 (q, 2H CH2), 2.95 (q, 2H CH2), 2.5 (m, 4H CH2), 1.20 (m, 30H CH2), 0.86 (t, 3H CH3),
corresponding to 1-(3,4-dihydroxyphenethyl)-3-octadecylurea:
Preparation of Dipping Solution of SuSoS1
23.4 mg of SuSoS1 (0.052 mmol) were dissolved in 80 ml of 2-propanol in a 100 ml graduated flask. The solution was subjected to ultrasound (using Sonorex Super 10 P equipment at 100%) until completely dissolved. Ultrapure water was added up to the mark on the flask and the solution was shaken vigorously, which caused an increase in the temperature of the solution. After the solution returned to ambient temperature, a few drops of water were added to adjust the volume to 100 ml. The solution was subjected to ultrasound for 10 seconds to degas it and to allow complete mixing of the water and the 2-propanol.
Immersion of Substrates of Gold, Polished Steel, Aluminium, Titanium Oxide and Ruby in the Dipping Solutions
Experimental Protocol A1
The samples of gold, polished steel, aluminium, titanium oxide and ruby were cleaned in a UV/ozone chamber for 30 minutes and immersed overnight in the solution of SuSoS1. The samples were then immersed in 2-propanol for 10 seconds, rinsed with 2-propanol and dried with a nitrogen flow. In the case of steel, the surfaces were lightly polished with a cloth soaked in 2-propanol, rinsed with additional 2-propanol and dried with a nitrogen flow (see Table 1A below). Or
Experimental Protocol B1
The same samples were immersed for 12 hours at ambient temperature in a solution of 0.5 mM of the molecule SuSoS1 in a mixture of heptane (96%) and 2-propanol (4%). The samples were rinsed with 2-propanol and dried under a flow of dry nitrogen (see Table 1B below).
2H,2H,3H,3H-Perfluoroundecanoic acid (1.354 g, 2.75 mmol), N-hydroxysuccinimide (348 mg, 3.02 mmol) and dicyclohexylcarbodiimide (622 mg, 3.02 mmol) were dissolved in ethyl acetate (120 ml) and stirred for 18 hours at ambient temperature. The white precipitate which formed (dicyclohexylurea, DCU) was filtered and the remaining solution was evaporated to dryness. The residue was recrystallised twice from ethyl acetate. Yield 1.00 g (62%) containing traces of DCU.
1H NMR (CDCl3, 300 MHz, ppm): 3.0 (m, 2H CH2), 2.88 (s, 4H CH2 NHS), 2.6 (m, 2H CH2).
3-Hydroxytyrosine hydrochloride (257.5 mg, 1.35 mmol) and N-methylmorpholine (241 μl) were dissolved in DMF (8 ml). The NHS perfluoro ester (800 mg) was added and the mixture was stirred under a nitrogen atmosphere overnight. Water (40 ml) was added and the precipitate that formed was filtered and washed with water. The solid was dissolved in ethyl acetate and the organic phase was dried with magnesium sulfate. The solvent was evaporated and the residue recrystallised from chloroform (30 ml, 4° C.). Yield 752 mg (88%).
Molecular weight: 627.29%
% by weight: C, 36.38; H, 2.25; F, 51.49; N, 2.23; O, 7.65
without H: C, 47.5; F, 42.5; N, 2.5; O, 7.5
1H NMR (CDCl3, 300 MHz, ppm): 8.7 (s broad, 2H OH), 8.08 (t, 1H NH), 6.7-6.4 (m, 3H dopamine), 3.2 (q, 2H CH2), 2.7-2.3 (m, 6H CH2), corresponding to N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide
Preparation of Dipping Solution of SuSoS2
33 mg of SuSoS2 (0.052 mmol) were dissolved in 35 ml of 2-propanol in a 100 ml graduated flask and shaken until completely dissolved. Ultrapure water was added up to the mark and the solution was again shaken vigorously, which caused an increase in the temperature of the solution. After the solution returned to ambient temperature, a few drops of water were added to adjust the volume to 100 ml. The solution was subjected to ultrasound for 10 seconds to degas it and to allow complete mixing of the water and the 2-propanol.
Immersion of Substrates of Gold, Polished Steel, Aluminium, Titanium Oxide and Ruby in the Dipping Solutions
The samples of gold, polished steel, aluminium, titanium oxide and ruby were cleaned in a UV/ozone chamber for 30 minutes and immersed overnight in the solution of SuSoS2. The samples were then immersed in 2-propanol for 10 seconds, rinsed with 2-propanol and dried with a nitrogen flow. In the case of steel, the surfaces were lightly polished with a cloth soaked in 2-propanol, rinsed with additional 2-propanol and dried with a nitrogen flow.
The monolayers formed by self-assembly on the various substrates were analysed by
The various substrates used are
The main parameters measured by VASE and CA are compiled in Tables 1A, 1B and 1C below.
Analysis by X-ray photoelectron spectroscopy (XPS) shows that the SuSoS1 molecules are present on all the surfaces by detection of the elements N.
These results show that an ultra-thin layer of SuSoS1 is obtained on all the substrates tested.
The advancing contact angle values with water are satisfactory for use as an epilame (greater than 100° or slightly less than this value but with spread values of less than 2% (as will be seen below).
Analysis by X-ray photoelectron spectroscopy (XPS) shows that the SuSoS2 molecules are present on all the surfaces by detection of the elements N and F.
These results show that an ultra-thin layer of SuSoS2, whose thickness, measured by ellipsometry, does not correspond exactly to the expected thickness of a well-ordered monolayer, is obtained on all the substrates tested.
The advancing contact angle values with water are satisfactory for use as an epilame (greater than 100°).
1) Preparation of Ultra-Fine Layers of SuSoS1 and Fixodrop on the Surfaces of the Various Substrates
Surfaces of substrates of gold, polished steel and ruby are covered with an ultra-fine layer of SuSoS1 as described in example 2A. The surface appearance is excellent and no mark resulting from the deposit can be distinguished.
Surfaces of substrates of gold, polished steel and ruby are covered with an ultra-fine layer of Fixodrop FK-BS in accordance with the manufacturer's instructions by dipping the substrates in a solution of tetradeca-fluorohexane.
The thickness of this layer measured by ellipsometry on gold is 1.0 nm for SuSoS1 and 1.7 nm for Fixodrop.
2) Measurement of Lubricant Spread
The spread of lubricants on a surface is characterised by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after depositing the drop and after 20 minutes. The spread corresponds to the relative variation in the average diameter after 20 minutes. A good lubricant behaviour corresponds to a spread of 2% or less. A spread greater than 10% can be observed by the naked eye and is not acceptable. The oil used for the tests is a watchmakers' oil “941” (Moebius et Fils, mixture of alkyl-aryl-monooleate and two C10-C13 diesters, viscosity of 110 cSt at 20° C., surface tension of 32.8 mN/m).
The spread obtained on surfaces of steel, ruby, aluminium, titanium dioxide and gold coated with the SuSoS1 molecule, and a gold surface coated with the commercial product Fixodrop FK-BS from Moebius et Fils in accordance with the manufacturer's instructions, is compared. For the SuSoS1 molecule, the spread is less than 2% in all cases and is comparable to that measured for Fixodrop, as shown by the table below.
3) Conclusion
For all the surfaces investigated, the contact angle obtained on the ultra-thin layers formed with the SuSoS1 molecule is greater than 100°, the surface energy is less than 20 mJ m−2 and the spread is less than 2%.
The layers exhibit good resistance to washing treatments on ruby, aluminium and titanium dioxide but less good on gold and steel.
The properties of the ultra-thin SuSoS1 layer are at least as good as those obtained with the commercial product Fixodrop.
1) Preparation of Ultra-Fine Layers of SuSoS2 and Fixodrop on the Surfaces of the Various Substrates
Surfaces of substrates of gold, polished steel and ruby are covered with an ultra-fine layer of SuSoS2 as described in example 2B. The surface appearance is excellent, especially for gold and ruby; the layer is invisible and no mark resulting from the deposit can be distinguished.
Surfaces of substrates of gold, polished steel and ruby are covered with an ultra-fine layer of Fixodrop FK-BS in accordance with the manufacturer's instructions by dipping the substrates in a solution of tetradeca-fluorohexane.
The thickness of this layer measured by ellipsometry on gold is 0.7 nm for SuSoS2 and 1.7 nm for Fixodrop.
2) Measurement of Contact Angles with Different Solvents and Determination of Surface Energies
The advancing contact angles with water, hexadecane, diiodomethane and ethylene glycol were measured by dynamic contact angle measurement using a goniometric technique similar to that used in example 3.
The dispersive and polar components of the surface energy were deduced from these measurements using the Owens-Wendt model (Owens D. K. and Wendt R. C., 1969, Journal of Applied Polymer Science, 13, 8, p. 1741).
The main results obtained are compiled in table 2B below.
For gold, steel and ruby, the contact angles with water, hexadecane, diiodomethane and ethylene glycol are acceptable for use as an epilame, and comparable with those measured for Fixodrop.
For gold, steel and ruby, the layer formed with SuSoS2 exhibits only a dispersive nature, as expected for a molecule of this type. The surface energy seems to vary with the material, but is in all cases less than 20 mJ/m2. The lowest energy (and therefore in principle the best behaviour) is obtained for steel, followed by ruby and gold.
3) Measurement of Lubricant Spread
The spread of lubricants on a surface is characterised by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after depositing the drop and after 20 minutes. The spread corresponds to the relative variation in the average diameter after 20 minutes. A good lubricant behaviour corresponds to a spread of 2% or less. A spread greater than 10% can be observed by the naked eye and is not acceptable. The oils used for the tests are a watchmakers' oil “941” (Moebius et Fils, mixture of alkyl-aryl-monooleate and two C10-C13 diesters, viscosity of 110 cSt at 20° C., surface tension of 32.8 mN/m) and a CESNIII test oil (Laboratoire Suisse de Recherches Horlogéres, silicone oil, surface tension of 23.1 mN/m, “La Suisse Horlogére” No 43, Jul. 11, 1974).
The spread obtained on surfaces of steel, ruby and gold coated with the SuSoS2 molecule, and a gold surface coated with the commercial product Fixodrop FK-BS from Moebius et Fils in accordance with the manufacturer's instructions, is compared. For the SuSoS2 molecule, the spread is less than 1% in all cases and is comparable to that measured for Fixodrop, as shown by the table below.
4) Conclusion
For all the surfaces investigated, the contact angle obtained on the ultra-thin layers formed with the SuSoS2 molecule is greater than 100°, the surface energy is less than 20 mJ m−2 and the spread is less than 1%.
The layers display good resistance to washing treatments on ruby, but less good on gold and steel.
The properties of the ultra-thin SuSoS2 layer are equivalent to, or at least as good as, those obtained with the commercial product Fixodrop, and a solvent that is environmentally friendly may be used.
| Number | Date | Country | Kind |
|---|---|---|---|
| 06405504 | Dec 2006 | EP | regional |
| 06405505 | Dec 2006 | EP | regional |
This application is a continuation-in-part of U.S. application Ser. Nos. 12/516,231 filed May 26, 2009, abandoned, which is a national stage of PCT/CH2007/000601 filed Nov. 29, 2007, 12/516,865 filed May 29, 2009, abandoned, which is a national stage of PCT/CH2007/000602 filed Nov. 29, 2007, and 12/517,121 filed Jul. 6, 2009, abandoned, which is a national stage of PCT/CH2007/000603 filed Nov. 29, 2007, the respective contents of which are hereby incorporated herein in their entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20120088099 A1 | Apr 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12516231 | US | |
| Child | 13323773 | US | |
| Parent | 12516865 | US | |
| Child | 12516231 | US | |
| Parent | 12517121 | US | |
| Child | 12516865 | US |
