EP2084253B1 - Ultra-thin water and oil repellent layer, manufacturing method and use in watchmaking as epilame - Google Patents

Description

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, γ _LV . A surface energy γ _SV between a solid and the surrounding air and a parameter γ _LS between the solid and the liquid is similarly defined. For a drop of equilibrium liquid on a surface, the Young equation states that γ _SV - γ _LS = γ _LV · cosθ, where θ 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.

• la composition chimique et la structure cristallographique du solide, et en particulier de sa surface,
• les caractéristiques géométriques de la surface et sa rugosité (et donc les défauts et/ou l'état de polissage),
• la présence de molécules adsorbées physiquement ou liées chimiquement à la surface, qui peuvent aisément masquer le solide et modifier considérablement son énergie de surface.

Surface energy depends on several factors ( JP Renaud and P. Dinichert, 1956, "Surface States and Spreading of Clockworks", Bulletin SSC III page 681 ):

• the chemical composition and the crystallographic structure of the solid, and in particular of its surface,
• the geometric characteristics of the surface and its roughness (and therefore the defects and / or the polishing state),
• the presence of molecules physically adsorbed or chemically bonded to the surface, which can easily hide the solid and significantly alter its surface energy.

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 that covers it. On a clean metal surface free of organic contamination, the contact angle in advance with a drop of water is less than 10 °. With a self-assembled monomolecular layer (SAM) molecule showing a -OH functional group (eg, HOC ₁₁ H ₂₂ SH), this contact angle is about 30 °, whereas it is about 110 ° for a functional group -CH ₃ (eg C ₁₂ H ₂₅ SH) and about 118 ° for a functional group -CF ₃ (eg C ₁₀ F ₁₇ H ₄ SH ).

The manufacturing techniques used in watchmaking left until the 1930s a surface condition minimizing the spread of lubricants by the presence of a film lowering the surface energy ( M. Osowiecki, 1957, "A new epilame resistant to washes", Bulletin SSC III, page 735 ). This film disappeared with the improvements made to the washing techniques, causing a more or less rapid spreading of the lubricants. In 1930, P. Woog of the Compagnie Française de Raffinage developed an anti-migration product based on stearic acid which he named "epilame". It was used in various branches of the industry until the end of the 60s. The name has remained and designates in watchmaking any product used to guarantee the resistance of lubricants on a surface.

Deposition of a compound on a functional surface to lower surface energy and control wettability and adhesion is a fairly common process. However, its application as barrier film or antimigration is limited to watchmaking ( M. Massin, "Epilames and associated lubricants with high stability: properties, application technology and results in watchmaking", Proceedings of the Franco-German Chronometry Congress, page 85, 1970 , and " Design of lubrication in micromechanics: new achievements by preparing surfaces associated with silicone fluids ", Proceedings of the Congress of the German and French Chronometry Societies, page 95, 1971 ), to the space industry ( M. Marchetti, "Global and Local Aspects of the Implementation of Fluid Lubrication in the Space Environment", PhD Thesis INSA, Lyon, 2000 ) and electronics. The first two areas have in common the difficulty of replacing a used or exhausted lubricant.

Products based on stearic acid diluted in toluene were used in watchmaking until the 1970s ( M.Osowiecki, reference above and P. Ducommun, 1956, "Synthetic clockwork oils", J. Switzerland Horl. Bij. 9-10, 117 ). Research undertaken in the late 1960s led to two important developments. On the one hand, a product based on silicone was developed (P. Massin, references above) but knew only limited success. On the other hand, products based on fluoropolymers were introduced in the course of the 1970s and are still used today. Requirement DD 238 812 A1 describes ultra-thin layers involving the implementation of silanes and perfluoroalkanes.

Currently, the vast majority of epilams available on the market, such as Moebius' Fixodrop FK-BS, or the 3M Fluorad (FC-722 and others) line, consist of a fluorinated polymer dissolved in a perfluorinated solvent.

The deposition of the compound on the substrate is carried out by soaking it in a solution of perfluorinated solvent loaded with polymer. The solvent used is generally tetradecafluorohexane (C ₆ F ₁₄ ) which, once volatilized, is a greenhouse gas since it remains stable for 3200 years in the air and has a greenhouse potential of 7400 equivalents. CO ₂ .

The object of the invention is to propose compounds that can be used as epilame and that can be attached to a solid substrate surface.

These objects are achieved by the invention as defined in the attached set of claims.

The invention indeed proposes a novel ultra-thin hydrophobic and oleophobic layer formed by self-assembly on a solid substrate surface of catechol foot compounds, and a process for preparing this ultra-thin layer which uses a non-fluorinated solvent, by for example a mixture of water and 2-propanol. Thanks to the catechol foot of the compounds used, this ultra-thin layer is firmly fixed to the surface of the solid substrate. This ultra-thin layer has satisfactory properties for use as an epilame, particularly a contact angle in advance with water and a spread of a drop of oil, quite comparable to those of the layer obtained from the reference product Fixodrop FK-BS.

1. A représente un groupe de formule
   
   dans laquelle
   • Z représente C ou N⁺,
   • X représente C-H ou C-L, L étant un groupe électroattracteur choisi parmi F, Cl, Br, I, CF₃, NO₂ et N(CH₃)₃ ⁺.
   • Y représente H ou CH₃, ou Y forme avec X un hétérocycle de 5 ou 6 atomes,
   • T représente NH, NH-CO, NH-CO-NH ou NH₂ ⁺U^-, U^-étant choisi parmi F^-, Cl^-, Br^-, I, OH^-, NO₃ ^-, HSO₄ ^-, SO₄ ^2-, CO₃ ^2-, HCO₃ ^- ou SCN^-, et
2. B représente un groupe alkyl linéaire aliphatique C₁-C₂₀ non substitué.

The catechol foot compounds have the general formula

AB

in which

1. A represents a group of formula
   
   in which
   • 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 N (CH ₃ ) ₃ ⁺ .
   • 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 chosen from F ^- , Cl ^- , Br ^- , I, OH ^- , NO ₃ ^- , HSO ₄ ^- , SO ₄ ^{2 -} , CO ₃ ^2- , HCO ₃ ^- or SCN ^- and
2. B represents an unsubstituted C ₁ -C ₂₀ aliphatic linear alkyl group.

The group A serves in particular to allow the attachment of the compounds to the surface of the solid substrate through the catechol group and the solubilization of the amphiphilic molecule A-B in the dipping solution.

Group B gives the ultra-thin layer its hydrophobic and oleophobic properties.

Interesting groups A are those selected from one of the following groups:

The compounds of formulas A-B can be obtained from known compounds using techniques and reactions well known to the organic chemist.

peut être obtenu en faisant réagir de l'octadécylisocyanate et 3-hydroxy-tyramine acide chlorhydrique en solution dans le DMF en présence de N-méthyl-morpholine.For example, 1- (3,4-dihydroxyphenethyl) -3-octadecylurea

can be obtained by reacting octadecylisocyanate and 3-hydroxy-tyramine hydrochloric acid in solution in DMF in the presence of N-methyl-morpholine.

The solid substrate on the surface of which the self-assembly is made can be any solid substrate involved in the operation of a mechanical movement, in particular consisting of a material selected from among gold, silver, silver steel, including 20AP steel, aluminum, brass, bronze, cuproberyllium, titanium dioxide, ruby, sapphire, silicon, nickel and nickel-phosphorus, as well as other surfaces metal, such as iron, chromium, tantalum, yttrium, silicon, germanium, copper, platinum, and metallic or ceramic oxides, such as zirconia and niobium (niobium oxide), this list not being limiting. As a substrate, it is also possible to use polymers such as polyethylenes, polystyrols, polyamides, polydimethylsiloxanes, polyvinyl chlorides and epoxy resins, this list not being so limiting. The substrate may also be a substrate in one of these materials or another whose surface has been coated or coated, for example by a galvanic deposition of gold, gold-copper-cadmium and gold, nickel, rhodium, tin-nickel, or treated by anodizing, as in the case of parts made of aluminum alloy or titanium, or modified by a surface treatment such as oxidation, carburization or nitriding.

The thickness of the ultra-thin layer measured in ellipsometry is 0.5 to 10 nm, which value will be higher for the definition of ultra-thin, preferably 1 to 4 nm.

To be considered as epilame, that is to say to prevent the spread of oil satisfactorily, the contact angle in advance with the water must generally be at least 100 °. Will also be considered as epilame a film whose contact angle may be substantially less than 100 °, for example between 90 and 100 °, but still prevents spreading, which remains less than 2%.

Preferably the ultra-thin layer of formula A-B remains functional as epilame after two watch washes.

The invention also relates to a timepiece characterized in that it comprises an ultra-thin layer as defined above.

The invention also relates to a process for preparing the ultra-thin layer defined above, characterized in that it comprises immersing the substrate in a solution of the compound of formula AB, for example in water, or a mixture of water and protic solvent such as, for example, 2-propanol, or a mixture of an aprotic solvent and a solvent protic such as 2-propanol.

The invention will be better understood with the aid of the following examples which have an illustrative and nonlimiting character.

Example 1 Synthesis of 1- (3,4-dihydroxyphenethyl) -3-octadecylurea (SuSoS1)

Octadecylisocyanate (668 mg, 2.26 mmol) was dripped into a solution of 3-hydroxy-tyramine hydrochloric acid (428 mg, 2.26 mmol) and N-methyl-morpholine (372 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 formed was filtered and washed with water (10 ml) and acetone (10 ml). Recrystallization from acetone (160 ml) at -20 ° C gave 870 mg of white powder.
Molecular weight: 448.68
% by weight: C 72.28; H, 7.78; N, 6.24; O 10.70 without H: C 84.375; N, 6.25; O, 9.373
¹ H 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 CH ₂ ), 2.95 (q, 2H CH ₂ ), 2.5 (m, 4H). CH ₂ ), 1.20 (m, 30H CH ₂ ), 0.86 (t, 3H CH ₃ ).

corresponding to 1- (3,4-dihydroxyphenethyl) -3-octadecylurea:

Example 2 Preparation of dipping solutions and immersion of different substrates therein Preparation of the soaking solution of SuSoS1

23.4 mg of SuSoS1 (0.052 mmol) in 80 ml of 2-propanol was dissolved in a graduated 100 ml flask. The solution was sonicated (with Sonorex super 10P 100%) until completely dissolved. Ultrapure water was added to the vial 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.

Immersion of gold, polished steel, aluminum, titanium oxide and ruby substrates in soaking solutions Experimental Protocol A

The gold, polished steel, aluminum, titania and ruby samples were cleaned in a UV / ozone chamber for 30 minutes and immersed overnight in the SuSoS1 solution. The samples were then immersed in 2-propanol for 10 seconds, rinsed with 2-propanol and dried with a stream of nitrogen. In the case of steel, the surfaces were slightly polished with a wipe impregnated with 2-propanol, rinsed with additional 2-propanol and dried with a stream of nitrogen (see Table 1A below). Or

Experimental Protocol B

The same samples were immersed for 12 hours at room temperature in a solution 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 stream of dry nitrogen (see Table 1B below).

Example 3 Analysis of ultra-thin layers formed by self-assembly on different substrates

• ellipsométrie spectroscopique à angle variable (VASE : Variable Angle Spectroscopique Ellipsometry ; cf. Feller et al. (2005). "Influence of poly(propylene sulfide-block-ethylene glycol) di-and triblock copolymer architecture on the formation of molecular adlayers on gold surfaces and their effect on protein résistance: A candidate for surface modification in biosensor research.", Macromolecules 38(25): 10503-10510 ),
• mesure d'angle de contact dynamique (dCA : Contact Angle dynamique ; cf. Tosatti et al. (2002) "Self-Assembled Monolayers of Dodecyl and Hydroxy-dodecyl Phosphates on Both Smooth and Rough Titanium and Titanium Oxide Surfaces", Langmuir 18(9): 3537-3548 ), comme suit : la mouillabilité de surface a été déterminée en mesurant les angles de contact d'avance et le recul sur une goutte (d'eau) sessile (Contact Angle Measuring System, G2/G40 2.05-D, Krüss GmbH, Hamburg, Germany); l'expérience a été conduite en automatique en augmentant et diminuant la taille de la goutte à une vitesse de 15 ml par minute ; 480 valeurs ont été mesurées pour l'angle de contact d'avance et 240 pour l'angle de contact de recul, sur 3 emplacements différents pour chaque échantillon) ; les données recueillies ont été analysées par la méthode des tangentes 2 (routine d'ajustement du programme de Drop-Shape Analysis en Version DSA 1.80.0.2 for Windows 9x/NT4/2000, (c) 1997 - 2002 KRUESS"), et
• spectrométrie spectroscopique à rayons X (XPS ; Tosatti et al. ci-dessus).

Monolayers formed by self-assembly on the different substrates were analyzed by

• variable angle spectroscopic ellipsometry (VASE: Variable Angle Spectroscopique Ellipsometry; Feller et al. (2005). "Influence of poly (propylene sulfide-block-ethylene glycol) di-and triblock copolymer architecture on the formation of molecular adlayers on their surfaces and their effect on protein resistance: A candidate for surface modification in biosensor research.", Macromolecules 38 (25 ): 10503-10510 )
• dynamic contact angle measurement (dCA: Dynamic angle contact; Tosatti et al. (2002) "Self-Assembled Monolayers of Dodecyl and Hydroxy-dodecyl Phosphates on Both Smooth and Rough Titanium and Titanium Oxide Surfaces", Langmuir 18 (9): 3537-3548 ), as follows: Surface wettability was determined by measuring contact angles in advance and recoil on a sessile (water) drop (Contact Angle Measuring System, G2 / G40 2.05-D, Krüss GmbH, Hamburg , Germany); the experiment was conducted automatically by increasing and decreasing the size of the drop at a rate of 15 ml per minute; 480 values were measured for the advance contact angle and 240 for the recoil contact angle, at 3 different locations for each sample); the data collected were analyzed by the method of tangents 2 (Drop-Shape Analysis program adjustment routine in DSA Version 1.80.0.2 for Windows 9x / NT4 / 2000, (c) 1997 - 2002 KRUESS "), and
• X-ray spectroscopic spectrometry (XPS, Tosatti et al., supra).

• des plaques de silicium recouverts d'une fine couche d'or
• des disques d'acier poli
• des disques de rubis poli
• des plaques d'aluminium
• des plaques de silicium recouverts d'une fine couche de dioxyde de titane

The different substrates used are

• silicon wafers covered with a thin layer of gold
• polished steel discs
• polished ruby discs
• aluminum plates
• silicon wafers coated with a thin layer of titanium dioxide

The main parameters measured by VASE and CA are summarized in Tables 1A and 1B below. <u> Table 1A Thickness measured by ellipsometry and advance contact angles with water (according to protocol A) </ u> substratum change Thickness measured by ellipsometry [nm] Contact angle in advance with water [°] Gold Clean - about 50 SuSoS1 1.0 93.4 ± 2.1 Polished steel Clean - <10 SuSoS1 2.7 108.5 ± 1.0 Aluminum Clean not measured <10 SuSoS1 not measured 98.8 ± 0.6 Titanium dioxide Clean - <10 SuSoS1 3.4 111.8 ± 0.7 Ruby Clean not measured <10 SuSoS1 not measured - substratum change Thickness measured by ellipsometry [nm] Contact angle in advance with water [°] Gold Clean - about 50 SuSoS1 not measured 108 ± 4 Polished steel Clean - <10 SuSoS1 not measured 107 ± 1 Aluminum Clean not measured <10 SuSoS1 not measured 105 ± 2 Titanium dioxide Clean - <10 SuSoS1 2.9 112 ± 3 Ruby Clean not measured <10 SuSoS1 not measured 106 ± 1

X-ray photoelectron spectroscopy (XPS) analysis shows that SuSoS1 molecules are present on all surfaces by the detection of N elements.

These results show that we obtain on all substrates tested an ultra-thin layer of SuSoS1.

Advantageous contact angle values with water are satisfactory for use as epilam (greater than 100 ° or slightly less than this value, but with smears less than 2% (as will be discussed later).

EXAMPLE 4 Comparison of the ultra-thin layers formed by self-assembly of SuSoS1 and Fixodrop FK-BS on surfaces of gold, polished steel and ruby. 1) Preparation of the ultra-thin layers of SuSoS1 and Fixodrop on the surfaces of the different substrates

An ultra-thin layer of SuSoS1 is coated with substrates of gold, polished steel and ruby as described in Example 2. The surface appearance is excellent and no markings can be distinguished due to the deposit .

An ultra-thin layer of Fixodrop FK-BS is coated with gold, polished steel and ruby substrates as specified by the manufacturer by dipping the substrates in a solution of tetradecafluorohexane.

The thickness of this layer measured by ellipsometry on gold is 1.0 nm for SuSoS1 and 1.7 nm for Fixodrop.

2) Flow measurement of lubricants

The spreading of the lubricants on a surface is characterized by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after the drop has been deposited and after 20 minutes. The spread corresponds to the relative variation of the average diameter after 20 minutes. A good performance of a lubricant corresponds to a spread of 2% or less. Spreading greater than 10% is noticeable in the eye and is not acceptable. The oil used for the tests is a watch oil "941" (Moebius and Fils house, mixture of alkyl-aryl-monooleate and two C ₁₀ -C ₁₃ di-esters, viscosity of 110 cSt at 20 ° C, surface tension of 32.8 mN / m).

The spread obtained is compared on surfaces of steel, ruby, aluminum, titanium dioxide, and gold coated with the SuSoS1 molecule, as well as a gold surface coated with the commercial product Fixodrop FK -BS of the Moebius and Son house as indicated by the manufacturer. For the SuSoS1 molecule, the spread is in all cases less than 2%, and is comparable to that measured for the Fixodrop, as shown in the table below. <u> Table 2 Spreading Lubricants </ u> Area Ultra thin layer Moebius 941 Oil Steel SuSoS1 -0.04% Aluminum SuSoS1 + 1.29% Titanium dioxide SuSoS1 + 0.23% Ruby SuSoS1 -0.97% Gold SuSoS1 + 0.09% Gold Fixodrop FK-BS -0.90%

3) Conclusion

For all the surfaces studied, the contact angle obtained on the ultra-thin layers made with the molecule SuSoS1 is greater than 100 °, the surface energy is less than 20 mJ m ^-2 , and the spread is less than 2%.

The layers are resistant to ruby, aluminum and titanium dioxide washings, but less well to gold and steel.

The properties of the ultra-thin layer SuSoS1 are at least as good as those obtained with the commercial product Fixodrop.

Claims (10)

1. An ultra-thin hydrophobic and oleophobic layer, of which the thickness measured in ellipsometry is 0.5 to 10 nm, formed by self-assembly on a solid substrate surface, of compounds of the general formula
   
           A-B
   
   in which

   A represents a group of the formula

   

   in which

   Z represents C or N⁺,

   X represents C-H or C-L, L being an electron-attracting group selected from F, Cl, Br, I, CF₃, NO₂ and N(CH₃)₃ ⁺,

   Y represents H or CH₃, or Y forms a 5- or 6-atom heterocycle with X,

   T represents NH, CO, NH-CO, NH-CO-NH or NH₂ ⁺U^-, U^- being selected from F^-, Cl^-, Br^-, I^-, OH^-, NO₃ ^-, HSO₄ ^-, SO₄ ^2-, CO₃ ^2-, HCO₃ ^- or SCN^-, and

   B represents an unsubstituted C₁-C₂₀ linear aliphatic alkyl group.
2. An ultra-thin layer as claimed in one of the preceding claims, wherein A is selected from one of the following groups:

   

   

   
3. An ultra-thin layer as claimed in one of the preceding claims characterised by a compound of the following formula:

   
4. An ultra-thin layer as claimed in one of the preceding claims, wherein the solid substrate is composed of a material selected from gold, silver, steel, aluminium, brass, bronze, copper-beryllium, titanium dioxide, ruby, sapphire, silicon, nickel and nickel phosphorus, as well as other metallic surfaces such as iron, chromium, tantalum, yttrium, germanium, copper, platinum, and metal oxides or ceramics, such as zirconia or niobia (niobium oxide), or polymers such as polyethylenes, polystyrenes, polyamides, polydimethylsiloxanes, polyvinyl chlorides, epoxy resins, or 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.
5. An ultra-thin layer as claimed in one of the preceding claims, wherein its advancing contact angle with water is at least 100°.
6. A timepiece, wherein it comprises an ultra-thin layer as claimed in one of the preceding claims.
7. A method of preparing an ultra-thin layer as claimed in one of claims 1 to 5, wherein it comprises the immersion of the substrate in a solution of the compound of formula A-B in water or a mixture of water and protic solvent.
8. A method as claimed in claim 7, wherein the protic solvent is 2-propanol.
9. A method of preparing an ultra-thin layer as claimed in one of claims 1 to 5, wherein it comprises the immersion of the substrate in a solution of the compound of formula A-B in a mixture of aprotic solvent and protic solvent.
10. Use of an ultra-thin layer as claimed in one of claims 1 to 5 as an epilame.