Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
• • 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
  • C10M105/02—Well-defined hydrocarbons
  • C10M105/04—Well-defined hydrocarbons aliphatic
• • 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
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
• • 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
  • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
  • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
  • C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B31/00—Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
  • G04B31/08—Lubrication
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/081—Thiols; Sulfides; Polysulfides; Mercaptals 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
  • C10M2223/0603—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/015—Dispersions of solid lubricants
  • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
• • 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
  • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

Definitions

• the present invention describes the highly advantageous properties of a mixture of thiol-perfluoropolyether molecules (PFPE) with perfluorinated bisphosphonic compounds (BP-PF).
• PFPE thiol-perfluoropolyether molecules
• BP-PF perfluorinated bisphosphonic compounds
• the epilamage of watchmaking mechanisms is a surface treatment which makes it possible to avoid the spreading of watchmaking lubricants (such as oils or greases) onto watch components (metal, ceramic and / or semiconducting surfaces). More generally, it is a question of increasing the lipophobicity, ie of reducing the surface energy of the surfaces with respect to the oils or fats, covering said surfaces for example with a monolayer consisting of alkyl-thiol or a fluoropolymer [Bonard J.-M., CIC 2004, pp. 131].
• the thiol molecules having the general formula H (CH 2 ) n SH can form layers self-assembled on gold (Bain CD et al., J. Am Chem Soc 1989), because the sulfur atoms bind to the metal surface while the alkyl chains point to the other side, aligning and arranging themselves in a uniform geometric pattern on the surface (resulting in the formation of "self-assembled" monolayers). These monolayers have on their surface alkyl molecules which give them a certain hydrophobicity. However, a major disadvantage to using such molecules is their odor. In addition, self-assembled layers consisting of perfluoroalkyl thiols often exhibit low temperature resistance and low resistance to oxidizing and reducing agents (Shi C. et al, J.
• the solvents used for the deposition of these molecules are conventional industrial organic solvents such as alcoholic solvents, aldehydes, ketones, ethers, etc. These compounds are capable of self-assembling monolayers on metallic materials such as iron, titanium, copper, aluminum, nickel, tin, or alloy metals (eg, steel, aluminum, stainless steel, brass, nickel silver, bronze, tin-nickel, nickel-phosphorus, copper-berylium).
• metallic materials such as iron, titanium, copper, aluminum, nickel, tin, or alloy metals (eg, steel, aluminum, stainless steel, brass, nickel silver, bronze, tin-nickel, nickel-phosphorus, copper-berylium).
• the present inventors have therefore developed for the first time an easy-to-use composition (ie containing an organic solvent, non-fluorinated), making it possible to effectively and durably avoid the spread of watch lubricants on surfaces made of any size.
• an easy-to-use composition ie containing an organic solvent, non-fluorinated
• metal including gold
• a ceramic material or a semiconductor material which metal (including gold), a ceramic material or a semiconductor material.
• the composition of the invention increases the lipophobicity of the treated surfaces vis-à-vis the lubricants conventionally used in the watch industry, while giving the treated surface a very good resistance to the products used for cleaning the watch components .
• the invention relates to the use, for increasing the lipophobicity of a surface intended for watchmaking or jewelery, of a composition comprising at least one thiol compound and at least one bisphosphonic compound or one of their salts, characterized in that said thiol compound is of formula:
• A is a group (CH 2 ) m - X-, m being an integer from 0 to 100, and X being a saturated or unsaturated, perfluorinated or partially fluorinated C 1 -C 10 alkyl group, the alkyl chain may be substituted or interrupted 0 to 10 cycloalkyl or aryl groups which can be perfluorinated or not;
• C is selected from: F (CF (CF 3 ) CF 2 O) n CF (CF 3 ) -,
• R is a hydrogen atom H or an OH group
• A is a group (CH 2 ) m - X-, where m is an integer between 0 and 100, X being a saturated or unsaturated, perfluorinated or partially fluorinated C 1 -C 10 alkyl group, the alkyl chain may be substituted or interrupted by 0 to 10 cycloalkyl or aryl groups which may or may not be perfluorinated;
• C is selected from: (CF (CF 3 ) CF 2 0) n CF (CF 3 ) -,
• n and p are integers between 1 and 100.
• This composition makes it possible to limit the spreading of greasy lubricants (oils or greases) and / or to increase the epilame effect on surfaces intended for the watchmaking or jewelery industry, for example any surface made up of more than 50% of :
• noble metals selected from gold, platinum, silver and copper; oxidized metals selected from iron, titanium, aluminum, nickel, ruthenium, rhodium and tin,
• alloys selected from steel, stainless steel, brass, nickel silver, bronze, tin-nickel, nickel-phosphorus, copper-berylium, palladium-nickel, copper-cobalt, or alloys comprising vanadium, chromium, manganese, zinc, tungsten, or zirconium, or an amorphous crystalline alloy, or
• said thiol compound is a thiol-perfluorinated compound of the following formula I:
• n is an integer of 1 to 100
• m is an integer of from 100 to 100
• x is an integer of 1 to 10 and said bisphosphonic compound is a perfluorinated bisphosphonic compound of the following formula II:
• n is an integer from 1 to 100
• m is an integer from 1 to 100
• x is an integer from 1 to 10.
• said bisphosphonic compounds and said thiol compounds are dissolved in an organic solvent selected from alcoholic solvents, particularly C 1 -C 6 alcohols, such as isopropanol. , ethanol, methanol, aldehydes, ketones such as acetone, ethers such as diethyl ether or tetrahydrofuran or alkanes, especially C 1 -C 8 alkanes, and mixtures thereof.
• the present invention is also a process for covering a surface intended for the watch or jewelery industry by a functionalization molecular layer, characterized in that it comprises at least the following stages:
• composition of the invention up to self-assembly of the thiol and / or bisphosphonic compounds in a monolayer covering said surface
• the present invention aims at the use of a functionalized surface obtained from the process defined above in mechanical parts intended for the watch or jewelery industry.
• the present invention aims at the use, for increasing the lipophobicity of a surface intended for the watch-making or the jewelery industry, or for increasing the epilam effect on a surface, of a composition containing the thiol compound of formula 1.3 ( as the only active agent):
• said surface is a metal surface consisting of more than 50% of a noble metal selected from gold, silver, copper and the compound of formula 1.3. is solubilized in isopropanol or in a solvent composed of hydrotreated naphthas.
• FIG. 1 shows thiols-PF (1.5) and thiols-PFPE (1.1 to 1.4 and 1.6) compounds of formula I according to the invention.
• FIG. 2 shows examples of BP-PF and BP-PFPE molecules of formula II according to the invention. Detailed description of invention
• a covering composition comprising i) thiol compounds, mixed with ii) bisphosphonic compounds, makes it possible to cover a large number of surfaces of watch components, including those made of gold, silver or their alloys. , silicon or glass, and to increase very effectively and durably the epilame effect of watch lubricants conventionally used on these surfaces.
• the monolayers formed as a result of the covering of the surfaces with the composition of the invention produce a very important epilam effect.
• this covering composition does not comprise a perfluorinated solvent.
• the present invention relates to the use of a covering composition, referred to herein as a "covering composition of the invention", comprising at least one thiol compound and at least one bisphosphonic compound, or one of their salts, to increase the lipophobicity of a surface intended for watchmaking or jewelery, in order to limit the spreading of fatty lubricants and thereby increase the epilame effect on these surfaces.
• the thiol compounds present in the coating composition of the present invention are of formula:
• A is a group (CH 2 ) m - X-, m being an integer from 0 to 100, and X being a saturated or unsaturated, perfluorinated or partially fluorinated C 1 -C 10 alkyl group, the alkyl chain may be substituted or interrupted 0 to 10 cycloalkyl or aryl groups which can be perfluorinated or not;
• B is a) a simple chemical bond, or an O, S atom, or a
• C is selected from: F (CF (CF 3 ) CF 2 O) n CF (CF 3 ) -,
• the bisphosphonic compound present in the covering composition of the present invention has the formula:
• R is a hydrogen atom H or an OH group
• A is a group (CH 2 ) m - X-, where m is an integer between 0 and 100, X being a saturated or unsaturated, perfluorinated or partially fluorinated C 1 -C 10 alkyl group, the alkyl chain may be substituted or interrupted by 0 to 10 groupings
• C is selected from: (CF (CF 3 ) CF 2 0) n CF (CF 3 ) -,
• C 1 -C 10 alkyl group is meant, in the sense of the present invention, a linear or branched saturated divalent hydrocarbon chain, comprising 0 at 100, preferably 1 to 10, carbon atoms.
• methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, pentylene or hexylene groups By “perfluorinated” is meant a molecule substituted with at least one CF3 (CF2) n group , n being preferably between 0 and 50, more preferably between 0 and 10.
• cycloalkyl is meant, in the sense of the present invention, a cyclic saturated hydrocarbon chain, preferably having between 3 and 7 ring carbon atoms.
• aryl means an aromatic group, preferably comprising from 6 to 10 carbon atoms, and comprising one or more contiguous rings, for example a phenyl or naphthyl group.
• aryl is an aromatic group, preferably comprising from 6 to 10 carbon atoms, and comprising one or more contiguous rings, for example a phenyl or naphthyl group.
• it is phenyl.
• Possible salts include, in particular, sodium or potassium salts, calcium or magnesium salts, or salts formed by suitable organic ligands such as quaternary ammonium salts.
• the salts are therefore preferably chosen from sodium, potassium, magnesium, calcium and ammonium salts.
• the thiol compound present in the covering composition of the invention is a perfluorinated thiol of the following formula I:
• n is an integer of 1 to 100
• m is an integer of 1 to 100
• x is an integer of 1 to 10, or a salt thereof, preferably the potassium salt, sodium, magnesium, calcium, or ammonium.
• n is between 1 and 20, and even more preferably between 1 and 10; preferably, m is between 1 and 20, and even more preferably between 1 and 10; preferably, x is between 1 and 5; more preferably, x is 1.
• the bisphosphonic compound present in the covering composition of the invention is a perfluorinated bisphosphonic compound of the following formula II:
• n is an integer of 1 to 100
• m is an integer of 1 to 100
• x is an integer of 1 to 10, or a salt thereof, preferably the potassium salt, sodium, magnesium, calcium, or ammonium.
• n is between 1 and 20, and even more preferably between 1 and 10; preferably, m is between 1 and 20, and even more preferably between 1 and 10; preferably, x is between 1 and 5; more preferably, x is 1.
• the bisphosphonates present in the covering composition of the invention therefore carry a grouping. perfluorinated (BP-PF) or perfluoropolyether (BP-PFPE) as described in the patent application No. FR2904784 and EP 2,054,165.
• BP-PF perfluorinated
• BP-PFPE perfluoropolyether
• These molecules are capable, because of the multiplicity of phosphonate groups (-PO3H 2 ), permanently grafted into self-assembled monolayers on mineral or metallic surfaces.
• the physicochemical characterization of the monolayer obtained from these molecules is described in detail in the article by Lecollinet et al. (Langmuir, 2009).
• the bisphosphonate molecules are fixed in self-assembled monolayers on metal or mineral materials, preferentially oxidized such as iron, titanium, copper, aluminum, nickel, tin or alloy metals (eg steel , stainless steel, brass, nickel silver, bronze, tin-nickel, nickel-phosphorus, copper-berylium), ruby, or sapphire.
• metal or mineral materials preferentially oxidized such as iron, titanium, copper, aluminum, nickel, tin or alloy metals (eg steel , stainless steel, brass, nickel silver, bronze, tin-nickel, nickel-phosphorus, copper-berylium), ruby, or sapphire.
• the reduction of the surface energy of the treated material is then important (surface energy ⁇ 20 mJ / m 2 ).
• the covering composition of the invention is used to limit the spreading of substances such as lubricants on metal, ceramic or semiconductor surfaces intended for watchmaking or jewelery.
• lubricant is meant, within the meaning of the present invention, oils or greases, in particular oils (or base oils in the case of greases) having a kinematic viscosity measured at 20 ° C between 10 and 2000 mm 2 / s, and a surface tension measured at 20 ° C between 25 and 40 mN / r.
• said covering composition makes it possible to increase the epilame effect on a surface intended for watchmaking or jewelery.
• the coating composition may be liquid, gaseous or supercritical.
• the coating composition of the invention may be an aqueous or organic composition.
• the solvent of the liquid composition is chosen so as to allow the solubilization of the two types of compounds present in the composition.
• This organic solvent may be chosen from alcoholic solvents, in particular C 1 -C 6 alcohols, such as isopropanol, ethanol, methanol, aldehydes, ketones such as acetone, ethers such as diethyl ether or tetrahydrofuran or alkanes, especially C 1 -C 8 alkanes, and their mixtures.
• the composition may be gaseous, the compounds BP and thiols may in particular be in the vapor state.
• “supercritical composition” is meant a composition which is in a supercritical fluid state.
• the coating composition of the invention is advantageously in the form of a solution, a suspension, an emulsion, a supercritical fluid, an aerosol or a foam.
• the content of bisphosphonic compounds in the liquid coating composition is advantageously between 0.0001 and 20% by weight, preferably between 0.001 and 5% by weight, and the content of thiol compounds in the liquid coating composition is advantageously between 0.0001 and 20% by weight, preferably between 0.001 and 5% by weight
• the thiol and BP compounds are incorporated in the coating composition of the invention at a molar concentration of between 10 -1 and 10-15 mol / L of each compound, preferably between 10 -3 and 10 "5 mol / L.
• the two compounds, thiol and bi sphosphonate have the same concentration.
• the surface of the watch component is made up of more than 50%, preferably more than 75%, even more preferably 85%:
• noble metals selected from gold (Au), platinum (Pt), silver (Ag) and copper (Cu),
• oxidized metals selected from iron (Fe), titanium (Ti), aluminum (Al), nickel (Ni), ruthenium (Ru), rhodium (Rh) and tin (Sn),
• alloys selected from steel (alloy of iron and carbon), stainless steel, brass (alloy of copper and zinc), nickel silver (alloy of copper, nickel, and zinc), bronze (copper alloy and tin), tin-nickel (Sn-Ni), nickel-phosphorus (Ni-P), copper-berylium (Cu-Be), palladium-nickel (Pd-Ni), copper-cobalt (Cu-Co) , or alloys comprising vanadium (V), chromium (Cr), manganese (Mn), zinc (Zn), tungsten (W), or zirconium (Zr), or an amorphous crystalline alloy, or
• ruby alloy of aluminum oxide and Chromium, CAS No. 12174-49-1
• sapphire aluminum oxide, CAS No. 1317-82-4
• zirconia zirconia, silica or alumina or
• semiconductors such as silicon (Si) or germanium (Ge), as well as their oxides, or diamond.
• an alloy is said to be "amorphous" when the atoms respect no order at medium and great distances (unlike crystallized compounds). Glasses and elastomers are amorphous compounds.
• the ceramics are of crystalline or partially crystalline structure, or glass, and formed of substantially inorganic and non-metallic substances, by a melt which solidifies on cooling, or which is formed and brought to maturity, at the same time or later, by the action of heat. It may be ceramics of oxides (aluminum oxides, zirconium), non-oxide ceramics (carbides, borides, nitrides, ceramics composed of silicon and atoms such as tungsten, magnesium, platinum, or titanium); or finally composite ceramics (combination of oxides and non-oxides, such as ruby).
• oxides aluminum oxides, zirconium
• non-oxide ceramics carbides, borides, nitrides, ceramics composed of silicon and atoms such as tungsten, magnesium, platinum, or titanium
• composite ceramics combination of oxides and non-oxides, such as ruby.
• the covering composition of the invention contains a thiol-perfluorinated compound of formula I as defined above, and a perfluorinated bisphosphonic compound of formula II as defined above.
• This mixture indeed demonstrates the best epilame effect (see examples below).
• the solvent of the liquid covering composition of the invention is chosen so as to allow the solubilization of the two types of compounds it contains.
• This solvent may be chosen from alcoholic solvents, in particular C 1 -C 6 alcohols, such as isopropanol, ethanol, methanol, aldehydes, ketones such as acetone and ethers such as diethyl ether. or tetrahydrofuran or alkanes, in particular alkanes to C 8 and mixtures thereof. Even more preferably, the solvent is isopropyl alcohol (IPA) (or isopropanol).
• IPA isopropyl alcohol
• the present invention relates to a process for covering a surface intended for the watch or jewelery industry by a functionalization molecular layer, characterized in that it comprises at least the following steps:
• the term "molecular functionalization layer” means a layer composed of molecules which are each anchored to the substrate by at least one of their terminations and arranged next to each other.
• the molecules are anchored to the substrate preferably by their thiol or bisphosphonic termini and are not covalently bonded to one another. Their organization on the surface and the different chemical groups they present make it possible to modify the chemical or physical properties of the surfaces thus covered.
• the thickness of the molecular layer obtained according to the method which is the subject of the present invention is advantageously of the order of one nanometer, that is to say between 0.1 nm and 50 nm.
• hydroxylated substrate means a substrate whose surface has -OH functions in the X-OH form (X being a constituent element of the surface). The more the surface of the substrate has -OH functions and the greater the density of gembisphosphonic compounds attached to this surface will be important.
• prior oxidation of the surface of the substrate so as to have a sufficient number of hydroxyl functions on the surface of the substrate (step b).
• the prior oxidation of the surface of the substrate will be done so as to have sufficient hydroxyl functions on the surface of the substrate to allow the attachment of bisphosphonic compounds, when said substrate is practically not provided or very little . It can also be done when it is desired to increase the number of hydroxyl functions already present, in order to obtain a greater coverage of the surface by the bisphosphonic compounds. It is for example advantageous to carry out this oxidation step on a surface essentially comprising silicon.
• the surface is brought into contact with a liquid covering composition containing the BP and thiol compounds until self-assembly of said compounds into a layer covering said surface (step c).
• the contacting time of the composition on the surface to be treated is between 10 seconds and 6 hours, preferably between 1 minute and 1 hour, even more preferably between 3 minutes and 30 minutes.
• the contacting of the liquid covering composition with the surface of the substrate is advantageously carried out by dipping, by spin-coating, by wiping, by spraying, by aerosol or by spraying.
• the covering composition is gaseous or supercritical, the contacting with the surface of the substrate can be carried out using a reactor whose pressure and temperature are controllable and which allows the injection of a gas such that the C0 2 .
• the covering composition (step d) is removed so as to eliminate from the surface the solvent and all the thiol and bisphosphonic solutes which did not attach to the substrate during contacting.
• the removal of the covering composition can be carried out by rinsing, or mechanically by draining, centrifugation or evaporation.
• the surface may be further rinsed including immersion in a suitable solvent, to ensure complete removal of unfixed solute.
• Said suitable solvent is preferably that used to prepare the solution.
• the method which is the subject of the present invention allows the covalent grafting of BPs and / or thiols on oxidized or ceramic metal surfaces (step e) possibly using dehydration techniques by heating under reduced pressure or otherwise which makes it possible to transform a electrostatic interaction in a POX covalent bond (X being a constituent element of the surface). It is advantageous to carry out this dehydration step on ruby, for example.
• the dehydration step of the surface is carried out thermally, advantageously under reduced pressure, in particular by means of a lyophilizer. More particularly, the dehydration of the surface of the substrate can be carried out by heating it at a temperature of between 20 ° C. and 150 ° C., preferably at about 50 ° C., at a pressure of between 0.01 mbar and 1 bar, preferably at 0.3 mbar, for a time of between 1 and 72 hours, preferably for about 15 hours. It is also possible to dehydrate the surface at atmospheric pressure for 15 hours at 120 ° C.
• the surface is rinsed (step f) in particular by immersion in a suitable solvent, to ensure complete elimination of the unfixed solute.
• This step can be performed using ultrasound.
• Said suitable solvent is preferably that used to prepare the solution.
• Steps e) and f) can be reversed, the rinsing taking place before dehydration of the coated surface.
• the surface can be dried (step g) under hot air flow, for example at 70 ° C for 2 minutes. Steps c) to f) of the recovery method of the invention can be iterated, which can improve the recovery efficiency.
• the method which is the subject of the present invention makes it possible to cover surfaces of watch components made up of more than 50%, preferably more than 75%, even more preferably 85%:
• noble metals selected from gold (Au), platinum (Pt), silver (Ag) and copper (Cu),
• oxidized metals selected from iron (Fe), titanium (Ti), aluminum (Al), nickel (Ni), ruthenium (Ru), rhodium (Rh) and tin (Sn), - alloys selected from steel (alloy of iron and carbon), stainless steel, brass (copper and zinc alloy), nickel silver (alloy of copper, nickel, and zinc), bronze (copper alloy and tin), tin-nickel (Sn-Ni), nickel-phosphorus (Ni-P), copper-berylium (Cu-Be), palladium-nickel (Pd-Ni), copper-cobalt (Cu-Co) , or alloys comprising vanadium (V), chromium (Cr), manganese (Mn), zinc (Zn), tungsten (W), or zirconium (Zr), or a structural alloy amorphous crystalline, or - ceramics or glasses such as ruby (alloy of aluminum oxide and chromium), sapphire (aluminum oxide), zir
• semiconductors such as silicon (Si) or germanium (Ge), as well as their oxides, or diamond.
• the surface is made of gold, steel, silicon, Ni, NiP, ruby or SnNi.
• the present invention relates to the use of a functionalised surface by the method of the invention in mechanical parts for the watch industry or jewelry.
• These mechanical parts are for example wheels, axes, gables, stones, anchors, lifts, springs, drums and barrel lids or blanks.
• compositions comprising an effective amount of the thiol and bisphosphonic compounds, preferably of formula (I) and (II), or of their toxicologically acceptable salts, capable of being fixed permanently on the surfaces of watch components to be protected and able to increase:
• said watch lubricant is an oil or a grease.
• the oils, or the base oils of greases, conventionally used in watchmaking have a kinematic viscosity measured at 20 ° C of between 10 and 2000 mm 2 / s and a surface tension measured at 20 ° C of between 25 and 40 mN / m. , such as 941 exhaust oil, SYNT-HP1300 high-pressure oil, SAL9040 high-speed oil (references from Moebius AG).
• the epilame effect is typically evaluated by measuring the contact angle of the watch lubricant or test liquid (water, CESN test liquids) on the surface of the component.
• composition of the invention must be such that this contact angle with a watch oil must be greater than 30 °, preferably 35 °, even more preferably 40 °, because a this angle corresponds to a very high efficiency of epilamization (see Renaud 1956, Osowiecki 1962 and Massin 1971).
• the present invention thus relates to the use of the coating composition of the invention to obtain a contact angle between a watch oil and the coated surface of at least 30 °.
• the covering composition of the invention makes it possible to increase the epilame effect towards horological oils exhibiting a viscosity of between 50 and 2000 mm 2 / s.
• an effective amount is meant that the amount of compound applied allows, after recovery, to form a monomolecular film increasing the epilame effect on the surfaces of watch components.
• the present invention relates to a cover composition
• the present invention therefore also relates to the use of a composition containing, as only active ingredient of recovery, the thiol compound of formula 1.3: to increase the lipophobicity of a surface intended for watchmaking or jewelery, and thus the epilame effect on such a surface.
• said surface consists of more than 50% gold, silver, or copper.
• This covering composition may be an aqueous or organic composition comprising an organic solvent chosen from alcoholic solvents, in particular C 1 -C 6 alcohols, such as isopropanol, ethanol, methanol, aldehydes and ketones. acetone, ethers such as diethyl ether or tetrahydrofuran or alkanes, especially C 1 -C 8 alkanes, and mixtures thereof.
• the solvent may also be composed of hydrotreated naphthas (for example the Biosane T212 solvent of the MMCC mark).
• the solvent is isopropanol and / or composed of hydrotreated naphthas.
• Compound 1.3 (identified in FIG. 1) may be prepared in four steps according to the synthesis scheme shown below.
• 6-aminohexan-1-ol 3.5 g, 29.7 mmol, 3 eq
• THF tetrahydrofuran
• methyl ester 1 10 g, 9.9 mmol
• the biphasic mixture is heated at 50 ° C until complete dissolution of the perfluorinated derivative (about 20 min) and then stirred at room temperature under argon for 17 hours.
• the syrup obtained is taken up in AcOEt (120 ml), washed with a 0.5 N hydrochloric acid solution (40 ml), then with distilled water (40 ml) and finally with brine (30 ml). ). The organic phase is dried (MgSO 4), filtered and then concentrated under vacuum (rotavapor then pallet pump). Amide 2 is obtained in the form of a colorless oil.
• the organic phase is dried (MgSO 4), filtered and then concentrated under vacuum (rotavapor).
• the colorless oil obtained (mesylate) is dissolved in 150 mL of EtOH, the solution is supplemented with potassium thioacetate KSAc (2.14 g, 2 eq.) And then heated under argon at 60 ° C. for 2 h. After cooling to room temperature, the mixture is concentrated in a rotary evaporator, the residue is taken up in AcOEt (120 ml) and then washed with distilled water (2 ⁇ 50 ml) and finally with brine (40 ml). The organic phase is dried (MgSO 4), filtered and then concentrated under vacuum (rotavapor). Thioacetate 3 is obtained in the form of an orange oil.
• the molecule II.1 can be prepared in four stages according to the following synthesis scheme:
• 6-aminohexan-1-ol is acylated with the methyl ester PFPE 1 in THF at room temperature to yield the corresponding amide 2.
• the alcohol function is then oxidized to carboxylic acid 3 by the action of Jones' reagent.
• compound 3 is converted to bisphosphonic acid IL1 via an acid chloride.
• Alcohol 2 (3.1 g, 3.3 mmol) is dissolved in 40 mL of acetone. A 2.67M solution of Jones reagent is added dropwise. After stirring for 15 minutes at room temperature, a few drops of isopropanol are added and the mixture is then filtered, concentrated, taken up in AcOEt and washed twice with water. The organic phase is dried, filtered and then concentrated under vacuum (rotavapor then pallet pump). The carboxylic acid 3 is obtained in the form of a colorless oil. Carboxylic acid 3 (3.1 g, 3.3 mmol) is mixed under argon with 8 ml of thionyl chloride. The mixture is then refluxed for 45 minutes and then concentrated in vacuo.
• the syrup obtained is placed under argon and then added P (OSiMe3) 3 (2.5 eq, 2.75 mL).
• the solution obtained is stirred under argon for 2 h, concentrated under vacuum and then added with 10 mL of methanol. After stirring, the mixture is concentrated.
• the syrup obtained is washed with water. Molecule II.1 is then dried at the paddle pump.
• BP-PFPE compounds are easily obtained according to a similar mode of synthesis, using the following compounds: perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-pentaoxaoctadecanoate methyl to obtain the compound II.2.
• the part that received the deposit is placed in an oven at 120 ° C for a period ranging from 6 to 15h (only for ruby and silicon),
• the solubilization of the molecules was carried out in the concentrations of use, namely between 10 -3 and 10 -5 M.
• the dissolution of the compounds was initially carried out with magnetic stirring and at ambient temperature in isopropanol (IPA) to obtain a solution S.
• This solution S was then diluted to 5% in the solvent in such a way that to obtain a final solution having concentrations between 10 "3 and 10 " 5 M.
• solubility of the thiol-bisphosphonate mixture can be varied according to the chain length of the molecules, their respective concentrations and the nature of the solvent used. All mixtures are soluble in ⁇ .
• the lipophobic effect was evaluated by measuring the contact angles of a surface tension test oil of 33 mN / m on the different surfaces. All surfaces showed a satisfactory epilame effect.
• the contact angles measured on drops of water, glycerol and diiodomethane on different materials before and after epilamization, made it possible to calculate the surface energies according to Owens Wendt's method.
• the two compounds of the invention 1.1 and II.1 were mixed either with 10 -3 M or 10 -4 M in the IPA and the contact with the gold lasted 0, 10, 30, 60 or 360 minutes.
• Table 5 contact angles of the test oil with the epilamated parts by means of a solution according to the invention (containing 10 -3 M of the compound 1.1 and 10 -3 M of the compound IL 1 or 10 -4 M of the compound 1.1 and 10 -4 M of the compound II.1) as a function of the recovery time (0, 10, 30, 60 and 360 minutes).
• mixture No. 1 comprising a mixture of 50% of the molecule 1.3 (at 10 -3 M) and 50% of bisphosphonate II.1 (at 10 -3 M).
• the proportion of each of the molecules in the mixture has some influence on the quality of the surface treatment, but all the mixtures and the different thiol and BP molecules tested make it possible to obtain a self-assembled layer with the properties of oleophobicity required for an application. watchmaking.
• the 1.3 molecule was chosen for the rest of the study, since the contact angles obtained for this molecule are the highest. Nevertheless, the other molecules also make it possible to obtain functional layers with a satisfactory epilame effect.
• results obtained are presented in the form of a contact angle of a drop of water, respectively a drop of a test oil, on different materials.
• Table 6 contact angles of water drops, respectively of test oil, with pieces of gilded brass (Au), ruby, AP steel, NiP and SnNi coating as a function of the soaking time in an epilame solution according to the invention (mixture of compounds 1.3 and II.1 at 10 -3 M).
• the resistance of the epilame layers of the invention was evaluated after 1 or more wash cycles by measuring the contact angles with H 2 0 and the test oil. Good resistance of epilame to the different materials evaluated was observed, even for several washing cycles.
• the molecule 1.3 corresponds to the molecule studied in Examples 1 and 3 above.
• the molecule 13-402 (1.6) has a longer aliphatic group.
• the following bisphosphonate molecules were tested II.1:
• Table 8 contact angle of gilded brass and steel parts with water and test oil, for cover molecules used at 10 "3 M in ⁇ .
• the standard deviations on three measurements are between 1 ° and 5 °. It is noted that the two types of molecules make it possible to functionally validate gilded substrates, but that thiols alone do not bind (or little) on steel.
• the tested mixtures are six in number; for mixture 1 (I.3 / II.1), reference should be made to Example 6 above.
• Table 9 epilame solutions according to the invention tested in the context of Example 9 (mixture of thiol compounds 1.3 and 1.6 with compounds bis spphhoosspphhonates II, II.2 and IL 5 at 10 "3 M and 10 " 4 M in IPA)
• the solubility was qualified by observation of the clarity of the solutions at the time of their mixing in isopropanol after 1 h and 24h.
• the concentrations tested are 10 -3 M and 10 -4 M for each of the molecules. In all these configurations, no loss of solubility has been demonstrated.
• the following table details the results obtained
• Table 10 contact angle of drops of water, respectively test oil, with gilded brass, steel and ruby parts coated by dipping in an epilame solution according to the invention (mixtures 1 and 4 to 8, according to Table 9, at 10 "3 M in ⁇ , soaking time of 5 minutes, repeated treatment twice)

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