EP2655577B1 - Zusammensetzung zur erhöhung der lipophobie einer komponente zur uhrherstellung - Google Patents

Zusammensetzung zur erhöhung der lipophobie einer komponente zur uhrherstellung Download PDF

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Publication number
EP2655577B1
EP2655577B1 EP11807913.6A EP11807913A EP2655577B1 EP 2655577 B1 EP2655577 B1 EP 2655577B1 EP 11807913 A EP11807913 A EP 11807913A EP 2655577 B1 EP2655577 B1 EP 2655577B1
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Prior art keywords
compound
nickel
thiol
perfluorinated
copper
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English (en)
French (fr)
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EP2655577A1 (de
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David Portet
Grégory LECOLLINET
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Rolex SA
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Rolex SA
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    • 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 Proceedings 2004, pp. 131 ].
  • Thiol molecules having the general formula H (CH 2 ) n SH can form layers self-assembled on gold ( Bath 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 organizing into 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.
  • a major disadvantage to using such molecules is their odor.
  • the self-assembled layers consisting of perfluoroalkyl thiols often have a low temperature resistance and a low resistance to oxidizing and reducing agents ( Shi C. et al., J. Supercriti. Fluids 2000 ).
  • the present inventors have therefore sought to develop an easy-to-use composition for effectively and durably increasing the epilame effect on surfaces of watch components.
  • This composition does not contain ideally fluorinated or perfluorinated solvent.
  • bisphosphonate compounds in particular bisphosphonic compounds bearing a perfluorinated group (BP-PF) or perfluoropolyether (BP-PFPE), modify the wettability properties and render the surfaces hydrophobic and lipophobic. They cover ( FR 2904784 and EP 2054165 ).
  • 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).
  • 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: HS -ABC
  • said thiol compound is a thiol-perfluorinated compound of the following formula I: wherein: n is an integer from 1 to 100, m is an integer of from 1 to 100, and x is an integer of from 1 to 10 and said bisphosphonic compound is a perfluorinated bisphosphonic compound of the following formula II: wherein: n is an integer from 1 to 100, m is an integer from 1 to 100, and x is an integer from 1 to 10.
  • said bisphosphonic compounds and said thiol compounds are dissolved in an organic solvent chosen from alcoholic solvents, in particular C 1 to 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.
  • alcoholic solvents in particular C 1 to 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 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.
  • 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.
  • a covering composition of the invention comprising at least one thiol compound and at least one bisphosphonic compound, or one of their salts
  • the thiol compounds present in the coating composition of the present invention are of formula: HS-ABC
  • the bisphosphonic compound present in the covering composition of the present invention has the formula:
  • C 0 -C 100 alkyl group is intended to mean a linear or branched saturated divalent hydrocarbon chain comprising from 0 to 100, preferably from 1 to 10, carbon atoms.
  • 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.
  • partially fluorinated is meant a molecule whose carbon atoms are substituted at least partially by fluorine atoms.
  • cycloalkyl is meant, in the sense of the present invention, a cyclic saturated hydrocarbon chain, preferably having between 3 and 7 ring carbon atoms.
  • cyclopropyl cyclopentyl, cyclohexyl and cycloheptyl groups.
  • 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: wherein: n is an integer of 1 to 100, m is an integer of 1 to 100, and 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: wherein: n is an integer of 1 to 100, m is an integer of 1 to 100, and 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 (-PO 3 H 2 ), to be 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 of 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 coating 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 / m.
  • 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 to 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 to 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 covering 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 bisphosphonate have the same concentration.
  • 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 is selected 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, ethers such as diethyl ether or tetrahydrofuran or alkanes, especially C 1 -C 8 alkanes, and mixtures thereof.
  • the solvent is isopropyl alcohol (IPA) (or isopropanol).
  • 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 higher the density of gem-bisphosphonic compounds fixed on 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 CO 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 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.
  • 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 a test liquid (water, C.E.S. test liquid) 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 covering composition
  • the present invention therefore also relates to the use of a composition containing, as the sole active principle of recovery, the thiol compound of formula I.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 to C 6 alcohols, such as isopropanol, ethanol, methanol, aldehydes and ketones. such as 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 on the figure 1 ) can 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 organic phase is dried (MgSO4), 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 (MgSO4), 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:
  • the 6-aminohexan-1-ol is acylated by 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 II.1 via an acid chloride.
  • the solubilization of the molecules was carried out in the concentrations of use, is 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 IPA.
  • 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 two compounds of the invention I.1 and II.1 were mixed with either 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 (containing 10 ⁇ sup> -3 ⁇ / sup> M of the compound I.1 and 10 ⁇ sup> -3 ⁇ / sup > M of the compound II.1 or 10 ⁇ sup> -4 ⁇ / sup> M of the compound I.1 and 10 ⁇ sup> -4 ⁇ / sup> M of the compound II.1) as a function of the recovery time (0 , 10, 30, 60 and 360 minutes).
  • the tested solution giving the best results is the 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.
  • the resistance of the epilame layers of the invention was evaluated after 1 or more washing cycles by measuring contact angles with H 2 O and the test oil. Good resistance of epilame to the different materials evaluated was observed, even for several washing cycles.
  • the different molecules also show good Rubisol-type washing resistance when the layer is made with a 10 -3 M concentrated solution of I.1 to I.5.
  • the lipophobic / hydrophobic effect of thiol and bisphosphonate molecules was tested for single molecules, then for their mixtures, in order to highlight the synergistic effect produced by the combination of the two types of molecules.
  • 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 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 thiols alone do not bind (or little) on steel.
  • Example 9 epilame solutions according to the invention tested in the context of Example 9 (mixture of thiol compounds 1.3 and 1.6 with bisphosphonate compounds II.1, II.2 and II.5 to 10 ⁇ sup> -3 ⁇ / sup> M and 10 ⁇ sup> -4 ⁇ / sup> M in IPA) Molecule II.1 II.2 II.5 I.3 Mixture 1 Mix 4 Mix 5 I.6 Mix 6 Mix 7 Mix 8
  • the solubility was qualified by observation of the clarity of the solutions at the time of their mixing in isopropanol after 1h 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.
  • 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, 10 ⁇ sup> -3 ⁇ / sup> M in IPA, soaking time of 5 minutes, repeated treatment twice)
  • the epilame functionality is good for all mixtures, with a contact angle always greater than 60 ° with the test oil and always greater than 100 ° with water.

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Claims (15)

  1. Verwendung einer Zusammensetzung, die mindestens eine Thiolverbindung und mindestens eine Bisphosphonverbindung oder eines von deren Salzen enthält,
    dadurch gekennzeichnet, dass die Thiolverbindung der folgenden Formel entspricht:

            HS-A-B-C

    in welcher:
    A eine (CH2)m-X--Gruppe ist, wobei m eine ganze Zahl zwischen 0 und 100 ist und X eine gesättigte oder nicht gesättigte, perfluorierte oder teilweise fluorierte C0-C100-Alkylgruppe ist, wobei die Alkylkette durch 0 bis 10 Cycloalkylgruppen oder Arylgruppen, die perfluoriert oder nicht perfluoriert sein können, substituiert oder unterbrochen sein kann;
    B
    a) eine einfache chemische Bindung oder ein Sauerstoffatom, Schwefelatom oder eine S(CO)-, (CO)S- oder NR-, (CO)NR-, NR(CO)-Gruppe ist, wobei R ein Wasserstoffatom oder ein C1-C10-Alkyl ist, oder
    b)
    Figure imgb0027
     ist und
    C ausgewählt ist aus: F(CF(CF3)CF2O)nCF(CF3)-, F(CF2CF(CF3)O)nCF2CF2-, F(CF2CF2CF2O)nCF2CF2- und F(CF2CF2O)nCF2-
    und CpF2p+1-, wobei n und p ganze Zahlen zwischen 1 und 100 sind, und dadurch gekennzeichnet, dass die Bisphosphonverbindung der folgenden Formel entspricht:
    Figure imgb0028
    in welcher:
    R ein Wasserstoffatom oder eine OH-Gruppe ist,
    A eine (CH2)m-X--Gruppe ist, wobei m eine ganze Zahl zwischen 0 und 100 ist, X eine gesättigte oder nicht gesättigte, perfluorierte oder teilweise fluorierte C0-C100-Alkylgruppe ist, wobei die Alkylkette durch 0 bis 10 Cycloalkylgruppen oder Arylgruppen, die perfluoriert oder nicht perfluoriert sein können, substituiert oder unterbrochen sein kann;
    B
    a) eine einfache chemische Bindung oder ein Sauerstoffatom, Schwefelatom oder eine S(CO)-, (CO)S- oder NR-, (CO)NR-, NR(CO)-Gruppe ist, wobei R ein Wasserstoffatom oder ein C1-C10-Alkyl ist, oder
    b)
    Figure imgb0029
     ist und
    C ausgewählt ist aus: (CF(CF3)CF2O)nCF(CF3)-, F(CF2CF(CF3)O)nCF2CF2-, F(CF2CF2CF2O)nCF2CF2-, F(CF2CF2O)nCF2 und
    CpF2p+1-, wobei n und p ganze Zahlen zwischen 1 und 100 sind,
    um die Lipophobie einer für die Uhren- oder Schmuckindustrie bestimmten Oberfläche zu erhöhen.
  2. Verwendung der Zusammensetzung nach Anspruch 1, um die Ausbreitung von fetten Schmierstoffen auf einer für die Uhren- oder Schmuckindustrie bestimmten Oberfläche zu begrenzen.
  3. Verwendung der Zusammensetzung nach Anspruch 1, um die Epilamwirkung einer für die Uhren- oder Schmuckindustrie bestimmten Oberfläche zu erhöhen.
  4. Verwendung nach einem der Ansprüche 1 bis 3, wobei die Oberfläche zu mehr als 50 % besteht:
    - aus Edelmetallen, die aus Gold (Au), Platin (Pt), Silber (Ag) und Kupfer (Cu) ausgewählt sind,
    - aus oxidierten Metallen, die aus Eisen (Fe), Titan (Ti), Aluminium (Al), Nickel (Ni), Ruthenium (Ru), Rhodium (Rh) und Zinn (Sn) ausgewählt sind,
    - aus Legierungen, die ausgewählt sind aus Stahl (Legierung aus Eisen und Kohlenstoff), rostfreiem Stahl, Messing (Legierung aus Kupfer und Zink), Neusilber (Legierung aus Kupfer, Nickel und Zink), Bronze (Legierung aus Kupfer und Zinn), Zinn-Nickel (Sn-Ni), Nickel-Phosphor (Ni-P), Kupfer-Beryllium (Cu-Be), Palladium-Nickel (Pd-Ni), Kupfer-Kobalt (Cu-Co) oder aus Legierungen, die Vanadium (V), Chrom (Cr), Mangan (Mn), Zink (Zn), Wolfram (W) oder Zirkonium (Zr) enthalten, oder aus einer Legierung mit amorpher kristalliner Struktur, oder
    - aus Keramiken oder Gläsern wie Rubin (Legierung aus Aluminiumoxid und Chrom), Saphir (Aluminiumoxid), Zirkon, Siliziumoxid oder Aluminiumoxid, oder
    - aus Halbleitern wie Silizium (Si) oder Germanium (Ge) sowie deren Oxiden, oder auch aus Diamant.
  5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Thiolverbindung ein Perfluorthiol der folgenden Formel I ist:
    Figure imgb0030
     in welcher: n eine ganze Zahl zwischen 1 und 100 ist, m eine ganze Zahl zwischen 1 und 100 ist und x eine ganze Zahl zwischen 1 und 10 ist.
  6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Bisphosphonverbindung ein perfluoriertes Bisphosphon der folgenden Formel II ist:
    Figure imgb0031
     in welcher: n eine ganze Zahl zwischen 1 und 100 ist, m eine ganze Zahl zwischen 1 und 100 ist und x eine ganze Zahl zwischen 1 und 10 ist.
  7. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Thiolverbindung ein Perfluorthiol der Formel I nach Anspruch 5 ist und die Bisphosphonverbindung ein perfluoriertes Bisphosphon der Formel II nach Anspruch 6 ist.
  8. Verwendung nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, dass die Perfluorthiol-Verbindung eine Verbindung der Formel I ist, in welcher n=6, m=4 und x=1 oder n=2, m=4 und x=1 oder n=6, m=5 und x=1 oder n=2, m=5 und x=1 oder n=10, m=5 und x=1, und die perfluorierte Bisphosphonverbindung eine Verbindung der Formel II ist, in welcher n=4, m=4 und x=1 oder n=8, m=5 und x=1, vorzugsweise, die Perfluorthiol-Verbindung eine Thiol-Perfluoropolyether-Verbindung der Formel I ist, in welcher n=6, m=5 und x=1, und die perfluorierte Bisphosphonverbindung eine Verbindung der Formel II ist, in welcher n=4, m=4 und x=1.
  9. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Bisphosphonverbindungen und die Thiolverbindungen in einem organischen Lösemittel gelöst sind, das ausgewählt ist aus Alkohollösungsmitteln, insbesondere C1- bis C6-Alkoholen wie Isopropanol, Ethanol, Methanol, Aldehyden, Ketonen wie Aceton, Ethern wie Diethylether oder Tetrahydrofuran oder Alkanen, insbesondere C1- bis C8-Alkanen sowie deren Gemischen.
  10. Verfahren zum Überdecken einer für die Uhren- oder Schmuckindustrie bestimmten Oberfläche durch eine molekulare Funktionalisierungsschicht, dadurch gekennzeichnet, dass es mindestens die folgenden Schritte umfasst:
    a) etwaiges Entfetten der Oberfläche durch Reinigen in einem Lösemittel und dann Trocknen,
    b) etwaige Oxidation der Oberfläche, derart, dass Hydroxylfunktionen an der Oberfläche des Substrats vorhanden sind,
    c) Inkontaktbringen der Oberfläche mit einer Zusammensetzung nach den Ansprüchen 1 bis 9 bis zum Selbstorganisieren der Thiolund/oder Bisphosphonverbindungen in einer Monoschicht, welche die Oberfläche überdeckt,
    d) Abnehmen des Überstandes,
    e) gegebenenfalls Dehydrierung der somit überdeckten Oberfläche,
    f) Spülen der funktionalisierten Oberfläche,
    g) Trocknen der funktionalisierten Oberfläche,
    wobei die Schritte c) bis f) vorzugsweise mindestens zwei Mal wiederholt werden.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die Oberfläche zu mehr als 50 % besteht:
    - aus Edelmetallen, die aus Gold (Au), Platin (Pt), Silber (Ag) und Kupfer (Cu) ausgewählt sind,
    - aus oxidierten Metallen, die aus Eisen (Fe), Titan (Ti), Aluminium (Al), Nickel (Ni), Ruthenium (Ru), Rhodium (Rh) und Zinn (Sn) ausgewählt sind,
    - aus Legierungen, die ausgewählt sind aus Stahl (Legierung aus Eisen und Kohlenstoff), rostfreiem Stahl, Messing (Legierung aus Kupfer und Zink), Neusilber (Legierung aus Kupfer, Nickel und Zink), Bronze (Legierung aus Kupfer und Zinn), Zinn-Nickel (Sn-Ni), Nickel-Phosphor (Ni-P), Kupfer-Beryllium (Cu-Be), Palladium-Nickel (Pd-Ni), Kupfer-Kobalt (Cu-Co) oder aus Legierungen, die Vanadium (V), Chrom (Cr), Mangan (Mn), Zink (Zn), Wolfram (W) oder Zirkonium (Zr) enthalten, oder aus einer Legierung mit amorpher kristalliner Struktur, oder
    - aus Keramiken oder Gläsern wie Rubin (Legierung aus Aluminiumoxid und Chrom), Saphir (Aluminiumoxid), Zirkon, Siliziumoxid oder Aluminiumoxid, oder
    - aus Halbleitern wie Silizium (Si) oder Germanium (Ge) sowie deren Oxiden, oder auch aus Diamant.
  12. Verwendung einer funktionalisierten, ausgehend von dem Verfahren nach Anspruch 10 und 11 erhaltenen Oberfläche in mechanischen Teilen, die für die Uhren- oder Schmuckindustrie bestimmt sind.
  13. Verwendung einer Zusammensetzung, enthaltend die Thiolverbindung der Formel I.3:
    Figure imgb0032
     oder eines von deren Salzen, um die Lipophobie einer Oberfläche und/oder die Epilamwirkung auf einer Oberfläche zu erhöhen, wobei die Oberfläche für die Uhren- oder Schmuckindustrie bestimmt ist.
  14. Verwendung nach Anspruch 13, wobei die Oberfläche eine Metalloberfläche ist, die zu mehr als 50 % aus Edelmetall besteht, das ausgewählt ist aus Gold, Silber und Kupfer.
  15. Verwendung nach einem der Ansprüche 13 bis 14, wobei die Verbindung der Formel I.3 in Isopropanol oder in einem Lösemittel, das aus mit Wasserstoff behandeltem Naphtha besteht, solubilisiert ist.
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EP2684942A1 (de) 2012-07-10 2014-01-15 The Swatch Group Research and Development Ltd. Mittel zur Oberflächenepilamisierung eines Artikels
JP6239813B2 (ja) 2012-07-18 2017-11-29 株式会社Ｓｃｒｅｅｎセミコンダクターソリューションズ 基板処理装置および基板処理方法
EP2865737A1 (de) * 2013-10-28 2015-04-29 The Swatch Group Research and Development Ltd. Edelprodukt aus Epilam
CN104226984B (zh) * 2014-10-14 2017-01-25 电子科技大学 具有蛋白增色增敏效应的硫醇衍生化纳米金材料的制备
EP3070133B1 (de) 2015-03-18 2019-02-20 The Swatch Group Research and Development Ltd. Uhr oder scmucktück, das eine mit epilamisierungsmittel bedeckte oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
EP3070152B1 (de) 2015-03-18 2018-02-28 The Swatch Group Research and Development Ltd. Substrat, das eine mit epilamisierungsmittel bedeckte oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
EP3420037B1 (de) 2016-02-22 2022-09-07 Surfactis Technologies Zusammensetzungen basierend auf biphosphonderivaten aufgelöst in einem fluorhaltigen lösungsmittel und ihre verwendung zum beschichten der oberfläche eines artikels
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US11392091B2 (en) * 2017-07-31 2022-07-19 Rolex Sa Watch pivot device
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