EP3192854B1 - Artikel, dessen oberfläche mit einem kopplungsmittel mit oleophoben und/oder hydrophoben eigenschaften behandelt wurde - Google Patents

Artikel, dessen oberfläche mit einem kopplungsmittel mit oleophoben und/oder hydrophoben eigenschaften behandelt wurde Download PDF

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EP3192854B1
EP3192854B1 EP16305041.2A EP16305041A EP3192854B1 EP 3192854 B1 EP3192854 B1 EP 3192854B1 EP 16305041 A EP16305041 A EP 16305041A EP 3192854 B1 EP3192854 B1 EP 3192854B1
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another
molecule
different
general formula
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French (fr)
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EP3192854A1 (de
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Franck Martin
Guillaume GRACY
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Sikemia
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Sikemia
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    • 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
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • 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
    • C10M105/72—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing sulfur, selenium or tellurium
    • 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
    • C10M105/76—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing silicon
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/023—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no 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
    • 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
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/0405—Phosphate esters 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C10M2223/0495—Phosphite 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
    • C10M2227/045—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes 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 relates to an article whose surface is treated with a coupling agent.
  • the present invention also relates to a method of treating a surface with a coupling agent.
  • the present invention also relates to a method for synthesizing a coupling agent.
  • an epilamate consisting of covering a surface of an epilame, that is to say covering a surface of a product or a substance allowing avoid that a liquid, for example a lubricant, does not spread but on the contrary it remains localized at a precise place (in a zone).
  • a liquid for example a lubricant
  • the application of an epilame makes it possible to reduce the surface energy of an article and to modify the surface tension thereof by applying a hydrophobic and / or oleophobic molecular layer.
  • the so-called “chemical” epilams (which are distinguished from so-called “mechanical” epilams) comprise two parts, namely (1) the anchor (or hook) which determines the attachment of the epilame to a surface and (2) ) the functional body which confers the epilame properties on the molecule, especially via fluorinated groups.
  • epilams or coupling agents do not preserve the latter in a durable and stable manner over time.
  • the current coupling agents deposited on the article surfaces have a low resistance to washing, which is mainly due to the fact that only weak chemical hooks between the epilames and the treated surfaces are currently obtained.
  • the current commercial epilamines are not stable over time, in particular because they have "fragile" functions that are particularly sensitive to hydrolysis in an acidic or basic medium, for example ester or amide functions.
  • the present invention aims to overcome the drawbacks of the state of the art by providing an article whose surface treated with a coupling agent does not deteriorate over time, that is to say whose surface remains covered (coated) by the coupling agent. Furthermore, the present invention aims to provide a chemical coupling agent whose properties are greater than those currently known, in terms of attachment (adhesion) with the treated surfaces and in terms of stability over time. In other words, the present invention intends to provide an article whose surface is treated by applying an epilame, this article having surface properties superior to those obtained with the current epilamage formulations, this in particular in terms of attachment of epilam on one surface and stability of the epilame over time (eg adequately and more adequately withstanding successive wash cycles).
  • each R 1 independent of each other, and identical or different from each other at each occurrence, are selected from the group consisting of (CR 5 R 6 ) n , where each R 5 and R 6 , identical or different from each other are selected independently in the group consisting of H, a linear or branched alkyl group having 1 to 8 carbon atoms, which is optionally substituted by at least one atom of the halogen family, an aryl group or an aralkyl group, n being included between 1 and 30.
  • each R 1 independent of one another, and identical or different from each other at each occurrence, are (CH 2 ) n and n is between 1 and 30.
  • each R ' independent of one another, and identical or different from each other at each occurrence, are selected from the group consisting of a bond, (CR 5 R 6 ) n , where each R 5 and R 6 , identical to or different from each other, are independently selected from the group consisting of H, a linear or branched alkyl group having 1 to 8 carbon atoms, which is optionally substituted with at least one atom of the halogen family, an aryl group or an aralkyl group, n being between 1 and 30.
  • each R ' independent of each other, and identical or different from each other at each occurrence, are a bond, (CH 2 ) n and n is between 2 and 12, preferentially each R 'is a bond.
  • repeating alkylene oxide units may be mentioned (O-CH 2 -CH 2 -O) m , (O-CH 2 -CH 2 -CH 2 O) m , (OCH 2 -CH (CH 3 )) m and (O-CH (CH 3 ) -CH 2 ) m , where m is between 1 and 100, preferably m is between 2 and 30, preferentially, m is between 3 and 10;
  • perfluoroalkyl groups comprising from 1 to 50 carbon atoms, the following compounds may be mentioned: perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorononyl and perfluorodecyl and the like.
  • the perfluoroalkyl group comprises 3 to 25 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the subject of the invention is also a process for treating a surface of an article with a molecule of general formula (I), said treatment method comprising a step of bringing said surface into contact with said molecule of general formula ( I).
  • the method of treating a surface of an article according to the invention comprises a preliminary step of pretreatment by a plasma process of said surface.
  • pretreatment of the surface by a plasma process for example by oxygen plasma or by air plasma, makes it possible to further optimize the adhesion of the surface.
  • the method of treating a surface of an article according to the invention comprises a preliminary step of dissolving in a solvent of said molecule of general formula (I) to form a surface treatment solution.
  • said preliminary step of dissolving in a solvent to form a surface treatment solution is carried out by dissolving in a solvent chosen from group consisting of isopropanol, ethanol, methanol, dimethylformamide, acetone, tetrahydrofuran, preferably isopropanol.
  • said preliminary step of dissolving in a solvent forms a surface treatment solution comprising said molecule of general formula (I) in a proportion of 0.01% to 10% v / v in a solvent, preferably in a proportion of 0.1% to 5% v / v.
  • said step of bringing said pretreated surface into contact with a molecule of general formula (I) is carried out by spraying, dipping, spraying, buffering, wiping, by spin coating and deep coating.
  • said surface to be treated is chosen from the group consisting of sapphire, brass, rhodium-plated brass, gold-plated brass, nickel, steel, copper, nickel, curable steel, iron, aluminum, titanium, lead, silver, gold, chromium, copper, manganese, vanadium, lithium, cobalt, silicon and various alloys and metal oxides of such metals. It is understood that any other surface that can be treated is within the scope of the present invention.
  • each R 1 independent of each other, and identical or different from each other at each occurrence, are selected from the group consisting of (CR 5 R 6 ) n , where each R 5 and R 6 , which are identical to or different from each other, are independently selected from the group consisting of H, a linear or branched alkyl group. comprising 1 to 8 carbon atoms, which is optionally substituted with at least one halogen group atom, an aryl group or an aralkyl group, n being between 1 and 30.
  • each R 1 independent of one another, and identical or different from each other at each occurrence, are (CH 2 ) n and n is between 1 and 30.
  • each R ' independent of one another, and identical or different from each other at each occurrence, are selected from the group consisting of a bond, (CR 5 R 6 ) n , where each R 5 and R 6 , identical to or different from each other, are independently selected from the group consisting of H, a linear or branched alkyl group having 1 to 8 carbon atoms, which is optionally substituted with at least one atom of the halogen family, an aryl group or an aralkyl group, n being between 1 and 30.
  • each R ' independent of each other, and identical or different from each other at each occurrence, are a bond, (CH 2 ) n and n is between 2 and 12, preferentially each R 'is a bond.
  • repeating alkylene oxide units may be mentioned (O-CH 2 -CH 2 -O) m , (O-CH 2 -CH 2 -CH 2 O) m , (OCH 2 -CH (CH 3 )) m and (O-CH (CH 3 ) -CH 2 ) m , where m is between 1 and 100, preferably m is between 2 and 30, preferentially, m is between 3 and 10.
  • perfluoroalkyl groups comprising from 1 to 50 carbon atoms
  • the following compounds may be mentioned: perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorononyl and perfluorodecyl and the like.
  • the perfluoroalkyl group comprises 3 to 25 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Such a synthesis method according to the invention makes it possible to obtain easily and quickly, starting from a molecule of general formula (II), a compound of general formula (I), this by simple substitution of at least one halogenated group.
  • X, Y of said molecule of general formula (II) by a group which can represent a hook (anchor) arranged to attach to a surface.
  • an epilame comprising at least, as an anchor, a group selected from the group consisting of PO 3 H 2 , OPO 3 H 2 , SH, and SiX 3 groups.
  • X H, Cl, OMe, OEt, OiPr, preferably PO 3 H 2 .
  • one or more intermediate steps can be carried out to obtain a molecule of general formula (I) starting from a molecule of general formula (II).
  • a molecule of general formula (II) For example, as an intermediate step, the step of substitution of the halogenated group by a phosphonate group and the step of hydrolysis of the latter in an acidic or basic medium could take place.
  • the present invention also relates to a use of a molecule of general formula (I) for a treatment of a surface of an article.
  • the present invention relates to a use of a molecule of general formula (I) for a surface treatment of a timepiece. It is understood that any other surface of any other article or product is within the scope of the present invention.
  • Step 2 starting from 10,11-bis (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9 heptadecafluorononyl) icosane-1, 20-diol (formula A)
  • 10,11-bis (9-bromononyl) -1,1,1,2,2,3,3,4,4,5,5, 6,6,7,7,8,8 is obtained , 13,13,14,14, 15,15,16,16,17,17,18,18,19,19,20,20,20 tetracyclafluoroicosane.
  • Step 3 starting from 10,11-bis (9-bromononyl) -1,1,1,2,2,3,3,4,4,5,5, 6,6,7,7,8,8, 13,13,14,14,15,15,16,16,17,17,18,18,19,19,20,20,20 tetratriacontafluoroicosane (formula B)
  • Step 4 starting from tetraethyl 10,11-bis (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl) -icosane -1,20-diylbisphosphonate (formula C)
  • This process for synthesizing a compound of general formula (I) according to the invention is therefore based on a substitution of at least one halogenated group of a starting molecule.
  • Step 4 starting from tetraethyl 10,11-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl) icosane-1,20-diylbisphosphonate (formula G)
  • This process for synthesizing a compound of general formula (I) according to the invention is therefore also based on a substitution of at least one halogenated group of a starting molecule.
  • the contact angle measurement reports the ability of a liquid (eg, an oil) to spread over a surface by wettability.
  • the method consists in measuring the angle of the tangent of the profile of a drop deposited on the substrate, with the surface of the substrate.
  • This measure makes it possible, in particular, to discriminate the polar or apolar nature of the interactions at the liquid-solid interface and thus to deduce the hydrophilic or hydrophobic nature of a surface.
  • the more a large angle is measured the more the surface has a hydrophobic / oleophobic character.
  • the smaller the angle the more hydrophilic the surface.
  • Krüss brand DSA100 associated with DSA4 version 2.0 software were used to perform these contact angle measurements.
  • the surfaces Prior to carrying out 7 successive washing cycles, the surfaces were treated by immersion for 5 minutes or 15 minutes in the various epilamating solutions containing an epilame at a rate of 2.5 ⁇ 10 -3 mol -1 in isopropanol as a solvent. Then, the treated substrates were drained for 1 minute and then dried under hot air (55 ° C) for 5 minutes.
  • a step of pretreatment by plasma of the surface to be treated with an epilame can be carried out before the actual treatment of the same surface by contact with a molecule of general formula (I) according to the invention.
  • a brass surface that has been pretreated with oxygen plasma or not has been treated with a molecule as described in Example 1 (molecule 1 - OLEOXEIN +) and corresponding to a molecule of general formula (I) according to invention (surface treatment by immersion for 5 or 15 minutes).
  • Oxygen plasma pretreatment was carried out with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.
  • the surface treatments, the washing cycles and the contact angle measurements were carried out according to the same protocols as those applied in Example 1.
  • pretreatment of the surface with oxygen plasma before treatment with a molecule of general formula (I) allows the latter to cling (to adhere) more strongly to the treated surface and in particular to resist better hydrolysis in an acidic or basic medium, this conferring on the epilame a high stability over time.
  • Oxygen plasma pretreatment was carried out with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.
  • the surface treatments and the contact angle measurements were carried out according to the same protocols as those applied to Example 1
  • Oxygen plasma pretreatment was carried out with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.
  • the surface treatments and the contact angle measurements were carried out according to the same protocols as those applied to Example 1
  • Oxygen plasma pretreatment was carried out with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.
  • the surface treatments and the contact angle measurements were carried out according to the same protocols as those applied to Example 1
  • the molecule 1 (corresponding to a molecule of general formula (I) according to the invention - OLEOXEIN +) was tested as 'epilame.
  • Oxygen plasma pretreatment was carried out with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.
  • the surface treatments and the contact angle measurements were carried out according to the same protocols as those applied to Example 1
  • Oxygen plasma pretreatment was carried out with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.
  • the surface treatments and the contact angle measurements were carried out according to the same protocols as those applied to Example 1

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
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Claims (12)

  1. Artikel, dessen Oberfläche mit einem Kupplermittel behandelt ist, das der folgenden allgemeinen Formel (I) entspricht:
    Figure imgb0025
     in der
    - jedes R1, das voneinander unabhängig und mit dem anderen bei jedem Vorkommen identisch oder unterschiedlich davon ist, aus einer Gruppe ausgewählt ist, die aus einer Verbindung (CR5R6)n besteht, in der R5 und R6, die miteinander identisch oder voneinander unterschiedlich sind, unabhängig von der Gruppe ausgewählt sind, die aus H, einer 1 bis 10 Kohlenstoffatome umfassenden Alkyl-Gruppe, die optional durch wenigstens ein Atom der Familie der Halogene substituiert ist, einer Aryl-Gruppe oder einer AralkylGruppe, wobei n zwischen 1 und 50 inbegriffen ist, und einer Polyalkylenoxid-Kette, die 1 bis 100 Wiederholungen von Alkylenoxid-Einheiten aufweist, gebildet ist;
    - jedes R', das voneinander unabhängig und mit dem anderen bei jedem Vorkommen identisch oder unterschiedlich davon ist, aus einer Gruppe ausgewählt ist, die aus einer Verbindung (CR5R6)n besteht, in der R5 und R6, die miteinander identisch oder voneinander unterschiedlich sind, unabhängig von der Gruppe ausgewählt sind, die aus H, einer 1 bis 10 Kohlenstoffatome umfassenden Alkyl-Gruppe, die optional durch wenigstens ein Atom der Familie der Halogene substituiert ist, einer Aryl-Gruppe oder einer AralkylGruppe, wobei n zwischen 1 und 50 inbegriffen ist, gebildet ist;
    - jedes R2, das voneinander unabhängig und mit dem anderen bei jedem Vorkommen identisch oder unterschiedlich davon ist, aus einer Gruppe ausgewählt ist, die aus einer Verbindung (CH2)n, O, S, S-S, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-Cs-NH, NH(CO)O, NH(CS)O,
    Figure imgb0026
     S(CO), (CO)S besteht und n zwischen 1 und 100 inbegriffen ist;
    - jedes R3, das gleich dem anderen oder voneinander unterschiedlich ist, aus der Gruppe ausgewählt ist, die aus einer Perfluoralkyl-Gruppe gebildet ist, umfassend 1 bis 50 Kohlenstoffatome, (CF(CF3)CF2O)n(CF2)2CF3, (CF2CF(CF3)O)n(CF2)2CF3, (CF2CF2CF2O)n(CF2)2CF3 und (CF2CF2O)n(CF2)CF3 und n ist zwischen 0 und 100 inbegriffen;
    - jedes R4, das gleich dem anderen oder voneinander unterschiedlich ist, aus der Gruppe ausgewählt ist, die aus H, einer Alykylgruppe, umfassend 1 bis 10 Kohlenstoffatome, die optional durch wenigstens ein Atom der Familie der Halogene substituiert ist, einer Arylgruppe oder einer Aralkylgruppe, bevorzugt ist jedes R4 H, gebildet ist;
    - T eine Verbindung (CH2)n O, S, S-S, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-CS-NH, NH(CO)O, NH(CS)O,
    Figure imgb0027
     S(CO), (CO)S ist und n zwischen 1 und 100 inbegriffen ist;
    - jedes F und F', die voneinander unabhängig und bei jedem Vorkommen miteinander identisch oder voneinander unterschiedlich sind, aus der Gruppe ausgewählt sind, die aus PO3H2, OPO3H2, SH und SiX3, X = H, Cl, OMe, OEt, OiPr, bevorzugt PO3H2, gebildet ist.
  2. Behandlungsverfahren einer Oberfläche eines Artikels mit einem Molekül der allgemeinen Formel (I) gemäß Definition in Anspruch 1, wobei das genannte Behandlungsverfahren einen Kontaktierungsschritt der genannten Oberfläche mit dem genannten Molekül der allgemeinen Formel (I) umfasst.
  3. Behandlungsverfahren einer Oberfläche eines Artikels gemäß Anspruch 2, umfassend einen Schritt vor der Vorbehandlung durch ein Plasmaverfahren der genannten Oberfläche.
  4. Behandlungsverfahren einer Oberfläche eines Artikels gemäß Anspruch 2 oder 3, dadurch gekennzeichnet, dass es einen Schritt vor dem Einbringen des genannten Moleküls der allgemeinen Formel (I) in eine Lösung in einem Lösungsmittel umfasst, um eine Lösung zur Oberflächenbehandlung zu bilden.
  5. Behandlungsverfahren einer Oberfläche eines Artikels gemäß Anspruch 4, dadurch gekennzeichnet, dass der genannte Schritt vor dem Einbringen in eine Lösung in ein Lösungsmittel, um eine Behandlungslösung der Oberfläche zu bilden, durch Einbringen in eine Lösung in ein Lösungsmittel realisiert ist, das aus der Gruppe ausgewählt ist, die aus Isopropanol, Ethanol, Methanol, Dimethylformamid, Aceton, Tetrahydrofuran, bevorzugt Isopropanol gebildet ist.
  6. Behandlungsverfahren einer Oberfläche eines Artikels gemäß Anspruch 4 oder 5, dadurch gekennzeichnet, dass der genannte Schritt vor dem Einbringen in eine Lösung in ein Lösungsmittel eine Behandlungslösung der Oberfläche bildet, umfassend das genannte Molekül der allgemeinen Formel (I) in einer Menge von 0,01 V/V-% bis 10 V/V-% in einem Lösungsmittel, bevorzugt in einer Menge von 0,1 % bis 5 V/V-%.
  7. Behandlungsverfahren einer Oberfläche eines Artikels gemäß irgendeinem der Ansprüche 2 bis 6, dadurch gekennzeichnet, dass der genannte Kontaktierungsschritt der genannten vorbehandelten Oberfläche mit einem Molekül der allgemeinen Formel (I) per Versprühen, per Eintauchen, per Bestäuben, per Pufferung, per Abwischen, per Spin Coating und per Deep Coating realisiert ist.
  8. Behandlungsverfahren einer Oberfläche eines Artikels gemäß irgendeinem der Ansprüche 2 bis 7, umfassend darüber hinaus wenigstens einen der folgenden zusätzlichen Schritte:
    - ein Abtropfen der genannten Oberfläche, die mit der genannten Behandlungslösung der Oberfläche kontaktiert ist und / oder
    - ein Waschen der genannten Oberfläche, die mit der genannten Behandlungslösung der Oberfläche kontaktiert ist und / oder
    - ein Trocknen der genannten Oberfläche, die mit der genannten Behandlungslösung der Oberfläche kontaktiert ist.
  9. Behandlungsverfahren einer Oberfläche eines Artikels gemäß irgendeinem der Ansprüche 2 bis 8, dadurch gekennzeichnet, dass die genannte, zu behandelnde Oberfläche aus der Gruppe ausgewählt ist, die aus Saphir, Messing, rhodiertem Messing, vergoldetem Messing, Nickel, Stahl, härtbarem Stahl, Eisen, Aluminium, Titan, Blei, Silber, Gold, Chrom, Kupfer, Mangan, Vanadium, Lithium, Kobalt, Silizium und verschiedenen Legierungen und Metalloxiden derartiger Metalle gebildet ist.
  10. Syntheseverfahren eines Kupplungsmittels, das der allgemeinen Formel (I) gemäß Definition in Anspruch 1 entspricht, ausgehend von einem Molekül der allgemeinen Formel (II), das der folgenden Formel entspricht:
    Figure imgb0028
     in der
    - jedes R1, das voneinander unabhängig und mit dem anderen bei jedem Vorkommen identisch oder unterschiedlich davon ist, aus einer Gruppe ausgewählt ist, die aus einer Verbindung (CR5R6)n besteht, in der R5 und R6, die miteinander identisch oder voneinander unterschiedlich sind, unabhängig von der Gruppe ausgewählt sind, die aus H, einer 1 bis 10 Kohlenstoffatome umfassenden Alkyl-Gruppe, die optional durch wenigstens ein Atom der Familie der Halogene substituiert ist, einer Aryl-Gruppe oder einer AralkylGruppe, wobei n zwischen 1 und 50 inbegriffen ist, und einer Polyalkylenoxid-Kette, die 1 bis 100 Wiederholungen von Alkylenoxid-Einheiten aufweist, gebildet ist;
    - jedes R', das voneinander unabhängig und mit dem anderen bei jedem Vorkommen identisch oder unterschiedlich davon ist, aus einer Gruppe ausgewählt ist, die aus einer Verbindung (CR5R6)n besteht, in der R5 und R6, die miteinander identisch oder voneinander unterschiedlich sind, unabhängig von der Gruppe ausgewählt sind, die aus H, einer 1 bis 10 Kohlenstoffatome umfassenden Alkyl-Gruppe, die optional durch wenigstens ein Atom der Familie der Halogene substituiert ist, einer Aryl-Gruppe oder einer AralkylGruppe, wobei n zwischen 1 und 50 inbegriffen ist, gebildet ist;
    - jedes R2, das voneinander unabhängig und mit dem anderen bei jedem Vorkommen identisch oder unterschiedlich davon ist, aus der Gruppe ausgewählt ist, die aus einer Verbindung (CH2)n, O, S, S-S, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-CS-NH, NH(CO)O, NH(CS)O,
    Figure imgb0029
     S(CO), (CO)S besteht und n zwischen 1 und 100 inbegriffen ist;
    - jedes R3, das gleich dem anderen oder voneinander unterschiedlich ist, aus der Gruppe ausgewählt ist, die aus einer Perfluoralkyl-Gruppe gebildet ist, umfassend 1 bis 50 Kohlenstoffatome, (CF(CF3)CF2O)n(CF2)2CF3, (CF2CF(CF3)O)n(CF2)2CF3, (CF2CF2CF2O)n(CF2)2CF3 und (CF2CF2O)n(CF2)CF3 und n ist zwischen 0 und 100 inbegriffen;
    - jedes R4, das gleich dem anderen oder voneinander unterschiedlich ist, aus der Gruppe ausgewählt ist, die aus H, einer Alykylgruppe, umfassend 1 bis 10 Kohlenstoffatome, die optional durch wenigstens ein Atom der Familie der Halogene substituiert ist, einer Arylgruppe oder einer Aralkylgruppe, bevorzugt ist jedes R4 H, gebildet ist;
    - T eine Verbindung (CH2)n O, S, S-S, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-CS-NH, NH(CO)O, NH(CS)O,
    Figure imgb0030
     S(CO), (CO)S ist und n zwischen 1 und 100 inbegriffen ist;
    - jedes X und Y, die voneinander unabhängig und bei jedem Vorkommen miteinander identisch oder voneinander unterschiedlich sind, stellen eine halogenierte Gruppierung oder eine ungesättigte organische Gruppierung dar;
    wobei das genannte Verfahren umfasst:
    - einen Substitutionsschritt wenigstens einer halogenierten Gruppierung X, Y des genannten Moleküls der allgemeinen Formel (II) durch eine Gruppierung, die direkt oder nach mehreren Syntheseschritten, einen Anker des genannten Kupplungsmittels darstellen kann und aus einer Gruppe ausgewählt ist, die aus den Gruppierungen PO3H2, OPO3H2, SH, bevorzugt PO3H2 gebildet ist, oder
    - einen Hinzufügungsschritt zu wenigstens einer ungesättigten, organischen Gruppierung X, Y des genannten Moleküls der allgemeinen Formel (II) einer Gruppierung, die direkt oder nach mehreren Syntheseschritten einen Anker des genannten Kupplungsmittels darstellen kann und aus der Gruppe ausgewählt ist, die aus Gruppierungen PO3H2, OPO3H2 und SiX3, X = H, Cl, OMe, OEt, OiPr, bevorzugt PO3H2, gebildet ist.
  11. Verwendung eines Moleküls der allgemeinen Formel (I) gemäß Definition in Anspruch 1 für eine Behandlung einer Oberfläche eines Artikels.
  12. Verwendung gemäß Anspruch 11 für eine Behandlung einer Oberfläche eines Uhrmachereistücks.
EP16305041.2A 2016-01-15 2016-01-15 Artikel, dessen oberfläche mit einem kopplungsmittel mit oleophoben und/oder hydrophoben eigenschaften behandelt wurde Active EP3192854B1 (de)

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