EP3192853B1 - Method for treating a surface in order to obtain a hydrophobic and/or oleophobic coating - Google Patents

Description

The present invention relates to a method of treating a surface selected from the group consisting of sapphire, brass, rhodium brass, gold brass, nickel, steel, hardenable steel, iron, aluminum, titanium, lead, silver, gold, chromium, copper, manganese, vanadium, lithium, cobalt, silicon and various metal alloys and oxides of such metals, said surface treatment method comprising a step of applying, on said surface, hydrophobic and/or oleophobic molecules and/or of applying an epilame.

Many surface treatments are known, such as those described in the documents US2014/087197 And EP2865737 .

More specifically, the document US2014/087197 relates to the application of a hydrophobic and/or oleophobic molecular layer so as to constitute an anti-fingerprint coating and the document EP2865737 relates to the production of an epilame consisting in covering a surface with an epilame (also called coupling agent), that is to say in covering a surface with a product or a substance making it possible to prevent a liquid, for example a lubricant, does not spread but on the contrary it remains localized in a precise place. The application of an epilame makes it possible to reduce the surface energy of an article and to modify its surface tension by applying a hydrophobic and/or oleophobic molecular layer. The so-called "chemical" epilames (which are distinguished from the so-called "mechanical" epilames) 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, in particular via fluorinated groups.

During the coating of a surface with hydrophobic and/or oleophobic molecules and/or an epilaming operation (that is to say during the application of an epilame by bringing it into contact with a surface to be treated), it is crucial to be able to ensure that the hydrophobic and/or oleophobic molecules and/or that the epilame will adhere strongly and durably to the surface. It is particularly appropriate to ensure that these molecules and/or that the epilame applied adhere so that the coating obtained can withstand successive washing cycles, in particular by resisting acid or basic hydrolysis. With regard to so-called "chemical" epilames, such attachment depends essentially on two factors, namely (1) the properties of the anchor of the epilame and (2) the properties of the surface on which the epilaming. Indeed, when the epilame forms a kind of coating on the treated surface, the interaction between the latter and the anchor of the epilame plays an essential and determining role.

In this sense, in order to ensure good adhesion of an epilame, the document EP2865737 relates to placing a bonding layer on a surface, this bonding layer being provided so that an epilame applied subsequently adheres more strongly to the surface comprising this bonding layer. The tie layer according to this prior document therefore constitutes an intermediate layer between the surface to be treated and the epilame itself. According to this prior document, such a tie layer can be applied using a vacuum evaporation technique, a flash evaporation technique or even by an atomic layer deposition technique.

In the same sense, the document US2014/087197 , having as its object an application of a hydrophobic and/or oleophobic molecular layer so as to constitute an anti-fingerprint coating on a surface, proposes an intermediate coating of this surface with a transition layer (“transition layer”) provided for ensure improved adhesion of the hydrophobic and/or oleophobic molecular layer. The transition layer according to this prior document is therefore an intermediate layer between the surface to be treated and the hydrophobic and/or oleophobic molecules.

In the request WO2013/167624 , it describes the use of amine molecules (N) and phosphonic compounds (P) to cover surfaces intended to be used in the field of watchmaking. These two types of compounds being alkaline and acid in nature form pairs of ions which interact with all types of surfaces, whether they are composed of mineral materials such as glass, metal, non-oxidized materials (including gold, rhodium and their alloys), or even polymeric materials.

In the request EP2687580 a timepiece is described comprising at least two elements in contact and movable relative to each other, at least one of said elements having a contact surface with the other element which is lubricated by means of a lubricating composition. The present invention also relates to such a lubricating composition, the use of chemical compounds as a lubricating agent and new chemical compounds.

In the request FR2967199A1 a threaded tubular component is described for drilling or operating hydrocarbon wells, said tubular component having at one of its ends as well as a threaded zone produced on its outer or inner peripheral surface depending on whether the threaded end is of the male or female type, in which at least a portion of the end is coated with at least one lubricating dry film comprising at least 65% by mass of a polyaryletherketone. The subject of the application is a process for depositing such a film which comprises the following steps:
The preparation of a mixture comprising a polyaryletherketone powder in suspension in water, in proportions of between 25 and 35% by mass, The application of the said mixture to a portion of the end of the said threaded tubular component, The drying of the portion of the end thus coated at a temperature of between 100 and 150° C. for a time of between 5 and 10 minutes, the placing at a temperature of between 350 and 450° C. for 5 to 15 minutes, of the portion of the end thus coated, according to a temperature rise rate of between 10 and 20°C per minute, followed by the cooling to ambient temperature of the portion of the end thus coated, according to a lower cooling rate at 10°C per minute, so as to obtain a mainly crystalline structure.

In the request US2012148875 there is disclosed a magnetic disk in which at least a magnetic layer, a protective layer and the lubricating layer are sequentially disposed on a substrate, the lubricating layer contains a lubricating compound for a magnetic disk, having a main chain of perfluoropolyether in the molecular structure and structure indicated as follows at a position near the center of the molecule: -0-CH2-CH(OH)-CH2-CH2-CH(OH)-CH2-0- or -0-CH2-CH(OH) -CH(OH)-CH2-0-.

Unfortunately, according to these surface treatment methods known from the state of the art, the application of an intermediate layer on the surface to be treated, that is to say the application of a bonding layer between the surface to be treated and the epilame or the hydrophobic and/or oleophobic molecules are required. This intermediate layer being made of a material different from that of the surface to be treated (to be functionalized), in addition to the fact that an additional treatment process step must be carried out to apply this intermediate layer, these processes of the state of the technique does not make it possible to guarantee optimal and lasting adhesion between the surface to be treated and the intermediate adhesion layer.

The object of the present invention is to overcome the drawbacks of the state of the art by providing a method minimizing the number of manufacturing process steps and optimizing the adhesion (the attachment) of epilames and/or hydrophobic molecules and /or oleophobic on a pretreated surface so that the anchors of the epilames and/or the hydrophobic and/or oleophobic molecules bind strongly and durably to the pretreated surface, thus allowing a high resistance of the coupling agents (epilames) and/ or hydrophobic and/or oleophobic molecules to successive washing cycles.

To solve this problem, there is provided according to the invention, a method for treating a surface as indicated at the beginning, characterized in that it comprises a step of pretreatment by a plasma method of said surface before said step of application of hydrophobic and/or oleophobic molecules and/or application of an epilame.

In the context of the present invention, it has been determined that a plasma pretreatment of said surface makes it possible to create attachment sites directly at the level of the latter in such a way that a subsequent treatment with a coupling agent (epilame ) and/or hydrophobic and/or oleophobic molecules of this same surface then comprising attachment sites is optimized. More specifically, he has been shown that a pretreatment by a plasma process with creation of hooks on the surface to be treated subsequently allows a coupling agent (epilame) and/or hydrophobic and/or oleophobic molecules to adhere more strongly and resist better to successive washing cycles.

It has in fact been demonstrated that a plasma treatment, for example by oxygen plasma or by nitrogen plasma, makes it possible to provide the surface, during a pretreatment step, with adequate attachment sites of the -OH or - type. NH ₂ , these attachment sites making it possible to ensure better adhesion of the epilames and/or of the hydrophobic and/or oleophobic molecules applied subsequently. Indeed, it has been demonstrated that the attachment sites formed by plasma treatment (oxygen, nitrogen or other) are nucleophilic sites favoring the attachment of the anchors of the epilames but also of hydrophobic and/or oleophobic molecules.

• d'un monomère répondant à la formule générale (I) suivante :
  
  où
  • chaque R₁, indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, sont sélectionnés dans le groupe constitué d'une liaison, (CR₅R₆)_n, où chaque R₅ et R₆, identiques ou différents l'un de l'autre sont sélectionnés indépendamment dans le groupe constitué de H, d'un groupe alkyl comprenant 1 à 10 atomes de carbone, lequel est optionnellement substitué par au moins un atome de la famille des halogènes, un groupe aryle ou un groupe aralkyle, n étant compris entre 1 et 50, et d'une chaine polyalkylène oxyde présentant de 1 à 100 répétitions d'unités alkylène oxyde ;
  • R' est sélectionné dans le groupe constitué d'une liaison, (CR₅R₆)_n, où chaque R₅ et R₆, identiques ou différents l'un de l'autre sont sélectionnés indépendamment dans le groupe constitué de H, d'un groupe alkyl comprenant 1 à 10 atomes de carbone, lequel est optionnellement substitué par au moins un atome de la famille des halogènes, un groupe aryle ou un groupe aralkyle, n étant compris entre 1 et 50 ;
  • chaque R₂ et R₂', indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, sont sélectionnés dans le groupe constitué d'une liaison, (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, S(CO), (CO)S, et
• n est compris entre 1 et 100 ;
  • R₃ est sélectionné dans le groupe constitué d'un groupe perfluoroalkyle comprenant de 1 à 50 atomes de carbone, (CF(CF₃)CF₂O)_n(CF₂)₂CF₃, (CF₂CF(CF₃)O)_n(CF₂)₂CF₃, (CF₂CF₂CF₂O)n(CF₂)₂CF₃ et (CF₂CF₂O)n(CF₂)CF₃, et n est compris entre 0 et 100 ;
  • F est sélectionné dans le groupe constitué de PO₃H₂ et OPO₃H₂, de préférence PO₃H₂ ;
    et/ou
• d'un dimère répondant à la formule générale (II) suivante :
  
  où
  • chaque R₁, indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, sont sélectionnés dans le groupe constitué d'une liaison, (CR₅R₆)_n, où chaque R₅ et R₆, identiques ou différents l'un de l'autre sont sélectionnés indépendamment dans le groupe constitué de H, d'un groupe alkyl comprenant 1 à 10 atomes de carbone, lequel est optionnellement substitué par au moins un atome de la famille des halogènes, un groupe aryle ou un groupe aralkyle, n étant compris entre 1 et 50, et d'une chaine polyalkylène oxyde présentant de 1 à 100 répétitions d'unités alkylène oxyde ;
  • chaque R', indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, sont sélectionnés dans le groupe constitué d'une liaison, (CR₅R₆)_n, où chaque R₅ et R₆, identiques ou différents l'un de l'autre sont sélectionnés indépendamment dans le groupe constitué de H, d'un groupe alkyl comprenant 1 à 10 atomes de carbone, lequel est optionnellement substitué par au moins un atome de la famille des halogènes, un groupe aryle ou un groupe aralkyle, n étant compris entre 1 et 50 ;
  • chaque R₂, indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, sont sélectionnés dans le
    
    groupe constitué d'une liaison, (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, ,S(CO), (CO)S,

et n est compris entre 1 et 100 ;

• chaque R₃, égaux ou différents l'un de l'autre sont sélectionnés dans le groupe constitué d'un groupe perfluoroalkyle comprenant de 1 à 50 atomes de carbone, (CF(CF₃)CF₂O)_n(CF₂)₂CF₃, (CF₂CF(CF₃)O)_n(CF₂)₂CF₃, (CF₂CF₂CF₂O)n(CF₂)₂CF₃ et (CF₂CF₂O)n(CF₂)CF₃, et n est compris entre 0 et 100 ;
• chaque R₄, égaux ou différents l'un de l'autre sont sélectionnés dans le groupe constitué de H, d'un groupe alkyl comprenant 1 à 10 atomes de carbone, lequel est optionnellement substitué par au moins un atome de la famille des halogènes, un groupe aryle ou un groupe aralkyle, préférentiellement chaque R₄ est H ;
• T est une liaison, (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,
  
  ,S(CO), (CO)S, et n est compris entre 1 et 100 ;
• chaque F et F', indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, sont sélectionnés dans le groupe constitué de PO₃H₂, OPO₃H₂, SH, et SiX₃ avec X= H, Cl, OMe, OEt, OiPr, de préférence PO₃H₂ ;

ledit monomère de formule générale (I) et/ou ledit dimère de formule générale (II) comprenant au moins, à une première extrémité de chaîne, un groupement phosphorylé représentant une accroche et au moins, à une deuxième extrémité de chaîne opposée à ladite première extrémité de chaîne, un groupement perfluoré.According to the method according to the invention, said step of applying, on said surface, hydrophobic and/or oleophobic molecules and/or applying an epilame is carried out by applying:

• of a monomer corresponding to the following general formula (I):
  
  Or
  • each R ₁ , independent of each other, 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 or different from each other, are independently selected from the group consisting of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the family halogens, a aryl group or an aralkyl group, n being between 1 and 50, and a polyalkylene oxide chain having from 1 to 100 repetitions of alkylene oxide units;
  • R' is selected from the group consisting of a bond, (CR ₅ R ₆ ) _n , wherein each R ₅ and R ₆ , the same or different from each other are independently selected from the group consisting of H, d an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom from the halogen family, an aryl group or an aralkyl group, n being between 1 and 50;
  • each R ₂ and R ₂ ', independent of each other, and identical or different from each other at each occurrence, are selected from the group consisting of a bond, (CH ₂ ) _n , O , S, SS, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-CS-NH, NH(CO)O,
    
    NH(CS)O, S(CO), (CO)S, and
• n is between 1 and 100;
  • R ₃ is selected from the group consisting of a perfluoroalkyl group comprising from 1 to 50 carbon atoms, (CF(CF ₃ )CF ₂ O) _n (CF ₂ ) ₂ CF ₃ , (CF ₂ CF(CF ₃ )O ) _n (CF ₂ ) ₂ CF ₃ , (CF ₂ CF ₂ CF ₂ O)n(CF ₂ ) ₂ CF ₃ and (CF ₂ CF ₂ O)n(CF ₂ )CF ₃ , and n is between 0 and 100;
  • F is selected from the group consisting of PO ₃ H ₂ and OPO ₃ H ₂ , preferably PO ₃ H ₂ ;
    and or
• of a dimer corresponding to the following general formula (II):
  
  Or
  • each R ₁ , independent of each other, 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 or different from each other, are independently selected from the group consisting of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the family halogens, an aryl group or an aralkyl group, n being between 1 and 50, and a polyalkylene oxide chain having from 1 to 100 repetitions of alkylene oxide units;
  • each R', independent of each other, 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 or different from each other, are independently selected from the group consisting of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the family halogens, an aryl group or an aralkyl group, n being between 1 and 50;
  • each R ₂ , independent of each other, and identical or different from each other at each occurrence, are selected from the
    
    group consisting of a bond, (CH ₂ ) _n , O, S, SS, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-CS -NH, NH(CO)O, NH(CS)O, ,S(CO), (CO)S,

and n is between 1 and 100;

• each R ₃ , equal to or different from each other, are selected from the group consisting of a perfluoroalkyl group comprising from 1 to 50 carbon atoms, (CF(CF ₃ )CF ₂ O) _n (CF ₂ ) ₂ CF ₃ , (CF ₂ CF(CF ₃ )O) _n (CF ₂ ) ₂ CF ₃ , (CF ₂ CF ₂ CF ₂ O)n(CF ₂ ) ₂ CF ₃ and (CF ₂ CF ₂ O)n(CF ₂ ) CF ₃ , and n is between 0 and 100;
• each R ₄ , equal to or different from each other, is selected from the group consisting of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the halogen family , an aryl group or an aralkyl group, preferably each R ₄ is H;
• T is a bond, (CH ₂ ) _n , O, S, SS, NH, O(CO), O(CS), NH(CO), NH(CS), NH(CO)NH, NH-CS-NH , NH(CO)O, NH(CS)O,
  
  ,S(CO), (CO)S, and n is between 1 and 100;
• each F and F', independent of each other, and identical or different from each other at each occurrence, are selected from the group consisting of PO ₃ H ₂ , OPO ₃ H ₂ , SH, and SiX ₃ with X= H, Cl, OMe, OEt, OiPr, preferably PO ₃ H ₂ ;

said monomer of general formula (I) and/or said dimer of general formula (II) comprising at least, at a first chain end, a phosphorylated group representing a hook and at least, at a second chain end opposite said first chain end, a perfluorinated group.

Preferably, 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 independently selected from the group consisting of H, a linear or branched alkyl group comprising from 1 to 8 carbon atoms, which is optionally substituted by at least one atom from the halogen family, an aryl group or an aralkyl group, n being between 1 and 30.

Preferably, each R ₁ , independent of each other, and identical or different from each other at each occurrence, are (CH ₂ ) _n and n is between 1 and 30.

Preferably, each R', independent of one another, and identical or different from one another 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 or different from each other, are independently selected from the group consisting of H, a linear or branched alkyl group comprising from 1 to 8 carbon atoms, which is optionally substituted by at least one atom from the halogen family, an aryl group or an aralkyl group, n being between 1 and 30.

Preferably, 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, preferably , each R' is a bond.

Among the repeated alkylene oxide units, can 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, preferably m is between 3 and 10.

Regarding non-limiting examples of 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.

Preferably, the perfluoroalkyl group comprises 3 to 25 carbon atoms, preferentially from 4 to 20 carbon atoms, more preferentially from 6 to 12 carbon atoms.

Preferably, the process for treating a surface according to the invention comprises a prior step of dissolving said hydrophobic and/or oleophobic molecules and/or said epilame in a solvent, therefore the monomer of general formula (I) and/or or the dimer of general formula (II) to form a surface treatment solution.

Advantageously, according to the invention, said prior step of dissolving in a solvent to form a surface treatment solution is carried out by dissolving in a solvent chosen from the group consisting of isopropanol, ethanol, methanol , dimethylformamide, acetone, tetrahydrofuran, preferably isopropanol.

Preferably, according to the invention, said prior step of dissolving in a solvent forms a surface treatment solution comprising said hydrophobic and/or oleophobic molecules and/or said epilame, therefore said monomer of general formula (I) and/ or said dimer of general formula (II), in a proportion of 0.01% to 10% v/v in a solvent, preferably in a proportion of 0.1% to 5% v/v.

• un égouttage dudit article mis en contact avec lesdites molécules hydrophobes et/ou oléophobes et/ou avec ledit épilame, donc avec ledit monomère de formule générale (I) et/ou avec ledit dimère de formule générale (II), et/ou
• un lavage de ladite surface mise en contact avec lesdites molécules hydrophobes et/ou oléophobes et/ou avec ledit épilame, donc avec ledit monomère de formule générale (I) et/ou avec ledit dimère de formule générale (II), et/ou
• un séchage dudit article mis en contact avec lesdites molécules hydrophobes et/ou oléophobes et/ou avec ledit épilame, donc avec ledit monomère de formule générale (I) et/ou avec ledit dimère de formule générale (II).

Advantageously, the method according to the invention further comprises at least one of the following additional steps:

• a draining of said article brought into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II), and/or
• washing of said surface brought into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II), and/or
• drying of said article brought into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II).

Preferably, according to the invention, said step of bringing said pretreated surface into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II), is produced by spraying, by dipping, by vaporization, by dabbing, by wiping, by spin coating and by deep coating.

Other embodiments of the process according to the invention are indicated in the appended claims.

The present invention also relates to an article (or a product), in particular to an article (or a product) for horology, automobiles, microelectronics, optics, aeronautics, nautical, medical, packing or construction, having at least a portion of surface treated according to the method according to the invention.

Other embodiments of an article according to the invention are indicated in the appended claims.

The present invention also relates to a use of hydrophobic and/or oleophobic molecules and/or of an epilame, therefore of a monomer of general formula (I) and/or of a dimer of general formula (II) in a treatment surface, in particular for a treatment of a surface of a timepiece, automotive, microelectronics, optical, aeronautical, nautical, medical, packing or construction part. Other embodiments for the use of hydrophobic and/or oleophobic molecules and/or of an epilame, for example of a monomer of general formula (I) and/or of a dimer of general formula (II), according to the invention are indicated in the appended claims.

• La figure 1 est un graphique illustrant les résultats obtenus, lors d'essais de résistance à des cycles de lavage successifs, en termes de mesures de valeurs d'angle de contact, pour surface en laiton traitée avec un agent de couplage suivant l'invention avec ou sans prétraitement par plasma.
• La figure 2 est un graphique illustrant les résultats obtenus, lors d'essais de résistance à des cycles de lavage successifs, en termes de mesures de valeurs d'angle de contact, pour une surface en laiton traitée avec différents agents de couplage selon l'invention avec ou sans prétraitement par plasma.
• La figure 3 est un graphique illustrant les résultats obtenus, lors d'essais de résistance à des cycles de lavage successifs, en termes de mesures de valeurs d'angle de contact, pour surface en laiton rhodié traitée avec un agent de couplage suivant l'invention avec ou sans prétraitement par plasma.
• La figure 4 est un graphique illustrant les résultats obtenus, lors d'essais de résistance à des cycles de lavage successifs, en termes de mesures de valeurs d'angle de contact, pour une surface en laiton rhodié traitée avec différents agents de couplage selon l'invention avec ou sans prétraitement par plasma.
• La figure 5 est un graphique illustrant les résultats obtenus, lors d'essais de résistance à des cycles de lavage successifs, en termes de mesures de valeurs d'angle de contact, pour surface en saphir traitée avec un agent de couplage suivant l'invention avec ou sans prétraitement par plasma.
• La figure 6 est un graphique illustrant les résultats obtenus, lors d'essais de résistance à des cycles de lavage successifs, en termes de mesures de valeurs d'angle de contact, pour une surface en saphir traitée avec différents agents de couplage selon l'invention avec ou sans prétraitement par plasma.

Other characteristics, details and advantages of the invention will emerge from the examples given below, on a non-limiting basis and with reference to the attached figures (graphs).

• There figure 1 is a graph illustrating the results obtained, during resistance tests to successive washing cycles, in terms of measurements of contact angle values, for a brass surface treated with a coupling agent according to the invention with or without plasma pretreatment.
• There picture 2 is a graph illustrating the results obtained, during resistance tests to successive washing cycles, in terms of measurements of contact angle values, for a brass surface treated with different coupling agents according to the invention with or without plasma pretreatment.
• There picture 3 is a graph illustrating the results obtained, during resistance tests to successive washing cycles, in terms of measurements of contact angle values, for a rhodium-plated brass surface treated with a coupling agent according to the invention with or without plasma pretreatment.
• There figure 4 is a graph illustrating the results obtained, during resistance tests to successive washing cycles, in terms of measurements of contact angle values, for a rhodium-plated brass surface treated with different coupling agents according to the invention with or without plasma pretreatment.
• There figure 5 is a graph illustrating the results obtained, during tests of resistance to successive washing cycles, in terms of measurements of contact angle values, for a sapphire surface treated with a coupling agent according to the invention with or without plasma pretreatment.
• There figure 6 is a graph illustrating the results obtained, during resistance tests to successive washing cycles, in terms of measurements of contact angle values, for a sapphire surface treated with different coupling agents according to the invention with or without plasma pretreatment.

EXAMPLES A. Synthesis of a compound of general formula (I) or of a compound of general formula (II) according to the invention I. Synthesis of a monomer of general formula (I) 1. Synthesis of ...

For example, a synthetic method such as that described in the document WO03/102003 can be implemented in order to obtain such a monomer of general formula (I).

2. Synthesis of a monomer of general formula (I) as indicated above but further comprising an ester function.

II. Synthesis of a dimer of general formula (II) 1. Synthesis of a compound of general formula (II): synthesis of the acid 10, 11 -bis (2,2,3,3,4,4,5,5,6,6,7,7,8 ,8,9,9,9 heptadecafluorononyl)icosane-1,20-diyldi-phosohonic Step 1 of synthesis of 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.

An equimolar mixture of undecenol (62.3 g; 370 mmol) and perfluoro-1- iodooctane (200 g; 370 mmol; 1 eq.) dissolved in 55 mL of dichloromethane. The reaction is heated at 50° C. for 3 hours, cooled with an ice bath and then 185 mL of an acetic acid-water-hydrochloric acid (12N) mixture (3/6/1) is added to the reaction medium. After reaction at room temperature for 3 hours, the reaction crude is washed successively with deionized water (x2) and with a saturated solution of sodium chloride, dried over anhydrous magnesium sulphate and then concentrated. The residue is purified by chromatography on a column of silica gel to give a white wax (109 g; 50%). In the end, 10,11-bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9 heptadecafluorononyl)icosane-1 is obtained ,20-diol.

Step 2 starting with 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)

To a solution of 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 (109 g; 93 mmol) dissolved in 1 L of dichloromethane, are added triphenylphosphine (53.3 g; 204 mmol; 2.2 eq.) and N-Bromosuccinimide (36.1 g; 204 mmol ; 2.2 eq.). The reaction takes place at room temperature for 3 hours. After evaporation of the dichloromethane, the residue is purified on a column of silica gel to give a colorless oil (108.6 g; 90%). In the end, 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 tetratriacontafluoroicosane.

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)

To a solution of 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 (108.6 g; 83 mmol), heated to 140°C, is added dropwise triethylphosphite (70.6 g; 73.6 mL; 417 mmol; 5 eq.). At the end of this addition, stirring and heating are maintained for 12 hours. After evaporation of the excess triethylphosphite, the reaction crude is purified by chromatography on a column of silica gel to give a colorless oil (94.2 g; 80%). In the end, tetraethyl 10,11-bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl)- is obtained. icosane-1,20-diylbisphosphonate.

Stage 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)

To a solution of 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 (94.2 g; 66 mmol) dissolved in 400 mL of anhydrous dichloromethane and placed under an inert atmosphere, is added with trimethylbromosilane (50.5 g; 43.5 mL, 330 mmol; 5 eq.). The reaction takes place at room temperature for 3 hours. After evaporation of the dichloromethane, 400 mL of methanol is added to the reaction medium and stirring is maintained at ambient temperature for 12 hours. The methanol is evaporated off and the reaction crude is purified by recrystallization to give a beige solid (77.6 g; 90%). In the end, the acid 10,11-bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9 heptadecafluorononyl)icosane is obtained -1,20-diyldi-phosphonic (formula D), this molecule corresponding to the general formula 1 according to the invention.

This process for the synthesis of 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.

2. Synthesis of a compound of general formula (I): synthesis of 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20 acid diyldiohosohonic Step 1 synthetic 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diol

An equimolar mixture of undecenol (4.1 g; 26.5 mmol) and of perfluoro-1-iodobutane (9.4 g; 26.5 mmol; 1 eq.) dissolved in 10 mL of dichloromethane. The reaction is heated at 50° C. for 3 hours, cooled with an ice bath and then 25 mL of an acetic acid-water-hydrochloric acid (12N) mixture (3/6/1) is added to the reaction medium. After reaction at room temperature for 3 hours, the reaction crude is washed successively with deionized water (x2) and with a saturated solution of sodium chloride, dried over anhydrous magnesium sulphate and then concentrated. The residue is purified by chromatography on a column of silica gel to give a white wax (9.7 g; 47%). In the end, 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diol is obtained.

Step 2 starting from 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diol (formula E)

To a solution of 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diol (9.7 g; 12.5 mmol) dissolved in 30 ml of dichloromethane are added with triphenylphosphine (7.2 g; 27 mmol; 2.2 eq.) and N-Bromosuccinimide (4.9 g; 27 mmol; 2.2 eq.). The reaction takes place at room temperature for 3 hours. After evaporation of the dichloromethane, the residue is purified on a silica gel column to give a colorless oil (9.7 g; 86%). In the end, 1,20-dibromo-10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl) icosane is obtained.

Step 3 starting from 1,20-dibromo-10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane (formula F)

To a solution of 1,20-dibromo-10,11-bis(2,2,3,3,4,4,5,5,5 nonafluoropentyl)icosane (9.7 g; 11 mmol) heated to 140°C is added dropwise triethylphosphite (9.1 g; 9.5 mL; 55 mmol; 5 eq.). At the end of the addition, stirring and heating are maintained for 12 hours. After evaporation of the excess triethylphosphite, the reaction crude is purified by chromatography on a gel column of silica to give a colorless oil (9.2 g; 84%). In the end, tetraethyl 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diylbisphosphonate is obtained.

Step 4 starting from tetraethyl 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diylbisphosphonate (formula G)

To a solution of dissolved tetraethyl 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20-diyl-bisphosphonate (9.2 g; 9 mmol) in 60 mL of anhydrous dichloromethane and placed under an inert atmosphere, is added trimethylbromosilane (7.1 g; 6.1 mL, 45 mmol; 5 eq.). The reaction takes place at room temperature for 3 hours. After evaporation of the dichloromethane, 400 mL of methanol is added to the reaction medium and stirring is maintained at ambient temperature for 12 hours. The methanol is evaporated to give a colorless oil (7.2 g; 88%). In the end, 10,11-bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)icosane-1,20 diyldiphosphonic acid (formula H) is obtained, this molecule responding to the general formula 1 according to the invention.

This process for the synthesis of 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.

B. Comparative tests: surface treatments with different epilames with or without plasma pre-treatment of the surfaces

In order to be able to determine the impact of a plasma pretreatment of a surface on the attachment (adherence) of the epilames (coupling agents) according to the invention (monomer of general formula (I) and/or dimer of general formula (II)), comparative studies, in terms of resistance of these epilames to successive washing cycles, were carried out by measuring the contact angle values with Moebius 9010/10 FL oil.

a) Pretreatment by a plasma process

According to the invention, a pretreatment with an oxygen plasma was carried out on the surfaces to be treated with the PICO LF PCCE apparatus for 4 minutes at a power of 100 W.

b) Surface treatment with an epilaming solution

Following step a) of pretreatment and prior to carrying out 7 successive washing cycles, the pretreated surfaces were treated by immersion for 5 minutes or 15 minutes in epilaming solutions containing a monomer of general formula (I) and/or a dimer of general formula (II) in an amount of 2.5×10 ^-3 molL ^-1 in isopropanol as solvent. Then, the treated substrates were drained for 1 minute and then dried under hot air (55° C.) for 5 minutes.

c) Wash cycles

Following the pretreatment and the treatment of the surfaces with the epilaming solutions, that is to say following steps a) and b), 7 successive washing cycles were carried out for each surface. Each washing cycle was carried out as follows: Tank 1 Tank 2 Tank 3 Tank 4 Drying Product Rubisol Rubisol Isopropanol Isopropanol / Duration 6min 4 mins 3 mins 2 min 5 min Hustle 150rpm 400rpm 150rpm 150rpm 150rpm Temperature Amb Amb Amb Amb 65°C US Yes No No No No

d) Contact angle measurement

The contact angle measurement accounts for the ability of a liquid (for example 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 measurement makes it possible in particular to perform the discrimination of the polar or apolar nature of the interactions at the liquid-solid interface and therefore to deduce the hydrophilic or hydrophobic nature of a surface. Concretely, the more a large angle is measured, the more the surface has a hydrophobic/oleophobic character. On the other hand, the more a small angle is measured, the more the surface has a hydrophilic character.

For an epilame within the meaning of the present invention, it is advisable to obtain a contact angle value that is as large as possible, which therefore means that this molecule is hydrophobic/oleophobic and therefore makes it possible to avoid spreading of a liquid oily, for example a spread of a lubricant.

In the context of the present invention, the DSA100 apparatus associated with the DSA4 version 2.0 software was used in order to carry out these contact angle measurements.

1. Comparative tests : treatment of a brass surface with a coupling agent according to the invention with or without plasma pretreatment

A brass surface pretreated or not by oxygen plasma was treated with a dimer (OLEOXEIN+) according to the invention corresponding to the general formula (II) and which is the following:

The results obtained during the contact angle measurements are presented in figure 1 . These results show that pretreatment of the brass surface by oxygen plasma, before treatment of this same surface with a molecule of general formula (II) according to the invention, significantly increases the resistance of the epilame to cycles successive washes.

In other words, a pretreatment of the surface by oxygen plasma before a treatment with a dimer of general formula (II) allows the latter to cling (adhere) more strongly to the treated surface and in particular to resist better. to hydrolysis in an acidic or basic medium, this giving the epilame a high stability over time.

2. Comparative tests: treatment of a brass surface with coupling agents according to the invention with or without plasma pretreatment

In the same perspective as the previous example, on a brass surface pretreated or not by oxygen plasma, various coupling agents (epilames) according to the invention were tested, namely a monomer (OLEOXEIN) corresponding to a molecule of formula general formula (I) according to the invention and a dimer (OLEOXEIN+) corresponding to a molecule of general formula (II) according to the invention. These two molecules (epilames) according to the invention are the following:

The results obtained during the contact angle measurements are presented in picture 2 . As can be seen, whether for the monomer (general formula (I)) or the dimer (general formula (II)) tested as coupling agent (epilame), pretreatment with oxygen plasma makes it possible to increase significantly the resistance of the epilame to successive washing cycles, whether the treatment of the surface by immersion in a solution containing the epilame lasted 5 or 15 minutes.

As for the previous example, this indicates that a pretreatment of the surface by oxygen plasma before a treatment with a molecule of general formula (I) or a molecule of general formula (II) allows the latter to cling ( to adhere) more strongly to the treated surface and in particular to better resist hydrolysis in an acidic or basic medium, this giving the epilame a high stability over time.

3. Comparative tests : treatment of a rhodium-plated brass surface with a coupling agent according to the invention with or without plasma pretreatment

In the same vein as the previous examples, on a rhodium-plated brass surface pretreated or not by oxygen plasma, a coupling agent (epilame) was tested, namely the same dimer (OLEOXEIN+) as that of example 1 responding to the general formula (II) according to the invention. The results obtained during the contact angle measurements are presented in picture 3 .

As can be seen, a pretreatment with oxygen plasma makes it possible to significantly increase the resistance to successive washing cycles, whether the treatment of the surface by immersion in a solution containing the epilame lasted 5 or 15 minutes.

This again indicates that a pretreatment of the surface by oxygen plasma, before a treatment with a molecule of general formula (II) according to the invention, allows the latter to cling (adhere) more strongly to the surface. treated and in particular better resist hydrolysis in an acidic or basic medium, this giving the epilame a high stability over time.

4. Comparative tests : treatment of a rhodium-plated brass surface with coupling agents according to the invention with or without plasma pretreatment

On a rhodium-plated brass surface, whether or not pretreated with oxygen plasma, various coupling agents (epilames) were tested, namely a monomer (OLEOXEIN) corresponding to a molecule of general formula (I) according to the invention and a dimer (OLEOXEIN+) corresponding to a molecule of general formula (II) according to the invention. These molecules (epilames) are identical to those tested in example 2. The results obtained during the contact angle measurements are presented in figure 4 .

As can be seen, whether for a monomer corresponding to a molecule of general formula (I) according to the invention or for a dimer corresponding to a molecule of general formula (II) according to the invention, a pretreatment with plasma d oxygen makes it possible to significantly increase the resistance to successive washing cycles, whether the treatment of the surface by immersion in a solution containing the epilame lasted 5 or 15 minutes.

As for the previous examples, this indicates that a pretreatment of the surface by oxygen plasma allows stronger attachment (adhesion) to the treated surface and in particular better resistance to hydrolysis in an acid or basic medium, this giving the epilame a high stability over time.

5. Comparative tests: treatment of a sapphire surface with a coupling agent according to the invention with or without plasma pretreatment

On a sapphire surface pretreated or not by oxygen plasma, a coupling agent (epilame), namely the same dimer (OLEOXEIN+) as that of example 1 corresponding to the general formula (II) according to l 'invention. The results obtained during the contact angle measurements are presented in figure 5 .

As can be seen, a pretreatment with oxygen plasma makes it possible to significantly increase the resistance to successive washing cycles, whether the treatment of the surface by immersion in a solution containing the epilame lasted 5 or 15 minutes. This again indicates that a pretreatment of the surface by oxygen plasma, before a treatment with a molecule of general formula (II) according to the invention, allows the latter to cling (adhere) more strongly to the surface. treated and in particular to better resist hydrolysis in the medium acidic or basic, this giving the epilame a high stability over time.

6. Comparative tests: treatment of a sapphire surface with coupling agents according to the invention with or without plasma pretreatment

On a sapphire surface pretreated or not with oxygen plasma, various coupling agents (epilames) were tested, namely a monomer (OLEOXEIN) corresponding to a molecule of general formula (I) according to the invention and a dimer ( OLEOXEIN+) corresponding to a molecule of general formula (II) according to the invention. These molecules (epilames) are identical to those tested in example 2. The results obtained during the contact angle measurements are presented in figure 6 .

As can be seen, whether for a monomer corresponding to a molecule of general formula (I) according to the invention or for a dimer corresponding to a molecule of general formula (II) according to the invention, a pretreatment by oxygen plasma makes it possible to significantly increase the resistance to successive washing cycles, whether the treatment of the surface by immersion in a solution containing the epilame lasted 5 or 15 minutes.

Just as for the preceding examples, this indicates that a pretreatment of the surface by oxygen plasma, before a treatment with a molecule of general formula (I) or of general formula (II) according to the invention, allows the latter to s cling (adhere) more strongly to the treated surface and in particular better resist hydrolysis in an acidic or basic medium, this giving the epilame high stability over time.

It is understood that the present invention is in no way limited to the embodiments described above and that many modifications can be made thereto without departing from the scope of the appended claims.

Claims (8)

1. A method for treating a surface selected from the group constituted of sapphire, brass, rhodium-plated brass, gold-plated brass, nickel, steel, hardenable steel, iron, aluminium, titanium, lead, silver, gold, chromium, copper, manganese, vanadium, lithium, cobalt, silicon and various metal alloys and oxides of such metals, said surface treatment method comprising a step of applying, on said surface, hydrophobic and/or oleophobic molecules and/or of applying an epilame, said method comprising a step of pretreating said surface by a plasma method prior to said step of applying hydrophobic and/or oleophobic molecules and/or of applying an epilame,

   characterised in that said step of applying, on said surface, hydrophobic and/or oleophobic molecules and/or of applying an epilame is carried out by applying

   - a monomer of the following general formula (I):

   

   wherein

   - each R₁, independent of one another, and identical to or different from one another on each occurrence, is selected from the group constituted of a bond, (CR₅R₆)_n, wherein each R₅ and R₆, identical to or different from one another, are selected independently from the group constituted of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the halogen family, an aryl group or an aralkyl group, n being contained between 1 and 50, and a polyalkylene oxide chain having from 1 to 100 repetitions of alkylene oxide units;

   - R' is selected from the group constituted of a bond, (CR₅R₆)_n, wherein each R₅ and R₆, identical to or different from one another, are selected independently from the group constituted of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the halogen family, an aryl group or an aralkyl group, n being contained between 1 and 50;

   - each R₂ and R₂', independent of one another, and identical to or different from one another on each occurrence, are selected from the group constituted of a bond, (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, S(CO), (CO)S,
   and

   - n is contained between 1 and 100;

   - R₃ is selected from the group constituted of a perfluoroalkyl group comprising from 1 to 50 carbon atoms, (CF(CF₃)CF₂O)_n(CF₂)₂CF₃, (CF₂CF(CF₃)O)_n(CF₂)₂CF₃, (CF₂CF₂CF₂O)n(CF₂)₂CF₃ and (CF₂CF₂O)n(CF₂)CF₃, and n is contained between 0 and 100;

   - F is selected from the group constituted of PO₃H₂ and OPO₃H₂, preferably PO₃H₂;
   and/or

   - a dimer of the following general formula (II):

   

   wherein

   - each R₁, independent of one another, and identical to or different from one another on each occurrence, is selected from the group constituted of a bond, (CR₅R₆)_n, wherein each R₅ and R₆, identical to or different from one another, are selected independently from the group constituted of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the halogen family, an aryl group or an aralkyl group, n being contained between 1 and 50, and a polyalkylene oxide chain having from 1 to 100 repetitions of alkylene oxide units;

   - each R', independent of one another, and identical to or different from one another on each occurrence, is selected from the group constituted of a bond, (CR₅R₆)_n, wherein each R₅ and R₆, identical to or different from one another, are selected independently from the group constituted of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the halogen family, an aryl group or an aralkyl group, n being contained between 1 and 50;

   - each R₂, independent of one another, and identical to or different from one another on each occurrence, is selected from the group constituted of a bond, (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, S(CO), (CO) S,

   

   and n is contained between 1 and 100;

   - each R₃, equal to or different from one another, is selected from the group constituted of a perfluoroalkyl group comprising from 1 to 50 carbon atoms, (CF(CF₃)CF₂O)_n(CF₂)₂CF₃, (CF₂CF(CF₃)O)_n(CF₂)₂CF₃, (CF₂CF₂CF₂O)n(CF₂)₂CF₃ and (CF₂CF₂O)n(CF₂)CF₃, and n is contained between 0 and 100;

   - each R₄, equal to or different from one another, is selected from the group constituted of H, an alkyl group comprising 1 to 10 carbon atoms, which is optionally substituted by at least one atom of the halogen family, an aryl group or an aralkyl group, preferably each R₄ is H;

   - T is a bond, (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,

   

   , S(CO), (CO)S, and n is contained between 1 and 100;

   - each F and F', independent of one another, and identical to or different from one another on each occurrence, are selected from the group constituted of PO₃H₂, OPO₃H₂, SH, and SiX₃ with X=H, Cl, OMe, OEt, OiPr, preferably PO₃H₂; said monomer of general formula (I) and/or said dimer of general formula (II) comprising at least, at a first chain end, a phosphorylated group representing an attachment and at least, at a second chain end opposite said first chain end, a perfluorinated group.
2. The method for treating a surface according to Claim 1, characterised in that it comprises a preliminary step of dissolving in a solvent said hydrophobic and/or oleophobic molecules and/or said epilame, therefore the monomer of general formula (I) and/or the dimer of general formula (II), in order to form a surface treatment solution.
3. The method for treating a surface according to Claim 2, characterised in that said preliminary step of dissolving in a solvent in order to form a surface treatment solution is carried out by dissolving in a solvent selected from the group constituted of isopropanol, ethanol, methanol, dimethylformamide, acetone, tetrahydrofuran, preferably isopropanol.
4. The method for treating a surface according to Claim 2 or 3, characterised in that said preliminary step of dissolving in a solvent forms a surface treatment solution comprising said hydrophobic and/or oleophobic molecules and/or said epilame, therefore said monomer of general formula (I) and/or said dimer of general formula (II), at the rate of 0.01% to 10% v/v in a solvent, preferably at the rate of 0.1% to 5% v/v.
5. The method for treating a surface according to any one of Claims 1 to 4, characterised in that it additionally comprises at least one of the following additional steps:

   - draining of said article brought into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II), and/or

   - washing of said surface brought into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II), and/or

   - drying of said article brought into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II).
6. The method for treating a surface according to any one of Claims 1 to 5, characterised in that said step of bringing said pretreated surface into contact with said hydrophobic and/or oleophobic molecules and/or with said epilame, therefore with said monomer of general formula (I) and/or with said dimer of general formula (II), is carried out by spraying, soaking, vaporisation, buffering, wiping, spin coating and deep coating.
7. An article, in particular a watchmaking, automotive, microelectronic, optical, aeronautical, nautical, medical, packing or construction article, having at least a part of the surface treated according to the method according to any one of Claims 1 to 6.
8. Use of hydrophobic and/or oleophobic molecules and/or an epilame, therefore of a monomer of general formula (I) and/or of a dimer of general formula (II), in a surface treatment according to any one of Claims 1 to 6, in particular for a treatment of a surface of a watchmaking, automotive, microelectronic, optical, aeronautical, nautical, medical, packing or construction article.

Images