EP3192854B1 - Item in which the surface is treated with a coupling agent having oleophobic and/or hydrophobic nature - Google Patents

Description

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.

Numerous surface treatments are known, for example the production of 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). More particularly, 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.

In the request WO2013 / 167624 , there is described the use of amine molecules (N) and phosphonic compounds (P) to cover surfaces for use in the field of watchmaking. These two types of compounds being of alkaline and acidic nature form pairs of ions that interact with all types of surfaces, whether composed of mineral materials such as glass, metal, or non-oxidized materials (among others the gold, rhodium and their alloys), or else polymeric materials.

Unfortunately, the articles currently treated on the surface with epilamizing agents (called epilams or coupling agents) do not preserve the latter in a durable and stable manner over time. Indeed, 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. Moreover, 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).

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) ou (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, OP(O)O₂ ^-, SH et SiX₃, X=H, Cl, OMe, OEt, OiPr, de préférence PO₃H₂.

To solve this problem, there is provided, according to the invention, an article whose surface is treated with a coupling agent 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, equal or different each other are independently selected from the group consisting of H, an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one family atom halogens, an aryl group or an aralkyl group, n being from 1 to 50, and a polyalkylene oxide chain having from 1 to 100 alkylene oxide unit repeats;
• 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, equal or different each other are independently selected from the group consisting of H, an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one family atom halogens, aryl or aralkyl, n being from 1 to 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 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 0 to 100;
• each R ₄ , equal to or different from each other are 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) or (CO) S, and n is from 1 to 100;
• each F and F ', independent of one another, 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 , OP ( O) O ₂ ^- , SH and SiX ₃ , X = H, Cl, OMe, OEt, OiPr, preferably PO ₃ H ₂ .

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 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.

Preferably, 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.

Preferably, 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.

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, preferentially each R 'is a bond.

Among the 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;
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, preferably 4 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.

In the context of the present invention, it has been determined that such an article whose surface is treated with such a coupling agent corresponding to the general formula (I) has surface properties superior to those obtained with the formulations of epilamization current, this in particular in terms of attachment of epilame on a surface and stability of the epilame over time (for example by adequately and increased resistance to successive washing cycles). In addition, it has been shown that such an article whose surface is treated with such a coupling agent corresponding to the general formula (I) does not deteriorate over time, in that it retains its properties of surface obtained by epilamation.

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).

In the context of the present invention, it has been demonstrated that such a treatment of a surface with a molecule of general formula (I) makes it possible to obtain a treated surface to which epilame (chemisorption) adheres strongly. that is to say the molecule of general formula (I). Moreover, the treatment according to the invention makes it possible to obtain epilamage which is stable over time and which is particularly resistant, in particular to hydrolyses in an acidic or basic medium.

Preferably, 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. It has been determined, in the context of the present invention, that 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. epilame on the surface treated by following, for example treated with a molecule of general formula (I). This pretreatment therefore makes it possible to ensure optimum grip of the epilame all the better, as well as its stability and in particular its resistance to successive washing cycles.

Advantageously, 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.

Preferably, according to the method of treating a surface of an article according to the invention, 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.

Preferably, according to the method of treating a surface of an article according to the invention, 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.

Advantageously, according to the method for treating a surface according to the invention, 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.

• un égouttage de ladite surface mise en contact avec ladite solution de traitement de surface, et/ou
• un lavage de ladite surface mise en contact avec ladite solution de traitement de surface, et/ou
• un séchage de ladite surface mise en contact avec ladite solution de traitement de surface.

According to a preferred embodiment, the method for treating a surface according to the invention also comprises at least one of the following additional steps:

• draining said surface contacted with said surface treatment solution, and / or
• washing said surface contacted with said surface treatment solution, and / or
• drying said surface contacted with said surface treatment solution.

Advantageously, according to the method of treating a surface according to the invention, 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.

Other embodiments of the method of treating a surface according to the invention are indicated in the appended claims.

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) ou (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 X et Y, indépendants l'un de l'autre, et identiques ou différents l'un de l'autre à chaque occurrence, représentent un groupement halogéné ou un groupement organique insaturé ;

ledit procédé comprenant :

• une étape de substitution d'au moins un groupement halogéné X, Y de ladite molécule de formule générale (II) par un groupement pouvant représenter, directement ou après plusieurs étapes de synthèses, une ancre dudit agent de couplage et étant sélectionné dans le groupe constitué des groupements PO₃H₂, OPO₃H₂, SH et de préférence PO₃H₂, ou
• une étape d'addition sur au moins un groupement organique insaturé X, Y de ladite molécule de formule générale (II) d'un groupement pouvant représenter, directement ou après plusieurs étapes de synthèses, une ancre dudit agent de couplage et étant sélectionné dans le groupe constitué des groupements PO₃H₂, OPO₃H₂, et SiX₃ , X=H, Cl, OMe, OEt, OiPr, de préférence PO₃H₂.

The present invention also relates to a process for the synthesis of a coupling agent corresponding to a general formula (I) as mentioned above, starting from a molecule of general formula (II) corresponding to the following formula:

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 , which are identical or different from one another, are independently selected from the group consisting of H, an alkyl group and 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 between 1 and 50, and a polyalkylene oxide chain having from 1 to 100 repeats 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, equal or different each other are independently selected from the group consisting of H, an alkyl group having 1 to 10 carbon atoms, which is optionally substituted by at least one family atom halogens, aryl or aralkyl, n being from 1 to 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) or (CO) S, and n is from 1 to 100;
• each R ₃ , equal to or different from each other are selected from the group consisting of a perfluoroalkyl group comprising 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 0 to 100;
• each R ₄ , equal to or different from each other are 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 from 1 to 100;
• each X and Y, independent of each other, and identical or different from each other at each occurrence, represent a halogenated group or an unsaturated organic group;

said method comprising:

• a step of substituting at least one X, Y halogen group of said molecule of general formula (II) with a group which can represent, directly or after several synthesis steps, an anchor of said coupling agent and being selected from the group consisting of PO ₃ H ₂ , OPO ₃ H ₂ , SH and preferably PO ₃ H _{2 groups} , or
• an addition step on at least one unsaturated organic group X, Y of said molecule of general formula (II) of a group which can represent, directly or after several synthesis steps, an anchor of said coupling agent and being selected in the group consisting of PO ₃ H ₂ , OPO ₃ H ₂ , and SiX _{3 groups} , X = H, Cl, OMe, OEt, OiPr, preferably PO ₃ H ₂ .

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 , 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.

Preferably, 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.

Preferably, 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.

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, preferentially each R 'is a bond.

Among the 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.

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, 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. In the context of the present invention, it has been determined that 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 . has an optimal grip (adhesion) on a surface and that this epilame is particularly stable over time, including resistance to many washing cycles but also to acidic hydrolysis and basic.

In the context of the present invention, those skilled in the art are quite able to determine which methodology to apply in order to obtain a molecule of general formula (II) from which, via a step of substitution of a grouping halogen, can be obtained a coupling agent of the general formula (I) according to the invention.

It is also well understood that 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). 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.

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

The present invention also relates to a use of a molecule of general formula (I) for a treatment of a surface of an article.

Preferably, 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.

Other forms of use of a molecule of general formula (I) 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, avec trois épilames (agents de couplage) différents : molécule 1 correspondant à une molécule de formule générale (I) suivant l'invention, molécule 2 et molécule 3.
• 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, avec différents épilames (agents de couplage) commerciaux (Episurf®, Fixodrop® FKBS, 3M® EGC-1700, 3M® EGC-2702 et Dupont Solrem® FS2) et avec une molécule (molécule 1) correspondant à une molécule de formule générale (I) suivant l'invention.
• 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 traitée avec un agent de couplage suivant l'invention avec ou sans prétraitement par un procédé 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 traitée avec différents agents de couplage avec ou sans prétraitement par un procédé 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 laiton rhodié traitée avec un agent de couplage suivant l'invention avec ou sans prétraitement par un procédé 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 laiton rhodié traitée avec différents agents de couplage avec ou sans prétraitement par un procédé plasma.
• La figure 7 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 un procédé plasma.
• La figure 8 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 avec ou sans prétraitement par un procédé plasma.

Other features, details and advantages of the invention will emerge from the examples given below, without limitation and with reference to the figures (graphics) attached.

• The figure 1 is a graph illustrating the results obtained during tests of resistance to successive washing cycles, in terms of measurements of contact angle values, with three different epilams (coupling agents): molecule 1 corresponding to a molecule of formula general (I) according to the invention, molecule 2 and molecule 3.
• The figure 2 is a graph illustrating the results obtained, in tests of resistance to successive washing cycles, in terms of measurements of contact angle values, with different commercial epilames (coupling agents) (Episurf®, Fixodrop® FKBS, 3M® EGC-1700, 3M® EGC-2702 and Dupont Solrem® FS2) and with a molecule (molecule 1) corresponding to a molecule of general formula (I) according to the invention.
• The figure 3 is a graph illustrating the results obtained, in tests of resistance to successive washing cycles, in terms of measurements of contact angle values, for brass surface treated with a coupling agent according to the invention with or without pretreatment by a plasma process.
• The figure 4 is a graph illustrating the results obtained, in tests of resistance to successive washing cycles, in terms of measurements of contact angle values, for a brass surface treated with different coupling agents with or without pre-treatment by a plasma process.
• The 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 rhodium-plated brass surface treated with a coupling agent according to the invention with or without pretreatment by a plasma process.
• The figure 6 is a graph illustrating the results obtained, in tests of resistance to successive washing cycles, in terms of measurements of contact angle values, for a rhodium-plated brass surface treated with different coupling agents with or without pretreatment by a plasma process.
• The figure 7 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 pretreatment by a plasma process.
• The figure 8 is a graph illustrating the results obtained, in tests of resistance to successive washing cycles, in terms of measurements of contact angle values, for a sapphire surface treated with different coupling agents with or without pre-treatment by a plasma process.

EXAMPLES A. Synthesis of a Compound of General Formula (I) According to the Invention 1. Synthesis of a Compound of General Formula (I): Synthesis of 10,11-bis (2,2,3,3,4,4,5,5,6,6,7,7,8 Acid , 8,9,9,9 heptadecafluorononyl) icosane-1,20-diyldi-phosphonic acid Synthetic Step 1 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.

To a zinc / copper dispersion (47 g, 740 mmol, 2 eq) in 70 mL of dichloromethane is added dropwise 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 a mixture of acetic acid-water-hydrochloric acid (12N) (3/6/1) is added to the reaction medium. After reaction at room temperature for 3 hours, the crude reaction product 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 column chromatography on silica gel to give a white wax (109 g, 50%). Finally, 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 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)

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 supplemented with triphenylphosphine (53.3 g, 204 mmol, 2.2 eq.) And N-bromosuccinimide (36.1 g, 204 mmol). 2.2 eq.). The reaction is carried out at ambient temperature for 3 hours. After evaporation of the dichloromethane, the residue is purified on a gel column of silica to give a colorless oil (108.6 g, 90%). In the final, 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)

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 tetracyclafluoroicosane (108.6 g, 83 mmol), heated to 140 ° C, is added drip of 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 crude reaction product is purified by column chromatography on silica gel to give a colorless oil (94.2 g, 80%). Finally, 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.

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)

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 trimethylbromosilane (50.5 g, 43.5 mL, 330 mmol, 5 eq.). The reaction is carried out at ambient temperature for 3 hours. After evaporation of the dichloromethane, 400 mL of methanol is added to the reaction medium and stirring is maintained at room temperature for 12 hours. The methanol is evaporated and the crude reaction product is purified by recrystallization to give a white solid (77.6 g, 90%). In final, is obtained 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-phosphonic acid (formula D), this molecule corresponding to the general formula 1 according to the invention.

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.

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 diyldiphosphonique Synthetic Step 1 of 10,11-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl) icosane-1,20-diol

To a zinc / copper dispersion (3.4 g, 53 mmol, 2 eq) in 10 mL of dichloromethane is added dropwise an equimolar mixture of undecenol (4.1 g, 26.5 mmol) and 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 a mixture of acetic acid-water-hydrochloric acid (12N) (3/6/1) is added to the reaction medium. After reaction at room temperature for 3 hours, the crude reaction product 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 column chromatography on silica gel to give a white wax (9.7 g, 47%). Finally, 10,11-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl) icosane-1,20-diol is obtained.

Step 2 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 supplemented with triphenylphosphine (7.2 g, 27 mmol, 2.2 eq) and N-bromosuccinimide (4.9 g, 27 mmol, 2.2 eq). The reaction is carried out at ambient temperature for 3 hours. After evaporation of the dichloromethane, the residue is purified on a column of silica gel to give a colorless oil (9.7 g, 86%). Finally, 1,20-dibromo-10,11-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl) icosane is obtained.

Step 3 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 triethylphosphite (9.1 g, 9.5 mL, 55 mmol, 5 eq) is added dropwise. At the end of the addition, stirring and heating are maintained for 12 hours. After evaporation of the excess triethylphosphite, the crude reaction product is purified by column chromatography on silica gel to give a colorless oil (9.2 g, 84%). Finally, 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 is carried out at ambient temperature for 3 hours. After evaporation of the dichloromethane, 400 mL of methanol is added to the reaction medium and stirring is maintained at room temperature for 12 hours. The methanol is evaporated to give a colorless oil (7.2 g, 88%). Finally, 10,11-bis (2,2,3,3,4,4,5,5,5-nonafluoropentyl) icosane-1,20 diyldiphosphonic acid (formula H) is obtained, this molecule corresponding to the general formula 1 according to the invention.

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.

B. Comparative tests of different epilames

In order to compare different epilams (coupling agents), comparative studies were performed by measuring contact angle values with Moebius 9010/10 FL oil.

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. Concretely, the more a large angle is measured, the more the surface has a hydrophobic / oleophobic character. In contrast, the smaller the angle, the more hydrophilic the surface.

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

In the context of the present invention, Krüss brand DSA100 associated with DSA4 version 2.0 software were used to perform these contact angle measurements.

1. Comparative tests of different coupling agents: resistance to successive washing cycles and contact angle measurements

• molécule 1 (OLEOXEIN+), correspondant à une molécule de formule générale (I) suivant l'invention :
  
• molécule 2 (OLEOXEIN) :
  
• molécule 3 (OLEOXEIN-ES) :
  

Tests of resistance to successive washing cycles were carried out with the following molecules used as epilams on a hardening steel surface of Durnico® type:

• molecule 1 (OLEOXEIN +), corresponding to a molecule of general formula (I) according to the invention:
  
• molecule 2 (OLEOXEIN):
  
• molecule 3 (OLEOXEIN-ES):
  

a) Surface treatment

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.

b) Washing cycles

Each washing cycle was carried out on EIP MC300 or Greiner Vibrograf ACS900 devices as follows: Tank 1 Tank 2 Tank 3 Tank 4 Drying Product Rubisol Rubisol isopropanol isopropanol / duration 6min 4min 3min 2 min 5 min agitation 150tr / min 400tr / min 150tr / min 150tr / min 150tr / min Temperature Amb Amb Amb Amb 65 ° C US Yes no no no no

c) Contact angle measurements

After each of the 7 wash cycles and after drying the treated surfaces, contact angle measurements were made (with the equipment mentioned above) on these surfaces by depositing a drop (0.2 μL) of Moebius 9010/10 FL oil. The results of these measurements, carried out with the DSA100 switchgear associated with DSA4 version 2.0 software, are presented to the figure 1 .

d) Results obtained: contact angles

As can be seen from figure 1 , the highest contact angle values were measured for the treated surfaces for 5 or 15 minutes with the molecule 1 (OLEOXEIN +) corresponding to a molecule of general formula (I) according to the invention. Indeed, after 7 washing cycles, significantly higher angle values and of the order of 75 to 80 ° were determined for surfaces treated with a molecule of general formula (I) according to the invention while Angle values of maximum 60 to 62 ° were measured for surfaces treated with molecules 2 (OLEOXEIN) and 3 (OLEOXEIN-ES).

These tests also show that the smallest difference between the angle value initially measured (85 to 90: washing cycle 0) and the measured angle value after 7 washing cycles (78 to 80: washing cycle 7 ) is observed when the surface is treated with a molecule of general formula (I) according to the invention. Indeed, when the surface is treated with the molecules 2 or 3, this difference between the initially measured angle value and the angle value measured after 7 washing cycles is significantly greater.

It thus follows from this comparative test that a molecule of general formula (I) according to the invention, presenting the best results in terms of oleophobia, is more resistant to washing, which means that this molecule adheres particularly well to the surface. and that it exhibits great stability over time, in particular by resisting hydrolysis (acidic or basic).

2. Comparative Tests of Different Coupling Agents: Coupling Agent According to the Invention and Commercial Coupling Agents

• molécule 1 (OLEOXEIN+) telle que reprise ci-dessus à l'exemple 1 et correspondant à une molécule de formule générale (I) suivant l'invention (traitement de surface par immersion durant 5 ou 15 minutes);
• agent de couplage commercial Episurf® (traitement de surface par immersion durant 5 ou 15 minutes);
• agent de couplage commercial Fixodrop® FKBS (traitement de surface par immersion durant 15 minutes) ;
• agent de couplage commercial 3M® EGC-1700 (traitement de surface par immersion durant 5 ou 15 minutes) ;
• agent de couplage commercial 3M® EGC-2702 (traitement de surface par immersion durant 5 minutes) ;
• agent de couplage commercial Dupont Solrem® FS2 (traitement de surface par immersion durant 15 minutes).

A second series of comparative tests was carried out on a hardening steel surface of Durnico® type with the following coupling agents (epilam):

• molecule 1 (OLEOXEIN +) as recited above in Example 1 and corresponding to a molecule of general formula (I) according to the invention (surface treatment by immersion for 5 or 15 minutes);
• Episurf® commercial coupling agent (immersion surface treatment for 5 or 15 minutes);
• Fixodrop® FKBS commercial coupling agent (surface treatment by immersion for 15 minutes);
• 3M® Commercial Coupling Agent EGC-1700 (surface treatment by immersion for 5 or 15 minutes);
• 3M® Commercial Coupling Agent EGC-2702 (surface treatment by immersion for 5 minutes);
• Dupont Solrem® FS2 commercial coupling agent (surface treatment by immersion for 15 minutes).

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. The results obtained during the contact angle measurements are presented in FIG. figure 2 .

This figure 2 clearly shows that the highest contact angle values were measured for the surfaces treated for 5 or 15 minutes with the molecule 1 (OLEOXEIN +) corresponding to a molecule of general formula (I) according to the invention. Indeed, after 7 washing cycles, significantly higher angle values and of the order of 78 to 80 ° were determined for surfaces treated with a molecule of general formula (I) according to the invention while angle values systematically less than 70 ° were measured for the surfaces treated with commercial coupling agents, they have fluorinated groups.

These tests also show that the smallest difference between the angle value initially measured (85 to 90: washing cycle 0) and the measured angle value after 7 washing cycles (78 to 80: washing cycle 7 ) is observed when the surface is treated with a molecule of general formula (I) according to the invention. Indeed, when the surface is treated with commercial coupling agents, this difference between the initially measured angle value and the angle value measured after 7 washing cycles is significantly greater.

It should also be noted that 3M® commercial coupling agents EGC-2702 and Dupont Solrem® FS2 give angle values under the allowable value of 45 °, only after 1 to 4 wash cycles.

It is thus again apparent from this comparative test that a molecule of general formula (I) according to the invention, presenting the best results in terms of oleophobia, is more resistant to washing than commercial coupling agents, which means that this molecule according to the invention adheres particularly well to the treated surface and that it has a high stability over time by resisting in particular acid or basic hydrolysis.

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

According to the invention, 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.

In this context, 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.

The results obtained during contact angle measurements are presented in figure 3 . These results show that pretreatment of the brass plasma oxygen surface before treatment of this same surface with a molecule of general formula (I) according to the invention significantly increases the resistance of epilame to cycles. successive washing.

In other words, 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.

4. Comparative tests: treatment of a brass surface with different coupling agents with or without plasma pretreatment

In the same context as the previous example, on a brass surface, whether or not pretreated with oxygen plasma, were tested various coupling agents (epilams), namely the molecule 1 (corresponding to a molecule of general formula (I) according to the invention - OLEOXEIN +) and the molecule 2 repeated in 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 results obtained during contact angle measurements are presented in figure 4 . As can be seen, whether for molecule 1 (OLEOXEIN +) or molecule 2 (OLEOXEIN) tested as coupling agent (epilame), oxygen plasma pretreatment clearly makes it possible to significantly increase the resistance. from epilam to successive wash cycles, that surface treatment by immersion in a solution containing epilam lasted 5 or 15 minutes.

As for the preceding example, this indicates that 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 surface. treated and in particular better resist hydrolysis in an acidic or basic environment, this conferring on epilame a high stability over time.

Note that the best contact angles are obtained for treatment with an epilame corresponding to a molecule of general formula (I) according to the invention.

5. 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 context as the preceding Examples 3 and 4, on a rhodium-plated brass surface that may or may not have been pretreated with an oxygen plasma, the molecule 1 (corresponding to a molecule of general formula (I) according to the invention was tested - OLEOXEIN + ).

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 results obtained during contact angle measurements are presented in figure 5 . As can be seen with the molecule 1 tested as a coupling agent (epilame), a pretreatment by oxygen plasma clearly makes it possible to significantly increase the resistance to successive washing cycles, that the treatment of the surface by immersion in a solution containing epilame lasted 5 or 15 minutes.

This again indicates that pretreatment of the surface by 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 better to resist hydrolysis in an acidic or basic environment, this conferring on the epilame a high stability over time.

6. Comparative tests: treatment of a rhodium-plated brass surface with different coupling agents with or without plasma pretreatment

In the same optics as the previous example, on a rhodium-plated brass surface, pretreated or not with oxygen plasma, were tested different coupling agents (epilams), namely the molecule 1 (corresponding to a molecule of general formula ( I) according to the invention - OLEOXEIN +) and the molecule 2 (OLEOXEIN) taken from 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 results obtained during contact angle measurements are presented in figure 6 . As can be seen, whether for molecule 1 (OLEOXEIN +) or molecule 2 (OLEOXEIN) tested as coupling agent (epilam), oxygen plasma pretreatment clearly makes it possible to significantly increase the resistance to successive washing cycles, that the surface treatment by immersion in a solution containing epilame lasted 5 or 15 minutes.

As for the previous examples, this indicates that 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 better resist hydrolysis in an acidic or basic medium, this conferring on epilame a high stability over time. Note that the best contact angles are obtained for treatment with an epilame corresponding to a molecule of general formula (I) according to the invention.

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

In the same context as the preceding examples, on a sapphire surface that may or may not have been pretreated with an oxygen plasma, 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

The results obtained during contact angle measurements are presented in figure 7 . As can be seen, oxygen plasma pretreatment clearly enables the resistance to successive washing cycles to be significantly increased, since the treatment of the surface by immersion in a solution containing epilam lasted 5 or 15 minutes. This again indicates that pretreatment of the surface by 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 better resist hydrolysis in an acidic or basic medium, this giving the epilame a high stability over time.

8. Comparative tests: treatment of a sapphire surface with different coupling agents with or without plasma pretreatment

In the same optics as the previous example, on a rhodium-plated brass surface, pretreated or not with oxygen plasma, were tested different coupling agents (epilams), namely the molecule 1 (corresponding to a molecule of general formula ( I) according to the invention - OLEOXEIN +) and the molecule 2 (OLEOXEIN) taken from 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 results obtained during contact angle measurements are presented in figure 8 . As can be seen, whether for molecule 1 (OLEOXEIN +) or molecule 2 (OLEOXEIN) tested as coupling agent (epilame), oxygen plasma pretreatment clearly makes it possible to significantly increase the resistance. at successive washing cycles, that the treatment of the surface by immersion in a solution containing epilame lasted 5 or 15 minutes.

As for the previous examples, this indicates that 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 better resist hydrolysis in an acidic or basic medium, this conferring on epilame a high stability over time. Note that the best contact angles are obtained for treatment with an epilame corresponding to a molecule of general formula (I) according to the invention.

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

Claims (12)

1. Article the surface of which is treated with a coupling agent of the following general formula:

   

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

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

   - each R₂, independent from one another, and identical or different in each instance, is selected from a group consisting in a bond, (CH₂)_n, O, S, S-S, NH, O(CO), O(CS), NH(CO), NH(CS)NH, NH-CS-NH, NH(CO)O, NH(CS)O,

   

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

   - each R₃, identical of different from one another, is selected from the group consisting in a perfluoroalkyl group having 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 between 0 and 100;

   - each R₄, identical or different from one another, is selected from the group consisting in H, an alkyl group containing 1 to 10 carbon atoms, which is optionally substituted by at least one halogen atom, 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, NH-CS-NH, NH(CO)O, NH(CS)O,

   

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

   - each F and F', independent from one another, and identical or different from one another in each instance, are selected from the group consisting in PO₃H₂, OPO₃H₂, SH and SiX3, X=H, Cl, OMe, OEt, OiPr, preferably PO₃H₂.
2. Process for treating a surface of an article with a molecule of general formula (I) as defined in claim 1, said treatment process including a step of contacting said surface with said molecule of general formula (I).
3. Process for treating a surface of an article according to claim 2, including a preliminary treatment step of said surface with a plasma process.
4. Process for treating a surface of an article according to claim 2 or 3, characterized in that it includes a preliminary step of solving said molecule of general formula (I) in a solvent to form a surface treatment solution.
5. Process for treating a surface of an article according to claim 4, characterized in that said preliminary step of preparing a solution in a solvent to form a surface treatment solution is performed by preparing the solution in a solvent selected from a group consisting in isopropanol, ethanol, methanol, dimethylformamide, acetone, tetrahydrofuran, preferably isopropanol.
6. Process for treating a surface of an article according to claim 4 or 5, characterised in that said preliminary of preparing a solution in a solvent forms a surface treatment solution comprising said molecule of general formula (I) in a content of 0,01% to 10% v/v in a solvent, preferably from 0,1% to 5% v/v.
7. Process for treating a surface of an article according to any of claims 2 to 6, characterised in that said step of contacting said preliminarily treated surface with a molecule of general formula (I) is performed by spraying, by dipping, by vaporisation, by dabbing, by wiping, by spin coating and by deep coating.
8. Process for treating a surface of an article according to any of claims 2 to 7, further including at least one of following additional steps:

   - dripping of said surface contacted with said surface treatment solution, and/or

   - washing of said surface contacted with said surface treatment solution, and/or

   - drying of said surface contacted with said surface treatment solution.
9. Process for treating a surface of an article according to any of claims 2 to 8, characterised in that said surface to be treated is selected from the group consisting in sapphire, brass, rhodium-plated brass, gold-plated brass, nickel, steel, hardenable steel, iron, aluminium, titanium, lead, silver, gold, copper, manganese, vanadium, lithium, cobalt, silicon and various alloys and oxides of such metals.
10. Synthesis process for a coupling agent of general formula (I) as defined in claim 1, starting with a molecule of general formula (II), having the following formula:

    

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

    - each R', independent from one another, and identical or different from one another in each instance, is selected from the group consisting in a bond, (CR₅R₆)_n where each R₅ and R₆, identical or different from one another, is independently selected from the group consisting in H, alkyl group comprising 1-10 carbon atoms, which is optionally substituted by at least one halogen atom, aryl or aralkyl group, n being comprised between 1 and 50;

    - each R₂, independent from one another, and identical or different from one another in each instance, is selected from the group consisting in 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 comprised between 1 and 100;

    - each R3, identical or different from one another, is selected from a group consisting in a perfluoroalkyl group having 1-50 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 between 0 and 100;

    - each R₄, identical or different from one another, is selected in the group consisting in H, an alkyl group containing 1-10 carbon atoms, which is optionally substituted by at least one halogen atom, 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 comprised between 1 and 100;

    - each X and Y, independent from one another, and identical or different from one another in each instance, represent a halogenated group or an unsaturated organic group;

    said process comprising:

    - a substitution step of at least one halogenated group X, Y of said molecule of general formula (II) by a group that may represent, either directly of after several synthesis steps, an anchor for said coupling agent, and being selected from the group consisting in PO₃H₂, OPO₃H₂, SH, preferably PO₃H₂, or

    - an addition step on at least one unsaturated organic group X, Y of said molecule of general formula (II) of a group that may represent, either directly or after several synthesis steps, an anchor for said coupling agent and being selected from the group consisting in PO₃H₂, OPO₃H₂ and SiX₃, X=H, Cl, OMe, OEt, OiPr, preferably PO₃H₂.
11. Use of a molecule of general formula (I) as defined in claim 1 for treating a surface of an article.
12. Use according to claim 11, for treating a surface of a watchmaking article.

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