A substrate comprising a surface coated with an epiram agent and a method for epiram coating such a substrate

Abstract

To provide an epilame agent that is not restricted by environmental reasons.SOLUTION: The invention provides a substrate comprising a surface covered with an epilame agent, comprising a compound in the form of a copolymer comprising units M and units N, where M and N are the middle and lowest formulas in the figure, respectively, where: R1 and R2 are each H, a C1-C10 alkyl group, or a C2-C10 alkenyl group; X and Y are each a spacer arm; A is an anchoring group to the substrate; and L is a halogenated ether group.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] The present invention relates to a substrate comprising a surface at least partially coated with an epilame agent. The present invention also relates to a method for epilame coating such a substrate.

Background Art

[0002] There are various methods for modifying the surface state of a substrate by treatment with an appropriate agent in order to specifically improve certain surface properties. For example, in the field of machinery, particularly in the field of watchmaking, and also in the field of jewelry, epilame coating of the surface of parts or components with an epilame agent is often carried out to control and reduce the surface energy of that surface during use. More specifically, the purpose of the epilame agent is to prevent oil or lubricant from spreading onto the components of a watch or jewelry by forming a hydrophobic and oleophobic surface that allows the lubricant to stay in a predetermined position on the treated surface.

[0003] However, the substances currently used for epilame coating have many drawbacks. For example, epilame agents such as Fixodrop (registered trademark) ES / BS from Moebius (registered trademark) and the Novec (trademark) series from 3M (trademark) do not have sufficient resistance to watch cleaning.

[0004] Patent application US2012 / 0088099 provides a partial solution to this problem by proposing the use of an epilame agent having a catechol functional group at the end of the chain. This catechol functional group can adhere firmly to the surface of certain substrates, but for substrates that are very common in the fields of watchmaking and jewelry such as gold and steel, it cannot improve the resistance to watchmaking cleaning. As a result, the use of known epilame agents is generally limited to specific materials, and users need to utilize different types of epilame agents depending on the nature of the surface to be treated.

[0005] One solution to this problem consists, for example, in using, as the epilam composition, a mixture of compounds of different properties (thiols and biphosphonates) which, by their synergistic effect, promote the adhesion of the epilam to the substrate. However, since the synthesis of each of these compounds requires at least four steps, the overall synthesis method for the epilam composition is long and complex.

[0006] Another solution is described, for example, in patents EP 3 070 133 and EP 3 070 152. Patent EP 3 070 133 describes an epilam agent comprising a random copolymer comprising a fluorinated motif, an anchoring motif, and optionally an additional hydrocarbon chain. EP 3 070 152 describes an epilam agent comprising a block copolymer comprising a fluorinated motif, an anchoring motif, and optionally an additional hydrocarbon chain. In particular, -C5F 11 and -C6F 13 types of fluorinated motifs are described.

[0007] However, perfluorohexanoic acid (PFHxA, CAS 307-24-4), its salts and related substances are under general regulatory pressure for environmental reasons.

SUMMARY OF THE INVENTION

[0008] An object of the present invention is, in particular, to overcome the various drawbacks of known epilam agents and epilam coating methods.

[0009] More specifically, one object of the present invention is to provide an epilam agent that is not considered to be under general regulatory pressure for environmental reasons.

[0010] Another object of the present invention is to provide an epilam agent having high wash resistance compared to known epilam agents. It is also an object of the present invention to provide a general-purpose epilam agent that can be used for all types of materials.

[0011] Another object of the present invention is to provide an environmentally friendly epilam coating method that makes it possible to eliminate the use of large amounts of contaminating fluorinated solvents. Another object of the present invention is to provide an economical epilam coating method that makes it possible to eliminate the use of large amounts of expensive fluorinated solvents.

[0012] Another object of the present invention is to provide an epilam agent and an epilam coating method that enable accurate measurement of the concentration of the epilam agent over time in order to make the entire epilam coating method more robust.

[0013] For this purpose, a first aspect of the present invention relates to a substrate comprising a surface at least partially coated with an epilam agent as recited in the claims.

[0014] According to the present invention, the epilam agent comprises at least one compound in the form of a copolymer comprising units M and units N. These units M and units N are bonded by a covalent bond through the main chain.

[0015] According to the present invention, M is

Chemical formula

[0016] Advantageously, Y may be the same or different and is C1-C 20It is selected from the group consisting of an ester group, an amide group, and a styrene-derived group. Optionally, Y may be the same or different and contains at least one heteroatom.

[0017] Advantageously, A is selected from the group consisting of glycidyl, thiol, thioether, thioester, sulfide, thioamide, silanol, alkoxysilane, halogenated silane, hydroxyl, phosphate, protected or unprotected phosphonic acid, protected or unprotected phosphonate, amine, ammonium, nitrogen heterocycle, carboxylic acid, anhydride and catechol.

[0018] According to the present invention, N is

Chemical formula

Chemical formula

[0019] Advantageously, Preferably, X, which may be the same or different, is selected from the group consisting of C1-C20 ester groups, amide groups, and styrene-derived groups. Optionally, X, which may be the same or different, contains at least one heteroatom.

[0020] Advantageously, L is an ether group that is at least partially fluorinated, for example, fully fluorinated. As used herein, the term "fully fluorinated" refers to an ether group in which each hydrogen atom has been replaced by a fluorine atom.

[0021] Advantageously, the copolymer is a random copolymer. Advantageously, units M and N are randomly distributed. Advantageously, the copolymer is a random copolymer and units M and N are randomly distributed.

[0022] Alternatively, and advantageously, the copolymer is a block copolymer. Advantageously, the block copolymer comprises at least one block of units M bonded by a covalent bond through the main chain and at least one block of units N bonded by a covalent bond through the main chain. Advantageously, the blocks are bonded to each other by a covalent bond through the main chain in a linear arrangement.

[0023] Advantageously, the unit N / unit M ratio is between 1 and 20, for example, between 2 and 18, or between 5 and 15.

[0024] Advantageously, and optionally, the copolymer according to the present disclosure further comprises unit V. Advantageously, unit V is bonded to units M and N by a covalent bond through the main chain. Advantageously, V is

Chemical formula

[0025] Advantageously, T, which may be the same or different, is a UV absorber group or a fluorophore.

[0026] Advantageously, the surface of the substrate, at least partially coated with the epiram agent, is made of a material selected from the group consisting of metals, metal oxides, polymers, sapphire, ruby, silicon, silicon oxide, silicon nitride, silicon carbide, diamond-like carbon (DLC), and alloys thereof.

[0027] A second aspect of the present invention relates to a method of epiram coating at least a part of the surface of a substrate as described in the appended claims.

[0028] The epiram coating method of the present invention includes preparing an epiram agent containing at least one copolymer as defined above. Optionally, the epiram coating method further includes preparing the surface of the substrate. The epiram coating method further includes contacting the surface of the substrate with the epiram agent.

[0029] Advantageously, the epiram agent is prepared (the preparation of the epiram agent is carried out) by copolymerization of a monomer capable of forming unit M and a monomer capable of forming unit N. Advantageously, units M and N are as described above. Advantageously, the monomers are selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, vinyl, and styrene monomers.

[0030] According to one embodiment of the epilam coating method, the epilam agent is prepared by preparing an epilam coating bath containing the epilam agent. Then, at least a part of the surface of the substrate is brought into contact with the epilam agent in the epilam coating bath, for example, by immersing the substrate in the epilam coating bath.

[0031] This preparation of the epilam agent is particularly suitable when the epilam agent contains at least one copolymer further containing unit V bonded to units M and N by a covalent bond through its main chain. Advantageously, unit V is as described above. The presence of unit V, particularly the presence of the tracer group, advantageously and optionally enables controlling the concentration of the epilam agent in the epilam coating bath before contact. Optionally, and after controlling the concentration of the epilam agent, the concentration of the epilam agent in the epilam coating bath can be readjusted.

[0032] According to another embodiment of the epilam coating method, the surface of the substrate is brought into contact with the epilam agent by arranging the substrate and the epilam agent in an enclosure at ambient pressure, and then the enclosure is sealed. Next, CO2 at a pressure composed of 25 bar to 74 bar, preferably 45 bar to 70 bar, and a temperature composed of 10 °C to 80 °C, preferably 15 °C to 50 °C, is introduced into the sealed enclosure. Thereafter, the pressure in the enclosure is reduced, and the epilam-coated substrate is taken out of the enclosure.

[0033] The third aspect of the present invention relates to using, as the epilam agent for at least a part of the surface of the substrate, a copolymer containing units M and N bonded by a covalent bond through its chain. Units M and N are as described above.

[0034] The present invention further relates to a timepiece or jewelry including a component containing the substrate of the first aspect of the present invention.

[0035] One of the advantages of the epilam agent according to the present invention is that while providing a high-performance epilam effect, it is not subject to regulatory pressure for environmental reasons. Another advantage is that it is resistant to cleaning, especially during watch manufacturing. The objectives, advantages, and features are shown in the following drawings, which are not limiting.

Brief Description of the Drawings

[0036]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Mode for Carrying Out the Invention

[0037] According to the present invention, the substrate includes a surface at least partially covered with an epilam agent. Advantageously, at least its surface, and optionally the entire substrate, is made of a material selected from the group consisting of metals, metal oxides, polymers, sapphire, ruby, silicon, silicon oxide, silicon nitride, silicon carbide, diamond-like carbon (DLC), and alloys thereof.

[0038] More specifically, the surface of the substrate can include or be made of a metal oxide, or polyoxymethylene or acrylamide, or an alloy thereof, regardless of whether the surface of the substrate is doped with a noble metal such as steel, or gold, rhodium, palladium, platinum, or a combination of two or more thereof, or an aluminum, zirconium, titanium, chromium, manganese, magnesium, iron, nickel, copper, zinc, molybdenum, silver, tungsten, or a combination of two or more thereof.

[0039] Advantageously, in the present invention, the substrate is a substrate of a component of a watch or jewelry.

[0040] Advantageously, the X groups, which may be the same or different, are C1-C 20 ester groups, preferably C2-C 10 ester groups, more preferably C2-C6 ester groups, still more preferably C2-C5 ester groups, preferably linear alkyl ester groups, amide groups and styrene-derived groups, and are selected from the group consisting of.

[0041] Advantageously, the Y groups, which may be the same or different, are preferably linear, C1-C 20 , preferably C2-C 10 , more preferably C2-C6, still more preferably C2-C5 ester groups, preferably alkyl ester groups, amide groups and styrene-derived groups, and are selected from the group consisting of.

[0042] Advantageously, the copolymer includes at least two different A groups. The target functional group A can react with the surface of the substrate to be epilam-coated so as to form a group for anchoring the epilam agent on the surface of the substrate. Advantageously, the A group can also be provided at the end of the copolymer.

[0043] The functional group L of interest contributes to the epilam effect. These contain at least one halogen atom Q. Advantageously, the halogen atoms Q, which may be the same or different, are fluorine atoms, iodine atoms, bromine atoms or chlorine atoms. Preferably, the halogen atom is a fluorine atom. When the L group contains several halogen atoms, these atoms may be the same or different. Advantageously, all the halogen atoms Q of the L group are fluorine atoms.

[0044] The functional group L of interest also contains a P group. The P groups, which may be the same or different, are advantageously C1-C 10 alkyl groups, C2-C 10 alkenyl groups or C2-C 10 alkynyl groups. The P group advantageously contains at least one halogen atom. Advantageously, the halogen atoms, which may be the same or different, are fluorine atoms, iodine atoms, bromine atoms or chlorine atoms. Preferably, the halogen atom is a fluorine atom. The P group may be linear or branched.

[0045] Advantageously, the P group is a C1-C 10 perfluoroalkyl group, preferably a C1-C6 perfluoroalkyl group, for example a C1-C4 perfluoroalkyl group such as CF3, C2F5, C3F7 or C4F9.

[0046] Advantageously and alternatively, the P group is a C2-C 10 perfluoroalkenyl group, preferably a C2-C6 perfluoroalkenyl group, for example a C2-C4 perfluoroalkenyl group such as C2F3, C3F5 and C4F7.

[0047] Advantageously and alternatively, the P group is a C2-C 10 perfluoroalkynyl group, preferably a C2-C6 perfluoroalkynyl group, for example a C2-C4 perfluoroalkynyl group such as C2F, C3F3 and C4F5.

[0048] Advantageously, in the target functional group L, p is selected between 1 and 4, preferably between 2 and 3.

[0049] Advantageously, in the target functional group L, n is selected between 1 and 20, for example between 1 and 16, preferably between 1 and 10, for example between 2 and 8.

[0050] A preferred target functional group L in the present invention has the structure (CF(CF3)OCF2) n represented by CF2CF3, that is, Q is a fluorine (F) atom, P is CF3, and p is 2. More specifically, the preferred structure of the L group is (CF(CF3)OCF2)5CF2CF3, that is, Q is a fluorine (F) atom, P is CF3, p is 2, and n is 5.

[0051] One of the copolymers preferably used in the present invention has the following structure (II).

Chemical formula

[0052] In other words, in this copolymer, X is C(O)O(CH2)2OC(O), Y is C(O)O, P is fluorine (F), Q is CF3, p is 2, and L is (CF(CF3)OCF2) n represented by CF2CF3. Preferably, in the copolymer represented by the structure (II), R1 and R2, which may be the same or different, are H or CH3.

[0053] Specific examples of the copolymer represented by the structure (II) include, but are not limited to, a copolymer in which n is 5, R1 is H, R2 is CH3, A is CH2(CHCH2O), and the m / p ratio is 9.

[0054] Optionally, the copolymer can further contain at least one unit U, where U is

Chemical formula

[0055] Advantageously, when the copolymer contains at least one unit U, the units U, M and N are bonded by a covalent bond through their main chains.

[0056] Advantageously, the functional group R5 of interest makes it possible to modify the properties of the epilam agent and / or provide other functions. For example, R5 can be an alkyl chain used to modify the resulting contact angle, or a chain capable of forming crosslinking points during complementary crosslinking steps.

[0057] Advantageously, the unit N / unit M ratio is between 1 and 20, preferably between 2 and 18, for example between 5 and 15, or between 7 and 12, for example 8, 9, 10 or 11.

[0058] Advantageously, the copolymer contains 0.1% to 50%, preferably 5% to 30%, more preferably 5% to 20% of unit M, this percentage being expressed with respect to the total number of units in the copolymer. Advantageously, the copolymer contains 1% to 99.9%, preferably 50% to 99.9%, more preferably 80% to 95% of unit N, this percentage being expressed with respect to the total number of units in the copolymer. Advantageously, the copolymer contains 0% to 50%, preferably 0% to 30%, more preferably 0% to 10% of unit U, this percentage being expressed with respect to the total number of units in the copolymer.

[0059] Optionally, the copolymer can further comprise at least one unit V, where V is as described above. Advantageously, when the copolymer comprises at least one unit V, the units V, M, and N are bonded to each other by covalent bonds through their main chains.

[0060] Advantageously, the Z groups, which may be the same or different, are C1-C 20 ester groups, preferably C2-C 10 ester groups, more preferably C2-C6 ester groups, even more preferably C2-C5 ester groups, preferably linear alkyl ester groups, amide groups, and groups derived from styrene, and are selected from the group consisting of.

[0061] Advantageously, the T group can be used, for example, for measuring the copolymer concentration by spectroscopy.

[0062] Advantageously, the Ts, which may be the same or different, are UV absorber groups derived from compounds selected from the group consisting of benzotriazole, triazine, phenone (especially benzophenone, acetophenone, hydroxyalkylphenone, hydroxyaryl phenone, aminoalkylphenone, and anthraquinone), and acylphosphine oxide.

[0063] Advantageously, the Ts, which may be the same or different, are fluorophore groups derived from compounds selected from the group consisting of fluorescein, naphthyl, anthracene, coumarin, rhodamine, and fluorobenzoate.

[0064] Advantageously, the copolymer comprises from 5 units to 500 units, preferably from 10 units to 350 units.

[0065] The copolymer can be a random copolymer or a block copolymer.

[0066] Advantageously, when the copolymer is a random copolymer, the units M, N, any unit V, and any unit U are randomly distributed. In other words, the units are statistically bonded to each other through the main chain.

[0067] Advantageously, when the copolymer is a block copolymer, the copolymer comprises at least one block of units M bonded by covalent bonds through the main chain and at least one block of units N bonded by covalent bonds through the main chain. Preferably, the block copolymer comprises a single block of units M and / or a single block of units N.

[0068] Optionally, the block copolymer further comprises at least one block of units V bonded by covalent bonds through their main chains. Preferably, and optionally, the block copolymer comprises a single block of units V.

[0069] Optionally, at least one of the block of units M, the block of units N, and any block of units V optionally comprises at least one unit U bonded by covalent bonds through their main chains. Advantageously, the blocks are bonded to each other by covalent bonds through their main chains in a linear arrangement. When the block copolymer further comprises at least one unit U, at least one of the block of units M, the block of units N, and any block of units V comprises at least one unit U, and the number of units U in the block of units M can vary depending on the number of units U in the block of units N and the number of units U in the block of units V (when the latter is included in the block copolymer).

[0070] Preferably, unit U is integrated and distributed within the block composed of unit N by, for example, forming a single block mainly composed of unit N by statistical copolymerization of unit U and unit N and assimilating into the block of unit N.

[0071] The present invention also relates to a method for epitaxial coating at least a part of the surface of a substrate, the method comprising preparing an epitaxial agent, optionally preparing the surface of the substrate, and contacting the surface of the substrate with the epitaxial agent.

[0072] Advantageously, the preparation of the epilaminate involves the copolymerization of a monomer capable of forming unit M, a monomer capable of forming unit N, a monomer capable of forming at least one unit V optionally, and a monomer capable of forming at least one unit U optionally.

[0073] Advantageously, the monomers are selected from the group comprising monomers of acrylates, methacrylates, acrylamides, methacrylamides, vinyls, dienes, styrenes and olefins.

[0074] Particularly preferred monomers for forming unit V containing the tracer group T are selected from the group comprising 2-H-benzotriazol-2-yl-hydroxyphenylethyl methacrylate, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, 4-allyloxy-2-hydroxybenzophenone, 2-naphthyl (meth)acrylate, fluorescein O-(meth)acrylate, 9-anthracenylmethyl (meth)acrylate, ethidium bromide-N,N'-bisacrylamide, N-(1-naphthyl)-N-phenylmethacrylamide, and 7-[4-(trifluoromethyl)coumarin]methacrylamide. Such monomers are commercially available and are polymerizable.

[0075] More preferably, the monomers for forming unit V containing the tracer group T are selected from the group comprising 2-H-benzotriazol-2-yl-hydroxyphenylethyl methacrylate, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, and 4-allyloxy-2-hydroxybenzophenone. These monomers contain a tracer group that can be monitored by UV-visible spectroscopy, which is much easier to set up in an industrial environment than fluorescence spectroscopy.

[0076] The overlapping technique includes those known to those skilled in the art. Optionally, the copolymerization is carried out in the presence of an initiator such as, but not limited to, azobisisobutyronitrile (AIBN). Optionally, the copolymerization is carried out at a high temperature.

[0077] The copolymer used in the present invention can be obtained in powder or viscous liquid form.

[0078] A particularly suitable polymerization method for obtaining a random copolymer is free radical copolymerization in solution or emulsion.

[0079] A particularly suitable polymerization method for obtaining a block copolymer is · a monomer capable of forming at least one block of unit M, optionally accompanied by a monomer capable of forming at least one unit U, · a monomer capable of forming at least one block of unit N, optionally accompanied by a monomer capable of forming at least one unit U (U being the same or different), and · optionally, a monomer capable of forming at least one block of unit V, optionally accompanied by a monomer capable of forming at least one unit U (U being the same or different) which is a continuous controlled radical copolymerization.

[0080] According to the first copolymerization mode, the copolymer can be obtained in one step by copolymerization, preferably radical copolymerization, of a monomer having a side chain Y-A, a monomer having a side chain X-L, optionally a monomer having a side chain Z-T, and optionally a monomer having a side chain R5.

[0081] According to another copolymerization method, the copolymer can be obtained by copolymerization, preferably radical copolymerization, of a monomer having a suitable side chain Y, a monomer having a suitable side chain X, optionally a monomer having a suitable side chain Z, and optionally a monomer having a side chain intended to have R5, and then the side chain is modified, for example, by "click chemistry" to introduce the target functional groups A, L, T (optional) and the R5 group (optional) therein.

[0082] Advantageously, when the copolymerization is radical copolymerization, the radical copolymerization is of the "free" type to obtain a random copolymer. Preferably, the radical copolymerization is of the "controlled" type to obtain a block copolymer.

[0083] Optionally, the preparation of the surface of the substrate may include cleaning and / or washing the surface to be epilam coated. Such cleaning or washing can be carried out using methods known to those skilled in the art. For example, especially when the substrate is a watch part, the cleaning may include cleaning according to standard watch manufacturing methods.

[0084] Alternatively, the preparation of the surface of the substrate may include treatment with CO2 at a temperature of 10 °C to 80 °C and a pressure of 25 bar to 250 bar, for example, over a time of 1 minute to 60 minutes. Advantageously, such treatment makes it possible to remove particulate dust and degrease the surface.

[0085] Advantageously, to obtain the epilam agent solution, the copolymer(s) is dissolved in a fluorinated solvent such as a perfluorinated or fluorinated hydrocarbon, perfluoropolyether, hydrofluoroolefin or hydrofluoroether, preferably at a concentration of 50 mg / L to 1 g / L.

[0086] According to a first embodiment of the epilam coating method, such an epilam agent solution is then used in an epilam coating bath. The same epilam coating bath can be used several times. Advantageously, when the same epilam coating bath is used several times, preferably before contacting the surface of the substrate with the epilam agent in the epilam coating bath, there are means for controlling the concentration of the epilam agent and optionally means for maintaining the concentration of the epilam agent to control and optionally maintain this concentration over time.

[0087] Such concentration control means may include the presence of at least one unit V as described above in the copolymer. In other words, the presence of at least one unit V containing a T group as described above makes it possible to control the concentration of the epilam agent in the epilam coating bath.

[0088] Advantageously, when the T group is a UV absorber group or a fluorophore, the concentration of the epilam agent is determined by spectroscopy (e.g., absorbance measurement). An intermediate step prior to the step of controlling the concentration of the epilam agent in the epilam coating bath provides the generation of a calibration curve for the copolymer. For this purpose, the copolymer is dissolved in a solvent at different concentrations, and for each solution, the absorbance as a function of wavelength is measured spectroscopically. The wavelength at which the absorbance is maximum is identified, and the calibration curve A = F(concentration) is plotted at that wavelength at which the absorbance is maximum. Then, the molar extinction coefficient of the polymer can be estimated (Beer Lambert's law A = εcl).

[0089] Then, to control the concentration of the epilam agent in the epilam coating bath, it is sufficient to spectrophotometrically measure the absorbance of the bath solution and then estimate the concentration of the epilam agent in the bath using the calibration curve established previously. Then, depending on the result, additional epilam agent can be added to the bath to accurately adjust the concentration.

[0090] After the surface of the substrate has been contacted with the epilam agent, the epilam coating method according to the invention may further include the step of drying the epilam-coated surface.

[0091] According to the second embodiment of the epiram coating method, the epiram agent solution as described above is used (including being disposed) in the enclosure. Alternatively, the epiram agent can also be disposed in the enclosure in a pure form.

[0092] Advantageously, the substrate and the epiram agent are disposed in the enclosure at the ambient environmental pressure, i.e., a pressure of 0.6 bar to 1.1 bar, and then the enclosure is sealed.

[0093] Next, CO2 is introduced into the sealed enclosure. Advantageously, CO2 is introduced over a period of 1 minute to 30 minutes, preferably 1 minute to 20 minutes, more preferably 3 minutes to 15 minutes.

[0094] Advantageously, the pressure of CO2 is from 25 bar to 74 bar, preferably from 45 bar to 70 bar, more preferably from 50 bar to 60 bar.

[0095] Advantageously, the temperature of CO2 is from 10°C to 80°C, preferably from 10°C to 60°C, more preferably from 15°C to 50°C.

[0096] Thereafter, the introduction of CO2 is stopped and the pressure inside the enclosure is reduced. Advantageously, the pressure drops to the ambient environmental pressure, i.e., a pressure of 0.6 bar to 1.1 bar.

[0097] Next, the epiram substrate is taken out of the enclosure.

[0098] Optionally, after the pressure in the enclosure drops and the epilam-coated substrate is taken out of the enclosure, the epilam-coated substrate can be heat-treated. For example, the epilam-coated substrate can be heated in the enclosure at a temperature of 250°C to 90°C, preferably 30°C to 80°C, for a time of 1 minute to 45 minutes, preferably 2 minutes to 30 minutes. Such heat treatment makes it possible to improve the fixation of the epilam agent on the surface of the treated substrate.

[0099] The epilam coating method according to the present invention can further include a complementary cross-linking step after the surface of the substrate is contacted with the epilam agent. Complementary cross-linking is advantageously made possible by the presence of suitable functional groups provided on the side chain R5 of unit U.

Example

[0100] Example 1 An epilam agent was produced by random copolymerization to obtain a perfluoroether copolymer.

[0101] In the first step, a perfluoroether acrylate monomer (“perfluoroether monomer”) was synthesized. Perfluoro-2,5,8,11,14-pentamethyl-3,6,9,12,15-pentaoxaoctadecanoyl fluoride (CAS 13252-15-8) was reacted with 2-hydroxyethyl acrylate (CAS 818-61-1) at room temperature in the presence of sodium fluoride. Figure 1 shows the obtained monomer, where n is 5 and R1 is H (hydrogen).

[0102] Next, the perfluoroether acrylate monomer was copolymerized by random copolymerization with glycidyl methacrylate shown in Figure 2 (A is CH2(CHCH2O), R2 is CH3 (CAS 106-91-2)) in the presence of initiator AIBN. Figure 3 shows the obtained epilam copolymer, where n is 5, R1 is H, R2 is CH3, A is CH2(CHCH2O), and the m / p ratio is 9.

[0103] Example 2 Using an epiramide coating bath, three types of epiramide agents were deposited on the surface of a steel substrate that had been previously surface-prepared. The first epiramide is the copolymer synthesized in Example 1. The second epiramide agent contains a C6 perfluoroalkyl group, i.e., a C6F 13 group, as the epiramide group. The third epiramide agent is a competing epiramide agent containing methyl nonafluoroisobutyl ether (CAS 163702-08-7), methyl nonafluorobutyl ether (CAS 163702-07-6), and a fluorinated aliphatic polymer.

[0104] Various tests were conducted to evaluate the properties of the epiramide agents.

[0105] As a first test, the surface energy was measured. This procedure, known to those skilled in the art, involves measuring the contact angles of three liquid droplets (using an OCA 15 contact angle measuring device from Dataphysics). These are water, diiodomethane, and ethylene glycol, each having a very different surface tension. From the obtained angles, the surface energy is calculated using the Owens, Wendt, Rabel and Kaelble (OWRK) method.

[0106] The results are shown in Table 1. The surface of the steel substrate that had undergone the surface preparation procedure but had no epiramide agent had a surface energy of 34.95 mN / m. All the epiramide agents showed a reduction in surface energy, with the epiramide agent of the present invention showing the lowest value. The lower the surface energy, the better the oil repellency.

Table 1

[0107] Example 3 Next, the three types of epiramide agents of Example 2 were used (applied) to several substrates with different compositions.

[0108] To evaluate the performance of the epilam agent, the contact angles were measured with test oil No. 3 and Moebius® oil 9010. Drops of both oils were deposited and the contact angles were measured using an optical device (Dataphysics OCA 15). To evaluate the resistance to watch manufacturing cleaning, the substrate was cleaned three times according to watch manufacturing cleaning (amine hydrocarbon solution), and then the contact angle was measured.

[0109] The target values for each measurement are as follows. · Test oil No. 3 - Initial (before cleaning): 60°. · Test oil No. 3 - After 3 washes: 35°. · Oil 9010 - Initial: 70°. · Oil 9010 - After 3 washes: 45°.

[0110] Figure 4 shows the results on different substrates for the copolymer of the present invention. Figure 5 shows the results for the C6F 13 type epilam agent, and Figure 6 shows the results for the competing epilam agent.

[0111] From Figure 6, it is clear that for any substrate, the target values of each oil are not achieved before and after 3 washes. On the other hand, the target values of oil 9010 are achieved with the copolymer of the present invention and the C6F type epilam agent. The target values of oil No. 3 are achieved on specific substrates with these two 13 epilam agents (Figures 4 and 5). epilam agents (Figures 4 and 5). <Supplementary Note> Item 1 A substrate comprising a surface at least partially coated with an epilam agent, wherein the epilam agent comprises at least one compound in the form of a copolymer containing units M and N bonded by a covalent bond through the main chain, where in, M is

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Claims

1. A substrate comprising a surface at least partially coated with an epilam agent, wherein the epilam agent comprises at least one compound in the form of a copolymer comprising units M and N bonded by a covalent bond through the main chain, wherein M is 【Chemical 1】 and N is 【Chemical Formula 2】 wherein, in the formula R 1 and R 2 may be the same or different and are H, C 1 to C 10 alkyl group, or C 2 to C 10 alkenyl group, and X and Y may be the same or different and are spacer arms consisting of heteroatoms or consisting of a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom, A may be the same or different and forms an anchoring group for the substrate, L may be the same or different and is a halogenated ether group according to the following formula (I) 【Chemical Formula 3】 wherein, in the formula Q is a halogen atom, P may be the same or different and is a C which contains at least one halogen atom and is linear or branched 1 -C 10 alkyl group or C 2 -C 10 alkenyl group, p is selected between 1 and 4, n is selected between 1 and 20, the copolymer is a block copolymer comprising at least one block of unit M bonded by a covalent bond through its main chain and at least one block of unit N bonded by a covalent bond through its main chain, and the blocks are bonded to each other by a covalent bond through their main chains in a linear arrangement, substrate.

2. A substrate comprising a surface at least partially coated with an epilam agent, wherein the epilam agent comprises at least one compound in the form of a copolymer comprising units M and N bonded by a covalent bond through the main chain, wherein M is 【Chemical Formula 1A】 and N is 【Chemical Formula 2A】 wherein, in the formula R 1 and R 2 may be the same or different and are H, C 1 ~C 10 alkyl group, or C 2 ~C 10 alkenyl group, X and Y may be the same or different and are spacer arms consisting of heteroatoms or consisting of a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom, A may be the same or different and forms an anchoring group for the substrate and is selected from the group consisting of glycidyl, thiol, thioether, thioester, sulfide, thioamide, silanol, alkoxysilane, halogenated silane, hydroxyl, amine, ammonium, nitrogen heterocycle, carboxylic acid, anhydride and catechol, L may be the same or different and is a halogenated ether group according to the following formula (I) ​ wherein, in the formula Q is a halogen atom, P may be the same or different and is a C which contains at least one halogen atom and is linear or branched 1 ~C 10 alkyl group or C 2 ~C 10 alkenyl group, p is selected between 1 and 4, n is selected between 1 and 20, substrate.

3. The base material according to claim 2, wherein the copolymer is a random copolymer and units M and N are randomly distributed.

4. The base material according to claim 1, wherein L is an at least partially fluorinated ether group.

5. The base material according to claim 1, wherein A is selected from the group consisting of glycidyl, thiol, thioether, thioester, sulfide, thioamide, silanol, alkoxysilane, halogenated silane, hydroxyl, phosphate, protected or unprotected phosphonic acid, protected or unprotected phosphonate, amine, ammonium, nitrogen heterocycle, carboxylic acid, anhydride, and catechol.

6. X and Y, which may be the same or different, are C 1 ~C 20 The base material according to claim 1, characterized in that it is selected from the group consisting of an ester group, an amide group, and a styrene-derived group, and X and Y, which may be the same or different, may contain at least one heteroatom.

7. The base material according to claim 1, wherein the unit N / unit M ratio (molar ratio) is between 1 and 20.

8. A base material comprising a surface at least partially coated with an epilam agent, wherein the epilam agent comprises at least one compound in the form of a copolymer comprising units M and N bonded by a covalent bond through the main chain, wherein M is 【Chemical Formula 1B】 and N is [Chemical Formula 2B] wherein, in the formula, R 1 and R 2 may be the same or different and are H, C 1 to C 10 alkyl group, or C 2 to C 10 alkenyl group, and X and Y may be the same or different and are spacer arms consisting of heteroatoms or a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom. A may be the same or different and forms an anchoring group for the base material. L may be the same or different and is a halogenated ether group according to the following formula (I) 【Chemical 3B】 wherein, in the formula, Q is a halogen atom. P may be the same or different and is a C which contains at least one halogen atom and is linear or branched 1 -C 10 alkyl group or C 2 -C 10 alkenyl group, and p is selected between 1 and 4. n is selected between 1 and 20. The copolymer further comprises a unit V bonded to units M and N by a covalent bond through its main chain, wherein V is 【Chemical Formula 4】 wherein, in the formula, R 4 may be the same or different and is H, C 1 ~C 10 alkyl group, or C 2 ~C 10 alkenyl group, and Z may be the same or different and is a spacer arm consisting of heteroatoms or a linear or branched hydrocarbon chain containing at least one carbon atom and at least one heteroatom. T may be the same or different and is a tracer group arranged to measure the concentration of the epilam agent in the epilam coating bath and is a UV absorber group or a fluorophore group. Base material.

9. The UV absorber group is derived from a compound selected from the group consisting of benzotriazole, triazine, phenone, and acylphosphine oxide, and the fluorophore group is derived from a compound selected from the group consisting of fluorescein, naphthyl, anthracene, coumarin, rhodamine, and fluorobenzoate. The substrate according to claim 8.

10. The surface of which at least a part is coated with the epilam agent is made of a material selected from the group consisting of metal, metal oxide, polymer, sapphire, ruby, silicon, silicon oxide, silicon nitride, silicon carbide, diamond-like carbon (DLC), and alloys thereof. The substrate according to claim 1.

11. A method for epilam coating at least a part of the surface of a substrate, A step of preparing an epilam agent containing at least one copolymer according to any one of claims 1 to 10, A step of bringing the surface of the substrate into contact with the epilam agent Including, the method.

12. The preparation of the epilam agent is carried out by copolymerization of a monomer capable of forming the unit M and a monomer capable of forming the unit N. The method for epilam coating according to claim 11.

13. A method for epilam coating at least a part of the surface of a substrate, A step of preparing an epilam agent containing at least one copolymer according to claim 8, A step of bringing the surface of the substrate into contact with the epilam agent Including, The epilam agent is prepared by preparing an epilam coating bath containing the epilam agent, and the surface of the substrate is brought into contact with the epilam agent in the epilam coating bath. The method.

14. A method for epilam coating at least a part of the surface of a substrate, A step of preparing an epilam agent containing at least one copolymer containing units M and N bonded by a covalent bond through the main chain, A step of bringing the surface of the substrate into contact with the epilam agent Including, where, M is 【Chemical Formula 1C】 Yes, N is 【Chemical 2C】 Yes, in the formula, R 1 and R 2 may be the same or different and are H, C 1 ~C 10 alkyl group, or C 2 ~C 10 alkenyl group, and X and Y may be the same or different and are spacer arms consisting of heteroatoms or a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom. A may be the same or different, forms an anchoring group for the substrate, L may be the same or different, and is a halogenated ether group represented by the following formula (I) [Chemical 3C] wherein, Q is a halogen atom, P may be the same or different and is a C which contains at least one halogen atom and is linear or branched 1 ~C 10 alkyl group or C 2 ~C 10 alkenyl group, and p is selected from 1 to 4, n is selected from 1 to 20, The step of bringing the surface of the substrate into contact with the epilam agent is the step of disposing the substrate and the epilam agent in an enclosure at ambient pressure, the step of sealing the enclosure, The step of introducing CO at a pressure of 25 bar to 74 bar and a temperature of 10°C to 80°C into the sealed enclosure 2 and the step of reducing the pressure inside the enclosure, and the step of taking out the substrate coated with epilam from the enclosure A method comprising.

15. Use of a copolymer containing units M and N bonded by a covalent bond through the main chain as an epilam agent for at least a part of the surface of a substrate, wherein M is 【Chemical Formula 5】 and N is 【Chemical Formula 6】 wherein, R 1 and R 2 may be the same or different and are H, C 1 to C 10 alkyl group, or C 2 to C 10 alkenyl group, and X and Y may be the same or different, and are spacer arms consisting of heteroatoms or consisting of a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom, A may be the same or different, forms an anchoring group for the substrate, L may be the same or different, and is a halogenated ether group represented by the following formula (I) [Chemical Formula 7] wherein, Q is a halogen atom, P may be the same or different and is a C that contains at least one halogen atom and is linear or branched 1 ~C 10 alkyl group or C 2 ~C 10 alkenyl group, p is selected from 1 to 10 and n is selected from 1 to 20, The copolymer is a block copolymer containing at least one block of unit M bonded by a covalent bond through its main chain and at least one block of unit N bonded by a covalent bond through its main chain, and the blocks are bonded to each other by a covalent bond through their main chains in a linear arrangement. Use.

16. A watch or jewelry including a component including the substrate according to any one of Claims 1 to 10.

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