Substrate comprising a surface covered with an epilame agent and method for coating such a substrate with epilame

Abstract

The invention relates to a substrate comprising a surface of which at least one part is covered with an epilame agent, characterized in that said epilame agent comprises at least one compound in the form of a polymer soluble in a non-halogenated organic solvent and comprising units N, where N is formula (N), where R2, which may be identical or different, is H, a C1-C10 alkyl group, a C2-C10 alkenyl group; X, which may be identical or different, is a spacer arm; and L, which may be identical or different, is a group according to formula (I), where R6, R7 and R8, which may be identical or different, are H; a C1-C10 alkyl group; a C2-C10 alkenyl group; -(CH2)dOC(O)C(R9)=CH2, or a group according to formula (II), wherein at least one of R6, R7 and R8 is according to formula (II), where R9, which may be identical or different, is H, a C1-C10 alkyl group, a C2-C10 alkenyl group, d is selected from between 1 and 20, R10 and R11, which may be identical or different, are H, a C1-C10 alkyl group, a C2-C10 alkenyl group; R12, which may be identical or different, is H, a C1- C10 alkyl group, a C2-C10 alkenyl group, -(CH2)δO(CH2)εCH3, or (CH2)ψOC(O)C(R13)=CH2, where R13, which may be identical or different, is H, a C1-C10 alkyl group, a C2-C10 alkenyl group, δ is selected from between 1 and 20, ε is selected from between 0 and 20, ψ is selected from between 1 and 20; and y is at least 1 and is selected such that the molar mass of the L group is between 200 g / mol and 30,000 g / mol. The invention also relates to a method for coating such a substrate with epilame, and to a timepiece or piece of jewellery comprising a component that includes such a substrate.

Description

SUBSTRATE COMPRISING A SURFACE COATED WITH A HAIR-REMOVAL AGENT AND A METHOD FOR HAIR-REMOVAL OF SUCH A SUBSTRATE Technical field of the invention

[0001] The present invention relates to a substrate comprising a surface, at least a portion of which is coated with an epilame agent. The invention also relates to methods for epilameing such a substrate. Technological background

[0002] Various processes exist for modifying the surface condition of a substrate by treating it with a suitable agent to specifically improve certain surface properties. For example, in the mechanical engineering field, and particularly in watchmaking, but also in jewelry making, the surface of a part or component is often treated with an epilame agent to control and reduce its surface energy during use. More specifically, an epilame agent aims to prevent the spreading of oils or lubricants on the components of a watch or jewelry piece by forming a hydrophobic and oleophobic surface that allows the lubricant to remain in a predetermined area of ​​the treated surface.

[0003] However, the substances currently used for depilation have several drawbacks. For example, depilation agents such as Fixodrop® ES / BS from Moebius® or the Novec™ range from 3M™ have insufficient resistance to watchmaking washes.

[0004] US patent application US2012 / 0088099 partially solves this problem by proposing the use of an epilame agent carrying a catechol group at the end of its chain. This catechol group is capable of binding firmly to the surface of certain substrates, but does not offer improved resistance to watchmaking washes for substrates such as gold and steel, which are very common substrates in the field of watchmaking or jewelry. Thus, the use of known epilating agents is generally limited to certain materials, which obliges the user to have different types of epilating agents at their disposal depending on the nature of the surfaces to be treated.

[0005] A solution to this problem is described, for example, in patent application WO 2012 / 085130. This solution consists of using a mixture of different compounds (thiol and bisphosphonic) as the epilame composition, the synergistic effect of which promotes the adhesion of the epilame to the substrate. However, the synthesis of each of these compounds requires at least four steps, making the synthesis process for the entire epilame composition lengthy and complex.

[0006] Another solution is described, for example, in patents EP 3 070 133 and EP 3 070 152, which describe an epilame agent comprising a statistical copolymer or a block copolymer, respectively, including a fluorinated motif, an anchoring motif, and optionally an additional hydrocarbon chain. In particular, fluorinated motifs of the type -C5F11 and -CeFi3 are described.

[0007] However, recent European regulations aim to ban the vast majority of fluorinated compounds, including fluorinated epilators, for environmental and health reasons.

[0008] Furthermore, fluorinated epilamins used in the industry are typically applied to the substrate surface using an epilamin bath containing the epilamin in solvents. The solvents used are often fluorinated solvents. This makes the epilamin process polluting. Summary of the invention

[0009] The invention aims in particular to overcome the various drawbacks of known hair removal agents and hair removal processes.

[0010] More specifically, one objective of the invention is to provide an epilame agent that is considered not to be under general regulatory pressure for environmental reasons. More particularly, it is an objective of the present invention to provide a non-fluorinated epilame agent. The invention also aims to provide an epilame agent that can be applied by environmentally friendly processes, more particularly processes using a significant reduction or even the absence of polluting solvents, such as fluorinated solvents, and / or hazardous solvents, for example, flammable or harmful to health (such as ethanol, methanol, tetrahydrofuran (THF), and toluene).

[0011] The invention also aims to provide an epilame agent offering increased resistance to washing compared to known epilame agents, particularly watchmaking washes. The invention further aims to provide a universal epilame agent that can be used on any type of material.

[0012] The invention also aims to provide an environmentally friendly hair removal process that eliminates the use of polluting and / or hazardous solvents (flammable or harmful to health), and more specifically, polluting fluorinated solvents. The invention further aims to provide an economical hair removal process that eliminates the use of a significant quantity of expensive fluorinated solvents.

[0013] The invention also aims to provide an epilame agent and an epilame process which allow precise knowledge of the epilame agent concentration over time, in order to provide robustness to the overall epilame process.

[0014] To this end, a first aspect of the present invention relates to a substrate comprising a surface of which at least a part is coated with an epilame agent according to the attached claims.

[0015] According to the invention, the epilame agent comprises at least one compound in the form of a polymer comprising N units. According to the invention, N is R2, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, and X, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom.

[0016] L is a hydrophobic and oleophobic group. L, whether identical or different, is a group according to formula (I). (I), where Re, R7 and Rs, whether identical or different, are - H, - an alkyl group in the C1-C10 position, - an alkenyl group in C2-C10, - -(CH2)dOC(O)C(R9)=CH2, where ■ R9, identical or different, is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and ■ d is chosen between 1 and 20, preferably between 2 and 10; - a grouping according to formula (II), Rio Rio and R11, whether identical or different, are H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and preferably H or CH3, R12, whether identical or different, is - H, - an alkyl group in the C1-C10 position, - an alkenyl group in C2-C10, - -(CH2)5O(CH2) £ CH3, WHERE ■ 5 is chosen from 1 to 20, preferably from 2 to 10, and ■ s is chosen between 0 and 20, preferably between 0 and 10, - (CH2) OC(O)C(RI3)=CH2, WHERE ■ R13, identical or different, is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and preferably H or CH3, and ■ i is chosen between 1 and 20, preferably between 2 and 10.

[0017] y is at least 1 and is chosen so that the molar mass of the L group is between 200 g / mol and 30000 g / mol, preferably between 250 g / mol and 25000 g / mol, more preferably between 300 g / mol and 20000 g / mol, e.g. between 400 g / mol and 15000 g / mol, or between 500 g / mol and 12500 g / mol.

[0018] At least one of Re, R7 and Rs is according to formula (II).

[0019] It should be noted that the polymer can include different L groups.

[0020] A first non-limiting example of the L group is a group in which Re and R? are CH3 and Rs is a group according to formula (II), where R10 and R11 are CH3 and R12 is C4H9.

[0021] A second non-limiting example of the grouping L is a grouping in which Rs and R7 are CH3 and Rs is a grouping according to formula (II), where R10 and R11 are CH3 and R12 is (CH2)qjOC(O)C(Ri3)=CH2, where i is 3 and R13 is CH3.

[0022] A third non-limiting example of the L group is a group in which Rs is CH3 and R7 and Rs are groups according to formula (II), where R10 and Ru are CH3 and R12 is C4H9.

[0023] Advantageously, X, identical or different, is chosen from the group comprising C1-C20 ester groups, amide groups, and styrene-derived groups. Optionally, X, identical or different, comprises at least one heteroatom.

[0024] Advantageously, the epilame agent of the present invention is at least partially, and preferably entirely, soluble in non-halogenated organic solvents, in particular conventional non-fluorinated organic solvents, e.g., alcohols and ethers. More particularly, the polymer is at least partially, and preferably entirely, soluble in non-halogenated organic solvents. Consequently, the polymer and the epilame agent according to the present invention enable the use of solvent-free epilame processes, or processes using such a non-halogenated organic solvent, thus eliminating the need to use polluting and / or hazardous organic solvents.

[0025] Advantageously, that is, optionally, the polymer is a copolymer further comprising M units. The M units are advantageously hydrophilic units. Surprisingly, the The inventors discovered that despite the presence of N units comprising the hydrophobic and oleophobic L group as described above, the copolymer is soluble in water. In other words, the inventors discovered that the presence of N units does not render the copolymer, which also includes hydrophilic M units, insoluble in water, contrary to the effect that a person skilled in the art would expect.

[0026] The M units and the N units are advantageously associated by covalent bonds through their main chains.

[0027] Advantageously, M is Ri, whether identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, Y, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, and B, whether identical or different, constitutes a polyether group.

[0028] Advantageously, Y, identical or different, is chosen from the group comprising C1-C20 ester groups, amide groups, and styrene-derived groups. Optionally, Y, identical or different, comprises at least one heteroatom.

[0029] Advantageously, B, identical or different, is a -((CH2)aO)[3-R3 group, where R3 is H, a C1-C10 alkyl group, a C2-C10 alkenyl group, and preferably H or CH3; a is chosen from 1 to 6, preferably from 2 to 3; and [3 is chosen from 1 to 30, preferably from 2 to 20, for example from 8 to 10 or from 18 to 20.

[0030] Advantageously, the copolymer is a statistical copolymer. Advantageously, the M units and the N units are randomly distributed. Advantageously, the copolymer is a statistical copolymer and the M units and the N units are randomly distributed.

[0031] Alternatively, and also advantageously, the copolymer is a block copolymer. Advantageously, the block copolymer comprises at least one block of M units covalently linked by their main chains, and at least one block of N units covalently linked by their main chains. Advantageously, the blocks are connected to each other by covalent bonds via their main chains in linear sequences.

[0032] Advantageously, and optionally, the polymer according to this disclosure is a copolymer comprising K units. Advantageously, the K units are associated with the N units by covalent bonds via their main chains. Advantageously, if the polymer is a copolymer comprising M units, the K units are also associated with these M units by covalent bonds via their main chains.

[0033] Advantageously, K is R4, identical or different, is H, an alkyl group in C1-C10, or an alkenyl group in C2-C10, and preferably H or CH3, W, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, and A, identical or different, constitutes a grouping of anchors to the substrate.

[0034] Advantageously, and optionally, the polymer according to this disclosure is a copolymer comprising V units. Advantageously, the V units are associated with the N units by covalent bonds via their main chains. Advantageously, if the polymer is a copolymer comprising M units and / or K units, the V units are also associated with these M units and / or K units by covalent bonds via their main chains.

[0035] Advantageously, V is R 5 t -'n , Or Rs, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, preferably H or CH3, Z, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, and T, identical or different, is a tracer group arranged to determine the concentration of epilame agent in an epilame bath.

[0036] Advantageously, T, whether identical or different, is a UV absorber group or a fluorophore.

[0037] A second aspect of the present invention relates to a method of depilating at least part of a surface of a substrate according to the attached claims.

[0038] The epilaming process according to the present invention includes preparing an epilaming agent comprising at least one polymer soluble in non-fluorinated organic solvents as defined above. Optionally, the depilation process also includes preparing the substrate surface. The depilation process further includes contacting the substrate surface with the depilation agent.

[0039] Advantageously, the epilame agent is prepared by polymerizing monomers capable of forming N units. Advantageously, the N units are as described above. Advantageously, the monomers are selected from the group comprising acrylate, methacrylate, acrylamide, methacrylamide, vinyl, and styrenic monomers.

[0040] According to one embodiment of the epilaming process, the epilaming agent is prepared by preparing an epilaming bath containing the epilaming agent dissolved in a non-halogenated organic solvent. Advantageously, when the epilaming agent comprises at least one copolymer containing N and M units, the epilaming bath is an aqueous epilaming bath containing the epilaming agent dissolved in water. Then, at least a portion of the substrate surface is brought into contact with the epilaming agent in the epilaming bath, for example, by immersing the substrate in the epilaming bath.

[0041] This preparation of the epilame agent is particularly suitable when the epilame agent comprises at least one copolymer further including V units associated with the N units by covalent bonds via their main chains. Advantageously, the V units are as described above. The presence of the V units, and in particular the tracer group, advantageously and optionally allows the concentration of epilame agent in the epilame bath to be controlled before contact. Advantageously, this control is achieved using the tracer group. Optionally, and after controlling the concentration of the epilame agent, the concentration of epilame agent in the epilame bath can be readjusted.

[0042] According to another embodiment of the epilaming process, the substrate surface is brought into contact with the epilaming agent by placing the substrate and the epilaming agent in a chamber at ambient pressure, followed by hermetically sealing the chamber. Then, CO2 at a pressure between 25 bar and 74 bar, preferably between 45 bar and 70 bar, and at a temperature between 10 °C and 80 °C, preferably between 15 °C and 50 °C, is introduced into the hermetically sealed chamber. The pressure in the chamber is then reduced, and the epilamed substrate is removed from the chamber.

[0043] A third aspect of the present invention relates to the use of a polymer comprising N units as an epilame agent for at least a portion of a substrate surface. The N units are as described above.

[0044] The present invention further relates to a watch or jewelry item comprising an element having a substrate according to the first aspect of the present invention.

[0045] One advantage of the epilame agents according to the present invention is that they are not subject to regulatory pressure for environmental reasons, although they offer a high-performance epilame effect. Another advantage is that the polymer contained in the epilame agent is soluble in organic solvents, possibly water, making fluorinated solvents redundant and offering a more environmentally friendly and often more economical alternative. Detailed description of the invention

[0046] According to the present invention, a substrate comprises a surface, at least a portion of which is coated with an epilame agent. Advantageously, at least the surface of the substrate, and optionally the entire substrate, is made of a material selected from the group comprising metals, optionally doped, metal oxides, and metallic nitrides, metallic carbides, metalloids, optionally doped, metalloid oxides, metalloid nitrides, metalloid carbides, alloys comprising at least one metallic element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more of these.

[0047] Preferably, the metal is copper, nickel, beryllium, iron, cobalt, titanium, zirconium, tungsten, silver, gold, platinum, chromium, manganese, magnesium, molybdenum, rhodium, palladium, or zinc. Unlimited examples of doped metals include nickel-phosphorus (NiP) and boron-doped platinum. Preferably, the metalloid is boron or silicon. Unlimited examples of alloys comprising at least one metallic element include brass, aluminum brass, and steel. Unlimited examples of steel include carbon steel and stainless steel. Unlimited examples of carbon steel include Finemac™, 15P (also noted as S15P), CK75, and 20AP.

[0048] Advantageously, in the present invention, the substrate is a substrate of an element of a watch or jewelry part.

[0049] The epilame agent comprises at least one compound in the form of a polymer comprising N units, the N units of which have an X group and an L group.

[0050] Advantageously, the X group, identical or different, is chosen from the group comprising ester groups in C1-C20, preferably in C2-C10, more preferably in C2-C6, and even more preferably in C2-C5, preferably alkyl ester groups, preferably linear, amide groups, and styrene-derived groups.

[0051] The functional group of interest L is responsible for the epilame effect. It does not include halogen atoms, that is to say the functional group of interest L is non-halogenated, more specifically non-fluorinated.

[0052] The functional grouping of interest L is a grouping according to formula (I) R6 If — Rg Rî (I)-

[0053] At least one of Re, R? and Rs is a siloxane group according to formula (II) Rio

[0054] A first example of the functional grouping of interest L is, according to formula (III): (III), where, according to formulas (I) and (II), Rs, R?, Rio and Ru are CH3 and Rs is a siloxane group according to formula (III) in which y is n+1 and R12 is C4H9. Advantageously, n and therefore y are chosen so that the L group has a molar mass between 500 g / mol and 10000 g / mol.

[0055] Advantageously, a polymer comprising N units including the L group according to formula (III) can be obtained by polymerization of an acrylate or methacrylate monomer, for example a methacrylate monomer according to formula (IV) (CAS 146632-07-7):

[0056] A second example of the functional grouping of interest L is according to formula (V): (V), where, according to formulas (I) and (II), Re, R7, R10 and R11 are CH3 and Rs is a siloxane group according to formula (III) in which y is n et R12 is a methacrylate group OC(O)C(CH3)=CH2. Alternatively, R12 can be an acrylate group OC(O)CH=CH2. Advantageously, n and y are chosen such that the group L has a molar mass between 250 g / mol and 25000 g / mol.

[0057] Advantageously, a polymer comprising N units having the L group according to formula (V) can be obtained by polymerization of an acrylate or methacrylate monomer, for example a methacrylate monomer according to formula (VI) (CAS 58130-03-3):

[0058] A third example of the functional grouping of interest L is according to formula (VII): (V | |), where, according to formulas ( I) and (II), Rs, Rio and Rn are CH3, and R7 and Rs are a siloxane group according to formula (III) in which y is n+1 and R12 is C4H9.

[0059] Advantageously, a polymer comprising N units including the L group according to formula (VII) can be obtained by polymerization of an acrylate or methacrylate monomer, for example a methacrylate monomer according to formula (VIII) (CAS 868684-55-3 or CAS 104780-61-2):

[0060] A fourth example of the functional grouping of interest L is, according to formula (IX): According to formulas (I) and (II), Re, R10 and R11 are CH3 and R7 and Rs are a siloxane group according to formula (III) in which y is n+1 and R12 is (CH2)3OCH3, that is to say R12 is a (CH2)0O(CH2) group £ CH3 WHERE 5 is 3 and s is 0.

[0061] Advantageously, a polymer comprising N units including the L group according to formula (IX) can be obtained by polymerization of an acrylate or methacrylate monomer, for example a methacrylate monomer according to formula (X), for example having a molar mass of about 1000 g / mol:

[0062] A fifth example of the functional grouping of interest L is according to formula (XI): according to formulas (I) and (II), Re, R? and Rs are a siloxane group according to formula (III) in which Rio, R11 and R12 are CH3 and y is n+1.

[0063] Advantageously, a polymer comprising N units including the L group according to formula (XI) can be obtained by polymerization of an acrylate or methacrylate monomer, for example a methacrylate monomer according to formula (XII):

[0064] A sixth example of the functional group of interest L can be obtained by polymerization of an acrylate or methacrylate monomer, for example a methacrylate monomer according to formula (XIII), for example having a molar mass between 650 g / mol and 1000 g / mol (CAS 1614238-37-7):

[0065] Advantageously, the polymer is a copolymer further comprising M units, of which the M units include a Y group and a B group.

[0066] Advantageously, group Y, whether identical or different, is chosen from the group comprising ester groups in C1-C20, preferably in C2-C10, more preferably in C2-C6, and even more preferably in C2-C5, preferably alkyl ester groups, preferably linear, amide groups, and styrene-derived groups.

[0067] The functional groups of interest B are hydrophilic groups. Advantageously, they are responsible for the solubility of the copolymer in water. Advantageously, the functional group of interest B comprises between 1 and 30, preferably between 2 and 20, ether groups. That is, the functional group of interest B is a polyether.

[0068] Advantageously, the ether group comprises between 1 and 6, preferably between 2 and 3, CH2 groups. For example, when a is 2, the ether group is of the ethyl ether type (CH2CH2O). For example, when a is 4, the ether group is of the butyl ether type (CH2CH2CH2CH2O).

[0069] Advantageously, the ratio of M units / N units is between 1:10 and 10:1, preferably between 1:5 and 5:1.

[0070] Optionally, the polymer may further comprise at least one K unit, of which the K unit comprises a W group and an A group.

[0071] Advantageously, the W group, identical or different, is chosen from the group comprising ester groups in C1-C20, preferably in C2-C10, more preferably in C2-C6, and even more preferably in C2-C5, preferably alkyl ester groups, preferably linear, amide groups, and styrene-derived groups.

[0072] The functional groups of interest A are capable of reacting with the surface of the substrate to be epilamed, so as to form anchoring groups of the epilaming agent to the substrate surface. Advantageously, A groups can also be provided at the end of the copolymer.

[0073] Advantageously, A is chosen from the group comprising glycidyl, thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, protected or unprotected phosphonic acids, protected or unprotected phosphonates, amines, ammoniums, nitrogen heterocycles, carboxylic acids, anhydrides, and catechols.

[0074] Optionally, the polymer is a copolymer further comprising at least one U unit, where U is R14, identical or different, is H, an alkyl group in C1-C10, or an alkenyl group in C2-C10, and preferably H or CH3, and R15, identical or different, is H, CH3, a hydrocarbon chain that may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.

[0075] Advantageously, when the copolymer comprises at least one U unit, the U unit and the N units, and the optional M and K units are associated by covalent bonds through their main chains.

[0076] Advantageously, the functional groups of interest R7 allow for modification of the properties of the epilame agent and / or the provision of additional functions. For example, R7 can be an alkyl chain used to modify the contact angle obtained, or it can also be a chain capable of forming crosslinking points during a complementary crosslinking step.

[0077] Optionally, the polymer may further comprise at least one V unit, of which the V unit comprises a Z group and a T group.

[0078] Advantageously, the Z group, identical or different, is chosen from the group comprising ester groups in C1-C20, preferably in C2-C10, more preferably in C2-C6, and even more preferably in C2-C5, preferably alkyl ester groups, preferably linear, amide groups, and styrene-derived groups.

[0079] Advantageously, the T group allows, for example, the determination of the copolymer concentration by spectroscopy.

[0080] Advantageously, T, identical or different, is a UV-absorbing group derived from a compound selected from the group comprising benzotriazoles, triazines, phenones (including benzophenone, acetophenone, hydroxyalkylphenone, hydroxyarylphenone, amino alkylphenone, and anthraquinone), and acyl-phosphine oxides.

[0081] Advantageously, T, identical or different, is a fluorophore group derived from a compound selected from the group comprising fluorescein, a naphthyl, anthracene, coumarin, rhodamine, and a fluorobenzoate.

[0082] Advantageously, when the polymer is a copolymer comprising N units, V units and optionally M units and / or K units, the copolymer comprises between 0.1% and 20% K units, preferably between 0.5% and 15%, more preferably between 1% and 10%, the percentages being expressed as a percentage of the total number of units in the copolymer.

[0083] When the polymer is a copolymer as described above, the copolymer can be a statistical copolymer or a block copolymer.

[0084] Advantageously, when the copolymer is a statistical copolymer, the N units and the other units (that is, one or more units chosen from the M units, K units, V units, and U units) are randomly distributed. In other words, the units are statistically linked to each other by their main chain.

[0085] Advantageously, when the copolymer is a block copolymer, the copolymer comprises at least one block of N units covalently linked by their main chains, and at least one block of the other units covalently linked by their main chains. Preferably, the block copolymer comprises a single block of N units. Alternatively or additionally, and preferably, the block copolymer comprises a single block of M units (if present), a single block of K units (if present) and / or a single block of V units (if present), associated by covalent bonds through their main chains.

[0086] Optionally, at least one of the N-unit block, the optional M-unit block, the optional K-unit block, and the optional V-unit block may include at least one U-unit, covalently linked by their main chains. Advantageously, the blocks are covalently linked by their main chains in linear sequences. If the block copolymer further includes at least one U-unit, then at least one of the N-unit block, the optional M-unit block, the optional K-unit block, and the optional V-unit block may include at least one U-unit, and the number of U-units in the N-unit block may vary from the number of U-units in the M-unit block, the number of U-units in the K-unit block, and the number of U-units in the V-unit block if these latter (M, K, and V) are included in the block copolymer.

[0087] Preferably, the U units are integrated and distributed within the block composed of the N units, for example by statistical copolymerization of U units with the N units to form a single block consisting mainly of N units and assimilated to a block of N units.

[0088] The present invention also relates to a method of depilating at least a part of a substrate surface comprising the preparation of a depilating agent, optionally the preparation of the substrate surface, and bringing the substrate surface into contact with the depilating agent.

[0089] Advantageously, the preparation of the epilame agent includes the polymerization of monomers capable of forming N units. Examples of monomers capable of forming an N unit are described above.

[0090] If the polymer is a copolymer further comprising one or more of the M units, K units, V units and U units, the Preparation of the epilame agent includes the copolymerization of monomers capable of forming N units, optionally monomers capable of forming at least one M unit, one K unit, one V unit and / or one U unit.

[0091] Advantageously, the monomers are chosen from the group comprising acrylate, methacrylate, acrylamides, methacrylamides, vinyl, diene, styrene and olefinic monomers.

[0092] The monomers particularly preferred for forming V units containing a tracer T group are chosen from the group comprising 2-H-benzotriazole-2-yl-hydroxyphenyl ethyl 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 polymerizable.

[0093] Even more preferentially, the monomers for forming the V units containing a tracer group T are chosen from the group comprising 2-H-benzotriazole-2-yl-hydroxyphenyl ethyl 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 tracer groups that can be tracked by UV-visible spectroscopy, which is much easier to implement in an industrial environment than fluorescence spectroscopy.

[0094] The polymerization techniques include those known to those skilled in the art. Optionally, (co)polymerization is carried out in the presence of an initiation system comprising an initiator, such as, but not limited to, azobisisobutyronitrile (AIBN). Optionally, (co)polymerization is carried out at an elevated temperature.

[0095] The polymers used in the present invention can be obtained in the form of powder or viscous liquid.

[0096] A particularly suitable polymerization method for obtaining a statistical copolymer is radical copolymerization, in solution or emulsion. Advantageously, the radical copolymerization is either a free radical copolymerization or a controlled radical copolymerization, preferably a controlled radical copolymerization.

[0097] A particularly suitable polymerization method for obtaining a block copolymer is successive controlled radical copolymerization: - of monomers capable of forming at least one block of N units and optionally with monomers capable of forming at least one U unit, U being identical or different, - optionally with monomers capable of forming at least one block of M units and optionally with monomers capable of forming at least one U unit, - optionally with monomers capable of forming at least one block of K units and optionally with monomers capable of forming at least one U unit, U being identical or different, and - optionally with monomers capable of forming at least one block of V units and optionally with monomers capable of forming at least one U unit, U identical or different.

[0098] According to a first mode of (co)polymerization, the (co)polymer can be obtained in a single step by (co)polymerization, preferably radical, of monomers bearing XL side chains, optionally with one or more monomers bearing YB side chains, WA side chains, ZT side chains, R? side chains.

[0099] According to another mode of (co)polymerization, the (co)polymer can be obtained by (co)polymerization, preferably radical, of monomers bearing the appropriate X side chains, optionally with monomers bearing the appropriate Y side chains, optionally with monomers bearing the appropriate W side chains, optionally with monomers bearing the appropriate Z side chains, and optionally with monomers bearing side chains intended to bear Ru, then the side chains are modified, for example by "click chemistry", to introduce the functional groups of interest L, B (optionally), A (optionally), T (optionally), and R15 groups (optionally).

[0100] Optional substrate surface preparation may include cleaning and / or washing the surface to be epilaminated. Such cleaning may be carried out using methods known to those skilled in the art. For example, and particularly when the substrate is a watch component, cleaning may include standard watchmaking procedures.

[0101] Alternatively, substrate surface preparation can include CO2 treatment at a temperature between 10°C and 80°C and a pressure between 25 bar and 250 bar, for example, for a duration of 1 to 60 minutes. Such treatment advantageously removes dust particles and degreases the surface.

[0102] Advantageously, the polymer(s) are dissolved in a solution comprising a non-halogenated organic solvent. Advantageously, the solution is an aqueous solution comprising between 0% and 15% by weight, preferably between 0% and 10% by weight, of the non-halogenated organic solvent, based on the total mass of the (aqueous) solution excluding the polymer(s). It is understood that when the aqueous solution contains no non-halogenated organic solvent (0% by volume), the aqueous solution is simply water.

[0103] Non-limited examples of non-halogenated organic solvents include alcohols, e.g. methanol, ethanol, n-butanol and isopropanol, as well as ethers, esters, ketones (such as acetone and butanone), amines and alkanes (such as pentane, hexane and heptane).

[0104] Advantageously, the epilame agent solution does not contain a halogenated solvent.

[0105] Advantageously, the polymer(s) are dissolved in the solution, for example in water, at concentrations between 50 mg / L and 1 g / L, in order to obtain a solution of epilame agent.

[0106] According to a first embodiment of the epilaming process, such a solution of epilaming agent is then used in an epilaming bath. The same epilaming bath can be used several times. Advantageously, when the same epilaming bath is used several times, means for controlling and optionally for maintaining the concentration of the epilaming agent are provided in order to control and optionally maintain this concentration over time, and preferably before contacting the substrate surface with the epilaming agent in the epilaming bath.

[0107] Such concentration control methods may include the presence of at least one V unit as described above in the (co)polymer. In other words, the presence of at least one V unit comprising a T group as described above allows for control of the epilame agent concentration in the epilame bath.

[0108] Advantageously, when the T group is a UV absorber or a fluorophore, the concentration of the epilame agent is determined by spectroscopy (e.g., absorbance measurement). An intermediate step, prior to the step of controlling the concentration of the epilame agent in the epilame bath, involves developing a calibration curve for the copolymer. For this, the The copolymer is dissolved at different concentrations in a solvent, and for each solution, the absorbance is measured spectroscopically as a function of wavelength. The wavelength at which the absorbance is maximum is identified, and then the calibration curve A = F(concentration) is plotted at the wavelength at which the absorbance is maximum. The molar extinction coefficient of the polymer can then be deduced (Beer-Lambert law A = scl).

[0109] To control the concentration of epilame in the epilame bath, simply measure the absorbance of the bath solution using spectroscopy, and then, using the previously established calibration curve, deduce the concentration of epilame in the bath. Depending on the result, additional epilame can then be added to the bath to precisely readjust the concentration.

[0110] The depilating process according to the invention may further include, after contacting the surface of the substrate with the depilating agent, a drying step of the depilated surface.

[0111] According to a second embodiment of the epilaming process, the epilame agent solution as described above is used (including being placed) in a chamber. Alternatively, the epilame agent can be placed in the chamber in its pure form.

[0112] Advantageously, the substrate and the epilame agent are placed in a chamber at ambient pressure, i.e., a pressure between 0.6 bar and 1.1 bar, followed by hermetically sealing the chamber. Then, CO2 is introduced into the hermetically sealed chamber. Advantageously, the CO2 is introduced for a duration of between 1 and 30 min, preferably between 1 and 20 min, and more preferably between 3 and 15 min.

[0113] Advantageously, the CO2 is at a pressure between 25 bar and 74 bar, preferably between 45 bar and 70 bar, and more preferably between 50 bar and 60 bar. Advantageously, the CO2 is at a temperature between 10 °C and 80 °C, preferably between 10 °C and 60 °C, and more preferably between 15 °C and 50 °C.

[0114] Then, the CO2 injection is stopped and the pressure in the chamber is reduced. Advantageously, the pressure is reduced to ambient pressure, i.e., a pressure between 0.6 bar and 1.1 bar. Then, the epilaminated substrate is removed from the chamber.

[0115] Optionally, after the pressure in the chamber has been reduced and the epilaminated substrate has been removed from the chamber, the epilaminated substrate can be heat-treated. For example, the epilaminated substrate can be heated in the chamber to a temperature between 250 °C and 90 °C, preferably between 30 °C and 80 °C, for a duration of between 1 and 45 minutes, preferably between 2 and 30 minutes. Such heat treatment improves the adhesion of the epilaminated agent to the surface of the treated substrate.

[0116] The de-icing process according to the invention may further comprise, after contacting the substrate surface with the de-icing agent, a complementary crosslinking step. This complementary crosslinking is advantageously made possible by the presence of the appropriate functional groups of interest provided on the R14 side chains of the U units.

Claims

DEMANDS 1. Substrate comprising a surface at least a portion of which is coated with an epilame agent, characterized in that said epilame agent comprises at least one compound in the form of a polymer comprising N units, where R2, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, X, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, characterized in that L, identical or different, is a group according to formula (I) R6 If — R8 R 7 (I), where Re, Ï and Rs, identical or different, are H, an alkyl group in C10-C10, an alkenyl group in C2-C10, -(CH2)dOC(O)C(R9)=CH2, or a group according to formula (II), Or R9, identical or different, is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and d is chosen between 1 and 20, preferably between 2 and 10, R10 and R11, whether identical or different, are H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and preferably H or CH3, R12, identical or different, is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, -(CH2)ÔO(CH2) £ CH3, OR (CH2) OC(O)C(RI3)=CH2, WHERE R13, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, 5 is chosen between 1 and 20, preferably between 2 and 10, s is chosen between 0 and 20, preferably between 0 and 10, i is chosen between 1 and 20, preferably between 2 and 10, and y is at least 1 and is chosen so that the molar mass of the L group is between 200 g / mol and 30000 g / mol, preferably between 250 g / mol and 25000 g / mol, in which at least one of Rs, R7 and Rs is according to formula (II), and in which R12 is not a C1-C10 alkyl group if one of Rs, R7 and Rs is according to formula (II).

2. Substrate according to claim 1, characterized in that Rs and R7 are CH3 and Rs is a grouping according to formula (II), or Rio and Rn are CH3 and R12 is (CH2)qjOC(O)C(Ri3)=CH2, where ip is 3 and R13 is CH3 or H.

3. Substrate according to claim 1, characterized in that Re is CH3 and R7 and Rs are groups according to formula (II), where R10 and R11 are CH3 and R12 is C4H9 or (CH2)qjOC(O)C(Ri3)=CH2, where ip is 3 and R13 is CH3 OR H.

4. Substrate according to claim 1, characterized in that Re, R7 and Rs are groups according to formula (II), where R10 and R11 are CH3 and R12 is C4H9 or (CH2) OC(O)C(Ri3)=CH2, where ip is 3 and R13 is CH3 or H.

5. Substrate according to any one of the preceding claims, characterized in that X, identical or different, is selected from the group comprising C1-C20 ester groups, amide groups, and styrene-derived groups, in which X, identical or different, optionally comprises at least one heteroatom.

6. Substrate according to any one of the preceding claims, characterized in that the polymer is a copolymer further comprising M units, said M units and said N units being associated by covalent bonds through their main chains, where M is Ri, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, Y, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, B, identical or different, is -((CH2)aO)p-R3, where R3 is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and preferably H or CH3, a is chosen between 1 and 6, preferably between 2 and 3, and [3 is chosen between 1 and 30, preferably between 2 and 20.

7. Substrate according to claim 6, characterized in that the copolymer is a statistical copolymer and the M units and the N units are randomly distributed.

8. Substrate according to claim 6, characterized in that the copolymer is a block copolymer comprising at least one block of M units associated by covalent bonds through their main chains, and at least one block of N units associated by covalent bonds through their main chains, said blocks being connected to each other by covalent bonds through their main chains in linear sequences.

9. Substrate according to any one of the preceding claims, characterized in that the polymer further comprises K units associated with N units and optional M units by covalent bonds through their main chains, where K is R4, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, W, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, and A, identical or different, is chosen from the group comprising glycidyl, thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, protected or unprotected phosphonic acids, protected or unprotected phosphonates, amines, ammoniums, nitrogen heterocycles, carboxylic acids, anhydrides, and catechols.

10. Substrate according to any one of the preceding claims, characterized in that the polymer further comprises V units associated with N units and optional M units by covalent bonds through their main chains, where V is Rs, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, Z, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, and T, identical or different, is a tracer group arranged to determine the concentration of epilame agent in an epilame bath, in which T, identical or different, is a UV absorber group or a fluorophore.

11. A process for removing at least part of a substrate surface comprising the steps of: - preparation of an epilame agent comprising at least one polymer as defined in the preceding claims, - optionally, preparation of the substrate surface, - bringing the substrate surface into contact with the epilame agent, characterized in that the preparation of the epilame agent comprises the preparation of an aqueous epilame bath containing the epilame agent dissolved in an aqueous solution optionally comprising a non-halogenated organic solvent and which does not contain a halogenated solvent; and the substrate surface is brought into contact with the epilame agent in the epilame bath, or the step of bringing the substrate surface into contact with the epilame agent comprises the steps of: - placement of the substrate and the epilame agent in a chamber at ambient pressure, - airtight seal of the enclosure, - introduction of CO2 into the hermetically sealed enclosure at a pressure between 25 bar and 74 bar, preferably between 45 bar and 70 bar, and at a temperature between 10 °C and 80 °C, preferably between 15 °C and 50 °C, - decrease in pressure within the enclosure, and - removal of the epilaminate substrate from the enclosure.

12. A depilating process according to claim 11, characterized in that the preparation of the depilating agent comprises the polymerization of monomers capable of forming N units, preferably wherein the monomers are selected from the group comprising acrylate, methacrylate, acrylamides, methacrylamides, vinyl, and styrenic, in which polymerization precedes, if present, the preparation of the depilating bath.

13. A hair removal process according to any one of claims 11 to 12, characterized in that the preparation comprises the preparation of the hair removal agent, the preparation of a hair removal bath, and the aqueous solution comprises between 0% by weight and 15% by weight of the non-halogenated organic solvent.

14. Epilaming process according to claim 13, characterized in that the epilaming agent comprises at least one copolymer as defined in claims 6 to 8, and the aqueous solution is water.

15. A hair removal method according to any one of claims 11 to 14, wherein the preparation of the epilame agent comprises the preparation of an epilame bath, characterized in that the polymer of the epilame agent is dissolved in the aqueous solution at concentrations between 50 mg / L and 1 g / L.

16. A hair removal method according to any one of claims 11 to 15, characterized in that the epilame agent comprises at least one copolymer as defined in claim 10, its preparation includes the preparation of an epilame bath, and the process includes, before contacting, a step of controlling the concentration of epilame agent in the epilame bath by means of the tracer group and, optionally, a step of readjusting the concentration of epilame agent in the epilame bath.

17. Use of a polymer comprising N units, where N is Or R2, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, and preferably H or CH3, X, identical or different, is a spacer arm consisting of a heteroatom or a hydrocarbon chain containing at least one heteroatom, linear or branched, comprising at least one carbon atom, characterized in that L, identical or different, is a group according to formula (I) Rs, R? and Rs, identical or different, are H, an alkyl group in C1-C10, an alkenyl group in C2-C10, -(CH2)dOC(O)C(Rg)=CH2, or a group according to formula (II), Rio R9, identical or different, is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and d is chosen between 1 and 20, preferably between 2 and 10, R10 and R11, whether identical or different, are H, an alkyl group at C1-C10, an alkenyl group at C2-C10, and preferably H or CH3, R12, identical or different, is H, an alkyl group at C1-C10, an alkenyl group at C2-C10, -(CH2)ÔO(CH2) £ CH3, OR (CH2) OC(O)C(RI3)=CH2, WHERE Ri3, identical or different, is H, an alkyl group in C1-C10, an alkenyl group in C2-C10, preferably H or CH3, 5 is chosen between 1 and 20, preferably between 2 and 10, s is chosen between 0 and 20, preferably between 0 and 10, i is chosen between 1 and 20, preferably between 2 and 10, and y is at least 1 and is chosen so that the molar mass of the L group is between 200 g / mol and 30000 g / mol, preferably between 250 g / mol and 25000 g / mol, and in which at least one of Re, R7 and Rs is according to formula (II) and R12 is not a C1-C10 alkyl group if one of Re, R7 and Rs is according to formula (II), as an epilame agent of at least a part of a surface of a substrate.

18. A watch or jewelry item comprising an element having a substrate according to any one of claims 1 to 10.

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