Substrates containing surfaces coated with epiram agents and methods for epiram coating such substrates

Abstract

The present invention relates to a substrate comprising a surface at least partially coated with an epiramid agent, said epiramid agent comprising at least one compound in the form of a copolymer comprising M and N units linked by a covalent bond through the backbone, wherein M is JPEG2026501559000018.jpg33160, and N is JPEG2026501559000019.jpg35160, wherein R1 and R2 are the same or different and each represent H, C1 to C 10 Alkyl group or C2-C 10 X and Y are the same or different and are spacer arms consisting of heteroatoms or linear or branched hydrocarbon chains containing at least one heteroatom and at least one carbon atom; B is the same or different and is a polyether group; L is a halogenated C1-C6 carbon group or a group represented by formula (I) JPEG2026501559000020.jpg41164, wherein Q is a halogen atom; P is the same or different, contains at least one halogen atom, and is linear or branched, C1-C 10 Alkyl group or C2-C 10 is an alkenyl group; p is selected from 1 to 4; and n is selected from 1 to 20, wherein the copolymer is water-soluble. The invention also relates to a method for epilam coating such a substrate, and to a watch or jewelry containing a component comprising such a substrate.

Description

[Technical Field]

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

[0002] There are various methods for modifying the surface condition of a substrate by treating it with suitable agents to specifically improve certain surface properties.For example, in the field of machinery, especially in the field of watches, and also in the field of jewelry, epilam coating of some surfaces or the surface of components is often carried out using epilam agent, so as to control and reduce the surface tension of the surface during use.More specifically, epilam agent is designed to form a hydrophobic and oleophobic surface, which allows the lubricant to remain in a predetermined place on the treated surface, thereby preventing oil or lubricant from spreading on the components of watches or jewelry.

[0003] However, the materials currently used for epilam coating have some drawbacks: for example, epilam agents such as Fixodrop® ES / BS by Moebius® or the Novec™ series by 3M™ have poor resistance to watch washing.

[0004] Patent Application No. US2012 / 0088099 partially solves this problem by proposing the use of epilaminants with catechol functionality at the end of the chain. This catechol functionality can adhere firmly to the surface of certain substrates, but does not improve the resistance to watch washing of substrates such as gold and steel, which are very common substrates in the watch and jewelry industry. As a result, the use of known epilaminants is generally limited to certain materials, and users must therefore use different types of epilaminants depending on the nature of the surface to be treated.

[0005] One solution to this problem is described, for example, in Patent Application WO2012 / 085130. This solution involves the use of a blend of compounds of different types (thiol and bisphosphonic acid) as an epiram composition, the synergistic effect of which promotes adhesion of the epiram to the substrate. However, the synthesis of each of these compounds requires at least four steps, making the synthesis of the epiram composition as a whole long and complicated.

[0006] Other solutions are described, for example, in patents EP 3 070 133 and EP 3 070 152. EP 3 070 133 describes epiramidal agents comprising statistical copolymers containing fluorinated units, anchoring units, and optionally further hydrocarbon chains. Patent EP 3 070 152 describes epiramidal agents comprising block copolymers containing fluorinated units, anchoring units, and optionally further hydrocarbon chains. In particular, -CF 11 and -CF 13 A fluorinated unit is described.

[0007] However, perfluorohexanoic acid (PFHxA, CAS 307-24-4), its salts, and related substances are under general regulatory scrutiny for environmental reasons. Furthermore, these epiram agents are typically applied to substrate surfaces using an epiram coating bath containing the epiram agent in a solvent. Furthermore, the solvents used are often fluorinated solvents. This makes the epiram coating process a polluting process. Summary of the Invention

[0008] The present invention is particularly aimed at overcoming various drawbacks of known epiram agents and epiram coating methods.

[0009] More specifically, one of the objectives of the present invention is to provide an epiram formulation that is not considered to be under general regulatory scrutiny for environmental reasons. Another objective of the present invention is to provide an epiram formulation that can be applied by an environmentally friendly method, more specifically, a method that involves a significant reduction in, or even the complete elimination of, polluting solvents such as fluorinated solvents.

[0010] Another object of the present invention is to provide an epiram formulation that has increased wash resistance compared to known epiram formulations, and a universal epiram formulation that can be used on any type of material.

[0011] The present invention also aims to provide an environmentally friendly epilam coating process that eliminates the use of solvents, more specifically polluting fluorinated solvents. The present invention also aims to provide a cost-effective epilam coating process that eliminates the need for large amounts of expensive fluorinated solvents.

[0012] It is also an object of the present invention to provide an epiram agent and an epiram coating method that allows for accurate measurement of epiram agent concentration over time, so as to increase the robustness of the overall epiram coating process.

[0013] To this end, a first aspect of the present invention relates to a substrate comprising a surface coated with an epilamidant as set forth in part in the accompanying claims.

[0014] According to the present invention, an epiram agent comprises at least one compound in the form of a copolymer comprising M and N units, the M and N units being linked by a covalent bond through the backbone.

[0015] According to the present invention, M is [ka] wherein: R1 may be the same or different and may be H, C1 to C 10 Alkyl groups, C2-C 10 an alkenyl group, preferably H or CH; Y is the same or different and is a spacer arm consisting of a heteroatom or a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom; B may be the same or different and is a polyether group.

[0016] Preferably, Y is the same or different and is selected from C1 to C 20 It is selected from the group comprising an ester group, an amide group and a styrene derivative group. Optionally, Y, the same or different, comprises at least one heteroatom.

[0017] Preferably, B is the same or different and is —((CH) α O) β -R group, R3 is H, C1~C 10 Alkyl groups, C2-C 10 an alkenyl group, preferably H or CH; α is selected from 1 to 6, preferably 2 to 3; β is selected from 1 to 30, preferably 2 to 20, for example, 8 to 10 or 18 to 20.

[0018] According to the present invention, N is [ka] and in the formula R2 may be the same or different and may be H, C1 to C 10 Alkyl groups, C2-C 10 an alkenyl group, preferably H or CH; X are the same or different and are spacer arms consisting of heteroatoms or linear or branched hydrocarbon chains containing at least one heteroatom and at least one carbon atom; L may be the same or different and represent a halogenated C1-C6 carbon group or a group represented by formula (I). [ka] is a halogenated ether group according to the formula: Q is a halogen atom, P is the same or different, contains at least one halogen atom, and is linear or branched, C1-C 10 Alkyl group or C2-C 10 is an alkenyl group, p is selected from 1 to 4, preferably 2 or 3; n is selected from 1 to 20, preferably 1 to 10.

[0019] Preferably, X is the same or different and is C1 to C 20 It is selected from the group comprising an ester group, an amide group and a styrene derivative group. Optionally, X, the same or different, comprises at least one heteroatom.

[0020] Preferably, L is a partially fluorinated, e.g., fully fluorinated, C1-C6 carbon group. Alternatively, and also preferably, L is an at least partially fluorinated, e.g., fully fluorinated, ether group. The term "fully fluorinated," as used in this disclosure, refers to a group in which each hydrogen atom is replaced by a fluorine atom.

[0021] The copolymer may contain different L groups, for example a blend of at least partially halogenated C1-C6 carbon groups and halogenated ether groups according to formula (I).

[0022] Preferably, the copolymer is a statistical copolymer. Preferably, the M and N units are randomly distributed. Preferably, the copolymer is a statistical copolymer, and the M and N units are randomly distributed.

[0023] Alternatively and also preferably, the copolymer is a block copolymer. Preferably, the block copolymer comprises at least one block of M units linked by covalent bonds through the backbone and at least one block of N units linked by covalent bonds through the backbone. Preferably, the blocks are linked together by covalent bonds through the backbone in a linear arrangement.

[0024] Suitably, the ratio of M units to N units is in the range of 1:10 to 10:1, preferably 1:5 to 5:1.

[0025] More specifically, B is the above-mentioned -((CH2) α O) β In the case of -R3 groups, the inventors have found that the optimal ratio of M units to N units depends on the value of β. The expression "optimal ratio of M units to N units" is understood to mean the ratio of M units to N units that allows achieving the optimal epilam effect. A good epilam effect results, but is not limited to, in low surface tension values, high water drop angle values ​​(in any case greater than 85°), and / or good resistance to cleaning, especially watch cleaning.

[0026] For example, when β is a value in the range of 1 to 10, preferably 5 to 10, more preferentially 8 to 10, such as equal to a value of 9, the optimal ratio of M units to N units is in the range of 1:1 to 2:1, more particularly 1:1 to 3:2, such as 1:1 to 11:9 or 1:1 to 10:9. For example, when β is a value in the range of 11 to 30, preferably 12 to 20, more preferentially 18 to 20, such as equal to a value of 19, the optimal ratio of M units to N units is in the range of 1:5 to 3:5, more particularly 2:5 to 1:2.

[0027] The present inventors have surprisingly discovered that the epiram agents of the present invention are at least partially, preferably completely, water-soluble. More specifically, the copolymers are at least partially, preferably completely, water-soluble. While not intending to be limited thereto, the present inventors believe that this excellent water solubility is the result of the specific composition of the copolymer. More specifically, the present inventors believe that the ratio of M units to N units allows the copolymer, preferably the epiram agent, to be dissolved in water. As a result, the copolymers and epiram agents described in the present invention allow for the use of aqueous epiram coating methods, thereby eliminating the need for contaminating organic solvents.

[0028] Preferably, and optionally, the copolymers according to the present disclosure also include K units. Preferably, the K units are linked to the M and N units by covalent bonds through the backbone. Preferably, K is [ka] and in the formula R4 may be the same or different and may be H, C1 to C 10 Alkyl group or C2-C 10 an alkenyl group, preferably H or CH; W is the same or different and is a spacer arm consisting of a heteroatom 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 form an anchoring group on the substrate.

[0029] Preferably, W is the same or different and is selected from C1 to C 20 It is selected from the group comprising an ester group, an amide group and a styrene derivative group. Optionally, W, the same or different, comprises at least one heteroatom.

[0030] Suitably, A is selected from the group comprising glycidyl, thiol, thioether, thioester, sulfide, thioamide, silanol, alkoxysilane, halogenated silane, hydroxyl, phosphate, protected or unprotected phosphate, protected or unprotected phosphonate, amine, ammonium, nitrogen heterocycle, carboxylic acid, anhydride and catechol.

[0031] Suitably, when the copolymer according to the present disclosure comprises K units, and β is equal to a value in the range of 8 to 10, the copolymer comprises, in the percentages indicated relative to the total number of units in the copolymer, 5% to 20%, preferably 7% to 15%, of K units, 30% to 65%, preferably 35% to 60%, of M units, and 25% to 60%, preferably 30% to 55%, of N units.

[0032] Suitably, when the copolymer according to the present disclosure comprises K units and β is equal to a value in the range of 18 to 20, the copolymer comprises 5% to 20%, preferably 7% to 15%, of K units, 15% to 45%, preferably 25% to 35%, of M units, and 50% to 75%, preferably 55% to 65%, of N units, the percentages being expressed relative to the total number of units in the copolymer.

[0033] Preferably, and optionally, the copolymers described herein further comprise V units. Preferably, the V units are linked to the M and N units by covalent bonds through the main chain. Preferably, V is [ka] and in the formula R5 may be the same or different and may be H, C1 to C 10 Alkyl groups, C2-C 10 an alkenyl group, preferably H or CH; Z is the same or different and is a spacer arm consisting of a heteroatom or a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom; T may be the same or different and is a tracer group designed to measure the concentration of the epiram agent in the epiram coating bath.

[0034] Suitably, T are the same or different and are a UV absorber group or a fluorophore.

[0035] Suitably, when the copolymers described herein contain V units, the copolymers contain 0.1% to 20%, preferably 0.5% to 15%, more preferentially 1% to 10% of K units, in the proportions indicated relative to the total number of units in the polymer.

[0036] Preferably, the surface of the substrate, at least a portion of which is coated with the epitaxial agent, is made of a material selected from the group comprising optionally doped metals, metal oxides, metal nitrides, metal carbides, optionally doped metalloids, metalloid oxides, metalloid nitrides, metalloid carbides, alloys containing at least one metal element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more thereof.

[0037] A second aspect of the present invention relates to a method for epilam coating at least a portion of a substrate surface as set forth in the accompanying claims.

[0038] The epiram coating method of the present invention includes preparing an epiram agent containing at least one water-soluble copolymer as defined above. Optionally, the epiram coating method further includes preparing a surface of a substrate. The epiram coating method further includes contacting the surface of the substrate with the epiram agent.

[0039] Preferably, the epiram agent is prepared by copolymerizing a monomer capable of forming an M unit with a monomer capable of forming an N unit. Preferably, the M unit and the N unit are as described above. Preferably, the monomer is selected from the group consisting of acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl monomers, and styrene monomers.

[0040] According to one embodiment of the epiram coating method, the epiram agent is prepared by preparing an epiram coating bath containing the epiram agent. Preferably, the epiram coating bath is an aqueous epiram coating bath containing the epiram agent dissolved in water. At least a portion of the substrate surface is then contacted with the epiram agent in the aqueous epiram coating bath, for example, by immersing the substrate in the aqueous epiram coating bath.

[0041] This method of preparing an epiram agent is particularly suitable when the epiram agent comprises at least one copolymer also comprising a V unit covalently linked to the M and N units through the main chain. Preferably, the V unit is as described above. The presence of the V unit, particularly the tracer group, preferably allows for testing the concentration of the epiram agent in the aqueous epiram coating bath before contacting. Preferably, this testing is carried out using the tracer group. Optionally, after testing the concentration of the epiram agent, the concentration of the epiram agent in the aqueous epiram coating bath may be readjusted.

[0042] According to another embodiment of the epilam coating method, the substrate and epilam agent are placed in an enclosure at ambient pressure, and the enclosure is then sealed, thereby contacting the surface of the substrate with the epilam agent. CO2 is then introduced into the sealed enclosure at a pressure ranging from 25 bar to 74 bar, preferably from 45 bar to 70 bar, and a temperature ranging from 10°C to 80°C, preferably from 15°C to 50°C. The pressure in the enclosure is then reduced, and the epilam-coated substrate is removed from the enclosure.

[0043] A third aspect of the present invention relates to the use of a copolymer comprising M and N units covalently linked through a chain as an epitaxial agent for at least a portion of the surface of a substrate. The M and N units are as described above. The copolymer is water-soluble.

[0044] The present invention further relates to a watch or piece of jewellery comprising a component comprising a substrate according to the first aspect of the invention.

[0045] One advantage of the epilam formulations described in the present invention is that they are not subject to regulatory scrutiny for environmental reasons, yet provide high-performance epilam effects. Another advantage is that the copolymers contained in the epilam formulations are water-soluble, eliminating the need for fluorinated solvents and providing a more environmentally friendly and often more economical alternative. Another advantage is that the epilam formulations described in the present invention have excellent resistance to cleaning, especially watch cleaning. [Brief explanation of the drawings]

[0046] Objectives, advantages and features are illustrated in the following non-limiting figures. [Figure 1] FIG. 1 shows the structure of an epiram copolymer of the present invention. [Figure 2] FIG. 2 shows contact angles measured on various substrates whose surfaces have been coated with epilamidic agents of the present invention. [Figure 3]FIG. 3 shows the contact angles measured on various substrates whose surfaces were coated with the reference C6F13 epiram agent. [Figure 4] FIG. 4 shows contact angles measured on various substrates whose surfaces were coated with competing epiram agents. DETAILED DESCRIPTION OF THE INVENTION

[0047] According to the present invention, the substrate comprises a surface at least partially coated with an epitaxial agent. Preferably, at least the surface of the substrate, and optionally the entire substrate, is made of a material selected from the group comprising optionally doped metals, metal oxides, metal nitrides, metal carbides, optionally doped semi-metals, semi-metal oxides, semi-metal nitrides, semi-metal carbides, alloys containing at least one metallic element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more thereof.

[0048] Preferably, the metal is copper, nickel, beryllium, iron, cobalt, titanium, zirconium, tungsten, silver, gold, platinum, chromium, manganese, magnesium, molybdenum, rhodium, palladium or zinc.

[0049] Non-limiting examples of doped metals include nickel-phosphorus (NiP) and boron-doped platinum.

[0050] Preferably, the metalloid is boron or silicon.

[0051] Non-limiting examples of alloys containing at least one metal element include brass, aluminum brass, and steel. Non-limiting examples of steel include carbon steel and stainless steel. Non-limiting examples of carbon steel include 15P (also referred to as S15P), CK75, and 20AP.

[0052] Preferably, in the present invention, the substrate is the substrate of a watch or jewellery component.

[0053] Preferably, the X groups are the same or different and are C1 to C 20 Ester group, preferably C2-C 10 It is preferably selected from the group comprising ester groups, more preferentially C2-C6 ester groups, even more preferentially C2-C5 ester groups, preferably alkyl ester groups, preferably linear alkyl ester groups, amide groups and styrene derivative groups.

[0054] Preferably, the Y groups are the same or different and are C1 to C 20 Ester group, preferably C2-C 10 It is preferably selected from the group comprising ester groups, more preferentially C2-C6 ester groups, even more preferentially C2-C5 ester groups, preferably alkyl ester groups, preferably linear alkyl ester groups, amide groups and styrene derivative groups.

[0055] The functional group B of interest is a hydrophilic group. Preferably, it is responsible for the water solubility of the copolymer. Preferably, the functional group B of interest contains 1 to 30, preferably 2 to 20, ether groups. In other words, the functional group B of interest is a polyether.

[0056] Suitably, the ether group contains 1 to 6, preferably 2 to 3 CH groups. For example, when α is 2, the ether group is of the ethyl ether type (CH2CH2O). For example, when α is 4, the ether group is of the butyl ether type (CH2CH2CH2CH2O).

[0057] The functional group L of interest is involved in the epitaxial effect. It contains at least one halogen atom. Preferably, the halogen atoms are the same or different and are fluorine, iodine, bromine, or chlorine atoms. Preferably, the halogen atom is a fluorine atom. When the L group contains several halogen atoms, these atoms can be the same or different. Preferably, all halogen atoms in the L group are fluorine atoms.

[0058] When the functional group of interest, L, is a halogenated C1-C6 carbon group, the group is preferably partially or fully halogenated. Suitably, when L is a halogenated C1-C6 carbon group, L is an at least partially fluorinated, preferably fully fluorinated, C1-C6 carbon group. When L is a halogenated C1-C6 carbon group, L may also contain a hydrogen atom on the terminal group.

[0059] When the functional group of interest, L, is a halogenated ether group, L also contains a P group. The P groups may be the same or different and are preferably C1 to C6 10 Alkyl groups, C2-C 10 Alkyl group or C2-C 10 It is an alkynyl group. The P group preferably contains at least one halogen atom. Preferably, the halogen atoms are the same or different and are fluorine, iodine, bromine, or chlorine atoms. Preferably, the halogen atom is a fluorine atom. The P group may be linear or branched.

[0060] Preferably, the P group is a C1-C 10 A perfluoroalkyl group, preferably a C1 to C6 perfluoroalkyl group, for example a C1 to C4 perfluoroalkyl group, such as CF3, C2F5, C3F7 or C4F9.

[0061] Preferably and alternatively, the P group is a C2-C 10 Perfluoroalkenyl groups, preferably C2 to C6 perfluoroalkenyl groups, for example C2 to C4 perfluoroalkenyl groups, such as C2F3, C3F5 and C4F7.

[0062] Preferably and alternatively, the P group is a C2-C 10 Perfluoroalkynyl groups, preferably C2 to C6 perfluoroalkynyl groups, for example C2 to C4 perfluoroalkynyl groups, such as C2F, C3F3 and C4F5.

[0063] Suitably, in the functional group of interest L, p is selected from 1 to 4, preferably 2 to 3.

[0064] Suitably, in the functional group of interest L, n is selected from 1 to 20, such as 1 to 16, preferably 1 to 10, such as 2 to 8.

[0065] One preferred functional group L of interest in the present invention is CF 13 It is shown by the structure.

[0066] Another preferred functional group L of interest in the present invention is (CF(CF3)OCF2) n It is represented by the structure CFCF, i.e., Q is a fluorine atom (F), P is CF, and p is 2. More specifically, the preferred structure for the L group is (CF(CF)OCF)CFCF, i.e., Q is a fluorine atom (F), P is CF, p is 2, and n is 5.

[0067] One of the copolymers preferably used in the present invention has the following structure (II): [ka] It has.

[0068] In other words, in this copolymer (II), X is C(O)O(CH2)2; Y is C(O)O; L is (CF2)5CF3; and α is 2, which means that B is ((CH2)2O) β Preferably, in the copolymer represented by structure (II), R1, R2 and R3 are the same or different and are H or CH3.

[0069] One particular example of this copolymer represented by structure (II) is, but is not limited to, a copolymer in which R1 is CH3, R2 is CH3, R3 is CH3, and the m to p ratio is 1:1 to 11:9 when the average value of β in the copolymer is 8 to 10, or 3:7 when the average value of β in the copolymer is 18 to 20.

[0070] Optionally, the copolymer may further comprise at least one K unit, where K is as defined above. Preferably, when the copolymer comprises at least one K unit, the K unit and the M and N units are linked by covalent bonds through the main chain.

[0071] Preferably, the W groups are the same or different and are C1 to C 20 Ester group, preferably C2-C 10 It is preferably selected from the group comprising ester groups, more preferentially C2-C6 ester groups, even more preferentially C2-C5 ester groups, preferably alkyl ester groups, preferably linear alkyl ester groups, amide groups and styrene derivative groups.

[0072] The functional group of interest, A, is capable of reacting with the surface of the substrate to be coated with epiram to form an anchoring group for the epiram agent on the surface of the substrate. Preferably, group A may also be provided at the terminus of the copolymer.

[0073] Optionally, the copolymer may further comprise at least one U unit, where U is [ka] wherein: R6 may be the same or different and may be H, C1 to C 10 Alkyl groups, C2-C 10 an alkenyl group, preferably H or CH; R7 may be the same or different and may be H, CH3, or a hydrocarbon chain containing at least two carbon atoms and which may contain at least one linear or branched, saturated or unsaturated heteroatom.

[0074] Preferably, when the copolymer comprises at least one U unit, the U unit and the M and N units are linked by covalent bonds through the main chain.

[0075] Preferably, the functional group of interest R7 allows for modifying the properties of the epiramidal agent and / or adding other functionality, for example, R7 may be an alkyl chain used to modify the resulting contact angle, or may be a chain capable of forming a crosslinking point in a further crosslinking step.

[0076] Optionally, the copolymer may further comprise at least one V unit, where V is as defined above. Suitably, when the copolymer comprises at least one V unit, the V unit and the M and N units are linked by covalent bonds through the main chain.

[0077] Preferably, the Z groups are the same or different and are C1 to C 20 Ester group, preferably C2-C 10 It is preferably selected from the group comprising ester groups, more preferentially C2-C6 ester groups, even more preferentially C2-C5 ester groups, preferably alkyl ester groups, preferably linear alkyl ester groups, amide groups and styrene derivative groups.

[0078] Suitably, the T group allows the concentration of the copolymer to be measured, for example by spectroscopic measurements.

[0079] Suitably, T are the same or different and are UV absorber groups derived from compounds selected from the group comprising benzotriazoles, triazines, phenones (especially benzophenones, acetophenones, hydroxylalkylphenones, hydroxyarylphenones, aminoalkylphenones and anthraquinones) and acylphosphine oxides.

[0080] Suitably, T are the same or different and are fluorophore groups derived from a compound selected from the group comprising fluorescein, naphthyl, anthracene, coumarin, rhodamine and fluorobenzoate.

[0081] Suitably, the copolymer contains from 5 to 500 units, preferably from 10 to 350 units.

[0082] The copolymer may be a statistical copolymer or a block copolymer.

[0083] Preferably, when the copolymer is a statistical copolymer, the M, N, optional K, optional V and optional U units are randomly distributed, in other words, the units are statistically linked to each other through the main chain.

[0084] Suitably, when the copolymer is a block copolymer, it comprises at least one block of M units covalently linked through its backbone and at least one block of N units covalently linked through its backbone, and preferably the block copolymer comprises a single block of M units and / or a single block of N units.

[0085] Optionally, the block copolymer further comprises at least one block of K units linked by a covalent bond through its backbone. Preferably and optionally, the block copolymer comprises a single block of K units.

[0086] Optionally, the block copolymer further comprises at least one block of V units linked by a covalent bond through its backbone. Preferably and optionally, the block copolymer comprises a single block of V units.

[0087] Optionally, at least one of the blocks of M units, N units, optional blocks of K units, and optional blocks of V units contains at least one U unit covalently bonded through its main chain. Preferably, the blocks are linearly arranged and covalently bonded through its main chain. When the block copolymer further contains at least one U unit, at least one of the M unit block, N unit block, optional K unit block, and optional V unit block contains at least one U unit, and the number of U units in the M unit block may be different from the number of U units in the N unit block, the number of U units in the K unit, and the number of U units in the V unit, when the latter (K ​​and V) are included in the block copolymer.

[0088] Preferably, U units are incorporated and distributed within blocks of N units, for example by statistical copolymerization of N and U units, to form a single block that is predominantly made up of N units and assimilates with the block of N units.

[0089] The present invention also relates to a method for epiram coating at least a portion of a surface of a substrate, the method comprising preparing an epiram agent, optionally preparing the surface of the substrate, and contacting the surface of the substrate with the epiram agent.

[0090] Preferably, the preparation of the epiram agent comprises copolymerizing a monomer capable of forming an M unit with a monomer capable of forming an N unit, optionally with a monomer capable of forming at least one K unit, optionally with a monomer capable of forming at least one V unit, and optionally with a monomer capable of forming at least one U unit.

[0091] Preferably, the monomers are selected from the group comprising acrylate, methacrylate, acrylamide, methacrylamide, vinyl, diene, styrene and olefin monomers.

[0092] Particularly preferred monomers for forming V units containing the tracer group T are selected from the group consisting of 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 acrylate (methacrylate), fluorescein O-acrylate (methacrylate), 9-anthracenylmethyl acrylate (methacrylate), 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 used to form the V units 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 tracer groups that can be monitored by UV-visible spectroscopy, which is much easier to set up in an industrial environment than fluorescence spectroscopy.

[0094] Polymerization techniques include those known to those skilled in the art. Optionally, the copolymerization is carried out in the presence of an initiator system, including an initiator such as, but not limited to, azobisisobutyronitrile (AIBN). Optionally, the copolymerization is carried out at elevated temperatures.

[0095] The copolymers used in the present invention may be prepared in powder or viscous liquid form.

[0096] A particularly suitable polymerization method for producing statistical copolymers is radical copolymerization in solution or emulsion, suitably free radical copolymerization or controlled radical copolymerization, preferably controlled radical copolymerization.

[0097] Particularly suitable polymerization methods for preparing block copolymers are: - of monomers capable of forming at least one block of M units with optionally monomers capable of forming at least one U unit - of a monomer capable of forming at least one block of N units with a monomer capable of forming optionally at least one U unit, where U is the same or different; - of a monomer capable of forming at least one block of optional K units with a monomer capable of forming at least one optional U unit, where U is the same or different; - of monomers capable of forming at least one block of optional V units with monomers capable of forming at least one optional U unit, where U is the same or different; It is a continuous controlled radical copolymerization.

[0098] According to a first copolymerization mode, the copolymer may be prepared in a single step by copolymerization, preferably radical copolymerization, of a monomer having a YB side chain with a monomer having an XL side chain, optionally a monomer having a WA side chain, optionally a monomer having a ZT side chain, and optionally a monomer having an R7 side chain.

[0099] According to another copolymerization mode, copolymers may be obtained by copolymerization, preferably radical copolymerization, of a monomer having a suitable Y side chain with a monomer having a suitable X side chain, optionally with a suitable W side chain, optionally with a suitable Z side chain, and optionally with a side chain for carrying R7, and then the side chains are modified, for example by "click chemistry", to introduce the functional groups of interest B, L, A (optional), T (optional), and R7 (optional).

[0100] Optional preparation of the substrate surface may include cleaning and / or washing of the surface to be coated with epiram. Such cleaning or washing may be carried out using methods known to those skilled in the art. For example, and particularly where the substrate is a watch component, cleaning may include cleaning according to standard watch methods.

[0101] Alternatively, preparation of the substrate surface may include a CO2 treatment at a temperature in the range of 10° C. to 80° C., a pressure in the range of 25 bar to 250 bar, for a period in the range of, for example, 1 minute to 60 minutes. Suitably, this treatment removes particulate dust and degreases the surface.

[0102] Preferably, the copolymer(s) are dissolved in an aqueous solution. Preferably, the aqueous solution contains 0% to 15% by volume, preferably 0% to 10% by volume, of a non-halogenated organic solvent, based on the total volume of the aqueous solution before the addition of the polymer(s). Therefore, when an aqueous solution does not contain a non-halogenated organic solvent (0% by volume), it is understood that the aqueous solution is water. Preferably, the copolymer(s) are dissolved in water. It is known that the addition of a non-halogenated organic solvent can aid in the dissolution of the polymer in water.

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

[0104] Preferably, the aqueous solution does not contain any halogenated solvents. Preferably, the epiramid solution does not contain any halogenated solvents.

[0105] Suitably, the copolymer(s) are dissolved in an aqueous solution, such as water, preferably at a concentration in the range of 50 mg / L to 1 g / L, to obtain an epiramid solution.

[0106] According to a first embodiment of the epiram coating method, the epiram agent solution is then used in an epiram coating bath. The same epiram coating bath may be used several times. Preferably, when the same epiram coating bath is used several times, there is a means for testing and, optionally, maintaining the concentration of the epiram agent over time, preferably before contacting the substrate surface with the epiram agent in the epiram coating bath.

[0107] Such concentration testing means may include the presence of at least one V unit as described above in the copolymer, in other words, the presence of at least one V unit containing a T group as described above allows for testing the epilam agent concentration in the epilating bath.

[0108] Preferably, when the T group is a UV absorber group or a fluorophore, the concentration of the epilam agent is measured by spectrophotometric measurements (e.g., absorbance measurements). An intermediate step before testing the concentration of the epilam agent in the epilam coating bath involves creating a calibration curve for the copolymer. To do this, the copolymer is dissolved in a solvent at various concentrations, and the absorbance of each solution is measured by spectrophotometric measurements at different wavelengths. The wavelength at which the absorbance is maximum is identified, and a calibration curve A = F (concentration) is plotted against the wavelength at which the absorbance is maximum. The molar extinction coefficient of the polymer can then be estimated (Beer-Lambert law A = εcl).

[0109] To test the concentration of epiram in the epiram coating bath, the absorbance of the bath solution is measured spectrophotometrically; a pre-established calibration curve can then be used to estimate the concentration of epiram in the bath. Depending on the results, additional amounts of epiram can then be added to the bath to accurately readjust the concentration.

[0110] The epiram coating method according to the present invention may also include a step of drying the epiram-coated surface after the substrate surface has been contacted with the epiram agent.

[0111] According to a second embodiment of the epilam coating method, an epilam agent solution as described above is used (including being placed) in the enclosure. Alternatively, the epilam agent may be placed in the enclosure in pure form.

[0112] Preferably, the substrate and epiramid are placed in an enclosure at ambient pressure, ie, a pressure in the range of 0.6 bar to 1.1 bar, and the enclosure is then sealed.

[0113] CO2 is then introduced into the sealed enclosure. Suitably, CO2 is introduced for a period ranging from 1 minute to 30 minutes, preferably from 1 minute to 20 minutes, and more preferentially from 3 minutes to 15 minutes.

[0114] Suitably, the CO2 is at a pressure in the range of 25 bar to 74 bar, preferably 45 bar to 70 bar, more preferentially 50 bar to 60 bar.

[0115] Suitably, the CO2 is at a temperature in the range of 10°C to 80°C, preferably 10°C to 60°C, and more preferentially 15°C to 50°C.

[0116] The introduction of CO2 is then stopped and the pressure in the enclosure is reduced, preferably to ambient pressure, i.e., a pressure in the range of 0.6 bar to 1.1 bar.

[0117] The epilam coated substrate is then removed.

[0118] Optionally, after reducing the pressure within the enclosure and removing the Epiram substrate from the enclosure, the Epiram substrate may be heat-treated. For example, the Epiram-coated substrate may be heated within the enclosure to a temperature ranging from 250°C to 90°C, preferably from 30°C to 80°C, for a period ranging from 1 minute to 45 minutes, preferably from 2 minutes to 30 minutes. This heat treatment improves anchoring of the Epiram agent to the treated substrate surface.

[0119] The epiram coating method according to the present invention may further comprise a further cross-linking step after contacting the substrate surface with the epiram agent, preferably enabled by the presence of a suitable functional group of interest provided on the R5 side chain of the U unit. [Example]

[0120] Example 1 Epiram was prepared by statistical copolymerization. 1H,1H,2H,2H-perfluorooctyl methacrylate monomer (CAS 2144-53-8, where R is CH, X is C(O)C(CH), and L is CF 13 (wherein R is CH, R is CH, α is 2, and Y is C(O)O) and 2-(methylthio)ethyl methacrylate monomer (CAS 14216-23-0; where R is CH, W is C(O)O, and A is (CH)SCH) were copolymerized with poly(ethylene glycol) methyl ether methacrylate monomer (CAS 26915-72-0; R is CH, R is CH, α is 2, and Y is C(O)O) and 2-(methylthio)ethyl methacrylate monomer (CAS 14216-23-0; R is CH, W is C(O)O, and A is (CH)SCH) by statistical copolymerization in the presence of an initiator system.

[0121] Figure 1 shows the resulting epiram copolymer, where R1 is CH3, R2 is CH3, R3 is CH3, R4 is CH3, and A is (CH2)2SCH3. The value of q is preferably 1 to 20 (if this group is present in the copolymer).

[0122] For an average value in the copolymer of β between 8 and 10, e.g., 9, the m / p / q ratio was 45:45:10. For an average value in the copolymer of β between 18 and 20, e.g., 19, the m / p / q ratio was 30:60:10.

[0123] Example 2 Three different epiram agents were deposited onto the surface of a steel substrate that had previously undergone a surface preparation treatment using an epiram coating bath.

[0124] The first epiram agent was the copolymer synthesized in Example 1. The epiram coating bath used was an aqueous epiram coating bath.

[0125] The second epiram agent has a C6 perfluoroakyl group as the epiram group, i.e., C6F 13 The epiram coating bath used was an epiram coating bath containing a fluorinated solvent.

[0126] The third epiram formulation is a competing epiram formulation containing methyl nonafluoroisobutyl ether (CAS 163702-08-7), methyl nonafluorobutyl ether (CAS 163702-07-6), and a fluoroaliphatic polymer. The epiram coating bath used was an epiram coating bath containing a fluorinated solvent.

[0127] A variety of tests were performed to evaluate the properties of the epiram drug.

[0128] As a first test, surface tension was measured. The method, known to those skilled in the art, consists of measuring the contact angles of drops of three liquids (using a Dataphysics OCA 15 contact angle measuring device): water, diiodomethane, and ethylene glycol, each with very different surface tensions. From the angles obtained, the surface tension is calculated using the Owens, Wendt, Rabel, and Kaelble (OWRK) method.

[0129] The results are shown in Table 1. The surface of the epilamin-free steel substrate that underwent the surface preparation procedure had a surface tension of 34.95 mN / m. All epilaminants showed a decrease in surface tension, with the epilaminant of the present invention exhibiting a decrease in surface tension of CF 13 The surface tension is comparable to that of Epiram (within the margin of measurement error) and is lower than that measured for competitive Epiram. The lower the surface tension, the better the oleophobicity.

[0130] This result shows that the epiram drug of the present invention is 13 It demonstrates how it is a superior alternative to epiram drugs while eliminating the need for fluorinated solvents. [Table 1]

[0131] Example 3 The three epilam formulations of Example 2 were then used (applied) to several substrates of different compositions.

[0132] To evaluate the performance of the epilam formulation, contact angles were measured with Test Oil #3 and Moebius® 9010 oil. Droplets of both oils were applied and the contact angles were measured using an optical device (Dataphysics OCA 15). To evaluate resistance to watch wash, the substrates were washed three times using watch wash (an amine hydrocarbon solution) and then the contact angles were measured.

[0133] The target values ​​for each measurement are as follows: - Test oil #3 - Initial (before cleaning): ≥ 60° -Test Oil #3 - After 3 washes: ≥ 35° -Oil 9010 - Initial (before cleaning): ≥ 70° -Oil 9010 - After 3 washes: ≥ 45°

[0134] Figure 2 shows the results for the copolymers of the present invention on various substrates. 13Figure 1 shows the results for epiram agents, and Figure 2 shows the results for competing epiram agents. From Figure 4, it is clear that the target values ​​for each oil before washing and after three washes were not achieved for any of the substrates. On the other hand, the copolymers and C6F 13 The target values ​​for oil #3 were achieved for the majority of substrates with these two epilam formulations (Figures 2 and 3).

Claims

1. A substrate comprising a surface at least partially coated with an epiramid agent, characterized in that the epiramid agent comprises at least one compound in the form of a copolymer comprising M and N units covalently linked through a main chain, wherein M is 【Chemistry 1】 and N is 【Chemistry 2】 where: R 1 and R 2 are the same or different, H, C 1 ~C 10 Alkyl group, C 2 ~C 10 Alkenyl groups, preferably H or CH 3 and X and Y are the same or different and are spacer arms consisting of heteroatoms or linear or branched hydrocarbon chains containing at least one heteroatom and at least one carbon atom; B may be the same or different and is -((CH 2 ) α O) β -R 3 and in the formula R 3 is H, C 1 ~C 10 Alkyl group, C 2 ~C 10 Alkenyl groups, preferably H or CH 3 and α is selected from 1 to 6, preferably 2 to 3; β is selected from 1 to 30, preferably from 2 to 20; L may be the same or different and may be a halogenated C 1 ~C 6 Carbon group or formula (I) 【Transformation 3】 is a halogenated ether group according to the formula: Q is a halogen atom, P is the same or different, contains at least one halogen atom, and is linear or branched; C 1 ~C 10 Alkyl group or C 2 ~C 10 is an alkenyl group, p is selected from 1 to 4, preferably 2 to 3; n is selected from 1 to 20, preferably from 1 to 10; the copolymer is water soluble and has a ratio of M units to N units in the range of 1:10 to 10:1; Base material.

2. 2. The substrate of claim 1, wherein the copolymer is a statistical copolymer, and the M units and the N units are randomly distributed.

3. 10. The substrate of claim 1, wherein the copolymer is a block copolymer comprising at least one block of M units covalently bonded through the backbone and at least one block of N units covalently bonded through the backbone, the blocks being linked together by covalent bonds through the backbone in a linear arrangement.

4. L is at least partially fluorinated, preferably fully fluorinated, C 1 ~C 6 a carbon group or an at least partially fluorinated, preferably fully fluorinated, ether group, C 1 ~C 6 10. A substrate according to any of the preceding claims, characterized in that it is carbon-based.

5. 10. The substrate of claim 1, wherein the ratio of M units to N units is in the range of 1:1 to 2:1 when the β value is in the range of 8 to 10, and the ratio of M units to N units is in the range of 1:5 to 3:5 when the β value is in the range of 18 to 20.

6. X and Y may be the same or different, and C 1 ~C 20 10. The substrate according to any of the preceding claims, characterized in that X and Y are selected from the group comprising ester groups, amide groups and styrene derivative groups, and are identical or different and optionally comprise at least one heteroatom.

7. The copolymer further comprises a K unit attached to the M and N units by a covalent bond through the backbone, wherein K is 【Chemistry 4】 where: R 4 are the same or different, H, C 1 ~C 10 Alkyl group, C 2 ~C 10 Alkenyl groups, preferably H or CH 3 and W is the same or different and is a spacer arm consisting of a heteroatom or a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom; A are the same or different and form anchoring groups on the substrate; A substrate according to any preceding claim.

8. The copolymer further comprises a V unit attached to the M and N units by a covalent bond through the main chain, wherein V is 【Transformation 5】 and in the formula R 5 are the same or different, H, C 1 ~C 10 Alkyl group, C 2 ~C 10 Alkenyl groups, preferably H or CH 3 and Z is the same or different and is a spacer arm consisting of a heteroatom or a linear or branched hydrocarbon chain containing at least one heteroatom and at least one carbon atom; T is the same or different, and is a tracer group designed to measure the concentration of the epiram agent in the epiram coating bath; A substrate according to any preceding claim.

9. 9. The substrate of claim 8, wherein T are identical or different and are UV absorber groups or fluorophores.

10. 10. The substrate according to any of the preceding claims, characterized in that the surface at least partially coated with the epitaxial agent is made of a material selected from the group comprising optionally doped metals, metal oxides, metal nitrides, metal carbides, optionally doped semi-metals, semi-metal oxides, semi-metal nitrides, semi-metal carbides, alloys containing at least one metallic element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more thereof.

11. 1. A method for epilam coating at least a portion of a surface of a substrate, comprising: - preparing an epiramidal formulation comprising at least one water-soluble copolymer according to the preceding claims; - optionally preparing the surface of said substrate; - contacting the surface of the substrate with the epiramid; A method comprising:

12. The epilam coating method according to claim 11, characterized in that the epilam agent is produced by copolymerizing a monomer capable of forming an M unit with a monomer capable of forming an N unit, and preferably the monomer is selected from the group comprising acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl monomers and styrene monomers.

13. 13. An epiram coating method according to any one of claims 11 to 12, wherein the epiram agent comprises at least one copolymer according to claims 8 to 9, and wherein the method is carried out by preparing an aqueous epiram coating bath containing the epiram agent dissolved in water, and contacting the surface of the substrate with the epiram agent in the aqueous epiram coating bath, and optionally the method comprises, prior to contacting, a step for testing the concentration of the epiram agent in the aqueous epiram coating bath using the tracer group, and a step for readjusting the concentration of the epiram agent in the aqueous epiram coating bath.

14. 13. The epiram coating method according to any one of claims 11 to 12, wherein the step of contacting the surface of the substrate with the epiram agent comprises: - placing said substrate and said epiramid in an enclosure at ambient pressure; - sealing the enclosure; CO at a pressure ranging from -25 bar to 74 bar, preferably from 45 bar to 70 bar, and at a temperature ranging from 10°C to 80°C, preferably from 15°C to 50°C. 2 into the sealed enclosure; - reducing the pressure in the enclosure; - removing the epilam coated substrate from the enclosure; A method comprising:

15. 1. Use of a water-soluble copolymer comprising M and N units covalently linked through the main chain as an epitaxial agent for at least a portion of the surface of a substrate, comprising: M is 【Transformation 6】 and N is 【Transformation 7】 where: R 1 and R 2 are the same or different, H, C 1 ~C 10 Alkyl group, C 2 ~C 10 Alkenyl groups, preferably H or CH 3 and X and Y are the same or different and are spacer arms consisting of heteroatoms or linear or branched hydrocarbon chains containing at least one heteroatom and at least one carbon atom; B is the same or different and is a polyether group; L may be the same or different and may be a halogenated C 1 ~C 6 Carbon group or formula (I) 【Transformation 8】 is a halogenated ether group according to the formula: Q is a halogen atom, P is the same or different, contains at least one halogen atom, and is linear or branched; C 1 ~C 10 Alkyl group or C 2 ~C 10 is an alkenyl group, p is selected from 1 to 4, preferably 2 to 3; n is selected from 1 to 20, preferably from 1 to 10; use.

16. A watch or piece of jewellery comprising a component comprising the substrate according to any one of claims 1 to 10.

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