EP4394022B1 - Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats - Google Patents

Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats

Info

Publication number
EP4394022B1
EP4394022B1 EP23206208.3A EP23206208A EP4394022B1 EP 4394022 B1 EP4394022 B1 EP 4394022B1 EP 23206208 A EP23206208 A EP 23206208A EP 4394022 B1 EP4394022 B1 EP 4394022B1
Authority
EP
European Patent Office
Prior art keywords
units
epilame
group
different
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP23206208.3A
Other languages
English (en)
French (fr)
Other versions
EP4394022A1 (de
Inventor
Mathieu AYER
Christophe Letondor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swatch Group Research and Development SA
Original Assignee
Swatch Group Research and Development SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to CN202380088411.8A priority Critical patent/CN120457191A/zh
Priority to JP2025537911A priority patent/JP2026501559A/ja
Priority to PCT/EP2023/087861 priority patent/WO2024141565A1/fr
Publication of EP4394022A1 publication Critical patent/EP4394022A1/de
Application granted granted Critical
Publication of EP4394022B1 publication Critical patent/EP4394022B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen

Definitions

  • 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.
  • 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.
  • depilatory agents such as Moebius ' Fixodrop® ES/BS or the 3M TM Novec TM range have insufficient resistance to watchmaking washes.
  • the patent application CH 713 789 relates to an epilaming agent comprising at least hydrophobic and oleophobic groups arranged to impart epilaming properties to said compound, and at least one hydrophilic group arranged to render said compound soluble in aqueous medium, said hydrophilic group being linked to the compound by at least one cleavable group.
  • EP 3 070 133 describes an epilame agent comprising a statistical copolymer including a fluorinated motif, an anchoring motif and optionally an additional hydrocarbon chain.
  • the patent EP 3 070 152 describes an epilame agent comprising a block copolymer including a fluorinated motif, an anchoring motif and optionally an additional hydrocarbon chain.
  • the fluorinated motifs of the type -C 5 F 11 and -C 6 F 13 are described.
  • perfluorohexanoic acid (PFHxA, CAS 307-24-4 ), its salts, and related substances are subject to general regulatory pressure for environmental reasons.
  • these epilamins 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.
  • the invention aims in particular to overcome the various drawbacks of known epilating agents and epilating processes.
  • one objective of the invention is to provide an epilame agent that is considered not to be under general regulatory pressure for environmental reasons.
  • the invention also aims to provide an epilame agent that can be applied by environmentally friendly processes, particularly processes using a significant reduction or even the absence of polluting solvents, such as fluorinated solvents.
  • the invention also aims to provide an epilame agent offering increased wash resistance compared to known epilame agents.
  • the invention further aims to provide a universal epilame agent that can be used on any type of material.
  • the invention also aims to provide an environmentally friendly hair removal process that eliminates the use of solvents, 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.
  • 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.
  • 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.
  • the epilame agent comprises at least one compound in the form of a copolymer comprising M units and N units. These M units and these N units are associated by covalent bonds by their main chains.
  • X is chosen from the group comprising C1 - C20 ester groups, amide groups, and styrene-derived groups.
  • X identical or different, comprises at least one heteroatom.
  • L is a C1 - C6 carbon group that is at least partially fluorinated, for example, fully fluorinated.
  • L is an ether group that is at least partially fluorinated, for example, fully fluorinated.
  • the term "fully fluorinated” as used in this disclosure denotes a group in which every hydrogen atom is replaced by a fluorine atom.
  • the copolymer may comprise different L groups, for example a mixture of C1 - C6 carbon groups at least partially halogenated and halogenated ether groups according to formula (I).
  • the copolymer is a statistical copolymer.
  • the M units and the N units are randomly distributed.
  • the copolymer is a statistical copolymer and the M units and the N units are randomly distributed.
  • the copolymer is a block copolymer.
  • 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.
  • the blocks are connected to each other by covalent bonds via their main chains in linear sequences.
  • the ratio of M units to N units depends on the value of ⁇ .
  • ⁇ is equal to a value between 1 and 10, preferably between 5 and 10, more preferably between 8 and 10, for example 9, the ratio of M units to N units is between 1:1 and 2:1, more particularly between 1:1 and 3:2, for example between 1:1 and 11:9, or between 1:1 and 10:9.
  • ⁇ is equal to a value between 11 and 30, preferably between 12 and 20, more preferably between 18 and 20, for example 19, the ratio of M units/N units is between 1:5 and 3:5, more particularly between 2:5 and 1:2.
  • the epilame agent of the present invention is at least partially, and preferably entirely, soluble in water. More particularly, the copolymer is at least partially, and preferably entirely, soluble in water. Without being limited to this, the inventors believe that this excellent water solubility is a result of the specific composition of the copolymer. More specifically, the inventors believe that the ratio of M units to N units allows the copolymer, and advantageously the epilame agent, to dissolve in water. Consequently, the copolymer and the epilame agent according to the present invention make it possible to use aqueous epilame processes, thus eliminating the need to use polluting organic solvents.
  • W is chosen from the group comprising C1 - C20 ester groups, amide groups, and styrene-derived groups.
  • W, identical or different comprises at least one heteroatom.
  • 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.
  • the copolymer according to this disclosure comprises K units, and when ⁇ is equal to a value between 8 and 10, the copolymer comprises between 5% and 20%, preferably between 7% and 15%, of K units, between 30% and 65%, preferably between 35% and 60%, of M units, and between 25% and 60%, preferably between 30% and 55%, of N units, the percentages being expressed with respect to the total number of units in the copolymer.
  • the copolymer according to this disclosure comprises K units, and when ⁇ is equal to a value between 18 and 20, the copolymer comprises between 5% and 20%, preferably between 7% and 15%, of K units, between 15% and 45%, preferably between 25% and 35%, of M units, and between 50% and 75%, preferably between 55% and 65%, of N units, the percentages being expressed with respect to the total number of units in the copolymer.
  • T is a UV absorber group or a fluorophore.
  • the copolymer according to this disclosure comprises V 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 with respect to the total number of units in the copolymer.
  • the surface of the substrate, at least part of which is coated with the epilame agent is made of a material selected from the group comprising metals, optionally doped, metal oxides, metal nitrides, metal carbides, metalloids, optionally doped, metalloidic oxides, metalloidic nitrides, metalloidic carbides, alloys comprising at least one metallic element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more of these.
  • a material selected from the group comprising metals, optionally doped, metal oxides, metal nitrides, metal carbides, metalloids, optionally doped, metalloidic oxides, metalloidic nitrides, metalloidic carbides, alloys comprising at least one metallic element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more of these.
  • 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.
  • the depilation process comprises preparing a depilation agent comprising at least one water-soluble copolymer as defined above.
  • the depilation process further comprises preparing the substrate surface.
  • the depilation process further comprises contacting the substrate surface with the depilation agent.
  • the epilame agent is prepared by copolymerizing monomers capable of forming M units with monomers capable of forming N units.
  • the M and N units are as described above.
  • the monomers are selected from the group comprising acrylate, methacrylate, acrylamide, methacrylamide, vinyl, and styrenic monomers.
  • the depilation agent is prepared by preparing a depilation bath containing the depilation agent.
  • the depilation bath is an aqueous depilation bath containing the depilation agent dissolved in water. Then, at least a portion of the substrate surface is brought into contact with the depilation agent in the aqueous depilation bath, for example, by immersing the substrate in the aqueous depilation bath.
  • 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 M and N units by covalent bonds via their main chains.
  • the V units are as described above.
  • the presence of the V units, and in particular the tracer group advantageously and optionally allows for monitoring the concentration of epilame agent in the bath before contact. of aqueous depilation.
  • this control is carried out using the tracer group.
  • the concentration of depilation agent in the aqueous depilation bath can be readjusted.
  • 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.
  • a third aspect of the present invention relates to the use of a copolymer comprising M units and N units, covalently linked by their chains, as an epilame agent for at least a portion of a substrate surface.
  • the M units and N units are as described above.
  • the copolymer is water-soluble.
  • 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.
  • epilame agents according to the present invention are not subject to regulatory pressure for environmental reasons, despite offering a high-performance epilame effect.
  • copolymer in the epilame agent is water-soluble, making fluorinated solvents redundant and providing a more environmentally friendly and often more economical alternative.
  • the epilame agents according to the present invention have excellent wash resistance, particularly to watchmaking wash.
  • a substrate comprises a surface, at least a portion of which is coated with an epilame agent.
  • 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, metal nitrides, metal carbides, metalloids, optionally doped, metalloidic oxides, metalloidic nitrides, metalloidic carbides, alloys comprising at least one metallic element, polymers, sapphire, ruby, diamond-like carbon (DLC), and combinations of two or more of these.
  • the metal is copper, nickel, beryllium, iron, cobalt, titanium, zirconium, tungsten, silver, gold, platinum, the chromium, manganese, magnesium, molybdenum, rhodium, palladium, or zinc.
  • Non-limited examples of doped metals include nickel-phosphorus (NiP) and boron-doped platinum.
  • the metalloid is boron or silicon.
  • alloys containing at least one metallic element include brass, aluminum brass, and steel.
  • steel include carbon steel and stainless steel.
  • carbon steel include 15P (also noted as S15P), CK75, and 20AP.
  • the substrate is a substrate of an element of a watch or jewelry part.
  • the group X 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.
  • the Y group 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.
  • the functional groups of interest B are hydrophilic groups.
  • they are responsible for the solubility of the copolymer in water.
  • 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.
  • the ether group comprises between 1 and 6, preferably between 2 and 3, CH2 groups.
  • the The ether group is of the ethyl ether type ( CH2CH2O ).
  • the ether group is of the butyl ether type (CH2CH2CH2CH2O ) .
  • the functional groups of interest L are responsible for the epilame effect. They comprise at least one halogen atom.
  • the halogen atom is a fluorine, iodine, bromine, or chlorine atom.
  • the halogen atom is a fluorine atom. If the L group comprises multiple halogen atoms, the atoms may be identical or different.
  • all the halogen atoms in the L group are fluorine atoms.
  • L is a halogenated C1 - C6 carbon group
  • the group is preferably partially or totally halogenated.
  • L is a C1 - C6 carbon group that is at least partially fluorinated, and preferably totally fluorinated.
  • L may also include a hydrogen atom on the terminal group.
  • L When the functional group of interest L is a halogenated ether group, L also includes a group P.
  • the group P which may be the same or different, is advantageously a C1 - C10 alkyl group, a C2 - C10 alkenyl group, or a C2 - C10 alkynyl group.
  • the group P advantageously includes at least one halogen atom.
  • the halogen atom which may be the same or different, is a fluorine, iodine, bromine, or chlorine atom.
  • the halogen atom is a fluorine atom.
  • the group P may be linear or branched.
  • the P group is a C1 - C10 perfluoroalkyl group, preferably a C1 - C6 perfluoroalkyl group, for example a C1 - C4 perfluoroalkyl group, such as CF3 , C2F5 , C3F7 or C4F9 .
  • the P group is a C2 - C10 perfluoroalkenyl group, preferably a C2 - C6 perfluoroalkenyl group, for example a C2 - C4 perfluoroalkenyl group, such as C2F3 , C3F5 and C4F7 .
  • the P group is a C2 - C10 perfluoroalkynyl group, preferably a C2 - C6 perfluoroalkynyl group, for example a C2 - C4 perfluoroalkynyl group, such as C2F , C3F3 , and C4F5 .
  • p is chosen between 1 and 4, preferably between 2 and 3.
  • n is chosen between 1 and 20, for example between 1 and 16, preferably between 1 and 10, for example between 2 and 8.
  • a functional group of interest L preferably in the present invention is represented by the structure C 6 F 13 .
  • Another functional group of interest L preferably in the present invention is represented by the structure (CF(CF 3 )OCF 2 ) n CF 2 CF 3 , i.e. Q is a fluorine atom (F), P is CF 3 , and p is 2. More particularly, a preferred structure of the group L is (CF(CF 3 )OCF 2 ) 5 CF 2 CF 3 , i.e. Q is a fluorine atom (F), P is CF 3 , p is 2, and n is 5.
  • One of the copolymers preferably used in the present invention represents the following structure (II)
  • X is C ( O)O( CH2 ) 2 ; Y is C(O)O; L is ( CF2 ) 5CF3 ; ⁇ is 2, which indicates that B is (( CH2 ) 2O ) ⁇ R3 .
  • R1 , R2 and R3 are H or CH3 .
  • a particular example of this copolymer shown by structure (II), without being limiting, is a copolymer in which R1 is CH3 , R2 is CH3 , R3 is CH3 , and the m/p ratio is between 1:1 and 11:9 when the average value of ⁇ in the copolymer is between 8 and 10, and 3:7 when the average value of ⁇ in the copolymer is between 18 and 20.
  • the copolymer may further comprise at least one K unit, where K is as described above.
  • the copolymer comprises at least one K unit, the K unit, the M units, and the N units are associated by covalent bonds along their main chains.
  • the W group 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.
  • 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.
  • a groups can also be provided at the end of the copolymer.
  • the copolymer comprises at least one U unit
  • the U unit and the M and N units are associated by covalent bonds through their main chains.
  • the functional groups of interest R7 allow for modification of the properties of the epilame agent and/or the provision of additional functions.
  • R7 could be an alkyl chain used to modify the contact angle obtained, or it could be a chain capable of forming crosslinking points during a complementary crosslinking step.
  • the copolymer may further comprise at least one V unit, where V is as described above.
  • V is as described above.
  • the V unit and the units M and N units are associated by covalent bonds through their main chains.
  • the Z group 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.
  • the T group allows, for example, the determination of the copolymer concentration by spectroscopy.
  • T 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.
  • T is a fluorophore group derived from a compound selected from the group comprising fluorescein, a naphthyl, anthracene, coumarin, rhodamine, and a fluorobenzoate.
  • the copolymer comprises between 5 and 500 units, preferably between 10 and 350 units.
  • the copolymer can be a statistical copolymer or a block copolymer.
  • the copolymer is a statistical copolymer
  • the M, N, K, V, and U optional units are randomly distributed.
  • the units are statistically linked to each other by their main chain.
  • the copolymer when the copolymer is a block copolymer, the copolymer comprises at least one block of M units linked by bonds covalently linked by their main chains, and at least one block of N units associated by covalent bonds through their main chains.
  • the block copolymer comprises a single block of M units and/or a single block of N units.
  • the block copolymer further comprises at least one block of K units covalently linked by their main chains.
  • the block copolymer comprises a single block of K units.
  • the block copolymer further comprises at least one block of V units covalently linked by their main chains.
  • the block copolymer comprises a single block of V units.
  • At least one of the M block, N block, optional K block, and optional V block may include at least one U unit, covalently linked by their main chains.
  • 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 M block, N block, optional K block, and optional V block includes at least one U unit, and the number of U units in the M block may vary from the number of U units in the N block, the number of U units in the K block, and the number of U units in the V block if the latter (K and V) are included in the block copolymer.
  • 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.
  • the present invention also relates to a method for removing hair from at least a portion of a substrate surface comprising the preparation of an epilame agent, optionally preparation of the substrate surface, and bringing the substrate surface into contact with the epilame agent.
  • the preparation of the epilame agent includes the copolymerization of monomers capable of forming M units with monomers capable of forming N units, optionally monomers capable of forming at least one K unit, optionally monomers capable of forming at least one V unit, and optionally monomers capable of forming at least one U unit.
  • the monomers are chosen from the group comprising acrylate, methacrylate, acrylamides, methacrylamides, vinyl, diene, styrene and olefinic monomers.
  • 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.
  • 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.
  • copolymerization is carried out in the presence of an initiation system comprising an initiator, such as, but not limited to, azobisisobutyronitrile (AIBN).
  • an initiator such as, but not limited to, azobisisobutyronitrile (AIBN).
  • copolymerization is carried out at an elevated temperature.
  • copolymers used in the present invention can be obtained in powder or viscous liquid form.
  • a particularly suitable polymerization method for obtaining a statistical copolymer is radical copolymerization, in solution or emulsion.
  • the radical copolymerization is either a free radical copolymerization or a controlled radical copolymerization, preferably a controlled radical copolymerization.
  • the copolymer can be obtained in a single step by copolymerization, preferably radical, of monomers bearing YB side chains with monomers bearing XL side chains, optionally monomers bearing WA side chains, optionally monomers bearing ZT side chains, and optionally monomers bearing R 7 side chains.
  • the copolymer can be obtained by copolymerization, preferably radical, of monomers bearing the appropriate Y side chains with monomers bearing the appropriate X side chains, optionally monomers bearing the appropriate W side chains, optionally monomers bearing the appropriate Z side chains, and optionally monomers bearing side chains intended to carry R7 , then the side chains are modified, for example by "click chemistry", to introduce the functional groups of interest B, L, A (optionally), T (optionally), and the R7 groups (optionally).
  • Optional substrate surface preparation may include cleaning and/or washing the surface to be epilaminated. Such cleaning or washing 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.
  • substrate surface preparation can include treatment with CO2 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.
  • treatment advantageously removes dust particles and degreases the surface.
  • the copolymer(s) are dissolved in an aqueous solution.
  • the aqueous solution comprises between 0% by volume and 15% by volume, preferably between 0% by volume and 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). It is understood that when the aqueous solution contains no non-halogenated organic solvent (0% by volume), the aqueous solution is simply water.
  • the copolymer(s) are dissolved in water. It is known that the addition of a non-halogenated organic solvent can help solubilize the polymer in water.
  • Non-limited 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.
  • the aqueous solution does not contain a halogenated solvent.
  • the epilame agent solution does not contain a halogenated solvent.
  • the copolymer(s) are dissolved in the aqueous solution, for example in water, at concentrations preferably between 50 mg/L and 1 g/L, in order to obtain a solution of epilame agent.
  • such a solution of epilaming agent is then used in an epilaming bath.
  • the same epilaming bath can be 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.
  • Such means of concentration control may include the presence of at least one V unit as described above in the copolymer.
  • the presence of at least one V unit comprising a T group as described above allows control of the concentration of epilame agent in the epilame bath.
  • the concentration of the epilame agent is determined spectroscopically (e.g., by measuring absorbance).
  • 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.
  • the epilame agent solution as described above is used (including being placed) in a chamber.
  • the epilame agent can be placed in the chamber in its pure form.
  • the substrate and the epilame agent are placed in an enclosure at ambient pressure, i.e. a pressure between 0.6 bar and 1.1 bar, followed by the hermetic closure of the enclosure.
  • CO2 is introduced into the hermetically sealed enclosure.
  • the CO2 is introduced for a period of between 1 and 30 minutes, preferably between 1 and 20 minutes, and more preferably between 3 and 15 minutes.
  • 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.
  • 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.
  • the introduction of CO2 is stopped and the pressure in the enclosure is reduced.
  • the pressure is reduced to ambient pressure, i.e., a pressure between 0.6 bar and 1.1 bar.
  • the epilame substrate was removed from the enclosure.
  • the epilaminated substrate can be heat-treated.
  • 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.
  • the epilaming process according to the invention may further comprise, after contacting the substrate surface with the epilaming agent, a complementary crosslinking step.
  • This complementary crosslinking is advantageously made possible by the presence of the groups appropriate functional interests provided on the R 5 side chains of the U units.
  • An epilame agent was produced by statistical copolymerization.
  • the monomer 1H,1H,2H,2H-perfluorooctyl methacrylate ( CAS 2144-53-8 ; R 2 being CH 3 , X being C(O)C(CH 2 ) 2 and L being C 6 F 13 ) was copolymerized by statistical copolymerization with the poly(ethylene glycol) methyl ether methacrylate monomer ( CAS 26915-72-0 ; R 1 being CH 3 , R 3 being CH 3 , ⁇ being 2 and Y being C(O)O) and the monomer 2-(methylthio)ethyl methacrylate ( CAS 14216-23-0 ; R 4 being CH 3 , W being C(O)O, A being (CH 2 ) 2 SCH 3 ), in the presence of a priming system.
  • Figure 1 represents the obtained epilame copolymer, in which R1 is CH3 , R2 is CH3 , R3 is CH3 , R4 is CH3 , A is ( CH2 ) 2SCH3 ).
  • the value of q is preferably between 1 and 20 (in the case where this group is present in the copolymer).
  • the m/p/q ratio was 45:45:10.
  • the m/p/q ratio was 30:60:10.
  • Three different epilame agents were deposited on the surface of a steel substrate, which had previously undergone surface preparation treatment, using an epilame bath.
  • the first epilame agent was the copolymer synthesized in Example 1.
  • the epilame bath used was an aqueous epilame bath.
  • the second epilame agent contains C6 perfluoroakyl groups, i.e. , C6F13 groups, as epilame groups, without containing any hydrophilic groups.
  • the epilame bath used was a fluorinated solvent epilame bath.
  • the third epilame agent is a competing epilame agent comprising methyl nonafluoroisobutyl ether ( CAS 163702-08-7 ), methyl nonafluorobutyl ether ( CAS 163702-07-6 ) and a fluoroaliphatic polymer.
  • the depilating bath used was a depilating bath containing fluorinated solvents.
  • the surface energy was determined.
  • the procedure known to those skilled in the art, consists of measuring (using a Dataphysics OCA 15 contact angle measuring device) the contact angles of droplets of three liquids. These are water, diiodomethane, and ethylene glycol, each of which has distinct surface tensions. From the angles obtained, the surface energy is calculated using the Owens, Wendt, Rabel, and Kaelble (OWRK) method.
  • the three epilames agents from Example 2 were then used (applied) to several substrates having a different composition.
  • the contact angle was measured with test oil #3 and with Moebius® oil 9010. Drops of both oils were deposited, and the contact angles were measured using an optical instrument (Dataphysics OCA 15). To assess resistance to watchmaking washes, the substrates were washed three times using a watchmaking wash (amine hydrocarbon solution), followed by measurement of the contact angles.
  • FIG. 2 represents the results on different substrates for the inventive copolymer.
  • the Figure 3 represents the results for the epilame agent type C 6 F 13
  • the Figure 4 represents the results for the competing agent epilame.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (15)

  1. Substrat mit einer Oberfläche, von der mindestens ein Teil mit einem Epilammittel überzogen ist, dadurch gekennzeichnet, dass dieses Epilammittel mindestens eine Verbindung in Form eines wasserlöslichen Copolymers umfasst, das M-Einheiten und N-Einheiten umfasst, die durch kovalente Bindungen über ihre Hauptketten miteinander verbunden sind, wobei
    M ist, N ist, wobei
    R1 und R2, gleich oder verschieden, H sind, eine C1-C10-Alkylgruppe oder eine C2-C10-Alkenylgruppe, vorzugsweise H oder CH3; X, gleich oder verschieden, ein Abstandshalterarm ist, bestehend aus einem Heteroatom oder einer Kohlenwasserstoffkette mit mindestens einem Heteroatom, linear oder verzweigt, mit mindestens einem Kohlenstoffatom; B, gleich oder verschieden, -((CH2)αO)β-R3 ist, wobei R3 H ist, eine C1-C10-Alkylgruppe oder eine C2-C10-Alkenylgruppe, vorzugsweise H oder CH3; α zwischen 1 und 6 gewählt ist, vorzugsweise zwischen 2 und 3; β zwischen 1 und 30 gewählt ist, vorzugsweise zwischen 2 und 20; L, gleich oder verschieden, eine halogenierte C1-C6-Kohlenstoffgruppe oder eine halogenierte Ethergruppe gemäß der Formel (I) ist, wobei
    Q ein Halogenatom ist,
    P, gleich oder verschieden, eine C1-C10-Alkylgruppe oder eine C2-C10-Alkenylgruppe ist, die mindestens ein Halogenatom umfasst und linear oder verzweigt ist,
    p zwischen 1 und 4 gewählt ist, vorzugsweise zwischen 2 und 3, und
    n zwischen 1 und 20 gewählt ist, vorzugsweise zwischen 1 und 10,
    dadurch gekennzeichnet, dass das Verhältnis der M-Einheiten/N-Einheiten bei einem β-Wert zwischen 1 und 10 zwischen 1:1 und 2:1 liegt und dass das Verhältnis der M-Einheiten/N-Einheiten bei einem β-Wert zwischen 11 und 30 zwischen 1:5 und 3:5 liegt, und dass Y, gleich oder verschieden, aus der Gruppe ausgewählt ist, die C1-C20-Estergruppen, Amidgruppen und Styrolderivate umfasst, optional umfassend mindestens ein Heteroatom.
  2. Substrat nach Anspruch 1, dadurch gekennzeichnet, dass das Copolymer ein statistisches Copolymer ist und dass die M- und N-Einheiten nach dem Zufallsprinzip aufgeteilt sind.
  3. Substrat nach Anspruch 1, dadurch gekennzeichnet, dass das Copolymer ein Block-Copolymer ist, umfassend mindestens einen Block M-Einheiten, die durch ihre Hauptketten kovalent verbunden sind, und mindestens einen Block N-Einheiten, die durch ihre Hauptketten kovalent verbunden sind, wobei diese Blöcke über ihre Hauptketten in linearen Sequenzen kovalent miteinander verbunden sind.
  4. Substrat nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass L eine C1-C6-Kohlenstoffgruppe ist, die mindestens teilweise fluoriert, vorzugsweise vollständig fluoriert ist, oder eine Ethergruppe, die mindestens teilweise fluoriert, vorzugsweise vollständig fluoriert ist.
  5. Substrat nach irgendeinem der zuvor genannten Ansprüche, dadurch gekennzeichnet, dass X, gleich oder verschieden, ausgewählt ist aus der Gruppe bestehend aus Estergruppen in C1-C20, Amidgruppen und Styrolderivatgruppen, wobei X, gleich oder verschieden, optional mindestens ein Heteroatom umfasst.
  6. Substrat nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass Y, gleich oder verschieden, ein Alkylester ist.
  7. Substrat nach irgendeinem der zuvor genannten Ansprüche, dadurch gekennzeichnet, dass das Copolymer ferner K-Einheiten umfasst, die mit den M- und N-Einheiten über ihre Hauptketten kovalent verbunden sind, wobei K ist, wobei
    R4, gleich oder verschieden, H ist, eine C1-C10-Alkylgruppe, eine C2-C10-Alkenylgruppe und vorzugsweise H oder CH3; W, gleich oder verschieden, ein Abstandshalterarm ist, bestehend aus einem Heteroatom oder einer Kohlenwasserstoffkette mit mindestens einem Heteroatom, linear oder verzweigt, mit mindestens einem Kohlenstoffatom; und A, gleich oder verschieden, eine Ankergruppe am Substrat bildet.
  8. Substrat nach irgendeinem der zuvor genannten Ansprüche, dadurch gekennzeichnet, dass das Copolymer zudem V-Einheiten umfasst, die durch ihre Hauptketten kovalent mit M- und N-Einheiten verbunden sind, wobei V ist, wobei
    R5, gleich oder verschieden, H ist, eine C1-C10-Alkylgruppe, eine C2-C10-Alkenylgruppe und vorzugsweise H oder CH3,
    Z, gleich oder verschieden, ein Abstandshalterarm ist, bestehend aus einem Heteroatom oder einer Kohlenwasserstoffkette mit mindestens einem Heteroatom, linear oder verzweigt, mit mindestens einem Kohlenstoffatom, und
    T, gleich oder verschieden, eine Tracer-Gruppe ist, die dazu vorgesehen ist, die Konzentration des Epilammittels in einem Epilamisierungsbad zu bestimmen.
  9. Substrat nach Anspruch 8, dadurch gekennzeichnet, dass T, gleich oder verschieden, eine UV-Sensorgruppe oder ein Fluorphor ist.
  10. Substrat nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Oberfläche, von der mindestens ein Teil mit dem Epilam bedeckt ist, aus einem Material gefertigt ist, das ausgewählt ist aus der Gruppe, die Metalle umfasst, wahlweise dotiert, Metalloxide, Metallnitriden, Metallkarbiden, Metalloide, wahlweise dotiert, Metalloideoxide, Metalloidenitriden, Metalloidenkarbiden, Legierungen, die mindestens ein Metallelement enthalten, Polymere, Saphir, Rubin, Diamond Like Carbon (DLC), und Kombinationen von zwei oder mehreren davon.
  11. Verfahren zur Epilamisierung mindestens eines Teils einer Oberfläche eines Substrats, das folgende Schritte umfasst:
    - Herstellen eines Epilammittels, umfassend mindestens ein wasserlösliches Copolymer gemäß den vorstehenden Ansprüchen,
    - optional, Herstellen der Oberfläche des Substrats,
    - Inkontaktbringen der Oberfläche des Substrats mit dem Epilammittel.
  12. Verfahren zur Epilamisierung nach Anspruch 11, dadurch gekennzeichnet, dass die Herstellung des Epilammittels durch Copolymerisation von Monomeren erfolgt, die in der Lage sind, die M-Einheiten mit Monomeren herzustellen, die in der Lage sind, die N-Einheiten zu bilden, vorzugsweise unter den Monomeren, die ausgewählt sind aus der Gruppe bestehend aus Acrylat-, Methacrylat-, Acrylamid-, Methacrylamid-, Vinyl- und Styrolmonomeren.
  13. Epilamisierungsverfahren nach irgendeinem der Ansprüche 11 bis 12, dadurch gekennzeichnet, dass das Epilammittel mindestens ein Copolymer gemäß den Ansprüchen 8 bis 9 umfasst, wobei seine Herstellung durch die Zubereitung eines wässrigen Epilamisierungsbades erfolgt, das das in Wasser gelöste Epilammittel enthält, und die Oberfläche des Substrats mit dem Epilammittel in dem wässrigen Epilamisierungsbad in Kontakt gebracht wird, wobei das Verfahren optional vor dem Inkontaktbringen einen Schritt zur Kontrolle der Konzentration des Epilammittels im wässrigen Epilamisierungsbad mittels der Tracer-Gruppe und optional einen Schritt zur Anpassung der Konzentration des Epilammittels im wässrigen Epilamisierungsbad umfasst.
  14. Verfahren zur Epilamisierung nach irgendeinem der vorstehenden Ansprüche 11 bis 12, dadurch gekennzeichnet, dass der Schritt zum Inkontaktbringen der Oberfläche des Substrats mit dem Epilammittel die folgenden Schritte umfasst:
    - Platzieren des Substrats und des Epilammittels in einem Gehäuse bei Umgebungsdruck,
    - bei luftdichtem Verschluss des Gehäuses,
    - Zugeben von CO2 in das luftdicht verschlossene Gehäuse bei einem Druck zwischen 25 und 74 bar, vorzugsweise zwischen 45 und 70 bar, bei einer Temperatur zwischen 10 °C und 80 °C, vorzugsweise zwischen 15 °C und 50 °C,
    - Senken des Drucks im Gehäuse und
    - Ablassen des epilamisierten Substrats aus dem Gehäuse.
  15. Verwenden eines wasserlöslichen Copolymers, umfassend M-Einheiten und N-Einheiten, die mit kovalenten Verbindungen über ihre Hauptkette verbunden sind, wobei
    M ist, N ist, wobei
    R1 et R2, gleich oder verschieden, H sind, einer C1-C10-Alkylgruppe, einer C2-C10-Algenylgruppe, vorzugsweise H oder CH3,
    X, identisch oder unterschiedlich ein Abteilarm ist ein Heteroatom oder eine Kohlenwasserstoffkette, das mindestens ein Heteroatom enthält, linear oder verzweigt, mit mindestens einem Kohlenstoffatom,
    B, gleich oder verschieden -((CH2)αO)β-R3 ist, wobei R3 H ist, einer C1-C10-Alkylgruppe, einer C2-C10-Algenylgruppe, vorzugsweise H oder CH3,
    α ausgewählt ist zwischen 1 und 6, vorzugsweise zwischen 2 und 3, und
    β, ausgewählt ist zwischen 1 und 30, vorzugsweise zwischen 2 und 20,
    L, gleich oder verschieden, eine halogenierte C1-C6-Kohlenstoffgruppe oder eine halogenierte Ethergruppe nach der Formel (I) ist, wobei
    Q ein Halogenatom ist,
    P, gleich oder verschieden, eine C1-C10-Alkylgruppe oder eine C2-C10-Alkenylgruppe ist, die mindestens ein Halogenatom hat und linear oder verzweigt ist,
    p ausgewählt wurde zwischen 1 und 4, vorzugsweise zwischen 2 und 3, und
    n ausgewählt wurde zwischen 1 und 20, vorzugsweise zwischen 1 und 10,
    dadurch gekennzeichnet, dass das Verhältnis der M-Einheiten/N-Einheiten bei einem β-Wert zwischen 1 und 10 zwischen 1:1 und 2:1 liegt, und dass das Verhältnis der M-Einheiten/N-Einheiten bei einem β-Wert zwischen 11 und 30 zwischen 1:5 und 3:5 liegt, und Y, gleich oder verschieden, ausgewählt ist aus der Gruppe, die aus C1-C20-Estergruppen besteht, in Amidgruppen, und Styrenderivatgruppen, wahlweise mit mindestens einem Heteroatom,
    als Epilammittel von mindestens einem Teil einer Oberfläche eines Substrats.
EP23206208.3A 2022-12-29 2023-10-26 Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats Active EP4394022B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202380088411.8A CN120457191A (zh) 2022-12-29 2023-12-27 包含涂覆有防油剂的表面的基材及防油涂覆此类基材的方法
JP2025537911A JP2026501559A (ja) 2022-12-29 2023-12-27 エピラム剤でコーティングされた表面を含む基板およびそのような基板をエピラムコーティングする方法
PCT/EP2023/087861 WO2024141565A1 (fr) 2022-12-29 2023-12-27 Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP22217103.5A EP4394021A1 (de) 2022-12-29 2022-12-29 Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats

Publications (2)

Publication Number Publication Date
EP4394022A1 EP4394022A1 (de) 2024-07-03
EP4394022B1 true EP4394022B1 (de) 2026-02-18

Family

ID=85036083

Family Applications (2)

Application Number Title Priority Date Filing Date
EP22217103.5A Withdrawn EP4394021A1 (de) 2022-12-29 2022-12-29 Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats
EP23206208.3A Active EP4394022B1 (de) 2022-12-29 2023-10-26 Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP22217103.5A Withdrawn EP4394021A1 (de) 2022-12-29 2022-12-29 Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats

Country Status (1)

Country Link
EP (2) EP4394021A1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8951630B2 (en) 2006-12-01 2015-02-10 Rolex S.A. Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame and in mechanical engineering as a barrier film
KR101529355B1 (ko) * 2007-12-12 2015-06-16 쓰리엠 이노베이티브 프로퍼티즈 컴파니 폴리(알킬렌 옥사이드) 반복 단위를 갖는 퍼플루오로폴리에테르 중합체를 포함하는 하드코트
US9714469B2 (en) 2010-12-23 2017-07-25 Rolex Sa Composition for increasing the lipophobicity of a watch-making component
EP3070152B1 (de) 2015-03-18 2018-02-28 The Swatch Group Research and Development Ltd. Substrat, das eine mit epilamisierungsmittel bedeckte oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
EP3070133B1 (de) 2015-03-18 2019-02-20 The Swatch Group Research and Development Ltd. Uhr oder scmucktück, das eine mit epilamisierungsmittel bedeckte oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
CH713789A2 (fr) * 2017-05-05 2018-11-15 Swatch Group Res & Dev Ltd Agent d'épilamage et procédé d'épilamage utilisant un tel agent.

Also Published As

Publication number Publication date
EP4394022A1 (de) 2024-07-03
EP4394021A1 (de) 2024-07-03

Similar Documents

Publication Publication Date Title
EP3070152B1 (de) Substrat, das eine mit epilamisierungsmittel bedeckte oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
EP3290451B1 (de) Substrat, das eine mit epilamisierungsmittel beschichtete oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
EP3070133B1 (de) Uhr oder scmucktück, das eine mit epilamisierungsmittel bedeckte oberfläche umfasst, und epilamisierungsverfahren eines solchen substrats
EP2084252A1 (de) Ultradünne hydrophobe und oleophobe schicht, herstellungsverfahren dafür und verwendung in der uhrmacherei als epilam
EP4394022B1 (de) Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats
EP3398978B1 (de) Epilamisierungsmittel und epilamisierungsverfahren, bei dem dieses epilamisierungsmittel verwendet wird
EP4394020B1 (de) Substrat mit einer mit einem epilammittel beschichteten oberfläche und verfahren zum epilamieren eines solchen substrats
WO2024141565A1 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat
CH713789A2 (fr) Agent d'épilamage et procédé d'épilamage utilisant un tel agent.
CH720410A2 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat
CH720411A2 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat
CH721921A2 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat
WO2025261829A1 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat
WO2008064512A1 (fr) Couche ultra-mince hydrophobe et oleophobe, procede de fabrication, son utilisation en mecanique comme film barriere
EP3315214A1 (de) Verfahren zur epilamisierung eines elements einer uhr oder eines schmuckstücks
WO2010149719A1 (fr) Procédé de préparation d'un film lubrifiant, support solide ainsi obtenu et kit de préparation
CH710889A2 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat.
EP3198054B1 (de) Oberflächenbehandlung von metallsubstraten
CH712872B1 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat.
CH710888A2 (fr) Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat.
HK40111386A (zh) 包含被防油剂覆盖的表面的基材和用防油剂涂布基材的方法
EP4726015A1 (de) Verwendung eines linearen polymers auf der basis von siloxanen als epilammittel
WO1997020641A1 (fr) Procede pour proteger contre la corrosion et/ou preparer a la mise en forme une piece metallique

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20241220

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20250218

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: APP_6838/2025

Effective date: 20250210

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20251017

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: F10

Free format text: ST27 STATUS EVENT CODE: U-0-0-F10-F00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260218

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: R17

Free format text: ST27 STATUS EVENT CODE: U-0-0-R10-R17 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260219

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602023012158

Country of ref document: DE