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    • 专利摘要:
    The invention relates to a copolymer and a substrate comprising a surface at least a portion of which is coated with an epilame agent comprising at least one compound in the form of a copolymer comprising V units, N units, optionally at at least one M unit and optionally at least one P unit, covalently associated by their main chains, where W, X, Y, Z are spacer arms, T is a tracer group arranged to determine the concentration of epilame agent in a epilamating bath, L is a halogenated, preferably fluorinated, C 1 -C 20 carbon group, A constitutes an anchoring group to the substrate, Q is H, CH 3, or a hydrocarbon chain different from T. also relates to a process for the epilamation of such a substrate, said method comprising a step of controlling the concentration of epilame agent in the epilamating bath by means of the tracer group and if necessary, a step of readjustment of the concentration of epilame agent in the epilamating bath.
    公开号:CH712872A2
    申请号:CH01133/16
    申请日:2016-09-01
    公开日:2018-03-15
    发明作者:Letondor Christophe；Rannoux Claire
    申请人:Swatch Group Res & Dev Ltd；
    IPC主号:
    专利说明:

    Description
    Field of the Invention The present invention relates to the field of mechanics and in particular to the field of watchmaking or jewelry. It relates more particularly to a copolymer, as well as a substrate, in particular a substrate of an element of a timepiece or of jewelry comprising a surface covered at least partially with an epilam agent comprising such a copolymer. It also relates to a method of epilamating such a substrate, as well as a timepiece or jewelry comprising an element comprising such a substrate.
    BACKGROUND OF THE INVENTION There are various methods for modifying the surface state of a substrate by treatment with an appropriate agent so as to specifically improve certain surface properties. For example, in the field of mechanics, and in particular in the field of watchmaking, but also in the field of jewelry, epilamage of a surface of a part or of an element is often carried out means of an epilam agent in order to control and reduce the surface energy of said surface during its use. More particularly, the purpose of an epilam agent is to prevent the spreading of oils or lubricants on the elements of a timepiece or of jewelry by forming a hydrophobic and lipophobic surface allowing the lubricant to remain at a predetermined place of the treated surface.
    The standard epilamation process is a dip coating process. It consists of immersing the timepieces in a waxing bath, that is to say a solution of the waxing agent in a solvent at a given concentration. The epilam effect depends on the concentration of epilam agent. Industrially, the same waxing bath is used to wax watch pieces for several months. As it is used, the amount of epilame agent in the bath decreases (part of the epilame agent remains adsorbed / hung on the timepieces) and the amount of solvent in the solution of epilame agent also decreases by evaporation. Thus, during use, the concentration of epilam agent in the waxing bath changes. To limit these fluctuations, industrially, a concentrated solution of epilam agent and / or solvent is regularly added to the epilamation bath. On the other hand, these additions are made very empirically since the current epilamage process does not provide precise information on the concentration of epilam agent. This leads to epilateral effects which vary significantly from one batch to another.
    Summary of the invention [0004] The aim of the invention is in particular to overcome the various drawbacks of epilamic agents and known epilamation methods.
    More specifically, an object of the invention is to provide an epilam agent as well as a depilamation process which make it possible to know precisely the concentration of epilam agent over time, in order to provide robustness. to the global epilamage process.
    To this end, the present invention relates to a copolymer comprising V units, N units, optionally at least one M unit and optionally at least one P unit, associated by covalent bonds by their main chains, where
    where F © R 2 , R 3 , R 4 , identical or different, are H, a C1-Ck alkyl group, C1-Ck alkenyl, and preferably H, CH3 W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom T, identical or different, is a tracer group arranged to determine the concentration of copolymer in an L medium, identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated
    A, identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, phosphonic acids, protected or not , protected or unprotected phosphonates, amines, ammoniums, nitrogenous heterocycles, carboxylic acids, anhydrides, catechol
    CH 712 872 A2
    Q, identical or different, is H, CH 3 , a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.
    The present invention also relates to a substrate comprising a surface at least part of which is covered with an epilam agent, said epilam agent comprises at least one compound in the form of a copolymer comprising V units, N units, optionally at least one M unit and optionally at least one P unit, associated by covalent bonds by their main chains, where
    where Ri, R 2 , R 3 , R4, identical or different, are H, a C1-C10 alkyl group, C1-C10 alkenyl, and preferably H, CH 3 W, X, Y, Z, identical or different , are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom T, identical or different, is a tracer group arranged to determine the concentration of epilame agent in a waxing bath
    L, identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated
    A, identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, phosphonic acids, protected or not , protected or unprotected phosphonates, amines, ammoniums, nitrogenous heterocycles, carboxylic acids, anhydrides, catechol
    Q, identical or different, is H, CH 3 , a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.
    [0008] Such an epilam agent makes it possible to control and follow the evolution of its concentration over time in the depilamation bath.
    The present invention also relates to a process for epilamating at least part of a surface of a substrate comprising the steps of:
    a) preparation of a hair removal bath containing an epilam agent comprising at least one copolymer as defined above
    b) optionally, preparation of the substrate surface
    c) control of the concentration of epilam agent in the epilamation bath by means of the tracer group
    d) optionally readjusting the concentration of epilam agent in the waxing bath
    e) bringing the surface of the substrate into contact with the epilam agent in the epilamation bath
    f) drying.
    The present invention also relates to the use, as an epilam agent of at least part of a surface of a substrate, in particular intended for watchmaking or jewelry, of a copolymer comprising V units, N units, optionally at least one M unit and optionally at least one P unit associated by covalent bonds by their main chains, where
    CH 712 872 A2
    where Ri, R 2 , R 3 , R 4 , identical or different, are H, a C1-C10 alkyl group, C1-C10 alkenyl, and preferably H, CH 3 W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom T, identical or different, is a tracer group arranged to determine the concentration as an epilam agent in a waxing bath
    L, identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated
    A, identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, phosphonic acids, protected or not , protected or unprotected phosphonates, amines, ammoniums, nitrogenous heterocycles, carboxylic acids, anhydrides, catechol
    Q, identical or different, is H, CH3, a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms, to control the concentration of agent epilam in a waxing bath.
    The present invention also relates to a timepiece or jewelry comprising an element comprising a substrate as defined above.
    Summary description of the drawings [0013] Other particularities and advantages will be clearly seen from the description which is given below, for information and in no way limitative, with reference to the attached drawings, in which:
    fig. 1 represents absorbance curves as a function of the wavelength for different concentrations of copolymer I in a solvent;
    fig. 2 is the calibration curve for the copolymer I representing the absorbance as a function of the concentration at the wavelength A = 336 nm FIG. 3 represents absorbance curves as a function of the wavelength for different concentrations of copolymer II in a solvent; and fig. 4 is the calibration curve for copolymer II representing the absorbance as a function of the concentration at the wavelength λ = 336 nm.
    Detailed description of the invention In accordance with the present invention, a substrate, in particular a substrate of an element of a timepiece or of jewelry, comprises a surface of which at least a part is covered with an agent. epilam, said epilam agent comprising at least one compound in the form of a copolymer comprising V units, N units, optionally at least one M unit and optionally at least one P unit, associated by covalent bonds by their main chains, where

    The
    CH 712 872 A2
    where Ri, R 2 , R3, R4, identical or different, are H, a C1-C10 alkyl group, C1-C10 alkenyl, and preferably H, CH 3 W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom T, identical or different, is a tracer group arranged to determine the concentration of agent epilam in a waxing bath
    L, identical or different, is a halogenated C 1 -C 2 carbon group, preferably fluorinated
    A, identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, phosphonic acids, protected or not , protected or unprotected phosphonates, amines, ammoniums, nitrogenous heterocycles, such as imidazole or pyridine, carboxylic acids, anhydrides, catechol Q, identical or different, is H, CH 3 , a hydrocarbon chain different from T, which may contain at least one heteroatom , linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.
    The invention also relates to a copolymer intended to form the epilam agent, and comprising V units, N units, optionally at least one M unit and optionally at least one P unit, associated by covalent bonds by their main chains , or

    The

    where Ri, R 2 , R 3 , R 4 , identical or different, are H, a C1-C10 alkyl group, C1-C10 alkenyl, and preferably H, CH 3 , W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom T, identical or different, is a tracer group arranged to determine the concentration of copolymer in an L medium, identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated
    A, identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, phosphonic acids, protected or not , protected or unprotected phosphonates, amines, ammoniums, nitrogenous heterocycles, such as imidazole or pyridine, carboxylic acids, anhydrides, catechol Q, identical or different, is H, CH3, a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.
    Preferably, the copolymer only comprises units V, N and optionally M and / or R [0017] The copolymer of the invention can be a random copolymer in which the units V, N, M and P are linked between them statistically by their main chain, that is to say distributed randomly, so that the random copolymer can be written in the form:
    Γ ΪΊ / r Ιί / r -CH 2 —ο- -ch 2 —c- - Γ ' ι | J z 1 L | JV x L
    '1
    CHp — d— / Ÿ ~
    CH
    Mo '. .T /
    CH 712 872 A2 The copolymer of the invention can be a block copolymer comprising at least one block of V units associated by covalent bonds by their main chains, at least one block of N units associated by covalent bonds by their main chains, at least one of the block of V units and of the block of N units optionally comprising at least one M unit and optionally at least one P unit, associated by covalent bonds by their main chains, said blocks being connected between them by covalent bonds by their main chains in linear sequences.
    The block copolymer can be written in the form:
    Preferably, the block copolymer comprises a single block of V units and a single block of N units, at least one of the block of V units and of the block of N units optionally comprising at least one unit. M and / or a P unit. When present, the number y1 of M units and the number w1 of P units in the block of V units can vary from the number y2 of M units and the number w2 of P units respectively in the block of N units.
    Preferably, the units P are integrated and distributed within the block composed of the units N, for example by statistical copolymerization of units P with the units N to form a single block consisting mainly of units N and assimilated to a block of N units.
    Preferably, the units M are integrated and distributed within the block composed of the units N, for example by statistical copolymerization of units M with the units N to form a single block consisting mainly of units N and assimilated to a block of N units.
    Advantageously, the groups W, X, Y, Z, identical or different, are chosen from the group comprising ester groups of Ci-C 20 , preferably C 2 -C 10 , more preferably in C 2 -C 6 , and even more preferably C 2 -C 5 , preferably alkyl ester groups, preferably linear, amide groups, and groups derived from styrene.
    Preferably, T, identical or different, is a UV absorber group or a fluorophore. Such groups make it possible, for example, to determine the concentration of copolymer by spectroscopy. It is obvious that any other type of tracer followed by appropriate detection and analysis means can be used.
    Advantageously, T, identical or different, is a UV absorber group derived from a compound chosen from the group comprising benzotriazoles, triazines, phenones (in particular benzophenone, acetophenone, hydroxyalkylphenone, hydroxyarylphenone, amino alkylphenone , anthraquinone), oxides of acylphosphine.
    Advantageously, T, identical or different, is a fluorophore group derived from a compound chosen from the group comprising fluorescein, a naphthyl, anthracene, coumarin, rhodamine, a fluorobenzoate.
    The functional groups of interest A are capable of reacting with the surface of the substrate to be epilated, so as to form groups for anchoring the epilam agent to the surface of the substrate. Advantageously, groups A can also be provided at the end of the copolymer.
    Advantageously, the copolymer comprises at least two different A groups.
    The functional groups of interest L are responsible for the epilam effect. They comprise at least one halogen atom, preferably a fluorine atom. In a preferred manner, L is a carbon group, ie an alkyl chain, which can be cyclic, preferably without heteroatom, in C 2 -C 20 , preferably in C 4 -C 10 , and more preferably in C 6 -Cg . L is partially or completely halogen. Advantageously, L is an at least partially fluorinated group, and preferably completely fluorinated. L can also include a hydrogen atom on the terminal group. L is preferably a perfluorinated alkyl chain.
    The functional groups of interest Q of the P units are used to modify the properties of the epilam agent and / or provide other functions. For example, Q can be an alkyl chain, preferably C 8 -C 20 , used to modify the contact angle obtained or a chain capable of constituting crosslinking points during a complementary crosslinking step (step g) . For example, the P units can be derived from stearyl methacrylate.
    Preferably, the copolymer comprises, in molar percentage, between 1% and 20%, preferably between 3% and 10% of V units, between 50% and 99%, preferably between 70% and 95% d '' N units, between 0% and 50%, preferably between 1% and 20%, and more preferably between 5% and 20% of M units, and between 0% and 50%, preferably between 0% and 20% , and more preferably between 0% and 10% of P units, the percentages being expressed relative to the total number of units (w + x + y + z).
    Advantageously, the copolymer comprises between 10 and 350 units (w + x + y + z).
    CH 712 872 A2 In a particularly advantageous manner, the units M, N, P are chosen to carry several groups A of different nature, several groups L, preferably of the same nature, and possibly one or more groups Q which may be the same or of a different nature, so as to refine and improve the properties of the epilam agent, in order to obtain more specifically a universal epilam agent and having an improved affinity with the substrate.
    Preferably, the surface of the substrate, at least part of which is covered with the epilam agent, is made of a material chosen from the group comprising metals, metal oxides, doped or not, polymers, sapphire, ruby, silicon, silicon oxides, silicon nitrides, silicon carbides, DLC (Diamond Like Carbon), and their alloys.
    More specifically, the surface of the substrate can be made of steel, or of noble metals such as gold, rhodium, palladium, platinum, or of metal oxides, doped or not with aluminum, zirconium, titanium, chromium, manganese, magnesium, iron, nickel, copper, zinc, molybdenum, silver, tungsten, or polyoxymethylene or acrylamide, and their alloys.
    The present invention also relates to a process for epilamating at least part of a surface of a substrate comprising the steps of:
    a) preparation of a hair removal bath containing an epilam agent comprising at least one copolymer as defined above
    b) optionally, preparation of the surface of the substrate, in particular by cleaning according to standard watchmaking processes,
    c) control of the concentration of epilam agent in the epilamation bath by means of the tracer group
    d) optionally readjusting the concentration of epilam agent in the waxing bath
    e) bringing the surface of the substrate into contact with the epilam agent in the epilamation bath
    f) drying.
    It is obvious that step a) can be implemented remotely over time from the other steps b), c), d) and f). Preferably, for example when the epilamation process is carried out continuously or when the same epilamage bath is used several times, steps c) and d) can be repeated in order to control the concentration of epilam agent over time so as to maintain this constant concentration for the implementation of step e).
    Advantageously, when the group T is a UV absorber group or a fluorophore, the concentration of the epilam agent is determined by spectroscopy (measurement of absorbance for example). An intermediate step, prior to step c) provides for the development of a copolymer calibration curve. For this, the copolymer is dissolved at different concentrations in a solvent (same solvent as that used for making the solution of epilam agent) and for each solution the absorbance is measured by spectroscopy as a function of the wavelength.
    The wavelength for which the absorbance is maximum is identified and then the calibration curve A = F (concentration) is plotted at the wavelength for which the absorbance is maximum. We deduce the molar extinction coefficient of the polymer (Beer Lambert's law A = ecl).
    To control the concentration of epilam agent in the epilamage bath according to step c), it suffices to measure the absorbance of the bath solution by spectroscopy, then using the previously established calibration curve of deduce the concentration of epilam agent therein in the epilamage bath. The operator can thus add solvent or concentrated solution of epilam agent to readjust the concentration precisely, in accordance with step d). In the context of a continuous epilamage process, for example, or when the same epilamage bath is used several times, several controls of the concentration of epilam agent make it possible to follow the evolution of the concentration of epilam agent during time so as to keep it constant.
    Preferably, the preparation of the epilam agent is carried out by random or block copolymerization of monomers capable of forming the V units with monomers capable of forming the N units, optionally with monomers capable of forming at least one unit. M and optionally with monomers capable of forming at least one R unit. Statistical or block copolymerization techniques are well known to those skilled in the art and do not require a detailed description. A particularly suitable mode of polymerization for random copolymerization is free radical copolymerization, in solution or in emulsion.
    In a first variant, the statistical copolymer can be obtained in a single step by copolymerization, preferably radical, of monomers carrying the side chains ZT with monomers carrying the side chains XL and optionally monomers carrying the side chains Y- A and / or optionally monomers carrying the side chains WQ.
    CH 712 872 A2 According to another variant, the random copolymer can be obtained by copolymerization, preferably radical, of monomers carrying the adequate side chains Z with monomers carrying the appropriate side chains X and optionally monomers carrying side chains intended to carry A and / or optionally monomers carrying side chains intended to carry Q, then the side chains are modified after polymerization (post-functionalization), for example by "click chemistry", in order to introduce therein the functional groups of interest T, L, and groups A and / or Q.
    A particularly suitable polymerization method for block copolymerization is the successive controlled copolymerization:
    - monomers capable of forming at least one block of V units and optionally with monomers capable of forming at least one M unit and / or monomers capable of forming at least one P unit
    - monomers capable of forming at least one block of N units, and optionally with monomers capable of forming at least one M unit and / or monomers capable of forming at least one identical or different P, M or P unit.
    Two polymerization methods for block copolymerization which are particularly suitable are radical copolymerization by atom transfer (ATRP) and radical polymerization controlled by reversible chain transfer by addition-fragmentation (RAFT), in solution or in emulsion.
    In a first variant, the block copolymer can be obtained by polymerization, preferably controlled radical, of monomers carrying the side chains ZT with optionally monomers carrying the side chains Y-A and / or optionally monomers carrying the side chains WQ, followed by the copolymerization, preferably free radical controlled, of monomers carrying the XL side chains with optionally monomers carrying the Y-A side chains and / or optionally monomers carrying the same or different WQ, Y-A and WQ side chains .
    According to another variant, the block copolymer can be obtained by polymerization, preferably controlled radical, of monomers carrying the adequate side chains Z with optionally monomers carrying side chains intended to carry A and / or optionally monomers carrying side chains intended to carry Q, followed by the copolymerization, preferably radical controlled, of monomers carrying the appropriate side chains X with optionally monomers carrying side chains intended to carry A and / or optionally monomers carrying side chains intended to carry Q, then the side chains are modified, for example by "click chemistry", to introduce the functional groups of interest T, L and the groups A and / or Q.
    Preferably, the monomers are chosen from the group comprising the acrylate, methacrylate, acrylamide, methacrylamide, vinyl, diene, styrenic and olefinic monomers. The acrylate, methacrylate, acrylamide, methacrylamide, vinyl and styrenic monomers are particularly preferred. These products are known and for the most part available on the market or accessible in a synthesis step.
    The monomers which are particularly preferred for forming the units V comprising a tracer group T are chosen from the group comprising 2-H-benzotriazole-2-yl-hydroxyphenyl ethyl methacrylate, 2- (2H-Benzotriazol2-yl) -4 -methyl-6- (2-propenyl) phenol, 2- (4-Benzoyl-3-hydroxyphenoxy) ethyl acrylate, 4-Allyloxy-2-hydroxybenzophenone, Ie2-Naphthyl (meth) acrylate, Fluorescein O- (meth ) acrylate, 9-Anthracenylmethyl (meth) acrylate, Ethidium bromide-N, N'-bisacrylamide, N- (1-Naphthyl) -N-phenylmethacrylamide, 7- [4- (Trifluoromethyl) coumarin] methacrylamide. Such monomers are commercially available and are polymerizable.
    Even more preferably, the monomers for forming the units V comprising a tracer group T are chosen from the group comprising 2-H-benzotriazole-2-yl-hydroxyphenyl ethyl methacrylate, 2- (2H-Benzotriazol2-yl) -4-methyl-6- (2-propenyl) phenol, 2- (4-Benzoyl-3-hydroxyphenoxy) ethyl acrylate, 4-Allyloxy-2-hydroxybenzophenone. These monomers contain tracer groups which can be monitored by UV-visible spectroscopy, which is much easier to set up in an industrial environment than fluorescence spectroscopy.
    The monomers which are particularly preferred for forming the units N, M and P are:
    CH 712 872 A2
    Ό .OR
    OR · ^ ° R <C 0R '
    R equal or different from R '= H, Alkyl, Si (Me),
    '0
    cf 3



    O (MeOfeSr (MeOfeMeSr {Me) 2 MeOSi '
    My



    PC. (0¾ f 2 hc ·, (CF 2 ) 7. (CF 2 ) j
    F, C '
    0 '' ° o z o z
    FsC. (0¾ N
    C II o
    NOT
    II
    VS
    Thus, the copolymer used as an epilam agent can be easily obtained in a single step or a limited number of steps from marketed products.
    One of the copolymers preferably used in the present invention is a random copolymer which has the following structure (I)
    CH 712 872 A2
    Another copolymer preferably used in the present invention is a random copolymer which has the following structure (II):
    The copolymers used in the invention can be obtained in the form of powder or viscous liquid. They can then be dissolved in a fluorinated solvent, such as perfluorinated or fluorinated hydrocarbons, perfluoropolyethers, hydrofluoroolefins, hydrofluoroethers, at concentrations preferably between 50 mg / L and 250 mg / L, in order to obtain a solution of epilam agent, which will be used for the treatment of the surfaces to be epilamated.
    According to the variants, the epilamage process according to the invention may further comprise, after step e), a step g) of additional crosslinking, made possible in particular by the presence of the functional groups of appropriate interest provided on the side chains Q of the P units.
    The substrate according to the invention has a surface covered with a simple and economical epilam agent to synthesize, having an affinity with any type of substrate and improved resistance to washing compared to known epilame agents. An element or a part having a substrate in accordance with the invention can be used in any type of application in the mechanical field, and more particularly in precision mechanics, and in particular watchmaking and jewelry.
    The method according to the invention makes it possible to control and monitor the concentration of epilam agent in the epilamising bath over time in order to be able to readjust the composition of the epilamizing agent epilam bath. Thus, the concentration of epilam agent in the depilamation bath is substantially constant so that the epilam effects are constant for all of the batches treated. This results in a robust epilamation process. The following examples illustrate the present invention without, however, limiting its scope.
    Synthesis of 3-methacryloxopropyl methyl thioether: (according to a procedure similar to that described in US patent 6,552,103) In a three-necked flask with magnetic stirring placed under nitrogen are added thiomethylpropanol (4.05mL) , dichloromethane (100mL) and triethylamine (8.2mL). The solution is cooled in an ice bath then me10 chloride
    CH 712 872 A2 thacrylate (3.8mL) is added dropwise over 10 min. The reaction mixture is stirred for 2 h at 0 ° C and then at room temperature overnight. 70 mL of water are added and the reaction mixture is transferred to a separatory funnel. The organic phase and the aqueous phase are separated. The organic phase is washed with an HCl solution (pH = 4) until pH = 7 is reached and then dried over Na 2 SO 4 . The solvent is then removed on a rotary evaporator to yield the expected product with a yield of 97%.
    1 H NMR (CDCI 3 , 500MHz): chemical shift (ppm): 6.10 (s, 1H), 5.56 (s, 1H), 4.24 (t, 2H), 2.58 (t, 2H), 2.11 ( s, 3H), 1.99 (m, 2H), 1.94 (s, 3H)
    Example 1 An epilam agent is synthesized in the form of a random copolymer by free radical polymerization of:
    - (3-methacryloxopropyl) dimethyl-methoxysilane
    - 1H, 1H, 2H, 2H-Perfluorooctylacrylate
    - 3-methacryloxopropyl methyl thioether prepared as indicated above
    - 2- [3- (2H-Benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate according to the following procedure:
    2- [3- (2H-Benzotriazol-2-yl) -4-hydroxyphenyljethyl methacrylate (148 mg), (3-methacryloxopropyl) are added to a Schlenk tube containing cyclohexanone (2 ml) previously degassed with nitrogen. ) dimethyl-methoxysilane (166pL), 3-Methacryloxopropyl methylthioether (111 μ L) then 1 H, 1 H, 2H, 2H-Perfluorooctylacrylate (2.0 mL). The reaction medium is bubbled for 5 min with nitrogen and then 0.8 ml of hydrofluoroether (Novec ™ HFE-72003M ™) previously bubbled with nitrogen are added. 0.5mL of a 0.228mol / L azobisisobutyronitrile (AIBN) solution is added. The reaction medium is stirred and heated at 80 ° C for 3 h. The polymer is coagulated in methanol and then rinsed with 3 * 30 ml of methanol. The polymer is obtained in the form of a slightly whitish gel (yield = 95%).
    The following random copolymer (I) is obtained:
    UV absorbance measurement:
    The copolymer (I) is dissolved at various concentrations in a fluorinated solvent, type Ecosolv (Moebius) identical to the solvent used in the hair removal bath. For each concentration, absorbance is measured by UV-visible spectroscopy. We obtain the curves shown in fig. 1. The wavelength for which the absorbance is maximum is identified at 336 nm, which makes it possible to determine the molar absorption coefficient of the polymer at the maximum absorption at 336 nm. We can then establish a calibration curve, as shown in fig. 2, representing the absorbance as a function of the concentration of copolymer. This calibration curve subsequently makes it possible to determine the concentration of copolymer in the depilamation bath at all times by a simple measurement of absorbance by UV-visible spectroscopy carried out from samples of epilamage bath taken. Depending on the result obtained, the operator knows whether to add solvent or a concentrated solution of epilam agent in order to precisely readjust the concentration of epilam agent to maintain a substantially constant concentration during the epilamation process.
    Example 2 An epilam agent is synthesized in the form of a random copolymer by free radical polymerization of:
    CH 712 872 A2
    - 2- (2,2-Diphenyl-benzo [1,3] dioxo-5-yl) -ethyl-acrylate (obtained by reaction between - (2,2-Diphenyl-benzo [1,3] dioxo-5- y I) ethylamine (commercially available) and acryloyl Chloride)
    - 1H, 1H, 2H, 2H-Perfluorooctylacrylate
    - 3-acryloxopropy! methyl thioether (obtained according to the procedure described in the literature: Preparation of biomimetic polymer hydrogel materials for contact lenses Bertozzi, Carolyn et al. US 6 552 103)
    - 2- [3- (2H-Benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate according to the following procedure:
    in a Schlenk tube containing cyclohexanone (2mL) degassed beforehand with nitrogen, are added 2- [3- (2H-Benzotriazol-2-yl) -4-hydroxyphenyljethyl methacrylate (162 mg), 2- (2 , 2-Diphenyl-benzo [1,3] dioxo-5-yl) -ethyl-acrylate (373 mg), 3-acryloxopropyl methylthioether (111 μΙ_) then 1H, 1H, 2H, 2H-Perfluorooctylacrylate (2.1 mL) . The reaction medium is bubbled for 5 min with nitrogen and then 0.8 ml of hydrofluoroether (Novec ™ HFE-72003M ™) previously bubbled with nitrogen are added. 0.55mL of a 0.228mol / L azobisisobutyronitrile (AIBN) solution is added. The reaction medium is stirred and heated at 80 ° C for 3 h. The polymer is coagulated in methanol and then rinsed with 3 * 30mL. The polymer is obtained in the form of a slightly whitish gel (yield = 92%).
    The following statistical copolymer is obtained:
    The protective group for the catechol function of the polymer is then removed (deprotection of the catechol function) according to the following procedure:
    The polymer obtained above is dissolved in 50 ml of fluorinated solvent (Novec ™ HFE-72003M ™), then 5 ml of Trifluoroacetic acid are added with stirring. The reaction is left stirring for 1 hour. The mixture is then washed with 4 x 40 mL of water, the organic phases are collected and the fluorinated solvent reduced to a minimum. The polymer is coagulated in methanol and then rinsed with 3 * 30mL. The polymer is obtained in the form of a slightly whitish gel (yield = 75%).
    The following random copolymer (II) is obtained:
    CH 712 872 A2
    UV absorbance measurement:
    The copolymer (II) is dissolved at various concentrations in a fluorinated solvent, type Ecosolv (Moebius), identical to the solvent used in the epilamation bath. For each concentration, absorbance is measured by UV-visible spectroscopy. We obtain the curves shown in fig. 3. The wavelength for which the absorbance is maximum is identified at 336 nm, which makes it possible to determine the molar absorption coefficient of the polymer at the maximum absorption at 336 nm. We can then establish a calibration curve, as shown in fig. 4, representing the absorbance as a function of the copolymer concentration. This calibration curve subsequently makes it possible to determine the concentration of copolymer in the depilamation bath at all times by a simple measurement of absorbance by UV-visible spectroscopy carried out from samples of epilamage bath taken. Depending on the result obtained, the operator knows whether to add solvent or a concentrated solution of epilam agent in order to precisely readjust the concentration of epilam agent to maintain a substantially constant concentration during the epilamation process.
    权利要求:
    Claims (25)
    [1]
    claims
    1. Copolymer comprising V units, N units, optionally at least one M unit and optionally at least one P unit associated by covalent bonds by their main chains, where
    TL where FL, R 2 , R 3 , R 4 , identical or different, are H, a C1-C10 alkyl group, C1-C10 alkenyl, and preferably H, CH 3 W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom
    T, identical or different, is a tracer group arranged to determine the concentration of copolymer in a medium L, identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated A, identical or different, constitutes a group d anchoring to the substrate, and is chosen from the group comprising 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, catechol
    CH 712 872 A2
    Q, identical or different, is H, CH 3 , a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.
    [2]
    2. Copolymer according to claim 1, characterized in that W, X, Y, Z, identical or different, are chosen from the group comprising C 1 -C 2 o, preferably C 2 -C 10 ester groups, amide groups, and groups derived from styrene.
    [3]
    3. Copolymer according to one of the preceding claims, characterized in that T, identical or different, is a UV absorber group or a fluorophore.
    [4]
    4. Copolymer according to one of the preceding claims, characterized in that T, identical or different, is a UV absorber group derived from a compound chosen from the group comprising benzotriazoles, triazines, phenones, acyl oxides phosphine.
    [5]
    5. Copolymer according to one of claims 1 to 3, characterized in that T, identical or different, is a fluorophore group derived from a compound chosen from the group comprising fluorescein, naphthyl, anthracene, coumarin, rhodamine, a fluorobenzoate.
    [6]
    6. Copolymer according to one of the preceding claims, characterized in that L is a C 2 -C 20 carbon group, preferably C 4 -C 10 .
    [7]
    7. Copolymer according to one of the preceding claims, characterized in that L is an at least partially fluorinated group, preferably completely fluorinated.
    [8]
    8. Copolymer according to one of the preceding claims, characterized in that it comprises, in molar percentage, between 1% and 20%, preferably between 3% and 10% of V units, between 50% and 99%, preferably between 70% and 95% of N units, between 0% and 50%, preferably between 1% and 20% of M units, and between 0% and 50%, preferably between 0% and 20% d 'P. units
    [9]
    9. Copolymer according to one of the preceding claims, characterized in that it comprises between 10 and 350 units.
    [10]
    10. Substrate comprising a surface at least part of which is covered with an epilam agent, characterized in that said epilam agent comprises at least one compound in the form of a copolymer comprising V units, N units, optionally at least a unit M and optionally at least one unit P, associated by covalent bonds by their main chains, where where Ri, R 2 , R 3 , R 4 , identical or different, are H, a C1-C10 alkyl group, alkenyl C1-C10, and preferably H, CH 3 W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom
    T, identical or different, is a tracer group arranged to determine the concentration of epilam agent in a waxing bath
    L, identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated A, identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising thiols, thioethers, thioesters, sulfides, thioamides, silanols, alkoxysilanes, silane halides, hydroxyls, phosphates, protected or unprotected phosphonic acids, protected or unprotected phosphonates, amines, ammoniums, nitrogenous heterocycles, carboxylic acids, anhydrides, catechol
    Q, identical or different, is H, CH3, a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms.
    [11]
    11. Substrate according to claim 10, characterized in that W, X, Y, Z, identical or different, are chosen from the group comprising C 1 -C 20 , preferably C 2 -C 10 ester groups, amide groups, and groups derived from styrene.
    CH 712 872 A2
    [12]
    12. Substrate according to one of claims 10 and 11, characterized in that T, identical or different, is a UV absorber group derived from a compound chosen from the group comprising benzotriazoles, triazines, phenones, oxides d acyl phosphine.
    [13]
    13. Substrate according to one of claims 10 and 11, characterized in that T, identical or different, is a fluorophore group derived from a compound chosen from the group comprising fluorescein, naphthyl, anthracene, coumarin, rhodamine, a fluorobenzoate.
    [14]
    14. Substrate according to one of claims 10 to 13, characterized in that L is a carbon group in C 2 -C 20 , preferably in C 4 -C 10 .
    [15]
    15. Substrate according to one of claims 10 to 14, characterized in that L is an at least partially fluorinated group, preferably completely fluorinated.
    [16]
    16. Substrate according to one of claims 10 to 15, characterized in that the copolymer comprises, in molar percentage, between 1% and 20%, preferably between 3% and 10% of V units, between 50% and 99 %, preferably between 70% and 95% of N units, between 0% and 50%, preferably between 1% and 20% of M units, and between 0% and 50%, preferably between 0% and 20 % of P. units
    [17]
    17. Substrate according to one of claims 10 to 16, characterized in that the copolymer comprises between 10 and 350 units.
    [18]
    18. Substrate according to one of claims 10 to 17, characterized in that its surface at least part of which is covered with the epilam agent is made of a material chosen from the group comprising metals, metal oxides, polymers , sapphire, ruby, silicon, silicon oxides, silicon nitrides, silicon carbides, DLC (Diamond Like Carbon), and their alloys.
    [19]
    19. A method of epilamating at least part of a surface of a substrate comprising the steps of:
    a) preparation of a hair removal bath containing an epilam agent comprising at least one copolymer as defined in claims 1 to 9
    b) optionally, preparation of the substrate surface
    c) control of the concentration of epilam agent in the epilamation bath by means of the tracer group
    d) optionally readjusting the concentration of epilam agent in the waxing bath
    e) bringing the surface of the substrate into contact with the epilam agent in the epilamation bath
    f) drying.
    [20]
    20. depilating method according to claim 19, characterized in that said depilating method is continuous and in that steps c) and d) are repeated over time.
    [21]
    21. depilamation method according to one of claims 19 and 20, characterized in that the preparation of the epilam agent is carried out by copolymerization of monomers capable of forming the V units with monomers capable of forming the N units, optionally with monomers capable of forming at least one M unit and optionally with monomers capable of forming at least one P unit.
    [22]
    22. epilamage method according to one of claims 19 to 21, characterized in that it further comprises, after step e), a step g) of additional crosslinking.
    [23]
    23. epilamage process according to one of claims 19 to 22, characterized in that the monomers are chosen from the group comprising the acrylate, methacrylate, acrylamide, methacrylamide, vinyl and styrenic monomers.
    [24]
    24. Use, as an epilam agent of at least part of a surface of a substrate, of a copolymer comprising V units, N units, optionally at least one M unit and optionally at least one P unit, associated by covalent bonds via their main chains, where where Ri, R 2 , R 3 , R 4 , identical or different, are H, a C1-C10 alkyl group, C1-C10 alkenyl, and preferably H, CH 3
    CH 712 872 A2
    W, X, Y, Z, identical or different, are spacer arms consisting of a heteroatom or of a hydrocarbon chain which may contain at least one heteroatom, linear or branched, comprising at least one carbon atom T, identical or different , is a tracer group arranged to determine the concentration of epilam agent in a waxing bath
    L, which is identical or different, is a halogenated C 1 -C 20 carbon group, preferably fluorinated A, which is identical or different, constitutes an anchoring group to the substrate, and is chosen from the group comprising 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, catechol
    Q, identical or different, is H, CH 3 , a hydrocarbon chain different from T, which may contain at least one heteroatom, linear or branched, saturated or unsaturated, comprising at least 2 carbon atoms, to control the concentration of epilam agent in a waxing bath.
    [25]
    25. Timepiece or jewelry comprising an element comprising a substrate according to any one of claims 10 to 18.
    CH 712 872 A2
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    同族专利:
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    引用文献:
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    CH01133/16A|CH712872B1|2016-09-01|2016-09-01|Substrate comprising a surface coated with an epilame agent and method of epilamating such a substrate.|CH01133/16A| CH712872B1|2016-09-01|2016-09-01|Substrate comprising a surface coated with an epilame agent and method of epilamating such a substrate.|
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