PHOTORETICULABLE VARNISH COMPOSITIONS AND METHODS OF APPLICATION

专利摘要:
The present invention relates to a photocurable cosmetic composition, in particular for the coating of a nail or false nail, and more particularly for the make-up of a nail or false nail, comprising, in a physiologically acceptable: at least one photocrosslinkable compound a) comprising at least one acrylate functional group (ALK) and at least one carboxylic acid function; at least one photocrosslinkable compound b) comprising at least one poly (urethane poly (ALK) acrylate compound, preferably polyurethane di (meth) acrylate, more preferably polyurethane dimethacrylate, the (s) photocrosslinkable compound (s) b) comprising a (poly) oxyalkylene unit, in particular comprising a (poly) oxyethylene unit, preferably comprising from 1 to 100 oxyalkylene units, preferably from 5 to 50 oxyalkylene units, and preferably from approximately 8 to 10 oxyalkylene units, at least one photocrosslinkable compound c) comprises comprising at least one (poly) urethane poly (ALK) acrylate compound, preferably polyurethane di (meth) acrylate, more preferably polyurethane dimethacrylate, comprising at least two carbamate units obtained by reaction with at least one isophorone diisocyanate diisocyanate (IPDI) . The present invention also relates to particular methods of application of such a composition.
公开号:FR3013975A1
申请号:FR1362084
申请日:2013-12-04
公开日:2015-06-05
发明作者:Guillaume Kergosien；Carl Riachi；Pape Marina Le
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] The present invention relates to novel photocurable varnish compositions. This type of composition preferably corresponds to a coating applied directly in contact with the nail and / or the false nail. In particular, this coating may be a colored coating. This coating can also be called a base coating or first coating in the case of a structure employing a plurality of coatings of distinct compositions. This coating can thus be coated with at least one second coating. In particular, this second coating may be a finishing coating or a colored coating. More particularly, the first coating may be coated with a colored coating as a second coating, itself coated with a finishing coating as a third coating. It also relates to methods for applying such compositions to nails and / or false nails, as well as the use of said compositions for the makeup and / or care of nails and / or false nails. The nail polish compositions can be used as a base for varnish (also called base coat in the English terminology), as a nail makeup product, or as a finishing composition (also called a topcoat according to the English terminology). saxon) to be applied to the nail makeup product, or even as a cosmetic nail care product. These compositions can be applied to both natural nails and false nails. Nail polishes are known from liquid cosmetic compositions, which are used by first depositing a coating on the nail and then subjecting said coating to the action of light radiation, which causes within said coating in situ polymerization and / or crosslinking reactions resulting in most often crosslinked polymer networks. Such photocurable compositions, commonly known as "UV gels" and generally based on crosslinkable compounds of monomeric (meth) acrylate type, make it possible to obtain a good hold of the coating deposited on the nail, and are described, for example, in CA 1 306. 954, US 5,456,905, US 7,375,144 and FR 2,823,105. However, the so-called conventional "soak-off" UV gels are generally kits comprising three distinct compositions consisting of a photocurable base composition, a composition photocrosslinkable color, and photocurable finish composition. The photocurable colored composition should be used in combination with the base composition and the finishing composition, otherwise the coating formed generally leads to gloss and hold problems. Which makes the application long and tedious. In addition, the so-called "soak-off" UV gels generally have holding problems when they are not applied by expert manicurists. They also generally require a nail polishing step to sand the nail to promote the holding of the photocured composition in the form of a film, thus significantly damaging the nail. Moreover, the removal of makeup of such compositions is often difficult and may require a step of scraping the nail with a metal tool, an electric sander, or an abrasive file, harmful to the integrity of the nail. Among the prior art patents to overcome these problems can be cited documents US2011 / 0081306, US2011 / 0082228, US2011 / 0274633 and US2012 / 0083547. The present invention is distinguished from this state of the art by the development of a composition having good gloss and good hold on the nails without the need to use base coat and topcoat. In addition, some products may have performance problems concerning, in particular, the quality of makeup. Furthermore, the step of removing make-up of the compositions of the prior art conventionally uses tools intended to scrape the surface of the nail to remove the photocured film of previously applied composition, which may damage the nails. Finally, the present invention aims at providing new photocurable compositions having, after photocrosslinking of the film, a low content of extractable compounds comprising reactive (meth) acrylate functions. The present invention thus aims to provide novel photocurable compositions which do not exhibit at least one of the disadvantages of the aforementioned compositions. In particular, the present invention aims to provide photocrosslinkable compositions which can be removed by conventional organic solvents, such as acetone, without requiring an abrasive tool for the nails. In particular, the present invention aims to provide photocurable compositions which have a good compromise between holding and removing makeup compared to photocurable compositions described in the prior art or existing.
[0002] The present invention also aims to provide photocurable compositions for makeup quality of the nails, particularly in terms of homogeneity of result and where appropriate color. The present invention aims to provide photocurable compositions that are easy to use, including by the user itself, thus saving time and money. The present invention relates to a photocurable cosmetic composition, in particular for coating a nail or false nail, and more particularly for making up a nail or false nail, comprising, in a physiologically acceptable medium at least one photocrosslinkable compound a) comprising at least one acrylate functional group (ALK) and at least one carboxylic acid function, at least one photocrosslinkable compound b) comprising at least one poly (urethane) poly (ALK) acrylate compound, preferably di (meth) acrylate polyurethane, more preferably polyurethane dimethacrylate, the (s) photocrosslinkable compound (s) b) comprising a (poly) oxyalkylene unit, in particular comprising a (poly) oxyethylene unit, preferably comprising from 1 to 100 units oxyalkylene, preferably from 5 to 50 oxyalkylene units, and preferably about 8 to 10 oxyalkylene units, at least one photocrosslinkable compound c) comprises at least one compound (poly) urethane poly (ALK) acrylate, preferably polyurethane di (meth) acrylate, more preferably polyurethane dimethacrylate, comprising at least two carbamate units obtained by reaction with at least one isophorone diisocyanate diisocyanate (IPDI) .
[0003] According to preferred embodiments answering at least one of the aforementioned problems: the photocrosslinkable compound (s) a) comprises (include) at least one photocrosslinkable compound corresponding to the following formula (I): Formula (I) Formula (I) in which: - R1, R2, R3, which may be identical or different, representing a hydrogen atom, a C1-C10 alkyl, preferably C1-alkyl group, preferably R1 being a methyl preferably, R2 and R3 being a hydrogen atom, n being an integer from 1 to 10, preferably 2, the bond between a and 3 of the carbonyloxy is a single bond, a double bond or is a bond included in a (hetero) ring comprising from 5 to 7 carbon atoms, preferably to 6 carbon atoms, (hetero) ring which may be aromatic or non aromatic, preferably aromatic, more preferably an aryl, such as a phenyl; The term "photocrosslinkable compounds of formula (I)" also means its optical isomers, its geometrical isomers and its base salts. the photocurable compound (s) a) have the formula (la): ## STR5 ## Formula (la) in which: R1, R2, R3, identical or different, representing a hydrogen atom, a C 1 -C 10 alkyl group, preferably C 1, preferably R 1 being methyl, preferably R 2 and R 3 being a hydrogen atom, n being an integer from 1 to 10, preferably equal to 2, the photocurable compound (s) a) have the formula (Ib): ## STR2 ## Formula (Ib) Formula (Ib) in which: R1, R2, R3 , identical or different, representing a hydrogen atom, a C 1 -C 10 alkyl group, preferably C 1, preferably R 1 being methyl, preferably R 2 and R 3 being a hydrogen atom, - n representing a whole number between 1 and 10, preferably equal to 2, the photocurable compound (s) a) have the formula (1c): ## STR2 ## Formula (Ic) Formula (Ic) in the formula (Ic) water: - R1, R2, R3, identical or different, representing a hydrogen atom, a C1-C10 alkyl group, preferably C1, preferably R1 being a methyl, preferably R2 and R3 being an atom; hydrogen, - n representing an integer between 1 and 10, preferably equal to 2, the (s) photocrosslinkable compound (s) a) is (are) chosen from compounds of formula (la) ), (Ib), and (Ic), as previously defined, and their mixture; the photocurable compound (s) comprises at least one photocrosslinkable compound corresponding to the following formula (V): R30 X 0 \ 10 Embedded image in which: R 1 and R 2, which are identical or different, represent a hydrogen atom, or a methyl group, or a group of the following formula (II): ## STR2 ## R5 (VI) R5 representing a hydrogen atom or a methyl group, preferably R1 and R2 representing a hydrogen atom; - R3 and R4, identical or different, represent a hydrogen atom or a methyl group; X represents a radical corresponding to one of the following formulas (VII), (VIII), (IX), (X), (XI), (XII), (XIII), or (XIV): ## STR2 ## (VIII) wherein m, n, and o, which may be identical or different, represent an integer from 0 to 10; ) Formula (XIII) in which p, q, r, and s, which may be identical or different, represent an integer between 0 and 10; O (XIV) R8. Formula (XIV) in which R6, R7 and R8, which may be identical or different , representing a hydrogen atom or a hydroxyl group; - the compound (s) a) (corresponds) to the following formula (V-1): (V-1) OH Formula (V-1) in wherein R1, R2, R3 and R4 are as defined above with reference to formula (V); - the photocurable compound (s) a), in particular corresponding to formula (I) and or (V), is (are) present (s) at a total content greater than or equal to 1% by weight, relative to the weight of the total dry extract of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% to 15% by weight, relative to weight of the total dry extract of the composition; the compound (s) b) corresponds to the following formula (II): ## STR2 ## Formula (II) Formula (II) in which: R1, R2, R3, R4, R5 and R6, identical or different, representing a hydrogen atom or a C1-C10 alkyl chain, preferably a hydrogen atom or a methyl group, - k and I, identical or different, between 1 and 10, preferably equal to 2, - m between 1 and 100, preferably between 5 and 50, preferably between about 8 and 10, n between 1 and 10, preferably equal to 1, - X and Y, identical or different, representing a C 1 -C 20 alkyl or cycloalkyl group; the photocrosslinkable compound (s) b), in particular corresponding to formula (II), is (are) present at a total content greater than or equal to 10% by weight relative to the weight the total solids content of the composition, in particular ranging from 20% to 80% by weight, in particular ranging from 30% to 70% by weight, preferably ranging from 40% to 60% by weight, relative to the weight of the product; total dry extract of the composition; the compound (s) c) is (respondent) to the following formula (XV): Formula (XV) Formula (XV) in which: R1, R2, R3 and R4, which may be identical or different, represent a hydrogen atom or a C1-C10 alkyl chain, preferably a hydrogen atom or a methyl group, between 1 and 10, preferably equal to 2, - A representing a C1-C10 alkyl group, or a polyurethane comprising from 2 to 20 carbamate units; the compound (s) c), in particular corresponding to the formula (XV), is (are) present (s) at a total content greater than or equal to 1% by weight relative to the total weight of the dry extract of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% to 20% by weight, relative to the weight of the total dry extract of the composition; The composition comprises at least one film-forming polymer, preferably selected from the group consisting of poly (meth) acrylates, polysaccharides and derivatives, and their mixture, preferably their mixture; the film-forming polymer (s) comprises (include) at least one poly (meth) acrylate corresponding to the following formula (III): Formula (III) Formula (III) in which: R1, R2 and R3, which may be identical or different, representing a hydrogen atom or a C1-C10 alkyl group, R1 preferably representing a C4-C10 alkyl group, and R2 and R3 preferably representing a hydrogen atom or a methyl group, - x and y, identical or different, representing an integer between 1 and 100, z representing an integer between 0 and 100, n representing an integer between 1 and 1000; the film-forming polymer (s) comprises (include) at least one polysaccharide or polysaccharide derivative chosen from nitrocellulose and the ethers and esters of polysaccharides, especially of C 2 -C 4, in particular from cellulose acetate butyrates, cellulose acetopropionates, ethylcelluloses, ethylguars, and mixtures thereof, more preferably chosen from nitrocellulose; the film-forming polymer (s) is (are) present at a total content greater than or equal to 2% by weight relative to the total weight of the dry extract of the composition, in particular ranging from 5% to 30% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 10% to 25% by weight, relative to the weight of the total solids content of the composition; the composition comprises at least one volatile solvent, preferably at least one polar volatile solvent, advantageously chosen from the group consisting of C 3 -C 6 esters and ketones and their mixtures; the volatile solvent (s) is (are) present at a total content greater than or equal to 10% by weight relative to the total weight of the composition, in particular ranging from 20% to 50% relative to total weight of the composition; the composition comprises at least one photoinitiator, preferably the photoinitiator is chosen from the group consisting of α-hydroxyketones, α-aminoketones, aromatic ketones preferably associated with a hydrogen-donor compound, aromatic α-diketones and oxides. acylphosphine, and mixtures thereof, advantageously in the group consisting of acylphosphine oxides; the composition furthermore comprises at least one (meth) acrylate monomer, preferably distinct from the compounds a), b) and c); - the composition is transparent; The present invention also relates, according to a second aspect of the invention, to a method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false nails, comprising at least the following steps: A) application on a nail or false nail of a composition as defined above, by which is deposited a coating consisting of at least one layer of said photocurable composition, this coating being applied directly in contact with the nail or nail-nail, and B) exposure of the coated nail or false nail obtained at the end of step A) to light, UV or visible radiation.
[0004] The present invention relates more particularly to a method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false nails, comprising at least the following steps: A) application on a nail or a false nail of a first composition such as a nail varnish or a photocrosslinkable composition, by which a first coating consisting of at least one layer of said first composition is deposited, this first coating being applied directly to the contact with the nail or false nail, B) possibly exposure of the nail or coated false nail obtained at the end of step A) to light, UV or visible radiation, C) application on the first coating resulting from step A) and B) of a second composition as defined above, distinct from the first composition, by which a second coating consisting of at least one layer of said second composition is deposited; osition, D) exposure of the coated nail or false nail obtained at the end of step C) to light, UV or visible radiation.
[0005] In such a process, the second coating is preferably a topcoat, optionally free of coloring agent. The present invention relates more particularly to a method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false nails, comprising at least the following steps: A) application on a nail or false nail of a first composition as defined above, by which a first coating consisting of at least one layer of said photocurable composition is deposited, this first coating being applied directly in contact with the nail or the false nail, B) exposure of the nail or coated false nail obtained at the end of step A) to light, UV or visible radiation, C) application to the first coating resulting from step A ) and B) of a second composition, distinct from the first composition, by which a second coating consisting of at least one layer of said second composition is deposited, D) exposure of the coated nail or nail-nail obtained to Lily sue from step C) to a light, UV or visible radiation. In such a process, the second coating is preferably a topcoat, optionally free of coloring agent.
[0006] Dry extract A composition according to the invention advantageously comprises a solids content greater than or equal to 30%, in particular 40%, and advantageously less than or equal to 60%, in particular 50%. For the purpose of the present invention, the "dry matter content" denotes the content of non-volatile matter. The amount of dry extract (abbreviated as ES) of a composition according to the invention is measured by means of a commercial halogen desiccant "HALOGEN MOISTURE ANALYZER HR 73" from METTLER TOLEDO. The measurement is based on the weight loss of a sample dried by halogen heating and thus represents the percentage of residual material once the volatiles have evaporated. The measurement protocol is as follows: about 2 g of the composition, hereinafter the sample, is spread on a metal cup. The sample is photocrosslinked under a stream of nitrogen (to prevent the oxygen in the air from inhibiting the crosslinking on the surface of the sample). The metal cup is then introduced into the halogen desiccant mentioned above. The sample is then subjected to a temperature of 105 ° C until a constant weight is obtained. The wet mass of the sample, corresponding to its initial mass before crosslinking, and the dry mass of the sample, corresponding to its mass after crosslinking and halogen heating, are measured by means of a precision balance. The experimental error related to the measurement is of the order of plus or minus 2%.
[0007] The content of dry extract is calculated as follows: Dry extract content (expressed in% by weight) = 100 × (Dry mass / Wet mass). Physiologically acceptable medium The cosmetic compositions according to the invention comprise a physiologically acceptable medium. By "physiologically acceptable medium" is meant a medium that is particularly suitable for applying a composition of the invention to keratin materials. The physiologically acceptable medium is generally adapted to the nature of the medium to which the composition is to be applied, as well as to the appearance under which the composition is to be packaged. Photocrosslinkable Compounds A composition in accordance with the present invention comprises at least the photo-crosslinkable compounds a), b) and c). In the context of the present invention, the term "photocrosslinkable compounds" denotes organic compounds capable of crosslinking under the action of light radiation, resulting in a crosslinked polymeric network. The photocrosslinkable compounds preferably comprise at least one (ALK) acrylate function, ie at least one H2C = C (R) -C (O) -O- function, with R preferably equal to H or ALK, it being understood that ALK represents an alkyl group in 0106, preferably in C1-C2, more preferably in C1 such that CH3, preferably R being equal to CH3.
[0008] Photocurable compound (s) a) The compositions according to the invention comprise at least one photocrosslinkable compound a) or a mixture of photocurable compound (s) a). The photocrosslinkable compound (s) a) are defined by the presence of at least one carboxylic acid function, namely a -COOH function, and at least one acrylate functional group (ALK), namely H 2 C functions. = C (R) -C (O) -O-, with R preferably equal to H or ALK, it being understood that ALK represents a C1-C6, preferably C1-C2 alkyl group, more preferably C1 such that CH3, preferably R being equal to CH3. Advantageously, the photocrosslinkable compound (s) a) comprises (include) at least one carboxylic acid function and at least one (meth) acrylate function. Advantageously, the photocrosslinkable compound (s) a) comprises (include) at least one carboxylic acid function and at least two (meth) acrylate functional groups. Preferably, the photo-crosslinkable compound (s) a) comprises (include) at least two carboxylic acid functions and at least two (meth) acrylate functions, preferably methacrylates. The photocrosslinkable compound (s) (a) is (are) preferably present in a total content greater than or equal to 1% by weight, based on the weight of the total dry extract of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% to 15% by weight, relative to the weight of the total dry extract of the composition. According to a first embodiment of the invention, the photocurable compound (s) a) comprise at least one compound corresponding to the following formula (I): ## STR2 ## Formula (I) Formula (I) ) in which: R1, R2, R3, which may be identical or different, representing a hydrogen atom, a C1-C10 alkyl group, preferably C1, preferably R1 being a methyl, preferably R2 and R3 being a hydrogen atom, - n representing an integer between 1 and 10, preferably equal to 2, - the bond between a and [3 carbonyloxy is a single bond, a double bond or is a bond included in a (hetero) a ring comprising from 5 to 7 carbon atoms, preferably 6 carbon atoms, (hetero) ring which may be aromatic or non-aromatic, preferably aromatic, more preferably aryl, such as phenyl. According to a particular embodiment, the photocurable compound (s) a) correspond to the formula (la): ## STR2 ## Formula (la) Formula (la) in which: R1, R2, R3 , identical or different, representing a hydrogen atom, a C 1 -C 10 alkyl group, preferably C 1, preferably R 1 being methyl, preferably R 2 and R 3 being a hydrogen atom, - n representing a whole number between 1 and 10, preferably 2. According to one preferred embodiment, the photocurable compound (s) a) have the formula (Ib): ## STR2 ## Formula (Ib) Formula (Ib) in which: - R1, R2, R3, which may be identical or different, representing a hydrogen atom, a C1-C10 alkyl, preferably C1-alkyl group, preferably R1 being a methyl, preferably R2 and R3 being a hydrogen atom, - n representing an integer between 1 and 10, preferably equal to 2. - the photorescribed compound (s) culable (s) a) correspond to formula (1c): ## STR2 ## Formula (Ic) Formula (Ic) in which: R1, R2, R3, identical or different, representing a hydrogen atom, an alkyl group C 1 -C 10, preferably C 1, preferably R 1 being methyl, preferably R 2 and R 3 being a hydrogen atom, n being an integer from 1 to 10, preferably 2; According to a particularly preferred embodiment, the photocrosslinkable compound (s) a) is (are) chosen from compounds of formula (Ia), (Ib), (Ic) such as above. defined, and their mixture. Preferably, the photocrosslinkable compound (s) of formula (I) is (are) chosen from methacryloyloxyethyl maleate, methacryloyloxyethyl succinate, and methacryloyloxyethyl phthalate. Preferably, the compound (s) comprise at least methacryloyloxyethyl maleate, bearing the INCI name HEMA MALEATE, and the name Chemical / IU PAC 2-Butenedioic Acid (2Z) -, Mono [2-Methyl-1-Oxo] Propenyl) Oxy] Ethyl] Ester.
[0009] The photocrosslinkable compound (s) a) of formula (I), more preferably methacryloyloxyethyl maleate, is (are) preferably present at a total content of greater than or equal to 1% by weight, by relative to the weight of the total solids content of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% to 15% by weight, relative to the weight of the total solids content of the composition. According to a second embodiment of the invention, the photocurable compound (s) a) comprises (include) at least one photocrosslinkable compound corresponding to the following formula (V): ## STR2 ## Wherein R 1 and R 2, which may be identical or different, represent a hydrogen atom, or a methyl group, or a group of formula (II) below: O / R 5 (VI) R 5 representing a hydrogen atom or a methyl group, preferably R 1 and R 2 representing a hydrogen atom. - R3 and R4, identical or different, represent a hydrogen atom or a methyl group; X represents a radical corresponding to one of the following formulas (VII), (VIII), (IX), (X), (XI), (XII), (XIII), or (XIV): HO (VII) Formula (XII) wherein m, n, and o, which may be identical or different, represent an integer from 0 to 10; Formula (XIII) wherein p, q, r, and s, which may be identical or different, represent an integer from 0 to 10; Embedded image in which R 6, R 7 and R 8, which may be identical or different, represent a hydrogen atom or a hydroxyl group. Preferably, the compound (s) a) is (responding) to the following formula (V-1): (V-1) OH Formula (V-1) wherein R1, R2, R3 and R4 being as defined above in formula (V). According to one embodiment, the compounds a) correspond to the formula (V) or (V-1) as defined above, in which R3 and R4 are methyl groups.
[0010] According to one embodiment, the compounds a) correspond to the formula (V) or (V-1) as defined above, in which R1 and R2, identical or different, represent a group of formula (VI-1) following: 0 (VI-1) Preferably, the photocurable compound (s) a) responds (responds) to the following formula (V-2): 20 O (V-2) The (S) photocrosslinkable compound (s) a), in particular having the formula (V), is (are) preferably present in a total content greater than or equal to 1% by weight, relative to the weight of the total dry extract of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% to 15% by weight, relative to the weight of the total dry extract of the composition. According to a third embodiment, a composition according to the invention comprises a mixture of photocrosslinkable compounds corresponding to formula (I) and to formula (V). Photocurable compound (s) b) A composition according to the invention comprises at least one photocrosslinkable compound b).
[0011] They may comprise a single photocurable compound b) or a mixture of several photocrosslinkable compounds b), preferably a single photocurable compound b). The photocrosslinkable compound (s) b) comprise at least one poly (urethane) poly (ALK) acrylate compound comprising a (poly) oxyalkylene unit. In general, the term "compound (poly) urethane poly (ALK) acrylate" means any compound comprising at least one urethane function -O-O (O) NH-, and comprising several functions (ALK) acrylate of formula H 2 C = C (R) -C (O) -O-, with R preferably equal to H or ALK, it being understood that ALK represents a C 1 -C 6 alkyl group, preferably C 1 -C 2, more preferably C 1, such as CH 3, preferably R being equal to CH3. The "urethane" function is also called the "carbamate" function. Preferably, the photocurable compound (s) (b) comprise several urethane or carbamate functions.
[0012] As a poly (urethane) poly (ALK) acrylate compound, poly (ALK) acrylate polyurethane compounds are preferred, especially di (ALK) acrylate polyurethane compounds, in particular di (meth) acrylate polyurethane compounds, more particularly compounds polyurethane dimethacrylates. Thus, the term "poly (meth) acrylate" denotes a compound comprising at least two methacrylate functions, or at least two acrylate functions, or at least one methacrylate function and at least one acrylate function, preferably at least two methacrylate functions. Advantageously, the average number of (meth) acrylate functional groups borne by the photocrosslinkable poly (urethane (meth) acrylate compound (s) intended to form, after crosslinking, a crosslinked polymeric network, is greater than or equal to 2 , for example between 2 and 6, better between 2 and 4, more preferably is 2. Preferably, the (the) photocurable compound (s) b) comprises (include) therefore at least one polyurethane compound dimethacrylate having a plurality of urethane functions -O-O (O) -NI-1, in particular at least two urethane functions, and a plurality of methacrylate functions of formula H 2 C = C (CH 3) -C (O) -O- , in particular at least two methacrylate functions. By "(poly) oxyalkylene" is meant a divalent group (poly) alkyleneoxy whose alkylene group is linear or branched and contains from 1 to 6 carbon atoms, the alkylene group being optionally substituted by one or more group (s) hydroxy, preferably being unsubstituted as corresponds to - [CH2] 2-0- or - O- [CH2] 2-.
[0013] By "(poly) urethane poly (ALK) acrylate compound comprising a (poly) oxyalkylene" unit, it is thus meant that the photocurable compound (s) b) comprises (include) at least one divalent group (poly ) oxyalkylene C1-C6, preferably O2, having from 1 to 100 alkyleneoxy units, in particular from 5 to 50 alkylene-oxy units, and more particularly from 8 to 10 alkylene-oxy units. Preferably, these (poly) oxyalkylenated groups are polyoxyethylene groups. The photocrosslinkable compound (s) (b) preferably have the following formula (II): ## STR2 ## Formula (II) Formula (II) in which which: R1, R2, R3, R4, R5 and R6, identical or different, representing a hydrogen atom or a C1-C10 alkyl chain, preferably a hydrogen atom or a methyl group, and I, identical or different between 1 and 10, preferably equal to 2, - m between 1 and 100, preferably between 5 and 50, preferably between about 8 and 10, n between 1 and 10, preferably equal to 1, - X and Y, identical or different, representing a C 1 -C 20 alkyl or cycloalkyl group. This (these) photocrosslinkable compound (s) (b), in particular of formula (II), advantageously has a molecular mass greater than or equal to 1000 g / mol, in particular ranging from 1000 to 5000 g / mol. preferably from 1000 to 3000 g / mol. The photocrosslinkable compound (s) b), in particular corresponding to formula (II), is (are) present at a total content greater than or equal to 10% by weight relative to the weight of the total dry extract of the composition, in particular ranging from 20% to 80% by weight, especially ranging from 30% to 70% by weight, preferably ranging from 40% to 60% by weight, relative to the weight of the total dry extract of the composition.
[0014] Photocurable compound (s) A composition according to the invention comprises at least one photocrosslinkable compound b). They may comprise a single photocurable compound b) or a mixture of several photocrosslinkable compounds b), preferably a single photocurable compound b). The photocrosslinkable compound (s) (b) comprise at least one (poly) urethane poly (ALK) acrylate compound, preferably free of (poly) oxyalkylene units.
[0015] In general, the term "compound (poly) urethane poly (ALK) acrylate" means any compound comprising at least one urethane function -O-O (O) NH-, and comprising several functions (ALK) acrylate of formula H 2 C = C (R) -C (O) -O-, with R preferably equal to H or ALK, it being understood that ALK represents a C 1 -C 6 alkyl group, preferably C 1 -C 2, more preferably C 1, such as CH 3, preferably R being equal to CH3. The "urethane" function is also called the "carbamate" function. Preferably, the photocurable compound (s) (b) comprise several urethane or carbamate functions. As a poly (urethane) poly (ALK) acrylate compound, poly (ALK) acrylate polyurethane compounds are preferred, especially di (ALK) acrylate polyurethane compounds, in particular di (meth) acrylate polyurethane compounds, more particularly compounds polyurethane dimethacrylates. Thus, the term "poly (meth) acrylate" denotes a compound comprising at least two methacrylate functions, or at least two acrylate functions, or at least one methacrylate function and at least one acrylate function, preferably at least two methacrylate functions. Advantageously, the average number of (meth) acrylate functional groups borne by the photocrosslinkable poly (urethane (meth) acrylate compound (s) intended to form, after crosslinking, a crosslinked polymeric network, is greater than or equal to 2 , for example between 2 and 6, better between 2 and 4, more preferably is 2. Preferably, the (the) photocurable compound (s) b) comprises (include) therefore at least one polyurethane compound dimethacrylate having a plurality of urethane functions -O-C (O) -NH-, in particular at least two urethane functions, and a plurality of methacrylate functions of formula H 2 C = C (CH 3) -C (O) -O-, in in particular at least two methacrylate functions.
[0016] Preferably, the compound (s) c) corresponds to the following formula (XV): ## STR2 ## Formula (XV) Formula (XV) in which: R1, R2, R3, and R4, which may be identical or different, representing a hydrogen atom or a C1-C10 alkyl chain, preferably a hydrogen atom or a methyl group, ranging from 1 to 10, preferably equal to 2, -A; representing a C 1 -C 10 alkyl group, or a polyurethane comprising from 2 to 20 carbamate units. (The) compound (s) c), in particular corresponding to formula (XV), is (are) present (s) to a total content greater than or equal to 1% by weight relative to the total weight of the extract dry composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% to 20% by weight, relative to the weight of the extract total dry of the composition. The photocrosslinkable compound (s) a), the photocrosslinkable compound (s) b), the photocurable compound (s) c), are preferably present at a respective total content such that they represent at least 50% by weight of the total dry extract of the composition, preferably 55 to 80% of the total dry extract of the composition. The photocrosslinkable compound (s) a), the photocrosslinkable compound (s) b), the photocurable compound (s) c), are preferably present at a respective total content such that they represent at least 50% by weight relative to the total weight of the (meth) acrylate compounds of the composition, preferably from 65% to 90% by weight, relative to the total weight of the compounds (meth ) acrylates of the composition. The photocrosslinkable compound (s) a), the photocrosslinkable compound (s) b), the photocurable compound (s) c), are preferably present at a respective total content such as the weight ratio of the photocurable compound (s) a), the photocurable compound (s) b) and the photocurable compound (s) (s) ) b) is 0.075 - 0.225 / 0.6 - 0.85 / 0.075 - 0.3. Film-forming polymer (s) The compositions according to the invention advantageously also comprise at least one film-forming polymer. They may comprise a single film-forming polymer or a mixture of several film-forming polymers, preferably a mixture of several film-forming polymers.
[0017] The film-forming polymer (s) has (a) function to impart resistance to the photo-crosslinkable composition and to promote the removal of make-up. Preferably, the compositions according to the invention comprise at least two film-forming polymers. The film-forming polymer (s) is (are) present at a total content greater than or equal to 2% by weight relative to the total weight of the solids content of the composition, in particular from 5% to 30% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 10% to 25% by weight, relative to the weight of the total solids content of the composition. For the purposes of the present invention, the term "film-forming polymer" denotes a polymer capable of forming on its own (ie, in the absence of an auxiliary film-forming agent or of an external stimulus, for example of the UV type), a isolable film, especially continuous and adherent, on a support, especially on the nails. This film-forming polymer may be chosen from the group consisting of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and their mixtures. A film-forming polymer that is suitable for the invention may be chosen from at least one poly (meth) acrylate compound, in particular from homopolymers and (meth) acrylate copolymers, preferably from (meth) acrylate copolymers. The poly (meth) acrylate compound (s), in particular the (meth) acrylate copolymer (s) present in the composition, is (are) advantageously capable of being obtained ( s) by: i) polymerizing at least one methyl methacrylate monomer (MMA) and at least one acrylic or methacrylic acid monomer (AA or MAA), or ii) polymerizing at least one monomer of methyl methacrylate (MMA), of at least one monomer having a glass transition temperature of less than 30 ° C such as butyl methacrylate (BMA), butyl acrylate (BA), or 2-ethylhexyl acrylate (2-EHA), and optionally at least one acrylic acid (AA) monomer or methacrylic acid (MAA) monomer. A composition according to the invention preferably comprises at least one poly (meth) acrylate film-forming polymer of type ii) obtained by polymerization of at least one methyl methacrylate monomer (MMA), at least one transition temperature monomer. vitreous material below 30 ° C such as butyl methacrylate (BMA), butyl acrylate (BA), or 2-ethylhexyl acrylate (2-EHA), and optionally at least one acid monomer acrylic (AA) or methacrylic acid (MAA). Such a poly (meth) acrylate-type film-forming polymer of type ii) preferably corresponds to the following formula (III): Formula (III) Formula (III) in which: R1, R2 and R3, which may be identical or different, represent an atom of hydrogen or a C1-C10 alkyl group, where R1 is preferably a C4-C10 alkyl group, and R2 and R3 preferably represent a hydrogen atom or a methyl group, - x and y, the same or different, representing an integer between 1 and 100, z representing an integer between 0 and 100, n representing an integer between 1 and 1000. Preferably, a composition according to the invention comprises at least one film-forming polymer. chosen from at least one polyacrylate compound of formula (III).
[0018] As a variant or preferably additionally, a film-forming polymer that is suitable for the invention may be chosen from polysaccharides and polysaccharide derivatives, such as cellulose or guar gum derivatives. A preferred polysaccharide derivative suitable for the invention may be nitrocellulose or a polysaccharide ester or alkyl ether. By "polysaccharide ester or alkyl ether" is meant a polysaccharide formed of repeating units comprising at least two identical or different rings and having a degree of substitution per saccharide unit of between 1.9 and 3, preferably of between 2.2 and 2.9, and more particularly between 2.4 and 2.8. By substitution is meant the functionalization of the hydroxyl groups as ester and / or alkyl ether functions, and / or the functionalization of the carboxylic groups as ester functions.
[0019] In other words, it may be a polysaccharide partially or totally substituted with ester and / or alkyl ether groups. Preferably, the hydroxyl groups may be substituted by ester and / or alkyl ether C2-04 functions. Mention may in particular be made of cellulose esters (such as cellulose acetobutyrates or cellulose acetopropianates), cellulose alkylethers (such as ethylcelluloses), and ethylguars. A film-forming polymer that is suitable for the invention may be chosen from synthetic polymers such as polyurethanes, acrylic polymers, vinyl polymers, polyvinyl butyrals, alkyd resins and ketone / aldehyde resins, resins derived from condensation products of aldehydes, such as arylsulfonamide formaldehyde resins such as toluene sulfonamide formaldehyde resin, epoxy aryl-sulfonamide resins or ethyl tosylamide resins. A film-forming polymer that is suitable for the invention may also be chosen from polymers of natural origin, such as plant resins such as dammars, elemi, copals, benzoin; gums such as shellac, sandalwood gum and putty gum. As film-forming polymer, the toluene sulfonamide formaldehyde resins "Ketjentflex MS80" from the company Akzo or "Santolite MHP", "Santolite MS 80" from the company Fontronno or "Resimpol 80" from the company Pan Americana, the alkyd resin, can especially be used. "BECKOSOL ODE 230-70-E" from the company DAINIPPON, the acrylic resin "ACRYLOID B66" of the company ROHM & HAAS, the polyurethane resin "TRIXENE PR 4127" from BAXENDEN, the acetophenone / formaldehyde resin marketed under the reference Synthetic Resin SK by Degussa. According to a particular preferred embodiment, the film-forming polymer is chosen from the group consisting of polysaccharides and polysaccharide derivatives, preferably from nitrocellulose and ethers and esters of polysaccharides, especially from C 2 -C 4, and more preferentially from acetobutyrates. cellulose, cellulose acetopropionates, ethylcelluloses, ethylguars, and mixtures thereof. According to an advantageous embodiment, the film-forming polymer is chosen from the group consisting of nitrocellulose, cellulose acetopropionate, cellulose acetate butyrate, and (meth) acrylate homopolymers and copolymers, and mixtures thereof. According to an advantageous embodiment, the compositions of the invention comprise at least one film-forming polymer chosen from nitrocellulose. According to a preferred embodiment of the invention, a composition according to the invention comprises: from 4 to 10% by weight of film-forming polymer (s) poly (meth) acrylate, in particular of type (ii), preferably, preferably corresponding to formula (III), relative to the weight of the total solids content of the composition, from 2 to 7% by weight of polysaccharides and polysaccharide derivatives, preferably nitrocellulose, relative to the weight of the total dry extract of the composition. According to this particular embodiment, the ratio between the weight of the film-forming polymer (s) chosen from the group consisting of polysaccharides and polysaccharide derivatives, in particular the weight of nitrocellulose, on the weight of the photocrosslinkable compounds, in particular the sum of the respective weight of the photocurable compounds a), b), c) is less than or equal to 1, and preferably between 0.05 and 0.5. According to an advantageous embodiment, the ratio between the total weight of film-forming polymer (s), in particular chosen from the group consisting of poly (meth) acrylate compounds, in particular of formula (III), and polysaccharides and polysaccharide derivatives, in particular nitrocellulose, on the weight of the photocrosslinkable compounds, in particular the sum of the respective weights of the photocrosslinkable compounds a), b), c), and optionally of one or more monomers (s) ( meth) acrylate (s), such as a tetrahydrofurfurylmethacrylate compound, is less than or equal to 1, and preferably between 0.05 and 0.5.
[0020] Volatile solvent (s) The compositions according to the invention also advantageously comprise at least one volatile solvent. They may therefore comprise a single solvent or a mixture of several volatile solvents, preferably a mixture of several volatile solvents.
[0021] The volatile solvent (s) is (are) present at a total content greater than or equal to 10% by weight relative to the total weight of the composition, in particular ranging from 20 to 50% by weight. total of the composition. For the purposes of the invention, the term "volatile solvent" is intended to mean a solvent capable of evaporating on contact with keratin materials in less than one hour at ambient temperature and atmospheric pressure. The volatile solvent (s) of the invention are liquid solvents at ambient temperature, having a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 50 Pa to 40,000 Pa (0.375 at 300 mmHg), in particular ranging from 100 Pa to 26664 Pa (0.75 to 200 mmHg), and more particularly ranging from 1000 Pa to 13332 Pa (7.5 to 100 mmHg). Such solvents are intended in particular to thin and reduce the solids content of the composition. The solvents are preferably chosen from polar solvents.
[0022] For the purposes of the present invention, the term "polar solvent" is intended to mean a solvent or an oil whose solubility parameter calculated beyond its melting point 6a is other than 0 (J / cm 3)%. The definition and calculation of the solubility parameters in the HANSEN three-dimensional solubility space are described in the article by C. M. Hansen: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967). According to this Hansen space: - 8D characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks; - 8p characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles; - 3h characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type, etc.); and - 6a is determined by the equation: 8a = (81) 2 + 6h2)%.
[0023] The parameters 3p, 3h, 8D and 6a are expressed in (J / cm3)%. In particular, by "polar" solvent is meant a solvent whose chemical structure is formed essentially or even consisting of carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen atom. , nitrogen, silicon or phosphorus.
[0024] Preferably, this polar volatile solvent is selected from the group consisting of C3-C6 esters and ketones and mixtures thereof.
[0025] As polar volatile solvent, mention may especially be made of acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and alkyl acetates in which the alkyl group comprises from 2 to 5 carbon atoms, such as methyl acetate. ethyl acetate, propyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and tert-butyl acetate. butyl. Preferably, the polar volatile solvent is selected from the group consisting of ethyl acetate, propyl acetate, such as n-propyl or isopropyl, n-butyl acetate or isobutyl or tert-butyl, isopropanol, and their mixture (s).
[0026] According to a preferred embodiment, the solvent is a mixture of butyl acetate and ethyl acetate. Butyl acetate and ethyl acetate are preferably present at a respective content ranging respectively from 2 to 10% by weight and from 15 to 25% by weight, relative to the total weight of the composition.
[0027] Photo-initiator (s) The compositions according to the invention also advantageously comprise at least one photoinitiator. They may comprise a single photoinitiator or a mixture of several photoinitiators, preferably a single photoinitiator. The photoinitiators that can be used according to the present invention are known in the art and are described, for example, in "Photoinitiators in the crosslinking of coatings", G. Li Bassi, Double Liaison - Chemistry of Paints, No. 361, November 1985, p. 34-41; "Industrial applications of photoinduced polymerization", Henri Strub, L'Actualité Chimique, February 2000, p.5-13; and "Photopolymers: Theoretical Considerations and Catch Response", Marc, J.M. Abadie, Double Liaison - Paint Chemistry, No. 435-436, 1992, p.28-34. These photoinitiators include: α-hydroxyketones, sold for example under the names DAROCU RO 1173 and 4265, IRGACURE® 184, 2959, and 500 by the company BASF, and ADDITOLO CPK by the company CYTEC, the a-aminoketones, marketed for example under the names IRGACURE® 907 and 369 by BASF, - the aromatic ketones marketed for example under the name Esacure® TZT by LAMBERTI. Mention may also be made of thioxanthones marketed for example under the name ESACURE® ITX by LAMBERTI, and quinones. These aromatic ketones most often require the presence of a hydrogen donor compound such as tertiary amines and especially alkanolamines. It is possible to mention the tertiary amine ESACURE® EDB sold by the company LAMBERTI. the α-dicarbonyl derivatives, the most common representative of which is benzyldimethylketal, marketed under the name IRGACURE® 651 by BASF. Other commercial products are marketed by LAMBERTI under the name ESACURE® KB1, and acylphosphine oxides, such as, for example, bis-acylphosphine oxides (BAPO) sold for example under the names IRGACURE® 819, 1700. , and 1800, DAROCUR® 4265, LUCIRIN® TPO, and LUCIRIN® TPO-L by BASF. Preferably, the photoinitiator is chosen from the group consisting of α-hydroxyketones, α-aminoketones, aromatic ketones preferably associated with a hydrogen-donor compound, aromatic α-diketones and acylphosphine oxides, and their mixtures. An acylphosphine oxide is preferably used in the photocurable composition of the invention. As a photoinitiator, mention may be made of LUCIRIN® TPO-L (BASF).
[0028] The total content of photoinitiator (s) depends on a large number of factors such as, for example, the reactivity of the various components of the mixture, the presence of coloring agent (s), the intensity of the light source or the exposure time. To obtain the desired properties, the (or) photoinitiator (s) is (are) preferably present (s) in a total content greater than or equal to 0.1% by weight relative to the total weight of the photocurable composition, preferably ranging from 0.2 to 5% by weight relative to the total weight of the photocurable composition. Other constituents According to a particular embodiment, a composition according to the invention may also comprise one or more (meth) acrylate monomer (s), such as a tetrahydrofurfurylmethacrylate compound. In particular this (these) monomer (s) (meth) acrylate (s) may (may) be present (s) in a second layer applied to the base layer to improve strength and mechanical property. Such a monomer may however be present in a base layer according to the invention. This (these) monomer (s) is (are) preferably present (s) at a content less than or equal to 10% by weight, relative to the total weight of the solids content of the composition. The compositions according to the invention may further comprise one or more stabilizers.
[0029] The compositions according to the invention may also contain adjuvants, or additives, chosen in particular from coloring agents such as pigments, plasticizers, coalescing agents, preserving agents, thickening agents, perfumes, cosmetic active agents. for nail care, spreading agents, anti-foaming agents, and dispersing agents.
[0030] Of course those skilled in the art will take care to choose these optional additives and additives so that the advantageous properties of the composition according to the invention are not, or not substantially impaired by the addition envisaged. When the composition comprises coloring agents, it is particularly appropriate to adapt the absorption spectrum of the coloring agents used to that of the photoinitiators, or conversely the absorption spectrum of the photoinitiators to that of the coloring agents used, in order to avoid that these two types of compounds absorb light at the same wavelengths. Indeed, the absorption of light by the coloring agents would make the photoinitiators present beyond a certain depth of the coating almost totally ineffective.
[0031] Preferably, the composition of the invention is transparent. As used herein, the term transparent means that the composition has a HAZEBYK index of less than 5 as measured with a KYKHAZEGLOSS type gloss meter. According to one embodiment, the composition of the invention further comprises a coloring agent chosen from the group consisting of soluble dyes, pigments, pearlescent agents and flakes. The coloring agent (s) may be present in a total content greater than or equal to 0.1% by weight relative to the total weight of the layer, preferably ranging from 1 to 5%, advantageously from 0.2 to 1% by weight relative to the total weight of the composition. By "soluble dyes" are meant organic, inorganic or organometallic compounds, soluble in the composition of the invention and intended to color said composition. The dyes are, for example, Sudan Red, DC Red 17, DC Green 6, 3-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5 , and yellow quinoline.
[0032] By "pigments" it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the composition of the invention and intended to color said composition. By "nacres", it is necessary to understand particles of any iridescent form, in particular produced by certain shellfish in their shell or else synthesized. The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxides, and oxides of zinc, iron (black, yellow or red) or chromium, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.
[0033] Mention may also be made of effect pigments such as particles comprising an organic or inorganic substrate, natural or synthetic, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics, aluminas and coated or not with metallic substances. such as aluminum, gold, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide, mineral or organic pigments and mixtures thereof. The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated with, inter alia, blue. ferric oxide or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It is also possible to use pigments with goniochromatic properties, in particular liquid crystal or multilayer. It is also possible to use optical brighteners or fibers optionally coated with optical brighteners. The compositions according to the invention may also comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. % in weight. By "fillers" is meant particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or the texture of the composition. The fillers can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (nylon) powders (Orgasol® from Atochem), poly-β-alanine and polyethylene, tetrafluoroethylene polymer powders (Teflon). ®), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as ExpanceIC) (Nobel Industrie), copolymers of acrylic acid (Polytrap® from Dow Corning) and silicone resin microbeads (Toshiba Tospearls®, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
[0034] Uses According to one embodiment, the compositions of the invention are intended to be applied to the nails and / or false nails, preferably for the makeup and / or care of the nails and / or false nails, more preferably for nail makeup and / or false nails.
[0035] In particular, the compositions according to the invention are intended to be used as photocurable nail polish. Preferably, the compositions according to the invention are intended to be applied directly to the nails and / or false nails as a base layer or coating. Such a base coating may optionally constitute a first coating for one or more subsequent coating (s). The present invention also relates to a method of makeup and / or care of the nails and / or false nails consisting of applying to a nail and / or a false nail a photocurable composition according to the invention. According to a particular embodiment, a method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false-nails, comprises at least the following steps: A) application on a nail or false nail of a composition according to the invention, by which is deposited a coating consisting of at least one layer of said photocurable composition, this coating being applied directly in contact with the nail or false -ongle, and B) exposure of the coated nail or false nail obtained at the end of step A) to light, UV or visible radiation. The radiation suitable for crosslinking the photocurable composition of the present invention has a wavelength of between 210 and 600 nm, preferably between 250 and 420 nm, preferably between 350 and 410 nm. We can also consider the use of lasers. In a preferred embodiment of the invention, use is made of an LED lamp, or a UV lamp and in particular a mercury vapor lamp, possibly doped with other elements, such as gallium, making it possible to modify the spectrum of emission of the light source.
[0036] The exposure time of the coating deposited on the radiation depends on various factors such as the chemical nature and the content of the reactive components or the desired crosslinking density. For nail polish, it will generally seek to obtain satisfactory results for an exposure time of between 10 seconds and 10 minutes, preferably between 30 seconds and 5 minutes. Such a method can implement a UV lamp with a power of approximately 36 W. Preferably, the thickness after drying of the photocurable composition coating deposited in step A) is less than or equal to 250 μm, preferably less than or equal to 250 μm. equal to 200 μm. At the end of the last crosslinking step, the coating deposited on the nail or the false nail may have a tacky layer on its surface requiring cleaning of the crosslinked coating using, for example, a solvent such as isopropanol. According to one embodiment, the method of the invention further comprises, before step B), a drying period of the coating deposited at the end of step A), the duration of which may vary from 10 seconds to 10 minutes, typically 30 seconds to 5 minutes. Said drying is generally carried out in air and at room temperature. A particular method according to the invention consists exclusively of a step A) and a step B) as defined above, possibly spaced apart from a drying period as defined above.
[0037] According to one embodiment, after the crosslinking step B), the coating deposited on the nail is covered with at least one colored composition and / or a finishing composition, also called "top-coat" according to the Anglo-Saxon terminology, these compositions being photocurable or not.
[0038] The crosslinked coating resulting from the crosslinking of step B) has a resistance over time, in terms of resistance to scaling and gloss, significant and especially at the scale of at least one week. It is thus resistant to water, friction and shock, and shows no significant wear or peeling within this time.
[0039] This coating also has an ability to solubilize or increase volume and therefore weight when it is brought into contact with a common make-up removal solvent. This ability to solubilize or swell, manifested by the crosslinked coating, is precisely advantageous for its removal when it is applied to the surface of a nail or false nail. Indeed, the coating can be easily removed by simple makeup removal with a conventional solvent. Thus, the composition of the invention is advantageously removable from solvents customary in the field of nail polish, and in particular by acetone and ethyl acetate, and mixtures thereof. The present invention also relates to a method for removing makeup from nails and / or false nails, comprising applying a make-up removal composition, such as a conventional solvent described above, to a coated nail or false nail. at least one layer obtained by crosslinking a layer of composition according to the invention, by which said crosslinked layer is removed. The first coating, or base coat, is preferably coated with a second coating. In particular, this second coating is chosen from a finishing coating or a colored coating. More particularly, the first coating may be coated with a colored coating as a second coating, and the second coating itself coated with a finishing coating as a third coating. Preferably, each coating consists of a respective photocurable composition and is photocrosslinked according to the conditions described above. According to a particular embodiment, a method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false-nails, comprises at least the following steps: A) application on a nail or false nail of a first composition according to the invention, by which is deposited a first coating consisting of at least one layer of said photocurable composition, the first coating being applied directly in contact with the nail or the false nail, and B) exposure of the coated nail or false nail obtained at the end of step A) to light, UV or visible radiation, C) application to the first coating resulting from the step A) and B) of a second composition, distinct from the first composition, by which a second coating consisting of at least one layer of said second composition is deposited, D) exposure of the nail or false nail coated at the end of step C) at a light, UV or visible radiation.
[0040] In such a process, the second coating is preferably a topcoat, optionally free of coloring agent. According to a particular embodiment, a method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false-nails, comprises at least the following steps: A) application on a nail or a false nail of a first composition such as a nail varnish or a photocrosslinkable composition, by which a first coating consisting of at least one layer of said first composition is deposited, this first coating being applied directly in contact with the nail or false nail, and B) optionally exposure of the nail or nail-coated nail obtained at the end of step A) to a light, UV or visible radiation, C) application on the first coating resulting from step A) and B) of a second composition according to the invention, distinct from the first composition, by which a second coating consisting of at least one layer of said second composition is deposited, D) expositio n of the coated nail or false nail obtained at the end of step C) to a light, UV or visible radiation, E) possibly applied to the second coating resulting from step C) and D) d a third composition, distinct from the first composition and the second composition, by which a third coating is deposited consisting of at least one layer of said third composition, F) exposure of the coated nail or nail-nail obtained at the outcome of step E) to a light radiation, UV or visible. In such a process, the second coating is preferably a colored layer comprising at least one coloring agent and the third coating is preferably a colorless agent-free topcoat.
[0041] According to a preferred embodiment, when a third coating of a third composition is applied, the second composition applied as the second coating comprises at least one coloring agent. According to a particularly preferred embodiment, the second coating corresponds to one or, preferably, to several colored layers, preferably identical, such as two, comprising at least one coloring agent, and the third coating is preferably a layer of finish, free of coloring agent.
[0042] According to a preferred embodiment, steps C) and D) are repeated a total of twice, the second composition being applied a first time and exposed to light, UV or visible radiation, then being applied a second time and exposed to a light radiation, UV or visible, preferably steps A) and B), as well as E) and F) are respectively implemented only once.
[0043] The present invention also relates to a kit comprising: - a photocurable cosmetic composition according to the invention, - an abrasive material having a particle size greater than or equal to 200, preferably less than 300, advantageously between 220 and 280, and - a LED lamp or UV lamp. The present invention also relates to a method of coating a nail and / or false nail, comprising the following steps: i) the friction of the surface of a nail or false nails with an abrasive material having a greater particle size or equal to 200, preferably less than 300, advantageously between 220 and 280, ii) the application of a photocurable cosmetic composition according to the invention to the surface of the nail or false nails which has been rubbed following step i), wherein a layer consisting of at least one layer of said composition according to the invention is deposited, iii) exposing the coated nail or false nails obtained following step ii) to a lamp LED or UV lamp, so that photocrosslinking is performed to obtain a crosslinked layer.
[0044] The friction step is performed for less than 10 seconds, preferably less than 5 seconds, for example for about 3 seconds.
[0045] The weight percentages given in this application can be likened to the percentage by weight of dry matter of the compounds used, unless the contrary is expressly mentioned.
[0046] The invention will be better understood on reading the description which follows, given solely by way of example. EXAMPLE According to a first exemplary embodiment, the following composition was prepared: Ingredients of the composition Content in% Methacryloyloxyethyl maleate 7.5 (HEMA MALEATE - ESSTECH, Inc.) Isophorone Urethane Dimethacrylate (X-851-1066 - ESSTECH, 10.5 Inc.) PEG-400 Urethane Dimethacrylate (X-726-0000 - ESSTECH, Inc.) TETRAHYDROFURFURYL METHACRYLATE 7 (X-958-7446 - ESSTECH, Inc.) METHYL METHACRYLATE (MMA) / 6.33 BUTYL METHACRYLATE (BMA) COPOLYMER (PARALOID) B 66 100% DOW CHEMICAL) Nitrocellulose 30% isopropyl alcohol (viscosity: E22 - 1 / 2s) 6.67 (IDYL E35 TX IPA 30% BERGERAC - SNPE) Ethyl acetate 21 Butyl acetate 6 Ethyl photoinitiator 2,4,6-trimethylbenzoylphenylphosphinate 4 (Lucirin TPO-L-BASF) Coloring agent 1 The ingredients of the composition are introduced into an opaque flask and placed under stirring in the absence of light with a laboratory mixer of the brand Rayneri until you get a mix e homogeneous. An aluminum foil will have been placed above the container to avoid evaporation of the solvents. On a nail previously frosted for less than 5 seconds using a file size 280, the composition described above was applied to said nail so as to form a base coat or base layer. After application, the nail is positioned under a 36W UV lamp for 3 minutes to crosslink the composition to form a film. The surface is cleaned with a cotton swab dipped in isopropanol to remove the sticky layer. In the two embodiments of the invention evaluated each comprising a base coating comprising a photocrosslinkable composition according to the invention, there is thus obtained a varnish having a good hold on the nail. To do this, the outfit was appreciated by simple observation at the naked eye after 14 days of its application. This outfit performance is achieved with a single unique composition to existing compositions on the market. Such a composition makes it possible to avoid the conventional invasive method of fixing a photocurable composition on the nails, by sanding the surface of the nail while retaining equivalent or better performance than the products currently on the market. In addition, the ingredients used in the compositions according to the invention make it possible to have, after photocrosslinking of the film, a content of extractable compounds comprising reactive (meth) acrylate functions, with potentially sensitizing effects, extremely low. The varnish can then be removed entirely after having been in contact with acetone for 15 minutes, again without any conventional invasive method using a metal tool, an electric sander, or an abrasive file rubbing against the surface of the nail made up to eliminate the composition. The gloss of the film obtained is good. Make-up removal easy. In the same way as previously described a second example of composition according to the present invention is prepared. Ingredients of the composition% PYROMELLITIC DIMETHACRYLATE (PMDM) content (X-865-0000, 6 ESSTECH, Inc.) Isophorone Urethane Dimethacrylate (X-851-1066 - ESSTECH, 10.5 Inc.) PEG-400 Urethane dimethacrylate (X-726 -0000 - ESSTECH, Inc.) TETRAHYDROFURFURYL METHACRYLATE 7 (X-958-7446 - ESSTECH, Inc.) METHYL METHACRYLATE METHACRYLATE (MMA) / 6.33 BUTYL METHACRYLATE (BMA) COPOLYMER (PARALOID B 66 100% DOW CHEMICAL) Nitrocellulose 30% isopropyl alcohol (viscosity: E22 - 1 / 2s) 6.67 (IDYL E35 TX IPA 30% BERGERAC - SNPE) Ethyl acetate 21 Butyl acetate 7.5 Photo-initiator ethyl-2,4,6-trimethylbenzoylphenylphosphinate 4 ( Lucirin TPO-L - BASF) Coloring agent 1 The same advantages as previously mentioned with reference to the preceding example are obtained with this composition.
[0047] Throughout the application, the wording "comprising a" or "comprising a" means "comprising at least one" or "comprising at least" one unless the contrary is specified.

权利要求:
Claims (20)
[0001]
REVENDICATIONS1. Photocurable cosmetic composition, in particular intended for the coating of a nail or false nail, and more particularly intended for the make-up of a nail or false nail, comprising, in a physiologically acceptable medium: at least a photocrosslinkable compound a) comprising at least one acrylate functional group (ALK) and at least one carboxylic acid functional group, at least one photocrosslinkable compound b) comprising at least one poly (urethane) poly (ALK) acrylate compound, preferably polyurethane di ( meth) acrylate, more preferably polyurethane dimethacrylate, the photocrosslinkable compound (s) b) comprising a (poly) oxyalkylene unit, in particular comprising a (poly) oxyethylene unit, preferably comprising from 1 to 100 oxyalkylene units, preferably from 5 to 50 oxyalkylene units, and preferably about 8 to 10 oxyalkylene units, - at least one photocrosslinkable compound c) comprising at least one compound (poly) ur thane poly (ALK) acrylate, preferably polyurethane di (meth) acrylate, more preferably polyurethane dimethacrylate, comprising at least two carbamate units obtained by reaction with at least one kind of diisocyanate Isophorone Diisocyanate (IPDI).
[0002]
2. Composition according to claim 1, in which the photocurable compound (s) comprises at least one photocrosslinkable compound corresponding to the following formula (I): Formula (I) Formula (I) in which: - R1, R2, R3, which may be identical or different, representing a hydrogen atom, a C1-C10 alkyl group, preferably C1, preferably R1 being a methyl, preferably R2 and R3; being a hydrogen atom, - n representing an integer between 1 and 10, preferably equal to 2, - the bond between a and [3 carbonyloxy is a single bond, a double bond or is a bond included in a (Hetero) ring comprising from 5 to 7 carbon atoms, preferably to 6 carbon atoms, (hetero) ring which may be aromatic or non aromatic, preferably aromatic, more preferably an aryl, such as a phenyl.
[0003]
3. Composition according to claim 1 or 2, wherein the photocurable compound (s) comprises at least one photocrosslinkable compound corresponding to the following formula (V): ## STR2 ## Wherein R 1 and R 2, which may be identical or different, represent a hydrogen atom, or a methyl group, or a group of the following formula (II): wherein R5 represents a hydrogen atom or a methyl group, preferably R1, R2, representing a hydrogen atom; - R3 and R4, identical or different, represent a hydrogen atom or a methyl group; X represents a radical corresponding to one of the following formulas (VII), (VIII), (IX), (X), (XI), (XII), (XIII), or (XIV): HO OH OH O (VIII) wherein m, n, and o, which may be identical or different, represent an integer between 0 and 10; HO OH (XIII) II) Formula (XIII) ) in which p, q, r, and s, which may be identical or different, represent an integer between 0 and 10; O (XIV) R8. Formula (XIV) in which R6, R7 and R8, which may be identical or different, represent an atom hydrogen or a hydroxyl group.
[0004]
The composition according to claim 3, wherein the compound (s) a) is (responding) to the following formula (V-1): (V-1) OH Formula (V-1) wherein R1, R2, R3 and R4 being as defined in claim 3.
[0005]
5. Composition according to any one of the preceding claims, in which the photocrosslinkable compound (s) a), in particular corresponding to formula (I) and / or (V), is (are) present. (s) at a total content greater than or equal to 1% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the extract total dry composition, in particular ranging from 5% to 15% by weight, relative to the weight of the total solids content of the composition.
[0006]
6. Composition according to any one of the preceding claims, in which the compound (s) b) (corresponds to) correspond to the following formula (II): ## STR2 ## Formula (II) Formula (II) in which: R1, R2, R3, R4, R5 and R6, identical or different, representing a hydrogen atom or a C1-C10 alkyl chain, preferably an atom hydrogen or a methyl group, k and I, identical or different, between 1 and 10, preferably between 2 and 1 m, preferably between 5 and 50, preferably between about 8 and 10, n between 1 and 10, preferably equal to 1, - X and Y, identical or different, representing a C 1 -C 20 alkyl or cycloalkyl group.
[0007]
7. Composition according to any one of the preceding claims, in which the photocrosslinkable compound (s) b), in particular corresponding to formula (II), is (are) present at a certain level. total greater than or equal to 10% by weight relative to the weight of the total solids content of the composition, in particular ranging from 20% to 80% by weight, in particular ranging from 30% to 70% by weight, preferably ranging from 40 to 60% by weight, relative to the weight of the total solids content of the composition.
[0008]
8. Composition according to any one of the preceding claims, in which the compound (s) c) responds (responds) to the following formula (XV): Formula (XV) Formula (XV) in which: R 2, R 3 and R 4, which may be identical or different, represent a hydrogen atom or a C 1 -C 10 alkyl chain, preferably a hydrogen atom or a methyl group, ranging from 1 to 10, preferably equal to 2, - A representing a C 1 -C 10 alkyl group, or a polyurethane comprising 2 to 20 carbamate units.
[0009]
9. Composition according to any one of the preceding claims, in which the compound (s) c), in particular corresponding to formula (XV), is (are) present at a total content greater than or equal to at 1% by weight relative to the total weight of the dry extract of the composition, in particular ranging from 2% to 20% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 5% at 20% by weight, relative to the weight of the total solids content of the composition. N R2 NH30
[0010]
10. Composition according to any one of the preceding claims, comprising at least one film-forming polymer, preferably chosen from the group consisting of poly (meth) acrylates, polysaccharides and derivatives, and their mixture, preferably their mixture.
[0011]
11. Composition according to any one of the preceding claims, in which the film-forming polymer (s) comprises (comprise) at least one poly (meth) acrylate corresponding to the following formula (III): Formula (III) Formula (III) in which: - R1, R2 and R3, which may be identical or different, represent a hydrogen atom or a C1-C10 alkyl group, R1 preferably representing a C4-C10 alkyl group, and R2 and R3 preferably representing a hydrogen atom or a methyl group, - x and y, identical or different, representing an integer between 1 and 100, - z representing an integer between 0 and 100, - n representing a whole number between 1 and 1000.
[0012]
12. Composition according to any one of the preceding claims, in which the film-forming polymer (s) comprises (comprise) at least one polysaccharide or polysaccharide derivative chosen from nitrocellulose and the ethers and esters of polysaccharides. in particular C2-C4, in particular from cellulose acetate butyrates, cellulose acetopropionates, ethylcelluloses, ethylguars, and mixtures thereof, more preferably chosen from nitrocellulose.
[0013]
13. The composition as claimed in any one of the preceding claims, in which the film-forming polymer (s) is (are) present at a total content of greater than or equal to 2%, by weight relative to the weight. total of the dry extract of the composition, in particular ranging from 5% to 30% by weight, relative to the weight of the total solids content of the composition, in particular ranging from 10% to 25% by weight, relative to weight of the total dry extract of the composition.
[0014]
14. Composition according to any one of the preceding claims, comprising at least one volatile solvent, preferably at least one polar volatile solvent advantageously chosen from the group consisting of esters and C3-C6 ketones and mixtures thereof.
[0015]
15. Composition according to any one of the preceding claims, in which the volatile solvent (s) is (are) present at a total content greater than or equal to 10% by weight relative to the total weight of the composition, in particular ranging from 20 to 50% relative to the total weight of the composition.
[0016]
16. Composition according to any one of the preceding claims, comprising at least one photoinitiator, preferably the photoinitiator is chosen from the group consisting of α-hydroxyketones, α-aminoketones, aromatic ketones preferably associated with a hydrogen donor compound. aromatic α-diketones and acylphosphine oxides, and mixtures thereof, advantageously in the group consisting of acylphosphine oxides.
[0017]
17. Composition according to any one of the preceding claims, further comprising at least one (meth) acrylate monomer.
[0018]
18. Composition according to any one of the preceding claims, characterized in that it is transparent.
[0019]
19. A method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false-nails, comprising at least the following steps: A) application on a fingernail or false nail of a composition according to any one of claims 1 to 18, by which is deposited a coating consisting of at least one layer of said photocurable composition, and B) exposure of the coated nail or false nail. at the end of step A) at a light, UV or visible radiation.
[0020]
20. A method of coating the nails and / or false nails, in particular makeup and / or care of the nails and / or false-nails, comprising at least the following steps: A) application on a fingernail or false nongle of a first composition by which a first coating consisting of at least one layer of said photocurable composition is deposited, this first coating being applied directly in contact with the nail or the false nail, and B) exposure of the nail or coated false nail obtained at the end of step A) to a light, UV or visible radiation, C) application to the first coating resulting from step A) and B) of a second composition according to any one of claims 1 to 18, distinct from the first composition, by which a second coating consisting of at least one layer of said second composition is deposited, D) exposure of the coated nail or false nail at the end of step C) to radiation bright, UV or visible.

类似技术:

---

公开号 | 公开日 | 专利标题

---

FR3013970A1|2015-06-05|PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE COATING AND METHODS OF APPLICATION

---

FR2998784A1|2014-06-06|HIGH-GLOSS PHOTORETICULAR COSMETIC COMPOSITION

---

FR3013975A1|2015-06-05|PHOTORETICULABLE VARNISH COMPOSITIONS AND METHODS OF APPLICATION

---

FR3013963A1|2015-06-05|PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE COATING AND METHODS OF APPLICATION

---

FR3013971A1|2015-06-05|PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE COATING AND METHODS OF APPLICATION

---

EP2928564B1|2018-05-23|Nail makeup method with photocrosslinkable varnish compositions

---

FR3013969A1|2015-06-05|PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE COATING AND METHODS OF APPLICATION

---

FR2998788A1|2014-06-06|NEW PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE LAYER

---

EP2928445B1|2018-01-31|Nail makeup method with photocrosslinkable varnish compositions

---

FR3013976A1|2015-06-05|PHOTORETICULABLE VARNISH COMPOSITIONS AS BASE COATING AND METHODS OF APPLICATION

---

LU100889B1|2020-01-27|Improved compositions as a makeup product applicable to the nails

---

FR2998797A1|2014-06-06|PHOTORETICULATE COSMETIC COMPOSITION NOT COLLAPSIBLE

---

FR2998796A1|2014-06-06|Making up and/or caring of nails and/or false nails, by applying flexible article comprising layer of film-forming polymer on nail and exposure of the nail to UV or visible light radiation by photocuring a photocurable compound

---

FR2998794A1|2014-06-06|Kit, useful for making up and/or caring for nails and/or false nails, comprises base composition comprising film-forming polymer, polish composition comprising block copolymer, and finishing composition comprising film-forming polymer

同族专利:

---

公开号 | 公开日

---

JP2016539154A|2016-12-15|

---

FR3013975B1|2015-11-20|

---

WO2015082336A1|2015-06-11|

---

EP3076934B1|2019-01-02|

---

ES2718702T3|2019-07-03|

---

US20160296455A1|2016-10-13|

---

EP3076934A1|2016-10-12|

---

CN105764481A|2016-07-13|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

EP0453628A2|1990-04-26|1991-10-30|Heraeus Kulzer GmbH|Process for preparing synthetic nail coatings|

---

US20120247496A1|2011-03-29|2012-10-04|Tammy Taylor|Fingernail and toenail base coat composition and method of applying the same|

---

DE102011102661A1|2011-05-27|2012-11-29|Costrade Beauty Consulting Gmbh|Easily removable nail polish composition|

---

GB2496990A|2011-11-24|2013-05-29|Chemence Ltd|Nail coating compositions|

---

US20130263875A1|2012-04-10|2013-10-10|Esschem, Inc.|Curable nail enhancements|

---

CA1306954C|1986-04-07|1992-09-01|Yosh Hokama|Hard durable nail polish and method of forming|

---

US5456905A|1988-08-23|1995-10-10|Ultraset Limited Partnership|Quick-drying nail coating method and composition|

---

FR2823105B1|2001-04-06|2004-03-12|Oreal|PHOTORETICULATING NAIL VARNISH FREE OF UNSATURATED MONOMERS|

---

US7375144B2|2005-06-16|2008-05-20|Eastman Chemical Company|Abrasion resistant coatings|

---

WO2012121704A1|2011-03-07|2012-09-13|Creative Nail Design, Inc.|Compositions and methods for uv-curable cosmetic nail coatings|

---

US8492454B2|2009-10-05|2013-07-23|Creative Nail Design, Inc.|Removable color layer for artificial nail coatings and methods therefore|

---

US8541482B2|2009-10-05|2013-09-24|Creative Nail Design, Inc.|Removable multilayer nail coating system and methods therefore|

---

FR2998784B1|2012-12-05|2015-02-13|Oreal|HIGH-GLOSS PHOTORETICULAR COSMETIC COMPOSITION|

---

WO2014157272A1|2013-03-29|2014-10-02|富士フイルム株式会社|Artificial nail composition, artificial nail, method for forming artificial nail, and nail art kit|US10004673B1|2017-02-08|2018-06-26|L'oreal|Hair treatment composition comprising Michael addition product and methods for treating hair|

---

JP6916512B2|2017-02-27|2021-08-11|ピアス株式会社|Artificial nail compositions, artificial nails, and artificial nail kits|

---

IT201800005494A1|2018-05-18|2018-08-18|Formulated for the cosmetic treatment of nails based on a UV photopolymerizable difunctional polyester urethane acrylate.|

---

JP6656662B1|2019-02-22|2020-03-04|里田化工株式会社|Artificial nail raw material composition, method for curing artificial nail raw material composition, method for producing artificial nail, and artificial nail|

法律状态:
2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |

---

2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |

---

2017-10-12| PLFP| Fee payment|Year of fee payment: 5 |

---

2018-10-11| PLFP| Fee payment|Year of fee payment: 6 |

---

2020-10-16| ST| Notification of lapse|Effective date: 20200905 |

优先权:

---

申请号 | 申请日 | 专利标题

---

FR1362084A|FR3013975B1|2013-12-04|2013-12-04|PHOTORETICULABLE VARNISH COMPOSITIONS AND METHODS OF APPLICATION|FR1362084A| FR3013975B1|2013-12-04|2013-12-04|PHOTORETICULABLE VARNISH COMPOSITIONS AND METHODS OF APPLICATION|

---

PCT/EP2014/075921| WO2015082336A1|2013-12-04|2014-11-28|Photo-crosslinkable varnish compositions and application methods|

---

US15/100,471| US20160296455A1|2013-12-04|2014-11-28|Photo-crosslinkable varnish compositions and application methods|

---

EP14803156.0A| EP3076934B1|2013-12-04|2014-11-28|Photo-crosslinkable varnish compositions and application methods|

---

JP2016536567A| JP2016539154A|2013-12-04|2014-11-28|Photocrosslinkable varnish composition and coating method|

---

CN201480065550.XA| CN105764481A|2013-12-04|2014-11-28|Photo-crosslinkable varnish compositions and application methods|

---

ES14803156T| ES2718702T3|2013-12-04|2014-11-28|Photoreticulable varnish compositions and application methods|