The present invention relates to a cosmetic product comprising at least two compositions that may be applied successively to the skin either of the face or of the body, to the lower and upper eyelids, to the lips and to the integuments, for instance the nails, the eyebrows, the eyelashes, or the hair. The present invention also relates to a process for making up the face and the body using these two compositions.
Each composition may be a foundation, a makeup rouge, an eyeshadow, a concealer product, a blusher, a loose or compacted powder, a lipstick, a lip balm, a lip gloss, a lip pencil, an eye pencil, a mascara, an eyeliner, a nail varnish, a body makeup product or a skin colouring product. One object of the present invention is to propose a composition that both has good staying power and is glossy.
Poor staying power may be reflected in particular by poor fastness of the colour and/or by poor staying power of the gloss. This poor staying power may be characterized by a modification of the colour (colour change or fading) generally following interaction with the sebum and/or sweat secreted by the skin in the case of a foundation or a makeup rouge, or interaction with saliva in the case of lipsticks, or a reduction in the gloss, in the case of a nail varnish. This obliges the user to reapply makeup very regularly,
which may constitute a loss of time.
To obtain transfer-resistant products with good staying power, volatile oils or polymers dispersed in a volatile solvent are often used. However, these products are not sufficiently glossy. A cosmetic product comprising two compositions has thus been envisaged, a first containing a polymer dispersed in a volatile solvent, onto which is applied a glossy and greasy second composition (FR-A-2 823 101) . The colour fastness of the makeup obtained with these compositions is good, but the disappearance of the second composition in the course of the day when it is worn results in a loss of the gloss desired by the consumer. The company Kose moreover proposed in its patent application J-A-O 5 221 829 the use of a gel based on perfluorinated materials, which is applied to a film of lipstick so as to prevent it from transferring onto other surfaces, the gel being incompatible with the film of lipstick. Mention may also be made of patent application WO-A-97/17057, which describes a method for increasing the staying power and transfer resistance properties, which consists in applying two compositions one over the other. The composition to be applied has a global Hildebrand solubility parameter of less than 8.5 (cal/cm3)1*, and the composition to be applied as topcoat must contain oils whose calculated partition
coefficient ClogP is at least equal to 13.
Patent US-A-β 001 374 proposes a makeup system, which consists in using an alcohol-soluble and water-insoluble resin, which may be applied as a basecoat or as a topcoat, and which has the advantage of not staining an object placed in contact with the makeup and of being resistant to water and to rubbing, while at the same time having a certain level of gloss. However, this composition contains a water-soluble alcohol, in particular ethanol, which is a compound of irritant nature that dries out the skin and more especially the lips, and which is particularly uncomfortable when the skin or the lips are damaged.
Patent application WO 02/067 877 describes a method for improving the aesthetic properties of a transfer-resistant composition, which consists in applying a second composition over a film of transfer- resistant composition. The second composition should not interact chemically with the transfer-resistant composition so as not to impair its cosmetic properties. Certain products described in the said document have an unpleasant odour and are tacky. Other products are not sufficiently glossy.
The aim of the present invention is to propose a novel route for formulating a cosmetic product, in particular a makeup product, of the type comprising two compositions to be applied successively
one after the other. This cosmetic product may advantageously have good gloss and/or staying power properties.
One subject of the present invention is thus a cosmetic product comprising a first composition and a second composition, the first composition containing at least one vinyl polymer containing units derived from carbosiloxane dendrimers, and the second composition, which is different from the first, comprising a cosmetically acceptable medium.
The product of the invention is in particular a makeup product for the skin, the nails or the hair.
The term "makeup product" means a product containing a colouring agent allowing the deposition of a colour onto a keratin material (the skin or the integuments) of a human being by applying to the keratin material products such as lipsticks, makeup rouges, eyeliners, foundations, self-tanning products or semi-permanent makeup products (tattoos) . The product according to the invention comprises at least two cosmetically acceptable compositions packaged separately or together in the same packaging article or in at least two separate packaging articles. Preferably, these compositions are packaged separately and advantageously in separate packaging articles.
The subject of the present invention is thus, in particular, a cosmetic makeup product in the form of a lipstick, a foundation, a mascara, a makeup rouge, an eyeliner, a lipstick, a nail varnish, a product especially having care properties, a mascara, an eyeliner, a concealer product or a makeup product for the body (such as a tattoo) or for the hair.
A subject of the invention is also a makeup kit containing a cosmetic makeup product as defined above, in which the various compositions are packaged separately and are advantageously accompanied by suitable application means. These means may be fine brushes, coarse brushes, pens, pencils, felts, feathers, sponges, tubes and/or foam tips. The first composition of the product according to the invention may constitute a basecoat applied onto the keratin material, and the second composition a topcoat. However, it is possible to apply under the first coat an undercoat that may or may not have the constitution of the second coat.
It is also possible to deposit an overcoat onto the second coat, which may have a constitution identical to or different from that of the first coat. Preferably, the makeup obtained is a two-coat makeup. The second composition may also constitute a basecoat applied to the keratin material and the first composition a topcoat.
In particular, the basecoat is a lipstick, a foundation, a mascara, a lip gloss, an eyeliner, a nail varnish, a nailcare product or a body makeup product, and the topcoat is a care or protective product. The invention also relates to a process for making up the skin and/or the lips and/or the integuments, which consists in applying a cosmetic product as defined above to the skin and/or the lips and/or the integuments. A subject of the invention is also a cosmetic process for caring for or making up human skin and/or lips and/or integuments, which consists in applying to the skin, the lips and/or the integuments a first coat of a first composition comprising a vinyl polymer containing units derived from carbosiloxane dendrimers, and then in applying, onto all or part of the first coat, a second coat of a second composition comprising a cosmetically acceptable medium.
This process may consist in applying to the human skin, lips and/or integuments a first coat of a first composition comprising at least one vinyl polymer containing units derived from carbosiloxane dendrimers, leaving the said first coat to dry, and then applying, onto all or part of the first coat, a second coat of a second composition comprising a cosmetically acceptable medium.
This process may also consist in applying to
human skin, lips and/or integuments a first coat of a composition comprising a cosmetically acceptable medium, leaving the said first coat to dry and then applying, onto all or part of the first coat, a second coat of a composition comprising a vinyl polymer containing units derived from carbosiloxane dendrimers. The product according to the invention may be applied to the skin of either the face or the scalp and of the body, the lips, the inner edge of the lower eyelids, and the integuments, for instance the nails, the eyelashes, the hair, the eyebrows, or even body hair. The second composition may form patterns and may be applied with a pen, pencil or any other instrument (sponge, finger, fine brush, coarse brush or feather) . This makeup may also be applied onto makeup accessories, for instance false nails, false eyelashes or wigs, or alternatively, onto dots or patches that adhere to the skin or the lips (such as beauty spots) . A subject of the invention is also a made-up support comprising a first coat of a first composition comprising a vinyl polymer containing units derived from carbosiloxane dendrimers, and a second coat of a second composition comprising a cosmetically acceptable medium, the said first coat being applied to the support first or over all or part of the second coat.
This support may be in particular a hairpiece such as a wig, false nails or false eyelashes, or
alternatively patches that adhere to the skin or the lips (such as beauty spots) .
The invention also relates to the cosmetic use of the cosmetic product defined above to improve the comfort properties, in particular the tack-proof and/or non-dehydrating and/or gloss and/or transfer and/or migration and/or staying power properties of the makeup on the skin and/or the lips and/or the integuments. Finally, a subject of the invention is the use of a cosmetic product comprising a first composition and a second composition, the first composition comprising a vinyl polymer containing units derived from carbosiloxane dendrimers as described below, and the second composition comprising a cosmetically acceptable medium, to give the skin and/or the lips and/or the integuments a comfortable and/or glossy and/or transfer-resistant and/or non-migrating and/or fast cosmetic makeup result. First composition
The first composition according to the invention comprises at least one vinyl polymer containing units derived from carbosiloxane dendrimers. The first composition advantageously contains at least one of the following compounds: at least one organic filler, at least one sebum-absorbing powder, at least one oil that represents between 10% and 50% by
weight relative to the weight of the vinyl polymer, at least one polymer having a glass transition temperature of less than or equal to 30°C, at least one film- forming polymer, other than the said vinyl polymer, at least one organic gelling agent, at least one semi- crystalline polymer, at least one fluid silicone compound, at least one polymer comprising at least one polyamide block, at least one volatile oil.
The first composition advantageously comprises at least one vinyl polymer containing at least one unit derived from a carbosiloxane dendrimer and at least one oil, the glass transition temperature of the said vinyl polymer being greater than or equal to 400C and the oil representing between 5% and 75% by weight relative to the weight of the said vinyl polymer. VINYL POLYMER GRAFTED WITH A CARBOSILOXANE DENDRIMER
The vinyl polymer present in the first composition comprises at least one unit derived from a carbosiloxane dendrimer. The vinyl polymer may especially have a skeleton and at least one side chain, which comprises a carbosiloxane dendrimer structure. The term "carbosiloxane dendrimer structure" in the context of the present invention represents a structure with branched groups of high molecular masses with high regularity in the radial direction starting from the simple skeleton. Such carbosiloxane dendrimer
structures are described in the form of a highly- branched siloxane-silylalkylene copolymer in the laid- open Japanese patent application Kokai 9-171 164.
The vinyl polymer contains units derived from carbosiloxane dendrimers that may be represented by the following general formula:
in which R1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms, and X1 represents a silylalkyl group which, when i = 1, is represented by the formula:
in which R1 is the same as defined above, R2 represents an alkylene group containing from 2 to 10 carbon atoms, R3 represents an alkyl group containing from 1 to 10 carbon atoms, X1+1 represents a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, an aryl group or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 which represents the generation of the said silylalkyl group, and a1 is an integer from 0 to 3; Y represents an
organic group that may be polymerized using radicals chosen from the group consisting of an organic group that contains a methacrylic group or an acrylic group and that is represented by the formulae:
and
in which R4 represents a hydrogen atom or an alkyl group, R5 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the methylene group and the propylene group being preferred; and an organic group that contains a styryl group and that is represented by the formula:
in which R6 represents a hydrogen atom or an alkyl group, R7 represents an alkyl group containing from 1 to 10 carbon atoms, such as a methyl group, ethyl group, a propyl group or a butyl group, the methyl group being preferred, R8 represents an alkylene group containing
from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the ethylene group being preferred, b is an integer from 0 to 4, and c is 0 or 1 such that if c is 0, -(R8)c- represents a bond,
R1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms, in which the alkyl group is preferably represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group, and in which the aryl group is preferably represented by a phenyl group and a naphthyl group, in which the methyl and phenyl groups are more particularly preferred, and the methyl group is preferred among all.
The vinyl polymer that contains a carbosiloxane dendrimer structure may be the product of polymerization of
(A) from 0 to 99.9 parts by weight of a monomer of vinyl type; and
(B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing an organic group that may be polymerized using radicals, represented by the general formula:
in which Y represents an organic group that may be polymerized using radicals, R1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms, and X1 represents a silylalkyl group which, when i = 1, is represented by the formula:
in which R
1 is the same as defined above, R
2 represents an alkylene group containing from 2 to 10 carbon atoms, R
3 represents an alkyl group containing from 1 to 10 carbon atoms, X
1+1 represents a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 that represents the generation of the said silylalkyl group, and a
1 is an integer from 0 to 3; in which the said organic group that may be polymerized with radicals contained in the component (B) is chosen from the group consisting of an organic group that contains a methacrylic group or an acrylic group and that is represented by the formulae:
and
in which R4 represents a hydrogen atom or an alkyl group, R5 represents an alkylene group containing from 1 to 10 carbon atoms; and an organic group that contains a styryl group and that is represented by the formula:
in which R6 represents a hydrogen atom or an alkyl group, R7 represents an alkyl group containing from 1 to 10 carbon atoms, R8 represents an alkylene group containing from 1 to 10 carbon atoms, b is an integer from 0 to 4, and c is 0 or 1. When c is 0, -(R8)c- represents a bond.
The monomer of vinyl type that is the component (A) in the vinyl polymer is a monomer of vinyl type that contains a radical-polymerizable vinyl group. There is no particular limitation as regards the type of such a monomer. The following are examples of
this type of vinyl monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate or a methacrylate of a lower alkyl analogue; glycidyl methacrylate; n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, methacrylic acid, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate or a higher-analogue methacrylate; vinyl acetate, vinyl propionate or a vinyl ester of a lower fatty acid analogue; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate or an ester of a higher fatty acid analogue; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinyl- pyrrolidone or similar vinylaromatic monomers; methacrylamide, N-methylolmethacrylamide, N-methoxy- methylmethacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide or similar monomers of vinyl type containing amide groups; hydroxyethyl methacrylate, hydroxypropyl methacrylate or similar monomers of vinyl type containing hydroxyl groups; methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or similar monomers of vinyl type containing a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol
monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether or a similar monomer of vinyl type with ether bonds; methacryloxypropyl- trimethoxysilane, polydimethylsiloxane containing a methacrylic group on one of its molecular ends, polydimethylsiloxane containing a styryl group on one of its molecular ends, or a similar silicone compound containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, of itaconic acid, of crotonic acid, of maleic acid or of fumaric acid; a radical- polymerizable unsaturated monomer containing a sulfonic acid group such as a styrenesulfonic acid group; a quaternary ammonium salt derived from methacrylic acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and a methacrylic acid ester of an alcohol containing a tertiary amine group, such as a methacrylic acid ester of diethylamine.
Multifunctional monomers of vinyl type may also be used. The following represent examples of such compounds: trimethylolpropane trimethacrylate, pentaerythrityl trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 4-butanediol
dimethacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane- trioxyethyl methacrylate, tris (2-hydroxyethyl) - isocyanurate dimethacrylate, tris (2-hydroxyethyl) - isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups containing divinylbenzene groups on both ends, or similar silicone compounds containing unsaturated groups.
The carbosiloxane dendrimer, which is the component (B) , is represented by the following formula:
The following represent the preferred examples of radical-polymerizable organic group Y: an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4- (2-propenyl)phenyl group, a 3- (2-propenyl)phenyl group, a 2- (4-vinylphenyl) ethyl group, a 2- (3-vinylphenyl) ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
R1 represents an alkyl group or an aryl group containing from 1 to 10 carbon atoms, in which the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an
isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group; and the aryl group may be a phenyl group or a naphthyl group. The methyl and phenyl groups are particularly preferred, the methyl group being preferred among all. X1 represents a silylalkyl group that is represented by the following formula, when i is equal to 1:
in which R2 represents an alkylene group containing from 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group or a similar linear alkylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1, 4-dimethylbutylene group or a similar branched alkylene group. The ethylene, methylethylene, hexylene, 1-methylpentylene and 1, 4-dimethylbutylene groups are preferred among all. R3 represents an alkyl group containing from 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl and isopropyl groups. R1 is the same as defined above. X1+1 represents a hydrogen atom, an alkyl group containing from 1 to 10 carbon atoms, an aryl group or the silylalkyl group with i = i + 1. a1 is an integer from 0 to 3, and i is an integer from 1 to 10 that indicates the generation
number, which represents the number of repetitions of the silylalkyl group.
For example, when the generation number is equal to 1, the carbosiloxane dendrimer may be represented by the first general formula shown below, in which Y, R1, R2 and R3 are the same as defined above, R12 represents a hydrogen atom or is identical to R1; a1 is identical to a1. Preferably, the mean total number of groups OR3 in a molecule is within the range from 0 to 7. When the generation number is equal to 2, the carbosiloxane dendrimer may be represented by the second general formula shown below, in which Y, R1, R2, R3 and R12 are the same as defined above; a1 and a2 represent the a1 of the indicated generation. Preferably, the mean total number of groups OR3 in a molecule is within the range from 0 to 25. When the generation number is equal to 3, the carbosiloxane dendrimer is represented by the third general formula shown below, in which Y, R1, R2, R3 and R12 are the same as defined above; a1, a2 and a3 represent the a1 of the indicated generation. Preferably, the total mean number of groups OR3 in a molecule is within the range from 0 to 79.
A carbosiloxane dendrimer that contains a radical-polymerizable organic group may be represented by the following mean structural formulae:
The carbosiloxane dendrimer may be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154. For example, it may be produced by subjecting an organosilicon compound containing a hydrogen atom linked to a silicon atom, represented by the following general formula:
and an organosilicon compound containing an alkenyl group, to a hydrosilylation reaction. In the above formula, the organosilicon compound may be represented by 3-methacryloxypropyltris (dimethylsiloxy) silane, 3-acryloxypropyltris (dimethylsiloxy) silane and 4-vinylphenyltris (dimethylsiloxy) silane. The organosilicon compound that contains an alkenyl group may be represented by vinyltris (trimethylsiloxy) silane, vinyltris (dimethylphenylsiloxy) silane, and 5- hexenyltris (trimethylsiloxy) silane. The hydrosilylation reaction is performed in the presence of a chloroplatinic acid, a complex of vinylsiloxane and of platinum, or a similar transition metal catalyst. In the vinyl polymer that contains a dendrimer structure, the polymerization ratio between the components (A) and (B) , in terms of the weight ratio between (A) and (B) , may be within the range from 0/100 to 99.9/0.1 and preferably within the range from 1/99 to 99/1. A ratio between the components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B) .
The vinyl polymer contains a carbosiloxane dendrimer structure and this polymer may be obtained by
copolyraerization of the components (A) and (B) , or by- polymerization of the component (B) alone. The polymerization may be a free-radical polymerization or an ionic polymerization, but free-radical polymerization is preferred. The polymerization may be performed by bringing about a reaction between the components (A) and (B) in a solution for a period of from 3 to 20 hours in the presence of a radical initiator at a temperature of from 500C to 1500C. A suitable solvent for this purpose is hexane, octane, decane, cyclohexane or a similar aliphatic hydrocarbon; benzene, toluene, xylene or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane or similar ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate or similar esters; methanol, ethanol, isopropanol, butanol or similar alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane or a similar organosiloxane oligomer. A radical initiator may be any compound known in the art for standard free-radical polymerization reactions. The specific examples of such radical initiators are 2, 2' -azobis (isobutyronitrile) , 2,2'- azobis (2-methylbutyronitrile) , 2,2' -azobis (2, 4- dimethylvaleronitrile) or similar compounds of azobis
type; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or a similar organic peroxide. These radical initiators may be used alone or in a combination of two or more. The radical initiators may be used in an amount of from 0.1 to 5 parts by weight per 100 parts by weight of the components (A) and (B) . A chain-transfer agent may be added. The chain-transfer agent may be 2- mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethyl- siloxane containing a mercaptopropyl group or a similar compound of mercapto type; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3- chloropropyltrimethoxysilane or a similar halogenated compound. In the manufacture of the polymer of vinyl type, after the polymerization, the residual unreacted vinyl monomer may be removed under conditions of heating under vacuum.
To facilitate the preparation of the mixture of the starting material of cosmetic products, the number-average molecular mass of the vinyl polymer containing a carbosiloxane dendrimer may be chosen within the range between 3000 and 2 000 000 and preferably between 5000 and 800 000. It may be a liquid, a gum, a paste, a solid, a powder or any other form. The preferred forms are solutions consisting of the dilution of a dispersion or of a powder in
solvents.
The vinyl polymer may be a dispersion of a polymer of vinyl type having a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol or water.
The vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain, in this embodiment, is the same as that described above. The liquid may be a silicone oil, an organic oil, an alcohol or water. The silicone oil may be a dimethylpolysiloxane with the two molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methyl-3, 3, 3-trifluoropropylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, or similar unreactive linear silicone oils, and also hexamethyl- cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclo- hexasiloxane or a similar cyclic compound. In addition to the unreactive silicone oils, modified polysiloxanes containing functional groups such as silanol groups, amino groups and polyether groups on the ends or within the side molecular chains may be used.
The organic oils may be liquid paraffin, isoparaffin, hexyl laurate, isopropyl myristate,
myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil, camellia oil, squalane, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, beef tallow, lard, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or a similar glycol ester oil; triglyceryl isostearate, the triglyceride of a fatty acid of coconut oil, or a similar oil of a polyhydric alcohol ester; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether or a similar polyoxyalkylene ether.
The alcohol may be any type that is suitable for use in combination with a cosmetic product starting material. For example, it may be methanol, ethanol, butanol, isopropanol or similar lower alcohols. A solution or a dispersion of the alcohol should have a viscosity within the range from 10 to 109 mPa at 25°C. To improve the sensory use properties in a cosmetic product, the viscosity should be within the range from 100 to 5 x 108 mPa.s. The solutions and dispersions may be readily prepared by mixing the vinyl polymer having a carbosiloxane dendrimer structure with a silicone oil,
an organic oil, an alcohol or water. The liquids may be present in the step of polymerization of the polymer of vinyl type having a carbosiloxane dendrimer structure. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric pressure or reduced pressure. In the case of a dispersion, the dispersity of the polymer of vinyl type may be improved by adding a surfactant. Such an agent may be hexyl- benzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethyl- ammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow- trimethylammonium hydroxide, coconut oil- trimethylammonium hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylenealkylphenol, a polyoxyalkylene alkyl ester, the sorbitol ester of polyoxyalkylene, polyethylene glycol, polypropylene glycol, an ethylene oxide additive of diethylene glycol trimethylnonanol, and nonionic surfactants of polyester type, and also mixtures. In addition, the solvents and dispersions may
be combined with iron oxide suitable for use with cosmetic products, or a similar pigment, and also zinc oxide, titanium oxide, silicon oxide, mica, talc or similar mineral oxides in powder form. In the dispersion, a mean oxide, titanium oxide, silicon oxide, mica, talc or similar mineral oxides in powder form. In the dispersion, a mean particle diameter of the polymer of vinyl type may be within a range of between 0.001 and 100 microns and preferably between 0.01 and 50 microns. The reason for this is that, outside the recommended range, a cosmetic product mixed with the emulsion will not have a nice enough feel on the skin or to the touch, or sufficient spreading properties or a pleasant feel. The vinyl polymer contained in the dispersion or the solution may have a concentration in the range between 0.1% and 95% by weight and preferably between 5% and 85% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 75% by weight.
The vinyl polymer may be one of the polymers described in the examples of patent application EP 0 963 751.
According to one embodiment, the vinyl polymer also comprises at least one organofluorine group.
Structures in which the polymerized vinyl
units constitute the skeleton and carbosiloxane dendritic structures and also organofluorine groups are attached to side chains are particularly preferred.
The organofluorine groups may be obtained by replacing with fluorine atoms all or some of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl groups and other alkyl groups of 1 to 20 carbon atoms, and also alkyloxyalkylene groups of 6 to 22 carbon atoms.
The groups represented by the formula: - (CH2)x- (CF2)y-R13 are suggested as examples of fluoroalkyl groups obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups. In the formula, the index "x" is 0, 1, 2 or 3 and "y" is an integer from 1 to 20. R13 is an atom or a group chosen from a hydrogen atom, a fluorine atom, -CH(CFa)2- and CF(CF3)2. Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulae presented below. -CF3, -C2F5, -nC3F7, -CF(CF3) 2, -nC4F9, CF2CF(CF3) 2, -nCsFu, -nC6Fi3, -nC8Fi7, -CH2CF3, -(CH (CF3) 2,
CH2CH ( CF3 ) 2-CH2 ( CF2 ) 2F, -CH2 (CF2 ) 3F, -CH2 ( CF2 J 4F, -CH2 ( CFz ) 6F, -CH2 (CF2 ) 8F, -CH2CH2CF3 , -CH2CH2 ( CFs ) 2F,
-CH2CH2 (CF2) 3F, -CH2CH2 (CF2) 4F, -CH2CH2 (CF2) 6F, -CH2CH2 (CF2) 8F, -CH2CH2(CF2)I0F, -CH2CH2 (CF2) i2F, -CH2CH2(CF2)I4F, -CH2CH2(CF2)I6F, -CH2CH2CH2CF3, -CH2CH2CH2(CFa)2F, -CH2CH2CH2 (CF2) 2H, -CH2 (CF2) 4H, and -CH2CH2(CFz)3H.
The groups represented by
-CH2CH2- (CF2)m-CFR14- [OCF2CF(CF3) Jn-OC3F7 are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups. In the formula, the index "m" is 0 or 1, "n" is 0, 1, 2, 3, 4 or 5, and R14 is a fluorine atom CF3. Such fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxy- fluoroalkylene groups represented by the formulae presented below:
-CH2CH2CF(CF3) - [OCF2CF(CF3) ]n-OC3F7, -CH2CH2CF2CF2-[OCF2CF(CF3) ]n-OC3F7.
The number-average molecular weight of the vinyl polymer used in the present invention may be between 3000 and 2 000 000 and more preferably between 5000 and 800 000.
This type of fluorinated vinyl polymer may be obtained by addition of a vinyl monomer (B) not containing any organofluorine groups in the molecule to a vinyl monomer containing organofluorine groups in the molecule (A) , and
a carbosiloxane dendrimer (C) containing radical- polymerizable organic groups represented by the general formula (III) :
in which Y is a radical-polymerizable organic group and R
1 and X
1 are as above, and by subjecting them to a copolymerization.
The vinyl monomers (A) containing organofluorine groups in the molecule are preferably monomers represented by the general formula:
- (CH2) =CR15COORf. In the formula, R15 is a hydrogen atom or a methyl group and Rf is an organofluorine group exemplified by the fluoroalkyl and fluoroalkyloxy- fluoroalkylene groups described above. The compounds represented by the formulae presented below are suggested as specific examples of the component (A) . In the formulae presented below λλ z" is an integer from 1 to 4 . CH2=CCH3COO-CF3 . CH2=CCH3COO-C2F5 . CH2=CCH3COO-nC3F7. CH2=CCH3COO-CF (CF3) 2 . CH2=CCH3COO-nC4F9 .
CH2=CCH3COO-CF2CF ( CF3 ) 2 • CH2=CCH3COO-nC5Fn . CH2=CCH3COO-nC6Fi3 . CH2=CCH3COO-nC8Fi7 . CH2=CCH3COO-CH2CF3 . CH2=CCH3COO-CH ( CF3 ) 2 • CH2=CCH3COO-CH2CH ( CF3 ) 2 • CH2=CCH3COO-CH2 (CF2 ) 2F .
CH2=CCH3COO-CH2 (CF2) 3F. CH2=CCH3COO-CH2 (CF2) 4F.
CH2=CCH3COO-CH2 (CF2) 6F. CH2=CCH3COO-CH2 (CF2) 8F.
CH2=CCH3COO-CH2CH2CF3. CH2=CCH3COO-CH2CH2 (CF2) 2F.
CH2=CCH3COO-CH2CH2 (CF2) 3F. CH2=CCH3COO-CH2CH2 (CF2) 4F-CH2=CCH3COO-CH2CH2 (CF2) 6F.
CH2=CCH3COO-CH2CH2 (CF2) 8F. CH2=CCH3COO-CH2CH2 (CF2) IOF.
CH2=CCH3COO-CH2CH2 (CF2) I2F. CH2=CCH3COO-CH2CH2 (CF2) 14F.
CH2=CCH3COO-CH2CH2 ( CF2 ) I6F . CH2=CCH3COO-CH2CH2CH2CF3.
CH2=CCH3COO-CH2CH2CH2 (CF2) 2F. CH2=CCH3COO-CH2CH2CH2 (CF2) 2H. CH2=CCH3COO-CH2 (CF2) 4H. CH2=CCH3COO-CH2CH2 (CF2) 3H.
CH2=CCH3COO-CH2CH2CF (CF3) - [OCF2CF (CF3) ] Z-OC3F7.
CH2=CCH3COO-CH2CH2CF2CF2- [OCF2CF (CF3) ] Z-OC3F7.
CH2=CHCOO-CF3. CH2=CHCOO-C2F5. CH2=CHCOO-nC3F7.
CH2=CHCOO-CF ( CF3 ) 2 • CH2=CHCOO-nC4F9. CH2=CHCOO-CF2CF (CF3) 2. CH2=CHCOO-nC5Fn.
CH2=CHCOO-nC6Fi3. CH2=CHCOO-nC8F17. CH2=CHCOO-CH2CF3.
CH2=CHCOO-CH ( CF3 ) 2. CH2=CHCOO-CH2CH ( CF3 ) 2 •
CH2=CHCOO-CH2 (CF2) 2F. CH2=CHCOO-CH2 (CF2) 3F.
CH2=CHCOO-CH2 (CF2) 4F. CH2=CHCOO-CH2 (CF2) 6F. CH2=CHCOO-CH2 (CF2) 8F. CH2=CHCOO-CH2CH2CF3.
CH2=CHCOO-CH2CH2 (CF2) 2F. CH2=CHCOO-CH2 (CF2) 3F.
CH2=CHCOO-CH2CH2 (CF2) 4F.
CH2=CHCOO-CH2CH2 (CF2) 6F. CH2=CHCOO-CH2CH2 (CF2) 8F.
CH2=CHCOO-CH2CH2 (CF2) I0F. CH2=CHCOO-CH2CH2 (CF2) I2F. CH2=CHCOO-CH2CH2(CF2)I4F. CH2=CHCOO-CH2CH2 (CF2) I6F.
CH2=CHCOO-CH2CH2CH2CF3. CH2=CHCOO-CH2CH2CH2 (CF2) 2F.
CH2=CHCOO-CH2CH2CH2 ( CF2 ) 2H . CH2=CHCOO-CH2 ( CF2 ) 4H .
CH2=CHCOO-CH2CH2 (CF2)3H.
CH2=CHCOO-CH2CH2CF(CF3) - [OCF2CF(CF3) ] Z-OC3F7.
CH2=CHCOO-CH2CH2CF2CF2-[OCF2CF(CF3) ] Z-OC3F7.
Among these, the vinyl polymers represented by the formulae presented below are preferable: CH2=CHCOO-CH2CH2 (CF2) 6F. CH2=CHCOO-CH2CH2 (CF2) 8F. CH2=CCH3COO-CH2CH2 (CF2) 6F. CH2=CCH3COO-CH2CH2 (CF2) 8F. CH2=CHCOO-CH2CF3. CH2=CCH3COO-CH2CF3
The vinyl polymers represented by the formulae presented below are particularly preferable. CH2=CHCOO-CH2CF3. CH2=CCH3COO-CH2CF3.
The vinyl monomers (B) not containing any organofluorine groups in the molecule may be any monomer containing radical-polymerizable vinyl groups illustrated, for example, by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate,
stearyl methacrylate, and other higher acrylates and methacrylates; vinyl acetate, vinyl propionate and other lower fatty acid vinyl esters; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, and other higher fatty acid esters; styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone, and other vinylaromatic monomers; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and other aminovinyl monomers, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethyl- methacrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and other vinylamide monomers; hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylic acid hydroxypropyl alcohol, methacrylic acid hydroxypropyl alcohol, and other hydroxyvinyl monomers; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and other vinylcarboxylic acid monomers; tetra- hydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycol acrylate, ethoxy- diethylene glycol methacrylate, polyethylene glycol
acrylate, polyethylene glycol methacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinyl monomers containing an ether bond; acryloxypropyl- trimethoxysilane, methacryloxypropyltrimethoxysilane, polydimethylsiloxanes containing acryl or methacryl groups at one of the ends, polydimethylsiloxanes containing alkenylaryl groups at one of the ends and other silicone compounds containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride, acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecylsuccinic anhydride; acryl glycidyl ether, methacryl glycidyl ether, 3,4-epoxy- cyclohexylmethyl acrylate, 3, 4-epoxycyclohexylmethyl- methacrylate, alkali metal salts, ammonium salts and organic amine salts of acrylic acid, of methacrylic acid, of itaconic acid, of crotonic acid, of fumaric acid, of maleic acid and of other radical-polymerizable unsaturated carboxylic acids, radical-polymerizable unsaturated monomers containing sulfonic acid groups, such as styrene sulfonic acid and also the alkali metal salts thereof, the ammonium salts thereof and the organic amine salts thereof; the quaternary ammonium salts derived from acrylic acid or methacrylic acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of a tertiary amine
alcohol, such as the diethylamine ester of methacrylic acid and quaternary ammonium salts thereof.
In addition, it is also possible to use as vinyl monomers (B) the polyfunctional vinyl monomers illustrated, for example, by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythrityl triacrylate, pentaerythrityl trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1,6-hexane- diol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane- trioxyethyl acrylate, trimethylolpropanetrioxyethyl methacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, tris (2-hydroxyethyl) isocyanurate dimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, polydimethylsiloxane in which the two ends of the molecular chain are blocked with alkenylaryl groups, and other silicone compounds containing unsaturated groups. As regards the ratio mentioned above in which the component (A) and the component (B) are copolymerized, the weight ratio of compound (A) to
compound (B) should be within the range from 0.1:99.9 to 100:0 and preferably within the range 1:99 to 100:0.
The carbosiloxane dendrimer (C) is represented by the general formula (III) indicated above. In formula (III), Y is a radical-polymerizable organic group, the type of which is not subject to any special limitations provided that it is an organic group capable of undergoing a radical addition reaction. Organic groups containing acryl and methacryl, organic groups containing alkenylaryl, or alkenyl groups of 2 to 10 carbon atoms represented by the general formulae presented below are suggested as specific examples.
In the formulae, R4 and R6 are hydrogen atoms or methyl groups, R5 and R8 are alkylene groups of 1 to 10 carbon atoms, and R7 is an alkyl group of 1 to 10 carbon atoms. The index "b" is an integer from 0 to 4 and "c" is 0 or 1. Acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl, 3-methacryloxypropyl, 4- vinylphenyl, 3-vinylphenyl, 4- (2-propenyl)phenyl, 3-(2- propenyl)phenyl, 2- (4-vinylphenyl) ethyl, 2- (3-
vinylphenyl) enyl, vinyl, allyl, methallyl, and 5- hexenyl are suggested as examples of such radical- polymerizable organic groups. The index "i" in formula (II), which is an integer from 1 to 10, is the number of generations of the said silylalkyl group, in other words the number of times that the silylalkyl group is repeated. Thus, the carbosiloxane dendrimer of this component with a generation number of 1 is represented by the general formula:
(in which Y, R1, R2 and R3 are as above and R12 is a hydrogen atom or such as R1 described above. The index "a1" is an integer from 0 to 3, the total mean of "a1" per molecule being from 0 to 7) . The carbosiloxane dendrimers of this component with a generation number of 2 are represented by the general formula:
(in which Y, R1, R2, R3 and R12 are as above and the indices "a1" and "a2" are integers from 0 to 3, the total mean of "a1" and of "a2" per molecule being from 0 to 25) .
The carbosiloxane dendrimers of this component with a generation number of 3 are represented by the general formula:
(in which Y, R
1, R
2, R
3 and R
12 are as above and the indices "a
1" and "a
2" and "a
3" are integers from 0 to 3, the total mean of "a
1", "a
2" and "a
3" per molecule being from 0 to 79) .
The component (C) is illustrated by carbosiloxane dendrimers represented by formulae of mean composition represented below.
The carbosiloxane dendrimers of the component (C) may be prepared using the process for preparing siloxane/silylalkylene branched copolymers described in document EP 1 055 674. For example, they may be prepared by subjecting organic alkenyl silicones and
silicone compounds comprising hydrogen atoms linked to silicon, represented by the general formula:
(in which R1 and Y are as above) to a hydrosilylation reaction. For example, 3-methacryloxypropyl- tris (dimethylsiloxy) silane, 3-acryloxypropyl- tris (dimethylsiloxy) silane and 4-vinylphenyl- tris (dimethylsiloxy) silane are used as silicon compounds represented by the above formula. Vinyl- tris (trimethylsiloxy) silane, vinyltris (dimethylphenyl- siloxy) silane and 5-hexenyltris (trimethylsiloxy) silane are used as organosilicon alkenyl compounds. In addition, it is preferable to perform the hydrosilylation reaction in the presence of a transition metal catalyst such as chloroplatinic acid and the platinium/vinylsiloxane complex.
The copolymerization ratio of the component (C) , in terms of its weight ratio relative to the total weight of compound (A) and (B) should be within the range from 0.1:99.9 to 99.9:0.1, preferably within the range from 1:99 to 99:1 and even more preferably within the range from 5:95 to 95:5.
Amino groups may be introduced into the side chains of the vinyl polymer using, included in the
component (B) , vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethyl- aminoethyl methacrylate, followed by performing a modification with potassium acetate monochloride, ammonium acetate monochloride, the aminomethylpropanol salt of monochloroacetic acid, the triethanolamine salt of monobromoacetic acid, sodium monochloropropionate, and other alkali metal salts of halogenated fatty acids; otherwise, carboxylic acid groups may be introduced into the side chains of the vinyl polymer using, included in the component (B) , vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid, and the like, followed by neutralizing the product with triethylamine, diethylamine, triethanolamine and other amines.
The fluorinated vinyl polymer may be one of the polymers described in the examples of patent application WO 03/045337.
The vinyl polymer may be present in a content ranging from 0.1% to 70% by weight, relative to the total weight of the composition, preferably ranging from 0.5% to 50% by weight, preferentially ranging from 1% to 40% by weight and more preferably ranging from 5% to 15% by weight. Organic filler:
The first composition according to the invention may comprise one or more organic fillers, especially in a content ranging from 0.01% to 50% by weight and preferably ranging from 0.01% to 30% by weight relative to the total weight of the first composition. The term "fillers" should be understood as meaning colourless or white, mineral or synthetic particles of any shape, which are insoluble in the medium of the first composition irrespective of the temperature at which the first composition is manufactured. Pigments and nacres are especially excluded from this definition.
According to one embodiment of the invention, the filler is an organic filler, i.e. a filler comprising at least one organic compound as mentioned in the above paragraph. An organic filler may be a) a filler consisting of at least one organic compound or b) a filler comprising at least one organic compound and at least one mineral compound. The organic filler may be a polymeric or non- polymeric organic filler.
The organic filler may be introduced into the first cosmetic composition so as to adjust its properties in terms of texture, or in other words to control its rheological properties.
The fillers may be of any form, platelet- shaped, spherical or oblong, irrespective of the
crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.) . Mention may be made of silica, polyamide (Nylon®) powder (Orgasol® from Atomchem) , poly-β-alanine powder and polyethylene powder, tetrafluoroethylene polymer (Teflon®) powders, starch, hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie) , or of acrylic acid copolymers (Polytrap® from the company Dow Corning) and silicone resin microbeads (for example Tospearls® from Toshiba) , metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate.
The organic filler may be a polymethyl methacrylate powder.
The polymethyl methacrylate powders are generally in the form of hollow or solid white spherical particles whose numerical mean size is generally on the micrometer scale, in particular ranging from 3 to 15 microns and generally from 3 to 10 microns. As representative and non-limiting polymethyl methacrylates that are suitable of the invention, mention may be made especially of the polymethyl methacrylate particles sold by the company Matsumoto Yushi Co. under the name "Micropearl MlOO",
by the company LCW under the name "Covabead LH 85" and those sold by the company Nihon Junyaku under the name "Jurymer MBl".
The polymethyl methacrylate particles may be present in a content ranging from 5% to 20% by weight relative to the total weight of the first composition, for example ranging from 7% to 18% by weight, for example ranging from 8% to 15% by weight.
The organic filler may be a polyurethane powder. In particular, the polyurethane powder is not film-forming, i.e. it does not form a continuous film when it is deposited onto a support such as the skin, after having been mixed with a volatile solvent to allow its deposition. Advantageously, the polyurethane powder is a powder of a copolymer of hexamethylenediisocyanate and of trimethylol hexyl lactone. Such a polyurethane powder is especially sold under the names "Plastic Powder D-400" and "Plastic Powder D-800" by the company Toshiki.
Another polyurethane powder that may be used is the product sold under the name "Plastic Powder CS-400" by the company Toshiki.
The polyurethane powder may be present in the first composition according to the invention in a content ranging from 0.5% to 30% by weight, preferably ranging from 1% to 15% by weight and preferentially
ranging from 5% to 15% by weight, relative to the total weight of the first composition.
The organic filler may be an elastomeric organopolysiloxane powder. The elastomeric organopolysiloxane is advantageously crosslinked and may be obtained by a crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen linked to silicon and of diorganopolysiloxane containing ethylenically unsaturated groups linked to silicon, especially in the presence of a platinum catalyst/ or by a condensation crosslinking dehydrogenation reaction between a diorganopolysiloxane with hydroxyl end groups and a diorganopolysiloxane containing at least one hydrogen , linked to silicon, especially in the presence of an organotin; or by crosslinking condensation reaction of a diorganopolysiloxane with hydroxyl end groups and of a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of an organoperoxide catalyst; or by crosslinking of organopolysiloxane by high-energy radiation such as gamma rays, ultraviolet rays or an electron beam.
Advantageously, the elastomeric organopolysiloxane is non-emulsifying.
The term "non-emulsifying" defines organopolysiloxane elastomers containing no hydrophilic
chains such as polyoxyalkylene or polyglycerolated units.
Spherical elastomeric organopolysiloxanes are especially described in patent applications JP-A-61-194 009, EP-A-242 219, EP-A-295 886 and EP-A-765 656, the content of which is incorporated by way of reference. Elastomeric organopolysiloxane powders that may be used include those sold under the names "Dow Corning 9505 Powder" and "Dow Corning 9506 Powder" by the company Dow Corning; these powders have the INCI name: dimethicone/vinyl dimethicone crosspolymer.
The elastomeric organopolysiloxane powder may comprise at least one elastomeric organopolysiloxane powder coated with silicone resin, especially with silasesquioxane resin, as described, for example, in patent US 5 538 793, the content of which is incorporated by way of reference. Such elastomeric powders are sold under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104" and "KSP-105" by the company Shin-Etsu, and have the INCI Name: vinyl dimethicone/methicone silsesquioxane crosspolymer.
Other elastomeric organopolysiloxanes in the form of spherical powders may be hybrid silicone powders functionalized with fluoroalkyl groups, sold especially under the name "KSP-200" by the company
Shin-Etsu; hybrid silicone powders functionalized with
phenyl groups, sold especially under the name "KSP-300" by the company Shin-Etsu.
The elastomeric organopolysiloxane powder, which is in particular non-emulsifying, and preferably spherical, may be present in the first composition in a content ranging from 5% to 25% by weight, preferably ranging from 7% to 15% by weight and preferentially ranging from 8% to 12% by weight, relative to the total weight of the first composition. In particular, the first composition according to the invention may comprise an elastomeric organopolysiloxane powder coated with silicone resin, especially with silasesquioxane resin, in a content ranging from 1% to 25% by weight, especially ranging from 1% to 25% by weight, preferably ranging from 2% to 8% by weight and preferentially ranging from 3% to 7% by weight, relative to the total weight of the first composition.
The organic filler may be an N-acylamino acid powder.
The N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitolyl, stearoyl or cocoyl group. The amino acid may be, for example, lysine, glutamic acid or alanine.
Advantageously, the N-acylamino acid powder may be a lauroyllysine powder.
The N-acylamino acid powder may be present in the first composition according to the invention in a content ranging from 5% to 20% by weight, preferably ranging from 7% to 18% by weight and preferentially ranging from 8% to 15% by weight, relative to the total weight of the first composition. Sebum-absorbing powder The first composition may contain at least one sebum-absorbing powder, which may be organic or mineral. The term "sebum-absorbing powder" means a powder capable of absorbing and/or adsorbing sebum.
The sebum uptake corresponds to the amount of sebum adsorbed onto the available surface of the powder. It is measured according to the Wet Point method described below.
Advantageously, the sebum uptake of the powder is greater than or equal to 1 ml/g, especially ranging from 1 ml/g to 20 ml/g, or even ranging from 1 ml/g to 15 ml/g, preferably greater than or equal to 1.5 ml/g, especially ranging from 1.5 ml/g to 20 ml/g, or even ranging from 1.5 ml/g to 15 ml/g, and preferentially greater than or equal to 2 ml/g, especially ranging from 2 ml/g to 20 ml/g, or even ranging from 2 ml/g to 15 ml/g.
Advantageously, the sebum-absorbing powder may have a BET specific surface area of greater than or equal to 300 m2/g, preferably greater than 500 m2/g and preferentially greater than 600 m2/g, and especially less than 1500 m2/g.
The λλBET specific surface area" is determined according to the BET (Brunauer - Emmet - Teller) method described in "The Journal of the American Chemical Society", vol. 60, page 309, February 1938 and corresponding to international standard ISO 5794/1
(appendix D) . The BET specific surface area corresponds to the total specific surface area (thus including micropores) of the powder.
The sebum-absorbing powder may be a mineral powder or an organic powder; it may be chosen from silica, polyamide (Nylon®) powders, acrylic polymer powders, especially polymethyl methacrylate powders such as those described above, polymethyl methacrylate/ethylene glycol dimethacrylate powder, polyallyl methacrylate/ethylene glycol dimethacrylate powder, ethylene glycol dimethacrylate/lauryl methacrylate copolymer powder; elastomeric silicone powders such as those described above, especially obtained by polymerization of organopolysiloxane containing at least two hydrogen atoms each linked to a silicon atom and of an organopolysiloxane comprising at least two ethylenically unsaturated groups (especially
two vinyl groups) in the presence of a platinum catalyst.
The sebum-absorbing powder may be a powder coated with a hydrophobic treatment agent. The hydrophobic treatment agent may be chosen from silicones, for instance methicones and dimethicones; fatty acids, for instance stearic acid; metal soaps, for instance aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups; amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.
The N-acylamino acids may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanonyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine.
The term "alkyl" mentioned in the compounds cited above especially denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.
The powder may especially be a pigment coated with a hydrophobic treatment agent, for instance iron oxide or titanium oxide coated with aluminium stearoyl- glutamate, sold under the references NAI-C33-8075-10, NAI-C33-134-10, NAI-C33-8073-10 and NAI-C47-051-10 by the company Myoshi Kasei.
Silica powders that may be mentioned include: the porous silica microspheres sold under the name Silica Beads SB-700 by the company Myoshi; "Sunsphere® H51", "Sunsphere® H33" and "Sunsphere® H53" by the company Asahi Glass; the polydimethylsiloxane-coated amorphous silica microspheres sold under the name "SA Sunsphere® H33" and "SA Sunsphere® H53" by the company Asahi Glass. Acrylic polymer powders that may be mentioned include: the polymethyl methacrylate powders sold under the name Covabead® LH85 by the company Wackher; the polymethyl methacrylate/ethylene glycol dimethacrylate powders sold under the name Dow Corning 5640 Microsponge® Skin Oil Adsorber by the company Dow Corning; Ganzpearl® GMP-0820 by the company Ganz Chemical; the polyallyl methacrylate/ethylene glycol dimethacrylate powders sold under the name Poly-Pore® L200 and Poly-Pore® E200 by the company Amcol;
the ethylene glycol dimethacrylate/lauryl methacrylate copolymer powders sold under the name Polytrap® 6603 by the company Dow Corning.
A Nylon powder that may be mentioned is the Nylon powder sold under the name Orgasol® 4000 or Orgasol 2002 by the company Arkema.
Elastomeric silicone powders that may be mentioned include the powders sold under the names "Trefil Powder E-505C" and "Trefil Powder E-506C" by the company Dow Corning.
The sebum-absorbing powder that is particularly preferred is silica powder, especially having the characteristics described above, in particular having a sebum uptake of greater than or equal to 2 ml/g and especially ranging from 2 ml/g to 20 ml/g. Such a silica powder is sold especially under the name "Sunsphere® H 33" by the company Asahi Glass. The sebum-absorbing powder may be present in the first composition according to the invention in a content ranging from 1% to 98% by weight, preferably ranging from 1% to 80% by weight, preferentially ranging from 1% to 60% by weight, more preferentially ranging from 1% to 35% by weight and even more preferentially ranging from 1% to 15% by weight, relative to the total weight of the first composition. Fibres
The first composition may contain fibres.
The term "fibre" should be understood as meaning an object of length L and diameter D such that L is very much greater than D, D being the diameter of the circle in which the cross section of the fibre is inscribed. In particular, the ratio L/D (or shape factor) is chosen within the range from 3.5 to 2500, preferably from 5 to 500 and better still from 5 to 150.
The fibres that may be used in the first composition of the invention may be fibres of synthetic or natural, mineral or organic origin. In particular, the fibres have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 1 mm to 3.5 mm. Their cross section may be within a circle of diameter ranging from 2 nm to 500 μm, preferably ranging from 100 nm to 100 μm and better still from 1 μm to 50 μm. The weight or yarn count of the fibres is often given in denier or decitex and represents the weight in grams per 9 km of yarn. Preferably, the fibres according to the invention have a yarn count chosen within the range from 0.15 to 30 denier and better still from 0.18 to 18 denier.
The fibres may be those described in patent application EP 1 201 221, the content of which is incorporated into the present patent application by way of reference.
Preferably, fibres of synthetic origin and in particular organic fibres are used, for instance those used in surgery. Water-insoluble fibres may advantageously be used. The fibres that may be used in the first composition according to the invention are preferably polyamide, cellulose, poly-p-phenylene- terephthamide or polyethylene fibres. Their length (L) may range from 0.1 mm to 5 mm and preferably from 0.25 mm to 1.6 mm, and their mean diameter may range from 1 μm to 50 μm. In particular, the polyamide fibres sold by Etablissements P. Bonte under the name "Polyamide 0.9 Dtex 3 mm", with a mean diameter of 6 μm, a yarn count of about 0.9 dtex and a length ranging from 0.3 mm to 5 mm, may be used. It is also possible to use poly-p-phenyleneterephthamide fibres with a mean diameter of 12 μm and a length of about 1.5 mm, for instance those sold under the name "Kevlar Floe" by the company DuPont Fibres, or else cellulose (or rayon) fibres with a mean diameter of 50 μm and a length ranging from 0.5 mm to 6 mm, for instance those sold under the name "Natural rayon flock fiber RClBE - N003 - M04" by the company Claremont Flock. Polyethylene fibres may also be used, for instance those sold under the name "Shurt Stuff 13 099 F" by the company Mini Fibers.
The fibres may be present in the first composition according to the invention in a content
ranging from 0.01% to 10% by weight, preferably from 0.1% to 5% by weight and better still from 0.3% to 2% by weight relative to the total weight of the first composition. Film-forming polymer:
According to one embodiment, the first composition contains at least one polymer that may be chosen from film-forming polymers. Certain film-forming polymers may be gelling agents. For the purposes of the invention, the term
"polymer" means a compound containing at least 2 repeating units and preferably at least 3 repeating units.
The term "film-forming polymer" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous film on a support, especially on keratin materials, preferably a cohesive film and better still a film whose cohesion and mechanical properties are such that the said film can be isolated from the said support.
The polymer may be present in the first composition in a content ranging from 0.1% to 60% by weight, preferably ranging from 0.1% to 50% by weight, preferably ranging from 0.5% to 40% by weight, preferentially ranging from 1% to 30% by weight and
more preferentially ranging from 1% to 25% by weight relative to the total weight of the first composition. In one embodiment, the film-forming organic polymer is at least one polymer chosen from the group comprising:
- film-forming polymers that are soluble in an organic liquid medium, in particular liposoluble polymers, when the organic liquid medium comprises at least one oil; - film-forming polymers that are dispersible in an organic solvent medium, in particular polymers in the form of non-aqueous dispersions of polymer particles, preferably dispersions in silicone oils or hydrocarbon- based oils; in one embodiment, the non-aqueous polymer dispersions comprise polymer particles that are surface-stabilized with at least one stabilizer; film-forming polymers in the form of aqueous dispersions of polymer particles, often known as "latices"; in this case, the first composition comprises an aqueous phase; water-soluble film-forming polymers; in this case, the first composition comprises an aqueous phase.
Among the film-forming polymers that may be used in the first composition of the present invention, mention may be made of synthetic polymers, of free- radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. Film-forming
polymers that may be mentioned in particular include acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose-based polymers, for instance nitrocellulose, silicone polymers, in particular silicone resins, silicone-grafted acrylic polymers, and polyamide polymers and copolymers.
The film-forming polymer may be chosen from the film-forming polymers described in patent application WO 04/028487, the content of which is incorporated into the present patent application by way of reference.
In particular, the film-forming polymer may be a crosslinked silicone compound as described in patent applications US 2003/0 103 918 and US 2003/0 049 216, the content of which is incorporated into the present patent application by way of reference. Film-forming polymers are especially described in the international patent application filed under No. PCT/FR03/02849, the content of which is incorporated by way of reference.
The film-forming polymer may be a film- forming linear ethylenic block polymer, which is advantageously styrene-free. More preferably, the block polymer comprises at least one first block and at least one second block that have different glass transition temperatures (Tg) , the said first and second blocks being linked together via an intermediate block
comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
The film-forming polymer may also be in the form of a dispersion of particles, which are preferably solid, of a grafted ethylenic polymer in a liquid fatty phase. Such a dispersion is especially described in the international patent application filed under No. PCT/FR03/03709, the content of which is incorporated by way of reference.
Advantageously, the grafted ethylenic polymer comprises an ethylenic skeleton that is insoluble in the said liquid fatty phase, and side chains that are covalently linked to the said skeleton and soluble in the said dispersion medium.
Polyamide polymer or copolymer
The polyamide polymer or copolymer may be chosen from polyamide homopolymers, polyamides branched with fatty chains, polyamide-organosiloxanes, polyamide-polyester copolymers and polyamide- polyacrylic copolymers, and mixtures thereof.
The polyamide polymer may be present in the first composition in a content ranging from 0.1% to 60% by weight, preferably ranging from 0.1% to 50% by weight, preferably ranging from 0.5% to 40% by weight, preferentially ranging from 1% to 30% by weight and
more preferentially ranging from 1% to 25% by weight, relative to the total weight of the first composition.
As polyamide polymers that may be used in the invention, mention may be made of the polymers described in patent application EP 1 343 458, the content of which is incorporated into the present patent application by reference, for example the polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds containing more than 2 carbonyl groups and 2 amine groups) , the carbonyl and amine groups of adjacent individual units being condensed via an amide bond. These polyamide resins are especially the products sold under the brand name Versamid® by the companies General Mills, Inc. and Henkel Corp.
(Versamid 9430, 744 or 1655) or by the company Olin Mathieson Chemical Corp., under the brand name Onamid®, especially Onamid S or C. These resins have a weight- average molecular mass ranging from 6000 to 9000. For further information regarding these polyamides, reference may be made to documents US-A-3 645 705 and US-A-3 148 125. Versamid® 930 or 744 is more especially used.
It is also possible to use the polyamides sold by the company Arizona Chemical under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623 and 2662) and the product sold under
the reference Macromelt 6212 by the company Henkel. For further information regarding these polyamides, reference may be made to the document US-A-5 500 209. It is also possible to use vegetable-based polyamide resins, for instance those described in patents US-A-5 783 657 and US-A-5 998 570.
As polyamide polymers that may be used in the invention, mention may be made of the polyamides branched with pendent fatty chains and/or terminal fatty chains containing from 6 to 120 carbon atoms, better still 8 to 120 and especially from 12 to 68 carbon atoms, each terminal fatty chain being linked to the polyamide skeleton via at least one bonding group, in particular ester. Preferably, these polymers comprise a fatty chain at each end of the polymer skeleton and in particular of the polyamide skeleton. Other bonding groups that may be mentioned include ether, amine, urea, urethane, thioester, thiourea and thiourethane groups. These polymers are more especially those described in document US-A-5 783 657 from the company Union Camp. Examples that may be mentioned include the commercial products sold by the company Arizona Chemical under the names Uniclear 80 and Uniclear 100. They are sold, respectively, in the form of a gel at 80% (of active material) in a mineral oil, and at 100% (of active material) . They have a softening point of
from 88 to 940C. These commercial products are a mixture of copolymers of a C36 diacid condensed with ethylenediamine, with a weight-average molecular mass of about 6000. The ester end groups result from the esterification of the remaining acid end groups with cetyl alcohol, stearyl alcohol or mixtures thereof (also known as cetyl stearyl alcohol) .
As polyamide polymers that may be used in the invention, mention may also be made of polyamides comprising at least one polyorganosiloxane group, consisting of from 1 to 1000 organosiloxane units in the main chain or in the form of a graft. The polymers are, for example, those described in documents US-A-5 874 069, US-A-5 919 444, US-A-β 051 216, US-A-5 981 680 and WO 04/054 524, the content of which is incorporated into the present patent application by way of reference.
The silicone polyamide may be a polymer comprising at least one unit of formula (IV) or (V) :
(IV) or
(V)
R4, R5, R6 and R7, which may be identical or different, represent a group chosen from: saturated or unsaturated, Ci to C4o linear, branched or cyclic hydrocarbon-based groups, which may contain in their chain one or more oxygen, sulfur and/or nitrogen atoms, and which may be partially or totally substituted with fluorine atoms,
Ce to Cio aryl groups, optionally substituted with one or more Ci to C4 alkyl groups, polyorganosiloxane chains possibly containing one or more oxygen, sulfur and/or nitrogen atoms,
X, which may be identical or different, represent a linear or branched Ci to C30 alkylenediyl group, which may contain in its chain one or more oxygen and/or nitrogen atoms,
Y is a Ci to C50 saturated or unsaturated, linear or branched alkylene, arylene, cycloalkylene,
alkylarylene or arylalkylene divalent group, which may comprise one or more oxygen, sulfur and/or nitrogen atoms, and/or which may bear as substitutent one of the following atoms or groups of atoms: fluorine, hydroxyl, C3 to C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 Ci to C3 alkyl, Ci to C3 hydroxyalkyl and Ci to C6 aminoalkyl groups, or n is an integer ranging from 2 to 500 and preferably from 2 to 200, and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200. Semi-crystalline polymer
The semi-crystalline polymer according to the invention preferably has a melting point of greater than or equal to 300C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC) such as the calorimeter sold under the name DSC 30 by the company Mettler, with a temperature rise of 5 or 100C per minute. (The melting point considered is the point corresponding to the temperature of the most endothermic peak in the thermogram) .
The semi-crystalline polymer comprises at least one crystallizable pendent chain or at least one crystallizable block. Aside from the crystallizable chains or blocks, the polymer blocks are amorphous.
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For the purposes of the invention, the term "crystallizable chain or block" means a chain or block which, if it was alone, would change from the amorphous state to the crystalline state reversibly, depending on whether it is above or below the melting point. For the purposes of the invention, a chain is a group of atoms that are pendent or lateral relative to the polymer skeleton. A block is a group of atoms belonging to the skeleton, this group constituting one of the repeating units of the polymer.
The semi-crystalline polymers that may be used in the invention are in particular: polyolefin block copolymers of controlled crystallization, the monomers of which are described in EP-A-O 951 897, polycondensates, especially of aliphatic or aromatic or aliphatic/aromatic polyester type, homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing in the skeleton at least one crystallizable block, for instance those described in document US-A-5 156 911, homopolymers or copolymers bearing at least one crystallizable side chain, in particular containing fluorinated group (s), as described in document WO-A-01/19333,
and mixtures thereof. In the last two cases, the crystallizable side chains or blocks are hydrophobic. As particular examples of semi-crystalline polymers that may be used in the first composition according to the invention, mention may be made of the Intelimer® IPA products from the company Landec. These polymers are in solid form at room temperature (25°C) . They bear crystallizable side chains.
The semi-crystalline polymer may also be chosen from fatty acid esters of dextrin such as those described in patent application FR 2 843 019, the degree of substitution of which is less than or greater than 2, especially Rheopearl TL or Rheopearl KL. According to one embodiment, the semi-crystalline polymer is a polymer of organic structure other than a fatty acid ester of dextrin.
Organic polymer with at least one glass transition below 300C
The first composition may contain at least one polymer with a glass transition below 300C, which may be chosen from the list of polymers described above. The polymer may have at least one glass transition below 200C, for example below 100C.
The theoretical glass transition temperature of the polymer or of a block of the polymer may be calculated from the theoretical Tg values of the constituent monomers of the polymer or of a block of
the polymer, which may be found in a reference manual such as the Polymer Handbook, 3rd edition, 1989, John Wiley, according to the following relationship, known as Fox's law:
<x>i being the mass fraction of the monomer i in the block under consideration and Tgi being the glass transition temperature of the homopolymer of the monomer i (in °K) .
The glass transition temperature of the polymer according to the invention may be measured using a differential scanning calorimeter, for example the calorimeter sold under the name MDSC 2920 by the company TA Inst., via the technique known as
Differential Scanning Calorimetry (DSC) , in which a temperature rise of 100C per minute is applied, for example.
The polymer with at least one glass transition below 300C is preferably a block polymer or a copolymer capable of generating two phases in the first composition according to the invention, and in particular in the liquid fatty phase of the first composition. Among the polymers with at least one glass transition below 300C that are especially preferred are the silicone polyamides as described above, the silicone polymers with a viscosity of greater than
1000 cSt and more particularly with a viscosity of greater than 10 000 cSt or even greater than 100 000 cSt, as described in patent US 6 074 654 and patent application EP 1 452 165, the content of which is incorporated into the patent application by way of reference.
Grafted or block silicone acrylic polymers; acrylic copolymers, for example obtained from butyl acrylate, isobutyl acrylate or ethylhexyl acrylate monomers; and ethylenic copolymers, are also preferred. Oil:
The first composition according to the invention may comprise at least one oil. The oil advantageously represents between 10% and 50% by weight relative to the weight of the vinyl polymer.
The oil may be chosen from hydrocarbon-based oils, silicone oils and fluoro oils.
The oil may be chosen from volatile oils and non-volatile oils, and mixtures thereof. The term "hydrocarbon-based oil" means an oil formed essentially from, or even consisting of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and containing no silicon or fluorine atoms; it may contain ester, ether, amine or amide groups. The oil may be chosen from volatile hydrocarbon-based oils.
The term "silicone oil" means an oil containing at least one silicon atom, and especially containing Si-O groups.
The term "fluoro oil" means an oil containing at least one fluorine atom.
The first composition according to the invention may comprise at least one volatile oil.
The term "volatile oil" means an oil (or nonaqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a non-zero vapour pressure, at room temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to
40 000 Pa (10~3 to 300 mm Hg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg) . In addition, the volatile oil generally has a boiling point, measured at atmospheric pressure, ranging from 1500C to 2600C and preferably ranging from 17O0C to 250°C.
The first composition according to the invention may comprise a volatile hydrocarbon-based oil chosen especially from hydrocarbon-based oils with a flash point ranging from 4O0C to 1020C, preferably
ranging from 400C to 550C and preferentially ranging from 400C to 500C.
Volatile hydrocarbon-based oils that may be mentioned include volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms and mixtures thereof, and especially branched C8-Ci6 alkanes, for instance Cg-Ci6 isoalkanes (also known as isoparaffins) , isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar or Permetyl, branched Cs-Ci6 esters, for instance isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon-based oil is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isododecane.
Volatile silicone oils that may be mentioned include linear or cyclic silicones containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclopenta- siloxane, dodecamethylcyclohexasiloxane, heptamethyl- hexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane, and mixtures thereof.
The volatile oil may be present in the first composition according to the invention in a content ranging from 0.1% to 90% by weight, preferably ranging from 1% to 70% by weight and preferentially ranging from 5% to 50% by weight, relative to the total weight of the first composition.
The first composition according to the invention may comprise at least one non-volatile oil. Non-volatile hydrocarbon-based oils that may be used include liquid paraffin (or petroleum jelly) , squalane, hydrogenated polyisobutylene (Parleam oil) , perhydrosqualene, mink oil, turtle oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, sesame seed oil, corn oil, arara oil, rapeseed oil, sunflower oil, cottonseed oil, apricot oil, castor oil, avocado oil, jojoba oil, olive oil or cereal germ oil; linoleic acid, oleic acid, lauric acid or stearic acid esters; fatty esters, especially of Ci2-C36, such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate or lactate, bis (2-ethylhexyl) succinate, diisostearyl malate, and glyceryl or diglyceryl triisostearate; behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid; higher fatty alcohols, especially of Ci6-C22, such as cetanol, oleyl
alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol or octyldodecanol; and mixtures thereof.
The non-volatile oil may be present in a content ranging from 0.1% to 70% by weight, preferably ranging from 0.5% to 60% by weight and preferentially ranging from 1% to 50% by weight relative to the total weight of the non-volatile liquid fatty phase. Liquid binder According to one embodiment of the invention, the first composition comprises at least one vinyl polymer containing at least one unit derived from a carbosiloxane dendrimer and at least one liquid binder that represents between 10% and 50% by weight relative to the weight of the vinyl polymer.
The term "liquid binder" means a compound or a mixture of compounds that is liquid at 300C, which, when combined with the vinyl polymer containing at least one unit derived from a carbosiloxane dendrimer, gives, where appropriate after evaporating off the volatile compounds of the first composition, a continuous deposit without there being any macroscopic segregation of the binder or of the polymer (i.e. without any demixing or pearling at the surface) . When the polymer alone gives multi-fractured deposits, which adhere poorly to the substrates, the liquid binder
makes it possible to obtain more homogeneous deposits, presenting little or no fracturing to the naked eye.
The liquid binder is preferably non-volatile. The term "non-volatile" means a compound whose vapour pressure is less than 0.13 Pa (10~3 mm Hg) .
The liquid binder is preferably hydrocarbon- based and may be chosen from: the family of hydrocarbon-based oils, for example squalane, - the family of fatty alcohols, for example 2-octyldodecanol, the family of esters and fatty esters, for instance citrates and in particular acetyl tributyl citrate, sebacates, for instance diethylhexyl sebacate, triglycerides, for instance glyceryl triheptanoate, and mixtures thereof.
The liquid binder may in particular be branched. It preferably has a molecular weight of less than 1000 g/mol, better still less than 700 g/mol, or even less than 500 g/mol.
The liquid binder may especially represent between 15% and 45% and for example between 15% and 35% by weight of the vinyl polymer containing at least one unit derived from a carbosiloxane dendrimer.
According to another embodiment, the first cosmetic composition comprises, in a cosmetically acceptable medium, at least one vinyl polymer containing at least one unit derived from a carbosiloxane dendrimer such that its glass transition temperature is greater than or equal to 400C, and at least one liquid binder, which represents between 5% and 75% by weight relative to the weight of the said vinyl polymer. In this embodiment, the glass transition temperature of the vinyl polymer may be greater than or equal to 500C. The liquid binder may represent between 10% and 60%, especially between 15% and 45% and for example between 15% and 35% by weight of the vinyl polymer containing at least one unit derived from a carbosiloxane dendrimer. Plasticizer (oil or solid) :
The first composition may comprise at least one plasticizer for the vinyl polymer containing a silicone dendrimer.
The term "compound that plasticizes the polymer" means a compound present in an amount sufficient to lower the glass transition temperature of the polymer according to the invention by at least 50C and preferably by at least 100C.
The glass transition temperature of the polymer according to the invention is measured using a
differential scanning calorimeter according to the method described above.
To evaluate the reduction in the glass transition temperature caused by the compound, the glass transition temperature of the pure polymer is first measured by the above method, and a mixture of the polymer and of the compound is then prepared and a measurement is taken by the same method under the same conditions. The amount of plasticizing compound in the first composition should be sufficient to cause an effective decrease or reduction in the glass transition temperature of the polymer. This decrease or reduction is at least 5°C and preferably at least 100C. The plasticizing compound may be one of the oils described above.
The plasticizing compound may be a solid chosen especially from aliphatic or aromatic polycarboxylic acid esters of aliphatic or aromatic alcohols comprising from 1 to 10 carbon atoms, and the plasticizers mentioned in document FR-A-2 782 917, the content of which is incorporated into the present patent application by way of reference. Wax or pasty substance The first composition may contain at least one wax, which may be present in the first composition in a content ranging from 0.1% to 40% by weight,
preferably ranging from 0.1% to 30% by weight and preferentially ranging from 0.5% to 25% by weight relative to the total weight of the first composition.
For the purposes of the present invention, the term "wax" means a lipophilic compound that is solid at room temperature (25°C), which undergoes a reversible solid/liquid change of state, and which has a melting point of greater than or equal to 300C, which may be up to 1200C. By bringing the wax to the liquid state
(melting) , it is possible to make it miscible with the oils that may be present and to form a microscopically homogeneous mixture, but on reducing the temperature of the mixture to room temperature, recrystallization of the wax in the oils of the mixture takes place. The melting point of the wax may be measured using a differential scanning calorimeter (DSC) , for example the calorimeter sold under the name DSC 30 by the company Mettler. The wax may also have a hardness ranging from
0.05 MPa to 15 MPa and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compressive force, measured at 200C using the texturometer sold under the name TA-TX2i by the company Rheo, equipped with a stainless-steel cylinder 2 mm in diameter travelling at a measuring speed of 0.1 mm/s,
and penetrating into the wax to a penetration depth of 0.3 mm.
The waxes may be hydrocarbon-based waxes, fluoro waxes and/or silicone waxes, and may be of plant, mineral, animal and/or synthetic origin. In particular, the waxes have a melting point of greater than 300C and better still greater than 45°C.
As waxes that may be used in the first composition of the invention, mention may be made of beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes, for instance polyethylene waxes or Fischer- Tropsch waxes, and silicone waxes, for instance alkyl or alkoxy dimethicones containing from 16 to 45 carbon atoms.
The first composition may contain a micronized wax, also known as a microwax.
As microwaxes that may be used in the first compositions according to the invention, mention may be made of carnauba microwaxes, such as the product sold under the name "MicroCare 350®" by the company Micro Powders, synthetic microwaxes, such as that product sold under the name "MicroEase 114S®" by the company Micro Powders, microwaxes consisting of a mixture of carnauba wax and polyethylene wax, such as the products sold under the names "Micro Care 300®" and "310®" by the company Micro Powders, microwaxes consisting of a
mixture of carnauba wax and of synthetic wax, such as the product sold under the name "Micro Care 325®" by the company Micro Powders, polyethylene microwaxes, such as the products sold under the names "Micropoly 200®", "220®", "220L®" and "250S®" by the company Micro
Powders, and polytetrafluoroethylene microwaxes such as the products sold under the names "Microslip 519®" and "519 L®" by the company Micro Powders.
Among the microwaxes mentioned above, some of them, for instance carnauba microwax, the synthetic microwax "MicroEase 114S®" or the microwax consisting of a mixture of carnauba wax and of synthetic wax "MicroCare 325"", have a starting melting point of greater than or equal to 450C. As a guide, the first composition may contain from 0.1% to 50% by weight and better still from 1% to 30% by weight of wax relative to the total weight of the first composition.
The first composition may contain at. least one pasty compound, which may be chosen advantageously from:
- lanolin and its derivatives
- polymeric or non-polymeric silicone compounds
- polymeric or non-polymeric fluoro compounds - vinyl polymers, especially:
• olefin homopolymers
• olefin copolymers
• hydrogenated diene hoπtopolymers and copolymers
• linear or branched oligomers, homopolymers or copolymers of alkyl (meth) acrylates preferably containing a C8-C30 alkyl group • oligomers, homopolymers and copolymers of vinyl esters containing C8-C30 alkyl groups
• oligomers, homopolymers and copolymers of vinyl ethers containing C8-C30 alkyl groups
- liposoluble polyethers resulting from the polyetherification between one or more C2-C100 and preferably C2-C50 diols
- esters, and
- mixtures thereof.
Among the esters, the following are especially preferred: esters of a glycerol oligomer, especially diglycerol esters, in particular condensates of adipic acid and of glycerol, for which some of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid, and 12-hydroxystearic acid, especially such as those sold under the brand name Softisan 649 by the company Sasol, the arachidyl propionate sold under the brand name Waxenol 801 by Alzo, phytosterol esters,
fatty acid triglycerides and derivatives thereof, pentaerythritol esters, non-crosslinked polyesters resulting from the polycondensation between a linear or branched C4- C50 dicarboxylic acid or polycarboxylic acid and a C2- C50 diol or polyol, aliphatic esters of an ester, resulting from the esterification of an aliphatic hydroxy- carboxylic acid ester with an aliphatic carboxylic acid, polyesters resulting from the esterification, with a polycarboxylic acid, of an aliphatic hydroxycarboxylic acid ester, the said ester comprising at least two hydroxyl groups, such as the products Risocast DA-H® and Risocast DA-L®, and mixtures thereof.
Among the pasty compounds of plant origin that will preferably be chosen is a mixture of soybean sterols and of oxyethylenated (5 OE) oxypropylenated (5 OP) pentaerythritol, sold under the reference Lanolide by the company Vevy. Fluid silicone
The first composition may contain at least one fluid silicone compound such as, especially, a silicone gum or a silicone oil of high viscosity.
The fluid silicone compound, which is preferably non-volatile, may be chosen from polydimethylsiloxanes; alkyldimethicones; polyphenyl- methylsiloxanes such as phenyldimethicones, phenyl- trimethicones and vinylmethylmethicones; and also silicones modified with aliphatic and/or aromatic groups, which are optionally fluorinated, or with functional groups such as hydroxyl, thiol and/or amine groups.
The fluid silicone compound may be chosen especially from the silicones of formula (I) :
(D in which :
Ri/ R2f R5 and R6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms,
R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical or an aryl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical, n and p being integers chosen so as to have a fluid compound.
A polydimethylsiloxane with a viscosity at 25°C of between 10 and 10 000 000 cSt, preferably between 1000 and 2 500 000 cSt, preferably between 500 and 1 000 000 cSt and more preferably between 10 000 and 60 000 cSt is selected, for example, as nonvolatile silicone of formula (I) .
The viscosity of this silicone may be measured according to ASTM standard D-445.
As fluid silicone that may be used according to the invention, mention may be made of those for which: the substituents Ri to Rξ and X represent a methyl group, for instance the product sold under the name SE30 by the company General Electric, and the product sold under the name AK 500000 by the company Waker, the substituents Ri to RQ and X represent a methyl group and p and n are such that the molecular weight is 250 000 g/mol, for instance the product sold under the name Silbione 70047 V by the company Rhodia, the substituents Ri, R2, R5, Re and X represent a methyl group, the substituents R3 and R4 represent a aryl group and n and p are such that the molecular weight of the polymer is 600 000 g/mol, for instance the product sold under the name 761 by the company Rhδne-Poulenc.
The fluid silicone may be chosen from the dimethicones described in patent US 4 152 416. They are sold, for example, under the references SE30, SE33, SE54 and SE76. The dimethicones according to the invention include polydimethylsiloxanes, (polydimethyl- siloxane) (methylvinylsiloxane) copolymers such as SE63 sold by GE Bayer Silicones, and poly(dimethyl- siloxane) (diphenyl) (methylvinylsiloxane) copolymers, and mixtures thereof.
The weight-average molecular mass of the fluid silicone may be between 1000 and 1 500 000 g/mol and especially between 200 000 and 1 000 000 g/mol. Gelling agent: The first composition may contain at least one gelling agent, which may be mineral or organic, and polymeric or non-polymeric. The gelling agent may be chosen to gel an aqueous phase or a fatty phase of the first composition, depending on the case. The term "gelling agent" means a compound that modifies the rheology of the medium into which it is incorporated.
The aqueous-medium gelling agent may be chosen from: - hydrophilic clays,
- hydrophilic fumed silica, water-soluble cellulose-based thickeners,
guar gum, xanthan gum, carob gum, scleroglucan gum, gellan gum, rhamsan gum, karaya gum or carrageenan gum, alginates, maltodextrins, starch and its derivatives, and hyaluronic acid and its salts, the polyglyceryl (meth) acrylate polymers sold under the names "Hispagel" or "Lubragel" by the companies Hispano Qimica or Guardian, polyvinylpyrrolidone, - polyvinyl alcohol, crosslinked acrylamide polymers and copolymers, such as those sold under the names "PAS 5161" or "Bozepol C" by the company Hoechst, "Sepigel 305" by the company SEPPIC by the company Allied Colloid, or alternatively the crosslinked methacryloyloxyethyltrimethyl- ammonium chloride homopolymers sold under the name "Salcare SC95" by the company Allied Colloid, associative polymers and especially associative polyurethanes.
Such gelling agents are described especially in patent application EP-A-I 400 234, the content of which is incorporated by way of reference.
The oily-medium gelling agent may be chosen from: organophilic clays; hydrophobic fumed silicas;
alkyl guar gums (with a Ci-Cβ alkyl group) , such as those described in EP-A-708 114; oil-gelling polymers, for instance triblock polymers or star polymers resulting from the polymerization or copolymerization of at least one monomer containing an ethylenic group, for instance the polymers sold under the name Kraton; polymers with a weight-average molecular mass of less than 100 000, comprising a) a polymer skeleton containing hydrocarbon-based repeating units containing at least one hetero atom, and optionally b) at least one pendent fatty chain and/or at least one terminal fatty chain, which are optionally functionalized, containing from 6 to 120 carbon atoms and being linked to these hydrocarbon-based units, as described in patent applications WO-A-02/056847 and WO-A-02/47619, the content of which is incorporated by way of reference; in particular, polyamide resins (especially comprising alkyl groups containing from 12 to 22 carbon atoms) such as those described in US-A-5 783 657, the content of which is incorporated by way of reference; the silicone-based polyamide resins as described in patent application EP-A-I 266 647 and in the French patent application filed under the number 0 216 039, the content of which is incorporated by way of reference.
Such gelling agents are especially described
in patent application EP-A-I 400 234, the content of which is incorporated by way of reference.
The gelling agent may be an organic gelling agent, i.e. an agent comprising at least one organic compound.
The organogelling agents may be chosen from those described in patent application WO-A-03/105 788, the content of which is incorporated by way of reference. Aqueous phase:
The first composition may thus comprise a hydrophilic medium comprising water or a mixture of water and of hydrophilic organic solvent (s), for instance alcohols and especially linear or branched lower monoalcohols containing from 2 to 5 carbon atoms, for instance ethanol, isopropanol or n-propanol, and polyols, for instance glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols, or alternatively hydrophilic C2 ethers and C2-C4 aldehydes.
The water or the mixture of water and of hydrophilic organic solvents may be present in the first composition according to the invention in a content ranging from 0.1% to 95% by weight and preferably ranging from 10% to 80% by weight relative to the total weight of the first composition.
In particular, the first composition may be
in any galenical form normally used for topical application, and especially in the form of an oily or aqueous solution, an oily or aqueous gel, or oil-in- water or water-in-oil emulsion, a multiple emulsion, a dispersion of oil in water by means of vesicles, the vesicles being at the oil/water interface, or a powder. Each first composition may be fluid or solid.
The first composition according to the invention may especially be in the form of a suspension, a dispersion, a solution, a gel, an emulsion, especially an oil-in-water (O/W) or water-in- oil (W/0) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W/0) , in the form of a cream, a foam, a stick, a dispersion of vesicles, especially of ionic or nonionic lipids, a two-phase or multi-phase lotion, a spray, a powder, a paste, especially a soft paste (especially a paste having a dynamic viscosity at 25°C of about from 0.1 to 40 Pa.s at a shear rate of 200 s"1, after 10 minutes of measurement in cone/plate geometry) . The first composition may be a leave-in first composition.
The first composition may have a continuous fatty phase; it may be in anhydrous form and may contain less than 5% water and better still less than 1% water relative to the total weight of the first composition, and may especially be water-free, the water not being added during the preparation of the
first composition, but corresponding to the residual water provided by the mixed ingredients.
The first composition may have the appearance of a lotion, a cream, a pomade, a soft paste, an ointment, a solid cast or moulded especially as a stick or a dish, or a compacted solid.
The first composition is in the form of a more or less rigid stick. Dyestuffs The first composition according to the invention may comprise at least one dyestuff.
The dyestuff may be chosen from pulverulent dyestuffs (especially pigments and nacres) and water- soluble dyestuffs. The term "pigments" should be understood as meaning white or coloured, mineral or organic particles of any form, which are insoluble in the physiological medium, and which are intended to colour the first composition. The term "nacres" should be understood as meaning iridescent particles of any form, produced especially by certain molluscs in their shell, or else synthesized.
The pigments may be white or coloured, and mineral and/or organic. Among the mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and
also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders, for instance aluminium powder or copper powder. Among the organic pigments that may be mentioned are carbon black, pigments of D & C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.
Mention may also be made of pigments with an effect, such as particles comprising a natural or synthetic, organic or mineral substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being uncoated or coated with metallic substances, for instance aluminium, gold, silver, platinum, copper or bronze, or with metal oxides, for instance titanium dioxide, iron oxide or chromium oxide, and mixtures thereof.
The nacreous pigments may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica coated with iron oxides, titanium mica coated especially with ferric blue or with chromium oxide, titanium mica coated with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.
Interference pigments, especially liquid-crystal or multilayer interference pigments, may also be used. Additives:
The first composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, trace elements, softeners, sequestrating agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, moisturizers and propellents, or mixtures thereof.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s), and/or the amount thereof, such that the advantageous properties of the corresponding first composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
A person skilled in the art may select the appropriate galenical form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and secondly the intended application for the first composition. Second composition
The cosmetic product according to the invention comprises a second composition containing a cosmetically acceptable medium.
The second composition is advantageously chosen such that it improves at least one cosmetic property of the first composition, when it is applied alone to the said keratin material. The second composition may especially improve the comfort of the first composition or may reduce its tacky nature. The second composition may also be chosen such that the product, once applied to the keratin materials, has satisfactory gloss properties.
The first composition and/or the second composition may be chosen such that the product, once applied to the keratin materials, has satisfactory gloss properties. Gloss
The mean gloss of the product measured at 200C, once the first composition and the second composition have been spread one over the other onto a support, may be advantageously greater than or equal to 30, preferably greater than or equal to 40, preferably greater than or equal to 50 and preferably greater than or equal to 60 out of 100. The term "mean gloss" denotes the gloss as may be conventionally measured using a gloss meter by the following method.
The gloss of a deposit of the first composition alone, the gloss of a deposit of the second composition alone, or the gloss of a deposit of product according to the invention consisting of the superposition of deposits of the first composition and of the second composition may be measured.
A coat of between 50 μm and 150 μm in thickness of a composition is spread using an automatic spreader onto a Leneta brand contrast card of reference Form IA Penopac.
The coat of composition or of product covers at least the white background of the card. The deposit is left to dry for 24 hours at a temperature of 300C, and the gloss at 20° is then measured on the white background using a Byk Gardner brand gloss meter of reference microTri-Gloss. This measurement (which is between 0 and 100) is repeated at least three times, and the mean gloss is the mean of the at least three measurements carried out. When it is desired to measure the gloss of the product according to the invention, a first coat of one of the two compositions is spread onto the contrast card, under the same conditions as described above. This first coat is left to dry for the required time, and a second coat of the other composition is then spread on top, under the same conditions as described above.
The mean gloss of the first composition, or of the second composition, or of the product of the invention, measured at 20° is advantageously greater than or equal to 30, better still greater than or equal to 35, better still greater than or equal to 40, better still greater than or equal to 45, better still greater than or equal to 50 out of 100, better still greater than or equal to 55, better still greater than or equal to 60, better still greater than or equal to 65, better still greater than or equal to 70 or better still, greater than or equal to 75 out of 100. For certain compositions according to the invention, such as nail varnishes, the gloss measured at 20° may be greater than or equal to 70, or even 80, out of 100. Preferably, the mean gloss of the first composition, or of the second composition, or of the product of the invention, once spread onto a support, measured at 60° is greater than or equal to 50, better still greater than or equal to 60, better still greater than or equal to 65, better still greater than or equal to 70, better still greater than or equal to 75, better still greater than or equal to 80, better still greater than or equal to 85, or even better still greater than or equal to 90 out of 100. The mean gloss at 60° is measured under the same conditions as those described above for measuring the mean gloss at 20°.
Staying power
The first composition and/or the second composition may also be chosen such that the product, once applied to the keratin materials, has satisfactory staying power properties.
In particular, the first composition preferably has a transfer index of greater than or equal to 80%, preferably greater than or equal to 85%, preferably greater than or equal to 90% and preferably greater than or equal to 95%.
The second composition may be chosen such that the transfer index of the product is greater than or equal to 80%, preferably greater than or equal to 85%, preferably greater than or equal to 90% and preferably greater than or equal- to 95%.
The transfer index of the deposit obtained with the composition according to the invention is determined according to the measuring protocol described below. A support (40 mm x 70 mm rectangle) consisting of an acrylic coating (hypoallergenic acrylic adhesive on polyethylene film sold under the name Blenderme ref. FH5000-55113 by the company 3M Sante) bonded onto a layer of polyethylene foam that is adhesive on the face opposite that onto which the adhesive tape is fixed (foam layer sold under the name
RE40X70EP3 by the company Joint Technique Lyonnais Ind.) is prepared.
The L*0a*0b*o colour of the support, on the acrylic coating face, is measured using a Minolta CR 300 colorimeter.
The support thus prepared is preheated on a hotplate maintained at a temperature of 400C such that the surface of the support is maintained at a temperature of 330C ± 1°C. While leaving the support on the hotplate, the composition is applied over the entire non-adhesive surface of the support (i.e. to the surface of the acrylic coating) by spreading it out using a fine brush to obtain a deposit of about 15 μm of the composition, and it is then left to dry for 10 minutes.
After drying, the L*a*b* colour of the film thus obtained is measured.
The colour difference ΔE1 between the colour of the film relative to the colour of the naked support is then determined by means of the following relationship:
= V(L*-L0*)2 + (a*-ao*)2 + (b*-bo *)2
ΔE1
The support is then bonded via its adhesive face (adhesive face of the foam layer) to an anvil 20 mm in diameter and equipped with a screw pitch. A sample of the support/deposit assembly is then cut out
using a punch 18 mm in diameter. The anvil is then screwed onto a press (Statif Manuel Imada SV-2 from the company Someco) equipped with a tensile testing machine (Imada DPS-20 from the company Someco) . A strip 33 mm wide and 29.7 cm long is drawn on a sheet of white photocopier paper with a basis weight of 80 g/m2, a first line is marked 2 cm from the edge of the sheet, then a second line is marked 5 cm from the edge of the sheet, the first and second lines thus delimiting a box on the strip; a first mark and a second mark located in the strip at reference points 8 cm and 16 cm, respectively, from the second line is then applied. 20 μl of water are placed on the first mark and 10 μl of refined sunflower oil (sold by the company Lesieur) are placed on the second mark.
The sheet of white paper is placed on the bed of the press and the sample placed on the box of the strip of paper is then pressed at a pressure of about 300 g/cm2 exerted for 30 seconds. Next, the press is lifted and the sample is again moved to just after the second line (i.e. next to the box), a pressure of about 300 g/cm2 is again exerted and, once the contact has been made, the paper is moved in a rectilinear manner at a speed of 1 cπi/s, over the entire length of the strip such that the sample passes through the water and oil deposits.
After removing the sample, some of the deposit has become transferred onto the paper. The L*1, a*1, b*1 colour of the deposit remaining on the sample is then measured. The colour difference ΔE2 between the colour of the deposit remaining on the sample relative to the colour of the naked support is then determined by means of the following relationship:
ΔE2s V(L*'-L0*)2 + (a*'-ao *)2 + (b*'-bo *)2
The transfer index of the composition, expressed as a percentage, is equal to the ratio: 100 x ΔE1/ΔE1.
The measurement is performed on 6 supports in succession and the transfer value corresponds to the mean of the 6 measurements obtained with the 6 supports.
The cosmetically acceptable medium of the second composition preferably comprises a liquid phase that is non-volatile at room temperature and atmospheric pressure.
The term "non-volatile liquid phase" means any medium capable of remaining on the skin or the lips for several hours. A non-volatile liquid phase in particular has a non-zero vapour pressure at room temperature and atmospheric pressure, of less than
0.02 mm Hg (2.66 Pa) and better still less than 10"3 mm
Hg (0.13 Pa) .
The non-volatile liquid phase of the second composition may be at least one hydrocarbon-based phase, a liquid silicone phase or a fluoro phase that is liquid at room temperature, or a mixture thereof. The term "non-volatile hydrocarbon-based liquid phase" means a phase comprising at least one oil predominantly containing carbon atoms and hydrogen atoms and in particular alkyl or alkenyl chains, for instance alkanes or alkenes, but also oils with alkyl or alkenyl chains comprising one or more ether, ester or carboxylic acid groups.
The non-volatile liquid phase of the second composition advantageously represents from 1% to 100%, preferably from 5% to 95%, better still from 20% to 80% and even better still from 40% to 80% of the total weight of the second composition.
Non-volatile silicone oil of the liquid phase The non-volatile liquid phase of the second composition advantageously contains at least one silicone oil, for example a phenylsilicone oil or a polydimethylsiloxane oil.
The non-volatile silicone oil may be chosen from polyalkylsiloxanes, polyarylsiloxanes and polyalkylarylsiloxanes, and mixtures thereof.
The non-volatile silicone oil may be chosen from:
- linear or branched non-volatile polydimethylsiloxanes (PDMS) ; - polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms;
- phenylsilicones, for instance the triphenylpenta- methylsiloxane sold under the reference DC 555, phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates. The polyalkylsiloxanes according to the invention include polydimethylsiloxanes, (polydimethyl- siloxane) (methylvinylsiloxane) copolymers, poly- (dimethylsiloxane) (diphenyl) siloxanes, poly(dimethyl- siloxane) (diphenyl) (methylvinylsiloxane) copolymers, and mixtures thereof.
The non-volatile silicone oil that is preferred is an oil chosen from the silicones of formula (II) :
(H)
in which :
Riv R2A RS and R6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical, X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical, n and p being chosen so as to give the oil a weight- average molecular mass of less than 200 000 g/mol, preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol.
A polydimethylsiloxane with a viscosity of between 0.5 and 60 000 cSt, preferably between 0.5 and 10 000 cSt and preferentially between 0.5 and 1000 cSt measured according to ASTM standard D-445, for example DC 200 of viscosity 350 cSt, or DC 555, sold by Dow Corning, is chosen, for example, as non-volatile silicone oil of formula (II) .
According to one embodiment, the second composition contains a non-volatile silicone oil of formula (II) such as a polydimethylsiloxane with a viscosity preferably of between 0.5 and 500 cSt and more preferably between 1 and 10 cSt, for example the polydimethylsiloxane sold under the name DC 200 of viscosity 5 cSt and of molecular weight 800, sold by Dow Corning.
The weight-average molecular mass of the nonvolatile silicone oil is preferably between 400 and 200 000, preferably between 4000 and 100 000, preferably between 4000 and 20 000, preferably between 400 and 2000 and more preferably between 400 and 1000 g/mol. Non-volatile fluoro oil of the liquid phase
The non-volatile liquid phase of the second composition may comprise at least one fluoro oil of formula (III) :
- R represents a linear or branched divalent alkylenyl group containing 1 to 6 carbon atoms, preferably a divalent methylenyl, ethylenyl, propylenyl or butylenyl group,
- Rf represents a fluoroalkyl radical, especially a perfluoroalkyl radical, containing 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, - Ri represent, independently of each other, a Ci-C2O, preferably Ci-C4 alkyl radical, a hydroxyl radical or a phenyl radical,
- m is chosen from 0 to 150 and preferably from 20 to 100, and
- n is chosen from 1 to 300 and preferably from 1 to 100.
The oils of formula (III) such that Rl is a methyl, R is an ethyl and Rf is CF3 are preferred. Fluorosilicone compounds of formula (III) that may especially be mentioned are those sold by the company Shin Etsu under the names "X22-819", "X22-820", "X22-821" and "X22-822" or "FL-100".
Among the fluoro oils that may also be mentioned are the fluoro polyethers chosen from the compounds of formula (IV) below:
R6- (CF2-CFR3-CF2O)p- (CFR4-CF2-O) q- (CFR5-O) r-R7 (IV) in which:
- R3 to Re represent, independently of each other, a monovalent radical chosen from -F, -(CF2Jn-CF3 and
-0- (CF2)n-CF3,
- R7 represents a monovalent radical chosen from -F and -(CF2Jn-CF3,
- with n ranging from 0 to 4 inclusive, - p ranging from 0 to 600, q ranging from 0 to 860, r ranging from 0 to 1500, and p, q and r being integers chosen such that the weight-average molecular mass of the compound ranges from 500 to 100 000 and preferably from 500 to 10 000. The fluoro oils may also be chosen from fluoroalkanes chosen from C2-Cso and preferably Cs-C3O perfluoroalkanes and fluoroalkanes, such as perfluoro-
decalin, perfluoroadamantane and bromoperfluorooctyl, and mixtures thereof.
Volatile oil of the liquid phase
The second composition may optionally contain a volatile oil.
These oils may be hydrocarbon-based oils or silicone oils optionally comprising alkyl or alkoxy groups that are pendent or at the end of a silicone chain, or a mixture of these oils. Preferably, the volatile oils are cosmetic oils chosen from oils with a flash point ranging from 400C to 1000C, and mixtures thereof. In addition, they advantageously have a boiling point at atmospheric pressure of less than 2200C and better still less than 21O0C, especially ranging from 110 to 210°C.
Preferably, these volatile oils are not monoalcohols containing at least 7 carbon atoms.
As volatile oils that may be used in the invention, mention may be made of linear or cyclic silicone oils with a viscosity at room temperature of less than 8 cSt and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups of 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octa- methylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltri-
siloxane, heptamethyloctyltrisiloxane, hexamethyl- disiloxane, octamethyltrisiloxane, decamethyltetra- siloxane and dodecamethylpentasiloxane, and mixtures thereof. As other volatile oils that may be used in the invention, mention may be made of hydrocarbon-based volatile oils containing from 8 to 16 carbon atoms and mixtures thereof, and especially C8-Ci6 branched alkanes, for instance Cg-Ci6 isoalkanes (also known as isoparaffins) , isododecane, isodecane and isohexa- decane, and for example the oils sold under the trade names Isopar or Permethyl, and Cg-Ci6 branched esters, for instance isohexyl neopentanoate, and mixtures thereof. Isododecane (Permethyl 99 A) , C8-Ci6 isoparaffins, for instance Isopar L, E, G or H, and mixtures thereof, optionally combined with decamethyl- tetrasiloxane or with cyclopentasiloxane, are preferably used. In general, the amount of volatile oil is used in an amount that is sufficient to improve the spreading qualities of the second composition. This amount will be adapted by a person skilled in the art as a function of the intensity of the desired properties.
The amount of volatile oil is chosen so that it does not reduce the gloss of the second composition.
According to one embodiment, the second composition contains no volatile oil.
The second composition may also contain at least one fatty substance chosen from waxes, pasty substances, fluid silicone compounds such as the silicone oils described above and the silicone polymers described below, for instance silicone gums or silicone oils of very high viscosity, and mixtures thereof.
High molecular weight polymer The second composition advantageously contains a high molecular weight polymer that is different from the non-volatile silicone oil described above.
When the second composition according to the invention is liquid, it advantageously comprises 20% to
50% by weight of a high molecular weight polymer. According to one embodiment, the second composition advantageously contains a mixture of a polydimethylsiloxane with a molecular mass of between 200 000 and 300 000 g/mol and a polydimethylsiloxane with a molecular mass of between 400 and 1000 g/mol. The mass proportion of the high molecular weight silicone compound/liquid silicone compound is preferably between 20/80 and 60/40 and preferentially between 35/65 and 45/55.
When the second composition according to the invention is solid, it advantageously comprises 2% to 40% by weight of a high molecular weight polymer.
The polymer is preferably a silicone polymer. This polymer may be liquid or solid at room temperature and its weight-average molecular mass is greater than or equal to 200 000 g/mol, preferably between 200 000 and 2 500 000 and preferentially between 200 000 and 2 000 000 g/mol. When the polymer is liquid, it is part of the non-volatile liquid phase of the second composition.
The viscosity of this polymer may be between 10 000 and 5 000 000 cSt, preferably between 100 000 and 1 000 000 cSt and more preferably between 300 000 and 700 000 cSt, measured according to ASTM standard D-445.
The high molecular weight polymer is advantageously an ungrafted polymer, i.e. a polymer obtained by polymerizing at least one monomer, without subsequent reaction of the side chains with another chemical compound. The polymer is preferably chosen from dimethiconols, fluorosilicones, dimethicones and mixtures thereof. The polymer is preferably a homopolymer. In particular, the polymer that may be used is a high molecular weight polymer corresponding to formula (V) :
(V) in which:
Rif R2r Rs and R6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms, optionally substituted with at least one fluorine atom,
R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical, X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical, a vinyl or allyl radical or an alkoxy radical containing from 1 to 6 carbon atoms, n and p being chosen such that the silicone compound has a weight-average molecular mass of greater than or equal to 200 000 g/mol. p is preferably equal to 0. The polymers of formula (V) such that Ri to R6 represent a methyl group and the substituent X represents a hydroxyl group are dimethiconols. Examples that are mentioned include the polymers of formula (V) such that p = 0 and n is between 2000 and 40 000 and preferably between 3000 and 30 000. Mention may also be made of polymers with a molecular mass of between 1 500 000 and 2 000 000 g/mol.
According to one embodiment, the high molecular weight polymer is the dimethiconol sold by
Dow Corning in a polydimethylsiloxane (5 cSt) under the reference D2-9085, the viscosity of the mixture being equal to 1550 cSt, or the dimethiconol sold by Dow Corning in a polydimethylsiloxane (5 cSt) under the reference DC 1503. The dimethiconol (of molecular weight equal to 1 770 000 g/mol) sold by Dow Corning under the reference Q2-1403 or Q2-1401, the viscosity of the mixture being equal to 4000 cSt, is also preferred. As high molecular weight polymers that may be used according to the invention, mention may be made of those for which: the substituents Ri to Re and X represent a methyl group, for instance the product sold under the name SE30 by the company General Electric, and the product sold under the name AK 500 000 by the company Wacker, the substituents Ri to Rg and X represent a methyl group and p and n are such that the molecular weight is 250 000 g/mol, for instance the product sold under the name Silbione 70047 V by the company Rhodia, the substituents Ri to Re represent a methyl group and the substituent X represents a hydroxyl group, for instance the products sold under the name Q2-1401 or Q2-1403 by the company Dow Corning, . the substituents Ri, R2, R5, Rε and X represent a methyl group, the substituents R3 and R4 represent an aryl group and n and p are such that the molecular
weight of the polymer is 600 000 g/mol, for instance the product sold under the name 761 by the company Rhδne-Poulenc.
The high molecular weight silicone polymer is preferably introduced into the composition in the form of a mixture with a liquid silicone, the viscosity of the said liquid silicone being between 0.5 and 10 000 cSt, preferably between 0.5 and 500 cSt and more preferably between 1 and 10 cSt. The fluid silicone may be chosen from poly- alkylsiloxanes, polyarylsiloxanes, polyalkylaryl- siloxanes and mixtures thereof. The liquid silicone may be a volatile silicone such as a cyclic polydimethyl- siloxane comprising 3 to 7 - (CH3) 2SiO- units. The liquid silicone may also be a nonvolatile polydimethylsiloxane silicone, especially with a viscosity of between 0.5 and 10 000 cSt and more preferably of the order of 5 cSt, for example the silicone sold under the reference DC 200 by Dow Corning.
The proportion of the high molecular weight silicone polymer in the high molecular weight silicone polymer/liquid silicone mixture is preferably between 10/90 and 20/80. The viscosity of the high molecular weight silicone polymer/liquid silicone mixture is preferably between 1000 and 10 000 cSt.
The high molecular weight dimethicones according to the invention include the dimethicones described in patent US 4 152 416. They are sold, for example, under the references SE30, SE33, SE54 and SE76.
The dimethicones according to the invention are, for example, compounds of formula (III) such that Ri to Rg and X are methyls and p = 0. The molecular weight of these polymers is preferably between 200 000 and 300 000 and preferentially between 240 000 and 260 000 g/mol.
The dimethicones according to the invention include polydimethylsiloxanes, (polydimethylsiloxane) (methylvinylsiloxane) copolymers and poly(dimethyl- siloxane) (diphenyl) (methylvinylsiloxane) copolymers, and mixtures thereof.
The high molecular weight fluorosilicones according to the invention preferably have a molecular weight of between 200 000 and 300 000 and preferentially between 240 000 and 260 000 g/mol.
According to one of the aspects of the invention, the second composition according to the invention comprises at least one apolar or sparingly polar compound, which may be chosen from oils, gums and/or waxes. The second composition preferably comprises more than 70%, preferably more than 80% by weight and preferentially 100% by weight of apolar or
sparingly polar compounds. These apolar or sparingly polar compounds comprise colouring agents or gelling agents.
According to one embodiment, the second composition comprises a mixture of a polymer with a molecular mass of greater than or equal to 200 000 g/mol and a silicone oil as described above.
According to one embodiment, the second composition is transparent. The term "transparent composition" means a transparent to translucent composition, i.e. a composition which is such that it transmits at least 40% of light and preferably at least 50% of light with a wavelength of 750 nm. The transmission is measured using a Gary 300
Scan UV-visible spectrophotometer from the company Varian, according to the following protocol:
The composition is poured above its melting point into a spectrophotometer cuvette of square cross section with a side length of 10 mm.
The sample of the composition is then cooled for 24 hours at 35°C, and then kept in a chamber thermostatically maintained at 200C for 24 hours.
The light transmitted through the sample of the composition is then measured by spectrophotometer by scanning wavelengths ranging from 700 nm to 800 nm, the measurement being performed in transmission mode.
The percentage of light transmitted through the sample of the composition at a wavelength of 750 nm is then determined.
When the second composition is transparent, it advantageously contains less than 5%, preferably less than 2% and more preferably less than 1% of pigments.
The high molecular weight polymer/liquid silicone compound mixture preferably represents more than 70%, preferably more than 80% by weight, preferably more than 90% by weight and more preferably more than 95% by weight of the second composition.
The second composition may comprise other compounds, which are preferably apolar or sparingly polar. These apolar or sparingly polar compounds are preferably silicone compounds, colouring agents or gelling agents.
According to one embodiment, the second composition comprises only apolar or sparingly polar ingredients. The second composition may comprise at least one wax, especially when it is in solid form. The waxes may be chosen from the waxes described above regarding the first composition.
The waxes may be present in a proportion of 0.5-30% by weight in the composition and better still from 5% to 20% and preferably between 5% and 15% of the composition.
Linear hydrocarbon-based waxes are preferred in the context of the present invention. Their melting point is advantageously greater than 350C, for example greater than 55°C and preferably greater than 800C. The linear hydrocarbon-based waxes are advantageously chosen from substituted linear alkanes, unsubstituted linear alkanes, unsubstituted linear alkenes and substituted linear alkenes, an unsubstituted compound being composed exclusively of carbon and hydrogen. The substituents mentioned above do not contain carbon atoms.
The linear hydrocarbon-based waxes include ethylene polymers and copolymers with a molecular weight of between 400 and 800, for example Polywax 500 or Polywax 400 sold by New Phase Technologies.
The linear hydrocarbon-based waxes include linear paraffin waxes, for instance the paraffins S&P 206, S&P 173 and S&P 434 from Strahl & Pitsch.
The linear hydrocarbon-based waxes include long-chain linear alcohols, for instance products comprising a mixture of polyethylene and of alcohols containing 20 to 50 carbon atoms, especially Performacol 425 or Performacol 550 (mixture in 20/80 proportions) sold by New Phase Technologies. The second composition advantageously contains a silicone wax, such as a dimethicone comprising alkyl groups at the end of a chain. These
alkyl groups preferably contain more than 18 carbon atoms, preferably between 20 and 50 and preferentially between 30 and 45 carbon atoms.
The silicone wax for example corresponds to formula (VI) or (VII)
N (Vl)
in which R is an alkyl, X is greater than or equal to zero and N and Y are greater than or equal to one.
R contains from 1 to 50 carbon atoms provided that the compound is solid at room temperature.
Examples of silicone waxes include:
- C20-24 alkyl methicone, C24-28 alkyl dimethicone, C20-24 alkyl dimethicone and C24-28 alkyl dimethicone sold by Archimica Fine Chemicals under the reference Silcare 41M40, SilCare 41M50, SilCare 41M70 and SilCare 41M80,
- the stearyl dimethicones of reference SilCare 41M65 sold by Archimica or of reference DC-2503 sold by Dow Corning,
- the stearoxytrimethylsilanes sold under the reference SilCare 1M71 or DC-580,
- the products Abil Wax 9810, 9800 or 2440 from Wacker- Chemie GmbH,
- the C30-45 alkyl methicones sold by Dow Corning under the reference AMS-C30 Wax, and also the C30-45 alkyl- dimethicones sold by General Electric under the reference SF 1642 or SF 1632.
When the first or the second composition is intended to be applied to the nails, the composition preferably contains a solvent chosen from: - ketones that are liquid at room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone;
- alcohols that are liquid at room temperature, such as ethanol, isopropanol, diacetone alcohol,
2-butoxyethanol or cyclohexanol;
- glycols that are liquid at room temperature, such as ethylene glycol, propylene glycol, pentylene glycol or glycerol; - propylene glycol ethers that are liquid at room temperature, such as propylene glycol monomethyl
ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-n-butyl ether;
- cyclic ethers such as γ-butyrolactone;
- short-chain esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isopentyl acetate, methoxypropyl acetate or butyl lactate;
- ethers that are liquid at room temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether;
- alkanes that are liquid at room temperature, such as decane, heptane, dodecane or cyclohexane;
- alkyl sulfoxides such as dimethyl sulfoxide; - aldehydes that are liquid at room temperature, such as benzaldehyde or acetaldehyde;
- heterocyclic compounds such as tetrahydrofuran;
- propylene carbonate or ethyl 3-ethoxypropionate;
- mixtures thereof. Methyl acetate, isopropyl acetate, methoxypropyl acetate, butyl lactate, acetone, methyl ethyl ketone, diacetone alcohol, γ-butyrolactone, tetrahydrofuran, propylene carbonate, ethyl 3-ethoxypropionate and dimethyl sulfoxide, and mixtures thereof, are particularly preferred.
The second composition may contain at least one pasty compound chosen from the pasty compounds
described above. The second composition may contain at least one colouring agent and/or one filler as described above.
The compositions of the product may be in the form of a cast product, for example in the form of a stick or wand, or in the form of a dish that may be used by direct contact or with a sponge. In particular, they find an application as cast foundations, cast makeup rouges or eyeshadows, lipsticks, lipcare bases or lipcare balms, concealer products and nail varnishes. They may also be in the form of a soft paste or a gel, a more or less fluid cream, or a liquid packaged in a tube.
The compositions of the product according to the invention may especially constitute a cosmetic care composition for the face, the neck, the hands or the body (for example a care cream, an antisun oil or a body gel) , a makeup composition (for example a makeup gel, a cream or a stick) or a composition for artificially tanning or protecting the skin.
The compositions of the product according to the invention may be in the form of a care composition for the skin and/or the integuments or in the form of an antisun composition or a body hygiene composition, especially in the form of a deodorant. They are then especially in uncoloured form. They may then be used as a care base for the skin, the integuments or the lips
(lip balms, for protecting the lips against the cold and/or sunlight and/or the wind, or a care cream for the skin, the nails or the hair) .
For the purposes of the invention, the term "cosmetically acceptable" means a composition of pleasant appearance, odour and feel.
Each composition of the product according to the invention may be in any galenical form normally used for topical application and especially in the form of an oily or aqueous solution, an oily or aqueous gel, an oil-in-water or water-in-oil emulsion, a multiple emulsion, a dispersion of oil in water using vesicles, the vesicles being located at the oil/water interface, or a powder. Each composition may be fluid or solid. According to one embodiment, the first or the second composition, or both, have a continuous fatty phase preferably in anhydrous form and may contain less than 5% water and better still less than 1% water relative to the total weight of the first or second composition.
Each first and second composition may have the appearance of a lotion, a cream, an ointment, a soft paste, a salve, a solid that has been cast or moulded, especially as a stick or a dish, or a compacted solid. According to one embodiment, at least one of the first and second compositions is in the form of a paste or a stick.
Each composition may be packaged separately in the same packaging article, for example in a two- compartment pen, the base composition being delivered from one end of the pen and the top composition being delivered from the other end of the pen, each end being especially closed in a leaktight manner with a lid.
Alternatively, each of the compositions may be packaged in a different packaging article.
Preferably, the composition that is applied as the first coat is in liquid or pasty form, which is highly desirable in the case of a lipstick or an eyeliner.
The product according to the invention may be advantageously used for making up the skin and/or the lips and/or the integuments depending on the nature of the ingredients used. In particular, the product of the invention may be in the form of a solid foundation, a lipstick wand or paste, a concealer product, an eye contour product, an eyeliner, a mascara, an eyeshadow, a body-makeup product or a skin-colouring product.
Advantageously, the second composition has care, gloss or transparency properties.
A subject of the invention is also a lip product, a varnish, a mascara, a foundation, a tattoo, a makeup rouge or an eyeshadow comprising a first and a second composition as described above.
The compositions of the product of the invention may be obtained by heating the various constituents to the melting point of the highest- melting waxes, followed by casting the molten mixture in a mould (dish or finger stall) . They may also be obtained by extrusion, as described in patent application EP-A-O 667 146.
The invention is illustrated in greater detail in the following examples. The percentages are percentages by weight.
Example 1: Lip makeup product
First composition: stick of lipstick
Mass % A Polyethylene 11.28
Ozokerite 4.1
B Hydrogenated polyisobutene 7.42
Simmondsia chinensis (jojoba) seed oil 0.31 Phenyl trimethicone 2.54
Octyldodecanol 2.24
VP/eicosene copolymer 4.07
Arachidyl propionate 3.25
BHT 0.03
C Titanium dioxide 2.74
Red 7 0.54
Blue 1 lake 0.16
Yellow 6 lake 2.58
Iron oxides 0.25
Mica (and) titanium dioxide (and) iron 2 oxides D Trifluoropropyl dimethicone 8
Isododecane 2.4
Butyl acrylate copolymer containing 46.09 dendritic silicone side chains:
[tris (trimethylsiloxy) siloxyethyldimethyl- siloxy] silylpropyl methacrylate in cyclopentasiloxane (D5) :20/80
(as prepared according to example 1, paragraph 40 of document EP0963751A2) Second composition: colourless lipstick
Weight %
Silicone oil (PDMS) 25
DC200 from Dow Corning (5 cSt)
Dimethicone (and) dimethiconol 61
D2-9085 from Dow Corning (1550 cSt) Trifluoropropyl dimethicone (100 cSt) 1 X22-897 from Shin-Etsu
C30-45 alkyl dimethicone 5
(SF 1642 from GE Bayer Silicone) Polyethylene wax (MW 500) 8
The silicone oil, the dimethiconol and the fluorinated dimethicone are mixed together with heating until a homogeneous mixture is formed. The C30-C45 alkyl dimethicone is then added to the above mixture maintained at 1100C. The polyethylene wax is then added
portionwise until a homogeneous mixture is obtained.
The mixture is cooled to 90-950C and then poured into moulds, which are placed at -200C for 30 minutes. The sticks are finally removed from the moulds.
Example 2: Lip makeup product
First composition: lip gloss
Phase Ingredient Mass
%
A Nylon-βll/dimethicone copolymer 9.7
Butyl acrylate copolymer containing 10 dendritic silicone side chains:
[tris (trimethylsiloxy) siloxyethyldimethyl- siloxy] silylpropyl methacrylate (as prepared according to example 1, paragraph 40 of document EP0963751A2)
Cyclopentasiloxane 10
Disteardimonium hectorite (and) 25 propylene carbonate
B Isododecane 36.63
Titanium dioxide 2.74
Red 7 0.54
Blue 1 lake 0.16
Yellow 6 lake 2.58
Iron oxides 0.25
C Mica (and) titanium dioxide (and) iron 2
oxides
D Fragrance 0.4
Second com osition: lip balm