EP0944379A1 - Cosmetic composition in the form of an aqueous dispersion containing at least a polymeric colouring agent - Google Patents

Cosmetic composition in the form of an aqueous dispersion containing at least a polymeric colouring agent

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Publication number
EP0944379A1
EP0944379A1 EP97952063A EP97952063A EP0944379A1 EP 0944379 A1 EP0944379 A1 EP 0944379A1 EP 97952063 A EP97952063 A EP 97952063A EP 97952063 A EP97952063 A EP 97952063A EP 0944379 A1 EP0944379 A1 EP 0944379A1
Authority
EP
European Patent Office
Prior art keywords
composition according
dye
mol
film
nails
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP97952063A
Other languages
German (de)
French (fr)
Inventor
Valérie de la Poterie
Patricia Lemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Publication of EP0944379A1 publication Critical patent/EP0944379A1/en
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Definitions

  • Cosmetic composition in the form of an aqueous dispersion comprising at least one polymeric dye
  • the subject of the invention is new compositions for making up the eyes, the skin, the nails and the lips, comprising at least one polymeric sulfopolyester dye, as well as a method for making up the eyes, the skin, the nails, the lips. .
  • Is usually used as coloring material in cosmetic compositions either inorganic or organic pigments or lacquers, which are generally insoluble in aqueous and organic media, or dyes dissolved in aqueous or organic media.
  • the pigments and lacquers used in the make-up field are of very diverse origin and chemical nature. Their physicochemical properties: particle size, specific surface, density etc. are therefore very different. These differences are reflected in variations in behavior: the ease of implementation, of dispersion, the stability to light, to temperature and the mechanical properties in the case of powders are specific to each coloring matter. These differences in behavior frequently require the formulator to readjust the composition of the formula when the shade of this formula is changed. They also limit the production of certain formulas in the form of monochrome. In particular, certain shades are impracticable because the pigments or lacquers which theoretically allow them to be obtained are incompatible with one another.
  • Mineral oxides are preferably used for coloring cosmetic compositions, because the organic lacquers and the solubiated dyes show too much bleeding, which in particular has the effect of staining the ocular lenses in the case of eyeliners or mascaras.
  • these mineral pigments are dull and bland in color, so it is necessary to introduce a large amount of them in the formulas of nail polish mascara and eyeliner to obtain a sufficiently saturated line.
  • This high percentage of mineral particles strongly affects the gloss of the makeup film.
  • the shiny compositions In the case of lipsticks, the problem is the same, the shiny compositions must be formulated with small amounts of pigments. In the field of make-up, therefore, coverage and saturation of color are often associated with dullness of the film.
  • a pigment paste generally comprises a pigment, a surfactant or a dispersant and a wetting agent, such as glycerine or propylene glycol.
  • aqueous-based nail varnishes from aqueous dispersions of polymers, having a hard, shiny, water-resistant film, but the problem of adhesion of the varnish to the nail is often encountered. .
  • the film can then film easily. It is therefore sometimes necessary to use adhesion promoters.
  • adhesion promoters have the disadvantage of harming other properties of the varnish film, such as gloss or hardness.
  • the use of dyes dissolved in makeup compositions has the effect of accentuating wrinkles or streaks of the skin and / or nails, the dye coming to be fixed, by migration, preferably in these wrinkles or streaks.
  • This effect is contrary to that of attenuation of the skin defects that one seeks to obtain by makeup.
  • These solubiated dyes often have the drawback of leaving spots on the skin and nails after makeup removal, with which they have a great affinity.
  • the solubiated dyes have a very high coloring power, which leads to using them in infinitesimal quantities. Consequently, their dosage in a cosmetic formula under reproducible conditions is an extremely delicate operation. Also, it is with astonishment that the applicant has discovered new cosmetic compositions, comprising at least one polymeric sulfopolyester dye, compositions which can be prepared according to invariable formulas, whatever the desired shade, with a very wide range of shades and very nuanced, with a high intensity of coloration associated with a shiny effect if desired, with good lightfastness, including when the composition also comprises photoreactive pigments.
  • compositions do not release dye on the skin, which avoids the appearance of streaks on the made-up skin or spots after makeup removal. They thus allow non-permanent coloring of the skin, nails, lips or eyelashes: after removing makeup, the skin, nails, lips or eyelashes are not colored. This gives a clean makeup removal. It is said that the compositions "do not scratch”.
  • compositions are prepared from quantities of polymeric dye low enough not to destabilize the formulas, but in quantities large enough to be easily dosed in a reproducible manner.
  • the subject of the invention is a cosmetic composition in the form of an aqueous dispersion, characterized in that it comprises at least one polymeric sulfopolyester dye and at least one film-forming polymer.
  • the subject of the invention is also the use of a sulfopolyester polymeric dye, in a makeup composition for the eyes, the skin, the nails, the lips in the form of an aqueous dispersion, to form a colored film on the skin, eyelashes, eyelids, nails, lips.
  • Another subject of the invention is the use of a sulfopolyester polymeric dye in a makeup composition for the eyes, the skin, the nails, the lips in the form of an aqueous dispersion, which does not color the eyelashes, eyes, nails, lips after makeup removal.
  • the subject of the invention is also a method for making up the eyes, the skin, the nails, the lips, characterized in that a composition is applied to the eyelashes, the eyelids, the skin, the nails, the lips. as defined above.
  • polymeric dye is meant a copolymer based on at least two distinct monomers, at least one of which is a monomeric organic dye.
  • Sulfopolyester polymeric dyes can result from the polymerization of several monomers including:
  • the dicarboxylic acid residues carrying a sulfonic group can be chosen from cycloaliphatic diacids such as the sulfo diacid 1,4-cyclohexane carboxylic acid, or alternatively from aromatic diacids such as sulfophthalic acids, 4-sulfonaphthalene-2,7- acid. dicarboxylic.
  • the diol residues can be chosen, for example, from ethylene glycol, 1, 2-propane diol, 1, 3-propane diol, 2-methyl-1, 3-propanediol, 1, 4-butane diol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,10-decane diol, 1,12-dodecane diol, 1,2-cyclohexane diol, 1,4-cyclohexanediol, 1,2-cyclohexane dimethanol, x, 8-bis (hydroxymethyl) -tricyclo- [5.2.1.0] decane, in which x represents 3, 4 or 5; diols comprising at least one oxygen atom in the chain such as, for example, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-bis (2-hydroxyethyl) benzene, 1,4-bis (2- hydroxyethyl) benzene
  • these diols contain 2 to 18 and preferably 2 to 12 carbon atoms.
  • the coloring sulfopolyester may contain dicarboxylic acid residues free of sulfonic group; such residues can be of aliphatic, alicyclic or aromatic type, such as, for example, terephthalic, isophthalic acids, 1,4-cyclohexane dicarboxylic, 1,3-cyclohexane dicarboxylic, succinic, glutaric, adipic, sebacic, 1,2 dodecanedioic, 2,6-naphthalene dicarboxylic, etc.
  • the organic dye monomers according to the invention must contain at least two substituents capable of reacting with at least one of the other monomers used for the preparation of the polymeric dye and must be stable at the temperature and under the conditions for preparing said polymer.
  • the chemical nature of the coloring monomers does not matter for the implementation of the invention.
  • These can, for example, be chosen from anthraquinones, methines, bis-methines, aza-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, 2,5-diarylaminoterephthalic acids and their esters, phthaloyiphenothiazines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinones, nitroarylamines, benzodifuran, 2 H-1-benzopyran-2-one, quinophthalenes, quinophthalones quinacridones, triphenodioxazines, fluoridines, 4-amino-1, 8-naphthalimides, thioxanthrones,
  • the substituents carried by the coloring monomer and capable of reacting with the other monomers can for example be chosen from the following groups: hydroxy, carboxy, ester,; amino, alkyli amino:
  • R represents a group chosen from alkyls, aryls.
  • R is chosen from C1-C8 alkyl groups and phenyl. Even more preferably, R is chosen from methyl, ethyl and phenyl groups.
  • the polymeric dye comprises at least 5% by weight of coloring monomer, and does not comprise more than 55% by weight.
  • the percentage by weight of coloring monomer relative to the total weight of the copolymer ranges from 10 to 40%.
  • a water-dispersible coloring polymer having linking groups comprising at least about 20 mol% of carbonyloxy and up to about 80 mol% of carbonylamido, said polymer containing sulfonate groups "solubility in water and having from about 0.01 to about 40 mol%, based on the total of all the equivalents of hydroxyl, carboxyl or amino reagents, of dye comprising one or more heat stable organic compounds initially having at least one condensable group, which has been reacted on or in the polymeric backbone.
  • the above-mentioned equivalents include their various condensable derivatives, including carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N- (alkyl) 2 carbamyloxy, alkylamino, N- phenylcarbamyloxy, cyclohexanoyloxy and carbocyclohexyloxy.
  • the coloring polymer contains carbonyloxy linking groups in the linear molecular structure, where up to 80% of said linking groups can be carbonylamido linking groups, the polymer having an inherent viscosity of about 0.1 to about 1.0, measured in a solution of 60-40 parts by weight of phenol / tetrachloroethane, at 25 ° C and at a concentration of 0.25 grams of polymer in 100 ml of the solvent, the polymer containing essentially equimolar proportions of acid equivalents (100 mole percent) relative to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction residues of the reactants (a), ( b), (c), (d) and (e) or of their ester-generating derivatives or esteramide-generating derivatives:
  • H- (OCH 2 -CH 2 ) n -OH n being an integer from 2 to about 20 or (2) from about 0.1 to less than about 15 mole percent, based on the total percentage in moles of hydroxy or hydroxy equivalents and d 'amino, are a polyethylene glycol of structural formula:
  • n being an integer between 2 and about 500, and provided that the mole percentage of said polyethylene glycol in said range is inversely proportional to the value of n in said range;
  • each R in reactants (c) or (d) is an H atom or an alkyl group having from 1 to 4 carbon atoms;
  • the water-dispersible coloring polymer comprises:
  • glycol monomer comprising from 45 to 60 mol% of diethylene glycol and from 55 to 40 mol% of 1, 4-cyclohexanedimethanol or of ethylene glycol or their mixture, (c) from 0.5 to 10 mol% of monomer dye
  • sulfopolyester polymeric dyes are described in US Pat. No. 4,804,719.
  • sulfopolyester polymeric dyes can be of the crystalline, semi-crystalline or amorphous type.
  • the sulfopolyester polymeric dyes have an intrinsic viscosity of at least 0.20 (measured according to the method described in US Patent 4804719).
  • the polymeric dye which can be used in the present invention may be in the form of a dispersible or soluble powder or of a solution or of a dispersion in an aqueous medium.
  • a dispersion in an aqueous medium of a water-insoluble polymeric dye can be prepared in a known manner from water, of crude polymeric dye as described in documents US Pat. No. 5,032,670; US-4,999,418; US-5, 106.942; US-5,030,708; US-5,102,980; US-5,043,376, US-5,194,463.
  • the sulfopolyester polymeric dye in the form of a powder or granule, and at least one ionic surfactant, preferably an anionic or amphoteric surfactant.
  • the anionic and amphoteric surfactants can be preferably chosen from alkaline salts of C12-C24 fatty acids, soy phosphatides, phospholipids, lysophospholipids. These ionic surfactants are introduced in amounts preferably between 0.5 and 30%, and even more preferably between 1 and 10% by weight relative to the weight of the polymeric sulfopolyester dye.
  • these dispersions further comprise at least one nonionic surfactant, which is advantageously chosen from polyoxyethylenated derivatives having a molecular weight greater than 300, preferably around 1000 to 15000 and a hydrophilic-lipophilic balance (or HLB balance) greater than or equal to 10.
  • an aqueous dispersion of polymeric dye can be prepared by following the following steps:
  • the volatile organic solvent which can be used for the implementation of this process must be immiscible with water and capable of dissolving the polymer.
  • its boiling point is less than 100 ° C. It can for example be chosen from: hydrocarbon solvents such as n-hexane, cyclohexane, cyclopentane; chlorinated solvents such as methylene chloride, chloroform; alkyl esters of carboxylic acids, such as ethyl acetate; dialkyl ethers such as diisopropyl ether.
  • a mixture of solvents is used for the implementation of this process, comprising, in addition to the solvents described above, a volatile, polar, water-miscible solvent, such as acetone or a low molecular weight alkanol.
  • a volatile, polar, water-miscible solvent such as acetone or a low molecular weight alkanol.
  • the water from the aqueous dispersions described above can then be evaporated, for example by atomization or by lyophilization, in order to obtain a powder of a polymeric dye composition dispersible in other media.
  • an aqueous dispersion comprising at least one polymeric dye as described above and at least one film-forming polymer dispersible in water, insoluble in water.
  • this polymeric dye can be incorporated in the form of an aqueous solution or dispersion or as it is, in the form of a dispersible powder or of crude powder.
  • the polyester polymeric dye can be incorporated in the form of an aqueous dispersion or in the form of a water-dispersible powder.
  • the polymeric dyes which can be used in the compositions according to the invention can be introduced in amounts ranging from 0.1 to 20%.
  • the polymeric dyes described above have the advantage of having the same general chemical structure and the same physicochemical properties, in very different color ranges. Thus, a red pigment will have the same behavior as a yellow pigment. This homogeneity of behavior allows the manufacture of make-up compositions in the form of monochrome. When mixing monochrome to achieve a shade, there is no problem of incompatibility between the different colors.
  • polymeric dyes used in the emulsions according to the invention have a coloring power very close to that of organic lakes, and have a very high light stability, this even in the presence of titanium dioxide or zinc. They can therefore be used in place of organic lacquers in all makeup formulas. Their high light stability makes it possible to present the cosmetic compositions comprising them in transparent packaging. Thus, the user can choose more precisely the color of the product she is buying. In addition, they do not interfere with oils and / or active ingredients.
  • the pigment particles are easily dissolved or dispersed in the medium, without the need for special additives. No sedimentation is observed, even after a long period of storage.
  • the adhesion of the varnish film on the nail is improved by the incorporation of polymeric dyes, so there is no need to use adhesion promoters.
  • aqueous compositions of nail polish which are both hard, shiny and non-peelable.
  • the dispersions according to the invention comprise, in an aqueous phase, at least one sulfopolyester polymeric dye according to the invention and at least one film-forming polymer dispersible in water insoluble in water.
  • composition according to the invention therefore comprises particles of film-forming polymer dispersed in an aqueous medium.
  • polyurethanes for example anionics, polyester-polyurethanes, polyether-polyurethanes, radical polymers in particular of acrylic, styrene and / or vinyl type , polyesters, alkyd resins, alone or as a mixture.
  • compositions can also comprise at least one water-soluble film-forming polymer or copolymer.
  • film-forming polymers in water solution include water-soluble copolymers, and water-dispersible polycondensates with sulfonate functions. Such polymers are described in particular in patent application FR-A-2722404.
  • water-soluble copolymers mention may, for example, be made of vinyl copolymers (vinyl alcohols, vinyl acetates, vinyl pyrrolidone, etc.), acrylics, acrylamides.
  • hydrodispersible polycondensates containing sulfonate functions are known products, they are described in particular in documents US Pat. No. 3,779,993
  • water-dispersible polycondensates containing sulfonate functions is preferably meant copolyesters or copolyesteramides.
  • the copolyesters are obtained by polycondensation of at least one dicarboxylic acid or an ester thereof, of at least one diol and at least one difunctional compound sulfoaryldicarboxylique substituted on the aromatic ring by -S0 3 M wherein M represents a hydrogen atom or a metal ion such as Na + , Li + or K + .
  • M represents a hydrogen atom or a metal ion such as Na + , Li + or K + .
  • the polyesteramides are obtained in the same way as the polyesters, but the polycondensation also involves a diamine and / or an amino alcohol.
  • the film-forming polymer is not colored, that is to say that it does not contain a coloring monomer.
  • the dispersion may also comprise an associative polymer of the polyurethane type or a natural gum such as xanthan gum.
  • the dispersion preferably has an active material content of 5 to 70% by weight.
  • compositions according to the invention comprise at least one film-forming polymer.
  • this polymer when this polymer has a glass transition temperature below room temperature, a increased hardness and gloss of the film.
  • the film-forming polymer is not in the form of an aqueous dispersion containing a sulfopolyester and a copolymer containing vinyl acetate and a fumarate or maleate dialkyl and for which the copolymer is polymerized in the aqueous dispersion of sulfopolyester.
  • composition according to the invention can also comprise any additive known to a person skilled in the art as being capable of being incorporated into such a composition, such as cosolvents, spreading agents, wetting agents, dispersing agents, defoamers, preservatives, UV filters, dyes, pigments, such as for example titanium dioxide, nacres, active ingredients such as N-butylformal, D-panthenol, phytantriol, vitamins and their derivatives, keratin and its derivatives, melanin, collagen, cystine, chitosan and its derivatives, ceramides, biotin, trace elements, glycerin, protein hydrolysates, phospholipids, hydrating agents.
  • additives such as cosolvents, spreading agents, wetting agents, dispersing agents, defoamers, preservatives, UV filters, dyes, pigments, such as for example titanium dioxide, nacres, active ingredients such as N-butylformal, D-panthenol, phytant
  • composition according to the invention can be prepared by the expert on "basic general knowledge and according to the state of the art.
  • composition according to the invention may be in the form of a product to be applied to the nails, such as a varnish, a base for nails or a care base for nails, in the form of a product to be applied to eyelashes, such as a mascara, of a product to be applied to the skin such as a foundation, cheek, eyeshadow, eyeliner, product to apply on the lips such as lipstick, lip lacquer, lip gloss.
  • a product to be applied to the nails such as a varnish, a base for nails or a care base for nails
  • eyelashes such as a mascara
  • a product to be applied to the skin such as a foundation, cheek, eyeshadow, eyeliner
  • product to apply on the lips such as lipstick, lip lacquer, lip gloss.
  • the gloss measurements are carried out using a Micro Tri Gloss gloss meter sold by the company BYK GARDNER at an angle of 60 °.
  • the hardness measurements are made according to standard NFT-30-016. This measurement is made on a film dried at 30 ° C under 50% relative humidity.
  • Example 1 Composition of eyeliner
  • coloring polyester comprising 10% of blue coloring monomer, prepared in accordance with Example 4 of US Pat. No. 4,804,719 put in aqueous solution with 21.6% of active material.
  • composition obtained by dispersion of all the components in water is stable over time, in particular no sedimentation is observed after several weeks of storage.
  • This composition is liquid and easy to apply, it gives a saturated, covering and shiny makeup.
  • the varnish obtained is slightly colored, pink, and translucent, it does not color the nail after makeup removal.
  • the varnish film is shiny, hard and water resistant, it is only moderately peelable.
  • the varnish obtained is very colorful, burgundy and translucent, it does not color the nail after removing make-up.
  • the varnish film is shiny, hard, water resistant and non-peelable. No sedimentation is observed over time.
  • the varnish obtained does not color the nail after removing makeup.
  • the varnish film is shiny, hard and water resistant.
  • the gloss of the varnish film is measured according to Example 4, it is 94.0.

Abstract

The invention concerns a makeup composition for the skin, eyes, nails, lips in the form of an aqueous dispersion characterised in that it contains at least a sulphopolyester polymeric colouring agent and at least a filmforming polymer. The invention also concerns a makeup method.

Description

Composition cosmétique sous la forme d'une dispersion aqueuse comprenant au moins un colorant polymérique Cosmetic composition in the form of an aqueous dispersion comprising at least one polymeric dye
L'invention a pour objet de nouvelles compositions de maquillage des yeux, de la peau, des ongles, des lèvres comprenant au moins un colorant polymérique sulfopolyester, ainsi qu'un procédé de maquillage des yeux, de la peau, des ongles, des lèvres.The subject of the invention is new compositions for making up the eyes, the skin, the nails and the lips, comprising at least one polymeric sulfopolyester dye, as well as a method for making up the eyes, the skin, the nails, the lips. .
On utilise habituellement comme matière colorante dans les compositions cosmétiques, soit des pigments minéraux ou organiques ou des laques, qui sont généralement insolubles dans les milieux aqueux et organiques, soit des colorants solubies dans les milieux aqueux ou organiques. Les pigments et laques utilisés dans le domaine du maquillage sont d'origine et de nature chimique très diverses. Leurs propriétés physicochimiques : granulométrie, surface spécifique, densité etc.. sont donc très différents. Ces différences se traduisent par des variations de comportement : la facilité de mise en oeuvre, de dispersion, la stabilité à la lumière, à la température et les propriétés mécaniques dans le cas des poudres sont propres à chaque matière colorante. Ces différences de comportement obligent fréquemment le formulateur à réadapter la composition de la formule lorsque la teinte de cette formule est modifiée. Elles limitent également la réalisation de certaines formules sous forme de monochromes. En particulier, certaines teintes sont irréalisables du fait que les pigments ou les laques qui permettraient théoriquement de les obtenir sont incompatibles entre eux.Is usually used as coloring material in cosmetic compositions, either inorganic or organic pigments or lacquers, which are generally insoluble in aqueous and organic media, or dyes dissolved in aqueous or organic media. The pigments and lacquers used in the make-up field are of very diverse origin and chemical nature. Their physicochemical properties: particle size, specific surface, density etc. are therefore very different. These differences are reflected in variations in behavior: the ease of implementation, of dispersion, the stability to light, to temperature and the mechanical properties in the case of powders are specific to each coloring matter. These differences in behavior frequently require the formulator to readjust the composition of the formula when the shade of this formula is changed. They also limit the production of certain formulas in the form of monochrome. In particular, certain shades are impracticable because the pigments or lacquers which theoretically allow them to be obtained are incompatible with one another.
On utilise de préférence les oxydes minéraux pour la coloration des compositions cosmétiques, car les laques organiques et les colorants solubies présentent un dégorgement trop important ce qui a en particulier pour conséquence de tâcher les lentilles oculaires dans le cas des eye-liners ou des mascaras. Cependant, ces pigments minéraux sont de couleur terne et fade, il est donc nécessaire d'en introduire une grande quantité dans les formules de mascara de vernis à ongle et d'eye-liner pour obtenir un trait suffisamment saturé. Ce fort pourcentage de particules minérales affecte fortement la brillance du film de maquillage. Dans le cas des rouges à lèvres, le problème est identique, les compositions brillantes doivent être formulées avec des petites quantités de pigments. Dans le domaine du maquillage, on associe donc souvent couvrance et saturation de la couleur, à matité du film.Mineral oxides are preferably used for coloring cosmetic compositions, because the organic lacquers and the solubiated dyes show too much bleeding, which in particular has the effect of staining the ocular lenses in the case of eyeliners or mascaras. However, these mineral pigments are dull and bland in color, so it is necessary to introduce a large amount of them in the formulas of nail polish mascara and eyeliner to obtain a sufficiently saturated line. This high percentage of mineral particles strongly affects the gloss of the makeup film. In the case of lipsticks, the problem is the same, the shiny compositions must be formulated with small amounts of pigments. In the field of make-up, therefore, coverage and saturation of color are often associated with dullness of the film.
Dans le domaine des vernis à ongles, des laques à lèvres, des mascaras et des eye-liners se posent plusieurs problèmes bien spécifique des dispersions, qu'elles soient aqueuses ou organiques : II s'agit tout d'abord de la difficulté pour disperser les particules de pigment, de la sédimentation de ces particules, et le problème de l'adhérence du film de vernis, qui est contrariée par les pigments. Il est souvent nécessaire de passer par une pâte pigmentaire pour disperser les pigments dans l'eau. Une pâte pigmentaire comprend généralement un pigment, un tensio-actif ou un dispersant et un mouillant, tels que la glycérine ou le propylène glycol. Ces différents additifs ont tendance à réduire la dureté du film de vernis et/ou la résistance à l'eau de ce film. Lorsque l'on emploie des pigments, on les empêche de sédimenter grâce à des gélifiants qui contrarient la fluidité des formules.In the field of nail varnishes, lip lacquers, mascaras and eyeliners, there are several very specific problems of dispersions, whether aqueous or organic: Firstly, it is the difficulty of dispersing the pigment particles, the sedimentation of these particles, and the problem of the adhesion of the varnish film, which is thwarted by the pigments. It is often necessary to go through a pigment paste to disperse the pigments in water. A pigment paste generally comprises a pigment, a surfactant or a dispersant and a wetting agent, such as glycerine or propylene glycol. These various additives tend to reduce the hardness of the varnish film and / or the water resistance of this film. When pigments are used, they are prevented from sedimenting thanks to gelling agents which interfere with the fluidity of the formulas.
II est possible de préparer des vernis à ongles à base aqueuse à partir de dispersions aqueuses de polymères, présentant un film dur, brillant, résistant à l'eau, mais on se heurte souvent au problème de l'adhérence du vernis sur l'ongle. Le film peut alors se pelliculer facilement. Il est donc parfois nécessaire d'avoir recours à des promoteurs d'adhérence. Mais ces derniers présentent l'inconvénient de nuire à d'autres propriétés du film de vernis, tels que la brillance ou la dureté.It is possible to prepare aqueous-based nail varnishes from aqueous dispersions of polymers, having a hard, shiny, water-resistant film, but the problem of adhesion of the varnish to the nail is often encountered. . The film can then film easily. It is therefore sometimes necessary to use adhesion promoters. However, the latter have the disadvantage of harming other properties of the varnish film, such as gloss or hardness.
Dans le domaine du maquillage, seules les laques organiques permettaient jusqu'à présent d'obtenir des couleurs vives et intenses (les oxydes minéraux ont une couleur très fade). Cependant, la plupart des laques organiques présentent une très mauvaise tenue à la lumière, qui se traduit par une atténuation très nette de leur couleur dans le temps. Ce phénomène est encore aggravé lorsque ces laques sont associées à des pigments photoréactifs comme le dioxyde de titane. Or ces pigments photo-réactifs sont très largement utilisés dans le maquillage pour la protection contre les rayonnement ultra-violets. Par conséquent, l'utilisation des laques organiques est assez limitée, ce qui a pour conséquence une limitation des teintes réalisables.In the field of make-up, only organic lacquers have so far made it possible to obtain bright and intense colors (the mineral oxides have a very bland color). However, most organic lacquers exhibit very poor light fastness, which results in a very clear attenuation of their color over time. This phenomenon is further aggravated when these lacquers are combined with photoreactive pigments such as titanium dioxide. However, these photo-reactive pigments are very widely used in makeup for protection against ultraviolet radiation. Consequently, the use of organic lacquers is fairly limited, which results in a limitation of the achievable shades.
L'association de certains pigments, en particulier les oxydes de fer, avec des huiles et certains actifs, dont notamment les vitamines a souvent pour conséquence l'oxydation de ces huiles et de ces actifs.The association of certain pigments, in particular iron oxides, with oils and certain active agents, including vitamins in particular, often results in the oxidation of these oils and these active agents.
Dans les compositions de vernis, de laques à lèvres, de mascaras et d'eye-liners on utilise jusqu'à 10 % de pigments d'oxydes minéraux pour obtenir une coloration visible et acceptable. Cependant, une aussi forte concentration de pigments entraîne une forte diminution des performances rhéologiques du vernis, et produit donc un maquillage hétérogène sur les ongles. Les laques organiques, qui permettent l'obtention de couleurs beaucoup plus vives à des pourcentages inférieurs sont peu utilisables pour cette application car comme on l'a déjà indiqué, elles dégorgent facilement et donc risquent de tâcher les ongles.In the compositions of varnishes, lip lacquers, mascaras and eyeliners, up to 10% of mineral oxide pigments are used to obtain a visible and acceptable coloration. However, such a high concentration of pigments leads to a strong decrease in the rheological performance of the varnish, and therefore produces a heterogeneous makeup on the nails. Organic lacquers, which allow much brighter colors to be obtained at lower percentages, are of little use for this application because, as already indicated, they disgorge easily and therefore risk staining the nails.
En outre, l'utilisation de colorants solubies dans des compositions de maquillage a pour effet d'accentuer les rides ou stries de la peau et/ou des ongles, le colorant venant se fixer, par migration, préférentiellement dans ces rides ou stries. Cet effet est contraire à celui d'atténuation des défauts de la peau que l'on cherche à obtenir par le maquillage. Ces colorants solubies présentent souvent l'inconvénient de laisser après le démaquillage des taches sur la peau et les ongles, avec lesquels ils ont une grande affinité.In addition, the use of dyes dissolved in makeup compositions has the effect of accentuating wrinkles or streaks of the skin and / or nails, the dye coming to be fixed, by migration, preferably in these wrinkles or streaks. This effect is contrary to that of attenuation of the skin defects that one seeks to obtain by makeup. These solubiated dyes often have the drawback of leaving spots on the skin and nails after makeup removal, with which they have a great affinity.
Enfin, si les pigments minéraux doivent être utilisés en grandes quantités pour obtenir une coloration satisfaisante, en revanche, les colorants solubies ont un pouvoir colorant très élevé, ce qui conduit à les utiliser en quantités infinitésimales. Par conséquent leur dosage dans une formule cosmétique dans des conditions reproductibles est une opération extrêmement délicate. Aussi, c'est avec étonnement que la demanderesse a découvert de nouvelles compositions cosmétiques, comprenant au moins un colorant polymérique sulfopolyester, compositions qui peuvent être préparées suivant des formules invariables, quelle que soit la teinte souhaitée, avec une gamme de teintes très large et très nuancée, avec une grande intensité de coloration associée à un effet brillant si cela est souhaité, avec une bonne tenue à la lumière, y compris lorsque la composition comprend, en outre, des pigments photoréactifs.Finally, if the mineral pigments must be used in large quantities to obtain a satisfactory coloring, on the other hand, the solubiated dyes have a very high coloring power, which leads to using them in infinitesimal quantities. Consequently, their dosage in a cosmetic formula under reproducible conditions is an extremely delicate operation. Also, it is with astonishment that the applicant has discovered new cosmetic compositions, comprising at least one polymeric sulfopolyester dye, compositions which can be prepared according to invariable formulas, whatever the desired shade, with a very wide range of shades and very nuanced, with a high intensity of coloration associated with a shiny effect if desired, with good lightfastness, including when the composition also comprises photoreactive pigments.
En particulier, ces compositions ne relarguent pas de colorant sur la peau, ce qui évite l'apparition de stries sur la peau maquillée ou de tâches après le démaquillage. Elles permettent ainsi une coloration non permanente de la peau, des ongles, des lèvres, ou des cils : après le démaquillage, la peau, les ongles, les lèvres ou les cils ne sont pas colorés. On obtient ainsi un démaquillage net. On dit que les compositions "ne griffent pas".In particular, these compositions do not release dye on the skin, which avoids the appearance of streaks on the made-up skin or spots after makeup removal. They thus allow non-permanent coloring of the skin, nails, lips or eyelashes: after removing makeup, the skin, nails, lips or eyelashes are not colored. This gives a clean makeup removal. It is said that the compositions "do not scratch".
Ces compositions sont préparées à partir de quantités de colorant polymérique suffisamment faibles pour ne pas déstabiliser les formules, mais en quantités suffisamment importantes pour être facilement dosées de façon reproductible.These compositions are prepared from quantities of polymeric dye low enough not to destabilize the formulas, but in quantities large enough to be easily dosed in a reproducible manner.
L'invention a pour objet une composition cosmétique sous la forme d'une dispersion aqueuse, caractérisée en ce qu'elle comprend au moins un colorant polymérique sulfopolyester et au moins un polymère filmogène.The subject of the invention is a cosmetic composition in the form of an aqueous dispersion, characterized in that it comprises at least one polymeric sulfopolyester dye and at least one film-forming polymer.
L'invention a aussi pour objet l'utilisation d'un colorant polymérique sulfopolyester, dans une composition de maquillage des yeux, de la peau, des ongles, des lèvres sous la forme d'une dispersion aqueuse, pour former un film coloré sur la peau, les cils, les paupières, les ongles, les lèvres.The subject of the invention is also the use of a sulfopolyester polymeric dye, in a makeup composition for the eyes, the skin, the nails, the lips in the form of an aqueous dispersion, to form a colored film on the skin, eyelashes, eyelids, nails, lips.
L'invention a encore pour objet l'utilisation d'un colorant polymérique sulfopolyester dans une composition de maquillage des yeux, de la peau, des ongles, des lèvres sous la forme d'une dispersion aqueuse, qui ne colore pas les cils, les yeux, les ongles, les lèvres après le démaquillage. L'invention a également pour objet un procédé de maquillage des yeux, de la peau, des ongles, des lèvres, caractérisé par le fait que l'on applique sur les cils, les paupières, la peau, les ongles, les lèvres une composition telle que définie précédemment.Another subject of the invention is the use of a sulfopolyester polymeric dye in a makeup composition for the eyes, the skin, the nails, the lips in the form of an aqueous dispersion, which does not color the eyelashes, eyes, nails, lips after makeup removal. The subject of the invention is also a method for making up the eyes, the skin, the nails, the lips, characterized in that a composition is applied to the eyelashes, the eyelids, the skin, the nails, the lips. as defined above.
Par colorant polymérique, on entend un copolymère à base d'au moins deux monomères distincts dont l'un au moins est un colorant organique monomérique.By polymeric dye is meant a copolymer based on at least two distinct monomers, at least one of which is a monomeric organic dye.
Les colorants polymériques sulfopolyesters peuvent résulter de la polymérisation de plusieurs monomères dont :Sulfopolyester polymeric dyes can result from the polymerization of several monomers including:
(i) au moins un résidu acide di-carboxylique portant au moins un groupement sulfonique; (ii) au moins un résidu diol ; et(i) at least one dicarboxylic acid residue carrying at least one sulfonic group; (ii) at least one diol residue; and
(iii) au moins un monomère colorant.(iii) at least one coloring monomer.
Les résidus acide dicarboxylique porteurs de groupement sulfonique peuvent être choisis parmi les diacides cycloaliphatiques comme le sulfo diacide 1 ,4- cyclohexane carboxylique, ou bien encore parmi les diacides aromatiques tels que les acides sulfophtaliques, l'acide 4-sulfonaphtalène-2,7-dicarboxylique. Les résidus diols peuvent être choisi par exemple parmi l'éthylène glycol, le 1 ,2- propane diol, le 1 ,3-propane diol, le 2-méthyl-1 ,3-propanediol, le 1 ,4-butane diol, le 2,2-diméthyl-1 ,3-propanediol, le 1 ,6-hexanediol, le 1 ,10-décane diol, le 1 ,12- dodécane diol, le 1 ,2-cyclohexane diol, le 1 ,4-cyclohexanediol, le 1 ,2- cyclohexane diméthanol, le x,8-bis(hydroxyméthyl)-tricyclo-[5.2.1.0]décane, dans lequel x représente 3, 4 ou 5 ; les diols comprenant au moins un atome d'oxygène dans la chaîne comme par exemple le diéthylène glycol, le triéthylène glycol, le dipropylène glycol, le 1 ,3-bis (2-hydroxyéthyl) benzène, le 1 ,4-bis (2- hydroxyéthyl)benzène, etc.The dicarboxylic acid residues carrying a sulfonic group can be chosen from cycloaliphatic diacids such as the sulfo diacid 1,4-cyclohexane carboxylic acid, or alternatively from aromatic diacids such as sulfophthalic acids, 4-sulfonaphthalene-2,7- acid. dicarboxylic. The diol residues can be chosen, for example, from ethylene glycol, 1, 2-propane diol, 1, 3-propane diol, 2-methyl-1, 3-propanediol, 1, 4-butane diol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,10-decane diol, 1,12-dodecane diol, 1,2-cyclohexane diol, 1,4-cyclohexanediol, 1,2-cyclohexane dimethanol, x, 8-bis (hydroxymethyl) -tricyclo- [5.2.1.0] decane, in which x represents 3, 4 or 5; diols comprising at least one oxygen atom in the chain such as, for example, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-bis (2-hydroxyethyl) benzene, 1,4-bis (2- hydroxyethyl) benzene, etc.
En règle générale, ces diols comprennent 2 à 18 et préférentiellement 2 à 12 atomes de carbone. En outre, les sulfopolyester colorant peuvent comporter des résidus acide di- carboxylique exempt de groupement sulfonique ; de tels résidus peuvent être de type aliphatique, alicyclique ou aromatique, comme par exemple les acides téréphtalique, isophtalique, 1 ,4-cyclohexane dicarboxylique, 1 ,3-cyclohexane di- carboxylique, succinique, glutarique, adipique, sébacique, 1 , 2-dodécanedioïque, 2,6-naphtalène dicarboxylique, etc.Generally, these diols contain 2 to 18 and preferably 2 to 12 carbon atoms. In addition, the coloring sulfopolyester may contain dicarboxylic acid residues free of sulfonic group; such residues can be of aliphatic, alicyclic or aromatic type, such as, for example, terephthalic, isophthalic acids, 1,4-cyclohexane dicarboxylic, 1,3-cyclohexane dicarboxylic, succinic, glutaric, adipic, sebacic, 1,2 dodecanedioic, 2,6-naphthalene dicarboxylic, etc.
Les monomères colorants organiques selon l'invention doivent comporter au moins deux substituants susceptibles de réagir avec au moins l'un des autres monomères employés pour la préparation du colorant polymérique et doivent être stables à la température et dans les conditions de préparation dudit polymère.The organic dye monomers according to the invention must contain at least two substituents capable of reacting with at least one of the other monomers used for the preparation of the polymeric dye and must be stable at the temperature and under the conditions for preparing said polymer.
Hormis ces deux conditions préliminaires, la nature chimique des monomères colorants n'a pas d'importance pour la réalisation de l'invention. Ceux-ci peuvent par exemple, être choisis parmi les anthraquinones, les méthines, bis-méthines, les aza-méthines, les arylidènes, les 3H-dibenzo[7,i-j] isoquinolines, les acides 2,5-diarylaminotéréphtaliques et leurs esters, les phtaloyiphénothiazines, les phtaloylphénoxazines, les phtaloylacridone, les anthrapyrimidines, les anthrapyrazoles, les phtalocyanines, les quinophtalones, les indophénols, perinones, les nitroarylamines, benzodifurane, les 2 H-1-benzopyran-2-one, les quinophtalones, les perylènes, les quinacridones, les triphénodioxazines, les fluoridines, les 4-amino-1 ,8-naphtalimides, les thioxanthrones, les benzanthrones, les indanthrones, les indigo, thioindigo, xanthène, acridine, azine, oxazine, etc. On pourra se référer aux brevets US-4,267,306 ; US-4,359,570 ; US-4,403,092 ; US-4,617,373 ; US-4,080,355 ; US-4,740,581 ; US-4,116,923 ; US-4,745,173 ; US-4,804,719, US-5, 194,463 ; WO92/07913 pour trouver des exemples de monomères colorants utilisables dans la préparation des colorants, polymériques.Apart from these two preliminary conditions, the chemical nature of the coloring monomers does not matter for the implementation of the invention. These can, for example, be chosen from anthraquinones, methines, bis-methines, aza-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, 2,5-diarylaminoterephthalic acids and their esters, phthaloyiphenothiazines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinones, nitroarylamines, benzodifuran, 2 H-1-benzopyran-2-one, quinophthalenes, quinophthalones quinacridones, triphenodioxazines, fluoridines, 4-amino-1, 8-naphthalimides, thioxanthrones, benzanthrones, indanthrones, indigo, thioindigo, xanthene, acridine, azine, oxazine, etc. Reference may be made to US Patents 4,267,306; US-4,359,570; US-4,403,092; US-4,617,373; US-4,080,355; US-4,740,581; US-4,116,923; US-4,745,173; US-4,804,719, US-5, 194,463; WO92 / 07913 for finding examples of coloring monomers which can be used in the preparation of polymeric dyes.
Les substituants portés par le monomère colorant et susceptibles de réagir avec les autres monomères peuvent par exemple être choisis parmi les groupements suivants: hydroxy, carboxy, ester, ; amino, alkyli amino :The substituents carried by the coloring monomer and capable of reacting with the other monomers can for example be chosen from the following groups: hydroxy, carboxy, ester,; amino, alkyli amino:
0 II 0 II O o- -c- -OR -o- -C- R -C — OR0 II 0 II O o- -c- -OR -o- -C- R -C - OR
0 I I o- -c- -NHR0 I I o- -c- -NHR
dans lesquels R représente un groupement choisi parmi les alkyles, les aryles. De préférence R est choisi parmi les groupements alkyles en C1-C8 et le phényle. Encore plus préférentiellement R est choisi parmi les groupements méthyle, éthyle et phényle.in which R represents a group chosen from alkyls, aryls. Preferably R is chosen from C1-C8 alkyl groups and phenyl. Even more preferably, R is chosen from methyl, ethyl and phenyl groups.
Habituellement, le colorant polymérique comprend au moins 5 % en poids de monomère colorant, et n'en comprend pas plus de 55% en poids. De préférence, le pourcentage en poids de monomère colorant par rapport au poids total du copolymère va de 10 à 40 %.Usually, the polymeric dye comprises at least 5% by weight of coloring monomer, and does not comprise more than 55% by weight. Preferably, the percentage by weight of coloring monomer relative to the total weight of the copolymer ranges from 10 to 40%.
Pour la préparation des colorants polymériques, on peut se reporter aux procédés décrits dans le brevet US-5,804,719.For the preparation of the polymeric dyes, reference may be made to the methods described in US Pat. No. 5,804,719.
Selon un mode particulier de l'invention, on peut utiliser un polymère colorant dispersible dans l'eau ayant des groupes de liaison comprenant au moins environ 20 % en moles de carbonyloxy et jusqu'à environ 80 % en moles de carbonylamido, ledit polymère contenant des groupes sulfonate" hydrosolubilisants et ayant d'environ 0,01 à environ 40 % en moles, sur la base du total de tous les équivalents d'hydroxy, de carboxy ou d'amino réactifs, de colorant comprenant un ou plusieurs composés organiques thermostables ayant initialement au moins un groupe condensable, que l'on a fait réagir sur ou dans le tronc polymère. Les équivalents susmentionnés englobent leurs divers dérivés condensables, y compris des carbalcoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyle, carbamyloxy, N-(alkyl)2 carbamyloxy, alkylamino, N- phénylcarbamyloxy, cyclohexanoyloxy et carbocyclohexyloxy.According to a particular embodiment of the invention, it is possible to use a water-dispersible coloring polymer having linking groups comprising at least about 20 mol% of carbonyloxy and up to about 80 mol% of carbonylamido, said polymer containing sulfonate groups "solubility in water and having from about 0.01 to about 40 mol%, based on the total of all the equivalents of hydroxyl, carboxyl or amino reagents, of dye comprising one or more heat stable organic compounds initially having at least one condensable group, which has been reacted on or in the polymeric backbone. The above-mentioned equivalents include their various condensable derivatives, including carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N- (alkyl) 2 carbamyloxy, alkylamino, N- phenylcarbamyloxy, cyclohexanoyloxy and carbocyclohexyloxy.
Dans une forme préférée de la présente invention, le polymère colorant contient des groupes de liaison carbonyloxy dans la structure moléculaire linéaire, où jusqu'à 80 % desdits groupes de liaison peuvent être des groupes de liaison carbonylamido, le polymère ayant une viscosité inhérente d'environ 0,1 à environ 1 ,0, mesurée dans une solution à 60-40 parties en poids de phénol/tétrachloroéthane, à 25 °C et à une concentration de 0,25 gramme de polymère dans 100 ml du solvant, le polymère contenant des proportions essentiellement équimolaires d'équivalents d'acide (100 pour cent en moles) par rapport aux équivalents d'hydroxy et d'amino (100 pour cent en moles), le polymère comprenant les résidus de réaction des réactifs (a), (b), (c), (d) et (e) suivants ou de leurs dérivés générateurs d'ester ou générateurs d'estéramide :In a preferred form of the present invention, the coloring polymer contains carbonyloxy linking groups in the linear molecular structure, where up to 80% of said linking groups can be carbonylamido linking groups, the polymer having an inherent viscosity of about 0.1 to about 1.0, measured in a solution of 60-40 parts by weight of phenol / tetrachloroethane, at 25 ° C and at a concentration of 0.25 grams of polymer in 100 ml of the solvent, the polymer containing essentially equimolar proportions of acid equivalents (100 mole percent) relative to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction residues of the reactants (a), ( b), (c), (d) and (e) or of their ester-generating derivatives or esteramide-generating derivatives:
(a) au moins un acide dicarboxylique difonctionnel(a) at least one difunctional dicarboxylic acid
(b) d'environ 4 à environ 25 pour cent en moles, sur la base d'un total de tous les équivalents d'acide, d'hydroxyle et d'amino étant égal à 200 pour cent en moles, d'au moins 1 sulfomonomere difonctionnel contenant au moins un groupe sulfonate cationique relié à un noyau aromatique ou cycloaliphatique où les groupes fonctionnels sont des hydroxy, carboxyle ou amino ;(b) from about 4 to about 25 mole percent, based on a total of all equivalents of acid, hydroxyl and amino being 200 mole percent, of at least 1 difunctional sulfomonomer containing at least one cationic sulfonate group linked to an aromatic or cycloaliphatic ring where the functional groups are hydroxy, carboxyl or amino;
(c) au moins un réactif difonctionnel choisi parmi un glycol ou un mélange d'un glycol et d'une diamine ayant deux groupes -NRH, le glycol contenant deux groupes -CH2-OH dont(c) at least one difunctional reagent chosen from a glycol or a mixture of a glycol and a diamine having two -NRH groups, the glycol containing two -CH 2 -OH groups of which
(1 ) au moins 10 pour cent en moles, sur la base du pourcentage total en moles d'équivalents d'hydroxy ou d'hydroxy et d'amino, sont un polyéthylèneglycol de formule structurale :(1) at least 10 mole percent, based on the total mole percentage of hydroxy or hydroxy and amino equivalents, is a polyethylene glycol of structural formula:
H-(OCH2-CH2)n-OH n étant un entier de 2 à environ 20 ou (2) d'environ 0,1 à moins d'environ 15 pour cent en moles, sur la base du pourcentage total en moles d'équivalents d'hydroxy ou d'hydroxy et d'amino, sont un polyéthylèneglycol de formule structurale :H- (OCH 2 -CH 2 ) n -OH n being an integer from 2 to about 20 or (2) from about 0.1 to less than about 15 mole percent, based on the total percentage in moles of hydroxy or hydroxy equivalents and d 'amino, are a polyethylene glycol of structural formula:
H-(OCH2-CH2)n-OHH- (OCH 2 -CH 2 ) n -OH
n étant un entier compris entre 2 et environ 500, et à condition que le pourcentage en moles dudit polyéthylèneglycol dans ladite gamme soit inversement proportionnel à la valeur de n dans ladite gamme ;n being an integer between 2 and about 500, and provided that the mole percentage of said polyethylene glycol in said range is inversely proportional to the value of n in said range;
(d) de zéro à au moins un réactif difonctionnel choisi parmi un acide hydroxycarboxylique ayant un groupe -C(R)2-OH, un acide aminocarboxylique ayant un groupe -NRH, et un amino-alcool ayant un groupe - C(R)2-OH et un groupe -NRH, ou des mélanges desdits réactifs difonctionnels ; où chaque R dans les réactifs (c) ou (d) est un atome H ou un groupe alkyle ayant de 1 à 4 atomes de carbone ; et(d) from zero to at least one difunctional reagent chosen from a hydroxycarboxylic acid having a group -C (R) 2 -OH, an aminocarboxylic acid having a group -NRH, and an amino alcohol having a group - C (R) 2 -OH and a group -NRH, or mixtures of said difunctional reagents; wherein each R in reactants (c) or (d) is an H atom or an alkyl group having from 1 to 4 carbon atoms; and
(e) d'environ 0,1 % en moles à environ 15 % en moles, sur la base d'un total de tous les équivalents d'acide, d'hydroxyle et d'amino étant égal à 200 % en moles, de colorant ayant au moins un groupe acide, hydroxy ou amino que l'on a fait réagir sur ou dans la chaîne polymère.(e) from about 0.1 mol% to about 15 mol%, based on a total of all the equivalents of acid, hydroxyl and amino being 200 mol%, dye having at least one acid, hydroxy or amino group which has been reacted on or in the polymer chain.
Avantageusement, le polymère colorant hydrodispersible comprend :Advantageously, the water-dispersible coloring polymer comprises:
(a) un monomère acide comprenant de 75 mole % à 84 mole % d'acide isophtalique et de 25 mole % à 16 mole % de sel de sodium de l'acide sulfo-5- isophtalique,(a) an acid monomer comprising from 75 mol% to 84 mol% of isophthalic acid and from 25 mol% to 16 mol% of sodium salt of 5-isophthalic acid,
(b) un monomère glycol comprenant de 45 à 60 mole % de diéthylène glycol et de 55 à 40 mole % de 1 ,4-cyclohexanediméthanol ou d'éthylèneglycol ou leur mélange, (c) de 0,5 à 10 mole % de monomère colorant De tels colorants polymériques sulfopolyesters sont décrits dans le brevet US- 4,804,719.(b) a glycol monomer comprising from 45 to 60 mol% of diethylene glycol and from 55 to 40 mol% of 1, 4-cyclohexanedimethanol or of ethylene glycol or their mixture, (c) from 0.5 to 10 mol% of monomer dye Such sulfopolyester polymeric dyes are described in US Pat. No. 4,804,719.
Ces colorants polymériques sulfopolyesters peuvent être de type cristallin, semi- cristallin ou amorphe.These sulfopolyester polymeric dyes can be of the crystalline, semi-crystalline or amorphous type.
Habituellement, les colorants polymériques sulfopolyesters ont une viscosité intrinsèque d'au moins 0,20 (mesurée selon la méthode décrite dans le brevet US 4804719).Usually, the sulfopolyester polymeric dyes have an intrinsic viscosity of at least 0.20 (measured according to the method described in US Patent 4804719).
Le colorant polymérique utilisable dans la présente invention peut se présenter sous la forme d'une poudre dispersible ou soluble ou d'une solution ou d'une dispersion en milieu aqueux.The polymeric dye which can be used in the present invention may be in the form of a dispersible or soluble powder or of a solution or of a dispersion in an aqueous medium.
Une dispersion en milieu aqueux d'un colorant polymérique insoluble dans l'eau peut être préparée de façon connue à partir d'eau, de colorant polymérique brut tel que décrit dans les documents US-5,032,670 ; US-4,999,418 ; US-5, 106,942 ; US-5,030,708 ; US-5,102,980 ; US-5,043,376, US-5,194,463. Par exemple on peut partir du colorant polymérique sulfopolyester sous forme de poudre ou de granulé, et d'au moins un tensio-actif ionique, de préférence un tensio-actif anionique ou amphotère. Les tensio-actifs anioniques et amphotères peuvent être choisis préférentiellement parmi les sels alcalins d'acides gras en C12-C24, les phosphatides de soja, les phospholipides, les lysophospholipides. Ces tensio- actifs ioniques sont introduits en quantités préférentiellement comprises entre 0,5 et 30%, et encore plus préférentiellement entre 1 et 10% en poids par rapport au poids du colorant polymérique sulfopolyester. De façon préférentielle, ces dispersions comprennent en outre au moins un tensioactif non-ionique, que l'on choisit avantageusement parmi les dérivés polyoxyéthylénés ayant un poids moléculaire supérieur à 300, préférablement aux alentours de 1000 à 15000 et une balance hydrophile-lipophile (ou balance HLB) supérieure ou égale à 10. Par exemple, on peut préparer une dispersion aqueuse de colorant polymérique en suivant les étapes suivantes :A dispersion in an aqueous medium of a water-insoluble polymeric dye can be prepared in a known manner from water, of crude polymeric dye as described in documents US Pat. No. 5,032,670; US-4,999,418; US-5, 106.942; US-5,030,708; US-5,102,980; US-5,043,376, US-5,194,463. For example, it is possible to start from the sulfopolyester polymeric dye in the form of a powder or granule, and at least one ionic surfactant, preferably an anionic or amphoteric surfactant. The anionic and amphoteric surfactants can be preferably chosen from alkaline salts of C12-C24 fatty acids, soy phosphatides, phospholipids, lysophospholipids. These ionic surfactants are introduced in amounts preferably between 0.5 and 30%, and even more preferably between 1 and 10% by weight relative to the weight of the polymeric sulfopolyester dye. Preferably, these dispersions further comprise at least one nonionic surfactant, which is advantageously chosen from polyoxyethylenated derivatives having a molecular weight greater than 300, preferably around 1000 to 15000 and a hydrophilic-lipophilic balance (or HLB balance) greater than or equal to 10. For example, an aqueous dispersion of polymeric dye can be prepared by following the following steps:
(i) préparation d'une émulsion huile dans eau à partir d'eau, d'une solution du colorant polymérique dans un solvant organique volatile dans lequel il est soluble, en présence d'au moins un tensio-actif ionique et éventuellement d'un tensio-actif non-ionique ; (ii) évaporation du solvant organique volatil.(i) preparation of an oil-in-water emulsion from water, of a solution of the polymeric dye in a volatile organic solvent in which it is soluble, in the presence of at least one ionic surfactant and optionally a nonionic surfactant; (ii) evaporation of the volatile organic solvent.
Le solvant organique volatile utilisable pour la mise en oeuvre de ce procédé doit être non miscible à l'eau et susceptible de solubiliser le polymère. De préférence son point d'ébullition est inférieur à 100°C. Il peut par exemple être choisi parmi : les solvants hydrocarbonés comme le n-hexane, le cyclohexane, le cyclopentane ; les solvants chlorés comme le chlorure de méthylène, le chloroforme ; les alkyl esters d'acides carboxyliques, comme l'acétate d'éthyle ; les dialkyléthers comme le diisopropyléther. On utilise préférentiellement pour la mise en oeuvre de ce procédé un mélange de solvants comprenant, outre les solvants décrits ci-dessus un solvant volatile, polaire, miscible à l'eau, comme l'acétone ou un alcanol de faible poids moléculaire.The volatile organic solvent which can be used for the implementation of this process must be immiscible with water and capable of dissolving the polymer. Preferably its boiling point is less than 100 ° C. It can for example be chosen from: hydrocarbon solvents such as n-hexane, cyclohexane, cyclopentane; chlorinated solvents such as methylene chloride, chloroform; alkyl esters of carboxylic acids, such as ethyl acetate; dialkyl ethers such as diisopropyl ether. Preferably, a mixture of solvents is used for the implementation of this process, comprising, in addition to the solvents described above, a volatile, polar, water-miscible solvent, such as acetone or a low molecular weight alkanol.
Pour plus d'information sur un tel procédé, on peut se référer aux brevet US 5,043,376 et US 5,104,913.For more information on such a process, reference can be made to US Patents 5,043,376 and US 5,104,913.
L'eau des dispersions aqueuses décrites ci-dessus peut ensuite être évaporée, par exemple par atomisation ou par lyophilisation, afin d'obtenir une poudre d'une composition de colorant polymérique dispersible dans d'autres milieux.The water from the aqueous dispersions described above can then be evaporated, for example by atomization or by lyophilization, in order to obtain a powder of a polymeric dye composition dispersible in other media.
En employant des méthodes connues de l'homme de métier, on prépare une dispersion aqueuse comprenant au moins un colorant polymérique tel que décrit ci-dessus et au moins un polymère filmogène dispersible dans l'eau, insoluble dans l'eau. Comme il vient d'être exposé, ce colorant polymérique peut être incorporé sous forme de solution ou de dispersion aqueuse ou tel quel, sous forme de poudre dispersible ou de poudre brute. De préférence, le colorant polymérique polyester peut être incorporer sous forme de dispersion aqueuse ou sous forme de poudre dispersible dans l'eau.Using methods known to those skilled in the art, an aqueous dispersion is prepared comprising at least one polymeric dye as described above and at least one film-forming polymer dispersible in water, insoluble in water. As has just been explained, this polymeric dye can be incorporated in the form of an aqueous solution or dispersion or as it is, in the form of a dispersible powder or of crude powder. Preferably, the polyester polymeric dye can be incorporated in the form of an aqueous dispersion or in the form of a water-dispersible powder.
Les colorants polymériques utilisables dans les compositions selon l'invention peuvent être introduits en quantités allant de 0,1 à 20%.The polymeric dyes which can be used in the compositions according to the invention can be introduced in amounts ranging from 0.1 to 20%.
Les colorants polymériques décrits ci-dessus ont l'avantage de présenter la même structure chimique générale et les mêmes propriétés physico-chimiques, dans des gammes de couleurs très différentes. Ainsi, un pigment rouge aura le même comportement qu'un pigment de couleur jaune. Cette homogénéité de comportement permet la fabrication des compositions de maquillages sous forme de monochromes. Lors du mélange des monochromes pour la réalisation d'une teinte, on n'observe aucun problème d'incompatibilité entre les différentes couleurs.The polymeric dyes described above have the advantage of having the same general chemical structure and the same physicochemical properties, in very different color ranges. Thus, a red pigment will have the same behavior as a yellow pigment. This homogeneity of behavior allows the manufacture of make-up compositions in the form of monochrome. When mixing monochrome to achieve a shade, there is no problem of incompatibility between the different colors.
Ces colorants ont un pouvoir colorant supérieur aux oxydes minéraux et proche de celui des laques organiques : 4 à 5 % suffisent à donner un mascara de couleur vive et intense. Les problèmes de rhéologie sont donc fortement atténués. De plus, ces polymères colorés ne relarguent pas de colorant. Il n'y a donc aucun problème d'apparition de stries, de tâchage de la peau ou des lentilles oculaires.These dyes have a coloring power superior to mineral oxides and close to that of organic lakes: 4 to 5% is enough to give a mascara of bright and intense color. The rheology problems are therefore greatly reduced. In addition, these colored polymers do not release dye. There is therefore no problem with the appearance of streaks, staining of the skin or ocular lenses.
Ces colorants polymériques, utilisés dans les émulsions selon l'invention ont un pouvoir colorant très proche de celui des laques organiques, et présentent une très grande stabilité à la lumière, ceci même en présence de dioxyde de titane ou de zinc. On peut donc les utiliser à la place des laques organiques dans toutes les formules de maquillage. Leur grande stabilité à la lumière permet de présenter les compositions cosmétiques les comprenant dans des emballages transparents. Ainsi, l'utilisatrice peut choisir avec plus de précision la couleur du produit qu'elle achète. En outre, ils n'interfèrent pas avec les huiles et/ou les actifs.These polymeric dyes, used in the emulsions according to the invention have a coloring power very close to that of organic lakes, and have a very high light stability, this even in the presence of titanium dioxide or zinc. They can therefore be used in place of organic lacquers in all makeup formulas. Their high light stability makes it possible to present the cosmetic compositions comprising them in transparent packaging. Thus, the user can choose more precisely the color of the product she is buying. In addition, they do not interfere with oils and / or active ingredients.
Ces colorants polymériques de couleurs vives et intenses, ont la particularité d'être suffisamment couvrants pour qu'une petite quantité soit suffisante pour colorer une formule cosmétique, telles celles citées ci-dessus. La brillance du film est donc nettement améliorée. On obtient un maquillage à la fois couvrant, saturé et brillant.These brightly colored and intense polymeric dyes have the particularity of being sufficiently covering so that a small amount is sufficient to color a cosmetic formula, such as those mentioned above. The gloss of the film is therefore significantly improved. We obtain a makeup that is both covering, saturated and shiny.
Les particules de pigment sont facilement solubilisées ou dispersées dans le milieu, sans qu'il soit besoin de recourir à des additifs particuliers. On n'observe aucune sédimentation, même après une longue période de stockage. En outre, l'adhérence du film de vernis sur l'ongle est améliorée par l'incorporation des colorants polymériques, on n'a donc pas besoin d'utiliser de promoteurs d'adhérence. Ainsi il est possible de préparer des compositions aqueuses de vernis à ongle qui soient à la fois dures brillantes et non pelables.The pigment particles are easily dissolved or dispersed in the medium, without the need for special additives. No sedimentation is observed, even after a long period of storage. In addition, the adhesion of the varnish film on the nail is improved by the incorporation of polymeric dyes, so there is no need to use adhesion promoters. Thus it is possible to prepare aqueous compositions of nail polish which are both hard, shiny and non-peelable.
Les dispersions selon l'invention comprennent dans une phase aqueuse, au moins un colorant polymérique sulfopolyester selon l'invention et au moins un polymère filmogène dispersible dans l'eau insoluble dans l'eau.The dispersions according to the invention comprise, in an aqueous phase, at least one sulfopolyester polymeric dye according to the invention and at least one film-forming polymer dispersible in water insoluble in water.
La composition selon l'invention comprend donc des particules de polymère filmogène en dispersion dans un milieu aqueux.The composition according to the invention therefore comprises particles of film-forming polymer dispersed in an aqueous medium.
Parmi les polymères filmogènes en dispersion dans l'eau susceptibles d'être utilisés, on peut citer les polyuréthannes, par exemple anioniques, les polyester- polyuréthannes, les polyéther-polyuréthannes, les polymères radicalaires notamment de type acrylique, acrylique styrène et/ou vinylique, les polyesters, les résines alkydes, seuls ou en mélange.Among the film-forming polymers in dispersion in water which may be used, mention may be made of polyurethanes, for example anionics, polyester-polyurethanes, polyether-polyurethanes, radical polymers in particular of acrylic, styrene and / or vinyl type , polyesters, alkyd resins, alone or as a mixture.
Ces compositions peuvent en outre comprendre au moins un polymère ou copolymère filmogène soluble dans l'eau. Parmi les polymères filmogènes en solution dans l'eau on peut citer les copolymères hydrosolubles, et les polycondensats hydrodispersibles à fonctions sulfonates. De tels polymères sont décrits en particulier dans la demande de brevet FR-A-2722404.These compositions can also comprise at least one water-soluble film-forming polymer or copolymer. Among the film-forming polymers in water solution include water-soluble copolymers, and water-dispersible polycondensates with sulfonate functions. Such polymers are described in particular in patent application FR-A-2722404.
Comme copolymères hydrosolubles, on peut citer par exemple les copolymères vinyliques (vinylalcools, vinylacétates, vinylpyrrolidone...), acryliques, acrylamides.As water-soluble copolymers, mention may, for example, be made of vinyl copolymers (vinyl alcohols, vinyl acetates, vinyl pyrrolidone, etc.), acrylics, acrylamides.
Les polycondensats hydrodispersibles à fonctions sulfonates sont des produits connus, ils sont décrits notamment dans les documents US-3779993, US-The hydrodispersible polycondensates containing sulfonate functions are known products, they are described in particular in documents US Pat. No. 3,779,993
4300580 et EP-A-540374. Par polycondensats hydrodispersibles à fonctions sulfonates on entend de préférence des copolyesters ou des copolyesteramides.4300580 and EP-A-540374. By water-dispersible polycondensates containing sulfonate functions is preferably meant copolyesters or copolyesteramides.
Les copolyesters sont obtenus par polycondensation d'au moins un acide dicarboxylique ou d'un de ses esters, d'au moins un diol et d'au moins un composé difonctionnel sulfoaryldicarboxylique substitué sur le noyau aromatique par un groupe -S03M dans lequel M représente un atome d'hydrogène ou un ion métallique tel que Na+, Li+ ou K+. Les polyesteramides sont obtenus de la même manière que les polyesters mais la polycondensation fait également intervenir une diamine et/ou un amino-alcool.The copolyesters are obtained by polycondensation of at least one dicarboxylic acid or an ester thereof, of at least one diol and at least one difunctional compound sulfoaryldicarboxylique substituted on the aromatic ring by -S0 3 M wherein M represents a hydrogen atom or a metal ion such as Na + , Li + or K + . The polyesteramides are obtained in the same way as the polyesters, but the polycondensation also involves a diamine and / or an amino alcohol.
En particulier, le polymère filmogène n'est pas coloré, c'est-à-dire qu'il ne contient pas de monomère colorant.In particular, the film-forming polymer is not colored, that is to say that it does not contain a coloring monomer.
La dispersion peut également comprendre un polymère associatif de type polyuréthanne ou une gomme naturelle telle que la gomme xanthane.The dispersion may also comprise an associative polymer of the polyurethane type or a natural gum such as xanthan gum.
La dispersion présente de préférence un taux de matière active de 5 à 70% en poids.The dispersion preferably has an active material content of 5 to 70% by weight.
Les compositions selon l'invention comprennent au moins un polymère filmogène. Dans les compositions selon l'invention, lorsque ce polymère a une température de transition vitreuse inférieure à la température ambiante, on observe une augmentation de la dureté et de la brillance du film. Ces effets sont particulièrement recherchés pour la préparation de vernis à ongles, d'eye-liners et de mascaras.The compositions according to the invention comprise at least one film-forming polymer. In the compositions according to the invention, when this polymer has a glass transition temperature below room temperature, a increased hardness and gloss of the film. These effects are particularly sought after for the preparation of nail varnishes, eyeliners and mascaras.
En particulier, lorsque la composition est sous la forme d'un vernis à ongles, le polymère filmogène n'est pas sous la forme d'une dispersion aqueuse contenant un sulfopolyester et un copolymère contenant de l'acétate de vinyle et un fumarate ou maléate de dialkyle et pour laquelle le copolymère est polymérisé dans la dispersion aqueuse de sulfopolyester.In particular, when the composition is in the form of a nail varnish, the film-forming polymer is not in the form of an aqueous dispersion containing a sulfopolyester and a copolymer containing vinyl acetate and a fumarate or maleate dialkyl and for which the copolymer is polymerized in the aqueous dispersion of sulfopolyester.
La composition selon l'invention peut en outre comprendre tout additif connu de l'homme du métier comme étant susceptible d'être incorporé dans une telle composition, tels que des cosolvants, des agents d'étalement, des agents mouillants, des agents dispersants, des anti-mousses, des conservateurs, des filtres UV, des colorants, des pigments, comme par exemple du dioxyde de titane, des nacres, des actifs tels que le N-butylformal, le D-panthénol, le phytantriol, les vitamines et leurs dérivés, la kératine et ses dérivés, la mélanine, le collagène, la cystine, le chitosane et ses dérivés, les céramides, la biotine, les oligo-éléments, la glycérine, les hydrolysats de protéines, les phospholipides, les agents hydratants. Bien entendu l'homme du métier veillera à choisir ce ou ces éventuels composés complémentaires, et/ou leur quantité, de manière telle que les propriétés avantageuses de la composition selon l'invention ne soient pas, ou substantiellement pas, altérées par l'adjonction envisagée.The composition according to the invention can also comprise any additive known to a person skilled in the art as being capable of being incorporated into such a composition, such as cosolvents, spreading agents, wetting agents, dispersing agents, defoamers, preservatives, UV filters, dyes, pigments, such as for example titanium dioxide, nacres, active ingredients such as N-butylformal, D-panthenol, phytantriol, vitamins and their derivatives, keratin and its derivatives, melanin, collagen, cystine, chitosan and its derivatives, ceramides, biotin, trace elements, glycerin, protein hydrolysates, phospholipids, hydrating agents. Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, altered by the addition considered.
La composition selon l'invention peut être préparée par l'homme du métier sur" base de ses connaissances générales et selon l'état de la technique.The composition according to the invention can be prepared by the expert on "basic general knowledge and according to the state of the art.
La composition selon l'invention peut se présenter sous la forme d'un produit à appliquer sur les ongles, tel qu'un vernis, une base pour ongles ou une base de soin pour ongles, sous la forme d'un produit à appliquer sur les cils, tel qu'un mascara, d'un produit à appliquer sur la peau tel qu'un fond de teint, d'un fard à joue, d'un fard à paupières, d'un eye liner, d'un produit à appliquer sur les lèvres tel qu'un rouge à lèvre, une laque à lèvres, un brillant à lèvres (gloss).The composition according to the invention may be in the form of a product to be applied to the nails, such as a varnish, a base for nails or a care base for nails, in the form of a product to be applied to eyelashes, such as a mascara, of a product to be applied to the skin such as a foundation, cheek, eyeshadow, eyeliner, product to apply on the lips such as lipstick, lip lacquer, lip gloss.
L'invention est illustrée plus en détail dans les exemples suivants.The invention is illustrated in more detail in the following examples.
Dans les exemples, les mesures de brillance sont réalisées à l'aide d'un Brillance-mètre Micro Tri Gloss commercialisé par la société BYK GARDNER sous un angle de 60°.In the examples, the gloss measurements are carried out using a Micro Tri Gloss gloss meter sold by the company BYK GARDNER at an angle of 60 °.
Les mesures de dureté sont faites suivant la norme NFT-30-016. Cette mesure est faite sur un film séché à 30°C sous 50% d'humidité relative.The hardness measurements are made according to standard NFT-30-016. This measurement is made on a film dried at 30 ° C under 50% relative humidity.
Exemple 1 : Composition d'eye-linerExample 1: Composition of eyeliner
Alcool polyvinyiique 2%Polyvinyl alcohol 2%
Propylène glycol 5%Propylene glycol 5%
Hydroxyéthylcellulose 0,1 %Hydroxyethylcellulose 0.1%
Laponite 0,2%0.2% Laponite
Lauryl sulfate de sodium 0,1 % Oxyde de fer noir 5% colorant polymérique bleu (*) 10%Sodium lauryl sulfate 0.1% Black iron oxide 5% blue polymer dye ( * ) 10%
SANCURE *) 18,7%SANCURE * ) 18.7%
Eau qsp 100Water qs 100
(*) polyester colorant comprenant 10% de monomère colorant bleu, préparé conformément à l'exemple 4 du brevet US-4, 804,719 mis en solution aqueuse à 21 ,6% de matière active. (**) polymère filmogène à 34% de matière active dispersé dans l'eau.( * ) coloring polyester comprising 10% of blue coloring monomer, prepared in accordance with Example 4 of US Pat. No. 4,804,719 put in aqueous solution with 21.6% of active material. ( ** ) film-forming polymer with 34% active material dispersed in water.
La composition obtenue par dispersion de tous les composants dans l'eau est stable dans le temps, en particulier on n'observe pas de sédimentation après plusieurs semaines de stockage. Cette composition est liquide et facile à appliquer, elle donne un maquillage saturé, couvrant et brillant.The composition obtained by dispersion of all the components in water is stable over time, in particular no sedimentation is observed after several weeks of storage. This composition is liquid and easy to apply, it gives a saturated, covering and shiny makeup.
Exemple 2 : Composition de vernis à onglesExample 2 Composition of Nail Polish
SANCURE 815 (SANNCOR)O 98,5%SANCURE 815 (SANNCOR) O 98.5%
Agent d'étalement 0,5% colorant polymérique rouge (**) 1 %Spreading agent 0.5% red polymer dye ( ** ) 1%
(*) Dispersion aqueuse de polyuréthane filmogène à 34% de matière active.( * ) Aqueous dispersion of film-forming polyurethane with 34% active material.
(**) polyester colorant comprenant 10% de monomère colorant rouge préparé conformément à l'exemple 1 du brevet US-4, 804, 719, en solution aqueuse à 29% de matière active.( ** ) coloring polyester comprising 10% of red coloring monomer prepared in accordance with Example 1 of US Pat. No. 4,804,719, in aqueous solution containing 29% of active material.
Le vernis obtenu est légèrement coloré, rose, et translucide, il ne colore pas l'ongle après démaquillage. Le film de vernis est brillant, dur et résistant à l'eau, il n'est que moyennement pelable.The varnish obtained is slightly colored, pink, and translucent, it does not color the nail after makeup removal. The varnish film is shiny, hard and water resistant, it is only moderately peelable.
La dispersion de polymère filmogène utilisée dans la préparation de ce vernis, lorsqu'elle est appliquée seule sur l'ongle, donne un film pelable facileThe dispersion of film-forming polymer used in the preparation of this varnish, when applied alone on the nail, gives an easy peelable film.
Exemple 3 : Composition de vernis à onglesExample 3 Composition of Nail Polish
LUHYDRAN LR8763 (BASF) (*) 65% Agent d'étalement 0,5% colorant polymérique rouge (**) 34,5%LUHYDRAN LR8763 (BASF) ( * ) 65% Spreading agent 0.5% red polymer dye ( ** ) 34.5%
(*) Dispersion aqueuse acrylique filmogène à 47% de matière active (**) polyester colorant comprenant 10% de monomère colorant rouge préparé conformément à l'exemple 1 du brevet US-4, 804,719, en solution aqueuse à 29% de matière active. On mesure une brillance du film de vernis de 89,9 et une dureté de 77,0. La dispersion de polymère filmogène utilisée dans cet exemple donne, dans les mêmes conditions d'application et de mesure, un film de dureté 25,5. Une telle dispersion ne pourrait donc pas être employée seule pour préparer une composition de vernis à ongles.(*) Acrylic film-forming dispersion at 47% of active material (**) polyester dye comprising 10% of red dye monomer prepared in accordance with Example 1 of patent US-4, 804,719, in aqueous solution with 29% of active material . A gloss of the varnish film of 89.9 and a hardness of 77.0 are measured. The film-forming polymer dispersion used in this example gives, under the same application and measurement conditions, a film with a hardness of 25.5. Such a dispersion could not therefore be used alone to prepare a composition of nail varnish.
Le vernis obtenu est très coloré, bordeaux et translucide, il ne colore pas l'ongle après démaquillage. Le film de vernis est brillant, dur, résistant à l'eau et non pelable. On n'observe aucune sédimentation au cours du temps.The varnish obtained is very colorful, burgundy and translucent, it does not color the nail after removing make-up. The varnish film is shiny, hard, water resistant and non-peelable. No sedimentation is observed over time.
Exemple 4 : Composition de vernis à onglesExample 4 Composition of Nail Polish
SANCURE 815 (SANNCOR)* 62,5%SANCURE 815 (SANNCOR) * 62.5%
Agent d'étalement 0,5% Colorant polymérique jaune 37%Spreading agent 0.5% Yellow polymeric dye 37%
(*) Dispersion aqueuse de polyuréthane filmogène à 34% de matière active (**) Polyester colorant comprenant 10% de monomère colorant jaune préparé conformément à l'enseignement du brevet US-4, 804, 719, en solution aqueuse à 27% de matière active.(*) Aqueous dispersion of film-forming polyurethane containing 34% of active material ( ** ) Dyeing polyester comprising 10% of yellow dye monomer prepared in accordance with the teaching of US Pat. No. 4,804,719, in 27% aqueous solution of active ingredient.
Le vernis obtenu ne colore pas l'ongle après démaquillage. Le film de vernis est brillant, dur et résistant à l'eau.The varnish obtained does not color the nail after removing makeup. The varnish film is shiny, hard and water resistant.
On mesure la brillance du film de vernis selon l'exemple 4, elle est de 94,0. La dispersion d'agent filmogène utilisée dans ce vernis, dans les mêmes conditions de mesure, donne un film de brillance de 91 ,2. The gloss of the varnish film is measured according to Example 4, it is 94.0. The dispersion of film-forming agent used in this varnish, under the same measurement conditions, gives a gloss film of 91.2.

Claims

REVENDICATIONS
1 - Composition de maquillage de la peau, des yeux, des ongles, des lèvres sous la forme d'une dispersion aqueuse, caractérisée en ce qu'elle comprend au moins un colorant polymérique sulfopolyester et au moins un polymère filmogène.1 - Composition for making up the skin, eyes, nails, lips in the form of an aqueous dispersion, characterized in that it comprises at least one sulfopolyester polymeric dye and at least one film-forming polymer.
2- Composition selon la revendication 1 , caractérisée en ce que le colorant polymérique sulfopolyester résulte de la polymérisation de plusieurs monomères dont : (i) au moins un résidu acide di-carboxylique portant au moins un groupement sulfonique; (ii) au moins un résidu diol ; et (iii) au moins un monomère colorant.2- Composition according to claim 1, characterized in that the sulfopolyester polymeric dye results from the polymerization of several monomers including: (i) at least one dicarboxylic acid residue carrying at least one sulfonic group; (ii) at least one diol residue; and (iii) at least one coloring monomer.
3- Composition selon l'une des revendications 1 ou 2, caractérisée en ce que le colorant polymérique sulfopolyester est un polymère colorant dispersible dans l'eau ayant des groupes de liaison comprenant au moins environ 20 % en moles de carbonyloxy et jusqu'à environ 80 % en moles de carbonylamido, ledit polymère contenant des groupes sulfonate hydrosolubilisants et ayant d'environ 0,01 à environ 40 % en moles, sur la base du total de tous les équivalents d'hydroxy, de carboxy ou d'amino réactifs, de colorant comprenant un ou plusieurs composés organiques thermostables ayant initialement au moins un groupe condensable, que l'on a fait réagir sur ou dans le tronc polymère3- Composition according to one of claims 1 or 2, characterized in that the sulfopolyester polymeric dye is a water-dispersible dye polymer having linking groups comprising at least about 20 mol% of carbonyloxy and up to about 80 mol% of carbonylamido, said polymer containing water-soluble sulphonate groups and having from approximately 0.01 to approximately 40 mol%, based on the total of all the equivalents of reactive hydroxy, carboxy or amino, dye comprising one or more thermostable organic compounds initially having at least one condensable group, which has been reacted on or in the polymeric backbone
4- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le colorant polymérique comprend 5 % à 55% en poids d'au moins un monomère colorant.4- Composition according to any one of the preceding claims, characterized in that the polymeric dye comprises 5% to 55% by weight of at least one dye monomer.
5- Composition selon la revendication 4, caractérisée en ce que le colorant polymérique comprend 10% à 40% en poids d'au moins un monomère colorant. 6- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le colorant polymérique sulfopolyester est un polymère colorant hydrodispersible comprenant :5- Composition according to claim 4, characterized in that the polymeric dye comprises 10% to 40% by weight of at least one coloring monomer. 6- Composition according to any one of the preceding claims, characterized in that the sulfopolyester polymeric dye is a water-dispersible dye polymer comprising:
(a) un monomère acide comprenant de 75 mole % à 84 mole % d'acide isophtalique et de 25 mole % à 16 mole % de sel de sodium de l'acide sulfo-5- isophtalique,(a) an acid monomer comprising from 75 mol% to 84 mol% of isophthalic acid and from 25 mol% to 16 mol% of sodium salt of 5-isophthalic acid,
(b) un monomère glycol comprenant de 45 à 60 mole % de diéthylène glycol et de 55 à 40 mole % de 1 ,4-cyclohexanediméthanol ou d'éthylèneglycol ou leur mélange, (c) de 0,5 à 10 mole % de monomère colorant.(b) a glycol monomer comprising from 45 to 60 mol% of diethylene glycol and from 55 to 40 mol% of 1, 4-cyclohexanedimethanol or of ethylene glycol or their mixture, (c) from 0.5 to 10 mol% of monomer dye.
7- Composition selon l'une quelconque des revendications 2 à 6, caractérisée en ce que le monomère colorant est choisi dans le groupe formé par les anthraquinones, les méthines, bis-méthines, les aza-méthines, les arylidènes, les 3H-dibenzo[7,i-j] isoquinolines, les acides 2,5-diarylaminotéréphtaliques et leurs esters, les phtaloylphénothiazines, les phtaloylphénoxazines, les phtaloylacridone, les anthrapyrimidines, les anthrapyrazoles, les phtalocyanines, les quinophtalones, les indophénols, perinones, les nitroarylamines, benzodifurane, les 2 H-1-benzopyran-2-one, les quinophtalones, les perylènes, les quinacridones, les triphénodioxazines, les fluoridines, les 4-amino-1 ,8- naphtalimides, les thioxanthrones, les benzanthrones, les indanthrones, les indigo, thioindigo, xanthène, acridine, azine, oxazine.7- Composition according to any one of claims 2 to 6, characterized in that the coloring monomer is chosen from the group formed by anthraquinones, methines, bis-methines, aza-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, 2,5-diarylaminoterephthalic acids and their esters, phthaloylphenothiazines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinones, perinones, perurins, 2 H-1-benzopyran-2-one, quinophthalones, perylenes, quinacridones, triphenodioxazines, fluoridines, 4-amino-1, 8-naphthalimides, thioxanthrones, benzanthrones, indanthrones, indigo, thioindigo , xanthene, acridine, azine, oxazine.
8- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comporte 0,1 à 20% en poids de colorant polymérique.8- Composition according to any one of the preceding claims, characterized in that it comprises 0.1 to 20% by weight of polymeric dye.
9- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comporte en outre au moins un composé choisi dans le groupe formé par le dioxyde de titane et le dioxyde de zinc.9- Composition according to any one of the preceding claims, characterized in that it also comprises at least one compound chosen from the group formed by titanium dioxide and zinc dioxide.
10- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère filmogène est choisi dans le groupe formé par les polyuréthannes, les polyester-polyuréthannes, les polyéther-polyuréthannes, les polymères radicalaires de type acrylique, acrylique styrène et/ou vinylique, les polyesters, les résines alkydes10- Composition according to any one of the preceding claims, characterized in that the film-forming polymer is chosen from the group formed by polyurethanes, polyester-polyurethanes, polyether-polyurethanes, radical polymers of acrylic, styrene and / or vinyl type, polyesters, alkyd resins
1 1- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère filmogène est sous la forme de particules en dispersion dans un milieu aqueux.1 1- Composition according to any one of the preceding claims, characterized in that the film-forming polymer is in the form of particles in dispersion in an aqueous medium.
12- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend en outre au moins un polymère filmogène soluble dans l'eau.12- Composition according to any one of the preceding claims, characterized in that it further comprises at least one film-forming polymer soluble in water.
13- Composition selon la revendication précédente, caractérisée en ce que le polymère filmogène est choisi dans le groupe formé par les copolymères hydrosolubles, et les polycondensats hydrodispersibles à fonctions sulfonates.13- Composition according to the preceding claim, characterized in that the film-forming polymer is chosen from the group formed by water-soluble copolymers, and water-dispersible polycondensates with sulfonate functions.
14- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend un polymère associatif de type polyuréthanne ou une gomme naturelle telle que la gomme xanthane.14- Composition according to any one of the preceding claims, characterized in that it comprises an associative polymer of polyurethane type or a natural gum such as xanthan gum.
15- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle présente un taux de matière active de 5 à 70% en poids.15- Composition according to any one of the preceding claims, characterized in that it has an active material content of 5 to 70% by weight.
16- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le polymère a une température de transition vitreuse inférieure à la température ambiante (25°C).16- Composition according to any one of the preceding claims, characterized in that the polymer has a glass transition temperature below room temperature (25 ° C).
17- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend au moins un additif dans le groupe formé par les cosolvants, les agents d'étalement, les agents mouillants, les agents dispersants, les anti-mousses, les conservateurs, les filtres UV, les colorants, les pigments, des nacres, les actifs, les vitamines, la kératine et ses dérivés, la mélanine, le collagène, la cystine, le chitosane et ses dérivés, les céramides, la biotine, les oligo-éléments, la glycérine, les hydrolysats de protéines, les phospholipides, les agents hydratants.17- Composition according to any one of the preceding claims, characterized in that it comprises at least one additive in the group formed by cosolvents, spreading agents, wetting agents, dispersing agents, anti-foaming agents, preservatives, UV filters, dyes, pigments, nacres, active ingredients, vitamins, keratin and its derivatives, melanin, collagen, cystine, chitosan and its derivatives, ceramides, biotin, trace elements, glycerin, protein hydrolysates , phospholipids, moisturizers.
18- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comporte au moins un émulsionnant.18- Composition according to any one of the preceding claims, characterized in that it comprises at least one emulsifier.
19- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'émulsionnant est choisi dans le groupe formé par les sels alcalins d'acides gras en C12-C24, les phosphatides de soja, les phospholipides, les lysophospholipides.19- Composition according to any one of the preceding claims, characterized in that the emulsifier is chosen from the group formed by alkali salts of C12-C24 fatty acids, soy phosphatides, phospholipids, lysophospholipids.
20- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle se présente sous la forme d'un vernis à ongles, d'une base pour ongles , d'une base de soin pour ongles, d'un mascara, d'un rouge à lèvres, d'une laque à lèvres, d'un brillant à lèvres, d'un fond de teint, d'un fard à paupières, d'un fard à joue.20- Composition according to any one of the preceding claims, characterized in that it is in the form of a nail varnish, a nail base, a nail care base, a mascara , a lipstick, a lip lacquer, a lip gloss, a foundation, an eyeshadow, a blush.
21- Utilisation d'un colorant polymérique sulfopolyester selon l'une quelconque des revendications 1 à 7, dans une composition de maquillage des yeux, de la peau, des ongles, des lèvres sous la forme d'une dispersion aqueuse, pour former un film coloré sur la peau, les cils, les paupières, les ongles, les lèvres.21- Use of a sulfopolyester polymeric dye according to any one of claims 1 to 7, in a composition for making up the eyes, the skin, the nails, the lips in the form of an aqueous dispersion, to form a film colored on the skin, eyelashes, eyelids, nails, lips.
22- Utilisation d'un colorant polymérique sulfopolyester dans une composition de maquillage des yeux, de la peau, des ongles, des lèvres sous la forme d'une dispersion aqueuse, qui ne colore pas les cils, les yeux, les ongles, les lèvres après le démaquillage.22- Use of a sulfopolyester polymeric dye in a makeup composition for the eyes, skin, nails, lips in the form of an aqueous dispersion, which does not color the eyelashes, the eyes, the nails, the lips after makeup removal.
23- Procédé de maquillage des yeux, de la peau, des ongles, des lèvres, caractérisé par le fait que l'on applique sur les cils, les paupières, la peau, les ongles, les lèvres une composition selon l'une quelconque des revendications 1 à 20. 23- Process for making up the eyes, the skin, the nails, the lips, characterized in that one applies to the eyelashes, the eyelids, the skin, the nails, lips a composition according to any one of claims 1 to 20.
EP97952063A 1996-12-16 1997-12-15 Cosmetic composition in the form of an aqueous dispersion containing at least a polymeric colouring agent Ceased EP0944379A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9615454 1996-12-16
FR9615454A FR2757048B1 (en) 1996-12-16 1996-12-16 COSMETIC COMPOSITION IN THE FORM OF AN AQUEOUS DISPERSION COMPRISING AT LEAST ONE POLYMERIC DYE
PCT/FR1997/002304 WO1998026753A1 (en) 1996-12-16 1997-12-15 Cosmetic composition in the form of an aqueous dispersion containing at least a polymeric colouring agent

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EP0944379A1 true EP0944379A1 (en) 1999-09-29

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JP (1) JP2000513004A (en)
CA (1) CA2274939A1 (en)
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FR2794021A1 (en) * 1999-04-28 2000-12-01 Oreal USE OF A COLORING SULFOPOLYESTER FOR OBTAINING FRICTION RESISTANT FILM
FR2793409B1 (en) 1999-05-11 2004-03-19 Oreal COSMETIC COMPOSITION COMPRISING AN AQUEOUS DISPERSION OF FILM-FORMING POLYMER AND ORGANOPOLYSILOXANE
FR2824268A1 (en) * 2001-05-04 2002-11-08 Oreal COLORFUL FILM-FORMING COSMETIC COMPOSITION
JP4502356B2 (en) * 2002-11-26 2010-07-14 株式会社シード Colored ink composition and colored contact lens using the same
JP4773858B2 (en) * 2006-03-28 2011-09-14 株式会社コーセー Oily liquid eyeliner
WO2015158465A1 (en) 2014-04-14 2015-10-22 Unilever N.V. Skin care composition

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JP2000513004A (en) 2000-10-03
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CA2274939A1 (en) 1998-06-25
WO1998026753A1 (en) 1998-06-25

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