Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
• • A—HUMAN NECESSITIES
  • A45—HAND OR TRAVELLING ARTICLES
  • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
  • A45D29/00—Manicuring or pedicuring implements
  • A45D29/001—Self adhesive nail coating blanks
• • A—HUMAN NECESSITIES
  • A45—HAND OR TRAVELLING ARTICLES
  • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
  • A45D31/00—Artificial nails
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0208—Tissues; Wipes; Patches
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

• Film of nail varnish with optical effect The present invention relates to a flexible article with optical effect, relief and / or olfactory and intended to be applied to the nails for their make-up and / or their care.
• makeup of the nails or false nails is carried out using liquid makeup compositions, also commonly called nail polish.
• This nail varnish is generally applied in the form of layers superimposed on the surface of the nail to be made up, by respecting an intermediate drying step between each layer of varnish applied.
• this makeup method is not entirely satisfactory. First of all, it takes a while to apply. In addition, this type of makeup implies being repeated at short notice due to its insufficient hold. In fact, very quickly, generally after three to five days, the varnish applied flakes off and its gloss decreases.
• the present invention aims precisely to propose a method of making up and / or caring for the nails or false nails which is precisely, in contrast to conventional liquid formulations of the nail varnish type, easy and rapid in terms of application, provided significantly improved resistance over time, significantly reduced in organic solvent (s) and also capable of imparting, in terms of make-up, an optical, relief and / or olfactory effect.
• the present invention relates, according to a first of its aspects, to a flexible article for making up and / or caring for the nails and / or false nails comprising: - at least one adhesive layer allowing the article to be fixed on the 'nail, - at least one organic film, and - at least one material with optical, relief and / or olfactory effect.
• the article may include at least two different organic films, superimposed on the adhesive layer.
• each of these films may contain at least one material with an optical, relief and / or olfactory effect. More particularly, one of them is devoid of such a material. In this embodiment, it is generally the film which is not contiguous to the adhesive layer.
• the film devoid of material with optical, relief and / or olfactory effect is preferably transparent.
• transparent means that the crosslinked coating has a HAZEBYK index of less than 5 as measured with a KYKHAZEGLOSS type gloss meter.
• the present invention relates to a method for preparing a flexible article for making up and / or caring for the nails, comprising at least the steps consisting in superimposing on a removable support: a) at least one layer of a composition based on at least one adhesive material, and b) at least one layer of at least one composition capable of forming, by crosslinking and / or evaporation of its organic or aqueous solvent phase, an organic film and containing at least one material to optical, relief and / or olfactory effect, the formation of said film being carried out following the deposition of said composition.
• the process comprises in step b) the deposition of a first composition and its transformation into an organic film and the deposition on the film thus formed, of a second composition different from the first composition and its transformation into a second organic film.
• said method comprises at the end of step b) a step of drying said article which is stopped before obtaining a completely dry state for said article.
• the article thus obtained is said to be partially dry.
• the present invention relates to a product for making up and / or caring for the nails and / or false nails comprising, in a packaging, substantially airtight, at least one article in accordance with the invention, the packaging being such that the article is kept there in a partially dry form.
• the term partially dry is intended to qualify the fact that the article obtained after formation of the organic film, that is to say by evaporation of the solvent phase, organic or aqueous, of a solution or dispersion at least one film-forming polymer, or by crosslinking of a crosslinkable composition, is not completely free of the residual solvent.
• this packaging comprises a reservoir, such as for example a pocket, flexible or not, capable of sealingly containing a product. It is in particular impermeable to air and / or to solvents.
• the present invention relates to a process for the preparation of a product as defined above comprising the steps consisting in superimposing on a removable support: a) at least one layer of a composition based on at least an adhesive material, b) at least one layer of at least one composition capable of forming, by crosslinking and / or evaporation of its organic or aqueous solvent phase, an organic film and containing at least one material with an optical relief and / or olfactory effect, the formation of said film being carried out following the deposition of said composition, c) if necessary the partial drying of said article thus obtained, and d) the conditioning of said article in a partially dry state within a substantially airtight packaging.
• the article acquires a completely dry appearance, and therefore its final shape only after application to the nail, by simple exposure to ambient air.
• the present invention relates to a method for making up and / or caring for the nails comprising applying to the natural or synthetic nail, the adhesive face of an article according to the invention.
• the term organic also covers materials of the composite type, that is to say associating an organic component with a inorganic component.
• the organic film can behave like an organic matrix in which is incorporated at least one inorganic material and which is capable of contributing as such to the production of the film.
• the term “flexible” describes sufficient flexibility of the article according to the invention.
• this article is in the form of a film capable of lending itself to mechanical deformations of the stretching type in order to adjust it to the surface of a nail.
• This deformability is notably characterized by the parameter of deformation at break 8r discussed below.
• the article according to the invention differs from an article of false nail type which is characterized by a rigidity incompatible with such mechanical deformation.
• Another difference between the article according to the invention and a false nail lies in the sensitivity of this article with respect to polar organic solvents of the acetone, ester and / or short alcohol type.
• the organic film appearing on the external face of the article according to the invention has an ability to swell, and which in particular can result in an increase in its weight when it is brought into contact with one of these solvents.
• a false nail is completely devoid of such sensitivity.
• This ability to swell, manifested by the article according to the invention is precisely advantageous for its elimination when the latter is applied to the surface of a nail or of a false nail.
• the article according to the invention can be easily removed by simple make-up removal using a conventional solvent, as opposed to a false nail which must be removed. More specifically, it can be removed with organic solvents and in particular with alkyl acetates and their mixtures.
• the article according to the invention is particularly advantageous in terms of make-up insofar as it allows access to a wide variety of original effects going beyond conventional colored effects.
• the inventors have in fact found that the film structure of the article is particularly advantageous for imparting effects other than simple conventional static colored effects and in particular for conditioning materials with an optical effect therein, of relief and / or olfactory, of very diverse natures.
• These materials can in particular be organic, inorganic and / or composite in nature. Of course, certain materials are capable of imparting several simultaneous effects to the articles according to the invention.
• particles with an optical effect can confer, in addition to the expected optical effect, a colored effect or even a relief effect if their particle size is sufficiently large.
• the quantities of these materials that can be used can vary significantly on the one hand depending on the desired effect, on the other hand depending on the nature of these materials and / or their size and / or form when they are in the form of particles and / or fibers. Those skilled in the art are able to make this adjustment according to the material considered.
• the flexible article according to the invention may contain at least one material with specific optical effect, in particular present in its organic film.
• this effect is different from a simple conventional tinting effect, that is to say, unified and stabilized as produced by conventional coloring materials such as, for example, monochromatic pigments.
• “stabilized” means devoid of any effect of variability in color with the angle of observation or even in response to a change in temperature.
• This material is present in sufficient quantity to produce an optical effect perceptible to the naked eye.
• it is an effect chosen from goniochromatic, metallic and in particular mirror, soft-focus, rainbow and / or thermochrome effects.
• this material can be chosen from particles with a metallic reflection, goniochromatic coloring agents, diffracting pigments, thermochromic agents, optical brighteners, as well as fibers, in particular interference fibers.
• these different materials can be combined so as to provide the simultaneous manifestation of two effects, or even of a new effect according to the invention.
• Particles with metallic reflection By “particles with metallic reflection”, we mean particles whose nature, size, structure and surface condition allow them to reflect the incident light, in particular in a non-iridescent manner. Particles having a substantially flat outer surface are also suitable, because they can more easily give rise, if their size, their structure and their surface state allow, to an intense specular reflection which can then be described as a mirror effect.
• the metallic reflection particles which can be used in the invention can, for example, reflect light in all the components of the visible without significantly absorbing one or more wavelengths.
• the spectral reflectance of these particles can for example be greater than 70% in the range 400-700 nm, and better still at least 80%, even 90% or even 95%.
• These particles generally have a thickness less than or equal to 1 ⁇ m, in particular less than or equal to 0.7 ⁇ m, in particular less than or equal to 0.5 ⁇ m.
• the total proportion of particles with a metallic reflection is notably less than or equal to 20% by weight and in particular less than or equal to 10% by weight relative to the total weight of the article.
• the particles with a metallic reflection which can be used in the invention are in particular chosen from: particles of at least one metal and / or at least one metal derivative, particles comprising a substrate, organic or inorganic, monomaterial or multimaterial, covered at least partially by at least one layer with metallic reflection comprising at least one metal and / or at least one metallic derivative, and - mixtures of said particles.
• the metals which may be present in said particles there may be mentioned for example Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te , Se and their mixtures or alloys.
• Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and their mixtures or alloys e.g.
• metals denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulfides.
• metallic derivatives which may be present in said particles, may especially mention metal oxides such as for example oxides of titanium, in particular TiO 2 , of iron in particular Fe 2 O 3 , of tin, of chromium, barium sulphate and the following compounds: MgF 2 , CrF 3 , ZnS , ZnSe, SiO 2 , Al 2 O 3 , MgO, Y 2 O 3 , SeO 3 , SiO, HfO 2 , ZrO 2 , CeO 2 , Nb 2 O 5 , Ta 2 O 5 , MoS 2 and their mixtures or alloys.
• the particles with a metallic reflection can be composed of at least one metal as defined above, of at least one metallic derivative as defined above or alternatively of one of their mixtures.
• These particles can be at least partially covered by a layer of another material, by an example of transparent material such as in particular rosin, silica, stearates, polysiloxanes, polyester resins, epoxy resins, polyurethane resins and acrylic resins.
• transparent material such as in particular rosin, silica, stearates, polysiloxanes, polyester resins, epoxy resins, polyurethane resins and acrylic resins.
• Illustrative of these particles include aluminum particles, such as those sold under the names Starbrite 1200 EAC ® by Siberline and METALURE® ® by the company Eckart.
• these particles can be particles comprising a substrate and which therefore have a multilayer structure, for example a bilayer.
• This substrate can be organic or mineral, natural or synthetic, single-material or multi-material, solid or hollow.
• the substrate When the substrate is synthetic, it can be produced with a shape favoring the formation of a reflective surface after coating, in particular after the deposition of a layer of materials with metallic reflection.
• the substrate may, for example, have a flat surface and the layer of metallic reflection materials a substantially uniform thickness.
• the substrate may in particular be chosen from metals and metal derivatives as mentioned above, and also from glasses, ceramics, aluminas, silicas, silicates and in particular aluminosilicates and borosilicates, synthetic mica such as fluorophlogopite , and mixtures thereof, this list not being exhaustive.
• the layer with a metallic reflection can coat all or part of the substrate and this layer can be at least partially covered by a layer of another material, for example a transparent material in particular as mentioned above.
• this layer with metallic reflection entirely coats, directly or indirectly, that is to say with the interposition of at least one intermediate metallic layer or not, the substrate.
• the metals or metal derivatives which can be used in the reflective layer are as defined above.
• it can be formed from at least one metal chosen from silver, aluminum, chromium, nickel, molybdenum, gold, copper, tin, magnesium and their mixtures (alloys ). More particularly, silver, chromium, nickel, molybdenum and their mixtures are used.
• Glass particles covered with a metallic layer in particular those described in documents JP-A-09188830, JP-A- 10158450, JP-A-10158541, JP -A-07258460 and JP-A-05017710.
• these particles comprising a glass substrate, mention may be made of those coated respectively with silver, gold or titanium, in the form of platelets, sold by the company NIPPON SHEET GLAS S under the names MICROGLASS METASHINE.
• Particles with a glass substrate coated with silver, in the form of platelets are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL.
• Particles with a glass substrate coated with a nickel / chromium / molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by this same company.
• Those coated either with brown iron oxide, or titanium oxide, tin oxide or a mixture thereof such as those sold under the name ® REFLECKS® by Engelhard or those sold under the reference Metashine MC 2080GP by the company NIPPON SHEET GLASS.
• These glass particles covered with metals can be coated with silica like those sold under the name METASHINE series PSS1 or GPS1 by the company NIPPON SHEET GLASS.
• Particles with a spherical glass substrate coated or not with a metal in particular those sold under the name PRIZMALITE MICROSPHERE by the company PRIZMALITE INDUSTRIES.
• a metal in particular those sold under the name PRIZMALITE MICROSPHERE by the company PRIZMALITE INDUSTRIES.
• the pigments from the METASHINE 1080R range marketed by the company NIPPON SHEET GLASS CO. LTD.
• These pigments more particularly described in patent application JP 2001-11340, are C-GLASS glass flakes comprising 65 to 72% of SiO2, covered with a layer of titanium oxide of rutile type (TiO2). These glass flakes have an average thickness of 1 micron and an average size of 80 microns, ie a ratio in average size / average thickness of 80.
• the particles with a metallic reflection can also be chosen from particles formed by a stack of at least two layers with different refractive indices. These layers can be of a polymeric or metallic nature and in particular include at least one polymeric layer.
• the particles with a metallic effect can be particles deriving from a multilayer polymeric film.
• the choice of materials intended to constitute the different layers of the multilayer structure is of course made so as to impart the desired metallic effect to the particles thus formed.
• Such particles are in particular described in WO 99/36477, US 6,299,979 and US 6,387,498 and more particularly identified below in the goniochromatic chapter.
• Diffracting pigment is meant in the sense of the present invention a pigment capable of producing a variation in color depending on the angle of observation when illuminated by white light, due to the presence of a structure which diffracts light.
• a diffractive pigment can comprise a diffraction grating, capable for example of diffracting in defined directions a ray of incident monochromatic light.
• the diffraction grating can comprise a periodic pattern, in particular a line, the distance between two adjacent patterns being of the same order of magnitude as the wavelength of the incident light. When the incident light is polychromatic, the diffraction grating will separate the different spectral components of the light and produce a rainbow effect.
• the diffracting pigment can be produced with patterns having different profiles, in particular triangular, symmetrical or not, in crenellations, of constant width or not, sinuosoidal.
• the spatial frequency of the network and the depth of the patterns will be chosen according to the degree of separation of the different orders desired.
• the frequency can vary for example between 500 and 3000 lines per mm.
• the particles of the diffracting pigment each have a flattened shape, and in particular are in the form of a wafer.
• the same pigment particle can comprise two crossed diffraction gratings, perpendicular or not.
• a possible structure for the diffracting pigment may include a layer of reflective material, covered at least on one side with a layer of dielectric material. The latter can give better rigidity and durability to the diffracting pigment.
• the dielectric material can then be chosen for example from the following materials: MgF 2 , SiO 2 , Al 2 O 3 , A1F 3 , CeF 3 , LaF 3 , NdF 3 , SmF 2 , BaF 2 , CaF 2 , LiF and their associations .
• the reflective material can be chosen for example from metals and their alloys and also from non-metallic reflective materials.
• the diffracting pigment may comprise a multilayer structure comprising a core of a dielectric material covered with a reflective layer at least on one side, or even completely encapsulating the core.
• a layer of dielectric material can also cover the reflective layer (s).
• the dielectric material used is then preferably inorganic, and can be chosen, for example, from metal fluorides, metal oxides, metal sulfides, metal nitrides, metal carbides and their associations.
• the dielectric material can be in the crystalline, semi-crystalline or amorphous state.
• the dielectric material, in this configuration can for example be chosen from the following materials: MgF 2 , SiO, SiO 2 , Al 2 O 3 , TiO 2 , WO, AIN, BN, B 4 C, WC, TiC, TiN, N 4 Si 3 , ZnS, glass particles, diamond type carbons and their associations.
• the diffracting pigment used can in particular be chosen from those described in American patent application US 2003/0031870 published on February 13, 2003.
• a diffracting pigment can for example have the following structure: MgF 2 / Al / MgF 2 , a diffracting pigment having this structure being marketed under the name SPECTRAFLAIR 1400 Pigment Silver by the company FLEX PRODUCTS, or SPECTRAFLAIR 1400 Pigment Silver FG.
• the proportion by weight of MgF 2 can be between 80 and 95% of the total weight of the pigment.
• Goniochromatic coloring agents Within the meaning of the invention, a goniochromatic coloring agent makes it possible to observe a change in color, also called “color flop”, as a function of the angle of observation, greater than that which can be observed. meet with mother-of-pearl. One or more goniochromatic coloring agents can be used simultaneously.
• the goniochromatic coloring agent can be chosen so as to exhibit a relatively significant color change with the angle of observation.
• the goniochromatic coloring agent can thus be chosen so that it is possible to observe, for a variation of the observation angle between 0 ° and 80 ° under 45 ° lighting, a variation in color ⁇ E of the cosmetic composition, measured in the CIE 1976 color space, of at least 2.
• the goniochromatic coloring agent can also be chosen so that one can observe, for lighting at 45 ° and a variation of l observation angle of between 0 ° and 80 °, a variation Dh of the shade angle of the cosmetic composition, in the CIE 1976 plane, of at least 30 ° or even at least 40 ° or at least 60 °, or even at least 100 °.
• the goniochromatic coloring agent can be chosen, for example, from multilayer interference structures and liquid crystal coloring agents.
• this can for example comprise at least two layers, each layer, independently or not of the (or) other (s) layer (s), being produced for example from at least one material chosen from the group consisting of the following materials: MgF 2 , CeF 3 , ZnS, ZnSe, Si, SiO 2 , Ge, Te, Fe 2 O 3 , Pt, Va, Al 2 O 3 , MgO, Y 2 O 3 , S 2 O 3 , SiO, HfO 2 , ZrO 2 , CeO 2 , Nb 2 O 5 , Ta 2 O 5 , TiO 2 , Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn , MoS 2 , cryolite, alloys, polymers and their associations.
• the multilayer structure may or may not have, with respect to a central layer, symmetry in terms of the chemical nature of the stacked layers.
• symmetrical interference multilayer structures which can be used in compositions produced in accordance with the invention are for example the following structures: Al / SiO 2 / Al / SiO 2 / Al, pigments having this structure being sold by the company DUPONT DE NEMOURS; Cr / MgF 2 / Al / MgF 2 / Cr, pigments having this structure being marketed under the name CHROMAFLAIR by the company FLEX; MoS 2 / SiO 2 / Al / SiO 2 / MoS 2 ; Fe 2 O 3 / SiO 2 / Al / SiO 2 / Fe 2 O 3 , and Fe 2 O 3 / SiO 2 / Fe 2 O 3 / SiO 2 / Fe 2 O 3 , pigments having these structures being marketed under the name SICOPEARL by BASF; MoS 2 / SiO 2 / mica-oxide
• these pigments can be the pigments with a silica / titanium oxide / tin oxide structure sold under the name XIRONA MAGIC by the company MERCK, the pigments with a silica / brown iron oxide structure sold under the name XIRONA INDIAN SUMMER by the company MERCK and the pigments of silica / titanium oxide / mica / tin oxide marketed under the name XIRONA CARRIBEAN BLUE by the company MERCK.
• polyethylene naphthalate (PEN) and its isomers for example 2.6-, 1.4-, 1 , 5-, 2,7- and 2,3-PEN
• polyalkylene terephthalates polyimides, polyetherimides, atactic polystyrenes, alkyl polycarbonates, polymethacrylates and polyacrylates, syndiotactic polystyrene (sPS), syndiotactic poly-alpha-methylstyrene, syndiotactic polydichlorostyrene, copolymers and mixture of its polystyrenes, cellulose derivatives, polyalkylene polymers, fluorinated polymers, chlorinated polymers, polysulfones, polyethersulfones, polyacrylonitriles, polyamides, silicone resins , epoxy resins, polyvinyl acetate, polyether amide
• copolymers e.g. PEN copolymers (e.g. 2.6-, 1.4- copolymers, 1,5-, 2,7-, and / or 2,3-naphthalene dicarboxylic acid or its esters with (a) terephthalic acid or its esters; (b) isophthalic acid or its esters; (c) phthalic acid or its esters; (d) alkane glycols; (e) cycloalkane glycols (for example cyclohexane dimethanol diol); (f) alkane dicarboxylic acids; and / or (g) cycloalkane dicarboxylic acids, polyalkylene terephthalate copolymers and styrene copolymers.
• PEN copolymers e.g. 2.6-, 1.4- copolymers, 1,5-, 2,7-, and / or 2,3-naphthalene dicarboxylic acid or its esters with (a
• each individual layer may include blends of two or more of the foregoing polymers or copolymers.
• the choice of materials intended to constitute the different layers of the multilayer structure is of course made so as to impart the desired optical effect to the particles thus formed. Mention may be made, by way of example of pigments with a polymeric multilayer structure, of those sold by the company 3M under the name COLOR GLITTER.
• Liquid crystal coloring agents include, for example, silicones or cellulose ethers onto which mesomorphic groups are grafted.
• liquid crystal goniochromatic particles that may be used include those sold by the company Chenix well as those sold under the name Helicone® ® HC by Wacker. These agents can also be in the form of dispersed goniochromatic fibers. Such fibers can for example have a size of between 50 ⁇ m and 700 ⁇ m, for example around 300 ⁇ m.
• interference fibers with a multilayer structure can be used. Fibers with a multilayer structure of polymers are described in particular in documents EP-A-921217, EP-A-686858 and US-A-5472798.
• the multilayer structure may comprise at least two layers, each layer, independently or not of the other layer (s), being made of at least one synthetic polymer.
• the polymers present in the fibers can have a refractive index ranging from 1.30 to 1.82 and better still ranging from 1.35 to 1.75.
• the preferred polymers for constituting the fibers are polyesters such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate; acrylic polymers such as polymethyl methacrylate; polyamides.
• Goniochromatic fibers with a polyethylene terephthalate / nylon-6 bilayer structure are sold by the company TEIJIN under the name MORPHOTEX. Alternatively, this goniochromatic coloring agent may be combined with at least one diffracting pigment.
• the combination of these two materials results in an article which exhibits an increased color variability, therefore which is likely to allow an observer to perceive a change in color, or even a movement of color, under numerous conditions of observation and 'illumination.
• the weight ratio of the diffracting pigment relative to the goniochromatic coloring agent is preferably between 85/15 and 15/85, better between 80/20 and 20/80, better still 60/40 and 40/60, for example of the order of 50/50. Such a relationship is favorable for obtaining a sustained rainbow effect and a sustained goniochromatic effect.
• Optical brighteners are compounds well known to those skilled in the art.
• optical brighteners mention may more particularly be made of stilbene derivatives, in particular polystyrylstilbene and triazinstilbene, coumarin derivatives, in particular hydroxycoumarins and aminocoumarins, oxazole, benzoxazole, imidazole, triazole, pyrazoline derivatives, derivatives of pyrene and porphyrin derivatives and mixtures thereof.
• stilbene derivatives in particular polystyrylstilbene and triazinstilbene
• coumarin derivatives in particular hydroxycoumarins and aminocoumarins
• oxazole benzoxazole
• imidazole triazole
• pyrazoline derivatives derivatives of pyrene and porphyrin derivatives and mixtures thereof.
• optical brighteners which can be used in the present invention can also be in the form of copolymers, for example acrylates and / or methacrylates, grafted by optical brightening groups as described in application FR 99 10942. They can be used as such or introduced into the film in the form of particles and / or fibers covered with said brightener, such as those described below. In particular, it is possible to use the fibers covered with optical brightener as marketed by the company LCW under the commercial reference Fiberlon 54 ZO3, having a length of approximately 0.4 mm and a titer of 0.5 denier.
• this relief effect may or may not be associated with an optical effect.
• a material of this type is generally present in sufficient quantity to impart a relief effect perceptible to the touch or even to the naked eye. It can in particular be a rough, granular and / or hammered effect. Material giving a rough appearance
• the article according to the invention is particularly advantageous for fixing particles or solid fibers at the level of its film thus giving an original make-up in relief.
• particles of substantially spherical or ovoid shape can impart a soft feel to the makeup.
• the solid particles have a substantially spherical shape, to allow their good distribution during their application to the first layer.
• the solid particles used according to the invention can have an average size ranging from 2.5 ⁇ m to 5 mm, and better still from 50 ⁇ m to 2 mm. The smaller the particles, the more satisfactory the behavior of the particles. The use of particles is also compatible with the production of patterns.
• the solid particles can be made of any material satisfying the density properties defined above.
• the solid particles can be of a material chosen from glass, zirconium oxide, tungsten carbide, plastics such as polyurethanes, polyamides, polytetrafluoroethylene, polypropylene, metals such as steel, copper, brass, chrome, wood, marble, onyx, jade, natural mother-of-pearl, precious stones (diamond, emerald, ruby, sapphire), amethyst, aquamarine. Glass beads such as those sold under the name "SILIBEADS ® " by the company SIGMUND LINDNER are preferably used; these beads also have the advantage of also imparting a shiny effect and a flicker to the makeup.
• plastics such as polyurethanes, polyamides, polytetrafluoroethylene, polypropylene
• metals such as steel, copper, brass, chrome, wood, marble, onyx, jade, natural mother-of-pearl, precious stones (diamond, emerald, ruby, sapphi
• the solid particles, deformable or not can be solid or hollow, colorless or colored, coated or not.
• the fibers which can be used according to the invention may be fibers of synthetic or natural, mineral or organic origin.
• fiber it is necessary to understand an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber is inscribed.
• the L / D ratio (or form factor) is chosen from the range going from 3.5 to 2500, preferably from 5 to 500, and better still from 5 to 150.
• the fibers are polyamide fibers (Nylon ®).
• Polyamide 0.9 Dtex 3mm having an average diameter of 6 ⁇ m, a titer of approximately 0.9 dtex and a length ranging from 0, 3 mm to 5 mm.
• Polyethylene fibers can also be used, such as those sold under the name “Shurt Stuff 13 099 F” by the company Mini Fibers.
• the flexible article in accordance with the invention is also suitable for packaging a material capable of imparting a granular or "plastered” appearance to the surface of the article.
• This granite effect material can be fragments of polymer film, colored or not, having two substantially flat faces, having a thickness ranging from 40 to 200 ⁇ m and the largest dimension of which ranges from 0.1 to 4 mm, the fragments being insoluble in the medium of the composition intended to form the organic film.
• the composition intended to form the film is applied to the adhesive layer or to a support, the film fragments are easily distributed in the deposited layer and are arranged randomly in its thickness.
• the crosslinking and / or drying of this composition then provides a film having more thicker than the average film thickness, distributed randomly over the surface of the film.
• the film surface then has a discontinuous relief, resistant to friction.
• An original relief makeup is thus obtained, both to the touch and to the view, having good adhesion to the made-up support and good hold.
• the fragment of colored polymer film can be obtained from radical polymers, and in particular from vinyl polymers such as acrylic polymers or polymers based on polyvinyl acetate, styrene-acrylic, vinyl / versatate, vinyl / ethylene copolymers. , vinyl / versatate / acrylate or vinyl / ethylene / chloride terpolymers.
• styrene / acrylic copolymers are used.
• Such fragments are in particular described in application EP 1 036 554.
• the thickness of the film fragment can range from approximately 70 ⁇ m to approximately 130 ⁇ m, and better still from approximately 90 ⁇ m to approximately 110 ⁇ m.
• Fragments of colored film used according to the invention are in particular marketed under the name MONOCOLOR by the company QUADRA INDUSTRIES.
• the organopolysiloxane can be chosen from polydimethylsiloxanes, polymethylethylsiloxanes, copolymers of dimethylsiloxane and methylvinylsiloxane, copolymers of dimethylsiloxane and up to 50 mole percent of phenylmethylsiloxane.
• organopolysiloxane use may in particular be made of those sold in solution in xylene under the name "Dow Corning 61 additive" by the company Dow Corning, or alternatively those sold under the name "Rhodorsil SIL AID 16" by the company Rhône-Poulenc .
• the organopolysiloxane can be present in the organic film in an effective content to obtain the hammered effect (crater formation) and in particular in a content ranging from 0.01% to 10% by weight, relative to the total weight of said film, preferably from 0.1% to 5% by weight.
• the organopolysiloxane and the metallic pigment can be present in the organic film in an organopolysiloxane / metallic pigment weight ratio ranging from 0.1 / 100 to 5/100, and better still from 0.5 / 100 to 1.5 / 100.
• the fumed silica present in the organic film can be in the form of hydrophilic fumed silica or hydrophobic fumed silica.
• hydrophilic fumed silica is used.
• Pyrogenic silicas can be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica.
• Such hydrophilic silicas are for example sold under the names “AEROSIL 130 ® “, “AEROSIL 200 ® “, “AEROSIL 255 ® “, “AEROSIL 300 ® “, “AEROSIL 380 ® “ by the company Degussa, "CAB-O- SIL HS-5 ® “,” CAB-O-SIL EH-5 ® “,” CAB-O-SIL LM-130 ® “,” CAB-O-SIL MS-55 ® ",” CAB-O-SIL M -5 ® "by the Cabot Company.
• the articles according to the invention can also be endowed with olfactory properties by incorporation in particular in their organic film, of at least one odoriferous material or even perfume substance.
• the fragrance substance can be chosen from any odoriferous substance well known to those skilled in the art, and in particular from essential oils and / or essences.
• This olfactory material can, if necessary, be introduced via a solvent-plasticizer.
• solvent-plasticizer is understood to mean a compound which at least partially solubilizes the olfactory material and which is capable of evaporating slowly.
• the solvent-plasticizer can be chosen from glycols such as dipropylene glycol, ethyldiglycol, n-propylglycol, n-butylglycol, methyldiglycol, n-butyldiglycol, alcohols such as cyclohexanol, ethyl-2 butanol, 3-methoxy butanol, 2-ethyl hexanol, phenoxyethanol, esters, such as glycol monoacetate, ethylglycol acetate, n-butylglycol acetate, ethyldiglycol acetate, n-butyldiglycol acetate, methyl abietate, isopropyl myristate, propylene glycol diacetate, propylene glycol methyl ether acetate, glycol ethers such as dipropylene glycol methyl ether , butyl ether of dipropylene glycol, alone or as a mixture
• the article according to the invention can be characterized by a high dry extract. In fact, it can have, in the dry state, an amount of dry matter greater than 80%, and in particular greater than 85% and in particular greater than 90% by weight relative to its total weight. In other words, the quantity of volatile solvent is less than 20%, in particular less than 15% and more particularly less than 10% by weight relative to the total weight of the article.
• the article according to the invention can advantageously be in a partially dry form. In this particular case, the article is advantageously packaged in a reservoir such as for example a pouch, flexible or not, sufficiently waterproof to preserve this partially dry appearance.
• the article according to the invention advantageously has a dry matter content of less than 80%, in particular less than 75%, in particular less than 70% relative to its total weight. Said article may also have a dry matter content greater than 60%, in particular greater than 65% by weight relative to its total weight.
• Such an article when extracted from the packaging of the product according to the invention, acquires, by exposure to ambient air, a dry state as defined above within 24 hours.
• the quantity of dry matter is measured by heating the sample by infrared rays of 2 ⁇ m to 3.5 ⁇ m in wavelength.
• the substances contained in said films which have a high vapor pressure, evaporate under the effect of this radiation. Measuring the sample weight loss helps determine
• the dry extract of the film are carried out using a commercial infrared dryer LP16 from Mettler. This technique is fully described in the device documentation provided by Mettler.
• Water recovery The article according to the invention is characterized in the dry state by water recovery brought to 25 ° C less than or equal to 20%, in particular less than or equal to 16%, and in particular less at 10%.
• water recovery of the film means the percentage of water absorbed by the article after 60 minutes of immersion in water, at 25 ° C (room temperature).
• the water uptake is measured for pieces of approximately 1 cm 2 cut from the dry article are weighed (measurement of the mass Ml) and then immersed in water for 60 minutes; after immersion, the piece of article is wiped to remove excess water from the surface and then weighed (measurement of mass M2).
• the difference M2 - Ml corresponds to the quantity of water absorbed by the article.
• the water uptake is equal to [(M2 - Ml) / Ml] x 100 and is expressed as a percentage of weight relative to the weight of the article.
• the article according to the invention is advantageously a film having a conservation module E' greater than or equal to 1 MPa, in particular ranging from 1 MPa to 5000 MPa, in particular greater than or equal to 5 MPa , in particular ranging from 5 to 1000 MPa, and more particularly greater than or equal to 10 MPa for example ranging from 10 to 500 MPa at a temperature of 30 ° C. and a frequency of 0.1 Hz.
• the measurement of the conservation module is carried out by DMTA (Dynamical and Mechanical Temperature Analysis). Viscoelasticimetry tests are carried out with a DMTA device from Polymer TA Instruments (model DMA2980), on a sample of article.
• the test pieces are cut (for example with a cookie cutter). These typically have a thickness of approximately 150 ⁇ m, a width of 5 to 10 mm and a useful length of approximately 10 to 15 mm.
• the measurements are carried out at a constant temperature of 30 ° C.
• the sample is stressed in tension and in small deformations (it is imposed for example a sinusoidal displacement of ⁇ 8 ⁇ m) during a frequency sweep, the frequency ranging from 0.1 to 20 Hz. We are thus working in the field linear, under low levels of deformation.
• E * E '+ iE "of the film of composition tested, E' being the conservation module and E" the so-called loss module.
• the articles according to the invention have, in the dry state, a deformation at break 8r greater than or equal to 5%, in particular ranging from 5 to 500%, preferably greater than or equal to 15%, in particular ranging from 15 to 400% and / or an energy at break per unit of volume W r greater than or equal to 0.2 J / cm 3 , in particular ranging from 0.2 to 100 J / cm 3 , preferably greater than 1 J / cm 3 , in particular ranging from 1 to 50 J / cm 3 .
• the strain at break and the energy at break per unit of volume are determined by tensile tests carried out on an article about 200 ⁇ m thick.
• the article is cut into dumbbell test pieces of useful length 33 ⁇ 1 mm and useful width 6 mm.
• the tests are carried out, for example, on a traction device sold under the name Lloyd ® LR5K. The measurements are carried out at room temperature (20 ° C). The test pieces are drawn at a displacement speed of 33 mm / min, corresponding to a speed of 100% elongation per minute. A displacement speed is therefore imposed and the elongation ⁇ L of the test piece and the force F necessary to impose this elongation are simultaneously measured.
• the strain at break ⁇ r is the maximum strain of the sample before the break point (in%).
• the energy at break per unit of volume W r in J / cm 3 is defined as the area under this stress / strain curve such that:
• the organic film of the article according to the invention can be obtained by crosslinking of a crosslinkable composition and / or by evaporation of the organic or aqueous solvent phase from a solution or dispersion of minus a film-forming polymer.
• CROSSLINKED FILM within the meaning of the present invention, a film qualified as crosslinked can be totally or partially crosslinked. In the case of partial crosslinking, this is of course sufficient to form the expected film.
• the compounds brought into contact are chosen, in particular according to the nature of the functions which they respectively possess, in order to be able to interact under the conditions of the crosslinking reaction considered.
• This crosslinking can thus be carried out thermally, photochemically and / or chemically, with or without the presence of a catalyst. The realization of this crosslinking falls within the competence of a person skilled in the art.
• the crosslinking reaction is similar to a polyaddition or polycondensation reaction carried out in the presence or in the absence of catalyst.
• the organic film can in particular derive from the crosslinking of a reactive system formed by: - at least one first compound (A) comprising at least two functions (X), and - at least one second compound (B) comprising at least two functions
• the reactive system has an average functionality (total number of functions X and Y / total number of molecules of compounds (A) and (B)) greater than 2 of so as to provide a three-dimensional network. More particularly, to obtain a satisfactory crosslinking effect, the average functionality of the reactive system can be at least equal to 2.2 and more particularly vary from 2.5 to 100.
• Compounds (A) and (B) may be of organic origin and in particular of the monomer, oligomer, polymer and / or copolymer type or of inorganic nature such as, for example, an inorganic particle, in which case they have on the surface the two functions (X) or ( Y) required.
• the functions X and Y reactive with one another are chosen from so-called reactive functions and functions comprising at least one labile hydrogen. More specifically, the reactive functions are chosen from isocyanate, epoxy and ethylene double bond functions and the functions with labile hydrogen (s) are of the carboxylic type, alcohol in particular phenolic, primary or secondary amine, amide, aminoalcohol and / or thiol. According to this variant, the compounds (A) and (B) brought into contact, respectively have at least two so-called reactive functions of epoxide and / or isocyanate type and at least two functions with labile hydrogen (s), in particular of amine type or amino alcohol and can in particular be chosen from the compounds mentioned above.
• X can be an epoxide and / or isocyanate function and Y can be chosen from a carboxylic acid function and / or an anhydride function and / or an amino function and / or a thiol function and / or a hydroxyl function, in particular phenolic.
• crosslinking can be carried out by bringing into the presence of compounds (A) and / or (B) having functions (X) and / or (Y) in a blocked form and capable of being unlocked beforehand or under the reaction conditions adopted for crosslinking. This alternative is well known to those skilled in the art and will not be described in detail.
• Compounds with isocyanate functions are known in the art. They may be polyisocyanates, including diisocyanates or triisocyanates, which may have a molecular mass of less than 500,000, or even less than 10,000. These polyisocyanates are generally obtained by polyaddition, polycondensation and / or grafting, carrying at least two functions isocyanates, either at the chain ends or on side groups.
• the polyisocyanates can be linear, branched, aliphatic, cycloaliphatic or aromatic. As polyisocyanate, there may in particular use the DESMODUR ® N of Bayer, Tolonate ® HDB-LV from Rhodia.
• Compounds with epoxy functions are also known from the state of the art. They can be of any chemical nature. They may be diepoxides or polyepoxides of low masses (less than or equal to 5000), or else oligomers or polymers of any chemical nature, obtained by polyaddition, polycondensation and / or grafting, carrying at least two epoxide functions free, either at the ends of chains, or in lateral groups.
• Polymers with epoxy functions are marketed under the names CYRACURE ® UVR-6110, CYRACURE ® UVR-6105, CYRACURE ® ERL-4221E, CYRACURE ® ERL-4206, CYRACURE ® UVR 6128, CYRACURE ® UVR 6216 by the company UNION CARBIDE, DER ® 439 by the company DOW CHEMICAL, the EPIKATES ® 828,1001,1004,1007 by the company SHELL, the ARALDITE ® ECN1299 by the company CIBA-GEIGY, the EPOXYNOVOLACS ® by the company DOW CHEMICAL.
• Compounds with ethylenic double bonds can be of any chemical nature. They may be chosen especially from: a) polyesters containing (meth) side acrylate and / or devices: Such polyesters are sold for example by UCB under the Ebecryl denominations ® (EBECRYL ® 450: molecular weight 1600, average 6 acrylate functions per molecule, EBECRYL ® 652: molar mass 1500, on average 6 acrylate functions per molecule, EBECRYL ® 800: molar mass 780, on average 4 acrylate functions per molecule, EBECRYL ® 810: molar mass 1000, on average 4 functions acrylate per molecule, EBECRYL ® 50,000: molar mass 1,500, on average 6 acrylate functions per molecule).
• Ebecryl denominations ® EBECRYL ® 450: molecular weight 1600, average 6 acrylate functions per molecule
• EBECRYL ® 652 molar mass 1500
• polyurethanes and / or polyureas with (meth) acrylate groups are sold, for example, under the name SR 368 (tris (2-hydroxyethyl) isocyanurate-triacrylate) or CRAYNOR ® 435 by the company CRAY VALLEY, or under the name EBECRYL ® by the company UCB (EBECRYL ® 210: molar mass 1500, 2 acrylate functions per molecule, EBECRYL ® 230: molar mass 5000, 2 acrylate functions per molecule, EBECRYL ® 270: molar mass 1500, 2 acrylate functions per molecule, EBECRYL ® 8402: molar mass 1000, 2 acrylate functions per molecule, EBECRYL ® 8804: molar mass 1300, 2 acrylate functions per molecule, EBECRYL ® 8804: molar mass 1300, 2 acrylate functions per molecule, EBECRYL
• Polyoxyethylenes-di (meth) acrylate of suitable molar mass are sold, for example, under the names SR 259, SR 344, SR 610, SR 210, SR 603 and SR 252 by the company CRAY VALLEY or under the name EBECRYL ® 11 by UCB .
• Triacrylates trimethylolpropane polyethoxylate are marketed for example under the names SR 454, SR 498, SR 502, SR 9035, SR 415 from Cray Valley or under the name EBECRYL ® 160 by the company UCB.
• Polypropoxylated trimethylolpropane triacrylates are sold, for example, under the names SR 492 and SR 501 by the company CRAY VALLEY. d) the epoxyacrylates obtained by reaction between:
• Such polymers are marketed for example under the names SR 349, SR 601, CD 541, SR 602, SR 9036, SR 348, CD 540, SR 480, CD 9038 by the company CRAY VALLEY, under the names EBECRYL ® 600 and EBECRYL ® 609, EBECRYL ® 150, EBECRYL ® 860, EBECRYL ® 3702 by the company UCB and under the names PHOTOMER ® 3005 and PHOTOMER ® 3082 by the company HENKEL.
• Such copolymers are marketed for example under the names IRR ® 375 ATO ® 480 and EBECRYL ® 2047 by UCB.
• ⁇ , ⁇ -diacrylate polydimethylsiloxanes are available from the company SHIN-ETSU under the references X-22-164 B and X-22-164C.
• dendrimers and hyperbranched polymers carrying terminal (meth) acrylate or (meth) acrylamide groups, in particular obtained respectively by esterification or amidation of dendrimers and hyperbranched polymers with hydroxyl or amino terminal functions, with (meth) acrylic acid.
• Hyperbranched polymers are polycondensates, generally of the polyester, polyamide or polyethyleneamine type, obtained from multifunctional monomers, which have a tree structure similar to that of dendrimers but much less regular than the latter (see for example WO-A-93 / 17060 and WO 96/12754).
• the company PERSTORP markets hyperbranched polyesters under the name BOLTORN ® . We will find under the name COMBURST ® of the company
• DENDRITECH hyperbranched polyethyleneamines Poly (esteramide) hyperbranched hydroxyl end groups are marketed by the company DSM under the name HYBRANE ®. These dendrimers and hyperbranched polymers esterified or amidified by acrylic and / or methacrylic acid are distinguished from the polymers described under points a) to h) above by the very large number of ethylenic double bonds present. This high functionality, most often greater than 5, makes them particularly useful by allowing them to play a role of "crosslinking node", that is to say of multiple crosslinking site. In a preferred embodiment of the invention, these dendritic and hyperbranched polymers will therefore be used in combination with one or more of the polymers and / or oligomers a) to h) above.
• the compounds carrying at least two functions with labile hydrogen which can be used in the present invention are also known. They can be organic compounds of low molecular mass or else oligomers or synthetic polymers, obtained by polyaddition, polycondensation and / or grafting, or natural polymers chemically modified. According to the present invention, the functions containing labile hydrogen are preferably chosen from the primary amine (-NH 2 ), secondary amine (> NH), hydroxyl (-OH), carboxylic acid (-COOH) or thiol (-SH) functions. .
• the labile hydrogen function is a hydroxyl function
• the function with labile hydrogen is an amino function (NH 2 )
• it can be a diamine, a polyamine, an amino alcohol, an oligomer, or a polymer with amino groups.
• carrier compounds functions labile hydrogens are: alkylene glycols Ci, glycerol, trimethylolpropane, pentaerythritol, poly (alkylene C ⁇ _ 4) glycols such as polyethylene glycol or polyproylèneglycol or copolymers thereof, the condensation product of propylene glycol and trimethylolpropane, castor oil, phytantriol, sugars and carbohydrates such as sucrose or cellulose, ethylenediamine, 1,3-diaminopropane, lysine, ramino-2-methyl -2-propanol-l, poly (alkyleneoxy) diamines such as Jeffamine ® products marketed by the TEXACO company, nitrocellulose, cellulose esters, especially those having a degree of substitution of less than 3, such as cellulose acetate butyrate cellulose and cellulose acetopropionate, cellulose ethers such as hydroxyethylcellulose, carboxymethylcellulose, hydroxypropyl
• crosslinking is carried out by photochemical route and uses at least two types of compounds, in particular (A) and (B) respectively having at least one unsaturated double bond in the presence of a photoinitiator.
• a and B are chosen so as to form a reactive system whose average valence is greater than 2.
• the valence of a compound is called the number of covalent bonds which it can establish with the compounds which are associated with it.
• the average valence is defined as being equal to the ratio of the sum of the valences of all compounds A and B divided by the total number of compound A and B
• the compounds A or B can be a compound comprising a function of the unsaturated double bond type and in particular as defined above, and / or a monomer containing ethylenic unsaturation.
• a particular group of advantageous photoinitiators according to the invention is that of copolymerizable photoinitiators. These are molecules comprising both a photoinitiator group capable of a photoinduced radical scission and at least one ethylenic double bond. To obtain satisfactory holding properties, a total amount of photoinitiator (s) will generally be used at least equal to 0.1% by weight and at most equal to
• the crosslinking can be carried out in the presence of a co-film-forming agent such as, for example, nitrocellulose or cellulose esters.
• the article comprises at least one polymeric film obtained by evaporation of the solvent phase, organic or aqueous, from a solution or dispersion of at least one film-forming polymer.
• film-forming polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, an isolable film, in particular continuous on a support, in particular on keratin materials.
• a single film-forming polymer or a mixture of film-forming polymers can be used. This film-forming polymer can be chosen from the group consisting of radical polymers, polycondensates and polymers of natural origin.
• Film-forming polymers which are soluble or dispersible in an organic solvent
• said polymeric film is derived from the evaporation of the organic solvent phase from a solution or dispersion of at least one film-forming polymer.
• the organic film-forming polymer is at least one polymer chosen from the group comprising: film-forming polymers soluble or dispersible in at least one class of organic solvent such as for example ketones, alcohols, glycols and ethers of propylene glycols, short chain esters, alkanes and their aqueous or non-aqueous mixtures.
• the corresponding polymers can be of any chemical nature.
• the weight average molecular weights (Mp) of these polymers can vary from 3,000 to 1,000,000, in particular from 5,000 to 800,000, and in particular from 10,000 to 500,000.
• Mp weight average molecular weights
• the polymers soluble or dispersible in organic solvents the following polymers are particularly suitable: a) homo- and co-polymers esters and / or acid amides
• (meth) acrylics in particular polymers resulting from the polymerization or copolymerization of acrylates and / or methacrylates of methyl, ethyl, propyl, butyl, isobutyl, tertiobutyl, pentyl, hexyl, cyclohexyl, ethyl 2-hexyl, heptyl, octyl, isobornyl , norbornyle, adamantyle, or the corresponding (meth) acrylamides.
• These polymers will preferably contain from 0 to 20% of a polar comonomer such as (meth) acrylic acid, (meth) acrylamide, (hydroxy meth) acrylate, 2- hydroxypropyl (meth) acrylate, and (meth) acrylonitrile. They can also result from copolymerization with styrene or a substituted styrene.
• a polar comonomer such as (meth) acrylic acid, (meth) acrylamide, (hydroxy meth) acrylate, 2- hydroxypropyl (meth) acrylate, and (meth) acrylonitrile.
• polyurethanes acrylic polyurethanes, polyureas, polyureas of polyurea, polyester polyurethanes, polyether polyurethanes, polyesters, polyester amides, fatty chain polyesters, epoxys, and arylsulfonamide and in particular tosylamide / formaldehyde condensates
• polycondensates in particular if they are used as film-forming or cofilmogenic of one or more nitrocelluloses and / or of a cellulose ester (class c), more particularly to mention: - polyesters, in particular fatty chain polyesters and more particularly copolymers of CTFA name: “phthalic anhydride / glycerol / glycidyl decanoate copolymer” and “adipic acid / neopentyl glycol / trimellitic anhydride copolymer” - alkyds, - tosyl amide
• Aqueous dispersions of polymer particles or film-forming latexes derives from the evaporation of the aqueous phase of an aqueous dispersion of particles of film-forming polymer (s).
• the film-forming polymer can be chosen from the dispersions aqueous particles of polymers or film-forming latexes, and in this case the composition according to the invention comprises at least one aqueous phase.
• the aqueous dispersion comprising one or more film-forming polymers can be prepared by a person skilled in the art on the basis of his general knowledge, in particular by emulsion polymerization or by dispersing the previously formed polymer.
• film-forming polymers of this type which can be used in the composition according to the present invention, mention may be made of synthetic polymers, of polycondensate type or of radical type, polymers of natural origin, and their mixtures. It is possible in particular to use, but in the form of latex, the polymers (homo- and co-polymers) which are mentioned above as polymers soluble or dispersible in an organic solvent medium, and more particularly the polymers of classes a, b and c.
• polycondensates there may be mentioned anionic, cationic, nonionic or amphoteric polyurethanes, acrylic polyurethanes, polyurethanes polyvinylpyrrolidones, polyester polyurethanes, polyether polyurethanes, polyureas, polyureas polyurethanes, and their mixtures . Mention may also be made of polyesters, polyester amides, fatty chain polyesters, polyamides and epoxy ester resins. The polyesters can be obtained, in a known manner, by polycondensation of aliphatic or aromatic diacids with aliphatic or aromatic diols or polyols.
• succinic acid succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or sebacic acid
• aromatic diacids terephthalic acid or isophthalic acid can be used, or alternatively a derivative such as phthalic anhydride.
• aliphatic diols ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexane dimethanol, 4,4 '- (1-methylpropylidene) bisphenol can be used.
• polyols glycerol, pentaerythritol, sorbitol, trimethylol propane can be used.
• the polymers of radical type can in particular be polymers, or copolymers, acrylic and / or vinyl.
• anionic radical polymers are used.
• the monomer carrying an anionic group which can be used during radical polymerization mention may be made of acrylic acid, acid methacrylic, crotonic acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid.
• the acrylic polymers can result from the copolymerization of monomers chosen from esters and / or amides of acrylic acid or methacrylic acid.
• ester type monomers mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate.
• monomers of amide type there may be mentioned Nt-butyl acrylamide and Nt-octyl acrylamide.
• the vinyl polymers can result from the homopolymerization or from the copolymerization of monomers chosen from vinyl esters, styrene or butadiene.
• vinyl esters examples include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. It is also possible to use acrylic / silicone copolymers or else nitrocellulose / acrylic copolymers. Mention may also be made of the polymers resulting from the radical polymerization of one or more radical monomers inside and / or partially at the surface, of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and / or alkyds. These polymers are generally called hybrid polymers.
• the dispersion can also comprise an associative polymer of polyurethane type or a natural gum, such as xanthan gum.
• an associative polymer of polyurethane type or a natural gum such as xanthan gum.
• aqueous dispersion there may be mentioned the dispersions of acrylic polymers sold under the names NEOCRYL XK-90 ® , NEOCRYL A- 1070 ® , NEOCRYL A- 1090 ® , NEOCRYL BT-62 ® , NEOCRYL A- 1079 ® , NEOCRYL A -523 ® by the company ZENECA, DOW LATEX 432 ® , by the company DOW CHEMICAL.
• aqueous dispersions of polyurethane and in particular the polyester polyurethanes sold under the names "AVALURE UR-405 ® “, “AVALURE UR-410 ® “, “AVALURE UR-425 ® “, “SANCURE 2060 ® “ by the company GOODRICH and the polyether-polyurethanes sold under the names "SANCURE 878 ® " by the company GOODRICH, "NEOREZ R-970 ® " by the company AVECIA. All of the above film-forming polymers can be combined with at least one auxiliary film-forming and / or coalescing agent.
• the film-forming auxiliary agent can be chosen from all the compounds known to a person skilled in the art as being capable of fulfilling the desired function, and can be chosen in particular from plasticizing agents and coalescing agents of the film-forming polymer.
• plasticizing agents and coalescing agents such as: - glycols and their derivatives such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or even diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether; - glycol esters, - propylene glycol derivatives and in particular propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol e
• plasticizer and / or coalescing agent can be chosen by those skilled in the art based on their general knowledge.
• the content of plasticizer and / or coalescing agent can range from 0.01% to 10% and in particular from 1% to 3% by weight relative to the total weight of the composition.
• ADHESIVE MATERIAL The article according to the invention has an adhesive external face. Such an adhesive face is generally obtained by virtue of the presence of at least one layer of at least one adhesive material.
• material is meant within the meaning of the present invention a polymer or a polymeric system which may comprise one or more polymers of different natures.
• This adhesive material can be in the form of a polymer solution or a dispersion of polymer particles in a solvent.
• This adhesive material may also contain a plasticizer as defined above.
• This adhesive material must have a certain tackiness defined by its viscoelastic properties.
• the viscoelastic properties of a material are conventionally defined by two characteristic values which are as follows: the elastic modulus which represents the elastic behavior of the material for a given frequency and which is conventionally denoted G ′, the viscous modulus which represents the viscous behavior of material for a given frequency and which is conventionally noted G ". These quantities are notably defined in the" Handbook of Pressure Sensitive Adhesive Technology "3 rd edition, D. Satas, chap. 9, p. 155 to 157.
• the adhesive materials which can be used according to the present invention have viscoelastic properties which are measured at a reference temperature of 35 ° C. and within a certain frequency range.
• adhesive materials in the form of a solution or dispersion of polymer in a volatile solvent such as water, a short ester, a short alcohol, acetone
• the viscoelastic properties of this material are measured under conditions in which it has a volatile solvent content of less than 30%, and in particular a volatile solvent content of less than 20%.
• the elastic modulus of the material is measured at three different frequencies: at low frequency, either at 2.10 2 Hz, at an intermediate frequency, or at 0.2 Hz, at high frequency, at 2 Hz, and the viscous module at the frequency of 0.2 Hz.
• said adhesive material meets the following conditions: - G '(2 Hz, 35 ° C)> 10 3 Pa, and - G' (35 ° C) ⁇ 10 8 Pa, in particular G '(35 ° C) ⁇ 10 7 Pa, - G '(2.10 "2 Hz, 35 ° C) ⁇ 3.10 5 Pa, in which: G' (2 Hz, 35 ° C) is the elastic shear modulus of said adhesive material, measured at the frequency of 2 Hz and at a temperature of 35 ° C, G '(35 ° C) is the elastic shear modulus of said adhesive material, measured at a temperature of 35 ° C, for any frequency between 2.10 "2 and 2 Hz, G '(2.10 "2 Hz, 35 ° C) is the elastic shear modulus of said adhesive material, measured at the frequency of 2.10 " 2 Hz and at the temperature of 35 ° C.
• the adhesive material also meets the following condition: - G "/ G '(0.2 Hz, 35 ° C)> 0.35.
• G" (0.2 Hz , 35 ° C) is the viscous shear modulus of said adhesive material, measured at the frequency of 0.2 Hz and at the temperature of 35 ° C
• - G '(0.2 Hz, 35 ° C) is the elastic modulus shear of said adhesive material, measured at the frequency of 0.2 Hz and at the temperature of 35 ° C.
• the adhesive materials according to the invention meet the following four conditions: - G' (2 Hz, 35 ° C) ⁇ 10 4 Pa, and - G '(35 ° C) ⁇ 10 8 Pa, in particular G' (35 ° C) ⁇ 10 7 Pa, - G '(2.10 "2 Hz, 35 ° C) ⁇ 5.10 4 Pa, and - G" / G '(0.2 Hz, 35 ° C)> 0.35.
• the adhesive is such that the said article cannot be peeled off when it is applied to the surface of a synthetic nail or natural after at least 24 hours of application.
• the adhesive materials according to the invention can be chosen from adhesives of the "Pressure Sensitive Adhesives" type, for example, those mentioned in the "Handbook of Pressure Sensitive Adhesive Technology "3 rd edition, D. Satas.
• the adhesive materials according to the invention are in particular polymers chosen from block or random copolymers comprising at least one monomer or a combination of monomers, the polymer of which resulting at a glass transition temperature below room temperature (25 ° C.), these monomers or associations of monomers being able to be chosen among butadiene, ethylene, propylene, isoprene, isobutylene, a silicone, and their mixtures.
• Examples of such materials are polymer blocks type styrene-butadiene-styrene, styrene- (ethylene-butylene) -styrene, styrene-isoprene-styrene such as those sold under the trade names "Kraton ®” from Shell Chemical Co. or "Vector ® " from EXXXON.
• the adhesive materials according to the invention are in particular adhesive polymers chosen from: polyurethanes, acrylic polymers, - silicones, butyl gums, in particular from polyisobutylenes, ethylene-vinyl acetate polymers, polyamides optionally modified with fatty chains, natural gums, and their mixtures.
• They may in particular be adhesive copolymers derived from the copolymerization of vinyl monomers with polymeric entities such as, for example, those described in US Pat. No. 6,136,296.
• the adhesive materials are for example chosen from polyisobutylenes having a relative molar mass Mv greater than or equal to 10,000 and less than or equal to 150,000.
• this relative molar mass is greater than or equal to 18,000 and less than or equal to 150 000.
• polyisobutylenes of respective molar masses Mv 40,000, 55,000 and 85,000 sold under the respective trade names "Oppanol B 10 ® ", "Oppanol B 12 ® “and” Oppanol B 15 ® “by BASF, and their mixtures.
• the adhesive material and the film have compatibility thanks to their chemical nature and their composition.
• the solvent of the adhesive is capable of leading to an increase in mass of the film brought into contact, in particular of at least 10% by weight relative to the initial weight of the film.
• the adhesive material in the article according to the invention is generally in the form of a layer having a thickness of 1 micron to 100 microns and in particular from 1 micron to 50 microns, preferably from 1 micron to 25 microns.
• the article may also comprise, in particular at the level of its organic film, at least one coloring, organic or inorganic material, in particular of the pigment or pearlescent type conventionally used in cosmetic compositions.
• the term “pigments” should be understood to mean white or colored, mineral or organic particles, insoluble in an aqueous solution, intended to color and / or opacify the resulting film.
• the pigments can be present in an amount of 0.01 to 15% by weight, in particular from 0.01 to 10% by weight, and in particular from 0.02 to 5% by weight, relative to the total weight of the article. .
• inorganic pigments which can be used in the invention, mention may be made of titanium, zirconium or cerium oxides as well as oxides of zinc, iron or chromium, ferric blue, manganese violet, ultramarine blue and chromium hydrate. It may also be a pigment having a structure which may, for example, be of the sericite / brown iron oxide / titanium dioxide / silica type. Such a pigment is marketed, for example, under the reference COVERLEAF NS or JS by the company CHEMICALS AND CATALYSTS and has a contrast ratio close to 30.
• the coloring matter may also comprise a pigment having a structure which may, for example, be of the microsphere type. silica containing iron oxide. An example of a pigment having this structure is that marketed by the company
• MIYOSHI under the reference PC BALL PC-LL-100 P this pigment being made up of silica microspheres containing yellow iron oxide.
• organic pigments which can be used in the invention, there may be mentioned carbon black, pigments of D & C type, lacquers based on cochineal carmine, barium, strontium, calcium, aluminum or else diketo pyrrolopyrrole (DPP ) described in documents EP-A-542669, EP-A-787730, EP-A-787731 and WO-A- 96/08537.
• nacres By “nacres”, it is necessary to understand colored particles of any shape, iridescent or not, in particular produced by certain molluscs in their shell or else synthesized and which exhibit a color effect by optical interference.
• the nacres can be chosen from pearlescent pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye as well as pearlescent pigments based on bismuth oxychloride. It can also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic coloring matters.
• nacres of natural mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride.
• FLAMENCO and DUOCHROME (based on mica) marketed by the company ENGELHARD, TIMIRON nacres marketed by the company MERCK, nacres based on PRESTIGE mica marketed by the company ECKART and nacres based on synthetic mica SUNSHINE marketed by the company SUN Chemical.
• the nacres can more particularly have a yellow or pink, red, bronze, orange, brown, gold and / or coppery color or reflection.
• nacres which can be used in the context of the present invention, mention may be made in particular of the gold-colored nacres sold in particular by the company ENGELHARD under the name of Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold in particular by the company MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company ENGELHARD under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown-colored mother-of-pearl in particular sold by the company ENGELHARD under the name of Brill
• the article according to the invention can also comprise water-soluble or liposoluble dyes in a content ranging from 0.01 to 10% by weight, in particular ranging from 0.01 to 5% by weight relative to the total weight of the article.
• the fat-soluble dyes are, for example, Sudan red, DC Red 17, DC Green 6, ⁇ -carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DC orange 5, quinoline yellow
• Water-soluble dyes are for example beet juice, methylene blue.
• formulation additives commonly used in cosmetics and more especially in the cosmetic and / or nail care field. They can in particular be chosen from vitamins, trace elements, softeners, sequestrants, basifying or acidifying agents, wetting agents, thickening agents, dispersing agents, anti-foaming agents, spreading agents, co-resins, film-forming polymers, plasticizers, coalescing agents, preservatives, UV filters, active ingredients, hydrating agents, neutralizers, stabilizers, antioxidants and their mixtures.
• active agents hardening agents for keratin materials and / or active agents for treating various affections localized at the level of the nail, such as for example onichomycosis.
• the amounts of these various ingredients are those conventionally used in this field and for example from 0.01 to 20% by weight, and in particular from 0.01 to 10% by weight relative to the total weight of the article.
• the article according to the invention generally has a thickness of 1 micron to 500 microns, in particular from 1 micron to 300 microns and in particular from 1 micron to 200 microns.
• the article according to the invention is coated at least on its adhesive external face with a removable support.
• a removable support can be of any kind compatible with the fact that although it is in contact with an adhesive material, it can nevertheless be separated from it.
• the removable support defined above can in particular be in the form of a protective layer consisting for example of a film, in particular of a plastic film or a paper or a textile structure of sheet type.
• this support is made of a transparent material in order to prevent any error in the choice of color. It may consist of one or more layers which may be of a different nature.
• plastic film which can be used, for example, in the article in accordance with the invention, mention may be made of films made of polyesters, for example polyethylene terephthalates, polybutylene terephthalates or polyethylene sebacates or made of polyethylene, polypropylene or polyamides such as polyhexamethylene adipate, polycaprolactam or poly (omega- ⁇ -undecanoic acid amide). Due to their surface characteristics, these plastics are of course not removable as such.
• the sheet type textile structure can be a woven or non-woven fabric.
• the article according to the invention is coated on its two faces with a removable support, identical or different.
• the article according to the present invention can be in various forms such as a star, a square, a circle, etc.
• the present invention also covers a product suitable for packaging an article in accordance with the present invention in a partially dry form. It is only once applied that the article according to the present invention is dried and then adopts its final structure by bringing it into contact with ambient air. An article in accordance with the invention can in particular be obtained with a device as described in US Pat. No. 4,903,840.
• the present invention also relates, as indicated above, to a process for preparing a flexible article for making up and / or caring for nails.
• the adhesive material is generally deposited in the form of a layer of material having a thickness which can range from 0.5 microns to 200 microns, and in particular from 1 micron to 100 microns.
• An article, according to the invention and the organic film of which is obtained by evaporation of the solvent phase, organic or aqueous, of a solution or dispersion of film-forming polymer (s) can for example be obtained by transposition of the process described in US Pat. No. 5,415,903.
• the material with an optical effect, relief and / or olfactory, is in this case introduced into the solvent phase considered.
• the article obtained, and in particular the excess film, is then generally cut out, before or after its application, according to the desired size and shape with small scissors, a nail clipper or by scraping the film.
• the present invention also relates to a method for making up the nails in which the article is applied as defined above.

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• 2004
  • 2004-05-19 FR FR0451004A patent/FR2870452B1/fr not_active Expired - Fee Related
• 2005
  • 2005-05-17 US US11/579,274 patent/US20090126316A1/en not_active Abandoned
  • 2005-05-17 EP EP05762737A patent/EP1746913A2/de not_active Withdrawn
  • 2005-05-17 WO PCT/FR2005/050335 patent/WO2005112687A2/fr active Application Filing

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