NAIL POLISH FILM WITH OPTICAL EFFECT

Abstract

The present invention provides a flexible article with an optical, relief, and/or olfactory effect for making up and/or caring for the nails, comprising: at least one adhesive layer for fixing the article to the nail; at least one organic film; and at least one material with an optical, relief, or olfactory effect.

Description

The present invention relates to a flexible article with an optical, relief, and/or olfactory effect for application to the nails to make them up and/or to care for them.

Conventionally, nails or false nails are made up using liquid makeup compositions, still generally known as nail polish. Such nail polish is generally applied to the surface of the nail to be made up in the form of superposed layers, allowing an intermediate drying step between each application of nail polish. In reality, such a makeup method is not entirely satisfactory.

Firstly, applying it requires a certain amount of time.

Further, that type of makeup has to be re-applied within a short period because it does not stay on sufficiently well. In three to five days in general, polish which has been applied flakes and loses its gloss. It must then be removed and fresh makeup needs to be re-applied.

Finally, conventional nail polish formulations generally involve the use of volatile solvents which generate a disagreeable odor during application.

The aim of the present invention is to propose a method of making up and/or caring for nails or false nails which, in contrast to conventional liquid type nail polish formulations, is easy and rapid to apply stays on significantly longer, has a significantly reduced organic solvent(s) content and also can provide an optical, relief, and/or olfactory cosmetic effect.

More precisely, in a first aspect, the present invention provides a flexible article for making up and/or caring for nails and/or false nails, comprising:

• • at least one adhesive layer for fixing the article to the nail;
  • at least one organic film; and
  • at least one material with an optical, relief, and/or olfactory effect.

In a variation, the article may comprise at least two different organic films superposed on the adhesive layer.

In particular, each of said films may contain at least one material with an optical, relief, and/or olfactory effect.

More particularly, one of them is free of said material. In that implementation, it is generally the film which is not contiguous with the adhesive layer.

In this variation of the invention, the film which is free of material with an optical, relief, and/or olfactory effect is preferably transparent.

As used here, the term “transparent” means that the cross-linked coating has a HAZEBYK index of less than 5 as measured with a KYKHAZEGLOSS type gloss meter.

In a second aspect, the present invention provides a method of preparing a flexible article for making up and/or caring for the nails comprising at least the following steps consisting of superposing, 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 which can form, by cross-linking and/or evaporation of its organic or aqueous solvent phase, an organic film containing at least one material with an optical, relief, and/or olfactory effect, said film being formed consecutively to deposition of said composition.

In a variation of the invention, the method comprises a step b) of depositing a first composition and transforming it into an organic film and depositing, onto the film thus formed, a second composition which differs from the first composition, and then transforming it into a second organic film.

In a further variation, said method comprises, at the end of step b), a step of drying said article which step is stopped before a completely dry condition is obtained for said article. The article obtained is termed “partially dry”.

In a third aspect, the present invention provides a substance for making up and/or caring for the nails and/or false nails comprising, in packaging which is substantially airtight, at least one article in accordance with the invention, the packaging being such that the article is preserved in a partially dry form.

Within the context of the present invention, the term “partly dry” is intended to mean that the article obtained after forming an organic film, i.e. after evaporating off the organic or aqueous solvent phase from a solution or dispersion of at least one film-forming polymer or by cross-linking a cross-linkable composition, is not entirely free of residual solvent. In particular, it has a dry matter content of less than 80%, in particular less than 75% and more particularly less than 70% by weight relative to its total weight.

In accordance with a particular implementation, said packaging comprises a reservoir, such as a pouch, which may or may not be flexible, and which is suitable for containing a substance in airtight manner. In particular, it is impermeable to air and/or solvents. Said packaging can preserve said article from prematurely drying out completely before it is used.

In a fourth aspect, the present invention provides a method of preparing a substance as defined above, comprising the following steps consisting of superposing, 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 which can form an organic film by cross-linking and/or evaporation of its organic or aqueous solvent phase, containing at least one material with an optical, relief, and/or olfactory effect, said film being formed consecutively to deposition of said composition;

c) if necessary, partially drying the article obtained; and

d) packaging said article in a partially dry condition within a substantially airtight packaging.

In this implementation, the article only becomes completely dry, and thus only achieves its definitive form, after application to the nail, simply by exposure to the ambient air.

In a fifth aspect, the present invention provides a method of making up and/or caring for the nails, the method comprising applying the adhesive face of an article in accordance with the invention to a natural or synthetic nail.

Within the context of the present invention, the term “organic” also encompasses composite type materials, i.e. associating an organic component with an inorganic component. As an example, the organic film may behave as an organic matrix into which at least one inorganic material is incorporated, and which may contribute per se to the production of the film.

Within the context of the present invention, the term “flexible” means sufficient flexibility for the article of the invention. More precisely, that article is in the form of a film which can accommodate stretch-type mechanical deformations to adjust to the surface of a nail. This deformability is characterized in particular by the deformation at break parameter ∈_r discussed below.

The article of the invention differs from a false nail type article, which is characterized by a stiffness which is incompatible with such mechanical deformation.

A further difference between the article of the invention and a false nail lies in the fact that this article is sensitive to polar organic solvents of the acetone, ester and/or lower alcohol type. The organic film on the outer face of the article of the invention, i.e. the face which does not adhere to the nail, can swell, which results in an increase in its weight when it is brought into contact with one of said solvents. A false nail is completely free of such sensitivity. This ability of the article of the invention to swell is advantageous since it can be eliminated when it is applied to the surface of a nail or a false nail. The article of the invention can readily be removed simply by using a conventional remover, as opposed to a false nail which has to be taken off. More precisely, it may be removed by organic solvents, in particular alkyl acetates and mixtures thereof.

It also stays on for a significant period on the scale of at least one week. It turns out to be resistant to water, friction and shocks and does not wear or flake significantly within that period.

Finally, as indicated above, the article of the invention is of particular advantage on the make-up front since it can produce a large variety of original effects which go beyond conventional colored effects. The inventors have shown that the film structure of the article is particularly advantageous in producing effects which are other than simple conventional static colored effects, in particular by packaging therewith materials with an optical, relief, and/or olfactory effect, of a wide variety of natures. Said materials may in particular be organic, inorganic and/or composite in nature.

Clearly, certain materials may produce a plurality of simultaneous effects on the articles of the invention. As an example, particles with an optical effect may, in addition to the expected optical effect, provide a colored or even a relief effect if their particle size is sufficiently large.

For obvious reasons, the quantities of these materials which may be used can vary significantly as a function of the desired effect and as a function of the nature of the materials and/or their size and/or their form when in the form of particles and/or fibers.

The skilled person will be capable of making that adjustment as a function of the material under consideration.

Optical Effect Material

The flexible article of the invention may contain at least one material with a specific optical effect, in particular present in its organic film.

As described above, this effect differs from a simple conventional hue effect, i.e. uniform and stabilized such as that produced by conventional coloring materials, for example monochromatic pigments. Within the context of the invention, the term “stabilized” means free of color variability with angle of observation or in response to a temperature change.

Said material is present in a quantity sufficient to produce an optical effect which is visible to the naked eye. Advantageously, it is an effect selected from goniochromatic, metallic especially mirror, soft-focus, rainbow and/or thermochromic effects.

As an example, said material may be selected from particles with a metallic glint, goniochromatic coloring agents, diffractive pigments, thermochromic agents, optical whitening agents, as well as fibers, in particular interferential fibers. Clearly, said various materials may be combined to simultaneously produce two effects or even a novel effect within the context of the invention.

Particles with a Metallic Glint

The term “particles with a metallic glint” denotes particles of nature, size, structure, and surface condition that allows them to reflect incident light, in particular in a non iridescent manner.

Particles with a substantially planar outer surface are also suitable since they can readily produce intense specular reflection which may be qualified as a mirror effect if their size, structure and surface condition allow.

The particles with a metallic glint of the invention may, for example, reflect light in all of its visible components without significantly absorbing one or more wavelengths. The spectral reflectance of said particles may, for example, be more than 70% in the 400 nm [nanometers] to 700 nm range, preferably at least 80% or even 90% or 95%.

Said particles are generally 1 μm [micrometer] or less in thickness, in particular 0.7 μm or less in thickness, and in particular 0.5 μm or less in thickness.

In particular, the total proportion of particles with a metallic glint is 20% by weight or less, in particular 10% by weight or less relative to the total weight of the article.

In particular, the particles with a metallic glint which are used in accordance with the invention are selected from:

• • particles of at least one metal and/or at least one metallic derivative;
  • particles comprising a substrate, which may be organic or mineral, a mono-material or a multi-material, at least partially covered with at least one layer with a metallic glint comprising at least one metal and/or at least one metallic derivative; and
  • mixtures of said particles.

Examples of metals which may be present in said particles which may be mentioned are Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, w, Zn, Ge, Te, Se and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr and their mixtures or alloys (for example bronzes and brasses) are preferred metals.

The term “metallic derivatives” means compounds derived from metals, in particular oxides, fluorides, chlorides and sulfides.

Examples that can be mentioned of metallic derivatives which may be present in said particles are metallic oxides such as oxides of titanium, in particular TiO₂, of iron, in particular Fe₂O₃, of tin, of chromium, barium sulfate and the following compounds: MgF₂, CrF₃, ZnS, ZnSe, SiO₂, Al₂O₃, MgO, Y₂O₃, SeO₃, SiO, HfO₂, ZrO₂, CeO₂, Nb₂O₅, Ta₂O₅, MoS₂ and their mixtures or alloys.

In a first variation, the particles with a metallic glint may be composed of at least one metal as defined above, at least one metallic derivative as defined above or a mixture thereof.

Said particles may be at least partially covered with a layer of another material, for example a transparent material such as colophany, silica, stearates, polysiloxanes, polyester resins, epoxy resins, polyurethane resins or acrylic resins.

Illustrative examples of such particles which may be mentioned are particles of aluminum, such as those sold under the trade names STARBRITE 1200 EAC® by SIBERLINE and METALURE® by ECKART.

It is also possible to mention copper powders or alloy mixtures such as reference 2844 sold by RADIUM BRONZE, metallic pigments such as aluminum or bronze, such as those sold under the trade name ROTOSAFE 700 by ECKART, particles of aluminum coated with silica sold under the trade name VISIONAIRE BRIGHT SILVER by ECKART and particles of metal alloy such as bronze powders (copper and zinc alloy) coated with silica sold as VISIONAIRE BRIGHT NATURAL GOLD by ECKART.

In a second variation, said particles may be particles comprising a substrate and which thus present a structure that is multilayered, for example two-layered. Said substrate may be organic or inorganic, natural or synthetic, a mono- or multi-material, solid or hollow. When the substrate is synthetic, it may be produced in a form encouraging the formation of a reflective surface after coating, in particular after depositing a layer of material with a metallic glint. The substrate may, for example, have a planar surface and the layer of materials with a metallic glint may have substantially uniform thickness.

In particular, the substrate may be selected from the metals and metallic derivatives 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 limiting.

The layer with a metallic effect may completely or partially coat the substrate and said layer may be at least partially coated with a layer of another material, for example a transparent material as mentioned above. In a particular implementation, said layer with a metallic glint completely coats the substrate directly or indirectly, i.e. with the interposition of at least one metallic or non metallic intermediate layer.

The metals or metallic derivatives which may be used in the reflective layer are as defined above. As an example, it may be formed by at least one metal selected from silver, aluminum, chromium, nickel, molybdenum, gold, copper, tin, magnesium and mixtures (alloys) thereof. More particularly, sliver, chromium, nickel, molybdenum and mixtures thereof may be used.

An illustrative example of said second type of particle which may be mentioned is as follows:

• • particles of glass coated with a metallic layer, in particular those described in Japanese patent documents JP-A-09188830, JP-A-10158450, JP-A-10158541; JP-A-07258460 and JP-A-05017710.

Illustrative examples of such particles comprising a glass substrate which may be mentioned are those coated respectively with silver, gold or titanium in the form of flakes sold by NIPPON SHEET GLASS under the MICROGLASS METASHINE trade names. Particles with a glass substrate coated with silver in the form of flakes are sold under the trade name MICROGLASS METASHINE REFSX 2025 PS by TOYAL. Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the trade name CRYSTAL STAR GF 550, GF 2525 by the same firm. Those coated with either brown iron oxide or titanium oxide, tin oxide or a mixture thereof such as those sold under the trade name REFLECKS® by ENGELHARD or those sold under the trade name METASHINE MC 2080GP by NIPPON SHEET GLASS are also known.

Said glass particles coated with metals may be coated with silica, such as those sold under the trade name METASHINE series PSS1 or GPS1 by NIPPON SHEET GLASS.

• • Particles with a spherical glass substrate which may or may not be coated with a metal, in particular those sold under the trade name PRIZMALITE MICROSPHERE by PRIZMALITE industries.
  • Pigments from the METASHINE 1080R range sold by NIPPON SHEET GLASS Co. LTD are also suitable. Said pigments, more particularly those described in Japanese patent JP 2001-11340, are C-GLASS glass flakes comprising 65% to 72% of SiO₂ coated with a layer of rutile (TiO₂) type titanium oxide. Said glass flakes have a mean thickness of 1 μm and a mean size of 80 μm, giving a mean size/mean thickness ratio of 80. They have blue, green, yellow or silver glints depending on the thickness of the TiO₂ layer.
  • Particles comprising a borosilicate substrate coated with silver, also known as “white nacres”.
  • Particles with a metallic substrate such as aluminum, copper, bronze, in the form of flakes, are sold under the trade name STARBRITE by SILBERLINE and under the trade name VISIONAIR by ECKART.
  • Particles comprising a synthetic mica substrate coated with titanium dioxide, for example particles with a dimension in the range 80 μm to 100 μm comprising a synthetic mica (fluorophlogopite) substrate coated with titanium dioxide representing 12% of the total weight of the particle are sold under the trade name PROMINENCE by NIHON KOKEN.
  • The particles with a metallic glint may also be selected from particles formed by a stack of at least two layers with different refractive indices. Said layers may be polymeric or metallic in nature and in particular may include at least one polymeric layer.

Thus, the particles with a metallic effect may be particles deriving from a multi-layered polymeric film.

The choice of materials intended to constitute the various layers of the multi-layered structure is clearly made so as to provide the particles formed with the desired metallic effect.

Such particles have in particular been described in International patent application WO-A-99/36477 and United States patents U.S. Pat. No. 6,299,979 and U.S. Pat. No. 6,387,498 and are more particularly identified in the section on goniochromatic effects.

Diffractive Pigments

The term “diffractive pigment” as used in the present invention means a pigment which is capable of producing a variation in color depending on the angle of observation when illuminated with white light, due to the presence of a structure which diffracts light.

A diffractive pigment may comprise a diffraction grating capable, for example, of diffractive an incident ray of monochromatic light in predefined directions.

The diffraction grating may comprise a periodic motif, in particular a line, the distance between two adjacent motifs 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 various spectral components of the light and produce a rainbow effect.

Reference concerning the structure of diffractive pigments can usefully be made to the article “Pigments exhibiting diffractive effects” by Alberto Argoitia and Matt Witzman, 2002, Society of Vacuum Coaters, 45^th Annual Technical Conference Proceedings, 2002.

The diffractive pigment may be produced from motifs having different profiles, in particular triangular, symmetrical or otherwise, crenellated, with a constant or non constant width, or sinusoidal.

The spatial frequency of the grating and the depth of the motifs will be selected as a function of the degree of separation of the various desired orders. The frequency may, for example, vary from 500 lines per mm [millimeter] to 3000 lines per mm.

Preferably, the particles of diffractive pigment each have a flattened form, in particular the form of a flake.

A single pigment particle may comprise two diffractive gratings which cross, perpendicularly or otherwise.

One possible structure for the diffractive pigment may comprise a layer of a reflective material, covered on at least one side with a layer of a dielectric material. This layer may provide the diffractive pigment with better rigidity and durability. The dielectric material may thus, for example, be selected from the following materials: MgF₂, SiO₂, Al₂O₃, AlF₃, CeF₃, LaF₃, NdF₃, SmF₂, BaF₂, CaF₂, LiF and combinations thereof. The reflective material may, for example, be selected from metals and their alloys and also from non metallic reflective materials. Some metals which may be used which may be mentioned are Al, Ag, Cu, Au, Pt, Sn, Ti, Pd, Ni, Co, Rd, Nb, Cr and compounds, combinations and alloys thereof. Such a reflective material may alone constitute the diffractive pigment which will then be a monolayer.

In a variation, the diffractive pigment may comprise a multi-layered structure comprising a core of a dielectric material covered on at least one side with a reflective layer, or it may completely encapsulate the core. A layer of a dielectric material may also cover the reflective layer or layers. The dielectric material used is thus preferably inorganic and may, for example, be selected from metallic fluorides, metallic oxides, metallic sulfides, metallic nitrides, metallic carbides and combinations thereof. The dielectric material may be in the crystalline, semi crystalline or amorphous state. In this configuration, the dielectric material may, for example, be selected from the following materials: MgF₂, SiO, SiO₂, Al₂O₃, TiO₂, WO, AlN, BN, B₄C, WC, TiC, TiN, N₄Si₃, ZnS, glass particles, diamond type carbon and combinations thereof.

The diffractive pigment used may in particular be selected from those described in United States patent application US 2003/0031870 published on Feb. 13, 2003.

A diffractive pigment may, for example, comprise the following structure: MgF₂/Al/MgF₂; a diffractive pigment with that structure is sold under the trade name SPECTRAFLAIR 1400 Pigment Silver by FLEX PRODUCTS, or SPECTRAFLAIR 1400 Pigment Silver FG. The proportion by weight of MgF₂ may be in the range 80% to 95% of the total pigment weight.

Goniochromatic Coloring Agents

Within the context of the invention, a goniochromatic coloring agent allows a color change, also termed a “color flop”, to be observed as a function of the angle of observation, which is higher than that which may be obtained with nacres. One or more goniochromatic coloring agents may be used simultaneously.

The goniochromatic coloring agent may be selected to present a relatively large color change with the angle of observation.

The goniochromatic coloring agent may thus be selected so that for a variation in the angle of observation in the range 0° to 80°, illuminated at 450, a variation ΔE of at least 2 is observed in the color of the cosmetic composition, measured in the CIE 1976 colorimetric space.

The goniochromatic coloring agent may also be selected so that for an illumination at 45° and a variation in the angle of observation in the range 0° to 80°, a variation Dh of at least 30° or even at least 40° or at least 60° or even at least 100° is observed in the angle of the hue of the cosmetic composition, using the CIE 1976 colorimetric space.

The goniochromatic coloring agent may, for example, be selected from interferential multi-layered structures and liquid crystal coloring agents.

In the case of a multi-layered structure, this may, for example, comprise at least two layers, each layer, independently or otherwise of the other layer(s) being produced, for example, from at least one material selected from the group constituted by the following materials: MgF₂, CeF₃, ZnS, ZnSe, Si, SiO₂, Ge, Te, Fe₂O₃, Pt, Va, Al₂O₃, MgO, Y₂O₃, S₂O₃, SiO, HfO₂, ZrO₂, CeO₂, Nb₂O₅, Ta₂O₅, TiO₂, Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS₂, cryolite, alloys, polymers and combinations thereof.

The multi-layered structure may or may not be symmetrical relative to a central layer as regards the chemical nature of the stacked layers.

Examples of symmetrical interferential multi-layered structures which may be used in compositions produced in accordance with the invention are as follows: Al/SiO₂/Al/SiO₂/Al, pigments with this structure being sold by DUPONT DE NEMOURS; Cr/MgF₂/Al/MgF₂/Cr, pigments with this structure being sold under the trade name CHROMAFLAIR by FLEX; MoS₂/SiO₂/Al/SiO₂/MoS₂; Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃, and Fe₂O₃/SiO₂/Fe₂O₃/SiO₂/Fe₂O₃, pigments having these structures being sold under the trade name SICOPEARL by BASF; MoS₂/SiO₂/mica-oxide/SiO₂/MoS₂; Fe₂O₃/SiO₂/mica-oxide/SiO₂/Fe₂O₃; TiO₂/SiO₂/TiO₂ and TiO₂/Al₂O₃/TiO₂; SnO/TiO₂/SiO₂/TiO₂/SnO; Fe₂O₃/SiO₂/Fe₂O₃; SnO/mica/TiO₂/SiO₂/TiO₂/mica/SnO, pigments having these structures being sold under the trade name XIRONA by MERCK (Darmstadt). By way of example, said pigments may be pigments with a silica/titanium oxide/tin oxide structure sold under the trade name XIRONA MAGIC by MERCK, pigments with a silica/brown iron oxide structure sold under the trade name XIRONA INDIAN SUMMER by MERCK and pigments with a silica/titanium oxide/mica/tin oxide structure sold under the trade name XIRONA CARIBBEAN BLUE by MERCK. INFINITE COLORS pigments by SHISEIDO may also be mentioned. Depending on the nature of the various layers, different effects are obtained. Thus, with the Fe₂O₃/SiO₂/Al/SiO₂/Fe₂O₃ structure, the color passes from golden green to red-gray for SiO₂ layers from 320 nm to 350 nm; from red to golden for SiO₂ layers from 380 nm to 400 nm; from violet to green for SiO₂ layers from 410 nm to 420 nm; from copper to red for SiO₂ layers from 430 nm to 440 nm.

It is also possible to use goniochromatic coloring agents with a multi-layered structure comprising alternating polymeric layers.

A non-limiting list of illustrative materials which may constitute the various layers of the multi-layered structure which may be mentioned is as follows: 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, polycarbonates, polymethacrylates and alkyl polyacrylates, syndiotactic polystyrene (sPS), syndiotactic poly-alpha-methylstyrenes, syndiotactic polydichlorostyrene, copolymers and mixtures of said polystyrenes, cellulose derivatives, polyalkylene polymers, fluorinated polymers, chlorinated polymers, polysulfones, polyethersulfones, polyacrylonitriles, polyamides, silicone resins, epoxy resins, polyvinyl acetate, polyether-amides, ionomeric resins, elastomers and polyurethanes. Copolymers are also suitable, for example copolymers of PEN (for example, copolymers of 2,6-, 1,4-, 1,5-, 2,7-, and/or 2,3-naphthalene dicarboxylic acid or its esters with (a) acid terephthalic 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, copolymers of polyalkylene terephthalates and styrene copolymers. Further, each individual layer may include mixtures of two or more of the preceding polymers or copolymers. The choice of materials intended to constitute the various layers of the multi-layered structure is clearly made so as to endow the particles formed with the desired optical effect.

Examples of pigments with a polymeric multi-layered structure which may be mentioned are those sold by 3M under the trade name COLOR GLITTER.

Liquid crystal coloring agents comprise, for example, silicones or cellulose ethers onto which mesomorphous groups are grafted.

Liquid crystal goniochromatic particles which may, for example, be used are those sold by Chenix as well as those sold under the trade name HELICONE® HC by WACKER.

Said agents may also be in the form of dispersed goniochromatic fibers. Said fibers may, for example, be of a size in the range 50 μm to 700 μm, for example about 300 μm.

In particular, it is possible to use interferential fibers with a multi-layered structure. Fibers with a multi-layered polymer structure have in particular been described in European patent documents EP-A-0 921 217 and EP-A-0 686 858 and in U.S. Pat. No. 5,472,798. The multi-layered structure may comprise at least two layers, each layer, independently or not of the other layer(s), being produced from at least one synthesized polymer. The polymers present in the fibers may have a refractive index of 1.30 to 1.82 and preferably 1.35 to 1.75. 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 two layered polyethylene terephthalate/nylon-6 structure are sold under the trade name TEIJIN under the trade name MORPHOTEX.

In a variation, said goniochromatic coloring agent may be associated with at least one diffractive pigment.

The combination of these two materials results in an article with an enhanced color variability, and thus which is capable of allowing an observer to perceive a color change or even color movement under a number of observation and illumination conditions.

The weight ratio of the diffractive pigment relative to the goniochromatic coloring agent is preferably in the range 85/15 to 15/85, more preferably in the range 80/20 to 20/80, still more preferably in the range 60/40 to 40/60, for example of the order of 50/50. Such a ratio is favorable to the production of a sustained rainbow effect and goniochromatic effect.

Optical Whitening Agents

Optical whitening agents are compounds which are well known to the skilled person. Such compounds have been described in “Fluorescent whitening agents, Encyclopedia of Chemical Technology, Kirk-Othmer”, vol 11, p. 227-241, 4^eme edition, 1994, Wiley.

More particularly, they can be defined as compounds which absorb essentially in the UVA region between 300 nm and 390 nm and emit essentially between 400 nm and 525 nm.

Optical whitening agents which may in particular be mentioned include stilbene derivatives, in particular polystyrylstilbenes and triazinstilbenes, coumarin derivatives, in particular hydroxycoumarins and aminocoumarins, oxazole, benzoxazole, imidazole, triazole, pyrazoline derivatives, pyrene derivatives and porphyrin derivatives and mixtures thereof.

Said compounds are readily available commercially. Examples which may be mentioned are as follows:

• • the stilbene derivative of naphtho-triazole sold under the trade name “Tinopal GS”, 4,4′-di-styryl-biphenyl sulfonate di-sodium salt (CTFA name: disodium distyrylbiphenyl disulfonate) sold under the trade name “Tinopal CBS-X”, the cationic derivative of aminocoumarin sold under the trade name “Tinopal SWN CONC.”, sodium 4,4′-bis[(4,6-dianilino-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disulfonate sold under the trade name “Tinopal SOP”, 4,4′-bis-[(4-anilino-6-bis(2-dihydroxyethyl)amino-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disulfonic acid sold under the trade name “Tinopal UNPA-GX”, 4,4′-bis-[anilino-6-morpholine-1,3,5-triazin-2-yl)amino]stilbene sold under the trade name “Tinopal AMS-GX”, 4,4′-bis-[(4-anilino-6-(2-hydroxyethyl)methyl amino-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disodium sulfonate sold under the trade name “Tinopal 5BM-GX”, all from CIBA Specialites Chimiques;

2,5-thiophene di-yl bis(5-ter-butyl-1,3-benzoxazole) sold under the trade name “Uvitex OB” by CIBA;

• • the anionic derivative of di-aminostilbene in dispersion in water, sold under the trade name “Leucophor BSB liquide” by CLARIANT;
  • optical whitening lakes sold under the trade name “COVAZUR” by WACKHERR.

The optical whitening agents which may be used in the present invention may also be in the form of copolymers, for example of acrylates and/or methacrylates, grafted with optical whitening agent groups as described in French patent application FR 99 10942.

They may be used as is or introduced into the film in the form of particles and/or fibers coated with said whitening agents, such as those described below.

In particular, it is possible to use fibers coated with optical whitening agents as sold by LCW under the trade name Fiberlon 54 ZO3, with a length of about 0.4 mm and a weight of 0.5 deniers.

Material with Relief Effect

As described above, this relief effect may or may not be associated with an optical effect. A material of this type is generally present in a quantity sufficient to produce a relief effect which is perceptible to the touch or even to the naked eye. It may also be a rough, grained and/or hammered effect.

Material Producing a Rough Effect

The article of the invention is particularly advantageous as regards binding solid particles or fibers in its film, thus producing an original make-up relief effect. Further, particles with a substantially spherical or ovoid form may produce a soft make-up touch effect.

Advantageously, the solid particles have a substantially spherical form to allow them to be properly distributed during application onto the first layer.

The solid particles used in accordance with the invention may have a mean size of 2.5 μm to 5 mm, preferably 50 μm to 2 mm. The smaller the particles, the better the staying power of the particles. Using particles is also compatible with producing motifs.

The solid particles may be formed from any material satisfying the density properties defined above. As an example, the solid particles may be formed from a material selected from glass, zirconium oxide, tungsten carbide, plastics such as polyurethanes, polyamides, polytetrafluoroethylene, polypropylene, metals such as steel, copper, brass, chromium, wood, marble, onyx, jade, natural nacre, precious stones (diamond, emerald, ruby, sapphire), amethyst, aquamarine. Preferably, glass beads are used, such as those sold under the trade name “SILIBEADS®” by SIGMUND LINDNER; said beads have the further advantage of also producing a glossy and scintillating cosmetic effect.

The solid particles, which may or may not be deformable, may be solid or hollow, colorless or colored, coated or otherwise.

Regarding the fibers used in the invention, they may be fibers of synthetic or natural, mineral or organic origin.

The term “fiber” means an object with a length L and a 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. In particular, the ratio L/D (or form factor) is selected so as to be in the range 3.5 to 2500, preferably in the range 5 to 500, more preferably in the range 5 to 150.

They may be fibers used in the fabrication of textiles, in particular fibers of silk, cotton, wool, linen, cellulose fibers, especially those derived from wood, vegetable or algae, rayon, polyamide (Nylon®), viscose, acetate, in particular rayon acetate, poly-(p-phenylene-terephthalamide) (or aramide) especially Kevlar®, acrylic polymer, especially polymethyl methacrylate or poly 2-hydroxyethyl methacrylate, polyolefin and especially polyethylene or polypropylene, glass, silica, carbon in particular in the form of graphite, polytetrafluoroethylene (such as Teflon®), insoluble collagen, polyesters, polyvinyl or polyvinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate and fibers formed by a mixture of polymers such as those mentioned above, such as polyamide/polyester fibers.

More particularly, the fibers are fibers of polyamide (Nylon®).

In particular, it is possible to use polyamide fibers sold by P Bonte under the trade name “Polyamide 0.9 Dtex 3 mm” having a mean diameter of 6 μm, a titer of about 0.9 dtex and a length of 0.3 mm to 5 mm. It is also possible to use cellulose (or rayon) fibers having a mean diameter of 50 μm and a length of 0.5 mm to 6 mm, such as those sold under the trade name “Natural rayon flock fiber RC1BE-N003-M04” by Claremont Flock. It is also possible to use polyethylene fibers such as those sold under the trade name “Shurt Stuff 13 099F” by Mini Fibers.

Material Producing a Crepe Effect

The flexible article of the invention is also suitable for containing a material which is capable of producing a grained or crepe effect on the article surface.

Said material with a grained effect may be fragments of a polymer film, which may or may not be colored, having two substantially planar faces, with a thickness of 40 μm to 200 μm with the largest dimension being from 0.1 mm to 4 mm, the fragments being insoluble in the medium of the composition intended to form the organic film.

When the composition intended to form the film is applied to the adhesive layer or to a support, the fragments of films are readily distributed in the deposited layer and are disposed in a random manner through its thickness. Cross-linking and/or drying said composition then produces a film having portions which are thicker than the mean thickness of the film, distributed in a random manner on the film surface. The film surface then has a discontinuous relief which is resistant to friction. An original cosmetic relief effect is thus obtained, both to the touch and visually, which adheres well to the made up support and has good staying power.

The colored polymer film fragment may be obtained from radical polymers, in particular 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. Preferably, styrene/acrylic copolymers are used. Such fragments have in particular been described in European patent application EP-A-1 036 554.

Advantageously, the thickness of the film fragment may be from 70 μm to about 130 μm, preferably from about 90 μm to about 110 μm.

Colored film fragments used in accordance with the invention are sold under the trade name MONOCOLOR by QUADRA INDUSTRIES.

Material Producing a Hammered Effect

The inventors have also established that it is possible for the film of the article of the invention to contain a material comprising a pyrogenated silica mixture, a metallic pigment and an organopolysiloxane compound to produce therein a hammered appearance.

Such a mixture has been described in European patent application EP-A-1 040 813.

• • The organopolysiloxane may be selected from polydimethylsiloxanes, polymethylethylsiloxanes, copolymers of dimethylsiloxane and methylvinylsiloxane, copolymers of dimethylsiloxane and up to 50 mole percent of phenylmethylsiloxane.

The organopolysiloxanes may in particular be those sold in solution in xylene under the trade name “Dow Corning 61 additive” by Dow Corning, or those sold under the trade name “Rhodorsil SIL AID 16” by Rhone-Poulenc.

The organopolysiloxane may be present in the organic film in an effective amount so as to produce the hammered effect (formation of a crater) and in particular in an amount of 0.01% to 10% by weight relative to the total weight of said film, preferably 0.1% to 5% by weight.

• • The metallic pigments which may be used are aluminum powders sold under the trade names “STAPA Non leafing grade”, “STAPA Metallic”, “METALURE L55350” by ECKART, “Aluminum Super 800” by WOLSTENHOLME International, “SILVET and 1630” by SILBERLINE; bronze powders sold under the trade names “STAPA Golden Bronze” by ECKART, “Pastel Standard” by WOLSTENHOLME International.

Preferably, the organopolysiloxane and the metallic pigment may be present in the organic film in an organopolysiloxane/metallic pigment weight ratio of 0.1/100 to 5/100, preferably 0.5/100 to 1.5/100. In this weight ratio, a film with a good hammered effect is obtained.

• • The pyrogenized silica present in the organic film may be in the form of hydrophilic or hydrophobic pyrogenized silica film. Preferably, hydrophilic pyrogenized silica is used.

The pyrogenized silicas may be obtained by high temperature hydrolysis of a volatile silicon compound in a hydrogen-oxygen flame, producing a finely divided silica. Such hydrophilic silicas are, for example, sold under the trade names “AEROSIL 130®”, “AEROSIL 200®”, “AEROSIL 255®”, “AEROSIL 300®”, “AEROSIL 380®” by 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 CABOT.

Material with an Olfactory Effect

Advantageously, the articles of the invention may also be provided with olfactory properties, especially by incorporating into their organic film at least one odorifying material or a fragrancing substance.

The fragrancing substance may be selected from any odorifying substance which is well known to the skilled person, in particular from essential oils and/or essences.

Said material olfactory may, if appropriate, be introduced via a solvent-plasticizer.

The term “solvent-plasticizer” means a compound which at least partially dissolves the olfactory material and which is capable of evaporating off slowly.

The solvent-plasticizer may be selected from glycols such as dipropylene glycol, ethyldiglycol, n-propylglycol, n-butylglycol, methyldiglycol, n-butyldiglycol, alcohols such as cyclohexanol, 2-ethyl 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, the acetate of propylene glycol methyl ether, glycol ethers such as dipropylene glycol-methyl ether or -butyl ether, used alone or as a mixture.

ARTICLE IN ACCORDANCE WITH THE INVENTION

The article of the invention may be characterized by a high dry extract. In the dry state, it may have a quantity of dry material of more than 80%, in particular more than 85%, in particular more 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 article weight.

However, in a further advantageous implementation, the article of the invention may advantageously be in the partially dry form. In this particular case, the article is advantageously packaged in a reservoir such as a pouch, for example, which may or may not be flexible, which is sufficiently airtight to preserve this partially dry aspect. Only when used, and as a result when it is brought into contact with air, will the article dry slowly to acquire the dry matter content defined above.

In one substance in accordance with the invention, the article of 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 of more than 60%, especially more than 65% by weight relative to the total weight.

Such an article, when removed from the packaging of the substance of the invention, becomes dry as defined above within 24 hours following exposure to ambient air.

Preferably, the quantity of dry matter, usually termed the “dry extract” of the films of the invention, is measured by heating a sample using infrared radiation with a wavelength of 2 μm to 3.5 μm. Substances contained in said films which have a high vapor pressure evaporate off under the effect of this radiation. Measuring the loss of mass of the sample allows the “dry extract” of the film to be determined. Said measurements are made using a commercial LP16 infrared dessicator from Mettler. That technique is fully described in the documentation furnished by Mettler accompanying the apparatus.

The following measurement protocol is followed.

About 10 g [grams] of sample is placed in a metal cup. After introduction into a dessicator, it is subjected to a temperature of 120° C. for one hour. The moist mass of the sample, corresponding to the initial mass and the dry mass of the sample, corresponding to the mass after exposure to radiation, are measured using a precision balance.

The dry matter content is calculated as follows:

Dry extract=100×(dry mass/moist mass).

Water Take-Up

The article of the invention is characterized in the dry state by a water take-up at 25° C. of 20% or less, in particular 16% or less, and more particularly less than 10%.

In the present application, the term “water take-up of a film” denotes the percentage of water absorbed by the article after immersion in water for 60 minutes at 25° C. (ambient temperature). The water take-up is measured using pieces of about 1 cm² cut from the dry article and weighed (measurement of mass M1) then immersed in water for 60 minutes; after immersion, the piece of the article is wiped to eliminate excess surface water then weighed (measuring mass M2). The difference, M2−M1, corresponds to the quantity of water absorbed by the article.

The water take-up is equal to [(M2−M1)/M1]×100 and is expressed as the percentage by weight relative to the weight of the article.

Storage Modulus E′

Further, the article of the invention is advantageously a film having a storage modulus E′ of 1 MPa [megapascals] or more, in particular 1 MPa to 5000 MPa, more particularly 5 MPa or more, in particular 5 to 1000 MPa and still more particularly 10 MPa or more, for example 10 MPa to 500 MPa at a temperature of 30° C. and a frequency of 0.1 Hz [Hertz].

The storage modulus is measured by DMTA (dynamic and mechanical temperature analysis).

The viscoelastic tests are carried out with a DMTA apparatus from Polymer TA Instruments (DMA2980 model) on a sample of the article. Specimens are cut out (for example using a punch). They have a typical thickness of about 150 μm, a width of 5 mm to 10 mm and a useful length of about 10 mm to 15 mm.

The measurements are carried out at a constant temperature of 30° C.

The sample is placed under tension and subjected to small deformations (for example a sinusoidal displacement of ±8 μm) during a frequency scan, the frequency being from 0.1 Hz to 20 Hz. Thus, the working region is linear, with small deformations.

Said measurements allow the complex modulus E*=E′+iE″ of the test composition film to be determined, E′ being the storage modulus and E″ the “lossy” modulus.

Deformation and/or Energy at Break

Advantageously, in the dry state the articles of the invention have a deformation at break ∈_r of 5% or more, in particular 5% to 500%, more preferably 15% or more, especially 15% to 400%, and/or an energy at break per unit volume W_r of 2 J/cm³ [joules/cubic centimeter] or more, in particular 0.2 J/cm³ to 100 J/cm³, preferably more than 1 J/cm³, in particular 1 J/cm³ to 50 J/cm³.

The deformation at break and the energy at break per unit volume are determined by tensile tests carried out on an article about 200 μm thick.

To carry out these tests, the article is cut into dumb-bell shaped test specimens with a useful length of 33±1 mm and a useful width of 6 mm. The section (S) of the specimen is thus defined as: S=width×thickness (cm²); this section is used for the stress calculation.

The tests are carried out, for example, using a commercial tensile apparatus sold under the trade name Lloyd® LR5K. The measurements are carried out at ambient temperature (20° C.).

The specimens are stretched at a displacement rate of 33 mm/min, corresponding to a 100% extension per minute.

Thus, a displacement rate is imposed and the extension ΔL of the specimen and the force F necessary to impose said extension are measured simultaneously. These data ΔL and F are used to determine the stress σ and deformation ∈ parameters.

A stress curve of σ=(F/S) is obtained as a function of the deformation ∈=(ΔL/L₀)×100, the test being carried out until the sample breaks, L₀ being the initial length of the sample.

The deformation at break ∈_r is the maximum deformation of the sample before the break point (as a %).

The energy at break per unit volume, W_r in J/cm², is defined as the area beneath the stress/deformation curve, i.e.:

$W_r={\int }_0^{{\varepsilon }_r}\sigma ·\varepsilon ·\varepsilon$

The organic film of the article of the invention may be obtained by cross-linking a cross-linkable composition and/or by evaporating off the organic or aqueous solvent phase of a solution or dispersion of at least one film-forming polymer.

Cross-Linked Polymer

Within the context of the present invention, a “cross-linked” film may be completely or partially cross-linked. In the case of partial cross-linking, this is clearly sufficient to form the expected film.

Clearly, the compounds used are selected, in particular depending on the nature of the functions they respectively possess, to be capable of interacting under the cross-linking reaction conditions under consideration.

Said cross-linking can thus be achieved by a thermal, photochemical and/or chemical route, in the presence or absence of a catalyst. The skilled person is capable of carrying out said cross-linking.

In a first variation, the cross-linking reaction is a polyaddition or polycondensation reaction carried out in the presence or absence of a catalyst.

In this first variation, the organic film may in particular derive from cross-linking 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 (Y), reactive towards the X functions.

Advantageously, the reactive system has a mean functionality (total number of X and Y functions/total number of molecules of compounds (A) and (B)) of more than 2 to produce a three-dimensional network.

More particularly, to obtain a satisfactory cross-linking effect, the mean functionality of the reactive system may be at least 2.2 and more particularly may be from 2.5 to 100.

Compounds (A) and (B) may be organic in origin and in particular of the monomer, oligomer, polymer and/or copolymer type, or they may be inorganic in nature, for example, like a mineral particle, in which case they have the two required functions (X) or (Y) on the surface.

Reactive functions X and Y are selected from “reactive” functions and functions comprising at least one labile hydrogen.

More precisely, the reactive functions are selected from isocyanates, epoxy compounds and ethylenically unsaturated double bonds and the functions with labile hydrogen(s) are of the carboxylic, alcohol (in particular phenol), primary or secondary amine, amide, aminoalcohol and/or thiol type.

In this variation, compounds (A) and (B) respectively have at least two reactive epoxy and/or isocyanate type functions and at least two functions with (a) labile hydrogen(s), in particular of the amine or aminoalcohol type, and may especially be selected from the compounds mentioned above.

As an example, X may be an epoxy and/or isocyanate function and Y may be selected from a carboxylic acid function and/or an anhydride function and/or an amine function and/or a thiol function and/or a hydroxyl function, in particular phenolic.

In this variation of the invention, cross-linking may be carried out by bringing compounds (A) and/or (B) having functions (X) and/or (Y) functions into contact in a blocked form which can be unblocked in advance or under the reaction conditions used for cross-linking. This alternative is well known to the skilled person and will not be described in detail.

Compounds with Isocyanate Functions

Compounds comprising at least two free isocyanate functions are known in the art. They may be polyisocyanates, including diisocyanates or triisocyanates, which may have a molecular mass of less than 500000, or even less than 10000. Said polyisocyanates are generally obtained by polyaddition, polycondensation and/or grafting, carrying at least two isocyanate functions, either at the chain extremities or on the lateral groups.

The poly isocyanates may be linear, branched, aliphatic, cycloaliphatic or aromatic.

Particular polyisocyanates which may be mentioned are DESMODUR® N from BAYER and TOLONATE® HDB-LV from RHODIA.

Compounds with Epoxy Functions

Compounds comprising at least two epoxy functions are also known in the art. They may have any chemical nature. They may be diepoxy compounds or polyepoxy compounds with low masses (5000 or less), or oligomers or polymers of any chemical nature, obtained by polyaddition, polycondensation and/or grafting, carrying at least two free epoxy functions either at the chain extremities or on the lateral groups.

Polymers with an epoxy function are sold under the trade names CYRACURE® UVR-6110, CYRACURE® UVR-6105, CYRACURE® ERL-4221E, CYRACURE® ERL-4206, CYRACURE® UVR 6128, CYRACURE® UVR 6216 by UNION CARBIDE, DER® 439 by DOW CHEMICAL, EPIKATES® 828, 1001, 1004, 1007 from SHELL, ARALDITE® ECN1299 from CIBA-GEIGY, EPOXYNOVOLACS® from DOW CHEMICAL.

Compounds with Ethylenically Unsaturated Double Bonds

Compounds carrying ethylenically unsaturated double bonds may have any chemical nature. In particular, they may be selected from:

a) polyesters with lateral and/or terminal (meth)acrylate groups:

Said polyesters are, for example, sold by UCB under the EBECRYL® (EBECRYL® 450: molar mass 1600, a mean of 6 acrylate functions per molecule, EBECRYL® 652: molar mass 1500, a mean of 6 acrylate functions per molecule, EBECRYL® 800: molar mass 780, a mean of 4 acrylate functions per molecule, EBECRYL® 810: molar mass 1000, a mean of 4 acrylate functions per molecule, EBECRYL® 50 000: molar mass 1500, a mean of 6 acrylate functions per molecule).

b) polyurethanes and/or polyureas with (meth)acrylate groups obtained by polycondensation:

• • said polyurethanes/polyureas with acrylate groups are, for example, sold under the trade name SR 368 (tris(2-hydroxyethyl)isocyanurate-triacrylate) or CRAYNOR® 435 by CRAY VALLEY, or under the trade name EBECRYL® by 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® 220: molar mass 1000, 6 acrylate functions per molecule, EBECRYL® 2220: molar mass 1200, 6 acrylate functions per molecule, EBECRYL® 1290: molar mass 1000, 6 acrylate functions per molecule, EBECRYL® 800: molar mass 800, 6 acrylate functions per molecule).

Hydrosoluble diacrylate aliphatic polyurethanes sold under the trade names EBECRYL® 2000, EBECRYL® 2001 and EBECRYL® 2002 can also be mentioned, along with diacrylate polyurethanes in aqueous dispersion sold by UCB under the trade names IRR® 390, IRR® 400, IRR® 422 IRR® 424.

c) Polyethers with (meth)acrylate groups obtained by esterification, by (meth)acrylic acid, of the terminal hydroxyl groups of homopolymers or copolymers of C₁-C₄ alkylene glycols, such as polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide preferably having a mass average molecular mass of less than 10000, and polyethoxylated or polypropoxylated trimethylolpropane.

Di(meth)acrylate polyoxyethylenes with a suitable molar mass are, for example, sold under the trade names SR 259, SR 344, SR 610, SR 210, SR 603 and SR 252 by CRAY VALLEY or under the trade name EBECRYL® 11 by UCB. Polyethoxylated trimethylolpropane triacrylates are sold, for example, under the trade names SR 454, SR 498, SR 502, SR 9035, SR 415 by CRAY VALLEY or under the trade name EBECRYL® 160 by UCB. Polypropoxylated trimethylolpropane triacrylates are, for example, sold under the trade names SR 492 and SR 501 by CRAY VALLEY.

d) Epoxyacrylates obtained by reaction between:

Such polymers are, for example, sold under the trade names SR 349, SR 601, CD 541, SR 602, SR 9036, SR 348, CD 540, SR 480, CD 9038 by CRAY VALLEY, under the trade names EBECRYL® 600 and EBECRYL® 609, EBECRYL® 150, EBECRYL® 860, EBECRYL® 3702 by UCB and under the trade names PHOTOMER® 3005 and PHOTOMER® 3082 by HENKEL.

e) C₁-C₅₀ alkyl poly(meth)acrylates comprising at least two ethylenically unsaturated double bonds carried by the lateral and/or terminal hydrocarbon chains.

Such copolymers are, for example, sold under the trade names IRR® 375, OTA® 480 and EBECRYL®2047 by UCB.

f) Polyorganosiloxanes with (meth)acrylate or (meth)acrylamide groups.

α,ω-diacrylate polydimethylsiloxanes are available from SHIN-ETSU under the trade names X-22-164 B and X-22-164C.

g) Hyper-branched dendrimers and polymers carrying (meth)acrylate or (meth)acrylamide terminal groups respectively obtained by esterification or amidification of dendrimers and hyper-branched polymers with hydroxyl or amino functions by (meth)acrylic acid.

Dendrimers (from the Greek dendron=tree) are “arborescent” polymer molecules, i.e. highly branched, invented by D A Tomalia and his team at the beginning of the 1990s (Donald A Tomalia et al, Angewandte Chemie, Int. Engl Ed, vol 29, n^o 2, pages 138-175). They are structures constructed around a generally polyvalent central motif. Linked around this central motif in a predetermined structure are branched chain extension motifs giving rise to mono-dispersed symmetrical macromolecules with a well defined chemical or stereochemical structure. Polyamidoamine type dendrimers are, for example, sold under the trade name STARBUST® by DENDRITECH.

Hyper-branched polymers are polycondensates, generally of the polyester, polyamide or polyethyleneamine type, obtained from multi-functional monomers which have an arborescent structure similar to that of dendrimers but much less regular (see, for example, WO-A-93/17060 and WO-A-96/12754).

PERSTORP sells hyper-branched polyesters under the trade name BOLTORN®. Hyper-branched polyethylene amines sold under the trade name COMBURST® can be obtained from DENDRITECH. Hyper-branched poly(esteramide)s with hydroxyl extremities are sold by DSM under the trade name HYBRANE®.

Said hyper-branched dendrimers and polymers esterified or amidified by acrylic acid and/or methacrylic acid are distinguished from polymers described in points a) to h) above by the very large number of ethylenically unsaturated double bonds present.

This high functionality, usually more than 5, renders them particularly useful, allowing them to act as a “cross-linking node”, i.e. a multiple cross-linking site.

In a preferred implementation of the invention, dendritic and hyper-branched polymers will as a result be used in association with one or more of the polymers and/or oligomers a) to h) above.

Compounds Carrying at Least Two Functions with Labile Hydrogen(s)

Compounds carrying at least two functions with a labile hydrogen which can be used in the present invention are also known. They may be organic compounds with a low molecular mass or oligomers or synthetic polymers obtained by polyaddition, polycondensation and/or grafting, or natural chemically modified polymers.

In accordance with the present invention, the functions with a labile hydrogen are preferably selected from primary amine (—NH₂), secondary amine (>NH), hydroxyl (—OH), carboxylic acid (—COOH) or thiol (—SH) functions.

• • when the function with a labile function is a hydroxyl function, aliphatic diols and polyols may be mentioned as categories of compounds;
  • when the function with a labile hydrogen is an amine function (NH₂), it may be a diamine, a polyamine, an aminoalcohol, an oligomer or a polymer with amine groups.

Particular examples of compounds carrying functions with labile hydrogen functions are: C₁-C₄ alkyleneglycols, glycerol, trimethylolpropane, pentaerythritol, poly C₁-C₄ alkylene glycols such as polyethylene glycol or polypropylene glycol or copolymers thereof, the condensation product of propylene glycol and trimethylolpropane, castor oil, phytantriol, sugars and carbohydrates such as saccharose or cellulose, ethylenediamine, 1,3-diaminopropane, lysine, 2-amino-2-methyl-propan-1ol, poly(alkyleneoxy)diamines such as JEFFAMINE® products sold by TEXACO, nitrocellulose, cellulose esters, especially those with a degree of substitution of less than 3 such as cellulose acetobutyrate or cellulose acetopropionate, cellulose ethers such as hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose or ethylcellulose, polyester resins, silicones, perfluoropolyethers, alkyds and polyketones with hydroxylated ends, polyvinyl alcohol and copolymers based on vinyl alcohol, allyl alcohol copolymers, copolymers based on C₂-C₁₀ hydroxyalkyl(meth)acrylate such as 2-hydroxyethyl or 2-hydroxypropyl(meth)acrylate sold under the trade name JONCRYL® SCX 910 by JOHNSON POLYMER or under the trade name CRODOPLAST® AC 5725 by CRODA, copolymers based on vinylamine or allylamine, silicones and perfluoroethers with primary or secondary amine extremities, hyper-branched dendrimers or polymers with hydroxyl or primary amine extremities such as hyper-branched polyesters with hydroxyl extremities sold by PERSTORP under the trade names BOLTORN® H40 TMP CORE and HBP POLYOL® 3G (described in International patent applications WO 93/17060 and WO 96/12754), or dendrimers of the polyamido-amine type with primary amine extremities described in the article by Tomalia, Angewandte Chemie, Int. Engl. Ed., vol. 29, n^o 2, pages 138-175.

In a second variation of the invention, cross-linking is carried out photochemically and employs at least two types of compounds, (A) and (B) respectively having at least one unsaturated double bond in the presence of a photoinitiator.

In this variation, A and B are selected so as to form a reactive system the mean valency of which is more than 2. The “valency” of a compound is the number of covalent bonds it may establish with the compounds with which it is associated. The mean valency is defined as being equal to the ratio of the sum of the valencies of all of compounds A and B divided by the total number of compounds A and B.

$V_m=\frac{\sum \mathrm{nivi}}{\sum \mathrm{ni}}$

In this variation of the invention, compounds A or B may be a compound comprising a function of the unsaturated double bond type and in particular as defined above, and/or a monomer with an ethylenically unsaturated bond.

One particular group of advantageous photoinitiators for use in the invention is that of copolymerizable photoinitiators. These are molecules comprising both a photoinitiator group capable of photoinduced radical scission and at least one ethylenically unsaturated double bond.

To obtain properties with satisfactory behavior, a total quantity of photoinitiator(s) of at least 0.1% by weight is generally used, at most 10% by weight, preferably in the range 0.2% to 5% by weight, compared with the total weight of compounds comprising ethylenically unsaturated double bonds.

In this variation, cross-linking may be carried out in the presence of a co-film-forming agent such as nitrocellulose or cellulose esters.

Film-Forming Polymer Particles

In a second variation of the invention, the article comprises at least one polymeric film obtained by evaporating off the organic or aqueous solvent phase from a solution or dispersion of at least one film-forming polymer.

The term “film-forming polymer” designates a polymer which can by itself form, or form in the presence of an auxiliary film-forming agent, an isolatable film, in particular a continuous film on a support, especially on keratinous substances.

To prepare a polymeric film in accordance with the invention, a single film-forming polymer or a mixture of film-forming polymers may be used. Said film-forming polymer may be selected from the group constituted by radical polymers, polycondensates and polymers of natural origin.

Film-Forming Polymers which are Soluble or Dispersible in an Organic Solvent

In a first variation of the invention, said polymeric film derives from evaporation of the organic solvent phase of a solution or dispersion of at least one film-forming polymer. In this implementation, the organic film-forming polymer is at least one polymer selected from the group comprising: film-forming polymers which are soluble or dispersible in at least one class of organic solvent such as ketones, alcohols, glycols or propylene glycol ethers, short chain esters, alkanes and their aqueous or non aqueous mixtures.

The corresponding polymers may have any chemical nature. In particular, they may result either from homo- or co-polymerization of unsaturated monomers, or from polycondensation, or from modification of natural polymers, in particular polysaccharides. The mass average molecular masses (Mp) of these polymers may be from 3000 to 1000000, in particular 5000 to 800000, in particular 10000 to 500000.

Particularly suitable polymers which are soluble or dispersible in organic solvents include the following:

a) (meth)acrylic acid ester and/or amide homo- and co-polymers, in particular polymers resulting from the polymerization or copolymerization of methyl, ethyl, propyl, butyl, isobutyl, tertiobutyl, pentyl, hexyl, cyclohexyl, 2-ethylhexyl, heptyl, octyl, isobornyl, norbornyl, adamantyl acrylates and/or methacrylates or the corresponding (meth)acrylamides. Said polymers preferably comprise 0 to 20% of a polar co-monomer such as (meth)acrylic acid, (meth)acrylamide, hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate and (meth)acrylonitrile. They may also result from copolymerization with styrene or a substituted styrene.

b) Vinyl ester or amide homo- and copolymers, in particular homo- and co polymers resulting from the polymerization of vinyl acetate, vinyl propionate, vinyl versatate, with or without the presence of a polar co-monomer such as crotonic acid, allyloxyacetic acid, maleic anhydride or acid, itaconic anhydride or acid, vinyl acetamide or vinyl formamide. Similarly, they may result from copolymerizing at least one of the monomers mentioned above with styrene or with a substituted styrene.

c) Celluloses and cellulose derivatives, such as nitrocelluloses and/or cellulose esters such as cellulose acetates, cellulose propionates, cellulose butyrates, cellulose acetopropionates or cellulose acetobutyrates.

d) Polycondensates which are soluble or dispersible in said solvents. They are generally used as a principal film-forming agent or as a co-film-forming agent with one of the polymer classes mentioned above (a to c), in particular if they have a low molecular weight (Mp<20000). They may be selected from the following polymers or copolymers: polyurethanes, acrylic polyurethanes, polyureas, polyurea polyurethanes, les polyester polyurethanes, polyether polyurethanes, polyesters, polyester-amides, fatty chain polyesters, epoxy compounds, and arylsulfonamide condensates, in particular tosylamide/formaldehydes.

Of these polycondensates, in particular if they are used as a film-forming agent or a co film-forming agent with one or more nitrocelluloses and/or a cellulose ester (class c), the following may in particular be mentioned:

• • polyesters, in particular fatty chain polyesters and more particularly copolymers with the CTFA name: “copolymer of glycidyl phthalic/glycerol/decanoate anhydride” and “adipic acid/neopentylglycol/trimellitic anhydride copolymer”;
  • alkyds;
  • tosyl amide/formaldehyde condensates;
  • polyurethanes and polyurea-urethanes;
  • acrylic resins;
  • silicone resins (non volatile or partially volatile).

Aqueous Dispersions of Polymer Particles or Film-Forming Latexes

In a second variation of the invention, said polymeric film derives from evaporating off the aqueous phase of an aqueous dispersion of film-forming polymer particles. In this case, the film-forming polymer may be selected from aqueous dispersions of polymer particles or film-forming latexes, and in this case the composition of the invention comprises at least one aqueous phase.

The aqueous dispersion comprising one or more film-forming polymers may be prepared by the skilled person using general knowledge, in particular by emulsion polymerization or by dispersing the formed polymer.

Film-forming polymers of this type which may be used in the composition of the present invention which may be mentioned are synthetic polymers of the polycondensate or radical type, polymers of natural origin, and mixtures thereof.

In particular, it is possible to use, in the form of a latex, polymers (homo and copolymers) which are mentioned above as polymers which are soluble or dispersible in an organic solvent medium, more particularly polymers of classes a, b and c.

Polycondensates which can thus be mentioned include anionic, cationic, non ionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea polyurethanes and mixtures thereof.

It is also possible to mention polyesters, polyester amides, fatty chain polyesters, polyamides and epoxy ester resins.

The polyesters may be obtained in known manner by polycondensation of aliphatic or aromatic dibasic acids with aliphatic or aromatic diols or polyols. Aliphatic dibasic acids which may be used are succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or sebacic acid. Aromatic dibasic acids which may be used are terephthalic acid or isophthalic acid, or a derivative such as phthalic anhydride. Aliphatic diols which may be used are ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, dimethanol cyclohexane and 4,41-(1-methylpropylidene)bisphenol. Polyols which may be used are glycerol, pentaerythritol, sorbitol and trimethylol propane.

Radical type polymers may in particular be acrylic and/or vinylic polymers or copolymers. Preferably, anionic radical polymers are used. Monomers carrying an anionic group which may be used during radical polymerization which may be mentioned are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid.

The acrylic polymers may result from copolymerization of monomers selected from esters and/or amides of acrylic acid or methacrylic acid. Examples of ester type monomers which may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate. Examples of amide type monomers which may be mentioned are N-t-butyl acrylamide and N-t-octyl acrylamide.

The vinyl polymers may result from the homopolymerization or copolymerization of monomers selected from vinyl esters, styrene and butadiene. Examples of vinyl esters which may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.

It is also possible to use acrylic/silicone copolymers or nitrocellulose/acrylic copolymers.

It is also possible to mention polymers resulting from radical polymerization of one or more radical monomers inside and/or partially on the surface of pre-existing particles of at least one polymer selected from the group constituted by polyurethanes, polyureas, polyesters, polyester amides and/or alkyds. Said polymers are generally termed hybrid polymers.

The dispersion may also comprise an associative polyurethane type polymer or a natural gum such as xanthan gum.

Polymers in aqueous dispersion which may be mentioned are dispersions of acrylic polymers sold under the trade names NEOCRYL XK-90®, NEOCRYL A-1070®, NEOCRYL A-1090®, NEOCRYL BT-62®, NEOCRYL A-1079®, NEOCRYL A-523® by ZENECA and DOW LATEX 432®, by DOW CHEMICAL. It is also possible to use aqueous dispersion of polyurethane, in particular polyester-polyurethanes sold under the trade names “AVALURE UR-405®”, “AVALURE UR-410®”, “AVALURE UR-425®”, “SANCURE 2060®” by GOODRICH and polyether-polyurethanes sold under the trade names “SANCURE 878®” by GOODRICH, “NEOREZ R-970®” by AVECIA.

The group of film-forming polymers mentioned above may be associated with at least one auxiliary film-forming and/or coalescing agent.

The auxiliary film-forming agent may be selected from any of the compounds known to the skilled person as being susceptible of fulfilling the desired function, and in particular may be selected from plasticizers and coalescence agents for the film-forming polymer.

In particular, it is possible to use, alone or as a mixture, the usual plasticizers or coalescence agents such as:

• • glycols and their derivatives such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether;
  • glycol esters;
  • propylene glycol derivatives, in particular propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether and diethylene glycol methyl ether, propylene glycol butyl ether;
  • esters, in particular of carboxylic acids such as citrates, in particular triethyl citrate, tributyl citrate, triethyl acetyl citrate, tributyl acetyl citrate, 2-triethylhexyl acetyl citrate; phthalates, in particular diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dipentyl phthalate, dimethoxyethyl phthalate; phosphates, in particular tricresyl phosphate, tributyl phosphate, triphenyl phosphate, tributoxyethyl phosphate; tartrates, in particular dibutyl tartrate; adipates; carbonates; sebacates; benzyl benzoate, butyl acetylricinoleate, glyceryl acetylricinoleate, butyl glycolate, camphor, glycerol triacetate, N-ethyl-o,p-toluenesulfonamide;
  • oxyethylenated derivatives such as oxyethylenated oils, in particular vegetable oils such as castor oil; silicone oils;
  • mixtures thereof.

The type and quantity of plasticizing and/or coalescence agent may be selected by the skilled person on the basis of general knowledge.

As an example, the amount of plasticizing and/or coalescence agent may be from 0.01% to 10%, in particular from 1% to 3% by weight relative to the total composition weight.

Adhesive Material

The article of the invention has an adhesive outer face. Said adhesive face is generally obtained by dint of the presence of at least one layer of at least one adhesive material.

The term “material” as used in the context of the present invention means a polymer or a polymeric system which may comprise one or more polymers of different natures. Said adhesive material may be in the form of a solution of polymer or a dispersion of polymer particles in a solvent. Said adhesive material may also contain a plasticizer as defined above. Said adhesive material may have a certain adhesive power as 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 the material for a given frequency which is conventionally denoted G″.

These magnitudes have been defined in the “Handbook of Pressure Sensitive Adhesive Technology” 3^rd edition, D. Satas, chap. 9, p. 155 a 157.

Adhesive materials which can be used in the context of the present invention have viscoelastic properties which are measured at a reference temperature of 35° C. and in a certain frequency range.

In the case of adhesive materials in the form of a solution or dispersion of polymer in a volatile solvent (such as water, a short chain ester, a short chain alcohol, acetone, etc), the viscoelastic properties of the material are measured under conditions under which it has a volatile solvent content of less than 30%, in particular a volatile solvent content of less than 20%.

In particular, the elastic modulus of the material is measured at three different frequencies:

• • at low frequency, i.e. 2×10⁻² Hz;
  • at an intermediate frequency, i.e. 0.2 Hz;
  • at high frequency, i.e. at 2 Hz;
  • and the viscous modulus at the frequency of 0.2 Hz.

These measurements allow the change of adhesive power of the adhesive material over time to be measured.

These viscoelastic properties are measured during dynamic tests under low amplitude sinusoidal stresses (small deformations) carried out at 35° C. over a frequency range of 2×10⁻² to 20 Hz using a “Haake RS50®” type rheometer under tension/shear stress, for example in cone/plane geometry (for example with a cone angle of 1°).

Advantageously, said adhesive material satisfies the following conditions:

G′(2 Hz,35° C.)≧10³ Pa; and

G′(35° C.)≦10⁸ Pa, in particular G′(35° C.)≦10⁷ Pa;

G′(2×10⁻² Hz,35° C.)≦3·10⁵ Pa;

in which:

• • G′ (2 Hz, 35° C.) is the elastic shear modulus of said adhesive material, measured at a 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 in the range 2×10⁻² to 2 Hz;
  • G′(2×10⁻² Hz, 35° C.) is the elastic shear modulus of said adhesive material, measured at a frequency of 2×10⁻² Hz and at a temperature of 35° C.

In a particular form of the invention, the adhesive material also satisfies the following condition:

G″/G′(0.2 Hz,35° C.)≧0.35.

in which:

• • G″ (0.2 Hz, 35° C.) is the viscous shear modulus of said adhesive material, measured at a frequency of 0.2 Hz and at a temperature of 35° C.;
  • G′ (0.2 Hz, 35° C.) is the elastic shear modulus of said adhesive material, measured at a frequency of 0.2 Hz and at a temperature of 35° C.

In a particular form of the invention, we have:

G′(2 Hz,35° C.)≧5×10³ Pa, and in particular, G′(2 Hz,35° C.)≧10⁴ Pa.

In a further particular form of the invention, we have:

G′(2×10⁻² Hz,35° C.)≦5×10⁴ Pa.

In particular, the adhesive materials of the invention satisfy the following four conditions:

G′(2 Hz,35° C.)≧10⁴ Pa; and

G′(35° C.)≦10⁸ Pa, in particular G′(35° C.)≦10⁷ Pa;

G′(2×10⁻² Hz,35° C.)≦5×10⁴ Pa; and

G″/G′(0.2 Hz,35° C.)≧0.35.

In general, the adhesive is such that said article cannot be removed by peeling when it is applied to the surface of a synthetic or natural nail after leaving for at least 24 hours.

More particularly, the adhesive materials of the invention may be selected 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 of the invention are polymers selected from block or random copolymers comprising at least one monomer or an association of monomers, the resulting polymer having a low glass transition temperature at ambient temperature (25° C.), said monomers or associations of polymers possibly being selected from butadiene, ethylene, propylene, isoprene, isbutylene, a silicone, and mixtures thereof. Examples of such materials are styrene-butadiene-styrene, styrene-(ethylene-butylene)-styrene, styrene-isoprene-styrene type block copolymers such as those sold under the trade name “Kraton®” by SHELL CHEMICAL Co. or “Vector®” from EXXON.

The adhesive materials of the invention are in particular adhesive polymers selected from:

• • polyurethanes,
  • acrylic polymers,
  • silicones,
  • butyl gums, in particular polyisobutylenes,
  • ethylene-vinyl acetate polymers,
  • polyamides, optionally modified by fatty chains,
  • natural gums,
  • and mixtures thereof.

In particular, they may be adhesive copolymers deriving from the copolymerization of vinyl monomers with polymeric entities such as those described in U.S. Pat. No. 6,136,296, for example. The invention also encompasses the adhesive copolymers described in U.S. Pat. No. 5,929,173 having a polymeric skeleton, with a Tg of 0° C. to 45° C., grafted by chains deriving from acrylic and/or methacrylic monomers and, in contrast, having a Tg of 50° C. to 200° C.

The adhesive materials are, for example, selected from polyisobutylenes having a relative molar mass Mv of 10000 or more and 150000 or less. In particular, said relative molar mass is 18000 or more and 150000 or less.

Commercially available products which are of particular service to the present invention which may be mentioned are polyisobutylenes with a relative molar mass Mv of 40000, 55000 and 85000 sold respectively under the trade names “Oppanol B 10®”, “Oppanol B 12®” and “Oppanol B 15®” by BASF, and mixtures thereof.

Advantageously, the adhesive material and the film are compatible because of their chemical nature and composition. In one particular implementation, the solvent for the adhesive can result in an increase in the mass of the film in contact therewith, in particular by at least 10% by weight relative to the initial weight of the film. In other words, this increase results in the film increasing in mass.

The adhesive material in the article of the invention is generally in the form of a layer with a thickness of 1 μm to 100 μm, in particular 1 μm to 50 μm, preferably 1 μm to 25 μm.

Other Additives

The organic film of the article may also comprise at least one coloring material, which may be organic or inorganic, in particular of the pigment or nacre type conventionally used in cosmetic compositions.

The term “pigments” means white or colored particles, mineral or organic, insoluble in an aqueous solution, intended to color and/or opacify the resulting film.

The pigments may be present in an amount of 0.01% to 15% by weight, in particular 0.01% to 10% by weight, more particularly 0.02% to 5% by weight, relative to the total article weight. Mineral pigments which are suitable in the context of the invention which may be mentioned are oxides of titanium, zirconium or cerium and oxides of zinc, iron or chromium, ferric blue, manganese violet, ultramarine blue and chromium hydrate.

It may also be a pigment with a structure which may, for example, be of the sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is, for example, sold under the reference COVERLEAF NS or JS by CHEMICALS AND CATALYSTS and has a contrast ratio of close to 30.

The coloring material may also comprise a pigment having a structure which may, for example, be of the silica microsphere type containing iron oxide. An example of a pigment having that structure is sold by MIYOSHI with reference number PC BALL PC-LL-100 P, said pigment being constituted by silica microspheres containing yellow iron oxide.

Organic pigments which may be used in the context of the invention which may be mentioned are carbon black, D&C type pigments, lakes based on cochineal carmine, barium, strontium, calcium, aluminum or the diketo pyrrolopyrroles (DPP) described in EP-A-0 542 669, EP-A-0 787 730, EP-A-0 787 731 and WO-A-96/08537.

The term “nacres” means colored particles of any form, iridescent or otherwise, produced in the shells of certain mollusks or synthesized, the color effect in which is produced by optical interference.

The nacres may be selected from nacreous pigments such as mica titanium covered with chromium oxide, mica covered with bismuth oxychloride, mica titanium covered with chromium oxide, mica titanium covered with an organic colorant and nacreous pigments based on bismuth oxychloride. It may also concern mica particles on the surface of which at least two successive layers of metallic oxides and/or organic coloring materials is superposed.

Examples of nacres which may be mentioned are natural mica covered with titanium oxide, iron oxide, natural pigment and bismuth oxychloride.

Commercially available nacres which may be mentioned are TIMICA, FLAMENCO and DUOCHROME (mica based) sold by ENGELHARD, TIMIRON nacres sold by MERCK, PRESTIGE mica based nacres sold by ECKART and SUNSHINE synthetic mica based nacres sold by SUN CHEMICAL.

More particularly, the nacres may have a color or a yellow, pink, red, bronze, orangey, brown, gold and/or coppery glint.

Illustrative examples of nacres which may be employed in the context of the present invention which may be mentioned are gold colored nacres, in particular those sold by ENGELHARD denoted Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze nacres sold by MERCK under the trade name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by ENGELHARD under the trade name Super bronze (Cloisonne); orange nacres sold by ENGELHARD under the trade name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by MERCK under the trade name Passion orange (Colorona) and Matte orange (17449) (Microna); nacres with a brown tint sold by ENGELHARD under the trade name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacres with a copper glint sold by ENGELHARD under the trade name Copper 340A (Timica); nacres with a red tint sold by MERCK under the trade name Sienna fine (17386) (Colorona); nacres with a yellow tint sold by ENGELHARD under the trade name Yellow (4502) (Chromalite); red tinted nacres with a gold tint sold by ENGELHARD under the trade name Sunstone G012 (Gemtone); pink nacres sold by ENGELHARD under the trade name Tan opale G005 (Gemtone); black nacres with a gold glint sold by ENGELHARD under the trade name Nu antique bronze 240 AB (Timica), blue nacres sold by MERCK under the trade name Matte blue (17433) (Microna), white nacres with a silver glint sold by MERCK under the trade name Xirona Silver and green-gold pink orange nacres sold by MERCK under the trade name Indian summer (Xirona).

The article of the invention may also comprise hydrosoluble or liposoluble colorants in an amount of 0.01% to 10% by weight, in particular 0.01% to 5% by weight relative to the total article weight. Examples of liposoluble colorants are Sudan red DC Red 17, DC Green 6, β-carotene, soya oil, Sudan brown, DC Yellow 11, DC Violet 2, DC orange 5 and quinoline yellow. Examples of hydrosoluble colorants are beetroot juice and methylene blue.

It may also contain one or more additives with a formulation currently used in cosmetics, and more especially in the field of cosmetics and/or nail care. They may also be selected from vitamins, oligo-elements, softeners, sequestrating agents, alkalinizing agents or acidifying agents, wetting agents, thickening agents, dispersing agents, anti-foaming agents, spreading agents, co-resins, film-forming agents, plasticizing agents, coalescence agents, preservatives, UV filters, active ingredients, moisturizing agents, neutralizing agents, stabilizing agents, antioxidants and mixtures thereof.

Thus, it is possible to incorporate, as active ingredients, hardening agents for keratinous materials and/or active ingredients to treat various diseases affecting the nails, such as onychomycosis.

The quantities of these various ingredients are those conventionally used in this field, for example 0.01% to 20% by weight, in particular 0.01% to 10% by weight relative to the total article weight.

The article of the invention generally has a thickness of 1 μm to 500 μm, in particular 1 μm to 300 μm, more particularly 1 μm to 200 μm.

As mentioned before, the article of the invention is coated at least on its outer adhesive face with a removable support.

Said support may have any nature compatible with the fact that while it is in contact with an adhesive material, it may also be separated therefrom.

The removable support defined above may be in the form of a protective layer consisting, for example, of a film, in particular a plastic or paper film or a paper or a sheet type textile structure.

Advantageously, said support is constituted by a transparent material to prevent any error in the choice of color. It may be constituted by one or more layers which may be of different natures. As an example, it may be a sheet of paper coated with one of the plastics mentioned above.

Suitable plastic films which may, for example, be used in the article of the invention which may be mentioned are films formed from polyesters, for example polyethylene terephthalates, polybutylene terephthalates or polyethylene sebacates or made from polyethylene, polypropylene or polyamides, such as polyhexamethylene adipate, polycaprolactame or poly(omega-ω-undecanoic acid amide). Because of their surface characteristics, said plastics are clearly not removable per se. To provide this characteristic, it is necessary to carry out a surface treatment using appropriate substances such as a treatment with silicones or, particularly advantageously, by a treatment with salts of long chain fatty acids such as C₁₂ to C₂₂, for example, said acids being saturated or possibly containing up to three olefinic bonds, and at least some divalent metals, in particular salts of heavy transition metals of this type and more particularly chromium salts.

The sheet type textile structure may be woven or non-woven.

In a particular implementation, both faces of the article of the invention are coated with identical or different removable support.

The article of the present invention may be in various forms such as a star, square, roundel, etc.

As described above, the present invention also encompasses a product suitable for packaging an article of the present invention in a partially dry form.

This means that once applied, the article of the present invention is dried and then adopts its definitive structure by contact with the ambient air.

An article of the invention may be obtained with a device as described in U.S. Pat. No. 4,903,840.

As indicated above, the present invention also provides a method of preparing a flexible nail cosmetic and/or nail care article.

The adhesive material is generally deposited in the form of a layer of material with a thickness of 0.5 μm to 200 μm, in particular 1 μm to 100 μm.

An article of the invention the organic film of which is obtained by evaporation of the organic or aqueous solvent phase from a solution or dispersion of film-forming polymer(s) may, for example, be obtained by transposing the method described in U.S. Pat. No. 5,415,903. The material with an optical, relief, and/or olfactory effect is in this case introduced into the solvent phase under consideration.

The article obtained, in particular excess film, is then generally cut out, before or after application thereof, to the desired shape and form with small scissors, nail clippers or by scratching the film.

The present invention also provides a method of making up the nails in which the article as defined above is applied.

Claims

1-52. (canceled)

53. A flexible article with an optical, relief, and/or olfactory effect for making up and/or caring for the nails and/or nails, comprising:

at least one adhesive layer for fixing the article to the nail;

at least one organic film; and

at least one material with an optical, relief, and/or olfactory effect.

54. An article according to claim 53, wherein said material is present within said film.

55. An article according to claim 53, wherein it comprises at least two films with distinct compositions, superposed on the adhesive layer.

56. An article according to claim 55, wherein each of the films contains at least one material with an optical, relief, and/or olfactory effect.

57. An article according to claim 55, wherein at least one of the organic films is free of material with an optical, relief, and/or olfactory effect.

58. An article according to claim 57, wherein said film is transparent.

59. An article according to claim 57, wherein it is a film which is not contiguous with the adhesive layer.

60. An article according to claim 53, wherein it has a dry matter content of more than 80% by weight or more.

61. An article according to claim 53, wherein it has a water take-up at 25° C. of 20% or less.

62. An article according to claim 53, wherein it has a storage modulus E′ of 1 MPa or more, at a temperature of 30° C. and a frequency of 0.1 Hz.

63. An article according to claim 53, wherein it has a deformation at break, ∈r, of 5% or more, and/or an energy at break per unit volume, Wr, of 0.2 J/cm3 or more.

64. An article according to claim 53, wherein said organic film derives from cross-linking a cross-linkable composition and/or from evaporating off the organic or aqueous solvent phase from a solution or dispersion of at least one film-forming polymer.

65. An article according to claim 64, wherein it comprises at least one polymeric film deriving from thermally, photochemically and/or chemically cross-linking a cross-linkable composition.

66. An article according to claim 65, wherein said composition comprises at least one reactive system formed by:

at least one first compound (A) comprising at least two functions (X);

at least one second compound (B) comprising at least two functions (Y), reactive towards the X functions, said reactive systems having a mean functionality (total number of X and Y functions/total number of molecules of compounds (A) and (B)) of more than 2.

67. An article according to claim 64, wherein said cross-linking is of the polyaddition and/or polycondensation type, of compounds comprising at least two isocyanate and/or epoxy functions with compounds having at least two labile hydrogen functions.

68. An article according to claim 67, wherein the compounds carrying reactive isocyanate type functions are selected from aliphatic, cycloaliphatic or aromatic diisocyanates, triisocyanates and polyisocyanates, with a molecular mass of less than 10000.

69. An article according to claim 64, wherein said cross-linking is carried out photochemically and employs at least two types of compounds respectively carrying at least one unsaturated double bond, in the presence of a photoinitiator.

70. An article according to claim 53, wherein it comprises at least one polymeric film obtained by evaporating off the organic or aqueous solvent phase from a solution or dispersion of at least one film-forming polymer.

71. An article according to claim 70, wherein said polymeric film derives from evaporating off the organic solvent phase of a solution or dispersion of at least one film-forming polymer.

72. An article according to claim 71, wherein said polymer is selected from homo- and copolymers of (meth) acrylic acid esters and/or amides, homo- and copolymers of vinyl esters or amides, celluloses and cellulose derivatives, polyurethanes, acrylic polyurethanes, polyureas, polyurea polyurethanes, polyester polyurethanes, polyether polyurethanes, polyesters, polyester amides, fatty chain polyesters, epoxy compounds and arylsulfonamide condensates.

73. An article according to claim 70, wherein said polymeric film derives from evaporating off the aqueous phase of an aqueous dispersion of film-forming polymeric particles and wherein the aqueous dispersion of film-forming polymer particles is a latex, pseudolatex or a mixture thereof.

74. An article according to claim 73, wherein said polymer is selected from polycondensates, anionic, cationic, non ionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea polyurethanes, polyesters, polyester amides, fatty chain polyesters, polyamides and epoxy ester resins, acrylic and/or vinyl polymers or copolymers, acrylic/silicone or nitrocellulose/acrylic copolymers, polymers resulting from radical polymerization of one or more radical monomers, inside and/or partially on the surface of pre-existing particles of at least one polymer selected from the group constituted by polyurethanes, polyureas, polyesters and polyesteramides and/or alkyds.

75. An article according to claim 53, wherein it comprises at least one material with an optical effect in a quantity sufficient to produce a specific optical effect perceptible to the naked eye, said specific optical effect being chosen from a metallic effect and in particular a mirror effect, a goniochromatic effect, a rainbow effect and a thermochromic effect.

76. An article according to claim 53, wherein it comprises at least one material with a relief effect present in a quantity sufficient to produce, on the surface of said art, a specific relief effect which is perceptible to the touch, said specific relief effect being chosen from a rough effect, a grained effect and a hammered effect.

77. An article according to claim 53, wherein it comprises at least one material with an olfactory effect in a quantity sufficient to produce a specific odorizing effect which is perceptible by the user, which is a fragrancing substance.

78. An article according to claim 53, wherein said adhesive layer comprises at least one adhesive material.

79. An article according to claim 53, wherein said adhesive material is such that said article cannot be removed by peeling when it is applied to the surface of a synthetic or natural nail after leaving for at least 24 hours.

80. An article according to claim 78, wherein said adhesive material is selected from copolymers deriving from copolymerizing vinyl monomers with polymeric entities, copolymers having a polymeric skeleton with a Tg of 0° C. to 45° C. grafted with chains deriving from acrylic and/or methacrylic monomers and, in contrast, having a Tg of 50° C. to 200° C., and polyisobutylenes having a relative molar mass, Mv, of 10000 or more and 150000 or less.

81. An article according to claim 53, wherein the surface of said adhesive layer is coated with a removable support constituted by a plastic film modified by a surface treatment with silicone or with salts of C12 to C22 fatty acids.

82. An article according to claim 53, wherein said removable support is constituted by a plastic film modified by a surface treatment with silicone or with salts of C12 to C22 fatty acids.

83. A substance for making up and/or for caring for nails and/or false nails comprising, in packaging, which is substantially airtight, at least one article according to claim 53, the packaging being such that said article is preserved in a partially dry form.

84. A substance according to claim 83, wherein said article has a dry matter content of less than 80% by weight relative to the total weight of said article.

85. A substance according to claim 83, wherein the packaging comprises a reservoir which may contain said article in a sealed manner.

86. A method of preparing a flexible article for making up and/or caring for the nails, comprising at least the following steps consisting of superposing 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 which can form, by cross-linking and/or evaporation of its organic or aqueous solvent phase, an organic film containing at least one material with an optical, relief, and/or olfactory effect, said film being formed consecutively to deposition of said composition.

87. A method according to claim 86, wherein it comprises in step b) deposition of a first composition and its transformation into an organic film, and depositing, onto the film formed, a second composition which differs from the first composition and transforming it into a second organic film.

88. A method according to claim 87, wherein each of the films contains a material with an optical, relief, and/or olfactory effect.

89. A method according to claim 86, wherein the second film is free of material with an optical, relief, and/or olfactory effect.

90. A method according to claim 86, wherein the article is a flexible article with an optical, relief, and/or olfactory effect for making up and/or caring for the nails and/or false nails, comprising:

at least one adhesive layer for fixing the article to the nail;

at least one organic film; and

at least one material with an optical, relief, and/or olfactory effect.

91. A method of preparing a substance according to claim 86, comprising the following steps consisting of superposing 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 which can form, by cross-linking and/or evaporation of its organic or aqueous solvent phase, an organic film containing at least one material with an optical, relief, and/or olfactory effect, said film being formed consecutively to deposition of said composition;

c) if necessary, partially drying said article obtained; and

d) packaging said article in a partially dry condition within a substantially airtight packaging.

92. A method of making up the nails using an article, comprising applying the adhesive face of an article as defined in claim 53 to a natural or synthetic nail.

93. An article according to claim 79, wherein said adhesive material is selected from copolymers deriving from copolymerizing vinyl monomers with polymeric entities, copolymers having a polymeric skeleton with a Tg of 0° C. to 45° C. grafted with chains deriving from acrylic and/or methacrylic monomers and, in contrast, having a Tg of 50° C. to 200° C., and polyisobutylenes having a relative molar mass, Mv, of 10000 or more and 150000 or less.

94. A substance according to claim 84, wherein the packaging comprises a reservoir which may contain said article in a sealed manner.

95. A method according to claim 87, wherein the second film is free of material with an optical, relief, and/or olfactory effect.