This application claims the benefit of priority to French Application No. 01 00623, filed Jan. 17, 2001, and to U.S. Provisional Application No. 60/330,767, filed Oct. 30, 2001.
The present invention relates to a composition for caring for and/or treating and/or making up the nails of human beings, comprising a liquid organic phase including a volatile organic solvent, structured by a specific polymer. This composition is provided in particular in the form of a nail polish stick.
The makeup composition can also be applied to makeup accessories (support), such as false nails.
In nail polishes comprising an organic solvent medium, it is standard practice to thicken the organic phase with thickening agents.
The term “liquid organic phase” is understood to mean, within the meaning of the invention, an organic phase which is liquid at ambient temperature (25° C.) and which is composed of one or more organic compounds which are liquid at ambient temperature, also known as organic solvents or oils, generally compatible with one another. Thickened compositions make it possible to make it easier to take the product from its container without significant loss, to distribute the polish over the surface of the nail or alternatively to be able to use the polish in sufficient amounts to obtained the desired cosmetic effect. Furthermore, the thickening agent makes it possible to prevent the sedimentation during storage of the pigments often present in nail polishes.
The use is known, for thickening the compositions, of clays such as organomodified montmorillonites, such as disclosed in Application GB-A-2021411. In point of fact, clays opacify the composition and do not make possible the preparation of a translucent composition. Furthermore, clays are often formulated with an agent which promotes their swelling, such as citric acid or orthophosphoric acid, which can lead to instability of the composition.
Furthermore, nail polishes known to date are generally provided in the form of a fluid composition which is applied using a brush or alternatively a pen (see in particular U.S. Pat. No. 4,712,571).
The need thus remains for a composition which does not exhibit the above disadvantages. Furthermore, it is desirable to be able to have available a novel nail polish pharmaceutical dosage form different from the nail polishes known to date.
A subject matter of the invention is specifically a composition for caring for and/or making up and/or treating the nails which makes it possible to overcome the abovementioned disadvantages.
The applicant has found, surprisingly, that the use of specific polymers in combination with one or more volatile organic solvents makes it possible to obtain structured nail polishes, in particular a gel and more particularly a stick, the application of which to the nails results in a film having good cosmetic properties.
The invention applies not only to products for making up the nails but also to products for caring for and/or treating the nails.
More specifically, a subject matter of the invention is a structured nail polish composition comprising at least one liquid organic phase comprising at least one volatile organic solvent, the liquid organic phase being structured by at least one first polymer with a weight-average molecular mass of less than or equal to 100 000 comprising a) a polymer backbone having hydrocarbonaceous repeat units which are provided with at least one heteroatom and b) optionally functionalized pendent and/or end fatty chains which have from 6 to 120 carbon atoms and which are bonded to these hydrocarbonaceous units.
Another subject matter of the invention is a stick nail polish composition comprising an organic phase comprising a volatile organic solvent and a first polymer with a weight-average molecular mass of less than or equal to 100 000 comprising a) a polymer backbone having hydrocarbonaceous repeat units which are provided with at least one heteroatom and b) optionally functionalized pendent and/or end fatty chains which have from 6 to 120 carbon atoms and which are bonded to these hydrocarbonaceous units.
A further subject matter of the invention is a cosmetic process for caring for, making up or treating the nails, comprising the application, to the nails, of the composition, in particular cosmetic composition, as defined above.
Another subject matter of the invention is the use in a nail polish composition, for producing a stick, of a liquid organic phase comprising at least one volatile organic solvent and of a sufficient amount of a first polymer with a weight-average molecular mass of less than or equal to 100 000 comprising a) a polymer backbone having hydrocarbonaceous repeat units which are provided with at least one heteroatom and b) optionally functionalized pendent and/or end fatty chains which have from 6 to 120 carbon atoms and which are bonded to these hydrocarbonaceous units.
The nail polish composition of the invention can be provided in the form of a paste, solid, gel, cream or thickened liquid. It can be an oil-in-water or water-in-oil emulsion or a stiff or soft anhydrous gel. In particular, it is provided in the form cast as a stick or as a dish and more especially in the form of a stiff anhydrous gel, in particular an anhydrous stick. More especially, it is provided in the form of a stiff gel which can be translucent or transparent, the liquid organic phase forming the continuous phase.
The gelling of the solvent phase can be adjusted according to the nature of the heteroatom-comprising polymer used and can be such that a stiff structure in the form of a tube or stick is obtained.
The structuring polymer of the composition of the invention is a solid which is nondeformable at ambient temperature (25° C.).
The term “functionalized chains” is understood to mean, within the meaning of the invention, an alkyl chain comprising one or more functional or reactive groups chosen in particular from amide, hydroxyl, ether, oxyalkylene or polyoxyalkylene, halogen, ester, siloxane or polysiloxane groups, the halogen groups including fluorinated or perfluorinated groups. In addition, the hydrogen atoms of one or more fatty chains can be at least partially substituted by fluorine atoms.
According to the invention, these chains can be bonded directly to the polymer backbone or can be bonded via an ester functional group or a perfluorinated group.
The term “polymer” is understood to mean, within the meaning of the invention, a compound having at least 2 repeat units and preferably at least 3 repeat units which are identical.
The term “hydrocarbonaceous repeat units” is understood to mean, within the meaning of the invention, a unit comprising from 2 to 80 carbon atoms and preferably from 2 to 60 carbon atoms, carrying hydrogen atoms and optionally oxygen atoms, which can be linear, branched or cyclic and saturated or unsaturated. In addition, these units each comprise from one to several heteroatoms which are advantageously nonpendent heteroatoms and which are found in the polymer backbone. These heteroatoms are chosen from nitrogen, sulfur or phosphorus atoms and their combinations, optionally in combination with one or more oxygen atoms. Preferably, the units comprise at least one nitrogen atom, in particular one nonpendent nitrogen atom. Advantageously, these units additionally comprise a carbonyl group.
The heteroatom-comprising units are in particular amide units, forming a backbone of the polyamide type, or carbamate and/or urea units, forming a polyurethane, polyurea and/or polyurea/urethane backbone. These units are preferably amide units. Advantageously, the pendent chains are bonded directly to at least one of the heteroatoms of the polymer backbone. According to one embodiment, the first polymer comprises a polyamide backbone.
The first polymer can comprise, between the hydrocarbonaceous units, silicone units or oxyalkylenated units.
In addition, the first polymer of the composition of the invention advantageously comprises a total number of fatty chains which represents from 40 to 98% of the total number of the heteroatom-comprising units and of the fatty chains and better still from 50 to 95%. The nature and the proportion of the heteroatom-comprising units depends on the nature of the organic phase and is in particular similar to the polar nature of the organic phase. Thus, the greater the polarity of the heteroatom-comprising units and the greater their proportion in the first polymer, which corresponds to the presence of several heteroatoms, the greater the affinity of the first polymer for polar oils. On the other hand, the lower the polarity of the heteroatom-comprising units, indeed even when they are nonpolar, or the lower their proportion, the greater the affinity of the first polymer for nonpolar oils.
The first polymer is advantageously a polyamide. Consequently, another subject matter of the invention is a structured nail polish composition comprising at least one liquid organic phase comprising at least one volatile organic solvent, the liquid organic phase being structured by at least one polyamide with a weight-average molecular mass of less than or equal to 100 000 comprising a) a polymer backbone having amide repeat units and b), optionally, optionally functionalized pendent and/or end fatty chains which have from 6 to 120 carbon atoms and which are bonded to these amide units.
Another subject matter of the invention is a stick nail polish composition comprising a volatile organic solvent and a first polyamide polymer with a weight-average molecular mass of less than or equal to 100 000 comprising a) a polymer backbone having amide repeat units and b) optionally functionalized pendent and/or end fatty chains which have from 6 to 120 carbon atoms and which are bonded to these amide units.
Preferably, the pendent fatty chains are bonded to at least one of the nitrogen atoms of the amide units of the first polymer.
In particular, the fatty chains of this polyamide represent from 40 to 98% of the total number of the amide units and of the fatty chains and better still from 50 to 95%.
Advantageously, the first polymer and in particular the polyamide of the composition according to the invention exhibits a weight-average molecular mass of less than or equal to 100 000 (ranging in particular from 1 000 to 100 000), especially of less than 50 000 (ranging in particular from 1 000 to 50 000) and more especially ranging from 1 000 to 30 000, preferably from 2 000 to 20 000 and better still from 2 000 to 10 000.
Mention may be made, as preferred first polymers which can be used in the invention, of polyamides branched by pendent fatty chains and/or end fatty chains having from 6 to 120 carbon atoms and better still from 8 to 120 and in particular from 12 to 68 carbon atoms, each end fatty chain being bonded to the polyamide backbone via at least one bonding group, in particular an ester group. Preferably, these polymers comprise a fatty chain at each end of the polymer backbone and in particular of the polyamide backbone. Mention may be made, as other bonding group, of ether, amine, urea, urethane, thioether, thioester, thiourea or thiourethane groups.
These first polymers are preferably polymers resulting from a polycondensation between a dicarboxylic acid having at least 32 carbon atoms (having in particular from 32 to 44 carbon atoms) with a diamine having at least 2 carbon atoms (in particular from 2 to 36 carbon atoms). The diacid is preferably a dimer resulting from a fatty acid comprising ethylenic unsaturation having at least 16 carbon atoms, preferably from 16 to 24 carbon atoms, such as oleic acid, linoleic acid or linolenic acid. The diamine is preferably ethylenediamine, hexylenediamine or hexamethylenediamine. For polymers comprising one or 2 end carboxylic acid groups, it is advantageous to esterify them with a monoalcohol having at least 4 carbon atoms, preferably from 10 to 36 carbon atoms and better still from 12 to 24 and even better still from 16 to 24, for example 18 carbon atoms.
These polymers are more especially those disclosed in the document U.S. Pat. No. 5,783,657 of Union Camp. Each of these polymers satisfies in particular the following formula (I):
in which n denotes a whole number of amide units such that the number of ester groups represents from 10% to 50% of the total number of the ester and amide groups; R1 is, in each case, independently an alkyl or alkenyl group having at least 4 carbon atoms and in particular from 4 to 24 carbon atoms; R2 independently represents, in each case, a C4 to C42 hydrocarbonaceous group, provided that 50% of the R2 groups represent a C30 to C42 hydrocarbonaceous group; R3 independently represents, in each case, an organic group provided with at least 2 carbon atoms, with hydrogen atoms and optionally with one or more oxygen or nitrogen atoms; and R4 independently represents , in each case, a hydrogen atom, a C1 to C10 alkyl group or a direct bond to R3 or to another R4, so that the nitrogen atom to which both R3 and R4 are bonded forms part of a heterocyclic structure defined by R4—N—R3, with at least 50% of the R4 groups representing a hydrogen atom.
In the specific case of the formula (I), the optionally functionalized end fatty chains within the meaning of the invention are end chains bonded to the final heteroatom, in this instance nitrogen, of the polyamide backbone.
In particular, the ester groups of the formula (I), which form part of the end and/or pendent fatty chains within the meaning of the invention, represent from 15 to 40% of the total number of the ester and amide groups and better still from 20 to 35%. Furthermore, n advantageously represents an integer ranging from 1 to 5 and better still of greater than 2, in particular ranging from 3 to 5. Preferably, R1 is a C12 to C22 alkyl group and preferably a C16 to C22 alkyl group. Advantageously, R2 can be a C10 to C42 hydrocarbonaceous (alkylene) group. Preferably, at least 50% and better still at least 75% of the R2 groups are groups having from 30 to 42 carbon atoms. The other R2 groups are C4 to C19 and even C4 to C12 hydrogenated groups. Preferably, R3 represents a C2 to C36 hydrocarbonaceous group or a polyoxyalkylenated group and R4 represents a hydrogen atom. Preferably, R3 represents a C2 to C12 hydrocarbonaceous group.
The hydrocarbonaceous groups can be linear, cyclic or branched and saturated or unsaturated groups. Furthermore, the alkyl and alkylene groups can be linear or branched and saturated or unsaturated groups.
The polymers of formula (I) are generally provided in the form of blends of polymers, it being possible for these blends to additionally comprise a synthetic product corresponding to a compound of formula (I) where n has the value 0, that is to say a diester.
Mention may be made, as examples of first polymers according to the invention, of the commercial products sold by Arizona Chemical under the names UNICLEAR 80 and UNICLEAR 100. They are sold respectively in the form of an 80% (as active material) gel in a mineral oil and of a 100% (as active material) gel. They have a softening point of 88 to 94° C. These commercial products are a blend of copolymers of a C36 diacid condensed with ethylenediamine, with a weight-average molecular mass of approximately 6 000. The end ester groups result from esterification of the remaining acid endings with cetyl alcohol, stearyl alcohol or their mixtures (also known as cetearyl alcohol).
Mention may also be made, as first polymer which can be used in the invention, of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and of a diamine (including compounds having more than 2 carbonyl groups and 2 amine groups), the carbonyl and amine groups of adjacent individual units being condensed via an amide bond. These polyamides are in particular those sold under the VERSAMID trademark by General Mills Inc. and Henkel Corp. (VERSAMID 930, 744 or 1655) or by Olin Mathieson Chemical Corp. under the ONAMID trademark, in particular ONAMID S or C. These resins have a weight-average molecular mass ranging from 6 000 to 9 000. For further information on these polyamides, reference may be made to the documents U.S. Pat No. 3,645,705 and U.S. Pat No. 3,148,125. More especially, VERSAMID 930 or 744 is used.
It is also possible to use the polyamides sold by Arizona Chemical under the UNI-REZ references (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) and the product sold under the reference MACROMELT 6212 by Henkel. For further information on these polyamides, reference may be made to the document U.S. Pat No. 5,500,209.
It is also possible to use polyamide resins resulting from vegetables, such as those disclosed in Patents U.S. Pat No. 5,783,657 and U.S. Pat No. 5,998,570, the contents of which are incorporated by way of reference in the present application.
The first polymer present in the composition according to the invention advantageously has a softening temperature of greater than 65° C. and which can range up to 190° C. Preferably, it exhibits a softening temperature ranging from 70 to 130° C. and better still from 80 to 105° C. The first polymer is in particular a nonwaxy polymer.
The first polymer according to the invention preferably corresponds to the formula (I) mentioned above. This first polymer exhibits, because of their fatty chain(s), good solubility in oils and thus results in macroscopically homogeneous compositions, even with a high level (at least 25%) of polymer, in contrast to polymers devoid of a fatty chain.
The first polymer can be present in the composition according to the invention in a content ranging from 0.1% to 60% by weight with respect to the total weight of the composition, preferably ranging from 0.5% to 30% by weight and better still ranging from 1% to 20% by weight.
The liquid organic phase of the composition according to the invention additionally comprises at least one volatile organic solvent, namely one or more volatile solvents.
The term “volatile organic solvent” is understood to mean, within the meaning of the invention, any nonaqueous medium capable of evaporating on contact with the skin or nails in less than one hour at ambient temperature and atmospheric pressure. The volatile solvent or solvents of the invention are organic solvents and in particular volatile cosmetic oils which are liquid at ambient temperature and which have a nonzero vapour pressure, at ambient temperature and atmospheric pressure, ranging in particular from 10−3 to 300 mm of Hg (0.013 Pa to 40 000 Pa) and preferably of greater than 0.1 mm of Hg (10 Pa) and better still of greater than 0.3 mm of Hg (30 Pa).
According to the invention, these volatile solvents in particular facilitate the application of the composition to the nails. These solvents can be hydrocarbonaceous solvents, silicone solvents optionally comprising pendent alkyl or alkoxy groups or alkyl or alkoxy groups at the end of the silicone chain, or a mixture of these solvents. Preferably, these solvents are not alcohols comprising at least 7 carbon atoms.
Advantageously, the liquid organic phase of the composition comprises at least one volatile organic solvent or a mixture of volatile organic solvents (within the meaning of the final mixture) exhibiting mean Hansen solubility parameters dD, dP and dH at 25° C. which satisfy the following conditions:
15≦dD≦19
dP≦10
dH≦10
Consequently, a subject matter of the invention is a cosmetic composition comprising an organic phase, a first polymer and a second additional film-forming polymer, the organic phase comprising at least one volatile organic solvent or a mixture of volatile organic solvents exhibiting mean Hansen solubility parameters dD, dP and dH at 25° C. which satisfy the conditions defined above.
Another subject matter of the invention is a nail polish composition comprising an organic phase, a first polymer and a second additional film-forming polymer, the organic phase comprising at least one volatile organic solvent or a mixture of volatile organic solvents exhibiting mean Hansen solubility parameters dD, dP and dH at 25° C. which satisfy the conditions defined above.
The definition of the solvents in the three-dimensional solubility space according to Hansen is described in the article by C. M. Hansen: “The three-dimensional solubility parameters”, J. Paint Technol., 39, 105 (1967):
The parameters dD, dP and dH are expressed in (J/cm3)1/2.
Use is preferably made of an organic solvent such that dP≦5; dH≦9.
Advantageously, dD, dP and dH obey the relationship
√{square root over (4(17−dD)2+dP2+dH2)}<L
L being equal to 10 (J/cm3)1/2 and better still 9 (J/cm3)1/2.
Mention may be made, as volatile organic solvent which can be used in the invention, of volatile hydrocarbonaceous oils having from 4 to 16 carbon atoms and their mixtures and in particular linear C6-C10 alkanes, such as n-hexane, n-heptane or n-octane, branched C8-C16 alkanes, such as C8-C16 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the tradenames of ISOPARS or PERMETYLS, esters having from 4 to 8 carbon atoms, such as ethyl acetate, n-propyl acetate, isobutyl acetate or n-butyl acetate, branched C8-C16 esters, such as isohexyl neopentanoate, and their mixtures. Preferably, the volatile organic solvent is chosen from volatile hydrocarbonaceous oils having from 4 to 10 carbon atoms and their mixtures.
Mention may be made, as other volatile organic solvent which can be used in the invention, of linear or cyclic silicone oils having a viscosity at ambient temperature of less than 8 centistokes (8 10−6 m2/s) and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. Mention may in particular be made, as volatile silicone oil which can be used in the invention, of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and their mixtures.
Use may also be made of volatile fluorinated solvents.
Use is preferably made of a volatile organic solvent chosen from ethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, heptane and their mixtures.
The volatile organic solvent can be present in the composition according to the invention in a content ranging from 20% to 98% by weight with respect to the total weight of the composition, preferably from 30% to 90% by weight and better still from 40% to 85% by weight.
The organic phase of the composition according to the invention can additionally comprise a nonvolatile oil which can be a polar oil or a nonpolar oil. The nonvolatile oil can be present in a content ranging from 0.01% to 10% by weight with respect to the total weight of the composition.
In particular, the polar oils can be chosen from:
The nonpolar oils according to the invention are in particular silicone oils, such as linear or cyclic polydimethylsiloxanes (PDMSs) which are liquid at ambient temperature; polydimethylsiloxanes comprising pendent alkyl, alkoxy or phenyl groups and/or alkyl, alkoxy or phenyl groups at the end of the silicone chain, which groups have from 2 to 24 carbon atoms; phenylated silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenyl-siloxanes, diphenyl dimethicones, diphenylmethyl-diphenyltrisiloxanes or (2-phenylethyl)trimethyl-siloxysilicates; linear or branched hydrocarbons of synthetic or mineral origin, such as liquid paraffins and its derivatives, petrolatum, liquid lanolin, polydecenes, hydrogenated polyisobutene, such as parleam, or squalane; and their mixtures.
Preferably, the oils are nonpolar oils and more especially an oil or a mixture of oils of the hydrocarbonaceous type of mineral or synthetic origin chosen in particular from hydrocarbons, especially alkanes, such as parleam oil, isoparaffins, such as isododecane and squalane, and their mixtures. Advantageously, these oils are used in combination with one or more phenylated silicone oils.
Preferably, use is made of a nonvolatile oil such that the mixture of volatile organic solvent and of nonvolatile oil exhibits mean Hansen solubility parameters dD, dP and dH at 25° C. which satisfy the conditions defined above.
According to a specific form of the invention, for a liquid organic phase structured by a polymer comprising a partially silicone-comprising backbone, this organic phase preferably comprises more than 40% of the total weight of the liquid organic phase and better still from 50 to 100% of silicone-comprising volatile organic solvent or of silicone-comprising nonvolatile oils with respect to the total weight of the liquid organic phase.
According to another specific form of the invention, for a liquid organic phase structured by a nonpolar polymer of the hydrocarbonaceous type, this organic phase advantageously comprises more than 40% by weight and better still from 50 to 100% of hydrocarbonaceous volatile organic solvent or of hydrocarbonaceous nonpolar nonvolatile oil with respect to the total weight of the liquid organic phase.
The total liquid organic phase represents, in practice, from 5 to 99% of the total weight of the composition, preferably from 20 to 75%.
According to the invention, the composition can be a stick having a hardness ranging from 30 to 300 g and better still from 30 to 250 g, in particular from 30 to 150 g, preferably from 30 to 120 g and, for example, from 30 to 50 g. The hardness of the composition according to the invention can be measured by the “cheesewire” method, which consists in cutting a stick of lipstick with a diameter of 12.7 mm and in measuring the hardness at 20° C. by means of a DFGHS 2 dynamometer from Indelco-Chatillon moving at a rate of 100 mm/minute. It is expressed as the shear force (expressed in grams) needed to cut a stick under these conditions.
The hardness of the composition can also be measured by the method of penetration of a probe into said composition and in particular using a texture analyzer (for example TA-XT2i from Rhéo) equipped with an ebonite cylinder with a height of 25 mm and a diameter of 8 mm. The hardness measurement is carried out at 20° C. at the center of five samples of said composition. The cylinder is introduced into each composition sample at a prerate of 2 mm/s, then at a rate of 0.5 mm/s and, finally, at a postrate of 2 mm/s, the total displacement being 1 mm. The value recorded of the hardness is that of the maximum peak. The measurement error is +/−50 g. According to this method, the hardness of the composition stick can range from 20 to 2 000 g, in particular from 20 to 1 500 g and better still from 20 to 900 g, for example from 50 to 600 g or even better still from 150 to 450 g.
The hardness of the composition according to the invention is such that the composition is advantageously self-supporting and can easily disintegrate to form a satisfactory layer on the nails. In addition, with this hardness, the composition of the invention possesses good impact strength.
The hardness of the composition according to the invention is such that the composition is self-supporting and can easily disintegrate to form a satisfactory layer on the nails. In addition, with this hardness, the composition of the invention possesses good impact strength.
Advantageously, the composition of the invention additionally comprises at least one subsidiary film-forming polymer other than said first polymer as described above.
The film-forming polymer can be chosen from cellulose polymers, such as nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate or ethyl cellulose, or alternatively polyurethanes, acrylic polymers, vinyl polymers, polyvinylbutyrals, alkyd resins, resins resulting from aldehyde condensation products, such as aryl-sulfonamide-formaldehyde resins, for example toluene-sulfonamide-formaldehyde resin, or arylsulfonamide-epoxy resins.
Use may in particular be made, as film-forming polymer, of nitrocellulose RS ⅛ sec.; RS ¼ sec.; ½ sec.; RS 5 sec.; RS 15 sec.; RS 35 sec.; RS 75 sec.; RS 150 sec.; AS ¼ sec.; AS ½ sec.; SS ¼ sec.; SS ½ sec.; SS 5 sec.; sold in particular by Hercules; toluenesulfonamide-formaldehyde resin “KETJENTFLEX MS80”from Akzo or “Santolite MHP” or “Santolite MS80” from Faconnier or “Resimpol 80” from Pan Americana, alkyd resin “BECKOSOL ODE 230-70-E” from Dainippon, acrylic resin “ACRYLOID B66” from Röhm & Haas, or polyurethane resin “TRIXENE PR 4127” from Baxenden.
The subsidiary film-forming polymer can be present in the composition according to the invention in a content ranging from 0.1% to 60% by weight with respect to the total weight of the composition, preferably ranging from 2% to 40% by weight and better still from 5% to 25% by weight.
The composition of the invention can additionally comprise any additive conventionally used in the field under consideration chosen in particular from coloring materials, antioxidants, preservatives, fragrances, fillers, waxes, neutralizing agents, cosmetic or dermatological active principles, such as, for example, emollients, moisturizers or vitamins, spreading agents, sunscreens, and their mixtures. These additives can be present in the composition in a proportion of 0 to 20% (in particular of 0.01 to 20%) of the total weight of the composition and better still of 0.01 to 10%.
Of course, a person skilled in the art will take care to choose the optional additional additives and/or their amount so that the advantageous properties of the composition according to the invention are not, or not substantially, detrimentally affected by the envisaged addition.
Of course, the composition of the invention must be cosmetically or dermatologically acceptable, namely must comprise a nontoxic physiologically acceptable medium capable of being applied to the skin or superficial body growths of human beings. The term “cosmetically acceptable” is understood to mean, within the meaning of the invention, a composition with a pleasant appearance, a pleasant smell and a pleasant feel.
The coloring material according to the invention can be chosen from lipophilic dyes, pigments and pearlescent agents commonly used in cosmetic or dermatological compositions, and their mixtures. This coloring material is generally present in a proportion of 0.01 to 10% of the total weight of the composition, preferably of 0.1 to 8%, if it is present.
The fat-soluble dyes are, for example, Sudan red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5 or quinoline yellow. They can represent from 0.1 to 10% of the weight of the compositions and better still from 0.1 to 6%.
The pigments can be white or colored, inorganic and/or organic and coated or uncoated. Mention may be made, among inorganic pigments, of titanium dioxide, which is optionally surface treated, zirconium or cerium oxides and iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Mention may be made, among organic pigments, of carbon black, pigments of D & C type and lakes based on cochineal carmine or on barium, strontium, calcium or aluminum. The pigments can represent from 0.1 to 50% and better still from 2 to 30% of the total weight of the composition, if they are present.
The pearlescent pigments can be chosen from white pearlescent pigments, such as mica covered with titanium oxide or with bismuth oxychloride, colored pearlescent pigments, such as titanium oxide-coated mica with iron oxides, titanium oxide-coated mica with in particular ferric blue or chromium oxide, or titanium oxide-coated mica with an organic pigment of the abovementioned type, and pearlescent pigments based on bismuth oxychloride. They can represent from 0.1 to 20% of the total weight of the composition and better still from 0.1 to 15%, if they are present.
The composition according to the invention can be manufactured by known processes used generally in the cosmetics or dermatological field.
The invention is illustrated in more detail in the following example. The percentages are given by weight.
A nail polish having the following composition was prepared:
The nail polish is provided in the form of a structured solid composition, such as a stick.
Number | Date | Country | Kind |
---|---|---|---|
01 00623 | Jan 2001 | FR | national |
Number | Name | Date | Kind |
---|---|---|---|
2379413 | Bradley | Jul 1945 | A |
2450940 | Cowan et al. | Oct 1948 | A |
2662068 | Floyd | Dec 1953 | A |
2663649 | Winkler | Dec 1953 | A |
2890097 | Coe | Jun 1959 | A |
2962461 | Toussaint et al. | Nov 1960 | A |
3086914 | Soloway | Apr 1963 | A |
3141787 | Goetze et al. | Jul 1964 | A |
3148125 | Strianse et al. | Sep 1964 | A |
3156572 | Carlick et al. | Nov 1964 | A |
3255082 | Barton | Jun 1966 | A |
3341465 | Kaufman et al. | Sep 1967 | A |
3412115 | Floyd et al. | Nov 1968 | A |
3615289 | Felton | Oct 1971 | A |
3645705 | Miller et al. | Feb 1972 | A |
3778394 | Lovald et al. | Dec 1973 | A |
3819342 | Gunderman et al. | Jun 1974 | A |
3857960 | Mackles | Dec 1974 | A |
3926655 | Miles | Dec 1975 | A |
3937811 | Papantoniou et al. | Feb 1976 | A |
3969087 | Saito et al. | Jul 1976 | A |
4049792 | Elsnau | Sep 1977 | A |
4051159 | Tsoucalas et al. | Sep 1977 | A |
4062819 | Mains et al. | Dec 1977 | A |
RE29871 | Papantoniou et al. | Dec 1978 | E |
4128436 | O'Hara et al. | Dec 1978 | A |
4137306 | Rubino et al. | Jan 1979 | A |
4148875 | Barnett et al. | Apr 1979 | A |
4150002 | Drawert et al. | Apr 1979 | A |
4275054 | Sebag et al. | Jun 1981 | A |
4275055 | Nachtigal et al. | Jun 1981 | A |
4278658 | Hooper et al. | Jul 1981 | A |
4279658 | Harvey et al. | Jul 1981 | A |
4337298 | Karim et al. | Jun 1982 | A |
4341671 | Bolze et al. | Jul 1982 | A |
4376194 | Tanaka et al. | Mar 1983 | A |
4387090 | Bolich, Jr. | Jun 1983 | A |
4438240 | Tanaka et al. | Mar 1984 | A |
4466936 | Schapel | Aug 1984 | A |
4536405 | Nara et al. | Aug 1985 | A |
4552693 | Hussain et al. | Nov 1985 | A |
4571267 | Drawert et al. | Feb 1986 | A |
4620492 | Vogg et al. | Nov 1986 | A |
4655836 | Drawert et al. | Apr 1987 | A |
4663428 | Okitu et al. | May 1987 | A |
4699779 | Palinczar | Oct 1987 | A |
4712571 | Remz et al. | Dec 1987 | A |
4769285 | Rasmussen | Sep 1988 | A |
4806338 | Smith | Feb 1989 | A |
4806345 | Bhattacharyya | Feb 1989 | A |
4820765 | Whyzmuzis | Apr 1989 | A |
4822601 | Goode et al. | Apr 1989 | A |
4871536 | Arraudeau et al. | Oct 1989 | A |
4937069 | Shin | Jun 1990 | A |
4952245 | Iwano et al. | Aug 1990 | A |
5034219 | Deshpande et al. | Jul 1991 | A |
5061289 | Clausen et al. | Oct 1991 | A |
5069897 | Orr | Dec 1991 | A |
5073364 | Giezendanner et al. | Dec 1991 | A |
5085859 | Halloran et al. | Feb 1992 | A |
5102656 | Kasat | Apr 1992 | A |
5186318 | Oestreich et al. | Feb 1993 | A |
5196260 | Dirshl et al. | Mar 1993 | A |
5223559 | Arraudeau et al. | Jun 1993 | A |
5268029 | Demangeon et al. | Dec 1993 | A |
5272241 | Lucarelli et al. | Dec 1993 | A |
5290555 | Guthauser et al. | Mar 1994 | A |
5302398 | Egidio et al. | Apr 1994 | A |
5342894 | Robeson et al. | Aug 1994 | A |
5362482 | Yoneyama et al. | Nov 1994 | A |
5372852 | Titterington et al. | Dec 1994 | A |
5389363 | Snyder et al. | Feb 1995 | A |
5472686 | Tsubaki et al. | Dec 1995 | A |
5486431 | Tuttle et al. | Jan 1996 | A |
5489431 | Ascione et al. | Feb 1996 | A |
5500209 | Mendolia et al. | Mar 1996 | A |
5505937 | Castrogiovanni et al. | Apr 1996 | A |
5510452 | Santhanam | Apr 1996 | A |
5536871 | Santhanam | Jul 1996 | A |
5538718 | Aul et al. | Jul 1996 | A |
5538793 | Inokuchi et al. | Jul 1996 | A |
5540853 | Trinh et al. | Jul 1996 | A |
5603925 | Ross et al. | Feb 1997 | A |
5605651 | Balzer | Feb 1997 | A |
5610199 | Cohen et al. | Mar 1997 | A |
5612043 | Deprez et al. | Mar 1997 | A |
5616331 | Allard et al. | Apr 1997 | A |
5618523 | Zysman et al. | Apr 1997 | A |
5620693 | Piot et al. | Apr 1997 | A |
5645632 | Pavlin | Jul 1997 | A |
5667770 | Szweda et al. | Sep 1997 | A |
5679357 | Dubief et al. | Oct 1997 | A |
5683817 | Kenmochi | Nov 1997 | A |
5702519 | Nitta et al. | Dec 1997 | A |
5719255 | Heucher et al. | Feb 1998 | A |
5747625 | Furukawa et al. | May 1998 | A |
5750125 | Lahanas et al. | May 1998 | A |
5750127 | Rokitowski | May 1998 | A |
5750489 | Garcia et al. | May 1998 | A |
5769902 | Samain | Jun 1998 | A |
5780517 | Cohen et al. | Jul 1998 | A |
5783657 | Pavlin et al. | Jul 1998 | A |
5800816 | Brieva et al. | Sep 1998 | A |
5807968 | Heinrich et al. | Sep 1998 | A |
5830444 | Miguel | Nov 1998 | A |
5830483 | Seidel et al. | Nov 1998 | A |
5837223 | Barone et al. | Nov 1998 | A |
5849275 | Calello et al. | Dec 1998 | A |
5849278 | Piot et al. | Dec 1998 | A |
5849333 | Nordhauser et al. | Dec 1998 | A |
5851517 | Mougin et al. | Dec 1998 | A |
5857903 | Ramspeck et al. | Jan 1999 | A |
5858338 | Piot et al. | Jan 1999 | A |
5866149 | Piot et al. | Feb 1999 | A |
5871764 | Diaz et al. | Feb 1999 | A |
5874069 | Mendolia et al. | Feb 1999 | A |
5882363 | Spaulding et al. | Mar 1999 | A |
5891424 | Bretzler et al. | Apr 1999 | A |
5897869 | Roulier et al. | Apr 1999 | A |
5902592 | Bara et al. | May 1999 | A |
5908631 | Arnaud et al. | Jun 1999 | A |
5911974 | Brieva et al. | Jun 1999 | A |
5919441 | Mendolia et al. | Jul 1999 | A |
5925337 | Arraudeau et al. | Jul 1999 | A |
5945095 | Mougin et al. | Aug 1999 | A |
5945112 | Flynn et al. | Aug 1999 | A |
5959009 | Konik et al. | Sep 1999 | A |
5961998 | Arnaud et al. | Oct 1999 | A |
5965112 | Brieva et al. | Oct 1999 | A |
5972095 | Graves et al. | Oct 1999 | A |
5972354 | de la Poterie et al. | Oct 1999 | A |
5972359 | Sine et al. | Oct 1999 | A |
5976514 | Guskey et al. | Nov 1999 | A |
5981680 | Petroff et al. | Nov 1999 | A |
5985298 | Brieva et al. | Nov 1999 | A |
5993787 | Sun et al. | Nov 1999 | A |
5998570 | Pavlin et al. | Dec 1999 | A |
6001980 | Borzo et al. | Dec 1999 | A |
6004567 | Marchi-Lemann et al. | Dec 1999 | A |
6007799 | Lee et al. | Dec 1999 | A |
6019962 | Rabe et al. | Feb 2000 | A |
6036947 | Barone et al. | Mar 2000 | A |
6045782 | Krog et al. | Apr 2000 | A |
6045823 | Vollhardt et al. | Apr 2000 | A |
6051216 | Barr et al. | Apr 2000 | A |
6054517 | Spaulding et al. | Apr 2000 | A |
6060072 | Konik et al. | May 2000 | A |
6063398 | Gueret | May 2000 | A |
6066328 | Ribier et al. | May 2000 | A |
6074654 | Drechsler et al. | Jun 2000 | A |
6103249 | Roulier et al. | Aug 2000 | A |
6106820 | Morrissey et al. | Aug 2000 | A |
6111055 | Berger et al. | Aug 2000 | A |
6156325 | Farer et al. | Dec 2000 | A |
6156804 | Chevalier et al. | Dec 2000 | A |
6165454 | Patel et al. | Dec 2000 | A |
6165971 | Oppenlander et al. | Dec 2000 | A |
6171347 | Kunz | Jan 2001 | B1 |
6177523 | Reich et al. | Jan 2001 | B1 |
6180117 | Berthiaume et al. | Jan 2001 | B1 |
6180123 | Mondet | Jan 2001 | B1 |
6190673 | Guskey et al. | Feb 2001 | B1 |
6197100 | Melbouci | Mar 2001 | B1 |
6203780 | Arnaud et al. | Mar 2001 | B1 |
6203807 | Lemann | Mar 2001 | B1 |
6214326 | Dupuis | Apr 2001 | B1 |
6214329 | Brieva et al. | Apr 2001 | B1 |
6221389 | Cannell et al. | Apr 2001 | B1 |
6224851 | Bara | May 2001 | B1 |
6242509 | Berger et al. | Jun 2001 | B1 |
6251375 | Bara | Jun 2001 | B1 |
6251409 | Hegyi et al. | Jun 2001 | B1 |
6254876 | de la Poterie et al. | Jul 2001 | B1 |
6254877 | De La Poterie et al. | Jul 2001 | B1 |
6264933 | Bodelin et al. | Jul 2001 | B1 |
6268466 | MacQueen et al. | Jul 2001 | B1 |
6280846 | Darby et al. | Aug 2001 | B1 |
6287552 | Tournilhac et al. | Sep 2001 | B1 |
6325994 | Collin et al. | Dec 2001 | B1 |
6348563 | Fukuda et al. | Feb 2002 | B1 |
6372235 | Livoreil et al. | Apr 2002 | B1 |
6376078 | Inokuchi | Apr 2002 | B1 |
6383502 | Dunshee et al. | May 2002 | B1 |
6399080 | Bara | Jun 2002 | B1 |
6399081 | Nakanishi et al. | Jun 2002 | B1 |
6402408 | Ferrari | Jun 2002 | B1 |
6423306 | Caes et al. | Jul 2002 | B1 |
6423324 | Murphy et al. | Jul 2002 | B1 |
6428773 | Oko et al. | Aug 2002 | B1 |
6432391 | Bara | Aug 2002 | B1 |
6447759 | Noguchi et al. | Sep 2002 | B1 |
6469131 | Lawson et al. | Oct 2002 | B1 |
6475500 | Vatter et al. | Nov 2002 | B1 |
6479686 | Nakanishi et al. | Nov 2002 | B1 |
6482400 | Collin | Nov 2002 | B1 |
6491931 | Collin | Dec 2002 | B1 |
6497861 | Wang et al. | Dec 2002 | B1 |
6506716 | Delplancke et al. | Jan 2003 | B1 |
6649173 | Arnaud et al. | Nov 2003 | B1 |
6682748 | De La Poterie et al. | Jan 2004 | B1 |
6726917 | Kanji et al. | Apr 2004 | B1 |
6761881 | Bara | Jul 2004 | B1 |
6875245 | Pavlin | Apr 2005 | B1 |
20010014312 | Nakanishi et al. | Aug 2001 | A1 |
20010028887 | Duin et al. | Oct 2001 | A1 |
20010031280 | Ferrari et al. | Oct 2001 | A1 |
20010033846 | Roulier et al. | Oct 2001 | A1 |
20020044918 | Bara | Apr 2002 | A1 |
20020058053 | Nakanishi et al. | May 2002 | A1 |
20020081323 | Nakanish et al. | Jun 2002 | A1 |
20020102225 | Hess et al. | Aug 2002 | A1 |
20020107314 | Pinzon et al. | Aug 2002 | A1 |
20020111330 | Pinzon et al. | Aug 2002 | A1 |
20020114771 | Nakanishi | Aug 2002 | A1 |
20020114773 | Kanji et al. | Aug 2002 | A1 |
20020119171 | Gruning et al. | Aug 2002 | A1 |
20020120036 | Pinzon et al. | Aug 2002 | A1 |
20020122781 | Pinzon et al. | Sep 2002 | A1 |
20020131947 | Nakanishi | Sep 2002 | A1 |
20020141958 | Maio et al. | Oct 2002 | A1 |
20020150602 | Livoreil et al. | Oct 2002 | A1 |
20020159964 | Nakanishi et al. | Oct 2002 | A1 |
20020168335 | Collin | Nov 2002 | A1 |
20020172696 | Ferrari | Nov 2002 | A1 |
20020189030 | Collin | Dec 2002 | A1 |
20020192168 | Blin et al. | Dec 2002 | A1 |
20030012764 | Collin | Jan 2003 | A1 |
20030026772 | Jager-Lezer et al. | Feb 2003 | A1 |
20030044367 | Simon et al. | Mar 2003 | A1 |
20030086883 | Feng et al. | May 2003 | A1 |
20030147837 | Cavazzuti et al. | Aug 2003 | A1 |
20030161807 | Lemann | Aug 2003 | A1 |
20030161848 | Ferrari et al. | Aug 2003 | A1 |
20030185780 | Ferrari et al. | Oct 2003 | A1 |
20030198613 | Feng et al. | Oct 2003 | A1 |
20040013625 | Kanji | Jan 2004 | A1 |
20040028636 | Collin | Feb 2004 | A1 |
20040042980 | Kanji et al. | Mar 2004 | A1 |
20040086478 | Ferrari | May 2004 | A1 |
20040091510 | Feng et al. | May 2004 | A1 |
20040126401 | Collin | Jul 2004 | A1 |
20040166076 | Ferrari et al. | Aug 2004 | A1 |
20040166133 | Cavazzuti et al. | Aug 2004 | A1 |
Number | Date | Country |
---|---|---|
2003346 | May 1990 | CA |
1319306 | Jun 1993 | CA |
38 39 136 | May 1990 | DE |
38 43 892 | Jun 1990 | DE |
42 08 297 | Sep 1993 | DE |
42 34 886 | Apr 1994 | DE |
195 43 988 | May 1997 | DE |
197 07 309 | Aug 1998 | DE |
197 50 246 | May 1999 | DE |
199 51 010 | Apr 2001 | DE |
0 169 997 | Feb 1986 | EP |
0 370 470 | May 1990 | EP |
0 374 332 | Jun 1990 | EP |
0 444 633 | Sep 1991 | EP |
0 295 886 | Jan 1992 | EP |
0 557 196 | Aug 1993 | EP |
0 602 905 | Jun 1994 | EP |
0 609 132 | Aug 1994 | EP |
0 623 670 | Nov 1994 | EP |
0 628 582 | Dec 1994 | EP |
0 412 710 | Jul 1995 | EP |
0 673 642 | Sep 1995 | EP |
0 708 114 | Apr 1996 | EP |
0 749 746 | Dec 1996 | EP |
0 749 747 | Dec 1996 | EP |
0 749 748 | Dec 1996 | EP |
0 775 483 | May 1997 | EP |
0 797 976 | Oct 1997 | EP |
0 820 764 | Jan 1998 | EP |
0 847 752 | Jun 1998 | EP |
0 877 063 | Nov 1998 | EP |
0 879 592 | Nov 1998 | EP |
0 887 073 | Dec 1998 | EP |
0 923 928 | Jun 1999 | EP |
0 925 780 | Jun 1999 | EP |
0 928 608 | Jul 1999 | EP |
0 930 058 | Jul 1999 | EP |
0 930 060 | Jul 1999 | EP |
0 943 340 | Sep 1999 | EP |
0 958 804 | Nov 1999 | EP |
0 958 805 | Nov 1999 | EP |
0 958 811 | Nov 1999 | EP |
0 959 066 | Nov 1999 | EP |
0 959 091 | Nov 1999 | EP |
0 976 390 | Feb 2000 | EP |
0 984 025 | Mar 2000 | EP |
1 002 514 | May 2000 | EP |
1 031 342 | Aug 2000 | EP |
1 048 282 | Nov 2000 | EP |
1 053 742 | Nov 2000 | EP |
1 062 944 | Dec 2000 | EP |
1 062 959 | Dec 2000 | EP |
1 064 919 | Jan 2001 | EP |
1 064 920 | Jan 2001 | EP |
1 066 814 | Jan 2001 | EP |
1 068 854 | Jan 2001 | EP |
1 068 855 | Jan 2001 | EP |
1 068 856 | Jan 2001 | EP |
1 086 945 | Mar 2001 | EP |
1 090 627 | Apr 2001 | EP |
1 095 959 | May 2001 | EP |
1 114 636 | Jul 2001 | EP |
1 213 011 | Jun 2002 | EP |
1 213 316 | Jun 2002 | EP |
1 529 329 | May 1968 | FR |
2 232 303 | Jan 1975 | FR |
2 674 126 | Sep 1992 | FR |
2 785 179 | May 2000 | FR |
2 796 270 | Jan 2001 | FR |
2 796 271 | Jan 2001 | FR |
2 796 272 | Jan 2001 | FR |
2 796 273 | Jan 2001 | FR |
2 796 276 | Jan 2001 | FR |
2 802 806 | Jun 2001 | FR |
2 804 017 | Jul 2001 | FR |
2 804 018 | Jul 2001 | FR |
2 810 562 | Dec 2001 | FR |
2 811 225 | Jan 2002 | FR |
2 811 552 | Jan 2002 | FR |
2 816 506 | May 2002 | FR |
2 817 739 | Jun 2002 | FR |
2 817 740 | Jun 2002 | FR |
2 817 743 | Jun 2002 | FR |
2 819 399 | Jul 2002 | FR |
2 819 400 | Jul 2002 | FR |
2 819 402 | Jul 2002 | FR |
1 117 129 | Jun 1968 | GB |
1 194 901 | Jun 1970 | GB |
1 194 902 | Jun 1970 | GB |
1 220 069 | Jan 1971 | GB |
1 273 004 | May 1972 | GB |
1 444 204 | Jul 1976 | GB |
2 014 852 | Sep 1979 | GB |
2 021 411 | Dec 1979 | GB |
2 021 411 | Dec 1979 | GB |
2 147 305 | May 1985 | GB |
2 196 978 | May 1988 | GB |
2 196 978 | May 1988 | GB |
5058242 | May 1975 | JP |
53043577 | Apr 1978 | JP |
56123909 | Sep 1981 | JP |
56166276 | Dec 1981 | JP |
61065809 | Apr 1986 | JP |
62061911 | Mar 1987 | JP |
2127568 | May 1990 | JP |
02200612 | Aug 1990 | JP |
2216279 | Aug 1990 | JP |
3014683 | Jan 1991 | JP |
04346909 | Dec 1992 | JP |
7179795 | Jul 1995 | JP |
7267827 | Oct 1995 | JP |
8225316 | Sep 1996 | JP |
920631 | Jan 1997 | JP |
09255560 | Sep 1997 | JP |
9295922 | Nov 1997 | JP |
10007527 | Jan 1998 | JP |
10120903 | May 1998 | JP |
10212213 | Aug 1998 | JP |
10259344 | Sep 1998 | JP |
11106216 | Apr 1999 | JP |
11335228 | Dec 1999 | JP |
11335242 | Dec 1999 | JP |
11335254 | Dec 1999 | JP |
2000038314 | Feb 2000 | JP |
2000038316 | Feb 2000 | JP |
2000038317 | Feb 2000 | JP |
2000038321 | Feb 2000 | JP |
2000086427 | Feb 2000 | JP |
2000086429 | Mar 2000 | JP |
2000086438 | Mar 2000 | JP |
WO 8604916 | Aug 1986 | WO |
WO 8703783 | Jul 1987 | WO |
WO 9112793 | Sep 1991 | WO |
WO 9321763 | Nov 1993 | WO |
WO 9323008 | Nov 1993 | WO |
WO 9418261 | Aug 1994 | WO |
WO 9421233 | Sep 1994 | WO |
WO 9515741 | Jun 1995 | WO |
WO 9524887 | Sep 1995 | WO |
WO 9533000 | Dec 1995 | WO |
WO 9615761 | May 1996 | WO |
WO 9640044 | Dec 1996 | WO |
WO 9717057 | May 1997 | WO |
WO 9736573 | Oct 1997 | WO |
WO 9817243 | Apr 1998 | WO |
WO 9817705 | Apr 1998 | WO |
WO 9822078 | May 1998 | WO |
WO 9827162 | Jun 1998 | WO |
WO 9842298 | Oct 1998 | WO |
WO 9847470 | Oct 1998 | WO |
WO 9852534 | Nov 1998 | WO |
WO 9858623 | Dec 1998 | WO |
WO 9924002 | May 1999 | WO |
WO 0027350 | May 2000 | WO |
WO 0040216 | Jul 2000 | WO |
WO 0061080 | Oct 2000 | WO |
WO 0061081 | Oct 2000 | WO |
WO 0074519 | Dec 2000 | WO |
WO 0151020 | Jul 2001 | WO |
WO 0152799 | Jul 2001 | WO |
WO 0197758 | Dec 2001 | WO |
WO 0197773 | Dec 2001 | WO |
WO 0203932 | Jan 2002 | WO |
WO 0203935 | Jan 2002 | WO |
WO 0203950 | Jan 2002 | WO |
WO 0203951 | Jan 2002 | WO |
WO 0247605 | Jun 2002 | WO |
WO 0247608 | Jun 2002 | WO |
WO 0247619 | Jun 2002 | WO |
WO 0247620 | Jun 2002 | WO |
WO 0247622 | Jun 2002 | WO |
WO 0247627 | Jun 2002 | WO |
WO 0247629 | Jun 2002 | WO |
WO 0247630 | Jun 2002 | WO |
WO 0247658 | Jun 2002 | WO |
WO 0249583 | Jun 2002 | WO |
WO 0249601 | Jun 2002 | WO |
WO 02055030 | Jul 2002 | WO |
WO 02055031 | Jul 2002 | WO |
WO 02056845 | Jul 2002 | WO |
WO 02056847 | Jul 2002 | WO |
WO 02056848 | Jul 2002 | WO |
WO 02092047 | Nov 2002 | WO |
WO 02092663 | Nov 2002 | WO |
WO 02102322 | Dec 2002 | WO |
Number | Date | Country | |
---|---|---|---|
20020192168 A1 | Dec 2002 | US |
Number | Date | Country | |
---|---|---|---|
60330767 | Oct 2001 | US |