Colored transparent or translucent cosmetic composition

Information

  • Patent Grant
  • 7030985
  • Patent Number
    7,030,985
  • Date Filed
    Tuesday, December 11, 2001
    23 years ago
  • Date Issued
    Tuesday, April 18, 2006
    18 years ago
Abstract
The invention relates to a transparent or translucent colored cosmetic composition for making up the skin, lips and superficial body growths comprising a transparent or translucent cosmetic base and at least one coloring agent in an amount such that the transmission of a 10 μm layer of the final composition, measured at the wavelength of the maximum of one of the absorption peaks of the coloring agent, is between 20% and 80%.
Description

The present invention relates to transparent or translucent cosmetic compositions capable of depositing a color on the skin, lips or superficial body growths, and to a process for preparing them.


The contribution of color to the skin, the lips and superficial body growths, in particular the hair, nails and eyelashes, has always been an important subject of research in the cosmetics field and very particularly in the field of make-up.


This contribution of color is generally carried out in the form of white or colored pigments, optionally in combination with dyes, in cosmetic bases giving rise to covering colored coats (lipstick, mascara, eye shadow, eyeliner, nail varnish, foundation) or semitransparent colored coats (foundation, eye shadow, lipstick, nail varnish), the desired effect generally being the production of an intense color or the masking of underlying imperfections.


In the field of foundations, for example, the masking of skin imperfections by covering or semicovering products is, however, virtually always accompanied, despite the application as a very fine layer, by a degree of visibility of the coat and by an unnatural appearance, which is generally undesirable.


Furthermore, there exist cosmetic compositions, such as care creams, which, after application as a fine layer, are entirely transparent or else sufficiently translucent (see WO 98/5234) to retain the natural appearance of the skin and to only lightly mask the imperfections of the latter. However, these products do not make it possible to color the physiological substrate on which they are deposited.


The inventors set a target of developing a novel range of noncovering make-up products which make it possible to deposit a color on the skin, lips or superficial body growths while remaining entirely “invisible”, that is to say products capable of giving coats which are sufficiently transparent or translucent to retain the natural appearance of the underlying surface.


A subject matter of the present invention is consequently transparent or translucent colored cosmetic compositions for making up the skin, lips and superficial body growths comprising a bulk transparent or translucent cosmetic base and at least one coloring agent in an amount such that the transmission of a 10 μm layer of the final composition, measured at the wavelength of the maximum of one of the absorption or scattering peaks of the coloring agent, is between 20% and 80%.


Another subject matter of the invention is a process for the preparation of a transparent or translucent colored cosmetic composition described above.


The cosmetic compositions which are a subject matter of the present invention thus make it possible to color the substrate on which they are applied while giving, by virtue of the high “transparency” of the coat obtained, a perfectly natural appearance to the surface thus covered.


The colored cosmetic compositions of the present invention have, as characteristic, not only the coloring capability and the transparency of the coat obtained but also a “bulk” transparent or translucent appearance. This property of bulk transparency or translucency means that a layer with a thickness arbitrarily set at 1 cm allows a portion of the visible light to pass through, either while scattering it (bulk translucent compositions) or without scattering it (bulk transparent compositions).


This transparent or translucent appearance is highly satisfactory from an esthetic viewpoint and can for this reason be of great commercial interest.


The cosmetic compositions of the present invention are characterized in that they have a transmission at a thickness of 10 μm, measured at the wavelength of the maximum of one of the absorption or scattering peaks of the coloring agent, of between 20% and 80%.


This layer thickness of 10 μm at which the measurements of transmission of the compositions of the present invention are carried out was chosen because it corresponds substantially to the thickness of a make-up coat obtained, for example, with a foundation or a lipstick. The values obtained by these measurements therefore give a good description of what is commonly known as “make-up rendering”, that is to say of the immediate visual impression which the make-up layer gives.


The transmission as defined here is equal to the ratio of the intensity of light transmitted by the sample (It) to the intensity of light transmitted by the control (I0), express as a %:

T(%)=It/I0


The inventors use specific sample carriers in order to be able to carry out measurements over a layer thickness of 10 μm.


They consist of a transparent glass or quartz slide, the size of which depends on the measuring cell of the spectrophotometer used (20 mm×10 mm×3 mm for a Cary 300), exhibiting at its surface a flat recess with a depth of 10 μm. This flat recess is filled with the sample and the excess is optionally leveled down using a slide, so as thus to obtain a perfectly even layer with a thickness of 10 μm.


The measurements are carried out using a double-beam UV/visible spectrophotometer, Cary 300 model from Varian, in transmission mode and by using, as control, a transparent slide (of quartz or of glass) with an identical thickness to that receiving the sample.


As indicated above, the transmission values indicated for the compositions according to the invention are those measured at the wavelength corresponding to the maximum of one of the absorption peaks (dye) or scattering peaks (pigment) of the coloring agent in the visible light region (λ=400 to 750 nm).


The error in the measurement of the transmission is ±5%.


The “bulk” transparency or translucency of the colored cosmetic compositions of the present invention is evaluated visually for a layer thickness of 1 cm.


The transparent or translucent colored cosmetic compositions are obtained by virtue of the combination of:

    • (1) a bulk transparent or translucent cosmetic base, and
    • (2) at least one appropriate coloring agent.


The cosmetic bases which can be used for the preparation of the compositions of the present invention can be composed of any cosmetically acceptable base which meets the conditions of transparency or of translucency essential for the production of the transparent or translucent colored cosmetic compositions.


These conditions of transparency or of translucency are:

    • (1) good bulk transparency or translucency of the colorant-free base, assessed visually for a thickness of 1 cm, and
    • (2) a transmission of the base comprising the colorant or colorants measured for a thickness of
    • 10 μm at the wavelength of the maximum of one of the absorption or scattering peaks of the coloring agent used of between 20% and 80%.
    • good bulk transparency or translucency of the colorant-free base, assessed visually for a thickness of 1 cm, and
    • a transmission of the base comprising the colorant or colorants, measured for a thickness of 10 μm at the wavelength of the maximum of one of the absorption or scattering peaks of the coloring agent used, of between 20% and 80%.


It can relate to hydrophilic or lipophilic phases with a liquid, thickened, gelled, pasty or solid consistency.


Preferably, the base of the composition is in the form of an aqueous or oily gel which is more or less rigid. More especially, this gel is a rigid gel presented in a dish or as a stick, preferably as a stick, and in the anhydrous form. In particular, this base is an anhydrous foundation or lipstick base.


The oily base comprises a fatty phase which is liquid at ambient temperature, such as those used conventionally in cosmetics. This fatty phase can comprise polar oils and/or nonpolar oils.


In particular, the polar oils of the invention are:

    • (1) hydrocarbonaceous vegetable oils with a high content of triglycerides composed of esters of fatty acids and of glycerol, the fatty acids of which can have various C4 to C24 chain lengths, it being possible for these chains to be linear or branched and saturated or unsaturated; these oils are in particular wheat germ, maize, sunflower, karite, castor, sweet almond, macadamia, apricot, soybean, cottonseed, alfalfa, poppy, pumpkinseed, sesame, cucumber, rapeseed, avocado, hazelnut, grape seed, blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, candlenut, passionflower or musk rose oil; or triglycerides of caprylic/capric acid, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel;
    • (2) synthetic oils or synthetic esters of formula RaCOORb in which Ra represents the residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and Rb represents a hydrocarbonaceous chain, in particular a branched hydrocarbonaceous chain, comprising from 1 to 40 carbon atoms, provided that Ra+Rb is ≧10 such as, for example, purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12 to C15 alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, isostearyl isostearate, or octanoates, decanoates or ricinoleates of alcohols or of polyalcohols; hydroxylated esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters;
    • (3) synthetic ethers having from 10 to 40 carbon atoms;
    • (4) C8 to C26 fatty alcohols, such as oleyl alcohol;
    • (5) C8 to C26 fatty acids, such as oleic acid, linolenic acid and linoleic acid; and
    • (6) mixtures thereof.


The nonpolar oils according to the invention are in particular silicone oils, such as volatile or nonvolatile and linear or cyclic polydimethylsiloxanes (PDMS) which are liquid at ambient temperature; polydimethylsiloxanes comprising alkyl or alkoxy side groups and/or alkyl or alkoxy groups at the chain end, which groups each have from 2 to 24 carbon atoms; phenylated silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or (2-phenylethyl)trimethylsiloxysilicates; volatile or nonvolatile and linear or branched hydrocarbons of synthetic or mineral origin, such as volatile liquid paraffins (isoparaffins, such as isododecane) or nonvolatile liquid paraffins, and their derivatives, liquid petrolatum, liquid lanolin, polydecenes, hydrogenated polyisobutene, such as parleam oil, squalane or arara oil; and their mixtures.


The oils are preferably 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 alkanes, such as parleam oil, isoparaffins, such as isododecane, squalane and their mixtures. These oils are advantageously used in combination with one or more phenylated silicone oils.


The liquid fatty phase preferably comprises at least one nonvolatile oil chosen in particular from hydrocarbonaceous oils of mineral, vegetable or synthetic origin, synthetic esters or ethers, silicone oils and their mixtures.


The total liquid fatty phase represents, in practice, from 5 to 99.95%, preferably from 10 to 80%, and more preferably from 20 to 75%, of the total weight of the composition.


This fatty phase is advantageously structured by a gelling agent for fatty phases, such as:

    • (1) gelling polyamides, in particular with a molecular mass of less than 100 000, and preferably less than 50 000, for example with a molecular mass ranging from 2 000 to 20 000, optionally comprising alkyl side groups or alkyl groups at the chain end having from 8 to 120 carbon atoms, and preferably from 12 to 60 carbon atoms,
    • (2) hydrophobic galactomannans comprising in particular from 1 to 6, and preferably from 2 to 4, OH groups per monosaccharide unit which are substituted by a C1-6, preferably C1-3, alkyl group,
    • (3) hydrophobic pyrogenic silicas,
    • (4) and the combinations of these gelling agents.


The gelling polyamides are, for example, the polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and of a diamine, including the compounds having more than 2 carboxyl groups and more than 2 amine groups, the carboxyl and amine groups of adjacent individual units being condensed by an amide bond. These polyamide resins 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 U.S. Pat. Nos. 3,645,705 and 3,148,125. More specifically, use is made of Versamid® 930 or 744.


Use may also be made of 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 U.S. Pat. No. 5,500,209.


The polyamides can also be those resulting from a polycondensation between a carboxylic diacid comprising at least 32 carbon atoms (in particular from 32 to 44 carbon atoms) and a diamine having at least 2 carbon atoms (in particular from 2 to 36 carbon atoms). The diacid is preferably a dimer of a fatty acid having at least 16 carbon atoms, such as oleic, linoleic or linolenic acid. The diamine is preferably ethylenediamine, hexylenediamine or hexamethylenediamine. If the polymers comprise one or two 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, more preferably from 12 to 24 carbon atoms, and even more preferably from 16 to 24 carbon atoms, for example, 18 carbon atoms.


These polymers are more especially those disclosed in U.S. Pat. No. 5,783,657 of Union Camp. Each of these polymers satisfies in particular the following formula (I):




embedded image



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; each of the R1 symbols independently denotes an alkyl or alkenyl group having at least 4 carbon atoms and in particular from 4 to 24 carbon atoms; each of the R2 symbols independently represents a C4 to C42 hydrocarbonaceous group, provided that 50% of the R2 groups represent a C30 to C42 hydrocarbonaceous group; each of the R3 symbols independently represents an organic group provided with at least 2 carbon atoms, with hydrogen atoms and optionally with one or more oxygen or nitrogen atoms; and each of the R4 symbols independently represents 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 side fatty chains within the meaning of the invention, represent from 15 to 40% of the total number of the ester and amide groups, and more preferably from 20 to 35%. Furthermore, n advantageously represents an integer ranging from 1 to 5, and preferably of greater than 2.


Preferably, R1 is a C12 to C22 alkyl group and more preferably a C16 to C22 alkyl group. Advantageously, R2 can be a C10 to C42 hydrocarbonaceous (alkylene) group. Preferably, at least 50%, and more preferably at least 75%, of the R2 symbols are groups having from 30 to 42 carbon atoms. The other R2 symbols are C4 to C19 and even C4 to C12 hydrogenated groups. Preferably, R3 represents a C2 to C36 hydrocarbonaceous group or a polyoxyalkylene group and R4 represents a hydrogen atom. More 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.


According to the invention, the structuring of the liquid fatty phase is preferably obtained using one or more polymers of formula (I). In general, the polymers of formula (I) are 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.


These polymers, because of their fatty chain(s), exhibit good solubility in oils and thus result in macroscopically homogeneous compositions, even with a high (at least 25%) level of polymer, in contrast to polymers devoid of a fatty chain.


Mention may be made, as preferred structuring polymers of formula (I) which can be used in the invention, of the polyamides modified by side fatty chains and/or end fatty chains having from 8 to 120 carbon atoms, and in particular from 12 to 68 carbon atoms, the end fatty chains being bonded to the polyamide backbone via ester groups. These polymers preferably comprise a fatty chain at each end of the polymer backbone and in particular of the polyamide backbone.


Mention may be made, as examples of structuring polyamides of formula (I) which can be used in the composition 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 respectively of approximately 600 or 4 000. The end ester groups result from the esterification of the remaining acid endings with cetyl alcohol or stearyl alcohol or their mixtures (also known as cetearyl alcohol).


The galactomannans are in particular ethylated guar derivatives having especially a degree of substitution of 2 to 3, such as those sold by Aqualon under the names N-Hance-AG-200® or N-Hance-AG-50®.


The pyrogenic silica preferably exhibits a particle size which can be nanometric to micrometric, for example ranging from approximately from 5 to 200 nm.


Pyrogenic silicas can be obtained by high temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas which exhibit a large number of silanol groups at their surfaces. Such hydrophilic silicas are, for example, sold under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by Degussa or under the names Cab-O-Sil HS-5®, Cab-O-Sil EH-5®, Cab-O-Sil LM-130®, Cab-O-Sil MS-55® and Cab-O-Sil M-5® by Cabot.


It is possible to chemically modify the surface of said silica by a chemical reaction which reduces the number of silanol groups. It is possible in particular to substitute silanol groups by hydrophobic groups and thus to obtain a hydrophobic silica. The hydrophobic groups can be:

    • (1) trimethylsiloxy groups, which are obtained in particular by treatment of pyrogenic silica in the presence of hexamethyldisilazane and are named “Silica silylate” according to the CTFA (6th edition, 1995); they are sold, for example, under the name Aerosil R812® by Degussa and under the name Cab-O-Sil TS-530® by Cabot;
    • (2) dimethylsilyloxy or polydimethylsiloxane groups, which are obtained in particular by treatment of pyrogenic silica in the presence of polydimethylsiloxane or of dimethyldichlorosilane and are named “Silica dimethyl silylate” according to the CTFA (6th edition, 1995); they are sold, for example, under the names Aerosil R972® and Aerosil R974® by Degussa and under the names Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by Cabot; and
    • (3) groups resulting from the reaction of the pyrogenic silica with alkoxysilanes or siloxanes; these treated silicas are, for example, those sold under the reference Aerosil R805® by Degussa.


When the gel is an aqueous gel, use may be made of any gelling agent for aqueous phases of the cellulose derivative type, such as hydroxyethylcellulose and carboxymethylcellulose, or acrylic derivative type, such as crosslinked copolymers of acrylic acid and of C10-30 alkyl acrylates, for example the Pemulen® series and Carbopol® 980, which are sold by Goodrich, clay derivatives of the sodium magnesium silicate type, such as Laponite XLS or XLG, sold by Laporte, and the combinations of these gelling agents. The aqueous gel can be a water-based gel or a gel based on a water/alcohol mixture.


The gelling agent represents from 0.05 to 90% by weight, preferably from 2 to 60% by weight, and more preferably from 5 to 40% by weight, of the total weight of the colored cosmetic composition.


The transparent or translucent cosmetic bases used according to the invention are preferably substantially colorless.


One or more coloring agents is introduced, according to the present invention, into these transparent or translucent cosmetic bases.


According to the present invention, the term “coloring agent” encompasses in particular water-soluble or fat-soluble dyes, pigments, pearlescence agents, lakes and their mixtures.


Mention may be made, as water-soluble dyes, of synthetic dyes, such as fuchsin, plant extracts, such as extracts of sorghum, of Pterocarpus soyauxii, of Monascus, of Lawsonia inermis, of Mercurialis perenis, of Helianthus aanus, of Impatiens balsamina, of Curcuma longa, of Phytolacca decandra, of Solidago aureus, of Juglans regia, of Iris germanica, of Alkanna tinctoria, of Chrozophoro tinctoria or of Isatis tinctoria, and the mixtures of these dyes.


The fat-soluble dyes are, for example, Sudan red III (CTFA: D&C Red 17), lutein, quinizarin green (CTFA: D&C Green 6), alizurol purple SS (CTFA: D&C Violet No. 2), carotenoid derivatives, such as lycopene, β-carotene, bixin or capsantein, annatto and fuchsin derivatives (see Example 2), and their mixtures.


A number of these dyes, such as extracts of Pterocarpus soyauxii, Monascus and Lawsonia inermis, have a strong affinity for the skin and can thus confer a semipermanent coloring thereon, that is to say a coloring which withstands being washed several times.


The term “pigments” should be understood as meaning white or colored, inorganic or organic and coated or uncoated particles. Mention may be made, for example, of titanium, zirconium or cerium dioxides, zinc, iron or chromium oxides, ferric blue, chromium hydrate, carbon black, ultramarines (polysulfides of aluminum silicates), manganese violet, manganese pyrophosphate and some metal powders, such as silver or aluminum powders, and their mixtures.


The term “pearlescence agents” is understood to mean white nacreous pigments, such as mica covered with titanium oxide or with bromuth oxychloride, and colored nacreous pigments, such as titanium oxide-coated mica covered with iron oxides, ferric blue or chromium oxide or with a precipitated typical organic pigment.


The lakes which can be used in the compositions of the present invention are, for example, lakes based on cochineal carmine or based on calcium, barium, aluminum, strontium or zirconium salts, on acid dyes, and their mixtures.


The amount of coloring agent is determined for the present invention. This is because this amount directly determines the transmission of the composition, which, for a thickness of 10 μm, has to be between 20% and 80% at the wavelength corresponding to the maximum of one of the absorption or scattering peaks of the coloring agent.


Below a certain amount of coloring agent (transmission at 10 μm of greater than 80%), the composition will give rise to a coat which is sufficiently transparent or translucent to retain the natural appearance of the skin, lips or superficial body growths but it will not allow a coloring visible to the naked eye to be introduced.


On the other hand, for an excessively high proportion of coloring agent (transmission at 10 μm of less than 20%), the color of the make-up coat will certainly be visible but the transparency or the translucency of the latter will be insufficient to retain the natural appearance of the skin. Furthermore, cosmetic compositions comprising an excessively high proportion of coloring agent will exhibit unsatisfactory bulk transparency or translucency.


In a preferred embodiment of the invention, the colored cosmetic compositions have a transmission, measured for a thickness of 10 μm, at the wavelength corresponding to the maximum of one of the absorption or scattering peaks of the coloring agent, of between 25% and 80%.


The process for determining the appropriate amount of coloring agent which makes it possible to obtain transparent or translucent colored compositions according to the present invention will be described in more detail below.


The appropriate amount of coloring agent will obviously depend on its physicochemical properties, such as its solubility in the cosmetic base, its particle size or its molar coefficient of absorption (ε).


The transparent or translucent colored cosmetic compositions according to the present invention generally comprise from 0.05% to 3% by weight, and preferably from 0.1 to 1% by weight, of coloring agent(s), on the basis of the total weight of the colored cosmetic composition. For the pearlescence agents, it is possible to range up to 3% by weight; for the pigments, the lakes or the dyes, the range preferably only extends up to 1% by weight.


In a preferred embodiment of the present invention, the colored cosmetic composition comprises at least one water-soluble or fat-soluble dye which is soluble in the cosmetic base.


In another particularly advantageous embodiment of the invention, the colored cosmetic composition comprises, as coloring agent(s), solely one or more dyes which are soluble in the cosmetic base and is devoid of insoluble coloring agents of pigment, pearlescence agent or lake type.


In a more particularly preferred embodiment of the present invention, the cosmetic base is a lipophilic base comprising one or more lipophilic dyes which are soluble in the latter.


This is because such compositions, comprising solely soluble dyes, have a good coloring power in combination with excellent transparency properties due to the absence of scattering of the light by insoluble particles.


Another subject matter of the present invention is a process for the preparation of the transparent or translucent colored cosmetic compositions of the present invention which has, as main characteristics:

    • (1) choosing an appropriate transparent or translucent cosmetic base, and
    • (2) apportioning the coloring agent(s), that is to say the incorporation of an appropriate amount of coloring agent(s) which makes it possible to solve the technical problem at the source of the invention, that is to say the production of a colored coat having a transmission (at 10 μm and at λmax) of between 20% and 80%.


The determination of the appropriate amount of coloring agent comprises the steps consisting of:

    • (1) selecting a transparent or translucent cosmetic base as described above,
    • (2) preparing a series of samples of this transparent or translucent cosmetic base comprising increasing amounts of a coloring agent dissolved or dispersed in said cosmetic base,
    • (3) spreading each of the samples thus prepared over a transparent slide exhibiting a recess with a depth of 10 μm,
    • (4) optionally leveling out the excess of the sample, so as to obtain a layer with a thickness of 10 μm,
    • (5) measuring, for each of the samples, the transmission of said layer at the wavelength corresponding to the maximum of one of the absorption or scattering peaks of the coloring agent, and
    • (6) plotting the transmission=f(concentration of the coloring agent) calibration curve.


Colored cosmetic compositions are subsequently prepared by incorporating one or more coloring agents in a transparent or translucent cosmetic base which is identical to or different than that selected in step (1) above and which is in the liquid state, each of the coloring agents being incorporated in an amount giving, from the calibration curve prepared for each coloring agent, a transmission (at 10 μm) of between 20% and 80%, preferably between 25% and 80%.


To receive the coloring agent, the cosmetic base must, of course, be in the liquid state. The liquid consistency can be a property of the base as such at ambient temperature or it can be the result of the melting or dissolution of a cosmetic base which is solid at ambient temperature.


The solid anhydrous cosmetic bases preferred according to the present invention are preferably liquefied by melting at a temperature slightly above their melting point.


The present invention is illustrated by the following examples:







EXAMPLE 1














Lipstick



















Uniclear ® 100
25%



Octyldodecanol
10%



Rocou ®
0.2% 




(coloring active material)



Parleam oil
q.s. for 100% by weight







Uniclear ® 100: condensate of a hydrogenated C36 diacid and of ethylenediamine esterified with stearyl alcohol (weight-average molar mass approximately 4 000), sold by Arizona Chemical.



Rocou ®: 4% solution of annatto seeds in soybean oil (CI: 75120), sold by Warner-Jenkinson.






The Uniclear® 100 and the oils are introduced into a casserole. The combined contents are stirred magnetically and are heated in a first step to 100° C. to bring the Uniclear to the liquid state. Heating is then continued as far as the temperature necessary to produce a homogeneous transparent liquid. The mixture is then placed at 10° C. above this temperature. The dye is introduced into the mixture and the combined contents are homogenized with magnetic stirring for 1 hour. The composition is cast in a mold heated at 45° C. to form a stick which is placed, after solidification has begun, in a freezer for 15 minutes (−21° C.).


The composition obtained has a bulk translucent appearance (1 cm) and gives rise to a completely transparent coat with an orange color having a transmission at 498 nm (λmax of the dye) and at a thickness of 10 μm of 78%.


EXAMPLE 2














Lipstick



















Uniclear ® 100
25%



Octyldodecanol
10%



MMB Red ® 33/3 complex
0.2% 




(coloring active material)



Parleam oil
q.s. for 100% by weight







Uniclear ® 100: condensate of a hydrogenated C36 diacid and of ethylenediamine esterified with stearyl alcohol (weight-average molar mass approximately 4 000), sold by Arizona Chemical.



MMB Red ® 33/3 complex: dye sold under this name by Phytocos and denoting the mixture: disodium salt of fuchsin acid D/lysine palmitate-myristate/dipropylene glycol/benzoic acid/phenoxyethanol/3% solution of D&C Red No. 33 (CI 17200)/preservatives: methyl, butyl, ethyl, propyl p-hydroxybenzoate.






A stick is prepared by the same process as in Example 1.


The composition obtained has a bulk translucent appearance (1 cm) and gives rise to a completely transparent coat with a fuchsia pink color having a transmission at 530 nm (λmax of the dye) and at a thickness of 10 μm of 40%.

Claims
  • 1. A transparent or translucent colored cosmetic composition for making up at least one of skin, lips and superficial body growths, comprising a bulk transparent or translucent cosmetic base and at least one coloring agent in an amount such that the transmission of a 10 μm layer of said cosmetic composition measured at the wavelength of the maximum of the absorption or scattering peak of the at least one coloring agent ranges from 20% to 80%.
  • 2. The colored cosmetic composition according to claim 1, wherein the transparent or translucent cosmetic base is a substantially colorless base.
  • 3. The colored cosmetic composition according to claim 1, wherein the cosmetic base is chosen from aqueous gels and oily gels.
  • 4. The colored cosmetic composition according to claim 3, wherein the gel is in stick form.
  • 5. The colored cosmetic composition according to claim 1, wherein the base is an anhydrous gel formed from a fatty phase which is liquid at ambient temperature comprising an oil chosen from polar oils and nonpolar oils, wherein the fatty phase is structured by a gelling agent for fatty phases which is chosen from at least one of hydrophobic pyrogenic silicas, gelling polyamides, and hydrophobic galactomannans.
  • 6. The colored cosmetic composition according to claim 5, wherein the gelling polyamide corresponds to the formula (I): in which n represents a whole number such that the number of ester groups ranges from 10% to 50% of the total number of the ester and amide groups;R1, which may be identical or different, represents a group chosen from alkyls having at least 4 carbon atoms and alkenyls having at least 4 carbon atoms;R2, which may be identical or different, represents a C4 to C42 hydrocarbonaceous group, provided that 50% of the R2 groups represent a C30 to C42 hydrocarbonaceous group;R3, which may be identical or different, represents an organic group having at least 2 carbon atoms, hydrogen atoms, and optionally at least one atom chosen from oxygen atoms and nitrogen atoms; andR4, which may be identical or different, represents a group chosen from hydrogen atoms, C1 to C10 alkyls, optionally directly bonded 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.
  • 7. The colored cosmetic composition according to claim 6, wherein R1, which may be identical or different, represents a group chosen from alkyls having 4 to 24 carbon atoms and alkenyls having 4 to 24 carbon atoms.
  • 8. The colored cosmetic composition according to claim 1, wherein the at least one coloring agent is chosen from at least one of water-soluble dyes, fat-soluble dyes, pigments, pearlescence agents, and lakes.
  • 9. The colored cosmetic composition according to claim 8, wherein the water-soluble dye is chosen from at least one of extracts of sorghum, Pterocarpus soyauxii, Monascus, Lawsonia inermis, Mercurialis perenis, Helianthus aanus, Impatiens balsamina, Curcuma longa, Phytolacca decandra, Solidago aureus, Juglans regia, Iris germanica, Alkanna tinctoria, Chrozophoro tinctoria, and Isatis tinctoria.
  • 10. The colored cosmetic composition according to claim 8, wherein the fat-soluble dye is chosen from at least one of Sudan red III, lutein, quinizarin green, alizural purple SS, carotenoid derivatives, annatto derivatives, and fuchsin derivatives.
  • 11. The colored cosmetic composition according to claim 10, wherein the carotenoid derivative is chosen from lycopene, β-carotene, bixin, and capsantein.
  • 12. The colored cosmetic composition according to claim 8, wherein the pigment is chosen from at least one of white inorganic pigments, colored inorganic pigments, white coated inorganic pigments, colored coated inorganic pigments, white organic pigments, and colored organic pigments.
  • 13. The colored cosmetic composition according to claim 12, wherein the pigment is chosen from at least one of titanium dioxide, zirconium dioxide, cerium dioxide, zinc oxide, iron oxide, chromium oxide, ferric blue, chromium hydrate, carbon black, ultramarines, manganese violet, manganese pyrophosphate, and metal powders.
  • 14. The colored cosmetic composition as claimed in claim 13, wherein the metal powder is chosen from silver powders and aluminum powders.
  • 15. The colored cosmetic composition according to claim 8, wherein the pearlescence agent is chosen from mica covered with at least one of titanium oxide and bismuth oxychloride and titanium oxide-coated mica covered with at least one of iron oxide, ferric blue, chromium oxide, and precipitated organic pigments.
  • 16. The colored cosmetic composition according to claim 8, wherein the lake is chosen from at least one of lakes based on cochineal carmine, lakes based on at least one of calcium salts, barium salts, aluminum salts, strontium salts, and zirconium salts, and lakes based on acid dyes.
  • 17. The colored cosmetic composition according to claim 8, wherein the composition comprises at least one dye chosen from water-soluble dyes and fat-soluble dyes, wherein the dye is soluble in the cosmetic base.
  • 18. The colored cosmetic composition according to claim 17, wherein the composition comprises, as the at least one coloring agent, at least one dye which is soluble in the cosmetic base and wherein the composition is devoid of insoluble coloring agents chosen from pigments, pearlescence agents, and lakes.
  • 19. The colored cosmetic composition according to claim 17, wherein the cosmetic base is a lipophilic base and wherein the composition comprises at least one lipophilic dye which is soluble in the lipophilic base.
  • 20. The colored cosmetic composition according to claim 1, wherein the at least one coloring agent is present in an amount such that the transmission of the 10 μm layer of the composition measured at the wavelength of the maximum of the absorption or scattering peak of the at least one coloring agent ranges from 25% to 80%.
  • 21. The colored cosmetic composition according to claim 1, wherein the amount of the at least one coloring agent ranges from 0.05% to 3% by weight with respect to the total weight of the composition.
  • 22. The colored cosmetic composition according to claim 1, wherein the amount of the at least one coloring agent ranges from 0.1% to 1% by weight with respect to the total weight of the composition.
  • 23. The colored cosmetic composition according to claim 1, wherein the composition is chosen from anhydrous lipstick forms and anhydrous foundation forms.
  • 24. A process for the preparation of a transparent or translucent colored cosmetic composition for making up skin, lips and superficial body growths, comprising a bulk transparent or translucent cosmetic base and at least one coloring agent in an amount such that the transmission of a 10 μm layer of the composition measured at the wavelength of the maximum of the absorption or scattering peak of the at least one coloring agent ranges from 20% to 80%, wherein the process comprises: (1) selecting the cosmetic base,(2) preparing a series of samples of the cosmetic base comprising increasing amounts of the at least one coloring agent dissolved or dispersed in the cosmetic base,(3) spreading each of the samples thus prepared over a translucent slide having a recess with depth of 10 μm,(4) optionally leveling the sample so as to obtain an even layer with a thickness of 10 μm,(5) measuring, for each of the samples, the transmission of the layer at the wavelength corresponding to the maximum of the absorption or scattering peak (λmax) of the at least one coloring agent,(6) plotting a calibration curve wherein the values of the transmission at (λmax) is a function of the concentration of the at least one coloring agent, and(7) incorporating the at least one coloring agent in a transparent or translucent cosmetic base which is identical or different from that selected in step (1) above and which is in a liquid state, the at least one coloring agent being incorporated in the cosmetic base in an amount which, according to the calibration curve prepared for each coloring agent, results in a transmission at 10 μm of ranging from 20% to 80%.
  • 25. The process as claimed in claim 24, wherein the transmission in step (7) ranges from 25% to 80%.
Priority Claims (1)
Number Date Country Kind
00/16178 Dec 2000 FR national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/FR01/03937 12/11/2001 WO 00 8/9/2002
Publishing Document Publishing Date Country Kind
WO02/47627 6/20/2002 WO A
US Referenced Citations (268)
Number Name Date Kind
2379413 Bradley Jul 1945 A
2450940 Cowan et al. Oct 1948 A
2463264 Graenacher Mar 1949 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
3157681 Fischer 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
4247411 Vanlerberghe et al. Jan 1981 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
4367390 Balleys et al. Jan 1983 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
4724137 Hoppe et al. Feb 1988 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
5166355 Leistner et al. Nov 1992 A
5186318 Oestreich et al. Feb 1993 A
5196260 Dirschl et al. Mar 1993 A
5223559 Arraudeau et al. Jun 1993 A
5237071 Leistner et al. Aug 1993 A
5252323 Richard et al. Oct 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 Ross 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
5585091 Pelzer et al. Dec 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
5695747 Forestier et al. Dec 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
5795565 Eteve et al. Aug 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
5849909 Richard 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 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
5955060 Huglin et al. Sep 1999 A
5959009 Konik et al. Sep 1999 A
5961998 Arnaud et al. Oct 1999 A
5962452 Haase 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
5976512 Huber Nov 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
6093385 Habeck et al. Jul 2000 A
6103249 Roulier et al. Aug 2000 A
6106820 Morrissey et al. Aug 2000 A
6111055 Berger et al. Aug 2000 A
6132745 Marchi-Lemann et al. Oct 2000 A
6156325 Farer et al. Dec 2000 A
6156804 Chevalier et al. Dec 2000 A
6159455 Habeck et al. Dec 2000 A
6165454 Patel et al. Dec 2000 A
6165971 Oppenlander et al. Dec 2000 A
6171347 Kunz et al. 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
6361764 Richard et al. Mar 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
6503522 Lawson et al. Jan 2003 B1
6506716 Delplancke et al. Jan 2003 B1
6545174 Habeck et al. Apr 2003 B1
6552160 Pavlin Apr 2003 B1
6649173 Arnaud et al. Nov 2003 B1
6682748 De La Poterie et al. Jan 2004 B1
6716420 Feng et al. Apr 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
20010014313 Roulier et al. Aug 2001 A1
20010028887 Douin et al. Oct 2001 A1
20010031280 Ferrari et al. Oct 2001 A1
20010033846 Roulier et al. Oct 2001 A1
20020010179 Richard et al. Jan 2002 A1
20020044918 Bara Apr 2002 A1
20020058053 Nakanishi et al. May 2002 A1
20020081323 Nakanishi 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
Foreign Referenced Citations (212)
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 26 184 Dec 1998 DE
197 50 246 May 1999 DE
197 55 649 Jun 1999 DE
198 55 649 Jun 2000 DE
199 51 010 Apr 2001 DE
0 169 997 Feb 1986 EP
0 295 886 Dec 1988 EP
0 370 470 May 1990 EP
0 374 332 Jun 1990 EP
0 412 710 Feb 1991 EP
0 444 633 Sep 1991 EP
0 507 692 Oct 1992 EP
0 517 104 Dec 1992 EP
0 518 772 Dec 1992 EP
0 518 773 Dec 1992 EP
0 557 196 Aug 1993 EP
0 570 838 Nov 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
0 669 323 Aug 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
0 775 698 May 1997 EP
0 790 243 Aug 1997 EP
0 796 851 Sep 1997 EP
0 797 976 Oct 1997 EP
0 820 764 Jan 1998 EP
0 847 752 Jun 1998 EP
0 863 145 Sep 1998 EP
0 877 063 Nov 1998 EP
0 878 469 Nov 1998 EP
0 879 592 Nov 1998 EP
0 887 073 Dec 1998 EP
0 893 119 Jan 1999 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
0 933 376 Aug 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
0 967 200 Dec 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
1 044 676 Oct 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
2 315 991 Jan 1977 FR
2 416 008 Aug 1979 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
2 796 550 Jan 2001 FR
2 802 806 Jun 2001 FR
2 804 014 Jul 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
2 817 742 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
1 539 625 Jan 1979 GB
2 014 852 Sep 1979 GB
2 021 411 Dec 1979 GB
2 147 305 May 1985 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
02127568 May 1990 JP
02200612 Aug 1990 JP
02207014 Aug 1990 JP
02216279 Aug 1990 JP
03014683 Jan 1991 JP
04346909 Dec 1993 JP
07179795 Jul 1995 JP
07267827 Oct 1995 JP
08225316 Sep 1996 JP
0920631 Jan 1997 JP
09255560 Sep 1997 JP
09295922 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 Mar 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 9304665 Mar 1993 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 9825922 Jun 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
WO9924002 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 0247606 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
WO 05013887 Feb 2005 WO
Related Publications (1)
Number Date Country
20030026772 A1 Feb 2003 US