WO1998026754A1

WO1998026754A1 - Cosmetic composition in the form of an organic solution or dispersion containing at least a polymeric colouring agent

Info

Publication number: WO1998026754A1
Application number: PCT/FR1997/002305
Authority: WO
Inventors: Valérie de la Poterie; Patricia Lemann; Isabelle Bara
Original assignee: L'oreal
Priority date: 1996-12-16
Filing date: 1997-12-15
Publication date: 1998-06-25
Also published as: JP2000513005A; EP0944380A1; FR2757052A1; FR2757052B1; CA2274941A1

Abstract

The invention concerns a cosmetic composition in the form of a solution or dispersion containing at least an organic solvent and at least a film forming polymer and at least a polyurethane polymeric colouring agent. The invention also concerns a makeup method for keratinous fibres.

Description

Cosmetic composition in the form of an organic solution or dispersion comprising at least one polymeric dye

The subject of the invention is new cosmetic compositions comprising at least one polyurethane polymer dye, in particular a composition for making up keratin materials.

Usually used as coloring material in cosmetic compositions, either inorganic or organic pigments or lacquers, which are generally insoluble in aqueous and organic media, or dyes soluble in aqueous or organic media.

The pigments and lacquers used in the make-up field are of very diverse origin and chemical nature. Their physicochemical properties: particle size, specific surface, density etc. are therefore very different. These differences are reflected in variations in behavior: the ease of implementation, of dispersion, the stability to light, to temperature and the mechanical properties in the case of powders are specific to each coloring matter. These differences in behavior frequently require the formulator to readjust the composition of the formula when the shade of this formula is changed. They also limit the production of certain formulas in the form of monochrome. In particular, certain shades are impracticable because the pigments or lacquers which theoretically allow them to be obtained are incompatible with one another.

Mineral oxides are preferably used for coloring cosmetic compositions, because the organic lacquers and the soluble dyes show too much bleeding, which in particular has the effect of staining the ocular lenses in the case of eye-iiners or mascaras. However, these mineral pigments are dull and bland, so it is necessary to introduce a large amount of them in the formulas of mascara, nail polish and eyeliner to obtain a sufficiently saturated line. This high percentage of mineral particles strongly affects the gloss of the makeup film. In the field of make-up, color coverage and saturation are therefore often associated with the dullness of the film.

In the field of nail varnishes and lip lacquers, there are several very specific problems of dispersions, whether aqueous or organic:

First of all, there is the difficulty in dispersing the pigment particles, the sedimentation of these particles, and the problem of the adhesion of the varnish film, which is thwarted by the pigments. When pigments are used, they are prevented from sedimenting thanks to gelling agents which interfere with the fluidity of the formulas. These additives also tend to reduce the hardness of the varnish film and / or the water resistance of this film. Certain organic lacquers reduce the hardness of the film.

In the field of make-up, only organic lacquers have so far made it possible to obtain bright and intense colors (the mineral oxides have a very bland color). However, most organic lacquers exhibit very poor light fastness, which results in a very clear attenuation of their color over time. This phenomenon is further aggravated when these lakes are combined with photoreactive pigments such as titanium dioxide. However, these photo-reactive pigments are very widely used in make-up for protection against ultraviolet radiation. Consequently, the use of organic lacquers is fairly limited, which results in a limitation of the achievable shades.

The association of certain pigments, in particular iron oxides, with oils and certain active agents, including vitamins in particular, often results in the oxidation of these oils and these active agents.

In the varnish compositions, up to 10% of mineral oxide pigments are used to obtain a visible and acceptable coloring on the nails. However, such a high concentration of pigments leads to a strong decrease in the rheological performance of the varnish, and therefore produces a heterogeneous makeup on the nails. Organic lacquers, which allow much brighter colors to be obtained at lower percentages, are of little use for this application because, as already indicated, they disgorge easily and therefore risk staining the nails.

In addition, the use of soluble dyes in certain makeup compositions has the effect of accentuating wrinkles or streaks of the skin and / or nails, the dye coming to be fixed, by migration, preferably in these wrinkles or streaks. This effect is contrary to that of attenuation of the defects of the skin and / or the nail which one seeks to obtain by makeup. These soluble dyes often have the drawback of leaving spots on the skin and nails after removing makeup, with which they have a great affinity.

Finally, if the mineral pigments must be used in large quantities to obtain a satisfactory coloring, on the other hand, the soluble dyes have a very high coloring power, which leads to using them in infinitesimal quantities. Consequently, their dosage in a cosmetic formula under reproducible conditions is an extremely delicate operation.

It is also known from patent CH 475763 of nail varnishes, in an organic solvent medium, comprising coloring polymers of vinyl or acrylic type. However, these varnishes being transparent, the coloring polymers must not be covering in order to preserve the transparency of the varnish applied to the nail. These polymers are therefore not suitable for obtaining covering makeup, that is to say one which is not transparent.

There therefore remained the need to have new coloring material making it possible to overcome the drawbacks of the prior art. Also, it is with astonishment that the applicant has discovered new cosmetic compositions, comprising at least one polyurethane polymer dye, compositions which can be prepared according to invariable formulas, whatever the desired shade, with a very wide range of shades and very nuanced, with a high intensity of coloring associated with a shiny effect if desired, good coverage, with good lightfastness, including when the composition also comprises photoreactive pigments. These compositions are prepared from quantities of polyurethane polymer dye sufficiently low not to destabilize the formulas, but in quantities large enough to be easily dosed in a reproducible manner.

In addition, these compositions do not release dye on the skin and on the nails, which avoids the appearance of streaks on the made-up skin or of spots after makeup removal.

The subject of the invention is therefore a cosmetic composition in the form of an organic solution or dispersion comprising at least one organic solvent and at least one film-forming polymer, characterized in that it comprises at least one polyurethane polymer dye.

The subject of the invention is also the use of a polyurethane polymeric dye, in a composition for making up keratin materials in the form of an organic solution or dispersion comprising at least one organic solvent and at least one film-forming polymer. , to form a colored film on said keratin materials.

Another subject of the invention is the use of a polyurethane polymeric dye in a composition for making up keratin materials in the form of an organic solution or dispersion comprising at least one organic solvent and at least one film-forming polymer, which does not color the said keratin materials. The subject of the invention is also a process for making up keratin materials, characterized in that a composition as defined above is applied to said keratin materials.

The invention also relates to a process for the preparation of such a composition, characterized in that the polymeric dye is introduced into the composition in the form of a powder.

In the present invention, the term “organic dispersion” is understood to mean a dispersion of solid particles.

By polymeric dye is meant in the present description, a copolymer based on at least two distinct monomers, at least one of which is an organic dye monomer.

Such polymeric dyes are known to those skilled in the art. One can, for example, refer to the documents: US-5, 194,463

It is stated in these documents that these dyes have the property of not migrating, of not exuding, of not being extractable or sublimable. They are also known to be light-stable and have a strong coloring power. However, the media in which their use is envisaged in these documents are thermoplastic media, essentially for the manufacture of packaging. Nothing suggests the astonishing properties of these polymers once they are incorporated into cosmetic compositions.

These polyurethane polymeric dyes can be of the crystalline, semi-crystalline or amorphous type.

Usually, polyurethane polymeric dyes have an intrinsic viscosity of at least 0.20 (according to the method described in US Pat. No. 5,194,463). and can result from the polymerization of several monomers including:

(i) at least one di-isocyanate residue; (ii) at least one diol residue; and (iii) at least one diol dye monomer.

The di-isocyanate residues can be of the aliphatic, alicycic or aromatic type, such as for example 2,4-toiylene di-isocyanate, 2,6-tolylene di-isocyanate, 4,4'-biphenylene di-isocyanate, p-xylene di-isocyanate, methylene di-p-phenyl di-isocyanate, p-phenylene di-isocyanate, m-phenylene di-isocyanate, hexamethylene di-isocyanate, isophorone di-isocyanate, etc.

The diol residues can be chosen, for example, from ethylene glycol, 1, 2-propane diol, 1, 3-propane diol, 2-methyl-1, 3-propanediol, 1, 4-butane diol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,10-decane diol, 1,12-dodecane diol, 1,2-cyclohexane diol, 1,4-cyclohexanediol, 1,2-cyclohexane dimethanol, x, 8-bis (hydroxymethyl) -tricyclo- [5.2.1.0] decane, in which x represents 3, 4 or 5; diols comprising at least one oxygen atom in the chain such as, for example, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-bis (2-hydroxyethyl) benzene, 1,4-bis (2- hydroxyethyl) benzene, etc.

As a rule, these diols contain 2 to 18 and preferably 2 to 12 carbon atoms.

In particular, the polyurethane polymeric dyes described in US-A-5194463 and corresponding to the following formula (!):

-O- (I)

in which :

R is a divalent radical chosen from C2-C10 alkylene, C3-C8 cycloalkylene, arylene, alkylene (C1-C4) -arylene-alkylene (C1-C4), alkylene (C1-C4) -cycioalkylene (C3- C8) -alkylene (C1-C4), alkylene (C1-C4) -1, 2,3,4,5,6,7-octahydronaphthalene-2,6-diyl-alkylene (C1-C4),

R ¹ is a divalent organic radical comprising (a) from 1 to 100 mol% of coloring organic diol in which the hydroxyl groups of said diol are linked by an alkylene unit to the rest of the coloring compound, and (b) from 0 to 99 mol% of organic diols of formula HO-R ² -OH, in which R ² is a divalent radical chosen from the radicals C2-C18 alkylene, C3-C8 cycloalkylene, (C1-C4) alkylene-arylene-C1-C4 alkylene radicals ), alkylene (C1-C4) -cycloalkylene (C3-C8) -alkylene (C1-C4), alkylene (C1-C4) -1, 2,3,4,5,6,7-octahydronaphthalene-2,6- diyl-alkylene (C1 -C4), alkylene (C2-C4) -0-alkylene (C2-C4), alkylene (C2-C4) -S-alkylene (C2-C4), alkylene (C2-C4) -0- alkylene (C2-C4) -0-alkylene (C2-C4), and n is 2 or more.

Preferably, R1 comprises from 5 to 50 mole percent of coloring diol, and n ranges from 2 to 100.

The coloring diol monomers are selected from a variety of classes of chromophores. These classes of chrompophores can be chosen from anthraquinones, methines, bis-methines, azo-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinones, nitroarylamines, benzodifurane, 2 H-1-benzopyran-2-one, quinophthalones, triphenodioxazines, fluoridines, benzanthrones, indigo, thioindigo, xanthene, acridine, azine, oxazine, etc., These coloring monomers must bear at least two hydroxyl groups.

Reference may be made to US Patents 5,194,463 to find examples of coloring monomers. Usually, the polymeric dye comprises at least 5% by weight of coloring monomer, and does not comprise more than 55% by weight. Preferably, the percentage by weight of coloring monomer relative to the total weight of the copolymer ranges from 10 to 40%.

For the preparation of the polymeric dyes, reference may be made to the methods described in US Pat. No. 5,804,719.

The polymeric dye which can be used in the present invention can be in crude form or in the form of a dispersible powder.

Preferably, a polymeric dye is used in the form of a crude powder soluble in organic media.

For the preparation of a dispersible powder: A dispersion in an aqueous medium can be prepared in a known manner from water, from crude polymer dye as described in patent US-5, 194,463. For example, it is possible to start from the polymeric dye in the form of a powder or granule, and at least one ionic surfactant, preferably an anionic or amphoteric surfactant. The aionic and amphoteric surfactants can be preferably chosen from alkaline salts of C12-C24 fatty acids, soy phosphatides, phospholipids, lysophospholipids. These ionic surfactants are introduced in amounts preferably between 0.5 and 30%, and even more preferably between 1 and 10% by weight relative to the weight of the polymeric dye. Preferably, these dispersions further comprise at least one nonionic surfactant, which is advantageously chosen from polyoxyethylenated derivatives having a molecular weight greater than 300, preferably around 1000 to 15000 and a hydrophilic-lipophilic balance (or HLB balance) greater than or equal to 10.

For example, an aqueous dispersion of polymeric dye can be prepared by following the following steps: (i) preparation of an oil-in-water emulsion from water, of a solution of the polymeric dye in a volatile organic solvent in which it is soluble, in the presence of at least one ionic surfactant and optionally a nonionic surfactant; (ii) evaporation of the volatile organic solvent.

The volatile organic solvent which can be used for the implementation of this process must be immiscible with water and capable of dissolving the polymer. Preferably its boiling point is less than 100 ° C. It can for example be chosen from: hydrocarbon solvents such as n-hexane, cyclohexane, cyclopentane; chlorinated solvents such as methylene chloride, chloroform; alkyl esters of carboxylic acids, such as ethyl acetate; dialkyl ethers such as diisopropyl ether. Preferably, for the implementation of this process, a mixture of solvents is used comprising, in addition to the solvents described above, a volatile, polar, water-miscible solvent, such as acetone or a low molecular weight alkanol.

For more information on such a process, reference can be made to US Patents 5,043,376 and US 5,104,913.

The water from the aqueous dispersions described above can then be evaporated, for example by atomization or by lyophilization, in order to obtain a polymeric dye powder dispersible in other media, in particular in organic media. A dispersion of the polyurethane polymer dye is thus obtained in an organic solvent medium.

As just explained, this polymeric dye can be incorporated in the form of crude powder or dispersible powder. It can also be incorporated in the form of an organic pigment paste. The preparation of such a pigment paste is known to a person skilled in the art. The polymeric dyes which can be used in the compositions according to the invention can be introduced in amounts ranging from 0.01 to 10% and preferably from 0.5 to 2%.

The polymeric dyes described above have the advantage of having the same general chemical structure and the same physicochemical properties, in very different color ranges. Thus, a red pigment will have the same behavior as a yellow pigment. This homogeneity of behavior allows the manufacture of make-up compositions in the form of monochrome. When mixing monochrome to achieve a shade, there is no problem of incompatibility between the different colors.

These dyes have a coloring power superior to mineral oxides and close to that of organic lacquers: 4 to 5% is enough to give a bright and intense color varnish. The rheology problems are therefore greatly reduced. In addition, these colored polymers do not release dye. There is therefore no problem of appearance of streaks, staining of the skin or nails.

These polymeric dyes, used in the compositions according to the invention have a coloring power very close to that of organic lakes, and have a very high light stability, this even in the presence of titanium dioxide or zinc. They can therefore be used in place of organic lacquers in all makeup formulas. Their high light stability makes it possible to present the cosmetic compositions comprising them in transparent packaging. Thus, the user can choose more precisely the color of the product she is buying. In addition, they do not interfere with oils and / or active ingredients.

These brightly colored and intense polymeric dyes have the particularity of being sufficiently covering so that a small quantity is enough to color a cosmetic formula. The gloss of the film is therefore significantly improved. We obtain a makeup that is both covering, saturated and shiny. The dye particles are easily dispersed in the medium, without the need for special additives. No sedimentation is observed, even after a long period of storage. These polymeric dyes do not reduce the hardness of the varnish film.

The compositions according to the invention comprise, in an organic phase, at least one polymeric dye according to the invention and at least one film-forming polymer. The composition according to the invention therefore comprises at least one film-forming polymer which can be chosen, in particular, from alkyd, acrylic and / or vinyl resins, polyurethanes and polyesters, celluloses and cellulose derivatives such as nitrocellulose, and resins resulting from the condensation of formaldehyde with an arylsuifonamide, and mixtures thereof. The film-forming polymer is generally in solution, for example at 5-25% by weight, in an organic solvent such as toluene, xylene, ethyl and / or butyl acetate, ketones, glycol ethers, esters and alcohols such as ethanol, isopropanol or butanol, and mixtures thereof. In particular, the film-forming polymer is not colored, that is to say that it does not contain a coloring monomer.

The composition can also comprise a plasticizing agent and optionally rheological agents.

Among the plasticizing agents, mention may be made of citrates, phthalates, esters and / or camphor, generally used in an amount of 5-30% by weight relative to the weight of the composition.

Among the rheological agents, mention may be made of organophilic bentonites, cellulose derivatives, crosslinked polyacrylic acid derivatives, guar or carob gums, and also xanthan gums. The composition according to the invention can comprise colloidal silicic acid in an amount of 0.1% to 5% by weight, preferably in an amount of 1-2% by weight relative to the total weight of the composition. The composition according to the invention can also comprise any additive known to a person skilled in the art as being capable of being incorporated into such a composition, such as spreading agents, wetting agents, dispersing agents, foams, preservatives, UV filters, dyes, pigments, nacres, active ingredients such as N-butylformal, D-panthenol, phytantriol, vitamins and their derivatives, keratin and its derivatives, melanin, collagen, cystine, chitosan and its derivatives, ceramides, biotin, trace elements, glycerin, protein hydrolysates, phospholipids, moisturizers. Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, affected by the addition considered.

The composition preferably has an active material content of 5 to 70% by weight.

The composition according to the invention can be prepared by a person skilled in the art on the basis of his general knowledge and according to the state of the art.

The composition according to the invention may constitute a makeup composition for keratin materials, in particular the skin, eyes, nails or lips. It can be in the form of a product to be applied to the nails, such as a varnish, a base for nails or a care base for nails, or in the form of a product to be applied to the eyelashes, such as a mascara, or in the form of a product to be applied to the lips such as a lipstick, a lip gloss, or in the form of a product to be applied to the skin such as a base of complexion, blush, eyeshadow, eyeliner.

The invention is illustrated in more detail in the following examples. Example 1 Composition of Nail Polish

Nitrocellulose 10.8% KETJENFLEX MS 80 ( ^* ) 10.7%

CITROFLEX A4 ( ^** ) 6.5%

Toluene 31%

Butyl acetate 21.6%

Ethyl acetate 9.3% Isopropyl alcohol 7.7%

Stearakonium hectorite 1, 3%

1% red coloring pigment ( ^*** )

Citric acid 0.1%

( ^* ) toluene sulfonamide formaldehyde resin sold by the company

AKZO.

( ^** ) tributyl acetyl citrate sold by the company PFIZER.

(***) Coloring polyurethane comprising 30% of red coloring monomer prepared in accordance with Example 1 of patent US-5, 194,463.

Claims

1 - Cosmetic composition in the form of an organic solution or dispersion comprising at least one organic solvent and at least one film-forming polymer, characterized in that it comprises at least one polyurethane polymer dye.

2- Composition according to claim 1, characterized in that the polyurethane polymer dye results from the polymerization of several monomers including:

(i) at least one di-isocyanate residue;

(ii) at least one diol residue; and

(iii) at least one diol coloring monomer.

3- Composition according to Claim 1, characterized in that the polyurethane polymer dye corresponds to the following formula (I):

in which :

R is a divalent radical chosen from the C2-C10 alkylene, C3-C8 cycloalkylene, arylene, alkylene (C1-C4) -arylene-alkylene (C1 -C4), alkylene (C1-C4) -cycloalkylene (C3-) radicals C8) -alkylene (C1-C4), alkylene (C1 -C4) -1, 2,3,4,5,6,7-octahydronaphthalene-2,6-diyl-alkylene (C1 -C4),

R ¹ is a divalent organic radical comprising (a) from 1 to 100 mol% of coloring organic diol in which the hydroxyl groups of said diol are linked by an alkylene unit to the rest of the coloring compound, and (b) from 0 to 99 mol% organic diols of formula HO-R ² -OH, in which R ² is a divalent radical chosen from C2-C18 alkylene, C3-C8 cycloalkylene, alkylene (C1 - C4) -arylene-alkylene (C1-C4), alkylene (C1-C4) -cycloaikylene (C3-C8) -alkylene (C1-C4), alkylene (C1-C4) -1, 2,3,4,5, 6,7-octahydronaphthalene-2,6-diyl-alkylene (C1-C4), alkylene (C2-C4) -0-alkylene (C2-C4), alkylene (C2-C4) -S-alkylene (C2-C4) , alkylene (C2-C4) -0-alkylene (C2-C4) -0-alkylene (C2-C4), and n is 2 or more.

4- Composition according to any one of the preceding claims, characterized in that the polymeric dye comprises 5% to 55% by weight of at least one coloring monomer.

5- Composition according to claim 4, characterized in that the polymeric dye comprises 10% to 40% by weight of at least one coloring monomer.

6- Composition according to any one of claims 2 to 5, characterized in that the dyeing monomer diol is chosen from anthraquinones, methines, bis-methines, azo-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinones, nitroarylamines, benzodifurane, 2 H-1- benzopyran-2-one, quinophthalones, quinophthalones fluoridines, benzanthrones, indigo, thioindigo, xanthene, acridine, azine, oxazine, these coloring monomers carrying at least two hydroxyl groups.

7- Composition according to any one of the preceding claims, characterized in that it comprises 0.01 to 10% of polymeric dye.

8- Composition according to any one of the preceding claims, characterized in that it comprises 0.5 to 2% of polymeric dye.

9- Composition according to any one of the preceding claims, characterized in that it also comprises at least one compound chosen from titanium dioxide and zinc dioxide. 10- Composition according to any one of the preceding claims, characterized in that the film-forming polymer is chosen from alkyd, acrylic and / or vinyl resins, polyurethanes and polyesters, celluloses and cellulose derivatives and resins resulting from condensation formaldehyde with an arylsulfonamide, and mixtures thereof.

11- Composition according to any one of the preceding claims, characterized in that it comprises 5 to 25% by weight of film-forming polymer.

12- Composition according to any one of the preceding claims, characterized in that the organic solvent is chosen from toluene, xylene, ethyl and / or butyl acetate, ketones, glycol ethers, esters and alcohols.

13- Composition according to any one of the preceding claims, characterized in that it comprises 5 to 30% of at least one plasticizing agent.

14- Composition according to any one of the preceding claims, characterized in that it comprises at least one rheological agent chosen from organophilic bentonites, cellulose derivatives, crosslinked poiyacrylic acid derivatives, guar or carob gums and xanthan gums.

15- Composition according to any one of the preceding claims, characterized in that it comprises at least one additive chosen from cosolvents, spreading agents, wetting agents, dispersing agents, anti-foaming agents, preservatives, UV filters, dyes, pigments, nacres, active ingredients, vitamins, keratin and its derivatives, melanin, collagen, cystine, chitosan and its derivatives, ceramides, biotin, trace elements , glycerin, protein hydrolysates, phospholipids, moisturizers. 16- Composition according to any one of the preceding claims, characterized in that it comprises an active material content of 5 to 70% by weight.

17- Composition according to any one of the preceding claims, characterized in that it comprises at least one emulsifier.

18- Composition according to the preceding claim, characterized in that the emulsifier is chosen from: alkali salts of C12-C24 fatty acids, soy phosphatides, phospholipids, lysophospholipids.

19- Composition according to any one of the preceding claims, characterized in that it is in the form of a composition for making up keratin materials.

20- Composition according to any one of the preceding claims, characterized in that it is in the form of a nail varnish, a nail base, a nail care base, a mascara , an eyeliner, an eyeshadow, a foundation, a lipstick, a lip gloss, a blush.

21- Use of a polyurethane polymeric dye according to any one of claims 1 to 6, in a composition for making up keratin materials in the form of an organic solution or dispersion comprising at least one organic solvent and at least a film-forming polymer, to form a colored film on said keratin materials.

22- Use of a polyurethane polymer dye according to any one of claims 1 to 6, in a makeup composition for keratin materials in the form of an organic solution or dispersion comprising at least one organic solvent and at least one film-forming polymer, which does not color said keratin materials.

23- Process for making up keratin materials, characterized in that a composition according to any one of claims 1 to 20 is applied to said keratin materials.