JP2010513247A - Use of colored or fluorescent hybrid particles to treat keratin fibers - Google Patents

Abstract

  The present invention relates to the use of hybrid particles obtained from organosilane compounds having colored molecules for dyeing keratin fibers, in particular hair. The invention also relates to a method for dyeing keratin fibres, in particular hair, comprising application to a keratin fibre of a composition comprising hybrid particles obtained from an organosilane compound having colored molecules in a cosmetic medium. The particles useful for the present invention can obtain rapid staining or optical brightening of keratin fibers, depending on the colored molecules attached to the organosilane.

Description

  The present invention relates to the use of colored or fluorescent organosilane particles in the field of cosmetics, in particular hair dyeing.

In the field of staining of keratin fibers, especially human keratin fibers such as hair, there are two main staining aspects:
-Direct staining or semi-permeable staining is to provide coloring via colored molecules that adsorb to the surface of keratin fibers and / or penetrate by diffusion into the surface layer of keratin fibers. In general, leave-on times are fairly short and mild staining conditions preserve keratin fiber integrity, but the color obtained through this staining mode is shown to be less wash resistant, and only 4 or 5 times. It falls off after shampooing. Furthermore, the range of shades obtained is generally limited;
Oxidative dyeing or permanent dyeing is a colorless or weakly colored molecule known as an oxidation base such as ortho- or para-phenylenediamine, ortho- or para-aminophenol, or heterocyclic compounds in the presence of an oxidizing agent. The oxidative condensation of This reaction leads to the formation of colored polymer compounds in keratin fibers. The main advantages of oxidative dyeing lie in the resistance to external stimuli such as washing and light, bad weather, perm treatment, perspiration, and rubbing, and in the lifetime of the resulting coloration in the production of a wide range of shades. However, chemical staining conditions such as pH and oxidizing media lead to keratin fiber degradation. Furthermore, this dyeing mode requires a relatively long leave-on time.

  In the field of cosmetics and pharmaceuticals, it is already well known to use sol-gel particles in which reagents are encapsulated. In particular, document WO 2004/082122 describes sol-gel particles encapsulated with dyes or fluorescent dyes, which could be used in hair care products or pharmaceuticals.

WO2004 / 081222

Because the particles are porous, when these particles are used in a cosmetic composition, the migration of the dye out of the particles is observed, which initially limits the light stability benefits it can obtain. The problem then lies in the fact that it has been found to reduce the harmlessness of the system.
Hybrid sol-gel nanoparticles composed of colloidal silica with covalently bound fluorescent dyes are already well known. Such nanoparticles may have a core / shell structure, where the core is derived from standard alkoxysilanes in sol-gel synthesis. Such particles are described, for example, in “Multicolour FRET silica nanoparticles by single wavelength excitation”, Lin Wang and Weihong Tan, Nano Letters, 2006, vol. 6, No. 1, 84-88; “Bright and stable core-shell fluorescent silica. nanoparticles ", Nano Letters, 2005, vol. 5, No. 1, 113-117. These nanoparticles are recommended for use in biological probes because of their very strong fluorescence power.

  The object of the present invention is to provide a novel system for staining keratin fibers which does not have the disadvantages of existing systems. In particular, the object of the present invention is to provide a novel dye system which simultaneously has the harmlessness, stability and completeness of the resulting coloration and the tolerance of keratin fibers, allowing a wide range of obtained shades. That is.

  This object is achieved according to the invention, and one subject of the invention is the use of hybrid particles obtained from organosilane compounds with colored molecules for dyeing keratin fibres, in particular hair.

  The subject of the present invention is also a method for dyeing keratin fibres, in particular hair, comprising the application to a keratin fibre of a composition comprising hybrid particles obtained from organosilane compounds having colored molecules in a cosmetic medium.

  Particles that are useful for the present invention can obtain rapid staining or optical lightening of keratin fibers, depending on the colored molecules attached to the organosilane. Furthermore, the present invention can provide rapid staining or optical brightening without degrading keratin fibers.

  For the purposes of the present invention, the term “optical lightening” refers to naturally or artificially colored keratin fibers without the use of compounds that destroy natural or artificial colored pigments present in keratin fibers. It means visual lightening effect.

  For the purposes of the present invention, the term “organosilane having a colored molecule” means that the colored molecule is bonded via a covalent bond of the organosilane to silicon.

  The colored molecule may be any group derived from a direct dye, pigment, or fluorescent dye that is standard in the field of dyeing. Examples include pigments, direct dyes, and fluorescent dyes conventionally used in hair dyeing. In particular, mention may be made of nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine, and nitrobenzene triarylmethane type dyes, or natural dyes.

  Non-limiting embodiments of the benzene direct dye include the following compounds: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-β-hydroxyethylaminobenzene, 1-amino 2-nitro-4-bis (β-hydroxyethyl) -aminobenzene, 1,4-bis (β-hydroxyethylamino) -2-nitrobenzene, 1-β-hydroxyethylamino-2-nitro-4-bis (β-hydroxyethylamino) benzene, 1-β-hydroxyethylamino-2-nitro-4-aminobenzene, 1-β-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) amino Benzene, 1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene, 1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene, 1,2-diamino-4- Nitrobenzene, 1-amino-2-β-hydroxyethylamino-5-nitrobenzene, 1,2- Bis (β-hydroxyethylamino) -4-nitrobenzene, 1-amino-2-tris (hydroxymethyl) ethylamino-5-nitrobenzene, 1-hydroxy-2-amino-5-nitrobenzene, 1-hydroxy-2-amino -4-nitrobenzene, 1-hydroxy-3-nitro-4-aminobenzene, 1-hydroxy-2-amino-4,6-dinitrobenzene. 1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene, 1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene, 1-methoxy-2-β-hydroxyethylamino-5- Nitrobenzene, 1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene, 1-β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene, 1-β-hydroxyethylamino-4-β, γ-hydroxypropyloxy-2-nitrobenzene, 1-β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, 1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene, 1-β β-hydroxyethylamino-3-methyl-2-nitrobenzene, 1-β-aminoethylamino-5-methoxy-2-nitrobenzene, 1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene, 1-hydroxy - 2-chloro-6-amino-4-nitrobenzene, 1-hydroxy-6-bis (β-hydroxyethyl) amino-3-nitrobenzene, 1-β-hydroxyethylamino-2-nitrobenzene, 1-hydroxy-4-β -Hydroxyethylamino-3-nitrobenzene.

  Azo direct dyes include the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714945, the contents of which form an interpolated part of the present invention.

  These compounds include, among others, the following dyes: 1,3-dimethyl-2-[[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2- [ (4-Aminophenyl) azo] -1H-imidazolium chloride, 1-methyl-4-[(methylphenylhydrorazono) methyl] pyridinium methyl sulfate.

  Azo direct dyes include the following dyes listed in the Color Index International 3rd edition: Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16 Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24, Disperse Black 9.

  Also mentioned are 1- (4′-aminodiphenylazo) -2-methyl-4-bis (β-hydroxyethyl) aminobenzene, and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid. It is done.

  The quinoline direct dyes include the following dyes: Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99, and the following compounds: 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1-aminopropylamino-4-methylamino Anthraquinone, 1-aminopropylaminoanthraquinone, 5-β-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylaminoanthraquinone, 1,4-bis (β, γ-dihydroxypropylamino) anthraquinone.

Azine dyes include the following compounds:
−Basic Blue 17 and Basic Red 2

  Triarylmethane dyes include the following compounds: Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7, Acid Violet 49, Basic Blue 26, Acid Blue 7.

Indoamine dyes include the following compounds:
-2-β-hydroxyethylamino-5- [bis (β-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone-2-β-hydroxyethylamino-5- (2'-methoxy-4 ' -Amino) anilino-1,4-benzoquinone-3-N- (2'-chloro-4'-hydroxy) phenylacetylamino-6-methoxy-1,4-benzoquinoneimine-3-N- (3'-chloro -4'-methylamino) phenylureido-6-methyl-1,4-benzoquinoneimine-3- [4'-N- (ethyl, carbamylmethyl) amino] phenylureido-6-methyl-1,4-benzoquinone Imin.

  Natural direct dyes that may be used according to the present invention include Lawson, juglone, alizarin, perpurine, carminic acid, kermesic acid, perprogalin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, and apigenidine.

  Useful fluorescent dyes include "Molecular Probes Handbook of Fluorescent Probes and Research Chemical", 6th edition, edited by RP Haugland (1996), or Ullmann's Encyclopaedia of Industrial Chemistry, 2004, 7th edition, "Fluorescent Dyes" chapter And fluorescent dyes described in 1).

  Conventionally, fluorescent dyes are aromatic or heteroaromatic compounds such as pyrene, anthracene, naphthalene, acridine, indole, benzindole, ketopyrrole, oxazole, benzoxazole, diazole, methine, carbocyanine, carbostyril, porphyrin, salicylate, anthracite Tranilate, azulene, perylene, pyrazine, pyridine, quinoline, coumarin, and xanthene.

  Examples of functionalized dyes to obtain organosilanes with colored molecules include tetramethylrhodamine 5- (and 6-) isothiocyanate (TRITC), Alexa Fluor® 488 C5 maleimide, Alexa Fluor® 488 Carboxylic acids and succinimidyl esters are mentioned.

Organosilanes may be represented by the general formula R _(4-n) SiX _{n where} X represents a hydrolyzable group such as methoxy, ethoxy, or 2-methoxyethoxy; R is mercapto, epoxy, A monovalent organic group containing 1 to 12 carbon atoms that may contain a functional organic group capable of reacting with a colored molecule, such as acrylyl, methacrylyl, or amino; n is an integer ranging from 0 to 4 , Preferably n is equal to 3, provided that at least one organosilane used to form the particle comprises an R group containing a functional organic group capable of reacting with the colored molecule. Examples of silanes that can be reacted to obtain silanes having colored molecules include 3-aminopropyltriethoxysilane, and 3-mercaptopropyltriethoxysilane.

  According to one particular embodiment, the hybrid particles are hybrid particles in which the colored molecule is a fluorescent molecule.

  According to one variant, the hybrid particles are coated with a silica sol-gel shell obtained from an alkoxysilane, preferably a trialkoxysilane or a tetraalkoxysilane. The particles may be composed of, for example, a uniform core and one or more layers covering the core to form a shell, and these layers may have different properties.

  According to one particular embodiment of this variant, the hybrid particles are fluorescent particles comprising a core composed of an organosilane having a fluorescent compound and a silica shell. The core of the particle may be obtained by reacting one or more fluorescent dyes with this or a reactive organosilane capable of reacting with these fluorescent dyes. The core is obtained via a condensation reaction of one or more (organo) alkoxysilanes. These (organo) alkoxysilanes make it possible to obtain one or more layers constituting the shell, these layers being the (organo) alkoxysilane used, the thickness of the shell, the continuity of the shell on the core And can have certain different properties as a function of the ratio of shell thickness to core.

  The size of the particles useful in the present invention may vary widely. However, these particles are generally nanoparticles, in particular nanoparticles having a number average diameter in the range of 1 to 100 nm, preferably between 1 and 50 nm. In certain preferred embodiments, these particles are nanoparticles having a diameter between 1 and 20 nm.

  Preferably these particles are monodisperse.

  In the context of the present invention, size and size distribution are measured by electron microscopy (SEM).

  The hybrid particles useful in the present invention are particles known in the art obtained via the sol / gel route. For example, these particles are described in the above-mentioned Nano Letters document and in the patent application US 2004/0101822. For further details on the nature of the precursors and the reaction mechanism in the sol-gel process, see the literature "Sol Gel Science", published by CJ Brinker and GW Scherer, Academic Press printing (ISBN 0-12-134970-5). good.

Hybrid particles are generally obtained via a sol-gel process performed using (organo) silanes. These organosilanes may be represented by the general formula R _(4-n) SiX _n described above.

  Thus, the reactive fluorescent dye tetramethylrhodamine isothiocyanate (TRITC) is reacted with a reactive organosilane such as 3-aminopropyltriethoxysilane to condense and thus covalently bond to the silica derivative thus formed. It is possible to obtain fluorescent hybrid particles useful in the present invention by forming hybrid particles enriched with. Depending on whether or not an organosilane having a colored molecule is isolated, one or two steps may be performed.

  In order to obtain a particle having a core and shell as described above, this first particle, which will be the core, will form a dense silica shell around the fluorescent core via a condensation reaction. Reaction with an alkoxysilane, preferably a tetraalkoxysilane, such as tetraethylorthosilicate.

  As an example, to obtain hybrid particles, TRITC and 3-aminopropyltriethoxysilane are reacted with an anhydrous medium in a molar ratio of 1:50 via an addition reaction. The product of this reaction is placed in a reactor in the presence of aqueous ammonia, water, and a solvent. The reaction is allowed to proceed overnight. After this reaction, tetraethylorthosilicate is introduced into the reaction medium to form a silica shell.

  According to one variant, uniform particles may be obtained by condensing all the reagents mentioned above and reacting them simultaneously.

  The particles may further be coated with one or more further organic and / or mineral layers, preferably having an affinity for the hair. Examples of organic layers include layers obtained with polyethylene glycol, polyurethane, dextrin, polyacryl, polyvinyl pyrrolidone, polyvinyl caprolactone, or a mixture of these materials.

  Examples of mineral layers include layers obtained with alumina, silica, or clay, or a mixture of these materials. These layers may be obtained via a sol-gel process using organosilane.

The particles useful in the present invention may be used incorporated into the composition. In this case, the composition is suitable for dyeing and is known as a dye support and comprises a cosmetic medium which generally consists of water or a mixture of water and at least one organic solvent. Examples of organic solvents, C ₁ -C ₄ lower alcohols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and aromatic Alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof are mentioned.

  The concentration of hybrid particles in the composition used according to the present invention is preferably in the range of 0.001% to 99%, more preferably 0.005% to 50%, ideally 0.01% to 20%. It is.

  The solvent is preferably present in a proportion of preferably between about 1 and 40% by weight, more preferably between about 5 and 30% by weight relative to the total weight of the dyeing composition.

  The dyeing composition according to the invention also contains various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric or amphoteric surfactants, or mixtures thereof, Anionic, cationic, nonionic, amphoteric, or amphoteric polymers, or mixtures thereof, inorganic or organic thickeners, especially anionic, cationic, nonionic, and amphoteric polymer associative thickeners, Oxidants, penetrants, sequestering agents, perfumes, buffers, dispersants, conditioning agents such as volatile or non-volatile, modified or unmodified silicones, film formers, ceramides, preservatives, and opacifiers May be included.

  The adjuvants are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

  The composition according to the invention preferably comprises a surfactant or a thickening polymer in addition to the nanoparticles.

  These surfactants and polymers may have nonionic, anionic, cationic, or amphoteric properties.

  The amount of surfactant and / or thickening polymer present in the composition according to the invention may range from 0.01 to 40%, preferably from 0.5 to 30% of the total weight of the composition. .

  It goes without saying that the person skilled in the art pays attention to choosing this or any of these further compounds, and the advantageous properties inherently relevant to the oxidation dyeing composition according to the invention are negatively influenced by the additions considered. Will not or will not be substantially negatively affected.

  The pH of the dyeing composition according to the invention is generally between about 3 and 12, preferably between about 5 and 11. The pH may be adjusted to the desired value by acidifying or basifying agents commonly used in keratin fiber staining, or alternatively using standard buffer systems.

  Acidifying agents include inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, or lactic acid, and sulfonic acids.

［式中、Ｗはヒドロキシル基またはＣ_１−Ｃ_４アルキル基で任意に置換されたプロピレン基であり；Ｒ_ａ、Ｒ_ｂ、Ｒ_ｃ及びＲ_ｄは、同一でも異なってもよく、水素原子またはＣ_１−Ｃ_４アルキル基またはＣ_１−Ｃ_４ヒドロキシアルキル基を表す］。 Basifying agents include aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and derivatives thereof, sodium hydroxide, potassium hydroxide, and compounds of the following formula (II) To mention:

Wherein W is a propylene group optionally substituted with a hydroxyl group or a C ₁ -C ₄ alkyl group; R _a , R _b , R _c and R _d may be the same or different and may be a hydrogen atom or C ₁ -C represents an _alkyl group or a _C 1 -C ₄ hydroxyalkyl groups.

  The dyeing composition according to the invention may be present in various forms, for example in the form of liquids, creams or gels, or in any other form suitable for dyeing keratin fibres, in particular human hair. . It may be present in the form of a dye, but it may also be present in the form of a shampoo, hair conditioner, lacquer, or hair shaping composition.

  Another subject of the invention is a method of treating keratin fibres, in particular human keratin fibres, such as hair, comprising the application of the composition according to the invention to the keratin fibres.

  According to one particular embodiment, the method of the invention is a method of staining keratin fibers. The composition of the present invention may be applied to wet or dry fibers. Subsequent to the application, there may be a step of washing and / or rinsing the keratin fibers.

  When the colored molecule is a fluorescent dye, the method of the present invention is applied to hair having a color tone of, for example, 4 or more, preferably 6 or more when applied to naturally or artificially colored dark hair. When done, an optical lightening of the hair can be obtained. Thus, significant lightening of the keratin fibers may be observed without bleaching the keratin fibers. The concept of “color tone” is based on the classification of natural shades, and one color tone can be distinguished from the color tone immediately before or after it. This definition and the classification of natural shades are well known to hair styling specialists and can be found in the document "Sceince des traitements capillaries [Hair treatment science]", Charles Zviak, 1988, printed by Masson, pp. 215 and 278. Published.

  As an example of keratin fiber coloring, 5% alkylpolyglucoside and 0.5% fluorescent red color prepared according to the method described in Examples 1 and 3 (pp. 12-13) of patent US2004 / 101822 An aqueous composition comprising core / shell nanoparticles may be applied to a natural gray hair mass containing 90% gray hair at room temperature. After the hair mass treated in this manner has been drained and dried, the red coloration of the hair mass can be observed.

Claims (16)

  Use of hybrid particles obtained from organosilane compounds having colored molecules for staining keratin fibers.   Use according to claim 1, wherein the colored molecule is selected from nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or nitrobenzene triarylmethane type direct dyes and natural dyes.   Use according to claim 1, wherein the colored molecule is a pigment.   Use according to claim 1 or 2, wherein the colored molecule is a fluorescent dye.   The colored molecule is pyrene, anthracene, naphthalene, acridine, indole, benzindole, ketopyrrole, oxazole, benzoxazole, diazole, methine, carbocyanine, carbostyril, porphyrin, salicylate, anthranilate, azulene, perylene, pyrazine, pyridine. The use according to claim 4, which is a fluorescent dye selected from quinoline, coumarin, and xanthene. The hybrid particles have the formula R _(4-n) SiX _n , wherein X represents a hydrolyzable group; R may contain a functional organic group capable of reacting with a colored molecule, 1 to 12 carbon atoms N is an integer ranging from 0 to 4, provided that at least one organosilane used to form the particle contains a functional organic group capable of reacting with a colored molecule Use according to any one of claims 1 to 5, obtained from an organosilane containing R groups.   7. Use according to any one of the preceding claims, wherein the hybrid particles are coated with a sol-gel silica shell obtained from alkoxysilane.   Use according to claim 7, wherein the shell is derived from a trialkylsilane and / or a tetraalkylsilane.   Use according to claim 7 or 8, wherein the shell comprises one or more layers.   Use according to any one of claims 1 to 9, wherein the size of the nanoparticles is between 1 and 100 nm, preferably between 1 and 50 nm.   Use according to any one of claims 1 to 10, for dyeing hair.   Dyeing composition comprising at least one hybrid particle as defined in any one of claims 1 to 11 in a suitable dyeing medium.   13. A composition according to claim 12, comprising at least one surfactant and / or one thickening polymer.   14. A composition according to claim 12 or 13, which is in the form of a dye, shampoo, hair conditioner, lacquer or hair shaping composition.   A method for staining keratin fibers, comprising applying the composition according to any one of claims 12 to 14 to keratin fibers.   A method for lightening keratin fibers comprising the application of the composition according to any one of claims 12 to 14 to keratin fibers having a color depth of 4 or more, preferably 6 or more.