WO2021123061A1 - Process for preparing a composition for dyeing the hair starting from a composition in powder form and an aqueous composition - Google Patents

Process for preparing a composition for dyeing the hair starting from a composition in powder form and an aqueous composition Download PDF

Info

Publication number
WO2021123061A1
WO2021123061A1 PCT/EP2020/086886 EP2020086886W WO2021123061A1 WO 2021123061 A1 WO2021123061 A1 WO 2021123061A1 EP 2020086886 W EP2020086886 W EP 2020086886W WO 2021123061 A1 WO2021123061 A1 WO 2021123061A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
composition
oil
aqueous
better still
Prior art date
Application number
PCT/EP2020/086886
Other languages
French (fr)
Inventor
Mickaël AGACH
Hanène MOUEDDENE
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'oreal filed Critical L'oreal
Publication of WO2021123061A1 publication Critical patent/WO2021123061A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9789—Magnoliopsida [dicotyledons]

Definitions

  • the subject of the present invention is a process for preparing a composition for dyeing the hair which consists in mixing a composition in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with an aqueous composition.
  • This dyeing method uses one or more oxidation dye precursors, usually one or more oxidation bases optionally combined with one or more couplers.
  • oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para- aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured species.
  • couplers are notably chosen from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.
  • oxidation bases and couplers allow a wide range of colours to be obtained. This type of dyeing also makes it possible to obtain permanent colourings, but the use of oxidizing agents may lead to degradation of the keratin fibres.
  • the second dyeing method comprises the application of direct dyes, which are molecules with affinity for the fibres and which colour even in the absence of an oxidizing agent added to the compositions containing them. Given the nature of the molecules used, they tend rather to remain on the surface of the fibre and penetrate relatively little into the fibre, when compared with the small molecules of oxidation dye precursors.
  • the direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes.
  • the chemical species used may be nonionic, anionic (acidic dyes) or cationic (basic dyes).
  • Direct dyes may also be natural dyes.
  • compositions containing one or more natural dyes are applied to the keratin fibres for a time necessary to obtain the desired colouring, and are then rinsed out.
  • the colourings resulting therefrom are colourings that may be particularly chromatic, but which are, however, only temporary or semi-permanent since their desorption from the surface and/or the core of the fibre is responsible for their weak dyeing power and their poor persistence with respect to washing.
  • these compositions require relatively long leave-on times. They may vary from several tens of minutes to several hours (overnight) depending on the desired intensity, with no ability to control the result. The result varies as a function of the fibres to be dyed and of the nature of the natural dye(s) used.
  • One of the aims of the present invention is to propose colourings which are based on natural dyes with varied shades, which are resistant and respect the nature of the hair, enabling a more comfortable application of the product on the head, in a presentation form that makes it possible to optimize the usage qualities and the comfort during application.
  • the invention aims in particular to reduce the amount of dye necessary and to facilitate the application, the distribution on the hair and the rinseability of the dye, while retaining an intense colouring.
  • a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with
  • the dye composition in powder form that is useful according to the invention is anhydrous.
  • anhydrous composition means that the composition comprises less than 5% by weight of water, preferably less than 2% by weight of water and better still the composition is free of water.
  • the composition is free of added water, the water optionally present being provided by the raw materials used.
  • Another subject of the invention is an aqueous dye composition
  • aqueous dye composition comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener (ready-to-use composition).
  • the invention further relates to a method for dyeing the hair comprising the application of this composition on the hair. It being possible for this composition to be obtained by mixing
  • a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, and
  • the process for preparing the dye composition according to the invention makes it possible to easily obtain a mixture that is stable, homogeneous and easy to apply to and spread on the hair. Moreover, the dyeing method according to the invention carried out using the composition of the invention makes it possible to rapidly obtain a good colour build-up, and makes it possible to result in good dye properties, in particular powerful, aesthetic colourings with varied shades.
  • a stable mixture is understood to mean a mixture whose viscosity varies little or not at all during storage. This stability can be evaluated after 2 months storage at room temperature or at 45°C and without phase separation.
  • the term “powdeP means a composition or an ingredient in pulverulent form, preferably essentially free of dust.
  • the particle size distribution of the particles is such that the weight ratio of particles less than or equal to 50 micrometres in size (dust content) and preferably less than or equal to 10 micrometres in size (dust content) is advantageously less than or equal to 5%, preferably less than 2% and more particularly less than 1 % (particle size evaluated using a Retsch AS 200 Digit particle size analyser; oscillation height: 1 .25 mm/screening time: 5 minutes).
  • the particle size is between 10 pm and 500 pm.
  • the term “at least one ” is equivalent to “one or more”.
  • the term “build-up” of the colour on keratin fibres means the variation in colouring between locks of undyed hair and locks of dyed hair.
  • natural dye means any dye or dye precursor from a natural source, in particular of plant origin.
  • the natural dyes may notably be obtained by extraction (and optionally purification) from a plant matrix, by grinding plants or plant parts, roots, wood, bark, berries, lichens, leaves, flowers, nuts or seeds. Natural dyes may also be obtained by fermentation.
  • the natural dye(s) are chosen, for example, from lawsone, juglone, alizarin, purpurin, camninic acid, kermesic acid, laccaic acid, purpurogallin, anthragallol, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, chlorophylls, chlorophyllins, orceins, haematin, haematoxylin, brazilin, brazilein, santalin, santarubin, carthamin, flavonoids (with, for example, morin, apigenidin and quercetin), anthocyans (such as apigeninidin), carotenoids and anthraquinones, or mixtures thereof.
  • lawsone juglone, alizarin, purpurin, camninic acid, kermesic acid, laccaic acid, purpurogallin, anthragallol, protocatechualdehy
  • extracts, decoctions or ground matter notably powders, containing these natural dyes and notably extracts, decoctions or ground matter obtained, for example, from pernambuco wood, campeachy wood, sandalwood, orchil, turmeric, madder, indigo-producing plants such as indigo plant, sorghum, carrot, annatto, Brazil wood, safflower, henna or mixtures thereof.
  • composition according to the invention may comprise indigo-producing plant powder and/or extract.
  • indigo-producing plant extract means “a dye extract from an indigo-producing plant”).
  • Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata, Indigofera arrecta, Indigo fera gerardiana, Indigofera argentea, Indigofera indica, Indigofera longiracemosa
  • Isatis such as Isatis tinctoria
  • Persicaria such as Polygonum tinctorium (Persicaria tinctoria ) - Wrightia such as Wrightia tinctoria ⁇ ,
  • Calanthe such as Calanthe veratrifolia
  • Baphicacanthus such as Baphicacanthus cusia.
  • the indigo-producing plant is of the genus Indigofera and more particularly is Indigofera tinctoria, suffruticosa or argentea, preferably Indigofera tinctoria.
  • Use may be made of all or part (in particular the leaves notably for Indigofera tinctoria) of the indigo- producing plant.
  • the dye that is useful according to the invention may be henna.
  • henna refers to a henna plant powder and/or a henna plant dye extract, preferably from a henna plant such as Lawsonia alba or Lawsonia inermis.
  • the henna plant powder and/or dye extract especially comprises lawsone and/or a glucosylated precursor thereof.
  • the henna used according to the present invention is in powder form.
  • the henna used in the invention is preferably red henna ( Lawsonia inermis, alba). Lawsone [83-72-7] (Cl Natural Orange 6; Cl 75420), also known as isojuglone, may be found in henna shrubs (Lawsonia alba, Lawsonia inermis).
  • the natural dye(s) useful according to the invention are in the form of powder(s).
  • the natural dye(s) are chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, and/or mixtures thereof.
  • the natural dye(s) are chosen from henna powder, indigo-producing plant powders, and mixtures thereof.
  • the dye composition of the invention is in powder form and preferably the natural dyes used are in powder form.
  • the composition of the invention comprises one or more other ingredients that enable the composition to be in powder form.
  • the total amount of natural dye(s) ranges from 30% to 99% by weight, preferably from 50% to 97% by weight and better still from 70% to 95% by weight, relative to the total weight of composition (A).
  • the total amount of natural dye(s) ranges from 1 % to 40% by weight, preferably from 2% to 35% by weight and better still from 5% to 30% by weight, relative to the total weight of the aqueous dye composition.
  • the composition of the invention comprises plants from the Cassia family, in particular chosen from Cassia angustifolia (senna) and/or Cassia auriculata or Cassia italica, or mixtures thereof.
  • the composition according to the invention may comprise a powder or a plant extract of the Cassia family, in particular of Cassia angustifolia and/or Cassia auriculata and/or Cassia italica, preferably Cassia angustifolia.
  • the composition of the invention comprises the natural dye(s) chosen from henna powder, indigo-producing plant powders, plant powders of the Cassia family, in particular Cassia angustifolia and/or Cassia auriculata and/or Cassia italica, and mixtures thereof.
  • the composition of the invention comprises the natural dye(s) chosen from henna powder, indigo-producing plant powders, Cassia angustifolia powders and mixtures thereof.
  • the term “dispersant’ means a compound added to a suspension to improve the diffusion on a surface or a liquid, to separate the particles, and that is capable of limiting, or even preventing, the agglomeration of the particles or powders and/or the sedimentation thereof.
  • Dispersant(s) according to the invention are, preferably, chosen from polymers of hydroxylated fatty acids and/or the salts and/or derivatives thereof.
  • fatty acid means a carboxylic acid comprising from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms and more preferentially from 15 to 20 carbon atoms.
  • the polymers of hydroxylated fatty acids may be homopolymers or copolymers of hydroxylated fatty acids.
  • Hydroxylated fatty acid derivatives that may notably be mentioned include hydroxylated fatty acid esters.
  • These polymers may contain one or more monomers other than the hydroxylated fatty acids and/or the salts or derivatives thereof, in particular non-hydroxylated fatty acids and/or salts or derivatives thereof.
  • the copolymers of hydroxylated fatty acids are obtained from one or more hydroxylated fatty acid monomers and optionally one or more hydroxylated fatty acid ester monomers.
  • the copolymers of hydroxylated fatty acids are obtained from one or more hydroxylated fatty acid monomers and optionally one or more non-hydroxylated fatty acid monomers.
  • the polymer of hydroxylated fatty acids may be chosen from polymers of hydroxylated carboxylic acids comprising from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms and more preferentially from 15 to 20 carbon atoms, and the salts thereof.
  • the polymers of hydroxylated fatty acids may be chosen from esters of hydroxylated fatty acid(s), preferably from esters of hydroxystearic acid, in particular of 12-hydroxystearic acid.
  • the polymers of hydroxylated fatty acids may be obtained from esters of hydroxylated fatty acids and of C4 to C20 and preferably Ce to C20 non-hydroxylated fatty acid, preferably from esters of polyhydroxystearic acid and of C4 to C20 and preferably Ce to C20 non-hydroxylated fatty acid.
  • the hydroxylated fatty acid ester is obtained from a C4 to C20 and preferably Ce to C20 fatty acid, preferably a hydroxystearic acid ester.
  • the polymer(s) of hydroxylated fatty acids are chosen from the polymers of esters of hydroxylated fatty acids, preferably from the oligomers of esters of 12-hydroxystearic acid and of Ce to C20 fatty acid such as poly(12-hydroxystearic acid) oligomer stearate.
  • hydroxystearic acid polymer is obtained from 12- hydroxystearic acid, optionally from a hydroxystearic acid ester, for example methyl or ethyl hydroxystearate, notably methyl 12-hydroxystearate, and optionally from other hydroxylated fatty acids, for example 12-hydroxydodecanoic acid.
  • the hydroxystearic acid polymer is obtained from 12- hydroxystearic acid and optionally from stearic acid.
  • the polymer of hydroxylated fatty acids is a 12-hydroxystearic acid homopolymer or copolymer.
  • salts of the polymers of hydroxylated fatty acids mention may be made of the potassium, sodium and ammonium salts.
  • polymers of hydroxylated fatty acids and/or salts and/or derivatives thereof examples that may be mentioned include oligomers of 12-hydroxystearic acid and of Ce to C20 fatty acid such as the oligomer of poly(12-hydroxystearic acid) with a molecular weight of about 750 g/mol such as the product sold by the company Innospec Active Chemicals under the reference Dispersun DSP-OL 100 or Dispersun DSP-OL 300 (INCI name: Polyhydroxystearic acid), esters of poly(12-hydroxystearic acid) with polyols such as glycerol or diglycerol, such as polyglyceryl-2 dipolyhydroxystearate (INCI name) sold under the reference Dehymuls® PGPH by the company Henkel, or the compound having the INCI name Polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Croda.
  • oligomers of 12-hydroxystearic acid and of Ce to C20 fatty acid
  • Use is preferably made of 12-hydroxystearic acid oligomers such as poly(12-hydroxystearic acid) oligomer stearate, for instance the product sold by the company Innospec Active Chemicals under the reference Dispersun DSP-OL 100 or Dispersun DSP-OL 300 (INCI name: polyhydroxystearic acid).
  • the dispersant(s) according to the invention may also be chosen from polycondensates of ethylene oxide and propylene oxide, in particular from polycondensates of ethylene oxide and propylene oxide of the following formula:
  • Synperonic® PE/F32 (INCI name: Poloxamer 108), Synperonic® PE/F108 (INCI name: Poloxamer 338), Synperonic® PE/ L44 (INCI name: Poloxamer 124), Synperonic® PE/L42 (INCI name: Poloxamer 122), Synperonic® PE/F127 (INCI name: Poloxamer 407), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/L64 (INCI name: Poloxamer 184), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/F87 (INCI name: Poloxamer 237) from the company Croda, or Lutrol
  • fatty diesters such as diisostearyl malate.
  • the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still from 0.1% to 10% by weight, even better still from 0.5% to 8% by weight, or even from 1 % to 5% by weight, relative to the total weight of composition (A).
  • the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still from 0.1% to 10% by weight, even better still from 0.1% to 5% by weight, or even from 0.1% to 2% by weight, relative to the total weight of the aqueous dye composition.
  • aqueous-phase thickened means compounds which, by their presence at a concentration of 0.05% by weight, increase the viscosity of an aqueous composition into which they are introduced by at least 20 cps, preferably by at least 50 cps, at room temperature (25°C), at atmospheric pressure and at a shear rate of 1 s 1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheometer or the like).
  • the aqueous-phase thickener(s) are preferentially chosen from non-associative thickening polymers bearing sugar units, non-associative thickening polymers without sugar units, associative thickening polymers, and mixtures of these compounds.
  • sugar unit is understood to mean, within the meaning of the present invention, an oxygen comprising hydrocarbon compound which has several alcohol functional groups, with or without aldehyde or ketone functional group, and which comprises at least 4 carbon atoms.
  • the sugar units can be optionally modified by substitution, and/or by oxidation and/or by dehydration.
  • the sugar units that may be included in the composition of the aqueous-phase thickening polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate and fructose.
  • non-associative thickening polymers bearing sugar units of native gums, such as: a) tree or shrub exudates, including:
  • gum arabic branched polymer of galactose, arabinose, rhamnose and glucuronic acid
  • - ghatti gum polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid
  • karaya gum polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid
  • gum tragacanth polymer of galacturonic acid, galactose, fucose, xylose and arabinose
  • gums derived from algae including:
  • locust bean gum polymer of mannose and galactose
  • microbial gums including:
  • - xanthan gum polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid
  • - gellan gum polymer of partially acylated glucose, rhamnose and glucuronic acid
  • These polymers can be physically or chemically modified. Mention may in particular be made, as physical treatment, of the temperature.
  • these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.
  • nonionic guar gums which can be used according to the invention can be modified by (poly)hydroxy(Ci-C6)alkyl groups.
  • guar gums are well known from the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.
  • the degree of hydroxyalkylation preferably ranges from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.
  • nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by the company Rhodia Chimie.
  • the botanical origin of the starch molecules that can be used in the present invention may be cereals or tubers.
  • the starches are, for example, chosen from maize starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch or pea starch.
  • the starches can be chemically or physically modified, in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation or heat treatments.
  • Distarch phosphates or compounds rich in distarch phosphate will preferentially be used, for instance the product sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) and Prejel 200 (gelatinized acetylated cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized maize distarch phosphate).
  • amphoteric starches these amphoteric starches comprising one or more anionic groups and one or more cationic groups.
  • the anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites; they are preferably bonded to the same reactive site.
  • the anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic type.
  • the cationic groups may be of primary, secondary, tertiary or quaternary amine type.
  • the starch molecules can result from any plant source of starch, such as in particular maize, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the abovementioned starches.
  • the starch preferably results from potato.
  • the non-associative thickening polymers of the invention can be cellulose polymers not comprising a C10-C30 fatty chain in their structure.
  • cellulose polymer is understood to mean, according to the invention, any polysaccharide compound having, in its structure, sequences of glucose residues joined via b-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives can be anionic, cationic, amphoteric or nonionic.
  • the cellulose polymers which can be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers. Among these cellulose polymers, cellulose ethers, cellulose esters and cellulose ether esters are distinguished.
  • cellulose esters are inorganic esters of cellulose (cellulose nitrates, sulfates, phosphates, etc.), organic esters of cellulose (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetatetrimellitates, etc.), and mixed organic/inorganic esters of cellulose, such as cellulose acetatebutyrate sulfates and cellulose acetatepropionate sulfates.
  • cellulose ester ethers mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.
  • Nonionic cellulose ethers without a C10-C30 fatty chain i.e. which are "non-associative", of (Ci-C 4 )alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example, Ethocel Standard 100 Premium from Dow Chemical); (poly)hydroxy(Ci-C 4 )alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example, Natrosol 250 HHR provided by Aqualon) and hydroxypropylcelluloses (for example, Klucel EF from Aqualon); mixed (poly)hydroxy(Ci- C 4 )alkyl/(Ci-C 4 )alkylcellulose celluloses, such as hydroxypropyl methylcelluloses (for example, Methocel E4M from Dow Chemical), hydroxyethyl methylcelluloses, hydroxyethyl ethylcelluloses (for example, Bemnocoll E 4
  • anionic cellulose ethers without a fatty chain mention may be made of (poly)carboxy(Ci- C 4 )alkylcelluloses and salts thereof.
  • examples that may be mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.
  • cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and notably described in patent US 4 131 576, such as (poly)hydroxy(Ci-C 4 )alkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses notably grafted with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • the commercial products corresponding to this definition are more particularly the products sold under the names Celquat® L 200 and Celquat® H 100 by the company National Starch.
  • non-associative thickening polymers not bearing sugar units that may be used according to the invention, mention may be made of crosslinked acrylic acid or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or as mixtures.
  • a first family of non-associative thickening polymers that is suitable for use is represented by crosslinked acrylic acid homopolymers.
  • homopolymers of this type mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, for instance the products sold under the names Carbopol 980, 981 , 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA.
  • These polymers have the I NCI name Carbomer.
  • the non-associative thickening polymers may also be crosslinked (meth)acrylic acid copolymers, such as the polymer sold under the name Aqua SF1 by the company Noveon.
  • the non-associative thickening polymers may be chosen from 2-acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked or non-crosslinked copolymers thereof.
  • 2-acrylamido-2-methylpropanesulfonic acid copolymers mention may be made of partially or totally neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of acrylamide; mention may be made in particular of the product described in Example 1 of document EP 503 853, and reference may be made to said document as regards these polymers.
  • the dye composition that is useful according to the invention may comprise, as non-associative thickening polymers, ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.
  • ammonium acrylate homopolymers that may be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst.
  • copolymers of ammonium acrylate and of acrylamide that may be mentioned is the product sold under the name Bozepol C Wunsch or the product PAS 5193 sold by the company Hoechst.
  • Use may also be made of cationic thickening polymers of acrylic type.
  • aqueous-phase-thickening polymers mention may also be made of associative polymers that are well known to those skilled in the art and especially of nonionic, anionic, cationic or amphoteric nature.
  • sociative polymers are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.
  • Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.
  • hydrophobic group means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
  • the hydrocarbon-based group is derived from a monofunctional compound.
  • the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene. Mention may be made, among the associative polymers of anionic type, of:
  • the ones that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether, and from 0 to 1 % by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.
  • a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.
  • crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth- 10), notably those sold by the company Ciba under the names Salcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10);
  • Alkyl esters of unsaturated carboxylic acids that are useful in the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
  • anionic associative polymers of this type that will be used more particularly are those constituted of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those constituted of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.
  • the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially Pemulen TR1®, and the product sold by the company SEPPIC under the name Coatex SX®.
  • maleic anhydride/C3o-C38 a-olefin/alkyl maleate terpolymers such as the product (maleic anhydride/C3o-C38 a-olefin/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies.
  • acrylic terpolymers comprising: i) about 20% to 70% by weight of an a,b-monoethylenically unsaturated carboxylic acid [A], ii) about 20% to 80% by weight of an a,b-monoethylenically unsaturated non-surfactant monomer other than [A], iii) about 0.5% to 60% by weight of a nonionic monourethane, which is the product of reaction of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in patent application EP-A-0 173 109 and more particularly the one described in Example 3, namely a methacrylic acid/methyl acrylate/ethoxylated (40 OE) behenyl alcohol dimethyl meta- isopropenyl benzyl isocyanate terpolymer as a 25% aqueous dispersion.
  • a monohydric surfactant with a monoethylenically unsaturated
  • these compounds also comprise as monomer an ester of an a,b-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.
  • Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer; and also Aculyn 88, also sold by the company Rohm & Haas.
  • amphiphilic polymers including at least one ethylenically unsaturated monomer bearing a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part. These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.
  • the ethylenically unsaturated monomers bearing a sulfonic group are notably chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(Ci- C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
  • (Meth)acrylamido(Ci-C22)alkylsulfonic acids for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n- butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2- methacrylamidododecylsulfonic acid or2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.
  • 2-Acrylamido-2-methylpropanesulfonic acid (AMPS) and also partially or totally neutralized forms thereof, will more particularly be used.
  • the polymers of this family may be chosen notably from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine ordi-n-alkylamine, and such as those described in patent application WO 00/31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, b-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • the preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer.
  • copolymers may also contain one or more ethylenically unsaturated monomers not including a fatty chain, such as (meth)acrylic acids, b-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • ethylenically unsaturated monomers not including a fatty chain such as (meth)acrylic acids, b-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • - terpolymers including from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-Ci8)alkylacrylamide units, such as those described in patent US-5 089 578. Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
  • cationic associative polymers mention may be made of:
  • Polyacrylate- 1 Crosspolymer is the product of polymerization of a monomer mixture comprising:
  • the alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably include from 8 to 30 carbon atoms.
  • the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
  • Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18-B® (C12 alkyl) and Quatrisoft LM-X 529-8® (C18 alkyl) sold by the company Aqualon, and the products Crodacel QM®, Crodacel QL® (C12 alkyl) and Crodacel QS® (C18 alkyl) sold by the company Croda and the product Softcat SL 100® sold by the company Aqualon.
  • cationic polyvinyllactam polymers Such polymers are for example described in patent application WO-OO/68282.
  • cationic poly(vinyllactam) polymers according to the invention vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammoniu m tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropylammonium tosylate or chloride terpolymers are notably used.
  • amphoteric associative polymers are preferably chosen from those including at least one noncyclic cationic unit. Even more particularly, those prepared from or comprising 1 to 20 mol%, preferably 1.5 to 15 mol% and even more particularly 1 .5 to 6 mol% of fatty-chain monomer relative to the total number of moles of monomers are preferred. Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.
  • amphoteric associative polymers the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.
  • the associative polymers of nonionic type that may be used according to the invention are preferably chosen from:
  • copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers including at least one fatty chain for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer
  • polyurethane polyethers including in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
  • polymers with an aminoplast ether backbone containing at least one fatty chain such as the Pure Thix® compounds sold by the company Sud-Chemie;
  • nonionic alkylhydroxyethylcelluloses such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (Ci6 alkyl) sold by Aqualon;
  • nonionic nonoxynylhydroxyethylcelluloses such as the product Amercell HM-1500 sold by Amerchol;
  • associative guar derivatives for instance hydroxypropyl guars modified with a fatty chain, such as the product Esaflor HM 22 (modified with a C22 alkyl chain) sold by the company Lamberti; the product Miracare XC 95-3 (modified with a C14 alkyl chain) and the product RE 205-146 (modified with a C20 alkyl chain) sold by Rhodia Chimie.
  • the polyurethane polyethers include at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being side chains or chains at the end of the hydrophilic block.
  • the polymer may include a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
  • the polyurethane polyethers may be multiblock, in particular in triblock form.
  • the hydrophobic blocks may be at each end of the chain (for example: triblock copolymer bearing a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer).
  • These same polymers may also be graft polymers or star polymers.
  • the nonionic fatty-chain polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain including from 50 to 1000 oxyethylene groups.
  • the nonionic polyurethane polyethers include a urethane bond between the hydrophilic blocks, whence the origin of the name.
  • nonionic fatty-chain polyurethane polyethers include those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
  • nonionic fatty-chain polyurethane polyethers that may be used in the invention, use may also be made of Rheolate 205® bearing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®.
  • the product DW 1206B® from Rohm & Haas bearing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.
  • Use may also be made of solutions or dispersions of these polymers, notably in water or in aqueous- alcoholic medium.
  • examples of such polymers that may be mentioned include Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox.
  • Use may also be made of the products DW 1206F and DW 1206J sold by the company Rohm & Haas.
  • polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. ScL, 271 , 380-389 (1993).
  • a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
  • Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%);
  • Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
  • the aqueous-phase thickeners that are useful according to the invention are chosen from non-associative polymers bearing sugar units.
  • aqueous-phase thickeners that are useful according to the invention are chosen from native gums.
  • the aqueous-phase thickeners that are useful according to the invention are chosen from guar gums, xanthan gums and mixtures thereof.
  • the total amount of aqueous-phase thickeners ranges from 0.1 % to 20% by weight, preferably from 0.5% to 10% by weight and better still from 1 % to 5% by weight, relative to the total weight of composition (A).
  • the total amount of aqueous-phase thickeners ranges from 0.1 % to 5% by weight, preferably from 0.2% to 5% by weight and better still from 0.3% to 2% by weight, relative to the total weight of the aqueous dye composition.
  • the aqueous composition of the invention comprises at least one natural dye chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, at least one Cassia angustifolia extract and/or powder and mixtures thereof, at least one polymer of hydroxylated fatty acids and/or salts and/or derivatives thereof chosen from hydroxystearic acid polymers and at least one aqueous-phase thickener chosen from native gums.
  • the process according to the invention is a process for preparing a composition for dyeing the hair which consists in mixing:
  • a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one organic solvent and/or at least one oil, with
  • the method for dyeing the hair comprises the application of this composition on the hair. It being possible for this composition to be obtained by mixing
  • a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one solvent and/or at least one oil, and
  • the aqueous dye composition then comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one organic solvent and/or at least one oil (ready-to-use composition).
  • the process according to the invention is a process for preparing a composition for dyeing the hair which consists in mixing:
  • a dye composition (A) in powder form comprising at least one natural dye chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, Cassia angustifolia extracts and/or powders and mixtures thereof, at least one polymer of hydroxylated fatty acids and/or salts and/or derivatives thereof chosen from hydroxystearic acid polymers, at least one aqueous-phase thickener chosen from native gums, at least one organic solvent chosen from propylene glycol, glycerol, hexylene glycol, benzyl alcohol or phenoxyethanol, ethanol and mixtures thereof and at least one oil chosen from avocado oil, olive oil, coconut oil, argan oil, sunflower oil, rapeseed oil and mixtures thereof, better still from coconut oil, rapeseed oil and mixtures thereof, with - an aqueous composition (B).
  • A in powder form comprising at least one natural dye chosen from lawsone, henna extract
  • organic solvent is intended to mean an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it.
  • the organic solvent(s) that are useful in the compositions of the invention is or are chosen from C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
  • C1-C4 lower alkanols such as ethanol and isopropanol
  • polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
  • the organic solvents that are useful in the compositions of the invention are chosen from C1-C4 lower alkanols; polyols and polyol ethers; aromatic alcohols; and mixtures thereof, preferably chosen from propylene glycol, glycerol, hexylene glycol, benzyl alcohol or phenoxyethanol, ethanol and mixtures thereof.
  • the total amount of organic solvents as defined above, when they are present ranges from 0.01 % to 30% by weight relative to the total weight of the composition in which they are found, preferably from 0.1% to 20% by weight, better still from 1 % to 10% by weight relative to the total weight of composition (A).
  • the total amount of organic solvents as defined above, when they are present ranges from 0.01 % to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.05% to 10% by weight, better still from 0.1% to 5% by weight relative to the total weight of the aqueous dye composition.
  • the term “o/f means a “fatty substance” that is liquid at a temperature of 30°C and at atmospheric pressure (760 mmHg).
  • the viscosity at 25°C is preferably less than 1200 cps and better still less than 500 cps (defined, for example, from the Newtonian plateau determined using an ARG2 rheometer from TA Instruments equipped with a spindle with cone-plate geometry 60 mm in diameter and with an angle of 2 degrees over a shear stress range of from 0.1 Pa to 100 Pa).
  • fatty substance means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5% by weight, preferably less than 1 % by weight and even more preferentially less than 0.1 % by weight). They generally have in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
  • THF tetrahydrofuran
  • nonsilicone oil or fatty substance refers to an oil or a fatty substance not containing any Si- O bonds and the term “silicone oil or fatty substance” refers to an oil or a fatty substance containing at least one Si-O bond.
  • oils that are useful according to the invention are not (poly)oxyalkylenated or (polyjglycerolated ethers.
  • oils that are useful according to the invention are not fatty acids in salified form giving water- soluble soaps.
  • oils that are useful according to the invention are chosen from nonsilicone oils and in particular C6-C16 hydrocarbons or hydrocarbons containing more than 16 carbon atoms and in particular alkanes; triglyceride oils of plant origin; essential oils; glycerides of synthetic origin, fatty alcohols; fatty acid and/or fatty alcohol esters other than triglycerides.
  • fatty alcohols, esters and acids more particularly bear at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising 6 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • C6-C16 liquid hydrocarbons they are linear, branched or optionally cyclic, and are preferably alkanes. Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, isododecane, tridecane or isoparaffins, such as isohexadecane or isodecane, or mixtures thereof.
  • the linear or branched hydrocarbons of mineral or synthetic origin comprising more than 16 carbon atoms are preferably chosen from liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleam®, or mixtures thereof.
  • liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic oroctanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, coconut oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
  • liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic oroctanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame oil, hazel
  • the liquid fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols including from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Examples that may be mentioned include octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol or linoleyl alcohol, or mixtures thereof.
  • liquid esters of fatty acids and/or of fatty alcohols other than the triglycerides mentioned above mention may be made notably of esters of saturated or unsaturated, linear C3-C29 or branched C4-C30 aliphatic monoacids or polyacids and of saturated or unsaturated, linear C3-C 29 or branched C4-C30 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.
  • Esters of a fatty acid and/or of a fatty alcohol for instance Purcellin oil (stearyl octanoate), isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate or 2-octyldodecyl myristate or lactate, may be used.
  • Purcellin oil stearyl octanoate
  • isopropyl myristate isopropyl palmitate
  • butyl stearate hexyl laurate
  • diisopropyl adipate isononyl isononanoate
  • 2-ethylhexyl palmitate 2-hexyldecyl laur
  • the oil(s) are chosen from C6-C16 alkanes, polydecenes, liquid esters of a fatty acid and/or of a fatty alcohol, in particular triglycerides of plant or synthetic origin, and liquid fatty alcohols, or mixtures thereof.
  • the fatty substance is chosen from liquid esters of a fatty acid and/or of a fatty alcohol, triglycerides of plant or synthetic origin, or mixtures thereof; more preferentially from triglycerides of plant or synthetic origin.
  • the oils are chosen from oils of natural origin, more particularly oils of plant origin, preferentially jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, com oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil and also rapeseed oil, borage oil, evening primrose oil, pomegranate oil, mango oil, palm oil and cottonseed oil, and mixtures thereof.
  • oils of natural origin more particularly oils of plant origin, preferentially jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, com oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil,
  • oils of plant origin that are useful according to the invention are chosen from avocado oil, olive oil, coconut oil, argan oil, sunflower oil, rapeseed oil and mixtures thereof, better still from coconut oil, rapeseed oil and mixtures thereof.
  • Use will preferably be made of the coconut oil with the I NCI name Cocos nucifera (coconut) oil and the rapeseed oil with the INCI name Brassica campestris (rapeseed) seed oil.
  • the total amount of oil(s), when it is (they are) present ranges from 0.1% to 10% by weight, more particularly from 0.5% to 8% by weight, preferentially from 1% to 6% by weight, better still from 1.5% to 5% by weight relative to the total weight of composition (A).
  • the total amount of oil(s), when it is (they are) present ranges from 0.01% to 10% by weight, more particularly from 0.05% to 5% by weight, preferentially from 0.1% to 3% by weight, better still from 0.1% to 2% by weight relative to the total weight of the aqueous dye composition.
  • the dye composition in powder form may further comprise one or more additional dyes in the form of powders.
  • additional dyes in powder form that are useful according to the invention, mention may be made of direct dyes different from the dyes in powder form as described above. These additional direct dyes may be synthetic.
  • the additional dyes may be contained in the aqueous composition mixed with the dye composition.
  • the synthetic direct dyes are preferably chosen from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or nonaromatic dyes such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine direct dyes, and fluorescent dyes.
  • aromatic and/or nonaromatic dyes such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azin
  • oxidation bases and/or couplers conventionally used to dye keratin fibres.
  • oxidation bases mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.
  • couplers mention may be made especially of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
  • the additional dye(s) is (are) preferably present in an amount of between 0.001% and 10% by weight of the total weight of the composition (s) under consideration.
  • compositions used in the process for preparing a dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as surfactants, polymers different from the dispersants as described above and from the aqueous-phase thickeners as described above and aqueous-phase thickeners different from the aqueous-phase thickeners as described above, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents different from the oils as described above, film-forming agents, ceramides, preserving agents and opacifiers.
  • adjuvants conventionally used in hair dye compositions, such as surfactants, polymers different from the dispersants as described above and from the aqueous-phase thickeners as described above and aqueous-phase thickeners different from the aqueous-phase thickeners as described above, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents different from the oils as described above, film
  • the process for preparing a composition for dyeing the hair according to the invention consists in mixing a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with an aqueous composition (B).
  • the process for preparing a composition for dyeing the hair according to the invention consists in mixing a dye composition in powder form (A) comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener and/or at least one organic solvent and/or at least one oil, with an aqueous composition (B).
  • composition (B) is water.
  • composition (A) By mixing composition (A) and composition (B), an aqueous hair dye composition is obtained that comprises at least one natural dye, at least one dispersant, at least one aqueous-phase thickener and/or at least one organic solvent and/or at least one oil.
  • the ready-to-use composition obtained by the preparation process according to the invention is obtained by extemporaneous mixing, at the time of use, of a composition (A) as described previously and of an aqueous composition (B).
  • compositions (A) and (B) are preferably performed less than 30 min before application, preferentially less than 15 min before application, better still less than 10 min before application, or even less than 5 min before application.
  • composition (B) is used at a temperature of between 10°C and 100°C, better still between 40°C and 100°C.
  • the mixing ratio between the composition (A) and composition (B) may range from 0.01 to 10, preferably from 0.1 to 5, preferentially from 0.15 to 1 , and better still from 0.2 to 0.5.
  • the hair dye composition of the invention comprises at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one organic solvent, at least one oil and water.
  • the hair dye composition comprises at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, water, optionally at least one organic solvent, and optionally at least one oil.
  • the total amount of natural dye(s) ranges from 1% to 40% by weight, preferably from 2% to 35% by weight, better still from 5% to 30% by weight
  • the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still 0.1% to 10% by weight, even better still from 0.1% to 5% by weight, or even 0.1 % to 2% by weight
  • the total amount of aqueous-phase thickeners ranges from 0.1% to 5% by weight, preferably from 0.2% to 5% by weight, and better still from 0.3% to 2% by weight
  • the total amount of organic solvents, when they are present ranges from 0.01% to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.05% to 10% by weight, better still from 0.1% to 5% by weight
  • the total amount of oil(s), when it is (they are) present ranges from 0.01% to 10% by weight, more particularly from 0.05%
  • Another subject of the present invention is a method for dyeing the hair using the hair dye composition
  • the hair dye composition comprising at least one natural dye, at least one dispersant, at least one aqueous-based thickener, water, optionally at least one organic solvent, and optionally at least one oil, which consists in applying this composition to dry or wet hair.
  • This composition may result from the preparation process as described above consisting in mixing the compositions (A) and (B) as described above.
  • composition is then left in place for a time usually ranging from 1 minute to 2 hours, preferably from 5 minutes to 1 hour 30 minutes and better still from 10 minutes to 1 hour.
  • the head of hair may be subjected to a heat treatment.
  • this operation may be performed using a hairstyling hood, a hairdryer, an infrared ray emitter or other standard heating appliances.
  • the temperature during the process is conventionally between room temperature (between 15 and 25°C) and 80°C and preferably between room temperature and 60°C.
  • the hair fibres are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried (mechanically with a towel or absorbent paper, or by heat) or left to dry.
  • Another subject of the invention is a multi-compartment hair treatment device or kit comprising at least two compartments.
  • the multi-compartment device comprises at least one compartment comprising the dye composition in powder form as described above comprising at least one dye, at least one dispersant and at least one aqueous-phase thickener and one second compartment comprising an aqueous composition.
  • the device according to the invention also comprises an additional composition comprising one or more treating agents.
  • compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means which may be identical or different, such as fine brushes, coarse brushes or sponges.
  • the device mentioned above may also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913. Examples
  • compositions A to F according to the invention were prepared.
  • the proportions of the ingredients are indicated in grams of active material per 100 g of composition, unless otherwise indicated.
  • each of the dye compositions A to F is mixed with three or four times its own weight of water at 50°C or 100°C.
  • Each of the mixtures is then applied to locks of natural hair containing 90% white hairs, in a proportion of 10 g of mixture per 1 g of hair.
  • the viscosity of the mixtures is evaluated after 24 hours of storage at room temperature. The measurement was taken using a Rheomat RM200 viscometer. The mixture is deposited in a cup thermostatically maintained at 25°C. A deviation unit (DU) is measured using a spindle of type 3 with a speed of 200 rpm for 30 seconds. Results
  • compositions A to F according to the invention mix readily with water, have a good stability, the final texture is homogeneous, shiny, soft and creamy.
  • the composition does not dry out during the leave-on time which enables a better, faster rinseability.
  • compositions A to F according to the invention make it possible to obtain colourings with varied shades.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Biotechnology (AREA)
  • Botany (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Cosmetics (AREA)

Abstract

The subject of the present invention is a process for preparing a composition for dyeing the hair starting from a dye composition in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, and an aqueous composition.

Description

PROCESS FOR PREPARING A COMPOSITION FOR DYEING THE HAIR STARTING FROM A COMPOSITION IN POWDER FORM AND AN AQUEOUS COMPOSITION
The subject of the present invention is a process for preparing a composition for dyeing the hair which consists in mixing a composition in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with an aqueous composition.
Two major methods for dyeing human keratin fibres, and in particular the hair, are known.
One of these two methods is oxidation dyeing or permanent dyeing. This dyeing method uses one or more oxidation dye precursors, usually one or more oxidation bases optionally combined with one or more couplers.
In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para- aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured species.
The shades obtained with these oxidation bases are quite often varied by combining them with one or more couplers, these couplers being notably chosen from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.
The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained. This type of dyeing also makes it possible to obtain permanent colourings, but the use of oxidizing agents may lead to degradation of the keratin fibres.
The second dyeing method, known as direct dyeing or semi-permanent dyeing, comprises the application of direct dyes, which are molecules with affinity for the fibres and which colour even in the absence of an oxidizing agent added to the compositions containing them. Given the nature of the molecules used, they tend rather to remain on the surface of the fibre and penetrate relatively little into the fibre, when compared with the small molecules of oxidation dye precursors.
The direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species used may be nonionic, anionic (acidic dyes) or cationic (basic dyes). Direct dyes may also be natural dyes.
Dyeing the hair using natural direct dyes has been known since ancient times.
Compositions containing one or more natural dyes are applied to the keratin fibres for a time necessary to obtain the desired colouring, and are then rinsed out.
However, the colourings resulting therefrom are colourings that may be particularly chromatic, but which are, however, only temporary or semi-permanent since their desorption from the surface and/or the core of the fibre is responsible for their weak dyeing power and their poor persistence with respect to washing. Moreover, these compositions require relatively long leave-on times. They may vary from several tens of minutes to several hours (overnight) depending on the desired intensity, with no ability to control the result. The result varies as a function of the fibres to be dyed and of the nature of the natural dye(s) used.
One of the aims of the present invention is to propose colourings which are based on natural dyes with varied shades, which are resistant and respect the nature of the hair, enabling a more comfortable application of the product on the head, in a presentation form that makes it possible to optimize the usage qualities and the comfort during application. The invention aims in particular to reduce the amount of dye necessary and to facilitate the application, the distribution on the hair and the rinseability of the dye, while retaining an intense colouring.
This objective is achieved by the present invention, one subject of which is a process for preparing a composition for dyeing the hair which consists in mixing:
- a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with
- an aqueous composition (B).
According to one embodiment, the dye composition in powder form that is useful according to the invention is anhydrous. For the purposes of the present invention, the term “anhydrous composition” means that the composition comprises less than 5% by weight of water, preferably less than 2% by weight of water and better still the composition is free of water. In particular, the composition is free of added water, the water optionally present being provided by the raw materials used.
Another subject of the invention is an aqueous dye composition comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener (ready-to-use composition).
The invention further relates to a method for dyeing the hair comprising the application of this composition on the hair. It being possible for this composition to be obtained by mixing
- a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, and
- an aqueous composition (B).
The process for preparing the dye composition according to the invention makes it possible to easily obtain a mixture that is stable, homogeneous and easy to apply to and spread on the hair. Moreover, the dyeing method according to the invention carried out using the composition of the invention makes it possible to rapidly obtain a good colour build-up, and makes it possible to result in good dye properties, in particular powerful, aesthetic colourings with varied shades.
Other subjects, features, aspects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow. A stable mixture is understood to mean a mixture whose viscosity varies little or not at all during storage. This stability can be evaluated after 2 months storage at room temperature or at 45°C and without phase separation.
For the purposes of the present invention, the term “powdeP means a composition or an ingredient in pulverulent form, preferably essentially free of dust. In other words, the particle size distribution of the particles is such that the weight ratio of particles less than or equal to 50 micrometres in size (dust content) and preferably less than or equal to 10 micrometres in size (dust content) is advantageously less than or equal to 5%, preferably less than 2% and more particularly less than 1 % (particle size evaluated using a Retsch AS 200 Digit particle size analyser; oscillation height: 1 .25 mm/screening time: 5 minutes). Advantageously, the particle size is between 10 pm and 500 pm.
In the description, the term “at least one ” is equivalent to “one or more”.
For the purposes of the present invention, the term “build-up” of the colour on keratin fibres means the variation in colouring between locks of undyed hair and locks of dyed hair.
Natural dye(s)
In the context of the invention, the term “ natural dye” means any dye or dye precursor from a natural source, in particular of plant origin. The natural dyes may notably be obtained by extraction (and optionally purification) from a plant matrix, by grinding plants or plant parts, roots, wood, bark, berries, lichens, leaves, flowers, nuts or seeds. Natural dyes may also be obtained by fermentation.
The natural dye(s) are chosen, for example, from lawsone, juglone, alizarin, purpurin, camninic acid, kermesic acid, laccaic acid, purpurogallin, anthragallol, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, chlorophylls, chlorophyllins, orceins, haematin, haematoxylin, brazilin, brazilein, santalin, santarubin, carthamin, flavonoids (with, for example, morin, apigenidin and quercetin), anthocyans (such as apigeninidin), carotenoids and anthraquinones, or mixtures thereof.
Use is made, in particular, of extracts, decoctions or ground matter, notably powders, containing these natural dyes and notably extracts, decoctions or ground matter obtained, for example, from pernambuco wood, campeachy wood, sandalwood, orchil, turmeric, madder, indigo-producing plants such as indigo plant, sorghum, carrot, annatto, Brazil wood, safflower, henna or mixtures thereof.
In particular, the composition according to the invention may comprise indigo-producing plant powder and/or extract. (For the purposes of the present invention, the term “indigo-producing plant extract” means “a dye extract from an indigo-producing plant”).
As indigo-producing plants, mention may be made of numerous species derived from the following genera:
- Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata, Indigofera arrecta, Indigo fera gerardiana, Indigofera argentea, Indigofera indica, Indigofera longiracemosa
- Isatis such as Isatis tinctoria;
- Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria ) - Wrightia such as Wrightia tinctoria·,
- Calanthe such as Calanthe veratrifolia and
- Baphicacanthus such as Baphicacanthus cusia.
Preferably, the indigo-producing plant is of the genus Indigofera and more particularly is Indigofera tinctoria, suffruticosa or argentea, preferably Indigofera tinctoria.
Use may be made of all or part (in particular the leaves notably for Indigofera tinctoria) of the indigo- producing plant.
The dye that is useful according to the invention may be henna.
According to the present invention, the term “henna” refers to a henna plant powder and/or a henna plant dye extract, preferably from a henna plant such as Lawsonia alba or Lawsonia inermis. The henna plant powder and/or dye extract especially comprises lawsone and/or a glucosylated precursor thereof.
Preferably, the henna used according to the present invention is in powder form.
The henna used in the invention is preferably red henna ( Lawsonia inermis, alba). Lawsone [83-72-7] (Cl Natural Orange 6; Cl 75420), also known as isojuglone, may be found in henna shrubs (Lawsonia alba, Lawsonia inermis).
Preferably, the natural dye(s) useful according to the invention are in the form of powder(s).
Preferably, the natural dye(s) are chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, and/or mixtures thereof.
More preferentially, the natural dye(s) are chosen from henna powder, indigo-producing plant powders, and mixtures thereof.
The dye composition of the invention is in powder form and preferably the natural dyes used are in powder form. When the natural dyes are not in powder form, the composition of the invention comprises one or more other ingredients that enable the composition to be in powder form.
According to one particular embodiment, the total amount of natural dye(s) ranges from 30% to 99% by weight, preferably from 50% to 97% by weight and better still from 70% to 95% by weight, relative to the total weight of composition (A).
According to one embodiment, the total amount of natural dye(s) ranges from 1 % to 40% by weight, preferably from 2% to 35% by weight and better still from 5% to 30% by weight, relative to the total weight of the aqueous dye composition.
According to one embodiment, the composition of the invention comprises plants from the Cassia family, in particular chosen from Cassia angustifolia (senna) and/or Cassia auriculata or Cassia italica, or mixtures thereof. Preferably, the composition according to the invention may comprise a powder or a plant extract of the Cassia family, in particular of Cassia angustifolia and/or Cassia auriculata and/or Cassia italica, preferably Cassia angustifolia. For example, the composition of the invention comprises the natural dye(s) chosen from henna powder, indigo-producing plant powders, plant powders of the Cassia family, in particular Cassia angustifolia and/or Cassia auriculata and/or Cassia italica, and mixtures thereof. According to a preferred embodiment, the composition of the invention comprises the natural dye(s) chosen from henna powder, indigo-producing plant powders, Cassia angustifolia powders and mixtures thereof. Dispersants
For the purposes of the present invention, the term “dispersant’ means a compound added to a suspension to improve the diffusion on a surface or a liquid, to separate the particles, and that is capable of limiting, or even preventing, the agglomeration of the particles or powders and/or the sedimentation thereof.
Dispersant(s) according to the invention are, preferably, chosen from polymers of hydroxylated fatty acids and/or the salts and/or derivatives thereof.
The term “fatty acid” means a carboxylic acid comprising from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms and more preferentially from 15 to 20 carbon atoms.
The polymers of hydroxylated fatty acids may be homopolymers or copolymers of hydroxylated fatty acids.
Hydroxylated fatty acid derivatives that may notably be mentioned include hydroxylated fatty acid esters.
These polymers may contain one or more monomers other than the hydroxylated fatty acids and/or the salts or derivatives thereof, in particular non-hydroxylated fatty acids and/or salts or derivatives thereof.
According to one embodiment, the copolymers of hydroxylated fatty acids are obtained from one or more hydroxylated fatty acid monomers and optionally one or more hydroxylated fatty acid ester monomers.
According to another embodiment, the copolymers of hydroxylated fatty acids are obtained from one or more hydroxylated fatty acid monomers and optionally one or more non-hydroxylated fatty acid monomers.
The polymer of hydroxylated fatty acids may be chosen from polymers of hydroxylated carboxylic acids comprising from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms and more preferentially from 15 to 20 carbon atoms, and the salts thereof.
The polymers of hydroxylated fatty acids may be chosen from esters of hydroxylated fatty acid(s), preferably from esters of hydroxystearic acid, in particular of 12-hydroxystearic acid.
The polymers of hydroxylated fatty acids may be obtained from esters of hydroxylated fatty acids and of C4 to C20 and preferably Ce to C20 non-hydroxylated fatty acid, preferably from esters of polyhydroxystearic acid and of C4 to C20 and preferably Ce to C20 non-hydroxylated fatty acid. When the polymer is obtained from a hydroxylated fatty acid ester, the hydroxylated fatty acid ester is obtained from a C4 to C20 and preferably Ce to C20 fatty acid, preferably a hydroxystearic acid ester.
In particular, the polymer(s) of hydroxylated fatty acids are chosen from the polymers of esters of hydroxylated fatty acids, preferably from the oligomers of esters of 12-hydroxystearic acid and of Ce to C20 fatty acid such as poly(12-hydroxystearic acid) oligomer stearate.
Polymers of hydroxystearic acid, in particular of 12-hydroxystearic acid, are used in particular. According to a particular embodiment, the hydroxystearic acid polymer is obtained from 12- hydroxystearic acid, optionally from a hydroxystearic acid ester, for example methyl or ethyl hydroxystearate, notably methyl 12-hydroxystearate, and optionally from other hydroxylated fatty acids, for example 12-hydroxydodecanoic acid.
According to another particular embodiment, the hydroxystearic acid polymer is obtained from 12- hydroxystearic acid and optionally from stearic acid.
According to one embodiment the polymer of hydroxylated fatty acids is a 12-hydroxystearic acid homopolymer or copolymer.
Among the salts of the polymers of hydroxylated fatty acids, mention may be made of the potassium, sodium and ammonium salts.
Among the polymers of hydroxylated fatty acids and/or salts and/or derivatives thereof, examples that may be mentioned include oligomers of 12-hydroxystearic acid and of Ce to C20 fatty acid such as the oligomer of poly(12-hydroxystearic acid) with a molecular weight of about 750 g/mol such as the product sold by the company Innospec Active Chemicals under the reference Dispersun DSP-OL 100 or Dispersun DSP-OL 300 (INCI name: Polyhydroxystearic acid), esters of poly(12-hydroxystearic acid) with polyols such as glycerol or diglycerol, such as polyglyceryl-2 dipolyhydroxystearate (INCI name) sold under the reference Dehymuls® PGPH by the company Henkel, or the compound having the INCI name Polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Croda.
Use is preferably made of 12-hydroxystearic acid oligomers such as poly(12-hydroxystearic acid) oligomer stearate, for instance the product sold by the company Innospec Active Chemicals under the reference Dispersun DSP-OL 100 or Dispersun DSP-OL 300 (INCI name: polyhydroxystearic acid). The dispersant(s) according to the invention may also be chosen from polycondensates of ethylene oxide and propylene oxide, in particular from polycondensates of ethylene oxide and propylene oxide of the following formula:
H-(0-CH2-CH2)a-(0-CH(CH3)-CH2)b-(0-CH2-CH2)a'-0H, in which a and a' range from 2 to 150 and b ranges from 1 to 100.
As polycondensates of ethylene oxide and propylene oxide that may be used according to the invention, mention may be made of the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the name Synperonic, for instance Synperonic® PE/F32 (INCI name: Poloxamer 108), Synperonic® PE/F108 (INCI name: Poloxamer 338), Synperonic® PE/ L44 (INCI name: Poloxamer 124), Synperonic® PE/L42 (INCI name: Poloxamer 122), Synperonic® PE/F127 (INCI name: Poloxamer 407), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/L64 (INCI name: Poloxamer 184), Synperonic® PE/F88 (INCI name: Poloxamer 238), Synperonic® PE/F87 (INCI name: Poloxamer 237) from the company Croda, or Lutrol® F68 (INCI name: Poloxamer 188) by the company BASF.
Among the dispersants that can be used according to the invention, mention may also be made of fatty diesters such as diisostearyl malate.
According to one embodiment, the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still from 0.1% to 10% by weight, even better still from 0.5% to 8% by weight, or even from 1 % to 5% by weight, relative to the total weight of composition (A).
According to one embodiment, the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still from 0.1% to 10% by weight, even better still from 0.1% to 5% by weight, or even from 0.1% to 2% by weight, relative to the total weight of the aqueous dye composition.
Aqueous-phase thickener
For the purposes of the present invention, the term “aqueous-phase thickened means compounds which, by their presence at a concentration of 0.05% by weight, increase the viscosity of an aqueous composition into which they are introduced by at least 20 cps, preferably by at least 50 cps, at room temperature (25°C), at atmospheric pressure and at a shear rate of 1 s 1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheometer or the like).
The aqueous-phase thickener(s) are preferentially chosen from non-associative thickening polymers bearing sugar units, non-associative thickening polymers without sugar units, associative thickening polymers, and mixtures of these compounds.
The term "sugar unit" is understood to mean, within the meaning of the present invention, an oxygen comprising hydrocarbon compound which has several alcohol functional groups, with or without aldehyde or ketone functional group, and which comprises at least 4 carbon atoms.
The sugar units can be optionally modified by substitution, and/or by oxidation and/or by dehydration. The sugar units that may be included in the composition of the aqueous-phase thickening polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate and fructose.
Mention may in particular be made, as non-associative thickening polymers bearing sugar units, of native gums, such as: a) tree or shrub exudates, including:
- gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);
- ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);
- karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid);
- gum tragacanth (polymer of galacturonic acid, galactose, fucose, xylose and arabinose); b) gums derived from algae, including:
- agar (polymer derived from galactose and anhydrogalactose);
- alginates (polymers of mannuronic acid and of glucuronic acid);
- carrageenans and furcellerans (polymers of galactose sulfate and of anhydrogalactose sulfate); c) gums derived from seeds or tubers, including:
- guar gum (polymer of mannose and galactose);
- locust bean gum (polymer of mannose and galactose);
- fenugreek gum (polymer of mannose and galactose);
- tamarind gum (polymer of galactose, xylose and glucose);
- konjac gum (polymer of glucose and mannose); d) microbial gums, including:
- xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);
- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);
- scleroglucan gum (glucose polymer); e) plant extracts, including:
- cellulose (glucose polymer);
- starch (glucose polymer);
- inulin.
These polymers can be physically or chemically modified. Mention may in particular be made, as physical treatment, of the temperature.
Mention may be made, as chemical treatments, of esterification, etherification, amidation or oxidation reactions. These treatments make it possible to lead to polymers that may in particular be nonionic, anionic or amphoteric.
Preferably, these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.
The nonionic guar gums which can be used according to the invention can be modified by (poly)hydroxy(Ci-C6)alkyl groups.
Mention may be made, by way of example, among the (poly)hydroxy(Ci-C6)alkyl groups, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known from the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.
The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.
Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120 by the company Rhodia Chimie.
The botanical origin of the starch molecules that can be used in the present invention may be cereals or tubers. Thus, the starches are, for example, chosen from maize starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch or pea starch.
The starches can be chemically or physically modified, in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation or heat treatments.
Distarch phosphates or compounds rich in distarch phosphate will preferentially be used, for instance the product sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) and Prejel 200 (gelatinized acetylated cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized maize distarch phosphate).
According to the invention, use may also be made of amphoteric starches, these amphoteric starches comprising one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites; they are preferably bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, preferably carboxylic type. The cationic groups may be of primary, secondary, tertiary or quaternary amine type.
The starch molecules can result from any plant source of starch, such as in particular maize, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the abovementioned starches. The starch preferably results from potato.
The non-associative thickening polymers of the invention can be cellulose polymers not comprising a C10-C30 fatty chain in their structure.
The term "cellulose" polymer is understood to mean, according to the invention, any polysaccharide compound having, in its structure, sequences of glucose residues joined via b-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives can be anionic, cationic, amphoteric or nonionic. Thus, the cellulose polymers which can be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers. Among these cellulose polymers, cellulose ethers, cellulose esters and cellulose ether esters are distinguished.
Among the cellulose esters are inorganic esters of cellulose (cellulose nitrates, sulfates, phosphates, etc.), organic esters of cellulose (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetatetrimellitates, etc.), and mixed organic/inorganic esters of cellulose, such as cellulose acetatebutyrate sulfates and cellulose acetatepropionate sulfates. Among the cellulose ester ethers, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.
Mention may be made, among nonionic cellulose ethers without a C10-C30 fatty chain, i.e. which are "non-associative", of (Ci-C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example, Ethocel Standard 100 Premium from Dow Chemical); (poly)hydroxy(Ci-C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example, Natrosol 250 HHR provided by Aqualon) and hydroxypropylcelluloses (for example, Klucel EF from Aqualon); mixed (poly)hydroxy(Ci- C4)alkyl/(Ci-C4)alkylcellulose celluloses, such as hydroxypropyl methylcelluloses (for example, Methocel E4M from Dow Chemical), hydroxyethyl methylcelluloses, hydroxyethyl ethylcelluloses (for example, Bemnocoll E 481 FQ from AkzoNobel) and hydroxybutyl methylcelluloses.
Among the anionic cellulose ethers without a fatty chain, mention may be made of (poly)carboxy(Ci- C4)alkylcelluloses and salts thereof. Examples that may be mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.
Among the cationic cellulose ethers without a fatty chain, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and notably described in patent US 4 131 576, such as (poly)hydroxy(Ci-C4)alkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses notably grafted with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat® L 200 and Celquat® H 100 by the company National Starch.
Among the non-associative thickening polymers not bearing sugar units that may be used according to the invention, mention may be made of crosslinked acrylic acid or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or as mixtures.
A first family of non-associative thickening polymers that is suitable for use is represented by crosslinked acrylic acid homopolymers. Among the homopolymers of this type, mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, for instance the products sold under the names Carbopol 980, 981 , 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA. These polymers have the I NCI name Carbomer.
The non-associative thickening polymers may also be crosslinked (meth)acrylic acid copolymers, such as the polymer sold under the name Aqua SF1 by the company Noveon.
The non-associative thickening polymers may be chosen from 2-acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked or non-crosslinked copolymers thereof.
Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made of partially or totally neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of acrylamide; mention may be made in particular of the product described in Example 1 of document EP 503 853, and reference may be made to said document as regards these polymers.
Mention may also be made of copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT 10 by the company SEPPIC.
The dye composition that is useful according to the invention may comprise, as non-associative thickening polymers, ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.
Among the examples of ammonium acrylate homopolymers that may be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst. Among the copolymers of ammonium acrylate and of acrylamide that may be mentioned is the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst. Reference may be made notably to FR 2416 723, US 2 798 053 and US 2923 692 as regards the description and preparation of such compounds.
Use may also be made of cationic thickening polymers of acrylic type.
Among the aqueous-phase-thickening polymers, mention may also be made of associative polymers that are well known to those skilled in the art and especially of nonionic, anionic, cationic or amphoteric nature.
It is recalled that “associative polymers” are polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.
Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.
The term "hydrophobic group" means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms. Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene. Mention may be made, among the associative polymers of anionic type, of:
- (a) those including at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly those of which the hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, more particularly still a vinylcarboxylic acid and most particularly an acrylic acid or a methacrylic acid or mixtures thereof.
Among these anionic associative polymers, the ones that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether, and from 0 to 1 % by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.
Among the latter polymers, those most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth- 10), notably those sold by the company Ciba under the names Salcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10);
- (b) those including i) at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and ii) at least one hydrophobic unit of the (C10-C30) alkyl ester of an unsaturated carboxylic acid type. (C10-C30) Alkyl esters of unsaturated carboxylic acids that are useful in the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4509 949.
Among the anionic associative polymers of this type that will be used more particularly are those constituted of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those constituted of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.
Among said polymers above, the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially Pemulen TR1®, and the product sold by the company SEPPIC under the name Coatex SX®.
Mention may also be made of the acrylic acid/lauryl methacrylate/vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.
- (c) maleic anhydride/C3o-C38 a-olefin/alkyl maleate terpolymers, such as the product (maleic anhydride/C3o-C38 a-olefin/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies.
- (d) acrylic terpolymers comprising: i) about 20% to 70% by weight of an a,b-monoethylenically unsaturated carboxylic acid [A], ii) about 20% to 80% by weight of an a,b-monoethylenically unsaturated non-surfactant monomer other than [A], iii) about 0.5% to 60% by weight of a nonionic monourethane, which is the product of reaction of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in patent application EP-A-0 173 109 and more particularly the one described in Example 3, namely a methacrylic acid/methyl acrylate/ethoxylated (40 OE) behenyl alcohol dimethyl meta- isopropenyl benzyl isocyanate terpolymer as a 25% aqueous dispersion.
- (e) copolymers including among their monomers an a,b-monoethylenically unsaturated carboxylic acid and an ester of an a,b-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.
Preferentially, these compounds also comprise as monomer an ester of an a,b-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.
An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer; and also Aculyn 88, also sold by the company Rohm & Haas.
- (f) amphiphilic polymers including at least one ethylenically unsaturated monomer bearing a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part. These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.
The ethylenically unsaturated monomers bearing a sulfonic group are notably chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids, N-(Ci- C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
(Meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n- butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2- methacrylamidododecylsulfonic acid or2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used. 2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will more particularly be used.
The polymers of this family may be chosen notably from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine ordi-n-alkylamine, and such as those described in patent application WO 00/31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, b-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
The preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer.
These same copolymers may also contain one or more ethylenically unsaturated monomers not including a fatty chain, such as (meth)acrylic acids, b-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds. These copolymers are described notably in patent application EP-A 750899, patent US 5089578 and in the following publications from Yotaro Morishima:
- Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336 ;
- Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, No. 10 (2000), 3694-3704;
- Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000), 5324-5332;
- Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem., 40(2), (1999), 220-221.
Among these polymers, mention may be made of:
- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, including from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide or (C8-Ci6)alkyl(meth)acrylate units relative to the polymer, such as those described in patent application EP-A 750899;
- terpolymers including from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-Ci8)alkylacrylamide units, such as those described in patent US-5 089 578. Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
Among the cationic associative polymers, mention may be made of:
(a) cationic associative polyurethanes;
(b) the compound sold by the company Noveon under the name Aqua CC and which corresponds to the INCI name Polyacrylate- 1 Crosspolymer.
Polyacrylate- 1 Crosspolymer is the product of polymerization of a monomer mixture comprising:
- a di(Ci-C4 alkyl)amino(Ci-C6 alkyl) methacrylate,
- one or more C1-C30 alkyl esters of (meth)acrylic acid,
- a polyethoxylated C10-C30 alkyl methacrylate (20-25 mol of ethylene oxide units),
- a 30/5 polyethylene glycol/polypropylene glycol allyl ether,
- a hydroxy(C2-C6 alkyl) methacrylate, and
- an ethylene glycol dimethacrylate.
(c) quaternized (poly)hydroxyethylcelluloses modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups including at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably include from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18-B® (C12 alkyl) and Quatrisoft LM-X 529-8® (C18 alkyl) sold by the company Aqualon, and the products Crodacel QM®, Crodacel QL® (C12 alkyl) and Crodacel QS® (C18 alkyl) sold by the company Croda and the product Softcat SL 100® sold by the company Aqualon.
(d) cationic polyvinyllactam polymers. Such polymers are for example described in patent application WO-OO/68282. As cationic poly(vinyllactam) polymers according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammoniu m tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropylammonium tosylate or chloride terpolymers are notably used.
The amphoteric associative polymers are preferably chosen from those including at least one noncyclic cationic unit. Even more particularly, those prepared from or comprising 1 to 20 mol%, preferably 1.5 to 15 mol% and even more particularly 1 .5 to 6 mol% of fatty-chain monomer relative to the total number of moles of monomers are preferred. Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.
Among the amphoteric associative polymers according to the invention, the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers. The associative polymers of nonionic type that may be used according to the invention are preferably chosen from:
(a) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers, of which examples that may be mentioned include:
- the products Antaron V216® or Ganex V216® (vinylpyrrolidone/hexadecene copolymer), sold by the company ISP;
- the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer), sold by the company ISP;
(b) copolymers of C1-C6 alkyl methacrylates or acrylates and of amphiphilic monomers including at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208®;
(c) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers including at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer;
(d) polyurethane polyethers including in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
(e) polymers with an aminoplast ether backbone containing at least one fatty chain, such as the Pure Thix® compounds sold by the company Sud-Chemie;
(f) celluloses or derivatives thereof, modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof in which the alkyl groups are of Ce, and in particular:
- nonionic alkylhydroxyethylcelluloses, such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (Ci6 alkyl) sold by Aqualon;
- nonionic nonoxynylhydroxyethylcelluloses, such as the product Amercell HM-1500 sold by Amerchol;
- nonionic alkylcelluloses, such as the product Bemnocoll EHM 100 sold by Berol Nobel;
(g) associative guar derivatives, for instance hydroxypropyl guars modified with a fatty chain, such as the product Esaflor HM 22 (modified with a C22 alkyl chain) sold by the company Lamberti; the product Miracare XC 95-3 (modified with a C14 alkyl chain) and the product RE 205-146 (modified with a C20 alkyl chain) sold by Rhodia Chimie.
Preferably, the polyurethane polyethers include at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being side chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more side chains to be envisaged. In addition, the polymer may include a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer bearing a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer). These same polymers may also be graft polymers or star polymers.
The nonionic fatty-chain polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain including from 50 to 1000 oxyethylene groups. The nonionic polyurethane polyethers include a urethane bond between the hydrophilic blocks, whence the origin of the name.
By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, use may also be made of Rheolate 205® bearing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®.
Mention may also be made of the product Elfacos T210® bearing a C12-C14 alkyl chain, and the product Elfacos T212® bearing a C18 alkyl chain, from Akzo.
The product DW 1206B® from Rohm & Haas bearing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.
Use may also be made of solutions or dispersions of these polymers, notably in water or in aqueous- alcoholic medium. Examples of such polymers that may be mentioned include Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox. Use may also be made of the products DW 1206F and DW 1206J sold by the company Rohm & Haas.
The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. ScL, 271 , 380-389 (1993).
It is even more particularly preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
Such polyurethane polyethers are notably sold by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
Preferably, the aqueous-phase thickeners that are useful according to the invention are chosen from non-associative polymers bearing sugar units.
More preferentially, the aqueous-phase thickeners that are useful according to the invention are chosen from native gums.
In a preferred variant of the invention, the aqueous-phase thickeners that are useful according to the invention are chosen from guar gums, xanthan gums and mixtures thereof.
According to one embodiment, the total amount of aqueous-phase thickeners ranges from 0.1 % to 20% by weight, preferably from 0.5% to 10% by weight and better still from 1 % to 5% by weight, relative to the total weight of composition (A).
According to one embodiment, the total amount of aqueous-phase thickeners ranges from 0.1 % to 5% by weight, preferably from 0.2% to 5% by weight and better still from 0.3% to 2% by weight, relative to the total weight of the aqueous dye composition.
According to one preferred embodiment, the aqueous composition of the invention comprises at least one natural dye chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, at least one Cassia angustifolia extract and/or powder and mixtures thereof, at least one polymer of hydroxylated fatty acids and/or salts and/or derivatives thereof chosen from hydroxystearic acid polymers and at least one aqueous-phase thickener chosen from native gums. According to one preferred embodiment, the process according to the invention is a process for preparing a composition for dyeing the hair which consists in mixing:
- a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one organic solvent and/or at least one oil, with
- an aqueous composition (B).
According to this variant, the method for dyeing the hair comprises the application of this composition on the hair. It being possible for this composition to be obtained by mixing
- a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one solvent and/or at least one oil, and
- an aqueous composition (B).
The aqueous dye composition then comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one organic solvent and/or at least one oil (ready-to-use composition).
According to this embodiment, preferably, the process according to the invention is a process for preparing a composition for dyeing the hair which consists in mixing:
- a dye composition (A) in powder form comprising at least one natural dye chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, Cassia angustifolia extracts and/or powders and mixtures thereof, at least one polymer of hydroxylated fatty acids and/or salts and/or derivatives thereof chosen from hydroxystearic acid polymers, at least one aqueous-phase thickener chosen from native gums, at least one organic solvent chosen from propylene glycol, glycerol, hexylene glycol, benzyl alcohol or phenoxyethanol, ethanol and mixtures thereof and at least one oil chosen from avocado oil, olive oil, coconut oil, argan oil, sunflower oil, rapeseed oil and mixtures thereof, better still from coconut oil, rapeseed oil and mixtures thereof, with - an aqueous composition (B).
Organic solvent
The term “organic solvent” is intended to mean an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it.
The organic solvent(s) that are useful in the compositions of the invention is or are chosen from C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol. Preferably, the organic solvents that are useful in the compositions of the invention are chosen from C1-C4 lower alkanols; polyols and polyol ethers; aromatic alcohols; and mixtures thereof, preferably chosen from propylene glycol, glycerol, hexylene glycol, benzyl alcohol or phenoxyethanol, ethanol and mixtures thereof.
According to one embodiment, the total amount of organic solvents as defined above, when they are present, ranges from 0.01 % to 30% by weight relative to the total weight of the composition in which they are found, preferably from 0.1% to 20% by weight, better still from 1 % to 10% by weight relative to the total weight of composition (A).
According to one embodiment, the total amount of organic solvents as defined above, when they are present, ranges from 0.01 % to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.05% to 10% by weight, better still from 0.1% to 5% by weight relative to the total weight of the aqueous dye composition.
Oil(s)
For the purposes of the invention, the term “o/f means a “fatty substance" that is liquid at a temperature of 30°C and at atmospheric pressure (760 mmHg). The viscosity at 25°C is preferably less than 1200 cps and better still less than 500 cps (defined, for example, from the Newtonian plateau determined using an ARG2 rheometer from TA Instruments equipped with a spindle with cone-plate geometry 60 mm in diameter and with an angle of 2 degrees over a shear stress range of from 0.1 Pa to 100 Pa).
The term “fatty substance" means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5% by weight, preferably less than 1 % by weight and even more preferentially less than 0.1 % by weight). They generally have in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
The term “nonsilicone oil or fatty substance" refers to an oil or a fatty substance not containing any Si- O bonds and the term “silicone oil or fatty substance” refers to an oil or a fatty substance containing at least one Si-O bond.
The oils that are useful according to the invention are not (poly)oxyalkylenated or (polyjglycerolated ethers.
The oils that are useful according to the invention are not fatty acids in salified form giving water- soluble soaps.
More particularly, the oils that are useful according to the invention are chosen from nonsilicone oils and in particular C6-C16 hydrocarbons or hydrocarbons containing more than 16 carbon atoms and in particular alkanes; triglyceride oils of plant origin; essential oils; glycerides of synthetic origin, fatty alcohols; fatty acid and/or fatty alcohol esters other than triglycerides.
It is recalled that, for the purposes of the invention, fatty alcohols, esters and acids more particularly bear at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising 6 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
As regards the C6-C16 liquid hydrocarbons, they are linear, branched or optionally cyclic, and are preferably alkanes. Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, isododecane, tridecane or isoparaffins, such as isohexadecane or isodecane, or mixtures thereof. The linear or branched hydrocarbons of mineral or synthetic origin comprising more than 16 carbon atoms are preferably chosen from liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleam®, or mixtures thereof.
Among the triglycerides of plant or synthetic origin, mention may be made of liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic oroctanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, coconut oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
The liquid fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols including from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Examples that may be mentioned include octyldodecanol, 2- butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol or linoleyl alcohol, or mixtures thereof.
As regards the liquid esters of fatty acids and/or of fatty alcohols other than the triglycerides mentioned above, mention may be made notably of esters of saturated or unsaturated, linear C3-C29 or branched C4-C30 aliphatic monoacids or polyacids and of saturated or unsaturated, linear C3-C29or branched C4-C30 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10. Esters of a fatty acid and/or of a fatty alcohol, for instance Purcellin oil (stearyl octanoate), isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate or 2-octyldodecyl myristate or lactate, may be used.
Among the essential oils that are useful according to the invention, mention may be made of those mentioned in Ullmann's Encyclopedia of Industrial Chemistry (“Flavors and Fragrances" , Karl-Georg Fahlbusch et al., Published Online: 15 Jan 2003, DOI: 10.1002/14356007.a11_141).
According to a preferred variant of the invention, the oil(s) are chosen from C6-C16 alkanes, polydecenes, liquid esters of a fatty acid and/or of a fatty alcohol, in particular triglycerides of plant or synthetic origin, and liquid fatty alcohols, or mixtures thereof. Better still, the fatty substance is chosen from liquid esters of a fatty acid and/or of a fatty alcohol, triglycerides of plant or synthetic origin, or mixtures thereof; more preferentially from triglycerides of plant or synthetic origin.
According to another most particularly preferred embodiment of the invention, the oils are chosen from oils of natural origin, more particularly oils of plant origin, preferentially jojoba oil, babassu oil, sunflower oil, olive oil, coconut oil, Brazil nut oil, marula oil, com oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil and also rapeseed oil, borage oil, evening primrose oil, pomegranate oil, mango oil, palm oil and cottonseed oil, and mixtures thereof.
More particularly, the oils of plant origin that are useful according to the invention are chosen from avocado oil, olive oil, coconut oil, argan oil, sunflower oil, rapeseed oil and mixtures thereof, better still from coconut oil, rapeseed oil and mixtures thereof.
Use will preferably be made of the coconut oil with the I NCI name Cocos nucifera (coconut) oil and the rapeseed oil with the INCI name Brassica campestris (rapeseed) seed oil.
According to a particular embodiment, the total amount of oil(s), when it is (they are) present, ranges from 0.1% to 10% by weight, more particularly from 0.5% to 8% by weight, preferentially from 1% to 6% by weight, better still from 1.5% to 5% by weight relative to the total weight of composition (A). According to a particular embodiment, the total amount of oil(s), when it is (they are) present, ranges from 0.01% to 10% by weight, more particularly from 0.05% to 5% by weight, preferentially from 0.1% to 3% by weight, better still from 0.1% to 2% by weight relative to the total weight of the aqueous dye composition.
Additional dye(s)
The dye composition in powder form may further comprise one or more additional dyes in the form of powders.
Among the additional dyes in powder form that are useful according to the invention, mention may be made of direct dyes different from the dyes in powder form as described above. These additional direct dyes may be synthetic.
The additional dyes may be contained in the aqueous composition mixed with the dye composition. The synthetic direct dyes are preferably chosen from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or nonaromatic dyes such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine direct dyes, and fluorescent dyes.
Among the additional dyes that are useful according to the invention, mention may also be made of oxidation bases and/or couplers conventionally used to dye keratin fibres. Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof. Among the couplers, mention may be made especially of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof. These bases and these couplers form a dye when they are in contact with an oxidizing agent.
When it is (they are) present, the additional dye(s) is (are) preferably present in an amount of between 0.001% and 10% by weight of the total weight of the composition (s) under consideration.
Adjuvants)
The compositions used in the process for preparing a dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as surfactants, polymers different from the dispersants as described above and from the aqueous-phase thickeners as described above and aqueous-phase thickeners different from the aqueous-phase thickeners as described above, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents different from the oils as described above, film-forming agents, ceramides, preserving agents and opacifiers.
Needless to say, those skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the composition or compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition (s).
Process for preparing a composition for dyeing the hair
The process for preparing a composition for dyeing the hair according to the invention consists in mixing a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with an aqueous composition (B).
In a second variant, the process for preparing a composition for dyeing the hair according to the invention consists in mixing a dye composition in powder form (A) comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener and/or at least one organic solvent and/or at least one oil, with an aqueous composition (B).
In a particular embodiment, composition (B) is water.
By mixing composition (A) and composition (B), an aqueous hair dye composition is obtained that comprises at least one natural dye, at least one dispersant, at least one aqueous-phase thickener and/or at least one organic solvent and/or at least one oil.
According to one embodiment, the ready-to-use composition obtained by the preparation process according to the invention is obtained by extemporaneous mixing, at the time of use, of a composition (A) as described previously and of an aqueous composition (B).
According to this embodiment, the mixing of compositions (A) and (B) is preferably performed less than 30 min before application, preferentially less than 15 min before application, better still less than 10 min before application, or even less than 5 min before application.
Preferably, composition (B) is used at a temperature of between 10°C and 100°C, better still between 40°C and 100°C.
The mixing ratio between the composition (A) and composition (B) may range from 0.01 to 10, preferably from 0.1 to 5, preferentially from 0.15 to 1 , and better still from 0.2 to 0.5.
Composition obtained by the preparation process according to the invention
According to one particular embodiment, the hair dye composition of the invention comprises at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, at least one organic solvent, at least one oil and water.
According to one particular embodiment, the hair dye composition comprises at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, water, optionally at least one organic solvent, and optionally at least one oil.
According to this embodiment, in this composition, the total amount of natural dye(s) ranges from 1% to 40% by weight, preferably from 2% to 35% by weight, better still from 5% to 30% by weight, the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still 0.1% to 10% by weight, even better still from 0.1% to 5% by weight, or even 0.1 % to 2% by weight, the total amount of aqueous-phase thickeners ranges from 0.1% to 5% by weight, preferably from 0.2% to 5% by weight, and better still from 0.3% to 2% by weight, the total amount of organic solvents, when they are present, ranges from 0.01% to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.05% to 10% by weight, better still from 0.1% to 5% by weight, the total amount of oil(s), when it is (they are) present, ranges from 0.01% to 10% by weight, more particularly from 0.05% to 5% by weight, preferentially from 0.1% to 3% by weight, better still from 0.1 % to 2% by weight, relative to the total weight of this composition.
Dyeing process
Another subject of the present invention is a method for dyeing the hair using the hair dye composition comprising at least one natural dye, at least one dispersant, at least one aqueous-based thickener, water, optionally at least one organic solvent, and optionally at least one oil, which consists in applying this composition to dry or wet hair.
This composition may result from the preparation process as described above consisting in mixing the compositions (A) and (B) as described above.
The composition is then left in place for a time usually ranging from 1 minute to 2 hours, preferably from 5 minutes to 1 hour 30 minutes and better still from 10 minutes to 1 hour.
Advantageously, after application of the hair dye composition, the head of hair may be subjected to a heat treatment. In practice, this operation may be performed using a hairstyling hood, a hairdryer, an infrared ray emitter or other standard heating appliances.
The temperature during the process is conventionally between room temperature (between 15 and 25°C) and 80°C and preferably between room temperature and 60°C.
After the treatment, the hair fibres are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried (mechanically with a towel or absorbent paper, or by heat) or left to dry.
Device or kit
Another subject of the invention is a multi-compartment hair treatment device or kit comprising at least two compartments.
The multi-compartment device comprises at least one compartment comprising the dye composition in powder form as described above comprising at least one dye, at least one dispersant and at least one aqueous-phase thickener and one second compartment comprising an aqueous composition. According to one variant, the device according to the invention also comprises an additional composition comprising one or more treating agents.
The compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means which may be identical or different, such as fine brushes, coarse brushes or sponges.
The device mentioned above may also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913. Examples
The compositions A to F according to the invention were prepared. The proportions of the ingredients are indicated in grams of active material per 100 g of composition, unless otherwise indicated.
[Table 1]
Figure imgf000026_0001
At the time of use, each of the dye compositions A to F is mixed with three or four times its own weight of water at 50°C or 100°C.
Each of the mixtures is then applied to locks of natural hair containing 90% white hairs, in a proportion of 10 g of mixture per 1 g of hair.
After leaving it on plates thermostatically maintained at 33°C for 30 minutes to 60 minutes, the hair is rinsed and dried.
The viscosity of the mixtures is evaluated after 24 hours of storage at room temperature. The measurement was taken using a Rheomat RM200 viscometer. The mixture is deposited in a cup thermostatically maintained at 25°C. A deviation unit (DU) is measured using a spindle of type 3 with a speed of 200 rpm for 30 seconds. Results
[Table 2]
Figure imgf000027_0001
Compositions A to F according to the invention mix readily with water, have a good stability, the final texture is homogeneous, shiny, soft and creamy.
Application to the hair is easy, the composition does not dry out during the leave-on time which enables a better, faster rinseability.
Compositions A to F according to the invention make it possible to obtain colourings with varied shades.

Claims

Claims
[Claim 1 ] Process for preparing a composition for dyeing the hair which consists in mixing:
- a dye composition (A) in powder form comprising at least one natural dye, at least one dispersant and at least one aqueous-phase thickener, with
- an aqueous composition (B).
[Claim 2] Process according to Claim 1 , in which the natural dye(s) is (are) chosen from lawsone, henna extracts and/or powders, indigo, indigo-producing plant extracts and/or powders, and mixtures thereof.
[Claim 3] Process according to any one of the preceding claims, in which the total amount of natural dye(s) ranges from 30% to 99% by weight, preferably from 50% to 97% by weight, better still from 70% to 95% by weight, relative to the total weight of the composition of (A).
[Claim 4] Process according to any one of the preceding claims, in which the dispersant(s) is (are) chosen from polymers of hydroxylated fatty acids, preferably from polymers of hydroxylated carboxylic acids comprising from 8 to 40 carbon atoms, preferably from 12 to 30 carbon atoms, more preferentially from 15 to 20 carbon atoms and/or salts thereof, preferentially from polymers of 12-hydroxystearic acid and/or salts thereof.
[Claim 5] Process according to the preceding claim, in which the polymer(s) of hydroxylated fatty acids is (are) obtained from esters of hydroxylated fatty acid(s), preferably from esters of hydroxystearic acid, in particular of 12-hydroxystearic acid.
[Claim 6] Process according to either one of the preceding Claims 4 and 5, in which the polymer(s) of hydroxylated fatty acids are obtained from esters of hydroxylated fatty acids and of C4 to C20 and preferably Cs to C20 non-hydroxylated fatty acid, preferably from esters of polyhydroxystearic acid and of C4 to C20 and preferably Cs to C20 non- hydroxylated fatty acid.
[Claim 7] Process according to any one of the preceding Claims 4 to 6, in which the polymer(s) of hydroxylated fatty acids are chosen from the polymers of esters of hydroxylated fatty acids, preferably from the oligomers of esters of 12-hydroxystearic acid and of Cs to C20 fatty acid such as poly(12-hydroxystearic acid) oligomer stearate.
[Claim 8] Process according to any one of the preceding claims, in which the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still from 0.1% to 10% by weight, even better still from 0.5% to 8% by weight, relative to the total weight of composition (A).
[Claim 9] Process according to any one of the preceding claims, in which the aqueous- phase thickener(s) are chosen from non-associative polymers bearing a sugar unit, preferably from native gums, more preferentially chosen from xanthan gums, guar gums and mixtures thereof.
[Claim 10] Process according to any one of the preceding claims, in which the total amount of aqueous-phase thickeners ranges from 0.1% to 20% by weight, preferably from 0.5% to 10% by weight, and better still from 1% to 5% by weight, relative to the total weight of composition (A).
[Claim 11 ] Process according to any one of the preceding claims, in which the composition (A) comprises at least one organic solvent, preferably chosen from propylene glycol, glycerol, hexylene glycol, benzoyl alcohol or phenoxyethanol, ethanol and mixtures thereof.
[Claim 12] Process according to any one of the preceding claims, in which the composition (A) comprises at least one oil, preferably chosen from oils of natural origin, preferably from avocado oil, olive oil, coconut oil, argan oil, sunflower oil, rapeseed oil and mixtures thereof, better still from coconut oil, rapeseed oil and mixtures thereof.
[Claim 13] Process according to any one of the preceding claims, in which a dye composition (A) according to any one of Claims 1 to 12 is mixed with an aqueous composition (B), preferably with water, the mixing ratio between composition (A) and composition (B) preferably ranging from 0.01 to 10, preferably from 0.1 to 5, preferentially from 0.15 to 1 , better still from 0.2 to 0.5.
[Claim 14] Hair dye composition comprising at least one natural dye, at least one dispersant, at least one aqueous-phase thickener, water, optionally at least one organic solvent, optionally at least one oil, the natural dyes, the dispersants, the aqueous-phase thickeners, the organic solvents when they are present, and the oils when they are present, are as defined in any one of the preceding claims.
[Claim 15] Hair dye composition according to the preceding claim, in which the total amount of natural dye(s) ranges from 1 % to 40% by weight, preferably from 2% to 35% by weight, better still from 5% to 30% by weight, the total amount of dispersant(s) ranges from 0.01% to 15% by weight, preferably from 0.05% to 12% by weight, better still 0.1 % to 10% by weight, even better still from 0.1 % to 5% by weight, or even 0.1 % to 2% by weight, the total amount of aqueous-phase thickeners ranges from 0.1% to 5% by weight, preferably from 0.2% to 5% by weight, and better still from 0.3% to 2% by weight, the total amount of organic solvents, when they are present, ranges from 0.01 % to 15% by weight relative to the total weight of the composition in which they are found, preferably from 0.05% to 10% by weight, better still from 0.1 % to 5% by weight, the total amount of oil(s), when it is (they are) present, ranges from 0.01% to 10% by weight, more particularly from 0.05% to 5% by weight, preferentially from 0.1 % to 3% by weight, better still from 0.1 % to 2% by weight, relative to the total weight of this composition.
[Claim 16] Method for dyeing the hair, in which the hair dye composition of Claims 14 and 15 is applied.
[Claim 17] Method for dyeing the hair according to the preceding claim, in which the hair dye composition results from the process as described in any one of Claims 1 to 13.
PCT/EP2020/086886 2019-12-20 2020-12-17 Process for preparing a composition for dyeing the hair starting from a composition in powder form and an aqueous composition WO2021123061A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FRFR1915370 2019-12-20
FR1915370A FR3104997B1 (en) 2019-12-20 2019-12-20 Process for Preparing a Composition for Coloring the Hair from a Composition In the Form of a Powder and an Aqueous Composition

Publications (1)

Publication Number Publication Date
WO2021123061A1 true WO2021123061A1 (en) 2021-06-24

Family

ID=70008797

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/086886 WO2021123061A1 (en) 2019-12-20 2020-12-17 Process for preparing a composition for dyeing the hair starting from a composition in powder form and an aqueous composition

Country Status (2)

Country Link
FR (1) FR3104997B1 (en)
WO (1) WO2021123061A1 (en)

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798053A (en) 1952-09-03 1957-07-02 Goodrich Co B F Carboxylic polymers
US2923692A (en) 1954-01-25 1960-02-02 Goodrich Co B F Mucilaginous composition comprising salt of crosslinked carboxylic polymer and method of preparing same
US3915921A (en) 1974-07-02 1975-10-28 Goodrich Co B F Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers
US4131576A (en) 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
FR2416723A1 (en) 1978-02-14 1979-09-07 Hoechst Ag USE OF CROSS-LINKED POLYMERS TO RAISE THE VISCOSITY OF COSMETIC, PHARMACEUTICAL OR TECHNICAL PRODUCTS
US4509949A (en) 1983-06-13 1985-04-09 The B. F. Goodrich Company Water thickening agents consisting of copolymers of crosslinked acrylic acids and esters
EP0173109A2 (en) 1984-08-23 1986-03-05 DeSOTO, INC. Alkali soluble latex thickeners
FR2586913A1 (en) 1985-09-10 1987-03-13 Oreal PROCESS FOR FORMING IN IN SITU A COMPOSITION CONSISTING OF TWO PARTS CONDITIONED SEPARATELY AND DISPENSING ASSEMBLY FOR IMPLEMENTING SAID METHOD
US5089578A (en) 1986-03-28 1992-02-18 Exxon Research And Engineering Company Hydrophobically associating terpolymers containing sulfonate functionality
EP0503853A2 (en) 1991-03-08 1992-09-16 Scott Bader Company Limited Water soluble polymeric thickeners for products for topical application
EP0750899A2 (en) 1995-06-30 1997-01-02 Shiseido Company Limited An emulsifier or solubilizer which consists of a water soluble amphiphilic polyelectrolyte, and an emulsified composition or a solubilized composition and an emulsified cosmetic or a solubilized cosmetic containing it
WO1998044012A1 (en) 1997-03-31 1998-10-08 Calgon Corporation Ampholyte polymers for use in personal care products
WO2000031154A1 (en) 1998-11-23 2000-06-02 Sofitech N.V. Invertible emulsions stabilised by amphiphilic polymers and application to bore fluids
WO2000068282A1 (en) 1999-05-07 2000-11-16 Isp Investments Inc. Conditioning/styling terpolymers
FR3004941A1 (en) * 2013-04-26 2014-10-31 Oreal COMPOSITION BASED ON HENNE OR INDIGO POWDER WITH OIL PRE-DISPERSION, HAIR COLORING METHOD USING THE SAME
FR3004943A1 (en) * 2013-04-26 2014-10-31 Oreal COMPOSITION COMPRISING HENNE AND / OR INDIGO, OIL AND SACCHARIDE, AND CAPILLARY COLORING METHOD IMPLEMENTING THE SAME
FR3075637A1 (en) * 2017-12-22 2019-06-28 L'oreal HAIR COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A PROCESSING STEP COMPRISING THE APPLICATION OF AQUEOUS PHASE, A FATTY PHASE AND A DIRECT COLOR

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798053A (en) 1952-09-03 1957-07-02 Goodrich Co B F Carboxylic polymers
US2923692A (en) 1954-01-25 1960-02-02 Goodrich Co B F Mucilaginous composition comprising salt of crosslinked carboxylic polymer and method of preparing same
US3915921A (en) 1974-07-02 1975-10-28 Goodrich Co B F Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers
US4131576A (en) 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
FR2416723A1 (en) 1978-02-14 1979-09-07 Hoechst Ag USE OF CROSS-LINKED POLYMERS TO RAISE THE VISCOSITY OF COSMETIC, PHARMACEUTICAL OR TECHNICAL PRODUCTS
US4509949A (en) 1983-06-13 1985-04-09 The B. F. Goodrich Company Water thickening agents consisting of copolymers of crosslinked acrylic acids and esters
EP0173109A2 (en) 1984-08-23 1986-03-05 DeSOTO, INC. Alkali soluble latex thickeners
FR2586913A1 (en) 1985-09-10 1987-03-13 Oreal PROCESS FOR FORMING IN IN SITU A COMPOSITION CONSISTING OF TWO PARTS CONDITIONED SEPARATELY AND DISPENSING ASSEMBLY FOR IMPLEMENTING SAID METHOD
US5089578A (en) 1986-03-28 1992-02-18 Exxon Research And Engineering Company Hydrophobically associating terpolymers containing sulfonate functionality
EP0503853A2 (en) 1991-03-08 1992-09-16 Scott Bader Company Limited Water soluble polymeric thickeners for products for topical application
EP0750899A2 (en) 1995-06-30 1997-01-02 Shiseido Company Limited An emulsifier or solubilizer which consists of a water soluble amphiphilic polyelectrolyte, and an emulsified composition or a solubilized composition and an emulsified cosmetic or a solubilized cosmetic containing it
WO1998044012A1 (en) 1997-03-31 1998-10-08 Calgon Corporation Ampholyte polymers for use in personal care products
WO2000031154A1 (en) 1998-11-23 2000-06-02 Sofitech N.V. Invertible emulsions stabilised by amphiphilic polymers and application to bore fluids
WO2000068282A1 (en) 1999-05-07 2000-11-16 Isp Investments Inc. Conditioning/styling terpolymers
FR3004941A1 (en) * 2013-04-26 2014-10-31 Oreal COMPOSITION BASED ON HENNE OR INDIGO POWDER WITH OIL PRE-DISPERSION, HAIR COLORING METHOD USING THE SAME
FR3004943A1 (en) * 2013-04-26 2014-10-31 Oreal COMPOSITION COMPRISING HENNE AND / OR INDIGO, OIL AND SACCHARIDE, AND CAPILLARY COLORING METHOD IMPLEMENTING THE SAME
FR3075637A1 (en) * 2017-12-22 2019-06-28 L'oreal HAIR COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A PROCESSING STEP COMPRISING THE APPLICATION OF AQUEOUS PHASE, A FATTY PHASE AND A DIRECT COLOR

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering", MACROMOLECULES, vol. 33, no. 10, 2000, pages 3694 - 3704
"Self-assembling amphiphilic polyelectrolytes and their nanostructures", CHINESE JOURNAL OF POLYMER SCIENCE, vol. 18, no. 40, 2000, pages 323 - 336
"Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers", POLYM. PREPRINT, DIV. POLYM. CHEM., vol. 40, no. 2, 1999, pages 220 - 221
"Ullmann's Encyclopedia of Industrial Chemistry", 15 January 2003, article "Flavors and Fragrances"
DATABASE GNPD [online] MINTEL; 4 April 2016 (2016-04-04), ANONYMOUS: "Temporary Hair Colouring Spray", XP055720661, retrieved from www.gnpd.com Database accession no. 3914317 *
DATABASE GNPD [online] MINTEL; 5 November 2018 (2018-11-05), ANONYMOUS: "100% Plant Hair Colourant", XP055720654, retrieved from www.gnpd.com Database accession no. 6100113 *
G. FONNUMJ. BAKKEFK. HANSEN, COLLOID POLYM. SCI., vol. 271, 1993, pages 380 - 389
LANGMUIR, SOLUTION PROPERTIES OF MICELLE NETWORKS FORMED BY NONIONIC MOIETIES COVALENTLY BOUND TO A POLYELECTROLYTE: SALT EFFECTS ON RHEOLOGICAL BEHAVIOR, vol. 16, no. 12, 2000, pages 5324 - 5332

Also Published As

Publication number Publication date
FR3104997A1 (en) 2021-06-25
FR3104997B1 (en) 2021-11-26

Similar Documents

Publication Publication Date Title
EP3389618B1 (en) Process for treating keratin fibres using an aqueous composition comprising a combination of particular alkoxysilanes
FR3075637B1 (en) HAIR COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A PROCESSING STEP COMPRISING THE APPLICATION OF AQUEOUS PHASE, A FATTY PHASE AND A DIRECT COLOR
WO2018115451A1 (en) Cosmetic composition for direct dyeing comprising an aqueous phase and a fatty phase that are visually distinct from each other
FR2944441A1 (en) Composition, useful to treat keratin material e.g. hair, comprises fatty substance (e.g. polydecene), surfactants (non-ionic, anionic, cationic/amphoteric surfactant) and hydrosoluble beneficial agents (e.g. amino acid)
WO2020127383A1 (en) Antimicrobial mixture containing 4-(3-ethoxy-4-hydroxyphenyl) butan-2-one, and 4-hydroxyacetophenone, and composition containing same
EP3003496A1 (en) Cosmetic composition comprising an aqueous phase and a fatty phase that are visually distinct
US9522106B2 (en) Composition for dyeing keratinous fibres comprising a direct dye having a disulphide/thiol functional group, a thickening polymer, an ethoxylated fatty alcohol and/or a nonionic surfactant, an alkaline agent and a reducing agent
EP2677996B1 (en) Composition for dyeing keratinous fibres comprising a direct dye having a disulphide/thiol functional group, a thickening polymer, an ethoxylated fatty alcohol and/or a nonionic surfactant, an alkaline agent and a reducing agent
US20220000754A1 (en) Perfume gel
EP3727287A1 (en) Hair dyeing process comprising a step of dyeing with henna and/or indigo and a treatment step comprising the application of a composition comprising a buffer system
ES2568884T3 (en) Cosmetic composition comprising a vinylformamide / vinylformamine copolymer and a thickening polymer
FR3075607A1 (en) CAPILLARY COLORING PROCESS COMPRISING A PROCESSING STEP WITH TITANIUM SALT AND A COLORING STEP COMPRISING THE APPLICATION OF AQUEOUS PHASE, A FATTY PHASE AND A DIRECT COLOR
JP7362237B2 (en) Method and kit for dyeing keratin fibers
WO2021123061A1 (en) Process for preparing a composition for dyeing the hair starting from a composition in powder form and an aqueous composition
US11273112B2 (en) Process for treating keratin fibers using a halochromic triarylmethane direct dye, an alkaline revealer and then an acidic eraser
WO2018115450A1 (en) Process for direct dyeing of keratin fibres comprising the application of two particular compositions
EP3813782A1 (en) Process for curling keratin fibres comprising the application to the fibres of a composition containing thiolactic acid
US11883512B2 (en) Alkaline composition comprising at least three different alkaline agents for the treatment of keratin fibres, methods and uses
JP7237469B2 (en) Method and kit for dyeing keratin fibers
WO2019121631A1 (en) Process for treating keratin fibers using a halochromic fluorescein direct dye, an alkaline revealer and then an acidic eraser
FR2944436A1 (en) Composition, useful to treat human keratin materials, preferably e.g. skin, comprises fatty substance, surfactants comprising nonionic, anionic or amphoteric surfactants, non-filter cationic species, and liposoluble agents in a medium
WO2019122330A1 (en) Aqueous composition comprising a direct dye, a buffer system, a hydrotropic solvent and a lower alcohol
FR3140273A1 (en) Cosmetic hair care composition comprising at least one particular amino silicone and at least one coloring agent and/or an optical brightener, and method for cosmetic treatment of hair
FR3104994A1 (en) Composition comprising a natural dye, a dispersing agent, an oil and a fatty phase thickener
FR3021216A1 (en) COMPOSITION COMPRISING A VISUALLY DISTINCT AQUEOUS PHASE AND A FATTY PHASE

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20835780

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20835780

Country of ref document: EP

Kind code of ref document: A1