WO2018115450A1 - Procédé de coloration directe de fibres kératiniques comprenant l'application de deux compositions individuelles - Google Patents

Procédé de coloration directe de fibres kératiniques comprenant l'application de deux compositions individuelles Download PDF

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Publication number
WO2018115450A1
WO2018115450A1 PCT/EP2017/084405 EP2017084405W WO2018115450A1 WO 2018115450 A1 WO2018115450 A1 WO 2018115450A1 EP 2017084405 W EP2017084405 W EP 2017084405W WO 2018115450 A1 WO2018115450 A1 WO 2018115450A1
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group
alkyl
weight
acid
chosen
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PCT/EP2017/084405
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English (en)
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Gérard Gabin
Leila Hercouet
Julia PUECH
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L'oreal
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Publication of WO2018115450A1 publication Critical patent/WO2018115450A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/03—Liquid compositions with two or more distinct layers
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • 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
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/882—Mixing prior to application
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/884—Sequential application

Definitions

  • the present invention relates to a process for direct dyeing of keratin fibres, preferably human keratin fibres such as the hair, comprising the application to the fibres of an aqueous composition (A) which comprises a thickener, a direct dye, an organic solvent and water and of an oily composition (B) which comprises a thickener and an oil, the compositions (A) and (B) being applied either separately one after the other, or together in one and the same composition.
  • aqueous composition A which comprises a thickener, a direct dye, an organic solvent and water
  • an oily composition which comprises a thickener and an oil
  • the first type of dyeing is "permanent" or oxidation dyeing, which uses dyeing compositions containing oxidation dye precursors, generally referred to as oxidation bases.
  • oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.
  • the second type of dyeing is "semi-permanent" dyeing or direct dyeing, which consists in applying, to the keratin fibres, direct dyes, which are coloured and colouring molecules that have affinity for said fibres, in leaving them on for a time, and then in rinsing them off.
  • the direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes, and natural dyes.
  • These dyes may be non-ionic, anionic, cationic or amphoteric.
  • compositions used in these dyeing processes must have good general performance qualities, especially as regards:
  • a subject of the invention is thus a process for direct dyeing of keratin fibres, in particular human keratin fibres such as the hair, characterized in that the following compositions are applied to said keratin fibres:
  • composition (A) comprising:
  • compositions (A) and (B) being applied either separately one after the other, or together in one and the same composition
  • the total content of direct dyes representing at least 0.1% by weight, relative to the total weight of the compositions (A) and (B) applied to the fibres,
  • the weight ratio of the amount of composition (B) to the amount of composition (A) being greater than 0.1.
  • One advantage of the process according to the invention is that it makes it possible to obtain excellent performance qualities in terms of dyeing on the fibre, while at the same time minimizing the staining of the scalp.
  • the oily phase (B) forms a protective layer at the surface of the scalp which isolates it from the aqueous composition (A) which comprises the direct dye(s).
  • compositions (A) and (B) have good working qualities, especially in terms of texture, ease of application and ease of spreading on the hair tips.
  • the process according to the invention also makes it possible to obtain excellent dyeing qualities, especially in terms of build-up, intensity, chromaticity, fastness and/or selectivity of the colouring obtained.
  • the process according to the invention makes it possible to obtain very good hair-conditioning and haircare qualities especially in terms of softness, suppleness and ease of disentangling of dyed hair.
  • the term "keratin fibres” mainly denotes human keratin fibres and in particular the hair.
  • the process according to the invention comprises the application of an aqueous composition (A) which comprises one or more direct dyes.
  • direct dye is intended to mean natural and/or synthetic dyes, other than oxidation dyes. They are dyes that will superficially diffuse on the fibre and dye the fibres by themselves.
  • the direct dye(s) that may be used according to the invention are preferentially chosen from natural or synthetic, cationic, anionic or non-ionic direct dyes.
  • natural dyes or “dyes of natural origin” is intended to mean dyes derived from natural materials (plant, mineral or animal origin), for instance extracts, ground material and decoctions, which have a greater or smaller concentration of dyes.
  • the natural dyes may be chosen especially from spinulosin, orceins, polyphenols or ortho-diphenols (also referred to as ODPs in the rest of the description) and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3- dione, indigoids including indigo, phthalocyanines and porphyrins in particular complexed to a metal, glycosyl or non-glycosyl iridoids, chromene dyes, anthraquinone and naphthoquinone dyes such as lawsone or henna, juglone, spinulosin, chromene or chroman dyes, such as neoflavanols and neoflavanones, flavanols; and anthocyanidols.
  • Use may also be made of extracts or decoctions containing these natural dyes and especially plant extracts or poultices
  • the direct dye(s) that may be used according to the invention are chosen from anionic dyes, commonly referred to as "acid" direct dyes on account of their affinity for alkaline substances.
  • the anionic direct dyes according to the invention may be natural or synthetic.
  • anionic direct dyes is intended to mean any direct dye comprising in its structure at least one C0 2 R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion.
  • the anionic dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
  • anionic (or acid) direct dyes that may be used according to the invention, mention may be made especially of the dyes of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII) below:
  • R 7 , Rs, R9, Rio, R'7, R's, R'9 and R'io which may be identical or different, represent a hydrogen atom or a group chosen from:
  • X, X' and X" which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
  • R"-S(0) 2 - with R" representing a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group; - R"'-S(0) 2 -X'- with R' " representing an alkyl or optionally substituted aryl group, X' as defined previously;
  • aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 ⁇ )-, M + and iv) alkoxy, with M + as defined previously;
  • Ar-N N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (0) 2 S(0 ⁇ )-, M + or phenylamino groups;
  • W represents a sigma bond ⁇ , an oxygen or sulfur atom, or a divalent radical i) -NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and Rb, which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and Rb form, with the carbon atom that bears them, a spiro cycloalkyl; preferentially, W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that formulae (I) and (II) comprise at least one sulfonate radical (0) 2 S(0 ⁇ )-, M + or one carboxylate radical (O)CO -, M + on one of the rings A, A', B, B' or C; preferentially sodium sulfonate.
  • dyes of formula (I) mention may be made especially of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2 and Food Yellow 3 or Sunset Yellow.
  • dyes of formula (II) mention may be made especially of: Acid Red 111, Acid Red 134 and Acid Yellow 38.
  • Ri i , Ri2 and Rn which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or (0) 2 S(0 ⁇ )-, M + with M + as defined previously;
  • - Ri4 represents a hydrogen atom, an alkyl group or a group C(0)0 " -, M + with M + as defined previously;
  • - Ri5 represents a hydrogen atom
  • Ri6 represents an oxo group, in which case R' i 6 is absent, or alternatively Ri5 with Ri6 together form a double bond;
  • Ri7 and Ris which may be identical or different, represent a hydrogen atom, or a group chosen from:
  • Ar represents an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups;
  • - Ri9 and R20 together form either a double bond, or a benzo group D', which is optionally substituted;
  • R' i6, R' i9 and R'20 which may be identical or different, represent a hydrogen atom or an alkyl or hydroxy 1 group;
  • R21 represents a hydrogen atom or an alkyl or alkoxy group
  • Ra represents a hydrogen atom and Rb represents an aryl group
  • - Y represents either a hydroxyl group or an oxo group
  • - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;
  • formulae (III) and (IV) comprise at least one sulfonate radical (0)2S(0 ⁇ )-, M + or one carboxylate radical C(0)0 " -, M + on one of the rings D or E; preferentially sodium sulfonate.
  • dyes of formula (III) mention may be made especially of: Acid Red 195, Acid Yellow 23, Acid Yellow 27 and Acid Yellow 76.
  • R22, R23, R24, R25, R26 and R27 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0 ⁇ )-, M + with M + as defined previously;
  • - Z' represents a hydrogen atom or a group NR28R2 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:
  • - aryl optionally substituted with one or more groups, more particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (0)2S(0 ⁇ )-, M + with M + as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents an alkyl group; - cycloalkyl; in particular cyclohexyl;
  • - Z represents a group chosen from hydroxyl and NR' 2 8R'29 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R 2 8 and R29 as defined previously;
  • formulae (V) and (VI) comprise at least one sulfonate radical (0) 2 S(0 )-, M + or one carboxylate radical C(0)0 " -, M + ; preferentially sodium sulfonate.
  • dyes of formula (V) mention may be made especially of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3 and EXT Violet N° 2.
  • R30, R31 and R32 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;
  • heterocycloalkyl such as piperidino, piperazino or morpholino
  • R30, R31 and R 32 represent a hydrogen atom
  • Rc and Rd which may be identical or different, represent a hydrogen atom or an alkyl group
  • W is as defined previously; W more particularly represents an -NH- group;
  • ALK represents a linear or branched divalent Ci-C 6 alkylene group; more particularly, ALK represents a -CH 2 -CH 2 - group;
  • - p represents an integer inclusively between 1 and 5;
  • - u is 0 or 1 ;
  • J represents a nitro or nitroso group; more particularly nitro;
  • J represents an oxygen or sulfur atom, or a divalent radical -S(0) m - with m representing an integer 1 or 2; more preferentially, J represents a radical -S0 2 -;
  • - M' represents a hydrogen atom or a cationic counterion; , which may be present or absent, represents a benzo group optionally substituted with one or more R30 groups as defined previously;
  • formulae (VII) and (VIII) comprise at least one sulfonate radical (0) 2 S(0 ⁇ )-, M + or one carboxylate radical C(0)0 " -, M + ; more preferentially sodium sulfonate.
  • dyes of formula (VII) mention may be made especially of: Acid Brown 13 and Acid Orange 3.
  • dyes of formula (VIII) mention may be made of: Acid Yellow 1, the sodium salt of 2,4-dinitro-l-naphthol-7-sulfonic acid, 2-piperidino-5- nitrobenzenesulfonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'- nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3-nitrobenzenesulfonic acid and EXT D&C Yellow 7.
  • R33, R34, R35 and R36 which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; more particularly an alkyl and benzyl group optionally substituted with a group (0) m S(0 ⁇ )-, M + with M + and m as defined previously;
  • R37, R38, R39, R40, R41 , R42, R43 and R44 which may be identical or different, represent a hydrogen atom or group chosen from:
  • X, X' and X" which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
  • R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: ⁇ ; with ⁇ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 ⁇ )-, M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X * -; viii) R°-X * -C(X)-; ix) R°-X'-C(X)- X"-; with M + , R°, X, X' and X" as defined previously;
  • R37 to R40 represent a hydrogen atom
  • R41 to R44 which may be identical or different, represent a hydroxyl group or (0)2S(0 ⁇ )-, M + ; and when R43 with R44 together form a benzo group, it is preferentially substituted with an (0) 2 S(0 group;
  • At least one of the rings G, H, I or ⁇ comprises at least one sulfonate radical (0)2S(0 ⁇ )- or a carboxylate radical C(0)0 " -; more preferentially sulfonate.
  • dyes of formula (IX) mention may be made especially of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.
  • R45, R46, R47 and R48 which may be identical or different, represent hydrogen or halogen atom
  • R49, R50, R51 and R52 which may be identical or different, represent hydrogen or halogen atom, or a group chosen from:
  • R49, R50, R51 and R52 represent a hydrogen or halogen atom
  • G represents an oxygen or sulfur atom or a group NRe with R e as defined previously; more particularly G represents an oxygen atom;
  • - L represents an alkoxide O " , M + ; a thioalkoxide S " , M + or a group NRf, with Rf representing a hydrogen atom or an alkyl group and M + as defined previously; M + is particularly sodium or potassium;
  • L' represents an oxygen or sulfur atom or an ammonium group: N + RfR g , with Rf and R g , which may be identical or different, representing a hydrogen atom, or an alkyl group or aryl group which is optionally substituted ; L' represents more particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (0) m S(0 ⁇ )-, M + groups with m and M + as defined previously;
  • Q and Q' which may be identical or different, represent an oxygen or sulfur atom; more particularly Q and Q' represent an oxygen atom;
  • dyes of formula (X) mention may in particular be made of: Acid Yellow 73; Acid Red 51 ; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9;
  • R53, R54, R55, R56, R57, R58, R59 and R50 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • X, X' and X" which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or an alkyl group;
  • G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; more particularly G represents an oxygen atom;
  • - Ri and Rh which may be identical or different, represent a hydrogen atom or an alkyl group
  • formula (XI) comprises at least one sulfonate radical (0) 2 S(0 ⁇ )-, M + or one carboxylate radical C(0)0 " -, M + ; more preferentially sodium sulfonate.
  • - Rei represents a hydrogen or halogen atom or an alkyl group
  • R52, R53, and R54 which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 ⁇ )-, M + with M + representing a hydrogen atom or a cationic counterion;
  • R51 with R52, or 51 with R54 together form a benzo group optionally substituted with one or more groups (0) 2 S(0 ⁇ )-, M + with M + representing a hydrogen atom or a cationic counterion; it being understood that formula (XII) comprises at least one sulfonate radical (0) 2 S(0 ⁇ )-, more preferentially sodium sulfonate.
  • dyes of formula (XII) mention may be made especially of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
  • anionic direct dye(s) that may be used according to the invention are preferentially chosen from those of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII) as defined above.
  • dyes of formulae (I) to (X) that may be used according to the invention are chosen from:
  • the anionic direct dye(s) that are particularly preferred according to the invention are chosen from l,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid (C.I. 58005), the monosodium salt of 2-[(9,10-dihydro-4-hydroxy-9,10-dioxo-l- anthracenyl)amino]-5-methylbenzenesulfonic acid (C.I. 60730), the monosodium salt of 4-[(2-hydroxy- 1 -naphthyl)azo]benzenesulfonic acid (C.I.
  • the direct dye(s) are chosen from anionic direct dyes.
  • the direct dye(s) represent(s) a total content of at least 0.1% by weight, preferably at least 0.15% by weight, preferably from 0.2%> to 5%> by weight, relative to the total weight of the compositions (A) and (B) applied to the fibres.
  • the aqueous composition (A) used in the process according to the invention comprises one or more aqueous-phase thickeners.
  • aqueous-phase thickener is intended to mean 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 ambient 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 rheo meter 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.
  • sucrose unit is intended to mean an oxygen-bearing hydrocarbon-based compound containing several alcohol functions, with or without aldehyde or ketone functions, and which comprises at least 4 carbon atoms.
  • the sugar units may 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 that may especially be mentioned include 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
  • gums resulting from algae including:
  • gums resulting from seeds or tubers 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
  • e) plant extracts including: - cellulose (glucose polymer);
  • These polymers can be physically or chemically modified.
  • physical treatment mention may in particular be made of the temperature.
  • Chemical treatments that may be mentioned include esterification, etherification, amidation and oxidation reactions. These treatments make it possible to produce polymers that may especially be non-ionic, anionic or amphoteric.
  • these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.
  • non- ionic guar gums that may be used according to the invention may be modified with Ci-C 6 (poly)hydroxyalkyl groups.
  • Ci-C 6 (poly)hydroxyalkyl groups mention may be made, by way of example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
  • guar gums are well known in 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 varies from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functional groups present on the guar gum.
  • non-ionic 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 may be used in the present invention may be cereals or tubers.
  • the starches are chosen, for example, from corn starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.
  • the starches may be chemically or physically modified, in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, 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) or Prejel 200 (gelatinized acetyl cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized corn distarch phosphate).
  • amphoteric starches may also be used, 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.
  • the cationic groups may be of primary, secondary, tertiary or quaternary amine type.
  • the starch molecules may be derived from any plant source of starch, in particular such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above.
  • the starch is preferably derived from potato.
  • the nonassociative thickening polymers of the invention may be cellulose- based polymers not comprising a C10-C30 fatty chain in their structure.
  • cellulose-based polymer is intended to mean any polysaccharide compound having in its structure sequences of glucose residues linked together via ⁇ -1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives may be anionic, cationic, amphoteric or non-ionic.
  • the cellulose polymers that may be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers.
  • cellulose ethers cellulose esters and cellulose ester ethers are distinguished.
  • cellulose esters are mineral esters of cellulose (cellulose nitrates, sulfates, phosphates, etc.), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates and acetatetrimellitates, etc.), and mixed organic/mineral 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.
  • non-ionic cellulose ethers without a C10-C30 fatty chain i.e. which are "non-associative"
  • anionic cellulose ethers without a fatty chain mention may be made of (poly)carboxy(Ci-C4)alkylcelluloses and salts thereof.
  • carboxymethylcelluloses for example Blanose 7M from the company Aqualon
  • carboxymethylhydroxyethylcelluloses for example Blanose 7M from the company Aqualon
  • cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in patent US 4 131 576, such as (poly)hydroxy(Ci-C4)alkyl celluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted in particular 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 ash mixtures.
  • a first family of nonassociative 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 INCI name Carbomer.
  • the nonassociative 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 nonassociative thickening polymers may be chosen from crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked acrylamide copolymers thereof.
  • the aqueous composition (A) may similarly comprise, as non-associative thickening polymers, ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.
  • ammonium acrylate homopolymer 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 non-ionic, 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 region and at least one hydrophobic region.
  • hydrophobic group is intended to mean 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 mono functional 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, such as, for example, polybutadiene.
  • 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 methy lenebisacrylamide .
  • 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 methy lenebisacrylamide .
  • the ones most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 OE) stearyl alcohol ether (Steareth 10), especially those sold by the company CIBA under the names Salcare SC80® and Salcare SC90®, which are aqueous 30%> emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth- 10 allyl ether (40/50/10).
  • (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 4 509 949. Use will more particularly be made, among anionic associative polymers of this type, of those composed of 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 else of those composed of 98%> to 96%o 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 above.
  • maleic anhydride/C3o-C38 a-olefin/alkyl maleate terpolymers such as the product (maleic anhydride/C3o-C38 a-olefm/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies.
  • a non-ionic monourethane which is the product of reaction of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate
  • Example 3 such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 OE) terpolymer, as an aqueous 25% dispersion.
  • a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 OE) terpolymer as an aqueous 25% dispersion.
  • copolymers comprising among their monomers an ⁇ , ⁇ - monoethylenically unsaturated carboxylic acid and an ester of an ⁇ , ⁇ - monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.
  • these compounds also comprise as monomer an ester of an ⁇ , ⁇ - 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 comprising 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 especially 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 or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.
  • APMS 2-Acrylamido-2-methylpropanesulfonic acid
  • the polymers of this family may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00/31154. These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, ⁇ -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 comprising a fatty chain, such as (meth)acrylic acids, ⁇ - 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.
  • monomers not comprising a fatty chain such as (meth)acrylic acids, ⁇ - 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 comprising 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-(C 6 - Ci8)alkylacrylamide units, such as those described in patent US-5 089 578.
  • Polyacrylate-1 Crosspolymer is the product of polymerization of a monomer mixture comprising:
  • the alkyl radicals borne by the above quatemized celluloses or hydroxy ethylcelluloses preferably comprise from 8 to 30 carbon atoms.
  • the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
  • Examples of quatemized alkylhydroxyethylcelluloses containing C 8 - 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® (Ci8 alkyl) sold by the company Aqualon, and the products Crodacel QM®, Crodacel QL® (C 12 alkyl) and Crodacel QS® (C 18 alkyl) sold by the company Croda and the product Softcat SL 100® sold by the company Aqualon.
  • vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacryl- amidopropylammonium tosylate terpolymers vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylami dopropylammonium tosylate terpolymers
  • vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamid -opropylammonium tosylate or chloride terpolymers are used in particular.
  • amphoteric associative polymers are preferably chosen from those comprising at least one noncyclic cationic unit. Even more particularly, those prepared from or comprising 1 mol% 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 non- ionic type that may be used according to the invention are preferably chosen from:
  • copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer
  • polyurethane poly ethers comprising 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;
  • non- ionic nonoxynylhydroxyethylcelluloses such as the product Amercell HM-1500 sold by the company Amerchol;
  • non- ionic alkylcelluloses such as the product Bermocoll EHM 100 sold by the company Berol Nobel;
  • 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 C 14 alkyl chain) and the product RE 205-146 (modified with a C20 alkyl chain) sold by Rhodia Chimie.
  • the polyurethane polyethers comprise 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 comprise 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 having 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 non-ionic fatty-chain polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups.
  • the non- ionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, hence the origin of the name.
  • non-ionic fatty-chain polyurethane polyethers include those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
  • non- ionic 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 C 12 -C 14 alkyl chain, and the product Elfacos T212® bearing a C 18 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, in particular in water or in aqueous/alcoholic medium.
  • examples of such polymers include Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox.
  • the products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.
  • polyurethane polyethers which can be used according to the invention are in particular those described in the paper by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 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 poly condensate 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 thickener(s) are chosen from polymers not comprising any sugar units.
  • the aqueous-phase thickener(s) are chosen from associative or non-associative thickening polymers bearing acrylic or methacrylic units, and polymers bearing 2-acrylamido-2-methylpropanesulfonic acid units and/or the salified form thereof.
  • the aqueous-phase thickener(s) are chosen from acrylic acid homopolymers or copolymers, in particular acrylic acid homopolymers, homopolymers or copolymers of 2-acrylamido-2- methylpropanesulfonic acid and/or the salified form thereof, in particular copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof, more particularly copolymers of 2-acrylamido-2-methylpropanesulfonic acid and/or the salified form thereof and of acrylamide or copolymers of 2-acrylamido-2- methylpropanesulfonic acid and/or the salified form thereof and of hydroxyethyl acrylate, said polymers possibly being crosslinked or non-crosslinked.
  • the aqueous-phase thickener(s) generally represent a total content ranging from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight and better still from 1.5% to 10%> by weight, relative to the total weight of the aqueous composition (A).
  • the aqueous-phase thickener(s) generally represent a total content ranging from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight and better still from 1% to 5% by weight, relative to the total weight of the compositions (A) and (B).
  • the aqueous composition (A) used in the process according to the invention also comprises one or more organic solvents.
  • the organic solvents which can be used are liquid at ambient temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 x 10 5 Pa).
  • the organic solvent(s) are chosen from linear or branched monoalcohols containing from 1 to 8 carbon atoms, polyols, polyethylene glycols, aromatic alcohols, and mixtures of these compounds.
  • the organic solvents are chosen from ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerol, sorbitol, benzyl alcohol and phenoxy ethanol, and mixtures of these compounds.
  • the organic solvent(s) are chosen from ethanol, dipropylene glycol and benzyl alcohol, and a mixture of these compounds.
  • the organic solvent(s) generally represent a total content ranging from 1% to 30% by weight, preferably from 2% to 25% by weight and better still from 10% to 20%) by weight, relative to the total weight of the aqueous composition (A).
  • the organic solvent(s) generally represent a total content ranging from 0.5% to 20% by weight, preferably from 1% to 15% by weight and better still from 5% to 10% by weight, relative to the total weight of the compositions (A) and (B).
  • the aqueous composition (A) used in the process according to the invention also comprises water.
  • the water represents at least 50% by weight, preferably from 50%> to 95% by weight, more preferably from 60% to 90% by weight and even better from 65% to 80% by weight relative to the total weight of the aqueous composition (A).
  • the water generally represents from 20% to 85% by weight, preferably from 30% to 70% by weight and more preferentially from 40% to 60% by weight relative to the total weight of the compositions (A) and (B).
  • the process according to the invention comprises the application of an oily composition (B).
  • the oily composition (B) used in the process according to the invention comprises one or more oils.
  • oil is intended to mean any fatty substance that is in liquid form at ambient temperature (25°C) and at atmospheric pressure.
  • fatty substance is intended to mean an organic compound that is insoluble in water at ambient temperature (25°C) and at atmospheric pressure (1.013x 10 5 Pa) (solubility of less than 5% by weight, preferably less than 1 % by weight and even more preferably less than 0.1% by weight). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms and/or a sequence of at least two siloxane groups.
  • 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.
  • organic solvents for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
  • the oil(s) present in the oily composition (B) used in the process according to the invention may be volatile or non-volatile.
  • the volatile or non-volatile oils may be hydrocarbon-based oils, especially of animal or plant origin, synthetic oils, silicone oils or fluoro oils, or mixtures thereof.
  • silicon oil is intended to mean an oil comprising at least one silicon atom and in particular at least one Si-0 group.
  • hydrocarbon-based oil is intended to mean an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and/or phosphorus atoms.
  • a hydrocarbon-based oil does not comprise any silicon atoms.
  • the oil(s) present in the oily composition (B) used in the process according to the invention may be non-volatile.
  • non-volatile oil is intended to mean an oil having a vapour pressure of less than 0.13 Pa (0.01 mmHg).
  • the non- volatile oils may be chosen especially from non- volatile hydrocarbon-based oils, which may be fluorinated, and/or non-volatile silicone oils.
  • oils of plant origin such as phytostearyl esters, such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutanate, for example sold under the name Eldew PS203 by Ajinomoto, triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C 4 to C 24 , these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially heptanoic or octanoic triglycerides, sweet almond oil, argan oil, avocado oil, groundnut oil, camellia oil, safflower oil, beauty- leaf oil, rapeseed oil, copra oil, coriander oil, marrow oil, wheatgerm oil, jojoba oil or liquid jojoba wax, linseed oil, macadamia oil, corn germ oil
  • linear or branched hydrocarbons of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and squalane, and mixtures thereof, and in particular hydrogenated polyisobutene;
  • esters for instance oils of formula RiCOOR 2 in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms provided that Ri + R 2 > 10.
  • the esters may be chosen especially from fatty acid esters, for instance:
  • isopropyl alcohol esters such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, isopropyl isostearate, isostearyl isostearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 2-ethylhexyl 4-diheptanoate, 2-ethylhe
  • fatty alcohols that are liquid at ambient temperature, bearing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol and 2-undecyl-pentadecanol;
  • non-salified higher fatty acids such as oleic acid, linoleic acid and linolenic acid, and mixtures thereof;
  • dialkyl carbonates the two alkyl chains possibly being identical or different, such as the dicaprylyl carbonate sold under the name Cetiol CC® by Cognis;
  • the non- volatile silicone oils are chosen, for example, from non- volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendent and/or at the ends of a silicone chain, these groups each having from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxy silicates, and dimethicones or phenyl trimethicones with a viscosity of less than or equal to 100 cSt, and mixtures thereof.
  • PDMSs non- volatile polydimethylsiloxanes
  • phenyl silicones for instance phenyl trimethicones, phenyl dimeth
  • the non- volatile oils may be chosen from mixtures of hydrocarbon-based and silicone non- volatile oils.
  • the oil(s) present in the oily composition (B) used in the process according to the invention may be volatile.
  • volatile oil is intended to mean an oil (or non-aqueous medium) that is capable of evaporating on contact with the skin in less than one hour, at ambient temperature and at atmospheric pressure.
  • the volatile oil is a volatile cosmetic oil, which is liquid at ambient temperature, especially having a non-zero vapour pressure, at ambient temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10 ⁇ 3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
  • the volatile hydrocarbon-based oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes (also known as isoparaffms), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar® or Permethyl®.
  • hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially branched Cs-Ci6 alkanes (also known as isoparaffms), for instance isododecane (also known as 2,2,4,4,6- pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar® or Permethyl®.
  • Volatile fluoro oils such as nonafluoromethoxybutane or perfluoromethyl- cyclopentane, and mixtures thereof, may also be used.
  • Volatile oils that may also be used include volatile silicones, for instance volatile linear or cyclic silicone oils, especially those with a viscosity ⁇ 8 centistokes (8x 10 "6 m 2 /s), and especially having from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
  • volatile silicones for instance volatile linear or cyclic silicone oils, especially those with a viscosity ⁇ 8 centistokes (8x 10 "6 m 2 /s), and especially having from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms.
  • volatile silicone oils that may be used in the invention, mention may be made especially of dimethicones with a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • the oil(s) are chosen from C 6 -Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, non-silicone oils of animal origin, oils of plant origin, fluoro oils, liquid fatty alcohols, liquid fatty esters, non-salified liquid fatty acids, silicone oils, and mixtures of these compounds.
  • fatty alcohol, ester or acid is intended to mean an alcohol, ester or acid comprising a linear or branched, saturated or unsaturated alkyl chain, comprising at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and more preferentially from 12 to 24 carbon atoms.
  • the oil(s) are chosen from C 6 -Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, liquid fatty alcohols, liquid fatty esters, oils of plant origin, especially hydrocarbon-based oils of plant origin, and mixtures of these compounds.
  • the oil(s) are chosen from C 6 -Ci6 alkanes, linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms, liquid fatty alcohols, oils of plant origin, especially hydrocarbon-based oils of plant origin, and mixtures of these compounds.
  • the oil(s) generally represent a total content ranging from 50% to 99% by weight, preferably from 70%> to 98%> by weight and better still from 80%> to 95% by weight, relative to the total weight of the oily composition (B).
  • the oil(s) represent a total content ranging from 8% to 50% by weight, preferably from 10% to 45% by weight and better still from 15% to 40% by weight, relative to the total weight of the compositions (A) and (B).
  • the oily composition (B) used in the process according to the invention also comprises one or more fatty-phase thickeners.
  • fatty-phase thickener is intended to mean compounds which, by their presence in a content of 0.05%> by weight, increase the viscosity of an oily composition into which they are introduced by at least 20 cps, preferably by at least 50 cps, at 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 rheo meter or the like).
  • the notion of a fatty-phase thickener is analogous to the notion of a lipophilic thickener.
  • the fatty-phase thickener(s) used in the oily composition (B) used in the process according to the invention may be chosen from mineral fatty-phase thickeners and organic fatty-phase thickeners, and mixtures of these compounds.
  • the mineral fatty-phase thickeners that may be used in the oily composition (B) used in the process according to the invention are preferably mineral particles constituted essentially of mineral oxides and/or hydroxides.
  • These particles are preferably insoluble in water at ambient temperature (25°C).
  • insoluble is intended to mean a solubility of less than 0.5% by weight.
  • the number-average primary size of these mineral particles ranges from 0.01 to 500 ⁇ , it preferably ranges from 0.1 to 200 ⁇ and even more preferentially it ranges from 1 to 100 ⁇ .
  • primary particle size is intended to mean the maximum dimension that it is possible to measure between two diametrically opposite points on an individual particle.
  • the size of the mineral particles may be determined by transmission electron microscopy or by measuring the specific surface area via the BET method or by laser particle size analysis.
  • the mineral particles that may be used in accordance with the invention may be in various forms, for example in the form of spheres, needles, flakes or platelets.
  • the mineral fatty-phase thickener(s) are platelet-shaped particles.
  • the mineral fatty-phase thickener(s) that may be used in the oily composition (B) used in the process according to the invention may preferably be chosen from silicas and silicates.
  • the silicates of the invention may be natural or chemically modified (or synthetic).
  • the silicates correspond to optionally hydrated silica in which some of the silicon atoms are replaced with metal cations such as Al 3+ , B 3+ , Fe 3+ , Ga 3+ , Be 2+ , Zn 2+ , Mg 2+ , Co 3+ , Ni 3+ , Na + , Li + , Ca 2+ , Cu 2+ .
  • metal cations such as Al 3+ , B 3+ , Fe 3+ , Ga 3+ , Be 2+ , Zn 2+ , Mg 2+ , Co 3+ , Ni 3+ , Na + , Li + , Ca 2+ , Cu 2+ .
  • the silicates that may be used in the context of the invention are chosen from clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the vermiculite, stevensite and chlorite families. These clays may be of natural or synthetic origin. Clays that are cosmetically compatible and acceptable with keratin materials are preferably used.
  • the silicate may be chosen from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof.
  • the silicate(s) are preferably chosen from bentonites and hectorites.
  • the silicates may be modified with a compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.
  • silicates that are suitable for use, mention may be made of quaternium-18 bentonites, such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; quaternium-18/benzalkonium bentonites, such as those sold under the names Claytone HT and Claytone PS by Southern Clay; quaternium-18 hectorites, such as those sold under the names Bentone Gel DO A, Bentone Gel EC05, Bentone Gel EUG, Bentone Gel IPP, Bentone Gel ISD, Bentone Gel SS71, Bentone Gel VS8 and Bentone Gel VS38 by Rheox, and Simagel M and Simagel SI 345 by Biophil.
  • the silicates that may be used in the oily composition (B) used in the process according to the invention may be chosen, in particular, from modified hectorites such as hectorite modified with C 10 -C 12 fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride.
  • the mineral fatty-phase thickener(s) that may be used in the oily composition (B) used in the process according to the invention may be silicas.
  • silica(s) that may be used in the oily composition (B) used in the process according to the invention are preferably fumed.
  • the fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas bearing a large number of silanol groups at their surface.
  • hydrophilic silicas are sold, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by the company Degussa, and Cab-O-Sil HS-5®, Cab-O-Sil EH- 5®, Cab-O-Sil LM-130®, Cab-O-Sil MS-55® and Cab-O-Sil M-5® by the company Cabot.
  • the hydrophobic groups may be:
  • dimethylsilyloxy or polydimethylsiloxane groups which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane.
  • Silicas thus treated are known as Silica dimethyl silylate according to the CTFA (6th Edition, 1995). They are sold, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and Cab-O- Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.
  • the fumed silicas that may be used in the oily composition (B) used in the process according to the invention are hydrophilic, such as the product sold under the name Aerosil 200®.
  • the mineral fatty-phase thickener(s) are chosen from organophilic clays and hydrophilic fumed silicas, and mixtures thereof.
  • the mineral fatty-phase thickener(s) are chosen from hectorites modified with C 10 -C 12 fatty acid ammonium chloride, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride, and hydrophilic fumed silicas such as the hydrophilic silicas sold under the name Aerosil 200®.
  • the mineral fatty-phase thickener(s) are chosen from hectorites modified with C 10 -C 12 fatty acid ammonium chloride, especially hectorite modified with distearyldimethylammonium chloride, such as the product sold under the name Bentone 38VCG by Elementis, and the hectorite modified with stearylbenzyldimethylammonium chloride, such as the product sold under the name Bentone 27V by Elementis.
  • the fatty-phase thickener(s) that may be used in the oily composition (B) used in the process according to the invention may also be chosen from organic fatty-phase thickeners.
  • the organic fatty-phase thickener(s) are chosen from semi- crystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, N-acylamino acid amide derivatives, polymers comprising an alkylene and/or styrene block, such as polystearyl acrylates, elastomeric organopolysiloxanes, solid fatty esters, in particular C8-C30 and preferably C18-C24 fatty acid esters, and mixtures of these compounds.
  • These copolymers may be diblock, triblock or multi-block polymers, radial-block polymers, also known as star copolymers, or alternatively comb polymers.
  • C8-C30 and preferably C18-C24 fatty acid esters mention may be made of mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of polyols, more particularly mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids of glycerol. Use may especially be made of a mixture of these compounds such as a mixture of mono-, di and triesters of behenic acid and of glycerol.
  • the organic fatty-phase thickener(s) are chosen from semi- crystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, polymers comprising an alkylene and/or styrene block, such as polystearyl acrylates, solid fatty esters, in particular C8-C30 and preferably C18-C24 fatty acid esters, and mixtures of these compounds.
  • the organic fatty-phase thickener(s) are chosen from saccharide or polysaccharide monoalkyl or polyalkyl esters, such as dextrin palmitate, C8-C30 and preferably C18-C24 fatty acid esters and mixtures thereof, better still mono- , di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of polyols, more particularly mono-, di- or triesters of C8-C30 and preferably C18-C24 fatty acids and of glycerol.
  • the fatty-phase thickener(s) are chosen from organic thickeners.
  • the fatty-phase thickener(s) generally represent a total content ranging from 1% to 40% by weight, preferably from 2% to 30% by weight and better still from 5% to 20% by weight, relative to the total weight of the oily composition (B).
  • the fatty-phase thickener(s) generally represent a total content ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and better still from 1%) to 8%) by weight, relative to the total weight of the compositions (A) and (B).
  • the oily composition (B) used in the process according to the invention may also comprise any usual liposoluble or lipodispersible additive, for instance other solid or pasty fatty substances such as waxes, fatty alcohols or fatty acids. It may also comprise compounds such as alkylene carbonates, for instance propylene carbonate, which can reinforce the efficacy of certain fatty-phase thickeners such as silicates.
  • the weight ratio of the amount of oily composition (B) to the amount of aqueous composition (A) is greater than 0.1.
  • this ratio is greater than 0.10 and less than or equal to 1, and preferably ranges from 0.15 to 0.7 and more preferentially from 0.25 to 0.5.
  • the aqueous composition (A) and the oily composition (B) used in the process according to the invention do not comprise surfactant.
  • the content of surfactants is less than 2% by weight, relative to the total weight of each composition containing them.
  • the aqueous composition (A) and the oily composition (B) used in the process according to the invention may contain additives conventionally used in the cosmetics field other than those described previously, and chosen from UV-screening agents, resins, fragrances, peptizers, vitamins, amino acids, preservatives, alkaline agents, acidifying agents, etc.
  • the above additives may in general be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of each composition containing them.
  • the aqueous composition (A) and the oily composition (B) are in the form of gels.
  • each of the two compositions (A) and (B) has a viscosity of greater than or equal to 0.1 Pa.s, preferentially ranging from 0.1 to 500 Pa.s, more preferentially ranging from 0.5 to 300 Pa.s and even more preferentially ranging from 1 to 200 Pa.s, at a temperature of 25°C, at atmospheric pressure and at a shear rate of 1 s "1 (measurable, for example, with a Haake RS600 rheometer).
  • each of the two compositions (A) and (B) has a threshold stress at 25°C ranging from 0.1 to 300 Pa, preferably from 1 to 250 Pa and more preferably from 10 to 200 Pa.
  • the threshold stress is determined by scanning under stress at 25°C.
  • An imposed-stress Thermo Haake RS600 rheometer with sandblasted cone-plate geometry is used.
  • the temperature is regulated by a Peltier-effect plate and an anti-evaporation device (solvent trap filled with water for the measurements at 25°C).
  • a logarithmic stress elevation from 0.5 to 500 Pa is performed over a period of 3 minutes.
  • Two adjustment lines corresponding to the stationary regimes (solid and liquid behaviours) are plotted on the curve representing the strain as a function of the stress (logarithmic coordinates). The intersection of these two lines gives the value of the stress threshold.
  • the pH of the aqueous composition (A) used in the process according to the invention generally ranges from 1.5 to 10 and preferably from 2 to 7. Even more preferentially, the pH of the aqueous composition (A) used in the process according to the invention is less than or equal to 5, better still ranging from 1.5 to 4 and even better still from 2 to 3.
  • compositions (A) and (B) used in the process according to the invention are applied either separately one after the other, or together in one and the same composition.
  • compositions (A) and (B) are applied separately one after the other.
  • these two compositions are applied without intermediate rinsing.
  • the oily composition (B) is applied before the aqueous composition (A).
  • compositions (A) and (B) are applied together in one and the same composition.
  • compositions (A) and (B) are applied together in one and the same composition prepared previously or obtained by extemporaneous mixing before application, and preferably prepared previously.
  • compositions (A) and (B) as defined previously can be prepared previously in the following way: a) a step of preparing, separately from each other, the compositions (A) and
  • compositions (A) and (B) b) a step of bringing the compositions (A) and (B) into contact.
  • the step of bringing the various compositions into contact can be carried out by means of one or more static or non-static mixers.
  • the ingredients of the composition (A) are mixed separately from the ingredients of the composition (B).
  • Each of the compositions is prepared in a tank specifically dedicated thereto.
  • Each composition is then separately introduced into a static or non- static mixer.
  • compositions (A) and (B) can be applied to dry or wet keratin fibres, having optionally undergone washing with a shampoo.
  • the compositions (A) and (B) are applied to dry keratin fibres.
  • the keratin fibres are generally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.
  • compositions (A) and (B), whether they are applied one after the other or in one and the same composition, are left on for from 1 to 30 minutes, preferably from 2 to 20 minutes.
  • aqueous compositions Al and A2 were prepared from the ingredients of which the contents are indicated in the table below.
  • the oily composition (B) was prepared from the ingredients of which the contents are indicated in the table below. Ingredients B
  • the process of applying this composition CI is according to the invention and is compared with the process of applying the composition A2 only.
  • the pH of the composition A2 is also equal to 3.
  • composition CI contains the same concentration of direct dyes as the composition A2.
  • the dyeing performance qualities are evaluated according to the protocol below:
  • compositions CI and A2 are applied to locks of natural hair containing 90% grey hairs, on a hotplate at 40°C (4 g of composition per gram of lock of hair).
  • the colorimetric measurements are taken using a CM-3660d spectrophotometer in the CIELab system (illuminant D65, angle 10°).
  • the colour variation ⁇ is calculated from the following equation:
  • the parameters L*, a* and b* represent the values measured on locks of hair after dyeing and the parameters Lo*, ao* and bo* represent the values measured on locks of untreated hair.
  • composition CI or A2 A standardized amount (50 ⁇ in an Eppendorf pipette) of composition CI or A2 is deposited on a polyurethane membrane (scalp model).
  • Leave-on time 15 min at 40°C (on a hotplate).
  • the colour variation ⁇ ' between the dyed membrane and the non-dyed membrane is then evaluated in the CIELab system using standardized photographs and then analysed with colorimetric measurement software.
  • ⁇ ' is calculated according to the preceding equation, L*, a* and b* representing here the values measured for the membrane after dyeing and the parameters Lo*, ao* and bo* representing the values measured for the untreated membrane.
  • Lo*, ao* and bo* representing the values measured for the untreated membrane.
  • the oily composition (B) was prepared from the ingredients of which the contents are indicated in the table below.
  • composition C 1 is obtained;
  • composition C2 is obtained;
  • compositions CI and C2 have a black phase and a white phase. They have the same contents of ingredients, with the exception of the total content of oils which is of 23.5%) by weight relative to the total weight of the composition CI , and of 5.9%> by weight relative to the total weight of the composition C2.
  • compositions CI and C2 are respectively applied to two identical locks of natural hair containing 90% grey hairs (one composition per lock).
  • the hair dyeing obtained according to the process of the invention comprising the application of the composition CI , leads to a staining of the scalp which is significantly less important than the hair dyeing obtained according to the comparative process comprising the application of the composition C2 containing less than 6% by weight of oils relative to the total weight of the composition C2, while presenting equivalent dyeing performances.

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Abstract

La présente invention concerne un procédé de coloration directe de fibres kératiniques, de préférence des fibres kératiniques humaines telles que des cheveux, comprenant l'application sur les fibres d'une composition aqueuse (A) qui comprend un épaississant, un colorant direct, un solvant organique et de l'eau et d'une composition huileuse (B) qui comprend un épaississant et une huile, les compositions (A) et (B) étant appliquées séparément l'une après l'autre, ou conjointement dans une composition unique.
PCT/EP2017/084405 2016-12-22 2017-12-22 Procédé de coloration directe de fibres kératiniques comprenant l'application de deux compositions individuelles WO2018115450A1 (fr)

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FR1663168 2016-12-22
FR1663168A FR3060985B1 (fr) 2016-12-22 2016-12-22 Procede de coloration directe des fibres keratiniques comprenant l'application de deux compositions particulieres

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CN113194913A (zh) * 2018-12-12 2021-07-30 莱雅公司 香味凝胶

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113194913A (zh) * 2018-12-12 2021-07-30 莱雅公司 香味凝胶
CN113194913B (zh) * 2018-12-12 2024-01-02 莱雅公司 香味凝胶

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