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WO2025132077A1 - Composition for colouring keratin fibres comprising at least one copolymer containing acetoacetate functions, at least one silicone, at least one colouring agent and at least one alcohol - Google Patents

Composition for colouring keratin fibres comprising at least one copolymer containing acetoacetate functions, at least one silicone, at least one colouring agent and at least one alcohol Download PDF

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Publication number
WO2025132077A1
WO2025132077A1 PCT/EP2024/086211 EP2024086211W WO2025132077A1 WO 2025132077 A1 WO2025132077 A1 WO 2025132077A1 EP 2024086211 W EP2024086211 W EP 2024086211W WO 2025132077 A1 WO2025132077 A1 WO 2025132077A1
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weight
composition
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alkyl
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French (fr)
Inventor
Arnaud Bonnamy
Laurent SABATIE
Fabien BROTHIER
Marie GRACIA
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LOreal SA
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LOreal SA
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    • 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
    • A61K8/81—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
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/892—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
    • 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
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30—Characterized by the absence of a particular group of ingredients
    • A61K2800/31—Anhydrous
    • 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
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes

Definitions

  • TITLE Composition for colouring keratin fibres comprising at least one copolymer containing acetoacetate functions, at least one silicone, at least one colouring agent and at least one alcohol
  • the present invention relates to the field of the cosmetic treatment of keratin fibres and notably to the dyeing of keratin fibres, preferably the hair. It thus aims to provide novel colouring compositions comprising a copolymer containing acetoacetate units, which offer excellent technical performance, notably in terms of wear property of the colourings which they make it possible to obtain.
  • the present invention relates to a composition intended for colouring human keratin fibres such as hair, comprising a particular copolymer formed from monomers bearing acetoacetate functions in combination with a non-amino silicone, a colouring agent and an alcohol.
  • the present invention also relates to a method for colouring keratin fibres such as the hair using this composition.
  • Another dyeing method consists in using pigments. Specifically, the use of pigments on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair, since the surface pigment masks the natural colour of the fibre. However, the colourings obtained via this dyeing method have the drawback of having poor resistance to shampoo washing and also to external agents such as sebum, perspiration, brushing and/or rubbing.
  • hair makeup products have recently been developed, which provide temporary hair colour that lasts for 1 to 3 shampoo washes.
  • they are a particularly attractive alternative to permanent hair dyeing, provided that a good wear property of the colour effect is guaranteed in contact with water and a few shampoo washes. This requirement may notably be satisfied by the use of effective film-forming agents.
  • document FR 2 741 530 proposes for this purpose, for the temporary colouring of keratin fibres, the use of a dispersion of film-forming polymer particles including at least one acidic function and at least one pigment dispersed in the continuous phase of said dispersion.
  • the colourings obtained via this dyeing method however have the drawback of being removed too quickly on shampoo washing.
  • compositions that allow keratin fibres to be dyed, with the advantage that the fibres are uniformly coloured, while forming a coating that is resistant to shampoo washing, sebum and the various attacking factors to which the hair may be subjected, such as brushing, perspiration and/or rubbing.
  • the present invention enables these needs to be met.
  • One subject of the present invention is therefore a cosmetic composition for colouring keratin fibres, comprising: i) at least one copolymer CP obtained by polymerization of
  • R a represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group
  • R b and R c which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
  • R d represents a linear or branched (Ci-C4)alkyl group
  • L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group
  • the copolymer CP does not comprise any monomer (A) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof; ii) at least one non-amino silicone; iii) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and iv) at least one alcohol chosen from polyols and monoalcohols other than fatty alcohols.
  • Such a composition makes it possible to obtain uniform and smooth coloured coatings. It provides visible colouring on all types of fibres, which is resistant to water and notably to shampoo washing and sebum.
  • Such a coating may be resistant to the various external attacking factors to which keratin fibres may be subjected, for instance blow-drying, brushing, rubbing and perspiration.
  • Another subject of the present invention is a method for colouring keratin fibres comprising the application of the above composition to said fibres.
  • the invention also relates to the use of this composition for colouring keratin fibres, and in particular the hair.
  • keratin fibres is particularly understood to mean human keratin fibres such as head hair, eyelashes, eyebrows, and body hair, preferentially head hair, eyebrows and eyelashes, even more preferentially head hair.
  • aminoalkyF radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group
  • hydroxyalkyF radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group
  • an "alkylene” radical denotes a linear or branched divalent saturated C1-C10 hydrocarbon group such as methylene, ethylene or propylene;
  • cycloalkyF or “ alicy cloalkyF radical denotes a saturated monocyclic or polycyclic, preferably monocyclic, cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 40 carbon atoms, in particular comprising from 3 to 24 carbon atoms, more particularly from 3 to 20 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl or isobomyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobomyl group;
  • an “aryl” radical is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic cyclic hydrocarbon radical, comprising from 6 to 30 carbon atoms, preferably between 6 and 14 carbon atoms, more preferentially between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl; preferably, the aryl group represents phenyl;
  • an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined previously;
  • an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously.
  • the invention is not limited to the examples illustrated.
  • the characteristics of the various examples may notably be combined within variants which are not illustrated.
  • composition according to the invention comprises at least one copolymer CP obtained by the polymerization of:
  • R a represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group
  • R b and R c which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
  • R d represents a linear or branched (Ci-C4)alkyl group
  • L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group
  • R a preferably represents a hydrogen atom or a methyl group, preferably a methyl group,
  • R b and R c preferably represent a hydrogen atom
  • R d preferably represents a methyl group
  • L preferably represents a (Ci-C4)alkylene group, and more preferentially L represents ethylene.
  • the monomer of formula (I) is chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.
  • the copolymer CP is a statistical copolymer.
  • R a represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group; preferably, R a represents a methyl group,
  • R b and R c which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group; preferably, R b and R c represent a hydrogen atom,
  • R d represents a linear or branched (Ci-C4)alkyl group; preferably, R d represents a methyl group, and
  • L represents a linear or branched (Ci-Ce)alkylene or cycloalkylene group; preferably, L represents a (Ci-C4)alkylene group, in particular ethylene.
  • the copolymer CP comprises from 5% to 15% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I) as described above.
  • monomer (B) is chosen from acetoacetoxyethyl acrylate, acetoacetoxy ethyl methacrylate, and mixtures thereof, and preferably, monomer (B) is acetoacetoxyethyl methacrylate.
  • Acetoacetoxy ethyl acrylate is a compound of empirical formula C9H12O5, and of semi -structural formula:
  • acetoacetoxyethyl acrylate mention may notably be made of the product sold under the name Butanoic acid, 3-oxo-2-[(l-oxo-2-propen-l-yl)oxy]ethyl ester by the company Alfa Chemistry.
  • Acetoacetoxyethyl methacrylate is a compound of empirical formula C10H 4O5, and of semi-structural formula:
  • acetoacetoxyethyl methacrylate mention may notably be made of the product sold under the name EastmanTM AAEM by the company Eastman.
  • the copolymer CP comprises from 80% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates.
  • C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates that can be used as monomers (C) mention may be made in particular of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertbutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and mixtures thereof.
  • monomer (C) is a C1-C4 alkyl acrylate, in particular chosen from butyl acrylate, isobutyl acrylate and tert-butyl acrylate.
  • Butyl acrylate is a compound of empirical formula C7H13O2 and of semi- structural formula:
  • butyl acrylate mention may notably be made of the product sold under the name Butyl acrylate by the company Sigma-Aldrich.
  • monomer (C) is at least one monomer chosen from C1-C4 alkyl acrylates and/or C1-C4 alkyl methacrylates, preferably chosen from C1-C4 alkyl acrylates, and more preferentially monomer (C) is at least butyl acrylate.
  • Isobutyl acrylate is a compound of empirical formula C7H12O2 and of semi- structural formula:
  • tert-Butyl acrylate is a compound of empirical formula C7H12O2 and of semi- structural formula: As tert-butyl acrylate, mention may notably be made of the product sold under the name tert-Butyl acrylate by the company Sigma-Aldrich.
  • the copolymer CP comprises from 80% to 90% by weight of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers.
  • a particularly preferred copolymer CP is obtained by copolymerizing isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, preferably in an isobutyl acrylate/tert-butyl acrylate/acetoacetoxyethyl methacrylate weight ratio of 25/65/10.
  • the composition according to the invention comprises the copolymer(s) CP in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight, and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
  • the composition according to the invention comprises at least one copolymer CP comprising from 80% to 90% by weight of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers, in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
  • C monomer
  • the composition according to the invention comprises at least one copolymer CP obtained by copolymerizing isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, preferably in an isobutyl acrylate/tert-butyl acrylate/acetoacetoxyethyl methacrylate weight ratio of 25/65/10, in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
  • composition according to the present invention comprises one or more non-amino silicones, that is to say one or more silicones different from amino silicones.
  • silicones are different from the copolymers CP described above and from the non-amino alkoxysilanes and their oligomers described below.
  • silicone denotes any organosilicon polymer or oligomer of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and constituted essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond -Si-O-Si-), optionally substituted hydrocarbon radicals being directly linked via a carbon atom to said silicon atoms.
  • amino silicone denotes any silicone including at least one primary, secondary or tertiary amine group and/or at least one quaternary ammonium group.
  • the non-amino silicones that may be used may be volatile or non-volatile.
  • non-amino silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in oil, wax, resin or gum form; silicone oils and silicone resins are preferred.
  • the volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and more particularly from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
  • Volatile Silicone FZ 3109 sold by the company Union Carbide;
  • cyclic silicones with silicon-based organic compounds such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and of oxy-1,1’- bis(2,2,2’,2’,3,3’-hexatrimethylsilyloxy)neopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5* 10’ 6 m 2 /s at 25°C, such as decamethyltetrasiloxane.
  • non-volatile silicones mention may be made, alone or as a mixture, of polydialkylsiloxanes and particularly polydimethyl siloxanes (PDMS), polydiarylsiloxanes, poly alkylaryl siloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon group, and preferably chosen from aryl groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.
  • PDMS polydimethyl siloxanes
  • organopolysiloxanes or organomodified polysiloxanes, or alternatively organomodified silicones
  • the organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.
  • the polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.
  • organopolysiloxanes including:
  • polyoxyethylene and/or polyoxypropylene groups optionally including G>- C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Coming under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (Ci2)alkylmethicone copolyols, and notably those sold by the company Dow Corning under the name Q2- 5200;
  • the silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethyl silyl end groups.
  • polydialkylsiloxanes mention may be made of the following commercial products:
  • oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm 2 /s;
  • CTFA dimethiconol
  • Products that may be used more particularly in accordance with the invention are mixtures such as:
  • CTFA dimethiconol
  • CTFA cyclic polydimethylsiloxane
  • the polyalkylarylsiloxanes are chosen particularly from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 * 10' 5 to 5* 10' 2 m 2 /s at 25°C.
  • oils of the SF series from General Electric such as SF 1023, SF 1154, SF 1250 and SF 1265.
  • the silicones may also be chosen from silicone resins.
  • the term “resin” means a compound whose structure is three-dimensional.
  • Silicone resins are also referred to as “siloxane resins”.
  • a polydimethylsiloxane is not a silicone resin.
  • the silicone resin(s) according to the invention may be chosen from silicone resins with a molecular weight of between 300 and 100 000 g/mol, preferably between 300 and 50 000 g/mol, more preferentially between 300 and 30 000 g/mol.
  • molecular weight means the average molecular weight (Mw).
  • silicone resins also known as siloxane resins
  • MDTQ silicone resins
  • the letter “M” represents the monofunctional unit of formula RlR2R3SiOi/2, the silicon atom being bonded to just one oxygen atom in the polymer comprising this unit.
  • the letter “D” means a difunctional unit RlR2SiO2/2 in which the silicon atom is bonded to two oxygen atoms.
  • T represents a trifunctional unit of formula RlSiO3/2.
  • R namely Rl, R2 and R3, represents a hydrocarbon radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxy group.
  • the letter “Q” means a tetrafunctional unit SiO4/2 wherein the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.
  • silicone resins that may be used in the compositions according to the invention, use may be made, for example, of silicone resins of MQ type, of T type or of MQT type.
  • silicone resins of MQ type mention may be made of the alkyl siloxy silicates of formula [(Rl)3SiOi/2] x (SiO2) y (MQ units) wherein x and y are integers ranging from 50 to 80, and such that the group Rl represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxy group, preferably a methyl group.
  • solid silicone resins of MQ type of trimethyl siloxysilicate type mention may be made of those sold under the reference SRI 000®, E 1 170-002® or SS 4230® by the company General Electric, under the reference TMS 803®, WACKER 803® and 804® by the company Wacker, under the name “KF-7312J®” by the company Shin-Etsu, “DC 749®”, “DC 593®” by the company Dow Coming, under the name Silsoft 74 by the company Momentive Performance Materials.
  • silicone resins comprising MQ siloxysilicate units
  • phenylpropyldimethylsiloxysilicate sold by the company General Electric.
  • the preparation of such resins is notably described in patent US 5 817 302.
  • silicone resins of type T examples include the polysilsesqui oxanes of formula (RSiO3/2)x (T units) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes also possibly comprising Si-OH end groups.
  • Polymethylsilsesquioxane resins that may preferably be used are those in which R represents a methyl group, for instance those sold:
  • Resin MK® such as Belsil PMS MK®: polymer comprising CHaSiCh/? repeating units (T units), which may also comprise up to 1% by weight of (CH ⁇ SiCh 2 units (D units) and having an average molecular weight of about 10 000 g/mol, or
  • Resins comprising MQT units that are notably known are those mentioned in US 5 110 890.
  • a preferred form of resins of MQT type are MQT-propyl (also known as MQTPr) resins.
  • MQTPr MQT-propyl
  • Such resins that may be used in the compositions according to the invention are notably the resins described and prepared in patent application WO 2005/075 542.
  • the MQ-T-propyl resin preferably comprises the units:
  • a hydrocarbon radical notably alkyl
  • the siloxane resin comprises the units:
  • R1 and R3 independently representing an alkyl group containing from 1 to 8 carbon atoms
  • R1 preferably being a methyl group and R3 preferably being a propyl group
  • a being between 0.05 and 0.5 and preferably between 0.15 and 0.4
  • c being greater than 0, preferably between 0.15 and 0.4
  • d being between 0.05 and 0.6, preferably between 0.2 and 0.6 or alternatively between 0.2 and 0.55
  • a + b + c + d 1, and a, b, c and d being mole fractions, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.
  • siloxane resins that may be used according to the invention may be obtained via a process comprising the reaction of:
  • an MQ resin comprising at least 80 mol% of units (R13SiOi/ 2 ) a and (SiO 4 / 2 )d,
  • R1 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than 0, the ratio a/d being between 0.5 and 1.5;
  • T-propyl resin comprising at least 80 mol% of units (R3SiO3/ 2 ) c ,
  • R3 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than 0, on condition that at least 40 mol% of the groups R3 are propyl groups, where the weight ratio A/B is between 95:5 and 15:85 and preferably the weight ratio A/B is 30:70.
  • the weight ratio A/B is between 95:5 and 15:85.
  • the ratio A/B is less than or equal to 70:30.
  • the composition according to the invention comprises at least one non-amino silicone chosen from polydialkylsiloxanes, notably cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); silicone resins, notably MQ-type resins and T-type resins, notably polymethylsilsesquioxane resins; and mixtures thereof.
  • polydialkylsiloxanes notably cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); silicone resins, notably MQ-type resins and T-type resins, notably polymethylsilsesquioxane resins;
  • the composition according to the invention comprises the non- amino silicone(s) in a total content ranging from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and even more preferentially ranging from 2% to 15% by weight, relative to the total weight of the composition.
  • the total content of non-amino silicone(s) chosen from polydialkylsiloxanes; silicone resins, notably MQ-type resins and T-type resins, in the composition ranges from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and even more preferentially from 2% to 15% by weight, relative to the total weight of the composition.
  • the total content of non-amino silicone(s) chosen from cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); polymethylsilsesquioxane resins; and mixtures thereof, in the composition ranges from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight and even more preferentially from 2% to 15% by weight, relative to the total weight of the composition.
  • composition according to the invention comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
  • the composition comprises at least one pigment.
  • pigment refers to any pigment that gives colour to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.
  • the pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in the Kirk-Othmer Encyclopedia of Chemical Technology and in Ullmann ’s Encyclopedia of Industrial Chemistry.
  • They may be natural, of natural origin, or non-natural.
  • These pigments may be in pigment paste or powder form. They may be coated or uncoated.
  • the pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.
  • the pigment may be a mineral pigment.
  • mineral pigment refers to any pigment that satisfies the definition in Ullmann’ s Encyclopedia in the chapter on inorganic pigments.
  • the pigment may be an organic pigment.
  • organic pigment refers to any pigment that satisfies the definition in Ullmann’ s Encyclopedia in the chapter on organic pigments.
  • the organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
  • the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470
  • the pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426.
  • These composite pigments may notably be composed of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.
  • the organic pigment may also be a lake.
  • the term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
  • the inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.
  • D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).
  • the pigment may also be a pigment with special effects.
  • pigments with special effects means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
  • pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
  • pigments with special effects include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride.
  • Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiCh-lake), Prestige sold by Eckart (mica-TiCE), Prestige Bronze sold by Eckart (mica-Fe2O3) and Colorona sold by Merck (mica-TiO2-Fe2O3).
  • particles including a borosilicate substrate coated with titanium oxide.
  • Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.
  • nacres examples include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
  • the pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light.
  • This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle.
  • the reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.
  • These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
  • the reflective particles may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.
  • the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.
  • the reflective particles may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material.
  • the substrate may be made of one or more organic and/or mineral materials.
  • glasses More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.
  • the reflective material may include a layer of metal or of a metallic material.
  • Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.
  • reflective particles including a mineral substrate coated with a layer of metal
  • Particles with a silver-coated glass substrate in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal.
  • Particles with a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.
  • Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
  • a metal substrate such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium
  • said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
  • Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiCh sold under the name Visionaire by the company Eckart.
  • interference pigments which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek).
  • Special-effect pigments also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
  • the variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.
  • the size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.
  • the pigments may be dispersed in the composition by means of a dispersant.
  • the dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof.
  • This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments.
  • These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium.
  • the pigments used in the composition may be surface-treated with an organic agent.
  • the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention.
  • organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
  • waxes for example carnauba wax and beeswax
  • the surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.
  • the surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.
  • the surface-treated pigments are coated with an organic layer.
  • the organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.
  • the surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.
  • An organic agent covalently bonded to the pigments will preferably be used.
  • the agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.
  • the surface treatments of the pigments are chosen from the following treatments:
  • PEG-silicone treatment for instance the AQ surface treatment sold by LCW;
  • methicone treatment for instance the SI surface treatment sold by LCW;
  • dimethicone treatment for instance the Covasil 3.05 surface treatment sold by LCW;
  • a dimethicone/trimethyl siloxysilicate treatment for instance the Covasil 4.05 surface treatment sold by LCW
  • a magnesium myristate treatment for instance the MM surface treatment sold by LCW
  • an aluminium dimyristate treatment for instance the MI surface treatment sold by Miyoshi;
  • an isostearyl sebacate treatment for instance the HS surface treatment sold by Miyoshi;
  • an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment for instance the FSA surface treatment sold by Daito;
  • a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment for instance the FS01 surface treatment sold by Daito;
  • an acrylate/dimethicone copolymer treatment for instance the ASC surface treatment sold by Daito;
  • an isopropyl titanium triisostearate treatment for instance the ITT surface treatment sold by Daito;
  • an acrylate copolymer treatment for instance the APD surface treatment sold by Daito;
  • PF + ITT surface treatment sold by Daito.
  • the dispersant is present with organic or mineral pigments in submicron-sized particulate form.
  • submicron-sized or submicronic refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.
  • the dispersant and the pigment(s) are present in a (dispersantpigment) amount, according to a weight ratio, of between 1 : 4 and 4: 1, particularly between 1.5: 3.5 and 3.5: 1 or better still between 1.75: 3 and 3: 1.
  • the dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type.
  • a silicone backbone such as silicone polyether and dispersants of amino silicone type.
  • suitable dispersants that may be mentioned are: - amino silicones, i.e. silicones comprising one or more amino groups, such as those sold under the following names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, sold by Genesee Polymers,
  • Tego® RC 902 Tego® RC 922, Tego® RC 1041, and Tego® RC 1043, sold by Evonik
  • PDMS polydimethylsiloxane
  • carboxylic groups such as X-22162 and X-22370 by Shin-Etsu
  • epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.
  • the dispersant(s) are of amino silicone type and are cationic.
  • the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.
  • the pigment(s) are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds.
  • the pigment(s) are mineral pigments.
  • the pigment(s) are chosen from iron oxides, notably red, brown or black iron oxides.
  • iron oxides notably red, brown or black iron oxides.
  • composition according to the invention can comprise one or more direct dye(s).
  • direct dye means natural and/or synthetic dyes, other than oxidation dyes. These are dyes which will spread superficially on the fibre. They may be ionic, for example cationic or anionic, or nonionic.
  • Suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
  • the direct dyes may be chosen from anionic direct dyes.
  • the anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances.
  • “Anionic direct dye” is understood to mean any direct dye including in its structure at least one CO2R 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.
  • R7, Rs, R9, Rio, R’7, R’s, R’9 and R’10 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’ ’ representing a hydrogen atom or an alkyl group, an aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;
  • R represents an optionally substituted alkyl or aryl group, X’ as defined previously;
  • aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M + and iv) alkoxy with M + as defined previously;
  • - cycloalkyl notably cyclohexyl
  • Ar-N N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (O)2S(O )-, M + or phenylamino groups;
  • W represents a sigma bond c, 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, together 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 (XIX) and (XIX’) comprise at least one sulfonate radical (O)2S(O )-, 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 (XIX) mention may be made 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 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; Food Yellow 3 or Sunset Yellow; and, as examples of dyes of formula (XIX’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (XX) and (XX’): in which formula
  • Rn, R12 and R13 which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O ), M + with M + as defined previously;
  • R14 represents a hydrogen atom, an alkyl group or a group -C(O)O', M + with M + as defined previously;
  • R15 represents a hydrogen atom
  • - Rie represents an oxo group, in which case R’i6 is absent, or alternatively R15 with Rie together form a double bond;
  • - Rn and Ris which may be identical or different, represent a hydrogen atom, or a group chosen from:
  • Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;
  • R’ 16, R’ 19 and R’20 which may be identical or different, represent a hydrogen atom or an alkyl or hydroxy group
  • R21 represents a hydrogen atom or an alkyl or alkoxy group
  • Ra and Rb which may be identical or different, are as defined previously; preferentially, Ra represents a hydrogen atom and Rb represents an aryl group;
  • - Y represents either a hydroxy group or an oxo group
  • formulae (XX) and (XX’) comprise at least one sulfonate radical (O)2S(O )-, M + or one carboxylate radical -C(O)O', M + on one of the rings D or E; preferentially sodium sulfonate.
  • dyes of formula (XX) mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XX’), mention may be made of: Acid Yellow 17; c) the anthraquinone dyes of formulae (XXI) and (XXI’):
  • R22, R23, R24, R25, R26 and R27 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • - Z’ represents a hydrogen atom or a group NR28R29 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, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, 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;
  • - Z represents a group chosen from hydroxy and NR’2sR’29 with R’28 and R’29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (XXI) and (XXF) comprise at least one sulfonate radical (O)2S(O )-, M + or one carboxylate radical -C(O)O', M + ; preferentially sodium sulfonate.
  • dyes of formula (XXI) mention may be made 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; EXT Violet No. 2; and, as an example of a dye of formula (XXF), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (XXII) and (XXIF):
  • 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 hydroxy groups, alkylthio optionally substituted with one or more hydroxy groups;
  • R30, R31 and R32 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 particularly represents an -NH- group;
  • ALK represents a linear or branched divalent Ci-Ce alkylene group; in particular, ALK represents a -CH2-CH2- group;
  • - p represents an integer inclusively between 1 and 5;
  • J represents a nitro or nitroso group; particularly nitro
  • J represents an oxygen or sulfur atom, or a divalent radical - S(O) m - with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;
  • - 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 groups R30 as defined previously; it being understood that formulae (XXII) and (XXII’) comprise at least one sulfonate radical (O)2S(O )-, M + or one carboxylate radical -C(O)O', M + ; preferentially sodium sulfonate.
  • dyes of formula (XXII) mention may be made of Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII’), 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; EXT D&C Yellow 7; e) the triarylmethane dyes of formula (XXIII):
  • 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; particularly an alkyl and benzyl group optionally substituted with a group (O) m S(O )-, 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 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;
  • R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: I’; with I’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M + ; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’- C(X)-X”-; with M + , R°, X, X’ and X” as defined previously; in particular, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxy group or (O)2S(O )-, M + ; and when R43 with R44 together form a benzo
  • dyes of formula (XXIII) mention may be made 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. f) the xanthene-based dyes of formula (XXIV):
  • R45, R46, R47 and R48 which may be identical or different, represent a hydrogen or halogen atom
  • R49, R50, R51 and R52 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • - (O)CO - M + with M + as defined previously;
  • R49, R50, R51 and R52 represent a hydrogen or halogen atom;
  • - G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; in particular, 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 optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O) m S(O')-, M + groups with m and M + as defined previously;
  • Q and Q’ which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q’ represent an oxygen atom;
  • dyes of formula (XXIV) mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9; g) the indole-based dyes of formula (XXV):
  • R53, R54, R55, R56, R57, R58, R59 and Reo 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; in particular, G represents an oxygen atom;
  • formula (XXIII) comprises at least one sulfonate radical (O)2S(O )-, M + or one carboxylate radical -C(O)O', M + ; preferentially sodium sulfonate.
  • dyes of formula (XXV) mention may be made of Acid Blue 74; h) the quinoline-based dyes of formula (XXVI):
  • - Rei represents a hydrogen or halogen atom or an alkyl group
  • R62, Res and R64 which may be identical or different, represent a hydrogen atom or a group (O)2S(O )-, M + with M + representing a hydrogen atom or a cationic counterion; or alternatively Rei with Re2, or Rei with Re4, together form a benzo group optionally substituted with one or more groups (O)2S(O )-, M + with M + representing a hydrogen atom or a cationic counterion; it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2S(O )-, M + , preferentially sodium sulfonate.
  • dyes of formula (XXVI) mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
  • the direct dyes are chosen from anionic direct dyes.
  • the colouring agent(s) as defined above are present in a total content ranging from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, and even better still from 1% to 10% by weight, relative to the total weight of the composition.
  • the colouring agent(s) are chosen from pigments.
  • the pigment(s) may be present in a total content ranging from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, and even better still from 1% to 10% by weight, relative to the total weight of the composition.
  • composition according to the invention comprises at least one alcohol other than fatty alcohols.
  • Said at least one alcohol is chosen from monoalcohols and from polyols.
  • fatty alcohols it is hereby meant a monoalcohol comprising from 8 to 40 carbon atoms (C8-C40 alkanols).
  • C1-C4 alkanols such as ethanol and isopropanol.
  • polyols use may be made of glycerol, propylene glycol, ethylene glycol, pentaerythritol, trimethylolpropane, 1,3-propanediol, pentane- 1,2-diol, caprylyl glycol (octane- 1,2-diol), butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, poly glycerols, such as glycerol oligomers like diglycerol, polyethylene glycols, and mixtures thereof.
  • the alcohol(s) are chosen from ethanol, hexylene glycol, and mixtures thereof.
  • the total content of alcohol(s) in the composition ranges from 5% to 60% by weight, preferably from 10% to 50% by weight, more preferentially from 15% to 40% by weight, relative to the total weight of the composition.
  • the composition may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W7O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two- phase or multi -phase lotion.
  • composition according to the invention may be aqueous or anhydrous.
  • the composition according to the invention is anhydrous.
  • an “anhydrous composition” means a composition comprising a water content of less than 5% by weight, preferably less than 3% by weight, relative to the weight of the composition. Preferably, this water content is less than 1% by weight, better still less than 0.5% or even less than 0.3% by weight, relative to the weight of the composition. More particularly, the composition does not comprise any water (0%).
  • said anhydrous composition does not comprise any water added during its preparation, the residual water that may be present possibly originating from the starting materials used during the preparation.
  • composition according to the invention may also comprise at least one hydrocarbon oil.
  • thermo means a water-immiscible non-aqueous compound that is liquid at room temperature (20°C) and at atmospheric pressure (760 mmHg).
  • hydrocarbon oil means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • composition may comprise at least one hydrocarbon oil chosen from:
  • branched Cs-Ci6 alkanes such as Cs-Ci6 and preferably Cs-Cu isoalkanes (also known as isoparaffins), such as isododecane (also known as 2, 2, 4,4,6- pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names, linear Cs-Ci6 alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (Cn) and of n-tridecane (C13) obtained in examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, and mixtures thereof,
  • esters having from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;
  • oils of plant origin such as triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else
  • hydrocarbons of mineral or synthetic origin comprising more than 16 carbon atoms, in particular petroleum jelly, poly decenes, hydrogenated polyisobutene, in particular Parleam®, squalane and liquid paraffins, and mixtures thereof,
  • oils of formula R1COOR2 in which Ri represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon chain containing from 1 to 40 carbon atoms, on condition that the sum of the number of carbon atoms in Ri and R2 is greater than or equal to 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2- hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, oc
  • - fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2 -undecylpentadecanol .
  • the hydrocarbon oil present in the compositions according to the present invention is apolar; it is formed solely of carbon and hydrogen atoms.
  • the hydrocarbon oil is chosen from:
  • Cs-Cie hydrocarbon oils and more preferentially from branched Cs-Ci4 alkanes such as isododecane or isodecane;
  • esters such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;
  • the total content of hydrocarbon oil(s) in the composition ranges from 5% to 80% by weight, preferably from 10% to 75% by weight, more preferentially from 20% to 70% by weight and better still from 35% to 65% by weight relative to the total weight of the composition.
  • the total content of hydrocarbon oil(s) chosen from branched Cs- C14 alkanes, C3-C8 short-chain esters and mixtures thereof ranges from 5% to 80% by weight, preferably from 10% to 75% by weight, more preferentially from 20% to 70% by weight, and better still from 35% to 65% by weight relative to the total weight of the composition.
  • composition according to the invention can also comprise one or more alkoxysilanes.
  • R a represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;
  • Rb and Re which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group, it being understood that if Ra does not represent an alkoxy group, then Rb and Re cannot simultaneously represent a hydrogen atom;
  • Ra and Re which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms;
  • - A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
  • - r denotes an integer ranging from 0 to 1.
  • alkoxysilanes of formula (I), oligomers thereof and/or mixtures thereof mention may notably be made of 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), 3-ureidopropyltrimethoxysilane and N-cy cl ohexy 1 aminomethy Itri ethoxy sil ane .
  • APTES 3 -aminopropyltri ethoxy silane
  • APIMDES 3- aminopropylmethyldiethoxysilane
  • 3-ureidopropyltrimethoxysilane and N-cy cl ohexy 1 aminomethy Itri ethoxy sil ane .
  • APTES may be purchased, for example, from the company Dow Coming under the name Xiameter OFS-6011 Silane or from the company Momentive Performance Materials under the name Silsoft A-l 100 or from the company Shin-Etsu under the name KBE-903.
  • the compounds of formula (I) may also denote Dynasylan SIVO 210 or Dynasylan 1505 sold by the company Evonik.
  • 3 -Ureidopropyltrimethoxy silane may be purchased, for example, from the company Gelest under the reference SIU9058.0.
  • N-Cycloheylaminomethyltriethoxysilane may be purchased, for example, from the company Wacker under the name Geniosil XL 926.
  • alkoxysilanes of formula (E), oligomers thereof and/or mixtures thereof mention may notably be made of N,N-bis[3- (trimethoxysilyl)propyl]ethylenediamine (CAS RN: 74956-86-8), Nl,Nl-bis[3- (triethoxysilyl)propyl]-l,2-ethanediamine (CAS RN: 457065-96-2), 1,2- ethanediamine, Nl-[3-(triethoxysilyl)propyl]-Nl-[3-(trimethoxysilyl)propyl]- (CAS RN: 1638528-78-5), and mixtures thereof.
  • alkoxysilane(s) of formula (I) are chosen from the compounds of formula (I) for which:
  • Ra represents an alkyl group containing from 1 to 10 carbon atoms, notably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy;
  • Rb and Re which may be identical or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, such as an ethyl;
  • Rd and R e which are identical, represent a hydrogen atom or Rd denotes a hydrogen atom and Re denotes a Cs-G, cycloalkyl radical such as cyclohexyl;
  • - A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
  • the alkoxysilane(s) of formula (I) are chosen from the compounds of formula (I) in which Ra represents an ethoxy group, Rb and Re are identical and represent ethyl, Rd and R e represent a hydrogen atom, A represents propylene and r denotes an integer equal to 0.
  • the alkoxysilane of formula (I) is 3- aminopropyltriethoxysilane (APTES).
  • R a represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;
  • Rb represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group;
  • R c represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms; it being understood that if Ra and R c do not represent an alkoxy group, then Rb cannot represent a hydrogen atom;
  • - k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;
  • Rf represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; or a group of formula (Ila) below: in which Rn represents a hydroxy group (OH); an alkyl group containing from 1 to 10 carbon atoms, preferably a methyl.
  • alkoxysilanes of formula (II), oligomers thereof and/or mixtures thereof mention may notably be made of tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltri ethoxy sil ane, i sobuty Itri ethoxy sil ane, pheny Itri ethoxy sil ane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane, octytri ethoxy sil ane (OTES) and mixtures thereof.
  • TEOS tetraethoxy
  • TEOS may be purchased, for example, from the company Evonik under the name Dynasylan® A or Dynasylan® A SQ.
  • MTES may be purchased, for example, from the company Evonik under the name Dynasylan® MTES.
  • DMDES may be purchased, for example, from the company Gelest under the reference SID3404.0.
  • alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof are such that:
  • R a represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methoxy or an ethoxy; or an alkyl group containing from 1 to 10 carbon atoms optionally substituted with an aryl group, preferably 1 to 2 carbon atoms optionally substituted with an aryl group;
  • Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
  • R c represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy;
  • - k denotes an integer ranging from 0 to 3, preferably equal to 0;
  • Rf represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as a methyl or an ethyl.
  • the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof are such that: - R a represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
  • Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
  • R c represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy;
  • Rf represents an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as a methyl or an ethyl.
  • the alkoxysilane(s) of formula (II) are chosen from octyltriethoxysilane (OTES), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) and mixtures thereof.
  • OTES octyltriethoxysilane
  • MTMS methyltrimethoxysilane
  • MTES methyltriethoxysilane
  • the alkoxysilane(s) of formula (II) are methyltrimethoxysilane (MTMS) and/or methyltriethoxysilane (MTES).
  • an “oligomer” means compound(s) comprising at least 2 silicon atoms, obtained by oligomerization or polymerization of compounds of formula (I), (f) or (II).
  • the alkoxysilane(s) are chosen from amino alkoxysilanes, notably from those of formula (I), such as 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), and mixtures thereof.
  • APTES 3 -aminopropyltri ethoxy silane
  • APIMDES 3- aminopropylmethyldiethoxysilane
  • composition comprises one or more alkoxysilanes
  • their total content is advantageously in the range of from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, more preferentially still from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of the composition.
  • composition according to the invention may contain any additive usually used in cosmetic compositions intended for treating keratin fibres.
  • the above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition.
  • Another subject of the present invention is a method for colouring keratin fibres comprising the application of the above composition to said fibres.
  • the process further comprises a step of applying an additional composition A, different from the composition according to the invention, and which comprises at least one aminoalkoxysilane chosen from the compounds of formula (I) or (T) as described above, oligomers thereof and/or mixtures thereof.
  • This step carried out sequentially with the application of the composition according to the invention, can be carried out before and/or after the application of the composition according to the invention, and preferably before the application of the composition according to the invention.
  • compositions to the keratin fibres may be performed on said fibres, which may be wet or dry.
  • the keratin fibres are hair.
  • the composition according to the invention may be applied to all types of light or dark, natural or dyed, permanent- waved, bleached or relaxed hair.
  • the application to the hair may be performed via any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.
  • the application of the composition to the hair is generally performed at room temperature (between 15°C and 25°C).
  • the hair may be left to dry or may be dried, for example at a temperature above or equal to 30°C.
  • the process according to the invention may also comprise, after applying the composition, a step of applying heat to the keratin fibres using a heating device.
  • Such a device may be, for example, a hood, a hair dryer, a straightening or curling iron, a Climazon, etc.
  • the step of applying heat is performed using a hair dryer.
  • a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.
  • the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.
  • the invention also relates to the use of this composition for colouring keratin fibres, and in particular the hair.
  • Example 1 Preparation of compositions The compositions below were prepared, by mixing the ingredients indicated in Table 1 below in which the contents are expressed as percentages by weight of starting material, relative to the total weight of the composition (a.m. signifying active material).
  • compositions A to D from Example 1 were evaluated on 1 g locks of natural hair containing 90% white hair.
  • the colouring protocol is as follows:
  • composition is applied to a lock of dry hair in a proportion of 0.6 g of composition (bath ratio of 0.6 g per g of hair). It is spread with a finger over the lock.
  • L*, a* and b* represent the values measured after colouring the hair and after having undergone 5 shampoo washes
  • Lo*, ao* and bo* represent the values measured after colouring the hair but before the 5 shampoo washes.
  • the locks of hair coloured with the three compositions according to the invention have a colour difference AE between the coloured locks before shampoo washing and then after having undergone 5 shampoo washes, which is much smaller than the lock coloured with composition A.
  • the persistence of the colouring obtained with compositions B, C and D according to the invention is therefore significantly improved compared with the colouring obtained with comparative composition A.
  • the coloured coating obtained by means of the compositions according to the invention has improved persistence with respect to shampoo washing.

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Abstract

The present invention relates to a cosmetic composition for colouring keratin fibres, comprising: i) at least one copolymer CP obtained by polymerization of: - 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I). - 80% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates; Wherein the copolymer CP does not comprise any monomer (A) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof; ii) at least one non-amino silicone; iii) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and iv) at least one alcohol chosen from monoalcohols other than fatty alcohols and from polyols. The present invention also relates to a method for colouring keratin fibres using such a composition and to the use of this composition for colouring keratin fibres.

Description

DESCRIPTION
TITLE: Composition for colouring keratin fibres comprising at least one copolymer containing acetoacetate functions, at least one silicone, at least one colouring agent and at least one alcohol
The present invention relates to the field of the cosmetic treatment of keratin fibres and notably to the dyeing of keratin fibres, preferably the hair. It thus aims to provide novel colouring compositions comprising a copolymer containing acetoacetate units, which offer excellent technical performance, notably in terms of wear property of the colourings which they make it possible to obtain.
More specifically, the present invention relates to a composition intended for colouring human keratin fibres such as hair, comprising a particular copolymer formed from monomers bearing acetoacetate functions in combination with a non-amino silicone, a colouring agent and an alcohol.
The present invention also relates to a method for colouring keratin fibres such as the hair using this composition.
Technical field
In the field of dyeing hair keratin fibres, it is known practice to dye fibres via various techniques using direct dyes or pigments in order to obtain non-permanent dyeing, or dye precursors in order to obtain permanent dyeing.
There are essentially three types of process for dyeing the hair: a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural colour and which uses oxidation dyes which penetrate into the hair fibre and form the dye via an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in dyeing keratin fibres with dye compositions containing direct dyes; c) temporary dyeing, which gives rise to a modification of the natural colour of the head of hair which lasts from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a hair “makeup” process. Another dyeing method consists in using pigments. Specifically, the use of pigments on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair, since the surface pigment masks the natural colour of the fibre. However, the colourings obtained via this dyeing method have the drawback of having poor resistance to shampoo washing and also to external agents such as sebum, perspiration, brushing and/or rubbing.
Thus, “hair makeup” products have recently been developed, which provide temporary hair colour that lasts for 1 to 3 shampoo washes. For consumers, they are a particularly attractive alternative to permanent hair dyeing, provided that a good wear property of the colour effect is guaranteed in contact with water and a few shampoo washes. This requirement may notably be satisfied by the use of effective film-forming agents.
Thus, document FR 2 741 530 proposes for this purpose, for the temporary colouring of keratin fibres, the use of a dispersion of film-forming polymer particles including at least one acidic function and at least one pigment dispersed in the continuous phase of said dispersion. The colourings obtained via this dyeing method however have the drawback of being removed too quickly on shampoo washing.
It is moreover proposed in FR 2 907 678 to perform coloured coating of the hair using a composition comprising a polysiloxane/polyurea block copolymer and a pigment. However, with such a composition, the coatings obtained are not always very uniform and the hair strand separation is not always satisfactory.
There is thus still a need for compositions that allow keratin fibres to be dyed, with the advantage that the fibres are uniformly coloured, while forming a coating that is resistant to shampoo washing, sebum and the various attacking factors to which the hair may be subjected, such as brushing, perspiration and/or rubbing.
The present invention enables these needs to be met.
Disclosure of the invention
One subject of the present invention is therefore a cosmetic composition for colouring keratin fibres, comprising: i) at least one copolymer CP obtained by polymerization of
- 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I):
Figure imgf000004_0001
in which:
• Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
• Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
• Rd represents a linear or branched (Ci-C4)alkyl group, and
• L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group;
- 80% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates; wherein the copolymer CP does not comprise any monomer (A) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof; ii) at least one non-amino silicone; iii) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and iv) at least one alcohol chosen from polyols and monoalcohols other than fatty alcohols.
The application of such a composition to keratin fibres makes it possible to obtain uniform and smooth coloured coatings. It provides visible colouring on all types of fibres, which is resistant to water and notably to shampoo washing and sebum. Such a coating may be resistant to the various external attacking factors to which keratin fibres may be subjected, for instance blow-drying, brushing, rubbing and perspiration.
Another subject of the present invention is a method for colouring keratin fibres comprising the application of the above composition to said fibres.
The invention also relates to the use of this composition for colouring keratin fibres, and in particular the hair.
Other subjects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.
In the present description, and unless otherwise indicated: - the expression “at least one” is equivalent to the expression “one or more” and can be replaced therewith;
- the expression “between... and...” is equivalent to the expression “ranging from... to...” and can be replaced therewith, and implies that the limits are included.
- For the purposes of the present invention, the expression “greater than” and, respectively, the term “less than” refer to an open range which is strictly greater, or, respectively, strictly less, and thus that the limits are not included.
- According to the present patent application, “keratin fibres” is particularly understood to mean human keratin fibres such as head hair, eyelashes, eyebrows, and body hair, preferentially head hair, eyebrows and eyelashes, even more preferentially head hair.
- For the purposes of the present invention, “the hair" is understood to mean head hair. This term does not correspond to body hair, the eyebrows or the eyelashes.
- an “alkyl” radical denotes a linear or branched saturated radical containing, for example, from 1 to 30 carbon atoms;
- an “aminoalkyF radical denotes an alkyl radical as defined previously, said alkyl radical comprising an NH2 group;
- a “hydroxyalkyF radical denotes an alkyl radical as defined previously, said alkyl radical comprising an OH group;
- an "alkylene" radical denotes a linear or branched divalent saturated C1-C10 hydrocarbon group such as methylene, ethylene or propylene;
- a “cycloalkyF or “ alicy cloalkyF radical denotes a saturated monocyclic or polycyclic, preferably monocyclic, cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 40 carbon atoms, in particular comprising from 3 to 24 carbon atoms, more particularly from 3 to 20 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl or isobomyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is then an isobomyl group;
- an “aryl” radical is a monocyclic, bicyclic or tricyclic, fused or non-fused, unsaturated and aromatic cyclic hydrocarbon radical, comprising from 6 to 30 carbon atoms, preferably between 6 and 14 carbon atoms, more preferentially between 6 and 12 carbon atoms; preferably, the aryl group comprises 1 ring of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted with one or more (Ci-C4)alkyl groups such as methyl, preferably tolyl, xylyl, or methylnaphthyl; preferably, the aryl group represents phenyl;
- an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined previously;
- an “alkoxy” radical denotes an alkyl-oxy radical with “alkyl” as defined previously.
Unless otherwise indicated, when compounds are mentioned in the present patent application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof or the salts thereof, alone or as a mixture.
The invention is not limited to the examples illustrated. The characteristics of the various examples may notably be combined within variants which are not illustrated.
Copolymers CP
The composition according to the invention comprises at least one copolymer CP obtained by the polymerization of:
- 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I):
Figure imgf000006_0001
in which:
• Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
• Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
• Rd represents a linear or branched (Ci-C4)alkyl group, and
• L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group;
- 80% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates; wherein the copolymer CP does not contain units from any monomer (A) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobomyl methacrylate, and mixtures thereof;
In this formula:
• Ra preferably represents a hydrogen atom or a methyl group, preferably a methyl group,
• Rb and Rc preferably represent a hydrogen atom,
• Rd preferably represents a methyl group, and
• L preferably represents a (Ci-C4)alkylene group, and more preferentially L represents ethylene.
According to a preferred embodiment, the monomer of formula (I) is chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.
Said copolymer CP may be a statistical, alternating (block) or gradient copolymer.
Preferably, the copolymer CP is a statistical copolymer.
For the purposes of the present invention, the term “statistical copolymer” means a copolymer formed of macromolecules in which the sequential distribution of the monomer units (B) and (C) obeys known statistical laws. In other words, in a statistical copolymer, the various monomers follow each other in any order. Statistical copolymers are also known as random copolymers. For example, the sequence of a statistical copolymer, formed from monomers A and B, may be as follows: A-A-B-A- B-B-B-B-A-A-B-A.
The copolymer CP according to the present invention is in particular free of monomer units different from monomers (B) and (C) defined above.
Monomer (B)
As indicated above, the copolymer CP comprises from 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I):
Figure imgf000007_0001
in which:
• Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group; preferably, Ra represents a methyl group,
• Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group; preferably, Rb and Rc represent a hydrogen atom,
• Rd represents a linear or branched (Ci-C4)alkyl group; preferably, Rd represents a methyl group, and
• L represents a linear or branched (Ci-Ce)alkylene or cycloalkylene group; preferably, L represents a (Ci-C4)alkylene group, in particular ethylene.
Preferably, the copolymer CP comprises from 5% to 15% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I) as described above.
In particular, monomer (B) is chosen from acetoacetoxyethyl acrylate, acetoacetoxy ethyl methacrylate, and mixtures thereof, and preferably, monomer (B) is acetoacetoxyethyl methacrylate.
Acetoacetoxy ethyl acrylate is a compound of empirical formula C9H12O5, and of semi -structural formula:
Figure imgf000008_0001
As acetoacetoxyethyl acrylate, mention may notably be made of the product sold under the name Butanoic acid, 3-oxo-2-[(l-oxo-2-propen-l-yl)oxy]ethyl ester by the company Alfa Chemistry.
Acetoacetoxyethyl methacrylate is a compound of empirical formula C10H 4O5, and of semi-structural formula:
Figure imgf000008_0002
As acetoacetoxyethyl methacrylate, mention may notably be made of the product sold under the name Eastman™ AAEM by the company Eastman.
Monomer (C) As indicated above, the copolymer CP comprises from 80% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates.
Among the C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates that can be used as monomers (C), mention may be made in particular of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertbutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and mixtures thereof.
Preferably, monomer (C) is a C1-C4 alkyl acrylate, in particular chosen from butyl acrylate, isobutyl acrylate and tert-butyl acrylate.
Butyl acrylate is a compound of empirical formula C7H13O2 and of semi- structural formula:
Figure imgf000009_0001
As a butyl acrylate, mention may notably be made of the product sold under the name Butyl acrylate by the company Sigma-Aldrich.
According to a preferred embodiment, monomer (C) is at least one monomer chosen from C1-C4 alkyl acrylates and/or C1-C4 alkyl methacrylates, preferably chosen from C1-C4 alkyl acrylates, and more preferentially monomer (C) is at least butyl acrylate.
Isobutyl acrylate is a compound of empirical formula C7H12O2 and of semi- structural formula:
Figure imgf000009_0002
As isobutyl acrylate, mention may notably be made of the product sold under the name Isobutyl acrylate by the company Sigma-Aldrich. tert-Butyl acrylate is a compound of empirical formula C7H12O2 and of semi- structural formula:
Figure imgf000009_0003
As tert-butyl acrylate, mention may notably be made of the product sold under the name tert-Butyl acrylate by the company Sigma-Aldrich.
According to another particularly preferred embodiment of the invention, the copolymer CP comprises from 80% to 90% by weight of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers.
A particularly preferred copolymer CP is obtained by copolymerizing isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, preferably in an isobutyl acrylate/tert-butyl acrylate/acetoacetoxyethyl methacrylate weight ratio of 25/65/10.
According to a preferred embodiment, the composition according to the invention comprises the copolymer(s) CP in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight, and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
According to a particularly preferred embodiment, the composition according to the invention comprises at least one copolymer CP comprising from 80% to 90% by weight of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers, in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
According to a more preferred embodiment, the composition according to the invention comprises at least one copolymer CP obtained by copolymerizing isobutyl acrylate, tert-butyl acrylate and acetoacetoxyethyl methacrylate, preferably in an isobutyl acrylate/tert-butyl acrylate/acetoacetoxyethyl methacrylate weight ratio of 25/65/10, in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
Non-amino silicones
The composition according to the present invention comprises one or more non-amino silicones, that is to say one or more silicones different from amino silicones. Such silicones are different from the copolymers CP described above and from the non-amino alkoxysilanes and their oligomers described below. In a manner known per se, the term “ silicone" denotes any organosilicon polymer or oligomer of linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and constituted essentially of a repetition of main units in which the silicon atoms are linked together via oxygen atoms (siloxane bond -Si-O-Si-), optionally substituted hydrocarbon radicals being directly linked via a carbon atom to said silicon atoms.
The term “amino silicone” denotes any silicone including at least one primary, secondary or tertiary amine group and/or at least one quaternary ammonium group.
The non-amino silicones that may be used may be volatile or non-volatile.
The non-amino silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in oil, wax, resin or gum form; silicone oils and silicone resins are preferred.
Silicones are notably described in detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.
The volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and more particularly from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
- octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia;
- cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type having the chemical structure:
Figure imgf000011_0001
Mention may be made of Volatile Silicone FZ 3109 sold by the company Union Carbide;
- mixtures of cyclic silicones with silicon-based organic compounds, such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and of oxy-1,1’- bis(2,2,2’,2’,3,3’-hexatrimethylsilyloxy)neopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5* 10’6 m2/s at 25°C, such as decamethyltetrasiloxane.
Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pages 27-32 - Todd & Byers Volatile silicone fluids for cosmetics,' mention may be made of the product sold under the name SH 200 by the company Toray Silicone.
Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and particularly polydimethyl siloxanes (PDMS), polydiarylsiloxanes, poly alkylaryl siloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon group, and preferably chosen from aryl groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.
The organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously. The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.
Among the organomodified silicones, mention may be made of organopolysiloxanes including:
- polyoxyethylene and/or polyoxypropylene groups optionally including G>- C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Coming under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (Ci2)alkylmethicone copolyols, and notably those sold by the company Dow Corning under the name Q2- 5200;
- thiol groups, such as the products sold under the names GP 72 A and GP 71 from Genesee;
- alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt; - hydroxylated groups, for instance polyorganosiloxanes bearing a hydroxyalkyl function;
- acyloxyalkyl groups, such as the polyorganosiloxanes described in patent US-A-4 957 732;
- anionic groups of the carboxylic acid type, as described, for example, in EP 186 507, or of the alkylcarboxylic type, such as the product X-22-3701E from the company Shin-Etsu; or alternatively of the 2-hydroxy alkyl sulfonate or 2- hydroxyalkylthiosulfate type, such as the products sold by the company Goldschmidt under the names Abil® S201 and Abil® S255.
The silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethyl silyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercial products:
- the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000;
- the oils of the Mirasil® series sold by the company Rhodia;
- the oils of the 200 series from the company Dow Corning, such as DC200, with a viscosity of 60 000 mm2/s;
- the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.
In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are poly(Ci-C2o)dialkylsiloxanes.
Products that may be used more particularly in accordance with the invention are mixtures such as:
- mixtures formed from a polydimethylsiloxane with a hydroxy-terminated chain, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by the company Dow Corning. The polyalkylarylsiloxanes are chosen particularly from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 * 10'5 to 5* 10'2 m2/s at 25°C.
Among these polyalkylarylsiloxanes, mention may be made of the products sold under the following names:
- the Silbione® oils of the 70 641 series from Rhodia;
- the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;
- the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;
- the silicones of the PK series from Bayer, such as the product PK20;
- the silicones of the PN and PH series from Bayer, such as the products PN1000 and PHlOOO;
- certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.
The silicones may also be chosen from silicone resins. Generally, the term “resin” means a compound whose structure is three-dimensional. “Silicone resins” are also referred to as “siloxane resins”. Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.
The silicone resin(s) according to the invention may be chosen from silicone resins with a molecular weight of between 300 and 100 000 g/mol, preferably between 300 and 50 000 g/mol, more preferentially between 300 and 30 000 g/mol. The term “molecular weight” means the average molecular weight (Mw).
The nomenclature of silicone resins (also known as siloxane resins) is known under the name “MDTQ”, the resin being described as a function of the various siloxane monomer units it comprises, each of the letters “MDTQ” characterizing a type of unit.
The letter “M” represents the monofunctional unit of formula RlR2R3SiOi/2, the silicon atom being bonded to just one oxygen atom in the polymer comprising this unit.
The letter “D” means a difunctional unit RlR2SiO2/2 in which the silicon atom is bonded to two oxygen atoms.
The letter “T” represents a trifunctional unit of formula RlSiO3/2.
Such resins are described, for example, in the Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley & Sons, New York, (1989), pp. 265- 270, and US 2 676 182, US 3 627 851, US 3 772 247, US 5 248 739 or US 5 082 706, US 5 319 040, US 5 302 685 and US 4 935 484.
In the units M, D and T defined previously, R, namely Rl, R2 and R3, represents a hydrocarbon radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxy group.
Finally, the letter “Q” means a tetrafunctional unit SiO4/2 wherein the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.
Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying as a function of the type of monomer (or units), of the nature and number of the R radical, of the length of the polymer chain, of the degree of branching and of the size of the pendent chains.
As silicone resins that may be used in the compositions according to the invention, use may be made, for example, of silicone resins of MQ type, of T type or of MQT type.
MQ resins:
As examples of silicone resins of MQ type, mention may be made of the alkyl siloxy silicates of formula [(Rl)3SiOi/2]x(SiO2)y (MQ units) wherein x and y are integers ranging from 50 to 80, and such that the group Rl represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxy group, preferably a methyl group.
As examples of solid silicone resins of MQ type of trimethyl siloxysilicate type, mention may be made of those sold under the reference SRI 000®, E 1 170-002® or SS 4230® by the company General Electric, under the reference TMS 803®, WACKER 803® and 804® by the company Wacker, under the name “KF-7312J®” by the company Shin-Etsu, “DC 749®”, “DC 593®” by the company Dow Coming, under the name Silsoft 74 by the company Momentive Performance Materials.
As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151® sold by the company General Electric). The preparation of such resins is notably described in patent US 5 817 302.
T resins:
Examples of silicone resins of type T that may be mentioned include the polysilsesqui oxanes of formula (RSiO3/2)x (T units) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes also possibly comprising Si-OH end groups.
Polymethylsilsesquioxane resins that may preferably be used are those in which R represents a methyl group, for instance those sold:
- by the company Wacker under the reference Resin MK®, such as Belsil PMS MK®: polymer comprising CHaSiCh/? repeating units (T units), which may also comprise up to 1% by weight of (CH^SiCh 2 units (D units) and having an average molecular weight of about 10 000 g/mol, or
- by the company Shin-Etsu under the references KR 220L®, which are composed of T units of formula CHaSiCh/? and contain Si-OH (silanol) end groups, under the reference KR-242A®, which comprise 98% of T units and 2% of dimethyl D units and contain Si-OH end groups, or else under the reference KR 251®, comprising 88% of T units and 12% of dimethyl D units and contain Si-OH end groups, or
- by the company Grant Industries under the name Granresin PMSQ ID containing 80% polymethylsilsesquioxane in isododecane.
MQT resins:
Resins comprising MQT units that are notably known are those mentioned in US 5 110 890.
A preferred form of resins of MQT type are MQT-propyl (also known as MQTPr) resins. Such resins that may be used in the compositions according to the invention are notably the resins described and prepared in patent application WO 2005/075 542.
The MQ-T-propyl resin preferably comprises the units:
(i) (Rl3SiOl/2)a
(ii) (R22SiO2/2)b
(iii) (R3SiO3/2)c and
(iv) (SiO4/2)d with Rl, R2 and R3 independently representing a hydrocarbon radical (notably alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or else a hydroxy group and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group, a, b, c and d being mole fractions, a being between 0.05 and 0.5, b being between 0 and 0.3, c being greater than 0, d being between 0.05 and 0.6, a + b + c + d = l, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.
Preferably, the siloxane resin comprises the units:
(i) (Rl3SiOl/2)a
(iii) (R3SiO3/2)c and
(iv) (SiO4/2)d
With R1 and R3 independently representing an alkyl group containing from 1 to 8 carbon atoms, R1 preferably being a methyl group and R3 preferably being a propyl group, a being between 0.05 and 0.5 and preferably between 0.15 and 0.4, c being greater than 0, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6 or alternatively between 0.2 and 0.55, a + b + c + d = 1, and a, b, c and d being mole fractions, provided that more than 40 mol% of the R3 groups of the siloxane resin are propyl groups.
The siloxane resins that may be used according to the invention may be obtained via a process comprising the reaction of:
A) an MQ resin comprising at least 80 mol% of units (R13SiOi/2)a and (SiO4/2)d,
R1 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than 0, the ratio a/d being between 0.5 and 1.5; and
B) a T-propyl resin comprising at least 80 mol% of units (R3SiO3/2)c,
R3 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than 0, on condition that at least 40 mol% of the groups R3 are propyl groups, where the weight ratio A/B is between 95:5 and 15:85 and preferably the weight ratio A/B is 30:70. Advantageously, the weight ratio A/B is between 95:5 and 15:85. Preferably, the ratio A/B is less than or equal to 70:30. These preferred ratios have proven to afford comfortable deposits.
Preferably, the composition according to the invention comprises at least one non-amino silicone chosen from polydialkylsiloxanes, notably cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); silicone resins, notably MQ-type resins and T-type resins, notably polymethylsilsesquioxane resins; and mixtures thereof.
Preferably, the composition according to the invention comprises the non- amino silicone(s) in a total content ranging from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and even more preferentially ranging from 2% to 15% by weight, relative to the total weight of the composition.
Preferably, the total content of non-amino silicone(s) chosen from polydialkylsiloxanes; silicone resins, notably MQ-type resins and T-type resins, in the composition ranges from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and even more preferentially from 2% to 15% by weight, relative to the total weight of the composition.
Preferably, the total content of non-amino silicone(s) chosen from cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); polymethylsilsesquioxane resins; and mixtures thereof, in the composition ranges from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight and even more preferentially from 2% to 15% by weight, relative to the total weight of the composition.
Colouring agents
The composition according to the invention comprises at least one colouring agent chosen from pigments, direct dyes and mixtures thereof.
Preferably, the composition comprises at least one pigment.
Pigments
The term “pigment” refers to any pigment that gives colour to keratin materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%. The pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in the Kirk-Othmer Encyclopedia of Chemical Technology and in Ullmann ’s Encyclopedia of Industrial Chemistry.
They may be natural, of natural origin, or non-natural.
These pigments may be in pigment paste or powder form. They may be coated or uncoated.
The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.
The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’ s Encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.
The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’ s Encyclopedia in the chapter on organic pigments.
The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771. Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:
- Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710);
- Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);
- Cosmenyl Orange GR: Orange 43 pigment (CI 71105);
- Cosmenyl Red R: Red 4 pigment (CI 12085);
- Cosmenyl Carmine FB: Red 5 pigment (CI 12490);
- Cosmenyl Violet RL: Violet 23 pigment (CI 51319);
- Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);
- Cosmenyl Green GG: Green 7 pigment (CI 74260);
- Cosmenyl Black R: Black 7 pigment (CI 77266).
The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.
The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.
Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).
An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850: 1).
The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
Several types of pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the nacres Cellini sold by BASF (mica-TiCh-lake), Prestige sold by Eckart (mica-TiCE), Prestige Bronze sold by Eckart (mica-Fe2O3) and Colorona sold by Merck (mica-TiO2-Fe2O3).
Mention may also be made of the gold-coloured nacres sold notably by the company BASF under the name Brilliant Gold 212G(Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super Bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion Orange (Colorona) and Matte Orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna Fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone GO 12 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan Opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu-antique Bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte Blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian Summer (Xirona), and mixtures thereof.
Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.
Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.
Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle.
The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.
These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.
When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.
When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and/or mineral materials.
More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.
The reflective material may include a layer of metal or of a metallic material.
Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.
Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver- coated borosilicate substrate.
Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with a nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.
Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiCh sold under the name Visionaire by the company Eckart.
Mention may also be made of interference pigments which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Special-effect pigments also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects. The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.
The pigments may be dispersed in the composition by means of a dispersant.
The dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxy stearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly( 12-hydroxy stearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or else polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.
As other dispersants that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
The pigments used in the composition may be surface-treated with an organic agent.
Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.
The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.
Preferably, the surface-treated pigments are coated with an organic layer.
The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.
The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.
An organic agent covalently bonded to the pigments will preferably be used.
The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.
Preferably, the surface treatments of the pigments are chosen from the following treatments:
- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;
- a methicone treatment, for instance the SI surface treatment sold by LCW;
- a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;
- a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW; - a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;
- an aluminium dimyristate treatment, for instance the MI surface treatment sold by Miyoshi;
- a perfluoropolymethyl isopropyl ether treatment, for instance the FHC surface treatment sold by LCW;
- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;
- a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;
- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;
- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;
- an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;
- an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito;
- an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;
- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito.
According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form.
The term “submicron-sized” or “ submicronic" refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm.
According to one embodiment, the dispersant and the pigment(s) are present in a (dispersantpigment) amount, according to a weight ratio, of between 1 : 4 and 4: 1, particularly between 1.5: 3.5 and 3.5: 1 or better still between 1.75: 3 and 3: 1.
The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type. Among the suitable dispersants that may be mentioned are: - amino silicones, i.e. silicones comprising one or more amino groups, such as those sold under the following names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, sold by Genesee Polymers,
- silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043, sold by Evonik,
- polydimethylsiloxane (PDMS) silicones bearing carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.
According to a particular embodiment, the dispersant(s) are of amino silicone type and are cationic.
Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.
In one variant of the invention, the pigment(s) are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) are mineral pigments.
Preferably, the pigment(s) are chosen from iron oxides, notably red, brown or black iron oxides. As an example of an iron oxide, mention may be made of the iron oxide sold by the company Sun Chemical under the name SunPuro® Red Iron Oxide.
Direct dyes
The composition according to the invention can comprise one or more direct dye(s).
The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes which will spread superficially on the fibre. They may be ionic, for example cationic or anionic, or nonionic.
Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances. “Anionic direct dye” is understood to mean any direct dye including in its structure at least one CO2R 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.
As acid dyes that are useful for the invention, mention may be made of the dyes of formulae (XIX), (XIX’), (XX), (XX’), (XXI), (XXI’), (XXII), (XXII’), (XXIII), (XXIV), (XXV) and (XXVI) below: a) the diaryl anionic azo dyes of formula (XIX) or (XIX’):
Figure imgf000028_0001
(XIX’), in which formulae (XIX) and (XIX’):
- R7, Rs, R9, Rio, R’7, R’s, R’9 and R’10, which may be identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- nitro, nitroso;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; 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; - (O)2S(O')-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously;
- R’ ’ -S(O)2-, with R’ ’ representing a hydrogen atom or an alkyl group, an aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferentially a phenylamino or phenyl group;
- R”’-S(O)2-X’- with R’” representing an optionally substituted alkyl or aryl group, X’ as defined previously;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+ and iv) alkoxy with M+ as defined previously;
- optionally substituted heteroaryl; preferentially a benzothiazolyl group;
- cycloalkyl, notably cyclohexyl;
- Ar-N=N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl, (O)2S(O )-, M+ or phenylamino groups;
- or alternatively two contiguous groups R? with Rs or Rs with R9 or R9 with Rio together form a fused benzo group A’; and R’7 with R’s orR’s with R’9 orR’9 with R’10 together form a fused benzo group B’; with A’ and B’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, 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”-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; with M+, R°, X, X’, X” and Ar as defined previously;
- W represents a sigma bond c, 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, together 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 (XIX) and (XIX’) comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical (O)CO -, M+ on one of the rings A, A’, B, B’ or C; preferentially sodium sulfonate.
As examples of dyes of formula (XIX), mention may be made 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 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; Food Yellow 3 or Sunset Yellow; and, as examples of dyes of formula (XIX’), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38; b) the pyrazolone anionic azo dyes of formulae (XX) and (XX’):
Figure imgf000030_0001
in which formulae (XX) and (XX’):
- Rn, R12 and R13, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O ), M+ with M+ as defined previously;
- R14 represents a hydrogen atom, an alkyl group or a group -C(O)O', M+ with M+ as defined previously;
- R15 represents a hydrogen atom;
- Rie represents an oxo group, in which case R’i6 is absent, or alternatively R15 with Rie together form a double bond; - Rn and Ris, which may be identical or different, represent a hydrogen atom, or a group chosen from:
- (O)2S(O')-, M+ with M+ as defined previously;
- Ar-O-S(O)2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups;
- R19 and R20 together form either a double bond, or a benzo group D’, which is optionally substituted;
- R’ 16, R’ 19 and R’20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxy group;
- R21 represents a hydrogen atom or an alkyl or alkoxy group;
- Ra and Rb, which may be identical or different, are as defined previously; preferentially, Ra represents a hydrogen atom and Rb represents an aryl group;
- Y represents either a hydroxy group or an oxo group;
<■* «■> W
> — represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group; it being understood that formulae (XX) and (XX’) comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O', M+ on one of the rings D or E; preferentially sodium sulfonate.
As examples of dyes of formula (XX), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of dyes of formula (XX’), mention may be made of: Acid Yellow 17; c) the anthraquinone dyes of formulae (XXI) and (XXI’):
Figure imgf000031_0001
Figure imgf000032_0001
(XXF), in which formulae (XXI) and (XXF):
- R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- hydroxyl, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferentially substituted with one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined previously;
- aryl(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (O)2S(O )-, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (O)2S(O')-, M+ with M+ as defined previously;
- Z’ represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from:
- alkyl;
- polyhydroxy alkyl such as hydroxy ethyl;
- aryl optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)2S(O )-, 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, notably cyclohexyl; - Z represents a group chosen from hydroxy and NR’2sR’29 with R’28 and R’29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously; it being understood that formulae (XXI) and (XXF) comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O', M+; preferentially sodium sulfonate.
As examples of dyes of formula (XXI), mention may be made 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; EXT Violet No. 2; and, as an example of a dye of formula (XXF), mention may be made of: Acid Black 48; d) the nitro dyes of formulae (XXII) and (XXIF):
Figure imgf000033_0001
(XXIF), in which formulae (XXII) and (XXII’):
- R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted with one or more hydroxy groups, alkylthio optionally substituted with one or more hydroxy groups;
- hydroxyl, mercapto;
- nitro, nitroso;
- polyhaloalkyl; - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R°, X, X’ and X” as defined previously;
- (O)2S(O')-, M+ with M+ as defined previously;
- (O)CO -, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R30, R31 and R32 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 particularly represents an -NH- group;
- ALK represents a linear or branched divalent Ci-Ce alkylene group; in particular, ALK represents a -CH2-CH2- group;
- n is 1 or 2;
- p represents an integer inclusively between 1 and 5;
- q represents an integer inclusively between 1 and 4;
- u is 0 or 1;
- when n is 1, J represents a nitro or nitroso group; particularly nitro;
- when n is 2, J represents an oxygen or sulfur atom, or a divalent radical - S(O)m- with m representing an integer 1 or 2; preferentially, J represents an -SO2- radical;
- M’ represents a hydrogen atom or a cationic counterion;
Figure imgf000034_0001
, which may be present or absent, represents a benzo group optionally substituted with one or more groups R30 as defined previously; it being understood that formulae (XXII) and (XXII’) comprise at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O', M+; preferentially sodium sulfonate.
As examples of dyes of formula (XXII), mention may be made of Acid Brown 13 and Acid Orange 3; as examples of dyes of formula (XXII’), 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; EXT D&C Yellow 7; e) the triarylmethane dyes of formula (XXIII):
Figure imgf000035_0001
(XXIII), in which formula (XXIII):
- 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; particularly an alkyl and benzyl group optionally substituted with a group (O) m S(O )-, 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 a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; 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;
- (O)2S(O')-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously;
- or alternatively two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused benzo group: I’; with I’ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (O)2S(O )-, M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’- C(X)-X”-; with M+, R°, X, X’ and X” as defined previously; in particular, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxy group or (O)2S(O )-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted with an (O)2S(O‘ )- group; it being understood that at least one of the rings G, H, I or I’ comprises at least one sulfonate radical (O)2S(O )- or one carboxylate radical -C(O)O'; preferentially sulfonate.
As examples of dyes of formula (XXIII), mention may be made 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. f) the xanthene-based dyes of formula (XXIV):
Figure imgf000036_0001
(XXIV), in which formula (XXIV):
- R45, R46, R47 and R48, which may be identical or different, represent a hydrogen or halogen atom;
- R49, R50, R51 and R52, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- (O)2S(O')-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously; particularly, R49, R50, R51 and R52 represent a hydrogen or halogen atom; - G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; in particular, 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+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom or an optionally substituted alkyl or aryl group; L’ particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O)mS(O')-, M+ groups with m and M+ as defined previously;
- Q and Q’, which may be identical or different, represent an oxygen or sulfur atom; particularly, Q and Q’ represent an oxygen atom;
- M+ is as defined previously.
As examples of dyes of formula (XXIV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9; g) the indole-based dyes of formula (XXV):
Figure imgf000037_0001
(XXV), in which formula (XXV):
- R53, R54, R55, R56, R57, R58, R59 and Reo, which may be identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”- with R° representing a hydrogen atom or an alkyl or aryl group; 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; - (0)2S(0‘)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO -, M+ with M+ as defined previously;
- G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; in particular, G represents an oxygen atom;
- Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XXIII) comprises at least one sulfonate radical (O)2S(O )-, M+ or one carboxylate radical -C(O)O', M+; preferentially sodium sulfonate.
As examples of dyes of formula (XXV), mention may be made of Acid Blue 74; h) the quinoline-based dyes of formula (XXVI):
Figure imgf000038_0001
(XXVI), in which formula (XXVI):
- Rei represents a hydrogen or halogen atom or an alkyl group;
- R62, Res and R64, which may be identical or different, represent a hydrogen atom or a group (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counterion; or alternatively Rei with Re2, or Rei with Re4, together form a benzo group optionally substituted with one or more groups (O)2S(O )-, M+ with M+ representing a hydrogen atom or a cationic counterion; it being understood that formula (XXVI) comprises at least one sulfonate radical (O)2S(O )-, M+, preferentially sodium sulfonate.
As examples of dyes of formula (XXVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and particularly henna-based poultices or extracts.
Preferably, the direct dyes are chosen from anionic direct dyes.
Advantageously, the colouring agent(s) as defined above are present in a total content ranging from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, and even better still from 1% to 10% by weight, relative to the total weight of the composition.
According to a preferred embodiment, the colouring agent(s) are chosen from pigments.
The pigment(s) may be present in a total content ranging from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, and even better still from 1% to 10% by weight, relative to the total weight of the composition.
Alcohols
The composition according to the invention comprises at least one alcohol other than fatty alcohols. Said at least one alcohol is chosen from monoalcohols and from polyols.
By “fatty alcohols”, it is hereby meant a monoalcohol comprising from 8 to 40 carbon atoms (C8-C40 alkanols).
As monoalcohols, use may be made of C1-C4 alkanols, such as ethanol and isopropanol.
As polyols, use may be made of glycerol, propylene glycol, ethylene glycol, pentaerythritol, trimethylolpropane, 1,3-propanediol, pentane- 1,2-diol, caprylyl glycol (octane- 1,2-diol), butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, poly glycerols, such as glycerol oligomers like diglycerol, polyethylene glycols, and mixtures thereof.
Preferably, the alcohol(s) are chosen from ethanol, hexylene glycol, and mixtures thereof.
Preferably, the total content of alcohol(s) in the composition ranges from 5% to 60% by weight, preferably from 10% to 50% by weight, more preferentially from 15% to 40% by weight, relative to the total weight of the composition. The composition may notably be in the form of a suspension, a dispersion, a gel, an emulsion, notably an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W7O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, notably of ionic or nonionic lipids, or a two- phase or multi -phase lotion.
The composition according to the invention may be aqueous or anhydrous.
Preferably, the composition according to the invention is anhydrous.
An “anhydrous composition” means a composition comprising a water content of less than 5% by weight, preferably less than 3% by weight, relative to the weight of the composition. Preferably, this water content is less than 1% by weight, better still less than 0.5% or even less than 0.3% by weight, relative to the weight of the composition. More particularly, the composition does not comprise any water (0%).
In particular, said anhydrous composition does not comprise any water added during its preparation, the residual water that may be present possibly originating from the starting materials used during the preparation.
Hydrocarbon oils
The composition according to the invention may also comprise at least one hydrocarbon oil.
The term “oi means a water-immiscible non-aqueous compound that is liquid at room temperature (20°C) and at atmospheric pressure (760 mmHg).
The term “hydrocarbon oil” means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
In particular, the composition may comprise at least one hydrocarbon oil chosen from:
- Cs-Cie hydrocarbon oils, and notably: branched Cs-Ci6 alkanes, such as Cs-Ci6 and preferably Cs-Cu isoalkanes (also known as isoparaffins), such as isododecane (also known as 2, 2, 4,4,6- pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names, linear Cs-Ci6 alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (Cn) and of n-tridecane (C13) obtained in examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, and mixtures thereof,
- C3-C8 short-chain esters (having from 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;
- hydrocarbon oils of plant origin such as triglycerides constituted of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else caprylic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois,
- synthetic ethers containing from 10 to 40 carbon atoms,
- linear or branched hydrocarbons of mineral or synthetic origin comprising more than 16 carbon atoms, in particular petroleum jelly, poly decenes, hydrogenated polyisobutene, in particular Parleam®, squalane and liquid paraffins, and mixtures thereof,
- synthetic esters such as oils of formula R1COOR2 in which Ri represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon chain containing from 1 to 40 carbon atoms, on condition that the sum of the number of carbon atoms in Ri and R2 is greater than or equal to 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2- hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters,
- fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2 -undecylpentadecanol .
Preferably, the hydrocarbon oil present in the compositions according to the present invention is apolar; it is formed solely of carbon and hydrogen atoms.
Preferably, the hydrocarbon oil is chosen from:
- Cs-Cie hydrocarbon oils, and more preferentially from branched Cs-Ci4 alkanes such as isododecane or isodecane;
- C3-C8 short-chain esters such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;
- and mixtures thereof.
Preferably, the total content of hydrocarbon oil(s) in the composition ranges from 5% to 80% by weight, preferably from 10% to 75% by weight, more preferentially from 20% to 70% by weight and better still from 35% to 65% by weight relative to the total weight of the composition.
Preferably, the total content of hydrocarbon oil(s) chosen from branched Cs- C14 alkanes, C3-C8 short-chain esters and mixtures thereof ranges from 5% to 80% by weight, preferably from 10% to 75% by weight, more preferentially from 20% to 70% by weight, and better still from 35% to 65% by weight relative to the total weight of the composition.
Alkoxysilanes
The composition according to the invention can also comprise one or more alkoxysilanes.
According to a preferred embodiment, the composition comprises at least one alkoxy silane chosen from the compounds of formula (I), (I’) or (II) hereinbelow, oligomers thereof and/or mixtures thereof.
The compounds of formula (I) or (T) have the following formulae:
Figure imgf000042_0001
Figure imgf000043_0001
in which:
- Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;
- Rb and Re, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group, it being understood that if Ra does not represent an alkoxy group, then Rb and Re cannot simultaneously represent a hydrogen atom;
- Ra and Re, which may be identical or different, represent a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms; a cycloalkyl group containing from 3 to 20 carbon atoms; an aryl group containing from 6 to 12 carbon atoms; an aminoalkyl group containing from 1 to 20 carbon atoms;
- A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
- Q represents a carbonyl group (CO);
- r denotes an integer ranging from 0 to 1.
Among the alkoxysilanes of formula (I), oligomers thereof and/or mixtures thereof, mention may notably be made of 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), 3-ureidopropyltrimethoxysilane and N-cy cl ohexy 1 aminomethy Itri ethoxy sil ane .
APTES may be purchased, for example, from the company Dow Coming under the name Xiameter OFS-6011 Silane or from the company Momentive Performance Materials under the name Silsoft A-l 100 or from the company Shin-Etsu under the name KBE-903.
The compounds of formula (I) may also denote Dynasylan SIVO 210 or Dynasylan 1505 sold by the company Evonik.
3 -Ureidopropyltrimethoxy silane may be purchased, for example, from the company Gelest under the reference SIU9058.0.
N-Cycloheylaminomethyltriethoxysilane may be purchased, for example, from the company Wacker under the name Geniosil XL 926.
Among the alkoxysilanes of formula (E), oligomers thereof and/or mixtures thereof, mention may notably be made of N,N-bis[3- (trimethoxysilyl)propyl]ethylenediamine (CAS RN: 74956-86-8), Nl,Nl-bis[3- (triethoxysilyl)propyl]-l,2-ethanediamine (CAS RN: 457065-96-2), 1,2- ethanediamine, Nl-[3-(triethoxysilyl)propyl]-Nl-[3-(trimethoxysilyl)propyl]- (CAS RN: 1638528-78-5), and mixtures thereof.
Preferably, the alkoxysilane(s) of formula (I) are chosen from the compounds of formula (I) for which:
- Ra represents an alkyl group containing from 1 to 10 carbon atoms, notably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, preferably a methyl, or an alkoxy group containing from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms, preferably an ethoxy;
- Rb and Re, which may be identical or different, represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, such as an ethyl;
- Rd and Re, which are identical, represent a hydrogen atom or Rd denotes a hydrogen atom and Re denotes a Cs-G, cycloalkyl radical such as cyclohexyl;
- A independently represents a linear or branched alkylene group containing from 1 to 10 carbon atoms, which may be interrupted with at least one heteroatom chosen from O, S, NH or a carbonyl group (CO), preferably NH;
- r denotes an integer equal to 0.
More preferentially, the alkoxysilane(s) of formula (I) are chosen from the compounds of formula (I) in which Ra represents an ethoxy group, Rb and Re are identical and represent ethyl, Rd and Re represent a hydrogen atom, A represents propylene and r denotes an integer equal to 0. According to a preferred embodiment, the alkoxysilane of formula (I) is 3- aminopropyltriethoxysilane (APTES).
The compounds of formula (II) have the following formula:
Figure imgf000045_0001
in which:
- Ra represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms;
- Rb represents a hydrogen atom or an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms and notably from 1 to 4 carbon atoms, notably an ethyl group;
- Rc represents an alkyl group containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferentially from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methyl, said alkyl group being optionally substituted with an aryl group; an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as an ethoxy, or an aryl group containing from 6 to 12 carbon atoms; it being understood that if Ra and Rc do not represent an alkoxy group, then Rb cannot represent a hydrogen atom;
- k denotes an integer ranging from 0 to 5, preferably ranging from 0 to 3;
- Rf represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms; or a group of formula (Ila) below:
Figure imgf000045_0002
in which Rn represents a hydroxy group (OH); an alkyl group containing from 1 to 10 carbon atoms, preferably a methyl. Among the alkoxysilanes of formula (II), oligomers thereof and/or mixtures thereof, mention may notably be made of tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), diethyldiethoxysilane, dipropyldiethoxysilane, propyltri ethoxy sil ane, i sobuty Itri ethoxy sil ane, pheny Itri ethoxy sil ane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, benzyltriethoxysilane, benzylmethyldiethoxysilane, dibenzyldiethoxysilane, acetoxymethyltriethoxysilane, octytri ethoxy sil ane (OTES) and mixtures thereof.
TEOS may be purchased, for example, from the company Evonik under the name Dynasylan® A or Dynasylan® A SQ.
MTES may be purchased, for example, from the company Evonik under the name Dynasylan® MTES.
DMDES may be purchased, for example, from the company Gelest under the reference SID3404.0.
Preferably, the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof are such that:
- Ra represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms such as a methoxy or an ethoxy; or an alkyl group containing from 1 to 10 carbon atoms optionally substituted with an aryl group, preferably 1 to 2 carbon atoms optionally substituted with an aryl group;
- Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
- Rc represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy;
- k denotes an integer ranging from 0 to 3, preferably equal to 0;
- Rf represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as a methyl or an ethyl.
Preferably, the alkoxysilane(s) of formula (II), oligomers thereof and/or mixtures thereof are such that: - Ra represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
- Rb represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms, such as a methyl or an ethyl;
- Rc represents an alkoxy group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and in particular from 1 to 2 carbon atoms, such as a methoxy or an ethoxy;
- k denotes an integer equal to 0;
- Rf represents an alkyl group containing from 1 to 10 carbon atoms and notably from 1 to 4 carbon atoms such as a methyl or an ethyl.
According to a preferred embodiment, the alkoxysilane(s) of formula (II) are chosen from octyltriethoxysilane (OTES), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) and mixtures thereof.
According to a more preferred embodiment, the alkoxysilane(s) of formula (II) are methyltrimethoxysilane (MTMS) and/or methyltriethoxysilane (MTES).
For the purposes of the present invention, an “oligomer” means compound(s) comprising at least 2 silicon atoms, obtained by oligomerization or polymerization of compounds of formula (I), (f) or (II).
Preferably, the alkoxysilane(s) are chosen from amino alkoxysilanes, notably from those of formula (I), such as 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), and mixtures thereof.
When the composition comprises one or more alkoxysilanes, their total content is advantageously in the range of from 0.01% to 20% by weight, more preferentially from 0.05% to 15% by weight, more preferentially still from 0.1% to 10% by weight, better still from 0.1% to 5% by weight, even better still from 0.2% to 2% by weight, relative to the total weight of the composition.
Additives
The composition according to the invention may contain any additive usually used in cosmetic compositions intended for treating keratin fibres.
Among the additives that may be contained in the composition, mention may be made of reducing agents, softeners, antifoams, moisturizers, clays, mineral fillers, UV-screening agents, peptizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the copolymers CP described previously, preserving agents, amino silicones, waxes other than silicones in wax form, and mixtures thereof.
The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition.
The colouring process
Another subject of the present invention is a method for colouring keratin fibres comprising the application of the above composition to said fibres.
According to a preferred embodiment, the process further comprises a step of applying an additional composition A, different from the composition according to the invention, and which comprises at least one aminoalkoxysilane chosen from the compounds of formula (I) or (T) as described above, oligomers thereof and/or mixtures thereof. This step, carried out sequentially with the application of the composition according to the invention, can be carried out before and/or after the application of the composition according to the invention, and preferably before the application of the composition according to the invention.
The application of the compositions to the keratin fibres may be performed on said fibres, which may be wet or dry.
Preferably, the keratin fibres are hair. The composition according to the invention may be applied to all types of light or dark, natural or dyed, permanent- waved, bleached or relaxed hair.
The application to the hair may be performed via any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.
The application of the composition to the hair is generally performed at room temperature (between 15°C and 25°C).
After applying the composition, the hair may be left to dry or may be dried, for example at a temperature above or equal to 30°C.
The process according to the invention may also comprise, after applying the composition, a step of applying heat to the keratin fibres using a heating device.
Such a device may be, for example, a hood, a hair dryer, a straightening or curling iron, a Climazon, etc. Preferably, the step of applying heat is performed using a hair dryer. During the step of applying heat to the hair, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through.
When the step of applying heat to the hair is performed using a hood or a hair dryer, the temperature is preferably between 30°C and 110°C, preferentially between 50°C and 90°C.
The invention also relates to the use of this composition for colouring keratin fibres, and in particular the hair.
The use is as described above, in the context of the colouring process.
The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the invention.
EXAMPLES
The examples below use an isobutyl acrylate/tert-butyl acrylate/ acetoacetoxy ethyl methacrylate (25/65/10) copolymer CP synthesized according to the protocol described below:
62.5 g of isobutyl acrylate, 162.5 g of tert-butyl acrylate, 25 g of acetoacetoxyethyl methacrylate, 2.5 g of Trigonox T21S radical initiator and 360 g of an isododecane/ethyl acetate (50/50) solvent are introduced into a 1 L pilot reactor. The medium is degassed with argon and then heated to 90°C with stirring. The reaction medium is kept for 7 hours at 90°C. Stripping with 300 ml of isododecane is then performed to remove the residual monomers. On conclusion of the reaction, a polymer in solution in isododecane is obtained.
Example 1 : Preparation of compositions The compositions below were prepared, by mixing the ingredients indicated in Table 1 below in which the contents are expressed as percentages by weight of starting material, relative to the total weight of the composition (a.m. signifying active material).
[Table 1]
Figure imgf000050_0001
Figure imgf000051_0001
(1) isobutyl acrylate/tert-butyl acrylate/acetoacetoxyethyl methacrylate (25/65/10 by weight) statistical copolymer obtained according to the synthesis process described above, as a 58.8% by weight solution in isododecane;
(2) sold under the name Tarox Iron Oxide R-516 HP by the company Titan Kogyo;
(3) sold under the name Belsil DM 60000 by the company Wacker;
(4) sold under the name Xiameter PMX-1501 Fluid by the company Dow;
(5) sold under the name Belsil PMS MK Powder Silicone Resin by the company Wacker.
Example 2: Evaluation of the compositions
The compositions A to D from Example 1 were evaluated on 1 g locks of natural hair containing 90% white hair.
The colouring protocol is as follows:
Each composition is applied to a lock of dry hair in a proportion of 0.6 g of composition (bath ratio of 0.6 g per g of hair). It is spread with a finger over the lock.
After a leave-on time of 2 minutes, the lock is dried using a thermal brush and a hair dryer.
Evaluations in terms of resistance of the colouring to shampoo washing were then carried out 24 hours after applying the composition.
The resistance to shampoo washing was evaluated by measuring the colorimetric data of each of the locks.
The colorimetric measurements were performed using a Konica Minolta 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included) in the CIELab system.
In this L*a*b* system, L* represents the lightness of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.
The persistence of the colouring is evaluated by the colour difference AE between the coloured locks before shampoo washing, then after having undergone 5 successive shampoo washes. The lower the AE value, the more persistent the colour with respect to shampoo washing. The AE value is calculated according to the following equation:
Figure imgf000052_0001
In this equation, L*, a* and b* represent the values measured after colouring the hair and after having undergone 5 shampoo washes, and Lo*, ao* and bo* represent the values measured after colouring the hair but before the 5 shampoo washes.
The results obtained are collated in Table 2 below.
[Table 2]
Figure imgf000052_0002
The locks of hair coloured with the three compositions according to the invention have a colour difference AE between the coloured locks before shampoo washing and then after having undergone 5 shampoo washes, which is much smaller than the lock coloured with composition A. The persistence of the colouring obtained with compositions B, C and D according to the invention is therefore significantly improved compared with the colouring obtained with comparative composition A. Thus, the coloured coating obtained by means of the compositions according to the invention has improved persistence with respect to shampoo washing.

Claims

1. Cosmetic composition for colouring keratin fibres, comprising: i) at least one copolymer CP obtained by polymerization of:
- 1% to 20% by weight, relative to the total weight of the monomers, of at least one monomer (B) of formula (I):
Figure imgf000053_0001
in which:
• Ra represents a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
• Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group,
• Rd represents a linear or branched (Ci-C4)alkyl group, and
• L represents a linear or branched (Ci-Ce)alkylene, or cycloalkylene, group;
- 80% to 99% by weight, relative to the total weight of the monomers, of at least one monomer (C) chosen from C1-C4 alkyl acrylates and C1-C4 alkyl methacrylates; wherein the copolymer CP does not comprise any monomer (A) chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof; ii) at least one non-amino silicone; iii) at least one colouring agent chosen from pigments, direct dyes and mixtures thereof; and iv) at least one alcohol chosen from polyols and monoalcohols other than fatty alcohols.
2. Composition according to Claim 1, characterized in that the copolymer CP comprises from 80% to 90% by weight of at least one monomer (C) chosen from Ci- C4 alkyl acrylates and C1-C4 alkyl methacrylates relative to the total weight of the monomers.
3. Composition according to Claim 1 or 2, characterized in that it comprises the copolymer(s) CP in a total content ranging from 1% to 30% by weight, preferably from 2% to 20% by weight, and more preferentially ranging from 5% to 15% by weight, relative to the total weight of the composition.
4. Composition according to any one of the preceding claims, characterized in that the non-amino silicone(s) are chosen from polydialkylsiloxanes, notably cyclic polydialkylsiloxanes containing from 3 to 7 silicon atoms, trimethylsilyl-terminated polydimethylsiloxanes, dimethylsilanol-terminated polydimethylsiloxanes (dimethiconols); silicone resins, notably MQ-type resins and T-type resins, notably polymethylsilsesquioxane resins; and mixtures thereof.
5. Composition according to any one of the preceding claims, characterized in that it comprises the non-amino silicone(s) in a total content ranging from 0.5% to 25% by weight, more preferentially from 1% to 20% by weight, and more preferentially still ranging from 2% to 15% by weight, relative to the total weight of the composition.
6. Composition according to any one of the preceding claims, characterized in that it comprises at least one pigment.
7. Composition according to any one of the preceding claims, characterized in that the colouring agent(s) are present in a total content ranging from 0.001% to 20% by weight, preferably from 0.01% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.5% to 10% by weight, and even better still from 1% to 10% by weight, relative to the total weight of the composition.
8. Composition according to any one of the preceding claims, characterized in that it also comprises at least one hydrocarbon oil, preferably chosen from:
- Cs-Cie hydrocarbon oils, and more preferentially branched Cs-Cu alkanes such as isododecane or isodecane;
- C3-C8 short-chain esters such as ethyl acetate, methyl acetate, propyl acetate or butyl acetate;
- and mixtures thereof.
9. Composition according to the preceding claim, characterized in that the total content of hydrocarbon oil(s) in the composition ranges from 5% to 80% by weight, preferably from 10% to 75% by weight, more preferentially from 20% to 70% by weight and better still from 35% to 65% by weight relative to the total weight of the composition.
10. Composition according to any one of the preceding claims, characterized in that the alcohol chosen from monoalcohols other than fatty alcohols and polyols is present in an amount ranging from 5% to 60% by weight, more preferentially from 10% to 50% by weight, more preferentially still from 15% to 40% by weight, relative to the total weight of the composition.
11. Composition according to any one of the preceding claims, characterized in that it also comprises one or more alkoxysilanes, preferably chosen from amino alkoxy silanes, such as 3 -aminopropyltri ethoxy silane (APTES), 3- aminopropylmethyldiethoxysilane (APMDES), and mixtures thereof.
12. Composition according to any one of the preceding claims, characterized in that it is anhydrous.
13. Method for colouring keratin fibres, preferably the hair, comprising the application to said fibres of a composition as defined in any one of the preceding claims.
14. Method according to the preceding claim, characterized in that it comprises, after application of the composition, a step of applying heat to the keratin fibres using a heating device.
15. Use of a composition as defined in any one of Claims 1 to 12, for colouring keratin fibres, and in particular the hair.
PCT/EP2024/086211 2023-12-20 2024-12-13 Composition for colouring keratin fibres comprising at least one copolymer containing acetoacetate functions, at least one silicone, at least one colouring agent and at least one alcohol Pending WO2025132077A1 (en)

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