WO2024094537A1 - Composition comprising a particular silicone, a particular silicone emulsion, a particular vinylic polymer and surfactants - Google Patents

Composition comprising a particular silicone, a particular silicone emulsion, a particular vinylic polymer and surfactants Download PDF

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WO2024094537A1
WO2024094537A1 PCT/EP2023/079908 EP2023079908W WO2024094537A1 WO 2024094537 A1 WO2024094537 A1 WO 2024094537A1 EP 2023079908 W EP2023079908 W EP 2023079908W WO 2024094537 A1 WO2024094537 A1 WO 2024094537A1
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alkyl
meth
weight
radical
cationic
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PCT/EP2023/079908
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French (fr)
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Sarish JOSHI
Harshada TULSYAN
Geeta Yadav
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L'oreal
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions 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
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/896Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/21Emulsions characterized by droplet sizes below 1 micron

Definitions

  • the present invention relates to a composition for treating keratin fibers, and in particular human keratin fibers such as hair, which comprises a particular amino silicone, a specific oil-in-water-type silicone emulsion, one or more cationic vinylic polymers, preferably comprising at least one cationic or quatemized (meth)acrylamide unit and one or more surfactants.
  • the invention also relates to a process for treating keratin fibres, preferably for washing and/or conditioning keratin fibres, comprising the application onto the keratin fibres of the composition according to the invention.
  • the invention relates to the use of such a composition for washing and/or conditioning keratin fibres, preferably the hair.
  • detergent cosmetic compositions such as shampoos and shower gels, based essentially on surfactants, for washing keratin materials especially such as the hair and the skin.
  • These compositions are applied to the keratin materials, which are preferably wet, and the lather generated by massaging or rubbing with the hands or a toiletry flannel makes it possible, after rinsing with water, to remove the diverse types of soiling initially present on the hair or the skin.
  • compositions contain substantial contents of "detergent” surfactants, which, in order to be able to formulate cosmetic compositions with good washing power, must especially give them good foaming power.
  • the surfactants that are useful for this purpose are generally of anionic, nonionic and/or amphoteric type, and particularly of anionic type.
  • compositions have generally a good washing power, but the intrinsic cosmetic properties associated with them nevertheless remain fairly poor, owing in particular to the fact that the relatively aggressive nature of such a cleaning treatment can, in the long run, lead to more or less pronounced damage to the hair fiber, this damage being associated in particular with the gradual removal of the lipids or proteins contained in or on the surface of this fiber.
  • conditioners are intended mainly to repair or limit the harmful or undesirable effects induced by the various treatments or aggressions to which the hair fibres are subjected more or less repeatedly. They may, of course, also improve the cosmetic behavior of natural hair.
  • the conditioners most commonly used to date in shampoos include cationic polymers, silicones and/or silicone derivatives, which give washed, dry or wet hair an ease-of disentangling, softness and smoothness which are markedly better than that which can be obtained with corresponding cleaning compositions from which they are absent.
  • compositions such as compositions for washing and/or conditioning keratin fibres, and in particular human keratin fibres, that make it possible to overcome the drawbacks described above, i.e. which effectively remove dirt and excess sebum and enhance cosmetic properties of said fibres, such as softness, smoothness, manageability and disentangling.
  • These cosmetic properties may also be long-lasting.
  • the composition should give a satisfactory silicone deposition onto the keratin fibres and should improve hair disentangling.
  • composition comprising: a) one or more amino silicones comprising amino end groups, preferably one or more amino silicones corresponding to formula (I): wherein:
  • radicals R independently of one another, represent a hydrogen atom or a C1-C4 alkyl group
  • radicals Rl, R2, R3 and R4 independently of one another, represent a hydrogen atom, a C1-C6 alkyl group or a C1-C6 aminoalkyl group, - x is between 0 and 6, y is between 0 and 6, and
  • - n is such that the weight-average molecular weight (Mw) of the amino silicone is between 5000 and 200 000, b) an oil-in-water emulsion having D50 particle size of less than 350 nm and comprising:
  • a silicone mixture comprising (i) a trialkylsilyl terminated dialkylpolysiloxane having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C and (ii) an amino silicone having a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone,
  • emulsifiers comprising one or more nonionic emulsifiers, wherein the mixture of emulsifiers has a HLB value of from 10 to 16, and
  • amphoteric or cationic vinylic polymers preferably comprising one or more cationic or quatemized acrylamide and/or methacrylamide unit(s), d) optionally one or more cationic polysaccharides, e) one or more anionic surfactants, f) one or more amphoteric or zwitterionic surfactants.
  • This composition when applied onto keratin fibres, in particular human keratin fibres such as hair and more particularly the sensitized hair, leads to an improvement of the condition and quality of hair, in terms of hair feel (e.g. smooth feel, soft feel, conditioned feel) and hair manageability, both on wet and dry hair (e.g., no or less frizz, manageability, easy to detangle and comb, styleability/shapeability).
  • the keratin fibres are particularly easy to disentangle and to comb.
  • composition according to the invention makes it possible to significantly improve the silicone deposition onto the keratin fibres.
  • composition according to the invention has a good detergent power.
  • composition according to the invention are particularly long-lasting.
  • the present invention also relates to a process for treating, in particular for washing and/or conditioning, keratin fibres, preferably human keratin fibres such as the hair, comprising the application onto keratin fibres of the above-defined composition.
  • Another subject-matter of the invention is the use of such a composition for washing and/or conditioning keratin fibres, preferably the hair.
  • Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the example that follows.
  • keratin fibres preferably denotes human keratin fibres, and more preferentially the hair.
  • composition according to the invention comprises one or more amino silicones comprising amine end groups; this means that the groups located at the chain end (the end groups in the alpha and omega positions) comprise an amino group.
  • composition according to the present invention comprises one or more amino silicones corresponding to formula (I): wherein:
  • radicals R independently of one another, represent a hydrogen atom or a C1-C4 alkyl group
  • radicals Rl, R2, R3 and R4 independently of one another, represent a hydrogen atom, a C1-C6 alkyl group or a C1-C6 aminoalkyl group,
  • the weight-average molecular weight (Mw) of the amino silicone is between 5000 and 200 000.
  • radicals R are identical and represent CH3 (methyl).
  • x y.
  • n is such that the weight-average molecular weight (Mw) of the silicone is between 10 000 and 150000 g/mol, or even between 15 000 and 100 000 g/mol.
  • the composition comprises a total content of amino silicone(s) with amino end groups a) ranging preferably from 0.01% to 10% by weight, preferentially from 0.05 % to 5% by weight, and better still from 0.08% to 1% by weight, relative to the total weight of the composition.
  • the composition comprises a total content of amino silicone(s) of formula (I) ranging preferably from 0.01% to 10% by weight, preferentially from 0.05 % to 5% by weight, and better still from 0.08% to 1% by weight, relative to the total weight of the composition.
  • a total content of amino silicone(s) of formula (I) ranging preferably from 0.01% to 10% by weight, preferentially from 0.05 % to 5% by weight, and better still from 0.08% to 1% by weight, relative to the total weight of the composition.
  • composition according to the present invention further comprises an oil- in-water (or silicone-in-water) emulsion having D50 particle size of less than 350 nm and containing:
  • a silicone mixture comprising (i) a trialkylsilyl terminated dialkylpolysiloxane having a viscosity of from 40,000 to less than 100,000 mPa.s at 25 °C and (ii) an amino silicone which is different from amino silicones comprising amino end groups and which has a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone,
  • emulsifiers comprising one or more nonionic emulsifiers, wherein the mixture of emulsifiers has a HLB value of from 10 to 16, and
  • one liquid phase (the dispersed phase) is dispersed in the other liquid phase (the continuous phase); in the present invention, the silicone mixture, or silicone phase, is dispersed in the continuous aqueous phase.
  • the silicone mixture, or silicone phase is dispersed in the continuous aqueous phase.
  • the silicone mixture comprises a trialkylsilyl terminated dialkylpolysiloxane that is preferably of formula (IX):
  • - R’ is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl, and
  • - p is an integer of from 500 to 2,000, preferably of from 1,000 to 2,000;
  • the trialkylsilyl terminated (or end-blocked or a,co-position) dialkylpolysiloxanes according to the invention have a viscosity of from 40,000 to less than 100,000 mPa.s (100,000 excluded) at 25°C, preferably a viscosity of from 40,000 to 70,000 mPa.s at 25°C, more preferably a viscosity of from 51,000 to 70,000 mPa.s at 25°C.
  • the trialkylsilyl terminated dialkylpolysiloxanes according to the invention are preferably linear but may contain additionally to the R’ 2 SiO 2 / 2 units (D-units) in formula (IX), RSiO3/ 2 units (T-units) and/or SiO4/ 2 units (Q-units), wherein R’, same or different, is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms.
  • R’ are alkyl radicals, preferably C1-C18 alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radicals, hexyl radicals, such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radicals, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-d
  • trialkylsilyl terminated dialkylpolysiloxanes are trimethylsilyl terminated PDMS (polydimethylsiloxanes or dimethicones).
  • the silicone mixture comprises an amino silicone that are preferably of formula (X):
  • R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl;
  • X is R or a hydroxyl (OH) or a Cl-C6-alkoxy group; preferably X is R, i.e. a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl;
  • R 1 is a Cl-C6-alkylene radical, preferably a radical of the formula -CH 2 CH 2 CH 2 - or -CH 2 CH(CH3)CH 2 -
  • R 2 same or different, is a hydrogen atom or a Cl-C4-alkyl radical, preferably a hydrogen atom
  • R 3 is a C1-C6- alkylene radical, preferably a radical of the formula -CH 2 CH 2 -, and x is 0 or 1;
  • - m+n is an integer from 50 to about 1000, preferably from 50 to 600.
  • A is an amino radical of the formula -R 1 -[NR 2 -R 3 -] X NR 2 2 , or the protonated amino forms of said amino radical, wherein R1 is -CH 2 CH 2 CH 2 - or - CH 2 CH(CH3)CH 2 -, R 2 are hydrogen atoms, R 3 is -CH 2 CH 2 -, and x is 1.
  • R same or different, are alkyl radicals, preferably C1-C18 alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radicals, hexyl radicals, such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radicals, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-do
  • the amino silicones according to the invention have an amine value of from 2 to 10 mg of KOH per gram of amino silicone, preferably of from 3.5 to 8 mg.
  • the mole percent of amine functionality is preferably in the range of from about 0.3 to about 8%.
  • amino silicones useful in the silicone mixture according to the invention include trialkylsilyl terminated amino silicone.
  • amino silicones are trimethylsilyl terminated aminoethylaminopropylmethylsiloxane, most preferably trimethylsilyl terminated aminoethylaminopropylmethylsiloxane - dimethylsiloxane copolymers.
  • the amino radical A can be protonated partially or fully by adding acids to the amino silicone, wherein the salt forms of the amino radical are obtained.
  • acids are carboxylic acids with 3 to 18 carbon atoms which can be linear or branched, such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, sorbic acid, benzoic acid, salicylic acid.
  • the acids are preferably used in amounts of from 0.1 to 2.0 mol per 1 mol of amino radical A in the amino silicone of formula (X).
  • the silicone mixture preferably comprises (i) one or more trialkylsilyl terminated dialkylpoly siloxanes having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C in a quantity of from 70 to 90% by weight, preferably from 75 to 85% by weight and (ii) one or more amino silicones having a viscosity of from 1,000 to 15,000 mPa.s at 25 °C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone, in a quantity of from 10 to 30% by weight, preferably from 15 to 25% by weight, relative to the total weight of the silicone mixture.
  • mixture of emulsifiers are examples of emulsifiers
  • the oil-in-water emulsion further comprises one or more nonionic emulsifiers. It could optionally comprise one or more cationic surfactants.
  • the mixture of emulsifiers has a HLB value from 10 to 16.
  • the nonionic emulsifiers can be chosen among the nonionic surfactants as described hereunder.
  • poly ethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyg
  • nonionic surfactants of alkyl(poly)glycoside type represented especially by the following general formula:
  • Ri represents a linear or branched alkyl or alkenyl radical comprising 6 to 24 carbon atoms and especially 8 to 18 carbon atoms, or an alkylphenyl radical whose linear or branched alkyl radical comprises 6 to 24 carbon atoms and especially 8 to 18 carbon atoms;
  • R 2 represents an alkylene radical comprising 2 to 4 carbon atoms
  • - G represents a sugar unit comprising 5 to 6 carbon atoms
  • - 1 denotes a value ranging from 0 to 10 and preferably 0 to 4,
  • - v denotes a value ranging from 1 to 15 and preferably 1 to 4.
  • alkylpoly glyco side surfactants are compounds of the formula described above in which:
  • Ri denotes a linear or branched, saturated or unsaturated alkyl radical comprising from 8 to 18 carbon atoms
  • R 2 represents an alkylene radical comprising 2 to 4 carbon atoms
  • - 1 denotes a value ranging from 0 to 3 and preferably equal to 0,
  • - G denotes glucose, fructose or galactose, preferably glucose
  • the degree of polymerization i.e. the value of v, possibly ranging from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2.
  • the glucoside bonds between the sugar units are generally of 1-6 or 1-4 type and preferably of 1-4 type.
  • the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant.
  • the nonionic emulsifiers could preferably be chosen among ethoxylated aliphatic alcohols, polyoxyethylene surfactants, carboxylic esters, polyethylene glycol esters, sorbitol ester and their ethoxylated derivatives, glycol esters of fatty acids, carboxylic amides, monoalkanolamine condensates, polyoxyethylene fatty acid amides.
  • nonionic emulsifiers are selected from:
  • polyoxy alkylene alkyl ethers especially (poly)ethoxylated fatty alcohols of formula:
  • R3 representing a linear or branched C8-C40 alkyl or alkenyl group, preferably C8- C30 alkyl or alkenyl group, optionally substituted with one or more hydroxyl groups, and
  • - c being an integer between 1 and 200 inclusive, preferentially between 2 and 150 and more particularly between 4 and 50, most preferably between 8 and 20.
  • the (poly)ethoxylated fatty alcohols are more particularly fatty alcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to 30 mol of ethylene oxide (1 to 30 OE);
  • polyoxyalkylene sorbitan (C8-C32) fatty acid esters especially polyethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; preferably polyoxyethylenated sorbitan (C10-C24) fatty acid esters preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; and
  • the nonionic emulsifiers could be selected from alkyl ether of polyalkyleneglycol and alkyl esters of polyalkyleneglycol; preferably of polyethyleneglycol (PEG).
  • Some useful emulsifiers are:
  • polyethyleneglycol octyl ether polyethyleneglycol lauryl ether; polyethyleneglycol tridecyl ether; polyethyleneglycol cetyl ether; polyethyleneglycol stearyl ether; among these, mention may be made more particularly of trideceth-3, trideceth-10 and steareth-6.
  • polyethyleneglycol nonylphenyl ether polyethyleneglycol dodecylphenyl ether; polyethyleneglycol cetylphenyl ether; polyethyleneglycol stearylphenyl ether;
  • polyethyleneglycol stearate and especially PEG- 100 stearate.
  • the nonionic emulsifiers are chosen among steareth-6, PEG- 100 stearate, trideceth-3 and trideceth-10 and their mixture; preferably, all these emulsifiers are present in the mixture of emulsifiers.
  • the mixture of emulsifiers could comprise one or more cationic emulsifiers that could be selected among tetraalkylammonium halides, tetraarylammonium halides, tetraalkylarylammonium halides, and their salts; quaternary ammonium compounds including salts; preferably, the cationic emulsifiers could be chosen among cetrimonium halides or behentrimonium halides, such as chloride.
  • the oil-in-water emulsion preferably comprises the mixture of emulsifiers in a total amount of from 5 to 15% by weight, more preferably of from 8 to 15% by weight, most preferably of from 10 to 12% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion preferably comprises nonionic emulsifiers in a total amount of from 5 to 15% by weight, more preferably of from 8 to 15% by weight, most preferably of from 10 to 12% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion preferably comprises cationic emulsifiers, when present, in a total amount of from 0.5 to 1.5% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion preferably comprises the silicone mixture in a total amount of from 40 to 60% by weight, more preferably of from 45 to 55% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion preferably comprises the trialkylsilyl terminated dialkylpolysiloxane(s) in a total amount of from 35 to 45% by weight, more preferably of from 38 to 42% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion preferably comprises the amino silicone(s) in a total amount of from 5 to 15% by weight, more preferably of from 8 to 12% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion comprises water preferably in an amount of from 25 to 50% by weight, more preferably of from 30 to 45% by weight, most preferably of from 35 to 42% by weight, relative to the total weight of the emulsion.
  • the oil-in-water emulsion could additionally comprise a biocide, such as phenoxyethanol, that could be present in the emulsion in a quantity of from 0.5 to 1% by weight, relative to the total weight of the emulsion.
  • a biocide such as phenoxyethanol
  • a method of preparation of the oil-in-water emulsion preferably comprises:
  • step - a step of adding, preferably step-wise, water, preferably demineralized water, to obtain an oil-in-water emulsion having D50 particle size of less than 350 nm.
  • the method of preparation of the oil-in-water emulsion could further comprise an additional step of adding a biocide.
  • Biocide could be added for preserving the emulsion against microbial contamination.
  • the biocide could be added at the level of for preserving emulsion against microbial contamination and obtaining the said emulsion.
  • the quantity of the biocide depends on the type of biocide and as recommended by the manufacturer.
  • the preparation of the mixture of emulsifiers could be made by mixing one or more nonionic emulsifiers.
  • the pH of the oil-in-water emulsion after neutralization is preferably of from 4 to 6.
  • the oil-in-water emulsion has D50 particle size of less than 350 nm, preferably from 100 to 300 nm, more preferably from 150 to 250 nm, even more preferentially from 150 to 225 nm, and most preferably from 160 to 200 nm. It corresponds to the average hydrodynamic particle diameter.
  • the D50 particle size is expressed in volume.
  • the D50 particle size could be measured by using a device ZetaSizer from Malvern, UK, model Nano-ZS, which is based on the Photon Correlation Spectroscopy (PCS) method. particle size measurement
  • Emulsion particle size could be measured by using a device ZetaSizer from Malvern, UK, model Nano-ZS which is based on the Photon Correlation Spectroscopy (PCS) method.
  • the D50 value of particle size (average hydrodynamic particle diameter) is measured, wherein the evaluating algorithm is “cumulants analysis”.
  • the viscosity is measured at 25°C and at atmospheric pressure.
  • the amine value is determined by acid-base titration using a potentiometer [Make: Veego; Model: VPT-MG]. 0.6 g of sample is taken in a 500 ml beaker and a toluene -butanol 1:1 mixture is added and stirred to mix the sample thoroughly; then the sample solution is titrated with a 0.1(N) HC1 solution. A determination of the blank value with the toluene -butanol 1:1 mixture is also done. The calculation of the amine value is done by the above-mentioned potentiometer.
  • the amine value is calculated according to the formula:
  • V Volume of HC1 required in ml, Vi>,i ;
  • ill k Volume of HC1 for blank value (without sample) with the toluene-butanol 1:1 mixture in ml;
  • HLB is well known to those skilled in the art, and denotes the hydrophilic-lipophilic balance of a surfactant or emulsifier.
  • HLB values refer to the values at 25 °C and at atmospheric pressure.
  • the HLB can be measured by experimental determination or can be calculated.
  • HLB (E + P)/5, with E being the weight percentage of oxyethylene content and P being the weight percentage of polyhydric alcohol content, described in to the publication Griffin, J. Soc. Cosm. Chem. 1954 (vol.5, n°4), pp.249-256.
  • the calculated HLB is the preferred HLB values that should be taken into account.
  • Said calculated HLB could be defined as being the following:
  • the hydrophilic part is naturally defined as being beyond the carbonyl group, starting from the fatty chain(s).
  • the HLB value of individual surfactant/emulsifier can be calculated applying the Davies formula as described in Davies JT (1957), "A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent", Gas/Liquid and Liquid/Liquid Interface (Proceedings of the International Congress of Surface Activity): 426-438.
  • the HLB is derived by summing the hydrophilic/hydrophobic contribution afforded by the structural components of the emulsifier:
  • HLB (hydrophilic groups numbers) - n(group number per CH2 group) +7.
  • HLB values for some cationic emulsifiers are given in Table IV, in “Cationic emulsifiers in cosmetics”, GODFREY, J. Soc. Cosmetic Chemists (1966) 17, ppl7-27.
  • the HLB Mix is said to be the required HLB for the mixture.
  • HLBA, HLBB the assigned HLB values for emulsifiers A and B;
  • HLBMI the HLB of the mixture.
  • Said oil-in-water emulsion is for example described in WO 2017/108824.
  • the composition according to the invention preferably comprises the oil-in- water emulsion b) in an amount ranging from 0.1% to 20% by weight, more preferably from 0.3 % to 15% by weight, even more preferably from 0.5% to 12% by weight, better from 1 to 10%, even better from 2 to 8% by weight, relative to the total weight of the composition.
  • the composition according to the invention preferably comprises the trialkylsilyl terminated dialkylpolysiloxane(s) having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C in a total amount ranging from 0.1% to 8% by weight, more preferably from 0.2 % to 5% by weight, even more preferably from 0.5% to 4% by weight, better from 1 to 3% by weight, relative to the total weight of the composition.
  • the composition according to the invention preferably comprises the amino silicone(s) having a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone, in a total amount ranging from 0.1% to 5% by weight, more preferably from 0.2 % to 3% by weight, even more preferably from 0.3% to 2% by weight, better from 0.4 to 1% by weight, relative to the total weight of the composition.
  • Amphoteric or cationic vinylic polymers having a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone, in a total amount ranging from 0.1% to 5% by weight, more preferably from 0.2 % to 3% by weight, even more preferably from 0.3% to 2% by weight, better from 0.4 to 1% by weight, relative to the total weight of the composition.
  • composition according to the invention further comprises one or more amphoteric or cationic vinylic polymers.
  • These polymers preferably comprise one or more cationic or quaternized acrylamide and/or methacrylamide unit(s).
  • These polymers are non-silicones, i.e. they do not contain any silicon (Si) atom.
  • cationic and/or amphoteric polymer(s) it is understood one or more cationic polymers, one or more amphoteric polymers or the mixture of one or more cationic polymers, and of one or more amphoteric polymers.
  • vinyl it is understood that the polymer derives from monomers comprising at least one vinylic monomer, preferably at least one (meth)acrylic monomer (i.e. monomer derived from acrylic or methacrylic acid, and its derivatives).
  • cationic polymer means any polymer comprising cationic groups and/or groups that can be ionized to cationic groups, and not comprising anionic groups and/or groups that can be ionized to anionic groups.
  • the cationic polymer is hydrophilic or amphiphilic.
  • the preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that may either form part of the main polymer chain or may be borne by a side substituent directly connected thereto.
  • amphoteric polymer means any polymer comprising cationic groups and/or groups that can be ionized to cationic groups, and comprising anionic groups and/or groups that can be ionized to anionic groups.
  • cationic or amphoteric polymers that can be used, mention may be made of:
  • R3 which may be identical or different, denote a hydrogen atom or a CH3 radical
  • - A which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxy alkyl group of 1 to 4 carbon atoms;
  • R4 R4, Rs and Re, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group containing from 1 to 6 carbon atoms;
  • Ri and R2 which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
  • - X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide;
  • crosslinked polymers of methacryloyloxy(Ci -Chalky ltri(Cl- C4)alkylammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide.
  • Use may be made more particularly of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil.
  • This dispersion is sold under the name Salcare® SC 92 by the company Ciba.
  • Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester.
  • These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company BASF;
  • R12 denotes a hydrogen atom or a methyl radical
  • - Rio and Rn independently of each other, denote a Ci-Ce alkyl group, a Ci- Cs hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively Rio and Rn may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidyl or morpholinyl; Rio and Rn, independently of each other, preferably denote a C1-C4 alkyl group;
  • - Y“ is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
  • these polymers may be in particular chosen from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
  • these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
  • These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium.
  • the weight-average molecular weight of said polymer measured by light scattering, may range from 1000 to 3 000000 g/mol, preferably from 10000 to 1 000 000 and more particularly from 100000 to 500000 g/mol.
  • the polymers comprising units of formula (A) and optionally units of formula (B) are notably sold under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products provided under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
  • amphoteric or cationic vinylic polymers are chosen from polymer(s) comprising one or more cationic or quaternized (meth) acrylamide units, and could be cationic or amphoteric.
  • the cationic charge density of the polymers comprising one or more cationic or quaternized (meth) acrylamide units may preferably be lower than or equal to 6 meq/g, more preferentially lower than or equal to 5 meq/g, and better still lower than or equal to 4 meq/g.
  • This cationic charge density advantageously ranges from 0.5 to 6 meq/g, better still from 1 to 5 meq/g, and even more preferably from 1.5 to 4 meq/g.
  • the polymers comprising one or more cationic or quaternized (meth)acrylamide units that can be used in the present invention are preferably chosen from homopolymers or copolymers comprising at least one of the units of the following formulae: in which:
  • - Ri which may be identical or different, denote a hydrogen atom or a CH3 radical
  • - R which may be identical or different, denote a linear or branched Cl -Cl 2 alkyl radical, preferably a linear C1-C6 alkyl radical, optionally substituted by one or more hydroxyl radicals;
  • R9 which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical, preferably methyl or ethyl;
  • - Y“ denotes an anion derived from a mineral or organic acid or a halide, preferably bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
  • polymers comprising cationic or quaternized (meth)acrylamide units are chosen from copolymers comprising at least one unit of formula (IV) as defined previously, and more preferably comprising at least one unit of formula (IV) in which Ri denotes a hydrogen atom, R represents a linear alkyl group having 3 carbon atoms and R5, Re and R7 represent a methyl.
  • the polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) may also contain one or more units derived from comonomers that may be selected from the families of acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters, preferably selected from the families of acrylamide and methacrylamides, and more preferentially acrylamide or methacrylamide .
  • homopolymers of acrylamidopropyltrimonium halides preferable Chloride, such as the product N-DURHANCE A- 1000 from ASHLAND
  • copolymers of acrylamidopropyltrimonium halides, preferably chloride, and acrylamide such as the product sold under the name Salcare® SC 60 by the company BASF or sold under the name N-Hance SP 100 or N-Durhance AA2000 by the company Ashland, or the product sold under the name of N-Hance 4572 (e.g.
  • Aquaion aqua 4572 conditioning polymer by the company Ashland, that is a mixture of guar hydroxypropyltrimonium chloride and of acrylamidepropyl-trimonium chloride/acrylamide copolymer, vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those sold under the name STYLEZE CC 10 by ISP, quatemized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name GAFQUAT HS 100 by the company ISP.
  • the polymers comprising one or more cationic or quaternized (meth)acrylamide units that can be used in the present invention can also be chosen from amphoteric polymers.
  • Amphoteric polymers can be chosen more particularly from amphoteric polymers comprising a repetition of:
  • the units derived from a monomer of (meth)acrylamide type (i) are units of structure (VI) below: in which:
  • - Ri denotes a hydrogen atom or CH3 radical
  • R2 denotes a NR3R4 radical, wherein R3 and R4, which may be identical or different, denote a hydrogen atom or a linear or branched Cl -Cl 2 alkyl radical, optionally substituted by one or more hydroxyl radicals, preferably R2 denotes an amino, a dimethylamino, a tert-butylamino, a dodecylamino or a -NH-CH2OH radical.
  • the said amphoteric polymer comprises a repetition of only one unit of formula (VI).
  • the units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) are units of structure (VII) below: in which:
  • - Ri denotes a hydrogen atom or CH3 radical
  • Re and R7 which may be identical or different, denote a linear or branched Cl- C6 alkyl radical, preferably a linear or branched C1-C4 alkyl radical;
  • - n denotes an integer ranging from 1 to 6, preferably from 1 to 4;
  • - Y“ denotes an anion derived from a mineral or organic acid or a halide, preferably bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
  • the said amphoteric polymer comprises a repetition of only one unit of formula (VII).
  • RI denotes a methyl radical
  • n is equal to 3
  • R5, R6 and R7 denote a methyl radical
  • Y- denotes a chloride anion.
  • the units derived from a monomer of (meth) acrylic acid type (iii) are units of formula (VIII): in which:
  • - Ri denotes hydrogen atom or CH3 radical
  • R2 denotes a hydroxyl radical or a NR3R4 radical, wherein R3 and R4, which may be identical or different, denote a hydrogen atom or a linear or branched Cl -Cl 2 alkyl radical optionally substituted by a sulfonic group (-SO3H), preferably R2 denotes a - NH-C(CH 3 )2-CH 2 -SO3H radical.
  • the preferred units of formula (VIII) correspond to the acrylic acid, methacrylic acid and 2-acrylamino-2-methylpropanesulfonic acid monomers.
  • the unit derived from a monomer of (meth)acrylic acid type of formula (VIII) is that derived from acrylic acid, for which Ri denotes a hydrogen atom and R 2 denotes a hydroxyl radical.
  • the acidic monomer(s) of (meth)acrylic acid type may be non-neutralized or partially or totally neutralized with an organic or mineral base.
  • the said amphoteric polymer comprises a repetition of only one unit of formula (VIII).
  • the amphoteric polymer(s) of this type comprise at least 30 mol% of units derived from a monomer of (meth) acrylamide type (i). Preferably, they comprise from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units derived from a monomer of (meth) acrylamide type.
  • the content of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) may advantageously be from 10 mol% to 60 mol% and preferentially from 20 mol% to 55 mol%.
  • the content of units derived from an acidic monomer of (meth)acrylic acid type (iii) may advantageously be from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol%.
  • amphoteric polymer of this type comprises:
  • Amphoteric polymers of this type may also comprise additional units, other than the units derived from a monomer of (meth) acrylamide type, of (meth)acrylamidoalkyltrialkylammonium type and of (meth)acrylic acid type as described above.
  • the said amphoteric polymers consist solely of units derived from monomers (i) of (meth)acrylamide type, (ii) of (meth)acrylamidoalkyltrialkylammonium type and (iii) of (meth)acrylic acid type.
  • amphoteric polymers that are particularly preferred, mention may be made of acrylamide/ methacrylamidopropyltrimethylammonium chloride/ acrylic acid terpolymers. Such polymers are listed in the CTFA Dictionary (International Cosmetic Ingredient Dictionary) under the name Polyquatemium 53. Corresponding products are especially sold under the names Merquat 2003 and Merquat 2003 PR by the company Nalco.
  • amphoteric polymers Another preferred type of amphoteric polymers is the polymer comprising a repetition of:
  • the monomer of (meth)acrylamidoalkyltrialkylammonium type and the acidic monomer of (meth)acrylic acid type are as described above.
  • the non ionic monomers (i) of (meth)acrylate type are preferably chosen from C1-C4 alky acrylates and methacrylates.
  • a preferred monomer is methyl acrylate.
  • amphoteric polymers As particularly preferred examples of such amphoteric polymers, mention may be made of acrylic acid/ methylacrylamidopropyltrimethylammonium chloride/ methyl acrylates terpolymers. Such polymers are listed in the CTFA International Cosmetic Ingredient Dictionary under the name polyquatemium 47. Corresponding products are especially sold under the names Merquat 2001 and Merquat 200 IN by the company Nalco.
  • the polymer(s) c) are preferably chosen from:
  • (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth)acrylamide copolymers preferably (meth)acrylamidopropyltrimonium chloride/ (meth) acrylamide copolymers, and more preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers,
  • (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide /(meth)acrylamide/(meth)acrylic acid terpolymers preferably (meth)acrylamidopropyltrimonium chloride / (meth)acrylamide / (meth)acrylic acid terpolymers, more preferably acrylamide/ methacrylamidopropyltrimethylammonium chloride/ acrylic acid terpolymers,
  • (meth)acrylamido(C 1 -C6 alkyl)tri(C 1 -C4 alkyl) ammonium halide/ (C 1 -C6 alkyl) (meth)acrylate / (meth)acrylic acid terpolymers preferably (meth)acrylamidopropyltrimonium chloride / (C1-C6 alkyl) (meth) acrylate / (meth)acrylic acid terpolymers; more preferably acrylic acid/ methylacrylamidopropyl-trimethyl-ammonium chloride/ methyl acrylates terpolymers, and mixtures thereof.
  • the polymer(s) c) are chosen from:
  • (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth)acrylamide copolymers better (meth) aery lamidopropyltrimonium chloride/ (meth)acrylamide copolymers, and most preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers.
  • the total amount of cationic or amphoteric vinylic polymer(s) c) present in the composition of the present invention ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 2% by weight, better from 0.04 to 1% by weight, and even better from 0.05 to 0.5% by weight, relative to the total weight of the composition.
  • the total amount of cationic or amphoteric vinylic polymer(s) c) comprising one or more cationic or quatemized (meth)acrylamide units present in the composition of the present invention ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 2% by weight, better from 0.04 to 1% by weight, and even better from 0.05 to 0.5% by weight, relative to the total weight of the composition.
  • the composition comprises polymer(s) c) chosen from (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth) acrylamide copolymers, in a total amount ranging from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 2% by weight, better from 0.04 to 1% by weight, and even better from 0.05 to 0.5% by weight, relative to the total weight of the composition.
  • Optional cationic polysaccharides The composition according to the invention can optionally comprise one or more cationic polysaccharides, that are different from the cationic or amphoteric vinylic polymers c).
  • composition according to the invention comprises one or more cationic polysaccharides.
  • cationic polysaccharide means any polysaccharide comprising cationic groups and/or groups that can be ionized to cationic groups, and not comprising anionic groups and/or groups that can be ionized to anionic groups.
  • cationic polysaccharides that can be used according to the invention, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
  • the cellulose ether derivatives comprising quaternary ammonium groups are especially described in French patent 1 492 597, and mention may be made of the polymers sold under the name UCARE POLYMER “JR” (JR 400 LT, JR 125 and JR 30M) or “LR” (LR 400 or LR 30M) by the company Dow chemical. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxy ethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group. The polyquatemium-10 is, for example, one of these polymers.
  • Cationic cellulose copolymers or cellulose derivatives grafted with a water- soluble quaternary ammonium monomer are described especially in US patent 4 131 576, and mention may be made of hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • the commercial products corresponding to this definition are more particularly the products sold under the names CELQUAT L 200, CELQUAT SC240C and CELQUAT H 100 by the company Nouryon.
  • guar gums comprising cationic trialkylammonium groups, preferably C1-C6 trialkylammonium groups.
  • Use is made, for example, of guar gums modified with a 2,3- epoxypropyltrimethylammonium salt (for example, chloride).
  • a 2,3- epoxypropyltrimethylammonium salt for example, chloride.
  • Such products are especially sold under the names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR Cl 62 by the company Rhodia.
  • the cationic polysaccharide(s) is(are) chosen from cationic celluloses, cationic galactomannan gums, and mixtures thereof.
  • the cationic polysaccharide(s) is(are) chosen from cellulose ether derivatives comprising quaternary ammonium groups, guar gums comprising cationic trialkylammonium groups, and mixtures thereof.
  • composition according to the invention comprises one or more cellulose ether derivatives comprising quaternary ammonium groups, better polyquaternium- 10.
  • the total amount of cationic polysaccharide(s) d) ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 3% by weight, better from 0.05 to 2% by weight, and even better from 0.1 to 1% by weight, relative to the total weight of the composition.
  • the total amount of cationic polysaccharide(s) from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 3% by weight, better from 0.05 to 2% by weight, and even better from 0.1 to 1% by weight, relative to the total weight of the composition.
  • the total amount of cationic polysaccharide ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 3% by weight, better from 0.05 to 2% by weight, and even better from 0.1 to 1% by weight, relative to the total weight of the composition.
  • composition according to the invention comprises:
  • amphoteric or cationic vinylic polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) c), preferably chosen from (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth) acrylamide copolymers, preferentially from (meth) acrylamide -propyltrimonium chloride/ (meth)acrylamide copolymers, and most preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers, - one or more cationic polysaccharides d) chosen from cellulose ether derivatives comprising quaternary ammonium groups, preferably polyquaternium-10.
  • Anionic surfactants chosen from cellulose ether derivatives comprising quaternary ammonium groups, preferably polyquaternium-10.
  • composition according to the invention further comprises one or more anionic surfactants.
  • anionic surfactant means a surfactant comprising, as ionic or ionizable groups, only anionic groups.
  • a species is termed as being "anionic" when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
  • anionic surfactants that may be used in the invention are different from the polymers b) as described previously.
  • the anionic surfactants may be sulfate, sulfonate and/or carboxylic (or carboxylate) surfactants. Needless to say, a mixture of these surfactants may be used.
  • - carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-COOH or -COO ) and may optionally also comprise one or more sulfate and/or sulfonate functions;
  • the sulfonate anionic surfactants comprise at least one sulfonate function (-SO3H or -SO3 ) and may optionally also comprise one or more sulfate functions, but do not comprise any carboxylate functions; and
  • the sulfate anionic surfactants comprise at least one sulfate function but do not comprise any carboxylate or sulfonate functions.
  • the sulfate anionic surfactants that may be used comprise at least one sulfate function (-OSO3H or -OSO3 ).
  • alkyl sulfates alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl poly ether sulfates, monoglyceride sulfates; and also the salts of these compounds.
  • the alkyl groups of these compounds comprise from 6 to 30 carbon atoms, especially from 8 to 28, better still from 10 to 24 or even from 12 to 22 carbon atoms; the aryl group preferably denotes a phenyl or benzyl group.
  • These compounds are possibly polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.
  • the said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magnesium salt.
  • amino alcohol salts examples include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2- methyl-1 -propanol salts, 2-amino-2-methyl-l,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
  • Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
  • the anionic surfactant(s) e) is(are) selected from the anionic surfactants of alkyl(ether) sulfate type, and better still from C12-C14 alkyl(ether) sulfate salts, and in particular lauryl ether sulfate salts.
  • anionic surfactants suitable in the composition of the present invention can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
  • the anionic surfactant(s) e) is(are) present in a total amount ranging from 0.1 % to 40% by weight, preferentially from 0.5% to 30%, more preferentially from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
  • the one or more anionic surfactants are chosen from those of alkyl(ether) sulfate type
  • the one or more surfactants of alkyl(ether) sulfate type are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
  • the one or more anionic surfactants are chosen from C12- C14 alkyl(ether) sulfate salts
  • the one or more C12-C14 alkyl(ether) sulfate salts are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
  • the one or more anionic surfactants are chosen from lauryl ether sulfate salts
  • the one or more lauryl ether sulfate salts are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
  • Amphoteric or zwiterionic surfactants are chosen from lauryl ether sulfate salts
  • the one or more lauryl ether sulfate salts are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total
  • composition according to the invention further comprises one or more amphoteric or zwitterionic surfactants.
  • amphoteric or zwitterionic surfactants are different from the polymers c) as described previously.
  • amphoteric or zwitterionic surfactant(s) that may be used in the present invention may especially be secondary or tertiary aliphatic amine derivatives, optionally quatemized, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulphate, phosphate or phosphonate group.
  • amphoteric or zwitterionic surfactant(s) is(are) chosen from (C8-C20 alkyl)betaines such as cocoylbetaine, (C8-C20 alkyl)amido(C2- C8 alkyl)betaines such as cocoylamido-propylbetaine, and mixtures thereof.
  • the one or more amphoteric or zwitterionic surfactants are present in a total amount ranging from 0.01 % to 15% by weight, more preferably from 0.1% to 10%, even more preferably from 0.5% to 5% by weight, better from 0.75% to 3% by weight, relative to the total weight of the composition.
  • the total amount of surfactants present in the composition ranges from 0.1% to 30% by weight, more preferably from 1% to 20% by weight and even more preferably from 5% to 15% by weight, relative to the total weight of the composition.
  • the total amount of anionic surfactants e) and amphoteric or zwitterionic surfactants f) ranges from 0.1% to 30% by weight, more preferably from 1% to 20% by weight and even more preferably from 5% to 15% by weight, relative to the total weight of the composition.
  • the composition according to the invention is a cosmetic composition, more preferably a hair composition such as a hair composition for cleansing and/or conditioning hair.
  • composition of the invention may also contain various additives conventionally used in hair compositions.
  • anionic or non-ionic polymers examples include anionic or non-ionic polymers, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, fatty substances different from silicones previously described, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, direct dyes, sequestrants, plasticizers, solubilizers, acidifying agents, mineral or organic thickeners, especially polymeric thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances and preserving agents, and mixtures thereof.
  • anionic or non-ionic polymers examples include panthenol, sunscreens, mineral or organic pigments, direct dyes, sequestrants, plasticizers, solubilizers, acidifying agents, mineral or organic thickeners, especially polymeric thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances and preserving agents, and mixtures thereof.
  • the present invention also relates to a process for treating keratin fibres, preferably for washing and/or conditioning keratin fibres such as the hair, comprising a step of application onto the keratin fibres of a composition as described above.
  • composition according to the invention is removed after an optional leave-on time.
  • the leave-on time of the composition on the keratin fibres may range from a few seconds to 15 minutes, better still from 5 seconds to 10 minutes and even better still from 10 seconds to 5 minutes.
  • composition may be applied to wet or dry keratin fibres; preferably on wet keratin fibres.
  • the composition could be a shampoo, a conditioner or a hair mask.
  • the present invention relates to the use of a composition as described above for washing and/or conditioning keratin fibres, preferably the hair.
  • amino silicone fluid trimethylsilyl-terminated aminoethyl- aminopropylmethylsiloxane - dimethylsiloxane copolymer with amine value of 7.2 mg of KOH/g sample, and a viscosity of 5,600 mPa.s at 25°C
  • 1,800 g of trimethylsilyl terminated dimethylsiloxane polymer fluid of viscosity 61,500 mPa.s at 25°C were introduced under stirring in the same tank. Both fluids were mixed for 2 hours at room temperature.
  • compositions A and B were prepared from the ingredients indicated in Table below (wt. % of active material referred to as AM):
  • compositions A and B above has been evaluated on locks of natural hair.
  • the evaluation has been performed with the WDXRF Optim’x Thermofisher (Wavelength Dispersion) XRF system.
  • the principle is based on radiation emissions characteristic of the chemical element, produced by the impact of high energy photons dispensed by an X-ray tube.
  • Protocol 0.4g of composition was applied for 1g of hair lock.
  • the shampoo was massaged 6 times using fingers from root to tip, to generate foam.
  • the lock was then rinsed under running water (25 °C) 10 second.
  • the lock was then dried at 45 °C in an oven. This procedure was counted as 1 wash and then followed for 4 more washes to complete 5 wash cycle.
  • the silicone deposition of the composition A and the composition B onto keratin fibres has been measured after one application and after 5 applications for each.
  • composition A composition of the invention
  • the hair treated with the composition A according to the invention presents better cosmetic properties than the hair treated with the comparative composition B.
  • the hair treated with composition A is easier to comb and to disentangle in wet stage, and presents a better smooth feel, than the hair treated with the comparative composition B.
  • Example 3 Compositions A and B of example 2 were applied on medium Indian bleached hair locks of 20 cm and 3 g, at a rate of 0,4 g of composition per 1 g of hair.
  • the shampoo was massaged 6 times using fingers from root to tip, to generate foam.
  • the lock was then rinsed under running water (25°C) 10 seconds.
  • the locks were then placed in a large beaker of water for 1 minute. Post removal of excess water, the locks were gently combed 5 times on each side with a thin teeth rubber comb. The locks were clamped onto a load cell and force measurements for 5 combing cycles were recorded.
  • the principle of the method is that a comb is driven through a tress of hair and the load required to achieve this is measured. Peak forces and work done can be calculated from the instrument output. The measurement is performed from roots to tips. The average force (for 5 measurements) is calculated and the evolution of the peak force is recorded to quantify the ease of combing along the hair length (from roots to tips) for each lock.
  • the statistical analysis is carried out with software SPSS version 20 and repeatability and reproducibility is validated at the level of 5%.
  • compositions A and B are indicated in the table below:
  • composition A (according to the invention) are significantly easier to comb than the hair locks treated with comparative composition B.

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Abstract

The present invention relates to a composition for treating keratin fibers, and in particular human keratin fibers such as hair, which comprises a particular amino silicone, a specific oil-in-water-type silicone emulsion, one or more cationic vinylic polymers, preferably comprising at least one cationic or quaternized (meth)acrylamide unit and one or more surfactants. The invention also relates to a process for treating keratin fibres, preferably for washing and/or conditioning keratin fibres, comprising the application onto the keratin fibres of the composition according to the invention. Finally, the invention relates to the use of such a composition for washing and/or conditioning keratin fibres, preferably the hair.

Description

COMPOSITION COMPRISING A PARTICULAR SILICONE, A PARTICULAR SILICONE EMULSION, A PARTICULAR VINYLIC POLYMER AND SURFACTANTS
The present invention relates to a composition for treating keratin fibers, and in particular human keratin fibers such as hair, which comprises a particular amino silicone, a specific oil-in-water-type silicone emulsion, one or more cationic vinylic polymers, preferably comprising at least one cationic or quatemized (meth)acrylamide unit and one or more surfactants.
The invention also relates to a process for treating keratin fibres, preferably for washing and/or conditioning keratin fibres, comprising the application onto the keratin fibres of the composition according to the invention.
Finally, the invention relates to the use of such a composition for washing and/or conditioning keratin fibres, preferably the hair.
It is common practice to use detergent cosmetic compositions such as shampoos and shower gels, based essentially on surfactants, for washing keratin materials especially such as the hair and the skin. These compositions are applied to the keratin materials, which are preferably wet, and the lather generated by massaging or rubbing with the hands or a toiletry flannel makes it possible, after rinsing with water, to remove the diverse types of soiling initially present on the hair or the skin.
These compositions contain substantial contents of "detergent" surfactants, which, in order to be able to formulate cosmetic compositions with good washing power, must especially give them good foaming power.
The surfactants that are useful for this purpose are generally of anionic, nonionic and/or amphoteric type, and particularly of anionic type.
These compositions have generally a good washing power, but the intrinsic cosmetic properties associated with them nevertheless remain fairly poor, owing in particular to the fact that the relatively aggressive nature of such a cleaning treatment can, in the long run, lead to more or less pronounced damage to the hair fiber, this damage being associated in particular with the gradual removal of the lipids or proteins contained in or on the surface of this fiber.
Thus, in order to improve the cosmetic properties of the above detergent compositions, and more particularly those which are to be applied to sensitized hair (i.e. hair which has been damaged or made brittle, in particular under the chemical action of atmospheric agents and/or hair treatments such as permanent-waving, dyeing or bleaching), it is now common to introduce additional cosmetic agents known as conditioners into these compositions. These conditioners are intended mainly to repair or limit the harmful or undesirable effects induced by the various treatments or aggressions to which the hair fibres are subjected more or less repeatedly. They may, of course, also improve the cosmetic behavior of natural hair.
The conditioners most commonly used to date in shampoos include cationic polymers, silicones and/or silicone derivatives, which give washed, dry or wet hair an ease-of disentangling, softness and smoothness which are markedly better than that which can be obtained with corresponding cleaning compositions from which they are absent.
In particular, it is known to use a mixture of silicone and cationic polymer. However, the compositions containing them still have numerous disadvantages, such as leading to an insufficient deposit of silicones on hair and impacting therefore strongly on their cosmetic properties.
Thus, there is a real need to provide compositions, such as compositions for washing and/or conditioning keratin fibres, and in particular human keratin fibres, that make it possible to overcome the drawbacks described above, i.e. which effectively remove dirt and excess sebum and enhance cosmetic properties of said fibres, such as softness, smoothness, manageability and disentangling. These cosmetic properties may also be long-lasting.
In particular, the composition should give a satisfactory silicone deposition onto the keratin fibres and should improve hair disentangling.
These objectives are achieved with the present invention, a subject-matter of which is a composition comprising: a) one or more amino silicones comprising amino end groups, preferably one or more amino silicones corresponding to formula (I):
Figure imgf000003_0001
wherein:
- the radicals R, independently of one another, represent a hydrogen atom or a C1-C4 alkyl group,
- the radicals Rl, R2, R3 and R4, independently of one another, represent a hydrogen atom, a C1-C6 alkyl group or a C1-C6 aminoalkyl group, - x is between 0 and 6, y is between 0 and 6, and
- n is such that the weight-average molecular weight (Mw) of the amino silicone is between 5000 and 200 000, b) an oil-in-water emulsion having D50 particle size of less than 350 nm and comprising:
- a silicone mixture comprising (i) a trialkylsilyl terminated dialkylpolysiloxane having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C and (ii) an amino silicone having a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone,
- a mixture of emulsifiers comprising one or more nonionic emulsifiers, wherein the mixture of emulsifiers has a HLB value of from 10 to 16, and
- water, c) one or more amphoteric or cationic vinylic polymers, preferably comprising one or more cationic or quatemized acrylamide and/or methacrylamide unit(s), d) optionally one or more cationic polysaccharides, e) one or more anionic surfactants, f) one or more amphoteric or zwitterionic surfactants.
This composition, when applied onto keratin fibres, in particular human keratin fibres such as hair and more particularly the sensitized hair, leads to an improvement of the condition and quality of hair, in terms of hair feel (e.g. smooth feel, soft feel, conditioned feel) and hair manageability, both on wet and dry hair (e.g., no or less frizz, manageability, easy to detangle and comb, styleability/shapeability). The keratin fibres are particularly easy to disentangle and to comb.
In addition, the composition according to the invention makes it possible to significantly improve the silicone deposition onto the keratin fibres.
The composition according to the invention has a good detergent power.
The observed properties of the composition according to the invention are particularly long-lasting.
The present invention also relates to a process for treating, in particular for washing and/or conditioning, keratin fibres, preferably human keratin fibres such as the hair, comprising the application onto keratin fibres of the above-defined composition.
Another subject-matter of the invention is the use of such a composition for washing and/or conditioning keratin fibres, preferably the hair. Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the example that follows.
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" is equivalent to the expression "ranging from" and can be replaced therewith, and implies that the limits are included;
- according to the present application, the term “keratin fibres” preferably denotes human keratin fibres, and more preferentially the hair. a} Amino silicones with amino end groups
The composition according to the invention comprises one or more amino silicones comprising amine end groups; this means that the groups located at the chain end (the end groups in the alpha and omega positions) comprise an amino group.
Preferably, the composition according to the present invention comprises one or more amino silicones corresponding to formula (I):
Figure imgf000005_0001
wherein:
- the radicals R, independently of one another, represent a hydrogen atom or a C1-C4 alkyl group,
- the radicals Rl, R2, R3 and R4, independently of one another, represent a hydrogen atom, a C1-C6 alkyl group or a C1-C6 aminoalkyl group,
- x is between 0 and 6, y is between 0 and 6, and
- n is such that the weight-average molecular weight (Mw) of the amino silicone is between 5000 and 200 000.
Preferably, the radicals R are identical and represent CH3 (methyl).
Preferably, Rl, R2, R3 and R4, independently of one another, represent a hydrogen atom, a C2-C4 alkyl group, which is preferably linear and saturated, in particular ethyl; or a C2-C4 aminoalkyl group, in particular of structure -(Ca H2a)-NH2 with a = 2 to 4; in particular aminoethyl (-CH2-CH2-NH2). Preferably, x is between 1 and 5, better still between 2 and 4, even better still x=3. Preferably, y is between 1 and 5, better still between 2 and 4, even better still y=3. Preferably, x=y.
Preferably, n is such that the weight-average molecular weight (Mw) of the silicone is between 10 000 and 150000 g/mol, or even between 15 000 and 100 000 g/mol.
In one preferred embodiment, the amino silicone corresponds to formula (I) wherein R=methyl, x=y=3 and R1=R2=R3=R4=H; it is then a Bis-aminopropyl Dimethicone (INCI name).
The composition comprises a total content of amino silicone(s) with amino end groups a) ranging preferably from 0.01% to 10% by weight, preferentially from 0.05 % to 5% by weight, and better still from 0.08% to 1% by weight, relative to the total weight of the composition.
In a particular embodiment of the invention, the composition comprises a total content of amino silicone(s) of formula (I) ranging preferably from 0.01% to 10% by weight, preferentially from 0.05 % to 5% by weight, and better still from 0.08% to 1% by weight, relative to the total weight of the composition. b) Oil-in-water emulsion
The composition according to the present invention further comprises an oil- in-water (or silicone-in-water) emulsion having D50 particle size of less than 350 nm and containing:
- a silicone mixture comprising (i) a trialkylsilyl terminated dialkylpolysiloxane having a viscosity of from 40,000 to less than 100,000 mPa.s at 25 °C and (ii) an amino silicone which is different from amino silicones comprising amino end groups and which has a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone,
- a mixture of emulsifiers comprising one or more nonionic emulsifiers, wherein the mixture of emulsifiers has a HLB value of from 10 to 16, and
- water.
In the oil-in-water emulsion, or silicone-in-water emulsion, one liquid phase (the dispersed phase) is dispersed in the other liquid phase (the continuous phase); in the present invention, the silicone mixture, or silicone phase, is dispersed in the continuous aqueous phase. ( i ) trialkylsilyl terminated dialkylpolysiloxanes
The silicone mixture comprises a trialkylsilyl terminated dialkylpolysiloxane that is preferably of formula (IX):
R’3SiO(R’2SiO)pSiR’3 wherein:
- R’ , same or different, is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl, and
- p is an integer of from 500 to 2,000, preferably of from 1,000 to 2,000;
The trialkylsilyl terminated (or end-blocked or a,co-position) dialkylpolysiloxanes according to the invention have a viscosity of from 40,000 to less than 100,000 mPa.s (100,000 excluded) at 25°C, preferably a viscosity of from 40,000 to 70,000 mPa.s at 25°C, more preferably a viscosity of from 51,000 to 70,000 mPa.s at 25°C.
The trialkylsilyl terminated dialkylpolysiloxanes according to the invention are preferably linear but may contain additionally to the R’2SiO2/2 units (D-units) in formula (IX), RSiO3/2 units (T-units) and/or SiO4/2 units (Q-units), wherein R’, same or different, is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms.
Preferably, R’, same or different, are alkyl radicals, preferably C1-C18 alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radicals, hexyl radicals, such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radicals, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n- octadecyl radical; alkenyl radicals such as the vinyl and ally radical; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as the o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals such as the benzyl radical and the a- and the b-phenylethyl radical. Most preferred is the methyl radical.
Preferably, the trialkylsilyl terminated dialkylpolysiloxanes are trimethylsilyl terminated PDMS (polydimethylsiloxanes or dimethicones).
( ii ) amino silicones The silicone mixture comprises an amino silicone that are preferably of formula (X):
XR2Si(OSiAR)n(OSiR2)mOSiR2X wherein:
- R, same or different, is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl;
- X, same or different, is R or a hydroxyl (OH) or a Cl-C6-alkoxy group; preferably X is R, i.e. a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl;
- A is an amino radical of the formula -R1-[NR2-R3-]XNR2 2, or the protonated amino forms of said amino radical, wherein R1 is a Cl-C6-alkylene radical, preferably a radical of the formula -CH2CH2CH2- or -CH2CH(CH3)CH2-, R2, same or different, is a hydrogen atom or a Cl-C4-alkyl radical, preferably a hydrogen atom, R3 is a C1-C6- alkylene radical, preferably a radical of the formula -CH2CH2-, and x is 0 or 1; and
- m+n is an integer from 50 to about 1000, preferably from 50 to 600.
Preferably, A is an amino radical of the formula -R1-[NR2-R3-]XNR2 2, or the protonated amino forms of said amino radical, wherein R1 is -CH2CH2CH2- or - CH2CH(CH3)CH2-, R2 are hydrogen atoms, R3 is -CH2CH2-, and x is 1.
Preferably, R, same or different, are alkyl radicals, preferably C1-C18 alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radicals, hexyl radicals, such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radicals, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n- octadecyl radical; alkenyl radicals such as the vinyl and ally radical; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as the o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals such as the benzyl radical and the a- and the b-phenylethyl radical. Most preferred is the methyl radical. The amino silicones according to the invention have a viscosity of from 1,000 to 15,000 mPa.s at 25°C, preferably of from 1,500 to 15,000 mPa.s.
The amino silicones according to the invention have an amine value of from 2 to 10 mg of KOH per gram of amino silicone, preferably of from 3.5 to 8 mg.
The mole percent of amine functionality is preferably in the range of from about 0.3 to about 8%.
Examples of amino silicones useful in the silicone mixture according to the invention include trialkylsilyl terminated amino silicone.
Most preferably, amino silicones are trimethylsilyl terminated aminoethylaminopropylmethylsiloxane, most preferably trimethylsilyl terminated aminoethylaminopropylmethylsiloxane - dimethylsiloxane copolymers.
The amino radical A can be protonated partially or fully by adding acids to the amino silicone, wherein the salt forms of the amino radical are obtained. Examples of acids are carboxylic acids with 3 to 18 carbon atoms which can be linear or branched, such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, sorbic acid, benzoic acid, salicylic acid. The acids are preferably used in amounts of from 0.1 to 2.0 mol per 1 mol of amino radical A in the amino silicone of formula (X).
The silicone mixture preferably comprises (i) one or more trialkylsilyl terminated dialkylpoly siloxanes having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C in a quantity of from 70 to 90% by weight, preferably from 75 to 85% by weight and (ii) one or more amino silicones having a viscosity of from 1,000 to 15,000 mPa.s at 25 °C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone, in a quantity of from 10 to 30% by weight, preferably from 15 to 25% by weight, relative to the total weight of the silicone mixture. mixture of emulsifiers
The oil-in-water emulsion further comprises one or more nonionic emulsifiers. It could optionally comprise one or more cationic surfactants.
The mixture of emulsifiers has a HLB value from 10 to 16.
The nonionic emulsifiers can be chosen among the nonionic surfactants as described hereunder.
Mention may be made of alcohols, a-diols and (Cl-20) alkylphenols, these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30; or alternatively these compounds comprising at least one fatty chain comprising from 8 to 30 carbon atoms and especially from 16 to 30 carbon atoms.
Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; poly ethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5, and in particular from 1.5 to 4, glycerol groups; ethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, fatty acid esters of sucrose, polyoxyalkylenated and preferably polyoxyethylenated fatty acid esters containing from 2 to 150 mol of ethylene oxide, including oxyethylenated plant oils, N-(C6-24 alkyl)glucamine derivatives, amine oxides such as (CIO- 14 alkyl)amine oxides or N-(C10-14 acyl)aminopropylmorpholine oxides.
Mention may also be made of nonionic surfactants of alkyl(poly)glycoside type, represented especially by the following general formula:
RiO-(R2O)t-(G)v in which:
- Ri represents a linear or branched alkyl or alkenyl radical comprising 6 to 24 carbon atoms and especially 8 to 18 carbon atoms, or an alkylphenyl radical whose linear or branched alkyl radical comprises 6 to 24 carbon atoms and especially 8 to 18 carbon atoms;
- R2 represents an alkylene radical comprising 2 to 4 carbon atoms,
- G represents a sugar unit comprising 5 to 6 carbon atoms,
- 1 denotes a value ranging from 0 to 10 and preferably 0 to 4,
- v denotes a value ranging from 1 to 15 and preferably 1 to 4.
Preferably, the alkylpoly glyco side surfactants are compounds of the formula described above in which:
- Ri denotes a linear or branched, saturated or unsaturated alkyl radical comprising from 8 to 18 carbon atoms,
- R2 represents an alkylene radical comprising 2 to 4 carbon atoms, - 1 denotes a value ranging from 0 to 3 and preferably equal to 0,
- G denotes glucose, fructose or galactose, preferably glucose;
- the degree of polymerization, i.e. the value of v, possibly ranging from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2.
The glucoside bonds between the sugar units are generally of 1-6 or 1-4 type and preferably of 1-4 type. Preferably, the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant. C8/C16 alkyl(poly)glycosides 1,4, and especially decyl glucosides and caprylyl/capryl glucosides, are most particularly preferred.
Among the commercial products, mention may be made of the products sold by the company COGNIS under the names PLANTAREN® (600 CS/U, 1200 and 2000) or PLANTACARE® (818, 1200 and 2000); the products sold by the company SEPPIC under the names ORAMIX CG 110 and ORAMIX NS 10; the products sold by the company BASF under the name LUTENSOL GD 70, or else the products sold by the company CHEM Y under the name AGIO LK.
The nonionic emulsifiers could preferably be chosen among ethoxylated aliphatic alcohols, polyoxyethylene surfactants, carboxylic esters, polyethylene glycol esters, sorbitol ester and their ethoxylated derivatives, glycol esters of fatty acids, carboxylic amides, monoalkanolamine condensates, polyoxyethylene fatty acid amides.
Preferably, nonionic emulsifiers are selected from:
(i) polyoxy alkylene alkyl ethers, especially (poly)ethoxylated fatty alcohols of formula:
R3-(OCH2CH2)COH with:
- R3 representing a linear or branched C8-C40 alkyl or alkenyl group, preferably C8- C30 alkyl or alkenyl group, optionally substituted with one or more hydroxyl groups, and
- c being an integer between 1 and 200 inclusive, preferentially between 2 and 150 and more particularly between 4 and 50, most preferably between 8 and 20.
The (poly)ethoxylated fatty alcohols are more particularly fatty alcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to 30 mol of ethylene oxide (1 to 30 OE);
(ii) polyoxyalkylene (C8-C32)alkylphenyl ethers,
(iii) polyoxyalkylene sorbitan (C8-C32) fatty acid esters, especially polyethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; preferably polyoxyethylenated sorbitan (C10-C24) fatty acid esters preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; and
(iv) polyoxyethylenated (C8-C32) fatty acid esters containing for example from 2 to 150 mol of ethylene oxide; preferably polyoxyethylenated (C10-C24) fatty acid esters containing for example from 2 to 150 mol of ethylene oxide. Preferably, the nonionic emulsifiers could be selected from alkyl ether of polyalkyleneglycol and alkyl esters of polyalkyleneglycol; preferably of polyethyleneglycol (PEG).
Some useful emulsifiers are:
- polyethyleneglycol octyl ether; polyethyleneglycol lauryl ether; polyethyleneglycol tridecyl ether; polyethyleneglycol cetyl ether; polyethyleneglycol stearyl ether; among these, mention may be made more particularly of trideceth-3, trideceth-10 and steareth-6.
- polyethyleneglycol nonylphenyl ether; polyethyleneglycol dodecylphenyl ether; polyethyleneglycol cetylphenyl ether; polyethyleneglycol stearylphenyl ether;
- polyethyleneglycol sorbitan monostearate, polyethyleneglycol sorbitan monooleate.
- polyethyleneglycol stearate, and especially PEG- 100 stearate.
Most preferably, the nonionic emulsifiers are chosen among steareth-6, PEG- 100 stearate, trideceth-3 and trideceth-10 and their mixture; preferably, all these emulsifiers are present in the mixture of emulsifiers.
The mixture of emulsifiers could comprise one or more cationic emulsifiers that could be selected among tetraalkylammonium halides, tetraarylammonium halides, tetraalkylarylammonium halides, and their salts; quaternary ammonium compounds including salts; preferably, the cationic emulsifiers could be chosen among cetrimonium halides or behentrimonium halides, such as chloride.
The oil-in-water emulsion preferably comprises the mixture of emulsifiers in a total amount of from 5 to 15% by weight, more preferably of from 8 to 15% by weight, most preferably of from 10 to 12% by weight, relative to the total weight of the emulsion.
The oil-in-water emulsion preferably comprises nonionic emulsifiers in a total amount of from 5 to 15% by weight, more preferably of from 8 to 15% by weight, most preferably of from 10 to 12% by weight, relative to the total weight of the emulsion.
The oil-in-water emulsion preferably comprises cationic emulsifiers, when present, in a total amount of from 0.5 to 1.5% by weight, relative to the total weight of the emulsion.
The oil-in-water emulsion preferably comprises the silicone mixture in a total amount of from 40 to 60% by weight, more preferably of from 45 to 55% by weight, relative to the total weight of the emulsion. The oil-in-water emulsion preferably comprises the trialkylsilyl terminated dialkylpolysiloxane(s) in a total amount of from 35 to 45% by weight, more preferably of from 38 to 42% by weight, relative to the total weight of the emulsion.
The oil-in-water emulsion preferably comprises the amino silicone(s) in a total amount of from 5 to 15% by weight, more preferably of from 8 to 12% by weight, relative to the total weight of the emulsion.
The oil-in-water emulsion comprises water preferably in an amount of from 25 to 50% by weight, more preferably of from 30 to 45% by weight, most preferably of from 35 to 42% by weight, relative to the total weight of the emulsion.
The oil-in-water emulsion could additionally comprise a biocide, such as phenoxyethanol, that could be present in the emulsion in a quantity of from 0.5 to 1% by weight, relative to the total weight of the emulsion.
A method of preparation of the oil-in-water emulsion preferably comprises:
- a step of mixing one or more trialkylsilyl terminated dialkylpoly siloxanes of viscosity of from 40,000 to less than 100,000 mPa.s at 25°C and one or more amino silicones of viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone, at a temperature of from 15 °C to 40°C, preferably at 25°C, to obtain a mixed silicone fluid, then
- a step of adding a mixture of emulsifiers comprising one or more nonionic emulsifiers, wherein the mixture of emulsifiers has a HLB value from 10 to 16, to the mixed silicone fluid to obtain a silicone-emulsifier-mixture, then
- a step of homogenizing the silicone-emulsifier-mixture, followed by
- a step of adding, preferably step-wise, water, preferably demineralized water, to obtain an oil-in-water emulsion having D50 particle size of less than 350 nm.
The method of preparation of the oil-in-water emulsion could further comprise an additional step of adding a biocide. Biocide could be added for preserving the emulsion against microbial contamination. The biocide could be added at the level of for preserving emulsion against microbial contamination and obtaining the said emulsion. The quantity of the biocide depends on the type of biocide and as recommended by the manufacturer.
The preparation of the mixture of emulsifiers could be made by mixing one or more nonionic emulsifiers.
The pH of the oil-in-water emulsion after neutralization (i.e. after addition of the biocide) is preferably of from 4 to 6. The oil-in-water emulsion has D50 particle size of less than 350 nm, preferably from 100 to 300 nm, more preferably from 150 to 250 nm, even more preferentially from 150 to 225 nm, and most preferably from 160 to 200 nm. It corresponds to the average hydrodynamic particle diameter. The D50 particle size is expressed in volume. The D50 particle size could be measured by using a device ZetaSizer from Malvern, UK, model Nano-ZS, which is based on the Photon Correlation Spectroscopy (PCS) method. particle size measurement
Emulsion particle size could be measured by using a device ZetaSizer from Malvern, UK, model Nano-ZS which is based on the Photon Correlation Spectroscopy (PCS) method. The D50 value of particle size (average hydrodynamic particle diameter) is measured, wherein the evaluating algorithm is “cumulants analysis”.
For example, take 0.5 g of the emulsion sample in a 250 ml beaker, 100 ml of demineralized water is poured into it and then mixed properly to get the sample test solution. The sample test solution is poured in the cuvette cell and is put into the slot of the instrument to measure the particle size of the emulsion. D50 is defined as the value of the particle diameter at 50% in the cumulative distribution. For example, if D50=170 nm, then 50% of the particles in the sample are larger than 170 nm, and 50% smaller than 170 nm or about 50% by volume of all droplets in said emulsion is 170 nm. viscosity measurement
The viscosity, especially of the silicones or of the emulsion, is measured at 25°C and at atmospheric pressure.
For viscosities between 1000 to 40,000 mPa.s at 25°C: the viscosity could be measured with an Anton Paar Rheometer; model MCR101, geometry single gap cylinder: CC27 spindle and shear rate of 1 s-1 for 2 minutes, at 25°C.
For viscosities between 40,000 to 100,000 mPa.s at 25°C: the viscosity could be measured with an Anton Paar Rheometer; model MCR101, 25-6 cone (Cone-plate geometry: 25 mm dia. / 6° cone); the “Zero gap” setting being made and with a shear rate of 1 s-1 for 2 minutes, at 25°C.
Three measurements are made for each sample and the viscosity value is taken at 60 seconds. MCR Rheometer Series products work as per USP (US Pharmacopeia Convention) 912 - Rotational Rheometer methods. amine value measurement
The amine value is determined by acid-base titration using a potentiometer [Make: Veego; Model: VPT-MG]. 0.6 g of sample is taken in a 500 ml beaker and a toluene -butanol 1:1 mixture is added and stirred to mix the sample thoroughly; then the sample solution is titrated with a 0.1(N) HC1 solution. A determination of the blank value with the toluene -butanol 1:1 mixture is also done. The calculation of the amine value is done by the above-mentioned potentiometer.
The amine value is calculated according to the formula:
56.11 x (V - VBiank) x N / W mg KOH/ g of sample, wherein
V= Volume of HC1 required in ml, Vi>,i;illk= Volume of HC1 for blank value (without sample) with the toluene-butanol 1:1 mixture in ml;
N= Normality of HC1, i.e. 0.1 N, W= weight of the sample taken in gram.
HLB Value
The term HLB is well known to those skilled in the art, and denotes the hydrophilic-lipophilic balance of a surfactant or emulsifier. In the present invention, HLB values refer to the values at 25 °C and at atmospheric pressure.
The HLB can be measured by experimental determination or can be calculated.
Calculation of HLB value of nonionic surfactant is calculated according to the equation: HLB = (E + P)/5, with E being the weight percentage of oxyethylene content and P being the weight percentage of polyhydric alcohol content, described in to the publication Griffin, J. Soc. Cosm. Chem. 1954 (vol.5, n°4), pp.249-256.
It can also experimentally be determined according to the book of F. Puisieux and M. Seiller, entitled "Galenica 5: Les systemes disperses - Tome I - Agents de surface et emulsions - Chapitre IV - Notions de HLB et de HLB critique, pp.153- 194 - paragraph 1.1.2. Determination de HLB par voie experimentale [Experimental determination of HLB], pp.164-180".
The calculated HLB is the preferred HLB values that should be taken into account.
Said calculated HLB could be defined as being the following:
“calculated HLB = 20 x molar mass of the hydrophilic part/total molar mass.” For an oxyethylenated fatty alcohol, the hydrophilic part corresponds to the oxyethylene units condensed onto the fatty alcohol and the “calculated HLB” then corresponds to the “Griffin HLB” as defined hereabove.
For an ester or an amide, the hydrophilic part is naturally defined as being beyond the carbonyl group, starting from the fatty chain(s).
For ionic surfactants/emulsifiers, the HLB value of individual surfactant/emulsifier can be calculated applying the Davies formula as described in Davies JT (1957), "A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent", Gas/Liquid and Liquid/Liquid Interface (Proceedings of the International Congress of Surface Activity): 426-438.
According to the formula, the HLB is derived by summing the hydrophilic/hydrophobic contribution afforded by the structural components of the emulsifier:
HLB = (hydrophilic groups numbers) - n(group number per CH2 group) +7.
Approximate HLB values for some cationic emulsifiers are given in Table IV, in “Cationic emulsifiers in cosmetics”, GODFREY, J. Soc. Cosmetic Chemists (1966) 17, ppl7-27.
When two emulsifiers A and B of known HLB are blended for use, the HLB Mix is said to be the required HLB for the mixture. This is expressed by the equation (WAHLBA + WBHLBB)/ (WA + WB) = HLBMI , where WA = the amount (weight) of the first emulsifier (A) used, and WB = the amount (weight) of the second emulsifier (B); HLBA, HLBB = the assigned HLB values for emulsifiers A and B; HLBMI = the HLB of the mixture.
Said oil-in-water emulsion is for example described in WO 2017/108824.
The composition according to the invention preferably comprises the oil-in- water emulsion b) in an amount ranging from 0.1% to 20% by weight, more preferably from 0.3 % to 15% by weight, even more preferably from 0.5% to 12% by weight, better from 1 to 10%, even better from 2 to 8% by weight, relative to the total weight of the composition.
The composition according to the invention preferably comprises the trialkylsilyl terminated dialkylpolysiloxane(s) having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C in a total amount ranging from 0.1% to 8% by weight, more preferably from 0.2 % to 5% by weight, even more preferably from 0.5% to 4% by weight, better from 1 to 3% by weight, relative to the total weight of the composition.
The composition according to the invention preferably comprises the amino silicone(s) having a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone, in a total amount ranging from 0.1% to 5% by weight, more preferably from 0.2 % to 3% by weight, even more preferably from 0.3% to 2% by weight, better from 0.4 to 1% by weight, relative to the total weight of the composition. c) Amphoteric or cationic vinylic polymers
The composition according to the invention further comprises one or more amphoteric or cationic vinylic polymers. These polymers preferably comprise one or more cationic or quaternized acrylamide and/or methacrylamide unit(s).
These polymers are non-silicones, i.e. they do not contain any silicon (Si) atom.
By “cationic and/or amphoteric polymer(s)”, it is understood one or more cationic polymers, one or more amphoteric polymers or the mixture of one or more cationic polymers, and of one or more amphoteric polymers.
By “vinylic”, it is understood that the polymer derives from monomers comprising at least one vinylic monomer, preferably at least one (meth)acrylic monomer (i.e. monomer derived from acrylic or methacrylic acid, and its derivatives).
The term "cationic polymer" means any polymer comprising cationic groups and/or groups that can be ionized to cationic groups, and not comprising anionic groups and/or groups that can be ionized to anionic groups. Preferably, the cationic polymer is hydrophilic or amphiphilic. The preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that may either form part of the main polymer chain or may be borne by a side substituent directly connected thereto.
The term "amphoteric polymer" means any polymer comprising cationic groups and/or groups that can be ionized to cationic groups, and comprising anionic groups and/or groups that can be ionized to anionic groups.
Among the cationic or amphoteric polymers that can be used, mention may be made of:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units having the following formula:
Figure imgf000018_0001
wherein:
- R3, which may be identical or different, denote a hydrogen atom or a CH3 radical;
- A, which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxy alkyl group of 1 to 4 carbon atoms;
- R4, Rs and Re, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group containing from 1 to 6 carbon atoms;
- Ri and R2, which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
- X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide;
The copolymers of family (1) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (Ci-C=) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Among these copolymers of family (1), mention may be made of:
- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules,
- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, such as the products sold under the name Bina Quat P 100 by the company Ciba Geigy, the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, such as the product sold under the name Reten by the company Hercules,
- quatemized or non-quatemized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937, dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as the copolymers sold under the name Styleze CC 10 by ISP, quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP,
- preferably crosslinked polymers of methacryloyloxy(Ci -Chalky ltri(Cl- C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. Use may be made more particularly of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company BASF;
(2) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the copolymers comprising units corresponding to formula (II) or (III):
Figure imgf000020_0001
wherein:
- k and t are equal to 0 or 1, the sum k + t being equal to 1;
- R12 denotes a hydrogen atom or a methyl radical;
- Rio and Rn, independently of each other, denote a Ci-Ce alkyl group, a Ci- Cs hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively Rio and Rn may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidyl or morpholinyl; Rio and Rn, independently of each other, preferably denote a C1-C4 alkyl group;
- Y“ is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
Mention may be made more particularly of the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide (INCI : Polyquaternium-7), notably sold under the name Merquat 550 or Merquat 7SPR;
(3) polymers comprising in their structure:
(a) one or more units corresponding to formula (A) below:
Figure imgf000020_0002
(b) optionally one or more units corresponding to formula (B) below:
Figure imgf000020_0003
In other words, these polymers may be in particular chosen from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
Preferably, these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium.
The weight-average molecular weight of said polymer, measured by light scattering, may range from 1000 to 3 000000 g/mol, preferably from 10000 to 1 000 000 and more particularly from 100000 to 500000 g/mol.
The polymers comprising units of formula (A) and optionally units of formula (B) are notably sold under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products provided under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
Preferably, the amphoteric or cationic vinylic polymers are chosen from polymer(s) comprising one or more cationic or quaternized (meth) acrylamide units, and could be cationic or amphoteric.
The cationic charge density of the polymers comprising one or more cationic or quaternized (meth) acrylamide units may preferably be lower than or equal to 6 meq/g, more preferentially lower than or equal to 5 meq/g, and better still lower than or equal to 4 meq/g. This cationic charge density advantageously ranges from 0.5 to 6 meq/g, better still from 1 to 5 meq/g, and even more preferably from 1.5 to 4 meq/g.
The polymers comprising one or more cationic or quaternized (meth)acrylamide units that can be used in the present invention are preferably chosen from homopolymers or copolymers comprising at least one of the units of the following formulae:
Figure imgf000021_0001
in which:
- Ri, which may be identical or different, denote a hydrogen atom or a CH3 radical;
- R, which may be identical or different, denote a linear or branched Cl -Cl 2 alkyl radical, preferably a linear C1-C6 alkyl radical, optionally substituted by one or more hydroxyl radicals;
- Rs, Re and R7, which may be identical or different, denote a linear or branched Cl- C18 alkyl radical or a benzyl radical, preferably a linear or branched C1-C6 alkyl radical;
- Rs and R9, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical, preferably methyl or ethyl; and
- Y“ denotes an anion derived from a mineral or organic acid or a halide, preferably bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
More particularly the polymers comprising cationic or quaternized (meth)acrylamide units are chosen from copolymers comprising at least one unit of formula (IV) as defined previously, and more preferably comprising at least one unit of formula (IV) in which Ri denotes a hydrogen atom, R represents a linear alkyl group having 3 carbon atoms and R5, Re and R7 represent a methyl.
The polymers comprising one or more cationic or quaternized (meth)acrylamide unit(s) may also contain one or more units derived from comonomers that may be selected from the families of acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters, preferably selected from the families of acrylamide and methacrylamides, and more preferentially acrylamide or methacrylamide .
Among these homo- or co-polymers, mention may be made of: homopolymers of acrylamidopropyltrimonium halides, preferable Chloride, such as the product N-DURHANCE A- 1000 from ASHLAND, copolymers of acrylamidopropyltrimonium halides, preferably chloride, and acrylamide, such as the product sold under the name Salcare® SC 60 by the company BASF or sold under the name N-Hance SP 100 or N-Durhance AA2000 by the company Ashland, or the product sold under the name of N-Hance 4572 (e.g. Aquaion aqua 4572 conditioning polymer) by the company Ashland, that is a mixture of guar hydroxypropyltrimonium chloride and of acrylamidepropyl-trimonium chloride/acrylamide copolymer, vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those sold under the name STYLEZE CC 10 by ISP, quatemized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name GAFQUAT HS 100 by the company ISP.
The polymers comprising one or more cationic or quaternized (meth)acrylamide units that can be used in the present invention can also be chosen from amphoteric polymers.
Amphoteric polymers can be chosen more particularly from amphoteric polymers comprising a repetition of:
(i) one or more units derived from a monomer of (meth) acrylamide type,
(ii) one or more units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type, and
(iii) one or more units derived from an acidic monomer of (meth) acrylic acid type.
Preferably, the units derived from a monomer of (meth)acrylamide type (i) are units of structure (VI) below:
Figure imgf000023_0001
in which:
- Ri denotes a hydrogen atom or CH3 radical; and
- R2 denotes a NR3R4 radical, wherein R3 and R4, which may be identical or different, denote a hydrogen atom or a linear or branched Cl -Cl 2 alkyl radical, optionally substituted by one or more hydroxyl radicals, preferably R2 denotes an amino, a dimethylamino, a tert-butylamino, a dodecylamino or a -NH-CH2OH radical.
Preferably, the said amphoteric polymer comprises a repetition of only one unit of formula (VI).
The unit derived from a monomer of (meth) acrylamide type of formula (VI) in which Ri denotes a hydrogen atom and R2 is an amino radical (NH2) is particularly preferred. It corresponds to the acrylamide monomer per se.
Preferably, the units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) are units of structure (VII) below:
Figure imgf000024_0001
in which:
- Ri denotes a hydrogen atom or CH3 radical;
- R5, Re and R7, which may be identical or different, denote a linear or branched Cl- C6 alkyl radical, preferably a linear or branched C1-C4 alkyl radical;
- n denotes an integer ranging from 1 to 6, preferably from 1 to 4; and
- Y“ denotes an anion derived from a mineral or organic acid or a halide, preferably bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
Preferably, the said amphoteric polymer comprises a repetition of only one unit of formula (VII).
Among these units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type of formula (VII), the ones that are preferred are those derived from the methacrylamidopropyltrimethylammonium chloride monomer, for which RI denotes a methyl radical, n is equal to 3, R5, R6 and R7 denote a methyl radical, and Y- denotes a chloride anion.
Preferably, the units derived from a monomer of (meth) acrylic acid type (iii) are units of formula (VIII):
Figure imgf000024_0002
in which:
- Ri denotes hydrogen atom or CH3 radical; and
- R2 denotes a hydroxyl radical or a NR3R4 radical, wherein R3 and R4, which may be identical or different, denote a hydrogen atom or a linear or branched Cl -Cl 2 alkyl radical optionally substituted by a sulfonic group (-SO3H), preferably R2 denotes a - NH-C(CH3)2-CH2-SO3H radical.
The preferred units of formula (VIII) correspond to the acrylic acid, methacrylic acid and 2-acrylamino-2-methylpropanesulfonic acid monomers.
Preferably, the unit derived from a monomer of (meth)acrylic acid type of formula (VIII) is that derived from acrylic acid, for which Ri denotes a hydrogen atom and R2 denotes a hydroxyl radical.
The acidic monomer(s) of (meth)acrylic acid type may be non-neutralized or partially or totally neutralized with an organic or mineral base.
Preferably, the said amphoteric polymer comprises a repetition of only one unit of formula (VIII).
Preferably, the amphoteric polymer(s) of this type comprise at least 30 mol% of units derived from a monomer of (meth) acrylamide type (i). Preferably, they comprise from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units derived from a monomer of (meth) acrylamide type.
The content of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii) may advantageously be from 10 mol% to 60 mol% and preferentially from 20 mol% to 55 mol%.
The content of units derived from an acidic monomer of (meth)acrylic acid type (iii) may advantageously be from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol%.
Preferably, the amphoteric polymer of this type comprises:
- from 30 mol% to 70 mol% and more preferably from 40 mol% to 60 mol% of units derived from a monomer of (meth)acrylamide type (i),
- from 10 mol% to 60 mol% and preferentially from 20 mol% to 55 mol% of units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type (ii), and
- from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol% of units derived from a monomer of (meth)acrylic acid type (iii).
Amphoteric polymers of this type may also comprise additional units, other than the units derived from a monomer of (meth) acrylamide type, of (meth)acrylamidoalkyltrialkylammonium type and of (meth)acrylic acid type as described above.
However, according to a preferred embodiment of the invention, the said amphoteric polymers consist solely of units derived from monomers (i) of (meth)acrylamide type, (ii) of (meth)acrylamidoalkyltrialkylammonium type and (iii) of (meth)acrylic acid type.
As examples of amphoteric polymers that are particularly preferred, mention may be made of acrylamide/ methacrylamidopropyltrimethylammonium chloride/ acrylic acid terpolymers. Such polymers are listed in the CTFA Dictionary (International Cosmetic Ingredient Dictionary) under the name Polyquatemium 53. Corresponding products are especially sold under the names Merquat 2003 and Merquat 2003 PR by the company Nalco.
Another preferred type of amphoteric polymers is the polymer comprising a repetition of:
(i) one or more non ionic units derived from a monomer of (meth)acrylate type,
(ii) one or more units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type, and
(iii) one or more units derived from an acidic monomer of (meth) acrylic acid type.
The monomer of (meth)acrylamidoalkyltrialkylammonium type and the acidic monomer of (meth)acrylic acid type (monomers (ii) and (iii) respectively) are as described above.
The non ionic monomers (i) of (meth)acrylate type are preferably chosen from C1-C4 alky acrylates and methacrylates. A preferred monomer is methyl acrylate.
As particularly preferred examples of such amphoteric polymers, mention may be made of acrylic acid/ methylacrylamidopropyltrimethylammonium chloride/ methyl acrylates terpolymers. Such polymers are listed in the CTFA International Cosmetic Ingredient Dictionary under the name polyquatemium 47. Corresponding products are especially sold under the names Merquat 2001 and Merquat 200 IN by the company Nalco.
The polymer(s) c) are preferably chosen from:
(meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth)acrylamide copolymers, preferably (meth)acrylamidopropyltrimonium chloride/ (meth) acrylamide copolymers, and more preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers,
(meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide /(meth)acrylamide/(meth)acrylic acid terpolymers, preferably (meth)acrylamidopropyltrimonium chloride / (meth)acrylamide / (meth)acrylic acid terpolymers, more preferably acrylamide/ methacrylamidopropyltrimethylammonium chloride/ acrylic acid terpolymers,
(meth)acrylamido(C 1 -C6 alkyl)tri(C 1 -C4 alkyl) ammonium halide/ (C 1 -C6 alkyl) (meth)acrylate / (meth)acrylic acid terpolymers, preferably (meth)acrylamidopropyltrimonium chloride / (C1-C6 alkyl) (meth) acrylate / (meth)acrylic acid terpolymers; more preferably acrylic acid/ methylacrylamidopropyl-trimethyl-ammonium chloride/ methyl acrylates terpolymers, and mixtures thereof.
Even more preferentially, the polymer(s) c) are chosen from:
(meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth)acrylamide copolymers, better (meth) aery lamidopropyltrimonium chloride/ (meth)acrylamide copolymers, and most preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers.
Preferably, the total amount of cationic or amphoteric vinylic polymer(s) c) present in the composition of the present invention ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 2% by weight, better from 0.04 to 1% by weight, and even better from 0.05 to 0.5% by weight, relative to the total weight of the composition.
Preferably, the total amount of cationic or amphoteric vinylic polymer(s) c) comprising one or more cationic or quatemized (meth)acrylamide units present in the composition of the present invention ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 2% by weight, better from 0.04 to 1% by weight, and even better from 0.05 to 0.5% by weight, relative to the total weight of the composition.
Preferentially, the composition comprises polymer(s) c) chosen from (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth) acrylamide copolymers, in a total amount ranging from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 2% by weight, better from 0.04 to 1% by weight, and even better from 0.05 to 0.5% by weight, relative to the total weight of the composition. d) Optional cationic polysaccharides The composition according to the invention can optionally comprise one or more cationic polysaccharides, that are different from the cationic or amphoteric vinylic polymers c).
Preferably, the composition according to the invention comprises one or more cationic polysaccharides.
The term "cationic polysaccharide" means any polysaccharide comprising cationic groups and/or groups that can be ionized to cationic groups, and not comprising anionic groups and/or groups that can be ionized to anionic groups.
Among the cationic polysaccharides that can be used according to the invention, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
The cellulose ether derivatives comprising quaternary ammonium groups are especially described in French patent 1 492 597, and mention may be made of the polymers sold under the name UCARE POLYMER “JR” (JR 400 LT, JR 125 and JR 30M) or “LR” (LR 400 or LR 30M) by the company Dow chemical. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxy ethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group. The polyquatemium-10 is, for example, one of these polymers.
Cationic cellulose copolymers or cellulose derivatives grafted with a water- soluble quaternary ammonium monomer are described especially in US patent 4 131 576, and mention may be made of hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names CELQUAT L 200, CELQUAT SC240C and CELQUAT H 100 by the company Nouryon.
The cationic galactomannan gums are described more particularly in US patents 3 589 578 and 4 031 307, and mention may be made of guar gums comprising cationic trialkylammonium groups, preferably C1-C6 trialkylammonium groups. Use is made, for example, of guar gums modified with a 2,3- epoxypropyltrimethylammonium salt (for example, chloride). Such products are especially sold under the names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR Cl 62 by the company Rhodia.
Preferably, the cationic polysaccharide(s) is(are) chosen from cationic celluloses, cationic galactomannan gums, and mixtures thereof.
Preferentially, the cationic polysaccharide(s) is(are) chosen from cellulose ether derivatives comprising quaternary ammonium groups, guar gums comprising cationic trialkylammonium groups, and mixtures thereof.
More preferentially, the composition according to the invention comprises one or more cellulose ether derivatives comprising quaternary ammonium groups, better polyquaternium- 10.
Preferably, the total amount of cationic polysaccharide(s) d) ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 3% by weight, better from 0.05 to 2% by weight, and even better from 0.1 to 1% by weight, relative to the total weight of the composition.
Preferably, when the cationic polysaccharide(s) d) is(are) chosen from cellulose ether derivatives comprising quaternary ammonium groups, the total amount of cationic polysaccharide(s) from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 3% by weight, better from 0.05 to 2% by weight, and even better from 0.1 to 1% by weight, relative to the total weight of the composition.
Preferably, when the cationic polysaccharide d) is polyquaternium- 10, the total amount of cationic polysaccharide ranges from 0.01 to 5% by weight, more preferentially from 0.015 to 4% by weight, even more preferentially from 0.02 to 3% by weight, better from 0.05 to 2% by weight, and even better from 0.1 to 1% by weight, relative to the total weight of the composition.
Preferably, the composition according to the invention comprises:
- one or more amphoteric or cationic vinylic polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) c), preferably chosen from (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth) acrylamide copolymers, preferentially from (meth) acrylamide -propyltrimonium chloride/ (meth)acrylamide copolymers, and most preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers, - one or more cationic polysaccharides d) chosen from cellulose ether derivatives comprising quaternary ammonium groups, preferably polyquaternium-10. e) Anionic surfactants
The composition according to the invention further comprises one or more anionic surfactants.
The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups.
In the present description, a species is termed as being "anionic" when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the invention (for example the medium or the pH) and not comprising any cationic charge.
The anionic surfactants that may be used in the invention are different from the polymers b) as described previously.
The anionic surfactants may be sulfate, sulfonate and/or carboxylic (or carboxylate) surfactants. Needless to say, a mixture of these surfactants may be used.
It is understood in the present description that:
- carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-COOH or -COO ) and may optionally also comprise one or more sulfate and/or sulfonate functions;
- the sulfonate anionic surfactants comprise at least one sulfonate function (-SO3H or -SO3 ) and may optionally also comprise one or more sulfate functions, but do not comprise any carboxylate functions; and
- the sulfate anionic surfactants comprise at least one sulfate function but do not comprise any carboxylate or sulfonate functions.
The sulfate anionic surfactants that may be used comprise at least one sulfate function (-OSO3H or -OSO3 ).
They may be chosen from the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl poly ether sulfates, monoglyceride sulfates; and also the salts of these compounds.
The alkyl groups of these compounds comprise from 6 to 30 carbon atoms, especially from 8 to 28, better still from 10 to 24 or even from 12 to 22 carbon atoms; the aryl group preferably denotes a phenyl or benzyl group. These compounds are possibly polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units.
When the anionic surfactant is in salt form, the said salt may be chosen from alkali metal salts, such as the sodium or potassium salt, ammonium salts, amine salts and in particular amino alcohol salts, and alkaline-earth metal salts, such as the magnesium salt.
Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2- methyl-1 -propanol salts, 2-amino-2-methyl-l,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
More preferentially, the anionic surfactant(s) e) is(are) selected from the anionic surfactants of alkyl(ether) sulfate type, and better still from C12-C14 alkyl(ether) sulfate salts, and in particular lauryl ether sulfate salts.
The anionic surfactants suitable in the composition of the present invention can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
Preferably, the anionic surfactant(s) e) is(are) present in a total amount ranging from 0.1 % to 40% by weight, preferentially from 0.5% to 30%, more preferentially from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
Preferably, when the one or more anionic surfactants are chosen from those of alkyl(ether) sulfate type, the one or more surfactants of alkyl(ether) sulfate type are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
Preferably, when the one or more anionic surfactants are chosen from C12- C14 alkyl(ether) sulfate salts, the one or more C12-C14 alkyl(ether) sulfate salts are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition.
Preferably, when the one or more anionic surfactants are chosen from lauryl ether sulfate salts, the one or more lauryl ether sulfate salts are present in a total amount ranging from 0.1 % to 40% by weight, more preferably from 0.5% to 30%, even more preferably from 1% to 25% by weight, even more preferentially is greater than or equal to 5% by weight, better from 5 % to 20% by weight, even better from 10 to 15% by weight, relative to the total weight of the composition. f) Amphoteric or zwiterionic surfactants
The composition according to the invention further comprises one or more amphoteric or zwitterionic surfactants.
The amphoteric or zwitterionic surfactants are different from the polymers c) as described previously.
The amphoteric or zwitterionic surfactant(s) that may be used in the present invention may especially be secondary or tertiary aliphatic amine derivatives, optionally quatemized, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulphate, phosphate or phosphonate group.
More preferentially, the amphoteric or zwitterionic surfactant(s) is(are) chosen from (C8-C20 alkyl)betaines such as cocoylbetaine, (C8-C20 alkyl)amido(C2- C8 alkyl)betaines such as cocoylamido-propylbetaine, and mixtures thereof.
Preferably, the one or more amphoteric or zwitterionic surfactants are present in a total amount ranging from 0.01 % to 15% by weight, more preferably from 0.1% to 10%, even more preferably from 0.5% to 5% by weight, better from 0.75% to 3% by weight, relative to the total weight of the composition.
Preferably, the total amount of surfactants present in the composition ranges from 0.1% to 30% by weight, more preferably from 1% to 20% by weight and even more preferably from 5% to 15% by weight, relative to the total weight of the composition. Preferably, the total amount of anionic surfactants e) and amphoteric or zwitterionic surfactants f) ranges from 0.1% to 30% by weight, more preferably from 1% to 20% by weight and even more preferably from 5% to 15% by weight, relative to the total weight of the composition.
Preferably, the composition according to the invention is a cosmetic composition, more preferably a hair composition such as a hair composition for cleansing and/or conditioning hair.
Optionally, the composition of the invention may also contain various additives conventionally used in hair compositions.
As additives that may be used in accordance with the invention, mention may be made of anionic or non-ionic polymers, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, fatty substances different from silicones previously described, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, direct dyes, sequestrants, plasticizers, solubilizers, acidifying agents, mineral or organic thickeners, especially polymeric thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances and preserving agents, and mixtures thereof.
Needless to say, a person skilled in the art will take care to select this or these optional additive(s) such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The present invention also relates to a process for treating keratin fibres, preferably for washing and/or conditioning keratin fibres such as the hair, comprising a step of application onto the keratin fibres of a composition as described above.
Optionally, after the step of application, the composition according to the invention is removed after an optional leave-on time.
The leave-on time of the composition on the keratin fibres may range from a few seconds to 15 minutes, better still from 5 seconds to 10 minutes and even better still from 10 seconds to 5 minutes.
The composition may be applied to wet or dry keratin fibres; preferably on wet keratin fibres.
The composition could be a shampoo, a conditioner or a hair mask. Finally, the present invention relates to the use of a composition as described above for washing and/or conditioning keratin fibres, preferably the hair.
In the above description, all the preferred embodiments with regard to the components may be used individually or in combination.
The examples that follow serve to illustrate the invention.
Examples
In the examples that follow and unless otherwise indicated, the amounts are given as weight percentages of active material (AM) relative to the total weight of the composition.
Example 1: Preparation of an oil-in-water emulsion
450 g of amino silicone fluid (trimethylsilyl-terminated aminoethyl- aminopropylmethylsiloxane - dimethylsiloxane copolymer with amine value of 7.2 mg of KOH/g sample, and a viscosity of 5,600 mPa.s at 25°C) were introduced in an emulsion tank. Stirring was started and 1,800 g of trimethylsilyl terminated dimethylsiloxane polymer fluid of viscosity 61,500 mPa.s at 25°C were introduced under stirring in the same tank. Both fluids were mixed for 2 hours at room temperature.
In a separate tank, 49 g of steareth-6 and 62 g of PEG- 100 stearate were introduced and heated to 60°C. The temperature was maintained till both emulsifiers became liquid. Then 31 g of trideceth-3 and 350 g of trideceth-10 (80% of active material) were added. These nonionic emulsifiers mixture had an HLB value = 11.25.
Then 80 g water and 6.2 g glacial acetic acid were added to the tank and the mixing started. The mixing was continued till whole mass became a creamy paste. The whole paste was introduced in the emulsion tank. Homogenization was carried out for 30 minutes at room temperature. 79.6 g demineralized water were added and homogenization was carried out for 60 minutes. 72.7 g demineralized water were added and homogenization was carried out for 50 minutes. 197.4 g demineralized water were added and homogenization was carried out for 5 minutes. 294.3 g demineralized water were added and homogenization was carried out for 5 minutes. 180 g demineralized water were added and homogenization was carried out for 5 minutes. 180 g demineralized water were added and homogenization was carried out for 5 minutes. 197.4 g demineralized water were added and homogenization was carried out for 5 minutes. 197.4 g demineralized water were added and homogenize for 3 minutes. 228.5 g demineralized water were added and homogenization was carried out for 3 minutes. Lastly 40.5 g 2-phenoxyethanol were added as a biocide and homogenization was carried out for 3 minutes.
A stable oil-in-water emulsion having D50 particle size of 170 nm was obtained. Example 2
The following compositions A (invention) and B (comparative) was prepared from the ingredients indicated in Table below (wt. % of active material referred to as AM):
Figure imgf000036_0001
The silicone deposition of compositions A and B above has been evaluated on locks of natural hair.
The evaluation has been performed with the WDXRF Optim’x Thermofisher (Wavelength Dispersion) XRF system. The principle is based on radiation emissions characteristic of the chemical element, produced by the impact of high energy photons dispensed by an X-ray tube.
Operational parameters: - Gas Flow Helium - Argon/Methane (90/10)
- X-ray tube (Rh), Crystal PET and detector FPC - Tension 25kv- 2mA
- 3 measurements / lock = 60s/ measurement
- Minimum sample size 250mg (2mm pieces)
Protocol: 0.4g of composition was applied for 1g of hair lock. The shampoo was massaged 6 times using fingers from root to tip, to generate foam. The lock was then rinsed under running water (25 °C) 10 second. The lock was then dried at 45 °C in an oven. This procedure was counted as 1 wash and then followed for 4 more washes to complete 5 wash cycle.
The silicone deposition of the composition A and the composition B onto keratin fibres has been measured after one application and after 5 applications for each.
The results are shown in the table below.
Figure imgf000037_0001
The combination of an amino silicone a) with an oil in water emulsion b) leads to much more efficient silicone deposition. This enables the composition of the invention (composition A) to bring stronger benefits to the hair, such as better combing on both wet and dry hair.
It has also been noted that the hair treated with the composition A according to the invention presents better cosmetic properties than the hair treated with the comparative composition B. In particular, the hair treated with composition A is easier to comb and to disentangle in wet stage, and presents a better smooth feel, than the hair treated with the comparative composition B.
Example 3 Compositions A and B of example 2 were applied on medium Indian bleached hair locks of 20 cm and 3 g, at a rate of 0,4 g of composition per 1 g of hair. The shampoo was massaged 6 times using fingers from root to tip, to generate foam. The lock was then rinsed under running water (25°C) 10 seconds.
The locks were then placed in a large beaker of water for 1 minute. Post removal of excess water, the locks were gently combed 5 times on each side with a thin teeth rubber comb. The locks were clamped onto a load cell and force measurements for 5 combing cycles were recorded.
The combing test is performed as follow:
Combing experiment parameters for wet combing:
- start position : 40mm
- tress length : 180mm
- combing speed : 1500mm/min.
The principle of the method is that a comb is driven through a tress of hair and the load required to achieve this is measured. Peak forces and work done can be calculated from the instrument output. The measurement is performed from roots to tips. The average force (for 5 measurements) is calculated and the evolution of the peak force is recorded to quantify the ease of combing along the hair length (from roots to tips) for each lock.
The statistical analysis is carried out with software SPSS version 20 and repeatability and reproducibility is validated at the level of 5%.
The lower the force, the better the detangling.
The results obtained with compositions A and B are indicated in the table below:
Figure imgf000038_0001
The hair locks treated with composition A (according to the invention) are significantly easier to comb than the hair locks treated with comparative composition B.

Claims

1. Composition comprising: a) one or more amino silicones comprising amino end groups, preferably one or more amino silicones corresponding to formula (I):
Figure imgf000039_0001
wherein:
- the radicals R, independently of one another, represent a hydrogen atom or a C1-C4 alkyl group,
- the radicals Rl, R2, R3 and R4, independently of one another, represent a hydrogen atom, a C1-C6 alkyl group or a C1-C6 aminoalkyl group,
- x is between 0 and 6, y is between 0 and 6, and
- n is such that the weight-average molecular weight (Mw) of the amino silicone is between 5000 and 200 000, b) an oil-in-water emulsion having D50 particle size of less than 350 nm and comprising:
- a silicone mixture comprising (i) a trialkylsilyl terminated dialkylpolysiloxane having a viscosity of from 40,000 to less than 100,000 mPa.s at 25°C and (ii) an amino silicone which is different from amino silicones comprising amino end groups and which has a viscosity of from 1,000 to 15,000 mPa.s at 25°C and an amine value of from 2 to 10 mg of KOH per gram of amino silicone,
- a mixture of emulsifiers comprising one or more nonionic emulsifiers, wherein the mixture of emulsifiers has a HLB value of from 10 to 16, and
- water, c) one or more amphoteric or cationic vinylic polymers, d) optionally one or more cationic polysaccharides, different from polymers c), e) one or more anionic surfactants, f) one or more amphoteric or zwitterionic surfactants.
2. Composition according to Claim 1, wherein the amino silicone a) of formula (I) is such that: - the radicals R are identical and represent CH3 (methyl); and/or
- the radicals Rl, R2, R3 and R4, independently of one another, represent a hydrogen atom, a C2-C4 alkyl group, which is preferably linear and saturated, in particular ethyl; or a C2-C4 aminoalkyl group, in particular of structure -(Ca H2a)-NH2 with a = 2 to 4; in particular aminoethyl (-CH2-CH2-NH2); and/or
- x is between 1 and 5, better still between 2 and 4, even better still x=3; and/or
- y is between 1 and 5, better still between 2 and 4, even better still y=3; and/or
- n is such that the weight- average molecular weight (Mw) of the silicone is between 10000 and 150000 g/mol, or even between 15000 and 100000 g/mol.
3. Composition as claimed in one of the preceding claims, wherein the amino silicone a) of formula (I) is such that R=methyl, x=y=3 and R 1=R2=R3=R4=H.
4. Composition according to any one of the preceding claims, wherein the total content of amino silicone(s) with amino end groups a) ranges from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and preferentially from 0.08% to 1% by weight, relative to the total weight of the composition.
5. Composition according to any one of the preceding claims, wherein said trialkylsilyl terminated dialkylpoly siloxane (i) is of formula (IX):
R’3SiO(R’2SiO)PSiR’3 wherein:
- R’ , same or different, is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl, and
- p is an integer of from 500 to 2,000, preferably of from 1,000 to 2,000; and preferably is trimethylsilyl terminated poly dimethylsiloxane.
6. Composition according to any one of the preceding claims, wherein said amino silicone (ii) is of formula (X):
XR2Si(OSiAR)n(OSiR2)mOSiR2X wherein:
- R, same or different, is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably from 1 to 6 carbon atoms, even better from 1 to 3 carbon atoms, more preferably methyl;
- X, same or different, is R or a hydroxyl (OH) or a Cl-C6-alkoxy group; preferably X is R;
- A is an amino radical of the formula -R1-[NR2-R3-]XNR22, or the protonated amino forms of said amino radical, wherein R1 is a Cl-C6-alkylene radical, preferably a radical of the formula -CH2CH2CH2- or -CH2CH(CH3)CH2-, R2, same or different, is a hydrogen atom or a Cl-C4-alkyl radical, preferably a hydrogen atom, R3 is a C1-C6- alkylene radical, preferably a radical of the formula -CH2CH2-, and x is 0 or 1; and
- m+n is an integer from 50 to about 1000, preferably from 50 to 600; preferably, A is an amino radical of the formula -R1-[NR2-R3-]XNR22, or the protonated amino forms of said amino radical, wherein R1 is -CH2CH2CH2- or - CH2CH(CH3)CH2-, R2 are hydrogen atoms, R3 is -CH2CH2-, and x is 1.
7. Composition according to any one of the preceding claims, wherein the mixture of emulsifiers comprises one or more nonionic emulsifiers chosen from:
(i) polyoxyalkylene alkyl ethers, especially (poly)ethoxylated fatty alcohols of formula:
R3-(OCH2CH2)COH with:
- R3 representing a linear or branched C8-C40 alkyl or alkenyl group, preferably C8- C30 alkyl or alkenyl group, optionally substituted with one or more hydroxyl groups, and
- c being an integer between 1 and 200 inclusive, preferentially between 2 and 150 and more particularly between 4 and 50, most preferably between 8 and 20. and more particularly fatty alcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to 30 mol of ethylene oxide (1 to 30 OE);
(ii) polyoxyalkylene (C8-C32)alkylphenyl ethers;
(iii) polyoxyalkylene sorbitan (C8-C32) fatty acid esters, especially polyethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; preferably poly oxyethylenated sorbitan (C10-C24) fatty acid esters preferably containing from 2 to 40 ethylene oxide units, most preferably from 2 to 20 ethylene oxide units; and
(iv) polyoxyethylenated (C8-C32) fatty acid esters containing for example from 2 to 150 mol of ethylene oxide; preferably polyoxyethylenated (C10-C24) fatty acid esters containing for example from 2 to 150 mol of ethylene oxide.
8. Composition according to any one of the preceding claims, wherein the polymer(s) c) is (are) chosen among amphoteric or cationic vinylic polymers comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s), preferably from homopolymers or copolymers comprising at least one of the units of the following formulae:
Figure imgf000042_0001
in which:
- Ri, which may be identical or different, denote a hydrogen atom or a CH3 radical;
- R, which may be identical or different, denote a linear or branched Cl -Cl 2 alkyl radical, preferably a linear C1-C6 alkyl radical, optionally substituted by one or more hydroxyl radicals;
- R5, Re and R7, which may be identical or different, denote a linear or branched Cl- C18 alkyl radical or a benzyl radical, preferably a linear or branched C1-C6 alkyl radical;
- Rs and R9, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical, preferably methyl or ethyl; and
- Y“ denotes an anion derived from a mineral or organic acid or a halide, preferably bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
9. Composition according to any one of the preceding claims, wherein the polymer(s) c) comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) is(are) chosen from amphoteric polymers, and preferably from amphoteric polymers comprising a repetition:
(i) one or more units derived from a monomer of (meth) acrylamide type,
(ii) one or more units derived from a monomer of (meth)acrylamidoalkyltrialkylammonium type, and
(iii) one or more units derived from an acidic monomer of (meth) acrylic acid type.
10. Composition according to any one of the preceding claims, wherein the polymer(s) c) comprising one or more cationic or quaternized acrylamide and/or methacrylamide unit(s) is(are) chosen from:
(meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (meth)acrylamide copolymers, preferably (meth)acrylamidopropyltrimonium chloride/ (meth) acrylamide copolymers, and more preferably acrylamidopropyltrimonium chloride/ acrylamide copolymers,
(meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide /(meth) aery lamide/(meth) acrylic acid terpolymers, preferably
(meth)acrylamidopropyltrimonium chloride / (meth)acrylamide / (meth)acrylic acid terpolymers, more preferably acrylamide/ methacrylamidopropyltrimethylammonium chloride/ acrylic acid terpolymers,
- (meth)acrylamido(Cl-C6 alkyl)tri(Cl-C4 alkyl) ammonium halide/ (C1-C6 alkyl) (meth)acrylate / (meth)acrylic acid terpolymers, preferably (meth)acrylamidopropyltrimonium chloride / (C1-C6 alkyl) (meth) acrylate / (meth)acrylic acid terpolymers; more preferably acrylic acid/ methylacrylamidopropyWrimethyl-ammonium chloride/ methyl acrylates terpolymers,
- and mixtures thereof.
11. Composition according to any one of the preceding claims, wherein the total amount of amphoteric or cationic vinylic polymer(s) c) ranges from 0.01 to 5% by weight, preferentially from 0.015 to 4% by weight, more preferentially from 0.02 to 2% by weight, even more preferentially from 0.04 to 1% by weight, and better from 0.05 to 0.5% by weight, relative to the total weight of the composition.
12. Composition according to any one of the preceding claims, wherein the composition comprises one or more cationic polysaccharide(s) d) preferably chosen from cationic celluloses, cationic galactomannan gums, and mixtures thereof; preferably from cellulose ether derivatives comprising quaternary ammonium groups, guar gums comprising cationic trialkylammonium groups, and mixtures thereof, preferentially from cellulose ether derivatives comprising quaternary ammonium groups, and more preferentially polyquaternium-10.
13. Composition according to any one of the preceding claims, wherein the anionic surfactant(s) e) is(are) selected from the anionic surfactants of alkyl(ether) sulfate type, and better still from C12-C14 alkyl(ether) sulfate salts, and in particular lauryl ether sulfate salts.
14. Composition according to any one of the preceding claims, wherein the amphoteric or zwitterionic surfactant(s) f) is (are) selected from (C8-C20 alkyl)betaines such as cocoylbetaine, (C8-C20 alkyl)amido(C2-C8 alkyl)betaines such as cocoylamido-propylbetaine, and mixtures thereof.
15. Process for treating keratin fibres, preferably for washing and/or conditioning keratin fibres, comprising the application onto the keratin fibres of a composition as defined in any one of the preceding claims.
PCT/EP2023/079908 2022-11-03 2023-10-26 Composition comprising a particular silicone, a particular silicone emulsion, a particular vinylic polymer and surfactants WO2024094537A1 (en)

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