[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2024141527A1 - Process for treating keratin materials using at least one alkoxysilane compound bearing acetoacetate functions and at least one crosslinking agent - Google Patents

Process for treating keratin materials using at least one alkoxysilane compound bearing acetoacetate functions and at least one crosslinking agent Download PDF

Info

Publication number
WO2024141527A1
WO2024141527A1 PCT/EP2023/087795 EP2023087795W WO2024141527A1 WO 2024141527 A1 WO2024141527 A1 WO 2024141527A1 EP 2023087795 W EP2023087795 W EP 2023087795W WO 2024141527 A1 WO2024141527 A1 WO 2024141527A1
Authority
WO
WIPO (PCT)
Prior art keywords
chosen
composition
formula
group
optionally
Prior art date
Application number
PCT/EP2023/087795
Other languages
French (fr)
Inventor
Laurent SABATIE
Boris STEVANT
Xavier FROGNEUX-PLE
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'oreal filed Critical L'oreal
Publication of WO2024141527A1 publication Critical patent/WO2024141527A1/en

Links

Classifications

    • 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
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • 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
    • A61K8/736Chitin; Chitosan; 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
    • A61K8/72Cosmetics 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
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/04Preparations containing skin colorants, e.g. pigments for lips
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/10Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • 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
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits
    • A61K2800/884Sequential application

Definitions

  • Cosmetic products conventionally require the use of one or more film-forming polymers in order to obtain a quality deposit of these products on keratin materials and in particular to satisfy the expectations detailed below.
  • dispersions of polymer particles of nanometric size are used in makeup products such as mascaras, eyeliners, eyeshadows or lipsticks, and in hair application products, and more particularly in their organic and notably oily phases, as film-forming agent.
  • patent EP 1 392 222 it is also known practice from patent EP 1 392 222 to use a cosmetic composition for caring for and/or treating keratin materials, comprising a supramolecular polymer including a polymer backbone and at least two groups that are capable of forming at least three hydrogen bonds, and from patent EP 1 435 900 to use a hair composition comprising a supramolecular polymer including a polymer backbone and at least two groups that are capable of forming at least three hydrogen bonds and a surfactant or a hair-conditioning agent.
  • a cosmetic composition for caring for and/or treating keratin materials comprising a supramolecular polymer including a polymer backbone and at least two groups that are capable of forming at least three hydrogen bonds
  • patent EP 1 435 900 to use a hair composition comprising a supramolecular polymer including a polymer backbone and at least two groups that are capable of forming at least three hydrogen bonds and a surfactant or a hair-conditioning agent.
  • compositions and processes for forming deposits on keratin substrates having good staying power over time, using compounds bearing acetoacetate functions and functionalized active agents in order to be covalently bonded to the keratin materials are also known from WO 2014/099108.
  • Japanese document JP2003326843 describes inks for inkjet printing comprising polymers with amino groups and coupling agents of silane type.
  • keratin materials is intended to denote notably the lips, skin, nails and keratin fibres, in particular the eyelashes, eyebrows and the hair, preferably the lips and/or the hair.
  • cosmetic active agent means an organic or organosilicon compound or a mineral compound which can be incorporated into a cosmetic composition to give an effect on keratin materials, whether this effect is immediate or provided by repeated applications.
  • composition means that said composition contains an amount of less than 5% by weight of water, preferentially less than 3% by weight of water, better still less than 1% by weight of water, relative to the total weight of the composition in question; even more preferentially, the composition under consideration is free of water.
  • the process for treating keratin materials according to the invention using the ingredients i), ii), optionally iii) and optionally iv), is a process for caring for the skin.
  • composition termed “C2”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow;
  • the process for treating keratin materials according to the invention uses a composition, termed “C2”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously, preferably, said composition “C2” comprising iii) water.
  • the treatment process according to the invention comprises a single step of applying composition “C2” or composition “C3” to said keratin materials.
  • one-gesture application mode means the direct application to the target keratin materials of a single composition in accordance with the invention, namely composition “C2” or “C3”.
  • composition “C2” or “C3” After application of composition “C2” or “C3”, a persistent, non-tacky deposit is advantageously obtained.
  • the deposit obtained is also resistant to food oils, water, sebum and friction.
  • two-gesture application mode means the successive application, to the target keratin material, of two different compositions, for example “Cl” and “C4”, or “C2” and “C4”, or “C3” and “C4”, preferably “Cl” and then “C4”, “C2” and then “C4”, or “C3” and then “C4”.
  • the process of the invention is performed in three gestures.
  • three-gesture application mode means the sequential application of three different compositions “Cl” to “C5”. According to this application mode, for example, according to one embodiment, successive application is performed on the keratin materials, a) of a composition “Cl”, then P) of a composition “C4”, then y) of a composition “C5”, preferably “Cl” then “C4” or, respectively, “C5” or “C5” or, respectively, “C4”.
  • the composition applied first for example “Cl”
  • the base coat is conventionally referred to as the “base coat”
  • the composition(s) superposed thereon are generally referred to as the “top coat”.
  • compositions “Cl” to “C5” After application of the various compositions “Cl” to “C5”, a persistent, non-tacky deposit is advantageously obtained.
  • the deposit obtained is also resistant to food oils, water and shampoo washing.
  • the keratin materials are dried after application of compositions “Cl” to “C5”, in particular after application of each different composition.
  • the drying step can be implemented with a drying device such as a helmet, a hair dryer or a climazon.
  • the drying temperature is comprised between 40 °C and 110 °C, preferably between 50 °C and 90°C.
  • a step of shaping the keratin fibers can be implemented with a hair straightener (“fer a lisser”), a straightening or curling iron or a steam iron, preferably a hair straightener or a steam iron.
  • the step of shaping the keratin fibres is carried out at a temperature ranging from 120 °C to 230 °C, notably from 150 °C to 210 °C, even more preferentially from 160 °C to 210 °C, better from 180 °C to 210 °C.
  • the iron can be applied to the keratin fibers in successive separate touches of a few seconds, or by progressive movement or sliding along the hair.
  • the application of the iron is done in continuous movement from the root to the tip of the hair, in one or more passes.
  • the present invention relates to a cosmetic treatment process for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the successive application of at least:
  • composition termed “Cl”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow; and then
  • compositions “C4” comprising ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow; at least one of the compositions “Cl” and/or “C4” containing at least one dyestuff, in particular as defined previously and hereinbelow, preferably at least one pigment, and more preferentially composition “Cl” comprises at least one pigment.
  • the present invention relates to a cosmetic treatment process for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the successive application of at least:
  • compositions “C2” or “C3” contain at least iv) one dyestuff, in particular as defined hereinbelow, and/or composition “C4” contains at least one dyestuff, in particular as defined hereinbelow; preferably composition “C2” or “C3” comprises at least one pigment.
  • the compound(s) of formula (I) according to the invention are such that R b and R c , which may be identical or different, represent a hydrogen atom and R d represents a linear or branched (Ci-C4)alkyl group, preferably R d represents a methyl group.
  • the compound(s) of formula (I) according to the invention are such that ALK represents a saturated or unsaturated, linear or branched, acyclic, divalent hydrocarbon-based group, comprising from 1 to 6 carbon atoms, preferably a (Ci-C4)alkylene group, more preferentially propylene.
  • the compound(s) of formula (I) or (I’) are such that X represents -O-. According to another preferred embodiment, the compound(s) of formula (I) or (I’) are such that X represents a group -N(R a )- with R a as defined previously, preferably X represents a group -N(H)-.
  • the compound(s) of formula (I) or (I’) are such that R 1 represents a (Ci-C4)alkyl group, preferably a (Ci-C2)alkyl group.
  • the compound(s) of formula (I) or (I’) are such that R 1 represents a methyl group.
  • the compound(s) of formula (I) or (I’) are such that R 1 represents an ethyl group.
  • the compound(s) of formula (I) or (I’) are such that R 1 represents a hydrogen atom.
  • the compound(s) of formula (I) or (I’) are such that R 2 represents a (Ci-C2)alkyl group.
  • the compound(s) of formula (I) or (I’) are such that R 2 represents a methyl group.
  • the compound(s) of formula (I) or (I’) can be obtained according to methods known to those skilled in the art.
  • the compound(s) of formula (I) or (I’) may be synthesized according to the routes described in JP2005314325, JP2016069290, WO2014027766, US20190315778, or in the publication “Photoactive Diazoketo-Functionalized Self- Assembled Monolayer for Biomolecular Patterning”, Langmuir (2009), 25(16), 8888-8893.
  • the compound(s) of formula (I) are used in a medium containing at least one water-soluble solvent.
  • a composition used in the treatment process according to the invention preferably comprises one or more water- soluble solvents, more preferentially ethanol, in a content ranging from 5% to 90%, better still from 10% to 85% by weight, preferably from 25% to 80% by weight, relative to the total weight of said composition.
  • the treatment process according to the invention as described previously comprises the application to keratin materials of (i) at least one or more compounds of formula (I), and (ii) at least one crosslinking agent.
  • crosslinking agent also termed “R” denotes a compound that is capable of establishing with at least one acetoacetate function of the compound(s) of formula (I) used in the treatment process according to the invention: at least one covalent bond, at least one donor-acceptor (dative) bond, and/or at least one coordination bond, and thus of crosslinking this or these compound(s).
  • crosslinking agent and “crosslinker” are equivalent.
  • crosslinking agent(s) R that are suitable for use in the invention may be chosen from compounds bearing amine, thiol, and/or acrylate functions.
  • a crosslinking agent R may also denote a metal alkoxide.
  • the metal alkoxide compounds are defined below.
  • non-polymeric compound means a compound which is not directly obtained via a monomer polymerization reaction.
  • (Poly)amine compounds that may be mentioned in particular include N-methyl-1,3- diaminopropane, N-propyl- 1,3 -diaminopropane, N-isopropyl- 1,3 -diaminopropane, N- cyclohexyl-l,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2- aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methylbis(3- aminopropyl)amine, N-(3-aminopropyl)-l,4-diaminobutane, N,N- dimethyldipropylenetriamine, 1 ,2-bis(3-aminopropylamino)ethane, N,N’ -bis(3- aminopropyl)
  • the (poly)amine compounds are monoamine compounds, i.e. they contain only one primary and/or secondary amine group, preferably a primary amine group (NH2).
  • RT is a linear or branched, saturated or unsaturated, cyclic or acyclic Ci-Ce hydrocarbon-based chain substituted with a group chosen from primary amine groups NH2 or secondary amine groups -N(H)R with R representing a C1-C4 alkyl, an aryl or a benzyl substituted with an amino group or with a C1-C4 aminoalkyl group; RT may be interrupted in its chain with a heteroatom (O, S, NH) or a carbonyl group (CO), R being linked to the silicon atom directly via a carbon atom,
  • a heteroatom O, S, NH
  • CO carbonyl group
  • the (poly)amine compounds are diamine compounds, i.e. they contain two primary and/or secondary amine groups, preferably primary amine groups (NH2).
  • formula (VII) is such that R a represents a hydroxyl or (Ci- C4)alkyl group, such as methyl, ALK 1 represents a (Cs-C6)alkylene group substituted with an NH group; preferably, ALK 1 represents -(CH2)3-N(H)-(CH2)2-, and m and n are such that the weight- average molecular mass of the compound of formula (VI) ranges from 5000 g.mol 1 to 500000 g.mol 1 .
  • the (poly)amine compounds are chosen from hyperbranched polymers comprising at least one amino group and dendrimers bearing at least one amino group, such as PAMAM polyamidoamine dendrimers with an ethylenediamine core and a terminal amine function.
  • - q denotes an integer greater than or equal to 2; preferably, q is between 2 and 10 inclusive and preferably between 2 and 5;
  • the (poly)thiol compound(s) are chosen from thiolated alkoxysiloxanes, such as those of formula (VIII’) below: R’i-Si(OR’2)z(R’ 3 )x (VIII’) in which formula (VIII’):
  • - 1 is an integer between 1 and 4, preferably 2;
  • - R 4 and R’ 4 which may be identical or different, represent a hydrogen atom or a (Ci-C6)alkyl group, such as methyl; - L 1 represents a divalent, saturated, linear or branched C1-C20 hydrocarbon-based radical.
  • the thiolated alkoxysiloxanes are chosen from those of formula (IX’) below: (R’ 1 O)(R’ 2 )(R’ 3 )Si-CH(R 4 )-CH(R 5 )-(L 2 ) q -SH (IX’) in which formula (IX’):
  • - X represents an oxygen or sulfur atom, preferably a sulfur atom
  • - R’ 1 denotes a (Ci-C6)alkyl radical
  • R 4 represents a hydrogen atom or a C1-C4 alkyl group, in particular methyl
  • - L 2 represents a linear or branched, saturated C1-C20 divalent hydrocarbon-based group, optionally interrupted with a heteroatom such as -N(H)-, and/or optionally substituted with one or more hydroxyl, thiol or amino groups.
  • the thiolated alkoxysilane(s) are chosen from 4-(trimethoxy silyl)- 1 -butanol, 3- (trimethoxy silyl)- 1 -propanol, 3-(triethoxysilyl)-l-propanol, 11 -(trimethoxy silyl)- 1- undecanethiol, 4-(trimethoxysilyl)-2-butanethiol, 2-(triethoxysilyl)ethanethiol, 3- (triethoxy silyl)- 1 -propanethiol, 2-(trimethoxysilyl)ethanethiol, 3 -(trimethoxy silyl)- 1- propanethiol and 3-(dimethoxymethylsilyl)-l-propanethiol.
  • the thiolated alkoxysilane(s) are chosen from 2- (triethoxysilyl)ethanethiol (18236-15-2) and 3 -(triethoxy silyl)- 1 -propanethiol (14814-09-6).
  • the (poly)thiol compound(s) are chosen from polymeric (poly)thiol compounds.
  • Examples that may be mentioned include the polymers described in the following articles: Polymers containing groups of biological activity, C.G. Overberger et al., Polytechnic Institute of Brooklyn, http://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf; EP 1 247 515 A2; US 3 676 440; and EP 1 572 778.
  • polymeric (poly)thiol compounds of the invention are preferably organic and/or silicone compounds, more preferentially of formula (X):
  • - POLY denotes a polymer-based radical, preferably carbon-based or silicone-based; POLY being optionally interrupted with one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and combinations thereof such as -O-, -O-C(X)-, -N(R)-C(X)-, -Si(R c )(Rd)-O- with R representing a hydrogen atom or a (C i -CoJal kyl group such as methyl; and/or POLY being optionally substituted with one or more halogen atoms, or a group chosen from R a (Rb)N- and -(X’) a -C(X)-(X”)b-R a ; X, X’ and X”, which may be identical or different, represent an oxygen or sulfur atom or a group N(Rb); a and b being 0 or 1, preferably the sum of a + b being 1; R a
  • the methods for preparing the polymeric (poly)thiol compounds used according to the invention are known to those skilled in the art; several methods are reported hereinbelow in a non-limiting manner.
  • the polymeric (poly)thiol compounds used according to the invention may be obtained by polymerization or polycondensation of monomer units bearing thiol or protected thiol functions, optionally as a copolymerization or co-polycondensation of monomer units free of thiol or protected thiol functions.
  • the polymeric (poly)thiol compounds used according to the invention are polymers which are soluble in cosmetic media, particularly in aqueous or aqueous -alcoholic media. They are more preferentially obtained from amino polymers and the ammonium salts thereof or from poly hydroxylated polymers.
  • the thiolated polymers used according to the invention are polymers that are soluble in lipophilic media.
  • the polythiol compound is a polymeric compound of formula (X) in which q denotes an integer greater than or equal to 2, and POLY denotes a carbon-based and/or silicon-based, preferably silicon-based, polymeric radical, POLY also possibly containing one or more heteroatoms chosen from O, N or S, and/or one or more functions chosen from (thio)ester, (thio)ketone, (thio)amide, (thio)urea and (thio)carbamate functions, and/or possibly being substituted with one or more linear or branched (Ci-Cio)alkyl or linear or branched (Ci-Cio)alkoxy groups, it being understood that when POLY is substituted, the thiol functions may be borne by the substituent(s).
  • formula (X) in which q denotes an integer greater than or equal to 2
  • POLY denotes a carbon-based and/or silicon-based, preferably silicon-based, polymeric radical
  • POLY also possibly
  • the weight-average molecular weight of the polythiol polymer compounds is generally between 500 and 400 000 g.moT 1 , preferably between 500 and 150000 g.moT 1 .
  • the polythiol compounds are chosen from polyorganosiloxanes including thiol groups on end chains, such as those of formula (XI) below:
  • R a and R b which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci-C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl;
  • n represents an integer greater than or equal to 1 and more particularly the value of n is such that the weight- average molecular weight of the silicone ranges from 500 to 55 000 g.moT 1 ; in particular, n is an integer ranging from 1 to 100, preferably ranging from 5 to 50 and preferentially ranging from 10 to 30, and
  • L 4 and L 5 which may be identical or different, preferably identical, represent a linear or branched, saturated or unsaturated, optionally cyclic hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, and in particular represent a covalent bond or a (Ci-C6)alkylene, (Ci-C6)alkylenoxy, oxy(Ci-C6)alkylene, (Ci-C6)alkylenoxy(Ci- C6)alkylene, (Ci-C6)alkylenoxy(Ci-C6)alkylenoxy or oxy(Ci-C6)alkylenoxy(Ci-C6)alkylene group, preferably a (Ci-C6)alkylene, (Ci-C6)alkylenoxy, oxy(Ci-C6)alkylene or (Ci- Ce) alky lenoxy (C i -Ce) alkylene group, preferably
  • the (poly)thiol compounds are polythiol polyorganosiloxanes, more preferentially polythiol poly dimethylsiloxanes, notably chosen from those of formula (XII): HS-L 4 -Si(CH3)2-O-[Si(CH3)2-O] n -Si(CH3) 2 -L 5 -SH (XII) in which formula (XII):
  • L 4 and L 5 are as defined previously in formula (IX), in particular L 4 and L 5 represent a (Ci- C6)alkylene, (Ci-C6)alkylenoxy, oxy(Ci-C6)alkylene or (Ci-C6)alkylenoxy(Ci-C6)alkylene group, more preferentially a divalent group chosen from -R2-, -O-R2-, -R2-O- and -R2- O-R2-, preferably -R2-O-R2-, with R2 representing a linear or branched, preferably linear, (C2-C6)alkylene group, such as ethylene or n-propylene, preferably n-propylene; and
  • polythiol compounds of formula (XII) mention may be made of mercaptosiloxanes or thiolated siloxanes in which the thiol functions are at the chain ends, sold by the company Shin-Etsu under the reference X-22-167B, and mercaptosiloxane in which the mercapto functions are pendent, sold by the company Shin-Etsu under the reference KF-2001, or polydimethylsiloxanes in which the thiol functions are at the chain ends, via thio-n-propyl, 80-120 groups, sold by the company Gelest under the name DMS-SM 21.
  • the polythiol compounds are chosen polyorganosiloxanes including thiol groups on side chains, such as those of formula (XIII): R a -Si(R b )(R d )-O-[Si(R a )(R b )-O] m -[Si(R b )(ALKi-SH)-O]ii-Si(R b )(R d )-R a (XIII) in which formula (XIII):
  • R a and R b are as defined in formula (XI) and R d is as defined for R a and R b , preferably R a , R b and R d , which are identical, represent a (Ci-C6)alkyl group, such as methyl;
  • R d may also represent a (Ci-C6)alkyl group substituted with a (Ci -Chalky lamino or amino or thiol group, preferably (Ci-C4)alkyl such as methyl;
  • the (poly)thiol compounds are chosen from hyperbranched polymers comprising at least one thiol group and dendrimers bearing at least one thiol group, such as thiolated PAMAM dendrimers.
  • the (poly)thiol compounds used according to the invention are chosen from polydiallylsiloxanes, notably polydimethylsiloxanes, including at least two thiol groups such as those of formula (XIII).
  • the crosslinking agent is a (poly)acrylate compound.
  • n which may be identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the weight- average molecular weight of said polyorganosiloxane is between 1000 and 55 000 g.mol 1 .
  • - Y is as defined previously, and is preferably an oxygen atom.
  • the (poly)acrylate compound is combined in its implementation with an amine catalyst as described, for example, in Progress in coating 129, 21-25 (2019) and Progress in coating 135, 510-516 (2019).
  • the amine catalyst(s) are chosen from piperidine, DMAP (dimethylaminopyridine), DBU (1,8- diazabicyclo[5.4.0]undec-7-ene), DABCO (l,4-diazabicyclo[2.2.2]octane) and DBN (1,5- diazabicyclo[4.3.0]non-5-ene), more preferentially chosen from DBU (1,8- diazabicyclo[5.4.0]undec-7-ene), DABCO (l,4-diazabicyclo[2.2.2]octane) and DBN (1,5- diazabicyclo[4.3.0]non-5-ene), and in particular the catalyst is DBU (1,8- diazabicy clo [5.4.0] unde
  • the (poly)acrylate compounds are chosen from those of formula (XIV), notably trimethylolpropane triacrylate, and those of formula (XV), notably copolymers of dimethylsiloxanes and of acryloxypropylmethylsiloxanes.
  • the organometallic compound(s) are chosen from the alkoxides of formula (XIVa), in which M represents an atom chosen from transition metals, such as zirconium or titanium, metals of the lanthanide family, posttransition metals, such as aluminium or tin, metalloids, such as boron, and alkaline-earth metals, such as magnesium, preferably M represents a titanium atom; n represents the valency of the atom represented by M, notably 1, 2, 3 or 4, in particular 4; Ri represents a methyl, ethyl, 2-ethylhexyl, propyl, isopropyl, n-butyl, isobutyl or t-butyl group.
  • M represents an atom chosen from transition metals, such as zirconium or titanium, metals of the lanthanide family, posttransition metals, such as aluminium or tin, metalloids, such as boron, and alkaline-earth metals, such
  • said (poly)thiol compounds B) are chosen from a) poly dialkylsiloxanes bearing thiol functions, and b) alkoxysilanes bearing thiol functions, and in particular are chosen from a) poly dialkylsiloxanes bearing thiol functions, preferentially poly dimethylsiloxanes comprising thiol groups on the side chain (such as mercaptopropyl), notably those of formula (XIII).
  • crosslinking agent(s) is(are) chosen from:
  • chitosans such as poly(D-glucosamine)
  • R a and R b which may be identical or different, preferably identical, represent a (Ci- C4)alkyl group, in particular methyl, a (Ci-C4)alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(Ci-C4)alkyl group, in particular benzyl, or an aryl(Ci-C4)alkoxy group, in particular benzoxy, preferably a (Ci-C4)alkyl group, more preferentially methyl,
  • n and m which may be identical or different, represent an integer greater than 2, and in particular the values of m and n are such that the weight-average molecular weight of said polyorganosiloxane is between 1000 and 55 000 g.mol 1 ;
  • the cosmetic active agent(s) iv) is(are) chosen from: a) dyestuffs (or colouring agents), in particular chosen from pigments, direct dyes and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV-screening agents, and d) mixtures thereof.
  • the term “pigment” means any compound that is capable of imparting colour to keratin materials. These compounds have a solubility in water at 25 °C and at atmospheric pressure (760 mmHg) of less than 0.05% by weight, and preferably less than 0.01% by weight.
  • a pigment that is suitable for use in the invention may be chosen from organic pigments.
  • special effect pigments those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
  • the direct dyes are chosen from the compounds of formulae (E) and (F) below: [Chem 3]
  • the direct dyes are chosen from anionic direct dyes.
  • the dyestuffs may be present in concentrations ranging from 0.01% to 30% by weight, preferably from 0.02% to 20% by weight and more particularly from 0.05% to 15% by weight relative to the total weight of the composition containing them.
  • At least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used comprises one or more care active agents, preferably in a proportion of at least 0.01% by weight relative to the total weight of the composition considered.
  • the care active agent may be at least one hydrophilic active agent and/or one lipophilic active agent, and preferably a hydrophilic care active agent.
  • the care active agent(s) may in particular be present, in the composition containing same, in a content ranging from 0.01% to 30% by weight, relative to the weight of the composition, and preferably from 0.02% to 25% by weight.
  • lipophilic UV-screening agent means any cosmetic or dermatological screening agent that can be fully dissolved in molecular form in a liquid fatty phase or that can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.
  • insoluble UV-screening agent means any cosmetic or dermatological screening agent which is not defined either as a lipophilic UV-screening agent or as a hydrophilic UV- screening agent, and which is in the form of particles in aqueous phase or liquid fatty phase.
  • the UV-screening agents of the composition according to the invention may afford UVA and/or UVB photoprotection.
  • compositions which are preferably cosmetic compositions, may comprise at least one organic and/or mineral UV-screening agent (for screening out the UV radiation of sunlight).
  • the UV-screening agent(s) may be mineral UV-screening agents, which are generally pigments.
  • the pigments may or may not be coated.
  • the mineral UV-screening agents may be chosen from coated or uncoated pigments, and in particular from coated titanium oxide pigments, silicone-treated titanium oxides, uncoated titanium oxide pigments, uncoated zinc oxide pigments, coated zinc oxide pigments, uncoated cerium oxide pigments, uncoated iron oxide pigments, coated iron oxide pigments, and mixtures thereof.
  • compositions “Cl” to “C5” are free of mineral UV- screening agents.
  • the amount of the mineral UV-screening agent(s) present in compositions “Cl”, “C2”, “C3”, “C4” or “C5” according to the invention may range from 0.01% to 20% by weight relative to the total weight of the composition containing same. It ranges, for example, from 1% to 15% by weight, relative to the total weight of the composition.
  • compositions comprise a combination of UV- screening agents as described in patent FR 2 977 490, patent application WO 2013/004777 or patent application US 2014/0134120.
  • the process for treating keratin materials notably keratin fibres, and compositions “Cl”, “C2”, “C3”, “C4” or “C5” use or comprise one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof, preferably pigments; more preferentially, the pigment(s) of the invention are chosen from carbon black, iron oxides, notably yellow, red and black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and violet triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol red B, even more preferentially red iron oxides, yellow iron oxides and azo pigments, notably red azo pigments, such as D&C Red 7. substances
  • the process of the invention uses v) one or more fatty substances, in particular one or more oils, preferably volatile oils.
  • compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process of the invention contains a fatty phase.
  • compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process of the invention comprises one or more fatty substances, in particular one or more oils, preferably volatile oils.
  • oils refers to a fatty substance that is liquid at room temperature (20°C) and atmospheric pressure (760 mmHg).
  • hydrocarbon-based oil means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • the oil(s) v) is(are) chosen from volatile oils, in particular:
  • oils containing from 8 to 16 carbon atoms in particular branched Cs-Ci6 alkanes, in particular isoalkanes, more particularly isoalkanes (also known as isoparaffins), preferably C13-C16 isoparaffins, isododecane, isodecane, isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, alone or as mixtures, preferably isododecane (also known as 2,2,4,4,6-pentamethylheptane), linear alkanes, in particular C11-C16 alkanes, alone or as mixtures, in particular hexane, decane, undecane, tridecane, isoparaffins, in particular n-dodecane (C12) and n-tetradecane (C14), the undecanetridecane mixture, mixtures of n-undecane (C11) and n-tridecane mixture, mixture
  • esters containing from 3 to 8 carbon atoms in total, in particular ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate;
  • RT-O-C(O)-O-R’2 in which RT and R’2 independently denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group, advantageously chosen more preferentially from dibutyl carbonate or dipentyl carbonate;
  • Ri and R2 independently of each other, denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group;
  • silicone oils in particular comprising from 2 to 7 silicon atoms, and optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms, in particular dimethicones of viscosity 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof; more preferentially, the volatile oil(s) v) are chosen from Cs-C
  • compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process according to the invention comprises one or more non-volatile oils, preferably chosen from:
  • non-volatile silicone oils in particular chosen from non-volatile silicones having the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyl trimethicone, diphenylsiloxy phenyl trimethicone; and also mixtures thereof;
  • the non-volatile carbonate oils may be chosen from the carbonates of formula Rs-O- C(O)-O-R9, with Rs and R9, which may be identical or different, representing a linear or branched C4 to C12 and preferentially Cf> to C10 alkyl chain;
  • the carbonate oils may be dicaprylyl carbonate (or dioctyl carbonate), bis(2-ethylhexyl) carbonate, dipropylheptyl carbonate, dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate;
  • Branched alkyl groups that may be mentioned include a 1,1 -dimethylpropyl group, a 3-methylhexyl group, a 5-methylhexyl group, an ethylhexyl group, a 2-ethylhexyl group, a 5-methyloctyl group, a 1-ethylhexyl group, a 1-butylpentyl group, a 2-butyloctyl group, an isotridecyl group, a 2-pentylnonyl group, a 2-hexyldecyl group, an isostearyl group, a 2 -heptylundecyl group, a 2-octyldodecyl group, a 1,3- dimethylbutyl group, a l-(l-methylethyl)-2-methylpropyl group, a 1,1,3,3-tetramethylbutyl group, a 3,5,5-trimethylhex
  • the non-volatile oil(s) are chosen from hydrogenated or non-hydrogenated polyisobutenes, preferably hydrogenated, in particular the non-volatile compounds of the Parleam® range; mixtures of C15-C19 alkanes, and from linear aliphatic hydrocarbon-based esters of formula R-C(O)-OR’ in which R-C(0)-0 represents a carboxylic acid residue containing from 2 to 40 carbon atoms, and R’ represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms, as defined previously, in particular isononyl isononanoate.
  • the process of the invention uses one or more hydrocarbon-based oils containing from 8 to 16 carbon atoms, and notably branched Cs-Ci6 alkanes, in particular isoalkanes, preferably C13-C16 isoparaffins, isododecane, isodecane, isohexadecane, alone or as mixtures, and more preferentially isododecane.
  • hydrocarbon-based oils containing from 8 to 16 carbon atoms, and notably branched Cs-Ci6 alkanes, in particular isoalkanes, preferably C13-C16 isoparaffins, isododecane, isodecane, isohexadecane, alone or as mixtures, and more preferentially isododecane.
  • the process for treating keratin materials according to the invention uses water, and the composition(s) “Cl” to “C5” used in the process of the invention comprise water.
  • compositions “Cl”, “C2”, “C3”, “C4” and/or “C5”, preferably “Cl”, “C2” and/or “C3”, are aqueous-alcoholic.
  • they comprise an ethanol/water mixture, in particular in a volume ratio of between 1/99 and 99/1, more particularly between 10/90 and 90/10, even more particularly between 20/80 and 80/20, preferably 40/60 and 60/40, such as 50/50.
  • compositions “Cl”, “C2”, “C3”, “C4” or “C5” may be in anhydrous, water-in-oil emulsion or oil-in-water emulsion form.
  • a composition “Cl”, “C2”, “C3”, “C4” or “C5” may be in the form of a makeup product, in particular a coloured makeup product, for the skin, in particular a foundation, optionally having care properties, a blusher, a face powder, an eyeshadow, a concealer, an eyeliner; a lip makeup product such as a lipstick, optionally having care properties, a lip gloss or lip pencils; a makeup product for the integuments such as the nails or eyelashes, in particular in the form of a cake mascara, or for the eyebrows and the hair, or a product for the temporary tattooing of bodily skin.
  • the present invention is also directed towards a multicompartment kit or device, notably a cosmetic kit or device, comprising:
  • the locks of hair are left at room temperature for 18 hours at 80% relative humidity.
  • the hair is dyed uniformly and intensely.
  • compositions D makes it possible to significantly improve the colour persistence compared to the application of a “base coat” only (composition E) or of a “top coat” only (compositions F).
  • the deposits are then evaluated according to the protocols of resistance to olive oil, to sebum and to water, and of resistance to adhesive tape, of the formulations on Bioskin.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention relates to a process for treating keratin materials, comprising the application to said keratin materials, in one or more successive steps, of at least i) one or more compounds of formula (I), and also the optical or geometrical isomers thereof and/or the solvates thereof, such as hydrates, or a composition containing same in which formula (I) X, R1, R2, Rb, Rc, Rd, ALK, m and n are as defined in the description, ii) at least one crosslinking agent, iii) optionally water.

Description

Description
Title: Process for treating keratin materials using at least one alkoxysilane compound bearing acetoacetate functions and at least one crosslinking agent
Technical field
The present invention relates more particularly to the cosmetic field of keratin materials, and notably to that of caring for and/or making up the skin and/or lips and/or eyelashes and/or eyebrows, and that of caring for, styling and/or colouring keratin fibres and preferably the hair.
The aim is thus notably to propose novel treatment processes, notably cosmetic treatment processes, comprising the application to keratin materials of an alkoxysilane compound bearing acetoacetate functions and of a crosslinking agent, which are most particularly advantageous in terms of their technical performance, notably in terms of the resistance of the deposits they make it possible to obtain, and the sensorial experience they give the user.
Prior art
Cosmetic products conventionally require the use of one or more film-forming polymers in order to obtain a quality deposit of these products on keratin materials and in particular to satisfy the expectations detailed below.
Thus, in the field of skin and/or lip makeup, it is most particularly expected that the deposit formed does not transfer on contact with the fingers or clothing.
It must also have good staying power on contact with water, notably rain or during showering or even perspiration, and also with sebum, even on contact with food fats, notably food oils when this deposit is formed on the lips. Moreover, this deposit must be comfortable, or even glossy.
For this purpose, dispersions of polymer particles of nanometric size are used in makeup products such as mascaras, eyeliners, eyeshadows or lipsticks, and in hair application products, and more particularly in their organic and notably oily phases, as film-forming agent.
However, the compositions of the prior art have unsatisfactory hold, in particular styling hold, over time. Moreover, in the field of haircare, a new range of products known as “Hair Makeup” has recently been developed. These products guarantee temporary hair dyeing that lasts after 1 to 3 shampoo washes.
They are thus a particularly attractive alternative for consumers to permanent hair dyeing, provided, of course, that the colouring effect is effectively guaranteed to last after contact with water and a few shampoo washes.
This requirement is also notably satisfied by the use of effective film-forming agents.
Thus, FR 2 741 530 proposes for this purpose, for the temporary dyeing of keratin fibres, the use of a dispersion of film-forming polymer particles including at least one acidic function and at least one pigment dispersed in the continuous phase of said dispersion. The colourings obtained via this dyeing method nevertheless have the drawback of being removed easily on shampoo washing.
It is moreover proposed in FR 2 907 678 to perform coloured coating of the hair using a composition comprising a poly siloxane/poly urea block copolymer and a pigment. However, with such a composition, the coating results obtained are not always very homogeneous and the individualization of the hair strands is not always very good.
It is also known practice from patent EP 1 392 222 to use a cosmetic composition for caring for and/or treating keratin materials, comprising a supramolecular polymer including a polymer backbone and at least two groups that are capable of forming at least three hydrogen bonds, and from patent EP 1 435 900 to use a hair composition comprising a supramolecular polymer including a polymer backbone and at least two groups that are capable of forming at least three hydrogen bonds and a surfactant or a hair-conditioning agent. However, with these two composition alternatives, the obtained performance with respect to styling hold over time or with respect to water resistance remains insufficient.
Compositions and processes for forming deposits on keratin substrates having good staying power over time, using compounds bearing acetoacetate functions and functionalized active agents in order to be covalently bonded to the keratin materials, are also known from WO 2014/099108.
Moreover, Japanese document JP2003326843 describes inks for inkjet printing comprising polymers with amino groups and coupling agents of silane type.
In general, the processes and treatments described above do not make it possible to obtain deposits, either on keratin fibres or on the skin and lips, which satisfy all the abovementioned requirements, namely very good water resistance, in particular to shampoo washing for the hair, and/or to fatty substances notably for the lips, which are moreover comfortable to wear for the users, which make it possible to adjust the gloss or invisibility qualities and which, in the case of haircare use, provide very satisfactory styling hold or colour persistence.
Disclosure of the invention
There is thus still a need for a treatment process, notably a cosmetic treatment process, intended for application to the skin, which makes it possible to obtain a deposit that is non- tacky, which transfers little, if at all, and which is glossy, comfortable and persistent.
There is also still a need for a treatment process, notably a cosmetic treatment process, which allows deposits to be obtained that are resistant to water and fatty substances, in particular sebum.
There is also still a need for a treatment process, notably a cosmetic treatment process, which affords deposits that have shiny and invisibility qualities and/or a volumizing effect.
There is also a need for a colouring treatment process, notably a cosmetic treatment process, which is intended for application to the hair and which affords deposits that have good resistance to water and shampoo washing in order to ensure a colour persistence over time that is comparable to direct dyeing.
There is also a need for a treatment process, notably a cosmetic treatment process, notably a non-colouring treatment process, which is intended for application to the hair and which affords water-resistant styling properties, notably curl hold.
The present invention is specifically directed toward meeting all or some of these needs.
Summary of the invention
These problems are solved by performing a process for treating keratin materials, comprising the application to said keratin materials, in one or more successive steps, of at least: i) one or more compounds of formula (I), and also the optical or geometrical isomers thereof, and/or solvates thereof, such as hydrates, or a composition containing same: [Chem 1]
Figure imgf000005_0001
in which formula (I):
- X represents -O- or -N(Ra) with Ra representing a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom,
- R1 represents a (Ci-C6)alkyl group, in particular a (Ci-C4)alkyl group, preferably a (Ci- C2)alkyl group, such as methyl or ethyl, or a hydrogen atom,
- R2 represents a (Ci-C2)alkyl group, in particular methyl,
- Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Rb and Rc represent a hydrogen atom,
- Rd represents a linear or branched (Ci-C4)alkyl group, preferably Rd represents a methyl group,
- ALK represents an aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic or acyclic, divalent hydrocarbon-based group, comprising from 1 to 10 carbon atoms, in particular a saturated or unsaturated, preferably saturated, linear or branched, acyclic hydrocarbon-based chain, preferably comprising from 1 to 6 carbon atoms, preferably a (Ci- C4) alkylene group, such as propylene;
- m is equal to 0, 1 or 2, and
- n is equal to 1, 2 or 3, it being understood that the sum of (m + n) is 3; it being understood that:
- when n is 2 or 3, then the radicals R1 are identical or different, preferably identical, and
- when m is 2 or 3, then the radicals R2 are identical or different, preferably identical; and ii) at least one crosslinking agent; iii) optionally water, preferably water.
According to a preferred embodiment, the treatment process of the invention comprises the application iii) of water to said keratin materials.
According to a preferred embodiment, the treatment process of the invention also comprises the application of at least iv) a cosmetic active agent, to said keratin materials. According to a preferred embodiment, the process according to the invention comprises the application i) of at least one compound of formula (I), the optical or geometrical isomers thereof, and/or the solvates thereof, such as hydrates, or of a composition containing same, the application ii) of at least one crosslinking agent, iii) of water and the application iv) of at least one cosmetic active agent, to said keratin materials.
The water iii) may be applied at the same time as i), as ii) or as iv), when iv) is present, or even at the same time as i) and as ii), and as optionally iv).
The water iii) may also be applied before i), ii) and optionally iv). The keratin materials may thus be damp or wet before application of i), of ii) and possibly of iv). By way of example, steps i), ii) and optionally iv), may be performed on damp keratin fibres, such as fibres just wrung out, for example after a shampoo wash, or on damp skin.
According to one embodiment, the process comprises the application of i), ii) and optionally iv) to damp or wet keratin materials.
According to another embodiment, the process comprises the application of i), ii), iii) and optionally iv) to dry keratin materials. According to this embodiment, the application of iii) is preferably carried out at an acidic pH, below 7, the water iii) then being acidified by at least one organic or mineral acid, in particular hydrochloric acid, lactic acid and/or citric acid.
The inventors thus found, surprisingly, that the application to keratin materials of the ingredients i), ii), and optionally iii) and iv), makes it possible to obtain deposits on the skin which have good resistance to external attacking factors, for instance water, oils, notably food oils, sweat and/or sebum, and which are thus endowed with very good staying power over time. Advantageously, the deposits obtained via the processes according to the invention are also very comfortable. Applying ingredients i), ii), and possibly iii) and iv) to keratin materials also affords deposits on the keratin fibres which show good resistance to shampoo washing and to water.
Definitions
For the purposes of the present invention, and unless otherwise indicated:
- For the purposes of the present invention, the term “keratin materials” is intended to denote notably the lips, skin, nails and keratin fibres, in particular the eyelashes, eyebrows and the hair, preferably the lips and/or the hair. - The term “cosmetic active agent” means an organic or organosilicon compound or a mineral compound which can be incorporated into a cosmetic composition to give an effect on keratin materials, whether this effect is immediate or provided by repeated applications. As examples of cosmetic active agents, mention may be made of coloured or uncoloured, fluorescent or non-fluorescent compounds such as optical brighteners, or UVA and/or UVB screening agents, anti-ageing active agents or active agents intended for providing a benefit to the skin such as active agents having action on the barrier function, deodorant active agents, antiperspirant active agents, desquamating active agents, antioxidant active agents, moisturizing active agents, sebum-regulating active agents, active agents intended for combating the effects of pollution, antimicrobial or bactericidal active agents, fragrances and dyestuffs such as direct dyes or pigments, preferably pigments.
Preferentially, the cosmetic active agents are chosen from a) dyestuffs chosen from pigments, direct dyes, and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV- screening agents, and d) mixtures thereof.
- For the purposes of the present invention, the term “fatty substance” means an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1% and even more preferentially less than 0.1%); in addition, the fatty substances are soluble in organic solvents under the same temperature and pressure conditions, for instance in halogenated solvents such as chloroform or dichloromethane, lower alcohols such as ethanol or aromatic solvents such as benzene or toluene.
- The term “(hetero)aryl” means aryl or heteroaryl groups.
- The term “(hetero)cycloalkyl” means cycloalkyl or heterocycloalkyl groups.
- The “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from:
• a Ci-C6 and preferably C1-C4 (poly)(hydroxy)alkyl radical;
. a halogen atom such as chlorine, fluorine or bromine;
. a hydroxyl group;
• a C1-C2 alkoxy radical; a C2-C4 (poly)hydroxyalkoxy radical;
. an amino radical;
. an amino radical substituted with one or two identical or different Ci-Ce and preferably C1-C4 alkyl radicals; . an acylamino radical (-N(R)-C(O)-R’) in which the radical R is a hydrogen atom;
• a C1-C4 alkyl radical and the radical R’ is a C1-C4 alkyl radical; a carbamoyl radical ((R)2N-C(O)-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;
. an alkylsulfonylamino radical (R’-S(O)2-N(R)-) in which the radical R represents a hydrogen atom or a C1-C4 alkyl radical and the radical R’ represents a C1-C4 alkyl radical, or a phenyl radical;
. an aminosulfonyl radical ((R)2N-S(O)2-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;
. a carboxylic radical in acid form or salified (preferably with an alkali metal or a substituted or unsubstituted ammonium) form;
. a cyano group (CN);
. a polyhalo(Ci-C4)alkyl group, preferentially trifluoromethyl (CF3).
- The cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the following groups:
. hydroxyl,
• C1-C4 alkoxy, C2-C4 (poly )hydroxy alkoxy;
. alkylcarbonylamino ((R-C(O)-NR’-), in which the radical R’ is a hydrogen atom or a C1-C4 alkyl radical and the radical R is a C1-C2 alkyl radical, amino substituted with one or two identical or different C1-C4 alkyl groups;
. alkylcarbonyloxy ((R-C(O)-O-), in which the radical R is a C1-C4 alkyl radical, amino substituted with one or two identical or different C1-C4 alkyl groups;
. alkoxycarbonyl ((R-O-C(O)-) in which the radical R is a C1-C4 alkyl radical, amino substituted with one or two identical or different C1-C4 alkyl groups;
- A cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted with one or more oxo groups.
- A hydrocarbon-based chain is unsaturated when it includes one or more double bonds and/or one or more triple bonds.
- An “aryl” radical represents a monocyclic or fused or non-fused polycyclic hydrocarbonbased group comprising from 6 to 14 carbon atoms, and at least one ring of which is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl. - A “heteroaryl” radical represents a monocyclic or fused or non-fused polycyclic, 5- to 14- membered group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl and xanthylyl.
- A “cyclic” or “cycloalkyl” radical is a monocyclic or fused or non-fused polycyclic, nonaromatic cyclic hydrocarbon -based radical containing from 5 to 14 carbon atoms, which may include one or more unsaturations; the cycloalkyl is preferably a cyclohexyl group.
- A “heterocyclic” or “heterocycloalkyl” radical is a monocyclic or fused or non-fused polycyclic 3- to 9-membered non-aromatic cyclic radical, including from 1 to 4 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms; preferably, the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidyl, morpholinyl and dithiolane.
- An “alkyl” radical is a linear or branched, in particular C i -Ce and preferably C1-C4 saturated hydrocarbon-based radical.
- An “alkoxy” radical is an alkyl-oxy radical for which the alkyl radical is a linear or branched Ci-Ce and preferentially C1-C4 hydrocarbon-based radical.
- A “(poly)(hydroxy)alkyl” radical denotes a Ci-Ce and preferably C1-C4 alkyl radical optionally substituted with one or more hydroxyl radicals, preferably substituted with from 1 to 4 hydroxyl groups, more particularly between 1 and 3.
- An “anionic counterion” is an anion or an anionic group associated with the cationic charge; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including Ci-Ce alkylsulfonates: Alk-S(O)2O“ such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: Ar-S(O)2O“ such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-O-S(O)O’ such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-O-S(O)O’ such as benzene sulfate and toluene sulfate; xi) alkoxy sulfonates: Alk-0-S(0)20’ such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O- S(O)2O'; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.
- The “solvates” represent hydrates and also the combination with linear or branched C1-C4 alcohols such as ethanol, isopropanol or n-propanol.
- The term “UV-A screening agent” means a chromophore derived from a compound which screens out (or absorbs) UV-A ultraviolet rays at a wavelength of between 320 and 400 nm. A distinction may be made between short UV-A screening agents (which absorb rays at a wavelength of between 320 and 340 nm) and long UV-A screening agents (which absorb rays at a wavelength of between 340 and 400 nm).
- The term “UV-B screening agent” means a chromophore derived from a compound which screens out (or absorbs) UV-B ultraviolet rays at a wavelength of between 280 and 320 nm.
- The term “ chromophore” means a radical derived from a colourless or coloured compound that is capable of absorbing UV and/or visible radiation at a wavelength Xabs of between 250 and 800 nm. Preferably, the chromophore is coloured, i.e. it absorbs wavelengths in the visible range, i.e. preferably between 400 and 800 nm. Preferably, the chromophores appear coloured to the eye, particularly between 400 and 700 nm (Ullmann’s Encyclopedia, 2005, Wiley-VcH, Verlag “Dyes, General Survey”, § 2.1 Basic Principle of Color);
- The term "'anhydrous composition” means that said composition contains an amount of less than 5% by weight of water, preferentially less than 3% by weight of water, better still less than 1% by weight of water, relative to the total weight of the composition in question; even more preferentially, the composition under consideration is free of water.
- The terms “colouring agent” and “dyestuff’ are equivalent.
It is understood that the treatment processes according to the invention, and also the compositions used, are non-therapeutic.
Detailed description
PROCESS FOR TREATING KERATIN MATERIALS
The first subject of the invention is a treatment process in one or more steps using, on keratin materials, notably keratin fibres or the skin: i) at least one compound of formula (I), as defined previously and hereinbelow, or a composition containing same; ii) at least one crosslinking agent, in particular as defined hereinbelow; iii) optionally water, preferably water; and iv) optionally at least one cosmetic active agent, in particular as defined hereinbelow.
According to a particular embodiment of the invention, the treatment process according to the invention involves the simultaneous application of the ingredients i), ii), optionally iii), and optionally iv).
According to another particular embodiment of the invention, the treatment process according to the invention comprises at least two steps in which the ingredients i), ii), optionally iii), and optionally iv) are applied in separate and successive steps to the keratin materials, it being understood that the cosmetic active agent(s) iv) may be present together with the ingredient i) and/or with the ingredient(s) ii) and/or with the ingredient iii), when it is present.
According to a particular embodiment, the ingredient(s) i) are applied to the keratin materials, and the ingredient(s) ii) are then applied to the keratin materials, it being understood that the ingredient iii), if it is present, may be applied with i) and/or with ii) and or with iv), when iv) is present, and that the ingredient(s) iv), when they are present, may be applied together with i) and/or ii) and/or iii), preferably with i) and/or ii).
According to another particular embodiment, the ingredient(s) ii) are applied to the keratin materials, and the ingredient(s) i) are then applied to the keratin materials, it being understood that the ingredient iii), when it is present, may be applied with i) and/or with ii) and/or with iv), when iv) is present, and that the ingredient(s) iii), when they are present, may be applied together with i) and/or ii).
According to a particular embodiment of the invention, the process for treating keratin materials is a process, notably a cosmetic process, for treating keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair.
According to a particular embodiment of the invention, the process for treating keratin materials is a cosmetic process for caring for, styling and/or colouring keratin fibres, preferably the hair.
According to another embodiment of the invention, the process for treating keratin materials is a process for caring for the skin. According to another embodiment of the invention, the process for treating keratin materials is a process for making up the skin, lips, eyelashes and eyebrows. According to this embodiment, the process comprises at least one cosmetic active agent chosen from dyestuffs, preferably pigments.
According to one aspect of the invention, the process for treating keratin materials according to the invention using the ingredients i), ii), optionally iii), and optionally iv), is a treatment for colouring keratin fibres.
According to another aspect of the invention, the process for treating keratin materials according to the invention using the ingredients i), ii), optionally iii) and optionally iv), is a process for caring for the skin.
According to one embodiment of the invention, the process according to the invention is a process for treating, notably for cosmetically treating, keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the application to said keratin materials of at least:
- a composition, termed “Cl”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow;
- a composition, termed “C2”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow;
- a composition, termed “C3”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow, and optionally iii) water;
- a composition, termed “C4”, comprising ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow, and optionally iii) water;
- a composition, termed “C5”, comprising iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow, and optionally iii) water; it being understood that: • the process uses, together or separately, i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, and optionally iii) water, and preferably water; and
• the compositions “Cl”, “C2”, “C3”, “C4” and “C5” may be anhydrous, aqueous, in particular aqueous -alcoholic, and/or comprise one or more fatty substances v), in particular as defined previously and hereinbelow.
According to one aspect of the invention, the process for treating keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, uses a composition, termed “Cl”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, optionally iii) water and optionally iv) at least one cosmetic active agent, in particular as defined hereinbelow, notably chosen from a) colouring agents, such as pigments, direct dyes, and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV-screening agents, and d) mixtures thereof, and notably at least one colouring agent, more particularly at least one pigment, preferably said composition “Cl” comprising iii) water.
According to another aspect, the process for treating keratin materials according to the invention, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, uses a composition, termed “C2”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously, preferably, said composition “C2” comprising iii) water.
According to another aspect, the process for treating keratin materials according to the invention, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, uses a composition, termed “C3”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, ii) at least one crosslinking agent, in particular as defined hereinbelow, iv) at least one cosmetic active agent, in particular as defined previously, and optionally iii) water, preferably said composition “C3” comprising iii) water. According to another aspect, the process for treating keratin materials according to the invention, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, uses a composition termed “Cl” and a composition termed “C4”, said composition “Cl” comprising i) at least one compound of formula (I), as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow, and said composition “C4” comprising ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow, preferably said process using a composition “Cl” comprising iii) water.
According to another variant of the process of the invention, the ingredient(s) i), optionally iii), and optionally iv) are applied together, i.e. simultaneously, to the keratin materials during a first step, and then, during a subsequent step, the ingredient(s) ii), optionally iii), and optionally iv) are applied to said materials.
According to a particular embodiment, the process according to the invention comprises two successive steps in which two different compositions are applied to said keratin materials. According to a particular embodiment of the process, during the first step a composition “Cl” is applied to the keratin materials, and a composition “C4” is then applied to said keratin materials.
According to yet another variant of the process of the invention, the ingredient(s) ii) and optionally iv) is(are) applied to the keratin materials, and then the ingredient(s) i), and optionally iv) at least one cosmetic active agent, in particular as defined previously, are applied to said keratin materials. In particular, composition “C4” is applied to the keratin materials and composition “Cl” is then applied, preferably composition “Cl” contains iii) water.
According to another variant of the process according to the invention, a composition “Cl” containing i), and iii) water, is applied, and sequentially a composition “C4” containing ii), optionally iii), and optionally iv), preferably composition “Cl” being applied before composition “C4”.
According to another variant of the process according to the invention, a composition “C2” containing i) at least one compound of formula (I), ii) at least one crosslinking agent, optionally iii) water, and optionally iv) at least one cosmetic active agent, is applied, and sequentially a composition “C4” containing ii) at least one crosslinking agent, optionally iii) water, and optionally at least one cosmetic active agent iv), composition “C2” preferably being applied before composition “C4”, and it being understood that the crosslinking agent(s) contained in composition “C2” may be identical to or different from the crosslinking agent(s) contained in composition “C4”; preferably, the crosslinking agent(s) are different. Compositions “Cl”, “C2”, “C3”, “C4” and/or “C5” of the process according to the invention, which comprise at least one fatty substance, notably at least one oil, and water, may be in the form of a direct or inverse emulsion.
Compositions “Cl”, “C2”, “C3”, “C4” and/or “C5” of the process according to the invention may thus be applied directly as such to the target keratin materials or may even be formed directly on the surface of these keratin materials.
According to the invention, three application methods known as the “one-gesture application mode”, the “two-gesture application mode” and the “three-gesture application mode” are thus distinguished.
According to one embodiment of the process of the invention, the process is performed in one gesture by applying composition “C2” or “C3”, as defined previously, to the keratin materials.
Thus, according to one embodiment, the treatment process according to the invention comprises a single step of applying composition “C2” or composition “C3” to said keratin materials.
The term “one-gesture application mode” means the direct application to the target keratin materials of a single composition in accordance with the invention, namely composition “C2” or “C3”.
After application of composition “C2” or “C3”, a persistent, non-tacky deposit is advantageously obtained. The deposit obtained is also resistant to food oils, water, sebum and friction.
According to another embodiment of the process of the invention, the process is performed in two gestures.
The term “two-gesture application mode” means the successive application, to the target keratin material, of two different compositions, for example “Cl” and “C4”, or “C2” and “C4”, or “C3” and “C4”, preferably “Cl” and then “C4”, “C2” and then “C4”, or “C3” and then “C4”. According to another embodiment, the process of the invention is performed in three gestures.
The term “three-gesture application mode” means the sequential application of three different compositions “Cl” to “C5”. According to this application mode, for example, according to one embodiment, successive application is performed on the keratin materials, a) of a composition “Cl”, then P) of a composition “C4”, then y) of a composition “C5”, preferably “Cl” then “C4” or, respectively, “C5” or “C5” or, respectively, “C4”.
According to another embodiment, sequential application is performed on the keratin materials, a) of a composition, for example “C4”, and P) of a composition “Cl” or “C2”, and also y) of a composition “C5”, preferably composition “C4” is applied before composition “Cl”.
In the two- or three-gesture application modes, the composition applied first, for example “Cl”, is conventionally referred to as the “base coat”, and the composition(s) superposed thereon are generally referred to as the “top coat”.
After application of the various compositions “Cl” to “C5”, a persistent, non-tacky deposit is advantageously obtained. The deposit obtained is also resistant to food oils, water and shampoo washing.
According to a particular embodiment, the compositions are applied to dry keratin materials. According to a particular embodiment, the compositions are applied to damp or wet keratin materials, i.e. keratin materials containing water on the surface.
According to a particular embodiment, the keratin materials are dried after application of compositions “Cl” to “C5”, in particular after application of each different composition. The drying step can be implemented with a drying device such as a helmet, a hair dryer or a climazon. When the drying step is implemented with a helmet or a hair dryer, the drying temperature is comprised between 40 °C and 110 °C, preferably between 50 °C and 90°C. After the drying step, a step of shaping the keratin fibers can be implemented with a hair straightener (“fer a lisser”), a straightening or curling iron or a steam iron, preferably a hair straightener or a steam iron. Preferably, the step of shaping the keratin fibres is carried out at a temperature ranging from 120 °C to 230 °C, notably from 150 °C to 210 °C, even more preferentially from 160 °C to 210 °C, better from 180 °C to 210 °C. The iron can be applied to the keratin fibers in successive separate touches of a few seconds, or by progressive movement or sliding along the hair. Preferably, the application of the iron is done in continuous movement from the root to the tip of the hair, in one or more passes.
According to one aspect, the present invention relates to a process, notably a cosmetic process, for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising a step of applying to the skin or said lips or the eyelashes or the eyebrows a composition “C2” or “C3”, notably containing at least one dyestuff, in particular as defined previously, and more particularly at least one pigment.
According to another of its aspects, the present invention relates to a cosmetic treatment process for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the successive application of at least:
- a composition, termed “Cl”, comprising i) at least one compound of formula (I), as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow; and then
- a composition, termed “C4”, comprising ii) at least one crosslinking agent, in particular as defined previously and hereinbelow, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously and hereinbelow; at least one of the compositions “Cl” and/or “C4” containing at least one dyestuff, in particular as defined previously and hereinbelow, preferably at least one pigment, and more preferentially composition “Cl” comprises at least one pigment.
According to another of its aspects, the present invention relates to a cosmetic treatment process for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the successive application of at least:
- a composition “Cl” as defined previously; and then
- a composition “C4” as defined previously; and then
- a composition “C5” as defined previously; it being understood that compositions “Cl” and/or “C4” and/or “C5” contain at least one dyestuff, in particular as defined hereinbelow, preferably at least one pigment. Preferably, composition “C5” comprises at least one pigment. According to another of its aspects, the present invention relates to a cosmetic treatment process for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the successive application of at least:
- a composition “C2” or “C3” as defined previously; and
- a composition “C4” as defined previously; it being understood that compositions “C2” or “C3” contain at least iv) one dyestuff, in particular as defined hereinbelow, and/or composition “C4” contains at least one dyestuff, in particular as defined hereinbelow; preferably composition “C2” or “C3” comprises at least one pigment.
COMPOUNDS OF FORMULA (I)
As indicated above, the treatment process according to the invention involves applying to keratin materials at least one or more compounds of formula (I) as defined previously.
According to a particular embodiment, the compound(s) of formula (I) according to the invention are such that Rb and Rc, which may be identical or different, represent a hydrogen atom and Rd represents a linear or branched (Ci-C4)alkyl group, preferably Rd represents a methyl group.
According to a particular embodiment, the compound(s) of formula (I) according to the invention are such that ALK represents a saturated or unsaturated, linear or branched, acyclic, divalent hydrocarbon-based group, comprising from 1 to 6 carbon atoms, preferably a (Ci-C4)alkylene group, more preferentially propylene.
More particularly, the compound(s) of formula (I) are of formula (I’), and also the optical and geometrical isomers thereof, and the solvates thereof, such as the hydrates: [Chem 2]
Figure imgf000018_0001
in which formula (I’) R1, R2, X, m and n are as defined in formula (I).
According to a preferred embodiment, the compound(s) of formula (I) or (I’) are such that X represents -O-. According to another preferred embodiment, the compound(s) of formula (I) or (I’) are such that X represents a group -N(Ra)- with Ra as defined previously, preferably X represents a group -N(H)-.
According to a preferred embodiment, the compound(s) of formula (I) or (I’) are such that R1 represents a (Ci-C4)alkyl group, preferably a (Ci-C2)alkyl group.
Preferably, the compound(s) of formula (I) or (I’) are such that R1 represents a methyl group. Preferably, the compound(s) of formula (I) or (I’) are such that R1 represents an ethyl group. According to a preferred embodiment, the compound(s) of formula (I) or (I’) are such that R1 represents a hydrogen atom. According to a preferred embodiment, the compound(s) of formula (I) or (I’) are such that R2 represents a (Ci-C2)alkyl group. Preferably, the compound(s) of formula (I) or (I’) are such that R2 represents a methyl group.
According to a preferred embodiment, the compound(s) of formula (I) or (I’) are such that m is equal to 0 or 1, in which case n is 3 or 2 respectively. Preferably, m is equal to 0 and n is 3.
According to a preferred embodiment, the compound(s) of formula (I) or (I’) are chosen from the compounds illustrated in the table below, and mixtures thereof: [Table 1]
Figure imgf000020_0001
Table 1
According to a preferred embodiment, the compound(s) of formula (I) or (I’) is at least 3- (triethoxysilyl)propyl 3-oxobutanoate.
The compound(s) of formula (I) or (I’) as defined previously are preferably present in a content ranging from 0.2% to 99% by weight, in particular from 0.3% to 60% by weight, more particularly from 0.5% to 20% by weight, relative to the total weight of composition “Cl”, “C2” or “C3” containing same.
The compound(s) of formula (I) or (I’) can be obtained according to methods known to those skilled in the art. For example, the compound(s) of formula (I) or (I’) may be synthesized according to the routes described in JP2005314325, JP2016069290, WO2014027766, US20190315778, or in the publication “Photoactive Diazoketo-Functionalized Self- Assembled Monolayer for Biomolecular Patterning”, Langmuir (2009), 25(16), 8888-8893. WATER-SOLUBLE SOLVENT
The compound(s) of formula (I) may be used in a medium containing at least one water- soluble solvent.
According to a preferred embodiment of the invention, the compound(s) of formula (I) are used in a medium containing at least one water-soluble solvent.
According to a preferred embodiment of the invention, the compound(s) of formula (I) are used in a medium containing at least one water-soluble solvent and iii) water.
In the present invention, the term “water-soluble solvent” denotes a compound which is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25°C and atmospheric pressure), i.e. forms a homogeneous mixture after mixing with water.
The water-soluble solvents that can be used in the process of the invention may also be volatile.
According to a preferred embodiment, the water-soluble solvents are polar protic solvents, in particular chosen from (poly)hydroxy(C2-C6)alkanes, preferably (C2-C4)alkanols, preferably ethanol.
Among the water-soluble solvents that can be used in the process according to the invention, mention may notably be made of the lower monoalcohols having from 2 to 5 carbon atoms, such as ethanol and isopropanol, the glycols having from 2 to 8 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol.
In particular, a process according to the invention uses as water-soluble solvent a lower monoalcohol having from 2 to 4 carbon atoms, and preferably ethanol.
A composition used in the treatment process according to the invention, in particular a composition “Cl”, “C2”, “C3”, “C4” and/or “C5”, preferably comprises one or more water- soluble solvents, more preferentially ethanol, in a content ranging from 5% to 90%, better still from 10% to 85% by weight, preferably from 25% to 80% by weight, relative to the total weight of said composition.
CROSSLINKING AGENT The treatment process according to the invention as described previously comprises the application to keratin materials of (i) at least one or more compounds of formula (I), and (ii) at least one crosslinking agent.
For the purposes of the invention, the term “crosslinking agent”, also termed “R”, denotes a compound that is capable of establishing with at least one acetoacetate function of the compound(s) of formula (I) used in the treatment process according to the invention: at least one covalent bond, at least one donor-acceptor (dative) bond, and/or at least one coordination bond, and thus of crosslinking this or these compound(s).
Preferably, the term “crosslinking agent”, also termed “R”, refers to a compound that is capable of establishing at least one covalent bond with an acetoacetate function of the compound(s) of formula (I) used in the treatment process according to the invention and thus of crosslinking this or these compound(s).
For the purposes of the present invention, it is understood that the terms “crosslinking agent” and “crosslinker” are equivalent.
Compositions “C2”, “C3” and “C4” as defined previously contain at least a crosslinking agent. The compositions of the invention may be aqueous-alcoholic compositions. They may comprise a fatty phase, an aqueous phase or may be in the form of a direct or inverse emulsion. Composition “C4” may be an aqueous composition.
According to one aspect, the treatment process of the invention uses a composition termed “C3”, in particular a cosmetic composition for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising i) at least one compound of formula (I) as defined previously, ii) at least one crosslinking agent, iv) at least one cosmetic active agent, notably as defined previously, in particular at least one colouring agent, more particularly at least one pigment, and optionally iii) water, preferably water.
The crosslinking agent(s) are preferably present in a mass content ranging from 0.2% to 60% by weight, in particular ranging from 0.5% to 40% by weight, more particularly from 1% to 20% by weight, even more particularly from 1% to 10% relative to the total weight of the composition containing same. In particular, the crosslinking agent(s) and the compound(s) of formula (I) are preferably present in a mass content ranging from 1% to 35% by weight, relative to the total weight of the composition comprising them.
More precisely, the crosslinking agent(s) R that are suitable for use in the invention may be chosen from compounds bearing amine, thiol, and/or acrylate functions. A crosslinking agent R may also denote a metal alkoxide.
Thus, according to a particular embodiment, the crosslinking agent R is chosen from (poly)amine, (poly)thiol, (poly)acrylate and metal alkoxide compounds, and mixtures thereof, and preferably chosen from (poly)amine, (poly)thiol and (poly)acrylate compounds, and mixtures thereof.
The term “(poly)amine, (poly)thiol and (poly)acrylate compounds” is intended to denote compounds including at least one primary or secondary amine, thiol or acrylate function, respectively.
The metal alkoxide compounds are defined below.
Figure imgf000023_0001
According to a preferred embodiment, the crosslinking agent R is chosen from (poly)amine compounds.
The (poly)amine compound may be chosen in particular from polyamine compounds bearing several primary and/or secondary amine groups or from amino alkoxysilanes, and more particularly from amino alkoxysilane compounds, diamine compounds, triamine compounds, and mixtures thereof.
The (poly)amine compound may be a compound comprising from 2 to 20 carbon atoms, notably a nonpolymeric compound; they may be acyclic or cyclic, linear or branched, saturated or unsaturated, conjugated or non-conjugated, aromatic or non-aromatic, optionally interrupted with one or more heteroatoms chosen from O, S, Si(R’)2, N(R”) preferably O, Si(R’)2, or combinations thereof such as -Si(R’)2-O- or -O-Si(R’)2-, with R’, which may be identical or different, representing a (Ci-C4)alkyl group such as methyl, and R” representing a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom.
The term “non-polymeric compound” means a compound which is not directly obtained via a monomer polymerization reaction. (Poly)amine compounds that may be mentioned in particular include N-methyl-1,3- diaminopropane, N-propyl- 1,3 -diaminopropane, N-isopropyl- 1,3 -diaminopropane, N- cyclohexyl-l,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2- aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methylbis(3- aminopropyl)amine, N-(3-aminopropyl)-l,4-diaminobutane, N,N- dimethyldipropylenetriamine, 1 ,2-bis(3-aminopropylamino)ethane, N,N’ -bis(3- aminopropyl)-l,3-propanediamine, ethylenediamine, 1,3 -propylenediamine, 1,4- butylenediamine, lysine, cystamine, xylenediamine, tris(2-aminoethyl)amine, 1,3- bis(aminomethyl)cyclohexane, 1 ,4-bis(aminomethyl)cyclohexane, diaminopropanol, 4,7,10-trioxa-l,13-tridecanediamine, spermidine and C36-alkylenediamines (Priamine™ 1071, 1073, 1074, 1075, respectively).
According to a particular embodiment of the invention, the (poly)amine compounds are monoamine compounds, i.e. they contain only one primary and/or secondary amine group, preferably a primary amine group (NH2).
The (poly)amine compound(s) may be chosen from amino alkoxysilanes, notably of formula RTSi(OR’2)z(R’3)x in which:
- RT is a linear or branched, saturated or unsaturated, cyclic or acyclic Ci-Ce hydrocarbon-based chain substituted with a group chosen from primary amine groups NH2 or secondary amine groups -N(H)R with R representing a C1-C4 alkyl, an aryl or a benzyl substituted with an amino group or with a C1-C4 aminoalkyl group; RT may be interrupted in its chain with a heteroatom (O, S, NH) or a carbonyl group (CO), R being linked to the silicon atom directly via a carbon atom,
- R’2 and RT, which may be identical or different, represent a linear or branched (Ci- Ce) alkyl group,
- z denotes an integer ranging from 1 to 3, and
- x denotes an integer ranging from 0 to 2, with z + x = 3.
In particular, R’ 1 is an acyclic chain. Preferably, RT is a linear or branched, saturated or unsaturated Ci-Ce hydrocarbon-based chain substituted with an amine -NH2 or -N(H)R group, with R representing a Ci-Ce alkyl, a C3-C6 cycloalkyl or a Cf> aromatic group. More preferentially, RT is a saturated linear Ci-Ce hydrocarbon-based chain substituted with an amine group NH2. Even more preferentially, R’ 1 is a saturated linear C2-C4 hydrocarbonbased chain substituted with an amine group NH2.
In particular, R’2 represents an alkyl group comprising from 1 to 4 carbon atoms; preferably, R’2 represents a linear alkyl group comprising from 1 to 4 carbon atoms and more preferentially R’2 represents an ethyl group.
In particular, R’3 represents an alkyl group comprising from 1 to 4 carbon atoms; preferably, R’3 represents a linear alkyl group comprising from 1 to 4 carbon atoms and more preferentially R’3 represents methyl or ethyl groups. Preferably, z is equal to 3.
In particular, the (poly)amine compound(s) are chosen from amino alkoxysilanes including only one primary and/or secondary, preferably primary (NH2), amine group, such as 3- aminopropyltriethoxysilane (APTES), 3 -aminoethyltriethoxy silane (AETES), 3- aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m- aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, and N-(2- aminoethylaminomethyl)phenethyltrimethoxysilane.
Preferably, the (poly)amine compound(s) are chosen from 3 -aminopropyltriethoxy silane (APTES), 3 -aminoethyltriethoxy silane (AETES), 3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferentially 3- aminopropyltriethoxysilane (APTES), in particular the product sold by Sigma Aldrich.
The (poly)amine compound may also be chosen from amino polymers, notably having a weight-average molecular weight ranging from 500 g.mol 1 to 1 000000 g.moT1, preferably ranging from 500 g.mol 1 to 500000 g.mol 1, and preferentially ranging from 500 g.mol 1 to 100000 g.mol 1.
According to a particular embodiment of the invention, the (poly)amine compounds are monoamine compounds and are chosen from polydialkylsiloxanes notably of formula (IV): H2N-ALK-Si(R’2)(R’3)-O-[ Si(R’2)(R’3)-O]n- Si(R’2)(R’3)-R’4 (IV) in which formula (IV):
- ALK represents a (C1-C4) alkylene group which is linear or branched, preferably linear, such as propylene,
- R’2 and R’3, which may be identical or different, preferably identical, represent a (Ci- C4)alkyl group, such as methyl, and
- R’4 represents a linear or branched (Ci-C6)alkyl group, preferably C4, such as n-butyl, n represents an integer greater than or equal to 2, preferably the value of n is such that the weight-average molecular weight of the polydimethylsiloxane ranges from 500 to 3000 g. mol 1. As examples of polydimethylsiloxanes (V), mention may be made of the products sold under the names “MCR-A11” and “MCR-A12” by the company Gelest.
According to a particular embodiment of the invention, the (poly)amine compounds are diamine compounds, i.e. they contain two primary and/or secondary amine groups, preferably primary amine groups (NH2).
More particularly, they are chosen from the compounds of formula (V) or (VI):
. ALK[(O-ALK’)m-NH2]2 (V) or
. H2N-ALK-Si(R’)2-[O-Si(R’)2]m-O-Si(R)2-ALK’-NH2 (VI) in which formulae (V) and (VI):
- ALK and ALK’, which may be identical or different, represent a linear or branched (Ci- C6)alkylene group, preferably a linear group such as propylene,
- R’, which may be identical or different, represents a (Ci-C4)alkyl group such as methyl,
- m represents an integer greater than or equal to 0; preferably, the value of m is such that the weight- average molecular weight of compound (V) or (VI) ranges from 500 g.mol 1 to 55 000 g.mol 1.
As examples of compounds of formula (VI), mention may be made of those sold under the names DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32 and DMS-A35 by the company Gelest.
The (poly)amines compounds that are diamines are particularly polyether diamines notably of formula H2N-ALK-O-[ALK’-O]m-ALK”-NH2 with ALK, ALK’ and ALK”, which may be identical or different, representing a linear or branched (Ci-C6))alkylene group, and m representing an integer greater than or equal to 0, such as 4,7,10-trioxa-l,13- tridecanediamine or the compounds known under the reference Jeffamine from the company Hunstman, and more particularly a,co-diamino polyethylene glycol and/or polypropylene glycol (with an amine function at the end of the chain) such as the products sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000 and ED-2003.
According to a particular embodiment of the invention, the (poly)amine compound(s) are triamine compounds, i.e. they contain three primary and/or secondary amine groups, preferably primary amine groups (NH2). More particularly, they are chosen from polyether triamines notably of formula ALK”’[(O-ALK’)m-NH2]3 with ALK’ as defined previously and ALK”’ representing a linear or branched trivalent (Ci-C6)alkylene group, and m representing an integer greater than or equal to 0.
As (poly)amine compounds that are triamine compounds, mention may be made in particular of polyether triamines, and notably a,co-triamino polyethylene glycol and/or polypropylene glycol (with an amine function at the end of the chain) such as the products sold under the names Jeffamine T-403.
According to another particular embodiment of the invention, the (poly)amine compound(s) include more than three primary and/or secondary amine groups, preferably primary amine groups (NH2).
In this variant, the (poly)amine compound(s) are chosen from poly(meth)acrylates or poly(meth)acrylamides bearing lateral primary or secondary amine functions, such as poly(3-aminopropyl)methacrylamide and poly (2- aminoethyl) methacrylate.
Preferably, the (poly)amine compounds are chosen from chitosans (notably polypglucosamine)) and polydimethylsiloxanes comprising primary amine groups at the end of the chain and/or on side chains.
According to this variant, the (poly)amine compound(s) are chosen in particular from poly((C2-C5)alkyleneimines), and preferably polyethylenimines and polypropyleneimines, notably poly(ethyleneimine), in particular the product sold under reference 408700 by the company Aldrich Chemical or under the trade name Lupasol by BASF, notably with a molecular weight of between 1200 and 25 000; poly(allylamine), in particular the product sold under reference 479136 by the company Aldrich Chemical; polyvinylamines and copolymers thereof, notably with vinylamides, in particular vinylamine/vinylformamide copolymers such as those sold under the name Lupamin® 9030 by the company BASF; polyamine acids containing NH2 groups, such as polylysine, in particular the product sold by the company JNC Corporation (formerly Chisso); amino dextran, in particular the product sold by the company CarboMer Inc; amino polyvinyl alcohol, in particular the product sold by the company CarboMer Inc; acrylamido(Ci-C6)alkylamine-based copolymers, notably acrylamidopropylamine-based copolymers; and poly(D-glucosamine), for example sold under the reference Kionutrime CSG® by the company Kytozyme.
According to a particular embodiment, the polydimethylsiloxanes comprising primary amine groups at the end of the chain and/or on side chains are chosen from the compounds of formula (VII) below: Ra-Si(Rb)(Rc)-O-[Si(Rb)(Rc)-O]m-[Si(ALK1-NH2)(Ra)-O]n-Si(Rb)(Rc)-Ra(VII) in which formula (VII):
Ra, which may be identical or different, represents a hydroxyl or (Ci-C4)alkyl group,
- Rb and Rc, which may be identical or different, preferably identical, represent a (Ci-C4)alkyl group, such as methyl,
- ALK1 represents a linear or branched (Ci-Ce) alkylene group, optionally interrupted with an N(H) group,
- m and n are integers greater than or equal to 1 ; preferably, m and n are such that the weightaverage molecular mass of the compound of formula (VII) ranges from 1000 g.mol 1 to 500000 g.mol 1.
According to a preferred variant, formula (VII) is such that Ra, Rb and Rc represent a methyl group, ALK1 represents a propylene group, the values of n and m are such that the weightaverage molecular weight of the poly dimethylsiloxane ranges from 1000 g.mol 1 to 55 000 g.mol 1.
As examples of polydimethylsiloxanes of formula (VI), mention may be made of those sold under the names AMS-132, AMS-152, AMS-162, AMS-163, AMS-191 and AMS-1203 by the company Gelest.
According to another variant, formula (VII) is such that Ra represents a hydroxyl or (Ci- C4)alkyl group, such as methyl, ALK1 represents a (Cs-C6)alkylene group substituted with an NH group; preferably, ALK1 represents -(CH2)3-N(H)-(CH2)2-, and m and n are such that the weight- average molecular mass of the compound of formula (VI) ranges from 5000 g.mol 1 to 500000 g.mol 1.
As amine polymer, mention may also be made of a,co-diamino polytetrahydrofurans (or polytetramethylene glycol) and a,co-diamino polybutadienes.
According to a particular embodiment of the invention, the (poly)amine compounds are chosen from hyperbranched polymers comprising at least one amino group and dendrimers bearing at least one amino group, such as PAMAM polyamidoamine dendrimers with an ethylenediamine core and a terminal amine function.
Thus, according to a preferred embodiment, the composition comprises a crosslinking agent R chosen from (poly)amine compounds, in particular chosen from chitosans, aminoalkoxysilanes, polydimethylsiloxanes comprising primary amine groups at the end of the chain or on side chains, amodimethicones, polyglucosamines and mixtures thereof. More preferentially, the composition comprises a crosslinking agent chosen from chitosans, aminoalkoxysilanes and polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains such as amodimethicones, and even more preferentially chosen from poly(D-glucosamine), 3 -aminopropyltriethoxy silane (APTES), 3- aminoethyltriethoxy silane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2- aminoethyl)-3-aminopropyltriethoxysilane and polydimethylsiloxanes comprising terminal amino groups at the end of the chain, such as bis-cetearyl amodimethicone, and even more preferentially is 3-aminopropyl triethoxysilane (APTES).
Figure imgf000029_0001
According to a preferred embodiment, the crosslinking agent R is chosen from (poly)thiol compounds, also known as ''(poly)mercaplo" compounds.
The (poly)thiol compound may in particular be organic or inorganic, preferably organic.
In a preferred embodiment, the (poly)thiol compound is silicon-based, i.e. it includes one or more thiol groups and it also includes at least one siloxane chain.
In a particular embodiment, the (poly)thiol compound is inorganic. Mention may be made, for example, of poly thiol silicones.
The (poly)thiol compound may in particular be chosen from non-polymeric (poly)thiol compounds.
For the purposes of the present invention, the term “non-polymeric compounds” means compounds which are not directly obtained via a monomer polymerization reaction.
According to one embodiment of the invention, the (poly)thiol compound(s) are organic, non-polymeric and of formula (VIII) below and also the solvates thereof such as hydrates: L(SH)q (VIII) in which formula (VIII):
- q denotes an integer greater than or equal to 2; preferably, q is between 2 and 10 inclusive and preferably between 2 and 5;
- L denotes a linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated, multivalent (at least divalent) group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms; L being optionally interrupted and/or terminated with one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and combinations thereof such as -O-, -O-C(X)-, -N(R)-C(X)-, -Si(Rc)(Rd)-O- with R representing a hydrogen atom or a (Ci-C6)alkyl group such as methyl; and/or L being optionally substituted with one or more groups chosen from: -N(Ra)Rb and -(X’)a-C(X)-(X”)b-Ra; with X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or a group N(Rb); a and b being 0 or 1, preferably the sum of a + b being 1; Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-Ce/alkyl or aryl(Ci-C4)alkyl group, such as benzyl, preferably Ra and Rb represent a hydrogen atom; and Rc and Rd, which may be identical or different, represent a (Ci-Ce/alkyl, aryl(Ci-C4)alkyl or (Ci-Cejalkoxy group.
According to a particular embodiment of the invention, the (poly)thiol compound(s) are chosen from polythiol compounds, notably polythiol compounds comprising from 2 to 20 carbon atoms.
According to a preferred embodiment, the (poly)thiol compound(s) are non-polymeric and notably of formula (VIII) defined above, in which q is an integer greater than or equal to 2, preferably q is an integer between 2 and 10 inclusive and preferably between 2 and 5.
The (poly)thiol compounds that are suitable for use in the invention are preferably dithiol compounds.
Preferably, L denotes a Cs-Cis multivalent radical, which is notably linear. Preferentially, the liposoluble polythiol is a notably linear Cs-Cis dithiol. Preferably, the Cs-Cis chain is a hydrocarbon-based chain, i.e. formed from carbon and hydrogen. In particular, the liposoluble polythiol is a linear Cs-Ci6 and notably C10-C14 dithiol. As (poly)thiol compounds of formula (VII), mention may be made more particularly of 1,8-octanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 1,14-tetradecanedithiol, 1,16-hexadecanedithiol and 1,18-octadecanedithiol. Use is preferably made of 1,10-decanedithiol, 1,12- dodecanedithiol and/or 1,14-tetradecanedithiol, preferentially 1,12-dodecanedithiol.
According to another particular embodiment of the invention, the (poly)thiol compound(s) are chosen from thiolated alkoxysiloxanes, such as those of formula (VIII’) below: R’i-Si(OR’2)z(R’3)x (VIII’) in which formula (VIII’):
- RT is a linear or branched, saturated or unsaturated, cyclic or acyclic C1-C12 hydrocarbonbased chain substituted with one or more groups chosen from thiol groups; and aryl, aryloxy, arylthio, arylamino, the aryl group being substituted with one or more thiol groups, or thiol(Ci-C6)alkyl, preferably thiol(Ci-C6)alkyl; and R’i is optionally interrupted in its hydrocarbon-based chain with one or more heteroatoms such as O, S, N, a carbonyl group C(O), or a combination thereof such as ester -C(O)-O-, or amide -C(O)-N(H)-, R’i being bonded to the silicon atom directly via a carbon atom,
- R’2 and R’3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl,
- z denotes an integer ranging from 1 to 3, and
- x denotes an integer ranging from 0 to 2, with z + x = 3.
Preferably, R’2 represents a linear or branched, preferably linear, alkyl group comprising from 1 to 4 carbon atoms, such as ethyl.
Preferably, R’3 represents a linear or branched, preferably linear, alkyl group comprising from 1 to 4 carbon atoms, such as methyl or ethyl.
Preferably, R’i is an acyclic chain, in particular R’i is a linear or branched, saturated or unsaturated, preferably saturated, Ci-Ce hydrocarbon-based chain substituted with one or more thiol groups, preferably substituted with one thiol group.
Preferably, R’i is a saturated linear Ci-Ce hydrocarbon-based chain substituted with a thiol group, and R’2 represents an alkyl group comprising from 1 to 4 carbon atoms.
Preferably, R’3 represents an alkyl group comprising from 1 to 4 carbon atoms.
Preferably, z is equal to 3.
According to a more particular embodiment of the invention, the thiolated alkoxy siloxanes are chosen from those of formula (IX) below: (R1O)(R2)(R3)Si-[CH(R4)]t-[N(R’4)-L1]p-SH (IX) in which formula (IX):
- p is 0 or 1 ;
- 1 is an integer between 1 and 4, preferably 2;
- R1 represents a (Ci-C6)alkyl radical;
- R2 and R3, which may be identical or different, preferably identical, are chosen from a (Ci- C6)alkyl group, in particular a C1-C4 alkyl group, such as methyl, and a (Ci-C6)alkoxy group, in particular a (Ci-C4)alkoxy group, such as methoxy;
- R4 and R’4, which may be identical or different, represent a hydrogen atom or a (Ci-C6)alkyl group, such as methyl; - L1 represents a divalent, saturated, linear or branched C1-C20 hydrocarbon-based radical.
According to a particular embodiment of the invention, the thiolated alkoxysiloxanes are chosen from those of formula (IX’) below: (R’1O)(R’2)(R’3)Si-CH(R4)-CH(R5)-(L2)q-SH (IX’) in which formula (IX’):
- q is equal to 0 or 1 ;
- X represents an oxygen or sulfur atom, preferably a sulfur atom;
- R’1 denotes a (Ci-C6)alkyl radical;
- R’2 and R’3, which may be identical or different, preferably identical, are chosen from a (Ci-C6)alkoxy group, in particular a C1-C4 alkoxy group, and a (Ci-C6)alkyl radical;
- R5 represents a hydrogen atom or a C1-C4 alkyl group optionally substituted with an amino, thiol or hydroxyl group;
- R4 represents a hydrogen atom or a C1-C4 alkyl group, in particular methyl;
- L2 represents a linear or branched, saturated C1-C20 divalent hydrocarbon-based group, optionally interrupted with a heteroatom such as -N(H)-, and/or optionally substituted with one or more hydroxyl, thiol or amino groups.
Preferably, the thiolated alkoxysilane(s) are chosen from 4-(trimethoxy silyl)- 1 -butanol, 3- (trimethoxy silyl)- 1 -propanol, 3-(triethoxysilyl)-l-propanol, 11 -(trimethoxy silyl)- 1- undecanethiol, 4-(trimethoxysilyl)-2-butanethiol, 2-(triethoxysilyl)ethanethiol, 3- (triethoxy silyl)- 1 -propanethiol, 2-(trimethoxysilyl)ethanethiol, 3 -(trimethoxy silyl)- 1- propanethiol and 3-(dimethoxymethylsilyl)-l-propanethiol.
More preferentially, the thiolated alkoxysilane(s) are chosen from 2- (triethoxysilyl)ethanethiol (18236-15-2) and 3 -(triethoxy silyl)- 1 -propanethiol (14814-09-6). According to a preferred embodiment of the invention, the (poly)thiol compound(s) are chosen from polymeric (poly)thiol compounds.
The polymeric (poly)thiol compounds may be star, comb, brush and dendritic homopolymers or copolymers bearing thiol units. The polymers may be of natural origin such as polysaccharides or polypeptides, or of synthetic origin such as acrylic polymers, polyesters or polyglycols. The thiol units may be present as terminal and/or side groups.
Examples that may be mentioned include the polymers described in the following articles: Polymers containing groups of biological activity, C.G. Overberger et al., Polytechnic Institute of Brooklyn, http://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf; EP 1 247 515 A2; US 3 676 440; and EP 1 572 778.
The polymeric (poly)thiol compounds of the invention are preferably organic and/or silicone compounds, more preferentially of formula (X):
POLY(SH)q (X) in which formula (X):
- q is greater than or equal to 2, preferably greater than or equal to 3;
- POLY denotes a polymer-based radical, preferably carbon-based or silicone-based; POLY being optionally interrupted with one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and combinations thereof such as -O-, -O-C(X)-, -N(R)-C(X)-, -Si(Rc)(Rd)-O- with R representing a hydrogen atom or a (C i -CoJal kyl group such as methyl; and/or POLY being optionally substituted with one or more halogen atoms, or a group chosen from Ra(Rb)N- and -(X’)a-C(X)-(X”)b-Ra; X, X’ and X”, which may be identical or different, represent an oxygen or sulfur atom or a group N(Rb); a and b being 0 or 1, preferably the sum of a + b being 1; Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci- Cio)alkyl or aryl(Ci-C4)alkyl group, such as benzyl, preferably Ra and Rb represent a hydrogen atom; and Rc and Rd, which may be identical or different, represent a (Ci-Cio)alkyl, aryl(Ci-C4)alkyl or (Ci-Cio)alkoxy group.
The methods for preparing the polymeric (poly)thiol compounds used according to the invention are known to those skilled in the art; several methods are reported hereinbelow in a non-limiting manner. The polymeric (poly)thiol compounds used according to the invention may be obtained by polymerization or polycondensation of monomer units bearing thiol or protected thiol functions, optionally as a copolymerization or co-polycondensation of monomer units free of thiol or protected thiol functions.
According to one embodiment of the invention, the polymeric (poly)thiol compounds used according to the invention are polymers which are soluble in cosmetic media, particularly in aqueous or aqueous -alcoholic media. They are more preferentially obtained from amino polymers and the ammonium salts thereof or from poly hydroxylated polymers.
According to another embodiment of the invention, the thiolated polymers used according to the invention are polymers that are soluble in lipophilic media.
According to one embodiment of the invention, the polythiol compound is a polymeric compound of formula (X) in which q denotes an integer greater than or equal to 2, and POLY denotes a carbon-based and/or silicon-based, preferably silicon-based, polymeric radical, POLY also possibly containing one or more heteroatoms chosen from O, N or S, and/or one or more functions chosen from (thio)ester, (thio)ketone, (thio)amide, (thio)urea and (thio)carbamate functions, and/or possibly being substituted with one or more linear or branched (Ci-Cio)alkyl or linear or branched (Ci-Cio)alkoxy groups, it being understood that when POLY is substituted, the thiol functions may be borne by the substituent(s).
The weight-average molecular weight of the polythiol polymer compounds, such as those of formula (X), is generally between 500 and 400 000 g.moT1, preferably between 500 and 150000 g.moT1.
According to a particular embodiment of the invention, the polythiol compounds are chosen from polyorganosiloxanes including thiol groups on end chains, such as those of formula (XI) below:
HS-L4-Si(Ra)(Rb)-O-[Si(Ra)(Rb)-O]n-Si(Ra)(Rb)-L5-SH (XI) in which formula (XI):
- Ra and Rb, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci-C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl;
- n represents an integer greater than or equal to 1 and more particularly the value of n is such that the weight- average molecular weight of the silicone ranges from 500 to 55 000 g.moT1; in particular, n is an integer ranging from 1 to 100, preferably ranging from 5 to 50 and preferentially ranging from 10 to 30, and
- L4 and L5, which may be identical or different, preferably identical, represent a linear or branched, saturated or unsaturated, optionally cyclic hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, and in particular represent a covalent bond or a (Ci-C6)alkylene, (Ci-C6)alkylenoxy, oxy(Ci-C6)alkylene, (Ci-C6)alkylenoxy(Ci- C6)alkylene, (Ci-C6)alkylenoxy(Ci-C6)alkylenoxy or oxy(Ci-C6)alkylenoxy(Ci-C6)alkylene group, preferably a (Ci-C6)alkylene, (Ci-C6)alkylenoxy, oxy(Ci-C6)alkylene or (Ci- Ce) alky lenoxy (C i -Ce) alkylene group .
Preferentially, the (poly)thiol compounds are polythiol polyorganosiloxanes, more preferentially polythiol poly dimethylsiloxanes, notably chosen from those of formula (XII): HS-L4-Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)2-L5-SH (XII) in which formula (XII):
- L4 and L5 are as defined previously in formula (IX), in particular L4 and L5 represent a (Ci- C6)alkylene, (Ci-C6)alkylenoxy, oxy(Ci-C6)alkylene or (Ci-C6)alkylenoxy(Ci-C6)alkylene group, more preferentially a divalent group chosen from -R2-, -O-R2-, -R2-O- and -R2- O-R2-, preferably -R2-O-R2-, with R2 representing a linear or branched, preferably linear, (C2-C6)alkylene group, such as ethylene or n-propylene, preferably n-propylene; and
- n is as defined in formula (XI).
As polythiol compounds of formula (XII), mention may be made of mercaptosiloxanes or thiolated siloxanes in which the thiol functions are at the chain ends, sold by the company Shin-Etsu under the reference X-22-167B, and mercaptosiloxane in which the mercapto functions are pendent, sold by the company Shin-Etsu under the reference KF-2001, or polydimethylsiloxanes in which the thiol functions are at the chain ends, via thio-n-propyl, 80-120 groups, sold by the company Gelest under the name DMS-SM 21.
Preferentially, the polythiol compounds are chosen polyorganosiloxanes including thiol groups on side chains, such as those of formula (XIII): Ra-Si(Rb)(Rd)-O-[Si(Ra)(Rb)-O]m-[Si(Rb)(ALKi-SH)-O]ii-Si(Rb)(Rd)-Ra (XIII) in which formula (XIII):
- Ra and Rb are as defined in formula (XI) and Rd is as defined for Ra and Rb, preferably Ra, Rb and Rd, which are identical, represent a (Ci-C6)alkyl group, such as methyl;
- Rd may also represent a (Ci-C6)alkyl group substituted with a (Ci -Chalky lamino or amino or thiol group, preferably (Ci-C4)alkyl such as methyl;
- ALKi represents a linear or branched, optionally cyclic, saturated or unsaturated divalent hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, a (thio)carbonyl group C(X) with X representing O or S, or combinations thereof such as -O- , -O-C(O)- or -C(O)-O-; preferably, ALKi represents a (Ci-C6)alkylene and more preferentially (Ci-C4)alkylene group such as propylene;
- n and m, which may be identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the weight- average molecular weight of said polyorganosiloxane is between 1000 and 55 000 g.mol 1. As examples of polythiol compounds of formula (XIII), mention may be made of those sold by the company Genesee Polymers under the names GP-367, GP-71-SS, GP-800 and GP- 710s, preferably GP-367, sold by the company Genesee Polymers.
The polythiol compounds are notably polydimethylsiloxanes including at least two thiol groups, for instance the products SMS-022, SMS-042 and SMS-992 sold by the company Gelest in https://www.gpcsilicones.com/products/silicone-fluids/mercapto-functional, https://www.shinetsusilicone-global.com/products/type/oil/detail/search/deg07.shtml, and 1053_Reactive Silicones_Silanes/Silicones - Gelest.
According to a particular embodiment of the invention, the (poly)thiol compounds are chosen from hyperbranched polymers comprising at least one thiol group and dendrimers bearing at least one thiol group, such as thiolated PAMAM dendrimers.
Preferably, the (poly)thiol compounds used according to the invention are chosen from polydiallylsiloxanes, notably polydimethylsiloxanes, including at least two thiol groups such as those of formula (XIII).
Figure imgf000036_0001
According to a particular embodiment, the crosslinking agent is a (poly)acrylate compound. The term ii(poly)acrylate” means a compound which comprises at least one acrylate ester group H2C=C(Re)-C(0)-Y- with Re representing a hydrogen atom or a (Ci-C4)alkyl group, such as methyl, preferably Re representing a hydrogen atom, and Y representing an oxygen atom or an amino group -N(H)-, preferably an oxygen atom.
More particularly, the (poly)acrylate(s) of the invention are of formula (XIV): L[-Y-C(0)-C(Re)=CH2]q (XIV) in which formula (XIV) q and L are as defined in formula (VIII), Y and Re being as defined previously, preferably Y = O and Re = H.
According to a preferred embodiment, the compounds of formula (XIV) are such that L represents a di- or trivalent, preferably trivalent, hydrocarbon-based chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, Y represents O, and Re represents a hydrogen atom.
According to a particular embodiment, the (poly)acrylate compounds are chosen from polyorganosiloxanes including at least one acrylate group on the side chain, such as those of formula (XV): Ra-Si(Rb)(Rd)-O-[Si(Ra)(Rb)-O]m-[Si(Rb)(ALKi-Y-C(O)-C(Re)=CH2)-O]n-Si(Rb)(Rd)-Ra (XV) in which formula (XV):
- Ra, Rb and Rd are as defined for formula (XIII), preferably Ra, Rb and Rd represent a (Ci- C6)alkyl group, such as methyl,
- ALKi is as defined for formula (XIII), preferably ALKi represents a (Ci-C6)alkylene group, more preferentially a (Ci-C4)alkylene group, such as propylene,
- n and m, which may be identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the weight- average molecular weight of said polyorganosiloxane is between 1000 and 55 000 g.mol 1.
- Y is as defined previously, and is preferably an oxygen atom.
More particularly, the (poly)acrylate compound may be chosen from 1,3 -butanediol diacrylate, 1,4-butanediol diacrylate, bis(trimethylolpropane) tetraacrylate, glyceryl 1,3- diglycerolate diacrylate, glyceryl propoxylate (1PO/OH) triacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol ethoxylate diacrylate, hydroxypivalyl hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol propoxylate (1PO/OH) diacrylate, pentaery thrityl tetraacrylate, pentaerythrityl triacrylate, polypropylene glycol) diacrylate, tricyclo[5.2.1.02,6]decanedimethanol diacrylate, trimethylolpropane ethoxylate (1EO/OH) methyl ether diacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tri(propylene glycol) diacrylate, and tris [2- (acryloyloxy)ethyl] isocyanurate.
The (poly)acrylate compound may also be chosen from N,N’ -methylenebisacrylamide.
According to this embodiment, the (poly)acrylate compound is combined in its implementation with an amine catalyst as described, for example, in Progress in coating 129, 21-25 (2019) and Progress in coating 135, 510-516 (2019). Preferably, the amine catalyst(s) are chosen from piperidine, DMAP (dimethylaminopyridine), DBU (1,8- diazabicyclo[5.4.0]undec-7-ene), DABCO (l,4-diazabicyclo[2.2.2]octane) and DBN (1,5- diazabicyclo[4.3.0]non-5-ene), more preferentially chosen from DBU (1,8- diazabicyclo[5.4.0]undec-7-ene), DABCO (l,4-diazabicyclo[2.2.2]octane) and DBN (1,5- diazabicyclo[4.3.0]non-5-ene), and in particular the catalyst is DBU (1,8- diazabicy clo [5.4.0] undec-7 -ene) . More particularly, the (poly)acrylate compounds are chosen from those of formula (XIV), notably trimethylolpropane triacrylate, and those of formula (XV), notably copolymers of dimethylsiloxanes and of acryloxypropylmethylsiloxanes.
D) Metal alkoxides
According to a particular embodiment, the crosslinking agent R is a compound chosen from the metal alkoxides of formulae (XIVa), (XlVb), (XIVc) and (XlVd) below and mixtures thereof:
. M-(ORl)n (XIVa)
. R-M-(ORi)n-i (XlVb)
. (RiO)n-i-M-R”-M’-(ORi’)n -i (XIVc)
. R-M(R’)-(0Ri)n-2 (XlVd) in which formulae (XIVa), (XlVb), (XIVc) and (XlVd):
- M and M’, which may be identical or different, represent an atom chosen from alkaline- earth metals, transition metals, metals of the lanthanide family, post-transition metals such as aluminium or tin and metalloids such as boron; preferably transition metals such as Ti and post-transition metals such as aluminium;
- n and n’ respectively represent the valencies of the atoms represented by M and M’;
- Ri and Rf , which may be identical or different, represent a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms, said hydrocarbon-based group being optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and P, notably O or N; and/or said hydrocarbonbased group being optionally substituted with one or more hydroxyl or carbonyl groups;
- R and R’, which may be identical or different, represent a hydrogen atom or a linear, branched, acyclic or cyclic, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P, notably O or N, and/or said hydrocarbonbased group being optionally substituted with one or more hydroxyl or carbonyl groups;
- R” represents -O-, -N(R2)-, -S- or a linear, cyclic or branched, saturated or unsaturated divalent hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and P, notably O or N, with R2 representing a linear, cyclic or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms.
Preferably, M and M’, which may be identical or different, represent an atom chosen from transition metals such as titanium or zirconium or alkaline-earth metals such as magnesium, more preferentially chosen from transition metals such as titanium or zirconium, even more preferentially titanium.
Preferably, the organometallic compound(s) are chosen from the alkoxides of formula (XIVa) as defined previously. According to this preferred embodiment, the organometallic compound(s) are more particularly chosen from the alkoxides of formula (XIVa), in which M represents an atom chosen from transition metals, metals of the lanthanide family, posttransition metals, such as aluminium, tin, metalloids, such as boron, or alkaline-earth metals, such as magnesium or calcium; n represents the valency of the atom represented by M; Ri represents a saturated, linear or branched, hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms.
According to another more preferred embodiment, the organometallic compound(s) are chosen from the alkoxides of formula (XIVa), in which M represents an atom chosen from transition metals, such as zirconium or titanium, metals of the lanthanide family, posttransition metals, such as aluminium or tin, metalloids, such as boron, and alkaline-earth metals, such as magnesium, preferably M represents a titanium atom; n represents the valency of the atom represented by M, notably 1, 2, 3 or 4, in particular 4; Ri represents a methyl, ethyl, 2-ethylhexyl, propyl, isopropyl, n-butyl, isobutyl or t-butyl group.
According to an even more preferred embodiment, the organometallic compound(s) are chosen from zirconium ethoxide (Zr(OC2Hs)4), zirconium propoxide (Zr(OCH2CH2CH3)4), zirconium isopropoxide (Zr(OCH(CH3)2)4), zirconium butoxide Zr(OCH2CH2CH2CH3)4, zirconium tert-butoxide (Zr(OC(CH3)3)4), titanium ethoxide (Ti(OC2Hs)4), titanium propoxide (Ti(OCH2CH2CH3)4), titanium isopropoxide (Ti(OCH(CH3)2)4), titanium butoxide (Ti(OCH2CH2CH2CH3)4), titanium tert-butoxide (Ti(OC(CH3)3)4), titanium 2- ethylhexyloxide (Ti(OCH2CH(C2Hs)(CH2)3CH3)4), and mixtures thereof, more preferentially chosen from zirconium propoxide, titanium propoxide, titanium butoxide and mixtures thereof. More preferentially, the crosslinking agent R is a compound of formula (XIVa) preferably in which M represents an atom chosen from transition metals, notably titanium such as titanium butoxide.
According to a preferred embodiment, the crosslinking agent is chosen from (poly)amine compounds A), (poly)thiol compounds B), (poly)acrylate compounds C), and preferably from (poly)amine compounds A) and (poly)thiol compounds B), and even more preferentially from (poly)amine compounds A).
In particular, said (poly)amine compounds A) are chosen from a) chitosans, such as polypglucosamine), b) polyether diamines, particularly polyethylene glycol a,co-diamine (bearing an amine function at the end of the chain), c) polyether triamines, such as polyetheramine (or Jeffamine), d) aminoalkoxysilanes, such as APTES, and d) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, such as bis(3-aminopropyl)- terminated poly(dimethoxysiloxane) (PDMS-diNEE) and amodimethicones comprising amine groups on side chains, such as bis-cetearyl amodimethicone, notably the product sold by Momentive Performance Materials.
According to a preferred embodiment, said (poly)amine compounds A) are chosen from a) chitosans, such as poly(D-glucosamine), d) aminoalkoxysilanes, such as APTES and d) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, such as bis(3- aminopropyl) -terminated poly(dimethoxy siloxane) (PDMS-diNFE) and amodimethicones comprising amine groups on side chains, such as bis-cetearyl amodimethicone, notably the product sold by Momentive Performance Materials.
In particular, said (poly)thiol compounds B) are chosen from a) poly dialkylsiloxanes bearing thiol functions, and b) alkoxysilanes bearing thiol functions, and in particular are chosen from a) poly dialkylsiloxanes bearing thiol functions, preferentially poly dimethylsiloxanes comprising thiol groups on the side chain (such as mercaptopropyl), notably those of formula (XIII).
In particular, said (poly)acrylate C) compounds are chosen from those of formula (XIV), notably trimethylolpropane triacrylate, and those of formula (XV), notably copolymers of dimethylsiloxanes and acryloxypropylmethylsiloxanes, preferably trimethylolpropane triacrylate.
According to a preferred embodiment, the crosslinking agent(s) is(are) chosen from:
A) (poly)amine compounds chosen from: ia) chitosans such as poly(D-glucosamine), ib) poly ether diamines, in particular a,co-diamino polyethylene glycol, bearing a chain-end amine function, ic) polyether triamines, in particular polyetheramines (or Jeffamine), id) aminoalkoxy silanes, in particular APTES, and ie) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly bis(3-aminopropyl)-terminated poly (dimethoxy siloxane) (PDMS-diNtk) and amodimethicones comprising amine groups on side chains, more particularly bis-cetearyl amodimethicone ;
B) (poly)thiol compounds chosen from: iia) polydialkylsiloxanes bearing thiol functions, and iib) alkoxysilanes bearing thiol functions, and in particular chosen from iia) polydialkylsiloxanes bearing thiol functions, preferably from polydimethylsiloxanes comprising thiol groups on the side chain, in particular mercaptopropyl, and more particularly chosen from the compounds of formula (XIII): Ra-Si(Rb)(Rd)-O-[Si(Ra)(Rb)-O]m-[Si(Rb)(ALKi-SH)-O]n-Si(Rb)(Rd)-Ra (XIII) in which formula (XIII):
- Ra and Rb, which may be identical or different, preferably identical, represent a (Ci- C4)alkyl group, in particular methyl, a (Ci-C4)alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(Ci-C4)alkyl group, in particular benzyl, or an aryl(Ci-C4)alkoxy group, in particular benzoxy, preferably a (Ci-C4)alkyl group, more preferentially methyl,
- Rd represents a (Ci-C4)alkyl group, in particular methyl, a (Ci-C4)alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(Ci-C4)alkyl group, in particular benzyl, an aryl(Ci-C4)alkoxy group, in particular benzoxy, or a (Ci-C6)alkyl group substituted with a (Ci-C4)alkylamino, amino or thiol group, and preferably a (Ci-C4)alkyl group, more preferentially methyl, and preferably Ra, Rb and Rd are identical and represent a (Ci-C6)alkyl group, more preferentially methyl,
- ALKi represents a linear or branched, optionally cyclic, saturated or unsaturated divalent hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, a (thio)carbonyl group C(X) with X representing O or S, or combinations thereof, in particular -O-, -O-C(O)- or -C(O)-O-; preferably, ALKi represents a (Ci-C6)alkylene and more preferentially (C1-C4) alkylene group, even more preferentially propylene,
- n and m, which may be identical or different, represent an integer greater than 2, and in particular the values of m and n are such that the weight-average molecular weight of said polyorganosiloxane is between 1000 and 55 000 g.mol 1; and
C) the (poly)acrylate compounds of formula (XIV): L[-Y-C(O)-C(Re)=CH2]q (XIV) in which formula (XIV):
- q represents an integer greater than or equal to 2, in particular n is between 2 and 10 inclusive and preferably between 2 and 5,
- L denotes a linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated, multivalent (at least divalent) group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms; L being optionally interrupted and/or terminated with one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and combinations thereof, in particular -O-, -O-C(X)-, -N(R)-C(X)-, -Si(Rc)(Rd)-O- with R representing a hydrogen atom or a (Ci-C6)alkyl group, in particular methyl; and/or L being optionally substituted with one or more groups chosen from: -N(Ra)Rb and -(X’)a-C(X)-(X”)b-Ra; with X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or a group N(Rb); a and b being 0 or 1, preferably the sum of a + b being 1; Ra and Rb, which may be identical or different, represent a hydrogen atom, a (Ci-Ce/alkyl group or an aryl(Ci-C4) alkyl group, in particular benzyl, preferably Ra and Rb represent a hydrogen atom, and Rc and Rd, which may be identical or different, represent a (Ci-Ce/alkyl, aryl(Ci-C4)alkyl or (Ci-Ce/alkoxy group, - Re represents a hydrogen atom or a (Ci-C4)alkyl group, in particular methyl; preferably, Re represents a hydrogen atom, and
- Y represents an oxygen atom or an amino group -N(H)-, preferably an oxygen atom, preferably Y is an oxygen atom and Re is a hydrogen atom, preferably L represents a di- or trivalent, preferably trivalent, hydrocarbon-based chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, and more preferentially, the compounds of formula (XIV) are trimethylolpropane triacrylate.
COSMETIC ACTIVE AGENTS iv)
According to a particular embodiment, the process of the invention also comprises the application of iv) at least one cosmetic active agent to said keratin materials.
More particularly, in the treatment process according to the invention, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used comprises one or more cosmetic active agents.
In particular, the cosmetic active agent(s) iv) is(are) chosen from: a) dyestuffs (or colouring agents), in particular chosen from pigments, direct dyes and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV-screening agents, and d) mixtures thereof.
According to a particular embodiment, the at least one cosmetic active agent iii) is chosen from dyestuffs, preferably chosen from pigments, direct dyes and mixtures thereof, more preferentially pigments.
Needless to say, a person skilled in the art will take care to select this or these optional cosmetic active agent(s), and/or the amount thereof, such that the advantageous properties of the corresponding composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.
According to a particular embodiment, the process of the invention uses one or more dyestuffs. More particularly, in the process of the invention, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used comprises at least one particulate or non-particulate, water- soluble or water-insoluble dyestuff, preferably in a proportion of at least 0.01% by weight relative to the total weight of the composition considered.
For obvious reasons, this amount is liable to vary significantly with regard to the intensity of the desired colour effect and of the colour intensity afforded by the dyestuffs under consideration, and its adjustment clearly falls within the competence of a person skilled in the art.
Preferably, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” comprises at least one dyestuff chosen from pigments, direct dyes and mixtures thereof, more preferentially pigments.
More preferentially, the pigment(s) of the invention are chosen from carbon black, iron oxides, in particular yellow, red and black iron oxides, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet triarylmethane pigments, in particular Blue 1 Lake, azo pigments, in particular red azo pigments, more particularly D&C Red 7, an alkali metal salt of lithol red, in particular the calcium salt of lithol red B, and even more preferentially chosen from red iron oxides, yellow iron oxides and azo pigments, in particular red azo pigments, more particularly D&C Red 7.
Pigments
For the purposes of the invention, the term “pigment” means any compound that is capable of imparting colour to keratin materials. These compounds have a solubility in water at 25 °C and at atmospheric pressure (760 mmHg) of less than 0.05% by weight, and preferably less than 0.01% by weight.
As pigments that are suitable for use in the invention, mention may notably be made of the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry.
These pigments may be synthetic or natural.
These pigments may be in pigment powder or paste form.
They may be coated or uncoated. These pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof. A pigment that is suitable for use in the invention may be chosen from mineral pigments.
The term “mineral pigment” means any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium, zirconium or cerium oxides or dioxides, and also of zinc, iron or chromium oxides.
It may also be a pigment having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts, and has a contrast ratio in the region of 30. They may also be pigments having a structure that may be, for example, of silica microsphere type containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL-100 P, this pigment consisting of silica microspheres containing yellow iron oxide.
Advantageously, the pigments may be iron oxides and/or titanium dioxides.
A pigment that is suitable for use in the invention may be chosen from organic pigments.
The term “organic pigment” means any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on organic pigments. Among the organic pigments that are useful in the present invention, mention may be made of nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds. In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.
Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names: Cosmenyl Yellow IOG: Yellow 3 pigment (CI 11710); Cosmenyl G yellow: Yellow 1 pigment (CI 11680); Cosmenyl GR orange: Orange 43 pigment (CI 71105); Cosmenyl R red: Red 4 pigment (CI 12085); Cosmenyl FB carmine: Red 5 pigment (CI 12490); Cosmenyl RL violet: Violet 23 pigment (CI 51319); Cosmenyl A2R blue: Blue 15.1 pigment (CI 74160); Cosmenyl GG green: Green 7 pigment (CI 74260); Cosmenyl R black: Black 7 pigment (CI 77266).
The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may particularly be composed of particles including an inorganic core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.
The organic pigment may also be a lake.
The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium. Among the dyes adsorbed on organic substrates, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985) D & C Green 5 (CI 61 570), D & C Yellow 10 (CI 77 002), D & C Green 3 (CI 42053), D & C Blue 1 (CI 42090), FDC Red 4, D & C Red 6, D & C Red 22, D & C Red 28, D & C Red 30, D & C Orange 4, D & C Yellow 8, D & C Green 5, D & C Red 17, D & C Green 6, D & C Yellow 11, D & C Violet 2, Sudan red, carotenes (P-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto, curcumin, betanin (beet), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocianine, black carrot, hibiscus, elderberry), caramel, riboflavin, beet juice and caramel. An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850:1).
The pigment may also be a pigment with special effects.
The term “pigments with special effects” refers to pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
Several types of special effect pigments exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.
The pigments may be dispersed in the composition by means of a dispersant.
This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12- hydroxy stearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof. As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Coming under the references DC2-5185 and DC2-5225 C. The pigments used in the composition may be surface-treated with an organic agent. According to a particular embodiment, the dispersant(s) are of amino silicone type other than the alkoxysilanes described previously and are cationic. Preferably, the pigment(s) is (are) chosen from mineral, mixed mineral-organic, or organic pigments.
According to a particular embodiment, the pigment(s) according to the invention are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds.
According to another embodiment of the invention, the pigment(s) according to the invention are mineral pigments.
Direct d es
According to a particular embodiment of the invention, the cosmetic active agent is a dyestuff chosen from one or more direct dyes.
The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes which will spread superficially over the fibre. They may be ionic or nonionic, preferably cationic or nonionic.
Among the direct dyes that are suitable for use in the invention, mention may be made of azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (A) and (B) below and the azo cationic dyes of formulae (C) and (D) below:
Het+-C(Ra)=N-N(Rb)-Ar, Q (A)
Het+-N(Ra)-N=C(Rb)-Ar, Q (B)
Het+-N=N-Ar, Q (C)
Ar+-N=N-Ar”, Q (D) in which formulae (A) to (D):
- Het+ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cs)alkyl group such as methyl; - Ar+ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri/Ci-Cs/alkylammonium, such as trimethylammonium;
Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as optionally substituted (Ci- Cs)alkyl, optionally substituted (Ci-Cs)alkoxy, (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, aryl(Ci-Cs)alkylamino, and optionally substituted N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino or alternatively Ar represents a julolidine group;
- Ar’ ’ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci-Cs)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Ci-Cs)alkoxy or phenyl groups;
- Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-Cs)alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;
- Q" represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate. In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (A) to (D) as defined previously, more particularly the cationic direct dyes bearing an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP 714 954.
Preferably, the direct dyes are chosen from the compounds of formulae (E) and (F) below: [Chem 3]
Figure imgf000049_0001
[Chem 4]
Figure imgf000050_0001
in which formulae (E) and (F):
- R1 represents a (Ci-C4)alkyl group such as methyl;
- R2 and R3, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, such as methyl;
- R4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cs)alkyl, optionally substituted (Ci-Cs)alkoxy, or (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; in particular, R4 is a hydrogen atom;
- Z represents a CH group or a nitrogen atom, preferentially CH;
- Q" is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesyl.
In particular, the dyes of formulae (E) and (F) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof with Q’ being an anionic counterion as defined previously, particularly a halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl. The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly referred to as “acid” direct dyes owing to their affinity for alkaline substances.
The term “anionic direct dye” means any direct dye including in its structure at least one CO2R’ or SO3R’ substituent with R’ denoting a hydrogen atom or a cation originating from a metal or an amine, or an ammonium ion.
The anionic direct dyes may be chosen from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.
Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and particularly hennabased poultices or extracts.
Preferably, the direct dyes are chosen from anionic direct dyes.
The dyestuffs, preferably the pigments, may be present in concentrations ranging from 0.01% to 30% by weight, preferably from 0.02% to 20% by weight and more particularly from 0.05% to 15% by weight relative to the total weight of the composition containing them.
The direct dye(s) may be present in concentrations ranging from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of the composition containing them.
Preferably, the cosmetic active agent(s), in particular the dyestuff(s) and more particularly the pigment(s), are introduced into at least compositions “Cl”, “C2”, “C3”, “C4” or “C5”.
Care active agents
According to a particular embodiment, the process of the invention uses one or more care active agents.
More particularly, in the process of the invention, according to one embodiment, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used comprises one or more care active agents, preferably in a proportion of at least 0.01% by weight relative to the total weight of the composition considered. In particular, the care active agent may be at least one hydrophilic active agent and/or one lipophilic active agent, and preferably a hydrophilic care active agent.
The term “hydrophilic active agent” means a water-soluble or water-dispersible active agent that is capable of forming hydrogen bonds.
The cosmetic care active agent(s) may notably be chosen from: a) vitamins and derivatives thereof, notably esters thereof, in particular tocopherol (vitamin E) and esters thereof (such as tocopheryl acetate), ascorbic acid (vitamin C) and derivatives thereof; b) humectants, in particular urea, hydroxyureas, glycerol, polyglycerols, glycerolglucoside, diglycerolglucoside, polyglycerylglucosides and xylitylglucoside, and in particular glycerol; c) C-glycoside compounds; d) antioxidant compounds; e)anti-ageing active agents, in particular hyaluronic acid compounds, and notably sodium hyaluronate, retinol and derivatives thereof, salicylic acid compounds and in particular n-octanoyl-5- salicylic acid (capryloyl salicylic acid), caffeine, adenosine, c-P-d-xylopyranoside-2-hydroxypropane and the sodium salt of 3-hydroxy-2-pentylcyclopentylacetic acid; f) skincare agents chosen from allantoin, panthenol and protein hydrolysates; g) polyphenols, notably escin, ruscus, diosmin, hesperidin and resveratrol, and h) and mixtures thereof.
In particular, in the process of the invention, according to one embodiment, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used comprises a moisturizer (also known as a humectant agent). Preferably, the care active agent is a moisturizer, and in particular is glycerine (glycerol).
The care active agent(s) may in particular be present, in the composition containing same, in a content ranging from 0.01% to 30% by weight, relative to the weight of the composition, and preferably from 0.02% to 25% by weight.
Figure imgf000052_0001
According to one embodiment of the process of the invention, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used comprises, as cosmetic active agent, at least one UV- screening agent.
The UV-screening agent is a UV-screening agent normally used in cosmetics.
It may be chosen from the positive list contained in Annex VI of (EC) Regulation No. 1223/2009, which specifies the list of UV-screening agents permitted in cosmetics.
The UV-screening agents that are suitable for use in the invention may be of varied nature. They may be lipophilic, hydrophilic or insoluble organic agents.
The term “ lipophilic UV-screening agent” means any cosmetic or dermatological screening agent that can be fully dissolved in molecular form in a liquid fatty phase or that can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.
The term “hydrophilic UV-screening agent” means any cosmetic or dermatological screening agent that can be fully dissolved in molecular form in a liquid aqueous phase or that can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.
The term “insoluble UV-screening agent” means any cosmetic or dermatological screening agent which is not defined either as a lipophilic UV-screening agent or as a hydrophilic UV- screening agent, and which is in the form of particles in aqueous phase or liquid fatty phase. The UV-screening agents of the composition according to the invention may afford UVA and/or UVB photoprotection.
According to a preferred embodiment, the compositions, which are preferably cosmetic compositions, may comprise at least one organic and/or mineral UV-screening agent (for screening out the UV radiation of sunlight).
In particular, the UV-screening agent(s) are chosen from bis-resorcinyl triazine derivatives, dibenzoylmethane derivatives, benzylidenecamphor derivatives, and mixtures thereof. The organic UV-screening agents may also be chosen from anthranilic derivatives; cinnamic derivatives; salicylic derivatives; benzophenone derivatives; phenylbenzotriazole derivatives; benzalmalonate derivatives, notably those mentioned in patent US 5 624 663; phenylbenzimidazole derivatives; imidazolines; 4,4-diarylbutadiene derivatives; bis- benzazolyl derivatives, as described in patents EP 6 693 23 and US 2 463 264; p- aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives, as described in patent applications US 5 237 071, US 5 166 355, GB 2 303 549, DE 197 26, 184 and EP 893 119; benzoxazole derivatives, such as those described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101 62 844; screening polymers and screening silicones such as those notably described in patent application WO 93/04665; a-alkylstyrene -based dimers such as those described in patent application DE 198 55 649; 4,4-diarylbutadienes such as those described in patent applications EP 0 967 200, DE 197 46 654, DE 197 55 649, EP 1 008 586, EP 1 133 980 and EP 133 981; other merocyanine derivatives such as those described in patent applications WO 04/006878, WO 05/058269 and WO 06/032741, and mixtures thereof.
According to a particular embodiment, the concentration of the organic UV-screening agents in the compositions ranges from 1% to 50%, preferably from 1% to 40% by weight, for example from 5% to 35% by weight, relative to the total weight of the composition.
The UV-screening agent(s) may be mineral UV-screening agents, which are generally pigments. The pigments may or may not be coated.
Thus, the mineral UV-screening agents may be chosen from coated or uncoated pigments, and in particular from coated titanium oxide pigments, silicone-treated titanium oxides, uncoated titanium oxide pigments, uncoated zinc oxide pigments, coated zinc oxide pigments, uncoated cerium oxide pigments, uncoated iron oxide pigments, coated iron oxide pigments, and mixtures thereof. According to a particular embodiment, compositions “Cl” to “C5” are free of mineral UV- screening agents.
According to a particular embodiment, the amount of the mineral UV-screening agent(s) present in compositions “Cl”, “C2”, “C3”, “C4” or “C5” according to the invention may range from 0.01% to 20% by weight relative to the total weight of the composition containing same. It ranges, for example, from 1% to 15% by weight, relative to the total weight of the composition.
According to a particular embodiment, at least one of the compositions “Cl” to “C5” also comprises one or more organic UV-screening agents and one or more mineral UV-screening agents.
According to a particular embodiment, the compositions comprise a combination of UV- screening agents as described in patent FR 2 977 490, patent application WO 2013/004777 or patent application US 2014/0134120.
Preferably, the process for treating keratin materials, notably keratin fibres, and compositions “Cl”, “C2”, “C3”, “C4” or “C5” use or comprise one or more dyestuffs chosen from pigments, direct dyes and mixtures thereof, preferably pigments; more preferentially, the pigment(s) of the invention are chosen from carbon black, iron oxides, notably yellow, red and black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and violet triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol red B, even more preferentially red iron oxides, yellow iron oxides and azo pigments, notably red azo pigments, such as D&C Red 7.
Figure imgf000054_0001
substances
According to a particular embodiment, the process of the invention uses v) one or more fatty substances, in particular one or more oils, preferably volatile oils.
In particular, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process of the invention contains a fatty phase.
In particular, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process of the invention comprises one or more fatty substances, in particular one or more oils, preferably volatile oils. The term “oil” refers to a fatty substance that is liquid at room temperature (20°C) and atmospheric pressure (760 mmHg).
The term “hydrocarbon-based oil” means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
According to one embodiment of the invention, the oil(s) v) is(are) chosen from volatile oils, in particular:
- hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular branched Cs-Ci6 alkanes, in particular isoalkanes, more particularly isoalkanes (also known as isoparaffins), preferably C13-C16 isoparaffins, isododecane, isodecane, isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, alone or as mixtures, preferably isododecane (also known as 2,2,4,4,6-pentamethylheptane), linear alkanes, in particular C11-C16 alkanes, alone or as mixtures, in particular hexane, decane, undecane, tridecane, isoparaffins, in particular n-dodecane (C12) and n-tetradecane (C14), the undecanetridecane mixture, mixtures of n-undecane (C11) and n-tridecane (C13), and mixtures thereof and also mixtures of n-undecane (C11) and n-tridecane (C13), and volatile C5-C12 cyclic, nonaromatic alkanes;
- short-chain esters containing from 3 to 8 carbon atoms in total, in particular ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate;
- carbonate hydrocarbon-based oils of structure RT-O-C(O)-O-R’2 in which RT and R’2 independently denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group, advantageously chosen more preferentially from dibutyl carbonate or dipentyl carbonate;
- ether oils of formula R1-O-R2 in which Ri and R2, independently of each other, denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group;
- silicone oils, in particular comprising from 2 to 7 silicon atoms, and optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms, in particular dimethicones of viscosity 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof; more preferentially, the volatile oil(s) v) are chosen from Cs-Ci6 alkanes, in particular branched alkanes, preferably isododecane.
In particular, at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process according to the invention comprises one or more non-volatile oils, preferably chosen from:
- non-volatile fluoro oils, in particular chosen from fluorinated polyethers, fluoro silicone oils and fluorosilicones;
- non-volatile silicone oils, in particular chosen from non-volatile silicones having the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyl trimethicone, diphenylsiloxy phenyl trimethicone; and also mixtures thereof;
- non-volatile apolar hydrocarbon-based oils, in particular chosen from linear or branched compounds of mineral or synthetic origin: i) liquid paraffin, ii) squalane, isoeicosane, iii) mixtures of linear, saturated hydrocarbons, more particularly C15-C28 hydrocarbons, in particular mixtures whose INCI names are (C15-C 19) Alkane, (C18-C21) Alkane, (C21- C28) Alkane, iv) hydrogenated or non-hydrogenated polybutenes; v) hydrogenated or nonhydrogenated polyisobutenes, preferably hydrogenated, vi) hydrogenated or nonhydrogenated polydecenes, vii) decene/butene copolymers, butene/isobutene copolymers and viii) mixtures thereof;
- non-volatile polar hydrocarbon-based oils, which may be chosen from: i) saturated, unsaturated, linear or branched C10-C26 fatty alcohols, preferably monoalcohols; in particular, the C10-C26 alcohols are fatty alcohols, which are preferably branched when they comprise at least 16 carbon atoms; preferably, the fatty alcohol comprises from 10 to 24 carbon atoms, and more preferentially from 12 to 22 carbon atoms, in particular such as lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecylpentadecanol, 2- hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof; ii) triglycerides consisting of fatty acid esters of glycerol, in particular the fatty acids of which may have chain lengths ranging from C4 to C36, and notably from Cis to C36, these oils possibly being linear or branched, and saturated or unsaturated; by way of example, mention may notably be made of heptanoic or octanoic triglycerides, caprylic/capric acid triglycerides, plant oils such as wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, com oil, apricot kernel oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, musk rose oil, groundnut oil, coconut oil, argan oil, kaya oil; the liquid fraction of shea butter, and the liquid fraction of cocoa butter; and also mixtures thereof; iii) linear aliphatic hydrocarbon-based esters of formula R-C(O)-OR’ in which R-C(O)-O- represents the carboxylic acid residue containing from 2 to 40 carbon atoms, and R’ represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms, aliphatic hydrocarbon-based esters of alkylene glycol, in particular ethylene glycol or propylene glycol; the total number of carbon atoms in particular being at least 10; notably chosen from isoamyl laurate, cetostearyl octanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate or isostearate, ethyl palmitate, 2-ethylhexyl palmitate, isostearyl isostearate, octyl stearate, isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate or tridecyl octanoate, 2- ethylhexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol bis(2-ethylhexanoate) and mixtures thereof, hexyl laurate, neopentanoic acid esters, such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate or 2- octyldodecyl neopentanoate, isononanoic acid esters, in particular isononyl isononanoate, isotridecyl isononanoate or octyl isononanoate, oleyl erucate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate or myristyl myristate; iv) hydroxylated esters, in particular polyglyceryl-2 triisostearate; v) aromatic esters, in particular tridecyl trimellitate, C12-C15 alcohol benzoate, the 2- phenylethyl ester of benzoic acid, and butyloctyl salicylate; vi) linear fatty acid esters with a total carbon number ranging from 35 to 70, in particular pentaerythrityl tetrapelargonate; vii) esters of C24-C28 branched fatty acids or fatty alcohols, in particular triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl tris(2- decyltetradecanoate), pentaerythrityl tetraisostearate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetrakis(2-decyltetradecanoate); viii) the polyesters obtained by condensation of dimer and/or trimer of unsaturated fatty acid and of diol, in particular those with the INCI name Dilinoleic Acid/Butanediol Copolymer or Dilinoleic Acid/Propanediol Copolymer; the polyesters obtained by condensation of fatty acid dimer and of diol dimer, in particular dimer dilinoleyl dimer dilinoleate; ix) synthetic ethers containing from 10 to 40 carbon atoms, in particular dicaprylyl ether; x) dialkyl carbonates, the two alkyl chains possibly being identical or different, in particular dicaprylyl carbonate; xi) vinylpyrrolidone copolymers, in particular vinylpyrrolidone/ 1 -hexadecene copolymer; and xii) mixtures thereof;
- the non-volatile carbonate oils may be chosen from the carbonates of formula Rs-O- C(O)-O-R9, with Rs and R9, which may be identical or different, representing a linear or branched C4 to C12 and preferentially Cf> to C10 alkyl chain; the carbonate oils may be dicaprylyl carbonate (or dioctyl carbonate), bis(2-ethylhexyl) carbonate, dipropylheptyl carbonate, dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate;
- oils known as non-volatile ether oils of formula R1-O-R2 in which Ri and R2 independently denote a linear, branched or cyclic C6-C24 alkyl group, preferably a Ce-Cis alkyl group, and preferably Cs-Ci2 alkyl group. It may be preferable for Ri and R2 to be identical. Linear alkyl groups that may be mentioned include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a behenyl group, a docosyl group, a tricosyl group and a tetracosyl group. Branched alkyl groups that may be mentioned include a 1,1 -dimethylpropyl group, a 3-methylhexyl group, a 5-methylhexyl group, an ethylhexyl group, a 2-ethylhexyl group, a 5-methyloctyl group, a 1-ethylhexyl group, a 1-butylpentyl group, a 2-butyloctyl group, an isotridecyl group, a 2-pentylnonyl group, a 2-hexyldecyl group, an isostearyl group, a 2 -heptylundecyl group, a 2-octyldodecyl group, a 1,3- dimethylbutyl group, a l-(l-methylethyl)-2-methylpropyl group, a 1,1,3,3-tetramethylbutyl group, a 3,5,5-trimethylhexyl group, a l-(2-methylpropyl)-3-methylbutyl group, a 3,7- dimethyloctyl group and a 2-(l,3,3-trimethylbutyl)-5,7,7-trimethyloctyl group. As cyclic alkyl groups, mention may be made of a cyclohexyl group, a 3 -methylcyclohexyl group and a 3,3,5-trimethylcyclohexyl group, dilauryl ether, diisostearyl ether, dioctyl ether, nonylphenyl ether, dodecyl dimethylbutyl ether, cetyl dimethylbutyl ether and mixtures thereof.
Preferably, the non-volatile oil(s) are chosen from hydrogenated or non-hydrogenated polyisobutenes, preferably hydrogenated, in particular the non-volatile compounds of the Parleam® range; mixtures of C15-C19 alkanes, and from linear aliphatic hydrocarbon-based esters of formula R-C(O)-OR’ in which R-C(0)-0 represents a carboxylic acid residue containing from 2 to 40 carbon atoms, and R’ represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms, as defined previously, in particular isononyl isononanoate.
More preferentially, the process of the invention uses one or more hydrocarbon-based oils containing from 8 to 16 carbon atoms, and notably branched Cs-Ci6 alkanes, in particular isoalkanes, preferably C13-C16 isoparaffins, isododecane, isodecane, isohexadecane, alone or as mixtures, and more preferentially isododecane.
In particular, the amount of oil(s) in at least one of the compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process according to the invention ranges from 1% to 50% by weight, relative to the total weight of the composition, more particularly from 2% to 30% by weight, preferentially from 3% to 20%, better still from 5% to 15% by weight, relative to the total weight of the composition.
COMPOSITIONS
According to a preferred embodiment, the process for treating keratin materials according to the invention uses water, and the composition(s) “Cl” to “C5” used in the process of the invention comprise water.
Thus, in particular, the composition “Cl” is aqueous or aqueous -alcoholic. Preferably, the composition “Cl” is aqueous -alcoholic.
In particular, the composition “C2” is aqueous or aqueous -alcoholic. Preferably, the composition “C2” is aqueous -alcoholic. In particular, the composition “C3” is aqueous or aqueous -alcoholic. Preferably, the composition “C3” is aqueous -alcoholic.
In particular, the composition “C4” is aqueous or aqueous -alcoholic. Preferably, the composition “C4” is aqueous.
In particular, the composition “C5” is aqueous or aqueous -alcoholic.
More particularly, the compositions “Cl”, “C2”, “C3”, “C4” and/or “C5”, preferably “Cl”, “C2” and/or “C3”, are aqueous-alcoholic. Preferably, they comprise an ethanol/water mixture, in particular in a volume ratio of between 1/99 and 99/1, more particularly between 10/90 and 90/10, even more particularly between 20/80 and 80/20, preferably 40/60 and 60/40, such as 50/50.
According to a particular embodiment, the compositions “Cl”, “C2”, “C3”, “C4” or “C5” may be in anhydrous, water-in-oil emulsion or oil-in-water emulsion form.
According to a particular embodiment, composition “C2” is anhydrous. In particular, composition “C2” is anhydrous, and it comprises at least one oil, in particular a volatile oil, preferably isododecane.
According to a particular embodiment, composition “C3” is anhydrous. In particular, composition “C3” is anhydrous, and it comprises at least one oil, in particular a volatile oil, preferably isododecane.
According to another particular embodiment of the invention, “Cl” is an anhydrous composition. According to another variant, composition “C4” is anhydrous. According to another variant, composition “C5” is anhydrous.
The compositions “Cl” to “C5” used in the process of the invention may also comprise one or more organic solvents, other than the water-soluble solvent(s) with which the compound(s) of formula (I) is(are) used.
The term “organic solvent” means an organic substance that is capable of dissolving another substance without chemically modifying it.
According to a particular embodiment, the composition also comprises one or more polyols, notably chosen from polyols notably containing from 2 to 10 carbon atoms, preferably containing from 2 to 6 carbon atoms, preferably glycerol.
The compositions “Cl”, “C2”, “C3”, “C4” or “C5” used in the process of the invention may also comprise one or more adjuvants commonly used in cosmetics, in particular chosen from thickeners, film-forming agents, gelling agents, trace elements, softeners, sequestrants, fragrances, basifying or acidifying agents, dispersants, preserving agents, fillers, surfactants, hair-loss counteractants, anti-dandruff agents, free-radical scavengers, propellants, polar additives and polymers, or mixtures thereof.
Another subject of the invention is a composition “Cl”, which is preferably aqueous or aqueous-alcoholic, comprising i) at least one compound of formula (I) as defined previously, iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously.
Another subject of the invention is a composition “C2”, which is preferably aqueous or aqueous-alcoholic, comprising i) at least one compound of formula (I) as defined previously, ii) at least one crosslinking agent, in particular as defined previously, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously.
Another subject of the invention is a composition “C3”, which is preferably aqueous or aqueous-alcoholic, comprising i) at least one compound of formula (I) as defined previously, ii) at least one crosslinking agent, in particular as defined previously, iv) at least one cosmetic active agent, in particular as defined previously, and optionally iii) water.
Another subject of the invention is the cosmetic use of composition “C2” or “C3” as defined previously, for treating keratin materials, in particular for caring for, styling and/or colouring keratin fibres, preferably the hair.
A composition “Cl”, “C2”, “C3”, “C4” or “C5” is generally suitable for application to keratin materials, in particular application to the skin, lips and/or keratin fibres, and thus generally comprises a physiologically acceptable medium, i.e. a medium that is compatible with keratin materials, in particular application to the skin, lips and/or keratin fibres, notably human keratin fibres such as the hair.
It is preferably a cosmetically acceptable medium, i.e. a medium which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort, i.e. stinging or tautness, liable to discourage the user from applying this composition.
A composition “Cl”, “C2”, “C3”, “C4” or “C5” may be in the form of a makeup product, in particular a coloured makeup product, for the skin, in particular a foundation, optionally having care properties, a blusher, a face powder, an eyeshadow, a concealer, an eyeliner; a lip makeup product such as a lipstick, optionally having care properties, a lip gloss or lip pencils; a makeup product for the integuments such as the nails or eyelashes, in particular in the form of a cake mascara, or for the eyebrows and the hair, or a product for the temporary tattooing of bodily skin.
According to a particular embodiment, a composition “Cl”, “C2”, “C3”, “C4” or “C5” is in the form of:
- either a coloured product for the lips;
- or a skincare product, which may be coloured, in particular a cream or a fluid having moisturizing and/or filling and/or tensor properties; or
- a haircare product, in particular a hair dyeing product or a styling product notably free of dyestuff, such as a lacquer, or a “styling” product of the mousse or gel type.
KIT
According to yet another of its aspects, the present invention is also directed towards a multicompartment kit or device, notably a cosmetic kit or device, comprising:
- at least one compartment containing i) at least one compound of formula (I) as defined previously, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously, in particular comprising composition “Cl” as defined previously;
- at least one compartment different from the one which contains i) and containing ii) at least one crosslinking agent, in particular as defined previously, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined previously, in particular comprising composition “C4” as defined previously; and
- optionally, at least one compartment different from those containing i) and ii), and containing iv) at least one cosmetic active agent, in particular as defined previously, which may be identical to or different from that/those optionally contained in the compartments comprising i) and ii).
Throughout the description, including the claims, the expression “comprising a” is to be understood as being synonymous with “comprising at least one” unless otherwise specified. The expressions “between ... and ...”, “comprises from ... to ...”, “formed from ... to ...” and “ranging from ... to ...” should be understood as being inclusive of the limits, unless otherwise specified. The invention is illustrated in greater detail by the examples presented below. Unless otherwise indicated, the amounts indicated are expressed as mass percentages.
Example
Methods and Measurements
Hair dyeing application
The hair dyeing evaluation protocol is detailed below:
The evaluations are conducted according to two different protocols: in 1 or 2 step(s), each on locks of natural hair containing 90% white hair strands. a} One -step protocol
The composition is applied to locks of dry natural hair containing 90% white hairs, at a rate of 1 g of composition per gram of lock.
The locks of hair are left for 5 minutes at room temperature.
The locks of hair are then combed and dried with a hairdryer for 3 minutes.
The locks of hair are left at room temperature for 18 hours at 80% relative humidity. The hair is dyed uniformly and intensely.
The locks of hair thus coloured are then subjected to a test of several repeated shampoo washes so as to evaluate the fastness (persistence) of the colouring obtained with respect to shampoo washing, according to the shampoo washing protocol described below. b) Two-step protocol
A first composition, termed the “base coat”, is applied to locks of dry natural hair containing 90% white hairs, in a proportion of 1 g of composition per gram of lock.
The locks are left for 5 minutes at room temperature. After this first gesture, a second composition, termed the “top coat”, is applied to the lock of hair, at a rate of 1 g per gram of lock.
The locks are left for 5 minutes at room temperature.
The locks of hair are then combed and dried with a hairdryer for 3 minutes.
The locks of hair are left at room temperature for 24 hours at 80% relative humidity. The hair is dyed uniformly and intensely.
The locks of hair thus coloured are then subjected to a test of several repeated shampoo washes so as to evaluate the fastness (persistence) of the colouring obtained with respect to shampoo washes, according to the shampoo washing protocol described below. Shampoo washins protocol
The locks of dyed hair are combed, moistened with water at 35°C and then passed between the fingers five times for 5 seconds. The locks of hair are then squeezed dry between two fingers.
A standard shampoo (Gamier Ultra Doux) is applied uniformly to the dyed locks, in a proportion of 0.4 g of standard shampoo per gram of locks, the locks of hair being massaged gently along the length (6 passes) for 15 seconds, from the root to the end.
The locks of hair are then placed on a watch glass and left to stand for 1 minute.
Next, the locks of hair are rinsed with water while passing the locks between the fingers (15 passes). The locks of hair are then squeezed dry between two fingers before the next shampoo wash.
Once the tests of several shampoo washes have been performed, the locks of hair are combed and dried with a hairdryer.
Persistence protocol
The persistence of the colour of the locks was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).
In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.
The persistence of the colouring is evaluated by the difference in colour AE between the dyed locks before shampoo washing, and then after undergoing one and three shampoo washes according to the protocol described above.
The lower the AE value, the more persistent the colour with respect to shampoo washing.
The AE value is calculated according to the following equation:
[Math 1]
Figure imgf000064_0001
In this equation, L*a*b* represent the values measured after dyeing the hair and after performing the shampoo washes, and Lo*ao*bo* represent the values measured after dyeing the hair but before shampoo washing.
Skin application The composition is applied to Bioskin synthetic skin from Maprecos (Bioskin plate #10) (skin-simulating support made of elastomer) using a film spreader (wet thickness of 100 pm). The deposit is left to dry for 24 hours.
After 24 hours of drying, the deposits are evaluated according to the protocols described hereinbelow.
Resistance to adhesive tape
A piece of adhesive tape (Scotch® Magic™ 810 from 3M; w = 19 mm, L = 5 cm) is applied to the deposit. A weight of approximately 1070 g is placed on the piece of adhesive tape for 30 seconds. The piece of adhesive tape is then removed and mounted on a slide holder so as to properly observe the result. The adherence of the film to the support is thus evaluated.
Resistance to olive oil/sebum/water
0.5 mL of olive oil, sebum or water is applied to the film of formulation. After 5 minutes, the olive oil, sebum or water is removed by wiping 15 times with cotton wool. The deterioration of the film following contact with the drop of attacking agents is thus examined. The resistance is evaluated according to the following scale:
+++: no attack of the deposit, which is as it was originally;
++: a little transfer but the deposit is as it was originally;
+: the deposit is slightly altered and some transfer is observed;
0: the deposit is completely degraded and there is a lot of transfer to the cotton wool.
Example 1: Preparation of the compound 3-(triethoxysilyl)propyl 3-oxobutanoate
[Chem 5]
Figure imgf000065_0001
The synthesis is represented by the following preparation scheme: [Chem 6]
Figure imgf000066_0001
Compound (1) (1 equivalent, 10 ml, 69.3 mmol) and the Karsted catalyst (3 x 10’5 equivalent, 2% Pt in xylene 46.4 pl) are introduced into a 250 ml three-necked round-bottomed flask under argon equipped with a thermometer and a reflux condenser, then the medium is stirred at 70°C.
Triethoxysilane (2) (1.1 equivalent, 14.81 ml, 76.23 mmol) is added dropwise, keeping the internal temperature below 90°C. At the end of the addition, the reaction medium is stirred for 16 hours at 70°C and the progress of the reaction is monitored by XH NMR.
At the end of the reaction, the reaction medium is left to return to room temperature and then the crude reaction product (about 25 g) is deposited on silica gel and purified by chromatography (gradient: Pentane 100% to Pentane/Et2OH 61:15).
3-(Triethoxysilyl)propyl 3-oxobutanoate (compound (3)) (13.22 g, 62% yield) is obtained in the form of a slightly soluble oil with a purity greater than or equal to 95%.
Example 2: Preparation of compositions A, B and C
Composition A, and compositions B and C, which are free of compound of formula (I) or crosslinker, are prepared using the contents indicated in the table below. The contents are expressed as weight percentages relative to the total weight of the composition. [Table 2]
Figure imgf000066_0002
Table 2 Compositions A, B and C are prepared at room temperature (at a temperature ranging from 18°C to 25°C), observing the following order of incorporation into the aqueous-alcoholic solvent (FEO/EtOH 50:50), with agitation on a vortex mixer for 30 s in order to homogenize the formula:
(i) red iron oxide,
(ii) 3-(triethoxysilyl)propyl 3-oxobutanoate, and then
(iii) APTES.
The same order is observed for the three compositions (depending on the presence of the compound).
Example 3: One-step hair application of compositions A, B and C
Compositions A, B and C are applied according to the one-step protocol described previously.
The evaluation results are summarized in the table below:
[Table 3]
Figure imgf000067_0001
Table 3: Colorimetric measurements
It is seen that the application of composition A according to the process of the invention makes it possible to significantly improve the colour persistence compared to the application of compositions B and C.
Example 4: Preparation of compositions I). E and F
Compositions D, E and F are prepared using the contents indicated in the table below. The contents are expressed as weight percentages relative to the total weight of the composition under consideration.
[Table 4]
Figure imgf000068_0001
Table 4
The “base coat” compositions are prepared at room temperature (at a temperature ranging from 18°C to 25°C) by dispersing the red iron oxide in the aqueous-alcoholic solvent (ILO/EtOH 50:50) and by then adding the 3- (triethoxy silyl)propyl 3-oxobutanoate thereto.
The formula is then homogenized on a vortex mixer for 30 s.
The “top coat” compositions are prepared at room temperature (at a temperature ranging from 18°C to 25°C) by adding the chitosan to the water and by then incorporating the lactic acid therein. The medium is then agitated on a vortex mixer for 30 s. When red iron oxide is present, this is dispersed in the previously prepared chitosan solution by agitation on a vortex mixer for 30 s.
Example 5: Two-step hair application of compositions D, E and F
Compositions D, E and F are applied according to the two-step protocol described previously.
The evaluation results are summarized in the table below: [Table 5]
Figure imgf000069_0001
Table 5: Colorimetric measurements
It is seen that the application of the compositions D according to the process of the invention makes it possible to significantly improve the colour persistence compared to the application of a “base coat” only (composition E) or of a “top coat” only (compositions F).
Example 6: Preparations of compositions G and H
Compositions G and H are prepared using the contents indicated in the table below. The contents are expressed as weight percentages relative to the total weight of the composition under consideration.
[Table 6]
Figure imgf000069_0002
Table 6 Compositions G and H are prepared by simply mixing the ingredients detailed in Table 6 using a Speed Mixer (mixing equipment which uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature (at a temperature ranging from 18 °C to 25 °C). Example 6: One-step skin application of compositions G and H
Compositions G and H are applied according to the skin application protocol described previously.
The deposits are then evaluated according to the protocols of resistance to olive oil, to sebum and to water, and of resistance to adhesive tape, of the formulations on Bioskin.
The evaluation results are summarized in the table below:
[Table 7]
Figure imgf000070_0001
Table 7 It is seen that the application of composition G according to the process of the invention allows a persistence to water, to sebum and to olive oil to be obtained which is improved in relation to the application of composition H, the deposit of composition G according to the invention being much more adherent and cohesive than the deposit of comparative composition H.
By virtue of the application of composition G according to the process of the invention, deposits which are resistant to everyday chemical (water/sebum/olive oil) and mechanical (adhesive tape test) attacks are thus obtained.

Claims

Claims
1. Process for treating keratin materials, comprising the application to said keratin materials, in one or more successive steps, of at least: i) one or more compounds of formula (I), and also the optical or geometrical isomers thereof, and/or solvates thereof, such as hydrates, or a composition containing same:
Figure imgf000071_0001
in which formula (I):
- X represents -O- or -N(Ra) with Ra representing a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom,
- R1 represents a (Ci-Ce/alkyl group, in particular a (Ci-C4)alkyl group, preferably a (Ci- C2)alkyl group, such as methyl or ethyl, or a hydrogen atom,
- R2 represents a (Ci-C2)alkyl group, in particular methyl,
- Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group, preferably Rb and Rc represent a hydrogen atom,
- Rd represents a linear or branched (Ci-C4)alkyl group, preferably Rd represents a methyl group,
- ALK represents an aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic or acyclic, divalent hydrocarbon-based group, comprising from 1 to 10 carbon atoms, in particular a saturated or unsaturated, preferably saturated, linear or branched, acyclic hydrocarbon-based chain, preferably comprising from 1 to 6 carbon atoms, preferably a (Ci- C4) alkylene group, such as propylene;
- m is equal to 0, 1 or 2, and
- n is equal to 1, 2 or 3, it being understood that the sum of (m + n) is 3; it being understood that:
- when n is 2 or 3, then the R1 radicals are identical or different, preferably identical, and
- when m is 2 or 3, then the R2 radicals are identical or different, preferably identical; and ii) at least one crosslinking agent; iii) optionally water, preferably water.
2. Treatment process according to the preceding claim, in which the compound(s) of formula (I) is(are) chosen from the compounds of formula (I’), and also the optical or geometrical isomers thereof, and the solvates thereof, such as hydrates:
Figure imgf000072_0001
(D in which formula (I’) R1, R2, X, m and n are as defined according to Claim 1.
3. Treatment process according to any one of the preceding claims, in which the compound(s) of formula (I) is(are) chosen from:
- 3-(Trimethoxysilyl)propyl acetoacetate;
- 3-(Triethoxysilyl)propyl 3-oxobutanoate;
- 3-(Dimethoxymethylsilyl)propyl 3-oxobutanoate;
- 3-(Diethoxymethylsilyl)propyl 3-oxobutanoate;
- 3-(Dihydroxymethylsilyl)propyl 3-oxobutanoate;
- 3-Oxo-N-[3-(trimethoxysilyl)propyl]butanamide;
- N-[3-(Dihydroxymethylsilyl)propyl]-3-oxobutanamide; and
- mixtures thereof.
4. Treatment process according to any one of the preceding claims, in which the compound of formula (I) is at least 3-(triethoxysilyl)propyl 3-oxobutanoate.
5. Treatment process according to any one of the preceding claims, comprising the application of at least iii) water to said keratin materials.
6. Treatment process according to any one of the preceding claims, in which the compound(s) of formula (I) are used in a medium containing at least one water-soluble solvent, in particular chosen from polar protic solvents, more particularly chosen from (poly)hydroxy(C2-C6)alkanes, preferably from (C2-C4)alkanols, and more preferentially is ethanol.
7. Treatment process according to any one of the preceding claims, in which the crosslinking agent(s) ii) is(are) chosen from (poly)amine, (poly)thiol, (poly)acrylate and metal alkoxide compounds, and mixtures thereof, and preferably chosen from (poly)amine, (poly)thiol and (poly)acrylate compounds, and mixtures thereof.
8. Treatment process according to any one of the preceding claims, in which the crosslinking agent(s) is(are) chosen from:
A) (poly)amine compounds chosen from: ia) chitosans such as poly(D-glucosamine), ib) polyether diamines, in particular polyethylene glycol a,co-diamines, bearing a chain-end amine function, ic) polyether triamines, in particular polyetheramines (or Jeffamine), id) aminoalkoxy silanes, in particular APTES, and ie) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly bis(3-aminopropyl)-terminated poly (dimethoxy siloxane) (PDMS-diNEE) and amodimethicones comprising amine groups on side chains, more particularly bis-cetearyl amodimethicone ;
B) (poly)thiol compounds chosen from: iia) polydialkylsiloxanes bearing thiol functions, and iib) alkoxysilanes bearing thiol functions, and in particular chosen from iia) polydialkylsiloxanes bearing thiol functions, preferably from polydimethylsiloxanes comprising thiol groups on the side chain, in particular mercaptopropyl, and more particularly chosen from the compounds of formula (XIII): Ra-Si(Rb)(Rd)-O-[Si(Ra)(Rb)-O]m-[Si(Rb)(ALKi-SH)-O]n-Si(Rb)(Rd)-Ra (XIII) in which formula (XIII):
- Ra and Rb, which may be identical or different, preferably identical, represent a (Ci- C4)alkyl group, in particular methyl, a (Ci-C4)alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(Ci-C4)alkyl group, in particular benzyl, or an aryl(Ci-C4)alkoxy group, in particular benzoxy, preferably a (Ci-C4)alkyl group, more preferentially methyl,
- Rd represents a (Ci-C4)alkyl group, in particular methyl, a (Ci-C4)alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(Ci-C4)alkyl group, in particular benzyl, an aryl(Ci-C4)alkoxy group, in particular benzoxy, or a (Ci-C6)alkyl group substituted with a (Ci-C4)alkylamino, amino or thiol group, and preferably a (Ci-C4)alkyl group, more preferentially methyl, and preferably Ra, Rb and Rd are identical and represent a (Ci-C6)alkyl group, more preferentially methyl,
- ALKi represents a linear or branched, optionally cyclic, saturated or unsaturated divalent hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, a (thio)carbonyl group C(X) with X representing O or S, or combinations thereof, in particular -O-, -O-C(O)- or -C(O)-O-; preferably, ALKi represents a (Ci-C6)alkylene and more preferentially (C1-C4) alkylene group, even more preferentially propylene,
- n and m, which may be identical or different, represent an integer greater than 2, and in particular the values of m and n are such that the weight-average molecular weight of said polyorganosiloxane is between 1000 and 55 000 g.mol 1; and
C) the (poly)acrylate compounds of formula (XIV):
L[-Y-C(O)-C(Re)=CH2]q (XIV) in which formula (XIV):
- q represents an integer greater than or equal to 2, in particular n is between 2 and 10 inclusive and preferably between 2 and 5,
- L denotes a linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated, multivalent (at least divalent) group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms; L being optionally interrupted and/or terminated with one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and combinations thereof, in particular -O-, -O-C(X)-, -N(R)-C(X)-, -Si(Rc)(Rd)-O- with R representing a hydrogen atom or a (Ci-C6)alkyl group, in particular methyl; and/or L being optionally substituted with one or more groups chosen from: -N(Ra)Rb and -(X’)a-C(X)-(X”)b-Ra; with X, X’ and X”, which may be identical or different, representing an oxygen or sulfur atom, or a group N(Rb); a and b being 0 or 1, preferably the sum of a + b being 1; Ra and Rb, which may be identical or different, represent a hydrogen atom, a (Ci-Ce/alkyl group or an aryl(Ci-C4) alkyl group, in particular benzyl, preferably Ra and Rb represent a hydrogen atom, and Rc and Rd, which may be identical or different, represent a (Ci-C6)alkyl, aryl(Ci-C4)alkyl or (Ci-C6)alkoxy group,
- Re represents a hydrogen atom or a (Ci-C4)alkyl group, in particular methyl; preferably, Re represents a hydrogen atom, and
- Y represents an oxygen atom or an amino group -N(H)-, preferably an oxygen atom, preferably Y is an oxygen atom and Re is a hydrogen atom, preferably L represents a di- or trivalent, preferably trivalent, hydrocarbon-based chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, and more preferentially, the compounds of formula (XIV) are trimethylolpropane triacrylate.
9. Treatment process according to any one of the preceding claims, in which iv) at least one cosmetic active agent is also applied to said keratin materials.
10. Treatment process according to the preceding claim, in which the cosmetic active agent(s) iv) are chosen from: a) dyestuffs, in particular chosen from pigments, direct dyes and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV-screening agents, and d) mixtures thereof; preferably, the cosmetic active agent(s) iv) are chosen from a) dyestuffs, preferably chosen from pigments, direct dyes and mixtures thereof; more preferentially, the pigment(s) are chosen from carbon black, iron oxides, in particular yellow, red and black iron oxides, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet triarylmethane pigments, in particular Blue 1 Lake, azo pigments, in particular red azo pigments, more particularly D&C Red 7, an alkali metal salt of lithol red, in particular the calcium salt of lithol red B, and even more preferentially from red iron oxides, yellow iron oxides and azo pigments, in particular red azo pigments, more particularly D&C Red 7.
11. Treatment process according to any one of the preceding claims, in which use is also made of v) at least one fatty substance, in particular at least one oil, preferably at least one volatile oil.
12. Treatment process according to the preceding claim, in which use is also made of v) at least one fatty substance chosen from volatile oils chosen from: - hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular branched Cs-Ci6 alkanes, in particular isoalkanes, more particularly isoalkanes (also known as isoparaffins), preferably C13-C16 isoparaffins, isododecane, isodecane, isohexadecane, for example the oils sold under the trade names Isopar or Permethyl, alone or as mixtures, preferably isododecane (also known as 2,2,4,4,6-pentamethylheptane), linear alkanes, in particular C11-C16 alkanes, alone or as mixtures, in particular hexane, decane, undecane, tridecane, isoparaffins, in particular n-dodecane (C12) and n-tetradecane (C14), the undecanetridecane mixture, mixtures of n-undecane (C11) and n-tridecane (C13), and mixtures thereof and also mixtures of n-undecane (C11) and n-tridecane (C13), and volatile C5-C12 cyclic, nonaromatic alkanes;
- short-chain esters containing from 3 to 8 carbon atoms in total, in particular ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate;
- carbonate hydrocarbon-based oils of structure R’ I-0-C(0)-0-R’2 in which R’i and R’2 independently denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group, advantageously chosen more preferentially from dibutyl carbonate or dipentyl carbonate;
- ether oils of formula R1-O-R2 in which Ri and R2, independently of each other, denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group;
- silicone oils, in particular comprising from 2 to 7 silicon atoms, and optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms, in particular dimethicones of viscosity 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof; more preferentially, the volatile oil(s) v) are chosen from Cs-Ci6 alkanes, in particular branched alkanes, preferably isododecane.
13. Process for treating, notably cosmetically treating, keratin materials according to any one of the preceding claims, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the application to said keratin materials of at least: - a composition, termed “Cl”, comprising i) at least one compound of formula (I) according to any one of Claims 1 to 4, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10;
- a composition, termed “C2”, comprising i) at least one compound of formula (I) according to any one of Claims 1 to 4, ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10;
- a composition, termed “C3”, comprising i) at least one compound of formula (I) according to any one of Claims 1 to 4, ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, and optionally iii) water;
- a composition, termed “C4”, comprising ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, and optionally iii) water;
- a composition, termed “C5”, comprising iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, and optionally iii) water; it being understood that:
• the process uses, together or separately, i) at least one compound of formula (I) according to any one of Claims 1 to 4, ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, and optionally iii) water, and preferably water; and
• the compositions “Cl”, “C2”, “C3”, “C4” and “C5” may be anhydrous, aqueous, in particular aqueous -alcoholic, and/or comprise one or more fatty substances v), in particular according to either of Claims 11 and 12.
14. Treatment process according to the preceding claim, characterized in that it comprises a single step of applying composition “C2” or composition “C3” to said keratin materials.
15. Treatment process according to Claim 13, characterized in that it comprises two successive steps of application, to said keratin materials, of two different compositions, preferably of composition “Cl” and then of composition “C4”.
16. Cosmetic treatment process for caring for, styling and/or colouring keratin fibres, preferably the hair, comprising the successive application of at least: - a composition, termed “Cl”, comprising i) at least one compound of formula (I) according to any one of Claims 1 to 4, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10; and then
- a composition, termed “C4”, comprising ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10; at least one of the compositions “Cl” and/or “C4” containing at least one dyestuff, in particular according to Claim 10, preferably at least one pigment, and more preferentially composition “Cl” comprises at least one pigment.
17. Composition “C2”, preferably an aqueous or aqueous -alcoholic composition, comprising i) at least one compound of formula (I) according to any one of Claims 1 to 4, ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, iii) optionally water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, said composition comprising a physiologically acceptable medium.
18. Composition according to Claim 17 termed “C3”, preferably an aqueous or aqueous -alcoholic composition, comprising i) at least one compound of formula (I) according to any one of Claims 1 to 4, ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, and optionally iii) water, said composition comprising a physiologically acceptable medium.
19. Cosmetic use of composition “C2” or “C3” according to Claim 17 or 18, for treating keratin materials, in particular for caring for, styling and/or colouring keratin fibres, preferably the hair.
20. Multi-compartment kit, in particular cosmetic kit, comprising:
- at least one compartment containing, in a physiologically acceptable medium, at least i) at least one compound of formula (I) according to any one of Claims 1 to 4, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, in particular comprising composition “Cl” according to either of Claims 13 and 16;
- at least one compartment different from the one which contains i) and containing, in a physiologically acceptable medium, ii) at least one crosslinking agent, in particular according to either of Claims 7 and 8, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, in particular comprising composition “C4” according to either of Claims 13 and 16; and
- optionally, at least one compartment different from those containing i) and ii), and containing, in a physiologically acceptable medium, iv) at least one cosmetic active agent, in particular according to either of Claims 9 and 10, which may be identical to or different from that/those optionally contained in the compartments comprising i) and ii).
PCT/EP2023/087795 2022-12-27 2023-12-26 Process for treating keratin materials using at least one alkoxysilane compound bearing acetoacetate functions and at least one crosslinking agent WO2024141527A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FRFR2214554 2022-12-27
FR2214554A FR3143997A1 (en) 2022-12-27 2022-12-27 Process for treating keratin materials using at least one alkoxysilane compound with acetoacetate functions and at least one crosslinking agent

Publications (1)

Publication Number Publication Date
WO2024141527A1 true WO2024141527A1 (en) 2024-07-04

Family

ID=86007601

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/087795 WO2024141527A1 (en) 2022-12-27 2023-12-26 Process for treating keratin materials using at least one alkoxysilane compound bearing acetoacetate functions and at least one crosslinking agent

Country Status (2)

Country Link
FR (1) FR3143997A1 (en)
WO (1) WO2024141527A1 (en)

Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19726C (en) A. NEUBECKER in Offenbach a. M. und E. WELZ in Breslau, Bismarckstrafse 21 Innovations in the lautering apparatus for breweries patented under P. R. No. 10157
DE184C (en) 1877-08-07 M. STEIB in Hamburg Bell shutters on umbrellas
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
US3676440A (en) 1970-02-26 1972-07-11 Grace W R & Co Isocyanurate-containing polythiols
EP0133981A2 (en) 1983-08-05 1985-03-13 Siemens Aktiengesellschaft Mechanical overload protection
EP0336428A2 (en) * 1988-04-08 1989-10-11 Nippon Paint Co., Ltd. Curable composition
US4925659A (en) * 1988-02-08 1990-05-15 L'oreal Cosmetic application of polysiloxanes containing a β-keto ester group and compositions employed
US5166355A (en) 1991-02-04 1992-11-24 Fairmount Chemical Co., Inc. Process for preparing substituted 2,2'-methylene-bis-[6-(2H-benzotriazol-2-yl)-4-hydrocarbyl-phenols]
FR2679771A1 (en) 1991-08-01 1993-02-05 Oreal Use of an insoluble pigment obtained by oxidative polymerisation of indole derivatives for the temporary dyeing of keratinous fibres
WO1993004665A1 (en) 1991-08-29 1993-03-18 L'oreal Filtering cosmetic composition containing a liposoluble filter polymer with hydrocarbonated structure and a filter silicone
US5237071A (en) 1991-01-22 1993-08-17 Fairmount Chemical Company, Inc. Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
EP0669323A1 (en) 1994-02-24 1995-08-30 Haarmann & Reimer Gmbh Utilization of benzazols as UV-absorbers, new benzazoles and process for their preparation
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
GB2303549A (en) 1995-07-22 1997-02-26 Ciba Geigy Ag Micronising organic UV absorbers with alkyl polyglucosides
US5624663A (en) 1987-08-28 1997-04-29 L'oreal Photostable cosmetic filter composition cotaining a UV-A filter and a substituted dialkylbenzalmalonate, the use of substituted dialkylbenzalmalonates in cosmetics as broad-band solar filters and novel substituted dialkyl malonates
FR2741530A1 (en) 1995-11-23 1997-05-30 Oreal USE FOR TEMPORARY COLORING OF HAIR OR HAIR OF ANIMALS OF A COMPOSITION BASED ON A DISPERSION OF FILM-GENERATING POLYMER AND A NON-MELANIC PIGMENT
EP0832642A2 (en) 1996-09-13 1998-04-01 3V SIGMA S.p.A Derivatives of Benzoxazole useful as uv filters
EP0893119A1 (en) 1997-07-26 1999-01-27 Ciba SC Holding AG UV-protection formulation
DE19746654A1 (en) 1997-08-13 1999-02-18 Basf Ag Use of 4,4-di:aryl-butadiene derivatives as photostable UV filter compounds
DE19755649A1 (en) 1997-12-15 1999-06-17 Basf Ag Use of 4,4-diarylbutadienes as photostable UV filters in cosmetics
EP0967200A1 (en) 1998-06-26 1999-12-29 Basf Aktiengesellschaft 4,4-Diarylbutadienes as water soluble, photostable UV-filters for cosmetic and pharmaceutical preparations
DE19855649A1 (en) 1998-12-03 2000-06-08 Basf Ag Dimeric alpha-alkyl-styrene derivatives as photostable UV filters in cosmetic and pharmaceutical preparations
EP1008586A1 (en) 1998-12-11 2000-06-14 Basf Aktiengesellschaft Oligomeric diarylbutadienes
EP1027883A2 (en) 1999-01-11 2000-08-16 3V SIGMA S.p.A Combinations of sunscreen agents with UV-A and UV-B filtering properties
EP1133980A2 (en) 2000-03-15 2001-09-19 Basf Aktiengesellschaft Use of combinations of photoprotectors comprising as essential components aminosubstituted hydroxybenzophenones as photostable UV-filters in cosmetic and pharmaceutical preparations
EP1184426A2 (en) 2000-09-01 2002-03-06 Toda Kogyo Corporation Composite particles, process for producing the same, and pigment, paint and resin composition using the same
EP1247515A2 (en) 2001-04-06 2002-10-09 L'oreal Photo-curable nail enamel without unsaturated monomers
EP1300137A2 (en) 2001-10-02 2003-04-09 3V SIGMA S.p.A Combinations of sunscreens
DE10162844A1 (en) 2001-12-20 2003-07-03 Beiersdorf Ag Cosmetic and dermatological light protection formulations containing bis-resorcinyltriazine derivatives and benzoxazole derivatives
JP2003326843A (en) 2002-05-17 2003-11-19 Fuji Photo Film Co Ltd Ink jet recording sheet
WO2004006878A1 (en) 2002-07-10 2004-01-22 Ciba Specialty Chemicals Holding Inc. Merocyanine derivatives for cosmetic use
EP1392222A1 (en) 2001-06-07 2004-03-03 L'oreal Cosmetic composition forming after application a supramolecular polymer
EP1435900A2 (en) 2001-10-17 2004-07-14 Unilever Plc Cosmetic and personal care compositions
WO2005058269A1 (en) 2003-12-17 2005-06-30 Ciba Specialty Chemicals Holding Inc. Merocyanine derivatives for cosmetic use
EP1572778A2 (en) 2002-12-20 2005-09-14 PPG Industries Ohio, Inc. Sulfide-containing polythiols
JP2005314325A (en) 2004-04-30 2005-11-10 Shin Etsu Chem Co Ltd MANUFACTURING METHOD OF beta-KETOESTER STRUCTURE-CONTAINING ORGANOSILICON COMPOUND
WO2006032741A1 (en) 2004-09-20 2006-03-30 L'oréal Silane merocyanine sulphone derivatives; photoprotecting compositions containing same; use thereof as uv filter
FR2907678A1 (en) 2006-10-25 2008-05-02 Oreal Cosmetic composition useful for hair dyeing, comprises polysiloxane/polyurea block copolymer, colored species or dye, non-siliconated volatile organic solvent
WO2013004777A1 (en) 2011-07-07 2013-01-10 L'oreal Photoprotective composition
WO2014027766A1 (en) 2012-08-16 2014-02-20 동우화인켐 주식회사 Acryl-based adhesive composition
WO2014099108A1 (en) 2012-12-18 2014-06-26 Avon Products, Inc. Enhanced substantivity of cosmetic ingredients on keratinous substrate
JP2016069290A (en) 2014-09-26 2016-05-09 信越化学工業株式会社 Primer composition
US20190315778A1 (en) 2018-04-16 2019-10-17 Evonik Degussa Gmbh Low-viscosity crosslinkers containing alkoxysilane groups
CN111607338A (en) * 2020-05-19 2020-09-01 中国乐凯集团有限公司 Adhesive composition, encapsulation film, and organic electronic device containing encapsulation film
FR3117852A1 (en) * 2020-12-23 2022-06-24 L'oréal Cosmetic composition comprising a copolymer based on acetoacetate functions
FR3117794A1 (en) * 2020-12-23 2022-06-24 L'oreal Aqueous dispersion of a specific copolymer and its cosmetic applications

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19726184A1 (en) 1997-06-20 1998-12-24 Beiersdorf Ag Oil-in-water or multiple emulsion with high concentration of suspended UVB filter

Patent Citations (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19726C (en) A. NEUBECKER in Offenbach a. M. und E. WELZ in Breslau, Bismarckstrafse 21 Innovations in the lautering apparatus for breweries patented under P. R. No. 10157
DE184C (en) 1877-08-07 M. STEIB in Hamburg Bell shutters on umbrellas
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
US3676440A (en) 1970-02-26 1972-07-11 Grace W R & Co Isocyanurate-containing polythiols
EP0133981A2 (en) 1983-08-05 1985-03-13 Siemens Aktiengesellschaft Mechanical overload protection
US5624663A (en) 1987-08-28 1997-04-29 L'oreal Photostable cosmetic filter composition cotaining a UV-A filter and a substituted dialkylbenzalmalonate, the use of substituted dialkylbenzalmalonates in cosmetics as broad-band solar filters and novel substituted dialkyl malonates
US4925659A (en) * 1988-02-08 1990-05-15 L'oreal Cosmetic application of polysiloxanes containing a β-keto ester group and compositions employed
EP0336428A2 (en) * 1988-04-08 1989-10-11 Nippon Paint Co., Ltd. Curable composition
US5237071A (en) 1991-01-22 1993-08-17 Fairmount Chemical Company, Inc. Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)
US5166355A (en) 1991-02-04 1992-11-24 Fairmount Chemical Co., Inc. Process for preparing substituted 2,2'-methylene-bis-[6-(2H-benzotriazol-2-yl)-4-hydrocarbyl-phenols]
FR2679771A1 (en) 1991-08-01 1993-02-05 Oreal Use of an insoluble pigment obtained by oxidative polymerisation of indole derivatives for the temporary dyeing of keratinous fibres
WO1993004665A1 (en) 1991-08-29 1993-03-18 L'oreal Filtering cosmetic composition containing a liposoluble filter polymer with hydrocarbonated structure and a filter silicone
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
EP0669323A1 (en) 1994-02-24 1995-08-30 Haarmann & Reimer Gmbh Utilization of benzazols as UV-absorbers, new benzazoles and process for their preparation
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
GB2303549A (en) 1995-07-22 1997-02-26 Ciba Geigy Ag Micronising organic UV absorbers with alkyl polyglucosides
FR2741530A1 (en) 1995-11-23 1997-05-30 Oreal USE FOR TEMPORARY COLORING OF HAIR OR HAIR OF ANIMALS OF A COMPOSITION BASED ON A DISPERSION OF FILM-GENERATING POLYMER AND A NON-MELANIC PIGMENT
EP0832642A2 (en) 1996-09-13 1998-04-01 3V SIGMA S.p.A Derivatives of Benzoxazole useful as uv filters
EP0893119A1 (en) 1997-07-26 1999-01-27 Ciba SC Holding AG UV-protection formulation
DE19746654A1 (en) 1997-08-13 1999-02-18 Basf Ag Use of 4,4-di:aryl-butadiene derivatives as photostable UV filter compounds
DE19755649A1 (en) 1997-12-15 1999-06-17 Basf Ag Use of 4,4-diarylbutadienes as photostable UV filters in cosmetics
EP0967200A1 (en) 1998-06-26 1999-12-29 Basf Aktiengesellschaft 4,4-Diarylbutadienes as water soluble, photostable UV-filters for cosmetic and pharmaceutical preparations
DE19855649A1 (en) 1998-12-03 2000-06-08 Basf Ag Dimeric alpha-alkyl-styrene derivatives as photostable UV filters in cosmetic and pharmaceutical preparations
EP1008586A1 (en) 1998-12-11 2000-06-14 Basf Aktiengesellschaft Oligomeric diarylbutadienes
EP1027883A2 (en) 1999-01-11 2000-08-16 3V SIGMA S.p.A Combinations of sunscreen agents with UV-A and UV-B filtering properties
EP1133980A2 (en) 2000-03-15 2001-09-19 Basf Aktiengesellschaft Use of combinations of photoprotectors comprising as essential components aminosubstituted hydroxybenzophenones as photostable UV-filters in cosmetic and pharmaceutical preparations
EP1184426A2 (en) 2000-09-01 2002-03-06 Toda Kogyo Corporation Composite particles, process for producing the same, and pigment, paint and resin composition using the same
EP1247515A2 (en) 2001-04-06 2002-10-09 L'oreal Photo-curable nail enamel without unsaturated monomers
EP1392222A1 (en) 2001-06-07 2004-03-03 L'oreal Cosmetic composition forming after application a supramolecular polymer
EP1300137A2 (en) 2001-10-02 2003-04-09 3V SIGMA S.p.A Combinations of sunscreens
EP1435900A2 (en) 2001-10-17 2004-07-14 Unilever Plc Cosmetic and personal care compositions
DE10162844A1 (en) 2001-12-20 2003-07-03 Beiersdorf Ag Cosmetic and dermatological light protection formulations containing bis-resorcinyltriazine derivatives and benzoxazole derivatives
JP2003326843A (en) 2002-05-17 2003-11-19 Fuji Photo Film Co Ltd Ink jet recording sheet
WO2004006878A1 (en) 2002-07-10 2004-01-22 Ciba Specialty Chemicals Holding Inc. Merocyanine derivatives for cosmetic use
EP1572778A2 (en) 2002-12-20 2005-09-14 PPG Industries Ohio, Inc. Sulfide-containing polythiols
WO2005058269A1 (en) 2003-12-17 2005-06-30 Ciba Specialty Chemicals Holding Inc. Merocyanine derivatives for cosmetic use
JP2005314325A (en) 2004-04-30 2005-11-10 Shin Etsu Chem Co Ltd MANUFACTURING METHOD OF beta-KETOESTER STRUCTURE-CONTAINING ORGANOSILICON COMPOUND
WO2006032741A1 (en) 2004-09-20 2006-03-30 L'oréal Silane merocyanine sulphone derivatives; photoprotecting compositions containing same; use thereof as uv filter
FR2907678A1 (en) 2006-10-25 2008-05-02 Oreal Cosmetic composition useful for hair dyeing, comprises polysiloxane/polyurea block copolymer, colored species or dye, non-siliconated volatile organic solvent
WO2013004777A1 (en) 2011-07-07 2013-01-10 L'oreal Photoprotective composition
FR2977490A1 (en) 2011-07-07 2013-01-11 Oreal PHOTOPROTECTIVE COMPOSITION
US20140134120A1 (en) 2011-07-07 2014-05-15 L'oreal Photoprotective composition
WO2014027766A1 (en) 2012-08-16 2014-02-20 동우화인켐 주식회사 Acryl-based adhesive composition
WO2014099108A1 (en) 2012-12-18 2014-06-26 Avon Products, Inc. Enhanced substantivity of cosmetic ingredients on keratinous substrate
JP2016069290A (en) 2014-09-26 2016-05-09 信越化学工業株式会社 Primer composition
US20190315778A1 (en) 2018-04-16 2019-10-17 Evonik Degussa Gmbh Low-viscosity crosslinkers containing alkoxysilane groups
CN111607338A (en) * 2020-05-19 2020-09-01 中国乐凯集团有限公司 Adhesive composition, encapsulation film, and organic electronic device containing encapsulation film
FR3117852A1 (en) * 2020-12-23 2022-06-24 L'oréal Cosmetic composition comprising a copolymer based on acetoacetate functions
FR3117794A1 (en) * 2020-12-23 2022-06-24 L'oreal Aqueous dispersion of a specific copolymer and its cosmetic applications

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Photoactive Diazoketo-Functionalized Self-Assembled Monolayer for Biomolecular Patterning", LANGMUIR, vol. 25, no. 16, 2009, pages 8888 - 8893
"Ullmann's Encyclopedia", 2005, WILEY-VCH, article "Dyes, General Survey"
C.G. OVERBERGER, INSTITUTE OF BROOKLYN, Retrieved from the Internet <URL:http://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf>
KIRK-OTHMER'S ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY AND IN ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY
PROGRESS IN COATING, vol. 135, 2019, pages 510 - 516

Also Published As

Publication number Publication date
FR3143997A1 (en) 2024-06-28

Similar Documents

Publication Publication Date Title
US7686849B2 (en) Oxidative hair dyes and related topical compositions
JP7512267B2 (en) Method for treating keratin fibers with acrylic anhydride polymers and amine compounds in oil dispersions - Patents.com
US20240307290A1 (en) Cosmetic composition comprising a copolymer based on acetoacetate functions
FR3040879A1 (en) ANHYDROUS FILTERING COMPOSITION COMPRISING A SILICONE FATTY PHASE
JP2019509869A (en) Device for applying a composition in the form of an emulsion comprising a film-forming agent and a non-volatile oil
ES2664720T3 (en) Water resistant compositions containing a heterocyclic compound and a compound having at least one functional group selected from an amino group and a hydroxyl group
US20230108877A1 (en) Oily dispersion comprising a polymeric particle and a stabilizer bearing a c9-c22 alkyl group, and process for treating keratin materials using the oily dispersion
WO2024126519A1 (en) Process for treating keratin fibres using a compound derived from the condensation of poly(thi)ol and of acetoacetate and a crosslinking agent
US11253459B2 (en) Dye composition based on copolymers derived from the polymerization of at least one crotonic acid monomer or crotonic acid derivative and of at least one thickening polymer bearing (meth)acrylic acid unit(s), and process for dyeing keratin fibers using same
WO2022136110A1 (en) Cosmetic composition comprising polymer particles based on acetoacetate functions
FR2922758A1 (en) ENHANCING AND / OR COLORING HUMAN KERATINIC FIBERS USING A COMPOSITION COMPRISING A PARTICULAR AMINOSILICIE COMPOUND AND COMPOSITION AND DEVICE
US20240108564A1 (en) Process for coating keratin materials which consists in applying to said materials a coating agent formed by hydrogen bonding interaction of a polyphenol with at least one nonionic polysaccharide
WO2020260641A1 (en) Process for treating keratin materials using an anhydride acrylic polymer in oily dispersion, a plasticizer and an amine compound
WO2024141527A1 (en) Process for treating keratin materials using at least one alkoxysilane compound bearing acetoacetate functions and at least one crosslinking agent
WO2024141526A1 (en) Process for treating keratin materials using at least one (co)polymer of polyvinyl alcohol (pva) bearing acetoacetate functions and at least one crosslinking agent
WO2024126625A1 (en) Keratin material treatment process using at least one polysaccharide compound bearing acetoacetate functions
WO2024126522A1 (en) Process for treating keratin materials using a compound derived from the condensation of poly(thi)ol and of acetoacetate and a crosslinking agent
WO2024141525A1 (en) Process for treating keratin fibres using at least one (co)polymer of polyvinyl alcohol (pva) bearing acetoacetate functions
WO2024141524A1 (en) Process for treating keratin materials using at least one oil bearing acetoacetate functions and at least one crosslinking agent
WO2024141523A1 (en) Process for treating keratin fibres using at least one oil bearing acetoacetate functions
US12138339B2 (en) Dye composition based on copolymers derived from the polymerization of at least one crotonic acid monomer or crotonic acid derivative and on silicone
FR2922761A1 (en) ENHANCING AND / OR COLORING HUMAN KERATINIC FIBERS USING A COMPOSITION COMPRISING A PARTICULAR AMINOSILICIE COMPOUND AND COMPOSITION AND DEVICE
US20200170919A1 (en) Dye composition based on copolymers derived from the polymerization of at least one crotonic acid monomer or crotonic acid derivative and on silicone

Legal Events

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

Ref document number: 23840730

Country of ref document: EP

Kind code of ref document: A1