EP4452201A1 - Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un mélange d'huile volatile et d'huile non volatile - Google Patents

Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un mélange d'huile volatile et d'huile non volatile

Info

Publication number
EP4452201A1
EP4452201A1 EP22844090.5A EP22844090A EP4452201A1 EP 4452201 A1 EP4452201 A1 EP 4452201A1 EP 22844090 A EP22844090 A EP 22844090A EP 4452201 A1 EP4452201 A1 EP 4452201A1
Authority
EP
European Patent Office
Prior art keywords
group
linear
alkyl
oil
carbon atoms
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP22844090.5A
Other languages
German (de)
English (en)
Inventor
Angélina ROUDOT
Romain GARCON
Julien PORTAL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
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 LOreal SA filed Critical LOreal SA
Publication of EP4452201A1 publication Critical patent/EP4452201A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/85—Products or compounds obtained by fermentation, e.g. yoghurt, beer, wine

Definitions

  • Cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing a(n) (un)saturated hydrocarbon-based chain and a mixture of volatile oil and non-volatile oil
  • the present invention relates to a cosmetic composition C1 comprising a) at least one polyhydroxyalkanoate (PHA) copolymer bearing (un)saturated hydrocarbon-based groups, b) at least one volatile oil, and c) at least one non-volatile oil, and also to a process for treating keratin materials using such a composition.
  • PHA polyhydroxyalkanoate
  • FR-A-2964663 describes a cosmetic composition comprising pigments coated with a C3-C21 polyhydroxyalkanoate, such as poly(hydroxybutyrate-co-hydroxyvalerate).
  • WO 2011/154508 describes a cosmetic composition
  • a cosmetic composition comprising a 4-carboxy-2- pyrrolidinone ester derivative and a film-forming polymer which may be a polyhydroxyalkanoate, such as polyhydroxybutyrate, polyhydroxyvalerate and polyhydroxybutyrate-co-polyhydroxyvalerate.
  • US-A-2015/274972 describes a cosmetic composition
  • a cosmetic composition comprising a thermoplastic resin, such as a polyhydroxyalkanoate, in aqueous dispersion and a silicone elastomer.
  • the majority of the polyhydroxyalkanoate copolymers are polymers derived from the polycondensation of polymeric repeating units that are for the most part identical and derived from the same carbon source or substrate. These documents do not describe the cosmetic use of copolymers derived from polycondensation using an aliphatic substrate or first carbon source, and at least one second substrate different from the first, comprising one or more (un)saturated hydrocarbon-based groups with PHAs. There is thus a need for a composition comprising polyhydroxyalkanoate copolymers which are lipophilic or soluble in a fatty phase. This makes it possible to obtain a film on keratin materials which has good cosmetic properties, notably good resistance to oils and to sebum, and also to be able to modify the gloss or the mattness.
  • composition C1 shows good stability, notably after storage for one month at room temperature (25°C).
  • Composition C1 notably after its application to keratin materials, makes it possible to obtain a film having good cosmetic properties, good persistence of the colour without running for when the composition, and also a matt or glossy appearance of the treated keratin materials.
  • the deposit For the application of film-forming polymers to keratin materials, it is preferable for the deposit to be supple, comfortable and non-tacky and to have a gloss that is acceptable for the intended use.
  • compositions C1 described hereinbelow make it possible to significantly improve the resistance to rubbing of polyhydroxyalkanoate (PHA) copolymer(s).
  • PHA polyhydroxyalkanoate
  • the compositions C1 according to the invention make it possible to obtain, after deposition, a film on keratin materials which has good cosmetic properties, notably good resistance to oils and to sebum, and good water resistance, and also to be able to modify the gloss or the mattness. These deposits are, moreover, supple and comfortable.
  • composition C1 comprising: a) one or more polyhydroxyalkanoate (PHA) copolymers which contain, and preferably consist of, several repeating units chosen from the units (A) below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • PHA polyhydroxyalkanoate
  • polymer units (A): - R 1 represents a saturated or unsaturated, linear or branched, non-cyclic hydrocarbon-based chain, or a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon-based chain, comprising from 5 to 28 carbon atoms; preferably, the hydrocarbon-based chain is chosen from i) linear or branched (C5-C28) alkyl, ii) linear or branched (Cs-C28)alkenyl, iii) linear or branched (Cs-C28)alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being:
  • R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (he
  • Another subject of the invention is a process for treating keratin materials, preferably a) keratin fibres, notably human keratin fibres such as the hair, or P) human skin, in particular the lips, using a) one or more PHA copolymers as defined previously, b) one or more volatile oils, c) one or more non-volatile oils, it being understood that the mass ratio between the volatile oil(s) and the non-volatile oil(s) is less than 900, preferably between 3 and 800, more preferentially between 4 and 200.
  • a subject of the invention is a non-therapeutic cosmetic process for treating keratin materials, comprising the application to the keratin materials of a composition C1 as defined previously or CT as defined hereinbelow.
  • the treatment process is in particular a process for caring for or making up keratin materials.
  • the term “cosmetic active agent’ means the radical of an organic or organosilicon compound which can be integrated into a cosmetic composition to give an effect on keratin materials, whether this effect is immediate or provided by repeated applications.
  • cosmetic active agents mention may be made of coloured or uncoloured, fluorescent or non-fluorescent chromophores such as those derived from optical brighteners, or chromophores derived from 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 other than mineral particles, antiperspirant active agents other than mineral particles, desquamating active agents, antioxidant active agents, moisturizing active agents, sebum-regulating active agents, active agents intended for limiting the sheen of the skin, active agents intended for combating the effects of pollution, antimicrobial or bactericidal active agents, antidandruff active agents, and fragrances.
  • 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 other than mineral particles, antiperspirant active agents other than mineral particles, desquamating active agents, antioxidant active agents, moisturizing active agents, sebum-regulating active
  • (hetero)aryk means aryl or heteroaryl groups
  • (hetero)cycloalky means cycloalkyl or heterocycloalkyl groups; the “aryk 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 halogen atom such as chlorine, fluorine or bromine
  • an acylamino radical (-NR-COR’) 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-CO-) 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’SC>2-NR-) 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 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 groups:
  • alkylcarbonylamino (RCO-NR’-), in which the radical R’ is a hydrogen atom or a Ci- 04 alkyl radical and the radical R is a C1-C2 alkyl radical or an amino radical substituted with one or two identical or different C1-C4 alkyl groups;
  • alkylcarbonyloxy (RCO-O-), in which the radical R is a C1-C4 alkyl radical or an amino radical substituted with one or two identical or different C1-C4 alkyl groups;
  • alkoxycarbonyl in which the radical R is a C1-C4 alkyl radical or an amino radical 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 “aryf’ radical represents a monocyclic or fused or non-fused polycyclic hydrocarbonbased group comprising from 6 to 22 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 poly
  • Sugar radicals that may be mentioned include: sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose;
  • the term “polysaccharide” refers to a polysaccharide sugar which is a polymer constituted of several saccharides bonded together via O-oside bonds, said polymers being constituted of monosaccharide units as defined previously, said monosaccharide units comprising at least 5
  • R1 and/or R 2 represent a hydrogen atom, or a (Ci-C4)alkylcarbonyl group such as acetyl, and more preferentially R1 represents a hydrogen atom and R2 represents a (Ci-C4)alkylcarbonyl group such as acetyl;
  • organic or mineral acid salf more particularly means organic or mineral acid salts in particular chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids: Alk-S(O)2OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(O)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-O- S(O)OH such
  • the chromophore is coloured, i.e. it absorbs wavelengths in the visible range, i.e. preferably between 400 and 800 nm.
  • 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);
  • fluorescent chromophore means a chromophore which is also capable of reemitting in the visible range at an emission wavelength tam of between 400 and 800 nm, and higher than the absorption wavelength, preferably with a Stoke’s shift, i.e.
  • fluorescent chromophores are derived from fluorescent dyes that are capable of absorbing in the visible range bs, i.e. at a wavelength of between 400 and 800 nm, and of re-emitting in the visible range at a tam of between 400 and 800 nm.
  • fluorescent chromophores are capable of absorbing at a tabs of between 420 and 550 nm and of re-emitting in the visible range tam of between 470 and 600 nm;
  • optical brightening chromophore means a chromophore derived from an optical brightening compound or “optical brighteners, optical brightening agents (OBAs)” or “fluorescent brightening agents (FBAs)” or “fluorescent whitening agents (FWAs)’’, i.e. agents which absorb UV radiation, i.e.
  • Optical brightening chromophores are thus colourless to the eye;
  • UV-A screening agenf 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.
  • short UV-A screening agents which absorb rays at a wavelength of between 320 and 340 nm
  • long UV-A screening agents which absorb rays at a wavelength of between 340 and 400 nm
  • UV-B screening agenf 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.
  • Composition C1 of the invention comprises as first ingredient a) one or more PHA copolymers which contain, or preferably consist of, at least two different repeating polymer units (A) as defined previously.
  • composition C1 or CT according to the invention comprises as first ingredient a) one or more PHA copolymers which contain, or preferably consist of, at least two different repeating polymer units chosen from the units (A) and (B) as defined previously.
  • composition C1 of the invention is a composition CT, preferably a cosmetic composition comprising: a) one or more polyhydroxyalkanoate (PHA) copolymers which contain, and preferably consist of, at least two different repeating polymer units chosen from the units (A) and (B) below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • PHA polyhydroxyalkanoate
  • R 1 represents a saturated or unsaturated, linear or branched, non-cyclic hydrocarbon-based chain, or a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon-based chain, comprising from 5 to 28 carbon atoms; particularly a hydrocarbon-based chain chosen from i) linear or branched (Cs-C 2 8) alkyl, ii) linear or branched (Cs-C 2 8)alkenyl, iii) linear or branched (Cs-C 2 8)alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being:
  • R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (he
  • R 2 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 3 to 30 carbon atoms optionally substituted with one or more atoms or groups a) to m) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; in particular chosen from linear or branched (Cs-C28)alkyl and linear or branched (Cs-C28)alkenyl, in particular a linear hydrocarbon-based group, more particularly (C4-C2o)alkyl or (C4-C2o)alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 1 from which two carbon atoms are subtracted; and b) one or more volatile oils; c) one or more non-vol
  • the mass ratio of the sum of the masses b) of volatile oi I (s)/the sum of the masses c) of non-volatile oil(s) is non-zero and less than 900, preferably between 3 and 800, more preferentially between 4 and 200.
  • co-polymer means that said polymer is derived from the polycondensation of polymeric repeating units that are different from each other, i.e. said polymer is derived from the polycondensation of polymeric repeating units (A) that are different from each other, or from the polycondensation of polymeric repeating units (A) with (B), it being understood that the polymeric units (A) are different from the polymeric units (B), it being possible for said copolymer to be obtained from a single saturated or unsaturated aliphatic carbon source which is optionally substituted and/or interrupted, preferably unsubstituted and uninterrupted, or from several carbon sources, in particular at least one of which is an uninterrupted unsubstituted saturated aliphatic and the other carbon source(s) are saturated or unsaturated aliphatic, optionally substituted notably with a halogen atom such as bromine, or with a cyano group, a Bunte salt, a dithiolane radical,
  • the copolymer according to the invention is derived from a single carbon source, preferably a single saturated or unsaturated aliphatic carbon source which is optionally substituted and/or interrupted, preferably unsubstituted and uninterrupted.
  • the copolymer according to the invention is derived from several carbon sources, preferably from 2 to 10 carbon sources, more preferentially 2 to 5 carbon sources and even more preferentially 2 carbon sources.
  • the copolymer according to the invention is derived from several carbon sources and at least one is saturated aliphatic.
  • the PHA copolymer(s) consist of two different repeating polymer units chosen from the units (A) and (B) as defined previously.
  • the PHA copolymer(s) comprise, preferably consist of, two different repeating polymer units chosen from the units (A) as defined previously, the units (B) such that R 2 represents a cyclic or non- cyclic, linear or branched, saturated or unsaturated hydrocarbon-based group comprising from 3 to 30 carbon atoms; in particular chosen from linear or branched (C3- C2s)alkyl and linear or branched (Cs-C28)alkenyl, in particular a linear hydrocarbonbased group, more particularly (C4-C2o)alkyl or (C4-C2o)alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 1 from which two carbon atoms are subtracted.
  • the PHA copolymer(s) according to the invention comprise the repeating unit of formula (I), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R 1 and R 2 are as defined previously;
  • m and n are integers greater than or equal to 1 ; preferably, the sum n + m is inclusively between 450 and 1400; preferably, m > n when R 1 and R 2 represent an unsubstituted and uninterrupted alkyl group - more preferentially, when R 1 and R 2 are linear alkyl, then R 1 is a C5-C13 alkyl group; and R 2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which two carbon atoms are subtracted such as a C3-C11 alkyl group; and preferably, m ⁇ n when R 1 represents a substituted and/or interrupted alkyl group, an optionally substituted and/or interrupted alkenyl group or an optionally substituted and/or interrupted alkynyl group, and R 2 represents an alkyl group.
  • the PHA copolymer(s) of composition a) contain three different repeating polymer units (A), (B) and (C), and preferably consist of three different polymer units (A), (B) and (C) below, and also the optical or geometrical isomers thereof and the solvates thereof such as hydrates:
  • R 3 represents a saturated or unsaturated, linear or branched, cyclic or non-cyclic, hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally substituted with one or more atoms or groups a) to m) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (Ci-C2s)alkyl, and linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbon-based group, more particularly (C4-C2o)alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms in the radical R 1 , or else corresponding to the number of carbon atoms in the radical R 1 minus at least three carbon atoms, preferably corresponding to the number of carbon atoms in the radical R 1 minus four carbon atoms; and it being
  • R 1 , R 2 and R 3 represent an unsubstituted and uninterrupted alkyl group
  • the molar percentage of units (A) is greater than the molar percentage of units (B), and greater than the molar percentage of units (C) - more preferentially, when R 1 , R 2 and R 3 are linear alkyl, then R 1 is a C5-C13 alkyl group
  • R 2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which two carbon atoms are subtracted
  • R 3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which four carbon atoms are subtracted
  • R 1 , R 2 and R 3 represent an unsubstituted and uninterrupted alkyl group
  • R 1 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group
  • the molar percentage of units (A) is less than the molar percentage of units (B) and less than the molar percentage of units (C) if R 2 represents an alkyl group and/or R 3 represents an alkyl group.
  • the PHA copolymer(s) comprise the repeating unit of formula (II), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R 1 , R 2 and R 3 are as defined previously; • m, n and p are integers greater than or equal to 1 ; preferably, the sum n + m + p is inclusively between 450 and 1400; and
  • R 1 , R 2 and R 3 represent an unsubstituted and uninterrupted alkyl group - more preferentially, when R 1 , R 2 and R 3 are linear alkyl, then R 1 is a C5-C13 alkyl group; and R 2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which two carbon atoms are subtracted such as a C3-C11 alkyl group, and R 3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which four carbon atoms are subtracted such as a C1-C9 alkyl group; and
  • R 1 represents a substituted and/or interrupted alkyl group, an optionally substituted and/or optionally interrupted alkenyl group or an optionally substituted and/or optionally interrupted alkynyl group, and R 2 and R 3 represent an alkyl group.
  • the PHA copolymer(s) of composition a) contain four different repeating polymer units (A), (B), (C) and (D), and preferably consist of four different polymer units (A), (B), (C) and (D), below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R 1 , R 2 and R 3 are as defined previously;
  • R 4 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbonbased group comprising from 3 to 30 carbon atoms optionally substituted with one or more atoms or groups a) to m) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (C4-C 2 s)alkyl optionally substituted with one or more atoms or groups a) to m) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; and it being understood that:
  • R 1 , R 2 , R 3 and R 4 represent an unsubstituted and uninterrupted alkyl group
  • the molar percentage of units (A) is greater than the molar percentage of units (B), greater than the molar percentage of units (C), and greater than the molar percentage of units (D) - more preferentially, when R 1 , R 2 , R 3 and R 4 are linear alkyl, then R 1 is a C5-C13 alkyl group
  • R 2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which two carbon atoms are subtracted such as a C3-C11 alkyl group
  • R 3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which four carbon atoms are subtracted such as a C1-C9 alkyl group
  • R 4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which six carbon atoms are
  • R 1 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group
  • the molar percentage of units (A) is less than the molar percentage of units (B) and less than the molar percentage of units (C), notably if R 2 represents an alkyl group and/or R 3 represents an alkyl group
  • R 4 represents an optionally substituted and/or optionally interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group.
  • the PHA copolymer(s) comprise the repeating unit of formula (III), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R 1 , R 2 , R 3 and R 4 are as defined previously;
  • n + m + p + v is inclusively between 450 and 1400;
  • R 1 , R 2 , R 3 and R 4 represent an unsubstituted and uninterrupted alkyl group, then m > n + p + q - more preferentially, when R 1 , R 2 , R 3 and R 4 are linear alkyl, then R 1 is a C5-C13 alkyl group; and R 2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which two carbon atoms are subtracted, R 3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which four carbon atoms are subtracted, and R 4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which six carbon atoms are subtracted; and
  • R 1 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group
  • R 2 and R 3 represent an alkyl group
  • R 4 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, then n > m + v; more preferentially n + p > m + v.
  • the PHA copolymer(s) of composition a) more particularly contain five different repeating polymer units (A), (B), (C), (D) and (E), and preferably consist of five different polymer units (A), (B), (C), (D) and (E), below, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and also the solvates thereof such as hydrates:
  • R 1 , R 2 , R 3 and R 4 are as defined previously;
  • R 5 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbonbased group comprising from 3 to 30 carbon atoms optionally substituted with one or more atoms or groups a) to m) and/or optionally interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (C4-C 2 s)alkyl optionally substituted with one or more atoms or groups a) to m) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; preferably, the hydrocarbonbased group has a carbon number corresponding to the number of carbon atoms of the radical R 4 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 4 from which at least two carbon atoms are subtracted, preferably from which two carbon atoms are subtracted; it being understood that:
  • R 1 , R 2 , R 3 , R 4 and R 5 represent an unsubstituted and uninterrupted alkyl group
  • the molar percentage of units (A) is greater than the molar percentage of units (B), greater than the molar percentage of units (C), greater than the molar percentage of units (D) and greater than the molar percentage of units (E) - more preferentially, when R 1 , R 2 , R 3 , R 4 and R 5 are linear alkyl, then R 1 is a C5-C13 alkyl group
  • R 2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which two carbon atoms are subtracted
  • R 3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which four carbon atoms are subtracted
  • R 4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which six carbon atoms are subtracted
  • R 5 represents
  • R 1 represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group
  • the molar percentage of units (A) is less than the molar percentage of units (B) and less than the molar percentage of units (C) notably if R 2 represents an alkyl group and/or R 3 represents an alkyl group, and R 4 and R 5 represent a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group.
  • the PHA copolymer(s) comprise the repeating unit of formula (IV), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R 1 , R 2 , R 3 , R 4 and R 5 are as defined previously; • m, n, p, v and z are integers greater than or equal to 1 ; preferably, the sum n + m + p + v + z is inclusively between 450 and 1400; and
  • R 1 , R 2 , R 3 , R 4 and R 5 represent an unsubstituted and uninterrupted alkyl group, then m > n + p + v + z;
  • R 1 represents a substituted and/or interrupted alkyl; optionally substituted and/or optionally interrupted alkenyl; or optionally substituted and/or optionally interrupted alkynyl group
  • R 2 and R 3 represent an alkyl group
  • the groups R 4 and R 5 represent a substituted and/or interrupted alkyl; optionally substituted and/or optionally interrupted alkenyl; or optionally substituted and/or optionally interrupted alkynyl group, then n > m + v + z; more preferentially n + p > m + v + z.
  • R 1 represents a linear or branched, preferably linear, (Cs-C28)alkyl hydrocarbon-based chain.
  • the PHA copolymer(s) are such that the radical R 1 is an alkyl group comprising 5 to 14 and preferably between 6 and 12 carbon atoms, more preferentially between 7 and 10 carbon atoms such as n-pentyl, n-hexyl, n-octyl or n- nonyl.
  • the hydrocarbon-based chain R 1 is unsubstituted. According to a particular embodiment of the invention, the hydrocarbon-based chain R 1 is uninterrupted.
  • the hydrocarbon-based chain of the radical R 1 of the invention is 1) either substituted, 2) or interrupted, 3) or substituted and interrupted.
  • the PHA copolymer(s) are such that R 1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is interrupted with one or more (preferably one) atoms or groups chosen from O, S, N(R a ) and carbonyl, or combinations thereof such as ester, amide or urea, with R a being as defined previously, preferably R a represents a hydrogen atom; preferably, R 1 represents an alkyl group which is interrupted with one or more atoms chosen from O and S, more preferentially with an O or S, notably S, atom.
  • R 1 is C7-C20, more particularly Cs-Cis and even more particularly C9-C16.
  • said interrupted hydrocarbon-based chain, notably alkyl is linear.
  • the PHA copolymer(s) are such that R 1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, substituted with one or more (preferably one) atoms or groups chosen from: a) to k) as defined previously.
  • R 1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, substituted with one or more (preferably one) atoms or groups chosen from: a) to k) as defined previously.
  • said hydrocarbon-based chain is substituted with only one atom or group chosen from: a) to k) as defined previously.
  • the PHA copolymer(s) are such that R 1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is substituted with one or more (preferably one) groups chosen from a) halogen such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(Ci-C4)(alkyl)amino and preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as anhydride, dithiolane or epoxide, j) a cosmetic active agent chosen from coloured or uncoloured, fluorescent or non-fluorescent chromophores such as optical brighteners, UV-screening agents, h) (hetero)aryl such as phenyl or furyl, k) R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloal
  • the PHA copolymer(s) are such that R 1 represents a hydrocarbon-based chain, notably an alkyl group as defined previously, which is substituted with one or more (preferably one) groups chosen from a) halogen such as chlorine or bromine, b) hydroxyl, d) (di)(Ci-C4)(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloalkyl such as a sugar radical, preferably a monosaccharide such as glucosyl, y) (hetero)aryl such as phenyl, and X representing a’) O, S or N(R a ),
  • said substituted hydrocarbon-based chain notably alkyl, is linear.
  • said substituted hydrocarbon-based chain notably alkyl, is branched.
  • the hydrocarbonbased chain of the radical R 1 of the invention is substituted and interrupted.
  • the hydrocarbon-based chain (notably an alkyl group as defined previously) of the radical R 1 of the invention is:
  • a cosmetic active agent chosen from coloured or uncoloured, fluorescent or non- fluorescent chromophores such as optical brighteners, UV-screening agents, h) (hetero)aryl such as phenyl or furyl, k) R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, y) (hetero)aryl such as phenyl, 6) a cosmetic active agent as defined previously and X
  • R a represents a hydrogen atom; preferably an alkyl group which is interrupted with one or more atoms chosen from O and S, more preferentially with an O or S, notably S, atom.
  • R 1 is C7-C20, more particularly Cs-Cis and even more particularly C9-C16.
  • the hydrocarbon-based chain (notably an alkyl group as defined previously) of the radical R 1 of the invention is:
  • R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, y) (hetero)aryl such as phenyl, and X representing a’) O, S or N(R a ), preferably S; R a representing a hydrogen atom or a (Ci-C4)alkyl group, preferably R a represents a hydrogen atom; and
  • R a represents a hydrogen atom; preferably an alkyl group which is interrupted with one or more atoms chosen from O and S, more preferentially with an O or S, notably S, atom.
  • R 1 is C7-C20, more particularly Cs-Cis and even more particularly C9-C16.
  • said substituted and interrupted hydrocarbon-based chain is notably alkyl, and is preferably linear.
  • said hydrocarbon-based chain R 1 is substituted, it is substituted at the end of the chain on the opposite side from the carbon atom which bears said radical R 1 .
  • said hydrocarbon-based chain R 1 has the following formula -(CH2) r -X-(ALK) u -G with X being as defined previously, in particular representing O, S or N(R a ), preferably S,
  • ALK represents a linear or branched, preferably linear, (Ci-Cw)alkylene and more particularly (Ci-Cs)alkylene chain
  • r represents an integer inclusively between 6 and 11 , preferably between 7 and 10 such as 8
  • u is equal to 0 or 1
  • G represents a hydrogen atom or a group chosen from hydroxyl, carboxyl, (di)(Ci-C4)(alkyl)amino, (hetero)aryl in particular aryl such as phenyl, cycloalkyl such as cyclohexyl, or a sugar, in particular a monosaccharide optionally protected with one or more groups such as acyl, preferably Sug.
  • G represents a cycloalkyl group such as cyclohexyl, or a sugar as defined previously.
  • G represents a hydrogen atom or a group chosen from hydroxyl, carboxyl, (di)(Ci-C4)(alkyl)amino or (hetero)aryl, in particular aryl such as phenyl.
  • the PHA copolymer(s) are such that R 1 represents (Cs-C28)alkyl substituted with one or more halogen atoms such as fluorine, chlorine or bromine, more particularly linear (C4-C2o)alkyl, even more particularly (Cs-Ci3)alkyl, substituted with a halogen atom such as bromine.
  • the halogen atom is substituted at the end of said alkyl group. More preferentially, R 1 represents 1 -halo- 5-yl such as 1 -bromo- 5-yl.
  • the PHA copolymer(s) are such that R 1 represents a (Cs-C28)alkyl group substituted with one or more groups chosen from g) cyano, and more particularly represents a (Cs-Ci3)alkyl group, which is preferably linear, substituted with a cyano group g), such as 1-cyano-3-propyl.
  • the PHA copolymer(s) are such that R 1 represents vii) a (hetero)aryl(Ci-C2)alkyl and more particularly aryl(Ci- C2)alkyl group, preferably phenylethyl.
  • the PHA copolymer(s) are such that R 1 represents a (Cs-C28)alkyl group substituted with one or more groups chosen from c) (hetero)cycloalkyl. More particularly, R 1 represents a (Cs-Ci3)alkyl group, which is preferably linear, substituted with a heterocycloalkyl group such as epoxide or dithiolane, preferably epoxide.
  • the PHA copolymer(s) are such that R 2 is chosen from linear or branched (Ci-C2s)alkyl, and linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbon-based group, more particularly (Cs-C2o)alkyl or (Cs-C2o)alkenyl, preferably linear or branched, and more particularly linear, (Cs-C2o)alkyl.
  • the PHA copolymer(s) are such that R 2 is chosen from linear or branched (Ci-C2s)alkyl, and linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbon-based group, more particularly (Cs-C2o)alkyl or (Cs-C2o)alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 1 from which two carbon atoms are subtracted.
  • the PHA copolymer(s) are such that the radical R 2 is a linear or branched, preferably linear, (C3-Cs)alkyl, in particular (C3- Ce)alkyl, preferably (C4-Ce)alkyl group such as n-pentyl or n-hexyl.
  • the PHA copolymer(s) comprise a branched (C3-Cs)alkyl, particularly (C4- Ce)alkyl radical R 2 , preferably a branched (C4-Cs)alkyl radical such as isobutyl.
  • the PHA copolymer(s) comprise units (A) bearing an alkyl radical R 1 comprising between 8 and 16 carbon atoms substituted with one or more (preferably one) groups chosen from hydroxyl, (di)(Ci-C4)(alkyl)amino, carboxyl, and R-X- as defined previously, preferably R-S- with R representing a cycloalkyl group such as cyclohexyl, heterocycloalkyl such as a sugar, more preferentially a monosaccharide such as glucose, optionally substituted aryl(Ci-C4)alkyl such as (Ci-C4)(alkyl)benzyl or phenylethyl, or heteroaryl(Ci-C4)alkyl such as furylmethyl.
  • R 1 alkyl radical
  • R 1 comprising between 8 and 16 carbon atoms substituted with one or more (preferably one) groups chosen from hydroxyl, (di)(Ci-C4)(alkyl)amino
  • the copolymer(s) comprise units (B) bearing a linear or branched, preferably linear, (C Cs)alkyl, particularly (C2-Ce)alkyl, preferably (C4-Cs)alkyl radical R 2 such as pentyl.
  • the unit (A) comprises a hydrocarbon-based chain as defined previously, in particular ii), said unit (A) preferably being present in a molar percentage ranging from 0.1% to 99%, more preferentially a molar percentage ranging from 0.5% to 50%, even more preferentially a molar percentage ranging from 1% to 40%, better still a molar percentage ranging from 2% to 30%, or a molar percentage ranging from 5% to 30%.
  • the unit (A) is preferably present in a molar percentage ranging from 0.5% to 99%.
  • the unit (A) when R 1 represents an unsubstituted and uninterrupted (Cs-C28)alkyl group, the unit (A) is preferably present in a molar percentage ranging from 0.5% to 99%, more preferentially from 50% to 99%, more particularly from 60% to 99% and even more preferentially from 70% to 99%.
  • the unit (B) is preferably present in a molar percentage ranging from 2% to 40%; and the unit (C) is preferably present in a molar percentage ranging from 0.5% to 20% relative to all the units (A), (B) and (C).
  • R 1 represents a hydrocarbon-based chain chosen from i) linear or branched (Cs-C28)alkyl, ii) linear or branched (Cs-C28)alkenyl, iii) linear or branched (Cs-C28)alkynyl
  • the hydrocarbon-based group is linear, said hydrocarbon-based chain being substituted with one or more atoms or groups a) to m) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined for R 1 ; it in particular represents a hydrocarbon-based group chosen from linear or branched (C4-C2s)alkyl, optionally substituted with one or more atoms or groups a) to m) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined previously
  • the unit (A) is preferably present in a molar percentage ranging from 0.5% to 99%, more preferentially
  • the PHA copolymer(s) of the invention comprise from 5 mol% to 95 mol% of units (B), notably from 10 mol% to 90 mol% of units (B).
  • the PHA copolymer(s) contain from 0.5 mol% to 10 mol% of units (C); more advantageously, the copolymer comprises from 5 mol% to 95 mol% of units (B), and from 0.5 mol% to 7 mol% of units (C).
  • the PHA copolymer(s) are such that, in the PHA copolymer(s) a):
  • the unit (A) comprises a hydrocarbon-based chain substituted with one or more atoms or groups a) to m) and/or interrupted with one or more heteroatoms or groups a’) to c’) as defined previously, said unit (A) being present in a molar percentage ranging from 0.1% to 99%, preferentially a molar percentage ranging from 0.5% to 50%, more preferentially a molar percentage ranging from 1 % to 40%, even more preferentially a molar percentage ranging from 5% to 30%, better still a molar percentage ranging from 5 mol% to 30 mol% of units (A); and
  • the unit (B) is present in a molar percentage ranging from 1% to 99.5%, preferentially a molar percentage from 1% to 90%, more preferentially a molar percentage from 2 mol% to 70 mol% of units (B); and/or
  • the unit (C) is present in a molar percentage ranging from 0.5% to 20%, preferentially a molar percentage from 1% to 10%, more preferentially from 0.5 mol% to 10 mol% of units (C).
  • R 1 of the unit (A) is a saturated unsubstituted and uninterrupted hydrocarbon-based chain
  • said unit (A) is present in a molar percentage of greater than 30%, more particularly greater than 50%, more preferentially greater than 60%, preferably between 60% and 90%.
  • the values of the molar percentages of the units (A), (B) and (C) of the PHA copolymer(s) are calculated relative to the total number of moles of (A) + (B) if the copolymer(s) do not comprise any additional units (C); otherwise, if the copolymer(s) of the invention contain three different units (A), (B) and (C), then the molar percentage is calculated relative to the total number of moles (A) + (B) + (C); otherwise, if the copolymer(s) of the invention contain four different units (A), (B), (C) and (D), then the molar percentage is calculated relative to the total number of moles (A) + (B) + (C) + (D); otherwise, if the copolymer(s) of the invention contain five different units (A), (B), (C), (D) and (E), then the molar percentage is calculated relative to the total number of moles (A) + (B) + (C)
  • the PHA copolymer(s) of the invention comprise the following repeating units (A), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates: in which repeating units A1 to A12:
  • ALKi represents a divalent linear or branched C1-C20, preferably linear or branched, more preferentially linear, C1-C10, hydrocarbon-based radical;
  • ALK2 represents a divalent linear or branched C1-C20, preferably linear or branched C1- C12, hydrocarbon-based radical;
  • Rr and Rw independently denote a hydrogen atom or a C1-C4 alkyl radical such as methyl; preferably, Rr and Rw are identical;
  • Hal represents a halogen atom such as bromine
  • - Ar represents a (hetero)aryl group such as phenyl
  • Cycl represents a cycloalkyl group such as cyclohexyl or heterocycloalkyl such as dithiolane, or epoxide, preferably epoxide;
  • - Fur represents a furyl group, preferably 2-furyl
  • - Sug represents a sugar group, in particular a monosaccharide optionally protected with one or more groups such as acyl, in particular acetyl; in particular, the stereochemistry of the carbon atoms bearing the radicals R 1 is of (R) configuration.
  • the PHA copolymer(s) of the invention comprise the repeating units (B) of formula (A12), and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates, it being understood that (B) is different from (A).
  • the PHA copolymer(s) of the invention comprise the following repeating units, and also the optical or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • Hal represents a halogen atom such as bromine and t represents an integer between 1 and 10, preferably between 3 and 8 such as 6.
  • Ar represents a (hetero)aryl group such as phenyl;
  • Ar’ represents a (Ci-C4)alkyl(hetero)aryl group such as t-butylphenyl, preferably 4-t- butylphenyl;
  • Cycl represents a cyclohexyl group
  • Fur represents a furyl group, preferably 2-furyl;
  • Sug represents a sugar group, in particular a monosaccharide optionally protected with one or more groups such as acyl; preferably, Sug represents:
  • stereochemistry of the carbon atoms bearing the radicals R 1 and R 2 is of the same (R) or (S) configuration, preferably of (R) configuration. [0076] More particularly, the stereochemistry of the carbon atoms bearing the radicals R 1 ,
  • R 2 and R 3 is of the same (R) or (S) configuration, preferably of (R) configuration. More particularly, the stereochemistry of the carbon atoms bearing the radicals R 1 , R 2 , R 3 and R 4 is of the same (R) or (S) configuration, preferably of (R) configuration.
  • the stereochemistry of the carbon atoms bearing the radicals R 1 , R 2 , R 3 , R 4 and R 5 is of the same (R) or (S) configuration, preferably of (R) configuration.
  • the PHA copolymer(s) have the following formula, and also the optical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • the PHA(s) of the invention are chosen from compounds (1), (2a), (10), (11), (15), (16), (17) and (20), more preferably (15), (16) and (17), notably (16).
  • the PHA(s) of the invention are chosen from compounds (1’), (2a’), (10’), (1 T), (15’), (16’), (17’) and (20’), more preferably (15’), (16’) and (17’), notably (16’).
  • the PHA a) of the invention is compound (23’).
  • the PHA(s) a) of the invention are chosen from compounds (25), (26), (31), (32), (33), (34a) (42), and (43), more preferably (25), (26), (31) and (32), notably (26).
  • the PHA copolymer(s) of the invention preferably have a number-average molecular weight ranging from 50 000 to 150 000.
  • the molecular weight may notably be measured by size exclusion chromatography. A method is described below in the examples.
  • the PHA copolymer(s) are particularly present in composition C1 according to the invention in a content ranging from 0.1 % to 65 % by weight and preferably ranging from 0.1 % to 60 % by weight relative to the total weight of the composition, particularly 1% to 50 % by weight and more particularly ranging from 5 % to 40 % by weight and preferably ranging from 10 % to 35 % by weight, and more preferably ranging from 20 % to 30 % by weight relative to the total weight of the composition.
  • the PHA copolymer(s) are particularly present in composition CT according to the invention in a content ranging from 0.1 % to 60 % by weight relative to the total weight of the composition, particularly 1 % to 50 % by weight and more particularly ranging from 3 % to 40 % by weight and preferably ranging from 5 % to 35 % by weight, more preferably ranging from 10 % to 30 %, and better ranging from 15 % to 20 % by weight relative to the total weight of the composition by weight relative to the total weight of the composition.
  • the term “functionalizable” means that the PHA copolymer(s) comprise a hydrocarbon-based chain comprising one or more atoms or groups that are capable of reacting chemically with another reagent - also referred to as “reactive atoms or reactive groups” - to give a Z covalent bond with said reagent.
  • the reagent is, for example, a compound comprising at least one nucleophilic group and said functionalized hydrocarbon-based chain comprises at least one electrophilic or nucleofugal atom or group, the nucleophilic group(s) reacting with the electrophilic group(s) to covalently graft Z the reagent.
  • the nucleophilic reagent may also react with one or more unsaturations of the alkenyl group(s) to also lead to grafting by covalent bonding of the functionalized hydrocarbon-based chain with said reagent.
  • the addition reaction may also be radical-based, an addition of Markovnikov or anti-Markovnikov type, or nucleophilic or electrophilic substitution.
  • the addition or condensation reactions may or may not take place via a radical route, with or without the use of catalysts or of enzymes, with heating preferably to a temperature less than or equal to 100°C or without supplying heat, under a pressure of greater than 1 atm or otherwise, under an inert atmosphere or otherwise, or under oxygen or otherwise.
  • nucleophilic refers to any atom or group which is electron-donating by an inductive effect +l and/or a mesomeric effect +M. Electron-donating groups that may be mentioned include hydroxyl, thiol and amino groups.
  • electrophilic refers to any atom or group which is electron-withdrawing by an inductive effect -I and/or a mesomeric effect -M. Electron-withdrawing species that may be mentioned include.
  • the microorganisms producing PHAs of the invention notably bearing a hydrocarbon-based chain may be naturally produced by the bacterial kingdom, such as Cyanobacteria of the order of Nostocales (e.g.: Nostoc muscorum, Synechocystis and Synechococcus) but mainly by the Proteobacteria, for example in the class of: -beta-Proteobacteria, of the order Burkholderiales (Cupriavidus negator synonym Ralstonia eutropha)
  • Nostocales e.g.: Nostoc muscorum, Synechocystis and Synechococcus
  • Proteobacteria for example in the class of: -beta-Proteobacteria, of the order Burkholderiales (Cupriavidus negator synonym Ralstonia eutropha)
  • Rhodobacter capsulatus marine and photosynthetic Rhodobacter capsulatus marine and photosynthetic
  • -gamma-Proteobacteria of the order Pseudomonales of the family Moraxellaceae (Acinetobacter junii).
  • the organisms which naturally produce PHAs bearing notably a C3-C5 hydrocarbonbased chain are notably Proteobacteria, such as gamma-Proteobacteria, and more particularly of the order Pseudomonales of the family Pseudomonas such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida GPo1 and Pseudomonas putida KT2440, preferably Pseudomonas putida and in particular Pseudomonas putida GPo1 and Pseudomonas put
  • Certain organisms may also naturally produce PHAs without belonging to the order of Pseudomonales, such as Commamonas testosteroni which belongs to the class of beta-Proteobacteria of the order Burkholderiales of the family of Comamonadaceae.
  • the microorganism producing PHAs according to the invention may also be a recombinant strain if a 3-oxidation PHA synthase metabolic pathway is present.
  • the 3- oxidation PHA synthase metabolic pathway is mainly represented by four classes of enzymes, EC: 2.3.1 B2, EC: 2.3.1 B3, EC: 2.3.1 B4 and EC: 2.3.1 B5.
  • the recombinant strain may be from the Bacteria kingdom, for instance Escherichia coli, or from the Plantae kingdom, for instance Chlorella pyrenoidosa (International Journal of Biological Macromolecules, 116, 552-562 “Influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (PHAs) by microalgae”) or from the Fungi kingdom, for instance Saccharomyces cerevisiae or Yarrowia lipolytica: Applied Microbiology and Biotechnology 91 , 1327-1340 (2011) “Engineering polyhydroxyalkanoate content and monomer composition in the oleaginous yeast Yarrowia lipolytica by modifying the p-oxidation multifunctional protein”).
  • PHAs polyhydroxyalkanoates
  • Use may also be made of genetically modified microorganisms, which may make it possible, for example, to increase the production of PHA, and/or to increase the oxygen consumption capacity, and/or to reduce the autolysis and/or to modify the monomer ratio.
  • the copolymer may be obtained in a known manner by biosynthesis, for example with the microorganisms belonging to the genus Pseudomonas, such as Pseudomonas resinovorans, Pseudomomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellol is, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida, and with a carbon source which may be a C2-C20, preferably Ce-Cis, carboxylic acid, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid, or an alkenoic acid such as undecy
  • the biosynthesis may optionally be performed in the presence of an inhibitor of the P-oxidation pathway, such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid or phenylpropionic acid, and preferably acrylic acid.
  • an inhibitor of the P-oxidation pathway such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid or phenylpropionic acid, and preferably acrylic acid.
  • the process for preparing the PHAs of the invention uses microbial cells which produce PHAs via genetically modified microorganisms (GMOs).
  • GMOs genetically modified microorganisms
  • the genetic modification may increase the production of PHA, increase the oxygen absorption capacity, increase the resistance to the toxicity of solvents, reduce the autolysis, modify the ratio of the PHA comonomers, and/or any combination thereof.
  • the modification of the comonomer ratio of the unit (A) increases the amount of predominant monomer versus (B) of the PHA of the invention which is obtained.
  • the PHA-producing microbial cells reproduce naturally.
  • a genetically modified microbial strain producing PHA that is functionalizable or comprising a reactive group that may be mentioned is Pseudomonas entomophila LAC23 (Biomacromolecules. 2014 Jun 9;15(6):2310-9. doi: 10.1021/bm500669s).
  • Nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium and iron, may also be used for the biosynthesis.
  • the appropriate known conditions of temperature, pH and dissolved oxygen (OD) can be used for the culturing of the microorganisms.
  • the microorganisms may be cultured according to any known method of culturing, such as in a bioreactor in continuous or batch mode, in fed or unfed mode.
  • the microbial strains producing PHA which is functionalizable or comprising a reactive group are, for example, of the genus Pseudomonas such as P. cichorii YN2, P. citronellolis, P. jessenii, and more generally with species of Pseudomonas putida such as Pseudomonas putida GPo1 (synonym of Pseudomonas oleovorans), P. putida KT2442, P. putida KT2440, P. putida KCTC 2407 and P. putida BM01, and in particular P. putida KT2440.
  • Pseudomonas such as P. cichorii YN2, P. citronellolis, P. jessenii
  • species of Pseudomonas putida such as Pseudomonas putida GPo1
  • One means for gaining access to the PHAs of the invention is to introduce one or more organic compounds into the culture medium, this or these organic compounds representing one or more carbon sources preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and a mixture thereof.
  • the organic compound(s) will preferably be chosen from alcohols, carboxylic acids and a mixture thereof.
  • the carbon source(s) may be classified in two categories:
  • the organic compound(s) are chosen from alcohols, in particular (Cs-C2o)alkanols, and/or carboxylic acids, in particular optionally substituted and/or interrupted (Cs-C2o)alkanoic acids, notably (Cs-C2o)alkanoic acids such as (C7-Cn)alkanoic acids, for instance nonanoic acid or pelargonic acid and/or (Cs-C2o)alkenoic acids, notably (Cs-C2o)alkenoic acids such as (C7-Cn)alkenoic acids, for instance undecylenic acid, and mixtures thereof.
  • alcohols in particular (Cs-C2o)alkanols
  • carboxylic acids in particular optionally substituted and/or interrupted (Cs-C2o)alkanoic acids, notably (Cs-C2o)alkanoic acids such as (C7-Cn)alkanoic acids, for instance nonanoic acid or pelarg
  • the carbon source(s) may be classified into three groups according to their intended use:
  • the organic compound may aid the growth of the productive strain and aids the production of PHA structural linked to the organic compound.
  • the organic compound may aid the growth of the strain but does not participate in the production of PHA structurally linked to the organic compound.
  • the integration of the substrate that is structurally linked to the reactive atom(s) or to the reactive group(s) of the PHA(s) of the invention is introduced directly into the medium as sole carbon source in a medium suitable for microbial growth.
  • group A for P. putida GPoT. alkenoic acid, notably terminal group A for P. putida GPoT. alkenoic acid, notably terminal.
  • the integration of the substrate that is structurally linked to the reactive atom(s), notably halogen, or to the reactive group(s) of the PHA(s) of the invention is introduced into the medium as carbon source with a second carbon source as co-substrate which is also structurally linked to the PHA, in a medium suitable for microbial growth.
  • group B for P. putida GPoT. haloalkanoic acids which are preferably terminal, such as terminal bromoalkanoic acids are preferably terminal, such as terminal bromoalkanoic acids.
  • the integration of the substrate that is structurally linked to the reactive atom(s), notably halogen, or to the reactive group(s) of the PHA(s) of the invention may be introduced directly into the medium as carbon source with a second carbon source as co-substrate which is also structurally linked to the PHA(s) and a third carbon source as co-substrate which is not structurally linked to the PHA(s), in a medium suitable for microbial growth.
  • group C glucose or sucrose group C glucose or sucrose
  • the p-oxidation pathway inhibitor is acrylic acid, 2-butynoic acid, 2-octynoic acid, phenylpropionic acid, propionic acid, trans-cinnamic acid, salicylic acid, methacrylic acid, 4-pentenoic acid or 3-mercaptopropionic acid, preferably acrylic acid.
  • the functionalized fatty acid is a functionalized hexanoic acid, functionalized heptanoic acid, functionalized octanoic acid, functionalized nonanoic acid, functionalized decanoic acid, functionalized undecanoic acid, functionalized dodecanoic acid or functionalized tetradecanoic acid.
  • the functionalization may be introduced by means of an organic compound chosen from precursors of the alcohol and/or carboxylic acid category, notably:
  • the fatty acid from group A is chosen from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and 5-cyanopentanoic acid.
  • the fatty acid from group A is chosen from halooctanoic acids such as 8-bromooctanoic acid.
  • the carbon source from group C is a monosaccharide, preferably glucose.
  • Another aspect of the invention is the use of the PHA-producing microbial strains in a medium that is suitable for microbial growth, said medium comprising: a substrate which is structurally linked to the PHA(s); at least one carbon source which is not structurally linked to the PHA(s); and at least one oxidation and notably p-oxidation pathway inhibitor.
  • the microbial cells synthesizing the PHA polymer(s) of the invention; preferably copolymer particularly containing more than 95% of identical units, which has a comonomer ratio of unit (A) and of unit (B) which differs from that obtained in the absence of the p-oxidation pathway inhibitor.
  • R 2 , m and n are as defined previously;
  • - Y represents a group chosen from Hal such as chlorine or bromine, hydroxyl, thiol, (di)(Ci-C4)(alkyl)amino, R-X with R representing a group chosen from a) cycloalkyl such as cyclohexyl, P) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, y) (hetero)aryl such as phenyl; 6) a cosmetic active agent as defined previously; c) (Ci-C2o)alkyl, (C2-C2o)alkenyl, (C2-C2o)alkynyl; and X representing a’) O, S, N(R a ) or Si(Rb)(R c ) or e) linear or branched (Ci-C2o)alkyl, with R a , Rb and R c as defined previously; q’ represents an integer inclusively between 2 and 20, preferably between
  • these unsaturations may be chemically modified: A) via addition reactions, such as radical additions, Michael additions, electrophilic additions, Diels-Alder, halogenation, hydration or hydrogenation reaction, and preferably hydrothiolation reaction with particles, chemical compounds or polymers.
  • addition reactions such as radical additions, Michael additions, electrophilic additions, Diels-Alder, halogenation, hydration or hydrogenation reaction, and preferably hydrothiolation reaction with particles, chemical compounds or polymers.
  • the hydrothiolation reactions may be performed in the presence of a thermal initiator, a redox initiator or a photochemical initiator and of an organic compound bearing a sulfhydryl group, notably chosen from: linear, branched, cyclic or aromatic alkanethiols including 1 to 14 carbon atoms, such as methane-, ethane-, propane-, pentane-, cyclopentane-, hexane-, cyclohexane-, heptane-, octane-, phenylethane-, 4-tert-butylphenylmethane- or 2- furanmethane-thiol, preferably hexane-, cyclohexane-, heptane-, octane-, phenylethane-, 4-tert-butylphenylmethane- or 2-furanmethane-thiol; organosi
  • initiators examples include: tert-butyl peroxy-2- ethylhexanoate, cumene perpivalate, tert-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2’-azobisisobutyronitrile, 2,2’-azobis(2-methylbutyronitrile), 2,2’-azobis(2,4- dimethylvaleronitrile), 2,2’-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1 , 1-bis(tert- butylperoxy)-3,3,5-trimethylcyclohexane, 1 , 1 -bis(tert-butylperoxy)cyclohexane, 1 ,4- bis(tert-butylperoxy)cyclohe
  • the epoxide structure may be obtained via a conventional method known to those skilled in the art, whether via biotechnological processes or via chemical processes such as oxidation of unsaturation as mentioned previously.
  • the peroxide group(s) may react with carboxylic acids, maleic anhydrides, amines, alcohols, thiols or isocyanates, all these reagents including at least one linear or branched, cyclic or acyclic, saturated or unsaturated C1-C20 hydrocarbon-based chain, or borne by an oligomer or polymer, in particular amino (poly)saccharides such as compounds derived from chitosan and (poly)sil(ox)anes; 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3- (trimethoxysilyl)propylcarbamic acid, diethanolamine, or 3-mercapto-1- propanesulfonate of alkali metal or al
  • M corresponds to an organic or inorganic nucleofugal group, which may be substituted with a nucleophilic group; preferably, said nucleophile is a heteroatom which is electrondonating via the +l and/or +M effect such as O, S or N.
  • the nucleofugal group M is chosen from halogen atoms such as Br, and mesylate, tosylate or triflate groups. This is a reaction known to those skilled in the art. Mention may be made, for example, of the following document: 10.1016/j.ijbiomac.2016.11.118, International Journal of Biological Macromolecules, vol. 95, 796-808 (2017).
  • a first step i) the PHA copolymer bearing a side chain containing a cyano or nitrile group reacts with an organo-alkali metal or organomagnesium compound Y- MgHal, Y-Li or Y-Na, followed by hydrolysis to give the PHA copolymer bearing a side chain containing a group Y grafted with a ketone function.
  • the ketone function may be converted into a thio ketone by thionation, for example with S8 in the presence of amine, or with Lawesson’s reagent.
  • Said thio ketone after total reduction ii) (for example by Clemmensen reduction), leads to the PHA copolymer bearing a side chain containing a group Y grafted with an alkylene group.
  • said thio ketone may undergo a controlled reduction iii) with a conventional reducing agent to give the PHA copolymer bearing a side chain containing a group Y grafted with a hydroxyalkylene group.
  • the cyano group of the starting PHA copolymer can react with water after hydration v) to give the amide derivative, after hydrolysis iv) to the carboxyl derivative.
  • the cyano group of the starting PHA copolymer can also, after reduction vi), give the amine derivative or the ketone derivative.
  • PHA copolymers with a hydrocarbon-based chain bearing a nitrile function are prepared via conventional methods known to those skilled in the art. Mention may be made, for example, of the document: 10.1016/0378-1097(92)90311-B, FEMS Microbiology Letters, vol. 103, 2-4, 207-214 (1992).
  • R 1 , R 2 , m, n and Y are as defined previously, and R’ 1 represents a hydrocarbon-based chain chosen from i) linear or branched (Ci-C2o)alkyl, ii) linear or branched (C2-C2o)alkenyl, iii) linear or branched (C2-C2o)alkynyl; preferably, the hydrocarbon-based group is linear; said hydrocarbon-based chain being substituted with one or more atoms or groups chosen from: a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) (thio)carboxyl, f) (thio)carboxamide - C(O)-N(R a ) 2 or -C(S)-N(R a ) 2 , f) cyano, g
  • Epoxidation of chain-end unsaturation and chain-end grafting of acid 10.14314/polimery.2017.317; Polimery, vol. 62, 4, 317-322 (2017);
  • X’ represents a reactive atom or group that is capable of reacting with an electrophilic E or nucleophilic atom or group to create a S covalent bond; if X’ is an electrophilic or nucleofugal group, then it can react with a reagent R’ 1 - if X’ is a nucleophilic group Wu, then it can react with R’ 1 - E to create a S covalent bond.
  • Composition C1 or CT according to the invention comprises one or more volatile oils.
  • oil denotes a water-immiscible compound which is liquid at 25°C and atmospheric pressure (1.013* 10 5 Pa).
  • the term “immiscible” means that the mixing of the same amount of water and oil, after stirring, does not result in a stable solution comprising only a single phase, under the abovementioned temperature and pressure conditions. Observation is performed by eye or using a phase-contrast microscope, if necessary, on 100 g of mixture obtained after sufficient stirring with a Rayneri blender to produce a vortex within the mixture (as a guide, 200 to 1000 rpm), the resulting mixture being left to stand, in a closed flask, for 24 hours at room temperature before observation.
  • volatile oil means an oil (or non-aqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and at atmospheric pressure.
  • the volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a non-zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10 _ 3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
  • non-volatile oil means an oil with a vapour pressure of less than 0.13 Pa.
  • the volatile oils are such that the flash points are less than 120°C and the vapour pressure is less than 5 Pa, more particularly the flash point is less than 90°C and the vapour pressure is greater than 1 Pa, even more preferentially the flash point is less than or equal to 60°C and the vapour pressure is greater than 5 Pa, and even more preferentially the flash point is less than 60°C and the vapour pressure is greater than 100 Pa.
  • hydrocarbon-based oil refers to an oil mainly containing carbon and hydrogen atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions. A hydrocarbon-based oil thus consequently does not comprise any silicon or fluorine atoms.
  • silicon oil refers to an oil comprising at least one silicon atom, and notably at least one Si-0 group, and more particularly an organopolysiloxane.
  • fluoro oil denotes an oil comprising at least one fluorine atom.
  • apolar hydrocarbon-based oil means an hydrocarbon-based oil comprising only carbon and hydrogen atoms, which is preferably non-aromatic (also called a hydrocarbon).
  • polar hydrocarbon-based oil denotes hydrocarbon-based oils mainly comprising carbon and hydrogen atoms and one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.
  • polar hydrocarbon-based oil denotes hydrocarbon-based oils mainly comprising carbon and hydrogen atoms and one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.
  • the volatile oils b) are volatile hydrocarbon-based oils such as:
  • hydrocarbon-based oils containing from 8 to 16 carbon atoms and notably:
  • isoalkanes also known as isoparaffins
  • isoalkanes such as Cs-Cg isoparaffin, Cn-C isoparaffin, isododecane, isodecane, isohexadecane, and for example the oils sold under the trade names Isopars or Permetyls, alone or as mixtures, preferably isododecane (also known as 2,2,4,4,6-pentamethylheptane), for example sold by Ineos, more preferentially isododecane;
  • - linear alkanes for example Ce-Ci6 alkanes, alone or as mixtures, for instance hexane, decane, undecane or tridecane, isoparaffins such as, or n-dodecane (C12) and n- tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, and mixtures thereof, and also mixtures of n- undecane (C11) and of n-tridecane (C13) Cetiol Ultimate® from the company BASF;
  • Ce-Ci6 alkanes alone or as mixtures, for instance hexane, decane, undecane or tridecane
  • isoparaffins
  • short-chain esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate or isobutyl acetate, for example sold by Solvay, Dow or Oxea;
  • R’I-O-C(O)-O-R’2 in which R’1 and R’2 independently denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group. It may be preferable for R1 and R2 to be identical. Preferably, R’1 and R’2 denote a linear butyl alkyl radical, a pentyl group.
  • the ether oil is chosen from dibutyl carbonate and dipentyl carbonate;
  • R1 and R2 independently denote a linear, branched or cyclic C4-C8 alkyl group, preferably a C4-C8 alkyl group. It is preferable for R1 and R2 to be identical.
  • Linear alkyl groups that may be mentioned include a butyl group and a pentyl group.
  • Branched alkyl groups that may be mentioned include a 1 -methylpropyl group, a 2- methylpropyl group, a t-butyl group and a 1 ,1 -dimethylpropyl group.
  • the ether oil is chosen from dicaprylyl ether and dicapryl ether, most particularly dicaprylyl ether.
  • the volatile hydrocarbon-based oil(s) are notably chosen from Ce-Ci6 alkanes and in particular alkanes such as dodecane, tetradecane, isohexadecane, mixtures of undecane and tridecane, and isoparaffins such as C13-C16 isoparaffin.
  • the volatile oil(s) b) are linear or branched hydrocarbon-based oils, which are volatile, notably chosen from undecane, decane, dodecane, isododecane, isohexadecane, tridecane, tetradecane and a mixture thereof preferably comprising isododecane and/or a mixture of undecane and tridecane.
  • the volatile oil(s) b) of the invention are a mixture of C9-C12 alkanes, preferably of natural origin, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes.
  • This mixture is notably known under the INCI name C9-12 Alkane, CAS 68608-12-8, Vegelight Silk® sold by BioSynthls.
  • the volatile oil(s) b) are silicone oils in particular comprising, from 2 to 7 silicon atoms, these silicone oils optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • As volatile silicone oils that may be used in the invention, mention may notably be made of dimethicones with viscosities of 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • the volatile oil(s) b) are chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, volatile silicone oils and mixtures thereof, such as Cetiol Ultimate® from the company BASF.
  • the volatile oil(s) b) are chosen from preferably branched C 8 -Ci6 alkanes and preferably isododecane.
  • the volatile oil(s) b) are chosen from preferably linear C 8 -Ci6 alkanes, and more preferentially are chosen from C9-C12 alkanes such as dodecane, as INCI C9-C12 Alkane, CAS 68608-12-8, Vegelight Silk® sold by BioSynthls, or a mixture of undecane and tridecane.
  • the volatile oil(s) b) are chosen from linear or branched C 8 -Ci6 alkanes, preferably mixtures of linear C 8 -Ci6 alkanes and branched C 8 - C alkanes, said mixture preferably containing at least isododecane or Vegelight Silk® or a mixture of undecane and tridecane.
  • the volatile oil(s) b) comprise(s) at least one silicone oil as defined above, preferably chosen from dodecamethylpentasiloxane such as the reference DM-Fluid-2cs sold by Shin-Etsu or cyclohexadimethylsiloxane such as the reference Xiameter PMX-0246 Cyclohexasiloxane sold by Dow Chemical.
  • dodecamethylpentasiloxane such as the reference DM-Fluid-2cs sold by Shin-Etsu or cyclohexadimethylsiloxane such as the reference Xiameter PMX-0246 Cyclohexasiloxane sold by Dow Chemical.
  • the volatile oil(s) b) are a mixture of at least one volatile hydrocarbon-based oil and of at least one volatile silicone oil
  • the amount of silicone oil is less than 30%, preferably less than 20%, preferably less than 10%, relative to the total mass of the composition.
  • the amount of volatile oil b) is between 5% and 95% by weight relative to the total weight of the composition, more particularly between 20% and 90% by weight, preferentially between 50% and 85% by weight, better still between 60% and 80% by weight relative to the total weight of the composition.
  • the non-volatile oil(s) is between 5% and 95% by weight relative to the total weight of the composition, more particularly between 20% and 90% by weight, preferentially between 50% and 85% by weight, better still between 60% and 80% by weight relative to the total weight of the composition.
  • Composition C1 or CT also comprises one or more non-volatile oils.
  • non-volatile oil means an oil whose vapour pressure at 25°C and atmospheric pressure is non-zero and is less than 2.66 Pa and more particularly less than 0.13 Pa.
  • the vapour pressure may be measured according to the static method or via the effusion method by isothermal thermogravimetry, depending on the vapour pressure of the oil (standard OCDE 104).
  • the non-volatile oil(s) of the invention are of natural or synthetic origin, preferably natural.
  • composition C1 or CT comprises one or more non-volatile oils.
  • non-volatile fluorino oils which may notably be chosen from among fluorinated polyethers, and also from the fluorosilicone oils and the fluoro silicones as described in EP-A-847752;
  • non-volatile silicone oils which may notably be chosen from the non-volatile silicones having the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyl trimethicone, diphenylsiloxyphenyl trimethicone; and also mixtures thereof.
  • non-volatile apolar hydrocarbon-based oils which may notably be chosen from linear or branched compounds of mineral or synthetic origin, for instance: i) liquid paraffin, ii) squalane such as the reference Neossance Squalane sold by Amyris, isoeicosane, iii) mixtures of linear, saturated hydrocarbons, particularly C14-C30 and more particularly C15- C28 hydrocarbons, such as mixtures whose INCI names are, for example, the following: (Ci5-Cig)Alkane, (Cis-C2i)Alkane, (C2i-C2s)Alkane, for instance the products Gemseal 40, Gemseal 60 and Gemseal 120 sold by Total, Emogreen L19 sold by SEPPIC, Emogreen L15 sold by SEPPIC, iv) hydrogenated or non-hydrogenated polybutenes, for instance the products of the Indopol range sold by INEOS Oligomers, products having the INC
  • non-volatile polar hydrocarbon-based oils which may be chosen from: i) saturated or unsaturated, linear or branched C10-C26 fatty alcohols, preferably monoalcohols.
  • 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, notably 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 C to C36, these
  • esters As examples of such esters, mention may be made of 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, cocoyl caprylate/caprate, tridecyl octanoate, 2-ethylhexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol bis(2- ethylhexanoate) and mixtures thereof
  • the non-volatile carbonate oils may be chosen from the carbonates of formula R 8 -O-C(O)- O-Rg, with R 8 and Rg, which may be identical or different, representing a linear or branched C4 to C12 and preferentially C 8 to C10 alkyl chain;
  • the carbonate oils may be dicaprylyl carbonate (or dioctyl carbonate), sold under the name Cetiol CC® by the company BASF, bis(2-ethylhexyl) carbonate, sold under the name Tegosoft DEC® by the company Evonik, dipropylheptyl carbonate (Cetiol 4 All from BASF), dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate;
  • 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-di methyl butyl group, a 1-(1-methylethyl)-2-methylpropyl group, a 1 ,1 ,3,3-tetramethylbutyl group, a 3,5,5-
  • 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.
  • non-volatile ether oils mention may be made of dicaprylyl ether, such as the reference Cetiol OE sold by BASF.
  • the non-volatile oil(s) c) are chosen from non-volatile silicone oils, non-volatile hydrocarbon-based oils, polar hydrocarbon-based oils as defined previously, and mixtures thereof preferably chosen from non-volatile hydrocarbon-based oils, polar hydrocarbon-based oils as defined previously and mixtures thereof.
  • the non-volatile hydrocarbon-based oil(s) c) comprise or consist of at least one non-volatile oil chosen 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, aliphatic hydrocarbon-based esters of alkylene glycol, in particular ethylene glycol or propylene glycol as defined previously, more preferentially chosen from isoamyl laurate, isopropyl myristate, isodecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, cocoyl caprylate/caprate and mixtures thereof, and better still denote isononyl isononanoate.
  • R-C(0)-0 represents a carboxylic acid residue containing from 2 to
  • the non-volatile hydrocarbon-based oil(s) c) comprise or consist of at least one non-volatile oil chosen from saturated or unsaturated, linear or branched C10-C26 fatty alcohols, preferably monoalcohols, which are preferably branched when they comprise at least 16 carbon atoms as described previously, in particular chosen from oleyl alcohol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol such as the reference Eutanol G sold by BASF, and mixtures thereof.
  • non-volatile oil chosen from saturated or unsaturated, linear or branched C10-C26 fatty alcohols, preferably monoalcohols, which are preferably branched when they comprise at least 16 carbon atoms as described previously, in particular chosen from oleyl alcohol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol such as the reference Eutanol G sold by
  • the non-volatile hydrocarbon-based oil(s) c) comprise or consist of at least one non-volatile oil chosen from triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may in particular have chain lengths ranging from C4 to C36, and notably from Cs to C36, it being possible for these oils to be linear or branched, and saturated or unsaturated as described previously, preferably chosen from heptanoic or octanoic triglycerides, caprylic/capric acid triglycerides and mixtures thereof, and more preferentially caprylic/capric acid triglycerides such as the reference Palmester 3585 sold by KLK Oleo.
  • the non-volatile hydrocarbon-based oil(s) c) comprise or consist of at least one non-volatile oil chosen from apolar hydrocarbonbased non-volatile oils as described previously, preferably chosen from mixtures of linear, saturated hydrocarbons, more particularly C15-C28 hydrocarbons, hydrogenated or non-hydrogenated poly(iso)butenes, and mixtures thereof.
  • the non-volatile hydrocarbon-based oil(s) c) comprise or consist of at least one non-volatile oil chosen from apolar hydrocarbonbased non-volatile oils chosen from the mixtures whose INCI names are, for example, the following: C15-C19 Alkane, C18-C21 Alkane, C21-C28 Alkane, for instance the products Gemseal 40, Gemseal 60, Gemseal 120 sold by Total, Emogreen L19 sold by SEPPIC, Emogreen L15 sold by SEPPIC, the products having the INCI name Hydrogenated Polyisobutene, and mixtures thereof.
  • apolar hydrocarbonbased non-volatile oils chosen from the mixtures whose INCI names are, for example, the following: C15-C19 Alkane, C18-C21 Alkane, C21-C28 Alkane, for instance the products Gemseal 40, Gemseal 60, Gemseal 120 sold by Total, Emogreen L19 sold by SEPPIC, Em
  • the non-volatile hydrocarbonbased oil(s) c) comprise or consist of at least one non-volatile oil chosen from isoamyl laurate, isopropyl myristate, isodecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, oleyl alcohol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol, caprylic/capric acid triglycerides, mixtures whose INCI names are, for example, the following: C15-C19 Alkane, C18-C21 Alkane, C21-C28 Alkane, for instance Gemseal 40, Gemseal, products having the INCI name Hydrogenated Polyisobutene, and mixtures thereof, more particularly chosen from products having the INCI name Hydrogenated Polyisobutene, mixtures
  • the non-volatile hydrocarbon-based oil(s) c) consist of one or more polar or apolar non-volatile hydrocarbon-based oil(s) as defined previously.
  • the non-volatile oil(s) of the invention are chosen from: hydrogenated or non-hydrogenated polyisobutenes, preferably hydrogenated, for instance the nonvolatile 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, notably isononyl isononanoate.
  • the non-volatile oil(s) c) comprise at least one silicone oil as defined above, preferably chosen from dimethicones, such as the grade Belsil DM 5 Plus Dimethicone sold by Wacker, the reference Dowsil SH 200 C Fluid 10 CST sold by Dow Chemical or the reference Xiameter PMX-200 Silicone Fluid 1000 CST sold by Dow Chemical, or Phenyl Trimethicone such as the reference Dowsil SH 556 Fluid sold by Dow Chemical.
  • dimethicones such as the grade Belsil DM 5 Plus Dimethicone sold by Wacker
  • Phenyl Trimethicone such as the reference Dowsil SH 556 Fluid sold by Dow Chemical.
  • the non-volatile oil(s) c) are a mixture of at least one nonvolatile hydrocarbon-based oil preferably chosen from apolar non-volatile hydrocarbonbased oils and polar non-volatile hydrocarbon-based oils with at least one volatile silicone oil
  • the amount of silicone oil is less than 30%, preferably less than 20%, preferably less than 10%, relative to the total mass of the composition.
  • the non-volatile oil(s) c) are present in composition C1 or C1’ in an amount of from 0.1% to 15%, preferably 0.12% to 12%, more preferentially between 0.15% and 10%, even more preferentially between 0.2% and 5% by weight relative to the total weight of the composition.
  • the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is nonzero and less than or equal to 900, preferably less than 900.
  • mass ratio or weight ratio noted means the ratio of the sum of the masses of non-volatile oil(s) (Z non-volatile oil(s) (NVO)) to the sum of the masses of volatile oil(s) (Z sum of volatile oil(s) (VO)) corresponding to the mathematical equation to be complied
  • said mass ratio must respect the following inequality 0 ⁇ ⁇ 900, better still 0 ⁇ ⁇ 900, particularly 1 ⁇ ⁇ 800, better still 1 ⁇ ⁇ 800; more particularly 700; preferentially 3 ⁇ 600, better still 3 ⁇ ⁇ 600; more preferentially 3.5 ⁇ ⁇ 600, better still 3.5 ⁇ ⁇ 600; even more preferentially 4
  • the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is non-zero and less than 800, preferably less than 700, more preferentially less than 600, notably less than 500 and even more preferentially less than 400.
  • the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is greater than zero, preferably greater than 0.01 , more preferentially greater than 0.5, even more preferentially greater than 1 , even more preferably greater than 2, most particularly greater than 2.5, and even more preferentially greater than 3, in particular greater than 4.
  • the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is between 4 and 200, notably between 4.5 and 300.
  • the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is preferably between 3 and 800, notably between 3 and 700, more particularly between 3.5 and 600, even more preferentially between 3.7 and 500 such as between 3.8 and 400, even more preferably between 3.9 and 300, even more preferentially between 4 and 200.
  • the composition of the invention comprises one or more waxes.
  • wax means a lipophilic compound that is solid at room temperature (25°C), with a reversible solid/liquid change of state, having a melting point of greater than or equal to 30°C, which may be up to 200°C and notably up to 120°C.
  • the wax(es) that are suitable for use in the invention may have a melting point of greater than or equal to 45°C and in particular of greater than or equal to 55°C.
  • Composition C1 or CT according to the invention preferably comprises a content of wax(es) ranging from 0.5% to 30% by weight relative to the total weight of the composition, in particular from 1 % to 20% and more particularly from 2% to 15%.
  • the composition of the invention is solid, in particular anhydrous. It may then be in stick form; use will be made of polyethylene microwaxes in the form of crystallites with an aspect ratio at least equal to 2, and with a melting point ranging from 70 to 110°C and preferably from 70 to 100°C, so as to reduce or even eliminate the presence of strata in the solid composition.
  • crystallites in needle form and notably the dimensions thereof may be characterized visually according to the following method.
  • the composition of the invention comprises one or more pasty compounds.
  • composition C1 or CT comprises b) one or more volatile oils, c) one or more nonvolatile oils, optionally e) water and optionally f) one or more organic solvents other than b) and c). d) Organic solvent(s) other than b) and c)
  • composition C1 or CT also comprises one or more organic solvents other than b) and c), which are apolar or polar, preferably polar, and which are protic or aprotic, more particularly protic and/or polar, preferably protic and polar.
  • the organic solvent(s) f) are water-miscible.
  • organic solvent(s) f) that may be used in composition C1 or CT of the invention may also be volatile.
  • organic solvents f) that may be used in composition C1 or CT according to the invention, mention may notably be made of polar protic or polar aprotic organic solvents, preferably polar protic organic solvents, particularly lower monoalcohols containing from 2 to 10 carbon atoms, such as ethanol, butanol and isopropanol, preferably ethanol.
  • composition C1 or CT of the invention comprises one or more organic solvents f), preferably chosen from monoalcohols containing from 2 to 6 carbon atoms such as ethanol, n-butanol and isopropanol.
  • composition C1 or CT comprises a) one or more polyhydroxyalkanoate (PHA) copolymers as defined previously; and b) one or more volatile oils as defined previously; and c) one or more non-volatile oils as defined previously; and f) one or more organic solvents chosen from monoalcohols containing from 2 to 6 carbon atoms, such as ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol or hexanol, preferably n-butanol or ethanol, even more preferentially ethanol.
  • PHA polyhydroxyalkanoate
  • the amount of organic solvent(s) f) is less than 70% by weight, more preferentially less than 50% by weight, relative to the total weight of composition C1 or CT.
  • composition C1 or CT comprises an amount of organic solvent(s) f) of greater than 0.5%, more particularly greater than or equal to 1% by weight relative to the total weight of the composition.
  • composition C1 or CT comprises between 2% and 50% by weight of organic solvent(s) f).
  • composition C1 or CT comprises e) water.
  • composition C1 or CT contains e) water, and optionally d) one or more surfactants as defined below.
  • the water that is suitable for use in the invention may be tap water, distilled water, spring water, a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a thermal water.
  • the surfactants may be tap water, distilled water, spring water, a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a thermal water.
  • composition C1 or CT also comprises f) one or more surfactants, preferably nonionic or ionic surfactants, or mixtures thereof.
  • composition C1 does not comprise any surfactant.
  • composition C1 or CT contains a) at least one PHA as defined previously and b) at least one volatile oil as defined previously, c) at least one non-volatile oil as defined previously, e) water and optionally f) one or more surfactants.
  • surfactant means a compound which modifies the surface tension between two surfaces.
  • the surfactant(s) d) are amphiphilic molecules, which have two parts of different polarity, one part being lipophilic (which retains fatty substances) which is apolar, the other hydrophilic part (miscible or soluble in water) being polar.
  • the lipophilic part is generally a fatty chain, and the other water-miscible part is polar, and/or protic.
  • ionic means anionic, cationic, amphoteric or zwitterionic.
  • fatty chain means a linear or branched, saturated or unsaturated hydrocarbon-based chain comprising more than 6 atoms, preferably between 6 and 30 carbon atoms and preferably from 8 to 24 carbon atoms.
  • the composition of the invention contains d) at least one silicone or non-silicone nonionic surfactant.
  • nonionic surfactants include fatty alcohols, a-diols and alkylphenols, these three types of compound being polyethoxylated, polypropoxylated and/or polyglycerolated and containing a fatty chain including, for example, 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging in particular from 2 to 50 and the number of glycerol groups possibly ranging in particular from 2 to 30.
  • polyethoxylated fatty amides preferably containing from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides including on average 1 to 5, and in particular 1.5 to
  • the surfactant(s) represent in total particularly from 0.01 % to 30% by weight, preferably from 0.5% to 15% by weight, even more preferentially from 1 % to 10% by weight and better still between 1% and 5% by weight of the composition, relative to the total weight of the composition.
  • composition C1 or CT comprises an aqueous phase.
  • the composition is notably formulated as water n-oil or oil-in-water emulsions or as multiple emulsions (oil4n-water4n-oil or water n-oil-in-water triple emulsions (such emulsions are known and described, for example, by C. Fox in “Cosmetics and Toiletries” - November 1986 - Vol. 101 - pages 101-112)).
  • composition C1 or CT is a direct emulsion, i.e. an emulsion of oil-in-water or O/W type.
  • the weight amount of oil is preferably less than 70% in the inverse emulsion, preferably less than or equal to 40%, more particularly less than or equal to 35% by weight relative to the total weight of the composition.
  • the amount of water is greater than or equal to 30% by weight relative to the total weight of the composition, more particularly greater than or equal to 40%, preferentially greater than or equal to 35%.
  • the composition of the invention is an inverse emulsion, i.e. of water-in-oil or W/O type.
  • the weight amount of oil is preferably greater than 30% in the inverse emulsion, preferably greater than 40%, more preferentially greater than or equal to 45% by weight relative to the total weight of the composition. More particularly, in the inverse emulsion, the amount of water is less than 40% by weight relative to the total weight of the composition, preferably less than or equal to 35% by weight.
  • Composition C1 or CT according to the invention preferably has a pH ranging from 3 to 9, depending on the support chosen.
  • the pH of the composition(s) is neutral or even slightly acidic.
  • the pH of the composition is between 6 and 7.
  • the pH of these compositions may be adjusted to the desired value by means of acidifying or basifying agents usually used in cosmetics, or alternatively using standard buffer systems.
  • the term “basifying agent’ or “base” means any agent for increasing the pH of the composition in which it is present.
  • the basifying agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic.
  • said agent is chosen from a) aqueous ammonia, b) (bi)carbonate, c) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, d) oxyethylenated and/or oxypropylenated ethylenediamines, e) organic amines, f) mineral or organic hydroxides, g) alkali metal silicates such as sodium metasilicates, h) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and i) the compounds of formula (F) below: in which formula (F):
  • Ci-Ce alkylene radical optionally substituted with one or more hydroxyl groups or a Ci-Ce alkyl radical, and/or optionally interrupted with one or more heteroatoms such as O or NR U ;
  • R x , R y , R z , Rt and R u which may be identical or different, represent a hydrogen atom or a Ci-Ce alkyl, Ci-Ce hydroxyalkyl or Ci-Ce aminoalkyl radical.
  • amines of formula (F) examples include 1 ,3- diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.
  • alkanolamine means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched Ci-Cs alkyl groups bearing one or more hydroxyl radicals.
  • mineral or organic hydroxides examples include those chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.
  • the mineral or organic hydroxides a) and b) are preferred.
  • acidifying agents for the compositions used in the invention examples include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • mineral or organic acids for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • the basifying agents and the acidifying agents as defined previously preferably represent from 0.001% to 20% by weight relative to the weight of the composition containing them, and more particularly from 0.005% to 8% by weight of the composition.
  • composition C1 or CT comprises an amount of water of less than or equal to 10% by weight relative to the total weight of the composition. Even more preferentially, composition C1 or CT comprises an amount of water of less than or equal to 5%, better still less than 2%, even better still less than 0.5%, and is notably free of water. Where appropriate, such small amounts of water may notably be introduced by ingredients of the composition that may contain residual amounts thereof.
  • the composition does not comprise any water.
  • composition C1 according to the invention comprises a physiologically acceptable medium.
  • the composition is a cosmetic composition.
  • physiologically acceptable medium means a medium that is compatible with human keratin materials, for instance the skin, the lips, the nails, the eyelashes, the eyebrows or the hair.
  • cosmetic composition means a composition that is compatible with keratin materials, which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort (stinging or tautness) liable to discourage the consumer from using it.
  • keratin materials means the skin (body, face, contour of the eyes, scalp), head hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips.
  • Composition C1 or CT according to the invention may comprise one or more cosmetic additives chosen from fragrances, preserving agents, fillers, colouring agents, UV-screening agents, oils other than the oils b) and the oils c), moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), thickeners or film-forming agents other than a), trace elements, softeners, sequestrants, agents for combating hair loss, anti-dandruff agents or propellants.
  • cosmetic additives chosen from fragrances, preserving agents, fillers, colouring agents, UV-screening agents, oils other than the oils b) and the oils c
  • moisturizers chosen from fragrances, preserving agents, fillers, colouring agents, UV-screening agents, oils other than the oils b) and the oils c
  • moisturizers chosen from fragrances, preserving agents, fillers, colouring agents, UV-screening agents, oils other than the oils b) and the oils c
  • composition C1 or CT according to the invention also comprises one or more colouring agents 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 black iron oxides, and micas coated with iron oxide, triaryl methane 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.
  • the pigment(s) of the invention are chosen from carbon black, iron oxides, notably black iron oxides, and micas coated with iron oxide, triaryl methane 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
  • composition C1 or CT according to the invention is a makeup composition, in particular a lip makeup composition, a mascara, an eyeliner, an eye shadow or a foundation.
  • Composition C1 or CT according to the invention may also comprise one or more fillers, notably in a content ranging from 0.01% to 30% by weight and preferably ranging from 0.01 % to 20% by weight relative to the total weight of the composition.
  • fillers should be understood as meaning colourless or white, mineral or synthetic particles of any shape, which are insoluble in the medium of the composition, irrespective of the temperature at which the composition is manufactured. These fillers notably serve to modify the rheology or texture of the composition.
  • Composition C1 or CT according to the invention may be in the form of an anhydrous composition, a water-in-oil emulsion or an oil-in-water emulsion.
  • the PHAs illustrated in the various examples were prepared in 3-litre chemostats and/or 5-litre Fernbach flasks depending on whether or not a p-oxidation pathway inhibitor was used. The isolation of the PHAs is similar for all the examples obtained.
  • the microorganism In a first step, the microorganism generates the PHAs which are stored in intracellular granules, the proportion of which varies as a function of the applied conditions such as the temperature or the nature of the culture medium. The generation of PHA granules may or may not be associated with the growth of the microorganism as a function of the nature of the microorganisms.
  • the biomass containing the PHAs is isolated, i.e. separated from the fermentation medium, and then dried. The PHAs are extracted from the biomass before being purified, if necessary.
  • a mixture of saturated and unsaturated carbon sources is, for certain examples, necessary for the stability of the PHA obtained.
  • Example 1 PHA bearing a side chain R 1 representing a linear 10% unsaturated n-octenyl group and R 2 representing an n-pentyl group
  • the microorganism used is Pseudomonas putida KT2440 ATCC® 47054TM.
  • the system is aerated with a flow of 0.5 vvm of air for a nominal dissolved oxygen (OD) value at 30% of saturation.
  • the pH is regulated with 15% aqueous ammonia solution.
  • the temperature of the fermentation medium is regulated at 30°C.
  • the fermentation medium is regulated in terms of temperature-pressure of dissolved oxygen and pH (not shown): see the attached fig. 1.
  • the production process is performed using three different culture media.
  • the first culture medium defined CM1 “inoculum”, is used for the preparation of the preculture.
  • the second culture medium defined CM2 “batch”, is used for unfed batch growth of the microorganism with the primary carbon sources in the Fernbach flasks.
  • the third culture medium defined CM3 “maintenance”, is used for the fed-batch or maintenance fermentation mode with the carbon sources of interest at a flow rate calibrated as a function of the growth of the microorganism.
  • composition of the Nutrient Broth is 37.5% beef extract and 62.5% peptone.
  • 100 mL of preculture are prepared by suspending a cryotube containing 1 mL of the strain with 100 mL of “inoculum” culture medium at a pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask and are then incubated at 30°C at 150 rpm for 24 hours.
  • the biomass is isolated by centrifugation and then washed three times with water.
  • the biomass is dried by lyophilization before being extracted with ethyl acetate for 24 hours.
  • the suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate composed of PHA dissolved in the ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.
  • the PHA may optionally be purified by successive dissolution and precipitation from an ethyl acetate/ethanol 70% methanol system, for example.
  • the PHA was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure.
  • Example T The copolymer of Example T (5% unsaturation and R 2 chain representing n-hexyl) was prepared according to the procedure described for Example 1, with the same composition of the microelement solution as described in Example 1 and with the following culture medium compositions:
  • Example 1 The PHA copolymer of Example T was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure, with a degree of unsaturation of 5%.
  • Example 1 PH A copolymer bearing a side chain R 1 representing a linear 10% unsaturated n-octenyl group and R 2 representing an n-hexyl group
  • Example 1 The copolymer of Example 1” (10% unsaturation and R 2 chain representing n-hexyl) was prepared according to the procedure described for Example 1 , with the same composition of the microelement solution as described in Example 1 and with the following culture medium compositions:
  • Example T PHA copolymer bearing a side chain R 1 representing a linear 30% unsaturated n-octenyl group and R 2 representing an n-pentyl group
  • Example T The copolymer of Example T” (30% unsaturated and R 2 chain representing n-pentyl) was prepared according to the procedure described for Example 1, with the same composition of the microelement solution as described in Example 1 and with the following culture medium compositions:
  • the PHA copolymer was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure.
  • Example 2 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 100% grafted with thiolactic acid (compound of Example 1 grafted with thiolactic acid TLA):
  • the grafted PHA of Example 2 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure.
  • Example 3 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 100% grafted with octanethiol (compound of Example 1 grafted with n-octanethiol)
  • reaction medium was then precipitated from a 100 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 3 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure.
  • Example 4 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 75% grafted with 8-mercapto- 1 -octanol (compound of Example 1 grafted with 8- mercapto- 1 -octanol)
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 4 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 75% or 7.5% of functions in total.
  • reaction medium was then precipitated from a 100 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 5 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 32% or 3.2% of functions in total.
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • Example 7 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 70% grafted with 2-furanmethanethiol (FT) (compound of Example 1 grafted with FT)
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 7 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 70% or 7% of functions in total.
  • Example 8 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 70% grafted with 1-thio-/3-D-glucose tetraacetate (compound of Example 1 grafted with TGT) b) [Chem. 31]:
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 8 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 70% or 7% of functions in total.
  • Example 9 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 50% grafted with 2-phenylethanethiol (PT) (compound of Example 1 grafted with PT)
  • [00306] [Chem. 32]: [00307] 100 mg of the compound of Example 1 and 26 mg of 2-phenylethanethiol were dissolved in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2- dimethoxy-2-phenylacetophenone (Irgacure 651) were added to the mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) and with stirring for at least 10 minutes.
  • Irgacure 651 2,2- dimethoxy-2-phenylacetophenone
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 9 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 50% or 5% of functions in total.
  • Example 10 Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturations 64% grafted with 4-tert-butyl benzyl mercaptan (TBM) (compound of Example 1 grafted with TBM)
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 10 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 64% or 6.4% of functions in total.
  • reaction medium was then precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 11 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 100%.
  • reaction medium was then precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • the grafted PHA of Example 12 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 100%.
  • Example 13 The PHA of Example 13 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Epoxidation to 100%.
  • reaction medium was then precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • Example 14 The PHA of Example 14 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Epoxidation to 100%.
  • Example 15 Poly(3-hydroxyoctanoate-co-undecenoate) containing 30% unsaturations
  • reaction medium was then precipitated from a 250 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • Example 15 The PHA of Example 15 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Epoxidation to 100%.
  • reaction medium was then precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. This step may be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and then dried under dynamic vacuum at 40°C to obtain a homogeneous film.
  • Example 16 The PHA of Example 16 was fully characterized by spectroscopic and spectrometric methods and is in accordance with the expected chemical structure. Grafting to 100%.
  • Example 17 Copolymer of PHA bearing a side chain R 1 representing an isohexenyl group and R 2 representing an isobutyl group
  • Example 17 The production process of Example 17 is an adaptation of Applied and Environmental Microbiology, Vol. 60, No. 9, 3245-3254 (1994) “Polyester Biosynthesis Characteristics of Pseudomonas citronellolis Grown on Various Carbon Sources, Including 3-M ethyl- Branched Substrate”. Mun Hwan Choi and Sung Chui Yoon.
  • the microorganism used is Pseudomonas citronellolis ATCC® 13674TM.
  • the culture method was performed under unfed batch axenic culture conditions in 5L Fernbach flasks (Corning® ref. 431685) containing 2 L of culture medium, shaken at 110 rpm at 30°C in an orbital incubator (orbit diameter of 2.5 cm).
  • the production process is performed using two different culture media.
  • the first culture medium defined CM1 “inoculum”, is used for the preparation of the preculture.
  • the second culture medium defined CM2 “batch”, is used for unfed batch culture growth of the microorganism with the carbon source of interest in the Fernbach flasks.
  • composition of the Nutrient Broth is 37.5% beef extract and 62.5% peptone.
  • Reference 233000 DIFCOTM BD The composition of the yeast extract, as a mass percentage, is 100% autolysate of the yeast Saccharomyces cerevisiae. Reference 210933 DIFCOTM BD.
  • 100 mL of preculture are prepared by suspending a cryotube containing 1 mL of the strain with 100 mL of “inoculum” culture medium at a pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask and then incubated at 30°C at 150 rpm for 24 hours.
  • the biomass is dried by lyophilization before being extracted with dichloromethane for 24 hours.
  • the suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate composed of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.
  • the PHA may optionally be purified by successive dissolution and precipitation, for instance using a dichloromethane/methanol system.
  • Example 18 Copolymer of PHA bearing a side chain R 1 representing an isohexyl group and R 2 representing an isobutyl group c) [Chem. 40]:
  • Example 18 is obtained by hydrogenation of the PHA copolymer of Example 17 using an H-Cube Midi® continuous hydrogenator from ThalesNano Technologies.
  • a solution of 2 g (8.83 mmol) of PHA of Example 3 is prepared with a mixture composed of 100 ml of ethyl acetate (Sigma-Aldrich - CAS: 141-78-6) and 100 mL of methanol (Sigma-Aldrich - CAS: 67-56-1) and is introduced at a flow rate of 3 mL per minute into a hydrogenation cartridge containing the catalyst containing 5% palladium on charcoal (MidiCard ref. DHS 2141 ; ThalesNano Technologies) maintained at 100°C under a pressure of 80 bar in the presence of hydrogen in the ThalesNano Technologies H-Cube Midi® system. The reduction of the double bond is monitored by NMR. After six consecutive cycles of reduction, the solution is concentrated by evaporation and then dried under vacuum to constant mass.
  • the PHA may optionally be purified by successive dissolution and precipitation, for instance using a dichloromethane/methanol system.
  • a polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054TM and octanoic acid.
  • the culture method was performed under batch axenic conditions in 5 L Fernbach flasks (Corning® ref. 431685) containing 2 L of culture medium, shaken at 110 rpm at 30°C in an orbital incubator (orbit diameter of 2.5 cm).
  • the synthetic process was performed using two different culture media.
  • the first culture medium, defined CM1 “inoculum”, was used for the preparation of the inoculum.
  • 100 ml of inoculum were prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of “inoculum” culture medium at a pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask and then incubated at 30°C at 150 rpm for 24 hours.
  • the suspension was clarified by filtration on a GF/A filter (Whatman®) and the filtrate containing the copolymer in solution in the dichloromethane, was concentrated by evaporation and then dried under high vacuum at 40°C to constant weight.
  • the crude polyhydroxyalkanoate was purified by precipitation of a solution of the latter in solution in 10 times its weight of dichloromethane from 10 volumes of the solution of cold methanol. The solid obtained was dried under high vacuum at 40°C to constant mass.
  • the molecular weight of the polyhydroxyalkanoate obtained was characterized by size exclusion chromatography, with detection by refractive index.
  • Empower GC Relative molar mass/conventional module
  • the analysis makes it possible to measure the weight-average molecular weight (Mw in g/mol), the number-average molecular weight (Mn in g/mol), the polydispersity index PI (Mw/Mn) and the degree of polymerization DPn.
  • the monomer composition of the polyhydroxyalkanoate obtained was defined by gas chromatography equipped with a flame ionization detector. The identification is performed by injection of commercial standards and the monomer composition was determined by a methanolysis and silylation treatment. To determine the monomer composition, 7 mg of the polyhydroxyalkanoate polymer were dissolved in 1.5 mL of chloroform and subjected to methanolysis in the presence of 1.5 mL of an MeOH/HCI solution (17/2, v/v) at 100°C for 4 hours. The organic phase was then washed with 1 m L of water and then dried over MgSO4.
  • Silylation of the methyl esters formed was performed by adding 100 pL of BSTFA (N,O- bis(trimethylsilyl)trifluoroacetamide) and 100 pL of pyridine to the methylated sample. The solution was heated at 70°C for 1 hour and then evaporated to dryness. The sample is then dissolved in 600 pL of dichloromethane and analysed by chromatography under the following conditions: ⁇ Hewlett Packard 6890 Series machine
  • a copolymer containing 91 % by weight of poly(3-hydroxyoctanoate), 6% by weight of poly(3-hydroxyhexanoate) and 3% by weight of poly(3-hydroxybutanoate) was thus obtained.
  • a polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054TM, octanoic acid and acrylic acid.
  • the production process was performed using three different culture media.
  • the first undefined culture medium (CM1) was used for the preparation of the inoculum.
  • the second defined culture medium (CM2) was used for the unfed batch growth of the microorganism in the fermenter.
  • the third defined culture medium (CM3) was used for the feeding, or maintenance, of the continuous fermentation containing octanoic acid and acrylic acid (inhibitor of the p-oxidation pathway).
  • the CM1 and CM2 media are identical to those described in Example 1.
  • the composition in grams per litre of the medium CM3 is described in Table 10 below:
  • 100 ml of inoculum were prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of Nutrient Broth at a pH adjusted to 7.0 with 2N NaOH in a 250 ml Fernbach flask and were then incubated at 30°C at 150 rpm for 24 h.
  • the system was maintained at 30°C with shaking at 700 ⁇ 200 rpm and regulated in cascade with oxygenation for about 16 hours and/or the time for the microorganism to be able to reach its growth plateau.
  • Feeding of the fermenter with the medium CM3 was initiated when the microorganism reached its growth plateau, and withdrawal was then performed so as to maintain the initial mass of fermentation medium. Once the equilibrium state was reached in continuous culture, a fraction of the withdrawn material was centrifuged in order to separate the biomass from the fermentation medium. The biomass was dried by lyophilization and then extracted with dichloromethane for 24 hours. The suspension obtained was clarified by filtration through a GF/A filter (Whatman®). The filtrate obtained, comprising the copolymer dissolved in dichloromethane, was concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.
  • the crude polyhydroxyalkanoate was purified by precipitation of a solution of the latter in solution in 10 times its weight of dichloromethane from 10 volumes of the solution of cold methanol.
  • the solid obtained was dried under high vacuum at 40°C to constant weight.
  • a copolymer comprising 96% by weight of poly(3-hydroxyoctanoate), 3% by weight of poly(3-hydroxyhexanoate) and 1% by weight of poly(3-hydroxybutanoate) was thus obtained.
  • a polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054TM, nonanoic acid and acrylic acid.
  • the system is aerated with a flow of 1 vvm of air for a nominal dissolved oxygen (OD) value at 30% of saturation.
  • the production process is performed using three different culture media.
  • the first culture medium (CM1) is used for the preparation of the inoculum.
  • the second culture medium (CM2) is used for batch growth of the microorganism in the fermenter.
  • the third culture medium (CM3) is used for the feeding, or maintenance, of the continuous fermentation containing the carbon source of interest and the p-oxidation pathway inhibitor (acrylic acid).
  • the composition in grams per litre of the three media CM1 , CM2 and CM3 is described in Table 11 below:
  • composition of the Nutrient Broth is 37.5% beef extract and 62.5% peptone.
  • composition of the microelement solution in grams per litre is described in Table 12 below.
  • the system is maintained at 30°C with shaking at 700 ⁇ 200 rpm and regulated in cascade with oxygenation for about 16 hours and/or the time for the microorganism to be able to reach its growth plateau.
  • Feeding of the fermenter with the CM3 “continuous” medium is initiated when the microorganism has reached its growth plateau, and withdrawal is then performed so as to maintain the initial mass of fermentation medium.
  • a fraction of the withdrawn material is centrifuged so as to separate the biomass from the fermentation medium.
  • the biomass is dried by lyophilization and is then extracted with dichloromethane for 24 hours.
  • the suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate composed of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.
  • the molecular weight of the polyhydroxyalkanoate obtained was characterized by size exclusion chromatography, with detection by refractive index.
  • Empower GC Relative molar mass/conventional module
  • the analysis makes it possible to measure the weight-average molecular weight (Mw in g/mol), the number-average molecular weight (Mn in g/mol), the polydispersity index PI (Mw/Mn) and the degree of polymerization DPn.
  • the monomeric composition of the polyhydroxyalkanoate obtained was defined by gas chromatography equipped with a flame ionization detector. The identification is performed by injection of commercial standards and the monomer composition was determined by a methanolysis and silylation treatment. To determine the monomer composition, 7 mg of the polyhydroxyalkanoate polymer were dissolved in 1.5 mL of chloroform and subjected to methanolysis in the presence of 1.5 mL of an MeOH/HCI solution (17/2, v/v) at 100°C for 4 hours. The organic phase was then washed with 1 m L of water and then dried over MgSC .
  • Silylation of the methyl esters formed was performed by adding 100 pL of BSTFA (N,O- bis(trimethylsilyl)trifluoroacetamide) and 100 pL of pyridine to the methylated sample. The solution was heated at 70°C for 1 hour and then evaporated to dryness. The sample is then dissolved in 600 pL of dichloromethane and analysed by chromatography under the following conditions:
  • a copolymer comprising 86% by weight of poly(3-hydroxynonanoate), 9% by weight of poly(3-hydroxyheptanoate) and 5% by weight of poly(3-hydroxypentanoate) was thus obtained.
  • a polymer was prepared according to the procedure of example 19 using nonanoic acid (instead of octanoic acid) and without acrylic acid.
  • a copolymer comprising 68% by weight of poly(3-hydroxynonanoate), 27% by weight of poly(3-hydroxyheptanoate) and 5% by weight of poly(3-hydroxypentanoate) was thus obtained.
  • a polymer was prepared according to the procedure of example 19 using dodecanoic acid (instead of octanoic acid).
  • a copolymer comprising 44% by weight of poly(3-hydroxydodecanoate), 38% by weight of poly(3-hydroxydecanoate) and 18% by weight of poly(3-hydroxyoctanoate) was thus obtained.
  • Example 24 Copolymer of PHA bearing a side chain R 1 representing an n-pentyl group and R 2 representing an n-propyl group
  • Example 24 is an adaptation of the article Biomacromolecules 2012, 13, 2926-2932: “Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer”
  • the microorganism used is Pseudomonas putida ATCC® 47054TM.
  • the system is aerated with a flow of 3 vvm of air for a nominal dissolved oxygen (OD) value at 30% of saturation.
  • the first undefined culture medium (CM1) is used for the preparation of the inoculum.
  • the second defined culture medium (CM2) is used for batch growth of the microorganism in the fermenter.
  • the third defined culture medium (CM3) is used for the feeding, or maintenance, of the continuous fermentation containing the carbon source of interest and the p-oxidation pathway inhibitor.
  • composition in grams per litre of the three media is described in Table 13.
  • Composition in grams per litre of the culture media for the inoculum and for maintenance. [00372] [Table 13]
  • composition of the Nutrient Broth is 37.5% beef extract and 62.5% peptone.
  • Reference 233000 DIFCOTM The composition of the microelement solution in grams per litre is described in Table 14: composition in grams per litre of the microelement solution
  • Fernbach flask and are then incubated at 30°C at 150 rpm for 24 hours.
  • the system is maintained at 30°C with shaking at 700 ⁇ 200 rpm and regulated in cascade with oxygenation for about 16 hours and/or the time for the microorganism to be able to reach its growth plateau.
  • Feeding of the fermenter with the medium CM3 is initiated when the microorganism has reached its growth plateau, and withdrawal is then performed so as to maintain the initial mass of fermentation medium. Once the equilibrium state is reached in continuous culturing, a fraction of the withdrawn material is centrifuged so as to separate the biomass from the fermentation medium. The biomass is dried by lyophilization and is then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate composed of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.
  • a GF/A filter Whatman®
  • the PHA may optionally be purified by successive dissolution and precipitation, for instance using a dichloromethane/methanol system.
  • the microorganism used is Pseudomonas putida KT2440 ATCC® 47054TM.
  • the system is aerated with a flow of 0.5 vvm of air for a nominal dissolved oxygen (OD) value at 30% of saturation.
  • the pH is regulated with a solution composed of ammonia and glucose at 15% and 40% final mass, respectively.
  • the temperature of the fermentation medium is regulated at 30°C.
  • the fermentation medium is regulated in terms of temperature-pressure of dissolved oxygen and pH (not shown).
  • the production process is performed using three different culture media.
  • the first culture medium defined CM1 “inoculum”, is used for the preparation of the preculture.
  • the second culture medium defined CM2 “batch”, is used for unfed batch growth of the microorganism with the primary carbon sources in the Fernbach flasks.
  • the third culture medium defined CM3 “maintenance”, is used for the fed-batch or maintenance fermentation mode with the carbon sources of interest at a flow rate calibrated as a function of the growth of the microorganism.
  • [00385] [Table 15]: [00386]The composition of the Nutrient Broth, as mass percentages, is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCOTM.
  • 100 mL of preculture are prepared by suspending a cryotube containing 1 mL of the strain with 100 mL of “inoculum” culture medium at a pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask and then incubated at 30°C at 150 rpm for 24 hours.
  • the biomass is isolated by centrifugation and then washed three times with water.
  • the biomass is dried by lyophilization before being extracted with ethyl acetate for 24 hours.
  • the suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate composed of PHA dissolved in the ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.
  • the PHA may optionally be purified by dissolution in ethyl acetate and successive precipitations from a 70/30 v/v% ethanol/water system, for example.
  • the compounds of Examples 1 to 25 may be mixed with one or more volatile solvent(s) b) and non-volatile solvent(s) c) as defined previously, respecting the mass ratio u as defined previously.
  • the mixing of the PHA(s) a) with the solvents b) and c) may be performed at room temperature, with stirring, preferably in the presence of a fatty substance d) and optionally of organic solvent(s) other than e) as defined previously.
  • water f) is added to the mixture of a), b), c) and d) and one or more organic solvents other than e) as defined previously are then optionally added.
  • compositions 27 (comparative) and 28 (invention) described in Table 17 below were prepared:
  • the PHA, isododecane and ethanol are stirred at 2500 rpm, at a temperature of 25°C.
  • the volatile oils b) and non-volatile oils c) are introduced and the medium is heated from 25°C to 80°C with stirring at 2500 rpm.
  • the medium is maintained at 80°C for 30 minutes with stirring at 3000 rpm and is then cooled from 80°C to 25°C with stirring at 2500 rpm.
  • the first step in this test consists in making a deposit.
  • the deposits are prepared on a Byko Chart Lenata contrast card using a film spreader and left to dry for 24 hours at 25°C and 45% RH.
  • the final thickness of the deposit is 30 pm.
  • a wear resistance test is performed on this dry deposit.
  • a hydrophilic steel ball is used as a friction device.
  • the load or normal force applied is 1 N, and the displacement speed is 50 mm.S’ 1 .
  • On each film are defined tracks on which the friction device makes multiple passes. In the case of wear measurements, permanent contact is maintained during the to and fro trips of the ball on the deposit. The number of passes is increased for each track.
  • the wear resistance is quantified as the minimum number of passes to completely wear out the deposit.
  • the number of passes per track are, respectively, 10 and 30 to 50 passes.
  • the sensitivity to stressors is evaluated after depositing a drop of stressor (20 pl for water) on the surface of the deposit. The evaluations are made after 1 hour of contact between the stressor and the deposit. The level of sensitivity to stressors is noted as follows.
  • compositions of the invention (Examples 27 to 29) remain water-resistant.
  • the presence of several oils has no impact on the water resistance of the films obtained.
  • Example 1 PH A copolymer bearing a side chain R 1 representing a 2% unsaturated n-octenyl group and R 2 representing an n-hexyl group unsaturated carried out in discontinuous culture fed with two sources of carbon in C9 and C11: 1 98/2
  • the fermentation medium is regulated in temperature-dissolved oxygen pressure and pH (not shown on the fig.).
  • the production process is carried out using three distinct culture media.
  • the first culture medium defined MC1 “inoculum” is used for the preparation of the preculture.
  • the second culture medium defined MC2 “bach” is used for the non-supplied discontinuous growth of the microorganism with the primary carbonaceous sources in the Fernbachs flasks.
  • the third culture medium defined (MC3 "maintenance") is used for the discontinuous feeding, or maintenance, of the fermentation with the carbonaceous sources of interest at a rate calibrated according to the growth of the microorganism.
  • Table 21 Composition in grams per liter of culture media for preculture and maintenance.
  • 100 mL of preculture are prepared by suspending a cryotube containing 1 mL of the strain with 100 mL “inoculum” culture media at pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask then incubating at 30° C at 150 rpm for 24 hours.
  • the introduction of the maintenance is carried out by applying the flow rate defined by equation 1.
  • the biomass is isolated by centrifugation then washed three times with some water.
  • the biomass is dried by freeze-drying before being extracted with dichloromethane for 24 hours.
  • the suspension is clarified by filtration on a GF/A filter (Wattman®) the filtrate, composed of PHA in solution in dichloromethane, is concentrated by evaporation then dried under high vacuum at 40°C until constant mass.
  • the PHA can optionally be purified by solubilization and successive precipitations such as a dichloromethane methanol system for example.
  • the PHA was characterized by gas chromatography equipped with an FID detector.
  • Example 11 Functionalization of mcl-PH A with linear side chain R 1 representing a n- octylenyl group and R 2 n-hexyl unsaturated at 2% of example 1” with thiolactic acid
  • compositions of example 30 to 35 comprise ingredients according to table 18
  • the first step in this test consists in making a deposit.
  • the deposits are prepared on a Byko Chart Lenata contrast card and left to dry for 24 hours at 25°C and 45% RH.
  • the final thickness of the deposit is 30 pm.
  • a wear resistance test is performed on this dry deposit.
  • a hydrophilic steel ball is used as a friction device.
  • the load or normal force applied is 1 N, and the displacement speed is 50 mm.s’ 1 .
  • On each film are defined tracks on which the friction device makes multiple passes. In the case of wear measurements, permanent contact is maintained during the to and fro trips of the ball on the deposit. The number of passes is increased for each track.
  • the wear resistance is quantified as the minimum number of passes to completely wear out the deposit.
  • the number of passes per track are, respectively, 10, 30, 50, 100, 200 and 300 passes. [00429] Each measurement was repeated five times.
  • compositions of the invention (Examples 30 to 36) remain very water-resistant in spite of the addition of non volatile and volatile oil. The presence of several oils has no impact on the water resistance of the films obtained.
  • the 2 deposits for examples 37 and 39 are very cohesive, deposit from example 39 according to the invention having a significant better wear resistance than deposit from example 37.

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)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention concerne une composition cosmétique comprenant a) un ou plusieurs copolymères de polyhydroxyalcanoate (PHA) qui contiennent, et de préférence sont constitués de plusieurs motifs répétés choisis parmi les motifs (A) ci-dessous, ainsi que leurs isomères optiques ou géométriques, leurs sels d'acides ou de bases, organiques ou minéraux, et leurs solvates, tels que des hydrates : -[-O-CH(R1)-CH2-C(O)-]- motif (A), motifs polymères (A) dans lesquels : - R1 est tel que défini dans la description ; b) une ou plusieurs huiles volatiles ; c) une ou plusieurs huiles non volatiles ; et étant entendu que le rapport massique U entre la somme des masses d'huiles volatiles b) et la somme des masses d'huiles non volatiles c) est non nul et inférieur à 900.
EP22844090.5A 2021-12-23 2022-12-22 Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un mélange d'huile volatile et d'huile non volatile Pending EP4452201A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2114367A FR3131210B1 (fr) 2021-12-23 2021-12-23 Composition cosmétique comprenant un copolymère polyhydroxyalcanoate à chaine hydrocarbonée (in)saturé, et un mélange d’huile volatile et non volatile
PCT/EP2022/087571 WO2023118481A1 (fr) 2021-12-23 2022-12-22 Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un mélange d'huile volatile et d'huile non volatile

Publications (1)

Publication Number Publication Date
EP4452201A1 true EP4452201A1 (fr) 2024-10-30

Family

ID=80786779

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22844090.5A Pending EP4452201A1 (fr) 2021-12-23 2022-12-22 Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un mélange d'huile volatile et d'huile non volatile

Country Status (6)

Country Link
EP (1) EP4452201A1 (fr)
JP (1) JP7817400B2 (fr)
KR (1) KR20240101621A (fr)
CN (1) CN118748936A (fr)
FR (1) FR3131210B1 (fr)
WO (1) WO2023118481A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2729218A2 (fr) 2010-12-30 2014-05-14 L'Oréal Compositions cosmétiques résistant au transfert, longue tenue, confortables à effet brillant et non collant
WO2018022614A1 (fr) 2016-07-29 2018-02-01 L'oreal Composition cosmétique a tenue de longue durée, résistante au transfert, présentant un pouvoir adhésif amélioré
EP3600558A1 (fr) 2017-03-30 2020-02-05 Bio-On S.p.A. Composition cosmétique comprenant un polyester biodégradable et une phase huileuse
WO2020128050A1 (fr) 2018-12-20 2020-06-25 L'oreal Composition cosmétique comprenant un polyhydroxyalcanoate dans un milieu huileux
WO2022208027A1 (fr) 2021-03-31 2022-10-06 Chanel Parfums Beaute Composition cosmétique comprenant au moins un polyhydroxyalcanoate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2756176B1 (fr) 1996-11-26 1998-12-18 Oreal Composition cosmetique comprenant un compose fluore et presentant un confort ameliore
WO2008155059A2 (fr) 2007-06-19 2008-12-24 Cognis Ip Management Gmbh Mélanges d'hydrocarbures et leur utilisation
EP2510037A4 (fr) 2009-12-07 2014-12-17 Univ Kingston Polymère de polyhydroxyalcanoate à longueur de chaîne moyenne et procédé de fabrication de celui-ci
FR2961093A1 (fr) 2010-06-09 2011-12-16 Oreal Composition cosmetique comprenant un polymere et un derive de 4-carboxy 2-pyrrolidinone, procede de traitement cosmetique et compose
FR2964663B1 (fr) 2010-09-14 2013-10-11 Oreal Composition cosmetique comprenant une matiere colorante, ladite matiere colorante et procede de traitement cosmetique
CA2887551A1 (fr) 2012-10-12 2014-04-17 Alzo International, Inc. Formation perfectionnee de film etanche et resistant au transfert

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2729218A2 (fr) 2010-12-30 2014-05-14 L'Oréal Compositions cosmétiques résistant au transfert, longue tenue, confortables à effet brillant et non collant
WO2018022614A1 (fr) 2016-07-29 2018-02-01 L'oreal Composition cosmétique a tenue de longue durée, résistante au transfert, présentant un pouvoir adhésif amélioré
EP3600558A1 (fr) 2017-03-30 2020-02-05 Bio-On S.p.A. Composition cosmétique comprenant un polyester biodégradable et une phase huileuse
WO2020128050A1 (fr) 2018-12-20 2020-06-25 L'oreal Composition cosmétique comprenant un polyhydroxyalcanoate dans un milieu huileux
WO2022208027A1 (fr) 2021-03-31 2022-10-06 Chanel Parfums Beaute Composition cosmétique comprenant au moins un polyhydroxyalcanoate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2023118481A1

Also Published As

Publication number Publication date
KR20240101621A (ko) 2024-07-02
JP7817400B2 (ja) 2026-02-18
CN118748936A (zh) 2024-10-08
FR3131210A1 (fr) 2023-06-30
FR3131210B1 (fr) 2024-07-26
WO2023118481A1 (fr) 2023-06-29
JP2024544005A (ja) 2024-11-26

Similar Documents

Publication Publication Date Title
US20250177281A1 (en) Cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing a (un)saturated hydrocarbon-based chain and an oligo/polyester
US20230120675A1 (en) Cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing a(n) (un)saturated hydrocarbon-based chain and a surfactant
EP4452201A1 (fr) Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un mélange d'huile volatile et d'huile non volatile
EP4452218A1 (fr) Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et une substance grasse cristallisable
US20250041201A1 (en) Cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing a(n) (un)saturated hydrocarbon-based chain and a clay
US20250381127A1 (en) Cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing a(n) (un)saturated hydrocarbon-based chain and a silicone polymer
WO2023118524A1 (fr) Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un polysaccharide modifié
WO2023118526A1 (fr) Composition cosmétique comprenant un copolymère de polyhydroxyalcanoate portant une chaîne hydrocarbonée (in)saturée et un polymère hydrocarboné
US20250352453A1 (en) Composition comprising a polyhydroxyalkanoate copolymer with a long hydrocarbon-based chain bearing ionic group(s), and method for treating keratin materials using the composition
US20250127706A1 (en) Cosmetic composition comprising a polyhydroxyalkanoate copolymer bearing a(n) (un)saturated hydrocarbon-based chain and a polysaccharide
FR3131204A1 (fr) Composition cosmétique comprenant un copolymère polyhydroxyalcanoate à chaine hydrocarbonée (in)saturé, et un plastifiant
FR3131208A1 (fr) Composition cosmétique comprenant un copolymère polyhydroxyalcanoate à chaine hydrocarbonée (in)saturé, et au moins un latex de polyuréthane

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240723

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA