Composition comprising a long-chain hydrocarbon polyhydroxyalkanoate copolymer with ionic group(s), process for treating keratinous materials implementing the composition

Abstract

Title: Composition comprising a long-chain hydrocarbon polyhydroxyalkanoate copolymer with ionic group(s), process for treating keratinous materials implementing the composition. The present invention relates to a process for treating keratinous materials, preferably α) keratinous fibers, particularly human fibers such as hair, or β) human skin, particularly lip skin, implementing a composition C1, preferably cosmetic, comprising a) one or more polyhydroxyalkanoate (PHA) copolymer(s) a) which contain one or more of the following units (A), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: -[-O-CH(R1)-CH2-C(O)-]- unit (A) polymeric units (A) in which: R1 represents a non-cyclic hydrocarbon chain, saturated or unsaturated, linear or branched, or cyclic saturated or unsaturated non-aromatic,comprising from 3 to 30 carbon atoms; said hydrocarbon chain being: substituted by one or more anionic (A-), cationic (C+) groups and their mixtures with A- and C+ as defined above; it being understood that: the R1 radicals may include in the same PHA both A- and C+ groups, in which case the counter-ions M+ and Q- may be absent while ensuring the electroneutrality of the PHA; and the composition comprises an amount less than or equal to 2% by weight of surfactants, relative to the total weight of the composition.

Description

Title of the invention: Composition comprising a long-chain hydrocarbon polyhydroxyalkanoate copolymer with ionic group(s), process for treating keratinous materials implementing the composition

[0001] The present invention relates to a composition, preferably cosmetic, comprising at least one polyhydroxyalkanoate (PHA) copolymer with hydrocarbon chains having ionic function(s), particular ionic PHAs, the use of the composition in cosmetics and a process for treating keratinous materials using the composition.

[0002] It is known to use film-forming polymers in cosmetics that are transportable in organic media such as hydrocarbon oils. Polymers are notably used as film-forming agents in makeup products such as mascaras, eyeliners, eyeshadows, or lipsticks.

[0003] Document FR-A-2964663 describes a cosmetic composition comprising pigments coated with a C3-C2i polyhydroxyalkanoate such as poly(hydroxybutyrate-co-hydroxyvalerate).

[0004] Document WO 2011 / 154508 describes a cosmetic composition comprising a 4-carboxy-2-pyrolidinone ester derivative and a film-forming polymer which may be a polyhydroxyalkanoate such as polyhydroxybutyrate, polyhydroxyvalerate and polyhydroxybutyrate-co-polyhydroxyvalerate.

[0005] US-A-2015 / 274972 describes a cosmetic composition comprising a thermoplastic resin, such as a polyhydroxyalkanoate, in aqueous dispersion and a silicone elastomer.

[0006] Most polyhydroxyalkanoates are polymers resulting from the polycondensation of largely identical repeating polymer units derived from the same carbon source or substrate. These documents do not describe the use of a copolymer resulting from the polycondensation of an aliphatic substrate or carbon source and at least a second substrate different from the first, comprising one or more ionic groups of a different chemical nature than the first carbon source.

[0007] There is therefore a need for compositions comprising PHAs with various functionalizations or which are functionalizable and can subsequently become more water-soluble despite the presence of a long aliphatic chain. This would make it possible to obtain a film on keratinous materials exhibiting good cosmetic properties, including good resistance to oils and sebum, as well as the ability to play on shine or matte finish.

[0008] Consumers are increasingly seeking cosmetic formulas with a low surfactant content (< 2% by weight relative to the total weight of the formula), or even without surfactants. However, it is known that it is difficult to obtain stable particles with long-chain PHAs, particularly carboxylated mcl-PHAs, without using surfactants [cf. “Stability of Aqueous Suspensions of Medium-Chain-Length Poly-3-Hydroxyalkanoate Particles”, Journal of Polymers and the Environment, vol. 24, p. 281-285 (2016)].

[0009] Unexpectedly, it was discovered that polyhydroxyalkanoate copolymers with hydrocarbon chains with ionic group(s), as defined below, can be easily implemented in aqueous media (particularly with predominantly water as the solvent), thus allowing homogeneous and easy-to-use compositions to be obtained, even using very little or no surfactant.

[0010] Furthermore, the composition exhibits good stability, particularly after one month of storage at room temperature (25°C). The composition, especially after application to keratinous materials, produces a film with good cosmetic properties, particularly good resistance to oils and sebum, as well as a matte or glossy finish. Moreover, the ionic groups allow the PHA polymers to interact with active ingredients, particularly organic ones, such as UV filters, chromophores (fluorescent or non-fluorescent), and anti-aging agents. These active ingredients contain ionic groups with ionicities opposite to those of the PHA polymers, and the active ingredients can then become more persistent once bonded to oils, water, and sebum.

[0011] Thus, the first object of the present invention is a process for treating keratinous materials, preferably a) keratinous fibers, particularly human such as hair, or |3) human skin, particularly lips, employing a composition Cl, preferably cosmetic, comprising a) one or more polyhydroxyalkanoate (PHA) copolymer(s) a) which contain one or more of the following units (A), as well as their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0012] -[-O-CH(R1)-CH2-C(O)-]- unit (A)

[0013] polymer units (A) in which: - R 1 represents a non-cyclic, saturated or unsaturated, linear or branched hydrocarbon chain, or a non-aromatic cyclic, saturated or unsaturated chain, comprising from 3 to 30 carbon atoms; preferably the chain hydrocarbon is chosen from i) (C5-C28)alkyl, linear or branched, ii) (C6-C28)alkenyl, linear or branched, iii) (C6-C28)alkynyl, linear or branched, iii) preferably the hydrocarbon chain is non-cyclic and linear; said hydrocarbon chain being: • substituted by one or more anionic (A), cationic (C+) groups and mixtures thereof; ** the group(s) A being chosen from -C(O)OH, -C(O)O , -SO3H, -S(O)2O , -OS(O)2OH, -OS(O)2O , -P(O)OH2, -P(O)O2, -P(O)2O , -P(OH)2, =P(O)-OH, -P(OH)O, =P(O)-O , =P-OH, and =P-O and mixtures thereof, the anionic parts comprise one or more cationic counterions M+ to achieve the electroneutrality of the PHA, such as i) an alkali metal, ii) an alkaline earth metal, iii) ammonium RaRbRcRdN+, iv) phosphonium RaRbRcRdP+ with R representing a hydrogen atom, a (Ci-C4)alkyl group, or (hetero)aryl(Ci-C4)alkyl group such as benzyl, preferably Ra represents a hydrogen atom or a (CrC4)alkyl group;Rb, Rc, and Rd, whether identical or different, represent a (Ci-C4)alkyl group possibly substituted by one or more hydroxy groups, (hetero)aryl, (hetero)aryl(Ci-C4)alkyl such as benzyl, (hetero)cycloalkyl, (hetero)cycloalkyl(Ci-C4)alkyl, or else Rb and Rc, or Rc and Rd, together with the nitrogen or phosphorus atom bearing them, represent a heterocycle, saturated or unsaturated, aromatic or non-aromatic, particularly (CrC4)alkyl possibly substituted by one or more hydroxy groups, v) the cationic forms of lysine or guanidine; ;

[0014] ** the cationic group(s) C+ being chosen from among the amine groups cationizable -NRbRc, ammonium -N+RaRbRc, phosphonium -P+RaRbRc, cationizable amidine -C(=NRa)-NRbRc, amidinium -C(=NRa)-N+RbRcRd, cationizable guanidine -N(Ra)-C(=NRa)-NRbRc, guanidinium -N(Ra)-C(=NRa)-N+RbRcRd, or cationizable imidazolyl possibly substituted by one or more Ra radicals as defined above, or imidazolium possibly substituted by one or more Ra radicals as defined above, and mixtures thereof, and Rb, Rc and Rd as defined above, the cationic parts comprising one or more anionic counter ions Q to achieve the electroneutrality of the PHA, such as a halide, a carboxylate such as acetate, glutamate; and possibly;

[0015] ***the R1 radicals may further be substituted by one or more atoms or groups selected from: a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) thiocarboxy, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl, k) cosmetic active; 1) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, m) thiosulfate; X representing a') O, S, N(R'a) or Si(R'b)(R'c), b') S(O)r, or (thio)carbonyl, c') or combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; R'a representing a hydrogen atom, or a (Ci-C4)alkyl group, or aryl(Ci-C4)alkyl such as benzyl, preferably Ra representing a hydrogen atom; R'b and R'c, whether identical or different, represent a (CrC4)alkyl or (Ci-C4)alkoxy group, particularly a single substituent, preferably chosen from b) halogen, and j) such as epoxide and / or • possibly interrupted by one or more a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, c') or associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide, preferably ester -OC(O)- or -C(O)-O- with r being 1 or 2, Ra being as defined previously, preferably Ra representing a hydrogen atom, Rb and Rc being as defined previously; b) possibly water;

[0016] it being understood that: - R1 radicals can include A and C+ groups in the same PHA, in which case the M+ and Q' counter-ions can be absent while ensuring the electroneutrality of the PHA; and - the composition comprises an amount less than or equal to 2% by weight of surfactants, relative to the total weight of the composition, particularly less than or equal to 1% by weight of surfactants, more particularly less than 0.5% by weight of surfactants relative to the total weight of the composition, preferably the composition is free of surfactants.

[0017] Another object of the invention is a composition, preferably cosmetic, Cl as defined above and or C' 1 below comprising a) one or more polyhydroxyalkanoate (PHA) copolymer(s) a) which contain, one or more units (A) in which: when R1 represents a hydrocarbon chain which is saturated, linear comprising 3 to 10 carbon atoms and substituted by one or more carboxy groups -C(O)OH then said chain is interrupted by heteroatoms or groups a') to c') as defined above.

[0018] Another object of the invention is a PHA copolymer as defined above in which (A) is such that: - R 1 represents a non-cyclic, saturated or unsaturated, linear or branched hydrocarbon chain, or a non-aromatic cyclic, saturated or unsaturated chain, comprising from 5 to 28 carbon atoms; preferably the chain the hydrocarbon chain is selected from i) (C5-C28)alkyl, linear or branched, ii) (C6-C28)alkenyl, linear or branched, iii) (C6-C28)alkynyl, linear or branched, iii) preferably the hydrocarbon chain is non-cyclic and linear; said hydrocarbon chain being: substituted by one or more anionic (A), cationic (C+) groups and mixtures thereof;

[0019] ** the group(s) A being chosen from -C(O)O, -SO3H, -S(O)2O, -OS(O)2OH, -OS(O)2O , -P(O)OH2, -P(O)O2, -P(O)2O, -P(OH)2, =P(O)-OH, -P(OH)O , =P(0)-0 , =P-OH, and =P-0 and their mixtures, the anionic parts comprise one or more cationic counter-ions M+;

[0020] ** the cationic group(s) C+ being chosen from among the amine groups cationizable -NRbR„ ammonium -N+RaRbRc, phosphonium -P+RaRbRc, cationizable amidine -C(=NRa)-NRbRc, amidinium -C(=NRa)-N+RbRcRd, cationizable guanidine -N(Ra)-C(=NRa)-NRbRc, guanidinium -N(Ra)-C(=NRa)-N+RbRcRd, or cationizable imidazolyl possibly substituted by one or more Ra radicals as defined above, or imidazolium possibly substituted by one or more Ra radicals as defined above, and their mixtures to achieve the electroneutrality of PHA, with Ra, Rb, Rc and Rd as defined above, the cationic parts comprising one or more anionic counter-ions Q, M+ and Q- being as defined above;

[0021] Preferably the PHA copolymer as defined above in which (A) is such that R1 represents a hydrocarbon chain, in particular i) (C5-C28)alkyl, linear or branched, which is substituted by one or more (preferably one) groups A selected from -C(O)O M+ with M+ as above, preferably ammonium RaRbRcRdN+, with Ra, Rb, Rc and Rd as defined above, preferably Ra represents a hydrogen atom; Rb, and Rc, identical or different, preferably identical, represent a (CrC4)alkyl group, linear or branched, preferably branched such as isopropyl or isobutyl, more preferably isopropyl; and Rd represents a (Ci-C4)alkyl group, linear or branched such as ethyl, more particularly M+ represents a diisopropylethylammonium group: (i-Pr)2N+(H)Et.

[0022] Another object of the invention is a process for preparing PHA with a carboxylate group.

[0023] More particularly, the invention relates to a cosmetic, non-therapeutic process for treating keratinous materials, comprising applying to the keratinous materials the composition Cl as defined above or Cl' as defined below. The treatment process is in particular a process for the care or makeup of keratinous materials.

[0024] For the purposes of the present invention, and unless otherwise indicated: - By "cosmetic active ingredient": we mean the radical of an organic compound or organosilicon compounds that can be incorporated into a cosmetic composition to have an effect on keratinous materials, whether this effect is immediate or achieved through repeated applications. Examples of cosmetic active ingredients include colored or non-colored, fluorescent or non-fluorescent chromophores such as those derived from optical brighteners, or chromophores derived from UVA and / or UVB filters; anti-aging active ingredients or those intended to provide benefits to the skin, such as those acting on the skin barrier function; deodorant active ingredients other than mineral particles; antiperspirant active ingredients other than mineral particles; desquamating active ingredients; antioxidant active ingredients; moisturizing active ingredients; sebum-regulating active ingredients; active ingredients intended to reduce shine; active ingredients intended to combat the effects of pollution; antimicrobial or bactericidal active ingredients; anti-dandruff active ingredients; and perfumes. - By "(hetero)aryl" we mean the aryl or heteroaryl groups; - By "(hetero)cycloalkyl" we mean cycloalkyl groups or heterocycloalkyl; - The "aryl" or "heteroaryl" radicals, or the aryl or heteroaryl part of a radical, can be substituted by at least one substituent attached to a carbon atom, chosen from: • an alkyl radical in Ci-C6, preferably in C1-C4; • a halogen atom such as chlorine, fluorine or bromine; • a hydroxy group; • a C1-C2 alkoxy radical; a C2-C4 (poly)-hydroxyalkoxy radical; • an amino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, in Ci-C6, Ci-C6, preferably in CrC4; • an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom, • an alkyl radical in Ci-C4 and the radical R' is an alkyl radical in Ci-C4; a carbamoyl radical ((R)2N-CO-) in which the radicals R, identical or not, represent a hydrogen atom, an alkyl radical in CrC4; an alkylsulfonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom, a CrC4 alkyl radical and the radical R' represents a C1-C4 alkyl radical, a phenyl radical; an aminosulfonyl radical ((R)2N-SO2-) in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical in CrC4; a carboxylic radical in acidic or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); a cyano group (CN); a polyhalogeno(Ci-C4)alkyl group, preferably trifluoromethyl (CF3); The cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent attached to a carbon atom chosen from the following groups: hydroxy, CrC4 alkoxy, C2-C4 (poly)hydroxyalkoxy, alkylcarbonylamino ((RCO-NR'-) in which the radical R' is a hydrogen atom, an alkyl radical in Ci-C4 and the radical R is an alkyl radical in CrC2, amino substituted by one or two identical or different alkyl groups in CrC4; alkylcarbonyloxy ((RCO-O-) in which the radical R is an alkyl radical in CrC4, amino substituted by one or two identical or different alkyl groups in CrC4; alkcoxycarbonyl ((RO-CO-) in which the radical R is an alkyl radical in CrC4, amino substituted by one or two identical or different alkyl groups in CrC4; a cyclic radical, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, can also be substituted by one or more oxo groups; A hydrocarbon chain is unsaturated when it contains one or more double bonds and / or one or more triple bonds; an "aryl" radical represents a mono- or polycyclic hydrocarbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl, preferably phenyl; a "heteroaryl" radical represents a mono- or polycyclic group, condensed or not, comprising 5 to 22 links, 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atoms, and of which at least one ring is aromatic; preferably a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl; a "cyclic" or "cycloalkyl" radical is a non-aromatic cyclic hydrocarbon radical, mono- or polycyclic, condensed or non-condensed, containing from 5 to 22 carbon atoms, which may have from 1 to several unsaturations, preferably the cycloalkyl is a cyclohexyl group; a "heterocyclic" or "heterocycloalkyl" radical is a non-aromatic mono- or polycyclic cyclic radical, condensed or not, containing 3 to 9 links, comprising 1 to 4 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atoms, preferably the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidinyl, morpholinyl; an "alkyl" radical is a saturated hydrocarbon radical, linear or branched, particularly in Ci-C6, preferably in Ci-C4; an "alkenyl" radical is an unsaturated hydrocarbon radical, linear or branched, comprising one or more double bonds, conjugated or not; an "alkynyl" radical is an unsaturated hydrocarbon radical, linear or branched, comprising one or more triple bonds, conjugated or not; an "alkoxy" radical is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in Ci-C6 preferably in Ci-C4; The term "organic or mineral acid salt" refers more specifically to organic or mineral acid salts, in particular those selected from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids: Alk-S(O)2OH such as methylsulfonic acid and ethylsulfonic acid; v) acids arylsulfonic acids: Ar-S(O)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid H3PO4; ix) triflic acid CF3SO3H and x) tetrafluoroboric acid HBF4;xi) of carboxylic organic acids R°-C(O)-OH (!') formula (!') in which R° represents a (hetero)aryl group such as phenyl, (hetero)aryl(Ci-C4)alkyl such as benzyl, or (Ci-Cio)alkyl said alkyl group being optionally substituted preferably by one or more hydroxy groups, amino radicals, or carboxy groups, R° preferably designating a (Ci-C6)alkyl group optionally substituted by 1, 2 or 3 hydroxy groups, or more preferably the monocarboxylic acids of formula (F) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid; and the polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof;and xii) amino acids containing more carboxylic acid radicals than amino groups such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid; an "anionic counter-ion" is an anion or anionic group associated with the cationic charge; more particularly the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates among which the Ci-C6 alkylsulfonates: Alk-S(O)2O such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O such as benzenesulfonate and toluenesulfonate or tosylate; (v) Carboxylates, in particular those of formula R'[C(O)OH]U, with R' representing a hydrocarbon chain comprising from 1 to 8 carbon atoms, in particular from 1 to 6, preferably from 1 to 4, saturated or unsaturated, linear or branched, possibly substituted by one or more hydroxyl or (di)(Ci-C6)(alkyl)amino groups and u an integer between 1 and 6, better between 1 and 4, even better 1, 2 or 3, such as citrate; succinate; tartrate; lactate;acetate, or glutamate; vi) alkyl sulfates: Alk-OS(O)O such as methyl sulfate and ethyl sulfate; vii) arylsulfates: Ar-OS(O)O such as benzene sulfate and toluene sulfate; vii) alkoxysulfates: Alk-OS(O)2O such as methoxy sulfate and ethoxysulfate; viii) the; aryloxysulfates: Ar-OS(O)2O, x) phosphate; ix) triflate; and x) borates such as tetrafluoroborate; a "cationic counter ion" is a cation or cationic group associated with the anionic charge; more particularly the cationic counter ion is chosen from the metals i) alkali such as sodium or potassium, preferably Na+; ii) alkaline earth metals such as Ca2+, Mg2+, iii) ammonium RaRbRcRdN+, iv) phosphonium RaRbRcRdP+ with R representing a hydrogen atom, or a (Ci-C4)alkyl group, or (hetero)aryl(Ci-C4)alkyl such as benzyl, preferably Ra represents a hydrogen atom or a (Ci-C4)alkyl group; R b, R c, and R d, identical or different, represent a (CrC4)alkyl, (hetero)aryl, (hetero)aryl(Ci-C4)alkyl group such as benzyl, (hetero)cycloalkyl, (hetero)cycloalkyl(Ci-C4)alkyl, particularly (CrC4)alkyl; or v) the cationic forms of lysine or guanidine; The R1 radicals can include in the same PHA groups A and C+ in which case the counter ions M+ and Q' can be absent while ensuring the electroneutrality of the PHA; for example the same PHA can include within it a number of carboxylate group(s) "n" and the same number of ammonium group(s) "n" so that the electroneutrality of the PHA is achieved, another case is a PHA which includes two carboxylate groups, and an alkaline earth metal Ca2+ so that the electroneutrality of the PHA is achieved. The term "solvates" refers to hydrates as well as associations with linear or branched CrC4 alcohols such as ethanol, isopropanol, and n-propanol; a "chromophore" is defined as a radical derived from a colorless or colored compound capable of absorbing UV and / or visible radiation at a wavelength Xabs between 250 and 800 nm; preferably, the chromophore is colored, i.e., it absorbs wavelengths in the visible range, preferably between 400 and 800 nm. Preferably, chromophores appear colored to the eye, particularly between 400 and 700 nm (Ullmann's Encyclopedia, 2005, Wiley-VcH, Verlag "Dies, General Survey", § 2.1 Basic Principle of Color); By "fluorescent chromophore" we mean a chromophore that is also capable of re-emitting in the visible range at an emission wavelength Xem between 400 and 800 nm, and greater than the absorption wavelength. Preferably with a Stokes shift, i.e., the difference between the maximum absorption wavelength and the wavelength The emission wavelength is at least 10 nm. Preferably, fluorescent chromophores are derived from fluorescent dyes capable of absorbing in the visible spectrum (Xabs), i.e., at a wavelength between 400 and 800 nm, and re-emitting in the visible spectrum (Xem) between 400 and 800 nm. More preferably, fluorescent chromophores are capable of absorbing at a wavelength (Xabs) between 420 nm and 550 nm and re-emitting in the visible spectrum at a wavelength (Xem) between 470 and 600 nm. - By "optical brightener chromophore," we mean a chromophore derived from optical brightener compounds or from "Optical brighteners, optical brightening agents (OBAs)," "fluorescent brightening agents (FBAs)," or "fluorescent whitening agents (FWAs)," i.e., which absorbs UV radiation at a wavelength Xabs between 250 and 350 nm and then re-emits this energy by fluorescence in the visible spectrum at an emission wavelength Xem between 400 and 600 nm, i.e., wavelengths between blue-violet and blue-green with a maximum in the blue. Optical brightener chromophores are therefore colorless to the naked eye. - By "UV-A filter" we mean a chromophore made from a compound that filters (or absorbs) UV-A ultraviolet rays at a wavelength between 320 and 400 nm. We can distinguish between short UV-A filters (absorbing rays at a wavelength between 320 and 340 nm) and long UV-A filters (absorbing rays at a wavelength between 340 and 400 nm). - By "UV-B filter" we mean a chromophore derived from a compound that filters (or absorbs) UV-B ultraviolet rays at a wavelength between 280 and 320 nm. Furthermore, unless otherwise specified, the limits defining the extent of a range of values ​​are included within that range of values. a) The PHA copolymer(s)

[0025] The composition according to the invention Cl comprises as a first ingredient a) one or more PHA polymer(s) which contain several different repeating polymeric units (A) as defined above.

[0026] By "co-polymer" it is understood that said polymer is obtained from the polycondensation of different repeating polymer units, for example when said polymer is obtained from the polycondensation of repeating polymer units (A) the units (A) are different from each other (more precisely the R1 groups are different from one repeating unit to another), and when said polymer is obtained from the polycondensation of repeating polymer units (A) with (B) the polymer units (A) are different from the polymer units (B) (more precisely R1 is different from R2).

[0027] Preferably, composition Cl, (preferably cosmetic) comprises a) one or more polyhydroxyalkanoate (PHA) copolymer(s) consisting of a succession of the following units (A), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0028] -[-O-CH(R1)-CH2-C(O)-]- unit (A) with R1 as defined previously.

[0029] According to a particular embodiment of the invention is a composition, preferably cosmetic, Cl as defined above and below comprising a) one or more polyhydroxyalkanoate (PHA) copolymer(s) a) which consists of a succession of units (A) as defined above in which where R1 represents a hydrocarbon chain which is saturated, linear comprising 3 to 10 carbon atoms and substituted by one or more carboxy groups -C(O)OH then said chain is interrupted by heteroatoms or groups a') to c') as defined above.

[0030] According to a particular embodiment of the invention, the composition according to the invention Cl' comprises as a first ingredient a) one or more PHA copolymer(s) which contain(s), or preferably consist of, at least two different repeating polymeric units chosen from units (A) as defined above and (B) as defined below.

[0031] Preferably the present invention is a composition Cl', preferably cosmetic, comprising a) one or more polyhydroxyalkanoate (PHA) copolymer(s) a) which contain(s), preferably consisting of, at least two different repeating polymeric units selected from the following units (A) and (B), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0032] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0033] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0034] polymeric units (A) and (B) in which: - R 1 represents a hydrocarbon chain, non-cyclic saturated or unsaturated, linear or branched, or cyclic saturated or unsaturated non-aromatic, comprising from 3 to 30 carbon atoms; preferably the hydrocarbon chain is chosen from i) (C5-C28)alkyl, linear or branched, ii) (C6-C28)alkenyl, linear or branched, iii) (C6-C28)alkynyl, linear or branched, iii) preferably the hydrocarbon chain is non-cyclic and linear; said hydrocarbon chain being: • substituted by one or more anionic (A), cationic (C+) groups and mixtures thereof; ** the group(s) A being chosen from -C(O)OH, -C(O)O, -SO3H, -S(O)2O, -OS(O)2OH, -OS(O)2O , -P(O)OH2, -P(O)O2, -P(O)2O , -P(OH)2, =P(O)-OH, -P(OH)O, =P(O)-O, =P-OH, and =P-O and mixtures thereof, the anionic parts comprise one or more cationic counterions M+ to achieve the electroneutrality of the PHA, such as i) an alkali metal, ii) an alkaline earth metal, iii) ammonium RaRbRcRdN+, iv) phosphonium RaRbRcRdP+ with R representing a hydrogen atom, a (Ci-C4)alkyl group, or (hetero)aryl(Ci-C4)alkyl such as benzyl, preferably Ra represents a hydrogen atom or a (Ci-C4)alkyl group;Rb, Rc, and Rd, whether identical or different, represent a (Ci-C4)alkyl group possibly substituted by one or more hydroxy groups, (hetero)aryl, (hetero)aryl(Ci-C4)alkyl such as benzyl, (hetero)cycloalkyl, (hetero)cycloalkyl(Ci-C4)alkyl, or else Rb and Rc, or Rc and Rd, together with the nitrogen or phosphorus atom bearing them, represent a heterocycle, saturated or unsaturated, aromatic or non-aromatic, particularly (CrC4)alkyl possibly substituted by one or more hydroxy groups, v) the cationic forms of lysine or guanidine; ;

[0035] ** the cationic group(s) C+ being chosen from among the amine groups cationizable -NRbR„ ammonium -N+RaRbRc, phosphonium -P+RaRbRc, cationizable amidine -C(=NRa)-NRbRc, amidinium -C(=NRa)-N+RbRcRd, cationizable guanidine -N(Ra)-C(=NRa)-NRbRc, guanidinium -N(Ra)-C(=NRa)-N+RbRcRd, or cationizable imidazolyl possibly substituted by one or more Ra radicals as defined previously, or imidazolium possibly substituted by one or more Ra radicals as defined previously, and mixtures thereof to achieve electroneutrality of PHA, with Ra, Rb, Rc and Rd as defined previously, the cationic parts comprising one or more anionic counter ions Q to ensure electroneutrality, such as a halide, a carboxylate such as acetate, the glutamate; and possibly;

[0036] ***the R1 radicals can further be substituted by one or more atoms or groups selected from: a) halogens such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) thiocarboxy, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl, k) cosmetic active; 1) RX with R representing a group selected from a) cycloalkyl such as cyclohexyl, 2) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, m) thiosulfate; X representing a') O, S, N(R'a) or Si(R'b)(R'c), b') S(O)r, or (thio)carbonyl, c') or combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; R'a representing a hydrogen atom, or a (CrC4)alkyl, or aryl(CrC4)alkyl group such as benzyl, preferably Ra representing a hydrogen atom; R'b and R'c, identical or different, represent a (CrC4)alkyl or (Ci-C4)alkoxy group, particularly a single substituent, preferably chosen from b) halogen, and j) such as epoxide and / or • possibly interrupted by one or more a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, c') or associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide, preferably ester -OC(O)- or -C(O)-O- with r being 1 or 2, Ra being as defined previously, preferably Ra representing a hydrogen atom, Rb and Rc being as defined previously; - R2 represents a hydrocarbon chain as defined previously for R1; preferably the hydrocarbon chain of the radical R2 has a number of carbons corresponding to the number of carbon atoms of the radical R1 less at least one carbon atom (in particular, only one carbon atom is subtracted when, for example, R1 is not interrupted and is substituted by a carboxy or carboxylate group), preferably corresponding to the number of carbon atoms of the radical R1 less two carbon atoms; and b) possibly water;

[0037] it being understood that: - (A) is different from (B) (i.e., R1, and is different from R2) - the radicals R 1 and R 2 can include in the same PHA groups A and C+ to which the counter ions M + and Q ' can be absent while ensuring the electroneutrality of the PHA;

[0038] According to a particular embodiment, R 1 represents a saturated, linear or branched hydrocarbon chain, optionally interrupted by S or -OC(O)- or -C(O)-O-, more preferably S, and substituted by one or more ionic (A) or cationic (C+) groups as defined above and mixtures thereof; preferably a (C5-C2o)alkyl chain substituted by an ionic (A) or cationic (C+) group as defined above and optionally interrupted by S or O or -OC(O)- or -C(O)-O-, more preferably S, and mixtures thereof. According to a particular embodiment, R 2 represents a saturated, unsubstituted, uninterrupted, linear or branched hydrocarbon chain, preferably linear, preferably (C5-C2o)alkyl.

[0039] According to a particular embodiment, the molar percentage in units (A) is less than the molar percentage in units (B).

[0040] By "co-polymer" it is understood that said polymer is formed by the polycondensation of different repeating polymer units, for example when when said polymer is obtained from the polycondensation of repeating polymeric units (A) the units (A) are different from each other (more precisely the R1 group is different from one repeating unit to another), and when said polymer is obtained from the polycondensation of repeating polymeric units (A) with (B) the polymeric units (A) are different from the polymeric units (B) (more precisely R1 is different from R2).

[0041] According to a particular embodiment of the invention, the PHA copolymer(s) consists of two different repeating polymeric units chosen from units (A) and (B) as defined above:

[0042] More particularly, the PHA copolymer(s) according to the invention comprise the formula repetition motif (I), as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0043] [Chem. 1]:

[0044]

[0045] Formula (I) wherein: • R1 and R2 are as defined previously; m and n are integers greater than or equal to 1; preferably the sum n + m is between 450 and 1400 inclusive, preferably m < n

[0046] According to a particular embodiment, the PHA copolymer(s) of composition a) contain three different repeating polymer units (A), (B) and (C), preferably consisting of the following 3 different polymer units (A), (B) and (C), as well as their optical isomers, geometric isomers and their solvates such as hydrates:

[0047] -[-O-CH(R1)-CH2-C(O)-]- unit (A)

[0048] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0049] -[-O-CH(R3)-CH2-C(O)-]- unit (C)

[0050] polymeric units (A), (B) and (C) in which: - R and R2 are as defined previously; - R 3 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated or unsaturated, comprising from 1 to 30 carbon atoms; - Optionally substituted by one or more groups selected from A and C+ as defined above and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular represents a hydrocarbon group selected from (Ci-C28)alkyl, linear or branched, substituted by A and / or C+ as defined above, preferably the hydrocarbon group having a number of carbon atoms corresponding to the number of carbon atoms of the radical R1 minus at least three carbon atoms, preferably corresponding to the number of carbon atoms of the radical R1 minus four carbon atoms; and it being understood that: - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and - preferably the molar percentage in unit (A) is less than the molar percentage in unit (B) and the molar percentage in unit (C) especially if R2 represents an alkyl group and / or R3 represent an alkyl group; preferably R3 represents an alkyl group with a number of carbons corresponding to the number of carbons in R2 less 2 carbon atoms.

[0051] According to a particular embodiment R3 represents a hydrocarbon chain, linear or branched, preferably linear, saturated, unsubstituted, unbroken, preferably (C5-C2o)alkyl and more preferably with a number of carbons reduced by 2 units compared to the number of carbon atoms of R2.

[0052] According to another particular embodiment R3 represents a hydrocarbon chain, linear or branched, preferably linear, saturated, said chain being substituted by one or more groups chosen from A and C+ as defined above and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1 and more preferably with a number of carbons reduced by 2 units compared to the number of carbon atoms of R1.

[0053] According to a particular embodiment of the invention, the PHA copolymer(s) comprise the formula repetition motif (II), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0054] [Chem. 2]:

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] Formula (II) in which: • R1, R2 and R3 are as defined previously; • m, n and p are integers greater than or equal to 1, preferably the sum n + m + p is between 450 and 1400 inclusive; and • preferably m < n + p, preferably R 3 represents an alkyl group with a number of carbons corresponding to the number of carbons in R 2 minus 2 carbon atoms. According to a particular embodiment, the PHA copolymer(s) of composition a) contain four different repeating polymer units (A), (B), (C), and (D), preferably consisting of the following four different polymer units (A), (B), (C), and (D), as well as their optical and geometric isomers and their organic or mineral acid or base salts, and their solvates such as hydrates: -[-O-CH(R*)-CH2-C(O)-]- unit (A) -[-O-CH(R2)-CH2-C(O)-]- unit (B) -[-O-CH(R3)-CH2-C(O)-]- unit (C) -[-O-CH(R4)-CH2-C(O)-]- unit (D) polymeric units (A), (B), (C) and (D) in which: R1, R2 and R3 are as defined previously; - R4 represents a saturated hydrocarbon group, cyclic or non-cyclic, linear or branched, comprising from 3 to 30 carbon atoms, optionally substituted by one or more groups selected from A and C+ as defined above and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular, represents a hydrocarbon group selected from (C4-C28)alkyl, linear or branched, optionally substituted by one or more groups selected from A and C+ as defined above and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; and it being understood that: - (A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), and (C) is different from (A), (B) and (D); and (D) is different from (A), (B) and (C); and - preferably the molar percentage in units (A) is less than the molar percentage in units (B), preferably R 3 represents an alkyl group with a number of carbons corresponding to the number of carbons in R2 less 2 carbon atoms, and R 4 represents an alkyl group possibly substituted and / or interrupted, alkenyl possibly substituted and / or interrupted or alkynyl possibly substituted and / or interrupted with a number of carbons corresponding to the number of carbons in R1 less 2 carbon atoms.

[0063] According to a particular embodiment R4 represents a hydrocarbon chain, linear or branched, preferably linear, saturated, unsubstituted, unbroken, preferably (C5-C2o)alkyl and more preferably with a number of carbons reduced by 4 units compared to the number of carbon atoms of R2.

[0064] According to a particular embodiment of the invention, the PHA copolymer(s) comprise the formula repeating motif (III), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0065] [Chem. 3]:

[0066]

[0067] Formula (III) wherein: • R \ R 2, R ', and R 4 are as defined previously; • m, n, p, and v are integers greater than or equal to 1; preferably, the sum n + m + p + v is between 450 and 1400 inclusive; and - preferably n > m + v; more preferably n + p > m + v - preferably R3 represents an alkyl group with a number of carbons corresponding to the number of carbons in R2 minus 2 carbon atoms, and R4 represents an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 or an alkynyl group substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 and / or possibly interrupted with a number of carbons corresponding to the number of carbons in R1 minus 2 carbon atoms.

[0068] According to one embodiment more particularly, the PHA copolymer(s) of composition a) contain five different repeating polymer units (A), (B), (C), (D), and (E) preferably consists of the following 5 different polymer units (A), (B), (C), (D), and (E), as well as their optical and geometric isomers and their organic or mineral acid or base salts, as well as their solvates such as hydrates:

[0069] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0070] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0071] -[-O-CH(R3)-CH2-C(O)-]- unit (C)

[0072] -[-O-CH(R4)-CH2-C(O)-]- unit (D)

[0073] -[-O-CH(R5)-CH2-C(O)-]- unit (E)

[0074] polymeric units (A), (B), (C), (D) and (E) in which: R1, R2, R3 and R4' are as defined previously; and - R 5 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated comprising from 3 to 30 carbon atoms, possibly substituted by one or more groups selected from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular represents a hydrocarbon group selected from (C4-C28)alkyl, linear or branched, possibly substituted by one or more groups selected from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1;preferably the hydrocarbon group has a number of carbon atoms corresponding to the number of carbon atoms of the R4 radical minus at least one carbon atom, preferably corresponding to the number of carbon atoms of the R4 radical minus at least two carbon atoms, preferably minus two carbon atoms; it being understood that: ; - (A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E), and (C) is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E) is different from (A), (B), (C) and (D); and - preferably the molar percentage in units (A) is less than the molar percentage in units (B), and is less than the molar percentage in units (C), in particular if R 2 represents an uninterrupted unsubstituted alkyl group and / or R 3 represents an alkyl group, and R 4 and R 5 represent an alkyl group possibly substituted by one or more groups chosen from A and C+ as defined above and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 ,alkenyl possibly substituted by one or more groups chosen from A and C+ as defined above and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 or alkynyl possibly substituted by one or more groups chosen from A and C+ as defined above and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1; preferably R3 represents an alkyl group with a number of carbons corresponding to the number of carbons in R2 minus 2 carbon atoms,and R 4 represents an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 or an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 with a number of carbons corresponding to the number of carbons in R1 minus 2 carbon atoms,and R 5 represents an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 or an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 with a number of carbons corresponding to the number of carbons in R1 minus 4 carbon atoms.

[0075] According to a particular embodiment R5 represents a hydrocarbon chain, linear or branched, preferably linear, saturated, unsubstituted, unbroken, preferably (C5-C2o)alkyl and more preferably with a number of carbons reduced by 6 units compared to the number of carbon atoms of R2.

[0076] According to a particular embodiment of the invention, the PHA copolymer(s) comprise the formula repetition motif (IV), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0077] [Chem. 4]:

[0078] (IV)

[0079] Formula (IV) wherein: • R \ R 2, R 3, R 41 and R 5 are as defined previously; • m, n, p, v and z are integers greater than or equal to 1, preferably the the sum n + m + p + v + z is inclusively between 450 and 1400; and - preferably when R 1 represents an alkyl group substituted by one or more groups chosen from A and C+ as defined above and possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1; alkenyl substituted by one or more groups chosen from A and C+ as defined above and possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1; or alkynyl substituted by one or more groups chosen from A and C+ as defined above and possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1, R2 and R3 represent an alkyl group and groups R4 and R5 represent an alkyl group possibly substituted by one or more groups chosen from A and C+ as defined above and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1;alkenyl possibly substituted by one or more groups chosen from A and C+ as defined above and possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1; or alkynyl possibly substituted by one or more groups chosen from A and C+ as defined above and possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1, then n > m + v + z; more preferably n+p>m+v+ z; preferably R3 represents an alkyl group with a number of carbons; corresponding to the number of carbon atoms in R2 minus 2 carbon atoms, and R4 represents an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 or an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 with a number of carbon atoms corresponding to the number of carbon atoms in R1 minus 2 carbon atoms,and R 5 represents an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 or an alkynyl group possibly substituted by one or more groups chosen from A and C+ as defined previously and / or possibly interrupted by one or more heteroatoms or groups a') to c') as defined for R1 with a number of carbons corresponding to the number of carbons in R1 minus 4 carbon atoms.

[0080] According to one embodiment, the hydrocarbon chain of the radical R1 of the invention is 1) either substituted by one or more groups chosen from A and C+ as defined above, preferably substituted by one or more A groups, and is uninterrupted, 2) or substituted by one or more groups chosen from A and C+ as defined above, preferably substituted by one or more A groups and interrupted by one or more heteroatoms or groups a') to c') as defined for R1, preferably heteroatoms such as O, or S, preferably S. More particularly, option 2) is preferred.

[0081] According to another embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a hydrocarbon chain, in particular an alkyl group as defined above, substituted by one or more (preferably one) group(s) chosen from A and C+ as defined above, preferably by a group A.

[0082] According to a particular embodiment of the invention, the PHA copolymer(s) are such that R1 represents a hydrocarbon chain, in particular i) (C5-C28)alkyl, linear or branched, which is substituted by one or more (preferably one) groups A selected from -C(O)-OH, -C(O)O, -SO3H, -S(O)2O, -OS(O)2OH, -OS(O)2O, -P(O)OH2, -P(O)O2, -P(O)2O, -P(OH)2, =P(O)-OH, -P(OH)O, =P(O)-O, =P-OH, and =P-0 and their mixtures, more preferentially chosen from -C(O)-OH, -C(O)0, -SO3H, -S(O)20, and -P(O)OH2, -P(O)O2.

[0083] According to a preferred embodiment A is chosen from the following groups carboxylate -C(O)O, sulfonate -S(O)2O, and phosphonate -P(O)O2 the anionic parts comprising one or more cationic counter ions M+ to achieve the electroneutrality of the PHA, as defined above in particular an alkali metal, an alkaline earth metal, ammonium: RaRbRcRdN+, or phosphonium: RaRbRcRdP+, preferably ammonium, with Ra, Rb, Rc and Rd as defined above, preferably Ra represents a hydrogen atom; Rb, and Rc, identical or different, preferably identical, represent a (Ci-C4)alkyl group, linear or branched, preferably branched such as isopropyl or isobutyl, more preferably isopropyl; and Rd represents a (Ci-C4)alkyl group, linear or branched such as ethyl, more particularly M+ represents a diisopropylethylammonium group: (i-Pr)2N+(H)Et.

[0084] More preferably A is a carboxylate group -C(O)O M+ with M+ as defined above.

[0085] According to another particular embodiment of the invention A represents a group selected from -C(O)-OH, -C(O)O M+ with M+ as defined above.

[0086] According to a particular embodiment of the invention, said substituted hydrocarbon chain, in particular alkyl, is linear.

[0087] According to another particular embodiment of the invention, said substituted hydrocarbon chain, in particular alkyl, is branched.

[0088] According to another particular embodiment of the invention, the hydrocarbon chain of the radical R 1 of the invention is substituted and interrupted.

[0089] According to a particular embodiment of the invention, the hydrocarbon chain (in particular an alkyl group as defined above) of the radical R 1 of the invention is: - replaced by one or more (preferably one) groups A as defined above; and - interrupted by one or more (preferably one) atoms or groups chosen from O, S, N(Ra), carbonyl, or their associations such as ester, amide, urea, with R a being as defined previously, preferably Ra represents a hydrogen atom; preferably interrupted by one or more atoms chosen from O, S, more preferably by an O atom, or S especially S. Particularly the radical R 1 represents an interrupted hydrocarbon chain, especially alkyl, is in C7-C20, more particularly in C8-Ci8, even more particularly in C9-Ci6.

[0090] According to one embodiment of the invention, the composition Cl or Cl' comprises a) one or more PHA copolymer(s) a) in which R 1 is substituted at the end of the chain on the opposite side of the carbon atom bearing said radical R1 by one or more anionic (A ), cationic (C+) groups, preferably a single anionic or cationic group.

[0091] According to a particular embodiment of the invention, the PHA copolymer(s) are such that R1 represents a (C3-C28)alkyl group substituted by one or more, preferably only 1 group, at the end of the chain (i.e. on the opposite side of the point of attachment of said alkyl group to the carbon atom of the -CH- of unit (A)), said group(s) being chosen from -C(O)O M+ with M+ as defined above and interrupted by a sulfur atom, preferably in beta of -C(O)O M+.

[0092] According to one embodiment of the invention, said hydrocarbon chain R1 has the following formula: -(CH2)rX-(ALK)uG with X being as defined above, in particular representing O, S, N(Ra), preferably S, ALK represents a (Cr Cio)alkylene chain, linear or branched, preferably branched, more particularly (Cr C8)alkylene, r represents an integer between 6 and 11 inclusive, preferably between 7 and 10 such that 8; u is 0 or 1; and G represents a group A or C+ as defined above, preferably A as defined above, in particular -C(O)O M+ with M+ as defined above.

[0093] In particular the PHA copolymer(s) are such that R 2 is selected from (Cr C28)alkyl, linear or branched, and (C2-C28)alkenyl linear or branched, in particular a linear hydrocarbon group, more particularly (C3-C20)alkyl or (C3-C20)alkenyl.

[0094] According to one embodiment, the hydrocarbon group has a number of carbon atoms corresponding to the number of carbon atoms of the radical R1 less at least one carbon atom, preferably corresponding to the number of carbon atoms of the radical R1 less two carbon atoms;

[0095] According to one embodiment of the invention, the PHA copolymer(s) are such that the radical R 2 is a (CrC8)alkyl group, linear or branched, preferably linear, particularly in (C2-C6)alkyl, preferably in (C4-C6)alkyl such as n-pentyl or n-hexyl.

[0096] According to another embodiment of the composition according to the invention, the PHA copolymer(s) of the invention comprise units (A) having an alkyl radical R1 as defined above, units (B) as defined above, and units (C) having a linear or branched (C6-C20)alkenyl radical, particularly (C7-Ci4)alkenyl, more particularly (C8-Ci0)alkenyl, preferably linear and comprising a single unsaturation at the end of the chain, in particular -[CR4(R5)]q- C(R6)=C(R7)-R8 with R4, R5, R6, R7 and R8, identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, preferably a hydrogen atom and q represents an integer between 2 and 20 inclusive, preferably between 3 and 10, more preferably between 4 and 8 such that 6, such that -[CH2]q-CH=CH2 and q represents an integer between 3 and 8 inclusive, preferably between 4 and 6, such that 5.

[0097] According to one embodiment of the composition according to the invention, the PHA copolymer(s) comprise units (A) having an alkyl radical R 1 comprising between 8 and 16 carbon atoms substituted by one or more (preferably one) groups selected from A or C+ as defined above, preferably A as defined above.

[0098] According to one embodiment of the composition according to the invention, the copolymer(s) comprise units (B) having a linear or branched R2(CrC8)alkyl radical, preferably linear, particularly (C2-C6)alkyl, preferably (C4-C5)alkyl such as pentyl.

[0099] According to another embodiment of the composition according to the invention, the PHA copolymer(s) comprise units (A) having an alkyl radical R 1 as defined above, units (B) as defined above and (C) having a linear or branched (C6-C20)alkenyl radical, particularly (C7-Ci4)alkenyl, more particularly (C8-Ci0)alkenyl, preferably linear and comprising a single unsaturation at the end of the chain such as -[CH2]P-CH=CH2 and p represents an integer inclusively between 3 and 8, preferably between 4 and 6, such as 5.

[0100] According to a particular embodiment of the invention in the PHA copolymer(s), unit (A) comprises a hydrocarbon chain R1 which is an alkyl group substituted by A or C+ as defined above and interrupted in particular by a heteroatom such as S, or an alkenyl group substituted by A or C+ as defined above and interrupted in particular by a heteroatom such as S, or an alkynyl group substituted by A or C+ as defined above and interrupted by a heteroatom such as S, as defined above, said unit (A) is present in a molar percentage from 0.1 to 80%, more preferably a molar percentage from 0.5 to 70%, even more preferably a molar percentage from 1 to 50%, even better a molar percentage from 2 to 40%, a molar percentage from 20 to 40%.

[0101] Preferably where R1 of unit (A) is an alkyl hydrocarbon chain substituted by A or C+ as defined above and interrupted in particular by a heteroatom such as S, an alkenyl chain substituted by A or C+ as defined previously and interrupted in particular by a heteroatom such as S, or alkynyl substituted by A or C+ as defined previously and interrupted in particular by a heteroatom such as S said unit (A) is present in a molar percentage greater than or equal to 10%, more particularly greater than 20%, preferably between 25 and 35%.

[0102] According to another particular embodiment, R1 is substituted by one or more C+ groups, in particular selected from among the cationizable amine groups -NRbRc, ammonium -N+RaRbRc, cationizable amidine -C(=NRa)-NRbRc, amidinium -C(=NRa)-N+RbRcRd, cationizable guanidine -N(Ra)-C(=NRa)-NRbRc, guanidinium -N(Ra)-C(=NRa)-N+RbRcRd, or cationizable imidazolyl, optionally substituted by one or more Ra radicals as defined above, or imidazolium, optionally substituted by one or more Ra radicals as defined above, and mixtures thereof to achieve the electroneutrality of the PHA, with Ra, Rb, Rc, Rd as defined above, the cationic parts comprising one or more anionic counter-ions Q such as a halide .

[0103] According to a more particular embodiment of the invention in the PHA copolymer(s), unit (A) is present in a molar percentage from 0.1% to 99%, preferably in a molar percentage from 0.5% to 80%, more preferably in a molar percentage from 1% to 70%, even more preferably in a molar percentage from 2% to 60%, better in a molar percentage from 5% to 50%; even better in a molar percentage from 10% to 40% and even more preferably in a molar percentage from 25% to 35% in moles of unit (A); unit (B) is present in a molar percentage from 1% to 99.9%; preferably in a molar percentage from 2% to 99.5%, more preferably in a molar percentage from 5% to 90% in moles of unit (B);and / or the unit (C) is present in a molar percentage ranging from 0.5% to 30%, preferably a molar percentage of 1% to 20%, more preferably from 2% to 10% by mole of unit (C).

[0104] According to a more particular embodiment of the invention in the PHA copolymer(s), unit (A) is present in a molar percentage from 0.1% to 80%, more preferably from 0.5% to 70%, even more preferably from 1% to 60%, even more preferably from 5% to 50%, or from 10% to 40%; unit (B) is present in a molar percentage from 30% to 99.5%, preferably from 40% to 95%; and unit (C) is present in a molar percentage from 0% to 30%, preferably from 1% to 25%, more preferably from 5% to 20%. Relative to the whole, unit (D) is present in a molar percentage ranging from 0% to 10%, preferably between 0.1% and 5%, more preferably between 0.5% and 2% relative to the whole and the unit (E) 0% to 10%, preferably between 0.1% and 5%, more preferably between 0.5% and 2% relative to the whole of the units. Advantageously, the PHA copolymer(s) of the invention comprise from 60% to 80% by mole of unit (B);

[0105] The molar percentage values ​​of units (A), (B) and (C) of the PHA copolymer(s) are calculated with respect to the total number of moles of (A) + (B) if the copolymer(s) do not include an additional unit (C), otherwise if the copolymer(s) of the invention contain 3 different units (A), (B) and (C) then the molar percentage is calculated with respect to the total number of moles (A) + (B) + (C); otherwise if the copolymer(s) of the invention contain 4 different units (A), (B), (C) and (D) then the molar percentage is calculated with respect to the total number of moles (A) + (B) + (C) + (D); otherwise if the copolymer(s) of the invention contain 4 different units (A), (B), (C), (D) and (E) then the molar percentage is calculated with respect to the total number of moles (A) + (B) + (C) + (D) + (E).

[0106] According to a preferred embodiment of the invention, the PHA copolymer(s) comprise the following repeating units (A) and (B) together with their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0107] [Chem. 5]:

[0108] (1A) -(CHgh-S-ALKi-C(O)-OH -AKU (2A) -(CH^-S-ALKi-(A) -ÂLK2 (3A) -(CH2)pS-ALKt-(Ç*) -AL K:

[0109]

[0110] [YES]

[0112] p is an integer between 3 and 15 ALKi designates a linear or branched C1-C15 hydrogen divalent radical ALK2 denotes a C3-C2o alkyl radical C+ and A are as defined previously.

[0113]

[0114]

[0115] Preferably, the PHA copolymer(s) of the invention comprise the following repeating units, as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: [Chem. 6]: IIIIIIIIIBIII H) -(CHsH-S-ÇH (CHs>C(O)-OH n-hexyl (2) -(CH2>-S-CH(ÇH2)-0(0)-0S M* n-hexyl

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] m and n are as defined previously; M+ is a cationic counter ion as defined previously; In particular, the stereochemistry of carbon atoms bearing the radicals R1, and R2 is the same configuration (R) or (S), preferably configuration (R). More specifically, the stereochemistry of the carbon atoms bearing the radicals R1, R2 and R3 is the same configuration (R) or (S), preferably configuration (R). More specifically the stereochemistry of the carbon atoms bearing the radicals R1, R2, R3, and R4 is even configuration (R) or (S), preferably configuration (R). More specifically, the stereochemistry of the carbon atoms bearing the radicals R1, R2, R3, R4, and R5 is the same configuration (R) or (S), preferably of configuration [Chem. 7]: |||||||||||||||||| llllllllll (T) -(GH2>-S-GH(CHs)-C(O)-OH g-hexyi n Bu (23 -(CH2)®-S-CH(GH2)-C(0)-0, M* p-hexyï n-Bu

[0124] [Chem.8] IIIBIII! lllllllllll (H -[CH;>-S-CH(CH3>C(O)-GH n-hexyl d-Bü Et (2”) -(CH2>S-CH (CHsJ-CiÔyO-, M* 0-hexyl n-8u Et The PHA copolymer(s) of the invention preferably have a number average molecular weight ranging from 50,000 to 500,000, more preferably from 50,000 to 150,000.

[0125] Molecular weight can be measured, in particular, by size exclusion chromatography. A method is described below in the examples.

[0126] The PHA copolymer(s) are particularly present in the composition according to the invention Cl or Cl' in a content ranging from 0.1 to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.1 to 25% by weight.

[0127] The PHA copolymer(s) preferably have a number average molecular weight ranging from 50,000 to 500,000, more preferably from 50,000 to 150,000.

[0128] Molecular weight can be measured, in particular, by size exclusion chromatography. One method is described below in the examples.

[0129] The copolymer can be present in the composition according to the invention Cl or Cl' in a content ranging from 0.1 to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.1 to 25% by weight.

[0130] Method of preparing the PHA copolymer(s):

[0131] The methods for preparing the PHA copolymer(s) of the invention are known to those skilled in the art. In particular, the use of microbial strains producing "functionalizable" PHA may be mentioned.

[0132] By "functionalizable" is meant that the PHA copolymer(s) comprises a hydrocarbon chain including one or more atoms or groups capable of reacting chemically with another reagent—also called "reactive atoms or reactive groups"—to lead to a covalent bond functionalized by said reagent. The reagent is, for example, a compound comprising at least one nucleophilic group, and said functionalized hydrocarbon chain includes at least one electrophilic or leaving group, the nucleophilic group(s) reacting with the electrophilic group(s) to covalently graft the reagent. The nucleophilic reagent can also react with one or more unsaturations of the alkylenyl group(s), leading to covalent grafting of the hydrocarbon chain functionalized by said reagent. The addition reaction can also be radical, a Markovnikov or anti-Markovnikov type addition, or a nucleophilic or electrophilic substitution. Addition or condensation reactions can be carried out radically or non-radically, with or without catalysts, enzymes or not, preferably at temperatures of 100°C or less, under pressures above 1 atm, in an inert atmosphere, or in the presence of oxygen.

[0133] By "nucleophile" we mean any atom or group that is electron-donating by inductive effect +1 and / or mesomeric +M. Examples of electron-donating groups include hydroxy, thiol, amino groups.

[0134] By "electrophile" we mean any atom or group which is electron-withdrawing by inductive effect -I and / or by mesomeric effect -M. Examples of electron-withdrawing atoms include.

[0135] The microorganisms producing PHAs of the invention, particularly those with a C3-C5 hydrocarbon chain, can be naturally produced by the bacterial kingdom, such as cyanobacteria of the order Nostocales (e.g., Nostoc muscorum, Synechocystis, and Synechococcus), but primarily by Proteobacteria, for example, in the class of:

[0136] -beta-Proteobacteria, of the order Burkholderiales (Cupriavidus negator synonym Rasltonia eutropha)

[0137] -alpha- Proteobacteria, of the order Rhodobacteriales (Rhodobacter capsulatus marine and photosynthetic)

[0138] -gamma-Proteobacteria, of the order Pseudomonales of the family Moraxellaceae (Acinetobacter Junii)

[0139] Among the microorganisms of the Bacterial kingdom, the genera Azotobacter, Hydrogenomomas, or Chromatium are the most representative of PHA-producing organisms.

[0140] Organisms that naturally produce PHAs with hydrocarbon chains, particularly in C3-C5, include Proteobacteria, such as gamma-Proteobacteria, and more particularly those of the order Pseudomonales in the family Pseudomonas, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis, and preferably Pseudomonas putida GPo 1 and Pseudomonas putida KT2440. Preferably Pseudomonas putida and Pseudomonas putida, and in particular Pseudomonas putida GPo 1 and Pseudomonas putida KT2440.

[0141] Some organisms can also naturally produce PHAs without belonging to the order Pseudomonales, such as Commamonas testosteroni, which belongs to the class of beta-Proteobacteria of the order Burkholderiales of the family Comamonadaceae.

[0142] The PHA-producing microorganism according to the invention may also be a recombinant strain if a PHA synthase 3-oxidation metabolic pathway is present. The PHA synthase 3-oxidation 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.

[0143] La souche recombinante peut être du règne Bacteria ex : Escherichia coli ou du règne Plantae ex : Chlorella pyrenoidosa : International Journal of Biological Macromoleculess, 116, 552-562 « Influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (PHAs) by microalgae ») ou du règne Fungi ex Saccaromyces cerevisiae ou Yarrowia lipotyca : Applied Microbiology and Biotechnology 91. 1327-1340 (2011) « Engineering polyhydroxyalkanoate content and monomer composition in the oleaginous yeast Yarrowia lipolytica by modifying the B-oxidation multifunctional protein”).

[0144] Genetically modified microorganisms can also be used, which can, for example, increase PHA production and / or increase oxygen consumption capacity, decrease autolysis, and / or modify the monomer ratio. It is known that for PHAs, a large part of the total production cost is attributed to the culture medium and primarily to the substrate / carbon source. Thus, genetically modified microorganisms can be used that require fewer nutrients (carbon sources) for their growth; for example, those that are photoautotrophic by nature, i.e., using light and CO2 as their primary energy source.

[0145] The copolymer can be obtained in a known manner by biosynthesis, for example with microorganisms belonging to the genus Pseudomonas, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida; and with a carbon source which can be a carboxylic acid in C2-C2o, preferably in C6-Ci8, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; a saccharide such as fructose, maltose, lactose, xylose, arabinose, etc.); an n-alkane such as hexane, octane, dodecane; an n-alcohol such as methanol, ethanol, octanol, glycerol; methane, carbon dioxide.

[0146] Biosynthesis can optionally be carried out in the presence of an inhibitor of the [3-oxidation pathway such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2- butynoic acid, 2-octynoic acid, phenylpropionic acid, and preferably acrylic acid.

[0147] According to one embodiment, the process for preparing PHAs of the invention uses microbial cells producing PHAs by genetically modified microorganisms (GMOs). The genetic modification can increase PHA production, increase oxygen uptake capacity, increase resistance to solvent toxicity, decrease autolysis, modify the PHA comonomer ratio, and / or any combination thereof. In some of these embodiments, modifying the comonomer ratio by unit (A) increases the amount of the predominant monomer vs. (B) of the PHA of the invention obtained. In another embodiment, the PHA-producing microbial cells reproduce naturally.

[0148] As an example of genetically modified microbial strains producing PHA, Pseudomonas entomophila LAC23 (Adv. Healthcare Mater. 2017, 1601017 (DOI: 10.1002 / adhm.201601017.)

[0149] By way of example, a genetically modified microbial strain producing functionalizable PHA or comprising a reactive group, Pseudomonas entomophila LAC23 (Biomacromolecules. 2014 Jun 9;15(6):2310-9. doi: 10.1021 / bm500669s)

[0150] It is also possible to use wild strains that produce 100% PHO (according to publication dx.doi.org / 10.1021 / bm2001999 I Biomacromolecules 2011, 12, 2126-2136)

[0151] It is also possible to use genetically modified microorganisms producing phenylvaleric co 3-Hydroxydodecanoic HDD copolymers (Sci China Life Sci, Shen R, et al., 57 No. 1, (2014) with a strain: Pseudomonas entomophila LAC23.

[0152] Nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium, iron can also be used for biosynthesis.

[0153] Appropriate known conditions of temperature, pH, dissolved oxygen (DO) can be used for the culture of microorganisms.

[0154] Microorganisms can be cultured by any known culture method, such as in a bioreactor in continuous, batch, fed or unfed mode.

[0155] The biosynthesis of the polymers used according to the invention is described in particular in the article "Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer", Xun Juan et al; Biomacromolecules 2012, 13, 2926-2932 and in application WO2011 / 069244.

[0156] Microbial strains producing functionalizable PHA or comprising a reactive group as defined above are for example of the genus Pseudomonas such as P. cichorii YN2, P. citronellolis, P. jessenii, and more generally by the species of Pseudomonas putida such as Pseudomonas putida GPol (synonym of Pseudomonas oleovorans), P. putida KT2442, P. putida KCTC 2407, P. putida BM01.

[0157] The carbon source(s):

[0158] One means of accessing the PHAs of the invention is to introduce one or more organic compounds into the culture medium, this or these organic compounds representing a source of carbon preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and their mixture.

[0159] In one embodiment, the organic compound(s) will preferably be chosen from alcohols, carboxylic acids and their mixture.

[0160] The carbon source(s) can be classified as follows: 1. Carbon source provided by one or more organic compounds introduced into the environment:# 2. According to a particular embodiment of the invention, the organic compound(s) are selected from alcohols, in particular (C5-C2o)alkanols, and / or carboxylic acids, in particular (C5-C2o)alkanoic acids possibly substituted and / or interrupted, in particular (C5-C20)alkanoic acids such as (C7-Cn)alkanoic acids like nonanoic acid or pelargonic acid and / or (C5-C20)alkenoic acids, in particular (C5-C20)alkenoic acids such as (C7-Cn)alkenoic acids like undecylenic acid, and mixtures thereof.

[0161] The carbon source(s) can be classified into 3 groups: - Group A, the organic compound can aid in the growth of the producing strain and aids in the production of PHA structurally linked to the organic compound. - group B, the organic compound may help the growth of the strain but does not participate in the production of PHA structurally linked to the organic compound. - group C: the organic compound does not participate in the growth of the strain.

[0162] Such microbiological processes are known to those skilled in the art, particularly in the scientific literature. Examples include: International Journal of Biological Macromolecules 28, 23-29 (2000); The Journal of Microbiology, 45, No. 2, 87-97, (2007).

[0163] According to one embodiment, the substrate, which is structurally linked to the reactive atom(s) or reactive group(s) of the PHA(s) of the invention, is introduced directly into the medium as a single carbon source in a medium suitable for microbial growth. (Example: group A for P. putida GPol: alkenoic acid, particularly terminals).

[0164] According to another embodiment, the substrate, which is structurally linked to the reactive atom(s), in particular halogen, or to the reactive group(s) of the PHA(s) of the invention, is introduced into the medium as a carbon source with a second carbon source as a co-substrate, which is also structurally linked to the PHA, in a medium suitable for microbial growth. (Example: group B for P. putida GPol: preferably terminal haloalkanoic acids such as terminal bromoalkanoic acids).

[0165] According to yet another embodiment, the substrate, which is structurally linked to the reactive atom(s), in particular halogen, or to the reactive group(s) of the PHA(s) of the invention, can be introduced directly into the medium as a carbon source with a second carbon source in co-substrate which is also structurally linked to the PHA(s) and a third carbon source in co-substrate which is not structurally linked to the PHA(s) in a medium suitable for microbial growth. (Example: C group glucose or sucrose).

[0166] In one embodiment, the beta-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.

[0167] In one embodiment of the first aspect, the functionalized fatty acid is 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.

[0168] The functionalization can be introduced by an organic compound chosen from the precursors of the alcohol and / or carboxylic acid category, in particular: - for functionalization of the PHA(s) with a branched or branched alkyl group: see e.g. Applied and Environmental Microbiology, 60. No.9, 3245-325 (1994); - for functionalization of the PHA(s) with a linear alkyl group including a terminal cyclohexyl motif: see e.g. doi.org / 10.1016 / S0141-8130(01)00144-1; - for functionalization of the PHA(s) with a preferably terminal unsaturated alkyl group see e.g. doi.org / 10.1021 / bm8005616); - for a functionalization of the PHA(s) with a linear alkyl group including a halogen preferably at the end of the hydrocarbon chain (doi.org / 10.1021 / ma00033a002); - for functionalization of the PHA(s) with an alkyl (hetero)aromatic group for example phenyl, benzoyl, phenoxy, see for example J.Microbiol. Biotechnol, 11. 3,435-442 (2001); - for functionalization of the PHA(s) with a linear alkyl group including a heteroatom, particularly at the end of the hydrocarbon chain, see e.g. DOI 10.1007 / s00253-011-3099-4; - for functionalization of the PHA(s) with a linear alkyl group including a cyano function, particularly at the end of the hydrocarbon chain, see e.g. .org / 10.1111 / j.l574-6968.1992.tb05839.x; - for functionalization of the PHA(s) with a linear alkyl group including an epoxy function, particularly at the hydrocarbon chain termination, see e.g. doi.org / 10.1016 / S1381-5148(97)00024-2;

[0169] The journal International Microbiology 16:1-15 (2013) doi:10.2436 / 20.1501.01.175) also mentions the majority of functionalized native PHAs.

[0170] In a particular embodiment of the invention, the group A fatty acid is selected from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenyl valeric acid, citronellol, and 5-cyanopentanoic acid, preferably 11-undecenoic acid.

[0171] In a particular embodiment of the invention, the group B fatty acid is selected from halogenooctanoic acids such as 8-bromooctanoic acid, and 11-bromoundecanoic acid.

[0172] In a particular embodiment of the invention, the carbon source of group C is a monosaccharide, preferably glucose. 1. Carbon source in the presence of an oxidation inhibitor introduced into the medium:#

[0173] Another aspect of the invention is the use of PHA-producing microbial strains in a suitable medium for microbial growth, said medium comprising: a substrate that is structurally bound to the PHA(s); at least one carbon source that is not structurally bound to the PHA(s); and at least one inhibitor of the oxidation pathway, in particular beta-oxidation. This allows the growth of microbial cells to occur in said medium, the microbial cells synthesizing the PHA polymer(s) of the invention; preferably a copolymer having particularly more than 95% identical units, which has a comonomer ratio of unit(s) (A) to unit(s) (B) that differs from that obtained in the absence of the beta-oxidation pathway inhibitor.

[0174] Example of functionalization of PHA copolymers according to the invention from PHA copolymer with unsaturated hydrocarbon chain according to scheme 1, in which compound (b) is prepared from PHA copolymer with unsaturated hydrocarbon chain (a) which undergoes an addition of a nucleophilic reagent YH, this reaction being able to be carried out by radical or thermal means, preferably radical, in particular in the presence of UV irradiation possibly in the presence of radical initiators or (photo)initiators such as 2-Hydroxy-2-MethylPropiophenone, this reaction can be carried out in a polar solvent (a) such as acetone, preferably under stirring at room temperature (25 °C) for at least 5 minutes, the molar amount of (b) vs. (a) is between 1 and 10 (molar excess of (b) > (a)), preferably between 2 and 8, more preferably between 3 and 7, such that 6;

[0175] [Chem. 9]: Diagram 1 in which: R2, m, and n are as defined previously; - Y represents a group chosen from -X-(ALK)PA, M+ -X-(ALK)P-C+, Q with p being 0 or 1; preferably 1, ALK is as defined previously, preferably represents a (Ci-C4)alkylene group such as methylene, or ethylene (1,1-ethylene), X being as defined previously, preferably X = S, A and C+ being as defined previously, M+ being a cationic counter ion as defined previously, and Q being an anionic counter ion as defined previously; - q' represents an integer between 2 and 20 inclusively, preferably between 3 and 10, more preferably between 4 and 8 such that 6, better between 3 and 8, preferably between 4 and 6, such that 5. - According to a preferred embodiment of the invention, the process for preparing PHA compounds with an R1 group having a hydrocarbon chain substituted by a carboxylate, with Y representing -X-(ALK)PC(O)O, M+ or -X-(ALK)pC(O)OH, with p being 0 or 1; preferably 1, ALK is as defined above, preferably representing a (CrC4)alkylene group such as methylene, or ethylene (1,1-ethylene), X being such that defined previously, preferably X = S, M+ being a cationic counter ion as defined previously; provided that if Y represents -X-(ALK)PC(O)OH, the reaction is followed by a salification reaction with an alkali agent such as an amine RbRbRcN with RbRbet Rc as defined above, preferably a tri(Ci-C4)alkylamine such as N,N-diisopropylethylamine (DIPEA), this reaction can be carried out in solution in particular in a polar solvent such as acetone, preferably at a temperature between 0 °C and 25 °C in particular between 15 and 25 °C, particularly with stirring, possibly followed by evaporation of solvent for example with a rotary evaporator.

[0177] Other addition reactions can be carried out from double or triple unsaturations such as Michael additions, Diels-Alder additions, catalytic hydrogenation (in particular with Pd, Ni) or non-catalytic hydrogenation, controlled or non-controlled oxidation, and reaction on electrophiles.

[0178] According to a particular embodiment of the invention, the PHA copolymers comprise a saturated linear or branched hydrocarbon chain R1, substituted and / or interrupted by atoms or groups as defined above for R1, comprising in total between 5 and 30 carbon atoms, preferably between 6 and 20 carbon atoms, more particularly between 7 and 11 carbons, and a hydrocarbon chain R2 representing a linear or branched (C3-C2O)alkenyl radical, particularly (C5-Ci4)alkenyl, more particularly (C7-CiO)alkenyl, preferably linear and comprising a single unsaturation at the end of the chain, in particular -[CR4(R5)]qC(R6)=C(R7)-R8, with R4, R5, R6, R7, and R8, identical or different, representing a hydrogen atom or a group (CrC4)alkyl such as methyl, preferably a hydrogen atom and q represents an integer inclusively between 2 and 20, preferably between 3 and 10, more preferably between 4 and 8 such that 6,such that -[CH2]q-CH=CH2 and q represents an integer inclusively between 3 and 8, preferably between 4 and 6, such that 5 includes between 1 and 99%, preferably between 2 and 50%, and even more preferably between 3 and 40% unsaturations, and even more particularly between 3 and 30% unsaturations, better between 5 and 20% unsaturations.

[0179] A) These unsaturations can be chemically modified by addition reactions, such as radical additions, Michael additions, electrophilic additions, Diels-Alder reactions, halogenation, hydration, hydrogenation, and preferably hydrothiolation with particles, chemical compounds, or polymers. In particular, hydrothiolation reactions can be carried out in the presence of a thermal initiator, a redox initiator, or an initiator photochemical and an organic compound bearing a sulfhydryl group, in particular selected from: - Linear, branched, cyclic or aromatic alkanethiols comprising 1 to 14 carbon atoms, such as methane-, ethane-, propane-, pentane-, cyclopentane-thiol, preferably hexane-, cyclohexane-, heptane-, octane, phenylethane-, 4-tert-butylphenylmethane-, 2-furanmethane-thiol; - Organosiloxanes carrying a thiol function, such as (3-mercaptopropyl)trimethoxysilane, (3-Mercaptopropyl)methyldimethoxysilane, 2-(Triethoxysilyl)ethanethiol, mercaptopropyl-isobutyl-POSS; - Thiolated silicone oils, in particular those described in document DOI: 10.1016 / j.actbio.2015.01.020); - Thiolated oligomers or polymers bearing a reactive function, such as an amine, an alcohol, an acid, a halogen, a thiol, an epoxide, a nitrile, an isocyanate, a heteroatom, preferably cysteine, cysteamine, N-acetylcysteamine, 2-Mercaptoethanol, l-Mercapto-2-propanol, 8-Mercapto-l-octanol, thiolactic acid, thioglycolic acid, mercapto-3-propionic acid, 11-mercaptoundecanoic acid, polyethylene glycol dithiol, 3-Mercaptopropionitrile, 1,3-Propanedithiol, 4-Cyano-l-butanethiol, 3-Chloro-l-propanethiol, l-Thio-[3-D-glucose tetraacetate; and - Thiols that can be obtained from the reduction of disulfide, such as phenyldisulfide, furfuryl disulfide. Examples of radical initiators include: tert-butyl peroxy-2-ethylhexanoate, cumin perpivalate, tert-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobis isobutyronitrile, 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-butylperoxycarbonyl)cyclohexane, 2,2-bis(tert-butylperoxy)octane, 4,4-bis(tert-butylperoxy)valerate of n-butyl, 2,2-bis(tert-butylperoxy)butane, 1,3-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-tert-butyl diperoxy isophthalate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butyl peroxy-a-methylsuccinate,di-tert-butyl peroxydimethylglutarate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate, 2,5-dimethyl-2,5-di(tertbutylperoxy)hexane, diethylene glycol bis(tert-, butylperoxycarbonate), di-tert-butyl peroxytrimethyladipate, tris(tert-butylperoxy)triazine, vinyltris(tert-butylperoxy)silane phenothiazine, tetracene, perylene, anthracene, diphenyl-9,10-anthracene, thioxanthone, benzophenone, acetophenone, xanthone, fluorenone, anthraquinone, 9,10-dimethylanthracene, 2-ethyl-9,10-dimethyloxyanthracene, 2,6-dimethylnaphthalene, 2,5-diphenyl-1-34-oxadiazole, xanthopinacol, 1,2-benzanthracene, 9-nitroanthracene. Each of these initiators can be used alone or in combination with others. - The chemical reactions mentioned above are known to those skilled in the art. The following documents can be cited in particular: Synthesis and preparation of modified PHAs with polyethylene glycol dithiol: 10.1021 / acs.biomac.9b00479; Biomacromolecules, 19. 3536-3548 (2018); - Synthesis and preparation of PHAs modified with mercaptohexanol: 10.1021 / acs.biomac.8b01257; Biomacromolecules, 20.2, 645-652 (2019); - Synthesis and preparation of modified PHAs with Hydroxy-, Cinnamic Acid-, Sulfate-, and Zosteric Acid: 10.1021 / bm049962e ^Biomacromolecules, 5, 4, 1452-1456(2004); - Radical addition of methyl methacrylate to a PHOUn: 10.1002 / 1521-3935(20010701)202:ll<2281::AID-MACP2281>3.0.CO;2-9 ; Macromolecular Chemistry and Physics, vol. 202, 11, 2281-2286 (2001); Synthesis and preparation of modified PHAs with a polysilsesquioxane (POSS): 10.1016 / j.polymer.2005.04.020; Polymer Vol. 46, 14, 5025-5031 (2005); - Grafting of thio-beta-glucose onto unsaturated side chains: 1022-1336 / 99 / 0202-0091 $17.50+.50 / 0; Macromol. Rapid Commun., 20, 91-94 (1999) B) These unsaturations can also be chemically modified by controlled or uncontrolled oxidation reactions, for example with concentrated or dilute alkali permanganates (preferably potassium permanganate), preferably concentrated, or ozonolysis, and allow the production of PHAs with terminal side chains of carboxy.

[0180] Example of functionalization of PHA copolymers according to the invention with an aliphatic chain terminated by a carboxy (c) or carboxylate (d) group from PHA copolymer with an unsaturated hydrocarbon chain (a) according to scheme 2,

[0181] which undergoes uncontrolled oxidation, particularly with concentrated or dilute alkali permanganates (preferably potassium permanganate), preferably concentrated, and / or in the presence of sodium or potassium carbonate, in water or alternatively in the presence of crown ether, preferably 18-crown-6, in a mixture of halogenated solvent and (Ci-C4)carboxylic acid such as acetic acid, or else the oxidation is carried out from osmium oxide OsO6, in the presence of polar protic solvent such as (Ci-C6)alkanol like t-BuOH and oxone, to lead to the PHA with an aliphatic chain terminated by a carboxy group (c), which can be salified for example with an alkaline agent M+OH to lead to the compound (d) of the invention;

[0182] another example of functionalization of aliphatic chain PHA copolymers according to the invention with an ammonium group (f) from an unsaturated hydrocarbon chain PHA copolymer (a) according to scheme 2, wherein (a) reacts with an amine RbRcNH to give rise to the cationizable amino group aliphatic chain PHA copolymer (e), the latter being able to then react with RaQ such as a Ra halide to give rise to the ammonium group aliphatic chain PHA (f)

[0183] [Chem. 10]:

[0184]

[0185] Scheme 2 in which:

[0186] R2, q', m, and n are such as defined above;

[0187] M+ being a cationic counter ion as defined above, and

[0188] Q being an anionic counterion as defined above and Ra, Rb, and Rc, are as defined above, particularly either a (Ci-C6)alkyl group optionally substituted by one or more hydroxyl groups, or else Rb and Rc together with the nitrogen atom bearing them form a heterocycle, mono or polycyclic, preferably monocyclic such as pyridino, morpholino, piperazino, piperidino, more preferably R' and R” represents a (hydroxy)(Cr C4)alkyl group such as hydroxyethyl.

[0189] The chemical reactions mentioned above are known to those skilled in the art. The following documents may be cited in particular:

[0190] 10.1021 / bm049337; Biomacromolecules, vol. 6, 2, 891-896 (2005); 10.1016 / S0032-3861(99)00347-X ; Polymer, vol. 41, 5, 1703-1709 (2000) ; 10.1021 / ma9714528 et 10.1016 / S1381-5148(97)00024-2 ; Macromolecules, 23, 15, 3705-3707 (1990) ; 10.1016 / S0032-3861(01)00692-9 ; Polymer, vol 43, 4, 1095-1101 (2002) ; 10.1016 / S0032-3861(99)00347-X ; Polymer, vol 41, 5, 1703-1709 (2000) ; et 10.1021 / bm025728h ; Biomacromolecules , vol 4, 2, 193-195 (2003).

[0191] Example of functionalization of PHA copolymers according to the invention from a hydrocarbon chain PHA copolymer with an epoxide group (g) according to scheme 3, in which the epoxide group PHA copolymer (g) reacts with the nucleophilic reagent YH as defined above, to give rise to the PHA according to the invention (h) with a hydrocarbon chain substituted by a hydroxy group and a Y group as defined above; the epoxide group PHA (g) can also react with an amine R'R”NH to give rise to the aliphatic chain PHA substituted by a hydroxy group and by an amino group (i) cationizable in the presence, for example, of acid HQ to give rise to the ammonium group PHA copolymer (j) or alternatively the copolymer (PHA) (i) can react with Ra-Q such as a Ra halide, preferably an alkyl halide, to give rise to the ammonium group PHA copolymer (k)

[0192] [Chem. 11]: Scheme 3 in which Y, m, n, q', and R2 are as defined in Scheme 1, or Y represents an R'R”N- group with R'R” representing a hydrogen atom or a (Ci-C6)alkyl group possibly substituted by one or more hydroxy groups, or R' and R” together with the nitrogen atom bearing them form a heterocycle, mono or polycyclic, preferably monocyclic such as pyridino, morpholino, piperazino, piperidino, more preferably R' and R” represent a (hydroxy)(Ci-C4)alkyl group such as hydroxyethyl.

[0194] The epoxide structure can be obtained by conventional methods known to those skilled in the art, whether by biotechnological processes or by chemical means such as unsaturation oxidation as previously mentioned. The epoxide group(s) can react with carboxylic acids, maleic anhydrides, amines, alcohols, thiols, and isocyanates, all of these reagents having at least one C1-C20 hydrocarbon chain, linear or branched, cyclic or acyclic, saturated or unsaturated; (di)(C1-C6)alkylamine, the alkyl group(s) being able to be substituted by one or more hydroxyl groups, such as diethanolamine or dihydroxyethanolamine. The amine groups can then be protonated or quaternized in a conventional manner.

[0195] The following documents can be cited in particular: - Preparation of PHA carrying charges from diethanolamine: 10.1021 / bm8005616, Biomacromolecules, vol 9, 8, 2091-2096 (2008); - Preparation of PHA bearing charges from sodium 3-mercapto-l-propanesulfonate: 10.1021 / acs.biomac.9b00870 Biomacromolecules, vol 20, 9, 3324-3332 (2019); - Preparation of PHA containing a native epoxide motif: 10.1016 / S1381-5148(97)00024-2); Reactive and Functional Polymers, vol 34,1, 65-77 (1997)

[0196] Example of functionalization of PHA copolymers according to the invention from a PHA copolymer with a hydrocarbon chain terminated by a leaving group NF (1) according to the following scheme 4 in which the PHA copolymer with an aliphatic chain and a leaving group (1) reacts with a nucleophilic compound YH to give rise to the PHA (m) with an aliphatic chain terminated by a group Y according to the invention:

[0197] [Chem. 12]:

[0198]

[0199] Scheme 4 in which Y, m, n, q', and R2 are as defined in Scheme 1. M corresponds to a leaving group, organic or inorganic, which can be substituted by a nucleophilic group, preferably said nucleophile being an electron-donating heteroatom by +1 and / or +M effect such as O, S, or N. Preferably, the leaving 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. For example, see the following document: 10.1016 / j.ijbiomac.2016.11.118, International Journal of Biological Macromolecules, vol. 95, 796–808 (2017).

[0200] Example of functionalization of PHA copolymers according to the invention from a hydrocarbon-chain PHA copolymer with a cyano group according to the following scheme 5 in which the aliphatic-chain PHA copolymer (p) is substituted by a cyano or nitrile group, which:

[0201] - In a first step i) the PHA side-chain copolymer with cyano group or nitrile reacts with an organoalkaline or organomagnesium compound Y-MgHal, Y-Li, or Y-Na, followed by hydrolysis to lead to the chain PHA copolymer a Y-side chain grafted with a ketone function (q) according to the invention. The ketone function can be changed to a thioketone by thionation, for example with S8 in the presence of an amine, or with Lawesson's reagent. The latter, after complete reduction ii) (for example, by Clemensen reduction), leads to the PHA copolymer with a Y-side chain grafted by an alkylene group. Alternatively, the latter can be reduced in a moderate manner iii) by a conventional reducing agent to lead to the PHA copolymer with a Y-side chain grafted by a hydroxyalkylene group. The cyano group of the starting PHA copolymer can react with water after hydration to lead to the amide derivative, and iv) after hydrolysis to the carboxy derivative (t) according to the invention. The latter can then be salified in the presence of an alkali metal M+OH to lead to the aliphatic carboxylate copolymer (u) according to the invention.The cyano group of the starting PHA copolymer can also, after reduction vi), lead to the cationizable amine derivative (v), which, after amine alkylation and / or salification reactions, leads to the aliphatic ammonium copolymer (w) according to the invention. PHA copolymers with a nitrile-functionalized side-chain hydrocarbon are prepared by conventional methods known to those skilled in the art. For example, see document: 10.1016 / 0378-1097(92)90311-B, FEMS Microbiology Letters, vol. 103, 214, 207-214 (1992).

[0202] [Chem. 13]:

[0203]

[0204] Scheme 5 in which Y, m, n, q', Y and R2, Ra, Rb, Rc, M+ and Q are as defined previously.

[0205] Example of functionalization of PHA copolymers according to the invention from PHA copolymer with a hydrocarbon chain at the end of the chain according to the following scheme 6:

[0206] [Chem. 14]:

[0207]

[0208] Scheme 6 in which R1, R2, m, n and Y are as defined previously, and R'1 represents a group chosen from -ALK-A , M+ or -ALK-C+, Q with ALK, A , C+, M+ and Q as defined previously.

[0209] These end-chain grafts are known to those skilled in the art on PHA polymers. The following documents may be cited as examples: - Preparation of PHA oligomers by thermal degradation: 10.1021 / bm0156274; Biomacromolecules, vol 3,1, 219-224 (2002); - Preparation of PHA oligomers by transesterification: 10.1021 / ma011420r, Macromolecules, vol 35, 3, 684-689 (2002); - Preparation of PHA oligomers by hydrolysis: 10.1016 / 0032-3861(94)90590-8 Polymeryol 35, 19, 4156-4162 (1994); - Preparation of PHA oligomers by methanolysis: 10.1021 / bm060981t, Biomacromolecules, vol 8, 4, 1255-1265 (2007);

[0210] Other methods known to a person skilled in the art may also be cited: - Synthesis and characterization of PHA grafted with ascorbic acid: 10.1016 / j.ijbiomac.2018.11.052; International journal of biological macromolecules, vol 123: 7 (2019); - Preparation of PHB-b-PHO copolymers by lipase-catalyzed polycondensation with divinyl adipate: 10.1021 / bm9011634, Biomacromolecules, vol 10, 12, 3176-3181 (2009); - Synthesis of PHB-b-PHO copolymers coupled by a diisocyanate junction: 10.1021 / ma012223v; Macromolecules, vol 35,13. 4946-4950 (2002); - Preparation of PHO oligomers on chitosan by condensation between the carboxylic acid end of PHO and the amine functions of chitosan: 10.1002 / app.24276; Journal of Applied Polymer Science, vol 103,1, (2006); - Transesterification of PHAs by propargyl alcohol to produce PHA oligomers modifiable by "click" chemistry: 10.1016 / j.reactfunctpolym.2011.12.005 ; Reactive and Functional Polymers, vol 72, 2,, 160-167 (2012); - Preparation of PHO-b-PCL copolymer: 10.1002 / mabi.200400104; Macromolecular Bioscience, vol 4, 11 (2004); - Preparation of PHO-b-PEG copolymer: 10.1002 / macp.201000562; Macromolecular Chemistry and Physics; vol 212, 3, (2010); - Unsaturation epoxidation at the end of the chain and acid grafting at the end of the chain: 10.14314 / polhnery.2017.317; Polimery, vol 62, 4, 317-322 (2017); - Grafting of organosiloxane motif at chain end on PHA: 10.1016 / j.reactfunctpolym.2014.09.008 ; Reactive and Functional Polymers, vol 84, 53-59 (2014).

[0211] The entire set of grafted PHA copolymers of the invention described above, according to diagram 7:

[0212]

[0213] [Chem. 15]:

[0214] Scheme 7 in which R'1, R2, m, n and Y are as defined above, and

[0215] X' represents a reactive atom or group capable of reacting with an atom or electrophilic group E or nucleophile Nu to create a convalent bond S if X' is an electrophilic or leaving group then it can react with a reagent R'1- Nu, if X' is a nucleophile Nu group then it can react with R'1- E to create a covalent bond S;

[0216] By way of example, the covalent bonds or S-bonding groups that can be generated from the condensation of electrophiles with nucleophiles are listed in the table below:

[0217] [Table 1]: Kœléophiles Liaisons c-cy •suites S Estera actives* Amines Carbcxamid es Azatores «fasses**. Amines, Carbohydrates, Aortic Cyanides, Amines, Carbohydrates, Aceryl Cyanides, Alcohols, Esters, Acyl Cyanides, Aceryl Esters, Aceryl Cyanides, Amines, Carbohydrates, Aceryl Acids, Amines, Aceryls, Hydrogens of Eyls, Carbonate Acids, Esters, Hydrogens of Ethyls, Thetes, Hydrogens, Acids, Acids, Hydrogens, Acids Theteêdters H^Bgémres d'arytes Amoebas Arylamines

[0218] It is also possible, starting from a PHA functionalized in side chain, to carry out the end-of-chain grafting in a second step as described in diagram 8. The converse is also true, where the end-of-chain grafting is feasible in the first step, then the functionalization of the functionalizable pendant side chain is carried out in a second step.

[0219] [Chem. 16]:

[0220]

[0221] Scheme 8 in which R'1, R2, m, n and Y are as defined above, and

[0222] All these chemical reactions are known to those skilled in the art. The following documents may be cited as examples: - Synthesis and preparation of thiol-ene modified PHAs, then reaction on new grafted function: 10.1021 / ma0304426; Macromolecules, vol 37, 2, 385-389(2004); - Grafting of PEG and PLA onto PHAs functionalized with acids: 10.1002 / marc.200900803 and 10.1002 / mabi.200390033; - Synthesis and preparation of modified PHAs with polyethylene glycol dithiol: 10.1021 / acs.biomac.9b00479. b) Water

[0223] The composition according to the invention Cl or Cl' preferably comprises water. The water suitable for 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.

[0224] Preferably, water represents the major ingredient by weight of the composition. According to one embodiment, the quantity by weight of water is between 20% and 99%, particularly between 30% and 95%, more preferably between 40% and 90% by weight relative to the total weight of the composition.

[0225] According to one embodiment, composition Cl or Cl' is an aqueous composition, more preferably a composition comprising less than 10% by weight of fats relative to the total weight of the composition considered, preferably less than 5%, even more preferably less than 2%, and according to a still more preferred form, is free of fats.

[0226] c) additional solvent

[0227] The composition may further comprise one or more additional solvents c) .

[0228] Preferably, the additional solvent(s) are chosen from among the solvents miscible with water.

[0229] By "water miscible solvent" according to the present invention, we mean a compound that is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25 °C and atmospheric pressure).

[0230] The additional solvents usable in composition Cl or C'1 of the invention may also be volatile. They may be polar or nonpolar, protic or aprotic, preferably polar. More particularly, protic and polar.

[0231] Among the additional solvents that may be used in composition Cl or C'1 according to the invention, mention may be made in particular of polar protic solvents such as alcohols, especially lower monoalcohols having from 2 to 6 carbon atoms such as ethanol and isopropanol,

[0232] According to one embodiment, the composition according to the invention Cl or Cl' comprises one or more additional solvents, preferably chosen from monoalcohols having 2 to 6 carbon atoms such as ethanol and isopropanol, preferably in an amount less than 70%, more preferably less than 20%, even more preferably less than 10%, more particularly less than 8% relative to the total weight of water and possibly fats d).

[0233] d) Fats

[0234] According to a particular embodiment of the invention, the composition further comprises one or more fatty substances.

[0235] The term "fatty substance" means an organic compound insoluble in water at ordinary room temperature (25°C) and atmospheric pressure (760 mm Hg) (solubility less than 5% and preferably less than 1%, or even more preferably less than 0.1%). Its structure includes at least one hydrocarbon chain comprising at least six carbon atoms or a chain of at least two siloxane groups. Furthermore, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as chloroform, ethanol, benzene, petrolatum, or decamethyl cyclopentasiloxane.

[0236] The fat(s) of the invention are of natural or synthetic origin, preferably natural, more preferably of vegetable origin. They differ from fatty acids because saline fatty acids constitute soaps that are generally soluble in aqueous media.

[0237] According to a particular embodiment of the invention, the composition comprises one or more non-liquid fats at 25 °C and atmospheric pressure.

[0238] The wax(s)

[0239] According to a particular embodiment, the composition of the invention comprises one or more waxes.

[0240] By "wax" is meant a lipophilic compound, solid at room temperature (25 °C), with a reversible solid / liquid change of state, having a melting point greater than or equal to 30 °C which can go up to 200 °C and in particular up to 120 °C.

[0241] In particular, the wax(s) suitable for the invention may have a melting point greater than or equal to 45 °C, and in particular greater than or equal to 55 °C.

[0242] The composition Cl or Cl' according to the invention preferably comprises a wax content(s) ranging from 0.5% to 30% by weight relative to the total weight of the composition, in particular from 1% to 20%, more particularly from 2% to 15% relative to the total weight of the composition.

[0243] According to a particular embodiment of the invention, the composition according to the invention, Cl or Cl', is solid, in particular anhydrous. It can then be in stick form. Polyethylene micro-waxes in the form of crystallites with a form factor of at least 2 and a melting point ranging from 70 to 110 °C, and preferably 70 to 100 °C, will be used in order to reduce or even eliminate the presence of layers in the solid composition. These needle-like crystallites, and in particular their dimensions, can be visually characterized according to the following method.

[0244] The paste compound(s)

[0245] According to a particular embodiment, the composition according to the invention Cl or Cl' comprises one or more paste compounds.

[0246] By "pasty compound" in the context of the present invention, we mean a lipophilic fatty compound with reversible solid / liquid phase change, having in the solid state an anisotropic crystalline organization, and comprising at a temperature of 23 °C a liquid fraction and a solid fraction.

[0247] According to one embodiment, the composition contains one or more fatty substances d) which are hydrocarbon-based liquid fatty substances at 25°C and atmospheric pressure.

[0248] The liquid hydrocarbon fat(s) are selected from hydrocarbons and are of C6-Ci6 or more than 16 carbon atoms up to 60 carbon atoms, preferably between C6 and Ci6, and in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides or fluorinated oils of synthetic origin, fatty alcohols, esters of fatty acids and / or fatty alcohols, silicones. In particular, the liquid fat(s) are selected from non-siliconized oils.

[0249] It is recalled that, for the purposes of the invention, alcohols, esters, and fatty acids more particularly have one or more hydrocarbon group(s), linear or branched, saturated or unsaturated, comprising 6 to 60 carbon atoms, optionally substituted, in particular by one or more hydroxyl group(s) OH (in particular from 1 to 4 hydroxyl group(s)). If they are unsaturated, these compounds may include one to three unsaturations preferably of 1 to 3 carbon-carbon double bonds, conjugated or not.

[0250] With regard to the C6-Ci6 alkanes, these are linear or branched, possibly cyclic; preferably the fat(s) of the invention are chosen from linear or branched C8-Ci4 alkanes, more preferably C9-Ci3, and even more preferably C9-Ci2. Examples include hexane, decane, undecane, dodecane, tridecane, and isoparaffins such as isohexadecane, isodecane, or isododecane. The linear or branched hydrocarbons with more than 16 carbon atoms may be chosen from paraffin oils, petrolatum, polydecenes, and hydrogenated polyisobutene such as Parleam®.

[0251] Among hydrocarbon liquid fats d) having an overall solubility parameter according to the HANSEN solubility space less than or equal to 20 (MPa)1 / 2, we can mention oils, which can be chosen from natural or synthetic hydrocarbon oils, possibly fluorinated, possibly branched, alone or in mixture.

[0252] According to a highly advantageous embodiment, the composition according to the invention Cl or Cl' comprises one or more fatty substances which is / are one or more hydrocarbon oil(s). The oil(s) may / may be volatile or non-volatile.

[0253] According to a preferred embodiment of the invention, the fat(s) (d) are hydrocarbon oils, linear or branched, which are volatile, in particular selected from undecane, decane, dodecane, isododecane, tridecane, and their mixture of different oils, preferably volatile, comprising isododecane in the mixture, or a mixture of undecane and tridecane.

[0254] According to another particular embodiment, the liquid fat(s) (d) are a mixture of a volatile hydrocarbon oil and a non-volatile hydrocarbon oil, the mixture of which preferably comprises dodecane or isododecane as the volatile oil.

[0255] In particular, the fat(s) d) of the invention are a mixture of C9-C12 alkanes, preferably of natural origin, whose chains comprise 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes. This mixture is notably known under the INCI name C9-C12 ALCANE, CAS 68608-12-8, VEGELIGHT SILK®, marketed by BioSynthls. This volatile, biodegradable oil mixture is obtained from coconut oil (viscosity is 0.9-1.1 cSt (40 °C) and a flash point of 65 °C).

[0256] According to one embodiment, the composition contains only liquid oils at 25°C and atmospheric pressure. According to another embodiment, the composition Cl contains at least 80% liquid oils at 25°C and atmospheric pressure. hydrocarbons preferably volatile more preferably chosen from isodecane, decane, Cetiol UT®, VEGELIGHT SILK®.

[0257] According to another embodiment, the composition may include volatile and non-volatile oils, in particular in a volatile oil / non-volatile oil ratio greater than or equal to 4.

[0258] According to another embodiment, the composition contains 0 to 10% silicone oils, preferably 0 to 5% silicone oils.

[0259] Examples of volatile silicone oils include volatile linear or cyclic silicone oils, in particular those having a viscosity less than or equal to 8 centistokes (cSt) (8 x 10⁶ m² / s), and having, in particular, from 2 to 10 silicon atoms, and in particular, from 2 to 7 silicon atoms, these silicones possibly comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. Examples of volatile silicone oils usable in the invention include, in particular, dimethicones of viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

[0260] Examples of non-volatile silicone oils include non-volatile linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes containing alkyl, alkoxy and / or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenyl ethyl trimethylsiloxysilicates and pentaphenyl silicone oils.

[0261] The hydrocarbon oil may be selected from:

[0262] * hydrocarbon oils having 8 to 14 carbon atoms, and in particular:

[0263] - C8-Cl4 branched alkanes such as C8-Cl4 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example the oils sold under the trade names Isopars' or Permetyls,

[0264] - linear alkanes, for example such as n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, and their mixtures, the undecane-tridecane mixture, the n-undecane (Cil) and n-tridecane (Cl3) mixtures obtained in examples 1 and 2 of application WO 2008 / 155059 of Cognis, and their mixtures as well as the n-undecane (Cil) and n-tridecane (Cl3) Cetiol Ultimate® mixtures of BASF.

[0265] * short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate

[0266] * vegetable hydrocarbon oils such as triglycerides of fatty acid and glycerol esters, the fatty acids of which can have varying chain lengths from C4 to C24, the latter being linear or branched, saturated or unsaturated; these oils include triglycerides of heptanoic acid or octanoic acid, or even wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, rosehip, coconut; shea butter; or caprylic / capric acid triglycerides such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by Dynamit Nobel,

[0267] * synthetic ethers having from 10 to 40 carbon atoms;

[0268] * linear or branched hydrocarbons, of mineral or synthetic origin such Vaseline, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane, paraffin oils, and mixtures thereof,

[0269] * esters such as oils of formula R'C(O)-O-R2 in which R1 represents the remainder of a linear or branched fatty acid comprising 1 to 40 carbon atoms and represents a hydrocarbon chain, particularly branched, containing 1 to 40 carbon atoms provided that R1 + R2 is #10, such as Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, benzoates of alcohols in C12 to C15, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate;polyol esters and pentaerythritol esters, more preferably linear or branched C8-Ci0 fatty acid esters and linear or branched Ci2-Ci8 fatty alcohol esters alone or in mixture with alkanes from the complete hydrogenation / reduction of fatty acids from Cocos Nucifera (Coconut) oil, particularly dodecane or cococaprylate / caprate mixtures with dodecane, such as those with the INCI name coconut alkanes (and) Coco-caprylate / caprate marketed under the name VEGELIGHT 1212LC® by Grant Industries.

[0270] * branched-chain fatty alcohols, liquid at room temperature and / or unsaturated having 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.

[0271] The composition according to the invention Cl or Cl', in addition to the liquid hydrocarbon oil, may include a silicone oil. If silicone oil is present in the composition according to the invention Cl or Cl', preferably it is present in an amount not exceeding 10% by weight relative to the weight of the composition, more particularly in an amount less than 5% by weight relative to the total weight of the composition.

[0272] In particular, the composition comprises at least one liquid hydrocarbon fat c) selected from:

[0273] - vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, macadamia, soybean, sweet almond, calophyllum, palm, grapeseed, corn, arara, cottonseed, apricot, avocado, jojoba, olive, coconut or cereal germ oil;

[0274] - linear, branched or cyclic esters, having more than 6 carbon atoms, including 6 to 30 carbon atoms; and in particular isononyl isononanoate;

[0275] and more particularly esters of formula Rd-C(O)-O-Re in which Rd represents the remainder of a higher fatty acid comprising 7 to 19 carbon atoms and Re represents a hydrocarbon chain comprising 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, in particular diisopropyl adipate and isopropyl myristate; more preferably esters of formula Rd-C(O)-O-Re in which Rd represents the remainder of a higher fatty acid comprising 8 to 10 carbon atoms and Re represents a hydrocarbon chain comprising 12 to 18 carbon atoms;

[0276] - hydrocarbons, and in particular linear, branched and / or cyclic alkanes, volatile or non-volatile, such as C5-C6o isoparaffins, possibly volatile such as undecane, dodecane, isododecane, tridecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or 'ISOPARs', and mixtures thereof; or alkanes from the complete hydrogenation / reduction of fatty acid mixtures from Cocos Nucifera (Coconut) oil such as dodecane, mixtures of C9-Ci2 alkanes, chains of which comprise 9 to 12 carbon atoms, preferably linear or branched alkanes, in particular C9-Ci2 including dodecane, or paraffin oils, petrolatum, or hydrogenated polyisobutylene;

[0277] - ethers having 6 to 30 carbon atoms;

[0278] - ketones having 6 to 30 carbon atoms;

[0279] - aliphatic fatty monoalcohols having 6 to 30 carbon atoms, the chain hydrocarbon not containing a substitution group, such as oleic alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleic alcohol;

[0280] - polyols having 6 to 30 carbon atoms, such as hexylene glycol; and

[0281] - their mixtures, such as mixtures of linear or branched fatty acid esters in C8-CiO and fatty alcohols in Ci2-Ci8 and alkanes from the complete hydrogenation / reduction of fatty acid mixtures from Cocos Nucifera (Coconut) oil, in particular dodecane such as cococaprylate / caprate and dodecane mixtures, examples include those with INCI name coconut alkanes (and) Coco-caprylate / caprate marketed under the name VEGELIGHT 1212LC® by Grant Industries; or mixtures of C9-C12 alkanes, whose chains comprise 9 to 12 carbon atoms, preferably linear or branched alkanes, in C9-Ci2 in particular including dodecane, examples include the oil mixture with INCI name C9-12 ALKANE, VEGELIGHT SILK® marketed by BioSynthls.

[0282] Preferably, the composition according to the invention Cl or Cl' comprises at least one liquid hydrocarbon fat c) selected from:

[0283] - vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides,

[0284] - esters of formula Rd-C(O)-O-Re in which Rd represents the remainder of an acid higher fatty acid comprising 7 to 19 carbon atoms and Re represents a hydrocarbon chain comprising 3 to 20 carbon atoms, more preferably esters of formula Rd-C(O)-O-Re in which Rd represents the remainder of a higher fatty acid comprising 8 to 10 carbon atoms and Re represents a hydrocarbon chain comprising 12 to 18 carbon atoms;

[0285] - linear or branched C8-C60 alkanes, volatile or non-volatile such as isododecane and alkanes from the complete hydrogenation / reduction of fatty acid mixtures from Cocos Nucifera (Coconut) oil, in particular dodecane;

[0286] - cyclic, non-aromatic, C5-Ci2 alkanes; volatile or non-volatile;

[0287] - ethers having 7 to 30 carbon atoms;

[0288] - ketones having 8 to 30 carbon atoms;

[0289] - aliphatic fatty monoalcohols having 12 to 30 carbon atoms, the chain hydrocarbon not containing a substitution group, and

[0290] - their mixtures.

[0291] Advantageously, the fat(s) of the invention, in particular liquids, are nonpolar, i.e. formed solely of carbon and hydrogen atoms.

[0292] The liquid hydrocarbon fat(s) are preferably chosen from hydrocarbon oils having 8 to 14 carbon atoms, in particular volatile, more particularly non-polar oils, described above.

[0293] Preferably the fat(s) of the invention, in particular liquids, are chosen from alkanes such as dodecane, decane, isododecane, fatty alcohols such as octyldodecanol, esters such as isononyl isononanoate, coco-caprylate / caprate and mixtures thereof, more preferably alkanes.

[0294] More particularly, the fat(s) d) of the invention, especially liquid, are selected from C6-C16 alkanes, linear or branched, preferably C8-C14, more preferably Cg-C13, even more preferably Cg-C1, and even more preferably the alkanes are volatile. More particularly, the liquid fat(s) iii) of the invention are volatile and selected from undecane, decane, dodecane, isododecane, tridecane, and mixtures thereof including dodecane, isododecane, or a mixture of undecane and tridecane.

[0295] Preferably, the fatty substance(s) d) of the invention, in particular liquid, is isododecane.

[0296] According to another embodiment of the invention, the oil(s) c) of the invention, in particular liquid(s), is / are a mixture of non-volatile oil(s) and volatile oil(s), preferably the mixture comprising isododecane, undecane, dodecane, isododecane, tridecane, and more preferably isododecane as the volatile oil. Examples of volatile and non-volatile oil mixtures include a mixture of isododecane and isononyl isononanoate or a mixture of isododecane and isononyl isononanoate.

[0297] More preferably when the fat or fats are a mixture of volatile and non-volatile oil, the quantity of volatile oil is greater than the quantity of non-volatile oil.

[0298] In particular, in the mixture the non-volatile oil is a phenyl silicone oil preferably chosen from pentaphenyl silicone oils.

[0299] According to one embodiment, the composition comprises one or more fats, in particular liquids at 25 °C and atmospheric pressure, preferably one or more oils, in a content ranging from 0.01 to 99.9% by weight, relative to the total weight of the composition, preferably ranging from 0.1 to 50% by weight, preferably ranging from 0.5 to 20% by weight, preferably ranging from 1 to 5% by weight.

[0300] According to one embodiment of the invention, composition Cl or Cl' does not comprise fats d) as defined above.

[0301] According to one embodiment of the invention, the composition according to the invention Cl or Cl' comprises d) one or more fats in particular liquid at 25 °C and atmospheric pressure, c) water and e) one or more surfactants.

[0302] e) Surfactants

[0303] According to a particular embodiment of the invention, the composition further comprises e) one or more surfactant(s), preferably non-ionic, ionic or mixtures thereof.

[0304] The term "surfactant" refers to a compound that modifies the surface tension between two surfaces. The surfactant(s) (d) are amphiphilic molecules, which have two parts of different polarities: one lipophilic (which attracts fats) and is nonpolar, and the other hydrophilic (miscible or soluble in water) and is polar. The lipophilic part is generally a fat chain, and the other part, miscible with water, is polar and / or protic.

[0305] By "ionic" we mean anionic, cationic, amphoteric, or zwitterionic.

[0306] By "fatty chain" is meant a hydrocarbon chain comprising more than 6 atoms, preferably between 6 and 30 carbon atoms, preferably from 8 to 24 carbon atoms, linear or branched, saturated or not.

[0307] According to a first particular embodiment, the composition of the invention contains d) at least one non-ionic surfactant, siliconed or non-siliconized.

[0308] Among the non-ionic surfactants according to the invention, one can cite, alone or in mixtures, fatty alcohols, alpha-diols, alkylphenols, these 3 types of compounds being polyethoxylated, polypropoxylated and / or polyglycerolated, and having a fatty chain comprising for example 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range in particular from 2 to 50 and the number of glycerol groups being able to range in particular from 2 to 30.Other examples include ethylene oxide and propylene copolymers, ethylene oxide and propylene oxide condensates on fatty alcohols; polyethoxylated fatty amides preferably having 2 to 30 moles of ethylene oxide, polyglycerol fatty amides having on average 1 to 5 glycerol groups and in particular 1.5 to 4; oxyethylenated sorbitan fatty acid esters having 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkyl polyglycosides, N-alkylglucamine derivatives, amine oxides such as (CiO-Ci4)alkylamine oxides or N-acylaminopropylmorpholine oxides.

[0309] The surfactant(s) represent in total a quantity less than or equal to 2% by weight of surfactants, in relation to the total weight of the composition in question Cl or Cl', particularly less than or equal to 1% by weight of surfactants, more particularly less than 0.5% by weight of surfactants in relation to the total weight of the composition of the composition in question Cl or Cl', preferably the composition Cl or Cl' is free of surfactant.

[0310] Form of composition:

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318] According to one embodiment of the invention, the composition comprises an aqueous phase. The composition is in particular formulated as aqueous lotions or as water-in-oil, oil-in-water, or multiple emulsions (triple oil-in-water-in-oil or water-in-oil-in-water emulsion (such emulsions are known and described for example by C. FOX in "Cosmetics and Toiletries" - November 1986 - Vol 101 - pages 101-112). The aqueous phase of the composition contains water and generally other solvents soluble or miscible in water such as protic and polar solvents as defined previously (see additional solvents). The composition according to the invention Cl or Cl' preferably has a pH ranging from 3 to 9 depending on the support chosen. According to a particular embodiment of the invention, the pH of the composition(s) is neutral or even slightly acidic. Preferably, the pH of the composition is between 6 and 7. The pH of these compositions can be adjusted to the desired value by means of acidifying or alkalizing agents commonly used in cosmetics or by means of conventional buffer systems. The term "alkalizing agent" or "base" means an agent that increases the pH of the composition in which it is found. The alkalizing agent is a Brønsted, Lowry, or Lewis base. It may be mineral or organic. In particular, the said agent is chosen from a) ammonia, b) (bi)carbonate, c) alkanolamines such as mono-, di-, and triethanolamines and their derivatives, 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, such as arginine, lysine, omithine, citrulline, and histidine, and i) compounds of the following formula (F): [Chem. 17]: Formula (F) in which: W is a divalent alkylene radical in Ci-C6 possibly substituted by one or more hydroxyl groups or an alkyl radical in Ci-C6, and / or possibly interrupted by one or more heteroatoms such as O, or NRU; • R x, R y, R z, R t, and R u, identical or different, represent a hydrogen atom, a Ci-C6 alkyl radical or a Ci-C6 hydroxyalkyl radical, or a Ci-C6 aminoalkyl radical.

[0319] Examples of amines of formula (E) include 1,3-diaminopropane, 1,3-diamino 2-propanol, spermine, spermidine.

[0320] By "alkanolamine" is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched alkyl groups, in Ci-C8 bearing one or more hydroxyl radicals.

[0321] Among the mineral or organic hydroxides, examples may be given of those selected from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as sodium or potassium hydroxides, c) the hydroxides of a transition metal, d) the hydroxides of lanthanides or actinides, quaternary ammonium hydroxides, and guanidinium hydroxide. Mineral or organic hydroxides a) and b) being preferred.

[0322] Among the acidifying agents of the compositions used in the invention, examples include mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

[0323] The alkalizing and acidifying agents as defined above preferably represent from 0.001% to 20% by weight of the composition containing them. More particularly, from 0.005% to 8% by weight of the composition.

[0324] According to one embodiment of the invention, the composition comprises a quantity of water less than or equal to 10% by weight relative to the total weight of the composition, more preferably comprises a quantity of water less than or equal to 5%, better less than 2%, even better less than 0.5%, and in particular is free of water. Where appropriate, such small quantities of water may be introduced, in particular, by ingredients of the composition that may contain residual amounts of it.

[0325] According to a non-preferred embodiment, the composition does not include water.

[0326] Advantageously, the composition according to the invention Cl or Cl' comprises a physiologically acceptable medium. In particular, the composition is a cosmetic composition.

[0327] By physiologically acceptable medium is meant a medium compatible with the keratinous materials of human beings, such as for example the skin, lips, nails, eyelashes, eyebrows, hair.

[0328] By cosmetic composition is meant a composition compatible with keratinous materials, which has a pleasant color, odor and feel, and which does not generate unacceptable discomfort (tingling, pulling, redness), likely to deter the consumer.

[0329] Keratinous materials include the skin (body, face, eye contour, scalp), hair, eyelashes, eyebrows, body hair, nails, and lips.

[0330] The composition according to the invention Cl or Cl' may include a cosmetic additive selected from perfumes, preservatives, fillers, coloring agents, UV filters, oils, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free radical scavengers, polymers other than the polyhydroxylacanoates of the invention, thickeners.

[0331] According to a particular embodiment of the invention, the composition comprises a) at least one coloring agent selected from pigments, direct colorants and their mixtures, preferably a) pigments.

[0332] The term "pigment" means all pigments that impart color to keratinous materials, whether of synthetic or natural origin. The solubility of pigments in water at 25 °C and atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

[0333] These are solid particles, white or colored, naturally insoluble in the hydrophilic and lipophilic liquid phases commonly used in cosmetics or rendered insoluble by formulation in the form of a lacquer, where appropriate. More specifically, the pigments are slightly or not at all soluble in hydroalcoholic media.

[0334] The pigments that may be used are chosen in particular from among the organic and / or mineral pigments known to the art, especially those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry. Examples of pigments include organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry, "Pigment Organics," 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002 / 14356007.a20 371 and ibid., "Pigments, Inorganic, 1. General," 2009, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 10.1002 / 14356007.a20_243.pub3

[0335] These pigments may be in the form of a powder or pigment paste. They may be coated or uncoated.

[0336] Pigments can, for example, be chosen from mineral pigments, organic pigments, lacquers, special effect pigments such as mother-of-pearl or glitter, and mixtures thereof.

[0337] The pigment may be a mineral pigment. By mineral pigment is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on inorganic pigments. Mineral pigments useful in this application include, but are not limited to, mineral pigments. invention, iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

[0338] The pigment may be an organic pigment. By organic pigment is meant any pigment that meets the definition in the Ullmann Encyclopedia in the chapter on organic pigments. The organic pigment may in particular be chosen from among the compounds nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

[0339] In particular, the white or colored organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments coded in the Color Index under references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments coded in the Color Index under references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under references Cl 61565, 61570, 74260, the pigments oranges coded in the Color Index under the references CI 11725, 15510, 45370, 71105, red pigments coded in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, pigments obtained by oxidative polymerization of indole derivatives,phenolic compounds as described in French patent FR 2 679 771.

[0340] According to a particular embodiment of the invention, pigment pastes of organic pigments such as the products sold by the company HOECHST under the name are used as pigment(s):

[0341] - COSMENYL YELLOW IOG: Pigment YELLOW 3 (Cl 11710);

[0342] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);

[0343] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);

[0344] - COSMENYL RED R: Pigment RED 4 (Cl 12085);

[0345] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);

[0346] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);

[0347] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);

[0348] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);

[0349] - COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

[0350] The pigments according to the invention may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed, in particular, of particles comprising:

[0351] - an inorganic nucleus,

[0352] - at least one binder ensuring the fixation of the organic pigments to the core, and

[0353] - at least one organic pigment covering at least partially the nucleus.

[0354] The term "lake" refers to colorants adsorbed onto insoluble particles, the resulting mixture remaining insoluble during use. Examples of inorganic substrates onto which the colorants are adsorbed include alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum. Examples of organic colorants include cochineal carmine.

[0355] Examples of lacquers include products known by the following names: D&C Red 21 (CI 45380), D&C Orange 5 (CI 45370), D&C Red 27 (CI 45410), D&C Orange 10 (CI 45425), D&C Red 3 (CI 45430), D&C Red 7 (CI 15850:1), D&C Red 4 (CI 15510), D&C Red 33 (CI 17200), D&C Yellow 5 (CI 19140), D&C Yellow 6 (CI 15985), D&C Green (CI 61570), D&C Yellow 10 (CI 77002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42 090).

[0356] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

[0357] Among the dyes, we can mention cochineal carmine. We can also mention the colorants known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).

[0358] As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850:1).

[0359] The pigment(s) may also be special effect pigments.

[0360] By "special effect pigments" is meant pigments which generally create a colored appearance (characterized by a certain shade, vibrancy and clarity) that is non-uniform and changes depending on the viewing conditions (light, temperature, viewing angles, etc.). They are thus distinguished from colored pigments which provide a uniform opaque, semi-transparent or conventional transparent tint.

[0361] There are several types of special effect pigments, those with a low refractive index such as fluorescent, photochromic or thermochromic pigments, and those with a higher refractive index such as mother-of-pearl or glitter.

[0362] Examples of special effect pigments include pearlescent pigments such as titanium mica coated with iron oxide, mica coated with iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, and titanium mica coated with an organic colorant, among others. of the aforementioned type, as well as pearlescent pigments based on bismuth oxychloride. It can also consist of mica particles on the surface of which are superimposed at least two successive layers of metallic oxides and / or organic coloring materials.

[0363] Mother-of-pearl may in particular have a yellow, pink, red, bronze, orange, brown, gold and / or copper colour or reflection.

[0364] By way of illustration of the mother-of-pearls that can be used in the context of the present invention, we can mention in particular the gold-colored mother-of-pearls marketed in particular by the company ENGELHARD under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze mother-of-pearls marketed in particular by the company MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona), by the company Eckart under the name Prestige Bronze and by the company ENGELHARD under the name Super bronze (Cloisonne); orange mother-of-pearls, notably marketed by the company ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna);brown mother-of-pearl, notably marketed by ENGELHARD under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-tinted mother-of-pearl, notably marketed by ENGELHARD under the name Copper 340A (Timica) and by Eckart under the name Prestige Copper; red-tinted mother-of-pearl, notably marketed by MERCK under the name Sienna fine (17386) (Colorona); yellow-tinted mother-of-pearl, notably marketed by ENGELHARD under the name Yellow (4502) (Chromalite); red-tinted mother-of-pearl with a gold tint, notably marketed by ENGELHARD under the name Sunstone G012 (Gemtone);black mother-of-pearl with a gold sheen, notably marketed by the company ENGELHARD under the name Nu antique bronze 240 AB (Timica); blue mother-of-pearl, notably marketed by the company MERCK under the names Matte blue (17433) (Microna), Dark Blue (117324) (Colorona); white mother-of-pearl with a silver sheen, notably marketed by the company MERCK under the name Xirona Silver; and orange-pink and golden-green mother-of-pearl, notably marketed by the company MERCK under the name Indian summer (Xirona), and their mixtures.

[0365] In addition to mother-of-pearl on a mica support, one can consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

[0366] Other examples include non-substrate interference pigments such as liquid crystals (Wacker's Helicones HC) and interference holographic glitter (Spectratek's Geometry Pigments or Spectra f / x). Special effect pigments also include fluorescent pigments, whether daylight fluorescent or ultraviolet fluorescent, phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots, marketed, for example, by Quantum Dots Corporation.

[0367] The variety of pigments that can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic, interference effects.

[0368] The size of the pigment used in the cosmetic composition according to the present invention is generally between 10 nm and 200 µm, preferably between 20 nm and 80 µm, and more preferably between 30 nm and 50 µm.

[0369] The pigments can be dispersed in the product by means of a dispersing agent.

[0370] By "dispersing agent" is meant a compound which makes it possible to protect the particles dispersed against their agglomeration or flocculation. This dispersing agent can be a surfactant, an oligomer, a polymer, or a mixture of several of these, possessing one or more functionalities with a strong affinity for the surface of the particles to be dispersed. In particular, they can bind physically or chemically to the surface of the pigments. These dispersing agents also possess at least one functional group compatible with or soluble in the continuous medium. The agent can be charged, anionic, cationic, zwitterionic, or neutral.

[0371] According to a particular embodiment of the invention, the dispersing agents used are chosen from among the esters of 12-hydroxystearic acid more particularly and of C8 to C2o fatty acids and of polyols such as glycerol, diglycerin, such as poly(12-hydroxystearic acid stearate) with a molecular weight of about 750 g / mol such as that sold under the name Solsperse 21 000 by the company Avecia, polygyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures.

[0372] As another dispersant that can be used in the compositions of the invention, we can mention quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by Avecia, poly dimethylsiloxane / oxypropylene mixtures such as those sold by Dow Corning under the references DC2-5185, DC2-5225 C.

[0373] The pigments used in the cosmetic composition according to the invention can be surface treated with an organic agent.

[0374] Thus, the surface-treated pigments useful within the scope of the invention are pigments that have undergone, totally or partially, a surface treatment of a chemical, electronic, electrochemical, mechanochemical, or mechanical nature with an organic agent such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64, before being dispersed in the composition according to the invention. These organic agents may, for example, be chosen from amino acids; waxes, for example, carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate;metal alkoxides; polysaccharides, for example chitosan, cellulose and its derivatives; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate motifs; proteins; alkanoamines; silicone compounds, for example silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes, siloxysilicates; fluorinated organic compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

[0375] The surface-treated pigments useful in the cosmetic composition according to the invention may also have been treated by a mixture of these compounds and / or have undergone several surface treatments.

[0376] The surface-treated pigments useful in the context of the present invention can be prepared using surface treatment techniques well known to those skilled in the art or found as such in the commercial market.

[0377] Preferably, the surface-treated pigments are covered by an organic layer.

[0378] The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments.

[0379] Surface treatment can thus be achieved, for example, by a chemical reaction of a surfactant with the surface of the pigments and the creation of a covalent bond between the surfactant and the pigments or fillers. This method is described in particular in US patent 4,578,266.

[0380] Preferably, an organic agent covalently linked to the pigments will be used.

[0381] The surface treatment agent can represent from 0.1 to 50% by weight of the total weight of the pigments treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 10% by weight.

[0382] Preferably, the surface treatments of the pigments are chosen from the following treatments: - a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW; - a Chitosan treatment such as the CTS surface treatment marketed by LCW; - a Triethoxycaprylylsilane treatment such as the AS surface treatment marketed by LCW; - a Methicone treatment such as the SI surface treatment marketed by LCW; - a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW; - a Dimethicone / Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW; - a Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW; - a Lauroyl Lysine Dimethicone treatment such as the LL / SI surface treatment marketed by LCW; - a Magnesium Myristate treatment such as the MM surface treatment marketed by LCW; - a Dimyristate Aluminium treatment such as the MI surface treatment marketed by Miyoshi; - a Perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW; - an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi; - a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi; - a Dimethicone / Disodium Stearoyl Glutamate treatment such as the SA / NAI surface treatment marketed by Miyoshi; - a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito; - an acrylate / dimethicone copolymer and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito; - a Polymethylhydrogen siloxane / Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito; - a Lauryl Lysine / Aluminium Tristearate treatment such as the LL-StAI surface treatment marketed by Daito; - an Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito; - an Octyltriethylsilane / Perfluoroalkyl Phosphate treatment such as the FOTS surface treatment marketed by Daito; - an Acrylate / Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito; - an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito; - a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment such as the AC surface treatment marketed by Daito; - a Cellulose treatment such as the C2 surface treatment marketed by Daito; - an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito; - a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito - The composition according to the present invention may further comprise one or more pigments not treated on the surface. - According to a particular embodiment of the invention, the pigment(s) are mineral pigments. - According to another particular mode of the invention, the pigment or pigments are chosen from among the mother-of-pearls.

[0383] According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in submicron-sized particulate form.

[0384] By "sub-micron" or in English "sub-micron" is meant pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (pm), in particular between 0.1 and 0.9 pm, and preferably between 0.2 and 0.6 pm

[0385] According to one embodiment, the dispersing agent and the pigment(s) are present in an amount (dispersant: pigment) between 0.5:1 and 2:1, particularly between 0.75:1 and 1.5:1 or better between 0.8:1 and 1.2:1.

[0386] According to a particular embodiment, the dispersing agent is adapted to disperse pigments and is compatible with a condensation-curable formulation.

[0387] By “compatible” is meant, for example, that said dispersing agent is miscible in the oily phase of the composition or dispersion containing the pigments, it does not delay or reduce hardening. The dispersing agent is preferably cationic.

[0388] The dispersing agent(s) may therefore have a silicone skeleton, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include: - amino-silicones, i.e. silicones comprising one or more amino groups, such as those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee les polymers, - silicone acrylates such as Tego ® RC 902, Tego ® RC 922, Tego ® RC 1041, and Tego ® RC 1043, marketed by Evonik, - polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695, by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412, by Evonik.

[0389] According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type and are positively charged.

[0390] Dispersing agents can also be cited as having chemical groups capable of reacting with the reagents of the oil phase and thus are likely to improve the 3D network formed from amino-silicone. For example, dispersing agents of silicone epoxy pigments can react chemically with the amino group(s) of the amino-silicone prepolymer to increase the cohesion of the amino-silicone film comprising the pigment(s).

[0391] Preferably the pigment(s) of the invention are chosen from carbon black, iron oxides in particular black and micas coated with iron oxide, triarylmethane pigments in particular blue and violet such as BLUE 1 LAKE, azo pigments in particular red such as D&C RED 7 alkali metal salt of lithol red such as the calcium salt of lithol red B, even more preferably red iron oxides.

[0392] The coloring agents may be chosen from direct colorants.

[0393] By "direct colorant" is meant natural and / or synthetic colorants, different Oxidation dyes. These are dyes that will diffuse superficially onto the fiber.

[0394] They may be ionic or non-ionic, preferably cationic or non-ionic, either as the sole colorants.

[0395] These direct dyes are for example chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethinic dyes, quinonic dyes and in particular neutral, acidic or cationic anthraquinone dyes, azinic direct dyes, triarylmethanic direct dyes, azomethine direct dyes and natural direct dyes.

[0396] Examples of suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines, and styryl, carbonyl, azinic, nitrate (hetero)aryl, tri-(hetero)aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

[0397] Preferably, the direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quatemized or quatemisable cationic group.

[0398] According to a particular embodiment of the invention, the direct dyes comprise at least one quantified cationic chromophore.

[0399] As direct dyes according to the invention, the following may be mentioned: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azoic, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzantrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthones; lactones; (poly)methines such as stilbene or styryl-type dimethines; naphthalimides; naphthanilides;naphtholactams; naphthoquinones; nitro, particularly nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes / carotenoids; porphyrins; pyrantrones; pyrazolantrones; pyrazolones; pyrimidinoantrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

[0400] For cationic azo dyes, particular mention can be made of those derived from the cationic dyes described in the Kirk Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 19 / 04 / 2010.

[0401] Among the azo dyes that can be used according to the invention, cationic azo dyes described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954 can be mentioned.

[0402] According to a preferred embodiment of the invention, the direct dye(s) are chosen from among the cationic dyes called "basic dyes".

[0403] The following compounds may be cited among the azo dyes described in the Colour Index International, 3rd edition:

[0404] - Basic Red 22 - Basic Red 76 - Basic Yellow 57 - Basic Brown 16 - Basic Brown 17.

[0405] Among the cationic quinone dyes, those mentioned in the aforementioned Colour Index International are suitable, and among these, the following dyes may be cited, among others:

[0406] - Basic Blue 22 - Basic Blue 99.

[0407] Suitable azinic dyes include those listed in the Colour Index International, for example the following dyes: - Basic Blue 17 - Basic Red 2.

[0408] Among the cationic triarylmethane dyes that can be used according to the invention, the following dyes may be mentioned, in addition to those listed in the Colour Index: - Basic Green 1 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Basic Blue 26.

[0409] Cationic dyes can also be cited in documents US 5888252, EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954. Also cited are those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academy Press vol 1 to 7, in the encyclopedia "Kirk Othmer" "Chemical technology", chapter "dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons.

[0410] Preferably, cationic direct dyes are chosen from those derived from azo and hydrazono type dyes.

[0411] According to a particular embodiment, the direct dyes are cationic azoic dyes, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850673, WO 850638, WO 9948433 9744004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943, FR 1212, 228 DE 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 3524842, US 5879413, EP 1062940, EP 113938, DE 61387, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52 ; Cytology (1968), 10(3), 403-5 ; Zh. Obshch. Khim. (1970), 40(1), 195-202 ; Ann. Say. (Rome) (1975), 65(5-6), 305-14 ; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Rome. Say. (1988), 33(4), 377-83 ; Text. Nothing. J. (1984), 54(2), 105-7 ; Say. Ind. (Milan) (1974), 56(9), 600-3 ; Khim. Technol. (1979), 22(5), 548-53 ; Word. Monatsh. Chem. (1975), 106(3), 643-8 ; MRL Bull. Nothing. Dev.(1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72. .

[0412] Preferably, the cationic direct dye(s) comprise a quaternary ammonium group, more preferably the cationic charge is endocyclic.

[0413] These cationic radicals are, for example, a cationic radical: - an exocyclic charge (di / tri)(Ci-C8)alkylammonium, or - an endocyclic charge such that it includes a heteroaryl cationic group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazole thiazolium thiazolopyridinium, thiazolimidazolium, thiopyryl, triazolium or xanthylium.

[0414] On peut citer les colorants cationiques hydrazono de formula (III) et (IV), les azoïques de formulas (V), et (VI) suivantes :

[0415] [Chem. 18]:

[0416] Hét+-C(Ra)=NN(Rb)-Ar, Q- HéU-NiRal-N^QlR^-Ar, Q- (IH) (IV) Hét+-N=N-Ar, Q- Ar-N = N-Ar”, Q- (V) (V!) formulas (III) to (VI) in which: ■ Het+ represents a cationic heteroaryl radical, preferably with endocyclic cationic charge such as imidazolium, indolium, or pyridinium, possibly preferentially substituted by at least one (CrC8)alkyl group such as methyl; ■ Ar+ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(Ci-C8)alkyl-ammonium such as trimethylammonium; ■ Ar represents an aryl group, in particular phenyl, possibly substituted, preferably by one or more electron-donating groups such as i) (Cr C8)alkyl possibly substituted, ii) (CrC8)alkoxy possibly substituted, iii) (di)(Ci-C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) N-(CrC8)alkyl-N-aryl(Ci-C8)alkylamino possibly substituted or else Ar represents a julolidine group; ■ Ar' ' represents a (hetero)aryl group possibly substituted such as phenyl or pyrazolyl possibly substituted, preferably by one or more (CrC8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Cr C8)alkoxy or phenyl groups; ■ Ra and Rb, identical or different, representing a hydrogen atom or a (CrC8)alkyl group possibly substituted, preferably by a hydroxyl group; ■ or the substituent Ra with a substituent of Het+ and / or Rb with a substituent of Ar together form with the atoms that bear them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (Cr C4)alkyl group possibly substituted by a hydroxyl group; ■ Q represents an organic or mineral anionic counter-ion such as a halide or an alkyl sulfate.

[0417] In particular, mention may be made of endocyclic cationic azo and hydrazono direct dyes of formula (III) to (VI) as defined above. More particularly, endocyclic cationic direct dyes of formula (III) to (VI) described in patent applications WO 95 / 15144, WO 95 / 01772 and EP-714954. Preferably, the following direct dyes:

[0418] [Chem. 19]:

[0419] (V-1)

[0420] formulas (III-1) and (V-1) in which: - R1 represents an (Ci-C4)alkyl group such as methyl; - R2 and R3, whether identical or different, represent a hydrogen atom or an (Ci-C4)alkyl group such as methyl; and - R4 represents a hydrogen atom or an electron-donating group such as (Cr C8)alkyl possibly substituted, (Ci-C8)alkoxy possibly substituted, (di)(Cr C8)(alkyl)amino possibly substituted on the alkyl group(s) by a hydroxyl group; particularly R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH, - Q is an anionic counterion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0421] In particular, dyes of formula (III-1) and (V-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives:

[0422] [Chem. 20]:

[0423] Basic Red 51 Basic Orange 31 Basic Yefiow 87

[0424] with Q an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesytyl.

[0425] According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined above.

[0426] Examples of fluorescent dyes include radicals derived from the dyes acridines, acridones, benzantrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyranes, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}bores (BODIPY®), diketopyrrolo-pyrroles, fluorindines, (poly)methines (including cyanines and styryls / hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes / carotenoids, squaranes, stilbenes, xanthenes.

[0427] We may also mention the fluorescent dyes described in documents EP 1133975, WO 03 / 029359, EP 860636, WO 95 / 01772, WO 95 / 15144, EP 714954 and those listed in K. Venkataraman's encyclopedia "The Chemistry of Synthetic Dye," 1952, Academy Press, vols. 1-7, in Kirk Othmer's "Chemical Technology," chapter "Dies and Dye Intermediates," 1993, Wiley and Sons, and in various chapters of Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Wiley and Sons, and in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 1st ed. Molecular Probes / Invitrogen - Oregon 2005 distributed via the Internet or in previous printed editions.

[0428] According to a preferred embodiment of the invention, the fluorescent dye(s) are cationic and comprise at least one quaternary ammonium radical such as those of the following formula (VII):

[0429] [Chem. 21] :

[0430] W+-[C(Rc)=C(R.)]m-Ar, Q (VH)

[0431] formula (VII) in which:

[0432] ■ W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium possibly substituted by one or more (CrC8)alkyl groups possibly substituted in particular by one or more hydroxyl groups;

[0433] ■ Ar representing an aryl group such as phenyl or naphthyl, possibly substituted preferably by i) one or more halogen atoms, such as chlorine or fluorine; ii) one or more (Ci-C8)alkyl groups, preferably Cr-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-C8)alkoxy groups such as methoxy; v) one or more hydroxy(Cr-C8)alkyl groups such as hydroxyethyl; vi) one or more amino or (di)(Ci-C8)alkylamino groups, preferably with the alkyl portion at Ci-C4. substituted by one or more hydroxyl groups such as (di)hydroxyethylamino, vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as pyperazinyl, pyperidinyl or 5 or 6-membered heteroaryl groups such as pyrrolidinyl, pyridinyl and imidazolinyl;

[0434] ■ m' represents an integer from 1 to 4, particularly m is equal to 1 or 2; more preferably; 1; ■ Rc, Rd, identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group possibly substituted, preferably at C1-C4, or else Rc contiguous to W+ and / or Rd contiguous to Ar form with the atoms that bear them a (hetero)cycloalkyl, particularly Rc is contiguous to W+ and form a (hetero)cycloalkyl such as cyclohexyl; ■ Q is an organic or mineral anionic counter-ion as defined previously.

[0435] Among the natural direct dyes that can be used according to the invention are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, and orceins. Extracts or decoctions containing these natural dyes, and in particular henna-based poultices or extracts, can also be used.

[0436] According to a particular embodiment of the invention, the quantity of colouring agents, in particular pigments, varies from 0.5% up to 40%, and preferably from 1 to 20% relative to the weight of the composition and dispersion comprising them.

[0437] Advantageously, the composition according to the invention Cl or Cl' is a makeup composition, in particular a lip makeup composition, mascara, eyeliner, eyeshadow, foundation.

[0438] Adjuvants

[0439] The composition according to the invention Cl or Cl' may further comprise one or more fillers, in particular in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 20% by weight. Fillers are understood to mean particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or texture of the composition.

[0440] The composition according to the invention Cl or Cl' may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, trace elements, emollients, sequestrants, perfumes, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, or mixtures thereof. The composition according to the invention Cl or Cl' can be in the form of an anhydrous composition, a water-in-oil emulsion or an oil-in-water emulsion or an aqueous composition.

[0441] An anhydrous composition is defined as a composition containing less than 2% by weight of water, or even less than 0.5% water, and in particular one that is water-free. Where applicable, such small quantities of water may be introduced by ingredients of the composition that may contain residual amounts of water.

[0442] The invention is illustrated in more detail in the following examples. Quantities are indicated as a percentage by weight. Examples

[0443] The PHAs presented in the various examples were prepared in 3-liter chemostats and / or 5-liter Fernbach flasks, depending on whether or not an inhibitor of the [3-oxidation pathway was used. The isolation of the PHAs was similar for all the examples obtained.

[0444] In a first step, the microorganism generates PHAs, which are stored in intracellular granules. The proportion of these granules varies depending on the applied conditions, such as 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, depending on the nature of the microorganisms. In the second step, the biomass containing the PHAs is isolated, i.e., separated from the fermentation medium, and then dried. The PHAs are extracted from the biomass and purified if necessary.

[0445] A mixture of saturated and unsaturated carbon sources is, for certain examples, necessary for the stability of the PHA obtained.

[0446] [Table 2]: Source of carscnë CAS Asds cspsyiiqde (RADIAC1D 308} 124-37-2 Assde ÇWUiéeŒricic acid) KJ » ©

[0447] [Table 3]: Source of cerdons Genus and species Origin Afâsnge ceprylsque and a Psetsdomænss putida ATÇO® 47054™ acidic mixture n©nano«$üe and undeeyàênque: Pse ùdsmon as puèîds ATCC® 47^54™ Example 1: PH A with side chain R1 representing a 30% linear unsaturated n-octalenyl group and R2 representing an n-hexyl group

[0448] [Chem. 22]:

[0449]

[0450] The process for obtaining PHA in Example 1 is adapted from the article: Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440, Z. Sun, JA Ramsay, M. Guay, BA Ramsay, Applied Microbiology Biotechnology, 82. 657-662. 2009.

[0451] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054™. The culture method is carried out under axenic conditions with discontinuous growth, fed with a maintenance solution containing a carbon source mixture at a rate of p=0.15h₁ in a 3L chemostat containing 2.5L of culture medium. The flow rate of the maintenance feed pump is proportional to the growth of the microorganism according to Equation 1:

[0452] st =2L=A.eV-t Yx / s Yjys

[0453] The system is aerated at an air flow rate of 0.5 vvm for a dissolved oxygen (DO) setpoint of 30% of saturation. The pH is regulated with a 15% ammonia solution. The temperature of the fermentation medium is regulated at 30°C.

[0454] Assembly of the batch growth fermentation mode fed:

[0455] The fermentation medium is regulated in terms of temperature, dissolved oxygen pressure and pH (not shown)

[0456] The production process is carried out using four distinct culture media. The first culture medium, defined as MCI "inoculum", is used for the preparation of the preculture. The second culture medium, defined as MC2 "batch", is used for the unfed, batch growth of the microorganism with the primary carbon sources in Fernbach flasks. The third culture medium, defined as MC3 "maintenance", is used for the batch feeding, or maintenance, of the fermentation with the carbon sources of interest at a flow rate calibrated according to the growth of the microorganism. Simultaneously, MC4 is added to medium MC3 with a volume ratio of MC3:MC4 = 1.25:1.

[0457] The composition in grams per litre of the three media is described in Table 4 [Tables 4] MCI "inoculum" MC2 "batch" MC3 "maintenance" MC4 (NH4)2SO4 4.7 4.7 / / Na2HPO4; 7H2O 12 9 / / KH2PO4 2.7 2.03 / / MgSO4;7H2O 0.8 1.03 / / Nutrient Broth 3 / / / Nonanoic acid / 0.7 700 / Undecylenic acid / 0.3 300 / Microelement solution s / 10 / / Acrylic acid / / / 12 Glucose / / / 240 NaOH 2N qsp pH 6.8 / / Water milliQ qsp m = 1000g / / The Nutrient Broth composition by mass percentage is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCO™.

[0458] The composition of the microelement solution in grams per litre is described in Table 5: [Tables 5] FeSO4-7H2O 10.0 g CaC12-2H2O 3.0 g ZnSO4-7H2O 2.2 g MnSO4-4H2O 0.5 g H3BO3 0.3 g CoC12-6H2O 0.2 g Na2MoO4-2H2O 0.15 g NiC12-6H2O 0.02 g CuSO4-5H2O 1.00 g MilliQ water (or 0.5N HCl) QSP 1000 g 100 mL of preculture is prepared by suspending a cryotube containing 1 mL of the strain with 100 mL of MCI inoculum culture medium at pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask. The inocum is then incubated at 30°C at 150 rpm for 24 hours. 1.9 L of MC2 "BATCH" culture medium is placed in a previously sterilized 3 L chemostat and inoculated at OD=0.1 with 100 mL of inocum. After 4 hours at 30°C at 850 rpm, the maintenance culture (MC3 + MC4) is introduced using the flow rate defined by equation 1.

[0459] At the end of the introduction, the biomass is isolated by centrifugation and then washed three times with water. The biomass is dried by freeze-drying before being extracted with ethyl acetate for 24 hours. The suspension is clarified by filtration through a GF / A filter (Wattman®). The filtrate, composed of PHA in solution in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40°C until constant mass is reached. The PHA thus obtained was purified twice by solubilization in a minimum of ethyl acetate and precipitation in a 70 / 30 v / v ethanol / water mixture.

[0460] The PHA of Example 1 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure.

[0461] Example 2: Functionalization of the 30% unsaturated linear side-chain PHA R=6 and R=8 from Example 1 with thiolactic acid

[0462] [Chem. 23]:

[0463]

[0464] 1 g of PHA from the example and 6 equivalents of thiolactic acid by unsaturation (1.2 g) were dissolved in 10 mL of acetone at room temperature with stirring. 0.08 equivalent of 2-hydroxy-2-methylpropiophenone (25 mg) were added to the mixture. The reaction mixture was then irradiated under a UV lamp (100 W, 365 nm) for at least 10 minutes. The solvent, excess thiol, and initiator were removed in an oven (24 h, 80°C) under reduced pressure.

[0465] The PHA grafted with thiolactic acid was characterized by proton NMR. The proton NMR spectrum shows that the characteristic signals of the unsaturations have completely disappeared, which confirms 100% thiolactic acid grafting onto the initially unsaturated chains.

[0466] Example 3: Post-dispersion in water of the linear side-chain PHA R=6 and R=8 unsaturated at 30% grafted with thiolactic acid obuenu in example 2 with diisopropylethylamine (DIPEA)

[0467] [Chem. 24]:

[0468]

[0469] 1 g of polymer from Example 2 (PHA functionalized with thiolactic acid) is solubilized in 5 g of acetone to obtain a 20% ma solution, then 0.2 g of N,N-diisopropylethylamine (DIPEA) (1.1 eq) is added to salify 100% of the acidic functions. 5 g of water is then added dropwise under vigorous stirring at with the help of an UltraTurrax (IKA T10 Basic). Finally, the acetone is evaporated under reduced pressure with the Rotavapor.

[0470] The polymer obtained at the end of the reaction is totally soluble in water (20% active material solution). Application examples

[0471] Evaluations in simplex formulas were conducted to show performance for skin application.

[0472] For one-step applications:

[0473] A formula containing the polymer solution, a pigment, and a solvent was prepared. This formula was applied to a Bioskin-type vitro substrate (elastomer skin equivalent substrate) using a film applicator (wet thickness 100 µm). The deposit was allowed to dry for 24 h.

[0474] The simplex formulation is carried out using a Speed ​​Mixer (2 minutes - 3500 rpm).

[0475] After 24 hours of drying, evaluations of the deposits are carried out:

[0476] Resistance to olive oil / water / sebum

[0477] 0.5 mL of olive oil (or water or sebum) are applied to the deposit obtained After drying. After 5 minutes, the olive oil (or water or sebum) is removed by 15 passes with a cotton ball. The deterioration of the film following contact with olive oil, water, or sebum is then observed - see [Fig. 1].

[0478] Bioskin formulation fragmentation test

[0479] As with the olive oil resistance tests, films are made on a Bioskin sample. After a day of drying, using hand strength, the Bioskin plate is stretched 10 times.

[0480] Then the result can be observed on the deposit (fragmentation or not).

[0481] Two example responses are shown in [Fig. 2], which is the result of the fragmentation test. Left: cohesive deposit, no fragmentation / Right: fragmentation with the appearance of deposit rupture under stress

[0482] For each simplex composition, the evaluations were conducted after drying. The objective was to observe the cosmetic properties improved by the compounds of the invention. In all cases, the improvement of at least one property was observed for the compounds of the invention compared to a compound not related to the invention.

[0483] The evaluation was carried out as follows:

[0484] +++: Cosmetic property evaluated as very effective

[0485] ++ : Cosmetic property evaluated as moderately effective

[0486] + : Cosmetic property evaluated as having low performance

[0487] 0: Cosmetic property evaluated as not performing [Tableauxô] Composition A (invention) Ingredients %MA Post aqueous dispersion at 20% ma of PHA Polymer of Example 3 97 Red iron oxide 3 [Paintings?] Composition B (comparative) Ingredients %MA Solution of the polymer from example 1 at 20% ma in isododecane 97 Red iron oxide 3 The evaluation results are summarized in the table below: [Tables8] Fragmentation Water Resistance Olive Oil Resistance Sebum Resistance Composition B (comparative) +++ +++ ++ + Composition A (Invention) +++ +++ +++ +++

[0488] After applying the compositions of the invention to keratinous materials such as synthetic skin, it appears that the deposits obtained are resistant to daily chemical (water / olive oil / sebum) and mechanical (Fragmentation) aggressions. Hair application:

[0489] Hairstyling evaluation protocol

[0490] A 1g strand of 90%BN hair is wrapped around a brush.

[0491] 2 g of a solution containing the PHA polymer of Example 3 at 10% in water is sprayed onto the strand. The strand was weighed before and after application. Approximately 0.5 g of the 10% solution is applied to the strand.

[0492] The wick is measured after application and 24 h after application (Wick left at room temperature).

[0493] A comparison was made with a wick on which only water was sprayed.

[0494] A 1g strand of keratin fibers (90% Natural White BN hair) is wrapped around a brush (approximate diameter 2cm over a length of 3cm).

[0495]

[0496] 2g of a 10% ma aqueous solution of polymer of example 3 was prepared. This solution was sprayed onto the keratin fiber wick.

[0497] The wicks were weighed before and after application (0.5 g of water or 10% aqueous solution of polymer of example 3 were deposited per wick.

[0498] Each wick is measured immediately after application and then 24 h after application (Wick left at room temperature 25 °C).

[0499] [Tables9] Examples Value after application (in cm) Value after 24h (in cm) Untreated wick 20.5 19 Wick treated with water 20.5 9 Wick treated with 10% aqueous polymer solution Example 3 20.5 5

[0500] It appears that the strands which have been treated with the composition of the invention and according to the process of the invention make it possible to obtain curls which after 24 h are more wavy since the top of the curls is significantly closer together according to the invention (5 cm) after 24 h vs. 9 cm with water alone and 19 cm without treatment.

Claims

1. Demands A process for treating keratinous materials, preferably a) keratinous fibers, in particular human fibers such as hair, or |3) human skin, in particular lip skin, which employs at least one composition, preferably cosmetic, comprising a) one or more PHA copolymer(s) selected from: r. r "2 KQ! R Ç -(CH^-S-ALKi-CfOJ-OH -ALKi (2Â) {CH^-ALKHA-} -ALKs (3A) -(CH2)pS-ALK!-(C+ï -ALK; p is an integer between 3 and 15, ALKi denotes a linear or branched divalent hydrocarbon radical in crc15 ALK2 denotes a C3-C20 alkyl radical m and n are integers greater than or equal to 1, preferably the sum n + m is between 450 and 1400 inclusive; preferably m < n; C+ denotes a cationic group; A denotes an anionic group, ** group A being chosen from -C(O)OH, -C(O)O , -SO3H, -S(O)2O , -OS(O)2OH, -OS(O)2O , -P(O)OH2, -P(O)O2, -P(O)2O , -P(OH)2, =P(O)-OH, -P(OH)O , =P(0)-0 , =P-OH, and =P-0 and their mixtures, the anionic parts include one or more cationic counter-ions M+ to achieve the electroneutrality of the PHA; ** the cationic group C+ being chosen from among the cationizable amine groups -NRbRc, ammonium -N+RaRbRc, phosphonium -P+RaRbRc, cationizable amidine -C(=NRa)-NRbRc, amidinium -C(=NRa)-N+RbRcRd, cationizable guanidine -N(Ra)-C(=NRa)-NRbR„ guanidinium -N(Ra)-C(=NRa)-N+RbRcRd, or cationizable imidazolyl possibly substituted by one or more Ra radicals as defined above, or imidazolium possibly substituted by one or more Ra radicals as defined above, and their

2. mixtures, the cationic parts comprising one or more anionic counter ions Q to achieve electroneutrality of the PHA, with R representing a hydrogen atom, a (Ci-C4)alkyl group, or (hetero)aryl(Ci-C4)alkyl such as benzyl, preferably Ra representing a hydrogen atom or a (CrC4)alkyl group; Rb, Rc, and Rd, identical or different, represent a (CrC4)alkyl group possibly substituted by one or more hydroxy groups, (hetero)aryl, (hetero)aryl(Ci-C4)alkyl such as benzyl, (hetero)cycloalkyl, (hetero)cycloalkyl(Ci-C4)alkyl, or else Rb and Rc, or Rc and Rd represent with the nitrogen or phosphorus atom which bears them a heterocycle, saturated or unsaturated, aromatic or not, particularly (Ci-C4)alkyl possibly substituted by one or more hydroxy groups; the cationic parts comprising one or more anionic counter ions Q to ensure electroneutrality;in particular, the stereochemistry of the carbon atoms bearing the radicals R1, and R2 is even configuration (R) or (S), preferably configuration (R); b) possibly water; it being understood that: - the composition comprises an amount less than or equal to 2% by weight of surfactants, relative to the total weight of the composition, particularly less than or equal to 1% by weight of surfactants, more particularly less than 0.5% by weight of surfactants relative to the total weight of the composition, preferably the composition is free of surfactants. A process according to claim 1 employing a composition comprising a) one or more PHA copolymer(s) selected from: iiiiiiiiiiiiiii qCH2>S-CH (CH <41 a-hexyi with m and n as defined in claim 1 and M+ represents a cationic counterion to achieve electroneutrality of the PHA, such as an alkali metal, an alkaline earth metal, ammonium: RaRbRcRdN+, or phosphonium: RaRbRcRdP+, preferably ammonium, with Ra, Rb, Rc, and Rd as defined in claim 1, preferably Ra representing a hydrogen atom; Rb and Rc, identical or different, preferably identical, represent a linear or branched (Ci-C4)alkyl group, preferably branched, such as isopropyl or isobutyl, more preferably isopropyl; and Rd represents a linear or branched (Cr-C4)alkyl group, such as ethyl, more particularly M represents a diisopropylethylammonium group: (i-Pr)2N+(H)Et; more particularly selected from iiiiiiiiiiiiiiiiiiiiiiii iiiOiil iiiiiiiii (0 4GH2^m(CH0-C(O)-OH Q-hexyl a-Bu £2} n-hexyî a-Bu with m, n, and p are integers greater than or equal to 1, preferably the sum n + m + p is between 450 and 1400 inclusive; and M+ is as defined previously; more particularly the stereochemistry of the carbon atoms bearing the radicals R1, R2 and R3 is even configuration (R) or (S), preferably configuration (R); even more specifically chosen from lllllllllllllllillllll^ iiiiliii iiiBiiii -{CHîJs-SÆHfCHsyCiQkOH. .a-aexys g-Bu Et (2'7 -(CHî>S-CH{GHsycO-Ot M* 8-hexy? S-Bu Et with m, n, p and v are integers greater than or equal to 1, preferably the sum n + m + p + v is between 450 and 1400 inclusive; and M+ is as defined previously; more particularly the stereochemistry of the carbon atoms bearing the radicals R1, R2, R3, and R4 is even configuration (R) or (S), preferably configuration (R).

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