Compositions containing polyhydroxyalkanoate copolymers having long hydrocarbon-based chains bearing ionic groups and methods for treating keratinous materials with the compositions - Patents.com

Abstract

The present invention relates to a method for treating keratinous materials, preferably α) keratinous fibres, in particular human keratinous fibres such as hair or β) human skin, in particular lips, using a composition, preferably a cosmetic composition, comprising a) one or more polyhydroxyalkanoate (PHA) copolymers a) comprising at least two different repeating polymer units selected from the following units (A) and (B) and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof and solvates thereof, such as hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A)-[-O-CH(R 2 )-CH2-C(O)-]- unit (B) (in the polymer units (A) and (B): -R 1 and R 2 is as defined in the description;-(A) is different from (B);-it is understood that the composition comprises a surfactant in an amount of 2% by weight or less, based on the total weight of the composition.

Description

[Technical field]

[0001] The present invention relates to a composition, preferably a cosmetic composition, comprising at least one polyhydroxyalkanoate (PHA) copolymer having a hydrocarbon-based chain carrying ionic groups, specific ionic polyhydroxyalkanoates (PHAs), the use of this composition in cosmetics and also a method for treating keratinous materials using this composition. [Background technology]

[0002] It is a known practice to use film-forming polymers in cosmetics that can be delivered in an organic medium, such as a hydrocarbon-based oil. The polymers are used as film formers, especially in make-up products such as mascara, eyeliner, eyeshadow, lipstick, etc.

[0003] (Patent Document 1) describes a C3-C 21 Cosmetic compositions are described that include a pigment coated with a polyhydroxyalkanoate.

[0004] US Patent No. 5,399,663 describes a cosmetic composition comprising a 4-carboxy-2-pyrrolidinone ester derivative and a film-forming polymer, which may be a polyhydroxyalkanoate, such as polyhydroxybutyrate, polyhydroxyvalerate, and polyhydroxybutyrate-co-polyhydroxyvalerate.

[0005] WO 02 / 06336 describes a cosmetic composition comprising a thermoplastic resin, such as a polyhydroxyalkanoate, in an aqueous dispersion, and a silicone elastomer.

[0006] The majority of polyhydroxyalkanoates are polymers derived from the polycondensation of polymeric repeating units that are for the most part identical and derived from the same carbon source or substrate. These documents do not describe the use of copolymers derived from the polycondensation using an aliphatic substrate or a first carbon source and a second substrate different from the first substrate that contains at least one ionic group or groups of a different chemical nature than the first carbon source.

[0007] It is therefore necessary to provide compositions containing PHAs that can be functionalized or can be functionalized in a variety of ways and subsequently become more water-soluble despite the presence of long-chain aliphatics, which makes it possible to obtain films on keratinous materials that have good cosmetic properties, in particular good oil and sebum resistance, and also to modify the gloss or matt feel.

[0008] Consumers are increasingly demanding cosmetic formulations that have a low surfactant content (<2% by weight relative to the total weight of the formulation) or are even surfactant-free. However, with long-chain PHAs, especially those of the mcl-PHA type that are carboxylated, it is known to be difficult to have stable particles without the need to use surfactants [cf. (Non-Patent Document 1)]. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] French Patent Application Publication No. A-2964663 [Patent Document 2] International Publication No. 2011 / 154508 Brochure [Patent Document 3] US Patent Application Publication No. A-2015 / 274972 [Non-patent literature]

[0010] [Non-Patent Document 1] “Stability of Aqueous Suspensions of Medium-Chain-Length Poly-3-Hydroxyalkanoate Particles”, Journal of Polymers and the Environment, vol. 24, p. 281-285 (2016) Summary of the Invention [Means for solving the problem]

[0011] Unexpectedly, it has been discovered that polyhydroxyalkanoate copolymers having a hydrocarbon-based chain carrying ionic groups, as defined below, can be easily used in aqueous media (in particular preferentially water as solvent), thus making it possible to obtain homogeneous compositions that are easy to use, even when using only small amounts of surfactants or no surfactants at all.

[0012] Moreover, the composition has good stability, especially after storage for one month at room temperature (25°C).The composition makes it possible to obtain a film with good cosmetic properties, especially good resistance to oil and sebum, and also a matte or glossy appearance, especially after its application to keratinous materials.Furthermore, it is possible to interact the PHA polymer with active agents, especially organic active agents, such as UV screen agents, fluorescent or non-fluorescent chromophores, anti-aging active agents, via ionic groups, which agents contain ionic groups of opposite ionicity to the PHA polymer, and which, when grafted, can be made more persistent, especially against oil, water and sebum.

[0013] A first subject of the present invention is therefore a method for treating keratinous materials, preferably α) keratinous fibres, in particular human keratinous fibres such as hair, or β) human skin, in particular the lips, which comprises a) one or more PHA copolymers a) comprising at least two different repeating polymer units selected from the following units (A) and (B) and also their optical or geometric isomers, their organic or mineral acid or base salts and their solvates, such as for example hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- Unit (B) (In the polymer units (A) and (B), -R 1 represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain or a saturated or unsaturated non-aromatic cyclic hydrocarbon-based chain containing 3 to 30 carbon atoms; preferably, the hydrocarbon-based chain is i) linear or branched (C5-C 28 ) alkyl, ii) linear or branched (C6-C 28 ) alkenyl, iii) linear or branched (C6-C 28 ) alkynyl, and iii) preferably the hydrocarbon-based chain is acyclic and linear; The hydrocarbon-based chain is Anionic group (A - ), cationic group (C + ) and mixtures thereof; (**A - The groups are -C(O)OH, -C(O)O - , -SO3H, -S(O)2O - , -OS(O)2OH, -OS(O)2O - , -P(O)OH2, -P(O)O2 - , -P(O)O - , -P(OH)2, =P(O)-OH, -P(OH)O - , =P(O)-O - , =P-OH and =PO - and mixtures thereof, the anionic portion being selected from one or more cationic counterions M to achieve electrical neutrality of the PHA. + , for example i) alkali metals, ii) alkaline earth metals, iii) ammonium R a R b R c R d N + , iv) phosphonium R a R bR c R d P + (R a is defined below), v) containing a cationic form of lysine or guanidine; **C + The cationic group is a cationizable amine group -NR b R c , ammonium group -N + R a R b R c , a phosphonium group -P + R a R b R c , a cationizable amidine group -C(=NR a )-NR b R c , amidinium group -C(=NR a )-N + R b R c R d , a cationizable guanidine group -N(R a )-C(=NR a )-NR b R c , a guanidinium group -N(R a )-C(=NR a )-N + R b R c R d or one or more R as defined below a a cationizable imidazolyl group optionally substituted with a group or one or more R a The cationic moiety is selected from imidazolium groups optionally substituted with groups, and mixtures thereof, and the cationic moiety is substituted with one or more anionic counterions Q to achieve electrical neutrality of the PHA. - , such as halides, carboxylates, such as acetate or glutamate, where R a represents a hydrogen atom, a (C1-C4) alkyl group or a (hetero)aryl(C1-C4) alkyl group, such as benzyl, preferably R arepresents a hydrogen atom or a (C1-C4) alkyl group; R b , R c and R d may be the same or different and represent one or more hydroxy, (hetero)aryl, (hetero)aryl(C-C)alkyl, (hetero)cycloalkyl or (hetero)cycloalkyl(C-C)alkyl groups optionally substituted with one or more hydroxy, (hetero)aryl, (hetero)aryl(C-C)alkyl groups, such as benzyl, or alternatively R b and R c or R c and R d represents, together with the nitrogen or phosphorus atom which bears it, a saturated or unsaturated, aromatic or non-aromatic heterocycle; in particular represents (C1-C4) alkyl, optionally substituted with one or more hydroxy groups; the cationic moiety may be substituted with one or more anionic counterions Q to ensure electroneutrality. - Includes; ***R 1 The groups are: a) halogen, such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(C1-C4)(alkyl)amino, e) thiocarboxy, f) (thio)carboxamido-C(O)-N(R a )2 or -C(S)-N(R a ) 2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl, and j) (hetero)cycloalkyl, k) cosmetically active agent, l) RX (R represents a group selected from α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl, such as phenyl), m) thiosulfate; X may also be substituted with one or more atoms or groups selected from a') O, S, N (R' a ) or Si(R' b )(R' c ), b') S(O) r or (thio)carbonyl, c') or a combination of a') and b'), such as a (thio)ester, (thio)amide, (thio)urea or sulfonamide; R' arepresents a hydrogen atom or a (C1-C4) alkyl group or an aryl(C1-C4) alkyl group, such as benzyl, preferably R a represents a hydrogen atom; R' b and R' c may be the same or different and represent a (C1-C4) alkyl or (C1-C4) alkoxy group, in particular the only one substituent is preferably selected from a) halogen and j) epoxide, etc., a') one or more heteroatoms, such as O, S, N(R a ) and Si(R b )(R c ), b') S(O) r , (thio)carbonyl, c') or a combination of a') and b'), such as (thio)esters, (thio)amides, (thio)ureas, sulfonamides, etc., preferably esters -OC(O)- or -C(O)-O-, where r is equal to 1 or 2 and R a is as previously defined; preferably, R a represents a hydrogen atom, and R b and R c is as previously defined); -R 2 is R 1 represents a hydrocarbon-based chain as defined for 2 The hydrocarbon-based chain of 1 Preferably the group R corresponds to the number of carbon atoms minus at least one carbon atom. 1 having a carbon number equal to the number of carbon atoms minus two carbon atoms); b) optionally water; using at least one composition, preferably a cosmetic composition, comprising -R 1 In the same PHA, the A - and C + group, in which case the counterion M + and Q - ensures the electroneutrality of the PHA and may be absent at the same time, -(A) is different from (B); -R1 and R 2 In the same PHA, the A - and C + group, in which case the counterion M + and Q - may be absent while ensuring the electroneutrality of the PHA; the composition comprises an amount of surfactant of less than or equal to 2% by weight relative to the total weight of the composition, in particular less than or equal to 1% by weight relative to the total weight of the composition, more particularly less than 0.5% by weight of surfactant, preferentially the composition is surfactant-free It is understood that.

[0014] According to a variant, the method for treating keratinous materials, preferably α) keratinous fibres, in particular human keratinous fibres such as hair, or β) human skin, in particular the lips, comprises a) one or more PHA copolymers a) comprising one or more of the following units (A) and also their optical or geometric isomers, organic or mineral acids or their basic salts and their solvates, such as for example hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) (In the polymer unit (A), -R 1 represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain or a saturated or unsaturated non-aromatic cyclic hydrocarbon-based chain containing 3 to 30 carbon atoms; preferably, the hydrocarbon-based chain is i) linear or branched (C5-C 28 ) alkyl, ii) linear or branched (C6-C 28 ) alkenyl, iii) linear or branched (C6-C 28 ) alkynyl, and iii) preferably the hydrocarbon-based chain is acyclic and linear; The hydrocarbon-based chain is Anionic group (A - ), cationic group (C + ) and mixtures thereof; (**This A - The groups are -C(O)OH, -C(O)O- , -SO3H, -S(O)2O - , -OS(O)2OH, -OS(O)2O - , -P(O)OH2, -P(O)O2 - , -P(O)O - , -P(OH)2, =P(O)-OH, -P(OH)O - , =P(O)-O - , =P-OH and =PO - and mixtures thereof, the anionic portion being selected from one or more cationic counterions M to achieve electrical neutrality of the PHA. + , for example i) alkali metals, ii) alkaline earth metals, iii) ammonium R a R b R c R d N + , iv) phosphonium R a R b R c R d P + (R a is as defined below), v) cationic forms of lysine or guanidine, etc.; **C + The cationic group is a cationizable amine group -NR b R c , ammonium group -N + R a R b R c , a phosphonium group -P + R a R b R c , a cationizable amidine group -C(=NR a )-NR b R c , amidinium group -C(=NR a )-N + R b R c R d , a cationizable guanidine group -N(R a )-C(=NR a )-NR b R c , a guanidinium group -N(R a )-C(=NRa )-N + R b R c R d or one or more R as defined below a a cationizable imidazolyl group optionally substituted with a group or one or more R a The cationic moiety is selected from imidazolium groups optionally substituted with groups, and mixtures thereof, and the cationic moiety is substituted with one or more anionic counterions Q to achieve electrical neutrality of the PHA. - , such as halides, carboxylates, such as acetate or glutamate; R a represents a hydrogen atom, a (C1-C4) alkyl group or a (hetero)aryl(C1-C4) alkyl group, such as benzyl, preferably R a represents a hydrogen atom or a (C1-C4) alkyl group; R b , R c and R d may be the same or different and represent one or more hydroxy, (hetero)aryl, (hetero)aryl(C-C)alkyl, (hetero)cycloalkyl or (hetero)cycloalkyl(C-C)alkyl groups optionally substituted with one or more hydroxy, (hetero)aryl, (hetero)aryl(C-C)alkyl groups, such as benzyl, or alternatively R b and R c or R c and R d together with the nitrogen or phosphorus atom bearing them, represent a saturated or unsaturated, aromatic or non-aromatic heterocycle; in particular, the (C1-C4) alkyl is optionally substituted with one or more hydroxy groups; the cationic moiety may be substituted with one or more anionic counterions Q to ensure electroneutrality. - Includes; ***R 1 Groups also include a) halogen, such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(C1-C4)(alkyl)amino, e) thiocarboxy, f) (thio)carboxamido-C(O)-N(R a )2 or -C(S)-N(R a) 2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl, and j) (hetero)cycloalkyl, k) cosmetically active agent, l) Rx (R represents a group selected from α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl, such as phenyl), m) thiosulfate; X may also be substituted with one or more atoms or groups selected from a') O, S, N (R' a ) or Si(R' b )(R' c ), b') S(O) r or (thio)carbonyl, c') or a combination of a') and b'), such as a (thio)ester, (thio)amide, (thio)urea or sulfonamide; R' a represents a hydrogen atom or a (C1-C4) alkyl group or an aryl(C1-C4) alkyl group, such as benzyl, preferably R a represents a hydrogen atom; R' b and R' c may be the same or different and represent a (C1-C4) alkyl or (C1-C4) alkoxy group, in particular the only one substituent is preferably selected from a) halogen and j) epoxide, etc., a') one or more heteroatoms, such as O, S, N(R a ) and Si(R b )(R c ), b') S(O) r , (thio)carbonyl, c') or a combination of a') and b'), such as (thio)esters, (thio)amides, (thio)ureas, sulfonamides, etc., preferably esters -OC(O)- or -C(O)-O- (r is equal to 1 or 2, R a is as previously defined; preferably, R a represents a hydrogen atom, and R b and R c is as defined previously)); b) optionally water The present invention may be a method of using at least one composition, preferably a cosmetic composition, comprising: -R 1 The group is A in the same PHA. - and C + group, in which case the counterion M + and Q - may be absent while ensuring the electroneutrality of this PHA; the composition comprises less than or equal to 2% by weight of surfactant relative to the total weight of the composition, in particular less than or equal to 1% by weight of surfactant, more particularly less than 0.5% by weight of surfactant relative to the total weight of the composition, and preferentially the composition is free of surfactant; is understood. [Brief description of the drawings]

[0015] [Figure 1] 0.5 mL of olive oil (or water or sebum) is applied to the deposit obtained after drying. After 5 minutes, the olive oil (or water or sebum) is removed by wiping 15 times with absorbent cotton. In this way, the deterioration of the film after contact with olive oil, water or sebum is examined. [Diagram 2] The results of the fragmentation test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] In one variant, the composition, preferably the cosmetic composition, may comprise a) one or more polyhydroxyalkanoate (PHA) copolymers as defined hereinbefore and hereinafter and containing one or more units (A), where R 1 represents a saturated and linear hydrocarbon-based chain containing 3 to 10 carbon atoms and substituted with one or more carboxyl -C(O)OH groups, this chain is interrupted by a heteroatom or a group a') to c') as previously defined.

[0017] In another aspect, the PHA copolymer can be a PHA copolymer as defined above, where (A) is: -R 1 represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain or a saturated or unsaturated non-aromatic cyclic hydrocarbon-based chain containing 5 to 28 carbon atoms; preferably, the hydrocarbon-based chain is i) linear or branched (C5-C 28 ) alkyl, ii) linear or branched (C6-C 28 ) alkenyl, iii) linear or branched (C6-C 28 ) alkynyl, iii) preferably the hydrocarbon-based chain is acyclic and linear; said hydrocarbon-based chain is selected from One or more anionic groups (A - ), cationic group (C + ) and mixtures thereof; (**A - The group is -C(O)O - , -SO3H, -S(O)2O - , -OS(O)2OH, -OS(O)2O - , -P(O)OH2, -P(O)O2 - , -P(O)O - , -P(OH)2, =P(O)-OH, -P(OH)O - , =P(O)-O - , =P-OH and =PO - and mixtures thereof, the anionic moiety being selected from one or more cationic counterions M + Includes; **C + The cationic group is a cationizable amine group -NR b R c , ammonium group -N + R a R b R c , a phosphonium group -P + R a R b R c , a cationizable amidine group -C(=NR a )-NR b R c , amidinium group -C(=NR a )-N + Rb R c R d , a cationizable guanidine group -N(R a )-C(=NR a )-NR b R c , a guanidinium group -N(R a )-C(=NR a )-N + R b R c R d or one or more R as defined above a a cationizable imidazolyl group optionally substituted with a group or one or more R a and mixtures thereof to achieve electroneutrality of the PHA, wherein R a , R b , R c and R d is as defined above), the cationic moiety is substituted with one or more anionic counterions Q - Including M + and Q - is as previously defined);

[0018] In one variation, (A) is R 1 However, hydrocarbon-based chains, especially i) -C(O)O - M + (M + is as above), preferably ammonium R a R b R c R d N + One or more (preferably one) A selected from - Substituted with a group, linear or branched (C5-C 28 ) alkyl, where R a , R b , R c and R d is as defined previously, preferably R a represents a hydrogen atom; R b and R cmay be identical or different, preferably identical, and represent a linear or branched, preferably branched, (C1-C4) alkyl group, such as isopropyl or isobutyl, more preferentially isopropyl; R d represents a linear or branched (C1-C4) alkyl group, such as ethyl, more specifically M + Diisopropylethylammonium group: (i-Pr)2N + (H) A PHA copolymer as previously defined, which is such that it represents Et.

[0019] In one variation, the process may be a process for preparing a PHA having carboxylate groups.

[0020] In one variant, a non-therapeutic cosmetic method for treating keratinous materials may comprise the application of the composition or of a PHA copolymer as defined above or as defined herein below to keratinous materials. This treatment method is in particular a method for caring for or making up keratinous materials.

[0021] In one variant, the non-therapeutic use may be the cosmetic use of the composition or of the PHA copolymer, as defined above or hereinafter, in particular for caring for or making up keratinous substances.

[0022] For purposes of this invention, unless otherwise specified: The term "cosmetic active agent" refers to a group of organic or organosilicon compounds that can be incorporated into cosmetic compositions to provide an effect on keratinous materials, whether this effect is immediate or provided by repeated applications. Examples of cosmetic active agents can include colored or colorless, fluorescent or non-fluorescent chromophores, such as those derived from optical brighteners, or chromophores derived from UVA and / or UVB blockers, anti-aging active agents or active agents with an effect on the barrier function, deodorant agents other than mineral particles, antiperspirant active agents other than mineral particles, desquamating active agents, antioxidant active agents, moisturizing active agents, sebum-regulating active agents, active agents intended to limit the shine of the skin, active agents intended to combat the effects of pollution, antibacterial or bactericidal active agents, active agents intended to provide benefits to the skin, such as antidandruff active agents, and fragrances. - the term "(hetero)aryl" means an aryl or heteroaryl group; - the term "(hetero)cycloalkyl" means a cycloalkyl or heterocycloalkyl group; - an "aryl" or "heteroaryl" group or an aryl or heteroaryl portion of a group, C1-C6 and preferably C1-C4 alkyl groups; Halogen atoms, such as chlorine, fluorine or bromine; Hydroxyl groups; ·C1-C2 alkoxy groups; C2-C4 (poly)hydroxyalkoxy groups; · Amino group; an amino group substituted with one or two identical or different C1-C6, preferably C1-C4 alkyl groups; · Acylamino groups (-NR-COR'), where the R group is a hydrogen atom; the C1-C4 alkyl group and the R' group are a C1-C4 alkyl group; a carbamoyl group ((R)2N-CO-), in which the R groups may be identical or different and represent a hydrogen atom or a C1-C4 alkyl group; alkylsulfonylamino groups (R'SO2-NR-) (wherein the R group represents a hydrogen atom or a C1-C4 alkyl group and the R' group represents a C1-C4 alkyl group or a phenyl group); aminosulfonyl groups ((R)2N-S(O)2-) (wherein the R groups, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group); carboxyl groups in acid or salt form (preferably salified with alkali metals or substituted or unsubstituted ammonium); · Cyano group (CN); Polyhalo(C1-C4)alkyl groups, preferentially trifluoromethyl (CF3) may be substituted by at least one substituent carried by a carbon atom selected from: The cyclic or heterocyclic moiety of the non-aromatic group is selected from the group: Hydroxyl, C1-C4 alkoxy, C2-C4 (poly)hydroxyalkoxy, alkylcarbonylamino (RCO-NR'-) (wherein the R' group is a hydrogen atom or a C1-C4 alkyl group and the R group is a C1-C2 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups); alkylcarbonyloxy (RCO-O-), where R is a C1-C4 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups; Alkoxycarbonyl ((RO-CO-) where R is a C1-C4 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups) may be substituted by at least one substituent carried by a carbon atom selected from: - a cyclic or heterocyclic group, or a non-aromatic portion of an aryl or heteroaryl group, may also be substituted by one or more oxo groups; - the hydrocarbon-based chain is unsaturated if it contains one or more double bonds and / or one or more triple bonds; - an "aryl" group denotes a monocyclic or fused or non-fused polycyclic group containing 6 to 22 carbon atoms, at least one ring of which is aromatic; preferentially, the aryl group is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, preferably phenyl; - "heteroaryl" group denotes a monocyclic or fused or non-fused polycyclic 5- to 22-membered group containing 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms, of which at least one ring is aromatic; preferentially, the heteroaryl group is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, isopropyl, ethyl ... selected from midazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthimidazolyl, naphthoxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrrylyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl and xanthryl; - a "cyclic" or "cycloalkyl" group is a monocyclic or fused or non-fused polycyclic, non-aromatic, cyclic hydrocarbon-based group containing from 5 to 22 carbon atoms and which may contain one or more unsaturations; cycloalkyl is preferably a cyclohexyl group; - a "heterocyclic" or "heterocycloalkyl" group is a monocyclic or fused or non-fused polycyclic 3- to 9-membered non-aromatic ring group containing 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms; preferably, heterocycloalkyl is selected from epoxide, piperazinyl, piperidyl and morpholinyl; - an "alkyl" group is a linear or branched, in particular C1-C6 and preferably C1-C4 saturated hydrocarbon-based group; - an "alkenyl" group is a linear or branched unsaturated hydrocarbon-based group containing one or more conjugated or non-conjugated double bonds; - an "alkynyl" group is a linear or branched unsaturated hydrocarbon-based group containing one or more conjugated or non-conjugated triple bonds; - "alkoxy group" is an alkyloxy group, the alkyl group being a linear or branched C1-C6, preferentially C1-C4, hydrocarbon-based group; - the term "organic or mineral acid salt" more specifically refers to i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid HSO, iv) alkylsulfonic acids: Alk-S(O)OH, such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(O)OH, 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, HPO; ix) triflic acid, CFSOH, and x) tetrafluoroboric acid, HBF; xi) organic carboxylic acids, R°-C(O)-OH(I'), where R° is a (hetero)aryl group, such as phenyl, a (hetero)aryl(C1-C4)alkyl group, such as benzyl, or a (C1-C4)alkyl group, such as phenyl, ... 10) alkyl, said alkyl group being preferably optionally substituted by one or more hydroxyl groups or by amino or carboxyl groups, R° preferably representing a (C1-C6) alkyl group, optionally substituted by one, two or three hydroxyl or carboxyl groups; more preferentially, the monocarboxylic acid of formula (I') is selected from acetic acid, glycolic acid, lactic acid and mixtures thereof, more particularly selected from acetic acid and lactic acid; and the polycarboxylic acid is selected from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof; and xii) organic or mineral acid salts, especially selected from salts derived from amino acids containing more carboxylic acid groups than amino groups, such as gamma-carboxyglutamic acid, aspartic acid or glutamic acid, in particular gamma-carboxyglutamic acid; - "anionic counterion" is an anion or anionic group associated with a cationic charge; more specifically, anionic counterions include: i) halides, such as chloride or bromide; ii) nitrates; iii) sulfonates, including C1-C6 alkylsulfonates: Alk-S(O)2O - , such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)O - benzenesulfonates and toluenesulfonates or tosylates; v) especially those of the formula R'[C(O)OH] u (R' represents a saturated or unsaturated, linear or branched, hydrocarbon-based chain containing 1 to 8, in particular 1 to 6 and preferably 1 to 4, carbon atoms, which is optionally substituted by one or more hydroxyl or (di)(C1-C6)(alkyl)amino groups and u represents an integer from 1 to 6, better still from 1 to 4 and even better still an integer of 1, 2 or 3), such as, for example, citrate; succinate; tartrate; lactate; acetate or glutamate, vi) alkyl sulfates: Alk-OS(O)O - vii) aryl sulfates: Ar—OS(O)O -viii) alkoxy sulfates: Alk-OS(O)O - , such as methoxy sulfate and ethoxy sulfate; xi) aryloxy sulfate: Ar—OS(O)O - x) phosphate; xi) triflate; and xii) borate, for example tetrafluoroborate; - A "cationic counterion" is a cation or cationic group associated with an anionic charge; more specifically, a cationic counterion is i) an alkali metal, such as sodium or potassium, preferably Na + ii) alkaline earth metals, e.g. Ca 2+ , Mg 2+ etc., iii) Ammonium R a R b R c R d N + , iv) phosphonium R a R b R c R d P + (R a represents a hydrogen atom or a (C1-C4) alkyl group or a (hetero)aryl(C1-C4) alkyl group, such as benzyl, preferably R a represents a hydrogen atom or a (C1-C4) alkyl group; R b , R c and R d may be the same or different and represent (C1-C4)alkyl, (hetero)aryl, (hetero)aryl(C1-C4)alkyl, such as benzyl, (hetero)cycloalkyl or (hetero)cycloalkyl(C1-C4)alkyl groups, in particular (C1-C4)alkyl groups; or v) cationic forms of lysine or guanidine. Selected from; -R 1 The group is A in the same PHA. - and C + group, in which case the counterion M + and Q -may not be present at the same time to ensure the electrical neutrality of the PHA; for example, the same PHA may contain therein a number "n" of carboxylate groups and the same number "n" of ammonium groups such that electrical neutrality of the PHA is achieved, and another scenario is where two carboxylate groups and an alkaline earth metal Ca group are present to achieve electrical neutrality of the PHA. 2+ It is a PHA containing. - "solvates" refers to hydrates and also to combinations with linear or branched C1-C4 alcohols, such as ethanol, isopropanol or n-propanol; the term "chromophore" refers to a compound that exhibits a wavelength λ of 250 to 800 nm. abs By "chromophore" is meant a group derived from a colourless or coloured compound capable of absorbing in the UV and / or visible range of 400 nm to 800 nm. Preferably, the chromophore is coloured, i.e. it absorbs in the visible range, i.e. preferably at wavelengths between 400 and 800 nm. Preferably, the chromophore appears coloured to the naked eye, in particular between 400 and 700 nm (Ullmann's Encyclopedia, 2005, Wiley-VcH, Verlag "Dyes, General Survey", § 2.1 Basic Principle of Colour); The term "fluorophore" refers to a group of chromophores with an emission wavelength λ between 400 and 800 nm and an absorption wavelength λ longer than the em By "fluorescent chromophores" is meant chromophores that are also capable of re-emitting light in the visible range of λ 2 . Preferably, the Stokes shift, i.e. the difference between the wavelength of maximum absorption and the wavelength of emission, is at least 10 nm. Preferably, fluorescent chromophores are capable of re-emitting light in the visible range λ 2 . abs , i.e., absorbs at wavelengths of 400 to 800 nm, and has a λ em More preferably, the fluorescent chromophore has a λ between 420 and 550 nm. abs Absorption is possible in the visible range λ between 470 and 600 nm. em It can be re-emitted with - the term "brightening chromophore" means a chromophore derived from an optical brightening compound or "optical brightener, optical brightener (OBA)" or "fluorescent brightening agent (FBA)" or "fluorescent whitening agent (FWA)", i.e. which emits light in the UV radiation range, i.e. at wavelengths λ between 250 and 350 nm; absThen, the light is absorbed at a wavelength λ of 400 to 600 nm. em They re-emit this energy by fluorescence in the visible range, i.e. between blue-violet and blue-green wavelengths, with a maximum in the blue range. Fluorescent brightener chromophores are therefore visually colorless. - the term "UV-A blocker" means a chromophore derived from a compound that blocks (or absorbs) UV-A ultraviolet radiation of wavelengths between 320 and 400 nm. A distinction can be made between short UV-A blockers (which absorb light of wavelengths between 320 and 340 nm) and long UV-A blockers (which absorb light of wavelengths between 340 and 400 nm); - The term "UV-B blocker" means a chromophore derived from a compound that blocks (or absorbs) UV-B ultraviolet radiation at wavelengths between 280 and 320 nm. Further, unless otherwise specified, limits defining the extent of a range of values ​​are included within that range of values.

[0023] a) PHA copolymer The composition according to the method of the invention comprises as a first component one or more PHA copolymers comprising a) at least two different repeating polymer units selected from the following units (A) and (B) as previously defined: In one variant, the composition may comprise as a first component one or more PHA copolymers containing a) several different repeating polymer units (A) as previously defined.

[0024] The term "copolymer" means that the polymer is derived from the polycondensation of different polymeric repeating units with each other; for example, if the polymer is derived from the polycondensation of polymeric repeating units (A) and (B), then the polymeric unit (A) is different from the polymeric unit (B) (more precisely, R 1 is R 2 In one variant, when the polymer is derived from the polycondensation of polymer repeat units (A), the units (A) are different from each other (more precisely, R 1 The group is different from one repeat unit to the next).

[0025] In one variant, the composition, preferably the cosmetic composition, may comprise a) one or more polyhydroxyalkanoate (PHA) copolymers consisting of the series of the following units (A) and also their optical or geometric isomers, their organic or mineral acid or base salts and their solvates, such as hydrates: -[-O-CH(R 1 )—CH2—C(O)—]— unit (A) (R1 is as previously defined).

[0026] In one variant, the composition, preferably the cosmetic composition, is as defined before and hereinafter and comprises a) one or more polyhydroxyalkanoate (PHA) copolymers a) consisting of a series of units (A) as defined before, where R 1 represents a saturated and linear hydrocarbon-based chain containing from 3 to 10 carbon atoms and substituted with one or more carboxyl -C(O)OH groups, said chain is interrupted by heteroatoms or groups a') to c') as previously defined).

[0027] The composition according to the invention comprises, as a first component, a) one or more PHA copolymers containing at least two different repeating polymer units selected from units (A) and (B) as previously defined.

[0028] The present invention relates to a) one or more polyhydroxyalkanoate (PHA) copolymers a) comprising at least two different repeating polymer units selected from the following units (A) and (B), and also their optical or geometric isomers, their organic or mineral acid or base salts and their solvates, such as hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- Unit (B) (In the polymer units (A) and (B), -R 1represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain or a saturated or unsaturated non-aromatic cyclic hydrocarbon-based chain containing 3 to 30 carbon atoms; preferably, the hydrocarbon-based chain is i) linear or branched (C5-C 28 ) alkyl, ii) linear or branched (C6-C 28 ) alkenyl, iii) linear or branched (C6-C 28 ) alkynyl, and iii) preferably, the hydrocarbon-based chain is acyclic and linear; The hydrocarbon-based chain is One or more anionic groups (A - ), cationic group (C + ) and mixtures thereof; (**A - The groups are -C(O)OH, -C(O)O - , -SO3H, -S(O)2O - , -OS(O)2OH, -OS(O)2O - , -P(O)OH2, -P(O)O2 - , -P(O)O - , -P(OH)2, =P(O)-OH, -P(OH)O - , =P(O)-O - , =P-OH and =PO - and mixtures thereof, the anionic portion being selected from one or more cationic counterions M to achieve electrical neutrality of the PHA. + , for example i) alkali metals, ii) alkaline earth metals, iii) ammonium R a R b R c R d N + , iv) phosphonium R a R b R c R d P + R a represents a hydrogen atom, a (C1-C4) alkyl group or a (hetero)aryl(C1-C4) alkyl group, such as benzyl, preferably R a represents a hydrogen atom or a (C1-C4) alkyl group; R b , Rc and R d may be the same or different and represent a (C1-C4)alkyl group, a (hetero)aryl group, a (hetero)aryl(C1-C4)alkyl group, such as benzyl, a (hetero)cycloalkyl group or a (hetero)cycloalkyl(C1-C4)alkyl group, optionally substituted with one or more hydroxyl groups, or else R b and R c or R c and R d represents, together with the nitrogen or phosphorus atom thereof, a saturated or unsaturated, aromatic or non-aromatic heterocyclic ring, in particular a (C1-C4) alkyl optionally substituted with one or more hydroxyl groups; v) including the cationic forms of lysine or guanidine; **C + The cationic group is a cationizable amine group -NR b R c , ammonium group -N + R a R b R c , a phosphonium group -P + R a R b R c , a cationizable amidine group -C(=NR a )-NR b R c , amidinium group -C(=NR a )-N + R b R c R d , a cationizable guanidine group -N(R a )-C(=NR a )-NR b R c , a guanidinium group -N(R a )-C(=NR a )-N + R b R c R d or one or more R as previously defined a a cationizable imidazolyl group optionally substituted with a group or one or more R aand mixtures thereof to achieve electroneutrality of the PHA, wherein R a , R b , R c and R d is as defined above), the cationic moiety is coupled to one or more anionic counterions Q to ensure electroneutrality. - , such as halides, carboxylates, such as acetate or glutamate; optionally; ***R 1 The groups include a) halogen, such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(C1-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamido-C(O)-N(R a )2 or -C(S)-N(R a ) 2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl, and j) (hetero)cycloalkyl, k) cosmetically active agents, l) RX (wherein R represents a group selected from α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl, such as phenyl), m) thiosulfate; X is a') O, S, N (R' a ) or Si(R' b )(R' c ), b') S(O) r or (thio)carbonyl, c') or a combination of a') and b'), such as a (thio)ester, (thio)amide, (thio)urea or sulfonamide; R' a represents a hydrogen atom, or a (C1-C4) alkyl group or an aryl(C1-C4) alkyl group, such as benzyl, preferably R a represents a hydrogen atom; R' b and R' cmay be the same or different and represent a (C1-C4) alkyl or (C1-C4) alkoxy group, in particular the only one substituent being preferably selected from a) halogen and j) epoxide, etc., and / or one or more a') heteroatoms, such as O, S, N(R a ) and Si(R b )(R c ), b') S(O) r , (thio)carbonyl, c') or a combination of a') and b'), such as (thio)esters, (thio)amides, (thio)ureas, sulfonamides, etc., preferably esters -OC(O)- or -C(O)-O-, where r is equal to 1 or 2 and R a is as previously defined; preferably R a represents a hydrogen atom, and R b and R c is as previously defined); -R 2 is R 1 represents a hydrocarbon-based chain as previously defined; preferably, R 2 The hydrocarbon-based chain of the group is R 1 The number of carbon atoms in the group minus at least one carbon atom is subtracted (especially, for example, R 1 is uninterrupted and minus only one carbon atom when substituted with a carboxyl or carboxylate group), preferably R 1 having a number of carbon atoms equal to the number of carbon atoms in the group minus 2 carbon atoms); and b) optionally water The composition may be a composition, preferably a cosmetic composition, comprising: -(A) is different from (B) (i.e., R 1 is R 2 (different from -R 1 and R 2 In the same PHA, the A - and C + group, in which case the counterion M + and Q -It is understood that may be absent while still ensuring electroneutrality of the PHA.

[0029] According to a particular embodiment, R 1 is optionally interrupted by S or -OC(O)- or -C(O)-O-, more preferentially by S, and contains one or more ionic groups (A) as previously defined. - ), cationic group (C + ) and mixtures thereof; preferably substituted with ionic groups (A) as previously defined. - ) or cationic group (C + ) optionally interrupted by S or -OC(O)- or -C(O)-O-, more preferentially S (C5-C 20 ) alkyl chains and mixtures thereof. According to a particular embodiment, R 2 is an unsubstituted, uninterrupted, linear or branched, preferably linear, saturated hydrocarbon-based chain, preferably (C5-C 20 ) alkyl.

[0030] According to a particular embodiment, the molar percentage of units (A) is less than the molar percentage of units (B).

[0031] The term "copolymer" means that the polymer results from the polycondensation of different polymer repeat units with each other; for example, if the polymer results from the polycondensation of polymer repeat units (A) and (B), then polymer unit (A) is different from polymer unit (B) (more precisely, R 1 is R 2 is different).

[0032] According to a particular embodiment of the invention, the PHA copolymer consists of two different repeating polymer units selected from units (A) and (B) as previously defined.

[0033] More specifically, the PHA copolymers according to the present invention comprise repeat units of formula (I) as well as optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates:

[0034] [ka] (In formula (I), ·R 1 and R 2 is as previously defined, m and n are integers of 1 or more; preferably, the sum of n+m is 450 to 1400, both inclusive; preferably, m <nである)。

[0035] According to a particular embodiment, the PHA copolymer a) of the composition contains three different repeating polymer units (A), (B) and (C), preferably consisting of the following three different polymer units (A), (B) and (C) and also their optical or geometric isomers and solvates thereof, such as hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- Unit (B) -[-O-CH(R 3 )-CH2-C(O)-]- Unit (C) (In the polymer units (A), (B) and (C), -R 1 and R 2 is as previously defined, -R 3 represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms; - A as previously defined - and C + and / or one or more heteroatoms or R 1Optionally interrupted by groups a') to c'); this is in particular the definition for A as previously defined. - and / or C. + Substituted linear or branched (C1-C 28 ) alkyl groups, preferably the hydrocarbon-based group is selected from the group R 1 The group R corresponds to the number of carbon atoms, preferably minus at least 4 carbon atoms. 1 The number of carbon atoms in the alkyl group corresponds to the number of carbon atoms in the alkyl group. -(A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); Preferably, especially R 2 represents an alkyl group, and / or R 3 represents an alkyl group, preferably R 3 However, two carbon atoms are subtracted from R 2 It is understood that when expressing an alkyl group having a carbon number corresponding to the carbon number of units (A), the mole percentage of units (A) is less than the mole percentage of units (B) which is less than the mole percentage of units (C).

[0036] According to a particular embodiment, R 3 is an unsubstituted, uninterrupted, linear or branched, preferably linear, saturated hydrocarbon-based chain, preferably (C5-C 20 ) alkyl, more preferentially R 2 It has two fewer carbon units compared to the number of carbon atoms in

[0037] According to another particular embodiment, R 3 represents a linear or branched, preferably linear, saturated, hydrocarbon-based chain, said chain comprising A as previously defined - and C + and / or one or more heteroatoms or R 1 Optionally interrupted by groups a') to c') as defined for 1It has two fewer carbon atoms compared to the number of carbon atoms of

[0038] According to a particular embodiment of the invention, the PHA copolymer comprises the repeating unit of formula (II) and also its optical or geometrical isomers, its solvates such as its organic or mineral acid or basic salts and hydrates: [Chemical formula] In formula (II), ·R 1 , R 2 and R 3 are as defined previously; ·m, n and p are integers of 1 or more; preferably, the sum of n + m + p is 450 to 1400 including both end values; ·Preferably, m < n + p, and preferably R 3 represents an alkyl group having a carbon number corresponding to the carbon number of R 2 from which two carbon atoms have been subtracted.

[0039] According to a particular embodiment, the PHA copolymer a) of the composition contains four different repeating polymer units (A), (B), (C) and (D), and preferably consists of the following four different polymer units (A), (B), (C) and (D) and also their optical or geometrical isomers, their solvates such as their organic or mineral acid or basic salts and hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- unit (B) -[-O-CH(R 3 )-CH2-C(O)-]- unit (C) -[-O-CH(R 4 )-CH2-C(O)-]- unit (D) (In polymer units (A), (B), (C) and (D), -R 1 , R 2 and R 3is as previously defined; -R 4 is A as defined before - and C + and / or one or more heteroatoms or R 1 represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, optionally interrupted by groups a') to c'); in particular this is the same as defined for A as previously defined. - and C + and / or one or more heteroatoms or R 1 Linear or branched (C4-C 28 ) alkyl; -(A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), (C) is different from (A), (B) and (D), and (D) is different from (A), (B) and (C); -preferably, the molar percentage of units (A) is less than the molar percentage of units (B), preferably R 3 is R with two carbon atoms subtracted. 2 Represents an alkyl group having a carbon number corresponding to the carbon number of R. 4 represents an optionally substituted and / or interrupted alkyl group, an optionally substituted and / or interrupted alkenyl group, or an optionally substituted and / or interrupted alkynyl group, and the carbon number is reduced by 2 carbon atoms. 1 The number of carbon atoms is equivalent to is understood).

[0040] According to a particular embodiment, R 4 is an unsubstituted, uninterrupted, linear or branched, preferably linear, saturated hydrocarbon-based chain, preferably (C5-C 20 ) alkyl, more preferably the number of carbon atoms is R 2 This is four units fewer than the number of carbon atoms in

[0041] According to a particular embodiment of the invention, the PHA copolymer comprises a repeat unit of formula (III) and also its optical or geometric isomers, its organic or mineral acid or base salts and its solvates, such as hydrates: [ka] (In formula (III): ·R 1 , R 2 , R 3 and R 4 is as previously defined; m, n, p, and v are integers of 1 or more; preferably, the sum of n+m+p+v is 450 to 1400, inclusive; -preferably n>m+v; more preferentially n+p>m+v; -preferably R 3 R is the compound with two carbon atoms subtracted. 2 represents an alkyl group having a carbon number corresponding to the carbon number of R 4 is A as defined before - and C + and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 R optionally interrupted and / or subtracted by 2 carbon atoms by groups a') to c') as defined for 1 represents an alkynyl group optionally interrupted at the number of carbon atoms corresponding to the number of carbon atoms in

[0042] According to one embodiment, the PHA copolymer of composition a) more specifically contains five different repeating polymer units (A), (B), (C), (D) and (E), preferably consisting of the five different polymer units (A), (B), (C), (D) and (E) and also their optical or geometrical isomers, their organic or mineral acid or base salts and also their solvates, such as hydrates: -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- Unit (B) -[-O-CH(R 3 )-CH2-C(O)-]- Unit (C) -[-O-CH(R 4 )-CH2-C(O)-]- Unit (D) -[-O-CH(R 5 )-CH2-C(O)-]- Unit (E) (In the polymer units (A), (B), (C), (D) and (E), -R 1 , R 2 R 3 and R 4 is as previously defined; -R 5 is A as defined before - and C + and / or one or more heteroatoms or R 1 represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, optionally interrupted by groups a') to c') as defined above; - and C + and / or one or more heteroatoms or R 1 Optionally interrupted by groups a') to c') as defined for 28 ) alkyl groups; preferably, the hydrocarbon-based group is selected from the group R4 minus at least one carbon atom, preferably the group R 4 minus at least 2 carbon atoms, preferably minus 2 carbon atoms; -(A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E); (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); Preferably, especially R 2 represents an unsubstituted and uninterrupted alkyl group, and / or R 3 represents an alkyl group, and R 4 and R 5 A as defined before - and C + and / or one or more heteroatoms or R 1 an alkyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 In the case where R represents an alkynyl group, optionally interrupted by groups a') to c') as defined for R, the molar percentage of units (A) is less than the molar percentage of units (B) and less than the molar percentage of units (C); preferably, R 3 R is the compound with two carbon atoms subtracted. 2 represents an alkyl group having a carbon number corresponding to the carbon number of R 4 is A as defined before - and C +and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for R 1 A as defined above having a carbon number corresponding to the carbon number of - and C + and / or one or more heteroatoms or R 1 represents an alkynyl group optionally interrupted by groups a') to c') as defined for 5 is A as defined before - and C + and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for R 1 A as defined above having a carbon number corresponding to the carbon number of - and C + and / or one or more heteroatoms or R 1 It is understood that the alkynyl group represents an alkynyl group optionally interrupted by groups a') to c') as defined for (a).

[0043] According to a particular embodiment, R 5 is an unsubstituted, uninterrupted, linear or branched, preferably linear, saturated hydrocarbon-based chain, preferably (C5-C 20 ) alkyl, more preferably the number of carbon atoms is R 2 This is 6 units less than the number of carbon atoms.

[0044] According to a particular embodiment of the invention, the PHA copolymer comprises a repeat unit of formula (IV) and also its optical or geometric isomers, its organic or mineral acid or base salts and its solvates, such as hydrates: [ka] (In formula (IV): ·R 1 , R 2 , R 3 , R 4 and R 5 is as previously defined, m, n, p, v, and z are integers of 1 or more; preferably, the sum of n+m+p+v+z is 450 to 1400 inclusive; Preferably, R 1 is A as defined before - and C + and / or one or more heteroatoms or R 1 an alkyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 represents an alkynyl group optionally interrupted by groups a') to c') as defined for 2 and R 3 represents an alkyl group, and the group R 4 and R 5 is A as defined before - and C + and / or one or more heteroatoms or R 1 an alkyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1an alkenyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 When R represents an alkynyl group, optionally interrupted by groups a') to c') as defined for 3 is R with two carbon atoms subtracted. 2 represents an alkyl group having a carbon number corresponding to the carbon number of R 4 is R with two carbon atoms subtracted. 1 A as defined above having a carbon number corresponding to the carbon number of - and C + and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 represents an alkynyl group optionally interrupted by groups a') to c') as defined for 5 R is the compound with 4 carbon atoms subtracted. 1 A as defined above having a carbon number corresponding to the carbon number of - and C + and / or one or more heteroatoms or R 1 an alkenyl group optionally interrupted by groups a') to c') as defined for - and C + and / or one or more heteroatoms or R 1 represents an alkynyl group optionally interrupted by groups a') to c') as defined for

[0045] According to one embodiment, R 1 The groups are 1) A as defined above - and C + and preferably one or more A - 2) or A as defined above, - and C + and preferably one or more A - group and has one or more heteroatoms or R 1 a') to c') groups as defined for (a) above, preferably interrupted by a heteroatom such as O or S, preferably S, more particularly 2).

[0046] According to another embodiment of the present invention, the PHA copolymer is 1 is a hydrocarbon-based chain, in particular A as defined previously - and C + One or more (preferably one) groups selected from, preferably A - It is intended to represent an alkyl group, as defined above, substituted with a group.

[0047] According to one particular embodiment of the invention, the pHA copolymer is 1 -C(O)-OH, -C(O)O - , -SO3H, -S(O)2O - , -OS(O)2OH, -OS(O)2O - , -P(O)OH2, -P(O)O2 - , -P(O)O - , -P(OH)2, =P(O)-OH, -P(OH)O - , =P(O)-O - , =P-OH and =PO - and mixtures thereof, more preferentially selected from -C(O)-OH, -C(O)O - , -SO3H, -S(O)2O - , -P(O)OH2 and -P(O)O2 -One or more (preferably one) A selected from - Hydrocarbon-based chains, especially i) linear or branched (C5-C 28 ) alkyl.

[0048] According to a preferred embodiment, A - is the following group: carboxylate -C(O)O - , sulfonate -S(O)O - and phosphonates -P(O)O2 - , one or more cationic counterions M to achieve the electroneutrality of the PHA, as defined above; + Anionic moieties, especially alkali and alkaline earth metals, ammonium: R a R b R c R d N + or phosphonium: R a R b R c R d P + , preferably ammonium, (R a , R b , R c and R d is as previously defined, preferably R a represents a hydrogen atom; R b and R c may be identical or different, preferably identical, and represent a linear or branched, preferably branched (C1-C4) alkyl group, such as isopropyl or isobutyl, more preferentially isopropyl; R d represents a linear or branched (C1-C4) alkyl group, such as ethyl, and more specifically, M + is the diisopropylethylammonium group: (i-Pr)2N + (H) Et.

[0049] More preferentially, A - is the carboxylate group -C(O)O - M + (M+ is as previously defined).

[0050] According to another particular embodiment of the present invention, A - -C(O)-OH, -C(O)O - M + A group selected from (M + is as previously defined).

[0051] According to a particular embodiment of the invention, said substituted hydrocarbon-based chain, in particular alkyl, is linear.

[0052] According to another particular embodiment of the invention, said substituted hydrocarbon-based chain, in particular alkyl, is branched.

[0053] According to another particular embodiment of the invention, the group R 1 The hydrocarbon-based chain of is substituted and interrupted.

[0054] According to a particular embodiment of the invention, the group R 1 The hydrocarbon-based chain (especially the alkyl group as defined above) of - one or more (preferably one) A as defined above - substituted with a group; -O,S,N(R a ) and carbonyl or a combination thereof, for example, an ester, an amide or a urea, interrupted by one or more (preferably one) atoms or groups selected therefrom, a is as defined above, preferably R a represents a hydrogen atom); preferably, it is interrupted by one or more atoms selected from O and S, more preferentially O or S, in particular S atoms. In particular, R 1 The group is an interrupted hydrocarbon-based chain, particularly C7-C 20 , more specifically C8-C 18 and even more specifically C9-C 16 Represents alkyl.

[0055] According to an embodiment of the present invention, the composition comprises R 1 However, the above R 1 At the end of the chain opposite the carbon atom bearing the group, an anionic group (A - ) and cationic groups (C + a) one or more PHA copolymers a) substituted with one or more groups selected from:

[0056] According to a particular embodiment of the present invention, the PHA copolymer is 1 is substituted at the end of the chain (i.e. opposite the point of attachment of the alkyl group to the -CH- carbon atom of unit (A)) with one or more groups, preferably exactly one group (said group being -C(O)O - M + Selected from M + is as defined above), preferably by a sulfur atom -C(O)O - M + interrupted at the beta position (C3-C 28 ) alkyl group.

[0057] According to a particular embodiment of the present invention, the PHA copolymer is 1 i) one or more (preferably one) -C(O)-OH, -C(O)O - M + (M + A is selected from - Linear or branched (C3-C 28 ) alkyl group, more preferably A - is a carboxylate group -C(O)O - M + (M + is as previously defined); more specifically, R is -C(O)O - M + (M +is as previously defined), and is interrupted by a sulfur atom, preferably in the beta position relative to -C(O)O-M+ (C3-C 28 ) alkyl group.

[0058] According to an embodiment of the invention, the hydrocarbon-based chain R 1 is the following formula -(CH2) r -X-(ALK) u -G(X is as previously defined, in particular O, S, N(R a ), preferably S), and ALK is linear or branched, preferably branched (C1-C 10 )alkylene, more specifically (C1-C8)alkylene, r represents an integer between 6 and 11 inclusive, preferably between 7 and 10, for example 8; u is 0 or 1; G is A as previously defined. - Or C + group, preferably A - For example, -C(O)O - M + (M + is as previously defined).

[0059] In particular, the PHA copolymer is 2 Linear or branched (C3-C 20 ) alkyl, and linear or branched (C3-C 20 ) alkenyl, especially straight-chain hydrocarbon-based groups, more particularly (C3-C 20 ) alkyl or (C3-C 20 ) alkenyl.

[0060] According to one embodiment, the hydrocarbon-based group is a group R 1 preferably a group R 1 It has a number of carbon atoms equal to the number of carbon atoms in minus two.

[0061] According to one embodiment of the present invention, the PHA copolymer comprises a group R 2 is a linear or branched, preferably linear, (C4-C6) alkyl group, such as n-pentyl or n-hexyl.

[0062] According to another embodiment of the composition according to the invention, the PHA copolymer of the invention is a copolymer comprising an alkyl group R as previously defined. 1 and units (B) as previously defined, and linear or branched (C6-C 20 ) alkenyl, especially (C7-C 14 ) alkenyl, more specifically (C8-C 10 ) alkenyl groups (preferably linear and containing only one unsaturation at the chain end) (C), in particular -[CR 4 (R 5 )] q -C(R 6 )=C(R 7 )-R 8 (In the formula, R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl, preferably a hydrogen atom, and q represents an integer from 2 to 20, preferably from 3 to 10, more preferentially from 4 to 8, including the terminal value, for example 6), for example -[CH2] q -CH=CH2, and the like, and q represents an integer of 3 to 8, preferably 4 to 6, for example 5, including the terminal values.

[0063] According to one embodiment of the composition according to the invention, the PHA copolymer has A as previously defined. - Or C + , preferably A as defined above - an alkyl group R having 8 to 16 carbon atoms, substituted with one or more (preferably one) groups selected from 1 The compound includes a unit (A) having the following formula:

[0064] According to one embodiment of the composition according to the invention, the copolymer is a copolymer having a linear or branched, preferably linear, (C4-C6) alkyl, preferably (C4-C5) alkyl group R 2 , for example pentyl.

[0065] According to another embodiment of the composition according to the invention, the PHA copolymer is a copolymer having an alkyl group R as previously defined. 1 and units (B) as defined above, and linear or branched (C6-C 20 ) alkenyl, especially (C7-C 14 ) alkenyl groups, more specifically (C8-C 10 ) Units (C) containing alkenyl groups, preferably linear and containing only one unsaturation at the chain end, e.g., -[CH2] q and the like, and p represents an integer of 3 to 8, preferably 4 to 6, inclusive, for example 5.

[0066] According to one particular embodiment of the invention, in the PHA copolymer, the units (A) are A as previously defined - Or C + an alkyl group substituted by, in particular interrupted by, a heteroatom, such as S, or A as defined above; - Or C + an alkenyl group substituted with, in particular interrupted by, a heteroatom, such as S, or A as defined above; - Or C + and a hydrocarbon-based chain R, which is an alkynyl group as defined above, interrupted by a heteroatom, e.g., S. 1 and said units (A) are present in a molar percentage ranging from 0.1% to 80%, more preferentially from 0.5% to 70%, even more preferentially from 1% to 50%, and better still from 2% to 40%, from 20% to 40%.

[0067] Preferably, R of unit (A)1 is A as defined before - Or C + alkyl hydrocarbon-based chains substituted with, in particular, heteroatoms, such as S, and interrupted by, A as defined above; - Or C + an alkenyl hydrocarbon-based chain substituted by, in particular interrupted by, a heteroatom, such as S, or A as defined above; - Or C + and in particular an alkynyl hydrocarbon-based chain interrupted by a heteroatom, such as S, said units (A) are present in a molar percentage greater than or equal to 10%, more particularly greater than 20%, preferably between 25% and 35%.

[0068] According to another particular embodiment, R 1 is a cationizable amine group -NR b R c , ammonium group -N + R a R b R c , a cationizable amidine group -C(=NR a )-NR b R c , amidinium group -C(=NR a )-N + R b R c R d , a cationizable guanidine group -N(R a )-C(=NR a )-NR b R c , a guanidinium group -N(R a )-C(=NR a )-N + R b R c R d or one or more R as previously defined a a cationizable imidazolyl group optionally substituted by a group, or one or more R aone or more C selected from imidazolium groups optionally substituted with groups and mixtures thereof to achieve electroneutrality of the PHA; + group, where R a , R b , R c and R d is as previously defined), the cationic moiety is substituted with one or more anionic counterions Q - , for example halides.

[0069] According to a particular embodiment of the invention, in the PHA copolymer, the units (A) are present in a molar percentage ranging from 0.1 mol% to 99 mol%, preferentially in a molar percentage ranging from 0.5 mol% to 80 mol%, more preferentially in a molar percentage ranging from 1 mol% to 70 mol%, even more preferentially in a molar percentage ranging from 2 mol% to 60 mol%, better still in a molar percentage ranging from 5 mol% to 50 mol%; and even better still in a molar percentage ranging from 10 mol% to 40 mol%, and even more preferentially in a molar percentage ranging from 1 mol% to 50 mol%. units (A) are present in a molar percentage ranging from 25 mol% to 35 mol%; units (B) are present in a molar percentage ranging from 1 mol% to 99.9 mol%; preferentially from 2 mol% to 99.5 mol% and more preferentially from 5 mol% to 90 mol% of units (B); and / or units (C) are present in a molar percentage ranging from 0.5 mol% to 30 mol%, preferentially from 1 mol% to 20 mol% and more preferentially from 2 mol% to 10 mol% of units (C).

[0070] According to a more particular embodiment of the invention in the PHA copolymer, units (A) are present in a molar percentage ranging from 0.1% to 80%, more preferentially from 0.5% to 70%, even more preferentially from 1% to 60%, even better from 5% to 50%, from 10% to 40%; units (B) are present in a molar percentage ranging from 30% to 99.5%, units (C) are present in a molar percentage ranging from 0% to 30%, preferably from 1% to 25%, more preferentially from 5% to 20%, relative to the total, units (D) are present in a molar percentage ranging from 0% to 10%, preferably from 0.1% to 5%, more preferentially from 0.5% to 2%, relative to the total, and units (E) are present in a molar percentage ranging from 0% to 10%, preferably from 0.1% to 5%, more preferentially from 0.5% to 2%, relative to the total of the units. Advantageously, the PHA copolymer of the invention comprises from 60% to 80% by mole of units (B).

[0071] The mole percentage values ​​of units (A), (B) and (C) of a PHA copolymer are calculated relative to the total number of moles of (A)+(B) if the copolymer does not contain additional units (C); otherwise, if the copolymer of the invention contains three different units (A), (B) and (C), the mole percentage is calculated relative to the total number of moles of (A)+(B)+(C); otherwise, if the copolymer of the invention contains four different units (A), (B), (C) and (D), the mole percentage is calculated relative to the total number of moles of (A)+(B)+(C)+(D); otherwise, if the copolymer of the invention contains five different units (A), (B), (C), (D) and (E), the mole percentage is calculated relative to the total number of moles of (A)+(B)+(C)+(D)+(E).

[0072] According to a particular embodiment of the invention, the PHA copolymer comprises the following repeat units (A) and (B) and also their optical or geometric isomers, their organic or mineral acid or base salts and their solvates, such as hydrates: [ka] (p is an integer from 3 to 15; m and n are as previously defined; ALK1 is a linear or branched divalent C1-C 15 represents a hydrocarbon-based group, ALK2 is C3-C 20 represents an alkyl group, C + and A - is as defined previously).

[0073] Preferentially, the PHA copolymers of the invention comprise the following repeat units, and also their optical or geometric isomers, their organic or mineral acid or basic salts and their solvates, such as hydrates: [ka] m and n are as previously defined; M + is a cationic counterion as previously defined; In particular, the group R 1 and R 2 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably the (R) configuration.

[0074] More specifically, the group R 1 , R 2 and R 3 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably of the (R) configuration. More specifically, the group R 1 , R 2 , R 3 and R 4 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably of the (R) configuration. More specifically, R 1 , R 2 , R 3 , R 4 and R 5The stereochemistry of the carbon atom bearing the group is of the same (R) or (S) configuration, preferably of the (R) configuration. [ka] where m and n are as previously defined. M + is as previously defined, p is as defined above); [ka] where m and n are as previously defined. M + is as previously defined, p is as defined above; v is an integer greater than or equal to 1. The PHA copolymer of the invention preferably has a number average molecular weight ranging from 50,000 to 500,000, more preferentially from 50,000 to 150,000.

[0075] Molecular weight can be measured inter alia by size exclusion chromatography, the method of which is described in the examples below.

[0076] The PHA copolymer is in particular present in the composition according to the invention in a content ranging from 0.1% to 30% by weight, preferably from 0.1% to 25% by weight, relative to the total weight of the composition. Advantageously, the PHA copolymer a) is present in a content ranging from 0.1% to 65% by weight, preferably from 0.1% to 60% by weight, in particular from 1% to 50% by weight, more particularly from 3% to 40% by weight, more preferably from 5% to 35% by weight, even more preferably from 10% to 30% by weight and better still from 15% to 20% by weight, relative to the total weight of the composition.

[0077] The PHA copolymer preferably has a number average molecular weight ranging from 50,000 to 500,000, more preferentially from 50,000 to 150,000.

[0078] Molecular weight can be measured inter alia by size exclusion chromatography, the method of which is described in the examples below.

[0079] The copolymer may be present in the composition according to the invention in a content ranging from 0.1% to 30% by weight, preferably from 0.1% to 25% by weight, relative to the total weight of the composition.

[0080] Methods for preparing PHA copolymers The methods for preparing the PHA copolymers of the invention are known to those skilled in the art. Particular mention may be made of the use of microbial strains which produce "functionalizable" PHAs.

[0081] The term "functionalizable" means that the PHA copolymer comprises a hydrocarbon-based chain that contains one or more atoms or groups - also referred to as "reactive atoms or groups" - that can chemically react with another reagent to give a Σ-covalent bond functionalized by said reagent. The reagent is, for example, a compound that contains at least one nucleophilic group, and said functionalized hydrocarbon-based chain contains at least one electrophilic or nucleofugic atom or group, which reacts with the electrophilic group to Σ-covalently graft the reagent. The nucleophilic reagent can also react with one or more unsaturations of the alkenyl group to result in the covalent grafting of the functionalized hydrocarbon-based chain with said reagent. The addition reaction can also be a radical-based, Markovnikov or reverse Markovnikov type addition or nucleophilic or electrophilic substitution. The addition or condensation reaction may or may not be carried out via a radical pathway, with or without the use of catalysts or enzymes, under an inert atmosphere or under oxygen, at pressures higher than 1 atmosphere, and preferably with heating at 100°C or less.

[0082] The term "nucleophilic" refers to any atom or group that exhibits electron donating properties through an inductive effect +I and / or a mesomeric effect +M. Electron donating groups that may be mentioned include hydroxyl groups, thiol groups and amino groups.

[0083] The term "electrophilic" refers to any atom or group that exhibits electron-withdrawing properties through inductive effect -I and / or mesomeric effect -M. Electron-withdrawing species that may be mentioned include:

[0084] Microorganisms producing the PHAs of the invention, especially those having a C3-C5 hydrocarbon-based chain, can be naturally produced by the kingdom Bacteria, for example the Cyanobacteria of the order Nostocales (e.g. Nostoc muscorum, Synechocystis and Synechococcus), but mainly by the phylum Proteobacteria, for example the following classes: -Betaproteobacteria of the order Burkholderiales (Cupriavidus negator synonym Ralstonia eutropha) - alphaproteobacteria of the order Rhodobacterales (Rhodobacter capsulatus marine and photosynthetic) - Gammaproteobacteria (Acinetobacter junii) of the order Pseudomonadales, family Moraxellaceae.

[0085] Among the microorganisms of the kingdom bacteria, the genera Azotobacter, Hydrogenomonas or Chromatium are the most representative of PHA-producing organisms.

[0086] Organisms which naturally produce PHAs, in particular having a C3-C5 hydrocarbon-based chain, are in particular those of the Proteobacteria, for example the gammaproteobacteria, more particularly those of the order Pseudomonadales of the family Pseudomonadaceae, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis, Pseudomonas chlororaphis and preferably Pseudomonas putida GPo1 and Pseudomonas putida KT2440. Preferred are Pseudomonas putida and Pseudomonas putida, and in particular Pseudomonas putida GPo1 and Pseudomonas putida KT2440.

[0087] Certain organisms can also naturally produce PHAs without belonging to the order Pseudomonadales, such as Commamonas testosteroni, which belongs to the class of Betaproteobacteria in the order Burkholderiales in the family Comamonadaceae.

[0088] The PHA producing microorganism according to the present invention can also be a recombinant strain, if a β-oxidation PHA synthase metabolic pathway is present. The β-oxidation PHA synthase metabolic pathway is represented mainly by four enzyme classes, EC:2.3.1 B2, EC:2.3.1 B3, EC:2.3.1 B4 and EC:2.3.1 B5.

[0089] The recombinant strain may be from the kingdom Bacteria, e.g. Escherichia coli, or the kingdom Plantae, e.g. Chlorella pyrenoidosa: International Journal of Biological Macromolecules, 116, 552-562 “Influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (PHAs) by microalgae” or the kingdom Fungi, e.g. Saccharomyces cerevisiae or Yarrowia lipolytica: Applied Microbiology and Biotechnology 91, 1327-1340 (2011) “Engineering polyhydroxyalkanoate content and monomer composition in the oleaginous yeast Yarrowia lipolytica by modifying the β-oxidation multifunctional protein”).

[0090] Genetically modified microorganisms may also be used, which may, for example, increase the production of PHA, and / or improve the oxygen consumption capacity, and / or reduce autolysis, and / or change the monomer ratio. For PHA, it is known that most of the total production cost is spent on the culture medium, mainly the substrate / carbon source. Therefore, genetically modified microorganisms may be used with less nutrients (carbon source) for their growth, for example microorganisms that are photoautotrophic in nature, i.e., microorganisms that use light and CO2 as the main energy source.

[0091] The copolymers can be produced by biosynthesis in a known manner, for example by using microorganisms belonging to the genus Pseudomonas, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis, preferably Pseudomonas putida; and C2-C 20 , preferably C6-C 18 , carboxylic acids such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid or dodecanoic acid; sugars such as fructose, maltose, lactose, xylose, arabinose; n-alkanes such as hexane, octane or dodecane; n-alcohols such as methanol, ethanol, octanol or glycerol; methane or carbon dioxide.

[0092] This biosynthesis can optionally be carried out in the presence of an inhibitor of the β-oxidation pathway, such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid or phenylpropionic acid, preferably acrylic acid.

[0093] According to one embodiment, the process for preparing the PHA of the present invention uses microbial cells that produce PHA via genetically modified microorganisms (GMOs). The genetic modification can be to increase PHA production, increase oxygen absorption capacity, increase resistance to solvent toxicity, reduce autolysis, modify the ratio of PHA comonomers, and / or any combination thereof. In some of these embodiments, modifying the comonomer ratio of unit (A) increases the amount of the predominant monomer relative to (B) in the resulting PHA of the present invention. In another embodiment, the PHA-producing microbial cells replicate naturally.

[0094] An example of a genetically modified PHA-producing microbial strain may include Pseudomonas entomophila LAC23 (Adv. Healthcare Mater. 2017, 1601017 (DOI: 10.1002 / adhm.201601017).

[0095] An example of a genetically modified microbial strain that produces PHAs that can be functionalized or contain reactive groups can include Pseudomonas entomophila LAC23 (Biomacromolecules, 2014 Jun 9;15(6):2310-9. doi:10.1021 / bm500669s).

[0096] It is also possible to use a wild-type strain that produces 100% PHO (according to publication dx.doi.org / 10.1021 / bm2001999|Biomacromolecules, 2011, 12, 2126-2136).

[0097] It is also possible to use genetically modified microorganisms that produce phenylvalerate-co-3-hydroxydodecanoic acid HDD copolymers by the strain Pseudomonas entomophila LAC23 (Sci. China Life Sci., Shen R., et al., 57 No. 1, (2014).

[0098] This biosynthesis may also use nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium and iron.

[0099] For microbial culture, temperature, pH, dissolved oxygen (O D ) may be used.

[0100] The microorganisms can be cultured according to any known culture method, for example in a bioreactor in continuous or batch mode, fed or unfed mode.

[0101] 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 WO 2011 / 069244.

[0102] As previously defined, microbial strains producing PHAs that are functionalizable or contain reactive groups are, for example, those of the genus Pseudomonas, such as P. cichorii YN2, P. citronellolis, P. jessenii, and more generally of the species Pseudomonas putida, such as Pseudomonas putida GPo1 (synonymous with Pseudomonas oleovorans), P. putida KT2442, P. putida KCTC 2407 and P. putida BM01.

[0103] Carbon source: One way to utilize the PHA of the present invention is to introduce one or more organic compounds into the culture medium, the or these organic compounds preferably representing a carbon source selected from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof. In one embodiment, the organic compounds are preferably selected from alcohols, carboxylic acids and mixtures thereof.

[0104] Carbon sources can be classified as follows: 1) A carbon source via one or more organic compounds introduced into the medium: 2) According to a particular embodiment of the invention, the organic compound is an alcohol, in particular (C5-C 20 ) alkanols and / or carboxylic acids, in particular optionally substituted and / or interrupted (C5-C 20 ) Alkanoic acids, especially (C5-C 20 ) alkanoic acids, e.g. (C7-C 11 ) alkanoic acids, such as nonanoic acid or pelargonic acid and / or (C5-C 20 ) Alkenic acids, especially (C5-C 20 ) alkenoic acids, e.g. (C7-C 11 ) alkenoic acids, such as undecylenic acid, and mixtures thereof.

[0105] Carbon sources can be divided into three groups: - Group A: The organic compound may aid in the growth of the producing strain and aid in the production of PHA that is structurally linked to the organic compound. - Group B: The organic compounds may aid in the growth of the strain but are not involved in the production of PHAs that are structurally linked to the organic compounds. - Group C: Organic compounds do not contribute to the growth of the strain.

[0106] Such microbiological processes are known to those skilled in the art and are described in the scientific literature, among others: International Journal of Biological Macromolecules 28, 23-29 (2000); The Journal of Microbiology, 45, No. 2, 87-97, (2007).

[0107] According to one variant, the integration of a substrate structurally linked to a reactive atom or reactive group of the PHA of the present invention is directly introduced into the medium as the sole carbon source in a medium suitable for microbial growth (e.g. group A: alkenoic acids, especially terminal, for P. putida GPo1).

[0108] According to another variant, the integration of a substrate structurally linked to a reactive atom, in particular a halogen, or to a reactive group of the PHA of the present invention is introduced into the medium as a carbon source in a medium suitable for the growth of a microorganism together with a second carbon source as a co-substrate also structurally linked to the PHA (e.g. group B for P. putida GPo1: haloalkanoic acids, preferably terminal, such as terminal bromoalkanoic acids).

[0109] According to yet another variant, the integration of a substrate structurally linked to a reactive atom, particularly a halogen or reactive group, of the PHA of the present invention can be directly introduced into the medium suitable for microbial growth as a carbon source together with a second carbon source as a co-substrate that is also structurally linked to the PHA and a third carbon source as a co-substrate that is not structurally linked to the PHA (e.g., group C glucose or sucrose).

[0110] 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.

[0111] In an embodiment of the first aspect, the functionalized fatty acid is a functionalized hexanoic acid, a functionalized heptanoic acid, a functionalized octanoic acid, a functionalized nonanoic acid, a functionalized decanoic acid, a functionalized undecanoic acid, a functionalized dodecanoic acid, or a functionalized tetradecanoic acid.

[0112] The functionalization can be introduced by means of organic compounds chosen from the alcohol and / or carboxylic acid categories of precursors, including in particular: For the functionalization of PHAs with branched alkyl groups, see, for example, Applied and Environmental Microbiology, 60, No. 9, 3245-325 (1994); -For functionalization of PHAs with linear alkyl groups containing terminal cyclohexyl units, see for example: doi.org / 10.1016 / S0141-8130(01)00144-1; for functionalization of PHAs with unsaturated alkyl groups, preferably terminal: see, for example, doi.org / 10.1021 / bm8005616); -For functionalization of PHAs with linear alkyl groups, preferably containing halogens at the end of the hydrocarbon-based chain, see (doi.org / 10.1021 / ma00033a002); -For functionalization of PHAs with (hetero)aromatic alkyl groups, e.g. phenyl, benzoyl, phenoxy, see, for example, J. Microbiol. Biotechnol., 11, 3, 435-442 (2001); - for the functionalization of PHAs with linear alkyl groups, in particular those containing heteroatoms at the end of the hydrocarbon-based chain, see for example DOI 10.1007 / s00253-011-3099-4; - for the functionalization of PHAs with linear alkyl groups, in particular those containing a cyano function at the end of the hydrocarbon-based chain, see for example doi.org / 10.1111 / j.1574-6968.1992.tb05839.x; For the functionalization of PHAs, in particular with linear alkyl groups containing epoxy functional groups at the end of the hydrocarbon-based chain, see, for example, doi.org / 10.1016 / S1381-5148(97)00024-2.

[0113] The journal International Microbiology 16:1-15 (2013) doi:10.2436 / 20.1501.01.175) also mentions a large proportion of functionalized native PHAs.

[0114] In a particular embodiment of the invention, the fatty acids from group A are chosen from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and 5-cyanopentanoic acid, preferably 11-undecenoic acid.

[0115] In a particular embodiment of the invention, the fatty acid from group B is selected from halooctanoic acids, such as 8-bromooctanoic acid and 1-bromoundecanoic acid.

[0116] In a particular embodiment of the invention, the carbon source from group C is a monosaccharide, preferably glucose.

[0117] 3) Carbon source in the presence of antioxidants introduced into the medium: Another aspect of the invention is the use of a PHA-producing microbial strain in a medium suitable for the growth of the microorganism, said medium comprising a substrate structurally linked to the PHA, at least one carbon source not structurally linked to the PHA, and at least one oxidation, in particular β-oxidation, pathway inhibitor, whereby the growth of the microbial cells is carried out in said medium, and the microbial cells synthesize a PHA polymer of the invention, preferably a copolymer, in particular containing more than 95% of identical units, in which the comonomer ratio of units (A) to units (B) is different from that obtained in the absence of the β-oxidation pathway inhibitor.

[0118] Example of functionalization of PHA copolymers according to the invention starting from a PHA copolymer with unsaturated hydrocarbon-based chains according to scheme 1, in which compound (b) is prepared from a PHA copolymer (a) with unsaturated hydrocarbon-based chains that undergoes addition of a nucleophile YH, the reaction can be carried out radically or thermally, preferably radically, in particular in the presence of UV irradiation, optionally in the presence of a radical (photo)initiator such as 2-hydroxy-2-methylpropiophenone, in a (non-)polar solvent such as acetone, preferably at ambient temperature (25°C) with stirring for at least 5 minutes, the molar amount of (b) to (a) being between 1 and 10 (molar excess of (b)>(a)), preferably between 2 and 8, more preferentially between 3 and 7, such as 6; [ka] (In Scheme 1, -R 2 , m and n are as previously defined; -Y is -X-(ALK) p -A - , M + -X-(ALK) p -C + , Q -(p is 0 or 1; preferably 1), ALK is as defined above and preferably represents a (C1-C4) alkylene group, such as methylene or ethylene (1,1-ethylene), X is as defined above and preferably X=S, A - and C + is as previously defined, and M + is a cationic counterion as previously defined, and Q - is an anionic counterion as previously defined; -q' represents an integer of 2 to 20, including the terminal values, preferably 3 to 10, more preferably 4 to 8, for example 6, more preferably 3 to 8, preferably 4 to 6, for example 5). According to a preferred embodiment of the present invention, R has a hydrocarbon-based chain substituted by a carboxylate. 1 Process for preparing PHA compounds having a -X-(ALK) group p -C(O)O - , M + or -X-(ALK) p represents -C(O)OH, p is 0 or 1; preferably 1, ALK is as defined above and preferably represents a (C1-C4) alkylene group, such as methylene or ethylene (1,1-ethylene), X is as defined above and preferably X=S, M + is a cationic counterion as previously defined); Y is -X-(ALK) p Following this reaction, the amine R b R b R c Alkaline agents such as N (R b、 R b and R cis as defined before), preferably with a tri(C1-C4)alkylamine, for example N,N-diisopropylethylamine (DIPEA), it being understood that this reaction may 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° C. and 25° C., in particular with stirring, optionally followed by evaporation of the solvent, for example using a rotary evaporator.

[0119] Other further reactions can be carried out with double or triple unsaturations, such as Michael or Diels-Alder additions, which may or may not be controlled, catalytic (especially with Pd or Ni) or non-catalytic hydrogenation reactions, oxidation reactions, and reactions with electrophiles.

[0120] According to one particular embodiment of the invention, the PHA copolymer comprises a PHA copolymer having a total of 5 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more particularly 7 to 11 carbons, R 1 a linear or branched, saturated hydrocarbon-based chain R substituted and / or interrupted by atoms or groups as previously defined for 1 and a hydrocarbon-based chain R 2 is linear or branched (C3-C 20 ) alkenyl, especially (C5-C 14 ) alkenyl, more particularly (C7-C 10 ) alkenyl, which is preferably linear and contains only one unsaturation at the chain end, in particular -[CR 4 (R 5 )] q -C(R 6 )=C(R 7 )-R 8 (R 4 , R 5 , R 6 , R 7 and R 8may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl, preferably a hydrogen atom; q represents an integer of 2 to 20, preferably 3 to 10, more preferentially 4 to 8, inclusive, for example 6, for example -[CH2] q represents -CH=CH2, q is an integer between 3 and 8, preferably between 4 and 6, inclusive, for example 5, and contains between 1% and 99%, preferentially between 2% and 50%, even more preferentially between 3% and 40% unsaturation, and even more specifically between 3% and 30% unsaturation, better still between 5% and 20% unsaturation. A) These unsaturations can be chemically modified via addition reactions with particles, chemical compounds or polymers, such as radical addition, Michael addition, electrophilic addition, Diels-Alder, halogenation, hydration or hydrogenation reactions, and preferably hydrothiolation reactions. In particular, hydrothiolation reactions are carried out using thermal, redox or photochemical initiators and organic compounds bearing sulfhydryl groups, in particular - linear, branched, cyclic or aromatic alkanethiols containing from 1 to 14 carbon atoms, such as methane-, ethane-, propane-, pentane- or cyclopentane-thiol, preferably hexane-, cyclohexane-, heptane-, octane-, phenylethane-, 4-tert-butylphenylmethane- or 2-furanmethane-thiol; -Organosiloxanes with thiol functional groups, such as (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldimethoxysilane, 2-(triethoxysilyl)ethanethiol or mercaptopropyl-isobutyl-POSS; - thiol-based silicone oils, in particular those described in the literature (DOI: 10.1016 / j.actbio.2015.01.020); - thiol-based oligomers or polymers with reactive functional groups, such as amines, alcohols, acids, halogens, thiols, epoxides, nitriles, isocyanates, heteroatoms, preferably cysteine, cysteamine, N-acetylcysteamine, 2-mercaptoethanol, 1-mercapto-2-propanol, 8-mercapto-1-octanol, thiolactic acid, thioglycolic acid, 3-mercaptopropionic acid, 11-mercaptoundecanoic acid, polyethylene glycol dithiol, 3-mercaptopropionitrile, 1,3-propanedithiol, 4-cyano-1-butanethiol, 3-chloro-1-propanethiol, 1-thio-β-D-glucose tetraacetate; and -thiols obtainable from disulfide reduction, such as phenyl disulfide or furfuryl disulfide The method may be carried out in the presence of a compound selected from: Examples of radical initiators that may be mentioned include tert-butylperoxy-2-ethylhexanoate, cumene perpivalate, tert-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy- 2,4-Dimethylvaleronitrile), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,4-bis(tert-butylperoxycarbonyl)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl 4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, 1,3-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5 -Bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-tert-butyldiperoxyisophthalate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butylperoxy-α-methylsuccinate, di-tert-butylperoxydimethylglutarate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, oxy)hexane, diethylene glycol bis(tert-butylperoxycarbonate), di-tert-butylperoxytrimethyladipate, tris(tert-butylperoxy)triazine, vinyltris(tert-butylperoxy)silane phenothiazine, tetracene, perylene, anthracene, 9,10-diphenylanthracene, thioxanthone, benzophenone, acetophenone, xanthone, fluorenone, anthraquinone, 9,10-dimethylanthracene, 2-ethyl-9,10-dimethyloxyanthracene, 2,Examples of initiators include 6-dimethylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, xanthopinacol, 1,2-benzanthracene, and 9-nitroanthracene. Each of these initiators may be used alone or in combination with the others. The chemical reactions mentioned above are known to those skilled in the art. The following documents may be mentioned, inter alia: Synthesis and preparation of PHAs modified 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 PHAs modified 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)202:11<2281::AID-MACP2281>3.0.CO;2-9;Macromolecular Chemistry and Physics,vol.202,11,2281-2286(2001);Synthesis and preparation of PHAs modified 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 unsaturated products can also be chemically modified, for example via controlled or uncontrolled oxidation reactions with concentrated or dilute, preferably concentrated, alkaline agents such as permanganates (preferably potassium permanganate), or via ozonolysis, which makes it possible to obtain PHAs with carboxyl groups at the terminal positions of the side chains. Example of functionalization of PHA copolymers according to the invention starting from a PHA copolymer (a) with an unsaturated hydrocarbon-based chain according to scheme 2, with an aliphatic chain terminating with a carboxyl group (c) or a carboxylate group (d), This is in particular carried out by uncontrolled oxidation with concentrated or diluted, preferably concentrated, alkaline agent permanganates (preferably potassium permanganate) and / or in the presence of sodium or potassium carbonate, in a mixture of a halogenated solvent and a (C1-C4) carboxylic acid, such as acetic acid, in water or else in the presence of a crown ether, preferably 18-crown-6, else the oxidation is carried out starting from osmium oxide OsO6 in the presence of a polar protic solvent, such as a (C1-C6) alkanol, for example t-BuOH and oxone, so that a PHA is obtained with an aliphatic chain (c) terminated by a carboxyl group (this carboxyl group can be, for example, obtained with an alkaline agent M + OH - (which can be identified using the formula (d) of the present invention); Another example of the functionalization of a PHA copolymer according to the invention having an aliphatic chain (f) bearing an ammonium group starts from a PHA copolymer (a) having an unsaturated hydrocarbon-based chain according to Scheme 2, where (a) is an amine R b R cNH to give a PHA copolymer (e) having an aliphatic chain with a cationizable amino group, which can then be reacted with a halide of Ra, such as RaQ, to give a PHA (f) having an aliphatic chain with an ammonium group. [ka] (In Scheme 2, -R 2 , q', m and n are as previously defined; M + is a cationic counterion as previously defined, Q - is an anionic counterion as previously defined, and R a , R b and R c is as previously defined, in particular a (C-C) alkyl group optionally substituted by one or more hydroxyl groups, or alternatively R b and R c together with the nitrogen atom carrying them form a monocyclic or polycyclic heterocycle, preferably a monocyclic heterocycle, such as pyridino, morpholino, piperazino, piperidino, and more preferentially R' and R" represent a (hydroxy)(C1-C4)alkyl group, such as hydroxyethyl).

[0121] The chemical reactions mentioned above are known to those skilled in the art. The following documents may in particular be mentioned: 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); and 10.1021 / bm025728h; Biomacromolecules, vol 4,2,193-195(2003).

[0122] Example of functionalization of PHA copolymers according to the invention starting from a PHA copolymer (g) bearing epoxide groups according to scheme 3, where the PHA copolymer (g) bearing epoxide groups can be reacted with a nucleophile YH as defined previously to give a PHA (h) according to the invention bearing a hydrocarbon-based group substituted with a hydroxyl group and a group Y as defined previously; the PHA (g) bearing epoxide groups can also be reacted with an amine R′R″NH to give a PHA (i) bearing an aliphatic chain substituted with a hydroxyl group and with an amino group, which can be catalyzed, for example, in the presence of an acid HQ, to give a PHA copolymer (j) bearing ammonium groups, or else the (PHA) copolymer (i) can be reacted with a nucleophile YH as defined previously to give a PHA (h) bearing a hydrocarbon-based group substituted with a hydroxyl group and with a group Y as defined previously; a -Q, e.g. R a with a halide, preferably an alkyl halide, to result in a PHA copolymer (k) having ammonium groups). [ka] (In Scheme 3: Y, m, n, q′ and R 2is as defined in scheme 1, or alternatively Y represents a group R'R"N-, where R'R" represents a hydrogen atom or a (C1-C6)alkyl group optionally substituted by one or more hydroxyl groups, or alternatively R' and R" together with the nitrogen atom they carry form a monocyclic or polycyclic heterocycle, preferably a monocyclic heterocycle, such as pyridino, morpholino, piperazino, piperidino, and more preferentially R' and R" represent a (hydroxyl)(C1-C4)alkyl group, such as hydroxyethyl).

[0123] The epoxide structure may be obtained through conventional methods known to those skilled in the art, either through biotechnological processes or through chemical processes such as the oxidation of unsaturation as previously mentioned. The epoxide group may be a carboxylic acid, maleic anhydride, an amine, an alcohol, a thiol, an isocyanate, at least one linear or branched, cyclic or acyclic, saturated or unsaturated C1-C 20 All of these reagents can react with hydrocarbon-based chains, including (di)(C1-C6) alkylamines, where the alkyl groups can be replaced with one or more hydroxyl groups, such as diethanolamine or dihydroxyethanolamine. The amino groups can then be protonated or quaternized in conventional manner.

[0124] In particular the following documents may be mentioned: -Preparation of PHA bearing charges starting with diethanolamine:10.1021 / bm8005616,Biomacromolecules,vol 9,8,2091-2096(2008); -Preparation of PHA bearing charges starting with sodium 3-mercapto-1-propanesulfonate:10.1021 / acs.biomac.9b00870 Biomacromolecules,vol.20,9,3324-3332(2019); -Preparation of PHA including a native epoxide unit:10.1016 / S1381-5148(97)00024-2);Reactive and Functional Polymers,vol.34,1,65-77(1997).

[0125] Example of functionalization of a PHA copolymer according to the invention, starting from a PHA copolymer having a hydrocarbon-based chain terminating in a nucleofugic group NF(l) according to the following scheme 4 (wherein a PHA copolymer having an aliphatic chain carrying a nucleofugic group (l) is reacted with a nucleophile YH, resulting in a PHA having an aliphatic chain terminating in a group Y (m) according to the invention): [ka] (In Scheme 4, Y, m, n, q′ and R 2 is as defined in scheme 1). M corresponds to an organic or inorganic nucleofugic group that can be substituted by a nucleophilic group, preferably said nucleophilic group is a heteroatom that donates electrons via the +I and / or +M effect, such as O, S or N. Preferably, the nucleofugic group M is selected 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, the following literature may be mentioned: 10.1016 / j.ijbiomac.2016.11.118, International Journal of Biological Macromolecules, vol.95,796-808(2017).

[0126] Example of functionalization of a PHA copolymer according to the invention starting from a PHA copolymer having a hydrocarbon-based chain with cyano groups according to the following scheme 5, where the PHA copolymer having an aliphatic chain (p) is substituted with a cyano or nitrile group: - in a first step i), a PHA copolymer having a side chain containing a cyano or nitrile group is reacted with an organo-alkali metal or organo-magnesium compound Y-MgHal, Y-Li or Y-Na, followed by hydrolysis to obtain a PHA copolymer (q) having a side chain containing a group Y grafted with a ketone function according to the invention. The ketone function can be converted by thionation, for example with S8 in the presence of an amine, or with Lawesson's reagent. The thioketone, after complete reduction ii) (for example by Clemmensen reduction), leads to a PHA copolymer having a side chain containing a group Y grafted with an alkylene group. Alternatively, the thioketone can be subjected to a controlled reduction iii) with conventional reducing agents to obtain a PHA copolymer having a side chain containing a group Y grafted with a hydroxyalkylene group. The cyano group of the starting PHA copolymer can be reacted with water, after hydration to give an amide derivative, followed by hydrolysis iv) to a carboxyl derivative (t) according to the invention. The latter can then be converted with an alkaline agent M + OH - in the presence of chlorination to obtain copolymers (u) with carboxylate aliphatic chains according to the invention. The cyano groups of the starting PHA copolymers can also be reduced vii) to obtain cationizable amine derivatives (v) which can then be subjected to amine alkylation and / or chlorination reactions to obtain copolymers (w) with ammonium aliphatic chains according to the invention. PHA copolymers with hydrocarbon-based chains with nitrile functional groups are prepared via conventional methods known to those skilled in the art. For example, the following literature can be mentioned: 10.1016 / 0378-1097(92)90311-B, FEMS Microbiology Letters, vol.103,2-4,207-214(1992). [ka] (In Scheme 5: Y, m, n, q′, Y and R 2 , R a , R b , R c , M + and Q -is as defined previously).

[0127] Example of functionalization of a PHA copolymer according to the invention starting from a PHA copolymer having a hydrocarbon-based chain at the chain end according to Scheme 6 below: [ka] (In Scheme 6: R 1 , R 2 , m, n and Y are as previously defined; R' 1 -ALK-A - , M + or -ALK-C + , Q - (ALK, A - , C + , M + and Q - represents a group selected from, as previously defined.

[0128] These chain end grafts onto PHA polymers are known to those skilled in the art. For example, the following documents may be mentioned: -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 Polymer,vol.35,19,4156-4162(1994); -Preparation of PHA oligomers by methanolysis:10.1021 / bm060981t, Biomacromolecules, vol. 8, 4, 1255-1265 (2007).

[0129] Other methods known to those skilled in the art may also be mentioned: -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 polycondensation with divinyl adipate catalysed with a lipase:10.1021 / bm9011634,Biomacromolecules,vol.10,12,3176-3181(2009); -Synthesis of PHB-b-PHO copolymers coupled via 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 the PHO and the amine functions of the chitosan:10.1002 / app.24276;Journal of Applied Polymer Science,vol.103,1,(2006); -Transesterification of PHAs with propargyl alcohol in order to produce PHA oligomers that are 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); -Epoxidation of chain-end unsaturation and chain-end grafting of acid:10.14314 / polimery.2017.317;Polimery,vol.62,4,317-322(2017); - Grafting of organosiloxane unit at chain end onto PHA:10.1016 / j.reactfunctpolym.2014.09.008;Reactive and Functional Polymers,vol.84, 53-59(2014).

[0130] Combination of the previously described grafted PHA copolymers of the invention according to Scheme 7: [ka] In Scheme 7, R' 1 , R 2, m, n and Y are as previously defined, and X' represents a reactive atom or group capable of reacting with an electrophilic E or nucleophilic Nu atom or group to form a Σ covalent bond; when X' is an electrophilic or nucleophilic group, the reagent R' 1 -Nu, and when X' is a nucleophilic group Nu, R' 1 -Can react with E to form a Σ covalent bond.

[0131] By way of example, the Σ covalent bonds or linking groups that may result from the condensation of electrophiles and nucleophiles are given in the table below:

[0132] [Table 1]

[0133] [Table 2]

[0134] It is also possible to start with a PHA functionalized on the side chain and perform the chain end grafting in a second step, as depicted in Scheme 8. Vice versa, the chain end grafting can be performed in a first step, followed by functionalization of the functionalizable pendant side chain in a second step. [ka] In Scheme 8, R' 1 , R 2 , m, n and Y are as previously defined, and

[0135] All these chemical reactions are known to those skilled in the art.) For example, the following documents may be mentioned: -Synthesis and preparation of PHAs modified with thiol-ene followed by reaction on the new grafted function:10.1021 / ma0304426;Macromolecules,vol.37,2,385-389(2004); -Grafting of PEG and of PLA onto PHAs functionalized with acids:10.1002 / marc.200900803 and 10.1002 / mabi.200390033; -Synthesis and preparation of PHAs modified with polyethylene glycol dithiol:10.1021 / acs.biomac.9b00479.

[0136] b) water The composition according to the invention preferably comprises water. Water suitable for use in the present invention may be tap water, distilled water, spring water, floral water, such as cornflower water and / or mineral water, such as Vittel water, Lucas water or La Roche Posay water and / or thermal water.

[0137] Preferably, water represents the main component by weight of the composition. According to one embodiment, the amount of water by weight is between 20% and 99%, in particular between 30% and 95% and more preferentially between 40% and 90% by weight relative to the total weight of the composition.

[0138] According to one embodiment, the composition is an aqueous composition, more preferentially a composition comprising less than 10% by weight of fatty substances relative to the total weight of the composition under consideration, preferably less than 5% and even more preferentially less than 2% and, according to one even more preferred embodiment, free of fatty substances.

[0139] c) Further solvent The composition may further comprise one or more further solvents c).

[0140] Preferably, the further solvent is selected from water-miscible solvents.

[0141] According to the present invention, the term "water-miscible solvent" denotes a compound that is liquid at room temperature and miscible with water (miscibility with water is greater than 50% by weight at 25° C. and atmospheric pressure).

[0142] Further solvents that may be used in the compositions of the invention may also be volatile. This or these may be polar or non-polar, protic or aprotic, preferably polar. More particularly, protic and polar.

[0143] Among the further solvents that may be used in the composition according to the invention, mention may be made in particular of polar protic solvents, such as alcohols, and in particular lower monoalcohols containing from 2 to 6 carbon atoms, such as ethanol and isopropanol.

[0144] According to one embodiment, the composition according to the invention comprises one or more further solvents, preferably chosen from monoalcohols containing from 2 to 6 carbon atoms, such as ethanol and isopropanol, preferably in an amount of less than 70%, more preferentially less than 20%, even more preferentially less than 10% and more particularly less than 8%, relative to the total weight of water, and optionally a fatty substance d).

[0145] d) fatty substances According to a particular embodiment of the invention, the composition also comprises one or more fatty substances.

[0146] The term "fatty substances" refers to organic compounds that are insoluble in water (solubility less than 5%, preferably less than 1%, and even more preferentially less than 0.1%) at normal room temperature (25°C) and atmospheric pressure (760 mmHg). They have in their structure at least one hydrocarbon-based chain containing at least 6 carbon atoms or at least two strings of siloxane groups. Moreover, fatty substances are generally soluble in organic solvents, such as chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane, under the same temperature and pressure conditions.

[0147] The fatty substances of the invention are of natural or synthetic origin, preferably of natural and more preferentially of vegetable origin. They differ from fatty acids, since salified fatty acids generally constitute soaps that are soluble in aqueous media.

[0148] According to a particular embodiment of the invention, the composition comprises one or more fatty substances that are not liquid at 25° C. and atmospheric pressure.

[0149] wax According to a particular embodiment, the composition of the invention comprises one or more waxes.

[0150] The term "wax" means a lipophilic compound that is solid at room temperature (25°C), has a reversible solid / liquid state change and has a melting point that may be above 30°C, up to 200°C, in particular up to 120°C.

[0151] In particular, waxes suitable for use in the present invention may have a melting point of 45°C or higher, in particular 55°C or higher.

[0152] The composition according to the invention preferably comprises a wax content ranging from 0.5% to 30% by weight, in particular from 1% to 20% by weight and more particularly from 2% to 15% by weight, relative to the total weight of the composition.

[0153] According to a particular embodiment of the invention, the composition according to the invention is solid, in particular anhydrous. It may be in the form of a stick, and a polyethylene microwax is used in microcrystalline form, with an aspect ratio at least equal to 2, and with a melting point ranging from 70 to 110°C, preferably from 70 to 100°C, so as to reduce or even eliminate the presence of layers in the solid composition. These needle-like crystallites, in particular their dimensions, can be visually characterized according to the following method:

[0154] Paste-like compound According to a particular embodiment, the composition according to the invention comprises one or more pasty compounds.

[0155] For the purposes of the present invention, the term "pasty compound" means a lipophilic fatty compound which undergoes a reversible solid / liquid state change, has an anisotropic crystalline structure in the solid state and comprises a liquid fraction and a solid fraction at a temperature of 23°C.

[0156] According to one embodiment, the composition contains one or more fatty substances d), which are hydrocarbon-based fatty substances that are liquid at 25° C. and atmospheric pressure.

[0157] Liquid fatty substances based on hydrocarbons are especially C6-C 16 Hydrocarbon or olefins containing more than 16 and up to 60 carbon atoms, preferably C6-C 16 and in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides or fluorinated oils of synthetic origin, fatty alcohols, fatty acids and / or fatty alcohol esters and silicones. In particular, the liquid fatty substance is selected from non-silicone oils.

[0158] For the purposes of the present invention, fatty alcohols, fatty esters and fatty acids more particularly come to mind those containing one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 60 carbon atoms, optionally substituted in particular with one or more hydroxyl groups OH (in particular with 1 to 4 hydroxyl groups). When they are unsaturated, these compounds may contain 1 to 3 unsaturated, preferably 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

[0159] C6-C 16 As regards alkanes, these compounds are linear or branched and optionally cyclic; preferably, the fatty substances c) of the invention are linear or branched C-C 14 , and more preferentially C9-C 13 , and more preferentially C9-C 12The linear or branched hydrocarbons containing more than 16 carbon atoms may be selected from liquid paraffins, liquid petroleum jelly, polydecene and hydrogenated polyisobutenes, such as Parleam®. Examples that may be mentioned include hexane, decane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isodecane and isododecane. The linear or branched hydrocarbons containing more than 16 carbon atoms may be selected from liquid paraffins, liquid petroleum jelly, polydecene and hydrogenated polyisobutene, such as Parleam®.

[0160] Comprehensive solubility parameter according to Hansen solubility space is 20 (MPa) 1 / 2 Among the hydrocarbon-based liquid fatty substances d) below, mention may be made of oils which may be chosen from natural or synthetic hydrocarbon-based oils, optionally fluorinated and optionally branched, either alone or as a mixture.

[0161] According to a very advantageous embodiment, the composition according to the invention comprises one or more fatty substances which are one or more hydrocarbon-based oils.The hydrocarbon-based oils can be volatile or non-volatile.According to a preferred embodiment of the invention, the fatty substance d) is a linear or branched hydrocarbon-based oil, which is volatile, in particular selected from undecane, decane, dodecane, isododecane, tridecane and mixtures of various of these volatile oils, preferably containing isododecane in the mixture or a mixture of undecane and tridecane.

[0162] According to another particular embodiment, the liquid fatty substance d) is a mixture of volatile and non-volatile hydrocarbon-based oils, which mixture preferentially comprises dodecane or isododecane as the volatile oil.

[0163] In particular, the fatty substances d) of the present invention are preferably of natural origin, C9-C 12 A mixture of alkanes, the chains of which have 9 to 12 carbon atoms, preferably linear or branched C9-C 12 This mixture contains alkanes, in particular those with the INCI name C9-C 12Alkane, CAS 68608-12-8, known as Vegelight Silk® sold by BioSynthIs. This volatile biodegradable mixture of volatile oils is obtained from coconut oil (viscosity is 0.9-1.1 cSt (40°C), which has a flash point of 65°C).

[0164] According to one embodiment, the composition contains only oils that are liquid at 25° C. and atmospheric pressure. According to another embodiment, the composition contains at least 80% of a hydrocarbon-based oil that is liquid at 25° C. and atmospheric pressure, which is preferably volatile and more preferentially selected from isodecane, decane, Cetiol UT® and Vegelight Silk®.

[0165] According to another embodiment, the composition may comprise volatile and non-volatile oils, especially in a volatile / non-volatile oil ratio of 4 or more.

[0166] According to another embodiment, the composition contains 0 to 10% silicone oil, preferably 0 to 5% silicone oil.

[0167] Among the volatile silicone oils that may be mentioned are volatile linear or cyclic silicone oils, in particular those with a viscosity of 8 centistokes (cSt) (8x10 -6 m 2 / s) or less, in particular those containing 2 to 10 silicon atoms, especially those containing 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups containing 1 to 10 carbon atoms. Volatile silicone oils that may be used in the present invention may include dimethicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof, in particular having a viscosity of 5 and 6 cSt.

[0168] Non-volatile silicone oils may include linear or cyclic non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes containing alkyl, alkoxy and / or phenyl groups, either pendant or at the end of the silicone chain, containing from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicone, phenyl dimethicone, phenyl trimethylsiloxy diphenyl siloxane, diphenyl dimethicone, diphenyl methyl diphenyl trisiloxane, 2-phenylethyl trimethylsiloxy silicate, and pentaphenyl silicone oil.

[0169] The hydrocarbon-based oil may be selected from: * Hydrocarbon-based oils containing 8 to 14 carbon atoms, and in particular: - Branched C8~C 14 Alkanes, e.g., C8-C derived from petroleum 14 Isoalkanes (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and oils sold, for example, under the trade names Isopar or Permethyl; linear alkanes, such as n-dodecane (C12) and n-tetradecane (C14), sold under the respective references Parafol 12-97 and Parafol 14-97 by Sasol, and also mixtures thereof, undecane-tridecane mixtures, mixtures of n-undecane (C11) and n-tridecane (C13) as obtained in examples 1 and 2 of patent application WO 2008 / 155059 from Cognis, and mixtures thereof, and also mixtures of n-undecane (C11) and n-tridecane (C13) Cetiol Ultimate® from BASF, *Short chain esters (containing 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate, or n-butyl acetate; *Hydrocarbon-based oils of plant origin, such as triglycerides composed of fatty acid esters of glycerol (these fatty acids are C4-C 24and the chains may optionally be linear or branched and saturated or unsaturated; these oils are in particular triglycerides of heptanoic or octanoic acid, or alternatively wheat germ oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazel oil, macadamia oil, jojoba oil, alfalfa oil, poppy seed oil, red kuri pumpkin oil, etc. squash oil, seam oil, pumpkin oil, rapeseed oil, black currant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, kukui oil, passionflower oil, musk rose oil or coconut oil; shea butter; or else caprylic / capric triglycerides, such as those sold by the company Stearinerie Dubois or under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, *Synthetic ethers containing 10 to 40 carbon atoms, * Linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutenes such as Parleam®, squalane and liquid paraffin and mixtures thereof; *Formula R 1 C(O)-OR 2 R oil etc. 1 represents a linear or branched fatty acid residue containing 1 to 40 carbon atoms, R 2 Especially R 1 +R 2 Branched, hydrocarbon-based chains containing 1 to 40 carbon atoms, provided that ≧10, e.g., Purcellin oil (cetosteryl octanoate), isopropyl myristate, isopropyl palmitate, C 12 -C 15Alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters, more preferentially linear or branched C8-C 10 Fatty acids and linear or branched C 12 -C 18 It denotes esters of fatty alcohols, alone or in mixtures with alkanes derived from the complete hydrogenation / reduction of fatty acids obtained from Cocos nucifera (coconut) oil, in particular dodecane or a mixture of cocoyl caprylate / caprate and dodecane; mention may be made of those with the INCI names Coconut Alkanes (and) Cococaprylate / Caprate, sold by Grant Industries under the trade name Vegelight 1212LC®), * Fatty alcohols which are liquid at room temperature and have a branched and / or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol.

[0170] In addition to the liquid fatty substances based on hydrocarbons, the composition according to the invention may contain silicone oil.When silicone oil is present in the composition according to the invention, its amount is preferably not more than 10% by weight relative to the weight of the composition, more particularly less than 5% by weight relative to the total weight of the composition.

[0171] In particular, the composition comprises at least one liquid fatty substance d) based on hydrocarbons selected from: vegetable oils formed by fatty acid esters of polyols, in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, calendula oil, palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil, coconut oil or cereal germ oil; - linear, branched or cyclic esters containing more than 6 carbon atoms, in particular 6 to 30 carbon atoms; in particular isononyl isononanoate; and more specifically, the formula R d -C(O)-OR e where R d represents a higher fatty acid residue containing 7 to 19 carbon atoms, and R e represents a hydrocarbon-based chain containing 3 to 20 carbon atoms, such as palmitate, adipate, myristate and benzoate, in particular diisopropyl adipate and isopropyl myristate; more preferentially, the formula R d -C(O)-OR e where R d represents a higher fatty acid residue containing 8 to 10 carbon atoms, and R e represents a hydrocarbon-based chain containing 12 to 18 carbon atoms); - Hydrocarbons and in particular volatile or non-volatile linear, branched and / or cyclic alkanes, for example optionally volatile C5-C 60 Isoparaffins such as undecane, dodecane, isododecane, tridecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane or Isopars and mixtures thereof; or alkanes obtained by complete hydrogenation / reduction of a mixture of fatty acids derived from Cocos nucifera (coconut) oil, such as dodecane, C9-C 12 A mixture of alkanes, the chains of which have from 9 to 12 carbon atoms, preferably linear or branched C9-C 12 alkanes, especially dodecane), or else liquid paraffin, liquid petroleum jelly or hydrogenated polyisobutylene; - ethers containing 6 to 30 carbon atoms; - ketones containing 6 to 30 carbon atoms; aliphatic fatty monoalcohols whose hydrocarbon-based chain does not contain any substituents and contain 6 to 30 carbon atoms, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; - polyols containing 6 to 30 carbon atoms, for example hexylene glycol; and - their mixtures, for example linear or branched C8-C 10 Fatty acids and C 12 -C 18 Mixtures of esters of alkanes, especially dodecanes, obtained from the complete hydrogenation / reduction of a mixture of fatty alcohols and fatty acids from Cocos nucifera (coconut) oil, such as a mixture of cococaprylate / caprate and dodecane; those with the INCI name Coconut Alkanes (and) Cococaprylate / caprate sold by Grant Industries under the trade name Vegelight 1212LC®; or C9-C 12 A mixture of alkanes, the chains of which contain from 9 to 12 carbon atoms, preferably linear or branched C9-C 12 Mention may be made of alkanes, including in particular dodecane; a mixture of oils having the INCI name C9-12 alkanes, Vegelight Silk® sold by BioSynthIs.

[0172] Preferably, the composition according to the invention comprises at least one hydrocarbon-based liquid fatty substance d) chosen from: vegetable oils formed by fatty acid esters of polyols, in particular triglycerides; -Formula R d -C(O)-OR e where R d represents a higher fatty acid residue containing 7 to 19 carbon atoms, and R e represents a hydrocarbon-based chain containing from 3 to 20 carbon atoms), more preferentially of the formula R d -C(O)-OR e where Rd represents a higher fatty acid residue containing 8 to 10 carbon atoms, and R e represents a hydrocarbon-based chain containing 12 to 18 carbon atoms); -Volatile or non-volatile linear or branched C8-C 60 Alkanes, such as isododecane and alkanes, especially dodecane, obtained by complete hydrogenation / reduction of the mixture of fatty acids obtained from Cocos nucifera (coconut) oil; -Volatile or non-volatile non-aromatic cyclic C5-C 12 Alkanes; - ethers containing 7 to 30 carbon atoms; - ketones containing 8 to 30 carbon atoms; - aliphatic fatty monoalcohols containing 12 to 30 carbon atoms, the hydrocarbon-based chain of which does not contain any substituents; and -A mixture of them.

[0173] Advantageously, the fatty substances d) according to the invention are in particular liquid and apolar, ie formed exclusively from carbon and hydrogen atoms.

[0174] The hydrocarbon-based liquid fatty substances are preferably chosen from the particularly volatile hydrocarbon-based oils containing from 8 to 14 carbon atoms, and more particularly from the apolar oils described above.

[0175] Preferentially, the fatty substances d) of the invention, in particular liquid, are chosen from alkanes, such as dodecane, decane, isododecane, fatty alcohols, such as octyldodecanol, esters, such as isononyl isononanoate, cocoyl caprylate / caprate, and mixtures thereof, more preferentially from alkanes.

[0176] More specifically, the fatty substances d) of the invention, which are in particular liquid, are linear or branched C6-C 16 , preferably C8-C 14 , and more preferentially C9-C 13 , and more preferentially C9-C 12More particularly, the liquid fatty substance d) of the invention is volatile and is selected from undecane, decane, dodecane, isododecane, tridecane and mixtures thereof, in particular mixtures containing dodecane, isododecane, or mixtures of undecane and tridecane.

[0177] Preferentially, the liquid fatty substance d) according to the invention, which is particularly liquid, is isododecane.

[0178] According to another embodiment of the invention, the inventive fatty substance d), which is in particular liquid, is a mixture of non-volatile and volatile oils; preferably, this mixture comprises as volatile oil undecane, dodecane, isododecane or tridecane, more preferentially isododecane. Mixtures of volatile and non-volatile oils which may be mentioned are mixtures of isododecane and of isononyl isononanoate or mixtures of isododecane and of isononyl isononanoate.

[0179] More preferentially, when the fatty substance is a mixture of volatile and of non-volatile oils, the amount of volatile oil is greater than the amount of non-volatile oil.

[0180] In particular, in this mixture, the non-volatile oil is a phenylsilicone oil, preferably chosen from pentaphenylsilicone oils.

[0181] According to one embodiment, the composition comprises one or more fatty substances, especially liquid at 25° C. and atmospheric pressure, preferably one or more oils, in a content ranging from 0.01% to 99.9% by weight, preferably in the range from 0.1% to 50% by weight, preferably in the range from 0.5% to 20% by weight, preferably in the range from 1% to 5% by weight, relative to the total weight of the composition.

[0182] According to one embodiment of the invention, the composition does not comprise fatty substances d) as previously defined.

[0183] According to one embodiment of the invention, the composition comprises d) one or more fatty substances that are liquid, in particular at 25° C. and atmospheric pressure, b) water and e) one or more surfactants.

[0184] e) Surfactants According to a particular embodiment of the invention, the composition also comprises e) one or more surfactants, preferably non-ionic or ionic surfactants or mixtures thereof.

[0185] The term "surfactant" refers to a compound that changes the surface tension between two surfaces. Surfactants e) are amphiphilic molecules that have two parts with different polarity, one part is lipophilic (holds fatty substances) which is non-polar, the other hydrophilic part (miscible or soluble in water) is polar. The lipophilic part is generally a fatty chain, the other water-miscible part is polar and / or protic.

[0186] The term "ionic" means anionic, cationic, amphoteric, or zwitterionic.

[0187] The term "fatty chain" means a linear or branched, saturated or unsaturated, hydrocarbon-based chain containing more than 6 atoms, preferably from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms.

[0188] According to a first particular embodiment, the composition of the invention comprises e) at least one silicone or non-silicone nonionic surfactant.

[0189] Among the nonionic surfactants according to the invention, mention may be made, alone or in mixtures, of fatty alcohols, α-diols and alkylphenols, these three compounds being polyethoxylated, polypropoxylated and / or polyglycerolated and containing, for example, a fatty chain containing from 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups being in particular in the range from 2 to 50 and the number of glycerol groups being in particular in the range from 2 to 30. Copolymers of ethylene oxide and propylene oxide; condensates of ethylene oxide and propylene oxide with fatty alcohols; polyethoxylated fatty amides, preferably containing from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containing on average from 1 to 5, in particular from 1.5 to 4, glycerol groups, oxyethylenated fatty acid esters of sorbitan containing from 2 to 30 mol of ethylene oxide, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkyl polyglycosides, N-alkylglucamine derivatives, amine oxides, such as, for example (C 10 -C 14 ) Alkylamine oxides or N-acylaminopropylmorpholine oxides may also be mentioned.

[0190] The surfactants correspond to a total of not more than 2% by weight of surfactant relative to the total weight of the composition, in particular not more than 1% by weight of surfactant, more particularly less than 0.5% by weight of surfactant relative to the total weight of the composition, and preferentially the composition is surfactant-free.

[0191] Form of the composition According to one embodiment of the present invention, the composition comprises an aqueous phase. The composition is especially formulated as an aqueous lotion, or as a water-in-oil or oil-in-water emulsion, or as a multiple emulsion (oil-in-water-in-oil or water-in-oil-in-water triple emulsion (such emulsions are known and are described, for example, by C. Fox in "Cosmetics and Toiletries" -November 1986-Vol.101-pages 101-112)).

[0192] The aqueous phase of the present compositions contains water and other water-soluble or water-miscible solvents, such as polar and protic solvents, generally as defined above (see Further Solvents).

[0193] The compositions according to the invention preferably have a pH in the range of 3 to 9, depending on the carrier selected.

[0194] According to a particular embodiment of the invention, the pH of the compositions is neutral or slightly acidic. Preferably, the pH of the compositions is between 6 and 7. The pH of these compositions can be adjusted to the desired value by acidifying or basifying agents commonly used in cosmetics or alternatively by using standard buffer systems.

[0195] The term "basifying agent" or "base" refers to any agent for increasing the pH of a composition in which it is present. The basifying agent is a Brønsted base, a Lowry base or a Lewis base. It can be mineral or organic. In particular, said agent is selected from a) aqueous ammonia, b) (bi)carbonates, c) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and their derivatives, d) oxyethylenated and / or oxypropylenated ethylenediamines, e) organic amines, f) mineral or organic hydroxides, g) alkali metal silicates such as sodium metasilicate, h) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and i) compounds of formula (F): [ka] (In formula (F), W is optionally substituted with one or more hydroxyl groups or C1-C6 alkyl groups, and / or one or more heteroatoms such as O or NR u is a divalent C1C6 alkylene group optionally interrupted by ·R x , R y , R z R t and R umay be the same or different and represent a hydrogen atom or a C1-C6 alkyl, C1-C6 hydroxyalkyl or C1-C6 aminoalkyl group).

[0196] Examples of amines of formula (E) that may be mentioned include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

[0197] The term "alkanolamine" refers to an organic amine containing a primary, secondary or tertiary amine functional group and one or more linear or branched C1-C8 alkyl groups bearing one or more hydroxyl groups.

[0198] Among the mineral or organic hydroxides, mention may be made of those selected from a) the hydroxides of alkali metals, b) the hydroxides of alkaline earth metals, such as sodium hydroxide or potassium hydroxide, c) the hydroxides of transition metals, d) the hydroxides of lanthanides or actinides, the quaternary ammonium hydroxides and the guanidinium hydroxide. The mineral or organic hydroxides a) and b) are preferred.

[0199] Among the acidifying agents for the compositions used in the invention, examples that may be mentioned include mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.

[0200] The basifying agents and acidifying agents as defined above preferably represent from 0.001% to 20% by weight relative to the weight of the composition containing them, and more particularly from 0.005% to 8% by weight relative to the weight of the composition.

[0201] According to one embodiment of the present invention, the composition comprises a water content of less than or equal to 10% by weight relative to the total weight of the composition, more preferentially less than or equal to 5%, better still less than 2% and even better still less than 0.5%, in particular anhydrous. Where appropriate, such small amounts of water may in particular be introduced by raw materials of the composition which may contain residual amounts of water.

[0202] According to a non-preferred embodiment, the composition does not contain water.

[0203] Advantageously, the composition according to the invention comprises a physiologically acceptable medium, and in particular it is a cosmetic composition.

[0204] The term "physiologically acceptable medium" means a medium that is compatible with human keratinous substances, such as the skin, lips, nails, eyelashes, eyebrows or hair.

[0205] The term "cosmetic composition" means a composition that is compatible with keratinous materials, has a pleasant color, odor and feel, and does not cause unacceptable discomfort (irritation, stiffness or redness) that would deter consumers from using it.

[0206] The term "keratinous material" means the skin (body, face, eye contour, scalp), hair, eyelashes, eyebrows, body hair, nails or lips.

[0207] The composition according to the present invention may contain cosmetic additives selected from fragrances, preservatives, fillers, colorants, UV blockers, oils, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free radical scavengers, polymers other than the polyhydroxyalkanoates of the present invention, and thickeners.

[0208] According to a particular embodiment of the invention, the composition comprises a) at least one colorant chosen from pigments, direct dyes and mixtures thereof, preferably a) a pigment.

[0209] The term "pigment" is understood to mean any pigment of synthetic or natural origin that imparts color to keratin materials. The solubility of the pigment in water at 25° C. and atmospheric pressure (760 mmHg) is less than 0.05% by weight, preferably less than 0.01%.

[0210] They are white or colored solid particles that are either inherently insoluble in the hydrophilic and lipophilic liquid phases commonly used in cosmetics, or are rendered insoluble, if necessary, by formulation in the form of lakes.More specifically, pigments have little or no solubility in aqueous-alcoholic media.

[0211] Pigments that may be used are selected in particular from organic and / or inorganic pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.Pigments that may be mentioned in particular include organic and mineral pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigments, Organic", 2005 Wiley-VCH Verlag GmbH&Co.KGaA, Weinheim 10.1002 / 14356007.a20 371 and "Pigments, Inorganic, 1. General" therein, 2009 Wiley-VCH Verlag GmbH&Co.KGaA, Weinheim 10.1002 / 14356007.a20_243.pub3.

[0212] These pigments may be in the form of a pigment powder or a paste. They may be coated or uncoated.

[0213] The pigments may be selected, for example, from inorganic pigments, organic pigments, lakes, special effect pigments such as mother of pearl or glitter flakes, and mixtures thereof.

[0214] The pigment may be a mineral pigment. The term "mineral pigment" means any pigment that meets the definition in the chapter on inorganic pigments of Ullmann's encyclopaedia. Among the mineral pigments useful in the present invention, mention may be made of iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

[0215] The pigment may be an organic pigment. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments of Ullmann's encyclopaedia. The organic pigment may be selected in particular from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

[0216] In particular, white or colored organic pigments are carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments classified in the Colour Index under the reference numbers CI 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments classified in the Colour Index under the reference numbers CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, green pigments classified in the Colour Index under the reference numbers CI 61565, 61570, 74260, orange pigments classified in the Colour Index under the reference numbers CI 11725, 15510, 45370, 71105, red pigments classified in the Colour Index under the reference numbers CI In particular, the pigments may be selected from the red pigments classified under FR 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, or from pigments obtained by oxidative polymerization of indole or phenol derivatives, as described in French Patent No. 2 679 771.

[0217] According to a particular embodiment of the invention, the pigment used is a pigment paste of an organic pigment, such as the product sold by the company Hoechst under the following name: -Cosmenyl Yellow 10G: Yellow 3 pigment (CI 11710); -Cosmenyl Yellow G:Yellow 1 pigment (CI 11680); -Cosmenyl Orange GR: Orange 43 pigment (CI 71105); -Cosmenyl Red R: Red 4 pigment (CI 12085); -Cosmenyl Carmine FB: Red 5 pigment (CI 12490); -Cosmenyl Violet RL: Violet 23 pigment (CI 51319); -Cosmenyl Blue A2R; Blue 15.1 pigment (CI 74160); -Cosmenyl Green GG: Green 7 pigment (CI 74260); -Cosmenyl Black R: Black 7 pigment (CI 77266).

[0218] The pigments according to the invention may also be in the form of composite pigments, such as those described in EP 1 184 426. These composite pigments may in particular be composed of particles comprising: - inorganic core, at least one binder for fixing the organic pigment to its core, and at least one organic pigment at least partially covering the core.

[0219] The term "lake" is understood to mean the adsorption of dyes onto insoluble particles, the mass thus obtained remaining insoluble during use. The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum. Among the organic dyes, mention may be made of cochineal carmine.

[0220] Examples of lakes that may be mentioned include the products 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 7 (CI 15 850:1), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green 5 (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0221] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium or calcium aluminium borosilicate and aluminium.

[0222] Among the dyes, mention may be made of cochineal carmine. 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 1O(CI 77 002), D&C Green 3(CI 42 053), D&C Blue 1(CI 42) 090) may also be mentioned.

[0223] As an example of a lake, mention may be made of the product known under the following names: D&C Red 7 (CI 15850:1).

[0224] The pigment may also be a special effect pigment.

[0225] The term "special effect pigments" refers to pigments that generally produce a colored appearance (characterized by a particular hue, a particular saturation, and a particular level of brightness) that is not uniform and that varies depending on the conditions of observation (light, temperature, angle of observation, etc.), thereby differing from colored pigments that exhibit a standard uniform opaque, translucent, or transparent hue.

[0226] 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 high refractive index, such as pearlescent or glitter flakes.

[0227] Examples of special effect pigments that may be mentioned include pearlescent pigments, such as titanic mica coated with iron oxide, mica coated with iron oxide, mica coated with bismuth oxychloride, titanic mica coated with chromium oxide, titanic mica coated with organic dyes, in particular of the type mentioned above, and also pearlescent pigments based on bismuth oxychloride. They may also be mica particles on the surface of which at least two successive layers of metal oxides and / or organic colorants are superimposed.

[0228] The nacreous layer may more specifically have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or shade.

[0229] Examples of pearlescent agents which may be used in the context of the present invention include the gold pearlescent agents sold in particular under the names Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze pearlescent agents sold in particular under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) by Merck, under the name Prestige Bronze by Eckart and under the name Super bronze (Cloisonne) by Engelhard; the bronze pearlescent agents sold in particular under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) by Engelhard, and under the names Passion orange (Colorona) and Matte orange (17449) (Microna); brown pearlescent agents sold in particular under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite) by the company Engelhard; pearlescent agents having a copper tint, sold in particular under the names Copper 340A (Timica) by the company Engelhard and Prestige Copper by the company Eckart; pearlescent agents having a red tint, sold in particular under the name Sienna fine (17386) (Colorona) by the company Merck; pearlescent agents having a yellow tint, sold in particular under the name Yellow (4502) (Chromalite) by the company Engelhard; red pearlescent agents having a golden tint, sold in particular under the name Sunstone G012 (Gemtone) by the company Engelhard; black pearlescent agents having a golden tint, sold in particular under the name Nu antique bronze 240 AB (Timica) by the company Engelhard;Mention may be made of blue pearlescent agents, such as those sold in particular under the names Matte blue (17433) (Microna), Dark Blue (117324) (Colorona) by Merck; white pearlescent agents with a silvery tinge, such as those sold in particular under the name Xirona Silver by Merck; and gold-green pink-orange pearlescent agents, such as those sold in particular under the name Indian summer (Xirona) by Merck, as well as mixtures thereof.

[0230] In addition to pearlescent agents on mica supports, multilayer pigments based on synthetic substrates such as alumina, silica, sodium calcium or calcium aluminum borosilicate and aluminum may also be envisaged.

[0231] Mention may also be made of interference pigments, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f / x from Spectratek), which are not bound to a substrate.Special effect pigments also include fluorescent pigments (these are materials that either fluoresce in daylight or that provide ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, for example, as sold by Quantum Dots Corporation.

[0232] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors, and also specific optical effects such as metallic or interference effects.

[0233] The size of the pigments used in the cosmetic composition according to the invention generally ranges from 10 nm to 200 μm, preferably from 20 nm to 80 μm and more preferentially from 30 nm to 50 μm.

[0234] The pigment may be dispersed in the product by a dispersant.

[0235] The term "dispersant" refers to a compound capable of preventing dispersed particles from flocculating or agglomerating. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several of these, having one or more functional groups that have a strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically bound to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. The agent may have a charge: it may be anionic, cationic, zwitterionic or neutral.

[0236] According to a particular embodiment of the invention, the dispersant used is a 12-hydroxystearic acid, more particularly a C8-C 20 Esters of fatty acids and of polyols, such as glycerol or diglycerol, are chosen, for example, from poly(12-hydroxystearic acid) stearates of approximately 750 g / mol molecular weight, such as the product sold under the trade name Solsperse 21 000 by Avecia, Polyglyceryl-2 Dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by Henkel, or also polyhydroxystearic acid, such as the product sold under the reference Arlacel P100 by Uniqema, and mixtures thereof.

[0237] Other dispersants that may be used in the compositions of the invention may include quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17000 sold by the company Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold under the references DC2-5185 and DC2-5225 C by the company Dow Corning.

[0238] The pigments used in the cosmetic composition according to the present invention may be surface treated with organic agents.

[0239] Thus, pre-surface-treated pigments which are useful in connection with the present invention are pigments which have been subjected, fully or partially, to a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with organic agents, such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53 to 64, and which are then dispersed in the compositions according to the invention. These organic agents may be selected, for example, from amino acids; waxes, such as carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, such as aluminium stearate or aluminium laurate; metal alkoxides; polysaccharides, such as chitosan, cellulose and derivatives thereof; polyethylene; (meth)acrylic polymers, such as polymethyl methacrylate; polymers and copolymers containing acrylate units; proteins; alkanolamines; silicone compounds, such as silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes and siloxysilicates; organofluorine compounds, such as perfluoroalkyl ethers; fluorosilicone compounds.

[0240] The surface-treated pigments useful in the cosmetic compositions according to the present invention may also be treated with mixtures of these compounds and / or may be subjected to several surface treatments.

[0241] The surface-treated pigments that are useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art, or can be as is commercially available.

[0242] Preferably, the surface treated pigment is coated with an organic layer.

[0243] The organic agents for treating the pigment may be deposited on the pigment by evaporating the solvent, by chemical reaction between molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0244] Thus, the surface treatment can be carried out, for example, by chemically reacting a surface treatment agent with the pigment surface to form a covalent bond between the surface treatment agent and the pigment or filler, as described, inter alia, in U.S. Pat. No. 4,578,266.

[0245] Organic agents which are covalently bonded to the pigment are preferably used.

[0246] The agent for surface treatment may represent an amount of 0.1% to 50% by weight, preferably 0.5% to 30% by weight and even more preferentially 1% to 10% by weight relative to the total weight of the pigment to be surface treated.

[0247] Preferably, the surface treatment of the pigment is selected from the following treatments: -PEG-silicone treatments, such as the AQ surface treatment sold by LCW; chitosan treatments, such as the CTS surface treatment sold by LCW; - triethoxycaprylylsilane treatments, such as the AS surface treatment sold by LCW; - methicone treatments, such as the SI surface treatment sold by LCW; - dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment sold by LCW; lauroyl lysine treatments, such as the LL surface treatment sold by LCW; -Lauroyl lysine dimethicone treatments, such as the LL / SI surface treatment sold by LCW; - magnesium myristate treatments, such as the MM surface treatment sold by LCW; -aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - perfluoropolymethylisopropyl ether treatments, such as the FHC surface treatment sold by LCW; isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - disodium stearoyl glutamate treatment, for example NAI surface treatment sold by Miyoshi Kasei Co., Ltd.; -Dimethicone / disodium stearoyl glutamate treatment, such as SA / NAI surface treatment sold by Kokasei Co., Ltd.; - perfluoroalkyl phosphate treatment agents, such as the PF surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment, such as FSA surface treatment sold by Daito Kasei Kogyo Co., Ltd.; - polymethylhydrosiloxane / perfluoroalkylphosphate treatment agent, such as FS01 surface treatment agent sold by Daito Chemical Industry Co., Ltd.; -Lauryl lysine / aluminum tristearate treatment agent, for example LL-StAl surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - octyltriethylsilane treatment agents, such as the OTS surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Octyltriethylsilane / perfluoroalkylphosphate treatment, such as the FOTS surface treatment sold by Daito Kasei Kogyo Co., Ltd.; - acrylate / dimethicone copolymer treatments, such as the ASC surface treatment sold by Daito Kasei Kogyo Co., Ltd.; isopropyl titanium triisostearate treatment agents, such as the ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - microcrystalline cellulose and carboxymethyl cellulose treatment agents, such as the AC surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - cellulose treatment agents, such as the C2 surface treatment agent sold by Daito Chemical Industry Co., Ltd.; - acrylate copolymer treatments, such as the APD surface treatment sold by Daito Chemical Industry Co., Ltd.; - Perfluoroalkylphosphate / isopropyl titanium triisostearate treatment, such as the PF+ITT surface treatment sold by Daito Kasei Kogyo Co., Ltd. is selected from. The composition according to the invention may further comprise one or more surface-untreated pigments. According to one particular embodiment of the invention, the pigment is a mineral pigment. According to another particular embodiment of the invention, the pigments are chosen from pearlescent agents.

[0248] According to a particular embodiment of the invention, the dispersant is present together with an organic or inorganic pigment in particulate form of submicron size.

[0249] The terms "submicron" or "submicron" refer to pigments that have a particle size that has been finely divided by a micronization process and have an average particle size of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, and preferably 0.2 to 0.6 μm.

[0250] According to one embodiment, the dispersant and the pigment are present in a (dispersant:pigment) ratio of 0.5:1 to 2:1, in particular 0.75:1 to 1.5:1 or better still 0.8:1 to 1.2:1.

[0251] According to certain embodiments, the dispersant is suitable for dispersing pigments and is compatible with the condensation curable formulation.

[0252] The term "compatible" means, for example, that the dispersant is miscible in the oil phase of the composition or in the pigment-containing dispersion and that it does not inhibit or reduce curing. The dispersant is preferably cationic.

[0253] Thus, the dispersant may have a silicone backbone, such as a silicone polyether, and may be an aminosilicone type dispersant. Suitable dispersants include: aminosilicones, i.e. silicones containing one or more amino groups, such as those sold by BYK under the names and reference numbers: BYK LPX 21879, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers; silicone acrylates, such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043 sold by Evonik; Polydimethylsiloxane (PDMS) silicones with carboxyl groups, such as X-22162 and X-22370 from Shin-Etsu Chemical Co., epoxy silicones, such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 from Genesee Polymers, or Tego® RC1401, Tego® RC1403, Tego® RC1412 from Evonik.

[0254] According to a particular embodiment, the dispersant is of the aminosilicone type and is positively charged.

[0255] Dispersants having chemical groups capable of reacting with the agents of the oil phase and thus improving the 3D network formed from the aminosilicone may also be mentioned. For example, a dispersant for an epoxysilicone pigment may chemically react with the amino groups of the aminosilicone prepolymer to increase the adhesion of the aminosilicone film containing the pigment.

[0256] Preferably, the pigments of the invention are chosen from: carbon black, iron oxides, in particular black iron oxide and mica coated with iron oxide, triarylmethane pigments, in particular blue and purple triarylmethane pigments such as Blue 1 Lake, azo pigments, in particular red azo pigments such as D&C Red 7, alkali metal salts of lithole red, for example the calcium salt of lithole red B, and even more preferentially red iron oxides.

[0257] The colorant may be selected from direct dyes.

[0258] The term "direct dyes" refers to natural and / or synthetic dyes other than oxidation dyes. These are dyes that diffuse superficially onto the fiber.

[0259] They may be ionic or non-ionic, preferably cationic or non-ionic dyes, ie as the only dye.

[0260] These direct dyes are, for example, selected from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and especially anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and neutral direct dyes.

[0261] Examples of suitable direct dyes that may be mentioned include, alone or as mixtures, azo direct dyes; (poly)methine dyes, such as cyanine, hemicyanine and styryl dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes.

[0262] Preferentially, the direct dye contains at least one quaternized cationic chromophore or at least one chromophore having a quaternized or quaternizable cationic group.

[0263] According to a particular embodiment of the invention, the direct dye comprises at least one quaternized cationic chromophore.

[0264] Direct dyes according to the invention include the following dyes: acridines; acridones, anthranthrones, anthrapyrimidines, anthraquinones, azines, (poly)azos, hydrazonos or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; 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 flavanthrones and flavones; fluorindins; formazans; indamines ; indanthrone; indigoids and pseudoindigoids; indophenol; indoaniline; isoindoline; isoindolinone; isoviolanthrone; lactone; (poly)methines, such as dimethines of the stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines, perilones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes / carotenoids; porphyrins; pyranthrones; pyrazoloanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squalanes; tetrazoliums; thiazines; thioindigo; thiopyronines; triarylmethanes or xanthenes may be mentioned.

[0265] Cationic azo dyes may include, in particular, those derived from the cationic dyes described in Kirk-Othmer's Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons (updated April 19, 2010).

[0266] Among the azo dyes that may be used in accordance with the invention, mention may be made of the cationic azo dyes described in WO 95 / 15144, WO 95 / 01772 and EP 714954.

[0267] According to a preferred embodiment of the invention, the direct dye is selected from the cationic dyes known as "basic dyes".

[0268] Among the azo dyes listed in the Colour Index International (3rd Edition), mention may be made in particular of the following compounds: -Basic Red 22 -Basic Red 76 -Basic Yellow 57 -Basic Brown 16 -Basic Brown 17.

[0269] Among the cationic quinone dyes, those mentioned in the Colour Index International above are suitable, and among these, particular mention may be made of the following dyes: -Basic Blue 22 -Basic Blue 99. Among the azine dyes that are suitable for use, mention may be made of those listed in the Colour Index International, such as the following dyes: -Basic Blue 17 -Basic Red 2. Among the cationic triarylmethane dyes which may be used according to the invention, in addition to those listed in the Colour Index, the following dyes may be mentioned: -Basic Green 1 -Basic Violet 3 -Basic Violet 14 -Basic Blue 7 -Basic Blue 26.

[0270] Mention may also be made of the cationic dyes described in U.S. Pat. No. 5,888,252, EP 1,133,975, WO 03 / 029359, EP 860,636, WO 95 / 01772, WO 95 / 15144 and EP 714,954. Mention may also be made of those listed in the encyclopedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, volumes 1-7, in the chapter "Dyes and Dye Intermediates" in "Kirk-Othmer Encyclopaedia of Chemical Technology", 1993, Wiley and Sons, and in various chapters of "Ullmann's Encyclopaedia of Industrial Chemistry", 7th edition, Wiley and Sons.

[0271] Preferably, the cationic direct dyes are chosen from those obtained from the azo and hydrazono type dyes.

[0272] According to a particular embodiment, the direct dyes are selected from the group consisting of those disclosed in EP 850636, FR 2788433, EP 920856, WO 99 / 48465, FR 2757385, EP 850637, EP 918053, WO 97 / 44004, FR 2570946, FR 2285851, DE 2538363, FR 2189006, FR 1560664, FR 1540423, FR 1567219, FR 1516943 , FR 1221122, DE 4220388, DE 4137005, WO 01 / 66646, U.S. Pat. No. 5708151, WO 95 / 01772, WO 515144, GB 1195386, U.S. Pat. No. 3524842, U.S. Pat. No. 5879413, EP 1062940, EP 1133976, GB 738585, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem,(1978),61(1),48-52;Tsitologiya(1968),10(3),403-5;Zh.Obshch.Khim.(1970),40(1),195-202;Ann.Chim.(Rome)(1975),65(5-6),305-14;Journal of the Chinese Chemical Society(Taipei)(1998),45(1),209-211;Rev.Roum.Chim.(1988),33(4),377-83;Text.Res.J.(1984),54(2),105-7;Chim .Ind.(Milan)(1974),56(9),600-3;Khim.Tekhnol.(1979),22(5),548-53;Ger.Monatsh.Chem.(1975),106(3),643-8;MRL Bull.Res.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.

[0273] Preferably, the cationic direct dye comprises a quaternary ammonium group; more preferentially, the cationic charge is within the ring.

[0274] These cationic groups are, for example: -(di / tri)(C1-C8) alkyl ammonium with exocyclic charge, or acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, cationic heteroaryl groups selected from azolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium, It is a cationic group.

[0275] Mention may be made of the hydrazono cationic dyes of formulae (III) and (IV) and the azo cationic dyes of formulae (V) and (VI) below: [ka] (In formulas (III) to (VI): Het + represents a cationic heteroaryl group, preferentially carrying an intracyclic cationic charge, such as, for example, imidazolium, indolium or pyridinium, optionally substituted, preferentially with at least one (C1-C8) alkyl group, such as methyl; ·Ar + represents an aryl group, such as phenyl or naphthyl, carrying an exocyclic cationic charge, preferentially ammonium, in particular tri(C1-C8)alkylammonium, such as trimethylammonium; Ar represents an aryl group, in particular phenyl, optionally substituted with one or more electron donating groups, such as i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8) (alkyl) amino, in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8) alkylamino, v) optionally substituted N-(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively Ar represents a julolidine group; Ar” represents a (hetero)aryl group, such as phenyl or pyrazolyl, optionally substituted, preferably with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; ·R a and R b represents a hydrogen atom or a (C1-C8) alkyl group, which may be identical or different and is optionally substituted with a hydroxyl group, preferentially; Or else, + Substituent R with the substituent a and / or R with substituents of Ar b together with the atom carrying them form a (hetero)cycloalkyl; in particular R a and R b represents a hydrogen atom or a (C1-C4) alkyl group optionally substituted with a hydroxyl group; Q -represents an organic or inorganic anionic counterion, such as a halide or alkyl sulfate).

[0276] Mention may in particular be made of the azo and hydrazono direct dyes having an in-ring cationic charge of formulae (III) to (VI) as defined above. More particularly, the cationic direct dyes having an in-ring cationic charge of formulae (III) to (VI) as described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954. Preferentially, the following direct dyes: [ka] (In formulas (III-1) and (V-1): -R 1 represents a (C1-C4) alkyl group such as methyl; -R 2 and R 3 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl; -R 4 represents a hydrogen atom or an electron donating group, such as an optionally substituted (C1-C8) alkyl, an optionally substituted (C1-C8) alkoxy or a (di)(C1-C8) (alkyl) amino optionally substituted in the alkyl group with a hydroxyl group; in particular R 4 is a hydrogen atom; -Z represents a CH group or a nitrogen atom, preferentially CH, -Q - is an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

[0277] In particular, the dyes of formulae (III-1) and (V-1) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof: [ka] (Q - is an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl).

[0278] According to a particular embodiment of the invention, the direct dyes are fluorescent, i.e. they contain at least one fluorescent chromophore as previously defined.

[0279] Among the fluorescent dyes that may be mentioned, there may be mentioned groups derived from the following dyes: acridine, acridone, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, coumarin, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}boron (BODIPY®), diketopyrrolopyrrole, fluorindine, (poly)methines (especially cyanines and styryl / hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyl), oxadiazoles, oxazines, perylones, perinones, perylenes, polyenes / carotenoids, squalanes, stilbenes and xanthenes.

[0280] Fluorescent dyes described in the documents EP 1 133 975, WO 03 / 029359, EP 860 636, WO 95 / 01772, WO 95 / 15144 and EP 714 954 as well as in the encyclopedias "The Chemistry of Synthetic Dyes", 1952, Academic Press, volumes 1-7, "Kirk-Othmer Encyclopaedia of Chemical Technology", chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, by K. Venkataraman, and in various chapters of "Ullmann's Encyclopaedia of Industrial Chemistry", 7th edition, Wiley and Sons, and in handbooks circulated on the Internet or in pre-printed versions - "A Guide to Fluorescent Probes and Labeling Technologies", 10th Ed., Molecular Probes / Invitrogen-Oregon 2005 may also be mentioned.

[0281] According to a preferred variant of the invention, the fluorescent dye is cationic and comprises at least one quaternary ammonium group, such as that of formula (VII) below: W + -[C(R C )=C(R d )] m’ -Ar, Q - (VII) (In formula (VII), ·W + represents a cationic heterocyclic or heteroaryl group, especially including quaternary ammonium optionally substituted with one or more (C1-C8) alkyl groups, optionally substituted with one or more hydroxyl groups; Ar represents an aryl group, such as phenyl or naphthyl, preferentially substituted by i) one or more halogen atoms, such as chlorine or fluorine; ii) one or more (C1-C8)alkyl, preferably (C1-C4)alkyl groups, such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8)alkoxy groups, such as methoxy; v) one or more hydroxy(C1-C8)alkyl groups, such as hydroxyethyl; vi) one or more amino groups or (di)(C1-C8)alkylamino groups, preferably in which the C1-C4 alkyl moiety is optionally substituted by one or more hydroxyl groups, such as (di)hydroxyethylamino; vii) one or more acylamino groups; viii) one or more heterocycloalkyl groups, such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl, such as pyrrolidinyl, pyridyl and imidazolinyl; m' represents an integer ranging from 1 to 4; in particular m' is 1 or 2, more preferentially 1; ·R c and R d are identical or different and represent a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferentially a C1-C4 alkyl group, or alternatively W + and R close to c and / or R adjacent to Ar d together with the atom carrying them form a (hetero)cycloalkyl; in particular R c is W + and adjacent to each other, they form a (hetero)cycloalkyl, such as cyclohexyl; Q - is an organic or inorganic anionic counterion as previously defined).

[0282] Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes may also be used, in particular poultices or extracts based on henna.

[0283] According to a particular embodiment of the invention, the amount of colorants, and in particular pigments, ranges from 0.5% to 40%, preferably from 1% to 20%, relative to the weight of the compositions and dispersions containing them.

[0284] Advantageously, the composition according to the invention is a make-up composition, in particular a lip make-up composition, a mascara, an eyeliner, an eyeshadow or a foundation.

[0285] Adjuvants The composition according to the invention may also contain one or more fillers, in particular in a content ranging from 0.01% to 30% by weight, preferably from 0.01% to 20% by weight, relative to the total weight of the composition. The term "fillers" should be understood to mean colorless or white mineral or synthetic particles of any shape that are insoluble in the medium of the composition, regardless of the temperature at which the composition is produced. These fillers serve in particular to modify the rheology or texture of the composition.

[0286] The compositions according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, trace elements, emollients, sequestering agents, fragrances, preservatives, sunscreens, surfactants, antioxidants, agents for loss control, antidandruff agents and propellants or mixtures thereof. The compositions according to the invention may be in the form of anhydrous compositions, water-in-oil emulsions or oil-in-water emulsions or aqueous compositions.

[0287] The term "anhydrous composition" means a composition containing less than 2% by weight of water, or less than 0.5% by weight of water, in particular a composition free of water. Where appropriate, such small amounts of water may be introduced, inter alia, by components of the composition which may contain residual amounts of water.

[0288] The invention is illustrated in more detail in the following examples, in which the amounts are given as percentages by weight. EXAMPLES

[0289] The PHAs illustrated in the various examples were prepared in a 3 L chemostat and / or a 5 L Fernbach flask depending on whether a β-oxidation pathway inhibitor was used or not. Isolation of the PHAs was similar for all the examples obtained.

[0290] In the first stage, the microorganism produces PHA, which is stored in intracellular granules, the proportion of which varies depending on the applied conditions, such as temperature or the nature of the culture medium. The production of PHA granules may or may not be associated with the growth of the microorganism, depending on the nature of the microorganism. During the second stage, the biomass containing PHA is isolated, i.e. separated from the fermentation medium, and then dried. The PHA is extracted from the biomass and then purified, if necessary.

[0291] For certain embodiments, a mixture of saturated and unsaturated carbon sources is necessary for the stability of the resulting PHA.

[0292] [Table 3]

[0293] [Table 4]

[0294] Example 1: Side chain R corresponds to a linear 30% unsaturated n-octenyl group 1 and R corresponding to an n-hexyl group 2 PHA having [ka] The process for obtaining PHA in Example 1 was adapted from the paper: 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 Microbiololy Biotechnology, 82. 657-662, 2009.

[0295] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054. The cultivation method is in a 3 L chemostat containing 2.5 L of culture medium at a rate of μ = 0.15 h. -1 Fed-batch cultivation is carried out under pure culture conditions using a maintenance solution containing a mixture of carbon sources at 200 C. The flow rate of the maintenance feed pump is proportional to the growth of the microorganism according to Equation 1:

number

[0296] Apparatus for fed-batch growth fermentation mode The fermentation medium is regulated with respect to temperature, dissolved oxygen pressure and pH (not shown).

[0297] The production process is carried out using four separate culture media. The first culture medium, defined as CM1 "inoculum", is used for the preparation of a pre-culture. The second culture medium, defined as CM2 "batch", is used to grow the microorganism in a non-fed-batch culture with a primary carbon source in a Fernbach flask. The third culture medium, defined as CM3 "maintenance", is used for feeding the fermentation, for batch or maintenance, with the carbon source of interest, at a flow rate calibrated according to the growth of the microorganism. Medium CM4 is added simultaneously with medium CM3, in a volume ratio of CM3:MC4=1.25:1).

[0298] The composition (grams per liter) of these four media is given in Table 6.

[0299] [Table 5]

[0300] The composition of the nutrient broth, by weight, is 37.5% beef extract and 62.5% peptone, reference 233000 DIFCO™.

[0301] The composition of the trace element solution (grams per liter) is given in Table 7.

[0302] [Table 6]

[0303] A 100 mL preculture is prepared by suspending a cryotube containing 1 mL of strain with 100 mL of "inoculum" culture medium CM1, pH adjusted to 6.8 with 2N NaOH, in a 250 mL Fernbach flask, then incubating the inoculum for 24 hours at 30° C. and 150 rpm. 1.9 L of CM2 "batch" culture medium in a presterilized 3 L chemostat is inoculated with 100 mL of inoculum at DO=0.1. After 4 hours at 30° C. and 850 rpm, the introduction of the maintenance culture medium (MC3+CM4) is carried out, applying the flow rate determined by equation 1.

[0304] At the end of the introduction, the biomass is isolated by centrifugation and washed three times with water. The biomass is dried by freeze-drying before being extracted with ethyl acetate for 24 h. The suspension is clarified by filtration on a GF / A filter (Whatman®) and the filtrate, consisting of the PHA in solution in ethyl acetate, is concentrated by evaporation and then dried to constant weight under high vacuum at 40° C. The PHA thus obtained was purified twice by dissolving in a minimum of AcOEt and precipitating from a 70 / 30 v / v ethanol / water mixture.

[0305] The PHA of Example 1 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the predicted chemical structure.

[0306] Example 2: Functionalization of PHA with 30% unsaturated R=6 and R=8 linear side chains from Example 1 with thiolactic acid [ka] 1 g of PHA from Example 1 and 6 equivalents of thiolactic acid / unsaturated (1.2 g) were dissolved in 10 mL of acetone at ambient temperature with stirring. 0.08 equivalents of 2-hydroxy-2-methylpropiophenone (25 mg) were added to the mixture. The reaction medium 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 under reduced pressure (24 h, 80 ° C).

[0307] The PHA grafted with thiolactic acid was characterized by proton NMR, which showed a complete disappearance of the characteristic signals of unsaturation, confirming 100% grafting of thiolactic acid onto the initially unsaturated chains.

[0308] Example 3: Post-dispersion in water of PHA with 30% unsaturated R=6 and R=8 linear side chains grafted with thiolactic acid obtained in Example 2 using diisopropylethylamine (DIPEA) [ka] Dissolve 1 g of polymer from Example 2 (PHA functionalized with thiolactic acid) in 5 g of acetone to obtain a 20% am solution, then add 0.2 g of N,N-diisopropylethylamine (DIPEA) (1.1 eq) to salify 100% of the acid functional groups. Then add 5 g of water dropwise while stirring vigorously with an UltraTurrax mixer (IKA T10 Basic). Finally, acetone is evaporated under reduced pressure using a rotary evaporator.

[0309] The polymer obtained at the end of the reaction is completely soluble in water (solution containing 20% ​​active substance).

[0310] Application examples To demonstrate performance for dermal application, evaluation was performed in a simplex formulation.

[0311] For one-time operation application: A formulation was prepared containing a solution of polymer, pigment and solvent. Using a film applicator, this formulation was applied (wet thickness 100 μm) to a Bioskin type vitro support (elastic skin equivalent support). The deposit was left to dry for 24 hours.

[0312] A simplex formulation is prepared using a Speed ​​Mixer (2 minutes - 3500 rpm).

[0313] After drying for 24 hours, an evaluation of the deposits is carried out.

[0314] Resistant to olive oil, water and sebum 0.5 mL of olive oil (or water or sebum) is applied to the deposit obtained after drying. After 5 minutes, the olive oil (or water or sebum) is removed by wiping 15 times with absorbent cotton. In this way, the deterioration of the film after contact with olive oil or water or sebum is investigated - see Figure 1.

[0315] Fragmentation testing of formulations on BioSkin To test the resistance to olive oil, a film is produced on a sample of BioSkin. After drying for one day, the Bioskin sheet is stretched ten times by hand. The results can then be observed on the deposit (fragmentation or no fragmentation).

[0316] Two example reactions are given in Figure 2, the results of a fragmentation test. Left: sticky deposit, no fragmentation / Right: fragmentation with the appearance of deposit breakage under stress.

[0317] Each simplex composition was evaluated after drying. The objective was to observe the improvement of cosmetic properties due to the compounds of the invention. In all cases, an improvement of at least one property was observed for the compounds of the invention compared to compounds outside the invention. The following was assessed: +++: The cosmetic properties are considered to be highly effective ++: The cosmetic properties are rated as moderately effective +: Cosmetic properties are rated as less effective 0: Cosmetic properties are rated as ineffective

[0318] [Table 7]

[0319] [Table 8]

[0320] The results of the evaluation are summarized in the table below:

[0321] [Table 9]

[0322] After application of the composition of the invention on keratinous materials such as synthetic skin, the resulting deposit appears to be resistant to everyday chemical (water / olive oil / sebum) and mechanical (fragmentation) aggressors.

[0323] For hair application: Hair Styling Evaluation Protocol A 1g bundle of 90% NG hair is wrapped around the brush. 2 g of a solution containing the PHA polymer from Example 3 at 10% in water is sprayed onto the tress. The mass of the tress is measured before and after application. Approximately 0.5 g of the 10% solution is deposited on the tress. The tresses are measured after application and 24 hours after application (the tresses are left at room temperature). A comparison was made with a tress sprayed with water only. A 1 g bundle of keratin fibers (90% natural grey NG hair) is wrapped around the brush (approximately 2 cm in diameter over a length of 3 cm). A 2 g aqueous solution was prepared containing 10% am of the polymer from Example 3. The solution was vaporized (sprayed) onto a bundle of keratin fibers. The mass of the tress was measured before and after application (0.5 g of water or an aqueous solution containing 10% am of the polymer from Example 3 was deposited per tress). Each tress was measured after application and 24 hours after application (tresses were placed at room temperature, 25° C.).

[0324] [Table 10]

[0325] After 24 hours, the hair tresses treated with the composition according to the process of the present invention appear to make it possible to obtain wavy curls, since the tops of the curls are significantly closer together (5 cm) according to the present invention, compared to 9 cm with water alone and 19 cm without treatment after 24 hours.

Claims

1. A method for treating keratinous materials, preferably α) keratinous fibres, in particular human keratinous fibres such as hair or β) human skin, in particular the lips, comprising the step of: a) one or more PHA copolymers a) and also optical or geometric isomers thereof, organic or mineral acids or basic salts thereof and solvates thereof, such as hydrates, comprising at least two different repeating polymer units selected from the following units (A) and (B): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) (In the polymer units (A) and (B), -R １ represents a saturated or unsaturated, linear or branched, non-cyclic hydrocarbon-based chain or a saturated or unsaturated, non-aromatic cyclic hydrocarbon-based chain containing 3 to 30 carbon atoms; preferably, said hydrocarbon-based chain is i) linear or branched (C ５ -C ２８ ) alkyl, ii) linear or branched (C ６ -C ２８ ) alkenyl, iii) linear or branched (C ６ -C ２８ ) alkynyl, iii) preferably said hydrocarbon-based chain is acyclic and linear; The hydrocarbon-based chain is Anionic group (A － ), cationic group (C ＋ ) and mixtures thereof; (**Aforementioned － The group is -C(O)OH, -C(O)O － , -SO ３ H, -S(O) ２ O － , -O-S(O) ２ OH, -OS(O) ２ O － , -P(O)OH ２ , -P(O)O ２ － , -P(O) ２ O － , -P(OH) ２ , =P(O)-OH, -P(OH)O － , =P(O)-O － , =P-OH and =P-O － and mixtures thereof, the anionic portion being selected from one or more cationic counterions M to achieve electroneutrality of the PHA. ＋ Including; **Above C ＋ The cationic group is a cationizable amine group, -NR ｂ R ｃ , ammonium group -N ＋ R ａ R ｂ R ｃ , a phosphonium group -P ＋ R ａ R ｂ R ｃ , a cationizable amidine group -C(=NR ａ )-NR ｂ R ｃ , an amidinium group -C(=NR ａ ) -N ＋ R ｂ R ｃ R ｄ , a cationizable guanidine group -N(R ａ ) -C(=NR ａ )-NR ｂ R ｃ , a guanidinium group -N(R ａ ) -C(=NR ａ ) -N ＋ R ｂ R ｃ R ｄ or one or more R as defined below ａ a cationizable imidazolyl group optionally substituted with a group, or one or more R ａ The cationic moiety is selected from imidazolium groups optionally substituted with groups, and mixtures thereof, and the cationic moiety is selected from one or more anionic counterions Q to achieve electroneutrality of the PHA. － where R ａ is a hydrogen atom, (C １ -C ４ ) alkyl group or (hetero)aryl group (C １ -C ４ ) an alkyl group, such as benzyl, preferably R ａ is a hydrogen atom or (C １ -C ４ ) represents an alkyl group; R ｂ , R ｃ and R ｄ may be the same or different and are optionally substituted with one or more hydroxyl groups (C １ -C ４ ) alkyl group, (hetero)aryl group, (hetero)aryl (C １ -C ４ ) alkyl groups, such as benzyl, (hetero)cycloalkyl groups or (hetero)cycloalkyl (C １ -C ４ ) alkyl group, or alternatively R ｂ and R ｃ Or R ｃ and R ｄ together with the nitrogen or phosphorus atom which bears them, a saturated or unsaturated, aromatic or non-aromatic heterocycle; in particular (C １ -C ４ ) the alkyl is optionally substituted with one or more hydroxyl groups; the cationic moiety is substituted with one or more anionic counterions Q to ensure electroneutrality; － Including; *** The above R １ The groups are a) halogen, such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(C １ -C ４ ) (alkyl)amino, e) thiocarboxy, f) (thio)carboxamido-C(O)-N(R ａ ) ２ or -C(S)-N(R ａ ) ２ , g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl, and j) (hetero)cycloalkyl, k) cosmetically active agents; l) R-X, where R represents α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl, such as phenyl, m) thiosulfate; X represents a′) O, S, N (R′ ａ ) or Si(R' ｂ ) (R' ｃ ), b') S(O) ｒ or (thio)carbonyl, c') or a combination of a') and b'), such as a (thio)ester, (thio)amide, (thio)urea or sulfonamide; R' ａ is a hydrogen atom, or (C １ -C ４ ) alkyl group or aryl (C １ -C ４ ) an alkyl group, such as benzyl, preferably R ａ represents a hydrogen atom; R' ｂ and R' ｃ may be the same or different, (C １ -C ４ ) alkyl or (C １ -C ４ ) an alkoxy group, in particular the only substituent is preferably selected from a) halogen and j) epoxide); A') one or more heteroatoms, such as O, S, N(R ａ ) and Si(R ｂ ) (R ｃ ), b') S(O) ｒ , (thio)carbonyl, c') or a combination of a') and b'), such as (thio)esters, (thio)amides, (thio)ureas, sulfonamides, preferably esters -O-C(O)- or -C(O)-O-, where r is equal to 1 or 2 and R ａ is as previously defined; preferably, R ａ represents a hydrogen atom, R ｂ and R ｃ is as previously defined); -R ２ is R １ preferably the group R ２ The hydrocarbon-based chain is １ the number of carbon atoms minus at least one carbon atom, preferably <1424 in said group R １ having a carbon number equal to the number of carbon atoms minus two carbon atoms; b) optionally water using at least one composition, preferably a cosmetic composition, comprising - The above R １ In the same PHA, the group A － and C ＋ group, in which case the counterion M ＋ and Q. － may be absent while ensuring the electroneutrality of the PHA, - (A) is different from (B); - The above R １ and R ２ The group is A in the same PHA. － and C ＋ group, in which case the counterion M ＋ and Q. － may be absent while ensuring the electroneutrality of said PHA; the composition comprises a surfactant in an amount equal to or less than 2% by weight relative to the total weight of the composition, in particular equal to or less than 1% by weight, more particularly less than 0.5% by weight relative to the total weight of the composition, and preferentially the composition is free of surfactants; is understood, the way.

2. a) one or more PHA copolymers a) comprising repeating units selected from those of formula (I) and also their optical or geometric isomers, their organic or mineral acid or base salts and their solvates, such as hydrates: 【Chemistry 1】 (In formula (I), ・R １ and R ２ is as defined in claim 1; m and n are integers equal to or greater than 1; preferably, the sum of n+m is between 450 and 1400, inclusive; preferably, m<n. The method of claim 1 , wherein a composition comprising:

3. a) one or more PHA copolymers a) (wherein R １ 1) A as defined in claim 1 － and C ＋ and preferably one or more groups selected from A － 2) or A as defined in claim 1, which is substituted with a group and is not interrupted; － and C ＋ and preferably one or more groups selected from A － group, and one or more heteroatoms or R １ 3. The method according to claim 1 or 2, wherein a composition is used that comprises a) which is a hydrocarbon-based chain, preferably interrupted by a heteroatom such as O or S, preferably S, more specifically 2).

4. a) one or more PHA copolymers a) (wherein R １ are hydrocarbon-based chains, in particular i) -C(O)-OH, -C(O)O － , -SO ３ H, -S(O) ２ O － , -O-S(O) ２ OH, -OS(O) ２ O － , -P(O)OH ２ , -P(O)O ２ － , -P(O) ２ O － , -P(OH) ２ , =P(O)-OH, -P(OH)O － , =P(O)-O － , =P-OH and =P-O － and mixtures thereof, more preferentially selected from -C(O)-OH, -C(O)O － , -SO ３ H, -S(O) ２ O － , -P(O)OH ２ and -P(O)O ２ － , more preferentially carboxylate -C(O)O － , sulfonate-S(O) ２ O － and phosphonate-P(O)O ２ － One or more (preferably one) A selected from － A linear or branched (C ５ -C ２８ ) alkyl, the anionic portion being one or more cationic counterions M to achieve electroneutrality of the PHA. ＋ , for example alkali metals and alkaline earth metals, ammonium: R ａ R ｂ R ｃ R ｄ N ＋ or phosphonium: R ａ R ｂ R ｃ R ｄ P ＋ , preferably ammonium, etc. (R ａ , R ｂ , R ｃ and R ｄ as defined in claim 1), preferably R is <1475 ａ represents a hydrogen atom; R ｂ and R ｃ may be the same or different, preferably the same, and may be linear or branched, preferably branched (C １ -C ４ ) an alkyl group, such as isopropyl or isobutyl, more preferentially isopropyl; R ｄ is linear or branched (C １ -C ４ ) an alkyl group, such as ethyl, more specifically M ＋ is a diisopropylethylammonium group: (i-Pr) ２ N ＋ The method according to any one of claims 1 to 3, wherein a composition comprising (H)Et is used.

5. a) one or more PHA copolymers a) (wherein R １ is an anionic group (A － ) and a cationic group (C ＋ ) one or more groups, preferably a single anionic or cationic group, selected from the group consisting of R １ The method according to any one of claims 1 to 4, wherein a composition comprising:

6. a) one or more PHA copolymers a) (wherein R １ is i) -C(O)-OH, -C(O)O － M ＋ One or more (preferably one) A selected from － A linear or branched substituted with a group (C ３ -C ２８ ) represents an alkyl group; ＋ is as defined in claim 4), more preferentially A － is a carboxylate group -C(O)O － M ＋ And M ＋ is as defined in claim 4); more specifically R １ is substituted at the end of the chain with one or more, preferably only one, group (C ３ -C ２８ ) alkyl group, said group being —C(O)O － M ＋ (M ＋ is as defined in claim 4), preferably -C(O)O － M ＋ The method according to any one of claims 1 to 5, wherein a composition comprising:

7. a) one or more PHA copolymers a) (wherein R １ is represented by the following formula -(CH ２ ) ｒ -X-(ALK) ｕ -G, where X is as defined in claim 1 and in particular O, S, N(R ａ ), preferably S), ALK is linear or branched, preferably branched (C １ -C １０ ) alkylene, more specifically (C １ -C ８ ) alkylene, r is an integer between 6 and 11, preferably between 7 and 10, inclusive, for example 8; u is 0 or 1; G is A as defined in claim 4 or 5; － group, preferably A － For example, -C(O)O － M ＋ (M ＋ The method according to any one of claims 1 to 6, using a composition comprising:

8. a) one or more PHA copolymers a) (wherein R ２ is linear or branched (C ３ -C ２０ ) alkyl and linear or branched (C ３ -C ２０ ) alkenyl, in particular linear hydrocarbon-based groups, more particularly (C ３ -C ２０ ) alkyl or (C ３ -C ２０ ) alkenyl, preferably said hydrocarbon-based group is selected from said group R １ minus at least one carbon atom, preferably the number of carbon atoms in the group R １ having a number of carbon atoms equal to the number of carbon atoms minus 2; preferentially R ２ (C ４ -C ６ 8. The method according to claim 1, wherein a composition is used which comprises a) an alkyl group, for example n-pentyl or n-hexyl.

9. The following: 【Chemistry 2】 (p is an integer from 3 to 15; m and n are as defined in any one of claims 2 to 8, A.L.K. １ is a linear or branched divalent C １ -C １５ represents a hydrocarbon-based group of the formula A.L.K. ２ is C ３ -C ２０ represents an alkyl group, C ＋ and A － is as defined in any one of claims 1 and 3 to 8, In particular, the R １ and R ２ the stereochemistry of the carbon atom bearing the group is selected from the same (R) or (S) configuration, preferably of the (R) configuration; More preferentially 【Chemistry 3】 m and n are as defined in any one of claims 2 to 8, M ＋ is selected from the group consisting of: More specifically: 【Chemistry 4】 m and n are as defined in any one of claims 2 to 8, M ＋ is as defined in any one of claims 1 to 8, p is as defined above; More specifically, the R １ , R ２ and R ３ The stereochemistry of the carbon atom bearing the group is of the same (R) or (S) configuration, preferably of the (R) configuration. Selected from: Even more specifically: 【Chemistry 5】 m and n are as defined in any one of claims 2 to 8, M ＋ is as defined in any one of claims 1 to 8, p is as defined above; v is an integer equal to or greater than 1; More specifically, the R １ , R ２ , R ３ and R ４ the stereochemistry of the carbon atoms bearing the groups being of the same (R) or (S) configuration, preferably of the (R) configuration; The method according to any one of claims 1 to 8, wherein a composition comprising

10. 10. The method according to claim 1, wherein the PHA copolymer a) is present in a content ranging from 0.1% to 65% by weight, preferably from 0.1% to 60% by weight, in particular from 1% to 50% by weight, more particularly from 3% to 40% by weight, more preferably from 5% to 35% by weight, even more preferably from 10% to 30% by weight and better still from 15% to 20% by weight, relative to the total weight of the composition.

Images