Cosmetic composition containing polyhydroxyalkanoate copolymer including at least two kinds of different polymer units that have (UN)saturated hydrocarbon-based chain in fatty medium

Abstract

To provide a composition containing solubilized polyhydroxyalkanoate by which a membrane having excellent cosmetic characteristics can be obtained.SOLUTION: A composition contains a) at least two kinds of different repeating polymer units selected from the following units (A) and (B): -[-O-CH(R1)-CH2-C(O)-]-unit (A) and -[-O-CH(R2)-CH2-C(O)-]-unit (B) and an optical isomer or a geometric isomer thereof, and a solvate thereof such as a hydrate; and b) a fatty medium including one or more kinds of fatty substances which are liquid preferably at 25°C and the atmospheric pressure, where it is to be understood that (A) is different from (B).SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a cosmetic composition comprising at least one polyhydroxyalkanoate copolymer comprising at least two different polymer units having saturated or unsaturated hydrocarbon-based chains in a fatty, preferably oily, medium, and to a method for treating keratinous materials using such a composition. [Background technology]

[0002] It is a known practice to use film-forming polymers in cosmetics that can be delivered in organic media, such as hydrocarbon-based oils. The polymers are used as film-forming agents, especially in makeup products such as mascara, eyeliner, eyeshadow, lipstick, etc. (Patent Document 1) describes C3-C hydroxybutyrate-co-hydroxyvalerate, etc. 21 Cosmetic compositions are described that include pigments coated with polyhydroxyalkanoates.

[0003] 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.

[0004] Patent Document 3 describes a cosmetic composition comprising a thermoplastic resin, such as a polyhydroxyalkanoate, in an aqueous dispersion, and a silicone elastomer. Patent Document 4, on the other hand, describes a cosmetic composition comprising at least one polyhydroxyalkanoate (PHA) in the form of particles having an average diameter (d50) of 0.1 μm to 100 μm, in an amount of 0.1% to 30% by weight, relative to the total weight of the composition, for absorbing oily substances such as sebum. However, the latter PHA is not acceptable as a film-forming polymer in fatty substances such as oils.

[0005] The main part of polyhydroxyalkanoates is a polymer derived from polycondensation of polymeric repeating units that are mostly the same and derived from the same carbon source or substrate. These documents do not describe the use of copolymers derived from polycondensation using a substrate composed of a mixture of an aliphatic carbon source and a carbon source that contains one or more reactive functional groups of different chemical nature from the first carbon source. Copolymers derived from polycondensation can also be prepared from an aliphatic substrate or a first carbon source and at least one second substrate different from the first that contains one or more reactive functional groups of different chemical nature from the first carbon source. [Prior art documents] [Patent documents]

[0006] [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. 2015 / 274972 [Patent Document 4] International Publication No. 2018 / 178899 Brochure Summary of the Invention [Problem to be solved by the invention]

[0007] There is therefore a need to have compositions comprising solubilized polyhydroxyalkanoates that make it possible to obtain films having good cosmetic properties, in particular good resistance to oil and sebum, as well as a good matte feel. [Means for solving the problem]

[0008] The applicant has discovered that polyhydroxyalkanoate copolymers comprising at least two different polymer units (A) and (B) as defined below can be easily used in a fatty, especially oily, medium, thus making it possible to obtain a homogeneous composition. Moreover, the PHA according to the invention is a film-forming polymer. This composition shows good stability, especially after storage for one month at room temperature (25°C). This composition makes it possible to obtain a film with good cosmetic properties, especially good resistance to oil and sebum, and a matte or glossy appearance, especially after application to keratinous materials.

[0009] The subject of the present invention is therefore a) The following units (A) and (B): -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- Unit (B) and also optical or geometric isomers and solvates thereof, such as hydrates, wherein in the polymer units (A) and (B), - R 1 i) branched (C5-C9) alkyl, ii) (C 10 ~C 30 ) alkyl; iii) linear or branched (C5-C 30 ) alkenyl; iv) linear or branched (C5-C 30 ) alkynyl; v) (hetero)aryl; vi) (hetero)cycloalkyl; preferably the group i) (C 10 ~C 20 ) alkyl or iii) (C8-C 20 ) alkenyl; - R 2 represents a cyclic or acyclic, linear or branched, saturated or unsaturated, hydrocarbon-based group containing from 1 to 30 carbon atoms; and b) a fatty medium comprising one or more fatty substances that are preferably liquid at 25° C. and atmospheric pressure wherein it is understood that (A) is different from (B).

[0010] Another subject of the invention is the use in a cosmetic product of a) one or more PHAs as defined above and b) one or more fatty substances as defined above.

[0011] Another subject of the present invention is a method for treating keratinous materials, preferably α) keratinous fibers, in particular human keratinous fibers such as hair, or β) human skin, in particular the lips, using a) one or more PHAs as defined above and b) one or more fatty substances as defined above.More particularly, a subject of the present invention is a method for treating keratinous materials, preferably α) keratinous fibers, in particular human keratinous fibers such as hair, or β) human skin, in particular the lips, by applying a composition as defined above to said materials.

[0012] More particularly, the subject of the present invention is also a non-therapeutic cosmetic method for treating keratinous materials, comprising applying to said materials a composition as defined above, said method of treatment being in particular a method for caring for or making up said materials. [Brief description of the drawings]

[0013] [Figure 1] 1 shows an apparatus for fed-batch culture. [Diagram 2] Tests of film degradation after contact with olive oil or sebum are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] For purposes of this invention, and unless otherwise indicated, - 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 can be substituted by at least one substituent bonded to a carbon atom selected from: C1-C6, preferably C1-C4 alkyl groups; Halogen atoms such as chlorine, fluorine or bromine; ·C1-C2 alkoxy groups; C2-C4 (poly)hydroxyalkoxy groups; · acylamino groups (-NR-COR') where the group R is a hydrogen atom; a carbamoyl group ((R)2N-CO-), in which the C1-C4 alkyl group and the group R' are C1-C4 alkyl groups, the groups R being identical or different, being a hydrogen atom or a C1-C4 alkyl group; an alkylsulfonylamino group (R'SO2-NR-), in which the group R represents a hydrogen atom or a C1-C4 alkyl group and the group R' represents a C1-C4 alkyl group or a phenyl group; an alkylsulfonylamino group (R'SO2-NR-), in which the group R represents a hydrogen atom or a C1-C4 alkyl group and the group R' represents a C1-C4 alkyl group or a phenyl group; · polyhalo(C1-C4)alkyl groups, preferentially trifluoromethyl (CF3); The cyclic or heterocyclic moiety of the non-aromatic group may be substituted with at least one substituent attached to a carbon atom selected from the following group: C1-C4 alkoxy, C2-C4 (poly)hydroxyalkoxy, alkylcarbonylamino (RCO-NR'-), in which the group R' is a hydrogen atom or a C1-C4 alkyl group and the group R 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-), in which the group 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-), in which the group R is a C1-C4 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups; - a cyclic or heterocyclic group or a non-aromatic portion of an aryl or heteroaryl group may 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 hydrocarbon-based chain containing 6 to 22 carbon atoms, at least one ring of which is aromatic, preferentially, an aryl group is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, more preferentially phenyl; - the "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, imidyl, selected from dazopyridyl, 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 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 5-9 membered non-aromatic ring group containing 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur atoms; preferably, heterocycloalkyl is selected from epoxide, piperazinyl, piperidyl and morpholinyl; - an "alkyl" group is a linear or branched, saturated, especially C1-C6, preferably C1-C4, 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; preferably, the group contains only one double bond at the end of the chain opposite the point of attachment to the rest of the molecule; - an "alkynyl" group is a linear or branched, unsaturated hydrocarbon-based group containing one or more conjugated or non-conjugated triple bonds; preferably, the group contains only one triple bond at the end of the chain opposite the point of attachment to the rest of the molecule; - "alkoxy group" is an alkyloxy group, in which alkyl is a linear or branched C1-C6, preferentially C1-C4, hydrocarbon-based group; - The term "organic or mineral acid salt" is more particularly intended to mean, in particular, i) hydrochloric acid, HCl; ii) hydrobromic acid, HBr; iii) sulfuric acid, H2SO4; iv) alkylsulfonic acids: Alk-S(O)2OH, e.g., methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(O)2OH, e.g., benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-OS(O)OH, e.g., methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids, e.g., tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid, H3PO4; ix) triflic acid, CF3SO3H; and x) tetrafluoroboric acid, HBF4; xi) organic carboxylic acids, R°-C(O)-OH(I'z) (wherein 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 substituted optionally 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'z) is selected from acetic acid, glycolic acid, lactic acid and mixtures thereof, more particularly 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 salts selected from the 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 particularly, anionic counterions are i) halides such as chloride or bromide; ii) nitrates; iii) C1-C6 alkylsulfonates: Alk-S(O)2O - , e.g., methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: Ar-S(O)O - for example benzenesulfonates and toluenesulfonates or tosylates; v) citrates; vi) succinates; vii) tartrates; viii) lactate; Ix) alkyl sulfates: Alk-OS(O)O - x) aryl sulfates: Ar-OS(O)O - , for example, benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-OS(O)O - xii) aryloxysulfates: Ar-OS(O)2O-; xiii) phosphates; xiv) acetates; xv) triflates; and xvi) borates, such as tetrafluoroborate. - "Solvates" refers to hydrates and combinations with linear or branched C1-C4 alcohols, such as ethanol, isopropanol or n-propanol. Further, unless specifically stated otherwise, the limits separating a numerical range are included within that numerical range.

[0015] a) PHA copolymer The composition of the present invention comprises as a first component a) one or more PHA copolymers containing, or preferably consisting of, at least two different repeating polymer units selected from units (A) and (B) as defined above.

[0016] The term "copolymer" means that the polymer is derived from the polycondensation of repeating polymer units which are different from one another, i.e., the polymer is derived from the polycondensation of repeating polymer units (A) and (B), it being understood that polymer unit (A) is different from polymer unit (B).

[0017] According to a particular embodiment of the invention, the PHA copolymer consists of two different repeating polymer units selected from units (A) and (B) defined above.

[0018] More particularly, the PHA copolymers according to the present invention comprise repeat units of formula (I) and also optical or geometric isomers thereof and solvates thereof, such as hydrates. [ka] In formula (I), ·R 1 and R 2 is as defined above, m and n are integers of 1 or more; preferably, the sum of n+m is 450 to 1400, inclusive; Preferably, R 1 and R 2 When represents an alkyl group, m>n and is preferably greater than -. 1 and R 2 When is alkyl, R1 is C5~C 13 is an alkyl group; and R 2 is R minus two carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R 1 represents an alkenyl group or an alkyl group, and R 2 When represents an alkyl group, m <nである。

[0019] 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 defined above, - R 3 represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, in particular linear or branched (C1-C 28 ) Alkyl and linear or branched (C2-C 28 ) alkenyl, in particular linear hydrocarbon-based groups, more particularly (C4-C 20 ) alkenyl, preferably the hydrocarbon-based group is the group R 1 or else the group R 1 the number of carbon atoms of the group R 1 having a number of carbon atoms corresponding to the number of carbon atoms in - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and - Preferably, R 1 , R 2 and R 3 represents an alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B) and greater than the mole percentage of units (C), and preferably greater than the mole percentage of units (C) 1 , R 2 and R 3 When is alkyl, R 1 is C5~C 13 is an alkyl group; and R 2 is R minus two carbon atoms. 1 and R 3 is R minus 4 carbon atoms. 1 represents an alkyl group having a carbon number corresponding to the carbon number of Preferably, R 1 When R represents an alkenyl or alkynyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and less than the mole percentage of units (C), in particular R 2 represents an alkyl group, and / or R 3 When represents an alkyl group, preferably, R 3 is R minus two carbon atoms. 2 It is understood that the alkyl group represents an alkyl group having a number of carbon atoms corresponding to the number of carbon atoms in the formula (I).

[0020] According to certain embodiments of the present invention, the PHA copolymer comprises repeat units of formula (II) and also optical or geometric isomers thereof and solvates thereof, such as hydrates. [ka] In formula (II), ·R 1 , R 2 and R 3 is as defined above; m, n, and p are integers of 1 or more; preferably, the sum of n+m+p is 450 to 1400, inclusive; Preferably, R 1 , R 2 and R 3 If represents an unsubstituted and uninterrupted alkyl group, m>n+p and preferably R 1 , R 2 and R 3 When is alkyl, R 1 is C5~C 13 is an alkyl group; and R 2 is R minus two carbon atoms. 1 and R 3 is R minus 4 carbon atoms. 1 represents an alkyl group having a carbon number corresponding to the carbon number of Preferably, R 1 represents an alkenyl group or an alkynyl group, R 2 and R 3 represents an alkyl group, preferably R 3 represents an alkyl group having a number of carbon atoms corresponding to the number of carbon atoms of R2 minus two carbon atoms, m <n+pである。

[0021] According to a particular embodiment, the PHA copolymer a) of the composition contains four different repeating polymer units (A), (B), (C) and (D), preferably consisting of the following four different polymer units (A), (B), (C) and (D) and also their optical or geometric isomers, organic or mineral acid or base salts 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) -[-O-CH(R 4 )-CH2-C(O)-]- Unit (D) In the polymer units (A), (B), (C) and (D), - R 1 , R 2 and R 3 is as defined above, - R 4 represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms; in particular linear or branched (C4-C 28 ) alkyl; and - (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); and - Preferably, R 1 , R 2 , R 3 and R 4 represents an alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), greater than the mole percentage of units (C), and greater than the mole percentage of units (D), and more preferentially than - R 1 , R 2 , R 3 and R 4 When is alkyl, R 1 is C5~C 13 is an alkyl group; and R 2 is R minus two carbon atoms. 1 and R 3 is R minus 4 carbon atoms. 1 and R 4 is R minus 6 carbon atoms. 1 represents an alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 When R represents an alkenyl or alkynyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and less than the mole percentage of units (C), in particular R 2 represents an alkyl group, and / or R3 represents an alkyl group, and R 4 When represents an alkenyl or alkynyl group, preferably, R 3 is R minus two carbon atoms. 2 and R 4 is R minus two carbon atoms. 1 It is understood that the term "alkyl" represents an alkenyl group or alkynyl group having a number of carbon atoms corresponding to the number of carbon atoms in the formula (I).

[0022] 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 defined above, m, n, p and v are integers equal to or greater than 1; preferably, the sum of n+m+p+v is between 450 and 1400 inclusive; and - Preferably, R 1 , R 2 , R 3 and R 4 When represents an alkyl group, m>n+p+q, and is preferably R 1 , R 2 , R 3 and R 4 When is alkyl, R 1 is C5~C 13 is an alkyl group; and R 2 is R minus two carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 3 is R minus 4 carbon atoms. 1 and R represents a linear alkyl group having a carbon number corresponding to the carbon number of 4is R minus 6 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 represents an alkenyl group or an alkynyl group, R 2 and R 3 represents an alkyl group, and R 4 When R represents an alkenyl or alkynyl group, n>m+v; more preferentially n+p>m+v; preferably, R 3 is R minus two carbon atoms. 2 and R 4 is R minus two carbon atoms. 1 represents an alkenyl group or alkynyl group having a number of carbon atoms corresponding to the number of carbon atoms in

[0023] According to a particular embodiment, the PHA copolymer a) of the composition contains five different repeating polymer units (A), (B), (C), (D) and (E), preferably consisting of the following five different polymer units (A), (B), (C), (D) and (E) and also their optical or geometric isomers, organic or mineral acid or base salts and also 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) -[-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 and R 3 is as defined above, - R 4represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, in particular linear or branched (C4-C 28 ) alkyl; and - R 5 represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, in particular linear or branched (C4-C 28 ) alkyl; preferably, the hydrocarbon-based group is a group R 4 , preferably with at least two carbon atoms subtracted, preferably with two carbon atoms subtracted, 4 having a number of carbon atoms corresponding to the number of carbon atoms in - (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); and - Preferably, R 1 , R 2 , R 3 , R 4 and R 5 represents an alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), greater than the mole percentage of units (C), greater than the mole percentage of units (D) and greater than the mole percentage of units (E), and more preferentially R 1 , R 2 , R 3 , R 4 and R 5 When is alkyl, R 1 is C5~C 13 is an alkyl group; and R 2 is R minus two carbon atoms. 1 represents an alkyl group having a carbon number corresponding to the carbon number of R 3 is R minus 4 carbon atoms. 1 represents an alkyl group having a carbon number corresponding to the carbon number of R4 is R minus 6 carbon atoms. 1 and R 5 is R minus 8 carbon atoms. 1 represents an alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 When R represents an alkenyl or alkynyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and less than the mole percentage of units (C), in particular R 2 represents an alkyl group, and R 3 represents an alkyl group, and R 4 and R 5 When represents an alkenyl or alkynyl group, preferably, R 3 is R minus two carbon atoms. 2 and R 4 is R minus two carbon atoms. 1 represents an alkenyl group or an alkynyl group having a carbon number corresponding to the carbon number of 5 is R minus 4 carbon atoms. 1 It is understood that the term "alkyl" represents an alkenyl group or alkynyl group having a number of carbon atoms corresponding to the number of carbon atoms in the formula (I).

[0024] 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 defined above; 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, and - Preferably, R 1 , R 2 , R 3 , R 4 and R 5 represents an alkyl group, then m>n+p+v+z; - Preferably, R 1 represents an alkenyl group or an alkynyl group, R 2 and R 3 represents an alkyl group, and the group R 4 and R 5 When R represents an alkenyl or alkynyl group, n>m+v+z; more preferentially n+p>m+v+z; preferably R 3 is R minus two carbon atoms. 2 and R 4 is R minus two carbon atoms. 1 represents an alkenyl group or an alkynyl group having a carbon number corresponding to the carbon number of 5 is R minus 4 carbon atoms. 1 represents an alkenyl group or alkynyl group having a number of carbon atoms corresponding to the number of carbon atoms in

[0025] According to one embodiment of the composition according to the invention, the PHA copolymer comprises a group R 1 is a branched alkyl containing 5 to 9 carbon atoms, such as 2-methyl-5-pentyl, 2-methyl-2-pentyl, isobutyl or 2-methylheptyl, preferably 2-methyl-5-pentyl.

[0026] According to another particular embodiment of the invention, the PHA copolymer is 1 ii) linear or branched, preferably linear (C 10 ~C 30 ) alkyl.

[0027] According to another particular embodiment of the invention, the PHA copolymer is 1 iii) linear or branched (C5 to C 30) alkenyl; more particularly linear and containing at least one unsaturation, preferably only one unsaturation, at the terminal end of said alkenyl group; even more particularly R 1 is selected from the group: -[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 between 2 and 20, preferably between 3 and 10, more preferentially between 4 and 8, for example 6, inclusive. More particularly, R 1 is selected from hexenyl, octenyl, undecenyl, 2-butenyl and 2-methyl-2-pentenyl.

[0028] In particular, the PHA copolymer is 2 is linear or branched (C1-C 28 ) Alkyl and linear or branched (C2-C 28 ) alkenyl, especially linear hydrocarbon-based groups, especially (C 20 ) alkyl or (C3-C 20 ) alkenyl; preferably, the hydrocarbon-based group is selected from the group R 1 , preferably minus at least two carbon atoms, 1 the number of carbon atoms of the group R 1 The number of carbon atoms corresponds to the number of carbon atoms in

[0029] According to one embodiment of the present invention, the PHA copolymer comprises a group R 2 is linear or branched, preferably linear (C1-C 10) alkyl, in particular (C2-C8) alkyl, preferably (C4-C6) alkyl, such as n-pentyl or n-hexyl, n-heptyl or n-nonyl.

[0030] According to another embodiment of the composition according to the invention, the PHA copolymer is preferably a branched (C3-C8) alkyl, in particular a (C4-C6) alkyl group R 2 , preferably a branched (C4-C5) alkyl group, such as isobutyl.

[0031] According to another embodiment of the composition according to the invention, the PHA copolymer of the invention comprises an alkyl group R 1 and the unit (B) defined above, and a linear or branched (C6 to C 20 ) alkenyl, especially (C7-C 14 ) alkenyl groups, more particularly (C8-C 10 ) alkenyl groups, preferably straight-chained and containing only one unsaturation at the chain end, e.g., -[CH2] q and a unit (C) containing -CH=CH2 (wherein q represents an integer of 3 to 8, preferably 4 to 6, for example 5, inclusive).

[0032] According to a particular embodiment of the invention, in the PHA copolymer, the unit (A) is a hydrocarbon-based chain R which may be an alkenyl or alkynyl group as defined above. 1 , in particular iii), said units (A) being present in a molar percentage ranging from 0.1% to 50%, more preferentially in a molar percentage ranging from 0.5% to 40%, even more preferentially in a molar percentage ranging from 1% to 40%, even better still in a molar percentage ranging from 2% to 30% or in a molar percentage ranging from 5% to 20%.

[0033] Preferably, R of unit (A) 1 When is an unsaturated hydrocarbon-based chain, said units (A) are present in a molar percentage of less than or equal to 30%, more particularly less than 20%, preferably between 8% and 13%.

[0034] According to a more particular embodiment of the invention, in the PHA copolymer, the unit (A) is a hydrocarbon-based chain R which is an alkenyl or alkynyl group as defined above. 1 , especially when it comprises iii), said units (A) are present in a molar percentage ranging from 0.1% to 50%, more preferentially from 0.5% to 40%, even more preferentially from 1% to 40%, even better still from 5% to 30%, even more preferentially from 8% to 20%, units (B) are present in a molar percentage ranging from 70% to 99.5%, preferably from 60% to 95%, and units (C) are present in a molar percentage ranging from 0 to 30%, preferably from 1% to 25%, even more preferentially from 5% to 24%, relative to the sum of units (A), (B) and (C). Advantageously, the PHA copolymer of the invention comprises 70% to 90% by mole of units (B) and 6% to 24% by mole of units (C).

[0035] Preferably, R of unit (A) 1 is a saturated hydrocarbon-based chain, said units (A) are present in a molar percentage of more than 30%, more particularly more than 50%, more preferentially more than 60%, preferably between 60% and 90%.

[0036] According to a more particular embodiment of the present invention, R 1 is an alkyl group, the PHA copolymer is - units (A) are present in a molar percentage ranging from 30% to 99%, preferentially in a molar percentage ranging from 40% to 95%, more preferentially in a molar percentage ranging from 50% to 85%, even more preferentially in a molar percentage ranging from 60% to 70%; and - the units (B) are present in a molar percentage ranging from 0.5% to 70%, preferentially in a molar percentage ranging from 2% to 10%, more preferentially in a molar percentage ranging from 5% to 35% of units (B); and / or - such that units (C) are present in a molar percentage ranging from 0% to 20%, preferentially in a molar percentage ranging from 0.1% to 10%, more preferentially in a molar percentage ranging from 0.5% to 7% of units (C).

[0037] According to a more particular embodiment of the invention, in the PHA copolymer, when the units (A) comprise a hydrocarbon-based chain R1, in particular iii), which is an alkenyl or alkynyl group as defined above, said units (A) are present in a molar percentage ranging from 0.1% to 50%, more preferentially from 0.5% to 40%, even more preferentially from 1% to 40%, even better still from 5% to 30%, from 8% to 20%, relative to the total; (B) is present in a molar percentage ranging from 70% to 99.5%, preferably from 60% to 95%; and units (C) are present in a molar percentage ranging from 0% to 30%, preferably from 1% to 25%, more preferentially from 5% to 24%, 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. Advantageously, the PHA copolymer of the invention comprises 70% to 90% by mole of units (B) and 6% to 24% by mole of units (C).

[0038] The mole percentage values ​​of units (A), (B), (C), (D) and (E) of a PHA copolymer are calculated based on the total number of moles of (A)+(B) if the copolymer does not contain any additional units (C), (D) or (E), or if the copolymer of the present invention contains three or more different units, i.e., (A), (B) and (C), (A), (B), (C) and (D) or (A), (B), (C), (D) and (E), the mole percentages are calculated based on the total number of moles, i.e., (A)+(B)+(C), (A)+(B)+(C)+(D) or (A)+(B)+(D)+(E), respectively.

[0039] Preferentially, the PHA copolymers of the invention comprise the following repeat units:

[0040] 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.

[0041] More particularly, 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.

[0042] More particularly, 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.

[0043] More particularly, the group R 1 , R 2 , R 3 , R 4 and R 5 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably of the (R) configuration.

[0044] More preferentially, the PHA copolymer of the invention comprises the following repeat units: [ka]

[0045] [Table 1]

[0046] [ka]

[0047] [Table 2]

[0048] [ka]

[0049] [Table 3]

[0050] [ka]

[0051] [Table 4]

[0052] [ka]

[0053] [Table 5]

[0054] According to one embodiment, the PHA copolymer of the present invention is different from compounds (2) and / or (2'), in particular from (2), more in particular from compounds (1) and (2) and / or (1') and (2'), in particular from (1) and (2).

[0055] The PHA copolymer of the present invention preferably has a number average molecular weight in the range of 50,000-150,000.

[0056] The molecular weight can be determined inter alia by size exclusion chromatography, the method of which is explained hereinafter in the Examples.

[0057] 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.

[0058] Method for preparing PHA copolymers Methods for the preparation of the PHA copolymers of the present invention are known to those skilled in the art. Mention may be made of the use of "functionalizable" PHA-producing microbial strains.

[0059] The term "functionalizable" means that the PHA copolymer comprises a hydrocarbon-based chain that comprises one or more atoms or groups that can chemically react with another reagent, also called "reactive atom or reactive group", to give a functionalized covalent bond with said reagent. The reagent is, for example, a compound that comprises at least one nucleophilic group, said functionalized hydrocarbon-based chain comprising at least one electrophilic or nucleofugic atom or group, which reacts with the electrophilic group to covalently graft the reagent. The nucleophilic reagent may also react with one or more unsaturations of the alkenyl group to bring about the covalent grafting of the functionalized hydrocarbon-based chain with said reagent. The addition may also be a radical-based, Markovnikov or anti-Markovnikov addition or a nucleophilic or electrophilic substitution. The addition or condensation reaction may be carried out with or without the use of catalysts or enzymes, under inert atmosphere or oxygen, at pressures higher than 1 atmosphere, preferably with heating up to 100° C., and may or may not be carried out via a radical route.

[0060] "Nucleophilic" refers to an 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, amino groups.

[0061] "Electrophilic" refers to any atom or group that exhibits electron-withdrawing properties by inductive effect -I and / or mesomeric effect -M. Electron-withdrawing species that may be mentioned include:

[0062] Microorganisms producing PHAs of the present invention, particularly those having C3-C5 hydrocarbon-based chains, can be naturally produced by the kingdom Bacteria, for example by cyanobacteria of the order Nostocales (e.g. Nostoc muscorum, Synechocystis and Synechococcus), but mainly by the phylum Proteobacteria, for example by the following classes: - Beta-proteobacteria of the order Burkholderiales (Cupriavidus negator synonym. Ralstonia eutropha) - Alpha-proteobacteria of the order Rhodobacteriales (Rhodobacter capsulatus marine and photosynthetic) - A gamma-proteobacterium (Acinetobacter junii) of the order Pseudomonales, family Moraxellaceae.

[0063] Among the microorganisms of the kingdom bacteria, the genera Azotobacter, Hydrogenomomas or Chromatium are representative of PHA-producing organisms.

[0064] Organisms which naturally produce PHAs having a C3-C5 hydrocarbon-based chain are in particular Proteobacteria, such as Gamma-Proteobacteria, more particularly those of the family Pseudomonadaceae, order Pseudomonales, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida. putida GPo1 and Pseudomonas putida KT2440.

[0065] Also, certain organisms can naturally produce PHA without belonging to the order Pseudomonales, such as Commamonas testosteroni, which belongs to the class of Beta-proteobacteria in the order Burkholderiales in the family Comamonadaceae.

[0066] Furthermore, the PHA-producing microorganism according to the present invention may be a recombinant strain when it has a 3-oxidized PHA synthase metabolic pathway, which is mainly represented by four enzymes, EC:2.3.1B2, EC:2.3.1B3, EC:2.3.1B4, and EC:2.3.1B5.

[0067] 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. Saccaromyces 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".

[0068] Genetically modified microorganisms may also be used, which may make it possible, for example, to increase PHA production, increase oxygen consumption capacity, reduce autolysis and / or alter monomer ratios.

[0069] It is known that in the case of PHA, a large part of the total production cost is spent on the culture medium, mainly the substrate / carbon source. Therefore, genetically modified microorganisms that grow with less nutrient source (e.g. methane or CO2) (carbon source) with lower additive value, such as microorganisms that are photoautotrophic in nature, i.e., microorganisms that use light and CO2 as the main energy source, can be used.

[0070] The copolymers can be biosynthesized in a known manner, for example from 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; C2-C 20 , preferably C6 to C 18 carboxylic acids, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; monosaccharides, such as fructose, maltose, lactose, xylose, arabinose, etc.; n-alkanes, such as hexane, octane or dodecane; n-alcohols, such as methanol, ethanol, octanol or glycerol; and a carbon source which may be methane or carbon dioxide.

[0071] 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.

[0072] According to one embodiment, the method for preparing the PHA of the present invention uses microbial cells that produce PHA via genetically modified microorganisms (GMOs). The genetic modification can 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 are naturally propagated.

[0073] As an example, a genetically modified microbial strain that produces PHAs containing reactive groups that can be functionalized or referred to is Pseudomonas entomophila LAC23 (Biomacromolecules. 2014 Jun 9;15(6):2310-9. doi:10.1021 / bm500669s).

[0074] It is also possible to use genetically modified microorganisms that produce phenylvaleric-co-3-hydroxydodecanoic acid copolymers using strains such as Pseudomonas entomophila LAC23 (Sci. China Life Sci., Shen R. et al., 57 No. 1, (2014)).

[0075] Nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium and iron may also be used in this biosynthesis.

[0076] Known suitable conditions of temperature, pH, and dissolved oxygen (OD) can be used to culture the microorganisms.

[0077] 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.

[0078] 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 (2012) and in WO 2011 / 069244.

[0079] Microbial strains producing PHAs that can be functionalized or that contain reactive groups, as defined above, 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, P. putida BM01.

[0080] Carbon source: One means for gaining access to the PHA of the present invention is to introduce into the culture medium one or more organic compounds, which or these organic compounds preferably represent a carbon source selected from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof.

[0081] In one embodiment, the organic compound is preferably selected from alcohols, carboxylic acids and mixtures thereof.

[0082] Carbon sources can be divided into two categories.

[0083] 1) A carbon source via one or more organic compounds introduced into the medium One means for gaining access to the PHAs of the present invention is to introduce one or more organic compounds into the culture medium, which are preferably carbon sources selected from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof.

[0084] According to a particular embodiment of the invention, the organic compound is an alcohol, in particular (C5-C 20 ) alkanols and / or carboxylic acids, especially (C5-C 20 ) alkanoic acids.

[0085] Carbon sources can be divided into three categories. - Group A: The organic compounds may promote the growth of the producing strain and promote the production of PHA structures linked to the organic compounds. - Group B: organic compounds can stimulate the growth of the strain but are not involved in the production of structural PHAs linked to the organic compounds. - Group C: Organic compounds do not contribute to the growth of the strain.

[0086] Such microbiological methods are known to those skilled in the art and are described in particular in the scientific literature: the following may be mentioned: International Journal of Biological Macromolecules 28, 23-29 (2000); The Journal of Microbiology, 45, No. 2, 87-97, (2007).

[0087] According to one variant, the integration of a substrate structurally linked to a reactive atom or reactive group of the PHA of the invention is directly introduced into the medium as the sole carbon source in a medium suitable for the growth of a microorganism (e.g. Group A: alkenoic acids, especially terminal, for P. putida GPo1).

[0088] According to another variant, the integration of a substrate structurally linked to a reactive atom, in particular a halogen or 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).

[0089] According to yet another variant, the integration of a substrate structurally linked to a reactive atom, in particular a halogen or reactive group, of the PHA of the present invention can be directly 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 that is also structurally linked to the PHA and a third carbon source as a co-substrate that is not structurally bound to the PHA (e.g., group C glucose or sucrose).

[0090] 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.

[0091] In one embodiment of the first aspect, the functionalized fatty acid is a functionalized hexanoic acid, functionalized heptanoic acid, functionalized octanoic acid, functionalized nonanoic acid, functionalized decanoic acid, functionalized undecanoic acid, functionalized dodecanoic acid, or functionalized tetradecanoic acid.

[0092] The functionalization can be introduced by organic compounds chosen from the classes of precursors of alcohols and / or carboxylic acids, 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 the functionalization of PHAs with linear alkyl groups containing terminal cyclohexyl units, see, for example, doi.org / 10.1016 / S0141-8130(01)00144-1. For the functionalization of PHAs with unsaturated alkyl groups, preferably terminal, see for example doi.org / 10.1021 / bm8005616). - for the 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 the functionalization of PHA with (hetero)aromatic alkyl groups, such as phenyl, benzoyl, phenoxy, see, for example, J. Microbiol. Biotechnol. 11, 3, 435-442 (2001). For the functionalization of PHAs, in particular with linear alkyl groups 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, in particular with linear alkyl groups 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 with linear alkyl groups, in particular those containing epoxy functional groups at the end of the hydrocarbon-based chain, see for example doi.org / 10.1016 / S1381-5148(97)00024-2. The review in International Microbiology 16:1-15 (2013) doi:10.2436 / 20.1501.01.175 also mentions major functionalized native PHAs.

[0093] In a particular embodiment of the invention, the fatty acids from group A are selected from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and 5-cyanopentanoic acid.

[0094] In certain embodiments of the invention, the fatty acid from group B is selected from halooctanoic acids, such as 8-bromooctanoic acid.

[0095] In a particular embodiment of the invention, the carbon source from group C is a monosaccharide, preferably glucose.

[0096] 2) 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 comprising more than 95% identical units, the comonomer ratio of units (A) and units (B) being different from that obtained in the absence of the β-oxidation pathway inhibitor.

[0097] b) Fatty medium The composition comprises as a second component a fatty medium, which is preferably oily.

[0098] The term "fatty medium" means that the composition of the invention comprises one or more fatty substances. The composition may also comprise water. Preferably, the composition of the invention comprises predominantly one or more fatty substances relative to the weight of water by weight.

[0099] 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 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.

[0100] The fatty substances of the invention are of natural or synthetic origin, preferably of natural and more preferentially of vegetable origin. These fatty substances are preferably not polyoxyethylated and not polyglycerolated. Salified fatty acids generally differ from fatty acids because they constitute soaps that are soluble in aqueous media.

[0101] 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.

[0102] wax According to a particular embodiment, the composition of the invention comprises one or more waxes.

[0103] 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.

[0104] 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.

[0105] The composition according to the invention preferably comprises a wax content ranging from 3% to 20% by weight, in particular from 5% to 15% by weight, more in particular from 6% to 15% by weight, relative to the total weight of the composition.

[0106] According to a particular embodiment of the invention, the composition of the invention is solid, in particular anhydrous. It may be in the form of a stick, and in order to reduce or even eliminate the presence of layers in the solid composition, a polyethylene microwax in microcrystalline form will be used, having an aspect ratio at least equal to 2 and a melting point ranging from 70 to 110°C, preferably from 70 to 100°C. These needle-like crystallites, in particular their dimensions, can be characterized visually according to the following method:

[0107] Paste-like compound According to a particular embodiment, the composition of the invention comprises one or more pasty compounds.

[0108] 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.

[0109] oil Preferably, the composition comprises one or more oils.

[0110] The term "oil" refers to a hydrophobic (i.e. water-immiscible), fatty (i.e. non-aqueous) substance that is liquid at room temperature (25° C.) and atmospheric pressure (1 atmosphere or 760 mmHg).

[0111] The term "liquid fatty substance" especially means a liquid fatty substance having a viscosity at 20° C. of preferably less than or equal to 7000 centipoise.

[0112] The liquid fatty substance of the invention is more particularly at a temperature of 25° C. and 1 s -1 at a shear rate of 2 Pa·s or less, more particularly 1 Pa·s or less, even more particularly 0·1 Pa·s or less, more preferentially 0·09 Pa·s or less.

[0113] According to a particular embodiment of the invention, the liquid fatty substance is dissolved in water at a temperature of 25° C. and at 1 s -1 At a shear rate of 0.001 Pa·s to 2 Pa·s, more particularly 0.01 to 1 Pa·s, even more particularly 0.014 to 0.1 Pa·s, and more preferentially 0.015 to 0.09 Pa·s.

[0114] The PHA copolymers according to the invention are soluble in liquid fatty substances at 25° C. and atmospheric pressure.

[0115] According to the invention, a medium is described as carbon-based if it comprises at least 50% by weight, in particular 50% to 100% by weight, for example 60% to 99% by weight, else 65% to 95% by weight or even 70% to 90% by weight, of carbon-based compounds that are liquid at 25° C., based on the total weight of the carbon-based medium.

[0116] Preferably, the liquid fatty substance has a viscosity of 20 (MPa) 1 / 2 or mixtures of such compounds having the full solubility parameters having the following Hansen solubility space:

[0117] The total solubility parameter δ in the Hansen solubility space is given by Grulke in the paper "Solubility parameter values" in the book "Polymer Handbook", 3rd Edition, Chapter VII, pages 519-559, as follows: δ = (dD2 + dP2 + dH2) 1 / 2 is defined by the relationship: -d D characterized the London dispersion forces resulting from the formation of dipoles upon molecular impact, -d p characterizes the Debye interaction force between permanent dipoles, -d H characterizes the strength of a particular interaction (hydrogen bonding, acid / base, donor / acceptor, etc.).

[0118] The definition of solvents in the Hansen three-dimensional solubility space is given in the paper by Hansen: "The three-dimensional solubility parameters", J. Paint Technol. 39, 105 (1967).

[0119] 20(MPa) 1 / 2Among the liquid carbon-based compounds having the following total solubility parameters according to the Hansen solubility space, mention may be made of liquid fatty substances, and in particular oils, which may be chosen from natural or synthetic, carbon-based or hydrocarbon-based oils, optionally fluorinated and optionally branched, alone or in mixtures.

[0120] Liquid fatty substances, especially C6~C 16 They are selected from hydrocarbons or hydrocarbons containing more than 16 carbon atoms and up to 60 carbon atoms, in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acids and / or fatty alcohol esters, non-silicone waxes and silicones.

[0121] For the purposes of the present invention, fatty alcohols, fatty esters and fatty acids are more particularly recalled to contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups containing from 6 to 30 carbon atoms, which are optionally substituted, in particular with one or more, in particular with 1 to 4, hydroxyl groups. When they are unsaturated, these compounds may contain 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

[0122] C6~C 16 As regards the alkanes, they are linear or branched, and in some cases cyclic. Examples that may be mentioned include hexane, dodecane, and isoparaffins such as isohexadecane and isodecane. Linear or branched hydrocarbons containing more than 16 carbon atoms may be selected from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecene, and hydrogenated polyisobutene.

[0123] According to a particular embodiment, the fatty substance used in the method of the invention is selected from volatile linear alkanes.

[0124] The term "one or more volatile linear alkanes" means, without distinction, "one or more volatile linear alkane oils".

[0125] Volatile linear alkanes suitable for use in the present invention are liquid at room temperature (about 25° C.) and atmospheric pressure (101325 Pa or 760 mmHg).

[0126] A "volatile linear alkane" suitable for use in the present invention is a linear alkane that can evaporate in less than one hour on contact with the skin at room temperature (25°C) and atmospheric pressure (101325 Pa), is liquid at room temperature, and has an evaporation rate of 0.01 to 15 mg / cm at room temperature (25°C) and atmospheric pressure (101325 Pa). 2 / min range.

[0127] Preferably, the volatile linear alkanes suitable for use in the present invention have a viscosity of 0.01 to 3.5 mg / cm at room temperature (25° C.) and atmospheric pressure (101325 Pa). 2 / min, and even better 0.01-1.5 mg / cm 2 / min range evaporation rate.

[0128] More preferably, the volatile linear alkanes suitable for use in the present invention have a molecular weight of 0.01 to 0.8 mg / cm at room temperature (25° C.) and atmospheric pressure (101325 Pa). 2 / min, preferentially 0.01-0.3mg / cm 2 / min, and even more preferentially 0.01 to 0.12 mg / cm 2 / min range evaporation rate.

[0129] The evaporation rate of volatile alkanes according to the invention (and more generally of volatile solvents) can be evaluated in particular by the protocols described in WO 06 / 013413 and more particularly by the protocols described below.

[0130] 15 g of a volatile hydrocarbon-based solvent was placed in a 0.3 ml container that was temperature (25°C) and humidity (50% relative humidity) conditioned. 3 The sample is placed in a crystallizing dish (diameter: 7 cm) placed on a balance inside the chamber.

[0131] The volatile hydrocarbon-based solvent is allowed to evaporate naturally without stirring, while ventilation is provided by a fan (Papst-Motoren, ref. 8550N, rotating at 2700 rpm) positioned vertically above the crystallizing dish containing the volatile hydrocarbon-based solvent, with the blade 20 cm away from the bottom of the crystallizing dish and directed towards it.

[0132] The mass of volatile hydrocarbon-based solvent remaining in the crystallizing dish is measured at regular intervals.

[0133] The amount of evaporated product (mg / cm) was then 2 ) as a function of time (min) to obtain the evaporation profile of the solvent.

[0134] Next, calculate the evaporation rate corresponding to the tangent to the origin of the obtained curve. The evaporation rate is calculated as 2 ) and mg of volatile solvent evaporated per unit time (min).

[0135] According to a preferred embodiment, the volatile linear alkanes suitable for use in the present invention have a non-zero vapor pressure (also known as the saturated vapor pressure) at room temperature, in particular a vapor pressure in the range of 0.3 Pa to 6000 Pa.

[0136] Preferably, the volatile linear alkanes suitable for use in the present invention have a vapour pressure at room temperature (25° C.) ranging from 0.3 to 2000 Pa, and even better still from 0.3 to 1000 Pa.

[0137] More preferably, the volatile linear alkanes suitable for use in the present invention have a vapour pressure at room temperature (25° C.) in the range of 0.4 to 600 Pa, preferentially 1 to 200 Pa, even more preferentially 3 to 60 Pa.

[0138] According to one embodiment, the volatile linear alkanes suitable for use in the present invention may have a flash point lying in the range of 30 to 120° C., more particularly 40 to 100° C. The flash point is measured in particular according to standard ISO 3679.

[0139] According to one embodiment, the volatile linear alkane suitable for use in the present invention may be a linear alkane containing from 7 to 15 carbon atoms, preferably from 8 to 14 carbon atoms, and even better from 9 to 14 carbon atoms.

[0140] More preferably, the volatile linear alkanes suitable for use in the present invention may be linear alkanes containing from 10 to 14 carbon atoms, even more preferentially from 11 to 14 carbon atoms.

[0141] Volatile linear alkanes suitable for use in the present invention may advantageously be of plant origin.

[0142] According to a particular embodiment of the invention, the fatty medium of the composition is oily. More particularly, the composition comprises one or more oils, preferably non-silicone oils and in particular hydrocarbon-based oils.

[0143] The term "hydrocarbon-based oil" means an oil composed of carbon and hydrogen atoms.

[0144] Preferably, the liquid fatty substances of the invention are chosen from hydrocarbons, fatty alcohols, fatty esters, silicones and fatty ethers or mixtures thereof. More particularly, the fatty substances of the invention are not (poly)oxyalkylenated.

[0145] The term "liquid hydrocarbon" refers to a hydrocarbon composed solely of carbon and hydrogen atoms that is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg; i.e. 1.013 x 10 5 This means that the liquid is at room temperature (at 200 Pa).

[0146] More particularly, the liquid hydrocarbon is - Linear or branched, optionally cyclic C6-C 16alkanes (examples that may be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane); - linear or branched hydrocarbons containing more than 16 carbon atoms, of mineral, animal or synthetic origin, such as liquid paraffin, liquid petroleum jelly, polydecenes, hydrogenated polyisobutenes, e.g. Parleam® and squalane is selected from.

[0147] In a preferred variant, the liquid hydrocarbon is selected from liquid paraffin and liquid petroleum jelly.

[0148] The term "liquid fatty alcohol" refers to a liquid fatty alcohol that is used at room temperature (25° C.) and atmospheric pressure (760 mmHg; i.e., 1.013×10 5 means non-glycerolized and non-oxyalkylenated fatty alcohols that are liquid at 200 .mu.m (Pa).

[0149] Preferably, the liquid fatty alcohol of the present invention has from 8 to 30 carbon atoms, more preferentially C 10 ~C 22 , and more preferentially C 14 ~C 20 , and even better C 16 ~C 18 Includes.

[0150] The liquid fatty alcohols of the present invention can be saturated or unsaturated.

[0151] The saturated liquid fatty alcohols are preferably branched. They may optionally contain at least one aromatic or non-aromatic ring in their structure. Preferably, they are acyclic.

[0152] More particularly, the saturated liquid fatty alcohol of the present invention is selected from octyldodecanol, isostearyl alcohol and 2-hexyldecanol.

[0153] According to another variant of the present invention, the fatty substance is selected from liquid unsaturated fatty alcohols.These liquid unsaturated fatty alcohols contain at least one double or triple bond in their structure.Preferably, the fatty alcohols of the present invention have one or more double bonds in their structure.When there are multiple double bonds, there are preferably two or three double bonds, which can be conjugated or non-conjugated.

[0154] These unsaturated fatty alcohols can be linear or branched.

[0155] They may optionally contain at least one aromatic or non-aromatic ring in their structure. Preferably, they are acyclic.

[0156] More particularly, the liquid unsaturated fatty alcohol of the present invention is selected from oleyl alcohol, linolyl alcohol, linolenyl alcohol and undecylenyl alcohol.

[0157] Oleyl alcohol is most particularly preferred.

[0158] The term "liquid fatty ester" or "ester oil" refers to a liquid fatty ester that contains one or more ester groups derived from fatty acids and / or fatty alcohols and has a viscosity that is stable at room temperature (25° C.) and atmospheric pressure (760 mmHg; i.e., 1.013×10 5 It means a compound that is liquid at 200 K (at 200 KPa).

[0159] The esters are preferably saturated or unsaturated, linear or branched C1-C 26 Aliphatic mono- or polyacids and saturated or unsaturated, linear or branched C1-C 26 A liquid ester of an aliphatic mono- or polyalcohol, the total number of carbon atoms in the ester being 10 or more.

[0160] Preferably, for esters of monoalcohols, at least one of the alcohol and acid from which the esters of the invention are derived is branched.

[0161] Among the monoesters of monoacids and monoalcohols, C esters such as alkyl myristates, such as ethyl palmitate, isopropyl palmitate, isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate, and isopropyl isostearate are particularly preferred. 10 ~C 22 , preferably C 12 ~C 20 Alkyl (iso)stearates may be mentioned.

[0162] C4~C 22 Dicarboxylic or tricarboxylic acids and C1-C 22 Esters of alcohols and mono-, di- or tricarboxylic acids with non-saccharides C4-C 26 Esters with dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.

[0163] In particular, mention may be made of diethyl sebacate, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate.

[0164] The composition comprises, as the liquid fatty ester, a C6-C 30 , preferably C 12 ~C 22Sugar esters and diesters of fatty acids may also be included. The term "sugar" is recalled to mean oxygen-containing hydrocarbon-based compounds having some alcohol functionality, with or without aldehyde or ketone functionality, and containing at least four carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

[0165] Examples of suitable sugars that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose and derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, for example methylglucose.

[0166] Sugar esters of fatty acids are in particular those of the abovementioned sugars and linear or branched, saturated or unsaturated C6-C 30 , preferably C 12 ~C 22 They may be selected from the group comprising esters or mixtures of esters of fatty acids. When unsaturated, these compounds may contain from 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

[0167] The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof.

[0168] These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate and arachidonate or mixtures thereof, such as especially oleopalmitate, oleostearate and palmitostearate mixed esters.

[0169] More particularly, mono- and diesters are used, especially sucrose, glucose or methylglucose mono- or diolates, stearates, behenates, oleopalmitates, linoleates, linolenates or oleostearates.

[0170] An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

[0171] Finally, natural or synthetic glycerol esters of mono-, di- or tri-acids may also be used.

[0172] Among these, mention may be made of vegetable oils.

[0173] As examples of oils of vegetable origin or synthetic triglycerides that may be used as liquid fatty esters in the compositions of the invention, mention may be made of: triglyceride oils of vegetable or synthetic origin, for example liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, such as heptanoic or octanoic triglycerides or for example sunflower oil, corn oil, soybean oil, mallow oil, grapeseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, 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, jojoba oil and shea butter oil Includes:

[0174] As esters according to the invention, liquid fatty esters derived from monoalcohols will preferably be used.

[0175] Isopropyl myristate or isopropyl palmitate is preferred.

[0176] The liquid fatty ether is selected from liquid dialkyl ethers, such as dicaprylyl ether.

[0177] According to a preferred embodiment of the invention, the composition comprises one or more hydrocarbon-based oils containing from 8 to 16 carbon atoms.

[0178] More particularly, the hydrocarbon base oil containing 8 to 16 carbon atoms is Branched C8~C 16 Alkanes, e.g., C8-C derived from petroleum 16 Isoalkanes (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane and oils commercially available, for example, under the trade names Isopar or Permethyl; □ Linear C8~C 16 Alkanes, such as n-dodecane (C 2 ), sold by Sasol under the references Parafol 12-97 and Parafol 14-97, respectively. 12 ) and n-tetradecane (C 14 ) and also mixtures thereof, undecane-tridecane mixtures, n-undecane (C 11 ) and n-tridecane (C 13 ), and A mixture of them is selected from.

[0179] The ester oil is in particular chosen from: □ Plant-derived oils, e.g., fatty acids of C4 to C 24triglycerides consisting of fatty acid esters of glycerol which may have various chain lengths, these chains being optionally linear or branched and saturated or unsaturated; these oils are in particular heptanoic or octanoic acid triglycerides. Oils of vegetable origin include wheat germ oil, sunflower oil, grapeseed oil, sesame oil, peanut oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, coconut oil, hazelnut oil, walnut oil, rice oil, linseed oil, macadamia oil, alfalfa oil, poppy seed oil, pumpkin oil, sesame oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil and argan oil; shea butter; or caprylic / capric triglycerides, such as those sold by Stearinerie Dubois or Miglyol by Dynamit Nobel. Such as those sold under the names 810®, 812® and 818®; □Formula R 9 -C(O)-OR 10 Monoester oil (wherein R 9 +R 10 R has ≥ 9 carbon atoms, preferably less than 29 carbon atoms. 9 represents a linear or branched hydrocarbon-based chain containing 5 to 19 carbon atoms; R 10 stands for linear or branched, especially branched, hydrocarbon-based chains containing 4 to 20 carbon atoms), such as palmitate, adipate, myristate and benzoate, especially diisopropyl adipate and isopropyl myristate; cetearyl octanoate (Percellin oil), isopropyl myristate, isopropyl palmitate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, 2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate or octyl octanoate; Lactic acid and C 10 ~C 20 Esters with alcohols, such as isostearyl lactate, 2-octyldodecyl lactate, myristyl lactate, C 12 ~C 13 Alkyl lactate (Cosmacol® Eli from Sasol), cetyl lactate or lauryl lactate; Malic acid and C 10 ~C 20 Diesters with alcohols, such as diisostearyl malate, di(C 12 ~C 13 alkyl)malate (Cosmacol® EMI from Sasol), dibutyl octyl malate, diethylhexyl malate or dioctyl dodecyl malate; Pentaerythritol and C8~C 22 Esters (especially tetraesters or diesters) with carboxylic acids, such as pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate, pentaerythrityl tetrabehenate, pentaerythrityl tetracaprylate / tetracaprate, pentaerythrityl tetracocoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrastearate, pentaerythrityl tetraisostearate, pentaerythrityl tetralaurate, pentaerythrityl tetramyristate, pentaerythrityl tetraoleate or pentaerythrityl distearate; □Formula R 11 -OC(=O)-R 12 -C(=O)-OR 13 where R 11 and R 13 may be the same or different, optionally containing at least one saturated or unsaturated, preferably saturated, C4-C linear or branched, saturated or unsaturated (preferably saturated) ring. 12 , with priority given to C5~C 10 Represents an alkyl chain, and R 12is a saturated or unsaturated C1-C4, preferably C2-C4 alkylene chain, such as succinate (in which case R 12 is a saturated C2 alkylene chain), maleate (in this case, R 12 is an unsaturated C2 alkylene chain), glutarate (in this case, R 12 is a saturated C3 alkylene chain) or adipate (in this case R 12 represents a saturated C4 alkylene chain), in particular R 11 and R 13 is selected from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl and isononyl; preferential mention may be made of dicaprylyl maleate or bis(2-ethylhexyl)succinate; □Formula R 14 -C(=O)-OR 15 -OC(=O)-R 16 where R 14 and R 16 may be the same or different, linear or branched, saturated or unsaturated (preferably saturated) C4-C 12 , with priority given to C5~C 10 Represents an alkyl chain, R 15 represents a saturated or unsaturated C1-C4, preferably C2-C4, alkylene chain). In particular, 1,3-propanediol dicaprylate (R 14 is C7 and R 16 is C3) or dipropylene glycol dicaprylate; Carbonate oil is represented by the following formula R 17 -OC(O)-OR 18 wherein R 17 and R 18 may be the same or different, linear or branched C4-C 12 , with priority given to C6~C 10represents an alkyl chain. The carbonate oil can be dicaprylyl carbonate (or dioctyl carbonate) sold under the name Cetiol CC by BASF, bis(2-ethylhexyl) carbonate sold under the name Tegosoft DEC by Evonik, dipropylheptyl carbonate (Cetiol 4 AII from BASF), dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate, preferably dioctyl carbonate.

[0180] In particular, the fatty substance b) vegetable oils formed from fatty acid esters of polyols, in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, almond oil, calendula oil, palm oil, grape seed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil or cereal germ oil; - linear, branched or cyclic esters containing more than 6 carbon atoms, in particular from 6 to 30 carbon atoms; and in particular isononyl isononanoate; more in particular esters of the formula RC(O)-O-R', in which R represents a higher fatty acid residue containing from 7 to 19 carbon atoms and R' represents a hydrocarbon-based chain containing from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, in particular diisopropyl adipate and isopropyl myristate; - Hydrocarbons and in particular volatile or non-volatile, linear, branched and / or cyclic alkanes, for example C5-C, optionally volatile 60 Isoparaffins, such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane or Isopars; or 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 containing 6 to 30 carbon atoms, the hydrocarbon-based chain of which does not contain any substituents, such as, for example, oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; - polyols containing 6 to 30 carbon atoms, for example hexylene glycol; and - A mixture of these is selected from.

[0181] Preferably, the composition comprises, in a fatty medium: - vegetable oils formed by fatty acid esters of polyols, in particular triglycerides; - esters of formula RCOOR', where R represents a higher fatty acid residue containing from 7 to 19 carbon atoms and R' represents a hydrocarbon-based chain containing from 3 to 20 carbon atoms, - Volatile or non-volatile, linear or branched, C8-C 30 Alkanes; - Linear or branched 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 these The oil comprises at least one oil selected from the group consisting of:

[0182] Preferably, when the copolymer is such that the alkyl group R1 contains 6 to 9 carbon atoms, the fatty substance b) is selected from apolar hydrocarbon-based oils containing 8 to 14 carbon atoms in the absence of monoalcohols containing 2 to 6 carbon atoms.

[0183] Preferably, the copolymer comprises an alkyl group R 1 is such that it contains 9 carbon atoms, then the fatty substance b) is selected from hydrogenated polyisobutylene.

[0184] In particular, the fatty substance is chosen from non-silicone oils; preferably, the liquid fatty substance is - ester oils, carbonate oils; and - Branched non-polar hydrocarbon base oils containing 8 to 14 carbon atoms - as a mixture with monoalcohols containing from 2 to 6 carbon atoms, preferably in a monoalcohol / branched non-polar hydrocarbon-based oil weight ratio ranging from 1 / 99 to 10 / 90; is selected from.

[0185] Advantageously, the composition comprises one or more fatty substances, preferably one or more oils, that are significantly liquid at 25°C and atmospheric pressure of the fatty medium, in a content ranging from 2% to 99.9% by weight, preferably ranging from 5% to 90% by weight, preferably ranging from 10% to 80% by weight, preferably ranging from 20% to 80% by weight, relative to the total weight of the composition.

[0186] Advantageously, the composition according to the invention comprises a physiologically acceptable medium, in particular it is a cosmetic composition.

[0187] 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.

[0188] 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, tightness or redness) that would deter consumers from its use.

[0189] The term "keratinous material" means the skin (body, face, eye contour, scalp), hair, eyelashes, eyebrows, body hair, nails or lips.

[0190] According to one embodiment of the present invention, the composition comprises an aqueous phase, in particular 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)).

[0191] The aqueous phase of the composition comprises water and other water-soluble or water-miscible solvents, such as polar and protic solvents, generally as defined below (see additional solvents).

[0192] Compositions according to the invention preferably have a pH in the range of 3 to 9, depending on the carrier selected.

[0193] 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 using acidifying or basifying agents commonly used in cosmetics or alternatively standard buffer systems.

[0194] The term "basifying agent" or "base" refers to any agent for increasing the pH of the 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, i) compounds of formula (E) below. [ka] (In formula (E), W is a divalent C1-C6 alkylene group optionally substituted by one or more hydroxyl groups or C1-C6 alkyl groups and / or optionally interrupted by one or more heteroatoms such as O or NRu; ·R x , R y , R z , R t and R u may be the same or different and represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 hydroxyalkyl group, or a C1-C6 aminoalkyl group).

[0195] Examples of amines of formula (E) that may be mentioned include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

[0196] The term "alkanolamine" refers to an organic amine having 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.

[0197] Among the mineral or organic hydroxides, mention may be made of those selected from a) alkali metal hydroxides, b) alkaline earth metal hydroxides, such as sodium hydroxide or potassium hydroxide, c) transition metal hydroxides, d) lanthanide or actinide hydroxides, quaternary ammonium hydroxides and guanidinium hydroxide. Preference is given to the mineral or organic hydroxides a) and b).

[0198] Among the acidifying agents of 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.

[0199] The basifying and acidifying agents 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.

[0200] According to a preferred embodiment of the present invention, the composition comprises water in an amount of 10% by weight or less relative to the total weight of the composition.Even more preferentially, the composition comprises water in an amount of 5% or less, better still 2% or less, even better still 0.5% or less, and in particular does not contain water.If appropriate, such small amounts of water can in particular be introduced by components of the composition that may contain residual amounts thereof.

[0201] Even more preferentially, the composition does not contain any water.

[0202] The compositions according to the invention may comprise cosmetic additives selected from water, fragrances, preservatives, fillers, colorants, UV-screening agents, surfactants, moisturizers, vitamins, ceramides, antioxidants, free radical scavengers, polymers and thickeners.

[0203] According to a particular embodiment of the invention, the composition also comprises one or more colorants, preferably pigments, chosen from pigments, direct dyes and mixtures thereof.

[0204] The term "pigment" refers to any pigment of synthetic or natural origin that imparts color to keratinous materials and has a solubility in water at 25° C. and atmospheric pressure (760 mmHg) of less than 0.05% by weight, preferably less than 0.01% by weight.

[0205] They are white or colored solid particles that are either inherently insoluble in the hydrophilic and lipophilic liquid phases commonly used in cosmetics, or that are rendered insoluble, if necessary, by incorporation in the form of lakes.More specifically, pigments have little or no solubility in aqueous-alcoholic media.

[0206] The pigments that may be used are selected from organic and / or mineral pigments known in the art, in particular those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in 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 "Pigment Organics", 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.

[0207] These pigments may be in the form of a pigment powder or a pigment paste. They may be coated or uncoated.

[0208] The pigments may be selected, for example, from mineral pigments, organic pigments, pigments with special effects such as lakes, pearlescent agents or glitter flakes, and mixtures thereof.

[0209] The pigment may be a mineral pigment. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann's encyclopedia. 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.

[0210] 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 in 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 and quinophthalone compounds.

[0211] In particular, the white or colored organic pigments are carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments classified in the Color Index under the reference numbers CI 42090, 69800, 69825, 73000, 74100, 74160, yellow pigments classified in the Color Index under the reference numbers CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, green pigments classified in the Color Index under the reference numbers CI 61565, 61570, 74260, orange pigments classified in the Color Index under the reference numbers CI 11725, 15510, 45370, 71105, red ... The red pigments may be selected from those classified under the reference numbers 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, or from the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described in French Patent No. 2 679 771.

[0212] In a particular embodiment of the invention, the pigments used are pigment pastes of organic pigments, such as the products sold by the company Hoechst under the following names: Cosmenyl Yellow IOG: Yellow 3 pigment (CI 11710); Cosmenyl G yellow: Yellow 1 pigment (CI 11680); Cosmenyl GR orange: Orange 43 pigment (CI 71105); Cosmenyl R red: Red 4 pigment (CI 12085); Cosmenyl FB carmine: Red 5 pigment (CI 12490); Cosmenyl RL violet: Violet 23 pigment (CI 51319); Cosmenyl A2R blue: Blue 15.1 pigment (CI 74160); Cosmenyl GG green: Green 7 pigment (CI 74260); Cosmenyl R black: Black 7 pigment (CI 77266).

[0213] The pigments according to the invention may 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: - Mineral core, - at least one binder for fixing the organic pigment to its core, and - at least one organic pigment at least partially covering said core.

[0214] The term "lake" refers to a dye adsorbed onto an insoluble particle, so that the composite thus obtained remains insoluble when used. The mineral substrates onto which the dye is adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum. Among the organic dyes, cochineal carmine may be mentioned.

[0215] 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).

[0216] The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0217] Among the dyes, mention may be made of cochineal carmine. Mention may also be made of the dyes known by the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15). 510), D&C Red 33(CI 17 200), D&C Yellow 5(CI 19 140), D&C Yellow 6(CI 15 985), D&C Green 5(CI 61 570), D&C Yellow 10(CI 77 002), D&C Green 3(CI 42 053), D&C Blue 1(CI) 42 090).

[0218] As an example of a lake, mention may be made of the product known under the following name: D&C Red 7 (CI 15 850:1).

[0219] The pigment may be a special effect pigment.

[0220] The term "special effect pigments" refers to pigments that generally produce colored appearances (characterized by a particular hue, a particular sparkle, and a particular level of brightness) that are non-uniform and vary depending on the conditions of observation (light, temperature, angle of observation, etc.) Thus, they differ from colored pigments that exhibit standard uniform shades of opaque, translucent, or transparent.

[0221] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a high refractive index, such as pearlescent agents, interference pigments or glitter flakes.

[0222] Examples of special effect pigments that may be mentioned are pearlescent pigments such as titania mica coated with iron oxide, titania mica coated with iron oxide, titania mica coated with bismuth oxychloride, titania mica coated with chromium oxide, in particular titania mica coated with organic dyes of the type mentioned above, and 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 dyes are superimposed.

[0223] The pearlescent agent may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or shade.

[0224] 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 orange 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) by Merck, and in particular Nu-antique copper by Engelhard. brown pearlescent agents sold in particular under the names Copper 340A (Timica) by Engelhard and Brown CL4509 (Chromalite); pearlescent agents with a copper tint sold in particular under the names Copper 340A (Timica) by Engelhard and Prestige Copper by Eckart; pearlescent agents with a red tint sold in particular under the name Sienna fine (17386) (Colorona) by Merck; pearlescent agents with a yellow tint sold in particular under the name Yellow (4502) (Chromalite) by Engelhard; red pearlescent agents with a golden tint sold in particular under the name Sunstone G012 (Gemtone) by Engelhard; black pearlescent agents with a golden tint sold in particular under the name Nu antique bronze 240 AB (Timica) by Engelhard;Mention may be made of the blue pearlescent agent sold in particular under the name Xirona Blue (117324) (Colorona), the white pearlescent agent with a silvery tinge sold in particular under the name Xirona Silver by the company Merck, as well as the gold-green, pink-orange pearlescent agents sold in particular under the name Indian summer (Xirona) by the company Merck, and mixtures thereof.

[0225] In addition to pearlescent agents on mica carriers, multi-layer pigments based on synthetic substrates such as alumina, silica, sodium calcium or calcium aluminum borosilicate and aluminum may also be envisaged.

[0226] Pigments that are not bound to the substrate and exhibit interference effects such as liquid crystals (Helicones HC from Wacker) or holographic luminescent flakes (Geometric Pigments or Spectra f / x from Spectratek) may also be mentioned. Special effect pigments also include fluorescent pigments (which can be either daylight fluorescent or ultraviolet fluorescent), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, such as those sold by Quantum Dots Corporation.

[0227] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic or interference effects.

[0228] 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.

[0229] The pigment may be dispersed in the product by means of a dispersant.

[0230] The term "dispersant" refers to a compound capable of preventing dispersed particles from agglomerating or flocculating. The dispersant may be a surfactant, an oligomer, a polymer or a mixture of several of these, having one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they may be physically or chemically bound to the pigment surface. The dispersant also contains at least one functional group that is miscible with or soluble in the continuous medium. The agent may have a charge. It may be anionic, cationic, zwitterionic or neutral.

[0231] In a particular embodiment of the invention, the dispersing agents used are chosen from: more particularly esters of 12-hydroxystearic acid and polyols, such as C8-C12 glycerol or diglycerol; 20 Fatty acid esters, for example poly(12-hydroxystearic acid) stearate with a molecular mass of about 750 g / mol, such as the product sold under the name Solsperse 21000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid, such as the product sold under the reference Arlacel P100 by the company Uniqema, as well as mixtures thereof.

[0232] 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 Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold under the trade names DC2-5185 and DC2-5225 C by Dow Corning.

[0233] The pigments used in the cosmetic compositions of the present invention may be surface treated with organic agents.

[0234] Thus, pre-surface-treated pigments useful in the context of the present invention are pigments which have been subjected, in whole or in part, to a chemical, electrical, electrochemical, mechanochemical or mechanical surface treatment, in particular with organic agents such as those described in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition 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.

[0235] The surface treated pigments useful in the cosmetic compositions herein may be further treated with mixtures of these compounds and / or may be subjected to multiple surface treatments.

[0236] The surface-treated pigments useful in connection with the present invention may be prepared according to surface treatment techniques well known to those skilled in the art, or may be commercially available as is.

[0237] Preferably, the surface treated pigment is coated with an organic layer.

[0238] The organic agents with which the pigment is treated 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.

[0239] Thus, the surface treatment can be carried out, for example, by chemically reacting a surface treatment agent with the pigment surface to produce a covalent bond between the surface treatment agent and the pigment or filler, as described, inter alia, in US Pat.

[0240] Preferably, an organic agent that is covalently bonded to the pigment will be used.

[0241] The agent for surface treatment may be present in 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.

[0242] 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; - surface treatment with chitosan, e.g. CTS sold by LCW; - surface treatment with triethoxycaprylylsilane, e.g. AS sold by LCW; - Methicone treatments, such as SI Surface Treatment from LCW, - dimethicone treatments, such as Covasil 3.05 surface treatment sold by LCW; - dimethicone / trimethylsiloxysilicate treatments, such as Covasil 4.05 surface treatment available from LCW; - surface treatment with lauroyl lysine, for example LL sold by LCW; - surface treatment with lauroyl lysine dimethicone, for example LL / SI sold by LCW; - Magnesium myristate treatment, for example MM Surface Treatment sold by LCW; - aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - surface treatment with perfluoropolymethyl isopropyl ether treatment, e.g. FHC sold by LCW; - isostearyl sebacate treatment, for example HS surface treatment sold by Miyoshi Kasei Co., Ltd.; - surface treatment with disodium stearoyl glutamate, for example NAI available from Miyoshi Kasei Co., Ltd.; - surface treatment with dimethicone / disodium stearoyl glutamate treatment, for example SA / NAI sold by Miyoshi; - perfluoroalkyl phosphate treatments, such as the PF surface treatment sold by Daito Chemical Industry Co., Ltd.; - acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment, such as FSA surface treatment sold by Daito Chemical Industry Co., Ltd. (Daito); - polymethylhydrogenosiloxane / perfluoroalkylphosphate treatment, such as FS01 surface treatment sold by Daito Chemical Industry Co., Ltd. (Daito); - Lauryl lysine / aluminum tristearate treatment, for example surface treatment with LL-StAl sold by Daito Chemical Industry Co., Ltd. (Daito); - surface treatment with octyltriethylsilane, e.g. OTS available from Daito Chemical Industry Co., Ltd.; - surface treatment with octyltriethylsilane / perfluoroalkylphosphate treatment, e.g. FOTS sold by Daito; - acrylate / dimethicone copolymer treatments, such as the ASC surface treatment sold by Daito Chemical Industry Co., Ltd.; - isopropyl titanium triisostearate treatment, for example ITT surface treatment sold by Daito Chemical Industry Co., Ltd. (Daito); - surface treatment with microcrystalline cellulose and carboxymethyl cellulose, for example AC sold by Daito Chemical Industry Co., Ltd.; - cellulose treatment, for example surface treatment with C2 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 treatments, such as PF+ITT surface treatments available from Daito Chemical Industry Co., Ltd. (Daito). The composition according to the invention may comprise one or more pigments whose surfaces have not been treated. In a particular embodiment of the invention, the pigment is a mineral pigment. In another particular embodiment of the invention, the pigment is chosen from pearlescent pigments.

[0243] In a particular embodiment of the invention, the dispersant is present together with the organic pigment or together with the inorganic pigment in the form of particles of submicron size in dispersion (A), and / or in compositions (B), and / or (C).

[0244] 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.

[0245] 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 even better still 0.8:1 to 1.2:1.

[0246] According to certain embodiments, the dispersant is suitable for dispersing pigments and is compatible with condensation curable formulations.

[0247] 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 does not impair or reduce its effectiveness. The dispersant is preferably cationic.

[0248] 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 under the name and trade designation BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 by Genesee Polymers; silicone acrylates, such as Tego® RC902, Tego® RC922, Tego® RC1041 and Tego® RC1043 sold by Evonik; - polydimethylsiloxane (PDMS) silicones carrying carboxyl groups, such as X-22162 and X-22370 from Shin-Etsu; 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.

[0249] According to a particular embodiment, the dispersant is of the aminosilicone type and is positively charged.

[0250] Dispersants carrying chemical groups capable of reacting with the agents of the oil phase and thus improving the 3D network formed by the aminosilicone may be mentioned. For example, a dispersant for an epoxysilicone pigment can chemically react with the amino groups of the aminosilicone prepolymer to increase the cohesive strength of the aminosilicone film containing the pigment.

[0251] The pigments of the present invention are preferably 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, for example 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 oxide.

[0252] The colorant may be selected from direct dyes.

[0253] The term "direct dyes" means natural and / or synthetic dyes other than oxidation dyes. These are dyes that will diffuse superficially onto the fiber.

[0254] These can be ionic or non-ionic, preferably cationic or non-ionic, either as single dyes.

[0255] 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, especially anthraquinone direct dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and neutral direct dyes.

[0256] Examples of suitable direct dyes that may be mentioned include azo direct dyes, alone or as mixtures; (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.

[0257] Preferentially, the direct dye contains at least one quaternized cationic chromophore or at least one chromophore having a quaternized or quaternizable cationic group.

[0258] According to a particular embodiment of the invention, the direct dye comprises at least one quaternized cationic chromophore.

[0259] 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, tetraazacarbocyanines or (poly)methines, diazines, diketopyrrolopyrroles, dioxazines, diphenylamines, diphenylmethanes, dithiaazines, flavonoids such as flavanthrones and flavones, fluorindines, formasans, Mention may be made of chromophores derived from indamines, indanthrones, indigoids and pseudoindigoids, indophenols, indoanilines, isoindolines, isoindolinones, isoviolanthrones, lactones, (poly)methines, such as dimethines of the stilbene or styryl type, naphthoquinones, nitro, especially nitro(hetero)aromatics, oxadiazoles, oxazines, perilones, perinones, perylenes, phenazines, phenoxazines, phenothiazines, phthalocyanines, polyenes / carotenoids, porphyrins, pyranthrones, pyrazolanthrones, pyrazolones, pyrimidinoanthrones, pyronines, quinacridones, quinolines, quinophthalones, squalanes, tetrazoliums, thiazines, thioindigo, thiopyronines, triarylmethanes or xanthenes.

[0260] 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 on 19 April 2010.

[0261] 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.

[0262] According to a preferred embodiment of the invention, the direct dye is selected from the cationic dyes known as "basic dyes".

[0263] Among the azo dyes mentioned 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 and Basic Brown 17.

[0264] Among the cationic quinone dyes, the chromophores mentioned in the Colour Index International above are suitable, and among these, the following dyes may be mentioned in particular: Basic Blue 22, Basic Blue 99.

[0265] Among the azine dyes 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.

[0266] 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.

[0267] 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, vol. 1-7; in "Kirk-Othmer Encyclopedia of Chemical Technology", chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons.

[0268] Preferably, the cationic direct dyes are chosen from those obtained from the azo and hydrazono type dyes.

[0269] 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 and 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.

[0270] Preferably, the cationic direct dye comprises a quaternary ammonium group, more preferentially the cationic charge is within the ring.

[0271] These cationic radicals include, for example: - (di / tri)(C1-C8) alkyl ammonium with an exocyclic charge, or cationic groups with an endocyclic charge, such as comprising cationic heteroaryl groups selected from the following: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.

[0272] Mention may be made of cationic dyes chosen from: - a hydrazono dye having the formula: (XVI)Het + -C(R' a )=NN(R' b )-Ar,Q - and (XVII) Het + -N(R'a )-N=C(R' a )-Ar,Q - , azo dyes having the formula: (XVIII)Het + -N=N-Ar, Q and (XIX)Ar + -N=N-Ar,Q (In formulas (XVI) to (XVIII), Het + represents a cationic heteroaryl group, such as imidazolium, indolium or pyridinium, preferentially carrying a cationic charge in the ring and 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 preferentially represents 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) an aryl group, in particular phenyl, optionally substituted with an optionally substituted N-(C1-C8) alkyl-N-aryl(C1-C8) alkylamino, or alternatively Ar represents a julolidine group; Ar″ represents an optionally substituted (hetero)aryl group, for example phenyl or pyrazolyl, preferentially optionally substituted with one or more (C1-C8)alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8)alkoxy or phenyl groups; R', which may be the same or different a and R' b represents a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferentially by a hydroxyl group; Otherwise, Het + R' having the substituenta and / or R' having a substituent of Ar b together with the atoms which carry 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 anionic counterion such as a halide or alkyl sulfate).

[0273] Mention may be made in particular of the azo and hydrazono direct dyes having an endocyclic cationic charge of the formulae (XII) to (XV) defined above, more particularly the cationic direct dyes having an endocyclic cationic charge of the formulae (XII) to (XV) as described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714954, preferentially the following direct dyes: [ka] In formulas (XVI-1) and (XVIII-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, in which the alkyl group is optionally substituted 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 mesyl.

[0274] In particular, the dyes of formulae (XVI-1) and (XVIII-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 mesyl.

[0275] According to a particular embodiment of the invention, the direct dyes are fluorescent, i.e. they contain at least one fluorescent chromophore as defined above.

[0276] Fluorescent dyes that may be mentioned include 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, peronones, perylenes, polyenes / carotenoids, squalanes, stilbenes and xanthenes.

[0277] Fluorescent dyes as described in EP 1 133 975, WO 03 / 029359, EP 860 636, WO 95 / 01772, WO 95 / 15144 and EP 714 954 and in the encyclopedia "The Chemistry of Synthetic Dyes", 1952, Academic Press, vols. 1-7 by K. Venkataraman, in the chapter "Dyes and Dye Intermediates", Kirk-Othmer Encyclopedia of Chemical Technology, 1993, Wiley and Sons, in various chapters of "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons and in handbooks circulated on the Internet or in printed versions - "A Guide to Fluorescent Probes and Labelling Technologies", 10th Ed., Molecular Probes / Invitrogen-Oregon 2005 may also be mentioned.

[0278] According to a preferred variant of the invention, the fluorescent dye is cationic and comprises at least one quaternary ammonium group such as of formula (XIII): W + -[C(R c )=C(R d )] m’ -Ar,Q - In formula (XIII), ·W + represents a cationic heterocyclic or heteroaryl group, including a quaternary ammonium optionally substituted, in particular by one or more hydroxyl groups, optionally substituted, in particular by one or more (C1-C8) alkyl groups; Ar preferentially represents i) one or more halogen atoms, such as chlorine or fluorine; ii) one or more (C1-C8) alkyl groups, preferably C1-C4 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, preferably having a C1-C4 alkyl moiety optionally substituted by one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) one or more acylamino groups; viii) an aryl group, such as phenyl or naphthyl, optionally substituted by one or more heterocycloalkyl groups, such as piperazinyl, piperidyl, or a 5- or 6-membered heteroaryl group, such as pyrrolidinyl, pyridyl and imidazolinyl; m' represents an integer from 1 to 4; in particular m' is 1 or 2, more preferentially 1; ·R, which may be the same or different c and R d represents a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferentially a C1-C4 alkyl group, or alternatively W + and adjacent R c and / or R adjacent to Ar d together with the atoms which carry 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.

[0279] 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, orcein. Extracts or decoctions containing these natural dyes may also be used, in particular henna-based poultices or extracts.

[0280] According to a particular embodiment of the invention, the amount of colorants, and in particular pigments, ranges from 0.5% to 40% and preferably from 1% to 20% relative to the weight of the compositions and dispersions containing them.

[0281] Advantageously, the composition according to the invention is a makeup composition, in particular a lip makeup composition, a mascara, an eyeliner, an eyeshadow or a foundation.

[0282] Additional Solvent According to a particular embodiment of the invention, the composition comprises one or more solvents, preferably polar and / or protic other than water, in a predominantly fatty medium.

[0283] The solvent other than water, which is preferably polar and / or protic, is present in the composition in a weight percentage of 0 to 10% by weight relative to the total weight of the solvent mixture, preferentially 0.5 to 8% by weight, more particularly 1 to 5% by weight, for example 2% by weight relative to the total weight of the composition. Preferably, the solvent is a polar protic solvent, such as an alkanol, more preferentially a C2-C6 alkanol, for example ethanol.

[0284] 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, which 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.

[0285] 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, loss control agents, antidandruff agents and propellants or mixtures thereof.

[0286] The invention is illustrated in more detail in the following examples, in which amounts are given as % by weight. EXAMPLES

[0287] The exemplified PHAs were prepared in 3 L chemostats and / or 5 L Fernbach flasks depending on whether a β-oxidation pathway inhibitor was used or not. Isolation of the PHAs was similar for all the examples obtained.

[0288] In the first stage, the microorganism produces PHA copolymer, which is stored in intracellular granules. The proportion varies as a function of the applied conditions, such as temperature or the nature of the culture medium. The production of PHA copolymer granules may or may not be associated with the growth of the microorganism, as a function of the nature of the microorganism. In the second stage, the biomass containing the PHA copolymer is isolated, i.e. separated from the fermentation medium, and then dried. The PHA copolymer is extracted from the biomass before being purified, if necessary.

[0289] In certain embodiments, a mixture of saturated and unsaturated carbon sources is necessary for the stability of the resulting PHA copolymer.

[0290] [Table 6]

[0291] [Table 7]

[0292] Example 1: Side chain R representing an n-octenyl group 1 and R represents an n-pentyl group. 2 A copolymer of PHA having [ka] The method for synthesizing the compound of 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 Microbiology Biotechnology, 82.657-662, 2009.

[0293] 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 The culture is carried out under fed-batch pure culture conditions using a maintenance medium containing a mixture of carbon sources.

[0294] Nominal Dissolved Oxygen (O D The system is aerated with an air flow of 0.5 vvm so that the pH is 30% saturated. The pH is adjusted with 15% aqueous ammonia solution. The temperature of the fermentation medium is adjusted to 30°C.

[0295] Apparatus for fed-batch fermentation mode The fermentation medium is regulated with respect to temperature, dissolved oxygen pressure and pH (not shown).

[0296] See Figure 1. The production method is carried out using three different 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 for the non-fed-batch cultivation of the microorganism with the primary carbon source in Fernbach flasks. The third culture medium, defined as CM3 "maintenance", is used for fed-batch or maintenance fermentation mode with the carbon source of interest at a flow rate calibrated as a function of the growth of the microorganism.

[0297] [Table 8]

[0298] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™.

[0299] [Table 9]

[0300] 100 mL of preculture is prepared by suspending a cryotube containing 1 mL of strain together with 100 mL of "inoculation" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then incubating for 24 hours at 30° C. and 150 rpm. 1.9 L of CM2 "batch" culture medium in a sterile 3 L chemostat is inoculated with 100 mL of preculture. O After 4 hours at 30° C. and 850 rpm, the introduction of the maintenance culture medium is carried out, applying a defined flow rate.

[0301] After the introduction is complete, the biomass is isolated by centrifugation and washed three times with water. The biomass is dried by freeze-drying and then extracted with ethyl acetate for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, which is the PHA copolymer dissolved in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass.

[0302] The PHA copolymer can optionally be purified by successive dissolution and precipitation, for example, from an ethyl acetate / ethanol 70% methanol system.

[0303] The PHA copolymer of Example 1 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 2 = 86.5 mol % of units (B) which are n-pentyl (79.1%) and n-hexyl (7.4%), and R 1 = 11.8 mol % of units (A) being n-octenyl (3.9%), units (C) n-hexenyl (6.7%) and units (D) n-butenyl (1.2%).

[0304] Example 2: Side chain R representing an n-octenyl group 1 and R representing an n-hexyl group. 2 A copolymer of PHA having [ka] The manufacturing method of Example 1 is adapted to that of Example 2 by replacing the n-octanoic acid carbon source of Example 1 with n-nonanoic acid.

[0305] The PHA copolymer of Example 2 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 2 = 87.2 mol % of units (B) being n-hexyl (64.1%), and units (C) n-butyl (23.1%) and R 1 = 10.6 mol % of units (A) being n-octenyl (3.9%), units (D) n-hexenyl (5.6%) and units (E) n-butenyl (1.1%).

[0306] Example 3: Side chain R representing an isohexenyl group 1 and R representing an isobutyl group. 2 A copolymer of PHA having [ka] The method for producing Example 3 was adapted from "Pseudomonas citronellolis Grown on Various Carbon Sources, Including 3-Methyl-Branched Substrate", Mun Hwan Choi and Sung Chul Yoon, Applied and Environmental Microbiology, Vol. 60, No. 9. 3245-3254 (1994). The microorganism used was Pseudomonas citronellolis ATCC (registered trademark) 13674 (trademark).

[0307] The cultivation process is carried out in an orbital incubator (orbital diameter 2.5 cm) with shaking at 30° C. and 110 rpm in 5 L Fernbach flasks (Corning® reference 431685) containing 2 L of culture medium - under fed-batch pure culture conditions.

[0308] The production method is carried out using two different 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 for the non-fed-batch cultivation of the microorganism with the carbon source of interest in Fernbach flasks.

[0309] [Table 10]

[0310] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™ BD.

[0311] The composition of the yeast extract, by weight, is 100% autolysate of the yeast Saccharomyces cerevisiae, reference number 210933 DIFCO® BD.

[0312] [Table 11]

[0313] A 100 mL preculture is prepared by suspending a cryotube containing 1 mL of strain together with 100 mL of "inoculum" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then incubating for 24 hours at 150 rpm at 30° C. 1.9 L of CM2 "batch" culture medium in a sterile 5 L Fernbach flask is inoculated with 100 mL of inoculum at OD=0.1.

[0314] After 70 hours at 30°C and 110 rpm, the biomass is dried by freeze-drying and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, consisting of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40°C until constant mass.

[0315] The PHA can optionally be purified by sequential dissolution and precipitation, for example using a dichloromethane / methanol system.

[0316] The PHA copolymer of Example 3 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 1 = 68 mol% of units (A) which are isohexenyl, R 2 = The amount of isobutyl units (B) was 32 mol %.

[0317] Example 4: Side chain R representing an isohexyl group 1 and R representing an isobutyl group. 2A copolymer of PHA having [ka] Example 4 is obtained by hydrogenating Example 3 using a H-Cube Midi® continuous hydrogenation apparatus manufactured by Thales Nano Technologie.

[0318] A solution of 2 g (8.83 mmol) of Example 3 is prepared using a mixture composed of 100 mL of ethyl acetate (Sigma-Aldrich-CAS: 141-78-6) and 100 mL of methanol (Sigma-Aldrich-CAS: 67-56-1) and introduced at a flow rate of 3 mL / min into a hydrogenation cartridge (MidiCard, reference DHS 2141; ThalesNano Technologie) containing a catalyst containing 5% palladium on charcoal, maintained at 100° C. under a pressure of 80 bar in the presence of hydrogen in a ThalesNano Technologie H-Cube Midi® system. The reduction of the double bond is monitored by NMR. After six successive reduction cycles, the solution is concentrated by evaporation and dried under vacuum to constant mass.

[0319] The PHA can optionally be purified by sequential dissolution and precipitation, for example using a dichloromethane / methanol system.

[0320] The PHA copolymer of Example 4 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 1 = 68 mol% of units (A) which are isohexyl, R 2 = The amount of isobutyl units (B) was 32 mol %.

[0321] Example 5: Non-inventive - Comparative - Copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, PHB-co-HV with 12 mol% HV - CAS number 80181-31-3, commercial reference: 403121 (Sigma-Aldrich)

[0322] Example 6: Solubility studies in polar protic solvents and oils The polymers of Examples 1-4 and a commercially available PHA polymer having a short saturated hydrocarbon-based chain (Example 5, not of the invention) were evaluated for solubility in various oils as listed in the table below.

[0323] 1 g of polymer was introduced into 4 g of liquid fatty substance (isododecane) in a flask. After heating for 1 hour, the flask was placed in an oven at 25 °C and the solubility was observed. For samples that contained insoluble matter after 1 hour at 70 °C, the heating time was extended to 2 hours at 70 °C and the solubility was observed again after returning to room temperature.

[0324] [Table 12]

[0325] The PHA copolymers of Examples 1-4, which were soluble in isododecane or isododecane / ethanol mixtures, were evaluated for their cosmetic properties in dry films.

[0326] evaluation: In the first step, a membrane is created on the contrast card using a membrane spreader (speed: 50 mm / sec - cylinder: 100 μm). The membrane is dried at room temperature for 24 hours. After drying, the membrane is approximately 40 μm thick (Figure 1).

[0327] The PHA copolymers of Examples 1-4, which were soluble in isododecane or isododecane / ethanol mixtures, were evaluated for their cosmetic properties in dry films.

[0328] In a first step, a membrane is made on the contrast card using a membrane spreader (speed: 50 mm / sec - cylinder: 100 μm). The membrane is dried at room temperature for 24 hours. After drying, the thickness of the membrane is about 40 μm.

[0329] Three evaluations are performed on the dry film: grease resistance, gloss, and tack.

[0330] Grease resistance measurement Three drops of olive oil or sebum or water were placed on the dry film present in the black area of ​​the contrast card, each drop corresponding to approximately 10 μL of olive oil (using a micropipette).

[0331] The droplets are left in contact with the dry film for two times: 5 minutes and 30 minutes. After the time has elapsed, the droplets of olive oil or sebum or water are wiped off and an observation of the degradation of the polymer film is carried out. If the film is damaged by the droplets of olive oil or sebum or water, the polymer film is considered to be not resistant to olive oil or sebum.

[0332] [Table 13]

[0333] It turns out that with the PHA copolymers of the invention it is possible to obtain dry homogeneous films which are particularly resistant to water, olive oil and sebum.

[0334] Gloss Measurement Measure the gloss with a glossmeter on the black part of the contrast card (Figure 2). The gloss is read at an angle of 20° (the angle at which it is easiest to distinguish).

[0335] [Table 14]

[0336] Tackiness was assessed sensorily and qualitatively by touching the dried film with a finger.

[0337] It can be seen that the tested Examples 1 and 2 have no tackiness.

[0338] [Table 15]

[0339] Preparation method: The polymer dissolved in isododecane or isododecane / ethanol is mixed with the pigment at 3500 rpm for 2 minutes.

[0340] The evaluation is carried out on BioSkin. In a first step, a film of each formulation is deposited on a sample of BioSkin by means of a film spreader. The wet film thickness is 100 μm. The film is allowed to dry at room temperature for 24 hours. Once the film is dry, the test can be carried out.

[0341] Resistant to olive oil / sebum 0.5 mL of olive oil or sebum is applied to the film of the formulation. After 5 minutes, the olive oil or sebum is removed by wiping 15 times with cotton wool. In this way, the degradation of the film after contact with olive oil or sebum is tested (see Figure 2).

[0342] Resistant to adhesive tape A strip of adhesive tape (Scotch® type) is applied to the film of the formulation. Weight is applied to the strip of adhesive tape for 30 seconds. The adhesive tape is then removed and mounted on a slide holder to observe the results.

[0343] In that way, the adhesion of the membrane to the support is evaluated (see FIG. 2).

[0344] [Table 16]

[0345] The results obtained show that the composition according to the invention has good resistance to oil and sebum and good durability. Thus, the lipstick composition applied to the lips makes it possible to obtain a makeup result that is resistant to oil and sebum, does not produce uneven coloring on the lips, and has good durability.

[0346] Example 7: C 11 Side chain R represents an alkyl group (n-undecyl group) 1 and R representing an n-nonyl group2 A copolymer of PHA having The method for obtaining Example 7 was adapted from "Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates" by Richard D. Ashby, Daniel K. Y. Solaiman and Thomas A. Foglia, ACS Symposium Series; American Chemical Society: Washington, DC, 2001.

[0347] The microorganism used is Pseudomonas resinovorans ATCC® 14235™. The cultivation mode is carried out under pure culture conditions in non-fed-batch discontinuous culture in 5 L Fernbach flasks (Corning® reference 431685) containing 2 culture medium, stirred at 110 rpm at 30°C in an orbital incubator (orbital diameter 2.5 cm).

[0348] The synthetic method is carried out using two separate culture media: the first culture medium, defined as MC1 "inoculum", is used for the preparation of a pre-culture; the second culture medium, defined as MC2 "batch", is used to grow a non-fed batch culture of the microorganism with the carbon source of interest in a Fernbach flask.

[0349] [Table 17]

[0350] The composition of the nutrient broth, by weight, is 37.5% beef extract and 62.5% peptone, reference 233000 DIFCO® BD.

[0351] [Table 18]

[0352] A 100 mL preculture is prepared by suspending a cryotube containing 1 mL of strain together with 100 mL of "inoculum" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then incubating for 24 hours at 150 rpm at 30° C. 1.9 L of "batch" MC2 culture medium in a sterile 5 L Fernbach flask is inoculated with 100 mL of inoculum at OD=0.1.

[0353] After 50 h at 30° C. and 110 rpm, the biomass was dried by freeze-drying and then extracted with dichloromethane for 24 h. The suspension was clarified by filtration through a GF / A filter (Whatman®), concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass.

[0354] The PHA can optionally be purified by dissolution and successive precipitation, for example with a dichloromethane-methanol mixture.

[0355] The PHA copolymer of Example 7 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure.

[0356] [Table 19]

[0357] The PHA copolymers of Example 7, which are soluble in isododecane or isododecane / ethanol mixtures, were evaluated for their cosmetic properties in dry films.

[0358] [Table 20]

[0359] It can be seen that with the PHA copolymer 7 according to the invention it is possible to obtain dry homogeneous films which are particularly resistant to water, olive oil and sebum.

[0360] Gloss Measurement Measure the gloss with a glossmeter on the black part of the contrast card (Figure 2). The gloss is read at an angle of 20° (the angle at which it is easiest to distinguish).

[0361] [Table 21]

[0362] Example 8: Poly(3-hydroxynonanoate-co-undecenoate) containing 100% epoxidized 5% unsaturation: [ka] 20 g of the PHA copolymer of Example 2 was dissolved in 80 mL of anhydrous dichloromethane. A suspension of 1.9 g of 77% m-CPBA was prepared with 20 mL of anhydrous dichloromethane and added to the mixture by stirring at room temperature for at least 120 hours.

[0363] The reaction medium was then precipitated from a 500 mL mixture of 70 / 30 v / v ethanol / water. A viscous white precipitate was obtained. This step can be repeated. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a uniform coating.

[0364] The PHA of Example 8 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. It is epoxidized to 100%.

[0365] [Table 22]

[0366] It can be seen that with the PHA copolymer 8 according to the invention it is possible to obtain dry homogeneous films which are particularly resistant to water, olive oil and sebum.

[0367] Gloss Measurement The gloss is measured using a glossmeter on the black part of the contrast card. The gloss is read at an angle of 20° (the angle at which it is most easily discerned).

[0368] Evaluation of the gloss of the pure polymer of Example 8 soluble in isododecane and isododecane / ethanol:

[0369] [Table 23]

[0370] The tackiness was evaluated by sensory and qualitative methods by touching the dried film with a finger, and it was found that the tested Example 8 had no tackiness.

Claims

1. a) 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) and also optical or geometric isomers and solvates thereof, such as hydrates, wherein in the polymer units (A) and (B), - R １ i) branched (C ５ ~C ９ ) alkyl, ii) (C １０ ~C ３０ ) alkyl; iii) linear or branched (C ５ ~C ３０ ) alkenyl; iv) linear or branched (C ５ ~C ３０ ) alkynyl; v) (hetero)aryl; vi) (hetero)cycloalkyl; preferably the groups i) (C １０ ~C ２０ ) alkyl or iii) (C ８ ~C ２０ ) alkenyl; - R ２ represents a cyclic or acyclic, linear or branched, saturated or unsaturated, hydrocarbon-based group containing from 1 to 30 carbon atoms; and b) a fatty medium comprising one or more fatty substances which are preferably liquid at 25° C. and atmospheric pressure; wherein it is understood that (A) is different from (B).

2. The PHA copolymer has the formula (I): 【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, R １ and R ２ When represents an alkyl group, m>n, and preferably R １ and R ２ When is alkyl, R １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ represents an alkenyl group or an alkyl group, and R ２ When represents an alkyl group, m<n. and also optical or geometric isomers thereof and solvates thereof, such as hydrates.

3. The PHA copolymer a) contains three different repeating polymer units (A), (B) and (C), preferably the following three different polymer units (A), (B) and (C): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) -[-O-CH(R ３ )-CH ２ -C(O)-]- unit (C) (In the polymer units (A), (B) and (C), - R １ and R ２ is as defined in claim 1; - R ３ represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon-based group containing 1 to 30 carbon atoms, in particular linear or branched (C １ ~C ２８ ) alkyl and linear or branched (C ２ ~C ２８ ) alkenyl, in particular linear hydrocarbon-based groups, more particularly (C ４ ~C ２０ ) alkenyl; preferably, the hydrocarbon-based group is １ or else the number of carbon atoms of said group R minus at least 3 carbon atoms. １ the number of carbon atoms of said group R １ having a number of carbon atoms corresponding to the number of carbon atoms in and also optical or geometric isomers thereof and solvates thereof, such as hydrates; and - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and Preferably, R １ , R ２ and R ３ represents an alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B) and greater than the mole percentage of units (C), and more preferentially, R １ , R ２ and R ３ When is alkyl, R １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ and R ３ is R minus 4 carbon atoms. １ represents an alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ When R represents an alkenyl or alkynyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and less than the mole percentage of units (C), in particular R ２ represents an alkyl group, and / or R ３ When represents an alkyl group, preferably, R ３ is R minus two carbon atoms. ２ It is understood that this represents an alkyl group having a number of carbon atoms corresponding to the number of carbon atoms of More preferentially, said PHA copolymer has formula (II): 【Chemistry 2】 (In formula (II), ・R １ , R ２ and R ３ is as defined above; m, n and p are integers equal to or greater than 1; preferably, the sum of n+m+p is between 450 and 1400, inclusive; Preferably, R １ , R ２ and R ３ If represents an unsubstituted and uninterrupted alkyl group, then m>n+p, and preferentially R １ , R ２ and R ３ When is alkyl, R １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ and R ３ is R minus 4 carbon atoms. １ represents an alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ represents an alkenyl group or an alkynyl group; R ２ and R ３ represents an alkyl group, preferably R ３ is R with two carbon atoms subtracted. ２ When m represents an alkyl group having a carbon number corresponding to the carbon number of m, m is less than n+p. and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof and solvates thereof, such as hydrates.

4. The PHA copolymer a) contains four different repeating polymer units (A), (B), (C) and (D), preferably the following four different polymer units (A), (B), (C) and (D): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) -[-O-CH(R ３ )-CH ２ -C(O)-]- unit (C) -[-O-CH(R ４ )-CH ２ -C(O)-]- unit (D) (In the polymer units (A), (B), (C) and (D), - R １ , R ２ and R ３ is as defined in claim 1 or 3; - R ４ represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms; in particular linear or branched (C ４ ~C ２８ ) alkyl, and also its optical or geometric isomers, its organic or mineral acid or base salts and also its solvates, such as hydrates; and - (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, R １ , R ２ , R ３ and R ４ represents an alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), greater than the mole percentage of units (C) and greater than the mole percentage of units (D); more preferentially, R １ , R ２ , R ３ and R ４ When is alkyl, R １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ and R ３ is R minus 4 carbon atoms. １ and R ４ is R minus 6 carbon atoms. １ represents an alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ When R represents an alkenyl or alkynyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and less than the mole percentage of units (C), in particular R ２ represents an alkyl group, and / or R ３ represents an alkyl group, and R ４ When represents an alkenyl or alkynyl group, preferably, R ３ is R minus two carbon atoms. ２ and R ４ is R minus two carbon atoms. １ It is understood that the carbon number of the alkenyl group or alkynyl group corresponds to the carbon number of the carbon atom of the formula (I) and (II). More preferentially, said PHA copolymer has formula (III): 【Chemistry 3】 (In formula (III), ・R １ , R ２ , R ３ and R ４ is as defined above, m, n, p and v are integers equal to or greater than 1; preferably, the sum of n+m+p+v is between 450 and 1400, inclusive; Preferably, R １ , R ２ , R ３ and R ４ When represents an alkyl group, m>n+p+q, and R １ , R ２ , R ３ and R ４ When is alkyl, R １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ３ is R minus 4 carbon atoms. １ and R ４ is R minus 6 carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ represents an alkenyl group or an alkynyl group; R ２ and R ３ represents an alkyl group, and R ４ When R represents an alkenyl or alkynyl group, n>m+v; more preferentially n+p>m+v; preferably, R ３ is R minus two carbon atoms. ２ and R ４ is R minus two carbon atoms. １ represents an alkenyl group or alkynyl group having a carbon number corresponding to the carbon number of and also its optical or geometrical isomers, its organic or mineral acid or base salts and its solvates, such as hydrates.

5. The PHA copolymer a) contains five different repeating polymer units (A), (B), (C), (D) and (E), preferably the following five different polymer units (A), (B), (C), (D) and (E): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) -[-O-CH(R ３ )-CH ２ -C(O)-]- unit (C) -[-O-CH(R ４ )-CH ２ -C(O)-]- unit (D) -[-O-CH(R ５ )-CH ２ -C(O)-]- unit (E) (In the polymer units (A), (B), (C), (D) and (E), - R １ , R ２ and R ３ is as defined in any one of claims 1 or 3 to 5; - R ４ represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, in particular linear or branched (C ４ ~C ２８ ) alkyl; and - R ５ represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, in particular linear or branched (C ４ ~C ２８ ) alkyl; preferably, said hydrocarbon-based group is selected from said group R ４ the number of carbon atoms of said group R ４ having a number of carbon atoms corresponding to the number of carbon atoms in and also its optical or geometric isomers, its organic or mineral acid or base salts and also its solvates, such as hydrates; - (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, R １ , R ２ , R ３ , R ４ and R ５ represents an alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), greater than the mole percentage of units (C), greater than the mole percentage of units (D) and greater than the mole percentage of units (E); more preferentially, R １ , R ２ , R ３ , R ４ and R ５ When is alkyl, R １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ represents an alkyl group having a carbon number corresponding to the carbon number of R ３ is R minus 4 carbon atoms. １ represents an alkyl group having a carbon number corresponding to the carbon number of R ４ is R minus 6 carbon atoms. １ and R ５ is R minus 8 carbon atoms. １ represents an alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ When R represents an alkenyl or alkynyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and less than the mole percentage of units (C), in particular R ２ represents an alkyl group, and R ３ represents an alkyl group, and R ４ and R ５ When represents an alkenyl or alkynyl group, preferably, R ３ is R minus two carbon atoms. ２ and R ４ is R minus two carbon atoms. １ represents an alkenyl group or alkynyl group having a carbon number corresponding to the carbon number of R ５ is R minus 4 carbon atoms. １ It is understood that the carbon number of the alkenyl group or alkynyl group corresponds to the carbon number of the carbon atom of the formula (I) and (II). More preferentially, said PHA copolymer has formula (IV): 【Chemistry 4】 (In formula (IV), ・R １ , R ２ , R ３ , R ４ and R ５ is as defined above; m, n, p, v and z are integers equal to or greater than 1; preferably, the sum of n+m+p+v+z is between 450 and 1400, inclusive; Preferably, R １ , R ２ , R ３ , R ４ and R ５ represents an alkyl group, m>n+p+v+z; Preferably, R １ represents an alkenyl group or an alkynyl group; R ２ and R ３ represents an alkyl group, and the group R ４ and R ５ When R represents an alkenyl or alkynyl group, n>m+v+z; more preferentially n+p>m+v+z; preferably R ３ is R minus two carbon atoms. ２ and R ４ is R minus two carbon atoms. １ represents an alkenyl group or alkynyl group having a carbon number corresponding to the carbon number of R ５ is R minus 4 carbon atoms. １ represents an alkenyl group or alkynyl group having a carbon number corresponding to the carbon number of and also its optical or geometrical isomers, its organic or mineral acid or base salts and its solvates, such as hydrates.

6. The PHA copolymer a) is １ is a branched alkyl containing 5 to 9 carbon atoms, such as 2-methyl-5-pentyl, 2-methyl-2-pentyl, isobutyl or 2-methylheptyl, preferably 2-methyl-5-pentyl, or R １ ii) linear or branched, preferably linear (C １０ ~C ３０ 6. The composition according to claim 1, wherein: R represents an alkyl radical.

7. The PHA copolymer a) is a copolymer having the group R １ , R ２ , R ３ , R ４ and R ５ The composition according to any one of claims 1 to 6, wherein the stereochemistry of the carbon atom having

8. The PHA copolymer a) is １ iii) linear or branched (C ５ ~C ３０ ) alkenyl, more particularly linear and containing at least one unsaturation, preferably only one, at the end of the alkenyl group, linear or branched (C ５ ~C ３０ ) alkenyl; even more particularly, R １ is selected from the group: -[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 are a hydrogen atom or a (C １ ~C ４ ) an alkyl group, preferably a hydrogen atom, and q represents an integer between 2 and 20, preferably between 3 and 10, more preferentially between 4 and 8, for example 6, inclusive; more particularly R １ The composition according to any one of claims 1 to 5 or 7, wherein is such that is selected from hexenyl, octenyl, undecenyl, 2-butenyl and 2-methyl-2-pentenyl.

9. The PHA copolymer a) is ２ is linear or branched (C １ ~C ２８ ) alkyl and linear or branched (C ２ ~C ２８ ) alkenyl, especially linear hydrocarbon-based groups, especially (C ３ ~C ２０ ) alkyl or (C ３ ~C ２０ ) alkenyl; preferably, the hydrocarbon-based group is selected from the group R １ the number of carbon atoms of said group R １ The composition according to any one of claims 1 to 8, wherein the carbon number corresponds to the number of carbon atoms of

10. The PHA copolymer a) is a copolymer having the group R ２ is linear or branched, preferably linear (C １ ~C ８ ) alkyl, especially (C ２ ~C ６ ) alkyl, preferably (C ４ ~C ６ ) alkyl group, such as n-pentyl or n-hexyl; or R2 is a branched (C ３ ~C ８ ) alkyl, especially (C ４ ~C ６ ) alkyl group, preferably branched (C ４ ~C ５ 10. The composition according to any one of claims 1 to 9, wherein the aryl group is aryl, aryl, aryl or aryl.

11. The PHA copolymer a) is １ is an alkyl group, said units (A) are present in a molar percentage ranging from 30% to 99%, preferentially in a molar percentage ranging from 40% to 95%, more preferentially in a molar percentage ranging from 50% to 85%, even more preferentially in a molar percentage ranging from 60% to 70%; and said units (B) are present in a molar percentage ranging from 0.5% to 70%, preferentially from 2% to 10% and more preferentially from 5% to 35% of units (B); and / or Composition according to any one of claims 1 to 7, 9 or 10, such that said units (C) are present in a molar percentage ranging from 0 to 20%, preferentially from 0.1% to 10% and more preferentially from 0.5% to 7% of units (C).

12. The PHA copolymer a) is １ is an alkenyl or alkynyl radical as defined above, said units (A) are present in a molar percentage ranging from 0.1% to 50%, more preferentially from 0.5% to 40%, even more preferentially from 1% to 40%, even better from 5% to 30%, from 8% to 20%, relative to the total; and said units (B) are present in a molar percentage ranging from 70% to 99.5%, preferably from 60% to 95%. and said units (C) are present in a molar percentage ranging from 0% to 30%, preferably from 1% to 25%, more preferentially from 5% to 24%, said 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 said 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.

13. The composition according to any one of claims 1 to 12, wherein the PHA copolymers a) are such that they comprise the following repeating units: 【Chemistry 5】 【Table 1】 More particularly, 【Chemistry 6】 【Table 2】 【Chemistry 7】 【Table 3】 【Chemistry 8】 【Table 4】 【Chemistry 9】 【Table 5】

14. The fatty medium is Branched C ８ ~C １６ Alkanes, e.g. petroleum-derived C ８ ~C １６ Isoalkanes (also known as isoparaffins), such as isododecane, isodecane or isohexadecane; Linear C ８ ~C １６ Alkanes, such as n-dodecane (C １２ ) and n-tetradecane (C １４ ) and also mixtures thereof, undecane-tridecane mixtures, n-undecane (C １１ ) and n-tridecane (C １３ ) and mixtures thereof; □ Fatty acid is C ４ ~C ２４ triglycerides consisting of fatty acid esters of glycerol which may have various chain lengths, the chains being optionally linear or branched and saturated or unsaturated, such as triglycerides, in particular ester oils chosen from oils of vegetable origin, in particular heptanoic or octanoic acid triglycerides, said oils of vegetable origin being wheat germ oil, sunflower oil, grapeseed oil, sesame oil, peanut oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sugar bean oil, almond oil, palm oil, rapeseed oil, cottonseed oil, coconut oil, hazelnut oil, walnut oil, rice oil, linseed oil, macadamia oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil and argan oil; shea butter; or an ester oil, which may alternatively be selected from caprylic / capric triglycerides; □Formula R ９ -C(O)-OR １０ (In the formula, R ９ +R １０ R has ≧9 carbon atoms, preferably less than 29 carbon atoms. ９ represents a linear or branched hydrocarbon-based chain containing from 5 to 19 carbon atoms, and R １０ represents a linear or branched, especially branched, hydrocarbon-based chain containing 4 to 20 carbon atoms), such as, for example, palmitate, adipate, myristate and benzoate, especially diisopropyl adipate and isopropyl myristate; cetearyl octanoate (Percellin oil), isopropyl myristate, isopropyl palmitate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, 2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate or octyl octanoate; Lactic acid and C １０ ~C ２０ Esters with alcohols, such as isostearyl lactate, 2-octyldodecyl lactate, myristyl lactate, C １２ ~C １３ Alkyl lactate, cetyl lactate or lauryl lactate; Malic acid and C １０ ~C ２０ Diesters with alcohols, such as diisostearyl malate, di(C １２ ~C １３ (alkyl) malate, dibutyl octyl malate, diethyl hexyl malate or dioctyl dodecyl malate; Pentaerythritol and C ８ ~C ２２ Esters (especially tetraesters or diesters) with carboxylic acids, such as pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate, pentaerythrityl tetrabehenate, pentaerythrityl tetracaprylate / tetracaprate, pentaerythrityl tetracocoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrastearate, pentaerythrityl tetraisostearate, pentaerythrityl tetralaurate, pentaerythrityl tetramyristate, pentaerythrityl tetraoleate or pentaerythrityl distearate; □Formula R １１ -OC(=O)-R １２ -C(=O)-OR １３ (In the formula, R １１ and R １３ may be the same or different, optionally containing at least one saturated or unsaturated, preferably saturated, ring, linear or branched, saturated or unsaturated (preferably saturated) C ４ ~C １２ , with priority given to C ５ ~C １０ represents an alkyl chain, and R １２ is saturated or unsaturated C １ ~C ４ , preferably C ２ ~C ４ Alkylene chains, such as succinates (where R １２ is saturated C ２ alkylene chain), maleate (in this case R １２ is unsaturated C ２ alkylene chain), glutarate (in this case R １２ is saturated C ３ alkylene chain) or adipate (in this case R １２ is saturated C ４ In particular, R １１ and R １３ is selected from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl and isononyl), of which preferential mention may be made of dicaprylyl maleate or bis(2-ethylhexyl)succinate; □Formula R １４ -C(=O)-OR １５ -OC(=O)-R １６ (In the formula, R １４ and R １６ may be the same or different, linear or branched, saturated or unsaturated (preferably saturated) C ４ ~C １２ , with priority given to C ５ ~C １０ represents an alkyl chain, and R １５ is saturated or unsaturated C １ ~C ４ , preferably C ２ ~C ４ diesters of 1,3-propanediol dicaprylate (C ７ R as １４ and C ３ R as １６ ) or dipropylene glycol dicaprylate; Carbonate oil is represented by the following formula R １７ -OC(O)-OR １８ wherein R １７ and R １８ may be the same or different, linear or branched C ４ ~C １２ , with priority given to C ６ ~C １０ represents an alkyl chain; said carbonate oil may be dicaprylyl carbonate (or dioctyl carbonate), bis(2-ethylhexyl) carbonate, dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate, preferably dioctyl carbonate; and □ Mixtures of these The composition according to any one of claims 1 to 13, comprising one or more substances selected from:

15. The composition according to any one of the preceding claims, wherein the fatty medium comprises one or more fatty substances in a content ranging from 2% to 99.9% by weight relative to the total weight of the composition, preferably ranging from 5% to 90% by weight, preferably ranging from 10% to 80% by weight and preferably ranging from 20% to 80% by weight relative to the total weight of the composition.

16. The fatty medium is preferably a solvent other than water, preferably a polar and / or protic solvent, more preferentially a C ２ ~C ６ 16. The composition according to any one of the preceding claims, comprising an alkanol, such as one selected from ethanol, propanol, butanol, pentanol and hexanol, preferably ethanol; more particularly, said solvent is present in the composition in a weight percentage of from 0 to 10% by weight relative to the total weight of the solvent mixture, preferentially from 0.5% to 8% by weight, more particularly from 1% to 5% by weight, for example 2% by weight relative to the total weight of the composition.

17. The composition according to any one of the preceding claims, wherein the fatty medium comprises one or more fatty substances in a content ranging from 2% to 99.9% by weight relative to the total weight of the composition, preferably ranging from 5% to 90% by weight, preferably ranging from 10% to 80% by weight and preferably ranging from 20% to 80% by weight relative to the total weight of the composition.

18. 18. The composition according to any one of claims 1 to 17, which also comprises one or more colorants, preferably pigments, chosen from pigments, direct dyes and mixtures thereof; more preferentially, said pigments of the present 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, also azo pigments, in particular red azo pigments, such as D&C Red 7, alkali metal salts of lithole red, such as the calcium salt of lithole red B, and even more preferentially red iron oxide.

19. 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, by applying a composition according to any one of claims 1 to 18.

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