Cosmetic composition comprising a (un)saturated hydrocarbon chain polyhydroxyalkanoate copolymer, and at least one polyurethane latex

Abstract

Title: Cosmetic composition comprising a polyhydroxyalkanoate copolymer with (un)saturated hydrocarbon chain, and at least one polyurethane latex. The present invention relates to a cosmetic composition C1 comprising a) at least one polyhydroxyalkanoate copolymer with (un)saturated hydrocarbon groups, b) at least one polyurethane latex, c) optionally at least one fat, d) optionally at least one surfactant and e) water, as well as a process for treating keratinous materials using such a composition.

Description

Title of the invention: Cosmetic composition comprising a polyhydroxyalkanoate copolymer with an (un)saturated hydrocarbon chain, and at least one polyurethane latex

[0001] The present invention relates to a cosmetic composition Cl comprising a) at least one polyhydroxyalkanoate copolymer with (un)saturated hydrocarbon groups, b) at least one polyurethane latex, c) optionally at least one fatty substance, d) optionally at least one surfactant and e) water as well as a process for treating keratin materials using such a composition.

[0002] It is known to use in cosmetics film-forming polymers which can be transported in organic media such as hydrocarbon oils. The polymers are used in particular as film-forming agents in makeup products such as mascaras, eyeliners, eye shadows or lipsticks.

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

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

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

[0006] Document US2011 / 0015279 describes the use of polyurethane (PUR) latex in skin care. Document EP1970391 describes the use of PUR latex to increase adhesion to hair and its shaping properties. Document WO2020074490 describes the use of PUR latex as a film-forming agent in the field of cosmetics and document WO2021198051 describes these derivatives in makeup applications. None of these documents describes the combination of PUR latex with polyhydroxyalkanoates. They do not discuss the technical problem of friction resistance or the potential improvement of adhesion to the substrate in a greasy environment.

[0007] Most polyhydroxyalkanoate copolymers are polymers resulting from the polycondensation of repeating polymer units that are largely identical and derived from the same carbon source or substrate. These documents do not describe the cosmetic use of copolymers resulting from the polycondensation from a substrate or first source of aliphatic carbon, and at least a second substrate different from the first comprising one or more (un)saturated hydrocarbon groups with polyurethane latexes. A need therefore exists to have a composition comprising hydrophilic or lipophilic polyhydroxyalkanoate copolymers soluble in the fatty phase. This makes it possible to obtain a film on keratin materials having good cosmetic properties, in particular good resistance to oils and sebum, as well as being able to play on the shine or mattness, which is easy to apply, non-sticky and flexible enough to be comfortable after application to keratin materials.

[0008] The applicant has discovered that polyhydroxyalkanoate copolymers with particular grafted or functionalized hydrocarbon groups, as defined below, can be easily implemented in fatty media, thus making it possible to obtain homogeneous compositions. The composition has good stability, in particular after storage for one month at room temperature (25°C). The composition, in particular after its application to keratin materials, makes it possible to obtain a film having good cosmetic properties, in particular good resistance to oils and sebum, as well as a matte or shiny appearance.

[0009] However, in many conditions of use of film-forming materials on keratin materials such as in makeup or coloring applications for example, it is desirable to have, in addition to good resistance to water and oils, particularly food oils such as olive oil, very good resistance to rubbing of the deposits of film-forming materials both to avoid transfer, for example, to clothing, and to maintain a uniform appearance of the deposits. If the resistance to rubbing is insufficient, deposits can be obtained which quickly become very unsightly for consumers, in particular if these deposits are colored as in makeup applications such as lipsticks, foundations or mascaras.In hair applications, the lack of friction resistance is also very problematic in all coloring applications because they cause transfer to clothing and create an unsightly appearance of the keratin fibers.

[0010] There is therefore a real need to obtain deposits of film-forming materials which are resistant to oils, particularly food oils, resistant to water and have very good resistance to friction. Furthermore, for cosmetic use, it is necessary that the shine or matt finish conform to the expectations of consumers depending on the intended use. Thus, for a gloss, a high shine will be sought, whereas for a foundation, the most natural appearance possible will be sought. In the hair sector, a shine may be sought which must nevertheless remain within an acceptable range, as too high a shine can be unsightly and a matt finish too high being a hindrance to use. It is therefore important to be able to modulate the gloss and / or mattness, for example by using specific additives when possible or by using mixtures of film-forming polymers whose gloss and mattness properties can be complementary. For example, it will be possible to combine a compound deemed too matt in an application with another glossy compound so that the combination of the two is of gloss or mattness consistent with the intended application.

[0011] This problem is solved by the use of compositions C1 described below, these compositions making it possible to significantly improve the friction resistance of the polyhydroxyalkanoate (PHA) copolymer(s). In addition, the compositions C1 according to the invention make it possible to obtain, after deposition, a film on keratin materials having good cosmetic properties, in particular good resistance to oils and sebum, good resistance to water as well as being able to play on the shine or mattness. The deposits obtained are non-sticky and flexible and therefore comfortable after application to keratin materials.

[0012] Thus the main object of the present invention is a composition Cl comprising:

[0013] a) one or more polyhydroxyalkanoate (PHA) copolymer(s) which contain(s), preferably consisting of, several repeating units chosen from the following units (A), as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0014] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0015] polymeric units (A) in which: - R 1 represents a hydrocarbon chain, non-cyclic, saturated or unsaturated, linear or branched, or cyclic, saturated or unsaturated, aromatic or non-aromatic, comprising from 5 to 28 carbon atoms; preferably the hydrocarbon chain is chosen from i) (C5-C28)alkyl, linear or branched, ii) (C5-C28)alkenyl, linear or branched, iii) (C5-C28)alkynyl, linear or branched, preferably the hydrocarbon group is linear; said hydrocarbon chain being: • optionally substituted by one or more atoms or groups chosen from: a) halogen such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active; 1) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, 6) cosmetic active, m) thiosulfate and X representing a') O, S, N(Ra) or Si(Rb )(RC), b') S(O)r, or (thio)carbonyl, c') or the combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; R a representing a hydrogen atom, or a (Ci-C4)alkyl group, or aryl(Ci-C4)alkyl such as benzyl, preferably Ra represents a hydrogen atom; R b and R c, identical or different, represent a (Ci-C4)alkyl or (C1-C4 )alkoxy group, particularly a single substituent; preferably chosen from b) halogen, and j) such as epoxide; and / or • optionally interrupted by one or more a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, c') or combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide with r being 1 or 2, R a being as defined above, preferably R a represents a hydrogen atom, R b and R c being as defined above; and (b) one or more polyurethane latexes; and

[0016] c) optionally one or more fatty substances; preferably liquid at 25°C and at atmospheric pressure; and

[0017] d) optionally one or more surfactants; and

[0018] e) water,

[0019] preferably the composition C1 comprises c) one or more fatty substances and d) one or more surfactants and e) water.

[0020] Another object of the invention is the use in cosmetics of a composition Cl comprising a) one or more PHA copolymer(s) as defined above, b) one or more polyurethane latexes as defined above, c) optionally one or more fatty substances as defined above, d) one or more surfactants and d) water, preferably comprising c) one or more fatty substances and d) one or more surfactants and e) water.

[0021] Another subject of the invention is a process for treating keratin materials, preferably a) keratin fibers, in particular human fibers such as hair, or |3) human skin, in particular the lips, using a) one or more PHA copolymer(s) as defined above, b) one or more polyurethane latexes as defined above, optionally c) one or more fatty substances as defined above, optionally d) one or more surfactants and d) water, preferably using a) and b) and c) and d) and e).

[0022] More particularly, the subject of the invention is a non-therapeutic cosmetic process for treating keratin materials, comprising the application to the keratin materials of a composition Cl as defined above. The treatment process is in particular a process for caring for or making up keratin materials.

[0023] For the purposes of the present invention, and unless otherwise indicated:

[0024] By “polyurethane latex” is meant an aqueous dispersion of polyurethane polymer as defined above; the terms “polyurethane polymer(s) latex” and “polyurethane latex” are equivalent;

[0025] By “Cosmetic active”: we mean the radical of an organic or organosilicon compound which can be integrated into a cosmetic composition to provide an effect on keratin materials, whether this effect is immediate or provided by repeated applications.Examples of cosmetic active ingredients include colored or non-colored, fluorescent or non-colored chromophores such as those derived from optical brighteners, or chromophores derived from UVA and / or UVB filters, anti-aging active ingredients or those intended to provide a benefit to the skin such as active ingredients having an action on the barrier function, deodorant active ingredients other than mineral particles, antiperspirant active ingredients other than mineral particles, desquamating active ingredients, antioxidant active ingredients, moisturizing active ingredients, sebum-regulating active ingredients, active ingredients intended to limit skin shine, active ingredients intended to combat the effects of pollution, antimicrobial or bactericidal active ingredients, anti-dandruff active ingredients, and perfumes. - By “(hetero)aryl” we mean aryl or heteroaryl groups; - By "(hetero)cycloalkyl" we mean cycloalkyl groups or heterocycloalkyl; - The “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom, chosen from: • a C1-C6 alkyl radical, preferably C1-C4; • a halogen atom such as chlorine, fluorine or bromine; • a hydroxy group; • a C1-C2 alkoxy radical; a C2-C4 (poly)-hydroxyalkoxy radical; • an amino radical; • an amino radical substituted by one or two alkyl radicals, identical or different, in C1-C6, C1-C6, preferably in C1-C4; • an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical and the radical R' is a C1-C4 alkyl radical; a carbamoyl radical ((R)2N-CO-) in which the radicals R, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical; an alkylsulfonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom, a CrC4 alkyl radical and the radical R' represents a CrC4 alkyl radical, a phenyl radical; an aminosulfonyl radical ((R)2N-SO2-) in which the radicals R, identical or not, represent a hydrogen atom, a C1-C4 alkyl radical; a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group (CN); a polyhalo(Ci-C4)alkyl group, preferably trifluoromethyl (CF3); the cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups: hydroxy, CrC4 alkoxy, C2-C4 (poly)hydroxyalkoxy, alkylcarbonylamino ((RCO-NR'-) in which the radical R' is a hydrogen atom, a CrC4 alkyl radical and the radical R is a CrC2 alkyl radical, amino substituted by one or two identical or different CrC4 alkyl groups; alkylcarbonyloxy ((RCO-O-) in which the radical R is a CrC4 alkyl radical, amino substituted by one or two identical or different C1-C4 alkyl groups; alkoxycarbonyl ((RO-CO-) in which the radical R is a Cr-C4 alkyl radical, amino substituted by one or two identical or different C1-C4 alkyl groups; a cyclic, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted by one or more oxo groups; a hydrocarbon chain is unsaturated when it contains one or more double bonds and / or one or more triple bonds; an “aryl” radical represents a mono or polycyclic hydrocarbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one cycle is aromatic; preferably the radical aryl is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl; a “heteroaryl” radical represents a mono or polycyclic group, condensed or not, comprising from 5 to 22 links, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, and of which at least one cycle is aromatic; preferably a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl; a “cyclic” or “cycloalkyl” radical is a non-aromatic, mono- or polycyclic, condensed or not, cyclic hydrocarbon radical containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations, preferably the cycloalkyl is a cyclohexyl group; a “heterocyclic” or “heterocycloalkyl” radical is a non-aromatic mono or polycyclic cyclic radical, condensed or not, containing from 3 to 9 members, comprising from 1 to 4 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, preferably the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidinyl, morpholinyl, dithiolane; an “alkyl” radical is a saturated, linear or branched hydrocarbon radical, in particular C1-C6, preferably C1-C4; an “alkenyl” radical is an unsaturated, linear or branched hydrocarbon radical, comprising one or more double bonds, conjugated or not; an “alkynyl” radical is an unsaturated, linear or branched hydrocarbon radical, comprising one or more triple bonds, conjugated or not; an “alkoxy” radical is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C1-C6, preferably in C1-C4; a "sugar" radical, is a monosaccharide radical, or polysaccharide, and their O-protected sugar derivatives such as esters of sugars and (Ci-C 6)alkylcarboxylic acids such as acetic acid, sugars with amine group(s) and (Ci-C4)alkyl derivatives, such as methylated derivatives like methylglucose. Examples of sugar radicals include: sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose; by "monosaccharide" is meant a monosaccharide sugar comprising at least 5 carbon atoms of formula CX(H2O)X, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x = 6, they can be of D or L configuration, and of alpha or beta anomer, as well as their salts and their solvates such as hydrates; by "polysaccharide" is meant a polysaccharide sugar which is a polymer consisting of several oses linked together by O-osidic bonds, said polymers being composed of monosaccharide units (also called mono-osidic) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the monosaccharide units are linked together in 1,4 or 1,6 in anomer α (alpha) or |3# (beta), each osidic unit being able to be of L or D configuration, as well as its salts and its solvates such as the hydrates of said monosaccharides;these are more particularly polymers formed from a certain number of oses (or monosaccharides) having the general formula: -[Cx(H2O)y)]w- or -[(CH2O)X]W-, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x = 6, and y an integer which represents x - 1, and w is an integer greater than or equal to 2, particularly inclusively between 3 and 3000, more particularly between 5 and 2500, preferably between 10 and 2300, particularly inclusively between 15 and 1000, more particularly between 20 and 500, preferably between 25 and 200; ; by "sugar with amine group(s)" is meant that the sugar radical is substituted by one or more amino group(s) NRiR2 ie at least one of the hydroxy groups of at least one saccharide unit of the sugar radical is replaced by an NRiR2 group, with Ri and R2, identical or different, representing i) a hydrogen atom, ii) a (Ci-C6)alkyl group, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, vii) -C(Y)-(Y')f-R'i with Y and Y', identical or different, representing an oxygen, sulfur or N(R'2) atom, preferably oxygen, f = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined above, and in particular R' i denoting a (Ci-C6)alkyl group such as methyl. Preferably R1 and / or R2 represent a hydrogen atom, or a (Ci-C4)alkylcarbonyl group such as acetyl and more preferably R1 represents a hydrogen atom and R2 represents a (Ci-C4)alkylcarbonyl group such as acetyl.by "organic or mineral acid salt" is meant more particularly the organic or mineral acid salts in particular chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids: Alk-S(O) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(O)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfmic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; (viii) phosphoric acid H3PO4; (ix) triflic acid CF3SO3H and (x) tetrafluoroboric acid HBF4;xi) organic carboxylic acids R°-C(O)-OH (l'z) formula (Fz) in which R° represents a (hetero)aryl group such as phenyl, (hetero)aryl(Ci-C4)alkyl such as benzyl, or (Ci-Cio)alkyl, said alkyl group being optionally substituted, preferably by one or more hydroxyl groups, amino radicals, or carboxy, R° preferably denoting a (Ci-C6)alkyl group optionally substituted by 1, 2 or 3 hydroxyl groups, or carboxy, more preferably the monocarboxylic acids of formula (l'z) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid; and the polycarboxylic acids are selected from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof;and xii) amino acids having more carboxylic acid radicals than amino groups such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid; ; an “anionic counterion” is an anion or an anionic group associated with the cationic charge; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including Ci-C6 alkylsulfonates: Alk-S(O)2O such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)2O such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfates: Alk-OS(O)O such as methylsulfate and ethylsulfate; x) aryl sulfates: Ar-OS(O)O such as benzenesulfate and toluenesulfate; xi) alkoxy sulfates: Alk-OS(O)2O such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-OS(O)2O, xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate. The "solvates" represent the hydrates as well as the association with linear or branched C1-C4 alcohols such as ethanol, isopropanol, n-propanol; by "chromophore" is meant a radical derived from a colorless or colored compound capable of absorbing UV and / or visible radiation at a wavelength Xabs between 250 and 800 nm; Preferably the chromophore is colored i.e. it absorbs wavelengths in the visible i.e. preferably between 400 and 800 nm. Preferably the chromophores appear colored to the eye; particularly between 400 and 700 nm (Ullmann's Encyclopedia, 2005, Wiley-VcH, Verlag "Dyes, General Survey", § 2.1 Basic Principle of Color); by "fluorescent chromophore" is meant a chromophore which is also capable of re-emitting in the visible range at an emission wavelength Xem of between 400 and 800 nm, and greater than the absorption wavelength. Preferably with a Stoke shift, i.e. the difference between the maximum absorption wavelength and the emission wavelength is at least 10 nm. Preferably, fluorescent chromophores are derived from fluorescent dyes capable of absorbing in the visible range Xabs, i.e. at a wavelength of between 400 and 800 nm, and of re-emitting in the visible range Xem of between 400 and 800 nm. More preferably, fluorescent chromophores are capable of absorbing at an Xabs between 420 nm and 550 nm and of re-emitting in the visible at an Xem between 470 and 600 nm. by "brightener chromophore" is meant a chromophore derived from optical brightener compound or "Optical brighteners, optical brightening agents (OBAs)" or "fluorescent brightening agents (FBAs)", or "fluorescent whitening agents (FWAs)" ie which absorbs UV radiation ie at a wavelength Xabs between 250 and 350 nm and then re-emits this energy by fluorescence in the visible at an emission wavelength Xem between 400 and 600 nm, i.e. the wavelengths between blue-violet and blue-green with a maximum in the blue. Optical brightener chromophores are therefore colorless to the eye. - A "UV-A filter" means a chromophore derived from a compound that filters (or absorbs) UV-A ultraviolet rays at a wavelength between 320 and 400 nm. A distinction can be made between short UV-A filters (absorbing rays at a wavelength between 320 and 340 nm) and long UV-A filters (absorbing rays at a wavelength between 340 and 400 nm). A "UV-B filter" means a chromophore derived from a compound that filters (or absorbs) UV-B ultraviolet rays at a wavelength between 280 and 320 nm. In addition, unless otherwise indicated, the limits delimiting the extent of a range of values ​​are included in this range of values. a) The PHA copolymer(s)

[0026] Composition C1 or C' 1 of the invention comprises as first ingredient a) one or more PHA copolymer(s) which contain(s) or preferably consist of at least two different repeating polymeric units of units (A) as defined above.

[0027] According to a particular embodiment of the invention, the composition according to the invention C1' comprises as first ingredient a) one or more PHA copolymer(s) which contain(s), or preferably consist of, at least two different repeating polymeric units chosen from units (A) and (B) as defined previously.

[0028] Preferably, the composition Cl of the invention is a composition Cl', preferably cosmetic, comprising a):

[0029] a) one or more polyhydroxyalkanoate (PHA) copolymer(s) which contain(s) and preferably consist of at least two different repeating polymeric units chosen from the following units (A) and (B), as well as their optical, geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0030] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0031] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0032] polymeric units (A) and (B) in which: - R 1 represents a hydrocarbon chain, non-cyclic saturated or unsaturated, linear or branched, or cyclic saturated or unsaturated aromatic or non-aromatic, comprising from 5 to 28 carbon atoms, particularly a hydrocarbon chain chosen from i) (C5-C28)alkyl, linear or branched, ii) (C5-C28)alkenyl, linear or branched, iii) (C5-C28)alkynyl, linear or branched, preferably the hydrocarbon group is linear; said hydrocarbon chain being: • optionally substituted by one or more atoms or groups chosen from: a) halogen such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active; 1) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, 6) cosmetic active, m) thiosulfate and X representing a') O, S, N(Ra) or Si(Rb )(RC), b') S(O)r, or (thio)carbonyl, c') or the combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; R a representing a hydrogen atom, or a (Ci-C4)alkyl group, or aryl(CrC4)alkyl such as benzyl, preferably Ra represents a hydrogen atom;R b and R c, identical or different, represent a (CrC4)alkyl or (CrC4)alkoxy group, particularly a single substituent; preferably chosen from b) halogen, and j) such as epoxide; and / or; • optionally interrupted by one or more a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, c') or the associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide with r being 1 or 2, R a being as defined previously, preferably R a represents a hydrogen atom, R b and R c being as defined previously; • R 2 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated or unsaturated, comprising from 3 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular chosen from (C3-C28)alkyl, linear or branched, and (C3-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C4-C20)alkyl or (C4-C20)alkenyl, preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 1 from which two carbon atoms are subtracted; and b) one or more polyurethane latex(es) as defined above and

[0033] c) optionally one or more fatty substances; preferably liquid at 25°C and at atmospheric pressure; and

[0034] d) optionally one or more surfactants; and

[0035] d) water,

[0036] preferably the composition C1 comprises c) one or more fatty substances and d) one or more surfactants and e) water.

[0037] By "co-polymer" is meant that said polymer is derived from the polycondensation of repeating polymer units which are different from each other, i.e. said polymer is derived from the polycondensation of repeating polymer units (A) with (B) it being understood that the polymer units (A) are different from the polymer units (B), said copolymer being obtainable from a single saturated or unsaturated aliphatic carbon source which is optionally substituted and / or interrupted, preferably unsubstituted uninterrupted, or from several carbon sources, in particular at least one of which is saturated aliphatic unsubstituted uninterrupted and the other carbon source(s) being saturated or unsaturated aliphatic, optionally substituted in particular by a halogen atom such as bromine, or by a cyano group, a bunte salt, a dithiolane radical, a carboxy, etc.

[0038] According to one embodiment, the copolymer according to the invention is derived from a single carbon source, preferably a single saturated or unsaturated aliphatic carbon source which is optionally substituted and / or interrupted, preferably unsubstituted or uninterrupted.

[0039] According to one embodiment, the copolymer according to the invention is derived from several carbon sources, preferably from 2 to 10 carbon sources, more preferably from 2 to 5 carbon sources, even more preferably from 2 carbon sources.

[0040] According to one embodiment, the copolymer according to the invention is derived from several carbon sources and at least one is saturated aliphatic.

[0041] According to a particular embodiment of the invention, the PHA copolymer(s) preferably comprise(s) two different repeating polymeric units chosen from units (A) as defined above units (B) such that R 2 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated or unsaturated, comprising from 3 to 30 carbon atoms; in particular chosen from (C3-C28)alkyl, linear or branched, and (C3-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C4-C20)alkyl or (C4-C20)alkenyl, preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 1 from which two carbon atoms are subtracted.

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

[0043] [Chem. 1]:

[0044]

[0045] Formula (I) in which: • R 1 and R 2 are as defined previously; • m and n are integers greater than or equal to 1, preferably the sum n + m is inclusively between 450 and 1400, preferably m > n when R 1 and R 2 represent an unsubstituted and uninterrupted alkyl group - more preferably when R1 and R2 are linear alkyl then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted such as a C3-Cn alkyl group; and

[0046] preferably m < n when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or interrupted alkenyl or optionally substituted and / or interrupted alkynyl, and R 2 represents an alkyl group.

[0047] According to a particular embodiment, the PHA copolymer(s) of composition a) contain three different repeating polymeric units (A), (B) and (C), preferably consists of the following 3 different polymeric units (A), (B) and (C), as well as their optical and geometric isomers and their solvates such as hydrates:

[0048] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0049] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0050] -[-O-CH(R3)-CH2-C(O)-]- unit (C)

[0051] polymeric units (A), (B) and (C) in which: - R \ and R 2 are as defined previously; - R 3 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated or unsaturated, comprising from 1 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular represents a hydrocarbon group chosen from (C1-C28)alkyl, linear or branched, and (C2-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C4-C20)alkenyl, preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R1, or corresponding to the number of carbon atoms of the radical R1 from which at least three carbon atoms are subtracted, preferably corresponding to the number of carbon atoms of the radical R1 from which four carbon atoms are subtracted; and it being understood that: - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and - preferably when R \ R 2 and R 2 represent an unsubstituted and uninterrupted alkyl group the molar percentage in unit (A) is greater than the molar percentage in unit (B), and greater than the molar percentage in unit (C) - more preferably when R1, R2 and R3 are linear alkyl, then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted, and R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R 1 from which 4 carbon atoms are subtracted, and - preferably when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, then the molar percentage in unit (A) is lower than the molar percentage in unit (B) and the molar percentage in unit (C) in particular if R2 represents an alkyl group and / or R3 represents an alkyl group.

[0052] According to a particular embodiment of the invention, the PHA copolymer(s) comprise the repeating unit of formula (II), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0053] [Chem. 2]:

[0054]

[0055] Formula (II) in which: • R1, R2 and R3 are as defined previously; • m, n and p are integers greater than or equal to 1, preferably the sum n + m + p is inclusively between 450 and 1400; and - preferably m > n + p when R \ R 2 and R 3 represent an unsubstituted and uninterrupted alkyl group - more preferably when R1, R2 and R3 are linear alkyl, then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted such as a C3-Cn alkyl group, and R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 4 carbon atoms are subtracted such as a C1-C9 alkyl group; and - preferably m < n + p when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, and R 2 and R 3 represent an alkyl group.

[0056] According to a particular embodiment, the PHA copolymer(s) of composition a) contain four different repeating polymeric units (A), (B), (C), and (D) preferably consists of the following 4 different polymeric units (A), (B), (C), and (D), as well as their optical and geometric isomers and their organic or mineral acid or base salts, as well as their solvates such as hydrates:

[0057] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0058] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0059] -[-O-CH(R3)-CH2-C(O)-]- unit (C)

[0060] -[-O-CH(R4)-CH2-C(O)-]- unit (D)

[0061] polymeric units (A), (B), (C) and (D) in which: R1, R2 and R3 are as defined above; - R 4 represents a saturated, cyclic or non-cyclic, linear or branched, hydrocarbon group comprising from 3 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular represents a hydrocarbon group chosen from (C4-C2s)alkyl, linear or branched, optionally substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined for R1; and it being understood that: - (A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), and (C) is different from (A), (B) and (D); and (D) is different from (A), (B) and (C); and - preferably when R \ R 2, R 3 and R 4 represent an unsubstituted and uninterrupted alkyl group the molar percentage in unit (A) is greater than the molar percentage in unit (B), greater than the molar percentage in unit (C), and greater than the molar percentage in unit (D) - more preferably when R1, R2, R3 and R4 are linear alkyl, then R1 is a C5-Ci3 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 2 carbon atoms such as a C3-Cn alkyl group, R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 4 carbon atoms such as a C1-C9 alkyl group, and R4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 6 carbon atoms, and - preferably when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, then the molar percentage in unit (A) is less than the molar percentage in unit (B), is less than the molar percentage in unit (B), and is less than the molar percentage in unit (C), in particular if R 2 represents an alkyl group and / or R 3 represents an alkyl group, and R 4 represents an optionally substituted and / or optionally interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl.

[0062] According to a particular embodiment of the invention, the PHA copolymer(s) comprise the repeating unit of formula (III), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates:

[0063] [Chem. 3]:

[0064] («D

[0065] Formula (III) in which: • R \ R 2, R ', and R 4 are as defined previously; • m, n, p, and v are integers greater than or equal to 1, - preferably the sum n + m + p + v is inclusively between 450 and 1400; and - preferably when R \ R 2, R 3 and R 4 represent an unsubstituted and uninterrupted alkyl group then m>n + p + q- more preferably when R1, R2, R3 and R4 are linear alkyl, then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted, R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 4 carbon atoms are subtracted, and R4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 6 carbon atoms are subtracted; and - preferably when R 1 represents a substituted and / or uninterrupted alkyl group, optionally substituted and / or uninterrupted alkenyl or optionally substituted and / or uninterrupted alkynyl, and R 2 and R 3 represent an alkyl group, and R 4 represents a substituted and / or uninterrupted alkyl group, optionally substituted and / or uninterrupted alkenyl or optionally substituted and / or uninterrupted alkynyl then n > m + v; more preferably n + p > m + v.

[0066] According to a more particular embodiment, the PHA copolymer(s) of composition a) contain five different repeating polymeric units (A), (B), (C), (D), and (E) preferably consists of the following 5 different polymeric units (A), (B), (C), (D), and (E), as well as their optical and geometric isomers and their organic or mineral acid or base salts, as well as their solvates such as hydrates:

[0067] -[-O-CH(R*)-CH2-C(O)-]- unit (A)

[0068] -[-O-CH(R2)-CH2-C(O)-]- unit (B)

[0069] -[-O-CH(R3)-CH2-C(O)-]- unit (C)

[0070] -[-O-CH(R4)-CH2-C(O)-]- unit (D)

[0071] -[-O-CH(R5)-CH2-C(O)-]- unit (E)

[0072] polymeric units (A), (B), (C), (D) and (E) in which: R \ R 2, R '' and R 4 are as defined previously; and - R 5 represents a saturated, linear or branched, cyclic or non-cyclic hydrocarbon group comprising from 3 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular represents a hydrocarbon group chosen from (C4-C28)alkyl, linear or branched, optionally substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined for R1, preferably the hydrocarbon group has a carbon number corresponding to the number of carbon atoms of the radical R4 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R4 from which at least 2 carbon atoms are subtracted, preferably from which 2 carbon atoms are subtracted; it being understood that: - (A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E), and (C) is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E) is different from (A), (B), (C) and (D); and - preferably when R \ R 2, R 3, R 4 and R 5 represent an unsubstituted and uninterrupted alkyl group the molar percentage in unit (A) is greater than the molar percentage in unit (B), greater than the molar percentage in unit (C), and greater than the molar percentage in unit (D), greater than the molar percentage in unit (E) - more preferably when R , R , R , R and R are linear alkyl, then R is a C5-Ci3 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted, R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 4 carbon atoms are subtracted, R4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 6 are subtracted carbon atoms, and R5 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 8 carbon atoms, and - preferably when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, then the molar percentage in unit (A) is less than the molar percentage in unit (B), and is less than the molar percentage in unit (C), in particular if R 2 represents an alkyl group and / or R 3 represents an alkyl group, and R 4 and R 5 represent a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl.

[0073] According to a particular embodiment of the invention, the PHA copolymer(s) comprise the repeating unit of formula (IV), as well as their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0074] [Chem. 4]:

[0075] (IV)

[0076] Formula (IV) in which: • R \ R 2, R 3, R 41 and R 5 are as defined previously; • m, n, p, v and z are integers greater than or equal to 1, preferably the sum n + m + p + v + z is between 450 and 1400 inclusive; and - preferably when R \ R 2, R 3, R 4 and R 5 represent an unsubstituted and uninterrupted alkyl group then m>n + p + v + z; - preferably when R 1 represents a substituted and / or interrupted alkyl group; optionally substituted and / or optionally interrupted alkenyl; or optionally substituted and / or optionally interrupted alkynyl, R 2 and R 3 represent an alkyl group and the groups R 4 and R 5 represent a substituted and / or interrupted alkyl group; optionally substituted and / or optionally interrupted alkenyl; or alkynyl possibly substituted and / or possibly interrupted, then n > m + v + z; more preferably n + p>m + v + z.

[0077] Preferably R 1 represents a linear or branched (C5-C28)alkyl hydrocarbon chain, preferably linear. According to one embodiment of the composition according to the invention, the PHA copolymer(s) are such that the radical R 1 is an alkyl group comprising 5 to 14, preferably between 6 and 12 carbon atoms, more preferably between 7 and 10 carbon atoms such as n-pentyl, n-hexyl, n-octyl, or n-nonyl.

[0078] According to a particular embodiment of the invention, the hydrocarbon chain R 1 is not substituted. According to a particular embodiment of the invention, the hydrocarbon chain R 1 is not interrupted.

[0079] According to another embodiment, the hydrocarbon chain of the radical R 1 of the invention is 1) either substituted, 2) or interrupted, 3) or substituted and interrupted.

[0080] According to a particular embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a hydrocarbon chain, in particular an alkyl group as defined above, which is interrupted by one or more (preferably one) atoms or groups chosen from O, S, N(Ra), carbonyl, or their combinations such as ester, amide, urea, with R a being as defined above, preferably Ra represents a hydrogen atom; preferably R 1 represents an alkyl group which is interrupted by one or more atoms chosen from O, S, more preferably by an O, or S atom, in particular S. Particularly the radical R 1 when it represents an interrupted hydrocarbon chain, in particular alkyl, is C7-C20, more particularly C8-C18, even more particularly C9-C16. Preferably, said interrupted hydrocarbon chain, in particular alkyl, is linear.

[0081] According to another embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a hydrocarbon chain, in particular an alkyl group as defined above, substituted by one or more (preferably one) atoms or groups chosen from: a) to k) as defined above. Preferably, said hydrocarbon chain is substituted by a single atom or group chosen from: a) to k) as defined above.

[0082] According to a particular embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a hydrocarbon chain, in particular an alkyl group as defined above, which is substituted by one or more (preferably one) groups chosen from a) halogen such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino and preferably amino, e) carboxy, i) (hetero)cycloalkyl such as anhydride, dithiolane or epoxide, j) cosmetic active agent chosen from colored or non-colored, fluorescent or non-fluorescent chromophores such as optical brighteners, filters UV, h) (hetero)aryl such as phenyl or furyl, k) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar radical preferably monosaccharide such as glucosyl, y) (hetero)aryl such as phenyl, 6) cosmetic active as defined above m) thiosulfate and X representing a') O, S, N(Ra), b') carbonyl, c') or their combinations of a') with b') such as ester, amide, urea; R a representing a hydrogen atom, a (Ci-C4)alkyl group, or aryl(Ci-C4)alkyl such as benzyl, preferably Ra represents a hydrogen atom.

[0083] Even more preferably, the PHA copolymer(s) are such that R 1 represents a hydrocarbon chain, in particular an alkyl group as defined above, which is substituted by one or more (preferably one) group(s) chosen from a) halogen such as chlorine or bromine, b) hydroxy, d) (di)(CrC4) (alkyl)amino, preferably amino, e) carboxy, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as a sugar radical, preferably a monosaccharide such as glucosyl, y) (hetero)aryl such as phenyl, and X representing a') O, S, N(Ra), preferably S; Ra representing a hydrogen atom, a (CrC4)alkyl group, preferably Ra represents a hydrogen atom.

[0084] According to one embodiment, said substituted hydrocarbon chain, in particular alkyl, is linear.

[0085] According to another embodiment, said substituted hydrocarbon chain, in particular alkyl, is branched. According to another particular embodiment of the invention, the hydrocarbon chain of the radical R 1 of the invention is substituted and interrupted.

[0086] According to a particular embodiment of the invention, the hydrocarbon chain (in particular an alkyl group as defined previously) of the radical R 1 of the invention is: - substituted by one or more (preferably one) groups chosen from a) halogen such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(CrC4) (alkyl)amino preferably amino, e) carboxy, i) (hetero)cycloalkyl such as anhydride, dithiolane or epoxide, j) cosmetic active agent chosen from colored or non-colored, fluorescent or non-fluorescent chromophores such as optical brighteners, UV filters, h) (hetero)aryl such as phenyl or furyl, k) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, 6) cosmetic active agent as defined above and X representing a') O, S, N(Ra), b') carbonyl, c') or their combinations of a') with b') such as ester, amide, urea; R a representing a hydrogen atom, a (Ci-C4)alkyl group, or aryl(Ci-C4)alkyl such as benzyl, preferably Ra represents a hydrogen atom; and - interrupted by one or more (preferably one) atoms or groups chosen from O, S, N(Ra), carbonyl, or their associations such as ester, amide, urea, with R a being as defined above, preferably Ra represents a hydrogen atom; preferably an alkyl group which is interrupted by one or more atoms chosen from O, S, more preferably by an O, or S atom, in particular S. Particularly the radical R 1 when it represents an interrupted hydrocarbon chain, in particular alkyl, is C7-C2o, more particularly C8-C18, even more particularly C9-C16.

[0087] According to a preferred embodiment of the invention, the hydrocarbon chain (in particular an alkyl group as defined previously) of the radical R 1 of the invention is: - substituted by one or more (preferably one) groups chosen from a) halogen such as chlorine or bromine, b) hydroxy, d) (di)(Ci-C4)(alkyl)amino preferably amino, e) carboxy, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, and X representing a') O, S, N(Ra) preferably S; R a representing a hydrogen atom, a (Ci-C4)alkyl group, preferably Ra represents a hydrogen atom; and - interrupted by one or more (preferably one) atoms or groups chosen from O, S, N(Ra), carbonyl, or their associations such as ester, amide, urea, with R a being as defined above, preferably Ra represents a hydrogen atom; preferably an alkyl group which is interrupted by one or more atoms chosen from O, S, more preferably by an O, or S atom, in particular S. Particularly the radical R 1 when it represents an interrupted hydrocarbon chain, in particular alkyl, is C7-C2o, more particularly C8-C18, even more particularly C9-C16.

[0088] Preferably, said substituted and interrupted hydrocarbon chain is in particular alkyl, and preferably is linear.

[0089] More preferably when said hydrocarbon chain R1 is substituted, it is substituted at the end of the chain on the opposite side of the carbon atom which carries said radical R1.

[0090] According to one embodiment of the invention, said hydrocarbon chain R1 is of the following formula -(CH2)rX-(ALK)uG with X being as defined above, in particular representing O, S, N(Ra), preferably S, ALK represents a (Ci-Cio)alkylene chain, linear or branched, preferably linear, more particularly (CrC 8)alkylene, r represents an integer inclusively between 6 and 11, preferably between 7 and 10 such that 8; u is 0 or 1; and G represents a hydrogen atom, or a group chosen from hydroxy, carboxy, (di)(Ci-C4)(alkyl)amino, (hetero)aryl, in particular aryl such as phenyl, cycloalkyl such as cyclohexyl, or sugar, in particular a monosaccharide optionally protected by one or more groups such as acyl, preferably Suc

[0091] [Chem. 5]:

[0092] with g* representing a group R -O(O)-. with S representing a group (Cs-OJalkyl such as methyl. Preferably when u is 0, G represents a group, cyclp^kyte such as sugar as defined previously. According to another advantageous variant when u is equal to k G represents a hydrogen atom, or a group chosen from hydroxy, (dïXCi- (hetero^ryl in particular style such as phenyl.

[0093] According to another particular embodiment of the invention, the PHA copolymer(s) are such that R 1 represents (C3-C30)alkyl substituted by one or more halogen atoms such as fluorine, chlorine, or bromine. More particularly (C4-C20)alkyl, even more particularly (C5-C13)alkyl, linear, substituted by a halogen atom such as bromine. Preferably the halogen atom is substituted at the end of said alkyl group. More preferably R1 represents 1-halo-5-yl such as 1-bromo-5-yl.

[0094] According to another particular embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a (C3-C30)alkyl group substituted by one or more groups chosen from a) cyano, more particularly represents a (C3-C13)alkyl group, preferably linear, substituted by a g) cyano group, such as l-cyano-3-propyl.

[0095] According to another particular embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a group vii) (hetero)aryl(Ci-C2)alkyl, more particularly aryl aryl(Ci-C2)alkyl, preferably phenylethyl.

[0096] According to another particular embodiment of the invention, the PHA copolymer(s) are such that R 1 represents a (C5-C28)alkyl group substituted by one or more groups chosen from c) (hetero)cycloalkyl. More particularly, R 1 represents a (C5-C13)alkyl group, preferably linear, substituted by a heterocycloalkyl group such as epoxide or dithiolane, preferably epoxide.

[0097] In particular, the PHA copolymer(s) are such that R 2 is chosen from (Ci-C28)alkyl, linear or branched, and (C2-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C3-C20)alkyl or (C3-C20)alkenyl, preferably (C3-C20)alkyl, linear or branched and more particularly linear.

[0098]

[0099] In particular, the PHA copolymer(s) are such that R 2 is chosen from (CrC28)alkyl, linear or branched, and (C2-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C3-C20)alkyl or (C3-C20)alkenyl, preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R1 from which two carbon atoms are subtracted;

[0100] According to one embodiment of the invention, the PHA copolymer(s) are such that the radical R 2 is a (C3-C8)alkyl group, linear or branched, preferably linear, particularly (C3-C6)alkyl, preferably (C4-C6)alkyl such as n-pentyl or n-hexyl.

[0101] According to another embodiment of the composition according to the invention, the PHA copolymer(s) comprise a branched (C3-C8)alkyl radical R 2 , particularly (C4-C6)alkyl, preferably branched (C4-C5)alkyl such as isobutyl.

[0102] According to another embodiment of the composition according to the invention, the PHA copolymer(s) of the invention comprise the units (A) having an alkyl radical R 1 as defined above, the units (B) as defined above and the units (C) having a linear or branched (C6-C2o)alkenyl radical, particularly (C7-C14)alkenyl, more particularly (C8-C10)alkenyl, preferably linear and comprising a single unsaturation at the end of the chain, in particular -[CR4(R5)]qC(R6)=C(R7)-R8 with R4, R5, R6, R7 and R8, identical or different, representing a hydrogen atom or a (C1-C4)alkyl group such as methyl, preferably a hydrogen atom and q represents an integer between 2 and 20 inclusive, preferably between 3 and 10, more preferably between 4 and 8 such as 6, such as -[CH2] q-CH=CH2 and q represents an integer between 3 and 8 inclusive, preferably between 4 and 6, such as 5.

[0103] According to one embodiment of the composition according to the invention, the PHA copolymer(s) comprise units (A) having an alkyl radical R 1 comprising between 8 and 16 carbon atoms substituted by one or more (preferably one) groups chosen from hydroxy, (di)(Ci-C4)(alkyl)amino, carboxy, and RX- as defined above, preferably RS- with R representing a cycloalkyl group such as cyclohexyl, heterocycloalkyl such as sugar or preferably monosaccharide such as glucose, optionally substituted aryl(Ci-C4)alkyl such as (Ci-C4)(alkyl)benzyl or phenylethyl, or heteroaryl(Ci-C4)alkyl such as furylmethyl,

[0104] According to one embodiment of the composition according to the invention, the copolymer(s) comprise units (B) having a radical R 2 (CrC8)alkyl, linear or branched, preferably linear, particularly (C2-C6)alkyl, preferably (C4-C5)alkyl such as pentyl.

[0105] According to another embodiment of the composition according to the invention, the PHA copolymer(s) comprise units (A) having an alkyl radical R 1 as defined above, units (B) as defined above and (C) having a linear or branched (C6-C2o)alkenyl radical, particularly (C7-Ci4)alkenyl, more particularly (C8-Ci0)alkenyl, preferably linear and comprising a single unsaturation at the end of the chain such that -[CH2]P-CH=CH2 and p represents an integer between 3 and 8 inclusive, preferably between 4 and 6, such as 5.

[0106] According to a particular embodiment of the invention in the PHA copolymer(s), unit (A) comprises a hydrocarbon chain as defined above, in particular ii), said unit (A) being preferably present in a molar percentage ranging from 0.1 to 99%, more preferably a molar percentage ranging from 0.5 to 50%, even more preferably a molar percentage ranging from 1 to 40%, even better a molar percentage ranging from 2 to 30%, a molar percentage ranging from 5 to 20%.

[0107] According to a more particular embodiment of the invention in the PHA copolymer(s), the unit (A) is preferably present in a molar percentage ranging from 0.5 to 99%.

[0108] According to one embodiment, when R 1 represents a (C3-C30)alkyl group, the unit (A) is preferably present in a molar percentage ranging from 0.5% to 99%, more preferably from 50% to 99%, more particularly from 60 to 99% and even more preferably from 70 to 99%. According to this embodiment, the unit (B) is preferably present in a molar percentage ranging from 2 to 40%; and the unit (C) is preferably present in a molar percentage ranging from 0.5 to 20% relative to all of the units (A), (B) and (C).

[0109] According to another embodiment when R 1 represents a hydrocarbon chain chosen from i) (C5-C28)alkyl, linear or branched, ii) (C5-C28)alkenyl, linear or branched, iii) (C5-C28)alkynyl, linear or branched, preferably the hydrocarbon group is linear, said hydrocarbon chain being substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined for R1;in particular represents a hydrocarbon group chosen from (C4-C28)alkyl, linear or branched, optionally substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined above, the unit (A) is preferably present in a molar percentage ranging from 0.5% to 99%, more preferably a molar percentage ranging from 1% to 50%, even more preferably a molar percentage ranging from 5% to 40%, even better a molar percentage ranging from 10% to 30%; the unit (B) is present in a molar percentage ranging from 1% to 99.5%, preferably from 1 to 90%, more preferably from 2 to 70%, very particularly from 2% to 40%; and unit (C) is present in a molar percentage ranging from 0.5% to 20% relative to all of units (A), (B) and (C). Advantageously, the PHA copolymer(s) of the invention comprise from 2% to 10% by mole of unit (B);and from 0.5% to 7% by mole of unit (C), more preferably the copolymer comprises from 5% to 35% by mole of unit (B); and from 0.5% to 7% by mole of unit (C). ;

[0110]

[0111] According to a more particular embodiment of the invention, the PHA copolymer(s) are such that in the PHA copolymer(s) a): - unit (A) comprises a hydrocarbon chain substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined above, said unit (A) being present in a molar percentage ranging from 0.1 to 99%, preferably a molar percentage ranging from 0.5 to 50%, more preferably a molar percentage ranging from 1 to 40%, even more preferably a molar percentage ranging from 2 to 30%, better still a molar percentage ranging from 5 to 20%; even better still a molar percentage ranging from 10 to 30% by mole of unit (A); and - unit (B) is present in a molar percentage ranging from 1 to 40%; preferably a molar percentage of 2 to 10%, more preferably a molar percentage of 5 to 35% in mole of unit (B); and / or - the unit (C) is present in a molar percentage ranging from 0.5 to 20%, preferably a molar percentage of 1 to 7%, more preferably from 0.5 to 7% in mole of unit (C).

[0112] Preferably when R 1 of unit (A) is an uninterrupted unsubstituted saturated hydrocarbon chain, said unit (A) is present in a molar percentage greater than 30%, more particularly greater than 50%, more preferably greater than 60%, preferably between 60 and 90%.

[0113] The values ​​of the molar percentages of the units (A), (B) and (C) of the PHA copolymer(s) are calculated relative to the total number of moles of (A) + (B) if the copolymer(s) do not comprise an additional unit (C), otherwise if the copolymer(s) of the invention contain 3 different units (A), (B) and (C) then the molar percentage is calculated relative to the total number of moles (A) + (B) + (C); otherwise if the copolymer(s) of the invention contain 4 different units (A), (B), (C) and (D) then the molar percentage is calculated relative to the total number of moles (A) + (B) + (C) + (D); otherwise if the copolymer(s) of the invention contain 5 different units (A), (B), (C), (D) and (E) then the molar percentage is calculated relative to the total number of moles (A) + (B) + (C) + (D) + (E).

[0114] According to one form of the invention, the PHA copolymer(s) of the invention comprise the following repeating units (A), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: R1 Al -ALKrS-ALK2-COOH A2 -ALKrS-ALK2-H A3 -ALKrS-ALK2-OH A4 -ALKrS-ALK2-NH2 A5 -ALKrS-Cycl' A6 -ALKrS-CH2-Fur A7 -ALKrS-Suc A8 -ALKi-S-ALK2-Ar A9 -ALKrHal A10 -ALKrCN Garlic -ALKrCH=CRrRw A12 -ALK2-H ALKi represents a linear or branched Ci-C2o divalent hydrocarbon radical, preferably linear or branched Ci-Cio, more preferably linear;

[0115] ALK2 represents a linear or branched CrC2o divalent hydrocarbon radical, preferably linear or branched C1-C12;

[0116] Rr and Rw independently denote a hydrogen atom or an alkyl radical (Cr C4 such as methyl, preferably Rr and Rw are identical;

[0117] Hal represents a halogen atom such as bromine;

[0118] Ar: represents a (hetero)aryl group such as phenyl;

[0119] Cycl': represents a cycloalkyl group such as cyclohexyl or heterocycloalkyl such as dithiolane or epoxide, preferably epoxide;

[0120] Fur: represents a furyl group, preferably 2-furyl;

[0121] Suc: represents a sugar group, in particular a monosaccharide optionally protected by one or more groups such as acyl, particularly acetyl.

[0122] Particularly the stereochemistry of the carbon atoms carrying the radicals R1 is of configuration (R).

[0123] According to one form of the invention, the PHA copolymer(s) of the invention comprise the repeating units (B) of formula (A12), as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates, it being understood that (B) is different from (A).

[0124] Preferably, the PHA copolymer(s) of the invention comprise the following repeating units, as well as their optical and geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0125] [Chem. 6]:

[0126] R*0 -(GH2>S-(CH3>-NH2 ​​-(GHsJi-CHa (5) -{GHsJs-S-Cyd 4CH2)4-CHî (S) -(CH2)sS-CH2-Fur -(CH2>-CH5 (7) -(CH2>-S-Suc -(CH2)4-CHa (8) -(CH2>-S-(CH2)2-Ar -(CH2)4-CH3 (9) -(CHalsrS-CHs-Ar' -(CHz)4-CHô (10) -(CHs]®-S-CH(CH3)-C(O)-OH -(CH2)sC.H3. (11) -(GH?)5-Haï -(CHsjâ-GHa (12) -(CHî)3-CN -fCHsJs-CHj. (19) -(CH2)s-CH(CH3)CH3 -CHê-CH(CH3)Cl 43 (20) -(GH2>-CH=CH2 -(GHsJs-GHî (21) 0Œ2>-CH=C(GH0CH3 -GHz-CHfCHsIGHa

[0127] m and n are as defined above, Hal represents a halogen atom such as bromine and t represents an integer between 1 and 10, preferably between 3 and 8 such as 6.

[0128] Ar: represents a (hetero)aryl group such as phenyl;

[0129] Ar': represents a (Ci-C4)alkyl(hetero)aryl group such as t-Butylphenyl, preferably 4-t-butylphenyl;

[0130] Cycl: represents a cyclohexyl group;

[0131] Fur: represents a furyl group, preferably 2-furyl;

[0132] Suc: represents a sugar group, in particular a monosaccharide optionally protected by one or more groups such as acyl, preferably Suc represents:

[0133] [Chem. 7]:

[0134] * Particularly OR"' with B; representing a group with representing a (Ci-C4)al^fe tefque methyl group. the stereochemistry of the carbon atoms bearing the radicals R1, and R2 is of the same (R) or (S) configuration, preferably of (R) configuration.

[0135] More particularly the stereochemistry of the carbon atoms bearing the radicals R1, R2 and R3 is the same configuration (R) or (S), preferably of configuration (R). More particularly the stereochemistry of the carbon atoms bearing the radicals R1, R2, R3, and R4 is the same configuration (R) or (S), preferably of configuration (R).

[0136] More particularly the stereochemistry of the carbon atoms carrying the radicals R1, R2, R3, R4, and R5 is the same configuration (R) or (S), preferably of configuration (R).

[0137] More preferably, the PHA copolymer(s) have the following formula, as well as their optical isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

[0138] [Chem. 8]:

[0139] Compounds R’ R2 (V) -(CH2)s-S-CbKCH3>C(O>OH -( CHz^-CHs (2) -(C Hz js-S-(GH2)7-CH3 -(GHz^-CHs (33 -(CH: )g-S-(CH2)s-OH -(CHs>ÇH3 H) -{CH2)s-S-(CH;K-NH2 -(CH2>CHï (S’) -{CHsJs-S-Cyd (6) -(€H2>S-CH2-Fur -(CH2>CH3 (T) 4CHà-S-SBC -<CHà-CH5. (04 -(CHsK-S-CH.W (1QQ 4QH^-S-CH{.Œ^ -(CHA-CHg. (If) -(CH2)§-CH3 (12) -(CH>)5-CH3 (13') Az 1 _£> y. (14') -(CHgVAr {15’) -(CHÀ-CHx (W) -(CH^-CHs -(CHsK-CH3 (17’) -(CHÂ-QHx (13') (19’) -CH-CHCCHsJCM (20') <OUrCH=CH^ (211 -(CHJrCH^ÇH^CHa -CHrCH(CH,)CHa {22) -(OUrCHs -(GHïV0^ (23Q (24') -(CHà-CHs n, Hal, t, Ar, Ar’, Cycl, Fur, and Suc are as defined previously for compounds (1) to (14). iiiii <1111111> R'' R: 35} -COiVCH^ 4CHA-CHs Œ} -(CH^-CRg -(CH^-CH, -CH. (27) ^ÇH^-CN ci,T 6 X ■CN -(CHs)s-CH-s o tx o x -Ar Compounds R; R: R' (29) -(CHj)s-CH=CHs (CH^-CH: (CH3-CH; HCH^CH-ÇW, (30) (W«- CHj (CH&3 CH,. -(CH3rCH=CH, -(CH8^CH=CHs (31) (CH3-CH? (CH3-CH, ■CH ^2) -(CH^-CHs ;CH < - CH fCH,k-CH: ■fCH,VCH, -ÇCHS)S-CH, {335 -:5-- ".-;>-t- CH;CH}-CiOF CH {CHsM" CH: (CHs-A- -(GHs>S-CH(€Hs)- CHfCHrl-CfOlOH (341 CH:: {CH;k-CH: {CHsir CH» -{C - (CH s}- CH s ACH^-SACHs)?-SH;j (35} GH {CH^' CH; (C%> CH:= HCH^-S-(CH:> œ □B) NHy ch3 - -fCHæ>S-(CHs}s-NHs -fC HlM-S- (CH NH; (37: -{CHs^S-Cÿæl (CH^ CHs :(CHS^ CH* -î.CK,;,ig-S-Gycl £38} Fur CH;s CHs -(CHsX^-CH^Fu) -(CH3>S-CH2-Fur - (CH sis- SS «sa (CHs> CH7 CHi;-CH:i -fCHjQs-S-Sssc -{CHs^S-SiiC (40) -{ÜHîl;-S~(CHg)g-Àr {CHs> CH: (CHsl®-CH-: -{CH^S-ÇCH^-Ar 4CH^-S-(CHs> Ar (41) ~(CHs>S-CW Af {CH:> CH: CH > - CH -{CHA^-CFfeW (42} CH(aH:j>C{Q}- {CHji';-CH: CHâ -(QH:AS-CH{CH:S}-C'O-OHl &H(GHS>C(O>GH -O OHk ix c'y □ D Ç XAA o Ç' x A

[0140] Preferably the PHA(s) a) of the invention are chosen from compounds (15), (16) and (17) in particular (16).

[0141] More particularly, the PHA(s) a) of the invention are chosen from compounds (15'), (16') and (17') in particular (16').

[0142] Preferably the PHA(s) a) of the invention are chosen from compounds (25), (26), (31) and (32) in particular (26).

[0143] The PHA copolymer(s) of the invention preferably have a number average molecular weight ranging from 50,000 to 150,000.

[0144] The molecular weight can be measured in particular by size exclusion chromatography. A method is described below in the examples.

[0145] The PHA copolymer(s) are particularly present in the composition according to the invention in a content ranging from 0.1 to 65% by weight, relative to the total weight of the composition, preferably ranging from 0.1 to 60% by weight.

[0146] Method of preparing the PHA copolymer(s):

[0147] The methods for preparing the PHA copolymer(s) of the invention are known to those skilled in the art. Mention may in particular be made of the use of microbial strains producing “functionalizable” PHA.

[0148] By "functionalizable" is meant that the PHA copolymer(s) comprises a hydrocarbon chain comprising one or more atoms or groups capable of reacting chemically with another reagent - also called "reactive atoms or reactive groups" - to lead to a covalent bond S with said reagent. The reagent is for example a compound comprising at least one nucleophilic group and said functionalized hydrocarbon chain comprises at least one electrophilic or nucleofugal atom or group, the nucleophilic group(s) reacting with the electrophilic group(s) to covalently graft S the reagent. The nucleophilic reagent may also react with one or more unsaturations of the alkylenyl group(s) to also lead to grafting by covalent bonding of the hydrocarbon chain functionalized by said reagent.The addition reaction can also be radical, a Markovnikov or anti-Markovnikov type addition, a nucleophilic or electrophilic substitution. Addition or condensation reactions can be carried out by radical or non-radical means, using catalysts. or not, enzymes or not, heat preferably at a temperature less than or equal to 100°C or without heat input, under pressure greater than 1 atm or not, under an inert atmosphere or not, or under oxygen or not.

[0149] By "nucleophile" is meant any atom or group that electron donates by inductive effect +1 and / or mesomeric +M. As electron donating group, mention may be made of hydroxy, thiol, amino groups.

[0150] By "electrophile" we mean any atom or group which is electron-withdrawing by inductive effect -I and / or by mesomeric effect -M. As electron-withdrawer we can cite.

[0151] The microorganisms producing PHAs of the invention, in particular with a hydrocarbon chain, can be naturally produced by the Bacterial kingdom such as Cyanobacteria of the order Nostocales (e.g. Nostoc muscorum, Synechocystis and Synechococcus) but mainly in the Proteobacteria, for example in the class of:

[0152] - beta-Proteobacteria, of the order Burkholderiales (Cupriavidus negator synonym Rasltonia eutropha)

[0153] -alpha- Proteobacteria, of the order Rhodobacteriales (marine and photosynthetic Rhodobacter capsulatus)

[0154] -gamma-Proteobacteria, of the order Pseudomonaes of the family Moraxellaceae (Acinetobacter Junii)

[0155] Among the microorganisms of the Bacterial kingdom, the genera Azotobacter, Hydrogenomomas, or Chromatium are the most representative of PHA-producing organisms.

[0156] The organisms naturally producing PHAs with a hydrocarbon chain, in particular in C3-C5, are in particular Proteobacteria, such as gamma-Proteobacteria, and more particularly of the order of Pseudomonales of the Pseudomonas family such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida GPo 1 and Pseudomonas putida KT2440, preferably Pseudomonas putida and in particular Pseudomonas putida GPo 1 and Pseudomonas putida KT2440.

[0157] Some organisms can also naturally produce PHAs without belonging to the order Pseudomonales such as Commamonas testosteroni which belongs to the class beta-Proteobacterium of the order Burkholderiales of the family Comamonadaceae.

[0158] The PHA-producing microorganism according to the invention may also be a recombinant strain if a 3-oxidation PHA synthase metabolic pathway is present. The 3-oxidation PHA synthase metabolic pathway is mainly represented by four enzyme classes EC: 2.3.1 B2; EC: 2.3.1 B3 EC: 2.3.1 B4 and EC: 2.3.1 B5.

[0159] The recombinant strain can be from the Bacteria kingdom such as for example Escherichia coli, or from the Plantae kingdom such as for example Chlorella pyrenoidosa (International Journal of Biological Macromoleculess, 116, 552-562 “Influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (PHAs) by microalgae”) or from the Fungi kingdom ex Saccaromyces cerevisiae or Yarrowia lipotyca: Applied Microbiology and Biotechnology 91, 1327-1340 (2011) “Engineering polyhydroxyalkanoate content and monomer composition in the oleaginous yeast Yarrowia lipolytica by modifying the B-oxidation multifunctional protein”).

[0160] Genetically modified microorganisms can also be used, which can allow, for example, an increase in PHA production, and / or an increase in oxygen consumption capacity, and / or a decrease in autolysis and / or a modification of the monomer ratio.

[0161] It is known that for PHAs, a large part of the total production cost is allocated to the culture medium and mainly to the substrate / carbon source. Thus, we can use genetically modified microorganisms using less nutrients (carbon source) for their growth, for example photo-autotrophic by nature, i.e. using light and CO2 as the main source of energy.

[0162] The copolymer can be obtained in a known manner by biosynthesis, for example with microorganisms belonging to the genus Pseudomonas, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida; and with a carbon source which can be a C2-C20, preferably C6-C18, carboxylic acid, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; an alkenoic acid such as undecylenic acid, a saccharide such as fructose, maltose, lactose, xylose, arabinose, etc.); an n-alkane such as hexane, octane, dodecane; an n-alcohol such as methanol, ethanol, octanol, glycerol; methane, carbon dioxide.

[0163] The biosynthesis can optionally be carried out in the presence of an inhibitor of the [3-oxidation] pathway such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid, phenylpropionic acid, and preferably acrylic acid.

[0164] According to one embodiment, the method for preparing the PHAs of the invention uses microbial cells producing PHAs by genetically modified microorganisms (GMOs). The genetic modification can increase PHA production, increase oxygen uptake capacity, increase resistance to solvent toxicity, decrease autolysis, modify the ratio of PHA comonomers, and / or any combination thereof. In some of these embodiments, the modification of the ratio of unit comonomers (A) increases the amount of predominant monomer vs (B) of the PHA of the invention obtained. In another embodiment, the PHA-producing microbial cells reproduce naturally.

[0165] As an example of a genetically modified microbial strain producing functionalizable PHA or comprising a reactive group, we can cite Pseudomonas entomophila LAC23 (Biomacromolecules. 2014 Jun 9;15(6):2310-9. doi: 10.1021 / bm500669s)

[0166] It is also possible to use genetically modified microorganisms producing phenylvaleric co 3-Hydroxydodecanoic copolymers (Sci China Life Sci, Shen R, et al.,.57 No.l, (2014) with a strain such as Pseudomonas entomophila LAC23.

[0167] It is also possible to use, for biosynthesis, nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium, iron.

[0168] Known appropriate conditions of temperature, pH, dissolved oxygen (DO) can be used for the cultivation of microorganisms.

[0169] The microorganisms can be cultured according to any known culture method, such as in a bioreactor in continuous mode, batch mode, in fed or unfed mode.

[0170] The biosynthesis of the polymers used according to the invention is notably described in the article “Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer”, Xun Juan et al; Biomacromolecules 2012, 13, 2926-2932 and in application WO 2011 / 069244.

[0171] The microbial strains producing functionalizable PHA or comprising a reactive group as defined above are, for example, of the genus Pseudomonas such as P. cichorii YN2, P. citronellolis, P. jessenii, and more generally by the species of Pseudomonas putida such as Pseudomonas putida GPol (synonym of Pseudomonas oleovorans), P. putida KT2442, P. putida KT2440, P. putida KCTC 2407, P. putida BM01 and in particular P. putida KT2440.

[0172] The carbon source(s):

[0173] One way to access the PHAs of the invention is to introduce one or more organic compounds into the culture medium, this or these organic compounds representing one or more carbon sources preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and their mixture.

[0174] In one embodiment, the organic compound(s) will preferably be chosen from alcohols, carboxylic acids and their mixture.

[0175] The carbon source(s) can be classified into 2 categories: 1. Source of carbon by one or more organic compounds introduced into the environment:# According to a particular embodiment of the invention, the organic compound(s) are chosen from alcohols, in particular (C5-C2o)alkanols, and / or carboxylic acids, in particular optionally substituted and / or interrupted (C5-C2o)alkanoic acids, in particular (C5-C20)alkanoic acids such as (C7-Cn)alkanoic acids such as nonanoic acid or pelargonic acid and / or (C5-C20)alkenoic acids, in particular (C5-C20)alkenoic acids such as (C7-Cn)alkenoic acids such as undecylenic acid, and mixtures thereof.

[0176] The carbon source(s) can be classified into 3 groups according to their destination: - group A, the organic compound can help the growth of the producing strain and helps the production of PHA structurally linked to the organic compound. - group B, the organic compound can help the growth of the strain but does not participate in the production of PHA structurally linked to the organic compound. - group C: the organic compound does not participate in the growth of the strain.

[0177] Such microbiological methods are known to those skilled in the art, particularly in the scientific literature. Examples include: International Journal of Biological Macromolecules 28, 23-29 (2000); The Journal of Microbiology, 45, No. 2, 87-97, (2007).

[0178] According to a variant, the integration of the substrate which is structurally linked to the reactive atom(s) or to the reactive group(s) of the PHA(s) of the invention is introduced directly into the medium as a sole carbon source in a medium suitable for microbial growth. (Example: group A for P.putida GPol: alkenoic acid, in particular terminals).

[0179] According to another variant, the integration of the substrate which is structurally linked to the reactive atom(s), in particular halogen, or to the reactive group(s) of the PHA of the invention is introduced into the medium as a carbon source with a second carbon source as a co-substrate which is also structurally related to the PHA in a medium suitable for microbial growth. (Example: Group B for P.putida GPol: preferably terminal haloalkanoic acids such as terminal bromoalkanoic acids).

[0180] According to yet another variant, the integration of the substrate which is structurally linked to the reactive atom(s), in particular halogen, or to the reactive group(s) of the PHA(s) of the invention can be introduced directly into the medium as a carbon source with a second carbon source as a co-substrate which is also structurally linked to the PHA(s) and a third carbon source as a co-substrate which is not structurally linked to the PHA(s) in a medium suitable for microbial growth. (Example: group C glucose or sucrose).

[0181] In one embodiment, the beta oxidation pathway inhibitor is acrylic acid, 2-butynoic acid, 2-octynoic acid, phenylpropionic acid, propionic acid, trans-cinnamic acid, salicylic acid, methacrylic acid, 4-pentenoic acid or 3-mercaptopropionic acid, preferably acrylic acid.

[0182] 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.

[0183] The functionalization can be introduced by an organic compound chosen from the precursors of the alcohol and / or carboxylic acid category, in particular: - for functionalization of the PHA(s) with a branched or branched alkyl group: see e.g. Applied and Environmental Microbiology, .60. No.9, 3245-325 (1994); - for functionalization of the PHA(s) with a linear alkyl group comprising a cyclohexyl terminal unit: see e.g. doi.org / 10.1016 / S0141-8130(01)00144-1; - for functionalization of the PHA(s) with an unsaturated alkyl group, preferably terminal, see e.g. doi.org / 10.1021 / bm8005616); - for functionalization of the PHA(s) with a linear alkyl group comprising a halogen preferably at the end of the hydrocarbon chain (doi.org / 10.1021 / ma00033a002); - for functionalization of the PHA(s) with an alkyl (hetero)aromatic group, for example phenyl, benzoyl, phenoxy, see e.g. J.Microbiol. Biotechnol, 11, 3,435-442 (2001); - for functionalization of the PHA(s) with a linear alkyl group comprising a heteroatom, in particular at the end of the hydrocarbon chain, see for example DOI 10.1007 / s00253-011-3099-4; - for functionalization of the PHA(s) with a linear alkyl group comprising a cyano function, in particular at the end of the hydrocarbon chain, see e.g. .org / 10.1111 / j.l574-6968.1992.tb05839.x; - for functionalization of the PHA(s) with a linear alkyl group comprising an epoxy function, in particular at the end of the hydrocarbon chain, see for example doi.org / 10.1016 / S1381-5148(97)00024-2; The journal International Microbiology 16:1-15 (2013) doi: 10.2436 / 20.1501.01.175) also mentions the majority of functionalized native PHAs.

[0184] In a particular embodiment of the invention, the fatty acid of group A is chosen from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenyl valeric acid, citronellol, and 5-cyanopentanoic acid.

[0185] In a particular embodiment of the invention, the fatty acid of group A is chosen from halooctanoic acids such as 8-bromooctanoic acid.

[0186] In a particular embodiment of the invention, the carbon source of group C is a monosaccharide, preferably glucose. 1. Carbon source in the presence of oxidation inhibitor introduced into the medium:#

[0187] Another aspect of the invention is the use of the PHA-producing microbial strains, in a medium suitable for microbial growth, said medium comprising: a substrate which is structurally linked to the PHA(s); at least one carbon source which is not structurally linked to the PHA(s); and at least one inhibitor of the oxidation pathway, in particular beta oxidation. This allows the growth of the microbial cells to occur in said medium, the microbial cells synthesize the PHA polymer(s) of the invention; preferably a copolymer having particularly more than 95% of identical unit, which has a co-monomer ratio of unit (A) and unit (B) which differs from that obtained in the absence of the inhibitor of the beta oxidation pathway.

[0188] The diagram below illustrates by way of example the functionalization of PHA copolymers according to the invention from PHA copolymer with unsaturated hydrocarbon chain according to the following diagram 1:

[0189] [Chem. 9]:

[0190]

[0191] Diagram 1 in which: R2, m, and n are as defined previously; - Y represents a group chosen from Hal such as chlorine or bromine, hydroxy, thiol, (di)(Ci-C4)(alkyl)amino, RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl; 6) cosmetic active as defined above; e) (Ci-C2o)alkyl, (C2-C2o)alkenyl, (C2-C20)alkynyl; and X representing a') O, S, N(Ra) or Si(Rb )(RC) or e) (Ci-C20)alkyl, linear or branched, with Ra, Rb and Rc as defined above; - q' represents an integer between 2 and 20 inclusive, preferably between 3 and 10, more preferably between 4 and 8 such as 6, better still between 3 and 8, preferably between 4 and 6, such as 5.

[0192] Other reactions can be carried out from double or triple unsaturations such as Michael additions, Diels-Alder additions, radical additions, catalytic hydrogenation reactions (in particular with Pd, Ni) or not, halogenation reactions in particular with bromine, hydration, controlled or uncontrolled oxidation, and reactions on electrophiles as shown diagrammatically below:

[0193] According to a particular embodiment of the invention, the PHA copolymers comprise - a linear or branched saturated hydrocarbon chain R1, substituted and / or interrupted by atoms or groups as defined previously for R1, comprising in total between 5 and 30 carbon atoms, preferably between 6 and 20 carbon atoms, more particularly between 7 and 11 carbon atoms and - a hydrocarbon chain R2 representing a linear or branched (C3-C20)alkenyl radical, particularly (C5-C14)alkenyl, more particularly (C7-C10)alkenyl, preferably linear and comprising a single unsaturation at the end of the chain, in particular -[CR4(R5)]qC(R6)=C(R7)-R8 with R4, R5, R6, R7 and R8, identical or different, representing a hydrogen atom or a (C1-C4)alkyl group such as methyl, preferably a hydrogen atom and q represents an integer between 2 and 20 inclusive, preferably between 3 and 10, more preferably between 4 and 8 such as 6, such as -[CH2]q-CH=CH 2 and q represents an integer between 3 and 8 inclusive, preferably between 4 and 6, such as 5, said R2 chain comprising between 1 and 99%, preferably between 2 and 50% and even more preferably between 3 and 40% of unsaturations, and even more particularly between 3 and 30% of unsaturations, better still between 5 and 20% of unsaturations. According to this particular embodiment of the invention in which the PHA copolymers comprise unsaturations, these unsaturations can be chemically modified:

[0194] A) by addition reactions, such as radical additions, Michael additions, electrophilic additions, Diels-Alder reaction, halogenation, hydration, hydrogenation, and preferably hydrothiolation with particles, chemical compounds or polymers.

[0195] In particular, the hydrothiolation reactions can be carried out in the presence of a thermal initiator, an oxidation-reduction (redox) initiator or a photochemical initiator and an organic compound bearing a sulfhydryl group, in particular chosen from: - Linear, branched, cyclic or aromatic alkanethiols containing 1 to 14 carbon atoms, such as methane-, ethane-, propane-, pentane-, cyclopentane-, hexane-, cyclohexane-, heptane-, octane, phenylethane-, 4-tert-butylphenylmethane-, 2-furanmethane-thiol, preferably hexane-, cyclohexane-, heptane-, octane, phenylethane-, 4-tert-butylphenylmethane-, 2-furanmethane-thiol; - Organosiloxanes bearing a thiol function, such as (3-mercaptopropyl)trimethoxysilane, (3-Mercaptopropyl)methyldimethoxysilane, 2-(Triethoxysilyl)ethanethiol, mercaptopropyl-isobutyl-POSS; - Thiolated silicone oils, in particular those described in the document DOI: 10.1016 / j.actbio.2015.01.020); - Thiolated oligomers or polymers carrying a reactive function, such as an amine, an alcohol, an acid, a halogen, a thiol, an epoxide, a nitrile, an isocyanate, a heteroatom, preferably cysteine, cysteamine, N-acetylcysteamine, 2-Mercaptoethanol, l-Mercapto-2-propanol, 8-Mercapto-l-octanol, thiolactic acid, thioglycolic acid, mercapto-3-propionic acid, 11-mercaptoundecanoic acid, polyethylene glycol dithiol, 3-Mercaptopropionitrile, 1,3-Propanedithiol, 4-Cyano-l-butanethiol, 3-Chloro-l-propanethiol, l-Thio-[3-D-glucose tetraacetate; and - Thiols that can be obtained from the reduction of disulfide, such as phenyldisulfide, furfuryl disulfide.

[0196] Examples of initiators that may be mentioned include: tert-butyl peroxy-2-ethylhexanoate, cumin perpivalate, tert-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobis isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,4-bis(tert-butylperoxycarbonyl)cyclohexane, 2,2-bis(tert-butylperoxy)octane, 4,4-bis(tert-butylperoxy)valerate of n-butyl, 2,2-bis(tert-butylperoxy)butane, 1,3-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-tert-butyl diperoxy isophthalate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butyl peroxy-a-methylsuccinate,di-tert-butyl peroxydimethylglutarate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, diethylene glycol bis(tert-butylperoxycarbon ate), di-tert-butyl peroxytrimethyladipate, tris(tert-butylperoxy) triazine, vinyltris(tert-butylperoxy)silane phenothiazine, tetracene, perylene, anthracene, diphenyl-9-10-anthracene, thioxanthone, benzophenone, acetophenone, xanthone, fluorenone, anthraquinone, 9, 10-dimethylanthracene, 2-ethyl-9, 10-dimethyloxyanthra cene, 2, 6-dimethyl-naphthalene, 2, 5-diphenyl-l-34-oxadiazole, xanthopinacol, 1, 2-benzanthracene, 9-nitro-anthracene. Each of these initiators can be used alone or in combination with others.

[0197] The chemical reactions mentioned above are known to those skilled in the art. The following documents may be cited in particular: Synthesis and preparation of PHAs modified with polyethylene glycol dithiol: 10.1021 / acs.biomac.9b0047 9; Biomacromolecules, 19. 3536-3548 (2018); Synthesis and preparation of PHAs modified with mercaptohexanol: 10.1021 / acs.biomac.8b01257; Biomacromolecules, 20, 2, 645-652 (2019); Synthesis and preparation of PHAs modified with Hydroxy-, Cinnamic Acid-, Sulfate-, and Zosteric Acid: 10.1021 / bm049962e ^Biomacromolecules, 5, 4, 1452-1456 (2004); Radical addition of methyl methacrylate to a PHOUn: 10.1002 / 1521-3935(20010701)202:ll<2281::AID-MACP2281>3.0.CO;2-9; Macromolecular Chemistry and Physics, vol. 202, 11. 2281-2286 (2001); Synthesis and preparation of PHAs modified with a polysilsesquioxane (POSS): 10.1016 / j.polymer.2005.04.020; Polymer Vol. 46, 14.5025-5031 (2005); Grafting of thio-beta-glucose onto unsaturated side chains: 1022-1336 / 99 / 0202-0091 $17.50+.50 / 0; Macromol. Rapid Commun., 20. 91-94 (1999).

[0198] And / or

[0199] B) by controlled or uncontrolled oxidation reactions, for example with concentrated or diluted alkaline agent permanganates, or ozonolysis, oxidation in the presence of a reducing agent, and make it possible to obtain new materials having hydroxy, epoxide or carboxy group side chains in the terminal position.

[0200] The chemical reactions mentioned above are known to those skilled in the art. The following documents may be cited in particular: 10.1021 / bm049337; Biomacromolecules, vol. 6, 2, 891-896 (2005); 10.1016 / 80032-3861(99)00347-X; Polymer, vol. 41, 5, 1703-1709 (2000); 10.1021 / ma9714528 and 10.1016 / S1381-5148(97)00024-2 ^Macromvlecules, 23, 15, 3705-3707 (1990); 10.1016 / S0032-3861(01)00692-9; Polymer, vol 43, 4, 1095-1101 (2002); 10.1016 / S0032-3861(99)00347-X; Polymer, vol 41, 5, 1703-1709 (2000); and 10.1021 / bm025728h; Biomacromolecules, vol 4, 2, 193-195 (2003).

[0201] Example of functionalization of PHA copolymers according to the invention from PHA copolymer with hydrocarbon chain with an epoxide group according to the following scheme 2:

[0202] [Chem. 10]:

[0203]

[0204] Scheme 2 in which Y, m, n, q', and R2 are as defined in Scheme 1.

[0205] The epoxidized structure can be obtained by a conventional method known to man of the trade, whether by biotechnological processes, or by chemical means such as oxidation of unsaturation as mentioned above. The peroxide group(s) can react with carboxylic acids, maleic anhydrides, amines, alcohols, thiols, isocyanates, all these reagents comprising at least one C1-C2o hydrocarbon chain, linear or branched, cyclic or acyclic, saturated or unsaturated, or carried by an oligomer or polymer in particular amino (poly)saccharides such as compounds derived from chitosan and (poly)sil(ox)anes; 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrieth oxysilane, 3-(trimethoxysilyl)propylcarbamic acid, diethanolamine, 3-mercapto-l-propanesulfonate of alkali or alkaline earth salts such as sodium. Epoxide groups can also react with water.

[0206] The following documents may be cited in particular: - Preparation of charge-bearing PHA from diethanolamine: 10.1021 / bm8005616, Biomacromolecules, vol 9, 8, 2091-2096 (2008); - Preparation of charge-bearing PHA from sodium 3-mercapto-1-propanesulfonate: 10.1021 / acs.biomac.9b00870 Biomacromolecules, vol 20, 9, 3324-3332 (2019); - Preparation of PHA comprising a native epoxide unit: 10.1016 / S1381-5148(97)00024-2); Reactive and Functional Polymers, vol 34,1,, 65-77 (1997)

[0207] Example of functionalization of PHA copolymers according to the invention from PHA copolymer with hydrocarbon chain with nucleofugal group according to the following scheme 3:

[0208] [Chem. 11]:

[0209]

[0210] Scheme 3 in which Y, m, n, q', and R2 are as defined in Scheme 1. M corresponds to a nucleofugal group, organic or inorganic, which can be substituted by a nucleophilic group, preferably said nucleophile is an electron-donating heteroatom by +1 and / or +M effect such as O, S, or N. Preferably the nucleofugal M is chosen from halogen atoms such as Br, and mesylate, tosylate or triflate groups. This is a reaction known to those skilled in the art. For example, the following document 10.1016 / j.ijbiomac.2016.11.118, International Journal of Biological Macromolecules, vol 95, 796-808 (2017) may be cited.

[0211] Example of functionalization of PHA copolymers according to the invention from PHA copolymer with hydrocarbon chain with a cyano group according to the following scheme 4:

[0212] [Chem. 12]:

[0213] Scheme 4 wherein Y, m, n, q', Y and R2 are as defined in Scheme 1.

[0214] In a first step i) the PHA copolymer with a cyano group side chain or nitrile reacts with an organoalkali or organomagnesium compound Y-MgHal, Y-Li, or Y-Na, followed by hydrolysis to yield the PHA copolymer with a Y-group side chain grafted with a ketone function. The ketone function can be changed into a thioketone by thionation, for example with S8 in the presence of amine, or with Lawesson's reagent. The latter, after total reduction ii) (for example by Clemensen reduction), yields the PHA copolymer with a Y-group side chain grafted with an alkylene group. Or the latter can be reduced in a controlled manner iii) by a conventional reducing agent to produce the PHA copolymer with a Y group side chain grafted with a hydroxyalkylene group. The cyano group of the starting PHA copolymer can react with water after hydration v) to produce the amide derivative, after hydrolysis iv) to produce the carboxy derivative. The cyano group of the starting PHA copolymer can also, after reduction vi), produce the amine derivative or the ketone derivative. PHA copolymers with a nitrile-functional hydrocarbon side chain are prepared by conventional methods known to those skilled in the art. For example, the document: 10.1016 / 0378-1097(92)90311-B, FEMS Microbiology Letters, vol. 103, 2^ 4, 207-214 (1992) can be cited.

[0215] Example of functionalization of PHA copolymers according to the invention from PHA copolymer with hydrocarbon chain at the end of the chain according to the following scheme 5:

[0216] [Chem. 13]:

[0217]

[0218] Scheme 5 in which R1, R2, m, n and Y are as defined above, and R'1 represents a hydrocarbon chain chosen from i) (Ci-C2o)alkyl, linear or branched, ii) (C2-C2o)alkenyl, linear or branched, iii) (C2-C20)alkynyl, linear or branched, iii) preferably the hydrocarbon group is linear; said hydrocarbon chain being substituted by one or more atoms or groups chosen from: a) halogen such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, f) cyano, g) iso(thio)cyanate, h) (hetero)aryl such as phenyl or furyl, and i) (hetero)cycloalkyl such as anhydride, or epoxide, j) cosmetic active agent chosen from colored or non-colored, fluorescent or non-colored chromophores such as those derived from optical brighteners, or chromophores derived from UVA and / or UVB filters, anti-aging active agents.

[0219] These end-of-chain grafts are known on PHA polymers by those skilled in the art. The following documents may be cited, for example: - Preparation of PHA oligomers by thermal degradation: 10.1021 / bm0156274; Biomacromolecules, vol 3,1, 219-224 (2002); - Preparation of PHA oligomers by transesterification: 10.1021 / ma011420r, Macromolecules, vol 35, 3, 684-689 (2002); - Preparation of PHA oligomers by hydrolysis: 10.1016 / 0032-3861(94)90590-8 Polymer_ vol 35, 19, 4156-4162 (1994); - Preparation of PHA oligomers by methanolysis: 10.1021 / bm060981t, Biomacromolecules, vol 8, 4, 1255-1265 (2007);

[0220] Other methods known to those skilled in the art may also be cited: - Synthesis and characterization of PHA grafted with ascorbic acid: 10.1016 / j.ijbiomac.2018.11.052; International journal of biological macromolecules, vol 123: 7 (2019); - Preparation of PHB-b-PHO copolymers by polycondensation with divinyl adipate catalyzed by a lipase: 10.1021 / bm9011634, Biomacromolecules, vol 10, 12, 3176-3181 (2009); - Synthesis of PHB-b-PHO copolymers coupled by a diisocyanate junction: 10.1021 / ma012223v; Macromolecules, vol 35,13. 4946-4950 (2002); - Preparation of PHO oligomers on chitosan by condensation between the carboxylic acid end of PHO and the amine functions of chitosan: 10.1002 / app.24276; Journal of Applied Polymer Science, vol 103,1, (2006); - Transesterification of PHAs by propargyl alcohol to produce PHA oligomers modifiable by click chemistry: 10.1016 / j.reactfunctpo lym.2011.12.005; Reactive and Functional Polymers, vol 72, 2,, 160-167 (2012); - Preparation of PHO-b-PCL copolymer: 10.1002 / mabi.200400104; Macromolecular Bioscience, vol 4, 11 (2004); - Preparation of PHO-b-PEG copolymer: 10.1002 / macp.201000562; Macromolecular Chemistry and Physics; vol 212, 3, (2010); - End-chain unsaturation epoxidation and end-chain acid grafting: 10.14314 / polhnery.2017.317; Polimery, vol 62, 4, 317-322 (2017); - Grafting of organosiloxane units at the end of the chain onto PHA: 10.1016 / j.reactfunctpolym.2014.09.008; Reactive and Functional Polymers, vol 84, 53-59 (2014).

[0221] All of the grafted PHA copolymers of the invention described previously, according to scheme 6:

[0222] [Chem. 14]:

[0223] X'

[0224] Scheme 6 in which R'1, R2, m, n and Y are as defined above, and

[0225] X' represents a reactive atom or group capable of reacting with an atom or electrophilic group E or nucleophile Nu to create a covalent bond S if X' is an electrophilic or nucleofuge group then it can react with a reagent R'1- Nu, if X' is a nucleophile group Nu then it can react with R'1- E to create a covalent bond S;

[0226] As an example, the covalent bonds or S-linking groups that can be generated are listed in the table below from condensation of electrophiles with nucleophiles:

[0227] [Table. 1]: Etectros dites ïE Nuciés^hiles Lis sors covsA Esters Arsines C arb-o xa rsi des Azataes Avises A iy; ,y- Carhcxsmides Hàtoqémi^ d'acyf SS- es A^s^is Esters Cyanures d'scytes Esters Cyanures d'acytes S—£ æ: j w-> iras ' œ ÿ Amibes Csftasamîdes >'l -SsW & œ HategeRures d-'s^y SC3 Acides sTS.^Sxy lœi ! ix< IS:3i Esters Halcgénuses d's^y ^s Thic^s Thiaesters y É (U 8 ET 3 23 2 01 u u' " “l 9 Ü 'ty C ■ / ! Si Aid s® 1ïs Thàais e.«rs-es.s Thoéthers Asiates extatiques SSiS et k èL^rs Acides esrhGxyliqyes Esters Àœdss ■sulfànâqxes sete ef is Ais&cis Ethers Anhydrides Aicseis Esters Anhydrides A^siReS Csrbcxs^ides Hate^érwes d'ar^k és Thteéthers Hricgémires d'ar^ es Araires Arylamines

[0228] It is also possible, starting from a PHA functionalized in the side chain, to carry out the grafting at the end of the chain in a second step as described in diagram 7. The converse is also true, where the grafting at the end of the chain is achievable in a first step, then the functionalization of the functionalizable pendant side chain is carried out in a second step.

[0229] [Chem. 15]:

[0230]

[0231] Scheme 7 in which R'1, R2, m, n and Y are as defined previously, and

[0232] All these chemical reactions are known to those skilled in the art. The following documents may be cited, for example: - Synthesis and preparation of PHAs modified by thiol-ene, then reaction on new grafted function: 10.1021 / ma0304426; Macromolecules, vol 37, 2, 385-389(2004); - Grafting of PEG and PLA onto PHAs functionalized with acids: 10.1002 / marc.200900803 and 10.1002 / mabi.200390033; - Synthesis and preparation of PHAs modified with polyethylene glycol dithiol: 10.1021 / acs.biomac.9b00479. b) the polyurethane latex(es)

[0233] The composition Cl or Cl' of the invention comprises one or more polyurethane latexes

[0234] By “polyurethane” or “polyurethane” is meant a urethane polymer, i.e. an organic polymer comprising the repetition of the function -N(R)-C(O)-O-.

[0235] The polyurethane latex(es) of the invention is(are) capable of being obtained from:

[0236] Bi) of at least one polyol chosen from: - Bn) a polyester polyol resulting from the reaction of: • at least one polyol Bin) with • at least one polycarboxylic acid B112) and • possibly Bn3) at least one monocarboxylic acid; - Bi2) a diol; and - the mixture of Bn) and Bn); and B2) at least one polyisocyanate, preferably a diisocyanate, in particular aliphatic or cycloaliphatic and mixtures thereof; and

[0237] B3) of at least one hydrophilic monomer chosen from: - B3i) compounds carrying an acid function, in particular carboxylic, or a basic function, in particular primary, secondary or tertiary amine, and further comprising at least one hydroxyl function, preferably at least one at least two hydroxyl functions, in particular two hydroxyl functions such as 2,2-bis(hydroxymethyl)propionic acid and - B32) diamine compounds of formula H 2 NR 5 -NH 2 (X) in which R 5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups; and B4) optionally at least one amino compound which is not substituted by one or more ionic or potentially ionic groups.

[0238] More particularly, the polyurethane latex(es) of the invention is(are) capable of being obtained from:

[0239] Bi) of at least one polyol chosen from: - Bn) at least one polyester polyol resulting from the reaction of: • at least one polyol Bm) such as neopentyl glycol, hexanediol, butanediol with • at least one polycarboxylic acid Bn2) such as adipic acid, succinic acid and optionally Bn3) at least one monocarboxylic acid, preferably abietic acid or rosin; and / or Bi2) at least one diol; and their mixture; and B2) of at least one polyisocyanate, preferably at least one diisocyanate, in particular aliphatic or cycloaliphatic such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane hexamethylene diisocyanate and their mixture; and

[0240] B3) of at least one hydrophilic monomer chosen from B3[) the carrier compounds of an acid function, for example a carboxylic function, or of a basic function, for example a primary, secondary or tertiary amine function, and further comprising at least one hydroxyl function, preferably at least two hydroxyl functions, in particular two hydroxyl functions such as 2,2-bis(hydroxymethyl)propionic acid and / or B32) at least one diamine compound of formula H 2 NR 5 -NH 2 (X) in which R 5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups such as carboxy; and

[0241] B4) optionally at least one amine compound which is not substituted by one or more ionic or potentially ionic groups.

[0242] B a ) Polyester Polyol

[0243] According to one form of the invention, the polyurethane polymer of the latex b) is prepared from at least one polyester polyol Bu) resulting from the reaction of at least one polyol Bm) with at least one polycarboxylic acid Bn2) and optionally Bn3) at least one monocarboxylic acid; and / or Bi2) at least one diol.

[0244] B ni ) Polyol

[0245] According to one form of the invention, the polyester polyol Bu) is obtained from at least one polyol component Bm). The polyol Bm) preferably comprises from 2 to 6 hydroxyl groups (-OH), in particular two, three or four hydroxyl groups.

[0246] According to one form of the invention, the polyester polyols Bu) are dihydroxylated polyesters resulting from the reaction of at least one dihydroxylated organic compound (diol) with at least one polycarboxylic acid.

[0247] According to a particular embodiment, the polyol Bm) is an organic compound comprising a hydrocarbon chain, linear or branched, acyclic or (poly)cyclic, saturated or unsaturated, aromatic or not, comprising from 3 to 18 carbon atoms, in particular from 4 to 12 carbon atoms, or even from 5 to 10 carbon atoms; and from 2 to 6 hydroxyl groups, said hydrocarbon chain being optionally interrupted by one or more oxygen atoms, in particular possibly having ether functions.

[0248] As examples of such polyols Bm), mention may be made, without this list being limiting, of i) oses such as pentoses such as ribose, arabinose, xylose, lyxose, ribulose, xylulose or hexoses such as allose, altrose, galactose, glucose, idose, mannose, talose, fructose, sorbose or deoxyhexoses such as fucose or rhamnose; ii) triols such as glycerol, iii) tetraols such as pentaerythritol (tetramethylolmethane), erythritol, diglycerol, iv) pentols such as xylitol, v) hexols such as sorbitol and mannitol, or dipentaerythritol or triglycerol, and mixtures thereof.

[0249] According to a particular embodiment, the polyol Bm) is a diol of formula (I) HO-ALK-OH (I) in which ALK represents a linear or branched C1-C18 alkylene group, in particular C1-C18, C1-C18. The polyol Bm) is then a (C1-C18)alkane diol. Examples of (C1-C18)alkane diols that may be mentioned, without this list being limiting, are ethylene glycol, butylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol.

[0250] According to a particular embodiment, the polyol Bm) is an alkane diol whose alkylene chain is interrupted by one or more oxygen atom(s) such as, for example, diethylene glycol, triethylene glycol, polyethylene glycol,

[0251] According to a particular embodiment, the polyol Bm) is an alkane diol whose alkylene chain is interrupted by one or more ester groups such as, for example, hydroxypivalic acid neopentyl glycol ester.

[0252] According to one embodiment, the polyol Bm) may be an oligomer derived from one or more diols of formula (I) above with a weight-average molecular mass of between 200 and 4,000 g.mol1, in particular between 300 and 3,000 g.mol '. By way of example, the compound of formula (I) is such that ALK represents a group (Ci-C6 )alkylene, the oligomer then being a poly(Ci-C6)alkane diol. Examples include polypropane diol (also known as polypropylene glycol) with a weight-average molecular mass of between 300 and 3,000 g.mol1, or polyethylene glycol with a weight-average molecular mass of between 300 and 3,000 g.mol1.

[0253] Among the dihydroxylated compounds Bm) which can be used according to the present invention, mention may in particular be made of compounds having two hydroxyl groups and a number-average molecular weight of approximately 700 to approximately 16,000, and preferably of approximately 750 to approximately 5,000. As examples of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers and mixtures thereof. Preferably, the hydroxylated compounds are chosen from polyol polyethers, polyhydroxylated polycarbonates and mixtures thereof.

[0254] According to another particular embodiment, the polyol Bm) can be chosen from organic polyols chosen from:

[0255] - triols, such as glycerol;

[0256] - tetraols, such as pentaerythritol (tetramethylolmethane), erythritol, diglycerol;

[0257] - pentols such as xylitol;

[0258] - hexols such as sorbitol and mannitol, or dipentaerythritol or triglycerol; and mixtures thereof.

[0259] According to a particular embodiment, the polyol Bm) comprises at least one compound chosen from glycerol, pentaerythritol and / or sorbitol. In particular, the polyol Bm) may be chosen from glycerol, pentaerythritol, sorbitol and mixtures thereof, more preferably glycerol.

[0260] According to another particular embodiment, the polyol Bm) comprises at least one diol of formula (I).

[0261] According to another embodiment, the polyol Bm) is a mixture of at least one diol of formula (I) and at least one diol such as a polyether.

[0262] B 112 ) Polyacid

[0263] According to one form of the invention, the polyurethane polymer of the latex b) is prepared from at least one polyester polyol Bu) resulting from the reaction of at least one polyol Bm) as described previously with at least one polycarboxylic acid Bm) also called in the remainder of the text “polyacid”, and optionally B113) at least one monocarboxylic acid.

[0264] Said polyacid Bn2) may be acyclic or (poly)cyclic, saturated or unsaturated, aromatic or not, linear or branched, and comprises at least two carboxyl groups -C(O)OH, in particular two to four groups -C(O)OH and more particularly two groups -C(O)OH.

[0265] It is understood that the polyester polyol Bu) can be prepared from a single polyacid or from a mixture of at least two polyacids. In the remainder of the text, unless otherwise indicated, the term "polyacid" or "polycarboxylic acid" means a single polyacid compound or a mixture of several polyacid compounds.

[0266] Said polycarboxylic acid Bn2) may be more particularly chosen from linear, branched and / or cyclic, saturated or unsaturated, or even aromatic, polycarboxylic acids comprising from 2 to 54 carbon atoms, in particular from 2 to 40 and more particularly from 3 to 36 carbon atoms, said acid comprising at least two carboxyl groups -C(O)OH, in particular from 2 to 4 carboxyl groups.

[0267] In particular, the polycarboxylic acid Bn2) may contain two carboxyl groups; it is then referred to as a dicarboxylic acid or diacid.

[0268] According to a particular embodiment, said polycarboxylic acid Bn2) may be chosen from polycarboxylic acids, in particular dicarboxylic acids, having a molecular molar mass MM less than or equal to 200 g.mol1. In particular, said polycarboxylic acid Bn2) may be chosen from oxalic acid, succinic acid, adipic acid, and mixtures thereof, as well as their optical, geometric isomers, their salts of organic or mineral bases, and their solvates such as hydrates.

[0269] According to another particular embodiment of the invention, the polycarboxylic acid Bn2) used to form the polyester polyol Bu) may be chosen from acids, in particular diacids, with a molecular molar mass MM greater than 200 g.mol1. In particular, the polycarboxylic acid Bn2) may be chosen from fatty acids (also called polyfatty acids), in particular dicarboxylic fatty acids (also called difatty acids), and in particular from fatty acid dimers.

[0270] The expression "fatty acid" is intended to denote a carboxylic acid comprising at least one aliphatic chain, linear or branched, preferably linear, saturated or unsaturated, which may contain at least one carbocycle, in particular one or two carbocycle(s), in particular of the mono- or polycyclic cycloalkyl type, for example cyclohexyl or decalinyl (cis or trans decalinyl). The fatty acids are C8 to C38 acids, in particular C8 to C36, in particular C10 to C34, it being understood that the number of carbons characterizing a fatty acid takes into consideration the aliphatic chain of the fatty acid and the carbon atom(s) of said carboxyl group(s). Preferably, the number of carbon atoms of the fatty acid is even.

[0271] The dicarboxylic fatty acids may be chosen from the compounds of the following formula (II), as well as their salts of organic or mineral bases, and their solvates such as hydrates: HO-C(O)-ALK'-C(O)-OH (II) in which ALK' represents an aliphatic chain as defined previously for the fatty acid, preferably C16 to C36, in particular C32 to C36, in particular C34.

[0272] Examples of dicarboxylic fatty acids include sebacic acid and fatty acid dimers. The term "fatty acid dimer" refers to the dimerization product of mono- or polyunsaturated fatty acids.

[0273] Thus, in a particular embodiment, the polyacid component Bn2) comprises at least, or is even formed from, a diacid of the fatty acid dimer type.

[0274] The fatty acids from which fatty acid dimers can be prepared can be more particularly chosen from oleic acid, linoleic acid, palmitoleic acid, linolenic acid, eleostearic acid and mixtures thereof.

[0275] The polyacid Bn2) may be a dimer of fatty acids from C[8 to C38, in particular from C34 to C38 and more particularly from C36.

[0276] In particular, the fatty acid dimer may be a diacid of formula (II) above, in which ALK' represents an aliphatic chain, preferably C16 to C36, in particular C32 to C36, in particular C34, incorporating at least one carbocycle group, preferably one or two carbocycle(s), and more preferably a central carbocycle group, in particular of the mono or polycyclic cycloalkyl type, in particular cyclohexyl or decalinyl, in particular cyclohexyl.

[0277] In a particular embodiment, the polycarboxylic acid Bn2) may be a diacid of the fatty acid dimer type, containing a cycloalkyl group, in particular cyclohexyl, connected to the -C(O)-OH groups via C2 to C10, in particular C4 to C8, in particular C6 alkylene chains, said cycloalkyl group having in particular pendant C4 to C12, in particular C7 to C9, in particular C8 alkyl groups.

[0278] In particular, the fatty acid dimer may be formed from C16-C20 fatty acids, in particular C18, for example from oleic acid and / or linoleic acid.

[0279] Fatty acid dimers may be commercially available. Examples include fatty acid dimers marketed by Croda under the references Pripol®, in particular Pripol®1009, cosmetic grade, with the following structure:

[0280] [Chem. 16] CH. in which n is an integer between 6 and 8.

[0281] According to a particular embodiment, the polyacid component Bn2) may comprise, or even consist of, diacid(s) of the fatty acid dimer type, for example Pripol®1009.

[0282] According to another embodiment, the polyacid component Bn2) may comprise, or even consist of, diacid(s) having a molecular molar mass MM less than or equal to 200 g.mol1, in particular chosen from oxalic acid, succinic acid, adipic acid, and mixtures thereof.

[0283] B in ) Monoacid

[0284] According to one form of the invention, the polyurethane polymer of the latex b) is prepared from at least one polyester polyol Bu) resulting from the reaction of at least one polyol Bm) as described previously with at least one polycarboxylic acid Bn2) as described previously, and at least one monocarboxylic acid Bn3).

[0285] The monocarboxylic acid is also called monocarboxylic acid, or “monoacid”, that is to say comprising a single carboxyl group -C(O)-OH.

[0286] The monocarboxylic acids Bn3) considered are more particularly acyclic or (poly)cyclic monocarboxylic acids, saturated or unsaturated, aromatic or not, linear or branched, comprising from 6 to 32 carbon atoms, in particular from 8 to 28 carbon atoms and more particularly from 10 to 20 carbon atoms.

[0287] It is understood that the polyester polyol Bu) can be prepared from a single monoacid Bn3) or from a mixture of at least two monoacids Bn3). In the remainder of the text, unless otherwise indicated, the term "monoacid" or "monocarboxylic acid" Bn3) thus means a single monoacid compound or a mixture of several monoacid compounds.

[0288] According to a particular embodiment, said monocarboxylic acid Bn3) is non-aromatic, saturated or unsaturated, linear or branched, cyclic or not, and comprises from 6 to 32 carbon atoms, in particular from 8 to 30 carbon atoms and more particularly from 10 to 28 carbon atoms, preferably from 12 to 26 carbon atoms. of carbon, more preferably from 16 to 24 carbon atoms, even more preferably from 18 to 22 carbon atoms.

[0289] Preferably, said monoacid component Bn3) is biosourced, in particular of plant origin.

[0290] When the monoacid Bm) used is of natural origin, it may in particular consist of mixtures comprising saturated acids and unsaturated acids with conjugated and / or non-conjugated unsaturations.

[0291] According to a particular embodiment, said monocarboxylic acid Bn3) is a fatty acid, saturated or unsaturated, preferably biosourced.

[0292] According to a first particular embodiment, said monoacid Bn3) is a monocarboxylic acid comprising an aliphatic chain, linear or branched, preferably linear, saturated or unsaturated, comprising more than 10 carbon atoms, in particular more than 14 carbon atoms, in particular from 14 to 30 carbon atoms, in particular from 14 to 26 carbon atoms and more particularly from 16 to 22 carbon atoms, even more preferably from 18 to 20 carbon atoms.

[0293] As examples, a monoacid Bm) may be chosen from isostearic acid (saturated branched C18), stearic acid (saturated linear C18), linoleic acid (polyunsaturated linear C18), arachidic acid (saturated linear C2o), behenic acid (saturated linear C22) and their mixtures, as well as their geometric isomers, their salts of organic or mineral bases.

[0294] According to another particular embodiment, said monoacid Bn3) is a (poly)cyclic, preferably polycyclic, monocarboxylic acid, comprising in particular a monocyclic, bicyclic, or fused tricyclic, saturated and / or unsaturated, preferably unsaturated, in particular non-aromatic, carbocycle, and comprising from 5 to 20 carbon atoms, said carbocycle being optionally substituted by one or more (Ci-C4)alkyl groups such as methyl. In particular, said monoacid Bn3) comprises a polycyclic, in particular C8-Ci4 fused tricyclic carbocycle, preferably unsaturated and non-aromatic, such as a phenantrenyl group, partially hydrogenated, in particular a decahydrophenantrenyl group.

[0295] It may in particular be abietic acid or one of its optical isomers, its salts of organic or mineral bases, and their solvates, such as hydrates. In particular, abietic acid may be derived from natural rosin.

[0296] According to another particular embodiment, said monoacid Bn3) may be rosin.

[0297] Rosin is a mixture comprising mainly organic acids called rosin acids of which abietic acid is the main constituent.

[0298] According to a particular embodiment, said monoacid Bn3) may comprise at least abietic acid or rosin. In particular, the monoacid Bn3) may be abietic acid or rosin.

[0299] B 12 ) Diols

[0300] According to one embodiment, the composition Cl or Cl' of the invention comprises one or more polyurethane polymer latexes b) obtained from Bi) at least one polyol chosen from B[2) at least one diol.

[0301] According to one embodiment, the diol B[2) is a “low molecular weight diol”, having a molecular weight of about 62 to 700, and preferably 62 to 200. These diols may comprise aliphatic, alicyclic or aromatic groups. Preferably, they comprise only aliphatic groups.

[0302] Preferably, B[2) represents a low molecular weight diol, having more than 20 carbon atoms, more preferably chosen from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, butyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl e)propane), and mixtures thereof.

[0303] The low molecular weight diols may optionally comprise ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described in particular in US patent 3,412,054. Such compounds are preferably chosen from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing a carboxyl group and mixtures thereof.

[0304] If lower molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of C(O)-OH per gram of polyurethane in the polyurethane dispersion are present.

[0305] According to another embodiment, the diol B[2) is a compound having two hydroxyl groups and a number-average molecular weight of about 700 to about 16,000, and preferably of about 750 to about 5,000. Examples of dihydroxylated compounds having a high molecular weight include polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compounds are selected from polyol polyethers, polyhydroxylated polycarbonates and their mixtures. In particular, polyalkylene glycols, such as polyethylene, polypropylene and / or polybutylene glycols, can be used.

[0306] B2) Polyisocyanate

[0307] As indicated previously, a polyurethane of latex b) is obtained from at least one polyisocyanate B2).

[0308] It is understood that the polyurethane of latex b) can be prepared from a single polyisocyanate or from a mixture of at least two distinct polyisocyanates. In the remainder of the text, unless otherwise indicated, the term "polyisocyanate" B2) is understood to mean a single polyisocyanate compound or a mixture of several polyisocyanates.

[0309] The polyisocyanates B2) used according to the invention may be aliphatic, cycloaliphatic or aromatic polyisocyanates capable of allowing the formation of polyurethanes.

[0310] In particular, the polyisocyanates B2) may be chosen from diisocyanates and triisocyanates, and more particularly diisocyanates.

[0311] The polyisocyanates which can be used according to the present invention are in particular chosen from organic diisocyanates having a molecular weight of approximately 112 to 1000, and preferably of approximately 140 to 400.

[0312] According to one form of the invention, the polyisocyanates B2) are chosen from diisocyanates and more particularly from those represented by the general formula R2(NCO)2, in which R2 represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Preferably, R2 represents an organic diisocyanate.Examples of organic diisocyanates that may be chosen include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, isomers of toluene diisocyanate (TDI) such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and optionally 2,2'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and mixtures thereof.Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, and are more . preferentially chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0313] According to another form of the invention, the diisocyanates B2) may be more particularly chosen from the compounds of the following formula (III) O=C=NRN=C=O with R representing a divalent hydrocarbon group, linear or branched, acyclic or (poly)cyclic, saturated or unsaturated, aromatic or not, comprising from 2 to 20 carbon atoms, in particular from 3 to 18 carbon atoms, in particular from 5 to 16 carbon atoms and more particularly from 6 to 14 carbon atoms.

[0314] The diisocyanates may more particularly be of formula (III) above, in which R represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 15 carbon atoms.

[0315] The diisocyanate(s) B2) which can be used for the preparation of a latex polyurethane b) according to the invention are advantageously chosen from tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, isomers of toluene diisocyanate (TDI) such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and mixtures with its isomers diphenylmethane 2,4-diisocyanate and optionally diphenylmethane 2,2'-diisocyanate, naphthalene-1,5-diisocyanate,and mixtures thereof. Preferably, the diisocyanate(s) are chosen from aliphatic and cycloaliphatic diisocyanates.

[0316] More particularly, a single polyisocyanate is used, in particular a single diisocyanate. In particular, the polyisocyanate B2) may be 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, also called isophorone diisocyanate (IPDI) or the bis(4,4'-isocyanatocyclohexyl)methane isomers, hexamethylene diisocyanate.

[0317] Said polyisocyanate(s) B2), for example isophorone diisocyanate, may be used to form the polyurethane of latex b).

[0318] B 3 ) Hydrophilic monomers

[0319] The composition C1 or C1' of the invention comprises one or more polyurethane polymer latexes obtained from B3) at least one hydrophilic monomer chosen from B3[) compounds carrying an acid function, for example a carboxylic function, or a basic function, for example a primary, secondary or tertiary amine function, and further comprising at least one hydroxyl function, preferably at least two hydroxyl functions, in particular two hydroxyl functions such as 2,2-bis(hydroxymethyl)propionic acid or B32) at least one diamine compound of formula H2N-R5-NH2 (X) in which R s represents an alkylene radical substituted by one or more ionic or potentially ionic groups;

[0320] Said hydrophilic compound, integrated at the level of a polyurethane latex polymer b) advantageously allows stabilization of the polymer thus formed in aqueous dispersion (latex), without requiring the addition of surfactant.

[0321] B31) Compounds carrying an acid, or basic, and hydroxyl function

[0322] According to one form of the invention, the composition Cl or Cl' comprises one or more polyurethane polymer latexes b) obtained from B3) of at least one hydrophilic monomer chosen from B3[) the compounds carrying an acid function or a basic function and further comprising at least one hydroxyl function.

[0323] These hydrophilic compounds B33) may be compounds carrying an acid function, for example a carboxylic function, or a basic function, for example a primary, secondary or tertiary amine function, and further comprising at least one hydroxyl function, preferably at least two hydroxyl functions, in particular two hydroxyl functions.

[0324] A polyurethane latex polymer b) can be obtained from a single hydrophilic monomer B33) or from a mixture of at least two hydrophilic monomers B3i). Preferably, it uses a single hydrophilic monomer.

[0325] The acid (respectively basic) functions of the hydrophilic monomers B33) can optionally be neutralized, partially or totally, by a base (respectively an acid), preferably organic.

[0326] Said hydrophilic compound(s) B3[) used in the preparation of a latex polyurethane polymer b) may be more particularly chosen from: compounds of formula (IV) R”-C(O)-OH in which R” represents a linear or branched, saturated or unsaturated, C1 to C10 alkyl group, substituted by one or more hydroxyl groups.

[0327] Preferably, R” represents a branched, saturated, C1 to C8, in particular C1 to C6, alkyl group substituted by one or more hydroxyl groups, in in particular by 1 to 4 hydroxyl groups, in particular by at least two hydroxyl groups, in particular by 2 to 4 hydroxyl groups, for example by two hydroxyl groups. As an example of a compound of formula (IV), mention may be made of 2,2-bis(hydroxymethyl)propionic acid (DMPA);

[0328] Said hydrophilic compound(s) B3i) used in the preparation of a polyurethane latex polymer b) may also be chosen from the compounds of formula (V) R i R 2 R 3 N in which R 1, R 2 and R 3 represent, independently of one another, a linear or branched, saturated or unsaturated, C 1 to C 10 alkyl chain, optionally substituted by one or more hydroxyl groups, or a hydrogen atom, it being understood that at least one of Rb R2 and R3 is other than a hydrogen atom and carries at least one hydroxyl group. Examples of compounds of formula (V) include N-methyldiethanolamine or N-tertbutyldiethanolamine.

[0329] According to a first embodiment variant, the hydrophilic monomer(s) B31) used in the composition of a polyurethane polymer latex b) are of formula (IV) above. In the context of this variant, said hydrophilic monomer(s) may more particularly be of formula (IV) in which R” represents a branched, saturated C1 to C10, in particular C1 to C8 and more particularly C1 to C6 alkyl chain, substituted by one or more hydroxyl groups.

[0330] According to one embodiment, a single hydrophilic monomer of formula (IV) above, in particular as defined above, is used in the composition of a polyurethane polymer latex b). In particular, it may be 2,2-bis(hydroxymethyl)propionic acid (DMPA).

[0331] According to another embodiment variant, the hydrophilic monomer(s) B3i) used in the composition of a polyurethane latex polymer b) are of formula (V) above. In the context of this variant, said hydrophilic monomer(s) may more particularly be of formula (V), in which R 1, R 2 and R 3 represent, independently of one another, a linear or branched, saturated or unsaturated, C 1 to C 10 alkyl chain, optionally substituted by one or more hydroxyl groups, or a hydrogen atom, provided that at least one of Rb, R2 and R3 is other than a hydrogen atom and carries at least one hydroxyl group.

[0332] According to one embodiment, a single hydrophilic monomer B31) of formula (V) above, in particular as defined above, is used in the composition of an alkyd-polyurethane polymer b). In particular, it may be N-methyldiethanolamine or N-tertbutyldiethanolamine.

[0333] A polyurethane latex polymer b) obtained from at least one additional hydrophilic monomer is advantageously neutralized, totally or partially, by adding a base or an acid (neutralizing agent), depending on the nature of the functions (acidic or basic) of the hydrophilic monomer(s) entering into the composition of the polyurethane polymer. It is up to the person skilled in the art to adjust the quantity of neutralizing agent to be introduced into the reaction medium to obtain the desired neutralization.

[0334] In particular, a neutralization percentage of a polyurethane polymer as described above may be greater than or equal to 70%, in particular between 70 and 100%. The neutralization percentage represents the percentage of acid (respectively basic) functions of the polyurethane polymer neutralized (in salt form). It may be evaluated relative to the amount of neutralization agent added.

[0335] Thus, the hydrophilic monomer B3i) can be chosen from the compounds of formula (IV) and (V) mentioned above in which the acid or basic functions are preferably neutralized, totally or partially, by adding a base or an acid, preferably organic.

[0336] In particular, in a polyurethane polymer of latex b) obtained from at least one additional hydrophilic monomer of formula (IV) above, the acid functions of the monomeric units may be in neutralized form, totally or partially, by an organic or mineral base, preferably organic, in particular chosen from primary, secondary or tertiary amines, which may or may not contain substituents, for example hydroxyl groups, such as for example amino-2-methyl-2-propanol, and the salified forms thereof.

[0337] According to a particular embodiment, a polyurethane of latex b), obtained from at least one additional hydrophilic monomer of formula (IV) above, can be neutralized by a tertiary amine such as diisopropylethylamine.

[0338] Other bases can also be used, such as potash, soda or ammonia.

[0339] In a polyurethane polymer of latex b) obtained from at least one additional hydrophilic monomer of formula (V) above, the amine functions of the monomeric units may advantageously be in neutralized form, totally or partially, by an organic or mineral acid, preferably organic. As examples, hydrochloric acid, acetic acid or tartaric acid may be mentioned.

[0340] According to a particular embodiment, the polyurethane of latex b) is prepared from at least one hydrophilic monomer, in particular a single hydrophilic monomer, of formula (IV) mentioned above, and more particularly 2,2-bis(hydroxymethyl)propionic acid (DMPA), the acid functions advantageously being, totally or partially neutralized, preferably by an organic base, in particular by a tertiary amine such as diisopropylethylamine.

[0341] B32) Diamines H 2N-R 5 -NH 2 (X),

[0342] According to one form of the invention, the composition C1 comprises one or more polyurethane polymer latexes b) obtained from B32) at least one diamine compound of formula H2N-R5-NH2 (X) in which R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups;

[0343] The diamines of formula (X), correspond to the compounds of general formula H 2 NR 5 -NH 2 in which R 5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups. Such compounds preferably have one ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Such compounds may optionally comprise two groups reactive with isocyanate groups and one ionic group or one capable of forming an ionic group.

[0344] The ionic or potentially ionic group may preferably be selected from ternary or quaternary ammonium groups or groups convertible into such groups, a carboxyl group, a carboxylate group, a sulfonic acid group and a sulfonate group. The conversion, at least partial, of the groups convertible into a salt of ternary or quaternary ammonium groups may take place before or during mixing with water.

[0345] According to a preferred form of the invention, the ionic group denotes a sulfonic acid group partially or totally neutralized by a preferably mineral base such as sodium hydroxide.

[0346] The diamines of formula (X) are preferably chosen from diaminosulfonates, such as for example the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0347] According to a preferred form of the invention, when diamines B32) are used in the preparation of polyurethane latex polymers b), amines B4) are also used.

[0348] B4) unsubstituted amine compound with ionic group(s)

[0349] According to one embodiment, the polyurethane polymer of latex b) is obtained from B4) at least one amine compound which is not substituted by one or more ionic or potentially ionic groups.

[0350] According to one embodiment, said amine compound not substituted by an ionic or potentially ionic group is a diamine compound.

[0351] According to one embodiment, the diamine compound not substituted by an ionic or potentially ionic group is a compound of formula (XI) H 2 NR 4 -NH 2 in which R4 represents an alkylene or alkylene oxide radical which is not substituted by one or more ionic or potentially ionic groups.

[0352] The diamines of formula (XI) are preferably chosen from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine-1,2, propylenediamine-1,3, 1,4-butylenediamine, 1,6-diamino hexane, piperazine; alkylene oxide diamines, such as 3-{2-[2-(3-aminopropoxy)ethoxy]-ethoxy]propylamine (also called dipropylamine diethylene glycol or DPA-DEG ​​available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexane diamine, isophorone diamine, 4,4-methylenedi-(cyclohexylamine), DPA series ether amines available from Tomah Products, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0353] The amino compounds B4) may also designate isophoronediamine, mixtures of 2, 2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethyl enediamine, diethylenetriamine, 4,4-diaminodicyclohexylmethane, hydrazine hydrate and / or dimethylethylenediamine.

[0354] According to one embodiment, the amine compound B4) denotes a compound comprising a primary and / or secondary amine and a hydroxyl group such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine.

[0355] According to one embodiment, the amine compound B4) denotes methylamine, ethylamine, propylamine, butylamine, roctylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine,

[0356] Dipropylamine, di-butylamine, N-methylaminopropylamine, diethyl (methyl)aminopropylamine, morpholine, piperidine,

[0357] According to a particular embodiment, the amine compound B4) is chosen from 1,2-ethylenediamine, bis(4-aminocyclohexyl)methane, 1,4-diaminobutane, isophoronediamine, ethanolamine, diethanolamine and diethylenetriamine.

[0358] According to a preferred form of the invention, when diamines B4) are used in the preparation of polyurethane latex polymers b), amines B32) as described above are also used.

[0359] According to one embodiment, when one or more amines B4) are used, these preferably comprise one or more amines of formula (XI).

[0360] According to a particular embodiment, when one or more amines B4) are used in the preparation of the latex polyurethane polymer b), the amine(s) B4) preferably comprise one or more diamines preferably of formula (XI), said polyurethane polymer also resulting from the use of one or more hydrophilic compounds B32).

[0361] According to a first variant, the latex polyurethane polymer b) is formed from: Bn) from 50 to 95% by weight, in particular from 60 to 90% by weight, in particular from 70 to 85% by weight, in particular from 75 to 80% by weight, of a polyester polyol Bu) as defined above, said polyester polyol being for example formed from at least: Bin) glycerol; Bn2) a dimer of C18 to C38 fatty acids, in particular C34 to C38 and more particularly C36, for example that marketed by the company Croda, under the reference Pripol®1009, of cosmetic grade; and Bn3) abietic acid or rosin; B2) from 5 to 50% by weight, in particular from 5 to 40% by weight, in particular from 10 to 30% by weight and more particularly from 15 to 20% by weight, of at least one polyisocyanate, in particular as defined above, in particular a diisocyanate such as isophorone diisocyanate; and, B3[) from 2 to 15% by weight, in particular from 3 to 10% by weight and more particularly from 3 to 5% by weight, of at least one hydrophilic monomer as defined above, in particular a single hydrophilic monomer as defined above; the acid or basic functions of said hydrophilic monomer being advantageously, totally or partially, neutralized; said hydrophilic monomer being for example 2,2-bis(hydroxymethyl)propionic acid (DMPA) with the acid functions being advantageously, totally or partially, neutralized, preferably by an organic base, in particular by a tertiary amine such as diisopropylethylamine;the mass percentages being defined in relation to the total weight of the components of the latex polyurethane polymer b).;

[0362] Preferably, the latex polyurethane polymer b) does not comprise any monomeric unit other than those derived from the aforementioned components Bu), B2), B3[). In other words, according to a particular embodiment, the sum of the mass contents of components Bu), B2), B3[), is equal to 100%.

[0363] According to a second variant, the latex polyurethanes b) are formed from B[2) at least one diol, Bu) optionally at least one polyester polyol (in particular the polyester polyol by reaction between hexandiol / neopentyl glycol and adipic acid), B2) at least one polyisocyanate, B32) and B4) at least one hydrophilic monomer (such as sodium N-(2-aminoethyl)-2-aminoethane sulfonate) and at least one amine compound.

[0364] More particularly, the polyurethane(s) present in the aqueous dispersions b) which can be used in the present invention are derived from the reaction of: • at least one prepolymer of the following formula (VI):

[0365] [Chem. 17] (VI)

[0366] Formula (VI) in which,

[0367] - R i represents a bivalent radical of a dihydroxylated compound,

[0368] - R 2 represents a radical of an aliphatic or cycloaliphatic polyisocyanate,

[0369] - R 3 represents a radical of a low molecular weight diol, optionally substituted by one or more ionic groups,

[0370] - n represents an integer ranging from 1 to 5, and

[0371] - m is greater than 1; • at least one chain extender according to the formula H 2 NR 4 -NH 2 (VII), in which R4 represents an alkylene or alkylene oxide radical which is not substituted by one or more ionic or potentially ionic groups; and • at least one chain extender according to the formula H 2 NR 5 -NH 2 (VIII), in which R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups.

[0372] Among the dihydroxylated compounds that can be used according to the present invention, mention may in particular be made of compounds having two hydroxyl groups and a number-average molecular weight of about 700 to about 16,000, and preferably of about 750 to about 5,000. As examples of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers and mixtures thereof. Preferably, the compounds hydroxylated are chosen from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates and their mixtures.

[0373] The polyisocyanates B2) which can be used according to the present invention are in particular chosen from organic diisocyanates having a molecular weight of approximately 112 to 1000, and preferably of approximately 140 to 400.

[0374] Preferably, the polyisocyanates are chosen from diisocyanates and more particularly from those represented by the general formula (VIII) R 2 (N=C=O) 2, in which R 2 represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0375] Preferably, (VI) represents an organic diisocyanate. Examples of organic diisocyanates that may be chosen include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, isomers of toluene diisocyanate (TDI) such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and optionally 2,2'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and mixtures thereof.

[0376] Preferably, the diisocyanates (VI) are aliphatic and cycloaliphatic diisocyanates, and are more preferably chosen from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0377] By "low molecular weight diol" is meant, according to the present invention, a diol having a molecular weight of about 62 to 700, and preferably of 62 to 200. These diols may comprise aliphatic, alicyclic or aromatic groups. Preferably, they comprise only aliphatic groups.

[0378] Preferably, B^) represents a low molecular weight diol, having more than 20 carbon atoms, more preferably chosen from ethylene glycol, diethylene glycol, propane 1,2-diol, propane 1,3-diol, butane 1,4-diol, butylene 1,3-glycol, neopentyl glycol, butyl-ethyl-propane diol, cyclohexane diol, 1,4-cyclohexane dimethanol, hexane 1,6-diol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl e)propane), and mixtures thereof.

[0379] The low molecular weight diols may optionally comprise ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are described in particular in US patent 3,412,054. Such compounds are preferably chosen from dimethylol butanoic acid, dimethylol propionic acid, polycaprolactone diols containing a carboxyl group and mixtures thereof.

[0380] If lower molecular weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of C(O)OH per gram of polyurethane in the polyurethane dispersion are present.

[0381] The prepolymer is extended using two families of chain extenders. The first family of chain extenders corresponds to compounds of general formula H2N-R4-NH2 (VII), in which R4 represents an alkylene or alkylene oxide radical which is not substituted by one or more ionic or potentially ionic groups.

[0382] The chain extenders of formula (VII) are preferably selected from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine; alkylene oxide diamines, such as 3-{2-[2-(3-aminopropoxy)ethoxy]-ethoxy}propylamine (also called dipropylamine diethylene glycol or DPA-DEG ​​available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexane diamine, isophorone diamine, 4,4-methylenedi-(cyclohexylamine), ether amines of the DPA series available from Tomah Products, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propane diol, dipropylamine 2-methyl-1,3-propane diol, dipropylamine 1,4-butane diol, dipropylamine 1,3-butane diol, dipropylamine 1,6-hexane diol and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0383] The second family of chain extenders corresponds to compounds of general formula H2N-R5-NH2 (VIII), in which R5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups. Such compounds preferably have one ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Such compounds may optionally comprise two groups reactive with isocyanate groups and an ionic group or one capable of forming an ionic group.

[0384] The ionic or potentially ionic group may preferably be selected from ternary or quaternary ammonium groups or groups convertible into such groups, a carboxyl group, a carboxylate group, a sulfonic acid group and a sulfonate group. The conversion, at least partial, of the groups convertible into a salt of ternary or quaternary ammonium groups may take place before or during mixing with water.

[0385] The chain extenders of formula (VIII) are preferably chosen from diaminosulfonates, such as for example the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0386] The polyurethane usable according to the present invention may optionally further comprise compounds which are respectively located at the ends of the chains and terminate said chains (chain terminators). Such compounds are described in particular in patents US 7,445,770 and / or US 7,452,770.

[0387] Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa.s at 23°C, more preferably less than 1500, and better still less than 1000. Even more preferably, the aqueous dispersion of polyurethane has a glass transition temperature of less than 0°C.

[0388] Also preferably, the aqueous polyurethane dispersion b) has a solids content (or active material, or dry matter) based on the weight of the dispersion of 20% to 60% by weight, more preferably 25% to 55% by weight and better still 30% to 50% by weight. This means that the polyurethane content (dry matter) of the aqueous dispersion is preferably 20% to 60% by weight, more preferably 25% to 55% by weight and better still 30% to 50% by weight, relative to the total weight of the dispersion.

[0389] Also preferably, the aqueous dispersion of polyurethane particles b) has a glass transition temperature (Tg) equal to or less than -25°C, preferably less than -35°C, and more preferably less than -40°C.

[0390] The polyurethane particles may have an average diameter of up to about 1000 nm, for example from about 50 nm to about 800 nm, more preferably from about 100 nm to about 500 nm. These particle sizes may be measured with a laser particle size analyzer (e.g. Brookhaven BI90).

[0391] As a non-limiting example of aqueous polyurethane dispersions, mention may be made of those sold under the name Baycusan® by Covestro such as, for example, Baycusan® C1000 (INCI name: polyurethane-34), Baycusan® C1001 (INCI name: polyurethane-34), Baycusan® C1003 (INCI name: polyurethane-32), Baycusan® C1004 (INCI name: polyurethane-35) and Baycusan® C1OO8 (INCI name: polyurethane-48).

[0392] According to a third variant, the latex polyurethane polymer is derived from: - B2) at least one aliphatic, araliphatic and / or polyisocyanate cycloaliphatic preferably chosen from HDI, IPDI, H12-MDI and their mixture; - at least one polyol with a number-average molar mass Mn > 330 and - < 6000 g / mol, preferably > 350 and < 5000 g / mol, preferably Bu) at at least one polyester polyol preferably derived from at least one diacid chosen from succinic acid, adipic acid and at least one diol chosen from 1,6 hexanediol, 1,4-butanediol and / or at least neopentyl glycol, and B i2) at least one polyether polyol; - optionally at least one amino compound B4) comprising at least two amino groups such as ethylenediamine, which can react with isocyanate functions, - optionally at least one hydrophilic monomer B3) chosen from compounds B32) as described above, in particular chosen from compounds substituted by an acidic ionic group such as 2-(2-aminoethylamino)ethanesulfonic acid or its salts such as its sodium salts; - optionally at least one alcohol comprising at least two hydroxy functions Bi2) and with a molar mass > 62 and < 399 g / mol, - e)_ possibly at least one compound of which one function is reactive vis- with respect to isocyanates,

[0393] As a non-limiting example of aqueous polyurethane dispersions, mention may be made of those sold under the name Baycusan® by Covestro such as, for example, Baycusan® eco E1000 (INCI name: polyurethane-93), Baycusan® eco E1001 (INCI name: polyurethane-99).

[0394] Particularly the polyurethane latex b) of the invention is (are) chosen from the polyurethanes with the following INCI names: polyurethane-32, polyurethane-32, polyurethane-34, polyurethane-35, polyurethane-48, polyurethane-93, and polyurethane-99 and their mixtures.

[0395] According to one embodiment, the total quantity of the aqueous dispersion(s) of polyurethane particles b) present in the composition C1 or C1' according to the invention is preferably between 0.01% and 60% by weight, more preferably from 0.1% to 55% by weight, and better still from 0.2% to 50% by weight, relative to the total weight of the composition.

[0396] According to one embodiment, the total quantity of polyurethane (dry matter), present in the composition Cl or Cl' according to the invention, is between 0.01% and 30% by weight, more preferably from 0.05% to 28% by weight, and better still from 0.1% to 25% by weight, relative to the total weight of the composition.

[0397] c) Fatty substances

[0398] According to a particular embodiment of the invention, the composition further comprises one or more fatty substances.

[0399] By "fatty substance" is meant an organic compound insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mm Hg) (solubility less than 5% and preferably 1%, even more preferably 0.1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, such as, for example, chloroform, ethanol, benzene, vaseline oil or decamethyl cyclopentasiloxane.

[0400] The fatty substance(s) of the invention are of natural or synthetic origin, preferably natural, more preferably of plant origin. They are different from fatty acids because salified fatty acids constitute soaps which are generally soluble in aqueous media.

[0401] According to a particular embodiment of the invention, the composition comprises one or more fatty substances which are not liquid at 25°C and at atmospheric pressure.

[0402] The wax(es)

[0403] According to a particular embodiment, the composition of the invention comprises one or more waxes.

[0404] By "wax" is meant a lipophilic compound, solid at room temperature (25°C), with a reversible solid / liquid state change, having a melting point greater than or equal to 30°C and up to 200°C and in particular up to 120°C.

[0405] In particular, the wax(es) suitable for the invention may have a melting point greater than or equal to 45°C, and in particular greater than or equal to 55°C.

[0406] The composition according to the invention preferably comprises a wax content ranging from 0.5% to 30% by weight relative to the total weight of the composition, in particular from 1 to 20%, more particularly from 2 to 15%.

[0407] According to a particular form of the invention, the composition of the invention is solid, in particular anhydrous. It can then be in the form of a stick; polyethylene micro-waxes will be used in the form of crystallites with a form factor of at least 2 having a melting point ranging from 70 to 110°C and preferably 70 to 100°C, in order to reduce or even eliminate the presence of layers in the solid composition. These needle-shaped crystallites and in particular their dimensions can be visually characterized using the following method.

[0408] The pasty compound(s)

[0409] According to a particular embodiment, the composition of the invention comprises one or more pasty compounds.

[0410] For the purposes of the present invention, the term "pasty compound" means a lipophilic fatty compound with a reversible solid / liquid state change, having an anisotropic crystalline organization in the solid state, and comprising at a temperature of 23°C a liquid fraction and a solid fraction.

[0411] Preferably the composition contains one or more fatty substances c) which are hydrocarbon fatty substances that are liquid at 25°C and atmospheric pressure.

[0412] The liquid hydrocarbon fatty substance(s) are in particular chosen from hydrocarbons and C6-Ci6 or with more than 16 carbon atoms up to 60 carbon atoms, preferably between C6 and C16, and in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides or fluorinated oils of synthetic origin, fatty alcohols, fatty acid and / or fatty alcohol esters, silicones. In particular, the liquid fatty substance(s) are chosen from non-silicone oils.

[0413] It is recalled that for the purposes of the invention, the alcohols, esters and fatty acids more particularly have one or more hydrocarbon group(s), linear or branched, saturated or unsaturated, comprising 6 to 60 carbon atoms, optionally substituted, in particular by one or more hydroxyl group(s) OH (in particular 1 to 4 hydroxyl group(s). If they are unsaturated, these compounds may comprise one to three unsaturations, preferably 1 to 3 carbon-carbon double bonds, conjugated or not.

[0414] As regards the C6-Ci6 alkanes, the latter are linear or branched, optionally cyclic, preferably the fatty substance(s) c) of the invention are chosen from linear or branched alkanes, C8-Ci4, more preferably C9-Ci3, even more preferably C9-Ci2. By way of example, mention may be made of hexane, decane, undecane, dodecane, tridecane, isoparaffins such as isohexadecane, isodecane or isododecane. Linear or branched hydrocarbons of more than 16 carbon atoms may be chosen from paraffin oils, vaseline oil, polydecenes, hydrogenated polyisobutene such as Parléam®.

[0415] Among the liquid hydrocarbon fatty bodies c) having an overall solubility parameter according to the HANSEN solubility space less than or equal to 20 (MPa)1 / 2, mention may be made of oils, which may be chosen from natural or synthetic oils, hydrocarbons, possibly fluorinated, possibly branched, alone or in mixture.

[0416] According to a very advantageous embodiment, the composition of the invention comprises one or more fatty substances which is (are) one or more hydrocarbon oil(s). The oil(s) may be volatile or non-volatile.

[0417] According to a preferred embodiment of the invention, the fatty substance(s) c) are linear or branched hydrocarbon oils, which are volatile, in particular chosen from undecane, decane, dodecane, isododecane, tridecane, and their mixture of different oils, volatile oils preferably comprising isododecane in the mixture, or a mixture of undecane and tridecane.

[0418] According to another particular embodiment, the liquid fatty body(ies) c) are a mixture of a volatile hydrocarbon oil and a non-volatile hydrocarbon oil, the mixture of which preferably comprises dodecane or isododecane as volatile oil.

[0419] Particularly the fatty substance(s) c) of the invention are a mixture of C9-C12 alkanes, preferably of natural origin, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes. This mixture is notably known under the INCI name C9-C12 ALKANE, CAS 68608-12-8, VEGELIGHT SILK® marketed by BioSynthls. This mixture of biodegradable volatile oils, volatile obtained from coconut oil (viscosity is 0.9-1.1 cSt (40 °C) and a flash point at 65 °C)

[0420] According to one embodiment, composition C1 contains only oils that are liquid at 25°C and atmospheric pressure.

[0421] According to another embodiment, the composition C1 contains at least 80% of hydrocarbon oils, liquid at 25°C and atmospheric pressure, preferably volatile, more preferably chosen from isodecane, decane, Cetiol UT®, VEGELIGHT SILK®.

[0422] According to another embodiment, the composition C1 may comprise volatile and non-volatile oils, in particular in a volatile oil / non-volatile oil proportion greater than or equal to 4.

[0423] According to another embodiment, the composition C1 contains from 0 to 10% of silicone oils, preferably from 0 to 5% of silicone oils.

[0424] As volatile silicone oils, mention may be made of volatile linear or cyclic silicone oils, in particular, those having a viscosity less than or equal to 8 centistokes (cSt) (8 x 10 6m2 / s), and having, in particular, from 2 to 10 silicon atoms, and in particular, from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, mention may be made, in particular, of dimethicones with viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

[0425] As non-volatile silicone oils, mention may be made of non-volatile, linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy and / or phenyl groups, pendant or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenyl ethyl trimethylsiloxysilicates and pentaphenyl silicone oils.

[0426] The hydrocarbon oil can be chosen from:

[0427] * hydrocarbon oils having from 8 to 14 carbon atoms, and in particular:

[0428] - branched C8-Ci4 alkanes such as C8-Ci4 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example oils sold under the trade names Isopars' or Permetyls,

[0429] - linear alkanes, for example such as n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and n-tridecane (Cl3) obtained in examples 1 and 2 of application WO 2008 / 155059 from Cognis, and their mixtures as well as the mixtures of n-undecane (C11) and n-tridecane (Cl3) Cetiol Ultimate® from BASF.

[0430] * short chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate

[0431] * hydrocarbon oils of vegetable origin such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths varying from C4 to C24, the latter being able to be linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or even wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose, coconut oils; shea butter; or also the triglycerides of caprylic / capric acids such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel,

[0432] * synthetic ethers having from 10 to 40 carbon atoms;

[0433] * linear or branched hydrocarbons, of mineral or synthetic origin such as than petrolatum, polydecenes, hydrogenated polyisobutene such as Parleam ®, squalane, paraffin oils, and mixtures thereof,

[0434] * esters such as oils of formula R'C(O)-O-R2 in which R1 represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms provided that R1 + R2 is #10, such as, for example, Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, benzoates of C12-C15 alcohols, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate, 2-octyl-dodecyl lactate;polyol esters and pentaerythritol esters, more preferably esters of linear or branched C8-Ci0 fatty acid and linear or branched C12-Ci8 fatty alcohol alone or in mixture with alkanes resulting from the complete hydrogenation / reduction of fatty acids from Cocos Nucifera (Coconut) oil, particularly dodecane or mixtures of cococaprylate / caprate with dodecane, we can cite those with the INCI name coconut alkanes (and) Coco-caprylate / caprate marketed under the name VEGELIGHT 1212LC® by Grant Industries. ;

[0435] * fatty alcohols that are liquid at room temperature with a branched carbon chain and / or unsaturated having from 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.

[0436] In particular, the composition comprises at least one liquid hydrocarbon fatty substance c) chosen from:

[0437] - vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, macadamia, soybean, sweet almond, calophyllum, palm, grape seed, corn, arara, cottonseed, apricot, avocado, jojoba, olive, coconut or cereal germ oil;

[0438] - linear, branched or cyclic esters, having more than 6 carbon atoms, in particular 6 to 30 carbon atoms; and in particular isononyl isononanoate;

[0439] and more particularly the esters of formula Rd-C(O)-O-Re in which Rd represents the residue of a higher fatty acid comprising from 7 to 19 carbon atoms and Re represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, in particular diisopropyl adipate and isopropyl myristate; more preferably the esters of formula Rd-C(O)-O-Re in which Rd represents the residue of a higher fatty acid comprising from 8 to 10 carbon atoms and Re represents a hydrocarbon chain comprising from 12 to 18 carbon atoms;

[0440] - hydrocarbons and in particular linear, branched and / or cyclic alkanes, volatile or non-volatile, such as C5-C6o isoparaffins, optionally volatile such as undecane, dodecane, isododecane, tridecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or 'ISOPARs', and their mixture; or alkanes resulting from the complete hydrogenation / reduction of mixtures of fatty acids from Cocos Nucifera (Coconut) oil such as dodecane, the mixture of C9-Ci2 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched alkanes, C9-Ci2 in particular comprising dodecane or paraffin oils, vaseline oils, or hydrogenated polyisobutylene;

[0441] - ethers having 6 to 30 carbon atoms;

[0442] - ketones having 6 to 30 carbon atoms;

[0443] - aliphatic fatty monoalcohols having 6 to 30 carbon atoms, the chain hydrocarbon having no substitution group, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol;

[0444] - polyols having 6 to 30 carbon atoms, such as hexylene glycol; and

[0445] - their mixtures, such as mixtures of linear or branched fatty acid esters in C8-Cio and C12-Ci8 fatty alcohol and alkanes derived from the complete hydrogenation / reduction of mixtures of fatty acids derived from Cocos Nucifera (Coconut) oil, in particular dodecane, such as mixtures of cococaprylate / caprate and dodecane, including those with the INCI name coconut alkanes (and) Coco-caprylate / caprate marketed under the name VEGELIGHT 1212LC® by Grant Industries; or mixtures of C9-Ci2 alkanes, the chains of which comprise 9 to 12 carbon atoms, preferably linear or branched alkanes, C9-Ci2 in particular comprising dodecane, including the oil mixture with the INCI name C9-12 ALKANE, VEGELIGHT SILK® marketed by BioSynthls.

[0446] Preferably, the composition of the invention comprises at least one liquid hydrocarbon fatty substance c) chosen from:

[0447] - vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides,

[0448] - esters of formula Rd-C(O)-O-Re in which Rd represents the residue of an acid higher fatty acid comprising 7 to 19 carbon atoms and Re represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, more preferably the esters of formula Rd-C(O)-O-Re in which Rd represents the residue of a higher fatty acid comprising from 8 to 10 carbon atoms and Re represents a hydrocarbon chain comprising from 12 to 18 carbon atoms;

[0449] - linear or branched C8-C6o alkanes, volatile or non-volatile such as isododecane and alkanes from the complete hydrogenation / reduction of fatty acid mixtures from Cocos Nucifera (Coconut) oil, particularly dodecane;

[0450] - cyclic, non-aromatic, C5-Ci2 alkanes; volatile or non-volatile;

[0451] - ethers having 7 to 30 carbon atoms;

[0452] - ketones having 8 to 30 carbon atoms;

[0453] - aliphatic fatty monoalcohols having 12 to 30 carbon atoms, the chain hydrocarbon containing no substitution group, and

[0454] - their mixtures.

[0455] Advantageously, the fatty body(ies) c) of the invention, in particular liquid, are apolar, i.e. formed solely of carbon and hydrogen atoms.

[0456] The liquid hydrocarbon fatty body(ies) are preferably chosen from hydrocarbon oils having from 8 to 14 carbon atoms, in particular volatile ones, more particularly the apolar oils, described above.

[0457] Preferably the fatty substance(s) c) of the invention, in particular liquid, are chosen from alkanes such as dodecane, decane, isododecane, fatty alcohols such as octyldodecanol, esters such as isononyl isononanoate, Coco-caprylate / caprate and mixtures thereof, more preferably alkanes.

[0458] More particularly, the fatty substance(s) c) of the invention, in particular liquid, are chosen from linear or branched C6-Ci6 alkanes, preferably C8-Ci4, more preferably C9-Ci3, even more preferably C9-Ci2, and even more preferably the alkanes are volatile. More particularly, the liquid fatty substance(s) iii) of the invention are volatile and chosen from undecane, decane, dodecane, isododecane, tridecane, and their mixture comprising in particular dodecane, isododecane or a mixture of undecane and tridecane.

[0459] Preferably, the fatty substance(s) c) of the invention, in particular liquid, are isododecane.

[0460] According to another advantageous embodiment of the invention, the fatty substance(s) c) of the invention, in particular liquid, is (are) a mixture of non-volatile oil(s) and volatile oil(s). The mixture preferably comprises isododecane, undecane, dodecane, isododecane, tridecane, and more preferably isododecane as volatile oil. As a volatile and non-volatile oil mixture, mention may be made of the mixture of isododecane and isononyl isononanoate or the mixture of isododecane with isononyl isononanoate.

[0461] More preferably when the fatty substance(s) are a mixture of volatile and non-volatile oil, the quantity of volatile oil is greater than the quantity of non-volatile oil.

[0462] In particular in the mixture the non-volatile oil is a phenylated silicone oil preferably chosen from pentaphenylated silicone oils.

[0463] Advantageously, the composition comprises one or more fatty substances, in particular liquid at 25°C and at atmospheric pressure, preferably one or more oils, 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, preferably ranging from 20 to 80% by weight.

[0464] According to a preferred embodiment of the invention, the composition Cl or Cl' according to the invention comprises c) one or more fatty substances, in particular liquid at 25°C and at atmospheric pressure, e) water and d) one or more surfactants.

[0465] Surfactants

[0466] According to a particular embodiment of the invention, the composition further comprises d) one or more surfactants, preferably non-ionic, ionic or mixtures thereof.

[0467] According to another particular embodiment of the invention, the composition does not comprise a surfactant.

[0468] By "surfactant" is meant a compound that modifies the surface tension between two surfaces. The surfactant(s) d) are amphiphilic molecules, which have two parts of different polarity, one lipophilic (which retains fatty substances) which is apolar, the other hydrophilic (miscible or soluble in water) is polar. The lipophilic part is generally a fatty chain, and the other water-miscible part is polar, and / or protic.

[0469] By "ionic" we mean anionic, cationic, amphoteric, or zwitterionic.

[0470] By “fatty chain” is meant a hydrocarbon chain comprising more than 6 atoms, preferably between 6 and 30 carbon atoms, preferably from 8 to 24 carbon atoms, linear or branched, saturated or unsaturated.

[0471] According to a first particular embodiment, the composition of the invention contains d) at least one non-ionic, silicone or non-silicone surfactant.

[0472] Among the non-ionic surfactants according to the invention, mention may be made, alone or in mixtures, of fatty alcohols, alpha-diols, alkylphenols, these 3 types of compounds being polyethoxylated, polypropoxylated and / or polyglycerolated, and having a fatty chain comprising, for example, 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range in particular from 2 to 50 and the number of glycerol groups being able to range in particular from 2 to 30.Mention may also be made of copolymers of ethylene and propylene oxide, condensates of ethylene and propylene oxide on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1.5 to 4; oxyethylenated sorbitan fatty acid esters having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (Ci0-Ci4)alkylamine oxides or N-acylaminopropylmorpholine oxides.

[0473] More particularly, the surfactant or surfactants of the invention are chosen from non-ionic surfactants, in particular chosen from: i) (poly)ethoxylated fatty alcohols; ii) (poly)glycerolated fatty alcohols; and iii) alkylpolyglycosides (APG).

[0474] As regards alkylpolyglycosides, these compounds are well known and can be more particularly represented by the formula R' i O-(R' 2 O) t> (G') v> in which: • R' represents a linear or branched alkyl and / or alkenyl radical containing approximately 8 to 24 carbon atoms, an alkylphenyl radical whose linear or branched alkyl radical contains 8 to 24 carbon atoms; • R' 2 represents an alkylene radical containing approximately 2 to 4 carbon atoms; • G' represents a sugar unit comprising 5 to 6 carbon atoms; • t' denotes an integer between 0 and 10 inclusive, preferably between 0 and 4, preferably between 0 and 4; and • v' denotes an integer between 1 and 15 inclusive.

[0475] Preferred alkylpolyglycosides according to the present invention are compounds of formula (V) in which R i denotes more particularly a saturated or unsaturated, linear or branched alkyl radical comprising from 8 to 18 carbon atoms, t' denotes a value ranging from 0 to 3 and more particularly still equal to 0, G' can denote glucose, fructose or galactose, preferably glucose. The degree of polymerization, i.e. the value of v' in formula (V), can range from 1 to 15, preferably from 1 to 4. The average degree of polymerization is more particularly between 1 and 2 and even more preferably from 1.1 to 1.5.

[0476] The glycosidic bonds between the sugar units are of the 1-6 or 1-4 type and preferably 1-4.

[0477] The (poly)ethoxylated fatty alcohols suitable for implementing the invention are more particularly chosen from alcohols comprising from 8 to 30 carbon atoms, and preferably from 12 to 22 carbon atoms.

[0478] The (poly)ethoxylated fatty alcohols more particularly have one or more hydrocarbon groups, linear or branched, saturated or unsaturated, comprising 8 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.

[0479] The (poly)ethoxylated fatty alcohols are more particularly fatty alcohols comprising from 8 to 22 carbon atoms and oxyethylenated by 1 to 30 moles of ethylene oxide (1 to 30 EO). Among them, mention may be made more particularly of lauryl alcohol 2 EO, lauryl alcohol 3 EO, decyl alcohol 3 EO, decyl alcohol 5 EO and oleyl alcohol 20 EO.

[0480] Mixtures of these (poly)oxyethylenated fatty alcohols can also be used.

[0481] Preferably, the non-ionic surfactants are chosen from (C6-C24)alkyl(poly)glycosides, and more particularly (C8-C18)alkyl(poly)glycosides, ethoxylated C8-C30 fatty acid esters of sorbitan, polyethoxylated C8-C30 fatty alcohols, polyoxyethylenated C8-C30 fatty acid esters, these compounds preferably having 2 to 150 moles of ethylene oxide, and mixtures thereof.

[0482] Among the non-ionic surfactants, C6-C24 alkyl polyglucosides and (poly)ethoxylated fatty alcohols are preferably used, and C8-C16 alkyl polyglucosides are more particularly used.

[0483] The total amount of non-ionic surfactants preferably ranges from 0.01% to 60% by weight relative to the total weight of the composition, preferably from 0.5% to 30% by weight, and more particularly from 2 to 10% by weight relative to the total weight of the composition of the invention.

[0484] According to a particular embodiment of the invention, the composition comprises one or more ionic surfactants.

[0485] According to a particular embodiment of the invention, the composition comprises one or more cationic surfactants. They are advantageously chosen from salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts, and mixtures thereof.

[0486] As quaternary ammonium salts, mention may in particular be made of quaternary ammonium salts of formula R s R9 R m RNN +, Q in which the groups R g to R h, which may be identical or different, represent a linear or branched aliphatic group, comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R8 to Ru comprising from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms; the linear or branched aliphatic groups may comprise heteroatoms such as in particular oxygen, nitrogen, sulfur, these heteroatoms being non-adjacent and halogens; and Q' is an anionic counterion chosen in particular from i) halides such as bromides, chlorides, iodides, fluorides, ii) phosphates, iii) acetates, iv) lactates, v) alkyl(Ci-C4)sulfates, vi) alkyl(Ci-C4)sulfonates and vii) alkyl(Ci-C4)arylsulfonates.

[0487] Mention may in particular be made of halides, in particular chlorides, of tetraalkylammonium such as dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains from 12 to 22 carbon atoms, in particular from 14 to 20 carbon atoms such as behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium (cetrimonium chloride) and benzyldimethylstearylammonium chlorides. Mention may also be made of halides, and in particular chlorides, of palmitylamidopropyltrimethylammonium or stearamidopropyldimethyl-(myristylacetate)-ammonium; in particular the product marketed under the name CERAPHYL® 70 by the company VAN DYK.

[0488] The anionic counterion Q is preferably a halide, preferably chloride, bromide or iodide, an alkyl(CrC4)sulfate, an alkyl(Ci-C4)sulfonate or an alkyl(CrC 4)aryl-sulfonate, a methanesulfonate, a phosphate, a nitrate, a tosylate, an anion derived from an organic acid such as an acetate or a lactate or any other anion compatible with ester-functional ammonium. The anionic counterion Q is more particularly a chloride, a methylsulfate or an ethylsulfate.

[0489] The composition according to the invention may contain, for example, a mixture of quaternary ammonium mono-, di- and triester salts with a majority by weight of diester salts. It is also possible to use the ammonium salts containing at least one ester function described in patents US-A-4874554 and US-A-4137180. It is also possible to use behenoylhydroxypropyltrimethylammonium chloride, for example, offered by the company KAO under the name Quartamin BTC 131.

[0490] Preferably, the ammonium salts containing at least one ester function contain two ester functions.

[0491] Preferably, the surfactant(s) are cationic and are chosen from cetyltrimethylammonium, behenyltrimethylammonium, dipalmitoylethylhydroxyethylmethylammonium and mixtures thereof; and more particularly among behenyltrimethylammonium chloride or methosulfate, cetyltrimethylammonium chloride or methosulfate, dipalmitoylethylhydroxyethylmethylammonium chloride or methosulfate and mixtures thereof.

[0492] More preferably, the cationic surfactant(s) according to the invention are chosen from alkyltrimethylammonium salts in which the alkyl group contains from 12 to 22 carbon atoms, more preferably from 14 to 20 carbon atoms and more particularly behenyltrimethylammonium salts, cetrimonium salts and in particular cetyltrimethylammonium chloride, behenyltrimethylammonium chloride or mixtures thereof in all proportions.

[0493] According to another particular embodiment of the invention, the composition comprises one or more anionic surfactants.

[0494] The term "anionic surfactant" means a surfactant comprising only anionic groups as ionic or ionizable groups. These anionic groups are preferably chosen from the groups -C(O)OH, -C(O)O, -SO3H, -S(O)2O, -OS(O)2OH, -OS(O)2O, -P(O)OH2, -P(O)2O, -P(O)O2, -P(OH)2, =P(O)OH, -P(OH)O, =P(O)O, =POH, =PO, the anionic parts comprising a cationic counterion such as those derived from an alkali metal, an alkaline earth metal, or from an amine or an ammonium.

[0495] As examples of anionic surfactants that can be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, salts of D-galactoside-uronic acids, alkyl ether-carboxylic acid salts, alkyl aryl ether-carboxylic acid salts, alkyl amidoether-carboxylic acid salts, and the corresponding non-salified forms of all these compounds,the alkyl and acyl groups of all these compounds containing from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.

[0496] These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

[0497] Among the anionic surfactants, it is preferred to use alkyl(C6-C24)sulfates, alkyl(C6-C24)ethersulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol, and alkaline earth metal salts, or a mixture of these compounds.

[0498] In particular, it is preferred to use alkyl(Ci2-C2o)sulfates, alkyl(Ci2-C20)ethersulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of salts of alkali metals, ammonium, amino alcohols, and alkaline earth metals, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate, in particular those containing 2.2 moles of ethylene oxide. More preferably alkyl(Ci2-C20)sulfates such as alkali metal lauryl sulfate such as sodium lauryl sulfate.

[0499] According to a particular embodiment of the invention, the composition comprises one or more amphoteric or zwitterionic surfactants. The amphoteric surfactants are in particular derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may in particular be made of alkyl(C8-C20)betaines, sulfobetaines, alkyl(C8-C20)amidoalkyl(C3-C8)betaines and alkyl(C8-C20)amidalkyl(C6-C8)sulfobetaines.

[0500] Among the amphoteric or zwitterionic surfactants cited above, use is preferably made of alkyl(C8-C20)betaines such as cocobetaine, alkyl(C8-C20)amidoalkyl(C3-C8)betaines such as cocamidopropylbetaine, and mixtures thereof. More preferably, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropylbetaine and cocobetaine.

[0501] According to a particular embodiment of the invention, the surfactant(s) have a high HLB, i.e. greater than 10, preferably greater than 15.

[0502] According to another particular embodiment of the invention, the surfactant(s) have an HLB or low, i.e. less than or equal to 10, more preferably between 1 and 6.

[0503] By "HLB" or Hydrophilic-Lipophilic Balance we mean a hydrophilic / lipophilic balance value, according to the definition of WC Griffin (Classification of Surface-Active Agents by HLB, Journal of the Society of Cosmetic Chemists J_, 311 (1949). It is possible to calculate the HLB by the classical method of JT Davies (Davies JT, A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent, Gas / Liquid and Liquid / Liquid Interface. Proceedings of the International Congress of Surface Activity (1957): 426-438).

[0504] Preferably, the surfactant(s) of the invention are chosen from: • N-lauroyl sarcosinates of alkali or alkaline earth metals such as sodium • laureth sulfates of alkali or alkaline earth metals such as sodium • behenyl trimethylammonium halides, preferably chloride • cetrimonium halides, preferably chloride • dodecyl sulfates of alkali or alkaline earth metals such as sodium • N-cocoyl glycinates of alkali or alkaline earth metals such as sodium and the non-ionic surfactant(s) are chosen from: • polyoxyethylenated lauryl alcohols 4 EO and / or 23 EO (laureth-23 and / or laureth-4) • polyoxyethylene sorbitan monopalmitate (20OE) and • polyglyceryl-4-isostearate (PG4-isosterarate). More preferably PG4-isosterarate.

[0505] According to a particular embodiment of the invention, the surfactant(s) are a mixture of non-ionic surfactants in ratios such that the HLB of the mixture is a high HLB, preferably the non-ionic surfactants are chosen from polyglyceryl-4 isostearate, polyoxyethylenated lauryl alcohols 4 EO and / or 23 EO (laureth-23 and / or laureth-4) and polyoxyethylenated sorbitan monopalmitate (20 EO).

[0506] Preferably, the surfactant(s) included in the composition of the invention is a single type of surfactant, preferably non-ionic.

[0507] By non-ionic surfactant is preferably meant LAURETH-23, LAURETH-4, oxyethylene sorbitan monopalmitate (20 EO), polyglyceryl-4-isostearate.

[0508] Examples of high HLB non-ionic surfactants include: oxyethylene sorbitan monopalmitate (20OE), Laureth-23.

[0509] Preferably, the surfactants of the invention are non-ionic and of low HLB, for example, laureth-4, polyglyceryl-4-isostearate, more preferably PG4-isosterarate.

[0510] According to another preferred embodiment of the invention, the composition comprises one or more silicone surfactants.

[0511] The composition according to the invention may comprise one or more silicone surfactants. The silicone surfactants may be water-soluble, spontaneously water-dispersible or non-water-soluble. Preferably, they are water-soluble or spontaneously water-dispersible.

[0512] Preferably the silicone surfactants are oxyalkylenated, preferably oxyethylenated.

[0513] The composition may comprise silicone surfactants. The silicone surfactants may be chosen from the compounds of formulae (Id), (Ild), (Illd), (IVd) and (Vd) below:

[0514] [Chem. 18]:

[0515]

[0516] [Chem. 19]:

[0517] (ild)

[0518] [Chem. 20]:

[0519] (IM)

[0520] [Chem. 21]:

[0521] I? J (IVd)

[0522] [Chem. 22]:

[0523] Ok | | University Hospital | 0¾ | (¾ I | t | I * 4 t | S lit । § s | | c& I to, L ( to. OM ta^ (Vd)

[0524] Formulas (Id) to (Vd) in which: • R i, identical or different, represents a linear or branched C1-C30 alkyl radical, or a phenyl radical; • R 3 and R 4, identical or different, denote a linear or branched C1-C12 alkyl radical, preferably a methyl radical; • R 2, identical or different, represents a group -(CH2)cO-(C2H4O)a'-(C6H6O)b'-R5 or -(CH2)cO-(C4H8O)a'-R5 in which a' varies from 0 to 50; b' varies from 0 to 50 and a'+b' is greater than or equal to 1; c varies from 0 to 4; and • R 5, identical or different, is chosen from a hydrogen atom, a linear or branched alkyl group, comprising from 1 to 12 carbon atoms; a linear or branched alkoxy group, comprising from 1 to 6 carbon atoms; a linear or branched acyl group, comprising from 2 to 12 carbon atoms; a hydroxyl group, a -SO3M group, a -OC(O)-R6 or -C(O)OR 6 group, a C1-C6 aminoalkoxy group optionally substituted on the amine by one or two C1-C4 alkyl radicals, optionally carrying at least one hydroxyl group; a C2-C6 aminoacyl group optionally substituted on the amine by one or two C1-C4 alkyl radicals, optionally carrying at least one hydroxyl group; a -NHCH2CH2 COOM group, a -N(CH2CH2COOM)2 group;a C1-C12 aminoalkyl group, optionally substituted on the amine and on the alkyl chain by one or two C1-C4 alkyl radicals, optionally carrying at least one hydroxyl group, a C1-C30 carboxyacyl group, a phosphono group optionally substituted by one or two substituted C1-C12 aminoalkyl groups, a -CO(CH2)dCOOM group, a -OCO-CHR7(CH2)dCOOM group, a -NHCO(CH2)dOH group, an ammonium -NH3Y group; in which M, identical or different, denotes a hydrogen atom, or a cationic counterion such as an alkali or alkaline earth metal such as Na, K, Li, NH4 or an organic amine; R6 denotes a linear or branched C1-C30 alkyl group; R7 denotes a hydrogen atom or an SO3M group; d varies from 1 to 10; and Y represents an anionic counterion such as a halide (chloride, bromide), a sulfate, or a carboxylate (acetate, lactate, citrate); ; • m varies from 0 to 20; m' varies from 1 to 20; n varies from 0 to 500; p varies from 1 to 50; • q varies from 0 to 20; w varies from 1 to 100; • a varies from 0 to 50; b varies from 0 to 50; and a+b is greater than or equal to 1, in the formula (IVb).

[0525] Mention may in particular be made of the silicone surfactants sold under the trade names FLUID DC193 and DC5225C by the company DOW CORNING, SILWET® L 77 by the company OSI and MAZIL ® 756 by the company MAZER PPG.

[0526] Preferably, the silicone surfactant is a mixture of silicones comprising hydrophilic grafts. It is preferably constituted by a mixture of oxyethylenated (EO) oxypropylenated (OP) polydimethylsiloxane (18 EO / 18 OP), cyclopentadimethylsiloxane and water (10 / 88 / 2) such as the product marketed under the name Dow Corning 5225C Formulation Aid by the company DOW CORNING.

[0527] According to a preferred embodiment of the invention, the surfactant(s) are silicone, optionally polyalkoxylated, in particular polyglycerolated (PEG) and / or are mixed with one or more non-ionic surfactants, in particular polyalkoxylated, such as polyglycerolated polyethylene glycol (PEG) or polypropylene glycol (PPG).

[0528] The composition according to the invention may comprise silicone surfactants in an amount ranging from 0.01% to 30% by weight, in particular from 0.1% to 20% by weight, particularly between 1% and 10% by weight, better still between 2% and 6% by weight relative to the total weight of the composition.

[0529] More particularly, the composition of the invention comprises d) one or more surfactants, in particular non-ionic, silicone or not, preferably chosen from: i. fatty alcohols, ii. alpha-diols, iii. alkylphenols, these 3 types of compounds being poly(Ci-C6)alkoxylated (polyethoxylated, polypropoxylated and / or polyglycerolated), and having a fatty chain comprising for example 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range in particular from 2 to 50 and the number of glycerol groups being able to range in particular from 2 to 30; in particular - polyethoxylated, polypropoxylated, polyglycerolated and / or polyethylene glycol C8-C3o fatty acid esters of C8 to C22 fatty alcohols such as PG4-isostearate, and - alkylpolyglycosides (APG), i. silicone surfactants, possibly polyalkoxylated in particular polyglycerolated (PG) and / or in a mixture with one or more non-ionic surfactants, in particular polyalkoxylated such as polyglycerolated (PEG), such as PEG-silicone like polymethylcetyl dimethyl methylsiloxane oxyethylene, or the mixture CETYL PEG / PPG-10 / 1 DIMETHICONE.

[0530] We can cite PEG-silicone such as polymethylcetyl dimethyl methylsiloxane oxyethylene, or the mixture CETYL PEG / PPG-10 / 1 DIMETHICONE sold for example by the company EVONIK GOLDSCHMIDT under the name AB IL EM 90.

[0531] The surfactant(s) represent(s) in total particularly from 0.01% to 30% by weight relative to the total weight of the composition, preferably from 0.5% to 15% by weight and even more preferably from 1% to 10% by weight, better still between 1% and 5% by weight of the composition. Water

[0532] According to a particular embodiment of the invention, the composition C1 comprises e) water.

[0533] According to a particular embodiment, the composition Cl or Cl' contains e) water, d) optionally one or more surfactants as defined previously and c) less than 10% by weight of fatty substances relative to the total weight of the composition, preferably less than 5% by weight of fatty substances, more preferably less than 2% by weight of fatty substances and even more preferably said composition Cl is free of fatty substances c).

[0534] The water suitable for the invention may be tap water, distilled water, spring water, floral water, such as cornflower water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and / or thermal water.

[0535] According to one embodiment, the composition Clou Cl' of the invention comprises e) water and at least one fatty substance c), in particular in a ratio between the mass of water and the mass of fatty substance c) of less than 1, preferably less than 0.9, more preferably less than 0.9 such as between 0.5 and 0.8.

[0536] According to another preferred embodiment of the invention, the composition Cl or Cl' comprises mainly water by weight vs. the quantity of fatty substances.

[0537] Form of the composition:

[0538] According to one embodiment of the invention, the composition comprises an aqueous phase. The composition is in particular formulated as aqueous lotions or as water-in-oil, oil-in-water emulsions, or as a multiple emulsion (triple oil-in-water-in-oil or water-in-oil-in-water emulsion (such emulsions are known and described for example by C. FOX in “Cosmetics and Toiletries” - November 1986 - Vol 101 - pages 101-112).

[0539] According to a particular embodiment of the invention, the composition is a direct emulsion, i.e. of the oil-in-water or Oil-in-water O / W type. The quantity of oil by weight is preferably less than 40% in the inverse emulsion, preferably less than or equal to 35%, more particularly less than or equal to 30% by weight relative to the total weight of the composition.

[0540] More particularly in the direct emulsion the quantity of water is greater than or equal to 40% by weight relative to the total weight of the composition, more particularly greater than or equal to 45%, preferably greater than or equal to 50%.

[0541] According to another particular embodiment of the invention, the composition of the invention is an inverse emulsion, i.e. of the water-in-oil or water-in-oil W / O type. The quantity of oil by weight is preferably greater than 30% in the inverse emulsion, preferably greater than 40%, more preferably greater than or equal to 45% by weight relative to the total weight of the composition. More particularly, in the inverse emulsion, the quantity of water is less than 40% by weight relative to the total weight of the composition, preferably less than or equal to 35% by weight.

[0542] The composition according to the invention preferably has a pH ranging from 3 to 9 depending on the support chosen.

[0543] According to a particular embodiment of the invention, the pH of the composition(s) is neutral or even slightly acidic. Preferably, the pH of the composition is between 6 and 7. The pH of these compositions can be adjusted to the desired value using acidifying or alkalizing agents usually used in cosmetics or even using conventional buffer systems.

[0544] By "alkalizing agent" or "base" is meant an agent for increasing the pH of the composition in which it is found. The alkalizing agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic. In particular, said agent is chosen from a) ammonia, b) (bi)carbonate, c) alkanolamines such as mono-, di- and triethanolamines and their derivatives, d) oxyethylenated and / or oxypropylenated ethylenediamines, e) organic amines, f) mineral or organic hydroxides, g) alkali metal silicates such as sodium metasilicates, h) preferably basic amino acids such as arginine, lysine, omithine, citruline and histidine, and i) compounds of the following formula (F):

[0545] [Chem. 23]:

[0546]

[0547] Formula (F) in which: - W is a divalent C1-C6 alkylene radical optionally substituted by one or more hydroxyl groups or a C1-C6 alkyl radical, 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, identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl radical.

[0548] Examples of amines of formula (F) include 1,3 diaminopropane, 1,3 diamino 2-propanol, spermine, spermidine.

[0549] By "alkanolamine" is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched CrC8 alkyl groups carrying one or more hydroxyl radicals.

[0550] Among the inorganic or organic hydroxides, mention may be made of those chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline earth metal, such as sodium or potassium hydroxides, c) hydroxides of a transition metal, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide. Inorganic or organic hydroxides a) and b) are preferred.

[0551] Among the acidifying agents of the compositions used in the invention, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

[0552] The alkalizing agents and the acidifying agents as defined above preferably represent from 0.001% to 20% by weight of the weight of the composition containing them. More particularly from 0.005% to 8% by weight of the composition.

[0553] According to a particular embodiment of the invention, the composition comprises a quantity of water less than or equal to 10% by weight relative to the total weight of the composition.

[0554] Advantageously, the composition according to the invention comprises a physiologically acceptable medium. In particular, the composition is a cosmetic composition.

[0555] By physiologically acceptable medium is meant a medium compatible with the keratin materials of human beings, such as for example the skin, lips, nails, eyelashes, eyebrows, hair.

[0556] By cosmetic composition is meant a composition compatible with keratin materials, which has a pleasant color, odor and feel, and which does not generate unacceptable discomfort (tingling, tightness, etc.), likely to put the consumer off it.

[0557] Keratin materials are understood to mean the skin (body, face, eye contour, scalp), hair, eyelashes, eyebrows, body hair, nails, lips.

[0558] The composition Cl according to the invention may comprise one or more cosmetic additives chosen from perfumes, preservatives, fillers, coloring agents, UV filters, oils other than fatty substances c), moisturizers, vitamins, ceramides, antioxidants, anti-free radical agents, polymers other than a), thickeners, trace elements, softeners, sequestrants, anti-hair loss agents, anti-dandruff agents, propellants.In particular, the composition according to the invention further comprises one or more coloring agents chosen from pigments, direct dyes and mixtures thereof, preferably pigments; more preferably the pigment(s) of the invention are chosen from carbon black, iron oxides, in particular black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet pigments such as BLUE 1 LAKE, azo pigments, in particular red pigments, such as D&C RED 7, alkali metal salt of lithol red, such as the calcium salt of lithol red B, even more preferably red iron oxides.

[0559] Advantageously, the composition according to the invention is a makeup composition, in particular a composition for lip makeup, mascara, eyeliner, eyeshadow, or foundation.

[0560] Additional solvents

[0561] According to a particular embodiment of the invention, the composition comprises one or more solvents, preferably polar and / or protic, other than water. Preferably, these polar and / or protic solvents are chosen from monoalcohols having from 2 to 6 carbon atoms such as ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, preferably n-butanol or ethanol, even more preferably ethanol.

[0562] According to one embodiment, the composition of the invention comprises one or more additional solvents, preferably chosen from monoalcohols having from 2 to 6 carbon atoms such as ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, preferably n-butanol or ethanol, even more preferably ethanol, in an amount of less than 70%, more preferably less than 20%, even more preferably less than 10%, more particularly less than 8% relative to the total weight of fatty substances c) and water e).

[0563] Adjuvants

[0564] The composition according to the invention may further comprise one or more fillers, in particular in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 20% by weight. By fillers, it is necessary to understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition whatever the temperature at which the composition is manufactured. These fillers are used in particular to modify the rheology or texture of the composition.

[0565] The composition according to the invention may be in the form of an aqueous composition, a water-in-oil emulsion or an oil-in-water emulsion,

[0566] According to a particular form of the invention, the composition C1 comprises a) one or more polyhydroxyalkanoate (PHA) copolymer(s) as defined above; and b) one or more polyurethane polymer latexes; and c) one or more fatty substances preferably liquid at 25°C and at atmospheric pressure; and f) optionally one or more polar and / or protic solvents chosen from monoalcohols having from 2 to 6 carbon atoms such as ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, preferably n-butanol or ethanol, even more preferably ethanol.

[0567] The invention is illustrated in more detail in the following examples. The amounts are indicated as a percentage by weight. Examples

[0568] The PHAs presented in the different examples were prepared in 3-liter chemostats and / or 5-liter Fernbachs flasks depending on whether or not an inhibitor of the [3-oxidation pathway was used. The isolation of the PHAs is similar for all the examples obtained.

[0569] In a first step, the microorganism generates PHAs which are stored in intracellular granules whose proportion varies depending on the conditions applied such as the temperature or the nature of the culture medium. The generation of PHA granules may or may not be associated with the growth of the microorganism depending on the nature of the microorganisms. In the second step, the biomass containing the PHAs is isolated, i.e. separated from the fermentation medium, and then dried. The PHAs are extracted from the biomass before being purified if necessary.

[0570] A mixture of saturated and unsaturated carbon sources is, for certain examples, necessary for the stability of the resulting PHA.

[0571] [Tables2] S-cs-srce of carbon CAS Assis capsy [RA-D j.£ S 24-07-2 Assis csriansspùe .-.-A ô o Aesde ündêcylèraque HC --U^seoesssoi s asidï

[0572] [Tables3] Source □ s csrbcne Genus and species Provenance mixed assde cspçyli décylè nique pUtidS: ATCC® 47054 ™ à & ü- ja ¢0 (P sside rwnsn niqsse s^ue et: putida ATCC® 47054 Example 1: PHA with side chain R 1 representing a 10% linear unsaturated n-octalenyl group and R2 representing an n-pentyl group

[0573] [Chem. 24]:

[0574]

[0575] The method for synthesizing the compound of Example 1 is adapted from the article: Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440, Z. Sun, JA Ramsay, M. Guay, BA Ramsay, Applied Microbiololy Biotechnology, 82. 657-662. 2009.

[0576] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054™. The culture method is carried out under axenic conditions in discontinuous growth supplied with a maintenance solution containing a mixture of carbon sources at a rate of p=0.15h 1 in a 3L chemostat containing 2.5L of culture medium.

[0577] The system is aerated at an air flow rate of 0.5 vvm for a dissolved oxygen (DO) setpoint at 30% of saturation. The pH is regulated with a 15% ammonia solution. The temperature of the fermentation medium is regulated at 30°C.

[0578] Assembly of the fed discontinuous growth fermentation mode:

[0579] The fermentation medium is regulated in temperature-dissolved oxygen pressure and pH (not shown) See [Fig.l] in appendix.

[0580] The production process is carried out using three separate culture media. The first culture medium defined as MCI “inoculum” is used for the preparation of the preculture. The second culture medium defined as MC2 “bach” is used for the non-fed discontinuous growth of the microorganism with the primary carbon sources in Fernbachs flasks. The third culture medium defined as MC3 “maintenance” is used for the discontinuous feeding, or maintenance, of fermentation with the carbon sources of interest at a flow rate calibrated according to the growth of the microorganism.

[0581] [Tables4] Ingrecients in by * rêoCU&îTï Æ L1C2 A&sfcÊLs MC3 4.7 12 § 2 7 2e£k3 ^SO4; W3 QS LOS 3 / ■■ Aæde caps^Fq^e? 0.8 BW. Acid 0.1 100 ScMm MiSTGefesenSs >■ 10 Assde r: NaOH 2N Eay QSF 1000 g

[0582] The composition of Nutrient Broth in mass percentage is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCO™.

[0583] [Tables5] ingredients in g

[0584] 100 mL of preculture is prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of “inoculum” culture media at pH adjusted to 6.8 with 2N NaOH in a 250 ml fembach flask then incubate at 30°C at 150 rpm for 24 hours. 1.9 L of MC2 “BATCH” culture medium placed in a previously sterilized 3 L chemostat are inoculated at OD = 0.1 with the 100 ml of preculture. After 4 hours at 30 °C at 850 rpm.

[0585] At the end of the introduction, the biomass is isolated by centrifugation and then washed three times with water. The biomass is dried by lyophilization before being extracted with ethyl acetate for 24 h. The suspension is clarified by filtration on a GF / A filter (Wattman®) the filtrate, composed of PHA in solution in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40°C until constant mass.

[0586] The PHA can optionally be purified by solubilization and successive precipitations in an ethyl acetate / Ethanol 70% methanol system for example.

[0587] The PHA has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure.

[0588] Preparation of Example 1': PHA copolymer with side chain R 1 representing a 5% unsaturated n-octalenyl group and R2 representing an n-hexyl group

[0589] [Chem. 25]:

[0590]

[0591] The copolymer of Example 1' (5% unsaturation and R2 chain representing n-hexyl) was prepared according to the procedure described for Example 1, with the same composition of the microelement solution as that described in Example 1 and with the following culture medium compositions: [Tableauxô] Ingredients in grams per liter MCI "inoculum" MC2 "batch" MC3 "maintenance" (NH4)2SO4 4.7 4.7 Na2HPO4 ; 7H2O 12 9 KH2PO4 2.7 2.03 MgSO4 ; 7H2O 0.8 1.03 Nutrient Broth 3 / Nonanoic acid / 0.95 950 Undecylenic acid 0.05 50 Microelement solution / 10 NaOH 2N QSP pH=6.8 Water milliQ QSP 1000 g The PHA copolymer of Example 1' has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure, with an unsaturation level of 5%.

[0592] Example 1”: PHA copolymer with side chain R 1 representing a 10% linear unsaturated n-octalenyl group and R2 representing an n-hexyl group

[0593] The copolymer of Example 1” (with 10% unsaturation and R2 chain representing n-hexyl) was prepared according to the procedure described for Example 1, with the same composition of the microelement solution as that described in Example 1 and with the following culture medium compositions: [Tables?] Ingredients In grams per liter MCI "inoculum" MC2 "batch" MC3 "maintenance" (NH4)2SO4 4.7 4.7 / Na2HPO4; 7H2O 12 9 / KH2PO4 2.7 2.03 / MgSO4; 7H2O 0.8 1.03 / Nutrient Broth 3 / / Nonanoic acid / 0.90 900 Undecylenic acid / 0.1 100 Microelement solution / 10 / NaOH 2N QSP pH=6.8 Water milliQ QSP 1000 g PHA has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure.

[0594] Example 1”': PHA copolymer with side chain R 1 representing a 30% linear unsaturated n-octalenyl group and R2 representing an n-pentyl group

[0595] The copolymer of Example 1'” (with 30% unsaturation and R2 chain representing n-pentyl) was prepared according to the procedure described for Example 1, with the same composition of the microelement solution as that described in Example 1 and with the following culture medium compositions: [Tables 8] Ingredients In grams per liter MCI "inoculum" MC2 "batch" MC3 "maintenance" (NH4)2SO4 4.7 4.7 / Na2HPO4; 7H2O 12 9 / KH2PO4 2.7 2.03 / MgSO4; 7H2O 0.8 1.03 / Nutrient Broth 3 / / Octanoic acid / 0.70 700 Undecylenic acid / 0.3 300 Microelement Solution / 10 / NaOH 2N QSP pH=6.8

[0596]

[0597]

[0598] MilliQ QSP Water 1000g The PHA copolymer has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Example 2: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted 100% with thiolactic acid (Compound of Example 1 grafted with thiolactic acid TLA): [Chem. 26]:

[0599]

[0600]

[0601]

[0602]

[0603]

[0604] 1 g of compound of Example 1 and 150 mg of thiolactic acid were solubilized in 20 mL of ethyl acetate at room temperature with stirring. 20 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) were added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes. 20 mL of the reaction medium was then precipitated in a 200 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film. The grafted PHA of Example 2 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. Example 3: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted 100% with octanethiol (Compound of Example 1 grafted with n-octanthiol) [Chem. 27]:

[0605] 0.5 g of compound of Example 1 and 125 mg of octanethiol were solubilized in 10 mL of ethyl acetate at room temperature with stirring. 15 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes.

[0606] The reaction medium was then precipitated in a 100 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0607] The grafted PHA of Example 3 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure.

[0608] Example 4: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 75% with 8-mercapto-l-octanol (Compound of Example 1 grafted with 8-mercapto-1-octanol)

[0609] [Chem. 28]:

[0610]

[0611] 50 mg of compound of Example 1 and 10 mg of 8-mercapto-l-octanol were solubilized in 5 mL of ethyl acetate at room temperature with stirring. 2 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes.

[0612] The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0613] The grafted PHA of Example 4 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. Grafting at 75% or 7.5% total function.

[0614] Example 5: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 32% with cysteamine (Compound of Example 1 grafted with cysteamine)

[0615] [Chem. 29]:

[0616]

[0617] 0.5 g of compound of Example 1 and 54 mg of cysteamine were solubilized in a mixture of 10 mL of dichloromethane and 2 mL of ethanol at room temperature with stirring. 10 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes.

[0618] The reaction medium was then precipitated in a 100 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0619] The grafted PHA of Example 5 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. Grafting at 32% or 3.2% total function.

[0620] Example 6: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 73% with cyclohexanethiol (CHT) (Compound of Example 1 grafted CHT)

[0621] [Chem. 30]:

[0622]

[0623]

[0624]

[0625]

[0626]

[0627]

[0628] 100 mg of compound of Example 1 and 26 mg of cyclohexanethiol were solubilized in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) were added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes. The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film. The grafted PHA of Example 6 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 73% grafting or 7.3% total function. Example 7: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 66% with 2-furanmethanethiol (FT) (Compound of Example 1 grafted FT) [Chem. 31]:

[0629] 100 mg of compound of Example 1 and 26 mg of 2-furanmethanethiol were solubilized in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) were added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes.

[0630]

[0631]

[0632]

[0633]

[0634] The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film. The grafted PHA of Example 7 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 66% grafting or 6.6% total function. Example 8: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 70% with 1-Thio-^-D-glucose tetraacetate (Compound of Example 1 grafted TGT) [Chem. 32]:

[0635]

[0636]

[0637]

[0638]

[0639]

[0640] 100 mg of compound of Example 1 and 26 mg of l-Thio-[3-D-glucose tetraacetate] were solubilized in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2-dimethoxy-2-Phenylacetophenone (IRGACURE 651) were added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes. The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film. The grafted PHA of Example 8 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 70% grafting or 7% total function. Example 9: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 50% with 2-phenylethanthiol (PT) (Compound of Example 1 grafted PT) [Chem. 33]:

[0641] 100 mg of compound of Example 1 and 26 mg of 2-phenylethanthiol were solubilized in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365 nm (reference) and stirred for at least 10 minutes.

[0642] The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0643] The grafted PHA of Example 9 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. Grafting at 50% or 5% total function.

[0644] Example 10: Poly(3-HydroxyOctanoate-co-Undecenoate) 10% unsaturations grafted at 64% with 4-tert-Butylbenzyl mercaptan (TBM) (Compound of Example 1 grafted TBM)

[0645] [Chem. 34]:

[0646]

[0647] 100 mg of compound of Example 1 and 26 mg of 4-tert-Butylbenzyl mercaptan have were solubilized in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365nm (reference) and stirred for at least 10 minutes.

[0648] The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0649] The grafted PHA of Example 10 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. 64% grafting or 6.4% total function.

[0650] Example 11: Poly(3-HydroxyNonanoate-co-Undecenoate) with 10% unsaturations grafted at 100% with thiolactic acid

[0651] [Chem. 35]:

[0652]

[0653] 0.1 g of compound of Example 1” and 15 mg of thiolactic acid were solubilized in 5 mL of chloroform at room temperature with stirring. 5 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365nm (reference) and stirred for at least 10 minutes.

[0654] The reaction medium was then precipitated in a 50 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0655] The grafted PHA of Example 11 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. 100% grafting.

[0656] Example 12: Poly(3-HydroxyNonanoate-co-Undecenoate) 5% unsaturations grafted at 100% with octanethiol

[0657] [Chem. 36]:

[0658]

[0659] 1 g of PHA copolymer of Example 1' and 150 mg of octanethiol were solubilized in 15 mL of ethyl acetate at room temperature with stirring. 20 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) was added to the mixture. The medium was then irradiated under a 100W UV lamp at 365nm (reference) and stirred for at least 10 minutes.

[0660] The reaction medium was then precipitated in a 500 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0661] The grafted PHA of Example 12 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. 100% grafting.

[0662] Example 13: Poly(3-HydroxyNonanoate-co-Undecenoate} 5% unsaturations 100% epoxidized

[0663] [Chem. 37]:

[0664]

[0665] 20 g of PHA copolymer of Example 1' are solubilized in 80 mL of anhydrous dichloromethane. A suspension of 1.9 g of m-CPBA 77% is prepared with 20 mL of anhydrous dichloromethane and added to the mixture with stirring, at room temperature for at least 120 hours.

[0666] The reaction medium was then precipitated in a 500 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0667] The PHA of Example 13 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 100% epoxidation.

[0668] Example 14: Poly(3-HydroxyNonanoate-co-Undecenoate) 10% unsaturations epoxidized to 100%

[0669] [Chem. 3 8]

[0670] 10 g of PHA copolymer of Example 1” (unsaturation level of 10)% are solubilized in 40 mL of anhydrous dichloromethane. A suspension of 1.9 g of m-CPBA 77% is prepared with 10 mL of anhydrous dichloromethane and added to the mixture with stirring, at room temperature for at least 120 hours.

[0671] The reaction medium was then precipitated in a 500 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0672] The PHA of Example 14 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 100% epoxidation.

[0673] Example 15: Poly(3-HydroxyOctanoate-co-Undecenoate) 30% unsaturations epoxidized to 100%

[0675] 10 g of PHA copolymer of Example 1”' (unsaturation level of 30%) are solubilized in 40 mL of anhydrous dichloromethane. A suspension of 6.2 g of m-CPBA 77% is prepared with 10 mL of anhydrous dichloromethane and added to the mixture with stirring, at room temperature for at least 120 hours.

[0676] The reaction medium was then precipitated in a 250 mL ethanol / water 70 / 30 vv mixture. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40°C, to obtain a homogeneous film.

[0677] The PHA of Example 15 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 100% epoxidation.

[0678] Example 16: Poly(3-HydroxyNonanoate-co-Undecenoate) 5% unsaturations grafted at 100% with 4-tert-Butylbenzyl mercaptan (TBM) (Compound of Example 1 'grafted TBM)

[0679] [Chem. 40]:

[0680]

[0681] 2 g of PHA copolymer of Example 1' and 300 mg of 4-tert-butylbenzylmercap tan were solubilized in 25 mL of ethyl acetate at room temperature with stirring. 25 mg of 2,2-Dimethoxy-2-Phenylacetophenone (IRGACURE 651) were added to the mixture. The medium was then irradiated under a 100W UV lamp at 365nm (reference) and stirred for at least 10 minutes.

[0682] The reaction medium was then precipitated in a 500 mL mixture of ethanol / water 70 / 30 vv. A viscous white precipitate was obtained. This step can be repeated. The product thus obtained is solubilized in a minimum of ethyl acetate, poured onto a Teflon plate, then dried under dynamic vacuum at 40 °C, to obtain a homogeneous film.

[0683] The PHA of Example 16 has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure. 100% grafting.

[0684] Example 17: PHA copolymer with side chain R 1 representing an isohexylenyl group and R2 representing an isobutyl group

[0685] [Chem. 41]:

[0686]

[0687] The method for obtaining Example 17 is an adaptation of Applied and Environmental Microbiology, Vol 60, No. 9. 3245-3254 (1994) “Polyester Biosynthesis Characteristics of Pseudomonas citronellolis Grown on Varions Carbon Sources, Including 3-Methyl-Branched Substrate”. MUN HWAN CHOI and SUNG CHUL YOON. The microorganism used is Pseudomonas citronellolis ATCC® 13674™. The culture method is carried out under axenic conditions in non-fed batch culture in 5L Fernbachs flasks (Corning® ref. 431685) containing 2 of culture medium, shaken at 1 lOrpm at 30°C in an orbital incubator (orbit diameter of 2.5cm).

[0688] The production process is carried out using two separate culture media. The first culture medium defined as MCI “inoculum” is used for the preparation of the preculture. The second culture medium defined as MC2 “bach” is used for the growth in non-fed discontinuous culture of the microorganism with the carbon source of interest in Fernbachs flasks.

[0689] [Tables9] îngrèdi'erits gram by air MCI “incQjhinn” Ô R cr co r 33^3 0^; 7HgQ 73 KHSFQ4 F1 NaHCQ? 0 3 GsGL:; 2HsO MgSC4 7HgQ' P kj œ 1.03 Ctamélld 5.5 broth L5 The composition of Nutrient Broth in mass percentage is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCO™ BD.

[0690] The composition of the yeast extract in mass percentage is 100% autolysate of the yeast Saccharomyces cerevisiae. Reference 210933 DIFCO™ BD.

[0691] [TableauxlO] idiots gram p aH Qïsan^é FeSQ^- r HgG ÎKS IR OI or Q KTj □ 3.0 9 ZtiSQrWgO 0.5&g 3.86 g HÆOs 0.5 g 5.82 g >3.88 g NsQb-SHsQ &.04 gni? th g cji S 0.34 g HC< 0.5N QSF 1800 g; 100 mL of preculture are prepared by suspending a cryotube containing 1 1 / 2 mL of the strain with 100 mL of “inoculum” culture media at pH adjusted to 6.8 with 2N NaOH in a 250 mL Fernbach flask and then incubating at 30°C at 150 rpm for 24 h. 1.9 L of MC2 “BATCH” culture medium placed in a previously sterilized 5 L Fernbach flask are inoculated at OD=0.1 with 100 mL of inoculum.

[0692] After 70 hours at 30°C at 1 lOrpm, the biomass is dried by freeze-drying before being extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF / A filter (Wattman®). The filtrate, composed of PHA in solution in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass.

[0693] The PHA can optionally be purified by solubilization and successive precipitations such as a dichloromethane methanol system for example.

[0694] The PHA copolymer of Example 3 has been fully characterized by spectroscopic and spectrometric method and conforms to the expected chemical structure with: 68 mol% of unit (A) of which R1 = isohexylenyl and 32 mol% of unit (B) of which R2 = isobutyl.

[0695] Example 18: PHA copolymer with side chain R 1 representing an isohexyl group and R2 representing an isobutyl group

[0696] [Chem. 42]:

[0697]

[0698] Example 18 is obtained by hydrogenation of the PHA copolymer of Example 17 via a continuous H-Cube Midi® hydrogenator from ThalesNanotechnologie.

[0699] A solution of 2 g (8.83 millimoles) of PHA from Example 17 is prepared with a mixture composed of 100 ml of ethyl acetate (SIGMA ALDRICH - CAS: 141-78-6) and 100 ml of methanol (SIGMA ALDRICH - CAS: 67-56-1) is introduced at a flow rate of 3 ml per minute into a hydrogenation cartridge containing the 5% palladium on carbon catalyst (MidiCard ref DHS 2141; Thalesnano technologie) maintained at 100°C under a pressure of 80 bars in the presence of hydrogen within the H-Cube Midi® ThalesNanotechnologie system. The reduction of the double bond is monitored by NMR. After 6 consecutive reduction cycles, the solution is concentrated by evaporation and then dried under vacuum to constant mass.

[0700] The PHA can optionally be purified by solubilization and successive precipitations such as a dichloromethane methanol system for example.

[0701] The PHA copolymer of Example 18 has been fully characterized by spectroscopic and spectrometric method and conforms to the expected chemical structure with: 68 mol% of unit (A) of which R1 = isohexyl 32 mol% of unit (B) of which R2 = isobutyl Example 19#:

[0702] A polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC 47054™, octanoic acid.

[0703] The culture mode was carried out under axenic batch conditions in 5 L Fernbachs flasks (Corning® ref. 431685) containing 2 L of culture medium, shaken at 110 rpm at 30°C in an orbital incubator (orbit diameter of 2.5 cm). The synthesis process was carried out using two separate culture media. The first culture medium defined MCI “inoculum” was used for the preparation of the inoculum. The second culture medium defined MC2 “batch” was used for the unfed discontinuous growth of the microorganism with octanoic acid in the Fernbachs flasks.

[0704] The composition in grams per liter of the two media is described in Table 11 below:

[0705] [Tableauxll] MCI « inoculum » MC2 « batch » 4.7 5.02 NaaHPOs : ?fLO 12 2.24 KH2PO4 2.7 0.5 Glucose 9 3.9 M0SO4 ; 7HzO 0.8 1.03 Citric acid 1.6 1.03 Btet MW) ; Ajide g&aoqlayg. 3.8 Solution Trace elements (2) 1.4 as D pH=S.8 Water QSPW€O g (2) The composition of the trace element solution in grams per liter is shown in Table 12 below:

[0706] [Table2] FeSO4.7H20 10.0g CaCb.2HsO 3.0 g ZnSO^.ÎHaQ 2.2 g 0..5 g HsBOa 0 3g CdCb.BHbO 02g NasMoOÆ HîO 0.15 g NsCLBHsO 0.002 g CuSO4. 1000 g 100 ml of inoculum were prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of culture media "inoculum" at pH adjusted to 6.8 with 2N NaOH in a 250 ml fembach flask and then incubated at 30°C at 150 rpm for 24 h. 1.9 l of MC2 "BATCH" culture medium placed in a 5 l fembach flask previously sterilized were inoculated at OD = 0.1 with 100 ml of inoculum. After 70 hours at 30°C at 110 rpm, the biomass was dried by lyophilization before being extracted with dichloromethane for 24 h. The suspension was clarified by filtration on a GF / A filter (Wattman®) the filtrate, containing the copolymer in solution in dichloromethane was concentrated by evaporation then dried under high vacuum at 40°C until constant mass. The crude polyhydroxyalkanoate was purified by precipitation of a solution of the latter in solution in 10 times its weight of dichloromethane, in 10 volumes of the cold methanol solution.The obtained solid was dried under high vacuum at 40°C until constant mass. The molecular weight of the obtained polyhydroxyalkanoate was characterized by size exclusion chromatography, detection Refractive index

[0707] ■ Eluent: THF

[0708] ■ Analytical flow rate: 1 mL / min ■ Injection: 100 pL ■ Columns: 1 Agilent PLGel Mixed-D 5pm column; 300 x 7.5mm; 1 Agilent PLGel Mixed-C 5pm column; 300 x 7.5mm; 1 Agilent Oligopore column; 300 x 7.5mm ■ at room temperature (25°C) ■ Detection: Waters 2487 Dual 1 Absorbance Detector, Waters 2414 Refractive

[0709] ■ Index Detector ■ Integrator: refractive index at 45°C and 64mV ■ Empower (GPC Module Relative / conventional Molar Mass)

[0710] ■ Empower injection duration 40 min ■ Standards: High-mass polystyrene / EasiVial PS-H 4 mL from Agilent Technology Part No. PL2010-0200

[0711] The analysis allows to measure the weight average molecular weight (Mw in g / mol), the number average molecular weight (Mn in g / mol), the polydispersity index Ip (Mw / Mn) and the degree of polymerization DPn.

[0712] The monomeric composition of the obtained polyhydroxyalkanoate was defined by gas chromatography equipped with a flame ionization detector. Identification is carried out via the injection of commercial standards and the monomeric composition was determined by methanolysis and sylylation treatment. To determine the monomeric composition, 7 mg of the polyhydroxyalkanoate polymer was dissolved in 1.5 mL of chloroform and was methanolyzed in the presence of 1.5 mL of a MeOH / HCl solution (17 / 2, v / v) at 100°C for 4 h. The organic phase was then washed with 1 mL of water and then dried over MgSO4. The sylilation of the formed methyl esters was carried out by adding 100 qL of BSTFA (N,Obis(trimethylsilyl)trifluoroacetamide) and 100 qL of pyridine to the methylated sample. The solution was heated at 70°C for 1 h and then evaporated to dryness. The sample was then dissolved in 600 qL of dichloromethane and analyzed by chromatography under the following conditions:

[0713] ■ Hewlett Packard 6890 Series Device ■ Phenomenex ZB-5 HT stationary phase column (length: 30 m, diameter: 0.25 mm) ■ Temperature: isothermal 60°C to 300°C in 6 min (heating rate: 10°C / min) ■ Gas: Helium; flow rate: 0.8 ml / min ■ Injector: Temperature: 250°C; 50 ml / min ■ Flame ionization detector; Temperature: 300°C ■ Injection: Volume 1 ql A copolymer was thus obtained containing 91% by weight of poly(hydroxy-3-octanoate), 6% by weight of poly(hydroxy-3-hexanoate) and 3% by weight of poly(hydroxy-3-butanoate). ■ Mn = 68,100 g / mol ■ Mw = 149 100 g / mol ■ Ip = 2.2 ■ DPn = 531

[0714] Example 20: A polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™, octanoic acid and acrylic acid.

[0715] The culture mode was carried out under continuous axenic conditions at a dilution of D=0.25h-l in a 3 L chemostat containing 1.1 L of culture medium. The system was aerated with air at a flow of 3 vvm (vvm = volume of air per volume of fermentation medium per minute) for a dissolved oxygen (DO) setpoint at 30% of saturation.

[0716] The production process was carried out using three separate culture media. The first undefined culture medium (MCI) was used for the preparation of the inoculum. The second defined culture medium (MC2) was used for the unfed discontinuous growth of the microorganism in the fermenter. The third defined culture medium (MC3) was used for the feeding, or maintenance, of the continuous fermentation containing octanoic acid and acrylic acid (inhibitor of the [3-oxidation] pathway). The MCI and MC2 media are identical to those described in Example 1. The composition in grams per liter of the MC3 medium is described in Table 13 below:

[0717] [Tableauxl3] MC3 « s (NH^SO^ 5 02; 7HàO 2.24 KH2PO4 0.5 Glucose 3 MqSCU; 7H?O 1.03 MMeclmue 1.03 Nutrient Broth (1) ? 3.8 Solution (2) 1.4 0.2 M2N QSP pH-6.8 tau Qsy 1000 q 100 mL of inoculum was prepared by suspending a cryotube containing 1 mL of the strain with 100 mL of Nutrient Broth at pH 7.0 adjusted with 2N NaOH in a 250 mL Fernbach flask and then incubated at 30°C at 150 rpm for 24 h.

[0718] The fermenter containing 1 liter of MC2 culture medium at 30°C was inoculated at an optical density of 0.1 at 630 nm (OD630=0.1). The system was maintained at 30°C with stirring at 700 + / -200 rpm and cascade-regulated with oxygenation for Approximately 16 hours or until the microorganism reaches its growth plateau. The feeding of the fermenter with the MC3 medium was initiated when the microorganism reached its growth plateau, the withdrawal was carried out in order to keep the initial mass of fermentation medium. Once the equilibrium state was reached in continuous culture, a fraction of the withdrawal was centrifuged in order to separate the biomass from the fermentation medium. The biomass was dried by lyophilization, then extracted with dichloromethane for 24 h. The suspension obtained was clarified by filtration on a GF / A filter (Wattman®). The filtrate obtained, comprising the copolymer in solution in dichloromethane, was concentrated by evaporation and then dried under high vacuum at 40°C until constant mass. The crude polyhydroxyalkanoate was purified by precipitation of a solution of the latter in solution in 10 times its weight of dichloromethane, in 10 volumes of the cold methanol solution. The solid obtained was dried under high vacuum at 40°C until constant mass. A copolymer comprising 96% by weight of poly(hydroxy-3-octanoate), 3% by weight of poly(hydroxy-3-hexanoate) and 1% by weight of poly(hydroxy-3-butanoate) was thus obtained.

[0719] ■ Mn = 67,900 g / mol: ■ Mw = 142,000 g / mol: ■ Ip = 2,l: ■ DPn = 611

[0720] Example 21: PHA copolymer with side chain R1 representing an n-hexyl group and R2 representing an n-butyl group

[0721] [Chem. 43]:

[0722]

[0723] A polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™, nonanoic acid and acrylic acid.

[0724] The culture mode is carried out in continuous axenic conditions at a dilution of D=0.25h-l in a 3L chemostat containing 1.1L of culture medium. The system is aerated with air at a flow rate of 1 vvm for a dissolved oxygen (DO) setpoint at 30% of saturation.

[0725] The production process is carried out using three separate culture media. The first culture medium (MCI) is used for the preparation of the inoculum. The second culture medium (MC2) is used for the batch growth of the microorganism in the fermenter. The third culture medium (MC3) is used for the feeding, or maintenance, of the continuous fermentation containing the carbon source of interest and the inhibitor of the [3-oxidation pathway (acrylic acid). The composition in grams per liter of the three media MCI, MC2 and MC3 is described in Table 14 below: [Tables 14] ingredients in grams per liter MCI "inocuium" MC2 "batch" MC3 "continuous" (NH4>SO4) 4.7 5.02 5.02 N32HPO4 ; 7HzO 12 2.24 2.24 RH2PO4 2.7 0.5 0.5 Glucose 9 3.9 39 MgSO4 ; 7H2O 0.8 1.03 103 Citric acid 1.6 1.03 1.03 Nutrient Broth 1 / Nonanoic acid 3.8 Microelement solution 1.4 1.4 Acrylic acid 0.2 NaOH 2 N QSPpH=6.8 Water miliiQ QSP m=1000g The composition of Nutrient Broth in mass percentage is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCO™.

[0726] The composition of the microelement solution in grams per liter is described in Table 15 below. [Tables 15] FëSQ+jHsO WO g G3Q22H2O 3.0 g ZnSO4-7Hs0 2.2 g MnS04H20 Q! uo 0 HsBOs 0.3 g CoC^-6H2O 02 g 0.15 g NiCh-SFhO 0.02 g CüSO4-5HsO 1.00 g Water MàiliQ QSP 1000 g 100 mL of inoculum are prepared by suspending a cryotube containing 1 mL at OD=10 of the strain with 100 mL of MCI “inoculum” at pH previously adjusted to 7.0 with 2N NaOH in a 500 mL fembach then incubate at 30°C at 150 rpm for 24 hours.

[0727] The 3L fermenter containing 1 liter of MC2 “batch” culture medium at 30°C is inoculated at an optical density of 0.1 at 600nm (OD600=0.1). The system is maintained at 30°C with stirring of 700rpm + / -200rpm regulated in cascade with oxygenation for approximately 16 hours and / or until the microorganism can reach its growth plateau.

[0728] Feeding the fermenter with the “continuous” MC3 medium is started once the microorganism has reached its growth plateau, the withdrawal is carried out in order to keep the initial mass of fermentation medium. Once the equilibrium state is reached in continuous culture, a fraction of the withdrawal is centrifuged in order to separate the biomass from the fermentation medium. The biomass is dried by lyophilization before being extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF / A filter (Wattman®) the filtrate composed of PHA in solution in dichloromethane is concentrated by evaporation then dried under high vacuum at 40°C until constant mass. The molecular weight of the obtained polyhydroxyalkanoate was characterized by size exclusion chromatography, Refractive Index detection

[0729] ■ Eluent: THF

[0730] ■ Analytical flow rate: 1 mL / min ■ Injection: 100 pL ■ Columns: 1 Agilent PLGel Mixed-D 5qm column; 300 x 7.5 mm; 1 Agilent PLGel Mixed-C 5qm column; 300 x 7.5 mm; 1 Agilent Oligopore column; 300 x 7.5 mm ■ at room temperature (25°C) ■ Detection: Waters 2487 Dual 1 Absorbance Detector, Waters 2414 Refractive

[0731] ■ Index Detector ■ Integrator: refractive index at 45°C and 64mV ■ Empower (GPC Module Relative / conventional Molar Mass)

[0732] ■ Empower injection duration 40 min ■ Standards: High-mass polystyrene / EasiVial PS-H 4 mL from Agilent Technology Part No. PL2010-0200

[0733] ​​The analysis allows to measure the weight average molecular weight (Mw in g / mol), the number average molecular weight (Mn in g / mol), the polydispersity index Ip (Mw / Mn) and the degree of polymerization DPn.

[0734] The monomeric composition of the obtained polyhydroxyalkanoate was defined by gas chromatography equipped with a flame ionization detector. Identification is carried out via the injection of commercial standards and the monomeric composition was determined by methanolysis and sylylation treatment. To determine the monomeric composition, 7 mg of the polyhydroxyalkanoate polymer was dissolved in 1.5 mL of chloroform and was methanolyzed in the presence of 1.5 mL of a MeOH / HCl solution (17 / 2, v / v) at 100°C for 4 h. The organic phase was then washed with 1 mL of water and then dried over MgSO4. The sylilation of the formed methyl esters was carried out by adding 100 qL of BSTFA (N,Obis(trimethylsilyl)trifluoroacetamide) and 100 qL of pyridine to the methylated sample. The solution was heated at 70°C for 1 h and then evaporated to dryness. The sample was then dissolved in 600 qL of dichloromethane and analyzed by chromatography under the following conditions:

[0735] ■ Hewlett Packard 6890 Series Device ■ Phenomenex ZB-5 HT stationary phase column (length: 30 m, diameter: 0.25 mm) ■ Temperature: isothermal 60°C to 300°C in 6 min (heating rate: 10°C / min) ■ Gas: Helium; flow rate: 0.8 ml / min ■ Injector: Temperature: 250°C; 50 ml / min ■ Flame ionization detector; Temperature: 300°C ■ Injection: Volume 1 ql

[0736] A copolymer comprising 86% by weight of poly(hydroxy-3-nonanoate), 9% by weight of poly(hydroxy-3-heptanoate and 5% by weight of poly(hydroxy-3-pentanoate) was thus obtained.

[0737] ■ Mn = 65,900 g / mol

[0738] ■ Mw = 143,600 g / mol

[0739] ■ Ip = 2.2

[0740] ■ DPn = 531 Example 22#:

[0741] A polymer was prepared according to the procedure of Example 19 using nonanoic acid (instead of octanoic acid) and without acrylic acid. A copolymer comprising 68% by weight of poly(hydroxy-3-nonanoate), 27% by weight of poly(hydroxy-3-heptanoate) and 5% by weight of poly(hydroxy-3-pentanoate) was thus obtained. ■ Mn = 55,800 g / mol ■ Mw = 124,500 g / mol ■ Ip = 2.2 ■ DPn = 469 Example 23#:

[0742] A polymer was prepared according to the procedure of Example 19 using dodecanoic acid (instead of octanoic acid).

[0743] A copolymer comprising 44% by weight of poly(hydroxy-3-dodecanoate) and 38% by weight of poly(hydroxy-3-decanoate), and 18% by weight of poly(hydroxy-3-octanoate) was obtained.

[0744] ■ Mn = 67,400 g / mol ■ Mw = 129,800 g / mol ■ Ip= 1.9 ■ DPn = 484

[0745] Example 24\ PHA copolymer with side chain R1 representing an n-pentyl group and R2 representing an n-propyl group

[0746] [Chem. 44]:

[0747]

[0748] The method for obtaining example 24 is an adaptation of the article Biomacromolecules 2012, 13, 2926-2932: “Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer”

[0749] The microorganism used is Pseudomonas putida ATCC® 47054™

[0750] The culture mode is carried out in continuous axenic conditions at a dilution of D=0.25h 1 in a 3L chemostat containing 1.1L of culture medium.

[0751] The system is aerated with air at a flow rate of 3 vvm for a dissolved oxygen (DO) setpoint at 30% of saturation.

[0752] Assembly:

[0753] See [Fig.2]

[0754] The production process is carried out using three separate culture media

[0755] The first indefinite culture medium (ICM) is used for the preparation of the inoculum.

[0756] The second defined culture medium (MC2) is used for the batch growth of the microorganism in the fermenter.

[0757] The third defined culture medium (MC3) is used for feeding, or maintaining, the continuous fermentation containing the carbon source of interest and the inhibitor of the [3-oxidation] pathway.

[0758] The composition in grams per liter of the three media is described in Table 16. Composition in grams per liter of culture media for inoculum and maintenance.

[0759] [Tables 16] « irssouhm > » MQ3 « » 4.7 5.02 12 2.24 2 7*4 ^^04 ü 5 0.5 Gfeccse § MgSO4 ; 7H2Q 1.Ô3 .Acid LS LGS 1,CS Acid. octsndic 3.8 .Sely^in ^microelements^ts 1.4 1.4 The composition of Nutrient Broth in mass percentage is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCO™.

[0760] The composition of the microelement solution in grams per liter is described in Table 17 composition in grams per liter of the microelement solution

[0761] [Tablesl7] peS O 4 ■ 7 H 2 OPP GaŒ'2H2O g 7 « Æ n J, 7 U '7 n &taSO4-«2O PP sa H3B03 p P ÔcCMHZO 0.2 g? A:C? -, 34., 3: g HiŒ-OHSÜ OuSO4-5H2O Wg £so WiQ 100 mL of inoculum is prepared by suspending a cryotube containing 1 mL of the strain with 100 mL of Nutrient Broth at pH adjusted to 7.0 with 2N NaOH in a 250 mL fembach and then incubating at 30°C at 150 rpm for 24 hours.

[0762] The fermenter containing 1 liter of MC2 culture medium at 30°C is inoculated at an optical density of 0.1 at 630nm (OD630=0.1). The system is maintained at 30°C with stirring of 700rpm + / -200rpm regulated in cascade with oxygenation for approximately 16 hours and or until the microorganism can reach its growth plateau.

[0763] Feeding the fermenter with the MC3 medium is started once the microorganism has reached its growth plateau, the withdrawal is carried out in order to keep the initial mass of fermentation medium. Once the equilibrium state is reached in continuous culture, a fraction of the withdrawal is centrifuged in order to separate the biomass from the fermentation medium. The biomass is dried by lyophilization before being extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF / A filter (Wattman®) the filtrate, composed of PHA in solution in dichloromethane is concentrated by evaporation then dried under high vacuum at 40°C until constant mass.

[0764] The PHA can optionally be purified by solubilization and successive precipitations such as a dichloromethane methanol system for example.

[0765] The PHA copolymer of Example 24 was fully characterized by spectrometric and spectroscopic methods. By gas chromatography equipped with a detector FID it appears that the copolymer contains 96% of radical R1 = n-pentyl and 4% of radical R2 = n-propyl.

[0766] Example 25: PHA with side chain R 1 representing a 5% linear 8-bromo-n-octanoyl group and R2 representing an n-hexyl group

[0767] [Chem. 45]:

[0768]

[0769] The method for synthesizing the compound of Example 1 is adapted from the article: Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440, Z. Sun, JA Ramsay, M. Guay, BA Ramsay, Applied Microbiololy Biotechnology, 82. 657-662. 2009.

[0770] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054™. The culture method is carried out under axenic conditions in discontinuous growth supplied with a maintenance solution containing a mixture of carbon sources at a rate of p=0.15h-l in a 3L chemostat containing 2.5L of culture medium.

[0771] The system is aerated at an air flow rate of 0.5 vvm for a dissolved oxygen (DO) setpoint at 30% of saturation. The pH is regulated with a solution composed of ammonia and glucose at 15% and 40% final mass respectively. The temperature of the fermentation medium is regulated at 30°C.

[0772] Assembly of the fed discontinuous growth fermentation mode:

[0773] The fermentation medium is regulated in temperature-dissolved oxygen pressure and pH (not shown).

[0774] The production process is carried out using three separate culture media. The first culture medium defined as MCI “inoculum” is used for the preparation of the preculture. The second culture medium defined as MC2 “bach” is used for the non-fed discontinuous growth of the microorganism with the primary carbon sources in Fernbachs flasks. The third culture medium defined as MC3 “maintenance” is used for the discontinuous feeding, or maintenance, of the fermentation with the carbon sources of interest at a flow rate calibrated according to the growth of the microorganism.

[0775] [Table 18]: ingredients in qram^ne for frying mci as „„„„„«. ha f 4,7 MC3 ^Euntenertcs s. ; 7HgO 12 § KHaPOs 2,7 2..C3 hîgSQ^ ; 7HjÜ O i?? LS3 ^utrieni Broth 3 Aside nenSRsique t 1 Aosde 1 1 - ü TJ 10 MsOH 2M Eay milO QSP iœ$g

[0776] The composition of Nutrient Broth in mass percentage is 37.5% beef extract and 62.5% peptone. Reference 233000 DIFCO™.

[0777] [Table. 19]: Ingredients in grams per Sitra Quantity W,0 g 3.3 g 2.2 g 0.5 § H» 0.3 g QsŒï-SHæQ P is 03 0.15 gb cp ÇdS Q 4; 5 H sG Esu (su HCI G, 5Hj SS P WG g

[0778] 100 mL of preculture is prepared by suspending a cryotube containing 1 ml of the strain with 100 ml of “inoculum” culture media at pH adjusted to 6.8 with 2N NaOH in a 250 ml fembach flask then incubate at 30°C at 150 rpm for 24 hours. 1.9 L of MC2 “BATCH” culture medium placed in a previously sterilized 3 L chemostat are inoculated at OD = 0.1 with the 100 ml of preculture. After 4 hours at 30 °C at 850 rpm, the introduction of the maintenance is carried out by applying the flow rate defined by equation 1.

[0779] At the end of the introduction, the biomass is isolated by centrifugation and then washed three times with water. The biomass is dried by lyophilization before being extracted with ethyl acetate for 24 h. The suspension is clarified by filtration on a GF / A filter (Wattman®). The filtrate, composed of PHA in solution in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40°C until constant mass.

[0780] The PHA can optionally be purified by solubilization and successive precipitations in an ethyl acetate / Ethanol 70% methanol system for example.

[0781] The PHA has been fully characterized by spectroscopic and spectrometric methods and conforms to the expected chemical structure: 95 mol% of unit (B) of which R2 = n-hexyl (71%) and n-butyl (24%) and 5 mol% of unit (A) of which RI = 8-bromo-n-octanyl (5.9%) and 6-bromo-n-hexyl (0.2%).

[0782]

[0783] Examples 26 to 32: Compositions of association examples and evaluation.

[0784] Preparation of the compositions:

[0785] The compositions described in Tables 20 and 21 below were prepared according to the following protocol:

[0786] Fat phase A was made by mixing all the ingredients of phase A using a SpeedMixer DAC 150 from Speedmixer™ for 5 minutes at 3500 rpm.

[0787] In parallel, aqueous phase B was also produced by mixing all the ingredients of phase B using a speedmixer for 5 minutes at 3500 rpm.

[0788] The two phases once formed were mixed using a speedmixer for 5 minutes at 3500 rpm.

[0789] Stable emulsions were thus obtained. [Tables20] IlilO iOOOMli itiOii® Compound iiiitOili A isododecane 45 45 45 45 Polyhydroxyalcanoate according to exemption 21 10- 10 10 1 CETYL PEG / PPG-10 / 1 D1MEÎH1CONE (produced by Evonik under the trade name ABU EM S0) 4 4 4 4 POLŸGLYGERYL-4 ISOSTEARATE produced by Evonik under the trade name 1SOLAN Gl 34) 1 1 1 1 B Decontaminated water 20 10 - 20 Polyurethane 93 20 30 40 - Polyurethane 93 - ■- - 20 [Tables21] lilial (invention) A Isadodèçané 45 45 55 Polyhydroxyatcanoat e according to exemption 21 10 10 10 CETYL PEG / PPG-10 / 1 DIMETH ICONE by Evonik under the trade name AB IL EM 90) 4 4 4 POLYGLYGERYL-4 ISOSTEARATE by Evonik under the trade name ; SOL AN G134) 1 1 1 B. Deionized water 10 - 40 Polyurethane 93 - - - Polyurethane 99 30 40 - Composition evaluations:

[0790] A deposit of each composition 26 to 32 is made on a Byko Chart Lenata contrast card using a film puller and left to dry for 24 hours at 25°C and 45% relative humidity. The final thickness of the deposit is 30 pm.

[0791] Water resistance was assessed according to the following protocol:

[0792] On the 30pm dry deposit, the water sensitivity is evaluated after depositing 20pl of water on the surface of the deposit. The evaluations are made after 1h of contact between the water and the deposit. The level of water sensitivity is evaluated as follows: [Tables 22] Sensitivity level Appearance of the deposit 1- solubilized the deposit is solubilized and the support visible 2- sticky the deposit is present but sticky to the finger 3- marked the deposit is present and after wiping the drop of water, the imprint of the drop is visible 4 - not solubilized the deposit remained intact after wiping the drop of water Wear resistance was assessed according to the following protocol:

[0793] On the 30pm dry deposit, a hydrophilic steel ball is used as a wiper. The applied normal load or force is IN, the displacement speed is 50 mm.s *. On each film, tracks are defined on which the wiper makes multiple passes.

[0794] In the case of wear measurements, permanent contact is maintained during the back and forth movements of the ball on the deposit. The number of passes increases for each of the tracks. The wear resistance is quantified as corresponding to the minimum number of passes to completely wear out the deposit.

[0795] In the case of this study the number of passages per track are respectively 10, 30, 50, 100, 200 and 300 passages.

[0796] Each measurement was replicated 5 times.

[0797] The results of the wear resistance tests will be quantified as described in the table below: [Tables23] Wear Resistance Ratings 0-10 ball passes — 10-30 ball passes - 30-50 ball passes +

Claims

Claims

1. Composition, in particular cosmetic, comprising: a) one or more polyhydroxyalkanoate (PHA) copolymer(s) comprising at least two different repeating polymeric units chosen from the following units (A) and (B), as well as their optical, geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: -[-O-CH(R1)-CH2-C(O)-]- unit (A) -[-O-CH(R2)-CH2-C(O)-]- unit (B) polymeric units (A) and (B) in which: • R 1 represents a hydrocarbon chain, non-cyclic, saturated or unsaturated, linear or branched, or cyclic, saturated or unsaturated, aromatic or non-aromatic, comprising from 5 to 28 carbon atoms; preferably the hydrocarbon chain is chosen from i) (C5-C28)alkyl, linear or branched, ii) (C5-C28)alkenyl, linear or branched, iii) (C5-C28)alkynyl, linear or branched, preferably the hydrocarbon group is linear; said hydrocarbon chain being: • optionally substituted by one or more atoms or groups chosen from: a) halogen such as chlorine or bromine, b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide -C(O)-N(Ra)2 or -C(S)-N(Ra)2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active; 1) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, 6) cosmetic active, m) thiosulfate and X representing a') O, S, N(Ra) or Si(Rb)(Rc), b') S(O)r, or (thio)carbonyl, c') or combinations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide; R a representing a hydrogen atom, or a (Ci-C4)alkyl group, or aryl(Ci-C 4) alkyl such as benzyl, preferably Ra represents a hydrogen atom; R b and R c, identical or different, represent a (Ci-C4)alkyl or (CrC4)alkoxy group, particularly a single substituent; preferably chosen from b) halogen, and j) such as epoxide; and / or • optionally interrupted by one or more a') heteroatoms such as O, S, N(Ra), and Si(Rb)(Rc), b') S(O)r, (thio)carbonyl, c') or the associations of a') with b') such as (thio)ester, (thio)amide, (thio)urea, sulfonamide with r being 1 or 2, R a being as defined previously, preferably R a represents a hydrogen atom, R b and R c being as defined previously; • R 2 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated or unsaturated, comprising from 3 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular chosen from (C3-C28)alkyl, linear or branched, and (C3-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C4-C20)alkyl or (C4-C20)alkenyl, preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R 1 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R 1 from which two carbon atoms are subtracted; b) one or more polyurethane latexes; c) optionally one or more fatty substances; preferably liquid at 25°C and at atmospheric pressure; d) optionally one or more surfactants; and e) water, it being understood that: (A) is different from (B) and - preferably the composition comprises c) one or more fatty substances and d) one or more surfactants and e) water.

2. Composition according to claim 1, in which the PHA copolymer(s) a) comprising the repeating unit chosen from those of formula (I), as well as their optical, geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: Formula (I) in which: • R 1 and R 2 are as defined in claim 1; • m and n are integers greater than or equal to 1, preferably the sum n + m is inclusively between 450 and 1400; preferably m > n when R 1 and R 2 represent an unsubstituted and uninterrupted alkyl group - more preferably when R1 and R2 are linear alkyl then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted; and preferably m < n when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or interrupted alkenyl or optionally substituted and / or interrupted alkynyl, and R 2 represents an alkyl group.

3. Composition according to claim 1, in which the PHA copolymer(s) a) comprise three different repeating polymeric units (A), (B) and (C), preferably consisting of the following 3 different polymeric units (A), (B) and (C), as well as their optical and geometric isomers and their solvates such as hydrates: -[-O-CH(R1)-CH2-C(O)-]- unit (A) -[-O-CH(R2)-CH2-C(O)-]- unit (B) -[-O-CH(R3)-CH2-C(O)-]- unit (C) polymeric units (A), (B) and (C) in which: - R \ and R 2 are as defined in claim 1; - R 3 represents a hydrocarbon group, cyclic or non-cyclic, linear or branched, saturated or unsaturated, comprising from 1 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1 in claim 1; in particular represents a hydrocarbon group chosen from (C1-C28)alkyl, linear or branched, and (C2-C28)alkenyl, linear or branched, in particular a linear hydrocarbon group, more particularly (C4-C20)alkenyl, preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R1, or corresponding to the number of carbon atoms of the radical R1 from which at least three carbon atoms are subtracted, preferably corresponding to the number of carbon atoms of the radical R1 from which four carbon atoms are subtracted; and it being understood that: - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and preferably when R \ R 2 and R 2 represent an unsubstituted and uninterrupted alkyl group the molar percentage in unit (A) is greater than the molar percentage in unit (B), and greater than the molar percentage in unit (C) - more preferably when R1, R2 and R3 are linear alkyl, then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted, and R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 4 carbon atoms are subtracted, and preferably when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted alkenyl and / or optionally interrupted or optionally substituted and / or optionally interrupted alkynyl, then the molar percentage in unit (A) is lower than the molar percentage in unit (B) and the molar percentage in unit (C) in particular if R2 represents an alkyl group and / or R3 represents an alkyl group; more preferably the PHA copolymer(s) a) contain the repeating unit of formula (II), as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates:

4. (II) Formula (II) in which: • R1, R2 and R3 are as defined previously; • m, n and p, are integers greater than or equal to 1, of preferably the sum n + m + p is inclusively between 450 and 1400; preferably m > n + p when R \ R 2 and R 3 represent an unsubstituted and uninterrupted alkyl group - more preferably when R1, R2 and R3 are linear alkyl, then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 less 2 carbon atoms, and R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 less 4 carbon atoms; and preferably m < n + p when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, and R 2 and R 3 represent an alkyl group. Composition according to any one of the preceding claims, in which the PHA copolymer(s) a) contains(contain) four different repeating polymeric units (A), (B), (C), and (D) preferably consists of the following 4 different polymeric units (A), (B), (C), and (D), as well as their optical, geometric isomers and their acid or base salts, organic or inorganic, as well as their solvates such as hydrates: -[-O-CH(R1)-CH2-C(O)-]- unit (A) -[-O-CH(R2)-CH2-C(O)-]- unit (B) -[-O-CH(R3)-CH2-C(O)-]- unit (C) -[-O-CH(R4)-CH2-C(O)-]- unit (D) polymeric units (A), (B), (C) and (D) in which: R1, R2 and R3 are as defined in any one of claims 1 to 3; - R 4 represents a saturated, linear or branched, cyclic or non-cyclic hydrocarbon group comprising from 3 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1 in any one of the preceding claims; in particular represents a hydrocarbon group chosen from (C4-C28)alkyl, linear or branched optionally substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined for R1 as defined previously; and it being understood that: - (A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), and (C) is different from (A), (B) and (D); and (D) is different from (A), (B) and (C); - preferably when R \ R 2, R 3 and R 4 represent an unsubstituted and uninterrupted alkyl group the molar percentage in unit (A) is greater than the molar percentage in unit (B), greater than the molar percentage in unit (C), and greater than the molar percentage in unit (D) - more preferably when R1, R2, R3 and R4 are linear alkyl, then R1 is an alkyl group in C5-Ci3; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 2 carbon atoms, R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 4 carbon atoms, and R4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 6 carbon atoms, and - preferably when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, then the molar percentage in unit (A) is less than the molar percentage in unit (B), is less than the molar percentage in unit (B), and is less than the molar percentage in unit (C), in particular if R 2 represents an alkyl group and / or R 3 represents an alkyl group, and R 4 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl; more preferably the PHA copolymer(s) comprise the repeating unit of formula (III), as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates: (HD Formula (HD in which: • R1, R2, R', and R4 are as defined previously; • m, n, p, and v are integers greater than or equal to 1, preferably the sum n + m + p + v is inclusively between 450 and 1400; preferably when R \ R 2, R 3 and R 4 represent an unsubstituted and uninterrupted alkyl group then m>n + p + q- more preferably when R1, R2, R3 and R4 are linear alkyl, then R1 is a C5-Ci3 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted, R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 4 carbon atoms are subtracted, and R4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 6 carbon atoms are subtracted;and preferably when R 1 represents a substituted and / or uninterrupted alkyl group, optionally substituted and / or uninterrupted alkenyl or optionally substituted and / or uninterrupted alkynyl group, and R 2 and R 3 represent an alkyl group, and R 4 represents a substituted and / or uninterrupted alkyl group, optionally substituted and / or uninterrupted alkenyl or optionally substituted and / or uninterrupted alkynyl group then n > m + v; more preferably n + p > m + v.;

5. Composition according to any one of the preceding claims, wherein the PHA copolymer(s) a) contain five different repeating polymeric units (A), (B), (C), (D), and (E) preferably consists of the following 5 different polymeric units (A), (B), (C), (D), and (E), as well as their optical, geometric isomers and their organic or inorganic acid or base salts, as well as their solvates such as hydrates: -[-O-CH(R1)-CH2-C(O)-]- unit (A) -[-O-CH(R2)-CH2-C(O)-]- unit (B) -[-O-CH(R3)-CH2-C(O)-]- unit (C) -[-O-CH(R4)-CH2-C(O)-]- unit (D) -[-O-CH(R5)-CH2-C(O)-]- unit (E) polymeric units (A), (B), (C), (D) and (E) in which: - R \ R 2, R 3 and R4 are as defined in any one of the preceding claims; and - R 5 represents a saturated, linear or branched, cyclic or non-cyclic hydrocarbon group comprising from 3 to 30 carbon atoms optionally substituted by one or more atoms or groups a) to m) and / or optionally interrupted by one or more heteroatoms or groups a') to c') as defined for R1; in particular represents a hydrocarbon group chosen from (C4-C28)alkyl, linear or branched, substituted by one or more atoms or groups a) to l) and / or interrupted by one or more heteroatoms or groups a') to c') as defined for R1; preferably the hydrocarbon group has a number of carbons corresponding to the number of carbon atoms of the radical R4 from which at least one carbon atom is subtracted, preferably corresponding to the number of carbon atoms of the radical R4 from which at least 2 carbon atoms are subtracted, preferably from which 2 carbon atoms are subtracted; it being understood that: - (A) is different from (B), (C), (D) and (E); (B) is different of (A), (C), (D) and (E), and (C) is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E) is different from (A), (B), (C) and (D); - preferably when R \ R 2, R 3, R 4 and R 5 represent an unsubstituted and uninterrupted alkyl group the molar percentage in unit (A) is greater than the molar percentage in unit (B), greater than the molar percentage in unit (C), and greater than the molar percentage in unit (D), greater than the molar percentage in unit (E) - more preferably when R1, R2, R3, R4 and R5 are linear alkyl, then R1 is a C5-C13 alkyl group; and R2 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 2 carbon atoms are subtracted, R3 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 from which 4 carbon atoms are subtracted, R4 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 6 carbon atoms, and R5 represents a linear alkyl group with a carbon number corresponding to the carbon number of R1 minus 8 carbon atoms, and - preferably when R 1 represents a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl, then the molar percentage in unit (A) is less than the molar percentage in unit (B), is less than the molar percentage in unit (B), and is less than the molar percentage in unit (C), in particular if R 2 represents an alkyl group and / or R 3 represent an alkyl group, and R 4 and R 5 represent a substituted and / or interrupted alkyl group, optionally substituted and / or optionally interrupted alkenyl or optionally substituted and / or optionally interrupted alkynyl; more preferably the PHA copolymer(s) comprise the repeating unit of formula (IV), as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates: (IV) Formula (IV) in which: • R \ R 2, R 3, R 41 and R 5 are as defined previously; • m, n, p, v and z are integers greater than or equal to 1, preferably the sum n + m + p + v + z is between 450 and 1400 inclusive; • preferably when R \ R 2, R 3, R 4 and R 5 represent an unsubstituted and uninterrupted alkyl group then m > n + p + v + z; • preferably when R 1 represents a substituted and / or interrupted alkyl group; optionally alkenyl

6. substituted and / or optionally interrupted; or optionally substituted and / or optionally interrupted alkynyl, R 2 and R 3 represent an alkyl group and the groups R 4 and R 5 represent a substituted and / or interrupted alkyl group; optionally substituted and / or optionally interrupted alkenyl; or optionally substituted and / or optionally interrupted alkynyl, then n > m + v + z; more preferably n + p>m + v + z. Composition according to any one of the preceding claims, in which R 1 represents a linear or branched (C5-C2s)alkyl hydrocarbon chain, preferably linear, more particularly R 1 is an alkyl group substituted by one or more atoms or groups a) to k), said alkyl group comprising 5 to 12, preferably between 6 and 10 carbon atoms, more preferably between 7 and 9 carbon atoms such as n-octyl;preferably R 1 represents a hydrocarbon chain, substituted by one or more (preferably one) groups chosen from b) hydroxy, c) thiol, d) (di)(Ci-C4)(alkyl)amino preferably amino, e) carboxy, i) (hetero)cycloalkyl such as anhydride, or epoxide, j) cosmetic active agent chosen from colored or non-colored, fluorescent or non-fluorescent chromophores such as optical brighteners, UV filters, h) (hetero)aryl such as phenyl or furyl, k) RX with R representing a group chosen from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, 6) cosmetic active agent as defined above and X representing a') O, S, N(Ra), b') carbonyl, c') or their combinations of a') with b') such as ester, amide, urea; Ra representing a hydrogen atom, a (Ci-C4)alkyl group, or aryl(Ci-C4)alkyl such as benzyl, preferably Ra represents a hydrogen atom; even more preferably the PHA copolymer(s) are such that R 1 represents a hydrocarbon chain, in particular an alkyl group as defined above, which is substituted by one or more (preferably one) groups chosen from a) halogen such as chlorine or bromine, b) hydroxy, d) (di)(Ci-C4)(alkyl)amino preferably amino, e) carboxy, i) (hetero)cycloalkyl such as epoxide, h) (hetero)aryl such as phenyl or furyl, k) RX with R representing a group selected from a) cycloalkyl such as cyclohexyl, |3) heterocycloalkyl such as sugar, preferably monosaccharide such as glucose, y) (hetero)aryl such as phenyl, and X representing a') O, S, N(Ra) preferably S; R a representing a hydrogen atom, a (Ci-C4)alkyl group, preferably Ra represents a hydrogen atom; better said hydrocarbon chain R1 is substituted at the end of the chain on the opposite side of the carbon atom which carries said radical R1.

7. Composition according to any one of the preceding claims, in which R1 is of the following formula -(CH2)rX-(ALK)uG with X being as defined above, in particular representing O, S, N(Ra), preferably S, ALK represents a (Ci-Cio)alkylene chain, linear or branched, preferably linear, more particularly (Ci-C8)alkylene, r represents an integer inclusively between 6 and 11, preferably between 7 and 10 such that 8; u is 0 or 1; and G represents a hydrogen atom, or a group chosen from hydroxy, carboxy, (di)(Ci-C4)(alkyl)amino, (hetero)aryl in particular aryl such as phenyl, cycloalkyl such as cyclohexyl, or sugar, in particular a monosaccharide optionally protected by one or more groups such as acyl, preferably Suc represents s with Re representing a group Rf-C(O)- , with Rf representing a (CrC4)alkyl group such as methyl. Preferably when u is 0, G represents a cycloalkyl group such as cyclohexyl, or sugar as defined above. According to another advantageous variant when u is 1, G represents a hydrogen atom, or a group chosen from hydroxy, carboxy, (di)(Ci-C4)(alkyl)amino, (hetero)aryl in particular aryl such as phenyl.

8. Composition according to any one of the preceding claims, in which the PHA copolymer(s) a) comprise a radical R 2 chosen from (C3-C20)alkyl, linear or branched, and (C3-C20)alkenyl, linear or branched, in particular a hydrocarbon group linear; preferably the hydrocarbon group has a carbon number corresponding to the number of carbon atoms of the radical R1 from which at least one carbon atom is removed, preferably corresponding to the number of carbon atoms of the radical R1 from which at least two carbon atoms are removed.

9. Composition according to any one of the preceding claims, in which the PHA copolymer(s) a) comprise a radical R 2 which is a linear or branched (C4-C6)alkyl group, preferably branched (C4-C5)alkyl such as isobutyl.

10. Composition according to any one of claims 3 to 9, in which the PHA copolymer(s) are such that, when R 1 represents a (C5-C28)alkyl group, unit (A) is present in a molar percentage ranging from 0.5% to 99%, more preferably from 50% to 99%, more particularly from 60% to 99% and even more preferably from 70% to 99%; unit (B) is present in a molar percentage ranging from 2 to 40%; and unit (C) is present in a molar percentage ranging from 0.5 to 20% relative to all units (A), (B) and (C).

11. Composition according to any one of claims 3 to 9, in which the PHA copolymer(s) a) are such that when R 1 represents a hydrocarbon chain chosen from i) (C5-C28)alkyl, linear or branched, ii) (C5-C28)alkenyl, linear or branched, iii) (C5-C 28)alkynyl, linear or branched, preferably the hydrocarbon group is linear, said hydrocarbon chain being substituted by one or more atoms or groups a) to m) and / or interrupted by one or more heteroatoms or groups a') to c') as defined for R1; - unit (A) is present in a molar percentage ranging from 0.1 to 99%, preferably a molar percentage ranging from 0.5 to 50%, more preferably a molar percentage ranging from 1 to 40%, even more preferably a molar percentage ranging from 2 to 30%, better still a molar percentage ranging from 5 to 20%; even better still a molar percentage ranging from 10 to 30% in moles of unit (A);and - unit (B) is present in a molar percentage ranging from 1% to 99.5%, preferably from 1% to 90%, plus; preferably from 2% to 70%, particularly from a molar percentage of 2 to 10%; and unit (C) is present in a molar percentage ranging from 0.5 to 20%, relative to all units (A), (B) and (C); advantageously, the PH A copolymer(s) of the invention comprise from 2% to 10% by mole of unit (B); and from 0.5% to 7% by mole of unit (C), more advantageously the copolymer comprises from 5% to 35% by mole of unit (B); and from 0.5% to 7% by mole of unit (C)

12. Composition according to any one of the preceding claims, in which the unit(s) (A) of the PHA copolymer(s) are chosen from the following repeating units (A), as well as their optical and geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: (A) R1 Al -ALKrS-ALK2-COOH A2 -ALKrS-ALK2-H A3 -ALKrS-ALK2-OH A4 -ALKrS-ALK2-NH2 A5 -ALKrS-Cycr A6 -ALKrS-CH2-Fur A7 -ALKrS-Suc A8 -ALKrS-ALK2-Ar A9 -ALKrHal A10 -ALKrCN Garlic -ALKrCH=CRrRw A12 -ALK2-H Repeater unit Al to A12 in which: - ALKi represents a linear or branched Ci-C2o divalent hydrocarbon radical, preferably linear or branched Ci-Cio, more preferably linear; - ALK2 represent a linear or branched divalent C1-C2o hydrocarbon radical, preferably linear or branched C1-C12; - Rr and Rw independently denote a hydrogen atom or an alkyl radical (CrC4 such as methyl, preferably Rr and Rw are identical; - Hal represents a halogen atom such as bromine; - Ar: represents a (hetero)aryl group such as phenyl; - Cycl': represents a cycloalkyl group such as cyclohexyl or heterocycloalkyl such as dithiolane or epoxide, preferably epoxide; - Fur: represents a furyl group, preferably 2-furyl; - Suc: represents a sugar group, in particular a monosaccharide optionally protected by one or more groups such as acyl, in particular acetyl; In particular, the stereochemistry of the carbon atoms carrying the radicals R1 is of (R) configuration.

13. Composition according to any one of the preceding claims, in which the PHA copolymer(s) a) comprise the following repeating units as well as their optical, geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates: n 9 ni © n * exposed iliiilllBlllli W -(G Hzjs-SC H(CHs )-G(O)-OH -(CH2)*-CHî Oj -(CHa^-S-^CHïjj-CHs -(CH2>CH3 (3) -(CHz )sS-(CHa)a -OH -(CH2>-CH3 (4) -(CH2>-S-(CHs)2-NH2 -(CH2>CHj <5j MS-^ycl -(CH2>CH3 (6) -(ChbJs-S-CHîÆïM' -(CHz>CH3 (7) -(CHz>-S-Suc -(CH2>CH3 (S) -(CH2>-S-(GH2)2-Ar -(CH2>-CHj 01 ^ŒMs-S-CHz-Àf -(CH2>-CH3 00) -(CHs>-S-CH(CHs)-C(O)-OH -(CH2)5-CHj (11) -{GH2)=-HaL -{GH2)5-CHs (12) -(CHs^-CN -(CH2>-CHA 03) J) -(CH2)5<ÎH3 (14) -(CHsJs-Âr -(CH2)5-GH3 (15) -{CH2>-GHj -(CHî)2-CH3 (16) -{CH2>GH3 -!Û-O)3-CH> (17) -(CHes-CHô -(CH2)ü-CHî (18) ^CH2>-CHs -(CHsJs-CHj (19) ”5 CHz^CHCCHîJCHî -CHz-CH(CH3)C -h (20) -(CH2>-CH=CHî. -(CHajs-QHî (21) H2U-CH=CfCHs)CHî -CH2-CH(CHs)C 43 m and n are as defined above, Hal represents a halogen atom such as bromine and t represents an integer between 1 and 10, preferably between 3 and 8 such as 6. Ar: represents a (hetero)aryl group such as phenyl; Ar': represents a (Ci-C4)alkyl(hetero)aryl group such as t-Butylphenyl, preferably 4-t-butylphenyl; Cycl: represents a cyclohexyl group; Fur: ​​represents a furyl group, preferably 2-furyl; Suc: represents a sugar group, in particular a monosaccharide optionally protected by one or more groups such as acyl, preferably Suc represents: with Re representing an Rf-C(O)- group, with Rf representing a (Ci-C4)alkyl group such as methyl; more preferably the PHA copolymer(s) have the following formula, as well as their optical isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates: 033333333333330 3333333330^333333333 03 -{QHï>s-ch^ -{CHs>CH3 (2J -(CH; te-CHs (4) (53 qCHa^-S-Cyd -(GHs>CH3 -ÜCHi^-S-dHî-Fur O -(CH^-S-SttC £83 -(CK0<CH:, CS') -(Ot^-S-CH^Af -{CHJs-ÇH, 0Q) -(CH^-S-CHfCHsKCOHJH ~{OHS)S-CH> fit') -(CHcrCN -{CH-ls-CH; ("3 G j (CH;.:., CH. (U) ■-(CH^-Ar -(CH;à-CHs 053 -(CH^-CH, (153 -(CH^rCHs -(CH^-CHs 07} -(CH0-CHs ~{CKy):î-CHx 083 -(CH^ca -(CH-.K-CH- 05} qCH^-GHlCH^CHs -CHrCHlCHOCH, 0(0 -(CHà-CH=CHj -{CHÛs-CHk (213 -(CHArCH^tCHjjCH, ^HrCH(CH;JCH5 (22) -ÇCH^rCHs ■{CH0.-CH. (23) -(CH0,-CHs -{CHs),-CHx 04) 4CHA-CWx M, n, Hal, t, Ar, Ar', Cycl, Fur, and Suc are as previously defined for compounds (1) to (14). iiiiiliiii) (25) >H,lGH, -(CH: iGHÇ.GH, -iCHJs-CH, 06) -(CH^-CHs -(CHJsrCH, -CH, (27) -(CH3-CN -(C ■HCR, CH-j.) -CN -0H;1>-DHS -Ar CsjiipOSSB; R' R' (295 ^CHA-CH^CH, (CHsV CH, (CH^ CH, -fCH;},-CH=CHs -iCKJs-CH^CH; {30} -(CH;;)5-CH=CH2 (GHÀ-CH, (CHÆ-CH3 -CCCH-^1-CH^S, (CHÆ-CH3 -CCCH-^1-CH^Hs). -CH, {32} (CH^ 0¾ (CHvl-QHS<CH4,-CH> (33} OOOO r '1 g 1 'v CH;: CH; C{O)-OH O xxa <• X Ô O b ü X (34) ZXDJO 0 x 1 AXA îf OZ (35) o X Ù CH: X & 7 o xX Z y. and XO New Zealand GH; CHy ' X 7 X P. •y' NH;: j si ' A CHsX- S-Cÿ c 1 -{CHï>S--Oy^ For GH; - (GH 2 s- F 'J r O 0 x 1 -(OHjjs-S-Sssc -{CH>>S-Sis (45) -Ar CH -f CH:?9 - ( ■" H Af Ar (44) “■v'di-S j>*“ Ar'- ' ( GH?2) GH: They £ OC- <xo-cr(43) -sGHsM-SaS CHi i44j OS .1 ' 'Vf si ' preferably the PHA(s) a) of the invention are chosen from compounds (15), (16) and (17) in particular (16); more particularly the PHA(s) a) of the invention are chosen from compounds (15'), (16') and (17') in particular (16'); more preferably the PHA(s) a) of the invention are chosen from compounds (25), (26), (31) and (32) in particular (26).

14. Composition according to any one of the preceding claims, in which b) the polyurethane latex(es) is(are) capable of being obtained from: Bi) of at least one polyol chosen from: - Bn) a polyester polyol resulting from the reaction of: • at least one polyol Bm) with • at least one polycarboxylic acid Bn2) and • optionally Bm) at least one monocarboxylic acid; - B i2) a diol; and - the mixture of Bu) and B[2); and B2) at least one polyisocyanate, preferably a diisocyanate, in particular aliphatic or cycloaliphatic and mixtures thereof; and B3) of at least one hydrophilic monomer chosen from: - B3i) compounds carrying an acid function, in particular carboxylic, or a basic function, in particular primary, secondary or tertiary amine, and further comprising at least one hydroxyl function, preferably at least two hydroxyl functions, in particular two hydroxyl functions such as 2,2-bis(hydroxymethyl)propionic acid and - B32) diamine compounds of formula H 2 NR 5 -NH 2 (X) in which R s represents an alkylene radical substituted by one or more ionic or potentially ionic groups; and B4) optionally at least one amino compound which is not substituted by one or more ionic or potentially ionic groups; more particularly the polyurethane latex(es) b) is(are) likely to be obtained from: B1) of at least one polyol chosen from: - Bn) at least one polyester polyol resulting from the reaction of: • at least one polyol Bm) such as neopentyl glycol, hexanediol, butanediol with • at least one polycarboxylic acid Bn2) such as adipic acid, succinic acid and optionally Bn3) at least one monocarboxylic acid, preferably abietic acid or rosin; and / or B[2) at least one diol; and their mixture; and B2) at least one polyisocyanate, preferably at least one diisocyanate, in particular aliphatic or cycloaliphatic such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohe xyl)-methane hexamethylene diisocyanate and their mixture;and B3) at least one hydrophilic monomer chosen from B3[) compounds carrying an acid function, for example a carboxylic function, or a basic function, for example a primary, secondary or tertiary amine function, and further comprising at least one hydroxyl function, preferably at least two hydroxyl functions, in particular two hydroxyl functions such as 2,2-bis(hydroxymethyl)propionic acid and / or B32) at least one diamine compound of formula H 2 NR 5 -NH 2 (X) in which R 5 represents an alkylene radical substituted by one or more ionic or potentially ionic groups such as carboxy; and B4) optionally at least one amine compound which is not substituted by one or more ionic or potentially ionic groups.;

15. Composition according to any one of the preceding claims, in which b) the polyurethane latex(es) b) is(are) chosen from polyurethanes with the following INCI names: polyurethane-32, polyurethane-32, polyurethane-34, polyurethane-35, polyurethane-48, polyurethane-93, and polyurethane-99 and mixtures thereof.

16. Composition according to any one of the preceding claims, in which: the total quantity of the polyurethane latex(es) b) in dry matter, present in the composition C1 or C1', is between 0.01% and 30% by weight, more preferably from 0.05% to 28% by weight, and better still from 0.1% to 25% by weight, relative to the total weight of the composition.

17. Composition according to any one of the preceding claims, which comprises c) one or more fatty substances, preferably liquid at 25°C and at atmospheric pressure, particularly chosen from: ■ hydrocarbons, in particular alkanes, oils of animal origin, ■ oils of vegetable origin, ■ glycerides or fluorinated oils of synthetic origin, ■ fatty alcohols, ■ esters of fatty acid and / or fatty alcohol, ■ non-silicone waxes, silicones; and ■ mixtures thereof; in particular the liquid hydrocarbon fatty body(ies) are preferably volatile hydrocarbon oils or are a mixture of different volatile oils, preferably chosen the volatile oil(s) are chosen from alkanes, linear or branched, in C8-Ci4, more preferably in C14-Ci3, even more preferably in C9-C12, more particularly chosen from undecane, dodecane, tridecane, and isododecane; or a mixture of different volatile oils preferably comprising isododecane in the mixture, or a mixture of undecane and tridecane.

18. Composition according to any one of the preceding claims, which comprises c) one or more fatty substances, preferably liquid at 25°C and at atmospheric pressure, particularly chosen from: - vegetable oils formed by esters of fatty acids and polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, macadamia, soybean, sweet almond, calophyllum, palm, grape seed, corn, arara, cotton, apricot, avocado, jojoba, olive or cereal germ oil; - linear, branched or cyclic esters having more than 6 carbon atoms, in particular 6 to 30 carbon atoms; and in particular isononyl isononanoate; and more particularly the esters of formula Rd-C(O)-O-Re in which Rd represents the residue of a higher fatty acid comprising from 7 to 19 carbon atoms and Re represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, in particular diisopropyl adipate and isopropyl myristate; more preferably the esters of formula Rd-C(O)-O-Re in which Rd represents the residue of a higher fatty acid comprising from 8 to 10 carbon atoms and Re represents a hydrocarbon chain comprising from 12 to 18 carbon atoms; - hydrocarbons and in particular linear, branched and / or cyclic alkanes, volatile or non-volatile, such as C5-C6o isoparaffins, possibly volatile such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or 'ISOPARs' and their mixture; or alkanes resulting from the complete hydrogenation / reduction of mixtures of fatty acids from Cocos Nucifera (Coconut) oil such as dodecane; or the mixture of C9-Ci2 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched alkanes, C9-Ci2 in particular comprising dodecane; or paraffin oils, vaseline oils, or hydrogenated polyisobutylene; - ethers having 6 to 30 carbon atoms; - ketones having 6 to 30 carbon atoms; - aliphatic fatty monoalcohols having 6 to 30 carbon atoms, the hydrocarbon chain not containing a substitution group, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; - polyols having 6 to 30 carbon atoms, such as hexylene glycol; and - their mixtures such as mixtures of esters of linear or branched C8-Ci0 fatty acids and C12-Ci8 fatty alcohols and alkanes resulting from the complete hydrogenation / reduction of mixtures of fatty acids from Cocos Nucifera (Coconut) oil, in particular dodecane, such as mixtures of cococaprylate / caprate and dodecane; or mixtures of C9-Ci2 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched alkanes, C9-Ci2 in particular comprising dodecane; preferably the liquid hydrocarbon fatty body(ies) iii) is (are) chosen from C6-Ci6 alkanes, linear or branched, preferably C8-CM, more preferably C9-Ci3, even more preferably C9-Ci2 and even more preferably the alkanes are volatile and chosen from undecane, dodecane, isododecane, tridecane, and their mixture comprising in particular dodecane, isododecane or a mixture of undecane and tridecane; or the liquid fatty substance(s) iii) is (are) a mixture of non-volatile oil(s) and volatile oil(s) in particular comprising as volatile oil isododecane, undecane, dodecane, isododecane, and / or tridecane, more preferably isododecane; as a mixture of volatile and non-volatile oil, mention may be made of the mixture of isododecane and isononyl isononanoate; and more preferably when the fatty substance(s) are a mixture of volatile and non-volatile oil, the quantity of volatile oil is greater than the quantity of non-volatile oil.

19. Composition according to any one of the preceding claims, which further comprises one or more coloring agents chosen from pigments, direct dyes and mixtures thereof, preferably pigments; more preferably the pigment(s) of the invention are chosen from carbon black, iron oxides, in particular black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet pigments such as BLUE 1 LAKE, azo pigments, in particular red pigments, such as D&C RED 7, alkali metal salt of lithol red, such as the calcium salt of lithol red B, even more preferably red iron oxides.

20. Process for treating keratin materials, preferably a) keratin fibres, in particular human such as hair, or |3) human skin, in particular the lips, by applying the composition as defined in any one of the preceding claims.

21. Cosmetic use of the composition according to any one of claims 1 to 19.

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