Cosmetic composition comprising a polyhydroxyalkanoate copolymer having an (un)saturated hydrocarbon-based chain and a crystalline fatty substance

Abstract

The present invention relates to a unit (A) of the following formula: -[-O-CH(R 1 )-CH2-C(O)-]- unit (A) (in polymer unit (A), -R 1 is as defined in the specification), and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates; and b) one or more fatty substances.

Description

[Technical field]

[0001] The present invention relates to a cosmetic composition comprising a) at least one polyhydroxyalkanoate copolymer having (un)saturated hydrocarbon-based groups, b) at least one crystalline fatty substance, c) optionally at least one oil, d) optionally at least one organic solvent, and e) optionally water, and to a process for treating keratinous materials using such a composition. [Background technology]

[0002] It is a known practice to use film-forming polymers in cosmetics that can be delivered in organic media, such as hydrocarbon-based oils. The polymers are used as film-forming agents, especially in makeup products such as mascaras, eyeliners, eyeshadows, lipsticks, etc.

[0003] (Patent Document 1) describes C3-C hydroxybutyrate-co-hydroxyvalerate, etc. 21 Cosmetic compositions are described that include pigments coated with polyhydroxyalkanoates.

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

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

[0006] [Patent Document 1] Specification FR-A-2964663 [Patent Document 2] International Publication No. 2011 / 154508 Brochure [Patent Document 3] US Patent Application Publication No. 2015 / 274972 Summary of the Invention [Problem to be solved by the invention]

[0007] The main part of polyhydroxyalkanoate copolymers is a polymer derived from polycondensation of polymeric repeating units that are mostly identical and derived from the same carbon source or substrate.These documents do not describe the cosmetic use of polysaccharides and copolymers derived from polycondensation with an aliphatic substrate or a first carbon source and at least one second substrate different from the first, which contains one or more (un)saturated hydrocarbon-based groups.Therefore, there is a need for a composition that contains a polyhydroxyalkanoate copolymer that is lipophilic or soluble in fatty phase.This makes it possible to obtain a film on keratinous materials that has good cosmetic properties, especially good oil and sebum resistance, and also to modify gloss or mattness. [Means for solving the problem]

[0008] The applicant has discovered that polyhydroxyalkanoate copolymers with specific grafted or functionalized hydrocarbon-based groups, as defined below, can be easily used in fatty media, thus making it possible to obtain homogeneous compositions. This composition C1 shows good stability, especially after storage for one month at room temperature (25°C). Composition C1 makes it possible to obtain a film with good cosmetic properties, good color durability without the composition running off, and a matte or glossy appearance of the treated keratinous material, especially after application to the keratinous material.

[0009] Crystalline fatty substances, especially waxes, are known and widely used in cosmetics as a retaining binder during compression for the formation of solid or semi-solid compositions, especially for the formation and molding of sticks, in the art of deodorant sticks, lipsticks, eyeshadows and mascaras. Creamy skin cleansers, especially for facial skin, have been used for many years, in particular the traditional cold cream, which is composed of mineral oil (50%-60%), beeswax (about 15%), borax (about 1%) and water (30%-40%). The beeswax contains cerotic acid, which is neutralized with borax to obtain an emulsifier and form the cream. Liquid and semi-solid glosses are formulated from mineral oils or animal or vegetable fats thickened with waxes (ozokerite), fatty alcohols (cetyl alcohol) or polymers (e.g. polyethylene), and are usually packaged in bottles or tubes. Waxes are also used for hair removal in mixtures of waxes and resins (rosin and beeswax) mixed with lipids, such as oleyl oleate, which melts at temperatures of 50°C to 55°C (Kirk-Othmer Encyclopedia of Chemical Technology. "Cosmetics", M. and A. Rieger, et al., pages 1-49). Beeswax is also associated with dihydroabietyl alcohol for mascara. However, resistance to water and friction is not always satisfactory.

[0010] In many conditions of use of film-forming substances on keratinous materials, such as makeup or coloring applications, it is desirable to have a very good resistance to rubbing of the deposit of film-forming substances, in addition to good resistance to water and oil, especially edible oils such as olive oil, for example, to avoid transfer to clothes and to maintain a homogeneous appearance of the deposit.If the resistance to rubbing is insufficient, the deposit obtained can quickly become very unsightly for consumers, especially if these deposits are colored, as in makeup applications such as lipstick, foundation or mascara.In hair applications, the lack of resistance to rubbing is very problematic in all coloring applications, since it causes transfer to clothes and causes an unsightly appearance of keratinous fibers.Therefore, it is necessary to improve the persistence of PHA contained in the aqueous phase.

[0011] There is therefore a real need to obtain deposits of film-forming materials which are resistant to oil, in particular edible oils, are water resistant and have very good resistance to abrasion.

[0012] If the deposits are coloured, these problems of resistance to humidity can lead to colour transfer onto clothing for example, which is a problem in itself and makes the deposits very unsightly.

[0013] These problems are solved by using compositions C1 described herein, which are capable of significantly improving the rub resistance of polyhydroxyalkanoate (PHA) copolymers.Furthermore, compositions C1 according to the invention make it possible to obtain films on keratinous materials that, after deposition, have good cosmetic properties, in particular good oil- and sebum-resistance, and also modify the gloss or mattness.

[0014] The subject of the present invention is therefore a) The following units (A): -[-O-CH(R 1 )-CH2-C(O)-]- Unit (A) (In the polymer unit (A), - R 1represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain, or a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon-based chain, containing 5 to 28 carbon atoms; preferably, the hydrocarbon-based chain is i) a linear or branched (C 28 ) alkyl, ii) linear or branched (C5-C 28 ) alkenyl, iii) linear or branched (C5-C 28 ) alkynyl; preferably, the hydrocarbon-based group is linear; The hydrocarbon-based chain is a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C1-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamido-C(O)-N(R a )2 or C(S)-N(R a ) 2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active agent, l) α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) cosmetic active agent, m) thiosulfate, and a′) O, S, N(R a ) or Si(R b )(R c ), b') S(O) r or (thio)carbonyl, or c') Rx with X representing a combination of a') and b'), such as (thio)ester, (thio)amide, (thio)urea or sulfonamide; R a represents a hydrogen atom, a (C1-C4) alkyl group, or an aryl(C1-C4) alkyl group such as benzyl, preferably R a represents a hydrogen atom; R b and R cmay be the same or different and represent a (C1-C4) alkyl or (C1-C4) alkoxy group, and in particular are preferably substituted by only one substituent selected from b) halogen and j) epoxide, and / or one or more a') heteroatoms, such as O, S, N(R a ) and Si(R b )(R c ), b') S(O) r , (thio)carbonyl, or c') a combination of a') and b'), such as (thio)ester, (thio)amide, (thio)urea, sulfonamide, etc.; r is 1 or 2; R a is as defined above, preferably R a represents a hydrogen atom, and R b and R c is as defined above), and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates; b) one or more fatty substances that are crystallizable at 25° C. and atmospheric pressure; c) optionally one or more oils, i.e. fatty substances, which are liquid at 25° C. and atmospheric pressure; d) optionally with one or more organic solvents, preferably polar aprotic or protic solvents, in particular polar and protic solvents; e) optionally with water; Composition C1 comprising: Preferably, composition C1 comprises component c), preferably components c)+d).

[0015] Another subject of the invention is the cosmetic use of a composition C1 comprising a) one or more PHA copolymers as defined above, b) one or more crystalline fatty substances as defined above, optionally c) one or more fatty substances other than b) as defined above, d) optionally one or more organic solvents as defined above, and e) optionally water.

[0016] Another subject of the invention is a process for treating keratinous materials, preferably α) keratinous fibres, in particular human keratinous fibres such as hair, or β) human skin, in particular the lips, using a) one or more PHA copolymers as defined above, b) one or more crystalline fatty substances, optionally c) one or more fatty substances other than b), optionally d) one or more organic solvents, and optionally e) water.

[0017] More particularly, the subject of the invention is a non-therapeutic cosmetic method for treating keratinous materials, comprising applying to said materials a composition C1 as defined above or C1' as defined below, said method of treatment being in particular a method for caring for or making up keratinous materials. [Brief description of the drawings]

[0018] [Figure 1] Assembly of fed-batch fermentation mode. [Diagram 2] assembly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] For purposes of this invention, and unless otherwise indicated, - the term "cosmetic active agent" means a group of organic or organosilicon compounds that can be incorporated into cosmetic compositions to provide an effect on keratin materials, whether this effect is immediate or provided by repeated applications. As examples of cosmetic active agents, mention may be made of colored or uncolored, fluorescent or non-fluorescent chromophores, such as those derived from optical brighteners, or chromophores derived from UVA and / or UVB screening agents, anti-aging active agents or active agents with an effect on the barrier function, deodorant agents other than mineral particles, antiperspirant active agents other than mineral particles, desquamating active agents, antioxidant active agents, moisturizing active agents, sebum-regulating active agents, active agents intended to limit the shine of the skin, active agents intended to combat the effects of pollution, antibacterial or bactericidal active agents, active agents intended to provide benefits to the skin, such as antidandruff active agents, as well as fragrances. - the term "(hetero)aryl" means an aryl or heteroaryl group; - the term "(hetero)cycloalkyl" means a cycloalkyl or heterocycloalkyl group; - an "aryl" or "heteroaryl" group or an aryl or heteroaryl portion of a group, C1-C6, preferably C1-C4 alkyl groups; Halogen atoms such as chlorine, fluorine or bromine; Hydroxyl groups; · C1-C2 alkoxy groups; C2-C4 (poly)hydroxyalkoxy groups; Amino groups; an amino group substituted with one or two identical or different C1-C6, preferably C1-C4 alkyl groups; acylamino groups (-NR-COR'), where the group R is a hydrogen atom; a carbamoyl group ((R)2N-CO-), in which the groups R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; an alkylsulfonylamino group (R'SO2-NR-), in which the group R is a hydrogen atom or a C1-C4 alkyl group and the group R' is a C1-C4 alkyl group or a phenyl group; the aminosulfonyl group ((R)2N-S(O)2-), in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; carboxyl radicals in the form of acids or chlorides (preferably alkali metal or substituted or unsubstituted ammonium); · Cyano group (CN); Polyhalo(C1-C4)alkyl groups, preferably trifluoromethyl (CF3) may be substituted by at least one substituent carried by a carbon atom selected from; the cyclic or heterocyclic part of the non-aromatic group is Hydroxyl, · C1-C4 alkoxy, C2-C4 (poly)hydroxyalkoxy; alkylcarbonylamino (RCO-NR'-), in which the group R' is a hydrogen atom or a C1-C4 alkyl group and the group R is a C1-C2 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups; alkylcarbonyloxy (RCO-O-), in which the group R is a C1-C4 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups; Alkoxycarbonyl ((RO-CO-)), in which the group R is a C1-C4 alkyl group or an amino group substituted by one or two identical or different C1-C4 alkyl groups. may be substituted by at least one substituent carried by a carbon atom selected from the group consisting of: - a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted by one or more oxo groups; - the hydrocarbon-based chain is unsaturated if it contains one or more double bonds and / or one or more triple bonds; - an "aryl" group denotes a monocyclic or fused or non-fused polycyclic hydrocarbon-based chain containing 6 to 22 carbon atoms, at least one ring of which is aromatic, preferably an aryl group is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl; - a "heteroaryl" group refers to a monocyclic or fused or non-fused polycyclic 5- to 22-membered group containing from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms, in which at least one ring is aromatic; preferably the heteroaryl group is acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazolyl, selected from azpyridyl, imidazolyl, indolyl, isoquinolyl, naphthimidazolyl, naphthoxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrrylyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl and xanthryl; - a "cyclic" or "cycloalkyl" group is a monocyclic or fused or non-fused polycyclic non-aromatic cyclic hydrocarbon-based group containing 5 to 22 carbon atoms and which may contain one or more unsaturations; cycloalkyl is preferably a cyclohexyl group; - a "heterocyclic" or "heterocycloalkyl" group is a monocyclic or fused or non-fused polycyclic 3- to 9-membered non-aromatic ring group containing 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms; preferably, heterocycloalkyl is selected from epoxide, piperazinyl, piperidyl, morpholinyl and dithiolane; - an "alkyl" group is a linear or branched, saturated, especially C1-C6, preferably C1-C4, hydrocarbon-based group; - an "alkenyl" group is a linear or branched unsaturated hydrocarbon-based group containing one or more conjugated or non-conjugated double bonds; - an "alkynyl" group is a linear or branched unsaturated hydrocarbon-based group containing one or more conjugated or non-conjugated triple bonds; - "alkoxy group" is an alkyloxy group, where alkyl is a linear or branched C1-C6, preferably C1-C4, hydrocarbon-based group; - "sugar" groups are mono- or polysaccharide groups and their O-protected sugar derivatives such as sugar esters of (C1-C6) alkyl carboxylic acids, e.g. sugar esters of acetic acid, sugars containing amine groups and (C1-C4) alkyl derivatives such as methyl derivatives, e.g. methylglucose. Sugar groups that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose; - The term "monosaccharide" refers to a compound of formula C, where x is an integer equal to or greater than 5. x (H2O) x where x is preferably 6 or more, in particular x is 5 to 7 (inclusive), preferably x=6, which may be in the D or L configuration, and in the alpha or beta anomers, and also in their solvates, such as salts and hydrates thereof; - the term "polysaccharides" refers to polysaccharides which are polymers composed of several saccharides linked by O-oside (said polymers are composed of monosaccharide units as defined above, said monosaccharide units containing at least 5, preferably 6 carbon atoms; in particular, the monosaccharide units are linked through 1,4 or 1,6 bonds as α (alpha) or β (β) anomers, each oside unit can be of L or D configuration), and also to their salts and their solvates, such as hydrates of said monosaccharides; more particularly, they are represented by the general formula: - [C x (H2O) y )] w -or-[(CH2O) x ]w - (wherein x is an integer of 5 or more, preferably x is 6 or more, in particular x is 5 to 7 (inclusive), preferably x=6, y is an integer representing x-1, and w is an integer of 2 or more, in particular 3 to 3000 (inclusive), more particularly 5 to 2500, preferably 10 to 2300, in particular 15 to 1000 (inclusive), more particularly 20 to 500, preferably 25 to 200); - the term "saccharide containing an amine group" means that the saccharide group is substituted by one or more amino groups NR1R2, i.e. at least one of the hydroxyl groups of at least one saccharide unit of the saccharide group is substituted by a group NR1R2, where R1 and R2 may be the same or different and are selected from the group i) hydrogen atom, ii) (C1-C6) alkyl group, iii) aryl group such as phenyl, iv) aryl(C1-C4) alkyl group such as benzyl, vii) -C(Y)-(Y') f -R'1 (wherein Y and Y' may be the same or different and represent an oxygen atom, a sulfur atom or N(R'2), preferably oxygen, f=0 or 1, preferably 0; and R'1 and R'2 represent i) to vi) of R1 and R2 defined above, in particular R'1 represents a (C1-C6) alkyl group such as methyl. Preferably, R1 and / or R2 represent a hydrogen atom or a (C1-C4) alkylcarbonyl group such as acetyl, more preferably R1 represents a hydrogen atom and R2 represents a (C1-C4) alkylcarbonyl group such as acetyl; - the term "organic or mineral acid salt" more specifically means i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids: Alk-S(O)2OH, such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(O)2OH, such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-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(I'z) (wherein R° is a (hetero)aryl group such as phenyl, a (hetero)aryl(C1-C4)alkyl group such as benzyl or a (C1-C4)alkyl group such as phenyl, ... 10 ) alkyl, said alkyl group being preferably substituted optionally by one or more hydroxyl groups or by amino or carboxyl groups, R° preferably representing a (C1-C6) alkyl group, optionally substituted by one, two or three hydroxyl or carboxyl groups; more preferably the monocarboxylic acid of formula (I'z) is selected from acetic acid, glycolic acid, lactic acid and mixtures thereof, more particularly selected from acetic acid and lactic acid; and the polycarboxylic acid is selected from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof); and xii) organic or mineral salts selected from amino acids containing more carboxylic acid groups than amino groups, such as salts derived from γ-carboxyglutamic acid, aspartic acid or glutamic acid, in particular γ-carboxyglutamic acid; - "anionic counterion" is an anion or anionic group that is associated with a cationic charge; more specifically, anionic counterions include i) halides, such as chloride or bromide; ii) nitrates; iii) C1-C6 alkylsulfonates: Alk-S(O)2O - , such as methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: Ar-S(O)O -for example benzenesulfonates and toluenesulfonates i.e. tosylates; v) citrates; vi) succinates; vii) tartrates; viii) lactates; ix) alkyl sulfates: Alk-OS(O)O - x) aryl sulfates: Ar-OS(O)O - , for example, benzene sulfate and toluene sulfate; xi) alkoxy sulfates, etc.; xi) alkoxy sulfates: Alk-OS(O)O - xii) aryloxysulfates: Ar-OS(O)2O-; xiii) phosphates; xiv) acetates; xv) triflates; and xvi) borates, such as tetrafluoroborate; - "solvates" refers to hydrates and combinations with linear or branched C1-C4 alcohols, such as ethanol, isopropanol or n-propanol; - The term "chromophore" refers to the wavelength λ of 250-800 nm. abs by "dyes", it means a group derived from a colourless or coloured compound capable of absorbing in the UV and / or visible light range of 100 nm; preferably the chromophore is coloured, i.e. it absorbs in the visible range, i.e. preferably at wavelengths between 400 and 800 nm. Preferably the chromophore appears coloured to the naked eye, in particular between 400 and 700 nm (Ullmann's Encyclopedia, 2005, Wiley-VcH, Verlag "Dyes, General Survey", § 2.1 Basic Principle of Colour); - the term "fluorophore" means a chromophore capable of re-emission in the visible range, with an emission wavelength λem higher than the absorption wavelength, between 400 and 800 nm, preferably with a Stokes shift, i.e. the difference between the maximum absorption wavelength and the emission wavelength, of at least 10 nm; preferably, the fluorescent chromophore is capable of re-emission in the visible range λem abs , i.e., absorbs at wavelengths from 400 to 800 nm, and in the visible region λ emMore preferably, the fluorescent chromophore has a wavelength of λ between 420 and 550 nm. abs and can be re-emitted in the visible range λem, between 470 and 600 nm. - the term "optical brightening chromophore" means any optical brightening compound or "optical brighteners, optical brightening agents (OBAs)" or "fluorescent brightening agents (FBAs)" or "fluorescent whitening agents (FWAs)", i.e., any compound that emits UV radiation, i.e. at wavelengths λ between 250 and 350 nm; abs This energy is then converted into fluorescence, with an emission wavelength of 400-600 nm, λ em , i.e. chromophores derived from agents which re-emit in the visible light range, at wavelengths between blue-violet and blue-green, with a maximum in the blue range. Fluorescent whitening chromophores are therefore colourless in appearance; - the term "UV-A screening agent" means a chromophore derived from a compound that blocks (or absorbs) UV-A ultraviolet radiation of wavelengths between 320 and 400 nm; a distinction may be made between short UV-A screening agents (which absorb light of wavelengths between 320 and 340 nm) and long UV-A screening agents (which absorb light of wavelengths between 340 and 400 nm); - The term "UV-B screening agent" means a chromophore derived from a compound that filters out (i.e. absorbs) UV-B ultraviolet radiation at wavelengths between 280 and 320 nm. Further, unless otherwise stated, the limits defining a range of values ​​are included within that range of values.

[0020] a) PHA copolymer The composition C1 of the present invention comprises, as a first component, a) one or more PHA copolymers containing, or preferably consisting of, at least two different repeating polymer units (A) as defined above.

[0021] According to a particular embodiment of the invention, the composition C1 according to the invention comprises, as a first component, a) one or more PHA copolymers containing, or preferably consisting of, at least two different repeating polymer units selected from units (A) and (B) as previously defined.

[0022] Preferably, the composition C of the invention comprises a) The following units (A) and (B): -[-O-CH(R 1 )-CH2-C(O)-]-Unit (A) -[-O-CH(R 2 )-CH2-C(O)-]-unit (B) (In polymer units (A) and (B): - R 1 represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain, or a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon-based chain, containing 5 to 28 carbon atoms; in particular, the hydrocarbon-based chain is i) a linear or branched (C5-C 28 ) alkyl, ii) linear or branched (C5-C 28 ) alkenyl, iii) linear or branched (C5-C 28 ) alkynyl; preferably, the hydrocarbon-based group is linear; The hydrocarbon-based chain is a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C1-C4)(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamido-C(O)-N(R a )2 or C(S)-N(R a ) 2, g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active agent, l) α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) cosmetic active agent, m) thiosulfate, and a′) O, S, N(Ra ) or Si(R b )(R c ), b') S(O) r or (thio)carbonyl, or c') Rx with X representing a combination of a') and b'), such as (thio)ester, (thio)amide, (thio)urea or sulfonamide; R a represents a hydrogen atom, a (C1-C4) alkyl group, or an aryl(C1-C4) alkyl group such as benzyl, preferably R a represents a hydrogen atom; R b and R c may be the same or different and represent a (C1-C4) alkyl or (C1-C4) alkoxy group, and in particular are preferably substituted by only one substituent selected from b) halogen and j) epoxide, and / or one or more a') heteroatoms, such as O, S, N(R a ) and Si(R b )(R c ), b') S(O) r , (thio)carbonyl, or c') a combination of a') and b'), such as a (thio)ester, (thio)amide, (thio)urea, or sulfonamide; r is 1 or 2; R a is as defined above, preferably R a represents a hydrogen atom, and R b and R c is as defined above; R 2 In particular, linear or branched (C3-C 28 ) alkyl and linear or branched (C3-C 28 ) alkenyl, especially straight-chain hydrocarbon-based groups, more especially (C 20 ) alkyl or (C4-C 20 ) alkenyl; R 1represents a cyclic or acyclic, linear or branched, saturated or unsaturated, hydrocarbon-based group containing 3 to 30 carbon atoms, optionally substituted with 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 (a) above; preferably, the hydrocarbon-based group is a group R 1 the group R 1 and one or more polyhydroxyalkanoate (PHA) copolymers containing, preferably consisting of, at least two different repeating polymer units selected from: b) one or more fatty substances that are crystallizable at 25° C. and atmospheric pressure; c) optionally one or more fatty substances other than b), which are preferably liquid at 25° C. and atmospheric pressure; d) optionally one or more organic solvents other than c); e) optionally with water A composition C1', preferably a cosmetic composition, comprising: however, - (A) is understood to be different from (B); and - composition C1 contains c) one or more fatty substances and e) water; Preferably, composition C1 contains components c)+d).

[0023] The term "copolymer" means that the polymer is derived from the polycondensation of different polymeric repeating units, i.e. the polymer is derived from the polycondensation of different polymeric repeating units (A) or from the polycondensation of polymeric repeating units (A) and (B), it being understood that the polymeric unit (A) is different from the polymeric unit (B), and the copolymer can be obtained from a single, optionally substituted and / or interrupted, preferably unsubstituted and uninterrupted, saturated or unsaturated aliphatic carbon source, or from multiple carbon sources, in particular at least one of which is uninterrupted and unsubstituted saturated aliphatic, the other carbon sources being saturated or unsaturated aliphatic, in particular optionally substituted with halogen atoms, such as bromine, or with cyano groups, Bunte salts, dithiolane groups, carboxyl, etc.

[0024] According to one embodiment, the copolymer according to the invention is derived from a single carbon source, preferably a single, optionally substituted and / or interrupted, saturated or unsaturated aliphatic carbon source, preferably unsubstituted and uninterrupted.

[0025] According to one embodiment, the copolymer according to the present invention is derived from multiple carbon sources, preferably from 2 to 10 carbon sources, more preferably from 2 to 5 carbon sources, and even more preferably from 2 carbon sources.

[0026] According to one embodiment, the copolymer according to the invention is derived from multiple carbon sources, at least one of which is saturated aliphatic. According to a particular embodiment of the invention, the PHA copolymer consists of two different repeating polymer units selected from units (A) and (B) as defined above.

[0027] According to a particular embodiment of the invention, the PHA copolymer contains or consists of two different repeating polymer units selected from the units (A) and (B) defined above, R 2 However, in particular, linear or branched (C3-C 28 ) alkyl and linear or branched (C3-C 28) alkenyl, especially straight-chain hydrocarbon-based groups, more especially (C 20 ) alkyl or (C4-C 20 ) alkenyl; represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon-based group containing 3 to 30 carbon atoms; preferably, the hydrocarbon-based group is selected from the group R 1 the group R 1 The number of carbon atoms in the alkyl group is such that it corresponds to the number of carbon atoms in the alkyl group.

[0028] More particularly, the PHA copolymer according to the invention has the formula (I) [ka] (In formula (I), R 1 and R 2 is as defined above, m and n are integers equal to or greater than 1; preferably, the sum of n+m is between 450 and 1400, inclusive; Preferably, R 1 and R 2 When R represents an unsubstituted and uninterrupted alkyl group, m>n, more preferably R 1 and R 2 When R is a linear alkyl group, 1 is C5~C 13 is an alkyl group; and R 2 is C3~C 11 R with two carbon atoms subtracted, such as an alkyl group 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R 1 represents a substituted and / or interrupted alkyl group, an optionally substituted and / or interrupted alkenyl group, or an optionally substituted and / or interrupted alkynyl group; R 2When it represents an alkyl group, it includes repeating units where m < n), and further includes its optical or geometric isomers, its organic or mineral acid or base salts, and its solvates such as hydrates.

[0029] According to a specific embodiment, the PHA copolymer a) of the composition contains three different repeating polymer units (A), (B), and (C), preferably the following three different polymer units (A), (B), and (C): -[-O-CH(R 1 )-CH2-C(O)-]- unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- unit (B) -[-O-CH(R 3 )-CH2-C(O)-]- unit (C) (In the polymer units (A), (B), and (C), -R 1 and R 2 are as defined above; -R 3 is a hydrocarbon-based group containing 1 to 30 carbon atoms, which is saturated or unsaturated, linear or branched, cyclic or acyclic, and is optionally substituted with one or more atoms or groups a) to m) as defined for R 1 and / or is optionally interrupted by one or more heteroatoms or groups a') to c'); in particular, linear or branched (C1-C 28 ) alkyl and linear or branched (C2-C 28 ) alkenyl, in particular a linear hydrocarbon-based group, more particularly a hydrocarbon-based group selected from (C4-C 20 ) alkenyl; preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the group R 1 or corresponding to the number of carbon atoms of the group R 1 with at least 3 carbon atoms subtracted, preferably corresponding to the number of carbon atoms of the group R 1 with 4 carbon atoms subtracted), and also includes its optical isomers or geometric isomers, and its solvates such as hydrates; however, - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and - Preferably, R 1 , R 2 and R 3 represents an unsubstituted and uninterrupted alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B) and greater than the mole percentage of units (C), more preferably R 1 , R 2 and R 3 When R is a linear alkyl group, 1 is C5~C 13 is an alkyl group, R 2 is R minus two carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 3 is R minus 4 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, R 2 represents an alkyl group and / or R 3 It is understood that when represents an alkyl group, the mole percentage of units (A) is less than the mole percentage of units (B) and the mole percentage of units (C) is less than the mole percentage of units (B).

[0030] According to a particular embodiment of the present invention, the PHA copolymer has formula (II): [ka] (In formula (II), R 1 , R 2 and R 3 is as defined above; · m, n, and p are integers greater than or equal to 1; preferably, the sum n + m + p is between 450 and 1400, inclusive; - Preferably, when R 1 , R 2 , and R 3 represent unsubstituted and uninterrupted alkyl groups, m > n + p; more preferably, when R 1 , R 2 , and R 3 are linear alkyls, R 1 is a C5 - C 13 alkyl group, R 2 is a linear alkyl group having the number of carbon atoms corresponding to the number of carbon atoms of R 11 with two carbon atoms subtracted, such as a C3 - C 1 alkyl group, and R 3 is a linear alkyl group having the number of carbon atoms corresponding to the number of carbon atoms of R 1 with four carbon atoms subtracted, such as a C1 - C9 alkyl group; and - Preferably, when R 1 represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, and R 2 and R 3 represent alkyl groups, m < n + p), repeating units, further including their optical or geometric isomers, their organic or mineral acid or base salts, and their solvates such as hydrates.

[0031] According to certain embodiments, the PHA copolymer a) of the composition contains four different repeating polymer units (A), (B), (C), and (D), preferably the following four different polymer units (A), (B), (C), and (D); -[-O-CH(R 1 )-CH2-C(O)-]- unit (A) -[-O-CH(R 2 )-CH2-C(O)-]- unit (B) -[-O-CH(R 3 )-CH2-C(O)-]- unit (C) -[-O-CH(R4 )-CH2-C(O)-]-unit (D) (In the polymer units (A), (B), (C) and (D), - R 1 , R 2 and R 3 is as defined above; - R 4 is R 1 R represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, optionally substituted by one or more atoms or groups of a) to m) as defined above, and / or optionally interrupted by one or more heteroatoms or groups of a') to c'). 1 A linear or branched (C4-C6) alkyl group optionally substituted by one or more atoms or groups of a) to m) defined with respect to the above and / or interrupted by one or more heteroatoms or groups of a') to c'). 28 ) alkyl), and also its optical or geometric isomers, organic or mineral acid or base salts and solvates thereof, such as hydrates; however, - (A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), (C) is different from (A), (B) and (D), and (D) is different from (A), (B) and (C); and - Preferably, R 1 , R 2 , R 3 and R 4 represents an unsubstituted and uninterrupted alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), which is greater than the mole percentage of units (C), which is greater than the mole percentage of units (D), and more preferably, R 1 , R 2 , R 3 and R 4 When R is a linear alkyl group, 1 is C5~C 13 is an alkyl group, R 2 is C3~C 11R with two carbon atoms subtracted, such as an alkyl group 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 3 is R with 4 carbon atoms subtracted, such as C1-C9 alkyl groups. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 4 is R minus 6 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 In particular, when R represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, 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, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, it is understood that the mole percentage of units (A) is less than the mole percentage of units (B) and the mole percentage of units (C) is less than the mole percentage of units (B).

[0032] According to a particular embodiment of the present invention, the PHA copolymer has formula (III): [ka] (In formula (III), R 1 , R 2 , R 3 and R 4 is as defined above, m, n, p and v are integers greater than or equal to 1; preferably, the sum of n+m+p+v is between 450 and 1400 inclusive; and - Preferably, R 1 , R 2 , R 3 and R4 When R represents an unsubstituted and uninterrupted alkyl group, m>n+p+q, more preferably R 1 , R 2 , R 3 and R 4 When R is a linear alkyl group, 1 is C5~C 13 is an alkyl group, R 2 is R minus two carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 3 is R minus 4 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 4 is R minus 6 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group; R 2 and R 3 represents an alkyl group, and R 4 represents an optionally substituted and / or optionally interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, then n>m+v; more preferably n+p>m+v), and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates.

[0033] According to one embodiment, the PHA copolymer a) of the composition contains five different repeating polymer units (A), (B), (C), (D) and (E), preferably the following five different polymer units (A), (B), (C), (D) and (E): -[-O-CH(R 1 )-CH2-C(O)-]-Unit (A) -[-O-CH(R 2)-CH2-C(O)-]-unit (B) -[-O-CH(R 3 )-CH2-C(O)-]-unit (C) -[-O-CH(R 4 )-CH2-C(O)-]-unit (D) -[-O-CH(R 5 )-CH2-C(O)-]-unit (E) (In the polymer units (A), (B), (C), (D) and (E), - R 1 , R 2 , R 3 and R 4 is as defined above, - R 5 is R 1 R represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, optionally substituted by one or more atoms or groups of a) to m) as defined above, and / or optionally interrupted by one or more heteroatoms or groups of a') to c'). 1 A linear or branched (C4-C6) alkyl group optionally substituted by one or more atoms or groups of a) to m) defined with respect to the above and / or interrupted by one or more heteroatoms or groups of a') to c'). 28 ) alkyl; and preferably the hydrocarbon-based group is selected from the group R 4 the number of carbon atoms of the group R 4 (having a number of carbon atoms corresponding to the number of carbon atoms of ), as well as their optical or geometric isomers, organic or mineral acid or base salts and also solvates thereof, such as hydrates; however, - (A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E); (C) is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E) is different from (A), (B), (C) and (D); and - Preferably, R 1 , R 2 , R 3 , R 4 and R 5 represents an unsubstituted and uninterrupted alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), which is greater than the mole percentage of units (C), which is greater than the mole percentage of units (D), which is greater than the mole percentage of units (E), and more preferably, R 1 , R 2 , R 3 , R 4 and R 5 When R is a linear alkyl group, 1 is C5~C 13 is an alkyl group, R 2 is R minus two carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 3 is R minus 4 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 4 is R minus 6 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of R 5 is R minus 8 carbon atoms. 1 represents a linear alkyl group having a carbon number corresponding to the carbon number of - Preferably, R 1 In particular, when R represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, 2 represents an alkyl group and / or R 3 represents an alkyl group; and R 4 and R 5represents an optionally substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, it is understood that the mole percentage of units (A) is less than the mole percentage of units (B) and the mole percentage of units (C) is less than the mole percentage of units (B).

[0034] According to a particular embodiment of the present invention, the PHA copolymer has formula (IV): [ka] (In formula (IV): R 1 , R 2 , R 3 , R 4 and R 5 is as defined above, m, n, p, v and z are integers equal to or greater than 1; preferably, the sum of n+m+p+v+z is between 450 and 1400, inclusive; and - Preferably, R 1 , R 2 , R 3 , R 4 and R 5 When represents an unsubstituted and / or uninterrupted alkyl group, m>n+p+v+z; - Preferably, R 1 represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group; R 2 and R 3 represents an alkyl group, and R 4 and when the R5 groups represent a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, n>m+v+z; more preferably n+p>m+v+z), as well as optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates.

[0035] Preferably, R 1 is a linear or branched, preferably linear (C5-C 28 ) represents an alkyl hydrocarbon-based chain. According to one embodiment of the composition C1 or C1′ according to the invention, the PHA copolymer comprises a group R 1 is an alkyl group containing 5 to 14, preferably 6 to 12, and more preferably 7 to 10 carbon atoms, such as n-pentyl, n-hexyl, n-octyl, or n-nonyl.

[0036] According to a particular embodiment of the invention, the hydrocarbon-based chain R 1 According to a particular embodiment of the invention, the hydrocarbon-based chain R 1 has not been interrupted.

[0037] According to another embodiment of the invention, the group R 1 The hydrocarbon-based chain of is either 1) substituted, or 2) interrupted, or 3) substituted and interrupted.

[0038] According to a particular embodiment of the present invention, the PHA copolymer is 1 are hydrocarbon-based chains, especially O, S, N(R a ) and carbonyl or a combination thereof, e.g., an ester, an amide or a urea, selected from one or more (preferably one) atoms or groups, as defined above, represented by R a is as defined above, preferably R a represents a hydrogen atom); preferably, R 1 is such that represents an alkyl group interrupted by one or more atoms selected from O and S, more preferably an O or S, especially an S atom. In particular, when representing an interrupted hydrocarbon-based chain, especially an alkyl, R 1 is C7~C 20 , more particularly C8~C 18 , especially C9~C 16Preferably, said interrupted hydrocarbon-based chain, in particular alkyl, is linear.

[0039] According to another embodiment of the present invention, the PHA copolymer is 1 represents a hydrocarbon-based chain, in particular an alkyl group, substituted by one or more (preferably one) atoms or groups selected from a) to k) as defined above. Preferably, said hydrocarbon-based chain is substituted by only one atom or group selected from a) to k) as defined above.

[0040] According to a particular embodiment of the present invention, the PHA copolymer is 1 is a hydrocarbon-based chain, in particular R representing a group selected from a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C1-C4)(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl, such as anhydride, dithiolane or epoxide, j) cosmetic active agents selected from colored or uncolored, fluorescent or non-fluorescent chromophores, such as optical brighteners, UV screens, h) (hetero)aryl, such as phenyl or furyl, k) α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as sugar groups, preferably monosaccharides, such as glucosyl, γ) (hetero)aryl, such as phenyl, δ) cosmetic active agents as defined above, m) thiosulfate, and a′) O, S, N(R a a) represents an alkyl group as defined above, substituted by one or more (preferably one) groups selected from a) to b) represents a carbonyl, or b) represents a combination of a) and b) such as an ester, amide or urea; a represents a hydrogen atom or a (C1-C4) alkyl group, preferably R a is such that it represents a hydrogen atom.

[0041] More preferably, the PHA copolymer is 1represents a hydrocarbon-based chain, in particular a group selected from a) halogen, such as chlorine or bromine, b) hydroxyl, d) (di)(C1-C4)(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl, such as epoxide, h) (hetero)aryl, such as phenyl or furyl, k) α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar group, preferably a monosaccharide, such as glucosyl, γ) (hetero)aryl, such as phenyl, and a′) O, S or N(R a ), preferably R X, with X representing S, a represents a hydrogen atom or a (C1-C4) alkyl group, preferably R a is such that it represents a hydrogen atom.

[0042] According to one embodiment, said substituted hydrocarbon-based chain, in particular alkyl, is linear.

[0043] According to another embodiment, said substituted hydrocarbon-based chain, in particular alkyl, is branched.

[0044] According to another particular embodiment of the invention, the group R 1 The hydrocarbon-based chain of is substituted and interrupted.

[0045] According to a particular embodiment of the invention, the group R 1 The hydrocarbon-based chain (in particular the alkyl group as defined above) of - a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C1-C4)(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl, such as anhydride, dithiolane or epoxide, j) cosmetic active agents selected from colored or uncolored, fluorescent or non-fluorescent chromophores, such as optical brighteners, UV-screening agents, h) (hetero)aryl, such as phenyl or furyl, k) RX, where R represents a group selected from α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, e.g. monosaccharides, such as sugars, preferably glucose, γ) (hetero)aryl, such as phenyl, δ) cosmetic active agents as defined above, X being a') O, S or N(R a a) represents a carbonyl; b) represents a carbonyl; c) represents a combination of a) and b) represents an ester, an amide, or a urea; R a represents a hydrogen atom or a (C1-C4) alkyl or aryl (C1-C4) alkyl group such as benzyl, preferably R a represents a hydrogen atom]; and - O, S, N(R a ) and carbonyl or a combination thereof, e.g., ester, amide or urea, interrupted by one or more (preferably one) atoms or groups selected from R a is as defined above, preferably R a represents a hydrogen atom; preferably represents an alkyl group interrupted by one or more atoms selected from O and S, more preferably an O or S, especially an S atom. In particular, when representing an interrupted hydrocarbon-based chain, especially an alkyl, R 1 is C7~C 20 , more particularly C8~C 18 , especially C9~C 16 It is.

[0046] According to a preferred embodiment of the present invention, the group R 1 The hydrocarbon-based chain (particularly the alkyl group as defined above) of - R representing a group selected from a) halogen, such as chlorine or bromine, b) hydroxyl, d) (di)(C1-C4)(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl, such as epoxide, h) (hetero)aryl, such as phenyl or furyl, k) α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar, preferably a monosaccharide, such as glucose, γ) (hetero)aryl, such as phenyl, and a′) O, S or N(R a ), preferably substituted by one or more (preferably one) groups selected from R a represents a hydrogen atom or a (C1-C4) alkyl group, preferably R a represents a hydrogen atom; and - O, S, N(R a ) and carbonyl or a combination thereof, e.g., ester, amide or urea, interrupted by one or more (preferably one) atoms or groups selected from R a is as defined above, preferably R a represents a hydrogen atom; preferably represents an alkyl group interrupted by one or more atoms selected from O and S, more preferably an O or S, especially an S atom. In particular, when representing an interrupted hydrocarbon-based chain, especially an alkyl, R 1 is C7~C 20 , more particularly C8~C 18 , especially C9~C 16 It is.

[0047] Preferably, said substituted and interrupted hydrocarbon-based chains are, in particular, alkyl, and are preferably linear.

[0048] More preferably, the hydrocarbon-based chain R 1 When R is substituted, the group R 1 is substituted at the chain end opposite the carbon atom bearing

[0049] According to one embodiment of the present invention, the hydrocarbon-based chain R 1 is the following formula -(CH2)r -X-(ALK) u -G, X being as defined above, in particular O, S or N(R a ), preferably S; ALK is a linear or branched, preferably linear (C1-C 10 ) alkylene, more particularly a (C1-C8) alkylene chain, r represents an integer between 6 and 11, preferably between 7 and 10, such as 8, u is equal to 0 or 1; and G represents a hydrogen atom or a group selected from hydroxyl, carboxyl, (di)(C1-C4)(alkyl)amino, (hetero)aryl, particularly aryl such as phenyl, cycloalkyl such as cyclohexyl, or a monosaccharide optionally protected by one or more groups such as a sugar, particularly acyl, preferably Sug. [ka] (In the formula, R e is the group R f -C(O)-, R f represents a (C1-C4) alkyl group, such as methyl. Preferably, when u is equal to 0, G represents a cycloalkyl group, such as cyclohexyl, or a sugar as defined above. According to another advantageous variant, when u is equal to 1, G represents a hydrogen atom or a group chosen from hydroxyl, carboxyl, (di)(C1-C4)(alkyl)amino or (hetero)aryl, in particular aryl, such as phenyl.

[0050] According to another particular embodiment of the invention, the PHA copolymer is 1 is substituted with one or more halogen atoms such as fluorine, chlorine or bromine (C5-C 28 ) alkyl, more particularly linear (C5-C 20 ) alkyl, more particularly (C5-C 13 ) alkyl substituted with a halogen atom such as bromine. Preferably, the halogen atom is substituted at the end of the alkyl group. More preferably, R 1 represents 1-halo-5-yl, such as 1-bromo-5-yl.

[0051] According to another particular embodiment of the invention, the PHA copolymer is 1 g) substituted with one or more groups selected from cyano (C5-C 28 ) alkyl group, more preferably a linear (C5-C6) alkyl group substituted with a cyano group such as 1-cyano-3-propyl. 13 ) alkyl group.

[0052] According to another particular embodiment of the invention, the PHA copolymer is 1 represents vii) a (hetero)aryl(C1-C2)alkyl group, more particularly an aryl(C1-C2)alkyl group, preferably phenylethyl.

[0053] According to another particular embodiment of the invention, the PHA copolymer is 1 c) (hetero)cycloalkyl (C5-C 28 ) alkyl groups. More particularly, R 1 is preferably a linear (C5-C ) substituted with a heterocycloalkyl group such as an epoxide or dithiolane, preferably an epoxide. 13 ) represents an alkyl group.

[0054] In particular, the PHA copolymer is 2 is linear or branched (C1-C 28 ) alkyl, and linear or branched (C2-C 28 ) alkenyl, especially linear hydrocarbon-based groups, more especially (C 20 ) alkyl or (C3-C 20 ) alkenyl, preferably linear or branched, more particularly linear (C 20 ) alkyl.

[0055] In particular, the PHA copolymer is 2 is linear or branched (C1-C 28) alkyl, and linear or branched (C2-C 28 ) alkenyl, especially straight-chain hydrocarbon-based groups, more especially (C 20 ) alkyl or (C3-C 20 ) alkenyl; preferably, the hydrocarbon-based group is selected from the group R 1 the group R 1 The number of carbon atoms corresponds to the number of carbon atoms in

[0056] According to one embodiment of the present invention, the PHA copolymer comprises a group R 2 is a linear or branched, preferably linear, (C3-C8) alkyl, in particular a (C3-C6) alkyl, preferably a (C4-C6) alkyl, group, such as n-pentyl or n-hexyl.

[0057] According to another embodiment of the composition C1 or C1′ according to the invention, the PHA copolymer is preferably a branched (C3-C8) alkyl, in particular a (C4-C6) alkyl group R 2 , preferably a branched (C4-C5) alkyl group, such as isobutyl.

[0058] According to another embodiment of the composition C1 or C1′ according to the invention, the PHA copolymer of the invention is a copolymer having an alkyl group R 1 and the unit (B) defined above, and a linear or branched (C6-C 20 ) alkenyl, especially (C7-C 14 ) alkenyl, more particularly (C8-C 10 ) an alkenyl group, preferably linear, having a chain end 1 Those containing only one unsaturation, especially -[CR 4 (R 5 )] q -C(R 6 )=C(R 7 )-R 8 (In the formula, R 4 , R 5 , R 6 , R7 and R 8 may be the same or different and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl, preferably a hydrogen atom; q represents an integer of 2 or more and 20 or less, preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less, for example, 6), for example, -[CH2] q and a unit (C) having -CH=CH2 (wherein q represents an integer of 3 or more and 8 or less, preferably 4 or more and 6 or less, for example 5).

[0059] According to one embodiment of the composition C1 or C1' according to the invention, the PHA copolymer comprises units (A) having an alkyl group R1 containing 8 to 16 carbon atoms substituted by one or more (preferably one) groups selected from hydroxyl, (di)(C1-C4)(alkyl)amino, carboxyl and RX- as defined above, preferably RS-, where R represents a cycloalkyl group such as cyclohexyl, a heterocycloalkyl group such as a sugar, more preferably a monosaccharide such as glucose, an optionally substituted aryl(C1-C4)alkyl group such as (C1-C4)(alkyl)benzyl or phenylethyl, or a heteroaryl(C1-C4)alkyl group such as furylmethyl.

[0060] According to one embodiment of the composition C1 or C1′ according to the invention, the copolymer is preferably a copolymer having linear or branched, preferably linear, (C1-C8) alkyl, in particular (C2-C6) alkyl, preferably (C4-C5) alkyl group R 2 , for example the unit B having pentyl.

[0061] According to another embodiment of the composition C1 or C1′ according to the invention, the PHA copolymer is a copolymer having an alkyl group R 1 and the unit (B) defined above, and a linear or branched (C6-C 20 ) alkenyl, especially (C7-C 14 ) alkenyl groups, more particularly (C8-C 10 ) alkenyl groups, preferably straight-chained and containing only one unsaturation at the chain end, e.g., -[CH2]q and a unit (C) containing -CH=CH2 (wherein p represents an integer of 3 or more and 8 or less, preferably 4 or more and 6 or less, for example 5).

[0062] According to a particular embodiment of the invention, in the PHA copolymer, units (A) comprise a hydrocarbon-based chain as defined above, in particular ii), said units (A) are preferably present in a molar percentage ranging from 0.1% to 99%, more preferably in a molar percentage ranging from 0.5% to 50%, even more preferably in a molar percentage ranging from 1% to 40%, better still in a molar percentage ranging from 2% to 30%, or in a molar percentage ranging from 5% to 20%.

[0063] According to a particular embodiment of the invention, in the PHA copolymer, units (A) are preferably present in a molar percentage ranging from 0.5% to 99%.

[0064] According to one embodiment, R 1 (C5~C 28 ) alkyl group, units (A) are preferably present in a molar percentage ranging from 0.5% to 99%, more preferably from 50% to 99%, more particularly preferably from 60% to 99%, even more preferably from 70% to 99%. According to this embodiment, units (B) are preferably present in a molar percentage ranging from 2% to 40%; and units (C) are preferably present in a molar percentage ranging from 0.5% to 20%, relative to all units (A), (B) and (C).

[0065] According to another embodiment, R 1 i) linear or branched (C5-C 28 ) alkyl, ii) linear or branched (C5-C 28 ) alkenyl, iii) linear or branched (C5-C 28 ) alkynyl, preferably the hydrocarbon-based group is linear and said hydrocarbon-based chain is selected from R 1and / or interrupted by one or more heteroatoms or groups a') to c'); it is in particular linear or branched (C4-C 28 ) alkyl, optionally substituted with one or more atoms or groups a) to m) as defined above and / or interrupted by one or more heteroatoms or groups a') to c'), with respect to all units (A), (B) and (C), units (A) are preferably present in a molar percentage ranging from 0.5% to 99%, more preferably in a molar percentage ranging from 1% to 50%, even more preferably in a molar percentage ranging from 5% to 40%, more preferably in a molar percentage ranging from 5% to 30%; units (B) are present in a molar percentage ranging from 1% to 99.5%, preferably in a molar percentage ranging from 1% to 99%, more preferably in a molar percentage ranging from 2% to 98%, and units (C) are present in a molar percentage ranging from 0.5% to 20%. Advantageously, the PHA copolymer of the invention comprises from 2 mol% to 98 mol% of units (B) and from 0.5 mol% to 10 mol% of units (C); more advantageously, the copolymer comprises from 5 mol% to 70 mol% of units (B) and from 0.5 mol% to 7 mol% of units (C).

[0066] According to a more specific embodiment of the present invention, the PHA copolymer comprises in PHA copolymer a): - the units (A) contain one or more atoms or groups a) to m) as defined above and / or comprise a hydrocarbon-based chain interrupted by one or more heteroatoms or groups a') to c'), said units (A) being present in a molar percentage ranging from 0.1% to 99%, preferably in a molar percentage ranging from 0.5% to 50%, more preferably in a molar percentage ranging from 1% to 40%, even more preferably in a molar percentage ranging from 2% to 30% and better still in a molar percentage ranging from 5 mol% to 30 mol% of units (A); and - the units (B) are present in a molar percentage ranging from 1% to 99.9%, preferably in a molar percentage ranging from 2% to 99%, more preferably in a molar percentage ranging from 5% to 70% of units (B); and / or - such that units (C) are present in a molar percentage ranging from 0.5% to 20%, preferably in a molar percentage ranging from 1% to 10%, more preferably in a molar percentage ranging from 0.5% to 7% of units (C).

[0067] Preferably, R of unit (A) 1 When is a saturated unsubstituted and uninterrupted hydrocarbon-based chain, said units (A) are present in a molar percentage of more than 30%, more particularly more than 50%, more preferably more than 60%, preferably between 60% and 90%.

[0068] The mole percent values ​​of the units (A), (B) and (C) of the PHA copolymer are calculated based on the total number of moles of (A)+(B) if the copolymer does not contain an additional unit (C), otherwise, if the copolymer of the present invention contains three different units (A), (B) and (C), the mole percent is calculated based on the total number of moles of (A)+(B)+(C). Otherwise, if the copolymer of the present invention contains four different units (A), (B), (C) and (D), the mole percent is calculated based on the total number of moles of (A)+(B)+(C)+(D). Otherwise, if the copolymer of the present invention contains five different units (A), (B), (C), (D) and (E), the mole percent is calculated based on the total number of moles of (A)+(B)+(C)+(D)+(E).

[0069] According to one aspect of the invention, the PHA copolymer of the invention comprises the following repeat unit (A): optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates.

[0070] [Table 1]

[0071] In the formula, repeating units A1 to A12: - ALK1 is a divalent linear or branched C1-C 20 , preferably linear or branched, more preferably linear C1-C 10 represents a hydrocarbon-based group; - ALK2 is a divalent linear or branched C1-C 20 , preferably linear or branched C1-C 12 represents a hydrocarbon-based group; - Rr and Rw independently represent a hydrogen atom or a C1-C4 alkyl group, such as methyl; preferably, Rr and Rw are the same; - 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 a heterocycloalkyl group, such as a dithiolane or an epoxide, preferably an epoxide; Fur: ​​represents a furyl group, preferably 2-furyl; - Sug: represents a sugar group, especially a monosaccharide optionally protected by one or more groups such as acyl, especially acetyl.

[0072] In particular, the group R 1 The stereochemistry of the carbon atom having the following structure is the (R) configuration.

[0073] According to one aspect of the invention, the PHA copolymer of the invention comprises a repeat unit (B) of formula (A12), as well as optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates, where it is understood that (B) is different from (A).

[0074] Preferably, the PHA copolymers of the present invention comprise the following repeat units, as well as optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates, such as hydrates thereof: [ka]

[0075] [Table 2]

[0076] [Table 3]

[0077] [Table 4]

[0078] m and n are as defined above, Hal represents a halogen atom such as bromine, t represents an integer of 1 to 10, preferably 3 to 8, for example 6, Ar: represents a (hetero)aryl group such as phenyl; Ar': a (C1-C4) alkyl(hetero)aryl group such as t-butylphenyl, preferably 4-t-butylphenyl; Cycl: represents a cyclohexyl group; Fur: ​​represents a furyl group, preferably 2-furyl; Sug: represents a sugar group, in particular a monosaccharide optionally protected by one or more groups such as acyl; preferably, Sug is: [ka] (In the formula, R e is the group R f -C(O)-, R f represents a (C1-C4) alkyl group such as methyl.

[0079] In particular, the group R 1 and R 2 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably the (R) configuration.

[0080] More particularly, the group R 1 , R 2 and R 3The stereochemistry of the carbon atom bearing the group R is of the same (R) or (S) configuration, preferably of the (R) configuration. 1 , R 2 , R 3 and R 4 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably of the (R) configuration.

[0081] More particularly, the group R 1 , R 2 , R 3 , R 4 and R 5 The stereochemistry of the carbon atom having the formula: is of the same (R) or (S) configuration, preferably of the (R) configuration.

[0082] More preferably, the PHA copolymer has the following formula, as well as its optical isomers, its organic or mineral acid or base salts, and solvates thereof, such as hydrates. [ka]

[0083] [Table 5]

[0084] [Table 6]

[0085] [Table 7]

[0086] M, n, Hal, t, Ar, Ar', Cycl, Fur and Sug are as defined above for compounds (1) to (14). [ka]

[0087] [Table 8]

[0088] [ka]

[0089] [Table 9]

[0090] [Table 10]

[0091] [Table 11]

[0092] [Table 12]

[0093] Preferably, the PHA of the present invention is selected from compounds (2a), (10), (15), (16), (17) and (20). More preferably, the PHA of the present invention is selected from compounds (15), (16) and (17), especially (16).

[0094] More preferably, the PHA of the present invention is selected from compounds (2a'), (10'), (15'), (16') and (17'). More particularly, the PHA of the present invention is selected from compounds (15'), (16') and (17'), especially (16').

[0095] More particularly, the PHAa) of the present invention is compound (23').

[0096] Preferably, the PHAa) of the present invention is selected from compounds (25), (26), (31), (32) and (34a), more preferably, the PHAa) of the present invention is selected from compounds (25), (26), (31) and (32), in particular (26).

[0097] The PHA copolymer of the present invention preferably has a number average molecular weight in the range of 50,000-150,000.

[0098] The molecular weight can be determined in particular by size exclusion chromatography, the method of which is described below in the Examples.

[0099] The PHA copolymer is in particular present in the composition C1 according to the invention in a content ranging from 0.1% to 65% by weight, preferably in the range from 0.1% to 60% by weight, relative to the total weight of the composition; in particular in a content ranging from 1% to 50% by weight, more in particular in the range from 3% to 40% by weight, preferably in the range from 5% to 35% by weight, more preferably in the range from 10% to 30% by weight and better still in the range from 15% to 20% by weight.

[0100] Method for preparing PHA copolymers Methods for the preparation of the PHA copolymers of the present invention are known to those skilled in the art. Mention may be made of the use of "functionalizable" PHA-producing microbial strains.

[0101] The term "functionalizable" means that the PHA copolymer comprises a hydrocarbon-based chain that comprises one or more atoms or groups that can chemically react with another reagent, also called "reactive atom or reactive group", to give a Σ covalent bond with said reagent. The reagent is, for example, a compound that comprises at least one nucleophilic group, and said functionalized hydrocarbon-based chain comprises at least one electrophilic or nucleofugic atom or group, which reacts with the electrophilic group to covalently graft the reagent Σ. The nucleophilic reagent also reacts with one or more unsaturations of the alkenyl group to give a covalent graft of the functionalized hydrocarbon-based chain with said reagent. The addition reaction can also be a radical-based, Markovnikov or reverse-Markovnikov type addition, or a nucleophilic or electrophilic substitution. The addition or condensation reaction may or may not be carried out via a radical route, may or may not use a catalyst or enzyme, and may be carried out with heating, preferably to a temperature of up to 100° C., or without the supply of heat, under a pressure of 1 atmosphere or more, under an inert atmosphere, or under oxygen, or otherwise.

[0102] "Nucleophilic" refers to an atom or group that exhibits electron donating properties through an inductive effect +I and / or a mesomeric effect +M. Electron donating groups that may be mentioned include hydroxyl groups, thiol groups, amino groups.

[0103] "Electrophilic" refers to any atom or group that exhibits electron-withdrawing properties by inductive effect -I and / or mesomeric effect -M. Electron-withdrawing species that may be mentioned include:

[0104] Microorganisms producing PHAs, particularly those having a hydrocarbon-based chain, according to the invention may be naturally produced by the kingdom Bacteria, for example by cyanobacteria of the order Nostocales (e.g. Nostoc muscorum, Synechocystis and Synechococcus), but mainly by the phylum Proteobacteria, for example the following classes: - Beta-proteobacteria of the order Burkholderiales (Cupriavidus negator synonym Ralstonia eutropha) - Alpha-proteobacteria of the order Rhodobacteriales (Rhodobacter capsulatus marine and photosynthetic) - A gamma-proteobacterium (Acinetobacter junii) of the order Pseudomonales, family Moraxellaceae.

[0105] Among the microorganisms of the kingdom bacteria, the genera Azotobacter, Hydrogenomomas or Chromatium are representative of PHA-producing organisms.

[0106] Organisms which naturally produce PHAs, in particular having a C3-C5 hydrocarbon-based chain, are in particular Proteobacteria, such as Gamma-Proteobacteria, more particularly those of the family Pseudomonadaceae, order Pseudomonales, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida. Pseudomonas putida GPo1 and Pseudomonas putida KT2440, preferably Pseudomonas putida, in particular Pseudomonas putida GPo1 and Pseudomonas putida KT2440.

[0107] Also, certain organisms can naturally produce PHA without belonging to the order Pseudomonales, such as Commamonas testosteroni, which belongs to the class of Beta-proteobacteria in the order Burkholderiales in the family Comamonadaceae.

[0108] Furthermore, the PHA-producing microorganism according to the present invention may be a recombinant strain when it has a 3-oxidized PHA synthase metabolic pathway, which is mainly represented by EC:2.3.1 B2, EC:2.3.1 B3, EC:2.3.1 B4, and EC:2.3.1 B5.

[0109] The recombinant strain may be from the bacterial kingdom, e.g., Escherichia coli, or from the plant kingdom, e.g., Chlorella pyrenoidosa (International Journal of Biological Macromolecules, 116, 552-562 “Influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (PHAs) by microalgae”) or from the fungal kingdom, e.g., Saccharomyces cerevisiae or Yarrowia lipolytica: Applied Microbiology and Biotechnology 91, 1327-1340 (2011) “Engineering polyhydroxyalkanoate content and monomer composition in the oleaginous yeast Yarrowia lipolytica by modifying the β-oxidation multifunctional protein”).

[0110] It is also possible to use genetically modified microorganisms, which may make it possible, for example, to increase the production of PHA and / or to increase the oxygen consumption capacity and / or to reduce autolysis and / or to modify the monomer ratio.

[0111] It is known that in the case of PHA, a large part of the total production cost is spent on the culture medium, mainly the substrate / carbon source, so genetically modified microorganisms that grow using a smaller amount of nutrient (carbon source), such as microorganisms that are photoautotrophic in nature, i.e., that use light and CO2 as the main energy source, can be used.

[0112] The copolymers can be biosynthesized in a known manner, for example from microorganisms belonging to the genus Pseudomonas, such as Pseudomonas resinovorans, Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis, preferably Pseudomonas putida; C2-C 20 , preferably C6 to C 18 carboxylic acids, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; monosaccharides, such as fructose, maltose, lactose, xylose, arabinose, etc.; n-alkanes, such as hexane, octane or dodecane; n-alcohols, such as methanol, ethanol, octanol or glycerol; and a carbon source which may be methane or carbon dioxide.

[0113] This biosynthesis can optionally be carried out in the presence of an inhibitor of the β-oxidation pathway, such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid, or phenylpropionic acid, preferably acrylic acid.

[0114] According to one embodiment, the process for preparing the PHA of the present invention uses microbial cells that produce PHA via genetically modified microorganisms (GMOs). The genetic modification can increase PHA production, increase oxygen absorption capacity, increase resistance to solvent toxicity, reduce autolysis, modify the ratio of PHA comonomers, and / or any combination thereof. In some of these embodiments, modifying the comonomer ratio of unit (A) increases the amount of the predominant monomer relative to (B) in the resulting PHA of the present invention. In another embodiment, the PHA-producing microbial cells are naturally propagated.

[0115] As an example, a genetically engineered microbial strain that produces PHAs containing reactive groups that can be functionalized or referred to as functionalizable is Pseudomonas entomophila LAC23 (Biomacromolecules. 2014 Jun 9;15(6):2310-9. doi:10.1021 / bm500669s).

[0116] It is also possible to use genetically modified microorganisms that produce phenylvaleric-co-3-hydroxydodecanoic acid copolymers using strains such as Pseudomonas entomophila LAC23 (Sci. China Life Sci., Shen R. et al., 57 No. 1, (2014)).

[0117] Nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium and iron may also be used in this biosynthesis.

[0118] Microbial cultivation requires temperature, pH, and dissolved oxygen (O D ) can be used.

[0119] The microorganisms can be cultured according to any known culture method, for example in a bioreactor in continuous or batch mode, fed or unfed mode.

[0120] The biosynthesis of the polymers used according to the invention is described in particular in the article "Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer", Xun Juan et al., Biomacromolecules 2012, 13, 2926-2932, and in WO 2011 / 069244.

[0121] Microbial strains producing PHAs which are functionalizable or which contain reactive groups as defined above are, for example, strains of the genus Pseudomonas, such as P. cichorii YN2, P. citronellolis, P. jessenii, and more generally Pseudomonas putida GPo1 (synonymous with Pseudomonas oleovorans), P. putida KT2442, P. putida KT2440, P. putida KCTC 2407 and P. putida BM01. putida species, in particular P. putida KT2440.

[0122] Carbon source: One means for gaining access to the PHA of the present invention is to introduce into the culture medium one or more organic compounds, which or these organic compounds preferably represent one or more carbon sources selected from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof.

[0123] In one embodiment, the organic compound is preferably selected from alcohols, carboxylic acids and mixtures thereof.

[0124] Carbon sources can be divided into two categories.

[0125] 1) A carbon source via one or more organic compounds introduced into the medium: According to a particular embodiment of the invention, the organic compound is an alcohol, in particular (C5-C 20 ) alkanols, and / or carboxylic acids, in particular optionally substituted and / or interrupted (C5-C 20 ) Alkanoic acids, especially (C5-C 20 ) Alkanoic acids, e.g. (C7-C 11 ) alkanoic acid, such as nonanoic acid or pelargonic acid, and / or (C 20 ) Alkenic acids, especially (C5-C 20 ) Alkenic acids, e.g. (C7-C 11 ) alkenoic acids, such as undecylenic acid, and mixtures thereof.

[0126] Carbon sources can be classified into three groups according to their intended use. - Group A: The organic compounds may aid in the growth of the producing strain and aid in the production of PHA structures linked to the organic compounds. - Group B: The organic compounds may aid the growth of the strain, but are not involved in the production of structural PHAs linked to the organic compounds. - Group C: Organic compounds do not contribute to the growth of the strain.

[0127] Such microbiological methods are known to those skilled in the art and are described in particular in the scientific literature: the following may be mentioned: International Journal of Biological Macromolecules 28, 23-29 (2000); The Journal of Microbiology, 45, No. 2, 87-97, (2007).

[0128] According to one variant, the integration of a substrate structurally linked to a reactive atom or reactive group of the PHA of the invention is directly introduced into the medium as the sole carbon source in a medium suitable for the growth of a microorganism (e.g. Group A: alkenoic acids, especially terminal, for P. putida GPo1).

[0129] According to another variant, the integration of a substrate structurally linked to a reactive atom, in particular a halogen or reactive group, of the PHA of the present invention is introduced into the medium as a carbon source in a medium suitable for the growth of a microorganism together with a second carbon source as a co-substrate also structurally linked to the PHA (e.g. Group B for P. putida GPo1: haloalkanoic acids, preferably terminal, such as terminal bromoalkanoic acids).

[0130] According to yet another variant, the integration of a substrate structurally linked to a reactive atom, in particular a halogen or reactive group, of the PHA of the present invention can be directly introduced into the medium as a carbon source in a medium suitable for the growth of a microorganism, together with a second carbon source as a co-substrate that is also structurally linked to the PHA and a third carbon source as a co-substrate that is not structurally bound to the PHA (e.g., group C glucose or sucrose).

[0131] 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.

[0132] 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.

[0133] The functionalization can be introduced by organic compounds chosen from the classes of precursors of alcohols and / or carboxylic acids, in particular: - for the functionalization of PHAs with branched alkyl groups, see, for example, Applied and Environmental Microbiology, 60, No. 9, 3245-325 (1994); - for the functionalization of PHAs with linear alkyl groups containing terminal cyclohexyl units, see for example: doi.org / 10.1016 / S0141-8130(01)00144-1; for the functionalization of PHAs with unsaturated alkyl groups, preferably terminal, see for example: doi.org / 10.1021 / bm8005616); - for the functionalization of PHAs with linear alkyl groups, preferably containing halogens at the end of the hydrocarbon-based chain, see (doi.org / 10.1021 / ma00033a002); - for the functionalization of PHA with (hetero)aromatic alkyl groups, such as phenyl, benzoyl, phenoxy, see, for example, J. Microbiol. Biotechnol., 11, 3, 435-442 (2001); - for the functionalization of PHAs with linear alkyl groups, in particular those containing heteroatoms at the end of the hydrocarbon-based chain, see for example DOI 10.1007 / s00253-011-3099-4; - for the functionalization of PHAs with linear alkyl groups, in particular those containing a cyano function at the end of the hydrocarbon-based chain, see for example doi.org / 10.1111 / j.1574-6968.1992.tb05839.x; - for the functionalization of PHAs with linear alkyl groups, in particular those containing epoxy functional groups at the end of the hydrocarbon-based chain, see for example doi.org / 10.1016 / S1381-5148(97)00024-2.

[0134] The review in International Microbiology 16:1-15 (2013) doi:10.2436 / 20.1501.01.175 also mentions major functionalized native PHAs.

[0135] In a particular embodiment of the invention, the fatty acids from group A are selected from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and 5-cyanopentanoic acid.

[0136] In certain embodiments of the invention, the fatty acids from group A are selected from halooctanoic acids, such as 8-bromooctanoic acid.

[0137] In a particular embodiment of the invention, the carbon source from group C is a monosaccharide, preferably glucose.

[0138] 2) Carbon source in the presence of antioxidants introduced into the medium: Another aspect of the invention is the use of a PHA-producing microbial strain in a medium suitable for the growth of the microorganism, said medium comprising a substrate structurally linked to the PHA, at least one carbon source not structurally linked to the PHA, and at least one oxidation, in particular β-oxidation pathway inhibitor, whereby the growth of the microbial cells is carried out in said medium, and the microbial cells synthesize a PHA polymer of the invention, preferably a copolymer, in particular comprising more than 95% identical units, the comonomer ratio of units (A) and units (B) being different from that obtained in the absence of the β-oxidation pathway inhibitor.

[0139] The following schemes show, by way of example, the functionalization of a PHA copolymer according to the invention, starting from a PHA copolymer having an unsaturated hydrocarbon-based chain, according to Scheme 1 below. [ka] In Scheme 1, - R 2 , m and n are as defined above; - Y is Hal, such as chlorine or bromine, hydroxyl, thiol, (di)(C1-C4)(alkyl)amino, α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as a sugar, preferably a monosaccharide, such as glucose, γ) (hetero)aryl, such as phenyl, δ) a cosmetic active agent as defined above, ε) (C1-C 20 ) Alkyl, (C2-C 20 ) alkenyl, (C2-C 20 a) R representing a group selected from alkynyl, and a') O, S, N(Ra ) or Si(R b )(R c ) or e) linear or branched (C1-C 20 ) Alkyl (R a , R b and R c is as defined above); q' represents an integer of 2 or more and 20 or less, preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less, for example, 6, more preferably 3 or more and 8 or less, preferably 4 or more and 6 or less, for example, 5.

[0140] Other reactions may be carried out using reactions with double or triple unsaturations such as Michael or Diels-Alder additions, radical reactions, catalytic or uncatalyzed hydrogenation reactions (especially with Pd or Ni), halogenation reactions, especially with bromine, hydration or oxidation reactions, which may be controlled or not, and may be carried out on electrophiles as represented diagrammatically below:

[0141] According to a particular embodiment of the invention, the PHA copolymer comprises: - R 1 a linear or branched saturated hydrocarbon-based chain R containing a total of 5 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more particularly 7 to 11 carbon atoms, substituted and / or interrupted by groups as defined above for 1 ,and - Linear or branched (C3-C 20 ) alkenyl, especially (C5-C 14 ) alkenyl, more particularly (C7-C 10 ) a hydrocarbon-based chain R representing an alkenyl group 2 which are preferably linear and contain only one unsaturation at the chain end, in particular -[CR 4 (R 5 )] q -C(R 6 )=C(R 7 )-R 8 (In the formula, R 4 , R5 , R 6 , R 7 and R 8 may be the same or different, and represent a hydrogen atom or a (C1-C4) alkyl group such as methyl, preferably a hydrogen atom; q represents an integer of 2 or more and 20 or less, preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less, for example, 6), for example, -[CH2] q -CH=CH2 (q is an integer of 3 or more and 8 or less, preferably 4 or more and 6 or less, for example, 5) and the chain R 2 contains 1% to 99%, preferably 2% to 50%, more preferably 3% to 40% unsaturation, more particularly 3% to 30% unsaturation, and better still 5% to 20% unsaturation. According to this particular embodiment of the invention in which the PHA copolymer contains unsaturation, these unsaturations are A) The particles may be chemically modified by addition reactions with chemical compounds or polymers, such as radical addition, Michael addition, electrophilic addition, Diels-Alder, halogenation, hydration or hydrogenation reactions, preferably hydrothiolation reactions.

[0142] In particular, the hydrothiolation reaction can be carried out using a thermal, redox or photochemical initiator and an organic compound having a sulfhydryl group, in particular - 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- or 2-furanmethane-thiol, preferably hexane-, cyclohexane-, heptane-, octane-, phenylethane-, 4-tert-butylphenylmethane- or 2-furanmethane-thiol; - organosiloxanes containing thiol functional groups, such as (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldimethoxysilane, 2-(triethoxysilyl)ethanethiol or mercaptopropyl-isobutyl-POSS; - thiolated silicone oils, in particular those described in the literature (DOI: 10.1016 / j.actbio.2015.01.020); - amines, alcohols, acids, halogens, thiols, epoxides, nitriles, isocyanates, heteroatoms, preferably cysteine, cysteamine, N-acetylcysteamine, 2-mercaptoethanol, 1-mercapto-2-propanol, 8-mercapto-1-octanol, thiolactic acid, thioglycolic acid, 3-mercaptopropionic acid, 11-mercaptoundecanoic acid, polyethylene glycol, 3-mercaptopropionitrile, 1,3-propanedithiol, 4-cyano-1-butanethiol, 3-chloro-1-propanethiol, 1-thio-β-D-glucose tetraacetate thiolated oligomers or polymers having reactive functional groups such as - thiols obtainable from disulfide reduction, such as phenyl disulfide or furfuryl disulfide The method may be carried out in the presence of a compound selected from:

[0143] Examples of initiators that may be mentioned include tert-butylperoxy-2-ethylhexanoate, cumene perpivalate, tert-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-diisopropyl)-2,2'-azobis(2,4-diphenylmethane), ... methylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,4-bis(tert-butylperoxycarbonyl)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl 4,4-bis(tert-butylperoxy)valerate, 2,2-bis (tert-butylperoxy)butane, 1,3-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, di-tert-butyldiperoxyisophthalate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butylperoxy-α-methylsuccinate, di-tert-butylperoxydimethylglutarate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, diethylene glycol bis(tert-butylperoxycarbonate), di-tert-butylperoxytrimethyladipate, tris(tert-butylperoxy)triazine, vinyltris(tert-butylperoxy)silane Phenothiazine, tetracene, perylene, anthracene, 9,10-diphenylanthracene, thioxanthone, benzophenone, acetophenone, xanthone, fluorenone, anthraquinone, 9,10-dimethylanthracene, 2-ethyl-9,10-dimethyloxyanthracene, 2,Examples of initiators include 6-dimethylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, xanthopinacol, 1,2-benzanthracene, and 9-nitroanthracene. These initiators may be used alone or in combination with one another.

[0144] The above chemical reactions are known to those skilled in the art. In particular, the following documents may be mentioned: Synthesis and preparation of PHAs modified with polyethylene glycol dithiol: 10.1021 / acs.biomac.9b00479; Biomacromolecules, 19, 3536-3548 (2018); Synthesis and preparation of PHAs modified with mercaptohexanol: 10.1021 / acs.biomac.8b01257; Biomacromolecules, 20, 2, 645-652 (2019); Synthesis and preparation of PHAs modified with hydroxycinnamic acid sulfate, and zosteric acid: acid):10.1021 / bm049962e;Biomacromolecules,5,4,1452-1456(2004);Radical addition of methyl methacrylate to a PHOUn:10.1002 / 1521-3935(20010701)202:11<2281:AID-MACP2281>3.0.CO;2-9;Macromolecular Chemistry and Physics,vol.202,11,2281-2286(2001);Synthesis and preparation of PHAs modified with a polysilsesquioxane(POSS):10.1016 / j.polymer.2005.04.020;Polymer Vol.46,14,5025-5031(2005);Grafting of thio-beta-glucose onto saturated side chains:1022-1336 / 99 / 0202-0091$17.50+.50 / 0;Macromol.Rapid Commun.,20,91-94(1999);. and / or B) Via oxidation reactions, which may or may not be controlled, for example by concentrated or dilute alkaline permanganates, or ozonolysis, oxidation in the presence of reducing agents, it is possible to obtain novel substances which have hydroxyl, epoxy or carboxyl groups in the terminal positions of the side chains.

[0145] The above chemical reactions are known to those skilled in the art. The following documents may in particular be mentioned: 10.1021 / bm049337; Biomacromolecules, vol. 6, 2, 891-896 (2005); 10.1016 / S0032-3861(99)00347-X; Polymer, vol. 41, 5, 1703-1709 (2000); 10.1021 / ma9714528 and 10.1016 / S1381-5148(97)00024-2;Macromolecules,23,15,3705-3707(1990);10.1016 / S0032-3861(01)00692-9;Polymer,vol.43,4,1095-1101(20 02);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).

[0146] Example of functionalization of a PHA copolymer according to the invention starting from a PHA copolymer having a hydrocarbon-based chain containing epoxide groups according to the following scheme 2: [ka] In Scheme 2, Y, m, n, q′ and R2 is as defined in Scheme 1.

[0147] The epoxide structures can be obtained via conventional methods known to those skilled in the art, whether via biotechnical or chemical processes such as oxidation of the above unsaturations. The peroxide groups can be reacted with carboxylic acids, maleic anhydrides, amines, alcohols, thiols or isocyanates, all of which are required to react with at least one linear or branched, cyclic or acyclic, saturated or unsaturated C1-C 20 They may contain hydrocarbon-based chains or may react with oligomers or polymers, in particular amino(poly)saccharides, such as compounds derived from chitosan and (poly)sil(oxy)anes, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3-(trimethoxysilyl)propylcarbamic acid, diethanolamine, or alkali metal or alkaline earth metal salts, such as sodium, of 3-mercapto-1-propanesulfonic acid. Epoxide groups may also react with water.

[0148] In particular the following documents may be mentioned: - Preparation of PHA bearing charges starting with diethanolamine: 10.1021 / bm8005616, Biomacromolecules, vol. 9, 8, 2091-2096 (2008); - Preparation of PHA bearing charges starting with sodium 3-mercapto-1-propanesulfonate: 10.1021 / acs.biomac.9b00870 Biomacromolecules, vol. 20, 9, 3324-3332 (2019); - Preparation of PHA including a native epoxide unit: 10.1016 / S1381-5148(97)00024-2; Reactive and Functional Polymers, vol. 34, 1, 65-77 (1997).

[0149] Example of functionalization of a PHA copolymer according to the invention, starting from a PHA copolymer having a hydrocarbon-based chain containing a nucleofugic group, according to the following scheme 3: [ka] In Scheme 3, Y, m, n, q′ and R 2 is as defined in scheme 1. M corresponds to an organic or inorganic nucleofugic group that can be substituted by a nucleophilic group, preferably said nucleophilic group is a heteroatom that donates electrons via the +I and / or +M effect, such as O, S or N. Preferably, the nucleophilic group M is selected from a halogen atom, such as Br, a mesylate, tosylate or triflate group. This is a reaction known to those skilled in the art. For example, the following literature may be mentioned: 10.1016 / j.ijbiomac.2016.11.118, International Journal of Biological Macromolecules, vol.95,796-808(2017).

[0150] Example of functionalization of a PHA copolymer according to the invention starting from a PHA copolymer having a hydrocarbon-based chain containing a cyano group according to Scheme 4 below: [ka] In Scheme 4, Y, m, n, q' and R 2 is as defined in Scheme 1.

[0151] In a first step i), a PHA copolymer having a side chain containing a cyano or nitrile group is reacted with an organoalkali metal or organomagnesium compound Y-MgHal, Y-Li or Y-Na, followed by hydrolysis to obtain a PHA copolymer having a side chain containing a group Y grafted by a ketone function. The ketone function can be converted, for example, by thionation with S8 in the presence of an amine, or by Lawesson's reagent. The thioketone, after total reduction ii) (for example by Clemmensen reduction), gives a PHA copolymer having a side chain containing a group Y grafted by an alkylene group. Alternatively, the thioketone can be subjected to a controlled reduction iii) with conventional reducing agents to obtain a PHA copolymer having a side chain containing a group Y grafted by a hydroxyalkylene group. The cyano group of the starting PHA copolymer can be reacted with water to obtain an amide derivative after hydration v) and hydrolysis iv) to the carboxyl derivative. Also, the cyano groups of the starting PHA copolymer can be reduced to give amine or ketone derivatives after reduction vi). PHA copolymers with a hydrocarbon-based chain containing nitrile functional groups are prepared via conventional methods known to those skilled in the art. For example, the following literature can be mentioned: 10.1016 / 0378-1097(92)90311-B, FEMS Microbiology Letters, vol.103,2-4,207-214(1992).

[0152] Example of functionalization of a PHA copolymer according to the invention starting from a PHA copolymer having a hydrocarbon-based chain at the chain end according to the following scheme 5: [ka] In Scheme 5, R 1 , R 2 , m, n and Y are as defined above, and R′1 is i) linear or branched (C1-C 20 ) alkyl, ii) linear or branched (C2-C 20 ) alkenyl, iii) linear or branched (C2-C 20and f) alkynyl; preferably, the hydrocarbon-based group is linear and the hydrocarbon-based chain is selected from a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C1-C4)(alkyl)amino, e) (thio)carboxyl, f) (thio)carboxamido-C(O)-N(R a )2 or -C(S)-N(R a ) 2, f) cyano, g) iso(thio)cyanato, h) (hetero)aryl such as phenyl or furyl, and i) (hetero)cycloalkyl such as anhydride or epoxide, j) colored or colorless, fluorescent or non-fluorescent chromophores, e.g. those derived from optical brighteners or chromophores derived from UVA and / or UVB screening agents, and cosmetic active agents selected from anti-aging active agents.

[0153] These chain end grafts onto PHA polymers are known to those skilled in the art. For example, the following documents may be mentioned: -Preparation of PHA oligomers by thermal degradation: 10.1021 / bm0156274; Biomacromolecules, vol. 3, 1, 219-224 (2002); -Preparation of PHA oligomers by transesterification: 10.1021 / ma011420r, Macromolecules, vol. 35, 3, 684-689 (2002); -Preparation of PHA oligomers by hydrolysis: 10.1016 / 0032-3861(94)90590-8 Polymer vol.35,19,4156-4162(1994); -Preparation of PHA oligomers by methanolysis: 10.1021 / bm060981t, Biomacromolecules, vol. 8, 4, 1255-1265 (2007).

[0154] Other methods known to those skilled in the art may also be mentioned: -Synthesis and characterization of PHA grafted with ascorbic acid:10.1016 / j.ijbiomac.2018.11.052;International Journal of Biological Macromolecules,vol.123:7(2019); -Preparation of PHB-b-PHO copolymers by polycondensation with divinyl adipate catalysed with a lipase: 10.1021 / bm9011634, Biomacromolecules, vol. 10, 12, 3176-3181 (2009); -Synthesis of PHB-b-PHO copolymers coupled via a diisocyanate junction: 10.1021 / ma012223v; Macromolecules, vol. 35, 13, 4946-4950 (2002); -Preparation of PHO oligomers on chitosan by condensation between the carboxylic acid end of the PHO and the amine functions of the chitosan:10.1002 / app.24276;Journal of Applied Polymer Science,vol.103,1,(2006); -Transesterification of PHAs with propargyl alcohol in order to produce PHA oligomers that are modifiable by “click” chemistry: 10.1016 / j.reactfunctpolym.2011.12.005; Reactive and Functional Polymers, vol. 72, 2, 160-167 (2012); -Preparation of PHO-b-PCL copolymer: 10.1002 / mabi.200400104; Macromolecular Bioscience, vol. 4, 11 (2004); -Preparation of PHO-b-PEG copolymer: 10.1002 / macp.201000562; Macromolecular Chemistry and Physics; vol. 212, 3, (2010); -Epoxidation of chain-end unsaturation and chain-end grafting of acid: 10.14314 / polimery.2017.317;Polimery,vol.62,4,317-322(2017); -Grafting of organosiloxane unit at chain end onto PHA: 10.1016 / j.reactfunctpolym.2014.09.008; Reactive and Functional Polymers, vol. 84, 53-59 (2014).

[0155] Combination of the above grafted PHA copolymers of the present invention according to Scheme 6: [ka] In Scheme 6, R' 1 , R 2 , m, n and Y are as defined above, and X' represents a reactive atom or group capable of reacting with an electrophilic E or nucleophilic Nu atom or group to form a Σ covalent bond, and when X' is an electrophilic or nucleophilic group, the reagent R' 1 -Nu, and when X' is a nucleophilic group Nu, R' 1 It can react with -E to form a Σ covalent bond.

[0156] As an example, the Σ covalent bonds or linking groups that can result from the condensation of electrophiles and nucleophiles are given in the table below.

[0157] [Table 13]

[0158] [Table 14]

[0159] It is also possible to start with a PHA functionalized on the side chain and perform the chain end grafting in a second step, as depicted in Scheme 7. It is also possible vice versa, that the chain end grafting is performed in a first step and then the functionalization of the functionalizable side chain in a second step. [ka] In Scheme 7, R' 1 , R 2 , m, n and Y are as defined above.

[0160] All these chemical reactions are known to those skilled in the art. For example, the following documents may be mentioned: -Synthesis and preparation of PHAs modified with thiol-ene followed by reaction on the new grafted function: 10.1021 / ma0304426; Macromolecules, vol. 37, 2, 385-389 (2004); -Grafting of PEG and of PLA onto PHAs functionalized with acids: 10.1002 / marc.200900803 and 10.1002 / mabi.200390033; -Synthesis and preparation of PHAs modified with polyethylene glycol dithiol: 10.1021 / acs.biomac.9b00479.

[0161] b) Crystalline fatty substances The composition C1 or C1' according to the invention comprises at least one crystalline fatty substance.

[0162] The term "fatty substances" refers to organic compounds that are insoluble in water (solubility less than 5%, preferably less than 1%, even more preferably less than 0.1%) at room temperature (25°C) and atmospheric pressure (760 mmHg). They have in their structure at least one hydrocarbon-based chain containing at least 6 carbon atoms or at least two strings of siloxane groups. Moreover, fatty substances are generally soluble in organic solvents, such as chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane, under the same temperature and pressure conditions.

[0163] The crystalline fatty substances of the invention are of natural or synthetic origin, preferably natural, more preferably of vegetable or animal origin from insects. Salified fatty acids generally differ from fatty acids, since they constitute soaps that are soluble in aqueous media.

[0164] For the purposes of the present invention, the term "crystalline fatty substance" means a deformable or non-deformable lipophilic compound which is solid at room temperature (25°C) and atmospheric pressure and has a melting point above 25°C, preferably between 25°C and 200°C, more preferably between 25°C and 120°C.

[0165] Some crystalline fatty substances are commonly referred to as waxes.

[0166] wax According to a particular embodiment, the composition C1 or C1' of the invention comprises one or more waxes.

[0167] The term "wax" means a lipophilic compound, which is solid at room temperature (25° C.) and atmospheric pressure, with a reversible solid / liquid state change, and has a melting point of 30° C. or higher, which may be up to 200° C., in particular 120° C. In particular, waxes suitable for use in the present invention may have a melting point of 45° C. or higher, in particular 55° C. or higher.

[0168] Melting point, within the meaning of the present invention, corresponds to the temperature of the maximum of the endothermic peak observed in thermal analysis (DSC), as described in ISO standard 11357-3:1999. The melting point of a crystalline fatty substance can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold by TA Instruments under the name MDSC 2920. Such a measurement method is described, for example, in PCT / EP2013 / 062964.

[0169] According to a particular embodiment of the invention, the composition C1 or C1' of the invention is solid, in particular anhydrous. It may be in the form of a stick, and in order to reduce or even eliminate the presence of layers in the solid composition, a polyethylene microwax in microcrystalline form will be used, having an aspect ratio at least equal to 2 and a melting point ranging from 70 to 110°C, preferably from 70 to 100°C. These needle-like crystallites, in particular their dimensions, can be characterized visually according to the method described above.

[0170] Paste-like compound According to a particular embodiment, the composition of the invention comprises b) one or more pasty compounds.

[0171] For the purposes of the present invention, the term "pasty compound" means a lipophilic fatty compound which undergoes a reversible solid / liquid state change, has an anisotropic crystalline structure in the solid state and comprises, at a temperature of 23° C., a liquid fraction and a solid fraction.

[0172] Among the crystalline fatty substances i) of fossil origin, mention may be made of 1) paraffin wax, 2) ozokerite, 3) ceresin and 4) microcrystalline waxes, especially those containing from 20 to 60 carbon atoms.

[0173] According to a particular embodiment of the invention, the crystalline fatty substance is of natural origin, in particular ii) of vegetable origin. The following may be mentioned: 5) carnauba wax, 6) candelilla wax, such as the product sold under the name SP 75 G by Strahl & Pitsch, 7) laurel wax, especially oleander wax, 8) sugar cane wax, 9) ceramides, 10) esparto wax, 11) olive tree wax, 12) rice wax, such as the product sold under the name NC 1720 by Cera Rica Noda, 13) sunflower seed wax, such as the product sold under the name Sunflower wax by Koster Keunen, 14) hydrogenated jojoba wax, 15) hydrogenated castor oil, 16) hydrogenated olive oil, 17) hydrogenated cottonseed oil, 18) polyglyceryl-3 esters of green mimosa, jojoba and sunflower wax, 19) absolute flower waxes, such as blackcurrant flower essential wax, 20) soy wax, 21) myrica fruit wax.

[0174] Other vegetable waxes may also be used as crystalline fatty substance b) according to the invention, in particular the following waxes: 22) Karandai wax, 23) Raffia wax, 24) Colombian wax, 25) Esparto wax, 26) Alfalfa wax, 27) Bamboo wax, 28) Hemp wax, 29) Douglas fir wax, 30) Cork wax, 31) Sisal wax, 32) Linseed wax, 33) Cotton wax, 34) Dammar wax, 35) Cereal wax, 36) Tea wax, 37) Coffee wax, 38) Okatira wax, 39) Palm wax, 40) Myrica wax, 41) Bayberry wax, 42) Ukuba wax, 43) Borneo wax, 44) Malabar wax, 45) Illipe wax and 46) Japan tallow wax or Japan wax, preferably Japan wax.

[0175] According to a particular embodiment of the invention, the crystalline fatty substance b) is 46) Japan wax. Japan wax is a wax obtained from the seeds of the sumac (Rhus succedanea) berry, native to Japan. It contains various fatty acids such as stearic acid, palmitic acid and heneicosyl acid, as well as certain C21 acids.

[0176] According to another particular embodiment of the invention, the crystalline fatty substance is iii) of animal origin and is in particular selected from 47) beeswax, 48) modified beeswax (Serra Verina), 49) lanolin and 50) spermaceti.

[0177] In particular, the crystalline fatty substance is selected from beeswax, which in particular comprises 60% to 90%, in particular 70% to 80% wax esters, 5% to 20%, in particular 10% to 15% by weight of free acids, 5% to 30%, in particular 10% to 20% by weight of paraffins, with small amounts of alkenes, isoparaffins, cholesterol esters and pollen pigments, the remainder being volatile diesters and triesters (Ullmann's Encyclopedia of Industrial Chemistry, "Waxes", E. Krendlinger, 2015 Wiley-VCH Verlag GmbH & Co KGaA, Weinheim 10.1002 / 14356007.a28_103.pub2).

[0178] Mention may also be made of more specialised beeswaxes, such as, for example, Gedda wax (Asia Apis indica, A. florea, A. dorsata), which may in particular be mixed with Indian beeswax, which contains 50% to 95% by weight of wax esters (in particular 78% to 80% by weight of wax esters), 1% to 10% by weight (for example 4%) of glycerides (fats), 2% to 8% by weight (in particular 5% to 6%) of free acids, 6% to 10% by weight (in particular 8% to 9%) of hydrocarbons and 0.5% to 4% by weight (in particular 1% to 2%) of partially resinous impurities. The acids in particular include 7- and 16-hydroxypalmitic acid and 7,16-dihydroxymargaric acid.

[0179] Mention may also be made of shellac wax from the resin exudate of the insect Laccifer lacca (formerly Tachardia lacca) of the Coccidae family, 51) this product being known as shellac, similar to beeswax, and essentially C 12 ~C 18 Even-numbered fatty acids (15% to 30% by mass, particularly 21% to 26% by mass of the total acids) and waxy acids (C 28 ~C 34 , mainly C 32 and C 34 ) in admixture with trihydroxypalmitic acid (aloe uronic acid). A particular component is trihydroxypalmitic acid (aloe uronic acid), which is present only in small amounts, specifically 0.5% to 1.0%. 28 ~C 32 Among alcohols, C 28 Components predominate (50% to 70% by weight, especially 62% to 65% of the total alcohol). The main hydrocarbon-based components are paraffins containing 27, 29 and 31 carbon atoms (Ullmann's Encyclopedia of Industrial Chemistry, "Waxes", E. Krendlinger, 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a28_103.pub2).

[0180] Crystalline fatty substances also include long chain crystalline alcohols and mixtures thereof, such as cetearyl alcohol (50 / 50 C 16 / C 18 ), stearyl alcohol, myristyl alcohol, cetyl alcohol and C 26 ~C 22 It may also be selected from alcohols.

[0181] The crystalline fatty substances may also be long chain crystalline esters and mixtures thereof, such as the INCI compound "cetyl ester (and) cetyl ester mixture of myristyl stearate and myristyl palmitate", or the INCI compound "myristyl stearate and myristyl palmitate mixture", myristyl myristate, behenyl behenate, glycol distearate, glycol stearate, cetyl palmitate, such as the product Ercawax CP V / O, isopropyl palmitate, C, available from the supplier Erca. 20 ~C 40 They may be chosen from alkyl stearates, long-chain crystalline esters of glycerol and mixtures thereof, such as the compound sold under the name Compritol 888 CG ATO by Gattefosse (INCI: glyceryl dibehenate (and) tribehenin (and) glyceryl behenate), or each of its components taken separately, tricaprin, trilaurin, trimyristin, tripalmitin, tristearin, glycerol distearate, glyceryl dipalmitate / stearate and linoleoyl polyoxyl-6 glycerides.

[0182] In one embodiment of the invention, the crystalline fatty substance b) is selected from fatty alcohols, glycol esters, glyceryl esters and glycerol esters. In one or more embodiments, the fatty substance comprises hydrogenated vegetable oil and glycol distearate.

[0183] Crystalline fatty substances also include crystalline fatty acids with long alkyl chains and mixtures thereof, such as the INCI compound "stearic acid", a mixture of stearic acid and palmitic acid, especially saturated C4-C 28 Fatty acids and unsaturated C4~C 28 It may be selected from fatty acids.

[0184] Other crystalline fatty substances which can be used according to the invention are in particular marine waxes, synthetic beeswax, synthetic microcrystalline waxes, polyethylene waxes or polyolefin waxes in general, such as α-oligomers of olefins, for example the polymers Performa V® 825, 103 and 260 sold by New Phase Technologies, ethylene / propylene copolymers, for example Performalene® EP 700, or Fischer-Tropsch waxes or mixtures thereof.

[0185] Preferably, the crystalline fatty material is C 10 ~C 36 Fatty alcohol and / or C 12 ~C 38 The crystalline mono / di / triesters are selected from fatty acid derived crystalline mono / di / triesters, and mixtures thereof.

[0186] According to a particular embodiment of the invention, the crystalline fatty substance is 10 ~C 30 Fatty alcohol and / or C 12 ~C 24 Esters of fatty acids, in particular of formula (Ib): R b -C(O)-OR b’ (In formula (Ib): R b and R b’ may be the same or different, but preferably different, and represent linear or branched, preferably linear, saturated or unsaturated, preferably saturated, hydrocarbon-based chains containing 10 to 38 carbon atoms; preferably, R b’is optionally substituted by one or more hydroxyl groups and / or optionally interrupted by one or more oxygen atoms, carbonyls, or combinations thereof, such as esters; 12 ~C 36 represents a hydrocarbon-based chain of the formula: b is in particular linear, saturated, unsubstituted and optionally interrupted by ester groups, C 12 ~C 38 R represents a hydrocarbon-based chain b’ is particularly linear, saturated and unsubstituted, C 12 ~C 30 The hydrates are also selected.

[0187] According to a particular embodiment of the invention, the crystalline fatty substance is chosen from compounds of formula (Ib), in particular cetyl palmitate or myricyl palmitate, and 18 ~C 38 alkyl hydroxystearoyl stearates.

[0188] Preferably, the crystalline fatty substance b) has the following formula (Ib'): [ka] (In formula (Ib'): R b’ , R b’’ and R b’’’ may be the same or different and are hydrogen atoms or linear or branched, preferably linear, saturated or unsaturated, preferably saturated, hydrocarbon-based chains containing 10 to 30 carbon atoms, preferably C 12 ~C 24 represents a hydrocarbon-based chain of the formula: ALK, ALK', ALK'' may be present or absent, may be identical or different and represent a linear or branched C1-C4 alkylene group, optionally substituted by at least one hydroxyl group; preferably, ALK' and ALK'' represent a methylene group -CH2- and ALK is absent; L, L' and L'' may be identical or different but are preferably identical and represent an ester group -C(O)-O- or -OC(O)-, preferably -OC(O)-; m, m' and m'' represent 0 or 1, preferably 1; It is understood that the three groups Rb', Rb'' and Rb'' cannot simultaneously represent a hydrogen atom), as well as optical and geometric isomers thereof, and solvates thereof, such as hydrates; Preferably, the crystalline fatty substance is selected from compounds of formula (I'b), such as glyceryl behenate, glyceryl dibehenate, trihydroxystearin, tribehenin, and mixtures thereof.

[0189] According to one embodiment of the invention, the crystalline fatty substance is present in a content ranging from 0.01% to 30% by weight, more particularly from 0.1% to 20% by weight, more particularly from 0.5% to 10% by weight, for example 5% by weight relative to the total weight of the composition.

[0190] Preferably, the crystalline fatty substance is present in a content ranging from 0.1% to 15% by weight, preferably from 0.5% to 12% by weight, preferably from 1% to 8% by weight and advantageously from 2% to 7% by weight relative to the total weight of the composition.

[0191] c) oil According to a preferred embodiment of the invention, composition C1 or C1' also comprises one or more oils, i.e. one or more fatty substances that are liquid at room temperature (25°C) other than the crystalline fatty substances b) defined above.

[0192] The oils of the invention are of natural or synthetic origin, preferably of natural and more preferably of vegetable origin. Salified fatty acids also differ from fatty acids, since they generally constitute soaps that are soluble in aqueous media.

[0193] According to a preferred embodiment, the oil c) is not a mineral oil.Preferably, the composition C1 or C1' does not contain a mineral oil, such as liquid petroleum jelly.

[0194] Preferably, the composition comprises one or more fatty substances c) which are hydrocarbon-based fatty substances that are liquid at 25° C. and atmospheric pressure.

[0195] According to a particular embodiment of the present invention, the composition C1 or C1′ is 16 Hydrocarbons or hydrocarbons containing more than 16 to 60 carbon atoms, preferably C6-C 16 The oils include one or more hydrocarbon-based oils selected from the group consisting of hydrocarbons, in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and / or fatty alcohol esters, and silicones. In particular, the oil is selected from non-silicone oils.

[0196] For the purposes of the present invention, fatty alcohols, fatty esters and fatty acids more particularly comprise one or more linear or branched, saturated or unsaturated hydrocarbon-based groups containing 6 to 60 carbon atoms, optionally substituted in particular with one or more hydroxyl groups OH, in particular with 1 to 4 hydroxyl groups. When they are unsaturated, these compounds may contain 1 to 3 unsaturated, preferably 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

[0197] According to a particular embodiment of the invention, the oil of the invention comprises C6-C 16 alkanes, which are linear or branched and optionally cyclic; preferably the oils c) of the invention are selected from linear or branched C-C 14 More preferably, C9 to C 13 , more preferably C9 to C12 The linear or branched hydrocarbons containing more than 16 carbon atoms may be selected from liquid paraffins, liquid petroleum jelly, polydecene, and hydrogenated polyisobutenes, such as Parleam®. Examples that may be mentioned include hexane, decane, undecane, dodecane, tridecane, and isoparaffins, such as isohexadecane, isodecane, or isododecane.

[0198] 20(MPa) 1 / 2 Among the hydrocarbon-based oils c) having the following total solubility parameters according to the Hansen solubility space, they may be chosen from natural or synthetic hydrocarbon-based oils, optionally fluorinated, optionally branched, alone or in mixtures.

[0199] According to a very advantageous embodiment, the composition C1 or C1' of the invention comprises one or more hydrocarbon-based oils, which may be volatile or non-volatile.

[0200] According to a preferred embodiment of the invention, the oil c) is a linear or branched hydrocarbon-based oil, which is volatile and is in particular selected from undecane, decane, dodecane, isododecane, tridecane and mixtures of these various volatile oils, preferably comprising isododecane in the mixture, or a mixture of undecane and tridecane.

[0201] According to another particular embodiment, oil c) is a mixture of volatile and non-volatile hydrocarbon-based oils, which mixture preferably comprises dodecane or isododecane as the volatile oil.

[0202] In particular, the oil c) of the invention is a C9-C oleate, preferably of natural origin, whose chain contains from 9 to 12 carbon atoms. 12 A mixture of alkanes, preferably linear or branched C9-C 12 This mixture has the INCI name C9-C 12Alkane, CAS 68608-12-8, is especially known in the Vegelight Silk® marketed by BioSynthIs. This biodegradable mixture of volatile oils is obtained from coconut oil (viscosity is 0.9-1.1 cSt (40°C) and has a flash point of 65°C).

[0203] According to one embodiment, composition C1 or C1' comprises at least 80% of hydrocarbon-based oils that are liquid at 25°C and atmospheric pressure, which are preferably volatile and more preferably selected from isodecane, decane, CetiolUT® and Vegelight Silk®.

[0204] According to another embodiment, composition C1 or C1' comprises c) a volatile oil and a non-volatile oil, in particular in a volatile / non-volatile oil ratio greater than or equal to 4.

[0205] According to another embodiment, composition C1 or C1' contains from 0 to 10% of silicone oil, preferably from 0 to 5% of silicone oil.

[0206] Among the volatile silicone oils that may be mentioned are volatile linear or cyclic silicone oils, in particular those with a viscosity of 8 centistokes (cSt) (8×10 -6 m 2 / s), in particular those containing 2 to 10 silicon atoms, in particular those containing 2 to 7 silicon atoms, these silicones optionally containing an alkyl or alkoxy group containing 1 to 10 carbon atoms.As volatile silicone oils that can be used in the present invention, mention may be made in particular of dimethicones having a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

[0207] Non-volatile silicone oils may include: linear or cyclic non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes containing alkyl, alkoxy and / or phenyl groups pendant to the silicone chain or at the end, these groups containing from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicone, phenyl dimethicone, phenyl trimethylsiloxy diphenyl siloxane, diphenyl dimethicone, diphenyl methyl diphenyl trisiloxane, 2-phenylethyl trimethylsiloxy silicate and pentaphenyl silicone oil.

[0208] The hydrocarbon-based oils c) of the invention are in particular chosen from: * Hydrocarbon-based oils containing 8 to 14 carbon atoms, in particular - Branched C8~C 14 Alkanes, e.g., C8-C derived from petroleum 14 Isoalkanes (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and oils sold, for example, under the trade names Isopar or Permethyl; linear alkanes, such as n-dodecane (C12) and n-tetradecane (C14) sold under the respective references Parafol 12-97 and Parafol 14-97 by Sasol, as well as mixtures thereof, undecane-tridecane mixtures, mixtures of n-undecane (C11) and n-tridecane (C13) as obtained in examples 1 and 2 of patent application WO 2008 / 155059 from Cognis, as well as mixtures of n-undecane (C11) and n-tridecane (C13) as obtained in examples 1 and 2 of patent application WO 2008 / 155059 from Cognis, as well as mixtures of n-undecane (C11) and n-tridecane (C13) Cetiol Ultimate® from BASF, * Short chain esters (containing 3-8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, and n-butyl acetate; * Hydrocarbon-based oils of plant origin, such as triglycerides composed of fatty acid esters of glycerol, where the fatty acids are C4-C 24and these chains may optionally be linear or branched, saturated or unsaturated; these oils are in particular heptanoic or octanoic triglycerides or wheat germ oil, sunflower oil, grape seed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea butter oil, avocado oil, olive oil, soybean oil, almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy seed oil, pumpkin oil, mallow oil, black currant oil, evening primrose oil, foxtail millet oil, barley oil, quinoa oil, rye oil, safflower oil, kukui oil, passionflower oil, rose moschata oil or coconut oil; shea butter; or else caprylic / capric triglycerides, such as those sold by Stearinerie Dubois or Miglyol Sold by Dynamit Nobel under the names 810 (registered trademark), 812 (registered trademark) and 818 (registered trademark). * Synthetic ethers containing 10 to 40 carbon atoms, * linear or branched hydrocarbons of mineral or synthetic origin, for example vaseline, polydecene, hydrogenated polyisobutenes such as Parleam®, squalane and liquid paraffin, and mixtures thereof; *Formula R 1 C(O)-OR 2 and the like, wherein R 1 represents a linear or branched fatty acid residue containing 1 to 40 carbon atoms, R 2 represents a hydrocarbon-based chain, particularly a branched chain, containing 1 to 40 carbon atoms, with the proviso that R 1 +R 2 is 10 or more, for example, pulsar oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, benzoic acid C 12 ~C 15Alkyl, hexyl laurate, isodecyl neopentanoate, isostearyl neopentanoate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldodecyl palmitate, 2-octyldodecyl myristate, alcohol or polyhydric alcohol heptanoates, octanoates, decanoates, or ricinoleates, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate, diisostearyl malate, and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters, more preferably linear or branched C8-C 10 Fatty acids and linear or branched C 12 ~C 18 Esters of fatty alcohols, alone or in mixtures with alkanes, especially with dodecane, obtained from the complete hydrogenation / reduction of fatty acids obtained from Cocos nucifera (coconut) oil, or with a mixture of cocoyl caprylate / capric acid and dodecane; mention may be made of the INCI names Coconut Alkanes (and) Cocoyl Caprylate / Caprate, sold under the name Vegelight 1212LC® by Grant Industries, * fatty alcohols which are liquid at room temperature and have a branched and / or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol; * carbonate oils which may be selected from carbonates of formula R8-OC(O)-O-R9, where R8 and R9 may be identical or different and may be linear or branched C4-C 12 , preferably C6 to C 10represents an alkyl chain; the carbonate oil may be dicaprylyl carbonate (or dioctyl carbonate) sold under the name Cetiol CC® by BASF, bis(2-ethylhexyl) carbonate sold under the name Tegosoft DEC® by Evonik, dipropylheptyl carbonate (Cetiol 4 AII from BASF), dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate, preferably dioctyl carbonate; * Volatile or non-volatile "ether oils" of formula R1-O-R2, in which R1 and R2 independently represent a linear, branched or cyclic C4 to C24 alkyl group, preferably a C6 to C18 alkyl group, and preferably a C8 to C12 alkyl group. It may be preferable that R1 and R2 are identical. Among the linear alkyl groups that may be mentioned are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hex ... Branched alkyl groups that may be mentioned include 1-methylpropyl, 2-methylpropyl, t-butyl, 1,1-dimethylpropyl, 3-methylhexyl, 5-methylhexyl, ethylhexyl, 2-ethylhexyl, 5-methyloctyl, 1-ethylhexyl, 1-butylpentyl, 2-butyloctyl, isotridecyl groups. , 2-pentylnonyl, 2-hexyldecyl, isostearyl, 2-heptylundecyl, 2-octyldodecyl, 1,3-dimethylbutyl, 1-(1-methylethyl)-2-methylpropyl, 1,1,3,3-tetramethylbutyl, 3,5,5-trimethylhexyl, 1-(2-methylpropyl)-3-methylbutyl, 3,7-dimethyloctyl, and 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl. Cyclic alkyl groups that may be mentioned include: Examples include cyclohexyl, 3-methylcyclohexyl and 3,3,5-trimethylcyclohexyl. Advantageously, the ether oil is chosen from dicaprylyl ether, dicapryl ether, dilauryl ether, diisostearyl ether, dioctyl ether, nonylphenyl ether, dodecyl dimethyl butyl ether, cetyl dimethyl butyl ether, cetyl isobutyl ether and mixtures thereof. Preferably, it is chosen from dicaprylyl ether and dicapryl ether.

[0209] In addition to the hydrocarbon-based oil, the composition C1 or C1' of the invention may contain a silicone oil.When a silicone oil is contained in the composition of the invention, it is preferably present in an amount not exceeding 10% by weight relative to the weight of the composition, more particularly in an amount less than 5% by weight, more preferably less than 2% by weight relative to the total weight of the composition.

[0210] In particular, the composition C1 or C1′ comprises at least one hydrocarbon-based liquid fatty substance c) chosen from: vegetable oils formed from fatty acid esters of polyols, in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, almond oil, calendula oil, palm oil, grape seed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil, coconut oil or cereal germ oil; - linear, branched or cyclic esters containing more than 6 carbon atoms, in particular containing from 6 to 30 carbon atoms; in particular isononyl isononanoate; More specifically, R d represents a higher fatty acid residue containing 7 to 19 carbon atoms, and R e Formula R represents a hydrocarbon-based chain containing 3 to 20 carbon atoms. d -C(O)-OR e Esters of, for example, palmitate, adipate, myristate and benzoate, especially diisopropyl adipate and isopropyl myristate; more preferably, R d represents a higher fatty acid residue containing 8 to 10 carbon atoms, and R e Formula R represents a hydrocarbon-based chain containing 12 to 18 carbon atoms. d -C(O)-OR e Esters of; - Hydrocarbons, in particular volatile or non-volatile linear, branched and / or cyclic alkanes, for example, optionally volatile C5-C 60Isoparaffins, such as undecane, dodecane, isododecane, tridecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or Isopars, and mixtures thereof; or alkanes obtained from the complete hydrogenation / reduction of a mixture of fatty acids derived from Cocos nucifera (coconut) oil, such as dodecane, C9-C, the chain of which contains 9 to 12 carbon atoms. 12 Alkanes, preferably linear or branched C9-C 12 mixtures of alkanes, especially those containing dodecane, or liquid paraffin, liquid petroleum jelly, or hydrogenated polyisobutylene; - ethers containing 6 to 30 carbon atoms; - ketones containing 6 to 30 carbon atoms; aliphatic fatty monoalcohols containing 6 to 30 carbon atoms whose hydrocarbon-based chain does not contain any substituents, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; - polyols containing 6 to 30 carbon atoms, for example hexylene glycol; and - Mixtures thereof, e.g. linear or branched C8-C 10 Fatty acids and C 12 ~C 18 Mention may be made of mixtures of alkanes, especially dodecanes, resulting from the complete hydrogenation / reduction of a mixture of fatty acids derived from Cocos nucifera (coconut) oil, such as a mixture of cocoyl caprylate / caprate and dodecane; those with the INCI name Coconut Alkanes (and) Cococaprylate / Caprate sold under the name Vegelight 1212LC® by Grant Industries; or C9-C, the chain of which contains 9 to 12 carbon atoms. 12 Alkanes, preferably linear or branched C9-C 12 Alkanes, especially C9-C including dodecane 12 Mixture of alkanes; INCI name C9~ sold by BioSynthIs 12Mention may be made of oil mixtures with alkanes, Vegelight Silk®.

[0211] Preferably, the composition C1 or C1′ of the invention comprises at least one hydrocarbon-based oil c) selected from: - vegetable oils formed by fatty acid esters of polyols, in particular triglycerides; - R d represents a higher fatty acid residue containing 7 to 19 carbon atoms, and R e Formula R represents a hydrocarbon-based chain containing 3 to 20 carbon atoms. d -C(O)-OR e More preferably, R d represents a higher fatty acid residue containing 8 to 10 carbon atoms, and R e Formula R represents a hydrocarbon-based chain containing 12 to 18 carbon atoms. d -C(O)-OR e Esters of; - Volatile or non-volatile, linear or branched, C8-C 60 Alkanes such as isododecane and alkanes obtained from the complete hydrogenation / reduction of a mixture of fatty acids derived from Cocos nucifera (coconut) oil, in particular dodecane; - Volatile or non-volatile non-aromatic cyclic C5-C 12 Alkanes; - ethers containing 7 to 30 carbon atoms; - ketones containing 8 to 30 carbon atoms; - aliphatic fatty monoalcohols, the hydrocarbon-based chain of which does not contain any substituents and which contain from 12 to 30 carbon atoms; - A mixture of them.

[0212] Advantageously, the oils c) of the invention are non-polar, i.e. made up exclusively of carbon and hydrogen atoms.

[0213] The hydrocarbon-based oil is preferably chosen from the hydrocarbon-based oils containing 8 to 14 carbon atoms which are particularly volatile, and more particularly the non-polar oils described above.

[0214] Preferably, the oils c) of the present invention are chosen from alkanes, such as dodecane, decane, isododecane, fatty alcohols, such as octyldodecanol, esters, such as isononyl isononanoate, cocoyl caprylate / caprate and mixtures thereof, more preferably from alkanes.

[0215] More specifically, the oil c) of the present invention is a linear or branched C6-C 16 , preferably C8 to C 14 More preferably, C9 to C 13 , more preferably C9 to C 12 More preferably, the oil c) of the present invention is volatile and is selected from undecane, decane, dodecane, isododecane, tridecane and mixtures thereof, including in particular dodecane, isododecane or a mixture of undecane and tridecane.

[0216] Preferably, the oil c) of the present invention is isododecane.

[0217] According to another advantageous embodiment of the invention, the oil c) of the invention is a mixture of a non-volatile oil and a volatile oil; preferably, the mixture comprises as volatile oil undecane, dodecane, isododecane or tridecane, more preferably isododecane. A mixture of a volatile oil and a non-volatile oil that may be mentioned is a mixture of isododecane and isononyl isononanoate or a mixture of isododecane and isononyl isononanoate.

[0218] More preferably, when the oil is a mixture of volatile and non-volatile oils, the amount of volatile oil is greater than the amount of non-volatile oil.

[0219] In particular, in the mixture, the non-volatile oil c) is a phenylsilicone oil, preferably chosen from pentaphenylsilicone oils.

[0220] Advantageously, composition C1 or C1' comprises one or more oils in a content ranging from 2% to 99.9% by weight, preferably ranging from 5% to 90% by weight, preferably ranging from 10% to 80% by weight and preferably ranging from 20% to 80% by weight, relative to the total weight of said composition.

[0221] According to a preferred embodiment of the invention, the composition C1 or C1' according to the invention comprises c) one or more fatty substances that are significantly liquid at 25° C. and atmospheric pressure, optionally e) water and d) one or more organic solvents other than c).

[0222] d) Organic solvents other than c) According to a particular embodiment of the invention, composition C1 or C1' also comprises one or more organic solvents other than c), which are non-polar or polar, preferably polar and protic or aprotic, more particularly protic and / or polar, preferably protic and polar.

[0223] Preferably, the organic solvent is water-miscible.

[0224] According to the present invention, the term "water-miscible solvent" refers to a compound that is liquid at room temperature and miscible with water (miscibility with water is greater than 50% by weight at atmospheric pressure at 25°C).

[0225] The organic solvents that may be used in the compositions C1 or C1' of the invention may be volatile.

[0226] Among the organic solvents that may be used in the compositions C1 or C1′ according to the invention, mention may be made in particular of polar protic or polar aprotic organic solvents, preferably polar protic organic solvents, in particular lower monoalcohols containing from 2 to 10 carbon atoms, such as ethanol and isopropanol, preferably ethanol.

[0227] According to one embodiment, composition C1 or C1' of the invention comprises one or more organic solvents, preferably chosen from monoalcohols containing from 2 to 6 carbon atoms, such as ethanol and isopropanol.

[0228] Preferably, the amount of organic solvent is less than 70% by weight, more preferably less than 50% by weight, relative to the total weight of the composition C1 or C1'. According to one embodiment of the present invention, the composition C1 or C1' comprises an organic solvent in an amount of at least 0.5% by weight, more particularly at least 1% by weight, relative to the total weight of the composition. In particular, the composition comprises from 2% to 50% by weight of organic solvent.

[0229] e) water According to a particular embodiment of the invention, composition C1 or C1' also comprises water.

[0230] Water suitable for use in the present invention may be tap water, distilled water, spring water, flower water such as cornflower water, and / or mineral water such as Vittel water, Lucas water, or La Roche Posay water, and / or thermal water.

[0231] According to one embodiment, the composition C1 or C1' of the invention comprises e) water and at least one fatty substance c). JPEG2025501738000033.jpg11JPEG2025501738000034.jpg11JPEG2025501738000035.jpg11

[0232] According to a particular embodiment of the present invention, composition C1 or C1' comprises water in an amount of not more than 5% by weight, in particular not more than 2% by weight, preferably not more than 1% by weight, more preferably not more than 0.5% by weight, relative to the total weight of the composition. More particularly, the compositions of the present invention are anhydrous, i.e. do not contain water. Where appropriate, such small amounts of water may in particular be introduced by components of the composition that may contain residual amounts thereof.

[0233] f) Surfactants According to a particular embodiment of the invention, composition C1 or C1' also comprises f) one or more surfactants, preferably a non-ionic or ionic surfactant, or a mixture thereof.

[0234] According to another particular embodiment of the invention, composition C1 or C1' does not comprise any surfactant.

[0235] The term "surfactant" refers to a compound that modifies the surface tension between two surfaces. Surfactants d) are amphiphilic molecules that have two parts with different polarity, one part is non-polar, lipophilic (holds fatty substances), the other hydrophilic part (miscible or soluble in water) is polar. The lipophilic part is generally a fatty chain, the other water-miscible part is polar and / or protic.

[0236] The term "ionic" means anionic, cationic, amphoteric, or zwitterionic.

[0237] The term "fatty chain" means a linear or branched, saturated or unsaturated hydrocarbon-based chain containing more than 6 atoms, preferably from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms.

[0238] According to a first particular embodiment, the composition of the invention comprises d) at least one silicone or non-silicone nonionic surfactant.

[0239] Among the nonionic surfactants according to the invention, mention may be made of fatty alcohols, α-diols and alkylphenols, either alone or in mixtures, these three compounds being polyethoxylated, polypropoxylated and / or polyglycerolated and comprising, for example, a fatty chain containing from 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups being in particular in the range from 2 to 50 and the number of glycerol groups being in particular in the range from 2 to 30. Ethylene oxide and propylene oxide copolymers, condensates of ethylene oxide and propylene oxide with fatty alcohols, polyethoxylated fatty amides, preferably having 2 to 30 ethylene oxide units, polyglycerolated fatty amides containing on average 1 to 5, in particular 1.5 to 4, glycerol groups, ethoxylated fatty acid esters of sorbitan containing 2 to 30 ethylene oxide units, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkyl polyglycosides, N-alkylglucamine derivatives, (C 10 ~C 14 ) Amine oxides such as alkylamine oxides or N-acylaminopropylmorpholine oxide may also be mentioned.

[0240] The surfactants in particular represent in total 0.01% to 30% by weight, preferably 0.5% to 15% by weight, more preferably 1% to 5% by weight and better still 1% to 5% by weight relative to the total weight of the composition.

[0241] Form of composition: According to one embodiment of the invention, the composition comprises an aqueous phase, in particular formulated as a water-in-oil or oil-in-water emulsion, or as a multiple emulsion (oil-in-water-in-oil or water-in-oil-in-water triple emulsion (such emulsions are known and are described, for example, by C. Fox in "Cosmetics and Toiletries" - November 1986 - Vol. 101 - pages 101-112)).

[0242] According to a particular embodiment of the invention, the composition is a direct emulsion, i.e. an oil-in-water or O / W emulsion. The weight of oil, in the inverse emulsion, is preferably less than 70% by weight, preferably less than or equal to 40% by weight and more particularly less than or equal to 35% by weight, relative to the total weight of the composition.

[0243] More particularly, in the direct emulsions, the amount of water is greater than or equal to 30% by weight, more particularly greater than or equal to 40% by weight and preferably greater than or equal to 35% by weight relative to the total weight of the composition.

[0244] According to another particular embodiment of the invention, the composition of the invention is an inverse emulsion, i.e. water-in-oil or W / O type. The mass of oil is preferably greater than 30% by mass, preferably greater than 40% by mass, more particularly greater than or equal to 45% by mass, relative to the total mass of the composition, in the inverse emulsion. More particularly, the amount of water is less than 40% by mass, preferably less than or equal to 30% by mass, relative to the total mass of the composition, in the inverse emulsion.

[0245] Composition C1 or C1' according to the invention preferably has a pH ranging from 3 to 9, depending on the carrier selected.

[0246] According to a particular embodiment of the invention, the pH of the compositions is neutral or slightly acidic. Preferably, the pH of the compositions is between 6 and 7. The pH of these compositions can be adjusted to the desired value using acidifying or basifying agents commonly used in cosmetics or alternatively standard buffer systems.

[0247] The term "basifying agent" or "base" refers to any agent for increasing the pH of the composition in which it is present. The basifying agent is a Brønsted base, a Lowry base or a Lewis base. It can be mineral or organic. In particular, said agent is selected from a) aqueous ammonia, b) (bi) carbonates, c) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and their derivatives, d) oxyethylenated and / or oxypropylenated ethylenediamines, e) organic amines, f) mineral or organic hydroxides, g) alkali metal silicates such as sodium metasilicate, h) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, i) compounds of formula (F) below: [ka] (In formula (F), - W is a divalent C1-C6 alkylene group optionally substituted by one or more hydroxyl groups or C1-C6 alkyl groups and / or optionally interrupted by one or more heteroatoms such as O or NRu; - R x , R y , R z , R t and R u may be the same or different and represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 hydroxyalkyl group, or a C1-C6 aminoalkyl group.

[0248] Examples of amines of formula (F) include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

[0249] The term "alkanolamine" refers to an organic amine having a primary, secondary or tertiary amine functional group and one or more linear or branched C1-C8 alkyl groups bearing one or more hydroxyl groups.

[0250] Among the mineral or organic hydroxides, mention may be made of those selected from a) alkali metal hydroxides, b) alkaline earth metal hydroxides, such as sodium hydroxide or potassium hydroxide, c) transition metal hydroxides, d) lanthanide or actinide hydroxides, quaternary ammonium hydroxides and guanidinium hydroxide. Preference is given to the mineral or organic hydroxides a) and b).

[0251] Among the acidifying agents for the compositions used in the invention, mention may be made, for example, of mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.

[0252] The basifying and acidifying agents defined above preferably represent from 0.001% to 20% by weight relative to the weight of the composition, and more particularly from 0.005% to 8% by weight relative to the weight of the composition.

[0253] According to a particular embodiment of the invention, the composition C1 or C1' comprises water in an amount of not more than 10% by weight relative to the total weight of the composition. Even more preferably, the composition C1 or C1' comprises water in an amount of not more than 5%, better still not more than 2%, even better still not more than 0.5%, and in particular does not contain water. Where appropriate, such small amounts of water may in particular be introduced by raw materials of the composition which may contain residual amounts of water.

[0254] According to a particular embodiment of the invention, the composition is free of water.

[0255] Advantageously, the composition C1 or C1' according to the invention comprises a physiologically acceptable medium. JPEG2025501738000037.jpg11JPEG2025501738000038.jpg11JPEG2025501738000039.jpg11JPEG2025501738000040.jpg11JPEG2025501738000041.jpg11In particular, the composition is a cosmetic composition.

[0256] The term "physiologically acceptable medium" means a medium that is compatible with human keratinous substances, such as the skin, lips, nails, eyelashes, eyebrows or hair. JPEG2025501738000042.jpg11

[0257] The term "cosmetic composition" means a composition that is compatible with keratinous materials, has a pleasant color, odor and feel, and does not produce unacceptable discomfort (irritation or tightness) that would deter consumers from using it.

[0258] The term "keratinous material" means the skin (body, face, eye contour, scalp), hair, eyelashes, eyebrows, body hair, nails or lips.

[0259] The composition C1 or C1' according to the invention may contain one or more cosmetic additives selected from fragrances, preservatives, fillers, colorants, UV screens, moisturizers, vitamins, ceramides, antioxidants, free radical scavengers, polymers other than a), thickeners or film formers other than b), trace elements, emollients, sequestering agents, anti-hair loss agents, anti-dandruff agents, accelerators. In particular, the composition C1 or C1' according to the invention also contains one or more colorants, preferably pigments, selected from pigments, direct dyes and mixtures thereof. More preferably, the pigments according to the invention are selected from carbon black, iron oxides, in particular black iron oxide, and mica coated with iron oxide, triarylmethane pigments, in particular blue and purple triarylmethane pigments, such as Blue 1 Lake, azo pigments, in particular red azo pigments, such as D&C Red 7, alkali metal salts of lithole red, such as calcium salt of lithole red B, and more preferably red iron oxide.

[0260] Advantageously, the composition C1 or C1' according to the invention is a makeup composition, in particular a makeup composition for the lips, a mascara, an eyeliner, an eyeshadow or a foundation.

[0261] Adjuvants Compositions C1 or C1' according to the invention may also contain one or more fillers, in particular in a content ranging from 0.01% to 30% by weight, preferably from 0.01% to 20% by weight, relative to the total weight of the composition. The term "fillers" should be understood to mean colorless or white mineral or synthetic particles of any shape, which are insoluble in the medium of the composition, regardless of the temperature at which the composition is produced. These fillers serve in particular to modify the rheology or texture of the composition.

[0262] Compositions C1 or C1' according to the invention may be in the form of an anhydrous composition, a water-in-oil emulsion or an oil-in-water emulsion.

[0263] The invention is illustrated in more detail in the following examples, in which amounts are given as % by weight. EXAMPLES

[0264] The PHAs illustrated in the various examples were prepared in 3 L chemostats and / or 5 L Fernbach flasks depending on whether or not a β-oxidation pathway inhibitor was used. Isolation of the PHAs was similar for all the examples obtained.

[0265] In the first stage, the microorganism produces PHA, which is stored in intracellular granules. The proportion varies as a function of the applied conditions, such as temperature or the nature of the culture medium. The production of PHA granules may or may not be associated with the growth of the microorganism, as a function of the nature of the microorganism. During the second stage, the biomass containing PHA is isolated, i.e. separated from the fermentation medium, and then dried. The PHA is extracted from the biomass before being purified, if necessary.

[0266] In certain embodiments, a mixture of saturated and unsaturated carbon sources is necessary for the stability of the resulting PHA.

[0267] [Table 15]

[0268] [Table 16]

[0269] Example 1: Side chain R represents a linear 10% unsaturated n-octenyl group 1 and R represents an n-pentyl group. 2 PHA having [ka]

[0270] The method for synthesizing the compound of Example 1 was adapted from the paper: Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440, Z. Sun, JA Ramsay, M. Guay, BA Ramsay, Applied Microbiology Biotechnology, 82.657-662, 2009.

[0271] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054. The cultivation method is in a 3 L chemostat containing 2.5 L of culture medium at a rate of μ = 0.15 h. -1 The culture is carried out under fed-batch pure culture conditions using a maintenance medium containing a mixture of carbon sources.

[0272] Nominal Dissolved Oxygen (O D The system is aerated with an air flow of 0.5 vvm so that the pH is 30% saturated. The pH is adjusted with 15% aqueous ammonia solution. The temperature of the fermentation medium is adjusted to 30°C.

[0273] Equipment for fed-batch fermentation mode: - The fermentation medium is regulated in terms of temperature - dissolved oxygen pressure and pH (not shown): see attached FIG. 1. - The production method is carried out using three different culture media. The first culture medium, defined as CM1 "inoculum", is used for the preparation of a pre-culture. The second culture medium, defined as CM2 "batch", is used for the non-fed-batch cultivation of the microorganism with the primary carbon source in Fernbach flasks. The third culture medium, defined as CM3 "maintenance", is used for fed-batch or maintenance fermentation mode with the carbon source of interest, with a flow rate calibrated as a function of the growth of the microorganism.

[0274] [Table 17]

[0275] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™.

[0276] [Table 18]

[0277] 100 mL of preculture is prepared by suspending a cryotube containing 1 mL of strain together with 100 mL of "inoculation" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then incubating for 24 hours at 30° C. and 150 rpm. 1.9 L of CM2 "batch" culture medium in a sterile 3 L chemostat is inoculated with 100 mL of preculture. D Inoculate with =0.1. After 4 h at 30°C and 850 rpm.

[0278] After the introduction is complete, the biomass is isolated by centrifugation and washed three times with water. The biomass is dried by freeze-drying and then extracted with ethyl acetate for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, consisting of PHA dissolved in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass.

[0279] The PHA may optionally be purified by successive dissolution and precipitation, for example, from an ethyl acetate / ethanol 70% methanol system.

[0280] The PHAs have been fully characterized by spectroscopic and spectrometric methods and are consistent with the predicted chemical structures.

[0281] Preparation of Example 1': Side chain R represents a 5% unsaturated n-octenyl group 1 and R representing an n-hexyl group. 2 PHA copolymer having [ka] The copolymer of Example 1' (5% unsaturation and R representing n-hexyl) 2 The medium (chain) was prepared according to the procedure described in Example 1, using a trace element solution of the same composition as that described in Example 1, with the following medium composition:

[0282] [Table 19]

[0283] The PHA copolymer of Example 1' was fully characterized by spectroscopic and spectrometric methods and was consistent with the expected chemical structure and had an unsaturation level of 5%.

[0284] Example 1: Side chain R represents a linear 10% unsaturated n-octenyl group 1 and R representing an n-hexyl group. 2 PHA copolymer having Copolymer of Example 1″ (10% unsaturation and R representing n-hexyl) 2 The medium (chain) was prepared according to the procedure described in Example 1, using a trace element solution of the same composition as that described in Example 1, with the following medium composition:

[0285] [Table 20]

[0286] The PHAs have been fully characterized by spectroscopic and spectrometric methods and are consistent with the predicted chemical structures.

[0287] Example 1': Side chain R represents a linear 30% unsaturated n-octenyl group 1 and R representing an n-pentyl group. 2 PHA copolymer having Copolymer of Example 1''' (30% unsaturation and R representing n-pentyl) 2 The medium (chain) was prepared according to the procedure described in Example 1, using a trace element solution of the same composition as that described in Example 1, with the following medium composition:

[0288] [Table 21]

[0289] The PHA copolymers have been fully characterized by spectroscopic and spectrometric methods and are consistent with the predicted chemical structures.

[0290] Example 2: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation 100% grafted with thiolactic acid (compound of Example 1 grafted with thiolactic acid TLA): [ka] 1 g of the compound of Example 1 and 150 mg of thiolactic acid were dissolved in 20 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 100 W UV lamp at 365 nm (reference) and with stirring for at least 10 minutes.

[0291] 20 mL of the reaction medium was then precipitated from a 200 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0292] The grafted PHA of Example 2 has been fully characterized by spectroscopic and spectroscopy techniques and conforms to the expected chemical structure.

[0293] Example 3: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 100% with octanethiol (compound of Example 1 grafted with n-octanethiol) [ka] 0.5 g of the compound of Example 1 and 125 mg of octanethiol were dissolved 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 for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0294] The reaction medium was then precipitated from a 100 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0295] The grafted PHA of Example 3 has been fully characterized by spectroscopic and spectroscopy techniques and conforms to the expected chemical structure.

[0296] Example 4: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 75% with 8-mercapto-1-octanol (compound of Example 1 grafted with 8-mercapto-1-octanol) [ka] 50 mg of the compound of Example 1 and 10 mg of 8-mercapto-1-octanol were dissolved in 5 mL of ethyl acetate at room temperature with stirring. 2 mg of 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651) was added to this mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) with stirring for at least 10 minutes.

[0297] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A viscous white precipitate was obtained. This step can be repeated. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and dried under dynamic vacuum at 40° C. to obtain a uniform film.

[0298] The grafted PHA of Example 4 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Overall grafting to 75% or 7.5% functional groups.

[0299] Example 5: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 32% with cysteamine (compound of Example 1 grafted with cysteamine) [ka] 0.5 g of the compound of Example 1 and 54 mg of cysteamine were dissolved 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 100 W UV lamp at 365 nm (reference) and with stirring for at least 10 minutes.

[0300] The reaction medium was then precipitated from a 100 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0301] The grafted PHA of Example 5 was fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure: 32% overall, or 3.2% grafting to functional groups.

[0302] Example 6: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 73% with cyclohexanethiol (CHT) (compound of Example 1 grafted with CHT) [ka] 100 mg of the compound of Example 1 and 26 mg of cyclohexanethiol were dissolved 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 for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0303] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0304] The grafted PHA of Example 6 was fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure: 73% overall or 7.3% grafting to functional groups.

[0305] Example 7: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 70% with 2-furanmethanethiol (FT) (Compound of Example 1 grafted with FT) [ka] 100 mg of the compound of Example 1 and 26 mg of 2-furanmethanethiol were dissolved 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 for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0306] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0307] The grafted PHA of Example 7 has been fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure: 70% overall, or 7% grafting to functional groups.

[0308] Example 8: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 70% with 1-thio-β-D-glucose tetraacetate (compound of Example 1 grafted with TGT) b) [ka] 100 mg of the compound of Example 1 and 26 mg of 1-thio-β-D-glucose tetraacetate were dissolved 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 for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0309] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0310] The grafted PHA of Example 8 has been fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure: 70% overall, or 7% grafting to functional groups.

[0311] Example 9: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 50% with 2-phenylethanethiol (PT) (Compound of Example 1 grafted with PT) [ka] 100 mg of the compound of Example 1 and 26 mg of 2-phenylethanethiol were dissolved in 5 mL of dichloromethane at room temperature with stirring. 5 mg of 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651) was added to the mixture. The medium was then irradiated for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0312] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0313] The grafted PHA of Example 9 has been fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure. Overall 50% grafting to 5% functional groups.

[0314] Example 10: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation grafted 64% with 4-tert-butylbenzyl mercaptan (TBM) (Compound of Example 1 grafted with TBM) [ka] 100 mg of the compound of Example 1 and 26 mg of 4-tert-butylbenzyl mercaptan were dissolved 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 for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0315] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0316] The grafted PHA of Example 10 has been fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure: 64% overall or 6.4% grafting to functional groups.

[0317] Example 11: Poly(3-hydroxynonanoate-co-undecenoate) containing 10% unsaturation 100% grafted with thiolactic acid [ka] 0.1 g of the compound of Example 1″ and 15 mg of thiolactic acid were dissolved in 5 mL of chloroform 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 for at least 10 minutes under a 100 W UV lamp at 365 nm (reference) and with stirring.

[0318] The reaction medium was then precipitated from a 50 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0319] The grafted PHA of Example 11 has been fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure. Grafting to 100%.

[0320] Example 12: Poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturation 100% grafted with octanethiol [ka] 1 g of the PHA copolymer of Example 1' and 150 mg of octanethiol were dissolved 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 100 W UV lamp at 365 nm (reference) and with stirring for at least 10 minutes.

[0321] The reaction medium was then precipitated from a 500 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0322] The grafted PHA of Example 12 has been fully characterized by spectroscopic and spectroscopic techniques and conforms to the expected chemical structure. Grafting to 100%.

[0323] Example 13: Poly(3-hydroxynonanoate-co-undecenoate) containing 100% epoxidized 5% unsaturation [ka] 20 g of the PHA copolymer of Example 1' was dissolved in 80 mL of anhydrous dichloromethane. A suspension of 1.9 g of 77% m-CPBA was prepared with 20 mL of anhydrous dichloromethane and added to the mixture by stirring at room temperature for at least 120 hours.

[0324] The reaction medium was then precipitated from a 500 mL mixture of 70 / 30 v / v ethanol / water. A viscous white precipitate was obtained. This step can be repeated. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and dried under dynamic vacuum at 40° C. to obtain a uniform film.

[0325] The PHA of Example 13 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. It is epoxidized to 100%.

[0326] Example 14: Poly(3-hydroxynonanoate-co-undecenoate) containing 10% unsaturation, 100% epoxidized 10 g of the PHA copolymer of Example 1'' was dissolved in 40 mL of anhydrous dichloromethane. A suspension of 1.9 g of 77% m-CPBA was prepared with 10 mL of anhydrous dichloromethane and added to the mixture by stirring at room temperature for at least 120 hours.

[0327] The reaction medium was then precipitated from a 500 mL mixture of 70 / 30 v / v ethanol / water. A viscous white precipitate was obtained. This step can be repeated. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and dried under dynamic vacuum at 40° C. to obtain a uniform film.

[0328] The PHA of Example 14 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. It is epoxidized to 100%.

[0329] Example 15: Poly(3-hydroxyoctanoate-co-undecenoate) containing 100% epoxidized 30% unsaturation [ka] 10 g of the PHA copolymer of Example 1'' was dissolved in 40 mL of anhydrous dichloromethane. A suspension of 6.2 g of 77% m-CPBA was prepared with 10 mL of anhydrous dichloromethane and added to the mixture by stirring at room temperature for at least 120 hours.

[0330] The reaction medium was then precipitated from a 250 mL mixture of 70 / 30 v / v ethanol / water. A viscous white precipitate was obtained. This step can be repeated. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and dried under dynamic vacuum at 40° C. to obtain a uniform film.

[0331] The PHA of Example 15 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. It is epoxidized to 100%.

[0332] Example 16: Poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturation 100% grafted with 4-tert-butylbenzyl mercaptan (TBM) (Compound of Example 1' grafted with TBM) [ka] 2 g of the PHA copolymer of Example 1' and 300 mg of 4-tert-butylbenzyl mercaptan were dissolved in 25 mL of ethyl acetate at room temperature with stirring. 25 mg of 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651) was added to the mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) and with stirring for at least 10 minutes.

[0333] The reaction medium was then precipitated from a 500 mL mixture of 70 / 30 v / v ethanol / water. A sticky white precipitate was obtained. This step can be repeated. The product thus obtained was dissolved in a minimum amount of ethyl acetate, poured onto a Teflon plate, and then dried under dynamic vacuum at 40° C. to obtain a homogenous film.

[0334] The PHA of Example 16 has been fully characterized by spectroscopic and spectroscopy techniques and conforms to the expected chemical structure. Grafting to 100%.

[0335] Example 17: Side chain R representing an isohexenyl group1 and R representing an isobutyl group. 2 A copolymer of PHA having [ka] The manufacturing process of Example 17 was adapted from "Polyester Biosynthesis Characteristics of Pseudomonas citronellolis Grown on Various Carbon Sources, Including 3-Methyl-Branched Substrate", Mun Hwan Choi and Sung Chul Yoon, Applied and Environmental Microbiology, Vol. 60, No. 9. 3245-3254 (1994). The microorganism used was Pseudomonas citronellolis ATCC (registered trademark) 13674 (trademark). The culture method was carried out under pure culture conditions in a non-fed-batch culture mode in a 5 L Fernbach flask (Corning (registered trademark) reference number 431685) containing 2 culture medium stirred at 30 °C and 110 rpm in an orbital incubator (orbital diameter 2.5 cm).

[0336] The production method is carried out using two different culture media: the first culture medium, defined as CM1 "inoculum", is used for the preparation of a pre-culture; the second culture medium, defined as CM2 "batch", is used for the non-fed-batch cultivation of the microorganism with the carbon source of interest in Fernbach flasks.

[0337] [Table 22]

[0338] [Table 23]

[0339] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™ BD.

[0340] The composition of the yeast extract, by weight, is 100% autolysate of the yeast Saccharomyces cerevisiae, reference number 210933 DIFCO® BD.

[0341] [Table 24]

[0342] A 100 mL preculture is prepared by suspending a cryotube containing 1 mL of strain together with 100 mL of "inoculation" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then incubating at 30° C. and 150 rpm for 24 hours. 1.9 L of CM2 "batch" culture medium in a sterile 5 L Fernbach flask is inoculated with 100 mL of O. D Inoculate at =0.1.

[0343] After 70 hours at 30°C and 110 rpm, the biomass is dried by freeze-drying and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, consisting of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40°C until constant mass.

[0344] The PHA can optionally be purified by sequential dissolution and precipitation, for example using a dichloromethane / methanol system.

[0345] The PHA copolymer of Example 17 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure.1 = 68 mol% of units (A) which are isohexenyl, R 2 = The amount of isobutyl units (B) was 32 mol %.

[0346] Example 18: Side chain R representing an isohexyl group 1 and R representing an isobutyl group. 2 A copolymer of PHA having [ka] Example 18 is obtained by hydrogenating the PHA copolymer of Example 17 using a H-Cube Midi® continuous hydrogenator manufactured by Thales Nano Technologies.

[0347] A solution of 2 g (8.83 mmol) of Example 3 is prepared using a mixture composed of 100 mL of ethyl acetate (Sigma-Aldrich-CAS: 141-78-6) and 100 mL of methanol (Sigma-Aldrich-CAS: 67-56-1) and introduced at a flow rate of 3 mL / min into a hydrogenation cartridge (MidiCard reference DHS 2141; ThalesNano Technologies) containing a catalyst containing 5% palladium on charcoal, maintained at 100° C. under a pressure of 80 bar in the presence of hydrogen in a ThalesNano Technologies H-Cube Midi® system. The reduction of the double bond is monitored by NMR. After six successive reduction cycles, the solution is concentrated by evaporation and dried under vacuum to constant mass.

[0348] The PHA can optionally be purified by sequential dissolution and precipitation, for example using a dichloromethane / methanol system.

[0349] The PHA copolymer of Example 4 has been fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. 1 = 68 mol% of units (A) which are isohexyl, R 2 = The amount of isobutyl units (B) was 32 mol %.

[0350] Example 19: The polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™ and octanoic acid.

[0351] The cultivation method was carried out under batch-wise pure culture conditions in 5 L Fernbach flasks (Corning® ref. 431685) containing 2 L of culture medium, shaken at 110 rpm at 30° C. in an orbital incubator (orbital diameter 2.5 cm). The synthesis process was carried out using two different culture media. The first culture medium, defined as CM1 “inoculum”, was used for the preparation of the inoculum. The second culture medium, defined as CM2 “batch”, was used for the non-fed-batch cultivation of the microorganisms with octanoic acid in Fernbach flasks.

[0352] The composition (unit: grams) of these two media per liter is shown in Table 8.

[0353] [Table 25]

[0354] (1) The composition of Nutrient Broth is, by weight, 37.5% beef extract and 62.5% peptone. Reference code 233000 DIFCO (trademark).

[0355] (2) The composition of the trace element solution (grams per liter) is set forth in Table 9 below.

[0356] [Table 26]

[0357] A 100 mL inoculum was prepared by suspending a cryotube containing 1 mL of strain with 100 mL of "inoculation" culture medium in a 250 mL Fernbach flask, with the pH adjusted to 6.8 with 2N NaOH, and then incubated at 30° C. and 150 rpm for 24 hours. 1.9 L of CM2 "batch" culture medium in a sterile 5 L Fernbach flask was inoculated with 100 mL of O. D =0.1. After 70 hours at 30°C and 110 rpm, the biomass was dried by freeze-drying and then extracted with dichloromethane for 24 hours. The suspension was clarified by filtration through a GF / A filter (Whatman®). The filtrate, which contained the copolymer as a solution in dichloromethane, was concentrated by evaporation and then dried to constant weight under high vacuum at 40°C. The crude polyhydroxyalkanoate was purified by precipitating it from a solution of 10 times the latter's mass in dichloromethane and 10 times the volume of the solution in cold methanol. The solid obtained was dried to constant weight under high vacuum at 40°C.

[0358] The molecular weight of the resulting polyhydroxyalkanoates was characterized by size exclusion chromatography with refractive index detection. □ Eluent: THF □ Analysis flow rate: 1mL / min □ Injection: 100μL □ Columns: 1 Agilent PLGel Mixed-D column (5 μm; 300 × 7.5 mm); 1 Agilent PLGel Mixed-C column (5 μm; 300 × 7.5 mm); 1 Agilent Oligopore column (300 × 7.5 mm) □ Room temperature (25℃) Detection: Waters 2487 Dual Absorbance Detector, Waters 2414 Refractometer Rate detector □ Integrator: Refractive index of 45℃, 64mV □ Empower (GC Relative Molecular Mass / Conventional Module) □ Empower injection time: 40 minutes □ Standard: High Mass / EasiVial PS-H 4 mL polystyrene from Agilent Technologies, Patent No. PL2010-0200

[0359] This analysis makes it possible to determine the weight average molecular weight (Mw: unit: g / mol), the number average molecular weight (Mn: unit: g / mol), the polydispersity index PI (Mw / Mn) and the degree of polymerization DPn.

[0360] The monomer composition of the polyhydroxyalkanoate obtained was established using gas chromatography equipped with a flame ionization detector. Identification was performed by injection of commercial standards, and the monomer composition was determined by methanolysis and silylation treatments. To determine the monomer composition, 7 mg of the polyhydroxyalkanoate polymer was dissolved in 1.5 mL of chloroform and subjected to methanolysis at 100 °C for 4 h in the presence of 1.5 mL of MeOH / HCl (17 / 2, v / v) solution. The organic phase was then washed with 1 mL of water and then dried over MgSO4. Silylation of the resulting methyl ester was performed by adding 100 μL of BSTFA (N,O-bis(trimethylsilyl)trifluoroacetamide) and 100 μL 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 μL of dichloromethane and analyzed by chromatography under the following conditions: □ Hewlett Packard 6890 series devices □ ZB-5 HT stationary phase column from Phenomenex (length: 30 m, diameter: 0.25 mm) □ Temperature: Constant temperature 60℃ to 300℃ (6 minutes) (heating rate: 10℃ / min) □ Gas: Helium; Flow rate: 0.8mL / min □ Injector: Temperature: 250℃; 50ml / min □ Hydrogen flame ionization detector; temperature: 300℃ □ Injection: Volume 1μL

[0361] The resulting copolymer contained 91% by weight poly(3-hydroxyoctanoate), 6% by weight poly(3-hydroxyhexanoate), and 3% by weight poly(3-hydroxybutanoate). Mn=68100g / mol Mw=149100g / mol □ Ip=2.2 □DPn=531.

[0362] Example 20: The polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™, octanoic acid, and acrylic acid. The cultivation method was a dilution D = 0.25 h in a 3 L chemostat containing 1.1 L of culture medium. -1 The system was run under continuous pure culture conditions at 30% saturation with nominal dissolved oxygen (O D Air was aerated at a flow rate of 3 vvm (vvm = volume of air per minute per volume of fermentation medium) to a value of 0.1 ml / min.

[0363] The production process was carried out using three different culture media. A first undefined culture medium (CM1) was used for the preparation of the inoculum. A second defined culture medium (CM2) was used for the non-fed-batch cultivation of the microorganism in the fermenter. A third defined culture medium (CM3) was used for the feeding or maintenance of the continuous fermentation containing octanoic acid and acrylic acid (inhibitors of the β-oxidation pathway). The CM1 and CM2 culture media are the same as those described in Example 1. The composition of CM3 medium per liter (in grams) is given in Table 10.

[0364] [Table 27]

[0365] A cryotube containing 1 mL of the strain was suspended in a 250 mL Fernbach flask together with 100 mL of nutrient broth whose pH had been adjusted to 7.0 with 2N NaOH, and then incubated at 30°C and 150 rpm for 24 hours to prepare 100 mL of inoculum.

[0366] A fermenter containing 1 liter of CM2 culture medium at 30°C was incubated at 4°C until the optical density at 630 nm reached 0.1 (O D630 = 0.1). The system was maintained at 30°C with stirring at 700 ± 200 rpm and regulated in cascade with oxygen for approximately 16 hours and / or a period allowing the microorganisms to reach their stationary phase of growth.

[0367] When the microorganism reached its stationary growth phase, the fermenter was started to be fed with CM3 culture medium and withdrawals were made to maintain the initial mass of the fermentation medium. When the equilibrium state of the continuous culture was reached, a portion of the withdrawn material was centrifuged to separate the biomass from the fermentation medium. The biomass was dried by freeze-drying and then extracted with dichloromethane for 24 hours. The resulting suspension was clarified by filtration through GF / A filter paper (Whatman®). The resulting filtrate, containing the copolymer dissolved in dichloromethane, was concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass. The crude polyhydroxyalkanoate was purified by precipitating it from a solution of 10 times the latter's mass in dichloromethane and 10 times the volume of the solution in cold methanol. The resulting solid was dried under high vacuum at 40° C. until constant mass.

[0368] The copolymer thus obtained contained 96% by weight poly(3-hydroxyoctanoate), 3% by weight poly(3-hydroxyhexanoate), and 1% by weight poly(3-hydroxybutanoate). Mn=67900g / mol Mw=142000g / mol □ Ip=2.1 □DPn=611.

[0369] Example 21: Side chain R representing an n-hexyl group 1 and R representing an n-butyl group. 2 A copolymer of PHA having [ka] The polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054, nonanoic acid, and acrylic acid. The culture method was a dilution D = 0.25 h in a 3 L chemostat containing 1.1 L of culture medium. -1 The nominal dissolved oxygen (O D The system is ventilated with an airflow of 1 vvm so that the ) value is 30% saturated.

[0370] The production process is carried out using three different culture media. The first culture medium (CM1) is used for the preparation of the inoculum. The second culture medium (CM2) is used for batch cultivation in a fermenter of the microorganism. The third culture medium (CM3) is used for feeding or maintaining the continuous fermentation containing the carbon source of interest and an inhibitor of the β-oxidation pathway (acrylic acid). The composition (in grams) per liter of the three media CM1, CM2 and CM3 is given in Table 11.

[0371] [Table 28]

[0372] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™.

[0373] The composition of the trace element solution (grams per liter) is given in Table 12 below.

[0374] [Table 29]

[0375] In a 500 mL Fernbach flask, add 100 mL of CM1 "inoculum" with the pH preadjusted to 7.0 with 2N NaOH. D Suspend cryotubes containing 1 mL of strain at 0.5% CO2 at 37° C. to prepare a 100 mL inoculum, then incubate at 30° C. and 150 rpm for 24 h.

[0376] A 3 L fermenter containing 1 liter of CM2 "batch" culture medium at 30°C was incubated at 4°C until the optical density at 600 nm reached 0.1 (O D600 The system is maintained at 30° C., with stirring at 700±200 rpm, and regulated in cascade with oxygen for approximately 16 hours and / or a period allowing the microorganism to reach its stationary phase of growth.

[0377] Once the microorganism has reached its stationary growth phase, the fermenter is started to be fed with CM3 "continuous" medium and withdrawals are made to maintain the initial mass of the fermentation medium. Once the equilibrium state of the continuous culture is reached, a portion of the withdrawn material is centrifuged to separate the biomass from the fermentation medium. The biomass is dried by freeze-drying and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, consisting of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass.

[0378] The molecular weight of the resulting polyhydroxyalkanoates was characterized by size exclusion chromatography with refractive index detection. □ Eluent: THF □ Analysis flow rate: 1mL / min □ Injection: 100μL □ Columns: 1 Agilent PLGel Mixed-D column (5 μm; 300 × 7.5 mm); 1 Agilent PLGel Mixed-C column (5 μm; 300 × 7.5 mm); 1 Agilent Oligopore column (300 × 7.5 mm) □ Room temperature (25℃) Detection: Waters 2487 Dual Absorbance Detector, Waters 2414 Refractometer Rate detector □ Integrator: Refractive index of 45℃, 64mV □ Empower (GC Relative Molecular Mass / Conventional Module) □ Empower injection time: 40 minutes □ Standard: High Mass / EasiVial PS-H 4 mL polystyrene from Agilent Technologies, Patent No. PL2010-0200

[0379] This analysis makes it possible to determine the weight average molecular weight (Mw: unit: g / mol), the number average molecular weight (Mn: unit: g / mol), the polydispersity index PI (Mw / Mn) and the degree of polymerization DPn.

[0380] The monomer composition of the resulting polyhydroxyalkanoates was confirmed using gas chromatography equipped with a flame ionization detector, identification was performed by injecting commercially available standards, and the monomer composition was determined by methanolysis and silylation treatments.

[0381] To determine the monomer composition, 7 mg of the polyhydroxyalkanoate polymer was dissolved in 1.5 mL of chloroform and subjected to methanolysis at 100° C. for 4 h in the presence of 1.5 mL of MeOH / HCl (17 / 2, v / v) solution. The organic phase was then washed with 1 mL of water and then dried over MgSO4. Silylation of the resulting methyl ester was carried out by adding 100 μL of BSTFA (N,O-bis(trimethylsilyl)trifluoroacetamide) and 100 μL 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 μL of dichloromethane and analyzed by chromatography under the following conditions: □ Hewlett Packard 6890 series devices □ ZB-5 HT stationary phase column from Phenomenex (length: 30 m, diameter: 0.25 mm) □ Temperature: Constant temperature 60℃ to 300℃ (6 minutes) (heating rate: 10℃ / min) □ Gas: Helium; Flow rate: 0.8mL / min □ Injector: Temperature: 250℃; 50ml / min □ Hydrogen flame ionization detector; temperature: 300℃ □ Injection: Volume 1μL

[0382] The copolymer thus obtained contained 86% by weight poly(3-hydroxynonanoate), 9% by weight poly(3-hydroxyheptanoate), and 5% by weight poly(3-hydroxypentanoate). Mn=65900g / mol Mw=143600g / mol □ Ip=2.2 □ DPn=531

[0383] Example 22: Following the procedure of Example 19, a polymer was prepared using nonanoic acid (instead of octanoic acid) and without the acrylic acid.

[0384] The resulting copolymer contained 68% by weight poly(3-hydroxynonanoate), 27% by weight poly(3-hydroxyheptanoate), and 5% by weight poly(3-hydroxypentanoate). Mn=55800g / mol Mw=124500g / mol □ Ip=2.2 □ DPn=469

[0385] Example 23: The polymer was prepared following the procedure of Example 19, using dodecanoic acid (instead of octanoic acid).

[0386] The resulting copolymer contained 44% by weight poly(3-hydroxydodecanoate), 38% by weight poly(3-hydroxydecanoate), and 18% by weight poly(3-hydroxyoctanoate). Mn=67400g / mol Mw=129800g / mol □ Ip=1.9 □ DPn=484

[0387] Example 24: Side chain R representing an n-pentyl group 1 and R representing an n-propyl group 2 A copolymer of PHA having [ka] The manufacturing process of Example 24 was adapted from the paper, Biomacromolecules 2012, 13, 2926-2932: “Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer”.

[0388] The microorganism used is Pseudomonas putida ATCC® 47054™.

[0389] The cultivation method was a dilution D = 0.25 h in a 3 L chemostat containing 1.1 L of culture medium. -1 The procedure is carried out under continuous pure culture conditions.

[0390] Nominal Dissolved Oxygen (O D The system is ventilated with an airflow of 3 vvm so that the Vp value is 30% saturated.

[0391] Assembly: See Figure 2.

[0392] The manufacturing process is carried out using three different culture media.

[0393] A first undefined culture medium (CM1) is used for the preparation of the inoculum.

[0394] A second defined culture medium (CM2) is used for batch cultivation of the microorganisms in a fermentor.

[0395] A third defined culture medium (CM3) was used to feed or maintain the continuous fermentation containing the carbon source of interest and an inhibitor of the β-oxidation pathway.

[0396] The composition of the three media in grams per liter is given in Table 13: Composition of Inoculum Medium and Maintenance Medium in grams per liter.

[0397] [Table 30]

[0398] [Table 31]

[0399] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™.

[0400] The composition of the trace element solution per liter (in grams) is given in Table 14 below: Composition of the trace element solution per liter (in grams).

[0401] [Table 32]

[0402] A 100 mL inoculum is prepared by suspending the cryotube containing 1 mL of strain with 100 mL of Nutrient Broth in a 250 mL Fernbach flask, with the pH adjusted to 7.0 with 2N NaOH, and then incubating at 30° C., 150 rpm for 24 hours.

[0403] A fermenter containing 1 liter of CM2 culture medium at 30°C was incubated at 4°C until the optical density at 630 nm reached 0.1 (O D630 The system is maintained at 30° C., with stirring at 700±200 rpm, and regulated in cascade with oxygen for approximately 16 hours and / or a period allowing the microorganism to reach its stationary phase of growth.

[0404] When the microorganism reaches its stationary growth phase, the fermenter is started to be fed with CM3 culture medium and withdrawals are made to maintain the initial mass of the fermentation medium. When the equilibrium state of the continuous culture is reached, a portion of the withdrawn material is centrifuged to separate the biomass from the fermentation medium. The biomass is dried by freeze-drying and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, consisting of PHA dissolved in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass.

[0405] The PHA can optionally be purified by sequential dissolution and precipitation, for example using a dichloromethane / methanol system.

[0406] The PHA copolymer of Example 24 was fully characterized by spectroscopic and spectrometric methods. By gas chromatography equipped with an FID detector, the copolymer was found to have 96% R 1 = n-pentyl and 4% of the group R 2 = It is known that it contains n-propyl.

[0407] Example 25: Side chain R represents a linear 5% unsaturated 8-bromo-n-octanoyl group 1 and R representing an n-hexyl group. 2 PHA having [ka] The method for synthesizing the compound of Example 1 was adapted from the paper: Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440, Z. Sun, JA Ramsay, M. Guay, BA Ramsay, Applied Microbiology Biotechnology, 82.657-662, 2009.

[0408] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054. The cultivation method is in a 3 L chemostat containing 2.5 L of culture medium at a rate of μ = 0.15 h. -1 The culture is carried out under fed-batch pure culture conditions using a maintenance medium containing a mixture of carbon sources.

[0409] Nominal Dissolved Oxygen (O D The system is aerated with an air flow of 0.5 vvm so that the pH value is 30% saturated. The pH is adjusted with a solution composed of ammonia and glucose at 15% and 40% final mass, respectively. The temperature of the fermentation medium is adjusted to 30°C.

[0410] Equipment for fed-batch fermentation mode: The fermentation medium is regulated with respect to temperature, dissolved oxygen pressure and pH (not shown).

[0411] The production method is carried out using three different culture media. The first culture medium, defined as CM1 "inoculum", is used for the preparation of a pre-culture. The second culture medium, defined as CM2 "batch", is used for the non-fed-batch cultivation of the microorganism with the primary carbon source in Fernbach flasks. The third culture medium, defined as CM3 "maintenance", is used for fed-batch or maintenance fermentation mode with the carbon source of interest at a flow rate calibrated as a function of the growth of the microorganism.

[0412] [Table 33]

[0413] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™.

[0414] [Table 34]

[0415] A 100 mL preculture is prepared by suspending a cryotube containing 1 mL of strain together with 100 mL of "inoculation" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then incubating at 30° C. and 150 rpm for 24 hours. The 100 mL preculture is added to 1.9 L of CM2 "batch" culture medium in a previously sterilized 3 L chemostat at 20° C. for 24 hours. D After 4 hours at 30° C. and 850 rpm, the introduction of the maintenance medium is carried out by applying a flow rate determined by equation 1.

[0416] After the introduction is complete, the biomass is isolated by centrifugation and washed three times with water. The biomass is dried by freeze-drying and then extracted with ethyl acetate for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®). The filtrate, consisting of PHA dissolved in ethyl acetate, is concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass.

[0417] The PHA may optionally be purified by dissolution in ethyl acetate followed by successive precipitation from, for example, a 70 / 30 v / v ethanol / water system.

[0418] The PHAs have been fully characterized by spectroscopic and spectrometric methods and have the predicted chemical structure: 2 = 95 mol % of units (B) which are n-hexyl (71%) and n-butyl (24%) and R 1 = 8-bromo-n-octanyl (5.9%) and 6-bromo-n-hexyl (0.2%), consistent with 5 mol % of units (A).

[0419] The compounds a) of Examples 1 to 25 may be mixed with one or more crystalline fatty substances b) as defined above in the presence of one or more liquid oils c) such as isododecane and optionally water e). Mixing of PHA a) with crystalline fatty substance b) may be carried out at room temperature, with stirring, preferably in the presence of a liquid fatty substance c) and optionally an organic solvent other than c) or d) as defined above. According to one variant, water e) is added to the mixture of a), b) and c), then optionally one or more organic solvents other than c) and d) as defined above are added.

[0420] Examples 26 to 34: Compositions 26 (comparative example) and 27 to 34 (invention) shown in Table 17 below were prepared.

[0421] [Table 35]

[0422] [Table 36]

[0423] Preparation of the composition: The PHA, isododecane and ethanol are stirred at 2500 rpm and at a temperature of 25° C. The crystalline fatty material is introduced and the medium is heated from 25° C. to 80° C. while stirring at 2500 rpm. It is maintained at 80° C. for 30 minutes while stirring at 3000 rpm and then cooled from 80° C. to 25° C. while stirring at 2500 rpm.

[0424] Performance evaluation Abrasion resistance Test Description: The first stage of the test consists of making the deposit. The deposit is prepared on a Byko Chart Lenata contrast card using a film spreader and left to dry for 24 hours at 25°C and 45% RH. The final deposit thickness is 30 μm.

[0425] An abrasion resistance test is carried out on this dry deposit. A hydrophilic steel ball is used as the friction device. The applied load or normal force is 1 N and the displacement speed is 50 mm.s. -1 On each coating, a track is defined over which a friction device makes multiple passes. For wear measurements, permanent contact is maintained while a ball passes back and forth over the deposit. With each track, the number of passes is incremented. Wear resistance is quantified as the minimum number of passes to completely wear down the deposit.

[0426] In this study, the number of passes per track was 10, 30, 50, 100, 200 and 300 passes, respectively.

[0427] Each measurement was repeated five times.

[0428] The results of the abrasion resistance test are quantified as shown in the table below.

[0429] [Table 37]

[0430] [Table 38]

[0431] It can be seen that the composition according to the invention is significantly better tolerated than the comparative composition which does not contain any crystalline fatty substance b).

[0432] Water resistance Test Description: On the same 30 μm dry deposits made for the abrasion test, the sensitivity to the stressor is evaluated after depositing a drop of stressor (20 μl for water) on the surface of the deposit. The evaluation is carried out after 1 hour of contact between the stressor and the deposit. The level of sensitivity to the stressor is noted as follows: All compositions of the invention (Examples 27-33) are found to be very resistant to water since the film remained intact.

[0433] Example 1": A 2% unsaturated n-octenyl group bearing side chain R, carried out in discontinuous culture fed with two carbon sources, C9 and C11:1 98 / 2 1 and R represents an unsaturated n-hexyl group. 2 PHA copolymer having [ka]

[0434] The process for obtaining Example 1″ is described in Appl Microbiol Biotechnol 82:657-662 (2009). Adapted from "Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440".

[0435] The microorganism used is Pseudomonas putida KT2440 ATCC® 47054™.

[0436] The cultivation mode is carried out under pure conditions of discontinuous cultivation in a 3 L chemostat containing 2.5 L of culture medium, where a maintenance solution containing a mixture of carbon sources is fed at a rate of μ = 0.15 h-1. The flow rate of the maintenance feed pump is proportional to the growth of the microorganism according to equation 1:

number

[0437] Equation 1: Theoretical equation that relates the amount of biomass and the amount of carbon source as a function of time, St = biomass X at time t t The amount of carbon source required to produce Y (g) X / S = biomass yield from the carbon source, X0 = initial biomass (g), μ = desired specific growth rate (h-1).

[0438] The system is aerated with an air flow of 0.5 vvm with a dissolved oxygen (DO) set point of 30% saturation. The pH is adjusted with a 15% ammonia solution. The temperature of the fermentation medium is adjusted to 30° C. The assembly of the fed-batch fermentation mode is made according to FIG. 1.

[0439] The fermentation medium is regulated by temperature, dissolved oxygen tension and pH (not shown).

[0440] The production process is carried out using three different media: The first culture medium, defined as MC1 "inoculum", is used for the preparation of a preculture.

[0441] A second culture medium, defined as MC2 "batch", is used for non-fed discontinuous growth of microorganisms with a primary carbon source in Fernbach flasks.

[0442] A third culture medium, defined as (MC3 "Maintenance"), is used for discontinuous feeding, or maintenance, of the fermentation with the carbon source of interest at a rate calibrated to the growth of the microorganism.

[0443] The composition of the three media in grams per liter is given in Table 19.

[0444] [Table 39]

[0445] Table 19: Composition in grams per liter of culture medium for pre-culture and maintenance.

[0446] The composition of Nutrient Broth, by weight, is 37.5% beef extract and 62.5% peptone, reference number 233000 DIFCO™.

[0447] The composition of the solution of trace elements in grams per liter is given in Table 20.

[0448] [Table 40]

[0449] Table 20: Composition of trace element solutions in grams per liter

[0450] A 100 mL preculture is prepared by suspending a cryotube containing 1 mL of the strain in 100 mL of "inoculation" culture medium in a 250 mL Fernbach flask, pH adjusted to 6.8 with 2N NaOH, and then cultivating for 24 hours at 30° C. and 150 rpm. 100 mL of preculture is inoculated at OD=0.1 into 1.9 L of MC2 "batch" culture medium, placed in a 3 L chemostat previously sterilized. After 4 hours at 30° C. and 850 rpm, a maintenance induction is carried out by applying a flow rate determined by equation 1. After the end of the induction, the biomass is isolated by centrifugation and washed three times with water. The biomass is dried by lyophilization and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration through a GF / A filter (Whatman®) and the filtrate, consisting of a solution of PHA in dichloromethane, is concentrated by evaporation and then dried under high vacuum at 40° C. until constant mass. The PHA can be optionally purified by solubilization and subsequent precipitation, for example, with a dichloromethane-methanol system.

[0451] The PHA was characterized by gas chromatography with FID detection and matched the expected chemical structure with 2% unsaturation.

[0452] Example 11': Linear side chain R representing the n-octylenyl group of Example 1'' 1 and 2% n-hexyl unsaturated R 2 Functionalization of mcl-PHA bearing thiolactic acid [ka] 2 g of the compound of Example 1'' and 180 mg of thiolactic acid were dissolved in 15 mL of ethyl acetate with stirring at room temperature. 5 mg of 2-hydroxy-2-methylpropiophenone (HMP) were added to the mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) for at least 10 minutes with stirring. The reaction medium thus obtained was poured onto a Teflon plate and dried under dynamic vacuum at 40°C, obtaining a homogeneous film. The PHA grafted with thiolactic acid was fully characterized by proton NMR. The proton NMR spectrum shows the complete disappearance of the characteristic signals of unsaturation.

[0453] The compositions of Examples 32-35 contain the ingredients according to Table 21.

[0454] [Table 41]

[0455] [Table 42]

[0456] Abrasion resistance Test Description: The first stage of the test consists of making a deposit. The deposit is prepared on a Byko Chart Lenata contrast card and left to dry for 24 hours at 25°C and 45% RH. The final deposit thickness is 30 μm.

[0457] An abrasion resistance test is carried out on this dry deposit. A hydrophilic steel ball is used as the friction device. The applied load or normal force is 1 N and the displacement speed is 50 mm.s. -1 On each coating, a track is defined over which a friction device makes multiple passes. For wear measurements, permanent contact is maintained while a ball passes back and forth over the deposit. With each track, the number of passes is incremented. Wear resistance is quantified as the minimum number of passes to completely wear down the deposit.

[0458] In this study, the number of passes per track was 10, 30, 50, 100, 200 and 300 passes, respectively.

[0459] Each measurement was repeated five times.

[0460] The results of the abrasion resistance test are quantified as shown in the table below.

[0461] [Table 43]

[0462] [Table 44]

[0463] Compared to the mcl-PHA formulation alone, the dry wear resistance was improved when wax was added. It should also be noted that the formulation made from scl-PHA did not produce deposits. It should also be noted that for Example 35 carried out with scl-PHA, no deposits could be obtained.

[0464] It can be seen that the compositions of the invention (Examples 32-34) remain very water resistant. The presence of some oil does not affect the water resistance of the resulting film.

Claims

1. Composition C1', a) the following units (A) and (B): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) (In polymer units (A) and (B): ・R １ represents a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain, or a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon-based chain, containing from 5 to 28 carbon atoms; preferably, said hydrocarbon-based chain is i) linear or branched (C ５ ~C ２８ ) alkyl, ii) linear or branched (C ５ ~C ２８ ) alkenyl, iii) linear or branched (C ５ ~C ２８ ) alkynyl; preferably, said hydrocarbon-based groups are linear; The hydrocarbon-based chain is a) halogens such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C １ ~C ４ ) (alkyl)amino, e) (thio)carboxy, f) (thio)carboxamido-C(O)-N(R ａ ) ２ or C(S)-N(R ａ ) ２ , g) cyano, h) iso(thio)cyanate, i) (hetero)aryl such as phenyl or furyl, j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) a cosmetic active agent, l) α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as a sugar, preferably a monosaccharide such as glucose, γ) (hetero)aryl such as phenyl, δ) a cosmetic active agent, m) thiosulfate, and a′) O, S, N(R ａ ) or Si(R ｂ ) (R ｃ ), b') S(O) ｒ or (thio)carbonyl, or c') R-X with X representing a combination of a') and b'), such as (thio)ester, (thio)amide, (thio)urea or sulfonamide; R ａ is a hydrogen atom, or (C １ ~C ４ ) alkyl group, or aryl such as benzyl (C １ ~C ４ ) represents an alkyl group, preferably R ａ represents a hydrogen atom; R ｂ and R ｃ may be the same or different, (C １ ~C ４ ) alkyl or (C １ ~C ４ ) an alkoxy group, which is particularly preferably substituted by only one substituent selected from b) halogen and j) epoxide; and / or one or more a′) heteroatoms, such as O, S, N(R ａ ) and Si(R ｂ ) (R ｃ ), b') S(O) ｒ , (thio)carbonyl, or c') a combination of a') and b'), such as (thio)ester, (thio)amide, (thio)urea, sulfonamide, etc.; r is 1 or 2; R ａ is as defined above, preferably R ａ represents a hydrogen atom, R ｂ and R ｃ is as defined above; and ・R ２ In particular, linear or branched (C ３ ~C ２８ ) alkyl and linear or branched (C ３ ~C ２８ ) alkenyl, especially linear hydrocarbon-based groups, more especially (C ４ ~C ２０ ) alkyl or C ４ ~C ２０ ) alkenyl; R １ represents a cyclic or acyclic, linear or branched, saturated or unsaturated, hydrocarbon-based group containing 3 to 30 carbon atoms, optionally substituted with one or more atoms or groups a) to m) and / or optionally interrupted with one or more heteroatoms or groups a') to c'), as defined for (a) above; preferably, said hydrocarbon-based group is a cyclic or acyclic, linear or branched, saturated or unsaturated, hydrocarbon-based group containing 3 to 30 carbon atoms, optionally substituted with one or more atoms or groups a) to m) and / or optionally interrupted with one or more heteroatoms or groups a') to c'), as defined for (a) above, minus at least one carbon atom; １ and preferably at least two carbon atoms are subtracted therefrom. １ and one or more polyhydroxyalkanoate (PHA) copolymers containing, preferably consisting of, at least two different repeating polymer units selected from: b) one or more fatty substances that are crystallizable at 25° C. and atmospheric pressure; c) optionally one or more oils, i.e. fatty substances, which are liquid at 25° C. and atmospheric pressure; d) optionally one or more organic solvents, preferably polar aprotic or protic solvents, in particular polar and protic solvents; e) optionally with water Including; however, - it is understood that (A) is different from (B), and said composition C1' preferably contains c); more preferably a composition C1' containing components c)+d).

2. The PHA copolymer a) is represented by the formula (I) 【Chemistry 1】 (In formula (I), ・R １ and R ２ is as defined in claim 1; m and n are integers equal to or greater than 1; preferably, the sum of n+m is between 450 and 1400, inclusive; Preferably, R １ and R ２ When R represents an unsubstituted and uninterrupted alkyl group, m>n, more preferably R １ and R ２ When R is a linear alkyl, １ is C ５ ~C １３ is an alkyl group; and R ２ is R minus two carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ represents a substituted and / or interrupted alkyl group, an optionally substituted and / or interrupted alkenyl group or an optionally substituted and / or interrupted alkynyl group, R ２ When m represents an alkyl group, m<n), and further optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates.

3. The PHA copolymer a) contains three different repeating polymer units (A), (B) and (C), preferably the following three different polymer units (A), (B) and (C): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) -[-O-CH(R ３ )-CH ２ -C(O)-]- unit (C) (In the polymer units (A), (B) and (C), - R １ and R ２ is as defined in claim 1 or 2; - R ３ is a saturated or unsaturated, linear or branched, cyclic or acyclic, hydrocarbon-based group containing 1 to 30 carbon atoms, １ and / or optionally interrupted by one or more heteroatoms or groups a') to c'); in particular linear or branched (C １ ~C ２８ ) alkyl and linear or branched (C ２ ~C ２８ ) alkenyl, especially linear hydrocarbon-based groups, more especially (C ４ ~C ２０ ) alkenyl; preferably, said hydrocarbon-based group is selected from the group R １ or the number of carbon atoms of said group R １ and preferably with 4 carbon atoms subtracted therefrom. １ (having a number of carbon atoms corresponding to the number of carbon atoms of 1 to 10), and also optical or geometric isomers thereof, and solvates thereof, such as hydrates; - (A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different from (A) and (B); and Preferably, R １ , R ２ and R ３ represents an unsubstituted and uninterrupted alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B) and greater than the mole percentage of units (C), more preferably R １ , R ２ and R ３ When R is a linear alkyl, １ is C ５ ~C １３ is an alkyl group, R ２ is R minus two carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of ３ is R minus 4 carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ In particular, when R represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, ２ represents an alkyl group and / or R ３ represents an alkyl group, it is understood that the mole percentage of units (A) is less than the mole percentage of units (B) and the mole percentage of units (C) is less than the mole percentage of units (B); More preferentially, said PHA copolymer a) has the formula (II): 【Chemistry 2】 (In formula (II), ・R １ , R ２ and R ３ is as defined above; m, n and p are integers equal to or greater than 1; preferably, the sum n+m+p is between 450 and 1400, inclusive; Preferably, R １ , R ２ and R ３ When R represents an unsubstituted and uninterrupted alkyl group, m>n+p, and more preferably, R １ , R ２ and R ３ When R is a linear alkyl, １ is C ５ ~C １３ is an alkyl group, R ２ is R minus two carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of ３ is R minus 4 carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group or an optionally substituted and / or optionally interrupted alkynyl group, R ２ and R ３ When m represents an alkyl group, m<n+p), and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates.

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

5. The PHA copolymer a) contains five different repeating polymer units (A), (B), (C), (D) and (E), and preferably the following five different polymer units (A), (B), (C), (D) and (E): -[-O-CH(R １ )-CH ２ -C(O)-]- unit (A) -[-O-CH(R ２ )-CH ２ -C(O)-]- unit (B) -[-O-CH(R ３ )-CH ２ -C(O)-]- unit (C) -[-O-CH(R ４ )-CH ２ -C(O)-]- unit (D) -[-O-CH(R ５ )-CH ２ -C(O)-]- unit (E) (In the polymer units (A), (B), (C), (D) and (E), - R １ , R ２ , R ３ and R ４ is as defined in any one of claims 1 to 4, - R ５ is R １ represents a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, optionally interrupted by one or more atoms or groups a) to l) as defined in relation to R, and / or optionally interrupted by one or more heteroatoms or groups a') to c'); １ Linear or branched (C ４ ~C ２８ ) alkyl; and preferably, said hydrocarbon-based group is selected from said group R ４ the number of carbon atoms of said group R ４ (having a number of carbon atoms corresponding to the number of carbon atoms of), as well as their optical or geometric isomers, organic or mineral acid or base salts and also solvates thereof, such as hydrates; - (A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E); (C) is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E) is different from (A), (B), (C) and (D); Preferably, R １ , R ２ , R ３ , R ４ and R ５ represents an unsubstituted and uninterrupted alkyl group, the mole percentage of units (A) is greater than the mole percentage of units (B), which is greater than the mole percentage of units (C), which is greater than the mole percentage of units (D), which is greater than the mole percentage of units (E), and more preferably, R １ , R ２ , R ３ , R ４ and R ５ When R is a linear alkyl, １ is C ５ ~C １３ is an alkyl group, R ２ is R minus two carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of ３ is R minus 4 carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of ４ is R minus 6 carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of ５ is R minus 8 carbon atoms. １ represents a linear alkyl group having a carbon number corresponding to the carbon number of Preferably, R １ In particular, when R represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, ２ represents an alkyl group and / or R ３ represents an alkyl group; and R ４ and R ５ represents an optionally substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, it is understood that the mole percentage of units (A) is less than the mole percentage of units (B) and the mole percentage of units (C) is less than the mole percentage of units (B); More preferentially, said PHA copolymer has formula (IV): 【Chemistry 4】 (In formula (IV): ・R １ , R ２ , R ３ , R ４ and R ５ is as defined above; m, n, p, v and z are integers equal to or greater than 1; preferably, the sum of n+m+p+v+z is between 450 and 1400, inclusive; Preferably, R １ , R ２ , R ３ , R ４ and R ５ represents an unsubstituted and / or uninterrupted alkyl group, then m>n+p+v+z; Preferably, R １ represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group; R ２ and R ３ represents an alkyl group, and the R ４ and R ５ Composition C1' according to any one of claims 1 to 4, comprising repeating units of the formula n>m+v+z; more preferably n+p>m+v+z, where n>m+v+z; if the group represents a substituted and / or interrupted alkyl group, an optionally substituted and / or optionally interrupted alkenyl group, or an optionally substituted and / or optionally interrupted alkynyl group, and also optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates.

6. R １ is linear or branched, preferably linear (C ５ ~C ２８ ) alkyl hydrocarbon-based chain; more particularly, R １ is an alkyl group substituted with one or more atoms or groups a) to k), said alkyl group containing 5 to 12, preferably 6 to 10 carbon atoms, more preferably 7 to 9 carbon atoms, such as n-octyl; preferably R １ b) hydroxyl, c) thiol, d) (di)(C １ ~C ４ a) (alkyl)amino, preferably amino; b) carboxyl; c) (hetero)cycloalkyl, such as an acid anhydride or an epoxide; d) a cosmetic active agent selected from colored or uncolored, fluorescent or non-fluorescent chromophores, such as optical brighteners, UV screening agents; e) (hetero)aryl, such as phenyl or furyl; k) R-X, where R represents a group selected from α) cycloalkyl, such as cyclohexyl; β) heterocycloalkyl, e.g. a monosaccharide, such as a sugar, preferably glucose; γ) (hetero)aryl, such as phenyl; δ) a cosmetic active agent as defined above, where X represents a group selected from a′) O, S, N(R ａ ), b') carbonyl, c') or a combination of those of a') and b') an ester, amide or urea, etc.; R ａ is a hydrogen atom or (C １ ~C ４ ) alkyl or aryl such as benzyl (C １ ~C ４ ) represents an alkyl group, preferably R ａ represents a hydrogen atom]; more preferably, the PHA copolymer is １ is a hydrocarbon-based chain, in particular a) a halogen, such as chlorine or bromine, b) a hydroxyl, d) a (di)(C １ ~C ４ e) (alkyl)amino, preferably amino; e) carboxyl; i) (hetero)cycloalkyl, such as epoxide; h) (hetero)aryl, such as phenyl or furyl; k) α) cycloalkyl, such as cyclohexyl; β) heterocycloalkyl, such as a sugar, preferably a monosaccharide, such as glucose; γ) (hetero)aryl, such as phenyl; and a′) O, S or N(R ａ R represents an alkyl group as defined above substituted by one or more (preferably one) groups selected from R-X, with X preferably representing S; ａ is a hydrogen atom or (C １ ~C ４ ) represents an alkyl group, preferably R ａ is such that it represents a hydrogen atom; More preferably, the hydrocarbon-based chain R １ is the group R １ Composition C1' according to any one of claims 1 to 5, which is substituted at the chain end opposite the carbon atom having

7. R １ but a hydrocarbon-based chain, especially an alkyl, especially C ７ ~C ２０ , more particularly C ８ ~C １８ , and more particularly C ９ ~C １６ Alkyl, O, S, N(R ａ ), carbonyl, or alkyl interrupted by one or more (preferably one) atoms or groups selected from ester, amide, or urea, or combinations thereof, ａ is as defined in claims 1 to 6, preferably R ａ Composition C1' according to any one of claims 1 to 6, wherein represents a hydrogen atom; preferably an alkyl group interrupted by one or more atoms selected from O and S, more preferably an O or S, in particular an S atom; preferably said interrupted hydrocarbon-based chain, in particular an alkyl, is linear.

8. R １ is represented by the following formula -(CH ２ ) ｒ -X-(ALK) ｕ -G, X is as defined above, in particular O, S or N(R ａ ), preferably S; ALK is a linear or branched, preferably linear (C １ ~C １０ ) alkylene, more particularly (C １ ~C ８ ) alkylene chain, r represents an integer between 6 and 11, preferably between 7 and 10, such as 8, u is equal to 0 or 1; and G represents a hydrogen atom or a hydroxyl, carboxyl, (di)(C １ ~C ４ ) (alkyl)amino, (hetero)aryl, in particular aryl such as phenyl, cycloalkyl such as cyclohexyl, or a sugar, in particular a monosaccharide optionally protected by one or more groups such as acyl, preferably Sug is 【Chemistry 5】 represents R ｆ is (C) such as methyl １ ~C ４ ) alkyl group; preferably, when u is equal to 0, G represents a cycloalkyl group, such as cyclohexyl, or a sugar as defined above; according to another advantageous variant, when u is equal to 1, G represents a hydrogen atom or a hydroxyl, carboxyl, (di)(C １ ~C ４ 8. Composition C1' according to any one of claims 1 to 7, in which C1' represents a group selected from: (alkyl)amino or (hetero)aryl, in particular aryl, such as phenyl.

9. The PHA copolymer a) is linear or branched (C １ ~C ２８ ) alkyl and linear or branched (C ２ ~C ２８ ) alkenyl, especially linear hydrocarbon-based groups, especially (C ３ ~C ２０ ) alkyl or (C ３ ~C ２０ ) a group R selected from alkenyl ２ Preferably, the hydrocarbon-based group is a group R １ the number of carbon atoms of said group R １ Composition C1' according to any one of claims 1 to 8, having a number of carbon atoms corresponding to the number of carbon atoms of:

10. The PHA copolymer a) is linear or branched, preferably linear (C １ ~C ８ ) alkyl, especially (C ２ ~C ６ ) alkyl, preferably (C ４ ~C ６ ) an alkyl group, such as n-pentyl or n-hexyl; or R ２ is branched (C ３ ~C ８ ) alkyl, especially (C ４ ~C ６ ) alkyl group, preferably branched (C ４ ~ C ５ ) a radical R which is alkyl, for example isobutyl ２ The composition C1' according to any one of claims 1 to 9, comprising:

11. The PHA copolymer is １ But (C ３ ~C ３０ 11. Composition C1' according to any one of claims 1 to 10, such that, relative to all units (A), (B) and (C), the units (A) are preferably present in a molar percentage ranging from 0.5% to 99%, more preferably in a molar percentage ranging from 1% to 50%, even more preferably in a molar percentage ranging from 5% to 40% and better still in a molar percentage ranging from 5% to 30%; the units (B) are present in a molar percentage ranging from 1% to 99.5%, preferably in a molar percentage ranging from 1% to 99%, more preferably in a molar percentage ranging from 2% to 98%; and the units (C) are present in a molar percentage ranging from 0.5% to 20%.

12. The PHA copolymer is １ i) linear or branched (C ５ ~C ２８ ) alkyl, ii) linear or branched (C ５ ~C ２８ ) alkenyl, iii) linear or branched (C ５ ~C ２８ ) alkynyl, preferably the hydrocarbon-based group is linear and said hydrocarbon-based chain is selected from R １ and / or interrupted by one or more heteroatoms or groups a') to c'); it is in particular linear or branched (C ４ ~C ２８ ) alkyl, optionally substituted with one or more atoms or groups a) to m) as defined above and / or interrupted by one or more heteroatoms or groups a') to c'), - said units (A) are present in a molar percentage ranging from 0.1% to 99%, preferably in a molar percentage ranging from 0.5% to 50%, more preferably in a molar percentage ranging from 1% to 40%, even more preferably in a molar percentage ranging from 2% to 30%, better still in a molar percentage ranging from 5% to 20%, and even better still in a molar percentage ranging from 10% to 30%; and - said units (B) are present in a molar percentage ranging from 1% to 99.9%, preferably in a molar percentage ranging from 2% to 99%, more preferably in a molar percentage ranging from 5% to 70%; and Composition C1' according to any one of claims 1 to 11, wherein said units (C) are present in a molar percentage ranging from 0.5% to 20%, based on the sum of said units (A), (B) and (C), advantageously the PHA copolymer of the invention comprises from 2 mol% to 98 mol% of units (B) and from 0.5 mol% to 10 mol% of units (C); more advantageously the copolymer is such that it comprises from 5 mol% to 70 mol% of units (B) and from 0.5 mol% to 7 mol% of units (C).

13. The PHA copolymer a) is selected from the group consisting of: 【Table 1】 (Wherein, repeating units A1 to A12: -ALK １ is a divalent linear or branched C １ ~C ２０ , preferably linear or branched, more preferably linear C １ ~C １０ represents a hydrocarbon-based group; -ALK ２ is a divalent linear or branched C １ ~C ２０ , preferably linear or branched C １ ~C １２ represents a hydrocarbon-based group; Rr and Rw are independently a hydrogen atom or a C alkyl group such as methyl. １ ~C ４ represents an alkyl group; preferably, Rr and Rw are the same; 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 a heterocycloalkyl group such as a dithiolane or an epoxide, preferably an epoxide; Fur: ​​represents a furyl group, preferably 2-furyl; Sug: represents a sugar group, in particular a monosaccharide, optionally protected by one or more groups such as acyl, in particular acetyl; In particular, the group R １ The stereochemistry of the carbon atom having the formula (I) is in the (R) configuration), and further comprising an optical isomer or geometric isomer thereof, an organic or mineral acid or base salt thereof, and a solvate such as a hydrate thereof.

14. The PHA copolymer comprises the following repeating units, as well as optical or geometric isomers thereof, organic or mineral acid or base salts thereof, and solvates thereof, such as hydrates thereof: 【Chemistry 6】 【Table 2】 【Table 3】 【Table 4】 m and n are as defined above, Hal represents a halogen atom such as bromine, t represents an integer from 1 to 10, preferably from 3 to 8, for example 6, Ar represents a (hetero)aryl group such as phenyl; Ar': t-butylphenyl, etc. １ ~C ４ ) an alkyl(hetero)aryl group, preferably 4-t-butylphenyl; Cycl: represents a cyclohexyl group; Fur: ​​represents a furyl group, preferably 2-furyl; Sug: represents a sugar group, in particular a monosaccharide optionally protected by one or more groups such as acyl; preferably Sug is: 【Chemistry 7】 (In the formula, R ｅ is a group R ｆ represents —C(O)—, R ｆ is methyl, etc. (C １ ~C ４ ) represents an alkyl group, More preferentially, the PHA copolymer has the following formula, and also its optical isomers, its organic or mineral acid or base salts, and its solvates, such as hydrates: 【Chemistry 8】 【Table 5】 【Table 6】 【Table 7】 M, n, Hal, t, Ar, Ar', Cycl, Fur and Sug are as defined above for compounds (1) to (14); 【Chemistry 9】 【Table 8】 【Chemistry 10】 【Table 9】 【Table 10】 【Table 11】 【Table 12】 Preferably, the PHA of the present invention is selected from compounds (2a), (10), (15), (16), (17) and (20); more preferably, the PHA of the present invention is selected from compounds (15), (16) and (17), especially (16); more preferably, the PHA of the present invention is selected from compounds (2a'), (10'), (15'), (16') and (17'); more especially, the PHA of the present invention is selected from compounds (15'), (16). Composition C1' according to any one of claims 1 to 13, wherein the PHAa) of the present invention is selected from the compounds (25), (26), (31), (32) and (34a), more preferably the PHAa) of the present invention is selected from the compounds (25), (26), (31) and (32), in particular (26).

15. Composition C1' according to any one of the preceding claims, in which the PHA copolymer a) is present in a content ranging from 0.1% to 65% by weight, preferably ranging from 0.1% to 60% by weight, relative to the total weight of the composition; in particular in a content ranging from 1% to 50% by weight, more in particular in the range from 3% to 40% by weight, preferably in the range from 5% to 35% by weight, more preferably in the range from 10% to 30% by weight and better still in the range from 15% to 20% by weight.

16. The crystalline fatty material is i) crystalline fatty substances of fossil origin, in particular 1) paraffin waxes, 2) ozokerite, 3) ceresin and 4) microcrystalline waxes, especially those containing from 20 to 60 carbon atoms; ii) crystalline fatty substances of vegetable origin, in particular 5) carnauba wax, 6) candelilla wax, 7) laurel wax, in particular oleander wax, 8) sugar cane wax, 9) ceramides, 10) esparto wax, 11) olive tree wax, 12) rice wax, 13) sunflower seed wax, 14) hydrogenated jojoba wax, 15) hydrogenated castor oil, 16) hydrogenated olive oil, 17) hydrogenated cottonseed oil, 18) polyglyceryl-3 esters of green mimosa, jojoba and sunflower wax, 19) absolute flower waxes such as blackcurrant flower essential wax, 20) soy wax, 21) myrica fruit wax, 22) currant wax, 23) raffia wax, 24) Colombian wax, 25) esparto wax , 26) alfalfa wax, 27) bamboo wax, 28) hemp wax, 29) Douglas fir wax, 30) cork wax, 31) sisal wax, 32) flax wax, 33) cotton wax, 34) dammar wax, 35) cereal wax, 36) tea wax, 37) coffee wax, 38) okatira wax, 39) palm wax, 40) myrica wax, 41) bayberry wax, 42) ukuba wax, 43) borneo wax, 44) malabar wax, 45) illipe wax and 46) japan tallow wax or japan wax, preferably japan wax; iii) crystalline fatty substances of animal origin, in particular those selected from 47) beeswax, 48) modified beeswax (sera verina), 49) lanolin, 50) spermaceti, and 51) shellac wax; Composition C1' according to any one of claims 1 to 15, wherein the crystalline fatty substance is preferably selected from 4) microcrystalline waxes, in particular those containing from 20 to 60 carbon atoms, 5) carnauba wax, 6) candelilla wax, 13) sunflower seed wax, 46) Japan tallow wax or Japan wax, preferably Japan wax or more preferably sunflower seed wax.

17. b) the crystalline fatty material is １０ ~C ３６ Fatty alcohol and / or C １２ ~C ３８ crystalline mono- / di- / tri-esters derived from fatty acids, and mixtures thereof, in particular iv) C １０ ~C ３０ Fatty alcohol and / or C １２ ~C ２４ Esters of fatty acids, in particular of formula (Ib) R ｂ -C(O)-O-R ｂ’ (In formula (Ib): R ｂ and R ｂ’ may be the same or different, but preferably different, and represent linear or branched, preferably linear, saturated or unsaturated, preferably saturated, hydrocarbon-based chains containing from 10 to 38 carbon atoms; preferably, R ｂ’ is optionally substituted by one or more hydroxyl groups and / or optionally interrupted by one or more oxygen atoms, carbonyls, or combinations thereof, such as esters; １２ ~C ３６ represents a hydrocarbon-based chain of the formula: ｂ is in particular linear, saturated, unsubstituted and optionally interrupted by ester groups, １２ ~C ３８ represents a hydrocarbon-based chain, R ｂ’ is in particular linear, saturated and unsubstituted, C １２ ~C ３０ In particular, cetyl palmitate or myricyl palmitate, and stearate C １８ ~C ３８ alkylhydroxystearoyl; and v) a compound of formula (Ib): 【Chemistry 11】 (In formula (Ib'): ・R ｂ’ , R ｂ’’ and R ｂ’’’ may be the same or different and are hydrogen atoms or linear or branched, preferably linear, saturated or unsaturated, preferably saturated, hydrocarbon-based chains containing 10 to 30 carbon atoms, preferably C １２ ~C ２４ represents a hydrocarbon-based chain of the formula: ALK, ALK', ALK'' may be present or absent, identical or different, and represent a linear or branched C1-C4 alkylene group, optionally substituted by at least one hydroxyl group; preferably ALK' and ALK'' are a methylene group -CH ２ - represents ALK is absent; L, L' and L'' may be the same or different, but are preferably the same, and represent an ester group -C(O)-O- or -O-C(O)-, preferably -O-C(O)-; m, m' and m'' represent 0 or 1, preferably 1; It is understood that the three groups Rb', Rb'' and Rb'' cannot simultaneously represent a hydrogen atom), as well as optical and geometric isomers thereof, and solvates thereof, such as hydrates; Composition C1' according to any one of claims 1 to 16, wherein the crystalline fatty substance is preferably chosen from compounds of formula (I'b), such as glyceryl behenate, glyceryl dibehenate, trihydroxystearin, tribehenin, and mixtures thereof.

18. b) said crystalline fatty substance is present in composition C1' in an amount ranging from 0.01% to 30% by weight, more particularly from 0.1% to 20% by weight, more particularly from 0.5% to 10% by weight, for example 5% by weight relative to the total weight of the composition; Composition C1' according to any one of the preceding claims, wherein the crystalline fatty substance is preferably present in a content ranging from 0.1% to 15% by weight, preferably from 0.5% to 12% by weight, preferably from 1% to 8% by weight and advantageously from 2% to 7% by weight relative to the total weight of said composition C1'.

19. c) is preferably liquid at 20° C. and atmospheric pressure, in particular Hydrocarbons, especially alkanes, oils of animal origin, □ Plant-derived oils, □ Glycerides or fluoro oils of synthetic origin, □ Fatty alcohols, □ Esters of fatty acids and / or fatty alcohols, □ Non-silicone wax, silicone, and □ Mixture of these comprising one or more fatty substances selected from In particular, the liquid hydrocarbon-based fatty substance is a hydrocarbon-based oil, preferably volatile or a mixture of different volatile oils; the volatile oil is preferably a linear or branched C ８ ~C １４ , more preferably C ９ ~C １３ , more preferably C ９ ~C １２ Composition C1' according to any one of claims 1 to 18, wherein the volatile oil is selected from alkanes, more particularly selected from undecane, dodecane, tridecane and isododecane; or the mixture of different volatile oils preferably comprises isododecane in said mixture, or is a mixture of undecane and tridecane.

20. c) is preferably liquid at 20° C. and atmospheric pressure, in particular vegetable oils formed by fatty acid esters of polyols, in particular triglycerides, such as, for example, sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, almond oil, calendula oil, palm oil, grape seed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil or cereal germ oil; linear, branched or cyclic esters containing more than 6 carbon atoms, in particular containing from 6 to 30 carbon atoms; in particular isononyl isononanoate; More specifically, R ｄ represents a higher fatty acid residue containing 7 to 19 carbon atoms, R ｅ represents a hydrocarbon-based chain containing 3 to 20 carbon atoms; ｄ -C(O)-O-R ｅ Esters of, for example, palmitate, adipate, myristate and benzoate, especially diisopropyl adipate and isopropyl myristate; more preferably, R ｄ represents a higher fatty acid residue containing 8 to 10 carbon atoms, R ｅ represents a hydrocarbon-based chain containing 12 to 18 carbon atoms; ｄ -C(O)-O-R ｅ Esters of; Hydrocarbons, in particular volatile or non-volatile linear, branched and / or cyclic alkanes, for example optionally volatile C ５ ~C ６０ Isoparaffins, such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or Isopars, and mixtures thereof; or alkanes obtained from the complete hydrogenation / reduction of a mixture of fatty acids derived from Cocos nucifera (coconut) oil, such as dodecane, C 2 O 4 with a chain containing 9 to 12 carbon atoms. ９ ~C １２ Alkanes, preferably linear or branched C ９ ~C １２ Mixtures of alkanes, especially those containing dodecane, or liquid paraffin, liquid petroleum jelly, or hydrogenated polyisobutylene; ethers containing from 6 to 30 carbon atoms; ketones containing from 6 to 30 carbon atoms; aliphatic fatty monoalcohols containing from 6 to 30 carbon atoms whose hydrocarbon-based chain does not contain any substituents, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; polyols containing 6 to 30 carbon atoms, for example hexylene glycol; and - Mixtures thereof, for example linear or branched C ８ ~C １０ Fatty acids and C １２ ~C １８ Esters with fatty alcohols and alkanes, especially mixtures of dodecanes, resulting from the complete hydrogenation / reduction of a mixture of fatty acids derived from Cocos nucifera (coconut) oil, for example mixtures of cocoyl caprylate / caprate and dodecane; or C ９ ~C １２ Alkanes, preferably linear or branched C ９ ~C １２ Alkanes, especially C including dodecane ９ ~C １２ Preferably, the hydrocarbon-based liquid fatty substance iii) comprises one or more fatty substances selected from a mixture of linear or branched C ６ ~C １６ , preferably C ８ ~C １４ , more preferably C ９ ~C １３ , more preferably C ９ ~C １２ Preferably, the alkane is selected from the group consisting of alkanes, more preferably the alkane is volatile and is selected from undecane, dodecane, isododecane, tridecane, and in particular dodecane, isododecane, or mixtures thereof consisting of mixtures of undecane and tridecane; Alternatively, the liquid fatty substance iii) is a mixture of non-volatile oil and volatile oil, in particular comprising as volatile oil isododecane, undecane, dodecane, isododecane and / or tridecane, more preferably isododecane; as a mixture of volatile and non-volatile oils, mention may be made of a mixture of isododecane and isononyl isononanoate; and more preferably, when the fatty substance is a mixture of volatile and non-volatile oil, the amount of volatile oil is greater than the amount of non-volatile oil. Composition C1' according to any one of claims 1 to 19.

21. Composition C1' according to any one of the preceding claims, comprising d) one or more organic solvents other than c) polar protic organic solvents or polar aprotic organic solvents, preferably polar protic organic solvents, in particular lower monoalcohols comprising from 2 to 10 carbon atoms such as ethanol and isopropanol, preferably ethanol, preferably the amount of organic solvent being less than 70% by weight, more preferentially less than 50% by weight relative to the total weight of said composition C1'; according to one embodiment of the invention, composition C1' comprises an amount of organic solvent greater than 0.5% by weight, more in particular greater than 1% by weight, relative to the total weight of the composition, in particular said composition comprises between 2% and 50% by weight of organic solvent.

22. 22. The composition according to any one of claims 1 to 21, which also comprises one or more colorants, preferably pigments, chosen from pigments, direct dyes and mixtures thereof; more preferentially, said pigments of the present invention are chosen from carbon black, iron oxides, in particular black iron oxide and mica coated with iron oxide, triarylmethane pigments, in particular blue and purple triarylmethane pigments, such as Blue 1 Lake, also azo pigments, in particular red azo pigments, such as D&C Red 7, alkali metal salts of lithole red, such as the calcium salt of lithole red B, and even more preferentially red iron oxide.

23. A method for treating keratinous materials, preferably α) keratinous fibres, in particular human keratinous fibres such as hair, or β) human skin, in particular the lips, by applying a composition according to any one of claims 1 to 22.

24. Cosmetic use of a composition according to any one of claims 1 to 22.

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