KR20240101621A - A cosmetic composition comprising a polyhydroxyalkanoate copolymer having an (un)saturated hydrocarbon-based chain and a mixture of volatile and non-volatile oils. - Google Patents

Abstract

This invention
a) at least one poly, preferably consisting of several repeating units selected from the following units (A) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof: Hydroxyalkanoate (PHA) copolymer:
-[-O-CH(R ¹ )-CH ₂ -C(O)-J- Unit (A)
[In polymer unit (A) : - R ¹ is as defined herein];
b) one or more volatile oils;
c) contains at least one non-volatile oil;
The mass ratio U between the sum of the masses of the volatile oil b) and the sum of the masses of the non-volatile oil c) is understood to be non-zero and less than 900.

Description

A cosmetic composition comprising a polyhydroxyalkanoate copolymer having an (un)saturated hydrocarbon-based chain and a mixture of volatile and non-volatile oils.

The present invention relates to a cosmetic composition comprising a) at least one polyhydroxyalkanoate (PHA) copolymer having (un)saturated hydrocarbon-based groups, b) at least one volatile oil, and c) at least one non-volatile oil. (C1), and also to a method of treating keratin materials using such compositions.

In cosmetics, it is known practice to use film-forming polymers that can be transferred in organic media such as hydrocarbon-based oils. In particular the polymers are used as film-forming agents in make-up products such as mascara, eyeliner, eye shadow or lipstick.

FR-A-2964663 describes cosmetic compositions comprising pigments coated with C ₃ -C ₂₁ polyhydroxyalkanoates, such as poly(hydroxybutyrate-co-hydroxyvalerate).

WO 2011/154508 discloses film-forming polymers which may be polyhydroxyalkanoates, such as polyhydroxybutyrate, polyhydroxyvalerate and polyhydroxybutyrate-co-polyhydroxyvalerate and 4-carboxy-2- A cosmetic composition comprising a pyrrolidinone ester derivative is described.

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

Most polyhydroxyalkanoate copolymers are polymers derived from the same carbon source or substrate and mostly from the polycondensation of identical polymer repeat units. These documents describe cosmetic applications of copolymers derived from polycondensation using PHA with an aliphatic substrate or a first carbon source and at least one second substrate different from the first substrate (comprising at least one (un)saturated hydrocarbon-based group). The purpose is not described. Accordingly, there is a need for compositions comprising polyhydroxyalkanoate copolymers that are lipophilic or soluble in the lipid phase. This makes it possible to obtain films on keratin materials with good cosmetic properties, in particular good resistance to oils and sebum, which can also be changed to glossy or matte.

The applicant has discovered that polyhydroxyalkanoate copolymers containing certain grafted or functionalized hydrocarbon-based groups as defined below can be readily used in fatty media and thus it is possible to obtain homogeneous compositions. did. Composition (C1) shows good stability, especially after 1 month of storage at room temperature (25° C.). The composition (C1) makes it possible to obtain films with good cosmetic properties, good persistence of color without run-off of the composition and also with a matte or glossy appearance of the treated keratin material, especially after application to the keratin material.

Many conditions involve the use of film-forming substances on keratinous materials, for example in make-up or coloring applications, in addition to good resistance to water and oils, especially food oils such as olive oil, for example to prevent staining on clothing. It is desirable to have a very good resistance to rubbing of deposits of film-forming material in order to prevent and maintain a uniform appearance of the deposits. If the rubbing resistance is not sufficient, the resulting deposits can quickly become very unsightly to the consumer, especially if these deposits are colored, such as in makeup applications such as lipstick, foundation or mascara. In hair applications, lack of rub resistance is very problematic in all coloring applications because it transfers to clothing and creates an unsightly appearance of the keratin fibers. Therefore, there is a need to improve the sustainability of PHA delivered in the aqueous phase.

There is therefore a real need to obtain deposits of film-forming substances that are resistant to oils, especially food oils, water-resistant and highly rub-resistant.

When the deposits are colored, these moisture resistance problems can cause the color to transfer, for example, to clothing, which is a problem in itself and makes the deposits very unsightly.

For application of film-forming polymers to keratin materials, it is desirable for the deposit to be soft, comfortable, non-sticky and have an acceptable gloss for the intended use.

These problems are solved by using the composition (C1) described below, which can significantly improve the rubbing resistance of polyhydroxyalkanoate (PHA) copolymer(s). In addition, the composition (C1) according to the invention makes it possible to obtain, after deposition, a film on keratin materials with good cosmetic properties, in particular good resistance to oils and sebum and good water resistance, and also has a gloss or Allows you to change the matte look. Moreover, these deposits are flexible and comfortable.

Therefore, the subject matter of the present invention is

a) at least one poly, preferably consisting of several repeating units selected from the following units (A) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof: Hydroxyalkanoate (PHA) copolymer:

-[-O-CH(R ¹ )-CH ₂ -C(O)-]- Unit (A)

[In polymer unit (A) :

- 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, comprising 5 to 28 carbon atoms; Preferably, the 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 ) is selected from alkynyl; Preferably, the hydrocarbon-based group is linear;

The hydrocarbon chain is:

a) 할로겐, 예컨대 염소 또는 브롬, b) 히드록실, c) 티올, d) (디)(C₁-C₄)(알킬)아미노, e) (티오)카르복시, f) (티오)카르복사미드 -C(O)-N(R_a)₂ 또는 C(S)-N(R_a)₂, g) 시아노, h) 이소(티오)시아네이트, i) (헤테로)아릴, 예컨대 페닐 또는 푸릴, 및 j) (헤테로)시클로알킬, 예컨대 무수물, 에폭시드 또는 디티올란, k) 미용 활성제; l) R-X (여기서 R은 α) 시클로알킬, 예컨대 시클로헥실, β) 헤테로시클로알킬, 예컨대 당, 바람직하게는 단당류, 예컨대 글루코스, γ) (헤테로)아릴, 예컨대 페닐, δ) 미용 활성제로부터 선택된 기를 나타내고 X는 a') O, S, N(R_a) 또는 Si(R_b)(R_c), b') S(O)_r, 또는 (티오)카르보닐, 또는 c') a')와 b')의 조합, 예컨대 (티오)에스테르, (티오)아미드, (티오)우레아 또는 술폰아미드를 나타내고; R _a 는 수소 원자, 또는 (C₁-C₄)알킬 기 또는 아릴(C₁-C₄)알킬 기, 예컨대 벤질을 나타내고, 바람직하게는 R_a는 수소 원자를 나타내고; R _b 및 R _c 는 동일하거나 상이할 수 있으며, (C₁-C₄)알킬 또는 (C₁-C₄)알콕시 기, 특히 오직 하나의 치환체를 나타냄), m) 티오술페이트로부터 선택되는; 바람직하게는 b) 할로겐, 및 j) 예컨대 에폭시드로부터 선택되는 하나 이상의 원자 또는 기로 선택적으로 치환되고/되거나;

a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide. -C(O)-N(R _a ) ₂ or C(S)-N(R _a ) ₂ , g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl. , and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active agent; l) R _{and ​ ​ ​} b'), such as (thio)esters, (thio)amides, (thio)ureas or sulfonamides; R _a represents a hydrogen atom, or a (C ₁ -C ₄ )alkyl group or an aryl(C ₁ -C ₄ )alkyl group such as benzyl, preferably R _a represents a hydrogen atom; R _b and R _c may be the same or different and are selected from (C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkoxy groups, especially representing only one substituent), m) thiosulfate; preferably b) halogen, and j) optionally substituted with one or more atoms or groups such as epoxides;

하나 이상의 a') 헤테로원자, 예컨대 O, S, N(R_a) 및 Si(R_b)(R_c), b') S(O)_r, (티오)카르보닐, 또는 c') a')와 b')의 조합, 예컨대 (티오)에스테르, (티오)아미드, (티오)우레아, 술폰아미드 (여기서, r은 1 또는 2이고, R _a 는 앞서 정의된 바와 같고, 바람직하게는 R _a 는 수소 원자를 나타내고, R _b 및 R _c 는 앞서 정의된 바와 같음)가 선택적으로 개재됨]; 및

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' ) and b'), such as (thio)esters, (thio)amides, (thio)ureas, sulfonamides (where r is 1 or 2, R _a is as defined above, preferably R _a represents a hydrogen atom, and R _b and R _c are as previously defined) are optionally interrupted; and

b) one or more volatile oils; and

c) one or more non-volatile oils

It is a composition (C1) comprising;

It is understood that the mass ratio R between the sum of the masses (weights) of the volatile oil b) and the sum of the masses of the non-volatile oil c) is not zero and is less than 900, preferably between 3 and 800 and more preferably between 4 and 200. .

Another subject of the invention is a keratin material, preferably A method for treating human keratin fibers, such as hair, or β) human skin, especially lips, wherein the mass ratio between volatile oil(s) and non-volatile oil(s) is less than 900, preferably 3 to 800, more preferred. It is understood that it is 4 to 200.

More specifically, the subject matter of the invention is a non- It is a therapeutic cosmetic method. The treatment method is specifically a method of caring for or making up keratinous substances.

For purposes of the present invention, and unless otherwise indicated,

- The term “ cosmetic active agent ” means a radical of an organic or organosilicon compound which can be incorporated into a cosmetic composition to give an effect on the keratinous material (whether this effect is immediate or is provided by repeated applications). Examples of cosmetic actives include pigmented or non-pigmented, fluorescent or non-fluorescent chromophores, such as those derived from optical brighteners, or chromophores derived from UVA and/or UVB screening agents, anti-aging actives or intended to provide benefits to the skin. Activated agents, such as those acting on barrier function, deodorizing active 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, skin sheen active agents. Active agents intended to limit, active agents intended to prevent the effects of contamination, antimicrobial or antibacterial actives, anti-dandruff actives, and fragrances may be mentioned.

- The term “ (hetero)aryl ” means an aryl or heteroaryl group;

- The term " (hetero)cycloalkyl " means a cycloalkyl or heterocycloalkyl group;

- The “ aryl ” or “ heteroaryl ” radical, or the aryl or heteroaryl part of the radical, may be substituted with at least one substituent carried by the carbon atom, selected from:

C₁-C₆ 및 바람직하게는 C₁-C₄ 알킬 라디칼;

C ₁ -C ₆ and preferably C ₁ -C ₄ alkyl radicals;

할로겐 원자, 예컨대, 염소, 불소 또는 브롬;

Halogen atoms such as chlorine, fluorine or bromine;

히드록실 기;

hydroxyl group;

C₁-C₂ 알콕시 라디칼, C₂-C₄ (폴리)히드록시알콕시 라디칼;

C ₁ -C ₂ alkoxy radical, C ₂ -C ₄ (poly)hydroxyalkoxy radical;

아미노 라디칼;

amino radical;

1개 또는 2개의 동일하거나 상이한 C₁-C₆ 및 바람직하게는 C₁-C₄ 알킬 라디칼로 치환된 아미노 라디칼;

an amino radical substituted by one or two identical or different C ₁ -C ₆ and preferably C ₁ -C ₄ alkyl radicals;

아실아미노 라디칼 (-NR-COR') (여기서, 라디칼 R은 수소 원자임);

acylamino radical (-NR-COR'), where the radical R is a hydrogen atom;

C₁-C₄ 알킬 라디칼 및 라디칼 R'은 C₁-C₄ 알킬 라디칼; 카르바모일 라디칼 ((R)₂N-CO-) (여기서, 라디칼 R은 동일하거나 상이할 수 있으며, 수소 원자 또는 C₁-C₄ 알킬 라디칼을 나타냄);

The C ₁ -C ₄ alkyl radical and the radical R' are C ₁ -C ₄ alkyl radicals; carbamoyl radical ((R) ₂ N-CO-), where the radicals R may be the same or different and represent a hydrogen atom or a C ₁ -C ₄ alkyl radical;

알킬술포닐아미노 라디칼 (R'SO₂-NR-) (여기서, 라디칼 R은 수소 원자 또는 C₁-C₄ 알킬 라디칼을 나타내고 라디칼 R'은 C₁-C₄ 알킬 라디칼 또는 페닐 라디칼을 나타냄);

alkylsulfonylamino radical (R'SO ₂ -NR-), wherein the radical R represents a hydrogen atom or a C ₁ -C ₄ alkyl radical and the radical R' represents a C ₁ -C ₄ alkyl radical or a phenyl radical);

아미노술포닐 라디칼 ((R)₂N-S(O)₂-) (여기서, 라디칼 R은 동일하거나 상이할 수 있으며 수소 원자 또는 C₁-C₄ 알킬 라디칼을 나타냄);

aminosulfonyl radical ((R) ₂ NS(O) ₂ -), where the radicals R may be the same or different and represent a hydrogen atom or a C ₁ -C ₄ alkyl radical;

산 또는 (바람직하게는 알칼리 금속 또는 치환 또는 비치환 암모늄으로) 염화된 형태의 카르복실 라디칼;

Carboxyl radicals in acid or chlorinated form (preferably with an alkali metal or substituted or unsubstituted ammonium);

시아노 기 (CN);

cyano group (CN);

폴리할로(C₁-C₄)알킬 기, 우선적으로 트리플루오로메틸 (CF₃);

polyhalo(C ₁ -C ₄ )alkyl groups, preferentially trifluoromethyl (CF ₃ );

- The cyclic or heterocyclic part of the non-aromatic radical may be substituted by at least one substituent carried by the carbon atom, selected from the following groups:

히드록실,

hydroxyl,

C₁-C₄ 알콕시, C₂-C₄ (폴리)히드록시알콕시;

C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly)hydroxyalkoxy;

알킬카르보닐아미노 (RCO-NR'-) (여기서, 라디칼 R'은 수소 원자 또는 C₁-C₄ 알킬 라디칼이고 라디칼 R은 C₁-C₂ 알킬 라디칼 또는 아미노 라디칼 (1개 또는 2개의 동일하거나 상이한 C₁-C₄ 알킬 기로 치환됨)임);

Alkylcarbonylamino (RCO-NR'-) (wherein the radical R' is a hydrogen atom or a C ₁ -C ₄ alkyl radical and the radical R is a C ₁ -C ₂ alkyl radical or an amino radical (one or two identical or substituted with different C ₁ -C ₄ alkyl groups);

알킬카르보닐옥시 (RCO-O-) (여기서, 라디칼 R은 C₁-C₄ 알킬 라디칼 또는 아미노 라디칼 (1개 또는 2개의 동일하거나 상이한 C₁-C₄ 알킬 기로 치환됨)임);

alkylcarbonyloxy (RCO-O-), wherein the radical R is a C ₁ -C ₄ alkyl radical or an amino radical (substituted by one or two identical or different C ₁ -C ₄ alkyl groups);

알콕시카르보닐 (RO-CO-) (여기서, 라디칼 R은 C₁-C₄ 알킬 라디칼 또는 아미노 라디칼 (1개 또는 2개의 동일하거나 상이한 C₁-C₄ 알킬 기로 치환됨)임);

alkoxycarbonyl (RO-CO-), wherein the radical R is a C ₁ -C ₄ alkyl radical or an amino radical (substituted by one or two identical or different C ₁ -C ₄ alkyl groups);

- The non-aromatic part of a cyclic or heterocyclic radical, or an aryl or heteroaryl radical, may also be substituted with one or more oxo groups;

- A hydrocarbon-based chain is unsaturated if it contains one or more double bonds and/or one or more triple bonds;

- " aryl " radical refers to a monocyclic or fused or non-fused polycyclic hydrocarbon group containing 6 to 22 carbon atoms, at least one of which is aromatic; Preferentially the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

- " Heteroaryl " radical refers to a monocyclic or fused or non-fused polycyclic 5- to 22-membered group (comprising 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms), of which At least one ring is aromatic; Preferentially heteroaryl radicals are acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetra Zolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazolyl Zinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrillyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, is selected from thiazoylimidazolyl, thiopyrylyl, triazolyl and xantylyl;

- a “ cyclic ” or “ cycloalkyl ” radical is a monocyclic or fused or non-fused polycyclic non-aromatic cyclic hydrocarbon radical containing 5 to 22 carbon atoms, which may contain one or more unsaturations; Cycloalkyl is preferably a cyclohexyl group;

- " heterocyclic " or " heterocycloalkyl " radical is a monocyclic or fused or non-fused polycyclic 3- to 9-membered non- It is an aromatic cyclic radical; Preferably, the heterocycloalkyl is selected from epoxides, piperazinyl, piperidyl, morpholinyl and dithiolane;

- “ alkyl” radicals are linear or branched, especially C ₁ -C ₆ and preferably C ₁ -C ₄ saturated hydrocarbon-based radicals;

- “ Alkenyl ” radicals are linear or branched unsaturated hydrocarbon-based radicals containing one or more conjugated or non-conjugated double bonds;

- “ alkynyl ” radicals are linear or branched unsaturated hydrocarbon-based radicals containing one or more conjugated or non-conjugated triple bonds;

- " Alkoxy " radicals are alkyl-oxy radicals in which the alkyl radical is a linear or branched C ₁ -C ₆ , preferentially C ₁ -C ₄ hydrocarbon-based radical;

- " sugar " radicals are monosaccharide or polysaccharide radicals, their O-protected sugar derivatives, such as sugar esters of (C ₁ -C ₆ )alkylcarboxylic acids, such as acetic acid, sugar-containing amine group(s) and (C ₁ - C ₄ )alkyl derivatives, such as methyl derivatives, for example methylglucose. Sugar radicals that may be mentioned include: sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose;

- The term " monosaccharide " refers to _a compound of the formula C _x (H ₂ O) x = 6), monosaccharide sugars containing at least 5 carbon atoms (which may be of D or L configuration and alpha or beta anomer) and also salts thereof and solvates thereof, such as hydrates;

- The term " polysaccharide " refers to a polysaccharide sugar, which is a polymer consisting of several saccharides joined together by O-osidic bonds, said polymer being composed of monomeric units as previously defined, said monosaccharide units being at least 5 , preferably contains 6 carbon atoms; Specifically, the monosaccharide units are linked together as α (alpha) or β (beta) anomers via 1,4 or 1,6 linkages, and each osidic unit is in the L or D configuration, and also salts thereof and solvents thereof. cargo, such as hydrates of the above monosaccharides; More specifically, it is a polymer formed from a certain number of saccharides (or monosaccharides) with the general formula: -[C _x (H ₂ O) _y )] _w - or -[(CH ₂ O) _x ] _w - ( Here, x is an integer of 5 or more, preferably x is 6 or more, specifically x is 5 to 7 (including the end point), preferably x is 6, y is an integer of x - 1, and w is 2 or more specifically 3 to 3000 (inclusive), more specifically 5 to 2500, preferably 10 to 2300, specifically 15 to 1000 (inclusive), more particularly 20 to 500, preferably 25 to 200. ;

- The term “sugar with amine group(s)” means one in which the sugar radical is substituted by one or more amino groups NR ₁ R ₂ , i.e. at least one of the hydroxyl groups of at least one saccharide unit of the sugar radical is substituted with the group NR ₁ R ₂ , where R ₁ and R ₂ may be the same or different and are i) a hydrogen atom, ii) a (C ₁ -C ₆ )alkyl group, iii) an aryl group such as phenyl, iv) represents an aryl(C ₁ -C ₄ )alkyl group such as benzyl, vii) -C(Y)-(Y') _f -R' ₁ , where Y and Y' may be the same or different, and oxygen, represents a sulfur atom or N(R' ₂ ), preferably oxygen, and f = 0 or 1, preferably 0; R' ₁ and R' ₂ represent i) to vi) of R ₁ and R ₂ as previously defined, specifically R' ₁ represents a (C ₁ -C ₆ )alkyl group, such as methyl. Preferably, R ₁ and/or R ₂ represent a hydrogen atom, or a (C ₁ -C ₄ )alkylcarbonyl group such as acetyl, more preferably R ₁ represents a hydrogen atom and R ₂ represents (C ₁ - C ₄ ) represents an alkylcarbonyl group such as acetyl;

- The term “ organic or inorganic acid salts ” more specifically refers to i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO ₄ , iv) alkylsulfonic acids: Alk-S(O) ₂ OH, for example methane. sulfonic acid and ethanesulfonic acid; v) Arylsulfonic acids: Ar—S(O) ₂ OH, such as benzenesulfonic acid and toluenesulfonic acid; vi) Alkoxysulfinic acids: Alk-OS(O)OH, such as methoxysulfinic acid and ethoxysulfinic acid; vii) Aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) Phosphoric acid H ₃ PO ₄ ; ix) triflic acid CF ₃ SO ₃ H and x) tetrafluoroboric acid HBF ₄ ; xi) Organic carboxylic acid R°-C(O)-OH (I'z) (in formula (I'z), R° is a (hetero)aryl group such as phenyl, (hetero)aryl(C ₁ -C ₄ ) represents an alkyl group, such as benzyl, or (C ₁ -C ₁₀ )alkyl, said alkyl group being preferably optionally substituted by one or more hydroxyl groups or amino or carboxyl radicals, and R° is preferably 1 , more preferably a (C ₁ -C ₆ )alkyl group optionally substituted with 2 or 3 hydroxyl or carboxyl groups; more preferentially, the monocarboxylic acids of formula (I'z) include acetic acid, glycolic acid, lactic acid and the like; mixtures of, more specifically selected from acetic acid and lactic acid; the polycarboxylic acid is selected from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof); and xii) amino acids comprising more carboxylic acid radicals than amino groups, such as γ-carboxyglutamic acid, aspartic acid or glutamic acid, especially salts derived from γ-carboxyglutamic acid;

- “Anionic counterion” is an anion or anionic group that is associated with a positive charge; More specifically, the anionic counterion is i) a halide, such as chloride or bromide; ii) nitrates; iii) sulfonates (C ₁ -C ₆ alkylsulfonates: Alk-S(O) ₂ O ^- , including for example methylsulfonate or mesylate and ethylsulfonate); iv) Arylsulfonates: Ar—S(O) ₂ O ^- , such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) Alkyl sulfates: Alk-OS(O)O ^- , such as methyl sulfate and ethyl sulfate; x) Aryl sulfates: Ar-OS(O)O ^- , such as benzene sulfate and toluene sulfate; xi) Alkoxy sulfates: Alk-OS(O) ₂ O ^- , such as methoxy sulfate and ethoxy sulfate; xii) Aryloxy sulfate: Ar-OS(O) ₂ O ^- ; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

- “ Solvate ” refers to hydrates and also combinations with linear or branched C ₁ -C ₄ alcohols, such as ethanol, isopropanol or n-propanol;

- The term “ chromophore ” means a radical derived from a colorless or colored compound capable of absorbing a wavelength λ _abs of 250 to 800 nm in the UV and/or visible radiation range. Preferably, the chromophore is colored, i.e. absorbs wavelengths in the visible range, preferably between 400 and 800 nm. Preferably, the chromophore appears colored to the eye, specifically between 400 and 700 nm ( Ullmann's Encyclopedia , 2005, Wiley-VcH, Verlag "Dyes, General Survey", § 2.1 Basic Principle of Color]);

- The term " fluorescent chromophore " means a chromophore that is also capable of re-emitting an emission wavelength λ _em (higher than the absorption wavelength) in the visible range from 400 to 800 nm, preferably with a Stoke shift, i.e. the maximum absorption wavelength and the emission The difference between the wavelengths is at least 10 nm. Preferably, the fluorescent chromophore is derived from a fluorescent dye capable of absorbing a wavelength in the visible range λ _abs , i.e. 400 to 800 nm and re-emitting in the visible range λ _em of 400 to 800 nm. More preferentially, the fluorescent chromophore is capable of absorption λ _abs from 420 to 550 nm and re-emission λ _em in the visible range from 470 to 600 nm;

- The term “optical brightening chromophore” refers to an optical brightening compound or “ optical brightener, optical brightening agent (OBA) ” or “ fluorescent whitening agent (FBA) ” or “ fluorescent whitening agent (FWA) ”, i.e. UV radiation, i.e. between 250 and 250 °C. This energy is absorbed by absorption at a wavelength λ _abs of 350 nm, and subsequently by fluorescence in the visible range with an emission wavelength λ _em of 400 to 600 nm, i.e. at a wavelength between blue-violet and blue-green (maximum in the blue range). refers to a chromophore derived from a re-emitting agent. The optical brightener chromophore therefore appears colorless to the eye;

- The term “ UV-A screening agent ” refers to a chromophore derived from a compound that screens (or absorbs) UV-A ultraviolet radiation at a wavelength of 320 to 400 nm. A distinction can be made between short UV-A screening agents (absorbing rays with a wavelength of 320 to 340 nm) and long UV-A screening agents (absorbing rays with a wavelength of 340 to 400 nm);

- The term “ UV-B screening agent ” refers to a chromophore derived from a compound that screens (or absorbs) UV-B ultraviolet radiation at a wavelength of 280 to 320 nm.

Additionally, unless otherwise indicated, limits delimiting the value range are included in the value range.

a) PHA copolymer(s)

The composition (C1) of the invention comprises a first component a) at least one PHA copolymer, which contains or preferably consists of at least two different repeating polymer units (A) as defined above.

According to a specific embodiment of the invention, the composition (C1) or composition (C1') according to the invention contains at least two different repeating polymer units selected from units (A) and (B) as previously defined, or , preferably consisting of a first component a) at least one PHA copolymer.

Preferably, the composition (C1) of the present invention:

a) contains at least two different repeating polymer units selected from the following units (A) and (B), and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof, One or more polyhydroxyalkanoate (PHA) copolymers, preferably consisting of:

-[-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 is a saturated or unsaturated, linear or branched, acyclic hydrocarbon-based chain, or a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon-based chain, comprising 5 to 28 carbon atoms; Specifically selected from 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. represents a hydrocarbon-based chain; Preferably, the hydrocarbon-based group is linear;

The hydrocarbon chain is:

a) 할로겐, 예컨대 염소 또는 브롬, b) 히드록실, c) 티올, d) (디)(C₁-C₄)(알킬)아미노, e) (티오)카르복시, f) (티오)카르복사미드 -C(O)-N(R_a)₂ 또는 C(S)-N(R_a)₂, g) 시아노, h) 이소(티오)시아네이트, i) (헤테로)아릴, 예컨대 페닐 또는 푸릴, 및 j) (헤테로)시클로알킬, 예컨대 무수물, 에폭시드 또는 디티올란, k) 미용 활성제; l) R-X (여기서 R은 α) 시클로알킬, 예컨대 시클로헥실, β) 헤테로시클로알킬, 예컨대 당, 바람직하게는 단당류, 예컨대 글루코스, γ) (헤테로)아릴, 예컨대 페닐, δ) 미용 활성제로부터 선택된 기를 나타내고 X는 a') O, S, N(R_a) 또는 Si(R_b)(R_c), b') S(O)_r, 또는 (티오)카르보닐, 또는 c') a')와 b')의 조합, 예컨대 (티오)에스테르, (티오)아미드, (티오)우레아 또는 술폰아미드를 나타내고; R _a 는 수소 원자, 또는 (C₁-C₄)알킬 기 또는 아릴(C₁-C₄)알킬 기, 예컨대 벤질을 나타내고, 바람직하게는 R_a는 수소 원자를 나타내고; R _b 및 R _c 는 동일하거나 상이할 수 있으며, (C₁-C₄)알킬 또는 (C₁-C₄)알콕시 기, 특히 오직 하나의 치환체를 나타냄), m) 티오술페이트로부터 선택되는; 바람직하게는 b) 할로겐, 및 j) 예컨대 에폭시드로부터 선택되는 하나 이상의 원자 또는 기로 선택적으로 치환되고/되거나;

a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide. -C(O)-N(R _a ) ₂ or C(S)-N(R _a ) ₂ , g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl. , and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active agent; l) R _{and ​ ​ ​} b'), such as (thio)esters, (thio)amides, (thio)ureas or sulfonamides; R _a represents a hydrogen atom, or a (C ₁ -C ₄ )alkyl group or an aryl(C ₁ -C ₄ )alkyl group such as benzyl, preferably R _a represents a hydrogen atom; R _b and R _c may be the same or different and are selected from (C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkoxy groups, especially representing only one substituent), m) thiosulfate; preferably b) halogen, and j) optionally substituted with one or more atoms or groups such as epoxides;

하나 이상의 a') 헤테로원자, 예컨대 O, S, N(R_a) 및 Si(R_b)(R_c), b') S(O)_r, (티오)카르보닐, 또는 c') a')와 b')의 조합, 예컨대 (티오)에스테르, (티오)아미드, (티오)우레아 또는 술폰아미드 (여기서, r은 1 또는 2이고, R _a 는 앞서 정의된 바와 같고, 바람직하게는 R _a 는 수소 원자를 나타내고, R _b 및 R _c 는 앞서 정의된 바와 같음)가 선택적으로 개재되고;

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' ) and b'), such as (thio)ester, (thio)amide, (thio)urea or sulfonamide (where r is 1 or 2, R _a is as defined above, preferably R _a represents a hydrogen atom and R _b and R _c are as previously defined) are optionally interrupted;

R ² 는 R¹에 대해 정의된 바와 같이 하나 이상의 원자 또는 기 a) 내지 m)으로 선택적으로 치환되고/되거나 하나 이상의 헤테로원자 또는 기 a') 내지 c')가 선택적으로 개재된, 3 내지 30개의 탄소 원자를 포함하는 환형 또는 비환형, 선형 또는 분지형, 포화 또는 불포화 탄화수소계 기를 나타내며; 구체적으로 선형 또는 분지형 (C₃-C₂₈)알킬 및 선형 또는 분지형 (C₃-C₂₈)알케닐, 구체적으로 선형 탄화수소계 기, 더 구체적으로 (C₄-C₂₀)알킬 또는 (C₄-C₂₀)알케닐로부터 선택되고; 바람직하게는, 탄화수소계 기는 적어도 하나의 탄소 원자가 차감된 라디칼 R ¹ 의 탄소 원자의 수에 상응하는, 바람직하게는 2개의 탄소 원자가 차감된 라디칼 R ¹ 의 탄소 원자의 수에 상응하는 탄소수를 가짐];

R ² 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') from 3 to 30 Represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon group containing 2 carbon atoms; specifically linear or branched (C ₃ -C ₂₈ )alkyl and linear or branched (C ₃ -C ₂₈ )alkenyl, specifically linear hydrocarbon-based groups, more specifically (C ₄ -C ₂₀ )alkyl or (C ₄ -C ₂₀ )alkenyl; Preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R ¹ minus at least one carbon atom, preferably corresponding to the number of carbon atoms of the radical R ¹ minus two carbon atoms] ;

b) one or more volatile oils;

c) contains at least one non-volatile oil;

d) optionally one or more surfactant(s); and

e) optionally water; and

f) optionally, one or more organic solvents other than b) and c)

A composition (C1') comprising: preferably a cosmetic composition;

- (A) is different from (B)

- The mass ratio R of b) the sum of the masses of the volatile oil(s)/c) the sum of the masses of the non-volatile oil(s) is not zero and is less than 900, preferably between 3 and 800 and more preferably between 4 and 200.

The term “ copolymer ” means that the polymer is derived from the polycondensation of polymeric repeat units that are different from each other, i.e., that the polymer is derived from the polycondensation of polymeric repeat units (A) that are different from each other, or polymeric repeat units (A) and (B), wherein the polymeric unit (A) is understood to be different from the polymeric unit (B), wherein the copolymer is optionally substituted and/or interrupted, preferably unpaired. ring and uninterrupted monosaturated or unsaturated aliphatic carbon sources, or from several carbon sources, specifically at least one of these being an uninterrupted unsubstituted saturated aliphatic and the other carbon source(s) being in particular a halogen atom such as bromine. or a saturated or unsaturated aliphatic optionally substituted with a cyano group, Bunte salt, dithiolane radical, carboxyl, etc.

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

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

According to one embodiment, the copolymer according to the invention is derived from several carbon sources, at least one of which is saturated aliphatic. According to a specific embodiment of the invention, the PHA copolymer(s) consist of two different repeating polymer units selected from units (A) and (B) as previously defined.

According to a specific embodiment of the invention, the PHA copolymer(s) comprise, preferably consist of, two different repeating polymer units selected from units (A) and units (B) as previously defined, ; wherein R ² represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon group containing 3 to 30 carbon atoms; specifically linear or branched (C ₃ -C ₂₈ )alkyl and linear or branched (C ₃ -C ₂₈ )alkenyl, specifically linear hydrocarbon-based groups, more specifically (C ₄ -C ₂₀ )alkyl or (C ₄ -C ₂₀ )alkenyl; Preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R ¹ minus at least one carbon atom, preferably corresponding to the number of carbon atoms of the radical R ¹ minus two carbon atoms.

More preferentially, the PHA copolymer(s) according to the invention comprise repeating units of formula (I) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof. :

[Formula 1]

In formula (I) :

R ¹ 및 R ² 는 이전에 정의된 바와 같고;

R ¹ and R ² are as previously defined;

m 및 n은 1 이상의 정수이고; 바람직하게는, 합 n + m은 450 내지 1400 (종점 포함)이고;

m and n are integers greater than or equal to 1; Preferably, the sum n + m is 450 to 1400 (inclusive);

Preferably, when R ¹ and R ² represent an unsubstituted and uninterrupted alkyl group, m > n, and more preferentially, when R ¹ and R ² are linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group. ; R ² represents a linear alkyl group having a carbon number corresponding to that of R ¹ minus two carbon atoms, such as a C ₃ -C ₁₁ alkyl group;

Preferably, if 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 and R ² represents an alkyl group, then m < It is n.

According to a specific embodiment, the PHA copolymer(s) a) of the composition contain three different repeating polymer units (A) , (B) and (C) , preferably three different repeating polymer units (A) ) , (B) and (C) , and also their optical or geometric isomers and solvates thereof, such as hydrates:

-[-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 polymer units (A) , (B) and (C) ,

- R ¹ and R ² are as previously defined;

- R ³ is 1 to 1, which 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') represents a hydrocarbon-based group, saturated or unsaturated, linear or branched, cyclic or acyclic, containing 30 carbon atoms; specifically selected from linear or branched (C ₁ -C ₂₈ )alkyl, and linear or branched (C ₂ -C ₂₈ )alkenyl, especially linear hydrocarbon-based groups, more particularly (C ₄ -C ₂₀ )alkenyl. represents a hydrocarbon-based group; Preferably, the hydrocarbon-based group corresponds to the number of carbon atoms of the radical R ¹ or else corresponds to the number of carbon atoms of the radical R ¹ minus at least 3 carbon atoms, preferably the radical R minus 4 carbon atoms. has a carbon number corresponding to the number of carbon atoms of ¹ ;

The following is understood:

- (A) is different from (B) and (C) , (B) is different from (A) and (C) , (C) is different from (A) and (B) ;

- Preferably, when R ¹ , R ² and R ³ represent unsubstituted and uninterrupted alkyl groups, the mole percentage of unit (A) is greater than the mole percentage of unit (B) and greater than the mole percentage of unit (C) , more preferentially, when R ¹ , R ² and R ³ are linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R 1 minus 4 carbon atoms;

- Preferably, if R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, then R ² represents an alkyl group. If it represents and/or R ³ represents an alkyl group, the mole percentage of unit (A) is less than the mole percentage of unit (B) and is less than the mole percentage of unit (C) .

According to a specific embodiment of the invention, the PHA copolymer(s) comprise repeating units of formula (II) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof. do:

[Formula 2]

In the above formula (II) ,

R ¹ , R ² 및 R ³ 은 앞서 정의된 바와 같고;

R ¹ , R ² and R ³ are as previously defined;

m, n 및 p는 1 이상의 정수이고; 바람직하게는, 합 n + m + p는 450 내지 1400 (종점 포함)이고;

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, if R ¹ , R ² and R ³ represent unsubstituted and uninterrupted alkyl groups, then m > n + p, more preferentially, if R ¹ , R ² and R ³ are linear alkyl, then R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, such as a C ₃ -C ₁₁ alkyl group, and R ³ has a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms. represents a linear alkyl group having, such as a C ₁ -C ₉ alkyl group;

- 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, and R ² and R When ³ represents an alkyl group, m < n + p.

According to a specific embodiment, the PHA copolymer(s) a) of the composition contain four different repeating polymer units (A) , (B) , (C) and (D) , preferably the following four different repeats It consists of the polymer units (A) , (B) , (C) and (D) , and also their optical or geometric isomers, their organic or inorganic acid or base salts, and their solvates such as hydrates:

-[-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 polymer units (A) , (B) , (C) and (D) ,

- R ¹ , R ² and R ³ are as previously defined;

- R ⁴ is 3 to 3, which 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') represents a cyclic or acyclic, linear or branched, saturated hydrocarbon group containing 30 carbon atoms; linear or branched (C ₄ ) optionally substituted with one or more atoms or groups a) to m) and/or interrupted by one or more heteroatoms or groups a') to c') as specifically defined for R ¹ -C ₂₈ ) represents a hydrocarbon-based group selected from alkyl;

The following is understood:

- (A) is different from (B) , (C) and (D) , (B) is different from (A) , (C) and (D) , and (C) is different from (A) , (B) and (D) , and (D) is different from (A) , (B) , and (C) ;

- Preferably, when R ¹ , R ² , R ³ and R ⁴ represent unsubstituted and uninterrupted alkyl groups, the mole percentage of unit (A) is greater than the mole percentage of unit (B) and the mole percentage of unit (C) greater than the percentage and greater than the molar percentage of unit (D) , and more preferentially, when R ¹ , R ² , R ³ and R ⁴ are linear alkyl, then R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, such as a C ₃ -C ₁₁ alkyl group, and R ³ has a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms. represents a linear alkyl group having, such as a C ₁ -C ₉ alkyl group, and R ⁴ represents a linear alkyl group having a carbon number corresponding to that of R ¹ minus 6 carbon atoms;

- Preferably, if R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, in particular R ² is alkyl If it represents a group and/or R ³ represents an alkyl group, the mole percentage of unit (A) is less than the mole percentage of unit (B) and less than the mole percentage of unit (C) ; R ⁴ represents an optionally substituted and/or optionally interrupted alkyl, an optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group.

According to a specific embodiment of the invention, the PHA copolymer(s) comprise repeating units of formula (III) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof. do:

[Formula 3]

In the above formula (III) ,

R ¹ , R ² , R ³ 및 R ⁴ 는 앞서 정의된 바와 같고;

R ¹ , R ² , R ³ and R ⁴ are as previously defined;

m, n, p 및 v는 1 이상의 정수이고;

m , n , p and v are integers greater than or equal to 1;

- Preferably, the sum n + m + p + v is from 450 to 1400 (inclusive);

- Preferably, when R ¹ , R ² , R ³ and R ⁴ represent unsubstituted and uninterrupted alkyl groups, m > n + p + q, more preferably R ¹ , R ² , R ³ and R When ⁴ is linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms, R ⁴ represents a linear alkyl group having a carbon number corresponding to that of R ¹ minus 6 carbon atoms;

- Preferably, R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, and R ² and R ³ represents an alkyl group, and if R ⁴ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, then n > m + v; ; More preferentially n + p > m + v.

According to one embodiment, the PHA copolymer(s) a) of the composition more specifically contain five different repeating polymer units (A) , (B) , (C) , (D) and (E) , preferably In other words, the following five different repeating polymer units (A), (B), (C), (D) and (E) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and also solvents thereof. It consists of cargo, such as baggage:

-[-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 polymer units (A) , (B) , (C) , (D) and (E) :

- R ¹ , R ² , R ³ and R ⁴ are as previously defined;

- R ⁵ is 3 to 3, optionally substituted with one or more atoms or groups a) to m) as defined for R ¹ and/or optionally interrupted by one or more heteroatoms or groups a') to c') represents a cyclic or acyclic, linear or branched, saturated hydrocarbon group containing 30 carbon atoms; It is a linear or branched ( ^C ₄ -C ₂₈ ) represents a hydrocarbon-based group selected from alkyl; Preferably, the hydrocarbon-based group corresponds to the number of carbon atoms of the radical R ⁴ minus at least one carbon atom, preferably of the radical R ⁴ minus at least two carbon atoms, preferably minus two carbon atoms. has a carbon number corresponding to the number of carbon atoms;

The following is understood:

- (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) ; (E) is different from (A) , (B), (C) and (D) ;

- Preferably, when R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent unsubstituted and uninterrupted alkyl groups, the mole percentage of unit (A) is greater than the mole percentage of unit (B) and unit (C ) is greater than the mole percentage of the unit (D) and greater than the mole percentage of the unit (E), more preferentially R ¹ , R ² , R ³ , When R ⁴ and R ⁵ are linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R 1 minus 4 carbon atoms, and R ⁴ represents represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus 6 carbon atoms, and R ⁵ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus 8 carbon atoms;

- Preferably, if R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, in particular R ² is alkyl If it represents a group and/or R ³ represents an alkyl group, then the mole percentage of unit (A) is less than that of unit (B) and less than the mole percentage of unit (C) , and R ⁴ and R ⁵ are substituted and/ or an interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group.

According to a specific embodiment of the invention, the PHA copolymer(s) comprise repeating units of formula (IV) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof. do:

[Formula 4]

In formula (IV) :

R ¹ , R ² , R ³ , R ⁴ 및 R ⁵ 는 앞서 정의된 바와 같고;

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as previously defined;

m, n, p, v 및 z는 1 이상의 정수이고; 바람직하게는, 합 n + m + p + v + z는 450 내지 1400 (종점 포함)이고;

m , n, p, v and z are integers greater than or equal to 1; Preferably, the sum n + m + p + v + z is between 450 and 1400 (inclusive);

- Preferably, when R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent unsubstituted and uninterrupted alkyl groups, m > n + p + v + z;

- Preferably, R ¹ is substituted and/or interrupted alkyl; represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, R ² and R ³ represent an alkyl group, and the groups R ⁴ and R ⁵ are substituted and/or interrupted. alkyl; optionally substituted and/or optionally interrupted alkenyl; or when representing an optionally substituted and/or optionally interrupted alkynyl group, n > m + v + z; More preferentially n + p > m + v + z.

Preferably, R ¹ represents a linear or branched, preferably linear (C ₅ -C ₂₈ )alkyl hydrocarbon-based chain. According to one embodiment of the composition (C1) or composition (C1') according to the invention, the PHA copolymer(s) have radicals R ¹ having 5 to 14, preferably 6 to 12 carbon atoms, more preferentially An alkyl group containing 7 to 10 carbon atoms, such as n-pentyl, n-hexyl, n-octyl or n-nonyl.

According to a specific embodiment of the present invention, the hydrocarbon-based chain R ¹ is unsubstituted. According to a specific embodiment of the present invention, the hydrocarbon-based chain R ¹ is uninterrupted.

According to another embodiment, the hydrocarbon-based chain of the radical R ¹ of the present invention is 1) substituted, 2) or interrupted, or 3) or substituted and interrupted.

According to a specific embodiment of the invention, the PHA copolymer(s) have R ¹ selected from O, S, N(R _a ) and carbonyl, or combinations thereof, such as esters, amides or ureas (preferably refers to a hydrocarbon-based chain, particularly an alkyl group as defined above, where R _a is as defined above, and preferably R _a represents a hydrogen atom; Preferably, R ¹ represents an alkyl group interrupted by one or more atoms selected from O and S, more preferentially O or S, especially S atoms. Specifically, when it denotes an interrupted hydrocarbon-based chain, especially alkyl, R ¹ is C ₇ -C ₂₀ , more particularly C ₈ -C ₁₈ and even more particularly C ₉ -C ₁₆ . Preferably, the intervening hydrocarbon-based chains, especially alkyls, are linear.

According to another embodiment of the invention, the PHA copolymer(s) are hydrocarbons, wherein R ¹ is substituted with one or more (preferably one) atoms or groups selected from a) to k) as previously defined. chain, especially an alkyl group as previously defined. Preferably, the hydrocarbon-based chain is substituted with only one atom or group selected from a) to k) as defined above.

According to a specific embodiment of the invention, the PHA copolymer(s) are such that R ¹ is a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )( alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl, such as anhydride, dithiolane or epoxide, j) cosmetic active agent selected from pigmented or non-pigmented, fluorescent or non-fluorescent chromophore, For example optical brighteners, UV-screening agents, h) (hetero)aryl, such as phenyl or furyl, k) RX, where R is α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as sugar radicals, preferred monosaccharides such as glucosyl, γ) (hetero)aryl such _as phenyl, δ) a group selected from cosmetic actives as previously defined and carbonyl, or c') a combination of a') and b'), such as an ester, amide or urea; R _a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl or aryl(C ₁ -C ₄ )alkyl group such as benzyl, preferably R _a represents a hydrogen atom), m) thiosulfate It refers to a hydrocarbon-based chain substituted with one or more (preferably one) groups, especially alkyl groups as defined above.

Even more preferentially, the PHA copolymer(s) are such that R ¹ is a) halogen, such as chlorine or bromine, b) hydroxyl, d) (di)(C ₁ -C ₄ )(alkyl)amino, preferably amino. , e) carboxyl, i) (hetero)cycloalkyl, such as epoxide, h) (hetero)aryl, such as phenyl or furyl, k) RX, where R is α) cycloalkyl, such as cyclohexyl, β) hetero represents a group selected from cycloalkyl, such as a sugar radical, preferably a monosaccharide, such as glucosyl, γ) (hetero)aryl, such as _phenyl , and represents; R _a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably R _a represents a hydrogen atom), a hydrocarbon-based chain substituted with one or more (preferably one) groups selected from the group consisting of: It represents an alkyl group as defined;

According to one embodiment, the substituted hydrocarbon-based chain, especially the alkyl, is linear.

According to another embodiment, the substituted hydrocarbon-based chain, especially the alkyl, is branched.

According to another specific embodiment of the present invention, the hydrocarbon-based chain of the radical R ¹ of the present invention is substituted or interrupted.

According to a specific embodiment of the invention, the hydrocarbon-based chain (in particular the alkyl group as previously defined) of the radical R ¹ of the invention is:

- a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero ) cycloalkyl, such as anhydride, dithiolane or epoxide, j) cosmetic active agent selected from colored or non-colored, fluorescent or non-fluorescent chromophores, such as optical brightener, UV-screening agent, h) (hetero)aryl, such as phenyl or furyl, k) RX, where R is α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, such as sugar, preferably monosaccharide, such as glucose, γ) (hetero)aryl, such as phenyl, δ) X represents a group selected from cosmetic actives as previously defined _and represents amide or urea; R _a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl or aryl(C ₁ -C ₄ )alkyl group such as benzyl, preferably R _a represents a hydrogen atom) (preferably is substituted with a group;

- is interrupted by one or more (preferably one) atoms or groups selected from O, S, N(R _a ) and carbonyl, or combinations thereof, such as esters, amides or ureas, where R _a is previously defined As described above, preferably R _a is a hydrogen atom; It preferably represents an alkyl group interrupted by one or more atoms selected from O and S, more preferentially O or S, especially S atoms. Specifically, when it represents an interrupted hydrocarbon-based chain, especially alkyl, R ¹ is C ₇ -C ₂₀ , more particularly C ₈ -C ₁₈ and even more particularly C ₉ -C ₁₆ .

According to a preferred embodiment of the invention, the hydrocarbon-based chain (in particular the alkyl group as previously defined) of the radical R ¹ of the invention is:

- a) halogen, such as chlorine or bromine, b) hydroxyl, d) (di)(C ₁ -C ₄ )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl, such as epoxides, h) (hetero)aryl such as phenyl or furyl, k) RX where R is α) cycloalkyl such as cyclohexyl, β) heterocycloalkyl such as sugars, preferably monosaccharides such as glucose, γ) represents a group selected from (hetero)aryl, such as phenyl, and X represents a') O, S or N(R _a ), preferably S; R _a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably R _a represents a hydrogen atom;

- is interrupted by one or more (preferably one) atoms or groups selected from O, S, N(R _a ) and carbonyl, or combinations thereof, such as esters, amides or ureas, where R _a is previously defined As described above, preferably R _a is a hydrogen atom; It preferably represents an alkyl group interrupted by one or more atoms selected from O and S, more preferentially O or S, especially S atoms. Specifically, when it represents an interrupted hydrocarbon-based chain, especially alkyl, R ¹ is C ₇ -C ₂₀ , more particularly C ₈ -C ₁₈ and even more particularly C ₉ -C ₁₆ .

Preferably, the substituted and interrupted hydrocarbon-based chains are especially alkyl, and are preferably linear.

More preferentially, when the hydrocarbon-based chain R ¹ is substituted, it is substituted at the end of the chain opposite from the carbon atom carrying the radical R ¹ .

According to one embodiment of the present invention, the hydrocarbon chain R ¹ has the following formula -(CH ₂ ) _r -X-(ALK) _u -G, N(R _a ), preferably S, ALK represents a linear or branched, preferably linear, (C ₁ -C ₁₀ )alkylene and more specifically (C ₁ -C ₈ )alkylene chain; , r represents an integer from 6 to 11, preferably from 7 to 10 inclusive, such as 8; u is 0 or 1; G is a hydrogen atom, or hydroxyl, carboxyl, (di)(C ₁ -C ₄ )(alkyl)amino, (hetero)aryl, especially aryl, such as phenyl, cycloalkyl such as cyclohexyl, or sugar, especially represents a group selected from monosaccharides (optionally protected with one or more groups such as acyl), preferably Sug.

[Formula 4]

Here, R ^e represents the group R ^f -C(O)- and R ^f represents a (C ₁ -C ₄ )alkyl group, such as methyl. Preferably, when u is 0, G represents a cycloalkyl group such as cyclohexyl, or a sugar as previously defined. According to another advantageous variant, when u is 1, G is a hydrogen atom or a group selected from hydroxyl, carboxyl, (di)(C ₁ -C ₄ )(alkyl)amino or (hetero)aryl, specifically Aryl, such as phenyl.

According to another specific embodiment of the present invention, the PHA copolymer(s) are selected from the group consisting of (C ₅ -C ₂₈ )alkyl wherein R ¹ is substituted with one or more halogen atoms such as fluorine, chlorine or bromine, more specifically linear (C ₄ -C ₂₀ )alkyl, more specifically, (C ₅ -C ₁₃ )alkyl substituted with a halogen atom such as bromine. Preferably, the halogen atom is substituted at the terminal of the alkyl group. More preferentially, R ¹ represents 1-halo-5-yl, such as 1-bromo-5-yl.

According to another specific embodiment of the invention, the PHA copolymer(s) are such that R ¹ represents a (C ₅ -C ₂₈ )alkyl group substituted with one or more groups selected from g) cyano, and more specifically a cyano group. g) substituted, preferably linear, (C ₃ -C ₁₃ )alkyl groups, such as 1-cyano-3-propyl.

According to another specific embodiment of the present invention, the PHA copolymer(s) have R ¹ selected from vii) (hetero)aryl(C ₁ -C ₂ )alkyl and more specifically aryl(C ₁ -C ₂ )alkyl groups, Preferably it represents phenylethyl.

According to another specific embodiment of the invention, the PHA copolymer(s) are such that R ¹ represents a (C ₅ -C ₂₈ )alkyl group substituted with one or more groups selected from c) (hetero)cycloalkyl. More specifically, R ¹ represents a heterocycloalkyl group, such as a (C ₅ -C ₁₃ )alkyl group, preferably linear, substituted with epoxide or dithiolane, preferably with epoxide.

Specifically, the PHA copolymer(s) may be selected from the groups in which R ² is a linear or branched (C ₁ -C ₂₈ )alkyl, and a linear or branched (C ₂ -C ₂₈ )alkenyl, particularly a linear hydrocarbon-based group, more specifically a linear hydrocarbon-based group. is selected from (C ₃ -C ₂₀ )alkyl or (C ₃ -C ₂₀ )alkenyl, preferably linear or branched, more specifically linear, (C ₃ -C ₂₀ )alkyl.

Specifically, the PHA copolymer(s) may be selected from the groups in which R ² is a linear or branched (C ₁ -C ₂₈ )alkyl, and a linear or branched (C ₂ -C ₂₈ )alkenyl, particularly a linear hydrocarbon-based group, more specifically a linear hydrocarbon-based group. is selected from (C ₃ -C ₂₀ )alkyl or (C ₃ -C ₂₀ )alkenyl; Preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R ¹ minus at least one carbon atom, preferably corresponding to the number of carbon atoms of the radical R ¹ minus two carbon atoms.

According to one embodiment of the invention, the PHA copolymer(s) are such that the radicals R ² are linear or branched, preferably linear, (C ₃ -C ₈ )alkyl, especially (C ₃ -C ₆ )alkyl, Preferred are (C ₄ -C ₆ )alkyl groups, such as n -pentyl or n -hexyl.

According to another embodiment of the composition (C1) or composition (C1') according to the invention, the PHA copolymer(s) are branched (C ₃ -C ₈ )alkyl, especially (C ₄ -C ₆ )alkyl. The radical R ² preferably comprises a branched (C ₄ -C ₅ )alkyl radical, such as isobutyl.

According to another embodiment of the composition (C1) or composition (C1') according to the invention, the PHA copolymer(s) of the invention comprise units (A) having an alkyl radical R ¹ as previously defined, as previously defined unit (B) as described above, and linear or branched (C ₆ -C ₂₀ )alkenyl, especially (C ₇ -C ₁₄ )alkenyl, preferably linear and containing only one unsaturation at the chain end. Kenyl, more particularly (C ₈ -C ₁₀ )alkenyl radical, especially -[CR ⁴ (R ⁵ )] _q -C(R ⁶ )=C(R ⁷ )-R ⁸ where R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl, preferably a hydrogen atom, and q is 2 to 20 (inclusive) ), preferably 3 to 10, more preferably 4 to 8, such as representing an integer of 6), such as -[CH ₂ ] _q -CH=CH ₂ (where q is 3 to 8 (inclusive), preferably ( representing 4 to 6, such as 5).

According to one embodiment of the composition (C1) or composition (C1') according to the invention, the PHA copolymer(s) have hydroxyl, (di)(C ₁ -C ₄ )(alkyl)amino, carboxyl, and _R C ₄ )alkyl, such as (C ₁ -C ₄ )(alkyl)benzyl or phenylethyl, or heteroaryl(C ₁ -C ₄ )alkyl, such as furylmethyl). ) and an alkyl radical R ¹ containing 8 to 16 carbon atoms substituted with a group (A) .

According to one embodiment of the composition (C1') according to the invention, the copolymer(s) are linear or branched, preferably linear, (C ₁ -C ₈ )alkyl, especially (C ₂ -C ₆ ) and units (B) having an alkyl, preferably (C ₄ -C ₅ )alkyl radical R ² , such as pentyl.

According to another embodiment of the composition (C1) or composition (C1') according to the invention, the PHA copolymer(s) comprise units (A) containing alkyl radicals R ¹ as previously defined, the same unit (B) and a linear or branched (C ₆ -C ₂₀ )alkenyl, especially (C ₇ -C ₁₄ )alkenyl radical, preferably linear and containing only one unsaturation at the chain end, and More specifically (C ₈ -C ₁₀ )alkenyl radicals, such as -[CH ₂ ] _q -CH=CH ₂ (p represents an integer from 3 to 8 (inclusive), preferably from 4 to 6, such as 5. ) and a unit (C) containing

According to a specific embodiment of the invention, in the PHA copolymer(s), unit (A) comprises a hydrocarbon-based chain as previously defined, specifically ii), and said unit (A) preferably contains 0.1% a mole percentage ranging from 1% to 99%, more preferably a mole percentage ranging from 0.5% to 50%, even more preferably a mole percentage ranging from 1% to 40%, even more preferably a mole percentage ranging from 2% to 30%, or in a mole percentage ranging from 5% to 30%.

According to a specific embodiment of the invention, in the PHA copolymer(s), unit (A) is preferably present in a mole percentage ranging from 0.5% to 99%.

According to one embodiment, when R ¹ represents an unsaturated and uninterrupted (C ₅ -C ₂₈ )alkyl group, units (A) are preferably from 0.5% to 99%, more preferably from 50% to 99%, more specifically It is present in a mole percentage ranging from 60% to 99%, even more preferentially from 70% to 99%. According to this embodiment, for all of units (A) , (B) and (C) , unit (B) is preferably present in a mole percentage ranging from 2% to 40%; Unit (C) is preferably present in a mole percentage ranging from 0.5% to 20%.

In another embodiment, R ¹ 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 ) When representing a hydrocarbon-based chain selected from alkynyl, preferably the hydrocarbon-based group is linear and said hydrocarbon-based chain is substituted by one or more atoms or groups a) to m) as defined for R ¹ /or is interrupted by one or more heteroatoms or groups a') to c') and is optionally substituted by one or more atoms or groups a) to m), specifically as defined above, and/or by one or more heteroatoms or groups a represents a hydrocarbon-based group selected from linear or branched (C ₄ -C ₂₈ )alkyl, interrupted by ') to c'), and for all of units (A) , (B) and (C) , unit (A) ) is preferably a mole percentage ranging from 0.5% to 99%, more preferably a mole percentage ranging from 1% to 50%, even more preferably a mole percentage ranging from 5% to 40%, even better from 5% to 5%. present in mole percentages in the range of 30%; Unit (B) is present in a mole percentage ranging from 1% to 99.5%, preferably from 1% to 90%, more preferentially from 2% to 70%, and unit (C) preferably ranges from 0.5% to 20%. It is present in mole percentage of . Advantageously, the PHA copolymer(s) of the invention comprise from 5 mol% to 95 mol% of units (B) , especially from 10 mol% to 90 mol% of units (B) . According to this embodiment, the PHA copolymer(s) contain 0.5 mol% to 10 mol% of units (C) ; More advantageously, the copolymer comprises from 5 mol% to 95 mol% of units (B) and from 0.5 mol% to 7 mol% of units (C) .

According to a more specific embodiment of the invention, the PHA copolymer(s) are, in PHA copolymer(s) a):

- Unit (A) comprises a hydrocarbon-based chain substituted by one or more atoms or groups a) to m) and/or interrupted by one or more heteroatoms or groups a') to c') as defined above, Unit (A) has a mole percentage ranging from 0.1% to 99%, preferably a mole percentage ranging from 0.5% to 50%, more preferably a mole percentage ranging from 1% to 40%, even more preferably a mole percentage ranging from 5% to 30%. is present in units (A) in mole percentages, even better in mole percentages ranging from 5 mole % to 30 mole %;

- the unit (B) is present in a mole percentage of unit (B) ranging from 1% to 99.5%, preferably in a mole percentage of 1% to 90%, more preferentially in a mole percentage of unit (B) ranging from 2 mol% to 70 mol%. ;

- the units (C) are present in a mole percentage of the units (C) ranging from 0.5 to 20%, preferentially from 1% to 10%, more preferentially from 0.5 mol% to 10 mol%.

Preferably, R ¹ of unit (A) is a saturated unsubstituted or uninterrupted hydrocarbon-based chain, wherein unit (A) has more than 30%, more particularly more than 50%, more preferably more than 60%, preferably more than 60%. It is present in a mole percentage of 60% to 90%.

If the copolymer(s) do not contain any additional unit units (C), the value of the mole percentages of units (A), (B) and (C) of the PHA copolymer(s) is (A) + (B ) is calculated for the total number of moles; Otherwise, if the copolymer(s) of the invention comprise three different units (A), (B) and (C), the mole percentage is the total number of moles of (A) + (B) + (C) is calculated for; Otherwise, if the copolymer(s) of the invention comprises four different units (A), (B), (C) and (D), the mole percentage is (A) + (B) + (C) + calculated for the total number of moles of (D); Otherwise, if the copolymer(s) of the invention comprises five different units (A), (B), (C), (D) and (E), the mole percentage is (A) + (B) Calculated for the total number of moles of + (C) + (D) + (E).

According to one form of the invention, the PHA copolymer(s) of the invention comprise the following repeating units (A) , and also their optical or geometric isomers, their organic or inorganic acid or base salts, and their solvates, such as hydrates: Includes:

In repeat units A1 to A12:

- ALK ₁ represents a divalent linear or branched C ₁ -C ₂₀ , preferably linear or branched, more preferentially linear, C ₁ -C ₁₀ , hydrocarbon-based radical;

- ALK ₂ represents a divalent linear or branched C ₁ -C ₂₀ , preferably linear or branched C ₁ -C ₁₂ , hydrocarbon-based radical;

- Rr and Rw independently represent a hydrogen atom or a C ₁ -C ₄ alkyl radical 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 heterocycloalkyl, such as 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 with one or more groups such as acyl, especially acetyl);

Specifically, the stereochemistry of the carbon atom carrying the radical R ¹ is the (R) configuration.

According to one form of the invention, the PHA copolymer(s) of the invention comprise repeating units (B) of formula (A12), and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvents thereof. Includes cargo, such as baggage, and (B) is understood to be different from (A) .

Preferentially, the PHA copolymer(s) of the invention comprise the following repeating units, and also their optical or geometric isomers, their organic or inorganic acid or base salts, and their solvates such as hydrates:

[Formula 5]

m and n are as previously defined, Hal represents a halogen atom, such as bromine, and t represents an integer from 1 to 10, preferably from 3 to 8, such as 6.

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

Ar': represents (C ₁ -C ₄ )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, specifically a monosaccharide (optionally protected with one or more groups such as acyl); Preferably, Sug represents:

[Formula 6]

Here, R ^e represents the group R ^f -C(O)- and R ^f represents a (C ₁ -C ₄ )alkyl group such as methyl.

Specifically, the stereochemistry of the carbon atoms carrying the radicals R ¹ and R ² are the same (R) or (S) configuration, preferably the (R) configuration.

More specifically, the stereochemistry of the carbon atoms carrying the radicals R ¹ , R ² and R ³ are the same (R) or (S) configuration, preferably the (R) configuration. More specifically, the stereochemistry of the carbon atoms carrying the radicals R ¹ , R ² , R ³ and R ⁴ are the same (R) or (S) configuration, preferably the (R) configuration.

More specifically, the stereochemistry of the carbon atoms carrying the radicals R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same (R) or (S) configuration, preferably the (R) configuration.

More preferentially, the PHA copolymer(s) have the formula:

[Formula 7]

M, n, Hal, t, Ar, Ar', Cycl, Fur and Sug are as previously defined for compounds (1) to (14).

Preferably, the PHA(s) of the present invention are compounds (1), (2a), (10), (11), (15), (16), (17) and (20), more preferably ( 15), (16) and (17), especially (16).

More specifically, the PHA(s) of the present invention include compounds (1'), (2a'), (10'), (11'), (15'), (16'), (17') and (20) '), more preferably selected from (15'), (16') and (17'), especially (16').

More specifically, the PHA a) of the present invention is compound (23').

Preferably, the PHA(s) a) of the present invention are compounds (25), (26), (31), (32), (33), (34a) (42), and (43), more preferably is selected from (25), (26), (31) and (32), especially (26).

The PHA copolymer(s) of the present invention preferably have a number average molecular weight in the range of 50 000 to 150 000.

Molecular weight can be determined in particular by size exclusion chromatography. The method is described below in the Examples.

The PHA copolymer(s) is specifically in the range of 0.1% to 65% by weight relative to the total weight of the composition, preferably in the range of 0.1% to 60% by weight, specifically in the range of 1% to 65% by weight relative to the total weight of the composition. in the range of 50% by weight, and more specifically in the range of 5% to 40% by weight, preferably in the range of 10% to 35% by weight, more preferably in the range of 20% to 30% by weight. is present in the composition (C1) according to the invention.

The PHA copolymer(s) specifically range from 0.1% to 60% by weight relative to the total weight of the composition, specifically in the range from 1% to 50% by weight relative to the total weight of the composition, and more specifically 3% by weight. in an amount ranging from 5% 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, even better in the range from 15% to 20% by weight. present in the composition (C1') according to the invention.

Method for preparing PHA copolymer(s):

Methods for preparing the PHA copolymer(s) of the present invention are well known to those skilled in the art. Particular mention may be made of the use of “ functionalizable ” PHA-producing microbial strains.

The term " functionalizable " refers to a hydrocarbon-based chain containing one or more atoms or groups capable of chemically reacting with another reagent - also referred to as a " reactive atom or reactive group " - to provide a Σ covalent bond with said reagent. It means that the PHA copolymer(s) comprises. A reagent is, for example, a compound comprising at least one nucleophilic group and the functionalized hydrocarbon-based chain comprises at least one electrophilic or binuclear atom or group, and the nucleophilic group(s) are electrophilic. Reaction with group(s) results in Σ covalent grafting of the reagent. Nucleophilic reagents can also react with one or more unsaturations of the alkenyl group(s), resulting in grafting by covalent linkage of the reagent with the functionalized hydrocarbon-based chain. The addition reaction may also be radical-based, Markovnikov or anti-Markovnikov type addition, or nucleophilic or electrophilic substitution. The addition or condensation reaction is carried out via a radical route, with or without catalysts or enzymes, preferably by heating to a temperature below 100° C. or without heat supply, under a pressure exceeding 1 atm or otherwise, under an inert atmosphere or Otherwise, it may or may not occur under oxygen or without oxygen.

The term “ nucleophilic ” refers to any atom or group that donates electrons by inductive effect +I and/or mesomeric effect +M. Electron-donating groups that may be mentioned include hydroxyl, thiol and amino groups.

The term “ electrophilic ” refers to any atom or group that is electron-withdrawing by the inductive effect -I and/or the mesomeric effect -M. Electron-withdrawing species that may be mentioned include:

In particular, microorganisms producing the PHA of the present invention with a hydrocarbon-based chain include Cyanobacteria of the order Nostocales (e.g. Nostoc muscorum , Synechocystis and It can be produced naturally by bacterial kingdoms such as Synechococcus , but mainly by Proteobacteria , for example in 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)

- Gamma-Proteobacteria ( Acinetobacter junii ) of the Pseudomonales order of the Moraxellaceae family.

Among microorganisms of the bacterial family, Azotobacter , Hydrogenomomas , or Chromatium genera are the most representative PHA-producing organisms.

In particular, organisms that naturally produce PHAs with C ₃ -C ₅ hydrocarbon-based chains are in particular Proteobacteria , such as Gamma-Proteobacteria , and more specifically those of the Pseudomonales order of the Pseudomonas family, such as Pseudomonas resinovorans , Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa , Pseudomonas citronellolis , Pseudomonas Mendo Sheena ( Pseudomonas mendocina ), Pseudomonas chlororaphis and preferably Pseudomonas putida GPo1 and Pseudomonas putida KT2440 , preferably Pseudomonas putida and specifically Pseudomonas putida GPo1 and Pseudomonas putida KT2440 .

Certain organisms not belonging to the order Pseudomonales , such as Commamonas testosteroni , belonging to the class Beta-Proteobacteria of the order Burkholderiales of the family Comamonadaceae . Additionally, PHA can be produced naturally.

Microorganisms producing PHA according to the invention may also be recombinant strains if a 3-oxidation PHA synthase metabolic pathway is present. The 3-oxidized PHA synthase metabolic pathway is mainly represented by four classes of enzymes, EC: 2.3.1 B2, EC: 2.3.1 B3, EC: 2.3.1 B4 and EC: 2.3.1 B5.

The recombinant strain is from the Bacteria family, such as Escherichia coli, or from the Plantae family, such as Chlorella pyrenoidosa ( International Journal of Biological Macromolecules , 116, 552-562 "Influence of nitrogen on growth, biomass composition, production, and properties of polyhydroxyalkanoates (PHAs) by microalgae"]) or the Fungi kingdom, such as Saccharomyces cerevisiae ) or Yarrowia lipolytica : Literature [ 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"] It may be of

For example, genetically modified microorganisms that may make it possible to increase the production of PHA and/or increase the oxygen consumption capacity and/or reduce autolysis and/or change the monomer ratio can also be used.

In the case of PHA, it is known that a large portion of the total production cost is used for culture medium and mainly substrate/carbon source. Therefore, it is possible to use genetically modified microorganisms that use fewer nutrients (carbon sources) for growth, for example, microorganisms that are essentially photoautotrophs, that is, using light and CO ₂ as their main energy sources.

The copolymer is, for example, microorganisms belonging to the genus Pseudomonas , such as Pseudomonas resinovorans , Pseudomonas putida, Pseudomonas fluorescens , Pseudomonas aeruginosa ), Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and preferably Pseudomonas putida; and C ₂ -C ₂₀ , preferably C ₆ -C ₁₈ , carboxylic acids such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid, or alkenoic acids such as undecylenic acid. ; Sugars 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; It can be obtained by biosynthesis by known methods using a carbon source that may be methane or carbon dioxide.

The biosynthesis is optionally carried out using β-acrylates such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid or phenylpropionic acid, and preferably acrylic acid. It can be performed in the presence of inhibitors of oxidative pathways.

According to one embodiment, the method for producing PHA of the present invention uses microbial cells that produce PHA through genetically modified microorganisms (GMO). Genetic modifications may result in increased PHA production, increased oxygen uptake capacity, increased resistance to solvent toxicity, decreased autolysis, altered PHA comonomer ratio, and/or any combination thereof. In some of these embodiments, changing the comonomer ratio of unit (A) increases the amount of dominant monomer relative to (B) of the resulting PHA of the invention. In another embodiment, the PHA-producing microbial cells reproduce naturally.

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

It is also possible to use genetically modified microorganisms that produce phenylvaleric-co-3-hydroxydodecane copolymer ( Sci. China Life Sci., Shen R., et al., 57 , No. 1, (2014) with a strain such as Pseudomonas entomophila LAC23 ]).

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

Appropriate known conditions of temperature, pH and dissolved oxygen (O _D ) can be used for culturing microorganisms.

Microorganisms can be cultured according to any known culture method, such as continuous or batch mode, fed or non-fed mode, for example in a bioreactor.

The biosynthesis of the polymers used according to the invention is described in particular in the paper ["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 patents. It is described in application WO 2011/069244.

As previously defined, microbial strains producing PHAs that are functionalizable or contain reactive groups are, for example, those of the genus Pseudomonas, such as P. P. cichorii YN2 , P. citronellolis , P. jessenii , and more commonly Pseudomonas putida species, such as Pseudomonas putida GPo1 (synonym for Pseudomonas oleovorans ), p. Putida KT2442, p. Putida KT2440 , p. Putida KCTC 2407 and p. Putida BM01 , and especially P. It is Putida KT2440 .

Carbon source(s):

One means to access the PHAs of the present invention is to introduce into the culture medium one or more organic compounds, which organic compounds preferably have one or more carbon sources selected from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof. represents.

In one embodiment, the organic compound(s) will preferably be selected from alcohols, carboxylic acids and mixtures thereof.

Carbon source(s) can be classified into two categories:

One) Carbon source by one or more organic compounds introduced into the medium:

According to a specific embodiment of the invention, the organic compound(s) are alcohols, in particular (C ₅ -C ₂₀ )alkanols, and/or carboxylic acids, in particular optionally substituted and/or interrupted (C ₅ - C ₂₀ )alkanoic acids, especially (C ₅ -C ₂₀ )alkanoic acids, such as (C ₇ -C ₁₁ )alkanoic acids, such as nonanoic acid or pelargonic acid and/or (C ₅ -C ₂₀ )alkenoic acids, especially ( C ₅ -C ₂₀ )alkenoic acids, such as (C ₇ -C ₁₁ )alkenic acids, such as undecylenic acid, and mixtures thereof.

Carbon source(s) can be classified into three groups depending on their intended use:

- Group A: Organic compounds can help the growth of production strains and the creation of PHA structures linked to organic compounds.

- Group B: Organic compounds can help the growth of strains, but do not participate in the production of PHA, which is structurally linked to organic compounds.

- Group C: Organic compounds do not participate in the growth of the strain.

These microbiological processes are known to the person skilled in the art, especially from 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)].

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

According to another variant, the incorporation of a substrate structurally linked to the reactive atom(s), especially the halogen, or reactive group(s) of the PHA(s) of the invention may be achieved by forming a cosubstrate also structurally linked to the PHA in a medium suitable for microbial growth. It is introduced into the medium as a carbon source along with a second carbon source. (e.g. Group B for P. putida GPo1 : preferably terminal haloalkanoic acids, such as terminal bromoalkanoic acids).

According to another variant, the incorporation of a substrate structurally linked to the reactive atom(s), especially the halogen, or reactive group(s) of the PHA(s) of the invention may also be carried out in the PHA(s) in a medium suitable for microbial growth. It can be directly introduced into the medium as a carbon source with a second carbon source as a structurally linked co-substrate and a third carbon source as a co-substrate that is not structurally linked to the PHA(s). (e.g. Group C glucose or sucrose).

In one embodiment, the β-oxidation pathway inhibitor is selected from acrylic acid, 2-butynic acid, 2-octic acid, phenylpropionic acid, propionic acid, trans-cinnamic acid, salicylic acid, methacrylic acid, 4-pentenoic acid, or 3-mercaptopropionic acid, Preferably it is acrylic acid.

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

In particular, functionalization can be introduced by means of organic compounds selected from the alcohol and/or carboxylic acid category of precursors:

- to functionalize PHA(s) with branched alkyl groups (see, for example, Applied and Environmental Microbiology, 60 , No. 9, 3245-325 (1994));

- to functionalize the PHA(s) with linear alkyl groups containing terminal cyclohexyl units (see e.g. doi.org/10.1016/S0141-8130(01)00144-1);

- to functionalize the PHA(s) with unsaturated alkyl groups, preferably terminal (see for example doi.org/10.1021/bm8005616);

- to functionalize the PHA(s) with a linear alkyl group containing halogen, preferably at the end of the hydrocarbon-based chain (document [doi.org/10.1021/ma00033a002]);

- for functionalizing PHA(s) with (hetero)aromatic alkyl groups such as phenyl, benzoyl, phenoxy (e.g. J. Microbiol. Biotechnol., 11 , 3, 435-442 (2001 )] reference);

- to functionalize the PHA(s) with linear alkyl groups containing heteroatoms, especially at the ends of the hydrocarbon-based chain (see, for example, DOI 10.1007/s00253-011-3099-4);

- for functionalizing the PHA(s) with linear alkyl groups containing cyano functional groups, especially at the end of the hydrocarbon-based chain (see e.g. doi.org/10.1111/j.1574-6968.1992.tb05839.x) );

- for functionalizing the PHA(s) with linear alkyl groups containing epoxy functional groups, especially at the ends of the hydrocarbon-based chain (see, for example, doi.org/10.1016/S1381-5148(97)00024-2) .

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

In a specific embodiment of the invention, the fatty acid from Group A is selected from 11-undecenoic acid, 10-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and 5-cyanopentanoic acid.

In a specific embodiment of the invention, the fatty acid from Group A is selected from halooctanoic acids, such as 8-bromooctanoic acid.

In certain embodiments of the invention, the carbon source from group C is a monosaccharide, preferably glucose.

2) Carbon source in the presence of oxidation inhibitors introduced into the medium:

Another aspect of the invention is the use of a PHA-producing microbial strain in a medium suitable for microbial growth, said medium comprising: a substrate structurally linked to the PHA(s); One or more carbon sources that are not structurally linked to the PHA(s); and at least one oxidation and especially β-oxidation pathway inhibitor. This allows growth of microbial cells to occur in the medium, wherein the microbial cells synthesize the PHA polymer(s) of the invention; Preferably the copolymer specifically contains more than 95% identical units, with a comonomer ratio of unit (A) and unit (B) different from that obtained in the absence of the β-oxidation pathway inhibitor.

The following reaction scheme illustrates, by way of example, the functionalization of the PHA copolymer according to the invention starting from a PHA copolymer with unsaturated hydrocarbon-based chains according to Scheme 1 below:

[Formula 8]

In Scheme 1:

- R ² , m and n are as previously defined;

- Y is Hal, such as chlorine or bromine, hydroxyl, thiol, (di)(C ₁ -C ₄ )(alkyl)amino, RX where R is α) cycloalkyl, such as cyclohexyl, β) heterocycloalkyl, For example sugars, preferably monosaccharides such as glucose, γ) (hetero)aryl such as phenyl; δ) cosmetic active agents as previously defined; ε) represents a group selected from (C ₁ -C ₂₀ )alkyl, (C ₂ -C ₂₀ )alkenyl, (C ₂ -C ₂₀ )alkynyl; _{and ​ ​ ​ ​ ​ ​ ​} Represents a group selected from (as previously defined);

- q' represents an integer generically between 2 and 20, preferably between 3 and 10, more preferably between 4 and 8, such as 6, even more preferably between 3 and 8, preferably between 4 and 6, such as 5.

Michael or Diels-Alder addition, radical reaction, catalytic (especially with Pd or Ni) or non-catalytic hydrogenation reaction, halogenation reaction (especially with bromine), hydration reaction or oxidation reaction (which may be controlled or uncontrolled), and other reactions using double or triple unsaturation, such as reactions with electrophiles as shown schematically below.

According to a specific embodiment of the present invention, the PHA copolymer is:

- linear or substituted and/or interrupted by groups as previously defined for R ¹ , comprising a total of 5 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more particularly 7 to 11 carbon atoms. branched, saturated hydrocarbon-based chain R ¹ , and

- linear or branched (C ₃ -C ₂₀ )alkenyl, especially (C ₅ -C ₁₄ )alkenyl and more particularly (C _{7 )} , preferably linear and containing only one unsaturation at the chain end -C ₁₀ )alkenyl radical, specifically -[CR ⁴ (R ⁵ )] _q -C(R ⁶ )=C(R ⁷ )-R ⁸ (wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl, preferably a hydrogen atom, and q is 2 to 20 (inclusive), preferably 3 to 10. , more preferentially represents an integer from 4 to 8, such as 6), such as -[CH ₂ ] _q -CH=CH ₂ (q represents an integer from 3 to 8 (inclusive), preferably from 4 to 6, such as 5 It includes a hydrocarbon-based chain R ² representing ,

Said chain R ² is 1% to 99% unsaturated, preferentially 2% to 50% and even more preferentially 3% to 40% unsaturated, even more particularly 3% to 30% unsaturated, even better. Contains 5% to 20% unsaturation. According to this specific embodiment of the invention in which the PHA copolymer comprises an unsaturation, such unsaturation may be chemically modified via:

A) Through addition reactions with particles, chemical compounds or polymers, such as radical addition, Michael addition, electrophilic subscripting, Diels-Alder, halogenation, hydration or hydrogenation reactions, and preferably hydrothiolation reactions.

Specifically, the hydrothiolation reaction can be carried out in the presence of a thermal initiator, a redox initiator or a photochemical initiator, especially selected from:

- linear, branched, cyclic or aromatic alkanethiols containing 1 to 14 carbon atoms, such as methane-, ethane-, propane-, pentane-, cyclopentane-, hexane-, cyclohexane-, heptane-, octane- , phenylethane-, 4-tert-butylphenylmethane- or 2-furanmethane-thiol, preferably hexane-, cyclohexane-, heptane-, octane-, phenylethane-, 4-tert-butylphenylmethane- or 2-furanmethane-thiol;

- Organosiloxanes with thiol functionality, such as (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldimethoxysilane, 2-(triethoxysilyl)ethanethiol or mercaptopropyl-isobutyl -POSS;

- thiolated siloxane oils, especially those described in DOI: 10.1016/j.actbio.2015.01.020;

- Reactive functional groups such as amines, alcohols, acids, halogens, thiols, epoxides, nitriles, isocyanates, heteroatoms, preferably cysteine, cysteamine, N-acetylcysteamine, 2-mercaptoethanol, 1-mer Capto-2-propanol, 8-mercapto-1-octanol, thiolactic acid, thioglycolic acid, 3-mercaptopropionic acid, 11-mercaptoundecanoic acid, polyethylene glycol dithiol, 3-mercaptopropionitrile, Thiolated oligomers or polymers with 1,3-propanedithiol, 4-cyano-1-butanethiol, 3-chloro-1-propanethiol, 1-thio-β-D-glucose tetraacetate; and

- Thiols obtainable from disulfide reduction, such as phenyl disulfide or furfuryl disulfide.

Examples of initiators that may be mentioned include: tert-butyl peroxy-2-ethylhexanoate, cumene perpivalate, tert-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octa. Noyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile ), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis(tert -Butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,4-bis(tert-butylperoxycarbonyl)cyclohexane, 2, 2-bis(tert-butylperoxy)octane, n-butyl 4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, 1,3-bis( tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, di- tert-butyl diperoxyisophthalate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butyl peroxy-α-methylsuccinate, di-tert-butyl peroxide Oxydimethyl glutarate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, diethylene Glycol bis(tert-butylperoxycarbonate), di-tert-butyl peroxytrimethyl adipate, tris(tert-butylperoxy)triazine, vinyltris(tert-butylperoxy)silane phenothiazine, tetra Cene, perylene, anthracene, 9,10-diphenylanthracene, thioxanthone, benzophenone, acetophenone, xanthone, fluorenone, anthraquinone, 9,10-dimethylanthracene, 2-ethyl-9,10-dimethyloxyanthracene , 2,6-dimethylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, xantopinacol, 1,2-benzanthracene, 9-nitroanthracene. Each of these initiators can be used alone or in combination with each other.

The chemical reactions mentioned above 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: literature [10.1021/acs.biomac.9b00479]; Biomacromolecules , 19 , 3536-3548 (2018); Synthesis and preparation of PHA modified with mercaptohexanol: literature [10.1021/acs.biomac.8b01257]; Biomacromolecules , 20 , 2, 645-652 (2019); Synthesis and preparation of PHA modified with hydroxycinnamic acid sulfate and zosteric acid: literature [10.1021/bm049962e; Biomacromolecules , 5 , 4, 1452-1456 (2004)]; Radical addition of methyl methacrylate to 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 PHA modified with polysilsesquioxane (POSS): literature [10.1016/j.polymer.2005.04.020; Polymer Vol. 46, 14 , 5025-5031 (2005)]; Grafting of thio-beta-glucose onto unsaturated side chains: literature [1022-1336/99/0202-0091$17.50+.50/0; Macromol. Rapid Commun., 20 , 91-94 (1999)];

and/or

B) oxidation reactions, which may or may not be controlled, for example using permanganates of concentrated or dilute alkaline agents, or ozonolysis, oxidation in the presence of reducing agents (hydroxyl, epoxide or through which it is possible to obtain new materials with carboxyl groups).

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

Example of functionalization of PHA copolymers according to the invention starting from PHA copolymers with hydrocarbon-based chains containing epoxide groups, according to Scheme 2:

[Formula 9]

In Scheme 2, Y, m, n, q' and R ² are as defined in Scheme 1.

Epoxide structures can be obtained through conventional methods known to those skilled in the art, whether through biotechnological processes or chemical processes such as oxidation of unsaturated substances as previously mentioned. The peroxide group(s) can react with carboxylic acids, maleic anhydride, amines, alcohols, thiols or isocyanates, all of which have at least one linear or branched, cyclic or acyclic, saturated or unsaturated C ₁ -C ₂₀ hydrocarbon-based chains, or oligomers or polymers having them, especially amino (poly)saccharides, such as chitosan and (poly)sil(ox)an; 3-Glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3-(trimethoxysilyl)propylcarbamic acid, diethanolamine, or 3-mercapto of alkali metal or alkaline earth metal salts such as sodium. Contains -1-propane sulfonate. Epoxide groups can also react with water.

In particular the following documents may be mentioned:

- Preparation of PHA-bearing fillers starting with diethanolamine: literature [10.1021/bm8005616], Biomacromolecules, vol. 9, 8 , 2091-2096 (2008)];

- Preparation of PHA-bearing fillers starting with sodium 3-mercapto-1-propanesulfonate: literature [10.1021/acs.biomac.9b00870 Biomacromolecules , vol. 20, 9, 3324-3332 (2019)];

- Preparation of PHAs containing native epoxide units: literature [10.1016/S1381-5148(97)00024-2); Reactive and Functional Polymers, vol. 34, 1 , 65-77 (1997)].

Examples of functionalization of PHA copolymers according to the invention starting from PHA copolymers with hydrocarbon-based chains containing nucleophilic groups according to Scheme 3:

[Formula 10]

In Scheme 3, Y, m, n, q' and R ² are as defined in Scheme 1. M corresponds to an organic or inorganic binuclear group that may be substituted by a nucleophilic group; Preferably, the nucleophile is a heteroatom such as O, S or N that donates electrons through +I and/or +M effects. Preferably, the binuclear group M is selected from halogen atoms such as Br, and mesylate, tosylate or triflate groups. This is a reaction known to those skilled in the art. For example, the following documents may be mentioned: 10.1016/j.ijbiomac.2016.11.118, International Journal of Biological Macromolecules , vol. 95, 796-808 (2017)].

Examples of functionalization of PHA copolymers according to the invention starting from PHA copolymers with hydrocarbon-based chains containing cyano groups according to Scheme 4:

[Formula 11]

In Scheme 4, Y, m, n, q' and R ² are as defined in Scheme 1.

In the first step i), the PHA copolymer with side chains containing cyano or nitrile groups is reacted with the organo-alkali metal or organomagnesium compounds Y-MgHal, Y-Li or Y-Na and then hydrolyzed to give ketone functional groups. PHA copolymers having side chains containing grafted groups Y are provided. The ketone functional group can be converted to a thio ketone, for example, by thiolation using S8 in the presence of an amine or using Lawesson's reagent. The thio ketone, after total reduction ii) (e.g. by Clemmensen reduction), produces a PHA copolymer with side chains containing groups Y grafted with alkylene groups. Alternatively, the thio ketone can undergo controlled reduction iii) using conventional reducing agents to give a PHA copolymer with side chains containing groups Y grafted with hydroxyalkylene groups. The cyano groups of the starting PHA copolymer may react with water after hydration v) to give amide derivatives and after hydrolysis iv) to carboxyl derivatives. The cyano groups of the starting PHA copolymer can also give amine derivatives or ketone derivatives after reduction vi). PHA copolymers having hydrocarbon-based chains with nitrile functional groups are prepared through conventional methods known to those skilled in the art. For example, the following documents may be mentioned: 10.1016/0378-1097(92)90311-B, FEMS Microbiology Letters , vol. 103, 2-4 , 207-214 (1992)].

Examples of functionalization of PHA copolymers according to the invention starting from PHA copolymers with hydrocarbon-based chains at the chain ends according to Scheme 5:

[Formula 12]

In Scheme 5, R ¹ , R ² , m, n and Y are as previously defined and R' ¹ is i) linear or branched (C ₁ -C ₂₀ )alkyl, ii) linear or branched ( C ₂ -C ₂₀ )alkenyl, iii) a hydrocarbon-based chain selected from linear or branched (C ₂ -C ₂₀ )alkynyl; Preferably, the hydrocarbon-based group is linear; The hydrocarbon-based chain is substituted with one or more atoms or groups selected from: a) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )(alkyl) amino, e) (thio)carboxyl, f) (thio)carboxamide -C(O)-N(R _a ) ₂ or -C(S)-N(R _a ) ₂ , f) cyano, g ) iso(thio)cyanate, h) (hetero)aryl, such as phenyl or furyl, and i) (hetero)cycloalkyl, such as anhydride, or epoxide, j) colored or uncolored, fluorescent or non-fluorescent chromophore , chromophores such as those derived from optical brighteners or from UVA and/or UVB screening agents, and anti-aging actives.

Such chain-end grafts on PHA polymers are known to those skilled in the art. For example the following documents may be mentioned:

- Preparation of PHA oligomers by pyrolysis: literature [10.1021/bm0156274]; Biomacromolecules , vol. 3, 1 , 219-224 (2002)];

- Preparation of PHA oligomers by transesterification: literature [10.1021/ma011420r, Macromolecules , vol. 35, 3 , 684-689 (2002)];

- Preparation of PHA oligomer by hydrolysis: Reference [10.1016/0032-3861(94)90590-8 Polymer vol. 35, 19, 4156-4162 (1994)];

- Preparation of PHA oligomers by methanolysis: literature [10.1021/bm060981t, Biomacromolecules , vol. 8, 4 , 1255-1265 (2007)].

Other methods known to those skilled in the art may also be mentioned:

- Synthesis and characterization of PHA grafted with ascorbic acid: literature [10.1016/j.ijbiomac.2018.11.052]; International Journal of Biological Macromolecules , vol. 123: 7 (2019)];

- Preparation of PHB-b-PHO copolymers by lipase-catalyzed polycondensation with divinyl adipate: literature [10.1021/bm9011634, Biomacromolecules , vol. 10, 12 , 3176-3181 (2009)];

- Synthesis of PHB-b-PHO copolymers coupled via diisocyanate linkages: literature [10.1021/ma012223v; Macromolecules , vol. 35, 13 , 4946-4950 (2002)];

- Preparation of PHO oligomers on chitosan by condensation between the carboxylic acid terminus of PHO and the amine function of chitosan: literature [10.1002/app.24276; Journal of Applied Polymer Science , vol. 103, 1 , (2006)];

- Transesterification of PHA with propargyl alcohol to produce PHA oligomers that can be modified by “click” chemistry: literature [10.1016/j.reactfunctpolym.2011.12.005]; Literature [ Reactive and Functional Polymers, vol. 72, 2, 160-167 (2012)];

- Preparation of PHO-b-PCL copolymer: literature [10.1002/mabi.200400104; Macromolecular Bioscience , vol. 4, 11 (2004)];

- Preparation of PHO-b-PEG copolymer: literature [10.1002/macp.201000562; Macromolecular Chemistry and Physics ; vol. 212, 3, (2010)];

- Epoxidation of chain-end unsaturation and chain-end grafting of acids: literature [10.14314/polimery.2017.317; Politics , vol. 62, 4 , 317-322 (2017)];

- Grafting of organosiloxane units from chain ends onto PHA: see 10.1016/j.reactfunctpolym.2014.09.008; Reactive and Functional Polymers, vol. 84, 53-59 (2014)].

Combination of the previously described grafted PHA copolymers of the invention according to Scheme 6:

[Formula 13]

In Scheme 6, R' ¹ , R ² , m, n and Y are as previously defined,

X' represents a reactive atom or group capable of reacting with an electrophilic E or nucleophilic Nu atom or group to produce a Σ covalent bond; If X' is an electrophilic or binuclear group it can react with the reagent R' ¹ -Nu; If X' is a nucleophilic group Nu, it can react with R' ¹ -E to produce a Σ covalent bond.

For example, Σ covalent bonds or bonding groups that can be created are listed in the table below as by condensation of an electrophile and a nucleophile:

[Table 1]

It is also possible to start with PHA functionalized at the side chain and perform chain end grafting in the second step as described in Scheme 7. The opposite is also possible, where chain end grafting can be performed in a first step and then functionalization of the functionalizable side chain can be performed in a second step.

[Formula 14]

In Scheme 7, R' ¹ , R ² , m, n and Y are as previously defined,

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 in new grafted functional groups: literature [10.1021/ma0304426; Macromolecules , vol. 37, 2 , 385-389 (2004)];

- Grafting of PEG and PLA onto PHA functionalized with acid: literature [10.1002/marc.200900803] and literature [10.1002/mabi.200390033];

- Synthesis and preparation of PHA modified with polyethylene glycol dithiol: literature [10.1021/acs.biomac.9b00479].

b) Volatile oil(s)

The composition (C1) or composition (C1') according to the invention comprises one or more volatile oils.

For the purposes of the present invention, the term “oil” means a water-immiscible compound that is liquid at 25° C. and atmospheric pressure (1.013×10 ⁵ Pa).

The term “immiscible” means that mixing equal amounts of water and oil does not, after agitation, produce a stable solution containing only a single phase at the temperature and pressure conditions described above. After sufficient stirring with a Rayneri blender to create a vortex in the mixture (as a guide, 200 to 1000 rpm), observation is performed with the naked eye or, if necessary, using a phase contrast microscope, for 100 g of the obtained mixture. It is left for 24 hours at room temperature in a previously closed flask.

The term “volatile oil” refers to an oil (or non-aqueous medium) that can evaporate in less than one hour upon contact with the skin at room temperature and atmospheric pressure. The volatile oil is a liquid at room temperature and has a vapor pressure other than zero at room temperature and atmospheric pressure, specifically a vapor pressure in the range of 0.13 Pa to 40 000 Pa (10 ^-3 to 300 mmHg), preferably 1.3 Pa to 13 000 Pa ( It is a volatile cosmetic oil in the range of 0.01 to 100 mmHg), preferentially in the range of 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

For the purposes of the present invention, the term “non-volatile oil” means an oil with a vapor pressure of less than 0.13 Pa.

According to one embodiment of the invention, the volatile oil has a flash point of less than 120°C and a vapor pressure of less than 5 Pa, more specifically a flash point of less than 90°C and a vapor pressure of more than 1 Pa, and even more preferentially a flash point of 60°C. or less and the vapor pressure is greater than 5 Pa, and even more preferentially the flash point is less than 60°C and the vapor pressure is greater than 100 Pa.

The term “hydrocarbon-based oil” refers to an oil comprising primarily carbon and hydrogen atoms and possibly one or more functional groups selected from hydroxyl, ester, ether and carboxyl functional groups. Hydrocarbon-based oils therefore do not contain any silicon or fluorine atoms.

The term “silicone oil” refers to an oil comprising at least one silicon atom, especially at least one Si—O group, more specifically organopolysiloxane.

The term “fluoro oil” means an oil containing at least one fluorine atom.

The term “non-polar hydrocarbon-based oil” refers to a hydrocarbon-based oil containing only carbon and hydrogen atoms (also referred to as hydrocarbon), preferably non-aromatic.

The term “polar hydrocarbon oil” refers to a hydrocarbon oil comprising mainly carbon and hydrogen atoms and one or more functional groups selected from hydroxyl, ester, ether and carboxyl functional groups.

The term “polar hydrocarbon oil” refers to a hydrocarbon oil comprising mainly carbon and hydrogen atoms and one or more functional groups selected from hydroxyl, ester, ether and carboxyl functional groups.

Volatile hydrocarbon-based or silicone oil

According to one embodiment, the volatile oil b) is a volatile hydrocarbon-based oil as follows:

* Hydrocarbon-based oils containing 8 to 16 carbon atoms, and especially

- C ₈ -C ₁₆ branched alkanes, such as isoalkanes (also known as isoparaffins), such as C ₈ -C ₉ isoparaffins, C ₁₃ -C ₁₆ isoparaffins, isododecane, isodecane, isohexa Decane, and oils (alone or in mixtures), sold for example under the trade names Isopars or Permetyls, preferably isododecane (2,2,4,4,6-pentamethylheptane) sold for example by Ineos also known), more preferentially isododecane;

- linear alkanes, such as C ₆ -C ₁₆ alkanes (alone or in mixtures), such as hexane, decane, undecane or tridecane, isoparaffin, or n-dodecane (C12) and n-tetradecane ( C14) (sold by Sasol under the references Parafol 12-97 and Parafol 14-97, respectively), undecane-tridecane mixture, obtained in examples 1 and 2 of patent application WO 2008/155059 from Cognis mixtures of n-undecane (C11) and n-tridecane (C13), and mixtures thereof, and also mixtures of n -undecane (C11) and n -tridecane (C13), Cetiol Ultimate from BASF ®;

- Volatile, non-aromatic cyclic C ₅ -C ₁₂ alkanes;

* Short-chain esters (containing a total of 3 to 8 carbon atoms), such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate or isobutyl acetate (sold for example by Solvay, Dow or Oxea);

* Structural formula R' ₁ -OC(O)-O-R' ₂ where R' ₁ and R' ₂ independently represent a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group. (represented) volatile carbonate hydrocarbon-based oil. R ₁ and R ₂ may preferably be the same. Preferably, R' ₁ and R' ₂ represent a linear butyl alkyl radical, a pentyl group. Advantageously, the ether oil is selected from dibutyl carbonate and dipentyl carbonate;

*Volatile ether oils of the formula R ₁ -OR ₂ wherein R ₁ and R ₂ independently represent a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group. R ₁ and R ₂ may preferably be the same.

Linear alkyl groups that may be mentioned include butyl groups and pentyl groups. Branched alkyl groups that may be mentioned include 1-methylpropyl group, 2-methylpropyl group, t-butyl group and 1,1-dimethylpropyl group. Advantageously, the ether oil is selected from dicaprylyl ether and dicapryl ether, most particularly dicaprylyl ether.

Volatile hydrocarbon-based oil(s) include in particular C ₆ -C ₁₆ alkanes and especially mixtures of alkanes such as dodecane, tetradecane, isohexadecane, undecane and tridecane, and isoparaffins such as C ₁₃ -C ₁₆ iso. It is selected from paraffin.

According to a preferred embodiment of the invention, the volatile oil(s) b) is preferably selected from undecane, decane, dodecane, isododecane, isohexadecane, tridecane, tetradecane and mixtures thereof. is a volatile, linear or branched hydrocarbon-based oil, comprising isododecane and/or a mixture of undecane and tridecane.

Specifically, the volatile oil(s) b) of the invention are preferably C ₉ -C ₁₂ alkanes of natural origin (whose chain comprises 9 to 12 carbon atoms), preferably linear or branched C ₉ alkanes. -C It is a mixture of ₁₂ alkanes. These mixtures are known inter alia as Vegelight Silk®, sold by INCI name C9-12 alkanes, CAS 68608-12-8, BioSynthIs.

According to one embodiment of the invention, the volatile oil(s) b) is a silicone oil, specifically containing 2 to 7 silicon atoms, which silicone oil is an alkyl or alkoxy oil containing 1 to 10 carbon atoms. Optionally includes a group.

Volatile silicone oils that can be used in the invention include, in particular, dimethicone, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, having a viscosity of 5 and 6 cSt. , dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof. there is.

According to one embodiment, the volatile oil(s) b) is selected from volatile hydrocarbon-based oils containing 8 to 16 carbon atoms, volatile silicone oils and mixtures thereof, such as Cetiol Ultimate® from BASF.

According to one embodiment, the volatile oil(s) b) is preferably selected from branched C ₈ -C ₁₆ alkanes and preferably isododecane.

According to one embodiment, the volatile oil(s) b) is preferably selected from linear C ₈ -C ₁₆ alkanes, more preferentially C ₉ -C ₁₂ alkanes, such as INCI C9-C12 alkanes, CAS 68608-12- Dodecane as 8, Vegelight Silk® sold by BioSynthIs, or a mixture of undecane and tridecane.

According to one embodiment, the volatile oil(s) b) is selected from linear or branched C ₈ -C ₁₆ alkanes, preferably mixtures of linear C ₈ -C ₁₆ alkanes and branched C ₈ -C ₁₆ alkanes, The mixture preferably comprises at least isododecane or Vegelight Silk® or a mixture of undecane and tridecane.

According to one embodiment, the volatile oil(s) b) comprises at least one silicone oil as defined above, preferably dodecamethylpentasiloxane, such as sold under the reference name DM by Shin-Etsu. -Fluid-2cs or cyclohexadimethylsiloxane, such as Xiameter PMX-0246 cyclohexasiloxane sold by Dow Chemical.

Preferably, if the volatile oil(s) b) is a mixture of at least one volatile hydrocarbon-based oil and at least one volatile silicone oil, the amount of silicone oil is less than 30%, preferably 20%, relative to the total mass of the composition. Less than, preferably less than 10%.

According to a specific embodiment of the invention, the amount of volatile oil b) is 5% to 95% by weight relative to the total weight of the composition, more specifically 20% to 90% by weight, preferentially 50% by weight, relative to the total weight of the composition. to 85% by weight, even better, 60% to 80% by weight.

c) Non-volatile oil(s)

Composition (C1) or composition (C1') also comprises one or more non-volatile oils.

The term “non-volatile oil” means an oil whose vapor pressure at 25° C. and atmospheric pressure is not zero and is less than 2.66 Pa, more specifically less than 0.13 Pa. For example, vapor pressure can be measured via static methods or via isothermal thermogravimetric effluent methods, depending on the vapor pressure of the oil (standard OCDE 104).

The non-volatile oil(s) of the invention may be of natural or synthetic origin, and are preferably of natural origin.

According to a specific embodiment of the invention, composition (C1) or composition (C1') comprises one or more non-volatile oils.

Among non-volatile oils, the following may be mentioned:

* Non-volatile fluorino oils, which may in particular be selected from fluorinated polyethers and may also be selected from fluorosilicone oils and fluorosilicones as described in EP-A-847752;

* Non-volatile silicone oils, which may in particular be selected from non-volatile silicones with the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl Dimethicone, phenyl trimethicone, diphenylsiloxyphenyl trimethicone; and also mixtures thereof.

These products are sold specifically by Dow Corning under the names PH-1555 HRI Cosmetic Fluid (trimethyl pentaphenyl trisiloxane) and Dow Corning 556 Cosmetic Grade Fluid (phenyl trimethicone); Diphenyl dimethicone, such as the products KF-54, KF54HV, KF-50-300CS, KF-53 d and KF-50-100CS sold by Shin-Etsu or diphenylsiloxy phenyl trimethicone KF56 A; Products Belsil PDM 1000 and Belsil PDM 20 (trimethylsiloxyphenyl dimethicone) sold by Wacker Chemie (alone or in mixtures);

* Non-volatile non-polar hydrocarbon-based oils, which may be chosen in particular from linear or branched compounds, for example of mineral or synthetic origin: i) liquid paraffin, ii) squalane, such as the reference name Neossance Squalane, isoeicosane sold by Amyris , iii) mixtures of linear, saturated hydrocarbons, especially C ₁₄ -C ₃₀ , more particularly C ₁₅ -C ₂₈ hydrocarbons, such as mixtures with the INCI names for example: (C ₁₅ -C ₁₉ )alkanes, (C ₁₈ -C ₂₁ )alkanes, (C ₂₁ -C ₂₈ )alkanes, for example the products Gemseal 40, Gemseal 60 and Gemseal 120 sold by Total, Emogreen L19 sold by SEPPIC, Emogreen L15 sold by SEPPIC, iv) hydrogenated or non-hydrogenated polybutenes, for example the Indopol family of products sold by INEOS Oligomers, products with the INCI name hydrogenated polyisobutene; v) hydrogenated or non-hydrogenated polyisobutene, preferably hydrogenated polyisobutene, for example non-volatile compounds of the Parleam® series sold by Nippon Oil Fats, vi) hydrogenated or non-hydrogenated polydecene, for example ExxonMobil the Puresyn® series of non-volatile compounds sold by the company, vii) decene/butene copolymers, butene/isobutene copolymers, and viii) mixtures thereof;

* Non-volatile polar hydrocarbon-based oils that may be selected from:

i) Saturated or unsaturated, linear or branched C ₁₀ -C ₂₆ fatty alcohols, preferably monoalcohols. Advantageously, the C ₁₀ -C ₂₆ alcohol is a fatty alcohol (preferably branched if it contains at least 16 carbon atoms; preferably, the fatty alcohol has 10 to 24 carbon atoms, more preferably 12 to 12 carbon atoms). containing 22 carbon atoms), especially such as lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol, octyl alcohol decanol and mixtures thereof;

ii) triglycerides consisting of fatty acid esters of glycerol (in particular the fatty acids thereof may have chain lengths ranging from C ₄ to C ₃₆ , and especially from C ₁₈ to C ₃₆ ), such oils possibly being linear or branched , and saturated or unsaturated; for example, heptanoic or octanoic triglycerides, caprylic/capric acid triglycerides, vegetable oils such as malt oil, sunflower oil, grape seed oil, sesame seed oil, corn oil, Apricot kernel oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, foreskin. (poppy) oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, sorghum oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion fruit. Liquid fractions of flower oil, musk rose oil, peanut oil, argan oil, passionflower oil, kaya oil, and mixtures thereof;

iii) Formula R-C(O)-OR', where R-C(O)- represents a carboxylic acid moiety containing 2 to 40 carbon atoms and R' represents a hydrocarbon-based chain containing 1 to 40 carbon atoms ), linear aliphatic hydrocarbon-based esters of alkylene glycols, especially ethylene glycol or propylene glycol, the total number of carbon atoms being advantageously at least 10. Examples of such esters are isoamyl laurate, cetostearyl octanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate or isostearate, ethyl palmitate, 2-ethylhexyl palmitate, isoste. Aryl isostearate, octyl stearate, isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate, cetyl octanoate, cocoyl capryl Rate/caprate, tridecyl octanoate, 2-ethylhexyl palmitate, alkyl benzoates, polyethylene glycol diheptanoate, propylene glycol bis(2-ethylhexanoate) and mixtures thereof, hexyl laurate, neophene Carbonic esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate or 2-octyldodecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, Isotridecyl isononanoate or octyl isononanoate, oleyl erucate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behe. Nate or myristyl myristate may be mentioned;

iv) hydroxylated esters such as polyglyceryl-2 triisostearate;

v) aromatic esters, such as tridecyl trimellitate, C ₁₂ -C ₁₅ alcohol benzoate, 2-phenylethyl ester of benzoic acid, and butyloctyl salicylate,

vi) linear fatty acid esters with a total carbon number ranging from 35 to 70, such as pentaerythrityl tetrapelargonate,

vii) Esters of C ₂₄ -C ₂₈ branched fatty acids or fatty alcohols, such as triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl tris(2-decyltetradecano) ate), pentaerythrityl tetraisostearate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetrakis(2-decyltetradecanoate);

viii) polyesters obtained by condensation of dimers and/or trimers of diols with unsaturated fatty acids, such as those with the INCI name dilinoleic acid/butanediol copolymer or dilinoleic acid/propanediol copolymer; Polyesters obtained by condensation of fatty acid dimers and diol dimers, such as dimer dilinoleyl dimer dilinoleate;

ix) synthetic ethers containing 10 to 40 carbon atoms, such as dicaprylyl ether;

x) dialkyl carbonates in which the two alkyl chains may be identical or different, such as dicaprylyl carbonate;

xi) Vinylpyrrolidone copolymers, such as vinylpyrrolidone/1-hexadecene copolymer (INCI name); and

xii) mixtures thereof;

* Non-volatile carbonate oils may be selected from carbonates of the formula R ₈ -OC(O)-OR ₉ where R ₈ and R ₉ may be the same or different and linear or branched C ₄ to C ₁₂ and preferentially C ₆ to C ₁₀ alkyl chains); Carbonate oils include dicaprylyl carbonate (or dioctyl carbonate), sold under the name Cetiol CC® by BASF, and bis(2-ethylhexyl) carbonate, sold under the name Tegosoft DEC® by Evonik. Bonate, dipropylheptyl carbonate (Cetiol 4 AII from BASF), dibutyl carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, It may be diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate.

* Formula R ₁ -OR ₂ where R ₁ and R ₂ are independently a linear, branched or cyclic C ₆ -C ₂₄ alkyl group, preferably a C ₆ -C ₁₈ alkyl group, preferably C ₈ -C ₁₂ Oils known as non-volatile ether oils (representing alkyl groups). R ₁ and R ₂ may preferably be the same. Linear alkyl groups that may be mentioned include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group. , octadecyl group, nonadecyl group, eicosyl group, behenyl group, docosyl group, tricosyl group and tetracosyl group. Branched alkyl groups that may be mentioned include 1,1-dimethylpropyl group, 3-methylhexyl group, 5-methylhexyl group, ethylhexyl group, 2-ethylhexyl group, 5-methyloctyl group, 1-ethylhexyl group. , 1-butylpentyl group, 2-butyloctyl group, isotridecyl group, 2-pentylnonyl group, 2-hexyldecyl group, isostearyl group, 2-heptylundecyl group, 2-octyldodecyl group, 1 ,3-dimethylbutyl group, 1-(1-methylethyl)-2-methylpropyl group, 1,1,3,3-tetramethylbutyl group, 3,5,5-trimethylhexyl group, 1-(2- Included are the methylpropyl)-3-methylbutyl group, 3,7-dimethyloctyl group and 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl group. As cyclic alkyl groups, cyclohexyl group, 3-methylcyclohexyl group and 3,3,5-trimethylcyclohexyl group, dilauryl ether, diisostearyl ether, dioctyl ether, nonylphenyl ether, dodecyl dimethylbutyl ether. , cetyl dimethylbutyl ether and mixtures thereof may be mentioned.

Among the non-volatile ether oils, mention may be made of dicaprylyl ethers, such as those sold under the reference name Cetiol OE sold by BASF.

According to one embodiment, the non-volatile oil(s) c) is selected from non-volatile silicone oils, non-volatile hydrocarbon-based oils, polar hydrocarbon-based oils, and mixtures thereof, as defined above, preferably as defined above. as selected from non-volatile hydrocarbon-based oils, polar hydrocarbon-based oils, and mixtures thereof.

According to one embodiment, the non-volatile hydrocarbon-based oil(s) c) has the formula R-C(O)-OR' as previously defined, where R-C(O)-O is a carboxyl group containing 2 to 40 carbon atoms. represents an acid residue and R' represents a hydrocarbon-based chain containing 1 to 40 carbon atoms), aliphatic hydrocarbon-based esters of alkylene glycols, especially ethylene glycol or propylene glycol, More preferentially selected from isoamyl laurate, isopropyl myristate, isodecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, cocoyl caprylate/caprate and mixtures thereof. , even better, comprising or consisting of at least one non-volatile oil representing isononyl isononanoate.

According to one embodiment, the non-volatile hydrocarbon-based oil(s) c) is a saturated or unsaturated, linear or branched C ₁₀ -C ₂₆ fatty alcohol, preferably a monoalcohol, having at least 16 carbon atoms as defined above. is preferably branched if it contains; It comprises or consists of at least one non-volatile oil, specifically selected from oleyl alcohol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol, such as Eutanol G sold by BASF under the reference name, and mixtures thereof. .

According to one embodiment, the non-volatile hydrocarbon-based oil(s) c) is triglyceride, consisting of esters of fatty acids and glycerol, the fatty acids specifically having a chain length in the range from C ₄ to C ₃₆ , especially from C ₈ to C ₃₆ . It comprises or consists of at least one non-volatile oil selected from cerides, which oils may be linear or branched, and saturated or unsaturated, as previously defined, and are preferably heptanoic or octanoic triglycerides, Caprylic/capric triglycerides and mixtures thereof, more preferably caprylic/capric triglycerides, such as the reference Palmester 3585 sold by KLK Oleo.

According to one embodiment, the non-volatile hydrocarbon-based oil(s) c) are preferably linear, saturated hydrocarbons, more specifically C ₁₅ -C ₂₈ hydrocarbons, selected from non-polar hydrocarbon-based non-volatile oils as previously defined, It comprises or consists of at least one non-volatile oil selected from hydrogenated or non-hydrogenated poly(iso)butene, and mixtures thereof.

According to one embodiment, the non-volatile hydrocarbon-based oil(s) c) comprises or consists of at least one non-volatile oil selected from non-polar hydrocarbon-based non-volatile oils, for example selected from mixtures with the following INCI names: Consists of: C ₁₅ -C ₁₉ alkanes, C ₁₈ -C ₂₁ alkanes, C ₂₁ -C ₂₈ alkanes, for example the products Gemseal 40, Gemseal 60, Gemseal 120 sold by Total, Emogreen L19 sold by SEPPIC, Emogreen L15 sold by SEPPIC, a product with the INCI name hydrogenated polyisobutene, and mixtures thereof.

According to a particular embodiment of the invention, the non-volatile hydrocarbon-based oil(s) c) is isoamyl laurate, isopropyl myristate, isodecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate. ate, oleyl alcohol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol, caprylic/capric triglycerides, for example mixtures with the following INCI names: C ₁₅ -C ₁₉ alkanes; C ₁₈ -C ₂₁ alkanes, C ₂₁ -C ₂₈ alkanes, for example Gemseal 40, Gemseal, products with INCI name hydrogenated polyisobutene, and mixtures thereof, more particularly INCI name hydrogenated polyisobutene phosphorus product, a mixture with the INCI name C ₁₅ -C ₁₉ alkanes, such as Emogreen L15 sold by SEPPIC, and isononyl isononanoate.

According to one embodiment, the non-volatile hydrocarbon-based oil(s) c) consists of one or more polar or non-polar non-volatile hydrocarbon-based oil(s) as defined above.

Preferably the non-volatile oil(s) of the invention are selected from: hydrogenated or non-hydrogenated polyisobutenes, preferably hydrogenated polyisobutenes, for example non-volatile compounds of the Parleam® family; A mixture of C ₁₅ -C ₁₉ alkanes, formula RC(O)-OR', where, as previously defined, RC(O)-O represents a carboxylic acid moiety containing 2 to 40 carbon atoms, and R ' represents a hydrocarbon-based chain containing 1 to 40 carbon atoms), linear aliphatic hydrocarbon-based esters, especially isononyl isononanoate.

According to one embodiment, the non-volatile oil(s) c) is preferably dimethicone, such as the grade Belsil DM 5 Plus Dimethicone sold by Wacker, the reference name Dowsil SH 200 C Fluid 10 CST sold by Dow Chemical or At least one silicone oil as defined above selected from the reference name Includes.

Preferably, the non-volatile oil(s) c) is a mixture of at least one non-volatile hydrocarbon-based oil and at least one volatile silicone oil, preferably selected from non-polar non-volatile hydrocarbon-based oils and polar non-volatile hydrocarbon-based oils. In this case, the amount of silicone oil is less than 30%, preferably less than 20%, preferably less than 10%, relative to the total mass of the composition.

According to a particular embodiment of the invention, the non-volatile oil(s) c) is present in an amount of from 0.1% to 15% by weight, preferably from 0.12% to 12% by weight, more preferentially from 0.15% to 0.15% by weight, relative to the total weight of the composition. It is present in the composition (C1) or composition (C1') in an amount of 10% by weight, even more preferentially from 0.2% to 5% by weight.

The mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is not zero and is less than 900, preferably less than 900.

The term "mass ratio" or weight ratio referred to as = the weight of the non-volatile oil(s) relative to the sum of the weights of the volatile oil(s) (sum of the Σ volatile oil(s) (VO)) according to the equation [Σ NVO]/[Σ VO] Means the ratio of the sum (Σ non-volatile oil(s) (NVO)).

Additionally, the mass ratio must comply with the following inequality: 0 < ≤ 900, even better 0 < < 900, specifically 1 < ≤ 800, even better 1 < <800; More specifically 2 < ≤ 700, and even better, 2 < <700; Priority 3 < ≤ 600, even better 3 < <600; More preferentially 3.5 < ≤ 600, even better 3.5 < <600; Even more preferentially 4 < ≤ 500, even better 4 < <500; More advantageously 4.5 < ≤ 400, even better 4.5 < <400.

According to one embodiment, the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is not zero and is less than 800, preferably less than 700, more preferentially less than 600, especially less than 500, even more. First of all, it is less than 400.

According to one embodiment, the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is greater than 0, preferably greater than 0.01, more preferentially greater than 0.5, even more preferentially greater than 1, even more preferably greater than 1. More preferably greater than 2, most specifically greater than 2.5, even more preferably greater than 3, especially greater than 4.

According to one embodiment, the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is between 4 and 200, in particular between 4.5 and 300.

According to one embodiment, the mass ratio between the volatile oil(s) b) and the non-volatile oil(s) c) is preferably between 3 and 800, in particular between 3 and 700, more specifically between 3.5 and 600, and even more preferably between 3.7. to 500, such as 3.8 to 400, even more preferably 3.9 to 300, even more preferably 4 to 200.

wax(es)

According to specific embodiments, the composition of the present invention includes one or more waxes.

The term "wax" refers to a lipophilic compound that is solid at room temperature (25°C), having a reversible solid/liquid state change, and having a melting point above 30°C (this may be up to 200°C, especially up to 120°C). do.

In particular, wax(es) suitable for use in the present invention may have a melting point of at least 45°C, and especially at least 55°C.

The composition (C1) or composition (C1') according to the invention preferably contains from 0.5% to 30% by weight, specifically from 1% to 20% by weight, more specifically from 2% to 15% by weight, relative to the total weight of the composition. It contains wax(es) in an amount in the range of weight percent.

According to a particular form of the invention, the composition of the invention is solid (in particular anhydrous). This may then exist in stick form; In order to reduce or even eliminate the presence of strata in the solid composition, the crystallite form has an aspect ratio of at least 2 and has a melting point in the range from 70° C. to 110° C., and preferably from 70° C. to 100° C. of polyethylene microwax will be used. These crystallites of needle form and in particular their dimensions can be visually characterized according to the following method.

Pasty compound(s)

According to specific embodiments, the compositions of the present invention include one or more pasty compounds.

For the purposes of the present invention, the term "pasty compound" refers to a lipophilic fatty compound that undergoes a reversible solid/liquid state change, has an anisotropic crystal configuration in the solid state, and comprises a liquid fraction and a solid fraction, at a temperature of 23° C. it means.

According to a particular embodiment of the invention, the composition (C1) or composition (C1') according to the invention comprises b) at least one volatile oil, c) at least one non-volatile oil, optionally e) water and optionally f) b ) and one or more organic solvents other than c).

d) Organic solvent(s) other than b) and c)

According to a particular embodiment of the invention, composition (C1) or composition (C1') also comprises at least one organic solvent other than b) and c), which is non-polar or polar, preferably polar, which is protic. or aprotic, more specifically protic and/or polar, preferably protic and polar.

Preferably, the organic solvent(s) f) are water-miscible.

The organic solvent(s) f) that may be used in the composition (C1) or composition (C1') of the invention may also be volatile.

Among the organic solvents f) that can be used in the composition (C1) or composition (C1') according to the invention, polar protic or polar aprotic organic solvents, preferably polar protic organic solvents, specifically 2 to 10 Particular mention may be made of lower monoalcohols containing carbon atoms, such as ethanol, butanol and isopropanol, preferably ethanol.

According to one embodiment, the composition (C1) or composition (C1') of the invention comprises one or more monoalcohols, preferably selected from monoalcohols containing 2 to 6 carbon atoms, such as ethanol, n-butanol and isopropanol. Contains organic solvent f).

According to a specific form of the invention, composition (C1) or composition (C1') comprises a) at least one polyhydroxyalkanoate (PHA) copolymer as defined above; and b) one or more volatile oils as previously defined; and c) at least one non-volatile oil as previously defined; and f) monoalcohols containing 2 to 6 carbon atoms, such as ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol or hexanol, preferably n-butanol or ethanol, even more It contains at least one organic solvent, preferentially selected from ethanol.

Preferably, the amount of organic solvent(s) f) is less than 70% by weight, more preferably less than 50% by weight, relative to the total weight of composition (C1) or composition (C1'). According to one embodiment of the invention, composition (C1) or composition (C1') comprises organic solvent(s) f) in an amount of more than 0.5% by weight, more specifically more than 1% by weight, relative to the total weight of the composition. . Specifically, composition (C1) or composition (C1') comprises from 2% to 50% by weight of organic solvent(s) f).

e) water

According to a particular embodiment of the invention, composition (C1) or composition (C1') comprises e) water.

According to a specific embodiment, composition (C1) or composition (C1') comprises e) water and, optionally, d) one or more surfactants as defined below.

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

f) surfactant

According to a specific embodiment of the invention, composition (C1) or composition (C1') also comprises f) one or more surfactants, preferably nonionic or ionic surfactants, or mixtures thereof.

According to another specific embodiment of the present invention, composition (C1) does not contain any surfactant.

According to a specific embodiment, composition (C1) or composition (C1') comprises a) at least one PHA as previously defined and b) at least one volatile oil as previously defined, c) at least one as previously defined. It comprises one non-volatile oil, e) water and optionally f) one or more surfactants.

The term “ surfactant ” refers to a compound that changes the surface tension between two surfaces. Surfactant(s) d) are amphipathic molecules having two parts of different polarity, one part being nonpolar, lipophilic (retains fatty substances) and the other part being polar, hydrophilic (miscible or soluble in water). Im). The lipophilic portion is usually a fatty chain, and the other water-miscible portion is polar and/or protic.

The term “ ionic ” means anionic, cationic, amphoteric or zwitterionic.

The term “fatty chain” means a linear or branched, saturated or unsaturated hydrocarbon-based chain comprising more than 6 carbon atoms, preferably 6 to 30 carbon atoms, and preferably 8 to 24 carbon atoms. .

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

Among the nonionic surfactants according to the invention, mention may be made, alone or in mixtures, of fatty alcohols, α-diols and alkylphenols, these three types of compounds being polyethoxylated or polypropoxylated and/or poly comprising a fatty chain that is glycerolated and comprises, for example, 8 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly especially ranging from 2 to 50, and the number of glycerol groups possibly In particular, it ranges from 2 to 30. ethylene oxide and propylene oxide copolymers, condensates of ethylene oxide and propylene oxide with fatty alcohols; Preferably polyethoxylated fatty amides containing 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups, and especially 1.5 to 4 glycerol groups, 2 to 30 moles of ethylene. Oxyethylenated fatty acid esters of sorbitan containing oxides, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (C ₁₀ -C ₁₄ ) Alkylamine oxides or N-acylaminopropylmorpholine oxide may also be mentioned.

The surfactant(s) may be present in a specifically total amount of 0.01% to 30%, preferably 0.5% to 15%, even more preferentially 1% to 10% by weight of the composition, relative to the total weight of the composition. Even better it accounts for 1% to 5% by weight.

Form of composition:

According to one embodiment of the invention, composition (C1) or composition (C1') comprises an aqueous phase. The composition may be used in particular as a water-in-oil or oil-in-water emulsion or as a multiple emulsion (oil-in-water or water-in-oil-in-water triple emulsion) (such emulsions are known and described for example in C. Fox, " Cosmetics and Toiletries " - November 1986 - Vol It is prepared as described in [101-pages 101-112].

According to a specific embodiment of the invention, composition (C1) or composition (C1') is a direct emulsion, ie an emulsion of oil-in-water or O/W type. The weight of oil is preferably less than 70% by weight, preferably less than 40% by weight, more specifically less than 35% by weight relative to the total weight of the composition in the inverse emulsion.

More specifically, in direct emulsions, the amount of water is at least 30% by weight, more particularly at least 40% by weight, preferably at least 35% by weight, relative to the total weight of the composition.

According to another specific embodiment of the invention, the composition of the invention is an inverse emulsion, i.e. an emulsion of water-in-oil or W/O type. The weight of the oil is preferably greater than 30% by weight, preferably greater than 40% and more preferably greater than 45% by weight relative to the total weight of the composition in the inverse emulsion. More specifically, in an inverse emulsion, the amount of water is less than 40% by weight, preferably less than 35% by weight, relative to the total weight of the composition.

The composition (C1) or composition (C1') according to the invention preferably has a pH in the range from 3 to 9, depending on the support selected.

According to specific embodiments of the invention, the pH of the composition(s) is neutral or even slightly acidic. Preferably, the pH of the composition is 6 to 7. The pH of these compositions can be adjusted to the desired value by acidifying or basicizing agents commonly used in cosmetics, or alternatively using standard buffering systems.

The term “ basifying agent ” or “ base ” means any agent for increasing the pH of the composition in which it is present. The alkalinizing agent is a Brønsted, Lowry or Lewis base. This may be an inorganic or organic alkalinizing agent. Specifically, the agent is selected from: a) aqueous ammonia, b) (bi)carbonates, c) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and their derivatives, d) oxyethylene. ethylenediamines, e) organic amines, f) inorganic or organic hydroxides, g) alkali metal silicates, such as sodium metasilicate, h) amino acids, preferably basic amino acids, such as arginine, lysine, Ornithine, citrulline and histidine, and i) compounds of formula (F) below:

[Formula 23]

In formula (F) ,

- W is a divalent C ₁ -C ₆ alkylene radical optionally substituted by one or more hydroxyl groups or C ₁ -C ₆ alkyl radicals and/or optionally interrupted by one or more heteroatoms, such as O or NR _u ;

- R _x , R _y , R _z , R _t and R _u may be the same or different and represent a hydrogen atom or a C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl or C ₁ -C ₆ aminoalkyl radical. represents.

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

The term “ alkanolamine ” refers to an organic amine comprising primary, secondary or tertiary amine functionality and at least one linear or branched C ₁ -C ₈ alkyl group bearing at least one hydroxyl radical.

Among the inorganic or organic hydroxides, a) hydroxides of alkali metals, b) hydroxides of alkaline earth metals, for example sodium hydroxide or potassium hydroxide, c) hydroxides of transition metals, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides. and guanidinium hydroxide. Inorganic or organic hydroxides a) and b) are preferred.

Among the acidifying agents for the compositions used in the invention, examples that may be mentioned are inorganic 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. Includes.

The alkalizing and acidifying agents as previously defined preferably represent from 0.001% to 20% by weight, more particularly from 0.005% to 8% by weight of the composition, relative to the weight of the composition containing them.

According to a particular embodiment of the invention, composition (C1) or composition (C1') comprises water in an amount of up to 10% by weight relative to the total weight of the composition. Even more preferentially, the composition (C1) or composition (C1') comprises water in an amount of less than 5%, even more preferably less than 2%, even more preferably less than 0.5%, and in particular is free of water. Where appropriate, such small amounts of water may be introduced particularly by components of the composition which may contain residual amounts of water.

According to specific embodiments of the invention, the composition does not contain any water.

Advantageously, the composition (C1) according to the invention comprises a physiologically acceptable medium. Specifically, the composition is a cosmetic composition.

The term “physiologically acceptable medium” means a medium that is compatible with human keratin material, such as skin, lips, nails, eyelashes, eyebrows or hair.

The term "cosmetic composition" refers to a composition that is compatible with keratinous substances, has a pleasant color, odor and feel, and does not cause unacceptable discomfort (tingling or pulling) that is likely to deter consumers from using the cosmetic composition. it means.

The term "keratinous material" means skin (body, face, around the eyes, scalp), hair, eyelashes, eyebrows, body hair, nails or lips.

The composition (C1) or composition (C1') according to the invention contains fragrances, preservatives, fillers, colorants, UV-screening agents, oils other than oil b) and oil c), moisturizers, vitamins, ceramides, antioxidants, free radicals. It may contain one or more cosmetic additives selected from removers, polymers other than a), thickeners or film-forming agents other than a), trace elements, emollients, sequestering agents, hair loss inhibitors, anti-dandruff agents or propellants. Specifically, the composition (C1) or composition (C1') according to the invention also comprises at least one colorant, preferably a pigment, selected from pigments, direct dyes and mixtures thereof; More preferentially, the pigment(s) of the invention include carbon black, iron oxide, especially black iron oxide, and mica coated with iron oxide, triarylmethane pigments, especially 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 Lithol Red, such as the calcium salt of Lithol Red B, and even more preferentially red iron oxides.

Advantageously, the composition (C1) or composition (C1') according to the invention is a makeup composition, in particular a lip makeup composition, mascara, eyeliner, eye shadow or foundation.

adjuvant

The composition (C1) or composition (C1') according to the invention may also contain one or more fillers, especially in the range of 0.01% to 30% by weight, preferably in the range of 0.01% to 20% by weight, relative to the total weight of the composition. It can be included in the content of. The term “filler” should be understood to mean colorless or white, mineral or synthetic particles of any shape that are insoluble in the medium of the composition, regardless of the temperature at which the composition is prepared. These fillers serve in particular to modify the rheology or texture of the composition.

The composition (C1) or composition (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.

The invention is illustrated in more detail in the examples below. Amounts are expressed as weight percentages.

Example

PHAs exemplified in the various examples were prepared in 3-liter chemostats and/or 5-liter Fernbach flasks depending on whether a β-oxidation pathway inhibitor was used. Isolation of PHA is similar in all examples obtained.

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

In certain instances, a mixture of saturated and unsaturated carbon sources is required for stability of the resulting PHA.

[Table 2]

[Table 3]

Example 1: Side chain R representing a linear 10% unsaturated n-octenyl group ^One and R representing n-pentyl group ² PHA with

[Formula 24]

The synthesis method of the compound of Example 1 is adapted from the following paper: Fed-batch production of unsaturated medium-chain-length polyhydroxyalkanoates with controlled composition by Pseudomonas putida KT2440, Z. Sun, J.A. Ramsay, M. Guay, B.A. Ramsay, Applied Microbiology Biotechnology, 82, 657-662, 2009].

The microorganism used was Pseudomonas putida KT2440 ATCC® 47054™. The culture method is carried out under aseptic conditions of fed-batch growth using a maintenance solution containing a mixture of carbon sources at the rate μ = 0.15 h ^-1 in a 3 L chemostat containing 2.5 L of culture medium.

The system is aerated with an air flow of 0.5 vvm for the nominal dissolved oxygen (O _D ) value at 30% saturation. The pH is adjusted with a 15% aqueous ammonia solution. The temperature of the fermentation medium is adjusted to 30°C.

Equipment for fed-batch growth fermentation mode:

- The fermentation medium is controlled in terms of temperature-pressure of dissolved oxygen and pH (not shown): see attached Figure 1.

- The production process is carried out using three different culture media. The first culture medium, defined as the CM1 “inoculum”, is used for preparation of the preculture. A second culture medium, defined as the CM2 “batch”, is used for non-batch growth of microorganisms with a primary carbon source in Fernbach flasks. CM3 A third culture medium, defined as “maintenance”, is used in fed-batch or maintenance fermentation mode with the carbon source of interest at a flow rate corrected as a function of microbial growth.

[Table 4]

The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone by mass percentage. Reference name 233000 DIFCO™.

[Table 5]

A 100 ml preculture was prepared by suspending 1 ml of the strain in a cryotube with 100 ml of “ inoculum ” culture medium adjusted to pH 6.8 using 2N NaOH in a 250 ml Fernbach flask, followed by incubation at 30°C. Incubate for 24 hours at 150 rpm. Add 1.9 L of CM2 "batch" culture medium to a pre-sterilized 3L chemostat and inoculate with 100 mL of preculture at _OD = 0.1. After 4 hours at 850 rpm at 30°C.

After introduction, the biomass is isolated by centrifugation and then washed three times with water. The biomass is dried by lyophilization before extraction with ethyl acetate for 24 hours. The suspension is purified by filtration on a GF/A filter (Wattman®) and the filtrate consisting of PHA dissolved in ethyl acetate is concentrated by evaporation and then dried under high vacuum at 40° C. to constant mass.

PHA can be selectively purified, for example by sequential dissolution and precipitation from an ethyl acetate/ethanol 70% methanol system.

PHA has been fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure.

Preparation of Example 1': PHA copolymer with 5% unsaturated side chains R ¹ representing n-octenyl groups and R ² representing n-hexyl groups

[Formula 25]

The copolymer of Example 1' (5% unsaturated and the R ² chain represents n-hexyl) was prepared according to the procedure described for Example 1 with the same trace element solution composition as described in Example 1 and the following culture medium composition: ) was prepared:

[Table 6]

The PHA copolymer of Example 1' was fully characterized by spectroscopic and spectrometric methods and matched the expected chemical structure and had an unsaturation of 5%.

Example 1'' : PHA copolymer with linear 10% unsaturated side chains R ¹ representing n-octenyl groups and R ² representing n-hexyl groups

The copolymer of Example 1'' (10% unsaturation and R ² representing n-hexyl) was prepared according to the procedure described for Example 1 with the same trace element solution composition as described in Example 1 and the following culture medium composition: chain) was prepared:

[Table 7]

PHA has been fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure.

Example 1''' : PHA copolymer with side chains R ¹ representing a linear 30% unsaturated n-octenyl group and R ² representing an n-pentyl group

The copolymer of Example 1''' (30% unsaturated and the R ² chain is n-pentyl) was prepared following the procedure described for Example 1 with the same trace element solution composition as described in Example 1 and the following culture medium composition. represents) was prepared:

[Table 8]

The PHA copolymer has been fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure.

Example 2: Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 100% grafted with thiolactic acid (compound of Example 1 grafted with thiolactic acid TLA):

[Formula 25]

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) with stirring for at least 10 minutes.

Then, 20 mL of reaction medium was precipitated from a 200 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 2 was fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure.

Example 3 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 100% grafted with octanethiol (compound of Example 1 grafted with n-octanethiol) :

[Formula 26]

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 while stirring. 15 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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 100 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 3 was fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure.

Example 4 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturated grafted 75% with 8-mercapto-1-octanol (8-mercapto-1-octanol) Compound of Example 1 grafted)

[Formula 27]

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 the mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 4 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting with 75% or 7.5% of total functional groups.

Example 5 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 32% grafted with cysteamine (compound of Example 1 grafted with cysteamine)

[Formula 28]

While stirring, 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. 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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 100 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 5 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting with 32% or 3.2% of total functional groups.

Example 6 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 73% grafted with cyclohexanethiol (CHT) (compound of Example 1 grafted with CHT)

a) [Formula 29]

100 mg of the compound of Example 1 and 26 mg of cyclohexanethiol were dissolved in 5 mL of dichloromethane at room temperature while stirring. 5 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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 6 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting with 73% or 7.3% of total functional groups.

Example 7 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 70% grafted with 2-furanmethanethiol (FT) (compound of Example 1 grafted with FT)

[Formula 30]

100 mg of the compound of Example 1 and 26 mg of 2-furanmethanethiol were dissolved in 5 mL of dichloromethane at room temperature while stirring. 5 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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 7 was fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure. Grafting with 70% or 7% of total functional groups.

Example 8 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 70% grafted with 1-thio-β-D-glucose tetraacetate (Example 1 grafted with TGT) of compounds)

b) [Formula 31]

Here, R ^e represents *-C(O)-CH ₃ group.

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 under a 100 W UV lamp at 365 nm (reference) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 8 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting with 70% or 7% of total functional groups.

Example 9 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 50% grafted with 2-phenylethanethiol (PT) (compound of Example 1 grafted with PT)

[Formula 32]

100 mg of the compound of Example 1 and 26 mg of 2-phenylethanethiol were dissolved in 5 mL of dichloromethane at room temperature while stirring. 5 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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 9 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting with 50% or 5% of total functional groups.

Example 10 : Poly(3-hydroxyoctanoate-co-undecenoate) containing 10% unsaturation, 64% grafted with 4-tert-butylbenzyl mercaptan (TBM) (Example 1 grafted with TBM) of compounds)

[Formula 33]

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 under a 100 W UV lamp at 365 nm (reference) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 10 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting with 64% or 6.4% of total functional groups.

Example 11: Poly(3-hydroxynonanoate-co-undecenoate) containing 10% unsaturation, 100% grafted with thiolactic acid

[Formula 34]

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) was added to the mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 50 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 11 was fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure. Grafting at 100%.

Example 12: Poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturation, 100% grafted with octanethiol

[Formula 35]

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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The grafted PHA of Example 12 was fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure. Grafting at 100%.

Example 13: Poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturated, 100% epoxidized

[Formula 37]

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 in 20 mL of anhydrous dichloromethane and added to the mixture with stirring at room temperature for at least 120 hours.

The reaction medium was precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The PHA of Example 13 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Epoxidized to 100%.

Example 14: Poly(3-hydroxynonanoate-co-undecenoate) containing 10% unsaturated, 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 in 10 mL of anhydrous dichloromethane and added to the mixture with stirring at room temperature for at least 120 hours.

The reaction medium was precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The PHA of Example 14 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Epoxidized to 100%.

Example 15: Poly(3-hydroxyoctanoate-co-undecenoate) containing 30% unsaturated, 100% epoxidized:

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 in 10 mL of anhydrous dichloromethane and added to the mixture with stirring at room temperature for at least 120 hours.

The reaction medium was precipitated from a 250 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The PHA of Example 15 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Epoxidized to 100%.

Example 16: Poly(3-hydroxynonanoate-co-undecenoate) containing 5% unsaturation, 100% grafted with 4-tert-butylbenzyl mercaptan (TBM) (Example 1' grafted with TBM) of compounds)

[Formula 38]

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) with stirring for at least 10 minutes.

The reaction medium was precipitated from a 500 mL mixture of 70/30 v/v ethanol/water. A viscous white precipitate was obtained. You can repeat this step. The product so obtained was dissolved in a minimum amount of ethyl acetate, poured into a Teflon plate and dried under dynamic vacuum at 40° C. to obtain a homogeneous film.

The PHA of Example 16 was fully characterized by spectroscopic and spectrometric methods and is consistent with the expected chemical structure. Grafting at 100%.

Example 17: Side chain R representing isohexenyl group ^One and R representing an isobutyl group ² Copolymer of PHA with

[Formula 39]

The production process of Example 17 was described in Applied and Environmental Microbiology , Vol. 60, no. 9, 3245-3254 (1994) "Polyester Biosynthesis Characteristics of Pseudomonas citronellolis Grown on Various Carbon Sources, Including 3-Methyl-Branched Substrate". It is an adaptation of [Mun Hwan Choi and Sung Chul Yoon]. The microorganism used is Pseudomonas citronellolis ATCC® 13674™. The culture method was performed under non-batch aseptic culture conditions in a 5 L Fernbach flask (Corning® ref. 431685) containing 2 L of culture medium, shaken at 110 rpm at 30°C in an orbital incubator (orbital diameter of 2.5 cm). did.

The production process is carried out using two different culture media. The first culture medium, defined as the CM1 “inoculum”, is used for preparation of the preculture. A second culture medium, defined as the CM2 “batch”, was used to grow unfed batch cultures of microorganisms with the carbon source of interest in Fernbach flasks.

[Table 6]

The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone by mass percentage. Reference name 233000 DIFCO™ BD.

The composition of the yeast extract is, in mass percentage, a 100% autolysate of the yeast Saccharomyces cerevisiae . Reference name 210933 DIFCO™ BD.

[Table 7]

A 100 ml preculture was prepared by suspending 1 ml of the strain in a cryotube with 100 ml of “ inoculum ” culture medium adjusted to pH 6.8 using 2N NaOH in a 250 ml Fernbach flask, followed by incubation at 30°C. Incubate for 24 hours at 150 rpm. Place 1.9 L of CM2 “batch” culture medium into a pre-sterilized 5 L Fernbach flask and inoculate with 100 mL of inoculum at O _D = 0.1.

After 70 hours at 30°C and 110 rpm, the biomass is dried by lyophilization before extraction with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate consisting of PHA dissolved in dichloromethane is concentrated by evaporation and then dried to constant mass under high vacuum at 40°C.

PHA can be selectively purified by sequential dissolution and precipitation using, for example, a dichloromethane/methanol system.

The PHA polymer of Example 17 was fully characterized by spectroscopic and spectrometric methods and is consistent with the following expected chemical structure: 68 mol% of unit (A) (where R ¹ = isohexenyl) and 32 mol% of Unit (B) (where R ² = isobutyl).

Example 18 : Side chain R representing isohexyl group ^One and R representing an isobutyl group ² Copolymer of PHA with

c) [Formula 40]

Example 18 is obtained by hydrogenation of the PHA copolymer of Example 17 using an H-Cube Midi® continuous hydrogenator from ThalesNano Technologies.

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

PHA can be selectively purified by sequential dissolution and precipitation using, for example, a dichloromethane/methanol system.

The PHA polymer of Example 4 was fully characterized by spectroscopic and spectrometric methods and is consistent with the following expected chemical structure: 68 mol% of units (A) (where R ¹ = isohexyl) and 32 mol% of units. (B) (where R ² = isobutyl).

Example 19:

The polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™ and octanoic acid.

The culture method was performed under batch aseptic conditions in a 5 L Fernbach flask (Corning® ref. 431685) containing 2 L of culture medium shaken at 110 rpm at 30°C in an orbital incubator (orbital diameter of 2.5 cm). The synthetic process was performed using two different culture media. The first culture medium, defined as CM1 “inoculum”, was used to prepare the inoculum. A second culture medium, defined as CM2 “batch”, was used for unfed batch growth of microorganisms with octanoic acid in Fernbach flasks.

The compositions (in grams/liter) of both media are described in Table 8 below:

[Table 8]

(1) The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone as a mass percentage. Reference name 233000 DIFCO™.

(2) The composition of the trace element solution (in grams/liter) is described in Table 9 below:

[Table 9]

A 100 ml inoculum was prepared by suspending 1 ml of the strain in a cryotube with 100 ml of " inoculum " culture medium adjusted to pH 6.8 using 2N NaOH in a 250 mL Fernbach flask, followed by incubation at 30°C. Incubation was performed at 150 rpm for 24 hours. 1.9 L of CM2 "batch" culture medium was placed in a pre-sterilized 5 L Fernbach flask and inoculated with 100 mL of inoculum at O _D = 0.1. After 70 h at 30°C at 110 rpm, the biomass was dried by lyophilization before extraction with dichloromethane for 24 h. The suspension was clarified by filtration on a GF/A filter (Wattman®) and the filtrate containing the copolymer in solution in dichloromethane was concentrated by evaporation and then dried under high vacuum at 40°C to constant mass. The crude polyhydroxyalkanoate was purified by precipitation of the latter solution in 10 times the weight of a dichloromethane solution from 10 times the volume of a cold methanol solution. The obtained solid was dried under high vacuum at 40°C to constant mass.

The molecular weight of the obtained polyhydroxyalkanoate was characterized by size exclusion chromatography using refractive index detection.

■ Eluent: THF

■ Analytical flow rate: 1 mL/min

■ Injection: 100 μL

■ Column: 1 Agilent PLGel Mixed-D 5 μm column; 300 x 7.5 mm; 1 Agilent PLGel Mixed-C 5 μm column; 300 x 7.5 mm; 1 Agilent Oligopore column; 300 x 7.5 mm

■ Room temperature (25℃)

■ Detection: Waters 2487 Dual l absorbance detector, Waters 2414 refractive index detector

■ Integrator: Refractive index at 45°C and 64 mV

Empower (GC relative molar mass/typical module)

■ Empower injection time: 40 min

■ Standard: High mass/EasiVial PS-H 4 mL polystyrene from Agilent Technologies, Part No. PL2010-0200

By analysis, the weight average molecular weight (Mw, in g/mol), the number average molecular weight (Mn, in g/mol), the polydispersity index PI (Mw/Mn) and the polymer degree DPn can be determined.

The monomer composition of the obtained polyhydroxyalkanoate was defined by gas chromatography equipped with a flame ionization detector.

Identification was performed by injection of commercial standards, and monomer composition was determined by methanolysis and silylation treatment.

To determine the monomer composition, 7 mg of polyhydroxyalkanoate polymer was dissolved in 1.5 mL of chloroform and methanol in the presence of 1.5 mL of MeOH/HCl solution (17/2, v/v) for 4 h at 100 °C. It was decomposed. The organic phase was then washed with 1 mL of water and then dried over MgSO ₄ . Silylation of the methyl ester formed 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 hour and then evaporated to dryness. The sample is then dissolved in 600 μL of dichloromethane and analyzed by chromatography under the following conditions:

■ Hewlett Packard 6890 series devices

■ ZB-5 HT stationary bed column from Phenomenex (length: 30 m, diameter: 0.25 mm)

■ Temperature: Isothermal 60℃ to 300℃ in 6 min (heating rate: 10℃/min)

■ Gas: Helium; Flow rate: 0.8 mL/min

■ Injector: Temperature: 250℃; 50ml/min

■ Flame ionization detector; Temperature: 300℃

■ Injection: Volume 1 μL

Thus, an aerial containing 91% by weight of poly(3-hydroxyoctanoate), 6% by weight of poly(3-hydroxyhexanoate) and 3% by weight of poly(3-hydroxybutanoate) A composite was obtained.

■ Mn = 68 100 g/mol

■ Mw = 149 100 g/mol

■ IP = 2.2

■ DPn = 531

Example 20:

The polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™, octanoic acid and acrylic acid.

The culture method was performed under continuous aseptic conditions with a dilution of D = 0.25 h ^-1 in a 3 L chemostat containing 1.1 L of culture medium. The system was aerated with a flow of 3 vvm (vvm = air volume per volume of fermentation medium per minute) for a nominal dissolved oxygen (O _D ) value of 30% saturation.

The production process was performed using three different culture media. The first undefined culture medium (CM1) was used to prepare the inoculum. A second defined culture medium (CM2) was used for unfed batch growth of microorganisms in the fermentor. A third defined culture medium (CM3) was used to feed or maintain the continuous fermentation containing octanoic acid and acrylic acid (inhibitors of the β-oxidation pathway). CM1 and CM2 media are identical to those described in Example 1. The composition of medium CM3 (in grams/liter) is described in Table 10 below:

[Table 10]

A 100 ml inoculum was prepared by suspending 1 ml of the strain in a cryotube with 100 ml of nutrient broth adjusted to pH 7.0 using 2N NaOH in a 250 ml Fernbach flask, followed by 150 rpm at 30°C. Incubation was performed for 24 hours.

A fermentor containing 1 liter of culture medium CM2 at 30°C was inoculated with an optical density of 0.1 at 630 nm (O _{D 630} = 0.1). The system was maintained at 30° C. with shaking at 700 ± 200 rpm and cascade-conditioned by oxygenation for about 16 hours and/or a time during which the microorganisms could reach their growth plateau.

When the microorganism reached its growth plateau, the fermenter was started to be fed medium CM3 and recovery was performed to maintain the initial weight of the fermentation medium. Once equilibrium was reached in the continuous culture, a portion of the recovered material was centrifuged to separate the biomass from the fermentation medium. The biomass was dried by lyophilization and then extracted with dichloromethane for 24 hours. The obtained suspension was clarified by filtration through a GF/A filter (Whatman®). The obtained filtrate, containing the copolymer dissolved in dichloromethane, was concentrated by evaporation and then dried under high vacuum at 40° C. to constant mass. The crude polyhydroxyalkanoate was purified by precipitation of the latter solution in 10 times the weight of a dichloromethane solution from 10 times the volume of a cold methanol solution. The obtained solid was dried at 40° C. under high vacuum to constant weight.

Thus, an aerosol comprising 96% by weight of poly(3-hydroxyoctanoate), 3% by weight of poly(3-hydroxyhexanoate) and 1% by weight of poly(3-hydroxybutanoate). A composite was obtained.

■ Mn = 67 900 g/mol:

■ Mw = 142 000 g/mol:

■ IP = 2.1:

■ DPn = 611

Example 21: Copolymer of PHAs with side chains R ¹ representing n-hexyl groups and R ² representing n-butyl groups

[Formula 42]

The polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054™, nonanoic acid and acrylic acid. The culture method is carried out under continuous aseptic conditions with a dilution of D = 0.25 h ^-1 in a 3 L chemostat containing 1.1 L of culture medium. The system is aerated with an air flow of 1 vvm for the nominal dissolved oxygen (O _D ) value at 30% saturation.

The production process is carried out using three different culture media. The first culture medium (CM1) is used for preparation of the inoculum. The second culture medium (CM2) is used for batch growth of microorganisms in the fermentor. A third culture medium (CM3) is used to feed or maintain the continuous fermentation containing the carbon source of interest and a β-oxidation pathway inhibitor (acrylic acid). The composition (in grams/liter) of the three media CM1, CM2 and CM3 is described in Table 11 below:

[Table 11]

The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone by weight percentage. Reference name 233000 DIFCO™.

The composition of the trace element solutions (in grams/liter) is described in Table 12 below.

[Table 12]

A 100 ml inoculum was prepared by suspending 1 ml of the strain in a cryotube at O _D = 10 with 100 ml of CM1 “inoculum” pre-adjusted to pH 7.0 using 2N NaOH in a 500 ml Fernbach flask. , followed by incubation at 30°C and 150 rpm for 24 hours.

A 3 L fermentor containing 1 liter of CM2 "batch" culture medium at 30°C was inoculated with an optical density of 0.1 at 600 nm (O _{D 600} = 0.1). The system is maintained at 30° C. with shaking at 700 ± 200 rpm and cascade-conditioned by oxygenation for about 16 hours and/or during such time that the microorganisms can reach their growth plateau.

When the microorganisms have reached their growth plateau, the fermentor begins to be fed with CM3 “continuous” medium and recovery is performed to maintain the initial weight of the fermentation medium. Once equilibrium is reached in continuous culture, a portion of the recovered material is centrifuged to separate the biomass from the fermentation medium. The biomass is dried by lyophilization and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate consisting of PHA dissolved in dichloromethane is concentrated by evaporation and then dried to constant mass under high vacuum at 40°C.

The molecular weight of the obtained polyhydroxyalkanoate was characterized by size exclusion chromatography using refractive index detection.

■ Eluent: THF

■ Analytical flow rate: 1 mL/min

■ Injection: 100 μL

■ Column: 1 Agilent PLGel Mixed-D 5 μm column; 300 x 7.5 mm; 1 Agilent PLGel Mixed-C 5 μm column; 300 x 7.5 mm; 1 Agilent Oligopore column; 300 x 7.5 mm

■ Room temperature (25℃)

■ Detection: Waters 2487 Dual l absorbance detector, Waters 2414 refractive index detector

■ Integrator: Refractive index at 45°C and 64 mV

Empower (GC relative molar mass/typical module)

■ Empower injection time: 40 min

■ Standard: High mass/EasiVial PS-H 4 mL polystyrene from Agilent Technologies, Part No. PL2010-0200

By analysis, the weight average molecular weight (Mw, in g/mol), the number average molecular weight (Mn, in g/mol), the polydispersity index PI (Mw/Mn) and the polymer degree DPn can be determined.

The monomer composition of the obtained polyhydroxyalkanoate was defined by gas chromatography equipped with a flame ionization detector. Identification was performed by injection of commercial standards, and monomer composition was determined by methanolysis and silylation treatment.

To determine the monomer composition, 7 mg of polyhydroxyalkanoate polymer was dissolved in 1.5 mL of chloroform and methanol in the presence of 1.5 mL of MeOH/HCl solution (17/2, v/v) for 4 h at 100 °C. It was decomposed. The organic phase was then washed with 1 mL of water and then dried over MgSO ₄ . Silylation of the methyl ester formed 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 hour and then evaporated to dryness. The sample is then dissolved in 600 μL of dichloromethane and analyzed by chromatography under the following conditions:

■ Hewlett Packard 6890 series devices

■ ZB-5 HT stationary bed column from Phenomenex (length: 30 m, diameter: 0.25 mm)

■ Temperature: Isothermal 60℃ to 300℃ in 6 min (heating rate: 10℃/min)

■ Gas: Helium; Flow rate: 0.8 mL/min

■ Injector: Temperature: 250℃; 50ml/min

■ Flame ionization detector; Temperature: 300℃

■ Injection: Volume 1 μL

Thus, an aerial comprising 86% by weight poly(3-hydroxynonanoate), 9% by weight poly(3-hydroxyheptanoate) and 5% by weight poly(3-hydroxypentanoate). A composite was obtained.

■ Mn = 65 900 g/mol

■ Mw = 143 600 g/mol

■ IP = 2.2

■ DPn = 531

Example 22:

The polymer was prepared according to the procedure of Example 19 without acrylic acid and using nonanoic acid (instead of octanoic acid).

Thus, an aerial comprising 68% by weight poly(3-hydroxynonanoate), 27% by weight poly(3-hydroxyheptanoate) and 5% by weight poly(3-hydroxypentanoate). A composite was obtained.

■ Mn = 55 800 g/mol

■ Mw = 124 500 g/mol

■ IP = 2.2

■ DPn = 469

Example 23:

The polymer was prepared following the procedure in Example 19 using dodecanoic acid (instead of octanoic acid).

Thus, an aerial comprising 44% by weight poly(3-hydroxydodecanoate), 38% by weight poly(3-hydroxydecanoate) and 18% by weight poly(3-hydroxyoctanoate). A composite was obtained.

■ Mn = 67 400 g/mol

■ Mw = 129 800 g/mol

■ IP = 1.9

■ DPn = 484

Example 24: Copolymer of PHAs with side chains R ¹ representing n-pentyl groups and R ² representing n-propyl groups

[Formula 41]

The production 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"].

The microorganism used is Pseudomonas putida ATCC® 47054™.

The culture method is carried out under continuous aseptic conditions with a dilution of D = 0.25 h ^-1 in a 3 L chemostat containing 1.1 L of culture medium.

The system is aerated with an air flow of 3 vvm for the nominal dissolved oxygen (O _D ) value at 30% saturation.

Assembly:

(see Figure 2)

The production process is carried out using three different culture media.

The first undefined culture medium (CM1) is used for preparation of the inoculum.

A second defined culture medium (CM2) is used for batch growth of microorganisms in the fermentor.

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

The compositions (in grams/liter) of the three media are described in Table 13. Composition of culture media for inoculation and maintenance (grams/liter).

[Table 13]

The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone by weight percentage. Reference name 233000 DIFCO™.

The composition of the trace element solution (in grams/liter) is described in Table 14: Composition of the trace element solution (in grams/liter)

[Table 14]

A 100 ml inoculum was prepared by suspending 1 ml of the strain in a cryotube with 100 ml of nutrient broth adjusted to pH 7.0 using 2N NaOH in a 250 ml Fernbach flask, followed by 150 rpm at 30°C. Incubate for 24 hours.

A fermentor containing 1 liter of culture medium CM2 at 30°C was inoculated with an optical density of 0.1 at 630 nm (O _{D 630} = 0.1). The system is maintained at 30° C. with shaking at 700 ± 200 rpm and cascade-conditioned by oxygenation for about 16 hours and/or during such time that the microorganisms can reach their growth plateau.

When the microorganisms reach their growth plateau, the fermenter begins to be fed with medium CM3 and recovery is performed to maintain the initial weight of the fermentation medium. Once equilibrium is reached in continuous culture, a portion of the recovered material is centrifuged to separate the biomass from the fermentation medium. The biomass is dried by lyophilization and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate consisting of PHA dissolved in dichloromethane is concentrated by evaporation and then dried to constant mass under high vacuum at 40°C.

PHA can be selectively purified by sequential dissolution and precipitation using, for example, a dichloromethane/methanol system.

The PHA copolymer of Example 24 was fully characterized by spectroscopic and spectrometric methods. Gas chromatography equipped with an FID detector showed that the copolymer contained 96% of the radicals R ¹ = n-pentyl and 4% of the radicals R ² = n-propyl.

Example 25: Side chain R representing a linear 5% unsaturated 8-bromo-n-octanoyl group ^One and R representing n-hexyl group ² PHA with

[Formula 44]

The synthesis method of the compound of Example 1 is adapted from the following 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].

The microorganism used was Pseudomonas putida KT2440 ATCC® 47054™. The culture method is carried out under aseptic conditions of fed-batch growth using a maintenance solution containing a mixture of carbon sources at the ratio μ = 0.15 h ^-1 in a 3 L chemostat containing 2.5 L of culture medium.

The system is aerated with an air flow of 0.5 vvm for the nominal dissolved oxygen (O _D ) value at 30% saturation. The pH is adjusted with a solution consisting of ammonia and glucose at a final mass of 15% and 40%, respectively. The temperature of the fermentation medium is adjusted to 30°C.

Equipment for fed-batch growth fermentation mode

The fermentation medium is controlled in terms of temperature-pressure of dissolved oxygen and pH (not shown).

The production process is carried out using three different culture media. The first culture medium, defined as the CM1 “inoculum”, is used for preparation of the preculture. A second culture medium, defined as the CM2 “batch”, is used for non-batch growth of microorganisms with a primary carbon source in Fernbach flasks. CM3 A third culture medium, defined as “maintenance”, is used in fed-batch or maintenance fermentation mode with the carbon source of interest at a flow rate corrected as a function of microbial growth.

[Table 15]:

The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone by weight percentage. Reference name 233000 DIFCO™.

[Table 16]:

A 100 ml preculture was prepared by suspending 1 ml of the strain in a cryotube with 100 ml of “ inoculum ” culture medium adjusted to pH 6.8 using 2N NaOH in a 250 ml Fernbach flask, followed by incubation at 30°C. Incubate for 24 hours at 150 rpm. Add 1.9 L of CM2 "batch" culture medium to a pre-sterilized 3 L chemostat and inoculate with 100 mL of preculture at _OD = 0.1. After 4 hours at 850 rpm at 30°C, introduction of the maintenance culture medium is performed by applying the flow rate defined by equation 1.

After introduction, the biomass is separated by centrifugation and then washed three times with water. The biomass is dried by lyophilization before extraction with ethyl acetate for 24 hours. The suspension is clarified by filtration on a GF/A filter (Whatman®) and the filtrate consisting of PHA dissolved in ethyl acetate is concentrated by evaporation and then dried under high vacuum at 40° C. to constant mass.

PHA can optionally be purified by dissolution in ethyl acetate and subsequent precipitation from, for example, a 70/30 v/v% ethanol/water system.

PHA has been fully characterized by spectroscopic and spectrophotometric methods and is consistent with the expected chemical structure. 95 mol% of units (B) where R ² = n-hexyl (71%) and n-butyl (24%) and 5 mol% of units (A) where R ¹ = 8-bromo -n-octanyl (5.9%) and 6-bromo-n-hexyl (0.2%).

The compounds of Examples 1 to 25 can be mixed with one or more volatile solvent(s) b) and non-volatile solvent(s) c) as previously defined, taking into account the mass ratio U as previously defined. Mixing of PHA(s) a) with solvents b) and c), preferably in the presence of fatty substance d) as defined above and, optionally, in the presence of organic solvent(s) other than e), with stirring. Can be performed at room temperature. According to one variant, water f) is added to the mixture of a), b), c) and d) and optionally one or more organic solvents other than e) as defined above.

Example 26 and Example 27:

Compositions 27 (comparative) and 28 (inventive) described in Table 17 below were prepared:

[Table 17]:

Composition (grams/100 g)

PHA, isododecane and ethanol are stirred at 2500 rpm at a temperature of 25°C. The volatile oil b) and the non-volatile oil c) are introduced and the medium is heated from 25° C. to 80° C. while stirring at 2500 rpm. The medium was kept at 80°C for 30 minutes with stirring at 3000 rpm and then cooled from 80°C to 25°C with stirring at 2500 rpm.

performance evaluation

wear resistance

Test description:

The first step of this test consists in making a deposit. The deposit is made on Byko Chart Lenata contrast card using a film spreader and left to dry at 25° C. and 45% RH for 24 hours. The final thickness of the deposit is 30 μm.

Abrasion resistance tests are performed on these dry deposits. Hydrophilic steel balls are used as friction devices. The applied load or normal force is 1N and the displacement rate is 50 mm.s ^-1 . Each film has a defined track through which the friction device passes several times. For wear measurements, permanent contact is maintained while the ball moves back and forth over the deposit. The number of passes is incremented for each track. Abrasion resistance is quantified as the minimum number of passes to completely wear away the deposit.

For this study, the number of passes per track is 10 and 30 to 50 passes, respectively.

Each measurement was repeated 5 times.

The results of the abrasion resistance test are quantified as described in the table below:

[Table 18]:

result:

[Table 19]:

water resistance

Test description:

For the same 30 μm dry deposit prepared for abrasion testing, sensitivity to the stressor is assessed after depositing a drop of stressor (20 μl for water) on the surface of the deposit. The assessment is performed after 1 hour of contact between the stressor and the deposit. The levels of sensitivity to stressors are as follows:

[Table 20]:

The compositions of the present invention (Examples 27-29) appear to maintain water resistance. The presence of various oils does not affect the water resistance of the resulting film.

Example 1'''': C9 and C11: side chain R showing 2% unsaturated n-octenyl group, carried out in discontinuous culture fed with two carbon sources at 1 98/2 ^One and R representing an unsaturated n-hexyl group. ² PHA copolymer with

The procedure to obtain 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"].

The microorganism used was Pseudomonas putida KT2440 ATCC® 47054™.

The culture mode is carried out under sterile conditions in a discontinuous fed-batch manner fed with a maintenance solution containing a mixture of carbon sources at a rate of μ = 0.15 h-1 in a 3 L chemostat containing 2.5 L of culture medium. . The flow rate of the maintenance feed pump is proportional to the growth of the microorganisms according to equation 1:

Equation 1: Theoretical equation relating the amount of biomass and carbon source as a function of time St = the amount of carbon source Xt required to produce biomass at time t (g);

_{Y ​}

The system is aerated with an air flow of 0.5 vvm to the dissolved oxygen (DO) set point at 30% saturation. The pH is adjusted with 15% ammonia solution. The temperature of the fermentation medium is adjusted to 30°C. Assembly of the fed-batch growth fermentation mode takes place according to Figure 1.

The fermentation medium is controlled in terms of temperature-dissolved oxygen pressure and pH (not shown in the figure).

The production process is carried out using three distinct culture media. The first culture medium, defined as the MC1 “inoculum”, is used for preparation of the preculture.

A second culture medium, defined as MC2 “batch”, is used for unfed discontinuous growth of microorganisms with a primary carbon source in Fernbachs flasks.

A defined third culture medium (MC3 “maintenance”) is used for discontinuous feeding or maintenance of fermentation using the carbon source of interest at a flow rate corrected according to microbial growth.

The compositions (in grams/liter) of the three media are described in Table 21:

[Table 21]:

Table 21: Composition of culture media for pre-culture and maintenance (grams/liter).

The composition of the nutritional broth is 37.5% beef extract and 62.5% peptone by mass percentage. Reference name 233000 DIFCO™.

The composition of the trace element solutions (in grams/liter) is described in Table 22:

[Table 22]:

Table 22: Composition of trace element solutions (grams/liter)

In a 250 ml Fernbach flask, 1 ml of the strain in a cryotube was suspended in 100 ml of " inoculum " culture medium adjusted to pH 6.8 using 2N NaOH, followed by incubation at 30°C and 150 rpm for 24 h. Prepare 100 ml preculture. Add 1.9 L of MC2 "batch" culture medium to a pre-sterilized 3 L chemostat and inoculate at OD=0.1 with 100 mL of preculture. After 4 hours at 850 rpm at 30°C, introduction of oil is carried out by applying the flow rate defined by equation 1. After introduction, the biomass is separated by centrifugation and then washed three times with a little water. The biomass is dried by freeze-drying and then extracted with dichloromethane for 24 hours. The suspension is clarified by filtration on a GF/A filter (Wattman®) and the filtrate consisting of PHA dissolved in dichloromethane is concentrated by evaporation and then dried under high vacuum at 40°C to constant mass. PHA can be selectively purified by solubilization and subsequent precipitation, for example in the dichloromethane methanol system.

PHA was characterized by gas chromatography equipped with an FID detector. This is consistent with the expected chemical structure and has an unsaturation rate of 2%.

Example 11': In Example 1'' at 2% with thiolactic acid, the linear side chain R representing the n-octylenyl group ^One and unsaturated n-hexyl R ² Functionalization of mcl-PHA with

2 g of the compound of Example 1'' and 180 mg of thiolactic acid were dissolved in 15 mL of ethyl acetate at room temperature with stirring. 5 mg of 2-hydroxy-2-methylpropiophenone (HMP)) was added to the mixture. The medium was then irradiated under a 100 W UV lamp at 365 nm (reference) with stirring for at least 10 minutes. The reaction medium thus obtained was poured into a Teflon plate and then dried under dynamic vacuum at 40° C. to obtain a homogeneous film. PHA grafted with thiolactic acid was fully characterized by proton NMR. The proton NMR spectrum shows that the characteristic signal of the unsaturated body has completely disappeared.

The compositions of Examples 30-35 included the ingredients according to Table 18.

[Table 23]:

[Table 24]

wear resistance

Test description:

The first step of this test consists in making a deposit. A deposit is made on Byko Chart Lenata contrast card and left to dry for 24 hours at 25°C and 45% RH. The final thickness of the deposit is 30 μm.

Abrasion resistance tests are performed on these dry deposits. Hydrophilic steel balls are used as friction devices. The applied load or normal force is 1 N and the displacement rate is 50 mm.s ^-1 . Each film has a defined track through which the friction device passes several times. For wear measurements, permanent contact is maintained while the ball moves back and forth over the deposit. The number of passes is incremented for each track. Abrasion resistance is quantified as the minimum number of passes to completely wear away the deposit.

For this study, the number of passes per track is 10, 30, 50, 100, 200, and 300 passes, respectively.

Each measurement was repeated 5 times.

The results of the abrasion resistance test are quantified as described in the table below:

[Table 22]:

result

Improvement in wear resistance was observed when non-volatile oil was added compared to PHA formulated only with volatile oil.

The compositions of the present invention (Examples 30-36) were shown to remain highly water resistant despite the addition of non-volatile and volatile oils. The presence of various oils does not affect the water resistance of the resulting film.

comparative test

result

On the other hand, in the case of Comparative Example 38, the deposit is not cohesive at all. This is a completely oily liquid. These deposits are inappropriate and ineffective.

On the other hand, the two deposits for examples 37 and 39 are very cohesive, and the deposit from example 39 according to the invention has significantly better wear resistance than the deposit from example 37.

Claims (23)

a) contains at least two different repeating polymer units selected from the following units (A) and (B), and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof, One or more polyhydroxyalkanoate (PHA) copolymers, preferably consisting of:
-[-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 5 to 28 carbon atoms; Preferably, the 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 ) is selected from alkynyl; Preferably, the hydrocarbon-based group is linear;
The hydrocarbon-based chain is:
oa) halogen, such as chlorine or bromine, b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )(alkyl)amino, e) (thio)carboxy, f) (thio)carboxamide. -C(O)-N(R _a ) ₂ or C(S)-N(R _a ) ₂ , g) cyano, h) iso(thio)cyanate, i) (hetero)aryl, such as phenyl or furyl. , and j) (hetero)cycloalkyl such as anhydride, epoxide or dithiolane, k) cosmetic active agent; l) R _{and ​ ​ ​} b'), such as (thio)esters, (thio)amides, (thio)ureas or sulfonamides; R _a represents a hydrogen atom, or a (C ₁ -C ₄ )alkyl group or an aryl(C ₁ -C ₄ )alkyl group such as benzyl, preferably R _a represents a hydrogen atom; R _b and R _c may be the same or different and are selected from (C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkoxy groups, especially representing only one substituent), m) thiosulfate; preferably b) halogen, and j) optionally substituted with one or more atoms or groups such as epoxides;
- 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 ') and b'), such as (thio)ester, (thio)amide, (thio)urea, sulfonamide (where r is 1 or 2, R _a is as defined above, preferably R _a represents a hydrogen atom and R _b and R _c are as previously defined) are optionally present;

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' ) and b'), such as (thio)ester, (thio)amide, (thio)urea or sulfonamide (where r is 1 or 2, R _a is as defined above, preferably R _a represents a hydrogen atom and R _b and R _c are as previously defined) are optionally interrupted;

R ² is 3 to 30, optionally substituted with one or more atoms or groups a) to m) as defined for R ¹ and/or optionally interrupted by one or more heteroatoms or groups a') to c') Represents a cyclic or acyclic, linear or branched, saturated or unsaturated hydrocarbon group containing 2 carbon atoms; specifically linear or branched (C ₃ -C ₂₈ )alkyl and linear or branched (C ₃ -C ₂₈ )alkenyl, specifically linear hydrocarbon-based groups, more specifically (C ₄ -C ₂₀ )alkyl or (C ₄ -C ₂₀ )alkenyl; Preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R ¹ minus at least one carbon atom, preferably corresponding to the number of carbon atoms of the radical R ¹ minus two carbon atoms. ;
b) one or more volatile oils;
c) one or more non-volatile oils; and
d) optionally one or more surfactant(s); and
e) optionally water; and
f) optionally, one or more organic solvents other than b) and c)
As a composition (C1') comprising;
- (A) is different from (B)
- the mass ratio R of b) the sum of the masses of the volatile oil(s)/c) the sum of the masses of the non-volatile oil(s) is not zero and is less than 900, preferably between 3 and 800, more preferably between 4 and 200, Composition (C1'). 2. The method of claim 1, wherein the PHA copolymer(s) a) contain repeating units of formula (I) and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof. , Composition (C1'):

In formula (I) :

R ¹ and R ² are as defined in clause 1;

m and n are integers greater than or equal to 1; Preferably, the sum n + m is 450 to 1400 (inclusive);
Preferably, when R ¹ and R ² represent an unsubstituted and uninterrupted alkyl group, m > n, and more preferentially, when R ¹ and R ² are linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group. ; R ² represents a linear alkyl group having a carbon number corresponding to that of R ¹ minus two carbon atoms;
Preferably, if 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 and R ² represents an alkyl group, then m < nim. 2. The method of claim 1, wherein the PHA copolymer(s) a) contains three different repeating polymer units (A) , (B) and (C) , preferably three different repeating polymer units (A) , Composition (C1') consisting of (B) and (C) and also their optical or geometric isomers and solvates such as hydrates thereof:
-[-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 polymer units (A) , (B) and (C) :
- R ¹ and R ² are as defined in clause 1 or clause 2;
- R ³ is optionally substituted with one or more atoms or groups a) to m) as defined for R ¹ in claim 1 or 2 and/or by one or more heteroatoms or groups a') to c') represents a saturated or unsaturated, linear or branched, cyclic or acyclic, hydrocarbon-based group containing 1 to 30 carbon atoms, optionally interrupted by specifically selected from linear or branched (C ₁ -C ₂₈ )alkyl, and linear or branched (C ₂ -C ₂₈ )alkenyl, especially linear hydrocarbon-based groups, more particularly (C ₄ -C ₂₀ )alkenyl. represents a hydrocarbon-based group; Preferably, the hydrocarbon-based group corresponds to the number of carbon atoms of the radical R ¹ or else corresponds to the number of carbon atoms of the radical R ¹ minus at least 3 carbon atoms, preferably the radical R minus 4 carbon atoms. has a carbon number corresponding to the number of carbon atoms of ¹ ;
- (A) is different from (B) and (C) , (B) is different from (A) and (C) , (C) is different from (A) and (B) ;
Preferably, when R ¹ , R ² and R ³ represent unsubstituted and uninterrupted alkyl groups, the mole percentage of unit (A) is greater than the mole percentage of unit (B) and greater than the mole percentage of unit (C) , More preferentially, when R ¹ , R ² and R ³ are linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms;
Preferably, if R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, in particular R ² represents an alkyl group. If it represents and/or R ³ represents an alkyl group, the mole percentage of unit (A) is understood to be less than the mole percentage of unit (B) and less than the mole percentage of unit (C) ;
More preferentially, the PHA copolymer(s) a) contain repeating units of formula (II) , and also their optical or geometric isomers, their organic or inorganic acid or base salts, and their solvates such as hydrates:

In formula (II) above:

R ¹ , R ² and R ³ are as previously defined;

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, and more preferentially when R ¹ , R ² and R ³ are linear alkyl, R ¹ is C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms;
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, and R ² and R ³ When representing an alkyl group, m < n + p. 4. The method according to any one of claims 1 to 3, wherein the PHA copolymer(s) a) contains four different repeating polymer units (A) , (B) , (C) and (D) , preferably is composed of the following four different repeating polymer units (A) , (B) , (C) and (D) , and also their optical or geometric isomers, their organic or inorganic acid or base salts, and also their solvates, such as hydrates. Composition (C1') consisting of:
-[-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 polymer units (A) , (B) , (C) and (D) :
- R ¹ , R ² and R ³ are as defined in any one of claims 1 to 3;
- R ⁴ is optionally substituted by one or more atoms or groups a) to m) as defined for R ¹ in any one of claims 1 to 3 and/or by one or more heteroatoms or groups a') to c') represent a cyclic or acyclic, linear or branched, saturated hydrocarbon-based group containing 3 to 30 carbon atoms, optionally interrupted; linear or optionally substituted with one or more atoms or groups a) to m) and/or interrupted by one or more heteroatoms or groups a') to c'), as specifically defined for R ¹ as defined above. represents a hydrocarbon-based group selected from branched (C ₄ -C ₂₈ )alkyl;
- (A) is different from (B) , (C) and (D) , (B) is different from (A) , (C) and (D) , and (C) is different from (A) , (B) and (D) , and (D) is different from (A) , (B) , and (C) ;
- Preferably, when R ¹ , R ² , R ³ and R ⁴ represent unsubstituted and uninterrupted alkyl groups, the mole percentage of unit (A) is greater than the mole percentage of unit (B) and the mole percentage of unit (C) greater than the percentage and greater than the molar percentage of unit (D) , and more preferentially, when R ¹ , R ² , R ³ and R ⁴ are linear alkyl, then R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ₁ minus four carbon atoms, R ₄ represents a linear alkyl group having a carbon number corresponding to that of R ¹ minus 6 carbon atoms;
- Preferably, if R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, in particular R ² is alkyl If it represents a group and/or R ³ represents an alkyl group, the mole percentage of unit (A) is less than the mole percentage of unit (B) and less than the mole percentage of unit (C) ; R ⁴ is understood to represent substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group;
More preferentially, the PHA copolymer(s) comprise repeating units of formula (III) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof:

In formula (III) :

R ¹ , R ² , R ³ and R ⁴ are as previously defined;

m, n, p and v are integers greater than or equal to 1; Preferably, the sum n + m + p + v is between 450 and 1400 (inclusive);
Preferably, when R ¹ , R ² , R ³ and R ⁴ represent unsubstituted and uninterrupted alkyl groups, m > n + p + q and, more preferentially, R ¹ , R ² , R ³ and R ⁴ When is linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms, R ⁴ represents a linear alkyl group having a carbon number corresponding to that of R ¹ minus 6 carbon atoms;
Preferably, R ¹ represents substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, and R ² and R ³ represent alkyl represents a group, and if R ⁴ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, then n > m + v; More preferentially n + p > m + v. 5. The method according to any one of claims 1 to 4, wherein the PHA copolymer(s) a) contain five different repeating polymer units (A) , (B) , (C) , (D) and (E). and preferably five different repeating polymer units (A), (B), (C), (D) and (E) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and Composition (C1'), which also consists of solvates thereof, such as hydrates:
-[-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 polymer units (A) , (B) , (C) , (D) and (E) :
- R ¹ , R ² , R ³ and R ⁴ are as defined in any one of claims 1 to 4;
- R ⁵ is 3 to 3, optionally substituted with one or more atoms or groups a) to m) as defined for R ¹ and/or optionally interrupted by one or more heteroatoms or groups a') to c') represents a cyclic or acyclic, linear or branched, saturated hydrocarbon group containing 30 carbon atoms; ^It is a linear or branched (C ₄ - C ₂₈ ) represents a hydrocarbon-based group selected from alkyl; Preferably, the hydrocarbon-based group corresponds to the number of carbon atoms of the radical R ⁴ minus at least one carbon atom, preferably of the radical R ⁴ minus at least two carbon atoms, preferably minus two carbon atoms. has a carbon number corresponding to the number of carbon atoms;
- (A) is different from (B) , (C), (D) and (E) ; (B) is different from (A) , (C), (D) and (E) ; (C) is different from (A) , (B), (D) and (E) ; (D) is different from (A) , (B), (C) and (E) ; (E) is different from (A) , (B), (C) and (D) ;
- Preferably, when R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent unsubstituted and uninterrupted alkyl groups, the mole percentage of unit (A) is greater than the mole percentage of unit (B) and unit (C ) greater than the mole percentage of the unit (D) greater than the mole percentage of the unit (E) , more preferentially R ¹ , R ² , R ³ , When R ⁴ and R ⁵ are linear alkyl, R ¹ is a C ₅ -C ₁₃ alkyl group; R ² represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus two carbon atoms, R ³ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus four carbon atoms, R ⁴ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus 6 carbon atoms, R ⁵ represents a linear alkyl group having a carbon number corresponding to the carbon number of R ¹ minus 8 carbon atoms,
- Preferably, if R ¹ represents a substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or an optionally substituted and/or optionally interrupted alkynyl group, in particular R ² is alkyl If it represents a group and/or R ³ represents an alkyl group, the mole percentage of unit (A) is less than the mole percentage of unit (B) and less than the mole percentage of unit (C) ; R ⁴ and R ⁵ are understood to represent substituted and/or interrupted alkyl, optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl groups;
More preferentially, the PHA copolymer(s) comprise repeating units of formula (IV) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates such as hydrates thereof:

In formula (IV) :

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as previously defined;

m , n, p, v and z are integers greater than or equal to 1; Preferably, the sum n + m + p + v + z is between 450 and 1400 (inclusive);

Preferably, when R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent unsubstituted and uninterrupted alkyl groups, m > n + p + v + z;

Preferably, R ¹ is substituted and/or interrupted alkyl; represents an optionally substituted and/or optionally interrupted alkenyl or optionally substituted and/or optionally interrupted alkynyl group, R ² and R ³ represent an alkyl group, and the groups R ⁴ and R ⁵ are substituted and/or interrupted. alkyl; optionally substituted and/or optionally interrupted alkenyl; or when representing an optionally substituted and/or optionally interrupted alkynyl group, n > m + v + z; More preferentially n + p > m + v + z. The method according to any one of claims 1 to 5, wherein R ¹ represents a linear or branched, preferably linear, (C ₅ -C ₂₈ )alkyl hydrocarbon-based chain; More specifically, R ¹ represents an alkyl group substituted with one or more atoms or groups a) to k), said alkyl group comprising 5 to 12, preferably 6 to 10 carbon atoms, more preferably 7 to 9 carbon atoms. ), such as n-octyl; Preferably, R ¹ is b) hydroxyl, c) thiol, d) (di)(C ₁ -C ₄ )(alkyl)amino, preferably amino, e) carboxyl, i) (hetero)cycloalkyl. , such as anhydrides, or epoxides, j) cosmetic actives selected from colored or non-colored, fluorescent or non-fluorescent chromophores, such as optical brighteners, UV-screening agents, h) (hetero)aryls such as phenyl or furyl, k ) R represents a group selected from the same cosmetic _active agent and represents; R _a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl or aryl(C ₁ -C ₄ )alkyl group such as benzyl, preferably R _a represents a hydrogen atom) (preferably represents a hydrocarbon-based chain substituted with one) group;
Even more preferentially, the PHA copolymer(s) are such that R ¹ is a) halogen, such as chlorine or bromine, b) hydroxyl, d) (di)(C ₁ -C ₄ )(alkyl)amino, preferably amino. , e) carboxyl, i) (hetero)cycloalkyl, such as epoxide, h) (hetero)aryl, such as phenyl or furyl, k) RX, where R is α) cycloalkyl, such as cyclohexyl, β) hetero cycloalkyl, such as sugar, preferably monosaccharide, such as glucose, γ) (hetero)aryl, such as phenyl, X represents a') O, S or N(R _a ), preferably S ; R _a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably R _a represents a hydrogen atom), a hydrocarbon-based chain substituted with one or more (preferably one) groups selected from the group consisting of: It represents an alkyl group as defined;
Even better, the composition (C1'), wherein the hydrocarbon-based chain R ¹ is substituted at the end of the chain opposite to the carbon atom carrying the radical R ¹ . _7. The method according to any one of claims 1 to 6, wherein R ¹ is one or more (preferably one) a hydrocarbon-based chain interrupted by an atom or group, especially alkyl, especially C ₇ -C ₂₀ , more particularly C ₈ -C ₁₈ and even more particularly C ₉ -C ₁₆ alkyl, R _a represents the first As defined in any one of clauses to 6; Preferably, R _a is a hydrogen atom; preferably represents an alkyl group interrupted by one or more atoms selected from O and S, more preferentially O or S, especially S atoms; Preferably, the interrupted hydrocarbon-based chains, especially alkyl, are linear. The method according to any one of claims 1 to 7, wherein R ¹ has the formula -(CH ₂ ) _r -X-(ALK) _u -G, or N(R _a ), preferably S, and ALK represents a linear or branched, preferably linear, (C ₁ -C ₁₀ )alkylene and more specifically (C ₁ -C ₈ )alkylene chain. and r represents an integer from 6 to 11, preferably from 7 to 10 (inclusive), such as 8; u is 0 or 1; G is a hydrogen atom, or hydroxyl, carboxyl, (di)(C ₁ -C ₄ )(alkyl)amino, (hetero)aryl, especially aryl, such as phenyl, cycloalkyl such as cyclohexyl, or sugar, especially represents a group selected from monosaccharides (optionally protected with one or more groups such as acyl), preferably Sug represents a ^group R ^f -C(O)- and R ^f represents a (C ₁ -C ₄ )alkyl group such as methyl; Preferably, when u is 0, G represents a cycloalkyl group such as cyclohexyl, or a sugar as previously defined; According to another advantageous variant, when u is 1, G is a hydrogen atom or a group selected from hydroxyl, carboxyl, (di)(C ₁ -C ₄ )(alkyl)amino or (hetero)aryl, specifically Composition (C1'), representing aryl, such as phenyl. 9. The method according to any one of claims 1 to 8, wherein the PHA copolymer(s) a) are linear or branched (C ₁ -C ₂₈ )alkyl, and linear or branched (C ₂ -C ₂₈ )alkenyl. , especially a radical R ² selected from linear hydrocarbon-based groups, especially (C ₃ -C ₂₀ )alkyl or (C ₃ -C ₂₀ )alkenyl; Preferably, the hydrocarbon-based group has a carbon number corresponding to the number of carbon atoms of the radical R ¹ minus at least one carbon atom, preferably corresponding to the number of carbon atoms of the radical R ¹ minus at least two carbon atoms. Composition (C1'). 10. The method according to any one of claims 1 to 9, wherein the PHA copolymer(s) a) are linear or branched, preferably linear, (C ₁ -C ₈ )alkyl, especially (C ₂ -C ₆ )alkyl, preferably ^a (C ₄ -C ₆ )alkyl group, such as n-pentyl or n- hexyl ; or R ² is a branched (C ₃ -C ₈ )alkyl, specifically a (C ₄ -C ₆ )alkyl group, preferably a branched (C ₄ -C ₅ )alkyl, such as isobutyl. ). 11. The method according to any one of claims 1 to 10, wherein the PHA copolymer(s) comprises units (A) , (B) and (C) when R ¹ represents a (C ₃ -C ₃₀ )alkyl group. For all, unit (A) is preferably in a mole percentage ranging from 0.5% to 99%, more preferably from 50% to 99%, more particularly from 60% to 99%, even more preferably from 70% to 99%. A composition ( C1'). 12. The method according to any one of claims 1 to 11, wherein the PHA copolymer(s) a) have R ¹ selected from 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, the hydrocarbon group is preferably linear, and the hydrocarbon chain ^is substituted by one or more atoms or groups a) to m) and/or interrupted by one or more heteroatoms or groups a') to c') as defined; This specifically refers to a linear or branched (C ₄ -C) group optionally substituted with one or more atoms or groups a) to m) and/or interrupted by one or more heteroatoms or groups a') to c') as previously defined. ₂₈ ) represents a hydrocarbon group selected from alkyl,
- the unit (A) has a mole percentage ranging from 0.1% to 99%, preferably a mole percentage ranging from 0.5% to 50%, more preferably a mole percentage ranging from 1% to 40%, even more preferably 2% to 30%. %, more preferably in the range of 5% to 20%, even more preferably in the range of 10% to 30%;
- Unit (B) is present in a mole percentage ranging from 1% to 99.5%, preferably from 1% to 90%, more preferentially from 2% to 70%, most particularly from 2% to 10%;
- Unit (C) is present in a mole percentage of 0.5% to 20% relative to the sum of units (A) , (B) and (C) ; Advantageously, the PHA copolymer(s) of the invention comprise from 2 mol% to 10 mol% of units (B) and from 0.5 mol% to 7 mol% of units (C) ; More advantageously, the copolymer comprises from 5 mol% to 35 mol% of units (B) and from 0.5 mol% to 7 mol% of units (C) . 13. The PHA copolymer(s) according to any one of claims 1 to 12, wherein the PHA copolymer(s) comprises the following repeating units (A) , and also optical or geometric isomers thereof, organic or inorganic acid or base salts thereof, and solvates thereof, Composition (C1'), comprising, for example, hydrates:


In repeat units A1 to A12:
- ALK ₁ represents a divalent linear or branched C ₁ -C ₂₀ , preferably linear or branched, more preferentially linear, C ₁ -C ₁₀ , hydrocarbon-based radical;
- ALK ₂ represents a divalent linear or branched C ₁ -C ₂₀ , preferably linear or branched C ₁ -C ₁₂ , hydrocarbon-based radical;
- Rr and Rw independently represent a hydrogen atom or a C ₁ -C ₄ alkyl radical 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 heterocycloalkyl, such as 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 with one or more groups such as acyl, especially acetyl);
Specifically, the stereochemistry of the carbon atom carrying the radical R ¹ is the (R) configuration. 14. The method according to any one of claims 1 to 13, wherein the PHA copolymer(s) a) comprises the following repeating units, and also their optical or geometric isomers, their organic or inorganic acid or base salts, and their solvates such as Composition (C1'), comprising hydrate:


m and n are as previously defined, Hal represents a halogen atom, such as bromine, and t represents an integer from 1 to 10, preferably from 3 to 8, such as 6.
Ar: represents a (hetero)aryl group such as phenyl;
Ar': represents (C ₁ -C ₄ )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: refers to a sugar group, specifically a monosaccharide (optionally protected with one or more groups such as acyl); Preferably, Sug represents:
Here, R ^e represents the group R ^f -C(O)- and R ^f represents a (C ₁ -C ₄ )alkyl group such as methyl.
More preferentially, the PHA copolymer(s) have the formula:


M, n, Hal, t, Ar, Ar', Cycl, Fur and Sug are as previously defined for compounds (1) to (14).



Preferably, the PHA(s) of the present invention are compounds (1), (2a), (10), (11), (15), (16), (17) and (20), more preferably ( 15), (16) and (17), especially (16); More specifically, the PHA(s) of the present invention include compounds (1'), (2a'), (10'), (11'), (15'), (16'), (17') and (20) '), more preferably selected from (15'), (16') and (17'), especially (16'); More specifically, the PHA a) of the present invention is compound (23'); Preferably, the PHA(s) a) of the present invention are compounds (25), (26), (31), (32), (33), (34a) (42), and (43), more preferably is selected from (25), (26), (31) and (32), especially (26). 15. The method according to any one of claims 1 to 14, wherein the PHA copolymer(s) a) is present in an amount ranging from 0.1% to 65% by weight, preferably from 0.1% to 60% by weight, relative to the total weight of the composition. range, specifically 1% to 50% by weight, more specifically 3% to 40% by weight, preferably 5% to 35% by weight, more preferably 10% by weight, relative to the total weight of the composition. Composition (C1') in an amount ranging from % to 30% by weight, better still from 15% to 20% by weight. 16. The method according to any one of claims 1 to 15, wherein b) the volatile oil(s) are selected from hydrocarbon-based oils and silicone oils; Specifically:
* Hydrocarbon-based oils containing 8 to 16 carbon atoms, and especially
- branched C ₈ -C ₁₆ alkanes, such as isoalkanes, such as iso-alkanes (also known as isoparaffins), such as C ₁₃ -C ₁₆ isoparaffins, isododecane, isodecane, isohexadecane, and for example the oils sold under the trade names Isopar or Permetyl (either alone or in mixtures), preferably isododecane (also known as 2,2,4,4,6-pentamethylheptane), more preferentially isododecane;
- linear alkanes, such as C ₁₁ -C ₁₆ alkanes (alone or in mixtures) such as hexane, decane, undecane, tridecane, isoparaffins such as or n-dodecane (C12) and n-tetradecane. (C14), undecane-tridecane mixture, mixture of n-undecane (C11) and n-tridecane (C13), and mixtures thereof and also n -undecane (C11) and n -tridecane (C13) mixture of;
- Volatile, non-aromatic cyclic C ₅ -C ₁₂ alkanes;
* Short-chain esters containing a total of 3 to 8 carbon atoms, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate,
* Structural formula R' ₁ -OC(O)-O-R' ₂ , advantageously selected from dibutyl carbonate or dipentyl carbonate, where R' ₁ and R' ₂ are independently linear, branched or cyclic carbonate hydrocarbon-based oils (representing C ₄ -C ₈ alkyl groups, preferably C ₄ -C ₈ alkyl groups);
* Ether oils of the formula R ₁ -OR ₂ wherein R ₁ and R ₂ independently represent a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group;
* Silicone oils, specifically containing 2 to 7 silicon atoms (such silicone oils optionally contain alkyl or alkoxy groups containing 1 to 10 carbon atoms), such as dimethicone with a viscosity of 5 and 6 cSt, cyclo Pentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldi siloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof;
More preferably, the volatile oil(s) b) is selected from C ₈ -C ₁₆ alkanes, especially branched alkanes such as isododecane, and mixtures of undecane and tridecane, more preferably volatile oils ( s) Composition (C1'), wherein b) is selected from C ₈ -C ₁₆ alkanes, especially branched alkanes, such as isododecane. 17. The method of any one of claims 1 to 16, wherein c) the non-volatile oil(s) are:
* Non-volatile fluoro oils, especially selected from fluorinated polyethers and fluorosilicone oils, fluorosilicones;
* Non-volatile silicone oils, especially selected from non-volatile silicones with the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone , phenyl trimethicone, diphenylsiloxy phenyl trimethicone; and also mixtures thereof;
* Oils based on non-volatile non-polar hydrocarbons, especially selected from linear or branched compounds of mineral or synthetic origin: i) liquid paraffin, ii) squalane, isoeicosane, iii) linear, saturated hydrocarbons, more specifically C ₁₅ -C ₂₈ mixtures of hydrocarbons, such as mixtures with INCI names (C ₁₅ -C ₁₉ )alkanes, (C ₁₈ -C ₂₁ )alkanes, (C ₂₁ -C ₂₈ )alkanes, iv) hydrogenated or non-hydrogenated polybutenes; v) hydrogenated or non-hydrogenated polyisobutene, preferably hydrogenated polyisobutene, vi) hydrogenated or non-hydrogenated polydecene, vii) decene/butene copolymer, butene/isobutene copolymer and viii) mixtures thereof;
* Non-volatile polar hydrocarbon-based oils that may be selected from:
i) saturated, unsaturated, linear or branched C ₁₀ -C ₂₆ fatty alcohol, preferably monoalcohol (advantageously, the C ₁₀ -C ₂₆ alcohol is preferably branched if it contains at least 16 carbon atoms) phosphorus, a fatty alcohol; preferably the fatty alcohol contains 10 to 24 carbon atoms, more preferably 12 to 22 carbon atoms), especially such as lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2 -butyloctanol, 2-undecylpentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof;
ii) triglycerides consisting of fatty acid esters of glycerol (in particular the fatty acids thereof may have chain lengths ranging from C ₄ to C ₃₆ , and especially from C ₁₈ to C ₃₆ ), such oils possibly being linear or branched , and saturated or unsaturated; for example, heptanoic or octanoic triglycerides, caprylic/capric acid triglycerides, vegetable oils such as malt oil, sunflower oil, grape seed oil, sesame seed oil, corn oil, Apricot kernel oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, foreskin. (poppy) oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, sorghum oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion fruit. liquid fractions of flower oil, musk rose oil, peanut oil, argan oil, passionflower oil, kaya oil, and mixtures thereof;
iii) especially isoamyl laurate, cetostearyl octanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate or isostearate, ethyl palmitate, 2-ethylhexyl palmitate, isostearyl isostear. octyl stearate, isostearyl heptanoate, octanoate, decanoate or ricinoleate of alcohol or polyalcohol, such as propylene glycol dioctanoate, cetyl octanoate or tridecyl octanoate, 2 -ethylhexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol bis(2-ethylhexanoate) and mixtures thereof, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, iso Tridecyl neopentanoate, isostearyl neopentanoate or 2-octyldodecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate or octyl isononanoate. selected from ate, oleyl erucate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate or myristyl myristate; Formula RC(O)-OR' (where RC(O)-O- represents a carboxylic acid moiety containing 2 to 40 carbon atoms and R' represents a hydrocarbon-based chain containing 1 to 40 carbon atoms linear aliphatic hydrocarbon-based esters of alkylene glycols, especially ethylene glycol or propylene glycol, the total number of carbon atoms being advantageously at least 10;
iv) hydroxylated esters such as polyglyceryl-2 triisostearate;
v) aromatic esters, such as tridecyl trimellitate, C ₁₂ -C ₁₅ alcohol benzoate, 2-phenylethyl ester of benzoic acid, and butyloctyl salicylate,
vi) linear fatty acid esters with a total carbon number ranging from 35 to 70, such as pentaerythrityl tetrapelargonate,
vii) Esters of C ₂₄ -C ₂₈ branched fatty acids or fatty alcohols, such as triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl tris(2-decyltetradecano) ate), pentaerythrityl tetraisostearate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetrakis(2-decyltetradecanoate);
viii) polyesters obtained by condensation of dimers and/or trimers of diols with unsaturated fatty acids, such as those with the INCI name dilinoleic acid/butanediol copolymer or dilinoleic acid/propanediol copolymer; Polyesters obtained by condensation of fatty acid dimers and diol dimers, such as dimer dilinoleyl dimer dilinoleate;
ix) synthetic ethers containing 10 to 40 carbon atoms, such as dicaprylyl ether;
x) dialkyl carbonates in which the two alkyl chains may be identical or different, such as dicaprylyl carbonate;
xi) Vinylpyrrolidone copolymers, such as vinylpyrrolidone/1-hexadecene copolymer; and
xii) mixtures thereof;
* Non-volatile carbonate oils may be selected from carbonates of the formula R ₈ -OC(O)-OR ₉ where R ₈ and R ₉ may be the same or different and have linear or branched C ₄ to C ₁₂ and preferentially represents a C ₆ to C ₁₀ alkyl chain); Carbonate oils include dicaprylyl carbonate (or dioctyl carbonate), bis(2-ethylhexyl) carbonate, dipropylheptyl carbonate, dibutyl carbonate, and dineopentyl carbonate. , dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate;
* Formula R ₁ -OR ₂ where R ₁ and R ₂ are independently a linear, branched or cyclic C ₆ -C ₂₄ alkyl group, preferably a C ₆ -C ₁₈ alkyl group, preferably C ₈ -C ₁₂ oils known as non-volatile ether oils (representing alkyl groups) (it may be preferred that R ₁ and R ₂ are the same. Linear alkyl groups that may be mentioned include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group) Syl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, behenyl group, docosyl group, tricosyl group and branched alkyl groups that may be mentioned include 1,1-dimethylpropyl group, 3-methylhexyl group, 5-methylhexyl group, ethylhexyl group, 2-ethylhexyl group, 5-methyloctyl group. , 1-ethylhexyl group, 1-butylpentyl group, 2-butyloctyl group, isotridecyl group, 2-pentylnonyl group, 2-hexyldecyl group, isostearyl group, 2-heptylundecyl group, 2- Octyldodecyl group, 1,3-dimethylbutyl group, 1-(1-methylethyl)-2-methylpropyl group, 1,1,3,3-tetramethylbutyl group, 3,5,5-trimethylhexyl group , 1-(2-methylpropyl)-3-methylbutyl group, 3,7-dimethyloctyl group and 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl group. As groups, cyclohexyl group, 3-methylcyclohexyl group and 3,3,5-trimethylcyclohexyl group, dilauryl ether, diisostearyl ether, dioctyl ether, nonylphenyl ether, dodecyl dimethyl butyl ether, cetyl. dimethyl butyl ether and mixtures thereof may be mentioned)
is selected from;
More preferentially c) the non-volatile oil(s) are squalene, hydrogenated or non-hydrogenated polyisobutene, preferably hydrogenated polyisobutene, for example non-volatile compounds of the Parleam® family; A mixture of C ₁₅ -C ₁₉ alkanes, formula RC(O)-OR', where, as previously defined, RC(O)-O represents a carboxylic acid moiety containing 2 to 40 carbon atoms, and R ' represents a hydrocarbon-based chain containing 1 to 40 carbon atoms), and is selected from linear aliphatic hydrocarbon-based esters, especially isononyl isononanoate. According to any one of claims 1 to 17,

The amount of volatile oil b) is 5% to 95% by weight relative to the total weight of the composition, more specifically 20% to 90% by weight, preferentially 50% to 85% by weight, even better, relative to the total weight of the composition. is 60% to 80% by weight;

The amount of non-volatile oil c) is 0.1% to 15% by weight, preferably 0.2% to 12% by weight, more preferably 0.15% to 10% by weight, even more preferably 0.2% by weight, relative to the total weight of the composition. to 5% by weight of composition (C1'). The mass ratio according to any one of claims 1 to 18, Composition (C1'): 0 < < 900, specifically 1 < ≤ 800, even better 1 < <800; More specifically 2 < ≤ 700, and even better, 2 < <700; Priority 3 < ≤ 600, even better 3 < <600; More preferentially 3.5 < ≤ 600, even better 3.5 < <600; Even more preferentially 4 < ≤ 500, even better 4 < <500; More advantageously 4.5 < ≤ 400, even better 4.5 < <400. 19. The method according to any one of claims 1 to 18, wherein e) c) at least one organic solvent other than a polar protic or polar aprotic organic solvent, preferably a polar protic organic solvent, especially 2 to 10 organic solvents. lower monoalcohols containing carbon atoms, such as ethanol and isopropanol, preferably ethanol; Preferably, the amount of organic solvent(s) is less than 70% by weight, more preferably less than 50% by weight, relative to the total weight of composition (C1'); According to one embodiment of the invention, composition (C1') comprises organic solvent(s) in an amount of more than 0.5% by weight, more specifically more than 1% by weight, relative to the total weight of the composition; Specifically, composition (C1'), wherein the composition comprises from 2% to 50% by weight of organic solvent(s). 21. The method according to any one of claims 1 to 20, further comprising at least one colorant, preferably a pigment, selected from pigments, direct dyes and mixtures thereof; More preferentially, the pigment(s) of the invention include carbon black, iron oxide, especially black iron oxide, and mica coated with iron oxide, triarylmethane pigments, especially blue and purple triarylmethane pigments, such as Blue 1 Lake, azo pigments, Compositions, especially selected from red azo pigments, such as D&C Red 7, alkali metal salts of Lithol Red, such as the calcium salt of Lithol Red B, and even more preferentially red iron oxides. The composition as defined in any one of claims 1 to 21 is applied to a keratinous material, preferably α) keratin fibers, especially human keratin fibers such as hair, or β) human skin, especially the lips. How to deal with it. Cosmetic use of the composition according to any one of claims 1 to 21.