[0001] The present invention relates to a cosmetic composition comprising at least one
polyhydroxyalkanoate copolymer comprising at least two different polymer units bearing a
saturated or unsaturated hydrocarbon-based chain in a fatty and preferably oily medium,
and also to a process for treating keratin materials using such a composition.
[0002] It is known practice to use, in cosmetics, film-forming polymers which can be conveyed
in organic media, such as hydrocarbon-based oils. Polymers are notably used as filmforming
agents in makeup products such as mascaras, eyeliners, eyeshadows or lipsticks.
[0003] FR-A-2964663 describes a cosmetic composition comprising pigments coated with a
C3-C21 polyhydroxyalkanoate, such as poly(hydroxybutyrate-co-hydroxyvalerate).
[0004] WO 2011/154508 describes a cosmetic composition comprising a 4-carboxy-2-
pyrrolidinone ester derivative and a film-forming polymer which may be a
polyhydroxyalkanoate, such as polyhydroxybutyrate, polyhydroxyvalerate and
polyhydroxybutyrate-co-polyhydroxyvalerate.
[0005] US-A-2015/274972 describes a cosmetic composition comprising a thermoplastic
resin, such as a polyhydroxyalkanoate, in aqueous dispersion and a silicone elastomer.
On the other hand, WO 2018/178899 describes a cosmetic composition comprising at least
one polyhydroxyalkanoate (PHA) in the form of particles with an average diameter (d50)
from 0.1 llm to 100 !lm, in an amount of from 0.1 %by weight to 30 %. by weight, with
respect to the total weight of the composition.in order to absorb oily substances, such as
sebum. Nevertheless the later PHAs are not acceptable film forming polymers in fatty
substances such as oil.
[0006] The majority of the polyhydroxyalkanoates are polymers derived from the
polycondensation of polymeric repeating units that are for the most part identical and
derived from the same carbon source or substrate. These documents do not describe the
use of copolymers derived from polycondensation using a substrate composed of a mixture
of aliphatic carbon sources and of carbon sources comprising one or more reactive
functions, of different chemical nature from the first carbon source. Copolymers derived
from polycondensation may also be prepared from an aliphatic substrate or first carbon
source, and at least one second substrate, different from the first, comprising one or more
reactive functions of different chemical nature from the first carbon source.
wo 2021/260048 2 PCT/EP2021/067220
[0007] A need thus exists to have available a composition compns1ng a solubilized
polyhydroxyalkanoate making it possible to obtain a film that has good cosmetic properties,
notably good resistance to oils and to sebum, and also good mattness.
[0008] The Applicant has discovered that polyhydroxyalkanoate copolymers comprising at
least two different polymer units (A) and (B) as defined below may be readily used in fatty
and notably oily media, thus making it possible to obtain homogeneous compositions.
Moreover, the PHA according to the invention are film forming polymers. The composition
shows good stability, notably after storage for one month at room temperature (25°C). The
composition, notably after its application to keratin materials, makes it possible to obtain a
film having good cosmetic properties, in particular good resistance to oils and to sebum,
and also a matt or glossy appearance.
[0009] Thus, the main subject of the present invention is a composition, notably a
cosmetic composition, comprising:
a) one or more polyhydroxyalkanoate (PHA) copolymers which contain, and preferably
consist of, at least two different repeating polymer units chosen from the units (A) and (B)
below, and also the optical or geometrical isomers thereof and the solvates thereof such as
hydrates:
-[-O-CH(R1)-CH2-C(O)-]- unit (A)
-[-O-CH(R2)-CH2-C(O)-]- unit (B)
in which polymer units (A) and (B):
R1 represents a hydrocarbon-based chain chosen from: i) branched (Cs-Cg)alkyl, ii) (C10-
C3o)alkyl; iii) linear or branched (Cs-C3o)alkenyl; iv) linear or branched (Cs-C3o)alkynyl;
v) (hetero)aryl; vi) (hetero)cycloalkyl; preferably the group i) (Cw-C2o)alkyl, or iii) (CsC2o)
alkenyl;
R2 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated
hydrocarbon-based group, comprising from 1 to 30 carbon atoms; and
b) a fatty medium comprising one or more fatty substances, which are preferably liquid at
25°C and at atmospheric pressure;
it being understood that (A) is different from (B).
[001 0] Another subject of the invention is the use a) of one or more PHAs as defined previously
and b) one or more fatty substances as defined previously, in cosmetics.
[0011] Another subject of the invention is a process for treating keratin materials, preferably
a) keratin fibres, notably human keratin fibres such as the hair, or 13) human skin, in
particular the lips, using a) one or more PHAs as defined previously and b) one or more
fatty substances as defined previously. More particularly, a subject of the invention is the
process for treating keratin materials, preferably a) keratin fibres, notably human keratin
fibres such as the hair, or 13) human skin, in particular the lips, by applying to said materials
the composition as defined previously.
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[0012] More particularly, a subject of the invention is also a non-therapeutic cosmetic process
for treating keratin materials, comprising the application to the keratin materials of a
composition as defined previously. The treatment process is in particular a process for
caring for or making up keratin materials.
[0013] For the purposes of the present invention and unless otherwise indicated:
the term "(hetero)aryf' means aryl or heteroaryl groups;
the term "(hetero)cyc/oa/kyf' means cycloalkyl or heterocycloalkyl groups;
the "aryf' or "heteroaryf' radicals or the aryl or heteroaryl part of a radical may be substituted
with at least one substituent borne by a carbon atom, chosen from:
o a C1-C6 and preferably C1-C4 alkyl radical;
o a halogen atom such as chlorine, fluorine or bromine;
o a C1-C2 alkoxy radical; a C2-C4 (poly)hydroxyalkoxy radical;
o an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom;
o a C1-C4 alkyl radical and the radical R' is a C1-C4 alkyl radical; a carbamoyl radical
((R)2N-CO-) in which the radicals R, which may be identical or different, represent a
hydrogen atom or a C1-C4 alkyl radical;
o an alkylsulfonylamino radical (R'S02-NR-) in which the radical R represents a hydrogen
atom or a C1-C4 alkyl radical and the radical R' represents a C1-C4 alkyl radical, or a
phenyl radical;
o a cyano group (CN);
o a polyhalo(C1-C4)alkyl group, preferentially trifluoromethyl (CF3);
the cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least
one substituent borne by a carbon atom, chosen from the groups:
o C1-C4 alkoxy, C2-C4 (poly)hydroxyalkoxy,
o alkylcarbonylamino (RCO-NR'-), in which the radical R' is a hydrogen atom or a C1-C4
alkyl radical and the radical R is a C1-C2 alkyl radical or an amino radical substituted
with one or two identical or different C1-C4 alkyl groups;
o alkylcarbonyloxy (RC0-0-), in which the radical R is a C1-C4 alkyl radical or an amino
radical substituted with one or two identical or different C1-C4 alkyl groups;
o alkoxycarbonyl ((RO-CO-) in which the radical R is a C1-C4 alkyl radical or an amino
radical substituted with one or two identical or different C1-C4 alkyl groups;
a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may
also be substituted with one or more oxo groups;
a hydrocarbon-based chain is unsaturated when it includes one or more double bonds
and/or one or more triple bonds;
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an "aryf' radical represents a monocyclic or fused or non-fused polycyclic hydrocarbonbased
group comprising from 6 to 22 carbon atoms, at least one ring of which is aromatic;
preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or
tetrahydronaphthyl and more preferentially phenyl;
a "heteroaryf' radical represents a monocyclic or fused or non-fused polycyclic, 5- to 22-
membered group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur
and selenium atoms, and at least one ring of which is aromatic; preferentially, a heteroaryl
radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl,
benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl,
tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl,
naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl,
oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl,
pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl,
thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl and xanthylyl;
a "cyclic" or "cycloalkyf' radical is a monocyclic or fused or non-fused polycyclic, nonaromatic
cyclic hydrocarbon-based radical containing from 5 to 22 carbon atoms, which
may include one or more unsaturations; the cycloalkyl is preferably a cyclohexyl group;
a "heterocyclic" or "heterocycloalkyf' radical is a monocyclic or fused or non-fused
polycyclic 5- to 9-membered non-aromatic cyclic radical, including from 1 to 4 heteroatoms
chosen from nitrogen, oxygen and sulfur atoms; preferably, the heterocycloalkyl is chosen
from epoxide, piperazinyl, piperidyl and morpholinyl;
an "alkyf' radical is a linear or branched, in particular C1-C6 and preferably C1-C4 saturated
hydrocarbon-based radical;
an "alkenyf' radical is a linear or branched unsaturated hydrocarbon-based radical,
comprising one or more conjugated or non-conjugated double bonds; preferably, the
radical comprises only one double bond at the chain end on the side opposite its point of
attachment to the rest of the molecule;
an "alkynyf' radical is a linear or branched unsaturated hydrocarbon-based radical,
comprising one or more conjugated or non-conjugated triple bonds; preferably, the radical
comprises only one triple bond at the chain end on the side opposite its point of attachment
to the rest of the molecule;
an "alkoxy radicaf' is an alkyl-oxy radical for which the alkyl radical is a linear or branched
C1-C6 and preferentially C1-C4 hydrocarbon-based radical;
the term "organic or mineral acid salf' more particularly means organic or mineral acid salts
in particular chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid
HBr, iii) sulfuric acid H2S04, iv) alkylsulfonic acids: Alk-S(0)20H such as methylsulfonic
acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(0)20H such as benzenesulfonic acid
and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-0-S(O)OH such as methoxysulfinic
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acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and
phenoxysulfinic acid; viii) phosphoric acid H3P04; ix) triflic acid CF3S03H and x)
tetrafluoroboric acid HBF4; xi) organic carboxylic acids W-C(O)-OH (l'z), in which formula
(l'z) W represents a (hetero)aryl group such as phenyl, (hetero)aryi(C1-C4)alkyl group such
as benzyl, or (C1-C10)alkyl, said alkyl group being optionally substituted preferably with one
or more hydroxyl groups or amino or carboxyl radicals, W preferably denoting a (C1-
C6)alkyl group optionally substituted with 1, 2 or 3 hydroxyl or carboxyl groups; more
preferentially, the monocarboxylic acids of formula (l'z) are chosen from acetic acid,
glycolic acid, lactic acid, and mixtures thereof, and more particularly from acetic acid and
lactic acid; and the polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric
acid, citric acid and mixtures thereof; and xii) amino acids including more carboxylic acid
radicals than amino groups, such as y-carboxyglutamic acid, aspartic acid or glutamic acid,
in particular y-carboxyglutamic acid;
an "anionic counterion" is an anion or an anionic group associated with the cationic charge;
more particularly, the anionic counterion is chosen from: i) halides such as chloride or
bromide; ii) nitrates; iii) sulfonates, including C1-C6 alkylsulfonates: Alk-S(0)20- such as
methanesulfonate or mesylate and ethanesulfonate; iv) arylsulfonates: Ar-S(0)20- such as
benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii)
lactate; ix) alkyl sulfates: Alk-0-S(O)O- such as methyl sulfate and ethyl sulfate; x) aryl
sulfates: Ar-0-S(O)O- such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-
0-8(0)20- such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O-S(0)20-;
xiii) phosphate; xiv) acetate; xv) triflate; and xvi) berates such as tetrafluoroborate.
the "so/vates" represent hydrates and also the combination with linear or branched C1-C4
alcohols such as ethanol, isopropanol or n-propanol.
Furthermore, unless otherwise indicated, the limits delimiting the extent of a range of values
are included in that range of values.
[0014] a) The PHA copolvmer(s)
[0015] The composition of the invention comprises as first ingredient a) one or more PHA
copolymers which contain, and which are preferably consist of, at least two different
repeating polymer units chosen from the units (A) and (B) as defined previously.
[0016] The term "copolymer" means that said polymer is derived from the polycondensation
of repeating polymer units that are different from each other, i.e. said polymer is derived
from the polycondensation of repeating polymer units (A) with (B), it being understood that
the polymer units (A) are different from the polymer units (B).
[0017] According to a particular embodiment of the invention, the PHA copolymer(s) consist
of two different repeating polymer units chosen from the units (A) and (B) as defined
previously.
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[0018] More particularly, the PHA copolymer(s) according to the invention comprise the
repeating unit of formula (1), and also the optical or geometrical isomers thereof and the
solvates thereof such as hydrates:
[0019] [Chem. 1]:
in which formula (1):
D R1 and R2 are as defined previously,
D m and n are integers greater than or equal to 1; preferably, the sum n + m is inclusively
between 450 and 1400;
preferably, m > n when R1 and R2 represent an alkyl group- more preferentially, when
R1 and R2 are alkyl, then R1 is a Cs-C13 alkyl group; and R2 represents a linear alkyl
group with a carbon number corresponding to the carbon number of R1 from which two
carbon atoms are subtracted; and
preferably, m < n when R1 represents an alkenyl or alkyl group, and R2 represents an
alkyl group.
[0020] According to a particular embodiment, the PHA copolymer(s) of composition a) contain
three different repeating polymer units (A), (B) and (C), and preferably consist of three
different polymer units (A), (B) and (C), below, and also the optical or geometrical isomers
thereof and the solvates thereof such as hydrates:
-[-O-CH(R1)-CH2-C(O)-]-
-[-O-CH(R2)-CH2-C(O)-]-
-[-O-CH(R3)-CH2-C(O)-]-
in which polymer units (A), (B) and (C):
R1 and R2 are as defined previously;
unit (A)
unit (B)
unit (C)
R3 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated
hydrocarbon-based group comprising from 1 to 30 carbon atoms, and in particular
represents a hydrocarbon-based group chosen from linear or branched (C1-C2s)alkyl
and linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbon-based group,
more particularly (C4-C2o)alkenyl; preferably, the hydrocarbon-based group has a
carbon number corresponding to the number of carbon atoms of the radical R1, or else
corresponding to the number of carbon atoms of the radical R1 from which at least three
carbon atoms are subtracted, preferably corresponding to the number of carbon atoms
of the radical R1 from which four carbon atoms are subtracted; and
it being understood that:
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(A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different
from (A) and (B); and
preferably, when R1
, R2 and R3 represent an alkyl group, the molar percentage of units
(A) is greater than the molar percentage of units (B), and greater than the molar
percentage of units (C)- more preferentially, when R1, R2 and R3 are alkyl, then R1 is a
Cs-C13 alkyl group; and R2 represents an alkyl group with a carbon number
corresponding to the carbon number of R1 from which two carbon atoms are subtracted,
and R3 represents an alkyl group with a carbon number corresponding to the carbon
number of R1 from which four carbon atoms are subtracted; and
preferably, when R1 represents an alkenyl or alkynyl group, then the molar percentage
of units (A) is less than the molar percentage of units (B) and less than the molar
percentage of units (C) notably if R2 represents an alkyl group and/or R3 represent an
alkyl group, preferably R3 represents an alkyl group with a carbon number
corresponding to the carbon number of R2 from which two carbon atoms are subtracted.
[0021] According to a particular embodiment of the invention, the PHA copolymer(s) comprise
the repeating unit of formula (II), and also the optical or geometrical isomers thereof and
the solvates thereof such as hydrates:
[0022] [Chem. 2] :
(U)
in which formula (II):
o R1
, R2 and R3 are as defined previously;
D m, n and p are integers greater than or equal to 1; preferably, the sum n + m + p is
inclusively between 450 and 1400;
preferably, m > n + p when R1
, R2 and R3 represent an unsubstituted and uninterrupted
alkyl group- more preferentially, when R1
, R2 and R3 are alkyl, then R1 is a Cs-C13 alkyl
group; and R2 represents an alkyl group with a carbon number corresponding to the
carbon number of R1 from which two carbon atoms are subtracted, and R3 represents
an alkyl group with a carbon number corresponding to the carbon number of R1 from
which four carbon atoms are subtracted; and
preferably, m < n + p when R1 represents an alkenyl or alkynyl group, R2 and R3
represent an alkyl group, preferably R3 represents an alkyl group with a carbon number
corresponding to the carbon number of R2 from which two carbon atoms are subtracted.
[0023] According to a particular embodiment, the PHA copolymer(s) of composition a) contain
four different repeating polymer units (A), (B), (C) and (D), and preferably consist of four
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different polymer units (A), (B), (C) and (D), below, and also the optical or geometrical
isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof
such as hydrates:
-[-O-CH(R1)-CH2-C(O)-]-
-[-O-CH(R2)-CH2-C(O)-]-
-[-O-CH(R3)-CH2-C(O)-]-
-[ -0-CH (R4)-CH2-C(O)-]-
unit (A)
unit (B)
unit (C)
unit (D)
in which polymer units (A), (B), (C) and (D):
R1
, R2 and R3 are as defined previously;
R4 represents a cyclic or non-cyclic, linear or branched saturated hydrocarbon-based
group comprising from 3 to 30 carbon atoms; in particular represents a hydrocarbonbased
group chosen from linear or branched (C4-C2s)alkyl; and
it being understood that:
(A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), (C) is different
from (A), (B) and (D), and (D) is different from (A), (B) and (C); and
preferably, when R1
, R2
, R3 and R4 represent an alkyl group, the molar percentage of
units (A) is greater than the molar percentage of units (B), greater than the molar
percentage of units (C), and greater than the molar percentage of units (D) - more
preferentially, when R1
, R2
, R3 and R4 are alkyl, then R1 is a Cs-C13 alkyl group; and R2
represents an alkyl group with a carbon number corresponding to the carbon number of
R1 from which two carbon atoms are subtracted, and R3 represents an alkyl group with
a carbon number corresponding to the carbon number of R1 from which four carbon
atoms are subtracted, and R4 represents an alkyl group with a carbon number
corresponding to the carbon number of R1 from which six carbon atoms are subtracted;
and
preferably, when R1 represents an alkenyl or alkynyl group, then the molar percentage
of units (A) is less than the molar percentage of units (B), and is less than the molar
percentage of units (C), notably if R2 represents an alkyl group and/or R3 represents an
alkyl group, and R4 represents an alkenyl or alkynyl group, preferably R3 represents an
alkyl group with a carbon number corresponding to the carbon number of R2 from which
two carbon atoms are subtracted, and R4 represents an alkenyl or alkynyl group with a
carbon number corresponding to the carbon number of R1 from which two carbon atoms
are subtracted.
[0024] According to a particular embodiment of the invention, the PHA copolymer(s) comprise
the repeating unit of formula (Ill), and also the optical or geometrical isomers thereof, the
organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[0025] [Chern. 3] :
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(Ill)
in which formula (Ill):
o R1
, R2
, R3 and R4 are as defined previously;
D m, n, p and v are integers greater than or equal to 1;
preferably, the sum n + m + p +vis inclusively between 450 and 1400; and
preferably, when R1
, R2
, R3 and R4 represent an alkyl group, then m > n + p + q- more
preferentially, when R1
, R2
, R3 and R4 are alkyl, then R1 is a Cs-C13 alkyl group; and R2
represents a linear alkyl group with a carbon number corresponding to the carbon
number of R1 from which two carbon atoms are subtracted, R3 represents a linear alkyl
group with a carbon number corresponding to the carbon number of R1 from which four
carbon atoms are subtracted, and R4 represents a linear alkyl group with a carbon
number corresponding to the carbon number of R1 from which six carbon atoms are
subtracted; and
preferably, when R1 represents an alkenyl or alkynyl group, R2 and R3 represent an alkyl
group, and R4 represents an alkenyl or alkynyl group, then n > m + v; more preferentially
n + p > m + v; preferably, R3 represents an alkyl group with a carbon number
corresponding to the carbon number of R2 from which two carbon atoms are subtracted,
and R4 represents an alkenyl or alkynyl group with a carbon number corresponding to
the carbon number of R1 from which two carbon atoms are subtracted.
[0026] According to a more particular embodiment, the PHA copolymer(s) of composition a)
contain five different repeating polymer units (A), (B), (C), (D) and (E), and preferably
consist of five different polymer units (A), (B), (C), (D) and (E), below, and also the optical
or geometrical isomers thereof, the organic or mineral acid or base salts thereof, and also
the solvates thereof such as hydrates:
-[-O-CH(R1)-CH2-C(O)-]- unit (A)
-[-O-CH(R2)-CH2-C(O)-]- unit (B)
-[-O-CH(R3)-CH2-C(O)-]- unit (C)
-[ -0-CH (R4)-CH2-C(O)-]- unit (D)
-[-O-CH(R5)-CH2-C(O)-]- unit (E)
in which polymer units (A), (B), (C), (D) and (E):
R1
, R2 and R3 are as defined previously;
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R4 represents a cyclic or non-cyclic, linear or branched saturated hydrocarbon-based
group comprising from 3 to 30 carbon atoms, and in particular represents a
hydrocarbon-based group chosen from linear or branched (C4-C2s)alkyl; and
R5 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbon-based
group comprising from 3 to 30 carbon atoms, and in particular represents a
hydrocarbon-based group chosen from linear or branched (C4-C2s)alkyl; preferably, the
hydrocarbon-based group has a carbon number corresponding to the number of carbon
atoms of the radical R4 from which at least one carbon atom is subtracted, preferably
corresponding to the number of carbon atoms of the radical R4 from which at least two
carbon atoms are subtracted, preferably from which two carbon atoms are subtracted;
it being understood that:
(A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E); (C)
is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E)
is different from (A), (B), (C) and (D); and
preferably, when R1
, R2
, R3
, R4 and R5 represent an alkyl group, the molar percentage
of units (A) is greater than the molar percentage of units (B), greater than the molar
percentage of units (C), greater than the molar percentage of units (D) and greater than
the molar percentage of units (E)- more preferentially, when R1, R2, R3, R4 and R5 are
alkyl, then R1 is a Cs-C13 alkyl group; and R2 represents an alkyl group with a carbon
number corresponding to the carbon number of R1 from which two carbon atoms are
subtracted, R3 represents an alkyl group with a carbon number corresponding to the
carbon number of R1 from which four carbon atoms are subtracted, R4 represents an
alkyl group with a carbon number corresponding to the carbon number of R1 from which
six carbon atoms are subtracted, and R5 represents an alkyl group with a carbon number
corresponding to the carbon number of R1 from which eight carbon atoms are
subtracted, and
preferably, when R1 represents an alkenyl or alkynyl group, then the molar percentage
of units (A) is less than the molar percentage of units (B), and is less than the molar
percentage of units (C), notably if R2 represents an alkyl group and R3 represents an
alkyl group, and R4 and R5 represent an alkenyl or alkynyl group, preferably R3
represents an alkyl group with a carbon number corresponding to the carbon number of
R2 from which two carbon atoms are subtracted, and R4 represents an alkenyl or alkynyl
group with a carbon number corresponding to the carbon number of R1 from which two
carbon atoms are subtracted, and R5 represents an alkenyl or alkynyl group with a
carbon number corresponding to the carbon number of R1 from which four carbon atoms
are subtracted.
[0027] According to a particular embodiment of the invention, the PHA copolymer(s) comprise
the repeating unit of formula (IV), and also the optical or geometrical isomers thereof, the
organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[0028] [Chern. 4]:
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(IV)
in which formula (IV):
o R1
, R2
, R3
, R4 and R5 are as defined previously;
D m, n, p, v and z are integers greater than or equal to 1; preferably, the sum n + m + p
+ v + z is inclusively between 450 and 1400; and
preferably, when R1
, R2
, R3
, R4 and R5 represent an alkyl group, then m > n + p + v + z;
preferably, when R1 represents an alkenyl or alkynyl group, R2 and R3 represent an alkyl
group and the groups R4 and R5 represent an alkenyl or alkynyl group, then n > m + v +
z; more preferentially n + p > m + v + z; preferably, R3 represents an alkyl group with a
carbon number corresponding to the carbon number of R2 from which two carbon atoms
are subtracted, and R4 represents an alkenyl or alkynyl group with a carbon number
corresponding to the carbon number of R1 from which two carbon atoms are subtracted,
and R5 represents an alkenyl or alkynyl group with a carbon number corresponding to
the carbon number of R1 from which four carbon atoms are subtracted.
[0029] According to one embodiment of the composition according to the invention, the PHA
copolymer(s) are such that the radical R1 is a branched alkyl comprising 5 to 9 carbon atoms
such as 2-methyl-5-pentyl, 2-methyl-2-pentyl, isobutyl or 2-methylheptyl, preferably 2-
methyl-5-pentyl.
[0030] According to another particular embodiment of the invention, the PHA copolymer(s) are
such that R1 represents ii) a linear or branched, preferably linear, (Cw-C3o)alkyl.
[0031] According to another particular embodiment of the invention, the PHA copolymer(s) are
such that R1 represents iii) linear or branched (Cs-C3o)alkenyl; more particularly linear,
comprising at least one unsaturation, preferably only one unsaturation, at the end of said
alkenyl group; even more particularly, R1 represents the following group: -[CR4(R5)]qC(
R6)=C(R7)-R8 with R4, R5, R6, R7 and R8, which may be identical or different, representing
a hydrogen atom or a (C1-C4)alkyl group such as methyl, preferably a hydrogen atom, and
q represents an integer inclusively between 2 and 20, preferably between 3 and 10, more
preferentially between 4 and 8, such as 6. More particularly, R1 is chosen from hexenyl,
octenyl, undecenyl, 2-butenyl and 2-methyl-2-pentenyl.
[0032] In particular, the PHA copolymer(s) are such that R2 is chosen from linear or branched
(C1-C2s)alkyl, and linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbonbased
group, more particularly (C3-C2o)alkyl or (C3-C2o)alkenyl; preferably, the hydrocarbonbased
group has a carbon number corresponding to the number of carbon atoms of the
radical R1 from which at least one carbon atom is subtracted, preferably corresponding to
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the number of carbon atoms of the radical R1 from which at least two carbon atoms are
subtracted, preferably to the number of carbon atoms of the radical R1 from which two
carbon atoms are subtracted.
[0033] According to one embodiment of the invention, the PHA copolymer(s) are such that the
radical R2 is a linear or branched, preferably linear, (C1-C10)alkyl, in particular (C2-Cs)alkyl,
preferably (C4-C6)alkyl group such as n-pentyl or n-hexyl, n-heptyl or n-nonyl.
[0034] According to another embodiment of the composition according to the invention, the
PHA copolymer(s) comprise a branched (C3-Cs)alkyl, particularly (C4-C6)alkyl radical R2
,
preferably a branched (C4-Cs)alkyl radical such as isobutyl.
[0035] According to another embodiment of the composition according to the invention, the
PHA copolymer(s) of the invention comprise the units (A) containing an alkyl radical R1 as
defined previously, the units (B) as defined previously and the units (C) containing a linear
or branched (C5-C2o)alkenyl and particularly (CrC14)alkenyl radical, more particularly a (CsC10)
alkenyl radical, which is preferably linear, and comprising only one unsaturation at the
chain end such as -[CH2]q-CH=CH2 and q represents an integer inclusively between 3 and
8, preferably between 4 and 6, such as 5.
[0036] According to a particular embodiment of the invention, in the PHA copolymer(s), the
units (A) comprises a hydrocarbon-based chain R1 which is an alkenyl or alkynyl group as
defined previously, in particular iii), said unit (A) is present in a molar percentage ranging
from 0.1% to 50%, more preferentially a molar percentage ranging from 0.5% to 40%, even
more preferentially a molar percentage ranging from 1% to 40%, better still a molar
percentage ranging from 2% to 30%, or a molar percentage ranging from 5% to 20%.
[0037] Preferably, when R1 of the unit (A) is an unsaturated hydrocarbon-based chain, said
unit (A) is present in a molar percentage of less than or equal to 30%, more particularly less
than 20%, preferably between 8% and 13%.
[0038] According to a more particular embodiment of the invention in the PHA copolymer(s),
when the unit (A) comprises a hydrocarbon-based chain R1 which is an alkenyl or alkynyl
group as defined previously, in particular iii), said unit (A) is present in a molar percentage
ranging from 0.1% to 50%, more preferentially a molar percentage ranging from 0.5% to
40%, even more preferentially a molar percentage ranging from 1% to 40%, better still a
molar percentage ranging from 5% to 30%, a molar percentage ranging from 8% to 20%;
the unit (B) is present in a molar percentage ranging from 70% to 99.5%, preferably between
60% and 95%; and the unit (C) is present in a molar percentage ranging from 0 to 30%,
preferably between 1% and 25%, more preferentially between 5% and 24% relative to the
sum of the units (A), (B) and (C). Advantageously, the PHA copolymer(s) of the invention
comprise from 70 mol% to 90 mol% of units (B), and from 6 mol% to 24 mol% of units (C).
wo 2021/260048 13 PCT/EP2021/067220
[0039] Preferably, when R1 of the unit (A) is a saturated hydrocarbon-based chain, said unit
(A) is present in a molar percentage of greater than 30%, more particularly greater than
50%, more preferentially greater than 60%, preferably between 60% and 90%.
[0040] According to a more particular embodiment of the invention when R1 is an alkyl group,
the PHA copolymer(s) are such that, in the PHA copolymer(s) a):
the unit (A) is present in a molar percentage ranging from 30% to 99%,
preferentially a molar percentage ranging from 40% to 95%, more preferentially
a molar percentage ranging from 50% to 85%, even more preferentially a molar
percentage ranging from 60% to 70%; and
the unit (B) is present in a molar percentage ranging from 0.5% to 70%,
preferentially a molar percentage ranging from 2% to 10%, more preferentially a
molar percentage ranging from 5% to 35% of units (B); and/or
the unit (C) is present in a molar percentage ranging from 0% to 20%,
preferentially a molar percentage ranging from 0.1% to 10%, more preferentially
from 0.5% to 7% of units (C).
[0041] According to a more particular embodiment of the invention in the PHA copolymer(s),
when the unit (A) comprises a hydrocarbon-based chain R1 which is an alkenyl or alkynyl
group as defined previously, in particular iii), said unit (A) is present in a molar percentage
ranging from 0.1% to 50%, more preferentially a molar percentage ranging from 0.5% to
40%, even more preferentially a molar percentage ranging from 1% to 40%, better still a
molar percentage ranging from 5% to 30%, a molar percentage ranging from 8% to 20%;
the unit (B) is present in a molar percentage ranging from 70% to 99.5%, preferably between
60% and 95%; and the unit (C) is present in a molar percentage ranging from 0 to 30%,
preferably between 1% and 25%, more preferentially between 5% and 24% relative to the
sum, the unit (D) is present in a molar percentage ranging from 0 to 10%, preferably
between 0.1% and 5%, more preferentially between 0.5% and 2% relative to the sum, and
the unit (E) 0 to 10%, preferably between 0.1% and 5%, more preferentially between 0.5%
and 2% relative to the sum. Advantageously, the PHA copolymer(s) of the invention
comprise from 70 mol% to 90 mol% of units (B), and from 6 mol% to 24 mol% of units (C).
[0042] The values of the molar percentages of the units (A), (B), (C), (D) and (E) of the PHA
copolymer(s) are calculated relative to the total number of moles of (A) + (B) if the
copolymer(s) do not comprise any additional units (C), (D) or (E), otherwise, if the
copolymer(s) of the invention contain more than two different units, i.e. (A), (B) and (C), (A),
(B), (C) and (D), or (A), (B), (C), (D) and (E), then the molar percentage is calculated relative
to the total number of moles, i.e. respectively (A) + (B) + (C), (A) + (B) + (C) +(D) or (A) +
(B) + (C) +(D) + (E).
[0043] Preferentially, the PHA copolymer(s) of the invention comprise the following repeating
units:
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In particular, the stereochemistry of the carbon atoms bearing the radicals R1 and R2 is of the
same (R) or (S) configuration, preferably of (R) configuration.
More particularly, the stereochemistry of the carbon atoms bearing the radicals R1
, R2 and R3
is of the same (R) or (S) configuration, preferably of (R) configuration.
More particularly, the stereochemistry of the carbon atoms bearing the radicals R1
, R2
, R3 and
R4 is of the same (R) or (S) configuration, preferably of (R) configuration.
More particularly, the stereochemistry of the carbon atoms bearing the radicals R1
, R2
, R3
, R4
and R5 is of the same (R) or (S) configuration, preferably of (R) configuration.
More preferentially, the PHA copolymer(s) of the invention comprise the following repeating
units:
[0044] [Chem. 5] :
Compounds
[0045] [Chem. 6] :
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Compounds
[0046] [Chern. 7] :
[0047] [Chern. 8] :
wo 2021/260048 16 PCT/EP2021/067220
[0048] [Chem. 9] :
[0049] According to an embodiment, the PHA copolymer(s) of the invention are different of
compound (2) and/or (2') especially (2), and more particularly are different from compounds
(1) and (2) and/or (1') and (2') especially (1) and (2).
The PHA copolymer(s) of the invention preferably have a number-average molecular weight
ranging from 50 000 to 150 000.
[0050] The molecular weight may notably be measured by size exclusion chromatography. A
method is described below in the examples.
[0051] The PHA copolymer(s) are particularly present in the composition according to the
invention in a content ranging from 0.1% to 30% by weight and preferably ranging from
0.1% to 25% by weight relative to the total weight of the composition.
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Method for preparing the PHA copolymer(s):
[0052] The methods for preparing the PHA copolymer(s) of the invention are known to those
skilled in the art. Mention may notably be made of the use of "functionalizable" PHAproducing
microbial strains.
[0053] The term "functionalizable" means that the PHA copolymer(s) comprise a hydrocarbonbased
chain comprising one or more atoms or groups that are capable of reacting
chemically with another reagent- also referred to as "reactive atoms or reactive groups" -
to give a covalent bond functionalized with said reagent. The reagent is, for example, a
compound comprising at least one nucleophilic group and said functionalized hydrocarbonbased
chain comprises at least one electrophilic or nucleofugal atom or group, the
nucleophilic group(s) reacting with the electrophilic group(s) to covalently graft the reagent.
The nucleophilic reagent may also react with one or more unsaturations of the alkenyl
group(s) to also lead to grafting by covalent bonding of the functionalized hydrocarbonbased
chain with said reagent. The addition may also be radical-based, an addition of
Markovnikov or anti-Markovnikov type, or nucleophilic or electrophilic substitution. The
addition or condensation reactions may or may not take place via a radical route, with or
without the use of catalysts or of enzymes, with heating preferably less than or equal to
100°C, under a pressure of greater than 1 atm, under an inert atmosphere or under oxygen.
[0054] The term "nucleophilic" refers to any atom or group which is electron-donating by an
inductive effect +I and/or a mesomeric effect +M. Electron-donating groups that may be
mentioned include hydroxyl, thiol and amino groups.
[0055] The term "electrophilic" refers to any atom or group which is electron-withdrawing by
an inductive effect -1 and/or a mesomeric effect -M. Electron-withdrawing species that may
be mentioned include.
[0056] The microorganisms which produce PHAs of the invention notably bearing a C3-Cs
hydrocarbon-based chain may be naturally produced by the bacterial kingdom, such as
Cyanobacteria of the order of Nostocales (e.g.: Nostoc muscorum, Synechocystis and
Synechococcus) but mainly by the Proteobacteria, for example in the class of:
-beta-Proteobacteria, of the order Burkholderiales ( Cupriavidus neg a tor synonym Rasltonia
eutropha)
[0057] -alpha-Proteobacteria, of the order Rhodobacteriales (Rhodobacter capsulatus marine
and photosynthetic)
[0058] -gamma-Proteobacteria, of the order Pseudomonales of the family Moraxellaceae
(Acinetobacter junii).
[0059] Among the microorganisms of the bacterial kingdom, the genera Azotobacter,
Hydrogenomomas or Chromatium are the most representative of the PHA-producing
organisms.
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[0060] The organisms which naturally produce PHAs bearing a C3-Cs hydrocarbon-based
chain are notably Proteobacteria, such as gamma-Proteobacteria, and more particularly of
the order Pseudomonales of the family Pseudomonas such as Pseudomonas resinovorans,
Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas aeruginosa,
Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas chlororaphis and
preferably Pseudomonas putida GPo1 and Pseudomonas putida KT2440.
[0061] Certain organisms may also naturally produce PHAs without belonging to the order of
Pseudomonales, such as Commamonas testosteroni which belongs to the class of betaProteobacteria
of the order Burkholderiales of the family of Comamonadaceae.
[0062] The PHA-producing microorganism according to the invention may also be a
recombinant strain if a 3-oxidation PHA synthase metabolic pathway is present. The 3-
oxidation PHA synthase metabolic pathway is mainly represented by four enzymes, EC:
2.3.1 82, EC: 2.3.1 83, EC: 2.3.1 84 and EC: 2.3.1 85.
[0063] The recombinant strain may be of the Bacteria kingdom, e.g.: Escherichia coli or of the
Plantae kingdom, e.g.: Chlorella pyrenoidosa: International Journal of Biological
Macromolecules, 116, 552-562 "Influence of nitrogen on growth, biomass composition,
production, and properties of polyhydroxyalkanoates (PHAs) by microalgae") or of the Fungi
kingdom, e.g. Saccaromyces cerevisiae or Yarrowia lipolytica: Applied Microbiology and
Biotechnology 91, 1327-1340 (2011) "Engineering polyhydroxyalkanoate content and
monomer composition in the oleaginous yeast Yarrowia lipolytica by modifying the
13-oxidation multifunctional protein").
[0064] Use may also be made of genetically modified microorganisms, which may make it
possible, for example, to increase the production of PHA, to increase the oxygen
consumption capacity, to reduce the autolysis and/or to modify the monomer ratio.
[0065] It is known that, for PHAs, a large portion of the total production cost is devoted to the
culture medium and mainly to the substrate/carbon source. Use may thus be made of
genetically modified microorganisms using a smaller amount of nutrient with little added
value (such as methane or C02) (carbon source) for their growth, for example photoautotrophic
by nature, i.e. using light and C02 as main energy source.
[0066] The copolymer may also be obtained in a known manner by biosynthesis, for example
with the microorganisms belonging to the genus Pseudomonas, such as Pseudomonas
resinovorans, Pseudomomonas putida, Pseudomonas fluorescens, Pseudomonas
aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina, Pseudomonas
chlororaphis and preferably Pseudomonas putida; and with a carbon source which may be
a C2-C2o, preferably C6-C1s, carboxylic acid, such as acetic acid, propionic acid, butyric acid,
hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; a saccharide,
such as fructose, maltose, lactose, xylose, arabinose, etc.); ann-alkane, such as hexane,
octane or dodecane; ann-alcohol, such as methanol, ethanol, octanol or glycerol; methane
or carbon dioxide.
wo 2021/260048 19 PCT/EP2021/067220
[0067] The biosynthesis may optionally be performed in the presence of an inhibitor of the
13-oxidation pathway, such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid,
salicylic acid, pentenoic acid, 2-butynoic acid, 2-octynoic acid or phenylpropionic acid, and
preferably acrylic acid.
[0068] According to one embodiment, the process for preparing the PHAs of the invention
uses microbial cells which produce PHAs via genetically modified microorganisms (GMOs).
The genetic modification may increase the production of PHA, increase the oxygen
absorption capacity, increase the resistance to the toxicity of solvents, reduce the autolysis,
modify the ratio of the PHA comonomers, and/or any combination thereof. In some of these
embodiments, the modification of the comonomer ratio of the unit (A) increases the amount
of predominant monomer versus (B) of the PHA of the invention which is obtained. In
another embodiment, the PHA-producing microbial cells reproduce naturally.
[0069] By way of example, a genetically modified microbial strain producing PHA that is
functionalizable or comprising a reactive group is Pseudomonas entomophi/a LAC23
(Biomacromolecu/es. 2014 Jun 9;15(6):2310-9. doi: 10.1021/bm500669s).
[0070] It is also possible to use genetically modified microorganisms which produce
phenylvaleric-co-3-hydroxydodecanoic copolymers (Sci. China Life Sci., Shen R., et al., 57
No. 1, (2014) with a strain: Pseudomonas entomophila LAC23.
[0071] Nutrients, such as water-soluble salts based on nitrogen, phosphorus, sulfur,
magnesium, sodium, potassium and iron, may also be used for the biosynthesis.
[0072] The known appropriate temperature, pH and dissolved oxygen (Oo) conditions may be
used for the culturing of the microorganisms.
[0073] The microorganisms may be cultured according to any known method of culturing, such
as in a bioreactor in continuous or batch mode, in fed or unfed mode.
[0074] The biosynthesis of the polymers used according to the invention is notably described
in the article "Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates
with Enriched Content of the Dominant Monomer'', Xun Juan et al., Biomacromolecu/es,
2012, 13, 2926-2932 (2012), and in patent application WO 2011/069244.
[0075] The microbial strains producing PHA which is functionalizable or comprising a reactive
group, as defined previously, are, for example, of the genus Pseudomonas such as
P. cichorii YN2, P. citronellolis, P. jessenii, and more generally with species of
Pseudomonas putida such as Pseudomonas putida GPo1 (synonym of Pseudomonas
o/eovorans), P. putida KT2442, P. putida KCTC 2407, P. putida BM01.
[0076] The carbon source(s):
[0077] One means for gaining access to the PHAs of the invention is to introduce one or more
organic compounds into the culture medium, this or these organic compounds representing
wo 2021/260048 20 PCT/EP2021/067220
a carbon source preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and a
mixture thereof.
[0078] In one embodiment, the organic compound(s) will preferably be chosen from alcohols,
carboxylic acids and a mixture thereof.
[0079] The carbon source(s) may be classified in two categories:
1) Carbon source via one or more organic compounds introduced into the medium:
One means for gaining access to the PHAs of the invention is to introduce one or more
organic compounds into the culture medium, this organic compound being a carbon source
preferably chosen from alkanes, alkenes, alcohols, carboxylic acids and mixtures thereof.
[0080] According to a particular embodiment of the invention, the organic compound(s) are
chosen from alcohols, in particular (Cs-C2o)alkanols, and/or carboxylic acids, in particular
(Cs-C2o)alkanoic acids.
[0081] The carbon source(s) may be classified in three groups:
group A: the organic compound may aid the growth of the productive strain and aid the
production of PHA structural linked to the organic compound.
group B: the organic compound may aid the growth of the strain but does not participate
in the production of PHA structural linked to the organic compound.
group C: the organic compound does not participate in the growth of the strain.
[0082] Such microbiological processes are known to those skilled in the art, notably in the
scientific literature. Mention may be made of: International Journal of Biological
Macromolecules 28, 23-29 (2000); The Journal of Microbiology, 45, No.2, 87-97, (2007).
[0083] According to one variant, the integration of the substrate that is structurally linked to the
reactive atom(s) or to the reactive group(s) of the PHAs of the invention is introduced directly
into the medium as sole carbon source in a medium suitable for microbial growth. (Example:
group A for P. putida GPo1: alkenoic acid, notably terminal).
[0084] According to another variant, the integration of the substrate that is structurally linked
to the reactive atom(s), notably halogen, or to the reactive group(s) of the PHAs of the
invention is introduced into the medium as carbon source with a second carbon source as
co-substrate which is also structurally linked to the PHA, in a medium suitable for microbial
growth. (Example: group B for P. putida GPo1: haloalkanoic acids which are preferably
terminal, such as terminal bromoalkanoic acids).
[0085] According to yet another variant, the integration of the substrate that is structurally
linked to the reactive atom(s), notably halogen, or to the reactive group(s) of the PHAs of
the invention may be introduced directly into the medium as carbon source with a second
carbon source as co-substrate which is also structurally linked to the PHAs and a third
carbon source as co-substrate which is not structurally linked to the PHAs, in a medium
suitable for microbial growth. (Example: group C glucose or sucrose).
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[0086] In one embodiment, the 13-oxidation pathway inhibitor is acrylic acid, 2-butynoic acid,
2-octynoic acid, phenylpropionic acid, propionic acid, trans-cinnamic acid, salicylic acid,
methacrylic acid, 4-pentenoic acid or 3-mercaptopropionic acid.
[0087] In one embodiment of the first aspect, the functionalized fatty acid is a functionalized
hexanoic acid, functionalized heptanoic acid, functionalized octanoic acid, functionalized
nonanoic acid, functionalized decanoic acid, functionalized undecanoic acid, functionalized
dodecanoic acid or functionalized tetradecanoic acid.
[0088] The functionalization may be introduced by means of an organic compound chosen
from precursors of the alcohol and/or carboxylic acid category, notably:
for functionalization of the PHA(s) with a branched alkyl group: see, for example Applied
and Environmental Microbiology,. 60, No. 9, 3245-325 (1994);
for functionalization of the PHA(s) with a linear alkyl group comprising a terminal
cyclohexyl unit: see, for example doi.org/10.1016/80141-8130(01)00144-1;
for functionalization of the PHA(s) with an unsaturated alkyl group which is preferably
terminal: see, for example doi.org/10.1021/bm8005616);
for functionalization of the PHA(s) with a linear alkyl group comprising a halogen
preferably at the end of the hydrocarbon-based chain (doi.org/10.1021/ma00033a002);
for functionalization of the PHA(s) with a (hetero)aromatic alkyl group, for example
phenyl, benzoyl, phenoxy, see, for example J. Microbial. Biotechnol., 11. 3,435-442
(2001);
for functionalization of the PHA(s) with a linear alkyl group comprising a heteroatom
notably at the end of the hydrocarbon-based chain, see, for example DOl
10.1007 /s00253-011-3099-4;
for functionalization of the PHA(s) with a linear alkyl group comprising a cyano function
notably at the end of the hydrocarbon-based chain, see, for example
doi.org/10.1111/j.1574-6968.1992.tb05839.x;
for functionalization of the PHA(s) with a linear alkyl group comprising an epoxy function
notably at the end of the hydrocarbon-based chain, see, for example
doi.org/1 0.1016/81381-5148(97)00024-2;
The review International Microbiology 16:1-15 (2013) doi:10.2436/20.1501.01.175) also
mentions the majority of the functionalized native PHAs.
[0089] In a particular embodiment of the invention, the fatty acid from group A is chosen from
11-undecenoic acid, 1 0-epoxyundecanoic acid, 5-phenylvaleric acid, citronellol and
5-cyanopentanoic acid.
[0090] In a particular embodiment of the invention, the fatty acid from group B is chosen from
halooctanoic acids such as 8-bromooctanoic acid.
[0091] In a particular embodiment of the invention, the carbon source from group C is a
monosaccharide, preferably glucose.
2) Carbon source in the presence of oxidation inhibitor introduced into the medium:
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[0092] Another aspect of the invention is the use of the PHA-producing microbial strains in a
medium that is suitable for microbial growth, said medium comprising: a substrate which is
structurally linked to the PHA(s); at least one carbon source which is not structurally linked
to the PHA(s); and at least one oxidation and notably 13-oxidation pathway inhibitor. This
allows the growth of the microbial cells to take place in said medium, the microbial cells
synthesizing the PHA polymer(s) of the invention; preferably copolymer particularly
containing more than 95% of identical units, which has a comonomer ratio of unit (A) and
of unit (B) which differs from that obtained in the absence of the 13-oxidation pathway
inhibitor.
b) The fatty medium
[0093] The composition comprises as second ingredient a fatty medium, which is preferably
oily.
[0094] The term "fatty medium" means that the composition of the invention comprises one or
more fatty substances. The composition may also comprise water. Preferably, the
composition of the invention predominantly comprises on a weight basis one or more fatty
substances versus the amount by weight of water.
[0095] The term "fatty substance" means an organic compound that is insoluble in water at
ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of
less than 5%, preferably 1% and even more preferentially 0.1 %). They bear in their structure
at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of
at least two siloxane groups. In addition, the fatty substances are generally soluble in
organic solvents under the same temperature and pressure conditions, for instance
chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane.
[0096] The fatty substance(s) of the invention are of natural or synthetic origin, preferably
natural, more preferentially of plant origin. These fatty substances are preferably neither
polyoxyethylenated nor polyglycerolated. They are different from fatty acids since salified
fatty acids constitute soaps which are generally soluble in aqueous media.
[0097] According to a particular embodiment of the invention, the composition comprises one
or more fatty substances that are not liquid at 25°C and at atmospheric pressure.
The wax(es)
[0098] According to a particular embodiment, the composition of the invention comprises one
or more waxes.
[0099] The term "wax'' means a lipophilic compound that is solid at room temperature (25°C),
with a reversible solid/liquid change of state, having a melting point of greater than or equal
to 30°C, which may be up to 200°C and notably up to 120°C.
wo 2021/260048 23 PCT/EP2021/067220
[00100] In particular, the wax(es) that are suitable for use in the invention may have a
melting point of greater than or equal to 45°C and in particular of greater than or equal to
55°C.
[001 01] The composition according to the invention preferably comprises a content of
wax(es) ranging from 3% to 20% by weight relative to the total weight of the composition,
in particular from 5% to 15% and more particularly from 6% to 15%.
[001 02] According to a particular form of the invention, the composition of the invention
is solid, in particular anhydrous. It may then be in stick form; use will be made of
polyethylene microwaxes in the form of crystallites with an aspect ratio at least equal to 2,
and with a melting point ranging from 70 to 11 ooc and preferably from 70 to 1 00°C, so as
to reduce or even eliminate the presence of strata in the solid composition. These
crystallites in needle form and notably the dimensions thereof may be characterized visually
according to the following method.
The pasty compound(s)
[001 03] According to a particular embodiment, the composition of the invention
comprises one or more pasty compounds.
[001 04] For the purposes of the present invention, the term "pasty compound' means a
lipophilic fatty compound that undergoes a reversible solid/liquid change of state, having
anisotropic crystal organization in the solid state, and including, at a temperature of 23°C,
a liquid fraction and a solid fraction.
The oil(s)
[00105]
[00106]
Preferably, the composition comprises one or more oils.
The term "oif' means a hydrophobic (i.e. water-immiscible) fatty (i.e. nonaqueous)
substance that is liquid at room temperature (25°C) and at atmospheric pressure
(1 atm or 760 mmHg).
[001 07] The term "liquid fatty substances" notably means liquid fatty substance(s)
preferably having a viscosity of less than or equal to 7000 centipoises at 20°C.
[001 08] The liquid fatty substance(s) of the invention more particularly have a viscosity
of less than or equal to 2 Pa.s, more particularly less than or equal to 1 Pa.s, even more
particularly less than or equal to 0.1 Pa.s, and more preferentially less than or equal to 0.09
Pa.s at a temperature of 25°C and at a shear rate of 1 s-1.
[001 09] According to a particular embodiment of the invention, the liquid fatty
substance(s) have a viscosity of between 0.001 Pa.s and 2 Pa.s, more particularly
inclusively between 0.01 and 1 Pa.s and even more particularly inclusively between 0.014
and 0.1 Pa.s, more preferentially inclusively between 0.015 and 0.09 Pa.s at a temperature
of 25°C and at a shear rate of 1 s-1.
[0011 0] The PHA copolymer(s) according to the invention are soluble in the liquid fatty
substances at 25°C and at atmospheric pressure.
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[00111] According to the invention, the medium is said to be carbon-based if it comprises
at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99%
by weight, or else from 65% to 95% by weight, or even from 70% to 90% by weight, relative
to the total weight of the carbon-based medium, of carbon-based compound, which is liquid
at 25°C.
[00112] Preferably, the liquid fatty substance(s) have an overall solubility parameter
according to the Hansen solubility space of less than or equal to 20 (MPa)112, or a mixture
of such compounds.
[00113] The global solubility parameter o according to the Hansen solubility space is
defined in the article "Solubility parameter values" by Grulke in the book "Polymer
Handbook", 3rd Edition, Chapter VII, pages 519-559, by the relationship o = (dD2 + dP2 +
dH2)112 in which:
- do characterizes the London dispersion forces derived from the formation of dipoles
induced during molecular impacts,
- dp characterizes the Debye interaction forces between permanent dipoles,
- dH characterizes the forces of specific interactions (such as hydrogen bonding, acid/base,
donor/acceptor, etc.).
[00114] The definition of solvents in the Hansen three-dimensional solubility space is
described in the article by Hansen: "The three-dimensional solubility parameters", J. Paint
Techno/. 39, 105 (1967).
[00115] Among the liquid carbon-based compounds having an overall solubility
parameter according to the Hansen solubility space of less than or equal to 20 (MPa)112,
mention may be made of liquid fatty substances, notably oils, which may be chosen from
natural or synthetic, carbon-based, or hydrocarbon-based oils, which are optionally
fluorinated, and optionally branched, alone or as a mixture.
[00116] The liquid fatty substances are notably chosen from C5-C16 hydrocarbons or
hydrocarbons comprising more than 16 carbon atoms and up to 60 carbon atoms and in
particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of
synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, and
silicones.
[00117] It is recalled that, for the purposes of the invention, the fatty alcohols, fatty esters
and fatty acids more particularly contain one or more linear or branched, saturated or
unsaturated hydrocarbon-based groups comprising 6 to 30 carbon atoms, which are
optionally substituted, in particular, with one or more (in particular 1 to 4) hydroxyl groups.
If they are unsaturated, these compounds may comprise one to three conjugated or
unconjugated carbon-carbon double bonds.
[00118] As regards the C5-C16 alkanes, they are linear or branched, and possibly cyclic.
Examples that may be mentioned include hexane, dodecane and isoparaffins such as
isohexadecane and isodecane. The linear or branched hydrocarbons containing more than
wo 2021/260048 25 PCT/EP2021/067220
16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly,
polydecenes, and hydrogenated polyisobutene.
[00119] According to a particular embodiment, the fatty substance(s) used in the
process of the invention are chosen from volatile linear alkanes.
[00120] The term "one or more volatile linear alkanes" means, without distinction, "one
or more volatile linear alkane oils".
[00121] A volatile linear alkane that is suitable for use in the invention is liquid at room
temperature (about 25°C) and atmospheric pressure (101 325 Pa or 760 mmHg).
[00122] The term "volatile linear alkane" that is suitable for use in the invention means
a linear alkane that can evaporate on contact with the skin in less than one hour, at room
temperature (25°C) and atmospheric pressure (101 325 Pa), which is liquid at room
temperature, notably having an evaporation rate ranging from 0.01 to 15 mg/cm2/minute, at
room temperature (25°C) and atmospheric pressure (1 01 325 Pa).
[00123] Preferably, the volatile linear alkanes that are suitable for use in the invention
have an evaporation rate ranging from 0.01 to 3.5 mg/cm2/minute and better still from 0.01
to 1.5 mg/cm2/minute, at room temperature (25°C) and atmospheric pressure (1 01 325 Pa).
[00125] More preferably, the volatile linear alkanes that are suitable for use in the
invention have an evaporation rate ranging from 0.01 to 0.8 mg/cm2/minute, preferentially
from 0.01 to 0.3 mg/cm2/minute and even more preferentially from 0.01 to
0.12 mg/cm2/minute, at room temperature (25°C) and atmospheric pressure (1 01 325 Pa).
[00126] The evaporation rate of a volatile alkane in accordance with the invention (and
more generally of a volatile solvent) may notably be evaluated by means of the protocol
described in WO 06/013 413, and more particularly by means of the protocol described
below.
[00127] 15 g of volatile hydrocarbon-based solvent are placed in a crystallizing dish
(diameter: 7 em) placed on a balance that is in a chamber of about 0.3 m3 with regulated
temperature (25°C) and hygrometry (50% relative humidity).
[00128] The volatile hydrocarbon-based solvent is allowed to evaporate freely, without
stirring it, while providing ventilation by means of a fan (Papst-Motoren, reference 8550 N,
rotating at 2700 rpm) placed in a vertical position above the crystallizing dish containing the
volatile hydrocarbon-based solvent, the blades being directed towards the crystallizing dish,
20 em away from the bottom of the crystallizing dish.
[00129] The mass of volatile hydrocarbon-based solvent remaining in the crystallizing
dish is measured at regular time intervals.
[00130] The evaporation profile of the solvent is then obtained by plotting the curve of
the amount of product evaporated (in mg/cm2
) as a function of the time (in min).
[00131] The evaporation rate is then calculated, which corresponds to the tangent to the
origin of the curve obtained. The evaporation rates are expressed in mg of volatile solvent
evaporated per unit area (cm2
) and per unit time (minutes).
[00132] According to a preferred embodiment, the volatile linear alkanes that are
suitable for use in the invention have a non-zero vapour pressure (also known as the
wo 2021/260048 26 PCT/EP2021/067220
saturation vapour pressure), at room temperature, in particular a vapour pressure ranging
from 0.3 Pa to 6000 Pa.
[00133] Preferably, the volatile linear alkanes that are suitable for use in the invention
have a vapour pressure ranging from 0.3 to 2000 Pa and better still from 0.3 to 1000 Pa, at
room temperature (25°C).
[00134] More preferably, the volatile linear alkanes that are suitable for use in the
invention have a vapour pressure ranging from 0.4 to 600 Pa, preferentially from 1 to 200
Pa and even more preferentially from 3 to 60 Pa, at room temperature (25°C).
[00135] According to one embodiment, a volatile linear alkane that is suitable for use in
the invention may have a flash point that is within the range from 30 to 120°C and more
particularly from 40 to 1 00°C. The flash point is in particular measured according to the
standard ISO 3679.
[00136] According to one embodiment, the volatile linear alkanes that are suitable for
use in the invention may be linear alkanes including from 7 to 15 carbon atoms, preferably
from 8 to 14 carbon atoms and better still from 9 to 14 carbon atoms.
[00137] More preferably, the volatile linear alkanes that are suitable for use in the
invention may be linear alkanes including from 10 to 14 carbon atoms and even more
preferentially from 11 to 14 carbon atoms.
A volatile linear alkane that is suitable for use in the invention may advantageously be of plant
origin.
[00138] According to a particular embodiment of the invention, the fatty medium of the
composition is oily. More particularly, the composition comprises one or more oils, preferably
non-silicone oils, notably hydrocarbon-based oils.
[00139] The term "hydrocarbon-based oif' means an oil consisting of carbon and
hydrogen atoms.
[00140] Preferably, the liquid fatty substances of the invention are chosen from
hydrocarbons, fatty alcohols, fatty esters, silicones and fatty ethers, or mixtures thereof.
More particularly, the fatty substances of the invention are not (poly)oxyalkylenated.
[00141] The term "liquid hydrocarbon" means a hydrocarbon composed solely of carbon
and hydrogen atoms, which is liquid at ordinary temperature (25°C) and at atmospheric
pressure (760 mmHg; i.e. 1.013x105 Pa).
[00142] More particularly, the liquid hydrocarbons are chosen from:
- linear or branched, optionally cyclic, C5-C16 alkanes. Examples that may be mentioned
include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance
isohexadecane, isododecane and isodecane;
- linear or branched hydrocarbons of mineral, animal or synthetic origin, containing more than
16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes
hydrogenated polyisobutene such as Parleam®, and squalane.
[00143] In a preferred variant, the liquid hydrocarbon(s) are chosen from liquid paraffins
and liquid petroleum jelly.
wo 2021/260048 27 PCT/EP2021/067220
[00144] The term "liquid fatty alcohof' means a non-glycerolated and nonoxyalkylenated
fatty alcohol that is liquid at ordinary temperature (25°C) and at atmospheric
pressure (760 mmHg; i.e. 1.013x105 Pa).
[00145] Preferably, the liquid fatty alcohols of the invention include from 8 to 30 carbon
atoms, more preferentially Cw-C22, even more preferentially C14-C2o, better still CwC1s.
[00146] The liquid fatty alcohols of the invention may be saturated or unsaturated.
[00147] The saturated liquid fatty alcohols are preferably branched. They may optionally
comprise in their structure at least one aromatic or non-aromatic ring. Preferably, they are
acyclic.
[00148] More particularly, the saturated liquid fatty alcohols of the invention are chosen
from octyldodecanol, isostearyl alcohol and 2-hexyldecanol.
[00149] According to another variant of the invention, the fatty substance(s) are chosen
from liquid unsaturated fatty alcohols. These liquid unsaturated fatty alcohols contain in their
structure at least one double or triple bond. Preferably, the fatty alcohols of the invention
bear in their structure one or more double bonds. When several double bonds are present,
there are preferably two or three of them, and they may be conjugated or non-conjugated.
[00150] These unsaturated fatty alcohols may be linear or branched.
[00151] They may optionally comprise in their structure at least one aromatic or nonaromatic
ring. Preferably, they are acyclic.
[00152] More particularly, the liquid unsaturated fatty alcohols of the invention are
chosen from oleyl alcohol, linolyl alcohol, linolenyl alcohol and undecylenyl alcohol.
[00153] Oleyl alcohol is most particularly preferred.
[00154] The term "liquid fatty ester" or "ester oif' means a compound comprising one or
more ester groups derived from a fatty acid and/or from a fatty alcohol and that is liquid at
ordinary temperature (25°C) and at atmospheric pressure (760 mmHg; i.e. 1.013x 105 Pa).
[00155] The esters are preferably liquid esters of saturated or unsaturated, linear or
branched C1-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear
or branched C1-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon
atoms in the esters being greater than or equal to 10.
[00156] Preferably, for the esters of monoalcohols, at least one from among the alcohol
and the acid from which the esters of the invention are derived is branched.
[00157] Among the monoesters of monoacids and of monoalcohols, mention may be
made of ethyl palmitate, isopropyl palmitate, alkyl myristates such as isopropyl myristate or
ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate,
isostearyl neopentanoate, and C10-C22 and preferably C12-C2o alkyl (iso)stearates such as
isopropyl isostearate.
[00158] Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and
esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C4-C26
dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
[00159] Mention may notably be made of diethyl sebacate, diisopropyl sebacate, bis(2-
ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-
wo 2021/260048 28 PCT/EP2021/067220
ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate,
triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl
citrate, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononanoate.
[00160] The composition may also comprise, as liquid fatty ester, sugar esters and
diesters of C6-C3o and preferably C12-C22 fatty acids. It is recalled that the term "sugar"
means oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions,
with or without aldehyde or ketone functions, and which include at least 4 carbon atoms.
These sugars may be monosaccharides, oligosaccharides or polysaccharides.
[00161] Examples of suitable sugars that may be mentioned include sucrose, glucose,
galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and
derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance
methylglucose.
[00162] The sugar esters of fatty acids may be notably chosen from the group
comprising the esters or mixtures of esters of sugars described previously and of linear or
branched, saturated or unsaturated C6-C3o and preferably C12-C22 fatty acids. If they are
unsaturated, these compounds may comprise one to three conjugated or unconjugated
carbon-carbon double bonds.
[00163] The esters according to this variant may also be chosen from mono-, di-, tri- and
tetraesters, polyesters, and mixtures thereof.
[00164] These esters may be, for example, oleates, laurates, palmitates, myristates,
behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or
mixtures thereof such as, notably, oleopalmitate, oleostearate and palmitostearate mixed
esters.
[00165] More particularly, use is made of monoesters and diesters and notably sucrose,
glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate,
linoleate, linolenate or oleostearate.
[00166] An example that may be mentioned is the product sold under the name
Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
[00167] Finally, use may also be made of natural or synthetic glycerol esters of mono-,
di- or triacids.
[00168]
[00169]
Among these, mention may be made of plant oils.
As oils of plant origin or synthetic triglycerides that may be used in the
composition of the invention as liquid fatty esters, examples that may be mentioned include:
- triglyceride oils of plant or synthetic origin, such as liquid fatty acid triglycerides including
from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or
alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil,
sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil,
avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company
Stearinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the
company Dynamit Nobel, jojoba oil and shea butter oil.
wo 2021/260048 29 PCT/EP2021/067220
[00170] Use will preferably be made, as esters according to the invention, of liquid fatty
esters derived from monoalcohols.
[00171]
[00172]
ether.
[00173]
Isopropyl myristate or isopropyl palmitate is preferred.
The liquid fatty ethers are chosen from liquid dialkyl ethers such as dicaprylyl
According to a preferred embodiment of the invention, the composition
comprises one or more hydrocarbon-based oils containing from 8 to 16 carbon atoms.
[00174] More particularly, the hydrocarbon-based oil(s) containing from 8 to 16 carbon
atoms are chosen from:
• branched Cs-C16 alkanes, such as Cs-C16 isoalkanes of petroleum origin (also known as
isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane),
isodecane, isohexadecane and, for example, the oils sold under the lsopar or Permethyl
trade names,
• linear Cs to C16 alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by
Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also
mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C11) and of
n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155059 from
the company Cognis, and mixtures thereof.
[00175] The ester oil(s) are particularly chosen from:
• oils of plant origin, such as triglycerides consisting of fatty acid esters of glycerol in which
the fatty acids may have varied chain lengths from c4 to c24, these chains possibly being
linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or
octanoic acid triglycerides. The oils of plant origin may be chosen from wheatgerm oil,
sunflower oil, grapeseed oil, sesame seed oil, groundnut oil, corn oil, apricot oil, castor oil,
shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil,
cottonseed oil, coconut oil, hazelnut oil, walnut oil, rice oil, linseed oil, macadamia oil, alfalfa
oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil,
evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil,
passion flower oil, musk rose oil and argan oil; shea butter; or alternatively caprylic/capric
acid triglycerides such as those sold by the company Stearinerie Dubois or those sold under
the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
• monoester oils of formula R9-C(O)-OR10 in which R9 represents a linear or branched
hydrocarbon-based chain including from 5 to 19 carbon atoms and R10 represents a linear
or branched, notably branched, hydrocarbon-based chain containing from 4 to 20 carbon
atoms, on condition that R9 + R10 :2: 9 carbon atoms and preferably less than 29 carbon
atoms, for instance palmitates, adipates, myristates and benzoates, notably diisopropyl
adipate and isopropyl myristate; cetearyl octanoate (purcellin oil), isopropyl myristate,
isopropyl palmitate, hexyllaurate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl
wo 2021/260048 30 PCT/EP2021/067220
isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate,
2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate or
cetyl octanoate;
• esters of lactic acid and of Cw-C2o alcohol, such as isostearyl lactate, 2-octyldodecyl
lactate, myristyl lactate, C12-C13 alkyl lactate (Cosmacol® Eli from Sasol), cetyl lactate or
lauryl lactate;
• diesters of malic acid and of Cw-C2o alcohol, such as diisostearyl malate, di(C12-C13 alkyl)
malate (Cosmacol® EMI from Sasol), dibutyloctyl malate, diethylhexyl malate or
dioctyldodecyl malate;
• esters of pentaerythritol and of Cs-C22 carboxylic acid (in particular tetraesters or
diesters), such as pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate,
pentaerythrityl tetrabehenate, pentaerythrityl tetracaprylate/tetracaprate, pentaerythrityl
tetracocoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisononanoate,
pentaerythrityl tetrastearate, pentaerythityl tetraisostearate, pentaerythrityl tetralaurate,
pentaerythrityl tetramyristate, pentaerythrityl tetraoleate or pentaerythrityl distearate;
• diesters of formula R11-0-C(=O)-R12-C(=O)-O-R13, with R11 and R13, which may be
identical or different, representing a linear or branched, saturated or unsaturated (preferably
saturated) C4 to C12 and preferentially Cs to C10 alkyl chain, optionally containing at least
one saturated or unsaturated, preferably saturated, ring, and R12 representing a saturated
or unsaturated C1 to C4, preferably C2 to C4, alkylene chain, for instance an alkylene chain
derived from succinate (in this case R12 is a saturated C2 alkylene chain), maleate (in this
case R12 is an unsaturated C2 alkylene chain), glutarate (in this case R12 is a saturated C3
alkylene chain) or adipate (in this case R12 is a saturated C4 alkylene chain); in particular,
R11 and R13 are chosen from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl,
2-ethylhexyl, cetyl, nonyl and isononyl; mention may be made preferentially of dicaprylyl
maleate or bis(2-ethylhexyl) succinate;
• diesters of formula R14-C(=O)-O-R15-0-C(=O)-R16, with R14 and R16, which may be
identical or different, representing a linear or branched, saturated or unsaturated (preferably
saturated) C4 to C12 and preferentially Cs to C10 alkyl chain and R15 representing a saturated
or unsaturated C1 to C4 and preferably C2 to C4 alkylene chain. Mention may notably be
made of 1 ,3-propanediol dicaprylate (R14 as C1 and R16 as C3), sold under the name Dub
Zenoat by the company Stearinierie Dubois, or dipropylene glycol dicaprylate;
• the carbonate oils may be chosen from the carbonates of the following formula R17-0-
C(O)-O-R18, with R17 and R18, which may be identical or different, representing a linear or
branched c4 to c12 and preferentially c6 to c10 alkyl chain; the carbonate oils may be
dicaprylyl carbonate (or dioctyl carbonate), sold under the name Cetiol CC® by the
company BASF, bis(2-ethylhexyl) carbonate, sold under the name Tegosoft DEC® by the
company Evonik, dipropylheptyl carbonate (Cetiol 4 All from BASF), dibutyl carbonate,
wo 2021/260048 31 PCT/EP2021/067220
dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl carbonate,
diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate.
[00176] In particular, the fatty substance(s) b) are chosen from:
- plant oils formed by fatty acid esters of polyols, in particular triglycerides, such as sunflower
oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, beauty-leaf oil,
palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil,
olive oil or cereal germ oil;
-linear, branched or cyclic esters containing more than 6 carbon atoms, notably 6 to 30 carbon
atoms; and notably isononyl isononanoate; and more particularly esters of formula R-C(0)-
0-R' in which R represents a higher fatty acid residue including from 7 to 19 carbon atoms
and R' represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such
as palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and
isopropyl myristate;
-hydrocarbons and notably volatile or non-volatile, linear, branched and/or cyclic alkanes, such
as Cs-C6o isoparaffins, which are optionally volatile, such as isododecane, Parleam
(hydrogenated polyisobutene), isohexadecane, cyclohexane or lsopars; or else liquid
paraffins, liquid petroleum jelly, or hydrogenated polyisobutylene;
-ethers containing 6 to 30 carbon atoms;
- ketones containing 6 to 30 carbon atoms;
- aliphatic fatty monoalcohols containing 6 to 30 carbon atoms, the hydrocarbon-based chain
not including any substitution groups, such as oleyl alcohol, decanol, dodecanol,
octadecanol, octyldodecanol and linoleyl alcohol;
- polyols containing 6 to 30 carbon atoms, such as hexylene glycol; and
- mixtures thereof.
[00177] Preferably, the composition comprises, in the fatty medium, at least one oil
chosen from:
- plant oils formed by fatty acid esters of polyols, in particular triglycerides,
- esters of formula RCOOR' in which R represents a higher fatty acid residue including from 7
to 19 carbon atoms and R' represents a hydrocarbon-based chain including from 3 to 20
carbon atoms,
- volatile or non-volatile, linear or branched Cs-C3o alkanes,
- volatile or non-volatile, non-aromatic cyclic Cs-C12 alkanes,
-ethers containing 7 to 30 carbon atoms,
- ketones containing 8 to 30 carbon atoms,
-aliphatic fatty monoalcohols containing 12 to 30 carbon atoms, the hydrocarbon-based chain
not including any substitution groups, and
- mixtures thereof.
wo 2021/260048 32 PCT/EP2021/067220
[00178] Preferably, when the copolymer is such that the alkyl group R1 comprises from
6 to 9 carbon atoms, the fatty substance(s) b) are chosen from apolar hydrocarbon-based
oils containing from 8 to 14 carbon atoms in the absence of monoalcohol containing from 2
to 6 carbon atoms.
[00179] Preferably, when the copolymer is such that the alkyl group R1 comprises 9
carbon atoms, the fatty substance(s) b) are chosen from hydrogenated polyisobutylenes.
[00180] In particular, the fatty substance(s) are chosen from non-silicone oils;
preferably, the liquid fatty substance(s) are chosen from:
ester oils, carbonate oils; and
branched apolar hydrocarbon-based oils containing from 8 to 14 carbon atoms;
as a mixture with
a monoalcohol containing from 2 to 6 carbon atoms preferably in a monoalcohol/branched
apolar hydrocarbon-based oil weight ratio ranging from 1/99 to 10/90.
[00181] Advantageously, the composition comprises one or more fatty substances,
which are notably liquid at 25°C and at atmospheric pressure, preferably one or more oils,
of the fatty medium in a content ranging from 2% to 99.9% by weight, relative to the total
weight of the composition, preferably ranging from 5% to 90% by weight, preferably ranging
from 10% to 80% by weight, preferably ranging from 20% to 80% by weight.
[00182] Advantageously, the composition according to the invention comprises a
physiologically acceptable medium. In particular, the composition is a cosmetic
composition.
[00183] The term "physiologically acceptable medium" means a medium that is
compatible with human keratin materials, for instance the skin, the lips, the nails, the
eyelashes, the eyebrows or the hair.
[00184] The term "cosmetic composition" means a composition that is compatible with
keratin materials, which has a pleasant colour, odour and feel and which does not cause
any unacceptable discomfort (stinging, tautness or redness) liable to discourage the
consumer from using it.
[00185] The term "keratin materials" means the skin (body, face, contour of the eyes,
scalp), head hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips.
[00186] According to one embodiment of the invention, the composition comprises an
aqueous phase. The composition is notably formulated as aqueous lotions or as water-inoil
or oil-in-water emulsions or as multiple emulsions (oil-in-water-in-oil or water-in-oil-inwater
triple emulsion (such emulsions are known and described, for example, by C. Fox in
"Cosmetics and Toiletries"- November 1986- Vol. 101 -pages 101-112)).
[00187] The aqueous phase of the composition contains water and in general other
water-soluble or water-miscible solvents such as polar and protic solvents as defined below
(see additional solvents).
wo 2021/260048 33 PCT/EP2021/067220
[00188] The composition according to the invention preferably has a pH ranging from 3
to 9, depending on the support chosen.
[00189] According to a particular embodiment of the invention, the pH of the
composition(s) is neutral or even slightly acidic. Preferably, the pH of the composition is
between 6 and 7. The pH of these compositions may be adjusted to the desired value by
means of acidifying or basifying agents usually used in cosmetics, or alternatively using
standard buffer systems.
[00190] The term "basifying agenf' or "base" means any agent for increasing the pH of
the composition in which it is present. The basifying agent is a Brrzmsted, Lowry or Lewis
base. It may be mineral or organic. Particularly, said agent is chosen from a) aqueous
ammonia, b) (bi)carbonate, c) alkanolamines such as monoethanolamine, diethanolamine,
triethanolamine and derivatives thereof, d) oxyethylenated and/or oxypropylenated
ethylenediamines, e) organic amines, f) mineral or organic hydroxides, g) alkali metal
silicates such as sodium metasilicates, h) amino acids, preferably basic amino acids such
as arginine, lysine, ornithine, citrulline and histidine, and i) the compounds of formula (E)
below:
[00191] [Chem. 10]:
in which formula (E):
/~
-N
.......
Rt {E)
D W is a divalent C1-C6 alkylene radical optionally substituted with one or more
hydroxyl groups or a C1-C6 alkyl radical, and/or optionally interrupted with one or more
heteroatoms such as 0 or NRu;
D Rx, Ry, Rz, Rt and Ru, which may be identical or different, represent a hydrogen
atom or a C1-C6 alkyl, C1-C6 hydroxyalkyl or C1-C6 aminoalkyl radical.
[00192] Examples of amines of formula (E) that may be mentioned include 1 ,3-
diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.
[00193] The term "alkanolamine" means an organic amine comprising a primary,
secondary or tertiary amine function, and one or more linear or branched C1-Cs alkyl groups
bearing one or more hydroxyl radicals.
[00194] Among the mineral or organic hydroxides, mention may be made of those
chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for
instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, d)
hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium
hydroxide. The mineral or organic hydroxides a) and b) are preferred.
[00195] Among the acidifying agents for the compositions used in the invention,
examples that may be mentioned include mineral or organic acids, for instance hydrochloric
wo 2021/260048 34 PCT/EP2021/067220
acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric
acid, citric acid or lactic acid, or sulfonic acids.
[00196] The basifying agents and the acidifying agents as defined previously preferably
represent from 0.001% to 20% by weight relative to the weight of the composition containing
them and more particularly from 0.005% to 8% by weight of the composition.
[00197] According to a preferred embodiment of the invention, the composition
comprises an amount of water of less than or equal to 10% by weight relative to the total
weight of the composition. Even more preferentially, the composition comprises an amount
of water of less than or equal to 5%, better still less than 2%, even better still less than 0.5%,
and is notably free of water. Where appropriate, such small amounts of water may notably
be introduced by ingredients of the composition that may contain residual amounts thereof.
[00198] Even more preferentially, the composition does not comprise any water.
[00199] The composition according to the invention may comprise a cosmetic additive
chosen from water, fragrances, preserving agents, fillers, colouring agents, UV-screening
agents, surfactants, moisturizers, vitamins, ceramides, antioxidants, free-radical
scavengers, polymers and thickeners.
[00200] According to a particular embodiment of the invention, the composition also
comprises one or more colouring agents chosen from pigments, direct dyes and mixtures
thereof, preferably pigments.
[00201] The term "pigment' refers to any pigment, of synthetic or natural origin, which
gives colour to keratin materials. The solubility of the pigments in water at 25°C and at
atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than
0.01%.
[00202] They are white or coloured solid particles which are naturally insoluble in the
hydrophilic and lipophilic liquid phases usually employed in cosmetics or which are rendered
insoluble by formulation in the form of a lake, where appropriate. More particularly, the
pigments have little or no solubility in aqueous-alcoholic media.
[00203] The pigments that may be used are notably chosen from the organic and/or
mineral pigments known in the art, notably those described in Kirk-Othmer's Encyclopedia
of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry. Pigments
that may notably be mentioned include organic and mineral pigments such as those defined
and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigments, Organic", 2005
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid,
"Pigments, Inorganic, 1. General" 2009 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim10.1002/14356007.a20_243.pub3.
[00204] These pigments may be in pigment powder or paste form. They may be coated
or uncoated.
wo 2021/260048 35 PCT/EP2021/067220
[00205] The pigments may be chosen, for example, from mineral pigments, organic
pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures
thereof.
[00206] The pigment may be a mineral pigment. The term "mineral pigment" refers to
any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on
inorganic pigments. Among the mineral pigments that are useful in the present invention,
mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue,
chromium hydrate, ferric blue and titanium oxide.
[00207] The pigment may be an organic pigment. The term "organic pigment" refers to
any pigment that satisfies the definition in Ullmann's encyclopaedia in the chapter on
organic pigments. The organic pigment may notably be chosen from nitroso, nitro, azo,
xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone,
isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine,
triphenylmethane and quinophthalone compounds.
[00208] In particular, the white or coloured organic pigments may be chosen from
carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue,
sorghum red, the blue pigments codified in the Color Index under the references Cl 42090,
69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under
the references Cl11680, 11710,15985,19140,20040,21100,21108,47000,47005, the
green pigments codified in the Color Index under the references Cl 61565, 61570, 74260,
the orange pigments codified in the Color Index under the references Cl 11725, 15510,
45370, 71105, the red pigments codified in the Color Index under the references Cl 12085,
12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865,
15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained
by oxidative polymerization of indole or phenolic derivatives as described in patent FR 2
679 771.
[00209] According to a particular embodiment of the invention, the pigment(s) used are
pigment pastes of organic pigments such as the products sold by the company Hoechst
under the name: Cosmenyl Yellow lOG: Yellow 3 pigment (CI 11710); Cosmenyl G yellow:
Yellow 1 pigment (CI 11680); Cosmenyl GR orange: Orange 43 pigment (CI 71105);
Cosmenyl R red: Red 4 pigment (CI 12085); Cosmenyl FB carmine: Red 5 pigment (CI
12490); Cosmenyl RL violet: Violet23 pigment (CI51319); Cosmenyl A2R blue: Blue 15.1
pigment (CI 74160); Cosmenyl GG green: Green 7 pigment (CI 74260); Cosmenyl R black:
Black 7 pigment (CI 77266).
[00210] The pigments in accordance with the invention may also be in the form of
composite pigments, as described in patent EP 1 184 426. These composite pigments may
be composed notably of particles including:
a mineral core,
at least one binder for fixing the organic pigments to the core, and
wo 2021/260048 36 PCT/EP2021/067220
at least one organic pigment at least partially covering the core.
[00211] The term "lake" refers to dyes adsorbed onto insoluble particles, the assembly
thus obtained remaining insoluble during use. The mineral substrates onto which the dyes
are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium
aluminium borosilicate and aluminium. Among the organic dyes, mention may be made of
cochineal carmine.
[00212] Examples of lakes that may be mentioned include the products known under
the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red
27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI
15 850:1), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI19 140),
D & C Yellow 6 (CI 15 985), D & C Green 5 (CI 61 570), D & C Yellow 10 (CI 77 002), D &
C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).
[00213] The mineral substrates onto which the dyes are adsorbed are, for example,
alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and
aluminium.
[00214] Among the dyes, mention may be made of cochineal carmine. Mention may also
be made of the dyes known under the following names: D & C Red 21 (CI 45 380), D & C
Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red
3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19
140), D & C Yellow 6 (CI 15 985), D & C Green 5 (CI 61 570), D & C Yellow 10 (CI 77 002),
D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).
[00215] An example of a lake that may be mentioned is the product known under the
following name: D&C Red 7 (CI 15 850:1).
[00216]
[00217]
The pigment(s) may also be pigments with special effects.
The term "pigments with special effects" refers to pigments that generally create
a coloured appearance (characterized by a certain shade, a certain vivacity and a certain
level of luminance) that is non-uniform and that changes as a function of the conditions of
observation (light, temperature, angles of observation, etc.). They thereby differ from
coloured pigments, which afford a standard uniform opaque, semi-transparent or
transparent shade.
[00218] Several types of pigments with special effects exist: those with a low refractive
index, such as fluorescent, photochromic or thermochromic pigments, and those with a
higher refractive index, such as nacres or glitter flakes.
[00219] Examples of pigments with special effects that may be mentioned include
nacreous pigments such as titanium mica coated with an iron oxide, mica coated with an
iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium
oxide, titanium mica coated with an organic dye notably of the abovementioned type, and
also nacreous pigments based on bismuth oxychloride. They may also be mica particles, at
wo 2021/260048 37 PCT/EP2021/067220
the surface of which are superposed at least two successive layers of metal oxides and/or
of organic dyestuffs.
[00220] The nacres may more particularly have a yellow, pink, red, bronze, orange,
brown, gold and/or coppery colour or tint.
[00221] As illustrations of nacres that may be used in the context of the present
invention, mention may notably be made of the gold-coloured nacres sold notably by the
company Engelhard under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold
4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by
the company Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353)
(Colorona), by the company Eckart under the name Prestige Bronze and by the company
Engelhard under the name Super bronze (Cloisonne); the orange nacres sold notably by
the company Engelhard under the names Orange 363C (Cloisonne) and Orange MCR 101
(Cosmica) and by the company Merck under the names Passion orange (Colorona) and
Matte orange (17449) (Microna); the brown-tinted nacres sold notably by the company
Engelhard under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509
(Chromalite); the nacres with a copper tint sold notably by the company Engelhard under
the name Copper 340A (Timica) and by the company Eckart under the name Prestige
Copper; the nacres with a red tint sold notably by the company Merck under the name
Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company
Engelhard under the name Yellow (4502) (Chromalite); the red-coloured nacres with a
golden tint sold notably by the company Engelhard under the name Sunstone G012
(Gemtone); the black nacres with a golden tint sold notably by the company Engelhard
under the name Nu-antique bronze 240 AB (Timica); the blue nacres sold notably by the
company Merck under the names Matte blue (17433) (Microna), Dark Blue (117324)
(Colorona); the white nacres with a silvery tint sold notably by the company Merck under
the name Xirona Silver; and the golden-green pinkish-orange nacres sold notably by the
company Merck under the name Indian summer (Xirona), and mixtures thereof.
[00222] In addition to nacres on a mica support, multilayer pigments based on synthetic
substrates such as alumina, silica, sodium calcium borosilicate or calcium aluminium
borosilicate, and aluminium, may be envisaged.
[00223] Mention may also be made of pigments with an interference effect which are
not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or
interference holographic glitter flakes (Geometric Pigments or Spectra fix from Spectratek).
Pigments with special effects also comprise fluorescent pigments, whether these are
substances that are fluorescent in daylight or that produce an ultraviolet fluorescence,
phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum
dots, sold, for example, by the company Quantum Dots Corporation.
wo 2021/260048 38 PCT/EP2021/067220
[00224] The variety of pigments that may be used in the present invention makes it
possible to obtain a wide range of colours, and also particular optical effects such as metallic
effects or interference effects.
[00225] The size of the pigment used in the cosmetic composition according to the
present invention is generally between 10 nm and 200 IJm, preferably between 20 nm and
80 1-1m and more preferentially between 30 nm and 50 IJm.
[00226]
[00227]
The pigments may be dispersed in the product by means of a dispersant.
The term "dispersant' refers to a compound which can protect the dispersed
particles from agglomerating or flocculating. This dispersant may be a surfactant, an
oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with
strong affinity for the surface of the particles to be dispersed. In particular, they may become
physically or chemically attached to the surface of the pigments. These dispersants also
contain at least one functional group that is compatible with or soluble in the continuous
medium. Said agent may be charged: it may be anionic, cationic, zwitterionic or neutral.
[00228] According to a particular embodiment of the invention, the dispersants used are
chosen from 12-hydroxystearic acid esters, more particularly, and from Cs to C2o fatty acid
esters of polyols such as glycerol or diglycerol, such as poly(12-hydroxystearic acid)
stearate with a molecular weight of approximately 750 g/mol, such as the product sold under
the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate
(CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or
polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the
company Uniqema, and mixtures thereof.
[00229] As other dispersants that may be used in the compositions of the invention,
mention may be made of quaternary ammonium derivatives of polycondensed fatty acids,
for instance Solsperse 17 000 sold by the company Avecia, and
polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow
Corning under the references DC2-5185 and DC2-5225 C.
[00230] The pigments used in the cosmetic composition according to the invention may
be surface-treated with an organic agent.
[00231] Thus, the pigments that have been surface-treated beforehand, which are
useful in the context of the invention, are pigments that have totally or partially undergone
a surface treatment of chemical, electronic, electrochemical, mechanochemical or
mechanical nature, with an organic agent such as those described notably in Cosmetics
and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the
composition in accordance with the invention. These organic agents may be chosen, for
example, from amino acids; waxes, for example carnauba wax and beeswax; fatty acids,
fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl
alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants;
wo 2021/260048 39 PCT/EP2021/067220
lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty
acids, for example aluminium stearate or laurate; metal alkoxides; polysaccharides, for
example chitosan, cellulose and derivatives thereof; polyethylene; (meth)acrylic polymers,
for example polymethyl methacrylates; polymers and copolymers containing acrylate units;
proteins; alkanolamines; silicone compounds, for example silicones, polydimethylsiloxanes,
alkoxysilanes, alkylsilanes and siloxysilicates; organofluorine compounds, for example
perfluoroalkyl ethers; fluorosilicone compounds.
[00232] The surface-treated pigments that are useful in the cosmetic composition
according to the invention may also have been treated with a mixture of these compounds
and/or may have undergone several surface treatments.
[00233] The surface-treated pigments that are useful in the context of the present
invention may be prepared according to surface-treatment techniques that are well known
to those skilled in the art, or may be commercially available as is.
[00234]
[00235]
Preferably, the surface-treated pigments are coated with an organic layer.
The organic agent with which the pigments are treated may be deposited on the
pigments by evaporation of solvent, chemical reaction between the molecules of the surface
agent or creation of a covalent bond between the surface agent and the pigments.
[00236] The surface treatment may thus be performed, for example, by chemical
reaction of a surface agent with the surface of the pigments and creation of a covalent bond
between the surface agent and the pigments or the fillers. This method is notably described
in patent US 4 578 266.

Claims
[Claim 1] Composition, notably a cosmetic composition, comprising:
a) one or more polyhydroxyalkanoate (PHA) copolymers which contain, and preferably
consist of, at least two different repeating polymer units chosen from the units (A) and (B)
below, and also the optical or geometrical isomers thereof and the solvates thereof such as
hydrates:
-[-O-CH(R1)-CH2-C(O)-]- unit (A)
-[-O-CH(R2)-CH2-C(O)-]- unit (B)
in which polymer units (A) and (B):
R1 represents a hydrocarbon-based chain chosen from: i) branched (Cs-Cg)alkyl, ii) (C10-
C3o)alkyl; iii) linear or branched (Cs-C3o)alkenyl; iv) linear or branched (Cs-C3o)alkynyl;
v) (hetero)aryl; vi) (hetero)cycloalkyl; preferably the group i) (Cw-C2o)alkyl, or iii) (Cs-
C2o)alkenyl;
R2 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated
hydrocarbon-based group, comprising from 1 to 30 carbon atoms;
and
b) a fatty medium comprising one or more fatty substances; preferably, the fatty
substance(s) are liquid at 25°C and at atmospheric pressure;
it being understood that (A) is different from (B).
[Claim 2] Composition according to Claim 1, in which the PHA copolymer(s) contain the
repeating unit of formula (1), and also the optical or geometrical isomers thereof and
the solvates thereof such as hydrates:
(I)
in which formula (1):
o R1 and R2 are as defined in the preceding claim;
D m and n are integers greater than or equal to 1; preferably, the sum n + m is inclusively
between 450 and 1400;
preferably, m > n when R1 and R2 represent an alkyl group- more preferentially, when
R1 and R2 are alkyl, then R1 is a Cs-C13 alkyl group; and R2 represents a linear alkyl
group with a carbon number corresponding to the carbon number of R1 from which two
carbon atoms are subtracted; and
preferably, m < n when R1 represents an alkenyl or alkyl group, and R2 represents an
alkyl group.
wo 2021/260048 64 PCT/EP2021/067220
[Claim 3] Composition according to Claim 1, in which the PHA copolymer(s) a) contain
three different repeating polymer units (A), (B) and (C), and preferably consist of three
different polymer units (A), (B) and (C), below, and also the optical or geometrical
isomers thereof and the solvates thereof such as hydrates:
-[-O-CH(R1)-CH2-C(O)-]-
-[-O-CH(R2)-CH2-C(O)-]-
-[-O-CH(R3)-CH2-C(O)-]-
in which polymer units (A), (B) and (C):
R1 and R2 are as defined in Claim 1;
unit (A)
unit (B)
unit (C)
R3 represents a cyclic or non-cyclic, linear or branched, saturated or unsaturated
hydrocarbon-based group comprising from 1 to 30 carbon atoms, and in particular
represents a hydrocarbon-based group chosen from linear or branched (C1-C2s)alkyl
and linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbon-based group,
more particularly (C4-C2o)alkenyl; preferably, the hydrocarbon-based group has a
carbon number corresponding to the number of carbon atoms of the radical R1, or else
corresponding to the number of carbon atoms of the radical R1 from which at least three
carbon atoms are subtracted, preferably corresponding to the number of carbon atoms
of the radical R1 from which four carbon atoms are subtracted; and
it being understood that:
(A) is different from (B) and (C), (B) is different from (A) and (C), and (C) is different
from (A) and (B); and
preferably, when R1
, R2 and R3 represent an alkyl group, the molar percentage of units
(A) is greater than the molar percentage of units (B), and greater than the molar
percentage of units (C)- more preferentially, when R1, R2 and R3 are alkyl, then R1 is a
Cs-C13 alkyl group; and R2 represents an alkyl group with a carbon number
corresponding to the carbon number of R1 from which two carbon atoms are subtracted,
and R3 represents an alkyl group with a carbon number corresponding to the carbon
number of R1 from which four carbon atoms are subtracted; and
preferably, when R1 represents an alkenyl or alkynyl group, then the molar percentage
of units (A) is less than the molar percentage of units (B) and less than the molar
percentage of units (C) notably if R2 represents an alkyl group and/or R3 represent an
alkyl group, preferably R3 represents an alkyl group with a carbon number
corresponding to the carbon number of R2 from which two carbon atoms are subtracted;
more preferentially, the PHA copolymer(s) comprise the repeating unit of formula (II),
and also the optical or geometrical isomers thereof, the organic or mineral acid or base
salts thereof, and the solvates thereof such as hydrates:
wo 2021/260048 65 PCT/EP2021/067220
in which formula (II):
o R1
, R2 and R3 are as defined previously;
D m, n and p are integers greater than or equal to 1; preferably, the sum n + m + p is
inclusively between 450 and 1400;
preferably, m > n + p when R1
, R2 and R3 represent an unsubstituted and uninterrupted
alkyl group- more preferentially, when R1
, R2 and R3 are alkyl, then R1 is a Cs-C13 alkyl
group; and R2 represents an alkyl group with a carbon number corresponding to the
carbon number of R1 from which two carbon atoms are subtracted, and R3 represents
an alkyl group with a carbon number corresponding to the carbon number of R1 from
which four carbon atoms are subtracted; and
preferably, m < n + p when R1 represents an alkenyl or alkynyl group, R2 and R3
represent an alkyl group, preferably R3 represents an alkyl group with a carbon number
corresponding to the carbon number of R2 from which two carbon atoms are subtracted.
[Claim 4] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) contain four different repeating polymer units (A), (B), (C) and (D), and
preferably consist of four different polymer units (A), (B), (C) and (D), below, and also
the optical or geometrical isomers thereof, the organic or mineral acid or base salts
thereof, and also the solvates thereof such as hydrates:
-[-O-CH(R1)-CH2-C(O)-]- unit (A)
-[-O-CH(R2)-CH2-C(O)-]- unit (B)
-[-O-CH(R3)-CH2-C(O)-]- unit (C)
-[-O-CH(R4)-CH2-C(O)-]- unit (D)
in which polymer units (A), (B), (C) and (D):
R1
, R2 and R3 are as defined in claims 1 and 3;
R4 represents a cyclic or non-cyclic, linear or branched saturated hydrocarbon-based
group comprising from 3 to 30 carbon atoms; in particular represents a hydrocarbonbased
group chosen from linear or branched (C4-C2s)alkyl; and
it being understood that:
(A) is different from (B), (C) and (D), (B) is different from (A), (C) and (D), (C) is different
from (A), (B) and (D), and (D) is different from (A), (B) and (C);
preferably, when R1
, R2
, R3 and R4 represent an alkyl group, the molar percentage of
units (A) is greater than the molar percentage of units (B), greater than the molar
percentage of units (C), and greater than the molar percentage of units (D) - more
preferentially, when R1, R2, R3 and R4 are alkyl, then R1 is a Cs-C13 alkyl group; and R2
wo 2021/260048 66 PCT/EP2021/067220
represents an alkyl group with a carbon number corresponding to the carbon number of
R1 from which two carbon atoms are subtracted, and R3 represents an alkyl group with
a carbon number corresponding to the carbon number of R1 from which four carbon
atoms are subtracted, and R4 represents an alkyl group with a carbon number
corresponding to the carbon number of R1 from which six carbon atoms are subtracted;
and
preferably, when R1 represents an alkenyl or alkynyl group, then the molar percentage
of units (A) is less than the molar percentage of units (B), and is less than the molar
percentage of units (C), notably if R2 represents an alkyl group and/or R3 represents an
alkyl group, and R4 represents an alkenyl or alkynyl group, preferably R3 represents an
alkyl group with a carbon number corresponding to the carbon number of R2 from which
two carbon atoms are subtracted, and R4 represents an alkenyl or alkynyl group with a
carbon number corresponding to the carbon number of R1 from which two carbon atoms
are subtracted;
more preferentially, the PHA copolymer(s) comprise the repeating unit of formula (Ill),
and also the optical or geometrical isomers thereof, the organic or mineral acid or base
salts thereof, and the solvates thereof such as hydrates:
{Ill) in
which formula (Ill):
o R1
, R2
, R3 and R4 are as defined previously;
m, n, p and v are integers greater than or equal to 1; preferably, the sum n + m + p + v
is inclusively between 450 and 1400;
preferably, when R1
, R2
, R3 and R4 represent an alkyl group, then m > n + p + q- more
preferentially, when R1
, R2
, R3 and R4 are alkyl, then R1 is a Cs-C13 alkyl group; and R2
represents a linear alkyl group with a carbon number corresponding to the carbon
number of R1 from which two carbon atoms are subtracted, R3 represents a linear alkyl
group with a carbon number corresponding to the carbon number of R1 from which four
carbon atoms are subtracted, and R4 represents a linear alkyl group with a carbon
number corresponding to the carbon number of R1 from which six carbon atoms are
subtracted; and
preferably, when R1 represents an alkenyl or alkynyl group, R2 and R3 represent an alkyl
group, and R4 represents an alkenyl or alkynyl group, then n > m + v; more preferentially
n + p > m + v; preferably, R3 represents an alkyl group with a carbon number
corresponding to the carbon number of R2 from which two carbon atoms are subtracted,
wo 2021/260048 67 PCT/EP2021/067220
and R4 represents an alkenyl or alkynyl group with a carbon number corresponding to
the carbon number of R1 from which two carbon atoms are subtracted.
[Claim 5] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) contain five different repeating polymer units (A), (B), (C), (D) and (E),
and preferably consist of five different polymer units (A), (B), (C), (D) and (E), below,
and also the optical or geometrical isomers thereof, the organic or mineral acid or base
salts thereof, and also the solvates thereof such as hydrates:
-[-O-CH(R1)-CH2-C(O)-]- unit (A)
-[-O-CH(R2)-CH2-C(O)-]- unit (B)
-[-O-CH(R3)-CH2-C(O)-]- unit (C)
-[-O-CH(R4)-CH2-C(O)-]- unit (D)
-[-O-CH(R5)-CH2-C(O)-]- unit (E)
in which polymer units (A), (B), (C), (D) and (E):
R1
, R2 and R3 are as defined in claims 1 and 3 to 5;
R4 represents a cyclic or non-cyclic, linear or branched saturated hydrocarbon-based
group comprising from 3 to 30 carbon atoms, and in particular represents a
hydrocarbon-based group chosen from linear or branched (C4-C2s)alkyl; and
R5 represents a cyclic or non-cyclic, linear or branched, saturated hydrocarbon-based
group comprising from 3 to 30 carbon atoms, and in particular represents a
hydrocarbon-based group chosen from linear or branched (C4-C2s)alkyl; preferably, the
hydrocarbon-based group has a carbon number corresponding to the number of carbon
atoms of the radical R4 from which at least one carbon atom is subtracted, preferably
corresponding to the number of carbon atoms of the radical R4 from which at least two
carbon atoms are subtracted, preferably from which two carbon atoms are subtracted;
it being understood that:
(A) is different from (B), (C), (D) and (E); (B) is different from (A), (C), (D) and (E); (C)
is different from (A), (B), (D) and (E); (D) is different from (A), (B), (C) and (E); and (E)
is different from (A), (B), (C) and (D);
preferably, when R1
, R2
, R3
, R4 and R5 represent an alkyl group, the molar percentage
of units (A) is greater than the molar percentage of units (B), greater than the molar
percentage of units (C), greater than the molar percentage of units (D) and greater than
the molar percentage of units (E)- more preferentially, when R1, R2, R3, R4 and R5 are
alkyl, then R1 is a Cs-C13 alkyl group; and R2 represents an alkyl group with a carbon
number corresponding to the carbon number of R1 from which two carbon atoms are
subtracted, R3 represents an alkyl group with a carbon number corresponding to the
carbon number of R1 from which four carbon atoms are subtracted, R4 represents an
alkyl group with a carbon number corresponding to the carbon number of R1 from which
six carbon atoms are subtracted, and R5 represents an alkyl group with a carbon number
corresponding to the carbon number of R1 from which eight carbon atoms are
subtracted, and
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preferably, when R1 represents an alkenyl or alkynyl group, then the molar percentage
of units (A) is less than the molar percentage of units (B), and is less than the molar
percentage of units (C), notably if R2 represents an alkyl group and R3 represents an
alkyl group, and R4 and R5 represent an alkenyl or alkynyl group, preferably R3
represents an alkyl group with a carbon number corresponding to the carbon number of
R2 from which two carbon atoms are subtracted, and R4 represents an alkenyl or alkynyl
group with a carbon number corresponding to the carbon number of R1 from which two
carbon atoms are subtracted, and R5 represents an alkenyl or alkynyl group with a
carbon number corresponding to the carbon number of R1 from which four carbon atoms
are subtracted;
more preferentially, the PHA copolymer(s) comprise the repeating unit of formula (IV),
and also the optical or geometrical isomers thereof, the organic or mineral acid or base
salts thereof, and the solvates thereof such as hydrates:
(IV)
in which formula (IV):
o R1
, R2
, R3
, R4 and R5 are as defined previously;
D m, n, p, v and z are integers greater than or equal to 1; preferably, the sum n + m + p
+ v + z is inclusively between 450 and 1400;
preferably, when R1
, R2
, R3
, R4 and R5 represent an alkyl group, then m > n + p + v + z;
preferably, when R1 represents an alkenyl or alkynyl group, R2 and R3 represent an alkyl
group and the groups R4 and R5 represent an alkenyl or alkynyl group, then n > m + v +
z; more preferentially n + p > m + v + z; preferably, R3 represents an alkyl group with a
carbon number corresponding to the carbon number of R2 from which two carbon atoms
are subtracted, and R4 represents an alkenyl or alkynyl group with a carbon number
corresponding to the carbon number of R1 from which two carbon atoms are subtracted,
and R5 represents an alkenyl or alkynyl group with a carbon number corresponding to
the carbon number of R1 from which four carbon atoms are subtracted.
[Claim 6] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) are such that R1 is a branched alkyl comprising from 5 to 9 carbon
atoms, such as 2-methyl-5-pentyl, 2-methyl-2-pentyl, isobutyl or 2-methylheptyl,
preferably 2-methyl-5-pentyl, or R1 represents ii) linear or branched, preferably linear,
(Cw-C3o)alkyl.
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[Claim 7] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) are such that the stereochemistry of the carbon atoms bearing the
radicals R1, R2, R3, R4 and R5 is of the same (R) or (S), preferably (R), configuration.
[Claim 8] Composition according to any one of Claims 1 to 5 and 7, in which the PHA
copolymer(s) a) are such that R1 represents iii) linear or branched (Cs-C3o)alkenyl; more
particularly linear, comprising at least one unsaturation, preferably only one
unsaturation, at the end of said alkenyl group; even more particularly, R1 represents
the following group: -[CR4(R5)]q-C(R6)=C(R7)-R8 with R4, R5
, R6, R7 and R8
, which may
be identical or different, representing a hydrogen atom or a (C1-C4)alkyl group such as
methyl, preferably a hydrogen atom, and q represents an integer inclusively between 2
and 20, preferably between 3 and 10, more preferentially between 4 and 8, such as 6;
more particularly, R1 is chosen from hexenyl, octenyl, undecenyl, 2-butenyl and 2-
methyl-2-pentenyl.
[Claim 9] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) are such that R2 is chosen from linear or branched (C1-C2s)alkyl, and
linear or branched (C2-C2s)alkenyl, in particular a linear hydrocarbon-based group,
particularly (C3-C2o)alkyl or (C3-C2o)alkenyl; preferably, the hydrocarbon-based group
has a carbon number corresponding to the number of carbon atoms of the radical R1
from which at least one carbon atom is subtracted, preferably corresponding to the
number of carbon atoms of the radical R1 from which at least two carbon atoms are
subtracted.
[Claim 1 0] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) are such that the radical R2 is a linear or branched, preferably linear,
(C1-Cs)alkyl, particularly (C2-C5)alkyl, preferably (C4-C6)alkyl group such as n-pentyl or
n-hexyl; or R2 is a branched (C3-Cs)alkyl, particularly (C4-C6)alkyl group, preferably a
branched (C4-Cs)alkyl such as isobutyl.
[Claim 11] Composition according to any one of Claims 1 to 7, 9 and 10, in which the PHA
copolymer(s) a) are such that, when R1 is an alkyl group:
the unit (A) is present in a molar percentage ranging from 30% to 99%,
preferentially a molar percentage ranging from 40% to 95%, more preferentially
a molar percentage ranging from 50% to 85%, even more preferentially a molar
percentage ranging from 60% to 70%; and
the unit (B) is present in a molar percentage ranging from 0.5% to 70%,
preferentially a molar percentage from 2% to 10%, more preferentially a molar
percentage from 5% to 35% of units (B); and/or
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the unit (C) is present in a molar percentage ranging from 0 to 20%, preferentially
a molar percentage from 0.1% to 10%, more preferentially from 0.5% to 7% of
units (C).
[Claim 12] Composition according to any one of Claims 1 to 5 and 7 to 10, in which the
PHA copolymer(s) a) are such that when R1 is an alkenyl or alkynyl group as defined
previously, said unit (A) is present in a molar percentage ranging from 0.1% to 50%,
more preferentially a molar percentage ranging from 0.5% to 40%, even more
preferentially a molar percentage ranging from 1% to 40%, better still a molar
percentage ranging from 5% to 30%, a molar percentage ranging from 8% to 20%; the
unit (B) is present in a molar percentage ranging from 70% to 99.5%, preferably
between 60% and 95%; and the unit (C) is present in a molar percentage ranging from
0 to 30%, preferably between 1% and 25%, more preferentially between 5% and 24%
relative to the sum, the unit (D) is present in a molar percentage ranging from 0 to 10%,
preferably between 0.1% and 5%, more preferentially between 0.5% and 2% relative
to the sum, and the unit (E) 0 to 10%, preferably between 0.1% and 5%, more
preferentially between 0.5% and 2% relative to the sum.
[Claim 13] Composition according to any one of the preceding claims, in which the PHA
copolymer(s) a) are such that they comprise the following repeating units:
Compounds
More especially :
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[Claim 14] Composition according to any one of the preceding claims, in which the fatty
medium comprises one or more substances chosen from:
• branched Cs-C16 alkanes such as Cs-C16 isoalkanes of petroleum origin (also known
as isoparaffins) such as isododecane, isodecane or isohexadecane,
• linear Cs-C16 alkanes, such as n-dodecane (C12) and n-tetradecane (C14), and also
mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C11) and
n-tridecane (C13), and mixtures thereof;
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• ester oils particularly chosen from oils of plant origin, such as triglycerides consisting
of fatty acid esters of glycerol in which the fatty acids may have varied chain lengths
from c4 to c24, these chains possibly being linear or branched, and saturated or
unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides. The
oils of plant origin may be chosen from wheatgerm oil, sunflower oil, grapeseed oil,
sesame seed oil, groundnut oil, corn oil, apricot oil, castor oil, shea oil, avocado oil,
olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, coconut
oil, hazelnut oil, walnut oil, rice oil, linseed oil, macadamia oil, alfalfa oil, poppy oil,
pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening
primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion
flower oil, musk rose oil and argan oil; shea butter; or alternatively caprylic/capric acid
triglycerides;
• monoester oils of formula R9-C(O)-OR10 in which R9 represents a linear or branched
hydrocarbon-based chain including from 5 to 19 carbon atoms and R10 represents a
linear or branched, notably branched, hydrocarbon-based chain containing from 4 to
20 carbon atoms, on condition that R9 + R10 :2: 9 carbon atoms and preferably less than
29 carbon atoms, for instance palmitates, adipates, myristates and benzoates, notably
diisopropyl adipate and isopropyl myristate; cetearyl octanoate (purcellin oil), isopropyl
myristate, isopropyl palmitate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl
palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate,
2-octyldodecyl myristate, 2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl
hexanoate, caprylyl heptanoate or cetyl octanoate;
• esters of lactic acid and of Cw-C2o alcohol, such as isostearyllactate, 2-octyldodecyl
lactate, myristyl lactate, C12-C13 alkyl lactate, cetyl lactate or lauryl lactate;
• diesters of malic acid and of Cw-C2o alcohol, such as diisostearyl malate, di(C12-C13
alkyl) malate, dibutyloctyl malate, diethylhexyl malate or dioctyldodecyl malate;
• esters of pentaerythritol and of Cs-C22 carboxylic acid (in particular tetraesters or
diesters), such as pentaerythrityl tetraoctanoate, pentaerythrityl tetraisostearate,
pentaerythrityl tetrabehenate, pentaerythrityl tetracaprylate/tetracaprate,
pentaerythrityl tetracocoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl
tetraisononanoate, pentaerythrityl tetrastearate, pentaerythrityl tetraisostearate,
pentaerythrityl tetralaurate, pentaerythrityl tetramyristate, pentaerythrityl tetraoleate or
pentaerythrityl distearate;
• diesters of formula R11-0-C(=O)-R12-C(=O)-O-R13, with R11 and R13, which may be
identical or different, representing a linear or branched, saturated or unsaturated
(preferably saturated) C4 to C12 and preferentially Cs to C10 alkyl chain, optionally
containing at least one saturated or unsaturated, preferably saturated, ring, and R12
representing a saturated or unsaturated C1 to C4, preferably C2 to C4, alkylene chain,
for instance an alkylene chain derived from succinate (in this case R12 is a saturated C2
wo 2021/260048 74 PCT/EP2021/067220
alkylene chain), maleate (in this case R12 is an unsaturated C2 alkylene chain), glutarate
(in this case R12 is a saturated C3 alkylene chain) or adipate (in this case R12 is a
saturated C4 alkylene chain); in particular, R11 and R13 are chosen from isobutyl, pentyl,
neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, cetyl, nonyl and isononyl; mention
may be made preferentially of dicaprylyl maleate or bis(2-ethylhexyl) succinate;
• diesters of formulaR14-C(=O)-O-R15-0-C(=O)-R16, with R14 and R16, which may be
identical or different, representing a linear or branched, saturated or unsaturated
(preferably saturated) C4 to C12 and preferentially Cs to C10 alkyl chain and R15
representing a saturated or unsaturated c1 to c4 and preferably c2 to c4 alkylene chain,
notably 1 ,3-propanediol dicaprylate (R14 as C1 and R16 as C3), or dipropylene glycol
dicaprylate;
• the carbonate oils may be chosen from the carbonates of the following formula R17-
0-C(O)-O-R18, with R17 and R18, which may be identical or different, representing a
linear or branched c4 to c12 and preferentially c6 to c10 alkyl chain; the carbonate oils
may be dicaprylyl carbonate (or dioctyl carbonate), bis(2-ethylhexyl) carbonate, dibutyl
carbonate, dineopentyl carbonate, dipentyl carbonate, dineoheptyl carbonate, diheptyl
carbonate, diisononyl carbonate or dinonyl carbonate and preferably dioctyl carbonate;
• and mixtures thereof.
[Claim 15] Composition according to any one of the preceding claims, in which the fatty
medium comprises one or more fatty substances in a content ranging from 2% to 99.9%
by weight, relative to the total weight of the composition, preferably ranging from 5% to
90% by weight, preferably ranging from 10% to 80% by weight, preferably ranging from
20% to 80% by weight relative to the total weight of the composition.
[Claim 16] Composition according to any one of the preceding claims, in which the fatty
medium comprises one or more solvents, preferably polar and/or protic solvents, other
than water, more preferentially C2-C6 alkanols, such as those chosen from ethanol,
propanol, butanol, pentanol and hexanol, preferably ethanol; more particularly, the
solvent(s) are present in the composition in a weight percentage of between 0 and 10%
relative to the total weight of the solvent mixture, preferentially between 0.5% and 8%,
more particularly between 1% and 5%, such as 2% by weight relative to the total weight
of the composition.
[Claim 17] Composition according to any one of the preceding claims, in which the fatty
medium comprises one or more fatty substances in a content ranging from 2% to 99.9%
by weight, relative to the total weight of the composition, preferably ranging from 5% to
90% by weight, preferably ranging from 10% to 80% by weight, preferably ranging from
20% to 80% by weight relative to the total weight of the composition.
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[Claim 18] Composition according to any one of the preceding claims, which also
comprises one or more colouring agents chosen from pigments, direct dyes and
mixtures thereof, preferably pigments; more preferentially, the pigment(s) of the
invention are chosen from carbon black, iron oxides, notably black iron oxides, and
micas coated with iron oxide, triarylmethane pigments, notably blue and violet
triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments,
such as D&C Red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol
red B, even more preferentially red iron oxides.
[Claim 19] Process for treating keratin materials, preferably a) keratin fibres, notably
human keratin fibres such as the hair, or 13) human skin, in particular the lips, by
applying the composition as defined in any one of the preceding claims.