The present invention relates to novel polymers of the polycondensate family of the modified alkyd type, and to their use in cosmetic compositions, in particular in lipsticks, to cosmetic compositions containing them and to methods for preparing the said polycondensates.
Numerous cosmetic compositions exist for which gloss properties of the film deposited, after application to keratin materials (skin, lips, superficial body growths), are desired. There may be mentioned, for example, lipsticks, nail varnishes or certain hair products.
In order to obtain such a result, it is possible to combine specific raw materials, in particular lanolins, with so-called glossy oils, such as polybutenes which have nevertheless a high viscosity; or esters of a fatty acid or a fatty alcohol in which the number of carbons is high; or alternatively certain vegetable oils; or else esters resulting from the partial or complete esterification of a hydroxylatect aliphatic compound with an aromatic acid, as described in patent application EP 1097699.
It is also known to combine lanolins with polyesters obtained by sequential reaction of castor oil with isostearic acid and then with succinic acid, as described in patent US 6342527.
To improve the gloss of the deposited film, and its staying power, it has also been proposed to use esters resulting from, the condensation of a polyol with a "new" type carboxylic acid, in particular in FR 2838049.
There may also be mentioned EP 1457201, which describes a composition combining a polyester of triglycerides of hydroxyiated carboxylic acids and an oil of low
molecular mass chosen from polybutylenes, hydrogenated polyisobutylenes, hydrogenated • or non-hydrogenated polydecenes, copolymers of vinylpyrrolidones, esters of linear fatty acids, hydroxylated esters, esters of branched C24-C28 fatty alcohols or fatty acids, silicone oils and/or oils of plant origin.
In patent application EP 0792637, a composition combining an aromatic ester or a polymer of the polybutene or polyisobutene type is described.
In patent application EP 1155687, a process is described which consists in incorporating, into an oily phase constituted of a cosmetically acceptable oil, an organopolysiloxane having at least 2 groups capable of establishing hydrogen bonds.
However, these compositions and combinations, even though they significantly improve the gloss, are still judged inadequate for the purpose of a .long staying power of this gloss, over time.
The aim of the present invention is to provide novel polymers which may confer a significant gloss on a deposit, in particular a film-forming deposit, while maintaining good stability of this gloss over time; it may find a particularly advantageous application in the field of lipsticks, Moreover, polymers are also sought which can additionally advantageously confer on the composition excellent staying power over time on keratin materials, in particular on the lips.
For this purpose, the applicant has sought novel alkyd-type polycondensates having the desired properties .
Alkyd resins constitute a particular class of polyesters in being the product of reaction of polyols and polycarbcxylic acids, generally modified by
unsaturaLed fatty acids, such as oleic acid, or by unsaturated oils, for example soybean or castor oil, which make it possible to modulate their film-forming properties, in particular their rate of drying, their hardness and their resistance.
Thus, there has been proposed in the document US 2915488 modified alkyd resins in which part of the fatty acids derived from soybean oil has been replaced by benzoic acid. These novel resins have improved properties in terms of resistance to alkalis and to detergents; the films containing them dry more rapidly and are harder. However, no application, in particular no cosmetic or topical application, has been envisaged for these resins.
Moreover, the fatty acids present in soybean oil are predominantly constituted of two unsaturated fatty acids: about 55% of linoleic acid (C18: 2) and 28% of oleic acid (018:1), according to "Surface Coatings Science and Technology", 2nd edition, John Wiley & Sons, pages 104 and 105. Now, it is known that certain unsaturated fatty acids can undergo, over time, auto-oxidation which may be responsible for the phenomena of rancidity, which can result in problems for preservation of compositions comprising these raw materials. Furthermore, the alkyd resins described in US 2915488, which comprise a high proportion of linoleic and oleic fatty acids, are not optimum, in particular in terms of stability, for use in cosmetics.
The crosslinking of alkyd resins by oxidation in air with formation of hydroperoxides plays a key role in, the rate of drying of the film and, consequently, in its final properties of hardness and resistance to external attacks, in the usual fields of application of these alkyd resins, namely paints, the rate of crosslinking, and therefore of drying, is generally
accelerated by the addition of particular metal salts, called "dryers", such aa cobalt naphtheriates and octsnoates which accelerate the decomposition of hydrcperoxides; this is in particular described in Principles of Polymerization, 4th edition, John Wiley & Sons, pages 737-738 and also in Surface Coatings Science and Technology, 2nd edition, John Wiley & Song, Tables 2.3 and 2.4 pages 526-530.
However, the use of such metal salts is obviously not desirable in cosmetics for obvious reasons of toxicity.
Moreover, most alkyd resins do not have suitable solubility in the oily media normally used in cosmetics, such as vegetable oils, alkanes, fatty esters, fatty alcohols, silicone oils, and in particular comprising isodcdecane, Parleam, isononyl isononanoate, octyldodecanol, phenyltriroethicone, C12-C15 alkyl benzoate and/or D5 (decamethylcyclopentasiloxane).
After major research studies, the applicant has discovered surprisingly and unexpectedly that certain polycondensates with a higher content of particular carboxylic acids, including non-aromatic monocarboxylic acids, could lead to improved performance in terms of gloss, maintenance of the said gloss, and additionally long staying power of the film obtained, while being capable of being carried in the customary cosmetic media, in particular the customary cosmetic oily media.
The subject of the present invention is therefore a cosmetic or pharmaceutical composition comprising, in a cosmetically or pharmaceutically acceptable medium, at least one polycondensate capable of being obtained by the reaction:
- of 10 to 30% by weight, relative to the total weight
of the polycondensate, of at least one polyol
comprising 3 to 6 hydroxyl groups;
- of 22 to 80% by weight, relative to the total weight
of the polycoadensate, of at least one linear,
branched and/or cyclic, saturated or ur; saturated,
non-aromatic monocarboxylic acid comprising 10 to 32
carbon atoms, and having a melting point greater
than or equal to 256C;
- of, 0.1 to 35% by weight, relative to the total
weight of the polycondensate, of at least one
linear, branched and/or cyclic, saturated or
unsaturated, non-aromatic monocarboxylic acid
comprising 6 to 32 carbon atoms and having a melting
point strictly less than 25"C;
- of 0.1 to 10% by weight, relative to the total
weight of the polycondensate, of at least one
aromatic monocarboxylic scid comprising 7 to 11
carbon atoms, optionally additionally substituted
with 1 to 3 linear, branched and/or cyclic,
saturated or unsaturated alkyl radicals which
comprise 1 to 32 carbon atoms;
of 1 to 40% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsaturated, or even aromatic, polycarboxylic acid comprising at least 2 carboxyl groups COOH, which may comprise heteroatoms; and/or a cyclic anhydride of such a polycarboxylic acid; and/or a lactone comprising at least one COOH group.
Another subject of -he invention is a polycondensate
which may be obtained by the reaction:
of 10 to 30% by weight, relative ~o the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups;
- of 22 to 80% by weight, relative to the total weight
of the polycondensate, of at least one linear,
branched and/or cyclic, saturated or unsatutated, non-aromatic monocarboxylic acid comprising 10 to 32 carbon atoms, and having a melting point greater than or equal to 25°C;
- of C.1 to 35% by weight, relative to the total
weight of the polycondeasate, of at least one
linear, branched and/or cyclic, saturated or
unsaturated, non-aromatic monocarboxylic acid
comprising 6 to 32 carbon atoms and having a melting
point strictly less than 25°C;
- of 0.1 to 10% by weight, relative to the total
weight of the polycondenaate, of at least one
aromatic monocarboxylic acid comprising 7 to 11
carbon atoms, optionally additionally substituted
with 1 to 3 linear/ branched and/or cyclic,
saturated or unsaturated alkyl radicals which
comprise 1 to 32 carbon atoms;
- of 1 to 40% by weightr relative to the total weight
of the polycondensate, of at least one linear,
branched and/or cyclic, saturated or unsaturated, or
even aromatic, polycarboxylic acid comprising . at
least 2 carboxyl groups COOH, in particular 2 to 4
COOH groups, and which may comprise one or more
heteroatoms; and/or a cyclic anhydride of such a
pclycarboxylic acid; and/or a lactone comprising at
least one COOH group.
Finally, the polycondensate therefore generally comprises these monomers, in the proportions indicated; most preferably the polycondensate is constituted (exclusively or solely comprises) of these monomers.
In particular, the cosmetic compositions exhibit good applicability and good covering power; good adhesion to the support, whether on the nail, the hair, the eyelashes, the skin or the lips; adequate flexibility and resistance of the film, so as to avoid cracks, for example in the case of lipsticks or varnish; and also
an excellent level of long-lasting gloss. The comfort and slip properties are also very satisfactory. These polycondensates can be easily carried in cosmetic solvent or oily media, in particular oils, fatty alcohols and/or fatty esters, which facilitates their use in the cosmetic field, in particular in lipsticks or foundations.
The polycondensates according to the invention nay be easily prepared, in a single synthesis step, and without producing waste, at low cost.
Moreover, it is possible to easily modify the structure and/or the properties of the polycondensates according to the invention by varying the chemical nature of the various constituents and/or their proportions.
The polycondensates according to the invention are advantageously branched; it is possible to think that this makes it possible to generate a network by entanglement of the polymer chains, and to therefore obtain the desired properties, in particular in terms of improved staying power, improved gloss, and in terms of solubility, It has indeed been observed that linear polycondensates do not make it possible to obtain a notable improvement in the staying power of the composition, and that polycondensates of the dendrimer type, whose chains are regular, do not have optimum solubility.
The polycondensa-es according to the invention are polycondensates of the alkyd -ype, and are therefore capable of being obtained by esterification/-polycondensation, according to methods known to a person skilled in the art, of the constituents described below.
One of the constituents necessary for the preparation of the polycondensates according to the invention is a compound comprising 3 to 6 hydroxyl (polyol) groups, in particular 3 to 4 hydroxyl groups. It is quite obviously possible to use a mixture of such polyols.
The said polyol may in particular be a saturated or unsaturated, linear, branched and/or cyclic carbon-containing, in particular hydrocarbon-containing, compound comprising 3 to 18 carbon atoms, in particular 3 to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxyl (OH) groups, and capable of additionally comprising one or more oxygen atoms intercalated in the chain (ether functional group).
The •said polyol is preferably a linear or branched, saturated hydrocarbon compound comprising 3 to 18 carbon atoms, in particular 3 to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxyl (OH) groups.
It may be chosen from, alone or as a mixture:
triolg, such as 1,2,4-butanetriol, 1,2,6-
hexanetriol, trimethylolethane, trimethylolpropane,
glycerol;
tetraols, such as pentaerythritol
(tetramethylolmethane), erythritol, diglycerol or
ditrimethylolpropane;
pentols such as xylitol;
- hexols such as sorbitol and mannitol; or alternatively dipentaerythritol or triglycerol.
Preferably, the polyol is chosen from glycerol, diglycerol, pentaerythritol, sorbitol and mixtures thereof; and better still is pentaerythritol. The polyol, ox the polyol mixture, preferably represents 10 to 3C% by weight, in particular 12 to 25% by weight, and even better 14 to 22% by weight, of the total weight of the final polycondensate.
Another constituent necessary for the preparation of the pclycondensates according to the invention is a linear, branched and/or cyclic, saturated or unsaturated, non-aromatic monocarboxylic acid comprising 10 to 32 carbon atoms, in particular 1.2 to 28 carbon atoms and better still 12 to 24 carbon atoms; and having a melting point greater than or equal to 25°C, in particular greater than or equal to 28°C, or even 30°C. It is quite obviously possible to use a mixture of such non-aromatic monocarboxylic acids.
It has been observed that when such an acid is used, in the quantities indicated, it is possible, on the one hand/ to obtain good gloss and staying power for the said gloss and, on the other hand, to reduce the quantity of waxes customarily present in the composition envisaged.
The expression non-aromatic monocarboxylic acid is understood to mean a compound of formula RCOOH, in which R is a linear, branched and/or cyclic, saturated or unsaturated hydrocarbon radical comprising 9 to 31 carbon atoms, in particular 11 to 27 carbon atoms, and better still 11 to 23 carbon atoms.
Preferably, the R radical is saturated. Better still, the said R radical is linear or branched, and is preferably C11-C21.
Among the non-aromatic monocarboxylic acids having a melting point greater than or equal to 25°C, which are liable to be used, there may be mentioned, alor.e or as a mixture;
among the saturated monocarboxylic acids: decanoic (capric) acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid,
arachxdonic acid, behenic acid, cerotic acid
(hexacosanoic) acid;
among the unsaturated but non-arometic
monocarboxylic acids: petroselinic acid, vaccenic
acid, elaidic acid, gondoic acid, gadoleic acid,
erucic acid, nervonic acid.
Preferably, it is possible to use lauric acid, palmitic acid, stearic acid, behenic acid and mixtures thereof, and better still stearic acid or behenic acid, alone..
The said non-aromatic monocarboxylic acid having a melting point greater than or equal to 25°C, or the mixture of the said acids, preferably represents 22 to 80% by weight, in particular. 25 to 75% by weightr or even 27 to 70% by weight, and even better 28 to 65% by weight, of the total weight of the final polycondensate.
Another constituent necessary for the preparation of the polyCondensates according to the invention is a linear/ branched and/or cyclic, saturated or unsaturated, non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms, in particular 8 to 28 carbon atoms and better still 10 to 20, or even 12 to 18, carbon atoms; and having a melting point strictly less than 25°C, in particular less than 20°C, or even 15°C. It is quite obviously possible to use a mixture of such non-aromatic monocarboxylic acids.
The expression non-aromatic monocarboxylic acid is understood to mean a compound of formula RCOCH, in which R is a linear, branched and/or cyclic, saturated ox unsaturated hydrocarbon radical comprising 5 to 31 carbon atoms, in particular 7 to 27 carbon atoms, and better still 9 to 19 carbon atoms, or even 11 to 17 carbon atoms.
Preferably, the R radical is saturated. Better still, the said R radical is linear or branched, and is preferably C5-C31.
Among the non-aromatic monocarboxylic acids having a melting point of less than 25°C, liable to be used, there may be mentioned, alone or as a mixture:
among the saturated monocarboxylic acids; caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-diraethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, isostearic acid;
among the unsaturated but non-aromatic monocarboxylic acids: caproleic acid, obtusilic acid, undecylenic acid, dodecylenic acid, linderic acid, myristoleic acid, physeteric acid, tsuzuic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid.
Preferably, it is possible to use isooctanoic acid, isononanoic acid, isostearic acid, and mixtures thereof, and better still isostearic acid alone.
The said non-aromatic monocarboxylic acid having a melting point of less than 25°C, or the mixture of the said acids, preferably represents 0.1 to 35% by weight, in particular 0.5 to 32% by weight, or even 1 to 30% by weight, and even better 2 to 28% by weight, of the total weight of the final polycondensate.
Preferably, the total quantity of non-aromatic monocarboxylic acids, namely those having a melting point greater than 25°C + those having a melting poir.t of less than 25°C, is advantageously between 30 and 8C% by weight, in particular between 40 and 70% by weight, or even 45 and 65% by weight, and better still between
50 and 60% by weight, of the total weight of the final polycondensate.
Another constituent necessary for the preparation of the pblycondensates according to the invention is an aromatic mcnocarboxylic acid comprising 7 to 11 carbon atoms, optionally additionally substituted with 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals which comprise ^ to 32 carbon atoms, in particular 2 to 12, or even 3 to 8 carbon atoms.
It is of course possible to use a mixture of such aromatic monocarboxylic acids.
The expression aromatic monocarboxylic acid is understood to neem a compound of the formula R'COOH, in which R' is an aromatic hydrocarbon radical comprising 6 to 10 carbon atoms, and in particular the benzols and naphthoic radicals. The said R' radical may be additionally substituted with 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms, in particular 2 to 12, or even 3 ~o 8 carbon atoms; and in particular chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, octyl or isooctyl.
Among the aromatic monccarboxylic acids liable to be used, there may be mentioned, alone or as a mixture, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butylbenzoic acid, l-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid.
Preferably, it is possible to use benzoic acid, 4-tert-butylbenzoic acid, o-toluic acid, m--oluic acid, 1-

naphthoic acid, alone or as mixtures; and better still benzole acid alone.
The said aromatic monocarboxylic acid, or the mixture of the said acids, preferably represents 0.1 to 10% by weight, in particular 0.5% to 9.95% by weight, better still from 1 to 9.5% by weight, or even 1.5 to 8% by weight, of the total weight of the final polycondensate.
Another constituent necessary for the preparation of the polycondensates according to the invention is a polycarboxylic acid, and/or a cyclic anhydride of such a polycarboxylic acid, and/or a lactone carrying at least one COOH group; and mixtures thereof.
The said polycarboxylic acid may in particular be chosen from saturated or unsaturated, or even aromatic, linear, branched and/or cyclic polycarboxylic acids comprising 2 to 50, in particular 2 to 40, carbon atoms, in particular 3 to 36, or even 3 to 18, and better still 4 to 12 carbon atoms, or even 5 to 10 carbon atoms; the said acid comprising at least two carboxyl groups COOH, preferably 2 to 4 COOH groups; and capable of comprising 1 to 10, preferably 1 to 6, heteroatoms, which are identical or different, chosen from 0, N and S; and/or capable of comprising at least one perfluorinated radical chosen from "CF2- (divalent) or -CF3.
Preferably, the said polycarboxylic acid is linear, saturated and aliphatic, and comprises 2 to 36 carbon atoms, in particular 3 to 18 carbon atoms, or even 4 to 12 carbon atoms; or else is aromatic and comprises 8•to 12 carbon atoms. It preferably comprises 2 to 4 COOH groups.
The said cyclic anhydride of such a polycarboxylic acid may in particular correspond to one of the following formulae:
(Formula Removed)
in which the A and B groups arer independently of each
other:
a hydrogen atom,
a linear, branched and/or cyclicr saturated or
unsaturated, aliphatic or aromatic carbon-containing
radical comprising 1 to 16 carbon atoms, in
particular 2 to 10 carbon atoms/ or even 4 to 8
carbon atoms, in particular methyl or ethyl;
or else A and B taken together form a saturated or
unsaturated, or even aromatic, ring comprising in
total 5 to 14, in particular 5 to 10, or even 6 to 1
carbon atoms.
Preferably, A and 3 represent a hydrogen atom or form together an aromatic ring comprising in total 6 to 10 carbon atoms.
Among the polycarboxylic acids or their anhydrides, which are liable to be used, there may be mentioned, alone or as a mixture:
dicaxboxylic acids such as decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedi-caxboxylic acid, 1,4~naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthal-enedicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric
acid, adipic acid, fumaric acid, maleic acid, itacor.ic acid, dimers of fatty acids (in particular as C36) such as the products marketed under the names Pripol 1006, 1009, 1013 and 1017,, by Uniqema; tricarboxylic acids such as cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1, 3, 5-beruenetricarboxylic acid;
- tetracarboxylic acids such as butanetetracarboxylic
acid and pyrromellitic acid,
- the cyclic anhydrides of these acids and in
particular phthalic anhydride, trimellitic
anhydride, maleic anhydride and succinic anhydride.
Preferably, it is possible to use adipic acid, phthalic anhydride and/or -isophthalic acid, and better still isophthalic acid alone.
There may also be mentioned the polycarboxylic acids
chosen from, alone or as a mixture:
(i) polycarboxylic acids having a linear or branched, saturated or unsaturated chain, comprising at least one heteroatom chosen from 0, N and/or S, in particular 1 to 10 heteroatoms which are identical or different, and/or comprising at least one perfluorinated radical -CF2- or -CF3 and having moreover at least 2 carboxyl groups COOH, in particular 2 to 4 CDOH groups; and/or a cyclic anhydride of such a polycarboxylic acid;
and/or
(ii) saturated cr unsaturated, or even aromatic, heterocyclic polycarboxylic acids comprising at least one heteroatora chosen from 0, N and/or S, in particular 1 to 10, ox even 1 to 4, heteroatoms which are identical or different, and at least 2 carboxyl groups COOH, in particular 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid;

and/or (iii) and/or (iv) and/or (v) polycarboxylic acids derived from sugar, which are liable to be obtained in particular by oxidation of an aldose, and comprising at least 2 carboxyl groups COOH, in particular 2 or 3 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid;
itaconic anhydride and the 1,4-rnonoanhydxide of 1,4,5,8-naphthalenetetracarboxylic acid;
polycarboxylic (including heterocydic) atrdno acids, that is to say polycarboxylic acids having a linear, branched and/or cyclic, saturated or unsaturated chain optionally comprising at least one heteroatom chosen from 0, N and/or 5, in particular 1 to 10 heteroatoms which are identical or different, and/or optionally comprising at least one perfluorinated radical -CF2- or -CF3; and additionally comprising at least one primary, secondary or tertiary amine functional group (in particular NR1R2 with Rl and R2, independently of each other, chosen from H and C1-C12 alkyl), in particular 1 to 3 amine functional groups, which are identical or different, and having moreover at least 2 carboxyl groups COOH, in particular 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid.
There may be mentioned most particularly, alone or as a
mixture, the following dicarboxylic acids:
(i)
2,2'-[1,5-pentanediylbis(thio)]bis-acetic acid
6,6'-[(1,2-dioxo-l,2-ethanediyl)diimino]bis-hexanoic
acid
2,2'-sulphinylbis-acetic acid
4r13-dioxo-3,5,12,14-tetraazahexadecanedioic acid poly(ethylene glycoi) disuccinater in particular having a mass of 250-600
poly(ethylene glycol)bis(carboxymethyl)ether, in particular having a mass of 250-600 poly [oxy(l,2-dicarboxy-l,2-ethanediyl) ], in particular having a DP < 10 8-[(carboxymethyl)amino]-8-oxooctanoic acid 2,2'-[methylenebis(sulphonyl)]bis-acetic acid 4,4'-(l,6-hexanediyldiimino)bis[4-oxo-butanoic] acid 4,9-dioxo-3,5,8,10-tetraazadodecanedioic acid 4-[(1-carboxyenhyl)amino]-4-oxo-butanoic acid 6-[(3-carboxy-l-oxopropyl)anino]hexanoic acid N,N'-(1,6-dioxo-l,6-hexanediyl)bis-glycine N,N'-(1,6-dioxo-l,6-hexanediyl)bis-phenylalanine N, N'-(1,3-dioxo-l,3-propanediyl)bis-glycine 4, 4' -[(1,4-dioxo-l,4-butanediyl)diimino]bis-butanoic acid
4, 4'-[ (1, 6-dioxo-l, 6-"nexenediyl}diimino]bis-butanoic acid
6,6'-[l,6-hexanediylbis(iminocarbonyliraino)]bis-hexanoic acid
N-benzoyl-S-(carboxymethyl)-Cysteine N,N'-(2,2,3,3-tetrafluoro-1,4-dioxo-l,4-butanediyl)bis-Glycine
N,N'-(2,2,3,3-tetrafluoro-1,4-dioxo-l,4-butanediyl)bis-Alanine
4,4'- [ (2,2,3,3-tetrafluoro-1,4-dioxo-l,4-butanoic acid
N,N'-(1,5-dioxo-l,5-pentanediyl)bis-Glycine N,Nr-(1,9-dioxo-l,9-nonanediyl}bis-Glycine N,N'-(1,10-dioxo-l,10-decanediyl)bis[N~methyl-Glycine
bis(3-carboxypropyl)ester of propanedioic acid 7,16-dioxo-6,8,15,17-tetraazadocosanedioic acid N-benzoyl-N-(2-carboxyethyl)-Glycine [2-[(2-carboxymethyl)amino]-2-oxoethyl]-benzenepropancic acid
[2-[(2-carboxyethyl)amino]-2-oxoethyl]-Benzenepropanoic acid
lii)
4, 7,9,12-tetraoxapentadecanedioic acid
• 2,3-pyridinedicarboxylic acid
4-pyranone-2,6-dicarboxylic acid
2,5-pyrazinedicarboxylic acid
2,5-pyridinedicarboxylic acid
• 1,3-benzofurandicarboxylic acid
• 7-oxabicyclo[2,2.1]heptane-2,3-dicarboxylic acid
3,4-pyridinedicarboxylic acid
2,4-pyridinedicarboxylic acid
3, 5-pyridinedicarbojcylic acid
2,6-pyridinedicarboxylic acid
lH-imidazole-4,5-dicarboxylic acid
2,3-quinolinedicarboxylic acid
6,6,7, 7-tetraflaoro-3-oxabicyclo [3 .2 . 0] heptane-2, 4-
dicarboxylic acid
2,6-pyrazinedicarboxylic acid
2, 6-dimethyl-3, 5-pyri'dinedicarboxylic acid
l-phenyl-lH-pyrazole-3,4-dicarboxylic acid
2,5-furandicarboxyIic acid
3,4-furandicarboxylic acid
1,2,S-thiadiazole-S,4~dicarboxylic acid
1,4-dihydro-l,2,4,5-tetrazine-3,6-dicarboxylic acid
2,3-furandicarboxylic acid
3,4-thiophenedicarboxylic acid
1H-1,2,3-triazole-4,5-dicarboxylic acid
2-methylimidazole-4, 5-dicarboxylic acid
2,4-quinolinedicarboxylic acid
• naphtho[2,l-b]furan-1,2-dicarboxylic acid
3,4-quinolinedicarboxylic acid
• 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid
2,3-quinoxalinedicarboxylic acid
1,4-piperazinedicarboxylic acid
2,5-dimethyl-3,4~furandicarboxylic acid
tetrahydro-2,5-thiophenedicarboxylic acid
4~phenyl-3,5-pyridinedicarboxylic acid
thieno[3,2-b]thiophene-2,5-dicarboxylic acid
3-rnethyl-2, 4-thiophenedicarboxylic acid
naphthostyr.il-5, 6-tiicarboxylic acid
3~phenyl-2,4-quinolinedicarboxylic acid
3,4-dimethyl-2,5-dicarboxythiophene
3,4-diphenyl-2,5-thiophenedicarboxylic acid
2,5-diphenyl-3,4-furandicarboxylic acid
7-oxo-7H-benzimidazO[2,l-a]benz[de]isoquinoline-3,4-
dicarboxylic acid
2,3-dihydro-1,3-dioxo-lH-benz[de]isoquinoline-6,1 -
dicarboxylic acid
3,4-bis(phenylmethoxy)-2,5-furandicarboxylic acid
4,4'-bibenzoic acid 2,2'-sulphone
2,7-diphenyl-m-anthrazoline-4,5-dicarboxylic acid
2,4-pyrimidined,icarboxylic acid
2~phenyl-4,5-thiazoledicarboxylic acid
6-phenyl-2,3-pyridinedicarboxylic acid
5,6-dimethyl-2, 3-pyra±xaedicarboxylic acid
3,7-dibenzothiophenedicarboxylic acid
S-oxo-gH-xanthene-ly 7-dicarboxylic acid
2-(1,1-dimethylethyl)-H-iraidazole-4,5-dicarboxylic
acid
6,7-quinolinediearboxylic acid
6-methyl-2,3-pyridinedicarboxylic acid
4,5-pyrimidinedicarboxylic acid
2-methyl-3,4-furandicarboxylic acid
1,2-indolizinedicaxboxylic acid
2,8-dibenzothiophenedicarboxylic acid
3,6-pyridazinedicarboxylic acid
1,10-phenanthtfoline-2,9-dicarboxylic acid
1,4,5, 6-tetrahydro"5,6"dioxo-2,3-pyrazine-
dicarboxylic acid
3,4-dimethoxy-2,S-furandicarboxylic acid
2-ethyl-4,5-imidazoledicarboxylic acid
2-propyl-lH-imidazole~4,5-dicarboxylic acid
4-phenyl-2,5-pyridinedicarboxylic acid
4,5-pyridazinedicarboxylic acid
1,4,5,8-tetxahydro-l,4:5,8-diepoxynaphthalene-4a,8a-
dicarboxylic acid
5,5~dioxide-2,8-dibenzothiophenedicarboxylic acid
pyrazolo[1,5-a]pyridine-2,3-dicarboxylic acid
2,3-dihydro-lH-pyrrolizine-l,7-dicarboxylxc acid
6-methyl-2, 4,5-pyridinetricarboxylxc acid
pyrxolo[2,l,5-cd]indolizine-5,6-dicarboxylic acid
3,4~bis(2,2,3,3,4,4,4-heptafluorobutyl)-lH~pyrrole-
2,5-dicarboxylic acid
6,7,9,10,17;13,2C,21-octahydrodibenzo~
[br k] [1,4,7,10,13,16]hexaoxacyclooctadecine-2,14-
dicarboxylic acid
6,7,9,10,17,13,20,21-octahydrodibenzo-
[b,k][1,4,7,10,13/16]hexaoxacyclooctadecine-2,13-
dicarboxylic acid
2-methyl-3,4-quinolinedicarboxylic acid
4,7-quinolinedicarboxylic acid
3,5-isoxazoledicaxboxylic acid
2- (trifluorosxethyl) -3, 4-furandicarboxylic acid
5-(trifluoromethyl)-2,4-furandicarboxylic acid
6-methyl-2,4-quinolinedicarboxylic acid
5-oxo-l,2-pyrrolidinedicarboxylic acid
5-ethyl-2f 3-pyridinedicarboxylic acid
lr2-dihydro-2-oxo-3,4-quinolinedicarboxylic acid
4,6-phenoxathiindicarboxylic acid
10,10-dioxide 1,S-phenoxathiindicarboxylic acid
3,4-dihydro-2H-l,4-thiazine-3,5-dicarboxylic acid
2,7-di(tert-butyl)-9,9-dimethyl-4,5-xanthene-
dicarboxylic acid
6-methyl-2,3-quinoxalinedicarboxylic acid
3,7-quinolinedicarboxylic acid
2,5-quinolinedicarboxylic acid
2-methyl-6-phenyl-3,4-pyridinedicarboxylic acid
3/4-dimethylthieno[2, 3-b]thiophene-2,5-dicarboxylic
acid
3,4-dimethoxythiophene-2,5-dicarboxylic acid
5-methyl-3,4-isoxazoledicarboxylic acid
2, 6-bis (aminocarborxyl) -3, 5-pyridinedicarboxylic acid
3,5-bis(aminocarbonyl)-2,6-pyrazinedicarboxylic acid
2,3-pyridinedicarboxylic acid
6- (1,l~dimethylethyl)-2-ethyl-3,4-pyridine-
dicarboxylic acid
3-methyl-5-phenyl-2,4~thiophenedicarboxylic acid
l,2-dihydro-2-oxo-6-phenyl-3,5-pyridinedicarboxylic
acid
B-methyl-2,4-quinolinedicarboxylic acid
4-ethyl-2,6-dimethyl-3,5-pyridinedicarboxylic acid
5-(phenoxynethyl)-2,4-furandicarboxylic acid
5-(acetylaniao)-3-methyl-2,4-tbiophenedicarboxylic
acid
2- (4-heptyiphenyI)-4,8-quinolirFedicarboxylic acid
2,8-bis(4-heptylphenyl)pyrido[3,2-g]quinoIine-4,6-
dicarboxylic acid
1,2,3,4,6,7,8,9-octahydro-2 ,8-cioxopyrido[3,2]-
quinoline-3,7-dicarboxylic acid
2,8-dimethylpyrido[3,2-g]quinoline-3,7-dicarboxylic
acid
5,6-quinolinedicarboxylic acid
6-ethyl-2-methylcinchomeronic acid
2-methyl-6-propylcinchomeronic acid
6-isopropyl-2-methylcinchomeronic acid
6-tert-butyl-2-methylcinchomeronic acid
1, 4-dimethyl-7-o5?abicyclo [2.2.1]heptane-2, 3-
dicarboxylic acid
1,2-dihydro-2-oxo-3,8-quinolinedicarboxylic acid
1,2-dihydxo-2-oxo-3,6-quinolinedicarbcxylic acid
1,2-dihydro-2-oxo-3,7-quinolinedicarbcxylic acid
3, 7~dimethyl-2, 8-diphenylpyrido [3, 2-g] quin,oline-4, 6-
dicarboxylic acid
8-raethyl-2,3-quinolinedicarboxylic acid
3-[[(1,1-dimethylethyl)amino]sulphonyl]-2, 5-
thiophenedicarboxylic acid
4-(acetylamino)-2,3-thiophenedicarboxylic acid
2,5-pyridinedicarboxylic acid
2,6-pyridinedicarboxylic acid
2,4-thiophenedicaxboxylic acid
2,5-thiophenedicarboxylic acid
- 1,4-pyran-2,6-dicarboxylic acid
(iii)
ribaric acid glucaric acid xylaric acid arabinaric acid
- mannaric ecid
- idaric acid
- altraric acid
L-glucaric acid
L-arabinaric acid
allaric acid
- galactaric acid
- meso-tartaric acid
- D-glucaric acid
L-idaric acid
hexaric acid
- 2,3-dihydroxybutanedioic acid
D-tartaric acid
- DL^tartaric acid
D-glucaric acid
tartaric acid
tetrahydroxysuccinic acid
2-carboxy-2,3-dideoxy-D-manno-2-octulopyranosonic acid
- methyl 3-deoxy-D-arabino-2-heptulopyranosaric acid
D-lyxo-2-heptulopyranosaric acid
2,6-anhydro-L-glycero-L-galactcheptaric acid
(iv)
1,4,5,8-naphthalenetetracarboxylic acid 1/4-
monoanhydride
itaconic anhydride
(v)
\ 1, 3-dihydro-4-oxo-2, 5-pyridinedicarboxylic acid
2,6-piperidinedicarboxylic acid lH-pyrrole-3,4-dicarboxylic acid 4-amino-2,6-dicarboxylic acid l-methyl-lH-pyrazole-3,4-dicarboxylic acid 2,3-piperidinedicarboxylic acid l^methyl-lH-imidazole-4,5-dicarboxylic acid 2,4-thiazolidinedicarboxylic acid
1- (phenylmethyl)-lH-imidazole-4,5-dicarboxylic acid 5-amino-6-0x0-2,3-piperidinedicaxboxylic acid 5-amino-6-oxo-2,4-piperidinedicarboxylic acid 5-amino-6-oxo-2,3-piperidinedicarboxylic acid 5-amino-6-oxo-[2S-(2α, 4ß,5α)]-2,4-piperidine¬dicarboxylic acid
(2S,4R}-2,4-pyrrolidinedicarboxylic acid (2S-cis)"2,4-pyrrolidinedicarbcxylic acid 2-amino-lH-imidazole-4,5-dicarboxylic acid 2,5-pyrrolidinedicarboxylic acid 4-amino-3,S-isothiazoledicarboxylic acid l-methyl-lH-pyrazole-3,5-dicarboxylic acid 7-(diethylamino)-2-oxo-2H-l-benzopyran-3,4-dicaxboxylic acid
3,4-diethyl-lH-pyrrole-2,5-dicarboxylic acid l-phenyl-lH-pyrrole-3,4-dicarboxylic acid cis-2,3-piperazinedicarboxylic acid 2,3-pipecazinedicarboxylic acid 2,5-piperozinedicarboxylic acid 2, 6-piperazinedicarboxylic acid 2-amino-3,5-pyridinedicarboxylic acid 2-methylpyrrole-3,4-dicarboxylic acid 4-(methylemino)-2,6-pyridinedicarboxylic acid 2-amino-G-methyl-3,4-pyridinedicarboxylic acid 5-aminot-2-methyl-3, 4-pyridinedicarboxylic acid 2-amino-6-merhy1-3,5-pyridinedicarboxylic acid 2,5-dimethylpyrrole-3,4-dicarboxylic acid 2-amino-6-hydroxy-3,5-pyridinedicarboxylic acid 2,4-pyrrolidinedicarboxylic acid lH-indole-2,4-dicarboxylic acid lH-indole-2,6-dicarboxylic acid
lH-indole-2,5-dicarboxylic acid
5-phenyl-2,4-pyxrolidinedicarboxylic acid
S-methyl-2,4-pyrrolidinedicarboxylic acid
trans-2,4-azetidinedicarboxylic acid
cis-2,4-azetidinedicarboxylic acid
3,5-piperidinedicarboxylic acid
2,3-pyrrolidinedicarboxylic acid
2,3-azetidinedicarboxylic acid
3,4-pyrrolidinedicarboxylic acid
2,3-dihydro-6H~l,4-dioxino[2,3-c]pyrrole-5,7-
dicarboxylic acid
lH-imidazole-2,4-dlcarboxylic acid
l^butyl-lH-pyrrole-2,3-dicarboxylic acid
3-anino-l-oxide-2,4-pyridinedicarboxylic acid
2,3-dihydro-5-phenyl'lH-pyrrolizine-6!7-dicarboxylic
acid
3a,4,5,9b-tetrahydro-3H-cyclopenta[c]quinoline-4/6-
dicarboxylic acid
3a,4,5,9b-tetrahydro-3H-cycLopenta[c]quinoXine-4,8-
dicarboxylic acid
2,3-dihydro-lH-imidazole-4,5-dicarboxylic acid
5-amino-6-methyllutidinic acid
lH-indole-37-dicarboxylic acid
3,3-dimethyl-2,6~piperidinedicarboxylic acid
l-butyl-2,5-pyrxolidinedicarboxylic acid
lH-indole-4,6-dicarboxylic acid
1-(phenylmethyl)-3,4-pyrroiidinedicarboxylic acid
3-(carboxymethyl)-lH-indole-2,6-dicarboxylic acid
3,4~bis(2,2,2-trifluoroethyl)-lH-pyrrole-2,5-
dicarboxylic acid
9-hexyl-9H-carbazoIe-3,6-dicarboxylic acid
3-methyl-5-(1-piperazinylsulphonyl)~2,4-thiophene-
dicarboxylic acid
2,3,4,9-tetrahydro-lH-carbazole-5,7-dicarboxylic
acid
2,3-dimethyl-lH-indole-4,6-dicarboxylic acid
7-amino-l,4-dihydro-4-oxo-3,6-quinolinedicarboxylic
acid
5-amino-3-methyl-2,4-thiophenedicarboxylic acid
(ra-tolylimino)diacetic acid
(o-tolylimino)diacetic acid
D-cystathionine
phenethyliminodiacetic acid
2-benzyl-2,2'-irainodiacetic acid
t-α-glutamyl-L-alanyl-L-alanine
N,N' -dibenzylethylenediarninediacetic acid
N-L-y-glutamyl-D-alanine
glycyl-L-glutamylglycine.
N-(carboxynethyl)-N-(tetrahydro-1,l-dioxido-3-
thienyl)glycxne
N- (2-carboxyethyl) -N-phenyl-ß-alanine
N-(carboxynethyl)-N-octylglycine
N-(tert-butoxycarbonyl)iminodiacetic acid
N-(carboxymethyl)-L-alanine
N- ( 6-amir.ohexyl) -N- (carboxymethyl) glycine
N-(carboxynethyl)-N-tetradecylglycine
N-(1-carboxyethyl)-D-alanine
N- (carbojcyraethyl) -D-alanine
decylimir.odiacetic acid
3,3'-(dimethylhydrazono)bispropanoic acid
N-(caxboxymethyl)-N-[2-(2,6-dioxo-4-morpholinyl)
ethyl]glycine
N-α-aspartylglycine
N-ß-aspartylglycine
N-L-α-aspartyl-(3-alanine
3,4-xylylamino-N,N-diacetic acid
N-(1-carboxyethyl)alanine
N-(carboxymethyl)alanine
N,N'-methylenebisglycine
N-(aminomethyl)-N-(carboxymethyl)glycine
2,2'-(methylhydrazono)bisacetic acid
N- (2-carboxyethyl) -N- (4-methylphenyl) -ß-alanine
N-(2-carboxyethyl)-N-(3-methylphenyl)-ß-alanine
3-[(carboxymethyl)amino]alanine
D-α-aspartyl-D-alanine
N^(2-carboxyethyl)-N-(l-oxohexadecyl)-ß-alanine
N-(2-carboxyethyl)-N-(1-oxodecyl)-ß-alanine
- N-(2-carboxyethyl)-N-(l-oxotetradecyl)-ß-alanine
amino[(carboxymethyl)thio]acetic acid
- N,N'-1,6-hexanediylbis-ß-alanine
- N-(carboxymethyl)~N-phenyl-ß-alanine
- N-(l-caxboxyethyl)-L-alanine
L-glutamic acid
L-aspartic acid
There may also be mentioned, alone or as a mixture, the following tricarboxylic and tetracarboxylic acids, and their anhydrides:
- 3,3',3"-[l,2,3-propanetriyltrls(oxy)tris-propanoic
acid
pyrazinetricarboxylic acid
- 4-(3-carboxyphenyl)-2,5-pyridinedicarboxylic acid
3-(carboxymethyl)-2, 4-guinolinedicarbcxylic acid
- 3-(carboxymethyl)-lH-indole-2,5-dicartaoxylic acid
3-C-carboxy-2-deoxy-D-threopentaric acid
hydroxycitric acid
D-glucopy:eaflurono5yl-D-arabino-2-hexulQfurano5idaric
acid
- 2,3,5,6-pyridinetetracarboxylic acid
N,N'-1,2-ethanediyIbis[N-(carboxymethyl)-ß-alanine
L-α-aspartyl"L-aspartic acid
4™[bis(carboxymethyl)amino]benzoic acid
7-[bis(caxboxymethyl)amino]heptanoic acid
N-(2-carboxyethyl)aspartic acid
3-[bis(2-carboxyethyl)amino]benzoic acid
- 4-[bis(2-carboxyethyl)amino]benzoic acid.
Preferably, it is possible to use 6,6'-[(l,2-dioxo-l,2-ethanediyl)diimino]bis-hexanoic acid, 2,2'-sulphinylbis-acetic acid, 4,13-dioxo-3p5,12,14-tetra-azahexadec=anedioic acid, poly (ethylene glycol)-disuccinate, poly(ethylene glycol)bis(carboxymethyl)-ether, 8-{(carboxymethyl)amino)-8-oxo-octanoic acid, 2,2'-[methylenebis(sulphonyl)]bis-acetic acid, 4,4'-

(1,6-hexanediyldiimino)bis[4-oxo-butanoic] acidp 4,9-dioxo-3,5,6,10-tetraazadodecanedioic acid, 4-[(l-carboxyethyl)amino]-4-oxc-butanoic acid, 6-[(3-carboxy-1-oxopropyl)amino]hexanoic acid, N,N'-(1,6-dioxo-l,6-hexenediyl)bis-glycine, N,N'- (1,3-dioxo-l,3-propane-diyDbis-glycine, 4,7, 9,12-tetraoxapentadecanedioic acid, 4-pyxanone-2,6-dicarboxylic acid, 2,5-pyrazine-dicarboxylic acid,, lH-imidazole-4,5-dicarboxylic acid, 2,6-pyrazinedicarboxylic acid, 2,5-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, 2,5-diphenyl-3,4-furandicarboxylic acid, 2-methyl-3,4-furandicarboxylic acid, D-tartaric acid, DL-tartaric acid, L-tartaric acid, galactaric acid, D-glucaric acid, 2,5-pyridinedicarboxylic acid, 2,5-pyrrolidinedicarboxylic acid, . l-phenyl-lH-pyrrole-3,4-dicarboxylic acid, 2,4-pyrrolidixiedicarboxylic acid, 5-phenyl-2,4-pyrrolidinedicarboxylic acid, 3,5-piperidinedicarboxylic acid, 3,4-pyrrolidine-dicarboxylic acid, l-butyl-2,5-pyrxolidinedicarboxylic acid, 1-(phenylmethyl)-3,4-pyrrolidinedicarboxylic acid, N-(2-carboxyethyl)-N-phenyl-ß-Alanine, N-(carboxynnethyl) -N-octyl-glycine, N- (1-carboxyethyl) -L-Alanine, L-glutam,ic acid, L-aspartic acid, N-(2-carboxyethyl)-Aspartic acid; and mixtures thereof.
Most particularly preferred are 2,2'-sulphinylbis-acetic acid, 2,2'-[methylenebis(sulphonyl)]bis-acetic acid, N,N'- (1,3-dioxo-l,3-propanediyl)bis-glycine, 2,5-furandicarboxylic acid, D-tartaric acid, DL-tartaric acid, L-tartaric acid, galactaric acid, L-glutamic acid, L-aspartic acid, and mixtures thereof.
It is also possible to use a lactone comprising at least one carboxyl group, in particular 1, 2 or 3 COOH groups. Preferably, the lactones comprise 5 to 14 carbon atoms, in particular 6 to 13, or even 6 to 12 carbon atoms.
The following lactones may be most particularly mentioned, alone or as a mixture:
- tetrahydro-2,2-dimethyl-5-oxo-3-furancarboxylic acid
- 4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-
carboxylic acid
4,6-dimethyl-2-oxo-2H-pyran-5-carboxylic acid 2-oxo-2H~pyran-5-carboxy-2-pentenedioic acid 2-oxo-2H-l-benzopyran-3-carboxylic acid
- 2-oxo-2H-pyran-6-carboxylic acid
1,3"dihydro-3-oxo-l-isobenzofurancarboxylic acid 4-iuethyl-2-oxo-2H-l-benzopyi:an-3-carboxylic acid l-oxo-lH-2-benzopyran-3-carboxylic acid 8-xnet;hoxy-2-oxc-2H^l-benzopyran-3-carboxylic acid 2-oxo-l-oxaspiro[4.5]decane-4-carboxylic acid 2-oxo-2H-pyran-3-carboxylic acid
- 4-methyl-2-oxo-2H-pyran"6-carboxylic acid
3-oxo-3H-naphtho[2,l-b]pyran-2-carboxylic acid
- tetrahydro-5-oxo-2,3-furandicarboxylic acid
1,3-dihydro-3-oxo-4-isobenzofurancarboxylic acid 1,3~dihydro-l-oxo-5-isobenzofurancarboxylic acid
- hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-7-
carboxylic acid
6-methyl"2,4-dioxo-2H~pyran-5-carboxylic acid l-oxo-3-isochromancarboxylic acid 2-oxo-2H-l-benzopyran-6'-carboxylic acid 6-methyl-2-oxo-2H-l-benzopyran-3-carboxylic acid
2,5-dihydro-4,5/5-trimethyl-2-oxo-3-furancarboxylic
acid
tetrahydro-5-oxo-2-phenyl-3-furancarboxylic acid
- tetrahydro-5-oxo-4-propyl-2-furoic acid
2-butyl-2,3-dideoxypentaric acid
2-oxo-2H-l-benzopyrar-7-carboxylic acid
- 2-oxo-l-oxaspiro[4.4]nonane-4-carboxylic acid
4-ethyltetrahydro-5-oxo-2-furoic acid
- 5-ethyltetrahydro-2,3-dimethyl-6-oxo-2H-pyran-2-
carboxylic acid
- 7-methoxy-2-oxo-2H-l-ber:ZOpyran-3-carboxylic acid
2-oxo-2H-l-benzcpyran~4-carboxylic acid
- 2-oxo-6-pentyl-2H-pyran-3-carboxylic acid
- 7-oxo-4-oxepanecarboxylic acid
- 3-(carbcxymethyl)-2,3-dideoxypentaric acid
- 2,3-dihydro-2-oxo-7-benzofurancarboxylic acid
- l,3,4,5-tetrahydro-l-oxo-2-benzoxepin-7-carboxylic
acid
- 3,4-dihydi:o-3-oxo-lH-2-ben20pyran-6-carboxylic acid
- 2,3,4,5-tetrahydro-2-oxo-l-benzoxepin-7-carbOxylic
acid
- 3,4-dihydro-l-oxo-lH-2-benzopyran-8-carboxyl,ic acid
1,3,4,5-tetrahydro-3-oxo-2-benzoxepin-9-carboxylic
acid
- 1,3, 4, 5-tetrahydro-3-oxo-2-benzoxepin-7-carboxylic
acid
- 3,4-dihycro-2-oxo-2H-l-benzopyran-8-carboxylic acid
- 1,3,4,5-tetrahydro-l-~oxo-2-benzoxepin-9-carboxylic
acid
- 3r4-dihydro-l-oxo-lH-2-benziOpyran-6-carboxylic acid
- 3,4-dihydro-3-oxo-lH-2-benzopyran-8-carboxylic acid
- 2,3,4,5-tetrahydro-2-oxo-l-benzoxepin-9-carboxylic
acid
isocirric acid lactone 5-oxo-2-tetrahydrofurancarboxylic acid.
Preferably, it is possible to use tetrahydro~5-oxo-2,3-furandicarboxylic acid, 1,3-dihydro-3-oxo-4-isobenzofurancarboxylic acid, 1,3-dihydro-l-oxo-5-isobenzofurancarboxylic acid, tetrahydro-5-oxo-2-phenyl-3-fucancarboxylic acid, isocitric acid lactone, 5-oxo-2-tetrahydrofurancarboxylic acid and mixtures thereof.
The said polycarboxylic acid and/or its cyclic anhydride and/or the lactone, and mixtures thereof, preferably represents 1 to 40% by weight, or even 5 to 35% by weight, in particular 10 to 30% by weight, and even better 14 to 25% by weight, of the total weight of the final polycondensate.
In a preferred embodiment of the invention/ the aromatic monocarboxylic acid is present in a molar quantity of less than or equal to that of the non-aromatic roonocarboxylic acids (of high and low melting points); in particular the ratio between the number of moles of aromatic monocarboxylic acid and the total number of moles of non-aromatic monocarboxylic acids is preferably between 0.08 and 0.70, in particular between 0.1C and 0.60, in particular between 0.12 and 0.40,
It is observed that this makes it possible in particular to obtain a polymer that is advantageously soluble in the oily media generally used to formulate cosmetic compositions of the lipstick or foundation type; moreover, the film obtained has sufficient rigidity and flexibility for its use in this type of formulation, while having a gloss and a gloss staying power as desired.
Preferably, the polycondensste according to the invention can be obtained by the reaction:
of at least one polyol chosen from, alone or as a mixture, 1,2,6-hexanetriol, trimethyiolethane, trimethylolpropane, glycerol; pentaerythritol, erythritol, diglycerol, ditrimethylolpropane; xylitol,
sorbitol, mannitol, dipentaerythritol and/or
triglycerol;
preferably present in a quantity of 10 to 3C% by
weight, in particular 12 to 25% by weight, and even
better 14 to 22% by weight, relative to the total
weight of the final polycondensate;
of at least one non-aromatic monocarboxylic acid having a melting point greater than or equal to 25"C, chosen from, alone or 33 a mixture, decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, cerotic acid, petroselinic acid, vaccenic acid, elaidic
acid, gondoic acid, gadoleic acid, erucic acid, nervonic acid;
preferably present in a quantity o£ 22 to 80% by weight, in particular 25 to 75% by weight, and even better 27 to 7G% by weight, relative to the total weight of the final polycondensate;
ox at least one non-aromatic monocarboxylic acid having a melting point of less than 25CC, chosen from, alone or as a mixture, capxoic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexsnoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isocctanoic acid, nonanoic acid, isononanoic acid, isostearic acid; caproleic acid, obtusilic acid, undecylenic acid, dodecylenic acidr linderic acid, myristoleic acid, physeteric acid, tsuzuic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid;
preferably present in a quantity of 0.1 to 35% by weight, in particular 0.5 to 32% by weight, and even better 1 to 30% by weight, relative to the total weight of the final polycondensate;
of at least one aromatic monocarboxylic acid chosen from, alone or as a mixture, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butylbenzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-l-naphthoic acid; preferably present in a quantity of 0.1 to 10% by weight, in particular 1 to 9.5% by weight, or even 1.5 to 8% by weight, relative to the total weight of the final polycondensate; and
of at least one polycarboxylic acid or one of its anhydrides, chosen from, alone or as a mixture, decanedioic acid, dodecanedioic acid, cyclopropanedicarboxyiic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, 1,4-naphthalene-dicarboxylic acid, 2,3-naphthalenedicarbOKylic acid, 2,6-naphthalenedicarboxylic acid, suberic acid, oxalic
acid, malonic acid, succiaic acid, phthaiic acid, terephthalic acid, isophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid; cyclohexanetricarboxylic acid, trimellitic dcid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, phthaiic anhydride, trimellitic anhydride, maleic anhydride, succinic anhydride, 2,2'-sulphinylbis-acetic acid, 2,2'-[methylenebis(sulphonyl)Ibis-acetic acid, N,N'-(1, 3-dioxo-l,3-propanediyl)bis-glycine, 2,5-furandi-carboxylic acid, D-tartaric acid, DL-tartaric acid, L-tartaric acid, galactaric acid and mixtures thereof; preferably present in a quantity of 1 to 40% by weight, irx particular 10 'to 30% by weight, and even better 14 to 25% by weight, relative to the total weight of the final polycondensate.
Preferably, the polycondensate according to the invention can be obtained by the reaction;
of at least one polyol chosen from, alone or as a mixture, glycerol, pentaerythritol, sorbii:ol and mixtures thereof, and better still pentaerythritol alone; present in a quantity of 10 to 30% by weight, in particular 12 to 25% by weight, and even better 14 to 22% by weight, relative ts the total weight of the final polycondensate;
of at least one non-aromatic monocarboxylic acid chosen from, alone or as a mixture, lauric acid, palmitic acid, stearic acid, behenic acid and mixtures thereof, and better still stearic acid alone; preferably present in a quantity of 22 to 80% by weight, in particular 25 to "75% by weight, and even better 27 to 70% by weight, relative to the total weight of the final polycondensate;
of at least one non-aromatic monocarboxylic acid chosen from, alone or as a mixture, igooctanoic acid, isononanoic acid, isostearic acid;
preferably present in a quantity of 0.1 to 35% by weight, in particular 0.5 to 32% by weight, and even, better 1 to 30% by weight, relative to the total weight of the final polycondensate;
of at least one aromatic monocarboxylic acid chosen from, alone or as a mixture, oenzoic acid, o-toluic acid, m-toluic acid, 1-naphthoic acid, and better still benzoic acid alone; present in a quantity of 0.1 to 10% by weight, in particular 1 to 9.5% by weight, or even 1.5 to 8% by weight relative to the total weight of the final polycondensate; and
of at least one polycarboxylic acid or one of its anhydrides, chosen from, alone or as a mixture, phthalic anhydride and isophthalic acid, and better still isophthalic acid alone; present in a quantity of 1 to 40% by weighs, in particular 10 to 30% by weight, and even better 14 to 25% by weight, relative to the total weight of the final polycondensate.
In a preferred embodiment of the invention, the polycondensate can be prepared exclusively (or solely) from the monomers/categories of monomers mentioned in the present description, that is to say that it does not comprise other additional monomers/categories of monomers; in this case, the said polycondensate is therefore constituted exclusively (or solely) of 10-30% by weight of polyol comprising 3 to 6 hydroxyl groups; from 22-80% by weight of linear, branched and/or cyclic, saturated or unsaturated, non-aromatic monocarboxylic acid comprising 10-32 carbon atoms, and having a melting point greater than or equal to 25"C; from 0.1 to 35% by weight, of linear, branched and/or cyclic, saturated or unsaturated, non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms, and having a melting point strictly less than 25 °C; from 0,1 to 10% by weight of aromatic monocarboxylic acid comprising 7-11 carbon atoms, optionally substituted with- 1-3 linear, branched and/or cyclic,

saturated or unsaturated alkyl radicals which comprise 1-32 carbon atoms; from 1 to 40% by weight of linear, branched and/or cyclic, saturated or unsaturated, or even aromatic, polycarboxylic acid comprising at least 2 carboxyl groups COOH which may comprise heteroatoms; and/or a cyclic anhydride of such a polycarboxylic acid; and/or a lactone comprising at least one COOH group.
Preferably, the polycondensate according to the invention has:
an acid value, expressed in mg of potassium hydroxide per g of polycondensate, greater than or equal to 1; in particular between 2 and 30, and better still between 2,5 and 15; and/or
a hydroxyl value, expressed in mg of potassium hydroxide per g of polycondensate, greater thsn or. equal to 30; in particular between 30 and 120, and better still between 40 and 90.
These acid and hydroxyl values can be easily determined by persons skilled in the art by the usual analytical methods.
Preferably, the polycondensate according to the invention has a viscosity, measured at 110'C, between 20 and 4000 mPa.s, in particular between 30 and 3500 mPa.s, or even between 4C and 3000 mPa.s, and better still between 50 and 2500 mPa.s. This viscosity is measured in the manner described before the example.
Preferably, the polycondensate according to the invention has a weight-average molecular mass (MwJ between 1500 and 300 000, or even between 2000 and 200 000, and in particular between 3000 and 100 000.
The average molecular weight rr.ay be determined by gel permeation Chromatography or by light scattering, depending or. the solubility of the polymer considered.
Moreover, the polycondensate is advantageously soluble in the cosmetic oily media customarily used, and in particular in vegetable oils, alkanes, fatty esters, fatty alcohols, silicone oils/ and ttore particularly in, media comprising isododecane, Parleam, isononyl isononanoate, octyldodecanol, phenyl trimethicone and/or C12-C15 alkyl benzoate.
The expression soluble is understood to mean that the polymer forms a clear solution in at least one solvent chosen from isododecane, Farleam, isononyl isononanoate, octyldcdecanol and C12-C15 alkyl benzoate, in an amount of at least 50% by weight, at 70°C. Some compounds even have a particularly advantageous solubility in certain fields of application, namely a solubility in at least one of the solvents mentioned above, in an amount of at least 50% by weight at 25°C.
The polycondensate according to the invention may be prepared by the estetification/polycor.dengation methods customarily used by persons skilled in the art. By way of illustration, a general method of preparation consists:
in mixing the polyol and the aromatic and non-aromatic monocarboxylic acids,
in heating the mixture under an inert atmosphere, first up to the ir.elting point (generally 100-130°C) and then at a temperature between 150 and 220DC until there is complete consumption of the monocarboxylic acids (obtained when the acid value is leas than or equal to 1), preferably while continuously distilling the water formed, and then
in optionally cooling the mixture to a temperature of between 90 and 150°C,
in adding the polycarboxylic acid and/or the cyclic anhydride and/or the lactone, all at once or sequentially, and, then
in again heating to a temperature less than or equal to 220°C, in particular between 170 and 220°C, preferably while continuing to remove the water formed, until the desired characteristics in terms of acid, value, viscosity, hydroxyl value and solubility are obtained,
Iz is possible to add conventional esterification catalysts, for example of the sulphonic acid type (in particular at a concentration by weight between 1 and 10%) or of the titanate type (in particular at a concentration by weight between 5 and 100 ppm).
It is also possible to carry out the reaction, entirely or partially, in an inert solvent such as xylene and/or under reduced pressure, in order to facilitate the removal of water.
Advantageously, neither catalyst nor solvent is used.
The said method of preparation may additionally comprise a step of adding at least one antioxidant to the reaction medium, in particular at a concentration by weight between 0.01 and 1%, relative to the total weight of monomers, so- as to limit the possible degradations linked to prolonged heating.
The antioxidant may be of the primary type or of the secondary type, and may be chosen from hindered phenols, aromatic secondary amines, organophosphate compounds, sulphur compounds, lac-ones, acrylated bisphenols; and mixtures thereof.
Among the antioxidants particularly preferred, thece may be mentioned in particular BHT, ERA, TBHQ, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene, octadecyl 3,5-di-tert-butyl-4-hydroxy-cinnamate, tetrakis-methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)prcpionate methane, octadecyl 3-(3,5-di-text-butyl-4-hydroxyphenyl)propionate, 2,5-di-tert™ butylhydroquinone, 2,2-methybis(4-methyl-6-tert-butylphencl), 2,2-methylenebis(4-ethyl-6-tert-butyl-phenol), 4,4-butylidenebis(6-tert-butyl-m-cresol), N,N-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydro-cinnamamide), pentaerythritol tetrakis(3-(3,5-di-ter--butyl-4-hydroxyphenyl)propionate), in particular that marketed by CIBA under the name IRGANOX 1010; octadecyl 3-(3,5-di-tert^butyl-4-hydroxyphenyl)pjropionate/ in particular that marketed by CIBA under the name IRGANOX 1076; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-l,3,5-triazine-2,4,6-(1H,3H,5H)trione, in particular that marketed by Mayzo of Norcrosa, Ga under the name BNX 3114; distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl"phosphite, in particular that marketed by CIBA under the name IRGAFOS 168; dilauryl thiodipropionate, in particular that marketed by CIBA under the name IRGANCX PS800; bis(2,4-di-tert-butyl)pentaerythritol diphosphite, in particular that marketed by CIBA under the IRGAFOS 126; bis(2,4-bis[2-phenylpropan-2-yl]phenyl)pentaerythritol diphosphite, triphenylphosphite, (2,4-di-rert-butylphenyl)penta¬erythritol diphosphite, in particular that marketed by GE Speciality Chemicals under the name ULTRANOX 626; tris(nonylphenyl)phosphite, in particular that marketed by CIBA under the name IRGAFOS TNPP; 1:1 mixture ' of N,N-hexamsthylenebis(3,5~di-tert-butyl-4-hydroxyhydro-cinnamamide) and of tris(2,4-di-tert-butylphenyl)-phosphate, in particular that marketed by CIBA under the name Irganox B 1171; tetrakis(2,4-di-tert-butylphenyl) phosphite, in particular that marketed by CIBA under the name IRGAFOS P-EPQ; distearyl
thiodipropionate, in particular that marketed by CIBA under the name IRGANOX PS802; 2, 4-bis (octylthiomethyl) -o-cresol, in particular that marketed by CIBA under the name IRGANOX 1520; 4, 6-bis (dodecylthiomethyl) -o-cresol, in particular that marketed by CIBA under the name IRGANOX 1726.
The polycondensates according to the invention may be used very advantageously in a composition, in particular a cosmetic or pharmaceutical composition, which comprises, moreover, a physiologically, in particular cosmetically or pharmaceutically, acceptable medium, that is to say a medium that is compatible with the cutaneous tissues such as the skin of the face or of the body, and keratin materials such as the hair, the eyelashes, the eyebrows of the nails.
The quantity of polycondensate present in the compositions of course depends on the type of composition and on the desired properties and may vary within a very broad range, generally between 0.1 and 70% by weight, preferably between 1 and 50% by weight, in particular between 10 and 45% by weight, or even between 20 and 40% by weight, and even better between 25 and 35% by weight, relative to the weight of the final cosmetic or pharmaceutical composition.
The composition may then comprise, depending on the application envisaged, the usual constituents for this of composition.
The composition according to the invention may advantageously comprise a liquid fatty phase, which may constitute a solvent medium for the polyttiers according to the invention, and which may comprise at least one compound chosen from volatile or non-volatile, carbonaceous, hydrocarbon, fluorinated and/or silicone oils ar.d/or solvents of inorganic, animal, plant or
synthetic origin, alone or as a mixture insofar as they form a homogeneous and stable mixture and are compatible with the use envisaged.
The expression "volatile" is understood to mean, for the purposes of the invention, any compound liable to evaporate on contact with keratin materials, or the lips, in less than one hour, at room temperature (25"C) and atmospheric pressure (1 atm) , In particular, this volatile compound has a non-zero vapour, pressure, at room temperature and atmospheric pressure, in particular ranging from 0.13 Pa to 40 000 Pa (10~3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg} . By contrast, the expression "non-volatile" is understood to mean a compound which remains on the keratin materials or the lips at room temperature and atmospheric pressure for at least one hour and which has in particular a vapour pressure of less than. 10-3 mmHg (0.13 Pa) ,
Preferably, the physiologically acceptable medium of the composition according to the invention may comprise, in a liquid fatty phase, at least one oil and/or solvent which may be chosen from, alone or as a mixture:
I/ Esters of monocarboxylic acids with monoalcohols and polyalcohols; advantageously, the said ester is a C12-C15 alkyl benzoate or corresponds to the following formula: R' i-COO-Rf 2 where:
R'i represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably of 7 to 19 carbon atoms, optionally comprising one or more ethylenic double bonds, optionally substituted and whose hydrocarbon chain may be interrupted by one or more heteroatoms chosen from N and 0 and/or one or more functional groups, and
R'z represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably of 3 tc 30 carbon atoms and even better of 3 to 20 carbon atoms, optionally comprising one or more ethylenic double bonds, optionally substituted and whose hydrocarbon chain may be interrupted by one or more heteroatomg chosen from N and 0 and/or one or more carbonyl functional groups.
The expression "optionally substituted" is understood to mean that R'1 and/or R'2 may carry one or more substituents chosen, for example, from the groups comprising one or more heteroatoms chosen from 0 and/or N, such as amino, amine, alkoxy, hydroxyl.
Examples of R'1 groups are those derived from fatty acids, preferably higher fatty acids, chosen from the group constituted of acetic, propionic, butyric, caproic, caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, arachidic, behenic, oleic, linolenic, linoleic, oleostearic, arachidonic and erucic acids, and mixtures thereof. Preferably, R' 1. is an unsubstituted branched alkyl group of 4 to 14 carbon atoms, preferably of 8 to
10 carbon atoms and R; is an unsubstituted branched
alkyl group of 5 to 15 carbon atoms, preferably of 9 to
11 carbon atoms.
There may preferably be mentioned in particular C8-C48 esters, optionally incorporating in their hydrocarbon chain one or more heteroatoms among N and 0 and/or one or mote carbonyl functional groups; and more particularly purcellin oil (cetostearyl octanoate), isononyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldodecyl steaxate, 2-octyldodecyl erucate, isostearyl iscstearate, C12 to C15 alcohol benzoate, hexyl laurate, diisopropyl adipate; and alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates,
for example fatty alcohols such as propylene glycol dioctanoate, and isopropyl N-lauroyl sarcosinate (in particular Eldew-205SL from Ajinomoto); hydxoxyl esters such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters; branched C8~C16 esters, in particular isohexyl neopentanoate,
2/ Plant hydrocarbon oils having a high content of triglycerides constituted of fatty acid esters of glycerol in which the fatty acids may have varied chain lengths from C« to C24, it being possible for these chains to be linear or branched, saturated or unsaturated; these oils are in particular wheatgerm oil, corn oil, sunflower oil, shea oil, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cotton seed oil, lucern oil, poppy seed oil, pumpkin seed oil, sesame oil, gourd oil, avocado oil, hazelnut oil, grape seed or blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quir.oa oil, olive oil, rye oil, saf flower oil, candlenut oil, passion flower oil, musk rose oil, jojoba oil, palm oil, calophyllum oil; or alternatively triglycerides of caprylic/capric acids 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.
3/ C6-C32, in particular C12-C26, alcohols, and in particular monoalcchols, such as oleyl alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol and octyldodecanol.
4/ Volatile on non-volatile, linear or branched hydrocarbon oils of synthetic or mineral origin, which may be chosen from hydrocarbon oils having from 5 to 100 carbon atoms, and in particular petroleum jelly, polydecenes, hydrogenated polyisobutenes such as
Parleam, squalane, perhydrosqualene and mixtures thereof.
There may be mentioned more particularly linear, branched and/or cyclic C5-C48 alkanes, and preferably branched C8-C16 alkanes such as C8-C16 isoalkanes of petroleum origin (also called isoparaffins); in particular decane, heptane, dodecane, cyclohexane; and isododecane, isodecane, isohexadecane.
5/ Volatile or non-volatile silicons oils; as volatile silicone oils, there may be mentioned linear or cyclic volatile silicone oils, in particular those- having a viscosity of less than 8 centistokes, and having in particular from 2 to 10 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 22 carbon atoms; and in particular octamethylcyclotetrasiloxane, decamethyl-cyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltri-siloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, methylhexyldimethylsiloxane and mixtures thereof.
The non-volatile silicone oils which can be used according to the invention may be polydimethylsilcxanes (PDMS), polydimethylsiloxanes containing alkyl or alkoxy groups which are pendent and/or at the silicone chain end, groups each having from 2 to 24 carbon atoms, phenylated silicones such as phenyltrimethicones, phenyldimethicones, phenyl-trimethylsiloxydiphenylsiloxanes, diphenyldimethicones, diphenylmethyldipher.yltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates.
Preferably, the physiologically acceptable medium of the composition according to the invention comprises, in a liquid fatty phase, at least one oil and/or
solvent chosen from, alone or as a mixture, isododecane, Parleam, isononyl isononanoate, octyldodecanol, phenyl trimethicone, C12-C15 alkyl benzoates and/or D5 (decamethylcyclopentasiloxane).
The liquid fatty phase may additionally comprise additional oils and/or solvents which may be chosen from, alone or as a mixture:
fluorina^ied oils such as perfluoropolyethers/ perfluoroalkanea, such as perfluorodecalin, perfluorodamantanes, monoesters, diesters and triesters of perfluoroalkyl phosphates and fluorinated ester, oils;
oils of animal origin;
C6 to C40, in particular C10-C40/ ethers; propyiene glycol ethers that are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol mono-n-butyl ether;
C8-C32 fatty acids, such as oleic acid, lir.oleic acid/ linolenic acid and mixtures thereof;
bifunctional oils, comprising two functional groups chosen from an ester and/or an amide and comprising from 6 to 30 carbon atoms, in particular 3 to 28 carbon atoms, even better from 1C to 24 carbons, and 4 heteroaroms chosen from 0 and N; preferably amide and ester functional groups being in the chain;
ketones that are liquid at room temperature (25°C) such as methyl enhyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone;
aldehydes that are liquid at room temperature, such as benzaldehyde, aceteldehyde.
The liquid fat~y phase may represent 1 to 90% by weight of the composition, in particular 5 to 75% by weight, in particular 10 to 60% by weight, or even 25 to 55% by weight, of the -otal weight of the composition.
The composition according to the invention may advantageously comprise a thickening agent which may be chosen in particular from:
silicas, in particular hydrophobic silicas, such as those described in the document EP-A-898960, and for example marketed under vhe references "AEROSIL R812®" by the company Degussa, "CAB-0-SIL TS-530®", "CAB-0-SIL TS-610®", VVCAB-O-SI1 TS-720®" by the company Cabot, "AEROSIL R972*", "AEROSIL R974®" by the company Degussa;
clays such as montmorillonite, modified clays such as bentones for example, stearalkonium hectorite, stearalkonium bentonite,
alkyl ethers of polysaccharides (in particular, whose alkyl group contains from 1 to 24 carbon atoms, preferably from 1 to 10, even better from 1 to 6, and more especially from 1 to 3) such as those described in the document EP-A-898958.
The quantity of thickening agent in the composition according to the invention may range fom 0.05 to 40% by weight, relative to the total weight of the composition, preferably from 0.5 to 20% and even better, from 1 to 15% by weight.
The composition according to the invention may also comprise at least one wax of plant, animal, mineral or synthetic origin, or even silicone wax.
There may be mentioned, in particular, alone or as a mixture, hydrocarbon waxes such as beeswax, Carnauba wax, Candelilla wax, Ouricoury wax, Japan wax, cork fibre wax or sugarcane wax; paraffin wax, lignite wax, macrocrystalline waxes; lanolin wax; Montan wax; ozokerites; polyethylene waxes; waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils, fatty esters and glycerides that are concrete at 25°C. It is also possible to use silicone waxes, among which there
may be mentioned alkyl polymethylsiloxane, alkoxy polymethylsiloxane and/or polymethylsilcxane esters.
The quantity of wax in the composition according to the invention may range from 0,1 to 701 by weight, relative to the total weight of the composition, preferably from 1 to 40% by weight, and even better from 5 to 30% by weight.
The composition according to the invention may also comprise one or more colouring matters chosen from pulverulent compounds such as pigments, fillers, pearlescent agents and glitter, and/or fat-soluble or water-soluble colorants.
The colouring matter, in particular the pulverulent colouring matter, may be present in the composition in an amount' of 0.01 to 50% by weight, relative to the weight of the composition, preferably 0.1 to 40% by weight, or even 1 to 30% by weight.
The expression pigments should be understood to mean particles of any shape, that are white or coloured, inorganic or organic, insoluble in physiological medium, intended to colour the compositions.
The expression pearlescent agents should be understood to mean iridescent particles of any shape, in particular produced by certain molluscs in their shell or else synthesized.
The pigments may be white or coloured, inorganic and/or organic, interferential or otherwise. There may be mentioned, among the inorganic pigments, titanium dioxide, optionally surface-treated, zirconium or cerium oxides, and iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments, there may be
mentioned carbon black, D&C type pigments, and carmine-, barium-, strontium-, calcium and alunutiium-based lacquers.
The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, coloured pearlescent pigments such as mica-titanium with iron oxides, mica-titanium with in particular ferric blue or chromium oxide, mica-titanium with an organic pigment of the abovementioned type and bismuth oxychloride-based pearlescent pigments.
The fillers nay be inorganic or organic, lamellar or spherical. There may be mentioned talc, mica, silica, kaolin, nylon and polyethylene powders, poly-ß-alanine and polyethylene powders, Teflon, lauroyllysine, starch, boron nitride, tetrafluoroethylene polymer powders, hollow microspheres such as Expancel (Nobel Industrie), polytrap (Dow Corning) and microbeads of silicone resin (Tospearls from Toshiba, for example), precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres (SILICA BEADS from MAPRECOS), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from S to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate or lithium stearate, zinc lauxate, magnesium myristate.
The fat-soluble colorants are for example Sudan red, DC Red 17, DC Green 6, ß-carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5, quinoline yellow. They may represent 0.01 10 20% of the weight of the composition, and even better from 0.1 to 6%.
The water-soluble colorants are, for example, beet juice, methylene blue, and may represent 0.01 to 6% of the total weight of the composition.
The composition may additionally comprise other ingredients commonly used in cosmetic compositions. Such ingredients may be chosen from antioxidants, perfumes, essential oils, preservatives, cosmetic active agents, moisturizers, vitamins, ceramides, sunscreens, surfactants, spreading agents, wetting agents, dispersing agents, antifoaitis, neutralizers, stabilizers,, polymers and in particular fat-soluble film-forming polymers, and mixtures thereof.
Of course, persons skilled in the art will be careful to choose this or these optional additional compounds, and/or their quantity, such that the advantageous properties of the composition for use according to the invention are not, or not substantially, impaired by the addition envisaged.
The compositions according to the invention may be provided in any acceptable and customary form for a cosmetic or pharmaceutical composition.
They may therefore be provided in the form of a suspension, a dispersion, in particular an cil-in-water dispersion by means of vesicles; an organic or oily solution that is optionally thickened or even gelled; an oil-in-water, water-in-cil or multiple emulsion; a gel or a foam; an oily or emulsified gel; a dispersion of vesicles, in particular lipid vesicles; a two-phase or multiphase lotion; a spray; a lotion/ a cream, an ointment, a soft paste, an unguent, a cast or moulded solid, and in particular as a stick or in a dish, or as a compact solid.
Persons skilled in the art will be able to choose the appropriate galenic form, and its method of preparation, on the basis of their general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the carrier, and, on the other hand, the application envisaged for the composition.
The compositions in accordance with the invention have improved gloss and staying power of the said gloss Compared with the state of the art, they can be used for caring for or making up keratin materials such as the hair, the skin, the eyelashes, the eyebrows, the nails, the lips, the scalp and more particularly for making up the lips, the eyelashes and/or the face.
They may therefore be provided in the form of a care and/or make-up product for the skin of the body or of the face, for the lips, the eyelashes, the eyebrows, the hair, the scalp or the nails; an anti-sun or a self-tanning product; a hair product, in particular for dyeing, conditioning and/or caring for the hair; they are advantageously provided in the form of a mascara, a lipstick, a lip gloss, a blusher or an eyeshadow, or a foundation.
The subject of the invention is also a method for the cosmetic treatment of keratin materials, in particular the skin of the body or of the face, the lips, the nails, the hair and/or the eyelashes, comprising the application to the said materials of a cosmetic composition as defined above.
This method according to the invention makes it possible in particular to care for or make up the lips by applying a lipstick or lip gloss composition according to the invention.
The invention is illustrated in greater detail in the following examples.
Method of measuring the viscosity
The viscosity at 80°C or 110°C of the polymer is measured with the aid of a cone plate viscometer of the BROOKFIELD CAP 1000+ type.
The appropriate cone plate is determined by persons skilled in the art on the basis of their general knowledge, in particular:
between 50 and 500 mPa.s, it is possible to use a
cone 02
between 500 and 1000 mPa.s: cone 03
- between 1000 and 4000 mPa.s: cone 05
- between 4000 and 10 000 mPa.s: cone 06
Example 1: Synthesis of pentaerybhrityl benzoata/isophthalate/isostearate/stearate
20 g of benzoic acid, 210 g of stearic acid, 10 g of isostearic acid and 100 g of pentaerythritol are loaded into a reactor equipped with mechanical stirring, an argon inlet and a distillation system, and then the mixture is gradually heated, under a gentle argon Stream, to 110-130°C in otder to obtain a homogeneous solution. The temperature is then gradually increased to 180'C and iz is maintained for about 2 hours. The temperature is again increased to 220°C and it is maintained until an acid value of less than or equal to 1 is obtained, which takes about 11 hours. The mixture is cooled to a temperature of between 100 and 130°C and then 100 g of isophthalic acid are introduced and the mixture is again gradually heated to 220'C for about 11 hours.
450 g of pentaerythrityl benzoate/isophthalate/-isostearate/stearate polycondensate are thus obtained in the form of a very thick oil.
The polycondensate has the following, characteristics:
- soluble at 50% by weight, at 70°C, in Parleam
acid value =7.1
n110°c = 850 mPa.s
- Mw = 28 500
ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of non-aromatic monocarboxylic acids: 0.166.
Example 2: Synthesia of pentaerythrityl behenate/benzoate/isophbhalate/iaostearate
20 g of benzole acid, 140 g of behenic acid, 140 g of isostearic acid and 100 g of pentaerythritol are loaded into a reactox equipped with mechanical stirring, an argon inlet and a distillation system, and then the mixture is gradually heated, under a gentle argon, stream, to 110-130°C in order to obtain a homogeneous solution. The temperature is then gradually increased to 180°C and it is maintained for about 2 hours. The temperature is again increased to 220°C and it is maintained until an acid value of less than or equal to 1 is obtained, which takes about 11 hours. The mixture is cooled to a temperature of between 100 and 130°C and then 100 g of isophthalic acid are introduced and the mixture is again gradually heated to 220°C for about 11 hours.
440 g of pentaerythrityl behenate/benzoate/-isophthalate/isostearate polycondensate are thus obtained in the form of a very thick oil.
The polycondensate has the following characteristics: soluble at 50% by weight, at 70°C, in Parleaw acid value = 4.2 = 2050 mFa.s
ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of non-aromatic monocarboxylic acids: 0.181.
Example 3
In a manner similar to the preceding examples, the following polycondensates are prepared (the % values are by weight):

(Table Removed)

"at 25°C" indicates that the polymer is soluble at 50% by weight, at 25°C, in Parlearr.;
"at 70°C" indicates that the polymer is soluble at 50% by weight, at 70°C, in Parleam.
Example 4
A lipstick having the following composition was
prepared:
polyconder.sate of Example C 30 g
polyethylene wax 11 g
pigments and fillers 7 g
Parleam (hydrogenated isoparaffin) qs 100 g
Example 5
A lipstick having the following composition was
prepared:
polycondensate of Example D 30 g
polyethylene wax 11 g
pigments and fillers 7 g
Parleam (hydrogenated isoparaffin) qs 100 g
Example 6
A lipstick having the following composition is
prepared:
- polycondensate of Example 1 10 g
polyethylene wax 11 g
- pigments and fillers 7 g
Parleam (hydrogenated iaoparaffin) qs 100 g

CLAIMS
1. Cosmetic or pharmaceutical composition comprising, in a cosmetically or pharmaceutically acceptable medium, at least one polycondensate capable of being obtained by the reaction:
- of 10 to 30% by weight, relative to the total weight
of the polycondensate, of at least one polyol
comprising 3 to 6 hydroxyl groups;
- of 22 to 80% by weight, relative to the total weight
of the polycondensate, of at least one linear,
branched and/or cyclic, saturated or unsaturated,
non-aromatic monocarboxylic acid comprising 10 to 32
carbon atoms, and having a melting point greater
than or equal tc 25°C;
- of 0.1 to 35% by weight, relative to the total
weight of the polycondensate, of at least one
linear, branched and/or cyclic, saturated or
unsaturated, non-aromatic monocarboxylic acid
comprising 6 to 32 carbon atoms and having a melting
point strictly less than 25°C;
- of 0,1 to 10% by weight, relative to the total
weight of the polycondensate, of at least one
aromatic monocarboxylic acid comprising 7 to 11
carbon atoms, optionally additionally substituted
with 1 to 3 linear, branched and/or cyclic,
saturated or unsaturated alkyl radicals which
comprise 1 to 32 carbon atoms;
- of 1 to 40% by weight, relative to the total weight
of the polycondensate, of at least one linear,
branched and/or cyclic, saturated or unsaturated, or
even aromatic, polycarboxylic acid comprising at
least 2 carboxyl groups COOH, which may comprise
heteroatcms; and/or a cyclic anhydride of such a
polycarboxylic acid; 'and/or a lactone comprising at
least one COOH group.
2. Composition according to Claim 1, in which the
polyol is chosen from, alone or: as a mixture:
- triols, such as 1,2,4-butanetriol, 1,2,6-
hexanetriol, trimethylclethane, trimethylolpropane,
glycerol;
tetraols, such as pentaerythritol, erythritol, ciglycerol or ditrifltethylolpropane;
- pentols such as xylitol;
hexols such as sorbitol and mannitol; or alternatively dipentaerythritol or triglycerol.
3. Composition according to either of the preceding
claims, in which the polyol, ox the mixture of polyols,
represents 12 to 25% by weight, and even better 14 to
22% by weight, of the total weight of the
polycondensate.
4. Composition according to any one of the preceding
claims, in which the non-aromatic monocarboxylic acid
having a melting point greater than or equal to 25°C is
chosen from, alone or as a mixture:
saturated monocarboxylic acids such as decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, cerotic (hexacosanoic) acid; unsaturated but non-aromatic monocarboxylic acids such as petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, nervonic acid.
5. Composition according to one of the preceding
claims, in which the non-aromatic monccarboxylic acid
having a melting point greater than or equal to 25°C,
or the mixture of the said acids, represents 25 to "75%
by weight, or even 27 to 70% by weight, and even better
28 to 65% by weight, of the total weight of the
polycondensate.
6. Composition according to one of the preceding
claims, in which the non-aromatic monocarboxylic acid
having a melting point of less than 25°C is chosen
from, alone or as £ mixture:
saturated monocarboxylic acids such as caproic acid, caprylic acid, isoheptarioic acid, 4~ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhejcarioic acid, octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, isostearic acid;
unsaiurated but non-aromatic monocarboxylic acids such as caproleic acid, obtusilic acid, undecylenic acid, dodecylenic acid, linderic acid, myristoleic acid, physeteric acid, tsuzuic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid.
7. Composition according to one of the preceding
claims, in which the non-aronatic monocarboxylic acid
having a melting point of less than 25°C, or the
mixture of the said acids, represents 0.5 to 32% by
weight, or even 1 to 30% by weight, and even better 2
to 28% by weight, of the total weight of the
polycondensate.
8. Composition according to one of the preceding
claims, in which the aromatic monocarboxylic acid is
chosen from, alone or as a mixture, benzoic acid, o-
toluic acid, m-toluic acid, p-tcluic acid, 1-naphthoic
acid, 2-naphthoic acid, 4-tert-butylbenzoic acid, 1-
methyl-2-naphthoic acid, 2-isopropyl-l-naphthoic acid.
9. Composition according to one of the preceding
claims, in which the aromatic monocarboxylic acid, or
the mixture of the said acids, represents 0.5 to 9.95%
by weight, in particular 1 to 9,5% by weight, and even
better 1.5 to 8% by weight, of the total weight of the polycondensate.
10. Composition according to one of the preceding claims, in which the polycarboxylic acid, its anhydride or the lactone, is chosen from, alone or as a mixture:
saturated or unsaturated, or even aromatic, linear, branched and/or cyclic polycarboxylic acids comprising 2 to 50 carbon atoms; the said acid comprising at least two caxboxyl groups COOH; and optionally capable of comprising 1 to 10 heteroatoms, which are identical or different, chosen from 0, N and S; and/or optionally capable of comprising at least one perfluor.inated radical chosen from -CFg- (divalent) or -CFs; and their anhydrides;
polycarboxylic acids having a linear ox branched, saturated or unsaturated chain comprising at least one heteroazom chosen from 0, N and/or S, in particular 1 to 10 heteroar,oras, which are identical or different, and/or comprising at least one perfluorinated radical -CF2- or -CF3 and h&ving moreover at least 2 carboxyl groups COOH; and their anhydrides;
saturated or unsaturated, or even aroir.atic, heterocyclic polycarboxylic acids comprising at least one hetecoatom chosen from 0, N and/or S, in particular 1 to 10 heteroatoms, which are identical or different, and at least 2 carboxyl groups COOH; and their anhydrides;
polycarboxylic acids derived from a sugar, which are liable to be obtained in particular by oxidation of an aldose, and comprising at leas- 2 carboxyl groups COOH; and their anhydrides;
itaconic anhydride and the 1,4-monoanhydride of 1,4,5,8-naphthalenetetracarboxylic acid;
polycarboxylic (including heterocyclic) amino acids, that is to say polycarboxylic acids having a linear, branched end/ox cyclic, saturated or unsaturated chain optionally comprising at least one
heteroatom chosen from 0, N and/or S, In particular 1 to 10 heteroatoms which are identical or different, and/or optionally comprising at least one perfluorinated radical -CF2- or -CF3; and additionally comprising at least one primary, secondary or tertiary amine functional group functional group and having moreover at least 2 carboxyl groups COQH; and their anhydrides;
lactones comprising 1, 2 or 3 COOH groups, and 5 to 14 carbon atoms, in particular 6 to 13, or even 6 to 12 carbon atoms.
11. Composition according to one of the preceding
claims, in which the polycarboxylic acid and/or its
cyclic anhydride and/or the lactone represents 5 to 35%
by weight, in particular 1C to 30% by weight, and even
better 14 to 25% by weight, of the total weight of the
final polycondensate.
12. Composition according to one of the preceding
claims, in which the polycondensate is present in a
quantity of between 0.1 and 70% by weight, preferably
between I and 50% by weight, in particular between 10
and 45% by weight, or even between 20 and 40% by
weight, and even better between 25 and 35% by weight,
relative to the weight of the final -cosmetic or
pharmaceutical composition.
13. Composition according to one of the preceding
claims, provided in the form of a care and/or make-up
product for the skin of the body or of the face, the
lips, the eyelashes, the eyebrows, the hair, the scalp
or the nails; sn anti-sun or a self-tanning product; a
hair product, in particular for dyeing, conditioning
and/or caring for the hair.
14. Method for the cosmetic treatment of keratin
materials, in particular the skin of the body or of the
face, the lipsr the nails, the hair and/Or the eyelashes, comprising the application to the said materials of a cosmetic composition as defined in one of Claims 1 to 13.
IS. Polycondensate capable of being obtained by the reaction;
- of 10 to 30% by weight, relative to the total weight
of the polycondensate, of at least one polyol
comprising 3 to 6 hydroxyl groups;
- of 22 to 80% by weight, relative to the total weight
of the polyconderisate, of at least one linear,
branched and/or cyclic, saturated or unsaturated,
non-aromatic monocarboxylic acid comprising 10 to 32
carbon atoms, and having a melting point greater
than or equal to 25°C;
of 0.1 to 35% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsatureted, non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms and having a rr.elting point strictly less than 25°C;
- of 0.1 to 10% by weight, relative to the total
weight of the polycondehsate, of at least one
aromatic monocarboxylic acid comprising 7 to 11
carbon atoms, optionally additionally substituted
with 1 to 3 linear, branched and/or cyclic,
saturated or unsaturated alkyl radicals which
comprise 1 to 32 carbon atoms;
- of 1 to 40% by weight, relative to the total weight
of the polycondensate, of at least one linear,
branched and/ox cyclic, saturated or unsaturated, or
even aromatic, polycarboxylic acid comprising at
least 2 carboxyl groups COOH, which may comprise
heteroatoms; and/or a cyclic anhydride of such a
polycarboxylic acid; and/or a lactone comprising at
least one COOH group.
16. Method of preparing the polycondensates according to Claim 15, consisting in:
mixing the polyol and the aromatic and non-aromatic monocarboxylic acids,
heating the mixture under an inert atmosphere, first up to the melting point, and then to a temperature of between 150 and 220°C until there is complete consumption of the monocarboxylic acids, and then
optionally cooling the mixture to a temperature of between 90 and 150°C,
adding the polycarboxylic acid and/or the cyclic anhydride and/or the lactone, and then
again heating to a temperature of less than or equal to 220°C.