Patent Application
20250032395
The present invention relates to a copolymer composition for thickening polar or apolar oils, to the process for manufacturing same and to topical formulations comprising this thickening composition.
There is a need to thicken oils in the cosmetics market. Gel formation requires the formation of a three-dimensional network by a gelling agent, enabling immobilization of the liquid phase or the solvent. Several strategies may be used to do this. They involve various types of interactions, including weak ones (hydrogen bonding, hydrophobic/hydrophobic, etc.) and absorption/adsorption phenomena.
The thickening solutions currently proposed offer significant performance and appreciable advantages in terms of versatility, but also drawbacks, notably the impact on the formula's sensory properties, and the formulation conditions. These substances are of varied chemical nature: silica derivatives, clays, polymers such as polyamide, polyacrylate, polyurethane, beeswax, hydrogenated plant oils or else sugar fatty esters or amides.
Although there are already oil thickeners on the market, of varied nature and performance, the relationships between their structures and properties are not clearly identified, which is the main scientific barrier, since the object is to find a structure obtained from materials of plant origin which would afford high performance with oils of any type of nature (polar to nonpolar), for different types of textures (compact to fluid) and attractive or at least non-prohibitive sensory properties (non-greasy, non-tacky, non-runny).
One of the difficulties thus lies in finding a single universal structure or substance allowing all types of oils, from the most apolar to the most polar, to be effectively thickened at low doses, the gelling mechanisms of course differing according to the nature of the oil and the gelling agent.
A solution of the present invention is a copolymer composition (C) for thickening polar or apolar oils (H2), comprising at least one oil (H1) and at least one poly(itaconate) (P), the at least one poly(itaconate) consisting of:
in which R′1—C(═O) represents a linear or branched, saturated or unsaturated hydrocarbon-based acyl radical containing from 12 to 24 carbon atoms, and more particularly a radical chosen from the elements of the group consisting of dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, eicosanoyl, docosanoyl, oleyl, linoleyl, linolenoyl or isostearyl radicals, and in which x represents a natural integer greater than or equal to 1 and less than or equal to 5, and
with Y1 and Y′1, which may be identical or different, representing the HO— radical or the radical of formula (Y11):
in which m is an integer greater than or equal to 2 and less than or equal to 10;
with Y2 and Y2 which may be identical or different, representing the HO— radical or the radical of formula (Y21):
with Y3 and Y′3, which may be identical or different, representing the HO— radical or the radical of formula (Y31):
with Y4 and Y′4, which may be identical or different, representing the HO— radical or the radical of formula (Y41):
with Y5 and Y′5, which may be identical or different, representing the HO— radical or the radical of formula (Y51):
O—(CH2)q—OH (Y51),
in which q is an integer greater than or equal to 1 and less than or equal to 12, more particularly greater than or equal to 3 and less than or equal to 8;
with Y8 and Y′8, which may be identical or different, representing the HO— radical or the radical of formula (Y81):
in which R′1—C(═O) represents a linear or branched, saturated or unsaturated hydrocarbon-based acyl radical including from 12 to 36 carbon atoms, and in which x represents a natural integer greater than or equal to 6 and less than or equal to 20.
When Y or Y′ are different and represent the HO— radical, the carboxylic acid function thus present in formula (AIId1) is in free acid form or partially or totally salified form.
When Y6 or Y′6 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIf1) is in free acid form or partially or totally salified form.
When Y7 or Y′7 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIg1) is in free acid form or partially or totally salified form.
When Y1 or Y′1 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIa1) is in free acid form or partially or totally salified form.
When Y2 or Y′2 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIb1) is in free acid form or partially or totally salified form.
When Y3 or Y′3 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIc1) is in free acid form or partially or totally salified form.
When Y4 or Y′4 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIc1′) is in free acid form or partially or totally salified form.
When Y5 or Y′5 are different and represent the HO— radical, the carboxylic acid function thus present in formula (IIe1) is in free acid form or partially or totally salified form.
Said thickening composition (C) allows polar and apolar oils (H2) to be thickened.
For the purposes of the present invention, the term “salified” means that the acid function present in a monomer is in an anionic form associated in salt form with a cation, notably alkali metal salts, such as the sodium or potassium cations, or such as cations of nitrogenous bases such as the ammonium salt, the lysine salt or the monoethanolamine salt (HOCH2—CH2—NH4+). They are preferably sodium or ammonium salts.
The term “saturated or unsaturated, linear or branched aliphatic hydrocarbon-based radical including from 6 to 36 carbon atoms, optionally substituted with one or more hydroxyl groups” denotes, for the radical R1 in formula (AIId1), in formula (Y61) and in formula (IIf1′) as defined above:
(CH3)(CH3)CH—(CH2)r—CH2—OH (1)
in which r represents an integer between 2 and 20, for example the isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoeicosyl or isodocosyl radicals; branched alkyl radicals, derived from Guerbet alcohols, of formula (2):
CH(CsH2s+1)(CtH2t+1)—CH2—OH (2)
in which t is an integer between 4 and 18, s is an integer between 2 and 18 and the sum s+t is greater than or equal to 6 and less than or equal to 22, for example the 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl or 2-tetradecyloctadecyl radicals.
According to an even more particular aspect, in the definition of formulae (AIId1) and (IIf1) as defined above, R1 represents the radical chosen from at least one of the elements of the group consisting of n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl and 12-hydroxyoctadecyl radicals.
According to a particular aspect, the poly(itaconate) (P) is a crosslinked poly(itaconate) (P).
For the purposes of the present invention, the term “crosslinked poly(itaconate) (P)” denotes poly(itaconate) as defined previously and also consisting of at least one monomer unit derived from a polyethylenic crosslinking monomer (AR).
The term “polyethylenic crosslinking monomer (AR)” denotes compounds whose chemical formula includes at least two ethylenic bonds and which allow two or more polymer chains to be linked during the radical polymerization reaction involving the monomers making up the poly(itaconate) as described above. The polyethylenic crosslinking monomers (AR) may be added to the monomers prior to initiation of the radical polymerization process allowing the crosslinked poly(itaconate) to be prepared.
The polyethylenic crosslinking monomers (AR) may also be constituents of the monomer compositions used in the radical polymerization process, as a result of the esterification between two or more itaconic acid molecules with one molecule of a polyol.
For the purposes of the present invention, the term “polyol” denotes an aliphatic molecule substituted with at least two hydroxyl groups.
For the purposes of the present invention, the term “polar oil” denotes a hydrophobic compound which comprises polar groups in its molecular structure, i.e. groups that are capable of creating electrostatic interactions with water molecules, of the permanent dipole/permanent dipole type.
For the purposes of the present invention, the term “apolar oil” denotes a hydrophobic compound which cannot create electrostatic interactions with water molecules of the permanent dipole/permanent dipole type.
For the purposes of the present invention, the term “hydrophobic compound” denotes a compound which cannot physically interact with water.
For the purposes of the present invention, the term “oil” denotes a compound and/or mixture of compounds that are hydrophobic and insoluble in water.
Depending on the case, the solution according to the invention may have one or more of the following features:
The mineral oils are preferably chosen from:
The plant oils are preferably chosen from oils belonging to the family:
According to a particular aspect, the compound of formula (IV) represents cocoyl caprylate caprate such as the product sold under the brand name DUB 810C, propyl cocoate, isopropyl cocoate, propyl palmitate, isopropyl palmitate, octyl palmitate.
The term “oil (H2)” means oils (H1) as defined previously, and more particularly mineral oils as described above and compounds of formula (V) in which R4-(C═O), R5-(C═O) and R6-(C═O), which may be identical or different, represent an acyl group chosen from the elements of the group consisting of octanoyl, decanoyl and dodecanoyl groups.
A subject of the present invention is also a topical formulation (F) comprising a composition (C) as defined previously. In other words, the topical formulation (F) comprises the mixture of composition (C) and at least one oil (H2).
The expression “for topical use” used in the definition of formulation (F) as defined above means that said formulation is prepared to allow its application to the skin, the hair, the scalp or the mucous membranes, whether it is direct application in the case of a cosmetic, dermocosmetic, dermopharmaceutical or pharmaceutical composition or an indirect application, for example in the case of a body hygiene product in the form of a textile or paper wipe, or sanitary products intended to be in contact with the skin or the mucous membranes.
Preferably, this topical formulation (F) will be a cosmetic formulation.
Said topical formulation (F) is generally in the form of an oily composition, in the form of a suspension, an emulsion, a microemulsion or a nanoemulsion, whether they are of water-in-oil, oil-in-water, water-in-oil-in-water or oil-in-water-in-oil type.
Said topical formulation (F) may be packaged in a bottle, in a device of pump-bottle type, in pressurized form in an aerosol device, in a device equipped with an openwork wall such as a grate or in a device equipped with a ball applicator (known as a roll-on).
In general, said topical composition (F) also includes excipients and/or active principles usually used in the field of formulations for topical use, in particular cosmetic, dermocosmetic, pharmaceutical or dermopharmaceutical formulations, such as thickening and/or gelling surfactants, stabilizers, film-forming compounds, hydrotropic agents, plasticizers, emulsifying and coemulsifying agents, opacifiers, nacreous agents, superfatting agents, sequestrants, chelating agents, antioxidants, fragrances, preserving agents, conditioning agents, bleaching agents intended for bleaching bodily hairs and the skin, active principles intended to provide a treating action with respect to the skin or the hair, sunscreens, pigments or mineral fillers, particles affording a visual effect or intended for the encapsulation of active principles, exfoliant particles or texturing agents.
The mixture of composition (C) as described previously and an oil (H2) will preferably be prepared at a temperature of between 50° C. and 85° C., more preferentially at a temperature of 80° C. The homogeneous oily composition obtained is then cooled to room temperature, between 15° C. and 30° C.
The thickening of the oil (H2) is finally assessed visually by qualifying the viscous or gelled liquid consistencies, by measuring a dynamic viscosity value.
For a composition (C) to be considered efficient, the viscous or gelled aspects must at least be achieved.
A subject of the present invention is also a process for preparing a thickening copolymer composition (C) according to the invention, comprising:
The term “thermal initiator” in step c) of the process as defined previously denotes a molecule which, when placed at a temperature specific to said structure, generates the production of at least two radicals by homolysis of at least one covalent bond, said radicals enabling the initiation of radical polymerization.
According to a particular aspect, the thermal initiator is chosen from the elements of the group consisting of lauroyl peroxide, azobis(isobutyronitrile) or AIBN, benzoyl peroxide or BPO, azobis((2-methylbutyronitrile) or AMBN, 4,4′-azobis(4-cyanovaleric acid) or ACVA, 2,2′-azobis(2,4-dimethylvaleronitrile), cumene hydroperoxide, di-tert-butyl peroxide or tert-butyl hydroperoxide.
The process for preparing the thickening composition (C) will preferably comprise one or more of the following features:
R1-OH (IId)
with R1 representing a linear or branched, saturated or unsaturated, hydrocarbon-based aliphatic radical including from 6 to 36 carbon atoms and optionally substituted with one or more hydroxyl groups.
According to a particular aspect, R1 represents a hydrocarbon-based aliphatic radical chosen from n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, oleyl, linoleyl, linolenyl, arachidyl, behenyl, erucyl and 12-hydroxystearyl radicals,
with R′1 representing a linear or branched, saturated or unsaturated, hydrocarbon-based aliphatic radical including from 6 to 36 carbon atoms and optionally substituted with one or more hydroxyl groups.
According to a particular aspect, R′1 represents a hydrocarbon-based aliphatic radical chosen from n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, oleyl, linoleyl, linolenyl, arachidyl, behenyl, erucyl and 12-hydroxystearyl radicals. More particularly, the compound of formula (IIf) is batyl alcohol, the structure of which is as follows:
and
For the purposes of the present invention, the term “polymerization inhibitor” denotes compounds which, when added to monomers, regulate or rapidly stop the undesired initiation of polymerization of said monomers; among these polymerization inhibitors, mention may be made of quinones, hydroquinone, methylhydroquinone, 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, catechols, for instance 4-tert-butylpyrocatechol, 2,6-di-tert-butylphenol, 6-tert-butyl-2,4-xylenol, tert-butylhydroquinone, 4-methoxyphenol, 2,6-di-tert-butyl-p-cresol, aromatic nitro compounds such as nitrobenzenes, nitrophenols, nitrocresols, nitroso compounds, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, and metal salts such as copper salts, for example copper(II) dibutyldithiocarbamate,
The stoichiometric mole ratio (IIa)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IIb)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IIc)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IId)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IIe)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IIf)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IIg)/(I) is greater than or equal to 0.25 and less than or equal to 2.0.
The stoichiometric mole ratio (IIh)/(I) is greater than or equal to 0.25 and less than or equal to 2.0. The compositions of itaconic acid mono- or oligoesters (A) are characterized by measurements of macroscopic indices (acid and ester numbers) and by their residual itaconic acid content measured by high-performance liquid chromatography (HPLC) coupled to an ultraviolet (UV) detector with internal calibration.
Finally, a degree of itaconic acid conversion is determined. A degree of conversion of greater than or equal to 75% must be achieved in order for the esterification reactions to be considered as having proceeded correctly.
Examples of foaming and/or detergent surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include anionic, cationic, amphoteric or nonionic foaming and/or detergent surfactants.
The foaming and/or detergent anionic surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include alkali metals salts, alkaline-earth metal salts, ammonium salts, amine salts or amino alcohol salts of alkyl ether sulfates, of alkyl sulfates, of alkylamido ether sulfates, of alkylaryl polyether sulfates, of monoglyceride sulfates, of α-olefin sulfonates, of paraffin sulfonates, of alkyl phosphates, of alkyl ether phosphates, of alkyl sulfonates, of alkylamide sulfonates, of alkylaryl sulfonates, of alkyl carboxylates, of alkylsulfosuccinates, of alkyl ether sulfosuccinates, of alkylamide sulfosuccinates, of alkylsulfoacetates, of alkyl sarcosinates, of acylisethionates, of N-acyl taurates, of acyl lactylates, of N-acylamino acid derivatives, of N-acyl peptide derivatives, of N-acyl protein derivatives, of N-acyl fatty acid derivatives.
The foaming and/or detergent amphoteric surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include alkyl betaines, alkylamido betaines, sultaines, alkylamidoalkyl sulfobetaines, imidazoline derivatives, phosphobetaines, amphopolyacetates and amphopropionates.
The foaming and/or detergent cationic surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) particularly include quaternary ammonium derivatives.
The foaming and/or detergent nonionic surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) more particularly include alkyl polyglycosides including a linear or branched and saturated or unsaturated aliphatic radical including from 8 to 16 carbon atoms, such as octyl polyglucoside, decyl polyglucoside, undecylenyl polyglucoside, dodecyl polyglucoside, tetradecyl polyglucoside, hexadecyl polyglucoside or 1,12-dodecanediyl polyglucoside; ethoxylated hydrogenated castor oil derivatives, such as the product sold under the INCI name PEG-40 hydrogenated castor oil; polysorbates, such as Polysorbate 20, Polysorbate 40, Polysorbate 60, Polysorbate 70, Polysorbate 80 or Polysorbate 85; coconut kernel amides; or N-alkylamines.
Examples of thickening and/or gelling surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include optionally alkoxylated alkyl polyglycoside fatty esters, such as ethoxylated methyl polyglucoside esters, for example the PEG 120 methyl glucose trioleate and the PEG 120 methyl glucose dioleate sold respectively under the names Glucamate™ LT and Glucamate™ DOE-120; alkoxylated fatty esters, such as the PEG 150 pentaerythrityl tetrastearate sold under the name Crothix™ DS53 or the PEG 55 propylene glycol oleate sold under the name Antil™ 141; fatty-chain polyalkylene glycol carbamates, such as the PPG-14 laureth isophoryl dicarbamate sold under the name Elfacos™ T211 or the PPG-14 palmeth-60 hexyl dicarbamate sold under the name Elfacos™ GT2125.
Examples of thickeners and/or gelling agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include polysaccharides consisting only of monosaccharides, such as glucans or glucose homopolymers, glucomannoglucans, xyloglycans, galactomannans in which the degree of substitution (DS) of the D-galactose units on the main D-mannose chain is between 0 and 1, and more particularly between 1 and 0.25, such as galactomannans originating from cassia gum (DS=⅕), from locust bean gum (DS=¼), from tara gum (DS=⅓), from guar gum (DS=½) or from fenugreek gum (DS=1).
Examples of thickening and/or gelling agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include polysaccharides consisting of monosaccharide derivatives, such as sulfated galactans and more particularly carrageenans and agar, uronans and more particularly algins, alginates and pectins, heteropolymers of monosaccharides and of uronic acids and more particularly xanthan gum, gellan gum, gum arabic exudates and karaya gum exudates, or glucosaminoglycans.
Examples of thickening and/or gelling agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include cellulose, cellulose derivatives, such as methyl cellulose, ethyl cellulose or hydroxypropyl cellulose, silicates, starch, hydrophilic starch derivatives or polyurethanes.
Examples of stabilizers that may be combined with said thickening composition (C) as defined previously in said composition (F) include monocrystalline waxes and more particularly ozokerite, mineral salts, such as sodium chloride or magnesium chloride, or silicone polymers, such as polysiloxane polyalkyl polyether copolymers.
Examples of solvents that may be combined with said thickening composition (C) as defined previously in said composition (F) include water, organic solvents, such as glycerol, diglycerol, glycerol oligomers, ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,2-propanediol, hexylene glycol, diethylene glycol, xylitol, erythritol, sorbitol, water-soluble alcohols, such as ethanol, isopropanol or butanol, or mixtures of water and of said organic solvents.
Examples of thermal or mineral waters that may be combined with said thickening composition (C) as defined previously in said composition (F) include thermal or mineral waters having a mineralization of at least 300 mg/I, in particular Avène water, Vittel water, Vichy basin water, Uriage water, La Roche-Posay water, La Bourboule water, Enghien-les-Bains water, Saint-Gervais-les-Bains water, Néris-les-Bains water, Allevard-les-Bains water, Digne water, Maizieres water, Neyrac-les-Bains water, Lons-le-Saunier water, Rochefort water, Saint Christau water, Les Fumades water and Tercis-les-Bains water. Examples of hydrotropic agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include xylenesulfonates, cumenesulfonates, hexyl polyglucoside, 2-ethylhexyl polyglucoside and n-heptyl polyglucoside.
Examples of emulsifying surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include nonionic surfactants, anionic surfactants or cationic surfactants.
Examples of emulsifying nonionic surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include fatty acid esters of sorbitol, for instance the products sold under the names Montane™ 40, Montane™ 60, Montane™ 70, Montane™ 80 and Montane™ 85; compositions comprising glyceryl stearate and stearic acid ethoxylated with between 5 mol and 150 mol of ethylene oxide, for instance the composition comprising stearic acid ethoxylated with 135 mol of ethylene oxide and glyceryl stearate sold under the name Simulsol™ 165; mannitan esters, ethoxylated mannitan esters; sucrose esters; methyl glucoside esters; alkyl polyglycosides including a linear or branched, saturated or unsaturated aliphatic radical, and including from 14 to 36 carbon atoms, for instance tetradecyl polyglucoside, hexyldecyl polyglucoside, octadecyl polyglucoside, hexadecyl polyxyloside, octadecyl polyxyloside, eicosyl polyglucoside, dodecosyl polyglucoside, 2-octyldodecyl polyxyloside, 12-hydroxystearyl polyglucoside; compositions of linear or branched, saturated or unsaturated fatty alcohols including from 14 to 36 carbon atoms and of alkyl polyglycosides as described previously, for example the compositions sold under the names Montanov™ 68, Montanov™ 14, Montanov™ 82, Montanov™ 202, Montanov™ S, Montanov™ WO18, Montanov™ L, Fluidanov™ 20X and Easynov™.
Examples of anionic surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include glyceryl stearate citrate, cetearyl sulfate, soaps, such as sodium stearate or triethanolammonium stearate, and N-acylamino acid derivatives which are salified, for example stearoyl glutamate. Examples of cationic emulsifying surfactants that may be combined with said thickening composition (C) as defined previously in said composition (F) include amine oxides, quaternium-82 and the surfactants described in patent application WO 96/00719 and mainly those whose fatty chain comprises at least 16 carbon atoms.
Examples of opacifying and/or nacreous agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include sodium palmitate, sodium stearate, sodium hydroxystearate, magnesium palmitate, magnesium stearate, magnesium hydroxystearate, ethylene glycol monostearate, ethylene glycol distearate, polyethylene glycol monostearate, polyethylene glycol distearate or fatty alcohols including from 12 to 22 carbon atoms.
Examples of texturing agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include N-acylamino acid derivatives, such as lauroyl lysine sold under the name Aminohope™ LL, starch octenylsuccinate sold under the name Dryflo™, myristyl polyglucoside sold under the name Montanov™ 14, cellulose fibers, cotton fibers, chitosan fibers, talc, sericite or mica. Examples of deodorant agents that may be combined with said thickening composition (C) as defined previously in said composition (F) include alkali metal silicates, zinc salts, such as zinc sulfate, zinc gluconate, zinc chloride or zinc lactate; quaternary ammonium salts, such as cetyltrimethylammonium salts or cetylpyridinium salts; glycerol derivatives, such as glyceryl caprate, glyceryl caprylate or polyglyceryl caprate; 1,2-decanediol, 1,3-propanediol; salicylic acid; sodium bicarbonate; cyclodextrins; metallic zeolites; Triclosan™; aluminum bromohydrate, aluminum chlorohydrates, aluminum chloride, aluminum sulfate, aluminum zirconium chlorohydrates, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate, aluminum zirconium octachlorohydrate, aluminum sulfate, sodium aluminum lactate, complexes of aluminum chlorohydrate and of glycol, such as the complex of aluminum chlorohydrate and of propylene glycol, the complex of aluminum dichlorohydrate and of propylene glycol, the complex of aluminum sesquichlorohydrate and of propylene glycol, the complex of aluminum chlorohydrate and of polyethylene glycol, the complex of aluminum dichlorohydrate and of polyethylene glycol, or the complex of aluminum sesquichlorohydrate and of polyethylene glycol.
Examples of waxes that may be combined with said thickening composition (C) as defined previously in said composition (F) include beeswax, carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fiber wax, sugarcane wax, paraffin waxes, lignite waxes, microcrystalline waxes, lanolin wax; ozokerite, polyethylene wax, silicone waxes, plant waxes, fatty alcohols and fatty acids that are solid at room temperature, or glycerides that are solid at room temperature. In the present patent application, the term “waxes” refers to compounds and/or mixtures of compounds which are water-insoluble, and which have a solid appearance at a temperature of greater than or equal to 45° C.
Examples of active principles that may be combined with said thickening composition (C) as defined previously in said composition (F) include vitamins and their derivatives, notably their esters, such as retinol (vitamin A) and its esters (for example retinyl palmitate), ascorbic acid (vitamin C) and its esters, sugar derivatives of ascorbic acid (such as ascorbyl glucoside), tocopherol (vitamin E) and its esters (such as tocopheryl acetate), vitamin B3 or B10 (niacinamide and its derivatives); compounds showing a lightening or depigmenting action on the skin, such as ω-undecylenoyl phenylalanine sold under the name Sepiwhite™ MSH, Sepicalm™ VG, the glycerol monoester and/or diester of ω-undecylenoyl phenylalanine, ω-undecylenoyl dipeptides, arbutin, kojic acid, hydroquinone; compounds showing a calmative action, notably Sepicalm™ S, allantoin and bisabolol; anti-inflammatory agents; compounds showing a moisturizing action, such as urea, hydroxyureas, glycerol, polyglycerols, glyceryl glucoside, diglyceryl glucoside, polyglyceryl glucosides, xylityl glucoside; polyphenol-rich plant extracts, such as grape extracts, pine extracts, wine extracts or olive extracts; compounds showing a slimming or lipolytic action, such as caffeine or its derivatives, Adiposlim™, Adipoless™, fucoxanthin; N-acyl proteins; N-acyl peptides, such as Matrixyl™; N-acyl amino acids; partial hydrolyzates of N-acyl proteins; amino acids; peptides; total hydrolyzates of proteins; soybean extracts, for example Raffermine™; wheat extracts, for example Tensine™ or Gliadine™; plant extracts, such as tannin-rich plant extracts, isoflavone-rich plant extracts or terpene-rich plant extracts; extracts of freshwater or marine algae; marine plant extracts; marine extracts in general, such as corals; essential waxes; bacterial extracts; ceramides; phospholipids; compounds showing an antimicrobial action or a purifying action, such as Lipacide™ C8G, Lipacide™ UG, Sepicontrol™ A5, Octopirox™ or Sensiva™ SC50; compounds showing an energizing or stimulating property, such as Physiogenyl™, panthenol and its derivatives, such as Sepicap™ MP; antiaging active agents, such as Sepilift™ DPHP, Lipacide™ PVB, Sepivinol™, Sepivital™, Manoliva™, Phyto-Age™, Timecode™; Survicode™; antiphotoaging active agents; active agents which protect the integrity of the dermoepidermal junction; active agents which increase the synthesis of the components of the extracellular matrix, such as collagen, elastins or glycosaminoglycans; active agents which act favorably on chemical cell communication, such as cytokines, or physical cell communication, such as integrins; active agents which create a sensation of “heating” on the skin, such as activators of cutaneous microcirculation (such as nicotinic acid derivatives) or products which create a sensation of “freshness” on the skin (such as menthol and derivatives); active agents which improve cutaneous microcirculation, for example venotonics; draining active agents; active agents having a decongestant purpose, such as Ginkgo biloba, ivy, horse chestnut, bamboo, Ruscus, butcher's broom, Centella asiatica, fucus, rosemary or willow extracts; agents for tanning or browning the skin, for example dihydroxyacetone (DHA), erythrulose, mesotartaric aldehyde, glutaraldehyde, glyceraldehyde, alloxan or ninhydrin, plant extracts, for example extracts of red woods of the genus Pterocarpus and of the genus Baphia, such as Pteropcarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida, such as those described in the European patent application EP 0 971 683; agents known for their action in facilitating and/or accelerating tanning and/or browning of human skin, and/or for their action in coloring human skin, for example carotenoids (and more particularly 3-carotene and γ-carotene), the product sold under the brand name Carrot Oil (INCI name: Daucus carrota, Helianthus annuus sunflower oil) by the company Provital, which contain carotenoids, vitamin E and vitamin K; tyrosine and/or its derivatives, known for their effect on accelerating the tanning of human skin in combination with exposure to ultraviolet radiation, for example the product sold under the brand name SunTan Accelerator™ by the company Provital, which contains tyrosine and riboflavins (vitamin B), the complex of tyrosine and of tyrosinase sold under the brand name Zymo Tan Complex by the company Zymo Line, the product sold under the brand name MelanoBronze™ (INCI name: Acetyl Tyrosine, Monk's pepper extract (Vitex agnus-castus)) by the company Mibelle, which contains acetyl tyrosine, the product sold under the brand name Unipertan VEG-24/242/2002 (INCI name: Butylene Glycol and Acetyl Tyrosine and Hydrolyzed Vegetable Protein and Adenosine Triphosphate) by the company Unipex, the product sold under the brand name Try-Excell™ (INCI name: Oleoyl tyrosine and Luffa cylindrica (seed) oil and oleic acid) by the company Sederma, which contains extracts of marrow seeds (or loofah oil), the product sold under the brand name Actibronze™ (INCI name: Hydrolyzed wheat protein and acetyl tyrosine and copper gluconate) by the company Alban Muller, the product sold under the brand name Tyrostan™ (INCI name: Potassium caproyl tyrosine) by the company Synerga, the product sold under the brand name Tyrosinol (INCI name: Sorbitan Isostearate, Glyceryl Oleate, Caproyl Tyrosine) by the company Synerga, the product sold under the brand name InstaBronze™ (INCI name: Dihydroxyacetone and Acetyl Tyrosine and Copper Gluconate) by the company Alban Muller, the product sold under the brand name Tyrosilane (INCI name: Methylsilanol and Acetyl Tyrosine) by the company Exymol; peptides known for their effect in activating melanogenesis, for example the product sold under the brand name Bronzing SF Peptide Powder (INCI name: Dextran and Octapeptide-5) by the company Infinitec Activos, the product sold under the brand name Melitane (INCI name: Glycerin and Aqua and Dextran and Acetyl Hexapeptide-1) comprising acetyl hexapeptide-1 known for its α-MSH agonist action, the product sold under the brand name Melatimes Solutions™ (INCI name: Butylene glycol, Palmitoyl Tripeptide-40) by the company Lipotec, sugars and sugar derivatives, for example the product sold under the brand name Tanositol™ (INCI name: inositol) by the company Provital, the product sold under the brand name Thalitan™ (or Phycosaccharide™ AG) by the company CODIF International (INCI name: Aqua and Hydrolyzed algin (Laminaria digitata) and magnesium sulfate and manganese sulfate) containing an oligosaccharide of marine origin (guluronic acid and mannuronic acid chelated with magnesium and manganese ions), the product sold under the brand name Melactiva™ (INCI name: Maltodextrin, Mucuna pruriens Seed Extract) by the company Alban Muller, compounds rich in flavonoids, for example the product sold under the brand name Biotanning (INCI name: Hydrolyzed citrus Aurantium dulcis fruit extract) by the company Silab and known to be rich in lemon flavonoids (of the hesperidin type); agents intended for treating head hair and/or bodily hair, for example agents for protecting the melanocytes of the hair follicle, intended to protect said melanocytes against cytotoxic agents responsible for the senescence and/or apoptosis of said melanocytes, such as mimetics of DOPAchrome tautomerase activity, chosen from those described in the European patent application published under the number EP 1 515 688 A2, synthetic SOD mimetic molecules, for example manganese complexes, antioxidant compounds, for example cyclodextrin derivatives, siliceous compounds derived from ascorbic acid, lysine or arginine pyrrolidone carboxylate, combinations of mono- and diesters of cinnamic acid and of vitamin C, and more generally those mentioned in the European patent application published under the number EP 1 515 688 A2.
Examples of antioxidants that may be combined with said thickening composition (C) as defined previously in said composition (F) include EDTA and its salts, citric acid, tartaric acid, oxalic acid, BHA (butylated hydroxyanisole), BHT (butylated hydroxytoluene), tocopherol derivatives, such as tocopheryl acetate, mixtures of antioxidant compounds, such as Dissolvine GL 47S sold by the company AkzoNobel under the INCI name: Tetrasodium Glutamate Diacetate.
Examples of sunscreens that may be combined with said thickening composition (C) as defined previously in said composition (F) include all those appearing in the amended Cosmetics Directive 76/768/EEC, Annex VII.
The organic sunscreens that may be combined with said thickening composition (C) as defined previously in said composition (F) include the family of benzoic acid derivatives, for instance para-aminobenzoic acids (PABA), notably monoglyceryl esters of PABA, ethyl esters of N,N25-propoxy PABA, ethyl esters of N,N-diethoxy PABA, ethyl esters of N,N-dimethyl PABA, methyl esters of N,N-dimethyl PABA and butyl esters of N,N-dimethyl PABA; the family of anthranilic acid derivatives, for instance homomenthyl-N-acetyl anthranilate; the family of salicylic acid derivatives, for instance amyl salicylate, homomenthyl salicylate, ethylhexyl salicylate, phenyl salicylate, benzyl salicylate and p-isopropanolphenyl salicylate; the family of cinnamic acid derivatives, for instance ethylhexyl cinnamate, ethyl 4-isopropylcinnamate, methyl 2,5-diisopropylcinnamate, p-methoxypropyl cinnamate, p-methoxyisopropyl cinnamate, p-methoxyisoamyl cinnamate, p-methoxyoctyl cinnamate (p-methoxy-2-ethylhexyl cinnamate), p-methoxy-2-ethoxyethyl cinnamate, p-methoxycyclohexyl cinnamate, ethyl-α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate or glyceryl di-para-methoxymono-2-ethylhexanoyl cinnamate; the family of benzophenone derivatives, for instance 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl 4′-phenylbenzophenone-2-5-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, 4-hydroxy-3-carboxybenzophenone; 3-(4′-methylbenzylidene)-d,l-camphor, 3-(benzylidene)-d,l-camphor, camphor benzalkonium methosulfate; urocanic acid, ethyl urocanate; the family of sulfonic acid derivatives, for instance 2-phenylbenzimidazole-5-sulfonic acid and salts thereof; the family of triazine derivatives, for instance hydroxyphenyltriazine, ethylhexyloxyhydroxyphenyl-4-methoxyphenyltriazine, 2,4,6-trianillino (p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine, 4,4-((6-(((1,1-dimethylethyl)amino)carbonyl)phenyl)amino)-1,3,5-triazine-2,4-diyldiimino)bis(2-ethylhexyl)benzoate, 2-phenyl-5-methylbenzoxazole, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methyphenyl)benzotriazole; dibenzazine; dianisoylmethane, 4-methoxy-4″-t-butylbenzoylmethane; 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one; the family of diphenylacrylate derivatives, for instance 2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate, ethyl 2-cyano-3,3-diphenyl-2-propenoate; the family of polysiloxanes, for instance benzylidene siloxane malonate.
The mineral sunscreens, also known as “mineral sunblocks”, that may be combined with said thickening composition (C) as defined previously in said composition (F) include titanium oxides, zinc oxides, cerium oxide, zirconium oxide, yellow, red or black iron oxides, or chromium oxides. These mineral sunblocks may or may not be micronized, may or may not have been subjected to surface treatments and may optionally be in the form of aqueous or oily predispersions.
The invention will now be described in greater detail by means of the examples below.
108.5 g (1 molar equivalent) of glyceryl monostearate (IIgA), 39.6 g (1 molar equivalent) of itaconic acid (I) and 1000 ppm (/reaction medium) of 4-methoxyphenol (or MEHQ) are introduced into a reactor at 135° C. with mechanical stirring. 0.5% (/reaction medium) of a 50% aqueous solution of H3PO2 is then added and the reaction medium is placed under controlled vacuum at about 500 mbar. The esterification reaction begins (distillation of the water formed) and is continued for 6 hours. After 6 hours, 125.7 g of glyceryl monostearate itaconate composition (AIIg) are isolated and characterized as such without any further steps.
The same procedure as described in paragraph E.1.1—was performed, replacing the 108.5 g (1 molar equivalent) of glyceryl monostearate (IIgA) and 39.6 g (1 molar equivalent) of itaconic acid (I) with 50.3 g (1 molar equivalent) of batyl alcohol (IIf) and 19.2 g (1 molar equivalent) of itaconic acid (I). 61.2 g of batyl alcohol itaconate composition (AIIf) are isolated and characterized.
The same procedure as described in paragraph E.1.1—was performed, replacing the 108.5 g (1 molar equivalent) of glyceryl monostearate (IIgA) and 39.6 g (1 molar equivalent) of itaconic acid (I) with 74.0 g (1 molar equivalent) of stearyl alcohol (IId17) and 35.9 g (1 molar equivalent) of itaconic acid (1). 100.3 g of stearyl alcohol itaconate composition (AIId17) are isolated and characterized.
The same procedure as described in paragraph E.1.1—was performed, replacing the 108.5 g (1 molar equivalent) of glyceryl monostearate (IIg) and 39.6 g (1 molar equivalent) of itaconic acid (1) with 160.1 g (1 molar equivalent) of polyglycerol-6 laurate (IIhB) and 32.3 g (1 molar equivalent) of itaconic acid (1). XXX g of the polyglyceryl-6 laurate itaconate composition (AIIh) are isolated and characterized.
The same procedure as described in paragraph E.1.3—was used, replacing the 1 molar equivalent of stearyl alcohol with 1 molar equivalent of an equimolar mixture of 1-eicosanol and 1-docosanol. 107.0 g of stearyl alcohol itaconate composition (AIId18) are isolated and characterized.
The analytical features of all the compositions (A) prepared are collated in table 1 below.
a)Determined by HPLC/UV in the presence of an internal standard,
b)Degree of conversion = [1-((mass composition (A) × % (I) residual)/mass itaconic acid at start)] × 100.
Overall, the esterification conditions described previously allow the isolation of compositions (A) having ester numbers of between 100 and 350 mg KOH/g, proving the significant formation of esterified species.
In all cases, the acid numbers are greater than 0, ranging between 60 and 350 mg KOH/g.
These values indicate that not all the carboxylic acid functions of itaconic acid (I) are esterified.
Finally, the degrees of conversion calculated from the final mass of composition (A) collected, the percentage of residual itaconic acid (I) contained in this final mass and determined by GC, and also the mass of itaconic acid (I) used initially, are systematically greater than 75%, indicating that the esterification reactions have proceeded satisfactorily.
23.3 g of composition (AIIf) and 4.3 g of composition (AIIh) are dissolved in 28.1 g of DUB 810 C in a reactor. The solution is homogenized with stirring at about 400 rpm at a temperature of 50° C., then sparged with nitrogen for 45 min so as to remove oxygen from the medium. The medium is then heated to a temperature of 80° C. 110 mg of lauroyl peroxide are then added to initiate the polymerization reaction. The medium becomes more viscous. After 2 h, 55 mg of lauryl peroxide are then introduced. After maintenance for a further 3 h, composition (C1) takes on a wax-like appearance and is conditioned while hot.
The same procedure as described in paragraph E.2.5—was performed, reducing the amount of composition (AIIf) from 23.3 to 20.5 g and increasing the amount of composition (AIIh) from 4.3 to 8.3 g. Composition (C2) was isolated.
The same procedure as described in paragraph E.2.5—was performed, replacing the 23.3 g of composition (AIIf) with 24.0 g of composition (AIIg) and replacing the 28.1 g of DUB 810 C with 28.1 g of Isopar™ M.
The same procedure as described in paragraph E.2.6—was performed, replacing the 20.5 g of composition (AIIf) with 20.5 g of composition (AIId18). Composition (C4) was isolated.
At 80° C., 0.7 g of compositions (C1) to (C3) are dissolved in 5 g of two different oils (H2): Primol™ 352 and Emogreen™ L19. The solutions thus obtained are cooled to room temperature and their thickening is assessed visually and/or measured at a temperature of 25° C. using a Brookfield (or BKF) viscometer of the LVT type fitted with a suitable spindle (M) and at a speed of 6 rpm (V6).
The results obtained for the observation at 25° C. are collated in Table 3 below.
The results obtained for the viscosity measurements performed using a BKF viscometer, spindle 3, speed 6 rpm at 25° C. are collated in Table 4 below.
In general, viscous or gelled consistencies were visualized for both oils (H2) differing in chemical structure and polarity.
Thickening is confirmed by measurement of the dynamic viscosities at 25° C., since at this same temperature of 25° C., Primol™ 352 shows a viscosity of 165 mPa·s (BKF LVT M2V6), DUB™ 810C shows a viscosity of 10 mPa·s (BKF LVT M2V6), and Emogreen™ L19 shows a viscosity of less than or equal to 10 mPa·s (BKF RVT M2V6).
None of the thickened oils, namely (C1) to (C4), show any runniness or tack or have a greasy feel on the skin after application to said skin (evaluated by a panel of duly qualified and trained evaluators).
These examples show that the process performed according to the invention advantageously allows a gelling agent to be obtained in liquid form, containing a polymer obtained by polymerization of monomers derived from starting materials of plant origin, which is ready for use immediately on preparation in the oil (H1), unlike the gelling polymers of the prior art which are in powder form.
| Number | Date | Country | Kind |
|---|---|---|---|
| FR2106666 | Jun 2021 | FR | national |
This application is the US national stage of PCT/EP2022/067062, filed Jun. 22, 2022 and designating the United States, which claims the priority of FR2106666, filed Jun. 23, 2021. The entire contents of each foregoing application are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/067062 | 6/22/2022 | WO |
