Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/042—Gels
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/91—Graft copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

• Polymer comprising water-soluble units and units with LCST, and aqueous composition comprising it
• the present invention relates to a new family of polymers and their salts, capable of being used in cosmetic or pharmaceutical compositions, in particular for modifying their rheological properties.
• compositions which become fluid in summer and are more viscous in winter can however have certain drawbacks, such as modifying the rheology of the composition as a function of changes in temperature (compositions which become fluid in summer and are more viscous in winter).
• Particular polymers are known in the state of the art, the solubility of which in water is modified beyond a certain temperature. These are polymers having a temperature of demixing by heating (or cloud point), thus defining their zone of solubility in water.
• the minimum demixing temperature obtained as a function of the polymer concentration is called "LCST" (Lower Critical Solution Temperature).
• polymers described in this application can be of any chemical nature; in particular they can be in the form of graft copolymers comprising a skeleton sensitive to pH with grafts sensitive to temperature; or conversely in the form of a temperature-sensitive skeleton carrying pH-sensitive grafts; or also in the form of block copolymers formed of pH-sensitive units and of temperature-sensitive units.
• the temperature-sensitive grafts or blocks therefore have an LCST type temperature as defined above.
• These blocks or grafts can be prepared by polymerization of vinyl monomers or by polymerization of cyclic ether monomers.
• these grafts or blocks may be in the form of poly (N-alkyl substituted) acrylamides or block copolymers of ethylene oxide and propylene oxide.
• the aim of the present invention is to overcome the drawbacks of the prior art and to propose a new family of polymers which makes it possible to control the rheology of aqueous compositions as a function of temperature, while retaining the compositions a certain transparency.
• this new family of polymers makes it possible on the one hand to prepare them on demand, whatever the nature of the backbone polymer and / or of the grafts, and / or their respective quantity and / or the desired structure (for example linear or trendy); this allows in particular to adapt the properties sought, depending on the applications envisaged.
• An object of the present invention is a polymer comprising water-soluble units carrying at least two reactive sites, and units having an LCST type temperature carrying at least one reactive site, capable of reacting with the reactive sites carried by the water-soluble unit, so as to form a covalent bond, said LCST units being made up of random copolymers of ethylene oxide and propylene oxide, having a number of ethylene oxide between 0 and 40 inclusive and a number d propylene oxide between 15 and 60 times, as well as the salts of this polymer.
• Another subject of the invention is a thickened or even gelled aqueous composition
• a thickened or even gelled aqueous composition comprising at least one polymer as defined above or one of its salts, and an aqueous phase.
• the salts of the polymers according to the invention can be of any kind, organic or mineral, for example sodium, magnesium, ammonium, triethanolamine salts.
• Water-soluble polymers are thus obtained, in particular having a solubility in water, at 20 ° C, of at least 10 g / l, preferably at least 20 g / l.
• These water-soluble polymers make it possible to control the rheology of aqueous compositions as a function of the temperature, while retaining their transparency to said compositions. Furthermore, it is possible to adjust at will the temperature range relevant for the cosmetic application envisaged, by appropriately choosing the chemical nature of the water-soluble units, of the units with LCST, as well as their respective quantities.
• the polymers according to the present invention may be block polymers (or blocks), or graft polymers, which comprise on the one hand water-soluble units and on the other hand units having a temperature of LCST type as defined below.
• the polymers used in the context of the invention can therefore be block polymers, comprising, for example, water-soluble blocks alternated with LCST blocks.
• These polymers can also be in the form of grafted polymers whose backbone is formed of water-soluble units, carrying LCST grafts. This structure can be partially crosslinked.
• water-soluble units units which are soluble in water, at 20 ° C., at a rate of at least 10 g / l, preferably at least 20 g / l.
• water-soluble units units which do not necessarily have the above-mentioned solubility, but which in solution at 1% by weight in water at 20 ° C. allow a solution to be obtained macroscopically.
• homogeneous and transparent i.e. having a maximum light transmittance value, whatever the wavelength between 400 and 800 nm, through a sample 1 cm thick, at least 80%, preferably at least 85%.
• the water-soluble units can be in the form of blocks within a block polymer, or constitute the skeleton of a grafted polymer. These water-soluble units do not have a demixing temperature by heating of the LCST type.
• These water-soluble units can be obtained by radical polymerization of vinyl monomers, or by polycondensation, or else can be constituted by existing natural or modified natural polymers.
• the water-soluble units employed carry at least two reactive sites.
• - R is chosen from H, -CH 3 , -C 2 H 5 or -CH 7
• R' is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 8 carbons, substituted by at least one hydroxy group (-OH); primary amine (-NH 2 ); secondary (-NHRi) or tertiary (-NR 1 R 2 ) amine with Ri and R 2 , independently of each other, representing a hydrocarbon radical, linear or branched, saturated or unsaturated, having 1 to 25 carbon atoms, provided that the sum of the carbon atoms of Ri + R 2 does not exceed 26; a halogen atom (iodine, bromine, chlorine, fluorine);
• R' and R are, independently of one another, hydrocarbon radicals, linear or branched, saturated or unsaturated having 1 to 25 carbon atoms , provided that the total number of carbon atoms of R '+ R "does not exceed 26, said R' and R" being optionally substituted by a hydroxy group (-OH); sulfonic (-SO 3 ); sulfate (-SO4); phosphate (-PO 4 H 2 ); primary amine (-NH 2 ); secondary (- NHR1), tertiary (-NR1R2) and / or quaternary (-N + R ⁇ R 2 Rs) amine with Ri, R 2 and R 3 being, independently of one another, a linear or branched hydrocarbon radical , saturated or unsaturated having 1 to 25 carbon atoms, provided that the sum of the carbon atoms of Ri + R 2 does not exceed 26, and that the sum of the carbon
• monomers B there may be mentioned, alone or as a mixture, the monomers below, taken as such or in the form of organic or inorganic salts, for example, in the form of sodium, magnesium, ammonium or of triethanolamine:
• - R is chosen from H, -CH 3 , -C 2 H 5 or -C 3 H 7 - X is chosen from alkyl oxides of -OR 'type where R' is a saturated linear or branched hydrocarbon radical or unsaturated, having from 1 to 8 carbons, optionally substituted by a sulphonic group (-SO 3 ), sulphate (-SO 4 ), phosphate (- PO 4 H 2 ); and / or quaternary amine (-N + R 1 R 2 R 3 ) with Ri, R 2 and R 3 being, independently of one another, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 25 carbon atoms, provided that the sum of the carbon atoms of Ri + R 2 + R3 does not exceed 27;
• N-vinyllactams such as N-vinylpyrrolidone, N-vinylcaprolactam and N-butyrolactam;
• - vinyl ethers of formula CH 2 CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 25 carbons; - the water-soluble derivatives of styrene, in particular styrene sulfonate;
• polycondensates and natural or modified natural polymers capable of constituting all or part of the water-soluble units mention may be made of: - water-soluble polyurethanes having at least two reactive sites, in particular carrying carboxylic acid functions,
• Rhodigel SM and Rhodigel 200 from Rhodia
• - cellulose derivatives and in particular carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose and quaternized hydroxyethylcellulose;
• - galactomannans and their derivatives such as Konjac gum, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups, guar chloride hydroxypropyl tri-methyl ammonium.
• the water-soluble units have a molar mass of between 10,000 g / mole and 5,000,000 g / mole when they constitute the water-soluble backbone of a grafted polymer.
• These water-soluble units preferably have a molar mass of between 5000 g / mole and 100,000 g / mole when they constitute a block of a multi-block polymer.
• the water-soluble units carry at least two reactive sites, capable of reacting with at least one reactive site. carried by the units to LCST, in order to give a covalent bond.
• This reactive site can in particular be chosen from the alcohol, isocyanate, primary, secondary or tertiary amine, carboxylic acid and halogen functions.
• a reactive site of the carboxylic acid type will generally react with a reactive site of the alcohol or amino type; an isocyanate site will rather react with an alcohol site, and a halogen site will rather react with an alcohol or amino site.
• units with LCST we mean units whose solubility in water is modified beyond a certain temperature. These are units with a temperature of demixing by heating (or cloud point) defining their zone of solubility in water.
• the minimum demixing temperature obtained as a function of the polymer concentration is called “LCST” (Lower Critical Solution Temperature). For each polymer concentration, this temperature of demixing by heating is observed; it is greater than the LCST which is the minimum point of the curve. Below this temperature, the polymer is soluble in water; above this temperature, the polymer loses its solubility in water.
• water soluble is meant that the units have a solubility at 20 ° C, of at least 1 g / l, preferably at least 2 g / l.
• the measurement of the LCST can be done visually: the temperature at which the cloud point of the aqueous solution appears is determined; this cloud point results in clouding of the solution, or loss of transparency.
• a transparent composition will have a maximum light transmittance value, whatever the wavelength between 400 and 800 nm, through a sample of 1 cm thickness, of at least 80%, preferably at least 90% (see EP291334). Transmittance can be measured by placing a 1 cm thick sample in the light ray of a spectrophotometer working in the wavelengths of the light spectrum.
• the LCST units used in the present invention consist of random copolymers of ethylene oxide and propylene oxide, which can be represented by the formula: (OE) m (OP) n in which m is a number between 0 and 40 inclusive and n is a number between 15 and 60 inclusive.
• m is between 1 and 20 inclusive and n is between 20 and 50 inclusive.
• the molar mass of the units with LCST is between 1500 and
• micellization aggregation on a microscopic scale
• the units with LCST must of course also carry at least one reactive site, capable of reacting with the reactive site carried by the water-soluble unit, so as to form a covalent bond.
• this reactive site can be chosen from alcohol, isocyanate, primary, secondary or tertiary amine, carboxylic acid, halogen.
• the reactive sites are distributed statistically along the water-soluble skeleton and those of the grafts are located at at least one of the ends of the LCST chains.
• the reactive sites are located at the ends of the water-soluble units and of the LCST units.
• the units with LCST can therefore in particular be in the form of random copolymers of ethylene oxide and of propylene oxide, amino, in particular monoamine, diamine or triamine.
• the units with LCST can also be in the form of polyalkylene glycols, random OE OP copolymers with OH ends, such as those sold under the name Polyglycols P41 and B11 by Clariant.
• Xanthan alginates, carboxymethylcellulose, hydroxypropylguar modified with sodium methylcarboxylate groups; or one of their organic or mineral salts;
• LCST grafts consisting of random copolymers of ethylene oxide and propylene oxide, amino, in particular monoaminates, diamines or triaminates.
• the mass proportion of the LCST units in the final polymer is preferably between 5% and 70%, in particular between 20% and 65%, and particularly between 30% and 60% by weight, relative to the final polymer.
• the demixing temperature by heating of the LCST type of said LCST units is between 5 ° C. and 40 ° C., preferably 10 ° C. and 35 ° C., for a mass concentration in water, of 1% in weight of said units at LCST.
• the polymers used in the context of the invention can be easily prepared by a person skilled in the art on the basis of his general knowledge.
• the final polymer when the final polymer is in the form of a grafted polymer, in particular having a water-soluble skeleton with grafted LCST units, it is possible to prepare it by grafting chains with LCST having at least one reactive end, in particular amine, on said water-soluble polymer forming the backbone, carrying at least 10% (by mole) of carboxylic acid groups.
• This reaction can be carried out in the presence of a carbodiimide such as dicyclohexylcarbodiimide or 1- (3-dimethyl! Aminopropyl) -3-ethyl carbodiimide hydrochloride, in a solvent such as N-methylpyrrolidone or water .
• thermoassociative polymers comprising a skeleton water-soluble polyacrylic acid, on which LCST units are grafted consisting of random copolymers of ethylene oxide and propylene oxide.
• the polymers described in this publication are not suitable in the present application because they have certain drawbacks in particular linked to the low molar mass of the grafts used; in particular the graft called PPO has a molar mass of 600.
• the gelation temperature of the final polymer does not quite correspond to the demixing temperature of the grafts with LCST; there may be a difference between these two temperatures of up to 15 to 20 ° C. Predicting thermogelling properties for industrial application then becomes complex.
• the quantity of LCST units to be incorporated into the polymer in order to have advantageous solution properties implies high grafting rates when the molar mass of the graft is small. This notably imposes the presence of a large proportion of reactive sites on the water-soluble skeleton, hence a certain limitation in terms of structure and synthesis. In addition, the association of grafts can become more difficult when they are smaller.
• LCST macromonomer LCST chain previously described with a vinyl end
• a water-soluble vinyl monomer such as acrylic acid or vinyl monomers having the formula (IIa ) or (llb).
• the final polymer is in the form of a block polymer, it is possible to prepare it by coupling between water-soluble units and LCST units having at each end complementary reactive sites.
• the polymers thus obtained are water-soluble and thermogelling.
• transparent solution or composition is understood to mean the conventional definition given in the dictionary.
• a transparent composition can easily be passed through by light and makes it possible to clearly distinguish objects through its thickness.
• Transmittance can be measured by placing a 1 cm thick sample in the light beam of a spectrophotometer working in the wavelengths of the light spectrum.
• compositions thus prepared can have a maximum light transmittance value, whatever the wavelength between 400 and 800 nm, through a sample 1 cm thick, at least 80%, preferably at least 85% (see EP291334).
• the polymers according to the invention are preferably present in the aqueous compositions in an amount preferably between 0.01 and 20% by weight, in particular from 0.05 to 15% by weight, and in particular from 0.1 to 10 % in weight. These compositions and the polymers which they comprise find a very particular application in the cosmetic and pharmaceutical fields.
• Said composition comprises, in addition to the polymer as defined above, an aqueous phase, which may comprise, in addition to water, floral water such as blueberry water, mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and / or thermal water.
• floral water such as blueberry water
• mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water
• thermal water such as thermal water.
• compositions according to the invention may contain an oily phase, for example, in the form of an oil-in-water emulsion, a water-in-oil emulsion or multiple emulsions such as water-in-emulsions oil-in-water.
• Said aqueous composition can form all or part of a cosmetic or pharmaceutical composition which can therefore also comprise a cosmetically or pharmaceutically acceptable medium, that is to say a medium compatible with an application to keratin materials such as skin, nails, hair, eyelashes and eyebrows, mucous membranes and semi-mucous membranes, and any other skin area of the body and face.
• a cosmetically or pharmaceutically acceptable medium that is to say a medium compatible with an application to keratin materials such as skin, nails, hair, eyelashes and eyebrows, mucous membranes and semi-mucous membranes, and any other skin area of the body and face.
• composition therefore finds a particular application as a cosmetic, make-up or care composition, capable of being applied to the skin, nails, hair, eyelashes and eyebrows, mucous membranes and semi-mucous membranes, and any other skin area. body and face.
• the final mixture is stirred for 12 hours at 60 ° C.
• the mixture is cooled to 20 ° C and then placed in a refrigerator at 4 ° C for 24 hours.
• the dicyclohexylurea crystals formed are removed by filtration from the reaction medium.
• the polymer is then neutralized using 19 g of 35% sodium hydroxide (4 times in excess relative to the number of moles of acrylic acid), which leads to its precipitation. After standing for 12 hours, the reaction medium is filtered in order to recover the precipitated polymer. This is dried under vacuum at 35 ° C for 24 hours.
• the mass proportion of the LCST units in the final polymer is 51%.
• the polymer thus obtained has a solubility in water, at 20 ° C, of at least 10 g / l.
• Example 2 In a similar manner to Example 1, the following five polymers are prepared, in which the grafts are always a copolymer (OE) 6 (OP) 3 9 statistical monoamine:
• Example 3 1.51 grams of polyacrylic acid with an average molar mass of 750,000 g / mole (Aldrich) are dissolved in 350 ml of deionized water with stirring at 20 ° C. for 12 hours in a 1 liter reactor fitted with a condenser. . The pH of the reaction medium is then adjusted to 8 using a 1M sodium hydroxide solution. 1.60 grams of copolymer (OE) 6 (OP) 39 are dissolved mono-amino statistic (Jeffamine M-2005 from Huntsman) in 100 ml of deionized water with stirring at 5 ° C for 30 minutes. The solution obtained is added dropwise to the reaction medium with vigorous stirring.
• OE copolymer
• OP mono-amino statistic
• the reaction medium is cooled to 20 ° C. then concentrated and precipitated in acetone.
• the polymer in solid form is recovered by filtration and washed with an excess of acetone.
• the powder is ground and dried under vacuum at 35 ° C.
• the polymers according to the invention are compared with the polymers of the prior art described in the publication Hourdet et al., Polymer, vol.38, no10, pp.2535-2547, 1997.
• the gelation temperature is determined using rheological curves measuring the viscosity as a function of temperature, for the polymer solution on the one hand and for an aqueous solution of water-soluble backbone at a concentration tration identical to the concentration of water-soluble units in the polymer solution.
• the gelation temperature reached is considered when the difference between the viscosity of the polymer solution and the viscosity of the water-soluble backbone solution is greater than 5%.
• the viscosity measurement method is given in Example 6.
• the demixing temperature is determined visually, for a solution in LCST grafts alone, at a concentration identical to the concentration of grafts in the polymer solution.
• the polymers according to the invention are compared with polymers of the prior art described in WO95 / 24430.
• absorbance -log transmittance
• Comparison 1 poly (N-isopropylacrylamide) and polyacrylic acid 24/76 block copolymer (FIG. 1 of WO95 / 24430)
• thermogelling gel comprising:
• This composition is prepared by simple introduction of the polymer into salt water with stirring for 2 hours at 20 ° C.
• the viscosity of the composition is measured, at 20 ° C. and at 32 ° C., using a Haake RS150 rheometer provided with a cone / plane geometry 3.5 cm / 2 ° or 6 cm / 2 ° and a temperature control system.
• the viscosity measurements are carried out in the flow mode by imposing a shear gradient equal to 10 s "1 .

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