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Abstract

The present invention concerns a dispersion formed of a dispersed phase in the form of drops and a continuous phase, comprising a fatty phase and an aqueous phase non-miscible with each other at ambient temperature and atmospheric pressure, one of the phases among the fatty phase and the aqueous phase being the dispersed phase and the other phase among the fatty phase and aqueous phase being the continuous phase, wherein the drops comprise at least one core and at least one shell formed of at least one anionic polymer and at least one cationic polymer, the cationic polymer being a compound having the following formula (I):

##STR00001## where: n is an integer of 1 to 5; X.sup.1 and X.sup.2, the same or different, are —O—, —CH.sub.2— or —NH—; R.sup.1, R.sup.2 and R.sup.3, the same or different, are each independently a divalent alkylene radical having 20 to 50 carbon atoms; R.sup.4 and R.sup.5, the same or different, are each independently H, OH or NH.sub.2, at least one of the groups R.sup.4 and R.sup.5 being NH.sub.2.

Claims

1. A dispersion formed of a dispersed phase in the form of drops and a continuous phase, comprising a fatty phase and an aqueous phase non-miscible with each other at ambient temperature and atmospheric pressure, one of the phases from among the fatty phase and the aqueous phase being the dispersed phase and the other phase among the fatty phase and the aqueous phase being the continuous phase, wherein the drops comprise at least one core and at least one shell formed of at least one anionic polymer and at least one cationic polymer, the cationic polymer being a compound having the following formula (I): ##STR00011## where: n is an integer of 1 to 5, preferably of 1 to 3, more preferably of 1 or 2; X.sup.1 and X.sup.2, the same or different, are each independently —O—, —CH.sub.2— or —NH—, preferably at least one of the groups X.sup.1 and X.sup.2, even X.sup.1 and X.sup.2, being —NH—; R.sup.1, R.sup.2 and R.sup.3, the same or different, are each independently a linear, cyclic or branched, divalent alkylene radical having 20 to 50 carbon atoms, preferably 25 to 45 carbon atoms, better still 30 to 40 carbon atoms, and most preferably 34 to 36 carbon atoms, R.sup.1, R.sup.2 and R.sup.3 possibly including a cycloalkylene radical having 3 to 10 carbon atoms, preferably having 6 carbon atoms, said cycloalkylene radical optionally being substituted by one or more alkyl chains having 6 to 10 carbon atoms; R.sup.4 and R.sup.5, the same or different, are each independently H, OH or NH.sub.2, at least one of the groups R.sup.4 and R.sup.5 being NH.sub.2.

2. The dispersion according to claim 1, wherein the fatty phase is the dispersed phase and the aqueous phase is the continuous phase preferably in gel form.

3. The dispersion according to claim 1 or 2, wherein the cationic polymer is a lipophilic polymer able to be ionized in contact with an aqueous phase, and the anionic polymer is a hydrophilic polymer able to be ionized.

4. The dispersion according to any of the preceding claims wherein, in formula (I), X.sup.1 and X.sup.2 are —NH—.

5. The dispersion according to any of the preceding claims wherein, in formula (I), R.sup.4 and R.sup.5 are NH.sub.2.

6. The dispersion according to any of the preceding claims, wherein the cationic polymer has the following formula (II): ##STR00012## where n, R.sup.1, R.sup.2 and R.sup.3 are such as defined in claim 1, R.sup.2 and R.sup.3 preferably being the same.

7. The dispersion according to any of the preceding claims, wherein the cationic polymer has the following formula (III): ##STR00013## where n, R.sup.1 and R.sup.2 are such as defined in claim 1.

8. The dispersion according to any of the preceding claims, wherein each drop comprises from 0.001% to 10%, preferably from 0.005% to 5%, better still from 0.01% to 2.5%, more particularly from 0.05% to 1%, even from 0.1% to 0.5% by weight of cationic polymer(s) relative to the total weight of the phase comprising the same, and in particular the fatty phase.

9. The dispersion according to any of the preceding claims, wherein the anionic polymer is a polymer comprising monomer units comprising at least one carboxylic acid chemical function, preferably selected from among carbomers or an acrylates/C.sub.10-30 alkyl acrylate Crosspolymer, and preferably a carbomer.

10. The dispersion according to any of the preceding claims, wherein said dispersion comprises from 0.01% to 10%, preferably from 0.05% to 5%, more preferably from 0.10% to 2.5%, even from 0.5% to 1% by weight of anionic polymer(s), of carbomers in particular, relative to the total weight of the phase comprising the same, even of said dispersion.

11. The dispersion according to any of the preceding claims, wherein the drops comprise a core that is liquid or at least partially gelled or at least partially thixotropic, said core being single-phase or comprising an intermediate drop of an intermediate phase and at least one, preferably only one, inner drop of an inner phase arranged in the intermediate phase, the intermediate phase and the inner phase being non-miscible with each other at ambient temperature and atmospheric pressure.

12. The dispersion according to any of the preceding claims, wherein the mean diameter of the drops of the dispersed phase is from 0.2 μm to 3 000 μm, preferably from 20 μm to 2 500 μm, in particular from 200 μm to 2 000 μm, and most preferably from 500 μm to 1 500 μm.

13. The dispersion according to any of the preceding claims, wherein the fatty phase further comprises at least one lipophilic gelling agent, preferably selected from among organic or mineral, polymeric or molecular lipophilic gelling agents; fats solid at ambient temperature and ambient pressure; and mixtures thereof, and is preferably selected from the group composed of polymeric lipophilic gelling agents, and in particular from the group composed of polyacrylates, esters of dextrin and fatty acid(s), esters of glycerol and fatty acid(s), polyamides, and mixtures thereof.

14. The dispersion according to any of the preceding claims, comprising from 0.5% to 70%, preferably from 1% to 60%, in particular from 1.5% to 50%, better still from 2% to 40%, in particular from 5% to 30%, and most preferably from 10% to 20% by weight of lipophilic gelling agent(s) relative to the total weight of the fatty phase comprising the same.

15. The dispersion according to any of the preceding claims, characterized in that it does not contain a surfactant.

16. A method for preparing a dispersion such as defined in any of the preceding claims, comprising the following steps: optionally, heating an oily fluid FI and/or an aqueous fluid FE, to a temperature of 40° C. to 150° C.; placing the aqueous fluid FE and the oily fluid FI in contact; and forming fatty phase drops composed of the oily fluid FI, dispersed in a continuous aqueous phase composed of the aqueous fluid FE, or conversely, said drops comprising a shell insulating the core of the drops, wherein: the oily fluid FI comprises at least one oil and at least one cationic polymer of formula (I) according to claim 1, and optionally also at least one lipophilic gelling agent; and the aqueous fluid FE at least comprises water and at least one anionic polymer, in particular a carbomer, and optionally also at least one hydrophilic texturizing agent.

17. A composition, in particular cosmetic composition, comprising at least one dispersion according to any of claims 1 to 15, optionally in association with at least one physiologically acceptable medium.

18. A non-therapeutic cosmetic treatment method, in particular make-up and/or care method, of keratin material in particular of the skin, lips or hair, comprising at least one step to apply to said keratin material at least one dispersion according to any of claims 1 to 15, or at least one composition according to claim 17.

Description

EXAMPLES

Example 1—Synthesis of a Cationic Polymer of the Invention

[0260] This Example 1 is based on use of the raw material marketed by Croda under the trade name Priamine® 1075.

TABLE-US-00001 TABLE 1 Priamine ® 1075 [00008] Property Unit Value Amine number mgKOH/g 205 Gardner colour  1 Dynamic viscosity mPa.s at 25° C. 210 ISCC PLUS bio-content % 100 certified sustainable

[0261] This Example 1 is based on use of the raw material marketed by Croda under the trade name Pripol® 1009:

TABLE-US-00002 TABLE 2 Pripol ® 1009 [00009] Property Unit Value Acid number mgKOH/g 196 APHA colour Hazen at 25° C.  50 lodine number mgKOH/g  7 ISCC PLUS bio-content % 100 certified sustainable

[0262] The purification solvent used is Cetiol® C5C (INCI: Coco-Capyrylate/Caprate) marketed by BASF.

Step 1—Synthesis:

[0263] 546 g of Priamine® 1075 and 142 g de Pripol® 1009 were placed in a 1 L reactor. The reaction mixture was left under mechanical agitation at 140° C. for 23 h in a vacuum. The reaction was monitored by infra-red, in particular by growth and stabilization of the peak related to the amide functions (CONH, 1646 cm.sup.−1). Size exclusion chromatography (SEC) with polystyrene calibration indicated the presence in the reaction product of 44% «Priamine» (Mn theoretical 546 g/mol), 35% trimers (Mn theoretical 1663 g/mol), 15% pentamers (Mn theoretical 2780 g/mol), and 6% high-order oligomers. The amine number of the reaction medium was measured by titration at 2.2 equivalents/kg.

Step 1—Purification:

[0264] 10 g of the reaction product obtained after step 1 and 90 g of Cetiol® C5C were mixed together. The mixture was centrifuged at 5000 rpm, at 15° C. for 15 minutes and placed at 4° C. overnight. The mixture was subsequently recentrifuged at 5000 rpm at 4° C., for 15 to 20 minutes. The residue containing «Priamine» (30%), trimers (37%), pentamers (20%) and high-order oligomers (13%) was removed. The percentage evaluated by gravimetric of formula (I) compound(s) in solution in the oil was about 8.2% and the composition thereof estimated by calculation was 38% «Priamine», 42% trimers, 14% pentamers and 6% high-order oligomers. The amine number: «formula (I) compounds/Cetiol® C5C» measured by titration was 0.205 eq/kg.

TABLE-US-00003 TABLE 3 Compound of formula (I) resulting from the reaction between Priamine ® 1075 and Pripol ® 1009 [00010]

Example 2—Skin Care Macroscopic Dispersions

[0265] For this Example, two dispersions A and B were prepared of macroscopic drops of a gelled fatty phase dispersed in a continuous aqueous phase, using a microfluidic device such as described in WO2017046305. The compositions of the (fluid) phases allowing the preparation of these two dispersions were as follows:

TABLE-US-00004 TABLE 4 A B (Comp.) (Invtn.) Fluid Name INCI % w/w % w/w IF DUB ININ Grade A Isononyl isononanoate q.s .* (gelled Meadowfoam oil Limnanthes alba seed oil 18.00 fatty Rheopearl ® KL2 Dextrin palmitate, Palmitic 15.00 phase) Acid, Aqua PHAT BLUE DC6204 CI 61565 (and) CI 60725 0.00092 CAS-3131 PILOT Amodimethicone 0.20 0 Cationic polymer of — 0 0.041 formula (III)** Total 100 OF Osmosis water Aqua q.s .* (continuous Microcare ® PE Phenoxyethanol, aqua 0.89 aqueous Microcare ® emollient PTG Pentylene glycol, aqua 2.22 phase) Glycerine codex Glycerin, aqua 11.11 Edeta BD Disodium EDTA 0.044 Carbopol ® ETD 2050 Carbomer 0.33 polymer Sodium hydroxide Sodium hydroxide 0.013 pellets PRS codex Total 100 BF Osmosis water Aqua q.s.* (base) Sodium hydroxide Sodium hydroxide 0.35 pellets PRS codex Total 100 *q.s.: as much as suffices **Cationic polymer of formula (III) obtained in Example 1, and hence in which R1 is a divalent alkylene radical having 34 carbon atoms, and R2 is a divalent alkylene radical having 36 carbon atoms.

[0266] Preparation Protocol:

[0267] For OF:

[0268] The Phenoxyethanol, Pentyleneglycol and EDTA are incorporated in water. The mixture is left under agitation for 5 min.

[0269] The carbomer is dispersed in the preceding mixture under agitation for 30 minutes using a dispersion blade.

[0270] After the addition of glycerine, the mixture is left under further agitation for 10 min.

[0271] The addition is then made of sodium hydroxide and the solution is mixed for 10 minutes.

[0272] For IF:

[0273] The lipophilic cationic polymer (i.e. amodimethicone or cationic polymer of formula (III)) is added to the isononyl isononanoate and mixed with a magnetic stir bar for 5 min. The colouring agent PHAT BLUE DC6204 is afterwards added under agitation.

[0274] Under agitation, the addition is made of Meadowfoam oil.

[0275] The mixture is heated to 80° C. and Rheopearl® micr KL2 is added under magnetic stirring until a homogeneous solution is obtained.

[0276] The heated IF solution is charged into a syringe connected to a heat source to maintain the IF at a warm temperature (80° C.). To reduce heat losses, the microfluidic device is installed directly at the syringe outlet.

[0277] BF: the sodium hydroxide and water are mixed with a magnetic stir bar for 5 min.

[0278] In these tests, the flow rates per nozzle given below were used:

TABLE-US-00005 OF   150 mL/hr IF  20.35 mL/hr BF 16.667 mL/hr

[0279] In both cases, dispersions were obtained comprising spherical drops having a mean diameter of 1000 μm.

[0280] The cationic polymer of formula (I) therefore does not hamper good formation of the dispersion or the robustness of the production method.

[0281] In addition, the kinetics of the reaction of the cationic polymer of formula (I) with the «carbomer», and hence the formation of a shell of coacervate, appear similar to those obtained with Amodimethicone.

[0282] The cationic polymer of formula (I) is therefore able to substitute for amodimethicone, at least for the production of dispersions and in particular dispersions having macroscopic drops.

[0283] Visual analysis was carried out of the kinetic stability of the two dispersions in terms of adhesion, aggregation and turbidity (or opacification) of the aqueous phase.

[0284] For this purpose, after production, each of the dispersions A and B was placed in three 30 ml polypropylene (PP) containers that were half filled. After 1 day at ambient temperature, each sample was subjected to one of the three shaker tests below (one container per test), namely: [0285] roll test (i.e. circular, horizontal movement): Wheaton reference, for 1 hour; [0286] orbital shaker (i.e. circular, vertical movement): Heidolph Unimax 1010 reference, for 1 hour; and [0287] 3D mixer (i.e. random movements): for 6 minutes.

TABLE-US-00006 TABLE 5 ADHESION AGGREGATION TURBIDITY Attaching of drops Agglomeration of drops together Transfer of the fatty phase to the wall (agrégation tends to promote into the continuous aqueous of packaging coalescence) phase

[0288] Score Criteria:

TABLE-US-00007 TABLE 6 SCORE CRITERIA 0 1 2 3 ADHESION No adhesion Slight Moderate Strong adhesion adhesion adhesion AGGREGATION No aggregation Slight Moderate Strong aggregation aggregation aggregation GEL TURBIDITY Transparent gel Slightly Moderately Cloudy cloudy gel cloudy gel gel

[0289] Results:

TABLE-US-00008 TABLE 7 A B (Comp.) Invtn.) ADHESION 1 1 AGGREGATION 0 0 GEL 0 0 TURBIDITY

[0290] It is concluded from the above that the impact of a cationic polymer of the invention in terms of kinetic stability on a dispersion which, in addition, is provided with macroscopic drops, is similar to that of amodimethicone.

Example 3—Macroscopic Dispersions of Foundation Type

[0291] For this Example, two dispersions C and D of macroscopic drops were prepared of a gelled fatty phase dispersed in a continuous aqueous phase using a microfluidic device such as described in WO2019145424. The compositions of the (fluid) phases allowing the preparation of these two dispersions were the following:

TABLE-US-00009 TABLE 8 C D (Comp.) (Invtn.) % w/W Name INCI name Phases AQUEOUS GEL PHASE (=OF) 100.00 A Osmosis water / Aqua q.s .* A1 MICROCARE ® Thor PHENOXYETHANOL, 0.87 A1 PE AQUA MICROCARE ® Thor PENTYLENE GLYCOL, 2.17 A1 EMOLLIENT AQUA PTG CARBOPOL Lubrizol CARBOMER 0.20 A3 ETD2050 ALCASEALAN Hakuto ALCALIGENES 0.02 A2 POLYSACCHARIDES GLYCERINE Interchimie GLYCERIN, AQUA 3.26 A4 CODEX GLUCAM E20 Lubrizol METHYL GLUCETH-20 3.26 A4 HUMECesTANT UNITAMURON ® Induchem BUTYLENE GLYCOL, 5.43 A5 H-22 TAMARINDUS INCA SEED GUM, PHENOXYETHANOL EDETA BD BASF DISODIUM EDTA 0.03 A1 SODIUM Panréac SODIUM HYDROXIDE 0.03 A6 HYDROXIDE PELLETS PRS CODEX OILY PHASE (=IF) 100.00 B DUB ININ A Stearinerie Isononyl Isononanoate q.s.* B1 Dubois DUB 810C/MB Stearinerie Coco-Caprylate/Caprate 10.00 B2 Dubois NIKKOL NIKKO LIMNANTHES ALBA SEED OIL, 10 B2 MEADOWFOAM CHEMICALS TOCOPHEROL OIL Estogel ® M Polymer Castor Oil/IPDI Copolymer (70- 8 B1 Expert 90%), Caprylic/Capric Triglyceride (10-30%) CAS-3131 Nusil AMODIMETHICONE 1.5 0 B3 PILOT Cationic Croda — 0 0.41 B3 polymer of formula (III)** ASL-1 TIO2 Daito Kasei CI77891, Aluminium hydroxide, 38.82 B2 CR-50 Sodium Lauroyl glutamate, Lysine, Magnesium chloride ASL-1 YELLOW Daito Kasei CI 77492, Sodium Lauroyl 3.85 B2 LL-100P glutamate, Lysine, Magnesium chloride ASL-1 RED Daito Kasei CI 77491, Sodium Lauroyl 1.02 B2 R-516P glutamate, Lysine, Magnesium chloride ASL-1 BLACK Daito Kasei CI 77499, Sodium Lauroyl 0.07 B2 BL-100P glutamate, Lysine, Magnesium choride * and **: see Table in Example 2.

[0292] Preparation Protocol:

[0293] For OF: the same protocol as described in Example 1

[0294] For IF:

[0295] B1: The DUB ININ A and Estogel® M are mixed at 80° C. for 30 minutes using a dispersion blade until homogenization.

[0296] B2: In another container, the DUB 810C/MB and NIKKOL MEADOWFOAM OIL are mixed together and the four ASL pigments are added. The mixture is homogenized with a spatula (=mixture B2).

[0297] The B2 mixture is gently incorporated in mixture 1 under gentle agitation at 80° C. (=mixture X).

[0298] B3: The cationic polymer (i.e. Amodimethicone or Cationic polymer of formula (III)) is finally added to mixture X and agitation is continued for 3 minutes at 80° C.

[0299] Parameters of the Microfluidic Method:

[0300] In these tests, the following flow rates and parameters were used:

TABLE-US-00010 TABLE 9 Parameters of the Flow rate microfluidic method (per nozzle; in ml/h) IF 20 OF 180 BF*** 21.6 ***Optionally, provision can be made to add a viscosity-increasing solution (BF) to the continuous phase, to improve suspending of the drops of the dispersed phase in the continuous phase, in particular such as described in WO2015055748. This solution BF in particular is a sodium hydroxide solution (NaOH).

[0301] The kinetic stability tests carried out in Example 1 (i.e. adhesion, aggregation and turbidity (or opacification) of the aqueous phase) were repeated with the dispersions C and D.

[0302] The results obtained show that, for a macroscopic dispersion provided with a dispersed phase having a high pigment content, the cationic polymer of the invention possesses the same advantageous technical effects as amodimethicone.

[0303] In addition, the dispersions C and D have similar advantageous properties firstly in terms of coverage of imperfections and colour, and secondly on the level of sensory perception, freshness, hydration and lightness.

CONCLUSION

[0304] A cationic polymer of formula (I) therefore affords a credible, non-silicone, biosourced alternative to amodimethicone for shell formation and for stabilization of dispersions, in particular macroscopic dispersions.