Cosmetic cleansing formulation

Abstract

A water-rinsable, aqueous cleansing formulation may include a cosmetic oily component. The formulation may foam and remain stable despite the presence of a cosmetic oily component, even when the oily component is present in potentially substantial amounts.

Claims

1. A water-rinsable, aqueous cleansing formulation, comprising: a) an anionic copolymer A comprising an ASE copolymer, a HASE copolymer, or a combination thereof; b) a cosmetic oil component B in an amount of from 1 to 40 wt. %, relative to a total formulation weight, in the form of droplets dispersed in the aqueous phase with a polydispersity, (D90%−D10%)/D50%, of less than 1.7, wherein the droplets of the cosmetic oil component B have a D50% of from 1 μm to 50 μm; and c) a surface-active agent C, wherein a Brookfield viscosity of the water-rinsable, aqueous cleansing formulation measured at 6 rpms at 20° C. is at least 19,600 mPa.Math.s, wherein the water-rinsable, aqueous cleansing formulation is prepared by a method comprising: (a) preparing an oil-in-water emulsion comprising, by weight, relative to a weight of the oil-in-water emulsion, from 0.5 to 4 wt. % of the anionic copolymer A comprising an ASE copolymer, a HASE copolymer, or a combination thereof; from 20 to 70 wt. % of the cosmetic oil component B; q.s.p. 100% water, by adding, under agitation at a speed of form 200 rpm to 10,000 rpm, the cosmetic oil component B to an aqueous phase (AP) having a pH at least 6.5, comprising the anionic copolymer A and water, and (b) mixing the oil-in-water emulsion obtained in the preparing (a) with an aqueous composition comprising the surface-active agent C.

2. The formulation of claim 1, wherein the polydispersity of the droplets of the oil component B is less than 1.6.

3. The formulation of claim 1, wherein the anionic copolymer A comprises: the ASE copolymer, which is prepared by polymerizing components comprising (a1) an anionic monomer comprising a polymerizable olefinic unsaturation; (a2) an ester of a compound derived from a carboxylic acid comprising a polymerizable olefinic unsaturation; (a4) optionally, a monomer comprising a polymerizable unsaturation and a sulfonic acid or phosphoric acid group; (a5) optionally, a hydroxy(C.sub.1-C.sub.6)-alkyl acrylate and/or a hydroxy(C1-C6)-alkyl methacrylate; and (a6) optionally, a cross-linking monomer or a monomer comprising a first olefinic unsaturation and a second olefinic unsaturation; the HASE copolymer, which is prepared by polymerizing components comprising: (a1) an anionic monomer comprising a polymerizable olefinic unsaturation; (a2) an ester of a compound derived from a carboxylic acid comprising a polymerizable olefinic unsaturation; (a3) an associative hydrophobic monomer: (a4) optionally, a monomer comprising a polymerizable olefinic unsaturation and a sulfonic acid or phosphoric acid group; (a5) optionally, a hydroxy(C1-C6)-alkyl acrylate and/or a hydroxy(C1-C6)-alkyl methacrylate; and (a6) optionally, a cross-linking monomer or a monomer comprising a first olefinic unsaturation and a second olefinic unsaturation, or a combination of the ASE copolymer and HASE copolymer.

4. The formulation of claim 3, wherein: the anionic monomer (a1) comprises acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, crotonic acid, an acrylic acid salt, a methacrylic acid salt, a maleic acid salt, a maleic anhydride salt, an itaconic acid salt, a crotonic acid salt, or a combination thereof; or the monomer (a2) an ester comprising, in esterified form, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, crotonic acid, or a combination thereof; or the monomer (a3) is a compound of the following formula (I):
R.sup.1-(EO).sub.m—(PO).sub.n—R.sup.2  (I), wherein m and n are independently 0 or an integer or decimal less than 150, and m or n is different from 0, EO is independently a CH.sub.2CH.sub.2O group, PO is independently CH(CH.sub.3)CH.sub.2O of CH.sub.2CH(CH.sub.3)O, R.sup.1 is a group comprising a polymerizable olefinic unsaturation, and R.sup.2 is a straight or branched C.sub.6-C.sub.40-alkyl group, a phenyl group, or a polyphenyl group; or the monomer (a4) comprises 2-acrylamido-2-methylpropane sulfonic acid, ethoxymethacrylate sulfonic acid, sodium methallyl sulfonate, styrene sulfonate hydroxyethyl acrylate phosphate, hydroxypropyl acrylate phosphate, hydroxyethylhexyl acrylate phosphate, hydroxyethyl methacrylate phosphate, hydroxypropyl methacrylate phosphate, and/or hydroxyethylhexyl methacrylate phosphate, or a combination thereof, optionally in salt form; or the monomer (a5) comprises hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, or a combination thereof.

5. The formulation of claim 1, comprising from 5 to 35 wt. %, relative to the total formulation weight, of the cosmetic oil component B.

6. The formulation of claim 1, wherein the surface-active agent C comprises an anionic surface-active agent, an amphoteric surface-active agent, a nonionic surface-active agent, or a combination thereof.

7. The formulation of claim 1, further comprising: a suspensivant agent.

8. The formulation of claim 1, having a pH of from 5 to 12.

9. The formulation of claim 1, which is a shower gel or a shampoo.

10. The formulation of claim 1, wherein the polydispersity of the droplets of the oil component B is less than 1.5.

11. The formulation of claim 3, wherein the anionic monomer (a1) comprises a polymerizable olefinic unsaturation and a carboxylic acid group.

12. The formulation of claim 1, wherein the D50% of the droplets of the cosmetic oil component B is from 1 μm to 30 μm.

13. A method of preparing a water-rinsable, aqueous cleansing formulation, the method comprising: (a) preparing an oil-in-water emulsion comprising, by weight, relative to a weight of the oil-in-water emulsion, from 0.5 to 4 wt. % of an anionic copolymer A comprising an ASE copolymer, a HASE copolymer, or a combination thereof; from 20 to 70 wt. % of a cosmetic oil component B; q.s.p. 100% water, by adding, under stirring, the cosmetic oil component B to an aqueous phase (AP) having a pH at least 6.5, comprising the anionic copolymer A and water, and (b) mixing the oil-in-water emulsion obtained in the preparing (a) with an aqueous composition comprising a surface-active agent C, wherein the water-rinsable, aqueous cleansing formulation, comprises: a) an anionic copolymer A comprising an ASE copolymer, a HASE copolymer, or a combination thereof; b) a cosmetic oil component B in an amount of from 1 to 40 wt. %, relative to a total formulation weight, in the form of droplets dispersed in the aqueous phase with a polydispersity, (D90%−D10%)/D50%, of less than 1.7, wherein the droplets of the cosmetic oil component B have a D50% of from 1 μm to 50 μm; and c) a surface-active agent C, wherein a Brookfield viscosity of the water-rinsable, aqueous cleansing formulation measured at 6 rpms at 20° C. is at least 19,600 mPa.Math.s.

14. The method of claim 2, wherein the aqueous phase (AP) is prepared by a method comprising: (a-i) mixing the anionic copolymer A comprising an ASE copolymer, a HASE copolymer, or a combination thereof and water; then (a-ii) adjusting the pH of the mixture obtained in the mixing (a-ii) to at least 6.5.

15. The method of claim 13, comprising, prior to the mixing (b): (a′) adjusting the pH of the oil-in-water emulsion obtained in the preparing (a) to a pH of from 5 to 12.

16. The method of claim 13, wherein the mixing (b) comprises adjusting the pH of the formulation to a pH of from 5 to 12.

17. A cleansing formulation, obtained by the method of claim 13, wherein the cosmetic oil component B is in the form of droplets dispersed in the aqueous phase and having a polydispersity, (D90%−D10%)/D50%, less than 1.7.

Description

EXAMPLES

(1) Raw Materials Anionic copolymer A: see method of preparation Rhodasurf® ID 030, Solvay: ethoxylated fatty acid, CAS #: 26183-52-8 Fancryl 512-AS, Hitachi Chemical: Dicyclopentenyl acrylate, CAS #: 65983-31-5 SLES=sodium laureth sulphate (Texapon NSO UP, BASF) CAPB=cocoamidopropyl betaine (Dehyton PK 45, BASF) PQ-7=polyquaternium-7 (Salecare super 7 AT 1, BASF) Sweet almond oil=oil Dulcis amygdalus prunus, CAS #: 8007-69-0/90320-37-9 Sesame seed oil=oil Sesamum Indicum, CAS #: 8008-74-0 Carbopol® Ultrez 20, Lubrizol=Acrylates/C10-30 Alkyl Acrylate Crosspolymer Emulium Delta, Gattefossé=Cetyl Alcohol (and) Glyceryl Stearate (and) PEG-75 Stearate (and) Ceteth-20 (and) Steareth-20 Rheostyl™ 100, Coatex=acrylates copolymer Phenoxyethanol, CAS #122-99-6 sodium hydroxide NaOH.

(2) Anionic Copolymer A—Preparation Method

(3) In a 1 L reactor under stirring and heated using an oil bath, mixture 1 is prepared by introducing deionised water and sodium lauryl sulphate (SLS) and optionally an ethoxylated fatty acid (Rhodasurf® ID 030).

(4) A mixture 2, called a monomer premixture, comprising deionised water, is prepared in a beaker: Methacrylic Acid (MAA), Ethyl Acrylate (EA), optionally a cross-linked monomer (Fancryl 512-AS), sodium lauryl sulphate (SLS), optionally an associative hydrophobic monomer, branched C.sub.16-alkyl (EO)25-methacrylate obtained from a Guerbet reaction or straight C.sub.12-alkyl (EO)23 methacrylate, optionally n-dodecylmercaptan.

(5) This premixture is stirred to form a monomer mixture.

(6) An initiator solution 1 is prepared comprising ammonium persulphate and deionised water. Optionally, an initiator solution 2 is prepared comprising ammonium persulphate and deionised water. All reagents and amounts used are listed in Table 1.

(7) In the reactor heated to the polymerisation temperature of ±1° C., the initiator solution 1 is injected, if applicable at the same time the initiator solution 2, then the monomer premixture for 2 hours (for CA3 in Table 1, the initiator solution 1 and the monomer premixture are injected in parallel for 2 hours and 30 minutes). The preparation is cooked for 30 minutes at the polymerisation temperature. The mixture is then cooled to room temperature.

(8) The polymers according to the invention were prepared under these conditions by varying the monomer compositions of the monomer premixtures. The compositions of the copolymers obtained are listed in Table 1.

(9) TABLE-US-00001 TABLE 1 Anionic Copolymer Amount (g) CA1 CA2 CA3 Mixture 1 Deionised water 474.6 468.0 476.5 SLES 6.5 6.4 0.3 Rhodasurf ® ID 030 5.4 0 0 AMPS 2405 50% 5.3 8.0 0 Premixture Deionised water 140.7 142.3 93.1 SLES 2.3 2.2 3.1 MAA 108.6 101.8 105.9 EA 158.1 150.1 200.2 Fancryl 512-AS cross-linking 0 0 0.6 monomer Straight C12-alkyl 0 34.4 0 (EO)23 methacrylate Branched C16-alkyl 21.6 1 0 0 (EO)25-methacrylate N-dodecyl mercaptan 0.07 0.3 0 Initiator 1 Deionised water 4.8 7.1 46.3 Ammonium persulphate 0.9 0.9 0.3 Initiator 2 Deionised water 4.8 4.4 0 Sodium methabisulphite 0.1 0.1 0 Polymerisation temperature 80° C. 80° C. 85° C.

(10) Copolymers (CA1), (CA2) and (CA3) are obtained.

(11) Protocol for Preparing Oil-In-Water Emulsions for Step a)

(12) Place the ingredients for phase P1 in a beaker and place under stirring in a VMI Rayneri-type stirrer. Neutralise the mixture with the sodium hydroxide solution for phase P2 to get a pH of 7. Lastly, gradually incorporate the oil in phase P3. For an emulsion comprising Emulium Delta, phase P1 should be heated at 70-80° C. until a homogeneous mixture is obtained. In Table 2, the percentages, %, are percentages by weight relative to the total weight of the oil-in-water emulsion. The “x” value corresponds to the solids content of the anionic copolymer A or of the Emulium Delta.

(13) TABLE-US-00002 TABLE 2 Ingredients % Phase P1 Water Qsp 100% Anionic copolymer A for the examples according x % to the invention or Emulium Delta for the comparative example Phase P2 Sodium hydroxide 20% Qsp pH 6.7-7.1 Phase P3 Oil 40

(14) Shower Gel Preparation Protocol

(15) In a beaker, under stirring using a stirrer, the Phase P′ 1 ingredients are added in the order in the following table. Once the mixture is homogeneous, the ingredients in Phase P′2 are added. Lastly, the pH is adjusted using the sodium hydroxide solution in Phase P′3. The ingredients and amounts used are shown in Table 3. The percentages, %, are percentages by weight relative to the total weight of the shower gel.

(16) TABLE-US-00003 TABLE 3 Ingredients % Phase P′1 Water Qsp 100% RHEOSTYL ™ 100 30% (or Carbopol ® Ultrez 20) 8.00% (or 0.5%) Oil-in-water emulsion from step a) containing 40% (y/0.4) % (or y %) oil for the examples according to the invention (or pure oil for comparative example 2) Texapon NSO UP Sodium Laureth Sulphate 28% 32.5% Dehyton PK 45 Cocamidopropylbetaine 45%  6.7% Phase P′2 Salcare Super 7 AT1 Polyquaternium-7 40% 0.28% Phenoxyethanol  0.5% Phase P′3 Sodium hydroxide 20% Qsp pH 6.7-7.1

Example 1

(17) An oil-in-water emulsion, O/W, is prepared according to the protocol described in the introduction (Table 2). Each emulsion comprises 1% by weight of anionic copolymer A chosen among the copolymer (CA1), the copolymer (CA2) or the copolymer (CA3), defined in Table 1. Each emulsion comprises 40% by weight of sweet almond oil.

(18) Each emulsion is then used to make a shower gel comprising 10% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (Table 3). Phase P′ 1 comprises 8% by weight of Rheostyl™ 10030%.

(19) A reference shower gel is also used, denoted as T, comprising all of the ingredients of the shower gel described in Table 3 except for the oil-in-water emulsion in step a) containing 40% oil. This reference shower gel also does not comprise oil.

(20) For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(21) The results are shown in Table 4, n/a denotes not applicable.

(22) TABLE-US-00004 TABLE 4 T CA1 CA2 CA3 Foam (mL) 114 101 130 113 Foam stability (%) 83 81 78 80 D50% in shower gel (μm) n/a 3.1 3 3.1 Shower gel polydispersity n/a 1.13 1.21 1.13 Viscosity 25° C., 6 rpm (mPa .Math. s) 4,400 19,600 24,400 19,600 Stability 1 month 50° C. n/a yes yes yes

Example 2

(23) An oil-in-water emulsion, O/W, is prepared according to the protocol described in the introduction (Table 2). Each emulsion comprises 0.7% or 1% or 1.5% by weight of anionic copolymer (CA1), defined in Table 1. Each emulsion comprises 40% by weight of sweet almond oil.

(24) Each emulsion is then used to make a shower gel comprising 10% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (Table 3). Phase P′ 1 comprises 8% by weight of Rheostyl™ 100 30.

(25) A reference shower gel is also used, denoted as T, comprising all of the ingredients of the shower gel described in Table 3 except for the oil-in-water emulsion in step a) containing 40% oil. This reference shower gel also does not comprise oil.

(26) For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(27) The results are shown in Table 5.

(28) TABLE-US-00005 TABLE 5 Shower Gel According to the invention Reference (CA1) content 0.18% 0.38% 0.25% 0 Foam (mL) 79 98 101 114 Foam stability (%) 85 83 81 83 D50% in shower gel (μm) 3.8 3 3.1 n/a Shower gel polydispersity 1.08 1.17 1.13 n/a Viscosity 25° C., 6 rpm 20,200 26,000 19,600 4,400 (mPa .Math. s) Stability 1 month 50° C. yes yes yes n/a

Example 3

(29) An oil-in-water emulsion, O/W, is prepared according to the protocol described in the introduction (Table 2). Each emulsion comprises 1% by weight of anionic copolymer (CA1), defined in Table 1. Each emulsion comprises 40% by weight of sweet almond oil. Each emulsion is then used to make a shower gel comprising 10% or 20% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (Table 3). Phase P′ 1 comprises 8% by weight of Rheostyl™ 100 30%.

(30) A reference shower gel is also used, denoted as T, comprising all of the ingredients of the shower gel described in Table 3 except for the oil-in-water emulsion in step a) containing 40% oil. This reference shower gel also does not comprise oil. For each shower gel, the content of sweet almond oil and anionic copolymer content (CA1) are shown.

(31) For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(32) The results are shown in Table 6.

(33) TABLE-US-00006 TABLE 6 Oil content 0 10.00% 20.00% (CA1) content 0 0.25% 0.50% Foam (mL) 114 101 83 Foam stability (%) 83 81 81 D50% in shower gel (μm) n/a 3.1 3.5 Shower gel polydispersity n/a 1.11 1.33 Viscosity 25° C., 6 rpm (mPa .Math. s) 4,400 19,600 55,300 Stability 1 month 50° C. n/a yes yes

Example 4

(34) An oil-in-water emulsion, O/W, is prepared according to the protocol described in the introduction (Table 2). Each emulsion comprises 1% by weight of anionic copolymer (CA1) defined in Table 1. Each emulsion comprises 40% by weight of a vegetable oil chosen among sweet almond oil or sesame seed oil.

(35) Each emulsion is then used to make a shower gel comprising 10% by weight, relative to the total weight of shower gel, of vegetable oil according to the protocol described in the introduction (Table 3). Phase P′ 1 comprises 8% by weight of Rheostyl™ 10030%.

(36) For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(37) The results are shown in Table 7.

(38) TABLE-US-00007 TABLE 7 Cosmetic oil B Prunus oil Sesame oil Foam (mL) 101 120 Foam stability (%) 81 78 D50% in shower gel (μm) 3.1 2.8 Shower gel polydispersity 1.13 0.92 Viscosity 25° C., 6 rpm (mPa .Math. s) 19,600 22,100 Stability 1 month 50° C. yes yes

Example 5

(39) An oil-in-water emulsion, O/W, is prepared according to the protocol described in the introduction (Table 2). Each emulsion comprises 1% by weight of anionic copolymer (CA1) defined in Table 1. Each emulsion comprises 40% by weight of sweet almond oil. Each emulsion is then used to make: a shower gel GD1 comprising 10% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (table 3) for which the P′1 phase comprises 8% by weight of Rheostyl™ 100 30% or a shower gel GD2 comprising 10% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (Table 3) for which phase P′ 1 comprises 0.5% by weight of Carbopol® Ultrez 20 or a GD3 shower gel with the composition given in Table 8.

(40) TABLE-US-00008 TABLE 8 Ingredients % Water Qsp 100% Oil-in-water emulsion from step a) containing 40% oil   25% Texapon NSO UP sodium laureth sulphate 28% 32.5% Dehyton PK 45 cocamidopropyl betaine 45%  6.7% Sodium hydroxide 20% Qsp pH 6.7-7.1

(41) The percentages, %, are percentages by weight relative to the total weight of the shower gel.

(42) For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(43) The results are shown in Table 9.

(44) TABLE-US-00009 TABLE 9 GD1 GD2 GD3 Foam (mL) 113 97 108 Foam stability (%) 80 80 84 D50% in shower gel (μm) 3.1 7.5 7.9 Shower gel polydispersity 1.13 1.17 0.96 Viscosity 25° C., 6 rpm (mPa .Math. s) 19,600 1,660 10 Stability 1 month 50° C. yes no* no* *creaming (oil particle migration)

Comparative Example 1

(45) Two shower gels, GD4 and GD5, each having the composition given in Table 10, are prepared.

(46) TABLE-US-00010 TABLE 10 GD4 GD5 Ingredients % % Water Qsp 100% Qsp 100% Sweet almond oil   0%   10% Texapon NSO UP sodium laureth 32.5% 32.5% sulphate 28% Dehyton PK 45 cocamidopropyl  6.7%  6.7% betaine 45% Sodium hydroxide 20% Qsp pH 6.7-7.1 Qsp pH 6.7-7.1

(47) The percentages, %, are percentages by weight relative to the total weight of the shower gel.

(48) A shower gel GD6 is also prepared according to the following protocol:

(49) An oil-in-water emulsion, O/W, is prepared according to the protocol in the introduction (Table 2), but using Emulium Delta instead of the anionic copolymer A. The emulsion comprises 6% by weight (solids content) of Emulium Delta. The emulsion comprises 40% by weight of sweet almond oil.

(50) This emulsion is then used to make a shower gel comprising 10% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (Table 3). Phase P′ 1 comprises 8% by weight of Rheostyl™ 100 30%. For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(51) The results are shown in Table 11, n.m denotes non-measurable and n/a denotes not applicable.

(52) TABLE-US-00011 TABLE 11 GD4 GD5 GD6 Foam (mL) 136 n.m 33 Foam stability (%) 81 n.m 91 D50% in shower gel (μm) n/a 23.8 3.1 Shower gel polydispersity n/a 1.74 1.21 Viscosity 25° C., 6 rpm (mPa .Math. s) 10 10 25,000 Stability 1 month 50° C. no no yes

(53) For the shower gel GD5, the mixture formed is unstable and does not allow measures to be taken.

Comparative Example 2

(54) In this comparative example, the sweet almond oil is introduced directly, without the preliminary step of producing an oil-in-water emulsion.

(55) Three shower gels, GD7, GD8 and GD9 are prepared, comprising respectively 0%, 10% or 20% by weight, relative to the total weight of shower gel, of sweet almond oil according to the protocol described in the introduction (Table 3), but by introducing the oil directly, i.e. without prior emulsion. Phase P′ 1 comprises 8% by weight of Rheostyl™ 100 30%.

(56) For each shower gel, we measure: the amount of foam, its stability, the D50% and the polydispersity ((D90%−D10%)/D50%) of the oil droplets in the shower gel and the viscosity and stability of the shower gel.

(57) The results are shown in Table 12, n/a denotes not applicable.

(58) TABLE-US-00012 TABLE 12 GD7 GD8 GD9 Oil content 0% 10% 20% Foam (mL) 114 125 111 Foam stability (%) 81 77 78 D50% in shower gel (μm) n/a 3.6 4.1 Shower gel polydispersity n/a 2.12 1.88 Viscosity 25° C., 6 rpm (mPa .Math. s) 4,400 7,660 8,240

(59) The distribution of the oil droplets is polydisperse.