WO2018195792A1

WO2018195792A1 - Composition comprising hydrophobic polymer for removing makeup on skin

Info

Publication number: WO2018195792A1
Application number: PCT/CN2017/081969
Authority: WO
Inventors: Ziquan Francis CHEN
Original assignee: L'oreal
Priority date: 2017-04-26
Filing date: 2017-04-26
Publication date: 2018-11-01
Also published as: CN111031997A

Abstract

The composition for removing makeup on keratin materials, comprising a dispersed fatty phase which comprises at least one oil selected from the group consisting of ester oil, ether oil, or a mixture thereof, at least one hydrophobic polymer chosen from the group consisting of ester terminated poly(ester-amide), and a continuous aqueous phase comprising at least one hydrophilic gelling agent. The composition presents a desired cosmetic efficacy, such as a good makeup remove ability, and meanwhile has an improved skin sensory, such as freshness feeling and cleanness feeling, thanks to the water droplets present during application.

Description

Composition comprising a hydrophobic polymer for removing makeup on the skin

Cleansing the skin and removing the makeups on the skin are very important for caring for the face, in particular, it is very important to consumers of makeup products to have an efficient makeup remover. It must be as efficient as possible because greasy residues, such as excess sebum, the remnants of cosmetic products used daily, and make-up products, in particular waterproof products, accumulate in the skin folds, and can block the pores of the skin and result in the appearance of spots.

Several types of makeup removing or cleansing products, for example, rinsable cleansing anhydrous oils and gels, solid makeup removers, or biphasic and wipe removers are known.

Rinsable anhydrous oils and gels have a makeup removing action by virtue of oils present in these formulations. These oils make it possible to dissolve fatty residues and to disperse make-up pigments. These products are effective and well tolerated. However, they exhibit the disadvantage of being heavy and of not conferring a feeling of freshness on application, which is disadvantageous from a cosmetic viewpoint.

Biphasic remover is effective but inconvenient to use as shaking is required before each use and the two phases are consumed at different rates.

Remover water leave fresh sensory but is ineffective； Remover lotion is also considered ineffective； Balm/Cream has Greasy touch, not suitable for eye area and unhygienic； wipe is convenient but inefficient against waterproof makeups and is unhygienic.

In the field of makeup removing compositions, "soft solid" compositions constitute a category of products that are appreciated by consumers for their efficacy on cleansing, makeup removability, rinse ability, and for their cosmetic qualities (soft, dry feeling, easy to use, etc. ) . They are known as solid compositions that soften under the effect of a stress such as spreading over the surface of the skin or, for example, by extrusion through a device with a perforated wall (grille) . Some known soft solid compositions useful for the cleansing of the skin and/or the removal of makeup comprise silica aerogel particles, waxes, hydrocarbon-based oils and non-ionic surfactants. However, there is still a need for solid compositions adapted to the removal of makeup with improved properties, such as usage properties, for example, easily spreading on the skin.

Among the disadvantages of the various types of products mentioned above, one of the key properties of a makeup remover product that attract the attention of consumers is the skin sensory after application while effectively and conveniently removes makeup. Consumers are looking for a convenient and efficient product which delivers a feeling of freshness and cleanness, without a greasy residue on the skin. None of the above mentioned products have disclosed such properties.

Thus there is a need for formulating a composition for removing the makeups on the skin, and meanwhile delivers a freshness and cleanness feeling after application.

The present invention is made to meet that need.

The aim of the present invention is to provide a composition with good efficacy such as makeup remove ability and with improved cosmetic properties such as feeling of freshness and cleanness after application.

Preferably, the aim of the present invention is to provide a composition with good efficacy such as makeup remove ability and with improved cosmetic properties such as feeling of freshness and cleanness after application, and meanwhile stable over time.

Another aim of the invention is to provide a composition for removing the makeups on the skin, which is easy to apply on keratin materials, in particular on the skin.

The aims of the present invention is realized by a composition comprising a dispersed fatty phase which comprises at least one oil selected from the group consisting of ester oil, ether oil, or a mixture thereof, at least one hydrophobic polymer chosen from the group consisting of ester terminated poly (ester-amide) , and a continuous aqueous phase comprising at least one hydrophilic gelling agent.

The aims of the present invention is realized by the composition as described above, which presents a very fresh feeling via the water droplets on keratin materials, in particular on the skin, and meanwhile a makeup removing ability.

Such a composition is stable over time and temperature change.

The present invention thus relates to a composition for removing makeups on keratin materials, comprising:

a) a dispersed fatty phase, comprising:

- at least one oil selected from the group consisting of ester oil, ether oil, or a mixture thereof,

- at least one hydrophobic polymer chosen from the group consisting of ester terminated poly (ester-amide) ； and

b) a continuous aqueous phase comprising at least one hydrophilic gelling agent.

The present invention also relates to a cosmetic process for removing makeups of the keratin materials, in particular the skin and/or lips, characterized in that it comprises a step of applying to the surface of the keratin materials at least one composition according to the invention.

The inventors discovered that with the compositions according to the invention, the makeup removing ability very good, meanwhile the skin sensory is improved.

The compositions according to the invention are also stable.

Definitions

By “rinse ability” , it may be meant the ease of being rinsed off by water after applying the composition of the present invention onto the skin.

By “non-residue feeling” , it may be meant the feeling of the skin being dry and fresh after rinsing off the composition of the present invention. In one embodiment, there is no greasy or waxy feeling of the skin after rinsing off the composition of the present invention.

The term "keratin materials" means the skin (of the body, face and around the eyes) , hair, eyelashes, eyebrows, bodily hair, nails, lips or mucous membranes, preferably skin.

Detailed description of the invention

The composition of the present invention aims at solving the problems as listed above.

Fatty phase

The composition of the invention comprises a dispersed fatty phase.

The fatty phase comprises at least one oil.

For the purposes of the invention, the oil means a fatty substance which is liquid at room temperature (25℃) and atmospheric pressure (760 mmHg, i.e. 101 kPa) . The oil means a non-aqueous liquid medium which is immiscible in all proportions with water.

The oil may be volatile or non-volatile. The expression “volatile oil” means any non-aqueous medium capable of evaporating on contact with the skin or the lips in less than one hour at room temperature and atmospheric pressure. The volatile oil is liquid at room temperature and has a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 10^-2 to 300 mmHg (1.33 to 40 000 Pa) and, for example, greater than 0.03 mmHg (4 Pa) and further example greater than 0.3 mmHg (40 Pa) . The expression “non-volatile oil” means an oil which remains on the skin or the lips at room temperature and atmospheric pressure for at least several hours, such as those having a vapor pressure of less than 10^-2 mmHg (1.33 Pa) .

The oil may be chosen from polar oils and apolar oils including hydrocarbon-based liquid oils and oily liquids at room temperature.

Preferably, the fatty phase is present in the composition in an amount ranging from 1 to 50％by weight, preferably from 1 to 30％by weight, more preferably from 1 to 20％by weight, relative to the total weight of the composition.

Oil (s)

According to the present invention, the composition comprises, in a dispersed fatty phase, at least one oil selected from ester oil, ether oil, or a mixture thereof.

The term “ester oil” means oil that is liquid at room temperature (25℃ comprising at least one ester functional group.

The at least one ester oil used herein is chosen, for example, from monoesters.

The ester oil may, for example, be chosen from the monoesters of formula (I) ,

R₁COOR₂ (I)

wherein R₁ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group comprising from 4 to 40 carbon atoms, preferably from 4 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms, phenyl group, or a R₁’-O-group, wherein R₁’represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based chains comprising from 4 to 40 carbon atoms, preferably from 4 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms, and even more preferably 8 carbon atoms, phenyl group；

R₂ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group comprising from 4 to 40 carbon atoms, preferably from 4 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms, and even more preferably 8 carbon atoms, or phenyl group.

Examples of the ester oils that may be mentioned include isopropyl myristate, isopropyl palmitate, isononyl isononanoate, octyl isononanoate, tridecyl isononanoate, isopropyl myristate, triethyl hexanoin, diisostearyl maleate, glyceryl palmitate, glyceryl stearate, glyceryl diisostearate, glyceryl tri (caprylate/caprate) , sorbitan isostearate, sorbitan stearate, sorbitan oleate, ethylhexyl stearate, decaprylyl carbonate, dodecyl benzoate, tetradecyl benzoate, hexadecyl benzoate, or a mixture thereof.

Advantageously, suitable ester oils of the present invention are commercially available for example:

C_12-15 alkyl benzoate, the products sold under the tradename benzoate

TN by Evonik Gold Schmidt, or Dub B1215 sold by Stearinerie Dubois；

dicaprylyl carbonate, the products sold under the tradename carbonates

CC from Cognis；

isopropyl myristate the products sold under the tradename Crodamol IPM-LQ- (MV) by Croda, or Dub IPM sold by Stearinerie Dubois；

ethylhexyl stearate, the products sold under the tradename

868 sold by Cognis.

According to some preferred embodiments, the current invention comprises C₁₂-C₁₅ alkyl benzoate such as the products sold under the tradename

TN by Evonik Gold Schmidt, or dicaprylyl carbonate sold under the tradename

CC by the company Cognis.

According to the present invention, the term “ether oil” means oil that is liquid at room temperature (25℃ comprising at least one ether functional group.

According to an embodiment, the composition of the present invention comprises at least one ether oil of formula (II) ,

R₃-O-R₄ formula (II)

In the formula (II) :

R₃ and R₄, which may be identical or different, denote a linear or branched C₆-C₂₅ alkyl or alkenyl radical, R₃ and R₄ being chosen such that the ether is liquid at a temperature of less than or equal to 25℃.

Preferably, the ether of formula (II) is chosen from compounds for which the radicals R₃ and R₄, which may be identical or different, denote a linear or branched C₆-C₁₂ alkyl or alkenyl radical.

More particularly, according to the present invention, the radicals R₃ and R₄ are identical alkyl radical.

Amongst ether of formula (II) , the preferred dialkyl ether is chosen from di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-n-nonyl ether, di-n-decyl ether, di-isodecyl ether, di-n-dodecyl ether, di-n-eteradecyl ether, di-n-hexadecyl ether, di-n-oxtadecyl ether, or a mixture thereof.

R₃ and R₄ preferentially denote a C₈ radical.

The dialkyl ethers that may be used according to the invention may be soluble or insoluble in the compositions, but are preferably insoluble.

These compounds may be prepared according to the process described in patent application DE 41 27 230.

Most preferably, a di-n-octyl ether (INCI name: dicaprylyl ether) that may be used in the context of the present invention. Such product is commercially available, for example those sold under the name

OE by the company Cognis (BASF) , or

OE by the company Ecogreen Oleochemicals.

According to a preferred embodiment, the at least one oil is present in the composition of the present invention ranging from 1 to 50％by weight, and preferably ranging from 3 to 20％by weight, relative to the total weight of the composition.

According to a preferred embodiment, the apolar oil, if exists, is present in an amount of less than or equal to 50％by weight, more preferably, less than or equal to 45％by weight, based on the total weight of the fatty phase.

Hydrophobic polymer

The composition according to the invention comprises, in a dispersed fatty phase, at least one hydrophobic polymer chosen from ester terminated poly (ester-amide) .

By “hydrophobic” it may be meant a polymer which is repelled from water, i.e. which is not miscible with water.

By “ester terminated” polymer it may be meant a polymer comprising at least one chemical function ester (R_a-C (O) -O-R’_a) as a terminal moiety. For example, such polymers and their methods of preparation are described in the WO 02/092663 patent application.

In one embodiment, said polymer comprises at least one dimer dilinoleate unit, optionally hydrogenated. Preferably, the hydrophobic polymer is bis-stearyl ethylenediamine/neopentyl glycol/hydrogenated dimer dilinoleate copolymer. Particular mention may be made of bis-stearyl ethylenediamine/neopentyl glycol/hydrogenated dimer dilinoleate copolymer, also called polyamide-8, commercialized by Arizona chemical under the name Sylvaclear^TM C75V or by Croda, Inc., under the name OleoCraft LP-20 (CAS RN is 678991-29-2) .

In one embodiment, the amount of the hydrophobic polymer is comprised from 0.1％to 15％by weight, preferably from 0.1％to 10％by weight, more preferably from 0.3％to 5％by weight, based on the total weight of the composition.

Aqueous phase

According to the present invention, the composition comprises a continuous aqueous phase. Said aqueous phase is preferably present in an amount ranging from 50％to 99％by weight, more preferably from 50％to 85％by weight of the total weight of the composition.

The continuous aqueous phase may comprise water, at least one organic solvent miscible with water or mixtures thereof.

Preferably, the continuous aqueous phase comprises at least one organic solvent miscible with water (at room temperature-25℃) such as for example monoalcohols having from 2 to 6 carbon atoms such as ethanol, isopropanol； polyols notably having from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, and preferentially having from 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, caprylylglycol, dipropylene glycol, diethylene glycol； glycol ethers (notably having from 3 to 16 carbon atoms) such as mono-, di-or tri-propylene glycol (C₁-C₄) alkyl ethers, mono-, di-or tri-ethylene glycol (C₁-C₄) alkyl ethers； and mixtures thereof.

The continuous aqueous phase of the composition of the invention preferably comprises water and at least a polyol, preferably glycerol or propylene glycol, and/or a monoalcohol, preferably ethanol.

Preferably, the continuous aqueous phase comprises water, a mixture of polyols, preferably glycerol and propylene glycol.

Preferably, water is present in an amount ranging from 20％to 80％by weight, more preferably from 30％to 70％by weight of the total weight of the composition.

Preferably, the organic solvent (s) miscible with water is (are) present in an amount ranging from 5％to 80％by weight, more preferably from 7％to 20％by weight of the total weight of the composition.

Hydrophilic gelling agent (s)

According to an embodiment, the composition of the present invention comprises, in a continuous aqueous phase, at least one hydrophilic gelling agent.

For the purposes of the present invention, the term "hydrophilic gelling agent" means a compound that is capable of gelling the aqueous phase of the compositions according to the invention.

The gelling agent is hydrophilic and is thus present in the aqueous phase of the composition.

The gelling agent may be water-soluble or water-dispersible.

As stated above, the aqueous phase of a composition according to the invention is gelled with at least one hydrophilic gelling agent optionally chosen from synthetic polymeric gelling agents.

For the purposes of the invention, the term "synthetic" means that the polymer is neither naturally existing nor a derivative of a polymer of natural origin.

The synthetic polymeric hydrophilic gelling agent under consideration according to the invention may or may not be particulate.

For the purposes of the invention, the term "particulate" means that the polymer is in the form of particles, preferably spherical particles.

Advantageously, a composition according to the invention comprises a polymeric hydrophilic gelling agent chosen from crosslinked acrylic homopolymers or copolymers； associative polymers, in particular associative polymers of polyurethane type； polyacrylamides and crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers； modified or unmodified carboxyvinyl polymers, and mixtures thereof, especially as defined below.

According to a preferred embodiment, the hydrophilic gelling agent is chosen from polymers comprising at least one monomer being acrylamido-2-methylpropanesulfonic acid

(or

polymers) .

In particular, the

polymers in accordance with the invention are crosslinked or non-crosslinked homopolymers or copolymers comprising at least the acrylamido-2-methylpropanesulfonic acid

monomer, in a form partially or totally neutralized with a mineral base other than ammonia, such as sodium hydroxide or potassium hydroxide.

They are preferably totally neutralized or virtually totally neutralized, i.e. at least 90％neutralized.

These

polymers according to the invention may be crosslinked or non-crosslinked.

When the polymers are crosslinked, the crosslinking agents may be chosen from the polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate, allylic ethers of alcohols of the sugar series, or other allylic or vinyl ethers of polyfunctional alcohols, and also allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

According to one embodiment of the invention, the crosslinking agent is chosen from methylenebis-acrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA) . The degree of crosslinking generally ranges from 0.01 mol％to 10 mol％and more particularly from 0.2 mol％to 2 mol％relative to the polymer.

The

polymers in accordance with the invention are water-soluble or water-dispersible. In this case they are:

- either "homopolymers" comprising only

monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above；

- or copolymers obtained from

and from one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above. When the said copolymers comprise hydrophobic ethylenically unsaturated monomers, these monomers do not comprise a fatty chain and are preferably present in small amounts.

For the purposes of the present invention, the term "fatty chain" means any hydrocarbon-based chain containing at least 7 carbon atoms.

The term "water-soluble or water-dispersible" means polymers which, when introduced into an aqueous phase at 25℃, to a mass concentration equal to 1％, make it possible to obtain a macroscopically homogeneous and transparent solution, i.e. a solution that has a maximum light transmittance value, at a wavelength equal to 500 nm, through a sample 1 cm thick, of at least 60％and preferably of at least 70％.

The "homopolymers" according to the invention are preferably crosslinked and neutralized, and they may be obtained according to the preparation process comprising the following steps:

(a) the monomer such as

in free form is dispersed or dissolved in a solution of tert-butanol or of water and tert-butanol；

(b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more mineral or organic bases, preferably ammonia NH₃, in an amount making it possible to obtain a degree of neutralization of the sulfonic acid functions of the polymer ranging from 90％to 100％；

(c) the crosslinking monomer (s) is (are) added to the solution or dispersion obtained in (b) ；

(d) a standard free-radical polymerization is performed in the presence of free-radical initiators at a temperature ranging from 10 to 150℃； the polymer precipitates in the solution or dispersion based on tert-butanol.

The

homopolymers according to the invention are preferably optionally crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymers, for instance the poly (2-acrylamido-2-methylpropanesulfonic acid) sold by the company Clariant under the name Hostacerin

(CTFA name: ammonium polyacryldimethyltauramide) .

The water-soluble or water-dispersible AMPS copolymers according to the invention contain preferably water-soluble ethylenically unsaturated monomers, hydrophobic monomers or mixtures thereof.

The water-soluble comonomers may be ionic or nonionic.

Among the ionic water-soluble comonomers, examples that may be mentioned include the following compounds and the salts thereof:

- (meth) acrylic acid,

- styrenesulfonic acid,

- vinylsulfonic acid and (meth) allylsulfonic acid,

- vinylphosphonic acid,

- maleic acid,

- itaconic acid,

- crotonic acid,

- the water-soluble vinyl monomers of formula (A) below:

in which:

- R₁ is chosen from H, -CH₃, -C₂H₅ and-C₃H₇

- X₁ is chosen from:

- alkyl ethers of -OR₂ type in which R₂ is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbon atoms, substituted with at least one sulfonic (-SO₃-) and/or sulfate (-SO₄-) and/or phosphate (-PO₄H₂-) group.

Among the nonionic water-soluble comonomers, examples that may be mentioned include:

- (meth) acrylamide,

- N-vinylacetamide and N-methyl-N-vinylacetamide,

- N-vinylformamide and N-methyl-N-vinylformamide,

- maleic anhydride,

- vinylamine,

- N-vinyllactams comprising a cyclic alkyl group containing 4 to 9 carbon atoms, such as n-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

- vinyl alcohol of formula CH₂＝CHOH,

- the water-soluble vinyl monomers of formula (B) below:

in which:

- R₁₅ is chosen from H, -CH₃, -C₂H₅ and-C₃H₇

- X₂ is chosen from:

- alkyl ethers of -OR₁₆ type in which R₁₆ is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbons, optionally substituted with a halogen atom (iodine, bromine, chlorine or fluorine) ； a hydroxyl group (-OH) ； ether.

Mention is made, for example, of glycidyl (meth) acrylate, hydroxyethyl methacrylate and (meth) acrylates of ethylene glycol, of diethylene glycol or of polyalkylene glycol.

Among the fatty-chain-free hydrophobic comonomers, examples that may be mentioned include:

- styrene and its derivatives, such as 4-butylstyrene, α-methylstyrene and vinyltoluene,

- vinyl acetate of formula CH₂＝CH-OCOCH₃；

- vinyl ethers of formula CH₂＝CHOR in which R is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbons；

- acrylonitrile,

- caprolactone,

- vinyl chloride and vinylidene chloride,

- silicone derivatives, which lead to silicone polymers after polymerization, such as methacryloxypropyltris (trimethylsiloxy) silane and silicone methacrylamides,

- the hydrophobic vinyl monomers of formula (C) below:

in which:

- R₂₃ is chosen from H, -CH₃, -C₂H₅ and-C₃H₇

- X₃ is chosen from:

- alkyl ethers of -OR₂₄ type in which R₂₄ is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbon atoms.

Mention is made, for example, of methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate and isobornyl acrylate and 2-ethylhexyl acrylate.

The water-soluble or water-dispersible

polymers of the invention preferably have a molar mass ranging from 50 000 g/mol to 10 000 000 g/mol, preferably from 80 000 g/mol to 8 000 000 g/mol and even more preferably from 100 000 g/mol to 7 000 000 g/mol.

Examples of water-soluble or water-dispersible AMPS homopolymers in accordance with the invention that may be mentioned include crosslinked or non-crosslinked polymers of sodium acrylamido-2-methylpropanesulfonate, such as the polymer used in the commercial product Simulgel^TM 800 (CTFA name: Sodium Polyacryloyldimethyltaurate) .

Examples of water-soluble or water-dispersible AMPS copolymers in accordance with the invention that may be mentioned include:

- acrylamide/sodium acrylamido-2-methylpropanesulfonate crosslinked copolymers, such as the copolymer used in the commercial product Sepigel 305 (CTFA name: Polyacrylamide/C₁₃-C₁₄ Isoparaffin/Laureth-7) or the copolymer used in the commercial product sold under the trade name Simulgel^TM 600 (CTFA name: Acrylamide/Sodium Acryloyldimethyltaurate/Isohexadecane/Polysorbate-80) by the company SEPPIC；

- copolymers of AMPS and of vinylpyrrolidone or of vinylformamide, such as the copolymer used in the commercial product sold under the name Aristoflex AVC by the company Clariant (CTFA name: Ammonium Acryloyldimethyltaurate/VP Copolymer) but neutralized with sodium hydroxide or potassium hydroxide；

- copolymers of AMPS and of sodium acrylate, for instance AMPS/sodium acrylate copolymer such as the copolymer used in the commercial product sold under the name Simulgel^TM EG by the company SEPPIC (CTFA name: Acrylamide/Sodium Acryloyldimethyltaurate/Isohexadecane/Polysorbate-80) ；

- copolymers of AMPS and of hydroxyethyl acrylate, for instance AMPS/hydroxyethyl acrylate copolymer, such as the copolymer used in the commercial product sold under the name Simulgel^TM NS by the company SEPPIC (CTFA name: Hydroxyethyl acrylate/Sodium Acryloyldimethyltaurate copolymer (and) Squalane (and) Polysorbate-60) .

The preferred polymers are more particularly sodium acrylamido-2-methylpropanesulfonate homopolymers, such as the homopolymer used in the commercial product Sepigel^TM 800, and

acrylate copolymers, such as the copolymer used in the commercial product sold under the name Simulgel NS.

According to one particularly preferred form of the invention, the

polymer or copolymer will be used in powder form.

The polymers derived from AMPS may further be those comprising:

- from 80 mol％to 99 mol％of 2-acrylamido-2-methylpropanesulfonic acid

units of formula (3) below:

in which X⁺is a proton, an alkali metal cation, an alkaline-earth metal cation or an ammonium ion； and

- 1 mol％to 20 mol％and preferably from 1 mol％to 15 mol％of units of formula (4) below:

in which n and p, independently of each other, denote a number of moles and ranges from 0 to 30 and preferably from 1 to 20, with the proviso that n+p is less than or equal to 30, preferably less than 25 and better still less than 20； R₁ denotes a hydrogen atom or a linear or branched C₁-C₆ alkyl radical (preferably methyl) and R₃ denotes a linear or branched alkyl comprising m carbon atoms, with m ranging from 6 to 30 and preferably from 10 to 25.

These polymers according to the invention may be obtained according to the standard free-radical polymerization processes in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN) , azobisdimethylvaleronitrile, 2, 2-azobis [2-amidinopropane] hydrochloride (ABAH ＝2, 2-azoBis- [2-Amidinopropane] hydrochloride) , organic peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc., mineral peroxide compounds such as potassium persulfate or ammonium persulfate, or H₂O₂ optionally in the presence of reducing agents.

The polymers are obtained especially by free-radical polymerization in tert-butanol medium from which they precipitate. Using polymerization in tert-butanol, it is possible to obtain a size distribution of the polymer particles that is particularly favourable for its uses.

The polymerization reaction may be performed at a temperature of between 0 and 150℃, preferably between 20 and 100℃, either at atmospheric pressure or under reduced pressure. It may also be performed under inert atmosphere, and preferably under nitrogen.

It is thus possible to use the polymers prepared from 2-acrylamido-2-methylpropanesulfonic acid

or a sodium or ammonium salt thereof, with an ester of (meth) acrylic acid and:

- of a C₁₀-C₁₈ alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₁ oxo alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₁ oxo alcohol oxyethylenated with 7 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₂-C₁₄ alcohol oxyethylenated with 7 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₂-C₁₄ alcohol oxyethylenated with 9 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₂-C₁₄ alcohol oxyethylenated with 11 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₆-C₁₈ alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₆-C₁₈ alcohol oxyethylenated with 11 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₆-C₁₈ alcohol oxyethylenated with 15 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₆-C₁₈ alcohol oxyethylenated with 20 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₆-C₁₈ alcohol oxyethylenated with 25 mol of ethylene oxide (Genapol

from the company Clariant) ,

- of a C₁₈-C₂₂ alcohol oxyethylenated with 25 mol of ethylene oxide,

- of a C₁₆-C₁₈ iso-alcohol oxyethylenated with 25 mol of ethylene oxide.

According to one preferred embodiment, the polymer is a copolymer of

and of a C₁₆-C₁₈ alcohol methacrylate comprising from 6 to 25 mol of oxyethylene groups, obtained from methacrylic acid or a methacrylic acid salt and from a C₁₆-C₁₈ alcohol oxyethylenated with 6 to 25 mol of ethylene oxide.

The polymer may also be a copolymer of

and of a C₁₂-C₁₄ alcohol methacrylate comprising from 6 to 25 mol of oxyethylene groups, obtained from methacrylic acid or a methacrylic acid salt and from a C₁₂-C₁₄ alcohol oxyethylenated with 6 to 25 mol of ethylene oxide.

As polymers of

type that are preferred according to the present invention, mention may be made of:

- the non-crosslinked copolymer obtained from 92.65 mol％of

and 7.35 mol％of a C₁₆-C₁₈ alcohol methacrylate comprising 8 oxyethylene groups (Genapol

) ,

- the non-crosslinked copolymer obtained from 91.5 mol％of

and 8.5 mol％of a C₁₂-C₁₄ alcohol methacrylate comprising 7 oxyethylene groups (Genapol

) ,

- the crosslinked copolymer obtained from 96.45 mol％of

and 3.55 mol％of a C₁₆-C₁₈ alcohol methacrylate comprising 25 oxyethylene groups (Genapol

) , the crosslinking agent is trimethylolpropane triacrylate,

- the crosslinked copolymer obtained from

and from a C₂₂ alcohol methacrylate comprising 25 oxyethylene groups； this polymer is sold under the name Aristoflex

by the company Clariant,

- the acrylamide/sodium 2-methyl-2- [ (1-oxo-2-propenyl) amino] -1-propanesulfonate

copolymer such as Simulgel

in the form of an emulsion containing polysorbate 80 as surfactant and containing isohexadecane as fatty phase, sold by the company SEPPIC, or alternatively Simulgel

Simulgel

and Simulgel

sold by the same company.

Simulgel

is described especially in document FR 2 785 801. It is more specifically a reverse latex. The

polyelectrolyte is 2-methyl-2- [ (1-oxo-2-propenyl) amino] -1-propanesulfonic acid partially or totally salified especially in sodium salt or ammonium salt form, to a proportion of from 30 mol％to 50 mol％in the mixture comprising the

and an acrylamide, which is itself in a proportion of 50％to 70％.

For the purpose of the present invention, the preferred polymers derived from

is the optionally crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymers, for instance the poly (2-acrylamido-2-methylpropanesulfonic acid) sold by the company Clariant under the name Hostacerin

(CTFA name: ammonium polyacryldimethyltauramide) .

According to a preferred embodiment, the amount of the hydrophilic gelling agent may range, for example, from 0.01％to 5％by weight, preferably from 0.1％to 1％by weight, relative to the total weight of the composition.

According to a preferred embodiment, the composition of the present invention is free of surfactants. In other words, the present invention is surfactant free.

By “surfactant free” we intend to mean a composition containing less than 2％by weight of surfactant, or even less than 0.5％of surfactants, and especially free of surfactants, the surfactant not being added during the preparation of the composition but corresponding to the residual surfactants provided by the mixed ingredients.

Adjuvants

In a known manner, the composition of the invention may also contain adjuvants that are common in cosmetics and/or dermatology, such as preserving agents, antioxidants, complexing agents, pH modifiers (acidic or basic) , fragrances, fillers, bactericides, odour absorbers, colorants (pigments and dyes) , film-forming polymers, additional oils such as silicone oil, or fluoro oils, and active ingredients.

Needless to say, a person skilled in the art will take care to select this or these optional additional compound (s) , and/or the amount thereof, such that the properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Galenical forms

The compositions according to the invention may be in the form of a lotion, cream, pomade or a gel whose viscosity may vary as a function of the desired application, the region of human keratin material to be treated and the desired conditioning.

According to a preferred embodiment, the composition of the present invention is in the form of oil in water gel.

In a particular embodiment, the composition of the present invention comprises:

a) a dispersed fatty phase, comprising:

- at least one oil selected from the group consisting of C_12-15 alkyl benzoate, dicaprylyl carbonate, dicaprylyl ether, or a mixture thereof,

- bis-stearyl ethylenediamine/neopentyl glycol/hydrogenated dimer dilinoleate copolymer； and

b) a continuous aqueous phase comprising poly (2-acrylamido-2-methylpropanesulfonic acid) .

Method and use

The present invention also relates to a cosmetic process for treating and/or caring for keratin materials, characterized in that it comprises applying to the surface of the keratin material at least one composition as defined previously.

The present invention also relates to a cosmetic process for removing the makeup on the keratin materials, which comprises applying to the surface of a keratin material at least one composition as defined previously.

The composition according to the invention has improved skin sensory.

Besides, the composition has a desired makeup removing ability.

In the patent application, unless specifically mentioned otherwise, the contents are expressed on a weight basis relative to the total weight of the composition.

The examples that follow are aimed at illustrating the compositions and processes according to this invention, but are not in any way a limitation of the scope of the invention.

All the parts and percentages in the examples are given on a weight basis and all the measurements were obtained at about 25℃, unless otherwise mentioned.

EXAMPLES

Example 1: Preparation examples

The following formulations were prepared as follows:

Ex. 2: the POLYAMIDE-8 is replaced by Silica silylate；

Ex. 3: the polyamide-8 is replaced by polymer dextrin myristate.

Method of preparation:

The compositions of examples 1 to 3 were prepared following the steps of:

1. Mixing the phase A in the main kettle with paddles and homogenizer at 65℃ for30 min or until homogeneous and lump-free；

2. Mixing phase B in an auxiliary kettle at 80℃ for 1 hour or until homogeneous and lump-free；

3. Slowly transport phase B into the main kettle while maintaining mixing and temperature at 65℃.

Cool the completed batch to room temperature while maintaining mixing.

Example 5: Evaluation example

Evaluation of cosmetic efficacy (makeup remove ability) as well as skin sensory (freshness, cleanness feeling) of the compositions of examples 1 to 3 was performed. The compositions of examples 1 to 3 were kept under room temperature (25℃) and 45℃for 2 months and+/-20 for 10 cycles.

The compositions of example 1 to 3 were applied in makeup removal test on 6 consumers less than 45 years old.

30 minutes after makeup (Foundation: L’Oréal Infaillible shade 220； Waterproof mascara: L’Oréal lash architect 4D black； Washable mascara: L’Oréal lash architect 4D black) , example 1 to 3 were applied with cotton pad, 2 pads for foundation and 3 pads for mascaras, respectively.

The residue makeup on the face were removed with L’Oréal BIFACIAL remover on cotton pads, the efficacy of tested products were evaluated according to the number of cotton pads required to completely remove the remaining makeup, the scale of which follows:

First cotton pad without residue: Very good

1 cotton pad remove residue: Good

2 cotton pad remove residue: Moderate

3 cotton pad remove residue: Bad

4 cotton pad remove residue: Very Bad

Besides, in terms of skin sensory, consumers considered that the feeling is acceptable (score 3 and above) , and that the skin feels fresh and clean:

5； very good performance；

4； good performance；

3； acceptable performance；

2. poor performane；

1. very poor performance.

The results are listed as follow:

It was observed that comparing to compositions of examples 2 and 3, the composition of the invention Ex. 1 shows improvements on skin sensory, such as freshness feeling and cleanness. Besides, Ex. 1 shows better makeup remove ability. Lastly, the invention example 1 is stable under various stability tests.

While illustrative examples of the invention have been described above, it is, of course, understood that many and various modifications will be apparent to those of ordinary skill in the relevant art, or may become apparent as the art develops, in the light of the foregoing description. Such modifications are contemplated as being within the spirit and scope of the invention or inventions disclosed in this specification.

Claims

A composition for removing makeups on keratin materials, comprising:

a) a dispersed fatty phase, comprising:

-at least one oil selected from the group consisting of ester oil, ether oil, or a mixture thereof,

-at least one hydrophobic polymer chosen from the group consisting of ester terminated poly (ester-amide) ； and

b) a continuous aqueous phase comprising at least one hydrophilic gelling agent.
The composition of claim 1, wherein the ester oil is selected from the compound of formula (I) ,

R₁COOR₂ (I)

wherein:

R₁ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group comprising from 4 to 40 carbon atoms, or a R₁’-O-group, wherein R₁’ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based chains comprising from 4 to 40 carbon atoms,

R₂ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group comprising from 4 to 40 carbon atoms；

preferably, in the formula (I) ,

R₁ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group from 4 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms, phenyl group, or a R₁’-O-group, wherein R₁’ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based chains comprising from 4 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms,

R₂ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group comprising from 4 to 30 carbon atoms, more preferably from 7 to 20 carbon atoms；

More preferably, in the formula (I) ,

R₁ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group of 8 carbon atoms, or phenyl group；

R₂ represents a linear, branched, cyclic, saturated, unsaturated hydrocarbon-based group comprising 8 carbon atoms, or phenyl group；

even more preferably, the ester oil is selected from the group consisting of C_12-15 alkyl benzoate, dicaprylyl carbonate, or a mixture thereof.
Composition of claim 1 or 2, wherein the ether oil is selected from the compound of formula (II) ,

R₃-O-R₄ formula (II)

wherein:

R₃ and R₄, which may be identical or different, denote a linear or branched C₆-C₂₅ alkyl or alkenyl radical, R₃ and R₄ being chosen such that the ether is liquid at a temperature of less than or equal to 25℃；

preferably, the ether of formula (II) is chosen from compounds for which the radicals R₃ and R₄, which may be identical or different, denote a linear or branched C₆-C₁₂ alkyl or alkenyl radical；

more preferably, the radicals R₃ and R₄are identical alkyl radical；

even more preferably, R₃ and R₄denote a C₈ radical.
Composition of any one of the preceding claims 1 to 3, wherein the at least one oil is present in an amount ranging from 1 to 50％by weight, and preferably ranging from 3 to 20％by weight, relative to the total weight ofthe composition.
Composition of any one of the preceding claims 1 to 4, wherein the hydrophobic ester terminated poly (ester-amide) polymer comprises at least one dimer dilinoleate unit； preferably the hydrophobic polymer is bis-stearyl ethylenediamine/neopentyl glycol/hydrogenated dimer dilinoleate copolymer.
The composition according to any one of the preceding claims 1 to 5, wherein the amount of the hydrophobic polymer is comprised from 0.1％to 15％by weight, preferably from 0.3％to 10％by weight, more preferably from 0.3％to 5％by weight, based on the total weight ofthe composition.
The composition according to any one of the preceding claims 1 to 6, wherein the hydrophilic gelling agent is chosen from polymers comprising at least one monomer being acrylamido-2-methylpropanesulfonic acid
preferably polymers of which at least one monomer of 2-acrylamido-2-methylpropanesulfonic acid is selected from the group consisting of crosslinked or non-crosslinked homopolymers or copolymers comprising at least the acrylamido-2-methylpropanesulfonic acid
monomer, in a form partially or totally neutralized with a mineral base other than ammonia, such as sodium hydroxide or potassium hydroxide； preferably selected from optionally crosslinked and/or neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymers, more preferably the hydrophilic gelling agent is poly (2-acrylamido-2-methylpropanesulfonic acid) .
The composition according to any one of the preceding claims 1 to 7, wherein the amount of the hydrophilic gelling agent may range, for example, from 0.01％to 5％by weight, preferably from 0.1％to 1％by weight, relative to the total weight of the composition.
Composition for removing makeups on keratin materials, comprising:

c) a dispersed fatty phase, comprising:

-at least one oil selected from the group consisting of C_12-15 alkyl benzoate, dicaprylyl carbonate, dicaprylyl ether, or a mixture thereof,

-bis-stearyl ethylenediamine/neopentyl glycol/hydrogenated dimer dilinoleate copolymer； and

d) a continuous aqueous phase comprising poly (2-acrylamido-2-methylpropanesulfonic acid) .
Cosmetic use of a composition according to any one of the preceding claims 1 to 8, for removing makeup from keratin materials, in particular from the skin.
Cosmetic process for removing the makeup on the keratin materials, which comprises a step of applying to the surface of a keratin material, in particular the skin, at least one composition as defined in any of the preceding claims 1 to 8.