WO2022124385A1 - Oil-in-water emulsion composition - Google Patents

Oil-in-water emulsion composition Download PDF

Info

Publication number
WO2022124385A1
WO2022124385A1 PCT/JP2021/045428 JP2021045428W WO2022124385A1 WO 2022124385 A1 WO2022124385 A1 WO 2022124385A1 JP 2021045428 W JP2021045428 W JP 2021045428W WO 2022124385 A1 WO2022124385 A1 WO 2022124385A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
less
composition
meth
oil
Prior art date
Application number
PCT/JP2021/045428
Other languages
French (fr)
Inventor
Nahoko Nakashima
Toru Koike
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2020202537A external-priority patent/JP2022090264A/en
Priority claimed from FR2100245A external-priority patent/FR3118702B1/en
Application filed by L'oreal filed Critical L'oreal
Publication of WO2022124385A1 publication Critical patent/WO2022124385A1/en

Links

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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • 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
    • A61K2800/548—Associative polymers
    • 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
    • A61K2800/59—Mixtures
    • A61K2800/594—Mixtures of polymers

Definitions

  • the present invention relates to an oil-in-water emulsion composition, preferably an oil-in-water skincare cosmetic composition.
  • Imparting texture to keratinous substances, such as skin is one of the key features of cosmetic products, in particular skin cosmetic products. So far, several technologies regarding emulsion compositions or gel-like compositions which impart an improved texture have been reported.
  • WO 2018/180316 discloses an emulsified cosmetic containing components A-E, wherein the content of component A is 0.1-1.0 mass%, the content of component B is 0.4 mass% or less, the content of component C is 0.3 mass% or less, the content of component D is 4.0 mass% or less, the mass ratio (component B/component A) of component B to component A is 0.10 or higher, the mass ratio (component C/component A) of component C to component A is 0.02 or higher, and the mass ratio (component D/component A) of component D to component A is 0.4-7.0, inclusive.
  • Component A is (acrylate/beheneth-25 methacrylate) copolymer.
  • Component B is carboxyvinyl polymer and/or alkyl-modified carboxyvinyl polymer.
  • Component C is xanthan gum.
  • Component D is phospholipid.
  • Component E is water.
  • JP-A-2016-121140 discloses a gel-like cosmetic composition
  • a gel-like cosmetic composition comprising a polyacrylic acid-based water-absorbing polymer of which the average particle diameter is 1 to 30 pm and the water absorption ratio is 5 to 50 g/g.
  • JP-A-2019- 182841 discloses a gel like cosmetic composition in an oil-in-water form comprising components (A), (B), (C), (D), and (E), wherein the content of component (D) is 0.1 to 1.0 mass%, the content of component (B) is 0.2 to 1.2 mass%, and the mass ratio of the content of component (B) to the content of component (A) [component (B) / component (A)] is 1.0 to 15.0.
  • Component (A) is a polymer comprising at least a structural unit derived from a (meth)acrylic acid and/or a (meth)acrylic alkyl ester and a structural unit derived from a (meth)acrylic acid polyoxyethylene alkyl ether.
  • Component (B) is a polymer comprising a structural unit derived from an aciyloyl dimethyl taurine acid salt.
  • Component (C) is one or more mono glyceryl fatty acid esters selected from the group consisting of glyceryl mono caprylate, glyceryl mono caprate, glyceryl mono laurate, glyceryl mono myristate, glyceryl mono palmitate, glyceryl mono stearate, glyceryl distearate, glyceryl mono isostearate, glyceryl diisostearate, glyceryl mono hydroxystearate, glyceryl mono oleate, glyceryl mono behenate, and glyceryl dibehenate.
  • Component (D) is a fatty alcohol having 12 to 24 carbon atoms.
  • Component (E) is water
  • organic UV filters are widely used to impart a UV protecting property to sun care compositions.
  • the use of organic UV filters may have a negative impact such as imparting oily, greasy, and sticky feelings during application. Therefore, there is a demand for sun care cosmetic compositions comprising organic UV filters, which impart an improved texture, such as a watery and fresh texture.
  • An objective of the present invention is to provide an oil-in-water sun care composition which can provide a watery and fresh sensation to a keratinous substance, such as skin.
  • an oil-in-water composition comprising:
  • the (a) associative polymer may further comprise one or more (meth)acrylic acid (Ci-Ci2)alkyl ester units.
  • the (a) associative polymer may further comprise one or more units derived from polyoxyalkylenated fatty alcohols.
  • the (b) neutralized poly(meth)acrylic acid polymer may be a crosslinked polymer.
  • the (b) neutralized poly(meth)acrylic acid polymer may be a homopolymer.
  • the (b) neutralized poly(meth)acrylic acid polymer may be partially neutralized.
  • the amount of the (a) associative polymer(s) may be 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
  • the amount of the (b) neutralized poly(meth)acrylic acid polymer(s) may be 0.05% by weight or more, preferably 0.1 % by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
  • the weight ratio of the (a) associative polymer(s) to the (b) neutralized poly(meth)acrylic acid polymer(s) in the composition may be 0.5 or more, preferably 0.8 or more, and in particular 0.9 or more, and/or may be 3 or less, preferably 2 or less, and in particular 1.5 or less.
  • the amount of the (c) organic UV filter(s) may be 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or may be 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition.
  • the amount of the (d) oils(s) may be 1 % by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, and in particular 6% by weight or more, and/or may be 20% by weight or less, preferably 15% by weight or less, more preferably 12% by weight or less, and in particular 10% by weight or less, relative to the total weight of the composition.
  • composition may further comprise at least one surfactant.
  • the surfactant may comprise a nonionic surfactant, an anionic surfactant, or a combination of a nonionic surfactant and an anionic surfactant.
  • the composition may further comprise water in an amount of 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, and in particular 50% by weight or more, and/or in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, and in particular 60% by weight or less, relative to the total weight of the composition.
  • the present invention also relates to a non-therapeutic cosmetic process for caring for and/or conditioning keratinous substances, such as skin, comprising: applying onto the keratinous substances an oil-in-water composition comprising:
  • composition according to the present invention is an oil-in-water composition comprising:
  • the composition may be a cosmetic composition, preferably a cosmetic composition for a keratinous substance, and more preferably a sun care cosmetic composition for a keratinous substance.
  • the keratinous substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, lips, and the like, and in particular skin.
  • the composition according to the present invention is an oil-in-water emulsion.
  • the form of the composition according to the present invention is not particularly limited, as long as it is in the form of an oil-in-water emulsion, such as an aqueous gel, an aqueous solution, or the like.
  • composition according to the present invention comprises (a) at least one associative polymer comprising one or more acrylic and/or methacrylic units, (b) at least one neutralized poly(meth)acrylic acid polymer, (c) at least one organic UV filter, and (d) at least one oil.
  • the ingredients in the composition will be described in a detailed manner below.
  • composition according to the present invention comprises (a) at least one associative polymer comprising one or more acrylic and/or methacrylic units.
  • a single type of associative polymer may be used, but two or more different types of associative polymers may be used in combination.
  • sociative polymer or “associative copolymer” refers to polymers or copolymers that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules.
  • the associative polymer of the present invention is preferably an associative copolymer of one or more acrylic and/or methacrylic units and of other units.
  • the associative copolymer more particularly comprises at least one hydrophilic part and at least one hydrophobic part.
  • hydrophobic group means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 16 to 30 carbon atoms.
  • the associative copolymer comprising one or more acrylic and/or methacrylic units means that the copolymer comprises at least one acrylic acid unit or at least one methacrylic acid unit or a mixture thereof.
  • the associative copolymer may comprise further units such as units formed by an alkyl ester of acrylic acid or methacrylic acid, preferably of acrylic acid, comprising less than 6 carbon atoms: for example, a C1-C4 alkylacrylate, for example, chosen from methyl acrylate, ethyl acrylate and butyl acrylate, called hereinafter "simple ester".
  • the associative copolymer according to the present invention comprises one or more (meth)acrylic acid (Ci-Ci2)alkyl ester units, more preferably one or more (meth)acrylic acid (Ci-C6)alkyl ester units.
  • the associative copolymer according to the present invention comprises one or more acrylic acid units. According to a further embodiment, the associative copolymer according to the present invention comprises one or more methacrylic acid units. According to another embodiment, the associative copolymer according to the present invention comprises one or more acrylic acid units and one or more methacrylic acid units.
  • the associative copolymer may comprise another unit derived from another monomer that is different from (meth)acrylic acid.
  • such monomer may be esters of ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid or itaconic acid, and of polyoxyalkylenated fatty alcohols.
  • the fatty alcohol moiety of the ester monomer can be linear or branched, preferably linear, saturated or unsaturated, preferably saturated, (Ci2-C3o)fatty alcohol, and in particular (Ci6-C26)fatty alcohol.
  • the polyoxyalkylene chain of the ester monomer preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units.
  • the number of oxyalkylene units generally ranges from 3 to 100, preferably from 7 to 50 and more preferably from 12 to 30.
  • the (a) associative copolymer that can be used according to the present invention may also be chosen from anionic associative copolymers containing acrylic and/or methacrylic units.
  • the (meth)acrylic anionic associative copolymer that may be used according to the present invention may be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type; and at least one hydrophobic unit of a type such as a (Cio-C3o)alkyl ester of an unsaturated carboxylic acid.
  • these (meth)acrylic associative copolymers are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (I) below: in which R 1 denotes H or CH3, i.e. acrylic acid or methacrylic acid units, and in which the hydrophobic unit of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (II) below: in which R 1 denotes H or CH3 (i.e. acrylate or methacrylate units), R 2 denoting a C10-C30 and preferably a C12-C22 alkyl radical.
  • (Cio-C3o)alkyl esters of unsaturated carboxylic acids according to formula (II) mention may more particularly be made of lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
  • (Meth)acrylic associative copolymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509949.
  • the (meth)acrylic associative copolymer that may be used according to the present invention may more particularly denote polymers formed from a mixture of monomers comprising:
  • crosslinking agent can mean a monomer containing the group and at least one other polymerizable group, the unsaturated bonds of the monomer being unconjugated relative to each other.
  • crosslinking agent that may be used according to the present invention, mention may especially be made of polyallyl ethers especially such as polyallyl sucrose and polyallylpentaerythritol.
  • the ones particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TRI, Pemulen TR2, Carbopol 1382, and more preferably still Pemulen TRI, and the product sold by the company S.E.P.C. under the name Coatex SX.
  • (meth)acrylic associative copolymer mention may also be made of the copolymer of methacrylic acid/methyl acrylate/dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated alcohol sold under the name Viscophobe DB 1000 by the company Amerchol.
  • (meth)acrylic associative copolymers that may be used according to the present invention may also be sulfonic polymers comprising at least one (meth)acrylic monomer bearing sulfonic group(s), in free form or partially or totally neutralized form and comprising at least one hydrophobic portion.
  • the said hydrophobic portion present in the said sulfonic polymers that may be used according to the present invention preferably comprises from 8 to 22 carbon atoms, more preferably from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.
  • these sulfonic polymers that maybe used according to the present invention are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
  • a mineral base sodium hydroxide, potassium hydroxide or aqueous ammonia
  • organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
  • These said sulfonic polymers generally have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000000 g/mol and even more preferably from 100000 to 1 500000 g/mol.
  • the sulfonic polymers that may be used according to the present invention may or may not be crosslinked.
  • Crosslinked polymers are preferably chosen.
  • the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol diacrylatedi(meth)acrylate or tetraethylene glycol diacrylatedi(meth)acrylate, trimethylolpropane triaciylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl
  • Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will be used more particularly.
  • the degree of crosslinking will generally range from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol% relative to the polymer.
  • the (meth)acrylic monomers bearing sulfonic group(s) of the sulfonic polymers that may be used according to the present invention are chosen especially from (meth)acryIamido(Ci-C22)alkylsulfonic acids and N-(Ci-C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
  • (Meth)acrylamido(Ci-C22)alkylsulfonic acids for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-aciylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.
  • 2-Acrylamido-2-methylpropanesulfonic acid (AMPS) and also partially or totally neutralized forms thereof, will even more particularly be used.
  • the (meth)acrylic associative thickeners that may be used according to the present invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or C6-C22 di-n-alkylamine, such as those described in patent application WO 00/31154 (which forms an integral part of the content of the description).
  • These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acids, P-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • the (meth)acrylic associative thickeners bearing sulfonic group(s) that may particularly preferably be used according to the present invention are preferably chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion containing from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.
  • copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, p-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • monomers not comprising a fatty chain such as (meth)acrylic acids, p-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
  • the ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably selected from the acrylates or acrylamides of formula (IV) below: in which R 5 and R 7 , which may be identical or different, denote a hydrogen atom or a linear or branched Ci-Ce alkyl radical (preferably methyl); Y denotes O or NH; R 6 denotes a hydrophobic hydrocarbon-based radical containing at least 8 to 50 carbon atoms, more preferentially from 8 to 22 carbon atoms, even more preferentially from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes the number of moles of alkylene oxide and ranges from 0 to 100.
  • R 5 and R 7 which may be identical or different, denote a hydrogen atom or a linear or branched Ci-Ce alkyl radical (preferably methyl); Y denotes O or NH; R 6 denotes a hydrophobic hydrocarbon-based radical
  • the radical R 6 is preferably chosen from linear Ce-Cis alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), or branched or cyclic Ce-Cis alkyl radicals (for example cyclododecane (C12) or adamantane (C10)); Ce-Cis perfluoroalkyl radicals (for example the group of formula -(CH2)2-(CF2) -CF3); the cholesteryl radical (C27) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene.
  • these radicals the ones that are more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.
  • the monomer of formula (IV) comprises at least one alkylene oxide unit (x > 1) and preferably a polyoxyalkylene chain.
  • the polyoxyalkylene chain preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units.
  • the number of oxyalkylene units generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
  • - copolymers which may or may not be crosslinked and which may or may not be neutralized, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide units or of (C8-Ci6)alkyl (meth)acrylate units, relative to the polymer, such as those described in patent application EP-A-750 899;
  • - terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-Ci8)alkylaciyla ide units, such as those described in patent US-5 089 578.
  • copolymers of totally neutralized AMPS and of dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
  • R 5 denotes methyl
  • R 8 represents a C16-C2 alkyl chain, such as a stearyl group, or behenyl group is particularly preferred.
  • the polymers for which X + denotes sodium or ammonium are more particularly preferred.
  • the (a) associative polymer(s) of the present invention may be present in an amount of 0.05% by weight or more, preferably 0.1 % by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be present in an amount of 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
  • the composition according to the present invention comprises (b) at least one neutralized poly(meth)acrylic acid polymer.
  • a single type of neutralized poly(meth)acrylic acid polymer may be used, but two or more different types of neutralized poly(meth)acrylic acid polymers may be used in combination.
  • the neutralized poly(meth)acrylic acid polymer of the present invention may have a water absorbing property. Therefore, the neutralized poly(meth)acrylic acid polymer can be a water absorbing polymer.
  • the neutralized poly(meth)acrylic acid polymer may have a water absorbing capacity of 10 g or more, preferably 20 g or more, and more preferably 50 g or more, and/or of 2,000 g or less, preferably 1,500 g or less, and more preferably 1,000 g or less, relative to 1 g of the polymer at 25°C and 1 atm.
  • the neutralized poly(meth)acrylic acid polymer may be provided in the form of particles, and preferably in the form of spherical particles.
  • the average primary particle size as D50 of the neutralized poly(meth)acrylic acid polymer is not particularly limited, but in general is 0.1 pm or more, preferably 0.5 pm or more, and more preferably 1 pm or more, and/or is 200 pm or less, preferably 100 pm or less, more preferably 50 pm or less.
  • the term “D50” herein means the particle size at which 50% by volume of the particles based on the total volume of the particles are smaller than or equal to D50 and 50% by volume of the particles based on the total volume of the particles are larger than D50.
  • the D50 value can be determined by laser diffraction, for example, using a laser diffraction particle size distribution analyzer, such as Mastersizer 2000 by Malvern Corp.
  • the neutralized poly(meth)acrylic acid polymer may be water soluble. Therefore, the neutralized poly(meth)acrylic acid polymer may be included in a water phase of the O/W emulsion composition ofthe present invention.
  • the neutralized poly(meth)acrylic acid polymer of the present invention may be neutralized totally or partially.
  • the neutralized poly(meth)aciylic acid polymer is partially neutralized.
  • the molar ratio of neutralized parts to un-neutralized parts is not particularly limited, but in general 10 mol% or more, 20 mol% or more, 30 mol% or more, or 40 mol% or more, and/or 90 mol% or less, 80 mol% or less, 70 mol% or less, or 60 mol% or less.
  • the neutralized poly(meth)acrylic acid polymer may be a homo- or copolymer.
  • the neutralized poly(meth)acrylic acid polymer is a homopolymer.
  • the neutralized poly(meth)acrylic acid polymer may be crosslinked.
  • the neutralized poly(meth)acrylic acid polymer is a crosslinked homopolymer.
  • Mention may in particular made of sodium polyaciylate sold under the name of AQUPEC MG N40R, which is crosslinked and partially neutralized and also called as sodium carbomer.
  • the (b) neutralized poly(meth)acrylic acid polymer(s) may be present in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be present in an amount of 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
  • the weight ratio of the (a) associative polymer to the (b) neutralized poly(meth)acrylic acid polymer in the composition is not particularly limited. In preferred embodiments of the present invention, the weight ratio of the (a) associative polymer to the (b) neutralized poly(meth)acrylic acid polymer in the composition is 0.5 or more, preferably 0.8 or more, and in particular 0.9 or more, and/or is 3 or less, preferably 2 or less, and in particular 1.5 or less.
  • composition according to the present invention may comprise at least one (c) organic UV filter.
  • a single type of the organic UV filter may be used, but two or more different types of organic UV filters may be used in combination.
  • UV here means ultraviolet radiation and comprises the UV-B region (260-320 nm in wavelength) and the UV-A region (320-400 nm in wavelength). Therefore, a UV filter means any material which has filtering effects on ultraviolet radiation in wavelengths of the UV-A and/or UV-B regions.
  • the UV filter(s) used for the present invention may be active in the UV-A and/or UV-B region, preferably in both of the UV-A and UV-B regions alone or in combination. Therefore, the UV filter(s) used in the present invention include(s) a UV-A filter capable of absorbing UV radiation from 320 to 400 nm, a UV-B filter capable of absorbing UV radiation from 280 to 320 nm, and a UV-A and UV-B filter capable of absorbing UV radiation from 280 to 400 nm.
  • the organic UV filters used for the present invention can be lipophilic organic UV filters and/or hydrophilic organic UV filters.
  • the composition according to the present invention comprises at least one lipophilic organic UV filter, and more preferably comprises a combination of at least one lipophilic organic UV filter and at least one hydrophilic organic UV filter.
  • lipophilic organic UV filter here means organic UV filters which are soluble in oils at a concentration of at least 1% by weight relative to the total weight of the oils at room temperature (25°C) and atmosphere pressure (10 5 Pa). Therefore, the lipophilic organic UV filter(s) is(are) present in the oily phase of the present invention.
  • the lipophilic organic UV-A filters used in the present invention may include, but are not limited to, aminobenzophenone compounds, dibenzoylmethane compounds, anthranilic acid compounds, and 4,4-diaiylbutadiene compounds.
  • n-hexyl 2-(4-diethlamino-2-hydroxybenzoyl)benzoate the alternative name of which is diethylamino hydroxybenzoyl hexyl benzoate (DHHB), sold under the trade name “Uvinul A+” from BASF.
  • DHHB diethylamino hydroxybenzoyl hexyl benzoate
  • dibenzoylmethane compounds mention may be made of 4-isopropyldibenzoylmethane, sold under the name of “Eusolex 8020” from Merck, l-(4-methoxy-l-benzofuran-5-yl)-3-phenylpropane-l, 3-dione, sold under the name of “Pongamol” from Quest, l-(4-(tert-butyl)phenyl)-3-(2-hydroxyphenyl)propane- 1,3-dione, and butyl methoxydibenzoylmethane, sold under the trade name “Parsol 1789” from Hoffrnann-La Roche.
  • 4,4-diarylbutadiene compounds mention maybe made of 1,1 -dicarboxy (2,2'-dimethylpropyl)-4,4-diphenylbutadiene and diphenyl butadiene malonates and malononitriles.
  • the lipophilic organic UV-B filters used in the present invention may include, but are not limited to, triazine compounds, para-aminobenzoic acid compounds, salicylic compounds, cinnamate compounds, P,P-diphenylacrylate compounds, benzylidenecamphor compounds, phenylbenzimidazole compounds, imidazoline compounds, benzalmalonate compounds, and merocyanine compounds.
  • triazine compounds mention may be made of ethylhexyl triazone, marketed under the name “UVINUL T- 150” by BASF, diethylhexyl butamido triazone, marketed under the name “UVASORB HEB” by SIGMA 2V, 2,4,6-tris(dineopentyl 4’-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4 ’ -aminoben leopardalonate)-s-triazine, 2,4-bis(dineopentyl 4’-aminobenzalmalonate)-6-(n-butyl 4’-aminobenzoate)-s-triazine, 2,4-bis(n-butyl 4 ’ -aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine.
  • UVINUL T- 150 by BASF
  • para-aminobenzoic acid derivatives mention may be made of para-aminobenzoates (PABA), for example, ethyl PABA (para-aminobenzoate), ethyl dihydroxypropyl PABA, and ethylhexyl dimethyl PABA, marketed under the name “ESCALOL 5972 from ISP.
  • PABA para-aminobenzoates
  • salicylic compounds mention may be made of homosalate, marketed under the name “Eusolex HMS” by Rona/EM industries, and ethylhexyl salicylate, marketed under the name “NEO HELIOPAN OS” by Symrise.
  • ethylhexyl methoxycinnamate marketed under the name “PARSOL CX” by DSM NUTRITIONAL PRODUCTS
  • isopropyl ethoxy cinnamate isoamyl methoxy cinnamate, marketed under the name “NEO HELIOPAN E 1000” by Symrise, diisopropyl methylcinnamate, cinoxate, and glyceryl ethylhexanoate dimethoxycinnamate.
  • 3-diphenylacrylate compounds mention may be made of octocrylene, marketed under the name “UVINUL N539” by BASF, and etocrylene, marketed under the name “UVENUL N35” by BASF.
  • benzylidenecamphor compounds mention may be made of 3-benzylidene camphor, marketed under the name “MEXORYL SD” from CHIMEX, methylbenzylidene camphor, marketed under the name “EUSOLEX 6300” by MERCK, polyacrylamidomethyl benzylidene Camphor, marketed under the name “MEXORYL SW” by CHIMEX, and terephthalylidene dicamphor sulfonic acid, marketed under the name “Mexoryl SX” by Chimex.
  • phenylbenzimidazole compounds mention may be made of phenylbenzimidazole sulfonic acid, marketed under the name “Eusolex 232” by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, marketed under the name “Neo Heliopan AP” by Haarmann and Reimer.
  • imidazoline compounds mention may be made of ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
  • benzalmalonate compounds mention may be made of polyorgandsiloxane containing a benzabnalonate moiety, for example, Polysilicone- 15, marketed under the name “Parsol SLX” by DSM NUTRITIONAL PRODUCTS, and di-neopentyl 4'-methoxybenzalmalonate.
  • the lipophilic organic UV filters of the present invention may comprise lipophilic UV-A and UV-B filters.
  • the following are non-limited examples of the lipophilic organic UV-A and UV-B filters:
  • Benzophenone compounds such as benzophenone- 1 marketed under the name “UVINUL 400” by BASF, benzophenone-2 marketed under the name “UVINUL 500” by BASF, benzophenone-3 or oxybenzone marketed under the name “UVINUL M40” by BASF, benzophenone-6 marketed under the name “Helisorb 11” by Norquay, benzophenone-8 marketed under the name “Spectra-Sorb UV-24” by American Cyanamid, benzophenone- 10, benzophenone-11, and benzophenone-12;
  • - benzotriazole compounds such as drometrizole trisiloxane marketed under the name “Silatrizole” by Rhodia Chimie and bumetrizole marketed under the name “TINOGUARTD AS” by CIBA-GEIGY, and 2,2'-Methylenebis[6-(2H-Benzotriazol-2-yl)-4-(l,l,3,3-Tetramethyl-Butyi) Phenol] (Methylene Bis-Benzotriazolyl Tetramethylbutylphenol) marketed as “TINOSORB M” by BASF;
  • the lipophilic organic UV filter of the present invention is selected from a combination of at least one lipophilic organic UV-A filter and at least one lipophilic organic UV-B filter.
  • the lipophilic organic UV filter(s) may be present in the composition in an amount of 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or may be present in an amount of 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition.
  • hydrophilic organic UV filter here means organic UV filters which are soluble in water at a concentration of at least 1% by weight relative to the total weight of the water at room temperature (25°C) and atmosphere pressure (10 5 Pa). Therefore, the hydrophilic organic UV filter(s) is(are) present in the aqueous phase of the present invention.
  • the hydrophilic organic UV-A filter includes, but is not limited to:
  • Bisbenzoxazolyl derivatives such as described in Patent, EP 669323 and US 2,463,264, more particularly the compound Disodium Phenyl Dibenzimidazole Tetrasulfonate and salts thereof, sold under the trade name “Neo Heliopan AP” by Haarmann and Reimer.
  • the hydrophilic organic UV-B filter includes, but is not limited to: p-Aminobenzoic (PABA) derivatives, such as PABA, Glyceryl PABA and PEG-25 PABA, and salts thereof such as sold under the name “Uvinul P25” by BASF, Phenylbenzimidazole Sulfonic Acid and salts thereof, such as sold in particular under the trade name “Eusolex 232” by Merck, Ferulic Acid and salts thereof,
  • PABA p-Aminobenzoic
  • Benzylidene Camphor Sulfonic Acid and salts thereof such as that manufactured under the name “Mexoryl SL” by Chimex,
  • Camphor Benzalkonium Methosulfate and salts thereof such as that manufactured under the name “Mexoryl SO” by Chimex.
  • the hydrophilic organic UV-A and UV-B filter includes, but is not limited to: Benzophenone-4 and salts thereof, such as those sold under the trade name “Uvinul MS40” by BASF,
  • the salts of the compounds that may be used are chosen in particular from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; salts of ammonium of formula NH 4+ ; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts.
  • Salts chosen from sodium, potassium, magnesium, strontium, copper, manganese or zinc salts are preferably used.
  • the sodium salt is preferentially used.
  • the hydrophilic organic UV filter(s) may be present in the composition in an amount of 0.1% by weight or more, more preferably 0.5% by weight or more, even more preferably 1 % by weight or more, and in particular 2% by weight or more, and/or may be present in an amount of 7% by weight or less, preferably 5% by weight or less, and in particular 4% by weight or less, relative to the total weight of the composition.
  • the (c) organic UV filter(s) may be present in an amount of 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or may be present in an amount of 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition.
  • composition according to the present invention may comprise at least one oil. If two or more oils are used, they may be the same or different.
  • oil means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg).
  • oils those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile.
  • the oil is different from the UV filter.
  • the oil can form the oily phase of the O/W emulsion of the composition according to the present invention. Therefore, the oil phase of the composition includes the oil.
  • the oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof.
  • the oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.
  • plant oils examples include, for example, linseed oil, camellia oil, macadamia nut oil, com oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.
  • animal oils mention may be made of, for example, squalene and squalane.
  • alkane oils such as isododecane and isohexadecane
  • ester oils such as isododecane and isohexadecane
  • ether oils such as triglycerides
  • the ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C1-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
  • esters of monoalcohols Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present invention are derived is branched.
  • monoesters of monoacids and of monoalcohols mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.
  • Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols may also be used.
  • esters of monocarboxylic, dicarboxylic, or tricarboxylic acids and of non-sugar C4-C26 dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols may also be used.
  • sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids.
  • sucrose means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.
  • suitable sugars include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.
  • esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters, and polyesters, and mixtures thereof.
  • esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, and arachidonates, or mixtures thereof such as, especially, oleopahnitate, oleostearate, and pahnitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.
  • monoesters and diesters and especially sucrose, glucose, or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearates.
  • ester oils mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hex
  • ether oils mention may be made of, for example, ether oils with a short hydrocarbon chain or chains, such as dicaprylyl ether.
  • artificial triglycerides mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate), and glyceryl tri(caprate/caprylate/linolenate).
  • capryl caprylyl glycerides glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate), and glyceryl tri(caprate/caprylate/linolenate).
  • silicone oils mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.
  • linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like
  • cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodeca
  • the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
  • PDMS liquid polydimethylsiloxanes
  • silicone oils may also be organomodified.
  • organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
  • Organopolysiloxanes are defined in greater detail in Walter Noll’s Chemistry and Technology of Silicones ( 1968), Academic Press. They may be volatile or non-volatile.
  • the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C.
  • Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.
  • CTFA dimethiconol
  • silicones containing aryl groups mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.
  • oils of the SF series from General Electric such as SF 1023, SF 1154, SF 1250, and SF 1265.
  • phenyl silicone oil phenyl trimethicone is preferable.
  • the organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.
  • Hydrocarbon oils may be chosen from:
  • hydrocarbon oils As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.
  • linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.
  • fatty in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols.
  • the fatty alcohol may be saturated or unsaturated.
  • the fatty alcohol may be linear or branched.
  • the fatty alcohol may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms.
  • R may be chosen from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.
  • fatty alcohol examples include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.
  • the fatty alcohol be a saturated fatty alcohol.
  • the fatty alcohol may be selected from straight or branched, saturated or unsaturated C6-C30 alcohols, preferably straight or branched, saturated C6-C30 alcohols, and more preferably straight or branched, saturated C12-C20 alcohols.
  • saturated fatty alcohol here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C6-C30 fatty alcohols. Among the linear or branched, saturated C6-C30 fatty alcohols, linear or branched, saturated C12-C20 fatty alcohols may preferably be used. Any linear or branched, saturated C16-C20 fatty alcohols may be more preferably used. Branched C16-C20 fatty alcohols may be even more preferably used.
  • saturated fatty alcohols mention maybe made of lauryl alcohol, cetyl alcohol, steaiyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.
  • cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol can be used as a saturated fatty alcohol.
  • the (d) oil(s) may be present in an amount of 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, and in particular 6% by weight or more, and/or may be present in an amount of 20% by weight or less, preferably 15% by weight or less, more preferably 12% by weight or less, and in particular 10% by weight or less, relative to the total weight of the composition.
  • the composition according to the present invention may comprise water.
  • the water can form the water phase of the O/W emulsion of the present invention. Therefore, the water phase of the composition may comprise water.
  • the water may be present in an amount of 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, and in particular 50% by weight or more, and/or may be present in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, and in particular 60% by weight or less, relative to the total weight of the composition.
  • composition according to the present invention may comprise at least one surfactant chosen from amphoteric, anionic, cationic, or nonionic surfactants, used alone or as a mixture.
  • the composition comprises at least one nonionic surfactant.
  • the composition comprises at least one anionic surfactant.
  • the composition comprises a combination of at least one nonionic surfactant and at least one anionic surfactant.
  • nonionic surfactants usable in the compositions of the present invention may include polyethoxylated fatty alcohols or polyglycerolated fatty alcohols, such as the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene units (Laureth-9 to Laureth-50 as the INCI names), in particular Laureth-9; esters of polyols and of a fatty acid possessing a saturated or unsaturated chain comprising, for example, from 8 to 24 carbon atoms, and their oxyalkylenated derivatives, that is to say comprising oxyethylene and/or oxypropylene units, such as esters of glycerol and of a C8-C24 fatty acid, and their oxyalkylenated derivatives, in particular polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), for example PEG-20 glyceryl triisostearate; esters of sugar and of ethylene
  • R-O-(G) X (1) in which R represents a branched and/or unsaturated alkyl radical comprising from 14 to 24 carbon atoms, G represents a reduced sugar comprising 5 or 6 carbon atoms and x denotes a value ranging from 1 to 10 and preferably from 1 to 4, and G in particular denotes glucose, fructose or galactose.
  • This alkyl polyglucoside can be used as a mixture with a coemulsifier, more especially with a fatty alcohol and in particular a fatty alcohol having the same fatty chain as that of the alkyl polyglucoside, that is to say comprising from 14 to 24 carbon atoms and having a branched and/or unsaturated chain, for example isostearyl alcohol when the alkyl polyglucoside is isostearyl glucoside and oleyl alcohol when the alkyl polyglucoside is oleyl glucoside.
  • fatty alcohol/alkylpolyglycoside mixtures that are particularly preferred, mention may be made of the products sold by the company SEPPIC under the name
  • Ci2-C2o alkyl glucoside (Montanov L®)
  • the polysaccharide may be selected from polyglucose or polyfructose.
  • Preferred polyglucoses are selected from cellulose, methyl cellulose, hydroxyethyl cellulose, amylose, amylopectin and dextrin.
  • a preferred polyfructose is inulin.
  • the hydrophobized polysaccharide as the nonionic surfactant is hydrophobized inulin.
  • the hydrophobic chains which can be connected or grafted onto the main chain of the polysaccharides may in particular be linear or branched, saturated or unsaturated hydrocarbon chains having 1 to 50 carbon atoms, such as alkyl, arylalkyl, alkylaryl and alkylene groups, divalent cycloaliphatic groups, or organopolysiloxane chains.
  • These hydrocarbon or organopolysiloxane chains may in particular comprise one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea and/or sulphonamide functions.
  • stearoyl inulin such as those sold under the names Lifidrem INST by Engelhard and Rheopearl INS by Ciba
  • palmitoyl inulin such as those sold under the names Lifidrem INUK and Lifidrem INUM by Engelhard
  • inulin laurylcarbamate such as that sold under the name Inutec SP1 by Orafti.
  • anionic surfactants usable in the compositions of the present invention may include alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl ether sulfonates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alpha-olefin sulfonates, beta alkyloxy alkene sulfonates, alkyl arylsulfonates, alkyl carbonates, succinamates, sulfosuccinates, sarcosinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, sulfated monoglycerides, fatty acid amino polyoxyethylene sulfates, isethionates, alkyl benzene sulfonic acids, polyoxyethylene alkyl ether sulfuric acids, polyoxyethylene alkyl ether carboxylic acids, and polyoxyethylene alkyl
  • the anionic surfactant be selected from the group consisting of (C6-C3o)alkyl sulfates, (Ce-C3o)alkyl ether sulfates, (C6-C o)alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; (C6-C3o)alkylsulfonates, (C6-C3o)alkylamide sulfonates, (Ce-C3o)alkylaryl sulfonates, a-olefin sulfonates, paraffin sulfonates; (C6-C3o)alkyl phosphates; (Cg-C3o)alkyl sulfosuccinates, (C6-C3o)alkyl ether sulfosuccinates, (C6-C3o)alkylamide sulfos
  • the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form.
  • the anionic surfactant be selected from salts of (Ce-C24)acyl glutamates, (C6-C3o)alkyl sulfate, (C6-C3o)alkyl ether sulfates or polyoxyalkylenated (Ce-C3o)alkyl ether carboxylic acid, that may or may not be salified.
  • the anionic surfactant may be selected from sodium salt of (Ce-C24)acyl glutamates, such as sodium stearoyl glutamate.
  • the nonionic surfactant(s) may be present in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, even more preferably 1.3% by weight or more, and in particular 1.5% by weight or more, and/or may be present in an amount of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, and in particular 3% by weight or less, relative to the total weight of the composition.
  • the anionic surfactant(s) may be present in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, even more preferably 0.2% by weight or more, and in particular 0.25% by weight or more, and/or may be present in an amount of 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
  • the surfactant(s) may be present in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, even more preferably 1.5% by weight or more, and in particular 1.7% by weight or more, and/or may be present in an amount of 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and in particular 3% by weight or less, relative to the total weight of the composition.
  • composition according to the present invention may comprise at least one thickener, which is different from the components (a) and (b) of the present invention. Two or more thickeners can be combined.
  • the thickener may be hydrophilic or lipophilic, and preferably lipophilic.
  • the lipophilic thickener may be in the form of polymer.
  • the lipophilic polymer thickener may be chosen from carboxyvinyl polymers such as the Carbopol products (carbomers) and the Pemulen products (acrylate/C10-C30-alkyl acrylate copolymer) or polymers having the INCI name "Poly C10-30 Alkyl Acrylate", such as the Intelimer® products from Air Products, such as the product Intelimer® IPA 13-1, which is a polystearyl acrylate, or the product 30 Intelimer® IPA 13-6 which is a behenyl polymer.
  • carboxyvinyl polymers such as the Carbopol products (carbomers) and the Pemulen products (acrylate/C10-C30-alkyl acrylate copolymer) or polymers having the INCI name "Poly C10-30 Alkyl Acrylate", such as the Intelimer® products from Air Products, such as the product Intelimer® IPA 13-1, which is a polystearyl acrylate, or the product 30
  • the amount of the thickener(s) in the composition may be from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, and more preferably from 0.3 to 3% by weight, relative to the total weight of the composition.
  • composition according to the present invention may comprise at least one cosmetically acceptable hydrophilic organic solvent.
  • hydrophilic here means substances having a solubility of at least 1 g/L, preferably at least 10 g/L, and more preferably at least 100 g/L, in water at room temperature (25°C) and atmospheric pressure (10 5 Pa). Therefore, the cosmetically acceptable hydrophilic organic solvent is included in the water phase, if present.
  • the cosmetically acceptable hydrophilic organic solvent(s) may include, for example, substantially linear or branched lower mono-alcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerine, propanediol, pentylene glycol, caprylyl glycol, sorbitol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol ethers, propylene glycol monomethylether, diethylene glycol alkyl ethers, such as diethylene glycol monoethylether or monobutylether; polyethylene glycols, such as PEG-4, PEG-6, PEG-8,
  • the amount of the cosmetically acceptable hydrophilic organic solvent(s) in the composition according to the present invention may be from 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and in particular 7% by weight or more, and/or may be 30% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less, relative to the total weight of the composition.
  • the composition according to the present invention may comprise at least one filler. Two or more fillers can be combined.
  • the filler can be inorganic or organic.
  • the filler also can be silicone powder.
  • inorganic filler mention may be made of talc, mica, silica, hollow silica, magnesium aluminum silicate, trimethyl siloxysilicate or silica silylate, kaolin, bentone, calcium carbonate, magnesium hydrogen carbonate, hydroxyapatite, boron nitride, fluorphlogopite, sericite, calcinated talc, calcinated mica, calcinated sericite, synthetic mica, perlite, lauroyl lysine, metal soap, bismuth oxychloride, barium sulfate, magnesium carbonate, and mixtures thereof, optionally hydrophilic- or hydrophobic-treated.
  • organic filler mention may be made of acrylic polymer powders, silicone powders, wax powders, polyamide powders, urethane polymer powders, tetrafluoroethylene polymer powders, polyacrylonitrile powders, poly-0-alanine powders, polyethylene powders, polytetrafluoroethylene powders, lauroyllysine, starch, cellulose powder, tetrafluoroethylene polymer powders and mixtures thereof.
  • silicone powders mention may be made of organopolysilsesquioxane powders, organopolysiloxane powders, and silicone resin powders.
  • the amount of the filler(s) in the composition may be 0.1% by weight or more, preferably 0.5%> by weight or more, and more preferably 1% by weight or more, and 15% by weight or less, preferably 10% by weight or less, and more preferably 5%> by weight or less, relative to the total weight of the composition.
  • the pH of the composition according to the present invention may be adjusted to the desired value using at least one pH adjusting agent, such as an acidifying or a basifying agent, for example, which are commonly used in cosmetic products.
  • at least one pH adjusting agent such as an acidifying or a basifying agent, for example, which are commonly used in cosmetic products.
  • the pH of the composition according to the present invention may be 8.0 or less, preferably 7.0 or less, more preferably 6.0 or less, even more preferably 5.0 or less, and in particular 4.5 or less, and/or may be 2.5 or more, preferably 3.0 or more, more preferably 3.5 or more, and in particular 4.0 or more at 25°C.
  • acidifying agents mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, ortho-phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, and lactic acid, and sulfonic acids.
  • mineral or organic acids such as hydrochloric acid, ortho-phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, and lactic acid, and sulfonic acids.
  • basifying agents mention may be made, by way of example, of hydroxides of an alkali metal or an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide; quaternary ammonium hydroxides and guanidinium hydroxide; alkali metal silicates, such as sodium metasilicates; amino acids, preferably basic amino acids, such as arginine, lysine, ornithine, citrulline and histidine; carbonates and bicarbonates; organic alkaline agents, for example, alkanolamines such as mono-, di- and tri-ethanolamine, and isopropanolamine; urea, guanidine and their derivatives; and the compounds of the following formula: in which
  • W is a Ci-C 6 alkylene residue optionally substituted with a hydroxyl group or a Ci-Ce alkyl group;
  • Rx, Ry, Rz and Rt which may be identical or different, represent a hydrogen atom or a Ci-Ce alkyl, Ci-C 6 hydroxyalkyl or Ci-Ce aminoalkyl group. Mention may especially be made of 1,3-diaminopropane, l,3-diamino-2-propanol, spermine and spermidine.
  • the pH adjusting agent(s) may be used in an amount ranging from 0.001 % to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.
  • composition according to the present invention may also comprise any adjuvant(s) usually used in the field of cosmetics, chosen, for example, from hydrophobic organic solvents, gums, resins, antioxidants, such as tocopherol, buffers, preserving agents, such as phenoxyethanol, co-preservatives, opacifying agents, fragrances, neutralizers, antiseptics, UV-screening agents, stabilizers or electrolyte, sequestering agents, such as trisodium ethylenediamine disuccinate, dispersing agents, buffers, dyes and/or pigments, emollients or collagen-protecting agents, and mixtures thereof.
  • adjuvant(s) usually used in the field of cosmetics chosen, for example, from hydrophobic organic solvents, gums, resins, antioxidants, such as tocopherol, buffers, preserving agents, such as phenoxyethanol, co-preservatives, opacifying agents, fragrances, neutralizers, antiseptics, UV-screening agents, stabilize
  • the adjuvants may be present in the composition of the present invention in an amount ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 0.5% to 10% by weight, relative to the total weight of the composition.
  • composition according to the present invention can be prepared by mixing the above-described essential and optional ingredients in a conventional manner. It is possible to further comprise mixing any of the optional ingredients and heating the composition until an ingredient is dissolved.
  • the present invention also relates to a non-therapeutic method or process, preferably a cosmetic method or process, and more preferably a cosmetic method or process for caring for and/or conditioning keratinous substances, such as skin, scalp, and lips, in particular skin, comprising: applying onto the keratinous substance an oil-in-water composition comprising:
  • the present invention also relates to a non-therapeutic method or process, preferably a cosmetic method or process, and more preferably a cosmetic method or process for caring for and/or conditioning keratinous substances, such as skin, scalp, and lips, in particular skin, comprising: applying onto the keratinous substance an oil-in-water composition comprising:
  • compositions comprising one or more acrylic and/or methacrylic units, the (b) neutralized poly(meth)acrylic acid polymer, the (c) organic UV filter, and the (d) oil in the composition according to the present invention above can be applied to the composition, the (a) associative polymer comprising one or more acrylic and/or methacrylic units, the (b) neutralized poly(meth)acrylic acid polymer, the (c) organic UV filter, and the (d) oil for the method and process according to the present inventions.
  • the composition used in the process and method according to the present invention may include any of the optional ingredients as explained above for the composition according to the present invention.
  • Homogeneous solution compositions according to the Examples and Comparative Examples were prepared by mixing the ingredients as listed in Tables 1 and 2. Specifically, in a first step, water and the ingredients in a water phase, i.e. water-soluble and water-dispersible ingredients, were mixed in water and the mixture was heated to 75 °C to obtain a homogenous water phase. The oils and ingredients in an oily phase, i.e. oil-soluble and oil-dispersible ingredients, were mixed in the oils and the mixture was heated to 75 °C to obtain a homogenous oily phase. The obtained oily phase was added to the water phase and they were homogenized at 8,000 rpm for 10 minutes at 75°C. The mixture was then cooled to less than 45°C.
  • the stickiness of each composition was measured by using Texture Analyzer TA.XT plus (Stable Micro Systems) with a 20-mm cylinder made of aluminum (P/20). The measurement conditions were as follows.
  • Substrate 30 mm x 30 mm flat bioskin
  • Sample 20 mg of composition which was applied to the surface of bioskin evenly by the fingers
  • Probe cylinder with 20-mm diameter
  • the average of 100 counts of negative force (g) was determined as the stickiness result. A lower result means that the composition becomes stickier.
  • N.A. means the test result was not available because the emulsion was not stable.
  • compositions according to the Examples which include the combination of the specific thickeners of the (a) associative polymer comprising one or more acrylic and/or methacrylic units and the (b) neutralized poly(meth)acrylic acid polymer according to the present invention, showed excellent skin sensation with regard to stickiness and watery fresh sensation, although they comprise organic UV filter at a high concentration.
  • compositions according to the Comparative Examples which do not comprise the specific combination of the (a) associative polymer comprising one or more acrylic and/or methacrylic units and the (b) neutralized poly(meth)acrylic acid polymer of the present invention 2, did not show improved watery fresh sensation.
  • the composition according to the present invention is very suitable as a cosmetic composition for caring and/or conditioning keratinous substances, such as skin, since it can provide stability as an O/W emulsion and improved skin sensation during application and good UV protecting effects due to a high concentration of organic UV filters.

Abstract

The present invention relates to an oil-in-water composition comprising: (a) at least one associative polymer comprising one or more acrylic and/or methacrylic units, (b) at least one neutralized poly(meth)acrylic acid polymer, (c) at least one organic UV filter, and (d) at least one oil..

Description

DESCRIPTION
TITLE OF INVENTION
OIL-IN-WATER EMULSION COMPOSITION
TECHNICAL FIELD
The present invention relates to an oil-in-water emulsion composition, preferably an oil-in-water skincare cosmetic composition.
BACKGROUND ART
Imparting texture to keratinous substances, such as skin, is one of the key features of cosmetic products, in particular skin cosmetic products. So far, several technologies regarding emulsion compositions or gel-like compositions which impart an improved texture have been reported.
For example, WO 2018/180316 discloses an emulsified cosmetic containing components A-E, wherein the content of component A is 0.1-1.0 mass%, the content of component B is 0.4 mass% or less, the content of component C is 0.3 mass% or less, the content of component D is 4.0 mass% or less, the mass ratio (component B/component A) of component B to component A is 0.10 or higher, the mass ratio (component C/component A) of component C to component A is 0.02 or higher, and the mass ratio (component D/component A) of component D to component A is 0.4-7.0, inclusive. Component A is (acrylate/beheneth-25 methacrylate) copolymer. Component B is carboxyvinyl polymer and/or alkyl-modified carboxyvinyl polymer.
Component C is xanthan gum. Component D is phospholipid. Component E is water.
Also, JP-A-2016-121140 discloses a gel-like cosmetic composition comprising a polyacrylic acid-based water-absorbing polymer of which the average particle diameter is 1 to 30 pm and the water absorption ratio is 5 to 50 g/g.
Also, JP-A-2019- 182841 discloses a gel like cosmetic composition in an oil-in-water form comprising components (A), (B), (C), (D), and (E), wherein the content of component (D) is 0.1 to 1.0 mass%, the content of component (B) is 0.2 to 1.2 mass%, and the mass ratio of the content of component (B) to the content of component (A) [component (B) / component (A)] is 1.0 to 15.0. Component (A) is a polymer comprising at least a structural unit derived from a (meth)acrylic acid and/or a (meth)acrylic alkyl ester and a structural unit derived from a (meth)acrylic acid polyoxyethylene alkyl ether.
Component (B) is a polymer comprising a structural unit derived from an aciyloyl dimethyl taurine acid salt.
Component (C) is one or more mono glyceryl fatty acid esters selected from the group consisting of glyceryl mono caprylate, glyceryl mono caprate, glyceryl mono laurate, glyceryl mono myristate, glyceryl mono palmitate, glyceryl mono stearate, glyceryl distearate, glyceryl mono isostearate, glyceryl diisostearate, glyceryl mono hydroxystearate, glyceryl mono oleate, glyceryl mono behenate, and glyceryl dibehenate.
Component (D) is a fatty alcohol having 12 to 24 carbon atoms.
Component (E) is water
In sun care cosmetic products, organic UV filters are widely used to impart a UV protecting property to sun care compositions. However, the use of organic UV filters may have a negative impact such as imparting oily, greasy, and sticky feelings during application. Therefore, there is a demand for sun care cosmetic compositions comprising organic UV filters, which impart an improved texture, such as a watery and fresh texture.
DISCLOSURE OF INVENTION
An objective of the present invention is to provide an oil-in-water sun care composition which can provide a watery and fresh sensation to a keratinous substance, such as skin.
The above objective of the present invention can be achieved by an oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)acrylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil.
The (a) associative polymer may further comprise one or more (meth)acrylic acid (Ci-Ci2)alkyl ester units.
The (a) associative polymer may further comprise one or more units derived from polyoxyalkylenated fatty alcohols.
The (b) neutralized poly(meth)acrylic acid polymer may be a crosslinked polymer.
The (b) neutralized poly(meth)acrylic acid polymer may be a homopolymer.
The (b) neutralized poly(meth)acrylic acid polymer may be partially neutralized.
The amount of the (a) associative polymer(s) may be 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
The amount of the (b) neutralized poly(meth)acrylic acid polymer(s) may be 0.05% by weight or more, preferably 0.1 % by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
The weight ratio of the (a) associative polymer(s) to the (b) neutralized poly(meth)acrylic acid polymer(s) in the composition may be 0.5 or more, preferably 0.8 or more, and in particular 0.9 or more, and/or may be 3 or less, preferably 2 or less, and in particular 1.5 or less.
The amount of the (c) organic UV filter(s) may be 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or may be 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition. The amount of the (d) oils(s) may be 1 % by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, and in particular 6% by weight or more, and/or may be 20% by weight or less, preferably 15% by weight or less, more preferably 12% by weight or less, and in particular 10% by weight or less, relative to the total weight of the composition.
The composition may further comprise at least one surfactant.
The surfactant may comprise a nonionic surfactant, an anionic surfactant, or a combination of a nonionic surfactant and an anionic surfactant.
The composition may further comprise water in an amount of 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, and in particular 50% by weight or more, and/or in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, and in particular 60% by weight or less, relative to the total weight of the composition.
The present invention also relates to a non-therapeutic cosmetic process for caring for and/or conditioning keratinous substances, such as skin, comprising: applying onto the keratinous substances an oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)acrylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil.
BEST MODE FOR CARRYING OUT THE INVENTION
After diligent research, the inventors have surprisingly discovered that a combination of specific thickeners of the (a) associative polymer comprising one or more acrylic and/or methacrylic units and the (b) neutralized poly(meth)aciylic acid polymer can provide improved texture, such as a less sticky and a watery and fresh sensation, to compositions even if they include organic UV filters at a high concentration, thus completing the present invention.
Thus, the composition according to the present invention is an oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)acrylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil.
Hereinafter, the composition, process, and method according to the present invention will be explained in a more detailed manner.
[Composition]
The composition may be a cosmetic composition, preferably a cosmetic composition for a keratinous substance, and more preferably a sun care cosmetic composition for a keratinous substance. The keratinous substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, lips, and the like, and in particular skin. The composition according to the present invention is an oil-in-water emulsion. The form of the composition according to the present invention is not particularly limited, as long as it is in the form of an oil-in-water emulsion, such as an aqueous gel, an aqueous solution, or the like.
The composition according to the present invention comprises (a) at least one associative polymer comprising one or more acrylic and/or methacrylic units, (b) at least one neutralized poly(meth)acrylic acid polymer, (c) at least one organic UV filter, and (d) at least one oil. The ingredients in the composition will be described in a detailed manner below.
(Associative Polymer)
The composition according to the present invention comprises (a) at least one associative polymer comprising one or more acrylic and/or methacrylic units. A single type of associative polymer may be used, but two or more different types of associative polymers may be used in combination.
For the purpose of the present invention, the term "associative polymer" or “associative copolymer” refers to polymers or copolymers that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules.
The associative polymer of the present invention is preferably an associative copolymer of one or more acrylic and/or methacrylic units and of other units.
The associative copolymer more particularly comprises at least one hydrophilic part and at least one hydrophobic part. For the puipose of the present invention, the term "hydrophobic group" means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 16 to 30 carbon atoms.
For the purpose of the present invention, the associative copolymer comprising one or more acrylic and/or methacrylic units means that the copolymer comprises at least one acrylic acid unit or at least one methacrylic acid unit or a mixture thereof. The associative copolymer may comprise further units such as units formed by an alkyl ester of acrylic acid or methacrylic acid, preferably of acrylic acid, comprising less than 6 carbon atoms: for example, a C1-C4 alkylacrylate, for example, chosen from methyl acrylate, ethyl acrylate and butyl acrylate, called hereinafter "simple ester".
In one preferred embodiment of the present invention, the associative copolymer according to the present invention comprises one or more (meth)acrylic acid (Ci-Ci2)alkyl ester units, more preferably one or more (meth)acrylic acid (Ci-C6)alkyl ester units.
According to a particular embodiment, the associative copolymer according to the present invention comprises one or more acrylic acid units. According to a further embodiment, the associative copolymer according to the present invention comprises one or more methacrylic acid units. According to another embodiment, the associative copolymer according to the present invention comprises one or more acrylic acid units and one or more methacrylic acid units.
In a particular embodiment, the associative copolymer may comprise another unit derived from another monomer that is different from (meth)acrylic acid. For example, such monomer may be esters of ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid or itaconic acid, and of polyoxyalkylenated fatty alcohols. Preferably, the fatty alcohol moiety of the ester monomer can be linear or branched, preferably linear, saturated or unsaturated, preferably saturated, (Ci2-C3o)fatty alcohol, and in particular (Ci6-C26)fatty alcohol. The polyoxyalkylene chain of the ester monomer preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, preferably from 7 to 50 and more preferably from 12 to 30.
We can mention the associative copolymer of the product sold under the commercial name: NOVETHIX L-10 POLYMER® (INCI name: ACRYLATES/BEHENETH-25 METHACRYLATE COPOLYMER) sold by LUBRIZOL, the product sold under the commercial name: Aculyn® 22 (INCI name: ACRYLATES/STEARETH-20 METHACRYLATE COPOLYMER) sold by DOW CHEMICAL, the product sold under the commercial name: Aculyn® 88 (INCI name: ACRYLATES/STEARETH-20 METHACRYLATE CROSSPOLYMER) sold by DOW CHEMICAL, the product sold under the commercial name: STRUCTURE® 2001 (INCI name: ACRYLATES/STEARETH-20 ITACONATE COPOLYMER) sold by AKZO NOBEL, and the product sold under the commercial name: STRUCTURE® 3001 (INCI name: ACRYLATES/CETETH-20 ITACONATE COPOLYMER ) sold by AKZO NOBEL
The (a) associative copolymer that can be used according to the present invention may also be chosen from anionic associative copolymers containing acrylic and/or methacrylic units.
The (meth)acrylic anionic associative copolymer that may be used according to the present invention may be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type; and at least one hydrophobic unit of a type such as a (Cio-C3o)alkyl ester of an unsaturated carboxylic acid.
More particularly, these (meth)acrylic associative copolymers are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (I) below:
Figure imgf000006_0001
in which R1 denotes H or CH3, i.e. acrylic acid or methacrylic acid units, and in which the hydrophobic unit of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (II) below:
Figure imgf000006_0002
in which R1 denotes H or CH3 (i.e. acrylate or methacrylate units), R2 denoting a C10-C30 and preferably a C12-C22 alkyl radical.
As (Cio-C3o)alkyl esters of unsaturated carboxylic acids according to formula (II), mention may more particularly be made of lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate. (Meth)acrylic associative copolymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509949.
The (meth)acrylic associative copolymer that may be used according to the present invention may more particularly denote polymers formed from a mixture of monomers comprising:
(i) acrylic acid and one or more esters of formula (III) below:
Figure imgf000007_0001
in which R3 denotes H or CH3, R4 denoting an alkyl radical having from 12 to 22 carbon atoms, and optionally a crosslinking agent, for instance those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer; or
(ii) essentially acrylic acid and lauryl methacrylate, such as the product formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.
For these embodiments of the present invention, the term “crosslinking agent" can mean a monomer containing the group
Figure imgf000007_0002
and at least one other polymerizable group, the unsaturated bonds of the monomer being unconjugated relative to each other. As the crosslinking agent that may be used according to the present invention, mention may especially be made of polyallyl ethers especially such as polyallyl sucrose and polyallylpentaerythritol.
Among the said (meth)aciylic associative copolymers above, the ones particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TRI, Pemulen TR2, Carbopol 1382, and more preferably still Pemulen TRI, and the product sold by the company S.E.P.C. under the name Coatex SX.
As the (meth)acrylic associative copolymer, mention may also be made of the copolymer of methacrylic acid/methyl acrylate/dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated alcohol sold under the name Viscophobe DB 1000 by the company Amerchol.
Other (meth)acrylic associative copolymers that may be used according to the present invention may also be sulfonic polymers comprising at least one (meth)acrylic monomer bearing sulfonic group(s), in free form or partially or totally neutralized form and comprising at least one hydrophobic portion.
The said hydrophobic portion present in the said sulfonic polymers that may be used according to the present invention preferably comprises from 8 to 22 carbon atoms, more preferably from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.
Preferentially, these sulfonic polymers that maybe used according to the present invention are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
These said sulfonic polymers generally have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000000 g/mol and even more preferably from 100000 to 1 500000 g/mol.
The sulfonic polymers that may be used according to the present invention may or may not be crosslinked. Crosslinked polymers are preferably chosen.
When they are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol diacrylatedi(meth)acrylate or tetraethylene glycol diacrylatedi(meth)acrylate, trimethylolpropane triaciylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will be used more particularly.
The degree of crosslinking will generally range from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol% relative to the polymer.
The (meth)acrylic monomers bearing sulfonic group(s) of the sulfonic polymers that may be used according to the present invention are chosen especially from (meth)acryIamido(Ci-C22)alkylsulfonic acids and N-(Ci-C22)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
(Meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-aciylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used. 2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will even more particularly be used.
The (meth)acrylic associative thickeners that may be used according to the present invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or C6-C22 di-n-alkylamine, such as those described in patent application WO 00/31154 (which forms an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acids, P-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
The (meth)acrylic associative thickeners bearing sulfonic group(s) that may particularly preferably be used according to the present invention are preferably chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion containing from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.
These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, p-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
These copolymers are described especially in patent application EP-A-750899, patent US 5 089 578 and in the following Yotaro Morishima publications:
- Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;
- Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, 2000, Vol. 33, No. 10 - 3694-3704;
- Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir, 2000, Vol. 16, No. 12, 5324-5332;
- Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221.
The ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably selected from the acrylates or acrylamides of formula (IV) below:
Figure imgf000009_0001
in which R5 and R7, which may be identical or different, denote a hydrogen atom or a linear or branched Ci-Ce alkyl radical (preferably methyl); Y denotes O or NH; R6 denotes a hydrophobic hydrocarbon-based radical containing at least 8 to 50 carbon atoms, more preferentially from 8 to 22 carbon atoms, even more preferentially from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes the number of moles of alkylene oxide and ranges from 0 to 100.
The radical R6 is preferably chosen from linear Ce-Cis alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), or branched or cyclic Ce-Cis alkyl radicals (for example cyclododecane (C12) or adamantane (C10)); Ce-Cis perfluoroalkyl radicals (for example the group of formula -(CH2)2-(CF2) -CF3); the cholesteryl radical (C27) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene. Among these radicals, the ones that are more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.
According to a particularly preferred form of the present invention, the monomer of formula (IV) comprises at least one alkylene oxide unit (x > 1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
Among these polymers, mention may be made of:
- copolymers, which may or may not be crosslinked and which may or may not be neutralized, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide units or of (C8-Ci6)alkyl (meth)acrylate units, relative to the polymer, such as those described in patent application EP-A-750 899;
- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-Ci8)alkylaciyla ide units, such as those described in patent US-5 089 578.
Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
Mention will be made of the copolymers constituted of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (V) below:
Figure imgf000010_0001
in which X+ is a proton, an alkali metal cation, an alkaline-earth metal cation or an ammonium ion; and units of formula (VI) below:
Figure imgf000010_0002
in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferentially from 7 to 25; R5 has the same meaning as that indicated above in formula (IV) and R8 denotes a linear or branched C6-C22 and more preferentially C10-C22 alkyl.
The polymers that are preferred are those for which x = 25, R5 denotes methyl and R8 represents n-dodecyl; they are described in the Morishima articles mentioned above.
Furthermore, in formula (IV), the use of the monomers where x = 20 to 25, R5 denotes methyl and R8 represents a C12-C24 alkyl group, preferably, for example, a lauryl group, myristyl group, palmityl group, stearyl group, or behenyl group is particularly preferred. Especially, the use of the monomers of the formula (IV), wherein x = 20 to 25, R5 denotes methyl and R8 represents a C16-C2 alkyl chain, such as a stearyl group, or behenyl group is particularly preferred.
The polymers for which X+ denotes sodium or ammonium are more particularly preferred.
The (a) associative polymer(s) of the present invention may be present in an amount of 0.05% by weight or more, preferably 0.1 % by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be present in an amount of 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
(Neutralized Poly(meth)aciylic Acid Polymer)
The composition according to the present invention comprises (b) at least one neutralized poly(meth)acrylic acid polymer. A single type of neutralized poly(meth)acrylic acid polymer may be used, but two or more different types of neutralized poly(meth)acrylic acid polymers may be used in combination.
The neutralized poly(meth)acrylic acid polymer of the present invention may have a water absorbing property. Therefore, the neutralized poly(meth)acrylic acid polymer can be a water absorbing polymer.
In one specific embodiment of the present invention, the neutralized poly(meth)acrylic acid polymer may have a water absorbing capacity of 10 g or more, preferably 20 g or more, and more preferably 50 g or more, and/or of 2,000 g or less, preferably 1,500 g or less, and more preferably 1,000 g or less, relative to 1 g of the polymer at 25°C and 1 atm.
The neutralized poly(meth)acrylic acid polymer may be provided in the form of particles, and preferably in the form of spherical particles. The average primary particle size as D50 of the neutralized poly(meth)acrylic acid polymer is not particularly limited, but in general is 0.1 pm or more, preferably 0.5 pm or more, and more preferably 1 pm or more, and/or is 200 pm or less, preferably 100 pm or less, more preferably 50 pm or less. The term “D50” herein means the particle size at which 50% by volume of the particles based on the total volume of the particles are smaller than or equal to D50 and 50% by volume of the particles based on the total volume of the particles are larger than D50. The D50 value can be determined by laser diffraction, for example, using a laser diffraction particle size distribution analyzer, such as Mastersizer 2000 by Malvern Corp.
The neutralized poly(meth)acrylic acid polymer may be water soluble. Therefore, the neutralized poly(meth)acrylic acid polymer may be included in a water phase of the O/W emulsion composition ofthe present invention.
The neutralized poly(meth)acrylic acid polymer of the present invention may be neutralized totally or partially. Preferably, the neutralized poly(meth)aciylic acid polymer is partially neutralized. The molar ratio of neutralized parts to un-neutralized parts is not particularly limited, but in general 10 mol% or more, 20 mol% or more, 30 mol% or more, or 40 mol% or more, and/or 90 mol% or less, 80 mol% or less, 70 mol% or less, or 60 mol% or less.
The neutralized poly(meth)acrylic acid polymer may be a homo- or copolymer. Preferably, the neutralized poly(meth)acrylic acid polymer is a homopolymer.
The neutralized poly(meth)acrylic acid polymer may be crosslinked.
In one preferred embodiment of the present invention, the neutralized poly(meth)acrylic acid polymer is a crosslinked homopolymer. Mention may in particular made of sodium polyaciylate sold under the name of AQUPEC MG N40R, which is crosslinked and partially neutralized and also called as sodium carbomer.
The (b) neutralized poly(meth)acrylic acid polymer(s) may be present in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or may be present in an amount of 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
The weight ratio of the (a) associative polymer to the (b) neutralized poly(meth)acrylic acid polymer in the composition is not particularly limited. In preferred embodiments of the present invention, the weight ratio of the (a) associative polymer to the (b) neutralized poly(meth)acrylic acid polymer in the composition is 0.5 or more, preferably 0.8 or more, and in particular 0.9 or more, and/or is 3 or less, preferably 2 or less, and in particular 1.5 or less.
(Organic UV Filter)
The composition according to the present invention may comprise at least one (c) organic UV filter. A single type of the organic UV filter may be used, but two or more different types of organic UV filters may be used in combination.
The term “UV” here means ultraviolet radiation and comprises the UV-B region (260-320 nm in wavelength) and the UV-A region (320-400 nm in wavelength). Therefore, a UV filter means any material which has filtering effects on ultraviolet radiation in wavelengths of the UV-A and/or UV-B regions.
The UV filter(s) used for the present invention may be active in the UV-A and/or UV-B region, preferably in both of the UV-A and UV-B regions alone or in combination. Therefore, the UV filter(s) used in the present invention include(s) a UV-A filter capable of absorbing UV radiation from 320 to 400 nm, a UV-B filter capable of absorbing UV radiation from 280 to 320 nm, and a UV-A and UV-B filter capable of absorbing UV radiation from 280 to 400 nm.
The organic UV filters used for the present invention can be lipophilic organic UV filters and/or hydrophilic organic UV filters. Preferably, the composition according to the present invention comprises at least one lipophilic organic UV filter, and more preferably comprises a combination of at least one lipophilic organic UV filter and at least one hydrophilic organic UV filter.
(i) Lipophilic organic UV filter
The term “lipophilic organic UV filter” here means organic UV filters which are soluble in oils at a concentration of at least 1% by weight relative to the total weight of the oils at room temperature (25°C) and atmosphere pressure (105 Pa). Therefore, the lipophilic organic UV filter(s) is(are) present in the oily phase of the present invention.
The lipophilic organic UV-A filters used in the present invention may include, but are not limited to, aminobenzophenone compounds, dibenzoylmethane compounds, anthranilic acid compounds, and 4,4-diaiylbutadiene compounds.
As the aminobenzophenone compounds, mention may be made of n-hexyl 2-(4-diethlamino-2-hydroxybenzoyl)benzoate, the alternative name of which is diethylamino hydroxybenzoyl hexyl benzoate (DHHB), sold under the trade name “Uvinul A+” from BASF.
As the dibenzoylmethane compounds, mention may be made of 4-isopropyldibenzoylmethane, sold under the name of “Eusolex 8020” from Merck, l-(4-methoxy-l-benzofuran-5-yl)-3-phenylpropane-l, 3-dione, sold under the name of “Pongamol” from Quest, l-(4-(tert-butyl)phenyl)-3-(2-hydroxyphenyl)propane- 1,3-dione, and butyl methoxydibenzoylmethane, sold under the trade name “Parsol 1789” from Hoffrnann-La Roche.
As the anthranilic acid compounds, mention may be made of menthyl anthranilate marketed under the name "NEO HELIPAN MA" by Symrise.
As the 4,4-diarylbutadiene compounds, mention maybe made of 1,1 -dicarboxy (2,2'-dimethylpropyl)-4,4-diphenylbutadiene and diphenyl butadiene malonates and malononitriles.
The lipophilic organic UV-B filters used in the present invention may include, but are not limited to, triazine compounds, para-aminobenzoic acid compounds, salicylic compounds, cinnamate compounds, P,P-diphenylacrylate compounds, benzylidenecamphor compounds, phenylbenzimidazole compounds, imidazoline compounds, benzalmalonate compounds, and merocyanine compounds.
As the triazine compounds, mention may be made of ethylhexyl triazone, marketed under the name “UVINUL T- 150” by BASF, diethylhexyl butamido triazone, marketed under the name “UVASORB HEB” by SIGMA 2V, 2,4,6-tris(dineopentyl 4’-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4 ’ -aminobenzahnalonate)-s-triazine, 2,4-bis(dineopentyl 4’-aminobenzalmalonate)-6-(n-butyl 4’-aminobenzoate)-s-triazine, 2,4-bis(n-butyl 4 ’ -aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine.
As the para-aminobenzoic acid derivatives, mention may be made of para-aminobenzoates (PABA), for example, ethyl PABA (para-aminobenzoate), ethyl dihydroxypropyl PABA, and ethylhexyl dimethyl PABA, marketed under the name “ESCALOL 5972 from ISP.
As the salicylic compounds, mention may be made of homosalate, marketed under the name “Eusolex HMS” by Rona/EM industries, and ethylhexyl salicylate, marketed under the name “NEO HELIOPAN OS” by Symrise.
As the cinnamate compounds, mention may be made of ethylhexyl methoxycinnamate, marketed under the name “PARSOL CX” by DSM NUTRITIONAL PRODUCTS, isopropyl ethoxy cinnamate, isoamyl methoxy cinnamate, marketed under the name “NEO HELIOPAN E 1000” by Symrise, diisopropyl methylcinnamate, cinoxate, and glyceryl ethylhexanoate dimethoxycinnamate.
As the P,|3-diphenylacrylate compounds, mention may be made of octocrylene, marketed under the name “UVINUL N539” by BASF, and etocrylene, marketed under the name “UVENUL N35” by BASF.
As the benzylidenecamphor compounds, mention may be made of 3-benzylidene camphor, marketed under the name “MEXORYL SD” from CHIMEX, methylbenzylidene camphor, marketed under the name “EUSOLEX 6300” by MERCK, polyacrylamidomethyl benzylidene Camphor, marketed under the name “MEXORYL SW” by CHIMEX, and terephthalylidene dicamphor sulfonic acid, marketed under the name “Mexoryl SX” by Chimex.
As the phenylbenzimidazole compounds, mention may be made of phenylbenzimidazole sulfonic acid, marketed under the name “Eusolex 232” by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, marketed under the name “Neo Heliopan AP” by Haarmann and Reimer.
As the imidazoline compounds, mention may be made of ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
As the benzalmalonate compounds, mention may be made of polyorgandsiloxane containing a benzabnalonate moiety, for example, Polysilicone- 15, marketed under the name “Parsol SLX” by DSM NUTRITIONAL PRODUCTS, and di-neopentyl 4'-methoxybenzalmalonate.
The lipophilic organic UV filters of the present invention may comprise lipophilic UV-A and UV-B filters. The following are non-limited examples of the lipophilic organic UV-A and UV-B filters:
- Benzophenone compounds, such as benzophenone- 1 marketed under the name “UVINUL 400” by BASF, benzophenone-2 marketed under the name “UVINUL 500” by BASF, benzophenone-3 or oxybenzone marketed under the name “UVINUL M40” by BASF, benzophenone-6 marketed under the name “Helisorb 11” by Norquay, benzophenone-8 marketed under the name “Spectra-Sorb UV-24” by American Cyanamid, benzophenone- 10, benzophenone-11, and benzophenone-12;
- benzotriazole compounds such as drometrizole trisiloxane marketed under the name “Silatrizole” by Rhodia Chimie and bumetrizole marketed under the name “TINOGUARTD AS” by CIBA-GEIGY, and 2,2'-Methylenebis[6-(2H-Benzotriazol-2-yl)-4-(l,l,3,3-Tetramethyl-Butyi) Phenol] (Methylene Bis-Benzotriazolyl Tetramethylbutylphenol) marketed as “TINOSORB M” by BASF;
- bis-resorcinyl triazine compounds, such as bis-ethylhexyloxyphenol methoxyphenyl triazine marketed under the name “TINOSORB S” by CIBA-GEIGY; and
- benzoxazole compounds, such as 2,4-bis[5-(l -dimethylpropyl) benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-l,3,5-triazine marketed under the name “Uvasorb K2A” by Sigma 3V Preferably, the lipophilic organic UV filter of the present invention is selected from a combination of at least one lipophilic organic UV-A filter and at least one lipophilic organic UV-B filter.
In one embodiment of the present invention, the lipophilic organic UV filter(s) may be present in the composition in an amount of 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or may be present in an amount of 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition.
(ii) Hydrophilic organic UV filter
The term “hydrophilic organic UV filter” here means organic UV filters which are soluble in water at a concentration of at least 1% by weight relative to the total weight of the water at room temperature (25°C) and atmosphere pressure (105 Pa). Therefore, the hydrophilic organic UV filter(s) is(are) present in the aqueous phase of the present invention.
The hydrophilic organic UV-A filter includes, but is not limited to:
Terephthalylidene Dicamphor Sulfonic Acid and salts thereof, such as that manufactured under the name “Mexoryl SX” by Chimex,
Bisbenzoxazolyl derivatives, such as described in Patent, EP 669323 and US 2,463,264, more particularly the compound Disodium Phenyl Dibenzimidazole Tetrasulfonate and salts thereof, sold under the trade name “Neo Heliopan AP” by Haarmann and Reimer.
The hydrophilic organic UV-B filter includes, but is not limited to: p-Aminobenzoic (PABA) derivatives, such as PABA, Glyceryl PABA and PEG-25 PABA, and salts thereof such as sold under the name “Uvinul P25” by BASF, Phenylbenzimidazole Sulfonic Acid and salts thereof, such as sold in particular under the trade name “Eusolex 232” by Merck, Ferulic Acid and salts thereof,
Salicylic Acid and salts thereof,
DEA methoxycinnamate and salts thereof,
Benzylidene Camphor Sulfonic Acid and salts thereof, such as that manufactured under the name “Mexoryl SL” by Chimex,
Camphor Benzalkonium Methosulfate and salts thereof, such as that manufactured under the name “Mexoryl SO” by Chimex.
The hydrophilic organic UV-A and UV-B filter includes, but is not limited to: Benzophenone-4 and salts thereof, such as those sold under the trade name “Uvinul MS40” by BASF,
Benzophenone-5 and salts thereof, and Benzophenone-9 and salts thereof.
The salts of the compounds that may be used are chosen in particular from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; salts of ammonium of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts. Salts chosen from sodium, potassium, magnesium, strontium, copper, manganese or zinc salts are preferably used. The sodium salt is preferentially used.
In one embodiment of the present invention, the hydrophilic organic UV filter(s) may be present in the composition in an amount of 0.1% by weight or more, more preferably 0.5% by weight or more, even more preferably 1 % by weight or more, and in particular 2% by weight or more, and/or may be present in an amount of 7% by weight or less, preferably 5% by weight or less, and in particular 4% by weight or less, relative to the total weight of the composition.
The (c) organic UV filter(s) may be present in an amount of 3% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or may be present in an amount of 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition.
(Oil)
The composition according to the present invention may comprise at least one oil. If two or more oils are used, they may be the same or different.
Here, “oil” means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile. Preferably the oil is different from the UV filter.
The oil can form the oily phase of the O/W emulsion of the composition according to the present invention. Therefore, the oil phase of the composition includes the oil.
The oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof.
The oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.
As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, com oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.
As examples of animal oils, mention may be made of, for example, squalene and squalane.
As examples of synthetic oils, mention may be made of alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.
The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C1-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present invention are derived is branched. Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.
Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols, and esters of monocarboxylic, dicarboxylic, or tricarboxylic acids and of non-sugar C4-C26 dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols may also be used.
Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.
As ester oils, one can use sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term “sugar” means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.
Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.
The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters, and polyesters, and mixtures thereof.
These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, and arachidonates, or mixtures thereof such as, especially, oleopahnitate, oleostearate, and pahnitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.
More particularly, use is made of monoesters and diesters and especially sucrose, glucose, or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearates.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.
As examples of ether oils, mention may be made of, for example, ether oils with a short hydrocarbon chain or chains, such as dicaprylyl ether.
As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate), and glyceryl tri(caprate/caprylate/linolenate).
As examples of silicone oils, mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.
Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.
These silicone oils may also be organomodified. The organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
Organopolysiloxanes are defined in greater detail in Walter Noll’s Chemistry and Technology of Silicones ( 1968), Academic Press. They may be volatile or non-volatile.
When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C.
Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.
Among these polydialkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:
- the Silbione® oils of the 47 and 70047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500000;
- the oils of the Mirasil® series sold by the company Rhodia;
- the oils of the 200 series from the company Dow Coming, such as DC200 with a viscosity of 60 000 mm2/s; and
- the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
Mention may also be made of polydimethylsiloxanes containing dimethyl silanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.
Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.
Examples that may be mentioned include the products sold under the following names:
- the Silbione® oils of the 70641 series from Rhodia;
- the oils of the Rhodorsil® 70633 and 763 series from Rhodia;
- the oil Dow Coming 556 Cosmetic Grade Fluid from Dow Coming;
- the silicones of the PK series from Bayer, such as the product PK20;
- certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250, and SF 1265.
As the phenyl silicone oil, phenyl trimethicone is preferable.
The organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.
Hydrocarbon oils may be chosen from:
- linear or branched, optionally cyclic, C5-C16 lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane, and isodecane; and
- linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.
As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.
The term “fatty” in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.
The fatty alcohol may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be chosen from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.
As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.
It is preferable that the fatty alcohol be a saturated fatty alcohol. Thus, the fatty alcohol may be selected from straight or branched, saturated or unsaturated C6-C30 alcohols, preferably straight or branched, saturated C6-C30 alcohols, and more preferably straight or branched, saturated C12-C20 alcohols.
The term “saturated fatty alcohol” here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C6-C30 fatty alcohols. Among the linear or branched, saturated C6-C30 fatty alcohols, linear or branched, saturated C12-C20 fatty alcohols may preferably be used. Any linear or branched, saturated C16-C20 fatty alcohols may be more preferably used. Branched C16-C20 fatty alcohols may be even more preferably used.
As examples of saturated fatty alcohols, mention maybe made of lauryl alcohol, cetyl alcohol, steaiyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as a saturated fatty alcohol.
The (d) oil(s) may be present in an amount of 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, and in particular 6% by weight or more, and/or may be present in an amount of 20% by weight or less, preferably 15% by weight or less, more preferably 12% by weight or less, and in particular 10% by weight or less, relative to the total weight of the composition.
(Water)
The composition according to the present invention may comprise water. The water can form the water phase of the O/W emulsion of the present invention. Therefore, the water phase of the composition may comprise water.
The water may be present in an amount of 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, and in particular 50% by weight or more, and/or may be present in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, and in particular 60% by weight or less, relative to the total weight of the composition.
(Surfactant)
The composition according to the present invention may comprise at least one surfactant chosen from amphoteric, anionic, cationic, or nonionic surfactants, used alone or as a mixture. Preferably, the composition comprises at least one nonionic surfactant. Preferably, the composition comprises at least one anionic surfactant. Preferably, the composition comprises a combination of at least one nonionic surfactant and at least one anionic surfactant.
Examples of nonionic surfactants usable in the compositions of the present invention may include polyethoxylated fatty alcohols or polyglycerolated fatty alcohols, such as the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene units (Laureth-9 to Laureth-50 as the INCI names), in particular Laureth-9; esters of polyols and of a fatty acid possessing a saturated or unsaturated chain comprising, for example, from 8 to 24 carbon atoms, and their oxyalkylenated derivatives, that is to say comprising oxyethylene and/or oxypropylene units, such as esters of glycerol and of a C8-C24 fatty acid, and their oxyalkylenated derivatives, in particular polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), for example PEG-20 glyceryl triisostearate; esters of sugar and of a C8-C24 fatty acid and their oxyalkylenated derivatives, such as polyethoxylated sorbitol esters of C8-C24 fatty acids, in particular Polysorbate 80, such as the product marketed under the name “TWEEN 80” by Croda; ethers of a sugar and of C8-C24 fatty alcohols, such as caprylyl/capryl glucoside; hydrophobized polysaccharides; polyoxyethylene alkyl ethers; polyoxyethylene oxypropylene alkyl ethers; fatty acid alkanol amides; alkyl amine oxides; alkyl polyglycosides and silicone surfactants, such as polydimethylsiloxane containing oxyethylene groups and/or oxypropylene groups, for example, PEG- 10 dimethicone, bis-PEG/PPG-14/14 dimethicone, bis-PEG/PPG-20/20 dimethicone, and PEG/PPG-20/6 dimethicone; and polyglyceryl fatty acid ester such as polyglyceryl-4 caprate, polyglyceryl- 10 laurate, polyglyceryl-6 dicaprate, polyglyceryl-6 dicaprate, polyglyceryl-6 dioleate, polyglyceryl-6 caprylate, polyglyceryl-2 oleate, and polyglyceryl-6 polyricinoleate; and mixtures thereof. In addition, mention can be made of alkylpolyglycosides as nonionic surfactants, represented by the following general formula (1):
R-O-(G)X(1) in which R represents a branched and/or unsaturated alkyl radical comprising from 14 to 24 carbon atoms, G represents a reduced sugar comprising 5 or 6 carbon atoms and x denotes a value ranging from 1 to 10 and preferably from 1 to 4, and G in particular denotes glucose, fructose or galactose. Mention may be made, as alkyl polyglycosides of this type, of alkyl polyglucosides (G = glucose in the formula (I)) and in particular the compounds of formula (I) in which R more particularly represents an oleyl radical (unsaturated Cis radical) or isostearyl (saturated Cis radical), G denotes glucose and x is a value ranging from 1 to 2, in particular isostearyl glucoside, oleyl glucoside and their mixtures. This alkyl polyglucoside can be used as a mixture with a coemulsifier, more especially with a fatty alcohol and in particular a fatty alcohol having the same fatty chain as that of the alkyl polyglucoside, that is to say comprising from 14 to 24 carbon atoms and having a branched and/or unsaturated chain, for example isostearyl alcohol when the alkyl polyglucoside is isostearyl glucoside and oleyl alcohol when the alkyl polyglucoside is oleyl glucoside.
In addition, it is particularly advantageous, according to the present invention, to use together a fatty alcohol and an alkylpolyglycoside of which the alkyl part is identical to that of the selected fatty alcohol. Among the fatty alcohol/alkylpolyglycoside mixtures that are particularly preferred, mention may be made of the products sold by the company SEPPIC under the name
Montano v®, such as the following mixtures:
- cetylstearyl alcohol/cocoyl glucoside (Montanov 82®),
- arachidyl alcohol and behenyl alcohol/arachidyl glucoside (Montanov 802®),
- myristyl alcohol/myristyl glucoside (Montanov 14®), - cetearyl alcohol/cetearyl glucoside (Montanov 68®),
- C14-C22 alcohol Ci2-C2o alkyl glucoside (Montanov L®),
- cocoyl alcohol/cocoyl glucoside (Montanov S®) and
- isostearyl alcohol/isostearyl glucoside (Montanov WO 18®). In the hydrophobized polysaccharides, the polysaccharide may be selected from polyglucose or polyfructose. Preferred polyglucoses are selected from cellulose, methyl cellulose, hydroxyethyl cellulose, amylose, amylopectin and dextrin. A preferred polyfructose is inulin. In one preferred embodiment of the present invention, the hydrophobized polysaccharide as the nonionic surfactant is hydrophobized inulin. In the hydrophobized polysaccharides, the hydrophobic chains which can be connected or grafted onto the main chain of the polysaccharides may in particular be linear or branched, saturated or unsaturated hydrocarbon chains having 1 to 50 carbon atoms, such as alkyl, arylalkyl, alkylaryl and alkylene groups, divalent cycloaliphatic groups, or organopolysiloxane chains. These hydrocarbon or organopolysiloxane chains may in particular comprise one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea and/or sulphonamide functions. In particular, illustrative and non-limitative instances of hydrophobized inulins that can be used in the compositions according to the present invention include stearoyl inulin, such as those sold under the names Lifidrem INST by Engelhard and Rheopearl INS by Ciba; palmitoyl inulin; undecylenoyl inulin, such as those sold under the names Lifidrem INUK and Lifidrem INUM by Engelhard; and inulin laurylcarbamate, such as that sold under the name Inutec SP1 by Orafti.
Examples of anionic surfactants usable in the compositions of the present invention may include alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl ether sulfonates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alpha-olefin sulfonates, beta alkyloxy alkene sulfonates, alkyl arylsulfonates, alkyl carbonates, succinamates, sulfosuccinates, sarcosinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, sulfated monoglycerides, fatty acid amino polyoxyethylene sulfates, isethionates, alkyl benzene sulfonic acids, polyoxyethylene alkyl ether sulfuric acids, polyoxyethylene alkyl ether carboxylic acids, and polyoxyethylene alkyl amide ether carboxylic acids, and salts thereof.
It is preferable that the anionic surfactant be selected from the group consisting of (C6-C3o)alkyl sulfates, (Ce-C3o)alkyl ether sulfates, (C6-C o)alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; (C6-C3o)alkylsulfonates, (C6-C3o)alkylamide sulfonates, (Ce-C3o)alkylaryl sulfonates, a-olefin sulfonates, paraffin sulfonates; (C6-C3o)alkyl phosphates; (Cg-C3o)alkyl sulfosuccinates, (C6-C3o)alkyl ether sulfosuccinates, (C6-C3o)alkylamide sulfosuccinates; (C6-C3o)alkyl sulfoacetates; (C6-C24)acyl sarcosinates; (Ce-C24)acyl glutamates; (C6-C3o)alkylpolyglycoside carboxylic ethers; (C6-C3o)alkylpolyglycoside sulfosuccinates; (C6-C3o)alkyl sulfosuccinamates; (Ce-C24)acyl isethionates; N-(Ce-C24)acyl taurates; C6-C30 fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (Cs-C2o)acyl lactylates; (C6-C3o)alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (C6-C3o)alkyl ether carboxylic acid salts; polyoxyalkylenated (C6-C3o)alkylaryl ether carboxylic acid salts; and polyoxyalkylenated (C6-C3o)alkylamido ether carboxylic acid salts; and corresponding acid forms.
Tn at least one embodiment, the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form.
It is more preferable that the anionic surfactant be selected from salts of (Ce-C24)acyl glutamates, (C6-C3o)alkyl sulfate, (C6-C3o)alkyl ether sulfates or polyoxyalkylenated (Ce-C3o)alkyl ether carboxylic acid, that may or may not be salified. In particular, the anionic surfactant may be selected from sodium salt of (Ce-C24)acyl glutamates, such as sodium stearoyl glutamate.
The nonionic surfactant(s) may be present in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, even more preferably 1.3% by weight or more, and in particular 1.5% by weight or more, and/or may be present in an amount of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, and in particular 3% by weight or less, relative to the total weight of the composition. The anionic surfactant(s) may be present in an amount of 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, even more preferably 0.2% by weight or more, and in particular 0.25% by weight or more, and/or may be present in an amount of 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
The surfactant(s) may be present in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, even more preferably 1.5% by weight or more, and in particular 1.7% by weight or more, and/or may be present in an amount of 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and in particular 3% by weight or less, relative to the total weight of the composition.
(Thickener)
The composition according to the present invention may comprise at least one thickener, which is different from the components (a) and (b) of the present invention. Two or more thickeners can be combined. The thickener may be hydrophilic or lipophilic, and preferably lipophilic.
The lipophilic thickener may be in the form of polymer.
The lipophilic polymer thickener may be chosen from carboxyvinyl polymers such as the Carbopol products (carbomers) and the Pemulen products (acrylate/C10-C30-alkyl acrylate copolymer) or polymers having the INCI name "Poly C10-30 Alkyl Acrylate", such as the Intelimer® products from Air Products, such as the product Intelimer® IPA 13-1, which is a polystearyl acrylate, or the product 30 Intelimer® IPA 13-6 which is a behenyl polymer.
The amount of the thickener(s) in the composition may be from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, and more preferably from 0.3 to 3% by weight, relative to the total weight of the composition.
(Hydrophilic Organic Solvent)
The composition according to the present invention may comprise at least one cosmetically acceptable hydrophilic organic solvent.
The term “hydrophilic” here means substances having a solubility of at least 1 g/L, preferably at least 10 g/L, and more preferably at least 100 g/L, in water at room temperature (25°C) and atmospheric pressure (105 Pa). Therefore, the cosmetically acceptable hydrophilic organic solvent is included in the water phase, if present.
The cosmetically acceptable hydrophilic organic solvent(s) may include, for example, substantially linear or branched lower mono-alcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerine, propanediol, pentylene glycol, caprylyl glycol, sorbitol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol ethers, propylene glycol monomethylether, diethylene glycol alkyl ethers, such as diethylene glycol monoethylether or monobutylether; polyethylene glycols, such as PEG-4, PEG-6, PEG-8, PEG- 10, and PEG-20, and their derivatives, and a combination thereof. The amount of the cosmetically acceptable hydrophilic organic solvent(s) in the composition according to the present invention may be from 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and in particular 7% by weight or more, and/or may be 30% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less, relative to the total weight of the composition.
(Filler)
The composition according to the present invention may comprise at least one filler. Two or more fillers can be combined. The filler can be inorganic or organic. The filler also can be silicone powder.
As the inorganic filler, mention may be made of talc, mica, silica, hollow silica, magnesium aluminum silicate, trimethyl siloxysilicate or silica silylate, kaolin, bentone, calcium carbonate, magnesium hydrogen carbonate, hydroxyapatite, boron nitride, fluorphlogopite, sericite, calcinated talc, calcinated mica, calcinated sericite, synthetic mica, perlite, lauroyl lysine, metal soap, bismuth oxychloride, barium sulfate, magnesium carbonate, and mixtures thereof, optionally hydrophilic- or hydrophobic-treated.
As the organic filler, mention may be made of acrylic polymer powders, silicone powders, wax powders, polyamide powders, urethane polymer powders, tetrafluoroethylene polymer powders, polyacrylonitrile powders, poly-0-alanine powders, polyethylene powders, polytetrafluoroethylene powders, lauroyllysine, starch, cellulose powder, tetrafluoroethylene polymer powders and mixtures thereof.
As the silicone powders, mention may be made of organopolysilsesquioxane powders, organopolysiloxane powders, and silicone resin powders.
The amount of the filler(s) in the composition may be 0.1% by weight or more, preferably 0.5%> by weight or more, and more preferably 1% by weight or more, and 15% by weight or less, preferably 10% by weight or less, and more preferably 5%> by weight or less, relative to the total weight of the composition.
(pH Adjusting Agent)
The pH of the composition according to the present invention may be adjusted to the desired value using at least one pH adjusting agent, such as an acidifying or a basifying agent, for example, which are commonly used in cosmetic products.
The pH of the composition according to the present invention may be 8.0 or less, preferably 7.0 or less, more preferably 6.0 or less, even more preferably 5.0 or less, and in particular 4.5 or less, and/or may be 2.5 or more, preferably 3.0 or more, more preferably 3.5 or more, and in particular 4.0 or more at 25°C.
Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, ortho-phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, and lactic acid, and sulfonic acids.
Among the basifying agents, mention may be made, by way of example, of hydroxides of an alkali metal or an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide; quaternary ammonium hydroxides and guanidinium hydroxide; alkali metal silicates, such as sodium metasilicates; amino acids, preferably basic amino acids, such as arginine, lysine, ornithine, citrulline and histidine; carbonates and bicarbonates; organic alkaline agents, for example, alkanolamines such as mono-, di- and tri-ethanolamine, and isopropanolamine; urea, guanidine and their derivatives; and the compounds of the following formula:
Figure imgf000025_0001
in which
W is a Ci-C6 alkylene residue optionally substituted with a hydroxyl group or a Ci-Ce alkyl group; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a Ci-Ce alkyl, Ci-C6 hydroxyalkyl or Ci-Ce aminoalkyl group. Mention may especially be made of 1,3-diaminopropane, l,3-diamino-2-propanol, spermine and spermidine.
The pH adjusting agent(s) may be used in an amount ranging from 0.001 % to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.
(Adjuvants)
The composition according to the present invention may also comprise any adjuvant(s) usually used in the field of cosmetics, chosen, for example, from hydrophobic organic solvents, gums, resins, antioxidants, such as tocopherol, buffers, preserving agents, such as phenoxyethanol, co-preservatives, opacifying agents, fragrances, neutralizers, antiseptics, UV-screening agents, stabilizers or electrolyte, sequestering agents, such as trisodium ethylenediamine disuccinate, dispersing agents, buffers, dyes and/or pigments, emollients or collagen-protecting agents, and mixtures thereof.
The adjuvants may be present in the composition of the present invention in an amount ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 0.5% to 10% by weight, relative to the total weight of the composition.
The composition according to the present invention can be prepared by mixing the above-described essential and optional ingredients in a conventional manner. It is possible to further comprise mixing any of the optional ingredients and heating the composition until an ingredient is dissolved.
[Cosmetic Process and Method]
The present invention also relates to a non-therapeutic method or process, preferably a cosmetic method or process, and more preferably a cosmetic method or process for caring for and/or conditioning keratinous substances, such as skin, scalp, and lips, in particular skin, comprising: applying onto the keratinous substance an oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)acrylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil. The present invention also relates to a non-therapeutic method or process, preferably a cosmetic method or process, and more preferably a cosmetic method or process for caring for and/or conditioning keratinous substances, such as skin, scalp, and lips, in particular skin, comprising: applying onto the keratinous substance an oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)acrylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil.
The same explanations for the composition, the (a) associative polymer comprising one or more acrylic and/or methacrylic units, the (b) neutralized poly(meth)acrylic acid polymer, the (c) organic UV filter, and the (d) oil in the composition according to the present invention above can be applied to the composition, the (a) associative polymer comprising one or more acrylic and/or methacrylic units, the (b) neutralized poly(meth)acrylic acid polymer, the (c) organic UV filter, and the (d) oil for the method and process according to the present inventions. The composition used in the process and method according to the present invention may include any of the optional ingredients as explained above for the composition according to the present invention.
EXAMPLES
The present invention will be described in more detail by way of examples which however should not be construed as limiting the scope of the present invention.
[Compositions]
Homogeneous solution compositions according to the Examples and Comparative Examples were prepared by mixing the ingredients as listed in Tables 1 and 2. Specifically, in a first step, water and the ingredients in a water phase, i.e. water-soluble and water-dispersible ingredients, were mixed in water and the mixture was heated to 75 °C to obtain a homogenous water phase. The oils and ingredients in an oily phase, i.e. oil-soluble and oil-dispersible ingredients, were mixed in the oils and the mixture was heated to 75 °C to obtain a homogenous oily phase. The obtained oily phase was added to the water phase and they were homogenized at 8,000 rpm for 10 minutes at 75°C. The mixture was then cooled to less than 45°C. Acrylates/beheneth-25 methacrylate copolymer, sodium Polyacrylate, carbomer, and/or ammonium acryloyldimethyltaurate/VP copolymer were added and homogenized at 8,000 rpm for 10 minutes. Finally, triethanolamine or potassium hydroxide was added and homogenized at 7,000 rpm for 5 minutes to obtain emulsion compositions. The numerical values for the amounts of the ingredients shown in Tables 1 and 2 are all based on “% by weight” as active raw materials.
Table 1
Figure imgf000027_0001
Table 2
Figure imgf000028_0001
[Evaluation]
(Stability)
50 g of each of the obtained emulsion compositions was put into a 50 ml glass bottle and it was kept at 55°C for one week in an incubator. The appearance of each sample was then observed with the naked eye after they were cooled to room temperature. Stability property was evaluated for each composition under the following criteria.
Good: Emulsion form was not changed
Bad: Oil leakage and/or creaming was observed
(Stickiness Analysis)
The stickiness of each composition was measured by using Texture Analyzer TA.XT plus (Stable Micro Systems) with a 20-mm cylinder made of aluminum (P/20). The measurement conditions were as follows.
Test mode: Compression
Substrate: 30 mm x 30 mm flat bioskin
Sample: 20 mg of composition which was applied to the surface of bioskin evenly by the fingers
Probe: cylinder with 20-mm diameter
Test Speed: 0.1 mm /s
Distance: 2 mm
Force: 150 g
Count: 100 times
The average of 100 counts of negative force (g) was determined as the stickiness result. A lower result means that the composition becomes stickier.
(Sensory Test)
30 mg of each of the compositions was applied on and around a 30 mm x 30 mm area of a panel member’s forearm (n=5) with the fingers. Stickiness and watery fresh sensation were evaluated for each composition under the following criteria.
- Stickiness
1: Sticky
2: Rather sticky
3 : It is not able to say whether it is sticky or not.
4: Rather not sticky
5: Not sticky at all
- Watery Fresh Sensation
1 : Not watery fresh at all
2 : Rather not watery fresh
3 : It is not able to say whether it is watery fresh or not
4: Rather watery fresh
5: Watery fresh
The results are shown in Table 3 below. The results of the sensory tests were represented with average scores of the panel members. Table 3
Figure imgf000030_0001
N.A. means the test result was not available because the emulsion was not stable.
As can be seen from Table 3, the compositions according to the Examples, which include the combination of the specific thickeners of the (a) associative polymer comprising one or more acrylic and/or methacrylic units and the (b) neutralized poly(meth)acrylic acid polymer according to the present invention, showed excellent skin sensation with regard to stickiness and watery fresh sensation, although they comprise organic UV filter at a high concentration.
On the other hand, the compositions according to the Comparative Examples, which do not comprise the specific combination of the (a) associative polymer comprising one or more acrylic and/or methacrylic units and the (b) neutralized poly(meth)acrylic acid polymer of the present invention 2, did not show improved watery fresh sensation. In addition, the compositions according to Comparative Examples 3, 5, 7, and 8, which did not include a sufficient quantity of thickeners, could not show stability as an emulsion.
Accordingly, it can be concluded that the composition according to the present invention is very suitable as a cosmetic composition for caring and/or conditioning keratinous substances, such as skin, since it can provide stability as an O/W emulsion and improved skin sensation during application and good UV protecting effects due to a high concentration of organic UV filters.

Claims

1. An oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)aciylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil.
2. The composition according to Claim 1, wherein the (a) associative polymer further comprises one or more (meth)aciylic acid (Ci -Ci2)alkyl ester units.
3. The composition according to Claim 1 or 2, wherein the (a) associative polymer further comprises one or more units derived from polyoxyalkylenated fatty alcohols.
4. The composition according to any one of the preceding claims, wherein the (b) neutralized poly(meth)acrylic acid polymer is a crosslinked polymer.
5. The composition according to any one of the preceding claims, wherein the (b) neutralized poly(meth)acrylic acid polymer is a homopolymer.
6. The composition according to any one of the preceding claims, wherein the (b) neutralized poly(meth)acrylic acid polymer is partially neutralized.
7. The composition according to any one of the preceding claims, wherein the amount of the (a) associative polymer(s) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or is 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition.
8. The composition according to any one of the preceding claims, wherein the amount of the (b) neutralized poly(meth)acrylic acid polymer(s) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more, and in particular 0.2% by weight or more, and/or is 3% by weight or less, preferably 2% by weight or less, more preferably 1 % by weight or less, and in particular 0.5% by weight or less, relative to the total weight of the composition. . The composition according to any one of the preceding claims, wherein the weight ratio of the (a) associative polymer(s) to the (b) neutralized poly(meth)aciylic acid polymer(s) in the composition is 0.5 or more, preferably 0.8 or more, and in particular 0.
9 or more, and/or is 3 or less, preferably 2 or less, and in particular 1.5 or less.
10. The composition according to any one of the preceding claims, wherein the amount of the (c) organic UV filter(s) is 3 % by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and in particular 20% by weight or more, and/or is 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less, and in particular 25% by weight or less, relative to the total weight of the composition.
11. The composition according to any one of the preceding claims, wherein the amount of the (d) oils(s) is 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, and in particular 6% by weight or more, and/or is 20% by weight or less, preferably 15% by weight or less, more preferably 12% by weight or less, and in particular 10% by weight or less, relative to the total weight of the composition.
12. The composition according to any one of the preceding claims, wherein the composition further comprises at least one surfactant.
13. The composition according to claim 12, wherein the surfactant comprises a nonionic surfactant, an anionic surfactant, or a combination of a nonionic surfactant and an anionic surfactant.
14. The composition according to any one of the preceding claims, wherein the composition further comprises water in an amount of 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, and in particular 50% by weight or more, and/or in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, and in particular 60% by weight or less, relative to the total weight of the composition.
15. A non-therapeutic cosmetic process for caring for and/or conditioning keratinous substances, such as skin, comprising: applying onto the keratinous substances an oil-in-water composition comprising:
(a) at least one associative polymer comprising one or more acrylic and/or methacrylic units,
(b) at least one neutralized poly(meth)acrylic acid polymer,
(c) at least one organic UV filter, and
(d) at least one oil.
PCT/JP2021/045428 2020-12-07 2021-12-03 Oil-in-water emulsion composition WO2022124385A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2020202537A JP2022090264A (en) 2020-12-07 2020-12-07 Oil-in-water emulsion composition
JP2020-202537 2020-12-07
FR2100245A FR3118702B1 (en) 2021-01-12 2021-01-12 Oil-in-water emulsion composition
FR2100245 2021-01-12

Publications (1)

Publication Number Publication Date
WO2022124385A1 true WO2022124385A1 (en) 2022-06-16

Family

ID=79170824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/045428 WO2022124385A1 (en) 2020-12-07 2021-12-03 Oil-in-water emulsion composition

Country Status (1)

Country Link
WO (1) WO2022124385A1 (en)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
US3915921A (en) 1974-07-02 1975-10-28 Goodrich Co B F Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers
US4509949A (en) 1983-06-13 1985-04-09 The B. F. Goodrich Company Water thickening agents consisting of copolymers of crosslinked acrylic acids and esters
US5089578A (en) 1986-03-28 1992-02-18 Exxon Research And Engineering Company Hydrophobically associating terpolymers containing sulfonate functionality
EP0669323A1 (en) 1994-02-24 1995-08-30 Haarmann & Reimer Gmbh Utilization of benzazols as UV-absorbers, new benzazoles and process for their preparation
EP0750899A2 (en) 1995-06-30 1997-01-02 Shiseido Company Limited An emulsifier or solubilizer which consists of a water soluble amphiphilic polyelectrolyte, and an emulsified composition or a solubilized composition and an emulsified cosmetic or a solubilized cosmetic containing it
WO2000031154A1 (en) 1998-11-23 2000-06-02 Sofitech N.V. Invertible emulsions stabilised by amphiphilic polymers and application to bore fluids
US20070178057A1 (en) * 2006-02-01 2007-08-02 Amcol International Corporation High efficiency sunscreen composition particularly useful for wipes and sprays
EP2266531A1 (en) * 2009-06-24 2010-12-29 L'Oréal Cosmetic composition comprising a superabsorbent polymer and an organic UV filter
WO2012059348A1 (en) * 2010-11-05 2012-05-10 L'oreal Fluid aqueous antisun composition based on a superabsorbent polymer and a crosslinked copolymer of methacrylic acid and of a c1-c4 alkyl acrylate
JP2016121140A (en) 2014-12-24 2016-07-07 日光ケミカルズ株式会社 Gel-like cosmetic
WO2016198581A1 (en) * 2015-06-11 2016-12-15 L'oreal Composition comprising a uv-screening agent, an anionic crosslinked hydrophilic polymer, a surfactant having an hlb less than or equal to 5 and a silicone copolymer
FR3060997A1 (en) * 2016-12-23 2018-06-29 L'oreal COMPOSITION COMPRISING BAICALIN
WO2018180316A1 (en) 2017-03-28 2018-10-04 株式会社マンダム Emulsified cosmetic
JP2019182841A (en) 2018-03-30 2019-10-24 株式会社マンダム Gel-like cosmetic

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
US3915921A (en) 1974-07-02 1975-10-28 Goodrich Co B F Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers
US4509949A (en) 1983-06-13 1985-04-09 The B. F. Goodrich Company Water thickening agents consisting of copolymers of crosslinked acrylic acids and esters
US5089578A (en) 1986-03-28 1992-02-18 Exxon Research And Engineering Company Hydrophobically associating terpolymers containing sulfonate functionality
EP0669323A1 (en) 1994-02-24 1995-08-30 Haarmann & Reimer Gmbh Utilization of benzazols as UV-absorbers, new benzazoles and process for their preparation
EP0750899A2 (en) 1995-06-30 1997-01-02 Shiseido Company Limited An emulsifier or solubilizer which consists of a water soluble amphiphilic polyelectrolyte, and an emulsified composition or a solubilized composition and an emulsified cosmetic or a solubilized cosmetic containing it
WO2000031154A1 (en) 1998-11-23 2000-06-02 Sofitech N.V. Invertible emulsions stabilised by amphiphilic polymers and application to bore fluids
US20070178057A1 (en) * 2006-02-01 2007-08-02 Amcol International Corporation High efficiency sunscreen composition particularly useful for wipes and sprays
EP2266531A1 (en) * 2009-06-24 2010-12-29 L'Oréal Cosmetic composition comprising a superabsorbent polymer and an organic UV filter
WO2012059348A1 (en) * 2010-11-05 2012-05-10 L'oreal Fluid aqueous antisun composition based on a superabsorbent polymer and a crosslinked copolymer of methacrylic acid and of a c1-c4 alkyl acrylate
JP2016121140A (en) 2014-12-24 2016-07-07 日光ケミカルズ株式会社 Gel-like cosmetic
WO2016198581A1 (en) * 2015-06-11 2016-12-15 L'oreal Composition comprising a uv-screening agent, an anionic crosslinked hydrophilic polymer, a surfactant having an hlb less than or equal to 5 and a silicone copolymer
FR3060997A1 (en) * 2016-12-23 2018-06-29 L'oreal COMPOSITION COMPRISING BAICALIN
WO2018180316A1 (en) 2017-03-28 2018-10-04 株式会社マンダム Emulsified cosmetic
JP2019182841A (en) 2018-03-30 2019-10-24 株式会社マンダム Gel-like cosmetic

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior", LANGMUIR, vol. 16, no. 12, 2000, pages 5324 - 5332
DATABASE GNPD [online] MINTEL; 24 October 2019 (2019-10-24), ANONYMOUS: "Day Unifying Bi-Gel Facial Sunscreen SPF 45", XP055859586, retrieved from https://www.gnpd.com/sinatra/recordpage/6972945/ Database accession no. 6972945 *
WALTER NOLL: "Chemistry and Technology of Silicones", 1968, ACADEMIC PRESS
YOTARO MORISHIMA: "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering", MACROMOLECULES, vol. 33, no. 10, 2000, pages 3694 - 3704
YOTARO MORISHIMA: "Self-assembling amphiphilic polyelectrolytes and their nanostructures", CHINESE JOURNAL OF POLYMER SCIENCE, vol. 18, no. 40, 2000, pages 323 - 336, XP009107054
YOTARO MORISHIMA: "Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers", POLYM. PREPRINT, DIV. POLYM. CHEM., vol. 40, no. 2, 1999, pages 220 - 221

Similar Documents

Publication Publication Date Title
ES2634898T3 (en) Cosmetic composition comprising a superabsorbent polymer and an organic UV filter
US6902722B2 (en) Aqueous antisun/sunscreen compositions comprising amphiphilic 2-acrylamidomethylpropanesulfonic acid polymers and water-soluble silicones
US20220387271A1 (en) Mineral sunscreen compositions
US20230310281A1 (en) Method of protecting keratin materials from pollutants
MX2009013647A (en) Cosmetic and/or dermatological composition based on n,n'-diarylmethyleneethylenediaminediacetic acid ester(s).
ES2884159T3 (en) Composition of oil-in-water emulsion
WO2018012557A1 (en) W/o sun care composition including porous organic particle
US9572759B2 (en) Sunscreen compositions having synergistic combination of UV filters
JP7158844B2 (en) Two-phase sun care composition
WO2022124385A1 (en) Oil-in-water emulsion composition
EP3393600B1 (en) Sun care composition based on small particle o/w emulsion
JP2022090264A (en) Oil-in-water emulsion composition
ES2335001T3 (en) WATER SOLAR COMPOSITION THAT UNDERSTANDS AT LEAST AN ACHYLMYL-2-METHYLPROPANOSULPHONIC ACID POLYMER AND A WATER SOLUBLE SILICONE AND USES OF THE SAME.
US9539195B1 (en) Sunscreen compositions having synergistic combination of UV filters
FR3118702A1 (en) Oil-in-water emulsion composition
US11833234B2 (en) Emulsions with a high internal oil phase
EP3374034A1 (en) Composition including thermoplastic hollow particle
US9539194B1 (en) Sunscreen compositions having synergistic combination of UV filters
EP3843689A1 (en) Foaming composition comprising oil
US20180116943A1 (en) Excellent Water Resistance and SPF Boosting Properties with an association of Polyester-5 and Styrene/Acrylates/Ammonium Methacrylate copolymer

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21835425

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21835425

Country of ref document: EP

Kind code of ref document: A1