EP2908795A1 - Sonnenschutzzusammensetzung mit einem (meth)acrylpolymer und pigmentpartikel - Google Patents

Sonnenschutzzusammensetzung mit einem (meth)acrylpolymer und pigmentpartikel

Info

Publication number
EP2908795A1
EP2908795A1 EP13786296.7A EP13786296A EP2908795A1 EP 2908795 A1 EP2908795 A1 EP 2908795A1 EP 13786296 A EP13786296 A EP 13786296A EP 2908795 A1 EP2908795 A1 EP 2908795A1
Authority
EP
European Patent Office
Prior art keywords
composition
copolymer
weight
monomer
composition according
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13786296.7A
Other languages
English (en)
French (fr)
Inventor
Renaud Souzy
Jean-Marc Suau
Olivier Guerret
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coatex SAS
Original Assignee
Coatex SAS
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 FR1259926A external-priority patent/FR2997015B1/fr
Priority claimed from FR1355318A external-priority patent/FR3005414A1/fr
Application filed by Coatex SAS filed Critical Coatex SAS
Publication of EP2908795A1 publication Critical patent/EP2908795A1/de
Withdrawn legal-status Critical Current

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
    • A61K8/18—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
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • 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

Definitions

  • the present invention relates to the technical field of cosmetics, in particular that of cosmetic sunscreen compositions. More particularly, the present invention relates to the use, in cosmetic compositions comprising pigment particles, as ultraviolet filtering agents, of novel additives as agents improving the UV-absorbing capacities of said compositions. The present invention also relates to sunscreen compositions comprising such agents.
  • UV-B rays with wavelengths between 280 nm and 320 nm, cause erythema and skin burns.
  • UV-A rays of wavelengths between 320 nm and 400 nm, which are responsible for the browning of the skin, are also likely to induce a skin. alteration of the latter, especially in the case of sensitive skin or skin continuously exposed to solar radiation. It is therefore desirable that the cosmetic sunscreen compositions are capable of filtering UV-A and UV-B radiation.
  • compositions intended for the UV-A and / or UV-B photoprotection of the skin typically comprise a UV radiation filtering agent.
  • a UV radiation filtering agent There are mainly two categories of filtering agents UV radiation: organic filters and pigment type filters, such as metal oxides, for example titanium dioxide and zinc oxide.
  • EP 1 142 564 (L'Oréal), which describes the combination in an oil-in-water emulsion cosmetic composition of a particular polyethylen mixture with an organic photoprotective system, is also mentioned.
  • Other documents of the prior art describe the use of composite particles whose object is both to obtain a better protection against radiation and to obtain a composition having particular textural properties.
  • EP 1 388 550 (Kao Corp) relating to the use of particles consisting of a metal oxide particle coated with a silicone or fluorinated compound.
  • FR 2 970 172 (L'Oréal) in which the composite particles comprise a matrix and an inorganic UV filter.
  • inorganic pigment type filters for example titanium dioxide (TiO 2 ), zinc oxide (ZnO), cerium oxide (CeOa) and / or iron oxides (Fe 3 O 4 , Fe 2 O 3 ) or composite mineral pigments, for example particles of titanium dioxide coated or having undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature, are products whose availability becomes more and more limited because they rely on a natural resource. This leads to an increase in their price, which is a problem for formulators of sunscreen compositions.
  • the inventors have therefore sought a solution to this problem of the availability of pigment particles, mineral pigments type and coated mineral pigment type. More specifically, the inventors have sought a solution to reduced amounts of pigment particles are used in cosmetic sunscreen compositions without reducing the expected properties of said compositions.
  • a number of documents of the prior art describe the use of dispersing agents which have the capacity to improve the state of dispersion of the pigments in cosmetic products. Nevertheless, despite the use of dispersing agents in cosmetic formulations intended for sun protection, the phenomenon of particle flocculation, in particular during the storage of the cosmetic composition and during the formation of the film on the skin, reduces the filtering efficiency of the agents. such as T1O2 and / or ZnO.
  • a solution to the technical problem of the availability of pigment particles, such as TiO 2 and / or ZnO, coated or not, is provided surprisingly by the use of a particular copolymer, of molecular weight and of specific structure .
  • the inventors demonstrate, in fact, " advantageously that it is possible to significantly reduce the quantity of pigment particles in the cosmetic sunscreen composition without reducing the UV-absorbing performance of said composition.
  • This technical prejudice is in particular incorporated in the introduction of the patent application FR 2 970 172.
  • the inventors furthermore demonstrate that the copolymers according to the invention have no intrinsic UV-absorbing property.
  • the present invention is therefore based on a particular combination of a UV radiation filtering agent, more particularly the pigment particles according to the invention, and a copolymer.
  • the inventors demonstrate, in fact, the increase in UV absorbance of a cosmetic composition which combines the copolymers according to the invention, of specific structure and molecular weight, and pigment particles as filtering agents, in comparison with a cosmetic composition which does not comprise the copolymers according to the invention, this also when the content of pigment particles of said composition has been reduced (for example by 20 or 40% by weight relative to the reference).
  • An object of the present invention is to improve the state of dispersion of the pigment particles in the cosmetic composition, by means of a particular copolymer, in order to increase the UV absorbing performances of the sunscreen compositions,
  • Another object of the present invention is to promote the filtering properties of pigment particles, such as in particular ⁇ iO 2 and / or ZnO, coated or not, while minimizing the necessary quantities of these pigments in sunscreen compositions. container.
  • Another object of the present invention is to reduce the amount of pigment particles, such as TiO 2 and / or ZnO, coated or not, without necessarily having to compensate for this decrease by adding another pigment in the composition.
  • Another object of the present invention is to enable a reduction in the amount of pigment particles, such as Ti0 2 and / or ZnO s coated (s) or not, in the cosmetic compositions of sunscreen without substantial modification of the cosmetic properties of those for example without changing the organoleptic, sensory or textural characteristics.
  • pigment particles such as Ti0 2 and / or ZnO s coated (s) or not
  • Another object of the present invention is to provide a copolymer which makes it possible to increase, compensate or improve the UV-absorbing performance of sunscreens prepared by reducing the dose of pigment particles, such as TiO 2 and / or ZnO, coated ( s) or not, without changing the organoleptic properties with good stability over time.
  • pigment particles such as TiO 2 and / or ZnO
  • the present invention therefore relates to the use, in a sunscreen composition comprising pigment particles, such as titanium dioxide or zinc oxide, coated or not, as an agent improving the UV-absorbing capacities of said composition of a water-soluble comb-type copolymer having a (meth) acrylic acid backbone and poly (alkylene glycol) side chains.
  • the present invention is based on the combination of a UV-filtering agent, namely the pigment particles such as TiO 2 and / or ZnO, coated or not, and a particular (meth) acrylic copolymer.
  • the present invention also relates to a sunscreen composition
  • a sunscreen composition comprising, in a cosmetically acceptable support, from 0.1 to 50% by weight, relative to the total weight of the composition, of pigment particles, such as TiO 2 and / or ZnO UV radiation and at least one water-soluble comb-type copolymer having an acid (meth) acrylic backbone and poly (alkylene glycol) side chains as the filtering agent,
  • pigment particle is meant a mineral compound, for example titanium dioxide (TiO 2 ), zinc oxide (ZnO), cerium oxide (CeO 2 ) and iron oxides (FesO 4 , Fe 2 0 3 ), coated or not, or a mixture of these compounds.
  • These pigment particles may, for example, have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical nature. These particles may have undergone a surface treatment with substances, for example of hydrophobic nature. hydrophilic or mineral.
  • pigment particles For example, for the surface treatment of pigment particles, one or more of the following compounds are used: amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium salts, potassium, zinc, iron or aluminum fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexarnetaphosphate.
  • the pigment particles according to the invention possess UV radiation filtration properties and thus constitute a UV-A filter and / or a UV-B filter. These particles are therefore characterized by their photoprotective activity. They may be in the form of micrometric and / or submicron and / or nanometric particles.
  • TiO 2 particles may be amorphous and / or crystallized and in rutile and / or anatase form for TiO 2 .
  • TiO 2 particles are conventionally obtained by conventional industrial processes from ore, for example by a sulphate process or by a chloride process.
  • the pigment particles are in predispersed form (for example suspensions or dispersions in a liquid) or in powder form. Such particles are commercially available.
  • poly (alkylene glycol) is meant a polymer of an alkylene glycol derived from an olefinic oxide.
  • the poly (alkylene glycol) according to the present invention is, for example, poly (ethylene glycol), poly (propylene glycol), poly (butylene glycol) or a poly (alkylene glycol) containing a proportion of ethylene-oxy group and / or a proportion of propylene-oxy group and / or a proportion of butylene-oxy group.
  • the poly (alkylene glycol) according to the present invention may for example comprise a major proportion of ethyleneoxy group in combination with a secondary proportion of propyleneoxy group.
  • alkylene glycol polymer examples include: polyalkylene glycols having an average molecular weight of 1,000, 4,000, 6,000, 10,000 and 20,000 g / mol (in the case of polyethylene glycol) 1000 5 PEG-4 QQ0 5 PEG-6000, PEG 10,000 PEG 5 20 000); polyethylene polypropylene glycols having a percentage of ethylene oxide of between 20 and 80% by weight and a percentage of propylene oxide of between 20 and 80% by weight,
  • copolymer according to the invention consists of:
  • R represents a polymerizable unsaturated functional group, in particular acrylate, methacrylate, methacrylurethane, vinyl or allyl,
  • R 5 denotes hydrogen or an alkyl group having 1 to 4 carbon atoms
  • X represents a structure comprising n unit (s) of ethylene oxide EO and m unit (s) of propylene oxide OP, arranged alternatively or statistically, m and n are 2 integers, between 0 and 150, at least one of which is non-zero, said copolymer having a molecular weight of between 25,000 g / mol and 50,000 000 g / mol, as detonated by size exclusion chromatography (CES) or in English "Gel Permeation Chromatography" (GPC).
  • CES size exclusion chromatography
  • GPC Garnier Permeation Chromatography
  • the copolymer does not comprise any hydrophobic monomer, such as, for example, selected from the group consisting of styrene, para-tert-butylstyrene, (meth) acrylic esters having from 1 to 4 carbon atoms on the ester group.
  • hydrophobic monomer such as, for example, selected from the group consisting of styrene, para-tert-butylstyrene, (meth) acrylic esters having from 1 to 4 carbon atoms on the ester group.
  • compositions according to the present invention are sunscreen compositions. These compositions are also called sunscreen compositions or photoprotective compositions for filtering, blocking or absorbing UV radiation (in English “UV blocker”, “UV filter” or “UV absorber”),
  • agent improving the UV-absorbing capacities of the sunscreen composition is meant an agent that makes it possible to obtain a cosmetic product whose absorption capacities for UV-A and / or UV-B radiation are improved.
  • UV-absorbent capacity developer agent is used.
  • improve means to increase or respectively imply an increase in the absorbance values of the UV spectrum on wavelengths at least between 310 and 340 nm, for example between 290 and 400 nm, compared to those obtained for the same formulation of sunscreen which comprises the same determined quantity of pigment particles, but no agent according to the invention.
  • the inventors are of the opinion that the copolymers according to the invention have properties which make it possible to space the pigment particles in the formulations, but also to maintain the separation of these particles during the step of forming the film on the surface of the skin and thus to improve the optical path of the light.
  • the UV absorbance of the sunscreen compositions is measured by means of a spectrometer from a sample of the compositions diluted in isopropanol.
  • the pigment particles according to the invention preferably have an average particle size greater than 5 nm and less than 100 nm. According to a particularly preferred embodiment of the invention, this size preferably varies from 10 nm to 50 nm. .
  • the pigment particles may be coated or uncoated.
  • the coated pigment particles are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds, such as amino acids, beeswax, fatty acids, fatty alcohols , aniomic surfactants, lecitines, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • the silicones used for coating the pigment particles according to the invention are for example chosen from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogensiloxanes.
  • the silicones are selected from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydro-genosiloxanes.
  • the pigment particles according to the invention may have undergone several treatments. For example, before their treatment with silicones, they may have been treated with other surfactants, in particular with cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or mixtures thereof. Examples of pigment particles according to the invention which are commercially available are, for example, coated titanium dioxide particles.
  • silica and / or alumina, and optionally aluminum stearate are silica and / or alumina, and optionally aluminum stearate,
  • silica, alumina, aluminum stearate and treated with a silicone
  • coated titanium dioxide particles examples are:
  • pigment particles according to the invention are, for example, uncoated titanium dioxide particles sold under the trade names;
  • pigment particles according to the invention are, for example, uncoated zinc oxide particles sold under the trade names:
  • pigment particles according to the invention are, for example, zinc oxide particles;
  • coated zinc oxide particles examples include the products of the OXIDE ZINC CS range (Toshibi),
  • pigment particles according to the invention are, for example, uncoated iron oxide particles sold under the trade names:
  • Formulations which contain mixtures of pigment particles, in particular of titanium dioxide and of cerium dioxide, of which the titanium dioxide / cerium dioxide dioxide mixture is coated with silica, as well as the mixture of titanium dioxide and zinc dioxide, may also be mentioned. coated with alumina, silica and silicone or titanium dioxide / zinc dioxide mixture coated with alumina, silica and glycerine.
  • the sunscreen composition according to the invention also comprises a water-soluble copolymer which, according to one aspect of the present invention, has a molecular mass of between 300 000 and 50 000 000 g / mol, for example between 300 000 and 20 000 000 g.
  • the water-soluble copolymer has a molecular weight of between 300,000 and 300,000. 000 000 g / mol, as determined by size exclusion chromatography (CES).
  • the water-soluble copolymer has a molecular weight of between 1,000,000 and 15,000,000 g / mol.
  • the sunscreen composition according to the invention also comprises a water-soluble copolymer which, according to another aspect of the present invention, has a molecular mass of between 25,000 and 15,000,000 g / mol, for example between 25,000 and 1,000,000. g / mol, as determined by steric exclusion chromatography (CES),
  • the water-soluble copolymer has a molecular weight of between 25,000 and 500,000 g / mol, as determined by size exclusion chromatography (CES).
  • the water-soluble copolymer has a molecular weight of between 25,000 and 400,000 g / mol.
  • said water-soluble copolymer is such that n is a non-zero integer less than 150 and m is an integer between 0 and 150.
  • m optionally takes the value of zero, which means that the poly (alkylene glycol) side chains of the copolymer, according to this.
  • aspect of the invention include only ethylene oxide units; in other words, according to this aspect of the invention, they are poly (ethylene glycol) side chains,
  • said water-soluble copolymer is such that n is an integer between 15 and 150 ⁇ m is an integer between 0 and 150.
  • said water-soluble copolymer is such that n and m are two integers of which at least one is non-zero and n + m> 17.
  • said water-soluble copolymer is such that n and m are two integers of which at least one is non-zero and n + m> 50.
  • the R function of monomer of formula (I) represents the methacrylate function.
  • the function R 'è & monomer of formula (I) represents H or Q ⁇ .
  • the R function of the monomer of formula (I) represents the methacrylate function and the R s function of the monomer of formula (I) represents H
  • said copolymer consists, based on the total weight of the copolymer, of;
  • said copolymer consists, relative to the total weight of the copolymer, of:
  • said composition comprises from 0.05 to 5% by weight of active ingredient of said copolymer, relative to the weight total of the composition.
  • said composition comprises from 0.1 to 3% by weight of active material of said copolymer, relative to the total weight of the composition.
  • said composition comprises from 0.2 to 50% by weight of pigment particles as described above.
  • said composition comprises from 0.4 to 40% by weight of particles of these pigment particles, for example from 0.4 to 30% by weight.
  • said formulation comprises at least titanium dioxide and / or zinc oxide and / or cerium oxide and / or coated or non-coated iron oxides.
  • said formulation further comprises another pigmentary inorganic filler selected from the group consisting of calcium carbonate, zinc oxide, kaolin and a silicate.
  • the pigment mineral fillers of the sunscreen formulation of the present invention comprise:
  • the sunscreen formulations of the present invention potentially comprise other complementary organic photoprotective agents, UV-A and / or UV-B active, hydrophilic, lipophilic, or insoluble in commonly used cosmetic solvents.
  • Said other additional hydrophilic or lipophilic organic photoprotective agents are for example selected from anthranilates; dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from alkylstyrene; 4,4-diarylbutadienes; and their mixtures.
  • PABA p-aminobenzoic acid derivatives
  • the additional photoprotective agents may be present in the formulations according to the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, for example ranging from 0.1% to 10% by weight relative to to the total weight of the formulation.
  • compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants chosen from softeners, humectants, opacifiers, stabilizers, emollients, silicones, defoamers, perfumes, preservatives, anionic surfactants, cationiqueSj nonionic, zwitterionic or amphoteric 5 loads f propellants, basifying or acidifying agents or any other ingredient usually used in cosmetics and / or dermatological composition.
  • cosmetic adjuvants chosen from softeners, humectants, opacifiers, stabilizers, emollients, silicones, defoamers, perfumes, preservatives, anionic surfactants, cationiqueSj nonionic, zwitterionic or amphoteric 5 loads f propellants, basifying or acidifying agents or any other ingredient usually used in cosmetics and / or dermatological composition.
  • the medium of the sunscreen composition according to the present invention is a physiologically and / or cosmetically acceptable medium. It may for example be monophasic of aqueous or non-aqueous / anhydrous type, that is to say essentially consisting of one or more oils.
  • the composition according to the present invention may also be multisphasic, that is to say comprise several phases.
  • the composition according to the present invention may be biphasic and comprise at least one anhydrous phase containing at least one polar oil.
  • compositions according to the invention may be in any form suitable for topical application, in particular in the form of aqueous gels, in the form of emulsions obtained by dispersing a fatty phase (also called oily phase) in an aqueous phase ( H / E) or conversely (W / O) or multiple emulsions (for example E / H / E or H7E / H or H7H / E), They can be more or less fluid and have the appearance of a cream white or colored, an ointment, a milk, a! ⁇ ote a serum, a paste, powder, solid stick and may optionally be packaged as an aerosol and be in the form of foam or These compositions are prepared according to the usual methods,
  • the sunscreen composition comprises, based on the total weight of the composition, a) from 10% to 99.9% by weight of aqueous phase,
  • the sunscreen composition comprises, based on the total weight of the composition, a) from 15% to 99.5% by weight of aqueous phase,
  • the sun protection composition comprises, with respect to the total weight of the composition, of: a) 50% to 70% by weight of aqueous phase,
  • the aqueous phase of the composition may consist of a mixture of water and organic solvents miscible with water (miscibility in water greater than 50% by weight at 25 ° C).
  • solvents are, for example, chosen from lower monoalcoois comprising from 1 to 5 carbon atoms such as ethanol, isopropanol and glycols containing from 2 to 8 carbon atoms such as propylene glycol and ethylene glycol. 1,3-butylene glycol, dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes and ethoxylated alcohols,
  • the non-aqueous phase (or fatty phase) of the cosmetic composition according to the present invention is capable of comprising natural or synthetic ingredients immiscible with water, liquid at room temperature (25 ° C.) and / or solid at room temperature.
  • An object of the present invention also consists of a method for preparing a sunscreen composition, consisting in implementing the copolymer according to the invention.
  • the sunscreen composition according to the present invention is generally not rinsed, but it can be rinsed if it constitutes a cleaning product including foaming.
  • the subject of the invention is also a process for the cosmetic treatment of a keratin material such as the skin, eyelashes, eyebrows, nails or mucous membranes, characterized in that a composition such as is applied to the keratin material defined above.
  • the invention also relates to a cosmetic assembly comprising:
  • the container can be in any suitable form. It may especially be in the form of a bottle, a tube, a pot, a case, a box, a bag or a case.
  • Said copolymer according to the invention is obtained by known methods of conventional radical copolymerization in solution, in direct or inverse emulsion in bulk, in suspension or precipitation in appropriate solvents, in the presence of known initiators and transfer agents, or also by controlled radical polymerization processes such as the method called Reversible Addition Fragmentation Transfer (RAFT), the method called Atom Transfer Radical Polymerization (ATRP), the method called Nitroxide Mediated Polymerization (NMP) or the method called Cobaloxime Mediated Free Radical Polymerization.
  • RAFT Reversible Addition Fragmentation Transfer
  • ATRP Atom Transfer Radical Polymerization
  • NMP Nitroxide Mediated Polymerization
  • Cobaloxime Mediated Free Radical Polymerization the method called Cobaloxime Mediated Free Radical Polymerization.
  • the molecular weight of the copolymers according to the invention is determined by size exclusion chromatography (CES).
  • Such a technique implements a WATERS TM brand liquid chromatography apparatus with two detectors.
  • One of these detectors combines the static dynamic scattering of light at an angle of 90 ° C to the viscometry measured by a VIESCOK TM MALVERN TM detector viscometer.
  • the other of these detectors is a WATERS TM brand refractometric concentration detector
  • This liquid chromatography apparatus is provided with steric exclusion columns appropriately selected by the trade in order to separate the different molecular weights of the polymers studied.
  • the liquid phase of elution is an aqueous phase containing 1% of KNO 3 .
  • the polymerization solution in the eluent of the CES which is a 1% solution of KNO 3
  • a 1% solution of KNO 3 is diluted to 0.9% by weight.
  • filtered at 0.2 ⁇ . 100 ⁇ ⁇ are then injected into the chromatograph (eluent: a 1% solution of KN0 3).
  • the liquid chromatography apparatus contains an isocratic pump (WATERS TM 515) whose flow rate is set at 0.8 ml / min.
  • the chromatography apparatus also comprises an oven which itself comprises in series the column system.
  • the detection system consists on the one hand of a RI WATERS TM 410 type refractometric detector and on the other side of a double viscometer detector and light diffusion at a 270 ° angle of 90 °.
  • DUAL DETECTOR MALVERN TM The oven is heated to a temperature of 55 ° C. and the refractometer is heated to a temperature of 45 ° C.
  • the chromatography apparatus is calibrated with a single standard of PEO 19k PoiyCAL TM MALVERN TM.
  • UVA & UVB the measurement of the ultraviolet absorbance
  • the measurements are performed on a Genesys UV UV TM Spectrometer (Cole Parmer), equipped with Rotilabo-Einmal Kuvetten PS vats, 4.5 mL. In a practical manner, the apparatus is preheated 10 minutes before use. A first measurement is first made using a vessel filled with 3.8 ml of isopropanol (the "white”). The measurement is then carried out with a vat filled with 3.8 ml of the homogeneous solution to be tested, that is to say 0.05 g of the solar formulation to be tested, diluted in 40 g of isopropanol. The absorbance is then measured at each wavelength between 290 nm and 400 nm.
  • the viscosity of said formulations is measured using a Brookfield viscometer, model RVT. Before measuring the viscosity, each of the formulations is allowed to stand for 24 hours at 25.degree. The mobile must be centered with respect to the opening of the bottle. The viscosity is then measured at 20 rpm using the appropriate module. The viscometer is allowed to rotate until the viscosity is stable. Finally, the viscoelasticity (or consistency) of different formulations is carried out using a Haake-RheoStress RS 150 rheometer. The variation of the modulus G * (Pa) as a function of the stress ⁇ (scan of 0 at 800 Pa) is measured at 25 ° C, thanks to the cone-plane module (1 °).
  • phase shift phase shift, creaming, exudation, release, deposition / sedimentation.
  • Phase A the various ingredients are introduced with stirring and the medium is heated to 65 ° C .;
  • Phase B in another beaker, all the ingredients except B-12 and B-13 are mixed, and heated to 65 ° C with stirring;
  • ingredient B-12 as well as ring ingredient B-13 are dispersed with stirring;
  • Phase C adding with moderate stirring the polymer C-15 (if present) and titanium dioxide C-14 (in the form of a powder);
  • Table 2 summarizes all of the polymers that were used as ingredient C-15 in the tests of this Example 1.
  • the amount of titanium dioxide indicated in the table is expressed as a quantity Y, that is to say a percentage by weight relative to the total weight of the composition.
  • Y is 5%
  • 5 g of C-15 is added for a formulation of 100 g of finished product.
  • Test 1-2 employs a quantity of titanium dioxide reduced by 20% relative to the reference (test 1-1), ie 80% of the amount of TiO 2 of the reference formulation.
  • Test 1-3 The ingredient C-15 is here a dispersant for TiO 2 of the type Polyglyceryl-10 Decaoleate
  • UVA and UVB absorbance spectra are shown in Figures I and 2.
  • Figure 1 demonstrates that: - by decreasing the amount of titanium dioxide by 20% by weight in the formulation, the UV absorbance of the formulation is reduced (test 1-2 of test 1);
  • the polymers according to the invention are not UV filters (tests 1-13 and 1-14). That is, they are not substances capable of filtering UV radiation.
  • the polymers of tests 1-5 to 1-12 make it possible to compensate, at least in part, for the loss of TiO 2, their UV absorbance spectrum being generally greater than that of test 1 -2 (reference - 20% TiO 2 ) ;
  • test polymer 1-5 makes it possible to completely compensate for the 20% loss of TiO 2 relative to the reference (test 1-1), its UV absorbance spectrum being generally equivalent to that of test 1-1 ( reference);
  • the polymers of the tests 1-11 and 1-12 make it possible not only to compensate, but, moreover, to improve the UV absorbance of the formulation, their UV absorbance spectrum being greater than that of the test 1-1 (reference with 100% TiO2).
  • the addition of one of the polymers according to the invention makes it possible to compensate, at least in part, the UV absorbance of sunscreens.
  • the two formulations have a number of freeze-thaw cycles before identical destabilization, namely five.
  • This example relates to the implementation of a polymer according to the invention in a sprayable sunscreen formulation, which is characterized by a particular rheological profile, from the following ingredients (the figures in the last column indicate the percentages by weight relative to to the total weight of the composition):
  • Phase A all the ingredients of Phase A are mixed
  • Phase B In another beaker, B-3 is introduced, then B-4 and then B-5 are successively dispersed. Ingredients B-6, B-7, optionally B-8 and finally B-9 are then added. - Phase B is then introduced into phase A.
  • Phase C dilute C-11 in C-10. This mixture is introduced into the mixture Phase A / Phase B.
  • the amount of titanium dioxide indicated in the table is expressed as a quantity Y, that is to say a percentage by weight relative to the total weight of the composition.
  • Y is 0.5%
  • 0.5 g of B-8 is added for a formulation of 100 g of finished product.
  • the table indicates this variation by indicating a percentage with respect to the amount of TiO 2 used in the reference formulation (test 2-1). .
  • test 2-5 implements a quantity of titanium dioxide reduced by 20% relative to the reference (test 2-1), ie 80% of the amount of TiO 2 of the formulation of reference.
  • the additive of the prior art used is dispersant of the Polyglyceryl-10 Decaoleate type.
  • UVA and UVB absorbance spectra are shown in Figure 3.
  • test 2-4 does not make it possible to compensate for the 20% reduction in TiO 2 , its UV absorbance spectrum being generally lower than that of test 2-2 (reference 20 % TI02);
  • the polymers of tests 2-5 to 2-8 make it possible to compensate, at least in part, for the loss of Ti0 2 , its UV absorbance spectrum being generally greater than that of test 2-2 (reference - 20% TiO2);
  • the polymers of tests 2-5, 2-6 and 2-8 make it possible not only to compensate for the 20% loss of TiO 2 , but also to improve the absorbance of the formulation on the UV spectrum, their spectrum of UV absorbance being higher than that of test 2-1 (reference with 100% T102).
  • the two formulations have a number of freeze-thaw cycles before identical destabilization, namely five.
  • the additives according to the invention are effective not only in formulations of the cream type (Example 1), but also in sprayable lotions (Example 2). Despite a reduction of 20% or even 40% by weight of the initial amount of UV filters of the TiCh type, the addition of the additives according to the invention makes it possible to maintain at least in part, or even to increase significantly the performances UV absorptive solar compositions (cream or lotion for example), Example 3 - Sunscreen
  • Phase A the various ingredients are introduced with stirring and the medium is heated to 65 ° C .;
  • Phase B In another beaker, all the ingredients are mixed, except B-12 and B-1 3, and heated to 65 ° C with stirring;
  • ingredient B-12 and ingredient B-13 are dispersed with stirring;
  • Phase A and B are mixed in order to obtain a viscous emulsion
  • Phase C C-15, if present, is added under very moderate stirring, followed by ingredient C-14, which is titanium dioxide marketed by Croda, and is in a form dispersed in an oil. cosmetic;
  • the pH is measured and it is verified that it is in the range 6.7 to 7.0.
  • Table 8 summarizes all the polymers used as ingredient C-15.
  • the amount of titanium dioxide indicated in the table is expressed as a quantity Y, that is to say a percentage by weight relative to the total weight of the composition.
  • Y is equal to 15%, 15 g of C-14 are added for a formulation of 100 g of finished product.
  • the table indicates this variation by indicating a percentage with respect to the amount of TiO 2 used in the reference formulation (test 3-1). .
  • test 3-3 implements a quantity of titanium dioxide reduced by 20% relative to the reference (test 3-1), ie 80% of the amount of TiO 2 of the formulation of reference.
  • UVA and UVB absorbance spectra are shown in Figure 4.
  • FIG. 4 demonstrates that the polymers of tests 3-3 and 3-4 make it possible not only to compensate for the 20% loss of TiO 2, but also to improve the UV absorbance of the formulation (its absorbance spectrum being higher than that of test 3-2, reference).
  • the preparation protocol of the formulation is identical to that of Example 1.
  • the titanium dioxide is replaced by zinc oxide (commercially available) in a powder form.
  • Table 10 summarizes all the polymers used as ingredient C-15.
  • FIG. 5 demonstrates that the polymer of tests 4-3 and 4-4 not only compensates for the 20% loss of ZnO, but also improves the absorbance of the formulation (its absorbance spectrum being greater than that of the formulation). test 5 4-2 reference).
  • the additives according to the invention are effective in formulations of the sunscreen type (Examples 1, 3 and 4) irrespective of the form in which the particles of titanium dioxide (powder or dispersed in an oil) occur. or zinc oxide particles (powder) as UV-absorbing filters, or cosmetic compositions of the sprayable type (Example 2).
EP13786296.7A 2012-10-18 2013-10-11 Sonnenschutzzusammensetzung mit einem (meth)acrylpolymer und pigmentpartikel Withdrawn EP2908795A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR1259926A FR2997015B1 (fr) 2012-10-18 2012-10-18 Composition de protection solaire comprenant un copolymere (meth)acrylique et du dioxyde de titane et/ou de l'oxyde de zinc.
US201261717695P 2012-10-24 2012-10-24
FR1355318A FR3005414A1 (fr) 2013-06-10 2013-06-10 Composition de protection solaire comprenant un copolymere (meth)acrylique et des particules pigmentaires.
PCT/FR2013/052436 WO2014060688A1 (fr) 2012-10-18 2013-10-11 Composition de protection solaire comprenant un copolymère (meth)acrylique et des particules pigmentaires

Publications (1)

Publication Number Publication Date
EP2908795A1 true EP2908795A1 (de) 2015-08-26

Family

ID=50487620

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13786296.7A Withdrawn EP2908795A1 (de) 2012-10-18 2013-10-11 Sonnenschutzzusammensetzung mit einem (meth)acrylpolymer und pigmentpartikel

Country Status (6)

Country Link
US (1) US9700505B2 (de)
EP (1) EP2908795A1 (de)
CN (1) CN104736129B (de)
BR (1) BR112015007288A2 (de)
MX (1) MX2015004427A (de)
WO (1) WO2014060688A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2371044B1 (de) 2008-12-03 2019-08-28 Innolume GmbH Halbleiterlaser mit geringem relativem intensitätsrauschen individueller longitudinalmoden und den laser umfassendes optisches übertragungssystem
WO2014053578A2 (en) * 2012-10-02 2014-04-10 L'oreal Novel cosmetic uses of dispersant polymers associated with at least one particle chosen from coloring materials and non-coloring fillers
US10814114B2 (en) * 2015-12-08 2020-10-27 Dusa Pharmaceuticals, Inc. Method and apparatus for applying a topical solution
CN109771306B (zh) * 2019-01-02 2021-11-30 江南大学 一种无机-有机防晒剂复合微球及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012172209A2 (fr) * 2011-04-26 2012-12-20 Coatex Utilisation de copolymeres acryliques peignes comme agent developpeur de couleur dans des compositions cosmetiques
EP2870205B1 (de) * 2012-07-06 2016-10-19 Coatex Verwendung von neuen additiven in einer lackformulierung mit titandioxidpartikeln als mittel zur verbesserung der trübung eines trockenen oder trocknenden films

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1202617A (de)
US4597963A (en) * 1984-10-05 1986-07-01 Charles Of The Ritz Group Ltd. Moisture-resistant skin treatment compositions
US5221533A (en) * 1992-01-31 1993-06-22 Perlman H Harris Skin lotion composition
FR2720632B1 (fr) * 1994-06-03 1996-07-05 Oreal Compositions cosmétiques photoprotectrices contenant un système filtrant les rayons UV et des polymères particuliers et utilisations.
JP2927701B2 (ja) * 1995-03-16 1999-07-28 共栄社化学株式会社 メタクリル系共重合物とその共重合物を含む非水系塗料用顔料の分散剤
US6090369A (en) * 1997-06-04 2000-07-18 Stewart; Ernest Glading Sunscreen formulation with avobenzone and method for stabilizing sunscreen formulation which contains avobenzone
FR2804600B1 (fr) 2000-02-08 2002-03-22 Oreal Compositions photoprotectrices comprenant un melange d'un polyethylene a fonction acide carboxylique terminale et d'un polyethylene
FR2810261B1 (fr) * 2000-06-15 2002-08-30 Coatex Sa Utilisation de copolymeres faiblement anioniques comme agent dispersant et/ou d'aide au broyage de suspension aqueuse de matieres minerales, suspensions aqueuses obtenues et leurs utilisations
US20060106129A1 (en) * 2002-05-08 2006-05-18 Michael Gernon Optimized alkanolamines for latex paints
US7153573B2 (en) 2002-08-08 2006-12-26 Kao Corporation Polymer composite particle comprising metal oxide and silicone and/or fluorine and method of producing the same
CN101090701B (zh) * 2005-03-21 2011-11-02 宝洁公司 包括视觉上不同的相的多相个人护理组合物
FR2970172A1 (fr) 2011-01-11 2012-07-13 Oreal Composition cosmetique anti-uv
FR2973241B1 (fr) * 2011-03-28 2013-04-19 Coatex Sas Polymeres peignes pour les cheveux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012172209A2 (fr) * 2011-04-26 2012-12-20 Coatex Utilisation de copolymeres acryliques peignes comme agent developpeur de couleur dans des compositions cosmetiques
EP2870205B1 (de) * 2012-07-06 2016-10-19 Coatex Verwendung von neuen additiven in einer lackformulierung mit titandioxidpartikeln als mittel zur verbesserung der trübung eines trockenen oder trocknenden films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2014060688A1 *

Also Published As

Publication number Publication date
MX2015004427A (es) 2015-06-24
CN104736129B (zh) 2018-04-20
US9700505B2 (en) 2017-07-11
WO2014060688A1 (fr) 2014-04-24
CN104736129A (zh) 2015-06-24
BR112015007288A2 (pt) 2017-07-04
US20150283057A1 (en) 2015-10-08

Similar Documents

Publication Publication Date Title
EP0966954B1 (de) Kosmetische Sonnenschutzmittel enthaltend ein Metalloxyd-Nanopigment und ein acrylisches Terpolymer und Verwendung dieser Mittel zum Schutz von Keratinmaterialen gegen UV-Strahlung
EP1353641B1 (de) Kosmetische zubereitung enthaltend minerale filter
FR2903599A1 (fr) Composition cosmetique a phase continue aqueuse comprenant au moins un polymere thermogelifiant, au moins un solvant organique volatil miscible dans l'eau et au moins un agent absorbant les radiations uv.
RU2709537C2 (ru) Состав для солнцезащитного крема
FR3004106A1 (fr) Composition contenant des particules composites filtrant les radiations uv de taille moyenne superieure a 0,1μm et des particules d'aerogel de silice hydrophobes
EP2512417A2 (de) Kosmetisches behandlungsverfahren mit einer in-situ-kondensierbaren verbindung und einem uv-strahlungsfiltermedium
FR2982147A1 (fr) Composition a phase huileuse continue contenant au moins un filtre uv organique lipophile et des particules d'aerogel de silice hydrophobes.
CA2592488A1 (fr) Utilisation cosmetique de particules concaves ou annulaires de materiau silicone comme agent permettant d'augmenter le facteur de protection solaire; composition photoprotectrice aqueuse les contenant
WO2011004133A2 (fr) Materiau composite comprenant des filtres uv et des particules plasmoniques et utilisation en protection solaire.
FR3026008A1 (fr) Composition a base de particules composites spheriques multicouches et d'un filtre uv
CN105431130B (zh) 包含部花青、有机uvb-遮蔽剂和附加的有机uva-遮蔽剂的化妆品或者皮肤病学组合物
EP2908795A1 (de) Sonnenschutzzusammensetzung mit einem (meth)acrylpolymer und pigmentpartikel
EP1745773A1 (de) Lichtschutzmittel enthaltend eine wässrige Phase und ein nicht-polares, niedrigschmelzendes Wachs
EP3573494B1 (de) Vorrichtung zum verpacken und ausgeben einer kosmetischen zusammensetzung
FR2986423A1 (fr) Composition solaire contenant un derive de 4-carboxy 2-pyrrolidinone et des particules d'aerogel de silice hydrophobe
WO2014006589A2 (fr) Composition cosmetique photoprotectrice
WO2022006408A1 (en) Organic and mineral filter hybrid sunscreen
FR3005414A1 (fr) Composition de protection solaire comprenant un copolymere (meth)acrylique et des particules pigmentaires.
FR2951078A1 (fr) Particules photoniques
FR3114503A1 (fr) COMPOSITION D’ÉCRAN SOLAIRE COSMÉTIQUE EN GEL AQUEUX, processus de fabrication de la COMPOSITION D’ÉCRAN SOLAIRE COSMÉTIQUE EN GEL AQUEUX et utilisation de la COMPOSITION D’ÉCRAN SOLAIRE COSMÉTIQUE EN GEL AQUEUX
FR3111798A1 (fr) Compositions cosmétiques anhydres, procédé de fabrication d’un composition cosmétique et utilisation des compositions cosmétiques anhydres
FR2997015A1 (fr) Composition de protection solaire comprenant un copolymere (meth)acrylique et du dioxyde de titane et/ou de l'oxyde de zinc.
FR2903598A1 (fr) Composition cosmetique aqueuse fluide filtrante comprenant au moins un polymere thermogelifiant et au moins un agent absorbant les radiations uv
FR3060982A1 (fr) Composition photoprotectrice aqueuse contenant des particules concaves de polyacrylate et au moins un filtre uv organique hydrosoluble
FR3064458A1 (fr) Article de cosmetique muni d'une maille

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150512

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SUAU, JEAN-MARC

Inventor name: SOUZY, RENAUD

Inventor name: GUERRET, OLIVIER

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20170516

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: A61K 8/27 20060101AFI20190429BHEP

Ipc: A61K 8/91 20060101ALI20190429BHEP

Ipc: A61K 8/29 20060101ALI20190429BHEP

Ipc: A61Q 17/04 20060101ALI20190429BHEP

Ipc: A61K 8/81 20060101ALI20190429BHEP

Ipc: A61K 8/86 20060101ALI20190429BHEP

INTG Intention to grant announced

Effective date: 20190522

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20191002