WO2018122121A1 - Formulations d'écran solaire sous forme de dispersion d'oxyde métallique dans huile - Google Patents

Formulations d'écran solaire sous forme de dispersion d'oxyde métallique dans huile Download PDF

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Publication number
WO2018122121A1
WO2018122121A1 PCT/EP2017/084221 EP2017084221W WO2018122121A1 WO 2018122121 A1 WO2018122121 A1 WO 2018122121A1 EP 2017084221 W EP2017084221 W EP 2017084221W WO 2018122121 A1 WO2018122121 A1 WO 2018122121A1
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WIPO (PCT)
Prior art keywords
meth
acrylate
oil
sunscreen
alkyl
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PCT/EP2017/084221
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English (en)
Inventor
Shawn Zhu
John Socrates Thomaides
Devon COCUZZA
John M. Morales
Andrew Richard BORACCI
Qiwei He
Gary Theodore Martino
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Akzo Nobel Chemicals International B.V.
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Publication of WO2018122121A1 publication Critical patent/WO2018122121A1/fr

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    • 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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; 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
    • A61K8/31—Hydrocarbons
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • 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

  • This application relates to personal care sunscreen oil dispersion formulations comprising an oil-based carrier, rheology modifiers and particulate sunscreen active agents, and to methods of stabilizing such oil dispersions using rheology modifiers.
  • Va ous types of sunscreen product formulations are available commercially to protect a user's skin from UVA and UVB rays that are present in solar radiation.
  • Sunscreen formulations are typically categorized as either aqueous or non-aqueous compositions.
  • Aqueous sunscreen compositions are typically creams formed as emulsions containing the active UV absorbing compounds and additional ingredients such as waterproofing agents, fragrances, emollients and other skin care ingredients.
  • Non-aqueous sunscreen formulations include solvent-based compositions that can be formed as gels for topical application or sprayed-on, for example from an alcohol based solution of the ingredients.
  • clear liquid oil sunscreen formulations containing oils and organic sunscreen active agents are also known. Sunscreen products may be in a solid form, a liquid form, a paste form, or a gelled stick form.
  • Sunscreen active agents include both organic agents and inorganic agents.
  • Inorganic sunscreen active agents include metal oxides such as titanium dioxide (Ti0 2 ), zinc oxide (ZnO), aluminum oxide (Al 2 0 3 ), and iron oxide (FeO). Such metal oxides exist as particles that are insoluble in aqueous systems, alcohol systems, emulsions, and oil-based systems.
  • Inorganic sunscreen active agents in the current art are typically used in aqueous based sunscreen formulations containing typically about 5% - 20% Ti0 2 (and/or ZnO), along with other cosmetically acceptable additives such as emollients.
  • Inorganic sunscreen active agents of proper particle sizes can block both UVA and UVB radiation, while organic sunscreen active agents generally only block either UVA or UVB radiation.
  • inorganic sunscreen active agents are chemically stable, while organic sunscreens may undergo chemical degradation when exposed to the sun.
  • Inorganic sunscreen active agents may be less preferred than organic sunscreen active agents in certain formulations because they can take longer to rub in, they may look "ashy" when dried, and they tend to have poor water resistance in aqueous or emulsion-based carrier systems. Water resistance is a key performance indicator for a sunscreen formulation for consumers who engage in outdoor water activities, or outdoor activities that may cause significant perspiration.
  • Prior efforts to provide stable dispersions of metal oxide powders in an oil vehicle have focused on incorporating an organic component with the metal oxide powder, such as by encapsulation, surface treatment, or covering a lipophilic base powder with metal oxide powder particles.
  • EP 2455061 discloses an oily dispersion containing only two components, namely, an oil dispersion medium and a surface-treated inorganic microparticle oxide powder treated with 1 - 30% by weight of the content of branched fatty acid containing isostearic acid as a primary constituent component, or a metal salt containing isostearic acid as a primary constituent component. Also disclosed is a cosmetic material having a high SPF value and using the oily dispersion.
  • Eospoly Sun Cream (XP-002659382) discloses a sun screen light day protection cream comprising spherical composites of titanium dioxide encapsulated into a polymer structure, and wherein the cream is an emulsion.
  • JP 2014 091735 A discloses an oil-in-water type emulsion comprising a crosslinked (meth) acrylic acid ester resin powder; acrylic acid/ sodium acryloyldimethyltaurine copolymer; a liquid oil agent; a hydrophobically treated powder; and water.
  • the hydrophobic powder can be any extender pigment or coloring pigment used in ordinary cosmetics, which includes metal oxides and others.
  • the hydrophobic treatment can be, for example, adsorption of fats and oils on the surface of the powder.
  • JP 2014 080377 A discloses an oil-in-water type emulsion stated to have excellent temporal stability and comprising a particulate zinc oxide subjected to surface coating treatment with trialkoxyalkyl silane and or alkyl titanate; a non-silicone based surfactant; an oil solution; a polyoxyethylene hardened castor oil; an acrylamide based thickener; and water.
  • EP 1576947 discloses an oily skin preparation comprising a complex powder (the surface of lipophilic base powder is covered with zinc oxide) and an oil component, wherein the complex powder is dispersed in the oil component, and wherein the zeta-potential of the lipophilic base powder is a negative value at the pH of skin.
  • the lipophilic base powder can be selected from silicone resin, silicone rubber, silicone resin-covering-silicone rubber, polyamide, polymethyl methacrylate and ethyl carbamate.
  • metal oxide oil dispersion sunscreen formulation that is storage stable and has good water resistance, and that allows for dispersion of the metal oxide particles without incorporation of the metal oxide particles with an organic component, such as by encapsulation, surface-coating, coating of the metal oxide on a lipophilic base powder, or other pre-treatment of the particles.
  • sunscreen formulations can be prepared comprising metal oxide particulate sunscreen active agents, one or more oils, and one or more selected polymeric rheology modifiers, to provide a thickened metal oxide oil dispersion sunscreen formulation in which the metal oxide particulates are dispersed in the formulation.
  • the thickened sunscreen formulations are dispersions having long-term storage stability, whereby the metal oxide particulates remain in the dispersed state in the formulations when stored over a long term.
  • the disclosure provides a thickened sunscreen formulation comprising an oil-based carrier comprising at least one oil, at least one particulate metal oxide sunscreen active agent, and at least one polymeric rheology modifier.
  • the formulation is not in the form of a water-in-oil or oil-in-water emulsion.
  • the metal oxide particles do not include an organic component.
  • the polymeric rheology modifier is obtainable by co-polymerizing a monomer mixture comprising at least one alkyl (meth)acrylate and at least one of the following monomers: a bicyclic (meth)acrylate ester different from the alkyl (meth)acrylate, and an aromatic vinyl monomer.
  • the polymeric rheology modifier comprises 5 to 50 wt% bicyclic (meth)acrylate ester, 25 to 70 wt% alkyl (meth)acrylate, and 10 to 40 wt% aromatic vinyl monomer.
  • the polymeric rheology modifier comprises 20 to 70 wt% bicyclic (meth)acrylate ester, and 30 to 80 wt% alkyl (meth)acrylate.
  • the bicyclic (meth)acrylate ester is isobornyl methacrylate
  • the alkyl (meth)acrylate is isobutyl methacrylate
  • the aromatic vinyl monomer is styrene.
  • the alkyl (meth)acrylate is a lower alkyl (meth)acrylate and/or a fatty alkyl (meth)acrylate and the polymeric rheology modifier is obtainable by co-polymerizing at least two of the following monomers: a bicyclic (meth)acrylate ester,
  • the polymeric rheology modifier is obtainable by co-polymerizing at least a bicyclic (meth)acrylate ester.
  • the polymeric rheology modifier comprises 10 to 30 wt% bicyclic (meth)acrylate ester, 10 to 25 wt% lower alkyl (meth)acrylate, 30 to 40 wt% fatty-alkyl (meth)acrylate, and 15 to 30 wt% aromatic vinyl monomer.
  • the bicyclic (meth)acrylate ester is isobornyl methacrylate
  • the lower alkyl (meth)acrylate is isobutyl methacrylate
  • the fatty alkyl (meth) acrylate is lauryl methacrylate
  • the aromatic vinyl monomer is styrene.
  • the polymeric rheology modifier is a cross-linked polymer.
  • the cross-linked polymeric rheology modifier provides both thickening of the formulation and suspension of the dispersed metal oxide particulates.
  • the polymeric rheology modifier is a cross-linked polymer that further comprises a cross-linking monomer in the amount of between about 20 ppm to about 2000 ppm, preferably about 200 ppm to about 1500 ppm, more preferably between 300 ppm and 1000 ppm, more preferably about 350 ppm to about 650 ppm.
  • the cross-linking monomer is a di-functional or multifunctional (meth) acrylate monomer, such as 1 ,6-hexanediol di(meth)acrylate or trimethylolpropane triacrylate.
  • the disclosure provides a method of making a thickened sunscreen formulation, the method comp sing combining an oil-based carrier comphsing at least one oil with at least one particulate metal oxide sunscreen active agent and at least one cross-linked polymeric rheology modifier, wherein the at least one particulate metal oxide sunscreen active agent is dispersed in the formulation.
  • the disclosure provides a method of protecting a user from the deleterious effects of UVA and/or UVB radiation, the method comphsing applying to the skin of a user a thickened sunscreen formulation comphsing an oil-based carrier comphsing at least one oil, at least one particulate metal oxide sunscreen active agent, and at least one cross-linked polymeric rheology modifier, wherein the at least one particulate metal oxide sunscreen active agent is dispersed in the formulation.
  • the disclosure provides a thickened formulation comphsing an oil-based carrier comphsing at least one oil, at least one particulate metal oxide sunscreen active agent, and at least one cross-linked polymeric rheology modifier, wherein the at least one particulate metal oxide sunscreen active agent is dispersed in the formulation, for use in reducing the deleterious effects of UVA and/or UVB radiation on the skin of a user.
  • oil carrier and "oil-based carrier” means that the vehicle of the formulation comprises an oil or combination of oils and that the formulation is not in the form of a water-in-oil or oil-in-water emulsion.
  • viscosity means Brookfield viscosity measured by Brookfield viscometers at 10 rpm at 22°C, unless stated otherwise. Viscosity was measured using a Brookfield DV-II+ Viscometer or a Brookfield DV-I Prime Viscometer as indicated in the examples below.
  • rheology modifier and “thickener” are used interchangeably to mean a material that when added at 3% w/w to an oil carrier increases the value of the viscosity of the composition as defined above by at least five times, preferably 10 times, more preferably at least 20 times, and more preferably at least 50 times as measured using a Brookfield viscometer at 10 rpm at 22°C.
  • shear-thinning refers to non-Newtonian fluids which have decreased viscosity when subjected to shear strain.
  • formulations have strong shear thinning property if the viscosity ratio of the formulation at 10 rpm and 100 rpm is greater than 2 as measured by a Brookfield viscometer.
  • the viscosity ratio is greater than 2, and typically greater than 2.5.
  • the term "substantially free of” in the context of a formulation means that the formulation contains less than 10 wt %, or less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt% or less than 1 wt%, of the indicated ingredient on basis of the total weight of the formulation.
  • the term "substantially free of in the context of a polymer or copolymer means that the polymer contains less than10 wt %, or less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt% or less than 1 wt%, of the indicated ingredient on basis of the total weight of the polymer.
  • (meth)acrylate refers to acrylate and methacrylate.
  • (co)polymer indicates polymer or copolymer.
  • copolymer indicates polymer or copolymer.
  • copolymer indicates polymer or copolymer.
  • a sunscreen formulation of the disclosure comprises 1 - 20%, preferably 2 - 20%, and more preferably 3 - 20% of one or more metal oxide particulate sunscreen active agents; wherein the formulation is a stable dispersion.
  • a sunscreen formulation of the disclosure has a viscosity of at least 100 mPas, preferably at least 300 mPas, more preferably at least 1000 mPas, still more preferably at least 4000 mPas.
  • a sunscreen formulation of the disclosure can be in the form of liquid or a gel.
  • sunscreen formulations of the disclosure are substantially free of water.
  • the sunscreen formulations of the disclosure are substantially free of organic solvents. In one embodiment, the sunscreen formulations are substantially free of organic solvents that are C C 3 alcohols. In one aspect the sunscreen formulations of the disclosure are substantially free of emulsifiers.
  • sunscreen formulations of the disclosure are substantially free of glycols.
  • the sunscreen formulations of the disclosure are substantially free of dispersants other than the recited polymeric rheology modifiers.
  • the sunscreen formulations of the disclosure are substantially free of emollients. In one aspect the sunscreen formulations of the disclosure are substantially free of ingredients that are not dermatologically acceptable, such as chemicals intended for use in agricultural applications, industrial uses, or other uses that are not related to personal care products.
  • Non-limiting examples of the metal oxide sunscreen active agents are titanium dioxide (Ti0 2 ), zinc oxide (ZnO), aluminum oxide (Al 2 0 3 ), iron oxide (Fe 2 0), and zirconium dioxide (Zr0 2 ).
  • the metal oxides are Ti0 2 or ZnO.
  • the most preferred metal oxide is Ti0 2 .
  • the metal oxide sunscreen active agents do not include an organic component.
  • the polymeric rheology modifiers selected for the formulations of the disclosure will be polymers that are dermatologically acceptable for use in personal care formulations.
  • the polymer is preferably soluble in the oil carrier of the formulation.
  • a polymer is soluble in an oil if at least 3 wt% of polymer can be dissolved in the oil. Solubility can be determined by adding 3 wt% of a polymer to the oil and observing the clarity of the oil with the naked eye. The oil with dissolved polymer will be clear or have a slight translucent color or turbidity in it due to light scattering, but will not contain detectable polymer particles or a separate polymer-rich phase.
  • the polyme c rheology modifier is obtainable by co-polymerizing a monomer mixture comp sing at least one alkyl (meth)acrylate and at least one of the following monomers: a bicyclic (meth)acrylate ester different from the alkyl (meth)acrylate, and an aromatic vinyl monomer.
  • the polymehc rheology modifier is a cross-linked polymer comphsing at least one alkyl (meth)acrylate monomer and at least one cyclic monomer, wherein the cyclic monomer is selected from the group consisting of a bicyclic (meth)acrylate ester, an aromatic vinyl monomer, and combinations thereof.
  • the cross-linked polymehc rheology modifier is obtainable by co-polymerizing at least two of the following ethylenically unsaturated monomers:
  • the polymehc rheology modifier is a cross-linked copolymer comphsing two or more monomers selected from a bicyclic (meth)acrylate ester, a lower alkyl (meth)acrylate, a fatty alkyl (meth)acrylate, and an aromatic vinyl monomer, as long as the monomers comphsing the copolymer include a bicyclic (meth)acrylate ester and/or an aromatic vinyl monomer.
  • lower alkyl (meth)acrylate means Ci-C 6 alkyl (meth)acrylate.
  • fatty alkyl (meth)acrylate means C 8 -C 24 alkyl (meth)acrylate.
  • total alkyl (meth)acrylate means the total of the weight percentages of any lower alkyl (meth)acrylates and fatty alkyl (meth)acrylates present in the copolymer.
  • the polymehc rheology modifier is a cross-linked copolymer comphsing at least one cyclic monomer and at least one alkyl (meth)acrylate monomer, wherein
  • said at least one cyclic monomer is selected from the group consisting of a bicyclic (meth)acrylate ester, an aromatic vinyl monomer, and combinations thereof;
  • said at least one alkyl (meth)acrylate monomer is selected from the group consisting of a lower alkyl (meth)acrylate, a fatty alkyl (meth)acrylate, and combinations thereof.
  • the polymeric rheology modifier comp ses 5 to 50 wt% bicyclic (meth)acrylate ester, 25 to 70 wt% total alkyl (meth)acrylate, and 10 to 40 wt% aromatic vinyl monomer.
  • the rheology modifier comphses 20 to 70 wt% bicyclic (meth)acrylate ester, and 30 to 80 wt% total alkyl (meth)acrylate.
  • the bicyclic (meth)acrylate ester is isobornyl methacrylate (IBOMA)
  • the lower alkyl (meth)acrylate is isobutyl methacrylate (IBMA)
  • the aromatic vinyl monomer is styrene.
  • the rheology modifier is a cross-linked copolymer comprising a lower alkyl (meth)acrylate and/or a fatty alkyl (meth)acrylate and the rheology modifier is obtainable by co- polymerizing at least two of the following monomers:
  • the monomers comprising the copolymer include a bicyclic (meth)acrylate ester and/or an aromatic vinyl monomer.
  • the polymeric rheology modifier comphses 10 to 30 wt% bicyclic (meth)acrylate ester, 10 to 25 wt% lower alkyl (meth)acrylate, 30 to 40 wt% fatty-alkyl (meth)acrylate, and 15 to 30 wt% aromatic vinyl monomer.
  • the bicyclic (meth)acrylate ester is isobornyl methacrylate
  • the lower alkyl (meth)acrylate is isobutyl methacrylate
  • the fatty alkyl (meth)acrylate is lauryl methacrylate
  • the aromatic vinyl monomer is styrene.
  • the cross-linked polymeric rheology modifier comphses isobornyl methacrylate and isobutyl methacrylate
  • the cross-linked polymeric rheology modifier comphses styrene and isobutyl methacrylate.
  • the cross-linked polymeric rheology modifier comphses styrene, isobutyl methacrylate and lauryl methacrylate,
  • the cross-linked polymeric rheology modifier comphses isobornyl methacrylate, styrene, and isobutyl methacrylate, In one embodiment, the cross-linked polymeric rheology modifier comphses isobornyl methacrylate, isobutyl methacrylate and lauryl methacrylate,
  • the cross-linked polymeric rheology modifier comphses isobornyl methacrylate, isobutyl methacrylate and ethylhexyl methacrylate, In one embodiment, the cross-linked polymeric rheology modifier comprises isobornyl methacrylate, styrene, isobutyl methacrylate and lauryl methacrylate.
  • the weight percentages of the monomer that constitute the copolymer are based on the total weight of the monomers used, whereby the total weight of the monomers adds up to 100 wt%.
  • the bicyclic (meth)acrylate ester of the disclosure contains a (meth)acryloyl radical bonded to a six-membered carbon atom b dged ring and said group of monomers include products like decahydronaphthyl (meth)acrylates, and adamantyl (meth)acrylates, but preferred are products according to formula (I)
  • R is H or -CH 3 ,
  • A is -CH 2 -, -CH(CH 3 )- or -C(CH 3 ) 2 -, and
  • one or more M is covalently bonded to any carbon of the bicyclic rings, preferably to a carbon atom of the six-membered ring, and is selected from the group consisting of hydrogen, halogen, methyl and methylamino group or a plurality thereof.
  • Non-limiting examples of the bicyclic (meth)acrylate esters include isobornyl (meth)acrylate, bornyl (meth)acrylate, fenchyl (meth)acrylate, isofenchyl (meth)acrylate, norbornyl (meth)acrylate, cis, (endo) 3-methylamino- 2-bornyl (meth)acrylate, 1 ,4,5,6,7,7-hexachlorobicyclo [2.2.1 ]-hept-5-ene-2-ol (meth)acrylate (HCBOMA) and 1 ,4,5,6,7,7-hexachlorobicyclo [2.2.1 ]-hept-5-ene-2 methanol (meth)acrylate (HCBMA), and mixtures of such bicyclic (meth)acrylates.
  • the bicyclic (meth)acrylate ester of the disclosure is a b dged bicyclic (meth)acrylate ester.
  • a bhdged bicyclic monomer means a monomer with two rings that share three or more atoms, separating the two bridgehead atoms by a bridge containing at least one atom.
  • a suitable bicyclic (meth)acrylate ester is isobornyl methacrylate.
  • the bicyclic (meth)acrylate esters are known per se and may be prepared in known fashion or may be obtained from commercial sources.
  • the bicyclic (meth)acrylate is preferably chosen from monomers which, when polymerized, form a homopolymer that is soluble in the oil carrier of the sunscreen formulation.
  • Alkyl (meth)acrylates of the disclosure include lower alkyl (meth)acrylates, fatty-alkyl (meth)acrylates and mixtures thereof.
  • the alkyl (meth)acrylates are linear or branched.
  • the alkyl (meth)acrylates are substituted.
  • Lower alkyl (meth)acrylates of the disclosure are C- ⁇ -C 6 alkyl (meth)acrylates.
  • lower alkyl (meth)acrylates of the disclosure are compounds wherein a (meth)acryloyl radical is bonded to a lower alkyl group, herein defined as a Ci-C 6 alkyl group, which can be linear or branched, substituted or unsubstituted, saturated or unsaturated.
  • Lower alkyl (meth)acrylates of the disclosure include compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate and hexyl (meth) acrylate.
  • a preferred lower alkyl (meth)acrylate is isobutyl (meth)acrylate.
  • the lower alkyl (meth )acry late is preferably chosen from monomers which, when polymerized, form a homopolymer that is soluble in one or more of the oils of the formulations of the disclosure, and combinations thereof.
  • the amount of this monomer in the polymeric rheology modifier is preferably limited to less than about 60%, more preferably less than 50% and more preferably less than about 40% by weight of the polymer.
  • Fatty-alkyl (meth)acrylates of the disclosure are C 8 -C 24 alkyl (meth)acrylates. More particularly, the fatty-alkyl (meth)acrylates of the disclosure are compounds wherein a (meth)acryloyl radical is bonded to a fatty alkyl group, herein defined as a C 8 -C 2 4 alkyl group, which can be linear or branched, substituted or unsubstituted, and saturated or unsaturated.
  • Examples of a fatty alkyl (meth)acrylate include 2-ethylhexyl (meth )acry late, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, methacrylate ester 13.0 (CAS#: 90551-76-1 ), tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, methacrylate ester 17.4 (CAS#: 90551 -84-1 ), and stearyl (meth)acrylate.
  • Preferred fatty-alkyl (meth)acrylates are chosen from monomers which, when polymerized, form a homopolymer which is soluble in the one or more of the oils of the formulations of the disclosure, and combinations thereof.
  • 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth )acry late, methacrylate ester 13.0 (CAS#: 90551-76-1 ), methacrylate ester 17.4 (CAS#: 90551 -84-1 ), and/or stearyl (meth)acrylate is used.
  • lauryl methacrylate or 2-ethylhexyl (meth)acrylate is used.
  • the aromatic vinyl monomers of the disclosure contain a vinyl group bonded to an aromatic group.
  • examples include styrene, substituted styrene, vinyl naphthalene, and mixtures thereof.
  • Preferred substituted styrenes include ortho-, meta- and/or para- alkyl, alkyloxy or halogen substituted styrenes, such as methyl styrene, 4-tert-butyl styrene, tert-butyloxy styrene, 2- chlorostyrene and 4-chlorostyrene.
  • the preferred aromatic vinyl monomer is styrene.
  • the use of styrene can increase the Tg of the polymer and reduce the cost.
  • the amount of this monomer in the polymeric rheology modifier is preferably limited to less than about 60%, more preferably less than 50% and more preferably less than about 40% by weight.
  • Other ethylenically unsaturated monomers different from the monomers above can also be included in the polymeric rheology modifier.
  • monomers such as (meth)acrylic acid, maleic acid, 2-acrylamido-2-methylpropane, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-[3-(dimethylamino) propyl] methacrylamide, N-[3- (dimethylamino) propyl] acrylamide, (3-acrylamidopropyl)-trimethyl-ammonium chloride, methacrylamido propyl trimethyl ammonium chloride, (meth)acrylamide, N-alkyl (meth)acrylamides, N-vinyl pyrrolidone, vinyl formamide, vinyl acetamide, and N-vinyl caprolactams.
  • monomers such as (meth)acrylic acid, maleic acid, 2-acrylamido-2-methylpropane, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N-[3-(di
  • the polymer rheology modifier contain less than 2.5%, more preferably, less than 1 .5% and most preferably less than 1 % by weight of these monomers.
  • the polymeric rheology modifier of the disclosure is largely free of the polymerized residues of polar monomers.
  • Polar monomers are defined as monomers that contain hydroxyl, carboxylic acid, nitrogen, or heterocyclic functionality.
  • the polymeric rheology modifiers are cross-linked polymers and further comprise suitable cross-linking monomers.
  • Cross-linking monomers contain two or more ethylenically unsaturated functionalities. These include, but are not limited to divinyl benzene, 1 ,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylol propane tri(meth)acrylate, trimethylolpropane triacrylatel, trimethylol propane diallyl ether, trimethylol propane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, and pentaerythritol tri(meth)acrylate.
  • the amount of cross-linker optionally present in the polymeric rheology modifier, based on the total weight of all monomers in the polymer, is from about 20 mg/kg to about 2000 mg/kg, preferably about 200 mg/kg to about 1500 mg/kg, more preferably about 300 mg/kg to about 1000 mg/kg, more preferably about 350 mg/kg to about 650 mg/kg.
  • the amount of cross- linker in the polymeric rheology modifier is 200 mg/kg, or 220 mg/kg, or 240 mg/kg, or 260 mg/kg, or 280 mg/kg, or 300 mg/kg, or 320 mg/kg, or 340 mg/kg, or 360 mg/kg, or 380 mg/kg, 400 mg/kg, or 420 mg/kg, or 440 mg/kg, or 460 mg/kg, or 480 mg/kg, 500 mg/kg, or 520 mg/kg, or 540 mg/kg, or 560 mg/kg, or 580 mg/kg, 600 mg/kg, or 620 mg/kg, or 640 mg/kg, or 660 mg/kg, or 680 mg/kg, or 700 mg/kg, or 720 mg/kg, or 740 mg/kg, or 760 mg/kg, or 780 mg/kg, 800 mg/kg, or 820 mg/kg, or 840 mg/kg, or 860 mg/kg, or 880 mg/kg, or 860 mg/
  • the amount of cross-linker will be selected to optimize the ability of the polymer to both thicken the oil and suspend the metal oxide particles. If the level of cross-linker is either too low or too high the particles will not remain in a stable dispersion.
  • the amount of cross-linker that will optimize system performance may vary depending on the selection of monomers, the relative proportions of the monomers in the polymer, the oil used as a carrier in the formulation, the size and type of particles to be suspended, and other ingredients to be included in the formulation.
  • the glass transition temperatures (Tg) of the polymeric rheology modifier is high enough that the polymer can be isolated and handled as a solid at room temperature (approximately 22 °C).
  • the Tg of the polymeric rheology modifier is greater than about 45 °C, more preferably greater than about 60 °C and more preferably greater than about 75 °C.
  • Tg can be measured using standard procedures such as differential scanning calorimetry. For the Tg values described herein, the Tg of the polymer was determined by placing a vial containing the polymer powder to be measured into a hot water bath (e.g., 75 °C) for 10 minutes.
  • the Tg of the powder was determined to be at least the temperature of the water bath.
  • the temperature of the water bath was increased incrementally until the polymer was no longer free flowing to determine the Tg where appropriate. In other instances, a Tg was determined to be "greater than" the last water bath temperature in cases were an upper end transition temperature was not determined.
  • the polymeric rheology modifiers of the present disclosure typically have a Tg > 75 °C.
  • the weight averaged molecular weight (Mw) of the copolymer of the invention when measured in accordance withthe method described below in Example 9, is preferably at least 20,000,000 Dalton (D), suitably at least 50,000,000 (D); 100,000,000 (D); 150,000,000; and/or at least 200,000,000 D.
  • the polymeric rheology modifier of the disclosure may be synthesized by conventional methods for vinyl addition polymerization known to those skilled in the art, such as, but not limited to, solution polymerization, precipitation polymerization, and dispersion polymerizations, including suspension polymerization and emulsion polymerization.
  • the preferred process is emulsion polymerization.
  • one or more monomers are dispersed in an aqueous phase and polymerization is initiated using a water soluble initiator.
  • the monomers are typically water insoluble or very poorly soluble in water, and a surfactant or soap is used to stabilize the monomer droplets in the aqueous phase.
  • Polymerization occurs in the swollen micelles and latex particles.
  • Other ingredients that might be present in an emulsion polymerization include chain transfer agents such as mercaptans (e.g. dodecyl mercaptan) to control molecular weight, small amounts of water soluble organic solvents such as but not limited to acetone, 2-butanone, methanol, ethanol, and isopropanol, to adjust the polarity of the aqueous phase, and electrolytes to control pH.
  • chain transfer agents such as mercaptans (e.g. dodecyl mercaptan) to control molecular weight
  • water soluble organic solvents such as but not limited to acetone, 2-butanone, methanol, ethanol, and isopropanol, to adjust the polarity of the aqueous phase, and electrolytes to control pH.
  • Suitable initiators include alkali metal or ammonium salts of persulfate such as ammonium persulfate, water-soluble azo compounds such as 2,2'-azobis(2- aminopropane)dihydrochloride, and redox systems such as Fe(ll) and cumene hydroperoxide, and tert-butyl hydroperoxide-Fe(ll)-sodium ascorbate.
  • Suitable surfactants include anionic surfactants such as fatty acid soaps (e.g. sodium or potassium stearate), sulfates and sulfonates (e.g.
  • Anionic surfactants and combinations of anionic surfactants and non-ionic surfactants are most commonly used.
  • Polymeric stabilizers such as polyvinyl alcohol-co-vinyl acetate) can also be used as surfactants.
  • the solid polymer product free of the aqueous medium can be obtained by a number of processes including destabilization/coagulation of the final emulsion followed by filtration, solvent precipitation of the polymer from latex, or spray drying of the latex.
  • the powder particle size of the powder is preferably smaller than 60 mesh size, more preferably smaller than 100 mesh size (or -150 microns).
  • the polymeric rheology modifiers of the present disclosure are preferably a free flowing powder obtained by a spray drying process or by any suitable drying processes known in the art. However, a liquid latex of polymeric rheology modifier can also be used if the application can tolerate the presence of some water.
  • mesh size refers to standard United States (US) mesh size. The mesh size number indicates the number of openings located along 1 linear inch of mesh.
  • the polymeric rheology modifiers used in the sunscreen formulations of the present disclosure comprise at least 5 wt% of bicyclic (meth)acrylate ester, in another aspect at least 10 wt%, in another aspect at least 20 wt%, in another aspect at least 40 wt%, in still another aspect at least 60 wt%, and in still another aspect at least 70 wt%.
  • the preferred range of bicyclic (meth)acrylate ester present in the rheology modifier is 5 to 50 wt%.
  • the preferred range of bicyclic (meth)acrylate ester present in the rheology is 10 to 30 wt%.
  • the preferred range of bicyclic (meth)acrylate ester present in the rheology is 20 to 70 wt%, or 25 to 60 wt%, or 30 to 55 wt%.
  • the amount of bicyclic (meth)acrylate ester in the polymeric rheology modifier is 5 wt%, or 10 wt%, or 15 wt% or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt% or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt% or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%.
  • the polymeric rheology modifiers used in the sunscreen formulations of the present disclosure comprise at least 25 wt% of total alkyl (meth)acrylates, in another embodiment at least 35 wt%, in another embodiment at least 50 wt%, in another embodiment at least 65 wt%, and in another embodiment at least 80 wt%.
  • the preferred range of total alkyl (meth)acrylate present in the rheology modifier is 25 to 70 wt%.
  • the preferred range of total alkyl (meth)acrylate present in the rheology is 30 to 80 wt%, or 40 to 75 wt%, or 45 to 70 wt%.
  • the amount of total alkyl (meth)acrylate in the polymeric rheology modifier is 25 wt%, or 30 wt%, or 35 wt% or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt% or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt% or 80 wt%, or 85 wt%, or 90 wt%.
  • polymeric rheology modifiers used in the sunscreen formulations of the present disclosure comprise at least 10 wt% of lower alkyl (meth)acrylates, in another embodiment at least 15 wt%, in another embodiment at least 20 wt%, in another embodiment at least 25 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt %, or at least 60 wt %, or at least 65 wt%, or at least 70 wt %, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%.
  • the preferred range of lower alkyl (meth)acrylate present in the rheology modifier is 50 to 90 wt%.
  • the polymeric rheology modifiers used in the sunscreen formulations of the present disclosure comprise at least 10 wt% of fatty alkyl (meth)acrylates, or at least 20 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt%.
  • the preferred range of fatty alkyl (meth)acrylate present in the rheology modifier is 20 to 40 wt%.
  • the polymeric rheology modifiers used in the sunscreen formulations of the present disclosure comprise less than about 40 wt% of aromatic vinyl monomers, in another embodiment less than about 35 wt%, less than about 30 wt%, less than about 25 wt%, in another embodiment less than about 20 wt%, and in another embodiment less than about 15 wt%.
  • the preferred range of aromatic vinyl monomer present in the rheology modifier is 10 to 40 wt%, or 15 to 30 wt%.
  • the polymeric rheology modifier used in the sunscreen formulations of the present disclosure is polymerized from a reaction mixture comprising:
  • the polymeric rheology modifier used in the sunscreen formulations of the present disclosure is polymerized from a reaction mixture comprising:
  • the polymeric rheology modifier used in the sunscreen formulations of the present disclosure is polymerized from a reaction mixture comprising:
  • the polymeric rheology modifier used in the sunscreen formulations of the present disclosure is obtainable by copolyme zing a lower alkyl (meth)acrylate monomer with at least one additional monomer selected from:
  • the monomers comprising the copolymer include a bridged bicyclic (meth)acrylate ester and/or an aromatic vinyl monomer, and wherein each of said monomers can be substituted or unsubstituted.
  • the weight percentages of the monomer that constitute the copolymer are based on the total weight of the monomers used, whereby the total weight of the monomers adds up to 100 wt%, except for the presence of cross-linker.
  • the monomers may be arranged in any fashion, such as in blocks or randomly.
  • the copolymer is a randomly arranged copolymer.
  • the rheology modifiers used in the sunscreen formulations of the present disclosure are preferably a free flowing powder obtained by a spray drying process or by any suitable drying processes known in the art. However, a liquid form can also be used.
  • oils are selected from one or more oils that are dermatologically acceptable and suitable for use in a sunscreen formulation, and are preferably in the liquid state at the temperature of application.
  • oils suitable for use in the sunscreen formulations of the disclosure include triglycerides, esters, silicone oils with aromatic groups, organic sunscreen active ingredients, and aromatic compounds.
  • Preferred triglycerides are plant de ved oils including soybean oil, sunflower oil, safflower oil, canola oil, rapeseed oil, corn oil, macadamia oil, and tea oil.
  • Non-limiting examples of triglycerides are caprylic capryl triglyceride, glycerol tri- 2-ethylhexyl, and oils of various plants.
  • More preferred triglycerides are caprylic capryl triglyceride and oils from various plants. More preferred oils from various plants are soy bean oil, rapeseed oil, canola oil, corn oil, and linseed oil. Preferred esters are fatty acid esters, lactates, maleates, adipates, citrates, succinates, and benzoate esters.
  • the fatty acid esters suitable for use in the formulations of the present disclosure refer to any dermatologically acceptable ester of an oil de ved from vegetables or animals, including but not limited to hydrogenated and non-hydrogenated, epoxidized and non- epoxidized, soy methyl esters, rapeseed methyl esters, canola methyl esters, safflower methyl esters, ricinoleic acid methyl esters, castor methyl esters, isopropyl myristate, isopropyl palmitate, methyl oleate, and C 8 -C 10 methyl esters.
  • the fatty acid esters of the disclosure are preferably plant dehved.
  • the preferred lactates are 2-ethylhexyl lactate, butyl lactate and propyl lactate.
  • the preferred maleate is diethyl maleate.
  • the preferred adipate is dimethyl adipate.
  • the preferred citrates are acetyl tributyl citrate, butyryltri-n-hexyl citrate, and tributyl citrate.
  • the preferred succinate is diethyl succinate.
  • the preferred benzoates are methyl benzoate, ethyl benzoate, and C12/15 benzoate.
  • the term "oil" can also include certain organic sunscreen active agents.
  • a "sunscreen active agent” or “sunscreen active” shall include all of those materials, singly or in combination, that are regarded as acceptable for use as active sunscreen ingredients based on their ability to absorb UV radiation. Such compounds are generally desc bed as being UV-A, UV-B, or UV-A/UV-B active agents. Approval by a regulatory agency is generally required for inclusion of active agents in formulations intended for human use.
  • Those active agents which have been or are currently approved for sunscreen use in the United States include organic and inorganic substances including, without limitation, para aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, diethanolamine methoxycinnamate, digalloy trioleate, ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, lawsone with dihydroxyacetone, red petrolatum.
  • organic and inorganic substances including, without limitation, para aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazo
  • sunscreen actives examples include ethylhexyl triazone, dioctyl butamido triazone, benzylidene malonate polysiloxane, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexyl benzoate, bis diethylamino hydroxybenzoyl benzoate, bis benzoxazoylphenyl ethylhexylimino triazine, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethylbutylphenol, and bis- ethylhexyloxyphenol methoxyphenyltriazine, 4-methylbenzylidenecamphor, and isopentyl 4- methoxy
  • the preferred organic sunscreen active ingredients are octyl salicylate, ethylhexyl methoxycinnamate, homosalate, octocrylene, and menthyl anthranilate (meradimate).
  • sunscreen active agents currently approved for human use but is readily applicable to those that may be allowed in the future.
  • organic sunscreen active ingredients are octyl salicylate, ethylhexyl methoxycinnamate, homosalate, octocrylene, and menthyl anthranilate (meradimate). Due to regulations in various countries, the amount of total organic sunscreen active ingredients in a formulation cannot be greater than 32%. Because of this limitation, if organic sunscreen active ingredients are used in the sunscreen formulations of the disclosure, at least one other oil of the disclosure is also used in the formulation.
  • Preferred silicone oils with aromatic groups include phenyl trimethicone (Dow Corning 556 oil). Mixtures of oils also can be used. Other dermatologically acceptable oils will be known to those skilled in the dermatological arts.
  • the sunscreen formulation comprises, based on total formulation weight, 40 - 99.5 wt% oil, preferably 60 - 80 wt% oil.
  • the amount of oil in the thickened oil composition is 40 wt%, or 45 wt%, or 50 wt% or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt% or 95 wt%, or 99.5 wt%.
  • the sunscreen formulation comprises, based on total formulation weight, 0.5 - 15% rheology modifier, or 1 - 10%, or 2 - 8% rheology modifier, or 3-5 % rheology modifier.
  • the amount of rheology modifier in the sunscreen formulation is 0.5 wt%, or 1 wt%, or 2 wt% or 3 wt%, or 4 wt%, or 5 wt%, or 6 wt% or 7 wt%, or 8 wt%, or 9 wt%, or 10 wt% or 1 1 wt%, or 12 wt%, or 13 wt%, or 14 wt% or 15 wt%.
  • the sunscreen formulation comprises, based on total formulation weight, metal oxide particulate sunscreen active agents at a concentration of between 2 to 50 wt%, preferably 3 - 40 wt%, and more preferably 4 - 35 wt%.
  • the weight percentages of the formulation are based on the total formulation weight, whereby the total weight of the formulation adds up to 100 wt%.
  • Other ingredients are based on the total formulation weight, whereby the total weight of the formulation adds up to 100 wt%.
  • the sunscreen formulations of the disclosure can optionally contain additional cosmetically acceptable ingredients, as long as those ingredients are either soluble in the formulation or are in the form of particulates that exist in stable dispersions in the formulations.
  • sunscreen formulations of the present disclosure can be polymeric or non-polymeric.
  • Non- limiting examples include the thickeners disclosed in "Diverse Technologies for Polymeric Oil Thickeners" posted on March 14, 2014 by George Deckner at http://knowledge.ulprospector.com/388/pcc-diverse-technologies-polymeric-oil-thickeners, the contents of which are incorporated herein by reference in their entirety.
  • rheology modifiers Asensa CL 300 (ethylene/vinyl acetate copolymer) and SC 401 (ethylene/acrylic acid copolymer) (both from Honeywell); Syncrowax ORM (Sorbitol/Sebacic Acid Copolymer Behanate) (Croda); Hostacerin DP (Dextrin Palmitate) (Clariant); Rheopearl ISK2/ISL2 (Stearoyl Inulin) (Chiba Flour Milling Ltd); Versagels (thickened oil gels) (Calumet Penreco); Intelimer IPA 13-6 and Intelimer IPA 13-1 (poly C10-30 alkyl acrylates)(Air Products and Chemicals);; Kraton G1702 Polymer (styrene and ethylene/propylene diblock copolymer); and hydrogenated castor oil.
  • Atlox Rheostrux 200 and Atlox Rheostrux 100 , and Oledilic Acid Copolymer
  • compositions of the present invention may contain a wide range of additional, optional components which are referred to herein as "cosmetic components", but which can also include components generally known as pharmaceutically active agents.
  • Cosmetic components include additional, optional components which are referred to herein as "cosmetic components", but which can also include components generally known as pharmaceutically active agents.
  • CTFA Cosmetic Ingredient Handbook Seventh Edition, 1997 and the Eighth Edition, 2000, which is incorporated by reference herein in its entirety, describes a wide variety of cosmetic and pharmaceutical ingredients commonly used in skin care compositions, which are suitable for use in the compositions of the present invention.
  • these functional classes disclosed in this reference include: abrasives, antioxidants, vitamins, biological additives, chemical additives, colorants, cosmetic astringents, cosmetic biocides, drug astringents, external analgesics, film formers, fragrance components, sunscreen agents, ultraviolet light absorbers, and SPF boosters.
  • Fragrances are aromatic substances which can impart an aesthetically pleasing aroma to the sunscreen composition.
  • Typical fragrances include aromatic materials extracted from botanical sources (i.e., rose petals, gardenia blossoms, jasmine flowers, etc.) which can be used alone or in any combination to create essential oils.
  • alcoholic extracts may be prepared for compounding fragrances.
  • One or more fragrances can optionally be included in the sunscreen composition in an amount ranging from about 0.001 to about 5 weight percent, preferably about 0.01 to about 0.5 percent by weight.
  • Essential oils can be included in the sunscreen formulations.
  • the preferred essential oils are sandalwood oil, cedarwood oil, chamomile oil, vanilla oil, tea tree oil, eucalyptus oil, peppermint oil, bergamot oil, lavender oil, rosemary oil, rose oil, cinnamon oil, frankincense oil, lemongrass oil, geranium oil, orange oil, vetiver oil, lemon oil, jasmine oil, cedar oil, and grapefruit oil. Pine oil and d-limonene also can be used.
  • such essential oils also can be thickened by the cross-linked polymeric rheology modifiers of the disclosure.
  • Additional preservatives may also be used if desired and include well known preservative compositions such as benzyl alcohol, phenyl ethyl alcohol and benzoic acid, diazolydinyl, urea, chlorphenesin, iodopropynyl and butyl carbamate, among others.
  • compositions of the invention may further include insect repelling components.
  • insect repelling active agent for personal care products is N,N-Diethyl-m-toluamide, frequently called "DEET" and available in the form of a concentrate containing at least about 95 percent DEET.
  • Other synthetic chemical repellents include ethyl butylacetylaminoproprionate (also known as IR 3535), dimethyl phthalate, ethyl hexanediol, indalone, di-n- propylisocinchoronate, bicycloheptene, dicarboximide and tetrahydrofuraldehyde.
  • Certain plant- derived materials also have insect repellent activity, including citronella oil and other sources of citronella (including lemon grass oil), limonene, rosemary oil and eucalyptus oil.
  • Choice of an insect repellent for incorporation into the sunscreen emulsion will frequently be influenced by the odor of the repellent.
  • the amount of repellent agent used will depend upon the choice of agent; DEET is useful at high concentrations, such as up to about 15 percent or more, while some of the plant-derived substances are typically used in much lower amounts, such as 0.1 percent or less.
  • the method of making the sunscreen formulations of this application comprises the steps of mixing the polymeric rheology modifier in the oil carrier with adequate agitation and for a sufficient period of time (usually ⁇ 30 minutes) to dissolve the rheology modifier in the carrier, and then mixing in the metal oxide particulates of desired size ( ⁇ 10 microns) with adequate agitation and for a sufficient period of time to obtain a dispersion. Additional ingredients can be added to the formulation either before the rheology modifier is added to the oil carrier, or after the rheology modifier has been added but before the metal oxide particulates are added, or after the metal oxide particulates are added. In most cases, the formulations can be prepared at room temperatures using an overhead stirrer.
  • heating may be used to facilitate dissolution of the rheology modifier into the oils.
  • homogenization add the rheology after homogenization or limit the homogenization duration to less than 3 minutes if the rheology modifier is in the formulation.
  • compositions of the invention described herein Typical application of the compositions of the invention described herein to skin of a human will provide enhanced protection against deleterious effects of ultraviolet radiation (UVR).
  • UVR ultraviolet radiation
  • the subject invention further provides a method for protecting human skin against the deleterious effects of solar radiation, more particularly UVR, which method comprises topically applying thereto an effective amount of the compositions as described herein.
  • An esthetically beneficial result of exposure of skin to UVR i.e., light radiation wavelengths of from 280 nm to 400 nm
  • Another benefit of sun exposure comes from production of vitamin D within the skin.
  • UVR is typically divided into UV-A (light wavelengths from 320 to 400 nm) and UV-B (wavelengths ranging from 280 to 320 nm) regions.
  • Overexposure to UV-B irradiation is generally understood to lead to skin burns and erythema.
  • overexposure to UV-A radiation may cause a loss of elasticity of the skin and the appearance of wrinkles, promoting premature skin aging.
  • Such irradiation promotes triggering of the erythemal reaction or amplifies this reaction in certain individuals and may even be the source of phototoxic or photoallergic reactions. It is increasingly believed that overexposure to UV-A may also lead to melanoma.
  • the application of the compositions of the invention to the skin of an individual will provide enhanced UVR photoprotection (UV-A and/or UV-B) of the skin of the individual.
  • the rheology modifiers of the disclosure have the ability to thicken personal care oils suitable for use as oil carriers in sunscreen formulations.
  • thickening a composition means to increase the viscosity of the oil carriers by at least five times, or at least 10 times, preferably at least 20 times, and more preferably at least 50 times in the presence of 3 %w/w or less of the rheology modifier compared to the same fluid in the absence of the rheology modifier.
  • Viscosity is measured by Brookfield viscometers at 10 rpm at 22 °C, using either a Brookfield DV-II+ Viscometer or a Brookfield DV-I Prime Viscometer as indicated in the examples below.
  • the viscosity of an oil is low and pure oils are generally Newtonian fluids.
  • fatty acid ester is less than 10 mPas and soy oil is ⁇ 50 mPas and they are Newtonian.
  • the thickened sunscreen formulations of the disclosure can be gel-like (very high viscosity) but preferably the viscosity of the formulations is less than -10000 mPas, preferably less than 5000 mPas.
  • the viscosity of the thickened sunscreen formulations of the disclosure is at least 150 mPas, preferably at least 300 mPas, more preferably at least 600 mPas, and still more preferably at least 1000 mPas.
  • the thickened sunscreen formulations of the disclosure display shear thinning property and the formulation viscosity does not increase by more than 50%, preferably not more than 30%, more preferably not more than 20%, and still more preferably not more than 10%, after storage tests.
  • shear-thinning refers to non-Newtonian fluids which have decreased viscosity when subjected to shear strain.
  • formulations have strong shear thinning property if the viscosity ratio of the formulation at 10 rpm and 100 rpm is greater than 2 as measured by a Brookfield viscometer. For a stable formulation in our examples, the viscosity ratio is greater than 2, and typically great than 2.5.
  • Exemplary polymeric rheology modifiers were made using different combinations of monomers.
  • Isobornyl methacrylate (IBOMA), isobutyl methacrylate (IBMA), 2-ethylhexylmethacrylate (2- EHMA) and isodecyl methacrylate (IsoCIO MA) were obtained from Sigma-Aldrich.
  • Lauryl methacrylate (LMA) was methacrylic ester 13.0 obtained from Evonik (VISIOMER ® terra CI S- MA).
  • VISIOMEFT i-BMA isobutyl methacrylate
  • VISIOMEFT Terra IBOMA isobornyl methacrylate
  • 2-EHMA isodecyl methacrylate
  • IDMA isodecyl methacrylate
  • Example 1 Synthesis of Cross-Linked Isobornyl methacrylate - Isobutyl methacrylate polymeric rheology modifier
  • Exemplary polymeric rheology modifier (Synthesis Example 1 ) was prepared according to the following basic procedure.
  • a 2 L, 4-neck round bottom flask was equipped with an overhead mechanical stirrer; a Y-tube equipped with a nitrogen purge outlet-topped condenser and a thermometer; and two septa.
  • deionized water and Aerosol OT-75 PG were charged to the flask.
  • Aerosol OT-75 PG Aerosol OT-75 PG
  • the reaction temperature was brought to about 48 °C.
  • a 12 minute sub-surface nitrogen purge was then initiated via a needle inserted through one of the septa while maintaining a 200 rpm agitation rate. While maintaining the nitrogen purge, the monomer mixture and acetone were charged to the reaction vessel. The sub-surface nitrogen purge was continued after the monomer/acetone addition.
  • a reductant solution consisting of sodium ascorbate and iron (II) sulfate heptahydrate dissolved in deionized water was prepared.
  • the iron (II) sulfate heptahydrate was added after the ascorbate had dissolved and just before use of the reductant solution.
  • reaction was purged for an additional 12 minutes after the monomer/acetone addition, and then the resulting dark blue ascorbate solution was added via syringe to the reaction vessel in one shot while maintaining the sub-surface nitrogen purge.
  • Solid polymer was isolated by adding the undiluted emulsion polymer to an excess of 0.5 N ammonium acetate in deionized water. The resulting precipitate was collected by vacuum filtration and washed extensively with water, and the solid was dried to a constant weight in a forced air oven at 60 °C.
  • solid polymer can be obtained by pan-drying or spray drying the liquid product at elevated temperatures with various techniques known to the skilled in the art. The solid obtained after drying can be further ground into a fine powder with various techniques known to the skilled in the art. The powder was passed through a 100 mesh screen in this example.
  • Example 2 Synthesis of Additional Polyme c Rheology Modifiers
  • Crosslinker "A” is 1 ,6-hexanediol diacrylate (1 ,6-HDDA);
  • Crosslinker “B” is trimethylolpropane triacrylate (TMPTA);
  • Crosslinker C is pentaerythritol allyl ether (PEAE);
  • t-BHP t-butyl hydroperoxide.
  • the oven dried powders were ground and passed through a 60 or 100 mesh screen before use
  • Powder can also be used without passing the 60-100 mesh screen
  • Example 3 Polyme c Rheology Modifier Thickening Performance in Fatty Acid Esters The viscosity of exemplary polymeric rheology modifiers of Table 2 in soy methyl ester (SME)
  • SME is a clear low viscosity liquid with a viscosity of about 3 - 8 mPas at room
  • the SME used was from Cargill (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Methyl soyate), Enviro Saver (trade name Meth
  • Viscosity of the thickened oil samples above was measured with a Brookfield
  • Table 4 shows that the rheology modifiers of the present disclosure can thicken mixtures of SME and soybean oil.
  • the thickening ability of various thickeners of the present disclosure in various oils was studied.
  • the studied samples contained 5% thickener and 95% oils.
  • Each sample was prepared by adding 5% thickener to 95% oil and immediately mixed vigorously for about 15 - 30 minutes.
  • Samples 4.8 - 4.22 and 4.32 of Table 4B_ were prepared at room temperature.
  • Samples 4.23 - 4.31 of Table 4B were prepared at ⁇ 70°C for 15 - 30 minutes. Samples were placed at room temperature overnight and were shaken by hand before observation to generate air bubbles. Appearance of each sample at room temperature and thickening of each were observed and recorded in Table 4B.
  • the thickening was determined qualitatively and it could be easily compared to the original organic liquid by eye estimate.
  • the thickening was observed by looking at how long the bubbles remained suspended in the liquid after shaking. Generally, the bubbles rise to the surface quickly (less than ⁇ 10 seconds) in pure oils after shaking because the viscosity of the oils are low (typically ⁇ 100 mPas). If thickening occurs, the bubbles in a thickened oil tend to remain suspended in the liquid for at least more than a few minutes, and in some cases at least 15 minutes longer than the bubbles in the pure oil. All samples in Table 4B were able to trap bubbles for more than 15 minutes longer than in the respective pure oils except where indicated.
  • estol 3609 (glycerol tri-2-
  • UV cocktail Avobenzone 9.37 wt%, Homosalate 40.62 wt%, Octisalate 15.63
  • Dispersion formulations were prepared using soy methyl ester as the oil component, exemplary rheology modifier 2.9, and Ti0 2 as the dispersed particulate.
  • the rheology modifier Ex. 2.9 was dissolved in the SME at room temperature first before adding Ti0 2 .
  • the Ti0 2 was Tiona® Ti0 2 569 from Cristal Global, the soy methyl ester was Methyl Soyate from Cargill, and the viscosity was measured with a Brookfield DV-II+ Viscometer.
  • Formulation C is a control sample.
  • the Ti0 2 was UV Titan M-170 from Presperse, the soy methyl ester was from Enviro Saver, and viscosity was measured with a Brookfield DV-I Prime. All viscosity measurements were taken at room temperature. The results are presented in Table 5A.
  • Example 5A Two dispersion formulations were prepared by the method of Example 5A. A drop of each formulation ( ⁇ 0.05 g) was deposited on the skin (back of the hand) of a user, and rubbed in gently. The skin feel was evaluated subjectively. Whiteness persistency was also evaluated subjectively with naked eyes. The water repellency was evaluated by rinsing the hand with the rubbed-in sample in tap water for three minutes. If the water droplets beaded up on the part of the skin with sample applied after the water rinsing period, the water repellency was rated "excellent". The results are presented in Table 5B.
  • Whiteness persistency is considered a desirable performance attribute in some market segments.
  • Example 6 Water Resistance Study Water resistance was evaluated by measuring SPF performance after initial application of the formulaton to a test sample and after immersion of the test samples in water, and comparing the results.
  • the sunscreen formulation was gently rubbed in with a gloved finger for 20 to 30 seconds, mimicking the application of sunscreen to a body. Once the sunscreen was spread, the sample was transferred to a 6cm x 6cm glassless slide mount and allowed to dry for 15 minutes. SPF measurements were made using the UV-1000S Ultraviolet Transmittance Analyzer. The SPF values given herein are the average of five measurements taken at different locations on each sample.
  • post-immersion SPF refers to the SPF of the sunscreen composition after being subjected to the following water immersion test
  • initial SPF refers to the SPF of the sunscreen composition prior to immersion in water for 80 minutes, as described herein. All SPF values and values for percent SPF rating decrease following water immersion given herein are based on in vitro testing.
  • each sunscreen sample in Table 6 was applied to a hydrated VITRO-SKIN® synthetic skin substrate and the initial SPF of the composition was measured as described above.
  • the sunscreen composition-treated VITRO-SKIN® samples were then transferred to a water bath at the same time at 40°C with agitation at 200 rpm for 80 minutes. The samples were removed from the water bath after 80 minutes, patted dry, and the post-immersion SPF of the samples was tested using the Labsphere UV-1000S Ultraviolet Transmittance Analyzer.
  • the post-immersion SPF values given herein are the average of five measurements taken at different locations on each sample.
  • a sunscreen formulation of the present invention was prepared.
  • the soy methyl ester was from Enviro saver.
  • Ti0 2 was UV Titan M-170 from Presperse.
  • the formulation was compared to a commercial product J&J Pure and FreeTM Baby Sunscreen Lotion (SPF 60) which states on the label that it has "Water resistance (80 minutes)".
  • the viscosity was measured by a Brookfield RVDV-I Prime Viscometer with RV -C(93) helipath @ 10rpm.
  • the rheology modifier was dissolved in the soy methyl ester. Then Ti02 was added and the sample was mixed using a regular mixer until homogeneous.
  • fatty acid ester formulations containing polymeric rheology modifiers of the disclosure were analyzed using talc model powder.
  • Talc model powder Talc-Luzena c 10 mo, particle size ⁇ 10 microns
  • SME soy methyl ester
  • Formulation samples (each 100 g in a 4 oz bottle) were prepared by mixing the thickener in the SME until dissolved into a clear liquid, followed by adding the talc. Overhead mixer was used to mix the sample for about 30 minutes at room temperature. The formulation samples were maintained at 50°C for 14 days in an oven. Some samples were maintained under this condition for 60 days.
  • the polymeric rheology modifier is considered an effective thickener (or suspension aid) if the sunscreen formulations containing 4 wt% polymeric rheology modifier are stable (no separation after 2 weeks storage at 50 ° to 54°C).
  • Top clear means the top portion of the composition containing no solid particle as visually observed and as measured in relation to the total composition height.
  • Example 8 Thickened oil composition and suspension of Ti0 2 in thickened oil compositions where organic sunscreen active ingredients are used as part of the oil
  • Molecular weight was determined by Hydrodynamic Chromatography with multiangle light scattering detection (MALS). This method is similar to a standard GPC/MALS, except a smaller pore size column is used compared to standard GPC/MALS, which results in all the separation taking place in the interstitial volume of the GPC column.
  • MALS Hydrodynamic Chromatography with multiangle light scattering detection
  • Samples were prepared by dissolving about 10 mg of sample in about 10 ml of butylated hydroxytoluene (BHT) stabilized tetrahyrofuran (THF). Some samples were further diluted 10- fold with THF as necessary.
  • BHT butylated hydroxytoluene
  • THF tetrahyrofuran

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Cette invention concerne une formulation d'écran solaire comprenant un véhicule de type huile, un agent actif d'écran solaire à base d'oxyde métallique particulaire et un modificateur de rhéologie polymère qui maintient l'agent actif d'écran solaire particulaire en dispersion stable dans la formulation. Selon un aspect, le modificateur de rhéologie polymère peut être obtenu par copolymérisation d'un mélange de monomères comprenant au moins un (méth)acrylate d'alkyle et au moins l'un des monomères suivants : ester (méth)acrylique bicyclique différent du (méth)acrylate d'alkyle, et monomère de vinyle aromatique. Dans un mode de réalisation, le modificateur de rhéologie polymère est réticulé.
PCT/EP2017/084221 2016-12-29 2017-12-21 Formulations d'écran solaire sous forme de dispersion d'oxyde métallique dans huile WO2018122121A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1576947A1 (fr) 2002-12-27 2005-09-21 Shiseido Co., Ltd. Preparation dermique huileuse a usage externe
EP2455061A1 (fr) 2009-07-13 2012-05-23 Tayca Corporation Dispersion huileuse et matière cosmétique incorporant cette dispersion huileuse
JP2014080377A (ja) 2012-10-12 2014-05-08 Kose Corp 水中油型乳化化粧料
JP2014091735A (ja) 2012-11-06 2014-05-19 Kao Corp 水中油型乳化化粧料
WO2016096660A1 (fr) * 2014-12-18 2016-06-23 L'oreal Composition comprenant des particules de polymère, une huile à base d'hydrocarbure et un élastomère de silicone, et son procédé d'utilisation
WO2016096627A1 (fr) * 2014-12-18 2016-06-23 L'oreal Composition comprenant des particules de polymère, une huile à base d'hydrocarbure et une résine de silicone, et procédé l'employant
US20160184211A1 (en) * 2014-12-18 2016-06-30 L'oréal Composition comprising polymer particles, alkylcellulose particles and water

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1576947A1 (fr) 2002-12-27 2005-09-21 Shiseido Co., Ltd. Preparation dermique huileuse a usage externe
EP2455061A1 (fr) 2009-07-13 2012-05-23 Tayca Corporation Dispersion huileuse et matière cosmétique incorporant cette dispersion huileuse
JP2014080377A (ja) 2012-10-12 2014-05-08 Kose Corp 水中油型乳化化粧料
JP2014091735A (ja) 2012-11-06 2014-05-19 Kao Corp 水中油型乳化化粧料
WO2016096660A1 (fr) * 2014-12-18 2016-06-23 L'oreal Composition comprenant des particules de polymère, une huile à base d'hydrocarbure et un élastomère de silicone, et son procédé d'utilisation
WO2016096627A1 (fr) * 2014-12-18 2016-06-23 L'oreal Composition comprenant des particules de polymère, une huile à base d'hydrocarbure et une résine de silicone, et procédé l'employant
US20160184211A1 (en) * 2014-12-18 2016-06-30 L'oréal Composition comprising polymer particles, alkylcellulose particles and water

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Eospoly Sun Cream", INTERNET CITATION, March 2008 (2008-03-01), pages 1, XP002659382, Retrieved from the Internet <URL:http://www.creationscouleurs.com/formulations/sun/low_spf/3103_1_2008eospolysuncr.pdf> [retrieved on 20110905] *
"The CTFA Cosmetic Ingredient Handbook", 1997
GEORGE DECKNER, DIVERSE TECHNOLOGIES FOR POLYMERIC OIL THICKENERS, 14 March 2014 (2014-03-14), Retrieved from the Internet <URL:http://knowledge.ulprospector.com/388/pcc-diverse-technologies-polymeric-oil-thickeners>

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