This invention relates to a particle comprising a polymeric shell and an ultraviolet absorbing compound. Such particles are useful, e.g., in cosmetic and dermatological formulations.
Encapsulation of a variety of active ingredients in polymeric materials is known. For example, U.S. Pat. No. 7,176,255 teaches encapsulation of perylene visible dyes in a polymer shell by means of miniemulsion polymerization. However, methods for encapsulating ultraviolet absorbing compounds in small particles are not known.
The problem addressed by this invention is to provide a small, stable particle containing an ultraviolet absorbing compound.
The present invention is directed to a particle having an average diameter from 80 to 500 nm and comprising: (a) a core comprising at least one compound having a λmax in the range from 250 to 400 nm; and (b) a shell comprising a polymer comprising 10-100 wt % monomer residues of at least one multiethylenically unsaturated compound and 0-90 wt % monomer residues of at least one monoethylenically unsaturated compound. The invention is further directed to a sunscreen formulation containing the particle and to a method for producing the particle by miniemulsion polymerization.
Percentages are weight percentages (wt %) and temperatures are in ° C., unless specified otherwise. As used herein the term “(meth)acrylic” refers to acrylic or methacrylic. Monomers useful in this invention include monoethylenically unsaturated compounds and multiethylenically unsaturated monomers, i.e., crosslinkers, including, e.g., divinylaromatic compounds, di- and tri-(meth)acrylate esters, di- and tri-vinyl ether compounds, allyl(meth)acrylate. Monoethylenically unsaturated monomers include, e.g., (meth)acrylic acids and their esters, amides and nitriles; styrene, chloro- and/or methyl-substituted styrenes, vinylpyridines, and vinyl esters, ethers and ketones. Monomers which are sufficiently insoluble in an aqueous phase are preferred. The term “styrenic polymer” indicates a copolymer polymerized from monomers comprising a styrene monomer (substituted or unsubstituted styrene, e.g., styrene, α-methylstyrene, ethylstyrene) and/or at least one crosslinker, wherein the combined weight of styrene and crosslinkers is at least 50 weight percent of the total monomer weight. In some embodiments, a styrenic polymer is made from a mixture of monomers that is at least 75% styrene and crosslinkers, alternatively at least 90% styrene and divinylaromatic crosslinkers, alternatively from a mixture of monomers that consists essentially of styrene and at least one divinylaromatic crosslinker. In other embodiments, a styrenic polymer is made from a monomer mixture consisting essentially of at least one divinylaromatic crosslinker. The term “acrylic polymer” indicates a copolymer formed from a mixture of vinyl monomers containing at least one (meth)acrylic acid, ester or amide, or (meth)acrylonitrile, along with at least one crosslinker (e.g., allyl methacrylate, ALMA; trimethylolpropane trimethacrylate, TMPTMA), wherein the combined weight of the (meth)acrylic acid(s) (acrylic acid, AA; methacrylic acid, MAA) or ester(s) (e.g., methyl methacrylate, MMA) or amide(s) or (meth)acrylonitrile and the crosslinker(s) is at least 50 weight percent of the total monomer weight; preferably at least 75%, more preferably at least 90%, and most preferably from a mixture of monomers that consists essentially of at least one (meth)acrylic acid or ester and at least one crosslinker. In some embodiments, a (meth)acrylic acid ester is a C2-C4 hydroxy-substituted alkyl ester, e.g., 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxypropyl acrylate (HPA). An “acrylic/styrenic polymer” is one formed from a mixture of vinyl monomers comprising at least 50%, alternatively at least 75%, alternatively at least 90% of acrylic and styrenic monomers, as defined above.
The average particle size given for the particles of this invention is a weight average determined by light scattering measurements. In some embodiments of the invention, the average particle size is at least 100 nm, alternatively at least 125 nm, alternatively at least 150 nm, alternatively at least 160 nm. In some embodiments, the average particle size is no more than 400 nm, alternatively no more than 300 nm, alternatively no more than 250 nm, alternatively no more than 230 nm, alternatively no more than 220 nm, alternatively no more than 210 nm, alternatively no more than 200 nm.
At least one ultraviolet absorbing compound in the core preferably has λmax of at least 275 nm, alternatively at least 300 nm. In some embodiments of the invention, at least two ultraviolet absorbing compounds are present in the core, one having λmax in the range from 250 to 325 nm, and one having λmax in the range from 325 to 400 nm. Preferably, ultraviolet absorbing compounds have an extinction coefficient at λmax of at least 3,000 L/cm-mole, alternatively at least 4,000 L/cm-mol, alternatively at least 5,000 L/cm-mol. Preferably, ultraviolet absorbing compounds are organic compounds, i.e., those containing carbon and having at most trace levels of metals, more preferably aromatic compounds. Visible dyes having λmax in the visible range, i.e., above 400 nm, are not considered ultraviolet absorbing compounds for the purposes of this invention. In some embodiments of the invention, the particle contains less than 1% of any visible dye, alternatively less than 0.5%, alternatively less than 0.2%, alternatively less than 0.1%, based on the weight of the particle. Examples of ultraviolet absorbing compounds may be found, e.g., in U.S. Pat. No. 7,316,809. Preferred ultraviolet absorbing compounds include, e.g., aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octocrylene, octyl methoxycinnamate, octyl salicylate, oxybenzone, Padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone and trolamine salicylate. A particularly preferred ultraviolet absorbing compound is avobenzone.
The shell polymer is a free-radical addition polymer. In some embodiments of the invention, it is an acrylic polymer, a styrenic polymer or an acrylic/styrenic polymer. In some embodiments of the invention, the shell polymer comprises at least 15% monomer residues of at least one multiethylenically unsaturated compound, alternatively at least 20%, alternatively at least 25%, alternatively at least 30%, alternatively at least 35%, alternatively at least 40%, alternatively at least 50%, alternatively at least 60%; and in some embodiments, no more than 95%, alternatively no more than 90%. In some embodiments of the invention, the shell polymer comprises no more than 85% monomer residues of at least one monoethylenically unsaturated compound, alternatively no more than 80%, alternatively no more than 70%, alternatively no more than 65%, alternatively no more than 60%, alternatively no more than 50%, alternatively no more than 40%; in some embodiments at least 5%, alternatively at least 10%. The aforementioned percentages are on the basis of the shell weight.
In some embodiments of the invention, preferably the monoethylenically unsaturated compound(s) used to make the shell polymer comprises at least one polar acrylic monomer, i.e., one having a hydroxy, carboxyl or amide group. Preferably the amounts of the polar acrylic monomer(s) are at least 1% based on polymer weight, alternatively at least 2%, alternatively at least 5%, alternatively at least 10%, alternatively at least 15%, alternatively at least 20%; preferably the amounts are no more than 50%, alternatively no more than 40%, alternatively no more than 30%, alternatively no more than 25%. Especially preferred monomers include HEMA, HPMA, HEA, HPMA, AA, MAA, acrylamide and methacrylamide. Preferably, the monoethylenically unsaturated compound(s) has a hydroxy group. Preferably, carboxylic acid monomer residues comprise no more than 5% of the polymer, alternatively no more than 3%, alternatively no more than 2%, alternatively no more than 1%. In some embodiments of the invention, the multiethylenically unsaturated compound(s) comprises at least one diethylenically unsaturated compound, e.g., allyl methacrylate (ALMA), allyl acrylate, divinylbenzene. In some embodiments of the invention, the multiethylenically unsaturated compound(s) comprises at least one triethylenically unsaturated compound, e.g., trimethylolpropane trimethacrylate.
In some embodiments of the invention, the core is at least 25% by weight of the particle, alternatively at least 35%, alternatively at least 45%, alternatively at least 50%, alternatively at least 55%, alternatively at least 60%, alternatively at least 65%, alternatively at least 70%, alternatively at least 75%, alternatively at least 80%; and in some embodiments no more than 95%, alternatively no more than 90%, alternatively no more than 85%. In some embodiments, the shell is at least 5% by weight of the particle, alternatively at least 10%, alternatively at least 15%; and in some embodiments, no more than 75%, alternatively no more than 65%, alternatively no more than 55%, alternatively no more than 50%, alternatively no more than 45%, alternatively no more than 40%, alternatively no more than 35%, alternatively no more than 30%, alternatively no more than 25%, alternatively no more than 20%. In some embodiments of the invention, the core contains at least two ultraviolet absorbing compounds, one of which absorbs most strongly in the UV-A range (290-325 nm) and one of which absorbs most strongly in the UV-B range (325-400 nm). Preferably, at least one UV-A absorber is from 20-100% of the core, alternatively from 25-80%, alternatively from 25-60%, alternatively from 30-50%, alternatively from 30-40%, percentages on the basis of core weight. One preferred UV-A absorber is avobenzene, and one preferred UV-B absorber is homosalate (3,3,5-trimethylcyclohexyl salicylate). When avobenzone is present in the particle, preferably octyl methoxycinnamate is not present unless a uv stabilizer for avobenzone is also present. In some embodiments of the invention, the core contains a UV-A absorber and a solvent which does not necessarily absorb strongly in the ultraviolet range. The solvent preferably has a boiling point greater than 100° C. at atmospheric pressure and is hydrophobic, i.e., it has an HLB (hydrophilic lipophilic balance) less than 10. One preferred solvent is isopropyl myristate.
The particle of this invention preferably is prepared by the technique of miniemulsion polymerization, as described, e.g., in G. H. Al-Ghamdi et al., J. Appl. Poly. Sci., vol. 101, pp. 3479-3486 (2006), or Landfester, K., Macromol. Rapid. Commun., vol. 22, pp. 896-936 (2001), and references cited therein, using an ultrasonic or high-pressure homogenizer, preferably with sufficient power to create 200 nm droplets. Preferably, polymerization is performed at temperatures ranging from 20° C. to 100° C. Free-radical initiators are suitable for initiating the polymerization, including both water- and oil-soluble initiators, e.g., persulfate and lauroyl peroxide. Surfactants suitable for conventional emulsion polymerization are suitable for miniemulsion polymerization. Anionic surfactants are preferred. Preferably, the solids content of the polymerization mixture is from 20-65%, alternatively from 20-60%, alternatively from 25-55%, alternatively from 30-50%.
The present invention further comprises a cosmetic or dermatological formulation comprising the particle. Such formulations are well known, as described, e.g., in U.S. Pat. No. 6,379,683, and references cited therein. In some embodiments of the invention, the cosmetic or dermatological formulation contains particulate scatterers such as SUNSPHERES™ Polymer sold by the Rohm and Haas Company, metal oxides, solid UV absorbers, such as TINOSORB™ S and TINOSORB™ M sold by the Ciba Chemical Company, zinc oxide, titanium dioxide, or other scatterers such as glass beads or polymer particles. These would be included at a level to achieve maximum efficiency in scattering without providing whitening on the skin, unless desired for a skin muting effect in some formulations. The desirable level is generally a maximum of 5% and a minimum of 0.1% by weight in the formulation.
The monomers, core compounds, initiator (persulfate), surfactant and water at a concentration of 30-50% solids are charged to a reactor. The mixture was agitated with an ultrasonic homogenizer at a starting temperature of 35° C., then heated to 75-85° C., and reached a maximum temperature due to exothermic reaction of about 95° C.
The procedure given above was used to prepare the following particles having varying cross-linking and shell content. Amounts of cross-linker (xl) and other monomers are relative to the shell polymer, and amounts of shell are relative to the entire particle. The core in particles B, C and E-G contained avobenzone and homosalate in a 31:69 weight ratio, and the core in particle H in a 33:67 weight ratio.
A sunscreen was formulated according to the following table. A typical laboratory overhead mixer (CAFRAMO BDC 2002) was used in the preparation. The procedure used was typical of sunscreen preparation with an aqueous phase being heated to 75° C., an oil phase being mixed to 75° C. separately, mixing of the two phases and cooling with stirring to form the emulsion. Samples of miniencapsulated avobenzone were evaluated along with a ‘control’ sample containing an equal amount of avobenzone in the formulation added through a typical emulsion process used in preparing sunscreens.
The materials listed above with tradenames are materials typically used in personal care formulations and are listed in the INCI (International Nomenclature of Cosmetic Ingredients) Dictionary published by the Cosmetics, Toiletries and Fragrance Association, Washington, D.C. (11th edition).
Data for in vitro SPF measurements (data is with a 1.5 mil spacer)
All SPF measurements have been normalized to the control, which contains the same level of homosalate and avobenzone added through the typical sunscreen emulsification procedure (See procedure and formulations below).
These two formulated sunscreen samples from above were submitted to IMS Inc. (Portland, Me.) for in vitro photostability of the avobenzone, to compare the stability of the polymer encapsulated avobenzone with the avobenzone that had been added through normal emulsification. The samples were measured by an in vitro technique where the sunscreen is spread on VITRO-SKIN at 2 μl/cm2, the standard application rate for sunscreens applied to the human body. The initial UVA/UVB ratio was measured and then the sample (on the VITRO-SKIN) was subjected to 5 MED (Minimal Erythermal Dose) from a 150 watt Xenon Arc Lamp (Solar Light Company). The UVA/UVB ratio was again determined. Then the sample was re-exposed to the 150 watt lamp for 10 more MED, for a total of MED. The UVA/UVB ratio was again determined. The resultant data appear below.
The following sunscreens were formulated as described above.
These measurements demonstrate that highly crosslinked particles provide better retention of uv-absorption properties after storage at elevated temperature.
Sunscreens were formulated according to the following table. A typical laboratory overhead mixer (CAFRAMO BDC 2002) was used in the preparation. The procedure used was typical of sunscreen preparation with an aqueous phase being heated to 75° C., an oil phase being mixed to 75° C. separately, mixing of the two phases and cooling with stirring to form the emulsion. One sample of miniencapsulated avobenzone was evaluated along with ‘control’ samples containing equal amounts of avobenzone in the formulation added through a typical emulsion process used in preparing sunscreens.
Data for in vitro SPF measurements (data is with a 1.0 mil spacer)
All SPF measurements have been normalized to the control which contains 1.0% avobenzone as stated above. All samples contain the same level of homosalate.
The avobenzone in ID samples A through C is added through the typical sunscreen emulsification procedure. In ID samples D through F the avobenzone is added through the encapsulated polymer. The level of avobenzone in sample A is the same as sample D, sample B has the same level as sample E and sample C matches the level of avobenzone as sample F.
Since sample A contains the same amount of avobenzone as sample D, while sample B has the same amount as sample E and sample C has the same amount as sample F, comparisons between these sample pairings can be made to note the effect of encapsulation.
This application claims the benefit of priority under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/132,180 filed on Jun. 16, 2008.
Number | Date | Country | |
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61132180 | Jun 2008 | US |