CN101932303A - Visibly transparent uv photoprotective compositions - Google Patents
Visibly transparent uv photoprotective compositions Download PDFInfo
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- CN101932303A CN101932303A CN2009801020565A CN200980102056A CN101932303A CN 101932303 A CN101932303 A CN 101932303A CN 2009801020565 A CN2009801020565 A CN 2009801020565A CN 200980102056 A CN200980102056 A CN 200980102056A CN 101932303 A CN101932303 A CN 101932303A
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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
- A61K8/27—Zinc; Compounds thereof
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0275—Containing agglomerated particulates
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Abstract
A broad-spectrum UV photoprotective composition is described. The composition is characterized in that the composition comprises mesoporous zinc oxide aggregates having an average aggregate size of at least 0.8 microns dispersed in a carrier and the composition is visibly transparent. Sufficient zinc oxide is included in the composition to achieve an SPF greater than 15, greater than 25, greater than 30, or greater than 50.
Description
Technical field
The present invention relates to the application of mesoporous zinc oxide aggregates in (visible light transmissive) compositions of visible transparent, described compositions provides the broad-spectrum light protection when being applied to substrate (substrate).
Background technology
With being exposed to ultraviolet light (UV) radiation (that is, having the light to the wavelength between the 400nm) at 290nm relevant unfavorable healthy result in scientific literature by wide coverage.The short-term sequela comprises erythema and sunburn (sunburn); Long-term results comprises the premature aging (showing as lines, wrinkle and nevus) of skin, precancerous sun cutin and skin carcinoma.More specifically, UVB radiation (290-320nm) is relevant with sunburn and erythema, and UVA radiation (320-400nm) is in the news and promotes too early skin aging and to the photosensitivity of some chemical substances.
UVA protects measured and conveys to consumer in many ways.In Europe; European Cosmetic Toiletry and Fragrance Association (COLIPA) has developed a kind of tagging scheme (labeling scheme), and the light protection product that has the UVA protection factor of at least 1/3 the sun protection factor (SPF) thus can be printed " UVA " in the circle on product container or the label.In Britain, company often utilizes their product of Boots Star system marks based on the ratio of UVA and UVB.In Japan, Japanese cosmetic TIA (Japan Cosmetic IndustryAssociation) has issued three-level system: the 2 protection factors (PFA) that arrive less than 4 are " PA+ "; 4 PFA that arrive less than 8 are " PA++ "; And the PFA more than 8 is " PA+++ ".In the U.S., Food and Drug Administration (Food andDrug Administration) (FDA) has issued for not writing out a prescription but the modification of the suggestion of the last monograph (Final Monograph on SunscreenProducts for Over-the-Counter Human Use) of the sunscreen product that the mankind that can legal sale use.The regulations of suggestion form the hierarchy system based on 1 to 4 stellar magnitude, the level of the UVA protection that it is designed to help consumer to identify and is provided by product.
Know zinc oxide blocking-up 290nm in this area up to the UV of about 375nm radiation.In addition, zinc oxide uses in cosmetics (beauty treatment) and sunscreen formulas for a long time owing to its antibiotic and non-sensitive performance.Although the performance that these are useful, the application of zinc oxide is limited, and mainly is because of the undesirable white residue that deposits on the substrate that has applied the product that comprises ZnO thereon.With regard to ZnO was integrated with cosmetics and sunscreen formulas, formulator minimized various levels and/or user applies product and bleaches with minimizing or make to bleach and minimize modestly or being lower than under the pointed level.Yet, to do like this, the light protection effect of product is weakened, and makes and must integrate with chemical UV absorbent to meet the SPF requirement.Similarly, in clear coat and overlay, bleach in the past and now do not expect.
After applying the light protection product that comprises ZnO, bleaching of substrate (as, skin) is attributable to diffuse-reflectance, the scattering of light on backward directions (that is, away from described substrate and towards the observer).On the contrary, the light in (by the described substrate) scattering that forwards makes progress helps the optical transmission ratio.This is known in this area as diffuse transmissivity.Therefore the total transmittance of the light protection product of incident illumination by comprising ZnO comprises the diffused light transmittance and does not have scattering and the light of transmission is called " minute surface " transmittance in the art.The diffusion of light component (diffusion composition) of total transmission causes " soft focus effect ", and the character of the high expectations of cosmetic product especially helps to reduce the appearance of microgroove and wrinkle.
The mean size (size) that the art methods of the problem that bleaches for the surface of being caused by the light protection product that comprises ZnO mainly concentrates on Zinc oxide particles is reduced to below the 0.2 μ m at least.The reducing of this granular size increased transparency and reduced whiteness (by reducing visible scattering of light).
United States Patent (USP) the 5th, 587 has been instructed a kind of local sunscreen formulas of visible transparent basically No. 148, comprises the dispersion that has less than the micronized particle of the zinc oxide of the average particulate diameter of about 0.2 μ m.United States Patent (USP) the 5th, 032 has been instructed sunscreen composition No. 390, comprise by weight 1% to 25% have the particulate oxidation zinc of 0.07 μ m to the mean diameter of 0.3 μ m.The compositions that discloses by further instruction comprise 1% to 25% have the particulate titanium dioxide of 0.03 μ m to the mean diameter of 0.07 μ m.The open WO2006/010214 of international monopoly has disclosed a kind of UV light protection compositions, comprises the Zinc oxide nanoparticle of 0.015 μ m of the oil that is combined with plant origin to the size range of 0.5 μ m.
Yet it is not have consequence that the ZnO particle diameter is reduced to nanoscale (for example, especially less than about 0.2 μ m).The particulate bigger useable surface area of nanometer size has increased the amount of flocculation, and then has increased the amount of caking (reunion).Therefore the particulate light protection product that comprises the nanometer size can show particles settling for unsettled, and under the situation of Emulsion, shows to be separated.This unstability can cause with in addition only based on particle diameter expection compare the whiteness of higher scattering of light and increase and the light protection level that reduces.
The known high grade of transparency that presents the refractive index of reduction and follow low reflection loss of the aluminium oxide of nano-pore and polymeric film.United States Patent (USP) 7,075,229 have instructed a kind of light-emitting device (luminescent device) of integrating with transparent nano porous aluminum oxide film.
U.S. Patent Publication has been instructed the method for the porous titanium oxide powder of the transparency that a kind of production has improvement for No. 2006/0188432.That open WO 03/080515 of international monopoly and German patent DE 10212680 have been instructed is nano level, high thermogenetic zinc oxide synthetic, with the form of the aggregation of anisotropic primary granule, this primary granule has the average diameter of 50-300nm.
The particulate high surface of the ZnO of nano-scale is relevant with high-caliber photocatalytic activity, causes being generally comprised within the polymerization composition degraded in cosmetics, plastics and the coating.In addition, in light protection personal care product, high photocatalytic activity can produce free radical, and it has been in the news and has caused deleterious healthy result.Referring to, for example, L.Jing et al. " TheSurface Properties and Photocatalytic Activities of ZnO UltrafineParticles ", Applied Surface Science, Vol.180, pp.308-314 (July2001).
Recently, propose the potential negative healthy result's that absorbs about the percutaneous of nano-particle problem, comprised the submicron sunscreen.Under the situation of local light protection product, according to authoritative institution, as Australian Therapeutic Goods Administration, the influence (weight) of evidence at present is that the nano-particle in the sunscreen cream rests on the surface of skin and in the horny layer.Yet, consumer's acceptance that passive sensation already and will these products of long lasting effect.
In the U.S., the use that FDA has ratified two kinds of reagent (medicament) is a safety and effective, is used in effect-zinc oxide (as mentioned above, it is as the physics blocker) and avobenzone to reduce UVA in the topical product, and it absorbs UVA via chemical reaction.And in the UV light protection compositions combination of avobenzone and zinc oxide be well known in the art-referring to; for example; United States Patent (USP) the 5th; 827, No. 508 (having instructed a kind of sunscreen composition that comprises the surface-treated zinc oxide of 0.1% to about 10% avobenzone and about 0.1% to about 20%)-this is combined in the U.S. and effectively is not allowed at present under the regulations now.If as in the last regulations to being modified in of FDA monograph of proposing 2007 8 the end of month, implement, then avobenzone/ZnO combination will be allowed to.
Yet, to know in this area, avobenzone is not that light is stable when being used in combination with other UV absorbent particularly.Trial with physics and the Photostabilised avobenzone of chemical reagent is described in United States Patent (USP) the 5th, 576, No. 354, the 5th, 587, No. 150, the 5th, 849, No. 273, the 5th, 985, No. 251, the 6th, 033, No. 649, the 6th, 071, No. 501, the 6th, 444, No. 195, the 7th, 235, No. 587 and the 7th, 244, in No. 416.For example, United States Patent (USP) the 7th, 244 has been instructed for No. 416 a kind ofly by adding the method for the avobenzone in the Photostabilised local light protection of the ensulizole prescription, and described prescription comprises the zinc oxide of about 6% to 25% concentration.
Scientific literature has reported that (shading filters agent to the organic sunscreen filtrate, sunscreenfilter) and the percutaneous of their catabolite sees through and whole body absorbs.This so produced health problem.Also reported the problem that the percutaneous about the pigment of nanometer size sees through.Do not consider whether these problems are proved or confirmed degree; existed and be still unsatisfied demand up to now for local UV light protection compositions; described compositions minimizes, and is perhaps preferred, do not comprise the physical sunscreen blocker of organic sunscreen filtrate and/or nanometer-size.
Had and still existed the demand to the light protection prescription that comprises zinc oxide, it provides bleaching of visible basically transparency or reduction, and its (because size) do not produce the problem that sees through about percutaneous.These demands satisfy by compositions of the present invention.
Summary of the invention
According to a first aspect of the invention; a kind of wide spectrum UV light protection compositions is provided; it is characterized in that described compositions comprises the mesoporous zinc oxide aggregates with average aggregate size (aggregate size) of at least 0.8 micron that is dispersed in the carrier, and described compositions is a visible transparent.In one form, described zinc oxide aggregates can have following average aggregate size one of at least: greater than 1.0 microns, greater than 2.0 microns or greater than 3.0 microns.
In one form, described mesoporous zinc oxide aggregates with effectively provide greater than 15, greater than 25, greater than 30 or exist greater than the amount of the SPF one of at least in 50.
The horizontal component ground of visible transparency depends on the percentage by weight of the zinc oxide that comprises in the compositions.In a kind of form of the present invention, when described compositions comprised zinc oxide aggregates by the weight at least 40% of total composition or 50% concentration, described compositions can have at the 550nm place 0.15 the total absorptance of being not more than of path by 20 microns.In another form, when described compositions comprised zinc oxide aggregates by weight 30% concentration of total composition, described compositions can have at the 550nm place 0.14 the total absorptance of being not more than of path by 20 microns.In another form, when described compositions comprised zinc oxide aggregates by weight at least 20% concentration of total composition, described compositions can have at the 550nm place 0.12 the total absorptance of being not more than of path by 20 microns.In another form, when described compositions comprised zinc oxide aggregates by weight at least 10% concentration of total composition, described compositions can have at the 550nm place 0.06 the total absorptance of being not more than of path by 20 microns.
In one form, described zinc oxide aggregates can have at least 3.0 microns average aggregate size, and described compositions has at the 550nm place 0.20 the total absorptance of being not more than of path by 20 microns.
In one form, described zinc oxide aggregates can have at least 2.0 microns average aggregate size, and described compositions has at the 550nm place 0.16 the total absorptance of being not more than of path by 20 microns.
Replacedly or additionally, described compositions may further include dibenzoylmethane derivative.Replacedly or additionally, described compositions can comprise and is less than 5% or be less than 3% organic sunscreen filtrate.In one form, visible transparent, wide spectrum UV light protection compositions is that light is stable, and described organic sunscreen filtrate is an avobenzone.
Replacedly or additionally, described zinc oxide aggregates can have following average aggregate size one of at least: greater than 1.0 microns, greater than 2.0 microns or greater than 3.0 microns, and described compositions has the soft focus factor greater than 40 at the 550nm place.
Replacedly or additionally, described zinc oxide aggregates can have following average aggregate size one of at least: greater than 1.0 microns, greater than 2.0 microns or greater than 3.0 microns, and described compositions has the CIE whiteness less than 25.Replacedly or additionally, described zinc oxide aggregates has following average aggregate size one of at least: greater than 1.0 microns, greater than 2.0 microns or greater than 3.0 microns, and described compositions has the CIE L less than 30
*Brightness.
Replacedly or additionally; described compositions can comprise one or more non-hole zinc oxide aggregates (MZOA) bright protective agents, and wherein said one or more non-mesoporous zinc oxide aggregates (MZOA) bright protective agents are so that the SPF of compositions improves the concentration existence of the SPF that is no more than 2 units.
According to a second aspect of the invention, provide a kind of method that provides protection to avoid ultraviolet radiation to mammal skin or hair, comprised skin or hair are contacted with according to a first aspect of the invention compositions.
According to a third aspect of the invention we, provide a kind of and treated the method for human skin section (human skin is sick to be learned) disease by applying the visible light that the comprises compositions according to a first aspect of the invention-transparent topical formulations for the treatment of effective dose, described department of dermatologry disease is selected from the group of being made up of acne, psoriasis, eczema, ichthyosis, pruritus, drying and dermatitis.
According to a forth aspect of the invention, provide a kind of visible transparent of describing with reference to embodiment and accompanying drawing as this paper basically, wide spectrum UV light protection compositions.
Description of drawings
In order to help understanding characteristic of the present invention in more detail, now with reference to accompanying drawing, only, describe the specific embodiment in detail with the form of example, wherein:
Fig. 1 diagram shows as utilize the aggregation size distribution of the prescription D of laser defusing measure for embodiment 1;
Fig. 2 diagram shows the influence of ZnO concentration to total visible transmission ratio;
Fig. 3 diagram shows the influence of ZnO concentration to the CIE whitness index; And,
Fig. 4 diagram shows the influence of ZnO concentration to total absorptance.
The specific embodiment
Unless otherwise defined, otherwise all technology used herein have the common identical implication of understanding with those skilled in the art with scientific terminology.Except as otherwise noted, otherwise as using in this application, numerical value percentage ratio refers to and is designated as gross weight by weight the percentage ratio of branch with respect to compositions.
Term micro-, " micron " and symbol " μ " and " μ m " are used interchangeably in whole this description, and being used to refer to for length is one meter millionth measurement unit.
As using in this application, term " MZOA " refers to the Zinc oxide particles that is included in a plurality of primary oxidation zinc crystallites that shared interface junction lumps together.The embodiment of MZOA of the present invention has the average crystallite dimension of about 10nm to about 20nm.
The MZOA that is included in the UV light protection compositions of the present invention is " mesopore ", and it means that bonded primary oxidation zinc crystallite forms the aggregation with the hole from about 2nm to about 100nm scope.
MZOA used among the present invention can comprise mechanochemistry technology (MCP), France and the American process and the sedimentation method by known method (technology) preparation.United States Patent (USP) the 6th, 203 No. 768 and the 6th, 503, has been described for No. 475 and have been utilized MCP to produce ultra-fine and aggregated particle such as ZnO.In French method, the zinc metal be heated to high temperature, gasification, subsequently in oxidizing atmosphere condensation with the porous aggregates of the crystallite that forms interconnection.In American process,, obtain zinc oxide aggregates with this zinc metal of rear oxidation by with carbon calcined oxide zinc ore.In depositing technology, soluble zinc salt such as zinc sulfate are crystallized into zinc oxide aggregates by adding alkali.With afterflush, and the sedimentary aggregation of sintering.The architectural feature that is applicable to the MZOA in the compositions of the present invention can be utilized any preceding method, adjusts by technology well known by persons skilled in the art.Be applicable to that the preferred L ZOA in the compositions of the present invention can be from Antaria Limited (Bentley, Australia) acquisition.
MZOA in the compositions of the present invention can have total mesoporous porosity of from 50% to about 75% MZOA volume.Closed porosity can utilize the helium pycnometry to measure (Micromeritics AccuPyc 1330).Open-cell porosity (percent opening) can utilize gas absorption techniques (Micromeritics Tristar), measure according to Barrett-Joyner-Helenda method (be described in Techniques de 1 ' Ingenieur[Techniques of the Engineer] in and be entitled as " Texture des solides poreux ou divises " [Texture of porous ordivided solids], p.3645-1 to 3645-13).In particularly preferred embodiment of the present invention, MZOA has the distribution of mesopore of the average pore size of about 35nm.
The UV light of the present invention that MZOA is integrated with as dispersion is protected in the compositions.Wherein can disperse the carrier of MZOA to comprise cosmetics for skin carrier well known by persons skilled in the art.Suitable carriers includes, but not limited to esters such as benzoic acid C
12-15Arrcostab, capric acid Trivent OCG, isopropyl palmitate, octyl stearate, dicaprylyl carbonate (dicaprylyl carbonate), natural oils such as macadamia oil, olive oil, simmondsia oil (Jojoba oil, jojoba oil), silicone such as cyclomethicone, simethicone (dimethicone) and methyl trimethoxy radical siloxane (methyl gathers trimethicone).
Refer to total size of isolating independently aggregation as the term " aggregation size " that uses below, described aggregation is dispersed in liquid, semisolid or the solid dielectric respectively.Described average aggregate size is defined according to following equation with counting:
<d
v>＝∑f
i*d
i
Wherein
＜d
vIt is weighted volumetrically average aggregate size;
d
iBe the aggregation diameter; And
f
iFor having d
iThe volume fraction of aggregation of diameter value.
The size basis of MZOA is as utilizing the distribution of the aggregation of microscope, light scattering and other commercial measurement well known by persons skilled in the art to express.The preferable methods of measuring the size distribution of MZOA is based on light scattering.For the application's purpose, the laser light scattering of the size utilization static state of MZOA is measured.
Compositions in the scope of the present invention provides the protection of broad-spectrum UV light.As employed among the present invention, term " wide spectrum UV light protection compositions " is to block, absorb or otherwise reduce to have the compositions of the electromagnetic radiation of the wavelength from 290nm to 400nm.
If compositions can be applied to substrate and light can seldom or not pass compositions to distortion, so that utilize eyes can be clear that described substrate by compositions, then described compositions is " visible transparent ".Transparency utilizes method known to those skilled in the art to measure.In this description, the measurement of total absorptance is used to show the level of the transparency of the various embodiments acquisitions that utilize claimed compositions.
As used herein, term " organic sunscreen filtrate (sunscreen filter) " is meant the organic compound of ultraviolet radiation-absorbing.The limiting examples of organic sunscreen filtrate comprises: para-amino benzoic acid (PABA), preferably up to 15%; Avobenzone is preferably up to 3%; Cinoxate is preferably up to 3%; Dioxybenzone is preferably up to 3%; Homosalate; Preferably up to 15%; Artificial neroli oil (methyl 2-aminobenzoate) is preferably up to 5%; Octocrilene is preferably up to 10%; Octyl methoxycinnamate (Octinoxate) is preferably up to 7.5%; Ethylhexyl salicylate is preferably up to 5%; Oxybenzone is preferably up to 6%; PADIMATE O is preferably up to 8%; Phenylbenzimidazolesulfonic acid (ensulizole) is preferably up to 4%; Sulisobenzone (sulisobenzone) is preferably up to 10%; Triethanolamine, preferred Salicylate is up to 12%; 4-UVINUL MBC95 (USAN Enzacamene); With trade mark Tinosorb
Methylene two-benzotriazole base tetramethyl butyl phenol (USANBisoctrizole) that M sells; With trade mark Tinosorb
Two-ethyl hexyl oxy phenol anisyl triazine (USAN Bemotrizinol) that S sells; With trade mark Mexoryl
The Terephthalidene Dicamphor Sulfonic Acid (USAN Ecamsule) that SX sells; With trade mark Mexoryl
The drometrizole trisiloxanes that XL sells; With trade mark Neo Heliopan
The phenyl bisbenzimidazole tetrasulfonic acid disodium that AP sells; With trade mark Uvinul
The diethylamino (2-hydroxybenzoyl) hexyl benzene formic acid esters that A Plus sells; With trade mark Uvinul
The octyl triazone that T 150 sells; With trade mark Uvasorb
The diethylhexyl amide-based small triazinone that HEB sells; With trade mark Parsol
The silicone-15 that SLX sells.
Term " non-MZOA bright protective agent " refers to organic sunscreen filtrate as defined above, and atresia metal oxide pigment granule, coating or uncoated, its ultraviolet blocking-up radiation.
When light run into the skin that presents aging sign (as, microgroove and wrinkle) time, the amount of reflected back observer's light is less than the amount from glabrous skin, the result, eyes are more black and more obvious thus skin area wrinkly with perception.If skin is coated with the thin layer of embodiment of the light protection compositions of the visible transparent that comprises MZOA of the present invention, then the diffusion of light transmittance by described layer reduces by diffusion rise the microgroove that light sensation from skin is subjected to and the appearance of wrinkle.
As used in this application, term " soft focus effect " refers to cosmetics by allowing the light of height diffusion, reduce the surface fine crack on the skin and the appearance of wrinkle, but keeps highly transparent simultaneously, showing natural beige, and expresses by following formula:
SFE=[is at the total transmittance (%) at 550nm place] * [diffuse transmissivity (%)]/100 at the 550nm place
According to the SFE of compositions visible light of the present invention-transparent, the protection of UV light greater than about 20, more preferably greater than about 30, also more preferably greater than about 40.
According to visible light of the present invention-transparent, wide spectrum UV light protection compositions can directly be applied to substrate (as, as cream, lotion, gel, foam, mousse or spray) or with the form of rag, towelette or non-woven fabric.These compositionss can be used as anhydrous composition (as, gel or spray) preparation, and, comprise Water-In-Oil, oil-in-water, silicone Bao Shui, water bag silicone, W/O/W, water bag silicone Bao Shui as the preparation of biphase or three-phase Emulsion.When described compositions was Emulsion, it comprised one or more surfactants, and its concentration counts about 0.01% to about 20%, preferred about 0.1% to about 15% and more preferably from about 0.5% to about 10% by the weight of total composition.Surfactant is selected from the group of being made up of following: amphoteric surfactant (for example, propionate compound, the alkyl dimethyl betaines, the alkyl amido betaine class, sulfobetaines class and imidazolines), anion surfactant (fatty alcohol sulphuric acid esters, the alpha-olefin sulfonic acid esters, the 2-Sulfosuccinic acid esters, phosphoric acid ester, metal carboxylate and sarcosine salt), cationic surfactant (alkyl quaternaries, the alkylamide quaternary ammonium salt, the imidazoline quaternary ammonium salt class), and/or non-ionic surface active agent (alkanolamide class, the ethoxylation amide-type, esters, the alkoxylate alcohols, the alkoxylated triglyceride class, the alkyl polyglucoside class, the oxidation amine, sorbitan (Sorbitol) esters and ethoxylate class) and silicone surfactant is (for example, dimethyl siloxane polyol class, alkyl dimethyl silicone copolyol class, silicone quaternary ammonium compound class, silicone phosphoric acid ester and silicone esters) and glycerol and sorbitan esters, as at O ' Lenick Jr., Surfactants:Strategic Personal Care Ingredients (further describes among Allured Publishing (2005) and the McCutcheon ' s Detergents and Emulsifiers (1986), its disclosure content is all incorporated into way of reference.
Can comprise one or more film former alternatively according to compositions of the present invention, this film former includes, but not limited to crosslink silicone polymers and non-silicone polymer, it comprises polymeric ethylenically unsaturated monomers, combines separately or with one or more organic moiety.Described crosslinked silicone polymer can be elastomer or resin.
Can also comprise the reagent that one or more improve the water proofing property of compositions alternatively according to compositions of the present invention.
One aspect of the present invention relates to the method that embodiment by the topical composition of using visible light of the present invention-transparent to provide to mammal skin and/or hair the photodamaged of broad spectrum protection to avoid being exposed to ultraviolet radiation and cause.Cosmetic, Toiletries ﹠amp; Fragrance Association International Cosmetic Ingredient Dictionary andHandbook (11
ThEdition, 2006) (" CTFA Dictionary ") described multiple non-limiting cosmetic and medicinal ingredient commonly used in skin nursing industry.Embodiment according to the local wide spectrum compositions of visible light of the present invention-transparent can comprise one or more plasticizers, structural agent, viscosity modifier, thickening agent and/or gellant, as at United States Patent (USP) the 6th, 492, No. 326 and the 6th, 277, No. 892 and U.S. Patent Publication further describe for No. 2004/0180020 and No. 2005/0142095.In addition, embodiment according to the local wide spectrum compositions of visible light of the present invention-transparent can comprise one or more skins or hair active component, comprise, but be not limited to antioxidant, free radical quencher, outside analgesic, antiinflammatory, wetting agent, wetting agent, skin smooth and/or consolidant, vitamin and derivant thereof, and can be used on the composition that reduces in microgroove, wrinkle and the Hyperpigmented appearance, as in ' 326 apply for openly with ' 892 patents and ' 020 and ' 095, describing.
Embodiments of the present invention can relate to by the visible light-transparent topical formulations that applies the treatment effective dose treats acne, psoriasis, eczema, ichthyosis, pruritus, drying and dermatitis.Such preparation may further include skin medicinal reagent well known by persons skilled in the art, and it is that treatment is effective in the interested dermatological disease of treatment.The suitable skin medicinal reagent is described in, for example, and Kerdel, et al., Dermatologic Therapeutics (2005) and Hardman et al., Goodman ﹠amp; Among the Gilman ' s:The PharmacologicalBasis of Therapeutics (10th Edition, 2001), incorporate its disclosure content into this paper with way of reference.
Embodiments of the present invention relate to the stable visible transparent of a kind of light that comprises avobenzone, wide spectrum UV light protection compositions.For the present invention, " product that light is stable " is the product of the usefulness (for example, SPF, lasting pigment darkening) that has expectation after UV radiation (for example, with the MED of specified amount).Referring to, the COLIPA Method for the In Vitro Determination of UVAProtection by Sunscreen Products (2007) provides incorporates its disclosure content into this paper with way of reference.For example, light stability can (be equipped with WG 320 filters up to the Solar of 35MED Light Company model16S solar simulator by increasing with 5MED, with emission greater than the radiation of 290nm) before the irradiation and afterwards, go up at Labsphere UV-1000S UltravioletTransmittance Analyzer (software version 1.27) and to measure absorptance and determine.Output is monitored by PMA 2105 UV-B DCS Detector (biology increases the weight of), and controls by PMA 2100 Automatic Dose Controller (Solar Light Co.).Be exposed to the radiation of 35MED in compositions after, measure the absorbance of each compositions to (U_b scope) between the 400nm at 290nm.
MZOA of the present invention for enough big sizes (size) so that they do not pass epidermal barrier.Therefore, a second aspect of the present invention relates to UV light protection compositions, and SPF and UVA protection that it provides expectation minimize simultaneously, or preferably, eliminate the physical sunscreen blocker of organic sunscreen filtrate and/or nanometer-size.
Following formulation Example is further specifying of embodiments of the present invention.Component and concrete composition show as typically, and in view of above-mentioned disclosure content, within the scope of the invention, the various modifications of can deriving.Except as otherwise noted, otherwise herein all percentage ratios, ratio and ratio all be by weight.Except as otherwise noted, otherwise all temperature all be degree centigrade.
Embodiment 1: the aggregation size
According to standardization program, prepare five prescriptions (being appointed as A-E) in the suitable carriers by in ball mill, grinding MZOA is distributed to.MZOA concentration is 50wt%.The carrier that uses: A and B are caprylic/capric triglyceride (CCTG) for prescription, and are benzoic acid C12-15 Arrcostab (AB) for prescription C-E.By prescription A-B and C-E, studied the influence of grinding condition (intensity) to the average aggregate size.
Table 1 shows the average aggregate size of the volume-weighting of each sample.In all prescriptions, the average aggregate size of MZOA dispersion is greater than 1 μ m.Theoretical consistent with received grinding, improve severity of grind and cause reducing of average aggregate size.
| Prescription | Carrier liquid | Severity of grind | Weighted volumetrically mean size |
| A | CCTG | High | 1.7μm |
| B | CCTG | In | 3.2μm |
| C | AB | High | 2.0μm |
| D | AB | In | 4.7μm |
| E | AB | Low | 6.9μm |
As utilize the aggregation size distribution of the prescription D of laser defusing measure to be presented among Fig. 1.
Embodiment 2: optical property
The prescription B of embodiment 1 and the optical property of C-particularly, total absorptance, soft-focus, CIE whitness index and CIE L
*Brightness-be listed in the table 2 is described in more detail below.The concentration of MZOA is 50% in each prescription.
It is in 20 microns the quartz cell (quartzy unit) that among prescription B and the C each is placed on optical path length.The Carey 300 bio UV-Vis spectrophotometers that utilization is equipped with integrating sphere carry out the optical transmittance measurement.
Total absorptance, A, calculated by total transmittance by following formula:
A＝-Ln[T(％)/100]
Wherein T equals to be expressed as percent, by 20 microns optical path length, to the total transmittance of the visible light at 550nm wavelength place.
The soft focus factor is calculated by the value of total transmittance and diffuse transmissivity.
The CIE whitness index and the L of prescription
*Brightness value is calculated by reflected value according to Australian Standard ASTM-E313.The CIE whitness index is presented at the interior color of rank and total approaching degree of whiteness of 0-100, and wherein said value is high more, and product is white more.Low CIE whitness index is the indication of the high grade of transparency.
Those skilled in the art will recognize that the CIE whitness index needn't be relevant with transparency, because it is influenced by color.For example, if color is a black, then the CIE whitness index is zero, and transparency is bad.CIE L
*Brightness provides the indication of the brightness impression of human eye relative with darkness on 0 to 100 rank, and does not rely on color.Therefore, CIE L
*Brightness is the good indication of whiteness for transparent material.
In order to compare purpose, table 2 also comprises the data of several prior art formula, and described prescription comprises the zinc oxide list microcrystal grain of the following type that is dispersed in the 40-60wt% among the CCTG:
A) the ZnO nano-particle that coats of silicone, it utilizes at United States Patent (USP) 6,503, and the method for describing in 475 prepares, and has the average particulate diameter of about 30nm;
B) the ZnO nano-particle that coats of stearic acid, it utilizes at United States Patent (USP) 6,503, and the method for describing in 475 prepares, and has the mean particle size of about 30nm;
C) the ZnO nano-particle of Silicon stone-coating, it utilizes at United States Patent (USP) 5,587, and the method preparation of describing in 148 has the mean particle size of 82nm.
The compositions of the present invention that comprises MZOA has than remarkable higher transparency of prior art formula relatively and lower diffuse reflectance.This causes lower absorptance (0.16) and lower whiteness (less than 25) and brightness (less than 27) value.Compare with prior art formula, prescription B and C also present the significantly higher soft focus factor.
Table 2:
| Prescription B | Prescription C | The ZnO nano-particle of silicone-coating | The ZnO nano-particle that stearic acid coats | The ZnO nano-particle that Silicon stone coats | |
| Mean particle size | 3.2m | 2.0m | 30nm | 30nm | 82nm |
| Total absorptance at the 550nm place | 0.20 | 0.16 | 0.2 | 0.35 | 0.68 |
| The soft focus factor at the 550nm place | 42.6 | 22.7 | 8.6 | 12.2 | 18.0 |
| The CIE whitness index | 22.2 | 19.5 | 34 | 53 | 60 |
| CIE?L *Brightness | 29.9 | 26.3 | 30 | 40 | 54 |
Embodiment 3: optical property-non-linear Beer Lambert Law behavior
By comprising concentration is that the prescription that 2.5% to 50wt% the dispersion of MZOA in sad tricaprin formed utilizes the laboratory ball mill to prepare.The Carey 300bio UV-Vis spectrophotometer that utilization is equipped with integrating sphere carries out the optical transmittance measurement.Sample is placed in the quartz cell of the optical path length with 0.02mm.
Fig. 2 shows the influence of zinc oxide concentration to the visible transmission ratio.Transmittance is measured and is located to carry out at 550nm (centre of visible spectrum), and path (pond thickness) is 20 microns.The result shows that transmittance reduces at first for the zinc oxide concentration greater than 25wt%, and level then becomes.
In the measurement of CIE whitness index, also observe similarly steadily, as shown in Figure 3.
The analysis of having carried out utilizing the transparency of Beer Lambert law to measure.
Total absorptance, A can be expressed as:
A＝-Ln[T(％)/100]
Wherein T equal to be expressed as percentage ratio to total transmittance at the visible light at the wavelength place of 550nm.
For the linear Beer-Lambert law behavior that will be presented, total absorptance should increase along with the oxidation zinc concentration is linear.
In Fig. 4, the value of total absorptance is drawn as the function of zinc oxide concentration.When low concentration, as passing through linear Beer-Lambert law behavior prediction, absorptance increases along with the concentration that increases is linear.When higher zinc oxide concentration, absorption becomes steadily along with the zinc oxide concentration that increases, and reaches maximum.The behavior is relevant with the qualitative change of light scattering, because the central hole structure of aggregation, the character of light scattering becomes continuous scattering from discrete scattering events under the high oxidation zinc concentration.The variation of light scattering mechanism is to cause the high grade of transparency that presented by dispersion and the reason of low whiteness.
Embodiment 4: sunscreen formulas 1
Following sunscreen formulas utilizes benzoic acid C
12-15Arrcostab prepares based on the prescription D that describes among the top embodiment 1 as carrier:
Prepare phase A and B respectively by chemical substance being mixed and is heated to about 80 ℃.Under 80 ℃, phase A is joined among the phase B lentamente, and mixed 15 minutes or up to evenly with mixer.Mixture is cooled to 40 ℃ then, and adds antiseptic (MTG).Mixture further is cooled to 30 ℃, grinds then up to evenly.SPF is 27 in the body of this prescription.
In order to characterize the optical property of described prescription, described prescription is carried out demulsification, and dry in the dark, and be applied on the quartz cell of the optical path length with 20 microns.The optical property of sunscreen formulas is summarized as follows:
Granule density 36wt% as the desciccator diaphragm of demulsification
The soft focus factor 31
CIE whitness index 34
CIE brightness 41
Embodiment 5: sunscreen formulas II
Comprise that the raw material of listing below according to the following sunscreen formulas utilization of the dispersion of of the present invention 20% MZOA prepares.
The measurement of SPF is according to Australian/New Zealand Standard in the body, and AS/NZS2604:1993 carries out.SPF is 31.2 in the body of measuring.The measurement of external UVAPF is instructed according to COLIPA and is carried out.The external UVAPFDx of Colipa is 12.98.
Embodiment 6: sunscreen formulas III
Prepared the following sunscreen formulas that comprises according to the dispersion of 20%MZOA of the present invention.
The SPF that utilizes testing in vitro to measure is 53.2.
Embodiment 7: the light stability of avobenzone
Preparation comprises according to the dispersion of 15%MZOA of the present invention and the following sunscreen formulas of 2% avobenzone (Parsol 1789) in the carrier below.
According to Australian/NewZealand Standard, AS/NZS 2604:1993 carries out under the measurement of external SPF and the UVA condition below.Based on these measurements, light stability is determined according to AS/NZS 2604:1993 standard.
Provide in the test result table below.The combination table of 15%MZOA and 2% avobenzone reveals 0.94 pre-irradiation UVA/UVB ratio, 378 critical wavelength and five-pointed star Boots grade.It is that light is stable that described prescription is shown.
Before the light degradation
| SPF | The UVA ratio | Star | Classification | Critical wavelength |
| 10.72 | 0.94 | ***** | Ultra | 378 |
Degraded back (utilizing MED 5.5)
| SPF | The UVA ratio | Star | Classification | Critical wavelength | Quantitative light stability | Qualitative light stability |
| 9.68 | 0.87 | ***** | Ultra | 375 | Be | Be |
Be apparent that for those skilled in the relevant art: under the situation that does not depart from basic inventive concept, can carry out multiple changes and improvements.Improvement that all are such and change are considered within the scope of the invention, and its character is determined by the description of front and appended claim.In statement of the present invention and description of the invention, the place that needs other modes except context owing to representation language or necessary hint, word " comprises (comprise) " or modification was used with the implication in being included in as " comprising (comprises) " or " comprising (comprising) ", promptly, specify the existence of the feature of statement, but be not precluded within the existence or the interpolation of the additional features in the various embodiment of the present invention.
Claims (19)
1. a wide spectrum UV light protection compositions is characterized in that described compositions comprises the mesoporous zinc oxide aggregates with average aggregate size of at least 0.8 micron that is dispersed in the carrier, and described compositions is a visible transparent.
2. compositions according to claim 1, wherein, described zinc oxide aggregates have greater than 1.0 microns, greater than 2.0 microns or greater than the average aggregate size one of at least in 3.0 microns.
3. compositions according to claim 1 and 2, wherein, described mesoporous zinc oxide aggregates with effectively provide greater than 15, greater than 25, greater than 30 or exist greater than the amount of the SPF one of at least in 50.
4. according to each described compositions in the claim 1 to 3, when described compositions comprised zinc oxide aggregates by the weight at least 40% of total composition or 50% concentration, described compositions had at the 550nm place 0.15 the total absorptance of being not more than of path by 20 microns.
5. according to each described compositions in the claim 1 to 3, when described compositions comprised zinc oxide aggregates by weight 30% concentration of total composition, described compositions had at the 550nm place 0.14 the total absorptance of being not more than of path by 20 microns.
6. according to each described compositions in the claim 1 to 3, when described compositions comprised zinc oxide aggregates by weight at least 20% concentration of total composition, described compositions had at the 550nm place 0.12 the total absorptance of being not more than of path by 20 microns.
7. according to each described compositions in the claim 1 to 3, when described compositions comprised zinc oxide aggregates by weight at least 10% concentration of total composition, described compositions had at the 550nm place 0.06 the total absorptance of being not more than of path by 20 microns.
8. according to each described compositions in the claim 1 to 3, wherein, described zinc oxide aggregates has at least 3.0 microns average aggregate size, and described compositions has at the 550nm place 0.20 the total absorptance of being not more than of path by 20 microns.
9. according to each described compositions in the claim 1 to 3, wherein, described zinc oxide aggregates has at least 2.0 microns average aggregate size, and described compositions has at the 550nm place 0.16 the total absorptance of being not more than of path by 20 microns.
10. according to each described compositions in the claim 1 to 9, further comprise dibenzoylmethane derivative.
11., comprise less than 5% or less than 3% organic sunscreen filtrate according to each described compositions in the claim 1 to 10.
12. the stable visible light of light according to claim 11-transparent, wide spectrum UV light protection compositions, wherein, described organic sunscreen filtrate is an avobenzone.
13. according to each described compositions in the claim 1 to 12, wherein, described zinc oxide aggregates have greater than 1.0 microns, greater than 2.0 microns or greater than the average aggregate size one of at least in 3.0 microns, and described compositions has at the 550nm place soft focus factor greater than 40.
14. according to each described compositions in the claim 1 to 13, wherein, described zinc oxide aggregates have greater than 1.0 microns, greater than 2.0 microns or greater than the average aggregate size one of at least in 3.0 microns, and described compositions has the CIE whitness index less than 25.
15. according to each described compositions in the claim 1 to 13, wherein, described zinc oxide aggregates have greater than 1.0 microns, greater than 2.0 microns or greater than the average aggregate size one of at least in 3.0 microns, and described compositions has the CIE L less than 30
*Brightness.
16. according to each described compositions in the claim 1 to 15; comprise one or more non-mesoporous zinc oxide aggregates bright protective agents; wherein, described one or more non-mesoporous zinc oxide aggregates bright protective agents exist with the concentration that the SPF with described compositions improves the SPF of no more than 2 units.
17. one kind provides protection for mammal skin or hair in order to avoid the method for ultraviolet radiation, comprises making described skin or hair and contacting according to each described compositions in the claim 1 to 16.
18. one kind by applying the method for the treatment of human skin section disease according to the topical formulations of the visible transparent of each described compositions in the claim 1 to 16 that comprises of treatment effective dose, described human skin section disease is selected from the group of being made up of acne, psoriasis, eczema, ichthyosis, pruritus, drying and dermatitis.
19. one kind have basically the visible transparent described with reference to embodiment and accompanying drawing as this paper, wide spectrum UV light protection compositions.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US639808P | 2008-01-11 | 2008-01-11 | |
| US61/006,398 | 2008-01-11 | ||
| PCT/US2009/030725 WO2009089523A1 (en) | 2008-01-11 | 2009-01-12 | Visibly transparent uv photoprotective compositions |
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| CN101932303A true CN101932303A (en) | 2010-12-29 |
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| EP (1) | EP2244691A1 (en) |
| JP (1) | JP2011509940A (en) |
| KR (1) | KR20100120656A (en) |
| CN (1) | CN101932303A (en) |
| AU (1) | AU2009203992A1 (en) |
| BR (1) | BRPI0906493A2 (en) |
| CA (1) | CA2710958A1 (en) |
| CL (2) | CL2010000748A1 (en) |
| EA (1) | EA201001128A1 (en) |
| IL (1) | IL206911A0 (en) |
| MX (1) | MX2010007498A (en) |
| NZ (1) | NZ587282A (en) |
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| CN105451815A (en) * | 2013-08-22 | 2016-03-30 | 默克专利有限公司 | Diffusion pigments in phototherapy |
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| BRPI1005345B1 (en) * | 2010-04-13 | 2017-06-13 | U.S. Cosmetics Corporation | Strengthening composition of sun protection factor |
| FR2977490B1 (en) * | 2011-07-07 | 2014-03-21 | Oreal | PHOTOPROTECTIVE COMPOSITION |
| SG11201400664WA (en) | 2011-09-16 | 2014-04-28 | Gilead Pharmassett Llc | Methods for treating hcv |
| PT2950786T (en) | 2013-01-31 | 2020-03-03 | Gilead Pharmasset Llc | Combination formulation of two antiviral compounds |
| US10172783B2 (en) * | 2014-06-04 | 2019-01-08 | L'oreal | High UV protection alcohol-free anhydrous clear system |
| EP3873480A4 (en) * | 2018-10-30 | 2022-10-19 | Advance Nanotek Ltd. | Anti-acne composition |
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| US5441726A (en) * | 1993-04-28 | 1995-08-15 | Sunsmart, Inc. | Topical ultra-violet radiation protectants |
| AUPP355798A0 (en) * | 1998-05-15 | 1998-06-11 | University Of Western Australia, The | Process for the production of ultrafine powders |
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- 2009-01-12 KR KR1020107017703A patent/KR20100120656A/en not_active Application Discontinuation
- 2009-01-12 WO PCT/US2009/030725 patent/WO2009089523A1/en active Application Filing
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| CN105451815A (en) * | 2013-08-22 | 2016-03-30 | 默克专利有限公司 | Diffusion pigments in phototherapy |
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| CA2710958A1 (en) | 2009-07-16 |
| KR20100120656A (en) | 2010-11-16 |
| CL2010000749A1 (en) | 2011-03-11 |
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| MX2010007498A (en) | 2010-10-15 |
| ZA201005490B (en) | 2011-04-28 |
| EA201001128A1 (en) | 2011-02-28 |
| JP2011509940A (en) | 2011-03-31 |
| AU2009203992A1 (en) | 2009-07-16 |
| BRPI0906493A2 (en) | 2017-06-13 |
| IL206911A0 (en) | 2010-12-30 |
| CL2010000748A1 (en) | 2011-03-11 |
| NZ587282A (en) | 2012-09-28 |
| EP2244691A1 (en) | 2010-11-03 |
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