Patent Application
20250099345
The present invention relates to a method for increasing sun protection factor (SPF) of a UV filter composition, use of closed-cell metal oxide particles for increasing SPF of a UV filter composition and UV filter compositions comprising the closed-cell metal oxide particles.
UV filter compositions are used to prevent adverse effects of solar radiations on human skin. A wide variety of UV absorbers are available, and a UV filter composition often comprises one or more UV absorber/s to achieve a high UV protection, i.e., a high sun protection factor (SPF).
However, challenges still exist for obtaining a UV filter composition having a high SPF. Several UV filters are characterized by a low solubility in the commonly used formulation media, and hence incorporation of a high amount of such a low-solubility UV filter in a UV filter composition becomes difficult. Further, the highest amount of a UV filter that can be incorporated in a UV filter composition is controlled by government regulations. Therefore, there exists a need for methods for increasing the SPF of a UV filter composition.
An agent used for increasing SPF of a UV filter composition may lead to undesired effects such as scattering of solar radiations, thereby resulting in an unpleasant appearance such as whitening of face. Therefore, it is desired that the method for increasing the SPF of a UV filter composition maintains its transparency and does not lead to undesired effects such as whitening effect.
Accordingly, it is an object of the invention to provide a method for increasing SPF of a UV filter composition. Further, it is an object of the invention to provide a UV filter composition that is not associated with adverse appearance problems such as whitening effect.
It has been surprisingly found that the sun protection factor (SPF) of a UV filter composition can be increased by adding closed-cell metal oxide particles to the UV filter composition.
Accordingly, an aspect of the presently claimed invention is directed to a method for increasing the sun protection factor of a UV filter composition, the method comprising adding closed-cell metal oxide particles to the UV filter composition. The closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed-cells, each closed-cell encapsulating a void volume, wherein the outer surface of the closed-cell metal oxide particles is defined by the array of closed-cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.
Another aspect of the presently claimed invention is directed to use of closed-cell metal oxide particles for increasing the sun protection factor of a UV filter composition. The closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed-cells, each closed-cell encapsulating a void volume, wherein the outer surface of the closed-cell metal oxide particles is defined by the array of closed-cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.
Yet another aspect of the presently claimed invention is directed to a UV filter composition comprising closed-cell metal oxide particles in the range of 0.1 to 25.0 wt. % based on total weight of the UV filter composition. The closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed-cells, each closed-cell encapsulating a void volume, wherein the outer surface of the closed-cell metal oxide particles is defined by the array of closed-cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.
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Before the present compositions and formulations of the presently claimed invention are described, it is to be understood that this invention is not limited to the particular compositions and formulations described, since such compositions and formulation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the presently claimed invention will be limited only by the appended claims.
If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms ‘first’, ‘second’, ‘third’ or ‘a’, ‘b’, ‘c’, etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the presently claimed invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms ‘first’, ‘second’, ‘third’ or ‘(A)’, ‘(B)’ and ‘(C)’ or ‘(a)’, ‘(b)’, ‘(c)’, ‘(d)’, ‘i’, ‘il’ etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
Furthermore, the ranges defined throughout the specification include the end values as well i.e., a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, applicant shall be entitled to any equivalents according to applicable law.
In the following passages, different aspects of the presently claimed invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Reference throughout this specification to ‘one embodiment’ or ‘an embodiment’ means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the presently claimed invention. Thus, appearances of the phrases ‘in one embodiment’ or ‘in an embodiment’ in various places throughout this specification are not necessarily all referring to the same embodiment but may refer to so.
Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the presently claimed invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.
It has been found that closed-cell metal oxide particles can be used to increase the SPF of a UV filter composition. The presently claimed invention provides a method for increasing SPF of a UV filter compositions and also provides UV filter compositions having a high SPF. Further, it is observed that the resultant UV filter composition does not show adverse appearance effects such as the whitening effect, which is usually associated with the addition of agents that scatter radiations.
The closed cell metal oxide particles are structural colorants that interact with UV and visible radiations via light interference effects. Structural colorants are materials containing nano-sized structured surfaces small enough to interfere with visible light and produce color. Bulk samples of closed-cell metal oxide particles exhibit saturated color with reduced unwanted light scattering when porosity and/or microsphere diameter and/or pore diameter are within a certain range. As a result, the presence of closed-cell metal oxide particles in a UV filter composition leads to a decrease in the amount of the radiations travelling through the UV filter composition layer. Thus, an overall decrease in transmittance of the dye or the UV absorber is achieved without increasing its concentration.
Accordingly, an aspect of the presently claimed invention is directed to a method for increasing the sun protection factor of a UV filter composition, the method comprising adding closed-cell metal oxide particles to the UV filter composition, wherein the closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed-cells, each closed-cell encapsulating a void volume, wherein the outer surface of the closed-cell metal oxide particles is defined by the array of closed-cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.
Another aspect of the presently claimed invention is directed to use of closed-cell metal oxide particles for increasing the sun protection factor of a UV filter composition, wherein the closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed-cells, each closed-cell encapsulating a void volume, wherein the outer surface of the closed-cell metal oxide particles is defined by the array of closed-cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.
In a preferred embodiment, the void volume is media inaccessible.
In the context of the present invention, the SPF factor (sun protection factor, SPF) serves to evaluate light protection preparations (UV filter compositions) on humans (in vivo). It indi-cates how much longer a person with a UV filter agent can be exposed to the sun without suffering sunburn than would be possible with the particular individual's self-protection time. The SPF is determined in vitro by measuring the diffuse transmission in the spectral range between 290 and 400 nm.
In the context of the present invention, the term “monodisperse” in reference to spheres, microspheres or nanospheres means particles having generally uniform shapes and generally uniform diameters. A present monodisperse population of spheres, microspheres or nanospheres may have 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the particles by number having diameters within +7%, +6%, +5%, +4%, +3%, +2% or +1% of the average diameter of the population.
In the context of the present invention, the terms ‘particles’, ‘microspheres’, ‘microparticles’, ‘nanospheres’, ‘nanoparticles’, ‘droplets’ etc. also refer to, for example, a plurality thereof, a collection thereof, a population thereof, a sample thereof, or a bulk sample thereof.
In the context of the present invention, the term ‘bulk sample’ refers to a population of particles. For example, a bulk sample of particles is simply a bulk population of particles, for example, ≥0.1 mg, ≥0.2 mg, ≥0.3 mg, ≥0.4 mg, ≥0.5 mg, ≥0.7 mg, ≥1.0 mg, ≥2.5 mg, ≥5.0 mg, ≥10.0 mg, or ≥25.0 mg. A bulk sample of particles may be substantially free of other components.
In the context of the present invention, the phrase “exhibits color observable by the human eye” means color will be observed by an average person. This may be for any bulk sample distributed over any surface area, for example, a bulk sample distributed over a surface area of, for example, from any of 1 cm2, 2 cm2, 3 cm2, 4 cm2, 5 cm2, or 6 cm2 to any of 7 cm2, 8 cm2, 9 cm2, 10 cm2, 11 cm2, 12 cm2, 13 cm2, 14 cm2, or 15 cm2. It may also mean observable by a CIE 1931 2° standard observer and/or by a CIE 1964 10° standard observer. The background for color observation may be any background, for example, a white background, black background, or a dark background anywhere between white and black.
In the context of the present invention, the terms ‘micro’ or ‘micro-scaled’, for example, when referring to particles, mean from 1 micrometer (μm) to less than 1000 μm. The term ‘nano’ or ‘nano-scaled’, for example, when referring to particles, mean from 1 nanometer (nm) to less than 1000 nm.
In the context of the present invention, the term “media-inaccessible” with reference to a volume means that the volume is shielded from infiltration by large molecules (e.g., molecules, such as polymers and oligomers, having a molecular weight greater than 5000 g/mol). The volume may be accessible to solvents, such as water, toluene, hexane, and ethanol.
In the context of the present invention, the terms “microspheres”, “nanospheres”, “droplets”, etc., referred to herein may mean for example a plurality thereof, a collection thereof, a population thereof, a sample thereof or a bulk sample thereof.
In the context of the present invention, the term “micro” or “micro-scaled” means from about 0.5 μm to about 999 μm. The term “nano” or “nano-scaled” means from about 1 nm to about 999 nm.
In the context of the present invention, the terms “spheres” and “particles” may be interchangeable.
Unless otherwise indicated, all parts and percentages mentioned herein are by weight. Weight percent (wt. %), if not otherwise indicated, is based on an entire composition free of any vol-atiles, that is, based on dry solids content.
In a preferred embodiment, the amount of the closed-cell metal oxide particles is in the range of 0.1 to 25.0 wt. % based on total weight of the UV filter composition.
In a preferred embodiment, the amount of the closed-cell metal oxide particles is in the range of 0.5 to 10.0 wt. % based on total weight of the UV filter composition.
In a preferred embodiment, the array of closed-cells is an ordered array.
In a preferred embodiment, the array of closed-cells is a disordered array.
The terms “ordered array” and “disordered array” of the closed-cells refer to the structure of the closed-cells defined by the metal oxides matrix. In case of an “ordered array”, the closed-cells have a structure of a repeating pattern in the matrix. According to a preferred embodiment, an ordered array results in an angle dependent colour. In case of an “disordered array”, the closed-cells have a random structure with no specific pattern in the matrix. According to a preferred embodiment, a disordered array results in an angle independent colour. The terms “ordered array of closed-cells” and “ordered voids” are meant to be understood interchangeably. The terms “disordered array of closed-cells” and “disordered voids” are meant to be understood interchangeably.
In a preferred embodiment, the closed-cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm; more preferably 1.0 μm to 75.0 μm; even more preferably 2.0 μm to 50.0 μm; and most preferably 3.0 μm to 25.0 μm.
In a preferred embodiment, the closed-cell metal oxide particles comprise mainly the metal oxide, that is, they may consist essentially of or consist of metal oxide.
In a preferred embodiment, the amount of metal oxide in the closed-cell metal oxide particles is in the range of 60.0 to 100.0 wt. %; more preferably 65.0 to 99.9 wt. %; even more preferably 70.0 to 99.9 wt. %; and most preferably 75.0 to 99.0 wt. %, based on total weight of the closed-cell metal oxide particles.
In a preferred embodiment, the closed-cell metal oxide particles have an average pore diameter in the range of 3 nm to 500 nm.
In a preferred embodiment, the closed-cell metal oxide particles have an average pore diameter in the range of 3 nm to 400 nm.
In a preferred embodiment, the closed-cell metal oxide particles have an average pore diameter in the range of 3 nm to 300 nm; more preferably 10 nm to 300 nm; even more preferably 25 nm to 250 nm; and most preferably 50 nm to 200 nm.
In a preferred embodiment, the closed-cell metal oxide particles have an average porosity in the range of 0.10 to 0.90.
In a preferred embodiment, the closed-cell metal oxide particles have an average porosity in the range of 0.10 to 0.80, more preferably 0.20 to 0.75; even more preferably 0.30 to 0.70; and most preferably 0.40 to 0.70.
In a preferred embodiment, the metal oxide matrix comprises silica.
In a preferred embodiment, the metal oxide matrix comprises alumina.
In a preferred embodiment, the metal oxide matrix comprises titania.
In a preferred embodiment, the metal oxide matrix comprises silica and alumina.
In a preferred embodiment, the metal oxide matrix comprises silica and titania.
In a preferred embodiment, the metal oxide matrix comprises silica and zinc oxide.
Metal oxide particles are used for the preparation of the metal oxide matrix.
In a preferred embodiment, the metal oxide particles fuse with each other during the preparation, and result in a continuous metal oxide matrix.
In a preferred embodiment, a combination of two or more different types of metal oxide particles is used for the preparation of the closed-cell metal oxide particles. The combination of metal oxide particles may contain two or more populations having different compositions and/or morphologies.
In a preferred embodiment, the metal oxide particles comprise two or more populations having different particle sizes.
In a preferred embodiment, the metal oxide particles comprise particles such that each particle is made of two or more different metal oxides.
In a more preferred embodiment, the metal oxide particles comprise particles such that each particle is made of silica and titania.
In a preferred embodiment, the closed-cells are monodisperse.
In a preferred embodiment, the closed-cells have a bimodal distribution of monodisperse closed-cells.
In a preferred embodiment, the closed-cells are polydisperse.
In a preferred embodiment, the closed-cell metal oxide particles are prepared using a polymeric sacrificial template.
According to one embodiment of the invention, the closed-cell metal oxide particles have an additional sealing layer. The sealing layer may span over several or all closed-cells of a closed-cell metal oxide particle. In a particularly preferred embodiment, the sealing layer comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof. It is most preferred that the sealing layer comprises silica.
According to another embodiment of the invention, the closed-cell metal oxide particles are free of a sealing layer.
In a preferred embodiment, the closed-cell metal oxide particles are prepared by a method comprising the following steps.
In a preferred embodiment, the first particles comprise net positive charged surfaces, and the second particles comprise net negative charged surfaces.
In a preferred embodiment, the first particles comprise net negative charged surfaces, and the second particles comprise net positive charged surfaces.
In a preferred embodiment, the surface charges drive the formation of the layer of the second particles on the first particles.
In a preferred embodiment, the polymer material comprises a polymer selected from poly(meth)acrylic acid, poly(meth)acrylates, polystyrenes, polyacrylamides, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, a co-polymer of methyl methacrylate and [2-(methacryloyloxy)ethyl] trimethylammonium chloride, derivatives thereof, salts thereof, copolymers thereof, or mixtures thereof.
In a preferred embodiment, the first particles have an average diameter from 50 nm to 500 nm.
In a preferred embodiment, the metal oxide material comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.
In a preferred embodiment, the second particles have an average diameter from 1 nm to 120 nm.
In a preferred embodiment, the generating the liquid droplets is performed using a microfluidic process.
In a preferred embodiment, the generating and drying the liquid droplets is performed using a spray-drying process.
In a preferred embodiment, the generating the liquid droplets is performed using a vibrating nozzle.
In a preferred embodiment, the drying the droplets comprises evaporation, microwave irradi-ation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.
In a preferred embodiment, the particle dispersion is an aqueous particle dispersion.
In a preferred embodiment, a weight ratio of the first particles to the second particles is selected from 1/10 to 10/1.
In a preferred embodiment, a weight ratio of the first particles to the second particles is selected from 2/3, 1/1, 3/2, or 3/1.
In a preferred embodiment, a particle size ratio of the second particles to the first particles is selected from 1/50 to 1/5.
In a preferred embodiment, the closed-cell metal oxide particles are prepared by a method comprising:
In a preferred embodiment, the polymer particles comprise net positive charged surfaces, and the sol-gel matrix of the metal oxide material comprises a net negative charge.
In a preferred embodiment, the polymer particles comprise net negative charged surfaces, and the sol-gel matrix of the metal oxide material comprises a net positive charge.
Advantageously, depending on the compositions of the metal oxide particles, their relative sizes, and shapes, a bulk sample of the closed-cell metal oxide particles may exhibit a color observable by the human eye, may appear white, or may exhibit properties in the range of UV spectrum.
A bulk sample of the closed-cell metal oxide particles described herein may exhibit angle-dependent color or angle-independent color. “Angle-dependent” color means that observed color has dependence on the angle of incident light on a sample or on the angle between the observer and the sample. “Angle-independent” color means that observed color has substantially no dependence on the angle of incident light on a sample or on the angle between the observer and the sample.
In a preferred embodiment, the angle dependent color is achieved with an ordered array of the closed-cells.
In a preferred embodiment, the angle independent color is achieved with a disordered array of the closed-cells.
In a preferred embodiment, the angle dependent color is achieved when the closed-cells are monodisperse.
In a preferred embodiment, angle independent color is achieved when the closed-cells are polydisperse.
In a preferred embodiment, angle independent color is achieved when the closed-cells exhibit a bimodal distribution of monodisperse polymer particles.
In a preferred embodiment, angle independent color is achieved independently of the poly-dispersity and shapes of the matrix particles.
Any of the embodiments exhibiting angle dependent or angle independent color may be modified to exhibit whiteness or effects in the ultraviolet spectrum.
In a preferred embodiment, the closed-cell metal oxide particles
In a preferred embodiment, the closed-cell metal oxide particles
In a preferred embodiment, the closed-cell metal oxide particles
In a preferred embodiment, the closed-cell metal oxide particles further comprise a light absorber.
In a preferred embodiment, the light absorber is present in the range of 0.1 to about 40.0 wt. %, more preferably 0.5 to 25.0 wt. %; and most preferably 1.0 to 10.0 wt. %.
In a preferred embodiment, the light absorber comprises at least one ionic species.
In a preferred embodiment, the closed-cell metal oxide particles exhibit color in the visible spectrum at a wavelength in the range of 380 nm to 800 nm.
In a preferred embodiment, the closed-cell metal oxide particles exhibit effect in a wavelength range in the ultraviolet spectrum selected from the group consisting of 100 nm to 400 nm.
In a preferred embodiment, the closed-cell metal oxide particles exhibit a wavelength range in the ultraviolet and visible spectrum selected from the group consisting of 200 nm to 500 nm.
In a preferred embodiment, the UV filter composition comprises an UV absorber selected from the group consisting of
Examples of p-aminobenzoic acid derivatives (d1) which can be employed according to the presently claimed invention, are 4-aminobenzoic acid (PABA); ethyldihydroxypropyl-PABA of the formula
PEG-25-PABA of the formula
wherein m, n and x have the same meaning, and each denote an integer from 1 to 25; octyl-dimethyl PABA of the formula
or glycyl aminobenzoate of the formula
Example for salicylic acid derivatives (d2) which can be employed according to the presently claimed invention, are
triethanolamine salicylate of the formula
amyl p-dimethylaminobenzoate of the formula
octyl salicylate of the formula
or 4-isopropylbenzyl salicylate of the formula
Example for benzophenone derivatives (d3) which can be employed according to the presently claimed invention, are:
wherein
In a more preferred embodiment, the UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.
Benzophenone derivatives (d3) also include dimeric benzophenone derivatives corresponding to the formula
wherein
or
wherein
In a more preferred embodiment, dimeric benzophenone derivatives of the formula
are employed as UV absorbers (d3).
Examples of dibenzoylmethane derivatives (d4) which can be employed according to the presently claimed invention are butylmethoxydibenzoylmethane-[1-(4-tert-butylphenyl)-3-(4-methoxyphenyl) propane-1,3-dione].
Examples of diphenylacrylate derivatives (d5) which can be employed according to the presently claimed invention are octocrylene-(2-ethylhexyl 2-cyano-3,3′-diphenylacrylate) or etocrylene (ethyl 2-cyano-3,3′-diphenylacrylate).
Examples of benzofuran derivatives (d7) which can be employed according to the presently claimed invention are 3-(benzofuranyl) 2-cyanoacrylate, 2-(2-benzofuranyl)-5-tert-butylben-zoxazole or 2-(p-aminophenyl)benzofuran and in particular the compounds of the formula
Examples of polymeric UV absorbers (d8) which can be employed according to the presently claimed invention and contain one or more organosilicon radicals are benzylidenemalonate derivatives, in particular the compound of the formula
wherein Ra denotes hydrogen or methoxy and r denotes approximately 7; the compound of the formula
or polysilicone-15 corresponding to the formula
Examples of cinnamic acid esters (d2) which can be employed according to the presently claimed invention are octyl methoxycinnamate (4-methoxycinnamic acid 2-ethylhexyl ester), diethanolamine methoxycinnamate (diethanolamine salt of 4-methoxycinnamic acid), isoamyl p-methoxycinnamate (4-ethoxycinnamic acid 2-isoamyl ester), 2,5-diisopropyl methycinnamate or a cinnamic acid amido derivative.
Examples of camphor derivatives (d10) which can be employed according to the presently claimed invention are 4-methylbenzylidenecamphor-[3-(4′-methyl)benzylidenebornan-2-one], 3-benzylidenecamphor-(3-benzylidenebornan-2-one), polyacrylamidomethylbenzyli-denecamphor {N-[2 (and 4)-2-oxyborn-3-ylidenemethyl)benzyl] acrylamide polymer), trimoni-umbenzylidenecamphor sulfate-[3-(4′-trimethylammonium)-benzylidenebornan-2-one me-thylsulfate], terephthalydenedicamphorsulfonic acid {3,3′-(1,4-phenylenedimethine)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]heptane-1-methanesulfonic acid} or salts thereof, or ben-zylidenecamphorsulfonic acid [3-(4′-sulfo)benzylidenebornan-2-one] or salts thereof.
Examples of hydroxyphenyltriazine derivatives (du) which can be employed according to the invention are, in particular, bis-resorcinyltriazines of the formula
wherein
or a radical of the formula (HPT-01h)
In a preferred embodiment, the compound class (du) are:
Examples of benzotriazole derivatives (d12) which can be employed according to the presently claimed invention correspond to the formula
wherein
In a preferred embodiment, compounds of the formula (BT-01), wherein
In a more preferred embodiment, the benzotriazole derivatives (d12) are compounds of the formula
In a more preferred embodiment, UV filters of the formula BT-01 are compounds wherein
In a more preferred embodiment, the benzotriazole derivatives (d12) are compounds of the formula
Examples of trianilino-s-triazine derivatives (d13) which can be employed according to the presently claimed invention correspond to the formula
wherein
In a preferred embodiment, trianilino-s-triazine derivatives (d13) compound is ethylhexyl triazone corresponding to the formula
or Diethylhexyl butamido triazone corresponding to the formula
or Ethylhexyl bis-Isopentylbenzoxazolylphenyl melamine corresponding to the formula
Examples of 2-phenylbenzimidazole-5-sulfonic acid, and salts thereof (d14) which can be employed according to the invention is Disodium 2,2′-(1,4-phenylene)bis(6-sulfo-1/-1,3-ben-zimidazole-4-sulfonate (Bisdisulizole disodium).
Examples of tris-biphenyl-triazine derivatives (d17) which can be employed according to the invention correspond to the formula
wherein
A denotes a radical of the formula
or
wherein in formula (TBT-01a) at least one of the radicals R2, R3 and R4 denotes a radical of the formula (TBT-01c);
In a preferred embodiment, the UV filters (d17) which can be employed according to the presently claimed invention correspond to the compounds of the formula
Examples of benzylidenemalonates (d19) which can be employed according to the invention correspond to the formula
wherein
a radical of the formula
or a radical of the formula
wherein
In a preferred embodiment, benzylidenemalonates (d19) which can be employed according to the presently claimed invention are listed in the following table:
An example of the phenylene-bis-diphenyltriazines (d21) which can be employed according to the presently claimed invention is 5,6,5,6-tetraphenyl-3,3′-(1,4-phenylene)-bis [1,2,4]triazine corresponds to the formula
An example of the imidazoline derivatives (d22) which can be employed according to the presently claimed invention, is Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.
An example of the diarylbutadiene derivatives (d23) which can be employed according to the presently claimed invention, is 1,1-dicarboxy-(2,2′-dimethylpropyl)-4,4-diphenylbutadiene.
Examples of amino hydroxybenzoyl hexyl benzoate derivatives (d24) which can be employed according to the invention is 2-(4-Diethylamino-2-hydroxybenzoyl)benzoicacid hexylester corresponds to the formula
Examples of bis-(diethylamino hydroxybenzoyl benzoyl)-piperazine derivatives (d25) which can be employed according to the invention corresponds to the formula
Each of the abovementioned UV filters (d1)-(d25) can be used according to the presently claimed invention as a mixture. For example, mixtures of two, three, four, five or six of the filter groups (d1)-(d25) can be used according to the presently claimed invention. Mixtures of two, three, four, five or six UV filters from one or more representatives of substance classes (d1)-(d25) can also be used according to the invention.
In a preferred embodiment, the UV filters (d) are representatives of the following compound classes:
In a more preferred embodiment, the following oil-soluble UV filters are used according to the invention:
In a more preferred embodiment, the following particulate UV filters are used according to the invention:
In a most preferred embodiment, the UV filter is at least one selected from the group consisting of
In a particularly preferred embodiment, the UV filter is a mixture of UV filters selected from the group consisting of (d9a), (d11a), (d13a) and (d3a).
In a preferred embodiment, the method or use protects the skin against ultraviolet radiation and high energy visible light.
In a preferred embodiment, the protects the skin against ultraviolet radiation having a wavelength in the range from 280 and 400 nm, and high energy visible light in the range of wavelength from 380 to 480 nm.
In a preferred embodiment, the method or use protects the skin against high energy visible light of wavelength in the range from 380 to 480 nm.
It has been observed that the increase in the absorbance due to the presence of closed-cell metal oxide particles is stronger in the UV spectral range compared to the visible range.
In a preferred embodiment, the method further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.
In a preferred embodiment, the use further minimizes or masks the whitening effect of the UV filter composition and maintains its transparency.
Another aspect of the presently claimed invention is directed to a UV filter composition comprising closed-cell metal oxide particles in the range of 0.1 to 25.0 wt. % based on total weight of the UV filter composition. The closed-cell metal oxide particles comprise a metal oxide matrix defining an array of closed-cells, each closed-cell encapsulating a void volume, wherein the outer surface of the closed-cell metal oxide particles is defined by the array of closed-cells. The metal oxide matrix comprises at least one metal oxide selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide, chromium oxide, and mixtures thereof.
In a preferred embodiment, the void volume is media inaccessible.
In a preferred embodiment, the UV filter composition comprises
In a preferred embodiment, the UV filter composition comprises
In a preferred embodiment, the UV filter composition comprises
In a preferred embodiment, the oil is present in the form of a discontinuous phase in the range of 5.0 to 50.0 wt. %, based on total weight of the UV filter composition.
In a preferred embodiment, the water is present in the form of a discontinuous phase in the range of 5.0 to 50.0 wt. %, based on total weight of the UV filter composition.
In a preferred embodiment, the UV filter composition comprises
In a preferred embodiment, the UV filter composition comprises
In a preferred embodiment, the amount of the metal oxide in the closed-cell metal oxide particles is in the range of 60.0 to 100.0 wt. %, based on total weight of the closed-cell metal oxide particles.
In a preferred embodiment, the closed-cell metal oxide particles have an average diameter in the range of 0.5 μm to 100.0 μm.
In a preferred embodiment, the closed-cell metal oxide particles have an average porosity in the range of 0.10 to 0.90.
In a preferred embodiment, the closed-cell metal oxide particles have an average porosity in the range of 0.10 to 0.80.
In a preferred embodiment, the closed-cell metal oxide particles have an average pore diameter in the range of 3 nm to 500 nm.
In a preferred embodiment, the closed-cell metal oxide particles further comprise a light (UV-visible) absorber.
In a preferred embodiment, the light (UV-visible) absorber is present in the range of 0.1 wt. % to 40.0 wt. %.
In a preferred embodiment, the UV filter composition further comprises an UV absorber selected from the group consisting of
Representative examples of the UV absorbers are described hereinabove.
In a preferred embodiment, the UV filter composition is sunscreen composition.
In a preferred embodiment, the UV filter composition is day care composition.
In a preferred embodiment, the UV filter composition is at least one selected from the group consisting of creams, gels, lotions, alcoholic solutions, aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders and ointments.
The final UV filter composition listed may exist in a wide variety of presentation forms, for example:
Of special importance as UV filter compositions for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
In addition the UV filter compositions may contain further adjuvants as described below.
In the context of the present invention, possible oily substances are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms (e.g. Eutanol® G), esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols and esters of branched C6-C13-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as e.g. myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C3-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, in particular diethylhexyl malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as e.g. propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C6-C10-fatty acids, liquid mono/di/triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, plant oils, branched primary alcohols, substituted cyclo-hexanes, linear and branched C6-C22-fatty alcohol carbonates, such as e.g. Dicaprylyl Carbonate (Cetiol® OE), Guerbet carbonates based on fatty alcohols having 6 to 18 preferably 8 to 10 C atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g. Fin-solv® TN), linear or branched, symmetric or unsymmetric dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as e.g. dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols (Hydagen® HSP, Sovermol® 750, Sovermol®1102), silicone oils (cyclomethicone, silicon methicone types and others) and/or aliphatic or naph-thenic hydrocarbons, such as e.g. mineral oil, vaseline, petrolatum, squalane, squalene, iso-hexadecane or dialkylcyclohexanes are suitable in consideration.
In certain embodiments, the oily substances are medium-polarity oils, in particular esters of C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms and/or linear and branched C6-C22-fatty alcohol carbonates, adipic acid esters of linear or branched alcohols having 1 to 22 carbon atoms, very particularly of linear alcohols having 1 to 6 carbon atoms, are particularly suitable here.
Linear and branched fatty alcohol carbonates, in particular dicaprylyl carbonate, are particularly preferably used as oily substance.
In a more preferred embodiment, dibutyl adipate is used as oily substance.
In a even more preferred embodiment, the oil phase is selected from C12-15 alkyl benzoate, dibutyl adipate, dicaprylyl carbonate, propylheptyl caprylate, caprylic/capric triglyceride, dicaprylyl ether, butylene glycol dicaprylate/dicaprate, coco-caprylate, octyldodecanol, di-propylheptyl carbonate, caprylyl-caprylate/caprate, cocoglycerides, ethylhexyl stearate, iso-hexadecane, isopropyl palmitate, and isopropyl myristate.
In another embodiment, the amount of oil phase is in the range of 20 to 35 wt. %, based on total weight of the UV filter composition.
In certain embodiments, the UV filter composition further comprises at least one surfactant in the range of 1.0 to 20.0 wt. %, based on total weight of the UV filter composition.
In certain embodiments, the surfactant is selected from an anionic surfactant, a nonionic surfactant, and a polymeric surfactant.
The anionic surfactants are characterized by one or more anionic group which confers solubility in water, such as e.g., a carboxylate, sulfate, sulfonate or phosphate group, and a lipo-philic radical. In addition, the molecule can contain polyglycol ether, ester, ether and hydroxyl groups. Anionic surfactants which are tolerated by skin are known to the person skilled in the art in large numbers from relevant handbooks and are commercially obtainable.
Representative examples of the preferred anionic surfactants are, in each case in the form of their salts, ether-carboxylic acids, acylsarcosides having 8 to 24 C-atoms in the acyl group, acyltaurides having 8 to 24 C-atoms in the acyl group, acylisethionates having 8 to 24 C-atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C-atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C-atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 C-atoms, linear alpha-olefinsulfonates having 8 to 24 C-atoms, alpha-sulfo-fatty acid methyl esters of fatty acids having 8 to 30 C-atoms, alkyl sulfates, alkyl polyglycol ether sulfates, esters of tartaric acid and citric acid, alkyl and/or alkenyl ether phosphates, sulfated fatty acid alkylene glycol esters, monoglyceride sulfates and monoglyceride ether sulfates as well as condensation products of C8-C30-fatty alcohols with protein hydrolysates and/or amino acids and derivatives thereof, so-called protein fatty acid condensates, e.g. Lamepon®, Gluadin®, Hosta-pon® KCG or Amisoft®.
The salts of these surfactants are preferably selected from the sodium, potassium and ammonium and the mono-, di- and trialkanalammonium salts having 2 to 4 C-atoms in the alkanol group.
Particularly suitable anionic surfactants are liquid at room temperature, preferably from 18 to 25° C. A desirable feature in particular of these anionic surfactants is that they have a low water content of at most 10 wt. %, preferably 0.1 to 5 wt. %, based on the total weight of the anionic surfactant.
In a most preferred embodiment, the anionic surfactants are alk(en)yl polyglycol ether citrates and in particular mixtures of mono-, di- and triesters of citric acid and alkoxylated alcohols which correspond to the formula (I):
wherein
R4(OCH2CHR5)n
wherein
Typical examples of the alcohol part of the esters are addition products of on average 1 to 20 mol, preferably 5 to 10 mol of ethylene oxide and/or propylene oxide on caproyl alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitolelyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical grade mixtures thereof.
Such alk (en) yl polyglycol ether citrates are advantageous for the agents according to the invention since they are liquid anionic surfactants having a low water content of maximum 5 wt. %, based on the anionic surfactant.
The anionic surfactants are preferably present in amounts in the range of 7 to 17 wt. %, based on total weight of the UV filter composition.
The agents according to the invention furthermore comprise at least (c) 0.5 to 25 wt. % of a further co-surfactant which differs from anionic surfactants.
Suitable co-surfactants are, in principle, zwitterionic, ampholytic, cationic and/or nonionic surfactants.
Those surface active compounds which carry at least one quaternary ammonium group and at least one —COO(−) or —SO3(−) group in the molecule are called zwitterionic surfactants. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example coco-alkyldimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinates, for example coco-acylamimopropyldime-thylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having in each case 8 to 18 C-atoms in the alkyl or acyl group, and coco-acylaminoethylhydroxyethyl-carboxymethyl glycinate. The fatty acid amide derivative known under the INCI name Cocam-idopropyl Betaine is a preferred zwitterionic surfactant. Tego® Betain 810 (INCI: Capryl/Capramidopropyl Betaine) and a surfactant mixture of Rewopol® SBCS 50K (INCI: Disodium PEG-5 Laurylcitrate Sulfosuccinate, Sodium Laureth Sulfate) and Tego® Betain 810 (Capryl/Capramidopropyl Betaine), in particular in the weight ratio of 1:4 to 4:1, very particularly preferably in the weight ratio of from 1:4 to 1:1, are particularly preferred according to the invention.
Ampholytic surfactants are understood as meaning those surface-active compounds which contain, apart from a C8-C18-alkyl or acyl group, at least one free amino group and at least one —COOH or —SO3H group in the molecule and are capable of formation of inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-al-kylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylgly-cines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids having in each case 8 to 18 C atoms in the alkyl group. Preferred ampholytic surfactants are N-coco-alkylaminopropionate, coco-acylaminoethylaminopropionate and C12-18-acylsar-cosine.
Quaternary ammonium compounds in particular can be used as cationic surfactants. Surfactants from this substance class have a particularly high affinity for the skin and can improve the degree of sensory smoothness. These include, inter alia, ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammo-nium chlorides and trialkylmethylammonium chlorides, e.g., cetyltrimethylammonium chlo-ride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldime-thylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammo-nium chloride. The very readily biodegradable quaternary ester compounds, such as, for example, the dialkylammonium methosulfates and methylhydroxyalkyldialkoyloxyalkylammo-nium methosulfates marketed under the trade name Stepantex® and the corresponding products of the Dehyquart& series, can furthermore be employed as cationic surfactants. The term “esterquats” is in general understood as meaning quaternized fatty acid triethanolamine ester salts. They impart to the compositions particularly soft feel. These are known substances which are prepared by the relevant methods of organic chemistry. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
Nonionic surfactants are particularly preferably present as co-surfactants, for example
The addition products of ethylene oxide and/or of propylene oxide on fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or on castor oil are known, commercially obtainable products. These are homologue mixtures, the average degree of alkoxylation of which corresponds to the ratio of the substance amounts of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. They are W/O or O/W emulsifiers, depending on the degree of ethoxylation. For the preparations according to the invention, the reaction products with 1-100 mol of ethylene oxide are particularly suitable.
Advantageous compounds from the group of nonionic surfactants are partial esters of polyols, in particular of C3-C6-polyols, such as, for example, glyceryl monoesters, partial esters of pentaerythritol or sugar esters, e.g. sucrose distearate, sorbitan monoisostearate, sorbitan ses-quiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquieru-cate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricino-leate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monoma-leate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical grade mixtures thereof. Addition products of from 1 to 30, preferably 5 to 10 mol of ethylene oxide on the sorbitan esters mentioned are also suitable nonionic surfactants.
Nonionic surfactants from the group of alkyl oligoglycosides are particularly skin-friendly and may therefore preferably be suitable in the context of the invention. C8-C22-alkyl mono- and oligoglycosides, their preparation and their use are known. Their preparation is carried out in particular by reaction of glucose or oligosaccharides with primary alcohols having 8 to 22 C atoms, preferably 12 to 22, and particularly preferably 12 to 18 C atoms. With respect to the glycoside radical, both monoglycosides in which a cyclic sugar residue is bonded glycosidically to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of up to preferably 8 are suitable. The degree of oligomerization here is a statistical mean based on a conventional distribution of homologues for such technical grade products Products which are available under the name Plantacare& contain a glucosidically bonded C8-C16-alkyl group on an oligoglucoside radical, the average degree of oligomerization of which is 1 to 2. The acylglucamides derived from glucamine are also suitable as nonionic surfactants.
Nonionic surfactants, preferably polyol and/or polyglycerol esters, are very particularly preferably present as co-surfactants in the agents according to the invention as component (c), and/or alkyl oligoglycosides.
The polyol component of these surfactants can be derived from substances which have at least two, preferably 3 to 12 and in particular 3 to 8 hydroxyl groups and 2 to 12 carbon atoms.
Typical examples are:
Reaction products based on polyglycerol are of particular importance because of their excel-lent use properties.
The acid component of these surfactants can be derived from straight-chain, branched, saturated and/or unsaturated carboxylic acids, optionally with functional groups, such as hydroxyl groups. The acid component is particularly preferably fatty acids having 12 to 22 carbon atoms, which optionally carry a hydroxyl group, and in particular hydroxystearic acid.
In a preferred embodiment of the invention the diester of polyhydroxystearic acid, polyglyceryl 2-dipolyhydroxystearate, which is marketed, for example, by BASF Personal Care and Nutri-tion GmbH under the name Dehymuls® PGPH is used as a glyceryl ester.
In a preferred embodiment of the invention Eumulgin® SG, Eumulgin® Prisma, Emulgade® sucro and Emulgade® Sucro Plus are used as surfactants.
In the agents according to the invention the further co-surfactants are conventionally present in an amount in the range of 0.5 to 25 wt. %; more preferably in the range of 3.0 to 18 wt. %; and particularly preferably in the range of 7 to 18 wt. %.
In certain embodiments, the UV filter composition further comprises additives selected from thickener, active ingredients, preservatives, and perfumes.
Suitable thickeners are anionic, zwitterionic, amphoteric and nonionic copolymers, such as, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, acrylamidopropyltrimethylammonium chlo-ride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert-butylaminoethyl meth-acrylate/2-hydroxypropyl methacrylate polymers, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam terpolymers and optionally polysaccharides, in particular xanthan gum, guar and guar derivatives, agar-agar, alginates and tyloses, cellulose and cellulose derivatives, such as carboxymethylcellulose, carboxymethylcellulose and hydroxycellulose and moreover silicones.
Preferably, thickeners selected from the group of polyacrylates and crosslinked polyacrylates, such as Rheocare TTA®, Cosmedia® SP, Rheocare® C Plus, Tinovis® ADE, Tinovis® GTC, are added.
Thickeners from the group of polysaccharides, such as Keltrol® T or Rheocare® XG, and thickeners such as Hydagen® 558P, Hydagen® Clean, Rheocare® XGN, Tinovis® GTC, Cosmedia® ACE are furthermore preferred.
Preferably, the amounts of thickener are in the range from 0.5 to 5 wt. %, in particular from 1 to 4 wt. %, calculated as active substance and based on total weight of the UV filter composition.
The thickeners can be added to the concentrated agent before the dilution with water is carried out or can be contained in the water with which the dilution of the concentrated agent is carried out.
According to a preferred process variant, the concentrated agent is mixed with the thickener, and water for dilution is added to this mixture and the further formulation constituents are optionally stirred in.
According to another preferred process variant, the water, the thickener and optionally the other auxiliary substances are stirred with one another and the concentrated agent is added to this mixture.
The final UV filter formulations prepared by the process according to the invention are often particularly finely divided O/W emulsion having an average particle size of <10 μm, preferably <5 μm.
Biogenic active compounds which are suitable according to the invention are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and fragmentation products thereof,-glucans, retinol, bisabo-lol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as e.g., Prunus extract, Bambara nut extract and vitamin complexes. Such active compounds are employed in final UV filter formulations as agents which trap free radicals and serve to regenerate the skin.
Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver complexes known by the name Surfacine®.
Perfume oils which may be mentioned are natural, plant and animal as well as synthetic odoriferous substances or mixtures thereof. Natural odoriferous substances are obtained, inter alia, by extraction of flowers, stems, leaves, fruit, fruit peel, roots and resins of plants. Animal raw materials are furthermore possible, such as, for example, civet and castoreum. Typical synthetic odoriferous compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Preferably, mixtures of various odoriferous substances which together generate a pleasant fragrance note are used.
In a preferred embodiment, the perfume is selected from limonene, citral, linalool, alpha-isomethylionon, geraniol, citronellol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyrane, 2-tert.-pentylcyclohexylacetate, 3-methyl-5-phenyl-1-pentanol, 7-acetyl-1,1,3,4,4,6-hexamethylte-traline, adipine acid diester, alpha-amylcinnamaldehyde, alpha-methylionon, amyl-C-bu-tylphenylmethylpropionalcinnamal, amylsalicylate, amylcinnamylalcohol, anisealcohol, ben-zoin, benzylalcohol, benzylbenzoate, benzylcinnamate, benzylsalicylate, bergamot oil, bitter orange oil, butylphenylmethylpropiol, cardamom oil, cedrol, cinnamal, cinnamylalcohol, cit-ronnellylmethylcrotonate, lemon oil, coumarin, diethylsuccinate, ethyllinalool, eugenol, evernia furfuracea extracte, evernia prunastri extracte, farensol, guajak wood oil, hexylcinnamal, hexylsalicylate, hydroxycitronellal, lavender oil, lemon oil, linaylacetate, mandarine oil, menthyl PCA, methylheptenone, nutmeg oil, rosemary oil, sweet orange oil, terpineol, tonka bean oil, triethylcitrate, and vanillin.
In certain embodiments, the final UV filter formulations further comprise auxiliary substances, such as moisture-retaining agents/skin-moisturizing agents, viscosity regulators, oils, fats and waxes, surfactants, pearlescent waxes, super-oiling agents, stabilizers, cationic, zwitterionic or amphoteric polymers, further UV filters, biogenic active compounds, film-forming agents, swelling agents, hydrotropic substances, preservatives, solubilizers, perfume oils, dyestuffs, insect repellent active compounds etc., which are listed below by way of example.
Moisture-retaining agents serve to further optimize the sensory properties of the composition and for moisture regulation of the skin. The moisture-retaining agents can be present in an amount in the range of 0 to 5.0 wt. %, based on total weight of the UV filter composition.
Suitable substances are, inter alia, amino acids, pyrrolidonecarboxylic acid, lactic acid and salts thereof, lactitol, urea and urea derivative, uric acid, glucosamine, creatinine, collagen cleavage products, chitosan or chitosan salts/derivatives, and in particular polyols and polyol derivatives (e.g. glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene gly-col, erythritol, 1,2,6-hexanetriol, polyethylene glycols, such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (inter alia fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sucrose, sor-bitylsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and salts thereof), ethoxylated sorbitol (sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40), honey and hardened honey, hardened starch hydrolysates and mixtures of hardened wheat protein and PEG-20/acetate copolymer. Substances which are preferably suitable according to the invention as moisture-retaining agents are glycerol, diglycerol, triglycerol and butylene glycol.
Possible insect repellants are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or 3-(N-n-butyl-N-acetylamino) propionic acid ethyl ester), which is marketed by Merck KGaA under the name Insect Repellent 3535, and butylacetylaminoproprionate. They are conventionally employed in the compositions according to the invention in an amount in the range of 0 to 6 wt. %, based on total weight of the UV filter composition.
The viscosity of the agents according to the invention can be achieved by addition of viscosity regulators. Possible viscosity regulators are, inter alia, agents which impart consistency, such as e.g., fatty alcohols or hydroxy-fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and partial glycerides, fatty acids having 12 to 22 carbon atoms or 12-hydroxy-fatty acids. A combination of these substances with alkyl oligoglucosides and/or fatty acid N-methylglucamides of the same chain length is also suitable, since such combinations deliver particularly stable and homogeneous emulsions. The viscosity regulators also include thick-ening agents, such as, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethyl- and hydroxypropylcellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (e.g. Carbopols® and Pemu-len types from Goodrich; Synthalens& from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), non-crosslinked and polyol-crosslinked pol-yacrylic acids, polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone. Bentonites, such as e.g., Bentone& Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, Disteard-imonium Hectorite and propylene carbonate, have also proved to be particularly effective. Surfactants, such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrowed homologue distribution, alkyl oligoglucosides and electrolytes, such as e.g., sodium chloride and ammonium chloride, can also be employed for regulation of the viscosity.
In the context of the invention fats and waxes are understood as meaning all lipids having a fat- or wax-like consistency which have a melting point above 20° C. These include, for example, the classic triacylglycerols, that is to say the triesters of fatty acids with glycerol, which can be of plant or animal origin. These can also be mixed esters, that is to say triesters of glycerol with various fatty acids, or a mixture of various glycerides. These also include mixtures of mono-, di- and triglycerides. So-called hardened fats and oils which are obtained by partial hydrogenation are particularly suitable according to the invention. Hardened fats and oils of plants are preferred, e.g., hydrogenated castor oil, groundnut oil, soya oil, rape oil, beet seed oil, cottonseed oil, soya oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, maize oil, olive oil, sesame oil, cacao butter and coconut fat. Oxidation-stable plant glycerides which are available under the name Cegesoft® or Novata® are particularly suitable.
Possible waxes are, inter alia, natural waxes, such as e.g. candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygium fat, ceresin, ozocerite (earth wax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), such as e.g. montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as e.g. polyalkylene waxes and polyethylene glycol waxes.
In addition to the fats, fat-like substances, such as lecithins and phospholipids, are also possible as additives. Lecithins are glycero-phospholipids which are formed from fatty acids, glycerol, phosphoric acid choline by esterification, and are often also called phosphatidylcholines (PC). Cephalins, which are also called phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids, may be mentioned as an example of natural lecithins. In contrast, phospholipids are usually understood as meaning mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates). Sphingosines and sphingolipids are also possible as fat-like substances.
Suitable pearlescent waxes are, for example, alkylene glycol esters, specifically ethylene gly-col distearate; fatty acid alkanolamides, specifically coconut fatty acid diethanolamide; partial glycerides, specifically stearic acid monoglyceride; esters of polybasic, optionally hydroxy-substituted carboxylic acids with C6-C22-fatty alcohols, specifically long-chain esters of tartaric acid; fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have at least 24 carbon atoms in total-specifically Lauron®; distearyl ether; fatty acids, such as stearic acid, C12-C22-hydroxy-fatty acids, behenic acid, ring-opening products of C12-C22-olefin epoxides with C12-C22-fatty alcohols and/or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
Super-oiling agents which can be used are substances such as, for example, lanolin and lecithin and polyethoxylated or acylated derivatives of lanolin and lecithin, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously serving as foam stabilizers.
So-called stabilizers which can be employed are metal salts of fatty acids, such as e.g., mag-nesium, aluminum and/or zinc stearate or ricinoleate.
Suitable cationic polymers which further optimize the sensory properties of the compositions according to the invention and impart to the skin a sensation of softness are, for example, cationic cellulose derivatives, such as e.g. a quaternized hydroxyethylcellulose which is obtainable from Amerchol under the name Polymer JR 4008, cationic starch, copolymers of di-allylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinylimidazole polymers, such as e.g. Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat®L/Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers, such as e.g. amodimethicone, copolymers of adipic acid and dimethylamino-hydroxypropyldiethylenetriamine (Cartaretine®/Sandoz), copolymers of acrylic acid with di-methyldiallylammonium chloride (Merquat® 550/Chemviron, polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives, such as, for example, quaternized chitosan, condensation products, optionally distributed in microcrystalline form, of dihaloalkyls, such as e.g. dibromobutane with bisdialkylamines, such as e.g. bis-dimethyl-amino-1,3-propane, cationic guar gum, such as e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.
Starch derivative can furthermore be employed to improve the skin sensation, e.g., Dry Flo® PC (INCI: Aluminum Starch Octenylsuccinate).
Suitable silicone compounds have already been mentioned with the oily substances. In addition to dimethylpolysiloxanes, methylphenylpolysiloxanes and cyclic silicones, amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which can be either liquid or resinous at room temperature, are also suitable. Sime-thicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and silicon dioxide or hydrogenated silicates, are furthermore suit-able.
So-called film-forming agents which lead to a further improvement in the sensory properties of the preparations according to the invention are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, collagen, hyaluronic acid and salts thereof and similar compounds, and the polyvinylpyrrolidones, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series and quaternized cellulose derivatives already mentioned under the viscosity regulators.
To improve the flow properties of the compositions according to the invention hydrotropic substances, such as, for example, ethanol, isopropyl alcohol, or polyols, can furthermore be employed. Polyols which are possible here have preferably 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or can be modified with nitrogen.
Dyestuffs which can be used are the substances which are suitable and approved for cosmetic purposes.
The presently claimed invention offers one or more of the following advantages:
In the following, there are provided a list of embodiments to further illustrate the present disclosure without intending to limit the disclosure to specific embodiments listed below.
While the presently claimed invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the presently claimed invention.
The presently claimed invention is illustrated in detail by non-restrictive working examples which follow. More particularly, the test methods specified hereinafter are part of the general disclosure of the application and are not restricted to the specific working examples.
The following materials are used in the Examples:
Euxyl® PE 9010 is Phenoxyethanol and Ethylhexylglycerin and is available from Ashland. Neo Heliopan® OS is Ethylhexyl Salicylate and is available from Symrise.
Average diameter or particle size: Particle size, as used herein, is synonymous with particle diameter and is determined, for example, by scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is synonymous with D50, meaning half of the population resides above this point, and the other half resides below this point. Particle size refers to primary particles. Particle size may be measured by laser light scattering techniques with dispersions or dry powders.
Average porosity and average pore diameter: Mercury porosimetry analysis can be used to characterize the porosity of the particles. Mercury porosimetry applies controlled pressure to a sample immersed in mercury. External pressure is applied for the mercury to penetrate into the voids/pores of the material. The amount of pressure required to intrude into the voids/pores is inversely proportional to the size of the voids/pores. A mercury porosimeter generates volume and pore size distributions from the pressure versus intrusion data generated by the instrument using the Washburn equation. Porosity, as reported herein for closed-cell metal oxide particles, is calculated as a ratio of unoccupied space and total particle volume. For example, porous silica particles containing voids/pores with an average size of 165 nm have an average porosity of 0.8.
Determination of the in vitro SPF of Formulation examples The determination of the in vitro SPF is performed by measuring the diffuse transmission in the UV-range using a Labsphere Ultraviolet Transmittance Analyzer 2000S. In order to simu-late the inhomogeneous surface structure of human skin, substrates with rough or porous surface are taken for such measurements. For this method Sandblasted 4-5 μm PMMA (PolyMethylMethacrylate) plates, from Helioscience (France), are used as substrate.
The sunburn protection factor (SPF) formalism was first introduced by Sayre in 1979 [1], by which an average of the inverse transmission (1/T) of the respective sunscreen in the spectral range between 290 and 400 nm is calculated, including weighting with the irradiance spectrum of a UV source, Ss (2), and the erythemal action spectrum, Ser (2):
Transparency/whitening method: Color measurements were performed with the prepared compositions applied on PMMA plates also used for in vitro SPF measurement. From the obtained L*a*b* parameters L* refers to the lightness of a sample. The difference of L* to a blank sample is expressed as delta L* and can be used to compare the transparency or whitening of the samples.
Preparation of closed-cell metal oxide particles
An aqueous dispersion of positively charged poly(meth)acrylate nanoparticle was diluted to 1 wt. % with deionized water and 3 wt. % of negatively charged silica nanoparticles was added. The mixture was sonicated for 30 seconds to prevent agglomeration. The aqueous nanoparticle dispersion and oil phase (a continuous oil phase containing 2 wt. % of polyethylene gly-col-co-perfluoro polyester surfactant in fluorinated oil) were each injected into a microfluidic device having a 50 μm droplet junction via syringe pumps. The system was allowed to equilibrate until monodispersed droplets were produced. The droplets were collected in a reservoir.
Collected droplets were dried in an oven at 50° C. for 4 hours. The dried powder was calcined by placing on a silicon wafer, heating from room temperature to 500° C. over a 4 hour period, holding at 500° C. for 2 hours, and cooling back to room temperature over a 4 hour period. The procedure resulted in monodispersed closed-cell silica particles having a diameter of 15 micrometers.
An aqueous suspension of positively charged spherical polymer nanoparticles (copolymer of methyl methacrylate and 2-(methacryloyloxy) ethyl] trimethylammonium chloride nanoparticles having an average diameter of 436 nm) and negatively charged silica nanoparticles (having an average diameter of 7 nm) was prepared. The polymer nanoparticles were present at 1.8 wt. % and the silica nanoparticles were present at 0.6 wt. % based on a weight of the aqueous suspension (a 3:1 weight to weight ratio of polymer nanoparticles to metal oxide nanoparticles). The aqueous suspension was spray dried under an inert atmosphere (nitrogen) at a 100° C. inlet temperature, a 40 mm spray gas pressure, a 100% aspirator rate, and a 30% flow rate (about 10 mL/min) using a BÜCHI lab-scale spray dryer.
The spray dried powder was removed from the spray dryer's collection chamber and spread onto a silicon wafer for sintering. The spray dried powder was then calcined in a muffle furnace with a batch sintering process to sinter and densify the silica nanoparticles and remove the polymer to produce the closed-cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 550° C. over a period of 5 hours, held at 550° C. for 2 hours, and then cooled back to room temperature over a period of 3 hours. The average closed-cell silica particles diameter was 3.2+1.4 μm.
The SEM images of a closed-cell silica particle produced as well as a cross-section of a closed-cell silica particle showed that the interior structure comprise an array of closed-cell silica shells that each encompass relatively monodisperse and ordered voids.
An aqueous suspension of negatively charged spherical polystyrene nanoparticles (having an average diameter of 197 nm) and positively charged titania nanoparticles (having an average diameter of 15 nm) was prepared. The polymer nanoparticles were present at 1.8 wt. % and the titania nanoparticles were present at 1.2 wt. % based on a weight of the aqueous suspension (a 3:2 weight to weight ratio of polymer nanoparticles to metal oxide nanoparticles). The aqueous suspension was spray dried under an inert atmosphere (nitrogen) at a 100° C. inlet temperature, a 55 mm spray gas pressure, a 100% aspirator rate, and a 30% flow rate (about 10 mL/min) using a BÜCHI lab-scale spray dryer.
The spray dried powder was removed from the spray dryer's collection chamber and spread onto a silicon wafer for sintering. The spray dried powder was then calcined in a muffle furnace with a batch sintering process to sinter and densify the titania nanoparticles and remove the polymer to produce the closed-cell titania particles. The heating parameters were as follows: the particles were heated from room temperature to 300° C. over a period of 4 hours, held at 300° C. for 6 hours, and then heated to 550° C. over a period of 2 hours, held at 550° C. for 2 hours, and cooled back to room temperature over a period of 4 hours. The average closed-cell titania particles diameter was 2.8+1.5 μm.
The SEM images of a closed-cell titania particle produced as well as a cross-section of a closed-cell titania particle showed that the interior structure comprises an array of closed-cell titania shells that each encompass relatively monodisperse voids.
An aqueous suspension of positively charged spherical polymer nanoparticles (copolymer of methyl methacrylate and 2-(methacryloyloxy) ethyl trimethylammonium chloride nanoparticles having an average diameter of 254 nm) and silica precursor tetramethyl orthosilicate (TMOS) was mixed in the pH range of 2-5. The polymer nanoparticles were present at 1.8 wt. % and the TMOS were present at 3.6 wt. % based on a weight of the aqueous suspension (a 1:3 weight to weight ratio of polymer nanoparticles to metal oxide). The aqueous suspension was spray dried under an inert atmosphere (nitrogen) at a 100° C. inlet temperature, a 40 mm spray gas pressure, a 100% aspirator rate, and a 30% flow rate (about 10 mL/min) using a BÜCHI lab-scale spray dryer.
The spray dried powder was removed from the spray dryer's collection chamber and spread onto a silicon wafer for sintering. The spray dried powder was then calcined in a muffle furnace with a batch sintering process to convert silica precursor to silica nanoparticles and densify the silica, and remove the polymer to produce closed-cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 200° C. over a period of 3 hours, held at 200° C. for 2 hours, and then heated to 550° C. over a period of 2 hours, held at 550° C. for 2 hours and cooled back to room temperature over a period of 3 hours. The average closed-cell silica particle diameter was 3.0+1.7 μm.
An aqueous suspension of two different sized (254 nm and 142 nm in diameter, respectively) positively charged spherical polymer nanoparticles (co-polymer of methyl methacrylate and 2-(methacryloyloxy) ethyl trimethylammonium chloride nanoparticles) and negatively charged silica nanoparticles (having an average diameter of 7 nm) was prepared. The polymer nanoparticles were present at 1.8 wt. % in total (0.9 wt. % of each) and the silica nanoparticles were present at 0.6 wt. % based on a weight of the aqueous suspension. The aqueous suspension was spray dried under an inert atmosphere (nitrogen) at a 100° C. inlet temperature, a 40 mm spray gas pressure, a 100% aspirator rate, and a 30% flow rate (about 10 mL/min) using a BÜCHI lab-scale spray dryer.
The spray dried powder was removed from the spray dryer's collection chamber and spread onto a silicon wafer for sintering. The spray dried powder was then calcined in a muffle furnace with a batch sintering process to convert silica precursor to silica nanoparticles and densify the silica, and remove the polymer to produce closed-cell silica particles. The heating parameters were as follows: the particles were heated from room temperature to 550° C. over a period of 6 hours, held at 550° C. for 2 hours, and then cooled back to room temperature over a period of 4 hours. The average closed-cell silica particle diameter was 2.1+1.2 μm.
The closed-cell silica particles (0.5 mg) were evenly distributed in a 20-mL clear glass vial having a 6 cm2 bottom surface. The sample exhibited an angle-independent blue color that was observable by the human eye.
Experiment 1: Sun protection factor (SPF) experiments
The UV-filter compositions according to Table 1 were prepared for the evaluation of SPF of the closed cell metal oxide particles.
Composition 1 was basic (placebo) composition which contained the following UV filters: Ethylhexyl Triazone, bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Diethylamino Hydroxybenzoyl Hexyl Benzoate and Ethylhexyl Salicylate. Suitable additives were also present in the composition.
Composition 2 was the composition of the presently claimed invention having 3.00 wt. % of closed-cell metal oxide particles prepared according to Example 2.
Composition 3 is a composition for comparative analysis having 3.00 wt. % of commercial SunSpheres™ polymer boosts for UV protection instead of the closed cell metal oxide particles.
Composition 4 was a composition for comparative analysis having 3.00 wt. % of commercial porous silica microspheres instead of the closed cell metal oxide particles.
The SPF values of these compositions was measured according to in vitro SPF method ISO24444 and the results are summarized in Table 2.
The composition 2 with 3 wt. % of closed cell metal oxide particles of Example 2 showed increased absorption over the whole UV range from 290 to 450 nm. The in vitro SPF of the composition could be increased by 27% with addition of 3 wt. % of closed-cell metal oxide particles according to example 2 as compared to the Placebo Composition 1. In contrast the in vitro SPF of composition 4 containing 3% porous metal oxide particles (silica, Sunsil-130) remained about the same as for the Placebo Composition 1.
It was evident from
The whitening effect was determined for the compositions 1, 2, and 3 prepared in experiment 2 by color measurement as described above. The results for formulations with UV-filters are summarized in
It was observed from
| Number | Date | Country | Kind |
|---|---|---|---|
| 22151984.6 | Jan 2022 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2023/050922 | 1/17/2023 | WO |
