权利要求：
1. A device for applying a cosmetic composition to an human integument or a synthetic human integument, comprising an application element having two or more surfaces having different surface properties, wherein at least one surface is a transfer surface adapted to hold a charge of said cosmetic composition and transfer it to said integument, and at least one surface is a repellent surface adapted to minimize interaction of said cosmetic composition with said repellent surface;
wherein said repellent surface is roughened and comprises a liquid and/or solid overlayer formed from adherence of a liquid to the roughened surface to form a liquid surface above the roughened surface such that the liquid is immobilized on the roughened surface without dewetting from the repellent surface;
wherein when said repellent surface comprises a solid overlayer, said solid overlayer is the solid formed from the liquid overlayer formed on said repellent surface (e.g., by applying heat to the liquid overlayer); and
the affinity of the roughened surface for the liquid and/or solid overlayer is greater than the affinity of the roughened surface for the cosmetic composition.
2. The device according to claim 1, wherein said roughened surface comprises features (e.g., protuberances and/or pits, etc.) having at least one dimension (e.g., width of protuberances and/or pits and/or height/depth, etc.) on the nanometer and/or micrometer scale.
3. The device according to claim 1, wherein said roughened surface is comprised of or composed of (or consists of) polymers (e.g., epoxy, polycarbonate, polyester, polypropylene, nylon, Teflon, thermoplastic polymer such as acrylonitrile butadiene styrene, etc.), metals (e.g., tungsten, aluminum, etc.), sapphire, glass (e.g., sapphire glass, etc.), carbon (e.g., diamond, graphite, black carbon, etc.), ceramics (e.g., alumina, silica, etc.), and combinations thereof.
4. The device according to claim 1, wherein the roughened surface is surface functionalized (e.g. functionalized with one or more functional groups independently selected from halogenated groups such as fluoro, fluoroalkyl, C1-C7 fluoroalkyl, C1-C7 perfluoroalkyl, trifluoromethyl, hydrocarbon groups including alkyl such as C1-C7 alkyl, and methyl, or combinations thereof, etc.).
5. The device according to claim 1, wherein the liquid which forms the liquid overlayer over the roughened surface comprises a perfluorocarbon oil, a partially fluorinated oil, a silicone liquid, a food-grade oil (e.g., a vegetable oil, olive oil, etc.), liquid hydrocarbon (e.g., a C5-C30 hydrocarbon such a paraffin oil, etc.), or combinations thereof.
6. The device according to claim 1, wherein the application element comprises a plurality of bristles, wherein the surface of at least one bristle of said plurality of bristles is at least partially composed of said repellent surface.
7. The device according to claim 1, wherein the transfer surface is flocked or partially flocked.
8. The device according to claim 1, wherein said composition is aqueous.
9. The device according to claim 1, wherein said cosmetic composition is non-aqueous (e.g., oil based such as silicone oil based, wax-based composition, etc.).
10. The device according to claim 1, wherein said transfer surface has a contact angle with water of less than 75° (e.g., less than 70°, less than 65°, less than 60°, etc.) and said repellent surface has a contact angle with water of greater than 80° (e.g., greater than 100°, greater than 110°, greater than 120°, etc.).
11. The device according to claim 10, wherein the difference in contact angles with water between the repellent surfaces and the transfer surface is greater than 10° (e.g., greater than 20°, greater than 30°, greater than 40°, greater than 50°, etc.).
12. The device according to claim 1, wherein said cosmetic composition is mascara, lip composition (e.g., lipstick, lip gloss, lip lacquer, lip balm, lip shimmer, etc.) eye composition (e.g., eyeliner, eyebrow composition, eye shadow, etc.) or nail composition (e.g., nail polish, nail care composition, etc.).
13. The device according to claim 1, wherein said device is a twisted wire brush, a molded applicator (e.g., brush), or a 3D printed applicator (e.g., brush).
14. The device according to claim 6, wherein the substantial majority (e.g., more than 70% or more than 80% or more than 90% by surface area, etc.) of the surface of at least one of said bristles is said repellent surface.
15. The device according to claim 6, wherein the surface area of the tip of said one or more of said plurality of bristles is composed of said repellent surface.
16. The device according to claim 1, wherein when said device comprises a handle and said distal end of the applicator element comprises one of said repellent surfaces such that when said application element is immersed in a reservoir containing said cosmetic composition and removed therefrom, the repellent surface prevents or reduces the formation of liquid communication between the application element and the reservoir following removal therefrom.
17. The device according to claim 1, wherein said device comprises a reservoir (e.g., in the handle and/or the stem, etc.) for holding a charge of said composition,
wherein said reservoir is in fluid communication with said transfer element such that said composition is transferred to said transfer element.
18. The device according to claim 1, wherein said device comprises a reservoir (e.g., in the handle and/or the stem, etc.) for holding a charge of said overcoat liquid,
wherein said reservoir is in fluid communication with said transfer element such that said composition is transferred to said repellent surface.
19. The device according to claim 1, wherein said human integument is skin, lip, eyebrow, eyelash, nail, or said synthetic human integument is a surface designed to mimic a keratinous surface (e.g., fake eyelash, fake nail, hair extension, etc.).
20. A kit comprising:
a) a device (e.g., the device according to claim 1) for application of a cosmetic composition to a human integument (e.g., keratinous surface, etc.),
b) a container comprising a reservoir charged with said cosmetic composition configured to receive said application portion such that said application portion is brought into contact with said cosmetic composition, and
c) a wiper for removing excess cosmetic composition from said device upon removal of said device from said container.
wherein the surface of said reservoir in fluid contact with said cosmetic composition and/or said wiper comprises one or more repellent surfaces.
发明内容：
[0006]In accordance with the foregoing objectives and others, the present invention provides applicators or tools for manipulating compositions on a surface and methods of using them. The applicators of the present invention are partially afforded such capability through the use of one or more repellent surfaces throughout the applicator. For example, these repellent surfaces may be on the application portion of the applicator in addition to the transfer elements capable of holding a charge of the cosmetic composition. It will be understood that cosmetic compositions include skin care compositions. The repellent surfaces are capable of repelling the cosmetic composition and preventing the product from being deposited thereon. Such repellent surfaces confer a complete range of functionalities such as prepping, grooming, dosing, transferring and detailing the human integument prior to, during, or after application of a cosmetic composition. Additionally, these repellent surfaces may prevent product from accumulating in undesirable locations of the applicator which cosmetic composition normally accumulates (e.g., the stem of the applicator, the wiper, the reservoir of cosmetic composition, etc.). The repellent surfaces may also ease the release of cosmetic composition onto the keratinous fiber.
[0007]Devices for manipulating (e.g., moving, styling, orienting, applying, etc.) a composition are provided comprising a repellent surface adapted to repel a composition or adapted to have reduced adhesion to the composition. In some embodiments, the composition is a flowable compositions (e.g., liquid, emulsion, gel, semi-solid, powder, etc.). In some embodiments, the applicator for a cosmetic composition may comprise an application portion capable of transferring cosmetic composition from the application portion to a human integument or a synthetic human integument such as a surface designed to mimic a keratinous surface (e.g., fake eyelash, fake nail, hair extension, etc.), wherein the application portion comprises one or more transfer surfaces capable of holding a charge of said cosmetic composition and wherein the applicator comprises one or more repellent surfaces capable of repelling the cosmetic composition. In other embodiments, more than 50% or more than 60% or more than 70% or more than 80% or more than 90% or more than 95% of the surface of the application portion and stem comprise repellent surfaces. It will be understood that the applicator is not limited for use with a specific composition (e.g., cosmetic composition, etc.). Rather, the recitation of compositions is illustrative of the characteristics of the repellent and transfer surfaces. In some embodiments, the repellent surfaces are on the application portion. In some embodiments, the composition is aqueous (e.g., an aqueous mascara or lip composition, etc.) and the one or more repellent surfaces are hydrophobic. In other embodiments, the composition comprises oil and the repellent surfaces are oleophobic. In some embodiments, the repellent surfaces are omniphobic. In certain embodiments, the applicator or tool is a medical brush.
[0008]In some embodiments, the applicator for applying a cosmetic composition to an integument (e.g., keratinous surface including hair, skin, nails, etc.) may comprise two or more surfaces having different surface properties, wherein at least one surface is a transfer surface adapted to hold a charge of said cosmetic composition and transfer it to said integument, and at least one surface is a repellent surface adapted to minimize interaction of said composition with said repellent surface. In certain embodiments, the composition is aqueous. For example, the composition may have a hydrophilicity such that when a dried film of the composition (e.g., mascara, etc.) is wetted, it may produce a contact angle with water of less than 100° or less than 90° or less than 80° or less than 70° or less than 60° or less than 50°. In other embodiments, the composition is non-aqueous. For example, the composition may be oily (e.g., the composition is immiscible with water, hydrophobic, lipophilic, etc.). In certain implementations, the transfer surfaces are hydrophilic and the repellant surfaces is hydrophobic. In some embodiments, the transfer surfaces are hydrophobic and the repellant surface are hydrophilic.
[0009]The applicator may be used for applying a cosmetic composition to a keratinous surface (e.g., skin, hair, nail, eyebrow, eyelash, hair of the head, hair of the scalp, etc.). In some embodiments, the method of applying a cosmetic composition to a keratinous surface may comprise charging a cosmetic composition onto an applicator comprising one or more repellent surfaces and applying the charged cosmetic composition onto the keratinous surface. The cosmetic composition may be transferred from the applicator to the keratinous surface with typical application means (e.g., rolling, brushing, stamping, combing, etc.). In some embodiments, the applicator or portion of the applicator may be used to align hairs prior to or during application of the cosmetic composition. Such aligning may be achieved through the use of an accessory, the surface of which is a repellent surface. In some embodiments, the aligning may be achieved through the use of transfer elements (e.g., bristles, fibers, etc.), wherein the tips of the transfer elements furthest from the stem comprise a repulsive surface. In some embodiments, a method of styling keratin fibers is provided comprising, in any order:
[0010](a) aligning keratin fibers; and
[0011](b) transferring cosmetic composition from an applicator to said keratin fibers;
wherein the aligning step and said transferring step are performed with the same applicator and a minimal or no amount of cosmetic composition is transferred between said keratinous fibers and applicator during said aligning step. As used herein, a “minimal” amount of cosmetic composition refers to a smaller amount of cosmetic composition that would be transferred between keratinous surface and applicator as compared to an otherwise identical applicator which does not comprise a repulsive surface. The keratin fibers may be aligned by, for example, combing, brushing, pulling, plucking, and combinations thereof.
[0012]Kits for applicators and cosmetic compositions are also provided comprising:
[0013]a) an applicator (or device),
[0014]b) a container comprising a reservoir capable of holding a charge of cosmetic composition and configured to receive the application portion of the applicator such that the application portion is brought into contact with the cosmetic composition, and
[0015]c) a wiper attached to the container for removing excess cosmetic composition from the applicator upon removal of said applicator from said container;
wherein the wiper and/or said container and/or said applicator comprises one or more repellent surfaces capable of repelling the cosmetic composition.
具体实施方式：
[0028]Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the invention that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the invention is intended to be illustrative, and not restrictive.
[0029]As used herein, “a” or “an” shall mean one or more. As used herein when used in conjunction with the word “comprising,” the words “a” or “an” mean one or more than one. As used herein “another” means at least a second or more.
[0030]The applicator may comprise two or more surfaces having different surface properties, wherein at least one surface is a transfer surface capable of holding a charge of said cosmetic composition and transferring said charged cosmetic composition to a keratinous surface, wherein at least one other surface is a repellent surface adapted to repel said cosmetic composition, and wherein said cosmetic composition is aqueous or non-aqueous (e.g., oil carriers such as silicone oil) based. The applicator may repel compositions comprising alcohol (e.g., ethanol), glycerols, wax, and/or polymers for example. In some embodiments, the composition may be wax-based or composed predominantly of wax (e.g., more than 50% wax by weight of the composition). In some embodiments, the non-aqueous composition may be oil-based, for example, and may be immiscible with water. Non-aqueous compositions will typically be hydrophobic.
[0031]In some embodiments, the applicator may be orient compositions without transferring the composition to a keratinous surface from the applicator (e.g., lash separators, medical brushes, etc.). In some embodiments, the applicator does not comprise a transfer surface capable of holding a charge of composition. In these embodiments, the substantial majority or the entire surface of the application portion and/or the stem may comprise one or more repellent surfaces. Such applicators may be, for example, cosmetic applicators, medical brushes, and the like. In some embodiments, the number of transfer elements (e.g., bristles, etc.) comprising only transfer surfaces to the number of transfer element comprising only repellent surfaces may be 5:1 to 1:5 (e.g., 2:1 to 1:2, 1:1, etc.).
[0032]Typically, the applicators comprise a handle, a stem, and an application portion. In some embodiments, the handle is not one of the portions with surface properties considered invention (i.e., the applicator and stem may be the only surfaces with either transfer or repellent surfaces). In some embodiments, the repellent surfaces are on the stem of the applicator which connects the application portion to a handle. In preferred embodiments, the handle, stem and application portion are oriented along the same major longitudinal axis of the applicator. In some embodiments the stem (or portions of the stem) and applicator are considered to be part of the applicator element. A cross-sectional view of an embodiment of the application portion is shown in FIG. 1. The cross-sectional view is perpendicular to the major longitudinal axis of the applicator. Application portion 10, comprises four transfer elements 12, 15, 18, and 21, each composed of a plurality of bristles extending from stem 11. In some embodiments, the one or more transfer elements are selected from bristles, fibers, projections, indentations, fins, tines, VELCRO® (e.g., hook and loop fasteners), teeth, grooves, sponge, foam, flocked surfaces, and combinations thereof. In some embodiments, the surface of said transfer element comprises said one or more repellent surfaces. In certain embodiments, the transfer elements comprise bristles or a plurality of bristles extending from the stem, wherein the surface of said bristle (e.g., the bristle tips, the entirety of the bristle, etc.) comprises one or more repellent surfaces. In preferred embodiments, the bristles may comprise a repellent surface located at the tip furthest from the stem. In most embodiments, the application portion comprises a major longitudinal axis extending toward the handle of the applicator. Referring to FIG. 1, the surface of transfer element 12 comprises two surfaces: repellent surface 14 capable of repelling cosmetic composition and transfer surface 13. Transfer surface 13 is capable of holding a charge of cosmetic composition and is capable of transferring the cosmetic composition to a keratinous surface (e.g., hair, skin, eyelashes, eyebrows, etc.). In the embodiment depicted, repellent surface 14 is disposed on transfer element 12 closest to stem 11. Transfer elements 15 and 18 have the repellent surface disposed furthest away from stem 11. The surface of transfer element 15 comprises a transfer surface 17 and repellent surface 16 and transfer element 18 comprises repellent surface 19 and transfer surface 20. The entire surface of transfer element 21 is a repellent surface 21 and transfer element 21 does not comprise a transfer surface capable of holding a charge of cosmetic. Such a configuration may offer a user multiple capabilities for aligning hair, applying cosmetic composition, and manipulating the cosmetic composition deposited on a keratinous surface. Each of these capabilities may be possessed with a single applicator. In preferred embodiments, the surface of the application portion is composed of repellent and transfer surfaces.
[0033]The repellent surfaces (e.g., the repellent surfaces of transfer elements, the repellent surfaces of the stem, etc.) may be produced by modifying the surface (e.g., by nano and/or micro etching, by printing a repellent pattern on a surface, by 3D printing the relevant portion of the applicator such that the 3D printed surface is repellent, by coating of polymers, particulates, etc.). In some embodiments, the repellent surfaces may arise from the characteristics of the material(s) from which the relevant portion of the applicator is composed. In some embodiments, the relevant portion of the applicator (e.g., the transfer element) are composed of repellent materials and a transfer surface is placed created thereon by surface modification.
[0034]The orientation of repellent surfaces on the transfer elements may afford the user a variety of different application properties. Cosmetic composition charged at the tips of the transfer element may be applied differently than cosmetic composition charged closer to the stem. Moreover, transfer elements 12, 15, and 18 each comprise a different ratio of repellent surface treatment to transfer surface capable of holding and transferring a charge of cosmetic composition. Upon insertion of the application portion into a reservoir comprising a cosmetic composition, only transfer surfaces 13, 17, and 20 become charged with cosmetic composition. By holding a different charge of cosmetic composition oriented in various geometries, transfer elements 12, 15, and 18 each transfer a different amount of cosmetic composition to a keratinous surface in each application in a different manner. For example, repellent surfaces located at bristle tips furthest away from the stem may help align the transfer elements during initial user application. Moreover, as the applicator is removed from the keratinous surface, the repellent surfaces at the tips prevent transfer of cosmetic composition back onto the applicator. Moreover, the plurality of bristles that make up transfer element 21 have an entirely repellent surface which may be used to spread cosmetic composition on a keratinous without becoming charged with the cosmetic composition. Transfer element 21 may be used, for example, to style and tune how hairs are separated and the coated product appears on the integument with cosmetic composition coated thereon.
[0035]The repellent surfaces may minimize the interaction of compositions with the repellent surface. For example, the repellent surface may reduce adhesion of the composition to the repellent surface, repel the composition from the repellent surface, or prevent or reduce absorption of the composition onto the surface. The repellent surfaces may minimize the interaction electrostatically, through surface tension, hydrophobic/oleophobic treatments, non-adhesive barriers (e.g., liquid overlayer, solid overlayer), or combinations thereof.
[0036]Conversely, the transfer surfaces are capable of holding a charge of cosmetic and transferring that charge to another surface (e.g., the surface of a human integument, etc.). In some embodiments, the transfer surface may be attractive surfaces to the composition (e.g., the electrostatic interactions, etc.). In some embodiments, the transfer surface may absorb the composition.
[0037]The repellent surfaces are constructed to repel a foreign material (typically the cosmetic composition), or to reduce the adhesion of the foreign material to the repellent surface. The construction of the repellent surface may be inspired by the self-cleaning abilities of many natural surfaces on animals, insects, and plants. It is believed that natural hydrophobic surfaces like the lotus leaf operate by providing roughness on a nano- or micro-meter scale. The hydrophobic protuberances reduce the effective contact area of the surface with water and thus prevent adhesion and spreading of water over the leaf. The repellent surfaces may be patterned in a similar manner. In some embodiments, the repellent surfaces have micro- or nano-meter scale roughness to repel liquids. In some embodiments, the micro- or nano-meter scale roughness may be etched into portions of the applicator producing the one or more repellent surfaces. The repellent surfaces may be patterned creating structure elements having dimensions in the range of 1 nm to 1 mm. Such patterned repellent surfaces and methods of producing them may be found, for example in US 2018/0120696, WO 01/74560, WO 2011/038741, or WO 2013/154582, each hereby incorporated by reference in their entirety.
[0038]Additionally, the repellent surfaces may be produced by the absorption or surface patterning of various components which confer the requisite roughness (e.g., micro- or nano-structure, etc.) of the repellent surface. In some embodiments, the repellent surface may comprise particles, polymers (e.g., coated polymers, electrochemically deposited polymers, etc.), be sand blasted, or micro or nano-etched. For example, the micro- or nano-scale structure of the repellent surfaces may come from hydrophobically modified metal oxides absorbed to the surfaces of the applicator. In some embodiments, the micro- or nano-scale structure may be produced by absorption of oleophobic or omniphobic (i.e., oleophobic and hydrophobic) particulates onto the surface of the applicator. Such particulates may be diatomaceous earth or surface modified diatomaceous earth as described in U.S. Pat. Nos. 8,216,674 and 8,497,021, each herein incorporated by reference. In some embodiments, the roughened surface is surface functionalized with one or more fluorinated groups. In some embodiments, the application element is composed of a repellent polymer with a transfer polymer coated thereon to produce the repellent and transfer surfaces. In other embodiments, the application element is composed of a transfer polymer with a repellent polymer coated thereon to produce the repellent and transfer surfaces.
[0039]The repellent surfaces may also be formed by forming a liquid overlayer attached to the surface, wherein the surface and the liquid of the liquid overlayer have an affinity for each other such that the liquid is substantially immobilized on the surface. In most embodiments with a liquid overlayer used to produce one or more repellent surfaces, the liquid overlayer has an affinity for the repellent surface greater than its affinity for the cosmetic composition. Accordingly, the liquid overlayer may prevent adherence of the foreign material (e.g., cosmetic composition) to the repellent surfaces of the product. The liquid of the liquid overlayer should be chemically inert to the cosmetic composition. Such may be produced as described in U.S. Pat. No. 9,353,646, hereby incorporated by reference in its entirety and particularly in reference to roughened surfaces and liquid overlayers.
[0040]Formation of the overlayer to form the repellent surfaces may occur by roughening one or more surfaces of an applicator (e.g., an applicator without hydrophilic and hydrophobic surfaces as described herein) having one or more functional groups attached thereto to form functionalized roughed surfaces. A liquid may be applied to the functionalized roughened surface, wherein the liquid has an appropriate affinity to the functionalized roughened surface in order to cover the functionalized surface with a thickness sufficient to form a liquid upper surface above one or more portions of the roughened surface. Typically, the functionalized roughened surface and the liquid have an affinity for each other such that, at atmospheric pressure, the liquid is substantially stably immobilized in, on, and/or over the functionalized surface, without dewetting from the substrate. Such affinity often forms the required repellent surface wherein cosmetic composition may adhere only to those surfaces not comprising the repellant surface (e.g., the liquid overlayer). For example, in some embodiments, the affinity of the roughened surface for the liquid which forms the overlayer is greater than the affinity of the roughened surface for the cosmetic composition. The roughened surface may have raised features having at least one dimension on the scale of nanometers to micrometers (e.g., from 10 nm to 100 μm). The roughened surface may comprise r features (e.g., protuberances and/or pits) having at least one dimension (e.g., width of protuberances and/or pits and/or height/depth) on the nanometer and/or micrometer scale.
[0041]Typically, the affinities between the roughened surface and the liquid is sufficient to form an overlayer over one or more portions of the roughened surface, which does not undergo dewetting. For example, the liquid overlayer may form such that once the liquid overlayer is formed, the liquid overlayer will not or has minimal retraction from the roughened surface. The liquid may comprise a perfluorocarbon oil, a partially fluorinated oil, a silicone liquid, a food-grade oil, liquid hydrocarbon. In some embodiments, the roughened surfaces may be functionalized with one or more functional groups independently selected from halogenated groups (e.g., fluoro, fluoroalkyl such as C1-C7 fluoroalkyl, C1-C7 perfluoroalkyl, trifluoromethyl), hydrocarbon groups (e.g., alkyl such as C1-C7 alkyl including methyl and ethyl), or combinations thereof.
[0042]In some embodiments, the formation of the liquid overlayer may comprising application of the liquid onto the roughened surface followed by one or more curing steps by which heat is applied (e.g., by placing in an oven) to the liquid overlayer. In some embodiments, the liquid overlayer is converted into a solid overlayer (e.g., through one or more curing steps).
[0043]In some embodiments, the substrate of the roughened surface comprises a porous material having a plurality of pores. These pores may be interconnected with each other in, for example three directions. Such interconnectivity may maximize the formation of the liquid overlayer.
[0044]The roughened surface may be a hierarchical surface containing surface features on multiple length scales. For example, the roughened surface may have a first topological feature having dimensions on the microscale and a second smaller topological feature having dimensions on the nanoscale. In such embodiments, the first topological feature may support the second topological feature. Typically, the smallest feature sizes of the roughened surface may include structures such as nanofibers, nanodots, bumps, rods, spheres, posts or mushrooms. In certain embodiments, the smallest feature may have dimensions that nanometers in size such as less than 200 nm or less than 100 nm or less than 50 nm or less than 10 nm or less than 5 nm or from 5 nm to 200 nm. For example, in some embodiments, the roughened surface comprises nanofibers having a diameter less than 200 nm or less than 100 nm or less than 50 nm or less than 10 nm or less than 5 nm or from 5 nm to 200 nm. The roughened surface may further comprise these nanoscale features incorporated onto larger structures such as those having feature sizes that are larger than 100 nm or larger than 150 nm or larger than 300 nm or larger than 500 nm or larger than 1000 nm or from 150 nm to 1000 nm or from 300 nm to 1000 nm or from 500 nm to 1000 nm. Furthermore, these nanoscale and microscale structures may also be incorporated onto an even larger set of structures (i.e., to form at least a three-tiered hierarchical structure). Such hierarchies may be described in PCT/US2011/044553 which is hereby incorporated by reference in its entirety and particularly in relation to hierarchical structures and concomitant wetting.
[0045]The roughened surface pattern may dictate the resultant thickness of the liquid overlayer. For example, the liquid overlayer may have a thickness of greater than 0.5 μm or greater than 1 μm or greater than 5 μm, each of which may be the height of one or more features of roughened surface, such as the hierarchical features and/or nanostructured posts.
[0046]In some embodiments, the roughened surface may comprise a periodic array of surface protrusions (e.g., posts, peaks, etc.) or any random patterns or roughness. In certain implementations, the size scale of the features producing a roughened surface ranges from 10 nm to 100 μm with geometries. These raised structures may be constant along their heights. In some embodiments, the raised structures have cross sections of circles, ellipses, or polygons (e.g., triangles, squares, pentagons, hexagons, octagons, etc.). The raised structures may be produced by, for example, conventional photolithography, projection lithography, e-beam writing or lithography, focused-ion beam lithography, deposition of nanowire arrays, grown nanostructures on the surface of the substrate, soft lithography, replica molding, solution deposition, solution polymerization, electropolymerization, electroplating, electroless deposition, vapor deposition, contact printing, etching, transfer patterning, microimprinting, or self-assembly. In some embodiments, the protrustions are substantially uniformly distributed over the roughened surfaces. In some embodiments, the protrusions are arranged in predetermined patterns over the roughened surfaces.
[0047]The roughened surface may be manufactured from materials suitable to produce the affinities to product the liquid overlayer and/or the required structures to form the overlayer. For example, the roughened surface may comprise polymers (e.g., epoxy, polycarbonate, polyester, nylon, Teflon, etc.), metals (e.g., tungsten, aluminum), sapphire, glass carbon (e.g., diamond, graphite, black carbon, etc.), ceramics (e.g., alumina, silica, etc.), and combinations thereof. For example, fluoropolymers such as polytetrafluoroethylene (PTFE), polyvinylfluoride, polyvinylidene fluoride, fluorinated ethylene propylene, or combinations thereof may be utilized to form one or more portions of the surface.
[0048]In certain embodiments, the liquid which forms over the liquid overlayers may form a substantially flat (e.g., molecularly flat, atomically flat, etc) surface when provided over the roughened surface. The flatness of the liquid overlayer may be determined by average height fluctuations as measured by AFM and be less than 1000 nm or less than 100 nm or less than 10 nm or less than 1 nm. Some flatness measurements are described in Xu et al., J Am Chem Soc 127 (2005): 854-855; Matsunaga et al., J Am Chem Soc 133 (2011): 5545-5553, each hereby incorporated by reference in their entirety and particularly in relation to surface roughness measurements. In certain implementations the liquid which forms the liquid overlayer may comprise perfluorinated hydrocarbons, organosilicone compounds such as silicone elastomers and polydimethylsiloxane (PDMS), or combinations thereof. In various implementations, liquid which forms the liquid overlayer may comprise perfluoroalkylamines (e.g., tertiary perfluoroalkylamines such as perfluorotri-n-pentylamine FC-70, perfluorotri-n-butylamine FC-40), perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers (e.g., FC-77), perfluoropolyethers (e.g., KRYTOX type lubricants), perfluoroalkylphosphines, perfluoroalkylphsphineoxides, or combinations thereof. In several implementations the liquid to form the liquid overlayer may comprise one or more perfluorohydrocarbons and one or more perfluoroalkylamines (e.g., tertiary perfluoroalkylamines such as perfluorotri-n-pentylamine FC-70, perfluorotri-n-butylamine FC-40), perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers (e.g., FC-77), perfluoropolyethers (e.g., KRYTOX type lubricants), perfluoroalkylphosphines, perfluoroalkylphsphineoxides, or combinations thereof. In several implementations, the liquid may comprise fluorinated or perfluorinated carboxylic acids (e.g., long chain fluorinated carboxylic acids such C10-C24 fluorinated carboxylic acids, C10-C24 perfluorinated carboxylic acids, perflurooctadecanoic acid), fluorinated phosphonic acids, fluorinated sulfonic acids, fluorinated silanes, or combinations thereof. The hydrocarbon group (e.g., the perfluoroalkyl group) for these liquid compounds may be linear or branched. In some embodiments one or more (e.g., all) of the linear or branched groups may be independently partially fluorinated or full fluorinated.
[0049]The overcoat liquid may be a hydrophobic liquid such as a hydrophobic hydrocarbon (e.g., fluorocarbons and perfluorocarbons, etc.), silicone fluid, or combinations thereof. In certain implementations the liquid for the overcoat, or “overcoat liquid” may comprise more than 50% or more than 60% or more than 70% or more than 80% or more than 90% fluorinated fluids such as perfluorinated hydrocarbons such as perfluoroalkylamines (e.g., tertiary perfluoroalkylamines such as perfluorotri-n-pentylamine FC-70, perfluorotri-n-butylamine FC-40), perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers (e.g., FC-77), perfluoropolyethers (e.g., KRYTOX type lubricants), or combinations thereof by weight of the overcoat liquid. In some embodiments, the liquid is volatile. In some embodiments, the liquid is non-volatile (e.g., has a vapor pressure of less than 760 mm Hg at STP. In certain aspects, the roughened surface may be composed of polydimethylsiloxane, polypropylene, polytetrafluoroethylene, or combinations thereof. In certain implementations, more than 30% or more than 40% or more than 50% or more than 60% or more than 70% or more than 80% or more than 90% or more than 95% or more than 99% of the surface area of the roughened is polydimethylsiloxane, polypropylene, polytetrafluoroethylene, or combinations thereof.
[0050]The overcoat may cover the entire roughened surface. In some embodiments, the overcoat may cover more than 10% or more than 20% or more than 30% or more than 40% or more than 50% or more than 60% or more than 70% or more than 80% or more than 90% or more than 95% or more than 99% of the surface area roughened surface.
[0051]The liquid which forms the liquid overlayer may have a density higher than the cosmetic compositions. For example, the liquid for the overlayer may have a density more than 1.0 g/cm3 or more than 1.6 g/cm3 or more than 1.9 g/cm3. Higher density may enhance repellency of the cosmetic composition. In various implementations, the high-density fluids may reduce the tendency of the cosmetic composition to move below the surface of the liquid overlayer and/or become entrapped therein.
[0052]The overlayer may be formed by placing the liquid onto the roughened surface for example by dipping the roughed surface into a reservoir carrying (e.g., such as a reservoir in the kit). In come embodiments, the liquid may be delivered to the roughened surface from within the applicator such as with an internal reservoir comprising the overlayer liquid in fluid communication with the roughened surface. In some embodiments, the device may comprise a reservoir (e.g., in the handle and/or the stem, etc.) for holding a charge of said overcoat liquid, wherein the reservoir is in fluid communication with said application element such that said composition is transferred to said repellent surface. In several implementations, the device may comprise a reservoir (e.g., in the handle and/or the stem, etc.), for holding a charge of the composition (e.g., cosmetic composition such as mascara or lip composition etc.) wherein the reservoir is in fluid communication with the transfer element such that the composition is transferred to the transfer element.
[0053]The liquid for the overlayer, or overlayer liquid, may be refreshed as needed when it has become depleted and/or used before every basis. In some embodiments, the device (or kit) will contain a liquid reservoir of the liquid overcoating for replenishing said liquid overlayer. In one embodiment, the device contains a first reservoir and a second reservoir, wherein said first reservoir contains said liquid for the liquid overcoat and said second reservoir contains a charge for said cosmetic composition (e.g. mascara composition such as an aqueous mascara composition comprising pigments, hydrophilic mascara composition optionally comprising pigments, etc.). The applicator may be inserted into said first and second reservoirs. Methods of applying the cosmetic composition are also provided, comprising inserting the applicator into the reservoir containing the overcoat liquid to form a liquid overcoat, removal from the overcoat reservoir and insertion into the reservoir containing the cosmetic composition. In some embodiments, the method comprises application of the cosmetic composition to a human integument (e.g., keratinous surface).
[0054]In some embodiments, the device (or kits for use with the device) may comprise a container having a reservoir therein, an opening for receiving an applicator element (e.g., an applicator element comprising one or more repellent surfaces such as those described herein, etc.), wherein the device (or kit) comprises a wiper such that the applicator element can be immersed or otherwise brought into contact with and a wiper element (e.g., when the applicator element is removed from the container). When the applicator element is brought in contact with the wiper, at least a portion of the composition (e.g., cosmetic composition, liquid composition, liquid cosmetic composition, mascara etc.) is wiped from the surface of said applicator element. In some embodiments, at least a portion of the wiper is a repellent surface. The repellent surface located on the wiper element may cause the wiper element to be resistant to clogging or formation of a dried residue of a cosmetic composition thereon.
[0055]In some embodiments, the device for manipulating (e.g., applying to a human integument, removing from a surface) a composition (e.g., cosmetic composition to a human integument, a biological composition such as blood) may comprise an application element having two or more surfaces having different surface properties, wherein at least one surface is a transfer surface adapted to hold a charge of said cosmetic composition and transfer it (e.g. to the integument), and at least one surface is a repellent surface adapted to minimize interaction of the composition with the repellent surface;[0056]wherein the repellent surface is roughened and comprises a liquid and/or solid overlayer formed from adherence of a liquid to the roughened surface to form a liquid surface above the roughened surface such that the liquid is immobilized in, on and over the roughened surface without dewetting from the repellent surface;[0057]wherein when said repellent surface comprises a solid overlayer, said solid overlayer is the solid formed from the liquid overlayer formed on said repellent surface (e.g., by applying heat to the liquid overlayer); and[0058]the affinity of the roughened surface for the liquid and/or solid of the overlayer is greater than the affinity of the roughened surface for the composition (e.g., cosmetic composition). In several implementations, the transfer surface does not comprise a liquid and/or solid overlayer.
[0059]In some embodiments, the one or more repellent surfaces are non-contiguous (i.e., each of the repellent surface are not adjacent or in contact with one another). In some embodiments, two or more portions of the repellent surface on the application portion are non-contiguous. In some embodiments, the repellent surface is a single contiguous surface. In some embodiments, two or more repellent surfaces are contiguous, but composed of different repellent surfaces (e.g., one repellent surface may comprise a liquid overlayer and may be adjacent to another repellent surface comprising micro etching or hydrophobic particulates).
[0060]The repellent and transfer surfaces may have different contact angles with water. The contact angle may be used to characterize the repellent or transfer nature of the surface. Typically, a higher contact angle with water may correlate with a higher repellent nature of a surface with water. For example, in some embodiments, the transfer surface may have a contact angle with water of less than 70° and the repellent surface may have a contact angle with water of greater than 70°. In some embodiments, the repellent surface may have a contact angle with water of greater than 70° or greater than 80° or greater than 90° or greater than 100° or greater than 110° or greater than 120°. In some embodiments, the contact angle of the repellent surface is at least 75° or at least 100° or at least 120°. The device may comprise one or more transfer surfaces having a contact angle with water of less than 75° (e.g., less than 70°, less than 65°, less than 60° , etc.) and one or more repellent surfaces having a contact angle with water of greater than 80° (e.g., greater than 100°, greater than 110°, greater than 120°, etc.). In some embodiments, the difference in contact angles with water between the repellent surfaces and the transfer surface is greater than 10° (e.g., greater than 20°, greater than 30°, greater than 40°, greater than 50°, etc.).
[0061]The contact angle may be measured by with water using a contact angle goniometer or other like method known in the art.
[0062]The repellent surface and the cosmetic composition should be chosen together such that repellent surface is able to repel or reduce the adhesion of the cosmetic composition to the repellent surface. In some embodiments, the applicator is configured for application of the cosmetic composition to keratin fibers (e.g., eye lashes, eyebrows, hair of the scalp, nails, etc.). In some embodiments, the cosmetic composition to be used with the cosmetic applicator may be, for example, mascara, eyeshadow, hair dye, lip gloss, nail polish, or a product used to provide nail art/effects (e.g., a stamp, etc.). In some embodiments, the composition (e.g., aqueous composition) may be a clear or pigmented composition. In some embodiments, the cosmetic composition may be a lip composition (e.g., lipstick, lip gloss, lip lacquer, lip balm, lip shimmer, etc.) eye composition (e.g., eyeliner, eyebrow composition, eye shadow, etc.) or nail composition (e.g., nail polish, nail care composition, etc.
[0063]Referring now to FIG. 2, a perspective view of an application portion 25 of an embodiment of the applicator is shown. Application portion 25 comprises four transfer elements 26, 29, 32, and 35 each composed of a plurality of bristles. The surfaces of the transfer elements have repellent surfaces 28, 31, 33, and 35 and transfer surfaces 27, 30, and 34. The entire surface of transfer element 35 is a repellent surface capable of transferring a charge to a keratinous surface. In some embodiments, the entire surface of a transfer element may be a transfer surface capable of holding of a charge of a composition and transferring the charge to another surface. Application portion 25 also comprises an accessory 36 in the shape of a comb. In other embodiments, the accessory may be in the form of a brush sleeve. In some embod