Cosmetic products, method of production and use thereof
Patent Information
- Application Number
- PCT/ES2024/070653
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-10-25
- Filing Date
- 2024-10-24
- Publication Date
- 2025-07-10
AI Technical Summary
Conventional cosmetic creams face challenges in combining bioactive ingredients to achieve stable, effective, and safe compositions, including compatibility, emulsification, stability, texture, and bioactivity, while also addressing skin penetration, absorption, and regulatory compliance.
The development of cosmetic products in the form of sheets or films made from ultrafine fibers using electro-hydrodynamic or aero-hydrodynamic processing techniques, which allow for the encapsulation of bioactive agents and improved skin absorption, while eliminating the need for water, oils, and preservatives.
These products provide enhanced bioactive delivery and absorption, improved skin compatibility, and increased sustainability by reducing weight, volume, and packaging complexity, while ensuring low water activity to prevent microbiological contamination.
Abstract
Description
[0001] DESCRIPTION
[0002] Cosmetic products, their preparation procedure and use
[0003] TECHNICAL SECTOR
[0004] The present invention falls within the area of polymeric materials based on ultra-fine fibers applied to the cosmetic sector, referring to its process and application for manufacturing solid products of high cosmetic efficiency in film format (layer or sheet) manufactured using electro-hydrodynamic, aero-hydrodynamic processing techniques or any combination of both.
[0005] BACKGROUND OF THE INVENTION
[0006] Cosmetic ingredients, also known as bioactive compounds, are compounds that include biomolecules, enzymes, liposomes, anti-inflammatory agents, probiotics, prebiotics, symbiotics, antioxidants, cell regenerators, anti-wrinkle agents, anti-shine agents, etc.
[0007] Conventional cream formulations face challenges when combining various ingredients to achieve a stable, effective, and safe composition. These challenges include ingredient compatibility, proper emulsification, preservation, stability, texture, appearance, bioactivity of active ingredients, skin penetration and absorption, allergens and irritation, and regulatory compliance. The use of solid creams in the form of micron- or submicron-sized fibers can overcome several of these problems.
[0008] The formation of ultrafine fibers prepared by electro-hydrodynamic or aero-hydrodynamic processing, e.g., electrospinning, also known as electro-spinning, allows the design of products for, for example, the immediate and deep absorption of cosmetic bioactives through the skin or to absorb skin oil more efficiently. In the electrospinning technique, the effect of voltage on the solution causes the solvent to evaporate rapidly, causing the fibers to form immediately and act as a cosmetic ingredient per se and / or efficiently trap the cosmetic ingredient in the fibers. In the latter case, the result is optimal encapsulation of the cosmetic ingredient within the fiber structure, as well as a reduction in the ability of its molecules to crystallize, thus maintaining an amorphous or quasi-morphous state, which facilitates its dissolution, diffusion, and adsorption.The micro / nano structure of these materials provides a higher surface area / volume ratio and improved mechanical properties compared to other techniques for generating, for example, cosmetic films that disappear into the skin. Furthermore, it allows for the preparation of cosmetic formulations in a solid state, without water or oils, and potentially without any preservatives or other stabilizing or emulsifying additives. By generating solid creams, the water activity is also ensured to be very low, thus eliminating the need for time-consuming testing to ensure the absence of microbiological contamination. These techniques increase the sustainability of the cosmetic product by reducing weight and volume and also simplifying packaging.However, not all biopolymers can be processed using these techniques, or they do not provide the required or desired characteristics in the cosmetic product in terms of cosmeticity, texture, appearance, bioactivity, skin penetration and absorption, skin adhesion, allergens and irritation, etc.
[0009] The present invention aims to solve the difficulties encountered in the state of the art by proposing cosmetic products with advantageous compositions that allow their optimal manufacturing or processing by means of electro-hydrodynamic or aero-hydrodynamic techniques and present the optimal properties or characteristics required for their use as cosmetics, such as those mentioned in the previous paragraph.
[0010] DESCRIPTION OF THE INVENTION
[0011] The present invention proposes a cosmetic product in the form of a sheet (e.g., in film, patch, or mask format), configured for application to the skin. This product may be formed by a single layer (monolayer) or form a multilayer system, capable of releasing bioactive agents beneficial to the skin or absorbing oil or grease from the skin. The cosmetic product is manufactured primarily using electrohydrodynamic or aerohydrodynamic processing techniques, or any combination thereof. The products may be manufactured monoaxial, coaxial, by co-deposition, or layer-by-layer, and may optionally contain one or more cosmetic or bioactive ingredients encapsulated therein. Each layer is composed of micrometric and / or submicrometric fibers.The bioactive agent, if present, is encapsulated using solutions, dispersions, or emulsions of the polymers and bioactives, which will form a solid product made of ultrafine fibers that facilitate the homogeneous and controlled release of the bioactives onto the skin instantly.
[0012] In general, the products of the invention are composed of at least one layer of hydrophilic or hydrophobic polymer fibers, which may be supported by a support layer also based on electrospun fibers, or a woven material, a non-woven woven material (also called TNT or non-woven), or by a continuous film, which may be transparent, colored or opaque, as well as a perforated film (Figure 1).
[0013] A first aspect of the present invention relates to a self-adhesive and highly soluble cosmetic product on the skin based on essentially hydrophilic polymers, which can optionally contain and release bioactive agents on the skin, said product comprising or consisting of: a layer of polymeric fibers (A), wherein said layer optionally comprises at least one encapsulated bioactive agent, the fibers having an average diameter size between 50 nm and 5 pm, more preferably between 100 nm and 3 pm, and even more preferably between 200 nm and 1 pm, measured by scanning electron microscopy (SEM); the layer of fibers has a surface density of at least 0.01 g / m 2 , more preferably between 0.1 and 300 g / m 2 , and even more preferably between 0.1 and 50 g / m 2and where the polymeric fibers are formed from polymer blends selected from the list consisting of: pullulan / elastin; pullulan / polyethylene glycol (PEG), pullulan / elastin / collagen and polyethylene oxide (PEO) / polyethylene glycol.
[0014] The characteristics and specific composition of this cosmetic product allow its rapid adherence and dissolution on moistened skin, providing an inherent cosmetic firming, soothing / anti-irritation, anti-wrinkle and moisturizing effect, which can be reinforced or complemented by encapsulated bioactive agents that are released onto the skin to collectively and optimally generate an enhanced anti-wrinkle, firming, soothing / anti-irritation, antibacterial, cleansing, nourishing, decongestant, antioxidant, depigmenting, regenerating, rejuvenating / anti-aging, moisturizing, emollient, illuminating, sebum-regulating, etc. effect. Furthermore, being made of very fine fibers, the high surface area / volume ratio of these fibers generates a homogeneous application on the skin, copying its topology and thus facilitating its application, the immediate release of the bioactive agents, improving their adsorption into the skin and, therefore, their effectiveness.
[0015] "Fiber" refers to elongated elements in which their length is greater than their width (diameter).
[0016] In a preferred embodiment, the polymeric fibers are made up of a Pullulan / Elastin mixture where the percentage by weight of elastin in the polymeric composition is between 3 and 8%, more preferably between 3 and 5% and even more preferably, 3%, the remainder would correspond to pullulan (up to 100% by weight of the polymeric mixture).
[0017] In a preferred embodiment, the polymeric fibers are made up of a Pullulan / PEG mixture where the percentage by weight of PEG in the polymeric composition is between 10 and 30%, more preferably between 20 and 30% and even more preferably, 25%, the remainder would correspond to the pullulan (up to 100% by weight of the polymeric mixture).
[0018] In a preferred embodiment, the polymeric fibers are made up of a Pullulan / Elastin / Collagen mixture where the percentage by weight of elastin in the polymeric composition is between 3 and 8%, that of collagen is between 10 and 50%; more preferably the percentage of elastin in the polymeric composition is between 3 and 5% and that of collagen is between 20 and 40% and even more preferably, the percentage of collagen is 43.3% and that of elastin is 3.3% the remainder would correspond to pullulan (up to adding up to 100% by weight of the polymeric mixture).
[0019] In a preferred embodiment, the polymeric fibers are made up of a PEO / PEG mixture where the percentage by weight of PEG in the polymeric composition is between 10 and 30%, more preferably, between 20 and 30%, even more preferably, 20%, the remainder would correspond to PEO (up to 100% by weight of the polymeric mixture).
[0020] Preferably, in any of the aforementioned embodiments, the elastin is of plant origin (plant elastin), more preferably, the elastin is hydrolyzed wheat protein. Preferably, in any of the aforementioned embodiments, the collagen is of non-animal origin, such as microbial collagen with or without genetic modification.
[0021] Preferably, in any of the aforementioned embodiments, the PEG is PEG 400.
[0022] Another aspect of the invention relates to a kit comprising the hydrophilic polymer-based cosmetic product described above and a water-based spray container (also known as a mist) with or without other cosmetic, balsamic, and / or odorizing products. The spray device allows the skin to be moistened before or after application of the cosmetic product so that it adheres to the skin easily and dissolves on its surface.
[0023] Another aspect of the invention also relates to a cosmetic product, similar to that described above in the first aspect of the invention, but based on hydrophobic polymers. In this case, the cosmetic product would not be soluble in the skin and would be used to remove grease or oil from the skin, preferably facial grease. Therefore, the present invention also relates to a cosmetic product for absorbing oil or grease from the skin, also called anti-shine, comprising or consisting of: a layer of polymeric fibers (B), where: said layer comprises an encapsulated bioactive agent, this bioactive agent being a grease or oil-absorbing material (also called an anti-shine agent) where the polymeric fibers are formed by polymers selected from the list consisting of: polyhydroxyalkanoates (PHA), such as PHB, PHV, medium-length chain polyhydroxyalkanoates (mcl-PHA),and all possible copolymers such as PHBV among others, polylactic acid (PLA) and all its copolymers such as PGLA, poly-e-caprolactone (PCL) and all its copolymers such as PEG-PCL and PCLA, polyesters such as polybutylene succinate (PBS), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and all possible copolymers of these such as poly(butylene adipate-co-terephthalate) (PBAT), polybutylene adipate succinate (PBAS), Poly(Butylene Adipate-co-Terephthalate) (PBAT), as well as any mixture of the above; or the polymeric fibers are made up of mixtures of polymers selected from the list consisting of: PHA / PBS, PHA / PCL, PHA / PBAT or PHA / PBSA, in this case the presence of a bioactive agent being optional, which is a fat-absorbent material and where the polymeric fibers have an average diameter size between 50 nm and 5 pm, more preferably between 100 nm and 3 pm and,even more preferably, between 200 nm and 1 pm, as measured by scanning electron microscopy (SEM); the fiber layer has a surface density of at least 0.01 g / m, 2 , more preferably between 0.1 and 500 g / m 2 , and even more preferably between 0.1 and 100 g / m 2 .
[0024] In an even more preferred embodiment, the polymer that makes up the polymeric fibers of layer (B) is selected from a mixture of PHA / PBS, PHA / PCL, PHA / PBAT or PHA / PBSA, where the PHA content in the mixture is at least 30% by weight with respect to said mixture, so that the non-PHA polymer content is less than 70% by weight in the mixture. These mixtures, given the characteristics of their composition, provide a more flexible and efficient cosmetic product by better absorbing fat or oil from the skin.
[0025] In an even more preferred embodiment, the polymer that makes up the polymeric fibers of layer (B) is selected from a mixture of PHA / PBS, PHA / PCL, PHA / PBAT or PHA / PBSA, where the content of the polymer that is not PHA is less than 70% by weight in the mixture and also comprises a bioactive agent that is a fat or oil absorbent material.
[0026] In a preferred embodiment, the grease-absorbent material, which may or may not have organomodifications to make the surface of the bioactive agent more compatible with the polymeric fibers and thus improve its dispersion and distribution in the fibers, is selected from: carbonaceous compounds such as activated carbon, carbon black, graphite, graphene, carbon fibers or tubes; silica, such as mesoporous silica, clays and nanoclays such as bentonites, kaolinites, vermiculites, laponites, sepiolite, or other porous minerals such as zeolites and other oil absorbers such as volcanic rock, as well as any combinations thereof. More preferably, the grease or oil-absorbent material is selected from carbonaceous materials, mesoporous silica, nanoclays or any mixture thereof. Even more preferably, the grease or oil-absorbent material is activated carbon.
[0027] The grease or oil absorbent material preferably has a micrometric or submicrometric particle size, i.e. nanometric, that is, at least one of its dimensions (on average) is less than 1000 nm, as measured by TEM (transmission electron microscopy) or SEM.
[0028] In a preferred embodiment, the content of grease- or oil-absorbent material in the layer of polymeric fibers is less than 25% by weight relative to the total weight of the layer, even more preferably less than 10%, and most preferably less than 3%. Preferably, the content of the material in the layer is at least 0.001% by weight.
[0029] In a preferred embodiment, the polymeric fiber layer (B) comprises the compound CTAB (hexadecyltr-methylammonium bromide) in an amount between 0.01 and 3% by weight relative to the total weight of the polymeric fiber layer. This compound is optionally added during the process for preparing the polymeric fiber layer as a surfactant and improves the effectiveness of the final product by promoting the dispersion and distribution of the bioactive ingredient in the fibers and contributing to the absorption of fat or oil from the skin.
[0030] In the present invention, when referring to the “product of the invention”, it includes both the product essentially based on hydrophilic polymers that serve in themselves to provide a cosmetic effect and that also optionally allow the release of bioactive agents for their absorption more effectively into the skin, as well as the one based on hydrophobic polymers, which serve in themselves to eliminate grease or oil from the skin and that also optionally carry anti-shine additives to reinforce the effect of eliminating grease or oil from the skin, unless one of the products in particular is specified.
[0031] In a preferred embodiment, the product of the invention comprises a support or substrate layer (S) on which the layer of polymeric fibers (A or B) is located, forming multilayer structures of the AS or BS type. This support layer (S) is formed by at least one layer of woven fibers, or non-woven fabrics (TNT) or a continuous film of one or more hydrophilic and / or hydrophobic polymers. This substrate layer (S) must have a surface density of at least 0.1 g / m 2 ; more preferably between 1 and 10,000 g / m 2 ; and even more preferably between 1 and 500 g / m 2 .
[0032] In a preferred embodiment, the support layer (S) comprises or consists of a continuous polysaccharide-based film, preferably the substrates comprise or consist of starch or cellulose such as cellulose acetate; or woven or nonwoven fabrics made of PCL or comprising or consisting of cellulose, or any combination thereof.
[0033] In the present invention, the areal density, typically expressed in g / m 2 For each layer, the density is calculated by weighing a sample with known dimensions. This weight is then divided by the sample's surface area. This process is performed on at least five samples from each layer to obtain an average surface density value for the entire layer.
[0034] In the present invention, the term "encapsulation" refers to the highly dispersed and distributed incorporation of the bioactive both inside the polymer fibers that make up each of the layers of the product that contain it, either forming a separate core-shell phase, or constituting a physical mixture with the polymeric material of the fiber, including what are known as solid solutions or dispersions; the bioactive can therefore be found both inside and on the surface of said fibers, or even in the interstitial spaces between them.
[0035] In a preferred embodiment, the self-adhesive cosmetic product, highly soluble and optionally allowing the release of bioactive agents on the skin, essentially based on hydrophilic polymers, additionally comprises another layer of polymeric fibers (A'), forming a structure of layers A-A' or A-A'-S, in case both are on a substrate (S). In this layer of polymeric fibers (A'), the fibers have an average diameter size between 50 nm and 5 pm, more preferably between 100 nm and 3 pm, and even more preferably between 200 nm and 1 pm, measured by scanning electron microscopy (SEM); it has a surface density of at least 0.01 g / m 2 , more preferably between 0.1 and 300 g / m 2 , and even more preferably between 0.1 and 50 g / m 2and the polymeric fibers are composed of polymer blends selected from the list consisting of: pullulan / elastin; pullulan / polyethylene glycol (PEG), pullulan / elastin / collagen, polyethylene oxide (PEO) / polyethylene glycol, or pullulan alone. The presence of bioactive agents in layer A' is also optional and may contain the same or different bioactive agents as layer A.
[0036] In a preferred embodiment, the cosmetic product based on hydrophobic polymers for removing grease or oil from the skin additionally comprises another layer of polymeric fibers (B'), forming a structure of layers B-B' or B-B'-S, if both are on a substrate (S). In this layer of polymeric fibers (B'), the fibers have an average diameter size between 50 nm and 5 pm, more preferably between 100 nm and 3 pm, and even more preferably between 200 nm and 1 pm, measured by scanning electron microscopy (SEM); the layer has a surface density of at least 0.01 g / m 2 , more preferably between 0.1 and 500 g / m 2 , and even more preferably between 0.1 and 100 g / m 2and polymeric fibers are made up of mixtures of polymers selected from the list consisting of; polyhydroxyalkanoates (PHA), such as PHB, PHV, medium chain length polyhydroxyalkanoates (mcl-PHA), and all possible copolymers thereof such as PHBV among others, polylactic acid (PLA) and all its copolymers such as PGLA, poly-β-caprolactone (PCL) and all its copolymers such as PEG-PCL and PCLA, polyesters obtained or not from natural precursors such as polybutylene succinate (PBS), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and all possible copolymers thereof such as poly(butylene adipate-co-terephthalate) (PBAT), polybutylene adipate succinate (PBAS), Poly(Butylene Adipate-co-Terephthalate) (PBAT), as well as any mixture of the above. The presence of bioactive agents in layer B' is optional and may carry the same or different bioactive agents as layer B.
[0037] In a preferred embodiment, the product of the invention consists of a layer of polymeric fibers (layer A or B) that will come into contact with the skin and a substrate layer (layer (S)). They will be multi-layer structures: AS or BS
[0038] In another preferred embodiment, the product of the invention consists of a layer of polymeric fibers (layer A or B) that will come into contact with the skin, a second layer of polymeric fibers (A' or B' respectively) and a substrate layer (S) on which the previous layers are located. They will be multilayer structures: A-A'-S or B-B'-S. In the present invention, the term "bioactive" refers, without limitation, to any natural or synthetic substance that is beneficial to the skin, and more preferably for use in cosmetics.
[0039] The bioactive agents that can be used in the products of the present invention are selected, without limitation, from any cosmetic bioactive that fulfills any of the following functions or combination of functions:
[0040] • Anti-wrinkle: such as peptides, botox-like bioactives (for example and in a limited sense, botulinum toxin type A, spilanthes acmella also known as biobotox, dermatorelaxants such as some polypeptides (th, tetra, penta, octapeptides), marine derivatives such as DMAE (dimethylaminoethanol), Tsubaki oil, Acetyl Hexapeptide-8, the famous Argireline (Acetyl Hexapeptide-3), or the improved version of the latter, known as SNAP-8), wakame seaweed extract, bakuchiol, etc.
[0041] • Firming: such as dimethylaminoethanol (DMAE), niacinamide (vitamin B3), collagen, elastin, etc.
[0042] • Soothing / Anti-irritation: such as Vitamin B12, cannabidiol (CBD), aloe vera extract, ceramides, etc.
[0043] • Antibacterials: such as azelaic acid, salicylic acid, melic acid, tea tree oil, etc.
[0044] • Cleanser: such as surfactants, betaine, coco glycosides, saponins, etc.
[0045] • Nutritious: such as kahté butter, almond oil, argan oil, vitamin E, etc.
[0046] • Decongestant: such as caffeine, guarana extract, ginseng extract, ginger extract, etc.
[0047] • Antioxidants: such as carotenoids, isoflavones, vitamin C, phytosterols, etc.
[0048] • Depigmentants: such as glycolic acid, kojic acid, hydroxytyrosol, arbutin, etc.
[0049] • Regenerators: such as centella asiatica, epidermal growth factors, retinol, retinal, etc.
[0050] • Rejuvenating or anti-aging: such as coenzyme Q10, jojoba oil, royal jelly, rosehip extract, etc.
[0051] • Moisturizer: such as hyaluronic acid, mucopolysaccharides, squalane, provitamin B, etc. • Emollient: such as oat extract, coconut oil, cucumber extract, sesame oil, etc.
[0052] • Illuminator: such as vitamin C, ferulic acid, lactic acid, mandelic acid, etc.
[0053] • Anti-brittleness: such as activated carbon, silica, clays such as bentonites, volcanic rock, etc.
[0054] • Sebum regulator: azeloglycine, silicon, witch hazel extract, benzoyl peroxide, etc.
[0055] • Flavorings: essential oils of Lemon, Tea Tree, Lavender, Mint, Rosemary, etc.
[0056] In another preferred embodiment, the bioactives used are of synthetic, natural, biotechnological origin, such as, for example, fermentation and / or recombinant, or any mixture of these.
[0057] In the present invention, the term "polymer" refers to macromolecular materials both in their pure ex-reactor state and as additives and post-processed in commercial formulas typically used by the chemical industry, more commonly known as plastic grades. Process additives, biodegradability promoters or those that confer stability, or other types of filler-type additives, may additionally be added to any of the polymers or plastic grades, either in micro, submicro or nanometric form to improve their physicochemical properties or their controlled perfume retention and release capacity. Such additives may be of the chemical, fiber, sheet or particle type.
[0058] In another preferred embodiment, any of the layers of the product of the invention may contain aromatic substances or aroma enhancers.
[0059] The product of the invention may also contain some type of pigment or logo-type print, either multicolor or monochrome, as a differentiating element on the sides of the product. In this case, the inks or pigments used are non-toxic, biocompatible, with good organoleptic properties, and do not affect the integrity of the product or the encapsulated bioactive. Any type of print or stamping may be used as long as it does not affect the integrity of the product's materials or the encapsulated bioactive. It may also have some type of texture. Furthermore, the product of the invention may have any size and shape or flat pattern, produced by any conventional cutting method, whether manual, using a die-cutting system, or laser cutting.
[0060] As for the manufacture of the fibers that make up the layers of the product of the invention, it is preferably carried out by any of the known electro-hydrodynamic and aero-hydrodynamic techniques for obtaining fibers, more preferably by electro-drawing (electrospinning), direct beam printing by electro-hydrodynamic processing (electrohydrodynamic direct writing), electro-drawing from the melt (melt electrospinning), solution blow spinning, or a combination and / or vahant thereof. However, any other method for obtaining fibers may also be used, such as centrifugal jet spinning or a combination of this and the aforementioned methods.Electrohydrodynamic and aerohydrodynamic techniques are based on the formation of polymeric micro or submicrofibers at room temperature or below, from a polymeric solution to which an electric field or gas pressure is applied. The fact that it is used in solution form makes it highly versatile, allowing various substances to be incorporated into the solution itself. At the same time, the fact that it can be processed at room temperature avoids certain problems such as bioactive degradation.
[0061] In a preferred embodiment, the product of the invention is manufactured using the electrospinning technique. In an even more preferred embodiment, it is carried out by electrospinning using multi-outlet or multi-emitter injectors, whether needle-type or similar, or made of porous materials. The advantage of these injectors over so-called free-surface injectors that do not have a controlled outlet, also known as needleless electrospinning or free-surface electrospinning, is greater control over the dispersion of fiber diameters and also homogeneity along the thickness. Control of fiber diameter dispersion facilitates reproducibility in release kinetics and therefore cosmetic certification.
[0062] In a preferred embodiment, the variation in fiber diameter is less than 35%, i.e., the variation in fiber diameter is less than ±17.5% of the mean value. This value is measured by scanning electron microscopy (SEM). In another preferred embodiment, the variation in fiber diameter for a given system with a multi-outlet injector is at least 15% less than that which would occur with uncontrolled outlet injectors.
[0063] In another preferred embodiment, the variation in fiber diameter for a given system with a multi-outlet injector is at least 5% less than that which would occur with uncontrolled outlet injectors.
[0064] Using these techniques and the aforementioned polymers, the present invention encapsulates the bioactive(s) in such a way that their release can also be sustained. To achieve this encapsulation, techniques are used, including, but not limited to: core-shell technology, co-deposition, surface modification electrospinning, side-by-side electrospinning to generate Janus-type structures, direct mixing, emulsion techniques, particle pre-encapsulation, layer-by-layer deposition, etc.
[0065] In the present invention, core-shell technology is used in the case of electrospinning and solution blow spinning, making use of a concentric nozzle through which the bioactive and / or nutraceutical is supplied in solution through the inner tube with or without polymers or simply polymers, while the encapsulating agent, in this case the polymer selected to prepare the corresponding layer, is passed through the outer tube. The use of nozzles with more than two concentric tubes (triaxial or similar) can give rise to more combinations of bioactive and polymer. In any case, this technology gives rise to tubular fibers inside which the bioactive and / or nutraceutical is housed. In this case, using non-water-soluble polymers, the molecules of the bioactive and / or nutraceutical diffuse through the wall of the fibers or through their internal porosity, thus controlling the release process.
[0066] In the present invention, co-deposition consists of a deposition process in which two injectors simultaneously deposit, for example, on one side, the polymer solution with the bioactive and, on the other, another polymer solution in which the bioactive is not soluble. This technique is used to control release. It is also used to deposit two solutions containing a different bioactive, or that have different types of polymers, thus generating different sizes and morphologies of fibers within the same membrane, and therefore a different release profile of the bioactive(s). Co-deposition can therefore be carried out with the bioactive(s) and fibers of the encapsulant, with particles and / or fibers and / or a mixture of both. Furthermore, simultaneous electrospinning allows the combination of various properties within the same membrane.
[0067] In the present invention, the direct mixing can be, without limitation, the encapsulant and the encapsulating agent, or a suspension of particles containing the pre-encapsulated bioactive and the encapsulating agent, by means of monoaxial electrospinning, resulting in cylindrical fibers in which the bioactive agent is embedded and dispersed within the fiber. This mixture can be a homogeneous solution or a heterogeneous suspension.
[0068] In the present invention, emulsion techniques refer to any emulsion, without limitation, of solvents or components, which result in encapsulation with various phases and are processed by processes known as electrohydrodynamic or aerohydrodynamic emulsion processing. An emulsion is a dispersion of a liquid (dispersed phase) in the form of tiny droplets within another liquid (continuous phase) with which it is generally not miscible. Emulsions can be direct, inverse, or multiple. Direct emulsions are those in which the dispersed phase is a lipophilic substance and the continuous phase is hydrophilic. These emulsions are usually referred to as L / H or O / W. Inverse emulsions, on the other hand, are those in which the dispersed phase is a hydrophilic substance and the continuous phase is lipophilic. These emulsions are usually abbreviated as H / L or W / O. They can also be O / O emulsions, with two immiscible organic phases.Multiple emulsions are those that, for example, contain an inverse emulsion as the dispersed phase and an aqueous liquid as the continuous phase. Multiple emulsions can be H / L / H or W / O / W or O / W / O. Emulsions can also be formulated using so-called Pickering emulsions, which use particles to separate and stabilize the phases, and any other type of emulsion technology. In this way, the bioactive is encapsulated within the fibers in the organic phase, and the release also occurs in a controlled manner.
[0069] In the present invention, pre-encapsulation in particles consists of obtaining charged fibers, or mixed in the case of co-deposition, with micro or nanoparticles in which the bioactive has been previously encapsulated. For this purpose, any encapsulation process that produces particles is used, such as, but not limited to, electrospray, air-assisted electrospray (EAPG), coacervation, emulsion-evaporation / emulsion-extraction, hot melt, interfacial polycondensation, complexation, gelation, fluid bed, atomization, lyophilization, extrusion, electrostatic proplet generation, superentic fluids, TFIOMS, etc., and mixtures thereof. These particles with bioactive and / or nutraceutical are typically added, in the case of direct mixing, to a solution of the selected polymer, such that, after any of the aforementioned processes, fibers with particles inside are obtained.In this case, the controlled release of the bioactive is carried out both by degradation of the particles and fibers, and by diffusion through the particles and fibers, or even the case may be that both release mechanisms occur simultaneously.
[0070] In the present invention, the layer-by-layer deposition method consists of using a system in which the layers are deposited sequentially within the same process. Thus, initially, one of the layers is electrospun until the desired thickness is reached, and then the second layer is electrospun on top of the first, obtaining an in situ multilayer system.
[0071] Therefore, another aspect of the invention relates to a process for obtaining any of the products of the invention (whether based on hydrophilic polymers or based on hydrophobic polymers), where said process is based on the electrospinning technique (i.e., electrospinning) comprising: preparation of a layer of fibers (A or B) from a solution, suspension or emulsion of the polymer or mixture of polymers that will form the fibers where the polymer or mixture of polymers is at a concentration of between 0.1 and 60% by weight; the voltage of the emitter used is between 0.01 and 500 kV and a voltage at the collector of between 0 kV and -500 kV, with a flow rate of between 0.0001 to 50,000 ml / h, at a temperature of between 1 ° C and 100 ° C, preferably between 20 and 40 ° C, even more preferably at 40 ° C; and a relative humidity preferably between 10 and 30%, and even more preferably 15%.
[0072] Optionally, one or more bioactive agents are added to the solution, suspension or emulsion of the polymer or polymer mixture. Preferably, the bioactive agent or agents are present at a total concentration of between 0.01 and 70% by weight in said solution, suspension or emulsion. Preferably, a solution of the polymer or polymer mixture is prepared, for which a solvent is chosen in which the polymers are soluble at the temperature at which the process is carried out. In the case of preparing mixtures of hydrophilic polymers (as is the case of the self-adhesive and highly soluble product with a cosmetic effect on the skin), the preferred solvents are water and alcohols, such as methane, ethanol, isopropanol, butanol and trifluoroethanol, or any mixture thereof; more preferably, the solvent used is water.In the case of hydrophobic polymers (as is the case of the cosmetic product for the absorption of oil or fat from the skin), the preferred solvents are alcohols and organic solvents, and more preferably they are chloroform, DMF (dimethylformamide), HFIP (hexafluoropropanol), ethanol, methanol, butanol, acetone, trifluoroethanol or any mixture of the above.
[0073] When the polymer that makes up the fibers is not chemically compatible with the bioactive to be encapsulated (there is no physical-chemical interaction between them) or the bioactive has low or very low solubility in the polymer solvent or solvents necessary to carry out the electrospinning process, then any known emulsion route can be used to encapsulate the bioactive(s), instead of the direct dissolution or suspension of the bioactive components. The solvents are preferably water, alcohols (such as methane, ethanol, isopropanol, butanol and trifluoroethanol, or any mixture thereof), organic solvents (such as chloroform, DMF (dimethylformamide), acetone or any combination thereof).
[0074] In a preferred embodiment, the layer of polymeric fibers (A or B) are prepared on a substrate layer (S), the substrate being as defined above.
[0075] In another preferred embodiment, a second layer of polymeric fibers (A' or B') is prepared on the first layer of fibers (A or B, respectively) or on a substrate (S), where said layer (A' or B') is also prepared by electrospinning from a solution, suspension or emulsion of the polymer or mixture of polymers that will form the fibers where the polymer or mixture of polymers is at a concentration between 0.1 and 60% by weight; the voltage of the emitter used is between 0.01 and 500 kV and a voltage at the collector between 0 kV and -500 kV, with a flow rate of between 0.0001 to 50,000 ml / h, at a temperature of between 1 ° C and 100 ° C, preferably between 20 and 40 ° C, even more preferably at 40 ° C; and a relative humidity preferably between 10 and 30%, and even more preferably 12% and where the bioactive agent or agents are optionally added to the solution, suspension or emulsion at a total concentration between 0.01 and 70% by weight.
[0076] A final aspect of the invention relates to the cosmetic use of the cosmetic product of the present invention based on essentially hydrophilic polymers to produce an inherently beneficial cosmetic effect on the skin, as well as for the controlled release of one or more bioactive agents in the skin, if the product comprises bioactive agents, or for the absorption of oil or fat from the skin, if the product is based on essentially hydrophobic polymers.
[0077] The term "inherently beneficial cosmetic effect" implies that the cosmetic product itself, based on essentially hydrophilic polymers, even without the presence of bioactive agents, is capable of producing a beneficial cosmetic effect on the skin. The "beneficial cosmetic effect" refers to a firming, soothing, anti-irritation, anti-wrinkle, and moisturizing effect.
[0078] Throughout the description and claims, the word "comprise" and its variants are not intended to exclude other technical features, additives, components, or steps. For those skilled in the art, other objects, advantages, and features of the invention will be apparent in part from the description and in part from the practice of the invention. The following examples and figures are provided for illustrative purposes only and are not intended to limit the scope of the present invention.
[0079] BRIEF DESCRIPTION OF THE FIGURES
[0080] Fig. 1. Example of configurations of the product of the invention based on hydrophilic polymers according to monolayer or multilayer systems.
[0081] Fig. 2. Product of Example 1
[0082] Fig. 3. Product of Example 3
[0083] Fig. 4. Graphs showing caffeine absorption through a synthetic membrane (Strat-M) simulating human skin versus the absorption of the same amount of caffeine from a cream simulant with the same composition (left); and caffeine absorption through human skin from the caffeine patch (right) described in Example 9.
[0084] Fig. 5 Product of Example 7, where it can be seen that the patch absorbs oil. EXAMPLES
[0085] The invention will now be illustrated by some examples provided by the inventors, which demonstrate the effectiveness of the product of the invention.
[0086] The polymers used in the examples for the preparation of the cosmetic products have been acquired commercially, as indicated below: Pullulan: CAS No.: 9057-02-7; PEG400: CAS No. 25322-68-3; Hydrolyzed wheat protein (Vegetable elastin) CAS No.: 222400-28-4 or 70084-87-6; Collagen of recombinant origin CAS No.: 9007-34-5; PEO: CAS No.: 25322-68-3.
[0087] Example 1: Bilayer product format with Antioxidant effect (Figure 2), using the Pullulan / PEG formula, in which the support layer is a continuous film of starch.
[0088] Hydrophilic fibers with encapsulated bioactive were deposited on the starch film (100 µm thick) placed on a rotating collector (200 rpm). This manufacturing process was carried out at a temperature of 40 ° C and a relative humidity of 15%. To do this, a solution of 11.2% by weight (wt.) of pullulan, 3.75% of polyethylene glycol (PEG400) and 0.076% of hydroxytyrosol commercially known as Olivan Antiox, in deionized water was used. In this polymer solution, the polymer:bioactive ratio was 99.5:0.5. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 25 kV was used, as well as a collector voltage of -25 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density was 5 g / m 2This product was cut into a specific shape for application to the cheek or forehead, as shown in Figure 2. In this type of patch, the layer containing the bioactive substance solubilises in partially moist skin.
[0089] Example 2: Two-layer product format with a firming effect, with the Pullulan / elastin formula in which the support layer is a cellulose acetate film.
[0090] Hydrophilic fibers with encapsulated bioactive were deposited on a cellulose acetate film (25 µm thick), placed on a rotating collector (200 rpm). This manufacturing was carried out at a temperature of 30 ° C and a relative humidity of 20%. For this, a solution of Pullulan at 14.55% by weight (wt.%), 0.45% hydrolyzed wheat protein (vegetable elastin), 0.625% Resveratrol and Biotin Liposomes (Caarrivec 7), and 0.048% Palmitoyl pentapeptide-4 and colloidal gold commercially called Matrigold, in deionized water, was used. In this polymer solution, the polymer:bioactive ratio was 95.7:4.3. Once both components were dissolved, the fiber mat was manufactured using the electrospinning technique in a five-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 35 kV was used, as well as a collector voltage of -25 kV. A flow rate of 5 ml / h was also employed.The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density was 5 g / m. 2 In this type of patch, the layer containing the bioactive is solubilized in partially moist skin.
[0091] Example 3: Three-layer product format with a humectant effect, using the pullulan / PEG formula, in which the support layer is a cellulose nonwoven fabric. (Figure 3)
[0092] On a 80 g / m cellulose nonwoven fabric 2 The hydrophilic fibers with encapsulated bioactive were deposited on a rotating collector (200 rpm). This production was carried out at a temperature of 30°C and a relative humidity of 20%.
[0093] In this case, a first layer was deposited starting from a solution of Pullulan at 11.25% by weight (wt.%), 3.75% polyethylene glycol (PEG400) and 0.474% Liposomes with a wetting effect Matrigoldy lubricant (Carrivec 1), and 0.316% Niacinamide and a mixture of Vitamins commercially called Beauplex VH-DSM NP, in deionized water. In this polymer solution, the polymer:bioactive ratio was 95:5. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. An emitter voltage of 30 kV was used to produce the fiber mesh, as well as a collector voltage of -25 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density is 5 g / m 2 .
[0094] Another layer of fibers was deposited on top of the previous layer, starting from a solution of 11.25% by weight (wt.) pullulan, 3.75% polyethylene glycol (PEG400) in deionized water. In this polymer solution, the ratio between the polymers is 75:25. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 25 kV was used, as well as a collector voltage of -25 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm) on top of the previous layer. In this case, the surface density is 1 g / m 2 .
[0095] This product was cut into a specific shape for application to dark circles (skin under the eyes) in Figure 3. In this type of patch, the water-soluble layers solubilize in partially moist skin.
[0096] Example 4: Three-layer product format with Vitamin C, using the Pullulan / PEG formula, in which the support layer is a cellulose acetate film
[0097] The hydrophilic fibers with encapsulated bioactive were deposited on a cellulose acetate film (25 µm thick) placed on a rotating collector (200 rpm). This production was carried out at a temperature of 30°C and a relative humidity of 20%.
[0098] In this case, a first layer was deposited starting from a solution of Pullulan at 11.2% by weight (wt.%), 3.75% polyethylene glycol (PEG400) and 0.625% Resveratrol and Biotin Liposomes (Caarrivec 7), and 0.08% gold microparticles with vitamin C commercially called Golden C in deionized water. In this polymer solution the polymer:bioactive ratio was 95.5:4.5. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mesh, an emitter voltage of 35 kV was used, as well as a collector voltage of -25 kV. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density is 5 g / m 2
[0099] Another layer of fibers was deposited on top of the previous layer, starting from a solution of 11.2% by weight (wt.) pullulan, 3.75% polyethylene glycol (PEG400) in deionized water. In this polymer solution, the ratio between the polymers is 75:25. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 25 kV was used, as well as a collector voltage of -25 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density is 1 g / m 2 In this type of patch, the water-soluble layers are solubilized in partially moist skin.
[0100] Example 5: Three-layer product format with Collagen and Hyaluronic Acid, using the Pullulan / elastin / collagen formula, in which the support layer is a starch film
[0101] The hydrophilic fibers with encapsulated bioactives were deposited on a starch film (100 µm thick) placed on a rotating collector (200 rpm). This production process was carried out at a temperature of 40°C and a relative humidity of 15%.
[0102] In this case, a first layer was deposited, starting from a solution of 8% pullulan, 0.5% hydrolyzed wheat protein (vegetable elastin), and 6.5% recombinant collagen by weight (wt.%) in deionized water. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 35 kV was used, as well as a collector voltage of -30 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density is 5 g / m 2
[0103] Another layer of fibers was deposited on top of the previous layer, starting from a solution of 14.4% pullulan and 0.8% hyaluronic acid by weight (wt.%), in a 90:10 mixture of deionized water / isopropanol. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mesh, an emitter voltage of 25 kV was used, as well as a collector voltage of -20 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density is 5 g / m 2 In this type of patch, the electrospun water-soluble layers solubilize in partially moist skin.
[0104] Example 6: Bilayer product format with Caffeine, using the Pullulan / PEG formula and in which the support layer is a layer of electrospun PCL fibers.
[0105] This product used a layer of electrospun fibers as the outer or support layer. To achieve this, a solution of 12% by weight of poly-e-caprolactone (PCL) in 79% by weight of chloroform and 9% methanol was prepared. To produce this layer, an emitter voltage of 23 kV and a collector voltage of -1 kV were used, and a flow rate of 10 ml / h was also used through a multi-outlet linear injector. This last layer must have a surface density between 12 g / m 2 Since its primary function is to protect and support the product, the hydrophilic fibers described below were placed on top of this layer.
[0106] A layer of fibers was deposited on the previous layer starting from a solution of Pullulan at 9% by weight (wt.%), 2.25% PEG400, 2.3% Caffeine, and 1.2% Oleic Acid, in Water / lysopropanol in a ratio of 92:8. In this polymer solution the polymer:Caffeine ratio was 80:20. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 25 kV was used, as well as a collector voltage of - 15 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the surface density is 20 g / m 2 . Processed at 30°C and 20% relative humidity.
[0107] Once manufactured, the layers are bonded together using a calendering technique at a speed of 2.56 rpm, heating only the roller in contact with the outer layer (PCL) to 40°C. This ensures adhesion between the layers and coalesces the fibers, reducing the porosity of the outer PCL layer. In this type of patch, the layer with the bioactive material solubilises in partially moist skin.
[0108] Example 7: Hydrophobic monolayer product format with anti-glare properties.
[0109] To manufacture this product, a solution of 5% by weight of Poly-e-caprolactone (PCL), 5% by weight of Ethyl cellulose as an additive, and 0.3% of activated carbon in Chloroform / Methanol in a 90:10 weight ratio was used. An emitter voltage of 23 kV and a collector voltage of -10 kV were used for production, and a flow rate of 10 ml / h was also used, through a multi-outlet linear injector. This last layer had a surface density of 12 g / m 2
[0110] This layer does not dissolve in the skin's moisture; its sole function is to absorb oil, thus eliminating the shine caused by excess oil. Figure 5 shows the oil-absorbing capacity of this patch as an example.
[0111] Example 8: Bilayer product format with Caffeine using the Pullulan / PEG formula and Hyaluronic Acid (HA) using the Pullulan formula produced by monoaxial co-electrospinning and the support layer is a starch film.
[0112] On a starch film (100 µm thick) placed in a roll-to-roll system, the substrate is allowed to pass under both injectors continuously, i.e., pullulan / HA and pullulan / PEG / caffeine are deposited simultaneously. This production was carried out at a temperature of 30°C and a relative humidity of 20%, using Fluidnatek LE-500 equipment from Bioinicia SL.
[0113] In this case, two different solutions were deposited simultaneously. For this purpose, a solution of 9% by weight (wt.%) Pullulan, 2.25% PEG400, 2.3% Caffeine, and 1.2% Oleic Acid, in Water / lysopropanol in a 92:8 ratio, was used. In this polymer solution, the polymer:Caffeine ratio was 80:20. Simultaneously, a solution of 14.4% by weight (wt.%) Pullulan and 0.8% Hyaluronic Acid was used. Both solutions were deposited simultaneously, achieving a combination of Pullulan / HA and Pullulan / PEG / Caffeine fibers in a layer with a surface density of 10 g / m 2 In this type of patch, the layer containing the bioactive is solubilized in partially moist skin.
[0114] Example 9: Bilayer product format using the PEO / PEG formula and containing Caffeine in which the support layer is a layer of electrospun PCL fibers.
[0115] As in previous examples, a layer of electrospun fibers was used as the outer or support layer for this product. To achieve this, a solution of 12% by weight of Poly-E-caprolactone (PCL) in 79% by weight of chloroform and 9% methanol was prepared. To produce this layer, an emitter voltage of 23 kV and a collector voltage of -1 kV were used, and a flow rate of 10 ml / h was also employed through a multi-outlet linear injector. This last layer had a surface density of 12 g / m 2 Since its primary function is to protect and support the product, the hydrophilic fibers described below were placed on top of this layer.
[0116] A layer of fibers was deposited on the previous layer starting from a solution of 9% by weight (wt.%) PEO, 2.25% PEG400, 3.2% Caffeine, and 1.6% Oleic Acid, in Chloroform / Methanol in an 80:20 ratio. In this polymer solution, the polymer:Caffeine ratio was 80:20. Once both components were dissolved, the fiber sheet was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. An emitter voltage of 20 kV was used to produce the fiber mat, as well as a collector voltage of -5 kV. A flow rate of 10 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm). In this case, the areal density is 73 g / m 2 . Processed at 30°C and 20% relative humidity.
[0117] As in Example 6, the different layers are bonded together using the calendering technique at a speed of 2.56 rpm, heating only the roller in contact with the outer layer (PCL) to 40°C. This ensures adhesion between layers, and coalesces the fibers, reducing the porosity of the outer PCL layer.
[0118] In this type of patch, the layer with the bioactive is solubilized in partially moist skin.
[0119] This patch was evaluated using a caffeine permeation study using a Franz cell system. 1 cm patches were used. 2, on a synthetic membrane (Strat-M) and on human skin. Where a pH buffer: 7.4 at 37 ° C under stirring was used in the receptor compartment. Each experiment was performed in triplicate. Figure 4 shows the caffeine permeation graphs in a synthetic membrane (Strat-M), both in patch format (square) and in a cream simulant with the same composition as the patch (triangle), where it can be seen that when it is in patch format, the caffeine permeation is greater than in liquid. On the other hand, the caffeine permeation graph in the skin is also shown, which justifies that the patch proposed in this patent facilitates the permeation of bioactives, such as caffeine in this case. Example 10: Bilayer product format with an antioxidant effect, manufactured with core-shell fibers using the Pullulan formulas and the Pullulan / elastin / collagen formula, using a non-woven cellulose fabric as a support layer.
[0120] On a 80 g / m cellulose non-woven fabric 2 The hydrophilic fibers with encapsulated bioactive were deposited on a rotating collector (200 rpm). This production was carried out at a temperature of 30°C and a relative humidity of 20%.
[0121] In this case, the fiber layer was deposited using a device consisting of coaxial nozzles. A 12% by weight (%wt) pullulan solution in deionized water was injected through the outer nozzle (Shell). A 8% solution of pullulan, 0.5% hydrolyzed wheat protein (vegetable elastin), and 6.5% by weight of recombinant collagen in deionized water was injected through the inner nozzle (Core). This results in the formation of tubular pullulan fibers in such a way that the collagen is encapsulated within them. For this production, an emitter voltage of 20 kV and a collector voltage of -10 kV were used, and a flow rate of 10 ml / h. In this case, the surface density is 10 g / m 2 In this type of patch, the layer containing the bioactive is solubilized in partially moist skin.
[0122] Example 11: Three-layer product format, with collagen and eucalyptus aroma, where the interlayer of fibers is produced by emulsion-electrospining based on the Pullulan formula and the support layer is a non-woven fabric (Non-woven) made of cellulose.
[0123] On a 80 g / m² cellulose non-woven fabric 2 The hydrophilic fibers with encapsulated bioactive were deposited on a rotating collector (200 rpm). This production was carried out at a temperature of 30°C and a relative humidity of 20%.
[0124] In this case, a first layer was deposited, starting from a 13% by weight solution of pullulan in water, and eucalyptus essential oil with 3% Span20 surfactant was added little by little to obtain a 5:1 polymer:essential oil emulsion. The system was homogenized using an UltraTurrax T-25 homogenizer (IKA, Staufen, Germany) at 17,000 rpm for 5 min, followed by 5 minutes of ultrasound (Bandelin Sonopuls, Berlin, Germany) and processed by electrospinning. For this, an emitter voltage of 20 kV and a collector voltage of -10 kV were used. A flow rate of 5 ml / h was also used through a 22G multi-needle linear injector. The fibers were deposited on a rotating collector (200 rpm). This layer has a surface density of 2 g / m 2 .
[0125] Another layer of fibers was deposited on top of the previous layer, starting from a solution of 8% by weight (wt.) pullulan and 2% collagen in deionized water. Once both components were dissolved, the fiber mat was manufactured using the electrospinning technique in a 5-needle linear multi-output injector. To produce the fiber mat, an emitter voltage of 25 kV was used, as well as a collector voltage of -25 kV. A flow rate of 5 ml / h was also used. The fibers were deposited on a rotating collector (200 rpm) over the previous layer. In this case, the surface density is 5 g / m 2 In this type of patch, the water-soluble layers are solubilized in partially moist skin.
Claims
CLAIMS 1. A self-adhesive, soluble cosmetic product for application to the skin, wherein the product comprises: a layer of polymeric fibers (A), where the fibers have an average diameter size between 50 nm and 5 pm; and are formed by polymer mixtures selected from the list consisting of: pullulan / elastin; pullulan / polyethylene glycol (PEG), pullulan / elastin / collagen and polyethylene oxide (PEO) / polyethylene glycol and where the layer (A) has a surface density of at least 0.01 g / m 2 .
2. Cosmetic product, according to claim 1, wherein said layer optionally comprises at least one encapsulated bioactive agent.
3. Cosmetic product, according to claim 1 or 2, where the polymeric fibers are made up of a pullulan / elastin mixture and the percentage by weight of elastin in the polymeric mixture is between 3 and 8% and the remainder would correspond to pullulan.
4. Cosmetic product, according to claim 1 or 2, where the polymeric fibers are made up of a pullulan / PEG mixture and the percentage by weight of PEG in the polymeric mixture is between 10 and 30% and the remainder would correspond to pullulan.
5. Cosmetic product, according to claim 1 or 2, where the polymeric fibers are made up of a pullulan / elastin / collagen mixture and the percentage by weight of elastin in the polymeric mixture is between 3 and 8%, that of collagen is between 10 and 50%, the remainder would correspond to pullulan.
6. Cosmetic product, according to claim 1 or 2, where the polymeric fibers are made up of a PEO / PEG mixture and the percentage by weight of PEG in the polymeric mixture is between 10 and 30% and the remainder corresponds to PEO.
7. Cosmetic product according to any of claims 1 to 3 or 5, wherein the elastin is vegetable elastin.
8. Cosmetic product according to claim 7, wherein the vegetable elastin is hydrolyzed wheat protein.
9. Cosmetic product according to any of claims 1, 2, 5, 7 or 8, wherein the collagen is of non-animal origin.
10. Cosmetic product for the absorption of oil or grease from the skin, comprising or consisting of: a layer of polymeric fibers (B), wherein: said layer comprises a bioactive agent, this bioactive agent being a grease or oil absorbent material, and where the polymeric fibers are formed by polymers selected from the list consisting of: polyhydroxyalkanoates (PHA), medium chain length polyhydroxyalkanoates (mcl-PHA), polylactic acid (PLA), poly-e-caprolactone (PCL), polybutylene succinate (PBS), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), copolymers of any of the foregoing, and any combinations thereof, or where said layer optionally comprises a bioactive agent, this bioactive agent being a grease or oil absorbent material, and where the polymeric fibers are formed by mixtures of polymers selected from the list consisting of: PHA / PBS, PHA / PCL, PHA / PBAT and PHA / PBSA,and where the polymeric fibers have an average diameter size between 50 nm and 5 pm and the fiber layer has a surface density of at least 0.01 g / m, 2 .
11. Cosmetic product, according to claim 10, wherein the polymer that forms the polymeric fibers of layer (B) is selected from a mixture of PHA / PBS, PHA / PCL, PHA / PBAT and PHA / PBSA, and where the PHA content in the mixture is at least 30% by weight with respect to the polymeric mixture.
12. Cosmetic product according to claim 10 or 11, comprising a grease or oil-absorbing material selected from: carbonaceous compounds, selected from activated carbon, carbon black, graphite, graphene, carbon fibers or tubes; silica, clays, selected from bentonites, kaolinites, vermiculites, laponites, sepiolite, zeolites, volcanic rock, as well as any combination thereof.
13. Cosmetic product according to any of claims 10 to 12, wherein the content of fat or oil absorbent material in the layer of polymeric fibers (B) is less than 25% by weight relative to the total weight of the layer.
14. Cosmetic product according to any of claims 10 to 13, wherein the layer of polymeric fibers (B) comprises hexadecyltrimethylammonium bromide in an amount between 0.01 and 3% by weight relative to the total weight of the layer of polymeric fibers (B).
15. Cosmetic product according to any of the preceding claims, comprising a support or substrate layer (S) on which the layer of polymeric fibers (A) or (B) is located.
16. Cosmetic product, according to claim 15, wherein the support or substrate layer (S) has a surface density of at least 0.1 g / m 2 .
17. Cosmetic product according to any of claims 15 or 16, wherein the support or substrate layer (S) comprises or consists of starch, cellulose, cellulose acetate, polycaprolactone (PCL) or any combination thereof.
18. Cosmetic product according to any of the preceding claims, wherein the layers of fibers (A) or (B) are obtained by electro-hydrodynamic, aero-hydrodynamic techniques or a combination thereof.
19. Cosmetic product according to claim 18, wherein the layers of fibers (A) or (B) are obtained by electrospinning.
20. Method for obtaining the cosmetic product defined in any of claims 1 to 19, wherein said method is based on the electrospinning technique comprising: preparing a layer of fibers (A or B) from a solution, suspension or emulsion of the polymer or mixture of polymers that will form the fibers, where the polymer or mixture of polymers is at a concentration of between 0.1 and 60% by weight and the process conditions are as follows: the voltage of the emitter used is between 0.01 and 500 kV and a voltage at the collector of between 0 kV and - 500 kV; a flow rate of between 0.0001 and 50,000 ml / h, a temperature of between 1 ° C and 100°C, and a relative humidity between 10 and 30%.
21. Method according to claim 20, wherein one or more bioactive agents are added to the solution, suspension or emulsion of the polymer or mixture of polymers at a total concentration between 0.01 and 70% by weight in said solution, suspension or emulsion.
22. Method according to claim 20 or 21, wherein the fiber layer (A) or (B) is prepared on a substrate layer (S).
23. Method according to any of claims 20 to 22, wherein controlled output, multi-output or multi-emitter injectors are used.
24. Method according to claim 23, where the variation in fiber diameter is less than 35%.
25. Cosmetic use of the cosmetic product defined in any of claims 1 to 9, 15 to 19 to produce a beneficial cosmetic effect on the skin.
26. Use of the product defined in any of claims 2 to 9, 15 to 19, for the controlled release of one or more bioactive agents on the skin in the event that the cosmetic product comprises at least one bioactive agent.
27. Cosmetic use of the cosmetic product defined in any of claims 9 to 19 for the absorption of oil or fat from the skin.
28. Kit comprising a cosmetic product, as described in claims 1 to 9 and 15 to 19 and a water-based spray container with or without other cosmetic, balsamic and / or odorant products.
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