Silicate-releasing fibers or fiber fragments, nonwoven fabrics and formulations made therefrom.

Abstract

The present invention relates to silica-releasing fibers or fiber fragments formed by preparing a spunable sol by hydrolysis condensation of at least one silane compound selected from the group consisting of tetraalkoxysilanes, trialkoxysilanes, halosilanes, and mixtures thereof, using an organic or inorganic acid with a pKs value of less than 2.5 as a catalyst, and then spinning the spunable sol into fibers. The spun fibers or fiber fragments are impregnated with the non-aqueous solution by contacting them with the non-aqueous solution. The present invention also relates to fiber nonwovens containing these silica-releasing fibers or fiber fragments. These fibers, fiber fragments, or fiber nonwovens are used in the fields of regenerative medicine, microbiology, pharmaceutical applications, the cosmetics industry, diagnostics, the food industry, filters, fiber reinforcement of materials, and optics.

Description

[Technical Field]

[0001] The present invention relates to silica-releasing fibers or fiber fragments formed by preparing a spunable sol by hydrolysis condensation of at least one silane compound selected from the group consisting of tetraalkoxysilanes, trialkoxysilanes, halosilanes, and mixtures thereof, using an organic or inorganic acid with a pKs value of less than 2.5 as a catalyst, and then spinning the spunable sol into fibers. The spun fibers or fiber fragments are impregnated with an aqueous solution by contacting them with an aqueous solution. The present invention also relates to nonwoven fabrics containing these silica-releasing fibers or fiber fragments. These fibers, fiber fragments, or nonwoven fabrics are used in regenerative medicine, microbiology, pharmaceutical applications, the cosmetics industry, diagnostics, the food industry, filters, fiber reinforcement of materials, and optics. [Background technology]

[0002] For topical application of active ingredients to the skin (for skin diseases, scar reduction, minor burns, acne, cosmetics, etc.), a carrier system is required that can be individually adapted to the application site, simultaneously exhibit (time-adjustable) release of the active ingredient, and subsequent dissolution behavior that is as complete and skin-compatible as possible.

[0003] For example, cosmetic active substances are applied by face masks to induce anti-aging or well-aging effects on or within the skin. Often, face masks are made of synthetic polymers such as cellulose (or its derivatives), proteins, or silicones, and are used to apply cosmetic active substances to the surface of the skin. All of these face masks must be removed after application to the skin, thus generating waste. A new generation of face masks or pads are being developed with efficacy and sustainability in mind. They should have the following characteristic profile: a) Face masks should have long-lasting cosmetic effects. b) The face mask should dissolve completely or mostly on the skin, and its breakdown products should be absorbed into the skin. Any remaining residue will decompose after the skin is washed off. This means there should be no residue from the face mask that needs to be discarded. c) The face mask should be completely dissolved in naturally occurring ingredients.

[0004] Orthosilicic acid (oKS), the only water-soluble form of silicic acid, has the potential to stimulate collagen production and, consequently, the formation of connective tissue in the dermis. Insufficient levels of silicic acid (KS) in the dermis are associated with blood cell counts. In particular, in older adults, a decrease in the natural Si content in serum has been observed, which is then reflected in the appearance of the skin (E. Bisse, Analytical Biochemistry 337 (2005) 130-135).

[0005] The connective tissue stimulating effect of silicic acid makes it suitable for use in cosmetics. However, transdermal administration presents significant challenges. Many condensed silicic acids or amorphous silicas exhibit very low dissolution rates (release of water-soluble orthosilicic acid) and are therefore not currently used / rarely used for transdermal administration.

[0006] Orthosilicic acid is also said to have positive effects on hair, strengthen nails, be involved in bone formation, and according to the latest research, may even be an important component in preventing Alzheimer's disease.

[0007] Current cosmetic silica products are based on bamboo-derived silica and are typically sold as nutritional supplements with advertised cosmetic effects, or as powders for application to the skin. It has been scientifically proven that polysilicic acids, such as bamboo-derived silica, are not absorbed by healthy skin and are not incorporated into metabolism (LA de Araujo et al., A. brasil. dermat. 2016, 91, 331).

[0008] Another approach in the prior art is to provide orthosilicic acid in the form of a tincture. Orthosilicic acid is only slightly soluble in aqueous solution at approximately 120 mg / l. Therefore, it is not possible to provide higher concentrations of orthosilicic acid in tincture form. In available liquid tinctures, orthosilicic acid remains in solution throughout the entire storage period, which can lead to intermolecular condensation, i.e., the formation of polysilicic acid. Competitors have attempted to avoid this condensation by using synthetic molecules as orthosilicic acid substitutes. One example of this is monomethylsilanetriol or maltodextrin-stabilized oKS (Anderson Oliveira Ferreira et al., Cosmetics 2018, 5, 41). In monomethylsilanetriol, the silanol group (-Si-OH) of orthosilicic acid is replaced with a methyl group (Si-CH3). This modification is classified as unnatural because the Si-C bond does not occur naturally.

[0009] One publication describes how orthosilicic acid can be stabilized with hydrolyzed marine collagen. This was applied in capsule form for oral administration, resulting in a significant improvement in skin texture, moisture, and firmness in the subjects (Petersen Vitello Kalil CL et al, Evaluation of cutaneous rejuvenation associated with the use of ortho-silicic acid stabilized by hydrolyzed marine collagen. J Cosmet Dermatol. 2018;17:814-820). [Prior art documents] [Non-patent literature]

[0010] [Non-Patent Document 1] E. Bisse, Analytical Biochemistry 337 (2005) 130-135 [Non-Patent Document 2] LA de Araujo et al., A. brasil. dermat. 2016, 91, 331 [Non-Patent Document 3] Anderson Oliveira Ferreira et al., Cosmetics 2018, 5, 41 [Non-Patent Document 4] Petersen Vitello Kalil CL et al, Evaluation of cutaneous rejuvenation associated with the use of ortho-silicic acid stabilized by hydrolyzed marine collagen. J Cosmet Dermatol. 2018;17:814-820 [Overview of the project] [Problems that the invention aims to solve]

[0011] Most face masks on the market are cloth masks that must be removed after use, thus generating waste. These are not related to the administration of orthosilicic acid through the skin barrier. There are also gel masks, but the gel must also be removed after application to the skin. Nonwoven face masks that are completely absorbed by the skin, thus generating no waste, and that transport silica into / through the skin do not exist on the market or in any specialized literature.

[0012] Based on this, the object of the present invention is to provide fibers or fiber fragments, as well as nonwoven fabrics and formulations containing them, that enable skin application and allow for the transport of silicic acid in or through the skin. [Means for solving the problem]

[0013] This objective is achieved by a fiber or fiber fragment having the features of claim 1, a nonwoven fabric having the features of claim 11, and a cosmetic agent having the features of claim 17. Further dependent claims describe advantageous developments.

[0014] Definition of Terms In the context of the present invention, the term "biodegradable" fiber refers to a fiber that is cytocompatible and degrades under physiological conditions.

[0015] Silicic acid is a compound having the general molecular formula H (2n+2) Si n O (3n+1) , such as monosilicic acid (Si(OH)₄ or H₄SiO₄), disilicic acid (H₆Si₂O₇), trisilicic acid (H₈Si₃O₁₀), other oligosilicic acids, polysilicic acids and cyclic (poly)silicic acids.

[0016] For the purposes of the present invention, the term "viscosity" means dynamic viscosity, which is preferably determined at a shear rate of 10 s -1 using an Anton Paar Physica MCR301 rheometer equipped with a coaxial cylinder measuring attachment of type CC17 / T200 / SS.

[0017] "Crosslinking of silane compounds" and covalent incorporation of organic acids into the network are exemplified in the following figure using the incorporation of methanesulfonic acid.

Chemical Formula

[0018] According to the present invention, there is provided a silicic acid-releasing fiber or fiber fragment formed by preparing a spinnable sol via hydrolytic condensation of at least one silane compound selected from the group consisting of tetraalkoxysilanes, trialkoxysilanes, halosilanes and mixtures thereof, and then spinning the spinnable sol into fibers, wherein the hydrolytic condensation is carried out with an organic acid having a pKs value of less than 2.5. The pKs should be lower than the isoelectric point.

[0019] The present invention is characterized in that the non-aqueous solution is permeated into the fibers by bringing the spun fibers or fiber fragments into contact with the non-aqueous solution.

[0020] Preferably, the non-aqueous solution is brought into contact with the fibers by spinning them in the non-aqueous solution as a spinning bath. Alternatively, and more preferably, this can also be done by spraying or spraying the non-aqueous solution onto the spun fibers or fiber fragments, or by placing the spun fibers or fiber fragments in the non-aqueous solution.

[0021] In the context of this invention, a non-aqueous solution is understood to mean a non-aqueous solvent or even a mixture of several non-aqueous solvents.

[0022] The non-aqueous solution is preferably selected from the group consisting of vegetable oils, mineral oils, glycerin, propylene glycol and their derivatives, esterified glycerols, polyethyl glycols, fatty acid esters, fatty acids, fatty alcohols, wax alcohols, waxes, resins, glucosides, terpenes, squalene, phospholipids, ceramides and mixtures thereof, and preferably sunflower oil, almond oil, jojoba oil, avocado oil, passion fruit oil, moringa oil, coconut oil fatty acid butylene glycol, and sodium laureth sulfate. Selected from the group consisting of IPA (and) cocoamidopropyl betaine, dicaprylyl ester (and) decyl glucoside (and) glyceryl oleate, ethylhexyl stearate, cetearyl isononanoate, caprylic acid, dicaprylyl caprate, octyldodecanol, phytosqualane, dimethiocone, isopropyl myristate, isopropyl palmitate, kerosene, linoleic acid, propylene glycol, butylene glycol, terpenes, and mixtures thereof.

[0023] Particularly preferred are non-aqueous solutions selected from the group consisting of sunflower oil, almond oil, jojoba oil, avocado oil, moringa oil, passion fruit oil, coconut oil fatty acid butylene glycol, laureth sulfate MIPA (and) cocoamidopropyl betaine, dicaprylyl ester (and) decyl glucoside (and) glyceryl oleate, ethylhexyl stearate, cetearyl isononanoate, caprylic acid, dicaprylyl caprate, octyldodecanol, phytosqualane, dimethiocone, isopropyl myristate, isopropyl palmitate, kerosene, linoleic acid, propylene glycol, butylene glycol, limonene, and mixtures thereof.

[0024] Non-aqueous solutions do not contain short-chain alcohols, especially C1-C4 alcohols such as methanol, ethanol, propanol, and butanol.

[0025] Other cosmetic or pharmaceutical active substances may preferably be dissolved or dispersed in a non-aqueous solution.

[0026] Preferably, the non-aqueous solution is in a liquid state, i.e., the viscosity of the solution is in the range of 0.5 to 10,000 mPa at 20°C, at a temperature of -20 to +80°C, particularly preferably in the range of +15 to +40°C. However, there are also potential applications where the non-aqueous matrix becomes liquid only at room temperature, with minimal exposure to body temperature or heat, or with another external trigger such as shear force or ultrasound.

[0027] It is more preferable that at least one organic or inorganic acid is selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, sulfonic acid, particularly methanesulfonic acid, carboxylic acid, carboxylic acid ester, sulfuric acid ester, amino acid, phosphonic acid, phosphate ester and mixtures thereof, or mixtures with other acids having a pKs value in the range of 2.5 to 7.0. Methanesulfonic acid is particularly preferred.

[0028] In preferred embodiments, at least one silane compound is of the general formula Si(OC) x H 2x+1)4 (wherein x=1 to 12) is selected from the group consisting of mixed or unmixed tetraalkoxysilanes, preferably from the group consisting of tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and mixtures thereof.

[0029] The fiber thickness is preferably in the range of 50 nm to 120 μm, and particularly preferably in the fiber diameter range of 30 to 70 μm.

[0030] The fibers used may be pure silica gel fibers, or they may be fibers in which cosmetic or medicinal active substances are incorporated into their fiber matrix.

[0031] The fibers are preferably processed in the following steps: a) A step of obtaining an alcoholic solution of at least one silane compound selected from the group consisting of tetraalkoxysilanes, trialkoxysilanes, halosilanes and mixtures thereof, wherein the alcohol is preferably selected from the group consisting of monovalent, divalent or trivalent, branched or unbranched alcohols, which may be aliphatic or aromatic, and is particularly preferably selected from the group consisting of ethanol, propanol, butanol, ethylene glycol, phenol and mixtures thereof; b) A step of obtaining an aqueous solution of at least one organic or inorganic acid having a pKs value of less than 2.5, wherein the organic acid is preferably 0.01N to 1N, and / or the content of the organic acid in the aqueous solution is preferably in the range of 0.01 to 2% by weight, preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0.5% by weight, relative to the total weight of the solution; c) Mix the solutions prepared in steps a) and b) and mix at a temperature of 20-70°C for 4 hours to 1 week; d) Remove at least some of the alcohol from the mixture from step c), then cool the concentrated mixture to a temperature of 20 to -25°C; e) The cooled mixture from step d) is stored until it reaches a viscosity of 10-75 Pa·s; f) A step of spinning the mixture from step e) into continuous fibers, Includes, Between steps c) and f), crosslinking of the silane compound occurs, and at least a portion of the organic or inorganic acid is incorporated into the resulting network and / or contributes to the crosslinking. It can be manufactured using the method.

[0032] In a more preferred embodiment of the present invention, the mixing in step c) is carried out by adding an aqueous solution of an organic or inorganic acid dropwise to the alcoholic silane solution, or by adding an alcoholic silane solution dropwise to an aqueous solution of an organic or inorganic acid, or by adding the alcoholic silane solution and the aqueous solution of an organic or inorganic acid simultaneously.

[0033] In a more preferred embodiment of the present invention, the mixing in step c) is carried out by stirring or shaking.

[0034] In a more preferred embodiment of the present invention, the mixture from step c) is stirred for 10 minutes to 168 hours, preferably 10 to 24 hours, and particularly preferably 16 to 18 hours. In another preferred embodiment of the present invention, the temperature in step c) is 4 to 70°C, preferably 10 to 50°C, and particularly preferably 25 to 40°C.

[0035] In a more preferred embodiment of the present invention, the pH of the mixture in step c) is less than 5.5, preferably 1 to 5, and particularly preferably 2 to 4.

[0036] In a more preferred embodiment of the present invention, the mixing in step c) is carried out by adding an aqueous solution of an organic or inorganic acid dropwise to an alcoholic silane solution, or by adding an alcoholic silane solution dropwise to an aqueous solution of an organic or inorganic acid, or by adding an alcoholic silane solution and an aqueous solution of an organic or inorganic acid simultaneously. The mixing in step c) is carried out by stirring, and the mixture from step c) is stirred for 10 to 144 hours, preferably 10 to 24 hours, and particularly preferably 16 to 18 hours, the temperature in step c) is 4 to 70°C, preferably 10 to 50°C, and particularly preferably 25 to 40°C, and the pH value of the mixture in step c) is less than 5, preferably 1 to 4.9, and particularly preferably 2 to 4.9.

[0037] In another preferred embodiment of the present invention, 40 to 80% by weight, preferably 45 to 75% by weight, and particularly preferably 50 to 65% by weight of the solvent mixture is removed during step d) based on the total mass of the batch prepared in step b).

[0038] In a more preferred embodiment of the present invention, the concentrated mixture from step d) is cooled to a temperature of 20 to -25°C, preferably 10 to -25°C, and particularly preferably 4 to -20°C.

[0039] In a more preferred embodiment, at least some of the water from step b) is also removed during step d).

[0040] In a more preferred embodiment of the present invention, during step d), 40 to 80% by weight, preferably 45 to 75% by weight, and particularly preferably 50 to 65% by weight of the solvent mixture is removed based on the total mass of the preparation produced in step b), the concentrated mixture from step d) is cooled to a temperature of 20 to -25°C, preferably 10 to -25°C, and particularly preferably 4 to -20°C, and at least a portion of the water from step b) is removed.

[0041] In a more preferred embodiment of the present invention, step e) is carried out until a viscosity of 10 to 70 Pa·s, preferably 10 to 40 Pa·s, and particularly preferably 20 to 25 Pa·s is reached.

[0042] Spinning is preferably carried out by electrospinning with the addition of a spinning aid at a voltage of 1 to 30 kV and a distance of 0.2 to 30 cm, particularly preferably at a voltage of 6 to 30 kV and a distance of 10 to 30 cm, or at a voltage of 1 to 5 kV and a distance of 0.2 to 2 cm, or by pressure spinning at a pressure of preferably 10 to 60 bar, particularly preferably 20 to 40 bar.

[0043] In a more preferred embodiment of the present invention, the method follows the following further method steps: g) Crushing, cutting or punching the continuous fibers obtained after spinning in step f), and / or h) Preferably includes sterilization of the fibers from step f) or g) by gamma radiation or automatic washing, treatment with a 70% ethanol solution of ethylene oxide, hydrogen peroxide, or chloroform.

[0044] During steps c) to f) of the manufacturing process, pre-crosslinking of the silane compound occurs, which steadily progresses over time, crosslinking the fiber matrix. When the fiber or fiber fragment is brought into contact with a non-aqueous liquid after step f) or g) or h), this liquid can penetrate the fiber or fiber fragment. The non-aqueous liquid inhibits further condensation (crosslinking) to form a dense inorganic network. Instead, only silica clusters with a low degree of crosslinking are present, which are further stabilized by intramolecular interactions with the non-aqueous liquid in fiber form. When mechanical action is applied while the material is in contact with the skin, silica clusters and silicic acid are released and absorbed into the skin (Figure 3). Upon initial contact with water, e.g., sweat or other bodily fluids, the silica clusters hydrolyze to silicic acid. This hydrolysis reaction can be accelerated by bringing an aqueous solution into contact with the ground fiber or fiber fragment.

[0045] In a more preferred embodiment of the present invention, the method is carried out sequentially or in batches.

[0046] In another preferred embodiment of the present invention, the method does not include any other process steps other than steps a) to h) described above and the penetration of a non-aqueous solution.

[0047] According to the present invention, a nonwoven fabric containing or consisting of the aforementioned silica-releasing fibers or fiber fragments is also provided.

[0048] Such nonwoven fabrics can be absorbed into the skin within seconds to minutes without leaving any residue; that is, the fibers are completely absorbed by the skin and transported through the epidermis.

[0049] The thickness of the nonwoven fabric can be adjusted, preferably in the range of 100 μm to 10 mm, and particularly preferably in the range of 400 μm to 2 mm.

[0050] The aqueous solution preferably has a pH of 3.7 to 9.0, and particularly preferably 4.7 to 7.5. The dissolution of the fibers is promoted as the solution becomes more alkaline.

[0051] The aqueous solution is • Surfactants, especially ionic and nonionic surfactants, saponins, fatty acids, phospholipids, ceramides, • Penetration enhancers, especially phospholipids, polyethylene glycol, • Cosmetic active additives, especially vitamins, provitamins, amino acids, heparin, hyaluronic acid, collagen (derivatives), plant extracts, probiotics, enzymes, hydrates, fragrances, colorants, preservatives, abrasives / particles It is even more preferable to include further additives selected from the group consisting of the following:

[0052] The absorption of silica into the skin can also be improved by using transport enhancers such as (unsaturated) phosphorides or polyethylene glycol, or by reducing the skin barrier through physical or chemical stimulation, such as ultrasound, micro-abrasion, or transport enhancers.

[0053] The present invention has the following advantages 1) Effective transdermal administration of orthosilicic acid: Silica gel nonwovens are amorphous fibrous solids that store silica precursors in a condensed form (silica gel). Upon contact with water (and surprisingly, even by acclimation with surfactant solutions and, surprisingly, without aqueous solutions), the nonwovens dissolve and are completely absorbed by the skin. This allows for the application of large amounts of silicic acid (depending on the weight of the nonwoven and the area of ​​skin to which it is applied), resulting in the achievement of orthosilicic acid effects in vivo.

[0054] Topical competing products act as balms / creams or aqueous tinctures, but in these cases only small amounts of orthosilicic acid are delivered. Alternatives are nutritional supplements for oral administration. If orthosilicic acid crosses the intestinal barrier, it is administered systemically rather than topically to the skin.

[0055] Methylated silicic acid is also used in the literature because it is stable in aqueous solutions and shows little to no self-condensation. This modification involves Si-C bonds that do not occur naturally. As a result, unnatural substances are released into the environment. According to the inventors' research, orthosilicic acid-releasing face masks do not currently exist on the market.

[0056] 2) Reduction of waste (and microplastics): Almost all face masks on the market consist of a carrier structure that is applied to the skin and then removed after cosmetic application. Each application generates household waste. These face masks are often made of synthetic materials such as cellulose or silicone. The present invention is completely absorbed by the skin and therefore leaves no waste. Only naturally occurring silicic acid is produced from silica gel fibers.

[0057] It is also possible to manufacture face masks that contain absolutely no (micro)plastics. This is true if the anhydrous liquid is also composed of natural or near-natural substances.

[0058] Fibers, fiber fragments, and nonwoven fabrics are used in the following application fields: a) Cosmetics (for human and animal use): • Topical application, especially to the skin, e.g., face masks, eye pads, forehead masks, scalp, nail beds, acne, and scars: silica-releasing pads. Oil-impregnated nonwoven fabric pieces / monofilaments / fiber fragments for formulations of lotions, ointments, creams (including toothpaste), and shower gels. • Topical silica-releasing pads for connective tissue debilitation, e.g., cellulite reduction, or scar formation / reduction. • Reduction of microbial contamination through the application of oil-impregnated nonwoven fabric (antibacterial effect of anhydrous liquid) b) Dietary supplements and food additives (for human and animal use): • KS release nonwoven fabric or monofilament immersed in (edible) oil / liquid for oral ingestion c) Pharmaceuticals (for human and animal use): For example, KS-releasing nonwoven fabrics / nonwoven pieces / monofibers / fiber fragments for the treatment or symptom relief of inflammatory and / or chronic skin diseases, acne, age spots, neurodermatitis, pressure ulcers, eczema, keratosis, psoriasis, dry skin, cellulite, cellulitis, or • As an insect repellent ·For skin irritation • For superficial burns • To assist in the treatment of skin diseases for the regeneration and formation of healthy skin. • Antibacterial effect of KS-releasing fibers applied with a waterless liquid. • Strengthening of connective tissue • Strengthening of blood vessel walls; reduction of bruising in people with weak blood vessel walls. d) Plants: • KS storage containers for plant cultivation and regeneration ·For plant protection

[0059] According to the present invention, cosmetic compositions having the above-mentioned fibers, fiber fragments, or nonwoven fabrics are also provided.

[0060] These cosmetics preferably take the form of skincare creams, emulsions, lotions, gels and oils, face masks, makeup bases (liquids, pastes, powders), face powders, body powders, foot powders, cosmetic soaps, deodorant soaps, perfumes, lotions and colognes, bath and shower additives (salts, foams, oils, gels), hair removal products, deodorants and antiperspirants, hair dyes, hair waving, hair straightening and hair styling products, hair styling products, hair cleansers (lotions, powders, shampoos), hair care products (lotions, creams, oils), styling aids (lotions, varnishes, Brilliantine), shaving products (including pre-care and after-care), makeup and makeup remover products, lip care products and cosmetics, dental care and oral care products, nail care products and cosmetics, external intimate area care products, sunscreens, self-tanning products, skin whitening products, and wrinkle-improving products.

[0061] The subject matter of the present invention will be described in more detail with reference to the following figures and examples, and is not limited to the specific embodiments shown herein. [Brief explanation of the drawing]

[0062] [Figure 1] This graph shows the results of ICP analysis of basal lateral media in transport studies for an in vitro epidermal model. [Figure 2] This is a cross-sectional image of the epidermis model in comparison with the model according to the present invention and the untreated model. [Figure 3] This is a photograph of human skin after application of the nonwoven fabric according to the present invention. [Modes for carrying out the invention]

[0063] [Example 1] 5 mol of tetraethoxysilane (Sigma Aldrich) was mixed in an ethanolic solution (230 mL). 163.5 g of 0.1 N methanesulfonic acid solution was added to this sol over 2 hours, and the resulting mixture was further stirred at 40°C for 18 hours. The solvent was then removed from the sol until a residual mass of 577 g remained in the flask. The sol was aged at -20°C to a honey-like viscosity (21 Pas measured at 4°C). The viscous liquid was filled into a pressurized vessel at a temperature of -15°C and extruded at a pressure of 20 bar through a nozzle plate equipped with seven nozzles (nozzle diameter: 150 μm). After dropping 2.5 m, the microfibers were recovered at 20% humidity and processed into a nonwoven fabric using a traverse table that moved in the x and y directions. A container filled with sunflower oil was placed on the traverse table, thereby allowing the individual microfibers to be directly deposited into the sunflower oil, forming a nonwoven fabric. The nonwoven fabric can be removed, cut to size, and applied to the skin without leaving any residue.

[0064] [Example 2] Silicate-releasing fibers were prepared in the same manner as in Example 1 and applied to the skin, allowing them to penetrate. The skin was then further treated with micellar water or an aqueous surfactant solution.

[0065] [Example 3] 5 mol of tetraethoxysilane (Sigma Aldrich) was mixed in an ethanolic solution (250 mL). 176.4 g of 0.1 N nitric acid solution was added to this sol over 2 hours, and the resulting mixture was further stirred at 40°C for 18 hours. The solvent was then removed from the sol until a residual mass of 616.2 g remained in the flask. The sol was aged at -20°C to a honey-like viscosity (32 Pas measured at 4°C). The viscous liquid was filled into a pressurized vessel at -15°C and extruded at a pressure of 20 bar through a nozzle plate equipped with 19 nozzles (nozzle diameter: 150 μm). After dropping 2.5 m, the fibers were recovered at 20% humidity and processed into a nonwoven fabric using a traverse table moving in the x and y directions. The container filled with sunflower oil was placed on a traverse table, which allowed the individual microfibers to settle directly in the sunflower oil, forming a nonwoven fabric. The nonwoven fabric can then be removed, cut to size, and applied to the skin without leaving any residue.

[0066] [Example 4] Silicate-releasing fibers were produced in the same manner as in Example 3, except that the fibers were spun using 0.1N methanesulfonic acid as a catalyst and then impregnated with sunflower oil. Impregnation was carried out using five different methods: 1) The nonwoven fabric was soaked in sunflower oil. 2) Place the nonwoven fabric inside the package filled with sunflower oil. 3) Using a pipette, sunflower oil was sprayed onto the nonwoven fabric. 4) Sunflower oil was sprayed onto the nonwoven fabric using a pump sprayer. 5) Using an airbrush system, sunflower oil was finely sprayed onto the nonwoven fabric.

[0067] [Example 5] Silicate-releasing fibers were produced in the same manner as in Example 3, but, as in Example 4, only the fibers were spun using 0.1N HCl as a catalyst, and then impregnated with sunflower oil.

[0068] [Example 6] Silica gel μ fibers were pressure-spun using methanesulfonic acid as a catalyst in the same manner as in Example 1, and spun into a nonwoven fabric using a traverse table moving in the x and y directions. After spinning, a non-aqueous solution was sprayed onto the μ fibers for less than 10 minutes. After cutting, the nonwoven fabric could be fully absorbed into the skin.

[0069] [Example 7] Silica gel μ fibers were pressure-spun using methanesulfonic acid as a catalyst in the same manner as in Example 1, and spun into a nonwoven fabric using a traverse table moving in the x and y directions. During spinning, a non-aqueous liquid was sprayed onto the fibers. After cutting, the nonwoven fabric could be fully absorbed into the skin.

[0070] [Example 8] Silica gel μ fibers are pressure-spun using methanesulfonic acid as a catalyst in the same manner as in Example 1, and spun into a nonwoven fabric using a traverse table moving in the x and y directions. The nonwoven fabric is cut to size, and then sprayed with a non-aqueous liquid and mixtures thereof. The nonwoven fabric can be fully absorbed into the skin.

[0071] The following substances and mixtures were tested as non-aqueous liquids: Sunflower oil, almond oil, jojoba oil, moringa oil, avocado oil, Cegesoft PFO (passion fruit oil), Cocoate BG, Lumorol K1056 (MIPA laureth sulfate (and) cocoamidopropyl betaine), Plantasil Micro (dicaprylyl ester (and) decyl glucoside (and) glyceryl oleate), Cetiol 868 (ethylhexyl stearate), Cetiol SN (cetearyl isononanoate), Cetiol RLF (caprylate), Cetiol CC (dicaprylyl caprate), Eutanol G (octyldodecanol), phytosqualane, Abil350 (dimethiocone), isopropyl myristate, isopropyl palmitate, linoleic acidure, propylene glycol, butylene glycol, kerosene.

[0072] [Example 9] 5 mol of tetraethoxysilane (Sigma Aldrich) was mixed in an ethanolic solution (230 mL). 163.5 g of 0.1 N methanesulfonic acid solution was added to this sol over 2 hours, and the resulting mixture was stirred at 40°C for 18 hours. The solvent was then removed from the sol until a residual mass of 577 g remained in the flask. The sol was aged at -20°C and had a honey-like viscosity (21 Pas measured at 4°C). The viscous sol was then heated to 4°C and directly diluted with 577 g (Mw = 50000 g / mol) of a mixture of 571 g of ethanol and 6 g of polyethylene glycol.

[0073] When there is a distance of 15 cm between the cannula and the rotating target, the spinning process is carried out at a delivery rate of 0.7 ml / hour, and a voltage of 13-16 kV is applied to the cannula. The resulting nonwoven fabric consists of fibers with a diameter of approximately 1 μm. The resulting nonwoven fabric is cut to size, and then sprayed or misted with a non-aqueous liquid or a mixture thereof. These nonwoven fabrics can be fully absorbed into the skin.

[0074] [Example 10] Application of impregnated silica gel fibers to 3D in-vitro epidermal models Experiment execution: For the experiment, an in-vitro epidermal model was constructed from primary cells (keratinocytes) of the Transwell system. In Example 1, a total of two silica gel (KG) fiber samples were prepared. Sample 1 was impregnated with sunflower oil (SB) (Sample 1 = KG + SB); and Sample 2 was impregnated with alkyl isononanoate ester (INSA) (Sample 2 = KG + INSA). Each sample—KG+SB and KG+SB-—was adapted to three different epidermal models, then PBS (physiological phosphate buffer) was added to the models, and the models were incubated for a further 24 hours. An epidermal model without silica gel fibers was used as a control. (In upstream experiments, SB and INSA alone did not show cytotoxicity in the epidermal model.) After stopping the experiment, the structure of the skin model was confirmed using hematoxylin-eosin (H / E) staining, cell viability was assessed using the MTT test, and the concentration of oKS transported through the skin was quantified using ICP analysis.

[0075] Evaluation of results: Both the KG+SB and KG+INSA samples showed sufficient performance. The cross-section of the model showed no abnormalities in terms of cytotoxic effect even after application of the two samples, and exhibited a physiological epidermal structure after H / E staining. The epidermal layer remains intact and closed even after application of the two samples. Determination of cell viability using the MTT test shows no cytotoxicity at values exceeding 70% compared with the negative control. The slight decrease in cell viability is caused by mechanical effects during conditioning of the epidermal model with a thickness of only about 200 to 300 μm. The TEER value of the epidermal model is 12,000 Ohm in all three samples compared with the untreated control * cm 2 decreased to 5,000 to 6,000 Ohm * cm 2 , that is, the barrier function of the epidermis still exists but is reduced. This may be caused by swelling of the skin due to lipophilic substances and aqueous solutions, and may also further promote the required oKS transport through the skin.

[0076] In both samples (KG+SB and KG+INSA), the mass transport of orthosilicic acid through the epidermis can also be tracked by ICP analysis. The skin model was cultured in two compartments of a so-called "Transwell setup". The epidermal model forms an interface between the two compartments. Compartment 1 represents the interface between the epidermis and air. In this compartment, the non-woven fabric was applied and conditioned to the model. The second compartment is filled with cell culture medium and supplies nutrients to the cells. If silicic acid is transported through the epidermal model, silicon (Si) should be detected by ICP analysis of the cell culture medium from compartment 2.

[0077] ICP analysis showed that the transported Si concentration was 1.7 to 2.5 μg / mL in both cases. This corresponds to an orthosilicic acid concentration (Si(OH)4) of 5.8 to 8.6 μg / mL. The Si concentration in plasma of people aged 18 to 29 years is about 0.3 μg / mL, and decreases to 0.2 μg / mL with age (over 50 years) (Analytical Biochemistry 337 (2005) 130-135).

[0078] Compared to physiological Si concentrations, the detected Si transport is higher than these physiological values. Considering that the transported oKS is further diluted in vivo by tissue fluid and blood, the determined values ​​are promising concentrations due to the anticipated anti-aging effects.

[0079] Figure 1 shows the results obtained. Silica gel nonwovens soaked in SB and INSA were applied. A model with only pure buffer solution applied was used as a reference. The experiment was performed in triplicate. oKS greater than 1 mg / l can be transported through the epidermis of the in-vitro model.

[0080] Figure 2 shows micrographs of hematoxylin-eosin stained cross-sections of paraffin-embedded in-vitro epidermal models. One model was used as a reference and treated with pure PBS alone. Two additional models were in contact with silica gel fibers impregnated with sunflower oil (SB) and alkyl isononanoate (INSA), and then post-treated with PBS for embedding and hematoxylin-eosin staining. All models retained an intact skin barrier even after contact with the impregnated fibers.

[0081] Figure 3 shows the application of the nonwoven fabric according to the present invention. The nonwoven fabric according to the present invention, which was directly sprayed with sunflower oil after spinning, was applied to human skin (A). By mechanically rubbing the nonwoven fabric against the skin, the nonwoven fabric was completely absorbed into the skin (B). After that, no fiber residue remained on the skin (C).

Claims

1. A spunable sol is prepared by hydrolysis condensation of at least one silane compound selected from the group consisting of tetraalkoxysilane, trialkoxysilane, halosilane, and mixtures thereof, using at least one organic or inorganic acid with a pKs value of less than 2.5 as a catalyst, and then the spunable sol is spun to form a fiber, thereby forming a silicic acid-releasing fiber or fiber fragment. A fiber or fiber fragment characterized by impregnating the fiber with a non-aqueous solution by bringing the spun fiber or fiber fragment into contact with the non-aqueous solution.

2. The fiber or fiber fragment according to claim 1, characterized in that the non-aqueous solution is brought into contact with the fiber by spinning the fiber in the non-aqueous solution as a spinning bath, by spraying or scattering the non-aqueous solution onto the spun fiber or fiber fragment, or by placing the spun fiber or fiber fragment in the non-aqueous solution.

3. The non-aqueous solution is selected from the group consisting of vegetable oils, mineral oils, glycerin, propylene glycol and their derivatives, esterified glycerols, polyethyl glycols, fatty acid esters, fatty acids, fatty alcohols, wax alcohols, waxes, resins, glucosides, terpenes, squalene, phospholipids, ceramides and mixtures thereof, preferably sunflower oil, almond oil, jojoba oil, avocado oil, passion fruit oil, moringa oil, coconut oil fatty acid butylene glycol, laureth sulfate MIPA (and) cocoamidopropyl The fiber or fiber fragment according to claim 1 or 2, characterized by being selected from the group consisting of betaine, dicaprylyl ester (and) decyl glucoside (and) glyceryl oleate, ethylhexyl stearate, cetearyl isononanoate, caprylic acid, dicaprylyl caprate, octyldodecanol, phytosqualane, dimethiocone, isopropyl myristate, isopropyl palmitate, kerosene, linoleic acid, propylene glycol, butylene glycol, terpenes, and mixtures thereof.

4. The non-aqueous solution comprises at least one further substance selected from the group consisting of cosmetic base substances, active substances, additives, auxiliary substances and combinations thereof, preferably selected from the group consisting of spreading agents, penetration enhancers, waxes, vitamins, especially fat-soluble vitamins, fragrances, hydrates, colorants, plasticizers, light stabilizers, emulsifiers, antioxidants, radical scavengers and preservatives and combinations thereof, wherein the at least one further substance is preferably present in a pure form or encapsulated form, characterized in that the fiber or fiber fragment according to any one of claims 1 to 3.

5. The fiber or fiber fragment according to any one of claims 1 to 4, characterized in that the organic or inorganic acid is selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, sulfonic acid, particularly methanesulfonic acid, carboxylic acid, sulfuric acid ester, amino acid, phosphonic acid, phosphate ester and mixtures thereof or mixtures with other acids having a pKs value in the range of 2.5 to 7.

0.

6. The at least one silane compound is of the general formula Si(OC) ｘ H ２ｘ＋１ ) ４ A fiber or fiber fragment according to any one of claims 1 to 5, characterized in that it is selected from the group consisting of mixed or unmixed tetraalkoxysilanes represented by the formula (wherein x = 1 to 12), preferably selected from the group consisting of tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and mixtures thereof.

7. The fiber or fiber fragment according to any one of claims 1 to 6, characterized in that the fiber has a diameter of 50 nm to 120 μm, preferably 30 μm to 70 μm.

8. The aforementioned fibers are produced in the following steps: a) A step of obtaining an alcoholic solution of at least one silane compound selected from the group consisting of tetraalkoxysilanes, trialkoxysilanes, halosilanes and mixtures thereof, wherein the alcohol is preferably selected from the group consisting of monovalent, divalent or trivalent, branched or unbranched alcohols, which may be aliphatic or aromatic, and is particularly preferably selected from the group consisting of ethanol, propanol, butanol, ethylene glycol, phenol and mixtures thereof; b) A step of obtaining an aqueous solution of at least one organic acid or inorganic acid having a pKs value of less than 2.5, wherein the organic acid is preferably 0.01 N to 1 N, and / or the content of the organic acid in the aqueous solution is preferably in the range of 0.01 to 2% by weight, preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0.5% by weight, based on the total weight of the aqueous solution; c) Mix the solutions prepared in steps a) and b) and mix at a temperature of 4 to 78°C, preferably 10 to 50°C, for 4 hours to 1 week; d) removing at least some of the alcohol from the mixture from step c), and then cooling the concentrated mixture to a temperature of 20 to -25°C; e) Store the cooled mixture from step d) until it reaches a viscosity of 10 to 75 Pa·s; f) A step of spinning the mixture from step e) into continuous fibers, The silane compound crosslinking occurs between steps c) to f), and at least a portion of the organic or inorganic acid is incorporated into the resulting network and / or contributes to the crosslinking. A fiber or fiber fragment according to any one of claims 1 to 7, characterized in that it can be manufactured by a method.

9. The fiber or fiber fragment according to any one of claims 1 to 8, characterized in that the spinning is preferably carried out by electrospinning at a voltage of 1 to 30 kV and a distance of 0.2 to 30 cm, particularly preferably at a voltage of 6 to 30 kV and a distance of 10 to 30 cm, or at a voltage of 1 to 5 kV and a distance of 0.2 to 2 cm, with the addition of a spinning aid, or by pressure spinning at a pressure of preferably 10 to 60 bar, particularly preferably 20 to 40 bar.

10. The fiber or fiber fragment according to any one of claims 1 to 9, characterized in that at least one further substance is contained in the sol, preferably in a pure form or in an encapsulated form.

11. A nonwoven fabric comprising, or consisting of, the silicate-releasing fibers and / or fiber fragments described in any one of claims 1 to 10.

12. The nonwoven fabric according to claim 11, characterized in that the release of silicic acid can be initiated and / or promoted by contacting the nonwoven fabric with an aqueous solution which may preferably contain at least one further substance selected from the group consisting of cosmetic base materials, active ingredients, additives, auxiliary materials, or mixtures thereof.

13. Nonwoven fabric for cosmetic and / or medical use, The nonwoven fabric according to claim 11 or 12, particularly for use with respect to human or animal tissues and organ barriers, such as skin, mucous membranes, intestines, and / or hair or nail beds, in particular for strengthening the connective tissue of the skin, or in particular for treating connective tissue weakness, preferably of the skin and blood vessel walls, or tissue weakness such as skin diseases, preferably inflammatory and / or chronic skin diseases, acne, age spots, neurodermatitis, pressure ulcers, eczema, keratosis, psoriasis, dry skin, cellulitis, cellulite, etc.

14. The nonwoven fabric according to claim 13, characterized by being brought into contact with an aqueous solution and made to blend with the skin.

15. The nonwoven fabric according to claim 14, characterized in that the aqueous solution preferably has a pH of 3.7 to 9.0, more preferably 4.7 to 7.

5.

16. The aforementioned aqueous solution • Surfactants, especially ionic and nonionic surfactants, saponins, fatty acids, phospholipids, ceramides, • Penetration enhancers, especially phospholipids, polyethylene glycol, glycols, ceramides, dimethyl sulfoxides, pyrrolidones, alcohols, urea or terpenes, • Cosmetic active additives, especially vitamins, provitamins, amino acids, heparin, hyaluronic acid, collagen (derivatives), plant extracts, probiotics, enzymes, hydrates, fragrances, colorants, preservatives, emollients, abrasives / particles, micelles or liposomes The nonwoven fabric according to claim 14 or 15, characterized by comprising a further additive selected from the group consisting of the following.

17. A cosmetic composition comprising a fiber or fiber fragment according to any one of claims 1 to 10, or a nonwoven fabric according to any one of claims 11 to 16.

18. The cosmetic composition according to claim 17, which is in the form of creams, emulsions, lotions, gels and oils for skincare, face masks, makeup bases (liquids, pastes, powders), face powders, body powders, foot powders, cosmetic soaps, deodorant soaps, perfumes, lotions and colognes, bath additives and shower additives (salts, foams, oils, gels), hair removal products, deodorants and antiperspirants, hair dyes, hair weaving, hair straightening and hair styling products, hair styling products, hair cleansers (lotions, powders, shampoos), hair care products (lotions, creams, oils), styling aids (lotions, varnishes, Brilliantine), shaving products (including pre-care and after-care), makeup and makeup remover products, lip care products and cosmetics, dental care and oral care products, nail care products and cosmetics, external delicate zone care products, sunscreens, self-tanning products, skin whitening products, and wrinkle-improving products.

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