Plaster preparation, polymer film, spray plaster spraying device, method for producing polymer fiber web, polymer fiber web, and use of plaster preparation

Abstract

The present invention relates to a plaster preparation comprising at least one absorbent polymer composed of at least three monomer units, particularly a terpolymer comprising monomers selected from the group consisting of trimethylene carbonate, glycolide, lactide (particularly (D,L-lactide), p-dioxanone, ε-caprolactone, and / or butyrolactone), at least one readily evaporating organic solvent, and at least one propellant. The present invention further relates to a polymer film, a spray-plaster spraying device, a method for producing a polymer fiber web, a polymer fiber web, and uses of the plaster preparation.

Description

[Technical Field]

[0001] The present invention relates to a plaster preparation, a polymer film produced by spraying the plaster preparation, a spray plaster spraying device for producing a polymer film or a polymer fiber web, a method for producing a polymer fiber web, a polymer fiber web, and use of the plaster preparation.

[0002] Known in the prior art are conventional spray plasters, which comprise acrylate-based, silicone-based or polyurethane-based polymers, solvents such as ethyl acetate, and propellants such as dimethyl ether, hydrocarbons, fluorine-containing hydrocarbons, CO2, nitrogen or rare gases.The drawbacks of such spray plasters are, in particular, the physiological safety of the polymer, its insufficient flexibility, especially in the case of thin films, and / or its adhesion to skin or wound, and its insufficient water permeability, especially due to its high hydrophobicity.

[0003] EP 0 509 203 A1 aims to provide physiologically harmless polymers that can be used on the skin and do not have the drawbacks of known lactic acid and glycolic acid monomers and copolymers, which are usually applied in the form of a solution and, according to the disclosure of EP 0 509 203 A1, are inherently relatively hard and have low flexibility, so that sprayed films quickly become brittle and crack after evaporation of the solvent and have limited adhesion to the skin or wound surface.

[0004] In EP 0 509 203 A1, known polymers of lactide and ε-caprolactone are described as generally rigid thermoplastic resins suitable for producing, for example, containers, but which are not suitable for topical application.

[0005] EP 0 509 203 A1 discloses the use of copolymers composed of racemic lactide and ε-caprolactone, δ-valerolactone, racemic γ-decalactone or β-hydroxybutyric acid for the purpose of improvement, which are prepared by reacting these monomers with known metal carboxylates as initiators in a lactide to reactant molar ratio of about 95-70:5-30 at a temperature of about 150° C. for a period of about 16-48 hours. By way of example, a solution of a copolymer of D,L-lactide and ε-caprolactone in a molar ratio of 85:15 is disclosed, which can be packed into known pump sprays or aerosol sprays.

[0006] EP 1077073 aims to improve absorbable and physiologically harmless copolylactides. In this regard, EP 1077073 discloses that application to intact skin requires a copolylactide with high adhesion, flexibility and extensibility. According to EP 1077073, an important criterion for use on damaged skin is water vapor permeability, and according to EP 1077073, this copolymer is hydrophobic and has low permeability (<60 ml / h / m 2 ), the water vapor permeability cannot be achieved by this copolymer alone. According to the disclosure of EP 1077073, it is necessary to have a relatively high proportion of monomers in the reaction product or to add a hygroscopic / hydrophilic substance (e.g., glycerin), which initially leads to high values ​​of vapor permeability (>150 ml / h / m 2 ) is achieved, but decreases over time (corresponding to wound secretions).

[0007] EP 1077073 discloses copolymers of racemic lactide with the comonomers ε-caprolactone, δ-valerolactone, 1,4-dioxanone-2, or 1,3-dioxanone-2, in which the molar ratio of lactide / comonomer is 90-80 / 10-20, and the copolymers are polymerized at approximately 160°C in the presence of tin(II) diethylhexanoate as an initiator and a cocatalyst, and have glass transition temperatures of 30-43°C, molecular weights Mn of 15,000-50,000, and polydispersities Pn (Mw / Mn) of 1.2 to 2. In particular, copolymers of D,L-lactide and 1,3-dioxanone-2 (also known as trimethylene carbonate) and D,L-lactide and ε-caprolactone thus prepared are disclosed. According to the teaching of EP 1077073, a low viscosity results in a sticky consistency that should result in adhesion to the applied textile (e.g., bandage). In contrast, a copolymer with the same lactide / comonomer ratio but a higher viscosity would be less flexible, stiffer, more brittle, and less sticky, according to EP 1077073. The target viscosity of the copolymer according to the invention in EP 1077073 is 0.30 to 0.75, preferably 0.55 to 0.67.

[0008] The present invention aims to provide a polymer-based plaster preparation suitable for producing both a polymer film and a polymer fiber web, wherein the plaster preparation has a high viscosity and the polymer film or polymer fiber web has high extensibility at a small thickness, and both the polymer film and the polymer fiber web exhibit good adhesion to skin (human or animal, dry or wet) or wounds, and high water vapor permeability, particularly water vapor permeability equivalent to that of skin (human or animal), is achieved without the need for additional additives. Furthermore, it is desirable to provide methods for producing the polymer film, the spray plaster spraying device, and the polymer fiber web.

[0009] The problem with plaster preparations is solved according to the invention by a plaster preparation having the features of claim 1. The polymer film according to the invention has the features set forth in claim 16. The spray plaster spraying device according to the invention is set forth in claim 22, the method for producing a polymer fiber web is set forth in claim 23, and the polymer fiber web is set forth in claim 24. Uses are set forth in claims 26 and 27. Advantageous configurations with useful developments of the invention are set forth in the respective dependent claims.

[0010] The plaster preparation comprises at least one absorbent polymer composed of at least three, in particular different, monomers, in particular a polymer comprising monomers selected from the group consisting of trimethylene carbonate, glycolide, lactide, in particular (D,L-lactide), p-dioxanone, ε-caprolactone and / or butyrolactone, and at least one readily evaporating organic solvent.

[0011] If the plaster preparation is a spray plaster preparation, it preferably comprises at least one propellant.

[0012] Surprisingly, the plaster preparations according to the invention allow for high intrinsic viscosities, where high viscosity in the sense of the invention means a viscosity of >0.75 dL / g, usually >1 dL / g. (According to the present application, viscosity is determined at 25°C with 1 g of polymer per ml of chloroform.) The polymer films and polymer fiber webs which can be produced using the plaster preparations according to the invention or spray plaster preparations have a small thickness (film: 10-50 μm; web: 80-200 μm) and are sufficiently strong for the intended purpose, providing good adhesion to the skin and wounds, good stretchability (film: 200-1500%, web: 150-200%), and different strengths (film: 0.4-15 N / mm). 2 , Web: 0.6~0.8N / mm 2 ), and good, especially suitable for the skin (human or animal, dry or wet), water vapor permeability (film: 15-80 g / m 2 / h, web 80-120g / m 2 / h). Thus, the plaster preparation according to the invention can be applied externally in a very thin form, in particular as a spray plaster preparation. The aforementioned adhesion is such that the polymer film or web cannot be peeled off from the application site without being destroyed. The polymer film or web can only be peeled off by hand in small pieces each time. In contrast, during washing / showering and when the skin is carefully dried, the polymer film or web remains intact and adheres tightly. The plaster preparation can also be applied to the application site (skin / wound) to which the plaster is to be applied as a pump spray or with a brush, for example.

[0013] In the sense of the present invention, an absorbable polymer is a polymer prepared by polymerization of at least three different monomers, and both the polymer and the monomers used are substantially hydrolytically degradable in vivo and in vitro. The polymer and its degradation products are medically harmless and non-allergenic. The monomers are further metabolized in vivo via the citric acid cycle or fatty acid metabolism.

[0014] Suitable polymers include, inter alia, trimethylene carbonate, glycolide, lactide, especially D,L-lactide, p-dioxanone, ε-caprolactone and / or butyrolactone.

[0015] In a preferred embodiment, the absorbable polymer comprises trimethylene carbonate, particularly lactide, especially D,L-lactide, ε-caprolactone, and trimethylene carbonate; particularly preferably, the terpolymer is composed of lactide, especially D,L-lactide, ε-caprolactone, and trimethylene carbonate. This has the added advantage that polymers with glass transition temperatures between 22°C and 37°C easily conform to the shape of the wound, promoting wound healing. The continuous release of monomers and the degradation of the polymer into monomers promote wound healing over a longer period of time. This effect can be enhanced by reapplication.

[0016] The polymer preferably comprises 60-90% by weight of D,L-lactide, 5-35% by weight of ε-caprolactone, and 5-35% by weight of trimethylene carbonate, and more particularly 70-85% by weight of D,L-lactide, 5-20% by weight of ε-caprolactone, and 5-20% by weight of trimethylene carbonate. This composition is particularly advantageous because it results in an amorphous structure that provides elastic and plastic behavior. Therefore, mobility is maintained in wounds, such as joints, covered with the plaster.

[0017] In a further embodiment, the polymer preferably has an intrinsic viscosity of 0.3 dl / g to 2.5 dl / g, in particular 0.75 to 1.6, very particularly preferably 0.9 to 1.6 dl / g (viscosity in this application measured at 1 mg of polymer per ml of chloroform at 25° C.), which has the additional advantage that the resulting film is mechanically sufficiently stable while still exhibiting the desired degradation properties.

[0018] In a further embodiment, the polymer preferably has a monomer content of 0.5-10% by weight, in particular 3-8% by weight, which has the added advantage that the release of the monomer accelerates wound healing and the film exhibits the desired plastic-elastic behavior, and the continuous release of the monomer over a long period of time (over several days) accelerates wound healing.

[0019] According to a further aspect of the present invention, the plaster preparation can further comprise at least one additional absorbable polymer, in particular poly-ε-caprolactone, polylactide, polyglycolide, polyethylene glycol, and / or at least one non-absorbable polymer, in particular one from the group consisting of polyacrylates and polyurethanes, the non-absorbable polymer being mixed in a preferred proportion of 1 to 50% relative to the terpolymer, in particular as a blend, which has the additional advantage of improving flowability (during film formation) while increasing adhesion.

[0020] Easily evaporating organic solvents within the meaning of the present invention are organic solvents having an evaporation number (VD) according to DIN 53170 of less than 35, in particular less than 10. Suitable organic solvents are in particular selected from the group consisting of acetone, methyl acetate, ethyl acetate, halogenated hydrocarbons, cyclopentane and / or mixtures thereof, with particular preference given to ethyl acetate, methyl acetate and / or acetone. Furthermore, the organic solvents DMSO and N-pyrrolidone are suitable.

[0021] The absorbent polymer may be present in a dissolved state in an organic solvent.

[0022] Propellants in the sense of the present invention are gaseous or gas-generating compounds that are used to transport and / or atomize other substances, in particular other liquids and / or gases. Suitable propellants are, for example, dimethyl ether, methane, ethane, propane, butane, pentane, halogenated hydrocarbons with a low boiling point (<50°C), noble gases, air and / or CO2.

[0023] In a further embodiment of the invention, the plaster preparation according to the invention can consist of a composition of 5-25% by weight of an absorbent polymer composed of at least three (different) monomer units and 75-95% by weight of an organic solvent.

[0024] When the plaster preparation is implemented as a spray plaster preparation, in a further embodiment of the present invention, the spray plaster preparation may consist of a composition of 2.8 to 7 wt. % of an absorbent polymer composed of at least three (different) monomer units, 31.5 to 65 wt. % of an organic solvent, and 30 to 64 wt. % of a propellant.

[0025] According to a further aspect of the invention, the plaster preparation may further comprise at least one bactericide, in particular an antibacterial active substance, in particular polyhexanide, phenoxyethanol, iodine, peroxide and / or silver, in which case the plaster preparation may comprise the bactericide in a weight proportion of 0.05% to 5% by weight, in particular 0.1% to 2% by weight.

[0026] Surprisingly, it has been found that the addition of a bactericidal agent to a plaster preparation can further increase the extensibility of the polymer film that can be produced or that has been produced therefrom. For example, by adding phenoxyethanol to a plaster preparation at a weight ratio of 1% by weight, a polymer film with an extensibility of up to 1500% can be produced. In this case, the polymer film can be particularly easily repeatedly deformed, and even after a stretch of, for example, 500%, it can spontaneously elastically deform and return to its original shape completely or almost completely. The polymer film that can be produced / produced from the plaster preparation has a low elastic modulus, making it completely or almost impossible for the wearer to feel the polymer film when applied to the skin. This makes it particularly comfortable to wear, especially when applied near joints. Furthermore, even if the polymer film is repeatedly stretched due to the movements of the person / animal wearing it, undesirable peeling of the polymer film from the application site can be more effectively prevented. At the same time, the durability of the plaster preparation can be improved, and the advantageous antibacterial properties of the polymer film produced therefrom can be realized.

[0027] The further additives may be cooling, soothing, caring or viricidal.

[0028] According to a further aspect of the invention, the plaster preparation may further comprise biologically active additives, such as antibacterial active substances, hemostatic substances, cytokines, growth factors, in particular TGF-β, anesthetics, and / or biologically inactive additives, such as UVA and / or UVB filters, dyes, further polymers, adhesives. The invention also relates to polymer films produced by spraying the plaster preparation according to the invention.

[0029] The polymer film produced using the plaster preparation according to the present invention, in particular the spray plaster preparation, has a small thickness (10-50 μm) and exhibits good adhesion to skin, hair and wounds, good extensibility (200-1000%) and high strength (0.4-15 N / mm), which is sufficient for the intended purpose. 2 ), as well as good, particularly skin-compatible water vapor permeability (15-80 g / m 2 / h) Therefore, the polymer film according to the present invention is highly comfortable to wear when applied to the skin and promotes wound healing through the release of lactate.

[0030] Advantageously, in one embodiment, the polymer film has a monomer content of <10% by weight, which has the additional advantage of achieving the desired mechanical properties for use as a plaster without the brittleness associated with plastic and elastic behavior.

[0031] In one embodiment, the polymer coating preferably has a strength of 1.5 to 1000 N / mm 2 , especially 1.7 to 450N / mm 2 This has the added advantage that the film does not exhibit stiffness, which promotes good adhesion to the skin.

[0032] In one embodiment, the polymer coating has an elongation of 100-1500%, in particular 250-1000%, which has the added advantage that the material is flexible enough to cover geometrically difficult body parts, especially in the joint area.

[0033] The polymer coating advantageously has a strength of 0.1 to 30 N / mm 2 , especially 1 to 20 N / mm 2 This has the added benefit of preventing the material from tearing, even when applied near joints or during movement.

[0034] According to a further advantageous embodiment, the polymer film has a thickness (measured after drying) of 5 to 30 μm. A polymer film of this thickness is particularly comfortable to wear and allows for better air and moisture exchange, which promotes wound healing.

[0035] The present invention also relates to a spray plaster spraying device for spraying the spray plaster preparation according to the present invention, which comprises a housing, in particular a cylindrical housing with a longitudinal axis, and a spray head for initiating the spraying process. The housing comprises a reservoir for the spray plaster preparation and a propellant channel with a diameter d1 for the propellant of the spray plaster preparation. In a first region, the propellant channel extends as a standpipe in the longitudinal direction of the housing, and in a second region within the spray head, it extends radially at an angle between the geodesic front surface of the standpipe and the spray opening of the spray head.

[0036] The second region has a diameter d2 smaller than the diameter d1 of the first region. The second region (d2) opens into a mixing region having a diameter d3. The mixing region radially connects the second region to the spray opening. A reservoir channel having a diameter d4 extends in the longitudinal direction and opens into the mixing region, with its diameter d4 being larger than the diameter d3. The spray opening has an expanding cone-shaped relief region having a maximum diameter d5, which extends between the mixing region and the spray opening.

[0037] The spray plaster spraying device according to the present invention has the advantage that the spray plaster preparation according to the present invention is surprisingly also suitable for producing polymer fibers that can be applied as a polymer fiber web to a surface, in particular to the skin (human or animal, dry or wet) or a wound by spraying with the spray plaster spraying device.This has the advantage that the plaster preparation according to the present invention can be applied to a wound, in particular a chronic wound, as a fiber-containing planar structure in order to alleviate wound pain and reduce the risk of maceration and / or infection in the wound, in particular a chronic wound.Furthermore, the polymer fiber web according to the present invention can be advantageously used to stimulate angiogenesis in wounds, in particular chronic wounds, and / or to build up the epidermis and dermis in the wound.

[0038] The present invention also relates to a method for producing a polymer fiber web comprising polymer fibers, in which a spray plaster preparation according to the present invention is sprayed by means of a spray plaster spraying device according to the present invention, the propellant of the spray plaster preparation is forced into a mixing region of a propellant channel at high speed, a polymer composed of at least three monomers of the spray plaster preparation and a solvent of the spray plaster preparation are transported by the channel (from a reservoir) to the mixing region and mixed with the propellant flowing at high speed, and the resulting mixture is transported to a pressure release chamber of a spray opening, in which the solvent evaporates upon exiting the spray opening to form polymer fibers, and the polymer fiber web comprising the polymer fibers is applied to a surface, in particular a human or animal skin surface, in particular a wound.

[0039] The thickness of the polymer fiber web produced can be selected as needed by selecting the spray time and repeating the spray process. The fiber thickness of the polymer fibers forming the web can be affected not only by the pressure and polymer concentration in the spray plaster spraying device, but also by the maximum opening width (= maximum inner diameter) of the spray opening. The higher the propellant pressure and the smaller the maximum opening width, the smaller the fiber thickness, and vice versa.

[0040] The present invention further relates to a polymer fiber web produced by the method according to the present invention. The polymer fiber web according to the present invention has the advantage that the fibers can surprisingly optimally adapt to the wound base. Furthermore, the polymer fiber web according to the present invention is substantially solvent-free, which allows for less painful treatment when spraying the fibers. Due to the web structure, it is also possible to better absorb wound fluid and transport wound secretions to the outside, which is particularly advantageous in the case of wounds with high secretions. Furthermore, the breathability of the application site to which the polymer fiber web is applied can be improved.

[0041] According to one embodiment, the polymer fiber web according to the present invention preferably has a density of 80 to 200 ml / m 2 / h. In this case, the polymer fiber web according to the invention has the advantage that the fluid in erosive wounds can be drained more easily.

[0042] The present invention also relates to the use of the plaster preparation according to the invention for the topical treatment of human or animal skin, in particular for wound treatment of epidermal and dermal wounds, in particular abrasions, cuts, burns and chronic wounds, in particular ulcerative wounds, in particular pressure-induced ulcers (pressure ulcers), arterial ulcers, venous ulcers, mixed arterial-venous ulcers, leg ulcers, arterial leg ulcers, venous leg ulcers, ulcers in diabetic foot syndrome and post-traumatic ulcers.

[0043] The present invention also relates to the use of the plaster preparation according to the invention for application to skin redness, especially sunburn, for sun protection, in cosmetic applications, especially for camouflage, or as an absorbent adhesive, which may contain suitable dyes for camouflage.

[0044] When used as a sunscreen, known and customary UVA and UVB filters are added to the plaster preparation itself.

[0045] Further advantages of the present invention will become apparent from the specification and drawings. The illustrated and described embodiments are not to be understood as an exhaustive list, but are of an exemplary nature for the explanation of the invention.

[0046] In each of the following examples, a standard spray head (= "standard nozzle") with the designation "Kosmos" and equipped with a valve PV22210-200149 from Precision Dispensing Solutions Europe GmbH was used. The diameters indicated in each case refer to the maximum opening width of the standard nozzle (d5 in Figure 1 of the drawings).

[0047] The values ​​in parentheses are understood to be weight percentages in weight percent. Note that the viscosities in this application are measured at 1 mg of polymer per ml of chloroform at 25° C.

[0048] Example 1 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) Polymer: 7% by weight Ethyl acetate: 63% by weight Dimethyl ether: 30% by weight The mixture was placed in a pressure can (standard nozzle with a diameter of 0.91 mm) as shown in Figure 1 and sprayed at a distance of approximately 10 cm and a pressure of approximately 5.1 bar (20°C). The thickness was approximately 12 μm and the water vapor transmission rate was approximately 30 ml / m. 2 / h of a transparent polymer film was formed. The longer the spray time, the greater the film thickness. At a film thickness of 40 μm, the water vapor permeability was approximately 18 ml / m 2 / h.

[0049] When sprayed onto a damp piece of flesh conditioned to 37°C, within about 1-2 minutes a polymer film formed that was sufficiently adhesive (it didn't slip and stayed in place when moved) to be used as a wound plaster.

[0050] When applied to moist, tempered meat, the polymer coating could be peeled off with tweezers after approximately 1-2 minutes.

[0051] They also formed a film on human skin (both dry and wet) that did not slip and remained in place, adhering tightly even when moving.

[0052] The uniaxial tensile tests gave the following mechanical values: modulus of elasticity (Young's modulus) in the linear range (DIN 53457), tensile strength as tensile stress at break (N / mm 2 ) and the elongation (%) at which each stress occurs. Measurements were performed at 20°C.

[0053] Young's modulus: approx. 250N / mm2 Elongation rate: Approximately 350% Tensile strength: approx. 7N / mm 2

[0054] This polymer film exhibits sufficient strength for use as a plaster even at a small thickness, has good adhesion to skin and wounds, and has a particularly high water vapor permeability comparable to that of skin without the need for additional additives.

[0055] Example 2 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) Polymer: 10% by weight [8% by weight] Ethyl acetate: 90% by weight [92% by weight] The mixture was placed in a pressurized can equipped with a standard nozzle (diameter 0.91 mm) according to Figure 1 and sprayed with compressed air at a pressure of approximately 5 bar at a distance of approximately 10 cm. The thickness was approximately 12 μm [10 μm], and the water vapor transmission rate was approximately 25 ml / m. 2 / h[40ml / m 2 / h]. The following mechanical values ​​were obtained from the uniaxial tensile test: Young's modulus: approx. 700N / mm2 Elongation rate: Approximately 300% Tensile strength: approx. 11N / mm 2

[0056] This polymer film exhibits sufficient strength for use as a plaster even at a small thickness, has good adhesion to skin and wounds, and has a particularly high water vapor permeability comparable to that of skin without the need for additional additives.

[0057] Example 3 A spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) and a purple dye, "D&C Violet No. 2," to visualize the spray area. Polymer: 3.6% by weight Purple dye: 0.0045% by weight Ethyl acetate: 41.3955% by weight Dimethyl ether: 55% by weight was placed in a pressure can equipped with a standard nozzle (diameter 0.91 mm) according to Figure 1 and sprayed at a distance of 10 cm and a pressure of approximately 5.1 bar (20 °C). The thickness was approximately 15 μm and the water vapor transmission rate was approximately 41 ml / m 2 A purple, but still transparent polymer film was formed at 1000 kJ / h. The following mechanical values ​​were obtained from the uniaxial tensile test: Young's modulus: approx. 616 N / mm 2 Elongation rate: Approximately 348% Tensile strength: approx. 8.7N / mm 2

[0058] This polymer film exhibits sufficient strength for use as a plaster even at a small thickness, has good adhesion to skin and wounds, and has a particularly high water vapor permeability comparable to that of skin without the need for additional additives.

[0059] Example 4 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) Polymer: 3.5% by weight Ethyl acetate: 31.5% by weight Dimethyl ether: 65% by weight was placed in a pressure can equipped with a standard nozzle (diameter 0.91 mm) according to Figure 1 and sprayed at a distance of approximately 10 cm and a pressure of approximately 5.1 bar (20 °C). The thickness was approximately 17 μm and the water vapor transmission rate was approximately 62 ml / m 2 / h, a transparent polymer film was formed. A very tightly adherent film was also formed on human skin (dry and wet). Due to the high propellant gas content, many small bubbles were generated during spraying, but a polymer film was still formed. The following mechanical values ​​were obtained from uniaxial tensile tests: Young's modulus: approx. 416N / mm 2 Elongation rate: Approximately 355% Tensile strength: approx. 7.5N / mm 2

[0060] This polymer film exhibits high strength at low thickness, has good adhesion to skin and wounds, and has a particularly high water vapor transmission rate comparable to that of skin without the need for additional additives.

[0061] Example 5 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) and cyanoacrylate Polymer: 3.6% by weight Cyanoacrylate: 0.045% by weight Ethyl acetate: 41.355% by weight Dimethyl ether: 55% by weight was placed in a pressure can equipped with a standard nozzle (diameter 0.91 mm) according to Figure 1 and sprayed at a distance of approximately 10 cm and a pressure of approximately 5.1 bar (20 °C). The thickness was approximately 14 μm and the water vapor transmission rate was approximately 29 ml / m 2 A transparent polymer film was formed with a viscosity of 1000 psi / h. It also formed a film that adhered very well to human skin (dry and wet). The following mechanical values ​​were obtained from uniaxial tensile tests: Young's modulus: approx. 248N / mm 2 Elongation rate: Approximately 486% Tensile strength: approx. 14.3N / mm 2

[0062] This polymer film exhibits high strength at low thickness, has good adhesion to skin and wounds, and has a particularly high water vapor transmission rate comparable to that of skin without the need for additional additives.

[0063] Example 6 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) Polymer: 13% by weight in ethyl acetate: 87% by weight Polymer: 13% by weight: 87% by weight in a 1:1 mixture of ethyl acetate / acetone Polymer: 16 wt% in acetone: 86 wt% was placed in a pressure canister with a spray head according to the invention according to Figure 1 and sprayed at a distance of about 30 cm and an air pressure of about 5 bar. Whitish polymer fibers were formed with an average thickness of about (A) 850 nm, (B) 1 μm, and (C) 2 μm. These polymer fibers formed a polymer fiber web according to the invention, which was also obtained with a standard nozzle (0.91 mm diameter) at low pressure (about 1 bar). This polymer fiber web adhered well to human skin. A polymer fiber web was formed that adhered very well to human skin (both dry and wet).

[0064] The polymer web (A) has a flow rate of about 111 ml / m 2 The uniaxial tensile test gave the following mechanical values: Young's modulus: approx. 21N / mm 2 Elongation rate: Approximately 184% Tensile strength: approx. 0.82N / mm 2

[0065] This polymer web exhibits high strength at a thickness of only 120 μm, has good adhesion to skin and wounds, and has a particularly high water vapor transmission rate comparable to that of skin without the need for further additives.

[0066] Example 7 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) Polymer: 15% by weight: 85% by weight in ethyl acetate Polymer: 17% by weight in ethyl acetate: 83% by weight Polymer: 19% by weight in ethyl acetate: 81% by weight The mixture was placed in a pressurized canister with a spray head according to the invention according to Figure 1 and sprayed at a distance of about 30 cm at an ambient pressure of about 8 bar. Whitish fibers were formed with an average thickness of about (A) 900 nm, (B) 1 μm, and (C) 2.5 μm. A polymer fiber web according to the invention was formed. This polymer fiber web adhered to human skin in a manner suitable for use as a plaster or skin protectant.

[0067] Example 8 Spray plaster preparation containing poly-D,L-lactide-trimethylene carbonate-ε-caprolactone (75 / 15 / 10) Polymer: 3.6% by weight Phenoxyethanol: 0.45% by weight Ethyl acetate: 40.95% by weight Dimethyl ether: 55% by weight was placed in a pressure can equipped with a standard nozzle (0.91 mm) according to Figure 1 and sprayed at a distance of approximately 10 cm and a pressure of approximately 5.1 bar (20 °C). The thickness was approximately 15 μm and the water vapor transmission rate was approximately 37 ml / m 2 / h, a transparent polymer film was formed. A very tightly adherent film was also formed on human skin (dry and wet). Due to the high propellant gas content, many small bubbles were generated during spraying, but a polymer film was still formed. The following mechanical values ​​were obtained from uniaxial tensile tests: Young's modulus: approx. 4N / mm 2 Elongation rate: Approximately 770% Tensile strength: approx. 2.6N / mm 2

[0068] Surprisingly, this polymer film exhibits very high extensibility at low thickness, good adhesion to skin and wounds, and in particular a high water vapor transmission rate comparable to that of skin without the need for further additives. [Brief explanation of the drawings]

[0069] [Figure 1] 1 is a diagram showing a schematic structure of a plaster spraying device according to an embodiment; [Figure 2] FIG. 1 shows an image of polymer fibers of a polymer fiber web produced according to Example 5, in which the polymer fibers were produced from plaster preparations (A) and (C) by spraying with a plaster spraying device according to the present invention. [Figure 3] 2 shows scanning electron microscope images of polymer fibers of polymer fiber webs produced from plaster preparations (A), (B) and (C) according to Example 5 by the plaster spraying device according to FIG. 1. FIG. [Figure 4] FIG. 1 shows a scanning electron microscope image of a polymer fiber web according to Example 6 produced by a spray fiber spraying apparatus according to the present invention.

[0070] In the drawings, identical or similar components are respectively provided with the same reference numerals. The embodiments shown in the drawings are of an exemplary nature for the purpose of explaining the invention and are not to be understood as limiting.

[0071] FIG. 1 shows a schematic diagram of the structure of a pressurized spray plaster spraying device 10 for spraying the plaster preparation according to the present invention, in particular for producing a polymer fiber web of the plaster preparation according to the present invention by the method for producing a polymer fiber web according to the present invention.

[0072] The spray plaster spray device 10 comprises a housing 12 having a movably arranged spray head 14 for initiating the spraying process. The housing 12 may be cylindrical, in particular, but may also have another shape. The housing 12 has a longitudinal axis L and comprises a reservoir 16 for the plaster preparation and a propellant channel 18 for the propellant T of the plaster preparation. The propellant channel 18 extends in a first region 20 in the direction of the longitudinal axis L of the housing as a standpipe 22 and in a second region 24 in the spray head 14 at an angle in the radial direction between the geodesic front surface of the standpipe 22 and the spray opening 26 of the spray head 14. The first region 20 has an inner diameter d1. The second region 24 has an inner diameter d2 that is smaller than the diameter d1 of the first region 20.

[0073] The second region 24 opens into a mixing region 28 having a diameter d3 that is advantageously smaller than or equal to the diameter d2. The mixing region 28 radially follows the second region 24 and fluidly connects the second region 24 with the spray openings 26.

[0074] The channel 30 of the reservoir 16, having a diameter d4, extends axially and opens into the mixing region 28. Here, the diameter d4 is larger than the diameters d3 and d2. By activating the spray head, a fluid connection is formed between the propellant T stored in the housing 12 and the spray opening 26. The remaining plaster preparation disposed in the housing 12 is drawn into the mixing region 28 by a suction force below ambient pressure mediated by the outflowing propellant.

[0075] The spray opening 26 has an expanding conical pressure relief area 32 which extends radially with respect to the longitudinal axis L between the mixing area 28 and the spray opening 26. The spray opening has a maximum inner diameter d5 (= opening width).

[0076] FIG. 2 shows a photographic image of a polymeric fiber web 100 comprising a plurality of polymeric fibers 102 produced according to Example 5 described above.

[0077] - Plaster preparation A shown in the top row of the image series, and - Plaster preparation C shown in the bottom row of the image group was sprayed onto a glass plate (not visible in FIG. 2) at a spray distance of 30 cm using a spray fiber spraying device 10 according to the present invention as shown in FIG. 1 to produce polymer fibers 102. The polymer fibers 102 of the polymer fiber web 100 are clearly visible.

[0078] 3 shows a scanning electron microscope image of polymer fiber webs 100 each containing polymer fibers 102 produced according to Example 5. The polymer fibers 102 were produced by spraying plaster preparations A, B, and C using the spray fiber spraying device 10 according to FIG.

[0079] The left image shows polymer fibers 102 produced from plaster preparation A. The center image shows polymer fibers 102 from plaster preparation B, and the right image shows polymer fibers 102 from plaster preparation C. All images are on a scale of 50 μm, i.e., a length of 1 cm in the drawing corresponds to 50 μm in real life. The polymer fibers 102 exhibit shape-bonding through entanglement, cohesion, and / or adhesion, which is typical of a web as a planar structure.

[0080] FIG. 4 shows a scanning electron microscope image of the polymer fiber web 100 according to Example 6 described above, which was produced using the spray fiber spraying device 10 according to the present invention according to FIG. 1. The scale corresponds to 50 μm. Each polymer solution was sprayed at an internal pressure of approximately 8 bar in the spray fiber spraying device 10. The polymer concentration was varied. Figure A shows the polymer fiber web 100 of solution A, Figure B shows the polymer fiber web 100 of solution B, and Figure C shows the polymer fiber web 100 of solution C. The polymer fibers 102 or polymer fiber web 100 exhibit sufficient adhesion to human skin for wound closure.

Claims

1. 1. A plaster preparation comprising: a. at least one absorbent polymer comprised of at least one terpolymer comprising monomers selected from the group consisting of trimethylene carbonate, glycolide, lactide, p-dioxanone, ε-caprolactone, and / or butyrolactone; b. at least one readily evaporating organic solvent, wherein the readily evaporating organic solvent is an organic solvent having an evaporation number (VD) according to DIN 53170 of less than 35; Including, The plaster preparation is a spray plaster preparation (16) containing at least one propellant T, The propellant T is dimethyl ether, methane, propane, butane, pentane, butene, low-boiling halogenated hydrocarbons, inert gases, air and / or CO ２ wherein the low boiling halogenated hydrocarbon boils at a temperature below 50°C; the plaster preparation further comprises at least one additional absorbent polymer; A plaster preparation, wherein the terpolymer has a monomer content of 0.5 to 10% by weight.

2. 2. The plaster preparation of claim 1, wherein the absorbent polymer comprises lactide, ε-caprolactone, and trimethylene carbonate.

3. 3. The plaster preparation according to claim 1, wherein the absorbent polymer comprises 60 to 90% by weight of D,L-lactide, 5 to 35% by weight of ε-caprolactone, and 5 to 35% by weight of trimethylene carbonate.

4. 4. The plaster preparation of claim 3, wherein the absorbent polymer has an intrinsic viscosity of 0.5 to 2.5 dl / g.

5. 5. The plaster preparation according to claim 1, wherein the terpolymer has a monomer content of 3 to 8% by weight.

6. 6. The plaster preparation according to claim 1, further comprising at least one further absorbable polymer and / or at least one non-absorbable polymer selected from the group consisting of poly-ε-caprolactone, polylactide, polyglycolide, polyethylene glycol, poloxamer.

7. 7. The plaster preparation according to claim 1, further comprising at least one additional absorbable polymer and / or at least one monomer selected from the group consisting of poly-ε-caprolactone, polylactide, polyglycolide and polyethylene glycol, which monomer polymerizes on the skin to a non-absorbable polymer, resulting in a polymer blend of absorbable and non-absorbable polymers.

8. 2. The plaster preparation according to claim 1, wherein the organic solvent is selected from the group consisting of acetone, methyl acetate, ethyl acetate, halogenated hydrocarbons, DMSO, N-pyrrolidone, cyclopentane and / or mixtures thereof.

9. 2. The plaster preparation of claim 1, wherein the terpolymer is present in a dissolved state in the organic solvent.

10. 2. The plaster formulation of claim 1, wherein the plaster formulation comprises 2.8 to 7% by weight of the terpolymer, 31.5 to 64.4% by weight of the organic solvent, and 30 to 65% by weight of the propellant.

11. 11. The plaster preparation according to any one of claims 1 to 10, wherein the plaster preparation further comprises at least one bactericide.

12. 12. The plaster preparation according to claim 1, further comprising UVA and / or UVB filters, cytokines, growth factors, local anesthetics, hemostatic or antibacterial active substances, and / or biologically inactive additives.

13. 13. A spray plaster spraying device (10) for spraying a plaster preparation according to any one of claims 1 to 12, said spray plaster spraying device (10) comprising a housing (12) having a longitudinal axis (I) and a spray head (14) for initiating the spraying process, said housing (12) comprising: The reservoir (16) of the plaster preparation and the propellant of the plaster preparation have a diameter d １ and a propellant channel (18) The propellant channel (18) extends in a first region (20) as a standpipe (22) in the axial direction of the housing, and in a second region (24) in the spray head (14) at an angle in the radial direction between the geodesic front face of the standpipe (22) and a spray opening (26) of the spray head (14), The second region (24) has a diameter d １ Diameter d smaller than ２ and The second region (24) has the diameter d ２ Diameter d smaller than ３ and opening into a mixing region (28) having the mixing region (28) is radially contiguous with the second region (24) and connects the second region (24) with the spray openings (26); Diameter (d ４ The channel (30) of the reservoir (16) having the diameter (d ４ ) is the diameter d ３ and the spray opening (26) has an expanding cone-shaped widening pressure relief area (32), which extends radially between the mixing area (28) and the spray opening (26).

14. A method for producing a polymer fiber web (100) containing polymer fibers (102), comprising spraying a spray plaster preparation according to any one of claims 1 to 9 using a spray plaster spraying device (10) according to claim 13, and forcing the propellant T of the spray plaster preparation into the mixing region (28) of the propellant channel (18) at high speed; The terpolymer of the spray plaster preparation and the solvent of the spray plaster preparation (16) are transported to the mixing region (28) through a channel (34) and mixed with the propellant T flowing at high velocity; The resulting mixture is transported to a pressure relief chamber (34) of the spray orifice (26), whereupon the solvent evaporates upon exiting the spray orifice (26) to form polymer fibers.

15. The polymer fiber web has a thickness of 80 to 200 g / m ２ 15. The method of claim 14, having a water vapor transmission rate of 1 / 2 h.

16. 13. A plaster preparation according to any one of claims 1 to 12 for use in the topical treatment of human or animal skin.

17. 13. A plaster preparation according to any one of claims 1 to 12 for external use in the treatment of reddened skin, for sun protection, for cosmetic purposes or as an absorbent adhesive.

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