EP4232105A1

EP4232105A1 - Plaster composition, polymer film, spray plaster spray device, method for producing a polymer fiber nonwoven material, polymer fiber nonwoven material, and uses of the plaster composition

Info

Publication number: EP4232105A1
Application number: EP21823564.6A
Authority: EP
Inventors: Heinrich Planck; Erhard Müller; Svenja Reimer; Christian PLANCK; Lisa Lang
Original assignee: Polymedics Innovations GmbH
Current assignee: Polymedics Innovations GmbH
Priority date: 2020-12-03
Filing date: 2021-12-03
Publication date: 2023-08-30
Also published as: JP2023551570A; MX2023006610A; US20230302193A1; DE102020215294A1; KR20230116854A; WO2022117842A1

Abstract

The invention relates to a plaster composition comprising at least one resorbable polymer made of at least three monomer units, in particular a terpolymer, comprising monomers selected from the group consisting of trimethylene carbonate, glycolide, lactide, in particular (DL-lactide), p—dioxanone, ε- caprolactone and/or butyrolactone, at least one readily vaporizable organic solvent, and at least one propellant. The invention additionally relates to a polymer film, to a spray plaster spray device, to a method for producing polymer fiber nonwoven materials, to a polymer fiber nonwoven material, and to uses of the plaster composition.

Description

Plaster preparation, polymer film, spray plaster spray device, method for producing a polymer nonwoven fabric, polymer nonwoven fabric and uses of the plaster preparation

The invention relates to a plaster preparation, a polymer film produced by spraying the plaster preparation, a spray plaster spray device for producing a polymer membrane or a polymer fiber fleece, a method for producing the polymer fiber fleece, a polymer fiber fleece and uses of the plaster preparation.

Conventional spray plasters comprising polymers based on acrylate, silicone or polyurethane, a solvent such as ethyl acetate and a propellant such as dimethyl ether, hydrocarbons containing fluorine Hydrocarbons, CO2, nitrogen or noble gases are known from the prior art. Disadvantages of such spray plasters include the physiological harmlessness of the polymers, their insufficient flexibility, particularly in the case of thin films, and/or adhesion to skin or wounds, and insufficient water permeability, particularly due to high hydrophobicity.

EP 0 509 203 A2 aims to provide physiologically harmless polymers that can be used on the skin without the disadvantages of known mono- and copolymers of lactic acid and glycolic acid. The known mono- and copolymers are usually applied in solutions and, according to the disclosure of EP 0 509 203 A2, are inherently relatively hard and not very flexible, so that sprayed-on films quickly become brittle and cracked after the solvent has evaporated and only have limited adhesion to the skin or wound surface.

Known polymers of lactide and s-caprolactone are described in EP 0 509 203 A2 as generally stiff thermoplastics which are suitable, for example, for the production of containers but are unsuitable for topical application.

EP 0 509 203 A2 discloses the use of copolymers of racemic lactide and ε-caprolactone, δ-valerolactone, racemic γ-decalactone or β-hydroxybutyric acid as an improvement, the copolymers being produced by reacting the monomers in a molar ratio of lactide to reactant of about 95 to 70 to 5 to 30 with the addition of metal carboxylates known per se as initiators at temperatures of about 150° C. for a period of about 16 to 48 hours. As an example, a solution of a D,L-lactide and s-caprolactone copolymer in a molar ratio of 85 to 15 is disclosed, which can be filled into known pump sprays or aerosol sprays.

EP 1 077 073 B1 aims to improve resorbable, physiologically harmless copolylactides. In this regard, EP 1 077 073 B1 discloses that use on uninjured skin requires copolylactides with high adherence, flexibility and extensibility. Water vapor permeability is according to EP 1 077 073 B1 is a decisive criterion for use on injured skin and, according to EP 1 077 073 B1, cannot be achieved by the copolymers alone, since these are hydrophobic and not very permeable (<60 ml/h/m ² ). According to the disclosure of EP 1 077 073 B1, either a relatively high proportion of monomers is required in the reaction product or the addition of hygroscopic/hydrophilic substances (eg glycerol) through which initially high vapor permeability values (>150 ml/h/m ² ) are achieved which decreases over days (corresponding to wound secretion).

EP 1 077 073 B1 discloses copolymers of racemic lactide and the comonomers ε-caprolactone, δ-valerolactone, 1,4-dioxanone-2 or 1,3-dioxanone-2 in a molar ratio of lactide/comonomer of 90-80/10-20 , which were polymerized in the presence of stannous diethylhexanoate as an initiator and a cocatalyst at about 160°C, and a glass transition temperature between 30 and 43°C, a molecular weight Mn from 15,000 to 50,000 and a polydispersity Pn (Mw / Mn) between 1.2 and 2. In particular, a copolymer of D,L-lactide and 1,3-dioxanone-2 (also known as trimethylene carbonate) prepared in this way is disclosed, as is a copolymer of D,L-lactide and s-caprolactone. According to the teaching of EP 1 077 073 B1, a low viscosity leads to a sticky consistency, which must lead to adhesions to textiles lying on top (e.g. bandage material). On the other hand, according to EP 1 077 073 B1, copolymers with the same lactide/comonomer ratio with high viscosity are not very flexible, stiff, brittle and have poor adhesion. The viscosity of the copolymers according to the invention sought in EP 1 077 073 B1 is between 0.30 and 0.75, preferably between 0.55 and 0.67.

The object of the invention is to provide a polymer-based plaster preparation which is suitable for the production of both polymer films and polymer fiber fleeces, with a high viscosity of the plaster preparation and a high extensibility of the polymer film or polymer fiber fleece being achieved at a low thickness, with both polymer films and Polymer fiber webs show good adhesion to skin (human or animal, dry or wet) or wounds and where a high water vapor permeability, in particular comparable to the water vapor permeability of the skin (human or animal), is achieved without the need for further additives. Furthermore, a polymer film, a spray plaster spray device, a method for producing a polymer fiber fleece are to be specified.

The task relating to the plaster preparation is achieved according to the invention by a plaster preparation having the features of claim 1. The polymer film according to the invention has the features specified in claim 16. The spray plaster spraying device according to the invention is specified in claim 22, the method for producing a polymer fiber fleece is specified in claim 23, the polymer fiber fleece is specified in claim 24. Uses are specified according to claims 26 and 27. Advantageous configurations with expedient developments of the invention are specified in the respective dependent claims.

The plaster preparation comprises at least one resorbable polymer made from at least 3, in particular different, monomers, in particular a polymer comprising monomers selected from the group consisting of trimethylene carbonate, glycolide, lactide, in particular (DL-lactide), p-dioxanone, s-caprolactone and/or Butyrolactone, at least one easily vaporizable organic solvent.

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

Surprisingly, the plaster preparation according to the invention permits a high inherent viscosity, a high viscosity for the purposes of the invention meaning a viscosity >0.75 dl/g, generally >1 dl/g. (According to the present application, the viscosity is to be determined with μg of polymer per 1 ml of chloroform at 25° C.). The polymer films and polymer fiber webs that can be produced using the plaster preparation or spray plaster preparation according to the invention show a low thickness (film: 10-50 μm; fleece: 80-200 μm) for the Application Sufficient adhesion to skin and wounds, good stretchability (film: 200-1500%; fleece 150-200%), with different strengths (film: 0.4 - 15 N/mm ² ; fleece: 0.6 - 0. 8 N/mm ² ) and good water vapor permeability, in particular adapted to the skin (human or animal, dry or wet) (film: 15-80 g/m ² /h; fleece 80-120 g/m ² /h). The plaster preparation according to the invention can therefore be applied externally very thinly, in particular as a spray plaster preparation. The aforementioned adhesion is such that the polymer film or the polymer fleece cannot be detached from its outer application site without being destroyed. Rather, the polymer film or the polymer fleece can only be detached by hand in small shreds. In contrast, when washing/showering and when carefully drying the skin, the polymer film or polymer fleece remains intact and adheres. The plaster preparation can also be applied as a pump spray or by means of a brush or the like to the application site (skin/wound) to be treated with a plaster.

Resorbable polymers within the meaning of the invention are polymers produced by polymerisation of at least three different monomers, with both the polymers and the monomers used being degraded in vivo and in vitro essentially by hydrolysis. The polymers and their degradation products are medically safe and non-allergenic. The monomers are further metabolized in vivo via the citric acid cycle or via the fatty acid metabolism.

Suitable polymers contain in particular trimethylene carbonate, glycolide, lactide, in particular D,L-lactide, p-dioxanone, s-caprolactone and/or butyrolactone.

In a preferred embodiment, the absorbable polymer contains trimethylene carbonate, in particular lactide, in particular D,L-lactide, ε-caprolactone and trimethylene carbonate; the terpolymer particularly preferably consists of lactide, in particular D,L-lactide, s-caprolactone and trimethylene carbonate. This has the additional advantage that the polymers with a glass transition point of 22°C - 37°C can be easily adapted to wound geometries and promote wound healing favor. The continuous release of the monomers and the degradation of the polymers to form monomers promote wound healing over a longer period of time. This effect can be increased by reapplication.

The polymer can preferably consist of 60 to 90% by weight D,L-lactide, 5 to 35% by weight s-caprolactone and 5 to 35% by weight trimethylene carbonate, in particular from 70 to 85% by weight D,L-lactide, 5 to 20% by weight % s-caprolactone and 5 to 20% by weight trimethylene carbonate. These compositions are particularly advantageous since amorphous structures are formed which produce elastic and plastic behavior. Thus, the mobility for wound areas covered with the plaster, for example on joints, is maintained.

In a further embodiment, the polymer preferably has an inherent viscosity between 0.3 dl/g and 2.5 dl/g, in particular between 0.75-1.6, very particularly preferably between 0.9-1.6 dl/g (viscosity in the present application measured with 1 mg of polymer per 1 ml of chloroform at 25° C.). This viscosity has the additional advantage that the resulting film is mechanically sufficiently stable and shows the desired degradation properties.

In a further embodiment, the polymer preferably has a monomer content of between 0.5 and 10% by weight, in particular a monomer content of between 3 and 8% by weight. This has the additional advantage that the release of the monomers promotes wound healing and the film exhibits the desired plastic, elastic behavior. The continuous release of the monomers over a longer period of time promotes wound healing (over several days).

According to a further aspect of the invention, the patch preparation can additionally comprise at least one further absorbable polymer, in particular a poly-s-caprolactone, polylactide, polyglycolide, polyethylene glycol and/or at least one non-absorbable polymer, in particular from the group consisting of Polyacrylates and polyurethanes, the non-resorbable polymers being added in particular as a blend with a preferred proportion of 1-50% based on the terpolymer. This has the added benefit of increasing adhesion and improving flow properties (when creating a film).

According to the invention, easily vaporizable organic solvents are organic solvents with an evaporation number (VD) according to DIN 53170 of <35, in particular <10 /or mixtures thereof, ethyl acetate, methyl acetate and/or acetone being particularly preferred. Organic solvents DMSO and N-pyrrolidone are also suitable.

The resorbable polymer can be dissolved in the organic solvent.

Propellants within the meaning of the invention are gaseous or gas-evolving compounds by means of which other substances, in particular other liquids and/or gases, are transported and/or atomized. Examples of suitable propellants are dimethyl ether, methane, ethane, propane, butane, pentane, low-boiling (<50°C) halogenated hydrocarbons, noble gases, air and/or CO2.

In a further embodiment of the invention, the plaster preparation according to the invention can consist of a composition of 5-25% by weight resorbable polymer of at least 3 (different) monomer units and 75-95% by weight organic solvent.

If the plaster preparation is designed as a spray plaster preparation, it can, in a further embodiment of the invention, consist of a composition of 2.8 to 7% by weight resorbable polymer of at least three (different) monomer units, 31.5 to 65% by weight organic solvent and 30 up to 64% by weight of propellant. According to a further aspect of the invention, the plaster preparation can additionally have at least one disinfectant, in particular an antibacterial substance, in particular polyhexanide, phenoxyethanol, iodine, peroxides and/or silver. The plaster preparation can have disinfectants with a proportion by weight of 0.05% by weight-5% by weight, in particular 0.1% by weight-2% by weight.

Completely surprisingly, it turned out that with the addition of a disinfectant to the plaster preparation, an even further increased extensibility of the polymer fil that can be produced therefrom can be achieved. So e.g. B. by adding a weight proportion of only 1 wt.% Phenoxyethanol in the plaster preparation, a polymer film can be produced, the extensibility of which is up to 1500%. The polymer film can be repeatedly deformed particularly easily and can even after stretching z. B. 500% completely or almost completely automatically elastically revert to its original shape. The modulus of the polymer film that can be produced from the plaster preparation is so small that the polymer membrane is hardly or not at all perceptible to the wearer when applied externally to the skin. This enables a particularly high wearing comfort, especially when applied close to the joint. In addition, undesired detachment of the polymer film from the application site can be counteracted even more efficiently as a result, even in the case of repetitive stretching of the polymer film accompanied by movement of the person/animal supplied with the polymer film. At the same time, the durability of the plaster preparation can be improved and an advantageous antibacterial property of the polymer film produced from it can be realized.

Other additives can be cooling, pain-relieving, caring or virucidal.

According to a further aspect of the invention, the plaster preparation can also contain biologically active additives, such as substances with an antibacterial effect, hemostatic substances, cytokines, growth factors, in particular TGFß, anesthetics and/or biologically inactive additives such as UVA and/or UVB filters, dyes, other polymers, adhesives.

The invention also relates to a polymer film produced by spraying the plaster preparation according to the invention.

Polymer films produced by means of the plaster preparation according to the invention, in particular spray plaster preparation, have a low thickness (10-50 μm) which is sufficiently good for the application on skin, fur and wounds, good extensibility (200-1000%) and high strength (0.4 - 15 N/mm ² ) and good water vapor permeability (15 - 80 g/m ² /h), in particular adapted to the skin. Polymer films according to the invention are therefore very comfortable to wear when used on the skin and accelerate wound healing due to the release of lactate.

In one embodiment, the polymer film preferably has a monomer content of <10% by weight. This has the additional advantage that the mechanical properties desired for the intended use as a plaster are achieved and no brittleness is found in connection with plastic and elastic behavior.

In one embodiment, the polymer film preferably has a modulus of elasticity between 1.5 and 1000 N/mm ² , in particular between 1.7 and 450 N/mm ² . This has the added benefit that the film is not stiff. This promotes sufficient adhesion to the skin.

In one embodiment, the polymer film has an extensibility of between 100 and 1500%, in particular between 250 and 1000%. This has the additional advantage that the material is sufficiently flexible even for body parts that are geometrically difficult to cover, especially in the area of joints.

The polymer film preferably has a strength of between 0.1 and 30 N/mm ² , in particular between 1 and 20 N/mm ² . This has the additional advantage that the material does not tear even when applied close to the joint and during movements.

According to a further advantageous embodiment, the polymer film has a thickness of between 5 and 30 μm (measured after drying). Polymer films of this thickness are particularly comfortable to wear, and there is also better air and moisture exchange. This promotes wound healing.

The invention also relates to a spray plaster spraying device for spraying the spray plaster preparation according to the invention, comprising a housing with a spray head for triggering the spraying process, in particular a cylindrical housing with a longitudinal axis. The housing comprises a reservoir for the spray plaster preparation and a propellant channel for a propellant of the spray plaster preparation with a diameter d _t . The propellant channel runs in a first area in the direction of the longitudinal axis in the housing as a riser and extends in a second area in the spray head at an angle radially between the geodetic end face of the riser and a spray opening of the spray head.

The second area has a diameter d ₂ which is smaller than the diameter di of the first area. The second area (d2) opens into a mixing area with a diameter d ₃ . The mixing area adjoins the second area in the radial direction and connects the second area to a spray opening. A channel of the reservoir with a diameter runs in the direction of the longitudinal axis and opens into the mixing area and with its diameter d ₄ being larger than the diameter d ₃ . The spray opening has a relaxation area which increases in the shape of an expansion cone and has a maximum diameter d ₅ , the relaxation area extending between the mixing area and the spray opening.

The spray plaster spraying device according to the invention brings with it the advantage that the spray plaster preparation according to the invention is surprisingly also suitable, by spraying using the spray plaster spraying device, to produce polymer fibers which, as a polymer fiber fleece, are applied to a surface, in particular a skin (human or animal, dry or wet) or wound can be deposited. This brings with it the advantage that the plaster preparation according to the invention can be applied as a fibrous sheet to a wound, for example a chronic wound, in order to reduce wound pain, reduce the risk of maceration and/or infection in a wound, in particular in the case of a chronic wound. Furthermore, the polymeric nonwoven fabric of the present invention may be advantageous for stimulating vascularization in a wound, particularly in a chronic wound, and/or for use in augmenting the epidermis and dermis of a wound.

The invention also relates to a method for producing a polymer fiber fleece comprising polymer fibers, the spray plaster preparation according to the invention being sprayed using the spray plaster spray device according to the invention, a propellant of the spray plaster preparation being pressed at high speed into a mixing area of a propellant channel, and a polymer made of at least 3 monomers of the spray plaster preparation and a solvent of the spray plaster preparation is transported by means of a channel (from a reservoir) into the mixing area and is mixed with the propellant flowing at high speed and the mixture obtained is transported into a relaxation space of a spray opening, the solvent evaporating on exiting the spray opening wherein polymer fibers are formed, and wherein a polymer fiber web comprising the polymer fibers on a surface, in particular on a human or animal skin surface, especially on a wound.

The thickness of the polymer fiber fleece to be produced can be selected as required by selecting the spraying time and repeating the spraying process.

The fiber thickness of the nonwoven-forming polymer fibers can be influenced by the pressure in the spray plaster spraying device, the polymer concentration and the maximum way the spray opening is opened (=maximum clear diameter). The greater the pressure of the blowing agent and the smaller the maximum opening width, the smaller the fiber strength and vice versa. The invention further relates to a polymer fiber fleece produced according to the method according to the invention. The polymer fiber fleece according to the invention brings with it the advantage that the fibers can, surprisingly, optimally adapt to the wound bed. In addition, they are almost entirely solvent-free, which means that the fibers can be treated with less pain when sprayed on. Thanks to the fleece structure, wound fluid can also be better absorbed and wound exudate can be transported to the outside, which is particularly advantageous in the case of heavily exuding wounds. In addition, the ventilation of the application site supplied with the polymer fiber fleece can be improved.

According to one embodiment, the polymer fiber fleece according to the invention preferably has a water vapor permeability of between 80 and 200 ml/m ² /h. The polymer fiber fleece according to the invention has the advantage that liquid from weeping wounds can be drained off more easily

The 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 wound treatment of epidermal and dermal wounds, in particular abrasions, cuts, burns and chronic wounds, in particular ulcer wounds, in particular pressure-induced ulcer (decubitus ulcer), arterial ulcer, venous ulcer , mixed arterial-venous ulcer, leg ulcers, arterial leg ulcers, venous leg ulcers, leg ulcers in diabetic foot syndrome and post-traumatic leg ulcers.

The invention also relates to the use of the plaster preparation according to the invention for use in redness of the skin, in particular in sunburn, for sun protection, in cosmetic applications, in particular for camouflage, or as an absorbable adhesive. Suitable dyes can be added to the plaster preparation for camouflage purposes.

When used as a sunscreen, conventional UVA and UVB filters known per se are added to the plaster preparation. Further advantages of the invention result from the description and the drawing. The embodiments shown and described are not to be understood as an exhaustive list, but rather have an exemplary character for the description of the invention.

In the following examples, a standard spray head ("standard nozzle") with the designation "Kosmos" and with the valve PV22210-200149 from Precision Despensing Solutions Europe GmbH was used. The diameter specified in each case relates to the maximum opening width (= d5 in Fig. 1 of the drawing) of the standard nozzle.

Numerical values given in round brackets are mass fractions in % by weight. It should be noted that viscosity values in the present application were each measured with 1 mg of polymer per 1 ml of chloroform at 25°C.

example 1

A spray patch formulation containing poly-D,L-lactide trimethylene carbonate E-caprolactone (75/15/10)

Polymer: 7% by weight

Ethyl acetate: 63% by weight

Dimethyl ether: 30% by weight was placed in a pressure can (standard nozzle with a diameter: 0.91 mm) as shown in FIG. 1 and sprayed from a distance of about 10 cm and a pressure of about 5.1 bar (at 20° C.). . A transparent polymer film with a thickness of about 12 μm and a water vapor permeability of about 30 ml/m ² /h formed. Increasing the spraying time increases the film thickness. With a layer thickness of 40 μm, the water vapor permeability was about 18 ml/m ² /h. When sprayed onto a moist piece of meat at a temperature of 37° C., a polymer film was formed within about 1-2 minutes that was sufficiently adhesive (non-displaceable and non-displaceable and non-moving) for use as a wound plaster.

When applied to tempered, moist meat, the polymer film was removed with tweezers after about 1 to 2 minutes.

Also on human skin (both dry and wet) a non-displaceable layer that remains adherent during movement was formed.

The following mechanical values were determined by means of uniaxial tensile tests: Modulus of elasticity (E-modulus) in the linear range (DIN 53457), the tensile strength as tensile stress at tearing (N/mm ² ) and the elongation (%) at which the individual stresses arose. The measurements were made at 20 °C

Modulus of elasticity: approx. 250 N/mm ²

Elongation: approx. 350%

Tensile strength: approx. 7 N/mm ²

The polymer film is sufficiently strong for use as a plaster with a low thickness, has good adhesion to skin or wounds and has high water vapor permeability, in particular comparable to the water vapor permeability of the skin, without the need for further additives.

example 2

Polymer: 10 wt% [8 wt%]

Ethyl acetate: 90 wt% [92 wt%] was placed in a pressure can with a standard nozzle (diameter: 0.91 mm) according to FIG. 1 and sprayed at a distance of about 10 cm and a pressure of about 5 bar compressed air. A transparent polymer film with a thickness of approx. 12 μm [10 μm] and a water vapor permeability of approx. 25 ml/m ² /h [40 ml/m ² /h] is formed. The following mechanical values resulted from uniaxial tensile tests:

Modulus of elasticity: approx. 700 N/mm ²

Elongation: approx. 300%

Tensile strength: approx. 11 N/mm ²

Example 3

A spray patch formulation containing poly-D,L-lactide trimethylene carbonate E-caprolactone (75/15/10) and violet dye "D&C Violet No.2" to visualize the sprayed area

Polymer: 3.6% by weight

Violet dye: 0.0045% by weight

Ethyl acetate: 41.3955% by weight

Dimethyl ether: 55% by weight was placed in a pressure can with a standard nozzle (diameter: 0.91 mm) as shown in FIG. 1 and sprayed at a distance of 10 cm and a pressure of about 5.1 bar (at 20° C.). A violet but still transparent polymer film with a thickness of approx. 15 μm and a Water vapor permeability of approx. 41 ml/m ² /h. The following mechanical values resulted from uniaxial tensile tests:

Modulus of elasticity: approx. 616 N/mm ²

Elongation: approx. 348%

Tensile strength: approx. 8.7 N/mm ²

example 4

Polymer: 3.5% by weight

Ethyl acetate: 31.5% by weight

Dimethyl ether: 65% by weight was placed in a pressure can with a standard nozzle (diameter: 0.91 mm) according to FIG. 1 and at a distance of approx. 10 cm and a pressure of approx. sprayed. A transparent polymer film with a thickness of approx. 17 μm and a water vapor permeability of approx. 62 ml/m ² /h is formed. A very firmly adhering layer also forms on human skin (both dry and wet). Due to the high propellant gas content, many small bubbles form when spraying, but a polymer film forms. The following mechanical values resulted from uniaxial tensile tests:

Modulus of elasticity: approx. 416 N/mm ²

Elongation: approx. 355% Tensile strength: approx. 7.5 N/mm ²

The polymer film shows high strength at low thickness, good adhesion to skin or wounds and has high water vapor permeability, in particular comparable to the water vapor permeability of the skin, without the need for further additives.

Example 5

A spray patch formulation containing poly-D,L-lactide trimethylene carbonate E-caprolactone (75/15/10) with 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 with a standard nozzle (diameter: 0.91 mm) according to FIG. 1 and at a distance of approx. 10 cm and a pressure of approx. 5.1 bar (at 20 °C). A transparent polymer film forms with a thickness of approx. 14 μm and a water vapor permeability of approx. 29 ml/m2/h. A very firmly adhering layer also forms on human skin (both dry and wet). The following mechanical values resulted from uniaxial tensile tests:

Modulus of elasticity: approx. 248 N/mm2

Elongation: approx. 486%

Tensile strength: approx. 14.3 N/mm2

The polymer film shows high strength at low thickness, good adhesion to skin or wounds and has high water vapor permeability, comparable in particular to the water vapor permeability of the skin without the need for further additives.

Example 6

Polymer: 13% by weight in ethyl acetate: 87% by weight

Polymer: 13% by weight in ethyl acetate/acetone mixture 1:1:87% by weight

Polymer: 16% by weight in acetone: 86% by weight was placed in a pressure can with a spray head according to the invention as shown in FIG. 1 and sprayed from a distance of about 30 cm and an air pressure of about 5 bar. Whitish polymer fibers formed with an average thickness of approx. (A) 850 nm (B) 1 pm (C) 2 pm. The polymer fibers formed a polymer fiber fleece according to the invention, which was also obtained with a standard nozzle (with a diameter of 0.91 mm) at low pressure (about 1 bar). The polymer fiber fleece adheres well to human skin. A very firmly adhering polymer fiber fleece also formed on human skin (both dry and wet).

The polymer fleece (A) had a water vapor permeability of about 111 ml/m ² /h. The following mechanical values resulted from uniaxial tensile tests:

Modulus of elasticity: approx. 21 N/mm ²

Elongation: approx. 184%

Tensile strength: approx. 0.82 N/mm ²

The polymer fleece shows high strength at a low thickness of 120 μm, good adhesion to skin or wounds and has high water vapor permeability, comparable in particular to the water vapor permeability of the skin without the need for further additives.

Example 7

Polymer: 15% by weight in ethyl acetate: 85% by weight

Polymer: 17% by weight in ethyl acetate: 83% by weight

Polymer: 19% by weight in ethyl acetate: 81% by weight was placed in a pressure can with a spray head according to the invention as shown in FIG. 1 and sprayed from a distance of about 30 cm and at an atmospheric pressure of about 8 bar. Whitish fibers formed with an average thickness of approx. (A) 900 nm (B) 1 pm (C) 2.5 pm. A polymer fiber fleece according to the invention was formed. The polymer fiber web adhered to human skin in a manner suitable for use as a patch or skin protector.

example 8

A spray plaster preparation containing poly-D,L-lactide

Trimethylene carbonate-s-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 with a standard nozzle (0.91 mm) according to FIG. 1 and sprayed at a distance of about 10 cm and a pressure of about 5.1 bar (at 20.degree. C.). A transparent polymer film with a thickness of approx. 15 μm and a water vapor permeability of approx. 37 ml/m ² /h is formed. A very firmly adhering layer also forms on human skin (both dry and wet). Due to the high propellant gas content, many small bubbles form when spraying, but a polymer film forms. The following mechanical values resulted from uniaxial tensile tests:

Modulus of elasticity: approx. 4 N/mm ²

Elongation: approx. 770%

Tensile strength: approx. 2.6 N/mm ²

Surprisingly, the polymer film exhibits very high extensibility at low thickness, good adhesion to skin or wounds and has high water vapor permeability, in particular comparable to the water vapor permeability of the skin, without the need for further additives.

Show in the drawing:

1 schematically shows the structure of a plaster spraying device according to an embodiment;

2 shows photographs of polymer fibers of a polymer fiber fleece produced according to Example 5, the polymer fibers being produced from plaster preparations (A) and (C) by spraying using a plaster spray device according to the invention;

3 shows scanning electron micrographs of polymer fibers of a polymer fiber fleece produced from plaster preparations (A), (B) and (C) according to example 5 using the plaster spray device according to FIG. 1; 4 shows scanning electron micrographs of polymer fiber webs according to Example 6, which were produced using a spray fiber spraying device according to the invention.

In the figures, the same or similar components are numbered with the same reference numbers. The embodiments shown in the figures are only of an exemplary nature for describing the invention and are not to be understood as limiting.

FIG. 1 schematically shows the structure of a pressurized spray plaster spray device 10 for spraying a plaster preparation according to the invention, in particular for producing a polymer fiber fleece according to the invention of the plaster preparation by a method according to the invention for producing the polymer fiber fleece.

The spray plaster spraying device 10 comprises a housing 12 with a movably arranged spray head 14 for triggering the spraying process. The housing 12 can in particular be cylindrical or have a different shape. The housing 12 has a longitudinal axis L and comprises a reservoir 16 for the plaster preparation, a propellant channel 18 for a propellant T of the plaster preparation. The propellant channel 18 runs in a first area 20 in the direction of the longitudinal axis L in the housing as a riser pipe 22 and extends in a second area 24 in the spray head 14 at an angle in a radial direction between the geodetic end face of the riser pipe 22 and a spray opening 26 of the spray head 14. The first area 20 has an inside diameter di. The second area 24 has an inside diameter d ₂ which is smaller than the diameter di of the first area 20 .

The second area 24 opens into a mixing area 28 with a diameter d ₃ , which is preferably smaller than or equal to the diameter d ₂ . The mixing area 28 adjoins the second area 24 in a radial direction and fluidically connects the second area 24 to the spray opening 26 . A channel 30 of the reservoir 16 with a diameter d4 runs in the axial direction and opens into the mixing area 28. The diameter d ₄ is larger here than the diameter d ₃ and the diameter d ₂ . Actuating the spray head creates a fluidic connection between the propellant T stored in the housing 12 and the spray opening 26 . The remainder of the patch preparation disposed within the housing 12 is drawn into the mixing region 28 by subatmospheric suction mediated by the outflowing propellant.

The spray opening 26 has a relaxation area 32 that widens in the shape of an expansion cone, which extends in a direction radial to the longitudinal axis L between the mixing area 28 and the spray opening 26 . The spray opening has a maximum inside diameter d ₅ (=opening width).

FIG. 2 shows photographs of a polymer fiber fleece 100 comprising a multiplicity of polymer fibers 102 which were produced according to Example 5 explained above.

The polymer fibers 102 were made by spraying plaster preparations

- A, shown in the top row of photographs, and

- C, shown in the lower row of photographs, produced by means of a spray fiber spraying device 10 according to the invention according to FIG. 1 onto a glass plate (not visible in FIG. 2) with a spraying distance of 30 cm. The polymer fibers 102 of the polymer fiber fleece 100 are clearly visible.

FIG. 3 shows scanning electron micrographs of polymer fiber webs 100 each comprising polymer fibers 102 produced according to example 5. The polymer fibers 102 were produced by spraying the plaster preparations A, B and C using the spray fiber spray device 10 according to FIG. The figure on the left shows polymer fibers 102 made from plaster preparation A. The figure in the middle shows polymer fibers 102 from plaster preparation B and the figure on the right shows polymer fibers 102 from plaster preparation C. All images are on a scale of 50 μm, ie a 1 cm section in the figure corresponds 50 pm in kind. The polymer fibers 102 exhibit a form fit typical of nonwoven fabrics as a fabric by entanglement, cohesion and/or adhesion.

FIG. 4 shows scanning electron micrographs of polymer fiber webs 100 according to example 6 explained above, which were produced by means of a spray fiber spray device 10 according to the invention according to FIG. The scale corresponds to 50 pm. The polymer solutions were each sprayed at an internal pressure of the spray fiber spray device 10 of approximately 8 bar. The polymer concentrations were varied. Figure A shows a polymer fiber fleece 100 of solution A, Figure B shows a polymer fiber fleece 100 of solution B, Figure C shows a polymer fiber fleece 100 of solution C. The polymer fibers 102 or polymer fiber fleece 100 show sufficient adhesion on human skin even for wound closure.

Claims

Claims A patch preparation comprising a. at least one resorbable polymer of at least 3 monomer units, in particular a terpolymer, comprising monomers selected from the group consisting of trimethylene carbonate, glycolide, lactide, in particular (D,L-lactide), p-dioxanone, s-caprolactone and/or butyrolactone; and b. at least one easily vaporizable organic solvent. Plaster preparation according to claim 1, characterized in that the plaster preparation is a spray plaster preparation (16) with at least one propellant T. Plaster preparation according to Claim 1 or 2, characterized in that the absorbable polymer consists of lactide, in particular (D,L-lactide), s-caprolactone and trimethylene carbonate. Plaster preparation according to one of the preceding claims, characterized in that the resorbable polymer consists of 60 to 90% by weight of D,L-lactide, 5 to 35% by weight of s-caprolactone and 5 to 35% by weight of trimethylene carbonate, in particular of 70 to 85% by weight D,L-lactide, 5 to 20% by weight s-caprolactone and 5 to 20% by weight trimethylene carbonate. Plaster preparation according to Claim 4, characterized in that the resorbable polymer has an inherent viscosity of between 0.5 and 2.5 dl/g, in particular 0.5 - 1.6 dl/g, in particular between 0.9 - 1.6 dl/g g.

24 Plaster preparation according to one of the preceding claims, characterized in that the terpolymer has a monomer content of between 0.5 and 10% by weight, in particular a monomer content of between 3 and 8% by weight. Plaster preparation according to one of the preceding claims, additionally comprising at least one further absorbable polymer, in particular a poly-s-caprolactone, polylactide, polyglycolide, polyethylene glycol, poloxamer, and/or at least one non-absorbable polymer, in particular from the group consisting of polyacrylates, polycyanoacrylates, and polyurethanes, the non-resorbable polymers being admixed in particular as a blend. Plaster preparation according to one of the preceding claims, additionally comprising at least one other absorbable polymer, in particular a poly-E-caprolactone, polylactide, polyglycolide, polyethylene glycol and / or at least one monomer, in particular cyanoacrylate, which polymerizes on the skin to form a non-absorbable polymer and a Polymer blend of an absorbable polymer and a non-absorbable polymer results. Plaster preparation according to Claim 1, characterized in that 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, in particular ethyl acetate, methyl acetate, acetone and/or Mixtures thereof with cyclopentane. Plaster preparation according to claim 1, characterized in that the terpolymer is dissolved in the organic solvent. Plaster preparation according to Claim 1, characterized in that the propellant is dimethyl ether, methane, propane, butane, pentane, butene, low-boiling halogenated hydrocarbons, noble gases, air and/or CO2. Plaster preparation according to Claim 1, characterized in that the plaster preparation contains 5 to 30% by weight of terpolymer and 70-95% by weight of organic solvent. Plaster preparation according to Claim 1, characterized in that the plaster preparation contains 2.8 to 7% by weight of terpolymer, 31.5 to 64.4% by weight of organic solvent and 30 to 65% by weight of propellant. Plaster preparation according to one of the preceding claims, characterized in that the plaster preparation additionally has at least one disinfectant, in particular an antibacterial substance, in particular polyhexanide, phenoxyethanol, iodine, peroxides and/or silver. Plaster preparation according to one of the preceding claims, characterized in that the plaster preparation additionally contains UVA and/or UVB filters, cytokines, growth factors, in particular TGF-ß, local anaesthetics, hemostatic or antibacterial substances and/or biologically inactive additives, in particular dyes or Contains cyanoacrylates. Polymeric film produced by applying or spraying a plaster composition according to any one of the preceding claims. Polymer film according to Claim 16, characterized in that the polymer film has a modulus of elasticity between 1.5 and 1000 N/mm ² , in particular between 1.7 and 450 N/mm ² . Polymer film according to Claim 16 or 17, characterized in that the polymer film has a monomer content of <10% by weight. Polymer film according to one of the preceding claims 16 to 18, characterized in that the polymer film has an extensibility of between 100 and 1500%, in particular between 250 and 600%. Polymer film according to one of the preceding claims 16 to 19, characterized in that the polymer film has a strength of between 0.1 and 30 N/mm ² , in particular between 1 and 20 N/mm ² . Polymer film according to any one of the preceding claims 16 to 20, characterized in that the polymer film has a thickness of between 5 and 30 µm. Spray plaster spray device (10) for spraying a plaster preparation according to one of claims 2 to 15, comprising a housing (12) with a spray head (14) for triggering the spraying process, in particular a cylindrical housing (12) with a longitudinal axis (I), the housing (12) comprising a reservoir (16) for the plaster preparation, a propellant channel (18) for a propellant of the plaster preparation with a diameter di, the propellant channel (18) in a first area (20) in the axial direction in the housing acting as a riser pipe (22 ) and extends in a second area (24) in the spray head (14) at an angle radially between the geodetic end face of the riser pipe (22) and a spray opening (26) of the spray head (14), the second area (24) having a diameter d ₂ which is smaller than the diameter di of the first region (20), the second region (24) opening into a mixing region (28) with a diameter d ₃ which is smaller than the diameter d ₂ , the mixing area (28) radially adjoining the second area (24) and connecting the second area (24) to a spray opening (26),

27 wherein a channel (30) of the reservoir (16) with a diameter (d4) runs in the direction of the longitudinal axis (I) and opens into the mixing area (28) and wherein the diameter (d4) is greater than the diameter d ₃ , and wherein the spray opening (26) has a relaxation area (32) which widens in the shape of an expansion cone and extends in the radial direction between the mixing area (28) and the spray opening (26). Method for producing a polymer fiber fleece (100) comprising polymer fibers (102), characterized in that a spray plaster preparation according to one of Claims 2 to 12 is sprayed by means of a spray plaster spray device (10) according to Claim 21, the propellant T of the spray plaster preparation being injected at high speed into the mixing area (28) of the propellant channel (18), and a terpolymer of the spray plaster preparation and a solvent of the spray plaster preparation (16) are transported by means of a channel (34) into the mixing area (28) and are mixed with the propellant T flowing at high speed and wherein the mixture obtained is transported into a relaxation space (34) of the spray opening (26), wherein the solvent evaporates when exiting the spray opening (26), polymer fibers being formed, and a polymer fiber fleece having the polymer fibers on one surface, in particular on a human or animal skin surface. Polymer fiber fleece produced by a method according to claim 23. Polymer fiber fleece according to claim 24, characterized in that the polymer fiber fleece has a water vapor permeability of between 80 and 200 g/m ² /h.

28 Use of a plaster preparation according to any one of claims 1 to 15 for the topical treatment of human or animal skin, in particular for the treatment of epidermal and dermal wounds, in particular abrasions, cuts, burns and chronic wounds, in particular ulcer wounds. Use of a plaster preparation according to one of Claims 1 to 15 for external application in the case of redness of the skin, in particular in the case of sunburn, for sun protection, in cosmetic applications, in particular for camouflage, or as an absorbable adhesive.

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