CZ308167B6 - A process for manufacturing polymeric fibres with a diameter of 100 nm to 10 μm, and a process for producing a linear, planar or spatial formation containing these polymeric fibres - Google Patents

Abstract

A method of producing polymer fibres with a diameter of 100 nm to 10 μm is described, where a drop (2) of a solution or melt of polymer of at least 0.001 μl is formed on the surface of the substrate (1), one elongated spinner element (3) on the surface of which and / or in its cavity a portion of the polymer solution or melt is retained from the drop (2), after which the spinner element (3) is moved by the manipulator on which it is deposited, and / or by moving substrate (1) to another place on the same or different substrate (1). The solution or melt of the polymer on its surface and / or in its cavity remains interconnected during this movement by the fibre (4) of the polymer solution or melt, whose the diameter, when the spinning element (3) and / or the substrate (1) moves, is decreased. The fibre (4) is anchored on subsequent contact of the end of the spinning element (3) with the surface of the substrate (2), thereby depositing a polymer fibre with a diameter of 100 nm to 10 μm on the surface of the substrate (2). Also described is a process for producing a linear, planar or spatial formation with polymeric fibres with a diameter of 100 nm to 10 μm, which is created in this way and is simultaneously deposited in the desired direction and relative orientation in the space or area.

Description

Technical field

The invention relates to a process for the production of polymer fibers with a diameter of 100 nm to 10 µm.

The invention also relates to a process for the production of linear, planar and spatial formations comprising polymer fibers having a diameter of 100 nm to 10 µm.

BACKGROUND OF THE INVENTION

Typical products of all known processes for the production of polymer nanofibres, ie fibers with a diameter of about 100 to 1000 nm by electrostatic spinning of solutions or melts of polymers using static needle spinning electrodes (nozzles, capillaries, etc.) or movable surface spinning electrodes (rotating cylinder - see eg CZ 299549, a moving string in the direction of its length or in a circular path - see eg CZ 299549 and CZ 300345, rotating spiral, disc, etc.), or by centrifugal spinning, when the polymer solution or melt is extruded / extruded by centrifugal force from holes formed in the housing of a rotating body in the form of a disc (see eg DE 102005048939) or a cylinder (see eg JP 2008127726) is a sheet of randomly deposited and interwoven polymer nanofibres. Although it has a wide range of applications in combination with other supporting or covering layers, especially in the field of filtration and hygiene products, it can be used only to a limited extent for many other areas and applications, such as tissue engineering, regenerative medicine, etc. In principle, these applications require rather flat or spatial nanofibrous structures with a specific internal structure and polymer nanofibres or even fibers of larger diameters oriented in the desired direction (s), defining the desired direction (s) of cell growth, respectively. cell colonization of this formation.

Although several procedures based on the use of air / gas streams have been proposed for orientation of polymer nanofibres during their production and possibly during their depositing onto the substrate (see eg US 6308509 with deposition of polymer nanofibres on a fiber core in a suction tube, or US 2005008776 with polymer of nanofibers by air flow immediately after their formation) or of alternating electric voltage (see eg US 2004013819, or analogous patent US 335999, or WO 2008106381 using a specially shaped collector on which polymer nanofibres are deposited, or US 2004061253 using auxiliary circular electrodes used for narrowing and rectifying the current of polymer nanofibres coming from the spinning electrode formed by the nozzle), none of them is usable in practice, because, as shown in practical testing, the orientation of polymer nanofibres occurs only to a limited extent and Structure created departments. it is still rather random and disordered.

It is an object of the present invention to provide a process for the production of polymer nanofibres, optionally polymeric microfibres with a diameter of up to 10 µm, which allows the greatest possible orientation (isotropy) of individual fibers and to create linear, planar and spatial formations containing these polymer fibers with desired orientation with a predetermined orientation. location.

SUMMARY OF THE INVENTION

The object of the invention is achieved by a process for the production of polymer fibers having a diameter of 100 nm to 10 µm, which comprises forming a drop of polymer solution or melt with a volume of at least 0.001 µl on the surface of the substrate. one elongated fiberising element. In doing so, on its surface and / or in its

A portion of the polymer solution or melt is retained in the cavity, whereupon the spinning element is moved by moving the manipulator on which it is deposited and / or by moving the substrate to another location on the same or different substrate, the polymer solution or melt on its surface; or in its cavity due to its viscosity and surface tension it remains interconnected / interconnected by a fiber whose diameter decreases as the spinner and / or the substrate moves, with a drop of solution or melt on the surface of the substrate. When the end of the spinner is subsequently contacted with the substrate surface, the fiber is anchored. In this way, a polymer fiber having a diameter of 100 nm to 10 µm with the desired length and orientation is formed and deposited on the surface.

The drop of polymer solution or melt can be formed on the surface of the substrate, for example by applying a polymer solution or melt by means of a coating device or manually, by applying a polymer solution or melt on the surface and / or in the spinner cavity, or by extruding the polymer solution or melt from the solution reservoir; melting the polymer through the cavity of the hollow spinner. In a preferred embodiment, the hollow spinning element is supported on the cartridge and its cavity communicates with the inner space of the cartridge or polymer melt.

A suitable hollow spinning element is a hollow conical needle whose outlet opening has a diameter of 0.1 to 1.2 mm or a tube with an outer diameter of 0.1 to 1.5 mm. However, a stick of this diameter may also be used.

In a preferred embodiment of the method according to the invention, the substrate remains static and only the spinning element moves, preferably along an arched trajectory, reaching a maximum speed of 1 to 100 m / min. However, if necessary, the speed may be higher.

In spinning some polymers such as polycaprolactone and the like, it is preferable that the transfer of the spinning element stops before contact with the surface of the substrate, and continues after at least partially solidifying the fiber. This results in a smaller diameter of the formed fiber, since no further material from the initial droplet is fed into it.

Preferably, an end drop of the polymer solution or melt is used to anchor the fiber end to the surface of the substrate, since in this case its anchorage is more secure, and the end drop material can additionally be used to form additional fibers. The end drop can be deposited on the same or different substrate than the starting drop of polymer solution or melt.

When a hollow spinner is used, the end drop is preferably formed by forcing at least 0.001 µl of polymer solution or melt from the interior of the spinner.

In order to create a suitable fiber material structure, it is advantageous if the fiber being produced is stimulated by an electric current, wherein a high DC voltage of any polarity is applied to the spinning element and to the electrically conductive substrate. The conformation of the macromolecules of the polymer is influenced, and the formed fiber thus achieves significantly better geometric and mechanical properties.

Suitable polymers for forming fibers with a diameter of 100 nm to 10 µm are especially polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polystyrene (PS), poly (methyl methacrylate) (PMMA), polycaprolactone (PCL), polyurethane (PU), a modified variant of any of them, or any mixture or copolymer of at least two of them.

The object of the invention is also achieved by a process for the production of a linear or planar body comprising polymeric fibers having a diameter of 100 nm to 10 µm, the principle being that the polymeric fibers having a diameter of 100 nm to 10 µm produced by the process according to the invention are

The surfaces of one or more substrates deposit side-by-side and / or stacked in the desired relative orientation, thereby forming a linear or sheet-like configuration.

In addition, the object of the invention is also achieved by a process for manufacturing a sheet or spatial formation comprising polymeric fibers of 100 nm to 10 µm diameter, wherein the polymeric fibers of 100 nm to 10 µm diameter produced by the method are repeatedly deposited in parallel and / or parallel to each other. In the same manner, polymer fibers of 100 nm to 10 µm diameter are formed from the same or different material and deposited thereon in the same or different orientation.

For further processing or removal of the thus formed structures, it is advantageous if the individual polymer fibers are anchored at their ends on a substrate other than that on which the initial drop of solution or melt of polymer from which the fibers are formed is deposited.

In the manufacture of the spatial formation, the polymeric fibers having a diameter of 100 nm to 10 µm can be deposited on the spatially shaped substrate, the fibers and the structure formed by them copying / copying at least partially its shape.

Clarification of drawings

In the accompanying drawings, Fig. 1 schematically illustrates the principle of the method of production of polymer fibers with a diameter of 100 nm to 10 µm according to the invention; Fig. 2 the principle of another variant of this method; Fig. 3 SEM image of a linear formation containing polymer nanofibers magnification 480x, SEM image of this linear formation at 100x magnification, Fig. 5 SEM image of this linear formation at 3000x magnification, Fig. 6 SEM image of this linear formation at 5000x magnification, Fig. 7 SEM image of linear formation containing a polymer nanofibers produced by the method according to the invention with an additional stopper at a magnification of 500x, FIG. 8 is a SEM image of a sheet containing parallel-arranged polymer nanofibers produced by the method according to the invention at a magnification of 500x; Fig. 10 is a SEM image of a surface pattern containing a grid of intersecting polymer nanofibres formed by a method of the invention planted with living cells at a magnification of 25 x; Fig. 11 is a SEM image of a surface pattern containing a grid of perpendicular polymer nanofibers. produced in accordance with the method according to the invention, loaded with living cells at a magnification of 100x, in FIG. 12, an SEM image of a sheet containing a grid of intersecting polymer nanofibres produced in the method according to the invention. and Fig. 14 is a SEM image of a sheet containing a grid of intersecting nanofibers of two polymers produced by the method of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The process for the production of polymer fibers with a diameter of 100 nm to 10 µm according to the invention is based on the use of the viscosity of a solution or a melt with the polymer and its polymer, respectively. its intermolecular forces to "pull the individual fibers from the solution / melt drop (s) / polymer deposited / deposited on the adhesive substrate." The principle of this method will be further explained with reference to FIGS. 1 and 2. In this method, first a drop 2 of a solution or melt of polymer is preferably formed on the surface of the adhesive substrate 1, preferably a volume of 0.001 to 4.2 µl, possibly larger, into which, during or after its formation, an elongated spinning element 3 is immersed in the form of a (conical) needle, tubing or rod, the end of which is formed by a flat surface, tip, bevel or rounding, etc.

As a rule, the polymer 3 in the part which is immersed in the solution drop or melt polymerizes 0.1 to 1.5 mm.

The spinning element 3 is preferably mounted on a manipulator not shown, which is capable of moving in at least two axes - vertically perpendicular to the substrate 1 (arrow y) and horizontally along the length of one of the dimensions of the substrate ± (arrow z) and preferably horizontally the length of the second of its dimensions (arrow x), optionally at an angle. However, any of these manipulator movements may be replaced or supplemented by the respective movement of the substrate. In addition, it is further advantageous to form more complex, e.g. spatial, polymer fiber formations if the manipulator or its spinning element portion 3 is capable of rotation about at least one axis.

By moving this manipulator, the spinning element 3 is then withdrawn from the solution drop or polymer melt 2 and following the trajectory T, which has an advantageous arcuate shape in Fig. 1, but generally may have any other shape (and e.g. if the substrate 1 is suitably the trajectory may be rectilinear), it moves in the desired direction and at a selected, even variable, speed to the desired distance from the solution droplet 2 or polymer melt, where again When immersing the spinning element 3 in a droplet 2, a small amount of polymer solution or melt adheres to its surface and / or its cavity, which remains due to the viscosity and surface tension of the material throughout the spinning element 3 movement. interconnected with the starting drop 2 by a thin fiber 4 of this material, and whose p the naturally small diameter decreases even further with its length (or with the travel length of the spinner 3). In this way, a separate polymer fiber of desired diameter, length and orientation is gradually formed. Upon subsequent contact of the spinner 3 with the surface of the substrate 1, this fiber 4 is terminated and its other end anchored to the surface of the substrate 1 (its first end is anchored in the starting drop 2). Due to the large surface area and the intense evaporation of the solvent (mainly caused by increasing capillary pressure within the drawn fiber), it solidifies relatively quickly, and it is advantageous if it solidifies at or just after the anchoring of its other end. In spinning some polymers, eg polycaprolactone, on the contrary, it is advantageous if the spinning element 3 moves along the trajectory T for a moment (units up to tens of seconds) and then continues only after the fiber 4 has partially solidified. then its smaller diameter is reached since no further material from the droplet 2 is supplied to it.

After the polymer fiber has been formed and anchored to the surface of the substrate 1, the spinning element 3 returns to the initial droplet 2 of the polymer solution or melt to submerge into it the material to pull another fiber 4. This process is then repeated in the same manner until forming the desired number of fibers or the desired linear, planar or spatial formation. In this case, it is advantageous if an end drop 20 of the polymer solution or melt is formed at the anchoring point of the other end of the formed fibers 4 on the surface of the substrate 1 so that the individual fibers 4 are formed or can be formed during the return phase. of the substrate 1 to form substantially any number of starting and / or end droplets 2, 20 of the polymer / polymer melt or melt, and to form essentially any planar fiber structure between 100 nm and 10 µm in diameter with one or more identical or different spinning elements 3 therebetween or more polymers. In this case, each drop 2, 20 can serve simultaneously as an end, i.e., anchor the end of the fiber 4 formed in the previous step, and at the same time as a source of material for the subsequent fiber 4 and vice versa.

After processing a predetermined amount of polymer solution or melt from the initial drop 2 and / or end drop 20, or after the initial drop 2 and / or end drop 20 solidifies, a new initial drop 2 or new end drop is formed in the same manner on the substrate. 20. This drop (s) 2, 20 may be formed on the surface of the substrate 1 by, for example, a non-illustrated metering device with forced or spontaneous movement of the polymer solution or melt,

Manually, or by applying the required amount of polymer solution or melt to the surface of substrate 1 by spinning element 3, which is previously immersed in a polymer solution or melt stored in or stored in a container (not shown) on substrate 1.

In a variant of the polymer fiber production method of the invention shown in Fig. 2, the polymer solution or melt is stored in the interior of the cartridge 5, which is divided by a piston 6 or membrane into two parts, one of which is connected to the cavity of the hollow elongate spinner. which in this variant is preferably a hollow conical needle (ie capillary) 30, but any other hollow spinning element 3 may be used, and the other is connected to a source of pressure medium (gas, preferably air or liquid), or is a piston 6 or a diaphragm in a not shown variant coupled / coupled with a mechanical drive. Due to the inertial effect, in the first variant it is advantageous if the source of the pressure medium is mounted on a stationary part of the polymer fiber generating device. The cartridge 5 is supported on a manipulator (not shown) capable of moving in at least two axes - vertically perpendicular to the substrate 1 (arrow y) and horizontally along the length of one of the dimensions of the substrate 1 (arrow z) and preferably horizontally along the longitudinal dimension. arrow x), optionally at any angle. However, any manipulation of the manipulator can be replaced or supplemented by the corresponding movement of the substrate. Furthermore, it is further advantageous for the formation of more complex, e.g. spatial, polymer fiber formations if the manipulator or its spinning element 3 is capable of rotation about at least one axis.

The conical hollow needle 30 is preferably made of an electrically conductive material (but may also be formed of an electrically non-conductive material) and its outlet opening has a diameter of 0.1 to 1.2 mm.

In this method of making polymer fibers, the tip of the hollow conical needle 30 is moved or contacted with the movement of the handle 30 to the surface of the substrate 1, and then pulsed with a pressure medium (eg gas or liquid) on the opposite side of the piston 6 or cartridge membrane 5 or of a mechanical drive (not shown) (see arrow P) pushes through the cavity of the conical needle 30 the required amount of solution or melt through the polymer (preferably 0.001 to 4.2 µl or more), thereby forming a droplet 2 of the material. Once formed, the hollow conical needle 30 is moved by manipulators along the trajectory T, which has a preferred arcuate shape in Fig. 2, but generally may have any other shape, in the desired direction to the desired distance from the solution droplet 2 or melt through the polymer, contact with the substrate 1. In this way, a separate polymer fiber 4 of the desired diameter, length and orientation is formed as described above. This is terminated and anchored upon subsequent contact of the hollow conical needle 30 with the surface of the substrate 1. Thereafter, the hollow conical needle 30 is returned by manipulation to the initial solution or melt droplet 2 with a polymer to contact or immerse it into the tip to retrieve the material to withdraw the other fiber 4, which is repeated until the desired number of fibers or desired linear is formed. , area or spatial formations.

Also in this variant, to achieve smaller diameters of the formed fibers 4, the extension described above can be used, whereby the movement of the hollow conical needle 30 along the trajectory T stops for a moment (tens of seconds), partially freezing the formed fiber 4.

In another embodiment (not shown), the movement of the piston 6 or diaphragm in the cartridge 5 can be replaced by the use of capillary forces, wherein an elongate guide element (e.g., (nano) tungsten wire) extends longitudinally in the cavity of the conical needle 30. and which naturally divides the solution or melt through the polymer into droplets, even with a smaller volume and with greater precision than the hollow conical needle 30.

The use of the cartridge 5, which moves in conjunction with the hollow conical needle 30, makes it possible to form an end drop 20 of the solution when anchoring the long end of the polymeric fiber 4 formed.

The polymer 4, which serves to securely anchor the end of the fiber to the surface of the substrate 1, and optionally also as a supply of material to form another polymer fiber (s) 4. The fiber 4 formed subsequently of the end drop material 20 may then be with the fiber. formed in the preceding stroke of the hollow conical needle 30 parallel to or may be arranged in any other desired manner. Thus, the hollow conical needle 30 can be reciprocated by means of a manipulator between two or more points on the surface of the substrate 1, at least one of which has an initial droplet 2 or an end droplet 20 of the polymer solution / melt, disposed thereon. or at any angle arranged or optionally intersecting fibers of different polymers and / or diameters and / or lengths.

Productivity can be increased if necessary by increasing the number of hollow conical needles 30 or other elongated spinning elements 3. At least some of the hollow conical needles may have a common manipulator or a common handle. If different hollow conical needles 30 have different cartridges 2 or are connected to different compartments of one cartridge 5 and / or if they have different dimensions and / or shape of their tip and / or outlet, it is possible simultaneously form fibers of different polymers and / or parameters, e.g. diameters.

Advantageously, the movement of the manipulator, in all the variants described above, takes place along an arched trajectory T, which in its initial and end phases is normal to the surface of the substrate 1. The manipulator moves with acceleration in its initial phase and deceleration, achieving a maximum speed of 1 to 100 m / min or higher.

The parameters of the polymer fibers produced are then determined by the properties of the spinning material and the speed of movement of the spinning element 3, and with suitable selection of these parameters it is possible to produce polymer fibers having a length of tenths of millimeters to units of meters. nm to 10 pm.

In this way, linear or planar formations can be produced on the surface of the substrate (s) with the desired orientation of the individual polymer fibers (wherein the individual fibers are stacked side by side with the desired relative orientation and possibly on top of each other) and layered these linear and / or planar formations. optionally using spatially shaped substrate 1 or more spatially formed substrates 1 in a space suitably disposed relative to one another. These formations made of biocompatible and possibly biodegradable polymer (eg polycaprolactone - PCL etc.) are then used especially as so-called "scaffolds". carriers for living cells in tissue engineering and regenerative medicine, where the orientation of their fibers, respectively. its inter-fiber spaces represents the direction of preferential deposition, respectively. cell growth, which makes it possible to produce, for example, functional replacements of various tissues with desired cell orientation, such as muscle, tendon, or neuronal tissues, etc. The structures formed in this way can be further modified by possible further mechanical processing, eg folding, coiling etc. then twist into the form of yarn (see eg Fig. 7), etc.

A suitable polymer for the production of polymer fibers by the process according to the invention in any variant thereof is, in particular, a polymer having a molecular weight close to or equal to 90,000, and a polymer having a relative molecular weight of at least 45,000 may also be used. ), polyvinyl butyral (PVB), polystyrene (PS), poly (methyl methacrylate) (PMMA), polycaprolactone (PCL), polyurethane (PU), etc. A suitable blend of these polymers or a copolymer of at least two of them may be fiberized, optionally a modified variant of any of them. The use of biocompatible and possibly biodegradable polymers approved for medical use is then a precondition for the manufacture of medical devices. At least one suitable substance or a precursor thereof, which is incorporated / incorporated into its structure during the formation of the fiber 4, can be added to the polymer solution or melt and provides suitable

-6308 308167 B6 or gives it special properties (eg antimicrobial properties, etc.).

The polymer or polymer blend is melted to form a melt. To form a solution, it is dissolved in an appropriate solvent, and when dissolved in an organic solvent (e.g., chloroform), the solvent is preferably stabilized with a suitable substance (e.g., ethanol).

During the formation of the polymer fibers by the method of the invention, it is possible to suitably combine different materials, or different variants of one material with different molecular weights, as well as fiber diameters, which allows eg to adjust the biological or possibly different degradation rate. from a material of lower molecular weight and possibly smaller diameter degrades more quickly.

The method of production of polymeric nanofibres according to any of the described variants proceeds in virtually any conditions, and in comparison with e.g. its performance is not significantly affected by the actual physico-chemical conditions in the spinning space. However, in order to limit the drying of the solution or solidification of the melt in the droplets 2, 20, it is preferred that at least the formation of the droplets 2, 20 or the entire polymer fiber production process takes place in an atmosphere with controlled gas composition and / or temperature.

Below are specific examples of manufacturing polycaprolactone (PCL) fibers, a biocompatible polymer approved for medical use, polyvinyl alcohol (PVA) and polyvinyl butyral (PVB).

Example 1

Dissolving polycaprolactone (PCL) with an average molecular weight of 90000 in a chloroform-ethanol solvent system (7: 3 ratio) produced a solution containing 24% by weight, (polycaprolactone), which was stored in the interior of the cartridge 5, which was divided by piston 6 two parts, one connected to the hollow conical needle 30 with a 0.62 mm diameter orifice, and the other connected to a compressed air source, with a pressure pulse of 0.6 bar, 0.15 s long, on the adhesive substrate 1 made of black paper (black was chosen as the contrast for the fibers to be formed) was displaced by a drop 2 of this solution of 0.065 µl. By means of a manipulator, the hollow conical needle cartridge 30 was then moved along the trajectory T to the endpoint on the surface of the substrate 1 at 80 mm from drop 2, wherein the maximum tip height of the hollow conical needle 30 above the surface of the substrate 1 was 16 mm. At the point of trajectory T, the end drop 20 of the polymer solution was formed on the surface of the substrate 1 in the same manner as drop 2, and fibers of the same polymer were formed in both phases of the reciprocating hollow conical needle 30. After every 100 fibers. by a manipulator moved 0.5 mm in a direction perpendicular to the trajectory plane T, where a new starting drop 2 and a new end drop 20 were formed. The manipulator was moving for the first 500 ms with acceleration while immediately reaching a speed of 8 m / min started to slow down and moved for another 1500 ms.

In this way, a linear formation formed of polycaprolactone nanofibers was formed, whose electron scanning microscope (SEM) images at 480x, 100x, 3000x and 5000x magnifications are shown in Figures 3-6.

In Fig. 7 there is an SEM image of a linear formation thus formed, which was subsequently bent by rotating a part of the substrate 1 with the ends of individual polymer nanofibres deposited.

In an analogous way, it is possible to create planar shapes with parallel arranged polymer fibers - see for example Fig. 8, or with fibers arranged at any angle into the grid - see

-7EN 308167 B6 eg Fig. 9. Especially these surface formations can be used, for example, as scaffolds, resp. carriers for the storage and cultivation of living cells, which colonize them preferably in the direction of the interfiber spaces - see, for example, Figs. 10-12, which show SEM images of these 3T3 murine fibroblasts; and Fig. 13 shows the image of the formation of Figs. 12 from a fluorescence microscope in which the bright spots represent the nuclei of the cells; direction of scaffold colonization.

Example 2

Dissolving polyvinyl alcohol (PVA) with an average molecular weight of 67,000 in demineralized water produced a solution containing 40% by weight of polyvinyl alcohol. Then two drops of this solution 2, 20 spaced 100 mm apart were formed on the surface of the substrate 1 (paper). By means of a manipulator, an elongated spinning element 3 consisting of a metal tube with an outer diameter of 0.4 mm was immersed in the initial droplet 2, which was then moved along the arched trajectory T and immersed in the final droplet 20 of the solution. The maximum height of the end of the elongated spinning element 3 above the surface of the substrate 1 was 20 mm. In this way, a polymer nanofiber was formed between the initial drop of solution 2 and the final drop of solution 20. By repeating this procedure, another polymer nanofibers were gradually formed in each phase of the spinning element 3 movement. While moving, the manipulator moved for the first 500 ms with acceleration, and after reaching a speed of 9 m / min, it began to move with a deceleration, thus moving an additional 1500 ms.

After forming the required number of polyvinyl alcohol nanofibres by dissolving polyvinylbutyral (PVB) of a relative molecular weight of 60,000 in ethanol, it formed a solution containing 15% by weight of polyvinylbutyral. This solution was spun as well as the polyvinyl alcohol solution and the formed nanofibres were deposited over polyvinyl alcohol nanofibres, creating a flat grid - see Fig. 14, where the lighter fibers are polyvinyl alcohol fibers (light color is achieved by adding a contrast medium AgNCb) and darker polyvinyl butyral nanofibers.

The process according to the invention can produce essentially any linear, planar or spatial formations with any precisely defined relative arrangement of the individual polymer fibers having a diameter of 100 nm to 10 µm. These formations are, after removal from the surface of the substrate 1, if necessary shaped or sized, e.g., cut out, or further processed, for example, by rolling, folding, and the like, before and / or after and it is possible to connect the individual fibers or groups of nanofibres of the formation to each other eg by their (partial) melting or etching (eg by vapors of a suitable solvent, or by applying an adhesive consisting of the same lower molecular weight polymer with lower solvent content). In another embodiment, the linear, planar or spatial formations may be applied directly to any suitable substrate 1, which is constituted directly by a layer of material that is used in conjunction with these fibers in the final application. Such a layer can be, for example, a fabric of any type, plastic or metal foil, a grid or a mesh, a layer of nanofibres, etc.

In one variation of the method for producing a spatial formation comprising polymeric fibers of 100 nm to 10 µm diameter, polymeric fibers of 100 nm to 10 µm diameter produced by the method of the invention are deposited parallel to each other and / or parallel and / or off-axis between different parts of a suitably shaped surface of a substrate. , or between two substrates placed e.g. against each other or in any other spatial arrangement.

By using the spinning element 3 and the substrate 1 of electrically conductive material, it is possible to stimulate the formed fiber 4 by an electric current, by closing an electric circuit between the substrate 1, the currently drawn fiber 4 and the spinning element 3. high DC voltage of any polarity, of magnitude in the range of units up to tens of kV. The fiber 4 is the most exposed part of this circuit and the conformations of its macromolecules are thus affected

Under the influence of an external electric field. This creates a material structure that improves the geometric and mechanical properties of the formed fiber. For safe implementation, it is necessary that the source of high DC voltage is controllable in the sense that the circuit is formed only at a distance of the spinner 3 from the surface of the substrate 1 greater than the breakdown distance of the applied high voltage.

PATENT CLAIMS

Claims (20)

Process for the production of polymer fibers having a diameter of 100 nm to 10 µm, characterized in that a drop (2) of a polymer solution or melt of at least 0.001 µl, during or after its formation, is formed on the surface of the substrate (1). immersing the end of the at least one elongated fiberising element (3) on whose surface and / or in its cavity a portion of the polymer solution or melt is retained from the drop (2), whereupon the fiberising element (3) is moved by the manipulator and / or by moving the substrate (1) moves to another location on the same or another substrate (1), wherein the polymer solution or melt on its surface and / or in its cavity remains interconnected by solution fiber (4) due to its viscosity and surface tension or a melt of polymer, the diameter of which decreases with the drop (2) on the surface of the substrate (1) as the spinner (3) and / or the substrate (1) moves, and this fiber (4) the end of the spinning element (3) is anchored to the surface of the substrate (1), thereby forming a polymer fiber having a diameter of 100 nm to 10 µm on the surface of the substrate (1). Method according to claim 1, characterized in that the drop (2) of the polymer solution or melt is formed on the surface of the substrate (1) by application of the polymer solution or melt by the application device or manually. Method according to claim 1, characterized in that the drop (2) of the polymer solution or melt is formed on the surface of the substrate (1) by applying a polymer solution or melt by means of a spinning element (3) onto which and / or or a polymer melt deposited by immersing it in a solution or melt of the polymer in the reservoir. Method according to claim 3, characterized in that the polymer solution or melt drop (2) is formed on the surface of the substrate (1) by forcing the polymer solution or melt from the solution or polymer melt through the cavity of the hollow spinner (3). Method according to claim 4, characterized in that the hollow spinning element (3) is mounted on the cartridge (5) and its cavity communicates with the interior of the cartridge (5) containing the solution or polymer melt. Method according to claim 4 or 5, characterized in that the hollow spinning element (3) is a hollow conical needle (30) whose outlet opening has a diameter of 0.1 to 1.2 mm or a tube with an outer diameter of 0.1 up to 1.5 mm. Method according to any one of the preceding claims, characterized in that the spinning element (3) is displaced along the trajectory (T) and the substrate (1) is static. Method according to claim 7, characterized in that the spinning element (3) is displaced along the arc trajectory (T). Method according to claim 7 or 8, characterized in that the displacement of the spinning element (3) is stopped before contact with the surface of the substrate (1) and continues after at least partially solidification of the fiber (4). -9EN 308167 B6 Method according to claim 7, 8 or 9, characterized in that the spinning element (3) is moved with a maximum speed of 1 to 100 m / min. Method according to claim 1, characterized in that the fiber (4) is anchored in the end drop (20) of the polymer solution or melt on the surface of the same or different substrate (1). Method according to claim 5 or 6 and 11, characterized in that the end drop (20) of the polymer solution or melt on the surface of the substrate (1) is formed by forcing at least 0.001 µl of polymer solution or melt from the interior of the cartridge (5). of the spinning element (3). Method according to claim 11 or 12, characterized in that at least one polymer fiber having a diameter of 100 nm to 10 µm is formed from the end drop (20) of the polymer solution or melt. Method according to claim 1, characterized in that a high DC voltage of any polarity is applied to the spinning element (3) and to the electrically conductive substrate (1) during the movement or interruption of the spinning element (3). The method of claim 1, wherein the polymer is a polymer selected from the group of polyvinyl alcohol PVA polyvinyl butyral PVB, polystyrene PS, poly (methyl methacrylate) PMMA, polycaprolactone PCL, polyurethane PU, a modified variant thereof, or any mixture or a copolymer of at least two of them. Method for producing a linear or planar formation comprising polymeric fibers having a diameter of 100 nm to 10 µm, wherein the individual polymeric fibers are formed by a method according to any one of claims 1 to 15, characterized in that the polymeric fibers thus formed are deposited on the substrate / substrates (1) repeatedly stacked side by side and / or stacked to form a linear or sheet-like structure. Method for producing a sheet or spatial formation comprising polymer fibers with a diameter of 100 nm to 10 µm, in which the individual polymer fibers are formed by a method according to any one of claims 1 to 15, characterized in that the polymer fibers thus formed are formed on the substrate / substrates (1) repeatedly deposited in parallel and / or in parallel, whereupon or wherein polymeric fibers of 100 nm to 10 µm diameter are formed in the same manner from the same or different material and deposited on them in a different orientation. A method for producing a spatial formation comprising polymeric fibers having a diameter of 100 nm to 10 µm, wherein the individual polymeric fibers are formed by a method according to any one of claims 1 to 15, characterized in that the polymeric fibers having a diameter of 100 nm to 10 µm produced by any of The methods according to claims 1 to 15 are laid parallel to each other and / or in parallel and / or out of alignment between different surface portions of one substrate (1) or between two substrates (1). Method according to claim 16 or 17, characterized in that the polymer fibers produced having a diameter of 100 nm to 10 µm are anchored at their ends on a substrate (1) other than the initial drop (2) of the polymer solution or melt, from which these fibers are formed. Method according to claim 17, characterized in that the formed polymer fibers with a diameter of 100 nm to 10 µm are deposited on the spatially shaped substrate (1).