EP3670714B1 - Système d'électrofilature et procédé de fabrication à grande échelle de matrices de fibres en 3d alignées - Google Patents
Système d'électrofilature et procédé de fabrication à grande échelle de matrices de fibres en 3d alignées Download PDFInfo
- Publication number
- EP3670714B1 EP3670714B1 EP19217414.2A EP19217414A EP3670714B1 EP 3670714 B1 EP3670714 B1 EP 3670714B1 EP 19217414 A EP19217414 A EP 19217414A EP 3670714 B1 EP3670714 B1 EP 3670714B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibres
- electrospinning
- capillary tube
- electrodes
- dimensional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
Definitions
- This invention relates to a continuous electrospinning system and process for the production of three-dimensional matrices of aligned polymeric fibres.
- the present invention has been applied in various areas, in the manufacture of products or structures, at the nanometric scale, which depend on the high surface area, such as biotechnology, pharmaceuticals, research, tissue engineering and medicine, particularly in regenerative medicine, such as cell therapy, cartilaginous and related tissue production, especially for the replacement and strengthening of joints.
- nanomaterials associated with the different possibilities of morphologies and functionalities reveal a series of possibilities for new fields of application and drive the progress in the processing of these nanostructures.
- the electrospinning or electrostatic spinning method is very advantageous, since the fibres obtained with this technique have a high surface area, combined with a low production cost and the possibility of being formed from a wide variety of polymers or composites.
- This technique is based on the application of high voltage (5-50 KV) and low current (0.5-1 ⁇ A) electric fields for the production of very small diameter fibres. In this process, the electrostatic forces control the formation and deposition of these fibres.
- the key configuration of a generic electroplating process consists of a syringe, where the molten polymer or polymeric solution is introduced, which is connected to a capillary tube, a diffuser pump, which controls the flow of the polymeric solution to be supplied, so that a drop of solution is always maintained at the tip of the capillary tube, a metal collector, maintained at zero potential (grounded), where the fibres produced will be collected, a high voltage source, responsible for producing a difference in potential between the tip of the capillary tube and the collector.
- a high voltage source responsible for producing a difference in potential between the tip of the capillary tube and the collector.
- the balance of electrostatic charges to which the droplet is subjected namely the surface tension force of the solution and the force exerted by the applied electric field, begins to suffer an imbalance and, from a certain critical value of electric field, a jet of polymeric material from the capillary tube is projected and accelerated towards the collector.
- the jet with the polymeric solution suffers evaporation of a large part of its solvent, thus ensuring that the fibres formed have enough rigidity to support their own weight.
- the solvent that remains in the solution such as moisture, allows the adhesion of one fibre to another, as they are deposited in layers, forming a non-woven web.
- the electrospun fibres form a two-dimensional, randomly oriented blanket or fabric due to the instability of the jet path.
- Oriented fibre networks have the possibility of developing anisotropic properties in materials. These relationships are quite obvious in the field of tissue engineering.
- Typical examples include the production of polymeric meshes, containing aligned fibres, used as substrates for culture and regeneration of neural cells, due to the inherently anisotropic nature of nerves and their regenerative mechanisms.
- the scaffold material has a three-dimensional structure of controlled porosity, so that it is possible to develop three-dimensional cell construction at the full depth of the matrix.
- This assembly system is the collector for production of fibre matrices, whose system comprises electrodes arranged in a 90° separated plane. The operation is based on the connection of the ground terminal to the electrodes arranged in the same line. The electrospun fibres are collected between the electrodes, which are connected to ground, and this connection is alternated between the pairs of electrodes with defined time intervals, allowing the formation of a mesh with layers of fibres with different arrangements ( Li, et al., Adv. Matter, 2004, 16:4, 361 ) .
- document US20110018174A1 discloses the production of aligned electrospun fibres, with location and orientation control of the fibres, using for this purpose a device that provides a voltage depending on the selected time, whereby that voltage is applied to a collector with multiple electrodes.
- said document does not disclose a process capable of forming a three-dimensional matrix of aligned fibres in any desired thickness.
- the present invention proposes to solve the problems of the state of the art above described, through the implementation of a system and process of production of three-dimensional matrices of aligned polymeric fibres, which can present several patterns of fibre alignment, along the thickness of the matrix, being this thickness dependent on the number of layers of deposited fibres, the thickness of fibres and the degree of compaction between layers.
- This invention relates to a continuous electrospinning system and process for the production of three-dimensional matrices of aligned polymeric fibres.
- three-dimensional matrices of aligned polymeric fibres occurs when one or more pairs of electrodes are exposed to the electrospinning capillary tube, thereby creating a layer of two-dimensional aligned fibres, on which are successively deposited, other layers formed by exposure of one or more pairs of electrodes to the capillary tube, accompanied, subsequently, by controlled movement away from the central collecting table of the capillary tube, after each layer of deposited fibres, in accordance with the claim 1.
- the process of the present invention allows the production of three-dimensional matrices of aligned polymeric fibres, which can present several patterns of fibre alignment along the thickness of the matrix, being this thickness dependent on the number of deposited fibre layers, fibre thickness and the degree of compaction between layers, in accordance with the claim 7.
- the produced matrices are used in various areas, such as biotechnology, pharmaceuticals, research, tissue engineering and medicine, in particular regenerative medicine, such as cell therapy and the production of cartilaginous and related tissue, in particular for joint replacement and strengthening, in accordance with the claim 9.
- the process of the present invention by using the proposed electrospinning system, has the additional advantage of being versatile, simple, inexpensive and working in a continuous mode, therefore not being necessary to produce series of layers with a certain alignment and to proceed to add other layers, with different alignment, to obtain three-dimensional matrices of polymeric fibres aligned with different patterns of fibre alignment and different thicknesses.
- the system of the present invention comprises an electrospinning capillary tube, a set of multi-electrodes, in which each electrode presents a controlled movement of exposure or retraction- occultation in relation to the electrospinning tube, and a central collecting table of the electrospun fibres, which comprises holes subject to vacuum pressure, with the possibility of regulating the distance between the electrospinning capillary tube and the electrodes in exposure position, and with controlled movement, towards the capillary tube axis, in accordance with the claim 12.
- the system of the present invention through the controlled movement of exposure or retraction-occultation of the electrodes, in relation to the electrospinning tube, with controlled vacuum production applied to the holes of the central collecting table, allows to secure the fibres to the table, as well as to achieve a certain degree of compaction (and consequently porosity in vertical direction) necessary for certain uses of the fibres.
- the controlled downward movement of the table allows the formation of three-dimensional aligned fibre structures.
- This invention relates to a system and a continuous electrospinning process for the production of three-dimensional matrices of aligned polymeric fibres, in particular for tissue engineering, with the possibility of producing several patterns of fibre alignment along the thickness of the matrix forming three-dimensional structures with controlled thicknesses.
- the system of the present invention comprises a module of fibre formation, which can consist basically of a syringe to contain a polymeric solution, connected to an injection pump, connected to a electrospinning capillary tube, which is connected to a voltage source, configured to provide positive polarity, the referred module is aligned longitudinally with the peripheral support in insulating material in which they are inserted longitudinally in holes in its multi-electrode surface, each electrode being provided with individual movement controlled towards the axis of the electrospinning capillary tube, with two positions, an exposure position and a retraction-occultation position with respect to the electrospinning capillary tube, as well as the possibility of selective activation of the negative polarities of these electrodes, when these electrodes are in the exposed position with respect to the electrospinning capillary tube, the alignment and distribution of these electrodes in the peripheral support delimit the area and shape of the central fibre collecting table.
- the fibre of polymeric material formed by electrospinning from the capillary tube with positive polarity, moves by the action of an electric field towards a collector module, which consists of a peripheral support in insulating material where are inserted longitudinally multi-electrodes and each electrode equipped with controlled movement towards the axis of the electrospinning capillary tube allowing its exposure or retraction-occultation with respect to the electrospinning capillary tube, a central collecting table delimited by the peripheral support of the multi-electrodes which consists of the region of accumulation of the electrospun fibres integrating these holes which extend from its upper surface to the inside of the chamber being this chamber connected to a vacuum pump with pressure control, this central collecting table has controlled movement towards the axis of the capillary tube allowing its separation or approach to the electrospinning capillary tube.
- peripheral support of the multi-electrodes and the central collecting table are mounted on a fixed platform where the length-adjustable bracket of the electrospinning capillary tube is placed, allowing the distance between the electrospinning capillary tube and the multi-electrodes to be adjusted.
- the exposure and retraction-occultation movement of the electrodes inserted into holes in the peripheral support to the electrospinning capillary tube results from a controlled electromagnetic force that develops at the end of the opposite electrode the upper surface of the peripheral support by the action of magnetic flux between a permanent magnet attached to the electrode and a fixed induction coil in the lower region of the peripheral support.
- Fibre flow is deposited and aligned when one or more electrode pairs are held in the exposure position with respect to the electrospinning capillary tube, and their respective negative polarities are activated, according to the intended fibre deposition orientation, thus forming an aligned two-dimensional fibre layer.
- the controlled movement away from the upper surface of the central collecting table of the electrospinning capillary tube, after each two-dimensional layer of aligned fibres has been deposited, allows the accumulation of successive fibre layers on the central collecting table thus allowing the formation of a three-dimensional fibre matrix structure in which its thickness is dependent on the number of layers of two-dimensional deposited fibres, the fibre thickness and the degree of intended compaction between layers by the vacuum system action.
- the successive two-dimensional layers of deposited fibres in the collector module, according to the referred electrospinning process, are kept in position in the central collecting table, between the multi-electrodes, by the action of vacuum generated in the holes of the upper surface of the central collecting table that communicate with a chamber connected to the vacuum pump inside it.
- the pressure control in the vacuum pump also has the purpose of controlling the degree of compaction between the two-dimensional fibre layers formed and so the porosity in the perpendicular direction to the plane of the deposited fibre layer.
- Control of the distance between the electrospinning capillary tube with positive polarity and the collector module, control of the exposure and retraction-occultation movements of the electrodes with negative polarity with regard to the electrospinning capillary tube, control of the movement of the upper surface of the central collecting table in reference to the electrospinning capillary tube, control of the negative polarity applied to the multi-electrodes and the control of the vacuum pump pressure are carried out by a computerised control unit which, depending on the fibre alignment intended for each two-dimensional layer deposited and the thickness of the matrix, program the sequence of all the movements, vacuum pressure and polarity of the necessary electrodes based on a computer program developed for that purpose.
- This invention has the ability to form matrices of aligned fibres of any thickness in continuous and with any alignment pattern along that thickness, because it combines different technical particularities, among them we highlight the use of multi-electrodes distributed spatially with the possibility of individual and controlled movements of exposure and retraction-occultation to the electrospinning capillary tube, thus allowing the possibility of controlling the alignment of deposited fibres, the support and deposit of the fibres on the central collecting table and the separation of the fibres from the ends of the electrodes during the retraction movement, the surface of the collecting table being provided with holes subject to vacuum pressure, which on one hand allow the fibres to be fixed to the table and also allow the control of the degree of compaction (porosity) between the different layers of deposited fibres, this capacity being also associated with the movement of the collecting table away from the electrospinning capillary tube, thus allowing the successive deposit of aligned fibre layers to the intended thickness.
- Electrospinning system for the production of three-dimensional matrices of aligned polymeric fibres
- the system of the present invention comprises, in a broad sense:
- the system of the present invention also comprises a permanent magnet, attached to each of the electrodes, to generate the forces of attraction and repulsion between the ends of the electrodes and the electromagnetic coils, also present in the system, a computerized control unit and the electronics necessary for its proper operation, actuators, including the actuator of the linear movement of the central collecting table, as well as all the electrical wiring for distribution of energy to the various components of the system.
- system (1) of this invention comprises:
- the electrospinning system (1) comprising the fibre (2) of polymeric material formed by electrospinning from the capillary tube (3) with positive polarity moves by the action of an electric field towards a collector module, which consists of a peripheral support (15) in insulating material where they are longitudinally inserted in holes (6) in its surface (20) multi-electrodes (7) (14) and each electrode (7) (14) equipped with controlled movement towards the axis of the electrospinning capillary tube (3) allowing its exposure (7) or retraction-occultation (14) with respect to the electrospinning capillary tube (3), a central collecting table (17) delimited by the peripheral support (15) of the multi-electrodes which consists of the region of accumulation of the electrospun fibres integrating this holes (16) which extend from its surface (19) to a chamber (21) in its interior being this chamber connected by a channel (18) to a vacuum pump (13) with pressure control, this central collecting table (17) has controlled movement towards the axis of the capillary tube (3) allowing its movement
- this continuous electrospinning system and process comprises the peripheral support (15) of the multi-electrodes mounted on a fixed platform (8) on which the length-adjustable support (5) of the electrospinning capillary tube (3) is supported, allowing the distance between the electrospinning capillary tube (3) and the electrodes in exposure position (7) to the electrospinning capillary tube to be adjusted (3).
- the movement of exposure (22) and retraction-occultation (23) of the electrodes (7) and (14) inserted into holes (6) of the peripheral support (15) to the electrospinning capillary tube (3) results from an electromagnetic force (22) (23) controlled by the computer control unit (9) which develops at the end of the electrode (7) (14) opposite the upper surface (20) of the peripheral support (15) by the action of magnetic flux between a permanent magnet (11) attached to the electrode (7) (14) and an induction coil (10) positioned in the lower region of the peripheral support (15).
- the deposit and alignment of the fibre flow (2) is carried out when one or more pairs of electrodes (7) are held in the exposed position in relation to the electrospinning capillary tube (3), and their respective negative polarities are activated by the computer control unit (8), according to the intended fibre deposition orientation thus forming successive aligned two-dimensional fibre layers (27) (28) (29) (30) (31) (34) (35) .
- the retraction-occultation movement of the electrodes (23), with respect to the electrospinning capillary tube (3), towards the interior of its hole (6) in the peripheral support (15) allows the support - deposit of the fibres (27) (28) (29) (30) (31) (33) (35) on the surface (19) of the central collecting table (17) followed by the separation - release of the fibres from the end of the electrodes (7).
- the successive two-dimensional fibre layers deposited (27) (28) (29) (30) (31) (33) (35) on the central collecting table (17) are maintained in position on the central collecting table (17) by the action of a suction force (25) generated by the vacuum pressure in the surface holes (19) of the central collecting table (17) that communicate with a chamber (21) in its interior connected by a channel (18) to the vacuum pump (13) .
- the pressure control in the vacuum pump (13) is also intended to control the suction forces (25) on the fibres and the degree of compaction between the formed two-dimensional fibre layers (27) (28) (29) (30) (31) (33) (35) and then the porosity in the perpendicular direction of the deposited fibre layer plane.
- Control of the distance between the electrospinning capillary tube (3) with positive polarity through its holder (5) and the exposed multi-electrodes (7) with negative charge, control of the exposure movements (22) and retraction-occultation (23) of the electrodes (7) with negative polarity with respect to the electrospinning capillary tube (3), control of the surface movement (19) of the central collecting table (17) with respect to the electrospinning capillary tube (3), the control of the negative polarity applied to the electrodes (7) and the control of the vacuum pump pressure (13) are carried out by a computer control unit (8) which, depending on the alignment (301) (302) (303) (304) (305) (306) (307) (308) (309) of fibres intended for each two-dimensional layer deposited (27) (28) (29) (30) (31) (33) (35) and the thickness (26) of the matrix, program the sequence of all movements, vacuum pressure and polarity of the required electrodes based on a computational program developed for this purpose.
- the process of the present invention is carried out in several steps with the use of the electrospinning system (1), as described in the previous section.
- the production of three-dimensional matrices of aligned polymeric fibres (2) occurs when one or more pairs of electrodes (7,14) are exposed to the capillary tube (3), according to the intended fibre orientation, thus forming a two-dimensional layer of aligned fibres, which are kept in adequate position on the central collecting table (17), after the movement of retraction-occultation of the electrodes, by action of the suction force generated by vacuum pressure in their holes.
- the controlled movement away from the central collecting table (17) of the electrospinning tube (3), after each deposited fibre layer, allows the accumulation of successive layers and the formation of a three-dimensional matrix with thickness depending on the number of deposited fibre layers, the fibre thickness and the degree of compaction between layers controlled by vacuum pressure.
- the production process of aligned three-dimensional matrices of polymeric fibres of the present invention comprises the following steps:
- the production of three-dimensional matrices of aligned polymeric fibres, with more than two layers, is performed by repeating steps (a), (b) and (c), as many times as the number of desired layers, to the process as described above.
- the process of the present invention comprises the following steps:
- one or more pairs of electrodes are used which are exposed (7) to the capillary tube (3), containing a certain polymeric solution, where the composition and concentration of the polymer in solution, as well as the solvents used, vary according to the purpose for which the matrix is intended.
- a certain negative voltage is applied, also selected according to the type of fibre and matrix to produce.
- Each one of the different alignments of the two-dimensional fibre layers is obtained by the sequential exposure (7), of a number of selected electrodes, to the electrospinning capillary tube (3) during a certain period, also selected according to the purpose for which the fibres and the matrices are intended.
- the different layers of deposited two-dimensional fibres thus result from the performance of consecutive cycles of various types of alignment, which is obtained by combining the variables or production factors described above.
- the set of different layers, differently aligned, forms an alignment pattern (200), which is repeated successively between the first (203), intermediate (205) and last (206) pattern, thus resulting in the thickness (26) of the three-dimensional matrix, which is delimited by the dimensions (202) and (201) of the central collecting table (17).
- the production process of three-dimensional matrices of aligned polymeric fibres is carried out continuously by successively carrying out the various steps for the formation of two-dimensional layers of polymeric fibres, according to the above described.
- the thickness of the obtained matrices varies therefore, not only in function of the type and quantity of polymer used, but also in function of the number of deposited fibre layers, the thickness of these fibres and the degree of compaction between layers, each one of these aspects being controlled by vacuum pressure exerted on the fibre layers deposited in the central collecting table.
- the alignment of the fibres in each layer is controlled by the different movements and number of electrodes exposed and/or concealed in each cycle of fibre formation.
- This example refers to the production of a matrix composed of 27 layers of aligned polymeric fibres for cartilage engineering, with a total thickness of 3,24 mm.
- the polymer used to manufacture the matrix was polycaprolactone (PCL) with a molecular weight of 80,000 Da.
- PCL was dissolved at concentrations of 12% dichloromethane (DCM) and dimethylformamide (DMF) at a ratio of 1:1 (v:v) after 12 hours of stirring at room temperature.
- DCM dichloromethane
- DMF dimethylformamide
- the molten polymer was electrospun using a capillary tube (3) with a flow of 2,5 mL/h, a voltage of 25 kV and a working distance of 15 cm to the central collecting table (17) .
- the central collecting table (17) has a diameter of 8mm, and the holes (16) on its surface are subjected to a vacuum pressure of 3300 Pa.
- Each of the different alignments of the two-dimensional fibre layers was obtained by sequential exposure (7) of pairs of electrodes to the electrospinning capillary tube (3) for 2.3 min.
- the 27 layers of deposited two-dimensional fibres resulted from the performance of 3 consecutive cycles (3 times) of 9 alignment patterns (301), (302), (303), (304), (305), (306), (307), (308) and (309) in this order, as follows:
- the central collecting table (17) has moved away from the electrospinning capillary tube about 0,12 mm, this being the value corresponding to the average thickness of each layer of deposited dimensional fibres.
- the central collecting table moved away about 3,24 mm, corresponding to the thickness of the matrix obtained at the end of the 27 deposited layers.
- the three-dimensional matrix of aligned fibres obtained in this example shows, like the native cartilage, a preferential alignment of the fibres in its surface area parallel to the surface, in the intermediate area there is no preferential alignment, and in the deepest area the fibres are aligned in a vertical manner to the surface.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Surgical Instruments (AREA)
Claims (15)
- Système d'électrofilage (1) comprenant (a) un module de formation de fibres, (b) un réseau multi-électrodes, (c) un module collecteur, pour collecter les fibres déposées, une alimentation électrique, une pompe à vide (13), caractérisé en ce que :a) Le module de formation de fibres consiste en un tube capillaire d'électrofilage (3) de polarité positive ;b) Le réseau multi-électrodes est inséré dans un support périphérique (15) et comprend :- plusieurs électrodes (7) (14), chacune étant équipée d'un mouvement contrôlé vers l'axe du tube capillaire d'électrofilage (3) ;- plusieurs aimants (11), chacun desquels étant attaché à une électrode (7, 14) pour générer une force électromagnétique (22, 23), conjointement avec la bobine d'induction (10), contrôlés par l'unité informatique (9) ;c) Le module collecteur comprend :- un support périphérique (15), où les électrodes (7) (14) sont insérées longitudinalement dans des trous (6) sur sa surface (20), ledit support (15) étant monté sur une plate-forme fixe (8), où le support réglable en longueur (5) du tube capillaire d'électrofilage (3) est supporté, pour ajuster la distance entre le tube capillaire d'électrofilage (3) et les électrodes en position d'exposition (7), par rapport au tube capillaire d'électrofilage (3) ;- une table collectrice centrale (17), délimitée par le support périphérique (15) précité, définissant une zone d'accumulation de fibres électrofilées, et présentant également des trous (16), qui s'étendent depuis sa surface (19) jusqu'à une chambre (21) ;- une chambre (21), qui est située à l'intérieur de la table centrale (17), cette chambre étant reliée par un canal (18) à une pompe à vide (13) ;dans lequel :- chaque électrode est capable d'être indépendamment exposée (7) ou rétractée/occluse (14), par rapport au tube capillaire d'électrofilage (3) ;- la pompe à vide (13) exerce une dépression contrôlée sur les trous (16) ; et- la table collectrice centrale (17) présente un mouvement contrôlé, vers l'axe du tube capillaire (3), permettant son déplacement (24) à l'écart ou à proximité du tube capillaire d'électrofilage (3).
- Système d'électrofilage (1) selon la revendication précédente comprenant une unité de contrôle informatique (9) et un programme informatique.
- Procédé de production de matrices tridimensionnelles de fibres polymères alignées en continu qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé en ce qu'il comprend les étapes suivantes :a) exposition d'une ou plus paires d'électrodes (7) au tube capillaire (3) contenant une solution d'un certain polymère adapté à la fonction de la matrice à produire, cette exposition étant réalisée selon l'orientation des fibres visée, en appliquant une tension négative aux électrodes sélectionnées, pendant un certain temps, pour former des couches de fibres alignées (30) ;b) application d'une dépression à la couche de fibres alignées obtenue en (a) à travers les trous (16) de la table collectrice centrale (17), avec mouvement de retrait-occultation des électrodes (14) ;c) séparation de la table collectrice centrale (17) du tube capillaire d'électrofilage (3), par action de déplacement (33) de l'actionneur (12) ;d) répétition de cycles séquentiels d'exposition de paires d'électrodes (7) au tube capillaire d'électrofilage (3) de (a), application d'une dépression à la couche de fibres alignées (b) et séparation de la table collectrice centrale (17) du tube capillaire d'électrofilage (3) de (c), autant de fois que nécessaire pour former une matrice en couche fibreuse bidimensionnelle (2), avec l'alignement requis ;e) répétition des cycles, tels que décrits aux étapes (a), (b) et (c), autant de fois que nécessaire, dans lesquels au moins un des facteurs d'électrofilage est modifié par rapport à ceux définis à l'étape (a), (b) ou (c) pour former une matrice de couches fibreuses bidimensionnelles (2), avec l'alignement requis, cet alignement étant différent de celui obtenu aux étapes (a), (b), (c) et (d) ;f) répétition des cycles d'exposition de (e) autant de fois que nécessaire, dans lesquels au moins un des facteurs d'électrofilage est modifié par rapport à ceux définis au cycle précédent pour former une matrice de couches fibreuses bidimensionnelles (2), avec l'alignement requis, cet alignement étant différent de celui obtenu au cycle précédentdans lequel :
le mouvement contrôlé d'éloignement du tube d'électrofilage par rapport à la table collectrice centrale après chaque couche de fibres déposées permet l'accumulation de couches successives et la formation d'une matrice tridimensionnelle dont l'épaisseur dépend du nombre de couches de fibres déposées, de l'épaisseur des fibres et du degré de compactage entre les couches est contrôlé par la dépression et la dépression fixe les fibres à la table. - Procédé de production de matrices tridimensionnelles de fibres polymères alignées en continu selon la revendication précédente, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé en ce que le support périphérique présente un réseau multi-électrodes et en ce que chaque électrode présente un déplacement individuel contrôlé en direction de l'axe du tube capillaire d'électrofilage, comportant deux positions, l'une d'exposition et l'autre de retrait-occultation par rapport au tube capillaire d'électrofilage.
- Procédé de fabrication de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 ou 4, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé en ce que la table collectrice centrale est délimitée par le support périphérique des multi-électrodes consistant en la zone d'accumulation de fibres électrofilées intégrant ces trous qui s'étend de sa surface jusqu'à une cavité à l'intérieur d'elle qui est ladite cavité reliée à une pompe à vide avec régulation de pression, dans lequel la table collectrice centrale a un mouvement contrôlé en direction de l'axe du tube capillaire permettant sa séparation ou son approche du tube capillaire d'électrofilage.
- Procédé de fabrication de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 5, qui aboutit dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé par le mouvement d'exposition et de retrait-occultation des électrodes insérées dans des trous du support périphérique vers le tube capillaire d'électrofilage résultant d'une force électromagnétique contrôlée qui se développe à l'extrémité de l'électrode opposée à la surface supérieure du support périphérique par l'action du flux magnétique entre un aimant permanent fixé sur l'électrode et une bobine d'induction positionnée dans la zone inférieure du support périphérique.
- Procédé de production de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 6, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé en ce que le dépôt et l'alignement du flux de fibres est effectué lorsqu'une ou plus paires d'électrodes sont maintenues en position exposée par rapport au tube capillaire d'électrofilage, et leurs polarités négatives respectives sont activées, selon l'orientation visée du dépôt de fibres formant ainsi une couche de fibres bidimensionnelles alignées.
- Procédé de fabrication de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 7, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé par le mouvement de retrait-occultation des électrodes, par rapport au tube capillaire d'électrofilage, vers l'intérieur de son trou dans le support périphérique pour supporter et le dépôt des fibres sur la table collectrice centrale suivi de la séparation des fibres des extrémités des électrodes.
- Procédé de production de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 8, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé par le mouvement d'éloignement contrôlé du tube capillaire d'électrofilage par rapport à la surface de la table collectrice centrale, après chaque couche bidimensionnelle de fibres alignées, pour accumuler des couches successives de fibres sur la table collectrice centrale pour la formation d'une structure matricielle de fibres tridimensionnelle dans laquelle son épaisseur dépend du nombre de couches de fibres bidimensionnelles déposées, de l'épaisseur des fibres et du degré de compactage entre les couches requis par l'action du système et la dépression.
- Procédé de fabrication de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 9, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé par les couches successives de fibres déposées dans le module collecteur, maintenues en position dans la table collectrice centrale, par action de la force de succion générée dans les trous de la surface de la table collectrice centrale par action de la dépression générée dans la chambre intérieure de la table collectrice centrale qui communique avec la pompe à vide.
- Procédé de production de matrices tridimensionnelles de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 10, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé par le contrôle de pression dans la pompe à vide contrôlant le degré de compactage entre les couches de fibres bidimensionnelles formées et la porosité dans la direction perpendiculaire du plan de couche de fibres déposées.
- Procédé de production de réseaux tridimensionnels de fibres polymères alignées en continu selon l'une quelconque des revendications précédentes 3 à 11, qui se manifeste dans le système selon l'une quelconque des revendications 1 ou 2 caractérisé en ce que les paramètres sont contrôlés par une unité de contrôle informatique (9) et les mouvements des électrodes étant contrôlés par un programme informatique.
- Matrices tridimensionnelles de fibres polymères alignées caractérisées par 27 couches de fibres polymères bidimensionnelles, avec 9 motifs d'alignement (301), (302), (303), (304), (305), (306), (307), (308) et (309), d'une épaisseur totale de 3,24 mm.
- Matrices tridimensionnelles de fibres polymères alignées, selon la revendication précédente, caractérisées par un alignement préférentiel des fibres, (i) parallèlement dans la surface qu'elles occupent, (ii) sans aucun alignement préférentiel dans la zone intermédiaire, et (iii) les fibres sont alignées d'une manière verticale vers la surface dans la zone la plus profonde.
- Matrices tridimensionnelles de fibres polymères alignées, telles que décrites dans l'une quelconque des revendications 13 ou 14, caractérisées en ce qu'elles sont appliquées en médecine, en médecine régénératrice et/ou en ingénierie du cartilage.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PT115228A PT115228B (pt) | 2018-12-21 | 2018-12-21 | Sistema e processo de fabricação em larga escala de matrizes tridimensionais de fibras alinhadas por eletrofiação |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3670714A1 EP3670714A1 (fr) | 2020-06-24 |
| EP3670714B1 true EP3670714B1 (fr) | 2021-12-29 |
Family
ID=68944584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19217414.2A Active EP3670714B1 (fr) | 2018-12-21 | 2019-12-18 | Système d'électrofilature et procédé de fabrication à grande échelle de matrices de fibres en 3d alignées |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP3670714B1 (fr) |
| PT (2) | PT115228B (fr) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115584563B (zh) * | 2022-10-26 | 2025-08-26 | 宁波方太厨具有限公司 | 中空线电极、静电纺丝装置及应用、静电纺丝方法 |
| CN120570716B (zh) * | 2025-08-05 | 2025-11-04 | 四川大学华西医院 | 一种植入假体和义肢密封的固定装置 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2349950A (en) | 1937-08-18 | 1944-05-30 | Formhals Anton | Method and apparatus for spinning |
| US7981353B2 (en) | 2005-12-12 | 2011-07-19 | University Of Washington | Method for controlled electrospinning |
| US7828539B1 (en) | 2007-03-26 | 2010-11-09 | Clemson University | Fabrication of three dimensional aligned nanofiber array |
| US8211352B2 (en) | 2009-07-22 | 2012-07-03 | Corning Incorporated | Electrospinning process for aligned fiber production |
| US9005604B2 (en) | 2009-12-15 | 2015-04-14 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Aligned and electrospun piezoelectric polymer fiber assembly and scaffold |
| CZ201093A3 (cs) * | 2010-02-05 | 2011-08-17 | Cpn S.R.O. | Zarízení pro výrobu dvojrozmerných nebo trojrozmerných vlákenných materiálu z mikrovláken nebo nanovláken |
| CN103906703B (zh) * | 2011-10-14 | 2016-08-24 | 应用材料公司 | 用于对准通过静电纺丝工艺沉积的纳米线的方法和设备 |
| US20130302595A1 (en) * | 2012-05-10 | 2013-11-14 | Biao Liu | Super-hydrophobic and oleophobic transparent coatings for displays |
| US20160004706A1 (en) | 2014-07-01 | 2016-01-07 | Microsoft Corporation | Security trimming of search suggestions |
-
2018
- 2018-12-21 PT PT115228A patent/PT115228B/pt active IP Right Grant
-
2019
- 2019-12-18 PT PT192174142T patent/PT3670714T/pt unknown
- 2019-12-18 EP EP19217414.2A patent/EP3670714B1/fr active Active
Also Published As
| Publication number | Publication date |
|---|---|
| PT115228B (pt) | 2023-04-18 |
| EP3670714A1 (fr) | 2020-06-24 |
| PT3670714T (pt) | 2022-03-23 |
| PT115228A (pt) | 2020-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Improving fiber alignment during electrospinning | |
| Burger et al. | Nanofibrous materials and their applications | |
| EP2531636B1 (fr) | Appareil pour la production de matériaux fibreux de microfibres et de nanofibres bidimensionnels ou tridimensionnels | |
| Teo et al. | A review on electrospinning design and nanofibre assemblies | |
| CN102084042B (zh) | 电纺丝纤维管状材料及其制备方法 | |
| Zhao et al. | Nanofibrous patterns by direct electrospinning of nanofibers onto topographically structured non-conductive substrates | |
| EP2045375B1 (fr) | Appareil et procédé pour l'électrofilature de structures 2D ou 3D de matériaux micro ou nano-fibreux | |
| CN101586288B (zh) | 阵列多喷头静电纺丝设备 | |
| JP4977336B2 (ja) | 高分子フィブリルを製造する装置およびその方法 | |
| EP2931951B1 (fr) | Procédé de production de nanofibres de polymère par filage de solution ou fusion de polymère dans un champ électrique et formation linéaire à partir de nanofibres de polymère préparées par ce procédé | |
| EP1992721A1 (fr) | Structures fibreuses, procédés et dispositifs pour les préparer | |
| Yousefzadeh et al. | Modeling performance of electrospun nanofibers and nanofibrous assemblies | |
| EP3670714B1 (fr) | Système d'électrofilature et procédé de fabrication à grande échelle de matrices de fibres en 3d alignées | |
| Liu et al. | Uniform field electrospinning for 3D printing of fibrous configurations as strain sensors | |
| WO2009102365A2 (fr) | Production de fibres électrofilées avec rapport de forme régulé | |
| Kessick et al. | Microscale electrospinning of polymer nanofiber interconnections | |
| Liu et al. | Simulation of electrospun nanofibre deposition on stationary and moving substrates | |
| Kim et al. | An applicable electrospinning process for fabricating a mechanically improved nanofiber mat | |
| EP3882385B1 (fr) | Fabrication automatique de matrices de cellules tridimensionnelles avec des nanofibres à alignement contrôlé et distribution uniforme de cellules | |
| ES2961325T3 (es) | Fabricación automatizada de matrices celulares tridimensionales con nanofibras de alineación controlada y distribución celular uniforme | |
| Haseeb | Controlled deposition and alignment of electrospun PMMA-g-PDMS nanofibers by novel electrospinning setups | |
| CN219297711U (zh) | 多功能静电纺丝设备 | |
| Lee et al. | Focused Patterning of Electrospun Nanofibers Using a Dielectric Guide Structure. Polymers 2021, 13, 1505 | |
| Khandaker et al. | Biofabrication techniques for neural tissue engineering | |
| Molnár et al. | Electrospun nanofibers for textile application–a finite element study |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20201022 |
|
| RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 5/02 20060101ALI20201208BHEP Ipc: D01D 5/00 20060101AFI20201208BHEP Ipc: D04H 1/728 20120101ALI20201208BHEP |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20210115 |
|
| GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| INTC | Intention to grant announced (deleted) | ||
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20210707 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1458722 Country of ref document: AT Kind code of ref document: T Effective date: 20220115 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602019010461 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Ref document number: 3670714 Country of ref document: PT Date of ref document: 20220323 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20220316 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220329 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20211229 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1458722 Country of ref document: AT Kind code of ref document: T Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220329 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220330 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220429 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602019010461 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20220930 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IE Payment date: 20221228 Year of fee payment: 4 Ref country code: FR Payment date: 20221222 Year of fee payment: 4 Ref country code: DE Payment date: 20221212 Year of fee payment: 4 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20221214 Year of fee payment: 4 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20221228 Year of fee payment: 4 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221218 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230920 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230920 |
|
| PGRI | Patent reinstated in contracting state [announced from national office to epo] |
Ref country code: PT Effective date: 20231010 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20191218 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602019010461 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20231218 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20231231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211229 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240702 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231218 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231218 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231218 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231218 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240702 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231231 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20250729 Year of fee payment: 7 |