EP1929074A1 - Konjugatelektrospinvorrichtungen, sowie damit hergestellte nanofasern enthaltendes konjugatvlies und -filament - Google Patents
Konjugatelektrospinvorrichtungen, sowie damit hergestellte nanofasern enthaltendes konjugatvlies und -filamentInfo
- Publication number
- EP1929074A1 EP1929074A1 EP05856366A EP05856366A EP1929074A1 EP 1929074 A1 EP1929074 A1 EP 1929074A1 EP 05856366 A EP05856366 A EP 05856366A EP 05856366 A EP05856366 A EP 05856366A EP 1929074 A1 EP1929074 A1 EP 1929074A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nozzles
- spinning dope
- spinning
- nozzle block
- nozzle
- 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.)
- Withdrawn
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 85
- 238000001523 electrospinning Methods 0.000 title claims abstract description 41
- 238000009987 spinning Methods 0.000 claims abstract description 233
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 40
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 230000003252 repetitive effect Effects 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 15
- 239000004020 conductor Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000004804 winding Methods 0.000 description 9
- 230000001939 inductive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 acryl Chemical group 0.000 description 2
- 239000002473 artificial blood Substances 0.000 description 2
- 230000002146 bilateral effect Effects 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000012811 non-conductive material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
Definitions
- the present invention relates to an conjugate electrospinning devices which can mass-produce two or more kinds of fibers having a nano level thickness (hereinafter, “nanofibers”) at a time by simultaneously electrospinning two or more different kinds of polymer spinning dope through nozzles aligned on one nozzle block.
- nanofibers nano level thickness
- the present invention relates to a conjugate non-woven fabric (herainfter, "conjugate nanofiber non-woven fabric) which is prepared by the aforementioned conjugate electrospinning devices and has two or more kinds of nanofibers mixed with each other. Moreover, the present invention relates to a continuous filament
- conjugate nanofiber filament which is prepared by the aforementioned conjugate electrospinning devices and has two or more kinds of nanofibers mixed with each other.
- Products such as non- woven fabrics, membranes, braids, etc., composed of nanofibers are widely used for commodities, agricultural applications, apparel, industrial applications, etc. Specifically, they are used in various fields such as artificial leather, artificial suede, hygienic band, clothing, diapers, packing material, miscellaneous goods, a variety of filter material, medical materials for gene carriers, military material like bulletproof vests and so on.
- the conventional electrospinning devices includes; a spinning dope main tank for storing a spinning dope; a metering pump for quantitatively supplying the spinning dope; a nozzle block having a plurality of nozzles aligned for discharging the spinning dope; a collector positioned at the lower end of the nozzles, for collecting the spun fibers; and a voltage generator for generating a voltage.
- the conventional process for preparing the nanofibers using the electronic spinning devices will now be described in detail.
- the spinning dope from the spinning dope main tank is consecutively quantitatively provided to the plurality of nozzles supplied with a high voltage through the metering pump.
- the spinning dope supplied to the nozzles is spun and collected on the collector supplied with the high voltage through the nozzles, thereby forming a single fiber web.
- the single fiber web is embossed or needle-punched to prepare the non- woven fabric.
- the conventional electrospinning devices and process for preparing the non-woven fabric using the same have a disadvantage in that an effect of electric force is reduced because the spinning dope is consecutively supplied to the nozzles having the high voltage.
- the electric force transmitted to the nozzles is dispersed to the whole spinning dope, and thus fails to overcome interface or surface tension of the spinning dopes.
- the electric force transmitted to the nozzles is dispersed to the whole spinning dope, and thus fails to overcome interface or surface tension of the spinning dopes.
- fiber formation effects by the electric force are deteriorated and the spinning dope is dropped in the form of drops (hereinafter, referred to as "droplet"), which deteriorates the quality of the product and hardly achieves mass production of the fiber.
- the conventional electrospinning devices can electrospin only one kind of polymer spinning dope through the nozzles aligned in one nozzle block, and thus cannot effectively satisfy various physical properties (features) of a nanofiber non-woven fabric required according to purpose.
- an object of the present invention to provide a conjugate electronic spinning devices which can mass-produce nano fibers by enhancing fiber formation effects by maximizing an electric force supplied to a nozzle block in electronic spinning, namely maintaining the electric force higher than interface or surface tension of a spinning dope, and which can mass-produce nanofibers of high quality by effectively preventing a droplet phenomenon.
- the present invention provides a conjugate nanofiber non-woven fabric and a conjugate nanofiber filament which have physical properties suitable for purpose by simple facilities and process by electrospinning two or more different kinds of polymer spinning dope through nozzles aligned on one nozzle block. Moreover, the present invention mass-produces two or more kinds of nanofibers of high quality at a time by maximizing an electric force in electrospinning and effectively preventing a droplet phenomenon.
- a conjugate electrospinning devices comprising: [I] nozzles for spinning two or more different kinds of spinning dope aligned on a nozzle block 4 regularly or in random order in repetitive units at the same ratio or in different ratios, aligned in random order at a predetermined ratio, or aligned thereon in random order at a predetermined ratio, or aligned thereon repetitively; [II] two or more spinning dope main tanks 1; and [III] a spinning dope drop device 3 installed between the spinning dope main tanks 1 and the nozzle block 4.
- the conjugate electrospinning devices of the present invention includes two or more spinning dope main tanks 1 for storing two or more different spinning dopes; a metering pump 2 for quantitatively supplying the spinning dope; a nozzle block 4 having block-type nozzles 5 composed of a plurality of pins, and discharging the spinning dope in a fiber shape; a collector 7 positioned at the upper or lower part of the nozzle block 4, for collecting spun single fibers; a voltage generator 9 for generating a high voltage; and a spinning dope discharger 12 connected to the top part of the nozzle block.
- FIG. 1 is a schematic view illustrating a process of preparing a conjugate nanofiber non-woven fabric using the conjugate electrospinning devices in accordance with the present invention.
- FIG. 2 is a schematic view illustrating a process of preparing a conjugate nanofiber non-woven filament using the conjugate electrospinning devices in accordance with the present invention.
- the nozzles for spinning two or more different kinds of polymer spinning dope are aligned on the nozzle block 4 regularly or in random order in repetitive units at the same ratio or in different ratios.
- the nozzles are repetitively aligned on the nozzle block alternately in a row in either transverse, longitudinal or diagonal direction.
- FIG. 3 is a pattern diagram illustrating nozzles for spinning two or more different kinds of polymer spinning dope aligned on a nozzle block alternately in a row in a diagonal direction.
- FIG. 4 is a pattern diagram illustrating nozzles for spinning two or more different kinds of polymer spinning dope aligned on a nozzle block regularly in repetitive units at the same ratio or in different ratios in accordance with the present invention.
- FIG. 5 is a pattern diagram illustrating nozzles for spinning two or more different kinds of polymer spinning dope, being aligned alternately in a row in a longitudinal direction and supplying the spinning dope.
- the number of spinning dope main tanks 1 and 1 ' for storing and supplying different polymer spinning dopes are two or more, and the spinning dope drop device 3 is arranged between the spinning dope main tanks and the nozzle blocks 4.
- outlets of the nozzles 5 installed on the nozzle block 4 are formed in an upward direction, though they may be formed in an upward direction as well as downward direction or horizontal direction. It is more preferable for mass production that the collector 7 is installed at an upper part of the nozzle block 4, though they may be installed at an upper part as well as lower part or horizontal position thereof.
- the conjugate electro spinning devices of the present invention description will be made with respect to a bottom up type electrospinning devices in which the outlets of nozzles 5 installed on a nozzle block 4 are formed in an upward direction, and a collector 7 is positioned at an upper part of the nozzle block 4.
- the present invention is not limited to the bottom up type electrospinning devices.
- the nozzle block 4 of the present invention includes: [I] a nozzle plate 4f on which nozzles 5 for spinning different spinning dopes are aligned regularly or in random order in repetitive units in the same ratio or in different ratios and two or more spinning dope supply plates 4h and 4h' positioned at the lower end of the nozzle plate and for supplying the spinning dope to the nozzles; [II] overflow removal nozzles 4a surrounding the nozzles 5, an overflow temporary storage plate 4g connected to the overflow removal nozzles and positioned at the right upper end of the nozzle plate and an overflow removal nozzle supporting plate 4e positioned at the right upper end of the overflow temporary storage plate and supporting the overflow removal nozzles; [III] air supply nozzles 4b surrounding the nozzles 5 and the overflow removal nozzles 4a, an air supply nozzle supporting plate 4c positioned at the top end of the nozzle block and supporting the air supply nozzles, and an air storage plate 4d positioned at the right lower end of
- the overflow removal nozzles 4a for removing unspun spinning dope and the air supply nozzle 4b for supplying air in order to increase the cumulative distribution of nanofibers are sequentially arranged around the nozzles 5 for electrospinning spinning dopes on the collector, thereby forming a triple tube shape.
- the nozzles 5 for spinning different spinning dopes are aligned on the nozzle block 4 of FIG. 6 alternately in a row in a diagonal direction.
- the outlets of the nozzles 5 for electrospinning the spinning dopes on the collector are enlarged in the shape of one or more flared tubes.
- the angle ⁇ of the nozzle 90 to 175°, more preferably, 95 to 150° is preferable so that the outlets of the nozzles 5 can form spinning dope drops of the same shape in the outlets of the nozzles 5. If the angle ⁇ of the nozzle outlet exceeds 175°, bigger drops are formed in the nozzle regions, thereby increasing the surface tension. As a result, in order to form nanofibers, a higher voltage is required. As spinning begins not at the center regions of drops, but at the edge parts of drops, the center regions of the drops are solidified, and this may block the nozzles.
- a nozzle length (L, L 1 , L2) is not specifically limited. However, it is preferred that the nozzle inner diameter (Di) is 0.01 to 5 mm and the nozzle outer diameter Do is 0.01 to 5mm. If the nozzle inner diameter or nozzle outer diameter is less than 0.01mm, the droplet phenomenon frequently occurs, and if the nozzle inner diameter or nozzle outer diameter exceeds 5mm, fiber formation may be impossible.
- FIGs. 8 and 9 illustrate the lateral side and plane of a nozzle having one enlarged part (angle) formed at a nozzle outlet
- FIGs. 10 and 11 illustrate the lateral side and plane of a nozzle having two enlarged parts (angle) formed at a nozzle outlet. That is, ⁇ i as illustrated in FIG. 10 is the angle of a first nozzle outlet which is a part for spinning the spinning dope, and ⁇ 2 is the angle of a second nozzle outlet which is a part for supplying the spinning dope.
- the nozzles 5 in the nozzle block 4 are aligned in plural number on the nozzle plate 4f, and the overflow removal nozzles 4a surrounding them and the air supply nozzles 4b are sequentially installed outside of the nozzles 5.
- the overflow removal nozzles 4a are provided for the purpose of preventing a droplet phenomenon, which occurs in the event that not every spinning dope formed in excessive amount at the outlets of the nozzles 5 is fiberized, and recovering an overflowing spinning dope, and it serves to collect an unfiberized spinning dope at the nozzle outlets and feed it to the overflow temporary storage plate 4g positioned at the right lower end of the nozzle plate 4f.
- the overflow removal nozzles 4a have a larger diameter than the nozzles 5, and are preferably made of insulating material.
- the overflow temporary storage plate 4g is made of insulating material, and serves to temporally store a residual spinning dope introduced through the overflow removal nozzles 4a and then feed it to the spinning dope supply plate 4h.
- the air storage plate 4d for supplying air is positioned at the upper end of the overflow temporary storage plate 4g, and supplies air to the air supply nozzles 4b surrounding the nozzles 5 and the overflow removal nozzles 4a.
- the air supply nozzle supporting plate 4c is installed on the top layer of the nozzle block 4 having the air supply nozzles 4b aligned thereon, and the supporting plate 4c is composed of non-conductive material.
- the air supply nozzle supporting plate 4c is positioned at the nozzle block, and thus an electric force applied between the collector 7 and the nozzles 5 is only concentrated on the nozzles 5 so that spinning can be done smoothly only in the nozzle 5 regions.
- the distance h from the upper tip of the nozzles 5 to the upper tip of the air supply nozzles 4b is 1 to 20mm, preferably, 2 to 15mm.
- the height of the air supply nozzles 4b is set 1 to 20mm, preferably, 2 to 15mm, greater than that of the nozzles 5. If h is 0, that is, the air supply nozzles 4b are positioned at the same height as the nozzles 5, jet streams are not effectively formed in the nozzle 5 regions, thereby reducing the area of nanofibers attached on the collector 7.
- the speed of air in the air supply nozzles 4b is 0.05 to 50m/ sec, more preferably, 1 to 30m/ sec. If the air speed is less than 0.05m/sec, the dispersibility of nanofibers collected on the collector is low, and thus the collecting area is not increased much. If the air speed exceeds 50m/ sec, the area of nanofibers collected on the collector is decreased due to a too high air speed, and thus the collection uniformity of the nanofibers is deteriorated.
- the conductor plate 4i having pins aligned in the same way as the nozzles is installed at the right lower end of the nozzle plate 4f, and the voltage generator 9 is connected to the conductor plate 4i.
- An indirect heating type heater (not shown) is installed at the right lower end of the spinning dope supply plate 4h.
- the conductor plate 4i serves to apply a high voltage to the nozzles 5, and the spinning dope storage plate 4h serves to store the spinning dope introduced to the nozzle block 4 from the spinning dope drop device
- the spinning dope supply tube 4h is made with a minimum space so as to minimize the storage quantity of the spinning dope.
- the spinning dope drop device 3 of the present invention is designed to have an overally sealed cylindrical shape as shown in FIGs. 12 (a) and 12(b), and serves to supply the spinning dope continuously inlet from the spinning dope main tank 1 to the nozzle block
- the spinning dope drop device 3 is designed to have an overally sealed cylindrical shape as shown in FIGs. 12(a) and 12(b).
- FIG. 12(a) is a cross sectional view of the spinning dope drop device.
- FIG. 12(b) is a perspective view of the spinning dope drop device.
- a spinning dope inducing tube 3c for inducing the spinning dope to the nozzle block and a gas inletting tube 3b are arranged side by side at the upper end of the spinning dope drop device 3.
- the spinning dope inducing tube 3c is formed slightly longer than the gas inletting tube 3b.
- the gas inlets from the lower end of the gas inletting tube, and an initial gas inletting portion of the gas inletting tube is connected to a filter 3d.
- a spinning dope discharge tube 3d for discharging the dropped spinning dope to the nozzle block 4 is formed at the lower end of the spinning dope drop device 3.
- the center portion of the spinning dope drop device 3 is hollow shape so that the spinning dope can be dropped from the end of the spinning dope inducing tube 3c.
- the spinning dope induced into the spinning dope drop device 3 is flown through the spinning dope inducing tube 3c, but dropped at the end thereof. Therefore, flowing of the spinning dope is intercepted at least
- An inert gas such as nitrogen or air can be used as the gas.
- the agitator l ie is connected to an agitator motor 1 1a by a
- dope dissolved using a mixed solvent for a long time dope dissolved using a mixed solvent for a long time.
- a spinning dope discharger 12 for forcibly feeding the spinning dope excessively supplied to the nozzle block to the spinning dope main tank 1 is connected to the top part of the nozzle block 4.
- the spinning dope discharger 12 forcibly feeds the spinning dope excessively supplied into the nozzle block to the spinning dope main tank 1 by suction air.
- a heater (not shown) of direct heating type or indirect heating type is installed (attached) to the collector 7 of the present invention, and the collector is fixed or continuously rotates.
- thermoplastic or thermosetting resin spinning dope respectively stored in the two main tanks 1 and 1 ' are measured by the respective metering pumps 2 and 2', and quantitatively supplied to the respective spinning dope drop devices 3 and 3'.
- Exemplary thermoplastic or thermosetting resins used to prepare the spinning dopes include polyester resins, acryl resins, phenol resins, epoxy resins, nylon resins, poly(glycolide/L-lactide) copolymers, poly(L-lactide) resins, polyvinyl alcohol resins and polyvinyl chloride resins.
- a resin molten solution or resin solution may be used as the spinning dopes.
- spinning dope drop devices 3 and 3' When the spinning dopes supplied to the spinning dope drop devices 3 and 3' passes through the spinning dope drop devices 3 and 3', flowing of the spinning dopes is dropped at least once in the mechanism described above. Thereafter, the spinning dopes are supplied to the spinning dope supply plate 4h of the nozzle block 4 having a high voltage and having the agitator l ie installed thereto.
- the spinning dope drop devices 3 and 3' serve to prevent electricity from flowing in the spinning dope main tanks 1 and 1' by intercepting flowing of the spinning dopes.
- the nozzle block 4 discharges the respective spinning dopes in a bottom-up fashion through the nozzles aligned alternately in a row in a diagonal direction.
- the spinning dopes are collected by the collector 7 supplied with the high voltage to prepare a non- woven fabric web.
- the spinning dopes .fed to the spinning dope supply tube 4h are discharged to the upper part of the collector 7 through the nozzles 5 to form fibers.
- the nanofibers electrospun from the nozzles 5 are widely spread by air sprayed from the air supply nozzles 4b and collected on the collector 7, and thus the collection area becomes wider and the cumulative density becomes uniform.
- the excessive spinning dope not fiberized in the nozzles 5 is collected in the overflow removal nozzles 4a, passes through the overflow temporary storage plate 4g, and is moved back to the spinning dope supply plate 4h.
- the spinning dope excessively supplied to the top part of the nozzle block is forcibly fed to the spinning dope main tanks 1 and 1 ' by the spinning dope dischargers 12 and 12'.
- a voltage over 1 kV, more preferably 20 kV is generated by the voltage generator 6 and transmitted to the conductor plate 4i and the collector 7 installed at the lower end of the nozzle block 4. It is advantageous in productivity to use an endless belt as the collector 7. It is preferable that the collector 7 reciprocates a predetermined distance to the left and right in order to make uniform the density of the non- woven fabric.
- the nanofiber web 5 formed on the collector 7 is consecutively processed by an web supporting roller 14, and the prepared non-woven fabric winds on a winding roller 16. Thus, the preparation of the non-woven fabric is finished.
- the conjugate nanofiber non-woven fabric prepared by the devices of the present invention can easily satisfy the physical properties suitable for various purposes by adjusting the type and ratio of spinning dope.
- the conjugate nanofiber non-woven fabric of the present invention is used for various purposes including artificial leather, medical materials such as hygienic band, filter, artificial blood vessel, etc., winter vest, semiconductor wipers, non-woven fabrics for batteries and so on.
- a conjugate nanofiber filament is prepared by firstly preparing a nanofiber web 15 in the same way as in the preparation of the above-described conjugate nanofiber non- woven fabric, twisting the prepared nanofiber web 15 while passing it though an air
- twisting machine 18 drawing it while sequentially passing it through a
- first roller 19 a second roller 20 and a third roller 22, and then winding it
- the prepared nanofiber web may be drawn by a
- thermosetting machine 21 between the drawing and winding steps.
- the above nanofiber web 15 is in a ribbon form.
- nanofiber web having the large width is cut by a web cutting machine, or
- the present invention can mass-produce two or more kinds of high
- FIG. 1 is a schematic view illustrating a process of preparing a
- FIG. 2 is a schematic view illustrating a process of preparing a discontinuous filament composed of conjugate nanofibers using the conjugate electrospinning devices in accordance with the present invention
- FIG. 3 is a pattern diagram illustrating nozzles for spinning two or more different kinds of polymer spinning dope aligned on a nozzle block alternately in a row in a diagonal direction in accordance with the present invention (O: one spinning dope component, #: another spinning dope component);
- FIG. 4 is a pattern diagram illustrating nozzles for spinning two or more different kinds of polymer spinning dope aligned on a nozzle block regularly in repetitive units at the same ratio or in different ratios in accordance with the present invention (O: one spinning dope component, •: another spinning dope component);
- FIG. 5 is a pattern diagram illustrating nozzles for spinning two or more different kinds of polymer spinning dope, being aligned on a nozzle block alternately in a row in a longitudinal direction and supplying the spinning dope in accordance with the present invention (O : one spinning dope component, •: another spinning dope component);
- FIG. 6 is a pattern diagram of the nozzle block 4 in accordance with the present invention.
- FIG. 7 is a cross sectional diagram of the nozzle block 4 in accordance with the present invention.
- FIG. 8 and FIG. 10 are pattern diagrams illustrating a side of the
- FIG. 9 and FIG. 11 are exemplary views of a plane of the nozzle 5;
- FIG. 12(a) is a cross sectional view of a spinning dope drop device 3
- FIG. 12(b) is a perspective view of the spinning dope drop device 3
- FIG. 13 is a strength-elongation graph for each kind (type) of
- FIG. 14 is a tear strength graph for each kind (type) of nanofiber
- nozzle 4b air supply nozzle 4c: air supply nozzle supporting plate
- non-conductive material 4d air storage plate 4e: overflow removal nozzle supporting plate
- nozzle 6 nanofiber 7: collector (conveyer belt)
- nozzle block bilateral reciprocating device 11a motor for agitator l ie
- feed pipe 14 web supporting roller 15: nanofiber web
- thermosetting machine (heater)
- Example 1 Poly ( ⁇ -caprolactone) polymer (product of Aldrich, USA) having a number average molecular weight of 80,000 was dissolved in a mixed solvent of methylene chloride and N,N-dimethyl formamide (volume ratio: 75/25) at a concentration of 13 wt%, to prepare a spinning dope.
- the surface tension of the polymer spinning dope was 35 mN/m
- the spinning dope viscosity was 35 centipoises at a room temperature
- the electric conductivity was 0.02 mS/m
- the permittivity was 90.
- Polyurethane resin (Pellethane 2103-80AE of Dow Chemical Company) having a number average molecular weight of 80,000 was dissolved in N, N dimethyl formamide at 8 wt.%.
- the two kinds of spinning dopes were stored in the main tanks 1 and 1', quantitatively measured by the metering pumps 2 and 2', and supplied to the spinning dope drop devices 3 and 3', thereby discontinuously changing the flow of the spinning dopes. Thereafter, the spinning dopes were supplied to the nozzle block 4 as shown in FIG. 6, and electrospun in a bottom-up fashion in a fiber shape through the nozzles 5. The spun fibers were collected on the collector 7, to prepare a nanofiber web 15.
- the prepared nanofiber web 15 passed through the web supporting roller 14, and wound on the winding roller 16, to prepare a conjugate nanofiber non-woven fabric.
- the nozzles for spinning the two kinds of spinning dopes are aligned on the nozzle block 4 as shown in FIG. 4.
- the percentage of the number of nozzles for spinning the poly ( ⁇ -caprolactone) spinning dope to the total number of nozzles was 66.7%
- the percentage of the number of nozzles for spinning the polyurethane resin spinning dope was 33.3%.
- each nozzle block included 9,720 nozzles, and four nozzle blocks were employed, the total number of nozzles was 38,880, the spinning distance was 15cm, and the nozzle block 4 reciprocates at 2m/min.
- An electric heater was installed on the collector 7 and thus the surface temperature of the collector was 35 °C when performing electrospinning.
- the spinning dope overflowing the top part of the nozzle block 4 during the spinning process was forcibly fed to the spinning dope main tank 1 by using the spinning dope discharger 12 using suction air.
- the angle ⁇ of the nozzle outlets was 120°
- the inner diameter Di of the nozzles was 0.9mm
- the outer diameter thereof was lmm.
- the inner diameter of the air supply nozzles was 20mm
- the outer diameter thereof was 23mm
- the distance h from the upper tip of the nozzles 5 to the upper tip of the air supply- nozzles 4b was 8mm.
- the air speed was 10m/ sec. Model CH 50 of Symco Corporation was used as the voltage generator.
- the strength-elongation graph of the conjugate nanofiber non- woven fabric W thus prepared was shown in FIG. 13, and the tear strength graph thereof was shown in FIG.
- Poly ( ⁇ -caprolactone) polymer (product of Aldrich, USA) having a
- dope viscosity was 35 centipoises at a room temperature, the electric conductivity was 0.02 mS/tn, and the permittivity was 90.
- Polyurethane resin (Pellethane 2103-80AE of Dow Chemical
- the two kinds of spinning dopes were stored in the main tanks 1
- the spun fibers were collected on the collector 7, to prepare a
- nanofiber web 15 The prepared nanofiber web 15 passed through the web supporting roller 14, and wound on the winding roller 16, to prepare a conjugate nanofiber non- woven fabric.
- each nozzle block included 9,720 nozzles, and four nozzle blocks were employed, the total number of nozzles was 38,880, the spinning distance was 15cm, and the nozzle block 4 reciprocates at 2m/min.
- An electric heater was installed on the collector 7 and thus the surface temperature of the collector was 35 °C when performing electrospinning.
- the spinning dope overflowing the top part of the nozzle block 4 during the spinning process was forcibly fed to the spinning dope main tank 1 by using the spinning dope discharger 12 using suction air.
- the angle ⁇ of the nozzle, outlets was 120°
- the inner diameter Di of the nozzles was 0.9mm
- the outer diameter thereof was lmm.
- the inner diameter of the air supply nozzles was 20mm
- the outer diameter thereof was 23mm
- the distance h from the upper tip of the nozzles 5 to the upper tip of the air supply nozzles 4b was 8mm.
- the air speed was 10m/ sec.
- Model CH 50 of Symco Corporation was used as the voltage generator.
- the strength-elongation graph of the conjugate nanofiber non-woven fabric X thus prepared was shown in FIG. 13, and the tear strength graph thereof was shown in FIG. 14.
- Comparative Example 1 Poly ( ⁇ -caprolactone) polymer (product of Aldrich, USA) having a number average molecular weight of 80,000 was dissolved in a mixed solvent of methylene chloride and N,N-dimethyl formamide (volume ratio: 75/25) at a concentration of 13 wt%, to prepare a spinning dope.
- the surface tension of the polymer spinning dope was 35 mN/m
- the spinning dope viscosity was 35 centipoises at a room temperature
- the electric conductivity was 0.02 mS/m
- the permittivity was 90.
- the spinning dope was stored in the main tank 1 of a typical bottom up type electrospinning devices, quantitatively measured by the metering pump 2, and supplied to the nozzle block 4 having a voltage of 35 kV, and electrospun in a bottom-up fashion in a fiber shape through the nozzles 5.
- the spun fibers were collected on the collector 7, to prepare a nano fiber web 15.
- the prepared nanofiber web 15 passed through the web supporting roller 14, and wound on the winding roller 16, to prepare a conjugate nanofiber non-woven fabric.
- the nozzles for spinning the one kind of spinning dope are diagonally aligned on the nozzle block 4.
- each nozzle block included 9,720 nozzles, and four nozzle blocks were employed, the total number of nozzles was 38,880, the spinning distance was 15cm, and the discharge amount of one nozzle was 1.2mg/min, and the nozzle block 4 reciprocates at 2m/min.
- An electric heater was installed on the collector 7 and thus the surface temperature of the collector was 35 °C when performing electrospinning.
- the spinning dope overflowing the top part of the nozzle block 4 during the spinning process was forcibly fed to the spinning dope main tank 1 by using the spinning dope discharger 12 using suction air.
- the angle ⁇ of the nozzle outlets was 120°, the inner diameter Di of the nozzles was 0.9mm, and the outer diameter thereof was lmm.
- the inner diameter of the air supply nozzles was 20mm, the outer diameter thereof was 23mm, and the distance h from the upper tip of the nozzles 5 to the upper tip of the air supply nozzles 4b was 8mm.
- the air speed was 10m/ sec.
- Model CH 50 of Symco Corporation was used as the voltage generator.
- the strength-elongation graph of the conjugate nanofiber non-woven fabric Y thus prepared was shown in FIG. 13, and the tear strength graph thereof was shown in FIG. 14.
- Polyurethane resin (Pellethane 2103-80AE of Dow Chemical Company) having a number average molecular weight of 80,000 was dissolved in N 5 N dimethyl formamide at 8 wt.%.
- the spinning dope was stored in the main tank 1 of a typical bottom up type electrospinning devices, quantitatively measured by the metering pump 2, and supplied to the nozzle block 4 having a voltage of 35 kV, and electrospun in a bottom-up fashion in a fiber shape through the nozzles 5.
- the spun fibers were collected on the collector 7, to prepare a nanofiber web 15.
- the prepared nanofiber web 15 passed through the web supporting roller 14, and wound on the winding roller 16, to prepare a conjugate nanofiber non-woven fabric.
- each nozzle block included 9,720 nozzles, and four nozzle blocks were
- the total number of nozzles was 38,880, the spinning distance
- the diameter thereof was lmm.
- the inner diameter of the air supply nozzles was 20mm, the outer diameter thereof was 23mm, and the distance h
- the present invention can be utilized for producing a conjugate nanofiber non-woven fabric and a conjugate nanofiber filament which are used as commodities such as artificial leather, air cleaning filter, wiping cloth, golf glove, wig, etc. and various industrial materials such as artificial filter for dialysis, artificial blood vessel, anti-adhesion agent, artificial bone, etc. because it has physical properties required for each purpose.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/KR2005/003183 WO2007035011A1 (en) | 2005-09-26 | 2005-09-26 | Conjugate electrospinning devices, conjugate nonwoven and filament comprising nanofibers prepared by using the same |
Publications (2)
Publication Number | Publication Date |
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EP1929074A1 true EP1929074A1 (de) | 2008-06-11 |
EP1929074A4 EP1929074A4 (de) | 2009-09-02 |
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Application Number | Title | Priority Date | Filing Date |
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EP05856366A Withdrawn EP1929074A4 (de) | 2005-09-26 | 2005-09-26 | Konjugatelektrospinvorrichtungen, sowie damit hergestellte nanofasern enthaltendes konjugatvlies und -filament |
Country Status (4)
Country | Link |
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US (1) | US20080102145A1 (de) |
EP (1) | EP1929074A4 (de) |
JP (1) | JP4769871B2 (de) |
WO (1) | WO2007035011A1 (de) |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009019300A (ja) * | 2007-07-11 | 2009-01-29 | Kyoto Institute Of Technology | 基材への繊維の固着方法及び積層シート体 |
EP2242385B1 (de) * | 2008-01-18 | 2012-12-12 | Mmi-Ipco, Llc | Verbundgewebe |
EP2258896A4 (de) * | 2008-03-27 | 2012-06-20 | Kurita Water Ind Ltd | Polymerfasermaterial, herstellungsverfahren dafür und filter zur flüssigkeitsfilterung |
EP2202336A1 (de) * | 2008-12-12 | 2010-06-30 | Eads Construcciones Aeronauticas S.A. | Verfahren zur Herstellung von Nanofasern von Epoxidharz für Verbundstofflaminate von aeronautischen Strukturen zur Verbesserung von deren elektromagnetischen Eigenschaften |
CN101929035B (zh) * | 2009-06-24 | 2011-11-16 | 中国科学院理化技术研究所 | 经纬双向静电纺丝制膜设备及设备的应用方法 |
JP5201118B2 (ja) * | 2009-10-16 | 2013-06-05 | パナソニック株式会社 | ナノファイバ膜製造装置およびナノファイバ膜製造方法 |
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EP2582868B1 (de) | 2010-06-17 | 2018-03-28 | Washington University | Biomedizinische pflaster mit ausgerichteten fasern |
JP5815230B2 (ja) * | 2010-12-06 | 2015-11-17 | トップテック・カンパニー・リミテッドTOPTEC Co., Ltd. | ナノ繊維製造装置 |
JP5802021B2 (ja) * | 2011-02-15 | 2015-10-28 | トップテック・カンパニー・リミテッドTOPTEC Co., Ltd. | 電界紡糸装置及びナノ繊維製造装置 |
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ITBO20120106A1 (it) * | 2012-03-05 | 2013-09-06 | Montrade Srl | Metodo e macchina per la produzione di filtri senza carta per articoli da fumo |
KR101323581B1 (ko) | 2012-04-26 | 2013-10-30 | 전북대학교산학협력단 | 나노섬유 제조용 방사튜브 및 이를 이용한 나노섬유의 제조방법 |
EP2897561B1 (de) | 2012-09-21 | 2020-11-04 | Washington University | Biomedizinische pflasterstreifen mit räumlich angeordneten fasern |
CN102943311B (zh) * | 2012-11-15 | 2015-01-07 | 西安工程大学 | 利用静电纺丝工艺规模化制备纳米纤维的装置及制备方法 |
US20160083868A1 (en) * | 2013-04-17 | 2016-03-24 | Finetex Ene, Inc. | Electrospinning apparatus |
US9314549B2 (en) | 2013-04-24 | 2016-04-19 | University Of South Carolina | Bone tissue biomimetic materials |
CN103628147B (zh) * | 2013-07-04 | 2015-11-25 | 青岛大学 | 一种制备异质螺旋缠绕纤维束和绞线的静电纺丝装置 |
CN103541149B (zh) * | 2013-08-29 | 2017-04-05 | 天津工业大学 | 一种增强静电纺纳米纤维膜的方法 |
CN103484954B (zh) * | 2013-10-11 | 2016-05-18 | 天津工业大学 | 一种制备纳米纤维的静电纺丝装置 |
US10227566B2 (en) | 2013-10-30 | 2019-03-12 | University Of South Carolina | Three dimensional matrix for cancer stem cells |
US9851341B2 (en) * | 2014-06-27 | 2017-12-26 | Eastman Chemical Company | Fibers with chemical markers used for coding |
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CN104593880A (zh) * | 2015-01-15 | 2015-05-06 | 东华大学 | 一种聚合物纳米纤维批量化生产的静电纺丝装置 |
WO2017130220A1 (en) | 2016-01-27 | 2017-08-03 | Indian Institute Of Technology Delhi | Apparatus and process for uniform deposition of polymeric nanofibers on substrate |
US10632228B2 (en) | 2016-05-12 | 2020-04-28 | Acera Surgical, Inc. | Tissue substitute materials and methods for tissue repair |
CN106119995B (zh) * | 2016-09-02 | 2018-04-13 | 天津工业大学 | 一种实心针头静电纺丝装置 |
CN106555234B (zh) * | 2016-11-28 | 2018-11-13 | 浙江大学 | 一种复合螺旋纤维纺丝装置与其纺丝方法 |
US10894019B2 (en) | 2017-08-15 | 2021-01-19 | University Of South Carolina | Drug delivery system and method for targeting cancer stem cells |
CZ309078B6 (cs) * | 2018-05-28 | 2022-01-19 | Contipro A.S. | Zařízení a způsob výroby nano- a/nebo mikrovlákenných vrstev se zvýšenou tloušťkovou rovnoměrností |
CN108823664A (zh) * | 2018-09-29 | 2018-11-16 | 安徽和邦纺织科技有限公司 | 一种实验室用纺丝设备 |
US11672767B2 (en) | 2019-05-13 | 2023-06-13 | University Of South Carolina | Enzymatically cleavable self-assembled nanoparticles for morphogen delivery |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005073442A1 (en) * | 2004-02-02 | 2005-08-11 | Raisio Chemicals Korea Inc. | A process of preparing continuous filament composed of nanofibers |
WO2005090653A1 (en) * | 2004-03-23 | 2005-09-29 | Hak-Yong Kim | A bottom-up electrospinning devices, and nanofibers prepared by using the same |
WO2006135147A1 (en) * | 2005-06-17 | 2006-12-21 | Industrial Cooperation Foundation Chonbuk National University | Method of manufacturing a continuous filament by electrospinning and continuous filament manufactured thereby |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE534423A (de) * | 1953-12-24 | |||
GB1231066A (de) * | 1968-05-29 | 1971-05-05 | ||
GB1527592A (en) * | 1974-08-05 | 1978-10-04 | Ici Ltd | Wound dressing |
US4134954A (en) * | 1975-07-19 | 1979-01-16 | Bayer Aktiengesellschaft | Spinning process and device with static mixing inserts |
JPH069672B2 (ja) * | 1985-10-18 | 1994-02-09 | 富士写真フイルム株式会社 | 磁性液塗布方法 |
US5045248A (en) * | 1989-09-22 | 1991-09-03 | E. I. Du Pont De Nemours And Company | Process for making a non-woven sheet |
JPH03167358A (ja) * | 1989-11-22 | 1991-07-19 | I C I Japan Kk | 繊維状集合体 |
US6110590A (en) * | 1998-04-15 | 2000-08-29 | The University Of Akron | Synthetically spun silk nanofibers and a process for making the same |
US20020084178A1 (en) * | 2000-12-19 | 2002-07-04 | Nicast Corporation Ltd. | Method and apparatus for manufacturing polymer fiber shells via electrospinning |
KR100406981B1 (ko) * | 2000-12-22 | 2003-11-28 | 한국과학기술연구원 | 전하 유도 방사에 의한 고분자웹 제조 장치 및 그 방법 |
US6991702B2 (en) * | 2001-07-04 | 2006-01-31 | Nag-Yong Kim | Electronic spinning apparatus |
KR100491228B1 (ko) * | 2003-02-24 | 2005-05-24 | 김학용 | 나노섬유로 구성된 연속상 필라멘트의 제조방법 |
ATE461299T1 (de) * | 2004-01-30 | 2010-04-15 | Hak-Yong Kim | Von unten nach oben arbeitende elektrospinnvorrichtung |
-
2005
- 2005-09-26 WO PCT/KR2005/003183 patent/WO2007035011A1/en active Application Filing
- 2005-09-26 JP JP2008532155A patent/JP4769871B2/ja active Active
- 2005-09-26 EP EP05856366A patent/EP1929074A4/de not_active Withdrawn
- 2005-09-26 US US11/722,873 patent/US20080102145A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005073442A1 (en) * | 2004-02-02 | 2005-08-11 | Raisio Chemicals Korea Inc. | A process of preparing continuous filament composed of nanofibers |
WO2005090653A1 (en) * | 2004-03-23 | 2005-09-29 | Hak-Yong Kim | A bottom-up electrospinning devices, and nanofibers prepared by using the same |
WO2006135147A1 (en) * | 2005-06-17 | 2006-12-21 | Industrial Cooperation Foundation Chonbuk National University | Method of manufacturing a continuous filament by electrospinning and continuous filament manufactured thereby |
Non-Patent Citations (1)
Title |
---|
See also references of WO2007035011A1 * |
Also Published As
Publication number | Publication date |
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JP4769871B2 (ja) | 2011-09-07 |
WO2007035011A9 (en) | 2007-06-07 |
JP2009510272A (ja) | 2009-03-12 |
EP1929074A4 (de) | 2009-09-02 |
US20080102145A1 (en) | 2008-05-01 |
WO2007035011A1 (en) | 2007-03-29 |
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