EP3559323A1 - Procédé de fabrication de fibres et de matière non tissée par filage en solution par soufflage et matériau non tissé ainsi fabriqué - Google Patents
Procédé de fabrication de fibres et de matière non tissée par filage en solution par soufflage et matériau non tissé ainsi fabriquéInfo
- Publication number
- EP3559323A1 EP3559323A1 EP17835818.0A EP17835818A EP3559323A1 EP 3559323 A1 EP3559323 A1 EP 3559323A1 EP 17835818 A EP17835818 A EP 17835818A EP 3559323 A1 EP3559323 A1 EP 3559323A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starting solution
- solution
- process gas
- nozzle
- water
- 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- Withdrawn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
- 238000009987 spinning Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 82
- 239000000835 fiber Substances 0.000 claims description 71
- 230000008569 process Effects 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920001410 Microfiber Polymers 0.000 claims description 2
- 210000004072 lung Anatomy 0.000 claims description 2
- 239000003658 microfiber Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 77
- 239000007789 gas Substances 0.000 description 41
- 150000002191 fatty alcohols Chemical class 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000010041 electrostatic spinning Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003871 sulfonates Chemical class 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- -1 Biodac ethoxylated C10 alcohol Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000047703 Nonion Species 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003302 UV-light treatment Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
-
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- 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
-
- 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
- D04H1/724—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 forming webs during fibre formation, e.g. flash-spinning
Definitions
- the invention relates to the use of an off ⁇ temporary solution for the production of fibers, in particular fibers micro- or Submikromaschinen or nanofibers by Solution-blow spinning, and such a spinning process for the production of fibers and a nonwoven fabric produced by the method.
- Solution-Blow-Blowing is a spinning process in which a source solution emerges from at least one exit nozzle and is transported to a collector under the action of a process gas to form solid fibers consequently synthetic fibers.
- Method For example, methods are known in which fibers are produced by extruding a liquid or viscous mass through openings. Such methods are referred to as melting, wet or dry spinning process, depending on how the mass in question has been asked ⁇ forth or liquefied.
- JP 2010-150712 A discloses a process for producing fibers by electrostatic spinning which uses aqueous solutions of water-soluble polymers.
- the electrostatic spinning has a Prinzipbe ⁇ dingt comparatively low productivity.
- fiber production by electrostatic spinning is very expensive.
- the electrostatic spinning can therefore be host ⁇ cally used only for the production of fibers, which are used in very high-priced products.
- a starting solution is used to prepare the fibers by means of solution-blow spinning, is used in the water as a solvent.
- ⁇ to minimum the proportion of water is ⁇ range from 30% to 99% as solvent Be, preferably 50% to 95%, more preferably 60% to 90%.
- solvent is Wenig ⁇ one, and preferably a water soluble polymer dissolved exactly least.
- the starting solution contains at least one surfactant.
- the surfactant is a surfactant, which may also be referred to as a surfactant.
- the fibers can be produced as microfibers, submicrofibers or nanofibers, ie with a fiber diameter in the micrometer range or sub-micrometre range or nanometer range by solution blow spinning.
- the order in which the substances added to the solvent are dissolved is not of considerable importance.
- the decisive factor is the composition of the output ⁇ solution.
- solution-blow spinning one or more jets of liquid are generated without atomizing the liquid into a spray.
- the liquid jets exit through a nozzle and are stretched by means of a Pro ⁇ zessgases, in particular compressed air. This fibers are formed.
- the liquid jets are preferably aligned substantially parallel to each other.
- the fibers preferably have a ratio of length to an average thickness of at least 100: 1, preferably at least 500: 1, preferably Minim ⁇ least 1000: 1 and more preferably at least 10000: 1.
- the fibers have a length of at least ei ⁇ nem millimeters, preferably of at least three Millime ⁇ tern, and more preferably of at least 5 millimeters.
- the at least one water-soluble polymer or the at least one surfactant are not considered as solvents.
- the initial solution has finally ⁇ from water-soluble polymers.
- Other water-insoluble polymers are not included in the starting solution.
- At least one of the water-soluble polymers contained in the starting solution may be polyvinyl alcohol and / or polyvinyl methyl ether and / or polyethylene oxide and / or polyvinylpyrrolidone and / or polyethylene glycol and / or polyacrylic acid and / or polyacrylamide.
- the concentration of water in the starting solution in the range of 30 wt% to 99 wt%, preferably from 50 wt% to 95 wt%, more preferably from 60 wt% to 90 wt%.
- the at least one water-soluble polymer can be selected from known polymers or polymer groups. The following list shows not complete ⁇ de Au drunk usable wasserlösch polymers:
- Cellulose derivatives such as methylcellulose, sodium carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose;
- - natural gums such as gelatine, metal alginates (Na, K, Ca, Zn, Al), agar;
- Starch derivatives such as hydroxyethyl starch ether, hydroxypropyl starch;
- Water-soluble polysaccharides such as xanthan, pullulan, ulvan;
- Polyamino acids with a free carboxyl group such as aspartic acid and glutamic acid;
- Polyalkylenglykol such as polyethylene and polypropylene glycol
- the starting solution also may contain a plasticizer for the presence of at least one polymer, such as polyethylene glycol, propylene glycol, Glyze ⁇ rin, trimethylolpropane, di- / or tripropylene glycol with the ⁇ sen related compounds.
- a plasticizer for the presence of at least one polymer, such as polyethylene glycol, propylene glycol, Glyze ⁇ rin, trimethylolpropane, di- / or tripropylene glycol with the ⁇ sen related compounds.
- the soft Some are attributed to the proportion of polymer and not the solvent ⁇ portion or the surfactant.
- the concentration of the at least one wasserlös ⁇ union polymer of the starting solution is preferably in the range of 1 wt .-% to 70 wt .-%, preferably in the range of 5 wt .-% to 50 wt .-%, and more preferably in the Be ⁇ rich from 10 wt .-% to 40 wt .-% including an optional plasticizer.
- the specified Kon ⁇ concentration applies both when only a water-soluble polymer in the starting solution is present, as well as for starting solutions with more water soluble polymers.
- the starting solution has exactly one water-soluble polymer which is suitable for a polymer used for the polymer
- Plasticizers can be added.
- the concentration of the at least one surfactant in the starting solution is in the range from 0.001% by weight to 50% by weight, and more Preferably in the range of 0.01 wt .-% to 5 wt .-%, and more preferably in the range of 0.1 wt .-% to
- any surfactant mentioned in the table below may be used.
- the commercial name of the surfactant and details of its composition are listed in the table.
- Cithrol A Cithrol A, ML, MO and
- Cithrol others glycol and glyceroleter
- Ethoxylated fatty alcohols for example, e.g. with blocked
- Geropon predominantly sulfosuccinates and taurates
- the starting solution may contain in acitedsbei ⁇ play solid particles, for example organic ⁇ -specific and / or inorganic solid particles, such as S 1O2 T 1O2, Z Ru2, CuO, ZnO or Ag, preferably with particle ⁇ diameters smaller than the average Fiber diameter are.
- solid particles for example organic ⁇ -specific and / or inorganic solid particles, such as S 1O2 T 1O2, Z Ru2, CuO, ZnO or Ag, preferably with particle ⁇ diameters smaller than the average Fiber diameter are.
- the starting solution has no further constituents.
- the solution solution is blown out during solution-blow spinning by at least one first outlet nozzle of a pre ⁇ direction.
- a process gas is emitted through at least one second outlet nozzle.
- Each first outlet nozzle is associated with at least one second outlet nozzle.
- the effluent process gas exits with high Ge ⁇ speed.
- the process gas is supplied under a pressure of 0.1 to 1000 psi, preferably from 5 to 80 psi and more preferably 10 to 60 psi of the at least two ⁇ th output nozzle.
- a process gas can be used in one embodiment, air or compressed air.
- the air may be from the at least one second ⁇ gangsdüse supplied under a pressure of 10 to 80 psi.
- the starting solution may be supplied to the at least one first outlet nozzle via a pumping device.
- a pumping device a metering pump, such as a gear pump, progressive cavity pump, reciprocating pump, peristaltic pump, diaphragm pump or other positive displacement ⁇ pe can be used.
- Each first exit nozzle may be associated with exactly one second exit nozzle.
- the second outlet nozzle, the first off ⁇ enclose gangsdüse partially or completely, preferably ⁇ annular manner.
- the second exit nozzles may be evenly distributed around the circumference of the first exit nozzles. Linear arrangements of the outlet nozzles can also be used.
- the discharge direction, a first outlet nozzle is defined by the least and the outlet ⁇ direction, the associated through a second output nozzle is defined at least can be ori sunt parallel ⁇ .
- the outlet direction of the at least one second outlet nozzle is inclined with respect to the outlet direction of the associated at least one first outlet nozzle.
- the emerging process gas forms at least at a distance of a few millimeters, for example from 0 to 100 mm or 0.5 to 20 mm or 1 to 5 mm, a liquid jet of the starting solution.
- This liquid jet is carried or transported by the process gas.
- the output ⁇ solution towards a collector to, preferably the solvent-containing and / or ent ⁇ holding surfactant substantially completely vaporized, for example at least 85% or at least 90% or at least 95% or at least 99 %.
- the polymer contained in the starting solution solidifies, which is then no longer dissolved in the solvent.
- the resulting fes ⁇ th fibers are collected on the collector.
- the die-to-collector distance of an exit nozzle to the collector is at least preferably at least 20 centimeters, and more preferably at least 25 centi ⁇ meter. In one embodiment, the nozzle-collector distance may be about 30 to 70 centimeters. Before ⁇ preferably the nozzle-to-collector distance is smaller than 200 cm, and further preferably alive less than 100 centime ⁇ ter.
- the boiling point of the Lö ⁇ sungsstoffs and / or the surfactant is so small that the solvent and / or the surfactant evaporates after emerging from the at least one first Crowse.
- the process gas may have a focusing and / or bundling effect on the exiting solution.
- the formation of a liquid jet emerging from ⁇ temporary solution by selection of process parameters such as the composition of the starting solution and / or the temperature of the starting solution and / or the temperature of the process gas and / or the ambient temperature ⁇ structure and / or the temperature of the output nozzle arrangement and / or the velocity of the process gas and / or the chemical composition of the process gas used and / or a suction capacity of a At the collector arranged suction device can be influenced.
- the fiber diameter of the fibers produced is typically one-twentieth to one-thousandth of the opening diameter of at least a first from ⁇ opening.
- the fiber diameter is smaller than the diameter of the emerging from the at least one first outlet opening ⁇ liquid jet.
- process parameters such as the speed of the emerging from ⁇ process gas, a reduction of the fiber diameter compared with the diameter of the emerging liquid jet can be obtained and set. If, for example, the exit velocity of the process gas is increased, the liquid jet is stretched as it were along its path, which reduces its diameter.
- the solvent and / or the surfactant is evaporated, so that the volume of liquid also decreases after it leaves the at least one first outlet nozzle.
- the Solution-blow spinning it is possible example ⁇ example, the produce a first output nozzle of, for example 0.2 to 1 mm, the fibers in the micron or submicron or nanometer range with diameters at least.
- HERGÉ ⁇ presented fibers have an average diameter of about 50 Na nometern to 3 micrometers.
- the process gas may in one embodiment with egg ⁇ ner temperature of 0 ° C to 100 ° C, preferably 10 ° C to 90 ° C and more preferably 20 ° C to 80 ° C to the least ⁇ least a second exit nozzle ( 21) are supplied.
- the fibers After the fibers have been produced, it may be advantageous if the fibers are aftertreated, for example by irradiation with high-energy radiation, such as UV light and / or heat treatment and / or plasma / corona treatment and / or a chemical treatment and / or other cross-linking treatments.
- high-energy radiation such as UV light and / or heat treatment and / or plasma / corona treatment and / or a chemical treatment and / or other cross-linking treatments.
- high-energy radiation such as UV light and / or heat treatment and / or plasma / corona treatment and / or a chemical treatment and / or other cross-linking treatments.
- FIG. 1 shows a schematic, block diagram-like representation of an apparatus for producing fibers by means of solution-blow spinning
- FIGS. 2 and 3 each show a schematic principle. Zip representation of different output nozzle arrangements, each having a first output nozzle and at least one associated second output nozzle in plan view of the output nozzles,
- FIGS. 4 and 5 show a schematic principle illustration of different linear outlet nozzle arrangements of a plurality of first and second outlet nozzles in plan view of the outlet nozzles
- Figures 6 and 7 are each a schematic cross-sectional view ⁇ an embodiment of an output ⁇ nozzle assembly each having at least a first Ausgangdüse and at least one associated second outlet nozzle, and
- FIG. 8 is a highly schematic representation of an embodiment of a manufactured fiber.
- FIG. 1 shows a device 10 for carrying out a solution-blow-spinning process.
- the device 10 has a reservoir 11 for providing a starting solution A.
- the starting solution A is conveyed by means of a pumping device 12 to a solvent fluid port 13 of a spinneret device 14.
- the spinneret device 14 has a process gas connection 15, by means of which the Spinndüsenein ⁇ direction 14 a pressurized process gas G is supplied ⁇ leads.
- the process gas G can be formed for example by air or compressed air. It can be taken from a pressure accumulator 16. Alternatively, instead of the pressure accumulator 16, a compressor or the like may be present be to suck in air from the environment and provide compressed air as process gas G.
- the process gas G may also be another gas such as nitrogen, helium or hydrogen.
- the spinning nozzle assembly 14 has at least one first outlet nozzle 20.
- Each first Ausgangdüse 20 is we ⁇ tendonss associated with a second outlet nozzle 21st If meh ⁇ eral first output nozzles 20 are present, these differently oriented outlet or emission directions can have, which is shown schematically in FIG. 1
- the at least one first exit nozzle 20 is fluidically connected to the solvent fluid port 13.
- the at least one second outlet nozzle 21 is fluidically connected to the process gas connection 15.
- the output solution A passes through the at least one first outlet nozzle 20 and the process gas G through the at least one second outlet nozzle 21.
- the collector 22 may have movable components on ⁇ , such as a moving conveyor belt which is moved on drive rollers 25th In a modification to the illustrated embodiment, the collector 22 may be immovable, static executed.
- the collector 22 is gas-permeable and may be formed, for example, by a mesh or mesh-shaped carrier, such as a fine-meshed net.
- a suction device 26 may be present on the spinneret 14 opposite side of the collector 22 .
- the suction means 26 may be adapted to move the fibers 24 forming between the spinneret 14 and the collector 22 by suction of an air flow towards the collector 22.
- the die-to-collector distance z between the ilias we ⁇ a first outlet nozzle 20 and the collector 22 and / or between the at least one second outlet nozzle 21 and the collector 22 is 20 centimeters or 25 centimeters. In the illustrated embodiment can be ⁇ wear of the nozzle-to-collector distance for about 30 to 70 centimeters. Preferably, the nozzle-collector distance z is less than 200 centimeters and more preferably less than 100 centimeters.
- FIG. 2 to 7 schematically illustrates exemplary different configurations each from ⁇ gear nozzle assembly 30 of the spinning nozzle device 14 are illustrated.
- the spinnerette assembly 14 may include one or more of the illustrated exit nozzle assemblies 30. These can be parallel or inclined to each other the spinning nozzle device 14 may be arranged or aligned.
- Each output nozzle device 30 has at least one and, for example, exactly one first output nozzle 20 for the starting solution A and at least one associated second output nozzle 21 for the process gas G.
- the output nozzle assembly exactly one ers ⁇ te outlet nozzle 20 and exactly one associated second off ⁇ gangsdüse 21.
- the first outlet nozzle 20 is arranged in the center of an annularly closed second outlet nozzle 21 which, in the exemplary embodiment, completely coaxially surrounds the first outlet nozzle 20.
- the exit nozzle group 30 has exactly one first exit nozzle 20 and a plurality of associated second exit nozzles 21, for example four second exit nozzles 21.
- the number of second exit nozzles 21 can vary, with at least two second outlet nozzles 21 are present.
- the second outlet nozzles 21 are preferably arranged uniformly distributed in the circumferential direction around the first outlet nozzle 20.
- the second exit nozzles can also be a curved one
- Slit shape and the first output nozzle 20 in de ⁇ ren circumferential direction partially enclose.
- the cross-sectional shape of the outlet ⁇ nozzles 20, 21 are arbitrarily selected. Illustrative of each circular or annular cross-sections are ver ⁇ anschaubit. Other polygonal or slot-shaped straight or curved cross-sectional contours can also be provided, in particular for the at least one second Exit nozzle 21 of each output nozzle group 30th
- Figures 4 and 5 show only by way of example that the output nozzles 20, 21 can be arranged in a linear arrangement in one or more rows next to each other.
- the central longitudinal axes of the outlet nozzles 20, 21 of an outlet nozzle group 30 shown in phantom can be oriented parallel to one another (FIG. 6) or, alternatively, they can be oriented inclined relative to one another (FIG. 7).
- the output direction for the process gas G is the Wenig ⁇ least inclined a second outlet nozzle 21 opposite the exit ⁇ direction of the initial solution A, according to the example in such a way that the process gas G at a plurality of circumferential positions per ⁇ wells obliquely to the central longitudinal axis or the exit ⁇ direction of the first output nozzle 20 is aligned.
- the mouth of the at least one first exit nozzle 20 is spaced from the mouth of the at least one associated second exit nozzle 21, and preferably downstream of the process gas stream.
- the distance may for example be 0.5 to 20 mm or 1 to 10 mm or 1 to 5 mm or 2 to 3 mm.
- the orientations of the exit directions according to FIGS. 6 and 7 can be provided both for the outlet nozzle group 30 from FIG. 2 and for the outlet nozzle group 30 from FIG. 3.
- the starting solution A at least and preferably exactly one water-soluble polymer from which the fibers 24 are to be formed is dissolved in a solvent and, for example, in water.
- the starting solution also contains at least one surfactant.
- a plasticizer may be contained in the starting solution A.
- the polymer may be dissolved in solid form, for example as a powder, in the form of small spheres or pellets or the like in the solvent-serving water of the starting solution A.
- the concentration of the at least one wasserlös ⁇ union polymer in the starting solution A may be 1 wt .-% to 70 wt .-%, preferably 5 wt .-% to 50 wt .-%, more preferably 10 wt .-% to 40 wt .-% amount. If a plasticizer is used for the at least one polymer, be ⁇ meet the specifications of the total concentration of the at least one polymer including the plasticizer.
- the concentration of water in the Ninth is in preferred embodiments
- the concentration of the surfactant in the solution réellelö ⁇ A is the embodiment wt .-% 0.001 to 50 wt .-%, preferably 0.01% to 5 wt .-%, and more preferably 0.1 part by weight before ⁇ % to 1.5% by weight.
- the process gas G can be supplied to the process gas connection 13 with a pressure of up to 1000 psi, preferably with a pressure of 5 to 80 psi. When using of air as process gas G, the pressure may be in the range of 10 to 60 psi.
- the process gas G does during feeding of spinning nozzle assembly 14 is a temperature in the range of 0 ° C to 100 ° C, preferably from 10 ° C to 90 ° C, and more preferably before ⁇ from 20 ° C to 80 ° C.
- Example According to the Pro ⁇ zessgastemperatur of the process gas G during feeding to the spinning nozzle device 14 is greater than the ambient temperature, for example a room temperature, and may range from 35 ° C to 70 ° C.
- the fibers 24 formed by the polymer chains are obtained in the process that on the way between the spinneret 14 and the collector 22, the solvent, here the water, and / or the at least one surfactant completely or at least partially evaporated. That is, the solvent and / or the surfactant to evaporate ⁇ least 85% or at least 90% or at least 95% or at least 99%.
- the fibers 24 are formed.
- a nonwoven fabric is formed from the fibers 24, which preferably have a fiber diameter in the micrometer range, in the submicron range or in the nanometer range.
- the fibers 24 consist essentially of the polymer present in the starting solution A, optionally additionally of the plasticizer used for the at least one polymer.
- the produced fibers 24 preferably have a ratio of length L to an average thickness D of at least 100: 1, preferably at least 500: 1, more preferably at least 1000 before ⁇ : 1, and even more preferably at least 10000: 1.
- the fibers 24 a length L of at least one millimeter, preferably at least three millimeters and more preferably at least five millimeters.
- Examples 1 to 4 are given below, which describe a possible composition of the starting solution A and features of the device 10.
- the distance between the at least one first outlet nozzle 20 and the collector ⁇ tor 22 is 65 cm.
- the hergestell ⁇ th with this method fibers 24 have fiber diameter with a diameter in a range of 50 to 400 nm.
- the average value of the diameter of the fibers 24 produced is 200 nm.
- the polymer solution is produced from 12 wt .-% polyvinyl alcohol (molecular weight 130000 u), which was dissolved in Destil ⁇ of water required, with the A in the starting solution 87 wt .-% is included.
- the starting solution A contains
- the method is carried out using compressed air as the process gas G, which is supplied at a pressure of 20 psi to the at least one second output ⁇ nozzle 21.
- the at least one first output ⁇ nozzle 20 has a diameter of 0.6 mm (at the outlet).
- the distance between the at least one first exit nozzle 20 and the collector 22 is 65 cm.
- the fibers 24 produced by this method have fiber diameters in a range of 100 to 450 nm.
- the mean value of the diameter of the fibers 24 produced is 240 nm.
- the process is carried out using compressed air as the process gas G, which is supplied to the at least one second outlet nozzle 21 at a pressure of 20 psi.
- the at least one first exit nozzle 20 has a diameter of 0.8 mm (at the exit opening).
- the distance between the at least one first exit nozzle 20 and the collector 22 is 65 cm.
- the fibers 24 produced by this method have fiber diameters in a range of 100 to 500 nm.
- the mean value of the diameter of the fibers 24 produced is 250 nm.
- polyethylene oxide (molecular weight 600,000 u) are dissolved in 96 wt .-% of distilled water.
- the starting solution A also contains 2% by weight of isopropanol.
- the process is carried out using compressed air as the process gas G, the Wenig ⁇ least a second output nozzle 21 is supplied with a pressure of 40 psi to the.
- the WE ⁇ tendonss a first outlet nozzle has a diameter of 0.6 mm.
- the distance between the at least one first exit nozzle 20 and the collector 22 is 65 cm.
- the fibers 24 produced by this method have a fiber diameter in a range of 100 to 500 nanometers.
- the mean value of the diameter of the fibers 24 produced is 250 nanometers.
- the spinning process according to the invention can be further optimized by the use of additional and / or alternative surfactants.
- any surfactant and / or polymer can be used which is included in the tables given in the description.
- the invention relates to the use of an off ⁇ A temporary solution in the process for producing fibers for a fiber fleece by means of a so-called blow-Solution-spinning.
- the solvent for the starting solution A water is used.
- the water of the starting solution A is at least one water-soluble polymer and preferably ge ⁇ exactly dissolved a water-soluble polymer.
- the starting solution A also contains at least one surfactant and optionally a plasticizer for the at least one respective Po ⁇ lymer used.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
Abstract
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016125182.8A DE102016125182A1 (de) | 2016-12-21 | 2016-12-21 | Verfahren zur Herstellung von Fasern und Vliesstoffen durch Solution-Blow-Spinnen und damit hergestellter Vliesstoff |
| PCT/EP2017/082973 WO2018114645A1 (fr) | 2016-12-21 | 2017-12-15 | Procédé de fabrication de fibres et de matière non tissée par filage en solution par soufflage et matériau non tissé ainsi fabriqué |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3559323A1 true EP3559323A1 (fr) | 2019-10-30 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17835818.0A Withdrawn EP3559323A1 (fr) | 2016-12-21 | 2017-12-15 | Procédé de fabrication de fibres et de matière non tissée par filage en solution par soufflage et matériau non tissé ainsi fabriqué |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20200095706A1 (fr) |
| EP (1) | EP3559323A1 (fr) |
| JP (1) | JP2020502383A (fr) |
| KR (1) | KR20190092568A (fr) |
| CN (1) | CN110325674A (fr) |
| CA (1) | CA3048069A1 (fr) |
| DE (1) | DE102016125182A1 (fr) |
| WO (1) | WO2018114645A1 (fr) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109537068B (zh) * | 2018-12-19 | 2021-08-06 | 上海固甲新材料科技有限公司 | 一种液喷纺丝装置 |
| CN110656402A (zh) * | 2019-01-21 | 2020-01-07 | 深圳维度新材料有限公司 | 一种无机纳米纤维制备方法及设备 |
| EP3925690A1 (fr) * | 2020-06-16 | 2021-12-22 | Gambro Lundia AB | Procédé et dispositif d'enrobage |
| EP3954811A1 (fr) | 2020-08-13 | 2022-02-16 | Gelatex Technologies OÜ | Dispositif et procédé de production de fibres polymère et leurs utilisations |
| CN112316567B (zh) * | 2020-10-19 | 2022-07-22 | 江苏大学 | 一种纳米纤维过滤薄膜及其制备方法和装置 |
| JP2022094643A (ja) * | 2020-12-15 | 2022-06-27 | 株式会社タマル製作所 | ナノファイバー吹き付け装置 |
| CZ310133B6 (cs) * | 2023-03-28 | 2024-09-18 | Contipro A.S. | Způsob přípravy vláken a zařízení k provádění tohoto způsobu |
| CN117904798A (zh) * | 2024-01-14 | 2024-04-19 | 海南医学院 | 一种淀粉纳米纤维膜及其制备方法与应用 |
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| WO2016011124A1 (fr) * | 2014-07-17 | 2016-01-21 | The Research Foundation For The State University Of New York | Membranes composites à base de graphène poreux destinées à la nanofiltration, au dessalement et à la pervaporation |
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| CA2070589C (fr) * | 1991-12-19 | 2000-11-28 | Kimberly-Clark Corporation | Methode de production de non-tisses en poly (alcool de vinyle) |
| US5411693A (en) * | 1994-01-05 | 1995-05-02 | Hercules Incorporated | High speed spinning of multi-component fibers with high hole surface density spinnerettes and high velocity quench |
| US5840423A (en) * | 1995-09-05 | 1998-11-24 | Kuraray Co., Ltd. | Polyvinyl alcohol-based fiber having excellent hot water resistance and production process thereof |
| DE19609143C1 (de) * | 1996-03-08 | 1997-11-13 | Rhodia Ag Rhone Poulenc | Melt-blown-Vlies, Verfahren zu dessen Herstellung und dessen Verwendungen |
| CN1170018C (zh) * | 2002-01-21 | 2004-10-06 | 中国科学院山西煤炭化学研究所 | 一种氧化铝-氧化硅纤维的制备方法 |
| ATE449203T1 (de) * | 2002-04-24 | 2009-12-15 | Polyamide High Performance Gmb | Hochfestes garn mit profilierten filamenten |
| TWI302171B (en) * | 2003-04-22 | 2008-10-21 | Asahi Kasei Fibers Corp | A spun bonded-type laminate nonwoven fabric and method therefor |
| US7846374B2 (en) * | 2004-11-05 | 2010-12-07 | E. I. Du Pont De Nemours And Company | Blowing gases in electroblowing process |
| JP2006323914A (ja) * | 2005-05-18 | 2006-11-30 | Fujifilm Holdings Corp | 光情報記録媒体の製造方法及び光情報記録媒体 |
| DE102005040000B4 (de) * | 2005-08-23 | 2010-04-01 | Lenzing Ag | Mehrfachspinndüsenanordnung und Verfahren mit Absaugung und Beblasung |
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2016
- 2016-12-21 DE DE102016125182.8A patent/DE102016125182A1/de not_active Ceased
-
2017
- 2017-12-15 KR KR1020197020862A patent/KR20190092568A/ko not_active Ceased
- 2017-12-15 WO PCT/EP2017/082973 patent/WO2018114645A1/fr not_active Ceased
- 2017-12-15 CA CA3048069A patent/CA3048069A1/fr not_active Abandoned
- 2017-12-15 US US16/472,081 patent/US20200095706A1/en not_active Abandoned
- 2017-12-15 JP JP2019532775A patent/JP2020502383A/ja active Pending
- 2017-12-15 CN CN201780079125.XA patent/CN110325674A/zh active Pending
- 2017-12-15 EP EP17835818.0A patent/EP3559323A1/fr not_active Withdrawn
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| WO2016011124A1 (fr) * | 2014-07-17 | 2016-01-21 | The Research Foundation For The State University Of New York | Membranes composites à base de graphène poreux destinées à la nanofiltration, au dessalement et à la pervaporation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2020502383A (ja) | 2020-01-23 |
| CA3048069A1 (fr) | 2018-06-28 |
| DE102016125182A1 (de) | 2018-06-21 |
| WO2018114645A1 (fr) | 2018-06-28 |
| CN110325674A (zh) | 2019-10-11 |
| KR20190092568A (ko) | 2019-08-07 |
| US20200095706A1 (en) | 2020-03-26 |
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