EP1731633A1 - Fibre d'acide polylactique extrêmement fine, structure fibreuse et procédé pour produire celles-ci - Google Patents

Fibre d'acide polylactique extrêmement fine, structure fibreuse et procédé pour produire celles-ci Download PDF

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Publication number
EP1731633A1
EP1731633A1 EP05720436A EP05720436A EP1731633A1 EP 1731633 A1 EP1731633 A1 EP 1731633A1 EP 05720436 A EP05720436 A EP 05720436A EP 05720436 A EP05720436 A EP 05720436A EP 1731633 A1 EP1731633 A1 EP 1731633A1
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EP
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Prior art keywords
fiber
fiber structure
lactic acid
fibers
stage
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EP05720436A
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German (de)
English (en)
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EP1731633A4 (fr
Inventor
Takanori c/o Teijin Limited Miyoshi
Kiyotsuna c/o Teijin Limited TOYOHARA
Hiroyoshi Minematsu
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Teijin Ltd
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Teijin Ltd
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Publication date
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Publication of EP1731633A1 publication Critical patent/EP1731633A1/fr
Publication of EP1731633A4 publication Critical patent/EP1731633A4/fr
Withdrawn legal-status Critical Current

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    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • 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
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • 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
    • D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—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 by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

Definitions

  • the present invention relates to fibers comprising biodegradable polylactic acid as a constituent component, and more specifically it relates to ultrafine polylactic acid fibers and a fiber structure, and to a process for their production.
  • Ultrafine fibers have a soft feel and are therefore used for such purposes as woven and knitted fabrics or artificial leather, for clothing or interior goods.
  • 6-nylon, polyethylene terephthalate, polypropylene and the like used for conventional ultrafine fibers do not decompose in soil or compost, they must be incinerated or buried after use and therefore create a major environmental load due to atmospheric pollution or prolonged durability after burial.
  • ultrafine fibers that decompose in soil or compost.
  • ultrafine fibers composed of a biodegradable thermoplastic aliphatic polyester with a single fiber diameter of no greater than 0.5 decitex (for example, see Patent document 1).
  • fibers composed of poly(L-lactic acid) with a fiber diameter of 100 nm-4 ⁇ m for example, see Patent document 2.
  • a method for improving the heat resistance of polylactic acid that has been of note recently is stereo complex formation with poly(L-lactic acid) and poly(D-lactic acid) (for example, see Patent document 3).
  • polylactic acid stereo complex fibers are mixtures of poly(L-lactic acid) single crystals and poly(D-lactic acid) single crystals, and their heat resistance has been insufficient.
  • Such fibers have large fiber diameters and the fiber structures formed from the fibers have exhibited inadequate flexibility (for example, see Patent documents 3 and 4).
  • the fibers of the invention must have a mean fiber diameter of no greater than 10 ⁇ m.
  • the mean fiber diameter of the fibers preferably does not exceed 10 ⁇ m because the obtained fiber structure will lack flexibility.
  • the mean fiber diameter of the fibers is preferably in the range of 0.01-5 ⁇ m.
  • the fibers of the invention also must have fiber lengths of 20 ⁇ m or greater. If the fiber lengths are less than 20 ⁇ m, the dynamic strength of the obtained fiber structure will be insufficient.
  • the fiber lengths are preferably at least 40 ⁇ m and more preferably at least 1 mm.
  • the fibers of the invention must have as the main constituent component a polylactic acid component with a melting point of 190°C or higher, and preferably they contain substantially no constituent component with a melting point of below 190°C.
  • the melting point of the fiber component is more preferably 195°C-250°C.
  • the fibers of the invention have as the main constituent component a polylactic acid component with a melting point of 190°C or higher.
  • the fibers of the invention more preferably have surface depressions with diameters of 0.01-1 ⁇ m, with the depressions constituting 10-95% of the fiber surfaces.
  • This kind of surface structure will increase the surface area of fiber structures formed from the fibers, thereby improving the rate of decomposition in soil or compost.
  • the diameters of the depressions are more preferably 0.02-0.5 ⁇ m, and the proportion of depressions on the fiber surfaces is more preferably 40-95%.
  • the polylactic acid component is a polymer comprising a condensate with at least 80 mol% lactic acid based on the total repeating units, and it may be copolymerized with other components so long as the features of the invention are not prevented.
  • Main constituent component means that the component constitutes at least 75 wt%, preferably at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% based on the total constituent components of the fibers of the invention.
  • the polylactic acid component preferably consists of a mixture of a condensate with at least 80 mol% L-lactic acid based on the total repeating units and a condensate with at least 80 mol% D-lactic acid based on the total repeating units.
  • a condensate with at least 80 mol% L-lactic acid based on the total repeating units means a content of 80-100 mol% L-lactic acid and 0-20 mol% of D-lactic acid or a copolymerizing component other than D-lactic acid.
  • a condensate with at least 80 mol% D-lactic acid based on the total repeating units means a content of 80-100 mol% D-lactic acid and 0-20 mol% of L-lactic acid or a copolymerizing component other than L-lactic acid.
  • copolymerizing components other than D-lactic acid and L-lactic acid there may be mentioned oxy acids, lactones, dicarboxylic acids and polyhydric alcohols. There may also be mentioned various polyesters, polyethers and polycarbonates comprising such components and having ester bond-forming functional groups.
  • the polylactic acid component is preferably a mixture comprising a condensate with at least 80 mol% L-lactic acid based on the total repeating units and a condensate with at least 80 mol% D-lactic acid based on the total repeating units, in a weight ratio of (6:4)-(4:6) .
  • the condensate with at least 80 mol% L-lactic acid based on the total repeating units and the condensate with at least 80 mol% D-lactic acid based on the total repeating units are mixed in substantially a 5:5 ratio.
  • the weight-average molecular weight of the polylactic acid component is more preferably 100,000 or greater for improved dynamic strength of the obtained fiber structure.
  • the fiber structure of the invention includes at least the aforementioned ultrafine polylactic acid fibers, but a "fiber structure" according to the invention may be any three-dimensional structure formed by weaving, knitting or laminating the fibers, and a nonwoven fabric may be mentioned as a preferred example.
  • the content of the ultrafine polylactic acid fibers in the fiber structure of the invention is not particularly limited, but the features of the ultrafine polylactic acid fibers can be exhibited with a content of 50 wt% or greater.
  • the content is more preferably 80 wt% or greater, and even more preferably the fiber structure is composed essentially of the polylactic acid fibers alone.
  • the fibers forming the fiber structure have a mean diameter of no greater than 10 ⁇ m and contain substantially no fibers with fiber lengths of less than 20 ⁇ m.
  • any process that yields the aforementioned fibers may be employed for production of a fiber structure of the invention, but there may be mentioned as a preferred mode of the production process one including a stage wherein a condensate with at least 80 mol% L-lactic acid based on the total repeating units and a condensate with at least 80 mol% D-lactic acid based on the total repeating units are combined in a weight ratio of (6:4)-(4:6) and then dissolved in a solvent to produce a solution, a stage wherein the solution is spun by an electrospinning method, and a stage wherein fibers are accumulated on a collecting plate by the spinning.
  • a production process including a stage wherein a condensate with at least 80 mol% L-lactic acid based on the total repeating units is dissolved in a solvent to produce a solution, a stage wherein a condensate with at least 80 mol% D-lactic acid based on the total repeating units is dissolved in a solvent to produce a solution, a stage in which the two solutions are mixed in a weight ratio of (6:4)-(4:6), a stage wherein the mixed solution is spun by an electrospinning method, and a stage wherein fibers are accumulated on a collecting plate by the spinning.
  • An electrospinning method is a method in which a solution of a fiber-forming compound is discharged into an electrostatic field formed between two electrodes, the solution is drawn toward the electrodes, and the resulting filamentous substance is accumulated on a collecting plate to obtain a fiber structure, where the filamentous substance need not be free of the solvent used to dissolve the fiber-forming compound but may also include the solvent.
  • melt spinning is carried out after melt kneading, or dry spinning is carried out from a solution containing the L-lactic acid condensate and poly(D-lactic acid) condensate, but in either case it has not been hitherto possible to completely eliminate a melting point of below 190°C.
  • fibers obtained by electrospinning have essentially no melting point below 190°C.
  • the aforementioned electrodes may be of any type such as metal, inorganic or organic substances so long as they exhibit electrical conductivity, and they may also have electrical conductive thin-films of metal, inorganic or organic substances on insulators.
  • the electrostatic field may be formed by a pair of or more electrodes, and a high voltage may be applied to any of the electrodes. This also includes cases of using, for example, a total of three electrodes where two are high-voltage electrodes with different voltage values (for example, 15 kV and 10 kV) and one is a grounded electrode, as well as cases of using more than three electrodes.
  • a solution containing the aforementioned polylactic acid components dissolved in a solvent is prepared, where the concentration of the polylactic acid components in the solution is preferably 1-30 wt%.
  • concentration of the polylactic acid components in the solution is preferably 1-30 wt%.
  • a low concentration of less than 1 wt% is not preferred because it will be difficult to form a fiber structure.
  • concentration is also preferably not greater than 30 wt% because the mean diameter of the obtained fibers will be increased.
  • the preferred concentration range is 2-25 wt%.
  • the solvent used to dissolve the polylactic acid components is not particularly restricted so long as it is capable of dissolving the polylactic acid components and evaporating off during the spinning stage of the electrospinning to form fibers.
  • a volatile solvent is a substance which has a boiling point of no higher than 200°C at atmospheric pressure and is a liquid at room temperature (for example, 27°C).
  • methylene chloride chloroform, dichloroethane, tetrachloroethane, trichloroethane, dibromomethane, bromoform, tetrahydrofuran, 1,4-dioxane, 1,1,1,3,3,3-hexafluoroisopropanol, toluene, xylene and dimethylformamide
  • methylene chloride, chloroform, dichloroethane, tetrachloroethane, trichloroethane, dibromomethane, bromoform, tetrahydrofuran and 1,4-dioxane are preferred and methylene chloride is most preferred.
  • solvents may be used alone, or a plurality of solvents may be combined for use as a mixed solvent.
  • any desired method may be employed for discharge of the solution into the electrostatic field, and for example, the solution may be supplied to a nozzle for appropriate positioning of the solution in the electrostatic field, and the solution drawn from the nozzle by the electrical field for formation into a filament.
  • An injection needle-shaped solution ejection nozzle (1 in Fig. 1) having a voltage applied by appropriate means such as a high-voltage generator (6 in Fig. 1) is fitted at the tip of the cylindrical solution-holder of a syringe (3 in Fig. 1), and the solution (2 in Fig. 1) is guided to the tip of the solution ejection nozzle.
  • the tip of the solution ejection nozzle (1 in Fig. 1) is situated at an appropriate distance from a grounded filamentous substance-collecting electrode (5 in Fig. 1), and the solution (2 in Fig. 1) is ejected from the tip of the solution ejection nozzle (1 in Fig. 1) to form a filamentous substance between the nozzle tip solution and the filamentous substance-collecting electrode (5 in Fig. 1).
  • fine droplets of the solution may be introduced into an electrostatic field, with the only condition being that the solution (2 in Fig. 2) is placed in the electrostatic field and held at a distance from the filamentous substance-collecting electrode (5 in Fig. 2) which allows formation into a filament.
  • an electrode (4 in Fig. 2) counter to the filamentous substance-collecting electrode may be inserted directly into the solution (2 in Fig. 2) in the holder (3 in Fig. 2) with the solution ejection nozzle (1 in Fig. 2).
  • the filamentous substance production speed can be increased by using a plurality of nozzles in parallel.
  • the distance between electrodes will depend on the charge, nozzle dimensions, ejection volume of the solution from the nozzle and the solution concentration, but a distance of 5-20 cm has been found to be suitable for approximately 10 kV.
  • the applied electrostatic potential will normally be 3-100 kV, preferably 5-50 kV and more preferably 5-30 kV.
  • the desired potential can be produced by any appropriate method known in the prior art.
  • the two modes described above employ an electrode as the collecting plate, but a material serving as the collecting plate may also be placed between the electrodes, to provide a collecting plate separate from the electrodes for collection of a filament laminate.
  • a belt-like substance for example, is placed between the electrodes and used as the collecting plate to allow continuous production.
  • a filamentous substance is formed by evaporation of the solvent, depending on the conditions, while the solution is drawn toward the collecting plate.
  • the solvent will usually evaporate completely during the period of collection on the collecting plate at room temperature, the drawing may be accomplished under reduced pressure conditions if the solvent evaporation is insufficient.
  • a fiber structure satisfying at least the fiber mean diameter and fiber length is formed upon collection on the collecting plate.
  • the temperature for drawing may be adjusted according to the evaporation behavior of the solvent and the viscosity of the spinning solution, and will normally be in the range of 0-100°C.
  • a relative humidity of 20-80% RH is preferred between the nozzle and collecting plate where the filamentous substance is formed. If the relative humidity is outside of this range, it will be difficult to accomplish stable spinning for prolonged periods.
  • a more preferred relative humidity range is 30-70% RH.
  • the fiber structure obtained by the production process of the invention may be used alone, but it may also be used in combination with other structural members depending on handleability and other essential factors.
  • a nonwoven fabric, woven fabric or film that can serve as a support material may be used as the collecting plate and the filament laminate formed thereover to allow fabrication of a member comprising a combination of the support material and the filament laminate.
  • the obtained fiber structure may also be subjected to heat treatment or chemical treatment, and the polylactic acid may be mixed with an emulsion or an organic or inorganic powder or filler at any stage prior to spinning.
  • any of various catalysts may be supported on the fiber structure of the invention for use as a catalyst-supporting base material.
  • Presence of fibers with fiber lengths of less than 20 ⁇ m Presence of fibers with fiber lengths of less than 20 ⁇ m:
  • a photograph taken of the surface of the obtained fiber structure (2000 magnification) using a scanning electron microscope (S-2400 by Hitachi, Ltd.) was observed to confirm the presence of fibers with fiber lengths of less than 20 ⁇ m.
  • the section defined by the established imaginary lines C, C' and the edges of the photograph was extracted with the image processing software, and the area percentage of depressions in the region was determined.
  • the area percentage was measured for each of 10 arbitrary locations of the fiber structure in the electron microscope photograph, and the average was determined.
  • the weight-average molecular weight was measured with a GPC-11 by Showa Denko K.K. (Column: SHODEX LF-804, solvent: chloroform, detector: RI, styrene equivalent).
  • a DSC curve for the obtained fiber structure was measured using a differential scanning calorimeter (DSC TA-2920 by Texas Instruments), and the melting point was determined from the isothermal peak.
  • the apparatus shown in Fig. 2 was used for discharge of the solution for 5 minutes onto a filamentous substance-collecting electrode 5.
  • the inner diameter of the ejection nozzle (1 in Fig. 2) was 0.8 mm
  • the voltage was 12 kV
  • the distance from the ejection nozzle (1 in Fig. 2) to the filamentous substance-collecting electrode (5 in Fig. 2) was 12 cm
  • the relative humidity was 35% RH.
  • the mean fiber diameter was 3 ⁇ m and no fibers were present with fiber lengths of less than 20 ⁇ m.
  • the mean diameter of the depressions on the fiber surfaces was 0.2 ⁇ m, and the percentage of the fiber surface area occupied by the depressions was 23%. Scanning electron microscope photographs of the fiber structure are shown in Figs. 3 and 4.
  • the melting point was 216°C and no endothermic peak was observed below 190°C.
  • the mean fiber diameter of the obtained fiber structure was 4 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m.
  • the mean diameter of the depressions on the fiber surfaces was 0.2 ⁇ m, and the percentage of the fiber surface area occupied by the depressions was 22%. Scanning electron microscope photographs of the fiber structure are shown in Figs. 5 and 6.
  • the melting point was 218°C and no endothermic peak was observed below 190°C.
  • a fiber structure was obtained in the same manner as Example 2, except for mixing 7 parts by weight of a solution of 1 part by weight of the poly(D-lactic acid) in 9 parts by weight of methylene chloride and 3 parts by weight of a solution of 1 part by weight of poly(L-lactic acid) in 9 parts by weight of methylene chloride.
  • the mean fiber diameter of the obtained fiber structure was 3 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m.
  • the mean diameter of the depressions on the fiber surfaces was 0.2 ⁇ m, and the percentage of the fiber surface area occupied by the depressions was 31%. Scanning electron microscope photographs of the fiber structure are shown in Figs. 7 and 8.
  • the main melting point was 219°C and a small endothermic peak was observed at 165°C.
  • a fiber structure was obtained in the same manner as Example 2, except that only a solution of 1 part by weight of poly(D-lactic acid) in 9 parts by weight of methylene chloride was used.
  • the mean fiber diameter of the obtained fiber structure was 2 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m.
  • the mean diameter of the depressions on the fiber surfaces was 0.2 ⁇ m, and the percentage of the fiber surface area occupied by the depressions was 21%. Scanning electron microscope photographs of the fiber structure are shown in Figs. 9 and 10.
  • the melting point was 174°C.
  • a fiber structure was obtained in the same manner as Example 2, except that only a solution of 0.7 part by weight of poly(L-lactic acid) in 9.3 parts by weight of methylene chloride was used.
  • the mean fiber diameter of the obtained fiber structure was 3 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m.
  • the mean diameter of the depressions on the fiber surfaces was 0.2 ⁇ m, and the percentage of the fiber surface area occupied by the depressions was 27%. Scanning electron microscope photographs of the fiber structure are shown in Figs. 11 and 12.
  • the melting point was 172°C.
  • a fiber structure was obtained in the same manner as Example 2, except that a methylene chloride/DMF mixed solvent (weight ratio: 8/2) was used instead of methylene chloride.
  • the mean fiber diameter of the obtained fiber structure was 2 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m. No fiber surface depressions were observed. Scanning electron microscope photographs of the fiber structure are shown in Figs. 13 and 14.
  • the melting point was 220°C and no endothermic peak was observed below 190°C.
  • a fiber structure was obtained in the same manner as Example 2, except for mixing 4 parts by weight of a solution of 1 part by weight of poly(D-lactic acid) in 9 parts by weight of a methylene chloride/DMF mixed solvent (weight ratio: 8/2) and 6 parts by weight of a solution of 1 part by weight of poly(L-lactic acid) in 9 parts by weight of a methylene chloride/DMF mixed solvent (weight ratio: 8/2).
  • the mean fiber diameter of the obtained fiber structure was 2 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m. No fiber surface depressions were observed. Scanning electron microscope photographs of the fiber structure are shown in Figs. 15 and 16.
  • the melting point was 221°C and no endothermic peak was observed below 190°C.
  • a fiber structure was obtained in the same manner as Example 2, except for mixing 3 parts by weight of a solution of 1 part by weight of poly(D-lactic acid) in 9 parts by weight of a methylene chloride/DMF mixed solvent (weight ratio: 8/2) and 7 parts by weight of a solution of 1 part by weight of poly(L-lactic acid) in 9 parts by weight of a methylene chloride/DMF mixed solvent (weight ratio: 8/2).
  • the mean fiber diameter of the obtained fiber structure was 2 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m. No fiber surface depressions were observed. Scanning electron microscope photographs of the fiber structure are shown in Figs. 17 and 18.
  • the main melting point was 221°C and a small endothermic peak was observed at 156°C.
  • a fiber structure was obtained in the same manner as Example 2, except that only a solution of 1 part by weight poly(D-lactic acid) in 9 parts by weight of a methylene chloride/DMF mixed solvent (weight ratio: 8/2) was used.
  • the mean fiber diameter of the obtained fiber structure was 1 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m. No fiber surface depressions were observed. Scanning electron microscope photographs of the fiber structure are shown in Figs. 19 and 20.
  • the melting point was 172°C.
  • a fiber structure was obtained in the same manner as Example 2, except that only a solution of 1 part by weight poly(L-lactic acid) in 9 parts by weight of a methylene chloride/DMF mixed solvent (weight ratio: 8/2) was used.
  • the mean fiber diameter of the obtained fiber structure was 3 ⁇ m, and no fibers were present with fiber lengths of less than 20 ⁇ m. Some corrugation of the fiber surfaces was seen, but no depressions were observed. Scanning electron microscope photographs of the fiber structure are shown in Figs. 21 and 22.
  • the melting point was 170°C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP05720436A 2004-03-16 2005-03-03 Fibre d'acide polylactique extrêmement fine, structure fibreuse et procédé pour produire celles-ci Withdrawn EP1731633A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004074011 2004-03-16
PCT/JP2005/004165 WO2005087988A1 (fr) 2004-03-16 2005-03-03 Fibre d'acide polylactique extrêmement fine, structure fibreuse et procédé pour produire celles-ci

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EP1731633A1 true EP1731633A1 (fr) 2006-12-13
EP1731633A4 EP1731633A4 (fr) 2007-12-19

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009042837A1 (fr) * 2007-09-28 2009-04-02 Natureworks Llc Fibres conjuguées de stéréocomplexes de polylactides
WO2009045877A1 (fr) * 2007-09-28 2009-04-09 Natureworks Llc Procédés de fabrication de fibres stéréocomplexes d'acide polylactique
EP2135887A1 (fr) 2008-06-18 2009-12-23 Instytut Biopolimeròw I Wlókien Chemicznych Procédé de production de poudre stéréocomplexe d'acide polylactique
CN104029443A (zh) * 2014-05-28 2014-09-10 中原工学院 一种pm2.5防护口罩用聚乳酸多层纤维膜的制备方法
WO2015155182A1 (fr) * 2014-04-10 2015-10-15 Purac Biochem Bv Membrane poly(lactique) et procédé de fabrication de la membrane

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007231480A (ja) * 2006-03-03 2007-09-13 Institute Of Physical & Chemical Research ステレオコンプレックス構造を有するポリ乳酸繊維およびその製造方法
JP4848224B2 (ja) * 2006-08-03 2011-12-28 太陽化学株式会社 ナノファイバー集合体
JP5028047B2 (ja) * 2006-08-08 2012-09-19 倉敷繊維加工株式会社 防風性、防水透湿性に優れる積層シート、それを用いた生地及びそれらの製造方法
JP4903595B2 (ja) * 2007-02-09 2012-03-28 パナソニック株式会社 ナノファイバー製造方法およびナノファイバー製造装置
JP2009006135A (ja) * 2007-05-31 2009-01-15 Teijin Ltd 嗜好性飲料抽出用フィルターをおよびこれを用いてなる嗜好性飲料抽出用バッグ
ES2370954T3 (es) * 2007-07-18 2011-12-26 Basf Se Método para la producción de nano-y mesofibras mediante electrohilado de dispersiones coloidales que contienen al menos un polímero esencialmente insoluble en agua.
US20110105695A1 (en) * 2007-09-28 2011-05-05 Schroeder Joseph D Method for making Plas stereocomplexes
US8242073B2 (en) * 2008-07-10 2012-08-14 The Hong Kong Polytechnic University Biodegradable and bioabsorbable biomaterials and keratin fibrous articles for medical applications
CN101831762A (zh) * 2010-04-08 2010-09-15 苏州大学 虎纹捕鸟蛛丝/聚乳酸复合纤维多孔膜及其制备方法
MY173719A (en) 2012-05-14 2020-02-18 Teijin Pharma Ltd Formed sheet product and hemostatic material
CN105274728B (zh) * 2014-05-28 2018-10-16 福建赛特新材股份有限公司 一种生物可溶解纤维毡及其制备方法和使用该毡的真空绝热板
US10786980B2 (en) * 2014-06-18 2020-09-29 Toray Industries, Inc. Laminate and production method therefor
JP6718159B2 (ja) * 2015-05-28 2020-07-08 国立大学法人京都工芸繊維大学 プラスチックナノファイバおよび光ファイバならびにプラスチックナノファイバの作製方法
KR101747825B1 (ko) 2015-12-22 2017-06-15 경희대학교 산학협력단 폴리-d-락트산 및 폴리-l-락트산의 스테레오컴플렉스 결정 구조를 포함하는 것을 특징으로 하는 압전소재
CN108754832B (zh) * 2018-04-10 2021-08-10 何炽斌 一种可生物降解的一次性拖地布及其生产方法
US11361893B2 (en) * 2018-11-27 2022-06-14 City University Of Hong Kong Soft body robotic device
CN115467084B (zh) * 2022-09-05 2023-08-08 南通大学 一种亲水性pla油水分离膜及其制备方法
CN116791233A (zh) * 2023-03-17 2023-09-22 东华大学 一种多孔聚乳酸抗菌纳米纤维及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2181207B (en) * 1985-10-04 1990-05-23 Ethicon Inc Improvements in electrostatically produced structures and methods of manufacturing thereof
JPH0781204B2 (ja) * 1987-04-21 1995-08-30 株式会社バイオマテリアルユニバ−ス ポリ乳酸繊維
JPH03220305A (ja) * 1989-11-21 1991-09-27 I C I Japan Kk 静電紡糸の製造方法
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
FR2709500B1 (fr) * 1993-08-02 1996-02-16 Fiberweb Sodoca Sarl Non-tissé à base de polymères dérivés de l'acide lactique, procédé de fabrication et utilisation d'un tel non-tissé.
JP3316306B2 (ja) * 1994-05-06 2002-08-19 カネボウ株式会社 高分子量ポリ乳酸成形品の製造方法
JP2002030523A (ja) * 2000-07-14 2002-01-31 Toray Ind Inc ポリ乳酸繊維
KR20020063020A (ko) * 2001-01-26 2002-08-01 한국과학기술연구원 미세 섬유상 고분자웹의 제조 방법
US6713011B2 (en) * 2001-05-16 2004-03-30 The Research Foundation At State University Of New York Apparatus and methods for electrospinning polymeric fibers and membranes
JP4056361B2 (ja) * 2002-11-14 2008-03-05 帝人株式会社 ポリグリコール酸繊維構造体、およびその製造方法
JP2004256974A (ja) * 2003-02-27 2004-09-16 Japan Vilene Co Ltd 静電紡糸方法及び静電紡糸装置
JP4383763B2 (ja) * 2003-03-28 2009-12-16 帝人株式会社 細胞培養基材およびその製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of WO2005087988A1 *
ZONG X ET AL: "Structure and process relationship of electrospun bioabsorbable nanofiber membranes" POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 43, no. 16, July 2002 (2002-07), pages 4403-4412, XP004373517 ISSN: 0032-3861 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009042837A1 (fr) * 2007-09-28 2009-04-02 Natureworks Llc Fibres conjuguées de stéréocomplexes de polylactides
WO2009045877A1 (fr) * 2007-09-28 2009-04-09 Natureworks Llc Procédés de fabrication de fibres stéréocomplexes d'acide polylactique
US8182725B2 (en) 2007-09-28 2012-05-22 Natureworks Llc Methods for making polylactic acid stereocomplex fibers
US8377353B2 (en) 2007-09-28 2013-02-19 Natureworks Llc Process of making conjugate fibers
CN101878330B (zh) * 2007-09-28 2014-07-23 自然工作有限责任公司 制造聚乳酸立体络合纤维的方法
EP2135887A1 (fr) 2008-06-18 2009-12-23 Instytut Biopolimeròw I Wlókien Chemicznych Procédé de production de poudre stéréocomplexe d'acide polylactique
WO2015155182A1 (fr) * 2014-04-10 2015-10-15 Purac Biochem Bv Membrane poly(lactique) et procédé de fabrication de la membrane
US10443154B2 (en) 2014-04-10 2019-10-15 Purac Biochem B.V. Poly(lactic acid) membrane and method of making the membrane
US11970790B2 (en) 2014-04-10 2024-04-30 Purac Biochem B.V. Poly(lactic acid) membrane and method of making the membrane
CN104029443A (zh) * 2014-05-28 2014-09-10 中原工学院 一种pm2.5防护口罩用聚乳酸多层纤维膜的制备方法
CN104029443B (zh) * 2014-05-28 2016-04-13 中原工学院 一种pm2.5防护口罩用聚乳酸多层纤维膜的制备方法

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JPWO2005087988A1 (ja) 2008-01-31
CA2560363A1 (fr) 2005-09-22
KR20060130732A (ko) 2006-12-19
CN1985032A (zh) 2007-06-20
EP1731633A4 (fr) 2007-12-19
US20070172651A1 (en) 2007-07-26
JP4243292B2 (ja) 2009-03-25

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