WO2007105479A1 - Procede de filage electrostatique a l'etat fondu et fibre extra fine - Google Patents

Procede de filage electrostatique a l'etat fondu et fibre extra fine Download PDF

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Publication number
WO2007105479A1
WO2007105479A1 PCT/JP2007/053560 JP2007053560W WO2007105479A1 WO 2007105479 A1 WO2007105479 A1 WO 2007105479A1 JP 2007053560 W JP2007053560 W JP 2007053560W WO 2007105479 A1 WO2007105479 A1 WO 2007105479A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
fiber
laser beam
resin
collector
Prior art date
Application number
PCT/JP2007/053560
Other languages
English (en)
Japanese (ja)
Inventor
Nobuo Ogata
Shinji Yamaguchi
Koji Nakane
Shigetoshi Amiya
Original Assignee
Kuraray Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Publication of WO2007105479A1 publication Critical patent/WO2007105479A1/fr

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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
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/04—Melting filament-forming substances
    • 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
    • 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

Definitions

  • the present invention relates to a melt-type electrospinning method using a laser beam as a heating means and fibers obtained by this method (particularly, ultrafine fibers having a fiber diameter of nanometer size).
  • an electrostatic spinning method is used in which fibers are formed by applying a high voltage to a polymer solution or polymer melt.
  • the former method using a polymer solution is referred to as a solvent-type electrospinning method
  • the latter method using a polymer melt is referred to as a melt-type electrospinning method. Since the melt-type electrospinning method is derived from the solvent-type electrospinning method, the spinning principle is basically the same.
  • the solvent-type electrospinning method first, a polymer solution is put into a syringe, and a high voltage is applied between a nozzle attached to the tip of the syringe and a collector.
  • the polymer solution into which the charge has been introduced flies by receiving an electrostatic attraction in the direction of the collector having the opposite charge, such as the nozzle tip, and in this process the solvent evaporates to form nanofibers.
  • the Such a solvent-type electrospinning apparatus is widely used because it can be easily produced, and nanofibers have been developed for many polymer materials that dissolve in solvents. Therefore, at present, it is no exaggeration to say that the electrospinning method refers to the solvent-type electrospinning method.
  • the melt-type electrospinning method imparts a charge to a molten polymer, and the melt is made by an electric attractive force between the charged melt and an electrode (collector) having a different charge. Voluntary This is a method of producing a fine fiber by stretching the film.
  • the point of action of the force (electric attraction) acting for draft drawing with a very small electric charge can be limited to a very small region. It is possible to make it smaller than the fiber diameter obtained.
  • the melt-type electrospinning method since no solvent is used, it is not necessary to collect the solvent, and it is not necessary to remove the remaining solvent from the collected fiber cartridge. Therefore, the melt-type electrospinning method can produce ultrafine fibers with high productivity that is friendly to the environment as compared with the solvent-type electrospinning method.
  • Non-patent Document 1 For example, Jason Lyons, Christopher Li, Trunk Ko., "Melt-electrospinning part I: processing parameters and geometric properties" (Non-patent Document 1) has a few findings regarding the melt-type electrospinning method.
  • a melt-type electrospinning apparatus is disclosed in which a melt-extrusion apparatus portion is grounded and a high voltage is applied to a fiber collector (collector). The reason for being grounded is to prevent the melt / extrusion device from being damaged by the discharge current generated when a high voltage is applied to the melt. Polypropylene fiber is manufactured Yes.
  • the temperature of the melt due to heat dissipation in the vicinity of the nozzle tends to decrease, and when the polymer melt is discharged, there is a tendency for the viscosity to increase rapidly.
  • the heater of the melt-extrusion device is likely to fail.
  • the melting / extrusion unit is grounded and a high voltage is acting on the collector, it is difficult to handle the collected fibers.
  • Non-patent Document 2 Steave Warner “Cost—Effective NanoFiber Formation-Melt Eiectrospinnin gj (Non-patent Document 2), a thermoplastic polymer (polypropylene) is placed in a syringe, and a plastic tube is wound around the syringe.
  • a method is disclosed in which a thermoplastic polymer is indirectly heated and melted by circulating a heat medium, and a high voltage is applied to a needle at the tip of a syringe to perform melt electrostatic spinning.
  • the temperature of the heat medium that can be circulated through the tube is limited, and it is difficult to produce ultrafine fibers using a high-functional polymer material having a high melting point.
  • Tokubyo 1 Jason Lyons, hnstopher Li, Frank Ko., “Melt— electrospinning part I: processing parameters and geometric properties, Polymer 45 (2004) 7597-7603
  • Patent Document 2 Steave Warner“ Cost— Effective NanoFiber Formation- Melt Electrosp inningj, National Textile Center, FY 2005 New Project Proposal, Project No. F05— MD01
  • an object of the present invention is to increase the fiber made of a thermoplastic resin, particularly an ultrafine fiber.
  • An object of the present invention is to provide a melt-type electrospinning method that can be manufactured with energy efficiency and workability, and fibers obtained by the method, particularly ultrafine fibers and a melt-type electrospinning apparatus.
  • Another object of the present invention is to provide a melt-type electrospinning method capable of producing continuous filament fibers even with a nanometer size, ultrafine fibers obtained by the method, and a melt-type electrospinning apparatus. There is to do.
  • Still another object of the present invention is to provide a melt-type electrospinning method capable of producing nanometer-sized ultrafine fibers, even for engineering plastics having a high melting point, the ultrafine fibers obtained by the method, and a melt It is to provide a type electrospinning apparatus.
  • the present inventors have found that, in the melt-type electrospinning method, when a laser beam is used as a heating means, fibers made of thermoplastic resin, particularly ultrafine fibers. Found that the fiber can be obtained with high energy efficiency and workability, and created the present invention.
  • a heating and melting step in which a thermoplastic resin is heated and melted by irradiating a laser beam, and a fiber that stretches by applying a voltage to the melted portion of the thermoplastic resin.
  • the fiber is manufactured through an electrospinning process that is collected in a collector.
  • a voltage may be applied between the electrode part for imparting electric charge to the thermoplastic resin and the collector, and the voltage may be applied to the molten part of the thermoplastic resin.
  • a linear body resin capable of irradiating a laser beam from a plurality of radiation directions is used, and the resin inserted in the hole formed in the electrode part is continuously supplied to the heating and melting part.
  • the laser beam for example, a laser beam having a beam diameter of 2 to 50 times the average diameter of the linear body resin may be used.
  • ultrafine fibers having an average fiber diameter of 5 m or less, particularly 50 to about LOOOnm can be obtained.
  • a biodegradable plastic or an engineering plastic may be used as the thermoplastic resin.
  • the present invention also includes fibers obtained by the above method, particularly ultrafine fibers. Also included are nanometer-sized ultrafine fibers composed of a resin having melt anisotropy. Furthermore, a fiber assembly including nanometer-sized ultrafine fibers is also included.
  • the present invention includes a heating for heating and melting the thermoplastic resin by irradiation with a laser beam. Also included is a melt-type electrospinning apparatus that includes a melting unit and an electrostatic spinning unit that applies a voltage to the heated and melted thermoplastic resin to collect the stretched fibers in a collector.
  • the heating and melting unit may have an electrode portion to which a voltage is applied between the collector and the collector, and an electric charge is applied to the molten portion of the thermoplastic resin.
  • the distance between the electrode part and the laser beam irradiation part may be about 0.5 to about LOmm.
  • the present invention includes a heating and melting step in which thermoplastic resin is heated and melted, and an electrospinning step in which voltage is applied to the melted portion of the thermoplastic resin to collect stretched fibers in a collector.
  • a laser beam to heat and melt the thermoplastic resin by irradiation is also included in the production of fibers through the above. The invention's effect
  • thermoplastic thermoplastic resin melted by irradiation with a laser beam is electrostatically spun, the obtained fiber without diffusing and releasing thermal energy can be easily taken out. That is, it is possible to produce fibers (especially even nano-sized fibers) made of thermoplastic resin with high energy efficiency and workability. In addition, thermal decomposition caused by long-term exposure of the resin to a high temperature state as in the conventional melt type electrospinning method is also suppressed. Even with nanometer-sized ultrafine fibers, continuous filament fibers can be obtained. Furthermore, because the thermoplastic resin can be melted locally and instantaneously with a single laser beam, even ultra-fine fibers of nanometer size can be manufactured even for engineering plastics with a high melting point that is not constrained by equipment. it can.
  • FIG. 1 is a schematic view showing an example of a production process in the melt type electrospinning method of the present invention.
  • FIG. 2 is a schematic plan view showing a step of irradiating a linear thermoplastic resin with a laser beam from three directions.
  • FIG. 3 is a graph showing the relationship between collector distance and fiber diameter in the fiber obtained in Example 1.
  • FIG. 4 is a graph showing the relationship between the laser output and the fiber diameter of the fiber obtained in Example 1.
  • FIG. 5 is a scanning photomicrograph of the fiber obtained in Example 1.
  • FIG. 6 is a graph showing the relationship between laser output and fiber diameter in the fiber obtained in Example 2.
  • FIG. 7 is a scanning photomicrograph of the fiber obtained in Example 2.
  • a heating and melting step in which a thermoplastic resin is irradiated with a laser beam to heat and melt the thermoplastic resin, and a voltage is applied to the melted portion of the thermoplastic resin to cause the stretched fiber to be collected by a collector (fiber The fiber is manufactured through an electrostatic spinning process for collecting in the collecting section.
  • FIG. 1 and FIG. 2 are schematic schematic diagrams showing an example of a manufacturing process and a manufacturing apparatus in the melt type electrospinning method of the present invention.
  • the linear thermoplastic resin 1 is inserted into the hole 3 of the electrode part 2 and continuously supplied to the heating and melting part 5 that is separated from the hole by a predetermined distance by the supply part 4. Is done.
  • a copper fine wire aggregate is disposed over the inner peripheral surface of the hole 3.
  • the linear body resin 1 is irradiated with a spot laser beam 7 from the laser light source 6 and instantaneously heated and melted.
  • thermoplastic resin examples include olefin-based resins (for example, polyethylene-based resins such as polyethylene, polypropylene-based resins such as polypropylene, etc.), styrene-based resins (for example, polystyrene, ABS resins) AS resin), vinyl resin (for example, polyvinyl chloride) -Salts such as rubbers, (meth) acrylic resins such as polymethyl methacrylate, ethylene-bule alcohol copolymer resins, etc., polyester resins (eg, poly (ethylene naphthalate)) , Polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate and other aromatic polyester resins, polylactic acid and other aliphatic polyester resins, polyarylate and other fully aromatic polyester resins, liquid crystal polyester Etc.), polyamide-based resins (for example, aliphatic polyamide-based resins such as polyamide 6, semi-aromatic polyamide-based resins such as nylon
  • thermoplastic resin for example, poly-phenylene ether
  • polyacetanol resin for example, polyoxymethylene
  • polyether ketone-based resin polyether ketone, polyether ether ketone, etc.
  • polysulfone-based resin for example, polysulfone, polysulfone, etc.
  • Ether sulfones etc.
  • thermoplastic resin can be used individually or in combination of 2 or more types.
  • thermoplastic resins low-viscosity thermoplastic resins are preferred from the viewpoint of easy formation of ultrafine fibers such as nanofibers.
  • thermoplastic resins even a biodegradable plastic for which it is difficult to select a solvent or an engineering plastic having a high melting point can be easily spun.
  • Examples of the biodegradable plastic include an aliphatic polyester-based resin and an aliphatic polyamide-based resin. Of these, aliphatic polyester-based rosin is preferred.
  • Examples of the aliphatic polyester resin include polyalkylene succinates such as polyethylene succinate, polypropylene succinate, and polyneopentylene succinate, and polyalkylene adipates such as polyethylene adipate, polybutylene adipate, and polyneopentylene adipate.
  • Polydalonic acid polylactic acid, polyoxycarboxylic acid such as polymalic acid, polypropatolatone, polylatatatone such as polylactonate, etc.
  • Engineering plastics include polyester resin, polyamide resin, poly Examples thereof include imide-based resins, polyphenylene ether-based resins, and polyphenylene sulfide-based resins.
  • thermopick liquid crystal polymers having melt anisotropy liquid crystal polyester-based resins, liquid crystal polyamide-based resins, liquid crystal polyester amide-based resins, etc.
  • the liquid crystalline polyester resin is a polyester resin having a mesogen group (group having liquid crystal forming ability) such as a P-substituted aromatic ring, a linear biphenyl group, and a substituted naphthyl group as a structural unit. Also good.
  • P-hydroxybenzoic acid diols (aromatic diols such as dihydroxybiphenyl, C-alkanediols such as ethylene glycol), aromatic dicarboxylic acids (terephrine)
  • Examples thereof include a copolymer obtained from at least one monomer selected from taric acid and the like and aromatic hydroxycarboxylic acid (such as oxynaphthoic acid). More specifically, a copolymer composed of p-hydroxybenzoic acid units and 4,4′-dihydroxybiphenyl units, P-hydroxybenzoic acid units, 4,4′-dihydroxybiphenyl units and terephthalate. A copolymer composed of acid units, a copolymer composed of p-hydroxybenzoic acid units and ethylene terephthalate units, and a copolymer composed of p-hydroxybenzoic acid units and 2oxy-6 naphthoic acid units. A polymer etc. are mentioned.
  • liquid crystalline polyester-based resins are listed under trade names such as “Vectra”, “Zaeder”, “Econol” and “X-7G”. Although the liquid crystal polymer has high mechanical properties, it is particularly suitable for the method of the present invention because of its excellent orientation and melt flowability.
  • the thermoplastic resin is used for various additives used for fibers, such as stabilizers (anti-oxidation inhibitors, ultraviolet absorbers, thermal stabilizers, etc.), flame retardants, antistatic agents, and colorants. , Fillers, lubricants, antibacterial agents, insecticides, acaricides, fungicides, matting agents, animal thermal agents, fragrances, fluorescent whitening agents, wetting agents, plasticizers, thickeners, dispersants, foaming agents, etc. It may contain. These additives can be used alone or in combination of two or more.
  • Each of these additives can be used at a ratio of 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, for example, 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass. The ratio is about the same as that of the part.
  • the thermoplastic resin may be melted in advance to form a semi-solid, but a solid is preferable from the viewpoint of simplicity and workability.
  • the shape of the thermoplastic resin is not particularly limited as long as it can be melted by irradiation with a laser beam, and may be indefinite. From the viewpoint of being able to melt locally and instantaneously by irradiating a laser beam, a linear body is preferable.
  • the cross-sectional shape is not particularly limited, and may be a polygonal shape (such as a triangle or a square shape), an elliptical shape, or an indefinite shape, but is usually a circular shape.
  • the average diameter of the linear body resin may be larger than the beam diameter of the laser beam to be irradiated, but is preferably smaller.
  • Such an average diameter is a force that can be selected according to the type of laser beam. For example, 0.1 to 2 mm, preferably 0.2 to 1.5 mm, more preferably 0.3 to: Lmm (especially 0.4 to 0 About 8mm).
  • the length of the linear body fat is not particularly limited, and may be selected according to the amount of necessary fiber.
  • 1S Usually 10 mm or more (for example, 10 to 500 mm), preferably 30 mm or more (for example, 30 to 300 mm), more preferably about 50 mm or more (for example, 50 to 200 mm).
  • the means for supplying the thermoplastic resin to the heating and melting part is not particularly limited as long as it can be delivered in a predetermined direction.
  • the wire using an electric driving force (rotation of a motor, etc.) is used.
  • It is a device having a mechanism (for example, a mechanism that converts the rotational motion of a motor into a linear motion) that can move the body grease at a constant speed.
  • a mechanism for example, a mechanism that converts the rotational motion of a motor into a linear motion
  • it may be a device having a holding part (chuck) capable of fixing the linear body resin.
  • the feed rate of the thermoplastic resin is higher in terms of productivity.
  • 1 to 10 OOmmZ time preferably 5 to 500mmZ time, more preferably 10 to 300mmZ It is about time (especially 50 to 200 mmZ hours).
  • the thermoplastic resin a plurality of the same or different types of linear resin resins may be continuously supplied to the heating and melting portion in the form of strands (rods).
  • a plurality of linear body resins having different polymer types are simultaneously supplied to a heating and melting section, melted separately, and then electrostatically spun in different states to be composed of a plurality of fibers. Fiber aggregates can also be obtained.
  • a plurality of linear body resins having different polymer types are heated and melted at the same time to obtain a molten polymer solution in which a plurality of types of polymers are bonded together, and then the solution is electrostatically spun to obtain a plurality of polymer types. It is also possible to obtain a fiber assembly composed of a composite fiber made of the above polymer.
  • thermoplastic resin supplied to the heating and melting part is melted by irradiation with a laser beam.
  • thermoplastic resin especially linear thermoplastic resin
  • the present invention can suppress the diffusion of thermal energy and the thermal decomposition of the thermoplastic resin, and it does not require any special device for the discharge and melts. Electrospinning is possible.
  • a thermoplastic resin having a high melting point for example, a liquid crystal polymer can be electrospun, and a fiber composed of a high melting point resin (such as a liquid crystal polymer), particularly an ultrafine fiber can be obtained.
  • YAG laser YAG laser
  • CO carbon dioxide
  • a laser beam by a carbon dioxide laser is preferable because the thermoplastic resin having high power efficiency and high meltability.
  • the wavelength of the laser beam is, for example, about 200 nm to 20 ⁇ m, preferably 500 nm to 18 ⁇ m, more preferably about 1 to 16 m (particularly 5 to 15 ⁇ m).
  • the method of irradiating the laser beam is not particularly limited, but a method of irradiating the laser beam in a spot shape is preferable from the viewpoint that the thermoplastic resin can be irradiated locally.
  • the size of the beam diameter for irradiating the thermoplastic resin with this spot-like laser beam can be selected according to the shape of the thermoplastic resin.
  • the specific beam diameter is, for example, in the case of a linear body resin, as long as the diameter is larger than the average diameter of the linear body resin, for example, 0.5 to 30 mm, preferably 1 to 20 mm, and more preferably Is about 2 to 15mm (especially 3 to 10mm).
  • the ratio of the average diameter of the linear body resin to the beam diameter is 1 to: about L00 times the average diameter of the linear body resin, preferably 2 to 50 times, More preferably, the beam diameter is about 3 to 30 times (particularly 5 to 20 times).
  • the output of the laser beam necessary for melting the thermoplastic resin may be controlled within a range that is equal to or higher than the melting point of the thermoplastic resin and lower than the ignition point of the thermoplastic resin. The larger one is preferable from the viewpoint of producing ultrafine fibers.
  • the specific output of the laser beam can be appropriately selected according to the physical properties (melting point, LOI value (limit oxygen index)) and shape of the thermoplastic resin used, the supply rate of the thermoplastic resin, etc. 0.1 to 50W, preferably 1 to 35W, more preferably 5 to 30W (especially 10 to 25W) .
  • the irradiation condition of the laser beam may be controlled by measuring the melting point of the thermoplastic resin, but if the thermoplastic resin is a linear body having a small diameter and a high voltage is applied, it is easy to use. From the point of view, it is preferable to control by the output of the laser beam.
  • the laser beam irradiation method may be applied from one direction, but from the point that the thermoplastic resin can be melted uniformly and sufficiently, the same melted part (especially, in the case of linear body resin) It is preferable to irradiate the front end portion locally from a plurality of directions, for example, a plurality of radiation directions.
  • the number of irradiations from a plurality of directions may be, for example, two or more directions, preferably 2 to 6 directions, and more preferably 3 to 5 directions.
  • Such irradiation from a plurality of directions may be performed using a plurality of laser light sources, but in order to efficiently melt the thermoplastic resin, a laser irradiated by a single laser light source is used. It is preferable to irradiate one light beam from a plurality of directions using a reflecting mirror.
  • the reflecting mirror is a first reflecting mirror located on the opposite side to the laser beam irradiation side with the heating and melting part of the resin as the center, and the laser beam reflected from the reflecting mirror is heated and melted by the thermoplastic resin.
  • a second reflecting mirror for re-reflecting to the part.
  • the position of the reflecting mirror is preferably arranged so that the laser beam is irradiated radially at equal intervals.
  • the light that is not absorbed by the thermoplastic resin is reflected by the first reflecting mirror and adjacent to it. It is incident on the second reflecting mirror.
  • the second reflecting mirror is arranged at a position where the laser beam incident from the first reflecting mirror can be irradiated again to the thermoplastic resin, and the one laser beam incident on the second reflecting mirror is irradiated again with the thermoplastic resin.
  • the laser beam may be finally absorbed by the laser beam absorber.
  • (2 n ⁇ 2) reflecting mirrors and 1 piece are arranged in a direction divided in 2n directions radially around a thermoplastic resin. If one laser beam is irradiated from the remaining one direction, and the laser beam irradiates the thermoplastic resin from n directions by reflection of (2n-2) reflecting mirrors. Good.
  • FIG. 2 is a schematic plan view showing a process of irradiating a linear body thermoplastic resin with laser beams from three directions.
  • the laser beam 21 irradiated from the laser irradiation part is a linear body oil 2
  • the first reflecting mirror 23 a the light that has not been absorbed by the linear body resin 22 is reflected by the first reflecting mirror 23 a.
  • the light reflected by the first reflecting mirror 23a is incident on the second reflecting mirror 23b disposed adjacent to the first reflecting mirror 23a at an angle of 60 ° in the radial direction centered on the linear body grease 22. Therefore it is reflected.
  • the second reflecting mirror 23b is arranged at an angle at which the light from the first reflecting mirror 23a is reflected and the linear body grease 22 can be irradiated again.
  • the linear body resin 22 is heated more uniformly than the resin irradiated from a single direction.
  • thermoplastic resin In the electrostatic spinning process, a voltage is applied to the melted portion of the thermoplastic resin melted in the above process, and the extending fibers are collected in the collector by electrical attraction. Specifically, in this process, a voltage is applied to the melted portion of the thermoplastic resin to apply an electric charge opposite to the collector to charge the molten resin, so that the molten resin can fly toward the collector. Then, it is electrospun by stretching or stretching.
  • thermoplastic resin As a method of applying a voltage to the melted part of the thermoplastic resin, specifically, a voltage is applied between the electrode part and the collector to apply a voltage to the melted part of the thermoplastic resin. Use the method.
  • electric charge is imparted to the thermoplastic resin through the electrode portion to which the voltage is applied in this way.
  • the thermoplastic resin is a linear body
  • the thermoplastic resin is inserted through the electrode portion by inserting the linear body resin into the hole formed in the electrode portion. Is charged.
  • the thermoplastic resin is electrostatically spun by electrostatic attraction with a collector charged at the opposite pole, both positive and negative. Usually, the thermoplastic resin is positively charged and the collector is negatively charged.
  • the method of applying a voltage to the melted part of the thermoplastic resin is a direct application method in which the laser beam irradiated part (heated melted part of the thermoplastic resin) and the electrode part for imparting electric charge are matched.
  • the laser beam is effectively used as the heat energy.
  • Indirect application method in which the laser beam irradiation part and the electrode part for applying electric charge are provided at separate positions because the laser beam can be converted into a single point, the laser beam reflection direction can be easily controlled, and the safety is high.
  • a method of providing a laser beam irradiation part on the downstream side in the thermoplastic resin supply direction is preferred.
  • the thermoplastic resin is irradiated with a laser beam on the downstream side of the electrode unit, and the distance between the electrode unit and the laser beam irradiation unit (for example, the downstream end of the electrode unit and the upstream end of the outer periphery of the laser spot) Is preferably adjusted to a specific range (for example, about 10 mm or less).
  • This distance can be selected according to the conductivity, thermal conductivity, glass transition point, laser beam irradiation amount, etc. of the thermoplastic resin, for example, 0.5 to: LOmm, preferably 1 to 8 mm, more preferably Is about 1.5 to 7 mm (especially 2 to 5 mm). If the distance force between the two is within this range, the molecular mobility of the thermoplastic resin in the vicinity of the irradiated area of the laser beam is increased, and sufficient electric charge can be imparted to the molten thermoplastic resin. Can be improved.
  • the voltage applied between the electrode section and the collector is preferably a high voltage within a range in which no discharge occurs, depending on the required fiber diameter, the distance between the electrode and the collector, the amount of laser beam irradiation, and the like. It can be selected as appropriate.
  • the general voltage is, for example, about 0.1 to 40 kVZcm, preferably about 1 to 30 kVZcm, more preferably about 5 to 25 kVZcm (particularly about 10 to 20 kVZcm).
  • the electrode portion may be made of a conductive material (usually a metal component).
  • a group 6A element such as chromium, a group 8 metal element such as platinum, a group 1B element such as copper or silver, etc.
  • Metal elements and alloys such as aluminum alloys and stainless steel alloys
  • 2B group elements such as zinc and 3B group elements
  • aluminum oxides such as silver oxide and acid aluminum
  • a freight etc. these metal components can be used alone or in combination of two or more. Of these metal components, copper, silver, aluminum, stainless steel alloy and the like are particularly preferable.
  • thermoplastic resin In order to charge the thermoplastic resin efficiently by the electrode part, a hole is formed in the electrode part, and the electric charge is injected to the thermoplastic resin inserted into the hole part through the hole. It is preferable to apply.
  • the hole part of the electrode part can be selected according to the shape and size of the thermoplastic resin. For example, in the case of a linear body resin having a circular cross section, the cross section having a larger pore diameter than the linear body resin circular The hole (hollow part) may be used.
  • the coil part has a coiled metal wire, a fine metal wire assembly, etc. on the surface of the hole part (especially substantially over the entire surface).
  • Metal wires may be provided.
  • the metal component constituting the metal wire the metal components exemplified in the electrode part can be used, and usually copper, silver, aluminum, stainless steel alloy and the like are used.
  • thermoplastic resin When a coiled metal wire is disposed in the hole, a high voltage can be easily applied to the thermoplastic resin inside the coil.
  • the metal fine wire aggregate when the metal fine wire aggregate is disposed in the hole, the metal fine wire softly surrounds the thermoplastic resin (particularly, the linear resin grease) (encloses the resin without being scratched) and the charge is thermoplastic. Can be given to rosin.
  • Such a metal wire is particularly useful when the supply direction of the thermoplastic resin is a vertical direction from the viewpoint of charge imparting property and the like.
  • the melted part of the thermoplastic resin When charges are applied to the melted part of the thermoplastic resin in this manner, the melted part gradually becomes conical (so-called tailored cone) by collecting and repelling charges on the surface. Further, in the formed tailor cone, when the repulsive force of the charge exceeds the surface tension, the molten liquid is ejected from the tip of the cone toward the collector by electrostatic attraction and becomes a fiber.
  • a voltage as described above is applied between the heating and melting part (laser beam irradiation part) and the collector, for example, 0.1 to 40 kVZcm, preferably 1 to 30 kVZcm, and more preferably.
  • An electric field of about 5-25kVZcm (especially 10-20kVZcm) is formed! / ⁇ .
  • the distance (collector distance) between the melted portion of the thermoplastic resin (tailor cone tip) and the collector is not particularly limited, and may be 5 mm or more. However, in order to efficiently produce ultrafine fibers, For example, it may be about 10 to 300 mm, preferably 15 to 200 mm, more preferably 20 to 130 mm (particularly 30 to LOOmm)! / ⁇ .
  • the space (spinning space) between the heat-melting part and the collector may be an inert gas atmosphere.
  • the inert gas include nitrogen gas, helium gas, argon gas, and carbon dioxide gas. Of these, nitrogen gas is usually used.
  • the inert gas is provided in the hole force spinning space by providing a passage for supplying the inert gas to the electrode part having the hole part and joining the hole part. Inert gas may be supplied.
  • the spinning space may be heated.
  • a heating method for example, a method using a heater (eg, a norogen heater, etc.), a method of irradiating a laser beam or the like can be mentioned.
  • the heating temperature can be selected according to the melting point of the thermoplastic resin, for example, from a temperature range of 50 ° C or higher and below the ignition point of the resin, but from the viewpoint of spinnability, the melting point of the thermoplastic resin A temperature below (eg, 100-5 ° C below the melting point, temperature range, etc.) is preferred!
  • the collector can be selected according to the use of the collected fiber, and examples thereof include a flat plate (for example, a fixed flat plate, a rotating disk, etc.), a rotating drum, and a belt conveyor. .
  • a rotating drum or a belt conveyor may be used when producing a fiber assembly that may use a rotating disk.
  • a belt conveyor may be used.
  • a rotating drum with a traverse mechanism is used. Also good.
  • the fiber arrangement is improved and high-performance fibers can be obtained.
  • continuous linear fibers can be obtained by continuously supplying the linear thermoplastic resin to the heating and melting part, and filaments and fiber aggregates having a fiber length of 100 mm or more can be obtained. Can do.
  • the collector When a high voltage is applied between the collector and the electrode portion, the collector may be grounded (grounded) from the viewpoint of handling of the fibers to be collected.
  • fibers particularly ultrafine fibers having a small fiber diameter
  • the average fiber diameter of the ultrafine fibers is, for example, 5 ⁇ m or less, and preferably about 10011111 to 3111.
  • the ultrafine fiber having such an average fiber diameter may include, for example, a fiber having a fiber diameter of about 50 to 1000 nm (particularly 100 to 500 nm).
  • ultrafine fibers can be obtained by a simple method.
  • it is suitable for spinning a liquid crystal polymer having a melt anisotropy, which has been difficult to obtain nano-sized ultrafine fibers by a conventional melt spinning method having a high melting point. It is possible to produce ultrafine fibers (nanofibers) with a fiber diameter of 1 ⁇ m or less.
  • the fiber length of the fiber is not particularly limited and may be selected depending on the application by adjusting the production conditions and the like.
  • the average fiber length is 0.5 mm or more, and the fiber length such as nonwoven fabric is used.
  • the fiber length When used as a fiber assembly, it may be, for example, about 1 to 50 mm, preferably 2 to 30 mm, more preferably about 3 to LOmm.
  • the ultrafine fibers are generally obtained as a fiber assembly.
  • the continuously supplied grease is irradiated with a laser beam, so that it can be obtained as filamentous fibers having an average fiber length of 100 mm or more. it can.
  • a continuous filament having an average fiber length of, for example, 150 mm or more, preferably 200 mm or more (for example, about 200 to 100 mm) may be used. Fibers with a wide range of fiber diameters can be manufactured by adjusting the output of the laser beam applied to the thermoplastic resin.
  • the cross-sectional shape of the fiber is not particularly limited, and may be an irregular cross-section, but is usually a round cross-section.
  • the fiber assembly obtained by the melt-type electrospinning method of the present invention is composed of ultrafine fibers (in particular, continuous nanometer-sized ultrafine fibers) containing nanofibers. Furthermore, in the method of the present invention, a fiber assembly having dispersion in the fiber diameter can also be produced.
  • the difference between the maximum fiber diameter and the minimum fiber diameter is, for example, 200 ⁇ m to 5 ⁇ m, preferably 300 nm to 4 ⁇ m, more preferably 400 nm to 3 m (particularly 500 nm). ⁇ 2 ⁇ m)! /.
  • Such a fiber assembly is usually a nonwoven fabric (mat-like deposit, cylindrical deposit, etc.).
  • Non-woven fabrics use conventional methods such as binder methods, partial hot-pressure fusion (such as hot embossing), and entanglement treatment (needle punching, hydroentanglement, etc.). Can also be obtained.
  • the non-woven fabric is in a range that does not impair the effect of the ultrafine fiber of the present invention (for example, 0.1 to 50% by mass, preferably about 1 to 30% by mass), and other fibers (synthetic fiber, semi-synthetic fiber) , Recycled fibers, natural fibers, etc.).
  • the form is usually a sheet, and the thickness is suitable for the application.
  • 0.1 ⁇ Force that can select a range force of about LOOmm Usually 0.5 to 50mm, preferably l to 30mm, more preferably about 3 to 20mm.
  • the basis weight of the nonwoven fabric can be selected according to the application, for example, about 30 to 500 gZm 2 , preferably 50 to 500 g / m 2 , more preferably 80 to 450 g / m 2 This is about 100 to 400 g / m 2 ).
  • the obtained filaments and fiber aggregates may be further subjected to post-processing treatment such as electrification cage charging treatment, plasma discharge treatment or hydrophilization treatment by corona discharge treatment. Next processing may be performed. Furthermore, the obtained fiber assembly such as a nonwoven fabric may be laminated and integrated with another nonwoven fabric (for example, a spunbond nonwoven fabric) or a woven or knitted fabric.
  • post-processing treatment such as electrification cage charging treatment, plasma discharge treatment or hydrophilization treatment by corona discharge treatment.
  • Next processing may be performed.
  • the obtained fiber assembly such as a nonwoven fabric may be laminated and integrated with another nonwoven fabric (for example, a spunbond nonwoven fabric) or a woven or knitted fabric.
  • the melt type electrospinning apparatus of the present invention is not particularly limited as long as the melt type electrospinning method can be realized.
  • heat melting for heating and melting a thermoplastic resin by irradiation with a laser beam is possible.
  • a unit and an electrospinning unit for applying a voltage to the heated and melted thermoplastic resin to collect the extending ultrafine fibers in the collector by an electric attractive force.
  • the heating and melting unit includes a laser light source for irradiating a laser beam and a laser beam absorbing unit for absorbing a powerful laser beam that is not absorbed by the thermoplastic resin.
  • a laser beam absorber for example, a member containing a laser beam absorber (for example, a plastic member containing a black pigment such as carbon black) can be used.
  • a reflection mirror for reflecting the laser beam to the heating and melting part and irradiating it from a plurality of directions may be provided.
  • the electrostatic spinning unit includes a supply unit for supplying thermoplastic resin to a heating and melting part (laser beam irradiation part), and an electrode part for imparting electric charge to the melting part of the thermoplastic resin. And a collector for collecting ultrafine fibers, and a voltage generation unit for applying a voltage between the electrode unit and the collector.
  • the electrode part and the heat-melting part are disposed so as to have a distance described in the section of the electrospinning process.
  • the fiber obtained by the method of the present invention is ultrafine in nano units, it has excellent flexibility and a large surface area, and thus has excellent properties such as liquid absorbency and filterability. Therefore, various applications, for example, electronic parts such as insulating separators, industrial materials (oil adsorbents, leather base fabrics, cement compounding materials, rubber compounding materials, various tape base materials, etc.), medical Hygiene materials (paper diapers, gauze, bandages, medical gowns, surgical tapes, etc.), lifestyle-related materials (wipers, printed materials, packaging materials, packaging materials, storage materials, air filters, liquid filters, etc.), clothing materials, interior materials (insulation) Materials, sound-absorbing materials, etc.), construction materials, agriculture / horticultural materials, civil engineering materials (soil stabilizers, filtering materials, sand flow prevention materials, reinforcement materials, etc.), shoes materials, etc.
  • industrial materials oil adsorbents, leather base fabrics, cement compounding materials, rubber compounding materials, various tape base materials, etc.
  • ultrafine fibers composed of biodegradable plastics are suitable for medical or agricultural fields that require high performance.
  • non-woven fabrics are tissue medical engineering materials (artificial membranes), It can be used as a scaffold for cell growth, and the filament or cylinder can be used for artificial blood vessels.
  • Nonwoven fabrics made of ultrafine fibers made of engineering plastics should be used in the field of electronics such as battery separators (alkali secondary batteries such as nickel-cadmium batteries and nickel-hydrogen batteries) and capacitor separators. Can do.
  • battery separators alkali secondary batteries such as nickel-cadmium batteries and nickel-hydrogen batteries
  • the fiber diameter in the examples was measured by the following method. In the examples, “%” is based on mass unless otherwise specified. Furthermore, the method for measuring the fiber diameter in the examples is as follows.
  • Example 1 Polylactic acid melt type electrospinning
  • Polylactic acid Cargildau, grade 6200D, number average molecular weight Mn: 79461, weight average molecular weight Mw: 148640, RV: 3.1, 0 body: 1.8%, L body: 98.2%, mp: 171 ° C
  • a linear sample having an average diameter of about 0.5 mm and a length of 70 mm or more was obtained using a flow tester (CFT500, manufactured by Shimadzu Corporation).
  • the production conditions were a melting temperature of 267 ° C., an extrusion pressure of 1 MPa, and a die area of 1 mm 2 . This linear sample was subjected to the following melt electrospinning experiment.
  • a heating and melting unit having a laser light source, a reflecting mirror, and a laser beam absorbing portion, and an electrospinning unit having a supply portion, a voltage generating portion, an electrode portion, and a collector were provided.
  • Ultrafine fibers were produced using a melt type electrospinning apparatus.
  • a hole is formed in the electrode part, and the linear sample is inserted into the hole.
  • a high voltage is applied to the electrode part, and an electric charge is applied to the linear sample through the hole of the electrode part while the linear sample is moving downward.
  • the electrode part is formed by forming a hole in a black aluminum electrode rod, and a copper wire assembly is disposed on the entire surface of the hole.
  • FIG. 3 is a graph showing the relationship between collector distance and fiber diameter with the laser output fixed at 3W.
  • the applied high voltage was a high voltage (25 to 41 kV). From this experimental result, it was found that the collector distance does not significantly affect the fiber diameter when the collector distance is in the range of 20 mm to 130 mm.
  • FIG. 4 is a graph showing the relationship between the laser output and the fiber diameter with the collector distance fixed at 50 mm and the high voltage fixed at 41 kV just before discharge. From this experimental result, it can be seen that as the laser power increases, the fiber diameter decreases exponentially. Furthermore, since some fibers have an average fiber diameter of around 1 ⁇ m, it is clear that nanofibers of 1 ⁇ m or less can be partially obtained.
  • Polylactic acid (Shimadzu Corporation, Lacty 9031, weight average molecular weight 168, 000) 1 part by weight methylene chloride (Wako Pure Chemical Industries, Ltd., special grade) 4.5 parts by weight and N, N-dimethyl Formamide (special grade, manufactured by Wako Pure Chemical Industries, Ltd.)
  • a solution was prepared by dissolving in 4.5 parts by weight of a mixed solvent at room temperature (22 ° C). This solution was spun using a general solvent-type electrostatic spinning apparatus, and the fibrous aggregate was collected on a flat plate collecting electrode.
  • the inner diameter of the ejection nozzle was 0.8 mm
  • the voltage was 20 kV
  • the distance from the ejection nozzle to the flat plate collection electrode was 10 cm
  • the relative humidity was 40%.
  • the obtained fiber assembly was measured with a scanning electron microscope (manufactured by Hitachi, Ltd., S-2300), it was observed that the average fiber diameter was 0 and the fiber surface was smooth.
  • a special apparatus is required for collecting the gas filled with methylene chloride and N, N-dimethylformamide vapor, which are harmful to the human body, in the spinning atmosphere. Further, these solvents remained in the obtained fiber, and in order to remove this residual solvent, the obtained fiber assembly had to be washed away with acetone.
  • Example 2 (Vectra L920 melt-type electrospinning)
  • a linear sample having a diameter of about 0.8 mm and a length of 70 mm or more was obtained from a Vectra (manufactured by Polyplastics Co., Ltd., Grade L920) chip using a flow tester (manufactured by Shimadzu Corporation, CFT500). Preparation conditions, melting temperature 280 ° C, pressure 3 MPa, a die area lmm 2.
  • This sample was used to produce ultrafine fibers in the same manner as in Example 1.
  • Figure 6 is a graph showing the relationship between laser output and fiber diameter with the collector distance fixed at 25 mm. Also in this experiment, the applied high voltage was set to a high voltage (18 to 25 kV) just before the start of discharge. From this experimental result, it can be seen that the fiber diameter decreases as the laser output increases. Furthermore, since some fibers have an average fiber diameter of around 1 ⁇ m, it is clear that fibers with a diameter of 1 ⁇ m or less can be partially obtained.

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  • 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

L'invention concerne une fibre extra fine composée d'une résine thermoplastique, fibre produite selon une haute efficacité énergétique et une haute maniabilité. La fibre extra fine est produite par une étape de fusion thermique d'une résine thermoplastique en l'irradiant par un faisceau laser (7), et une étape de filage électrostatique pour collecter les fibres allongées dans une assembleuse (8) en faisant agir une tension sur la partie en fusion de la résine thermoplastique. Une tension peut être amenée à agir sur la partie en fusion de la résine thermoplastique en appliquant une tension entre une partie électrode (2) pour transmettre des charges à la résine thermoplastique et l'assembleuse (8). Par ailleurs, une résine linéaire (1) qui peut être irradiée par le faisceau laser (7) en provenance d'une pluralité de directions de rayonnement peut être utilisée et la résine (1) insérée dans un trou (3) formé dans la partie électrode (2) peut être acheminée de manière continue dans la partie de fusion thermique. Pour ce qui est du faisceau laser (7), un faisceau laser ayant un diamètre de faisceau faisant 2 à 50 fois le diamètre moyen de la résine linéaire peut être utilisé. Selon le procédé, une fibre extra fine ayant un diamètre moyen de fibre de 5 μm ou moins (en particulier, un diamètre de fibre de 50 à 1000 nm) peut être obtenue.
PCT/JP2007/053560 2006-03-06 2007-02-27 Procede de filage electrostatique a l'etat fondu et fibre extra fine WO2007105479A1 (fr)

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