WO2004072336A1 - Fibre poreuse, structure fibreuse poreuse et procede de production correspondant - Google Patents

Fibre poreuse, structure fibreuse poreuse et procede de production correspondant Download PDF

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Publication number
WO2004072336A1
WO2004072336A1 PCT/JP2004/001453 JP2004001453W WO2004072336A1 WO 2004072336 A1 WO2004072336 A1 WO 2004072336A1 JP 2004001453 W JP2004001453 W JP 2004001453W WO 2004072336 A1 WO2004072336 A1 WO 2004072336A1
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WO
WIPO (PCT)
Prior art keywords
fiber
hydrophobic solvent
porous
organic compound
fibrous structure
Prior art date
Application number
PCT/JP2004/001453
Other languages
English (en)
Japanese (ja)
Inventor
Takanori Miyoshi
Shinya Komura
Hiroyoshi Minematsu
Original Assignee
Teijin Limited
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 Teijin Limited filed Critical Teijin Limited
Priority to DE602004026561T priority Critical patent/DE602004026561D1/de
Priority to EP04710522A priority patent/EP1600533B1/fr
Priority to KR1020057012732A priority patent/KR101056982B1/ko
Priority to AT04710522T priority patent/ATE464408T1/de
Priority to US10/544,112 priority patent/US20060204750A1/en
Priority to JP2005504973A priority patent/JP4361529B2/ja
Publication of WO2004072336A1 publication Critical patent/WO2004072336A1/fr

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Classifications

    • 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
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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

Definitions

  • Porous fiber, porous fiber structure and method for producing the same are Porous fiber, porous fiber structure and method for producing the same
  • the present invention relates to a porous fiber formed without the need for a coagulating liquid, a fibrous structure comprising the same, and a method for producing the same.
  • the present invention relates to a porous fiber and a fiber structure mainly composed of a polymer soluble in a hydrophobic solvent and an organic compound having a plurality of hydroxyl groups, and a method for producing the same.
  • porous body In the field of regenerative medicine, a porous body may be used as a substrate (scaffold) when culturing cells.
  • Known porous materials include freeze-dried absorbent organic materials, foams, and fiber structures (see, for example, Non-Patent Document 1).
  • the fiber structures obtained by these conventional methods have too large a fiber diameter, so that the surface area to which cells can adhere is insufficient.
  • a fiber structure with a smaller fiber diameter is desired. Had been rare.
  • an electrostatic spinning method for example, see Patent Documents 1 and 2.
  • a liquid for example, a solution containing a fiber-forming substance is introduced into an electric field, and A step of drawing more liquid toward the electrode to form a fibrous substance.
  • the fiber-forming material is cured while being drawn from the solution.
  • Curing may be effected, for example, by cooling (eg, when the spinning liquid is solid at room temperature), chemical curing (eg, treatment with curing steam), or evaporation of the solvent.
  • the obtained fibrous substance is collected on an appropriately arranged receptor, and can be separated therefrom if necessary.
  • the electrospinning method can directly obtain a nonwoven fabric-like fibrous substance, there is no need to form a fibrous structure once the fibers are formed, and the operation is simple.
  • Non-Patent Document 2 It is known that a fibrous structure obtained by the electrospinning method is used as a substrate for culturing cells. For example, it has been studied to regenerate blood vessels by forming a fiber structure made of polylactic acid by an electrostatic spinning method and then culturing smooth muscle cells thereon (for example, see Non-Patent Document 2).
  • the fiber structure obtained by using these electrostatic spinning methods tends to have a dense structure in which the distance between fibers is short because the fiber diameter is small.
  • the cultured cells accumulate on the surface of the fiber forming the fiber structure as the culture proceeds, and the surface of the fiber structure is thickly covered with cells. I will.
  • Non-Patent Document 3 A method for forming a fibrous structure having regular holes has been reported (see Non-Patent Document 3 and Patent Document 3).
  • this method only the surface of the fiber has pores, and it is difficult to make the inside of the fiber porous.
  • a fibrous structure is formed from a solution containing a hydrophilic polymer and a hydrophobic polymer by an electrostatic spinning method, and the resulting fibrous structure is immersed in water to extract the hydrophilic polymer, thereby forming a porous fiber.
  • a method of forming is also reported (see Non-Patent Document 4 and Patent Document 3).
  • the finally obtained porous fiber is substantially composed of only a hydrophobic polymer, and has a problem that the hydrophilicity of the fiber structure cannot be controlled.
  • Patent Document 3 International Publication No. 02/16680 Pamphlet
  • Non-Patent Document 1 Noriya Ohno and Masuo Aizawa, Representative, “Regenerative Medicine”, N.T.I.S, Ltd., January 31, 2002, p.258
  • Non-Patent Document 2 Joel D. Stitchell, Christine J. Pauloski, Gerry Neck, David J. Simpson, Gerry El Powellin (Joel D. S titze 1, Kr istin J. Wnek, David G. S imps on, Gary L. Bow 1 in), Journal of Biomaterials Applications 2001 (Journalof Biomaterials Applicati ons 2001). ) ", Volume 16, (US), 22— P. 33,
  • Non-Patent Document 3 Michael Bonicky, Wolfgang Chad, Thomas Fleece, Andrews Shapa, Michael Hellwig, Martin Steinhart, Andrews Greina, Joa Kim Jäichi Pendrov (Michael Bogngnitzki, Wolfgang Czado, Thoma s F rese, An dreas S chaper, Michael He 11 wig, Martin Steinh art, And reas G reiner, Joach im H. Wend roff) ou rnalof Advanced Materials 2001) ”, Volume 13, (USA), pp. 70-72.
  • Non-Patent Document 4 Michael Bonicky, Thomas Fries, Martin Steinhart, Andries Greiner, Joakim Jä ⁇ ich Endrov (Michael Bognitzki, Thomas Fresse, Martin Steinh art, Andreas Greiner , Joach im H. Wend roff), "Polymer Engineering and Science 2001", Vol. 41, (USA), pp. 982-989.
  • a first object of the present invention is to provide a material that is suitable as a substrate for cell culture in the field of regenerative medicine. Specifically, a solution containing nutrients and the like necessary for cell culture can be easily dispersed throughout the cell. Fibers that can move, and fibers It is to provide a structure.
  • a second object of the present invention is to provide a production method capable of obtaining a hydrophilic fibrous porous fiber structure without requiring complicated steps such as an extraction operation.
  • FIG. 1 is a schematic diagram of a manufacturing apparatus for explaining one embodiment of the manufacturing method of the present invention.
  • FIG. 2 is a schematic diagram of a manufacturing apparatus for explaining one embodiment of the manufacturing method of the present invention.
  • FIG. 3 is an electron micrograph (magnification: 2000 ⁇ ) of the surface of the fibrous structure obtained by the operation of Example 1.
  • FIG. 4 is an electron micrograph (100,000 magnification) of a cross section of the fiber obtained by the operation of Example 1.
  • FIG. 5 is an electron micrograph (magnification: 20000) of the surface of the fibrous structure obtained by the operation of Example 2. '
  • FIG. 6 is an electron micrograph (100,000 magnification) of a cross section of the fiber obtained by the operation of Example 2.
  • FIG. 7 is an electron micrograph (magnification: 2000 ⁇ ) of the surface of the fibrous structure obtained by the operation of Example 3.
  • FIG. 8 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Example 3.
  • FIG. 9 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Example 4.
  • FIG. 10 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Example 4.
  • FIG. 11 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Example 5.
  • FIG. 12 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Example 5.
  • FIG. 13 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Example 6.
  • FIG. 14 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Example 6.
  • FIG. 15 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Example 7.
  • FIG. 16 is an electron micrograph (100,000 magnification) of a cross section of the fiber obtained by the operation of Example 7 taken.
  • FIG. 17 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Example 8.
  • FIG. 18 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Example 8.
  • FIG. 19 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Example 9.
  • FIG. 20 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Example 9.
  • FIG. 21 is an electron micrograph (200 ⁇ magnification) of the surface of the fibrous structure obtained by the operation of Comparative Example 1.
  • FIG. 22 is an electron micrograph (100,000 magnification) of a cross section of the fiber obtained by the operation of Comparative Example 1. '
  • FIG. 23 shows a photograph of the surface of the fiber structure obtained by the operation of Comparative Example 2. It is an electron micrograph (photographing magnification of 2000 times).
  • FIG. 24 is an electron micrograph (100,000 magnification) of a cross section of the fiber obtained by the operation of Comparative Example 2.
  • FIG. 25 is an electron micrograph (200 ⁇ magnification) of the surface of the fiber structure obtained by the operation of Comparative Example 3.
  • FIG. 26 is an electron micrograph (magnification: 1000 ⁇ ) of a cross section of the fiber obtained by the operation of Comparative Example 3.
  • the fibrous structure refers to a three-dimensional structure formed by laminating, weaving, knitting, or other methods obtained by laminating one or more porous fibers.
  • Specific forms of the fibrous structure include, for example, nonwoven fabrics, and tubes, meshes, and the like processed based on the nonwoven fabrics are also preferably used in the field of regenerative medicine.
  • porous fiber and the fiber structure of the present invention contain a polymer that can be dissolved in a hydrophobic solvent.
  • the hydrophobic solvent of the present invention is an organic substance that cannot dissolve 5% or more of water at normal temperature (for example, 27 ° C.) and is a liquid.
  • a halogen element-containing hydrocarbon is preferred because of its good polymer solubility.
  • More preferred hydrophobic solvents include methylene chloride, chloroform, dichloroethane, tetrachloroethane, trichloroethane, dibromomethane, bromoform and the like, with methylene chloride being particularly preferred.
  • the medium is an organic substance that has a boiling point of 200 ° C or less at normal pressure and is a liquid at normal temperature (for example, 27 ° C).
  • dissolvable means that a solution containing 1% by weight of a polymer is stably present at room temperature (for example, 27 ° C) without precipitation.
  • the polymer that can be dissolved in the hydrophobic solvent include polylactic acid, polylactic acid-polyglycolic acid copolymer, aliphatic polyesters such as polycaprolactone, polycarbonate, polystyrene, polyarylate, polymethyl methacrylate, and polyethyl.
  • Examples include methacrylate, cellulose diacetate, cellulose triacetate, polyvinyl acetate, polyvinyl methyl ether, poly (N-vinylpyrrolidone) ', polybutylene succinate, polyethylene succinate, and copolymers thereof. .
  • polylactic acid polyprolactone
  • polycarbonate polystyrene
  • polyarylate polyarylate
  • the porous fiber and the fibrous structure of the present invention may contain only one kind of polymer soluble in the hydrophobic solvent, or may contain two or more kinds thereof.
  • the porous fiber and fiber structure of the present invention contain an organic compound having a plurality of hydroxyl groups.
  • a target porous fiber cannot be obtained, a fibrous structure composed of the porous fiber cannot be obtained stably, and cell culture becomes difficult. This may not be desirable.
  • the number average molecular weight of the organic compound having a hydroxyl group is preferably 62 or more and 300 or less. When the number average molecular weight is larger than 300, it is difficult or not preferable to form a porous fiber.
  • Examples of the organic compound having a molecular weight of 62 and having a plurality of hydroxyl groups include: One example is ethylene glycol, but there is substantially no organic compound having a molecular weight of less than 62 and a plurality of hydroxyl groups. The more preferable number average molecular weight of the organic compound is 62 or more and 250 or less.
  • Examples of such an organic compound having a plurality of hydroxyl groups include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, triethylene glycol, glycerin, and Penri Erysuri! Water, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block polymer and the like.
  • a polymer soluble in a hydrophobic solvent and another polymer other than an organic compound having a plurality of hydroxyl groups or other compounds are used in combination (for example, polymer copolymerization, polymer blending, (Mixture of compounds).
  • the porous fiber and the fiber structure of the present invention are formed from porous fibers having an average fiber diameter of 0.1 to 20 Xm. If the average fiber diameter is less than 0.1 m, it is not preferable for use as a cell culture substrate for regenerative medicine because the biodegradability is too fast. On the other hand, if the average fiber diameter is larger than 20 m, the area to which cells can adhere is small, which is not preferable. A more preferable average fiber diameter is 0.2 to 15 m, and a particularly preferable average fiber diameter is 0.2 to 10 m.
  • the fiber diameter indicates the diameter of the fiber when the fiber cross section is circular. However, sometimes the cross section of the fiber may be elliptical.
  • the fiber diameter is calculated as an average of the length of the elliptical major axis direction and the minor axis direction.
  • the fiber diameter is calculated by approximating a circle or an ellipse.
  • the porous fiber of the present invention preferably has a fiber length of 20 im or more. More preferably, if the fiber length is less than 20 zx m, the mechanical strength of the resulting fiber structure will be insufficient.
  • the fiber length is preferably 40 m or more, more preferably 1 mm or more.
  • the porous fiber in the present invention refers to a fiber having an independent hole and a Z or a communication hole on the fiber surface and inside the fiber, wherein the independent hole or communication hole inside the fiber forms a hollow portion,
  • the fibers may be hollow fibers as a whole.
  • the fibrous structure of the present invention comprises a porous fiber having a porosity of at least 5%.
  • the porosity refers to the independent holes and communication holes reaching the fiber surface and the independent holes and communication holes inside the fiber in the fiber cross section cut at random, ie, the fiber-forming substance (hydrophobic solvent soluble).
  • the total area of the fiber-free space that does not contain any polymer, organic compound having multiple hydroxyl groups, and other necessary polymers and other compounds) is at least 5% of the total area of the fiber cross-section including those spaces. Means occupied. If the porosity is less than 5%, a solution containing nutrients or the like during cell culture does not sufficiently penetrate into the inside of the substrate, which is not preferable.
  • the porosity is preferably 10% or more.
  • a preferred embodiment of the present invention comprises a polymer soluble in a hydrophobic solvent and an organic compound having a plurality of hydroxyl groups, has an average fiber diameter of 0.1 to 20 ⁇ , and has a porosity of at least 5%. It is a porous fiber and a fibrous structure composed of the same. It is preferable to use aliphatic polyester, polycarbonate, polystyrene, or polyallylate as a polymer that can be dissolved in a hydrophobic solvent.
  • the method for producing the fiber structure of the present invention is not particularly limited as long as it is a method capable of obtaining fibers having the above-mentioned fiber diameter, but an electrostatic spinning method is preferable.
  • an electrostatic spinning method is preferable.
  • the method of manufacturing by the electrostatic spinning method will be described in detail.
  • a solution in which a polymer soluble in a hydrophobic solvent and an organic compound having a plurality of hydroxyl groups are dissolved in the hydrophobic solvent is discharged into an electrostatic field formed between the electrodes, and the solution is discharged.
  • the fiber structure can be obtained by spinning toward the electrode and accumulating the formed fibrous substance on the collecting substrate.
  • the fibrous substance is accumulated, the porous fibers of the present invention have already been formed.
  • the term “fibrous substance” refers to not only a state in which the solvent in the solution has already been distilled off to form a porous fiber and a fibrous structure, but also a state in which the solvent of the solution is still contained.
  • the electrode used in the present invention may be any metal, inorganic substance, or organic substance as long as it exhibits conductivity. Further, a thin film of a conductive metal, inorganic substance, or organic substance may be provided over an insulator.
  • the electrostatic field in the present invention is formed between a pair or a plurality of electrodes, and a high voltage may be applied to any of the electrodes. This includes, for example, two high-voltage electrodes with different voltage values (for example, 15 kV and 10 kV) and three electrodes connected to the ground, or more than three electrodes. This includes the case where a number of electrodes are used.
  • the concentration of the polymer soluble in the hydrophobic solvent in the solution in the production method of the present invention is preferably 1 to 30% by weight. If the concentration of the polymer soluble in the hydrophobic solvent is less than 1% by weight, it is difficult to form a fiber structure because the concentration is too low. Also, if it is more than 30% by weight, The fiber diameter of the fiber structure becomes large, which is not preferable. A more preferred concentration of the polymer soluble in the hydrophobic solvent is 2 to 20% by weight.
  • the concentration of the organic compound having a plurality of hydroxyl groups in the solution in the present invention is preferably 2 to 50% by weight. If the concentration of the organic compound having a plurality of hydroxyl groups is less than 2% by weight, the total area of the recesses and voids in the fiber cross section is undesirably small. On the other hand, if it is more than 50% by weight, it is difficult to form a fiber structure, which is not preferable. A more preferred concentration of the organic compound having a plurality of hydroxyl groups is 4 to 30% by weight.
  • the organic compound may partially evaporate together with the solvent during spinning by the electrostatic spinning method.
  • a more preferred content is 5 to 60% by weight, and a still more preferred content is 10 to 60% by weight.
  • the hydrophobic solvent may be used alone, or a plurality of hydrophobic solvents may be combined. Further, other solvents may be used in combination as long as the object of the present invention is not impaired. Specific examples of the hydrophobic solvent are as described above.
  • an appropriate device By supplying the solution (2 in Fig. 1) to the nozzle, the solution is placed at an appropriate position in the electrostatic field, and the solution is drawn from the nozzle by an electric field to fibrillate.
  • an appropriate device can be used.
  • an appropriate means such as a high-voltage device is provided at the tip of the cylindrical solution holding tank (3 in FIG. 1) of the syringe.
  • An injection needle-shaped solution ejection nozzle (in Fig. 1;) with a voltage applied by the generator (6 in Fig. 1) is installed, and the solution is guided to its tip.
  • the tip of the jet nozzle (1 in Fig. 1) is placed at an appropriate distance from the grounded fibrous substance collection electrode (5 in Fig. 1), and the solution (2 in Fig. 1) is discharged from the jet nozzle (2 in Fig. 1). When leaving the tip of 1), a fibrous substance is formed between this tip and the fibrous substance collecting electrode (5 in Fig. 1).
  • fine droplets of the solution can be introduced into an electrostatic field by a method obvious to those skilled in the art, and a preferred embodiment thereof will be described below with reference to FIG.
  • the droplet be placed in an electrostatic field and held away from the fibrous material collection electrode (5 in Figure 2) such that fibrillation can occur.
  • the production rate of the fibrous substance can be increased by using several nozzles.
  • the distance between the electrodes depends on the charge amount, the nozzle size, the spinning solution flow rate, the spinning solution concentration, etc., but when the voltage is about 10 kV, a distance of 5 to 20 cm was appropriate.
  • the applied electrostatic potential is generally 3 to 100 kV, preferably 5 to 50 kV, more preferably 5 to 30 kV.
  • the desired electrostatic potential may be created by any appropriate method among conventionally known techniques.
  • the electrode also serves as the collecting substrate.
  • a collecting substrate may be further provided between the electrodes, and the fiber structure may be collected there.
  • a fibrous structure can be produced continuously by installing a belt-like substance between the electrodes and using this as a collecting substrate.
  • the step of obtaining the fiber structure accumulated on the collecting substrate will be described.
  • the solvent evaporates according to the conditions to form a fibrous substance.
  • the porous fibers of the present invention are formed at the latest at the time of collection on the collection substrate.
  • the spinning temperature depends on the evaporation behavior of the solvent and the viscosity of the spinning solution, but is usually 0 to 50 ° C. Then, the porous fibers are further accumulated on the collecting substrate to produce the fiber structure of the present invention.
  • a preferred embodiment of the production method of the present invention includes a step of producing a solution in which a polymer soluble in a hydrophobic solvent and an organic compound having a plurality of hydroxyl groups are dissolved in a hydrophobic solvent, and the step of electrospinning the solution. And a step of obtaining a fibrous structure accumulated on the collecting substrate, wherein the fiber has an average fiber diameter of 0.1 to 20 m and a porosity of at least 5%.
  • a polymer that can be dissolved in the hydrophobic solvent aliphatic polyester, polycarbonate, polystyrene, or polyarylate is a preferred embodiment of the present invention, and a volatile solvent is used as the water-phobic solvent. preferable.
  • the fibrous structure obtained by the present invention may be used alone, or may be used in combination with other members according to handleability and other requirements.
  • a nonwoven fabric, a woven fabric, a film, or the like that can be a supporting base material is used as a collecting substrate, and a fiber structure is formed thereon to create a member combining the supporting base material and the fiber structure. You can do it.
  • the use of the fiber structure obtained by the present invention is not limited to the cell culture substrate for regenerative medicine, but is a feature of the present invention, such as various filters and catalyst-supporting substrates, such as recesses and pores. Can be used for various applications where come.
  • Example 1 the use of the fiber structure obtained by the present invention is not limited to the cell culture substrate for regenerative medicine, but is a feature of the present invention, such as various filters and catalyst-supporting substrates, such as recesses and pores. Can be used for various applications where come.
  • a scanning electron micrograph of the cross section of the obtained porous fiber or fiber in the fiber structure was taken (100,000 magnification).
  • S-240 scanning electron microscope
  • the surface of the obtained fiber structure was photographed (magnification: 800,000 times) with a scanning electron microscope (“S-240” manufactured by Hitachi, Ltd.), and a photograph obtained was observed. It was checked whether fibers less than 0 m were present.
  • the solution was discharged to the fibrous substance collecting electrode for 5 minutes using the apparatus shown in FIG.
  • the inner diameter of the ejection nozzle was 0.8 mm, the voltage was 12 kV, and the distance from the ejection nozzle to the fibrous material collecting electrode was 10 cm.
  • the obtained fiber structure was measured with a scanning electron microscope (“S-2400” manufactured by Hitachi, Ltd.), the average fiber diameter was 3 m, and fibers having a fiber diameter of 20 / m or more were observed. Did not. In addition, fibers with a fiber length of less than 20 xm were not observed.
  • FIGS. 3 and 4 show scanning electron microscope photographs of the surface of the fiber structure and the cross section of the fiber.
  • Example 2 The same operation as in Example 1 was carried out except that 1 part by weight of diethylene dalicol (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ethylene dalicol.
  • the average fiber diameter was 4 / m, and fibers with a fiber diameter of 20 m or more were not observed. Also, fibers with a fiber length of less than 20 / m were not observed. 2004/001453
  • FIGS. 5 and 6 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber.
  • FIGS. 7 and 8 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber.
  • Example 5 The same operation was performed as in Example 1, except that 1 part by weight of polyethylene daricol (average molecular weight: 200, manufactured by Wako Pure Chemical Industries, Ltd., reagent class 1) was used instead of ethylene glycol.
  • the average fiber diameter was 2 m, and fibers with a fiber diameter of 20 or more were not observed. Also, fibers with a fiber length of less than 20 xm were not observed.
  • the porosity was about 15%, and the polyethylene glycol content in the fiber structure was 50.0% by weight.
  • FIGS. 9 and 10 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber.
  • Example 5 ' The average fiber diameter was 2 m, and fibers with a fiber diameter of 20 or more were not observed. Also, fibers with a fiber length of less than 20 xm were not observed.
  • the porosity was about 15%, and the polyethylene glycol content in the fiber structure was 50.0% by weight.
  • FIGS. 9 and 10 show scanning electron micrograph
  • FIGS. 11 and 12 show scanning electron microscope photographs of the surface of the fiber structure and the cross section of the fiber.
  • Example 6 (1,2-propanediol) (Wako Pure Chemical Industries, Ltd., reagent grade) The same operation was performed except that 1 part by weight was used. The average fiber diameter was 4 m, and fibers with a fiber diameter of 20 m or more were not observed. Further, fibers having a fiber length of less than 20 xm were not observed. The porosity was about 15%, and the content of 1,2-propanediol in the fibrous structure was 15.3% by weight.
  • FIGS. 11 and 12 show scanning electron microscope photographs of the surface of the fiber structure and the cross section of the fiber.
  • Example 6 (1,2-propanediol) (Wako Pure Chemical Industries, Ltd., reagent grade) The same operation was performed except that 1 part by weight was used. The average fiber diameter was 4 m, and fibers with a fiber diameter of 20 m or more were not observed. Further, fibers
  • Example 7 The same operation was performed as in Example 1, except that 1 part by weight of poly-prolactone (average molecular weight of about 70,000 to 100,000, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of polylactic acid.
  • the average fiber diameter was 4 xm, and fibers with a fiber diameter of 20 m or more were not observed. Also, fibers with a fiber length of less than 20 fim were not observed.
  • the porosity was about 15%, and the ethylene glycol content in the fiber structure was 16.7% by weight. Scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber are shown in Figs. Example 7
  • Example 2 The same operation as in Example 1 was performed, except that 1 part by weight of Poly-Riki-Iponate (manufactured by Teijin Chemicals Ltd .: trade name “Pan 1 ite LI 250”) was used in place of polylactic acid. went.
  • the average fiber diameter was 3, and fibers with a fiber diameter of 20 im or more were not observed. Also, fibers with a fiber length of less than 20 m were not observed.
  • the porosity was about 35%, and the ethylene glycol content in the fiber structure was 12.3% by weight.
  • Fiber structure FIGS. 15 and 16 show scanning electron micrographs of the surface of the structure and the cross section of the fiber. '' Example 8
  • Example 9 The same operation was performed as in Example 1, except that 1 part by weight of polystyrene (average molecular weight: 250000, manufactured by Kanto Chemical Co., Ltd.) was used instead of polylactic acid.
  • the average fiber diameter was 6 xm, and fibers with a fiber diameter of 20 / m or more were not observed. No fibers with a fiber length of less than 20 m were observed.
  • the porosity was about 35%, and the ethylene glycol content in the fiber structure was 11.2% by weight.
  • FIGS. 17 and 18 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber.
  • Example 1 The same operation as in Example 1 was performed, except that 1 part by weight of polyarylate (trade name: “U-Polymer U-100”) was used instead of polylactic acid in Example 1.
  • the average fiber diameter was 3 / xm, and fibers with a fiber diameter of 20 / m or more were not observed. Also, fibers with a fiber length of less than 20 zm were not observed.
  • the porosity was about 35%, and the ethylene glycol content in the fibrous structure was 12.5% by weight.
  • FIGS. 19 and 20 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber. Comparative Example 1
  • Example 2 The same operation was performed as in Example 1, except that 9 parts by weight of methylene chloride was used instead of ethylene glycol.
  • the average fiber diameter is 2 / m Yes, fibers with a fiber diameter of 20 / m or more were not observed. Also, fibers with a fiber length of less than 20 m were not observed. No depressions or voids were found in the fiber cross section, and the porosity was 0%.
  • the content of the organic compound having a hydroxyl group in the fibrous structure was 0% by weight.
  • FIGS. 21 and 22 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber. Comparative Example 2
  • Example 2 The same operation was performed as in Example 1, except that 1 part by weight of polyethylene glycol (average molecular weight: 400, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) was used instead of ethylene glycol.
  • the average fiber diameter was 3 x m, and fibers having a fiber diameter of 20 or more were not observed. Also, fibers with a fiber length of less than 20 m were not observed. No depressions or voids were found in the fiber cross section, and the porosity was 0%.
  • the polyethylene glycol content in the fibrous structure was 50.0% by weight.
  • FIGS. 23 and 24 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber. Comparative Example 3,,,,
  • Example 2 The same operation was performed as in Example 1, except that 1 part by weight of polyethylene glycol (average molecular weight: 600, manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) was used instead of ethylene glycol.
  • the average fiber diameter was 3 m, and fibers with a fiber diameter of 20 im or more were not observed. Further, fibers having a fiber length of less than 20 im were not observed. No depressions or voids were found in the fiber cross section, and the porosity was 0%.
  • the content of polyethylene glycol in the fiber structure was 50.0% by weight.
  • FIGS. 25 and 26 show scanning electron micrographs of the surface of the fiber structure and the cross section of the fiber.

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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)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Filtering Materials (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un procédé de production d'une structure fibreuse consistant à préparer une solution contenant un solvant hydrophobe et un polymère soluble dans un solvant hydrophobe ainsi qu'un composé organique renfermant une pluralité de groupes hydroxyle, à soumettre la solution à un filage électrostatique, et à obtenir une structure fibreuse formée par accumulation sur une matière de base en vue d'une capture. Ce procédé permet la production d'une fibre poreuse et d'une structure fibreuse comprenant cette fibre poreuse. Ladite structure peut être utilisée comme substrat pour la culture de cellules en médecine régénérative. Elle présente une grande surface active et un grand interstice et permet une régulation de son degré d'hydrophilie.
PCT/JP2004/001453 2003-02-13 2004-02-12 Fibre poreuse, structure fibreuse poreuse et procede de production correspondant WO2004072336A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE602004026561T DE602004026561D1 (de) 2003-02-13 2004-02-12 Poröse faser, poröses fasergebilde und herstellungsverfahren
EP04710522A EP1600533B1 (fr) 2003-02-13 2004-02-12 Fibre poreuse, structure fibreuse poreuse et procede de production correspondant
KR1020057012732A KR101056982B1 (ko) 2003-02-13 2004-02-12 다공질 섬유, 다공질 섬유 구조체 및 그 제조방법
AT04710522T ATE464408T1 (de) 2003-02-13 2004-02-12 Poröse faser, poröses fasergebilde und herstellungsverfahren
US10/544,112 US20060204750A1 (en) 2003-02-13 2004-02-12 Porous fiber, porous fiber structure and method for production thereof
JP2005504973A JP4361529B2 (ja) 2003-02-13 2004-02-12 多孔質繊維、多孔質繊維構造体およびその製造方法

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JP2003034779 2003-02-13
JP2003-034779 2003-02-13
JP2003094176 2003-03-31
JP2003-094176 2003-03-31

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WO2004072336A1 true WO2004072336A1 (fr) 2004-08-26

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EP (1) EP1600533B1 (fr)
JP (1) JP4361529B2 (fr)
KR (1) KR101056982B1 (fr)
AT (1) ATE464408T1 (fr)
DE (1) DE602004026561D1 (fr)
ES (1) ES2340927T3 (fr)
TW (1) TW200424385A (fr)
WO (1) WO2004072336A1 (fr)

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EP1717309A2 (fr) * 2005-04-25 2006-11-02 Japan Agency for Marine-Earth Science and Technology Biodispositifs et bioréacteurs linéaires et de type membrane
WO2011059102A1 (fr) 2009-11-11 2011-05-19 帝人株式会社 Article à base de fibres moulées
CN102787444A (zh) * 2012-08-18 2012-11-21 东华大学 纳米纤维素/二氧化硅多孔网络结构纤维膜的制备方法
JP2012231743A (ja) * 2011-05-02 2012-11-29 National Institute For Materials Science 短繊維足場材料、短繊維−細胞複合凝集塊作製方法及び短繊維−細胞複合凝集塊
WO2013172472A1 (fr) 2012-05-14 2013-11-21 帝人株式会社 Moulage de feuille et matière hémostatique
WO2019114575A1 (fr) * 2017-12-12 2019-06-20 中国科学院大连化学物理研究所 Matériau d'électrode à structure de fibres et sa préparation

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US7901611B2 (en) * 2007-11-28 2011-03-08 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method for predicting and optimizing system parameters for electrospinning system
US8263029B2 (en) * 2008-08-25 2012-09-11 Kent State University Method for preparing anisotropic particles and devices thereof
CN101805940A (zh) * 2010-03-23 2010-08-18 浙江大学 聚合物静电纺丝纤维及其制备方法和应用
EP2864535B1 (fr) * 2012-06-26 2018-11-14 Cabot Corporation Structures isolantes souples et leurs procédés de fabrication et d'utilisation
WO2014066297A1 (fr) * 2012-10-22 2014-05-01 North Carolina State University Matières fibreuses non tissées
CN107447296B (zh) * 2017-09-29 2019-08-23 上海沙驰服饰有限公司 一种感温感湿纺织纤维及制备方法

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JPS5140476A (fr) * 1974-08-05 1976-04-05 Ici Ltd
JPS5751809A (en) * 1980-09-15 1982-03-26 Freudenberg Carl Anti-static spun fiber comprising high molecular material
JPH03284326A (ja) * 1990-03-29 1991-12-16 Kuraray Co Ltd 多孔性の中空糸膜
WO2002016680A1 (fr) * 2000-08-18 2002-02-28 Creavis Gesellschaft Für Technologie Und Innovation Mbh Fabrication de fibres polymeres a morphologies nanometriques

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1717309A2 (fr) * 2005-04-25 2006-11-02 Japan Agency for Marine-Earth Science and Technology Biodispositifs et bioréacteurs linéaires et de type membrane
EP1717309A3 (fr) * 2005-04-25 2006-11-08 Japan Agency for Marine-Earth Science and Technology Biodispositifs et bioréacteurs linéaires et de type membrane
WO2011059102A1 (fr) 2009-11-11 2011-05-19 帝人株式会社 Article à base de fibres moulées
JP5563590B2 (ja) * 2009-11-11 2014-07-30 帝人株式会社 繊維成形体
JP2012231743A (ja) * 2011-05-02 2012-11-29 National Institute For Materials Science 短繊維足場材料、短繊維−細胞複合凝集塊作製方法及び短繊維−細胞複合凝集塊
WO2013172472A1 (fr) 2012-05-14 2013-11-21 帝人株式会社 Moulage de feuille et matière hémostatique
CN102787444A (zh) * 2012-08-18 2012-11-21 东华大学 纳米纤维素/二氧化硅多孔网络结构纤维膜的制备方法
WO2019114575A1 (fr) * 2017-12-12 2019-06-20 中国科学院大连化学物理研究所 Matériau d'électrode à structure de fibres et sa préparation

Also Published As

Publication number Publication date
EP1600533A1 (fr) 2005-11-30
US20060204750A1 (en) 2006-09-14
TW200424385A (en) 2004-11-16
JP4361529B2 (ja) 2009-11-11
KR101056982B1 (ko) 2011-08-16
ATE464408T1 (de) 2010-04-15
EP1600533B1 (fr) 2010-04-14
JPWO2004072336A1 (ja) 2006-06-01
EP1600533A4 (fr) 2006-10-18
ES2340927T3 (es) 2010-06-11
KR20050098861A (ko) 2005-10-12
DE602004026561D1 (de) 2010-05-27

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