WO2010082603A1 - 無機系繊維構造体及びその製造方法 - Google Patents
無機系繊維構造体及びその製造方法 Download PDFInfo
- Publication number
- WO2010082603A1 WO2010082603A1 PCT/JP2010/050347 JP2010050347W WO2010082603A1 WO 2010082603 A1 WO2010082603 A1 WO 2010082603A1 JP 2010050347 W JP2010050347 W JP 2010050347W WO 2010082603 A1 WO2010082603 A1 WO 2010082603A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- inorganic
- inorganic fiber
- fiber structure
- spinning
- fiber
- Prior art date
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6224—Fibres based on silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62807—Silica or silicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M3/00—Tissue, human, animal or plant cell, or virus culture apparatus
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N5/00—Undifferentiated human, animal or plant cells, e.g. cell lines; Tissues; Cultivation or maintenance thereof; Culture media therefor
- C12N5/0068—General culture methods using substrates
-
- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—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 by electro-spinning
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/441—Alkoxides, e.g. methoxide, tert-butoxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5252—Fibers having a specific pre-form
- C04B2235/5256—Two-dimensional, e.g. woven structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5264—Fibers characterised by the diameter of the fibers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N2533/00—Supports or coatings for cell culture, characterised by material
- C12N2533/10—Mineral substrates
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/762—Nanowire or quantum wire, i.e. axially elongated structure having two dimensions of 100 nm or less
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
Definitions
- the present invention relates to an inorganic fiber structure (particularly a functional inorganic fiber structure) and a method for producing the same.
- the inorganic fiber structure of the present invention can be used, for example, for cell culture carriers, scaffolds, antibacterial materials, and the like.
- Such an electrospinning method is a method of spinning by supplying a spinning stock solution to a spinning space, drawing an applied electric field on the supplied spinning stock solution, and accumulating it on a counter electrode.
- the fibers drawn and spun by the action of the electric field are accumulated on the counter electrode directly by the electric field, so that a paper-like nonwoven fabric is formed.
- it is preferable that it is a bulky nonwoven fabric.
- This bulky nonwoven fabric is a low-density, cotton-like nonwoven fabric in which the fibers are not bonded to each other or bonded extremely weakly, so it can be applied to applications that do not require shape retention and strength. In applications that require shape retention and strength, such as filtration, the nonwoven fabric form could not be maintained and was not suitable for practical use.
- the method (1) it is extremely difficult to make a nanofiber by an electrostatic spinning method.
- the method (2) is inferior in strength because it is difficult to uniformly apply the binder to the entire inorganic fiber nonwoven fabric (particularly up to the inside of the nonwoven fabric).
- the method (3) the voids of the inorganic fiber nonwoven fabric are crushed, the bulkiness cannot be maintained, and the porosity is lowered.
- the fiber structure including such an inorganic fiber nonwoven fabric can be applied to a culture carrier.
- a culture carrier In order to culture cells in a state close to the environment in the living body, there is a tissue formation induction technique by three-dimensional culture of cells.
- this culture carrier films, particles, hollow fibers, fiber assemblies, foams and the like are known.
- these culture carriers have insufficient surface area to serve as a scaffold for cells necessary for three-dimensional culture, so that high-density culture of cells is difficult and cell tissue-forming ability similar to the in vivo environment is possessed. Often not.
- a scaffold containing nanofibers produced by an electrospinning method As a culture carrier capable of solving such problems of conventional culture carriers and capable of three-dimensional culture, “a scaffold containing nanofibers produced by an electrospinning method” has been proposed (Patent Document 3).
- nanofibers made of silica and PVA are used.
- a scaffold containing such nanofibers has low cell proliferation ability, is difficult to perform high-density culture, and is difficult to express cell functions.
- a metal ion-containing compound is imparted to impart a function to the fiber structure.
- a function for example, it is involved in a wide range of biological reactions such as cell division / proliferation / differentiation, blood coagulation, muscle contraction, neurosensory cell excitement, phagocytosis, antigen recognition, antibody secretion, and various hormone secretions.
- calcium that forms hydroxyapatite crystals and deposits on the matrix structure of bones and teeth to give strength
- sodium that works to maintain the osmotic pressure of extracellular fluid, oxygen transport, and electron transporter (cytochrome C) in energy metabolism
- Iron which is an essential component of bone
- magnesium which is the main inorganic component of bones and teeth
- potassium that maintains nerve excitability, muscle contraction, and intracellular osmotic pressure, or copper, iodine, selenium, chromium
- a cell culture substrate capable of improving cell function by applying a metal such as zinc or molybdenum to the fiber structure, or It can be used as a fiber structure having a bacterial performance.
- Patent Document 3 proposes “a scaffold comprising nanofibers surface-modified with a cell adhesion factor (particularly calcium phosphate) produced by an electrospinning method” (claims 1, 8, and 9).
- the silica nanofibers synthesized by the sol-gel method are suitable, the silica nanofibers can be made hydrophilic or hydrophobic depending on the firing temperature of the silica nanofibers, the cell adhesion rate can be manipulated, and the silica nanofibers are incubated in artificial body fluids
- phosphorous lime can be deposited on the surface of the nanofiber and is useful as a cell carrier for artificial bone (paragraph numbers 0015, 0018, 0025, etc.).
- scaffolds containing such nanofibers have low cellular functions.
- the object of the present invention is to solve these problems of the prior art, and to provide a bulky inorganic fiber structure that can be used for applications that require shape retention and strength.
- Inorganic fiber structures that can perform high-density culture, easily develop cell functions, control fiber density and thickness, and easily observe the culture state, have high cell functions, and antibacterial properties
- An object of the present invention is to provide an inorganic fiber structure excellent in functionality, such as excellent, and a method for producing the same.
- the present invention (1) An inorganic fiber structure composed of inorganic nanofibers having an average fiber diameter of 3 ⁇ m or less, the whole including the inside being bonded with an inorganic adhesive, and an inorganic fiber structure having a porosity of 90% or more; (2) The inorganic fiber structure according to (1), which has a tensile strength at break of 0.2 MPa or more; (3) The inorganic fiber structure according to (1) or (2), wherein the amount of hydroxyl group per unit weight of fiber is 50 ⁇ mol / g or more; (4) An inorganic fiber assembly produced by irradiating and accumulating ions having a polarity opposite to that of the inorganic fiber to the inorganic fiber spun by the electrostatic spinning method.
- a method for producing an inorganic fiber structure comprising: (9) (ii) The method for producing an inorganic fiber structure according to (8), wherein in the step of forming the inorganic fiber aggregate, heat treatment is performed after the inorganic fiber aggregate is formed; (10) The method for producing an inorganic fiber structure according to (9), wherein the heat treatment temperature is 500 ° C. or lower; (11) (iii) The method for producing an inorganic fiber structure according to any one of (8) to (10), wherein in the step of forming the inorganic fiber structure, the excess inorganic sol solution for bonding is removed by aeration and then heat treatment is performed.
- the inorganic fiber structure of the present invention (1) is excellent in shape retention and has sufficient strength because the entire structure including the inside is bonded with an inorganic adhesive. In particular, even in a liquid, it has excellent shape retention and sufficient strength.
- the porosity of the inorganic fiber structure is 90% or more, it is preferably used for bulky applications such as heat insulation applications, filtration applications, culture carrier applications such as cells, scaffold applications, and antibacterial material applications. Can be applied.
- the tensile strength at break is 0.2 MPa or more, it has excellent shape retention and sufficient strength.
- the amount of hydroxyl groups per unit weight of fiber is 50 ⁇ mol / g or more, apatite and the like can be precipitated on the fiber surface, and the inorganic fiber structure Functions can be added.
- fibers spun by an electrospinning method are used, and since the fiber diameter is small, the surface area is large. Furthermore, since the pore size distribution is uniform, a uniform space exists inside the inorganic fiber structure. As a result, the function can be sufficiently exhibited. For example, when used as a culture carrier, since the surface area serving as a scaffold for cells is large, three-dimensional culture in a uniform space having a large surface area is possible. In addition, the efficiency of adhesion between the cells and the fibers that serve as the scaffolds for the cells is improved, and the supply efficiency of nutrients and oxygen essential to the cells is improved.
- irradiation with ions having the opposite polarity to the inorganic fiber is performed and accumulated to form an inorganic fiber aggregate, that is, a result of a high porosity (bulk) of 90% or more derived from the neutral spinning method.
- the fiber density is low, the inside of the inorganic fiber structure can be used effectively. For example, when used as a culture substrate, since the fiber density is low, there is an effect that the cells easily spread to the inside of the culture carrier.
- ions having the opposite polarity to the inorganic fiber are irradiated and accumulated to form an inorganic fiber aggregate, the fiber density is increased and the fiber density and thickness until observable can be controlled.
- the ions having the opposite polarity to the fibers are irradiated and accumulated, a high porosity of 90% or more is obtained. Furthermore, since it is an inorganic fiber assembly, the thickness is not crushed when an inorganic adhesive is applied. As a result, the fiber density and thickness can be controlled. Therefore, when used as a culture substrate, it is easy to observe the culture state. Furthermore, since it adhere
- the cells When used as a culture substrate, the cells can be cultured in three dimensions, and the cells are cultured in a state close to the tissue environment, so that cell functions are easily expressed. Furthermore, since the inorganic fiber structure is bonded with an inorganic adhesive throughout the whole including the inside, it is possible to maintain a porosity of 90% or more. For example, when used as a culture carrier, it is possible to improve the supply efficiency of nutrients and oxygen indispensable for cells, and because there are many scaffolds necessary for cell culture, high-density culture can be performed.
- the inorganic fiber structure is bonded with an inorganic adhesive without forming a film between the inorganic fibers in the whole including the inside. Therefore, it is possible to maintain a porosity of 90% or more.
- a culture carrier when used as a culture carrier, it is possible to improve the supply efficiency of nutrients and oxygen indispensable for cells, and because there are many scaffolds necessary for cell culture, high-density culture can be performed.
- the metal ion-containing compound since the metal ion-containing compound is provided and contained, it has excellent functionality such as high cell function and excellent antibacterial properties.
- the average fiber diameter is as small as 3 ⁇ m or less, so the surface area is wide.
- the adhesion efficiency between the cells and the fibers that serve as a scaffold for the cells is improved, and the supply efficiency of nutrients and oxygen essential to the cells is improved.
- attaches with the inorganic type adhesive agent a form can be maintained also in a culture solution.
- the bulky structure of the inorganic fiber structure can be maintained, it can be cultured in three dimensions, and the cells are cultured in a state close to the tissue environment, so that cell functions are easily expressed.
- the inorganic fiber structure of the present invention can be produced.
- the excess inorganic sol solution for bonding is removed by ventilation, the entire state including the inside is bonded with an inorganic adhesive without forming a film between inorganic fibers.
- An inorganic fiber structure having excellent shape retention and strength can be produced while maintaining the same.
- the structure and heat resistance of the inorganic fiber structure are used because (ii) in the step of forming the inorganic fiber aggregate, heat treatment is performed after the inorganic fiber aggregate is formed. Sex is stable.
- the heat treatment temperature is 500 ° C. or lower, the hydrophilicity of the inorganic fiber structure can be increased.
- the inorganic sol solution for surplus adhesion is removed by aeration and then heat-treated, The strength and heat resistance of the fiber structure are improved.
- the heat treatment temperature is 500 ° C. or lower, the hydrophilicity of the inorganic fiber structure can be increased.
- the spinning inorganic sol solution and / or the bonding inorganic sol solution contains a metal ion-containing compound, It is possible to produce an inorganic fiber structure having excellent functionality such as containing, high cell function, and excellent antibacterial properties.
- the metal ion-containing compound-containing solution is imparted to the inorganic fiber structure, the antibacterial containing the metal ion-containing compound and having high cell function. It is possible to produce an inorganic fiber structure having excellent functionality, such as excellent properties.
- FIG. 10 is a graph showing changes in the number of cells per unit dish of CHO-K1 cells up to 14 days of culture in each culture carrier shown in FIG.
- FIG. 6 is a graph showing changes in the number of cells per unit dish of HepG2 cells up to 14 days in culture in the culture carrier A of the present invention prepared in Example 10 and the comparative culture carriers a to c prepared in Comparative Examples 8 to 10.
- FIG. is there. It is a graph which shows the result of having measured the ammonia removal ability (ammonia concentration change per unit dish) in the culture medium which the HepG2 cell brings up to 14 days of culture
- FIG. 6 is a graph showing changes in the number of cells of the inorganic fiber structures of Examples 11 to 13, which are preferred embodiments of the present invention, and human osteosarcoma MG63 cells cultured for 21 days on each sample of Examples 14 to 15 of the present invention. is there.
- FIG. 15 is a graph showing the time course of enzyme activity (unit: ABS / 10 3 cells) per unit cell of alkaline phosphatase (ALP) secreted by human osteosarcoma MG63 cells in the culture shown in FIG.
- ALP alkaline phosphatase
- the production method of the present invention comprises: (1) A step of spinning inorganic fibers by an electrospinning method from an inorganic sol solution for spinning containing a compound mainly composed of inorganic components (spinning step); (2) Irradiating ions having the opposite polarity to the inorganic fibers and stacking them to form an inorganic fiber aggregate (stacking step); (3) An adhesive inorganic sol solution containing a compound mainly composed of an inorganic component is applied to the entire structure including the inside of the inorganic fiber aggregate, and the excess inorganic sol solution for bonding is removed by aeration.
- the process of forming an inorganic fiber structure bonded with an inorganic adhesive in the whole including (adhesion process) Including, if desired, (4)
- a step of applying a metal ion-containing compound-containing solution to the inorganic fiber structure and imparting functionality to the inorganic fiber structure can further be included.
- an inorganic sol solution for spinning used in the spinning step (1) instead of the metal ion-containing compound-containing solution application step (4), or in addition to the step (4), an inorganic sol solution for spinning used in the spinning step (1), and Alternatively, a metal ion-containing compound can be added to the bonding inorganic sol solution used in the bonding step (3).
- FIG. 1 is an explanatory view schematically showing one aspect of an electrostatic spinning apparatus capable of performing the spinning step (1) and the accumulating step (2) in the production method of the present invention.
- an electrostatic spinning device 1 is disposed below a spinning nozzle 2 that discharges an inorganic sol solution for spinning containing a compound mainly composed of an inorganic component, which is a raw material of a fiber, and a lower end of the spinning nozzle 2.
- a collection member for example, a net, a conveyor, etc.
- a fiber collection container 3 which is a fiber collection device.
- the counter electrode 5 is disposed opposite to the spinning nozzle 2 and is an ion generating means for generating ions having a polarity opposite to that of the fibers formed by being discharged, and is provided with a counter electrode 5 that can electrically attract the fibers.
- the spinning nozzle 2 is connected to a sol solution supply device 6 for supplying an inorganic sol solution for spinning.
- the spinning nozzle 2 and the counter electrode 5 are respectively provided with a first high voltage power source 7 and a second high voltage power source 8. It is connected.
- the fiber collection container 3 is provided with a suction machine 9 for sucking fibers into the fiber collection container 3.
- a metal / nonmetal pipe having an inner diameter of about 0.01 to 5 mm can be used as the spinning nozzle 2.
- a rotating saw-tooth gear 20 is immersed in a sol solution container 22 containing an inorganic sol solution 21 for spinning, and the tip 20a of the saw-tooth gear 20 toward the counter electrode 5 is connected to the electrode.
- the wire 20 b is rotated in the sol solution container 22 by a roller 23, and the conveyor-like wire 20 b to which the spinning inorganic sol solution 21 is attached can be used as an electrode.
- the counter electrode (not shown) is arranged perpendicular to the paper surface. Further, various conventional electrospinning electrodes can be used.
- a corona discharge needle (which may be applied with high voltage or ground), a corona discharge wire (which may be applied with high voltage or ground), an AC discharge element, or the like can be used.
- a creeping discharge element as shown in FIG. 4 can be used as the AC discharge element. That is, in FIG. 4, the creeping discharge element 25 is provided with a discharge electrode 27 and an induction electrode 28 with a dielectric substrate 26 (for example, an alumina film) interposed therebetween, and an alternating high voltage is applied between these electrodes, thereby Creeping discharge is generated at the electrode 27 portion, and positive and negative ions can be generated.
- a step of forming an inorganic sol solution for spinning containing a compound mainly composed of inorganic components is performed.
- "mainly composed of inorganic components” means that the inorganic components occupy 50 mass% or more, more preferably 60 mass% or more, and 75 mass% or more. Is more preferable.
- This spinning-based inorganic sol solution hydrolyzes a solution (raw material solution) containing a compound containing an element constituting the inorganic fiber finally obtained by the production method of the present invention at a temperature of about 100 ° C. or less, It can be obtained by condensation polymerization.
- the solvent of the raw material solution is, for example, an organic solvent (for example, alcohol) or water.
- the elements constituting this compound are not particularly limited.
- Examples of the compound include oxides of the above elements, and specifically include SiO 2 , Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , CeO 2 , FeO, and Fe 3 O. 4, Fe 2 O 3, VO 2, V 2 O 5, SnO 2, CdO, LiO 2, WO 3, Nb 2 O 5, Ta 2 O 5, In 2 O 3, GeO 2, PbTi 4 O 9, LiNbO 3 , BaTiO 3 , PbZrO 3 , KTaO 3 , Li 2 B 4 O 7 , NiFe 2 O 4 , SrTiO 3 and the like.
- the inorganic component may be composed of one component oxide or may be composed of two or more component oxides. For example, it can be composed of two components of SiO 2 —Al 2 O 3 .
- the above-mentioned inorganic sol solution for spinning needs to have a viscosity that enables spinning in the step of forming fibers to be described later.
- the viscosity is not particularly limited as long as it is a spinnable viscosity, but is preferably 0.1 to 100 poise, more preferably 0.5 to 20 poise, particularly preferably 1 to 10 poise, and most preferably 1 to 5 poise. This is because when the viscosity exceeds 100 poise, it is difficult to make fine fibers, and when the viscosity is less than 0.1 poise, the fiber shape tends to be not obtained.
- a nozzle if the atmosphere at the nozzle tip is the same solvent gas atmosphere as the raw material solution, spinning may be possible even with an inorganic sol solution for spinning exceeding 100 poise. .
- the spinning inorganic sol solution used in the spinning step (1) can contain an organic component in addition to the inorganic component as described above.
- the organic component include organic materials such as silane coupling agents and dyes. Examples thereof include low molecular compounds and organic polymer compounds such as polymethyl methacrylate. More specifically, when the compound contained in the raw material solution is a silane compound, it may contain a polycondensation of a silane compound organically modified with a methyl group or an epoxy group.
- the raw material solution is used to hydrolyze the compound contained in the raw material solution, for example, a solvent that stabilizes the compound contained in the raw material solution (for example, an organic solvent (for example, alcohol such as ethanol, dimethylformamide) or water). And a catalyst (for example, hydrochloric acid, nitric acid, etc.) that smoothly proceeds the hydrolysis reaction.
- the raw material solution is, for example, a chelating agent that stabilizes the compound, a silane coupling agent for stabilizing the compound, a compound that can impart various functions such as piezoelectricity, an improvement in adhesion, and flexibility.
- an organic compound for example, polymethyl methacrylate
- fragmentility fragmentation-renesulfate
- an additive such as a dye
- the raw material solution may contain inorganic or organic fine particles.
- the inorganic fine particles include titanium oxide, manganese dioxide, copper oxide, silicon dioxide, activated carbon, and metal (for example, platinum), and examples of the organic fine particles include dyes and pigments.
- the average particle size of the fine particles is not particularly limited, but is preferably 0.001 to 1 ⁇ m, more preferably 0.002 to 0.1 ⁇ m. By including such fine particles, an optical function, porosity, catalytic function, adsorption function, ion exchange function, or the like can be provided.
- the said raw material solution can also contain the metal ion containing compound explained in full detail at a metal ion containing compound containing solution provision process (4), and can also contain it.
- the reaction temperature may be equal to or lower than the boiling point of the solvent used, but the lower the reaction rate, the moderately slow the reaction rate and the easier to form a spinnable sol solution. Since it is difficult for the reaction to proceed even if it is too low, it is preferably 10 ° C. or higher.
- the process of forming an inorganic fiber aggregate by the electrostatic spinning device 1 as described above is performed as follows. First, an inorganic sol solution for spinning, which is a raw material of the fiber to be spun, is supplied from the sol solution supply machine 6 to the spinning nozzle 2. Next, in a state where a high voltage is applied between the spinning nozzle 2 and the counter electrode 5, the spinning inorganic sol solution is discharged from the tip of the spinning nozzle 2. Then, the solvent of the charged liquid sol solution is volatilized and solidifies to become a gel-like inorganic fiber and proceeds toward the counter electrode 5 [the spinning step (1)].
- ions 5 a are irradiated toward the fiber from the counter electrode 5 disposed facing the spinning nozzle 2. This ion neutralizes the charging of the fiber, loses the flying force due to the electrostatic force, falls according to gravity, or is recovered in the fiber recovery container 3 by the breeze. Accordingly, it is possible to obtain a low-density and cotton-like inorganic fiber aggregate [collecting step (2)].
- the generation and irradiation of ions can be performed continuously or discontinuously. Further, an electric field may be generated between the spinning nozzle 2 and the counter electrode 5, and a high voltage may be applied to only one of them and the other may be grounded. Further, the spinning nozzle 2 may be heated or not heated.
- FIG. 5 is an explanatory view schematically showing another aspect of the electrostatic spinning apparatus capable of performing the spinning step (1) and the accumulating step (2) in the production method of the present invention.
- the electrostatic spinning device 1 ⁇ / b> A can generate ions in the first embodiment, and can replace the counter electrode 5 that can suck fibers, and an ionizing radiation source 10 that can irradiate ionizing radiation, and a net-like shape that can suck fibers.
- the configuration is the same as that of the electrostatic spinning device 1 except that the counter electrode 5 (connected to the third high-voltage power supply 11) is used, and redundant description is omitted.
- a predetermined voltage is applied to the spinning nozzle 2 and / or the counter electrode 5 by the first high voltage power source 7 and / or the third high voltage power source 11, so that the spinning nozzle 2 and the counter electrode 5 A potential difference is generated between them, and the fibers are electrically attracted and fly toward the counter electrode 5 [the spinning step (1)].
- the flying fiber is irradiated with ionizing radiation 10a, ionizes the gas, and acts as an ion source. As a result, the charging of the fibers is neutralized, the flying force due to the electrostatic force is lost, and the fibers are recovered in the fiber recovery container 3 by dropping according to the gravity or by the breeze.
- the dose can be adjusted independently of the formation of a potential difference between the spinning nozzle 2 and the counter electrode 5, so that an inorganic fiber assembly can be obtained stably. It is.
- various radiation sources can be used as the ionizing radiation source 10, and an X-ray irradiation apparatus is particularly desirable.
- the counter electrode 5 only needs to have a potential difference with the spinning nozzle 2, and may be grounded or a voltage may be applied.
- the ionizing radiation source 10 only needs to be able to irradiate the fibers with radiation, and need not be located behind the counter electrode 5.
- the counter electrode 5 does not need to be net-shaped, and various members can be used as long as ionizing radiation can be transmitted, and even a vapor deposition film can be used.
- FIG. 6 is an explanatory view schematically showing still another aspect of the electrostatic spinning apparatus capable of performing the spinning step (1) and the accumulating step (2) in the production method of the present invention.
- a first spinning nozzle 2a and a second spinning nozzle 2b are arranged to face each other.
- the first spinning nozzle 2a is connected to a first sol solution supply device 6a for supplying an inorganic sol solution for spinning and a first high voltage power source 7 for applying a high voltage, and the second spinning nozzle 2b is used for spinning.
- a second sol solution supply unit 6b that supplies an inorganic sol solution and a second high voltage power source 8 that applies a high voltage having a polarity opposite to that of the first high voltage power source 7 are connected to each other.
- the rest of the configuration is the same as that of the electrostatic spinning device 1, and a duplicate description is omitted.
- the first spinning nozzle 2a and the second spinning voltage 2 are applied to the first spinning nozzle 2a and the second spinning nozzle 2b by applying voltages having opposite polarities to the first spinning nozzle 2a and the second spinning nozzle 2b, respectively.
- An inorganic sol solution for spinning is discharged from the second spinning nozzle 2b [spinning step (1)]. Then, the fibers charged to opposite polarities are contacted and approached by being discharged oppositely, the charge is neutralized, the flying force due to the electrostatic force is lost, the fibers are dropped according to gravity, or the fibers are recovered by the wind. Collected in container 3. Accordingly, it is possible to obtain a low-density, cotton-like inorganic fiber aggregate [collecting step (2)].
- the fiber diameters are different, the composition of the fiber constituent materials is different, etc.
- An inorganic fiber assembly in which different types of inorganic fibers are mixed can be manufactured.
- the inorganic sol solution for spinning from the first spinning nozzle 2a and the second spinning nozzle 2b can be discharged continuously or discontinuously. Moreover, an electric field should just generate
- electrostatic spinning device 1A In the above-described electrostatic spinning device 1, electrostatic spinning device 1A, and electrostatic spinning device 1B, one spinning nozzle is used for one spinning nozzle 2, 2a, and 2b. There is no need for one, and two or more spinning nozzles can be provided to increase productivity.
- the suction device 9 is provided below the collecting member 4 so that the air velocity in the spinning space can be 5 to 100 cm / second, preferably 10 to 50 cm / second.
- a blower device can be provided above the collection member 4.
- the inorganic fiber aggregate obtained in the accumulation step (2) can be subjected to the next bonding step (3) on the accumulated inorganic fiber aggregate, or after heat treatment
- the next bonding step (3) can also be performed.
- this heat treatment hereinafter, sometimes referred to as post-integration heat treatment when it is necessary to distinguish from the heat treatment for adhesion described later
- the structure and heat resistance of the inorganic fiber aggregate are stabilized.
- heat processing can be implemented using oven, a sintering furnace, etc., The temperature is suitably set with the inorganic component which comprises an inorganic type fiber assembly.
- the post-accumulation heat treatment temperature is preferably 200 ° C. or higher, and preferably 300 ° C. or higher.
- the post-accumulation heat treatment temperature is 500 ° C. or less
- the hydrophilicity of the inorganic fiber structure can be enhanced.
- the inorganic fiber has a hydroxyl group
- the amount of hydroxyl group per unit weight of the fiber can be increased to 50 ⁇ mol / g or more by performing post-accumulation heat treatment at a temperature of 500 ° C. or lower, so that hydrophilicity is improved. .
- the hydrophobicity can be increased and the adhesion of the cells can be enhanced.
- the cells When used as a culture substrate, the cells are in sheet form. It is easy to culture and, furthermore, the adhesive strength between the inorganic fibers increases, so the strength of the inorganic fiber structure can be increased.
- an inorganic sol solution for bonding containing a compound mainly composed of an inorganic component is applied to the whole including the inside of the inorganic fiber aggregate obtained in the steps so far, for surplus bonding.
- the inorganic sol solution was removed by aeration to form an inorganic fiber assembly containing the inorganic sol solution for bonding (hereinafter, the first half of the bonding step (3) is referred to as the bonding inorganic sol solution applying step).
- the inorganic fiber structure containing the inorganic sol solution for bonding is heat-treated (or naturally dried at room temperature), and the entire structure including the inside is bonded with an inorganic adhesive.
- a body is formed (hereinafter, the latter half of the bonding step (3) may be referred to as a bonding heat treatment step).
- the heat treatment in the bonding heat treatment step may be referred to as bonding heat treatment.
- the raw material (compound) constituting the inorganic sol solution for bonding is the same as the compound containing the elements constituting the inorganic fiber, but is the same as the inorganic sol solution for spinning as long as it penetrates into the inorganic fiber assembly. Or different. For example, it does not need to be spinnable and may not be spinnable.
- grains may be contained.
- a spinning inorganic sol solution may be diluted, and the concentration can be appropriately selected.
- attachment can contain the metal ion containing compound explained in full detail at a metal ion containing compound containing solution provision process (4), and can also contain it.
- the adhesive inorganic sol solution to the inorganic fiber assembly is uniform throughout, that is, the adhesive inorganic sol solution reaches the inside sufficiently, similarly to the outer portion of the inorganic fiber assembly.
- it is not particularly limited.
- it can be carried out by immersing the inorganic fiber aggregate in an inorganic sol solution for bonding.
- the post-accumulation heat treatment of the inorganic fiber aggregate is performed in the accumulation step (2), it is difficult to separate even if the immersion treatment is performed.
- Excess inorganic sol solution for adhesion contained in the inorganic fiber aggregate after immersion is removed by aeration. Since the inorganic fiber assembly is composed of inorganic fibers, even if aeration and / or pressurization allow ventilation, the thickness is not crushed and a film is formed between the entire fibers including the inside. In addition, an inorganic fiber assembly containing an inorganic sol solution for bonding to which an inorganic sol solution for bonding is applied can be obtained.
- the inorganic fiber assembly containing the inorganic sol solution for bonding obtained in the step of applying the inorganic sol solution for bonding is dried, and a film is formed between the inorganic fibers in the whole including the inside. And an inorganic fiber structure bonded with an inorganic adhesive can be produced.
- the heat treatment for bonding is not particularly limited as long as it can volatilize the solvent and the like contained in the inorganic sol solution for bonding, and is carried out, for example, by holding at a temperature of 80 to 150 ° C. for 10 to 30 minutes. can do. In addition, it can also be naturally dried at room temperature.
- the “adhesion heat treatment” in the present specification includes the following firing treatment in addition to the drying by heating and the natural drying at room temperature.
- the bonding inorganic sol solution and / or the inorganic fiber included in the bonding inorganic sol solution-containing inorganic fiber aggregate is optionally added after the bonding heat treatment for volatilizing the solvent and the like.
- a baking treatment can be performed. By carrying out this firing treatment, the strength and heat resistance of the inorganic adhesive bonded to the fiber intersections of the inorganic fiber aggregate are improved. Moreover, the strength and heat resistance of the inorganic fiber are improved.
- the firing treatment can be performed using, for example, a sintering furnace, and the temperature is appropriately set depending on the inorganic components constituting the inorganic adhesive and the inorganic fibers. In general, the firing temperature is preferably 200 ° C.
- the inorganic fiber structure which has the functionality which provided the apatite, it is preferable to implement at the calcination temperature mentioned later.
- the hydrophilicity of an inorganic fiber structure can be improved as this heat processing temperature for adhesion is 500 degrees C or less.
- this heat processing temperature for adhesion is 500 degrees C or less.
- the inorganic fiber has a hydroxyl group
- the amount of hydroxyl group per unit weight of the fiber can be increased to 50 ⁇ mol / g or more by performing the heat treatment for adhesion at a temperature of 500 ° C. or lower, and thus the hydrophilicity is improved. .
- the hydrophobicity can be increased and the adhesion of cells can be increased.
- the cells are in sheet form.
- the adhesive strength between the inorganic fibers can be increased, the strength and heat resistance of the inorganic fiber structure can be increased.
- Such a heat treatment for bonding can be performed using, for example, an oven, a sintering furnace, or the like.
- an inorganic fiber structure having functionality can be formed by applying the metal ion-containing compound-containing solution to the inorganic fiber structure.
- the metal constituting the metal ion-containing compound include calcium, sodium, iron, magnesium, potassium, copper, iodine, selenium, chromium, zinc, and molybdenum. These metals exhibit cell function inducers or antibacterial effects.
- the metal ion-containing compound can be, for example, a metal salt.
- the metal salt include chloride, sulfate, phosphate, carbonate, hydrogen phosphate, hydrogen carbonate, nitrate, hydroxide and the like.
- an inorganic fiber structure having a function to which a calcium ion-containing salt, a magnesium ion-containing salt, or apatite (apatite) is added can perform cell culture with enhanced cell function.
- Examples of the method for applying the metal ion-containing compound include a method of immersing the inorganic fiber structure in the metal ion-containing compound-containing solution, a method of applying or spraying the metal ion-containing compound-containing solution to the inorganic fiber structure, and the like. Can be mentioned.
- the inorganic fiber is silica fiber, it is preferable to apply a metal ion-containing compound at a high concentration by immersing, coating or spraying the metal ion-containing compound, followed by heat treatment (firing treatment).
- the functional inorganic fiber structure to which a calcium ion-containing salt or a magnesium ion-containing salt is added is, for example, a solution in which a calcium salt or a magnesium salt is dissolved in an appropriate solvent (for example, a lower alcohol). Further, it can be obtained by immersing the inorganic fiber structure, or by applying or spraying the solution.
- the inorganic fiber structure which has the functionality which provided the apatite immerses the inorganic fiber (especially silica fiber) containing a hydroxyl group on the surface in the artificial body fluid containing at least phosphate ion and calcium ion.
- apatite can be deposited on the inorganic fiber.
- the inorganic fiber is a silica fiber (particularly when the fiber structure is used for a bone culture substrate)
- the post-accumulation heat treatment can be performed in the accumulation step (2) or can be omitted.
- the inorganic fiber aggregate is preferably heat-treated at a temperature of 500 ° C. or less, more preferably 120 to 300 ° C.
- the amount of hydroxyl groups per unit weight of the fiber can be set to 50 ⁇ mol / g or more, preferably 100 ⁇ mol by not performing the post-accumulation heat treatment or by performing the post-accumulation heat treatment at 500 ° C. or less. / G or more.
- heat treatment for bonding (drying and / or firing) is performed in the same temperature range, and the amount of hydroxyl group per unit weight of fiber is 50 ⁇ mol / g or more ( More preferably, it is preferably 100 ⁇ mol / g or more.
- the inorganic fiber structure of the present invention is an inorganic fiber produced by a process of irradiating and accumulating ions having a polarity opposite to that of the inorganic fiber to the inorganic fiber spun by an electrostatic spinning method.
- An inorganic fiber structure in which the fiber assembly is bonded to the whole including the inside with an inorganic adhesive, and a metal ion-containing compound is provided if desired.
- the inorganic fiber structure of the present invention can be produced, for example, by the production method of the present invention.
- the inorganic fiber in the present invention includes, for example, an inorganic gel fiber, an inorganic dry gel fiber, or an inorganic sintered fiber.
- the inorganic gel fiber is a fiber containing a solvent.
- the inorganic fiber material is tetraethoxysilane (TEOS), ethanol, water, hydrochloric acid, the substance with the highest boiling point is water. Therefore, it is a fiber that has been heat-treated or not heat-treated at a temperature of less than 100 ° C.
- the inorganic dry gel fiber means a state in which the solvent contained in the gel fiber is removed.
- the raw material of the inorganic fiber is tetraethoxysilane (TEOS), ethanol, water, and hydrochloric acid
- TEOS tetraethoxysilane
- the material having the highest boiling point is water, and thus the fiber is heat-treated at a temperature of 100 ° C. or higher.
- the inorganic sintered fiber means a state where the inorganic dry gel fiber (porous) is sintered (nonporous).
- the fiber is heat-treated at 800 ° C. or higher.
- the average fiber diameter of the inorganic nanofiber is 3 ⁇ m or less so that the surface area is large and the functionality is excellent. Preferably it is 2 micrometers or less, More preferably, it is 1 micrometer or less. “Average fiber diameter” refers to the arithmetic average value of fiber diameters at 50 points, and “fiber diameter” refers to the thickness of the fiber measured based on a 5000 ⁇ electron micrograph of the inorganic fiber structure.
- the form of the inorganic fiber structure includes a two-dimensional form such as a non-woven fabric, a three-dimensional form such as a hollow cylindrical form, and a cylindrical form.
- the three-dimensional inorganic fiber structure can be produced, for example, by molding a two-dimensional inorganic fiber aggregate such as a nonwoven fabric.
- the inorganic fiber structure according to the present invention has a low fiber density as a result of a high porosity (bulkness) of 90% or more, the inside of the inorganic fiber structure can be used effectively.
- a preferable porosity is 91% or more, more preferably 92% or more, still more preferably 93% or more, and still more preferably 94% or more.
- an upper limit is not specifically limited, It is preferable that it is 99.9% or less so that it may be excellent in form stability.
- the porosity can be calculated from the following equation.
- P [1-Wf / (V ⁇ SG)] ⁇ 100
- P represents the porosity (%)
- Wf represents the fiber weight (g)
- V represents the volume (cm 3 )
- SG represents the specific gravity (g / cm 3 ) of the fiber.
- P ⁇ 1-Wn / (t ⁇ SG) ⁇ ⁇ 100
- P is the porosity (%)
- Wn is the basis weight (g / m 2 )
- t is the thickness ( ⁇ m)
- SG is the specific gravity (g / cm 3 ) of the fiber.
- the basis weight is a value obtained by measuring the area and weight of the surface having the largest area and converting the weight per 1 m 2 , and the thickness is set so that the load on the surface having the largest area is 100 g / cm 2. It is a value measured by the set micrometer method.
- the tensile strength at break is 0.2 MPa or more so as to have excellent shape retention and sufficient strength. More preferably, it is 0.3 MPa or more, More preferably, it is 0.4 MPa or more, More preferably, it is 0.5 MPa or more, More preferably, it is 0.55 MPa or more.
- This tensile breaking strength is a quotient obtained by dividing the cutting load by the cross-sectional area of the inorganic fiber structure.
- the cutting load is a value measured under the following conditions, and the cross-sectional area is a value obtained from the product of the width and thickness of the test piece at the time of measurement.
- Product name Small tensile tester Model: TSM-01-cre Search Co., Ltd. Test size: 5 mm width x 40 mm length Chuck spacing: 20 mm Tensile speed: 20 mm / min. Initial load: 50mg / 1d
- the amount of hydroxyl groups per unit weight of the fiber is preferably 50 ⁇ mol / g or more, more preferably 100 ⁇ mol / g or more, still more preferably 200 ⁇ mol / g or more, and 300 ⁇ mol / g so that the hydrophilicity is excellent. More preferably, it is more preferably 400 ⁇ mol / g or more, and further preferably 500 ⁇ mol / g or more.
- the amount of hydroxyl groups per unit weight of the fiber is a quotient obtained by dividing the amount of hydroxyl groups of the inorganic fiber structure by the amount of fibers (unit: g) of the inorganic fiber structure used for measuring the hydroxyl amount.
- the amount of hydroxyl groups is a value quantified using a neutralization titration method. That is, after dispersing the inorganic fiber structure in 50 mL of 20 vol% sodium chloride aqueous solution, 0.1N sodium hydroxide aqueous solution was dropped to the neutralization point, and from the amount of sodium hydroxide dropped required for neutralization, Determine the amount of hydroxyl groups in the fiber structure (see references). (References) George W S., Determination of Specific Sufface Area of Colloidal Silica by Titration with Sodium Hydroxide, Anal.Cheam .; 28, 1981-1983, (1956)
- the inorganic fiber structure of the present invention is bonded with an inorganic adhesive without forming a film between inorganic fibers throughout the whole including the inside, it can maintain a porosity of 90% or more. Is possible.
- a culture carrier when used as a culture carrier, it is possible to improve the supply efficiency of nutrients and oxygen indispensable for cells, and because there are many scaffolds necessary for cell culture, high-density culture can be performed.
- the inorganic fiber structure having the functionality of the present invention is obtained by adding a metal ion-containing compound to the inorganic fiber structure having a porosity of 90% or more as described above.
- the metal constituting the metal ion-containing compound include calcium, sodium, iron, magnesium, potassium, copper, iodine, selenium, chromium, zinc, and molybdenum. These metals exhibit cell function inducers or antibacterial effects.
- the metal ion-containing compound can be, for example, a metal salt.
- the metal salt include chloride, sulfate, phosphate, carbonate, hydrogen phosphate, hydrogen carbonate, nitrate, hydroxide and the like.
- an inorganic fiber structure having a function to which a calcium ion-containing salt, a magnesium ion-containing salt, or apatite (apatite) is added can perform cell culture with enhanced cell function.
- the obtained sol solution was used as a spinning solution (inorganic sol solution for spinning), and a neutral spinning method (excluding Comparative Examples 6 and 7) or a flat plate spinning method (Comparative Examples 6 and 7) which is an electrostatic spinning method.
- a gel-like silica fiber web was prepared.
- the neutral spinning method was performed under the same spinning conditions as in Example 8 of JP-A-2005-264374. That is, the counter electrode (creeping discharge element 25) of FIG. 4 was used as the counter electrode 5 of FIG. Details are shown below.
- Spinning nozzle 0.4mm inner diameter metal injection needle (cut end)
- Distance between spinning nozzle and counter electrode 200mm
- Counter electrode and ion generation electrode also serving as both electrodes: A 1 mm thick alumina film (dielectric substrate) is sprayed on a stainless steel plate (induction electrode), and a tungsten wire (discharge electrode) having a diameter of 30 ⁇ m is formed thereon by 10 mm.
- First high-voltage power supply -16 kV
- Second high-voltage power supply ⁇ 5 kV (peak voltage along the AC surface: 5 kV, 50 Hz)
- Airflow Horizontal direction 25cm / sec, Vertical direction 15cm / sec Spinning chamber atmosphere: temperature 25 ° C., humidity 40% RH or less
- Continuous spinning time 30 minutes or more
- the flat plate spinning method was performed according to the following procedure.
- the spinning device the device shown in FIG. 1 of JP-A-2005-194675 was used.
- the spinning solution is supplied to a stainless steel nozzle having an inner diameter of 0.4 mm at a rate of 1 g / hour by a pump, and the spinning solution is discharged from the nozzle to the spinning space (temperature: 26 ° C., relative humidity: 40% or less).
- ( ⁇ 16 kV) is applied, the stainless steel non-porous roll (distance to the nozzle: 10 cm) as a collector is grounded, and the diameter is reduced by applying an electric field to the spinning solution to form silica gel fibers, which are rotated.
- the gel-like silica fiber web was formed by accumulating on a non-porous roll.
- Inorganic sol solution application process for bonding (4) As an inorganic sol solution for bonding used for bonding between fibers, tetraethoxysilane as a metal compound, ethanol as a solvent, water for hydrolysis, and nitric acid as a catalyst, 1: 7.2: 7: 0.0039 The mixture was reacted at a temperature of 25 ° C. and a stirring condition of 300 rpm for 15 hours. After the reaction, it was diluted with ethanol so that the solid content concentration of silicon oxide was 0.25%, and a diluted silica sol solution (adhesive inorganic sol solution) was obtained.
- Examples 1 to 9 and Comparative Example 7 were immersed in the diluted silica sol solution, and then the excess diluted silica sol solution was removed by suction [Table 1 A silica fiber web containing a silica sol dilute solution was prepared by the method A] described in the step (4) column.
- the silica fiber web obtained in the above step was immersed in the silica sol dilute solution, and then the excess silica sol dilute solution was removed using a two-roll press [Step (4 in Table 1)
- the silica fiber web containing the silica sol dilute solution was prepared by the method C] described in the column).
- a silica fiber nonwoven fabric was produced by performing a heat treatment for bonding at the heat treatment temperature (200 ° C. or 500 ° C.) described in the step (5) column (second heat treatment step for bonding).
- the second heat treatment step for bonding was not performed.
- Example 1 to Example 9 and Comparative Examples 1 to 7 The 16 types of silica fiber nonwoven fabrics (Example 1 to Example 9 and Comparative Examples 1 to 7) prepared in (1) were cut into a size of 10 cm ⁇ 10 cm, and various measurements were performed. The results are shown in Table 1.
- the average fiber diameter of the nanofibers constituting the silica fiber nonwoven fabric was 0.8 ⁇ m.
- the nonwoven thickness is a value measured by a micrometer method was set to be weighted 100 g / cm 2, apparent density basis weight (of 1 m 2 size in terms of the weight) and divided by the thickness, respectively means.
- the conditions of cutting load measurement are shown below.
- Comparative Example 8 The gel-like silica fiber web obtained in Comparative Example 1 was used as a comparative culture carrier (hereinafter referred to as culture carrier a) used in the following evaluation tests.
- the average fiber diameter of the nanofibers constituting the culture carrier was 0.8 ⁇ m.
- Comparative Example 9 The silica fiber web obtained in Comparative Example 3 was used as a comparative culture carrier (hereinafter referred to as culture carrier b) used in the following evaluation tests.
- the average fiber diameter of the nanofibers constituting the culture carrier was 0.8 ⁇ m.
- Example 10 Tetraethoxysilane as a metal compound, ethanol as a solvent, water for hydrolysis, and nitric acid as a catalyst are mixed in a molar ratio of 1: 7.2: 7: 0.0039 at a temperature of 25 ° C. and a stirring condition of 300 rpm. After reacting for 15 hours, it was diluted with ethanol so that the solid content concentration of silicon oxide was 0.5% to obtain a diluted silica sol solution (adhesive inorganic sol solution). The silica fiber web obtained in Comparative Example 3 was immersed in the silica sol dilute solution, and then the excess sol solution was removed by suction to prepare a silica sol dilute solution-containing silica fiber web.
- the silica fiber web containing the silica sol dilute solution was kept in an atmosphere at 110 ° C. for 30 minutes (first heat treatment step for bonding). Subsequently, this silica sol dilute solution-containing silica fiber web was subjected to a second heat treatment for bonding at a temperature of 500 ° C. to produce a silica fiber nonwoven fabric (porosity: 93%, tensile strength at break: 0.572 MPa, hydroxyl group amount: 35 ⁇ mol / g). .
- This silica fiber nonwoven fabric was used as a culture carrier (culture carrier A). The average fiber diameter of the nanofibers constituting the culture carrier was 0.8 ⁇ m.
- a voltage 24 kV
- a non-porous stainless steel roll distance to the nozzle: 10 cm
- an electric field is applied to the spinning solution to reduce the diameter.
- the PVA fiber web was heat-treated at 150 ° C. for 30 minutes and then heat-treated for insolubilization.
- the obtained PVA-electrospun nonwoven fabric (porosity: 83%) was used as a culture carrier (culture carrier c).
- the average fiber diameter of the nanofibers constituting the culture carrier was 0.2 ⁇ m.
- a culture carrier for evaluation (1 cm ⁇ 1 cm) was placed in each well of a 24-well plate, and 1 mL of CHO-K1 cells (5 ⁇ 10 5 cells / mL) was seeded every day. The medium was changed.
- FIG. 9 shows the cell adhesion rate on the first day of culture showing cell adhesion ability
- FIG. 10 shows the change in the number of cells per unit dish up to 14 days.
- the cell adhesion ability is expressed by the formula: (Number of cells on carrier / number of seeded cells) ⁇ 100 The cell adhesion rate calculated by (1) was evaluated.
- the culture carrier A of the present invention As shown in FIG. 7, CHO-K1 cells adhered and expanded on the entire surface of the carrier and proliferated, whereas in the comparative culture carrier c, the surface of the culture carrier was spherical. It proliferated while forming a cell mass.
- the culture carrier A and the culture carriers a to c are compared with respect to cell adhesion ability, as shown in FIG. 9, the culture carrier A has the highest adhesion rate between the cells and the carrier, and the cells adhere well on the fibers. It was.
- One of the causes of the cell form of the culture carrier c is a weak interaction related to the adhesion between the carrier and the cells. As shown in FIG.
- the culture carrier A of the present invention had a markedly improved cell proliferation ability than the culture carriers a to c.
- the culture carriers a and b were difficult to observe and poor in operability because the fibers were unwound in the culture solution after several days from the start of the culture and the carrier expanded.
- the culture carrier c was too dense to be observed, and was poor in operability.
- the culture carriers a and b produced by the neutral spinning method have a sufficient surface area as a scaffold for cells necessary for three-dimensional culture, but have no adhesion between fibers or have a very weak adhesion structure. Poor shape retention in liquid. For this reason, a uniform space serving as a scaffold for cells cannot be maintained, and good cell growth hardly occurs.
- the culture carrier A has sufficient cell scaffolds necessary for cell growth, and has good shape retention in the culture solution because of interfiber adhesion, and has a porosity of 90% or more and uniform culture. Since space can be maintained, cell culture can be performed at high density. In addition, the supply efficiency of nutrients and oxygen essential to the cells can be improved, and favorable cell growth is possible. Control of the fiber density and thickness in the cell culture carrier of the present invention has led to the improvement of these cell growth capacities.
- a culture carrier for evaluation (1 cm ⁇ 1 cm) is placed in each well of a 24-well plate, 1 mL of HepG2 cells (5 ⁇ 10 5 cells / mL) are seeded, and the medium is changed every day. Went.
- FIG. 11 shows changes in the number of cells per unit dish up to 14 days for the culture carrier A of the present invention prepared in Example 10 and the comparative culture carriers a, b, and c prepared in Comparative Examples 8 to 10.
- Fig. 12 shows the results of measuring the ammonia removal ability in the medium brought about by the cells up to 14th
- Fig. 13 shows the change in albumin concentration of the cells up to 14th.
- the cell growth ability of the culture carrier A was significantly improved over that of the culture carriers a to c. It was. Comparing the ammonia removal ability, as shown in FIG. 12, during the 2-week culture period, the culture carriers a to c did not show an increase in the function of cells, and conversely, they secreted ammonia. However, the culture carrier of the present invention has improved cell function and improved detoxification ability (ammonia removal ability), which is one of the original functions of hepatocytes.
- HepG2 cells secrete ammonia in monolayer culture (two-dimensional culture on a dish), but have a characteristic that, when three-dimensionally cultured in three dimensions, functions to absorb and metabolize ammonia are born. Therefore, although the effect of the three-dimensional cell is not seen in the comparative cell culture carrier, the culture carrier A of the present invention is three-dimensionally cultured and cultured in a state closer to the state of hepatocytes in vivo. Has been. Looking at the change in albumin concentration of the HepG2 cells cultured on the culture carrier A, as shown in FIG. 13, since the albumin concentration increased during the culture period, the HepG2 cells cultured on the culture carrier A grew normally. Yes.
- the neutral spinning method was performed under the same spinning conditions as in Example 8 of JP-A-2005-264374. That is, the counter electrode (creeping discharge element 25) of FIG. 4 was used as the counter electrode 5 of FIG. Details are shown below.
- Spinning nozzle 0.4mm inner diameter metal injection needle (cut end)
- Distance between spinning nozzle and counter electrode 200mm
- Counter electrode and ion generation electrode also serving as both electrodes: A 1 mm thick alumina film (dielectric substrate) is sprayed on a stainless steel plate (induction electrode), and a tungsten wire (discharge electrode) having a diameter of 30 ⁇ m is formed thereon by 10 mm.
- First high-voltage power supply -16 kV
- Second high-voltage power supply ⁇ 5 kV (peak voltage along the AC surface: 5 kV, 50 Hz)
- Airflow Horizontal direction 25cm / sec, Vertical direction 15cm / sec Spinning chamber atmosphere: temperature 25 ° C., humidity 40% RH or less
- Continuous spinning time 30 minutes or more
- the obtained gel-like fiber web (inorganic fiber aggregate) was accumulated at a temperature of 800 ° C., 120 ° C., or 500 ° C. and then heat treated, and the fired inorganic fiber aggregate (in order “Sample 1”, “Sample 2”, “ Sample 3 ”) was formed.
- Tetraethoxysilane as a metal compound, ethanol as a solvent, water for hydrolysis, and nitric acid as a catalyst are mixed in a molar ratio of 1: 7.2: 7: 0.0039 at a temperature of 25 ° C. and a stirring condition of 300 rpm. After reacting for 15 hours, it was diluted with ethanol so that the solid content concentration of silicon oxide was 0.25% to obtain a diluted silica sol solution (an inorganic sol solution for adhesion). The samples 1 to 3 were immersed in this inorganic sol solution for bonding (solid content concentration: 0.25%), and then the excess silica sol dilute solution was removed by suction, and the sample was placed in an atmosphere at 110 ° C. for 30 minutes. By holding, the solvent of the silica sol dilute solution was removed to form an adhesion sample 1, an adhesion sample 2 and an adhesion sample 3, respectively (first heat treatment for adhesion).
- the adhesive sample 1 was subjected to a second heat treatment (firing treatment) for bonding at a temperature of 500 ° C. for 3 hours to obtain a fired adhesive sample 1 of Example 14 (porosity: 94.3%, tensile breaking strength: 0.568 MPa, hydroxyl group content) : 37 ⁇ mol / g).
- the adhesion sample 2 was set to Example 15 (porosity: 93.5%, tensile breaking strength: 0.292 MPa, hydroxyl group content: 1500 ⁇ mol / g).
- a fired adhesive sample 3 (porosity: 94.2%, tensile strength at break: 0.513 MPa, hydroxyl group amount: 54 ⁇ mol / g) obtained by firing the adhesive sample 3 at 500 ° C. for 3 hours was used as a calcium chloride ethanol solution (concentration: 0.1N) for 3 hours, calcined at 500 ° C. for 3 hours, and further washed with water to prepare a calcium-containing fiber structure 1 as Example 11.
- the calcium element ratio was 14.36%.
- the calcium element ratio of the fired adhesion sample 3 was 0.51%.
- a magnesium-containing fiber structure 2 was prepared and used as Example 12.
- the magnesium element ratio was 22.54%.
- the magnesium element ratio of fired adhesion sample 3 was 0.94%.
- Human osteosarcoma MG63 cells (IFO50108) were cultured on the fibrous structures or samples, respectively, and comparative studies were conducted on the differentiation ability into adult bones.
- a culture medium a MEM medium (Invitrogen) supplemented with 10% fetal bovine serum (FBS), antibiotics, and 0.1% non-essential amino acids was used. 1 mL of 2 ⁇ 10 5 cells / mL was seeded on the sample or fiber structure, and the culture was evaluated for 21 days.
- the cell number transition is shown in FIG. Further, the time course of the enzyme activity per unit cell (unit: ABS / 10 3 cells) of alkaline phosphatase (ALP), which is an enzyme secreted when bone cells differentiate into bone, is shown in FIG.
- ALP activity was determined by washing each fiber structure or sample with a phosphate buffer, adding 100 ⁇ L of 1% Triton X-100-containing phosphate buffer, shaking at 37 ° C. for 30 minutes, It was determined by adding 100 ⁇ L of 0.006 g / mL p-nitrophenyl phosphate, shaking for 2 hours, and measuring the absorbance of the reaction solution at a wavelength of 405 nm.
- the fiber structure (Examples 14 and 15) of the present invention containing no metal ion-containing compound is a calcium-containing fiber structure 1 (Example 11) which is a preferred embodiment of the present invention.
- the cell growth ability is superior to that of the magnesium-containing fiber structure 2 (Example 12) and the apatite-containing fiber structure 3 (Example 13), cells having a low cell function are cultured. Comparing the ALP activity of each fiber structure on the 14th day of culture, the fiber structures of Examples 11 to 13 had higher ALP activity than Example 14 or 15, and the lowest value of Example 12 showing the highest value.
- the value of Example 15 has a 1.5-fold difference in ALP activity, and the cells are easily induced to differentiate into bone. Therefore, the functional fiber structure which is a preferred embodiment of the present invention is effective when cell culture with enhanced cell function is desired.
- the inorganic fiber structure is heat treated at 120 ° C., and is then per unit fiber weight after ethanol sterilization or autoclave sterilization.
- the amount of hydroxyl groups is also listed.
- the amount of hydroxyl group per unit weight of fiber can be 50 ⁇ mol / g or more, and when the temperature is 300 ° C. or less, the amount of hydroxyl group per unit weight of fiber is 100 ⁇ mol / g. If the temperature is 250 ° C. or less, the amount of hydroxyl groups per unit weight of the fiber can be 400 ⁇ mol / g or more. If the temperature is 200 ° C. or less, the amount of hydroxyl groups per unit weight of the fiber is 500 ⁇ mol. / G or more was found to be possible. Moreover, it turned out that the amount of hydroxyl groups per fiber unit weight after ethanol sterilization or after autoclave sterilization is not different from that before sterilization.
- the culture carrier has a large amount of hydroxyl groups and high hydrophilicity, so that spheroid-shaped cells can be easily cultured, and the culture carrier has a small amount of hydroxyl groups and high hydrophobicity. It was found that morphological cells were easy to culture.
- the inorganic fiber structure of the present invention can be applied to, for example, a heat insulating material, a filter material, an analysis tool, a culture carrier such as a cell, a catalyst carrier, an antibacterial material, and the like.
- the cell culture carrier can be applied to all fields using cell culture. Examples include analysis tools using cell culture, regenerative medicine, and production of useful substances. As mentioned above, although this invention was demonstrated along the specific aspect, the deformation
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biomedical Technology (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Cell Biology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Virology (AREA)
- Sustainable Development (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
このような静電紡糸法は、紡糸原液を紡糸空間へ供給するとともに、供給した紡糸原液に対して電界を作用させて延伸し、対向電極上に集積させることによって紡糸する方法である。このように、電界の作用により延伸し、紡糸された繊維は対向電極上に、直接電界の力で集積するため、ペーパー状の不織布になる。しかしながら、断熱材の用途、濾過用途などに使用する場合には、嵩高な不織布であるのが好ましい。
この嵩高な不織布は、繊維同士が接着していないか、あるいは、極めて弱く接着した低密度で綿状の不織布であるため、保形性や強度を必要としない用途には適用できたが、液体濾過など、保形性や強度を必要とする用途においては、不織布形態を保つことができず、実用に適さない場合があった。
(1)無機系繊維を抄造して無機系繊維不織布を製造する方法
(2)無機系繊維不織布にバインダーをスプレーし、乾燥する方法
(3)無機系繊維不織布をバインダー浴に浸漬した後、2本ロールプレス機(圧をかける装置)に通して余剰バインダーを除き、その後乾燥する方法
しかしながら、これら培養担体は3次元培養に必要な細胞の足場となる表面積が不充分であるため、細胞の高密度培養が困難であったり、生体内環境に類似した細胞の組織形成能を保有していない場合が多い。
このような従来の培養担体の問題点を解決し、3次元培養できる培養担体として、「エレクトロスピニング法により作製したナノファイバーを含むスキャフォールド」が提案されている(特許文献3)。具体的な実施例においては、シリカ、PVAからなるナノファイバーを使用している。
しかしながら、このようなナノファイバーを含むスキャホールドであっても、細胞増殖能が低く、高密度培養を行うことが困難であり、また、細胞機能も発現しにくいものであった。更には、繊維密度や厚みの制御が困難であり、また細胞塊が不均一に形成されることから、培養状態を観察することが困難であった。
しかしながら、このようなナノファイバーを含むスキャフォールドは細胞機能の低いものであった。
(1)平均繊維径3μm以下の無機系ナノファイバーからなる無機系繊維構造体であり、内部を含む全体が無機系接着剤で接着した、空隙率が90%以上の無機系繊維構造体;
(2)引張破断強度が0.2MPa以上である、(1)の無機系繊維構造体;
(3)繊維単位重量あたりの水酸基量が50μmol/g以上である、(1)又は(2)の無機系繊維構造体;
(4)静電紡糸法により紡糸された無機系繊維に対して、前記無機系繊維とは反対極性のイオンを照射し、集積させる工程を含んで製造された無機系繊維集合体を、内部を含む全体において、無機系接着剤で接着した、(1)~(3)の無機系繊維構造体;
(5)無機系繊維間に被膜を形成していない、(1)~(4)の無機系繊維構造体;
(6)(1)~(5)の無機系繊維構造体に金属イオン含有化合物を付与した、機能性を有する無機系繊維構造体;
(7)培養担体として用いる、(1)~(6)の無機系繊維構造体;
(8)(i)無機成分を主体とする化合物を含む紡糸用無機系ゾル溶液から、静電紡糸法により無機系繊維を紡糸する工程、
(ii)前記無機系繊維とは反対極性のイオンを照射し、集積させ、無機系繊維集合体を形成する工程、
(iii)前記無機系繊維集合体の内部を含む全体に、無機成分を主体とする化合物を含む接着用無機系ゾル溶液を付与し、余剰の接着用無機系ゾル溶液を通気により除去し、内部を含む全体において、無機系接着剤で接着した無機系繊維構造体を形成する工程、
を含む、無機系繊維構造体の製造方法;
(9)(ii)無機系繊維集合体を形成する工程において、無機系繊維集合体を形成した後に熱処理する、(8)の無機系繊維構造体の製造方法;
(10)熱処理温度が500℃以下である、(9)の無機系繊維構造体の製造方法;
(11)(iii)無機系繊維構造体を形成する工程において、余剰の接着用無機系ゾル溶液を通気により除去した後に熱処理する、(8)~(10)の無機系繊維構造体の製造方法;
(12)熱処理温度が500℃以下である、(11)の無機系繊維構造体の製造方法;
(13)前記紡糸用無機系ゾル溶液及び/又は接着用無機系ゾル溶液が金属イオン含有化合物を含有する、(8)~(12)の無機系繊維構造体の製造方法;
(14)(iii)無機系繊維構造体を形成する工程を実施した後に、金属イオン含有化合物含有溶液を前記無機系繊維構造体に付与する、(8)~(13)の無機系繊維構造体の製造方法
に関する。
前記(3)の本発明の別の好適態様によれば、繊維単位重量あたりの水酸基量が50μmol/g以上であるため、アパタイト等を繊維表面に析出させることができ、無機系繊維構造体に機能を付与することができる。
また、無機系繊維とは反対極性のイオンを照射し、集積し、無機系繊維集合体を形成している、つまり、中和紡糸法に由来する90%以上の高い空隙率(嵩高)の結果、繊維密度が低いため、無機系繊維構造体内部を有効に利用することができる。例えば、培養基材として使用した場合、繊維密度が低いため、細胞が培養担体内部まで広がりやすいという効果を奏する。また、無機系繊維とは反対極性のイオンを照射し、集積し、無機系繊維集合体を形成しているため、嵩高となり、観察可能なまでの繊維密度と厚みの制御が可能である。また、繊維とは反対極性のイオンを照射し、集積するため90%以上の高い空隙率となる。
更に、無機系繊維集合体であるため、無機系接着剤を付与する際に厚さが潰れない。その結果、繊維密度と厚みの制御が可能である。そのため、培養基材として使用した場合、培養状態を観察しやすい。
更に、無機系接着剤で接着されているため、溶液中など様々な使用条件下で形態を維持でき、そのため無機系繊維構造体内部を有効に利用できる。培養基材とした場合、3次元に培養でき、細胞が組織環境に近い状態で培養されるため、細胞機能を発現しやすい。
更に、無機系繊維構造体は内部を含む全体において、無機系接着剤で接着されているため、90%以上の空隙率を保持することが可能である。例えば、培養担体として使用した場合、細胞に必要不可欠な栄養素や酸素などの供給効率を向上させることができ、かつ、細胞培養に必要な足場が多いため、高密度培養できる。
前記(7)の本発明の更に別の好適態様によれば、本発明の無機系繊維構造体を培養担体として使用した場合、平均繊維径が3μm以下と細いため、表面積が広い。その結果、細胞と、細胞との足場となる繊維との接着効率が向上し、更に、細胞に必要不可欠な栄養素や酸素などの供給効率が向上するため、細胞増殖能に優れ、高密度培養できる。
また、無機系接着剤で接着されているため、培養液中においても形態を維持できる。その結果、無機系繊維構造体の嵩高な構造を維持できるため、3次元に培養でき、細胞が組織環境に近い状態で培養されるため、細胞機能を発現しやすい。
前記(10)の本発明の別の好適態様によれば、熱処理温度が500℃以下であるため、無機系繊維構造体の親水性を高めることができる。また、培養基材として使用する場合には、細胞をスフェロイド形態で培養しやすい。
前記(12)の本発明の更に別の好適態様によれば、熱処理温度が500℃以下であるため、無機系繊維構造体の親水性を高めることができる。また、培養基材として使用する場合には、細胞をスフェロイド形態で培養しやすい。
前記(14)の本発明の更に別の好適態様によれば、金属イオン含有化合物含有溶液を無機系繊維構造体に付与しているため、金属イオン含有化合物を含有する、細胞機能が高い、抗菌性に優れるなど、機能性に優れる無機系繊維構造体を製造できる。
本発明の製造方法は、
(1)無機成分を主体とする化合物を含む紡糸用無機系ゾル溶液から、静電紡糸法により無機系繊維を紡糸する工程(紡糸工程)、
(2)前記無機系繊維とは反対極性のイオンを照射し、集積させ、無機系繊維集合体を形成する工程(集積工程)、
(3)前記無機系繊維集合体の内部を含む全体に、無機成分を主体とする化合物を含む接着用無機系ゾル溶液を付与し、余剰の接着用無機系ゾル溶液を通気により除去し、内部を含む全体において、無機系接着剤で接着した無機系繊維構造体を形成する工程(接着工程)
を含み、所望により、
(4)金属イオン含有化合物含有溶液を前記無機系繊維構造体に付与し、無機系繊維構造体に機能性を付与する工程(金属イオン含有化合物含有溶液付与工程)
を更に含むことができる。
本発明の製造方法では、前記金属イオン含有化合物含有溶液付与工程(4)に代えて、あるいは、前記工程(4)に加えて、紡糸工程(1)で使用する紡糸用無機系ゾル溶液、及び/又は、接着工程(3)で使用する接着用無機系ゾル溶液に金属イオン含有化合物を添加することができる。
図1において、静電紡糸装置1は、繊維の原料となる、無機成分を主体とする化合物を含む紡糸用無機系ゾル溶液を吐出する紡糸ノズル2と、この紡糸ノズル2の先端下方に配置された繊維回収装置である繊維回収容器3内に配置された捕集部材(例えばネット、コンベアなど)4とを備えている。さらに、紡糸ノズル2に対向して配置され、吐出されて形成する繊維とは反対極性のイオンを発生するイオン発生手段であると共に、電気的に繊維を吸引できる対向電極5を備えている。紡糸ノズル2には、紡糸用無機系ゾル溶液を供給するゾル溶液供給機6が接続されており、紡糸ノズル2及び対向電極5にはそれぞれ第1高電圧電源7及び第2高電圧電源8が接続されている。また、繊維回収容器3には、繊維を繊維回収容器3に吸引する吸引機9が設けられている。
触媒として塩基を使用すると、曳糸性のゾル溶液を得ることが困難になるため、塩基を使用しないのが好ましい。
反応温度は使用溶媒の沸点以下であれば良いが、低い方が適度に反応速度が遅く、曳糸性のゾル溶液を形成しやすい。あまり低すぎても反応が進行しにくいため、10℃以上であるのが好ましい。
図5において、静電紡糸装置1Aは、実施形態1におけるイオンを発生できると共に、繊維を吸引できる対向電極5に替えて、電離放射線を照射できる電離放射線源10と、繊維を吸引できるネット状の対向電極5(第3高電圧電源11に接続されている)を用いた以外は、静電紡糸装置1と同様な構成であり、重複する説明は省略する。
図6において、静電紡糸装置1Bは、第1紡糸ノズル2aと第2紡糸ノズル2bとが、互いに対向して配置されている。第1紡糸ノズル2aには、紡糸用無機系ゾル溶液を供給する第1ゾル溶液供給機6a及び高電圧を印加する第1高電圧電源7が接続され、第2紡糸ノズル2bには、紡糸用無機系ゾル溶液を供給する第2ゾル溶液供給機6b及び第1高電圧電源7とは反対極性の高電圧を印加する第2高電圧電源8がそれぞれ接続されている。その他は、静電紡糸装置1と同様な構成であり、重複する説明は省略する。
なお、熱処理はオーブン、焼結炉等を用いて実施することができ、その温度は無機系繊維集合体を構成する無機成分によって適宜設定する。
無機系繊維間に被膜を形成することなく、また、空隙率を下げないように、無機系接着剤で接着する際には、無加重で焼成を実施することが好ましい。
金属イオン含有化合物を構成する金属としては、例えば、カルシウム、ナトリウム、鉄、マグネシウム、カリウム、銅、ヨウ素、セレン、クロム、亜鉛、又はモリブデンなどを挙げることができる。これらの金属は、細胞機能誘導因子又は抗菌作用を奏する。
金属イオン含有化合物は、例えば、金属塩であることができる。金属塩としては、例えば、塩化物、硫酸塩、リン酸塩、炭酸塩、リン酸水素塩、炭酸水素塩、硝酸塩、水酸化物などを挙げることができる。特に、カルシウムイオン含有塩、マグネシウムイオン含有塩、アパタイト(りん灰石)を付与した機能性を有する無機系繊維構造体は、細胞機能を高めた細胞培養を行うことができる。
また、接着用無機系ゾル溶液を付与した後、接着工程(3)において、同様の温度範囲で接着用熱処理(乾燥及び/又は焼成)し、繊維単位重量あたりの水酸基量を50μmol/g以上(より好ましくは100μmol/g以上)とすることが好ましい。
無機系ゲル状繊維とは、溶媒を含む状態の繊維であり、例えば、無機系繊維の原料がテトラエトキシシラン(TEOS)、エタノール、水、塩酸からなる場合は、最も沸点の高い物質が水であるため、100℃未満の温度で熱処理をした、又は熱処理をしていない繊維である。
「平均繊維径」は50点における繊維径の算術平均値をいい、「繊維径」は無機系繊維構造体を撮影した5000倍の電子顕微鏡写真をもとに測定した繊維の太さをいう。
P=[1-Wf/(V×SG)]×100
ここで、Pは空隙率(%)、Wfは繊維重量(g)、Vは体積(cm3)、SGは繊維の比重(g/cm3)をそれぞれ表す。
例えば、不織布のように厚さが均一な場合は、次の式から算出することができる。
P={1-Wn/(t×SG)}×100
ここで、Pは空隙率(%)、Wnは目付(g/m2)、tは厚さ(μm)、SGは繊維の比重(g/cm3)をそれぞれ表す。
なお、目付は、最も面積の広い面の面積と重量を測定し、1m2当たりの重量に換算した値であり、厚さは、最も面積の広い面における荷重が100g/cm2となるように設定したマイクロメーター法で測定した値である。
製品名:小型引張試験機
型式:TSM-01-cre サーチ株式会社製
試験サイズ:5mm幅×40mm長
チャック間間隔:20mm
引張速度:20mm/min.
初荷重:50mg/1d
なお、水酸基量は中和滴定法を用いて定量した値である。つまり、無機系繊維構造体を20vol%の塩化ナトリウム水溶液50mL中に分散させた後、0.1N水酸化ナトリウム水溶液を中和点まで滴下し、中和に必要な水酸化ナトリウム滴下量から、無機繊維構造体の水酸基量を決定する(参考文献参照)。
(参考文献)
George W S.,Determination of Specific Sufface Area of Colloidal Silica by Titration with Sodium Hydroxide,Anal.Cheam.;28,1981-1983,(1956)
金属イオン含有化合物を構成する金属としては、例えば、カルシウム、ナトリウム、鉄、マグネシウム、カリウム、銅、ヨウ素、セレン、クロム、亜鉛、又はモリブデンなどを挙げることができる。これらの金属は、細胞機能誘導因子又は抗菌作用を奏する。
金属イオン含有化合物は、例えば、金属塩であることができる。金属塩としては、例えば、塩化物、硫酸塩、リン酸塩、炭酸塩、リン酸水素塩、炭酸水素塩、硝酸塩、水酸化物などを挙げることができる。特に、カルシウムイオン含有塩、マグネシウムイオン含有塩、アパタイト(りん灰石)を付与した機能性を有する無機系繊維構造体は、細胞機能を高めた細胞培養を行うことができる。
(1)シリカ繊維不織布の作製
本実施例では、表1に記載の16種類のシリカ繊維不織布(実施例1~実施例9、比較例1~比較例7)を作製し、その評価を行った。
金属化合物としてのテトラエトキシシラン、溶媒としてのエタノール、加水分解のための水、及び触媒として1規定の塩酸を、1:5:2:0.003のモル比で混合し、温度78℃で10時間の還流操作を行い、次いで、溶媒をロータリーエバポレーターにより除去して濃縮した後、温度60℃に加熱して、粘度が2ポイズのゾル溶液を形成した。得られたゾル溶液を紡糸液(紡糸用無機系ゾル溶液)として用い、中和紡糸法(比較例6及び7を除く)又は静電紡糸法である平板紡糸法(比較例6及び7)によりゲル状シリカ繊維ウエブを作製した。
紡糸ノズル:内径0.4mmの金属製注射針(先端カット)
紡糸ノズルと対向電極との距離:200mm
対向電極及びイオン発生電極(両電極を兼ねる):ステンレス板(誘起電極)上に厚さ1mmのアルミナ膜(誘電体基板)を溶射し、その上に直径30μmのタングステンワイヤ(放電電極)を10mmの等間隔で張った沿面放電素子(タングステンワイヤ面を紡糸ノズルと対向させると共に接地し、ステンレス板とタングステンワイヤ間に交流高電圧電源により50Hzの交流高電圧を印加)
第1高電圧電源:-16kV
第2高電圧電源:±5kV(交流沿面のピーク電圧:5kV、50Hz)
気流:水平方向25cm/sec、鉛直方向15cm/sec
紡糸室内の雰囲気:温度25℃、湿度40%RH以下
連続紡糸時間:30分以上
次に、前記工程で得られたゲル状シリカ繊維ウエブを、実施例7及び比較例1を除いて、表1の工程(3)欄に記載の熱処理温度(120℃、300℃、500℃、又は800℃)で集積後熱処理することにより、シリカ繊維ウエブ(目付:10g/m2)を作製した。
繊維間接着のために用いる接着用無機系ゾル溶液として、金属化合物としてテトラエトキシシラン、溶媒としてエタノール、加水分解のための水、及び触媒として硝酸を、1:7.2:7:0.0039のモル比で混合し、温度25℃、攪拌条件300rpmで15時間反応させた。反応後、酸化ケイ素の固形分濃度が0.25%となるようにエタノールで希釈し、シリカゾル希薄溶液(接着用無機系ゾル溶液)とした。
前記工程で得られたシリカ繊維ウエブの内、実施例1~実施例9、及び比較例7について、前記シリカゾル希薄溶液に浸漬した後、吸引により余剰のシリカゾル希薄溶液を除去すること[表1の工程(4)欄に記載の方法A]により、シリカゾル希薄溶液含有シリカ繊維ウエブを作製した。
実施例1~実施例9、及び比較例7について、無機系接着剤(シリカゾル希薄溶液)に含まれる溶媒の乾燥除去のために、シリカゾル希薄溶液含有シリカ繊維ウエブを110℃の雰囲気中に30分保持した(接着用第一熱処理工程)。一方、比較例1~6については、接着用第一熱処理工程を実施しなかった。
続いて、実施例2、実施例3、実施例5、実施例6、比較例4、比較例5、比較例7について、前記工程で得られたシリカゾル希薄溶液含有シリカ繊維ウエブを、表1の工程(5)欄に記載の熱処理温度(200℃又は500℃)で接着用熱処理すること(接着用第二熱処理工程)により、シリカ繊維不織布を作製した。
一方、実施例1、実施例4、実施例7~9、比較例1~3、比較例6については、接着用第二熱処理工程を実施しなかった。
前記(1)で作製した16種類のシリカ繊維不織布(実施例1~実施例9、比較例1~7)について、10cm×10cmのサイズに切断し、各種測定を実施した結果を表1に示す。なお、いずれのシリカ繊維不織布においても、それを構成するナノファイバーの平均繊維径は0.8μmであった。
なお、不織布の厚みは、加重100g/cm2となるように設定したマイクロメーター法で測定した値、見掛密度は目付(1m2の大きさに換算した重量)を厚みで除した値をそれぞれ意味する。
また、切断荷重測定の条件を以下に示す。
製品名:小型引張試験機
型式:TSM-01-cre サーチ株式会社製
試験サイズ:5mm×40mm
チャック間隔:20mm
引張速度:20mm/min
初荷重:50mg/1d
空隙率は、下記式:
[空隙率(%)]=[1-(目付/厚み/比重)]×100
(目付の単位=g/m2、厚みの単位=μm、シリカの比重=2g/cm3)
により算出した。
比較例8
前記比較例1で得られたゲル状シリカ繊維ウエブを、以下の評価試験で使用する比較用の培養担体(以下、培養担体aと称する)とした。培養担体を構成するナノファイバーの平均繊維径は0.8μmであった。
前記比較例3で得られたシリカ繊維ウエブを、以下の評価試験で使用する比較用の培養担体(以下、培養担体bと称する)とした。培養担体を構成するナノファイバーの平均繊維径は0.8μmであった。
金属化合物としてテトラエトキシシラン、溶媒としてエタノール、加水分解のための水、及び触媒として硝酸を、1:7.2:7:0.0039のモル比で混合し、温度25℃、攪拌条件300rpmで15時間反応させた後、酸化ケイ素の固形分濃度が0.5%となるようエタノールで希釈し、シリカゾル希薄溶液(接着用無機系ゾル溶液)とした。
前記比較例3で得たシリカ繊維ウエブを前記シリカゾル希薄溶液中に浸漬した後、吸引により余剰のゾル溶液を除去し、シリカゾル希薄溶液含有シリカ繊維ウエブを調製した。
シリカゾル希薄溶液に含まれる溶媒の乾燥除去のために、シリカゾル希薄溶液含有シリカ繊維ウエブを110℃の雰囲気中に30分保持した(接着用第一熱処理工程)。
次いで、このシリカゾル希薄溶液含有シリカ繊維ウエブを温度500℃で接着用第二熱処理し、シリカ繊維不織布(空隙率:93%、引張破断強度:0.572MPa、水酸基量:35μmol/g)を製造した。このシリカ繊維不織布を培養担体(培養担体A)とした。培養担体を構成するナノファイバーの平均繊維径は0.8μmであった。
PVA(重合度1000、完全ケン化型)を15wt%の濃度に調整したものを、紡糸液として使用した。
紡糸装置としては、特開2005-194675号公報の図1に記載の装置を使用した。先に調製した紡糸液を、内径が0.4mmのステンレス製ノズルに、ポンプにより0.5g/時間で供給し、ノズルから紡糸液を紡糸空間(温度26℃、相対湿度50%)へ吐出するとともに、ノズルに電圧(24kV)を印加し、捕集体であるステンレス製無孔ロール(ノズルとの距離:10cm)をアースして、紡糸液に電界を作用させることによって細径化し、PVA繊維を形成し、回転する無孔ロール上に集積させ、PVA繊維ウエブを形成した。
このPVA繊維ウエブに150℃、30分間の集積後熱処理を行なうことにより、不溶化処理を実施した。得られたPVA-静電紡糸不織布(空隙率:83%)を培養担体(培養担体c)とした。培養担体を構成するナノファイバーの平均繊維径は0.2μmであった。
(1)チャイニーズハムスター卵巣細胞由来CHO-K1を用いた評価
CHO-K1細胞(ATCC:CCL-61、参考文献:Puch TT,et al., Genetics of somatic mammalian cells III. Long-term cultivation of euploid cells from human and animal subjects., J.Exp.Med.108:945-956,4958.PudMed:13598821)の培養は、DMEM(Dulbecco's Modified Eagle's Medium)に、10%FBS、及び抗生物質(60μg/mLペニシリン及び100μg/mLストレプトマイシン)を添加した培地を使用し、37℃、5%CO2条件下にて実施した。
培養環境としては、24ウェルプレートの各ウェル内に、評価用の培養担体(1cm×1cm)を載置し、CHO-K1細胞(5×105cells/mL)1mLを播種し、1日毎に培地交換を行った。
(担体上の細胞数/播種細胞数)×100
により算出した細胞接着率で評価した。
細胞接着能について培養担体Aと培養担体a~cを比較すると、図9に示すように、培養担体Aは細胞と担体との接着率が一番高く、繊維上に細胞が良好に接着していた。前記の培養担体cの細胞形態は、担体と細胞の接着に関わる相互作用が弱いことが原因の一つである。
図10に示すように、2週間の培養において、本発明の培養担体Aは、培養担体a~cよりも細胞増殖能が著しく向上していた。培養担体a~bは、培養開始から数日経過すると、培養液中にて繊維が解れ、担体の膨張が見られたため、観察しにくく、また、操作性の悪いものであった。また、培養担体cは、構造が緻密すぎて、観察しにくく、また、操作性の悪いものであった。
本発明の細胞培養担体における繊維密度および厚みの制御がこれらの細胞増殖能の向上をもたらしていた。
HepG2細胞(ATCC:HB-0865、参考文献:Knowles BB, et al., Human hepatocellular carcinoma cell lines secrete the major plasma proteins and hepatitis B surface antigen., Science 209:497-499,1980.PubMed:6248960)の培養は、Williams’s Medium E(購入会社名:シグマ社)に、10%ウシ胎児血清(FBS)、抗生物質(60μg/mLペニシリン及び100μg/mLストレプトマイシン)、及び1mmol/L NH4Clを添加した培地を使用し、37℃、5%CO2条件下にて実施した。
培養環境としては、24ウェルプレートの各ウェル内に、評価用の培養担体(1cm×1cm)を載置し、HepG2細胞(5×105cells/mL)1mLを播種し、1日毎に培地交換を行った。
アンモニア除去能を比較すると、図12に示すように、2週間の培養期間中、培養担体a~cは細胞の高機能化が見られず、逆にアンモニアを分泌する方向にあった。しかし、本発明の培養担体は、細胞機能が向上し、肝細胞本来の機能の一つである解毒能(アンモニア除去能)が向上していた。
HepG2細胞は、単層培養(ディッシュ上での2次元培養)では、アンモニアを分泌するが、3次元にして立体的に培養すると、アンモニアを吸収・代謝する機能が生まれてくるという特徴を持つ。よって、比較用の細胞培養担体では細胞の3次元化による効果は見られないが、本発明の培養担体Aは3次元的に培養され、より生体内での肝細胞の状態に近い状態で培養されている。
培養担体Aで培養したHepG2細胞のアルブミン濃度変化をみても、図13に示すように、培養期間中にアルブミン濃度が上昇しているため、培養担体Aで培養したHepG2細胞は正常に増殖している。
上記(1)及び(2)の結果に基づく総合評価を表2に示す。
表2における細胞増殖能については、比較例10(PVA)を基準として評価した。細胞接着性については、概ね、約30%以下を「×」、約30%~50%を「△」、約50%以上を「○」とした。
金属化合物としてテトラエトキシシラン、溶媒としてエタノール、加水分解のための水、及び触媒として1規定の塩酸を、1:5:2:0.003のモル比で混合し、温度78℃で10時間の還流操作を行い、次いで、溶媒をロータリーエバポレーターにより除去して濃縮した後、温度60℃に加熱して、粘度が2ポイズのゾル溶液を形成した。得られたゾル溶液を紡糸液(紡糸用無機系ゾル溶液)として用い、中和紡糸法により、つまり、静電紡糸法により紡糸するとともに、反対極性のイオンを照射して集積させ、ゲル状繊維ウエブ(無機系繊維集合体)を形成した。
紡糸ノズル:内径0.4mmの金属製注射針(先端カット)
紡糸ノズルと対向電極との距離:200mm
対向電極及びイオン発生電極(両電極を兼ねる):ステンレス板(誘起電極)上に厚さ1mmのアルミナ膜(誘電体基板)を溶射し、その上に直径30μmのタングステンワイヤ(放電電極)を10mmの等間隔で張った沿面放電素子(タングステンワイヤ面を紡糸ノズルと対向させると共に接地し、ステンレス板とタングステンワイヤ間に交流高電圧電源により50Hzの交流高電圧を印加)
第1高電圧電源:-16kV
第2高電圧電源:±5kV(交流沿面のピーク電圧:5kV、50Hz)
気流:水平方向25cm/sec、鉛直方向15cm/sec
紡糸室内の雰囲気:温度25℃、湿度40%RH以下
連続紡糸時間:30分以上
この接着用無機系ゾル溶液(固形分濃度:0.25%)中に、前記試料1~3をそれぞれ浸漬した後、吸引により余剰のシリカゾル希薄溶液を除去し、110℃の雰囲気中に30分保持することにより、シリカゾル希薄溶液の溶媒を除去し、それぞれ接着試料1、接着試料2、接着試料3を形成した(接着用第一熱処理)。
以下の実施例11~15について、培養担体としての各種機能評価を実施した。なお、いずれの繊維構造体においても、それを構成するナノファイバーの平均繊維径は0.8μmであった。
(実施例11) カルシウム含有繊維構造体1
(実施例12) マグネシウム含有繊維構造体2
(実施例13) アパタイト含有繊維構造体3
(実施例14) 焼成接着試料1
(実施例15) 接着試料2
培養14日目の各繊維構造体のALP活性を比較すると、実施例11~13の繊維構造体は実施例14又は15よりもALP活性が高く、最も高い値を示した実施例12と最も低い値の実施例15とでは、1.5倍のALP活性の差があり、骨への分化誘導が起こりやすい細胞となっている。
そのため、本発明の好適態様である、機能性を有する繊維構造体は細胞機能を高めた細胞培養を行いたい場合に有効である。
(1)無機系繊維構造体の作製と水酸基量測定
前記比較例1で得られたゲル状シリカ繊維ウエブ(未焼成)を、1℃/min.の速度で温度120℃、200℃、250℃、300℃、500℃及び800℃まで昇温し、3時間保持して、それぞれの温度で熱処理した時の、繊維単位重量あたりの水酸基量を測定した。なお、いずれのシリカ繊維不織布、あるいは、焼成前のゲル状シリカ繊維ウエブにおいても、それを構成するナノファイバーの平均繊維径は0.8μmであった。
結果を図17に示す。なお、図17においては、無機系繊維構造体を細胞培養担体に用いる場合を考慮して、無機系繊維構造体を120℃で熱処理した後に、エタノール殺菌後又はオートクレーブ殺菌後の繊維単位重量あたりの水酸基量も掲載している。
また、エタノール殺菌後又はオートクレーブ殺菌後における繊維単位重量あたりの水酸基量は殺菌前と変わらないこともわかった。
前記比較例1で得られたゲル状シリカ繊維ウエブ(未焼成)を、1℃/min.の速度で温度100℃、300℃、又は500℃まで昇温し、その温度で3時間保持することにより、培養担体を調製した。
これらの各培養担体(更に対照として、焼成前のゲル状シリカ繊維ウエブ)を用いて、先述した培養条件に従って、ヒト肝癌由来細胞株HepG2の細胞培養を14日間実施した。
14日間培養した後に撮影したSEM写真を、図18(参考例1:未焼成)、図19(参考例2:100℃で焼成)、図20(参考例3:300℃で焼成)、図21(参考例4:500℃で焼成)に示す。
以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は本発明の範囲に含まれる。
Claims (14)
- 平均繊維径3μm以下の無機系ナノファイバーからなる無機系繊維構造体であり、内部を含む全体が無機系接着剤で接着した、空隙率が90%以上の無機系繊維構造体。
- 引張破断強度が0.2MPa以上である、請求項1に記載の無機系繊維構造体。
- 繊維単位重量あたりの水酸基量が50μmol/g以上である、請求項1又は2に記載の無機系繊維構造体。
- 静電紡糸法により紡糸された無機系繊維に対して、前記無機系繊維とは反対極性のイオンを照射し、集積させる工程を含んで製造された無機系繊維集合体を、内部を含む全体において、無機系接着剤で接着した、請求項1~3のいずれか一項に記載の無機系繊維構造体。
- 無機系繊維間に被膜を形成していない、請求項1~4のいずれか一項に記載の無機系繊維構造体。
- 請求項1~5のいずれか一項に記載の無機系繊維構造体に金属イオン含有化合物を付与した、機能性を有する無機系繊維構造体。
- 培養担体として用いる、請求項1~6のいずれか一項に記載の無機系繊維構造体。
- (i)無機成分を主体とする化合物を含む紡糸用無機系ゾル溶液から、静電紡糸法により無機系繊維を紡糸する工程、
(ii)前記無機系繊維とは反対極性のイオンを照射し、集積させ、無機系繊維集合体を形成する工程、
(iii)前記無機系繊維集合体の内部を含む全体に、無機成分を主体とする化合物を含む接着用無機系ゾル溶液を付与し、余剰の接着用無機系ゾル溶液を通気により除去し、内部を含む全体において、無機系接着剤で接着した無機系繊維構造体を形成する工程、
を含む、無機系繊維構造体の製造方法。 - (ii)無機系繊維集合体を形成する工程において、無機系繊維集合体を形成した後に熱処理する、請求項8に記載の無機系繊維構造体の製造方法。
- 熱処理温度が500℃以下である、請求項9に記載の無機系繊維構造体の製造方法。
- (iii)無機系繊維構造体を形成する工程において、余剰の接着用無機系ゾル溶液を通気により除去した後に熱処理する、請求項8~10のいずれか一項に記載の無機系繊維構造体の製造方法。
- 熱処理温度が500℃以下である、請求項11に記載の無機系繊維構造体の製造方法。
- 前記紡糸用無機系ゾル溶液及び/又は接着用無機系ゾル溶液が金属イオン含有化合物を含有する、請求項8~12のいずれか一項に記載の無機系繊維構造体の製造方法。
- (iii)無機系繊維構造体を形成する工程を実施した後に、金属イオン含有化合物含有溶液を前記無機系繊維構造体に付与する、請求項8~13のいずれか一項に記載の無機系繊維構造体の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080004861.7A CN102308038B (zh) | 2009-01-14 | 2010-01-14 | 无机类纤维结构体及其制造方法 |
JP2010546642A JP5424354B2 (ja) | 2009-01-14 | 2010-01-14 | 無機系繊維構造体及びその製造方法 |
KR1020117018183A KR101681972B1 (ko) | 2009-01-14 | 2010-01-14 | 무기계 섬유 구조체 및 그 제조 방법 |
EP20100731272 EP2381022B1 (en) | 2009-01-14 | 2010-01-14 | Inorganic fiber structure and process for producing same |
US13/144,632 US9023743B2 (en) | 2009-01-14 | 2010-01-14 | Inorganic fiber structure and process for producing same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-005678 | 2009-01-14 | ||
JP2009005678 | 2009-01-14 | ||
JP2009171857 | 2009-07-23 | ||
JP2009-171857 | 2009-07-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010082603A1 true WO2010082603A1 (ja) | 2010-07-22 |
Family
ID=42339857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/050347 WO2010082603A1 (ja) | 2009-01-14 | 2010-01-14 | 無機系繊維構造体及びその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9023743B2 (ja) |
EP (1) | EP2381022B1 (ja) |
JP (1) | JP5424354B2 (ja) |
KR (1) | KR101681972B1 (ja) |
CN (2) | CN102308038B (ja) |
WO (1) | WO2010082603A1 (ja) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010185164A (ja) * | 2009-01-14 | 2010-08-26 | Japan Vilene Co Ltd | 無機系繊維不織布及びその製造方法 |
JP2012016323A (ja) * | 2010-07-09 | 2012-01-26 | Japan Vilene Co Ltd | 高機能繊維構造体 |
JP2012219420A (ja) * | 2011-04-13 | 2012-11-12 | Panasonic Corp | ナノファイバ製造装置、および、ナノファイバ製造方法 |
KR101249952B1 (ko) * | 2010-12-20 | 2013-04-03 | 대림대학교산학협력단 | 에르븀이 첨가된 이산화티타늄 나노섬유의 제조방법 |
CN103175723A (zh) * | 2011-12-22 | 2013-06-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 激光共聚焦扫描显微镜高分子纤维可视化的制备方法 |
JP2014018121A (ja) * | 2012-07-16 | 2014-02-03 | Japan Vilene Co Ltd | 初代細胞の培養方法 |
CN103614803A (zh) * | 2013-11-29 | 2014-03-05 | 苏州大学 | 一种制备电离辐射防护材料的方法 |
JP2014093979A (ja) * | 2012-11-09 | 2014-05-22 | Japan Vilene Co Ltd | 薬効評価方法 |
JP2015045098A (ja) * | 2013-08-27 | 2015-03-12 | 日本バイリーン株式会社 | 構造体及び構造体の製造方法 |
JP2015159778A (ja) * | 2014-02-28 | 2015-09-07 | 日本バイリーン株式会社 | 光学的測定用細胞培養担体、光学的測定用ウェルプレート、及び細胞の光学的測定方法 |
CN109786681A (zh) * | 2017-12-28 | 2019-05-21 | 湖南长远锂科有限公司 | 一种具有导电性复合包覆层的锂离子电池正极材料及其制备方法 |
JP7426815B2 (ja) | 2019-12-18 | 2024-02-02 | 日本バイリーン株式会社 | 細胞培養担体 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013179218A1 (en) | 2012-05-28 | 2013-12-05 | L-M-J Nation Security Llc | Fire resistant paint for application to an outdoor or indoor surface, articles of manufacture, an apparatus for manufacture and a process for manufacture thereof |
CZ2012549A3 (cs) * | 2012-08-14 | 2013-06-19 | Technická univerzita v Liberci | Nanovlákenná struktura s imobilizovaným organickým agens a zpusob její výroby |
FI127747B (en) | 2017-05-24 | 2019-01-31 | Fortum Power & Heat Oy | New ion-exchange materials |
CN108547006A (zh) * | 2018-04-24 | 2018-09-18 | 胡权 | 一种静电纺丝接收装置及其静电纺丝方法 |
CN109338483B (zh) * | 2018-09-30 | 2020-12-29 | 西安工程大学 | 自支撑纳米纤维超高温过滤膜材料的制备方法 |
EP3670713A1 (de) * | 2018-12-21 | 2020-06-24 | PresCon AG | Verwendung von elektrospinn-verfahren zum konservieren und restaurieren von kulturgütern und vorrichtung dafür |
US11618975B1 (en) * | 2019-07-10 | 2023-04-04 | American Nano Llc. | Electrospinning apparatus and methods |
CN113957566B (zh) * | 2021-11-20 | 2023-07-07 | 福州大学 | 一种固体氧化物电池复合纳米纤维及其制备方法 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55163248A (en) * | 1979-06-06 | 1980-12-19 | Edami Negishi | Porous metal material and method |
JPS62196342A (ja) * | 1986-02-20 | 1987-08-29 | Mitsubishi Chem Ind Ltd | 複合材用炭素繊維プリフオ−ムの製造方法 |
JP2003073964A (ja) * | 2001-06-08 | 2003-03-12 | Japan Vilene Co Ltd | 無機系構造体の製造方法、及び無機系構造体 |
JP2004238749A (ja) | 2003-02-04 | 2004-08-26 | Japan Vilene Co Ltd | 静電紡糸方法及び静電紡糸装置 |
JP2005194675A (ja) | 2004-01-09 | 2005-07-21 | Japan Vilene Co Ltd | 繊維集合体の製造方法 |
JP2005264374A (ja) | 2004-03-18 | 2005-09-29 | Japan Vilene Co Ltd | 静電紡糸法による繊維集合体の製造方法及び繊維集合体製造装置 |
JP2007217826A (ja) * | 2006-02-16 | 2007-08-30 | Teijin Ltd | 綿状体および綿状体の製造方法 |
JP2007217836A (ja) * | 2006-02-17 | 2007-08-30 | Japan Vilene Co Ltd | 無機系極細繊維シート及びその製造方法 |
JP2007231505A (ja) * | 2001-06-08 | 2007-09-13 | Japan Vilene Co Ltd | 無機系構造体の製造方法、及び無機系構造体 |
JP2007319074A (ja) | 2006-05-31 | 2007-12-13 | Kyushu Univ | ナノファイバーを含む新規スキャフォールドおよびその用途 |
JP2008199897A (ja) * | 2005-05-16 | 2008-09-04 | Applied Cell Biotechnologies Inc | 細胞培養用基材及び細胞培養方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60210165T2 (de) * | 2001-06-08 | 2006-08-10 | Japan Vilene Co., Ltd. | Verfahren zur Herstellung eines anorganischen Gegenstandes |
EP1686208A4 (en) | 2003-11-10 | 2009-06-24 | Teijin Ltd | NON-WOVEN CARBON FIBER TISSUE AND METHODS OF MAKING AND USING SAME |
JP4971789B2 (ja) * | 2004-03-04 | 2012-07-11 | 日本板硝子株式会社 | プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜および燃料電池 |
WO2006001403A1 (ja) | 2004-06-23 | 2006-01-05 | Teijin Limited | 無機系繊維、繊維構造体およびその製造方法 |
EP1829141B1 (en) * | 2004-12-09 | 2013-05-29 | Nanosys, Inc. | Nanowire-based membrane electrode assemblies for fuel cells |
WO2006092986A1 (ja) * | 2005-03-02 | 2006-09-08 | Ibiden Co., Ltd. | 無機繊維集合体、無機繊維集合体の製造方法、ハニカム構造体及びハニカム構造体の製造方法 |
CN101238249B (zh) * | 2005-08-10 | 2012-09-19 | 东丽株式会社 | 海绵状结构体和粉末以及它们的制造方法 |
CN100342068C (zh) * | 2005-08-29 | 2007-10-10 | 中国民用航空学院 | 废旧聚苯乙烯泡沫塑料的静电纺丝方法 |
JP2007063683A (ja) * | 2005-08-29 | 2007-03-15 | Hyogo Prefecture | 静電噴霧法を用いて紡糸化したシリカ不織布及びその製造方法 |
JP4938279B2 (ja) * | 2005-09-29 | 2012-05-23 | 帝人株式会社 | 繊維構造体の製造方法 |
JP5410307B2 (ja) * | 2009-01-14 | 2014-02-05 | 日本バイリーン株式会社 | 無機系繊維不織布及びその製造方法 |
-
2010
- 2010-01-14 JP JP2010546642A patent/JP5424354B2/ja active Active
- 2010-01-14 KR KR1020117018183A patent/KR101681972B1/ko active IP Right Grant
- 2010-01-14 WO PCT/JP2010/050347 patent/WO2010082603A1/ja active Application Filing
- 2010-01-14 CN CN201080004861.7A patent/CN102308038B/zh active Active
- 2010-01-14 CN CN201510036727.XA patent/CN104611836A/zh active Pending
- 2010-01-14 US US13/144,632 patent/US9023743B2/en active Active
- 2010-01-14 EP EP20100731272 patent/EP2381022B1/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55163248A (en) * | 1979-06-06 | 1980-12-19 | Edami Negishi | Porous metal material and method |
JPS62196342A (ja) * | 1986-02-20 | 1987-08-29 | Mitsubishi Chem Ind Ltd | 複合材用炭素繊維プリフオ−ムの製造方法 |
JP2003073964A (ja) * | 2001-06-08 | 2003-03-12 | Japan Vilene Co Ltd | 無機系構造体の製造方法、及び無機系構造体 |
JP2007231505A (ja) * | 2001-06-08 | 2007-09-13 | Japan Vilene Co Ltd | 無機系構造体の製造方法、及び無機系構造体 |
JP2004238749A (ja) | 2003-02-04 | 2004-08-26 | Japan Vilene Co Ltd | 静電紡糸方法及び静電紡糸装置 |
JP2005194675A (ja) | 2004-01-09 | 2005-07-21 | Japan Vilene Co Ltd | 繊維集合体の製造方法 |
JP2005264374A (ja) | 2004-03-18 | 2005-09-29 | Japan Vilene Co Ltd | 静電紡糸法による繊維集合体の製造方法及び繊維集合体製造装置 |
JP2008199897A (ja) * | 2005-05-16 | 2008-09-04 | Applied Cell Biotechnologies Inc | 細胞培養用基材及び細胞培養方法 |
JP2007217826A (ja) * | 2006-02-16 | 2007-08-30 | Teijin Ltd | 綿状体および綿状体の製造方法 |
JP2007217836A (ja) * | 2006-02-17 | 2007-08-30 | Japan Vilene Co Ltd | 無機系極細繊維シート及びその製造方法 |
JP2007319074A (ja) | 2006-05-31 | 2007-12-13 | Kyushu Univ | ナノファイバーを含む新規スキャフォールドおよびその用途 |
Non-Patent Citations (4)
Title |
---|
GEORGE W S.: "Determination of Specific Surface Area of Colloidal Silica by Titration with Sodium Hydroxide", ANAL. CHEAM., vol. 28, 1956, pages 1981 - 1983 |
KNOWLES BB ET AL.: "Human hepatocellular carcinoma cell lines secrete the major plasma proteins and hepatitis B surface antigen.", SCIENCE, vol. 209, 1980, pages 497 - 499 |
PUCH TT ET AL.: "Genetics of somatic mammalian cells III. Long-term cultivation of euploid cells from human and animal subjects.", J. EXP. MED., vol. 108, pages 945 - 956,4958 |
See also references of EP2381022A4 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010185164A (ja) * | 2009-01-14 | 2010-08-26 | Japan Vilene Co Ltd | 無機系繊維不織布及びその製造方法 |
JP2012016323A (ja) * | 2010-07-09 | 2012-01-26 | Japan Vilene Co Ltd | 高機能繊維構造体 |
KR101249952B1 (ko) * | 2010-12-20 | 2013-04-03 | 대림대학교산학협력단 | 에르븀이 첨가된 이산화티타늄 나노섬유의 제조방법 |
JP2012219420A (ja) * | 2011-04-13 | 2012-11-12 | Panasonic Corp | ナノファイバ製造装置、および、ナノファイバ製造方法 |
CN103175723B (zh) * | 2011-12-22 | 2015-11-18 | 上海纳米技术及应用国家工程研究中心有限公司 | 激光共聚焦扫描显微镜高分子纤维可视化的制备方法 |
CN103175723A (zh) * | 2011-12-22 | 2013-06-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 激光共聚焦扫描显微镜高分子纤维可视化的制备方法 |
JP2014018121A (ja) * | 2012-07-16 | 2014-02-03 | Japan Vilene Co Ltd | 初代細胞の培養方法 |
JP2014093979A (ja) * | 2012-11-09 | 2014-05-22 | Japan Vilene Co Ltd | 薬効評価方法 |
JP2015045098A (ja) * | 2013-08-27 | 2015-03-12 | 日本バイリーン株式会社 | 構造体及び構造体の製造方法 |
CN103614803A (zh) * | 2013-11-29 | 2014-03-05 | 苏州大学 | 一种制备电离辐射防护材料的方法 |
JP2015159778A (ja) * | 2014-02-28 | 2015-09-07 | 日本バイリーン株式会社 | 光学的測定用細胞培養担体、光学的測定用ウェルプレート、及び細胞の光学的測定方法 |
CN109786681A (zh) * | 2017-12-28 | 2019-05-21 | 湖南长远锂科有限公司 | 一种具有导电性复合包覆层的锂离子电池正极材料及其制备方法 |
CN109786681B (zh) * | 2017-12-28 | 2021-03-16 | 湖南长远锂科股份有限公司 | 一种具有导电性复合包覆层的锂离子电池正极材料及其制备方法 |
JP7426815B2 (ja) | 2019-12-18 | 2024-02-02 | 日本バイリーン株式会社 | 細胞培養担体 |
Also Published As
Publication number | Publication date |
---|---|
EP2381022B1 (en) | 2013-11-20 |
EP2381022A4 (en) | 2012-06-27 |
JPWO2010082603A1 (ja) | 2012-07-05 |
CN104611836A (zh) | 2015-05-13 |
CN102308038A (zh) | 2012-01-04 |
US9023743B2 (en) | 2015-05-05 |
CN102308038B (zh) | 2015-10-21 |
KR101681972B1 (ko) | 2016-12-02 |
KR20110119684A (ko) | 2011-11-02 |
EP2381022A1 (en) | 2011-10-26 |
US20110274927A1 (en) | 2011-11-10 |
JP5424354B2 (ja) | 2014-02-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5424354B2 (ja) | 無機系繊維構造体及びその製造方法 | |
Zong et al. | Designing function-oriented artificial nanomaterials and membranes via electrospinning and electrospraying techniques | |
JP5747341B2 (ja) | 高機能繊維構造体 | |
Singh et al. | Development of novel silk fibroin/polyvinyl alcohol/sol–gel bioactive glass composite matrix by modified layer by layer electrospinning method for bone tissue construct generation | |
CN101376567B (zh) | 具有纳米孔的复合生物活性玻璃超细纤维及其制备方法 | |
Kasuga et al. | Siloxane-poly (lactic acid)-vaterite composites with 3D cotton-like structure | |
AU2013278347B2 (en) | Method for producing porous calcium phosphate body, and porous calcium phosphate body produced thereby | |
JP5912716B2 (ja) | 無機系繊維構造体及びその製造方法 | |
CN101288780A (zh) | 可降解力学增强型生物玻璃基多孔复合材料及其制备方法 | |
Aly et al. | Preparation and characterization of wollastonite/titanium oxide nanofiber bioceramic composite as a future implant material | |
KR100751504B1 (ko) | 나노-마크로 사이즈의 계층적 기공구조를 가지는 생체재료및 이의 합성 방법 | |
Bretcanu et al. | Electrospun nanofibrous biodegradable polyester coatings on Bioglass®-based glass-ceramics for tissue engineering | |
JP5410307B2 (ja) | 無機系繊維不織布及びその製造方法 | |
Faridi-Majidi et al. | The effect of synthesis parameters on morphology and diameter of electrospun hydroxyapatite nanofibers | |
Sakai et al. | Prospective use of electrospun ultra‐fine silicate fibers for bone tissue engineering | |
JP6058994B2 (ja) | 細胞培養担体及びその使用方法 | |
Kim et al. | Interlayer structure of bioactive molecule, 2-aminoethanesulfonate, intercalated into calcium-containing layered double hydroxides | |
JP6157070B2 (ja) | 初代細胞の培養方法 | |
CN114425100A (zh) | 一种压电纳米复合材料及其制备方法、具有压电性和体内示踪能力的3d打印骨修复支架 | |
JP5783554B2 (ja) | 骨充填材の製造方法 | |
JP6778099B2 (ja) | 無機系繊維シート及びその製造方法 | |
JP5598812B2 (ja) | 繊維集合体 | |
Feng et al. | Group Replacement–Rearrangement-Triggered Linear-Assembly Nonaqueous Precipitation Synthesis of Hydroxyapatite Fibers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080004861.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10731272 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010546642 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13144632 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010731272 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 3043/KOLNP/2011 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 20117018183 Country of ref document: KR Kind code of ref document: A |