WO2013137206A1 - Conductive fiber structure, metal porous structure, electrode material for battery and battery - Google Patents
Conductive fiber structure, metal porous structure, electrode material for battery and battery Download PDFInfo
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- WO2013137206A1 WO2013137206A1 PCT/JP2013/056679 JP2013056679W WO2013137206A1 WO 2013137206 A1 WO2013137206 A1 WO 2013137206A1 JP 2013056679 W JP2013056679 W JP 2013056679W WO 2013137206 A1 WO2013137206 A1 WO 2013137206A1
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- 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
- D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/48—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
- D04H1/485—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation in combination with weld-bonding
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- 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
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/02—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by mechanical methods, e.g. needling
- D04H5/03—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by mechanical methods, e.g. needling by fluid jet
-
- 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
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/06—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by welding-together thermoplastic fibres, filaments, or yarns
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- porous structures have been proposed as conductive porous structures used in various electronic parts such as battery materials such as electrode materials, electromagnetic wave sealing materials, filters, accessories, and grounding materials. Yes.
- a conductive porous structure for example, a sponge-like material made of resin such as urethane foam is subjected to a treatment such as plating, vacuum deposition, or chemical vapor deposition, and the surface thereof is nickel, copper, chromium, cobalt, or the like.
- a conductive porous structure having a metal film formed thereon is known.
- disappearing urethane foam (henceforth "metal porous structure") Is also known as a conductive porous structure.
- a conductive porous structure in which a metal film is formed on a sponge-like material is uniform in the thickness direction, length direction, and width direction of the sheet, and is therefore suitable for use as a conductor.
- a conductive porous structure using foamed urethane and a metal porous structure obtained by firing foamed urethane have the disadvantages of low sheet strength and poor workability.
- a fiber structure using a polyolefin fiber, an acrylic fiber, or a carbon fiber instead of urethane foam as a material for forming a conductive porous structure or the like has been proposed.
- a conductive fiber structure hereinafter also referred to as “conductive fiber structure”
- a conductive fiber structure in which a metal film is formed on a fiber structure such as a nonwoven fabric produced using the fiber and a conductive fiber structure
- Patent Document 1 disclose a conductive fiber structure using a nonwoven fabric using synthetic fibers, a metal porous structure, and a battery electrode material using them. is there.
- Patent Document 4 is cited as a document disclosing conductive fiber structures and metal porous structures using acrylic fibers, and documents disclosing conductive fiber structures and metal porous structures using carbon fibers.
- patent document 5 is cited as a document disclosing conductive fiber structures and metal porous structures using acrylic fibers, and documents disclosing conductive fiber structures and metal porous structures using carbon fibers.
- the present invention also provides various batteries using the battery electrode material as an electrode material, preferably a positive electrode material.
- the conductive fiber structure of the present invention is a conductive fiber structure in which a metal film is formed on the fiber surface of the fiber structure, and the fiber structure includes at least one short fiber layer and at least one short fiber layer.
- the long fiber sheet has long fibers continuously extending in one direction of the sheet, and long fibers continuously extending in a direction intersecting the one direction, and the fiber structure
- the fibers constituting the short fiber layer, the fibers constituting the short fiber layer, and the long fibers constituting the long fiber sheet are entangled.
- a fiber structure refers to a structure in which a metal film is not formed
- a conductive fiber structure refers to a structure in which a metal film is formed.
- the metal film forms a network having good continuity, and has excellent electrical properties. Shows conductivity.
- the long fiber is a yarn (for example, spun yarn), a multifilament, a monofilament, or the like in which short fibers are aggregated and continuously extend.
- the long fiber sheet-like material include sheet-like materials such as a warp stretched nonwoven fabric, a woven fabric, a knitted fabric, a net-like sheet, and a mesh-like sheet.
- the thickness of the long fiber sheet is preferably 5 mm or less when measured with a 2.94 cN / cm 2 load. A more preferable thickness is 0.03 mm or more and 3 mm or less, and a particularly preferable thickness is 0.05 mm or more and 1 mm or less. When the thickness of the sheet-like material is 5 mm or less, the productivity of the conductive fiber structure can be increased, and the obtained conductive fiber structure is easy to handle.
- the mesh size of the net-like material is more preferably 1 mm or more and 15 mm or less, particularly preferably 2 mm or more and 10 mm or less, and most preferably 3 mm or more and 9 mm or less.
- the mesh formed by continuous fibers extending in one direction for example, the MD direction
- the mesh formed by continuous fibers extending in the direction intersecting the one direction for example, the CD direction
- the fiber diameter of the long fibers is 1000 ⁇ m or less, it is avoided that the long fiber sheet is too hard or difficult to bend. Therefore, in the process of laminating the short fiber layer on the long fiber sheet during the production of the conductive fiber structure, the productivity does not decrease and the handleability of the conductive fiber structure does not decrease.
- the longitudinal and transverse stretched nets are stretched in both the longitudinal direction and the transverse direction, the tensile strength is high in any direction and the handleability is excellent. Therefore, the strength of the conductive fiber structure can be increased by using the longitudinal and lateral stretched nets.
- a net obtained by stretching an unstretched extruded net in at least one direction in the longitudinal direction and the transverse direction is not only bonded at the intersection of continuous fibers continuous in different directions, but also at the intersection at the time of manufacture. By extending the thermoplastic resin in the vicinity of the intersection, the shape of the intersection expands in the plane direction.
- the cross-sectional shape of the long fiber may be any shape. Specifically, in addition to a long fiber having a circular (perfect circle) cross section, a long fiber having a non-circular cross-sectional shape, that is, a so-called irregular cross-section long fiber can be used.
- a so-called irregular cross section a polygonal shape, an elliptical shape, a flat shape, a so-called multileaf shape (specifically, a multileaf shape of 3 to 32 leaves) having a number of branch portions on the fiber surface, Examples are a star shape, a C shape, a Y shape, a W shape, and a well shape.
- the long fiber may be a solid fiber that does not have a hollow portion that is continuous in the length direction in the fiber cross section, or may be a hollow fiber that has one or more hollow portions that are continuous in the length direction. Good.
- the short fiber layer refers to a fiber aggregate in which short fibers are opened and accumulated, and is a concept that includes a fiber bonded to each other.
- the type of fiber constituting the short fiber layer, the fiber diameter, the fineness, the cross-sectional shape of the fiber, and the fiber length are not particularly limited, and various fiber webs such as the basis weight, thickness, porosity, and air permeability of the short fiber layer
- the physical properties are not particularly limited.
- the sheath component of the heat-adhesive conjugate fiber is a polyolefin resin
- a fiber structure excellent in chemical resistance such as acid resistance, alkali resistance, and organic solvent resistance
- the constituent fibers are strongly heat-bonded by heat-processing the short fiber layer containing the heat-adhesive conjugate fiber of the polyolefin resin as the sheath component. Fibrous structures can be obtained at relatively low thermal processing temperatures.
- thermoplastic resin preferably used for the core component of the heat-adhesive conjugate fiber examples include relatively high melting point polyolefin resins such as polypropylene and polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. Polyester resins such as nylon 66, nylon 12, and nylon 6 can be exemplified as the high melting point synthetic resin.
- the high melting point synthetic resin used for the core component is a thermoplastic resin having a melting point of 60 ° C. or higher than the melting point of the polyolefin resin contained in the sheath component, or a melting point of 180 ° C. or higher.
- the thermoplastic resin is preferably used. More preferably, the core component is made of a thermoplastic resin having a melting point higher by 80 ° C. or more than the melting point of the polyolefin resin, or a thermoplastic resin having a melting point of 200 ° C. or more.
- Examples of such high melting point synthetic resins include polyester resins and polyamide resins.
- the core-sheath type composite fiber in which the core component includes a polyester-based resin and the sheath component includes a polyolefin-based resin is the temperature of the polyester-based resin that is the core component at a temperature at which the polyolefin-based resin is melted to bond the fibers together. Less likely to soften, deform or melt. Therefore, such a heat-adhesive conjugate fiber has high heat resistance as compared with a heat-adhesive conjugate fiber using a polyolefin resin as a core component, and even if a heat-bonding treatment described later is performed, the fiber structure This is advantageous in that the structure is well maintained.
- the composite ratio of the heat-adhesive conjugate fiber is more preferably 2.5 / 7.5 or more and 7.5 / 2.5 or less, particularly preferably 3/7 or more and 7/3 or less, Most preferably, it is 3.5 / 6.5 or more and 6.5 / 3.5 or less.
- the ratio of the heat-bondable fibers contained in the short fiber layer is not particularly limited. Preferably, 20 mass% or more of heat bondable fibers are contained with respect to the mass of the short fiber layer.
- the short fiber layer contains 20% by mass or more of the heat-adhesive conjugate fiber, the constituent fibers of the short fiber layer and / or the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet are obtained. Can be well bonded.
- the proportion of the heat-bondable fibers contained in the short fiber layer is more preferably 50% by mass or more, particularly preferably 80% by mass or more, and 100% by mass with respect to the mass of the short fiber layer. Most preferred.
- the short fiber layer may contain fibers other than the heat-adhesive fibers or provide heat-adhesive properties as long as it provides desired electrical characteristics when a metal film is formed on the fiber surface of the fiber structure containing the short-fiber layer. You may comprise only fibers other than a fiber.
- fibers other than the heat-adhesive fibers are also referred to as “non-heat-adhesive fibers”.
- Non-thermoadhesive fibers are, for example, fibers that are selected from the natural fibers, the regenerated fibers, and the synthetic fibers and that do not exhibit thermal adhesiveness in the process of manufacturing a conductive fiber structure, and carbon fibers.
- the fiber diameter and fiber length of the non-thermal adhesive fiber, and the composite ratio in the case of a composite fiber are not particularly limited. However, if the fiber diameter and fiber length of the non-thermoadhesive fiber are significantly different from those of the thermoadhesive fiber, the productivity of the short fiber layer may be lowered, and the effect of the present invention may be impaired. is there. Therefore, the fiber diameter of the non-thermoadhesive fiber is also preferably 5 ⁇ m or more and 80 ⁇ m or less, more preferably 8 ⁇ m or more and 50 ⁇ m or less, particularly preferably 10 ⁇ m or more and 35 ⁇ m, and more preferably 15 ⁇ m or more and 25 ⁇ m or less. Most preferably.
- the fiber length of the non-thermoadhesive fiber is preferably 20 mm or more and 110 mm or less, more preferably 25 mm or more and 85 mm or less, particularly preferably 30 mm or more and 80 mm or less, 42 mm or more and 64 mm or less. Most preferably: The range of the fiber length of the preferable non-heat-bondable fiber by the manufacturing method of the short fiber layer is the same as that of the heat-bondable fiber.
- the heat-adhesive conjugate fiber has both a core component and a sheath component. It is preferable that it consists of polyolefin resin. This is because the battery electrode material is generally used by being immersed in an alkaline solution or an organic solvent.
- a preferred core / sheath combination is, for example, polypropylene / high density polyethylene.
- the fiber diameter of the heat-adhesive fiber exceeds 35 ⁇ m, the formation of the short fiber layer is deteriorated, that is, the uniformity is lowered. Therefore, an active material mixture is added to the conductive fiber structure or the metal porous structure. When filling, the active material mixture may fall off in rough parts.
- the preferred fiber diameter is the same as that of the thermal adhesive fibers. If there is a difference in the fiber diameter between the heat-adhesive fiber and the non-heat-adhesive fiber, the productivity of the short fiber layer may be lowered, and the active material mixture may not be uniformly filled.
- the basis weight of the short fiber layer is too small, unevenness may occur in the short fiber layer, and hence the fiber structure, and the active material mixture may fall off when filling the active material mixture.
- the basis weight is small, the mechanical strength of the obtained conductive fiber structure becomes small, and breakage or the like may occur during the production of the battery electrode material.
- the basis weight of the short fiber layer is too small, the resulting conductive fiber structure may be reduced in volume and difficult to be processed to a desired thickness.
- the specific volume of the short fiber layer is preferably 5 cm. 3 / g or more and 80 cm 3 / g or less, more preferably 10 cm 3 / g or more and 70 cm 3 / g or less.
- the specific volume is within this range, the active material mixture can be filled efficiently and sufficiently.
- the specific volume of the short fiber layer is too small, the gap between the constituent fibers becomes small, and a sufficient amount of the active material mixture may not be filled in the conductive structure or the metal porous structure.
- the specific volume of the short fiber layer is too large, gaps between the constituent fibers become large, and the active material mixture may fall off when filling the active material mixture.
- the short fibers constituting the fiber web are arranged so that the fiber length direction is perpendicular to the thickness direction.
- the conductive fiber structure provided with a metal film on the laminated fiber structure, and the metal porous structure obtained by firing the structure the metal-coated fiber end and the metal fiber end are not upright, and the needle-like structure Protrusion is unlikely to occur. Therefore, when these are filled with an active material, various electrode materials in which dendrite is hardly generated can be easily obtained as compared with an electrode material using a conventional urethane foam.
- the tensile strength in the MD direction is more preferably 40 N / 50 mm or more and 160 N / 50 mm or less, and particularly preferably 50 N / 50 mm or more and 150 N / 50 mm or less.
- the tensile strength in the CD direction is more preferably 15 N / 50 mm or more and 100 N / 50 mm or less, and particularly preferably 25 N / 50 mm or more and 80 N / 50 mm or less.
- the method for imparting conductivity by forming a metal film on the surface of the constituent fiber constituting the laminated fiber structure is not particularly limited, and a known method is used.
- Known methods include, for example, electroless plating, electrolytic plating (also referred to as “electroplating”), and plating methods such as molten metal plating, vacuum deposition methods, sputtering methods (also referred to as “sputtering methods”), Various physical vapor deposition methods such as resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, and ion beam deposition, thermal chemical vapor deposition (also called “thermal CVD”), photochemical vapor deposition Chemical vapor deposition such as plasma chemical vapor deposition (also called “plasma CVD”), flame spraying, high-speed flame spraying, arc spraying, etc. These are spraying methods such as plasma spraying and line explosion spraying. In consideration of productivity and cost, a plating method is preferably used.
- sulfuric acid baths mainly composed of tin sulfate, sulfuric acid, cresol sulfonic acid and formalin
- borofluoride baths mainly composed of tin borofluoride, tetrafluoroboric acid and formalin, or stannic acid
- a basic tin plating bath whose main composition is potassium and potassium hydroxide may be used.
- the metal porous structure of the present invention may be composed only of hollow metal fibers having a wall thickness of 1 ⁇ m or more, or may be composed only of metal fibers having a short side in the fiber cross section of 2 ⁇ m or more, or both. Good.
- the metal porous structure of the present invention may be provided in a compressed state as will be described later. In that case, before the compression treatment, the metal fiber which was a hollow fiber having a thickness of 1 ⁇ m or more becomes a state in which the hollow portion is lost or becomes extremely small due to compression, and the fiber regardless of whether there is a hollow or not.
- the metal porous structure of the present invention is composed of metal fibers that satisfy the above-mentioned thickness or short side conditions.
- the metal porous structure includes short metal fibers and long metal fibers having different fiber lengths.
- the metal porous structure includes at least one short metal fiber layer including the short metal fibers and the long metal fibers. Including at least one long metal fiber layer.
- the long metal fiber layer includes a long metal fiber extending continuously in one direction of the layer and a long metal fiber extending in a direction crossing the one direction.
- the short metal fiber layer is laminated on the long metal fiber layer, and at least a part of the short metal fiber is bonded to the long metal fiber at an intersection with the long metal fiber.
- the metal fiber constituting the metal porous structure of the present invention is not limited as long as it is a metal fiber that satisfies the above-mentioned thickness or short side condition, but as the metal fiber, a thin metal fiber having a relatively small fiber diameter and It is preferable that a thick metal fiber having a relatively large fiber diameter exists.
- the presence of large-diameter metal fibers having a large fiber diameter in the metal porous structure leads to the presence of metal fibers having a large cross-sectional area, that is, low electrical resistance, and the electrical resistance of the entire metal porous structure tends to be low. Because.
- both the small-diameter metal fiber and the large-diameter metal fiber may be flattened by the compression. It is. That is, in the process involving compression, when the compression ratio is particularly large, both the thin metal fiber and the large metal fiber have the same thickness (that is, the short side) in the direction parallel to the compression direction. It is because it can compress until it becomes.
- the cross-sectional shape of the metal fiber constituting the metal porous structure of the present invention is not particularly limited. Therefore, any cross-sectional shape can be used.
- the cross-sectional shape may be a non-circular cross-section, that is, a so-called irregular cross-section.
- an irregular cross section a polygonal shape, an elliptical shape, a flat shape, a so-called multileaf shape (specifically, a multileaf shape of 3 to 32 leaves) having a number of branch portions on the fiber surface, Examples are a star shape, a C shape, a Y shape, a W shape, and a well shape.
- the short side is particularly preferably 4 ⁇ m or more and 30 ⁇ m or less.
- the long side in the fiber cross section of the large-diameter metal fiber is preferably 50 ⁇ m or more and 800 ⁇ m or less, the short side is preferably 4 ⁇ m or more and 250 ⁇ m or less, and the long side is 100 ⁇ m or more. Particularly preferably, it is 300 ⁇ m or less and the short side is 4 ⁇ m or more and 200 ⁇ m or less.
- the conductive structure of the present invention and the metal porous structure formed therefrom are particularly suitable for filling pastes with a viscosity in this range.
- the long side and the short side of the metal fiber (large diameter metal fiber / small diameter metal fiber) constituting the metal porous structure were measured by the following method. First, the porous metal structure to be measured is cut and fixed to a holder so that the cut surface can be observed, and then the cut surface of the metal porous structure is observed with a scanning electron microscope in the fiber cross section of the metal fiber. Measure the length of the long and short sides. The long side and the short side are measured at 10 different points, and the average value is taken as the length of the long side and the short side of the sample.
- the measurement of the long side and the short side in the fiber cross section of the metal fiber constituting the metal porous structure can be measured by cutting the metal porous structure and observing the cut surface, and various electrode materials filled with an active material Even so, it can be measured by observing the cut surface.
- Sheet 1 Polypropylene monofilaments are arranged at equal intervals in the MD and CD directions, and the monofilament in the MD direction (filament fiber diameter: 174 ⁇ m) and the CD direction monofilament (filament fiber diameter: 187 ⁇ m) are orthogonal to each other.
- the thickness of the portion is 521 ⁇ m (intersection portion thickness / filament fiber diameter: 1.54), the mesh is 6 mm ⁇ 6 mm, the opening area is 36 mm 2 , the basis weight is 19 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 6 mm square (Conx (registered trademark) net product number R05340 manufactured by JX Nippon Mining & Metals Corporation ANCI Corporation)
- the thickness of the portion is 427 ⁇ m (intersection portion thickness / filament fiber diameter: 1.25), the mesh is 6 mm ⁇ 6 mm, the opening area is 36 mm 2 , the basis weight is 33 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 6 mm square (Conwed (registered trademark) net product number R03018 manufactured by JX Nippon Mining & Metals ANCI Corporation) Sheet 4: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilament in the MD direction (filament fiber diameter: 220 ⁇ m) and the monofilament in the CD direction (filament fiber diameter: 167 ⁇ m) are orthogonal to each other.
- the thickness of the part is 368 ⁇ m (intersection part thickness / filament fiber diameter: 1.07), the mesh is 1 mm ⁇ 1 mm, the opening area is 1 mm 2 , the basis weight is 100 g / m 2 , the opening Orthogonal net-like object whose shape is a 1 mm square (JX Nippon Mining & Metals ANCI Corporation Conwed (registered trademark) net product number X06065)
- Sheet 6 Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilaments in the MD direction (filament fiber diameter: 146 ⁇ m) and the CD direction monofilaments (filament fiber diameter: 351 ⁇ m) are orthogonal to each other.
- the thickness of the part is 244 ⁇ m (intersection part thickness / filament fiber diameter: 0.70), the mesh is 1 mm ⁇ 4 mm, the opening area is 4 mm 2 , the basis weight is 32 g / m 2 , the opening Orthogonal net-like object whose shape is a rectangle of 1 mm ⁇ 4 mm (Conx (registered trademark) net product number R03330, manufactured by JX Nippon Mining & Metals ANCI Corporation)
- a columnar water flow having a water pressure of 0.98 MPa (10 kgf / cm 2 ) is applied to the laminate having the three-layer structure by using a nozzle in which orifices having a hole diameter of 0.1 mm are provided at intervals of 0.6 mm.
- One injection was carried out.
- the laminate after the hydroentanglement treatment is dried at 110 ° C. using a hot air blowing type heat treatment machine, and then further subjected to heat treatment at 140 ° C. for 13 seconds using a hot air blowing type heat treatment machine. Were thermally bonded to obtain a laminated fiber structure.
- the obtained laminated fiber structure was cut into a size of 17.6 cm ⁇ 28 cm, and a catalyst treatment (catalyst) using a solution containing stannous chloride, palladium chloride and the like was performed on the laminated fiber structure. Then, in addition to a water-soluble nickel compound, an electroless nickel plating solution containing a known complexing agent and reducing agent is impregnated with the laminated fiber structure that has been subjected to the catalytic treatment, electroless plating is performed, and nickel is applied to the fiber surface. A film was formed to obtain a conductive fiber structure. In this conductive fiber structure, the amount of nickel attached to the fiber surface was 0.111 g, and the plating amount per unit area was 4.53 g / m 2 .
- Examples 2 to 12 Laminated fiber structure in the same procedure as that used in the production of Example 1 except that the fibers constituting the short fiber layer and the long fiber sheet were changed to those shown in Tables 1 and 2, respectively. In addition, a conductive fiber structure was obtained.
- Example 1 A single-layer fiber structure was obtained by heat bonding. A nickel film was formed on the fiber surface of the obtained fiber structure to obtain a conductive fiber structure. The nickel film was formed by the same procedure as that adopted in Example 1.
- the MD / CD ratio of electrical resistance was measured and evaluated.
- the laminated fiber structures of Examples 1 to 12 and the single layers of Comparative Examples 1 to 5 were measured before the treatment for forming the metal film on the constituent fiber surface.
- Tables 1 and 2 show the basis weight, thickness, density, specific volume, MD direction, tensile strength in the CD direction, and MD / CD ratio of tensile strength of the structural fiber structure. Further, scanning micrographs obtained by photographing the surfaces of the conductive fiber structures of Examples 2 and 7 are shown in FIGS.
- the conductive fiber structures of Examples 1 to 12 having a three-layer structure in which the middle layer is a long fiber sheet-like material are conductive layers having a single layer structure manufactured using the same short fibers.
- the electrical resistance in at least one of the MD direction and the CD direction was low. This is considered to be because the short fibers are entangled well due to the presence of the long fiber sheet.
- Example 4 shows a lower total electrical resistance. It was.
- the total sum of electric resistances is the sum of the electric resistance value in the MD direction and the electric resistance value in the CD direction. This is because if the fiber diameter of the long fibers is thick, the fibers in the short fiber layer are not easily entangled with the long fibers, or the fibers in the short fiber layer are not easily entangled with each other, and the continuity of the metal film is slightly reduced. It is thought that.
- Example 13 First, the fiber structure of Example 13 will be described. Using a parallel card machine, a parallel card web having a basis weight of 15 g / m 2 was produced as a short fiber layer using only the fiber 2. Next, the sheet 1 was placed on the card web made of the fibers 2. A parallel card web made of the fibers 2 and having a basis weight of 15 g / m 2 was further laminated on the sheet 1 to produce a laminate having a three-layer structure in which the sheet 1 was arranged at the center. . A hydroentanglement process using a high-pressure water stream was performed on the laminate having the three-layer structure.
- Nickel plating was performed for Example 7 and Comparative Examples 1, 2, 4, and 5 so that the amount of nickel per unit area was 400 g / m 2 .
- the nickel amount per unit area was 350 g / m 2 .
- the conductive structure was subjected to a heat treatment to remove the heat-dissipating substance constituting the fiber structure to obtain a metal porous structure. Thereafter, the conductive fiber structure was processed to have a thickness of 1.5 mm. In the heat treatment, after removing the heat-dissipating substance at 600 ° C., nickel was reduced in a reducing atmosphere at 1000 ° C. (using ammonia decomposition gas or the like).
- the conductive fiber structure and metal porous structure of the present invention can be used for various electronic parts such as electromagnetic wave sealing materials, filters, accessories, and grounding materials.
- battery electrode materials for example, nickel-hydrogen batteries
- electrode material characteristics for example, current collection characteristics
- Various electrode materials for alkaline secondary batteries and lithium ion secondary batteries can be obtained.
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Abstract
In the present invention, a conductive fiber structure is obtained by forming a metal coating on the fiber surface of a laminated fiber structure in which integrated are at least one short fiber layer and at least one long fiber sheet-like article that includes the following: a long fiber that continuously extends in one direction of a sheet; and a long fiber that continuously extends in a direction intersecting the one direction.
Description
本発明は、繊維表面に金属皮膜が形成された導電性繊維構造物、前記導電性繊維構造物を焼成することで得られる金属多孔構造物、及び前記導電性繊維構造物または金属多孔構造物を用いた電池用電極材、及びそれらの電池用電極材を用いた電池に関する。
The present invention provides a conductive fiber structure in which a metal film is formed on a fiber surface, a metal porous structure obtained by firing the conductive fiber structure, and the conductive fiber structure or metal porous structure. It is related with the battery electrode material used, and the battery using those battery electrode materials.
電極材を始めとする電池用部材等の各種電子部品、電磁波シール材、フィルター、アクセサリー、及びアース接地材料等に使用される、導電性を有する多孔質構造物として、様々なものが提案されている。
Various porous structures have been proposed as conductive porous structures used in various electronic parts such as battery materials such as electrode materials, electromagnetic wave sealing materials, filters, accessories, and grounding materials. Yes.
導電性の多孔質構造物として、例えば、発泡ウレタン等の樹脂からなるスポンジ状物に、めっき、真空蒸着、または化学蒸着などの処理を行って、その表面にニッケル、銅、クロム、またはコバルトなどの金属皮膜を形成した導電性の多孔構造物が知られている。さらに、金属皮膜を形成した導電性の多孔質構造物を焼成し、発泡ウレタンを消失させて得られる、金属の繊維状物からなる多孔質構造物(以下、「金属多孔構造物」とも称す)もまた、導電性の多孔質構造物として知られている。スポンジ状物に金属皮膜を形成した導電性の多孔構造物は、シートの厚み方向、長さ方向、及び巾方向において均一であることから、導電体として用いるのに適している。しかし、発泡ウレタンを用いた導電性の多孔構造物及び発泡ウレタンを焼成して得られる金属多孔構造物は、シート強度が低く、加工性に乏しいという欠点を有している。
As a conductive porous structure, for example, a sponge-like material made of resin such as urethane foam is subjected to a treatment such as plating, vacuum deposition, or chemical vapor deposition, and the surface thereof is nickel, copper, chromium, cobalt, or the like. A conductive porous structure having a metal film formed thereon is known. Furthermore, the porous structure which consists of a metallic fibrous material obtained by baking the electroconductive porous structure which formed the metal membrane | film | coat, and lose | disappearing urethane foam (henceforth "metal porous structure") Is also known as a conductive porous structure. A conductive porous structure in which a metal film is formed on a sponge-like material is uniform in the thickness direction, length direction, and width direction of the sheet, and is therefore suitable for use as a conductor. However, a conductive porous structure using foamed urethane and a metal porous structure obtained by firing foamed urethane have the disadvantages of low sheet strength and poor workability.
また、発泡ウレタンを用いた導電性の多孔構造物及び金属多孔構造物の製造に際しては、発泡ウレタンを実際に使用される用途に適した厚みに切断する(スライスする)必要がある。発泡ウレタンを切断すると、図10に示すように、骨格部分が切断された端部が数多く形成され、その一部は、図11に示すように、切断面に対して垂直方向に直立した針状突起を形成することがある。この針状突起は、例えば、導電性の多孔構造物または金属多孔物を電極材として電池に組み込んだ際、デンドライトが形成される要因となる。このデンドライトが成長すると電池内部のセパレータを貫通及び/または破損し、短絡を引き起こす可能性がある。
Also, in the production of a conductive porous structure and a metal porous structure using foamed urethane, it is necessary to cut (slice) the foamed urethane to a thickness suitable for the practical use. When the foamed urethane is cut, as shown in FIG. 10, a large number of end portions where the skeleton portion is cut are formed, and a part thereof is a needle-like shape that stands upright in the direction perpendicular to the cut surface as shown in FIG. Protrusions may be formed. For example, the needle-like projections cause dendrite to be formed when a conductive porous structure or a metal porous material is incorporated into a battery as an electrode material. When this dendrite grows, it may penetrate and / or break the separator inside the battery, causing a short circuit.
そこで、導電性の多孔構造物等を構成するための材料として、発泡ウレタンに代えて、ポリオレフィン系繊維、アクリル系繊維、または炭素繊維を使用した繊維構造物が提案されている。具体的には、前記繊維を用いて作製した不織布等の繊維構造物に金属皮膜を形成した導電性を有する繊維構造物(以下、「導電性繊維構造物」とも称す)、導電性繊維構造物を焼成して不織布を消失させた金属多孔構造物、及びそれらを用いた電池用電極材が提案されている。合成繊維を用いた不織布を使用した導電性繊維構造物、金属多孔構造物、及びそれらを用いた電池用電極材を開示する文献として、例えば、特許文献1、特許文献2、及び特許文献3がある。また、アクリル系繊維を使用した導電性繊維構造物及び金属多孔構造物を開示する文献として、特許文献4が挙げられ、炭素繊維を使用した導電性繊維構造物及び金属多孔構造物を開示する文献として特許文献5がある。
Therefore, a fiber structure using a polyolefin fiber, an acrylic fiber, or a carbon fiber instead of urethane foam as a material for forming a conductive porous structure or the like has been proposed. Specifically, a conductive fiber structure (hereinafter also referred to as “conductive fiber structure”), a conductive fiber structure in which a metal film is formed on a fiber structure such as a nonwoven fabric produced using the fiber, and a conductive fiber structure A porous metal structure in which a nonwoven fabric is eliminated by baking and a battery electrode material using them has been proposed. For example, Patent Document 1, Patent Document 2, and Patent Document 3 disclose a conductive fiber structure using a nonwoven fabric using synthetic fibers, a metal porous structure, and a battery electrode material using them. is there. Patent Document 4 is cited as a document disclosing conductive fiber structures and metal porous structures using acrylic fibers, and documents disclosing conductive fiber structures and metal porous structures using carbon fibers. There exists patent document 5.
導電性繊維構造物及び金属多孔構造物に対しては、より高い電気伝導性を有することが要求される。電気伝導性は種々の要因により影響を受ける。例えば、より高い電気伝導性は、導電性繊維構造物または金属多孔構造物において、導電体である金属皮膜がより高い連続性をもって存在する(即ち、導電体の不連続箇所がより少ない)ことで確保される。導電体の連続性は、金属皮膜が形成される繊維構造物の構造による影響を受ける。
It is required that the conductive fiber structure and the metal porous structure have higher electrical conductivity. Electrical conductivity is affected by various factors. For example, higher electrical conductivity is due to the presence of a conductive metal film having a higher continuity in a conductive fiber structure or a metal porous structure (ie, fewer discontinuities in the conductor). Secured. The continuity of the conductor is affected by the structure of the fiber structure on which the metal film is formed.
また、上記特許文献に開示される導電性繊維構造物、金属多孔構造物、及びそれらを用いた電池用電極材は、いずれも有機材料からなる繊維(炭素繊維を含む)の不織布を使用している。そのため、それらは柔軟であり、電池用電極材として使用した場合、巻回してもその性能が低下しない。したがって、それらは、発泡ウレタンを用いた導電性の多孔構造物及び金属多孔構造物と比較して加工性に優れたものであるが、以下の欠点を有する。まず、前記特許文献5に開示される、炭素繊維を用いた導電性繊維構造物は、原料となる炭素繊維が熱接着性を有しないため、繊維構造物を作製するに際し、バインダーとなる樹脂が必要である。
In addition, the conductive fiber structure, the metal porous structure, and the battery electrode material using the same disclosed in the above-mentioned patent documents all use a nonwoven fabric of fibers (including carbon fibers) made of an organic material. Yes. Therefore, they are flexible, and when used as a battery electrode material, their performance does not deteriorate even if they are wound. Therefore, they are excellent in processability as compared with conductive porous structures and metal porous structures using urethane foam, but have the following drawbacks. First, in the conductive fiber structure using carbon fiber disclosed in Patent Document 5, since the carbon fiber used as a raw material does not have thermal adhesiveness, a resin serving as a binder is required when producing the fiber structure. is necessary.
次に、前記特許文献4に開示される導電性繊維構造物は、アクリル繊維を用い、水流交絡法によって得られた不織布を用いている。この不織布は、見掛け密度が0.2g/cm3以上と高く、繊維間の空隙が少ない不織布である。見掛け密度が高い不織布を用いて作製した導電性繊維構造物は、発泡ウレタンを用いたシートに金属皮膜を形成した導電性の多孔構造物に比べて、通気度が低いか、あるいはその取り扱い性が悪く、後加工性が低下するという課題を有している。また、前記導電性繊維構造物または前記金属多孔構造物の内部に充填物を詰める用途に使用する際、繊維間の空隙が少ないため、充填物の充填性が悪くなる。
Next, the conductive fiber structure disclosed in Patent Document 4 uses an acrylic fiber and a nonwoven fabric obtained by a hydroentanglement method. This nonwoven fabric is a nonwoven fabric having a high apparent density of 0.2 g / cm 3 or more and few voids between fibers. The conductive fiber structure produced using a non-woven fabric with a high apparent density has a lower air permeability or is easier to handle than a conductive porous structure in which a metal film is formed on a sheet using urethane foam. It is bad and has the subject that post-processability falls. Moreover, when using for the use which fills the inside of the said conductive fiber structure or the said metal porous structure, since the space | gap between fibers is few, the filling property of a filler worsens.
また特許文献1~3に開示されているポリオレフィン系樹脂からなる芯鞘型複合繊維を用いた不織布は、前記芯鞘型複合繊維の鞘成分の融点と、芯成分の融点との差が小さいため、加熱処理によって、不織布全体の嵩が減少する、いわゆる“へたり”が発生する場合がある。導電性繊維構造物において、構成繊維同士の接着がはずれると、各種電気特性が低下する原因となるため、構成繊維同士が強固に接着していることが求められる。そのため、繊維同士を接着する際の加熱処理の温度を、より高温で行うことが求められる。しかし、加熱処理をより高温で行うほど、不織布の“へたり“が顕著になる。不織布の“へたり“により、不織布の嵩、及び繊維間空隙が減少し、不織布が密なものになる。そのため、前記特許文献4に関連して説明したような課題が生じる。
In addition, the nonwoven fabric using the core-sheath composite fiber made of polyolefin resin disclosed in Patent Documents 1 to 3 has a small difference between the melting point of the sheath component of the core-sheath composite fiber and the melting point of the core component. The heat treatment may cause so-called “sagging” in which the bulk of the nonwoven fabric decreases. In the conductive fiber structure, when the constituent fibers are not bonded to each other, various electrical characteristics are deteriorated. Therefore, the constituent fibers are required to be firmly bonded to each other. Therefore, it is required that the temperature of the heat treatment for bonding the fibers is higher. However, as the heat treatment is performed at a higher temperature, the “sagging” of the nonwoven fabric becomes more prominent. Due to the “sagging” of the nonwoven fabric, the bulk of the nonwoven fabric and the inter-fiber gap are reduced, and the nonwoven fabric becomes dense. Therefore, the problem described in relation to Patent Document 4 occurs.
また、前記特許文献1~4に記載の導電性繊維構造物、金属多孔構造物、及びそれらを用いた電池用電極材は、繊維ウェブ、例えばカードウェブを用いた不織布から製造されている。繊維ウェブ、特にカードウェブを用いて製造した不織布は、構成繊維が一方向、特に不織布のMD方向(以下、縦方向または生産方向とも称す)に配向する傾向がある。そのため、得られる導電性繊維構造物、金属多孔構造物、及びそれらを用いた電池用電極材においては、その力学的特性、例えば引張強力は、不織布のMD方向において高く、CD方向(以下、横方向または巾方向とも称す)において低くなる傾向がある。さらに、得られた導電性繊維構造物及び金属多孔構造物の電気伝導性が、MD方向においては高く、CD方向においては低くなる傾向がある。
Also, the conductive fiber structure, metal porous structure, and battery electrode material using them described in Patent Documents 1 to 4 are manufactured from a nonwoven fabric using a fiber web, for example, a card web. In a nonwoven fabric produced using a fiber web, particularly a card web, the constituent fibers tend to be oriented in one direction, particularly in the MD direction of the nonwoven fabric (hereinafter also referred to as the longitudinal direction or production direction). Therefore, in the obtained conductive fiber structure, metal porous structure, and battery electrode material using them, the mechanical properties, such as tensile strength, are high in the MD direction of the nonwoven fabric, and the CD direction (hereinafter referred to as the transverse direction). Tend to be low in the direction or width direction). Furthermore, the electrical conductivity of the obtained conductive fiber structure and metal porous structure tends to be high in the MD direction and low in the CD direction.
本発明は、良好な電気特性を有し、好ましくは嵩高であり、かつ好ましくは力学的特性及び電気伝導特性において方向依存性が低い導電性繊維構造物及び金属多孔構造物、及びそれらを用いた電池用電極材、並びにそれらを組み込んだ各種電池を提供することを目的とする。
The present invention has a conductive fiber structure and a metal porous structure having good electrical characteristics, preferably bulky, and preferably low in direction dependency in mechanical characteristics and electrical conductivity characteristics, and using the same It aims at providing the electrode material for batteries, and the various batteries incorporating them.
本発明者は、前記課題を解決すべく検討を行い、短繊維層に、所定の長繊維シート状物を積層してなる積層物に、めっきなどの電気伝導性を付与する処理を行うことで、上記課題を解決する導電性繊維構造物を得ることができることを見いだした。
The present inventor has studied to solve the above-mentioned problems, and performs a treatment for imparting electrical conductivity such as plating to a laminate formed by laminating a predetermined long fiber sheet-like material on a short fiber layer. The present inventors have found that a conductive fiber structure that solves the above problems can be obtained.
本発明は、繊維構造物の繊維表面に金属皮膜が形成されてなる導電性繊維構造物であって、
前記繊維構造物は、少なくとも1つの短繊維層と、少なくとも1つの長繊維シート状物とを含み、
前記長繊維シート状物は、シートの一方向に連続して延びる長繊維と、前記一方向と交差する方向に連続して延びる長繊維を含み、
前記繊維構造物において、前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とが交絡している、
導電性繊維構造物を提供する。 The present invention is a conductive fiber structure in which a metal film is formed on the fiber surface of the fiber structure,
The fiber structure includes at least one short fiber layer and at least one long fiber sheet.
The long fiber sheet-like material includes long fibers continuously extending in one direction of the sheet, and long fibers continuously extending in a direction crossing the one direction,
In the fiber structure, the fibers constituting the short fiber layer, and the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet are entangled.
A conductive fiber structure is provided.
前記繊維構造物は、少なくとも1つの短繊維層と、少なくとも1つの長繊維シート状物とを含み、
前記長繊維シート状物は、シートの一方向に連続して延びる長繊維と、前記一方向と交差する方向に連続して延びる長繊維を含み、
前記繊維構造物において、前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とが交絡している、
導電性繊維構造物を提供する。 The present invention is a conductive fiber structure in which a metal film is formed on the fiber surface of the fiber structure,
The fiber structure includes at least one short fiber layer and at least one long fiber sheet.
The long fiber sheet-like material includes long fibers continuously extending in one direction of the sheet, and long fibers continuously extending in a direction crossing the one direction,
In the fiber structure, the fibers constituting the short fiber layer, and the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet are entangled.
A conductive fiber structure is provided.
本発明はまた、金属繊維で構成された金属多孔構造物を提供する。本発明の金属多孔構造物は、肉厚が1μm以上の中空金属繊維、及び繊維断面において、短辺が2μm以上である金属繊維から選択される少なくとも1種類の金属繊維で構成される金属多孔構造物であって、
前記金属多孔構造物を構成する金属繊維として、繊維長の異なる短金属繊維と長金属繊維が存在し、
前記金属多孔構造物は、前記短金属繊維を含む少なくとも1つの短金属繊維層と、前記長金属繊維を含む少なくとも1つ長金属繊維層を含み、
前記長金属繊維層は、シートの一方向に連続して延びる長金属繊維と、前記一方向と交差する方向に連続して延びる長金属繊維を含み、
前記短金属繊維の少なくとも一部は、前記長金属繊維との交点で前記長金属繊維に接合していることを特徴とする金属多孔構造物である。 The present invention also provides a metal porous structure composed of metal fibers. The metal porous structure of the present invention is a metal porous structure composed of at least one metal fiber selected from hollow metal fibers having a thickness of 1 μm or more and metal fibers having a short side of 2 μm or more in the fiber cross section. A thing,
As metal fibers constituting the metal porous structure, there are short metal fibers and long metal fibers having different fiber lengths,
The metal porous structure includes at least one short metal fiber layer including the short metal fiber, and at least one long metal fiber layer including the long metal fiber,
The long metal fiber layer includes a long metal fiber continuously extending in one direction of the sheet, and a long metal fiber continuously extending in a direction intersecting the one direction,
At least a part of the short metal fiber is a porous metal structure characterized in that the short metal fiber is bonded to the long metal fiber at an intersection with the long metal fiber.
前記金属多孔構造物を構成する金属繊維として、繊維長の異なる短金属繊維と長金属繊維が存在し、
前記金属多孔構造物は、前記短金属繊維を含む少なくとも1つの短金属繊維層と、前記長金属繊維を含む少なくとも1つ長金属繊維層を含み、
前記長金属繊維層は、シートの一方向に連続して延びる長金属繊維と、前記一方向と交差する方向に連続して延びる長金属繊維を含み、
前記短金属繊維の少なくとも一部は、前記長金属繊維との交点で前記長金属繊維に接合していることを特徴とする金属多孔構造物である。 The present invention also provides a metal porous structure composed of metal fibers. The metal porous structure of the present invention is a metal porous structure composed of at least one metal fiber selected from hollow metal fibers having a thickness of 1 μm or more and metal fibers having a short side of 2 μm or more in the fiber cross section. A thing,
As metal fibers constituting the metal porous structure, there are short metal fibers and long metal fibers having different fiber lengths,
The metal porous structure includes at least one short metal fiber layer including the short metal fiber, and at least one long metal fiber layer including the long metal fiber,
The long metal fiber layer includes a long metal fiber continuously extending in one direction of the sheet, and a long metal fiber continuously extending in a direction intersecting the one direction,
At least a part of the short metal fiber is a porous metal structure characterized in that the short metal fiber is bonded to the long metal fiber at an intersection with the long metal fiber.
本発明の金属多孔構造物は、好ましくは、前記短繊維層及び前記長繊維シート状物が熱消失性物質からなる前記導電性繊維構造物を加熱処理に付して、熱消失性物質を加熱除去してなるものである。
In the metal porous structure of the present invention, preferably, the heat-dissipative substance is heated by subjecting the conductive fiber structure, in which the short fiber layer and the long fiber sheet are made of a heat-dissipative substance, to a heat treatment. It is removed.
本発明はまた、前記導電性繊維構造物または前記金属多孔構造物に、活物質合剤が充填されている、電池用電極材を提供する。
The present invention also provides a battery electrode material in which the conductive fiber structure or the metal porous structure is filled with an active material mixture.
本発明はまた、前記電池用電極材を電極材、好ましくは正極材として使用した各種電池を提供する。
The present invention also provides various batteries using the battery electrode material as an electrode material, preferably a positive electrode material.
本発明の導電性繊維構造物、金属多孔構造物、及び電池用電極材は、特定の長繊維シート状物と、短繊維層とを含み、構成繊維同士が交絡している繊維構造物を有する、またはこの繊維構造物を用いて製造されることを特徴とする。この特徴により、本発明の導電性繊維構造物、金属多孔構造物、及び電池用電極材は、良好な電気伝導性を有する。また、長繊維シート状物を用いることにより力学的特性及び電気伝導特性において方向依存性が低い導電性繊維構造物、金属多孔構造物、及びそれらを用いた電池用電極材を得ることができる。特に、本発明の導電性繊維構造物を出発原料として電極材を製造する場合には、導電性繊維構造物の力学的特性及び電気伝導特性の方向依存性が低いだけでなく、電極材に不可欠な活物質を、その充填量を均一にして充填できるので、高品質の電極材を安定して製造することが可能となる。
The conductive fiber structure, metal porous structure, and battery electrode material of the present invention include a specific long fiber sheet-like material and a short fiber layer, and have a fiber structure in which constituent fibers are entangled with each other. Or manufactured using this fiber structure. With this feature, the conductive fiber structure, metal porous structure, and battery electrode material of the present invention have good electrical conductivity. Further, by using a long fiber sheet-like material, it is possible to obtain a conductive fiber structure, a metal porous structure, and a battery electrode material using them, which are low in direction dependency in mechanical characteristics and electrical conduction characteristics. In particular, when an electrode material is produced using the conductive fiber structure of the present invention as a starting material, not only the direction dependency of the mechanical and electrical conduction characteristics of the conductive fiber structure is low, but also indispensable for the electrode material. Therefore, it is possible to stably produce a high-quality electrode material.
本発明の導電性繊維構造物は、繊維構造物の繊維表面に金属皮膜が形成されてなる導電性繊維構造物であって、前記繊維構造物が、少なくとも1つの短繊維層と、少なくとも1つの長繊維シート状物を含み、前記長繊維シート状物は、シートの一方向に連続して延びる長繊維と、前記一方向と交差する方向に連続して延びる長繊維を有し、前記繊維構造物において、前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とが交絡していることを特徴とする。本明細書において、繊維構造物は、金属皮膜が形成されていない構造物を指し、導電性繊維構造物は金属皮膜が形成されている構造物を指す。この導電性繊維構造物は、長繊維シート状物の存在によって、短繊維層の繊維同士が良好に交絡しているために、金属皮膜が良好な連続性を有するネットワークを形成し、優れた電気伝導性を示す。
The conductive fiber structure of the present invention is a conductive fiber structure in which a metal film is formed on the fiber surface of the fiber structure, and the fiber structure includes at least one short fiber layer and at least one short fiber layer. Including a long fiber sheet, the long fiber sheet has long fibers continuously extending in one direction of the sheet, and long fibers continuously extending in a direction intersecting the one direction, and the fiber structure In the product, the fibers constituting the short fiber layer, the fibers constituting the short fiber layer, and the long fibers constituting the long fiber sheet are entangled. In this specification, a fiber structure refers to a structure in which a metal film is not formed, and a conductive fiber structure refers to a structure in which a metal film is formed. In this conductive fiber structure, since the fibers of the short fiber layer are entangled well due to the presence of the long fiber sheet, the metal film forms a network having good continuity, and has excellent electrical properties. Shows conductivity.
また、前記長繊維シート状物は、短繊維層と比較して特定の一方向、例えばMD方向に構成繊維が配向する割合が大きくなく、前記特定の一方向と交差する方向、例えばCD方向にも繊維が配向している。それにより、導電性繊維構造物において、前記特定の一方向だけでなく、当該一方向と交差する方向にも高い導電性を与える。その結果、例えば、MD方向の電気抵抗とCD方向の電気抵抗の差が小さくなり得る。また、長繊維シート状物は、導電性繊維構造物において、特定の一方向だけでなく、当該一方向と交差する方向にも良好な力学的特性を与えることができ、例えば、MD方向の引張強力とCD方向の引張強力の差を小さくすることができる。
In addition, the long fiber sheet-like material is not large in the proportion of the constituent fibers oriented in a specific direction, for example, the MD direction, compared to the short fiber layer, and in a direction intersecting the specific direction, for example, the CD direction. Also the fibers are oriented. Thereby, in the conductive fiber structure, high conductivity is given not only in the specific one direction but also in a direction intersecting with the one direction. As a result, for example, the difference between the electrical resistance in the MD direction and the electrical resistance in the CD direction can be reduced. Further, the long fiber sheet-like material can give good mechanical properties not only in one specific direction but also in a direction intersecting the one direction in the conductive fiber structure, for example, in the MD direction. The difference between the strength and the tensile strength in the CD direction can be reduced.
以下に、本発明の導電性繊維構造物を構成する長繊維シート状物について説明する。本発明の導電性繊維構造物を構成する長繊維シート状物は、シートの一方向に連続して延びる長繊維と、前記特定の一方向と交差する方向に連続して延びる長繊維を有する。「長繊維」とは、これを含むシート状物を所定の大きさで使用したときに、当該大きさのシート状物内で所定の方向において連続して延びる繊維をいう。長繊維シート状物に含まれる長繊維は、150mm以上の繊維長を有するものであれば充分な長さを有しているが、好ましくは、前記所定の大きさのシート内で連続している、即ち、シートの一方向の両端部の間で連続している。長繊維は、短繊維が集合して連続して延びる糸条(例えば、紡績糸)、マルチフィラメント、及びモノフィラメント等である。長繊維シート状物としては、例えば、経緯延伸配列不織布、織物、編物、ネット状シート、メッシュ状シートなどのシート状物が挙げられる。長繊維シート状物の厚みは、2.94cN/cm2荷重で測定したときに、5mm以下であることが好ましい。より好ましい厚みは、0.03mm以上、3mm以下であり、特に好ましい厚みは0.05mm以上、1mm以下である。シート状物の厚みが5mm以下であると、導電性繊維構造物の生産性を高くすることができ、また、得られる導電性繊維構造物が取り扱いやすい。
Below, the long fiber sheet-like material which comprises the electroconductive fiber structure of this invention is demonstrated. The long fiber sheet-like material constituting the conductive fiber structure of the present invention has long fibers continuously extending in one direction of the sheet and long fibers continuously extending in a direction intersecting with the specific one direction. “Long fiber” refers to a fiber that continuously extends in a predetermined direction in a sheet-like material having a predetermined size when a sheet-like material including the same is used in a predetermined size. The long fiber contained in the long fiber sheet has a sufficient length as long as it has a fiber length of 150 mm or more, but is preferably continuous in the sheet having the predetermined size. That is, it is continuous between both ends in one direction of the sheet. The long fiber is a yarn (for example, spun yarn), a multifilament, a monofilament, or the like in which short fibers are aggregated and continuously extend. Examples of the long fiber sheet-like material include sheet-like materials such as a warp stretched nonwoven fabric, a woven fabric, a knitted fabric, a net-like sheet, and a mesh-like sheet. The thickness of the long fiber sheet is preferably 5 mm or less when measured with a 2.94 cN / cm 2 load. A more preferable thickness is 0.03 mm or more and 3 mm or less, and a particularly preferable thickness is 0.05 mm or more and 1 mm or less. When the thickness of the sheet-like material is 5 mm or less, the productivity of the conductive fiber structure can be increased, and the obtained conductive fiber structure is easy to handle.
長繊維シート状物としては、ネット状のシート(以下、単に「ネット状物」とも称す)を使用することが好ましい。ネット状物とは、少なくとも異なる2つの方向に連続して延びる連続繊維によって囲まれる開口部を有するシートを指す。前記ネット状物を長繊維シート状物として用いると、短繊維層の繊維同士がより良好に交絡して、金属皮膜の連続性が向上し、優れた電気伝導性が得られる。
As the long fiber sheet, it is preferable to use a net-like sheet (hereinafter also simply referred to as “net-like”). The net-like material refers to a sheet having an opening surrounded by continuous fibers extending continuously in at least two different directions. When the net-like material is used as a long fiber sheet material, the fibers of the short fiber layer are entangled better, the continuity of the metal film is improved, and excellent electrical conductivity is obtained.
前記ネット状物について説明する。ネット状物において、連続繊維とみなす長繊維は、使用時に所定の大きさに切断したときに、当該大きさのシート状物内で一方向、及びその一方向と交差する方向において連続している繊維を含む。ネット状物は、少なくとも異なる2つの方向に配向し、連続して延びる連続繊維を並べることで形成されている。連続繊維は異なる2つの方向に配向するように配置されてもよいし、異なる3以上の方向に配向するように配置されてもよいし、あるいは完全にランダムな状態で配置されてもよい。ネット状物は、連続繊維を異なる4以下の方向に配向させて並べて形成されることが好ましく、異なる2方向に連続繊維を配向させて形成されることが特に好ましい。
The net-like object will be described. In a net-like material, long fibers regarded as continuous fibers are continuous in one direction and in a direction crossing the one direction in a sheet-like material of that size when cut into a predetermined size at the time of use. Contains fiber. The net-like object is formed by arranging continuous fibers that are oriented in at least two different directions and extend continuously. The continuous fibers may be arranged to be oriented in two different directions, may be arranged to be oriented in three or more different directions, or may be arranged in a completely random state. The net-like material is preferably formed by aligning continuous fibers in four or less different directions, and particularly preferably formed by aligning continuous fibers in two different directions.
ネット状物においては、異なる2以上の方向に配向して並べられた連続繊維によって囲まれた開口部が形成される。前記連続繊維が完全にランダムな状態で並べられていた場合、開口部の形状もそれに伴いランダムな形状になる。前記のように、連続繊維は4以下の方向に配向させて並べることが好ましく、2方向に配向させて並べることが特に好ましい。よって前記開口部分の形状は三角形、正方形、長方形、または菱形であることが好ましく、正方形、長方形、または菱形であることが特に好ましい。
In the net-like material, an opening surrounded by continuous fibers aligned in two or more different directions is formed. When the continuous fibers are arranged in a completely random state, the shape of the opening also becomes a random shape accordingly. As described above, the continuous fibers are preferably aligned in four or less directions, and particularly preferably aligned in two directions. Therefore, the shape of the opening is preferably a triangle, square, rectangle, or rhombus, and is particularly preferably a square, rectangle, or rhombus.
ネット状物において、シートを構成する特定の一方向に連続して延びる連続繊維が配向する方向はいずれの方向であってよい。また、ネット状物において、前記特定の一方向に延びる連続繊維と、当該一方向と交差する方向に連続して延びる連続繊維とは、いかなる角度で交差、あるいは交差した点で接合していてもよい。異なる2方向に連続して延びる連続繊維は、好ましくは30°以上、90°以下、より好ましくは45°以上、90°以下、特に好ましくは60°以上、90°以下の鋭角を形成して交差、あるいは交差した点で接合する。そのような鋭角を形成して、2つの方向に連続繊維が配向しているネット状物は、導電性繊維構造物の電気特性、及び/または力学的特性の方向依存性をより少なくする。
In the net-like material, the direction in which the continuous fibers continuously extending in one specific direction constituting the sheet is oriented may be any direction. Further, in the net-like object, the continuous fiber extending in one specific direction and the continuous fiber extending continuously in the direction intersecting with the one direction may be joined at any angle or at a crossing point. Good. The continuous fibers extending continuously in two different directions preferably form an acute angle of 30 ° or more and 90 ° or less, more preferably 45 ° or more and 90 ° or less, and particularly preferably 60 ° or more and 90 ° or less. Or join at the crossing point. A net that forms such an acute angle and the continuous fibers are oriented in two directions makes the electrical and / or mechanical properties of the conductive fiber structure less dependent on direction.
前記のネット状物は、異なる2つの方向に配向して連続繊維が並べられ、特定の一方向に連続する連続繊維と、これと交差する連続繊維が直交したネット状物(以下、「直交ネット状物」とも呼ぶ)であることが好ましい。直交ネット状物は入手しやすく、導電性繊維構造物の電気特性、及び/または力学的特性の方向依存性をより少なくする効果が高いためである。
The net-like material is a net-like material in which continuous fibers are aligned in two different directions and a continuous fiber that is continuous in one specific direction and a continuous fiber that intersects the continuous fiber are orthogonal (hereinafter referred to as an “orthogonal net” It is also preferable to be referred to as a “form”. This is because the orthogonal net-like material is easily available and has a high effect of reducing the direction dependency of the electrical properties and / or mechanical properties of the conductive fiber structure.
ネット状物において、ネット状物を構成する連続繊維の間隔(以下、単に「目合い」と称す)は特に限定されず、例えば、1mm以上、20mm以下であることが好ましい。目合いが1mm未満であると、導電性繊維構造物の通気度が低下し、通気度を必要とする用途には適さなくなるおそれがある。また、目合いが狭すぎると、ネット状物を構成する連続繊維の繊維径によっては、硬くなったり、曲げにくくなったりすることがあり、ネット状物及びそれを含む導電性繊維構造物の取扱い性及び後加工性が低下するおそれがある。さらに、目合いが狭すぎると、後述する短繊維層とネット状物を交絡させる場合、特に2つの短繊維層の間にネット状物を挟んで交絡一体化させる際に、短繊維層の繊維とネット状物を構成する連続繊維との交絡性、あるいはネット状物の両側に位置する2つの短繊維層の繊維同士の交絡性が低下する傾向にある。交絡性の低下は、得られる導電性構造物における電気伝導性の低下を招くことがある。
In the net-like material, the interval between the continuous fibers constituting the net-like material (hereinafter simply referred to as “mesh”) is not particularly limited, and is preferably 1 mm or more and 20 mm or less, for example. If the mesh size is less than 1 mm, the air permeability of the conductive fiber structure is lowered, and there is a possibility that it is not suitable for applications requiring air permeability. If the mesh is too narrow, depending on the fiber diameter of the continuous fibers constituting the net-like material, it may become hard or difficult to bend. Handling of the net-like material and the conductive fiber structure including the net-like material may be difficult. And post-processability may be deteriorated. Furthermore, when the mesh is too narrow, when the short fiber layer and the net-like material to be described later are entangled, particularly when the net-like material is sandwiched between the two short fiber layers and entangled and integrated, the fibers of the short fiber layer There is a tendency that the entanglement between the fibers and the continuous fibers constituting the net-like object, or the entanglement between the fibers of the two short fiber layers located on both sides of the net-like object is reduced. A decrease in confounding may cause a decrease in electrical conductivity in the obtained conductive structure.
一方、目合いが20mmを越えると、導電性繊維構造物の力学的特性及び/または電気伝導特性の方向依存性を少なくする効果が低下することがあるだけでなく、ネット状物そのものの取り扱い性が悪くなり、導電性繊維構造物の生産性が低下することがある。ネット状物の目合いは1mm以上、15mm以下であることがより好ましく、2mm以上、10mm以下であることが特に好ましく、3mm以上、9mm以下であることが最も好ましい。ネット状物内で一方向(例えばMD方向)に延びる連続繊維が形成する目合い及びその一方向と交差する方向(例えばCD方向)に延びる連続繊維が形成する目合いは、いずれも上記範囲を満たすことが好ましい。また、連続繊維は各目合いが上記範囲内であって、異なる目合いがランダムに(不規則に)生じるように配列されていてよいが、連続繊維は、目合いが規則正しい値(例えば目合いが3mmと5mmの繰り返し)となるように配列されていることが好ましく、特定の値に統一された目合いとなるように配列されていることが特に好ましい。また一方向の連続繊維が形成する目合いと、前記一方向と交差する方向の連続繊維が形成する目合いが異なっていてもよいが、両者が同じ値であることが特に好ましい。
On the other hand, if the mesh size exceeds 20 mm, not only the effect of reducing the direction dependency of the mechanical and / or electrical conductive properties of the conductive fiber structure may be lowered, but also the handling property of the net-like material itself. May deteriorate and the productivity of the conductive fiber structure may decrease. The mesh size of the net-like material is more preferably 1 mm or more and 15 mm or less, particularly preferably 2 mm or more and 10 mm or less, and most preferably 3 mm or more and 9 mm or less. The mesh formed by continuous fibers extending in one direction (for example, the MD direction) and the mesh formed by continuous fibers extending in the direction intersecting the one direction (for example, the CD direction) both within the above range. It is preferable to satisfy. In addition, continuous fibers may be arranged so that each mesh is within the above range, and different meshes are randomly generated (irregularly). Is preferably arranged so as to be a repetition of 3 mm and 5 mm, and particularly preferably arranged so as to have a uniform scale of a specific value. Further, the mesh formed by the continuous fibers in one direction and the mesh formed by the continuous fibers in the direction intersecting the one direction may be different, but it is particularly preferable that both have the same value.
前記長繊維シート状物において、少なくとも2つの方向に連続して延びる長繊維が形成する開口部の面積(以下、単に「開口部面積」と称す)は特に限定されないが、1mm2以上、500mm2以下であることが好ましい。開口部面積が1mm2未満であると、導電性繊維構造物の通気度が低下し、通気度を必要とする用途には適さなくなるおそれがある。また、開口部面積が小さすぎると、長繊維シート状物を構成する長繊維の繊維径によっては、硬くなったり、曲げにくくなったりすることがあり、長繊維シート状物及び、それを含む導電性繊維構造物の取扱い性及び後加工性が低下するおそれがある。さらに、開口部面積が小すぎると、後述する短繊維層と長繊維シート状物を交絡させる場合、特に2つの短繊維層の間に長繊維シート状物を挟んで交絡一体化させる際に、短繊維層の繊維と長繊維シート状物を構成する長繊維との交絡性、あるいは長繊維シート状物の両側に位置する2つの短繊維層の繊維同士の交絡性が低下する傾向にある。交絡性の低下は、得られる導電性構造物における電気伝導性の低下を招くことがある。
In the long fiber sheet-like material, the area of the opening formed by the long fibers continuously extending in at least two directions (hereinafter simply referred to as “opening area”) is not particularly limited, but is 1 mm 2 or more and 500 mm 2. The following is preferable. When the opening area is less than 1 mm 2 , the air permeability of the conductive fiber structure is lowered, and there is a possibility that it is not suitable for an application requiring air permeability. In addition, if the opening area is too small, depending on the fiber diameter of the long fibers constituting the long fiber sheet-like material, it may become hard or difficult to bend. The handleability and post-processability of the porous fiber structure may be reduced. Furthermore, if the opening area is too small, when the short fiber layer and the long fiber sheet material to be described later are entangled, especially when the long fiber sheet material is sandwiched between the two short fiber layers, The confounding property between the fibers of the short fiber layer and the long fibers constituting the long fiber sheet material, or the confounding property between the fibers of the two short fiber layers located on both sides of the long fiber sheet material tends to decrease. A decrease in confounding may cause a decrease in electrical conductivity in the obtained conductive structure.
一方、開口部面積が500mm2を越えると、導電性繊維構造物の力学的特性及び/または電気伝導特性の方向依存性を少なくする効果が低下することがあるだけでなく、長繊維シート状物そのものの取り扱い性が悪くなり、導電性繊維構造物の生産性が低下することがある。長繊維シート状物の開口部面積は4mm2以上、250mm2以下であることがより好ましく、9mm2以上、100mm2以下であることが特に好ましく、12mm2以上、80mm2以下であることが最も好ましい。
On the other hand, if the opening area exceeds 500 mm 2 , not only the effect of reducing the direction dependency of the mechanical and / or electrical conduction characteristics of the conductive fiber structure may be deteriorated, but also the long fiber sheet-like material. The handleability itself may deteriorate, and the productivity of the conductive fiber structure may decrease. The opening area of the long fiber sheet is more preferably 4 mm 2 or more and 250 mm 2 or less, particularly preferably 9 mm 2 or more and 100 mm 2 or less, and most preferably 12 mm 2 or more and 80 mm 2 or less. preferable.
長繊維シート状物(メッシュ不織布、経緯延伸配列不織布、及びネット状物を含む)を構成する長繊維の繊維径は特に限定されないが、0.5μm以上、1000μm以下であることが好ましい。長繊維の繊維径が0.5μm以上であると、長繊維シート状物において、繊維密度が密になりすぎること、及び繊維間空隙が少なくなりすぎることが避けられ、短繊維層の繊維と良好に交絡する。また、長繊維の繊維径が0.5μm以上であると、長繊維シート状物において、長繊維表面に金属皮膜を形成すると、電気的特性の優れた長繊維シート状物を得ることができる。長繊維の繊維径が1000μm以下であると、長繊維シート状物が硬すぎること、または曲げにくくなることが避けられる。そのため、導電性繊維構造物の製造中、短繊維層を長繊維シート状物に積層する工程において、生産性が低下せず、また、導電性繊維構造物の取扱い性が低下しない。
The fiber diameter of the long fibers constituting the long fiber sheet (including mesh nonwoven fabric, weft stretched nonwoven fabric, and net-like material) is not particularly limited, but is preferably 0.5 μm or more and 1000 μm or less. When the fiber diameter of the long fiber is 0.5 μm or more, in the long fiber sheet-like material, it is avoided that the fiber density becomes too dense and the inter-fiber voids become too small, which is good with the fibers of the short fiber layer. Entangled in. Further, when the fiber diameter of the long fiber is 0.5 μm or more, a long fiber sheet-like product having excellent electrical characteristics can be obtained by forming a metal film on the long fiber surface. When the fiber diameter of the long fibers is 1000 μm or less, it is avoided that the long fiber sheet is too hard or difficult to bend. Therefore, in the process of laminating the short fiber layer on the long fiber sheet during the production of the conductive fiber structure, the productivity does not decrease and the handleability of the conductive fiber structure does not decrease.
長繊維シート状物が、少なくとも異なる2つの方向に連続して延びる連続繊維によって囲まれる開口部を有するネット状物である場合、連続繊維の繊維径は、30μm以上、500μm以下であることがより好ましく、50μm以上、300μm以下であることが特に好ましく、80μm以上、250μm以下であることが最も好ましい。また、ネット状物を構成する連続繊維は、短繊維が集合して連続して延びる糸条(例えば、紡績糸)、マルチフィラメント、及びモノフィラメント等であってよく、好ましくはモノフィラメントもしくはマルチフィラメントであり、特に好ましくはモノフィラメントである。長繊維シート状物が不織布である場合、前記長繊維の繊維径は1μm以上、100μm以下であることが好ましく、3μm以上、50μm以下であることがより好ましく、5μm以上、30μm以下であることが特に好ましい。
When the long fiber sheet is a net-like material having an opening surrounded by continuous fibers extending continuously in at least two different directions, the fiber diameter of the continuous fibers is more preferably 30 μm or more and 500 μm or less. Preferably, it is 50 μm or more and 300 μm or less, and most preferably 80 μm or more and 250 μm or less. The continuous fibers constituting the net-like material may be yarns (for example, spun yarn), multifilaments, monofilaments, etc., in which short fibers are gathered and continuously extended, preferably monofilaments or multifilaments. Particularly preferred are monofilaments. When the long fiber sheet is a non-woven fabric, the fiber diameter of the long fibers is preferably 1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. Particularly preferred.
長繊維シート状物が、少なくとも異なる2つの方向に連続して延びる連続繊維によって囲まれる開口部を有するネット状物である場合、ネット状物の製造方法は特に限定されない。ネット状物は、溶融させた熱可塑性樹脂を押出成形した、押出しネットであることが好ましい。押出しネットは未延伸の状態、すなわち縦方向、横方向など、いずれの方向にも延伸されていない状態のものを使用することができる。未延伸状態の押出しネットを縦方向、横方向の少なくとも一方向に延伸したネットはより好ましい。押出しネットを縦方向、横方向いずれの方向にも延伸した、縦横延伸ネットを用いることが特に好ましい。縦横延伸ネットは縦方向、横方向のどちらの方向にも延伸されているため、引張強度がどの方向に対しても高く、取り扱い性に優れている。したがって、縦横延伸ネットを使用することで導電性繊維構造物の強度が高められる。また、未延伸状態の押出しネットを縦方向、横方向の少なくとも一方向に延伸したネットは、異なる方向に連続している連続繊維の交点が接着しているだけでなく、製造時に交点を中心に交点付近の熱可塑性樹脂を延伸することで、交点の形状が平面方向に広がりを有している。交点部分においてそのような形状を有するネットを本発明の導電性繊維集合物に使用すると、スパッタリングあるいは電解めっきなどで導電性を付与した際、交点付近の広がった(引き延ばされた樹脂の)部分も導電性を有し、導電性を持った部分の面積が広くなる。その結果、本発明の導電性繊維集合物及びこれを用いた各種電極材の電気抵抗が低下し、集電性も高められる。
When the long fiber sheet is a net having an opening surrounded by continuous fibers extending continuously in at least two different directions, the method for producing the net is not particularly limited. The net-like product is preferably an extruded net obtained by extruding a molten thermoplastic resin. The extruded net can be used in an unstretched state, that is, in a state where it is not stretched in any direction such as the longitudinal direction and the transverse direction. A net obtained by stretching an unstretched extruded net in at least one direction of the vertical direction and the horizontal direction is more preferable. It is particularly preferable to use a longitudinal and transverse stretched net obtained by stretching an extruded net in both the longitudinal direction and the transverse direction. Since the longitudinal and transverse stretched nets are stretched in both the longitudinal direction and the transverse direction, the tensile strength is high in any direction and the handleability is excellent. Therefore, the strength of the conductive fiber structure can be increased by using the longitudinal and lateral stretched nets. In addition, a net obtained by stretching an unstretched extruded net in at least one direction in the longitudinal direction and the transverse direction is not only bonded at the intersection of continuous fibers continuous in different directions, but also at the intersection at the time of manufacture. By extending the thermoplastic resin in the vicinity of the intersection, the shape of the intersection expands in the plane direction. When a net having such a shape at the intersection is used for the conductive fiber assembly of the present invention, when the conductivity is given by sputtering or electrolytic plating, the vicinity of the intersection spreads (of the stretched resin) The portion also has conductivity, and the area of the portion having conductivity is increased. As a result, the electrical resistance of the conductive fiber assembly of the present invention and various electrode materials using the same is reduced, and the current collecting property is also improved.
長繊維シート状物が、少なくとも1方向に延伸したネット状物であると、ネット状物を構成する長繊維同士が交差・接合している部分(以下、単に交点と称す)が、周囲から隆起し、高さのある突起部を形成していることがある。本発明において前記ネット状物を使用する場合、長繊維同士の交点が隆起し、突起部を形成しているネット状物を使用することが好ましい。そのようなネット状物を使用することで、隆起した突起部分によってネット状物が短繊維層に係止されやすくなり、生産性が高められるだけでなく、ネット状物と短繊維層が剥離しにくくなる。また、長繊維同士の交点が隆起し、突起状になっていることで、長繊維の部分や開口部分が交点部分よりも薄い、交点からくぼんだ形状となる。これにより、繊維ウェブとネット状物を交絡させた際、短繊維層を構成する短繊維が突起となっている交点部分をよけて交絡するので、交点以外の部分、例えば開口部分に繊維ウェブが集まるため、ネットの開口部を含め、不織布全体が嵩高なものとなる。また、短繊維層を構成する短繊維が突起となっている交点部分をよけてネットと交絡するので、短繊維層を構成する短繊維がネット状物の開口部分にも充填されやすくなり、短繊維層とネット状物がより強固に一体化される。また、開口部分にも短繊維が密に充填されるため、導電性を付与することで導電性短繊維によるネットワークがネット状物の開口部にも形成される。その結果、開口部分での電気的特性の低下が避けられ、この部分に充填された活物質からも効果的に集電することが可能な、電気的特性の均一な導電性繊維構造物や各種電池用電極材が得られる。
When the long fiber sheet-like material is a net-like material stretched in at least one direction, a portion where the long fibers constituting the net-like material intersect and are joined (hereinafter simply referred to as an intersection) is raised from the periphery. However, there is a case where a protruding portion having a height is formed. When using the said net-like thing in this invention, it is preferable to use the net-like thing which the intersection of long fibers protrudes and forms the projection part. By using such a net-like material, the net-like material is easily locked to the short fiber layer by the raised protrusions, and not only the productivity is improved, but also the net-like material and the short fiber layer are peeled off. It becomes difficult. Further, the intersection of the long fibers is raised and formed in a protrusion shape, so that the long fiber portion and the opening portion are thinner than the intersection portion and have a shape recessed from the intersection. Thereby, when the fiber web and the net-like object are entangled, the short fibers constituting the short fiber layer are entangled by avoiding the intersection part where the protrusion is formed, so that the fiber web is formed at a part other than the intersection point, for example, the opening part. Therefore, the entire nonwoven fabric including the opening of the net becomes bulky. In addition, because the short fibers constituting the short fiber layer are entangled with the net by avoiding the intersection portion where the protrusions are formed, the short fibers constituting the short fiber layer are easily filled into the opening portion of the net-like material, The short fiber layer and the net-like material are more firmly integrated. In addition, since the short fibers are densely filled in the opening portions, a network of the conductive short fibers is also formed in the openings of the net-like object by imparting conductivity. As a result, a decrease in electrical characteristics at the opening is avoided, and conductive fiber structures with uniform electrical characteristics that can effectively collect current from the active material filled in this part and various types A battery electrode material is obtained.
前記ネット状物において、長繊維同士の交点部分が、周囲から隆起した突起部を形成しているかどうかは、長繊維の繊維径と、交点部分の厚さ(高さ)を比較することで測定できる。前記ネット状物においては、長繊維同士の交点の厚さと、長繊維の繊維径との比が1.1以上、すなわち(長繊維同士の交点の厚さ)/(長繊維の繊維径)が1.1以上であることが好ましい。交点の厚さが、長繊維の繊維径に対し1.1倍以上であると、前述した効果が得られ、様々な用途に適した導電性繊維構造物、及び電気的特性にムラのない、均一な電池用電極材を容易に製造できる積層繊維構造物が得られる。長繊維同士の交点の厚さと長繊維の繊維径との比は1.2以上であることがより好ましく、1.3以上であることが特に好ましい。長繊維同士の交点の厚さと長繊維の繊維径との比は、その上限が特に限定されない。当該比が4より大きくなると、突起部が高すぎる、すなわち交点が厚すぎるため、積層繊維構造物の地合不良を招くことがある。また、当該比が4より大きくなると、この積層繊維構造物を用いて導電性繊維構造物や各種電極材を製造した際、突起部が金属突起となって表面に露出するおそれもある。前記長繊維同士の交点の厚さと長繊維の繊維径との比は4以下であると好ましく、2.5以下がより好ましく、2以下が特に好ましく、1.8以下が最も好ましい。なお、ネット状物を構成する長繊維の繊維径が長繊維によって差がある場合(例えばMD方向の長繊維と、CD方向の長繊維とで繊維径が異なる場合)、より繊維径が大きい方の繊維径を用いて長繊維同士の交点の厚さと長繊維の繊維径との比を求めることとする。
In the net-like object, whether or not the intersection part of the long fibers forms a protrusion protruding from the periphery is measured by comparing the fiber diameter of the long fiber and the thickness (height) of the intersection part. it can. In the net-like product, the ratio of the thickness of the intersection of long fibers to the fiber diameter of the long fibers is 1.1 or more, that is, (the thickness of the intersection of long fibers) / (fiber diameter of the long fibers). It is preferable that it is 1.1 or more. When the thickness of the intersection is 1.1 times or more of the fiber diameter of the long fiber, the above-described effect is obtained, and there is no unevenness in the conductive fiber structure suitable for various applications, and electrical characteristics. A laminated fiber structure capable of easily producing a uniform battery electrode material is obtained. The ratio between the thickness of the intersection of long fibers and the fiber diameter of the long fibers is more preferably 1.2 or more, and particularly preferably 1.3 or more. The upper limit of the ratio between the thickness of the intersection between the long fibers and the fiber diameter of the long fibers is not particularly limited. If the ratio is greater than 4, the protrusions are too high, that is, the intersections are too thick, which may cause poor formation of the laminated fiber structure. Moreover, when the ratio is larger than 4, when the conductive fiber structure or various electrode materials are manufactured using the laminated fiber structure, the protrusion may be exposed as a metal protrusion on the surface. The ratio between the thickness of the intersection of the long fibers and the fiber diameter of the long fibers is preferably 4 or less, more preferably 2.5 or less, particularly preferably 2 or less, and most preferably 1.8 or less. In addition, when the fiber diameter of the long fiber which comprises a net-like thing has a difference by long fiber (For example, when the fiber diameter differs in the long fiber of MD direction and the long fiber of CD direction), the one where fiber diameter is larger The ratio of the thickness of the intersection between the long fibers and the fiber diameter of the long fibers is determined using the fiber diameter.
長繊維シート状物を形成する材質(原料)は特に限定されない。長繊維シート状物は、例えば、コットン、及びケナフ繊維等のセルロース系の天然繊維、シルク、及びウール等の動物由来の天然繊維、ビスコースレーヨン、キュプラ、及び溶剤紡糸セルロース繊維(例えば、レンチングリヨセル(登録商標)及びテンセル(登録商標))等の再生繊維、合成繊維、及び炭素繊維から選ばれる1種または複数の繊維で形成されてよい。本発明の導電性繊維構造物から、金属繊維からなる金属多孔構造物を製造する場合、長繊維シート状物を構成する繊維は、熱消失性物質からなるものであることを要する。「熱消失性物質」とは、高い温度(但し、金属皮膜を構成する金属が変形しない温度)で加熱されたときに、分解または燃焼して消失する性質を有する物質である。
The material (raw material) for forming the long fiber sheet is not particularly limited. Long fiber sheet materials include, for example, cellulosic natural fibers such as cotton and kenaf fibers, animal-derived natural fibers such as silk and wool, viscose rayon, cupra, and solvent-spun cellulose fibers (for example, lentigryocell). (Registered Trademark) and Tencel (Registered Trademark)) may be formed of one or more fibers selected from recycled fibers, synthetic fibers, and carbon fibers. In the case of producing a metal porous structure made of metal fibers from the conductive fiber structure of the present invention, the fibers constituting the long fiber sheet material need to be made of a heat-dissipating substance. “Heat-dissipating substance” is a substance having the property of decomposing or burning and disappearing when heated at a high temperature (however, the metal constituting the metal film does not deform).
長繊維シート状物が合成繊維からなる場合、合成繊維は熱可塑性樹脂から成る繊維であれば特に限定されない。熱可塑性樹脂として、具体的には、
ポリエチレン(高密度、低密度、直鎖状低密度ポリエチレンを含む)、ポリプロピレン、ポリブテン、ポリブチレン、ポリメチルペンテン、ポリブタジエン、エチレン系共重合体(例えば、エチレン-αオレフィン共重合体)、プロピレン系共重合体(例えば、プロピレン-エチレン共重合体)、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、及びエチレン-(メタ)アクリル酸メチル共重合体等などのポリオレフィン系樹脂、
ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンナフタレート、ポリ乳酸、ポリブチレンサクシネート及びその共重合体などのポリエステル樹脂、
ナイロン66、ナイロン12、及びナイロン6などのポリアミド系樹脂、
アクリル系樹脂、
ポリカーボネート、ポリアセタール、ポリスチレン及び環状ポリオレフィンなどのエンジニアリング・プラスチック、
それらの混合物、ならびに
それらのエラストマー系樹脂
が挙げられる。上記の熱可塑性樹脂を1種類用いた単一成分の長繊維、または上記の熱可塑性樹脂を2種類以上用いた複合長繊維を長繊維シート状物に使用することができる。後述するように短繊維層が熱接着性繊維を含む場合、熱接着性繊維との熱接着性を考慮すると、長繊維シート状物を構成する長繊維は、少なくともその表面がポリオレフィン系樹脂を含む成分で構成された長繊維であることが好ましい。 When the long fiber sheet is made of synthetic fiber, the synthetic fiber is not particularly limited as long as the synthetic fiber is a fiber made of a thermoplastic resin. Specifically, as a thermoplastic resin,
Polyethylene (including high density, low density, linear low density polyethylene), polypropylene, polybutene, polybutylene, polymethylpentene, polybutadiene, ethylene copolymer (eg, ethylene-α olefin copolymer), propylene copolymer Polymers (eg, propylene-ethylene copolymers), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, and ethylene-methyl (meth) acrylate copolymers Polyolefin resins such as polymers,
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene succinate and copolymers thereof,
Polyamide resins such as nylon 66, nylon 12 and nylon 6,
Acrylic resin,
Engineering plastics such as polycarbonate, polyacetal, polystyrene and cyclic polyolefin,
These mixtures, as well as their elastomeric resins. A single-component long fiber using one kind of the above-mentioned thermoplastic resin or a composite long fiber using two or more kinds of the above-mentioned thermoplastic resins can be used for the long-fiber sheet-like material. As will be described later, when the short fiber layer includes a heat-adhesive fiber, considering the heat adhesion with the heat-adhesive fiber, at least the surface of the long fiber constituting the long-fiber sheet-like material includes a polyolefin-based resin. It is preferably a long fiber composed of components.
ポリエチレン(高密度、低密度、直鎖状低密度ポリエチレンを含む)、ポリプロピレン、ポリブテン、ポリブチレン、ポリメチルペンテン、ポリブタジエン、エチレン系共重合体(例えば、エチレン-αオレフィン共重合体)、プロピレン系共重合体(例えば、プロピレン-エチレン共重合体)、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、及びエチレン-(メタ)アクリル酸メチル共重合体等などのポリオレフィン系樹脂、
ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンナフタレート、ポリ乳酸、ポリブチレンサクシネート及びその共重合体などのポリエステル樹脂、
ナイロン66、ナイロン12、及びナイロン6などのポリアミド系樹脂、
アクリル系樹脂、
ポリカーボネート、ポリアセタール、ポリスチレン及び環状ポリオレフィンなどのエンジニアリング・プラスチック、
それらの混合物、ならびに
それらのエラストマー系樹脂
が挙げられる。上記の熱可塑性樹脂を1種類用いた単一成分の長繊維、または上記の熱可塑性樹脂を2種類以上用いた複合長繊維を長繊維シート状物に使用することができる。後述するように短繊維層が熱接着性繊維を含む場合、熱接着性繊維との熱接着性を考慮すると、長繊維シート状物を構成する長繊維は、少なくともその表面がポリオレフィン系樹脂を含む成分で構成された長繊維であることが好ましい。 When the long fiber sheet is made of synthetic fiber, the synthetic fiber is not particularly limited as long as the synthetic fiber is a fiber made of a thermoplastic resin. Specifically, as a thermoplastic resin,
Polyethylene (including high density, low density, linear low density polyethylene), polypropylene, polybutene, polybutylene, polymethylpentene, polybutadiene, ethylene copolymer (eg, ethylene-α olefin copolymer), propylene copolymer Polymers (eg, propylene-ethylene copolymers), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, and ethylene-methyl (meth) acrylate copolymers Polyolefin resins such as polymers,
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene succinate and copolymers thereof,
Polyamide resins such as nylon 66, nylon 12 and nylon 6,
Acrylic resin,
Engineering plastics such as polycarbonate, polyacetal, polystyrene and cyclic polyolefin,
These mixtures, as well as their elastomeric resins. A single-component long fiber using one kind of the above-mentioned thermoplastic resin or a composite long fiber using two or more kinds of the above-mentioned thermoplastic resins can be used for the long-fiber sheet-like material. As will be described later, when the short fiber layer includes a heat-adhesive fiber, considering the heat adhesion with the heat-adhesive fiber, at least the surface of the long fiber constituting the long-fiber sheet-like material includes a polyolefin-based resin. It is preferably a long fiber composed of components.
長繊維の断面形状はいずれの形状であってよい。具体的には、円形(真円)断面の長繊維の他、断面形状が非円形の長繊維、いわゆる異形断面の長繊維を用いることができる。異形断面としては、多角型形状、楕円型形状、扁平型形状、繊維表面に多数の枝状部を有する、いわゆる多葉型形状(具体的には3葉から32葉の多葉型形状)、星型形状、C字型形状、Y字型形状、W字型形状、及び井型形状が例示される。さらに、長繊維は、繊維断面に長さ方向に連続する空洞部分を有さない中実繊維であってよく、あるいは長さ方向に連続する1箇所以上の空洞部分を有する中空繊維であってもよい。
The cross-sectional shape of the long fiber may be any shape. Specifically, in addition to a long fiber having a circular (perfect circle) cross section, a long fiber having a non-circular cross-sectional shape, that is, a so-called irregular cross-section long fiber can be used. As an irregular cross section, a polygonal shape, an elliptical shape, a flat shape, a so-called multileaf shape (specifically, a multileaf shape of 3 to 32 leaves) having a number of branch portions on the fiber surface, Examples are a star shape, a C shape, a Y shape, a W shape, and a well shape. Further, the long fiber may be a solid fiber that does not have a hollow portion that is continuous in the length direction in the fiber cross section, or may be a hollow fiber that has one or more hollow portions that are continuous in the length direction. Good.
長繊維シート状物の目付は特に限定されないが、2g/m2以上、100g/m2以下であることが好ましい。長繊維シート状物の目付が2g/m2以上であると、長繊維シート状物を含む本発明の導電性繊維構造物が機械的特性においても優れたものとなる。長繊維シート状物の目付が100g/m2以下であると、長繊維シート状物を含む本発明の導電性繊維構造物が、適度な厚みを持つものとなり、取扱い性、及び後加工性が良好なものとなりうる。前記長繊維シート状物の目付は3g/m2以上、70g/m2以下であることがより好ましく、4g/m2以上、50g/m2以下であることが特に好ましく、5g/m2以上、40g/m2以下であることが最も好ましい。
Basis weight of the long fiber sheet is not particularly limited, it is preferably 2 g / m 2 or more and 100 g / m 2 or less. When the basis weight of the long fiber sheet is 2 g / m 2 or more, the conductive fiber structure of the present invention including the long fiber sheet is excellent in mechanical properties. When the basis weight of the long fiber sheet is 100 g / m 2 or less, the conductive fiber structure of the present invention including the long fiber sheet has an appropriate thickness, and handling properties and post-processability are improved. Can be good. The basis weight of the long fiber sheet is more preferably 3 g / m 2 or more and 70 g / m 2 or less, particularly preferably 4 g / m 2 or more and 50 g / m 2 or less, and 5 g / m 2 or more. 40 g / m 2 or less is most preferable.
本発明の導電性繊維構造物に加熱処理を行い金属多孔構造物とし、この金属多孔構造物に活物質合剤を充填させて、電池用電極材を製造する場合、長繊維シート状物は、繊維径70μm以上、300μm以下の連続繊維、好ましくはモノフィラメントで構成される直交ネット状物であって、目合いが、いずれの方向共に2mm以上、10mm以下であって、開口部面積が4mm2以上、100mm2以下の直交ネット状物であることが好ましい。このような直交ネット状物は、繊維構造物において、短繊維層の構成繊維同士、及び短繊維層の構成繊維と直交シート状物のモノフィラメントとが良好に交絡することを可能にする。
When the conductive fiber structure of the present invention is subjected to a heat treatment to form a metal porous structure, and this metal porous structure is filled with an active material mixture to produce a battery electrode material, the long fiber sheet is An orthogonal net-like material composed of continuous fibers having a fiber diameter of 70 μm or more and 300 μm or less, preferably monofilaments, having a mesh size of 2 mm or more and 10 mm or less in any direction, and an opening area of 4 mm 2 or more. It is preferably an orthogonal net-like material of 100 mm 2 or less. Such an orthogonal net-like material enables the constituent fibers of the short fiber layer and the constituent fibers of the short fiber layer and the monofilaments of the orthogonal sheet-like material to be entangled satisfactorily in the fiber structure.
市販されているメッシュ不織布としては、例えば、JX日鉱日石ANCI株式会社から販売されているワリフ(登録商標)があり、市販されている経緯延伸配列不織布としては、例えば、JX日鉱日石ANCI株式会社から販売されているミライフ(登録商標)がある。これらの長繊維シート状物は寸法安定性に優れるだけでなく、種類が豊富であることから、導電性繊維構造物が求められる特性に応じて最適の厚み、及び目付のものを選ぶことができる。
As a commercially available mesh nonwoven fabric, there is, for example, Warif (registered trademark) sold by JX Nippon Mining & Metals Anci Co., Ltd. There is Milife (registered trademark) sold by the company. These long fiber sheets are not only excellent in dimensional stability, but also have a wide variety, so that the optimum thickness and basis weight can be selected according to the characteristics required of the conductive fiber structure. .
市販されているネット状物としては、例えば、JX日鉱日石ANCI株式会社から販売されているコンウェッド(登録商標)ネット、DelStar社(DelStar Technologies,Inc.) から販売されているDelnet(登録商標)などがある。コンウェッド(登録商標)ネットは、種類が豊富であり、導電性繊維構造物に求められている特性に応じて最適の厚み、目付、目合い、及び開口部面積のものが選べるため、好ましい。
Examples of commercially available net-like products include, for example, Conwed (registered trademark) net sold by JX Nippon Mining & Metals Anci Corporation, Delnet (registered trademark) sold by DelStar (DelStar Technologies, Inc.). and so on. Conwed (registered trademark) nets are preferred because they are abundant in types and can be selected to have the optimum thickness, basis weight, mesh size, and opening area according to the characteristics required of the conductive fiber structure.
次に、本発明の導電性繊維構造物を構成する短繊維層について説明する。短繊維層は、短繊維が開繊されて集積された繊維集合物をいい、繊維同士が接着しているものも含む概念である。短繊維層を構成する繊維の種類、繊維径、繊度、繊維の断面形状、及び繊維長は、特に限定されず、また短繊維層の目付、厚み、空隙率、通気度等の繊維ウェブの各種物性も特に限定されない。
Next, the short fiber layer constituting the conductive fiber structure of the present invention will be described. The short fiber layer refers to a fiber aggregate in which short fibers are opened and accumulated, and is a concept that includes a fiber bonded to each other. The type of fiber constituting the short fiber layer, the fiber diameter, the fineness, the cross-sectional shape of the fiber, and the fiber length are not particularly limited, and various fiber webs such as the basis weight, thickness, porosity, and air permeability of the short fiber layer The physical properties are not particularly limited.
短繊維層は、公知の繊維、例えば、コットン、及びケナフ繊維等のセルロース系の天然繊維、シルク、及びウールなどの動物由来の天然繊維、ビスコースレーヨン、キュプラ、及び溶剤紡糸セルロース繊維(例えば、レンチングリヨセル(登録商標)及びテンセル(登録商標))等の再生繊維、合成繊維、及び炭素繊維から選択される1種または複数の繊維で形成されていてよい。本発明の導電性繊維構造物から、金属繊維からなる金属多孔構造物を製造する場合、短繊維シート状物を構成する繊維は、熱消失性物質からなるものであることを要する。
The short fiber layer is made of known fibers, for example, cellulose-based natural fibers such as cotton and kenaf fibers, animal-derived natural fibers such as silk and wool, viscose rayon, cupra, and solvent-spun cellulose fibers (for example, It may be formed of one or a plurality of fibers selected from regenerated fibers such as lentigo lyocell (registered trademark) and tencel (registered trademark), synthetic fibers, and carbon fibers. When producing a metal porous structure made of metal fibers from the conductive fiber structure of the present invention, it is necessary that the fibers constituting the short fiber sheet are made of a heat-dissipating substance.
短繊維層が合成繊維からなる場合、合成繊維は、熱可塑性樹脂から成る繊維であれば特に限定されない。熱可塑性樹脂として、具体的には、
ポリエチレン(高密度、低密度、直鎖状低密度ポリエチレンを含む)、ポリプロピレン、ポリブテン、ポリブチレン、ポリメチルペンテン、ポリブタジエン、エチレン系共重合体(例えば、エチレン-αオレフィン共重合体)、プロピレン系共重合体(例えば、プロピレン-エチレン共重合体)、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、及びエチレン-(メタ)アクリル酸メチル共重合体等などのポリオレフィン系樹脂、
ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンナフタレート、ポリ乳酸、ポリブチレンサクシネート及びその共重合体などのポリエステル樹脂、
ナイロン66、ナイロン12、及びナイロン6などのポリアミド系樹脂、
アクリル系樹脂、
ポリカーボネート、ポリアセタール、ポリスチレン及び環状ポリオレフィンなどのエンジニアリング・プラスチック、
それらの混合物、ならびに
それらのエラストマー系樹脂
が挙げられる。上記の熱可塑性樹脂を1種類用いた単一繊維、または上記の熱可塑性樹脂を2種類以上用いた複合繊維を短繊維層に使用できる。 When the short fiber layer is made of a synthetic fiber, the synthetic fiber is not particularly limited as long as it is a fiber made of a thermoplastic resin. Specifically, as a thermoplastic resin,
Polyethylene (including high density, low density, linear low density polyethylene), polypropylene, polybutene, polybutylene, polymethylpentene, polybutadiene, ethylene copolymer (eg, ethylene-α olefin copolymer), propylene copolymer Polymers (eg, propylene-ethylene copolymers), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, and ethylene-methyl (meth) acrylate copolymers Polyolefin resins such as polymers,
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene succinate and copolymers thereof,
Polyamide resins such as nylon 66, nylon 12 and nylon 6,
Acrylic resin,
Engineering plastics such as polycarbonate, polyacetal, polystyrene and cyclic polyolefin,
These mixtures, as well as their elastomeric resins. A single fiber using one kind of the above thermoplastic resin or a composite fiber using two or more kinds of the above thermoplastic resins can be used for the short fiber layer.
ポリエチレン(高密度、低密度、直鎖状低密度ポリエチレンを含む)、ポリプロピレン、ポリブテン、ポリブチレン、ポリメチルペンテン、ポリブタジエン、エチレン系共重合体(例えば、エチレン-αオレフィン共重合体)、プロピレン系共重合体(例えば、プロピレン-エチレン共重合体)、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、及びエチレン-(メタ)アクリル酸メチル共重合体等などのポリオレフィン系樹脂、
ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンナフタレート、ポリ乳酸、ポリブチレンサクシネート及びその共重合体などのポリエステル樹脂、
ナイロン66、ナイロン12、及びナイロン6などのポリアミド系樹脂、
アクリル系樹脂、
ポリカーボネート、ポリアセタール、ポリスチレン及び環状ポリオレフィンなどのエンジニアリング・プラスチック、
それらの混合物、ならびに
それらのエラストマー系樹脂
が挙げられる。上記の熱可塑性樹脂を1種類用いた単一繊維、または上記の熱可塑性樹脂を2種類以上用いた複合繊維を短繊維層に使用できる。 When the short fiber layer is made of a synthetic fiber, the synthetic fiber is not particularly limited as long as it is a fiber made of a thermoplastic resin. Specifically, as a thermoplastic resin,
Polyethylene (including high density, low density, linear low density polyethylene), polypropylene, polybutene, polybutylene, polymethylpentene, polybutadiene, ethylene copolymer (eg, ethylene-α olefin copolymer), propylene copolymer Polymers (eg, propylene-ethylene copolymers), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, and ethylene-methyl (meth) acrylate copolymers Polyolefin resins such as polymers,
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polylactic acid, polybutylene succinate and copolymers thereof,
Polyamide resins such as nylon 66, nylon 12 and nylon 6,
Acrylic resin,
Engineering plastics such as polycarbonate, polyacetal, polystyrene and cyclic polyolefin,
These mixtures, as well as their elastomeric resins. A single fiber using one kind of the above thermoplastic resin or a composite fiber using two or more kinds of the above thermoplastic resins can be used for the short fiber layer.
前記短繊維の断面形状はいずれの形状であってよい。具体的には、円形(真円)断面の短繊維の他、断面形状が非円形の短繊維、いわゆる異形断面の短繊維を用いることができる。異形断面としては、多角型形状、楕円型形状、扁平型形状、繊維表面に多数の枝状部を有する多葉型形状(具体的には3葉から32葉の多葉型形状)、星型形状、C字型形状、Y字型形状、W字型形状、及び井型形状が例示される。さらに、短繊維は、繊維断面に長さ方向に連続する空洞部分を有さない中実繊維であってよく、あるいは長さ方向に連続する1箇所以上の空洞部分を有する中空繊維であってもよい。
The cross-sectional shape of the short fiber may be any shape. Specifically, short fibers having a non-circular cross section, that is, short fibers having a so-called irregular cross section can be used in addition to short fibers having a circular (perfect circle) cross section. The irregular cross section includes a polygonal shape, an elliptical shape, a flat shape, a multi-leaf shape having a large number of branches on the fiber surface (specifically, a multi-leaf shape having 3 to 32 leaves), a star shape Examples include a shape, a C shape, a Y shape, a W shape, and a well shape. Further, the short fiber may be a solid fiber that does not have a hollow portion that is continuous in the length direction in the fiber cross section, or may be a hollow fiber that has one or more hollow portions that are continuous in the length direction. Good.
短繊維層は、熱接着性繊維を含み、この熱接着性繊維によって短繊維層を構成する繊維同士が接着している、及び/又は短繊維層を構成する繊維と長繊維シート状物を構成する長繊維とが接着していることが好ましい。熱接着性繊維によって、繊維同士が接着した交点は導電性繊維構造物全体の強度を大きくする。また、その交点の表面に形成された金属皮膜は一体化されていて、導電性繊維構造物(ならびにこれから熱消失性物質を除去して得た金属多孔構造物)が良好な電気伝導性を有することを確保する。熱接着性繊維は、単一繊維であってよく、あるいは2以上の樹脂成分からなる複合繊維であってよい。
The short fiber layer includes a heat-adhesive fiber, and the fibers constituting the short fiber layer are bonded to each other by the heat-adhesive fiber, and / or the fiber constituting the short fiber layer and the long fiber sheet are formed. It is preferable that the long fibers to be bonded are bonded. The intersection where the fibers are bonded to each other by the heat bonding fiber increases the strength of the entire conductive fiber structure. In addition, the metal film formed on the surface of the intersection is integrated, and the conductive fiber structure (and the metal porous structure obtained by removing the heat-dissipating substance therefrom) has good electrical conductivity. To ensure that. The thermoadhesive fiber may be a single fiber or a composite fiber composed of two or more resin components.
熱接着性繊維は、熱接着処理の際の加工性を考慮すると、低温で熱接着性を示す低融点合成樹脂を繊維表面の少なくとも一部に含むことが好ましい。具体的には、熱接着性繊維は、低融点合成樹脂と、前記低融点合成樹脂の融点よりも10℃以上融点が高い高融点合成樹脂(すなわち、低融点合成樹脂の融点(℃)≦高融点合成樹脂の融点-10(℃)を満たす2種類の樹脂)で構成され、繊維表面の少なくとも一部に低融点合成樹脂が露出している複合繊維であることが好ましい。
It is preferable that the heat-adhesive fiber contains a low-melting-point synthetic resin that exhibits heat-adhesion properties at a low temperature in at least a part of the fiber surface in consideration of workability during the heat-adhesion treatment. Specifically, the heat-adhesive fiber includes a low-melting synthetic resin and a high-melting synthetic resin having a melting point of 10 ° C. or more higher than the melting point of the low-melting synthetic resin (that is, the melting point (° C.) of the low-melting synthetic resin ≦ high The composite fiber is preferably a composite fiber in which the low melting point synthetic resin is exposed on at least a part of the fiber surface.
熱接着性複合繊維の複合形態としては、芯鞘型複合繊維(高融点の芯成分の重心位置が繊維の重心位置からずれている偏心芯鞘型複合繊維を含む)、並列型複合繊維(「サイドバイサイド型複合繊維」とも称す)、低融点合成樹脂からなる海成分と、高融点合成樹脂からなる島成分で構成される海島型複合繊維、及び高融点合成樹脂と低融点合成樹脂が繊維断面において交互に配置されている分割型複合繊維(例えば、繊維断面において、柑橘類の房状の樹脂成分が交互に配置されている分割型複合繊維)などが挙げられる。本発明において、短繊維層に使用する熱接着性複合繊維の複合形態は限定されず、いずれの複合形態の熱接着性複合繊維も使用できる。繊維間の熱接着性を考慮すると、芯鞘型複合繊維を用いることが好ましい。
As the composite form of the heat-adhesive conjugate fiber, the core-sheath type conjugate fiber (including the eccentric core-sheath type conjugate fiber in which the center of gravity of the high melting point core component is shifted from the center of gravity of the fiber), the parallel type conjugate fiber (“ Side-by-side type composite fiber), sea-island type composite fiber composed of a sea component composed of low-melting synthetic resin and island component composed of high-melting synthetic resin, and high-melting synthetic resin and low-melting synthetic resin in the fiber cross section Examples include split-type composite fibers arranged alternately (for example, split-type composite fibers in which citrus tufted resin components are alternately arranged in the fiber cross section). In this invention, the composite form of the heat bondable conjugate fiber used for a short fiber layer is not limited, The heat bondable conjugate fiber of any composite form can be used. In consideration of thermal adhesiveness between fibers, it is preferable to use a core-sheath type composite fiber.
熱接着繊維として前記芯鞘型複合繊維を用いる場合、前記のように鞘成分を低融点合成樹脂で構成し、芯成分を前記低融点合成樹脂の融点よりも10℃以上融点が高い高融点合成樹脂で構成する。鞘成分の低融点合成樹脂と芯成分の高融点合成樹脂の組み合わせは特に限定されない。以下に、熱接着性複合繊維の鞘成分及び芯成分について説明する。
When the core-sheath type composite fiber is used as the heat-bonding fiber, the sheath component is composed of a low-melting synthetic resin as described above, and the core component is a high-melting-point synthetic material having a melting point of 10 ° C. or more higher than the melting point of the low-melting synthetic resin. Consists of resin. The combination of the low melting point synthetic resin of the sheath component and the high melting point synthetic resin of the core component is not particularly limited. Hereinafter, the sheath component and the core component of the thermoadhesive conjugate fiber will be described.
前記芯鞘型複合繊維の鞘成分として、ポリオレフィン系樹脂、ならびに共重合ポリエステル、ポリブチレンサクシネート、及びポリブチレンサクシネートアジペート(「ポリブチレンサクシネートアジテート」とも称す)などの低融点合成樹脂を使用することができる。本発明で使用する熱接着複合繊維においては、鞘成分がポリオレフィン系樹脂を含む樹脂からなることが好ましい。ポリオレフィン系樹脂には、ポリエチレン、ポリプロピレン、ポリブテン、ポリブチレン、ポリメチルペンテン、及びポリブタジエン等の各種ポリオレフィン系樹脂の他、エチレン-αオレフィン共重合体等のエチレン系共重合体、プロピレン-エチレン共重合体、エチレン-プロピレン-ブテン三元共重合体などのプロピレン系共重合体、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸メチル共重合体等、ならびにエチレン、プロピレン、もしくはブテンと、他のモノマーとで構成される各種共重合体が含まれる。ポリエチレンとしては、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン等がある。
As the sheath component of the core-sheath type composite fiber, polyolefin resin and low melting point synthetic resin such as copolymer polyester, polybutylene succinate, and polybutylene succinate adipate (also referred to as “polybutylene succinate agitate”) are used. can do. In the heat-bonding conjugate fiber used in the present invention, the sheath component is preferably made of a resin containing a polyolefin resin. Polyolefin resins include various polyolefin resins such as polyethylene, polypropylene, polybutene, polybutylene, polymethylpentene, and polybutadiene, ethylene copolymers such as ethylene-α-olefin copolymers, and propylene-ethylene copolymers. , Propylene copolymers such as ethylene-propylene-butene terpolymers, ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meta ) Methyl acrylate copolymer and the like, as well as various copolymers composed of ethylene, propylene, or butene and other monomers. Examples of polyethylene include high density polyethylene, low density polyethylene, and linear low density polyethylene.
前記熱接着性複合繊維の鞘成分がポリオレフィン系樹脂であると、耐酸性、耐アルカリ性、及び耐有機溶媒性といった耐薬品性に優れる繊維構造物を得ることができる。また、ポリオレフィン系樹脂の多くは比較的低融点であるため、鞘成分がポリオレフィン系樹脂の熱接着性複合繊維を含む短繊維層を熱加工することによって、構成繊維同士が強固に熱接着された繊維構造物を、比較的低温の熱加工温度で得ることが可能である。本発明において使用する熱接着性複合繊維は、前記鞘成分が、ポリエチレン、エチレン系共重合体、エチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、及びエチレン-(メタ)アクリル酸メチル共重合体から選ばれる少なくとも1種類のポリオレフィン系樹脂を含むものであることが好ましく、より好ましくは鞘成分がポリエチレンを含むものであり、特に好ましくは、鞘成分がポリエチレンのみからなるものである。
When the sheath component of the heat-adhesive conjugate fiber is a polyolefin resin, a fiber structure excellent in chemical resistance such as acid resistance, alkali resistance, and organic solvent resistance can be obtained. In addition, since many of the polyolefin resins have a relatively low melting point, the constituent fibers are strongly heat-bonded by heat-processing the short fiber layer containing the heat-adhesive conjugate fiber of the polyolefin resin as the sheath component. Fibrous structures can be obtained at relatively low thermal processing temperatures. In the heat-adhesive conjugate fiber used in the present invention, the sheath component is polyethylene, ethylene-based copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer. It is preferable that the polymer contains at least one polyolefin resin selected from a copolymer and an ethylene-methyl (meth) acrylate copolymer, more preferably the sheath component contains polyethylene, and particularly preferably the sheath component. Is made only of polyethylene.
熱接着性複合繊維において、芯成分に含まれる高融点合成樹脂は、鞘成分の融点(鞘成分が複数の樹脂からなる場合には、最も融点が高い樹脂の融点とする)よりも10℃以上融点が高い樹脂であれば特に限定されない。芯成分が二種以上の樹脂からなる場合には、最も融点が低い樹脂の融点が、前記鞘成分の融点よりも10℃以上高くなるように、二種以上の樹脂を選択する。前記熱接着性複合繊維の芯成分に好ましく使用される熱可塑性樹脂としては、例えば、ポリプロピレン及びポリメチルペンテン等の比較的高融点のポリオレフィン系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリトリメチレンテレフタレートなどのポリエステル樹脂、ナイロン66、ナイロン12、及びナイロン6などのポリアミド系樹脂を高融点合成樹脂として例示できる。
In the heat-adhesive conjugate fiber, the high melting point synthetic resin contained in the core component is 10 ° C. or higher than the melting point of the sheath component (when the sheath component is composed of a plurality of resins, the melting point of the resin having the highest melting point). If it is resin with high melting | fusing point, it will not specifically limit. When the core component is composed of two or more kinds of resins, the two or more kinds of resins are selected so that the melting point of the resin having the lowest melting point is higher by 10 ° C. or more than the melting point of the sheath component. Examples of the thermoplastic resin preferably used for the core component of the heat-adhesive conjugate fiber include relatively high melting point polyolefin resins such as polypropylene and polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. Polyester resins such as nylon 66, nylon 12, and nylon 6 can be exemplified as the high melting point synthetic resin.
芯鞘型複合繊維(熱接着性複合繊維)における樹脂の組み合わせ(芯/鞘)として、ポリプロピレン/高密度ポリエチレン、ポリプロピレン/低密度ポリエチレン、ポリプロピレン/直鎖状低密度ポリエチレン、ポリエチレンテレフタレート/高密度ポリエチレン、ポリエチレンテレフタレート/低密度ポリエチレン、ポリエチレンテレフタレート/直鎖状低密度ポリエチレン、ポリエチレンテレフタレート/共重合ポリエステル、ポリプロピレン/エチレン-プロピレン共重合体、ポリエチレンテレフタレート/エチレン-プロピレン共重合体、ポリアミド/高密度ポリエチレン、ポリアミド/低密度ポリエチレン、ポリアミド/直鎖状低密度ポリエチレン、ポリアミド/ポリプロピレン、ポリ乳酸/ポリエチレン、ポリ乳酸/ポリブチレンサクシネート、及びポリ乳酸/ポリブチレンサクシネートアジペートに例示される熱可塑性樹脂の組み合わせが挙げられる。
As resin combinations (core / sheath) in the core-sheath type composite fiber (thermal adhesive composite fiber), polypropylene / high density polyethylene, polypropylene / low density polyethylene, polypropylene / linear low density polyethylene, polyethylene terephthalate / high density polyethylene Polyethylene terephthalate / low density polyethylene, polyethylene terephthalate / linear low density polyethylene, polyethylene terephthalate / copolyester, polypropylene / ethylene-propylene copolymer, polyethylene terephthalate / ethylene-propylene copolymer, polyamide / high density polyethylene, Polyamide / low density polyethylene, polyamide / linear low density polyethylene, polyamide / polypropylene, polylactic acid / polyethylene, polylactic acid / polybuty Nsakushineto, and combinations of the thermoplastic resin exemplified in polylactic acid / polybutylene succinate adipate.
鞘成分がポリオレフィン系樹脂を含む場合、芯成分に使用する高融点合成樹脂は、鞘成分に含まれるポリオレフィン系樹脂の融点よりも60℃以上高い融点を有する熱可塑性樹脂、または融点が180℃以上の熱可塑性樹脂からなることが好ましい。より好ましくは、芯成分は、前記ポリオレフィン系樹脂の融点よりも80℃以上高い融点を有する熱可塑性樹脂、または融点が200℃以上の熱可塑性樹脂からなる。このような高融点合成樹脂として、ポリエステル系樹脂及びポリアミド系樹脂が挙げられる。高融点合成樹脂は、好ましくはポリエステル系樹脂であり、より好ましくは、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリトリメチレンテレフタレートから選ばれる少なくとも1種のポリエステル系樹脂であり、特に好ましくは、ポリエチレンテレフタレートである。
When the sheath component contains a polyolefin resin, the high melting point synthetic resin used for the core component is a thermoplastic resin having a melting point of 60 ° C. or higher than the melting point of the polyolefin resin contained in the sheath component, or a melting point of 180 ° C. or higher. The thermoplastic resin is preferably used. More preferably, the core component is made of a thermoplastic resin having a melting point higher by 80 ° C. or more than the melting point of the polyolefin resin, or a thermoplastic resin having a melting point of 200 ° C. or more. Examples of such high melting point synthetic resins include polyester resins and polyamide resins. The high melting point synthetic resin is preferably a polyester resin, more preferably at least one polyester resin selected from polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, particularly preferably polyethylene terephthalate. is there.
芯成分がポリエステル系樹脂を含み、鞘成分がポリオレフィン系樹脂を含む芯鞘型複合繊維は、ポリオレフィン系樹脂を溶融させて繊維同士を接着させるときの温度にて、芯成分であるポリエステル系樹脂の軟化、変形、または溶融が発生しにくい。そのため、そのような熱接着性複合繊維は、ポリオレフィン系樹脂を芯成分に用いた熱接着性複合繊維と比較して高い耐熱性を有し、後述する熱接着処理を行っても繊維構造物の構造が良好に維持されるという点で好都合である。さらに、そのような熱接着性複合繊維は、繊維構造物の嵩を大きくすることができる。芯成分がポリエチレンテレフタレートを含む又はこれからなり、鞘成分がポリエチレン(高密度ポリエチレン、低密度ポリエチレン、及び直鎖状低密度ポリエチレンから選択される1種または複数)を含む又はこれからなる熱接着性複合繊維は特に好ましく用いられる。
The core-sheath type composite fiber in which the core component includes a polyester-based resin and the sheath component includes a polyolefin-based resin is the temperature of the polyester-based resin that is the core component at a temperature at which the polyolefin-based resin is melted to bond the fibers together. Less likely to soften, deform or melt. Therefore, such a heat-adhesive conjugate fiber has high heat resistance as compared with a heat-adhesive conjugate fiber using a polyolefin resin as a core component, and even if a heat-bonding treatment described later is performed, the fiber structure This is advantageous in that the structure is well maintained. Further, such a heat-adhesive conjugate fiber can increase the bulk of the fiber structure. A heat-adhesive conjugate fiber in which the core component contains or consists of polyethylene terephthalate, and the sheath component contains or consists of polyethylene (one or more selected from high-density polyethylene, low-density polyethylene, and linear low-density polyethylene) Is particularly preferably used.
短繊維層に好ましく使用される熱接着性複合繊維において、耐熱性が重視される場合には、前記のように芯成分がポリエステル系樹脂を含むことが好ましい。しかし、芯成分を構成する樹脂はポリエステル系樹脂に限定されず、重視する性能によって芯成分を構成する樹脂を他の合成樹脂から選択してよいことは言うまでもない。例えば、本発明の導電性繊維構造物または金属皮膜を形成する前の繊維構造物をアルカリ溶液、またはジメチルホルムアミド及びm-クレゾール等の有機溶媒に接触させる場合には耐薬品性が求められる。その場合には、熱接着性複合繊維の芯成分は、ポリプロピレンまたはポリメチルペンテンで構成することが好ましい。
In the heat-adhesive conjugate fiber preferably used for the short fiber layer, when heat resistance is important, the core component preferably contains a polyester resin as described above. However, the resin that constitutes the core component is not limited to the polyester-based resin, and it goes without saying that the resin that constitutes the core component may be selected from other synthetic resins depending on the performance that is important. For example, when the conductive fiber structure of the present invention or the fiber structure before forming the metal film is brought into contact with an alkaline solution or an organic solvent such as dimethylformamide and m-cresol, chemical resistance is required. In that case, the core component of the heat-adhesive conjugate fiber is preferably composed of polypropylene or polymethylpentene.
熱接着性複合繊維において、芯成分と鞘成分との複合比(芯成分/鞘成分 体積比)は特に限定されない。熱接着性複合繊維の紡糸性、熱加工時の易熱接着性、熱加工時の熱に対する耐久性などを考慮すると、複合比は2/8以上、8/2以下であることが好ましい。前記複合比が2/8以上であると、繊維自体にコシがあり、熱加工時の耐久性に優れた熱接着性繊維となりうる。前記複合比が8/2以下であると、構成繊維間を熱接着した際、繊維間接着が強固なものとなる。熱接着性複合繊維の複合比は、2.5/7.5以上、7.5/2.5以下であることがより好ましく、3/7以上、7/3以下であることが特に好ましく、3.5/6.5以上、6.5/3.5以下であることが最も好ましい。
In the heat-adhesive conjugate fiber, the composite ratio of the core component and the sheath component (core component / sheath component, volume ratio) is not particularly limited. Considering the spinnability of the heat-adhesive conjugate fiber, easy heat adhesion during heat processing, durability against heat during heat processing, and the like, the composite ratio is preferably 2/8 or more and 8/2 or less. When the composite ratio is 2/8 or more, the fiber itself is stiff and can be a heat-adhesive fiber having excellent durability during heat processing. When the composite ratio is 8/2 or less, adhesion between fibers becomes strong when the constituent fibers are thermally bonded. The composite ratio of the heat-adhesive conjugate fiber is more preferably 2.5 / 7.5 or more and 7.5 / 2.5 or less, particularly preferably 3/7 or more and 7/3 or less, Most preferably, it is 3.5 / 6.5 or more and 6.5 / 3.5 or less.
熱接着性繊維(単一繊維及び複合繊維を含む)の繊維径は、特に限定されないが、5μm以上、80μm以下であることが好ましい。熱接着性複合繊維の繊維径が5μm以上であると、繊維間空隙が確保され、熱加工を行っても熱による変形及び収縮の少ない短繊維層が得られ、繊維表面に金属皮膜を形成したときに、電気的特性の優れた繊維構造物を得ることができる。熱接着性繊維の繊維径が80μm以下であると、短繊維層の生産性が低下することがなく、また、得られた短繊維層が硬すぎることに起因して短繊維層及び本発明の導電性繊維構造物の取扱い性が低下することもない。短繊維層に含まれる熱接着性繊維の繊維径は8μm以上、50μm以下であることがより好ましく、10μm以上、35μm以下であることが特に好ましい。
The fiber diameter of the heat-adhesive fibers (including single fibers and composite fibers) is not particularly limited, but is preferably 5 μm or more and 80 μm or less. When the fiber diameter of the heat-adhesive conjugate fiber is 5 μm or more, a gap between fibers is secured, and a short fiber layer that is less likely to be deformed and contracted by heat is obtained even when heat processing is performed, and a metal film is formed on the fiber surface. Sometimes, a fiber structure having excellent electrical characteristics can be obtained. When the fiber diameter of the heat-adhesive fiber is 80 μm or less, the productivity of the short fiber layer does not decrease, and the obtained short fiber layer is too hard. The handling property of the conductive fiber structure is not lowered. The fiber diameter of the heat-adhesive fiber contained in the short fiber layer is more preferably 8 μm or more and 50 μm or less, and particularly preferably 10 μm or more and 35 μm or less.
熱接着性繊維(単一繊維及び複合繊維を含む)の繊維長は、本発明の導電性繊維構造物の効果、及び短繊維層の生産性を損なわない範囲であれば特に限定されない。熱接着性繊維の繊維長は20mm以上、110mm以下であることが好ましい。熱接着性繊維の繊維長がこの範囲内にあると、熱接着性繊維を含む短繊維層の生産性が高くなり、本発明の導電性繊維構造物の効果も損なわれない。熱接着性繊維の繊維長はより好ましくは25mm以上、85mm以下、特に好ましくは30mm以上、80mm以下、最も好ましくは42mm以上、64mm以下である。
The fiber length of the heat-bonding fibers (including single fibers and composite fibers) is not particularly limited as long as it does not impair the effects of the conductive fiber structure of the present invention and the productivity of the short fiber layer. The fiber length of the heat-adhesive fiber is preferably 20 mm or more and 110 mm or less. When the fiber length of the heat-adhesive fiber is within this range, the productivity of the short fiber layer containing the heat-adhesive fiber is increased, and the effect of the conductive fiber structure of the present invention is not impaired. The fiber length of the heat-adhesive fiber is more preferably 25 mm or more and 85 mm or less, particularly preferably 30 mm or more and 80 mm or less, and most preferably 42 mm or more and 64 mm or less.
本発明の導電性繊維構造物を構成する短繊維層の製造方法は特に限定されず、公知の方法で得ることができる。例えば、カード機を用いてパラレルウェブ、セミランダムウェブ、ランダムウェブ、クロスレイウェブ、またはクリスクロスウェブを作製し、これを短繊維層とすることができる。この場合、熱接着性繊維の繊維長は30mm以上、110mm以下であることが好ましい。カード機を用いて作製したウェブは、短繊維層と長繊維シートとを繊維同士の交絡により一体化する場合、特に好ましく用いられる。あるいは、短繊維層は、エアレイ法を用いたエアレイウェブであってよく、その場合、熱接着性繊維の繊維長は20mm以上、30mm以下であることが好ましい。
The method for producing the short fiber layer constituting the conductive fiber structure of the present invention is not particularly limited, and can be obtained by a known method. For example, a parallel web, a semi-random web, a random web, a cross lay web, or a Chris cross web can be produced using a card machine, and this can be made into a short fiber layer. In this case, the fiber length of the heat-adhesive fiber is preferably 30 mm or more and 110 mm or less. The web produced using a card machine is particularly preferably used when the short fiber layer and the long fiber sheet are integrated by interlacing of fibers. Alternatively, the short fiber layer may be an air array web using an air array method, and in that case, the fiber length of the heat-adhesive fiber is preferably 20 mm or more and 30 mm or less.
短繊維層に含まれる熱接着性繊維は、1種類のみである必要はない。繊維の断面形状、樹脂成分の複合形態、組み合わせる合成樹脂の種類、繊維径、繊維長、芯鞘比、繊度、及び/または熱接着性繊維の製造条件などが異なる、2種類以上の熱接着性繊維を組み合わせて用いてもよい。例えば、熱接着性繊維のうち、少なくとも一種が、鞘成分に親水性の樹脂を含む熱接着性複合繊維であると、繊維構造物に金属皮膜を形成した際、形成された金属皮膜が固定されやすくなり、金属皮膜が熱接着性複合繊維から剥離または脱落しにくくなり、本発明の導電性繊維構造物の電気的特性が向上しうる。親水性の樹脂は、例えば、エチレン-ビニルアルコール共重合体、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸アルキル共重合体、エチレン-(無水)マレイン酸共重合体、及びエチレン-アクリル酸-無水マレイン酸共重合体などの親水性のポリオレフィン系樹脂である。
It is not necessary that only one type of thermal adhesive fiber is included in the short fiber layer. Two or more types of thermal adhesiveness with different fiber cross-sectional shapes, composite forms of resin components, types of synthetic resin to be combined, fiber diameter, fiber length, core-sheath ratio, fineness, and / or manufacturing conditions for thermal adhesive fibers A combination of fibers may be used. For example, if at least one of the heat-adhesive fibers is a heat-adhesive conjugate fiber containing a hydrophilic resin in the sheath component, the formed metal film is fixed when the metal film is formed on the fiber structure. It becomes easy, and it becomes difficult for a metal membrane | film | coat to peel or drop | omit from a heat bondable composite fiber, and the electrical property of the conductive fiber structure of this invention can improve. Examples of hydrophilic resins include ethylene-vinyl alcohol copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid alkyl copolymers, ethylene- (anhydrous) maleic acid copolymers, And a hydrophilic polyolefin-based resin such as an ethylene-acrylic acid-maleic anhydride copolymer.
短繊維層に含まれる熱接着性繊維の割合は特に限定されない。好ましくは、短繊維層の質量に対して、熱接着性繊維が20質量%以上含まれる。短繊維層が20質量%以上の熱接着性複合繊維を含むことによって、短繊維層の構成繊維同士及び/又は短繊維層を構成する繊維と長繊維シート状物を構成する長繊維とが、良好に接着され得る。前記短繊維層に含まれる熱接着性繊維の割合は、短繊維層の質量に対して50質量%以上であることがより好ましく、80質量%以上であることが特に好ましく、100質量%であることが最も好ましい。
The ratio of the heat-bondable fibers contained in the short fiber layer is not particularly limited. Preferably, 20 mass% or more of heat bondable fibers are contained with respect to the mass of the short fiber layer. When the short fiber layer contains 20% by mass or more of the heat-adhesive conjugate fiber, the constituent fibers of the short fiber layer and / or the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet are obtained. Can be well bonded. The proportion of the heat-bondable fibers contained in the short fiber layer is more preferably 50% by mass or more, particularly preferably 80% by mass or more, and 100% by mass with respect to the mass of the short fiber layer. Most preferred.
短繊維層は、それを含む繊維構造物の繊維表面に金属皮膜が形成されたときに、所望の電気的特性を与える限りにおいて、熱接着性繊維以外の繊維を含んでもよく、あるいは熱接着性繊維以外の繊維のみで構成されてよい。以下、熱接着性繊維以外の繊維を、「非熱接着性繊維」とも呼ぶ。非熱接着性繊維は、例えば、前記天然繊維、前記再生繊維、前記合成繊維から選択される、導電性繊維構造物の製造過程において熱接着性を示さない繊維、及び炭素繊維などである。合成繊維が非熱接着性繊維として使用される場合、その繊維断面形状、合成樹脂の種類、及び数、ならびに複数の樹脂成分からなる複合繊維においては、合成樹脂の組み合わせ及び構成樹脂の複合形態は特に限定されない。
The short fiber layer may contain fibers other than the heat-adhesive fibers or provide heat-adhesive properties as long as it provides desired electrical characteristics when a metal film is formed on the fiber surface of the fiber structure containing the short-fiber layer. You may comprise only fibers other than a fiber. Hereinafter, fibers other than the heat-adhesive fibers are also referred to as “non-heat-adhesive fibers”. Non-thermoadhesive fibers are, for example, fibers that are selected from the natural fibers, the regenerated fibers, and the synthetic fibers and that do not exhibit thermal adhesiveness in the process of manufacturing a conductive fiber structure, and carbon fibers. When synthetic fibers are used as non-thermoadhesive fibers, the fiber cross-sectional shape, the type and number of synthetic resins, and the composite fibers composed of multiple resin components, the combination of synthetic resins and the composite form of the constituent resins are There is no particular limitation.
前記非熱接着性繊維の繊維径、及び繊維長、ならびに複合繊維である場合にはその複合比は、特に限定されない。但し、非熱接着性繊維の繊維径及び繊維長が、熱接着性繊維のそれらと大きく異なると、短繊維層の生産性が低下することがあり、また、本発明の効果が損なわれることがある。したがって、非熱接着性繊維の繊維径も5μm以上、80μm以下であることが好ましく、8μm以上、50μm以下であることがより好ましく、10μm以上、35μmであることが特に好ましく、15μm以上、25μm以下であることが最も好ましい。
The fiber diameter and fiber length of the non-thermal adhesive fiber, and the composite ratio in the case of a composite fiber are not particularly limited. However, if the fiber diameter and fiber length of the non-thermoadhesive fiber are significantly different from those of the thermoadhesive fiber, the productivity of the short fiber layer may be lowered, and the effect of the present invention may be impaired. is there. Therefore, the fiber diameter of the non-thermoadhesive fiber is also preferably 5 μm or more and 80 μm or less, more preferably 8 μm or more and 50 μm or less, particularly preferably 10 μm or more and 35 μm, and more preferably 15 μm or more and 25 μm or less. Most preferably.
また非熱接着性繊維の繊維長は、20mm以上、110mm以下であることが好ましく、25mm以上、85mm以下であることがより好ましく、30mm以上、80mm以下であることが特に好ましく、42mm以上、64mm以下であることが最も好ましい。短繊維層の製造方法による好ましい非熱接着性繊維の繊維長の範囲は、熱接着性繊維のそれらと同じである。
The fiber length of the non-thermoadhesive fiber is preferably 20 mm or more and 110 mm or less, more preferably 25 mm or more and 85 mm or less, particularly preferably 30 mm or more and 80 mm or less, 42 mm or more and 64 mm or less. Most preferably: The range of the fiber length of the preferable non-heat-bondable fiber by the manufacturing method of the short fiber layer is the same as that of the heat-bondable fiber.
短繊維層の目付は特に限定されないが、短繊維層の目付は3g/m2以上、100g/m2であることが好ましい。短繊維層の目付が3g/m2以上であると、得られる導電性繊維構造物が嵩高となり、機械的特性においても優れたものとなる。繊維ウェブの目付が100g/m2以下であると、得られる導電性繊維構造物が適度な厚みを有し、取扱い性及び後加工性が良好なものとなりうる。短繊維層の目付は5g/m2以上、80g/m2以下であることがより好ましく、10g/m2以上、70g/m2以下であることが特に好ましく、10g/m2以上、50g/m2以下であることが最も好ましい。
The basis weight of the short fiber layer is not particularly limited, but the basis weight of the short fiber layer is preferably 3 g / m 2 or more and 100 g / m 2 . When the basis weight of the short fiber layer is 3 g / m 2 or more, the resulting conductive fiber structure is bulky and excellent in mechanical properties. When the basis weight of the fiber web is 100 g / m 2 or less, the resulting conductive fiber structure can have an appropriate thickness, and the handleability and post-processability can be good. Basis weight of the short fiber layer is 5 g / m 2 or more, more preferably 80 g / m 2 or less, 10 g / m 2 or more, particularly preferably at 70 g / m 2 or less, 10 g / m 2 or more, 50 g / Most preferably m 2 or less.
本発明の導電性繊維構造物を加熱処理に付して、金属多孔構造物とし、この金属多孔構造物に活物質合剤を充填させて、電池用電極材を製造する場合、短繊維層は、芯成分がポリエステル系樹脂からなり、鞘成分がポリエチレンからなる熱接着性複合繊維を、好ましくは20質量%以上、より好ましくは50質量%以上、特に好ましくは80質量%以上、最も好ましくは100質量%含む。ポリエステル系樹脂は、好ましくはポリエチレンテレフタレートである。ポリエチレンは、好ましくは高密度ポリエチレンである。
When the conductive fiber structure of the present invention is subjected to heat treatment to form a metal porous structure, and this metal porous structure is filled with an active material mixture to produce a battery electrode material, the short fiber layer is The heat-adhesive conjugate fiber whose core component is made of a polyester resin and whose sheath component is made of polyethylene is preferably 20% by mass or more, more preferably 50% by mass or more, particularly preferably 80% by mass or more, and most preferably 100%. Including mass%. The polyester resin is preferably polyethylene terephthalate. The polyethylene is preferably high density polyethylene.
電池用電極材は、その製造過程において、厚み調整工程に付されて、均一な厚みを有するように加工される。そのため、導電性繊維構造物またはこれから作製される金属多孔構造物は、ある程度の嵩を有していて、圧縮され得ることが望ましい。芯/鞘がポリエステル系樹脂/ポリエチレンである熱接着性複合繊維を使用すると、繊維同士が強固に熱接着されて高い強度を有し、かつ嵩高な導電性繊維構造物を実現できるので、電池用電極材を後加工によって所望の厚みに調整することが容易となる。
In the manufacturing process, the battery electrode material is subjected to a thickness adjusting step and processed to have a uniform thickness. Therefore, it is desirable that the conductive fiber structure or the metal porous structure produced therefrom has a certain amount of bulk and can be compressed. Use of heat-adhesive conjugate fibers with a core / sheath made of polyester resin / polyethylene makes it possible to realize a bulky conductive fiber structure that is strongly heat-bonded to each other and has high strength. It becomes easy to adjust the electrode material to a desired thickness by post-processing.
電池用電極材を、導電性繊維構造物に活物質合剤を充填させて製造する場合(即ち、熱消失性物質を除去しない場合)、熱接着性複合繊維は、芯成分及び鞘成分が共にポリオレフィン系樹脂からなるものであることが好ましい。電池用電極材は一般に、アルカリ溶液または有機溶剤に浸漬されて使用されるためである。芯/鞘の好ましい組み合わせは、例えば、ポリプロピレン/高密度ポリエチレンである。
When the battery electrode material is manufactured by filling an active fiber mixture in a conductive fiber structure (that is, when the heat-dissipating material is not removed), the heat-adhesive conjugate fiber has both a core component and a sheath component. It is preferable that it consists of polyolefin resin. This is because the battery electrode material is generally used by being immersed in an alkaline solution or an organic solvent. A preferred core / sheath combination is, for example, polypropylene / high density polyethylene.
本発明の導電性繊維構造物それ自体に、またはこれを金属多孔構造物としてから、活物質合剤を充填させて、電池用電極材とする場合、熱接着性繊維の繊維径は、10μm以上、35μm以下であることが好ましく、15μm以上、30μm以下であることがより好ましい。熱接着性繊維の繊維径が10μm未満であると、所定の目付の短繊維層において、繊維の表面積が大きくなるため所定の厚みの金属皮膜を得るのにより多くの金属が必要とされる。このことは、所望の厚みの金属皮膜を得ることを難しくすることがある。また、繊維径の小さい繊維で短繊維層を構成すると、繊維密度が高くなり、所望の量の活物質合剤を充填できないことがある。さらに、熱接着性繊維の繊維径が小さいと、金属多孔構造物において得られる金属繊維の繊維径も小さくなり、金属繊維が破断されやすくなることで、破断された金属繊維が金属異物の原因となったり、電池においてデンドライド発生の原因となったりすることがある。
When the conductive fiber structure itself of the present invention itself or a metal porous structure is filled with an active material mixture to obtain a battery electrode material, the fiber diameter of the heat-adhesive fiber is 10 μm or more. 35 μm or less, preferably 15 μm or more and 30 μm or less. When the fiber diameter of the heat-adhesive fiber is less than 10 μm, the surface area of the fiber is increased in the short fiber layer having a predetermined basis weight, so that more metal is required to obtain a metal film having a predetermined thickness. This can make it difficult to obtain a metal film of the desired thickness. Moreover, when a short fiber layer is comprised with a fiber with a small fiber diameter, a fiber density will become high and a desired quantity of active material mixture may not be filled. Furthermore, if the fiber diameter of the heat-adhesive fiber is small, the fiber diameter of the metal fiber obtained in the metal porous structure is also small, and the metal fiber is easily broken. Or may cause dendrites in the battery.
一方、熱接着性繊維の繊維径が35μmを超えると、短繊維層の地合が悪くなる、即ち、均一性が低下するので、導電性繊維構造物または金属多孔構造物に活物質合剤を充填させるときに、粗な部分において活物質合剤が脱落することがある。
On the other hand, when the fiber diameter of the heat-adhesive fiber exceeds 35 μm, the formation of the short fiber layer is deteriorated, that is, the uniformity is lowered. Therefore, an active material mixture is added to the conductive fiber structure or the metal porous structure. When filling, the active material mixture may fall off in rough parts.
電池用電極材を製造する場合に、短繊維層が非熱接着性繊維を含む場合、その好ましい繊維径は、熱接着性繊維のそれと同じである。熱接着性繊維と非熱接着性繊維の繊維径において差が生じると、短繊維層の生産性が低下することがあり、また、活物質合剤が均一に充填されないことがある。
When producing a battery electrode material, when the short fiber layer contains non-thermal adhesive fibers, the preferred fiber diameter is the same as that of the thermal adhesive fibers. If there is a difference in the fiber diameter between the heat-adhesive fiber and the non-heat-adhesive fiber, the productivity of the short fiber layer may be lowered, and the active material mixture may not be uniformly filled.
電池用電極材を構成する場合、その厚みを小さくして巻回性を確保する必要があることから、短繊維層の目付をある程度小さくする必要がある。本発明の導電性繊維構造物それ自体に、またはこれを金属多孔構造物としてから、活物質合剤を充填して電池用電極材とする場合、短繊維層の目付は10g/m2以上、70g/m2以下であることが好ましく、10g/m2以上、50g/m2以下であることがより好ましい。目付がこの範囲内にあると、活物質合剤を良好に充填させることができる。また、導電性繊維構造物の取扱い性及び後加工性が損なわれない。短繊維層の目付が小さすぎると、短繊維層、ひいては繊維構造物において、ムラが生じて、活物質合剤を充填する際に活物質合剤の脱落が生じることがある。また、目付が小さいと、得られる導電性繊維構造物の機械的強度が小さくなり、電池用電極材の製造中に破断等が生じることがある。さらに、短繊維層の目付が小さすぎると、得られる導電性繊維構造物の嵩が小さくなり、所望の厚みに加工することが困難となることがある。
In the case of constituting a battery electrode material, it is necessary to reduce the thickness of the battery electrode material to ensure the winding property, and therefore it is necessary to reduce the basis weight of the short fiber layer to some extent. When the conductive fiber structure of the present invention itself or a metal porous structure thereof is filled with an active material mixture to form a battery electrode material, the basis weight of the short fiber layer is 10 g / m 2 or more, It is preferably 70 g / m 2 or less, more preferably 10 g / m 2 or more and 50 g / m 2 or less. When the basis weight is within this range, the active material mixture can be satisfactorily filled. Moreover, the handleability and post-processability of the conductive fiber structure are not impaired. If the basis weight of the short fiber layer is too small, unevenness may occur in the short fiber layer, and hence the fiber structure, and the active material mixture may fall off when filling the active material mixture. In addition, when the basis weight is small, the mechanical strength of the obtained conductive fiber structure becomes small, and breakage or the like may occur during the production of the battery electrode material. Furthermore, if the basis weight of the short fiber layer is too small, the resulting conductive fiber structure may be reduced in volume and difficult to be processed to a desired thickness.
短繊維層の目付が大きすぎると、得られる導電性繊維構造物が取扱い性及び後加工性において劣ることがあり、また、電池用電極材の巻回性が低下することがある。また、短繊維層の目付が大きすぎると、活物質合剤を充填させることが困難となり、所望の量の活物質合剤が充填された電池用電極材が得られないことがある。
If the basis weight of the short fiber layer is too large, the resulting conductive fiber structure may be inferior in handleability and post-processability, and the winding property of the battery electrode material may be reduced. Moreover, when the fabric weight of a short fiber layer is too large, it will become difficult to fill an active material mixture, and the battery electrode material with which the desired amount of active material mixture was filled may not be obtained.
本発明の導電性繊維構造物それ自体に、またはこれを金属多孔構造物としてから、活物質合剤を充填させて、電池用電極材とする場合、短繊維層の比容積は、好ましくは5cm3/g以上、80cm3/g以下であり、より好ましくは10cm3/g以上、70cm3/g以下である。比容積がこの範囲内にあると、活物質合剤を効率よくかつ十分に充填させることができる。短繊維層の比容積が小さすぎると、構成繊維間の空隙が小さくなって、十分な量の活物質合剤を導電性構造物または金属多孔構造物に充填させられないことがある。短繊維層の比容積が大きすぎると、構成繊維間の空隙が大きくなって、活物質合剤を充填する際に活物質合剤の脱落が生じることがある。
When the conductive fiber structure of the present invention itself or a metal porous structure is filled with an active material mixture to form a battery electrode material, the specific volume of the short fiber layer is preferably 5 cm. 3 / g or more and 80 cm 3 / g or less, more preferably 10 cm 3 / g or more and 70 cm 3 / g or less. When the specific volume is within this range, the active material mixture can be filled efficiently and sufficiently. When the specific volume of the short fiber layer is too small, the gap between the constituent fibers becomes small, and a sufficient amount of the active material mixture may not be filled in the conductive structure or the metal porous structure. When the specific volume of the short fiber layer is too large, gaps between the constituent fibers become large, and the active material mixture may fall off when filling the active material mixture.
次に、前記短繊維層と前記長繊維シート状物とを含み、繊維表面に金属皮膜が形成された、本発明の導電性繊維構造物について説明する。
導電性繊維構造物は、短繊維層と長繊維シート状物を一体化させてから、繊維表面に金属皮膜を形成する方法で製造してよく、あるいは短繊維層及び長繊維シート状物の繊維表面に金属皮膜を形成してから、それらを積層し、好ましくは一体化させる方法で製造してよい。導電性繊維構造物は、工程性及び電気特性の点から、先に短繊維層と長繊維シート状物を一体化させた積層体(以下、金属皮膜を形成する前の短繊維層と長繊維シート状物とを含む積層体を「積層繊維構造物」とも呼ぶ)を得た後に、金属皮膜を繊維表面に形成する方法で製造されることが好ましい。 Next, the conductive fiber structure of the present invention including the short fiber layer and the long fiber sheet and having a metal film formed on the fiber surface will be described.
The conductive fiber structure may be manufactured by a method of forming a metal film on the fiber surface after integrating the short fiber layer and the long fiber sheet, or the fibers of the short fiber layer and the long fiber sheet. After forming a metal film on the surface, they may be laminated and preferably integrated. From the viewpoint of processability and electrical characteristics, the conductive fiber structure is a laminate in which the short fiber layer and the long fiber sheet are first integrated (hereinafter referred to as the short fiber layer and the long fiber before forming the metal film). It is preferable to produce the laminate including a sheet-like material by a method of forming a metal film on the fiber surface after obtaining a laminate (also referred to as “laminated fiber structure”).
導電性繊維構造物は、短繊維層と長繊維シート状物を一体化させてから、繊維表面に金属皮膜を形成する方法で製造してよく、あるいは短繊維層及び長繊維シート状物の繊維表面に金属皮膜を形成してから、それらを積層し、好ましくは一体化させる方法で製造してよい。導電性繊維構造物は、工程性及び電気特性の点から、先に短繊維層と長繊維シート状物を一体化させた積層体(以下、金属皮膜を形成する前の短繊維層と長繊維シート状物とを含む積層体を「積層繊維構造物」とも呼ぶ)を得た後に、金属皮膜を繊維表面に形成する方法で製造されることが好ましい。 Next, the conductive fiber structure of the present invention including the short fiber layer and the long fiber sheet and having a metal film formed on the fiber surface will be described.
The conductive fiber structure may be manufactured by a method of forming a metal film on the fiber surface after integrating the short fiber layer and the long fiber sheet, or the fibers of the short fiber layer and the long fiber sheet. After forming a metal film on the surface, they may be laminated and preferably integrated. From the viewpoint of processability and electrical characteristics, the conductive fiber structure is a laminate in which the short fiber layer and the long fiber sheet are first integrated (hereinafter referred to as the short fiber layer and the long fiber before forming the metal film). It is preferable to produce the laminate including a sheet-like material by a method of forming a metal film on the fiber surface after obtaining a laminate (also referred to as “laminated fiber structure”).
積層繊維構造物においては、短繊維層と長繊維シート状物とが、繊維同士の交絡により一体化している。繊維ウェブと長繊維シート状物とを一体化する処理は特に限定されず、公知の方法で一体化される。一体化は、例えば、高圧水流で構成繊維を交絡一体化させる水流交絡法による処理、ニードルパンチ法による処理などの物理的衝撃によって構成繊維を交絡一体化する処理により実施してよい。物理的衝撃によって構成繊維を交絡一体化する処理は、短繊維層と長繊維シート状物との一体化と、短繊維層の構成繊維同士の交絡を同時に実施して積層繊維構造物を与える。これらの交絡処理に加えて、サーマルボンド、ケミカルボンド、またはステッチボンド等の処理を実施してよい。
In the laminated fiber structure, the short fiber layer and the long fiber sheet are integrated by interlacing of fibers. The treatment for integrating the fiber web and the long fiber sheet is not particularly limited, and the fiber web and the long fiber sheet are integrated by a known method. The integration may be performed, for example, by a process of confounding and integrating the constituent fibers by a physical impact such as a process using a hydroentanglement method in which the constituent fibers are entangled and integrated with a high-pressure water stream or a needle punch method. The process of confounding and integrating the constituent fibers by physical impact simultaneously performs the integration of the short fiber layer and the long fiber sheet and the confounding of the constituent fibers of the short fiber layer to give a laminated fiber structure. In addition to these entanglement processes, a process such as a thermal bond, a chemical bond, or a stitch bond may be performed.
物理的衝撃として高圧水流を用いる水流交絡法は、繊維同士を強固に交絡させるので、より好ましい。水流交絡法を用いる場合、公知の方法を用いることができ、適切な水圧、水流を噴射する回数、水流を噴射するノズルの径及び間隔が選択される。また、水流交絡処理の際に、必要に応じて、積層繊維構造物に特定形状を付与する、いわゆるパターニングを施してよく、あるいは、高圧水流によって、積層繊維構造物に開孔を設けてもよい。
The hydroentanglement method using a high-pressure water stream as a physical impact is more preferable because the fibers are firmly entangled with each other. When using the water entangling method, a known method can be used, and an appropriate water pressure, the number of times of jetting the water flow, the diameter and interval of the nozzles for jetting the water flow are selected. In addition, during the hydroentanglement treatment, if necessary, so-called patterning may be performed to give a specific shape to the laminated fiber structure, or openings may be provided in the laminated fiber structure by high-pressure water flow. .
本発明の導電性繊維構造物を製造するにあたり、繊維ウェブと長繊維シート状物を交絡、一体化させ、積層繊維構造物とする水流交絡処理は、例えば次のような条件で実施することができる。まず、繊維ウェブと長繊維シート状物の積層物を80メッシュから100メッシュの平織の支持体の上に載せて、孔径0.05mm以上、0.5mm以下のオリフィスが0.5mm以上、1.5mm以下の間隔で設けられたノズルから、水圧が0.1MPa以上、10MPa以下、好ましくは水圧が0.5MPa以上、5MPa以下、特に好ましくは水圧が0.7MPa以上、3.0MPa以下の柱状水流を前記積層物に噴射することにより実施してよい。柱状水流を噴射するのは、表面のみ、裏面のみ、表裏両面、のいずれであってもよく、噴射する回数も1回以上、5回以下であれば特に限定されないが表面、裏面と交互になるように、0.7MPa以上、3.0MPa以下の高圧水流を表面、裏面にそれぞれ1回または2回噴射することが好ましい。柱状水流を噴射した積層繊維構造物において、繊維ウェブを構成する短繊維は、その繊維長方向が厚み方向に対して垂直になるように配置されている。この積層繊維構造物に金属皮膜を設けた導電性繊維構造物、また、これを焼成して得られる金属多孔構造物においては、金属被覆繊維端や金属繊維端が直立しておらず、針状突起が発生しにくい。そのため、これらに活物質を充填すると、従来のウレタンフォームを使用した電極材と比較してデンドライトが発生しにくい各種電極材が容易に得られる。従って、本発明の導電性繊維構造物を各種電極材に使用する場合には、上記条件で柱状水流を噴射した積層繊維構造物を使用することが好ましい。水流交絡処理を行い、交絡・一体化した繊維ウェブと長繊維シート状物の積層物は後述する条件で乾燥・熱接着処理を行うことが好ましい。
In producing the conductive fiber structure according to the present invention, the hydroentanglement process in which the fiber web and the long fiber sheet are entangled and integrated to form a laminated fiber structure can be carried out under the following conditions, for example. it can. First, a laminate of a fibrous web and a long fiber sheet is placed on a plain mesh support of 80 mesh to 100 mesh, and an orifice having a pore diameter of 0.05 mm or more and 0.5 mm or less is 0.5 mm or more. Columnar water flow with a water pressure of 0.1 MPa or more and 10 MPa or less, preferably a water pressure of 0.5 MPa or more and 5 MPa or less, particularly preferably a water pressure of 0.7 MPa or more and 3.0 MPa or less from a nozzle provided at intervals of 5 mm or less. May be carried out by spraying onto the laminate. The columnar water stream may be jetted only on the front surface, only on the back surface, or both on the front and back surfaces, and is not particularly limited as long as the number of times of spraying is 1 or more and 5 or less. Thus, it is preferable to inject a high-pressure water flow of 0.7 MPa or more and 3.0 MPa or less once or twice on the front surface and the back surface, respectively. In the laminated fiber structure in which the columnar water stream is jetted, the short fibers constituting the fiber web are arranged so that the fiber length direction is perpendicular to the thickness direction. In the conductive fiber structure provided with a metal film on the laminated fiber structure, and the metal porous structure obtained by firing the structure, the metal-coated fiber end and the metal fiber end are not upright, and the needle-like structure Protrusion is unlikely to occur. Therefore, when these are filled with an active material, various electrode materials in which dendrite is hardly generated can be easily obtained as compared with an electrode material using a conventional urethane foam. Accordingly, when the conductive fiber structure of the present invention is used for various electrode materials, it is preferable to use a laminated fiber structure in which a columnar water stream is jetted under the above conditions. It is preferable to perform a hydroentanglement treatment, and the laminate of the entangled / integrated fiber web and the long fiber sheet is subjected to a drying / thermal bonding treatment under the conditions described later.
本発明の導電性繊維構造物は、少なくとも1つの短繊維層と、少なくとも1つの長繊維シート状物からなる層を有している限りにおいて、各層の数及び積層順序は、特に限定されない。好ましくは、積層繊維構造物は、両表面を構成する層が短繊維層であるように、各層の数及び積層順序を選択して形成される。これは、積層繊維構造物において、両表面を構成する層の少なくとも一方が長繊維シート状物であると、表面層となった長繊維シート状物が短繊維層から剥離しやすくなるためである。特に、積層繊維構造物は、長繊維シート状物を中層とし、その両表面に短繊維層を配置した3層構造の積層物であることが特に好ましい。
As long as the conductive fiber structure of the present invention has at least one short fiber layer and at least one layer composed of a long fiber sheet, the number of layers and the stacking order are not particularly limited. Preferably, the laminated fiber structure is formed by selecting the number of layers and the order of lamination so that the layers constituting both surfaces are short fiber layers. This is because, in a laminated fiber structure, when at least one of the layers constituting both surfaces is a long fiber sheet, the long fiber sheet that has become the surface layer is easily peeled from the short fiber layer. . In particular, the laminated fiber structure is particularly preferably a laminate having a three-layer structure in which a long fiber sheet is used as an intermediate layer and short fiber layers are disposed on both surfaces thereof.
積層繊維構造物において、短繊維層及び長繊維シート状物のうち、少なくとも一方が複数層設けられる場合、複数積層する層は同一の層であってもよく、異なる構成及び/または特性の層であってもよい。例えば、短繊維層を2つ以上積層する場合、短繊維層は互いに構成繊維の原料、繊維径、及び/または繊維長が異なるものであってよく、ならびに/あるいは目付が互いに異なるものであってよい。長繊維シート状物を2つ以上積層する場合、長繊維シート状物は互いに構成繊維の原料、繊維径、及び/または製造方法が異なるものであってよく、ならびに/あるいは目付及び開口部の面積の異なるものであってもよい。
In a laminated fiber structure, when at least one of a short fiber layer and a long fiber sheet is provided with a plurality of layers, the layers to be laminated may be the same layer, or layers having different configurations and / or characteristics. There may be. For example, when two or more short fiber layers are laminated, the short fiber layers may have different constituent fiber materials, fiber diameters, and / or fiber lengths, and / or have different basis weights. Good. When two or more long fiber sheet materials are laminated, the long fiber sheet materials may have different constituent fiber materials, fiber diameters, and / or manufacturing methods, and / or areal weight and area of openings. May be different.
積層繊維構造物においては、短繊維層が熱接着繊維を含み、短繊維層を構成する繊維同士及び/又は短繊維層を構成する繊維と長繊維シート状物を構成する長繊維とが熱接着していることが好ましい。積層繊維構造物において繊維同士が熱接着していると、繊維の接着交点で結ばれた連続した繊維ネットワークが形成されて、より良好な電気伝導性、高い引張強力、及び嵩高性を得ることができる。熱接着処理を行う時期は特に限定されない。例えば、短繊維層を長繊維シート状物に積層した後、熱接着処理を行って得られた積層繊維構造物をそのまま金属皮膜を形成するための処理に付してよい。あるいは、水流交絡法で短繊維層と長繊維シート状物と一体化させた後、熱接着処理を実施してよい。その場合、熱接着処理は、水流交絡処理後の積層繊維構造物を比較的低い温度(熱接着繊維が熱接着しない温度)で乾燥させてから、実施してよく、あるいは、水流交絡処理後の乾燥処理と同時に実施してよい。即ち、乾燥処理において熱接着処理を実施してよい。
In the laminated fiber structure, the short fiber layer includes heat-bonding fibers, and the fibers constituting the short fiber layer and / or the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet-like material are thermally bonded. It is preferable. When fibers are thermally bonded to each other in a laminated fiber structure, a continuous fiber network formed by bonding points of fibers is formed, and better electrical conductivity, high tensile strength, and bulkiness can be obtained. it can. There is no particular limitation on the timing for performing the thermal bonding treatment. For example, after laminating the short fiber layer on the long fiber sheet, the laminated fiber structure obtained by performing the heat bonding treatment may be subjected to a treatment for forming a metal film as it is. Alternatively, after the short fiber layer and the long fiber sheet are integrated by the hydroentanglement method, the heat bonding treatment may be performed. In that case, the thermal bonding treatment may be performed after drying the laminated fiber structure after the hydroentanglement treatment at a relatively low temperature (a temperature at which the thermal adhesion fiber is not thermally bonded), or after the hydroentanglement treatment. It may be carried out simultaneously with the drying process. That is, a thermal bonding process may be performed in the drying process.
熱接着処理温度は特に限定されず、短繊維層及び/または長繊維シート状物を構成する熱接着性繊維の少なくとも一部が溶融する温度で実施する。熱接着性繊維が複合繊維である場合には、低融点合成樹脂の融点よりも10℃以上高い温度で熱接着処理を実施することが好ましい。例えば、熱接着処理温度は、100℃以上、200℃以下であることが好ましく、110℃以上、180℃以下であることがより好ましく、120℃以上、170℃以下であることが特に好ましく、120℃以上、160℃以下であることが最も好ましい。
The heat bonding treatment temperature is not particularly limited, and is performed at a temperature at which at least a part of the heat bonding fibers constituting the short fiber layer and / or the long fiber sheet is melted. When the heat-adhesive fiber is a composite fiber, it is preferable to perform the heat-adhesion treatment at a temperature higher by 10 ° C. or more than the melting point of the low-melting-point synthetic resin. For example, the heat bonding treatment temperature is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 110 ° C. or higher and 180 ° C. or lower, particularly preferably 120 ° C. or higher and 170 ° C. or lower, 120 Most preferably, it is not lower than 160 ° C and not higher than 160 ° C.
積層繊維構造物の目付は特に限定されず、例えば、10g/m2以上、150g/m2以下であることが好ましい。積層繊維構造物の目付が10g/m2以上であると、得られる導電性繊維構造物が機械的特性に優れるだけでなく、繊維間空隙が多く嵩高なものとなる。積層繊維構造物の目付が150g/m2以下であると、積層構造物自体が過度に厚くなること、及び/または繊維間空隙が過度に少ない、密なものになることを避けることができ、また、適度な柔らかさを有する。そのような積層繊維構造物は、良好な取扱い性及び後加工性を有する。積層繊維構造物の目付は、15g/m2以上、100g/m2以下であることがより好ましく、20g/m2以上、70g/m2以下であることが特に好ましく、25g/m2以上、60g/m2以下が最も好ましい。
The basis weight of the laminated fiber structure is not particularly limited, and is preferably 10 g / m 2 or more and 150 g / m 2 or less, for example. When the basis weight of the laminated fiber structure is 10 g / m 2 or more, the obtained conductive fiber structure is not only excellent in mechanical properties, but also has a large inter-fiber gap and becomes bulky. When the basis weight of the laminated fiber structure is 150 g / m 2 or less, it can be avoided that the laminated structure itself becomes excessively thick and / or the inter-fiber void is excessively small and dense. Moreover, it has moderate softness. Such a laminated fiber structure has good handleability and post-processability. The basis weight of the laminated fiber structure is more preferably 15 g / m 2 or more and 100 g / m 2 or less, particularly preferably 20 g / m 2 or more and 70 g / m 2 or less, 25 g / m 2 or more, Most preferred is 60 g / m 2 or less.
本発明の導電性繊維構造物それ自体に、またはこれを金属多孔構造物としてから、活物質合剤を充填させて、電池用電極材とする場合に、積層繊維構造物の目付はこれらの範囲を満たすことが望ましい。活物質合剤の充填の容易性及び充填量は、積層繊維構造物の目付と関係するからである。目付が小さすぎると、活物質合剤を充填する際に活物質合剤が脱落することがあり、また、活物質合剤が均一に充填されないことがある。目付が大きすぎると、十分な量の活物質合剤が充填されないことがある。
When the conductive fiber structure of the present invention itself or a metal porous structure is filled with an active material mixture to obtain a battery electrode material, the basis weight of the laminated fiber structure is within these ranges. It is desirable to satisfy. This is because the ease of filling and the filling amount of the active material mixture are related to the basis weight of the laminated fiber structure. If the basis weight is too small, the active material mixture may fall off when filling the active material mixture, and the active material mixture may not be filled uniformly. If the basis weight is too large, a sufficient amount of the active material mixture may not be filled.
積層繊維構造物の厚みは特に限定されないが、0.2mm以上、10mm以下であることが好ましい。積層繊維構造物及び導電性繊維構造物の取り扱い性及び後加工性を考慮すると、積層繊維構造物の厚みは0.3mm以上、5mm以下であることがより好ましく、0.3mm以上、2mm以下であることが特に好ましく、0.4mm以上、1.5mm以下であることが最も好ましい。
The thickness of the laminated fiber structure is not particularly limited, but is preferably 0.2 mm or more and 10 mm or less. Considering the handleability and post-processability of the laminated fiber structure and the conductive fiber structure, the thickness of the laminated fiber structure is more preferably 0.3 mm or more and 5 mm or less, and 0.3 mm or more and 2 mm or less. It is particularly preferable that the thickness is 0.4 mm or more and 1.5 mm or less.
積層繊維構造物が嵩高で、繊維間空隙が多いものかどうかを表す指標として、積層繊維構造物の密度が挙げられる。積層繊維構造物の密度は特に限定されないが、0.01g/cm3以上、0.20g/cm3以下であることが好ましい。密度が0.01g/cm3以上であると、取扱い性及び後加工性、ならびに力学的特性が極端に低下することがない。積層繊維構造物の密度が0.20g/cm3以下であると、積層繊維構造物及び本発明の導電性繊維構造物が充分に嵩高で、繊維間空隙の多いものとなる。積層繊維構造物の密度は0.014g/cm3以上、0.125g/cm3以下であることがより好ましく、0.02g/cm3以上、0.1g/cm3以下であることが特に好ましく、0.025g/cm3以上、0.1g/cm3以下であることが最も好ましい。
As an index indicating whether the laminated fiber structure is bulky and has many interfiber gaps, the density of the laminated fiber structure can be mentioned. The density of the laminated fiber structure is not particularly limited, but is preferably 0.01 g / cm 3 or more and 0.20 g / cm 3 or less. When the density is 0.01 g / cm 3 or more, handleability, post-processability, and mechanical properties are not extremely deteriorated. When the density of the laminated fiber structure is 0.20 g / cm 3 or less, the laminated fiber structure and the conductive fiber structure of the present invention are sufficiently bulky and have many interfiber spaces. The density of the laminated fiber structure 0.014 g / cm 3 or more, more preferably 0.125 g / cm 3 or less, 0.02 g / cm 3 or more, particularly preferably at 0.1 g / cm 3 or less 0.025 g / cm 3 or more and 0.1 g / cm 3 or less is most preferable.
積層繊維構造物の密度と同様、積層繊維構造物が嵩高で、繊維間空隙が多いものかどうかを表す指標として、積層繊維構造物の比容積が挙げられる。積層繊維構造物の比容積は特に限定されないが、5cm3/g以上、100cm3/g以下であることが好ましい。比容積が5cm3/g以上であると積層繊維構造物及び本発明の導電性繊維構造物が充分に嵩高で、繊維間空隙の多いものとなる。比容積が100cm3/g以下であると、取扱い性及び後加工性、ならびに力学的特性が極端に低下することがない。積層繊維構造物の比容積は8cm3/g以上、70cm3/g以下であることがより好ましく、10cm3/g以上、50cm3/g以下であることが特に好ましく、10cm3/g以上、40cm3/g以下であることが最も好ましい。
Similar to the density of the laminated fiber structure, the specific volume of the laminated fiber structure is an index that indicates whether the laminated fiber structure is bulky and has many interfiber gaps. The specific volume of the laminated fiber structure is not particularly limited, but is preferably 5 cm 3 / g or more and 100 cm 3 / g or less. When the specific volume is 5 cm 3 / g or more, the laminated fiber structure and the conductive fiber structure of the present invention are sufficiently bulky and have many inter-fiber voids. When the specific volume is 100 cm 3 / g or less, handling property, post-processing property, and mechanical properties are not extremely deteriorated. Specific volume of the laminated fiber structure 8 cm 3 / g or more, more preferably 70cm 3 / g or less, 10 cm 3 / g or more, 50 cm 3 / g, especially preferably not more than, 10 cm 3 / g or more, Most preferably, it is 40 cm 3 / g or less.
本発明の導電性繊維構造物それ自体に、またはこれを金属多孔構造物としてから、活物質合剤を充填させて、電池用電極材とする場合に、積層繊維構造物の密度及び比容積が、上記の範囲を満たすことが望ましい。活物質合剤の充填の容易性及び充填量は、積層繊維構造物の密度と関係するからである。前記積層繊維構造物の密度が小さすぎると、活物質合剤を充填する際に活物質合剤が脱落することがあり、また、活物質合剤が均一に充填されないことがある。前記積層繊維構造物の密度が大きすぎると、十分な量の活物質合剤が充填されないことがある。
When the conductive fiber structure of the present invention itself or a metal porous structure is filled with an active material mixture to form a battery electrode material, the density and specific volume of the laminated fiber structure are It is desirable to satisfy the above range. This is because the ease and amount of filling of the active material mixture are related to the density of the laminated fiber structure. If the density of the laminated fiber structure is too small, the active material mixture may fall off when the active material mixture is filled, and the active material mixture may not be filled uniformly. If the density of the laminated fiber structure is too large, a sufficient amount of the active material mixture may not be filled.
積層繊維構造物のMD方向の引張強力及びCD方向の引張強力は特に限定されないが、MD方向の引張強力は30N/50mm以上であることが好ましく、CD方向の引張強力は12N/50mm以上であることが好ましい。MD方向及びCD方向の引張強力が前記範囲を満たすと、積層繊維構造物の力学的特性が優れたものとなり、積層繊維構造物及び本発明の導電性繊維構造物が取扱い性、及び後加工性に優れたものになる。また、そのような引張強力を有する積層繊維構造物から製造される導電性繊維構造物は、使用中に破損するおそれの少ないものとなりうる。MD方向の引張強力は、40N/50mm以上、160N/50mm以下であることがより好ましく、50N/50mm以上、150N/50mm以下であることが特に好ましい。CD方向の引張強力は、15N/50mm以上、100N/50mm以下であることがより好ましく、25N/50mm以上、80N/50mm以下であることが特に好ましい。
The tensile strength in the MD direction and the tensile strength in the CD direction of the laminated fiber structure are not particularly limited, but the tensile strength in the MD direction is preferably 30 N / 50 mm or more, and the tensile strength in the CD direction is 12 N / 50 mm or more. It is preferable. When the tensile strength in the MD direction and the CD direction satisfy the above ranges, the laminated fiber structure has excellent mechanical properties, and the laminated fiber structure and the conductive fiber structure of the present invention are easy to handle and post-process. It will be excellent. Moreover, the conductive fiber structure manufactured from the laminated fiber structure having such tensile strength can be less likely to break during use. The tensile strength in the MD direction is more preferably 40 N / 50 mm or more and 160 N / 50 mm or less, and particularly preferably 50 N / 50 mm or more and 150 N / 50 mm or less. The tensile strength in the CD direction is more preferably 15 N / 50 mm or more and 100 N / 50 mm or less, and particularly preferably 25 N / 50 mm or more and 80 N / 50 mm or less.
積層繊維構造物は、長繊維が一方向だけでなく、一方向と交差する方向にも配向している長繊維シート状物を少なくとも1層含む。そのため、一般的な繊維集合物、特に、カードウェブのみを用いて作製した不織布において、MD方向の物性値とCD方向の物性値が異なるのに対し、積層繊維構造物においては、それらの値の差が小さくなる傾向にある。
The laminated fiber structure includes at least one layer of a long fiber sheet in which long fibers are oriented not only in one direction but also in a direction crossing one direction. Therefore, in a general fiber assembly, particularly in a nonwoven fabric produced using only a card web, the physical property value in the MD direction and the physical property value in the CD direction are different, whereas in a laminated fiber structure, those values are The difference tends to be smaller.
このような傾向を示す物性値として、積層繊維構造物の引張強力及び伸度が挙げられる。カードウェブのみを用いて作製した不織布のように、構成繊維のMD方向への配向性が強い繊維集合物においては、構成繊維の配向に起因して、MD方向の引張強力がCD方向の引張強力と比較して大きくなる。そのような繊維構造物において、例えば、CD方向の引張強力に対するMD方向の引張強力の比(生産方向/巾方向)が3程度になることがあり、繊維の配向がより強くなると、これより大きい比となることもある。逆に、MD方向への配向性が強い繊維集合物において、MD方向の伸度はCD方向の伸度と比較して小さくなり、CD方向の伸度に対するMD方向の伸度の比(生産方向/巾方向)が0.7程度になることがあり、繊維の配向がより強くなると、これより小さい比となることもある。
The physical property values showing such a tendency include the tensile strength and elongation of the laminated fiber structure. In a fiber assembly having a strong orientation in the MD direction of the constituent fibers, such as a non-woven fabric produced using only the card web, the tensile strength in the MD direction is different from the tensile strength in the CD direction due to the orientation of the constituent fibers. Compared to In such a fiber structure, for example, the ratio of the tensile strength in the MD direction to the tensile strength in the CD direction (production direction / width direction) may be about 3, which is larger when the fiber orientation becomes stronger. It may be a ratio. On the other hand, in a fiber assembly having a strong orientation in the MD direction, the MD direction elongation is smaller than the CD direction elongation, and the ratio of the MD direction elongation to the CD direction elongation (production direction). / Width direction) may be about 0.7, and if the fiber orientation becomes stronger, the ratio may be smaller.
積層繊維構造物において、構成繊維の配向度合いを判断する指標として、CD方向の引張強力に対するMD方向の引張強力の比(以下、単に「引張強力のMD/CD比」とも称す)、あるいはCD方向の伸度に対するMD方向の伸度の比(以下、単に「伸度のMD/CD比」とも称す)を用いることができる。積層繊維構造物において、引張強力のMD/CD比は0.7以上、3以下であることが好ましく、0.8以上、2.5以下であることがより好ましい。積層繊維構造物において、伸度のMD/CD比は、特に限定されず、例えば、0.7以上、2.5以下であるとより好ましく、0.8以上、2以下であるとより好ましい。
In the laminated fiber structure, as an index for determining the degree of orientation of the constituent fibers, the ratio of the tensile strength in the MD direction to the tensile strength in the CD direction (hereinafter, also simply referred to as “MD / CD ratio of tensile strength”), or the CD direction The ratio of the elongation in the MD direction to the elongation (hereinafter also simply referred to as “MD / CD ratio of elongation”) can be used. In the laminated fiber structure, the MD / CD ratio of tensile strength is preferably 0.7 or more and 3 or less, and more preferably 0.8 or more and 2.5 or less. In the laminated fiber structure, the MD / CD ratio of elongation is not particularly limited, and is, for example, preferably 0.7 or more and 2.5 or less, and more preferably 0.8 or more and 2 or less.
次に、前記積層繊維構造物の構成繊維表面に金属皮膜を形成して導電性を付与し、本発明の導電性繊維構造物を得る方法を説明する。
Next, a method for obtaining a conductive fiber structure of the present invention by forming a metal film on the surface of the constituent fibers of the laminated fiber structure to impart conductivity will be described.
前記積層繊維構造物を構成する構成繊維の表面に金属皮膜を形成して導電性を付与する方法は特に限定されず、公知の方法が用いられる。公知の方法は、例えば、無電解めっき、電解めっき(「電気めっき」とも称される)、及び溶融金属めっきなどのめっき法、真空蒸着法、スパッタリング法(「スパッタ法」とも称される)、抵抗加熱蒸着法、電子ビーム蒸着法、分子線エピタキシー法、及びイオンビームデポジションなどの各種物理気相成長法、熱化学気相成長法(「熱CVD」とも称される)、光化学気相成長法(「光CVD」とも称される)、及びプラズマ化学気相成長法(「プラズマCVD」とも称される)等の化学気相成長法、ならびにフレーム溶射法、高速フレーム溶射法、アーク溶射法、プラズマ溶射法、及び線爆溶射法等の溶射法である。生産性及びコスト面を考慮すると、めっき法が好ましく用いられる。
The method for imparting conductivity by forming a metal film on the surface of the constituent fiber constituting the laminated fiber structure is not particularly limited, and a known method is used. Known methods include, for example, electroless plating, electrolytic plating (also referred to as “electroplating”), and plating methods such as molten metal plating, vacuum deposition methods, sputtering methods (also referred to as “sputtering methods”), Various physical vapor deposition methods such as resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, and ion beam deposition, thermal chemical vapor deposition (also called “thermal CVD”), photochemical vapor deposition Chemical vapor deposition such as plasma chemical vapor deposition (also called “plasma CVD”), flame spraying, high-speed flame spraying, arc spraying, etc. These are spraying methods such as plasma spraying and line explosion spraying. In consideration of productivity and cost, a plating method is preferably used.
まず、めっき法によって、積層繊維構造物の構成繊維の表面に金属皮膜を形成する方法についてまず説明する。めっきする金属は特に限定されない。めっきする金属として、例えば、金、銀、銅、白金、ロジウム、ニッケル、クロム、コバルト、スズ、亜鉛、カドミウム、アルミニウム、チタン、マンガン、鉄、及び鉛等が挙げられる。これらの金属から選択される1または複数の金属を選択し、前述した公知のめっき法を用いて、繊維表面に金属皮膜を形成する。めっき法は、無電解めっき法、または電解めっき法であることが好ましい。めっき処理を行う回数は特に限定されない。めっき処理は1回行ってよく、あるいは複数回行ってもよい。めっき処理を複数回行う場合、種類の異なるめっき法を組み合わせてもよいし、同一のめっき法を繰り返してもよい。
First, a method for forming a metal film on the surface of the constituent fiber of the laminated fiber structure by plating will be described first. The metal to be plated is not particularly limited. Examples of the metal to be plated include gold, silver, copper, platinum, rhodium, nickel, chromium, cobalt, tin, zinc, cadmium, aluminum, titanium, manganese, iron, and lead. One or more metals selected from these metals are selected, and a metal film is formed on the fiber surface using the above-described known plating method. The plating method is preferably an electroless plating method or an electrolytic plating method. The number of times of performing the plating process is not particularly limited. The plating process may be performed once or a plurality of times. When the plating treatment is performed a plurality of times, different types of plating methods may be combined, or the same plating method may be repeated.
無電解めっき法について説明する。無電解めっき法は、初めに触媒化工程を行い、次に無電解めっき工程を行う手順で実施するとよい。触媒化工程は、被めっき繊維の表面に触媒を付与する工程である。触媒付与の方法としては、例えば、被めっき繊維を塩化第一スズの塩酸水溶液で処理した後に塩化パラジウムの塩酸水溶液で触媒化する方法、又はアンモニアの水素原子の1個またはそれ以上が炭化水素残基で置換されたアミン系錯化剤と、塩化パラジウムとを含む塩酸溶液のみで固定化する方法等が挙げられる。
The electroless plating method will be described. The electroless plating method may be performed in the procedure of first performing the catalyst step and then performing the electroless plating step. The catalyzing step is a step of imparting a catalyst to the surface of the fiber to be plated. Examples of the method for providing the catalyst include a method in which the fiber to be plated is treated with an aqueous solution of stannous chloride in hydrochloric acid and then catalyzed with an aqueous solution of palladium chloride in hydrochloric acid, or one or more of the hydrogen atoms of ammonia are hydrocarbon residues. And a method of immobilizing only with a hydrochloric acid solution containing an amine complexing agent substituted with a group and palladium chloride.
無電解めっき工程は、析出させる金属を含む溶剤と還元剤とを含む無電解めっき液を使用して、金属膜を形成する工程である。無電解めっき液には、必要に応じて、錯化剤、pH調整剤、緩衝剤、促進剤、安定剤、及び改良剤等を加えてもよい。析出させる金属を含む溶剤は、金属塩を含む溶剤であれば特に限定されない。例えば、ニッケル皮膜を形成する場合、ニッケル塩は、硫酸ニッケル、塩化ニッケル、硝酸ニッケル、またはスルファミン酸ニッケル等であり、還元剤は、例えば、塩酸ヒドラジン、硫酸ヒドラジン、水和ヒドラジン等のヒドラジン誘導体又はヒドラジン、次亜リン酸ナトリウム、またはジメチルアミンボラン等である。
The electroless plating step is a step of forming a metal film using an electroless plating solution containing a solvent containing a metal to be deposited and a reducing agent. You may add a complexing agent, a pH adjuster, a buffering agent, a promoter, a stabilizer, an improving agent, etc. to an electroless-plating liquid as needed. The solvent containing the metal to be deposited is not particularly limited as long as it contains a metal salt. For example, when forming a nickel film, the nickel salt is nickel sulfate, nickel chloride, nickel nitrate, or nickel sulfamate, and the reducing agent is, for example, a hydrazine derivative such as hydrazine hydrochloride, hydrazine sulfate, hydrated hydrazine, or the like. Examples thereof include hydrazine, sodium hypophosphite, dimethylamine borane and the like.
次に、電解めっき法(電気めっき法とも称す)について説明する。電解めっきは、金属塩を溶解させためっき浴を用いて、電気分解により、カソード上に金属を析出させる方法である。ここで、カソードは被めっき繊維で構成される。また、アノードは、めっき浴及び析出させる金属に応じて、適時選択される。
Next, the electrolytic plating method (also referred to as electroplating method) will be described. Electroplating is a method in which a metal is deposited on a cathode by electrolysis using a plating bath in which a metal salt is dissolved. Here, the cathode is made of a fiber to be plated. Further, the anode is appropriately selected according to the plating bath and the metal to be deposited.
電解めっきに用いられるめっき浴について説明する。例えば、電解ニッケルめっきを実施する場合、硫酸ニッケル、塩化ニッケル、及びホウ酸が主組成であるワット浴、塩化ニッケル、及びホウ酸が主組成である塩化浴、塩化ニッケル、スルファミン酸ニッケル、及びホウ酸が主組成であるスルファミン酸浴、ホウフッ化ニッケル、及びホウ酸が主組成であるホウフッ化浴、塩化浴に更に塩化水素を添加して浴を強酸性にしたストライク浴(ウッド浴)、または黒色ニッケルめっき浴が用いられる。前記電解めっき浴には、必要に応じて、芳香族スルホン酸類(例えばベンゼンスルホン酸)、芳香族スルホン酸アミド類(例えばp-トルエンスルホンアミド)、及び芳香族スルホン酸イミド類(例えばサッカリン)等の一次光沢剤、アルデヒド類(例えばホルムアルデヒド)、アリル、ビニル化合物類(例えばアリルスルホン酸)、アセチレン化合物類(例えば2-ブチン-1,4-ジオール)、及びニトリル類(例えばエチルシアンヒドリン)等の二次光沢剤、また各種界面活性剤を加えてもよい。
The plating bath used for electroplating will be described. For example, when performing electrolytic nickel plating, a watt bath whose main composition is nickel sulfate, nickel chloride and boric acid, a nickel chloride and a chloride bath whose main composition is boric acid, nickel chloride, nickel sulfamate and boron. A sulfamic acid bath whose acid is the main composition, nickel borofluoride, and a borofluoride bath whose main composition is boric acid, a strike bath (wood bath) in which hydrogen chloride is further added to the chloride bath to make the bath strongly acidic, or A black nickel plating bath is used. In the electrolytic plating bath, aromatic sulfonic acids (for example, benzenesulfonic acid), aromatic sulfonic acid amides (for example, p-toluenesulfonamide), aromatic sulfonic acid imides (for example, saccharin), etc. Primary brighteners, aldehydes (eg formaldehyde), allyl, vinyl compounds (eg allyl sulfonic acid), acetylene compounds (eg 2-butyne-1,4-diol), and nitriles (eg ethyl cyanohydrin) Secondary brighteners such as, and various surfactants may be added.
電解銅めっきを実施する場合、硫酸銅、及び硫酸が主組成である硫酸銅浴、ホウフッ化銅、及びテトラフルオロホウ酸が主組成であるホウフッ化銅浴、シアン化銅、シアン化ナトリウム、及び水酸化ナトリウムが主組成であるシアン化銅浴、またはピロリン酸第二銅、ピロリン酸カリウム、及びアンモニアが主組成であるピロリン酸銅浴が用いられる。
When performing electrolytic copper plating, copper sulfate and a copper sulfate bath whose main composition is sulfuric acid, copper borofluoride, and a copper borofluoride bath whose main composition is tetrafluoroboric acid, copper cyanide, sodium cyanide, and A copper cyanide bath whose main composition is sodium hydroxide, or a copper pyrophosphate bath whose main composition is cupric pyrophosphate, potassium pyrophosphate and ammonia are used.
電解クロムめっきを実施する場合、酸化クロム(VI)、及び硫酸が主組成であるサージェント浴、または酸化クロム(VI)、硫酸、及びケイフッ酸が主組成であるケイフッ酸浴が用いられる。
When carrying out electrolytic chromium plating, a sergeant bath mainly composed of chromium (VI) oxide and sulfuric acid, or a hydrofluoric acid bath mainly composed of chromium (VI) oxide, sulfuric acid and silicic acid is used.
電解亜鉛めっきを実施する場合、硫酸亜鉛、硫酸アルミニウム、塩化ナトリウム、及びホウ酸が主成分である硫酸亜鉛浴、塩化亜鉛、及び塩化アンモニウムが主組成である塩化亜鉛浴、シアン化亜鉛、シアン化ナトリウム、及び水酸化ナトリウムが主組成であるシアン浴、または酸化亜鉛、及び水酸化ナトリウムが主組成であるジンケート浴を用いてよい。
When carrying out electrolytic galvanization, zinc sulfate bath mainly composed of zinc sulfate, aluminum sulfate, sodium chloride and boric acid, zinc chloride bath composed mainly of zinc chloride and ammonium chloride, zinc cyanide, cyanide You may use the cyanate bath whose main composition is sodium and sodium hydroxide, or the zincate bath whose main composition is zinc oxide and sodium hydroxide.
電解スズめっきを実施する場合、硫酸スズ、硫酸、クレゾールスルホン酸、及びホルマリンが主組成である硫酸浴、ホウフッ化スズ、テトラフルオロホウ酸、及びホルマリンが主組成であるホウフッ化浴、またはスズ酸カリウム、及び水酸化カリウムが主組成である塩基性スズめっき浴を用いてよい。
When carrying out electrolytic tin plating, sulfuric acid baths mainly composed of tin sulfate, sulfuric acid, cresol sulfonic acid and formalin, borofluoride baths mainly composed of tin borofluoride, tetrafluoroboric acid and formalin, or stannic acid A basic tin plating bath whose main composition is potassium and potassium hydroxide may be used.
電解金めっきを実施する場合、シアン化第一金カリウム、及びシアン化カリウムが主組成であるシアン浴、シアン化第一金カリウム、リン酸ナトリウム、及びリン酸水素ナトリウムが主組成である中性浴、またはシアン化第一金カリウム、及びクエン酸が主組成である酸性浴を用いてよい。
When carrying out electrolytic gold plating, potassium cyanide cyanide and a cyan bath whose main composition is potassium cyanide, neutral bath whose main composition is potassium gold cyanide, sodium phosphate, and sodium hydrogen phosphate, Alternatively, an acidic bath mainly composed of potassium gold cyanide and citric acid may be used.
電解銀めっきを実施する場合、シアン化銀、シアン化カリウム、及び炭酸カリウムが主組成であるストライク浴を用いてよい。
When performing electrolytic silver plating, a strike bath whose main composition is silver cyanide, potassium cyanide, and potassium carbonate may be used.
電解ロジウムめっきを実施する場合は、金属ロジウム、及び硫酸が主組成である硫酸めっき浴、または金属ロジウム、及びリン酸が主組成であるリン酸めっき浴を用いてよい。
When electrolytic rhodium plating is performed, a sulfuric acid plating bath whose main composition is metal rhodium and sulfuric acid, or a phosphoric acid plating bath whose main composition is metal rhodium and phosphoric acid may be used.
電解白金めっきを実施する場合、塩化白金(IV)、リン酸水素アミン、及びリン酸水素アンモニウムが主組成であるリン酸塩浴、またはジアミノ亜硝酸白金、亜硝酸ナトリウム、硝酸アンモニウム、及びアンモニア水が主成分であるジアミノ亜硝酸塩浴を用いてよい。
When electrolytic platinum plating is carried out, a phosphate bath mainly composed of platinum (IV) chloride, hydrogen phosphate amine, and ammonium hydrogen phosphate, or diaminoplatinum nitrite, sodium nitrite, ammonium nitrate, and aqueous ammonia A diaminonitrite bath, which is the main component, may be used.
物理気相成長法について説明する。真空蒸着法は、10-3から10-8Pa程度の真空度に調整した真空中で、加熱蒸発させた金属、金属化合物又は無機化合物を積層繊維構造物の構成繊維の表面に付着させて金属皮膜を形成する方法である。スパッタリング法は、金属(例えば、ニッケル、アルミニウム、銅、チタン、銀、金といった単体の金属や、ニッケルとクロムの合金、チタンとアルミニウムの合金、ニッケルと銅といった各種合金)、金属化合物(例えば、酸化チタン、窒化チタン)、又は無機化合物(例えば、酸化インジウムスズ(ITO)、酸化ケイ素)で作られたターゲットにイオン化した希ガス元素等を衝突させて、衝突によりターゲットからはじき飛ばされた金属を積層繊維構造物の構成繊維の表面に付着させて金属皮膜を形成する方法である。他の物理気相成長方法は、例えば、放電プラズマ、または電子ビーム等により、金属の一部又は全部をイオン化させ、負の電荷が印加された基板上に堆積させる方法である。
The physical vapor deposition method will be described. In the vacuum deposition method, a metal, a metal compound or an inorganic compound evaporated by heating is attached to the surface of the constituent fiber of the laminated fiber structure in a vacuum adjusted to a vacuum degree of about 10 −3 to 10 −8 Pa. This is a method of forming a film. Sputtering methods include metals (for example, single metals such as nickel, aluminum, copper, titanium, silver, and gold, alloys of nickel and chromium, alloys of titanium and aluminum, and various alloys such as nickel and copper), metal compounds (for example, A target made of titanium oxide, titanium nitride) or an inorganic compound (for example, indium tin oxide (ITO), silicon oxide) is collided with an ionized rare gas element or the like, and a metal that is repelled from the target by the collision is laminated. It is a method of forming a metal film by adhering to the surface of the constituent fiber of the fiber structure. Another physical vapor deposition method is a method in which a part or all of a metal is ionized and deposited on a substrate to which a negative charge is applied by, for example, discharge plasma or electron beam.
積層繊維構造物を構成する繊維の表面に金属皮膜として付着させる金属の単位面積あたりの質量(以下、単に単位面積あたりの「金属皮膜量」とも称す)は特に限定されない。しかし、単位面積あたりの金属皮膜量は1g/m2以上であることが好ましく、2g/m2以上、500g/m2以下であることがより好ましい。単位面積あたりの金属皮膜量が1g/m2未満であると、金属付着量が不十分となり、導電性繊維構造物の各種電気的特性が損なわれることがあり、特に十分な電気伝導性が得られないことがある。単位面積あたりの金属皮膜量が500g/m2を超えるように金属皮膜を形成しても、導電性繊維構造物の電気的特性の大幅な向上は得られない。むしろ、金属皮膜が構成繊維間の空隙を塞ぐために、導電性繊維構造物が硬いものとなり、その取扱い性及び後加工性が低下することがある。単位面積あたりの金属皮膜量は、2g/m2以上、480g/m2以下であることがより好ましく、3g/m2以上、470g/m2以下であることが特に好ましく、4g/m2以上、450g/m2以下であることが最も好ましい。
There is no particular limitation on the mass per unit area of metal (hereinafter, also simply referred to as “amount of metal coating” per unit area) to be deposited as a metal coating on the surface of the fibers constituting the laminated fiber structure. However, the amount of the metal film per unit area is preferably 1 g / m 2 or more, more preferably 2 g / m 2 or more and 500 g / m 2 or less. If the amount of the metal film per unit area is less than 1 g / m 2 , the amount of metal adhesion becomes insufficient, and various electrical characteristics of the conductive fiber structure may be impaired, and particularly sufficient electrical conductivity is obtained. It may not be possible. Even if the metal film is formed so that the amount of the metal film per unit area exceeds 500 g / m 2 , the electrical characteristics of the conductive fiber structure cannot be significantly improved. Rather, since the metal film closes the gaps between the constituent fibers, the conductive fiber structure may become hard, and the handleability and post-workability may deteriorate. Metal coating amount per unit area, 2 g / m 2 or more, more preferably 480 g / m 2 or less, 3 g / m 2 or more, particularly preferably at 470 g / m 2 or less, 4g / m 2 or more Most preferably, it is 450 g / m 2 or less.
積層繊維構造物を構成する繊維の表面に金属皮膜として付着させる金属の単位面積あたりの質量(金属皮膜量)は、導電性繊維構造物や金属多孔構造物の用途によって適宜調整される。導電性繊維構造物や金属多孔構造物を各種蓄電デバイスの電極材、例えば、活物質合剤を充填してニッケル-水素電池の正極といった用途に使用する場合、金属皮膜量は120g/m2以上、480g/m2以下であることがより好ましく、150g/m2以上、470g/m2以下であることが特に好ましく、180g/m2以上、450g/m2以下であることが最も好ましい。導電性繊維構造物や金属多孔構造物を電磁波シール材、フィルター、及びアース接地材料などの各種電子部品等の用途に使用する場合、金属皮膜量は2g/m2以上、200g/m2以下であることがより好ましく、3g/m2以上、150g/m2以下であることが特に好ましく、4g/m2以上、100g/m2以下であることが最も好ましい。
The mass per unit area of the metal (metal coating amount) deposited as a metal film on the surface of the fiber constituting the laminated fiber structure is appropriately adjusted depending on the use of the conductive fiber structure or the metal porous structure. When conductive fiber structures and metal porous structures are used for applications such as electrode materials for various electricity storage devices, such as positive electrodes for nickel-hydrogen batteries filled with active material mixtures, the amount of metal film is 120 g / m 2 or more. It is more preferably 480 g / m 2 or less, particularly preferably 150 g / m 2 or more and 470 g / m 2 or less, and most preferably 180 g / m 2 or more and 450 g / m 2 or less. When conductive fiber structures and metal porous structures are used for various electronic parts such as electromagnetic wave sealing materials, filters, and grounding materials, the amount of metal film should be 2g / m 2 or more and 200g / m 2 or less. More preferably, it is 3 g / m 2 or more and 150 g / m 2 or less, most preferably 4 g / m 2 or more and 100 g / m 2 or less.
単位面積あたりの金属皮膜量(g/m2)は次の方法で測定される。まず、積層繊維構造物の質量W1(g)を測定する。次に、金属皮膜を形成する処理を行い、積層繊維構造物の構成繊維表面に金属皮膜を形成する。金属皮膜を形成する処理を1回、或いは複数回行い、金属皮膜を形成する処理を終了した後、得られた導電性繊維構造物の質量W2(g)、及び面積A(cm2)を測定する。測定した積層繊維構造物の質量W1、導電性繊維構造物の質量W2、及び導電性繊維構造物の面積Aから、下記式(4)に従って単位面積あたりの金属皮膜量を算出する。
単位面積あたりの金属皮膜量(g/m2)=1×104×(W2-W1)/A (4) The amount of metal film (g / m 2 ) per unit area is measured by the following method. First, the mass W 1 (g) of the laminated fiber structure is measured. Next, the process which forms a metal membrane | film | coat is performed and a metal membrane | film | coat is formed in the constituent fiber surface of a laminated fiber structure. After the process for forming the metal film is performed once or a plurality of times and the process for forming the metal film is completed, the mass W 2 (g) and the area A (cm 2 ) of the obtained conductive fiber structure are calculated. taking measurement. From the measured mass W 1 of the laminated fiber structure, mass W 2 of the conductive fiber structure, and area A of the conductive fiber structure, the amount of the metal film per unit area is calculated according to the following formula (4).
Metal film amount per unit area (g / m 2 ) = 1 × 10 4 × (W 2 −W 1 ) / A (4)
単位面積あたりの金属皮膜量(g/m2)=1×104×(W2-W1)/A (4) The amount of metal film (g / m 2 ) per unit area is measured by the following method. First, the mass W 1 (g) of the laminated fiber structure is measured. Next, the process which forms a metal membrane | film | coat is performed and a metal membrane | film | coat is formed in the constituent fiber surface of a laminated fiber structure. After the process for forming the metal film is performed once or a plurality of times and the process for forming the metal film is completed, the mass W 2 (g) and the area A (cm 2 ) of the obtained conductive fiber structure are calculated. taking measurement. From the measured mass W 1 of the laminated fiber structure, mass W 2 of the conductive fiber structure, and area A of the conductive fiber structure, the amount of the metal film per unit area is calculated according to the following formula (4).
Metal film amount per unit area (g / m 2 ) = 1 × 10 4 × (W 2 −W 1 ) / A (4)
本発明の導電性繊維構造物の電気抵抗は特に限定されない。導電性繊維構造物のCD方向の電気抵抗に対するMD方向の電気抵抗の比(以下、単に「電気抵抗のMD/CD比」とも称す)は0.35以上、3以下であることが好ましい。電気抵抗のMD/CD比がこの範囲内にあると、導電性繊維構造物において、電気伝導特性の方向依存性が低くなる。電気抵抗のMD/CD比は0.4以上、2.5以下であることがより好ましく、0.45以上、2.25以下であることが特に好ましく、0.5以上、2以下であることが最も好ましい。なお、本発明の導電性繊維構造物において、その電気抵抗は、日置電機株式会社製HITESTERを使用して、周波数は60kHz、オートモードで、導電性繊維構造物のMD方向及びCD方向について測定される。
The electrical resistance of the conductive fiber structure of the present invention is not particularly limited. The ratio of the electrical resistance in the MD direction to the electrical resistance in the CD direction of the conductive fiber structure (hereinafter also simply referred to as “MD / CD ratio of electrical resistance”) is preferably 0.35 or more and 3 or less. When the MD / CD ratio of the electrical resistance is within this range, the direction dependency of the electrical conduction characteristics is lowered in the conductive fiber structure. The MD / CD ratio of electrical resistance is more preferably 0.4 or more and 2.5 or less, particularly preferably 0.45 or more and 2.25 or less, and 0.5 or more and 2 or less. Is most preferred. In addition, in the conductive fiber structure of the present invention, the electrical resistance is measured in the MD direction and the CD direction of the conductive fiber structure with a frequency of 60 kHz and an auto mode using HITESTER manufactured by Hioki Electric Co., Ltd. The
次に、本発明の金属多孔構造物について説明する。本発明の金属多孔構造物は、金属繊維で構成された金属の多孔性構造物であり、前記金属繊維として、肉厚が1μm以上の中空金属繊維、及び繊維断面において、短辺が2μm以上である金属繊維から選択される少なくとも1種類の金属繊維を含む。肉厚が1μm以上の中空金属繊維及び/または繊維断面における短辺が2μm以上の金属繊維で構成された金属多孔構造物は、加熱により分解・消失する熱分解性物質からなる繊維の表面に、厚さ1μm以上の金属皮膜を設けた導電性繊維からなる繊維構造物を還元雰囲気中で加熱・焼成することで容易に得ることができる。本発明でいう、繊維断面における金属繊維の長辺とは、金属繊維を、金属繊維の長さ方向に垂直な面で切断した面において、金属繊維断面の外周上における異なる2点間を結ぶ線分の中で、最も長さが長い線分のことを指す。そして、本発明でいう、繊維断面における金属繊維の短辺とは、金属繊維を、金属繊維の長さ方向に垂直な面で切断した面において、金属繊維断面の外周上における異なる2点間を結ぶ線分の中で、前記長辺に垂直に交わる線分の中で最も長いものを指す。
Next, the metal porous structure of the present invention will be described. The metal porous structure of the present invention is a metal porous structure composed of metal fibers. As the metal fiber, a hollow metal fiber having a wall thickness of 1 μm or more, and a short side in a fiber cross section having a short side of 2 μm or more. It contains at least one metal fiber selected from certain metal fibers. A metal porous structure composed of hollow metal fibers having a wall thickness of 1 μm or more and / or metal fibers having a short side of 2 μm or more in the fiber cross section is formed on the surface of the fiber made of a pyrolyzable material that decomposes and disappears by heating It can be easily obtained by heating and firing a fiber structure composed of conductive fibers provided with a metal film having a thickness of 1 μm or more in a reducing atmosphere. The long side of the metal fiber in the fiber cross section referred to in the present invention is a line connecting two different points on the outer periphery of the metal fiber cross section in a plane obtained by cutting the metal fiber along a plane perpendicular to the length direction of the metal fiber. This refers to the longest line segment in a minute. And the short side of the metal fiber in the fiber cross section as referred to in the present invention means that between two different points on the outer periphery of the metal fiber cross section on the surface obtained by cutting the metal fiber along a plane perpendicular to the length direction of the metal fiber. Among the connecting line segments, the longest line segment perpendicular to the long side is indicated.
本発明の金属多孔構造物は、肉厚が1μm以上の中空金属繊維のみで構成されてよく、あるいは繊維断面における短辺が2μm以上の金属繊維のみで構成されてよく、あるいは両者により構成されてよい。本発明の金属多孔構造物は、後述するように、圧縮処理された状態で提供されることがある。その場合には、圧縮処理される前には、肉厚が1μm以上の中空繊維であった金属繊維が、中空部が圧縮により無くなる又はきわめて小さくなった状態となり、中空の有無にかかわらず、繊維断面における短辺が2μm以上(即ち、1μmの肉厚を二つ合わせた寸法)の金属繊維(例えば、扁平形状の金属繊維)となる。そのような場合を考慮して、ここでは、2種類の異なる形状または形態の金属繊維を、金属多孔構造物を構成する繊維として特定している。
The metal porous structure of the present invention may be composed only of hollow metal fibers having a wall thickness of 1 μm or more, or may be composed only of metal fibers having a short side in the fiber cross section of 2 μm or more, or both. Good. The metal porous structure of the present invention may be provided in a compressed state as will be described later. In that case, before the compression treatment, the metal fiber which was a hollow fiber having a thickness of 1 μm or more becomes a state in which the hollow portion is lost or becomes extremely small due to compression, and the fiber regardless of whether there is a hollow or not. The short side in the cross section is a metal fiber (for example, a flat-shaped metal fiber) having a short side of 2 μm or more (that is, a dimension obtained by combining two 1 μm thicknesses). Considering such a case, here, two types of metal fibers having different shapes or forms are specified as fibers constituting the metal porous structure.
本発明の金属多孔構造物は、上記の肉厚もしくは短辺の条件を満たす金属繊維で構成される。そして、金属多孔構造物には繊維長が異なる短金属繊維と長金属繊維が存在し、前記金属多孔構造物は、前記短金属繊維を含む少なくとも1つの短金属繊維層と、前記長金属繊維を含む少なくとも1つの長金属繊維層を含む。前記長金属繊維層は、この層の一方向に連続して延びる長金属繊維と、前記一方向と交差する方向に延びる長金属繊維を含んでいる。前記長金属繊維層には、前記短金属繊維層が積層され、前記短金属繊維の少なくとも一部は、前記長金属繊維との交点で前記長い金属繊維に接合している。本発明の金属多孔構造物は、連続して延びる長金属繊維が金属多孔構造物全体においてネットワークを構成する長金属繊維層と、繊維本数が多く、緻密なネットワークを構成している、短金属繊維層とが接合、一体化している。これにより、金属多孔構造物は連続した金属繊維のネットワーク、密に張り巡らされた金属繊維のネットワークの両方を有するものとなり、優れた電気伝導性を示す。
The metal porous structure of the present invention is composed of metal fibers that satisfy the above-mentioned thickness or short side conditions. The metal porous structure includes short metal fibers and long metal fibers having different fiber lengths. The metal porous structure includes at least one short metal fiber layer including the short metal fibers and the long metal fibers. Including at least one long metal fiber layer. The long metal fiber layer includes a long metal fiber extending continuously in one direction of the layer and a long metal fiber extending in a direction crossing the one direction. The short metal fiber layer is laminated on the long metal fiber layer, and at least a part of the short metal fiber is bonded to the long metal fiber at an intersection with the long metal fiber. The metal porous structure of the present invention comprises a long metal fiber layer in which continuously extending long metal fibers form a network in the entire metal porous structure, and a short metal fiber having a large number of fibers and forming a dense network. The layers are joined and integrated. As a result, the metal porous structure has both a continuous metal fiber network and a densely stretched metal fiber network, and exhibits excellent electrical conductivity.
本発明の金属多孔構造物は、少なくとも1つの短金属繊維層と、少なくとも1つの長金属繊維層を有している限りにおいて、特に限定されないが、好ましくは、金属多孔構造物は、その両表面が短金属繊維層で構成される。これは、金属多孔構造物において、両表面を構成する層の少なくとも一方が長金属繊維層であると、表面層である長金属繊維層が、短金属繊維層から剥離しやすくなるためである。特に、金属多孔構造物は、長金属繊維層が金属多孔構造物の中心付近(言い換えるならば金属多孔構造物の内部)に存在し、その両表面に、短金属繊維層が配置された3層構造であることが好ましい。
The metal porous structure of the present invention is not particularly limited as long as it has at least one short metal fiber layer and at least one long metal fiber layer. Preferably, the metal porous structure has both surfaces thereof. Is composed of a short metal fiber layer. This is because in the metal porous structure, when at least one of the layers constituting both surfaces is a long metal fiber layer, the long metal fiber layer as the surface layer is easily peeled from the short metal fiber layer. In particular, the metal porous structure has three layers in which the long metal fiber layer is present near the center of the metal porous structure (in other words, inside the metal porous structure), and the short metal fiber layer is disposed on both surfaces thereof. A structure is preferred.
長金属繊維層は、金属多孔構造物の一方向に連続して延びる長金属繊維と、前記特定の一方向と交差する方向に連続して延びる長金属繊維を有するものであれば特に限定されない。ここでいう「連続して延びる長金属繊維」とは、これを含む金属多孔構造物を所定の大きさで使用したときに、当該大きさの金属多孔構造物内で所定の方向において連続して延びている金属繊維をいう。本発明の金属多孔構造物を構成する長金属繊維層は、一方向に連続して延びる長金属繊維と、前記特定の一方向と交差する方向に連続して延びる長金属繊維を有する層であれば特に限定されないが、好ましくは少なくとも異なる2つの方向に連続して延びる長金属繊維によって囲まれる開口部を有するネット状物である。
The long metal fiber layer is not particularly limited as long as it has a long metal fiber continuously extending in one direction of the metal porous structure and a long metal fiber continuously extending in a direction intersecting the specific one direction. The term “long continuous metal fiber” as used herein means that when a metal porous structure including the metal fiber is used in a predetermined size, the metal porous structure including the metal fiber is continuously in a predetermined direction within the metal porous structure of the size. An extending metal fiber. The long metal fiber layer constituting the metal porous structure of the present invention may be a layer having a long metal fiber continuously extending in one direction and a long metal fiber continuously extending in a direction crossing the one specific direction. Although it is not particularly limited, it is preferably a net having an opening surrounded by long metal fibers extending continuously in at least two different directions.
長金属繊維層がネット状物である場合、連続して延びる長金属繊維は異なる2つの方向に配向するように配置されてもよいし、異なる3以上の方向に配向するように配置されてもよいし、あるいは完全にランダムな状態で配置されてもよい。長金属繊維層がネット状物である場合、長金属繊維層は、連続して延びる長金属繊維を異なる4以下の方向に配向させて並べて形成されることが好ましく、異なる2方向に配向させて形成されることが特に好ましい。長金属繊維層がネット状物である場合、異なる2以上の方向に配向して並べられた長金属繊維によって囲まれた開口部が形成される。前記長金属繊維が完全にランダムな状態で並べられている場合、開口部の形状もそれに伴いランダムな形状になる。前記のように、長金属繊維は4以下の方向に配向させて並べることが好ましく、2方向に配向させて並べることが特に好ましいため、開口部分の形状は三角形、正方形、長方形、菱形であることが好ましく、正方形、長方形、菱形であることが特に好ましい。
When the long metal fiber layer is a net-like material, the continuously extending long metal fibers may be arranged in two different directions, or may be arranged in three or more different directions. Alternatively, they may be arranged in a completely random state. When the long metal fiber layer is a net-like material, the long metal fiber layer is preferably formed by aligning long metal fibers extending continuously in four or less different directions, and orienting in two different directions. It is particularly preferred that it be formed. When the long metal fiber layer is a net-like material, an opening surrounded by long metal fibers aligned in two or more different directions is formed. When the long metal fibers are arranged in a completely random state, the shape of the opening also becomes a random shape accordingly. As described above, the long metal fibers are preferably aligned in the direction of 4 or less, and particularly preferably aligned in the two directions, so that the shape of the opening portion is a triangle, a square, a rectangle, or a rhombus. Are preferable, and a square, a rectangle and a rhombus are particularly preferable.
前記長金属繊維層がネット状物である場合、特定の一方向に連続して延びる長金属繊維が配向する方向はいずれの方向であってよい。また、本発明の金属多孔構造物を構成する、長金属繊維からなるネット状物において、前記特定の一方向に延びる長金属繊維と、当該一方向と交差する方向に連続して延びる長金属繊維とはいかなる角度で交差、あるいは交差した点で接合していてもよい。異なる2方向に連続して延びる、長金属繊維は、好ましくは30°以上、90°以下、より好ましくは45°以上、90°以下、特に好ましくは60°以上、90°以下の鋭角を形成して交差、あるいは交差した点で接合している。金属多孔構造物を構成する長金属繊維層が、このような鋭角を形成して、2つの方向に金属繊維が配向したネット状物であると、金属多孔構造物の電気特性及び/または力学的特性の方向依存性がより少なくなる。
When the long metal fiber layer is a net-like material, the direction in which the long metal fibers continuously extending in one specific direction are oriented may be any direction. Further, in the net-like object composed of long metal fibers constituting the metal porous structure of the present invention, the long metal fibers extending in the specific one direction and the long metal fibers continuously extending in the direction intersecting the one direction. And may intersect at any angle or may be joined at the intersecting point. Long metal fibers extending continuously in two different directions preferably form an acute angle of 30 ° or more and 90 ° or less, more preferably 45 ° or more and 90 ° or less, particularly preferably 60 ° or more and 90 ° or less. Intersect or join at the intersection. When the long metal fiber layer constituting the metal porous structure is a net-like material in which such an acute angle is formed and the metal fibers are oriented in two directions, the electrical characteristics and / or mechanical properties of the metal porous structure are obtained. The direction dependency of the characteristics becomes less.
本発明の金属多孔構造物を構成する金属繊維は、前記の肉厚もしくは短辺の条件を満たす金属繊維であれば限定されないが、前記金属繊維として、比較的繊維径の小さい細径金属繊維と、比較的繊維径の大きな太径金属繊維が存在することが好ましい。金属多孔構造物に繊維径の大きな太径金属繊維が存在することで、断面積が大きい、すなわち電気抵抗の小さい金属繊維が存在するようになり、金属多孔構造物全体の電気抵抗が低くなりやすいためである。また、細径金属繊維が存在することで、金属多孔構造物が柔軟なものとなるだけでなく、細径金属繊維によって、金属多孔構造物全体に金属繊維のネットワークが密に張り巡らされる。また、細径金属繊維を含む金属多孔構造物を各種電極材に使用した場合、活物質の保持性能が高められ、活物質の脱落が抑えられやすくなる。
The metal fiber constituting the metal porous structure of the present invention is not limited as long as it is a metal fiber that satisfies the above-mentioned thickness or short side condition, but as the metal fiber, a thin metal fiber having a relatively small fiber diameter and It is preferable that a thick metal fiber having a relatively large fiber diameter exists. The presence of large-diameter metal fibers having a large fiber diameter in the metal porous structure leads to the presence of metal fibers having a large cross-sectional area, that is, low electrical resistance, and the electrical resistance of the entire metal porous structure tends to be low. Because. In addition, the presence of the fine metal fibers not only makes the metal porous structure flexible, but the metal metal network is densely stretched around the metal porous structure by the fine metal fibers. Moreover, when the metal porous structure containing a thin metal fiber is used for various electrode materials, the retention performance of the active material is enhanced, and the falling off of the active material is easily suppressed.
まず細径金属繊維について説明する。本発明の金属多孔構造物を構成する細径金属繊維は、繊維の長さ方向に垂直な面で切断した面を観察した際、その繊維断面が、9μm以上、170μm以下の長辺、及び2μm以上、100μm以下の短辺を有する。細径金属繊維の繊維断面における短辺が2μm以上であることで、金属多孔構造物の強度が充分なものとなり、工程性や使用時の耐久性に富む金属多孔構造物が得られる。また、細径金属繊維の繊維断面における長辺が170μm以下であることで、金属多孔構造物の加工性が損なわれることや、重量増加を招くこともない。細径金属繊維の繊維断面における長辺は15μm以上、140μm以下であると好ましく、20μm以上、100μm以下であるとより好ましく、25μm以上、80μm以下であると特に好ましく、30μm以上、60μm以下であると最も好ましい。細径金属繊維の繊維断面における短辺は2μm以上、80μm以下であると好ましく、3μm以上、65μm以下であるとより好ましく、4μm以上、55μm以下が特に好ましい。なお、細径金属繊維が真円に近い形状(具体的には、前記細径金属繊維の長辺/前記細径金属繊維の短辺が1.1未満の細径金属繊維)である場合、この細径金属繊維は、断面形状が真円の細径金属繊維として扱い、細径金属繊維の長辺を直径とみなす。この場合、細径金属繊維の繊維径(すなわち細径金属繊維の直径であり、直径とみなした長辺を含む)は7μm以上、120μm以下であることが好ましく、10μm以上、80μm以下であることがより好ましく、12μm以上、65μm以下であることが特に好ましい。
First, the thin metal fiber will be described. The thin metal fiber constituting the metal porous structure of the present invention has a cross section of 9 μm or more and 170 μm or less and a long side of 2 μm when the surface cut by a plane perpendicular to the fiber length direction is observed. As described above, it has a short side of 100 μm or less. When the short side in the fiber cross section of the thin metal fiber is 2 μm or more, the strength of the metal porous structure becomes sufficient, and a metal porous structure having excellent processability and durability during use can be obtained. Moreover, when the long side in the fiber cross section of a thin metal fiber is 170 micrometers or less, the workability of a metal porous structure is not impaired and a weight increase is not caused. The long side in the fiber cross section of the thin metal fiber is preferably 15 μm or more and 140 μm or less, more preferably 20 μm or more and 100 μm or less, particularly preferably 25 μm or more and 80 μm or less, and 30 μm or more and 60 μm or less. And most preferred. The short side in the fiber cross section of the thin metal fiber is preferably 2 μm or more and 80 μm or less, more preferably 3 μm or more and 65 μm or less, and particularly preferably 4 μm or more and 55 μm or less. When the thin metal fiber has a shape close to a perfect circle (specifically, the long metal fiber has a long side / the short metal fiber has a short side of less than 1.1), This thin metal fiber is treated as a thin metal fiber having a perfect cross-sectional shape, and the long side of the thin metal fiber is regarded as the diameter. In this case, the fiber diameter of the fine metal fiber (that is, the diameter of the fine metal fiber, including the long side regarded as the diameter) is preferably 7 μm or more and 120 μm or less, and preferably 10 μm or more and 80 μm or less. Is more preferably 12 μm or more and 65 μm or less.
次に太径金属繊維について説明する。本発明の金属多孔構造物を構成する太径金属繊維は、繊維の長さ方向に垂直な面で切断した面を観察した際、その繊維断面が、35μm以上、1300μm以下の長辺、及び2μm以上、830μm以下の短辺を有する。太径金属繊維の繊維断面における短辺が2μm以上であることで、金属多孔構造物の強度が充分なものとなり、工程性や使用時の耐久性に富む金属多孔構造物が得られるだけでなく、金属多孔構造物の電気的特性が良好になりやすい。また、太径金属繊維の繊維断面における長辺が1300μm以下であることで、金属多孔構造物の加工性が損なわれることや、重量増加を招くこともない。太径金属繊維の長辺は60μm以上、800μm以下であると好ましく、80μm以上、500μm以下であるとより好ましく、100μm以上、400μm以下であると特に好ましく、150μm以上、350μm以下であると最も好ましい。太径金属繊維の短辺は2μm以上、500μm以下であると好ましく、3μm以上、300μm以下であるとより好ましく、4μm以上、250μm以下であると特に好ましい。なお、太径金属繊維が真円に近い形状(具体的には、前記太径金属繊維の長辺/前記太径金属繊維の短辺が1.1未満の太径金属繊維)である場合、この太径金属繊維は、断面形状が真円の太径金属繊維として扱い、太径金属繊維の長辺を直径とみなす。この場合、太径金属繊維の繊維径(直径及び直径とみなした長辺を含む)は35μm以上、1300μm以下であることが好ましく、60μm以上、800μm以下であることがより好ましく、80μm以上、500μm以下であることが特に好ましく、100μm以上、400μm以下であることが最も好ましい。
Next, the large-diameter metal fiber will be described. The large-diameter metal fiber constituting the metal porous structure of the present invention has a fiber cross-section of 35 μm to 1300 μm long side and 2 μm when a surface cut by a plane perpendicular to the fiber length direction is observed. As described above, it has a short side of 830 μm or less. When the short side of the fiber cross section of the large-diameter metal fiber is 2 μm or more, the strength of the metal porous structure becomes sufficient, and not only a metal porous structure with excellent processability and durability during use can be obtained. The electrical characteristics of the metal porous structure are likely to be good. Moreover, the workability of a metal porous structure is not impaired, and a weight increase is not caused because the long side in the fiber cross section of a large diameter metal fiber is 1300 micrometers or less. The long side of the large-diameter metal fiber is preferably 60 μm or more and 800 μm or less, more preferably 80 μm or more and 500 μm or less, particularly preferably 100 μm or more and 400 μm or less, and most preferably 150 μm or more and 350 μm or less. . The short side of the large-diameter metal fiber is preferably 2 μm or more and 500 μm or less, more preferably 3 μm or more and 300 μm or less, and particularly preferably 4 μm or more and 250 μm or less. When the large-diameter metal fiber has a shape close to a perfect circle (specifically, the long side of the large-diameter metal fiber / the large-side metal fiber having a short side of the large-diameter metal fiber of less than 1.1), This large-diameter metal fiber is handled as a large-diameter metal fiber having a perfect cross-sectional shape, and the long side of the large-diameter metal fiber is regarded as the diameter. In this case, the fiber diameter (including the long side regarded as the diameter and the diameter) of the large-diameter metal fiber is preferably 35 μm or more and 1300 μm or less, more preferably 60 μm or more and 800 μm or less, and more preferably 80 μm or more and 500 μm. Or less, and most preferably 100 μm or more and 400 μm or less.
前述した細径金属繊維の繊維断面における短辺と、太径金属繊維の繊維断面における短辺において、その取り得る範囲は重複している。これは、金属多孔構造物に対し、圧延加工や厚み加工などの圧縮を伴う処理を行った場合、細径金属繊維、及び太径金属繊維のいずれもが圧縮により扁平化する可能性があるためである。即ち、前記圧縮を伴う処理において、圧縮する割合が特に大きい場合、細径金属繊維及び太径金属繊維のいずれもが、圧縮する方向に対し平行な方向の厚さ(すなわち短辺)が同程度になるまで圧縮されうるからである。この場合、細径金属繊維と太径金属繊維それぞれの繊維断面における長辺は大きく異なり、細径金属繊維の長辺と、太径金属繊維の長辺の比は、具体的には、(細径金属繊維の長辺):(太径金属繊維の長辺)=1:1.5から1:30、より好ましくは1:2から1:20、特に好ましくは1:3から1:10となる。
The possible range overlaps between the short side of the fiber cross section of the thin metal fiber and the short side of the fiber cross section of the large metal fiber described above. This is because when a metal porous structure is subjected to a process involving compression such as rolling or thickness processing, both the small-diameter metal fiber and the large-diameter metal fiber may be flattened by the compression. It is. That is, in the process involving compression, when the compression ratio is particularly large, both the thin metal fiber and the large metal fiber have the same thickness (that is, the short side) in the direction parallel to the compression direction. It is because it can compress until it becomes. In this case, the long side in the fiber cross section of each of the small diameter metal fiber and the large diameter metal fiber is greatly different, and the ratio of the long side of the small diameter metal fiber to the long side of the large diameter metal fiber is specifically: Long side of diameter metal fiber): (Long side of large diameter metal fiber) = 1: 1.5 to 1:30, more preferably 1: 2 to 1:20, particularly preferably 1: 3 to 1:10 Become.
前記細径金属繊維と前記太径金属繊維の繊維長は特に限定されないが、細径金属繊維が比較的短い金属繊維であり、太径金属繊維が比較的長い金属繊維であることが好ましい。言い換えるならば、細径金属繊維が前記短金属繊維であり、太径金属繊維が前記長金属繊維であることが好ましい。本発明の金属多孔構造物を構成する金属繊維のうち、太径金属繊維は、その断面積が大きいことから細径金属繊維よりも電気抵抗が低い傾向にある。よって、これが一方向に連続して延びる長金属繊維であることで、電気抵抗の小さい金属繊維が切れ目の少ない、あるいは切れ目のない導電性領域を金属多孔構造物内部に形成するため、金属多孔構造物全体の電気的特性が向上し、電気抵抗が低下すると考えられる。
The fiber lengths of the thin metal fiber and the large metal fiber are not particularly limited, but the thin metal fiber is preferably a relatively short metal fiber, and the large metal fiber is preferably a relatively long metal fiber. In other words, it is preferable that the thin metal fiber is the short metal fiber and the large metal fiber is the long metal fiber. Among the metal fibers constituting the metal porous structure of the present invention, the large-diameter metal fibers tend to have lower electrical resistance than the small-diameter metal fibers because of their large cross-sectional area. Therefore, since this is a long metal fiber continuously extending in one direction, the metal fiber having a low electrical resistance forms a conductive region with little or no cut inside the metal porous structure. It is considered that the electrical characteristics of the whole object are improved and the electrical resistance is lowered.
前記太径金属繊維が、前述の長金属繊維である場合、この繊維を含む層は、この層の一方向に連続して延びる太径金属繊維と、前記一方向と交差する方向に延びる太径金属繊維を含んでいる。この太径金属繊維は、前記二つの方向に連続して延びる金属繊維であれば限定されないが、二つの方向に連続した、太径金属繊維の連続繊維(フィラメント)であることが好ましく、二つの方向に延びる太径金属繊維の連続繊維がネット状となっていることが特に好ましい。連続する太径金属繊維がネット状になっている場合、一方向に連続した太径金属繊維は略等間隔で配置されていることが好ましい。その場合、太径金属繊維同士の間隔が1mm以上、15mm以下であることが好ましく、2mm以上、10mm以下であることがより好ましく、3mm以上、9mm以下であることが特に好ましい。
When the large-diameter metal fiber is the above-described long metal fiber, the layer containing the fiber has a large-diameter metal fiber continuously extending in one direction of the layer and a large diameter extending in a direction intersecting the one direction. Contains metal fibers. The large-diameter metal fiber is not limited as long as it is a metal fiber continuously extending in the two directions, but is preferably a continuous fiber (filament) of a large-diameter metal fiber that is continuous in two directions. It is particularly preferable that the continuous fibers of large-diameter metal fibers extending in the direction have a net shape. When continuous large-diameter metal fibers are in a net shape, the large-diameter metal fibers continuous in one direction are preferably arranged at substantially equal intervals. In that case, the interval between the large-diameter metal fibers is preferably 1 mm or more and 15 mm or less, more preferably 2 mm or more and 10 mm or less, and particularly preferably 3 mm or more and 9 mm or less.
本発明の金属多孔構造物においては、前記の通り細径金属繊維と太径金属繊維とが存在していることが好ましい。このうち細径金属繊維の少なくとも一部は前記太径金属繊維との交点で接合していることを特徴とする。細径金属繊維の少なくとも一部が太径金属繊維と交点にて接合し一体化していることで、細径金属繊維を流れる電流が、より繊維径の太い、すなわち電気抵抗の低い部分を流れるようになり、結果として金属多孔構造物の電気抵抗が低下すると考えられる。
In the metal porous structure of the present invention, it is preferable that a small-diameter metal fiber and a large-diameter metal fiber exist as described above. Among these, at least a part of the small-diameter metal fiber is bonded at the intersection with the large-diameter metal fiber. Because at least a part of the thin metal fiber is joined and integrated with the large metal fiber at the intersection, the current flowing through the thin metal fiber flows through a portion with a larger fiber diameter, that is, a lower electrical resistance. As a result, it is considered that the electrical resistance of the metal porous structure is lowered.
前記太径金属繊維は金属多孔構造物において細径金属繊維と共に存在していれば、金属多孔構造物のどこに存在していてもよく、表面付近、あるいは表面に存在していてもよい。太径金属繊維は、金属多孔構造物の内部に存在する(言い換えるならば、表面には露出しない)ことが好ましく、金属多孔構造物の中心付近に存在することがより好ましい。太径金属繊維は繊維径が細径金属繊維よりも大きく、太径金属繊維と細径金属繊維との接合箇所が、細径金属繊維同士の接合箇所よりも少ないため、太径金属繊維と細径金属繊維との接合が、細径金属繊維同士の接合よりも弱くなる傾向がある。そのため、金属多孔構造物の表面に太径金属繊維が存在すると、細径金属繊維との接合が外れ、細径金属繊維が脱落する可能性がある。また、太径金属繊維が金属多孔構造物の厚み方向における中心付近に存在することで、太径金属繊維は、一方の表面を構成する細径金属繊維と、もう一方の表面を構成する細径金属繊維の両方ともと容易に接合することができるため、得られる金属多孔構造物の電気的特性が向上しやすくなると考えられる。
The large-diameter metal fiber may be present anywhere in the metal porous structure as long as it is present together with the thin metal fiber in the metal porous structure, or may be present near or on the surface. The large-diameter metal fiber is preferably present inside the metal porous structure (in other words, not exposed on the surface), and more preferably present in the vicinity of the center of the metal porous structure. Large metal fibers have a larger fiber diameter than thin metal fibers, and there are fewer joints between large metal fibers and small metal fibers than joints between small metal fibers. There exists a tendency for joining with a diameter metal fiber to become weaker than joining between small diameter metal fibers. Therefore, when a large-diameter metal fiber is present on the surface of the metal porous structure, there is a possibility that the connection with the fine-diameter metal fiber is released and the fine-diameter metal fiber falls off. In addition, since the large-diameter metal fiber is present near the center in the thickness direction of the metal porous structure, the large-diameter metal fiber has a small-diameter metal fiber constituting one surface and a small-diameter constituting the other surface. Since both metal fibers can be easily joined, it is considered that the electrical characteristics of the obtained metal porous structure are easily improved.
本発明の金属多孔構造物を構成する金属繊維において、その断面形状は特に限定されない。そのため、あらゆる断面形状とすることができ、例えば、円形(真円)断面の他、断面形状が非円形、いわゆる異形断面であってもよい。異形断面としては、多角型形状、楕円型形状、扁平型形状、繊維表面に多数の枝状部を有する、いわゆる多葉型形状(具体的には3葉から32葉の多葉型形状)、星型形状、C字型形状、Y字型形状、W字型形状、及び井型形状が例示される。
The cross-sectional shape of the metal fiber constituting the metal porous structure of the present invention is not particularly limited. Therefore, any cross-sectional shape can be used. For example, in addition to a circular (perfect circle) cross-section, the cross-sectional shape may be a non-circular cross-section, that is, a so-called irregular cross-section. As an irregular cross section, a polygonal shape, an elliptical shape, a flat shape, a so-called multileaf shape (specifically, a multileaf shape of 3 to 32 leaves) having a number of branch portions on the fiber surface, Examples are a star shape, a C shape, a Y shape, a W shape, and a well shape.
金属多孔構造物は、前述した断面形状の金属繊維で構成されているが、使いやすい厚みにするため、圧延加工や厚み加工といった圧縮処理を行って製造することが多い。前記の圧縮処理を行った場合、金属多孔構造物を構成する細径金属繊維及び太径金属繊維はいずれも扁平化する傾向にある。導電性繊維が扁平化した金属多孔構造物において、細径金属繊維の繊維断面における長辺は15μm以上、140μm以下、短辺は4μm以上、50μm以下であると好ましく、長辺が25μm以上、80μm以下、短辺が4μm以上、30μm以下であると特に好ましい。また導電性繊維が扁平化した金属多孔構造物において、太径金属繊維の繊維断面における長辺は50μm以上、800μm以下、短辺は4μm以上、250μm以下であると好ましく、長辺が100μm以上、300μm以下、短辺が4μm以上、200μm以下であると特に好ましい。
The metal porous structure is composed of the above-described metal fibers having a cross-sectional shape, and is often manufactured by performing a compression process such as a rolling process or a thickness process in order to obtain a thickness that is easy to use. When the compression treatment is performed, both the small-diameter metal fiber and the large-diameter metal fiber constituting the metal porous structure tend to be flattened. In the metal porous structure in which the conductive fiber is flattened, the long side in the fiber cross section of the thin metal fiber is preferably 15 μm to 140 μm, the short side is preferably 4 μm to 50 μm, and the long side is 25 μm to 80 μm. Hereinafter, the short side is particularly preferably 4 μm or more and 30 μm or less. In the metal porous structure in which the conductive fiber is flattened, the long side in the fiber cross section of the large-diameter metal fiber is preferably 50 μm or more and 800 μm or less, the short side is preferably 4 μm or more and 250 μm or less, and the long side is 100 μm or more. Particularly preferably, it is 300 μm or less and the short side is 4 μm or more and 200 μm or less.
前記本発明の金属多孔構造物は、前記本発明の導電性繊維構造物を構成する熱分解性物質を除去することを含む加熱処理によって得ることができる。導電性繊維構造物中の熱消失性物質を除去する方法は特に限定されない。例えば、熱消失性物質は、空気中などの酸化性雰囲気下で加熱処理を行って、除去してよい。この場合、熱消失性物質が除去された後に残存する金属皮膜を、水素、またはアンモニアなどの還元性雰囲気下で焼成して、金属が還元されるようにする必要がある。あるいは、熱消失性物質は、窒素、ヘリウム、またはアルゴン等の不活性気体雰囲気中で、700℃から2000℃で、30秒から30分間処理することによって、除去してよい。
The metal porous structure of the present invention can be obtained by a heat treatment including removing a thermally decomposable substance constituting the conductive fiber structure of the present invention. The method for removing the heat-dissipating substance in the conductive fiber structure is not particularly limited. For example, the heat-dissipating substance may be removed by performing a heat treatment in an oxidizing atmosphere such as air. In this case, the metal film remaining after the heat-dissipating substance is removed must be fired in a reducing atmosphere such as hydrogen or ammonia so that the metal is reduced. Alternatively, the heat-dissipating substance may be removed by treatment at 700 ° C. to 2000 ° C. for 30 seconds to 30 minutes in an inert gas atmosphere such as nitrogen, helium, or argon.
加熱により除去される熱消失性物質は、積層繊維構造物を構成する繊維であり、具体的には、天然繊維、再生繊維、合成繊維、または炭素繊維である。これらの繊維を構成する物質は、加熱により、分解または燃焼等して、導電性繊維構造物から除去される。熱消失性物質の除去後には、繊維表面を覆っていた金属皮膜が骨格として残存し、残存した金属皮膜は消失前の繊維をかたどって金属繊維を形成する。また、積層繊維構造物における繊維間空隙は、熱消失性物質の除去後も維持されて、微細な孔を与える。このようにして、導電性繊維構造物から熱消失性物質を除去した後には、金属繊維からなる金属多孔構造物が形成される。金属皮膜が積層繊維構造物を作製した後に形成される場合、繊維の交差点及び接合点においては、その全体が金属皮膜で覆われる。そのため、金属多孔構造物の金属繊維同士の交差点及び接合点においては、交差している個々の繊維が判然とせず、金属繊維が一体化している。
The heat-dissipating substance removed by heating is a fiber constituting the laminated fiber structure, and specifically, natural fiber, regenerated fiber, synthetic fiber, or carbon fiber. Substances constituting these fibers are removed from the conductive fiber structure by heating or the like by decomposition or combustion. After removal of the heat-dissipating substance, the metal film covering the fiber surface remains as a skeleton, and the remaining metal film forms a metal fiber by following the fiber before disappearance. In addition, the inter-fiber voids in the laminated fiber structure are maintained even after removal of the heat-dissipating substance to give fine pores. Thus, after removing the heat-dissipating substance from the conductive fiber structure, a metal porous structure made of metal fibers is formed. When the metal film is formed after producing the laminated fiber structure, the whole is covered with the metal film at the intersections and joining points of the fibers. Therefore, at the intersections and junctions between the metal fibers of the metal porous structure, the intersecting individual fibers are unclear and the metal fibers are integrated.
本発明の電池用電極材について説明する。電池用電極材は、芯体に活物質合剤が充填されているものである。本発明の電池用電極材においては、芯体が、本発明の導電性繊維構造物またはそれから得られる金属多孔構造物である。活物質合剤は、活物質粒子、電極の特性を改善するための添加剤粒子、活物質粒子及び添加剤粒子を芯体に結着するための結着剤を含む。
The battery electrode material of the present invention will be described. The battery electrode material has a core body filled with an active material mixture. In the battery electrode material of the present invention, the core is the conductive fiber structure of the present invention or a metal porous structure obtained therefrom. The active material mixture includes active material particles, additive particles for improving the characteristics of the electrode, active material particles, and a binder for binding the additive particles to the core.
電池用電極材がニッケル水素電池の正極材である場合、活物質粒子は水酸化ニッケル粒子である。水酸化ニッケル粒子は、ニッケルの平均価数が2よりも大の高次水酸化ニッケル粒子であってもよい。また水酸化ニッケル粒子は、コバルト、亜鉛、またはカドミウム等を固溶していてもよく、あるいはコバルト化合物で表面が被覆されていてもよい。
When the battery electrode material is a positive electrode material of a nickel metal hydride battery, the active material particles are nickel hydroxide particles. The nickel hydroxide particles may be higher-order nickel hydroxide particles having an average nickel valence of greater than 2. Further, the nickel hydroxide particles may be solid-solved with cobalt, zinc, cadmium, or the like, or the surface may be coated with a cobalt compound.
添加剤は、例えば、酸化イットリウム;酸化コバルト、金属コバルト、及び水酸化コバルト等のコバルト化合物;金属亜鉛、酸化亜鉛、及び水酸化亜鉛等の亜鉛化合物;ならびに酸化エルビウム等の希土類化合物から選択される。
The additive is selected from, for example, yttrium oxide; cobalt compounds such as cobalt oxide, metal cobalt, and cobalt hydroxide; zinc compounds such as metal zinc, zinc oxide, and zinc hydroxide; and rare earth compounds such as erbium oxide. .
結着剤としては、親水性または疎水性のポリマーを用いることができる。具体的には、ヒドロキシプロピルセルロース(HPC)、カルボキシメチルセルロース(CMC)、及びポリアクリル酸ナトリウム(SPA)から選択される1または複数のポリマーを使用することができる。結着剤は、例えば活物質粒子100質量部に対して0.1質量部以上0.5質量部以下の量で使用してよい。
As the binder, a hydrophilic or hydrophobic polymer can be used. Specifically, one or more polymers selected from hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), and sodium polyacrylate (SPA) can be used. For example, the binder may be used in an amount of 0.1 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the active material particles.
活物質合剤の充填は、前記成分をイオン交換水に分散させてペーストを作製し、このペースト状物に、芯体を浸漬して圧力を加え、芯体の表面からペーストを圧入する方法、またはペーストを、芯体の表面に吹き付ける方法により実施してよい。ペーストは、粘度が1Pa・sから10Pa・sとなるように作製して、充填することが好ましい。粘度が小さいペーストを用いると、活物質合剤の濃度が小さいため、所望の量の活物質合剤を充填させることが難しくなる。粘度が大すぎると、ペーストが芯体内部に十分に充填されず、やはり所望の量の活物質合剤を充填させることが難しくなる。本発明の導電性構造物及びそれから形成される金属多孔構造物は、この範囲の粘度のペーストを充填させるのに特に適している。
The filling of the active material mixture is a method in which the above components are dispersed in ion-exchanged water to prepare a paste, and a pressure is applied by immersing the core in this paste-like material, and the paste is pressed from the surface of the core, Or you may implement by the method of spraying a paste on the surface of a core. The paste is preferably prepared and filled so as to have a viscosity of 1 Pa · s to 10 Pa · s. When a paste having a low viscosity is used, it is difficult to fill a desired amount of the active material mixture because the concentration of the active material mixture is small. When the viscosity is too large, the paste is not sufficiently filled in the core body, and it is difficult to fill the active material mixture in a desired amount. The conductive structure of the present invention and the metal porous structure formed therefrom are particularly suitable for filling pastes with a viscosity in this range.
ペースト充填後の芯体は、通常、乾燥処理及びロールによる圧延処理に付される。このようにして、電池用電極材を得ることができる。この電池用電極材に集電部を設けて、所定の寸法に裁断して、電極を得る。この電極を、他の部品または要素(この電極と対となる電極(通常は負極)、セパレータ、及び電解質)と共に、電池容器に密封すると、電池を得ることができる。
The core after paste filling is usually subjected to a drying process and a rolling process using a roll. In this way, a battery electrode material can be obtained. The battery electrode material is provided with a current collector and cut into a predetermined size to obtain an electrode. When this electrode is sealed in a battery container together with other parts or elements (an electrode paired with this electrode (usually a negative electrode), a separator, and an electrolyte), a battery can be obtained.
以下、実施例を用いて本発明をさらに具体的に説明する。なお、本発明は下記の実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.
本発明における各種試験の測定・評価法は次のとおりである。
The measurement and evaluation methods for various tests in the present invention are as follows.
[目付]
短繊維層及び積層繊維構造物の目付(g/m2)は、試料を20cm×20cmに切り出し、その質量を測定して算出した。 [Unit weight]
The basis weight (g / m 2 ) of the short fiber layer and the laminated fiber structure was calculated by cutting a sample into 20 cm × 20 cm and measuring its mass.
短繊維層及び積層繊維構造物の目付(g/m2)は、試料を20cm×20cmに切り出し、その質量を測定して算出した。 [Unit weight]
The basis weight (g / m 2 ) of the short fiber layer and the laminated fiber structure was calculated by cutting a sample into 20 cm × 20 cm and measuring its mass.
[厚み]
厚みは、厚み測定機((株)大栄科学精器製作所製、THICKNESS GAUGEモデルCR-60A)を用い、試料1cm2あたり2.94cNの荷重を加えた状態で測定した。この方法で測定した厚みと、前記方法で求めた繊維構造物の目付から、繊維構造物の密度(g/cm3)を算出した。 [Thickness]
The thickness was measured using a thickness measuring machine (THICKNESS GAUGE model CR-60A, manufactured by Daiei Kagaku Seisakusho Co., Ltd.) with a load of 2.94 cN applied per 1 cm 2 of the sample. From the thickness measured by this method and the basis weight of the fiber structure obtained by the above method, the density (g / cm 3 ) of the fiber structure was calculated.
厚みは、厚み測定機((株)大栄科学精器製作所製、THICKNESS GAUGEモデルCR-60A)を用い、試料1cm2あたり2.94cNの荷重を加えた状態で測定した。この方法で測定した厚みと、前記方法で求めた繊維構造物の目付から、繊維構造物の密度(g/cm3)を算出した。 [Thickness]
The thickness was measured using a thickness measuring machine (THICKNESS GAUGE model CR-60A, manufactured by Daiei Kagaku Seisakusho Co., Ltd.) with a load of 2.94 cN applied per 1 cm 2 of the sample. From the thickness measured by this method and the basis weight of the fiber structure obtained by the above method, the density (g / cm 3 ) of the fiber structure was calculated.
[引張強力、伸度]
JIS-L-1096に準じ、幅5cm、長さ15cmの試料片をつかみ間隔10cmで把持し、定速伸長型引張試験機((株)オリエンテック製、UCT-1T)を用いて引張速度30cm/min.で伸長し、切断時の荷重値及び伸長率をそれぞれ引張強力及び伸度とした。 [Tensile strength, elongation]
In accordance with JIS-L-1096, a sample piece having a width of 5 cm and a length of 15 cm is gripped at an interval of 10 cm, and a tensile speed of 30 cm is used using a constant speed extension type tensile tester (Orientec Co., Ltd., UCT-1T). The tensile strength and elongation were taken as the load value and elongation rate at the time of cutting, respectively.
JIS-L-1096に準じ、幅5cm、長さ15cmの試料片をつかみ間隔10cmで把持し、定速伸長型引張試験機((株)オリエンテック製、UCT-1T)を用いて引張速度30cm/min.で伸長し、切断時の荷重値及び伸長率をそれぞれ引張強力及び伸度とした。 [Tensile strength, elongation]
In accordance with JIS-L-1096, a sample piece having a width of 5 cm and a length of 15 cm is gripped at an interval of 10 cm, and a tensile speed of 30 cm is used using a constant speed extension type tensile tester (Orientec Co., Ltd., UCT-1T). The tensile strength and elongation were taken as the load value and elongation rate at the time of cutting, respectively.
[地合い]
繊維構造物を目視で観察し、下記の基準に従って評価した。
+++:ムラがなく、地合いが均一である。
++:多少ムラがあるが、判別しにくく、地合が良好である。
+:ムラが顕著に認められるが、穴(繊維が存在しない不連続な部分)は存在しない。
-:穴が存在する。 [Ground]
The fiber structure was visually observed and evaluated according to the following criteria.
+++: There is no unevenness and the texture is uniform.
++: Although there is some unevenness, it is difficult to distinguish and the formation is good.
+: Unevenness is noticeable, but there are no holes (discontinuous portions where no fiber is present).
-: A hole exists.
繊維構造物を目視で観察し、下記の基準に従って評価した。
+++:ムラがなく、地合いが均一である。
++:多少ムラがあるが、判別しにくく、地合が良好である。
+:ムラが顕著に認められるが、穴(繊維が存在しない不連続な部分)は存在しない。
-:穴が存在する。 [Ground]
The fiber structure was visually observed and evaluated according to the following criteria.
+++: There is no unevenness and the texture is uniform.
++: Although there is some unevenness, it is difficult to distinguish and the formation is good.
+: Unevenness is noticeable, but there are no holes (discontinuous portions where no fiber is present).
-: A hole exists.
[単位面積あたりのめっき量]
単位面積あたりのめっき量(g/m2)は先に説明した方法に従って、前記式(4)から算出した。 [Plating amount per unit area]
The plating amount (g / m 2 ) per unit area was calculated from the formula (4) according to the method described above.
単位面積あたりのめっき量(g/m2)は先に説明した方法に従って、前記式(4)から算出した。 [Plating amount per unit area]
The plating amount (g / m 2 ) per unit area was calculated from the formula (4) according to the method described above.
[金属繊維の長辺・短辺]
金属多孔構造物を構成する金属繊維(太径金属繊維・細径金属繊維)の長辺及び短辺の測定を下記の方法にて行った。
まず測定する金属多孔構造物を切断し、その切断面を観察できるようにホルダーに固定した後、走査型電子顕微鏡にて、金属多孔構造物の前記切断面を観察して金属繊維の繊維断面における長辺及び短辺の長さを測定する。長辺、短辺の測定は異なる10点を測定し、その平均値を、その試料における長辺、短辺の長さとする。
金属多孔構造物を構成する金属繊維の繊維断面における長辺及び短辺の測定は、金属多孔構造物を切断し、その切断面を観察することで測定できる他、活物質を充填した各種電極材であっても、その切断面を観察することで測定することができる。 [Long and short sides of metal fibers]
The long side and the short side of the metal fiber (large diameter metal fiber / small diameter metal fiber) constituting the metal porous structure were measured by the following method.
First, the porous metal structure to be measured is cut and fixed to a holder so that the cut surface can be observed, and then the cut surface of the metal porous structure is observed with a scanning electron microscope in the fiber cross section of the metal fiber. Measure the length of the long and short sides. The long side and the short side are measured at 10 different points, and the average value is taken as the length of the long side and the short side of the sample.
The measurement of the long side and the short side in the fiber cross section of the metal fiber constituting the metal porous structure can be measured by cutting the metal porous structure and observing the cut surface, and various electrode materials filled with an active material Even so, it can be measured by observing the cut surface.
金属多孔構造物を構成する金属繊維(太径金属繊維・細径金属繊維)の長辺及び短辺の測定を下記の方法にて行った。
まず測定する金属多孔構造物を切断し、その切断面を観察できるようにホルダーに固定した後、走査型電子顕微鏡にて、金属多孔構造物の前記切断面を観察して金属繊維の繊維断面における長辺及び短辺の長さを測定する。長辺、短辺の測定は異なる10点を測定し、その平均値を、その試料における長辺、短辺の長さとする。
金属多孔構造物を構成する金属繊維の繊維断面における長辺及び短辺の測定は、金属多孔構造物を切断し、その切断面を観察することで測定できる他、活物質を充填した各種電極材であっても、その切断面を観察することで測定することができる。 [Long and short sides of metal fibers]
The long side and the short side of the metal fiber (large diameter metal fiber / small diameter metal fiber) constituting the metal porous structure were measured by the following method.
First, the porous metal structure to be measured is cut and fixed to a holder so that the cut surface can be observed, and then the cut surface of the metal porous structure is observed with a scanning electron microscope in the fiber cross section of the metal fiber. Measure the length of the long and short sides. The long side and the short side are measured at 10 different points, and the average value is taken as the length of the long side and the short side of the sample.
The measurement of the long side and the short side in the fiber cross section of the metal fiber constituting the metal porous structure can be measured by cutting the metal porous structure and observing the cut surface, and various electrode materials filled with an active material Even so, it can be measured by observing the cut surface.
金属多孔構造物を構成する金属繊維の繊維断面における長辺及び短辺の測定は、金属多孔構造物を切断し、その切断面を観察することで測定できる他、活物質を充填した各種電極材であっても、その切断面を観察することで測定することができる。その場合、各種電極材から充填した活物質を除去し、取り出した金属多孔構造物を切断して観察する。金属多孔構造物に活物質を充填して製造された各種電極材から活物質を除去する方法は種々知られており、希酢酸水溶液に電極材を浸漬して活物質を除去する方法、市販されている超音波洗浄機などを用いて超音波で活物質を除去する方法などがある。それらの方法は任意に用いることができる。例えば、希酢酸水溶液を使用する場合には、酢酸の濃度を1mol/lに調製した希酢酸水溶液に、電極材を12時間浸漬することで、活物質のみを除去することができる。
The measurement of the long side and the short side in the fiber cross section of the metal fiber constituting the metal porous structure can be measured by cutting the metal porous structure and observing the cut surface, and various electrode materials filled with an active material Even so, it can be measured by observing the cut surface. In that case, the active material filled from various electrode materials is removed, and the extracted metal porous structure is cut and observed. Various methods for removing an active material from various electrode materials produced by filling a metal porous structure with an active material are known. A method for removing an active material by immersing the electrode material in a dilute acetic acid aqueous solution is commercially available. For example, there is a method of removing an active material with ultrasonic waves using an ultrasonic cleaner or the like. Those methods can be arbitrarily used. For example, when a dilute acetic acid aqueous solution is used, only the active material can be removed by immersing the electrode material in a dilute acetic acid aqueous solution adjusted to a concentration of 1 mol / l of acetic acid for 12 hours.
[電気抵抗]
導電性繊維構造物の電気抵抗は日置電機株式会社製HITESTERを使用し、周波数は60kHz、オートモードで、導電性繊維構造物のMD方向、CD方向について測定した。 [Electric resistance]
The electrical resistance of the conductive fiber structure was measured with respect to the MD direction and the CD direction of the conductive fiber structure by using HITESTER manufactured by Hioki Electric Co., Ltd., with a frequency of 60 kHz and an auto mode.
導電性繊維構造物の電気抵抗は日置電機株式会社製HITESTERを使用し、周波数は60kHz、オートモードで、導電性繊維構造物のMD方向、CD方向について測定した。 [Electric resistance]
The electrical resistance of the conductive fiber structure was measured with respect to the MD direction and the CD direction of the conductive fiber structure by using HITESTER manufactured by Hioki Electric Co., Ltd., with a frequency of 60 kHz and an auto mode.
(繊維ウェブ及び積層繊維構造物の作製)
本発明の導電性繊維構造物を構成する短繊維層を作製するために、下記の繊維を用意し、長繊維シート状物として下記のシートを用意した。 (Production of fiber web and laminated fiber structure)
In order to produce the short fiber layer constituting the conductive fiber structure of the present invention, the following fibers were prepared, and the following sheets were prepared as long fiber sheets.
本発明の導電性繊維構造物を構成する短繊維層を作製するために、下記の繊維を用意し、長繊維シート状物として下記のシートを用意した。 (Production of fiber web and laminated fiber structure)
In order to produce the short fiber layer constituting the conductive fiber structure of the present invention, the following fibers were prepared, and the following sheets were prepared as long fiber sheets.
[短繊維層の構成繊維]
繊維1:芯成分がポリエチレンテレフタレート(PET 紡糸前の融点:256℃)からなり、鞘成分が高密度ポリエチレン(HDPE 紡糸前の融点:130℃)からなり、芯成分と鞘成分の芯鞘比が44/76(芯/鞘 体積比)である、繊維径16μm(2.2dtex)、繊維長51mmの同心円構造の熱接着性芯鞘型複合繊維。
繊維2:繊維径が19μm(3.3dtex)であること以外は繊維1と同じ構成及び繊維長を有する熱接着性芯鞘型複合繊維。
繊維3:繊維径が32μm(8.9dtex)であること以外は繊維1と同じ構成及び繊維長を有する熱接着性芯鞘型複合繊維。
繊維4:繊維長が38mmであること以外は繊維1と同じ構成及び繊維径を有する熱接着性芯鞘型複合繊維。 [Constituent fibers of the short fiber layer]
Fiber 1: The core component is made of polyethylene terephthalate (melting point before PET spinning: 256 ° C.), the sheath component is made of high-density polyethylene (melting point before HDPE spinning: 130 ° C.), and the core-sheath ratio of the core component to the sheath component is 44/76 (core / sheath volume ratio), a heat-adhesive core-sheath composite fiber having a concentric structure with a fiber diameter of 16 μm (2.2 dtex) and a fiber length of 51 mm.
Fiber 2: A heat-adhesive core-sheath composite fiber having the same configuration and fiber length as Fiber 1 except that the fiber diameter is 19 μm (3.3 dtex).
Fiber 3: A heat-adhesive core-sheath composite fiber having the same configuration and fiber length as Fiber 1 except that the fiber diameter is 32 μm (8.9 dtex).
Fiber 4: A heat-adhesive core-sheath composite fiber having the same configuration and fiber diameter as the fiber 1 except that the fiber length is 38 mm.
繊維1:芯成分がポリエチレンテレフタレート(PET 紡糸前の融点:256℃)からなり、鞘成分が高密度ポリエチレン(HDPE 紡糸前の融点:130℃)からなり、芯成分と鞘成分の芯鞘比が44/76(芯/鞘 体積比)である、繊維径16μm(2.2dtex)、繊維長51mmの同心円構造の熱接着性芯鞘型複合繊維。
繊維2:繊維径が19μm(3.3dtex)であること以外は繊維1と同じ構成及び繊維長を有する熱接着性芯鞘型複合繊維。
繊維3:繊維径が32μm(8.9dtex)であること以外は繊維1と同じ構成及び繊維長を有する熱接着性芯鞘型複合繊維。
繊維4:繊維長が38mmであること以外は繊維1と同じ構成及び繊維径を有する熱接着性芯鞘型複合繊維。 [Constituent fibers of the short fiber layer]
Fiber 1: The core component is made of polyethylene terephthalate (melting point before PET spinning: 256 ° C.), the sheath component is made of high-density polyethylene (melting point before HDPE spinning: 130 ° C.), and the core-sheath ratio of the core component to the sheath component is 44/76 (core / sheath volume ratio), a heat-adhesive core-sheath composite fiber having a concentric structure with a fiber diameter of 16 μm (2.2 dtex) and a fiber length of 51 mm.
Fiber 2: A heat-adhesive core-sheath composite fiber having the same configuration and fiber length as Fiber 1 except that the fiber diameter is 19 μm (3.3 dtex).
Fiber 3: A heat-adhesive core-sheath composite fiber having the same configuration and fiber length as Fiber 1 except that the fiber diameter is 32 μm (8.9 dtex).
Fiber 4: A heat-adhesive core-sheath composite fiber having the same configuration and fiber diameter as the fiber 1 except that the fiber length is 38 mm.
[長繊維シート状物]
シート1:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:174μm)とCD方向のモノフィラメント(フィラメントの繊径:187μm)が直交し、交点部分の厚さが298μm(交点部分の厚さ/フィラメントの繊維径:1.59)となっている、目合いが4mm×4mm、開口部面積が16mm2、目付が10g/m2、開口部の形状が4mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03650)
シート2:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(モノフィラメントの繊維径:338μm)とCD方向のモノフィラメント(フィラメントの繊径:337μm)が直交し、交点部分の厚さが521μm(交点部分の厚さ/フィラメントの繊維径:1.54)となっている、目合いが6mm×6mm、開口部面積が36mm2、目付が19g/m2、開口部の形状が6mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R05340) [Long fiber sheet]
Sheet 1: Polypropylene monofilaments are arranged at equal intervals in the MD and CD directions, and the monofilament in the MD direction (filament fiber diameter: 174 μm) and the CD direction monofilament (filament fiber diameter: 187 μm) are orthogonal to each other. The thickness of the portion is 298 μm (intersection portion thickness / filament fiber diameter: 1.59), the mesh is 4 mm × 4 mm, the opening area is 16 mm 2 , the basis weight is 10 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 4 mm square (Conwed (registered trademark) net product number R03650 manufactured by JX Nippon Mining & Metals ANCI Corporation)
Sheet 2: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilaments in the MD direction (monofilament fiber diameter: 338 μm) and the CD direction monofilaments (filament fiber diameter: 337 μm) are orthogonal to each other. The thickness of the portion is 521 μm (intersection portion thickness / filament fiber diameter: 1.54), the mesh is 6 mm × 6 mm, the opening area is 36 mm 2 , the basis weight is 19 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 6 mm square (Conx (registered trademark) net product number R05340 manufactured by JX Nippon Mining & Metals Corporation ANCI Corporation)
シート1:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:174μm)とCD方向のモノフィラメント(フィラメントの繊径:187μm)が直交し、交点部分の厚さが298μm(交点部分の厚さ/フィラメントの繊維径:1.59)となっている、目合いが4mm×4mm、開口部面積が16mm2、目付が10g/m2、開口部の形状が4mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03650)
シート2:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(モノフィラメントの繊維径:338μm)とCD方向のモノフィラメント(フィラメントの繊径:337μm)が直交し、交点部分の厚さが521μm(交点部分の厚さ/フィラメントの繊維径:1.54)となっている、目合いが6mm×6mm、開口部面積が36mm2、目付が19g/m2、開口部の形状が6mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R05340) [Long fiber sheet]
Sheet 1: Polypropylene monofilaments are arranged at equal intervals in the MD and CD directions, and the monofilament in the MD direction (filament fiber diameter: 174 μm) and the CD direction monofilament (filament fiber diameter: 187 μm) are orthogonal to each other. The thickness of the portion is 298 μm (intersection portion thickness / filament fiber diameter: 1.59), the mesh is 4 mm × 4 mm, the opening area is 16 mm 2 , the basis weight is 10 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 4 mm square (Conwed (registered trademark) net product number R03650 manufactured by JX Nippon Mining & Metals ANCI Corporation)
Sheet 2: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilaments in the MD direction (monofilament fiber diameter: 338 μm) and the CD direction monofilaments (filament fiber diameter: 337 μm) are orthogonal to each other. The thickness of the portion is 521 μm (intersection portion thickness / filament fiber diameter: 1.54), the mesh is 6 mm × 6 mm, the opening area is 36 mm 2 , the basis weight is 19 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 6 mm square (Conx (registered trademark) net product number R05340 manufactured by JX Nippon Mining & Metals Corporation ANCI Corporation)
シート3:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:301μm)とCD方向のモノフィラメント(フィラメントの繊径:341μm)が直交し、交点部分の厚さが427μm(交点部分の厚さ/フィラメントの繊維径:1.25)となっている、目合いが6mm×6mm、開口部面積が36mm2、目付が33g/m2、開口部の形状が6mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03018)
シート4:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:220μm)とCD方向のモノフィラメント(フィラメントの繊径:167μm)が直交し、交点部分の厚さが288μm(交点部分の厚さ/フィラメントの繊維径:1.30)となっている、目合いが8mm×9mm、開口部面積が72mm2、目付が5g/m2、開口部の形状が8mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03235) Sheet 3: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and CD direction, and the monofilaments in the MD direction (filament fiber diameter: 301 μm) and the CD direction monofilaments (filament fiber diameter: 341 μm) are orthogonal to each other. The thickness of the portion is 427 μm (intersection portion thickness / filament fiber diameter: 1.25), the mesh is 6 mm × 6 mm, the opening area is 36 mm 2 , the basis weight is 33 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 6 mm square (Conwed (registered trademark) net product number R03018 manufactured by JX Nippon Mining & Metals ANCI Corporation)
Sheet 4: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilament in the MD direction (filament fiber diameter: 220 μm) and the monofilament in the CD direction (filament fiber diameter: 167 μm) are orthogonal to each other. The thickness of the portion is 288 μm (intersection thickness / filament fiber diameter: 1.30), the mesh is 8 mm × 9 mm, the opening area is 72 mm 2 , the basis weight is 5 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 8 mm square (Conx (registered trademark) net product number R03235, manufactured by JX Nippon Mining & Metals ANCI Corporation)
シート4:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:220μm)とCD方向のモノフィラメント(フィラメントの繊径:167μm)が直交し、交点部分の厚さが288μm(交点部分の厚さ/フィラメントの繊維径:1.30)となっている、目合いが8mm×9mm、開口部面積が72mm2、目付が5g/m2、開口部の形状が8mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03235) Sheet 3: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and CD direction, and the monofilaments in the MD direction (filament fiber diameter: 301 μm) and the CD direction monofilaments (filament fiber diameter: 341 μm) are orthogonal to each other. The thickness of the portion is 427 μm (intersection portion thickness / filament fiber diameter: 1.25), the mesh is 6 mm × 6 mm, the opening area is 36 mm 2 , the basis weight is 33 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 6 mm square (Conwed (registered trademark) net product number R03018 manufactured by JX Nippon Mining & Metals ANCI Corporation)
Sheet 4: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilament in the MD direction (filament fiber diameter: 220 μm) and the monofilament in the CD direction (filament fiber diameter: 167 μm) are orthogonal to each other. The thickness of the portion is 288 μm (intersection thickness / filament fiber diameter: 1.30), the mesh is 8 mm × 9 mm, the opening area is 72 mm 2 , the basis weight is 5 g / m 2 , the opening Orthogonal net-like object whose shape is a square of 8 mm square (Conx (registered trademark) net product number R03235, manufactured by JX Nippon Mining & Metals ANCI Corporation)
シート5:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:345μm)とCD方向のモノフィラメント(フィラメントの繊径:288μm)が直交し、交点部分の厚さが368μm(交点部分の厚さ/フィラメントの繊維径:1.07)となっている、目合いが1mm×1mm、開口部面積が1mm2、目付が100g/m2、開口部の形状が1mm四方の正方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 X06065)
シート6:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:146μm)とCD方向のモノフィラメント(フィラメントの繊径:351μm)が直交し、交点部分の厚さが244μm(交点部分の厚さ/フィラメントの繊維径:0.70)となっている、目合いが1mm×4mm、開口部面積が4mm2、目付が32g/m2、開口部の形状が1mm×4mmの長方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03330) Sheet 5: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and monofilaments in the MD direction (filament fiber diameter: 345 μm) and CD direction monofilaments (filament fiber diameter: 288 μm) are orthogonal to each other. The thickness of the part is 368 μm (intersection part thickness / filament fiber diameter: 1.07), the mesh is 1 mm × 1 mm, the opening area is 1 mm 2 , the basis weight is 100 g / m 2 , the opening Orthogonal net-like object whose shape is a 1 mm square (JX Nippon Mining & Metals ANCI Corporation Conwed (registered trademark) net product number X06065)
Sheet 6: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilaments in the MD direction (filament fiber diameter: 146 μm) and the CD direction monofilaments (filament fiber diameter: 351 μm) are orthogonal to each other. The thickness of the part is 244 μm (intersection part thickness / filament fiber diameter: 0.70), the mesh is 1 mm × 4 mm, the opening area is 4 mm 2 , the basis weight is 32 g / m 2 , the opening Orthogonal net-like object whose shape is a rectangle of 1 mm × 4 mm (Conx (registered trademark) net product number R03330, manufactured by JX Nippon Mining & Metals ANCI Corporation)
シート6:ポリプロピレンからなるモノフィラメントがMD方向及びCD方向に等間隔で配置され、MD方向のモノフィラメント(フィラメントの繊維径:146μm)とCD方向のモノフィラメント(フィラメントの繊径:351μm)が直交し、交点部分の厚さが244μm(交点部分の厚さ/フィラメントの繊維径:0.70)となっている、目合いが1mm×4mm、開口部面積が4mm2、目付が32g/m2、開口部の形状が1mm×4mmの長方形である直交ネット状物(JX日鉱日石ANCI株式会社製 コンウェッド(登録商標)ネット 品番 R03330) Sheet 5: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and monofilaments in the MD direction (filament fiber diameter: 345 μm) and CD direction monofilaments (filament fiber diameter: 288 μm) are orthogonal to each other. The thickness of the part is 368 μm (intersection part thickness / filament fiber diameter: 1.07), the mesh is 1 mm × 1 mm, the opening area is 1 mm 2 , the basis weight is 100 g / m 2 , the opening Orthogonal net-like object whose shape is a 1 mm square (JX Nippon Mining & Metals ANCI Corporation Conwed (registered trademark) net product number X06065)
Sheet 6: Monofilaments made of polypropylene are arranged at equal intervals in the MD direction and the CD direction, and the monofilaments in the MD direction (filament fiber diameter: 146 μm) and the CD direction monofilaments (filament fiber diameter: 351 μm) are orthogonal to each other. The thickness of the part is 244 μm (intersection part thickness / filament fiber diameter: 0.70), the mesh is 1 mm × 4 mm, the opening area is 4 mm 2 , the basis weight is 32 g / m 2 , the opening Orthogonal net-like object whose shape is a rectangle of 1 mm × 4 mm (Conx (registered trademark) net product number R03330, manufactured by JX Nippon Mining & Metals ANCI Corporation)
(実施例1)
パラレルカードを用い、上記繊維1のみを使用して、目付が15g/m2であるパラレルカードウェブを短繊維層として2枚作製した。次に、前記シート1の両表面に、繊維1からなるカードウェブを短繊維層として積層し、両表面が繊維1からなるカードウェブである3層構造の積層物を形成した。この3層構造の積層物に対し、高圧水流を用いた水流交絡処理を施した。水流交絡処理は、孔径0.1mmのオリフィスが0.6mm間隔で設けられたノズルを用いて、前記3層構造の積層物に向けて、水圧0.98MPa(10kgf/cm2)の柱状水流を1回噴射して実施した。次いで、水流交絡処理後の積層物を、熱風吹き付け型熱処理機を用いて、110℃で乾燥した後、更に熱風吹き付け型熱処理機を用いて、140℃、13秒間熱処理を行うことによって構成繊維間を熱接着させ、積層繊維構造物を得た。 (Example 1)
Using a parallel card, two parallel card webs having a basis weight of 15 g / m 2 were produced as short fiber layers using only the fiber 1. Next, a card web made of fibers 1 was laminated as a short fiber layer on both surfaces of the sheet 1 to form a laminate having a three-layer structure in which both surfaces were card webs made of fibers 1. A hydroentanglement process using a high-pressure water stream was performed on the laminate having the three-layer structure. In the hydroentanglement treatment, a columnar water flow having a water pressure of 0.98 MPa (10 kgf / cm 2 ) is applied to the laminate having the three-layer structure by using a nozzle in which orifices having a hole diameter of 0.1 mm are provided at intervals of 0.6 mm. One injection was carried out. Next, the laminate after the hydroentanglement treatment is dried at 110 ° C. using a hot air blowing type heat treatment machine, and then further subjected to heat treatment at 140 ° C. for 13 seconds using a hot air blowing type heat treatment machine. Were thermally bonded to obtain a laminated fiber structure.
パラレルカードを用い、上記繊維1のみを使用して、目付が15g/m2であるパラレルカードウェブを短繊維層として2枚作製した。次に、前記シート1の両表面に、繊維1からなるカードウェブを短繊維層として積層し、両表面が繊維1からなるカードウェブである3層構造の積層物を形成した。この3層構造の積層物に対し、高圧水流を用いた水流交絡処理を施した。水流交絡処理は、孔径0.1mmのオリフィスが0.6mm間隔で設けられたノズルを用いて、前記3層構造の積層物に向けて、水圧0.98MPa(10kgf/cm2)の柱状水流を1回噴射して実施した。次いで、水流交絡処理後の積層物を、熱風吹き付け型熱処理機を用いて、110℃で乾燥した後、更に熱風吹き付け型熱処理機を用いて、140℃、13秒間熱処理を行うことによって構成繊維間を熱接着させ、積層繊維構造物を得た。 (Example 1)
Using a parallel card, two parallel card webs having a basis weight of 15 g / m 2 were produced as short fiber layers using only the fiber 1. Next, a card web made of fibers 1 was laminated as a short fiber layer on both surfaces of the sheet 1 to form a laminate having a three-layer structure in which both surfaces were card webs made of fibers 1. A hydroentanglement process using a high-pressure water stream was performed on the laminate having the three-layer structure. In the hydroentanglement treatment, a columnar water flow having a water pressure of 0.98 MPa (10 kgf / cm 2 ) is applied to the laminate having the three-layer structure by using a nozzle in which orifices having a hole diameter of 0.1 mm are provided at intervals of 0.6 mm. One injection was carried out. Next, the laminate after the hydroentanglement treatment is dried at 110 ° C. using a hot air blowing type heat treatment machine, and then further subjected to heat treatment at 140 ° C. for 13 seconds using a hot air blowing type heat treatment machine. Were thermally bonded to obtain a laminated fiber structure.
得られた積層繊維構造物を17.6cm×28cmの大きさに切断し、塩化第一スズ、塩化パラジウムなどを含む溶液を用いた触媒化処理(キャタリスト)を積層繊維構造物に行った。それから、水溶性ニッケル化合物の他、公知の錯化剤、還元剤を含む無電解ニッケルめっき液に、触媒化処理を行った積層繊維構造物を含浸させ、無電解めっきを行い、繊維表面にニッケル皮膜を形成して、導電性繊維構造物を得た。この導電性繊維構造物において、繊維表面に付着したニッケルの量は0.111gであり、単位面積あたりのめっき量は4.53g/m2であった。
The obtained laminated fiber structure was cut into a size of 17.6 cm × 28 cm, and a catalyst treatment (catalyst) using a solution containing stannous chloride, palladium chloride and the like was performed on the laminated fiber structure. Then, in addition to a water-soluble nickel compound, an electroless nickel plating solution containing a known complexing agent and reducing agent is impregnated with the laminated fiber structure that has been subjected to the catalytic treatment, electroless plating is performed, and nickel is applied to the fiber surface. A film was formed to obtain a conductive fiber structure. In this conductive fiber structure, the amount of nickel attached to the fiber surface was 0.111 g, and the plating amount per unit area was 4.53 g / m 2 .
(実施例2~12)
短繊維層を構成する繊維、長繊維シート状物を、それぞれ表1~2に示すものに変更したこと以外は、実施例1を作製するときに採用した手順と同じ手順で、積層繊維構造物を得、さらに導電性繊維構造物を得た。 (Examples 2 to 12)
Laminated fiber structure in the same procedure as that used in the production of Example 1 except that the fibers constituting the short fiber layer and the long fiber sheet were changed to those shown in Tables 1 and 2, respectively. In addition, a conductive fiber structure was obtained.
短繊維層を構成する繊維、長繊維シート状物を、それぞれ表1~2に示すものに変更したこと以外は、実施例1を作製するときに採用した手順と同じ手順で、積層繊維構造物を得、さらに導電性繊維構造物を得た。 (Examples 2 to 12)
Laminated fiber structure in the same procedure as that used in the production of Example 1 except that the fibers constituting the short fiber layer and the long fiber sheet were changed to those shown in Tables 1 and 2, respectively. In addition, a conductive fiber structure was obtained.
(比較例1)
パラレルカードを用い、上記繊維1のみを使用して、目付が30g/m2である、繊維1の単一層からなるウェブを作製した。このウェブに対し、高圧水流を用いた水流交絡処理を施した。水流交絡処理は、孔径0.1mmのオリフィスが0.6mm間隔で設けられたノズルを用いて、前記ウェブに向けて、水圧0.98MPa(10kgf/cm2)の柱状水流を1回噴射して実施した。次いで、水流交絡処理後のウェブを、熱風吹き付け型熱処理機を用いて、110℃で乾燥した後、更に熱風吹き付け型熱処理機を用いて、140℃、13秒間熱処理を行うことによって構成繊維間を熱接着させ、単層の繊維構造物を得た。得られた繊維構造物の繊維表面にニッケル皮膜を形成して、導電性繊維構造物を得た。ニッケル皮膜の形成は、実施例1で採用した手順と同じ手順で実施した。 (Comparative Example 1)
Using a parallel card, a web composed of a single layer of fiber 1 having a basis weight of 30 g / m 2 was produced using only fiber 1 described above. The web was subjected to hydroentanglement treatment using a high-pressure water stream. In the hydroentanglement treatment, a columnar water flow having a water pressure of 0.98 MPa (10 kgf / cm 2 ) is sprayed once toward the web using a nozzle having orifices with a hole diameter of 0.1 mm provided at intervals of 0.6 mm. Carried out. Next, the web after the hydroentanglement treatment is dried at 110 ° C. using a hot air blowing type heat treatment machine, and further subjected to heat treatment at 140 ° C. for 13 seconds using a hot air blowing type heat treatment machine, thereby separating the constituent fibers. A single-layer fiber structure was obtained by heat bonding. A nickel film was formed on the fiber surface of the obtained fiber structure to obtain a conductive fiber structure. The nickel film was formed by the same procedure as that adopted in Example 1.
パラレルカードを用い、上記繊維1のみを使用して、目付が30g/m2である、繊維1の単一層からなるウェブを作製した。このウェブに対し、高圧水流を用いた水流交絡処理を施した。水流交絡処理は、孔径0.1mmのオリフィスが0.6mm間隔で設けられたノズルを用いて、前記ウェブに向けて、水圧0.98MPa(10kgf/cm2)の柱状水流を1回噴射して実施した。次いで、水流交絡処理後のウェブを、熱風吹き付け型熱処理機を用いて、110℃で乾燥した後、更に熱風吹き付け型熱処理機を用いて、140℃、13秒間熱処理を行うことによって構成繊維間を熱接着させ、単層の繊維構造物を得た。得られた繊維構造物の繊維表面にニッケル皮膜を形成して、導電性繊維構造物を得た。ニッケル皮膜の形成は、実施例1で採用した手順と同じ手順で実施した。 (Comparative Example 1)
Using a parallel card, a web composed of a single layer of fiber 1 having a basis weight of 30 g / m 2 was produced using only fiber 1 described above. The web was subjected to hydroentanglement treatment using a high-pressure water stream. In the hydroentanglement treatment, a columnar water flow having a water pressure of 0.98 MPa (10 kgf / cm 2 ) is sprayed once toward the web using a nozzle having orifices with a hole diameter of 0.1 mm provided at intervals of 0.6 mm. Carried out. Next, the web after the hydroentanglement treatment is dried at 110 ° C. using a hot air blowing type heat treatment machine, and further subjected to heat treatment at 140 ° C. for 13 seconds using a hot air blowing type heat treatment machine, thereby separating the constituent fibers. A single-layer fiber structure was obtained by heat bonding. A nickel film was formed on the fiber surface of the obtained fiber structure to obtain a conductive fiber structure. The nickel film was formed by the same procedure as that adopted in Example 1.
(比較例2~5)
使用した繊維を表2に記載のものに変更したこと以外は、比較例1を作製するときに採用した手順と同じ手順で、積層繊維構造物を得、さらに導電性繊維構造物を得た。 (Comparative Examples 2 to 5)
A laminated fiber structure was obtained in the same procedure as that used when producing Comparative Example 1 except that the used fiber was changed to that shown in Table 2, and a conductive fiber structure was obtained.
使用した繊維を表2に記載のものに変更したこと以外は、比較例1を作製するときに採用した手順と同じ手順で、積層繊維構造物を得、さらに導電性繊維構造物を得た。 (Comparative Examples 2 to 5)
A laminated fiber structure was obtained in the same procedure as that used when producing Comparative Example 1 except that the used fiber was changed to that shown in Table 2, and a conductive fiber structure was obtained.
得られた実施例1~12の導電性繊維構造物、比較例1~5の導電性繊維構造物について、前記の方法で単位面積あたりのめっき量、MD方向の電気抵抗、CD方向の電気抵抗、電気抵抗のMD/CD比を測定及び評価した。またこれらの結果と共に、各実施例及び比較例において、構成繊維表面に金属皮膜を形成する処理の前に測定した、実施例1~12の積層繊維構造物、及び比較例1~5の単層構造の繊維構造物の目付、厚み、密度、比容積、MD方向、CD方向の引張強力、引張強力のMD/CD比を表1~2に示す。さらに、実施例2、7の導電性繊維構造物の表面を撮影した走査型顕微鏡写真を図1~3に示す。
For the obtained conductive fiber structures of Examples 1 to 12 and the conductive fiber structures of Comparative Examples 1 to 5, the plating amount per unit area, the electric resistance in the MD direction, the electric resistance in the CD direction by the above-described methods. The MD / CD ratio of electrical resistance was measured and evaluated. In addition to these results, in each of the examples and comparative examples, the laminated fiber structures of Examples 1 to 12 and the single layers of Comparative Examples 1 to 5 were measured before the treatment for forming the metal film on the constituent fiber surface. Tables 1 and 2 show the basis weight, thickness, density, specific volume, MD direction, tensile strength in the CD direction, and MD / CD ratio of tensile strength of the structural fiber structure. Further, scanning micrographs obtained by photographing the surfaces of the conductive fiber structures of Examples 2 and 7 are shown in FIGS.
表1~2に示すように、中層が長繊維シート状物である三層構造を有する実施例1~12の導電性繊維構造物は、同じ短繊維を使用して作製した単層構造の導電性繊維構造物と比較して、MD方向及びCD方向の少なくとも一方の電気抵抗が低かった。これは、長繊維シート状物の存在により、短繊維が良好に交絡していることによると考えられる。
As shown in Tables 1 and 2, the conductive fiber structures of Examples 1 to 12 having a three-layer structure in which the middle layer is a long fiber sheet-like material are conductive layers having a single layer structure manufactured using the same short fibers. As compared with the conductive fiber structure, the electrical resistance in at least one of the MD direction and the CD direction was low. This is considered to be because the short fibers are entangled well due to the presence of the long fiber sheet.
目合いが同じであるが、モノフィラメント(長繊維)の繊維径が異なる直交ネット状物を用いた実施例4と、実施例6とを比較すると、実施例4がより低い電気抵抗の総和を示した。前記電気抵抗の総和とは、MD方向の電気抵抗値とCD方向の電気抵抗値の和である。これは、長繊維の繊維径が太いと、短繊維層の繊維が長繊維と交絡しにくくなる、または短繊維層の繊維同士が交絡しにくくなって、金属皮膜の連続性がやや低下することによると考えられる。
Comparing Example 4 and Example 6 using orthogonal nets having the same scale but different monofilament (long fiber) fiber diameters, Example 4 shows a lower total electrical resistance. It was. The total sum of electric resistances is the sum of the electric resistance value in the MD direction and the electric resistance value in the CD direction. This is because if the fiber diameter of the long fibers is thick, the fibers in the short fiber layer are not easily entangled with the long fibers, or the fibers in the short fiber layer are not easily entangled with each other, and the continuity of the metal film is slightly reduced. It is thought that.
金属皮膜を形成する前の繊維構造物の力学的特性について考察する。比較例1、2、3においては、MD方向の引張強力が高く、CD方向の引張強力はMD方向と比較して極端に低くなり、引張強力のMD/CD比が3より大きくなっていた。これに対して、実施例に使用した積層繊維構造物は中層に長繊維シート状物を挿入したことで、引張強力のMD方向とCD方向の値の差が小さくなり、いずれも3未満であった。そのため、これらの実施例の積層繊維構造物は取り扱いやすく、金属皮膜を形成した後も、取り扱いやすいものであった。
Consider the mechanical properties of the fiber structure before forming the metal film. In Comparative Examples 1, 2, and 3, the tensile strength in the MD direction was high, the tensile strength in the CD direction was extremely lower than that in the MD direction, and the MD / CD ratio of tensile strength was larger than 3. On the other hand, the laminated fiber structures used in the examples had a difference in tensile strength between the MD direction and the CD direction by inserting a long fiber sheet into the middle layer, and both were less than 3. It was. Therefore, the laminated fiber structures of these examples were easy to handle and easy to handle even after the metal film was formed.
なお、実施例には、地合の良いものも、悪いものも含まれている。地合の良いものは、電極材及びろ過精度の高い耐熱フィルターを形成するのに好ましく用いられる。地合の悪いものも、例えば、粗塵フィルターのように、地合が製品の品質に影響を及ぼさない用途、または地合に粗密を有することが望まれる用途において使用できる。
In addition, the example includes a good one and a bad one. Those having good formation are preferably used for forming an electrode material and a heat-resistant filter having high filtration accuracy. Those with poor formation can also be used in applications where the formation does not affect the quality of the product, such as a coarse dust filter, or where it is desired that the formation be dense.
実施例の導電性繊維構造物と、比較例の導電性繊維構造物を比較する。ニッケル皮膜を形成する前の積層繊維構造物において、比較例1~5の積層繊維構造物は引張強力のMD/CD比が大きく、引張強力の方向依存性があるのに対し、実施例1~12のそれらはMD/CDが1に近い。これは実施例1~12で用いた繊維構造物が異なる2以上の方向に延びる長繊維で構成される長繊維シートを含むことで、短繊維層の方向依存性が緩和されたためと考えられる。また、積層繊維構造物の力学的特性の方向依存性が小さいため、導電性繊維構造物を生産する際の工程性や取り扱い性が向上し、さらに、導電性繊維構造物の強度が方向によって大きく異なることがなくなるため、導電性繊維構造物の取り扱い性が向上すると考えられる。
The conductive fiber structure of the example is compared with the conductive fiber structure of the comparative example. In the laminated fiber structure before forming the nickel film, the laminated fiber structures of Comparative Examples 1 to 5 have a high tensile strength MD / CD ratio and are dependent on the direction of the tensile strength. 12 of them have MD / CD close to 1. This is presumably because the fiber structure used in Examples 1 to 12 includes a long fiber sheet composed of long fibers extending in two or more different directions, thereby reducing the direction dependency of the short fiber layer. In addition, since the direction dependency of the mechanical properties of the laminated fiber structure is small, the processability and handleability when producing the conductive fiber structure are improved, and the strength of the conductive fiber structure is increased depending on the direction. Since there is no difference, it is considered that the handleability of the conductive fiber structure is improved.
実施例1~12の導電性繊維構造物と比較例の導電性繊維構造物を比較すると、比較例の導電性繊維構造物は、MD方向とCD方向の電気抵抗を合計した値が3.2Ωを超えるのに対し、本発明の導電性繊維構造物は全て3Ω未満となっている。これは本発明の導電性繊維構造物が長繊維シート状物を含み、それにより内部に連続した導電性領域が形成されたことにより電気抵抗が低下したためと考えられる。また、実施例1~12の導電性繊維構造物において、MD方向、CD方向いずれ方向の電気抵抗も1.8Ω未満であり、電気抵抗のMD/CD比は0.4以上、1.5以下の範囲である。このことから、本発明の導電性繊維構造物の電気的特性が方向依存性の少ないものとなっていることを確認できる。これは、本発明の導電性繊維構造物が異なる二方向に延びる長繊維シートを含むことによると考えられる。
When the conductive fiber structures of Examples 1 to 12 and the conductive fiber structure of the comparative example are compared, the conductive fiber structure of the comparative example has a sum of electric resistances in the MD direction and the CD direction of 3.2Ω. In contrast, all the conductive fiber structures of the present invention are less than 3Ω. This is presumably because the conductive fiber structure of the present invention includes a long fiber sheet-like material, thereby forming a continuous conductive region therein, thereby reducing the electrical resistance. In the conductive fiber structures of Examples 1 to 12, the electric resistance in either the MD direction or the CD direction is less than 1.8Ω, and the MD / CD ratio of the electric resistance is 0.4 or more and 1.5 or less. Range. From this, it can be confirmed that the electrical characteristics of the conductive fiber structure of the present invention are less directional dependent. This is considered because the conductive fiber structure of the present invention includes a long fiber sheet extending in two different directions.
(金属多孔構造物 電極材の作製)
実施例7、比較例1、2、4、5において作製した繊維構造物と、新たに実施例13の繊維構造物を準備して電池用電極材を作製した。 (Production of porous metal structure electrode material)
The fiber structure produced in Example 7 and Comparative Examples 1, 2, 4, and 5 and the fiber structure of Example 13 were newly prepared to produce battery electrode materials.
実施例7、比較例1、2、4、5において作製した繊維構造物と、新たに実施例13の繊維構造物を準備して電池用電極材を作製した。 (Production of porous metal structure electrode material)
The fiber structure produced in Example 7 and Comparative Examples 1, 2, 4, and 5 and the fiber structure of Example 13 were newly prepared to produce battery electrode materials.
(実施例13)
まず、実施例13の繊維構造物について説明する。パラレルカード機を用い、上記繊維2のみを使用して、目付が15g/m2であるパラレルカードウェブを短繊維層として作製した。次に、前記繊維2からなるカードウェブの上に前記シート1を載置した。このシート1の上に、前記繊維2からなる、目付が15g/m2であるパラレルカードウェブをさらに積層して、中心部に前記シート1が配置されている3層構造の積層物を作製した。この3層構造の積層物に対し、高圧水流を用いた水流交絡処理を施した。水流交絡処理は、孔径0.1mmのオリフィスが1.0mm間隔で設けられたノズルを用いて、前記3層構造の積層物に向けて、水圧1.47MPa(15kgf/cm2)の柱状水流を前記3層構造の積層物に1回噴射した後、同じ面に水圧2.45MPa(25kgf/cm2)の柱状水流を1回噴射して実施した。次いで、水流交絡処理後の積層物を、熱風吹き付け型熱処理機を用いて、135℃で熱処理を行い、乾燥と同時に構成繊維間を熱接着させ、積層繊維構造物を得た。 (Example 13)
First, the fiber structure of Example 13 will be described. Using a parallel card machine, a parallel card web having a basis weight of 15 g / m 2 was produced as a short fiber layer using only the fiber 2. Next, the sheet 1 was placed on the card web made of the fibers 2. A parallel card web made of the fibers 2 and having a basis weight of 15 g / m 2 was further laminated on the sheet 1 to produce a laminate having a three-layer structure in which the sheet 1 was arranged at the center. . A hydroentanglement process using a high-pressure water stream was performed on the laminate having the three-layer structure. In the hydroentanglement treatment, a columnar water flow having a water pressure of 1.47 MPa (15 kgf / cm 2 ) is applied to the laminate having the three-layer structure by using a nozzle in which orifices having a hole diameter of 0.1 mm are provided at intervals of 1.0 mm. After spraying once on the laminate having the three-layer structure, a columnar water flow having a water pressure of 2.45 MPa (25 kgf / cm 2 ) was sprayed once on the same surface. Next, the laminate after the hydroentanglement treatment was heat-treated at 135 ° C. using a hot air blowing type heat treatment machine, and the constituent fibers were thermally bonded simultaneously with drying to obtain a laminated fiber structure.
まず、実施例13の繊維構造物について説明する。パラレルカード機を用い、上記繊維2のみを使用して、目付が15g/m2であるパラレルカードウェブを短繊維層として作製した。次に、前記繊維2からなるカードウェブの上に前記シート1を載置した。このシート1の上に、前記繊維2からなる、目付が15g/m2であるパラレルカードウェブをさらに積層して、中心部に前記シート1が配置されている3層構造の積層物を作製した。この3層構造の積層物に対し、高圧水流を用いた水流交絡処理を施した。水流交絡処理は、孔径0.1mmのオリフィスが1.0mm間隔で設けられたノズルを用いて、前記3層構造の積層物に向けて、水圧1.47MPa(15kgf/cm2)の柱状水流を前記3層構造の積層物に1回噴射した後、同じ面に水圧2.45MPa(25kgf/cm2)の柱状水流を1回噴射して実施した。次いで、水流交絡処理後の積層物を、熱風吹き付け型熱処理機を用いて、135℃で熱処理を行い、乾燥と同時に構成繊維間を熱接着させ、積層繊維構造物を得た。 (Example 13)
First, the fiber structure of Example 13 will be described. Using a parallel card machine, a parallel card web having a basis weight of 15 g / m 2 was produced as a short fiber layer using only the fiber 2. Next, the sheet 1 was placed on the card web made of the fibers 2. A parallel card web made of the fibers 2 and having a basis weight of 15 g / m 2 was further laminated on the sheet 1 to produce a laminate having a three-layer structure in which the sheet 1 was arranged at the center. . A hydroentanglement process using a high-pressure water stream was performed on the laminate having the three-layer structure. In the hydroentanglement treatment, a columnar water flow having a water pressure of 1.47 MPa (15 kgf / cm 2 ) is applied to the laminate having the three-layer structure by using a nozzle in which orifices having a hole diameter of 0.1 mm are provided at intervals of 1.0 mm. After spraying once on the laminate having the three-layer structure, a columnar water flow having a water pressure of 2.45 MPa (25 kgf / cm 2 ) was sprayed once on the same surface. Next, the laminate after the hydroentanglement treatment was heat-treated at 135 ° C. using a hot air blowing type heat treatment machine, and the constituent fibers were thermally bonded simultaneously with drying to obtain a laminated fiber structure.
実施例7、比較例1、2、4、5において作製した繊維構造物と、前記製造方法で製造した実施例13の繊維構造物に対し、金属ニッケルをターゲットにしたスパッタリング処理を行い、繊維構造物の構成繊維表面にニッケル皮膜を形成させた。スパッタリングはアルゴンガスを用いたイオンビームスパッタ法で行い、上記繊維構造物の構成繊維表面に対して均一なニッケル皮膜を形成した。この導電性繊維構造物に対し、硫酸ニッケル、塩化ニッケルを主成分とするワット浴を用い、ニッケル金属をアノードとして、繊維構造物にニッケルめっきを施し、導電性繊維構造物を得た。ニッケルめっきは、実施例7、比較例1、2、4、5に対しては単位面積あたりのニッケル量が400g/m2となるように実施した。実施例13に対しては単位面積あたりのニッケル量が350g/m2となるように実施した。次いで、導電性構造物を加熱処理に付して繊維構造物を構成する熱消失性物質を除去して、金属多孔構造物を得た。その後、導電性繊維構造物が1.5mmの厚みになるように厚み加工を施した。加熱処理では、600℃で熱消失物質を除去した後、1000℃の還元雰囲気下(アンモニア分解ガス等を使用)、ニッケルを還元処理した。
The fiber structure manufactured in Example 7 and Comparative Examples 1, 2, 4, and 5 and the fiber structure of Example 13 manufactured by the above manufacturing method were subjected to sputtering treatment using metallic nickel as a target, and the fiber structure A nickel film was formed on the surface of the constituent fibers of the article. Sputtering was performed by ion beam sputtering using argon gas, and a uniform nickel film was formed on the constituent fiber surfaces of the fiber structure. The conductive fiber structure was subjected to nickel plating using a Watt bath mainly composed of nickel sulfate and nickel chloride and nickel metal as an anode to obtain a conductive fiber structure. Nickel plating was performed for Example 7 and Comparative Examples 1, 2, 4, and 5 so that the amount of nickel per unit area was 400 g / m 2 . For Example 13, the nickel amount per unit area was 350 g / m 2 . Next, the conductive structure was subjected to a heat treatment to remove the heat-dissipating substance constituting the fiber structure to obtain a metal porous structure. Thereafter, the conductive fiber structure was processed to have a thickness of 1.5 mm. In the heat treatment, after removing the heat-dissipating substance at 600 ° C., nickel was reduced in a reducing atmosphere at 1000 ° C. (using ammonia decomposition gas or the like).
得られた金属多孔構造物に、活物質粒子として水酸化ニッケル、添加剤として水酸化コバルト、結着剤としてヒドロキシプロピルセルロース(HPC)を含むペーストを塗布し、活物質合剤を充填させた。ペーストの塗布は、粘度4Pa・sのペーストに金属多孔構造物を連続的に浸漬することにより実施した。ペーストを塗布した後、乾燥、圧延処理して、所定寸法の電池用電極材を得た。
A paste containing nickel hydroxide as active material particles, cobalt hydroxide as an additive, and hydroxypropyl cellulose (HPC) as a binder was applied to the obtained metal porous structure, and the active material mixture was filled. The paste was applied by continuously immersing the metal porous structure in a paste having a viscosity of 4 Pa · s. After applying the paste, it was dried and rolled to obtain a battery electrode material having a predetermined size.
得られた実施例7と比較例2の電極材を用いて、電極材を構成している金属多孔構造物の金属繊維を観察し、太径金属繊維、細径金属繊維それぞれの繊維断面における長辺及び短辺を測定した。測定は前記の通り、まず金属多孔構造物に充填された活物質を除去して金属多孔構造物を取り出した後、取り出した金属多孔構造物を切断し、走査型電子顕微鏡にて切断面を観察して測定した。その結果を表3に示す。
Using the obtained electrode material of Example 7 and Comparative Example 2, the metal fibers of the metal porous structure constituting the electrode material were observed, and the lengths of the fiber cross-sections of the large-diameter metal fiber and the small-diameter metal fiber were respectively long. Sides and short sides were measured. As described above, first, after removing the active material filled in the metal porous structure and taking out the metal porous structure, the taken metal porous structure is cut and the cut surface is observed with a scanning electron microscope. And measured. The results are shown in Table 3.
得られた電池用電極材における、単位面積あたりの活物質粒子の質量を測定した。活物質粒子の質量の測定は、粘度4Pa・sのペーストに、連続的に浸漬された金属多孔構造物を乾燥した後、単位面積あたりの活物質粒子の質量を5m間隔で測定する方法により実施した。測定値から、単位面積あたりの活物質粒子の質量の標準偏差、及び最大値と最小値の差を求めた。その結果を表3に示す。標準偏差、及び最大値と最小値の差が小さいほど、活物質粒子が均一に充填され、均一な特性を有する電池用電極材が得られたことを示す。
The mass of active material particles per unit area in the obtained battery electrode material was measured. The mass of the active material particles is measured by a method of measuring the mass of the active material particles per unit area at intervals of 5 m after drying a metal porous structure continuously immersed in a paste having a viscosity of 4 Pa · s. did. From the measured values, the standard deviation of the mass of the active material particles per unit area and the difference between the maximum value and the minimum value were determined. The results are shown in Table 3. The smaller the standard deviation and the difference between the maximum value and the minimum value, the more uniformly the active material particles are filled, indicating that a battery electrode material having uniform characteristics was obtained.
本発明の電極材である実施例7、実施例13と、比較例の電極材を比較すると、充填された活物質量の最大値と最小値の差が、比較例の電極材よりも本発明の電極材のほうが小さくなっている。従って本発明の導電性繊維構造物及び金属多孔構造物を用いると、従来のそれらよりも活物質充填量が安定し、電極材の性能が均一な電極材を容易に製造できる。本発明の電極材において活物質充填量が安定化した原因は特定できない。一つの考えられる理由は、本発明の導電性繊維構造物を用いて製造した金属多孔構造物に活物質を含むペーストを塗布して活物質を充填するときに、連続する長金属繊維(実施例では太径金属繊維でもある)によって金属多孔構造物の空隙形状がつぶれにくくなり、活物質の充填性が場所により変動しにくくなった、あるいは連続する金属繊維によって活物質が脱落しにくくなったことである。
When Example 7 and Example 13 which are the electrode materials of the present invention are compared with the electrode material of the comparative example, the difference between the maximum value and the minimum value of the amount of filled active material is greater than that of the electrode material of the comparative example. The electrode material is smaller. Therefore, when the conductive fiber structure and the metal porous structure of the present invention are used, an electrode material with more stable active material filling and uniform performance of the electrode material can be easily produced than those of the prior art. The reason why the active material filling amount is stabilized in the electrode material of the present invention cannot be specified. One possible reason is that when a metal porous structure manufactured using the conductive fiber structure of the present invention is coated with a paste containing an active material and filled with the active material, continuous long metal fibers (Examples) In this case, the void shape of the metal porous structure is less likely to be crushed, and the filling of the active material is less likely to vary depending on the location, or the active material is less likely to fall off due to the continuous metal fiber. It is.
金属多孔構造物の表面を観察した図5から、本発明の金属多孔構造物では、長金属繊維が金属多孔構造物の中に連続して存在することが確認できる。このことから、連続する長金属繊維によって、金属多孔構造物に対し、連続している繊維の延びる方向に良好な電気的特性をもたらしていると考えられる。そして、連続する長金属繊維が、異なる2方向以上の方向に配向することで、電気的特性の偏り(異方性)を抑えていると考えられる。また、図6及び図8から、細径金属繊維である短金属繊維は太径金属繊維である長金属繊維と接合していることが確認される。このことから、本発明の金属多孔構造物は、比較的繊維径が細く、密に詰まった細径金属繊維と、断面積が大きく、電気抵抗の小さな太径金属繊維が、多くの交点で接合して、細径金属繊維及び太径金属繊維が一体化した金属多孔構造物となっており、この金属多孔構造物は本発明の導電性繊維構造物を用いることで容易に得られることがわかる。
From FIG. 5 in which the surface of the metal porous structure was observed, it can be confirmed that long metal fibers are continuously present in the metal porous structure in the metal porous structure of the present invention. From this, it can be considered that the continuous long metal fiber brings good electrical characteristics to the metal porous structure in the extending direction of the continuous fiber. And it is thought that the continuous long metal fiber is oriented in two or more different directions, thereby suppressing the bias (anisotropy) of the electrical characteristics. Moreover, it is confirmed from FIG.6 and FIG.8 that the short metal fiber which is a thin metal fiber is joined with the long metal fiber which is a large diameter metal fiber. Therefore, the metal porous structure of the present invention has a relatively small fiber diameter, a tightly packed thin metal fiber, and a large-diameter metal fiber having a large cross-sectional area and a small electric resistance joined at many intersections. Thus, a metal porous structure in which a thin metal fiber and a large metal fiber are integrated, and this metal porous structure can be easily obtained by using the conductive fiber structure of the present invention. .
また、図5から、本発明の金属多孔構造物においては、従来の発泡ウレタンを用いた金属多孔構造物にみられる骨格部分が切断された端部がほとんど形成されていないことが確認できる。これに加え、金属多孔構造物のベースとなる積層繊維構造物を作製するときに柱状水流を噴射したことで、繊維が厚さ方向に対して垂直になるように再配列されるため繊維端が直立せず、従来の発泡ウレタンを用いた金属多孔構造物にみられる垂直方向に直立した針状突起が形成されていないことが図7から確認できる。これらのことから本発明の金属多孔構造物あるいは導電性繊維構造物は、活物質を充填して各種電極材に使用した際デンドライトを形成しにくくセパレータの破損、短絡が発生しにくい電極材となる。
Further, from FIG. 5, it can be confirmed that in the metal porous structure of the present invention, almost no end portion is formed by cutting the skeleton portion found in the metal porous structure using conventional foamed urethane. In addition, the fiber ends are realigned so that the fibers are perpendicular to the thickness direction by jetting the columnar water flow when producing the laminated fiber structure that is the base of the metal porous structure, so that the fiber ends are aligned. It can be confirmed from FIG. 7 that the needle-like protrusions which do not stand upright and are upright in the vertical direction as seen in the conventional metal porous structure using urethane foam are not formed. From these facts, the metal porous structure or conductive fiber structure of the present invention is an electrode material that hardly forms dendrites when filled with an active material and is used for various electrode materials, and is less prone to breakage of the separator and short circuit. .
これらの特徴を有する、本発明の金属多孔構造物は、本発明の導電性繊維構造物に電解めっきを施したり、電解めっきを施した導電性繊維構造物を熱処理することで熱消失性物質を消失させたりすることで容易に得られる。これは、少なくとも1層の長繊維シート状物を有する導電性繊維構造物に対し、電解めっきを施したり、場合によっては、熱消失性物質が消失する温度で熱処理を施したりしても、導電性繊維構造物の構造が維持されるためである。このことは、図1、2に示す導電性繊維構造物の写真と、図5、6に示す金属多孔構造物の写真を比較した場合、電解めっきにより厚い金属皮膜が形成され、構成繊維(長繊維、短繊維)の繊維径が変化するものの、長繊維及び短繊維が存在する構造、及び長繊維に短繊維が接合している構造には変化がみられないことから確認できる。
The porous metal structure of the present invention having these characteristics is obtained by subjecting the conductive fiber structure of the present invention to electrolytic plating or heat-treating the conductive fiber structure subjected to electrolytic plating to a heat-dissipating substance. It can be easily obtained by disappearing. This is because the conductive fiber structure having at least one layer of long fiber sheet is subjected to electroplating or, in some cases, subjected to heat treatment at a temperature at which the heat-dissipating substance disappears, This is because the structure of the conductive fiber structure is maintained. 1 and 2 and the porous metal structure shown in FIGS. 5 and 6 are compared, a thick metal film is formed by electroplating, and the constituent fibers (long Although the fiber diameter of the fibers and the short fibers is changed, it can be confirmed that there is no change in the structure in which the long fibers and the short fibers are present and the structure in which the short fibers are bonded to the long fibers.
本発明の導電性繊維構造物及び金属多孔構造物は、電磁波シール材、フィルター、アクセサリー、及びアース接地材料などの各種電子部品等に用いることができる。特に本発明の導電性繊維構造物及び金属多孔構造物に活物質合剤を充填することによって種々の電極材特性(例えば集電特性)に優れた電池用電極材(例えばニッケル-水素電池などの各種アルカリ二次電池やリチウムイオン二次電池の電極材)を得ることができる。
The conductive fiber structure and metal porous structure of the present invention can be used for various electronic parts such as electromagnetic wave sealing materials, filters, accessories, and grounding materials. In particular, by filling the conductive fiber structure and metal porous structure of the present invention with an active material mixture, battery electrode materials (for example, nickel-hydrogen batteries) excellent in various electrode material characteristics (for example, current collection characteristics) Various electrode materials for alkaline secondary batteries and lithium ion secondary batteries) can be obtained.
Claims (21)
- 繊維構造物の繊維表面に金属皮膜が形成されてなる導電性繊維構造物であって、
前記繊維構造物は、少なくとも1つの短繊維層と、少なくとも1つの長繊維シート状物とを含み、
前記長繊維シート状物は、シートの一方向に連続して延びる長繊維と、前記一方向と交差する方向に連続して延びる長繊維を含み、
前記繊維構造物において、前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とが交絡している、
導電性繊維構造物。 A conductive fiber structure in which a metal film is formed on the fiber surface of the fiber structure,
The fiber structure includes at least one short fiber layer and at least one long fiber sheet.
The long fiber sheet-like material includes long fibers continuously extending in one direction of the sheet, and long fibers continuously extending in a direction crossing the one direction,
In the fiber structure, the fibers constituting the short fiber layer, and the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet are entangled.
Conductive fiber structure. - 前記繊維構造物は、前記長繊維シート状物の両面に前記短繊維層が積層された三層構造を有する、請求項1に記載の導電性繊維構造物。 The conductive fiber structure according to claim 1, wherein the fiber structure has a three-layer structure in which the short fiber layers are laminated on both sides of the long fiber sheet-like material.
- 前記長繊維シート状物は、ネット状物である、請求項1または2に記載の導電性繊維構造物。 The conductive fiber structure according to claim 1 or 2, wherein the long fiber sheet is a net.
- 前記長繊維シート状物を構成する、シートの一方向に連続して延びる長繊維、及び前記一方向と交差する方向に連続して延びる長繊維の繊維径が1000μm以下である、請求項1~3のいずれか1項に記載の導電性繊維構造物。 The fiber diameter of the long fibers constituting the long fiber sheet-like material and continuously extending in one direction of the sheet and continuously extending in the direction intersecting the one direction is 1000 μm or less. 4. The conductive fiber structure according to any one of 3 above.
- 前記長繊維シート状物において、長繊維に囲まれた開口部面積が500mm2以下である、請求項1~4のいずれか1項に記載の導電性繊維構造物。 The conductive fiber structure according to any one of claims 1 to 4, wherein in the long fiber sheet-like material, an opening area surrounded by the long fibers is 500 mm 2 or less.
- 前記短繊維層は、熱接着性繊維を含み、熱接着性繊維によって、前記短繊維層を構成する繊維同士、及び/または前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とが熱接着されている、請求項1~5のいずれか1項に記載の導電性繊維構造物。 The short fiber layer includes heat-adhesive fibers, and the heat-adhesive fibers constitute fibers constituting the short fiber layer and / or fibers constituting the short fiber layer and the long fiber sheet. The conductive fiber structure according to any one of claims 1 to 5, wherein the long fiber is thermally bonded.
- 前記熱接着性繊維は、芯成分がポリエステル系樹脂を含み、鞘成分がポリオレフィン系樹脂を含む、熱接着性芯鞘型複合繊維である、請求項6に記載の導電性繊維構造物。 The conductive fiber structure according to claim 6, wherein the heat-adhesive fiber is a heat-adhesive core-sheath composite fiber in which a core component includes a polyester-based resin and a sheath component includes a polyolefin-based resin.
- 前記短繊維層及び前記長繊維シート状物が熱消失性物質からなる、請求項1~7のいずれか1項に記載の導電性繊維構造物。 The conductive fiber structure according to any one of claims 1 to 7, wherein the short fiber layer and the long fiber sheet are made of a heat-dissipating substance.
- 少なくとも1つの短繊維層と、少なくとも1つの長繊維シート状物とを含み、
前記長繊維シート状物は、シートの一方向に連続して延びる長繊維と、前記一方向と交差する方向に連続して延びる長繊維を含み、
前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とが交絡している、
導電性繊維構造物用の繊維構造物。 Including at least one short fiber layer and at least one long fiber sheet,
The long fiber sheet-like material includes long fibers continuously extending in one direction of the sheet, and long fibers continuously extending in a direction crossing the one direction,
The fibers constituting the short fiber layer, and the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet are entangled,
A fiber structure for a conductive fiber structure. - 肉厚が1μm以上の中空金属繊維、及び繊維断面において、短辺が2μm以上である金属繊維から選択される少なくとも1種類の金属繊維で構成される金属多孔構造物であって、
前記金属多孔構造物を構成する金属繊維として、繊維長の異なる短金属繊維と長金属繊維が存在し、
前記金属多孔構造物は、前記短金属繊維を含む少なくとも1つの短金属繊維層と、前記長金属繊維を含む少なくとも1つ長金属繊維層を含み、
前記長金属繊維層は、シートの一方向に連続して延びる長金属繊維と、前記一方向と交差する方向に連続して延びる長金属繊維を含み、
前記短金属繊維の少なくとも一部は、前記長金属繊維との交点で前記長金属繊維に接合していることを特徴とする金属多孔構造物。 A metal porous structure composed of at least one metal fiber selected from hollow metal fibers having a wall thickness of 1 μm or more and metal fibers having a short side of 2 μm or more in the fiber cross section,
As metal fibers constituting the metal porous structure, there are short metal fibers and long metal fibers having different fiber lengths,
The metal porous structure includes at least one short metal fiber layer including the short metal fiber, and at least one long metal fiber layer including the long metal fiber,
The long metal fiber layer includes a long metal fiber continuously extending in one direction of the sheet, and a long metal fiber continuously extending in a direction intersecting the one direction,
At least a part of the short metal fiber is bonded to the long metal fiber at an intersection with the long metal fiber. - 前記金属多孔構造物は、前記長金属繊維層の両面に前記短金属繊維層が積層された三層構造を有する、請求項10に記載の金属多孔構造物。 The metal porous structure according to claim 10, wherein the metal porous structure has a three-layer structure in which the short metal fiber layers are laminated on both surfaces of the long metal fiber layer.
- 前記長金属繊維層が、前記長金属繊維からなるネット状物である、請求項10または11に記載の金属多孔構造物。 The metal porous structure according to claim 10 or 11, wherein the long metal fiber layer is a net-like material made of the long metal fiber.
- 前記金属繊維として、繊維径の異なる細径金属繊維及び太径金属繊維が存在する、請求項10~12のいずれか1項に記載の金属多孔構造物。 The metal porous structure according to any one of claims 10 to 12, wherein a thin metal fiber and a large metal fiber having different fiber diameters are present as the metal fiber.
- 前記細径金属繊維が前記短金属繊維であり、前記太径金属繊維が前記長金属繊維である、請求項10~13のいずれか1項に記載の金属多孔構造物。 The metal porous structure according to any one of claims 10 to 13, wherein the thin metal fiber is the short metal fiber and the large metal fiber is the long metal fiber.
- 前記細径金属繊維が、繊維の長さ方向に垂直な面で切断した面において、長辺が9μm以上、170μm以下、短辺が2μm以上、100μm以下である繊維断面を有し、
前記太径金属繊維が、繊維の長さ方向に垂直な面で切断した面において、長辺が359μm以上、1300μm以下、繊維断面の短辺が2μm以上、830μm以下である繊維断面を有している、請求項13または14に記載の金属多孔構造物。 The fine metal fiber has a fiber cross section in which a long side is 9 μm or more and 170 μm or less, and a short side is 2 μm or more and 100 μm or less on a plane cut by a plane perpendicular to the length direction of the fiber,
The large-diameter metal fiber has a fiber cross section having a long side of 359 μm or more and 1300 μm or less and a short side of the fiber cross section of 2 μm or more and 830 μm or less on a plane cut by a plane perpendicular to the length direction of the fiber. The metal porous structure according to claim 13 or 14. - 請求項1~8のいずれか1項に記載の導電性繊維構造物を加熱処理に付して、熱消失性物質を除去してなる、金属多孔構造物。 A metal porous structure formed by subjecting the conductive fiber structure according to any one of claims 1 to 8 to a heat treatment to remove a heat-dissipating substance.
- 請求項1~8のいずれか1項に記載の導電性繊維構造物、または請求項10~16のいずれかに記載の金属多孔構造物に、活物質合剤が充填されている、電池用電極材。 An electrode for a battery, wherein the conductive fiber structure according to any one of claims 1 to 8 or the metal porous structure according to any one of claims 10 to 16 is filled with an active material mixture. Wood.
- 請求項17に記載の電池用電極材を電極として含む、電池。 A battery comprising the battery electrode material according to claim 17 as an electrode.
- シートの一方向に連続して延びる長繊維と、前記一方向と交差する方向に連続して延びる長繊維を含む長繊維シート状物の少なくとも一方の表面に、熱接着性繊維を含む短繊維層を積層して、積層体を得ること、
前記積層体を水流交絡処理に付して、前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とを交絡させること、
前記水流交絡処理に付した積層体に熱接着処理を施し、前記短繊維層を構成する繊維同士、及び/または前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とを、前記熱接着性繊維によって熱接着させること、及び
前記熱接着処理に付した積層体を構成する繊維の表面に金属皮膜を形成すること
を含む、導電性繊維構造物の製造方法。 A short fiber layer containing a heat-adhesive fiber on at least one surface of a long fiber sheet-like material comprising a long fiber continuously extending in one direction of the sheet and a long fiber extending continuously in a direction crossing the one direction. To obtain a laminate,
Subjecting the laminate to hydroentanglement treatment to entangle the fibers constituting the short fiber layer, and the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet,
The laminate subjected to the hydroentanglement treatment is subjected to a thermal bonding treatment, and the fibers constituting the short fiber layer and / or the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet-like material A method for producing a conductive fiber structure, comprising: heat-adhering an adhesive layer with the heat-adhesive fiber; and forming a metal film on a surface of a fiber constituting the laminate subjected to the heat-adhesion treatment. - 導電性繊維構造物を、
シートの一方向に連続して延びる熱消失性物質からなる長繊維と、前記一方向と交差する方向に連続して延びる熱消失性物質からなる長繊維を含む長繊維シート状物の少なくとも一方の表面に、熱消失性物質からなる繊維からなり、かつ熱消失性物質からなる熱接着性繊維を含む短繊維層を積層して、積層体を得ること、
前記積層体を水流交絡処理に付して、前記短繊維層を構成する繊維同士、及び前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とを交絡させること、
前記水流交絡処理に付した積層体に熱接着処理を施し、前記短繊維層を構成する繊維同士、及び/または前記短繊維層を構成する繊維と前記長繊維シート状物を構成する長繊維とを、前記熱接着性繊維によって熱接着させること、及び
前記熱接着処理に付した積層体を構成する繊維の表面に金属皮膜を形成すること
を含む方法によって得ること、及び
前記導電性繊維構造物を加熱処理に付して、前記熱消失性物質を除去すること
を含む、金属多孔構造物の製造方法。 Conductive fiber structure
At least one of long fibers made of a heat-dissipating substance continuously extending in one direction of the sheet and long-fiber sheet-like material comprising long fibers made of a heat-dissipating substance continuously extending in a direction intersecting the one direction Laminating a short fiber layer made of a fiber made of a heat-dissipating substance and containing a heat-adhesive fiber made of a heat-dissipating substance on the surface to obtain a laminate,
Subjecting the laminate to hydroentanglement treatment to entangle the fibers constituting the short fiber layer, and the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet,
The laminate subjected to the hydroentanglement treatment is subjected to a thermal bonding treatment, and the fibers constituting the short fiber layer and / or the fibers constituting the short fiber layer and the long fibers constituting the long fiber sheet-like material Is obtained by a method including heat-adhering with the heat-adhesive fiber, and forming a metal film on the surface of the fiber constituting the laminate subjected to the heat-adhesion treatment, and the conductive fiber structure The manufacturing method of a metal porous structure including attaching | subjecting to heat processing and removing the said heat-dissipative substance. - 請求項20の製造方法によって金属多孔構造物を得ること、及び
前記金属多孔構造物に活物質合剤を充填すること
を含む、電池用電極材の製造方法。 The manufacturing method of the battery electrode material including obtaining a metal porous structure by the manufacturing method of Claim 20, and filling the active material mixture in the said metal porous structure.
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JP2016519399A (en) * | 2013-05-03 | 2016-06-30 | ジェナックス インコーポレイテッド | Nonwoven fabric current collector, battery manufacturing method and system using the same |
JP2019091669A (en) * | 2017-11-17 | 2019-06-13 | 旭化成株式会社 | Nonwoven fabric current collector for secondary battery |
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KR102211696B1 (en) * | 2019-11-08 | 2021-02-03 | 중앙대학교 산학협력단 | Porous fiber, preparation method thereof, and fiber type energy storage devaice |
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