WO2016148259A1 - 構造体及びコア材 - Google Patents

構造体及びコア材 Download PDF

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Publication number
WO2016148259A1
WO2016148259A1 PCT/JP2016/058590 JP2016058590W WO2016148259A1 WO 2016148259 A1 WO2016148259 A1 WO 2016148259A1 JP 2016058590 W JP2016058590 W JP 2016058590W WO 2016148259 A1 WO2016148259 A1 WO 2016148259A1
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WO
WIPO (PCT)
Prior art keywords
core material
fiber
porous layer
fibers
laminate
Prior art date
Application number
PCT/JP2016/058590
Other languages
English (en)
French (fr)
Inventor
育生 植松
直哉 速水
健哉 内田
Original Assignee
株式会社 東芝
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社 東芝 filed Critical 株式会社 東芝
Priority to JP2016555387A priority Critical patent/JP6139805B2/ja
Priority to EP16765088.6A priority patent/EP3272517B1/en
Priority to CN201680000969.6A priority patent/CN106163793A/zh
Publication of WO2016148259A1 publication Critical patent/WO2016148259A1/ja
Priority to US15/384,673 priority patent/US10099447B2/en
Priority to US16/126,573 priority patent/US10906266B2/en

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Definitions

  • Embodiments of the present invention relate to a structure including a core material made of fibers and a core material constituting the structure.
  • a structure including a core material made of fibers has been considered.
  • a fiber constituting this type of structure for example, a fine fiber made of a polymer material as disclosed in Patent Document 1 can be considered.
  • the structure in which the core material is made of fibers has a problem that the strength is weak due to its structure.
  • JP 2002-249966 A Japanese Patent No. 5105352 JP 2012-197644 A
  • the present embodiment relates to a structure including a core material made of fibers, and provides a structure capable of improving the strength and a core material constituting the structure.
  • a structure capable of arbitrarily changing the compressive strength is provided.
  • the structure according to the present embodiment includes a core material composed of fibers and a core material that constitutes the core material and suppresses deformation of the core material.
  • a structure including at least one porous layer including a fiber including a thermosetting resin and an electrolyte is provided.
  • a structure including a laminate including a plurality of porous layers is provided.
  • the plurality of porous layers contain fibers having a density of 0.5 g / cm 3 or more and 3 g / cm 3 or less and having an average diameter of 30 nm or more and less than 5 ⁇ m.
  • the porosity of the porous layer is in the range of 45% to 95%.
  • a structure including a core material composed of fibers and a core material that constitutes the core material and is in contact with the core material.
  • FIG. 1 is a cross-sectional view illustrating a configuration example of a structure according to the present embodiment.
  • FIG. 2 is a cross-sectional view illustrating a configuration example of the structure according to the embodiment.
  • FIG. 3 is a cross-sectional view illustrating a configuration example of the structure according to the embodiment.
  • FIG. 4 is a perspective view showing an example of a core material included in the structure.
  • FIG. 5 is a perspective view showing another example of the core material included in the structure.
  • FIG. 6 is a cross-sectional view illustrating a configuration example of the structure according to the embodiment.
  • FIG. 7 is a cross-sectional view illustrating a configuration example of the structure according to the embodiment.
  • FIG. 1 is a cross-sectional view illustrating a configuration example of a structure according to the present embodiment.
  • FIG. 2 is a cross-sectional view illustrating a configuration example of the structure according to the embodiment.
  • FIG. 3 is a cross-sectional view illustrating a configuration
  • FIG. 8 is a cross-sectional view showing an example of a laminated structure of a laminated film.
  • FIG. 9 is a schematic view showing an example of use as a biomaterial sheet.
  • FIG. 10 is an electron micrograph showing an example of an oriented collagen sheet.
  • FIG. 11 is a schematic diagram illustrating an example of an insulating material and an insulating auxiliary material.
  • FIG. 12 is a schematic diagram showing an example of use as a water droplet shock absorbing material.
  • 13 is a cross-sectional view taken along line XIII-XIII in FIG.
  • FIG. 14 is a schematic diagram showing an example of use as an adhesive layer.
  • FIG. 15 is a schematic diagram showing an example of use of the diaphragm as a surface layer.
  • FIG. 16 is a schematic diagram showing a projected view of fibers with respect to the observation direction.
  • a structure 10 illustrated in FIG. 1 has a configuration in which a core material 11 constituting a main part thereof is accommodated in a surface forming material 12.
  • the core material 11 includes fibers 13 and a core material 14.
  • the surface forming material 12 constitutes a surface portion of the structure 10.
  • the surface forming material 12 is composed of a sheet material made of any one of a metal material, an organic material, an inorganic material, or a combination thereof.
  • the surface forming material 12 is configured in a bag shape that can accommodate the core material 11 including the fibers 13 and the core material 14.
  • the core material 14 is covered with fibers 13.
  • the surface forming material 12 may be configured to cover a part of the core material 11 instead of covering the entire core material 11.
  • the fibers 13 are formed of resin fibers that are randomly intertwined.
  • the fibers 13 are formed by an electrospinning method.
  • the fiber 13 produced by the electrospinning method becomes a thin fiber having an outer diameter of about 0.1 nm to 10 ⁇ m, and a long fiber having a length that is, for example, 1000 times or more of the outer diameter.
  • generated by the electrospinning method makes the crimped shape curved not at all linearly but at random. Therefore, the entanglement between the fibers increases.
  • the fiber 13 is formed of an organic polymer having a density lower than that of glass.
  • the weight of the fiber 13 can be reduced by forming the fiber 13 with a polymer having a density lower than that of glass.
  • the fibers 13 are polystyrene, polycarbonate, polymethyl methacrylate, polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyoxymethylene, polyamideimide, polyimide, polysulfane, polyethersulfane, polyetherimide, polyether.
  • ether ketone polyphenylene sulfide, modified polyphenylene ether, syndiotactic polystyrene, liquid crystal polymer, urea resin, unsaturated polyester, polyphenol, melamine resin, epoxy resin and copolymers containing these It can be formed by blending the above polymers.
  • the polymer is made into a solution.
  • the solvent include isopropanol, ethylene glycol, cyclohexanone, dimethylformamide, acetone, ethyl acetate, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, toluene, xylene, methyl ethyl ketone, diethyl ketone, butyl acetate, tetrahydrofuran, dioxane,
  • a volatile organic solvent such as pyridine or water can be used.
  • the solvent may be one kind selected from the above solvents, or a plurality of kinds may be mixed.
  • the solvent applicable to this embodiment is not limited to the said solvent.
  • the said solvent is an illustration to the last.
  • the fibers 13 are formed by the electrospinning method, the entanglement between the fibers can be increased, so that it is possible to form a nonwoven fiber sheet at the same time as spinning. Further, by forming the fibers 13 by an electrospinning method, it is possible to obtain a nano-order fiber diameter from a micro-order.
  • the fiber diameter of the fiber 13 is preferably about 5 ⁇ m or less, more preferably 1 ⁇ m or less, that is, a nano-order fiber diameter.
  • the fiber 13 may be added with various inorganic fillers such as silicon oxide, metal hydroxide, carbonate, sulfate, and silicate.
  • inorganic fillers such as silicon oxide, metal hydroxide, carbonate, sulfate, and silicate.
  • examples of the inorganic filler to be added include wollastonite, potassium titanate, zonotlite, gypsum fiber, aluminum porate, MOS (basic magnesium sulfate), aramid fiber, carbon fiber, glass fiber, talc, mica, glass flake, etc. It is done.
  • the core material 14 is made of, for example, an acrylic resin material and has a strength that can withstand stress.
  • the core material 14 has a porous structure having a large number of fine voids. Thereby, the core material 14 can be reduced in weight, and the core material 11 and the structure 10 can be reduced in weight.
  • the core material 14 has a function of suppressing the deformation of the core material 11 due to stress and a function of suppressing the compression of the fibers 13.
  • the shape of the core material 11 made of the fibers 13, in other words, the shape of the structure 10 can be stably maintained.
  • the strength of the core material 11 and thus the strength of the structure 10 can be improved.
  • the core material 14 is good to make the corner
  • the structural body 10 includes the core material 14 in the core material 11, so that the amount of the fiber 13 used is suppressed as compared with a structure in which the core material 11 is entirely composed of the fiber 13.
  • the structure 10 includes the core material 14 in the core material 11 as described above, thereby suppressing the thickness of the fiber layer made of the fibers 13.
  • the fibers 13 constituting the core material 11 are compressed according to the applied force.
  • the thickness of the fiber layer existing between the surface forming material 12 and the core material 14, that is, the amount of the fibers 13 is suppressed. Therefore, the compression amount of the fiber 13 can be suppressed as compared with the configuration in which the fiber 13 is accommodated in the entire surface forming material 12.
  • a core material 14 for suppressing deformation of the core material 11 is provided in the core material 11 with respect to the structure 10 including the core material 11 constituted by the fibers 13. It was. Thereby, compared with the case where the whole core material is comprised with a fiber, the improvement of the intensity
  • the core material 14 is porous, it is possible to reduce the weight of the core material 14. As a result, the core material 11 and the structure 10 can be reduced in weight. Can be planned.
  • the structure according to the present embodiment includes a core material composed of fibers and a core material that constitutes the core material and suppresses deformation of the core material. According to this configuration, the strength of the structure including the core material made of fibers can be improved.
  • the material of the core member 14 may be composed of, for example, a resin material, a metal material, or an inorganic material, and the material can be changed as appropriate.
  • the fiber 13 may be a glass fiber instead of a resin fiber, or a fiber made of a material containing an organic substance.
  • the organic substance may be an organic substance derived from a living body.
  • the structure 10 may be one in which the inside of the surface forming material 12 containing the core material 11 is decompressed.
  • the structure according to the present embodiment can be used for various purposes, for example, an artificial joint, a filter, a pillow, a packing material for valuables, a bed, and the like. Moreover, it can also be used for seats such as seats mounted on automobiles, bullet trains, airplanes, and child seats. It can also be used for masks, bandages, conductive sheets and the like.
  • the structure according to this embodiment is used for, for example, an artificial joint or a bandage
  • the structure is suitable as a member for providing a space for wetting.
  • the structure according to the present embodiment can be used in air as well as in liquid. It can also be used as a separator between those having different environments.
  • a structure including a porous layer is provided.
  • the porous layer is one in which one or a plurality of fibers are accumulated, deposited, laminated or assembled.
  • the fibers are intertwined and contacted at a plurality of locations to form contacts, and the fibers are arranged three-dimensionally.
  • the fibers may be bonded or welded to each other, but may not be bonded or welded.
  • the orientation of the fibers at the contacts can be changed by an external force applied to the porous layer. It can be said that the porous layer has a nonwoven fabric shape.
  • the pores present in the porous layer may be independent pores, continuous pores, or through-holes, and a plurality of types such as independent pores and continuous pores may exist.
  • the fibers contained in the porous layer include (a) a first fiber containing a thermosetting resin and an electrolyte, or (b) a resin having a density of 0.5 g / cm 3 or more and 3 g / cm 3 or less, and 30 nm.
  • a second fiber having a diameter of 5 ⁇ m or less may be included. Both the first fiber and the second fiber may be contained in the same porous layer. It is possible that the first fiber and the second fiber are the same fiber.
  • the average diameter, the degree of entanglement, and the arrangement of the fibers can be freely changed.
  • a structure that can be arbitrarily changed can be provided.
  • Such a structure can be used for, for example, a heat insulator, a biomaterial sheet, an insulating material, an insulating auxiliary material, a water droplet shock absorbing material, an adhesive layer, a diaphragm, and the like in addition to the above-described applications.
  • the first fiber, the second fiber having a density of 1 g / cm 3 or more and 2 g / cm 3 or less, or the porous layer containing these fibers can increase the compressive strength, Crushing can be suppressed.
  • the porous structure of the porous layer can be maintained for a long period of time, the shape stability of the porous layer is improved. Therefore, a structure having high compressive strength and high shape stability can be realized.
  • Such a structure can be used for, for example, a heat insulator, a biomaterial sheet, an insulating material, an insulating auxiliary material, a water droplet shock absorbing material, an adhesive layer, a diaphragm, and the like in addition to the above-described applications.
  • the porous layer can have a structure with a thin fiber diameter and a high porosity so that the thermal conductivity can be reduced, so that the heat insulation of the structure can be improved.
  • thermosetting resin contained in the first fiber is the main component of the fiber.
  • a main component is a component with the highest ratio among the structural components of a fiber.
  • the thermosetting resin is desirably contained in the fiber by 50% by weight or more. Thereby, the compressive strength of a porous layer can be improved.
  • the range of the relative dielectric constant of the thermosetting resin is desirably 1 or more and 1000 or less. Thereby, a porous layer having high compressive strength and low thermal conductivity is obtained. This makes it easy to control the fiber formation when the porous layer is produced by the electrospinning method, and makes adjustments such as reducing the fiber diameter and making the fiber arrangement (or entanglement) complicated. This is because it becomes easier.
  • a more preferable range of the relative dielectric constant is in the range of 50 to 1000.
  • the relative dielectric constant can be measured, for example, by the resonator method.
  • thermosetting resins examples include epoxy resins.
  • the relative dielectric constant of the epoxy resin is in the range of 1 to 1000.
  • the electrolyte contributes to the improvement of the compressive strength and heat insulation of the porous layer containing the epoxy resin-containing fiber.
  • the reason is as follows.
  • the electrolyte can increase the dielectric constant and conductivity of the raw material solution used when the porous layer is produced by the electrospinning method. Compared with the case where no electrolyte is added, for example, the relative dielectric constant can be increased by about 2 to 100 times. As a result, it becomes easy to control the fiber formation in the electrospinning process, and it is easy to make adjustments such as reducing the diameter of the fibers and complicating the arrangement (or entanglement) of the fibers. In addition to such effects, the electrolyte can enhance the conductivity of the epoxy resin-containing fiber.
  • Examples of the electrolyte include inorganic salts, ammonium salts, and ionic liquids. It is desirable that the electrolyte is excellent in affinity with the thermosetting resin and solubility in the solvent.
  • Examples of inorganic salts include LiBr, LiCl, NaCl, LiCl, MgCl 2 , NaOH, KMnO 4 , K 2 CrO 4 and the like.
  • Examples of ammonium salts include NH 4 Cl, NH 4 Br, and the like.
  • examples of the ionic liquid include 1-butyl-3-methylimidazolium hexafluorophosphate.
  • the type of electrolyte can be one type or two or more types. LiBr is excellent in solubility in an organic solvent (for example, cyclohexanone) used as a solvent for the raw material solution. LiBr also has the advantage of being inexpensive. Furthermore, LiBr is thermally and chemically stable.
  • the content of the electrolyte in the first fiber can be in the range of 0.01% by weight to 10% by weight. If the electrolyte content is low, fibers with a small diameter cannot be obtained. On the other hand, if the electrolyte content is large, the content of the thermosetting resin is insufficient and the compressive strength of the porous layer may be reduced. A more preferred range is from 0.1% by weight to 2% by weight.
  • the average diameter of the first fibers is preferably in the range of 30 nm to 5 ⁇ m.
  • the heat conductivity of a porous layer can be made low and heat insulation can be improved.
  • the pressure loss of the porous layer can be reduced.
  • a more preferable range is 30 nm or more and less than 5 ⁇ m
  • a further preferable range is 400 nm or more and 800 nm or less
  • a further preferable range is 400 nm or more and 600 nm or less.
  • the compressive strength of the second fiber can be increased.
  • the resin having a density of 1 g / cm 3 or more and 2 g / cm 3 or less include an epoxy resin.
  • the thermal conductivity of the porous layer can be lowered by setting the average diameter of the second fibers to a range of 30 nm or more and less than 5 ⁇ m.
  • the pressure loss of the porous layer can be reduced. Therefore, the porous layer containing the second fiber has high compressive strength and low thermal conductivity.
  • a more preferable range is 400 nm to 800 nm, and a further preferable range is 400 nm to 600 nm.
  • the thermal conductivity of the first fiber and the second fiber having a density of 1 g / cm 3 or more and 2 g / cm 3 or less is, for example, in the range of 0.01 W / m ⁇ K to 5 W / m ⁇ K.
  • the thermal conductivity of the resin constituting the fiber is regarded as the thermal conductivity of the fiber.
  • the thermal conductivity of the fiber containing the epoxy resin is in the range of 0.01 W / m ⁇ K to 5 W / m ⁇ K.
  • the porosity of the porous layer including at least one of the first fiber and the second fiber is in the range of 45% to 95%. By increasing the porosity, the heat insulation of the porous layer can be enhanced. A more preferable range is 70% or more and 95% or less.
  • the porosity of the laminate including a plurality of the porous layers is preferably in the range of 45% to 95%. By increasing the porosity, the heat insulation of the porous layer can be enhanced. A more preferable range is 70% or more and 95% or less.
  • the porosity P 1 (%) of the porous layer is calculated from the following equation (1).
  • V 1 is a volume including the pores of the porous layer. From the longitudinal length L 1 of the porous layer, the lateral length L 2 of the porous layer, and the thickness L 3 of the porous layer, the following (2 ). The volume V 1 including the pores of the porous layer is performed in a state where the porous layer is not filled with a material such as a liquid. When the porous layer is filled with a material such as a liquid, the measurement is performed after removing the material by washing the porous layer. Each dimension L 1 , L 2, and L 3 depends on the scale in a state where the porous layer prepared on the base material or the core material is peeled off from the base material and the core material, and then the porous layer is placed on a plane. measure.
  • V 1 L 1 ⁇ L 2 ⁇ L 3 (2)
  • V 2 is the net volume of the porous layer, which is the weight of the porous layer divided by the density of the porous layer.
  • the porosity P 2 (%) of the laminate is calculated from the following equation (3).
  • V 3 is a volume including the pores of the laminated body, and is calculated by the following formula (4) from the vertical length L 4 of the laminated body, the lateral length L 5 of the laminated body, and the thickness L 6 of the laminated body. Is done.
  • the volume V 3 including the holes of the stacked body is performed in a state where the stacked body is not filled with a material such as a liquid.
  • the measurement is performed after removing the material by washing the laminate.
  • the dimensions L 4, L 5 and L 6 is measured by the scale a laminate in a state placed on a flat surface.
  • V 3 L 4 ⁇ L 5 ⁇ L 6 (4)
  • V 4 is the net volume of the laminate, which is the weight of the laminate divided by the density of the laminate.
  • the average diameter of the first fiber and the second fiber is measured, for example, by the method described below.
  • the porous layer is observed with a scanning electron microscope (SEM). At this time, the porous layer is observed from the direction of the arrow shown in FIG. All the diameters of the fibers in focus in the resulting image are measured.
  • the diameter of the fiber is the length of the short side in the projected view of the fiber with respect to the observation direction indicated by the arrow in FIG.
  • FIG. 16 shows a projection view 33 of the fiber obtained by projecting the fiber 31 with respect to the observation direction indicated by the arrow 32.
  • the projection 33 is a rectangle.
  • the length L of the short side of the rectangular projection 33 is regarded as the diameter of the fiber 31.
  • the average value calculated from the obtained measured values is taken as the average diameter of the fibers.
  • the observation range and magnification are changed so that the number of fibers whose diameter can be measured is 10 or more.
  • the structure of the embodiment can include a stacked body including a plurality of porous layers.
  • the laminated body can be subjected to integration of the porous layer by pressing, bundling of the porous layer together with an exterior member, or the like.
  • an exterior member a laminate is placed in a frame, a plate is placed on the outermost layer of the laminate, and the laminate is sandwiched between plates, and the laminate is placed in a housing, a bag (for example, the surface forming material 12), etc. Includes storage.
  • the structure of the embodiment can include a core material.
  • the core material is preferably superior in mechanical strength to the porous layer.
  • the core material can be reinforced with the porous layer or the core material composed of fibers to reinforce the porous layer, so that deformation due to compression of the porous layer can be suppressed, and the structure Can be stably maintained.
  • the core material desirably has a porous structure. Thereby, weight reduction of a core material and by extension, a structure can be achieved.
  • the core material may have a rounded corner. Thereby, the force which the corner
  • the core material can be made of, for example, an acrylic resin material.
  • the porous layer including at least one of the first fiber and the second fiber is produced by, for example, an electrospinning method.
  • a thermosetting resin main component and an electrolyte are dispersed or dissolved in an organic solvent to prepare a raw material solution containing the thermosetting resin main component and an electrolyte. After adding a curing agent to the raw material solution, it is temporarily cured by heating.
  • a porous layer is formed by an electrospinning method using the temporarily cured raw material solution. Ground the base material to make an earth electrode. The raw material solution is charged by the voltage applied to the spinning nozzle, and the amount of charge per unit volume of the raw material solution increases due to volatilization of the solvent from the raw material solution.
  • the raw material solution discharged from the spinning nozzle extends in the longitudinal direction and accumulates on the substrate as nano-sized thermosetting resin-containing fibers.
  • a Coulomb force is generated between the thermosetting resin-containing fiber and the base material due to a potential difference between the nozzle and the base material. Therefore, the contact area with the substrate can be increased by the nano-sized thermosetting resin-containing fibers, and the thermosetting resin-containing fibers can be deposited on the substrate by Coulomb force.
  • the dielectric constant and electrical conductivity of the raw material solution can be increased.
  • the raw material solution can be sufficiently charged when a voltage is applied to the raw material solution, control to the target fiber diameter, control of the fiber arrangement, and the like are facilitated.
  • setting the range of the relative dielectric constant of the thermosetting resin to 1 or more and 1000 or less contributes to the improvement of the dielectric constant of the raw material solution, so that the control of fiberization becomes easier.
  • the organic solvent of the type described above can be used as the organic solvent contained in the raw material solution.
  • a core material may be used, or a material different from the core material may be used.
  • the porous layer formed on the base material is used after being separated from the base material.
  • the substrate include paper and aluminum foil.
  • the structure shown in FIG. 2 includes a laminate 3 and a bag-shaped exterior member 4 in which the laminate 3 is accommodated.
  • the laminated body 3 includes a plurality of core materials 1 and a plurality of porous layers 2.
  • the core material 1 has a porous structure, for example, can have the structure shown in FIG. 4 or FIG.
  • the core material 1 shown in FIG. 4 is a metal mesh-shaped porous sheet.
  • the core material 1 shown in FIG. 5 is a lattice-shaped porous sheet. Each sheet has a rounded corner.
  • the core material 1 and the porous layer 2 are laminated
  • the bag-shaped exterior member 4 is obtained, for example, by processing a laminated film into a bag shape by heat sealing. On the side wall of the exterior member 4, a location 5 where the laminate films are bonded together by thermal fusion is located.
  • a laminate film including a layer containing aluminum or an aluminum alloy and a resin layer can be used.
  • FIG. 8 The laminate film 4 shown in FIG. 8 has a five-layer structure from the first layer constituting the outer surface of the exterior member 4 to the fifth layer constituting the inner surface of the exterior member 4, and polyethylene terephthalate (PET) is formed on the first layer 4a.
  • the core material 1 and the porous layer 2 may be arranged alternately, even if the core material 1 is arranged on one outermost layer and the porous layer 2 is arranged on the other outermost layer. Alternatively, the core material 1 may be disposed on both outermost layers.
  • the structure shown in FIG. 3 has the same structure as FIG. 2 except that the arrangement of the core material 1 and the porous layer 2 in the laminate 3 is different.
  • the porous layer 2 is disposed in both outermost layers of the laminate in which a plurality of core materials 1 are laminated.
  • One or two or more porous layers 2 can be disposed in each outermost layer.
  • the structure shown in FIGS. 2 and 3 includes the exterior member and the core material, but may not include the exterior member and the core material.
  • a laminated body 6 of a plurality of porous layers 2 can be used as the structure of the first embodiment.
  • the laminate 6 shown in FIG. 6 can be accommodated in the exterior member 4.
  • the same members as those in FIGS. 2 and 3 are denoted by the same reference numerals, and description thereof is omitted.
  • the structure laminate includes the core material, so that deformation due to compression of the porous layer can be suppressed, and the collapse of the pores can be further suppressed. Therefore, the compressive strength of the laminate can be further increased.
  • the porosity can be increased by reducing the amount of fibers used in the porous layer, so the thermal conductivity of the laminate is reduced to a structure with a small fiber diameter and high porosity. Can be further reduced.
  • the porous layer is located between the core materials, so that radiant heat transfer can be suppressed. Moreover, the heat conduction through the core material can be suppressed by the porous layer.
  • the structure of the laminate can be simplified and can be easily produced.
  • the structure of the embodiment can be used for, for example, a heat insulator, a biomaterial sheet, an insulating material and an insulating auxiliary material, a water droplet shock absorbing material, an adhesive layer, a diaphragm, and the like in addition to the above-described uses.
  • a substrate such as a glass or resin petri dish, a base material for plaster, a sheet, a porous body (for example, a film or sponge-like liquid is applied to a base material on which a core material or a porous layer is formed.
  • a porous body for example, a film or sponge-like liquid is applied to a base material on which a core material or a porous layer is formed.
  • the adhesive bandage base material include urethane nonwoven fabric, vinyl chloride sheet, stretchable cotton fabric, sponge sheet, urethane film, and olefin film.
  • FIG. 9 An example of using a container such as a petri dish as a substrate is shown in FIG.
  • the oriented collagen sheet 16 is accommodated in the petri dish 15, and the culture solution 17 is filled on the oriented collagen sheet 16.
  • FIG. 9 An example of the oriented collagen sheet 16 is shown in FIG.
  • the oriented collagen sheet 16 can be obtained, for example, by using a biomaterial such as collagen instead of a thermosetting resin such as an epoxy resin.
  • the porous layer, laminate or structure of the embodiment can be used as an insulating material and / or an insulating auxiliary material.
  • the porous layer 19 impregnated with the insulating resin 20 can be used as the insulating material and / or the insulating auxiliary material 18.
  • PC polycarbonate
  • PES polyethersulfone
  • PAN polyacrylonitrile
  • PEN polyethylene naphthalate
  • thermosetting resin instead of thermosetting resin or in combination with thermosetting resin as a material constituting the fiber
  • PU polyurethane
  • UF acrylic resin
  • PMMA polyamide
  • PA polystyrene
  • PS polyimide
  • PAI polyamideimide
  • the porous layer, laminate or structure of the embodiment can be used as a water droplet impact buffer.
  • the substrate on which the core material or the porous layer is temporarily formed include a resin substrate such as fiber reinforced plastic (FRP).
  • FRP fiber reinforced plastic
  • FIG. 12 shows a main part including the wing part 21 of the power generation wind turbine.
  • FIG. 13 shows a cross-sectional view of the wing 21 taken along the line XIII-XIII.
  • the surface of the blade portion 21 of the power generation wind turbine can be covered with a porous layer 22.
  • the material constituting the fiber other resins can be used instead of the thermosetting resin or in combination with the thermosetting resin. Examples of other resins include those similar to those exemplified for the insulating material / insulating auxiliary material.
  • the porous layer, laminate or structure of the embodiment can be used as an adhesive layer.
  • the adhesive layer can be formed thinly and uniformly on the substrate or the like.
  • the adhesive force of the adhesive layer can be increased by filling or impregnating the pores of the porous layer in the adhesive layer with another type of adhesive.
  • ink, magnetic material, or the like may be carried in the pores of the porous layer.
  • the base material on which the core material or the porous layer is temporarily formed include thin base materials used for printing paper, photographs, films, sheets and the like.
  • FIG. 14 shows an example in which a porous layer 24 is disposed as an adhesive layer between base materials 23a and 23b such as paper.
  • the porous layer, laminate or structure of the embodiment may be formed on the surface of a diaphragm used for gas separation or gas-liquid separation.
  • a diaphragm used for gas separation or gas-liquid separation.
  • strength of a diaphragm, a weather resistance, durability, etc. can be improved.
  • a porous layer having fine fibers and a high porosity is formed on the surface of the diaphragm, the separation efficiency can be improved.
  • An example is shown in FIG.
  • a porous layer 26 is formed on one side of a diaphragm 25 used for gas separation or gas-liquid separation.
  • Other resins can be used as the material constituting the fibers of the porous layer 26 instead of the thermosetting resin or in combination with the thermosetting resin. Examples of other resins include those similar to those exemplified for the insulating material / insulating auxiliary material.
  • inorganic nanofibers for example, TiO 2 , SnO 2 , SiO 2 , etc.
  • processing such as firing together with the above types of fibers or instead of the above types of fibers.
  • ZrO 2, Fe 2 O 3, BaTiO 3, NiFe 2 O 4 can be used carbon fibers.
  • N which is a solvent.
  • a solution was prepared by adding 1% by weight of LiBr to an epoxy resin main agent diluted by 50% by weight with N-dimethylformamide (DMF).
  • a 40% by weight amount of a curing agent was added to this solution with respect to the epoxy resin main component and heated to 70 ° C. to be temporarily cured to obtain a raw material solution.
  • the obtained raw material solution was supplied from the spinning nozzle to the surface of the substrate using a metering pump at a supply rate of 1 mL / h.
  • a high voltage generator applying a voltage of 60 kV to the spinning nozzle and transporting the substrate at 0.15 / min, moving the spinning nozzle in a range of 200 mm perpendicular to the substrate transport direction Fibers were deposited on the surface of the substrate to form a porous layer.
  • Aluminum foil was used for the substrate.
  • the fibers constituting the obtained porous layer contained 99% by weight of epoxy resin and 1% by weight of LiBr. Moreover, the density of the epoxy resin was 1.2 g / cm 3 and the relative dielectric constant was 11. Since the thermal conductivity of the epoxy resin is regarded as the thermal conductivity of the fiber, the thermal conductivity of the fiber is 0.3 W / m ⁇ K. The average fiber diameter was 800 nm when the SEM magnification was 2000 times and the number of fibers measured for diameter was 20 by the above-described method. When the porosity of the porous layer was measured by the method described above, it was 78%. The porous layer had a longitudinal length of 150 mm, a lateral length of 150 mm, and a thickness of 21 mm.
  • a porous plate made of an acrylic resin (polymethyl methacrylate: PMMA) having the structure shown in FIG. 5 and having a longitudinal length of 150 mm, a lateral length of 150 mm, a thickness of 10 mm, and a porosity of 80% was prepared.
  • the porous layer and the core material were alternately laminated to obtain a laminated body in which the porous film was positioned in both outermost layers.
  • a laminate of 30 porous layers was used as one unit, and three units and two cores were alternately stacked to obtain a laminate.
  • the number of layers of the porous layer in the laminate was 90 and the number of layers of the core material was 2, the number of layers of the porous layer and the core material is not limited thereto.
  • the porosity of the laminate was 80%.
  • the laminate film has a five-layer structure shown in FIG. 8, wherein the first layer 4a is a polyethylene terephthalate (PET) layer having a thickness of 16 ⁇ m, the second layer 4b is a polyamide (PA) layer having a thickness of 30 ⁇ m, and the third layer 4c.
  • PET polyethylene terephthalate
  • PA polyamide
  • An aluminum vapor deposition layer having a thickness of less than 1 ⁇ m, an ethylene / vinyl alcohol copolymer resin (EVOH) layer having a thickness of 20 ⁇ m for the fourth layer 4e, and a polyethylene (PE) layer having a thickness of 60 ⁇ m for the fifth layer 4d are used. .
  • Example 2 It was 7 mW / m * K when the heat conductivity of the structure of obtained Example 1 was measured with the heat conductivity meter.
  • Example 2 A porous layer and a core material prepared by the same method as in Example 1 were prepared. As shown in FIG. 3, the porous layer was laminated
  • Example 3 As a core material, an acrylic resin porous plate having the structure shown in FIG. 4, having a longitudinal length of 150 mm, a lateral length of 150 mm, a thickness of 5 mm, and a porosity of 80% was prepared.
  • the raw material solution prepared in the same manner as in Example 1 was supplied from the spinning nozzle to the surface of the substrate using a metering pump at a supply rate of 1 mL / h.
  • a high voltage generator applying a voltage of 60 kV to the spinning nozzle and transporting the substrate at 0.15 / min, moving the spinning nozzle in a range of 200 mm perpendicular to the substrate transport direction Fibers were deposited on the surface of the substrate to form a porous layer.
  • Aluminum foil was used for the substrate.
  • the fibers constituting the obtained porous layer contained 99% by weight of epoxy resin and 1% by weight of LiBr. Moreover, the density of the epoxy resin was 1.2 g / cm 3 and the relative dielectric constant was 11. Since the thermal conductivity of the epoxy resin is regarded as the thermal conductivity of the fiber, the thermal conductivity of the fiber is 0.3 W / m ⁇ K. The average fiber diameter was 800 nm when the SEM magnification was 2000 times and the number of fibers measured for diameter was 20 by the above-described method. When the porosity of the porous layer was measured by the method described above, it was 80%. The porous layer had a longitudinal length of 150 mm, a lateral length of 150 mm, and a thickness of 21 mm.
  • the porous layer and the core material were alternately laminated to obtain a laminated body in which the porous film was positioned in both outermost layers.
  • the number of porous layers in the laminate was 50 per unit of laminated porous layers.
  • the porosity of the laminate was 80%.
  • the exterior member After storing the obtained laminate in a bag-shaped exterior member made of a laminate film having the same five-layer structure as in Example 1, the exterior member is evacuated using a vacuum pump, and the exterior member is sealed by heat sealing To obtain a structure.
  • Example 4 A porous layer and a core material prepared by the same method as in Example 3 were prepared. As shown in FIG. 3, the porous layer was laminated
  • the exterior member After storing the obtained laminate in a bag-shaped exterior member made of a laminate film having the same five-layer structure as in Example 1, the exterior member is evacuated using a vacuum pump, and the exterior member is sealed by heat sealing To obtain a structure.
  • Example 5 A porous layer was formed in the same manner as in Example 1 except that 0.1 wt% LiCl was used instead of LiBr as the electrolyte.
  • the fibers constituting the obtained porous layer contained 99.9% by weight of epoxy resin and 0.1% by weight of LiCl.
  • the density and relative dielectric constant of the epoxy resin, the thermal conductivity of the fiber, the average diameter of the fiber, the porosity of the porous layer, the vertical length, the horizontal length, and the thickness of the porous layer were the same as in Example 1. . Some of these data are shown in Table 1.
  • Example 6 A structure was produced in the same manner as in Example 1 except that the obtained porous layer was used. Table 1 shows the thermal conductivity of the structure measured with a thermal conductivity meter. (Example 6) A porous layer was formed in the same manner as in Example 1 except that 0.1 wt% benzyltriethylammonium chloride was used as the electrolyte instead of LiBr.
  • the fibers constituting the obtained porous layer contained 99.9% by weight of epoxy resin and 0.1% by weight of benzyltriethylammonium chloride.
  • the density and relative dielectric constant of the epoxy resin, the thermal conductivity of the fiber, the average diameter of the fiber, the porosity of the porous layer, the vertical length, the horizontal length, and the thickness of the porous layer were the same as in Example 1. . Some of these data are shown in Table 1.
  • Example 7 A structure was produced in the same manner as in Example 1 except that the obtained porous layer was used.
  • Table 1 shows the thermal conductivity of the structure measured with a thermal conductivity meter.
  • Example 7 In the electrospinning process, N. which is a solvent.
  • a porous layer was formed in the same manner as in Example 1 except that an epoxy resin main component diluted with N-dimethylformamide (DMF) at 45% by weight was used to make the average diameter of the epoxy resin-containing fibers 450 nm.
  • DMF N-dimethylformamide
  • the density and relative dielectric constant of the epoxy resin, the thermal conductivity of the fiber, the vertical length, the horizontal length, and the thickness of the porous layer were the same as in Example 1.
  • Table 1 shows the porosity of the porous layer and the porosity of the laminate.
  • Example 8 A structure was produced in the same manner as in Example 1 except that the obtained porous layer was used. Table 1 shows the thermal conductivity of the structure measured with a thermal conductivity meter.
  • Example 8 Polystyrene was dissolved in N, N-dimethylformamide (DMF) as a solvent to prepare a 20 wt% solution, which was used as a raw material solution.
  • DMF N, N-dimethylformamide
  • the obtained raw material solution was supplied from the spinning nozzle to the surface of the substrate using a metering pump at a supply rate of 1 mL / h.
  • a high voltage generator applying a voltage of 60 kV to the spinning nozzle and transporting the substrate at 0.15 / min, moving the spinning nozzle in a range of 200 mm perpendicular to the substrate transport direction Fibers were deposited on the surface of the substrate to form a porous layer.
  • Aluminum foil was used for the substrate.
  • the fibers constituting the obtained porous layer contained 100% by weight of polystyrene.
  • Table 1 shows the polystyrene density, relative dielectric constant, fiber thermal conductivity, fiber average diameter, and porosity of the porous layer.
  • the vertical length, horizontal length, and thickness of the porous layer were the same as in Example 1.
  • the same acrylic resin porous plate as in Example 1 was prepared.
  • Example 9 Polyamideimide 30% was dissolved in N, N-dimethylacetamide (DMAc) as a solvent to prepare a 30 wt% solution as a raw material solution.
  • DMAc N, N-dimethylacetamide
  • the obtained raw material solution was supplied from the spinning nozzle to the surface of the substrate using a metering pump at a supply rate of 1 mL / h.
  • a high voltage generator applying a voltage of 60 kV to the spinning nozzle and transporting the substrate at 0.15 / min, moving the spinning nozzle in a range of 200 mm perpendicular to the substrate transport direction Fibers were deposited on the surface of the substrate to form a porous layer.
  • Aluminum foil was used for the substrate.
  • the fibers constituting the obtained porous layer contained 100% by weight of polyamideimide.
  • Table 1 shows the density of polyamideimide, the relative dielectric constant, the thermal conductivity of the fiber, the average diameter of the fiber, and the porosity of the porous layer.
  • the vertical length, horizontal length, and thickness of the porous layer were the same as in Example 1.
  • the same acrylic resin porous plate as in Example 1 was prepared.
  • a laminated body and a structure were produced in the same manner as in Example 1.
  • Table 1 shows the porosity of the laminate and the thermal conductivity of the structure measured with a thermal conductivity meter.
  • a porous sheet made of glass fiber was prepared. The porous sheet had a longitudinal length of 150 mm, a lateral length of 150 mm, and a thickness of 1 mm. The density of the glass was 2.5 g / cm 3 . Since the thermal conductivity of glass is regarded as the thermal conductivity of the fiber, the thermal conductivity of the fiber is 1 W / m ⁇ K. When the average diameter of the fiber was measured by the same method as in Example 1, it was 5 ⁇ m. When the porosity of the porous layer was measured by the method described above, it was 95%.
  • the thermal conductivity of the obtained structure of the comparative example was measured with a thermal conductivity meter, and found to be 8 mW / m ⁇ K.
  • the displacement and reaction force were measured while pressing a contact-type pressure gauge (force gauge) on the laminate in which the fiber membrane layers were laminated to a thickness of about 150 ⁇ m.
  • the measurement results are plotted with the laminate thickness on the horizontal axis and the reaction force on the vertical axis, and the slope of the straight line connecting the obtained plots is shown in Table 1 as the compressive strength.
  • the structures using the epoxy resins of Examples 1 to 7 have a lower thermal conductivity than the structures of Examples 8 to 9 and Comparative Examples.
  • the structures using the epoxy resins of Examples 1 to 7 are superior in compression strength to the structures using the other resin materials shown in Examples 8 to 9, and have a low thermal conductivity.
  • the first fiber containing the thermosetting resin and the electrolyte and / or the resin having a density of 0.5 g / cm 3 or more and 3 g / cm 3 or less. Since it contains the porous layer containing the second fiber having an average diameter of 30 nm or more and less than 5 ⁇ m, it is possible to provide a structure capable of arbitrarily changing the compressive strength.
  • DESCRIPTION OF SYMBOLS 10 ... Structure, 11 ... Core material, 13 ... Fiber, 14 ... Core material, 1 ... Core material, 2, 19, 22, 24, 26 ... Porous layer, 3, 6 ... Laminated body, 4 ... Exterior member, DESCRIPTION OF SYMBOLS 5 ... Fusion part, 15 ... Petri dish, 16 ... Oriented collagen sheet, 17 ... Culture solution, 18 ... Insulating material and / or insulating auxiliary material, 20 ... Insulating resin, 21 ... Feather part of a generator windmill, 23a, 23b ... Base material, 25 ... diaphragm.

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Abstract

　実施形態によれば、繊維により構成されるコア材と、コア材を構成するものであって、コア材と接触している芯材とを備える構造体が提供される。

Description

構造体及びコア材
　本発明の実施形態は、繊維からなるコア材を備える構造体、並びに、この構造体を構成するコア材に関する。
　従来より、繊維からなるコア材を備える構造体が考えられている。この種の構造体を構成する繊維としては、例えば特許文献１に開示されているような高分子材料からなる微細な繊維が考えられる。しかしながら、コア材を繊維で構成した構造体は、その構造上、強度が弱いという課題がある。
特開２００２－２４９９６６号公報 特許５１０５３５２号公報 特開２０１２－１９７６４４号公報
　本実施形態は、繊維からなるコア材を備える構造体に関し、その強度の向上を図ることができる構造体、並びに、この構造体を構成するコア材を提供する。
　また、実施形態によれば、圧縮強度を任意に変化させることが可能な構造体が提供される。
　本実施形態に係る構造体は、繊維により構成されるコア材と、前記コア材を構成するものであって、前記コア材の変形を抑制する芯材と、を備える。
　また、実施形態によれば、熱硬化性樹脂及び電解質を含む繊維を含む多孔質層を少なくとも一層含む、構造体が提供される。
　実施形態によれば、複数の多孔質層を含む積層体を含む構造体が提供される。複数の多孔質層は、密度が０．５ｇ／ｃｍ３以上３ｇ／ｃｍ３以下の樹脂を含有し、かつ３０ｎｍ以上５μｍ未満の平均直径を有する繊維を含む。多孔質層の空孔率が４５％以上９５％以下の範囲である。
　さらに、実施形態によれば、繊維により構成されるコア材と、コア材を構成するものであって、コア材と接触している芯材とを備える構造体が提供される。
図１は、本実施形態に係る構造体の構成例を示す断面図である。 図２は、実施形態に係る構造体の構成例を示す断面図である。 図３は、実施形態に係る構造体の構成例を示す断面図である。 図４は、構造体に含まれる芯材の一例を示す斜視図である。 図５は、構造体に含まれる芯材の別の例を示す斜視図である。 図６は、実施形態に係る構造体の構成例を示す断面図である。 図７は、実施形態に係る構造体の構成例を示す断面図である。 図８は、ラミネートフィルムの積層構造の例を示す断面図である。 図９は、生体材料シートとしての使用例を示す模式図である。 図１０は、配向コラーゲンシートの一例を示す電子顕微鏡写真である。 図１１は、絶縁材及び絶縁補助材の一例を示す模式図である。 図１２は、水滴衝撃緩衝材としての使用例を示す模式図である。 図１３は、図１２のXIII－XIII線に沿って切断した断面図である。 図１４は、接着層としての使用例を示す模式図である。 図１５は、隔膜の表面層としての使用例を示す模式図である。 図１６は、観察方向に対する繊維の投影図を示す模式図である。
　以下、一実施形態について図面を参照しながら説明する。図１に例示する構造体１０は、その主体部を構成するコア材１１を表面形成材１２内に収容した構成である。コア材１１は、繊維１３と芯材１４を備える。表面形成材１２は、構造体１０の表面部を構成する。表面形成材１２は、金属材料、有機材料、無機材料の何れか、または、その組み合わせからなるシート材で構成されている。この場合、表面形成材１２は、繊維１３および芯材１４からなるコア材１１を収容可能な袋状に構成されている。表面形成材１２内において、芯材１４は繊維１３により覆われる。なお、表面形成材１２は、コア材１１の全体を覆うのではなく、コア材１１の一部を覆う構成としてもよい。
　繊維１３は、ランダムに絡み合った樹脂繊維で形成されている。この場合、繊維１３は、エレクトロスピニング法で成形されている。エレクトロスピニング法で生成された繊維１３は、外径が０．１ｎｍ～１０μｍ程度となる細い繊維となり、且つ、長さが外径の例えば１０００倍以上となる長い繊維となる。また、エレクトロスピニング法で生成された繊維１３は、全体的に直線状ではなく、ランダムに湾曲した縮れ形状をなす。そのため、繊維同士の絡み合いが多くなる。
　この場合、繊維１３は、ガラスよりも密度の小さな有機系のポリマーで形成されている。繊維１３をガラスよりも密度の小さなポリマーで形成することにより繊維１３の軽量化を図ることができる。繊維１３は、ポリスチレン、ポリカーボネート、ポリメタクリル酸メチル、ポリプロピレン、ポリエチレン、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、ポリアミド、ポリオキシメチレン、ポリアミドイミド、ポリイミド、ポリサルファン、ポリエーテルサルファン、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリフェニレンサルファイド、変性ポリフェニレンエーテル、シンジオタクチックポリスチレン、液晶ポリマー、ユリア樹脂、不飽和ポリエステル、ポリフェノール、メラミン樹脂、エポキシ樹脂やこれらを含む共重合体などから選択される１種類、または２種類以上のポリマーの混紡によって形成することができる。
　繊維１３をエレクトロスピニング法で形成する場合、上記ポリマーを溶液化する。溶媒としては、例えば、イソプロパノール、エチレングリコール、シクロヘキサノン、ジメチルホルムアミド、アセトン、酢酸エチル、ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、ヘキサン、トルエン、キシレン、メチルエチルケトン、ジエチルケトン、酢酸ブチル、テトラヒドロフラン、ジオキサン、ピリジンなどの揮発性の有機溶剤や水を用いることができる。また、溶媒としては上記溶媒より選ばれる一種でもよく、また、複数種類が混在してもよい。なお、本実施形態に適用可能な溶媒は、上記溶媒に限定されるものではない。上記溶媒は、あくまでも例示である。
　繊維１３をエレクトロスピニング法で形成する場合、繊維同士の絡み合いを多くすることができるから、紡糸すると同時に、不織布状の繊維シートを形成することが可能である。また、繊維１３をエレクトロスピニング法で形成することによりマイクロオーダからナノオーダの繊維径を得ることができる。
　なお、繊維１３の繊維径は約５μｍ以下とすることが好ましく、さらに好ましくは１μｍ以下、つまりナノオーダの繊維径とすることが好ましい。また、繊維１３は、例えばケイ素酸化物、金属の水酸化物、炭酸塩、硫酸塩、ケイ酸塩など各種の無機フィラーを添加してもよい。添加する無機フィラーとしては、例えば、ウォラスナイト、チタン酸カリウム、ゾノトライト、石膏繊維、アルミニウムポレート、ＭＯＳ（塩基性硫酸マグネシウム）、アラミド繊維、炭素繊維、ガラス繊維、タルク、マイカ、ガラスフレークなどが考えられる。
　芯材１４は、例えばアクリル系の樹脂材料で構成されるものであり、応力に耐え得る強度を有する。また、この場合、芯材１４は、多数の微細な空隙を有する多孔質構造となっている。これにより、芯材１４の軽量化、ひいては、コア材１１、構造体１０の軽量化を図ることができる。この芯材１４は、応力によるコア材１１の変形を抑制する機能を有するほか、繊維１３の圧縮を抑制する機能を有する。この芯材１４を備えることにより、繊維１３からなるコア材１１の形状、換言すれば構造体１０の形状を安定的に維持することができる。また、コア材１１の強度、ひいては、構造体１０の強度を向上することができる。なお、芯材１４は、角部が丸みをおびた形状とするとよい。これにより、芯材１４の角部が表面形成材１２に与える力を緩和することができる。
　構造体１０は、コア材１１内に芯材１４を備えることで、コア材１１全体を繊維１３で構成したもの比べ、繊維１３の使用量を抑えたものとなっている。また、構造体１０は、このようにコア材１１内に芯材１４を備えることで、繊維１３からなる繊維層の厚さを抑えたものとなっている。コア材１１に外部から何らかの力が加わる場合には、そのコア材１１を構成する繊維１３が、加えられた力に応じて圧縮される。しかし、本実施形態に係る構造体１０によれば、表面形成材１２と芯材１４の間に存在する繊維層の厚さ、即ち繊維１３の量が抑えられている。そのため、表面形成材１２内全体に繊維１３を収容した構成に比べ、繊維１３の圧縮量を抑えることができる。
　本実施形態に係る構造体１０によれば、繊維１３により構成されるコア材１１を備える構造体１０に関し、コア材１１内に、当該コア材１１の変形を抑制するための芯材１４を設けた。これにより、コア材全体を繊維により構成する場合に比べ、コア材１１の強度の向上を図ることができ、ひいては、構造体１０全体の強度の向上を図ることができる。
　また、本実施形態に係る構造体１０によれば、芯材１４は多孔質であることから、芯材１４の軽量化を図ることができ、ひいては、コア材１１、構造体１０の軽量化を図ることができる。
　本実施形態に係る構造体は、繊維により構成されるコア材と、前記コア材を構成するものであって、前記コア材の変形を抑制する芯材と、を備える。この構成によれば、繊維からなるコア材を備える構造体に関し、その強度の向上を図ることができる。
　本実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。本実施形態およびその変形は、発明の範囲および要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。
　例えば、芯材１４の材質は、例えば樹脂材料のほか、金属材料や無機材料で構成してもよく、その材質を適宜変更して実施することができる。また、繊維１３は、樹脂繊維ではなく、ガラス繊維であってもよし、有機物を含む材料からなるファイバであってもよい。繊維を、有機物を含むファイバで構成する場合、その有機物は生体由来の有機物であってもよい。また、構造体１０は、コア材１１を収容した表面形成材１２内を減圧したものであってもよい。
　本実施形態に係る構造体は、様々な用途に用いることができ、例えば、人工関節、フィルタ、枕、貴重品用梱包材、ベッドなどに使用することができる。また、例えば自動車、新幹線、飛行機に搭載されるシートや、チャイルドシートなどといったシート類にも使用することができる。また、マスク、絆創膏、導電性シートなどにも使用することができる。本実施形態に係る構造体を、例えば人工関節や絆創膏に使用する場合には、構造体は、湿潤のための空間を設けるための部材として好適である。また、本実施形態に係る構造体は、空気中で使用できるほか、液体中でも使用できる。また、相互に環境が異なるものの間にセパレータとして使用することも可能である。
　実施形態の構造体について、さらに説明する。
　実施形態によれば、多孔質層を含む構造体が提供される。
　多孔質層は、１本又は複数本の繊維が集積、堆積、積層又は集合したものである。多孔質層では、繊維同士が絡み合い、複数箇所で接して接点が形成されており、繊維が三次元的に配置されている。接点において、繊維同士は接着又は溶着されていても良いが、接着も溶着もされていなくても良い。接点における繊維の配向は、多孔質層に外部から加えられた力等によって変動し得る。多孔質層は、不織布形状を有しているとも言える。
　多孔質層に存在する孔は、独立気孔、連続気孔、貫通孔いずれであっても良く、独立気孔と連続気孔というように複数種が存在していても良い。
　多孔質層に含まれる繊維は、（ａ）熱硬化性樹脂及び電解質を含む第1の繊維か、（ｂ）密度が０．５ｇ／ｃｍ３以上３ｇ／ｃｍ３以下の樹脂を含み、かつ３０ｎｍ以上５μｍ未満の直径を有する第２の繊維を含み得る。第１の繊維と第２の繊維の双方が、同じ多孔質層に含まれていても良い。第１の繊維と第２の繊維が同じ繊維であることもあり得る。
　第1の繊維、第２の繊維または第１の繊維及び第２の繊維を含む多孔質層によれば、繊維の平均直径、絡まり度合い及び配列を自在に変化させることができるため、圧縮強度を任意に変化させることが可能な構造体を提供することができる。このような構造体は、前述した用途に加え、例えば、断熱体、生体材料シート、絶縁材、絶縁補助材、水滴衝撃緩衝材、接着層、隔膜等にも使用可能なものである。
　また、第1の繊維、密度が１ｇ／ｃｍ３以上２ｇ／ｃｍ３以下の第２の繊維、またはこれらの繊維を含む多孔質層は、圧縮強度を高めることができるため、圧縮による空孔のつぶれを抑えることができる。その結果、多孔質層の多孔質構造を長期間に亘って維持することができるため、多孔質層の形状安定性が向上される。よって、圧縮強度に優れた形状安定性の高い構造体を実現することができる。このような構造体は、前述した用途に加え、例えば、断熱体、生体材料シート、絶縁材、絶縁補助材、水滴衝撃緩衝材、接着層、隔膜等にも使用可能なものである。
　また、多孔質層の圧縮強度が向上された結果、多孔質層中に使用する繊維量を少なくして空孔率を高めることができる。よって、多孔質層は、繊維径が細く、かつ空孔率の高い構造にして熱伝導率を小さくすることができるため、構造体の断熱性を改善することができる。
　第1の繊維に含まれる熱硬化性樹脂は、繊維の主成分であることが望ましい。ここで、主成分とは、繊維の構成成分のうち最も割合が高い成分である。熱硬化性樹脂は、繊維中に５０重量％以上含まれることが望ましい。これにより、多孔質層の圧縮強度を向上することができる。
　熱硬化性樹脂の比誘電率の範囲は、１以上１０００以下であることが望ましい。これにより、圧縮強度が高くて熱伝導率の小さい多孔質層が得られる。これは、多孔質層をエレクトロスピニング法で作製する際の繊維化の制御が容易になり、繊維の直径を細くしたり、繊維の配列（又は絡まり）を複雑なものにする等の調整がしやすくなるためである。比誘電率の範囲のより好ましい範囲は、５０以上１０００以下の範囲である。比誘電率の測定は、例えば、共振器法により測定可能である。
　熱硬化性樹脂の例には、エポキシ樹脂が含まれる。エポキシ樹脂の比誘電率は、１以上１０００以下の範囲である。
　電解質は、エポキシ樹脂含有繊維を含む多孔質層の圧縮強度及び断熱性の改善に寄与する。その理由は以下の通りである。電解質は、多孔質層をエレクトロスピニング法で作製する際に用いる原料溶液の誘電率及び導電率を高めることができる。電解質無添加の場合と比較すると、例えば、比誘電率を２～１００倍程度高めることが可能となる。その結果、エレクトロスピニング工程における繊維化の制御が容易になり、繊維の直径を細くしたり、繊維の配列（又は絡まり）を複雑なものにする等の調整がしやすくなる。このような効果に加え、電解質は、エポキシ樹脂含有繊維の導電性を高めることができる。電解質の例に、無機塩、アンモニウム塩、イオン液体が含まれる。電解質は、熱硬化性樹脂に対する親和性と、溶媒に対する溶解性に優れていることが望ましい。無機塩の例に、ＬｉＢｒ、ＬｉＣｌ、ＮａＣｌ、ＬｉＣｌ、ＭｇＣｌ２、ＮａＯＨ、ＫＭｎＯ４、Ｋ２ＣｒＯ４などが含まれる。また、アンモニウム塩の例に、ＮＨ４Ｃｌ、ＮＨ４Ｂｒなどが含まれる。一方、イオン液体の例に、ヘキサフルオロリン酸１－ブチル－３－メチルイミダゾリウムなどが含まれる。電解質の種類は、１種類又は２種類以上にすることができる。ＬｉＢｒは、原料溶液の溶剤に使用される有機溶剤(例えば、シクロヘキサノン)への溶解性に優れている。また、ＬｉＢｒは、安価であるという利点も有する。さらに、ＬｉＢｒは、熱的及び化学的に安定である。
　第1の繊維中の電解質の含有量は、０．０１重量％以上１０重量％以下の範囲にすることができる。電解質含有量が少ないと、直径が細い繊維を得られない。一方、電解質含有量が多いと、熱硬化性樹脂の含有量が不足して多孔質層の圧縮強度が低下する恐れがある。さらに好ましい範囲は、０．１重量％以上２重量％以下の範囲である。
　第1の繊維の平均直径は、３０ｎｍ以上５μｍ以下の範囲であることが望ましい。これにより、多孔質層の熱伝導率を低くして断熱性を高めることができる。また、多孔質層の圧力損失を小さくすることも可能となる。より好ましい範囲は３０ｎｍ以上５μｍ未満で、さらに好ましい範囲は４００ｎｍ以上８００ｎｍ以下で、さらに好ましい範囲は４００ｎｍ以上６００ｎｍ以下である。
　第２の繊維に含まれる樹脂の密度を１ｇ／ｃｍ３以上２ｇ／ｃｍ３以下の範囲にすることにより、第２の繊維の圧縮強度を高めることができる。密度が１ｇ／ｃｍ３以上２ｇ／ｃｍ３以下の樹脂の例に、エポキシ樹脂が含まれる。
　第２の繊維の平均直径を３０ｎｍ以上５μｍ未満の範囲にすることにより、多孔質層の熱伝導率を低くすることができる。また、多孔質層の圧力損失を小さくすることも可能となる。よって、第２の繊維を含む多孔質層は、圧縮強度が高く、かつ熱伝導率が低い。より好ましい範囲は４００ｎｍ以上８００ｎｍ以下で、さらに好ましい範囲は４００ｎｍ以上６００ｎｍ以下である。
　第１の繊維及び密度が１ｇ／ｃｍ３以上２ｇ／ｃｍ３以下の第２の繊維の熱伝導率は、例えば、０．０１Ｗ／ｍ・Ｋ以上５Ｗ／ｍ・Ｋ以下の範囲になる。ここで、繊維を構成する樹脂の熱伝導率を繊維の熱伝導率とみなす。エポキシ樹脂を含む繊維の熱伝導率は、０．０１Ｗ／ｍ・Ｋ以上５Ｗ／ｍ・Ｋ以下の範囲となる。
　第1の繊維及び第２の繊維のうち少なくとも一方を含む多孔質層の空孔率は、４５％以上９５％以下の範囲にすることが望ましい。空孔率を高くすることにより、多孔質層の断熱性を高めることができる。より好ましい範囲は７０％以上９５％以下である。
　また、上記多孔質層を複数含む積層体の空孔率は、４５％以上９５％以下の範囲にすることが望ましい。空孔率を高くすることにより、多孔質層の断熱性を高めることができる。より好ましい範囲は７０％以上９５％以下である。
　多孔質層の空孔率Ｐ１（％）は、下記（１）式から算出される。
　　Ｐ１（％）＝｛（Ｖ１－Ｖ２）×１００｝／Ｖ１　　（１）
　（１）式において、Ｖ１は多孔質層の空孔を含む体積で、多孔質層の縦長さＬ１、多孔質層の横長さＬ２、及び多孔質層の厚みＬ３から下記（２）式により算出される。多孔質層の空孔を含む体積Ｖ１は、多孔質層に液体等の材料が充填されていない状態で行われる。多孔質層に液体等の材料が充填されている場合、多孔質層の洗浄等によって材料を除去した後に測定を行う。また、各寸法Ｌ１、Ｌ２及びＬ３は、基材又は芯材上に作製した多孔質層を基材及び芯材から剥離した後、多孔質層を平面上に置いた状態でスケールにより計測する。
　　Ｖ１＝Ｌ１×Ｌ２×Ｌ３　　（２）
　また、Ｖ２は多孔質層の正味の体積で、多孔質層の重量を多孔質層の密度で割ったものである。
　積層体の空孔率Ｐ２（％）は、下記（３）式から算出される。
　　Ｐ２（％）＝｛（Ｖ３－Ｖ４）×１００｝／Ｖ３　　（３）
　（３）式において、Ｖ３は積層体の空孔を含む体積で、積層体の縦長さＬ４、積層体の横長さＬ５、及び積層体の厚みＬ６から下記（４）式により算出される。積層体の空孔を含む体積Ｖ３は、積層体に液体等の材料が充填されていない状態で行われる。積層体に液体等の材料が充填されている場合、積層体の洗浄等によって材料を除去した後に測定を行う。また、各寸法Ｌ４、Ｌ５及びＬ６は、積層体を平面上に置いた状態でスケールにより計測する。
　　Ｖ３＝Ｌ４×Ｌ５×Ｌ６　　（４）
　また、Ｖ４は積層体の正味の体積で、積層体の重量を積層体の密度で割ったものである。
　第1の繊維及び第２の繊維の平均直径は、例えば、以下に説明する方法で測定される。走査型電子顕微鏡（ＳＥＭ）にて多孔質層を観察する。この際、図６に示す矢印の方向から多孔質層を観察する。得られた像内における焦点が合っている繊維の直径を全て測定する。ここで、繊維の直径は、図６の矢印で示す観察方向に対する繊維の投影図における短辺の長さである。図１６に、繊維３１を矢印３２で示す観察方向に対して投影することにより得られる繊維の投影図３３を示す。図１６の例では、投影図３３が長方形である。長方形の投影図３３の短辺の長さＬを繊維３１の直径とみなす。得られた測定値から算出した平均値を、繊維の平均直径とする。ただし、直径を測定可能な繊維が１０本以上になるように観察範囲や倍率を変更するものとする。
　実施形態の構造体は、複数の多孔質層を含む積層体を含むことができる。積層体には、プレスにより多孔質層を一体化する、外装部材で多孔質層を一つに束ねる等を施すことができる。外装部材を用いる例には、枠内に積層体をはめる、積層体の最外層に板材を配置して板材により積層体を挟む、積層体を筐体、袋（例えば表面形成材１２）等に収納するなどが含まれる。
　実施形態の構造体は、芯材を含むことができる。芯材は、多孔質層よりも機械的強度に優れていることが望ましい。それにより、芯材を多孔質層又は繊維から構成されたコア材と接触させることで多孔質層の補強を担うことができるため、多孔質層の圧縮による変形を抑制することができ、構造体の形状を安定的に維持することができる。芯材は、多孔質構造を有することが望ましい。これにより、芯材の軽量化、ひいては構造体の軽量化を図ることができる。芯材は、角部が丸みをおびた形状とするとよい。これにより、芯材の角部が外装部材に与える力を緩和することができる。また、芯材は、例えばアクリル系の樹脂材料で構成することができる。
　第1の繊維及び第２の繊維のうち少なくとも一方を含む多孔質層は、例えば、エレクトロスピニング法により作製される。熱硬化性樹脂主剤及び電解質を有機溶剤に分散又は溶解させ、熱硬化性樹脂主剤及び電解質を含む原料溶液を調製する。原料溶液に硬化剤を添加した後、加熱により仮硬化させる。仮硬化させた原料溶液を用いてエレクトロスピニング法により多孔質層を形成する。基材をアースしてアース電極とする。紡糸ノズルに印加された電圧により原料溶液が帯電すると共に、原料溶液からの溶媒の揮発により原料溶液の単位体積当たりの帯電量が増加する。溶媒の揮発とそれに伴う単位体積あたりの帯電量の増加が連続して生じることで、紡糸ノズルから吐出された原料溶液は長手方向に延び、ナノサイズの熱硬化性樹脂含有繊維として基材に堆積する。熱硬化性樹脂含有繊維と基材間には、ノズルと基材間の電位差によりクーロン力が生じる。よって、ナノサイズの熱硬化性樹脂含有繊維により基材との接触面積を増加させることができ、この熱硬化性樹脂含有繊維をクーロン力により基材上に堆積することができる。
　原料溶液に電解質を含有させることにより、原料溶液の誘電率及び導電率を高くすることができる。その結果、原料溶液に電圧を印加した際に原料溶液を十分に帯電させることができるため、目的とする繊維直径への制御、繊維の配列の制御等が容易になる。また、熱硬化性樹脂の比誘電率の範囲を１以上１０００以下にすることは、原料溶液の誘電率の向上に寄与するため、繊維化の制御がより容易になる。
　原料溶液に含まれる有機溶剤には、上述した種類の有機溶剤を使用することができる。
　基材には、芯材を用いても良いし、芯材とは異なるものを使用しても良い。芯材とは異なるものを使用する場合、基材上に形成した多孔質層は、基材から分離した後に使用される。基材の例には、紙、アルミニウム箔が挙げられる。
　実施形態の構造体の一例を図２及び図３に示す。図２に示す構造体は、積層体３と、積層体３が収容される袋状の外装部材４とを含む。積層体３は、複数の芯材１と、複数の多孔質層２とを含む。芯材１は、多孔質構造を有し、例えば図４又は図５に示す構造を有することができる。図４に示す芯材１は、金網形状の多孔質シートである。一方、図５に示す芯材１は、格子形状の多孔質シートである。いずれのシートも、コーナ部がＲ形状になっている。積層体３において、芯材１と多孔質層２とが交互に積層され、両方の最外層に多孔質層２が位置している。袋状の外装部材４は、例えば、ラミネートフィルムを熱融着により袋状に加工したものである。外装部材４の側壁に、ラミネートフィルム同士が熱融着により貼り合わされた箇所５が位置している。ラミネートフィルムには、例えば、アルミニウム又はアルミニウム合金を含む層と、樹脂層とを含むものを使用することができる。ラミネートフィルムの具体例を図８に示すが、これに限られるものではない。図８に示すラミネートフィルム４は、外装部材４の外面を構成する第１層から外装部材４の内面を構成する第５層までの５層構造を有し、第１層４ａにポリエチレンテレフタレート（ＰＥＴ）、第２層４ｂにポリアミド（ＰＡ）、第３層４ｃにアルミニウム蒸着層、第４層４ｅにエチレン・ビニルアルコール共重合樹脂（ＥＶＯＨ）、第５層４ｄにポリエチレン（ＰＥ）が用いられる。図２に示す積層体では、芯材１と多孔質層２が互い違いに配置されていれば良く、一方の最外層に芯材１、他方の最外層に多孔質層２が配置されていても、あるいは両方の最外層に芯材１が配置されていても良い。
　図３に示す構造体は、積層体３中の芯材１と多孔質層２の配置が異なること以外は、図２と同様な構造を有する。積層体３は、複数の芯材１が積層されたものの両方の最外層に多孔質層２が配置されている。各最外層には、１層又は２層以上の多孔質層２を配置することができる。
　図２及び図３に示す構造体は、外装部材及び芯材を備えているが、外装部材及び芯材を備えていなくても良い。例えば図６に示すように、複数の多孔質層２の積層体６を、第１の実施形態の構造体として用いることができる。また、図７に示すように、図６に示す積層体６を、外装部材４に収容することもできる。なお、図７において、図２及び図３と同じ部材には同符号を付して説明を省略する。
　図２及び図３に例示されるように、構造体の積層体が芯材を含むことにより、多孔質層の圧縮による変形を抑制して気孔のつぶれをさらに抑えることができる。そのため、積層体の圧縮強度をさらに高めることができる。圧縮強度が向上された結果、多孔質層に使用する繊維量を少なくして空孔率を高めることができるため、繊維径が細く、かつ空孔率の高い構造にして積層体の熱伝導率をさらに小さくすることができる。
　図２に例示されるように多孔質層と芯材が交互に配置されていると、芯材の間に多孔質層が位置するため、輻射伝熱を抑制することができる。また、芯材を介した熱伝導を多孔質層によって抑制することができる。
　一方、図３に例示されているように多孔質層の間に芯材を配置することにより、積層体の構造を単純にすることができ、かつ簡便に作製できる。
　実施形態の構造体は、上述した用途に加え、例えば、断熱体、生体材料シート、絶縁材及び絶縁補助材、水滴衝撃緩衝材、接着層、隔膜等に用いることができる。
　生体材料シートの場合、芯材又は多孔質層が形成される基材に、ガラスもしくは樹脂製のシャーレなどの容器、絆創膏用基材、シート、多孔質体（例えばフィルム状もしくはスポンジ状で液体を保持する物）などが挙げられる。絆創膏用基材の例として、ウレタン不織布、塩化ビニルシート、伸縮性綿布、スポンジシート、ウレタンフィルム、オレフィンフィルムが挙げられる。
　基材としてシャーレなどの容器を用いる例を図９に示す。図９に示すように、シャーレ１５内に配向コラーゲンシート１６が収容され、配向コラーゲンシート１６上に培養液１７が充填される。配向コラーゲンシート１６の一例を図１０に示す。配向コラーゲンシート１６は、例えば、エポキシ樹脂などの熱硬化性樹脂の代わりにコラーゲン等の生体材料を使用することにより得ることが可能である。
　実施形態の多孔質層、積層体あるいは構造体を絶縁材及び／または絶縁補助材として用いることが可能である。また、図１１に例示されるように、多孔質層１９に絶縁性樹脂２０を含浸させたものを絶縁材及び／または絶縁補助材１８として使用可能である。繊維を構成する材料として熱硬化性樹脂の代わりにあるいは熱硬化性樹脂と併用して、例えば、ポリカーボネート（ＰＣ）、ポリエーテルサルホン（ＰＥＳ）、ポリアクリロニトリル（ＰＡＮ）、ポリエチレンナフタレート（ＰＥＮ）、ポリウレタン（ＰＵ）、ユリア樹脂（ＵＦ）、アクリル樹脂（ＰＭＭＡ）、ポリアミド（ＰＡ）、ポリスチレン（ＰＳ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）等が使用可能である。
　実施形態の多孔質層、積層体あるいは構造体を水滴衝撃緩衝材として用いることが可能である。芯材又は多孔質層が一時的に形成される基材として、繊維強化プラスチック（ＦＲＰ）のような樹脂製基材が挙げられる。一例を図１２及び図１３に示す。図１２に、発電風車の羽部２１を含む要部を示す。また、図１３に、羽部２１のXIII－XIII線に沿って切断した断面図を示す。図１３に示すように、発電風車の羽部２１の表面を多孔質層２２で被覆することができる。これにより、羽部２１に水滴等の液滴が衝突した際の衝撃を緩和することができる。また、繊維を構成する材料として熱硬化性樹脂の代わりにあるいは熱硬化性樹脂と併用して、他の樹脂を使用することができる。他の樹脂の例には、絶縁材・絶縁補助材で挙げたものと同様なものが挙げられる。
　また、実施形態の多孔質層、積層体あるいは構造体を接着層として用いることが可能である。その結果、接着層を基材等に薄く均一に形成することができる。また、接着層中の多孔質層の空孔に他種接着剤を充填又は含浸させることにより、接着層の接着力を高めることができる。あるいは、多孔質層の空孔にインク、磁性材料等を担持させても良い。芯材又は多孔質層が一時的に形成される基材として、紙、写真、フィルム、シート等の印刷に使用されるような薄い基材を挙げることができる。接着層を構成する繊維の材料としては、熱硬化性樹脂の代わりにあるいは熱硬化性樹脂と併用して、水溶接着剤、ゴム系接着剤、エポキシ系接着剤、シアノアクリル系接着剤、ビニール系接着剤、シリコーンゴム系接着剤、プラスチック系接着剤等を使用可能である。図１４に、紙等の基材２３ａ及び２３ｂの間に接着層として多孔質層２４を配置する例を示す。
　実施形態の多孔質層、積層体あるいは構造体を、ガス分離あるいは気液分離に使用される隔膜の表面に形成しても良い。これにより、隔膜の強度、耐候性、耐久性などを向上させることができる。また、微細な繊維と高い空孔率を有する多孔質層が隔膜表面に形成されるため、分離効率を向上させることができる。一例を図１５に示す。ガス分離あるいは気液分離に使用される隔膜２５の片面に多孔質層２６が形成されている。多孔質層２６の繊維を構成する材料として熱硬化性樹脂の代わりにあるいは熱硬化性樹脂と併用して、他の樹脂を使用することができる。他の樹脂の例には、絶縁材・絶縁補助材で挙げたものと同様なものが挙げられる。
　以上説明した多孔質層に含まれる繊維として、上記種類の繊維と併せて、あるいは上記種類の繊維の代わりに、焼成等の加工をした無機ナノファイバー（例えば、ＴｉＯ２、ＳｎＯ２、ＳｉＯ２、ＺｒＯ２、Ｆｅ２Ｏ３、ＢａＴｉＯ３、ＮｉＦｅ２Ｏ４）、炭素繊維を用いることができる。
　以下、実施例を図面を参照して詳細に説明する。
（実施例１）
　溶剤であるＮ．Ｎ－ジメチルホルムアミド（ＤＭＦ）で５０重量％希釈したエポキシ樹脂主剤に、ＬｉＢｒを１重量％添加して溶解させて溶液を調製した。この溶液にエポキシ樹脂主剤に対して４０重量％量の硬化剤を加えて７０℃に加熱して仮硬化させ、原料溶液を得た。
　得られた原料溶液を、定量ポンプを使用して１ｍＬ／ｈの供給速度で紡糸ノズルから基材の表面に供給した。高電圧発生器を用いて、紡糸ノズルに６０ｋＶの電圧を印加し、基材を０．１５／ｍｉｎで搬送しながら、この紡糸ノズルを基材搬送方向に対して垂直に２００ｍｍの範囲を動かしながら基材の表面に繊維を堆積させて多孔質層を形成した。基材にはアルミニウム箔を用いた。
　得られた多孔質層を構成する繊維は、エポキシ樹脂を９９重量％、ＬｉＢｒを１重量％含有するものであった。また、エポキシ樹脂の密度は１．２ｇ／ｃｍ３で、比誘電率は１１であった。エポキシ樹脂の熱伝導率を繊維の熱伝導率とみなすため、繊維の熱伝導率は０．３Ｗ／ｍ・Ｋである。繊維の平均直径を、前述の方法でＳＥＭの倍率を２０００倍、直径を測定した繊維の本数を２０本として測定したところ、８００ｎｍであった。多孔質層の空孔率を前述の方法で測定したところ、７８％であった。多孔質層の縦長さ１５０ｍｍ、横長さ１５０ｍｍ、厚み２１ｍｍであった。
　芯材として、図５に示す構造を有し、縦長さ１５０ｍｍ、横長さ１５０ｍｍ、厚み１０ｍｍ、空孔率が８０％のアクリル樹脂（polymethyl methacrylate:PMMA）製の多孔質板を用意した。
　図２に示すように、多孔質層と芯材を交互に積層し、両方の最外層に多孔質膜が位置する積層体を得た。具体的には、３０枚の多孔質層を積層したものを１つのユニットとし、３つのユニットと２枚の芯材とを互い違いに積層し、積層体を得た。積層体中の多孔質層の層数は９０で、芯材の層数は２であったが、多孔質層及び芯材の層数はこれに限定されるものではない。積層体の空孔率は８０％であった。
　得られた積層体をラミネートフィルム製の袋状外装部材に収納した後、真空ポンプを用いて外装部材内を真空状態にし、外装部材をヒートシールにより封止して構造体を得た。ラミネートフィルムは、図８に示す５層構造を有し、第１層４ａが厚さ１６μｍのポリエチレンテレフタレート（ＰＥＴ）層、第２層４ｂに厚さ３０μｍのポリアミド（ＰＡ）層、第３層４ｃに厚さ１μｍ未満のアルミニウム蒸着層、第４層４ｅに厚さ２０μｍのエチレン・ビニルアルコール共重合樹脂（ＥＶＯＨ）層、第５層４ｄに厚さ６０μｍのポリエチレン（ＰＥ）層が用いられている。
　得られた実施例１の構造体の熱伝導率を熱伝導率計で測定したところ、７ｍＷ／ｍ・Ｋであった。
（実施例２）
　実施例１と同様な方法で作製した多孔質層と芯材を用意した。図３に示すように、芯材１の両方の最外層に多孔質層を積層し、積層体を得た。多孔質層の積層数は、芯材の片側当たり１０層とした。積層体の空孔率は８０％であった。
得られた積層体を、実施例１と同様な５層構造のラミネートフィルム製の袋状外装部材に収納した後、真空ポンプを用いて外装部材内を真空状態にし、外装部材をヒートシールにより封止して構造体を得た。
　得られた実施例２の構造体の熱伝導率を熱伝導率計で測定したところ、６ｍＷ／ｍ・Ｋであった。
（実施例３）
　芯材として、図４に示す構造を有し、縦長さ１５０ｍｍ、横長さ１５０ｍｍ、厚み５ｍｍ、空孔率が８０％のアクリル樹脂製の多孔質板を用意した。
　実施例１と同様にして調製した原料溶液を、定量ポンプを使用して１ｍＬ／ｈの供給速度で紡糸ノズルから基材の表面に供給した。高電圧発生器を用いて、紡糸ノズルに６０ｋＶの電圧を印加し、基材を０．１５／ｍｉｎで搬送しながら、この紡糸ノズルを基材搬送方向に対して垂直に２００ｍｍの範囲を動かしながら基材の表面に繊維を堆積させて多孔質層を形成した。基材にはアルミニウム箔を用いた。
　得られた多孔質層を構成する繊維は、エポキシ樹脂を９９重量％、ＬｉＢｒを１重量％含有するものであった。また、エポキシ樹脂の密度は１．２ｇ／ｃｍ３で、比誘電率は１１であった。エポキシ樹脂の熱伝導率を繊維の熱伝導率とみなすため、繊維の熱伝導率は０．３Ｗ／ｍ・Ｋである。繊維の平均直径を、前述の方法でＳＥＭの倍率を２０００倍、直径を測定した繊維の本数を２０本として測定したところ、８００ｎｍであった。多孔質層の空孔率を前述の方法で測定したところ、８０％であった。多孔質層の縦長さ１５０ｍｍ、横長さ１５０ｍｍ、厚み２１ｍｍであった。
　図２に示すように、多孔質層と芯材を交互に積層し、両方の最外層に多孔質膜が位置する積層体を得た。積層体中の多孔質層の層数は、多孔質層を積層した１ユニット当たり５０であった。積層体の空孔率は８０％であった。
　得られた積層体を実施例１と同様な５層構造のラミネートフィルム製の袋状外装部材に収納した後、真空ポンプを用いて外装部材内を真空状態にし、外装部材をヒートシールにより封止して構造体を得た。
　得られた実施例３の構造体の熱伝導率を熱伝導率計で測定したところ、７ｍＷ／ｍ・Ｋであった。
（実施例４）
　実施例３と同様な方法で作製した多孔質層と芯材を用意した。図３に示すように、芯材１の両方の最外層に多孔質層を積層し、積層体を得た。多孔質層の積層数は、芯材の片側当たり１０層とした。積層体の空孔率は９２％であった。
　得られた積層体を実施例１と同様な５層構造のラミネートフィルム製の袋状外装部材に収納した後、真空ポンプを用いて外装部材内を真空状態にし、外装部材をヒートシールにより封止して構造体を得た。
　得られた実施例４の構造体の熱伝導率を熱伝導率計で測定したところ、６ｍＷ／ｍ・Ｋであった。
（実施例５）
　電解質としてＬｉＢｒの代わりに０．１重量％のＬｉＣｌを用いること以外は、実施例１と同様にして多孔質層を形成した。
　得られた多孔質層を構成する繊維は、エポキシ樹脂を９９．９重量％、ＬｉＣｌを０．１重量％含有するものであった。また、エポキシ樹脂の密度と比誘電率、繊維の熱伝導率、繊維の平均直径、多孔質層の空孔率、多孔質層の縦長さ、横長さ、厚みは実施例１と同様であった。これらのうち一部のデータを表１に示す。
　得られた多孔質層を用いること以外は実施例１と同様にして構造体を作製した。熱伝導率計で測定した構造体の熱伝導率を表１に示す。
（実施例６）
　電解質としてＬｉＢｒの代わりに０．１重量％のベンジルトリエチルアンモニウムクロライドを用いること以外は、実施例１と同様にして多孔質層を形成した。
　得られた多孔質層を構成する繊維は、エポキシ樹脂を９９．９重量％、ベンジルトリエチルアンモニウムクロライドを０．１重量％含有するものであった。また、エポキシ樹脂の密度と比誘電率、繊維の熱伝導率、繊維の平均直径、多孔質層の空孔率、多孔質層の縦長さ、横長さ、厚みは実施例１と同様であった。これらのうち一部のデータを表１に示す。
　得られた多孔質層を用いること以外は実施例１と同様にして構造体を作製した。熱伝導率計で測定した構造体の熱伝導率を表１に示す。
（実施例７）
　エレクトロスピニング工程において、溶剤であるＮ．Ｎ－ジメチルホルムアミド（ＤＭＦ）で４５重量％希釈したエポキシ樹脂主剤を用いることによりエポキシ樹脂含有繊維の平均直径を４５０ｎｍにすること以外は、実施例１と同様にして多孔質層を形成した。エポキシ樹脂の密度と比誘電率、繊維の熱伝導率、多孔質層の縦長さ、横長さ、厚みは実施例１と同様であった。多孔質層の空孔率、積層体の空孔率を表１に示す。
　得られた多孔質層を用いること以外は実施例１と同様にして構造体を作製した。熱伝導率計で測定した構造体の熱伝導率を表１に示す。
（実施例８）
　溶剤であるＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）にポリスチレンを溶解して２０ｗｔ％溶液を調製し、原料溶液とした。
　得られた原料溶液を、定量ポンプを使用して１ｍＬ／ｈの供給速度で紡糸ノズルから基材の表面に供給した。高電圧発生器を用いて、紡糸ノズルに６０ｋＶの電圧を印加し、基材を０．１５／ｍｉｎで搬送しながら、この紡糸ノズルを基材搬送方向に対して垂直に２００ｍｍの範囲を動かしながら基材の表面に繊維を堆積させて多孔質層を形成した。基材にはアルミニウム箔を用いた。
　得られた多孔質層を構成する繊維は、ポリスチレンを１００重量％含有するものであった。また、ポリスチレンの密度、比誘電率、繊維の熱伝導率、繊維の平均直径、多孔質層の空孔率を表１に示す。多孔質層の縦長さ、横長さ、厚みは実施例１と同様であった。
　芯材として、実施例１と同様なアクリル樹脂製の多孔質板を用意した。
　実施例１と同様にして積層体及び構造体を作製した。積層体の空孔率と、熱伝導率計で測定した構造体の熱伝導率を表１に示す。
（実施例９）
　溶剤であるＮ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）にポリアミドイミド３０％を溶解して３０ｗｔ％溶液を調製し原料溶液とした。
　得られた原料溶液を、定量ポンプを使用して１ｍＬ／ｈの供給速度で紡糸ノズルから基材の表面に供給した。高電圧発生器を用いて、紡糸ノズルに６０ｋＶの電圧を印加し、基材を０．１５／ｍｉｎで搬送しながら、この紡糸ノズルを基材搬送方向に対して垂直に２００ｍｍの範囲を動かしながら基材の表面に繊維を堆積させて多孔質層を形成した。基材にはアルミニウム箔を用いた。
　得られた多孔質層を構成する繊維は、ポリアミドイミドを１００重量％含有するものであった。また、ポリアミドイミドの密度、比誘電率、繊維の熱伝導率、繊維の平均直径、多孔質層の空孔率を表１に示す。多孔質層の縦長さ、横長さ、厚みは実施例１と同様であった。
　芯材として、実施例１と同様なアクリル樹脂製の多孔質板を用意した。
　実施例１と同様にして積層体及び構造体を作製した。積層体の空孔率と、熱伝導率計で測定した構造体の熱伝導率を表１に示す。
（比較例）
　ガラス繊維からなる多孔質シートを用意した。多孔質シートは、縦長さ１５０ｍｍ、横長さ１５０ｍｍ、厚さが１ｍｍであった。ガラスの密度は２．５ｇ／ｃｍ３であった。ガラスの熱伝導率を繊維の熱伝導率とみなすため、繊維の熱伝導率は１Ｗ／ｍ・Ｋである。繊維の平均直径を、実施例１と同様な方法で測定したところ、５μｍであった。多孔質層の空孔率を前述の方法で測定したところ、９５％であった。
　多孔質シートを２３枚積層して積層体を得た。積層体の空孔率は９２％であった。得られた積層体を実施例１と同様な５層構造のラミネートフィルム製の袋状外装部材に収納した後、真空ポンプを用いて外装部材内を真空状態にし、外装部材をヒートシールにより封止して構造体を得た。
　得られた比較例の構造体の熱伝導率を熱伝導率計で測定したところ、８ｍＷ／ｍ・Ｋであった。
　実施例１～９及び比較例の構造体について、繊維膜層を厚みが約１５０μｍとなるように積層した積層体について、接触式圧力計（フォースゲージ）を押し付けながら変位と反力とを測定し、積層体の厚みを横軸に、反力を縦軸として測定結果をプロットし、得られたプロットを結んだ直線の傾きを圧縮強度として表１に示す。
Figure JPOXMLDOC01-appb-T000001
　表１から明らかな通り、実施例１～７のエポキシ樹脂を使用した構造体は、実施例８～９および比較例の構造体と比較して、低熱伝導率である。また、実施例１～７のエポキシ樹脂を使用した構造体は、実施例８～９に示す他の樹脂材料を使用した構造体よりも圧縮強度に優れており、かつ低熱伝導率である。
　以上説明した少なくとも一つの実施形態及び実施例の構造体によれば、熱硬化性樹脂及び電解質を含む第１の繊維及び／又は密度が０．５ｇ／ｃｍ３以上３ｇ／ｃｍ３以下の樹脂を含有し、かつ３０ｎｍ以上５μｍ未満の平均直径を有する第２の繊維を含む多孔質層を含むため、圧縮強度を任意に変化させることが可能な構造体を提供することができる。
　１０…構造体、１１…コア材、１３…繊維、１４…芯材、１…芯材、２，１９，２２，２４，２６…多孔質層、３，６…積層体、４…外装部材、５…融着部、１５…シャーレ、１６…配向コラーゲンシート、１７…培養液、１８…絶縁材及び／または絶縁補助材、２０…絶縁性樹脂、２１…発電風車の羽部、２３ａ，２３ｂ…基材、２５…隔膜。

Claims (16)

  1. 　繊維により構成されるコア材と、
    　前記コア材を構成するものであって、前記コア材の変形を抑制する芯材と、を備える構造体。
  2. 　前記芯材は、前記コア材内に設けられ、前記繊維からなる繊維層の厚さを抑えることにより前記繊維の圧縮量を抑制する請求項１に記載の構造体。
  3. 　前記芯材は、前記コア材内に設けられることにより、前記繊維の使用量を抑える請求項１または２に記載の構造体。
  4. 　前記芯材は、多孔質である請求項１から３の何れか１項に記載の構造体。
  5. 　前記コア材の少なくとも一部を覆う表面形成材を備える請求項１から４の何れか１項に記載の構造体。
  6. 　請求項１から５の何れか１項に記載の構造体に備えられるコア材。
  7. 　熱硬化性樹脂及び電解質を含む繊維を含む多孔質層を少なくとも一層含む、構造体。
  8. 　前記熱硬化性樹脂がエポキシ樹脂で、かつ前記電解質が臭化リチウムである、請求項７に記載の構造体。
  9. 　前記繊維が３０ｎｍ以上５μｍ以下の平均直径を有する、請求項７または請求項８に記載の構造体。
  10. 　前記熱硬化性樹脂の比誘電率の範囲は１以上１０００以下である、請求項７～９いずれか１項に記載の構造体。
  11. 　密度が０．５ｇ／ｃｍ３以上３ｇ／ｃｍ３以下の樹脂を含有し、かつ３０ｎｍ以上５μｍ未満の平均直径を有する繊維を含む空孔率が４５％以上９５％以下の多孔質層を複数含む積層体を含む、構造体。
  12. 　前記密度が１ｇ／ｃｍ３以上２ｇ／ｃｍ３以下である、請求項１１に記載の構造体。
  13. 　前記積層体の空孔率が４５％以上９５％以下である、請求項１１または１２に記載の構造体。
  14. 　前記繊維の熱伝導率が０．０１Ｗ／ｍ・Ｋ以上５Ｗ／ｍ・Ｋ以下である、請求項１１～１３のいずれか1項に記載の構造体。
  15. 　前記樹脂がエポキシ樹脂である、請求項１１～１４のいずれか１項に記載の構造体。
  16. 　繊維により構成されるコア材と、
    　前記コア材を構成するものであって、前記コア材と接触している芯材と、
    を備える構造体。
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