Rigid polymer molded body and method for producing rigid polymer molded body

Abstract

A method for producing a rigid polymer molded body according to the present invention comprises: a step in which a rigid polymer molded body is formed by depositing a rigid polymer on at least one of a first electrode and a second electrode from a rigid polymer dispersion that is obtained by dispersing the rigid polymer in a polar medium; and a step in which the rigid polymer molded body is dried. In the step in which a rigid polymer molded body is formed, a surface of the at least one electrode, on which the rigid polymer is to be deposited, has a projected part or a recessed part, which is larger than the thickness of the rigid polymer molded body.

Description

[Technical Field]

[0001] The present invention relates to a rigid-rod polymer molded article and a method for producing the same. [Background technology]

[0002] It is known that nanofiber molded bodies can be formed from nanofiber dispersions in which nanofibers are dispersed in a solvent. The use of nanofiber molded bodies as a substitute for paper phenolic plates is being considered. Furthermore, because nanofiber molded bodies are biodegradable, their use as disposable protective plates is being considered. Furthermore, because cellulose nanofibers have extremely high oil resistance, the use of cellulose nanofiber molded bodies as gaskets in oil is being considered (see Patent Document 1).

[0003] Patent Document 1 describes the production of a molded microfibrillated cellulose body from a suspension of microfibrillated cellulose nanofibers in which microfibrillated cellulose is dispersed. In the production method described in Patent Document 1, a microfibrillated cellulose suspension is prepared in which microfibrillated cellulose is dispersed in water, an organic solvent, or a mixed solvent of water and an organic solvent, and the microfibrillated cellulose suspension is pre-dehydrated and molded under heat and pressure in a sealed state to produce a molded microfibrillated cellulose body. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-100466 Summary of the Invention [Problem to be solved by the invention]

[0005] However, with the manufacturing method described in Patent Document 1, it may not be easy to form a nanofiber molded article in a desired shape.

[0006] The present invention has been made in view of the above problems, and an object of the present invention is to provide a rigid polymer molded article that can be easily formed into a desired shape, and a method for producing the rigid polymer molded article. [Means for solving the problem]

[0007] The method for producing a rigid polymer molded body according to the present invention includes the steps of: forming a rigid polymer molded body by depositing a rigid polymer on at least one of a first electrode and a second electrode from a rigid polymer dispersion in which the rigid polymer is dispersed in a polar medium; and drying the rigid polymer molded body. In the step of forming the rigid polymer molded body, the at least one electrode has, on its surface on which the rigid polymer is deposited, protrusions or recesses that are larger than the thickness of the rigid polymer molded body.

[0008] In one embodiment, in the step of forming the rigid-polymer molded article, the rigid polymer includes a polysaccharide having a linear main chain structure.

[0009] In one embodiment, in the step of forming the rigid polymer molded body, the electric field strength at the at least one electrode is 500 V / cm or less.

[0010] In one embodiment, in the step of forming the rigid polymer molded body, the at least one electrode has an insulating base and a conductive film covering the surface of the base.

[0011] In one embodiment, the method for producing a rigid polymer molded body further includes a step of dissolving the base.

[0012] In one embodiment, the conductive film is dissolved in the step of forming the rigid polymer molded body.

[0013] The rigid polymer molding according to the present invention has a first main surface, a second main surface, and a side surface connecting the first main surface and the second main surface, wherein one of the first main surface and the second main surface has a convex portion that is larger than the height of the side surface, and the other of the first main surface and the second main surface has a concave portion that is larger than the height of the side surface.

[0014] In one embodiment, the rigid polymer comprises a polysaccharide having a linear main chain structure.

[0015] In one embodiment, the rigid polymer molded article has a degree of orientation of 20% or more.

[0016] In one embodiment, the rigid polymer has a bionanofiber or a rigid main chain structure. [Effects of the Invention]

[0017] According to the present invention, a rigid polymer molded article can be easily formed into a desired shape. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a schematic diagram of a manufacturing device for manufacturing a rigid polymer molded article according to the present embodiment. [Figure 2] 1 is a flowchart showing a method for producing a rigid polymer molded article according to the present embodiment. [Figure 3] 1 is a schematic diagram of a manufacturing device for manufacturing a rigid polymer molded article according to the present embodiment. [Figure 4] 1(a) to 1(c) are schematic diagrams illustrating the method for producing a rigid polymer molded article according to the present embodiment. [Figure 5] 1 is a schematic diagram of a manufacturing device for manufacturing a rigid polymer molded article according to the present embodiment. [Figure 6] 1(a) to 1(c) are schematic diagrams illustrating the method for producing a rigid polymer molded article according to the present embodiment. [Figure 7](a) is a schematic diagram of a rigid polymer molding produced by applying a voltage at a relatively low electric field strength, (b) is a schematic diagram showing the orientation of the rigid polymer molding of (a), and (c) is a schematic diagram of a rigid polymer molding produced by drying the rigid polymer molding of (a). [Figure 8] (a) is a schematic diagram of a rigid polymer molding deposited by applying a voltage at a moderate electric field strength, (b) is a schematic diagram showing the orientation of the rigid polymer molding of (a), and (c) is a schematic diagram of a rigid polymer molding after the rigid polymer molding of (a) has been dried. [Figure 9] (a) is a schematic diagram of a rigid polymer molding produced by applying a voltage with a relatively high electric field strength, (b) is a schematic diagram showing the orientation of the rigid polymer molding of (a), and (c) is a schematic diagram of a rigid polymer molding produced by drying the rigid polymer molding of (a). [Figure 10] FIG. 1(a) is a schematic diagram of a rigid polymer molded article of this embodiment, and FIG. 1(b) is a schematic diagram of the rigid polymer molded article of (a) used in a microneedle. [Figure 11] FIG. 2 is a schematic perspective view of an electrode in a manufacturing device for manufacturing a rigid polymer molded article of the present embodiment. [Figure 12] 1 is a flowchart showing a method for producing a rigid polymer molded article according to the present embodiment. [Figure 13] FIG. 1(a) is a schematic diagram of a rigid-rod polymer molded article of the present embodiment, and FIG. 1(b) is a schematic diagram of the rigid-rod polymer molded article dried from (a). [Figure 14] FIG. 1(a) is a schematic diagram of an electrode in a manufacturing device for manufacturing a rigid polymer molded article of the present embodiment, and FIG. 1(b) is a schematic exploded perspective view of the electrode of FIG. [Figure 15] 1 is a flowchart showing a method for producing a rigid polymer molded article according to the present embodiment. [Figure 16]FIG. 1(a) is a schematic perspective view of an electrode in a manufacturing device for manufacturing a rigid polymer molded article of the present embodiment, FIG. 1(b) is a schematic diagram of an aerogel nanofiber molded article produced on the electrode of FIG. 1(a), and FIG. 1(c) is a schematic diagram showing the internal structure of the aerogel nanofiber of FIG. 1(b). [Figure 17] 1 is a flowchart showing a method for producing a rigid polymer molded article according to the present embodiment. [Figure 18] (a) is a schematic perspective view of an electrode in a manufacturing device for manufacturing a rigid polymer molded body of this embodiment, (b) is a schematic diagram of a hydrogel nanofiber molded body deposited on the electrode of (a), and (c) is a schematic diagram of an aerogel nanofiber molded body produced by drying (b). [Figure 19] 1(a) to 1(d) are diagrams illustrating a method for producing a cellulose nanofiber molded article of this example. [Figure 20] (a) is a diagram showing a cellulose nanofiber molded product produced by applying a voltage of 1 V in this example; (b) is a diagram showing a microscopic image of the cellulose nanofiber molded product of (a); (c) is a diagram showing a cellulose nanofiber molded product produced by applying a voltage of 5 V in this example; (d) is a diagram showing a microscopic image of the cellulose nanofiber molded product of (c); (e) is a diagram showing a cellulose nanofiber molded product produced by applying a voltage of 30 V in this example; and (f) is a diagram showing a microscopic image of the cellulose nanofiber molded product of (e). [Figure 21] FIG. 1(a) is a diagram showing a cellulose nanofiber molded article immediately after being produced by the production method of this example, and FIG. 1(b) is a diagram showing the cellulose nanofiber molded article after being dried. [Figure 22] (a) is a diagram showing the electrode used in producing the nanofiber molding of this example, (b) is a diagram showing the hydrogel cellulose nanofiber molding formed in this example, and (c) is a diagram showing the aerogel nanofiber formed in this example. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the rigid polymer molded article and the method for producing the rigid polymer molded article according to the present invention will be described. However, the present invention is not limited to the following embodiments, and can be embodied in various aspects without departing from the gist of the present invention. Note that where the explanation is redundant, the explanation may be omitted as appropriate.

[0020] [Embodiment 1] First, a rigid polymer molded body and a method for manufacturing a rigid polymer molded body according to this embodiment will be described with reference to Figures 1 to 9. Figure 1 is a schematic diagram of a manufacturing device 100 for manufacturing a rigid polymer molded body according to this embodiment.

[0021] 1, the manufacturing device 100 includes a container 110 and an electrode 120. The electrode 120 includes an electrode 122 and an electrode 124. At least a portion of the electrode 122 and the electrode 124 are disposed within the container 110.

[0022] The container 110 stores a rigid polymer dispersion LN. The rigid polymer dispersion LN can be prepared by dispersing a rigid polymer in a polar medium. For example, the rigid polymer dispersion LN is a nanofiber dispersion. The nanofiber dispersion can be prepared by dispersing nanofibers in a polar medium.

[0023] Typically, the rigid polymer dispersion LN is a suspension. The polar medium is, for example, water. The rigid polymer dispersion LN is produced by mixing a polar medium with a rigid polymer. In this specification, the rigid polymer dispersion LN may be simply referred to as the dispersion LN.

[0024] A pair of electrodes, electrode 122 and electrode 124, are immersed in the dispersion liquid LN. Thereafter, a DC voltage is applied between electrode 122 and electrode 124 for a predetermined time, thereby depositing rigid polymers (not shown in FIG. 1 ) on the surface of at least one of electrode 122 and electrode 124 in accordance with the shape of the electrode surface. When the DC voltage is applied, one of electrode 122 and electrode 124 becomes an anode, and the other of electrode 122 and electrode 124 becomes a cathode. When a rigid polymer that is negatively charged in a polar medium is used, the application of the DC voltage causes the rigid polymer to deposit on the surface of the anode. On the other hand, when a rigid polymer that is positively charged in a polar medium is used, the application of the DC voltage causes the rigid polymer to deposit on the surface of the cathode.

[0025] [Rigid polymer] A rigid polymer is a polymer having a rigid main chain structure. Typically, a rigid polymer is a nanofiber. However, a rigid polymer does not have to be a nanofiber.

[0026] [Nanofiber] Nanofibers are fibrous materials with a fiber diameter on the nano-order. The average fiber diameter (diameter) of nanofibers is 1 nm or more and 500 nm or less. The average fiber diameter of nanofibers may be 1 nm or more and 400 nm or less, or 1 nm or more and 350 nm or less. Typically, the length of nanofibers is 100 times or more the fiber diameter.

[0027] The nanofibers may be bionanofibers, which are biological polymers, or may be synthetic polymers.

[0028] The nanofibers may be cellulose nanofibers, chitinose nanofibers, or chitosan nanofibers, or a mixture thereof.

[0029] For example, cellulose nanofibers can be produced by bleaching and defibrating wood chips to form pulp fibers, followed by further defibration. Raw materials for cellulose nanofibers include, for example, bleached softwood kraft pulp, hardwood pulp, cotton pulp (more specifically, cotton linters, etc.), straw pulp, and bagasse pulp.

[0030] In this embodiment, the rigid polymer may be something other than a bionanofiber. Typically, a polymer with a rigid main chain structure exhibits liquid crystallinity and flow birefringence. When a concentrated aqueous solution of a rigid polymer is prepared at a certain concentration or higher, the rigid polymer forms a liquid crystal state in the solution. Furthermore, when an aqueous solution containing the rigid polymer is caused to flow, the polymer orients in the direction of flow and exhibits liquid crystallinity (flow birefringence). For example, it is preferable that the rigid polymer exhibits liquid crystallinity or flow birefringence at an aqueous solution concentration of 2% by weight or higher.

[0031] For example, typically, the polymer used as the rigid polymer in this embodiment includes a polysaccharide having a rigid main chain structure. The polysaccharide may have a linear main chain structure. For example, the rigid polymer in this embodiment includes carboxymethyl cellulose, alginic acid, hyaluronic acid, chondroitin sulfate, carrageenan, and xanthan gum. When producing these rigid polymers, the rigid polymer is deposited on the surface of the anode by application of a DC voltage.

[0032] [Polar medium] The polar medium is, for example, water, a polar organic solvent, or a mixture thereof. For example, polar organic solvents include methanol, ethanol, 2-propanol, acetone, dimethyl sulfoxide, ethylene glycol, acetonitrile, dioxane, and dimethylformamide. In order to obtain a rigid polymer dispersion containing rigid polymers at a higher concentration while further reducing production costs, water is preferred as the polar medium, and distilled water is more preferred.

[0033] [Rigid polymer dispersion LN] The rigid polymer dispersion LN is prepared by adding a rigid polymer to a polar medium. The rigid polymer dispersion LN contains the rigid polymer at a content of 0.01% by mass or more and 5% by mass or less. Typically, the electrical conductivity (specific electrical conductivity) of the rigid polymer dispersion LN is 0.80 mS / m or more and 35.00 mS / m or less. The specific electrical conductivity may be 0.80 mS / m or more and 30.00 mS / m or less, 0.80 mS / m or more and 20.00 mS / m or less, or 0.83 mS / m or more and 15.00 mS / m or less.

[0034] [Container 110] The rigid polymer dispersion liquid LN is stored in the container 110. For example, the container 110 is a beaker.

[0035] [Electrode 120] The electrode 120 is placed in the container 110. The electrode 120 includes an electrode 122 and an electrode 124. The electrode 122 and the electrode 124 are, for example, carbon electrodes, gold electrodes, platinum electrodes, silver electrodes, copper electrodes, or iron electrodes. The electrode 122 and the electrode 124 may be electrodes made of the same type of material, or may be electrodes made of different types of materials. In order to suppress dissolution of the electrode 122 and the electrode 124 when the rigid polymer is deposited, the electrode 122 and the electrode 124 are preferably a pair of carbon electrodes, a pair of gold electrodes, or a pair of platinum electrodes, and more preferably a pair of carbon electrodes.

[0036] In order to obtain a rigid polymer molding containing a higher concentration of rigid polymer while further reducing manufacturing costs, the distance between electrode 122 and electrode 124 may be 0.1 mm or more and 5000 mm or less, 1 mm or more and 500 mm or less, or 10 mm or more and 50 mm or less.

[0037] In order to obtain a rigid polymer molded body containing a higher concentration of rigid polymer while further reducing production costs, the length of the portion of electrode 122 and electrode 124 immersed in dispersion liquid LN may be 10 mm or more and 1000 mm or less, 10 mm or more and 500 mm or less, or 10 mm or more and 100 mm or less.

[0038] In order to obtain a rigid polymer molded article containing a higher concentration of rigid polymers while further reducing production costs, the DC voltage applied between electrode 122 and electrode 124 may be 0.1 V to 100,000 V, 1 V to 10,000 V, 1 V to 1,000 V, or 10 V to 100 V. For example, when a DC voltage of 0.1 V to 100,000 V is applied between electrode 122 and electrode 124, the DC current value between electrode 122 and electrode 124 is, for example, 0.001 A to 200 A.

[0039] To obtain a rigid polymer molded article containing a higher concentration of the rigid polymer, the time for applying the DC voltage (application time) may be 1 minute or more, or 5 minutes or more, and to further reduce production costs, the application time of the DC voltage may be 15 minutes or less, or 10 minutes or less.

[0040] After the rigid polymer is deposited to form a rigid polymer molded body on the surface of at least one of the electrodes 122 and 124, the rigid polymer molded body is, for example, separated from the electrode. When the rigid polymer is a bionanofiber, the nanofiber molded body is used as a naturally-derived material that can reduce the environmental burden (more specifically, as an industrial material, food additive, cosmetic additive, etc.).

[0041] Nanofiber molded products exhibit antiviral properties against the novel coronavirus. For example, nanofiber molded products can inactivate 99.8% of the novel coronavirus compared to commercially available PET films.

[0042] The method for producing a rigid-rod polymer molding according to this embodiment has been described above, but the method for producing a rigid-rod polymer molding according to the present invention is not limited to the above-described embodiment.

[0043] Next, a method for producing a rigid-rod polymer molded article according to this embodiment will be described with reference to Figures 1 and 2. Figure 2 is a flowchart showing the method for producing a rigid-rod polymer molded article according to this embodiment.

[0044] 2, in step S102, a rigid polymer dispersion is prepared. Typically, a rigid polymer is added to a polar medium to prepare a rigid polymer dispersion in which the rigid polymer is dispersed in the polar medium.

[0045] In step S104, the manufacturing device 100 is set up. Typically, the rigid polymer dispersion liquid LN is poured into the container 110 of the manufacturing device 100. Then, the electrodes 122 and 124 of the manufacturing device 100 are immersed in the rigid polymer dispersion liquid LN.

[0046] In step S106, a voltage is applied between the electrode 122 and the electrode 124. When a voltage is applied between the electrode 122 and the electrode 124, the rigid polymers in the rigid polymer dispersion LN migrate toward one of the electrode 122 and the electrode 124 and are deposited on one of the electrode 122 and the electrode 124. As a result, the charged state of the rigid polymers disappears at one of the electrode 122 and the electrode 124 and gels, thereby forming a rigid polymer molded article at one of the electrode 122 and the electrode 124.

[0047] Typically, the rigid polymer molded body formed on one of the electrodes 122 and 124 is dried. The dried rigid polymer molded body exhibits insulating properties. Thereafter, the rigid polymer molded body is separated from one of the electrodes 122 and 124. The rigid polymer molded body may be used in a state where it is deposited on one of the electrodes 122 and 124. For example, the electric field strength at the electrode on which the rigid polymer molded body is deposited, of the electrodes 122 and 124, is 500 V / cm or less. In this manner, a rigid polymer molded body can be produced on one of the electrodes 122 and 124.

[0048] Fig. 3 is a schematic diagram of a manufacturing device 100 for manufacturing a rigid polymer molding of this embodiment. The manufacturing device 100 in Fig. 3 has the same configuration as the manufacturing device 100 in Fig. 1, except that the arrangement and shape of the electrodes 120 are different, and therefore, redundant explanations will be omitted to avoid redundancy.

[0049] 3, the electrode 120 is immersed in the dispersion liquid LN. The electrode 122 is disposed at the bottom of the container 110, and the electrode 124 is disposed near the upper surface of the dispersion liquid LN.

[0050] Examples of materials that can be used to form the electrode 120 include metal materials and conductive metal oxide materials. When a metal material is used to form the electrode 120, usable metal materials include, for example, copper, silver, and nickel. When a conductive metal oxide material is used to form the electrode 120, usable conductive metal oxide materials include, for example, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO).

[0051] The rigid polymer is deposited on at least one of the electrodes 122 and 124. As the rigid polymer is deposited, a rigid polymer molded body is formed on at least one of the electrodes 122 and 124. The rigid polymer molded body is formed to conform to the shape of the surface of the electrode 122 or the electrode 124 on which the rigid polymer is deposited. Therefore, the rigid polymer molded body can be formed according to the shape of the electrode 122 and / or the electrode 124.

[0052] Here, the electrode 122 has a three-dimensional shape. The electrode 122 has at least one of a protrusion and a recess. When the rigid polymer is deposited on the electrode 122, the rigid polymer molded body can be formed into a shape corresponding to the three-dimensional shape of the electrode 122.

[0053] In one example, the electrode 122 has a flat portion 122a and a protruding portion 122b. The flat portion 122a and the protruding portion 122b are conductive. Here, the protruding portion 122b is disposed on the flat portion 122a and faces the electrode 124. For example, the protruding portion 122b is conical.

[0054] A rigid polymer is deposited on the surface 122s of the protrusion 122b that faces the electrode 124. Here, a convex portion that protrudes toward the electrode 124 is provided on the surface 122s of the protrusion 122b. Therefore, the surface 122s has regions with different normal directions. Note that, although the surface 122s of the protrusion 122b shown in FIG. 3 has a convex portion that protrudes toward the electrode 124, the surface 122s of the protrusion 122b may have a recessed portion.

[0055] Next, a method for producing a rigid-rod polymer molded article according to this embodiment will be described with reference to Figures 3 to 4(c). Figures 4(a) to 4(c) are schematic diagrams for explaining the method for producing a rigid-rod polymer molded article according to this embodiment.

[0056] As shown in FIG. 4(a), when a voltage is applied between electrode 122 and electrode 124 in the rigid polymer dispersion LN, the rigid polymer is deposited on electrode 122 to form a rigid polymer molded body NFh. The rigid polymer molded body NFh contains a rigid polymer and a polar medium. The rigid polymer molded body NFh is in a so-called gel state. When the polar medium of the rigid polymer dispersion LN is water, the rigid polymer molded body NFh is a hydrogel.

[0057] The rigid polymer molded bodies NFh adhere to the surface of the electrode 122 by, for example, Coulomb force or van der Waals force. Typically, the rigid polymer molded bodies NFh are deposited to a certain thickness on the electrode 122. The rigid polymer molded bodies NFh are formed according to the surface shape of the electrode 122. Here, the rigid polymer molded bodies NFh are formed according to the shape of the protrusions 122b.

[0058] When the rigid polymer is a cellulose nanofiber, the cellulose nanofiber is deposited on the anode electrode 122. When the rigid polymer is a chitinose nanofiber or a chitosan nanofiber, the chitinose nanofiber or the chitosan nanofiber is deposited on the cathode electrode 122.

[0059] As shown in Figure 4(b), when the polar medium evaporates from the rigid polymer molded material NFh and the rigid polymer molded material NFh dries, the rigid polymer molded material NFh shrinks to form a rigid polymer molded material NF. Typically, the rigid polymer molded material NFh is removed together with the electrode 122 from the rigid polymer dispersion liquid LN and left to stand, whereby the polar medium evaporates from the rigid polymer molded material NFh, forming a rigid polymer molded material NF. When the gel-like rigid polymer molded material NFh dries, the rigid polymer molded material NF shrinks while maintaining a constant thickness on the electrode 122. Typically, the thickness of the rigid polymer molded material NF is 100 nm or more and 200 µm or less.

[0060] As shown in Fig. 4(c), the rigid polymer molding NF is peeled off from the electrode 122. Here, the rigid polymer molding NF has a bent thin plate shape. The surface area of ​​the rigid polymer molding NF can be changed depending on the region of the electrode 122 where the rigid polymer is deposited.

[0061] The rigid polymer molded body NF contains nanofibers. The rigid polymer molded body NF may contain components other than nanofibers (other components). Examples of other components include resins (binder resins). When resins are used as other components, examples of resins that can be used include epoxy resins, polyurethane resins, acrylic resins, fluororesins, phenolic resins, silicone resins, polystyrene resins, polylactic acid resins, polycarbonate resins, polyethylene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride resins, polypropylene resins, and polyester resins.

[0062] According to this embodiment, the surface 122s of the electrode 122 on which the rigid polymer is deposited has protrusions or recesses that are larger than the thickness of the rigid polymer moldings NFh or rigid polymer moldings NF. This allows the rigid polymer moldings NF to be formed three-dimensionally on the surface 122s of the electrode 122. Therefore, the rigid polymer moldings NF can be formed into a shape that corresponds to the three-dimensional shape of the electrode 122.

[0063] In this embodiment, the rigid polymer molded body NF has a first main surface S1, a second main surface S2 that is the opposite side of the first main surface S1, and a side surface Ss connecting the first main surface S1 and the second main surface S2. Because the rigid polymer molded body NF is formed by depositing a rigid polymer on the three-dimensional electrode 122, the first main surface S1 and the second main surface S2 typically have shapes corresponding to the convex or concave portions of the electrode 122, and the shortest distance between the first main surface S1 and the second main surface S2 is constant. In this case, the normal direction of the first main surface S1 is antiparallel to the normal direction of the second main surface S2. One of the first main surface S1 and the second main surface S2 has a convex portion that is larger than the height Hs of the side surface Ss, and the other of the first main surface S1 and the second main surface S2 has a concave portion that is larger than the height Hs of the side surface Ss.

[0064] The rigid polymer molded body NF has advantages such as transparency, light weight, high strength, high heat resistance, high gas barrier, biodegradability, and sustainability. For example, the rigid polymer molded body NF can be used as a substitute for paper. In one example, the rigid polymer molded body NF can be used as wrapping paper or packaging. Alternatively, the rigid polymer molded body NF can be used as a substitute for plastic. For example, the rigid polymer molded body NF can be used as a straw or the like.

[0065] 3 and 4, the entire conductive electrode 122 has a three-dimensional structure, but this embodiment is not limited to this. The entire conductive electrode 122 does not have to have a three-dimensional structure.

[0066] Next, the production of a rigid polymer molding of this embodiment will be described with reference to Fig. 5. Fig. 5 is a schematic diagram of a production device 100 for producing a rigid polymer molding of this embodiment. The production device 100 of Fig. 5 has a configuration similar to that of the production device 100 of Fig. 3, except that only a portion of the three-dimensional electrode 120 is conductive, and therefore, to avoid redundancy, a duplicated description will be omitted.

[0067] 5, only a portion of the three-dimensional electrode 120 is conductive. Here, the electrode 122 has a three-dimensional structure, and only a portion of the electrode 122 is conductive.

[0068] The electrode 122 includes a base 122c and a conductive film 122d. The base 122c is insulating, and the conductive film 122d is conductive. For example, the base 122c has a conical shape. The conductive film 122d is disposed so as to cover the side surface of the base 122c. The conductive film 122d is formed by sputtering.

[0069] Next, the production of a rigid-rod polymer molded article of this embodiment will be described with reference to Figures 5 and 6. Figures 6(a) to 6(c) are schematic diagrams for explaining the production method of a rigid-rod polymer molded article of this embodiment.

[0070] As shown in Fig. 6(a), in the rigid polymer dispersion liquid LN, by applying a voltage between the electrode 122 and the electrode 124, the rigid polymer is deposited on the surface of the electrode 122 to form a rigid polymer molded body NFh. The rigid polymer molded body NFh is formed on the surface of the conductive film 122d. The rigid polymer molded body NFh is formed according to the surface shape of the conductive film 122d. The rigid polymer molded body NFh is gelled.

[0071] 6(b), the polar medium is evaporated from the rigid polymer molding NFh to form a dried rigid polymer molding NF. When the rigid polymer molding NFh dries, it shrinks to fit the surface shape of the electrode 120, and a dry rigid polymer molding NF is formed.

[0072] As shown in FIG. 6(c), the rigid polymer molding NF is separated from the electrode 122. For example, the rigid polymer molding NF may be peeled off from the electrode 122. Alternatively, at least a portion of the electrode 122 may be dissolved. For example, the base 122c may be dissolved. The base 122c may be dissolved by either heating or chemical treatment. In this manner, a rigid polymer molding NF corresponding to the shape of the electrode 122 can be produced.

[0073] 6(a), the conductive film 122d remains on the base 122c when the rigid polymer molded body NFh is formed, but this embodiment is not limited to this. The conductive film 122d may be ionized as the rigid polymer is deposited and dissolved in the rigid polymer dispersion liquid LN, and when the rigid polymer molded body NFh is formed, the conductive film 122d may disappear from the base 122c and dissolve in the rigid polymer dispersion liquid LNh.

[0074] The orientation direction of the rigid polymer molded body can be controlled. Specifically, the orientation direction of the rigid polymer molded body depends on the electric field strength near the electrode when the rigid polymer is deposited. For example, when the rigid polymer molded body is randomly oriented, the degree of orientation of the rigid polymer molded body is less than 15%. On the other hand, when the rigid polymer molded body is oriented horizontally or vertically, a rigid polymer molded body with an orientation degree of 20% or more can be formed. The degree of orientation of the rigid polymer molded body varies greatly depending on the applied voltage. For example, when oriented horizontally or vertically, the degree of orientation of the rigid polymer molded body is 20% or more and 90% or less. The degree of orientation of the rigid polymer molded body may be 40% or more and 80% or less, or 60% or more and 85% or less.

[0075] Next, rigid polymer molded articles having different orientation directions and a method for producing the same will be described with reference to FIGS.

[0076] First, referring to Figures 7(a) to 7(c), we will explain the rigid polymer molding deposited by applying a voltage at a relatively low electric field strength. Figure 7(a) is a schematic diagram of a rigid polymer molding NFh1 deposited by applying a voltage at a relatively low electric field strength, Figure 7(b) is a schematic diagram showing the orientation of rigid polymers in the rigid polymer molding NFh1 of Figure 7(a), and Figure 7(c) is a schematic diagram of the rigid polymer molding NF1 obtained by drying the rigid polymer molding NFh1 of Figure 7(a).

[0077] When a relatively low voltage is applied to the rigid polymer dispersion LN, the rigid polymers are deposited on the upper surface of the electrode 122 to form a rigid polymer molded body NFh1. Here, the rigid polymers are deposited on the micro-sized electrode 122.

[0078] As shown in FIGS. 7(a) and 7(b), when a voltage is applied with a relatively low electric field strength, the rigid polymers are layered in parallel to the surface of the electrode 122 in the rigid polymer molded body NFh1.

[0079] As shown in FIG. 7(c), the rigid polymer molded body NFh1 shrinks as it dries, becoming a rigid polymer molded body NF1. Typically, when the rigid polymer molded body NFh1 is removed from the rigid polymer dispersion liquid LN and left to stand, the polar medium evaporates from the rigid polymer molded body NFh1. The evaporation of the polar medium causes the rigid polymer molded body NFh1 to dry, becoming a shrunk rigid polymer molded body NF1. In this case, the rigid polymer molded body NFh1 shrinks parallel to the surface of the electrode 122.

[0080] In this way, by applying a voltage of a relatively low electric field strength to the electrode 122 in the rigid polymer dispersion LN, it is possible to form a rigid polymer molded body NFh1 in which the rigid polymers are oriented parallel to the surface of the electrode 122. For example, by applying a voltage of an electric field strength of 0.01 V / cm or more and 1 V / cm or less to the electrode 122 in the rigid polymer dispersion LN, it is possible to form a rigid polymer molded body NFh1 in which the rigid polymers are oriented parallel to the surface of the electrode 122.

[0081] The degree of orientation of the rigid-rod polymer molded body NFh1 or the rigid-rod polymer molded body NF1 can be measured using X-rays. For example, the degree of orientation of the rigid-rod polymer molded body is 70%.

[0082] Next, with reference to Figures 8(a) to 8(c), a rigid polymer molding deposited by applying a voltage at a moderate electric field strength will be described. Figure 8(a) is a schematic diagram of a rigid polymer molding NFh2 deposited by applying a voltage at a moderate electric field strength, Figure 8(b) is a schematic diagram showing the orientation of the rigid polymer molding NFh2 of Figure 8(a), and Figure 8(c) is a schematic diagram of a rigid polymer molding NF2 obtained by drying the rigid polymer molding NFh2 of Figure 8(a).

[0083] 8(a) and 8(b), when a moderate voltage is applied to the rigid polymer dispersion LN, the rigid polymer molded body NFh2 is deposited on the upper surface of the electrode 122. Here, the rigid polymer is deposited on the micro-sized electrode 122. In the rigid polymer molded body NFh2, the rigid polymer is randomly layered on the surface of the electrode 122.

[0084] As shown in FIG. 8(c), when the rigid polymer molded body NFh2 dries, it becomes a rigid polymer molded body NF2. Typically, when the rigid polymer molded body NFh2 is removed from the rigid polymer dispersion liquid LN and left to stand, the polar medium evaporates from the rigid polymer molded body NFh2. The evaporation of the polar medium causes the rigid polymer molded body NFh2 to dry and become a rigid polymer molded body NF2 in which the rigid polymer molded body NFh2 has shrunk. In this case, the rigid polymer molded body NFh2 shrinks in multiple directions relative to the surface of the electrode 122.

[0085] In this way, by applying a voltage of a medium electric field strength to the electrode 122 in the rigid polymer dispersion LN, it is possible to form a rigid polymer molded body NFh2 in which the rigid polymers are randomly oriented on the surface of the electrode 122. For example, by applying a voltage of an electric field strength of 2.1 V / cm or more and 5 V / cm or less to the electrode 122 in the rigid polymer dispersion LN, it is possible to form a rigid polymer molded body NFh2 in which the rigid polymers are randomly oriented on the surface of the electrode 122.

[0086] The degree of orientation of the rigid polymer molded body NFh2 or the rigid polymer molded body NF2 can be measured using X-rays. When the rigid polymers are randomly oriented with respect to the surface of the electrode 122, the degree of orientation of the rigid polymer molded body is 5%.

[0087] Next, a rigid polymer molding produced by applying a voltage at a relatively high electric field strength will be described with reference to Figures 9(a) to 9(c). Figure 9(a) is a schematic diagram of a rigid polymer molding NFh3 produced by applying a voltage at a relatively high electric field strength, Figure 9(b) is a schematic diagram showing the orientation of the rigid polymer molding NFh3 of Figure 9(a), and Figure 9(c) is a schematic diagram of a rigid polymer molding NF3 obtained by drying the rigid polymer molding NFh3 of Figure 9(a).

[0088] 9(a) and 9(b), when a voltage with a relatively high electric field strength is applied to the rigid polymer dispersion LN, the rigid polymer molded body NFh3 is deposited on the upper surface of the electrode 122. Here, the rigid polymer is deposited on the micro-sized electrode 122. In the rigid polymer molded body NFh3, the rigid polymer is layered in a direction perpendicular to the surface of the electrode 122.

[0089] As shown in FIG. 9(c), when the rigid polymer molded body NFh3 dries, it becomes a rigid polymer molded body NF3. Typically, when the rigid polymer molded body NFh3 is removed from the rigid polymer dispersion liquid LN and left to stand, the polar medium evaporates from the rigid polymer molded body NFh3. The evaporation of the polar medium causes the rigid polymer molded body NFh3 to dry and shrink, becoming a rigid polymer molded body NF3. In this case, the rigid polymer molded body NFh3 shrinks in a direction perpendicular to the surface of the electrode 122.

[0090] In this way, by applying a voltage with a relatively high electric field strength to the electrode 122 in the rigid polymer dispersion LN, it is possible to form a rigid polymer molded body NFh3 in which the rigid polymers are oriented in a direction perpendicular to the surface of the electrode 122. For example, by applying a voltage with an electric field strength of 5.1 V / cm or more and 50 V / cm or less to the electrode 122 in the rigid polymer dispersion LN, it is possible to form a rigid polymer molded body NFh3 in which the rigid polymers are oriented in a direction perpendicular to the surface of the electrode 122.

[0091] The degree of orientation of the rigid polymer molded body NFh3 or the rigid polymer molded body NF3 can be measured using X-rays. When the rigid polymer is oriented in the direction perpendicular to the surface of the electrode 122, the degree of orientation of the rigid polymer molded body is 70%.

[0092] As described above, by controlling the electric field strength applied to the electrode 122 in the rigid polymer dispersion LN, the orientation direction of the rigid polymer in the rigid polymer molded body NFh can be controlled.

[0093] 3 to 6, when forming the rigid polymer molding NF according to the surface of the electrode 122, it is preferable to set the electric field strength of the electrode 122 to 0.01 V / cm or more and 2 V / cm or less to form a rigid polymer molding NFh1 in which the rigid polymers are oriented in the horizontal direction relative to the surface of the electrode 122. This makes it possible to prevent the rigid polymer molding NF from cracking when the rigid polymer molding NFh shrinks, even if the rigid polymer molding NF is relatively thin.

[0094] Furthermore, it has been confirmed that rigid polymer molded articles formed by horizontal orientation have low friction properties, particularly in the hydrogel state before drying. For example, rigid polymer molded articles formed by horizontal orientation can reduce the friction coefficient to approximately 1 / 3 to 1 / 27 of that of rigid polymer molded articles formed by random orientation. Therefore, rigid polymer molded articles formed by horizontal orientation can be suitably used for artificial cartilage and / or lubricating coatings.

[0095] As described above, the rigid polymer molded body can be formed into a three-dimensional shape according to the surface shape of the electrode. The rigid polymer molded body may also be formed into a protrusion shape. For example, the rigid polymer molded body can be applied to a microneedle.

[0096] [Embodiment 2] Next, the rigid polymer molded body and the method for manufacturing the rigid polymer molded body of this embodiment will be described with reference to Figures 10 to 15. Figure 10(a) is a schematic diagram of the rigid polymer molded body of this embodiment, and Figure 10(b) is a schematic diagram of the rigid polymer molded body of Figure 10(a) used in a microneedle.

[0097] As shown in FIG. 10(a), the rigid polymer molding NF has a plurality of protrusions Np. Here, the plurality of protrusions Np are arranged in a matrix. For example, the height of the protrusions Np is 100 μm or more and 500 μm or less. The width of the protrusions Np is 5 μm or more and 1 mm or less. In this case, the rigid polymer molding NF is suitably used for injecting a drug solution into the skin for intradermal injection.

[0098] As shown in Figure 10(b), the rigid polymer molded body NF can be used as a microneedle. When a drug solution is applied to the protrusions Np of the rigid polymer molded body NF and the rigid polymer molded body NF is pressed against the skin, the tips of the protrusions Np of the rigid polymer molded body NF penetrate the stratum corneum Sc and the epidermis Ep, reaching the interface between the epidermis Ep and the dermis De. Therefore, the drug solution can be injected into the interface between the epidermis Ep and the dermis De without the rigid polymer molded body NF reaching the pain sensory nerves.

[0099] Here, we have explained that the medicinal solution for intradermal injection is injected into the interface between the epidermis Ep and the dermis De, but the height of the protrusion Np may be adjusted depending on the type of medicinal solution for subcutaneous injection, intravenous injection, and intramuscular injection.

[0100] As described above, the rigid polymer molded body NF can be suitably applied to microneedles.

[0101] Next, the production of the rigid polymer molded body NF of this embodiment will be described with reference to Fig. 11. Fig. 11 is a schematic perspective view of an electrode 122 used in the production of the rigid polymer molded body NF of this embodiment.

[0102] 11, the electrode 122 has an insulating plate 122n and conductive portions 122e. The conductive portions 122e are arranged in a matrix on the insulating plate 122n.

[0103] The insulating plate 122n has electrical insulation properties. Examples of materials for the insulating plate 122n include polyimide resin, a paper-phenolic resin composite material in which paper is impregnated with phenolic resin, and a glass-epoxy resin composite material in which glass woven fabric (cloth) is impregnated with epoxy resin. The thickness of the insulating plate 122n is, for example, 10 μm or more and 5 mm or less.

[0104] A plurality of openings are provided in the insulating plate 122n. The plurality of openings are arranged in a matrix on the insulating plate 122n. Conductive portions 122e are provided in the openings of the insulating plate 122n. Therefore, the conductive portions 122e are arranged in a matrix on the insulating plate 122n.

[0105] The width of the conductive portions 122e is, for example, 5 μm or more and 1 mm or less. The interval between the conductive portions 122e is, for example, 5 μm or more and 1 mm or less. The rigid polymer molded bodies are formed corresponding to the conductive portions 122e.

[0106] The rigid polymer molding NF is generated in correspondence with the conductive portion 122e of the electrode 122. Typically, the protrusions Np of the rigid polymer molding NF are formed so as to protrude from the conductive portion 122e on the upper surface at positions corresponding to the conductive portion 122e of the electrode 122. Therefore, the rigid polymer molding NF shown in FIG. 10(a) can be formed using the electrode 122 shown in FIG. 11.

[0107] Next, a method for producing a rigid-rod polymer molding NF according to this embodiment will be described with reference to Figures 10 to 12. Figure 12 is a flowchart showing the method for producing a rigid-rod polymer molding NF according to this embodiment.

[0108] In step S102, a rigid polymer dispersion liquid LN is prepared. Typically, the rigid polymer dispersion liquid LN can be prepared by adding a rigid polymer to a polar medium, in which the rigid polymer is dispersed in the polar medium.

[0109] In step S104, the manufacturing device 100 is set up. Typically, the rigid polymer dispersion liquid LN is poured into the container 110. The electrodes 122 and 124 of the manufacturing device 100 are immersed in the rigid polymer dispersion liquid LN. For example, in the manufacturing device 100, the electrode 122 shown in FIG. 11 is placed in the rigid polymer dispersion liquid LN.

[0110] In step S106, a voltage is applied between the electrode 122 and the electrode 124. The application of the voltage generates an electric field strength in a matrix pattern at the electrode 122. This allows the formation of a rigid polymer molding NF on the electrode 122, in which the protrusions Np are arranged in a matrix pattern.

[0111] Next, the rigid polymer molding NF of this embodiment will be described with reference to Fig. 13. Fig. 13(a) is a schematic diagram of the rigid polymer molding NFh of this embodiment before drying, and Fig. 13(b) is a schematic diagram of the rigid polymer molding NF of this embodiment after drying.

[0112] 13(a), a rigid polymer molding NFh is formed on the surface of a substrate S. The rigid polymer molding NFh has a plurality of protrusions Nph. The protrusions Nph are arranged on the upper surface of the substrate S in a matrix pattern.

[0113] The substrate S has electrical insulation properties. When the substrate S is immersed in the rigid polymer dispersion liquid LN, it is preferable that the rigid polymer dispersion liquid LN can penetrate or penetrate the substrate S in the thickness direction. The substrate S is porous. The pores of the substrate S may be formed by the constituent material of the substrate S, or may be through-holes that physically penetrate the substrate S. For example, the substrate S may be paper. Alternatively, the substrate S may contain a polyimide resin, a paper-phenolic resin composite material in which paper is impregnated with a phenolic resin, or a glass-epoxy resin composite material in which glass woven fabric (cloth) is impregnated with an epoxy resin. The thickness of the substrate S is, for example, 10 μm or more and 5 mm or less.

[0114] As shown in Figure 13(b), the polar medium evaporates from the rigid polymer molding NFh, forming a dried rigid polymer molding NF. In the rigid polymer molding NF, the protrusions Np are located in a matrix on the upper surface of the substrate S, similar to the protrusions Nph of the rigid polymer molding NFh. However, the protrusions Np in the rigid polymer molding NF are smaller than the protrusions Nph of the rigid polymer molding NFh. Typically, the height of the protrusions Np is 100 µm or more and 500 µm or less, and the width of the protrusions Np is 5 µm or more and 1 mm or less.

[0115] Next, the production of a rigid polymer molding of this embodiment will be described with reference to Fig. 14. Fig. 14(a) is a schematic diagram of the vicinity of an electrode 122 of a manufacturing device 100, and Fig. 14(b) is a schematic exploded perspective view of the electrode 122 of Fig. 14(a).

[0116] 14(a) and 14(b), the electrode 122 has a conductive plate 122f, a substrate S, and a mask member 122m. The substrate S is disposed on the conductive plate 122f. The mask member 122m is disposed on the substrate S. The substrate S is located between the conductive plate 122f and the mask member 122m.

[0117] The rigid polymer dispersion liquid permeates at least a part of the substrate S. The substrate S may be porous. Alternatively, the substrate S may have a plurality of through-holes.

[0118] A mask member 122m is placed on the substrate S. The mask member 122m is made of an insulating material. The mask member 122m is provided with predetermined through holes 122h. Typically, the mask member 122m has the predetermined through holes 122h arranged in a matrix.

[0119] When a voltage is applied to the conductive plate 122f, a rigid polymer molding is formed in an area of ​​the conductive plate 122f that corresponds to the through-holes 122h of the mask member 122m. Because the through-holes 122h are arranged in a matrix, the rigid polymer molding has a plurality of protrusions that correspond to the through-holes 122h.

[0120] FIG. 15 is a flowchart showing the method for producing a rigid polymer molding of this embodiment.

[0121] 15, in step S102, a rigid polymer dispersion is prepared. Typically, a rigid polymer is added to a polar medium to prepare a rigid polymer dispersion in which the rigid polymer is dispersed in the polar medium.

[0122] In step S104a, the manufacturing device 100 is set up. Typically, the rigid polymer dispersion liquid LN is poured into the container 110 of the manufacturing device 100. Then, the electrodes 122 and 124 of the manufacturing device 100 are immersed in the rigid polymer dispersion liquid LN. Here, the substrate S and the mask member 122m are attached to the electrode 122 of the manufacturing device 100.

[0123] In step S106, a voltage is applied between the electrode 122 and the electrode 124. By applying the voltage, protrusions of the rigid polymer molding NFh are formed in a matrix pattern on the electrode 122. This allows the formation of a rigid polymer molding NF on the electrode 122, with protrusions Np arranged in a matrix pattern.

[0124] As described above, according to this embodiment, the rigid polymer molded body NF can be formed from the rigid polymer dispersion LN.

[0125] The rigid-rod polymer molded body NF may have heat insulating properties. For example, the rigid-rod polymer may be dried into an aerogel state so as to have heat insulating properties.

[0126] [Embodiment 3] Next, the rigid polymer molding and the method for manufacturing the rigid polymer molding of this embodiment will be described with reference to Figures 16 to 18. Figure 16(a) is a schematic perspective view of an electrode 122 in a manufacturing device for manufacturing the rigid polymer molding of this embodiment, Figure 16(b) is a schematic diagram of an aerogel-like rigid polymer molding NFe formed on the electrode 122 of Figure 16(a), and Figure 16(c) is a schematic diagram showing the structure of the rigid polymer molding NFe of Figure 16(b).

[0127] 16(a), the electrode 122 here has a rectangular parallelepiped shape. The electrode 122 is used in a manufacturing device 100 that manufactures rigid polymer molded articles. Typically, a rigid polymer dispersion LN is poured into a container 110. The electrodes 122 and 124 of the manufacturing device 100 are immersed in the rigid polymer dispersion LN.

[0128] By applying a voltage between the electrode 122 and the electrode 124, the rigid polymer is deposited on the electrode 122, forming a gel-like rigid polymer molded product. Thereafter, by freeze-drying or supercritical drying the gel-like rigid polymer molded product, the polar medium in the gel-like rigid polymer molded product is replaced with air, and an aerogel-like rigid polymer molded product can be formed.

[0129] In freeze-drying, the polar medium in the rigid polymer molded body NFh is solidified at a temperature below its freezing point, and then the polar medium is removed by sublimation while the body is still in this state and dried. After freezing the polar medium in the rigid polymer molded body NFh by adjusting the temperature inside the dryer, the rigid polymer molded body is heated under low pressure to evaporate the polar medium by sublimation. This allows the polar medium to be removed from the rigid polymer molded body NFh while maintaining the rigid polymer framework in the rigid polymer molded body NFh, resulting in the formation of an aerogel-like rigid polymer molded body NFe.

[0130] In supercritical drying, the polar medium in the rigid polymer molded body NFh is removed and dried using a supercritical fluid. Typically, carbon dioxide is used as the supercritical fluid. After the polar medium in the rigid polymer molded body NFh is replaced with carbon dioxide using high-temperature, high-pressure carbon dioxide, the temperature and pressure are returned to room temperature and atmospheric pressure, and the carbon dioxide is further replaced with air. This allows the polar medium in the rigid polymer molded body NFh to be removed while maintaining the rigid polymer framework in the rigid polymer molded body NFh, resulting in the formation of an aerogel-like rigid polymer molded body NFe.

[0131] 16(b), the rigid polymer molding NFe covers the electrode 122. The rigid polymer molding NFe is formed in accordance with the surface shape of the electrode 122.

[0132] As shown in Figure 16(c), in the aerogel-like rigid polymer molding NFe, the rigid polymer skeleton is filled with air, which allows the rigid polymer molding NFe to exhibit high thermal insulation performance.

[0133] For example, rigid polymer molded articles are preferably used to cover pipes through which high-temperature liquids flow, to cover IC chips to protect them from ambient heat, or to utilize their heat insulating properties in space-related equipment.

[0134] Next, a method for producing a rigid polymer molding of this embodiment will be described with reference to Figures 16 and 17. Figure 17 is a flowchart showing the method for producing a rigid polymer molding of this embodiment.

[0135] 17, in step S102, a rigid polymer dispersion is prepared. Typically, a rigid polymer is added to a polar medium to prepare a rigid polymer dispersion in which the rigid polymer is dispersed in the polar medium.

[0136] In step S104, the manufacturing device 100 is set up. Typically, the rigid polymer dispersion liquid LN is poured into the container 110 of the manufacturing device 100. Then, the electrodes 122 and 124 of the manufacturing device 100 are immersed in the rigid polymer dispersion liquid LN.

[0137] In step S106, a voltage is applied between the electrode 122 and the electrode 124. This allows a gel-like rigid polymer molded object to be formed on one of the electrode 122 and the electrode 124. When the polar medium of the rigid polymer dispersion liquid LN is water, the rigid polymer molded object is a hydrogel.

[0138] In step S108, the rigid polymer molded body is freeze-dried or supercritically dried to form an aerogel-like rigid polymer molded body.

[0139] As described above, according to this embodiment, an aerogel-like rigid polymer molded product can be formed from the rigid polymer dispersion.

[0140] Next, a method for producing a rigid polymer molding of this embodiment will be described with reference to Fig. 18. Fig. 18(a) is a schematic perspective view of an electrode 122 used in producing a rigid polymer molding of this embodiment, Fig. 18(b) is a schematic diagram of a rigid polymer molding NFh obtained by depositing a rigid polymer on the electrode 122 of Fig. 18(a), and Fig. 18(c) is a schematic diagram of a rigid polymer molding NFe obtained by freeze-drying or supercritical drying the rigid polymer molding NFh of Fig. 18(b).

[0141] 18(a), an electrode 122 is prepared. Here, the electrode 122 has a substantially rectangular parallelepiped shape. In the rigid polymer dispersion liquid LN, a voltage is applied between the electrode 122 and the electrode 124. As a result, a rigid polymer molded body NFh is formed on the electrode 122.

[0142] 18(b), the rigid polymer molding NFh is formed so as to cover the electrode 122. Therefore, the rigid polymer molding NFh is formed according to the surface shape of the electrode 122. Thereafter, the rigid polymer molding NFh is freeze-dried or supercritically dried to form the rigid polymer molding NFe.

[0143] As shown in FIG. 18(c), the rigid polymer molding NFe is formed so as to cover the electrode 122. The rigid polymer molding NFe is an aerogel. The rigid polymer molding NFe is formed by evaporating the polar medium from the rigid polymer molding NFh while the skeleton of the rigid polymer molding NFh is generally maintained. Therefore, the rigid polymer molding NFe is formed in accordance with the surface shape of the electrode 122.

[0144] In this manner, a rigid polymer molded body NFe of aerogel having high heat insulating properties can be formed in accordance with the surface shape of the electrode 122. [Example]

[0145] Examples of the present invention will be described below, but the present invention is not limited to the scope of the following examples.

[0146] [Example 1] [Preparation of cellulose nanofiber dispersion] First, 2 g of cellulose nanofibers was added to 1000 g of water to prepare a cellulose nanofiber dispersion. The average fiber diameter of the cellulose nanofibers was 3 nm and the average length was 300 nm.

[0147] [Formation of cellulose nanofiber molded body] As shown in Figure 19(a), an electrode mold was prepared, with the surface of a pentagonal pyramid made of wax covered with a conductive thin film. The electrode mold was used as the anode and the fabricated device was set up. The distance between the anode and cathode was 4 cm.

[0148] Next, the anode and cathode were immersed in the cellulose nanofiber dispersion, and a voltage of 1 V was applied between the anode and cathode to form a cellulose nanofiber product on the surface of the anode. When the voltage was applied, the electric field strength near the anode was 0.25 V / cm.

[0149] As shown in Figure 19(b), cellulose nanofibers were deposited on the anode using an electrode mold to form a cellulose nanofiber molded product.

[0150] As shown in FIG. 19(c), when the cross section of the cellulose nanofiber product was cut, it was confirmed that the cellulose nanofibers were oriented parallel to the surface of the anode.

[0151] As shown in Figure 19(d), the anode was heated to melt the wax, and the cellulose nanofiber product was separated from the anode, forming a hollow pentagonal pyramid-shaped cellulose nanofiber product.

[0152] Next, the anode and cathode were immersed in the cellulose nanofiber dispersion, and a voltage of 1 V was applied between the anode and cathode to form a cellulose nanofiber molded product on the surface of the anode. At this time, the electric field strength of the anode was 0.25 V / cm.

[0153] [Orientation direction of samples A to C] Using the above-mentioned cellulose nanofiber dispersion, the voltage between the anode and cathode was changed to measure the orientation of samples A to C according to the electric field strength of the anode. Here, an electrode measuring 5 mm square was used as the anode.

[0154] Sample A was produced by applying a voltage of 1 V between the anode and the cathode. Figure 20(a) shows Sample A. When a voltage of 1 V was applied between the anode and the cathode, the electric field strength of the anode was 0.25 V / cm. Sample A was photographed under a microscope.

[0155] 20(b) shows a microscope image of Sample A. In Sample A, the cellulose nanofibers were oriented parallel to the surface of the electrode.

[0156] Sample B was produced by applying a voltage of 5 V between the anode and the cathode. Figure 20(c) shows Sample B. When a voltage of 5 V was applied between the anode and the cathode, the electric field strength of the anode was 1.25 V / cm. Sample B was photographed under a microscope.

[0157] 20(d) shows a microscope image of Sample B. In Sample B, the cellulose nanofibers were oriented in multiple directions relative to the surface of the electrode.

[0158] Sample C was produced by applying a voltage of 30 V between the anode and the cathode. Figure 20(e) shows Sample C. When a voltage of 30 V was applied between the anode and the cathode, the electric field strength of the anode was 7.5 V / cm. Sample C was photographed under a microscope.

[0159] 20(f) shows a microscope image of Sample C. In Sample C, the cellulose nanofibers were oriented perpendicular to the surface of the electrode.

[0160] [Example 2] The anode was formed by placing paper and a mask on a 40 mm square conductive plate. The mask was made of acrylic and measured 40 mm square. Through-holes with a diameter of 500 μm were formed in a matrix pattern in the mask. Adjacent through-holes were spaced 1.5 mm apart.

[0161] Next, an anode and a cathode were immersed in the cellulose nanofiber dispersion and a voltage of 30 V was applied between the anode and cathode to form a cellulose nanofiber product on the surface of the paper. The electric field strength of the anode was 7.5 V / cm.

[0162] As shown in Figure 21(a), a cellulose nanofiber molding with multiple protrusions on the paper was formed.

[0163] The cellulose nanofiber product was then left to dry at room temperature for 1 hour. As shown in Figure 21(b), the protrusions had shrunk compared to before drying.

[0164] [Example 3] As shown in Figure 22(a), a large-headed dog-shaped iron anode with a textured surface was used. This anode and a flat cathode were immersed in the cellulose nanofiber dispersion of the fabricated device. Then, a voltage was applied between the anode and cathode in the cellulose nanofiber dispersion.

[0165] As shown in Figure 22(b), hydrogel cellulose nanofibers were deposited on the surface of the anode by applying a voltage. Because the hydrogel cellulose nanofibers were deposited to a nearly constant thickness on the surface of the anode, the surface shape of the hydrogel cellulose nanofiber molded product was roughly the same as that of the anode.

[0166] The hydrogel cellulose nanofibers were then supercritically dried to form aerogel nanofibers using supercritical CO2 at a temperature of 40°C and a pressure of 10 MPa.

[0167] By supercritical drying, the water evaporated from the hydrogel cellulose nanofiber molded body, forming an aerogel nanofiber molded body, as shown in Figure 22(c). The surface shape of the aerogel cellulose nanofiber molded body was also roughly the same as that of the anode.

[0168] [Antiviral test] An aqueous solution containing SARS CoV 2 (JPN / TY / WK 521) virus strain was dropped onto a film of hydrogel cellulose nanofibers, and the solution was collected after 2 hours to evaluate the infectious titer. For comparison, the infectious titer of the virus was evaluated in comparison with that of a commercially available PET film.

[0169] [Table 1]

[0170] In the above table, TCID50 indicates 50% tissue culture infectious dose, and LRV indicates log reduction value.

[0171] As can be seen from the table above, it was confirmed that the hydrogel cellulose nanofiber molded body inactivated 99.8% of viruses compared to the commercially available PET film.

[0172] [Friction test] The friction coefficient of the nanofiber molded body formed with horizontal orientation was evaluated. A constant load test was performed using a measuring device (Tribogear TYPE14FW, manufactured by Shinto Scientific). In the constant load test, a 30 mm flat indenter with a load of 100 g was applied by moving it from a distance of 100 mm at a speed of 300 mm / m.

[0173] Cellulose nanofiber hydrogels formed with random and horizontal orientation were prepared as test samples. For random orientation of the cellulose nanofiber hydrogel, a voltage of 5 V was applied between the anode and cathode, with the anode field strength set to 1.25 V / cm. For horizontal orientation of the cellulose nanofiber hydrogel, a voltage of 1 V was applied between the anode and cathode, with the anode field strength set to 0.25 V / cm. Furthermore, alginate hydrogels formed with random and horizontal orientation were prepared as test samples.

[0174] [Table 2]

[0175] As can be seen from the table above, the static and dynamic friction coefficients of both the cellulose nanofiber hydrogel and the alginate hydrogel were lower for horizontal orientation than for random orientation. In particular, the dynamic friction coefficient was reduced to approximately 1 / 3 for the cellulose nanofiber hydrogel and to approximately 1 / 27 for the alginate hydrogel.

[0176] The above describes embodiments and examples of the present invention with reference to the drawings. However, the present invention is not limited to the above embodiments and examples and can be embodied in various forms without departing from the spirit and scope of the present invention. Furthermore, various inventions can be formed by appropriately combining multiple components disclosed in the above embodiments. For example, some components may be omitted from all components shown in the embodiments and examples. Furthermore, components from different embodiments may be appropriately combined. The drawings mainly show each component in a schematic manner to facilitate understanding. The thickness, length, number, spacing, etc. of each illustrated component may differ from the actual components due to the convenience of drawing. Furthermore, the materials, shapes, dimensions, etc. of each component shown in the above embodiments are merely examples and are not particularly limited. Various modifications are possible within a scope that does not substantially deviate from the effects of the present invention. [Industrial Applicability]

[0177] The rigid polymer molded article according to the present invention can be used, for example, as a paper substitute, a plastic substitute, a medical device, and / or a heat insulating material. [Explanation of symbols]

[0178] 100 Manufacturing Devices 110 Container 120 electrodes 122 electrodes 124 electrodes

Claims

1. a step of forming a rigid polymer molded body by depositing a rigid polymer on at least one of a first electrode and a second electrode from a rigid polymer dispersion in which the rigid polymer is dispersed in a polar medium; a step of drying the rigid polymer molded body; It encompasses in the step of forming the rigid polymer molded body, the at least one electrode has, on a surface on which the rigid polymer is deposited, a protrusion or a recess that is larger than a thickness of the rigid polymer molded body, In the step of forming the rigid polymer molded body, a voltage is applied to the at least one electrode so that the electric field strength is 0.01 V / cm or more and 1 V / cm or less, thereby orienting the rigid polymer parallel to the surface of the at least one electrode.

2. A process for forming a rigid polymer molded body by depositing a rigid polymer on at least one of a first electrode and a second electrode from a rigid polymer dispersion in which the rigid polymer is dispersed in a polar medium; a step of drying the rigid polymer molded body; It encompasses in the step of forming the rigid polymer molded body, the at least one electrode has, on a surface on which the rigid polymer is deposited, a protrusion or a recess that is larger than a thickness of the rigid polymer molded body, In the step of forming the rigid polymer molded body, a voltage is applied to the at least one electrode so that the electric field strength is 5.1 V / cm or more and 50 V / cm or less, thereby orienting the rigid polymer in a direction perpendicular to a surface of the at least one electrode.

3. A process for forming a rigid polymer molded body by depositing a rigid polymer on at least one of a first electrode and a second electrode from a rigid polymer dispersion in which the rigid polymer is dispersed in a polar medium; a step of drying the rigid polymer molded body; It encompasses in the step of forming the rigid polymer molded body, the at least one electrode has, on a surface on which the rigid polymer is deposited, a protrusion or a recess that is larger than a thickness of the rigid polymer molded body, In the step of forming the rigid polymer molded body, a voltage is applied to the at least one electrode so as to have an electric field strength of 1.25 V / cm or more and 5 V / cm or less, thereby orienting the rigid polymer in random directions with respect to the surface of the at least one electrode.

4. 4. The method for producing a rigid polymer molded body according to claim 1, wherein in the step of forming the rigid polymer molded body, the rigid polymer contains a polysaccharide having a linear main chain structure.

5. 4. The method for producing a rigid polymer molded body according to claim 1, wherein in the step of forming the rigid polymer molded body, the degree of orientation of the rigid polymer molded body is controlled according to the electric field strength in the at least one electrode.

6. 2. The method for producing a rigid polymer molded body according to claim 1, wherein in the step of forming the rigid polymer molded body, a voltage is applied to the at least one electrode so as to have an electric field strength of 0.01 V / cm or more and 1 V / cm or less, and the rigid polymer molded body is formed with an orientation degree of 40% or more in a direction parallel to a surface of the at least one electrode.

7. 3. The method for producing a rigid polymer molding according to claim 2, wherein in the step of forming the rigid polymer molding, a voltage is applied to the at least one electrode so as to achieve an electric field strength of 5.1 V / cm or more and 50 V / cm or less, and the rigid polymer molding is formed with an orientation degree of 40% or more in a direction perpendicular to a surface of the at least one electrode.

8. 4. The method for producing a rigid polymer molded body according to claim 1, wherein in the step of forming the rigid polymer molded body, the at least one electrode has an insulating base and a conductive film covering a surface of the base.

9. The method for producing a rigid polymer molded article according to claim 8 , further comprising the step of dissolving the base.

10. The method for producing a rigid polymer molded body according to claim 8 , wherein the conductive film is dissolved in the step of forming the rigid polymer molded body.

11. A method for manufacturing a rigid polymer molded body described in any one of claims 1 to 3, wherein in the process of forming the rigid polymer molded body, the rigid polymer molded body is formed having a plurality of protrusions arranged in a matrix pattern.

12. A method for manufacturing a rigid polymer molded body as described in claim 11, wherein in the step of forming the rigid polymer molded body, a substrate and a mask member formed from an insulating material and having a plurality of through holes arranged in a matrix pattern as the recesses are attached to the at least one electrode, and the voltage is applied to form the rigid polymer molded body on the surface of the substrate on the at least one electrode, with the plurality of protrusions arranged in areas corresponding to the plurality of through holes in the mask member.

13. A method for producing a rigid polymer molded body described in any one of claims 1 to 3, wherein in the step of drying the rigid polymer molded body, the rigid polymer molded body is freeze-dried or supercritically dried to obtain an aerogel-like rigid polymer molded body.

14. A rigid polymer molded article comprising a rigid polymer, A first major surface; a second main surface that is the back surface of the first main surface; a side surface connecting the first main surface and the second main surface, the first main surface has a protrusion that is greater in height than the side surface, the second main surface has a recess that is larger than the height of the side surface, The rigid-rod polymer molded article, wherein the rigid-rod polymers are oriented parallel to the first main surface.

15. A rigid polymer molded article comprising a rigid polymer, A first major surface; a second main surface that is the back surface of the first main surface; a side surface connecting the first main surface and the second main surface, the first main surface has a protrusion that is greater in height than the side surface, the second main surface has a recess that is larger than the height of the side surface, The rigid-rod polymer molded article has the rigid-rod polymer oriented in a direction perpendicular to the first main surface.

16. The rigid polymer molded article according to claim 14 or 15, wherein the rigid polymer comprises a polysaccharide having a linear main chain structure.

17. The rigid polymer molded article according to claim 14 , having a degree of orientation of 40% or more in a direction parallel to the first main surface.

18. The rigid polymer molded article according to claim 15 , having a degree of orientation of 40% or more in a direction perpendicular to the first main surface.

19. The rigid polymer molded article according to claim 14 or 15, wherein the rigid polymer has a bionanofiber or a rigid main chain structure.

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