JP4906539B2 - Honeycomb structure, method for manufacturing honeycomb structure, and image display device - Google Patents

Description

  The present invention relates to a honeycomb structure, a method for manufacturing a honeycomb structure, and an image display device.

  CRTs and liquid crystal displays are widely used as display terminals for so-called images such as characters, still images, and moving images. They can display and rewrite digital data instantly, but it is not easy to always carry the device. In addition, since it is a self-luminous device, there are problems such as eye fatigue when working for a long time and display not being maintained when the power is turned off. On the other hand, when a character or a still image is distributed or stored as a document, it is recorded on a paper medium by a printer. This paper medium is widely used as a so-called hard copy. Since hard copy sees reflections due to multiple scattering, it has better visibility than a self-luminous device and is less tiring. Moreover, since it is lightweight and excellent in handling, it can be read in a free posture. However, the hard copy is discarded after it is used. Some of them are recycled, but the recycling requires a lot of labor and cost, and there are problems in terms of resource saving. In recent years, with the development of information equipment, information processing such as document creation has been performed on a computer, and the opportunity to read text on a display terminal has greatly increased.

  Under such circumstances, there is a growing need for a paper-like display medium that can be rewritten with the advantages of both display and hard copy and that is suitable for the act of reading. Recently, a display medium using a polymer dispersed liquid crystal, a bistable cholesteric liquid crystal, an electrochromic element, an electrophoretic element, etc. has been actively researched and developed as a reflective display medium that can display brightly and has a memory property. Has been done. Among these, a display medium using an electrophoretic element is excellent in terms of display quality and power consumption during display operation. For example, Patent Document 1 discloses a principle invention.

  In an electrophoretic display medium, a dispersion liquid in which a plurality of electrophoretic particles having a color different from the color of the dispersion medium is dispersed in a colored dispersion medium between a pair of transparent electrodes. . In this case, the electrophoretic particles (also simply referred to as electrophoretic particles) are charged on the particle surface in the dispersion medium, and when a voltage for attracting the electrophoretic particles is applied to one transparent electrode side. Electrophoretic particles are attracted and accumulated on the transparent electrode side, and the color of the electrophoretic particles is observed. When a voltage repelling the charge of the electrophoretic particles is applied, the electrophoretic particles move to the opposite transparent electrode side. The color of the dispersion medium is observed. Display can be performed by using this change.

  Such an electrophoretic element is an individual image element, and in order to obtain an image display device, a large number of electrophoretic elements arranged in a fine region are required. Therefore, a structure for arranging these elements is required. A honeycomb structured sheet, which is an aggregate of a plurality of hollow structures, is known as a material suitable for arranging and arranging such fine elements. An electrophoretic particle and a dispersion medium are arranged in each honeycomb and one image element is formed at a time, so that an image display device can be obtained as a whole.

  For example, Patent Document 2 discloses an electrophoretic display and a manufacturing method thereof. This electrophoretic display is composed of a plurality of cells, each cell comprising 1) a wall for partitioning the cells, 2) a dispersion of charged dye particles dispersed in a dielectric solvent or solvent mixture, and 3 ) Formed by curing a supernatant layer of a sealing composition having a specific gravity smaller than that of the dispersion and formed by phase separation on the dispersion, so as to confine the dispersion in each cell. And a polymeric sealing layer that seals and adheres to the surface. This cell is formed as a plurality of cup-shaped recesses by microembossing or image exposure.

  In Patent Document 3, a plurality of honeycomb-shaped cells partitioned by partition walls are provided on a base material, electrophoretic particles composed of white particles and black particles in the cells, and a transparent dispersion medium that disperses the electrophoretic particles. There is disclosed an electrophoretic display panel in which a dispersion system comprising: As for the size of this cell, one side is 10 to 50 μm, the height is 30 to 50 μm, and the partition wall thickness is 0.5 to 10 μm. The honeycomb cell manufacturing method is such that a polymer solution in which a polymer is dissolved in a solvent is applied onto a substrate, and dried and fixed in a high-humidity environment to form a two-dimensional polymer network. Cell partition walls are produced by growing the substrate in the vertical direction of the substrate.

Moreover, as a manufacturing method of a honeycomb structure, a manufacturing method of an adhesion preventing material made of a biodegradable film having a honeycomb structure described in Patent Document 4 is disclosed. This honeycomb structure is formed of a biodegradable polymer and a phosphorus surfactant, and has a function of preventing adhesion of the honeycomb structure to the living body due to the effect of the surfactant. The film thickness of the honeycomb structure is approximately 13 μm.
JP 2004-189487 A Japanese Patent No. 3680996 JP 2005-148680 A International Publication No. 2004/148680 Pamphlet

  When the honeycomb structure is applied as a display unit matrix of an image display device such as an electrophoretic display, in order to obtain a display image with high reflectivity and high contrast, the pixel aperture ratio is large, that is, in the honeycomb hollow structure. It is preferable that the thickness of the partition wall, particularly the thickness of the partition wall on the display surface side opening, is small.

  In Patent Document 2, the honeycomb structure is formed by microembossing or image exposure, and the thickness of the wall partitioning each concave portion is not particularly described. However, for example, in microembossing for transferring a mold shape It is considered that it is difficult to form a structure with a partition wall thickness of 10 μm or less and a height of 5 times or more. (Cannot fill the mold groove, can not release).

  In Patent Document 3, it is possible to form a thin structure having a partition wall thickness of 10 μm or less. However, since it requires evaporation of an organic solvent or evaporation of water droplet groups arranged on the surface of a polymer solution, it takes a long manufacturing time. There is. In addition, since a process for evaporating the organic solvent is included, a dedicated chamber and a vapor recovery process are required in consideration of the influence on the environment and the human body, and the equipment becomes expensive. In addition, the opening shape tends to be a circular cell, and if the partition wall of the opening is thinned so as to increase the opening ratio, it is difficult to increase the opening ratio because the partition wall between the cells is thinned and connected to adjacent cells.

  In view of such problems, it is an object of the present invention to provide a honeycomb structure having a high aperture ratio and a thin partition wall, an efficient manufacturing method thereof, and an image display device using the honeycomb structure.

  The present inventors have found a method of forming a honeycomb structure using the force of gas expansion of a plurality of small bubbles in a film of a plastic material, and obtaining a honeycomb structure having a large aperture ratio and thin partition walls, It came to a solution. Specifically, the thin film stability of the honeycomb structure is enhanced by mixing an energy ray curable resin and a substance that lowers the surface tension thereof. By using a surfactant that is excellent in reducing the surface tension, the surfactant adsorbed on the surface of the thinned material flows during foaming to lower the surface tension, and the surface of the membrane due to the affinity between the surfactants. It is considered that the thin film state can be stabilized by obtaining effects such as homogeneous stabilization. The means for solving the problems of the present invention will be described below.

  According to the present invention, a plastic deformation film including a plastically deformable curable material that is cured by energy rays and a surface tension lowering agent that lowers the surface tension of the curable material is disposed on a substrate having a plurality of concave portions, and the concave portions The honeycomb structure obtained by irradiating and curing energy rays after forming a plurality of cells by being deformed by the volume expansion of the gas present in the substrate is included.

  The present invention includes the honeycomb structure, wherein the surface tension lowering agent is a surfactant.

  The present invention includes the honeycomb structure, wherein the surfactant is a fluorine-containing surfactant.

  The present invention includes the honeycomb structure in which the fluorine-containing surfactant has a fluoroalkyl group.

  The present invention includes the honeycomb structure in which the curable material is a nonionic resin, and the fluorosurfactant is a nonionic surfactant.

  The present invention includes the honeycomb structure in which the curable material is an ultraviolet curable resin.

  The present invention includes the honeycomb structure in which the ultraviolet curable resin is hydrophilic.

  The present invention includes the honeycomb structure, wherein the ultraviolet curable resin is a urethane acrylate resin.

  The present invention includes the honeycomb structure, wherein the ultraviolet curable resin is an epoxy acrylate resin.

  The present invention includes the honeycomb structure, wherein the ultraviolet curable resin is an alkoxy acrylate resin.

  The present invention includes an image display device in which a display unit is formed by inserting a display medium into each cell of the honeycomb structure.

  The present invention includes the object image display device in which the cell is filled with electrophoretic particles and an electrophoretic medium.

  The present invention includes a step of closely attaching a plastic deformation film including a plastically deformable curable material that is cured by energy rays and a surface tension lowering agent that lowers the surface tension of the curable material to a substrate surface having a plurality of recesses, A step of forming the plurality of cells by deforming the plastic deformation film by volume expansion of a gas existing in a concave portion on the surface of the base material; and a step of curing the plastic deformation film formed with the plurality of cells by irradiating energy rays. The manufacturing method of the honeycomb structure which has this.

  According to the present invention, it is possible to provide a honeycomb structure having a high aperture ratio and a thin partition wall, an efficient manufacturing method thereof, and an image display device using the honeycomb structure.

  The present invention relates to a plastic deformation film including a plastically deformable film-shaped cured material that is cured by energy rays such as ultraviolet rays and a surface tension lowering agent that lowers the surface tension of the cured material on a substrate having a plurality of recesses. The gas in the bubbles present in the recesses is arranged so as to be in close contact with the surface of the substrate while leaving bubbles in the recesses, and the pressure is reduced from the side opposite to the surface in close contact with the substrate surface of the film-like cured material. It is obtained by deforming the curable material by volume expansion of the material, hollowing the portions facing the respective recesses to form a plurality of cells, and irradiating the curable material on which the cells are formed with energy rays and curing. Honeycomb structure. In the present invention, by using a surfactant excellent in the effect of lowering the surface tension of the curable material, the surfactant in the cured material thinned during gas foaming flows to lower the surface tension of the curable material. It is considered that the effect of homogenous stabilization of the film surface due to the affinity between the surfactants can be expressed and the state of the thin film can be stabilized. By such an action, the stability of the honeycomb structure made of the thin film cured material is enhanced. In such a state, the honeycomb structure can be fixed by irradiating the cured material with energy rays and curing it.

  In general, when a similar hollow structure is formed using an energy curable resin such as an ultraviolet curable resin, there is an advantage that the process time can be shortened because a drying step is not required. However, since there are few volatile components, there is little volume shrinkage at the time of hardening, and when the partition was made thin, the partition was easy to tear and it was said that thickness reduction was difficult. Further, the ultraviolet curable resin does not cure or increase in viscosity until it is irradiated with ultraviolet rays, and if a thickness difference is caused when thinning proceeds during foaming, the thin portion may be easily broken. In the case of a radical-reactive UV curable resin, the curing reaction is hindered at the gas-liquid interface that comes into contact with oxygen in the air, and it becomes harder to cure as the cell becomes thinner. For this reason, when a difference in thickness occurs in the cell, the thinned portion is harder to be cured, is not sufficiently cured, is easily broken, and is difficult to manufacture.

  On the other hand, by mixing a substance that lowers the surface tension of the energy ray curable resin into the curable material, the film thickness unevenness is reduced when the film is thinned, and when a gas is blown into the film of the curable material, bubbles of bubbles are formed. It was confirmed that it was easy to occur and the lifetime of the generated bubbles was prolonged. Moreover, when irradiating the foam film with energy rays, it was confirmed that the bubble-like foam could be uniformly cured in the form of a thin film. It is considered that the influence of the inhibition of the curing reaction by oxygen is reduced by adsorbing the surfactant on the surface layer of the film. The effect of foam film formation and foam stabilization is particularly remarkable when using a fluorosurfactant that is particularly effective in reducing surface tension. When forming a hollow structure by the foaming method, the partition wall thickness is 10 μm. It is preferable to obtain a honeycomb structure having the following thin film.

  A method for manufacturing a honeycomb structure of the present invention will be described with reference to FIGS. 1, 2, and 3. 1 and 2 are production process diagrams for explaining an example of a method for producing a honeycomb structure of the present invention. FIG. 3 is a process diagram for making a honeycomb structure from a gelatin aqueous solution film as a reference example. First, as a basic method for manufacturing a honeycomb structure, a manufacturing process using a gelatin film in FIG. 3 will be described. A gelatin aqueous solution 3 is applied in a film form on a substrate 1 provided with a plurality of minute recesses on the surface of glass, metal, plastic or the like ((a) material application). A film of the gelatin aqueous solution 3 is formed so that the gas 6 remains in the recess space. When the surface of the substrate 1 and the film of the gelatin aqueous solution 3 are in close contact, the surface side of the film of the gelatin aqueous solution 3 is decompressed, and the gas 6 in the space of the recess is expanded. The gas 6 expands the film of the gelatin aqueous solution 3 so as to push the gelatin aqueous solution 3 upward on the surface side (upward in the figure), and forms a hollow in the film of the gelatin aqueous solution 3. At this time, since the gas 6 generated from each recess forms a hollow, the entire membrane has a honeycomb structure ((b) material deformation). If the honeycomb structure of the gelatin aqueous solution 3 is dried as it is, a gelatinous honeycomb structure is obtained ((c) material hardening).

  The manufacturing method of the honeycomb structure shown in FIG. 1 is similar to the manufacturing method of the gelatinous honeycomb structure described above, but uses an ultraviolet curable resin 4 containing a surfactant at the stage of material application. The ultraviolet curable resin 4 may be attached to the surface of the base material 1 after being formed into a film or sheet ((a) material application), or may be attached while spreading the material on the surface of the base material 1. Good. (B) The material deformation may be the same as in the case of the gelatin aqueous solution. At this time, the surfactant exerts an effect to facilitate the formation of a honeycomb structure having thin partition walls. In this case, the thickness of the honeycomb structure can be adjusted by the degree of decompression. (C) In the material curing, the ultraviolet curable resin 4 is cured by irradiating ultraviolet rays. Also in this case, the surfactant exhibits an effect, and it is easy to form a honeycomb structure having thin partition walls.

  Normally, energy ray curable materials such as ultraviolet rays have almost no volatile components, and unlike the process using gelatin aqueous solution as a material (FIG. 3), it does not require a drying step that takes several minutes. It is. In general, the energy ray curable material can be cured within 10 seconds, so that the process time can be greatly reduced.

  The manufacturing method of the honeycomb structure shown in FIG. 2 is a modification of the manufacturing method of the honeycomb structure shown in FIG. 1, and the material of the ultraviolet curable resin 4 is applied to the surface of the base material 1 by the substrate 2 that functions as a restraining plate. It is adhered while developing ((a) material application). Then, while the substrate 2 is arranged in a film shape of the ultraviolet curable resin 4, the upper portion of the substrate 2 is reduced in pressure to form a honeycomb structure in the film of the ultraviolet curable resin 4 ((b) material deformation). While the ultraviolet curable resin 4 is in close contact with the substrate 1 and the substrate 2, the substrate 2 is separated from the substrate 1, whereby the ultraviolet curable resin 4 is pulled up and down, and the space in the concave portion of the substrate 1 is decompressed by the stress. And the gas therein may be expanded. In this case, the thickness of the honeycomb structure can be adjusted by the moving distance upward of the substrate 2. When the honeycomb structure is formed, ultraviolet irradiation is performed to cure the ultraviolet curable resin 4 to form a honeycomb structure ((c) material curing). If the substrate 2 is made of ultraviolet transmissive glass or the like, ultraviolet irradiation can be performed while the substrate 2 is placed.

  In this case, unlike the gelatin aqueous solution, there is no need to provide an arousal space for drying the material after foaming under reduced pressure. Therefore, the above-described decompression foaming and curing steps are performed with the UV curable resin 4 sandwiched between the substrate 1 and the substrate 2. As a result, the honeycomb structure can be directly formed on the target substrate on which a fine honeycomb structure is to be formed. Therefore, there is an advantage that the bonding process of the honeycomb structure and the transfer process of transferring to the substrate can be omitted.

  In the present invention, a structure forming material having a plastic deformation function is applied to the upper surface of a mold substrate having a large number of minute recesses arranged on the upper surface at a high density to cover the upper surface of the mold substrate. The structure forming material is stretched by the gas pressure in the sealed space by the layers, and the plurality of spaces are expanded and stretched at the same time, thereby forming a large number of thin hollow bodies with thin partition walls of micron order in a certain direction. Thus, a honeycomb structure can be configured. The concave portions on the substrate are not connected to the adjacent concave portions and exist independently.

  In the honeycomb structure of the present invention, the cross-sectional structure of each cavity of the honeycomb structure can be changed depending on the arrangement form of the recesses on the substrate. For example, when the recesses on the substrate are arranged in a hexagonal close-packed state (hexagonal close-packed state), the opening shape (cavity cross-sectional structure) of the deformed honeycomb structure can be a hexagon. Moreover, if the arrangement of the recesses on the substrate is a square lattice, the shape of the opening of the honeycomb structure can be a square. FIG. 4 is a schematic diagram of a square lattice-shaped recess, and FIG. 5 is a schematic diagram of a hexagonal close-packed recess. Here, a sheet-like structure in which a large number of cells are arranged is used as the honeycomb structure regardless of the cross-sectional structure including both. In general, when the cell aperture ratio becomes higher than a certain level, the cell cross-sectional shape becomes hexagonal or quadrangular. However, when the cell aperture ratio is low and the ratio of the partition walls is high, the cell cross-sectional shape tends to be circular.

  As shown in FIGS. 4 and 5, it is preferable that the opening of the recess is smaller than the internal cross section, that is, the wall surface width in the recess is equal to or greater than the entrance width. In this way, it is possible to secure a sufficient gas volume to expand into the recess, while ensuring a sufficient contact area between the substrate and the film of the curable material. 4 and 5, the shape of the opening of the recess is a circle or an ellipse, and the internal cross-sectional shape is a square or a hexagon, but the shape of the recess is a shape that can secure a sufficient gas volume to expand. Anything can be used.

  In the method for manufacturing a honeycomb structure using foaming as described above, in order to reduce the cell partition walls, it is desirable that the material layer on the substrate is formed into a foam film by gas expansion. According to the Young-Laplus equation indicating the properties of the foam film, the curvature R and angle of the intersecting portion of the foam film depend on the pressure difference on both sides of the foam film and the surface tension of the foam film. Therefore, it is necessary to lower the surface tension in order to form a hollow structure with a fine hexagonal opening shape. It is known that a foam film can be easily formed by using a number of surfactants such as alkyl sulfates in aqueous solution-based materials. It is necessary to evaporate moisture, which is not preferable as a method for manufacturing a honeycomb structure.

  A specific configuration example of the honeycomb structure will be described. It is a sheet-like structure in which hollow spaces partitioned by thin partition walls are arranged, and depending on how the partition walls are partitioned, a honeycomb structure in which hollow portions are opened in a hexagonal shape, a structure in which square openings are arranged in a lattice shape, and openings are Circular ones can also be formed. Only one side of the sheet may be opened, or both sides may be opened. When used as a matrix of a display unit of an image forming apparatus, the contrast and reflectance of an image are lowered unless the aperture ratio is high. Therefore, the partition wall thickness is preferably within 10 μm.

Here, an example of the partition wall thickness h of the honeycomb structure obtained by the above-described manufacturing method using gas expansion will be described with reference to FIG.
(A) A honeycomb structure of the present invention manufactured by a manufacturing method shown in FIG. 1 or 2 with a cured material obtained by adding a fluorosurfactant to an ultraviolet curable resin: partition wall thickness of 0.01 to 5 μm
(B) A honeycomb structure manufactured by a manufacturing method shown in FIG. 1 or 2 with a hardening material made only of an ultraviolet curable resin: a partition wall thickness of 10 μm or more (c) A hardening material made of a gelatin material is manufactured by the manufacturing method shown in FIG. Manufactured honeycomb structure: partition wall thickness 0.01 to 5 μm
As described above, the honeycomb structure of the present invention of (a) and the honeycomb structure made of the gelatin material of (c) have a partition wall thickness cell height (cell height) of 10 μm. It has a shape suitable as a constituent material of the part.

  In general, in an energy ray curable material, it may be difficult to use a surfactant having a low water content and effective in an aqueous solution system as a surface tension reducing agent as it is. In this respect, energy beam curable materials that are soluble in both aqueous and organic solvent systems and have an excellent effect of lowering the surface tension have a remarkable effect on thinning the hollow structure film. . Oligomers in which fluoroalkyl groups are introduced only at the ends have high orientation at the gas / liquid (water or organic solvent) interface, and the fluoroalkyl segments introduced at the ends do not repel each other, but aggregate in the opposite direction. It is known to exhibit a facile property, and this property is believed to act particularly effectively in stabilizing the foam film formed.

The honeycomb structure of the present invention will be described with reference to various embodiments.
(Embodiment 1)
The honeycomb structure produced by the manufacturing method shown in FIG. 2 is, for example, in the form of a sheet, and is a honeycomb structure having an opening of each cell on at least one side of the sheet. As the energy ray curable substance, for example, a substance that cures by a crosslinking reaction or a polymerization reaction by absorption of energy rays such as ultraviolet rays, electron beams, and far infrared rays may be used. Any deformable state may be used. Any substance that lowers the surface tension can be used as long as it is mixed with the energy ray-curable substance and adsorbed on the interface between the solvent, the dispersion, and the gas-liquid interface. The substance that lowers the surface tension may be organic, inorganic, silicon, low molecule, oligomer, or polymer, and is preferably a substance that lowers the surface tension of the energy ray curable substance by 5 dyne / cm or more. A substance that lowers by 10 dyne / cm or more is preferable.

  The wall thickness between each cell of the honeycomb structure can be formed in a range of 0.01 to 10 μm. By using each cell of the honeycomb structure as a pixel of each electrophoretic display element, display characteristics can be improved. An excellent image display device can be obtained. The fine honeycomb structure composed of the curable material used in the present invention can have a thinner wall thickness than that using only the ultraviolet curable resin. Since the partition wall does not contribute to display, the reflectance and contrast are improved by being thinned. The partition wall thickness is preferably about 0.05 to 5 μm. This is because when the partition wall thickness is 0.05 μm or less, the strength of the honeycomb structure is weak, and when it is 5 μm or more, the characteristics in terms of reflectance and contrast are not good.

  In the manufacture of honeycomb structure, it is possible to select an energy ray-curable material with a small amount of volatile components, which does not require drying time and is cured in a short time with a commercially available energy ray light source such as an ultraviolet light source. Therefore, the equipment is inexpensive, the process time can be shortened, and the productivity can be improved.

  In addition, the honeycomb structure of the present invention can be directly formed on a base film by using an energy ray curable material having a small amount of volatile components (since it is formed by a manufacturing method in which bubbles are expanded). Thus, when used in an image display device or the like, productivity can be improved by omitting a process such as bonding the completed honeycomb structure to another member.

(Embodiment 2)
The honeycomb structure of the second embodiment is manufactured in the same manner as the honeycomb structure of the first embodiment, but an electron beam curable resin containing a surfactant is used as the energy beam curable resin. For example, as an electron beam curable resin, unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, unsaturated acrylic resin, unsaturated silicone, unsaturated fluorine resin, etc. (preferably urethane acrylate type, epoxy acrylate type) May be used.

  Any surfactant that lowers the surface tension of the electron beam curable resin can be used as long as it is an amphiphilic substance that mixes with the electron beam curable resin and is dissolved, dispersed, or adsorbed on the gas-liquid interface to lower the surface tension. good. The surfactant is a substance having a hydrophilic part and a hydrophobic part, and may be an organic, inorganic, silicon, low molecule, oligomer, or polymer. The surface tension of the energy ray curable substance is 5 dyne / cm or more. A substance that lowers the surface tension is preferable, and a substance that lowers the surface tension by 10 dyne / cm or more is preferable. For example, silicone surfactants with polyorganosiloxane as a hydrophobic group exhibit a great ability to lower surface tension, and polyoxyalkylene, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, ammonium salt, etc. are modified as hydrophilic groups. A modified silicone surfactant contained as a group may be used.

  The wall thickness between the cells of this fine honeycomb structure can be formed in the range of 0.01 to 10 μm. By using such a honeycomb structure for an electrophoretic display device, display characteristics are improved. In addition, it has the same function and action as the first embodiment.

(Embodiment 3)
The honeycomb structure according to the third embodiment is manufactured in the same manner as the honeycomb structure according to the second embodiment, but a fluorine-based surfactant, particularly a fluorine-containing amphiphile is used as the surfactant. The fluorosurfactant is a substance containing fluorine and having a hydrophobic part and a hydrophilic part, and may be a low molecule, an oligomer or a polymer, and lowers the surface tension of the energy ray curable substance by 5 dyne / cm or more. A substance is preferable, and a substance that lowers the surface tension by 10 dyne / cm or more is particularly preferable. This form of honeycomb structure also has the same performance and characteristics as the honeycomb structures of Embodiments 1 and 2 described above, and can be used for similar applications.

(Embodiment 4)
The honeycomb structure of the fourth embodiment is manufactured in the same manner as the honeycomb structure of the third embodiment, but a surfactant having a fluoroalkyl group is used as the surfactant. The surfactant having a fluoroalkyl group may be an amphiphilic substance having a fluoroalkyl group which is mixed with the energy ray curable substance and is dissolved, dispersed, or adsorbed on the gas-liquid interface to lower its surface tension. It ’s fine. It is a substance having a fluoroalkyl group and having a hydrophobic part and a hydrophilic part, and may be a low molecule, an oligomer, or a polymer, and a substance that lowers the surface tension of the energy ray curable substance by 5 dyne / cm or more is good. A substance that lowers the surface tension by 10 dyne / cm or more is desirable.

  The surfactant having a fluoroalkyl group preferably contains a perfluoroalkyl group in which all hydrogen in the alkyl group is substituted with fluorine, but may be one in which hydrogen at the end of the alkyl group is substituted with fluorine. Alternatively, the hydrogen at the terminal end of the alkoxy group may be substituted with fluorine. Examples of fluorosurfactants include perfluoroalkyl group-containing amphiphilic oligomers, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group-containing sulfonates, perfluoroalkyl group-containing carboxylates, and perfluoroalkyls. Group-containing carboxylic acid, perfluoroalkyl group-containing phosphate ester, perfluoroalkyl group-containing sulfonamide, perfluoroalkyl group-containing ammonium phosphate salt, perfluoroalkyl group-containing carboxylic acid ammonium salt, perfluoroalkyl group-containing acrylate polymer, and Such a copolymer may be used.

  This type of honeycomb structure also has the same performance and characteristics as the honeycomb structures of Embodiments 1, 2, and 3 described above, and can be used for similar applications.

(Embodiment 5)
The honeycomb structure of Embodiment 5 is made of a material containing a nonionic energy ray curable resin and a nonionic surfactant. For example, this honeycomb structure has a sheet shape, and corresponds to a structure in which a plurality of hollow cells each having an opening of each cell of the honeycomb structure are arranged on at least one side of the sheet. The nonionic energy ray curable substance may be any nonionic resin that cures by a crosslinking reaction or a polymerization reaction by absorption of energy rays such as ultraviolet rays, electron beams, and far infrared rays. The state may be any state that can be plastically deformed. For example, epoxy acrylate, urethane acrylate, or the like may be used as the nonionic resin.

  Any nonionic surfactant may be used as long as it is an amphiphilic substance that is mixed with an energy ray-curable substance and is dissolved, dispersed, or adsorbed on the gas-liquid interface to lower its surface tension. Organic, inorganic, silicon-based, low-molecular, oligomer, and high-molecular materials may be used, and a material that lowers the surface tension of the energy ray-curable material by 5 dyne / cm or more is preferable, and desirably the surface tension is lowered by 10 dyne / cm or more. The substance is good. For example, examples of nonionic surfactants include perfluoroalkyl group-containing amphiphilic oligomers, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group-containing sulfonamides, perfluoroalkyl group-containing acrylate polymers, and copolymers thereof. It may be used.

  The honeycomb structure of this form also has the same performance and characteristics as the honeycomb structures of Embodiments 1 to 4 described above, and can be used for similar applications. Furthermore, since the honeycomb structure does not have ionicity due to the nonionic property that is a characteristic of nonionic materials, when used in an image display device, it is electrically connected to pixel components such as electrophoretic particles fixed to the inner wall. It is possible to prevent problems caused by various factors.

(Embodiment 6)
The honeycomb structure of Embodiment 6 uses a curable material containing an ultraviolet curable resin and a substance that lowers the surface tension. The ultraviolet curable resin may be a substance that cures by a crosslinking reaction or a polymerization reaction by absorption of ultraviolet rays, and may be in a state in which the state before ultraviolet irradiation can be plastically deformed. For example, polyester acrylate, polyether acrylate, acrylic oligomer acrylate, urethane acrylate, epoxy acrylate, polybutadiene acrylate, silicone acrylate UV curable resin (preferably urethane acrylate, epoxy acrylate) is relatively quick Since it cures, it is suitable for obtaining a stable shape. In addition to this UV curable resin material, a photopolymerization initiator for absorbing ultraviolet rays to initiate polymerization, a sensitizer for sensitizing light absorption sensitivity at an arbitrary wavelength, and sensitivity by interaction with the polymerization initiator It is effective to add a polymerization accelerator or the like to increase the degree of curing.

  Any substance that lowers the surface tension can be used as long as it is mixed with the energy ray-curable substance and adsorbed on the interface between the solvent, the dispersion, and the gas-liquid interface. The substance that lowers the surface tension may be organic, inorganic, silicon, low molecule, oligomer, or polymer, and the substance that lowers the surface tension of the energy ray curable substance by 5 dyne / cm or more is preferable. It is preferable to use a substance that lowers 10 dyne / cm or more.

  The honeycomb structure of this form also has the same performance and characteristics as the honeycomb structures of Embodiments 1 to 4 described above, and can be used for similar applications. When urethane acrylate resin is used as the main component of the curable material, the honeycomb structure has excellent flexibility and can improve reliability when used in an image display device for a thin display. Furthermore, the urethane acrylate resin is excellent in chemical resistance, can be prevented from being compatible with an electrophoretic liquid composed of a hydrophobic organic solvent, and can obtain stable display characteristics over time. Further, when the epoxy acrylate resin is used as the main component of the curable material, when the honeycomb structure is used in the image display device, the bondability with the electrode material can be improved. In addition, it is excellent in chemical resistance, can be prevented from being compatible with an electrophoretic liquid composed of a hydrophobic organic solvent, and can obtain stable display characteristics over time. When an alkoxy acrylate resin is used as the main component of the curable material, compatibility with an electrophoretic liquid composed of a hydrophobic organic solvent can be prevented, and when used in an image display device, stable display characteristics over time. Obtainable.

(Embodiment 7)
The honeycomb structure of the seventh embodiment uses a curable material made of a material containing a hydrophilic ultraviolet curable resin and a substance that lowers the surface tension in the honeycomb structure of the seventh embodiment. This honeycomb structure is, for example, a sheet shape, and corresponds to a structure in which a plurality of hollow cells having openings of each cell of the honeycomb structure are arranged on at least one side of the sheet. The hydrophilic ultraviolet curable resin is a substance that contains a hydrophilic functional group and has a water-soluble structure or a high affinity with water, and is cured by a crosslinking reaction or a polymerization reaction by absorption of ultraviolet rays. What is necessary is just to be a state in which the state before ultraviolet irradiation can be plastically deformed. For example, polyalkoxy acrylate-based, urethane acrylate-based, epoxy acrylate-based UV curable resins and the like are suitable for obtaining a stable shape because they cure relatively quickly.

  In addition to hydrophilic UV curable resin, photopolymerization initiator for initiating polymerization by absorbing ultraviolet rays, sensitizer for sensitizing light absorption sensitivity at any wavelength, sensitivity by interaction with polymerization initiator It is effective to add a polymerization accelerator or the like to increase the degree of curing.

  Any substance that lowers the surface tension can be used as long as it is mixed with the ultraviolet curable resin and adsorbed on the interface between the solvent, the dispersion, or the gas-liquid interface. The substance that lowers the surface tension may be organic, inorganic, silicon, low molecule, oligomer, or polymer, and the substance that lowers the surface tension of the energy ray curable substance by 5 dyne / cm or more is preferable. It is preferable to use a substance that lowers 10 dyne / cm or more.

  The honeycomb structure of this form also has the same performance and characteristics as the honeycomb structures of Embodiments 1 to 4 described above, and can be used for similar applications. In addition, since the hydrophilic UV curable resin is the main component of the honeycomb structure, it is easy to prevent compatibility with the electrophoretic liquid composed of a hydrophobic organic solvent. When used in a display device using electrophoresis Thus, stable display characteristics can be obtained over time.

(Embodiment 8)
Embodiment 8 is an image display device using the above honeycomb structure. An image display apparatus according to Embodiment 8 is an apparatus using any of the above-described honeycomb structures of the present invention as a pixel matrix of an image display section, and an electrophoretic agent (electrophoretic particles) is placed inside the cells of the honeycomb structure. And an electrophoretic medium slurry), an liquid crystal display filled with a liquid crystal material, an EL display filled with a fluorescent material, and an electrowetting display. A honeycomb structure having a large number of fine cells has a cell partition wall thickness thinner than that used as a curing material using only an ultraviolet curable resin. Since the partition walls of the cells do not contribute to display, the reflectance and contrast are improved by being thinned. The partition wall thickness of the cell of the pixel matrix of the image display device is preferably about 0.05 to 5 μm. This is because when the partition wall thickness is 0.05 μm or less, the strength of the honeycomb structure is weak, and when it is 5 μm or more, the characteristics in terms of reflectance and contrast are not good.

  In the image display device of this embodiment, since the honeycomb structure having fine cells of the present invention is used, the partition wall thickness of the display portion matrix can be 10 μm or less, and the reflectance is increased by the high aperture ratio of the cells of the display portion matrix. And image characteristics with excellent contrast can be obtained.

(Embodiment 9)
Embodiment 9 is an electrophoretic image display device in which an electrophoretic agent is filled in the cells of the honeycomb structure among the above-described image display devices using the honeycomb structure. This electrophoretic image display device is a device using a honeycomb structure as a pixel matrix of an image display unit, and is an electrophoretic display in which an electrophoretic agent is filled in a cell. The fine honeycomb structure has a thinner wall thickness than that of the conventional example using the ultraviolet curable resin. Since the partition wall does not contribute to display, the reflectance and contrast are improved by being thinned. The partition wall thickness is preferably about 0.05 to 5 μm. When the partition wall thickness is 0.05 μm or less, the strength of the honeycomb structure is weak, and when it is 5 μm or more, the characteristics in terms of reflectance and contrast are not good. In the image display device of this embodiment, since the honeycomb structure having fine cells of the present invention is used, the partition wall thickness of the display portion matrix can be 10 μm or less, and the reflectance is increased by the high aperture ratio of the cells of the display portion matrix. And image characteristics with excellent contrast can be obtained.

(Embodiment 10)
A honeycomb structure manufacturing apparatus and manufacturing method will be described. Examples of the honeycomb structure manufacturing apparatus are shown in FIGS. FIG. 8 is an apparatus that executes a step of applying a hardening material for a honeycomb structure onto a substrate, and FIG. 9 is an apparatus that converts the hardening material applied onto the substrate into a honeycomb structure. A honeycomb structure manufacturing apparatus 20 shown in FIG. 8 is an apparatus that applies a curing material 30 to a mold 23 bonded to a glass substrate 22 with good flatness, and controls the temperature of the curing material 30 and then slits it from a discharge pump 29. A uniform film is formed on the mold 23 by moving the coating table 21 simultaneously with the feeding of the curable material 30 to the head 24. The mold 23 can be any material such as nickel, silicon, glass having a resist pattern formed thereon, copper-clad plate (copper / polyimide laminated substrate), glass, and other resin materials (polyimide, PTE, acrylic, etc.). be able to. Etching was performed as a method for forming the recess.

When the formation of the film is completed, the mold on which the film has been formed is fed together with the glass substrate into the decompression chamber 40 shown in FIG. 9, and the decompression chamber 40 is decompressed to foam the film. FIG. 9 is a diagram of the decompression device used at this time. The glass substrate is automatically supplied into the chamber and decompressed to a certain degree of vacuum to form a honeycomb. The ultimate pressure at this time is 5 × 10 ² Pas, and the cured material is cured by irradiating ultraviolet rays with an ultraviolet irradiation device (not shown) as it is, and the film that has become a honeycomb structure after curing is taken out together with the glass substrate. It is. The height of the honeycomb at this time was about 100 μm.

  Thereafter, the honeycomb film can be released from the mold to form a honeycomb structure. When functional material is injected into the honeycomb formed at this time, it is injected from the opening formed in the mold release surface. If the opening is insufficient depending on the mold shape, the opening diameter is controlled by exposing soluble material. May be. Further, this was sealed with a polymer material, and an image was displayed by applying an electric field of 10V.

Hereinafter, the present invention will be described in more detail with reference to specific examples.
Example 1
Irgacure 500 (manufactured by Ciba Specialty Chemicals Co., Ltd.) consisting of 1-hydroxy-cyclohexyl phenyl ketone and benzophenone as a reaction initiator is used as an epoxy acrylate-based UV curable resin, which is a liquid beam set AQ9 (Arakawa Chemical Industries). ) Was used. Here, fluorine surfactant Novec FC-4430 (manufactured by 3M) (0.5 wt%) is added to the AQ9 solution to lower the surface tension of the epoxy acrylate. This solution is applied onto a mold base having a recess using a slit coater to form an epoxy acrylate film on the mold substrate. A substrate such as a film with a transparent conductive film is disposed on the epoxy acrylate film, put into a decompression device to reduce the pressure, and the air in the recess is expanded. When a certain degree of vacuum is reached and a cell having a desired shape is formed, the epoxy acrylate film on which the hollow layer (cell) is formed is irradiated with ultraviolet rays to cure the epoxy acrylate.

  When epoxy acrylate is used as a plastically deformable material, the wall thickness h of each cell is 0.01 to 5 μm, the opening wall thickness i is 0.01 to 1 μm, and the intersection of the wall of each cell and the wall of the opening A honeycomb structure having a radius of curvature j of 0.1 to 5 μm and an opening m of 140 μm can be manufactured (see FIG. 6 for symbols of each part). At the same time, bonding with a mating substrate such as a film with a transparent conductive film is performed, and a honeycomb structure with a film with a transparent conductive film is obtained. Since joining with a mating substrate such as a film with a transparent conductive film is performed simultaneously with the manufacture of the honeycomb structure, the number of processes is small, and there is an effect that the cost for equipment cost and processing time can be reduced.

(Example 2)
In this example, a urethane acrylate ultraviolet curable resin is used as an ultraviolet curable resin, and a polyether-modified silicone surfactant is added as a substance that lowers the surface tension (0.5 wt%), and used as a honeycomb structure material. .
Here, Loctite 3301 (manufactured by Henkel Technologies), which is a urethane acrylate ultraviolet curable resin containing a mercapto group, was used. Add siloxane-polyalkylene oxide copolymer: NIAX Silicone L-650 (manufactured by GE Toshiba Silicone) (0.5 wt%), which is a polyether-modified silicone surfactant, to the Loctite 3301 solution to lower the surface tension of urethane acrylate. . This solution is applied using a slit coater to form a urethane acrylate film on the mold substrate. A substrate such as a film with a transparent conductive film is placed thereon, and the pressure is reduced to expand the air. When a certain degree of vacuum is reached and a cell having a desired shape is formed, the urethane acrylate film on which the hollow layer (cell) is formed is irradiated with ultraviolet rays to cure the urethane acrylate. When urethane acrylate is used as a plastically deformable material, the wall thickness h of each cell is 0.01 to 5 μm, the opening wall thickness i is 0.01 to 1 μm, and the intersection of the wall of each cell and the wall of the opening A honeycomb structure having a radius of curvature j of 0.1 to 5 μm and an opening m of 140 μm can be manufactured (see FIG. 6). In the same manner as in Example 1, bonding with a mating substrate such as a film with a transparent conductive film is simultaneously performed. Since the bonding with the mating substrate is simultaneously performed, the number of processes is small, and there is an effect that the cost for equipment cost and processing time can be reduced.

Example 3
This is an example in which a urethane acrylate ultraviolet curable resin as a nonionic ultraviolet curable resin and FC4430 (0.5 wt%) as a nonionic surfactant are used as a honeycomb structure material.
As a plastically deformable material, a urethane acrylate ultraviolet curable resin which is a nonionic ultraviolet curable resin is used. As the urethane acrylate ultraviolet curing material, Irgacure 500 (3 wt.) Composed of 1-hydroxy-cyclohexyl phenyl ketone and benzophenone as a reaction initiator is used as a beam initiator AQ17 (manufactured by Arakawa Chemical Industries) which is a mixed solution of polyurethane acrylate and an acrylic monomer. %) Was used. Here, nonionic fluorine-containing surfactant Novec FC-4430 (manufactured by 3M) (0.5 wt%) is added to the AQ17 solution to lower the surface tension of the urethane acrylate solution. This uncured resin liquid is applied using a slit coater to form a urethane acrylate film on the mold substrate. A substrate such as a film with a transparent conductive film is placed thereon, and the pressure is reduced to expand the air. When a certain degree of vacuum is reached and a cell having a desired shape is formed, the urethane acrylate film on which the hollow layer (cell) is formed is irradiated with ultraviolet rays to cure the urethane acrylate ultraviolet curable resin.

  When urethane acrylate is used as a plastically deformable material, the wall thickness h of each cell is 0.01 to 5 μm, the opening wall thickness i is 0.01 to 1 μm, and the intersection of the wall of each cell and the wall of the opening A honeycomb structure having a radius of curvature j of 0.1 to 5 μm and an opening m of 140 μm can be manufactured (see FIG. 6). At the same time, bonding with a mating substrate such as a film with a transparent conductive film is performed. Since the bonding with the mating substrate is simultaneously performed, the number of processes is small, and there is an effect that the cost for equipment cost and processing time can be reduced.

Example 4
In this example, an alkoxy acrylate ultraviolet curable resin is used as a hydrophilic ultraviolet curable resin, and a hydrocarbon acrylate-perfluorocarbon acrylate copolymer is added as a fluoroalkyl group-containing surfactant (0.5 wt%) and used as a honeycomb structure material.
As the plastically deformable material, an alkoxy acrylate UV curable resin which is a hydrophilic UV curable resin is used. Specifically, Irgacure 500 (Ciba Specialty Chemicals Co., Ltd.) comprising 1-hydroxy-cyclohexyl phenyl ketone and benzophenone as a reaction initiator using polyethylene glycol diacrylate having a high affinity with water: PEG400DA (manufactured by Daicel Cytec). Manufactured) (3 wt%) was used. Here, the surface tension of the alkoxy acrylate liquid is lowered by adding (0.5 wt%) hydrocarbon acrylate-perfluorocarbon acrylate copolymer: F-top EF802 (manufactured by Gemco) into the PEG 400DA liquid. This uncured liquid is applied using a slit coater to form an alkoxy acrylate film on the mold substrate. A substrate such as a film with a transparent conductive film is placed thereon, and the pressure is reduced to expand the air. When a certain degree of vacuum is reached and a cell having a desired shape is formed, the alkoxy acrylate film on which the hollow layer (cell) is formed is irradiated with ultraviolet rays to cure the alkoxy acrylate ultraviolet curable resin.

  When alkoxy acrylate is used as a plastically deformable material, the wall thickness h of each cell is 0.01 to 5 μm, the opening wall thickness i is 0.01 to 1 μm, and the intersection between the wall of each cell and the wall of the opening A honeycomb structure having a radius of curvature j of 0.1 to 5 μm and an opening m of 140 μm can be manufactured (see FIG. 6). At the same time, bonding with a mating substrate such as a film with a transparent conductive film is performed. Since the bonding with the mating substrate is simultaneously performed, the number of processes is small, and there is an effect that the cost for equipment cost and processing time can be reduced.

(Comparative example)
Water-soluble resin (aqueous solution) As a plastically deformable material, gelatin which is a water-soluble resin is used. Gelatin is dissolved in water to about 5-30 wt%. Using this solution, a gelatin film is formed on the mold substrate using a slit coater. This is decompressed and air is expanded. Residual moisture in the gelatin is evaporated in a vacuum, dried and solidified (see FIG. 3). In addition to gelatin, polyurethane (Dainippon Ink Industries Hydran WLS-201), polyvinyl alcohol (Kuraray Poval PVA117), and the like can be used as the plastically deformable material.

  When gelatin is used as a plastically deformable material, the wall thickness h of each cell shown in FIG. 6 is 0.01 to 5 μm, and the opening and the wall thickness i (ceiling portion) opposite to the opening are 0.01 to 2 μm (center). A honeycomb structure having a radius of curvature j of 0.1 to 20 μm and an opening m of 140 μm at the intersection between each cell wall and the opening or the wall (ceiling) opposite to the cell can be produced. However, it takes time to evaporate residual moisture in the gelatin, and to dry and solidify it. Moreover, since there is a drying step, a honeycomb structure integrated with a substrate such as a film with a transparent conductive film cannot be produced.

(Comparative Example 2)
Manufacture of honeycomb structure using only UV curable resin as plastic deformable material. Epoxy acrylate ultraviolet curable resin AQ9 (manufactured by Arakawa Chemical Industries) was used, and Irgacure 500 (manufactured by Ciba Specialty Chemicals Co., Ltd.) (3 wt%) comprising 1-hydroxy-cyclohexyl phenyl ketone and benzophenone was used as a reaction initiator. Coating is performed using a slit coater to form an epoxy acrylate film on the mold substrate. A substrate such as a film with a transparent conductive film is placed thereon, decompressed, and air is expanded to form a honeycomb structure (see FIG. 2). When a certain degree of vacuum is reached and a cell having a desired shape is formed, the epoxy acrylate film on which the hollow layer (cell) is formed is irradiated with ultraviolet rays to cure the epoxy acrylate. If a substance that lowers the surface tension is not added to the epoxy acrylate-based UV curable resin, increasing the vacuum during decompression to reduce the thickness of the cell partition when forming a honeycomb structure will cause the cell partition to break and There is a tendency to be connected. When the honeycomb structure is formed at a degree of vacuum in which the partition walls are not broken and connected to the adjacent cells, the wall thickness h of each cell is as thick as 10 to 40 μm, the opening wall thickness i is 0.01 to 5 μm, and the opening m is 100 A thick cell structure having a thickness of about 130 μm is produced (see FIG. 6). The opening shape is substantially circular.

(Example 5)
FIG. 7 shows a cross-sectional structure of an electrophoretic image display apparatus according to the fifth embodiment of the present invention. As shown in FIG. 7, the image display device 10 uses a honeycomb structure having cells having a height of 50 μm and a width of 150 μm as pixels.
The main structure of the image display device 10 includes a film 13 with a transparent conductive film, a partition wall 12 of a honeycomb structure, an electrophoretic agent 11 filled in the partition wall 12, a sealing material 14 for the lower electrophoretic agent 11, Insulation / adhesive 15 and voltage drive circuit 16.
The film 13 with the transparent conductive film only needs to be integrated with the honeycomb structure at the time of manufacturing the honeycomb structure. The transparent PET film for protecting the electrophoretic material is coated with ITO, which is a transparent common electrode by a sputtering method or the like. (Indium Tin Oxide) layers are stacked. The electrophoretic agent 11 is a slurry-like mixture of electrophoretic particles and electrophoretic media that are pigment particles, and the electrophoretic particles move up and down in the cell when a voltage is applied. This is a part that is a source of a pixel that displays. The voltage application is controlled by a voltage driving circuit 16 that can apply different voltages to the upper ITO common electrode and the lower cells.

  The honeycomb structure forming the partition walls 12 is a hexagonal close-packed shape having an opening on one side, and the material is a urethane acrylate ultraviolet curable resin added with a fluorosurfactant. The sealing material 14 is made of gelatin, and the coating method is slit coating. In addition, an equivalent material can be obtained by using a water-soluble resin sealing material such as polyurethane or polyvinyl alcohol. The method may be spin coating or curtain coating. The material of the adhesive layer 15 is an epoxy resin, and the coating method is a slit coat. In addition, an equivalent can be obtained by using an ultraviolet curable adhesive, a hot melt, or the like. The same coating method can be obtained by spin coating and curtain coating. The parts excluding the electrophoretic agent (a slurry mixture of electrophoretic particles and electrophoretic medium) are joined together.

  As the display characteristics of the image display device 10, display characteristics of white reflectance 40%, black reflectance 1%, and contrast 40 can be obtained. In the image display device 10, the breakage of the partition walls and the separation of the joint portion do not occur with respect to the bending with the curvature of 200 mm. For comparison, when the same electrophoretic solution is displayed in a 10 mm square cell with a depth of 50 μm (other structures are the same), the display characteristics are white reflectance 43%, black reflectance 1%, and contrast 43. It was.

Honeycomb structure forming method using ultraviolet curable resin (1) Honeycomb structure forming method using UV curable resin (2) Method for forming honeycomb structure using gelatin aqueous solution Square lattice-shaped recess Hexagonal close-packed recess Explanatory drawing of outline shape and partition wall thickness of honeycomb structure Electrophoretic image display device Manufacturing apparatus for honeycomb structure Vacuum chamber configuration diagram

Explanation of symbols

1: Substrate 2: Substrate 3: Gelatin aqueous solution 4: UV curable resin 5: UV curable resin 6: Gas 10: Image display device 11: Electrophoretic material 12: Partition wall 13: Film with transparent conductive film 14: Sealing material 15 : Insulation / adhesive material 16: Voltage drive circuit 20: Honeycomb structure manufacturing apparatus 21: Application table 22: Glass substrate 23: Mold 24: Slit head 25: Application table feed motor 26: Gap following roller 27: Curing material bowl 28: Gap adjustment stage 29: Constant discharge pump 30: Curing material 31: Heat hose 32: Heater 33: Vacuum gauge 34: Release valve 35: Vacuum pump 40: Depressurization chamber

Claims (13)

  A plastic deformation film containing a plastically deformable curable material that is cured by energy rays and a surface tension lowering agent that lowers the surface tension of the curable material is disposed on a substrate having a plurality of recesses, and the gas present in the recesses A honeycomb structure obtained by forming a plurality of cells by being deformed by volume expansion, and then irradiating and curing energy rays.   The honeycomb structure according to claim 1, wherein the surface tension lowering agent is a surfactant.   The honeycomb structure according to claim 2, wherein the surfactant is a fluorine-containing surfactant.   The honeycomb structure according to claim 3, wherein the fluorine-containing surfactant has a fluoroalkyl group.   The fine honeycomb structure according to claim 3 or 4, wherein the curable material is a nonionic resin, and the fluorine-based surfactant is a nonionic surfactant.   The honeycomb structure according to any one of claims 1 to 5, wherein the curable material is an ultraviolet curable resin.   The honeycomb structure according to claim 6, wherein the ultraviolet curable resin is hydrophilic.   The honeycomb structure according to claim 7, wherein the ultraviolet curable resin is a urethane acrylate resin.   The honeycomb structure according to claim 7, wherein the ultraviolet curable resin is an epoxy acrylate resin.   The honeycomb structure according to claim 7, wherein the ultraviolet curable resin is an alkoxy acrylate resin.   An image display apparatus, wherein a display unit is formed by inserting a display medium into each cell of the honeycomb structure according to any one of claims 1 to 10.   The image display device according to claim 11, wherein the cell is filled with electrophoretic particles and an electrophoretic medium.   A step of closely attaching a plastic deformation film including a plastically deformable curable material that is cured by energy rays and a surface tension lowering agent that lowers a surface tension of the curable material to a substrate surface having a plurality of recesses; A step of deforming the plastic deformation film by volume expansion of a gas present in the recess to form a plurality of cells, and a step of irradiating the plastic deformation film formed with the plurality of cells with an energy beam to cure. A method for manufacturing a featured honeycomb structure.

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