JP5106887B2 - Honeycomb structure sheet manufacturing substrate and honeycomb structure sheet manufacturing method - Google Patents

Description

  The present invention relates to a substrate for manufacturing a composite cell structure and a method for manufacturing the composite cell structure.

  CRTs and liquid crystal displays are widely used as display terminals for so-called images such as characters, still images, and moving images. These can display and rewrite digital data instantly, but it is not easy to carry the device easily. 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 or the like, it is recorded on a paper medium by a printer or the like. 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. On the other hand, 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 has the advantages of both display and hard copy, is rewritable and has good recording properties, and is easy on the eyes. Recently, display media using polymer-dispersed liquid crystals, bistable cholesteric liquid crystals, electrochromic elements, electrophoretic elements, and the like are attracting attention as reflective display media that can display bright images and have memory properties. . 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 a typical electrophoretic display medium, a dispersion liquid in which electrophoretic particles having a color different from the color of the dispersion medium is dispersed in a colored dispersion medium is enclosed between a pair of transparent electrodes. . Electrophoretic particles (also simply referred to as electrophoretic particles) have a charge on the particle surface in the dispersion medium. When a voltage that attracts the charge of the electrophoretic particles is applied to one transparent electrode side, the electrophoretic particles are transferred to the transparent electrode. The color of the migrating particles is observed by being attracted and accumulated on the side, and when a voltage repelling the charge of the migrating particles is applied, the migrating particles move to the opposite transparent electrode side, so the color of the dispersion medium is observed. The Display can be performed by using the change in color.

  An electrophoretic display element using such an electrophoretic display medium is an individual image display element. In order to obtain an image display device, many electrophoretic display elements are arranged in a minute area. An aggregate of is required. Therefore, a structure for arranging these elements is required. A sheet having a honeycomb structure, which is an aggregate of a plurality of hollow structures, is known as a structure for an image display element suitable for dividing such fine elements and arranging them at high density. An electrophoretic particle and a dispersion medium are arranged in each honeycomb to form one image element, and an image display device as a whole can be obtained.

  For example, Patent Document 2 discloses an electrophoretic display and a manufacturing method thereof. This electrophoretic display has a plurality of cup-shaped recesses formed by microembossing or image exposure, and the recesses are filled with a solvent and a dispersion of charged pigment particles dispersed in the solvent, and have a specific gravity smaller than that of the dispersion. It is formed by curing an overcoat layer of a sealing composition that is immiscible with the dispersion and is sealed to confine the dispersion in the recess.

  In the case of micro-embossing, a precursor layer of a thermoplastic material or a thermosetting material coated on a conductor film by a male pattern provided with a pattern in advance is embossed. The precursor layer is then cured by radiation, cooling, solvent evaporation or other means and removed from the mold. If the thickness of the wall is reduced by this method, the male concave portion (between the convex portion and the convex portion) becomes very thin.

  In the case of forming a structure by image exposure, the conductive film coated with the radiation curable layer is subjected to image exposure, and then the non-exposed area is removed after the exposed area becomes hard. In the case of this method, radiation is irradiated through a mask, or a pattern is directly drawn on the radiation curable layer with finely squeezed radiation.

As a method for manufacturing a honeycomb structure, a method for manufacturing an adhesion preventing material made of a biodegradable film having a honeycomb structure described in Patent Document 3 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 International Publication No. 2004/148680 Pamphlet

  When an image display structure (also referred to as a composite cell 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, an image display It is preferable that the aperture ratio of the structure is large, that is, the partition wall thickness in the cell structure of the composite cell structure, particularly the partition wall on the display surface side is thin. Further, the display unit matrix of the image display device is required to have a uniform shape of each display element and a uniform partition wall thickness between the display elements.

  In the case of the micro-embossing method described in Patent Document 2, when trying to reduce the thickness of the partition wall, the male concave portion (between the convex portion and the convex portion) becomes very thin, and the precursor does not sufficiently enter the concave portion. The shape of the mold cannot be faithfully transferred, the strength of the precursor is insufficient, and the precursor remains in the recess of the mold when releasing, creating a hollow structure with a thin wall thickness difficult. Further, since a heating resin is used, there is a problem that a cooling time for curing is required and a cycle time becomes long. Although the thickness of the wall partitioning each concave portion of the structure is not particularly described, there is a limit to the thickness and aspect ratio of the partition wall considering the process of transfer to the male mold and peeling. For example, according to studies by the inventors, in micro-embossing to transfer a mold shape, a micro-emboss structure having a partition wall thickness of 10 μm or less and a height suitable for an image display structure is formed. Is considered difficult.

  In the case of the structure formation method by image exposure, radiation is irradiated through a mask, or a pattern is drawn directly on the radiation curable layer with finely squeezed radiation, but the radiation wraps around the radiation curable layer. It is difficult to make a high aspect ratio wall by scattering. In addition, a method using photolithography is likely to be costly because of the increased number of steps, and is not suitable for forming a structure having a large area.

  In view of such problems, an object of the present invention is to provide a composite cell structure manufacturing substrate for manufacturing a composite cell structure having a large aperture ratio, and thus a thin cell partition and a uniform cell structure, and The object is to provide a method of manufacturing a composite cell structure using the same.

The means for solving the problems of the present invention will be described below.
The present invention covers a surface having a plurality of spaced recesses with a deformable material so that a space remains in the recess, and forms a plurality of cells in the deformable material by the gas expansion pressure in the space of the recess. A honeycomb structure sheet manufacturing substrate (hereinafter, the honeycomb structure sheet is referred to as a composite cell structure body, and the honeycomb structure sheet manufacturing substrate is referred to as a composite cell structure manufacturing substrate) , The composite cell structure manufacturing substrate includes at least two regions having different affinity for the deformable material.

  The present invention is characterized in that the plurality of spaced-apart recesses are regularly arranged, and at least one of the regions having different affinity for the deformable material surrounds each recess. The composite cell structure manufacturing substrate is included.

  The present invention includes the composite cell structure manufacturing substrate, wherein the region surrounding the recess is regularly arranged.

  The present invention is characterized in that, among the regions having different affinity for the deformable material, the region having high affinity for the deformable material is formed into the shape of the partition wall of the opening of the composite cell structure. Including a substrate for manufacturing a structure.

  In the present invention, among the regions having different affinity for the deformable material, the region having high affinity for the deformable material is a region in which a plurality of dots having high affinity for the deformable material are formed. The composite cell structure manufacturing substrate is included.

  In the composite cell structure manufacturing method, the region having low affinity for the deformable material among the regions having different affinity for the deformable material is a plurality of discontinuous regions. Includes substrate.

  The present invention includes the substrate for manufacturing a composite cell structure, wherein the low affinity region surrounds a recess.

  The present invention includes the substrate for manufacturing a composite cell structure, wherein the low affinity region is a region in which a fine concavo-convex shape that is difficult to wet with a deformable material is formed.

The present invention includes the substrate for manufacturing a composite cell structure, wherein the low affinity region is a region where an alkyl ketene dimer layer is formed .

The present invention is a coating step of coating the surface of a substrate having a plurality of spaced recesses with a deformable material so that a space remains in the recesses;
A cell forming step of forming a plurality of cells in the deformable material by gas expansion pressure in the space of the recess,
The substrate includes a method for manufacturing a composite cell structure, wherein the substrate is a substrate for manufacturing the composite cell structure.

  The present invention includes the method of manufacturing the composite cell structure, wherein in the coating step, the deformable material covering the surface of the substrate is a sheet.

  The present invention includes the method for manufacturing the composite cell structure, including a curing step of curing the deformable material formed with the plurality of cells to fix the shape of the cells.

  According to the present invention, a substrate for manufacturing a composite cell structure for manufacturing a composite cell structure having a uniform cell structure with a large aperture ratio and thus a thin partition between cells, and a composite cell structure using the same The manufacturing method of can be provided.

  Before explaining the composite cell structure manufacturing substrate and the composite cell structure manufacturing method of the present invention, in order to facilitate understanding of the composite cell structure manufacturing substrate and the composite cell structure manufacturing method of the present invention, A method for manufacturing a composite cell structure that has been studied by the present inventors will be briefly described. FIG. 2 is an explanatory view of a method of manufacturing a composite cell structure that has been studied conventionally. The manufacturing method of a composite cell structure will be described with reference to FIG. 2. First, a substrate 1 having a fine recess 3 corresponding to the cell structure formed on the surface is prepared. The surface of the substrate 1 preferably has good adhesion to the deformable material 2 that is a precursor of the composite cell structure. The surface of the substrate 1 is covered with a sheet-like deformable material 2 that is a precursor of the composite cell structure. At this time, a space is left between the concave portion 3 on the surface of the substrate 1 and the coated deformable material 2.

  In this state, an expansion force is applied to the gas (usually air) existing in the space of the recess 3 while the substrate 1 and the deformable material 2 are kept in close contact with each other. As a method for imparting the gas expansion force, if the deformable material 2 in close contact with the substrate 1 is introduced into a decompression chamber or the like and the pressure on the surface side of the deformable material 2 is reduced, The gas has a relatively high pressure and an expansion force is generated. Since the substrate 1 is a rigid material, it is not deformed, and the deformable material 2 is pushed up by the gas expansion pressure. Since the deformable material 2 is in intimate contact with the surface area of the substrate 1 that does not have the recesses 3, independent voids are generated in a state of foaming at positions facing the respective recesses 3 due to gas expansion pressure. The voids are arranged in the deformable material 2 as independent spaces. When this space becomes large to some extent, the sheet-like deformable material 2 swells as a whole and takes a sheet-like form having a honeycomb structure.

  The sheet-like deformable material 2 having the honeycomb structure is cured and solidified so as not to deform the honeycomb structure to obtain a honeycomb structure sheet. For the curing, a method such as drying curing or ultraviolet irradiation curing is adopted in accordance with the characteristics of the deformable material 2.

  The honeycomb structure sheet is released from the substrate 1 to form a composite cell structure. With such a manufacturing method, it is possible to manufacture a composite cell structure having a relatively deep cell depth between the cells.

  In this method of manufacturing a composite cell structure, in order to obtain a desired cell structure and at the same time thin the partition walls between cells, and at the same time strictly control the uniformity, the adjustment of the deformable material 2 and the surface of the substrate 1 There is a lot of know-how in the formation of the substrate and the adjustment of the adhesion between the substrate 1 and the deformable material 2, and a composite cell structure with high uniformity cannot be easily formed. For example, as shown in FIG. 3A, the cell shape and partition walls of the composite cell structure may vary depending on variations in tension of the deformable material 2 and variations in adhesion between the deformable material 2 and the surface of the substrate 1. In some cases, the thickness of the film varied.

  On the other hand, the substrate for manufacturing a composite cell structure of the present invention has at least two types of regions having different affinity for the deformable material on the surface where the recesses are formed. As described above, this composite cell structure manufacturing substrate covers a surface having a plurality of spaced recesses with a deformable material so that spaces remain in the recesses, and the gas in the spaces of the recesses is formed. It is a substrate for manufacturing a composite cell structure in which a plurality of cells are formed in a deformable material by an expansion pressure.

  The composite cell structure manufacturing substrate of the present invention and the composite cell structure manufacturing method using the substrate will be described with reference to the composite cell structure forming step of the present invention shown in FIG. The composite cell structure forming step shown in FIG. 1 differs from the composite cell structure manufacturing method shown in FIG. 2 in the surface characteristics of the composite cell structure manufacturing substrate. The substrate 1 shown in FIG. 2 was merely provided with the recesses 3 arranged regularly, but the substrate 1 shown in FIG. 1 was formed with a composite cell structure so as to surround each recess 3. The high affinity region 4 having a high affinity for the deformable material is formed as a strip-shaped turtle shell pattern. The process from the coating process of the deformable material 2 onto the substrate 1 in FIG. 2 to the mold release process of the composite cell structure is the same as the process shown in FIG.

  And the cell structure of the obtained composite cell structure is different. In other words, in the method for manufacturing the composite cell structure shown in FIG. 2, the partition walls between the cells of the composite cell structure vary in thickness or are relatively thick. On the other hand, in the composite cell structure according to the method for manufacturing the composite cell structure shown in FIG. 1, the partition walls between the cells are the same as the width of the strip-shaped high affinity region 4, If the width is narrowed, the partition between cells can be made thin.

  This difference will be described with reference to FIG. In the method of manufacturing the composite cell structure shown in FIG. 2, as shown in FIG. 3a), the gas sandwiched between the substrate 1 and the deformable material 2 is in accordance with the difference between the external pressure (which is reduced in pressure). The thickness of the cell partition wall changes depending on the pressure to stretch and spread the material 2 and the balance between the adhesion of the material film to the substrate 1 and the tension of the material film. As the volume inside the cell increases, the wall becomes thinner, and the width x of the portion where the material 2 and the substrate 1 are in contact, that is, the thickness x of the partition opening is also reduced. When the thickness x of the opening is reduced, the thickness of the whole partition is further reduced. Since the adhesive force and tension vary depending on the material 2, the partition wall thickness varies greatly, and it may be difficult to obtain a desired partition wall thickness. In addition, even in the same material, the position of the formed cell structure due to the variation in the amount of gas sandwiched between the recesses 3 between the material 2 and the substrate 1 or the unevenness of the thickness of the material 2 when applied to the substrate 1 May cause unevenness of the partition wall thickness.

  On the other hand, in the method for producing a composite cell structure of the present invention shown in FIG. 1, as shown in FIG. 3b), on the surface of the composite cell structure production substrate (template) of the present invention used for forming the composite cell structure, By providing a high-affinity pattern corresponding to the shape of the opening of the cell of the composite cell structure thus formed in a strip shape, the cell partition wall thickness x ′ is controlled, and a cell having a partition wall having a desired thickness can be stabilized. Obtainable.

  FIG. 4 schematically shows the state of cell formation and partition formation in the honeycomb structure forming step by gas expansion. From the left, a) an example using the substrate 1 having a low affinity with the deformable material 2, b) an example using the substrate 1 having a high affinity with the deformable material 2, c) the surface of the present invention can be deformed An example is shown in which a substrate 1 having two types of regions having different affinity from the material 2 is used. There is almost no difference in each case until voids are generated on the surface of the deformable material 2 due to the expansion force of the gas in the recesses and a certain amount of space is formed.

  When the cell space becomes larger than a predetermined charge, a) In the example using the substrate 1 having a low affinity with the deformable material 2, the adhesion between the deformable material 2 and the substrate 1 having a low affinity is reduced. It is weak and the cells may be connected. B) In the example using the substrate 1 having a high affinity with the deformable material 2, the adhesive force between the deformable material 2 and the substrate 1 with a high affinity is too strong and can be deformed into the opening of the cell. The remaining material 2 remains, and the honeycomb structure becomes a honeycomb structure having a variation in the thickness of partition walls between cells having narrow openings.

  On the other hand, c) In the example using the substrate 1 having two types of regions having different affinity with the deformable material 2 of the present invention on the surface, the deformable material 2 has a high affinity at the opening of the cell. It adheres only to the region 4 and peels off from the low affinity region 5. That is, the thickness of the partition between cells in the cell opening is controlled by the width of the band of the high affinity region 4. And according to this, the width of the partition walls in the cells other than the openings is also controlled.

  Hereinafter, the present invention will be specifically described with reference to some embodiments and examples. In addition, this invention is not restricted to the following embodiment and Example, The example shown to embodiment or the Example can be changed and deform | transformed according to the objective of this invention.

(Embodiment 1: Substrate for manufacturing composite cell structure)
Embodiment 1 of the composite cell structure forming substrate of the present invention is shown in FIG. FIG. 5 shows the surface of a substrate (a substrate for forming a composite cell structure corresponding to the substrate 1 shown in FIG. 2) to which a sheet-like deformable material to be a composite cell structure is adhered. . This substrate is a composite cell structure forming substrate corresponding to the substrate 1 shown in FIG. On the surface of this substrate, a recess 3 arranged in a hexagonal close-packed structure is formed. A low-affinity region 5 having a low affinity for the deformable material that is a cell forming material and a high-affinity region 4 having a high affinity for partitioning the low-affinity region 5 are formed around the recess 3. . These regions have a turtle shell pattern drawn by a continuous hexagonal high affinity region 4 band. A recess is arranged at the center of each hexagon.

  In FIG. 5, the recesses 3 are arranged in a hexagonal close-packed structure. However, the recesses 3 may be arranged in a square lattice shape, and the high affinity regions 4 may be formed in a square lattice shape so as to surround the respective recesses. . The substrate may be formed of an inorganic substance such as a rigid metal, glass, or ceramic, or an organic substance such as a resin that does not deform when the material forming the composite cell structure is deformed, or a composite material thereof. Examples of the substrate material include nickel, silicon, glass having a resist pattern formed on glass, a copper-clad plate (copper / polyimide laminated substrate), glass, and other resin materials (polyimide, PET, acrylic, etc.). Specific examples include a nickel mold by electrodeposition, a glass having a resist pattern formed on glass, a copper-clad plate (copper / polyimide laminated substrate), etched glass, silicon, and the like. The high affinity region 4 and the low affinity region 5 may be appropriately selected according to the type of the base material and the deformable material. However, when the base material is made of metal and the deformable material is a resin, the low affinity region 4 and the low affinity region 5 are low. The affinity region 5 may be a metal surface of the substrate as it is, and a material that can be deformed to the metal surface as the high affinity region 4 may be a resin or an organic adhesive having a high affinity for the resin.

  As will be described in detail later, when such a substrate is used to form a composite cell structure, a uniform honeycomb structure in which the cell partition wall thickness is thin can be obtained, depending on the width of the high affinity region 4. It is also possible to control the thickness of the cell partition walls.

(Embodiment 2: Manufacturing method of composite cell structure (A))
The manufacturing method of the composite cell structure of the present invention includes a coating step of covering a surface of a substrate having a plurality of spaced recesses with a deformable material so that a space remains in the recess, and a gas in the space of the recess A method of manufacturing a composite cell structure including a cell forming step of forming a plurality of cells in the deformable material by an expansion pressure, and the substrate is the substrate 1 described in the first embodiment.

  A method for producing a composite cell structure of the present invention is shown in FIG. In FIG. 6, first, (a) the substrate 1 described in the first embodiment is used, and this is covered with a sheet 2 made of a thermoplastic resin (for example, PET) as a deformable material 2. At this time, the sheet 2 is brought into close contact with the surface of the substrate 1 while leaving the space of the concave portion of the substrate 1. Next, (b) as a material deformation step, the substrate 1 covered with the PET sheet 2 is introduced into a decompression chamber, and the decompression chamber is decompressed at a temperature at which the PET sheet 2 can be deformed. If it does so, the area | region which faces the recessed part of the sheet | seat 2 will swell, and a cell will be formed corresponding to each recessed part. The sheet 2 is a sheet having a honeycomb structure as a whole. When the desired honeycomb structure is obtained, the temperature is lowered while maintaining the pressure (decompression) of the decompression chamber. When the temperature is sufficiently lowered and the PET sheet 2 is cured, the honeycomb structured sheet is peeled from the substrate. When the peeling is completed, the pressure in the decompression chamber is returned to the normal pressure, and the manufacturing method of the composite cell structure of the present invention is completed. Normally, the honeycomb structured sheet is elastically deformed even if the pressure in the decompression chamber is returned to the normal pressure before the honeycomb structured sheet is peeled off the substrate, but if the sheet is peeled off from the substrate, the original honeycomb structured sheet is restored. Return.

(Embodiment 3: Manufacturing method of composite cell structure (B))
A method for producing a composite cell structure of the present invention is shown in FIG. Since the manufacturing process shown in FIG. 7 is similar to that of the second embodiment, a portion different from that of the second embodiment will be described. The parts that are not described are the same as those in the second embodiment. In this embodiment, a gelatin aqueous solution sheet 2 is used as the deformable material 2. The gelatin aqueous sheet 2 is heated to such an extent that it does not gel. Then, a) the substrate 1 is coated with the sheet 2, and b) the sheet 2 is foamed under reduced pressure in the decompression chamber while the substrate 1 is coated, thereby forming a honeycomb structure. c) Moisture is removed in a dry air stream with the honeycomb structure-formed sheet 2 under reduced pressure or under reduced pressure. The gelatin sheet from which moisture has been removed hardens while maintaining the honeycomb structure. The cured honeycomb structure sheet can be peeled off from the substrate to produce the composite cell structure of the present invention. In this embodiment, an inexpensive and easy-to-handle gelatin aqueous solution is used, so the apparatus is simple and easy to manufacture.

(Embodiment 4: Method for producing composite cell structure (C))
Furthermore, the manufacturing method of the composite cell structure of this invention is shown in FIG. In the manufacturing process shown in FIG. 8, an ultraviolet curable resin sheet 2 was used as the deformable material 2. For this reason, the honeycomb structured sheet 2 formed by foaming in the step b) is cured by irradiating with ultraviolet rays. Other steps are the same as those in the third and fourth embodiments. In this embodiment, since the ultraviolet irradiation process can be completed in a short time, the manufacturing time can be greatly shortened.

(Embodiment 5: Manufacturing method (D) of composite cell structure)
Furthermore, the manufacturing method of the composite cell structure of this invention is shown in FIG. In the manufacturing process shown in FIG. 9, an ultraviolet curable resin sheet 2 was used as the deformable material 2. When there are few volatile components from a material like an ultraviolet curable resin, as shown in FIG. 9, after mounting the sheet | seat 2 on the board | substrate 1 in a (a) process, as shown in FIG. (B) a step of deforming the material by the expansion of the gas sandwiched between the recesses between the substrate 1 and the sheet 2, and (c) energy from the outside. The composite cell structure can be manufactured by the process of applying and hardening the deformed material.

  In this way, by controlling the distance between the substrate 1 and the pressing plate 7, it becomes easy to control the thickness of the sheet of the cell structure, and after peeling from the substrate 1, the sheet 1 adheres to the pressing plate 7. Since the cell structure can be handled in a state, it can be easily handled without damaging the cell structure.

  In the method for producing these composite cell structures, the deformable materials include polyvinyl alcohol, polyvinyl pyrrolidone, polyurethane, pullulan, albumin, CMC, polyacrylic acid, cellulose, starch, gelatin, alginate, guar gum, gum arabic, Color ginnan, tragacanth, pectin, dextrin, casein, collagen, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol, ethylene oxide, agar, locust bean gum, xanthan gum, cyclodextrin, tannic acid, karaya gum, duran gum, far celeran , Trang gum, lecithin, chitin chitosan, chondroitin sodium sulfate, lignin sulfonic acid, methylcellulose, hydroxy Examples include methylcellulose, polyacrylamide, polyethyleneimine, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, polyethylene oxide, polyallylamine, urethane acrylic UV curable resin, epoxy acrylic UV curable resin, and alkoxy acrylic UV curable resin. . Specifically, for example, for polyurethane, Hydran WLS-201 (manufactured by Dainippon Ink & Chemicals), water-soluble resin. For gelatin, MC-243 (manufactured by Zerais Co., Ltd.) can be used, and it can be dissolved in water to about 5 to 30 wt%. For polyvinyl alcohol, Poval PVA117 (manufactured by Kuraray) can be used. For example, polyvinyl alcohol may be used by dissolving it in water at about 5 to 30 wt%.

(Example)
Hereinafter, a specific substrate for producing a composite cell structure will be shown as an example. The structure of the region having a different affinity with the deformable material formed on the surface of the substrate 1 differs depending on the material of the deformable material and the material of the substrate. Therefore, in the following embodiments, the configuration of regions having different affinity with the corresponding deformable material is illustrated for each combination of the material of the deformable material and the material of the substrate.

The hydrophilicity, lipophilicity, water repellency and oil repellency of the substrate surface will be described. The hydrophilicity of the substrate surface is a property that is easily wetted by water, has a small contact angle with water, and a substrate having a high energy surface with a surface energy of about 50 erg / cm ² or more is used as the hydrophilic substrate. A glass surface, a metal surface, PVA, cellulose, a crosslinked polymer electrolyte surface, a grafted resin surface, and the like correspond to the hydrophilic substrate surface. The lipophilic surface is a surface with a small contact angle with a hydrocarbon (for example, n-decane, etc.), the surface energy is about 20 to 50 erg / cm ² , and it is difficult to wet with water. Shows hydrophobicity. The surface includes PE, PP, polyester, nylon, PMMA, and the like. The water-repellent and oil-repellent surfaces are surfaces that repel water and oil, respectively, have a surface energy of about 20 erg / cm ² or less, and the surfaces of fluorine-based resins and silicone resins are applicable. (References on surface energy: surface science, industrial books (1990) Yoshito Kan)
Example 1
In the case of hydrophilic material 1 and hydrophilic substrate (protein solution such as gelatin + glass substrate, metal substrate)
1) Glass substrate + gelatin (1)
As shown in FIG. 10, alkyltrialkoxysilane, HMDS (hexamethyl) is left on the glass substrate surface, which is a hydrophilic substrate, leaving the glass substrate surface as a strip-shaped hydrophilic region 11 surrounding the concave portion 3. A silane coupling agent such as (disilazane) was applied in a hexagonal shape surrounding the recess 3 to form the lipophilic region 12. Similarly, a substrate in which a thermal oxide film is formed on a silicon substrate may be used.

  As a method for forming the oleophilic region 12, a substance having an affinity for the substrate surface is applied or transferred in a pattern using a printing method such as an ink jet method, a screen printing method, or a micro contact printing method, and then dried or heated. A fixing method is effective. In Example 1, a thin film of a 15% aqueous solution of gelatin is formed on the surface of a substrate having an affinity pattern formed by the above method. As a thin film forming method, a general liquid film coating means may be used, and a method of placing a soap film on the surface of the substrate 1 while forming a soap film is also effective. Thereafter, as shown in FIG. 5, the substrate 1 was decompressed to about 1 to 50 kPa in a decompression tank, and the gas sandwiched between the gelatin thin film and the substrate was expanded to deform the gelatin material and to be separated by the partition walls. A cell shape is formed. Gelatin can be solidified while maintaining its cell shape by gelatinization and moisture drying.

At this time, when there is no hydrophilic region on the substrate surface, it is difficult to control the wall thickness of the cell partition wall itself, and in addition, a thin film protruding from the substrate surface is formed between the partition wall and the substrate, so that the opening shape is formed. Although it is difficult to stabilize, when a substrate having a hydrophilic region is used as in this embodiment, the thickness of the gelatin partition wall can be controlled according to the width of the hydrophilic region of the substrate. The material is preferably a water-soluble protein that gels, such as gelatin, but it is also possible to use other proteins with excellent foamability.
2) Metal substrate + gelatin (1)
The above glass substrate (glass substrate + gelatin) shown in FIG. 10 was changed to a metal substrate, and a lipophilic region was formed on the surface of the metal substrate by forming a turtle shell pattern such as alkanethiol. As the metal substrate, a substrate having a film of Au, Ag, Cu or the like having a high affinity with alkanethiol on the surface is suitable, and the alkanethiol film is formed on the metal surface in a tortoiseshell pattern using a printing method. By forming, a new oily region in which the methyl group ends of the alkanethiol are arranged on the surface can be formed.

  Examples of the alkanethiol include n-decanethiol, n-undecanethiol, n-dodecanethiol, n-tetradecanethiol, n-pentadecanethiol, n-hexadecanethiol, n-heptadecanethiol, n-octadecanethiol, n-nona. Decanethiol, n-eicosanethiol, etc. can be used.

3) Glass substrate + gelatin (2)
As shown in FIG. 11, a silane cup having a fluorinated carbon end such as HFDS or fluorinated alkyltrimethoxysilane, leaving a hydrophilic region 11 which is a surface of a belt-shaped turtle shell pattern on the surface of a glass substrate having a plurality of recesses. The water-repellent pattern region 13 was formed by providing a ring agent layer. The shape of the pattern is a tortoiseshell pattern in which the surface of the glass substrate is left in a strip shape (hereinafter, the pattern shapes are all the same tortoiseshell pattern).

4) Metal substrate + gelatin (2)
The glass substrate + gelatin glass substrate shown in FIG. 11 is changed to a metal substrate, and the HFDT fluorinated alkanethiol is left on the surface of the metal substrate having a plurality of recesses, leaving the hydrophilic region 11 that is the surface of the belt-shaped turtle shell pattern. A water-repellent region 14 having fluorocarbon ends aligned on the surface was formed by forming a film such as the above. The micro contact printing method can be used as a patterning method.

5) Glass substrate or metal substrate + gelatin (1)
As shown in FIG. 12, a water-repellent region 14 with fine irregularities was formed on the surface of a glass substrate or metal substrate having a plurality of recesses, leaving the hydrophilic region 11 that is the surface of a strip-shaped turtle shell pattern. In this case, the affinity with the deformable material 2 can be changed by adjusting the fine structure of the surface without applying a drug or the like to the substrate surface.

6) Glass substrate or metal substrate + gelatin (2)
As shown in FIG. 13, a water-repellent region 15 having a fine unevenness self-similar shape was formed on the surface of a glass substrate or metal substrate having a plurality of recesses, leaving a hydrophilic region 11 that is a surface of a strip-shaped turtle shell pattern. . In this case, the affinity with the deformable material 2 can be changed by adjusting the fine structure of the surface without applying a drug or the like to the substrate surface.

7) Glass substrate or metal substrate + gelatin (3)
As shown in FIG. 13, an alkyl ketene dimer is used instead of forming a fine concavo-convex self-similar shape by leaving a hydrophilic region 11 which is a surface of a band-shaped turtle shell pattern on the surface of a glass substrate or metal substrate having a plurality of recesses. A water-repellent region 15 was formed by layer formation. Alkyl ketene dimers such as stearyl ketene dimer and behenyl ketene dimer are generally used as a sizing agent for preventing ink from bleeding on paper in the printing field, like alkenyl succinic anhydride. It is known that the alkyl ketene dimer has a self-similarity called “fractal” in its crystal surface structure and has a large actual surface area, so that water forms a surface that is difficult to wet to the back of a fine surface shape. The water-repellent region can be obtained by forming a film of this alkyl ketene dimer in a pattern on the substrate surface using an inkjet or other printing means and recrystallizing by remelting and cooling.

(Example 2)
In case of hydrophilic material 2 and hydrophilic substrate (hydrophilic UV curable resin + glass substrate, metal substrate)
1) Glass substrate + hydrophilic UV curable resin (1)
As shown in FIG. 10, a layer of a silane coupling agent such as alkyltrialkoxysilane or HMDS (hexamethyldisilazane) is provided on the surface of a glass substrate having a plurality of recesses, leaving the hydrophilic region 11 in a tortoiseshell pattern. As a result, the lipophilic region 12 was formed.

2) Metal substrate + hydrophilic UV curable resin (1)
The glass substrate shown in FIG. 10 is replaced with a metal substrate, and the hydrophilic region 11 is left in the pattern of a tortoiseshell pattern on the surface of the metal substrate having a plurality of recesses, and the lipophilic region 12 is formed by forming a film of alkanethiol or the like 3) Glass substrate + hydrophilic UV curable resin (2)
As shown in FIG. 11, the hydrophilic region 11 is left in a tortoiseshell pattern pattern on the surface of the glass substrate having a plurality of recesses, and a layer of a silane coupling agent such as HFDS or fluorinated alkyltrimethoxysilane is provided to provide water repellency. A pattern area was formed.

4) Metal substrate + hydrophilic UV curable resin (2)
The glass substrate shown in FIG. 11 is replaced with a metal substrate, and the hydrophilic region 11 is left in the pattern of a turtle shell pattern on the surface of the metal substrate having a plurality of recesses, and the water-repellent region 13 is formed by forming a film of HFDT or alkanethiol fluoride. Formed.

5) Glass substrate or metal substrate + hydrophilic UV curable resin (1)
As shown in FIG. 12, the hydrophilic region 11 was left in a turtle shell pattern on the surface of a glass substrate or metal substrate having a plurality of recesses to form a water-repellent region 14 with fine irregularities.

6) Glass substrate or metal substrate + hydrophilic UV curable resin (2)
As shown in FIG. 13, the water-repellent region 15 having a self-similar shape was formed by leaving the hydrophilic region 11 in a turtle shell pattern on the surface of a glass substrate or metal substrate having a plurality of recesses.

6) Glass substrate or metal substrate + hydrophilic UV curable resin (3)
As shown in FIG. 13, the water-repellent region 15 is formed by forming an alkyl ketene dimer layer on the self-similar surface, leaving the hydrophilic region 11 in a turtle shell pattern on the surface of the glass substrate or metal substrate having a plurality of recesses. Formed.

  It is possible to manufacture a honeycomb structure that does not deform by forming a cell structure by gas expansion using a deformable ultraviolet curable resin on a substrate having a hydrophilic pattern as described above, and then curing the substrate by ultraviolet curing. it can.

  For example, as in the process example shown in FIG. 9, a layer of water-soluble urethane acrylic ultraviolet curable resin Loctite 3301 is formed on the substrate 1, and a glass pressing plate 7 is placed thereon to sandwich the resin. By adjusting the gap between the two plates of the substrate 1 and the pressing plate 7, the layer thickness of the honeycomb structure can be controlled. In this state, the two plates sandwiching the resin are decompressed to about 1 to 50 kPa, and the resin shape is deformed by expanding the gas between the recess 3 of the substrate 1 and the resin to form a cell structure. A cell structure can be obtained by curing the resin by irradiating ultraviolet rays in a reduced pressure state after deformation. At this time, when there is no hydrophilic region on the substrate surface, it is difficult to control the thickness of the partition wall between cells, and a thin film protruding from the substrate surface is formed between the partition wall and the substrate 1, so It is difficult to stabilize the opening shape. However, when the substrate having the hydrophilic region of the present invention is used, the thickness of the partition between the cells can be controlled according to the width of the hydrophilic region of the substrate 1. In addition, although the example of hydrophilic UV curable resin was shown as a material, it is also possible to mix and use an additive for this.

(Example 3)
In the case of hydrophilic material 1 and lipophilic substrate (protein solution such as gelatin + resin substrate)
1) Hydrophilic region by excimer laser exposure As shown in FIG. 14, a tortoiseshell pattern of the hydrophilic region 17 is formed on the surface of the resin substrate, which is the lipophilic region 16 having a plurality of recesses. The formation of the turtle shell pattern is formed by exposing the surface of the resin substrate having lipophilicity to a strip-shaped turtle shell pattern-shaped light-shielding mask and exposing to an excimer laser. Alternatively, it is also effective to write corresponding to the turtle shell pattern using a laser scanning means. The other steps are the same as in the case of gelatin in Example 1.
FIG. Example of forming hydrophilic region by excimer laser exposure on lipophilic substrate 2) Hydrophilic region by irradiation with vacuum ultraviolet light As shown in FIG. 14, the hydrophilic region is formed on the surface of the resin substrate which is the lipophilic region 16 having a plurality of recesses. The pattern of the turtle shell pattern of the sex region 17 is formed. The formation of the turtle shell pattern is performed by irradiating the surface of the resin substrate having lipophilicity with a band-shaped turtle shell pattern-shaped light-shielding mask and irradiating it with vacuum ultraviolet light. The other steps are the same as in the case of gelatin in Example 1.

Example 4
In the case of hydrophilic material 2 and lipophilic substrate (hydrophilic UV curable resin + resin substrate)
1) Formation of hydrophilic region by excimer laser exposure As shown in FIG. 14, a tortoiseshell pattern of the hydrophilic region 17 is formed on the surface of the resin substrate, which is the lipophilic region 16 having a plurality of recesses. The formation of the turtle shell pattern is formed by exposing the surface of the resin substrate having lipophilicity to a strip-shaped turtle shell pattern-shaped light-shielding mask and exposing to an excimer laser. Alternatively, it is also effective to write corresponding to the turtle shell pattern using a laser scanning means. The other steps are the same as in the case of the hydrophilic UV curable resin of Example 1.

2) Formation of hydrophilic region by irradiation with vacuum ultraviolet light As shown in FIG. 14, a tortoiseshell pattern of the hydrophilic region 17 is formed on the surface of the resin substrate, which is the lipophilic region 16 having a plurality of recesses. The formation of the turtle shell pattern is performed by irradiating the surface of the resin substrate having lipophilicity with a band-shaped turtle shell pattern-shaped light-shielding mask and irradiating it with vacuum ultraviolet light. The other steps are the same as in the case of the hydrophilic UV curable resin of Example 1.

(Example 5)
In the case of hydrophilic material 1 and water-repellent substrate (protein aqueous solution such as gelatin + PDMS substrate, Teflon substrate)
1) Formation of hydrophilic region by plasma treatment As shown in FIG. 15, a turtle-shell pattern of a band-like water-repellent region 19 is formed on the surface of a PDMS substrate which is a water-repellent region 18 having a plurality of recesses. The formation of the turtle shell pattern is performed by applying oxygen plasma treatment to the surface of the water-repellent resin substrate with a band-shaped turtle shell pattern-shaped light shielding mask. The other steps are the same as in the case of gelatin in Example 1.

2) Formation of a titanium oxide layer + hydrophilic region by ultraviolet light irradiation As shown in FIG. 15, a tortoiseshell pattern of the band-like water-repellent region 19 is formed on the surface of the PDMS substrate, which is a water-repellent region 18 having a plurality of recesses. Form. The pattern formation of the turtle shell pattern is formed by forming a titanium oxide layer in a band-shaped turtle shell pattern pattern on the surface of a water-repellent resin substrate and irradiating with ultraviolet light using a light-shielding mask on other portions. Other steps are the same as in the case of the gelatin of Example 1.

3) Hydrophilic region formation by titanium oxide particle embedding + ultraviolet light irradiation On the surface of the PDMS substrate, which is the water repellent region 18 having a plurality of recesses, a turtle-shell pattern of the band-like water repellent region 19 is formed as shown in FIG. Form. The formation of the turtle shell pattern is formed by embedding fine titanium oxide particles in a band-like turtle shell pattern pattern on the surface of a water-repellent resin substrate and irradiating with ultraviolet light using a light-shielding mask in other portions. The hydrophilic region 19 is a hydrophilic region composed of a set of dots. Other steps are the same as in the case of the gelatin of Example 1.

(Example 6)
In the case of hydrophilic material 2 and water-repellent substrate (hydrophilic UV resin + PDMS substrate, Teflon substrate)
1) Formation of hydrophilic region by plasma treatment As shown in FIG. 15, a turtle-shell pattern of a band-like water-repellent region 19 is formed on the surface of a PDMS substrate which is a water-repellent region 18 having a plurality of recesses. The formation of the turtle shell pattern is performed by applying oxygen plasma treatment to the surface of the water-repellent resin substrate with a band-shaped turtle shell pattern-shaped light shielding mask. The other steps are the same as in the case of the hydrophilic UV resin of Example 1.

2) Formation of a titanium oxide layer + hydrophilic region by ultraviolet light irradiation As shown in FIG. 15, a tortoiseshell pattern of the band-like water-repellent region 19 is formed on the surface of the PDMS substrate, which is a water-repellent region 18 having a plurality of recesses. Form. The pattern formation of the turtle shell pattern is formed by forming a titanium oxide layer in a band-shaped turtle shell pattern pattern on the surface of a water-repellent resin substrate and irradiating with ultraviolet light using a light-shielding mask on other portions. The other steps are the same as in the case of the hydrophilic UV curable resin of Example 1.

3) Hydrophilic region formation by titanium oxide particle embedding + ultraviolet light irradiation As shown in FIG. 16, a turtle shell pattern of the band-like water repellent region 19 is formed on the surface of the PDMS substrate which is the water repellent region 18 having a plurality of concave portions. Form. The formation of the turtle shell pattern is formed by embedding fine titanium oxide particles in a band-like turtle shell pattern pattern on the surface of a water-repellent resin substrate and irradiating with ultraviolet light using a light-shielding mask in other portions. The hydrophilic region 19 is a hydrophilic region composed of a set of dots. The other steps are the same as in the case of the hydrophilic UV curable resin of Example 1.

(Example 7)
In the case of lipophilic material and hydrophilic substrate (lipophilic UV curable resin + glass substrate, metal substrate)
1) Lipophilic region formation by silane coupling agent on glass substrate surface As shown in FIG. 17, a glass substrate surface having a plurality of recesses 3 is formed in a hexagonal shape around each recess 3 and hydrophilic regions are formed on the glass substrate surface. 11, a film of a silane coupling agent such as an alkyltrialkoxysilane is formed as a lipophilic region 12 in the form of a band at the hexagonal boundary.

  As a method for forming the oleophilic region 12, a method of applying and fixing a pattern of an oleophilic substance such as a silane coupling agent by a printing method or the like, a substance applied on the surface layer is given affinity in a pattern shape by UV light irradiation. In addition to the above methods, a lipophilic substance is mixed in a material that easily forms the desired foam cell thickness (for example, an aqueous solution containing a surfactant), and heated in a pattern shape formed by a foaming process to make it lipophilic. A method of fixing a substance on a substrate is also effective.

2) Formation of a lipophilic region such as alkanethiol on the surface of the metal substrate As shown in FIG. 17, a hydrophilic region 11 is formed on the surface of the glass substrate having a plurality of recesses 3 in a hexagonal shape around each recess 3. Then, a film of alkanethiol or the like is formed as a lipophilic region 12 in a strip shape at the hexagonal boundary. The method for forming the lipophilic region 12 may be the same as the method for forming the lipophilic region with the silane coupling agent on the surface of the glass substrate.

(Example 8)
In case of lipophilic material and lipophilic substrate (lipophilic UV curable resin + resin substrate)
1) Formation of fine uneven regions on the surface of the resin substrate As shown in FIG. 18, regions having fine unevenness formed on hexagonal regions surrounding the respective recesses 3 on the surface of the resin substrate 1 having a plurality of recesses 3 are oil-repellent regions. 22, and the surface of the resin substrate 1 is left in a strip shape at each hexagonal boundary to form an oleophilic region 21.

2) Formation of self-similar shape fine unevenness region on resin substrate surface As shown in FIG. 19, self-similar shape fineness is formed in a hexagonal region surrounding each recess 3 on the surface of resin substrate 1 having a plurality of recesses 3. The region having the irregular shape is formed as the oil-repellent region 23, and the surface of the resin substrate 1 is left in a strip shape at each hexagonal boundary to form the lipophilic region 21.

3) Formation of an oil-repellent region on the surface of the resin substrate As shown in FIG. 19, an oil-repellent region 23 formed by an alkyl ketene dimer layer is formed in a hexagonal region surrounding each recess 3 on the surface of the resin substrate 1 having a plurality of recesses 3. The resin substrate 1 surface is formed in a strip shape at each hexagonal boundary to form a lipophilic region 21.

Example 9
Lipophilic material and water-repellent substrate (Oleophilic UV curable resin + PTFE fluororesin substrate)
1) Formation of fine uneven regions on the surface of the resin substrate As shown in FIG. 20, the hexagonal regions surrounding the respective recesses 3 on the surface of the fluororesin substrate 1 having a plurality of recesses 3 are left as the oil-repellent regions 24. The lipophilic region 25 is formed in a strip shape at the hexagonal boundary. The surface of the fluororesin substrate 1 forms a tortoiseshell pattern of the lipophilic region 25.

For the formation of the lipophilic region 25, an ArF excimer laser is irradiated on the fluororesin in trimethylboron gas (B (CH ₃ ) ₃ ). The photodissociated B extracts F atoms from the C—F bonds of the fluororesin excited at the same time and diffuses into the gas as BF ₃ . CH ₃ is substituted for C from which F has been removed, and thus has lipophilicity. (Reference: No. 3340501, Tokai Univ., Masataka Murahara et al.)
The properties of the deformable material shown in the above embodiment, the hexagonal region around the concave portion of the substrate surface with respect to the substrate (the concave portion peripheral pattern), and the properties of the turtle shell pattern region (partition wall pattern) formed at the boundary of this hexagon Are summarized in Table 1.

Composite cell structure manufacturing method Conventional method of manufacturing a composite cell structure Cross-sectional view of cell structure during gas expansion Cross-sectional view of cell structure formation during gas expansion Example of substrate surface pattern Example of vacuum foaming process (A) Example of vacuum foaming process (B) Example of vacuum foaming process (C) Example of vacuum foaming process between two substrates Example of forming a lipophilic pattern Example of forming a water-repellent pattern Example of forming a water-repellent pattern with fine irregularities Example of water-repellent pattern formed by self-similar fine irregularities Example of forming hydrophilic region on lipophilic substrate (A) Example of forming hydrophilic region on water repellent substrate (A) Example of forming hydrophilic region on water repellent substrate (B) Example of forming hydrophilic region on lipophilic substrate (B) Example of forming an oil-repellent region on an oleophilic substrate (A) Example of forming an oil-repellent region on a lipophilic substrate (B) Example of forming a lipophilic region on a water-repellent substrate

Explanation of symbols

1: Substrate 2: Deformable material 3: Recessed portion 4: High affinity region 5: Low affinity region 6: Cell 7: Press plate 11: Hydrophilic region 12: Lipophilic region 13: Water repellent region 14: Water repellent region Region 15: Water repellent region 16: Lipophilic region 17: Hydrophilic region 18: Water repellent region 19: Hydrophilic region 20: Titanium oxide particles 21: Lipophilic region 22: Oil repellent region 23: Oil repellent region 24: Oil repellent region Area 25: lipophilic area

Claims (12)

A composite cell structure in which a surface having a plurality of spaced recesses is coated with a deformable material so that a space remains in the recess, and a plurality of cells are formed in the deformable material by gas expansion pressure in the recess space. A body manufacturing substrate,
The substrate for manufacturing a honeycomb structure sheet, wherein the surface including the concave portion has at least two regions having different affinity for the deformable material. The plurality of spaced-apart recesses are regularly arranged, and at least one of the regions having different affinity for the deformable material surrounds each recess. The substrate for manufacturing a honeycomb structured sheet according to the description. The substrate for manufacturing a honeycomb structure sheet according to claim 1 or 2, wherein the region surrounding the concave portion is regularly arranged. The region having a high affinity for the deformable material among the regions having different affinity for the deformable material is formed into the shape of the partition wall of the opening of the composite cell structure. A substrate for manufacturing a honeycomb structure sheet according to any one of the above. Of the regions having different affinity for the deformable material, the region having high affinity for the deformable material is a region in which a plurality of dots having high affinity for the deformable material are formed. The honeycomb structure sheet manufacturing substrate according to any one of claims 1 to 4. The region having low affinity for the deformable material among the regions having different affinity for the deformable material is defined as a plurality of discontinuous regions. The substrate for manufacturing a honeycomb structured sheet according to the description. The substrate for manufacturing a honeycomb structure sheet according to claim 6, wherein the low affinity region surrounds the concave portion. The substrate for manufacturing a honeycomb structure sheet according to claim 6 or 7, wherein the low affinity region is a region in which a fine uneven shape that is difficult to wet is formed on a deformable material. The substrate for manufacturing a honeycomb structure sheet according to claim 6 or 7, wherein the low affinity region is a region where an alkyl ketene dimer layer is formed . A coating step of coating the surface of the substrate having a plurality of spaced recesses with a deformable material so that a space remains in the recesses;
A method of manufacturing a honeycomb structured sheet , comprising a cell forming step of forming a plurality of cells in the deformable material by an expansion pressure of a gas in the space of the recess,
The substrate is a honeycomb-structured sheet manufacturing method, which is a honeycomb-structured sheet for producing a substrate according to any one of claims 1-9. The method for manufacturing a honeycomb structured sheet according to claim 10, wherein in the coating step, the deformable material covering the surface of the substrate is in a sheet form. The method for manufacturing a honeycomb structured sheet according to claim 10 or 11, further comprising a curing step of curing the deformable material formed with the plurality of cells to fix the shape of the cells.

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