JP5046387B2 - Manufacturing method of honeycomb structure - Google Patents

Description

  The present invention relates to a method for manufacturing a honeycomb structure, and more particularly to a method for manufacturing a honeycomb structure having excellent heat resistance and chemical resistance.

  In recent years, honeycomb structures are expected to be applied to various fields of optical / electronic engineering and biotechnology. In the field of optics and electronics, for example, application to high-functional composite materials, catalysts, nonlinear optical materials, memory elements and the like is expected. In the field of biotechnology, it has been shown that in a porous film having a honeycomb structure, the honeycomb pattern provides a cell adhesion surface, and the porous structure provides access to a cell support base and a nutrient supply route. .

  As a method for obtaining a honeycomb structure having uniform pores of about submicron to 100 microns, there is a mold technique including nanoimprint. However, in this method, since the shape of the voids collapses when the mold is peeled off, it is difficult in principle to accurately reflect the structure of the mold.

  Further, there is known a method of drying a colloidal fine particle dispersion and obtaining a honeycomb-shaped porous film using the collected colloidal crystals as a template, but it takes time to collect, and after pouring the material, There were problems such as having to remove the mold.

  Therefore, a technique for manufacturing a honeycomb structure using a self-organization phenomenon has been studied for the above method. This is a method in which a honeycomb structure can be manufactured by self-accumulating droplets condensed from the air or the like and a polymer deposited at the solvent interface in the three-phase boundary region. Specifically, it is a method of obtaining a honeycomb-like porous film using a water droplet generated by applying (casting) a polymer solution on a solid substrate and blowing air of high humidity. The method using this self-organization phenomenon is a highly accurate honeycomb structure without using a complicated manufacturing apparatus and without requiring a long time for manufacturing as in the manufacturing method using the above-described mold technology. Can be manufactured.

  However, the honeycomb structure manufactured by the above-described method using the self-organization phenomenon uses a material that is not all crosslinked. Therefore, there was a problem with heat resistance and chemical resistance. As described above, the honeycomb structure is expected to be applied to a wide range of fields. However, in application, it is necessary to provide a honeycomb structure that is stable against various solvents.

  Therefore, the present invention has been made in view of the above problems, and an object thereof is to provide a honeycomb structure having excellent heat resistance and chemical resistance using an organic material having photocrosslinkability. It is in.

  As a result of considering the above problems, the present inventors can provide a honeycomb structure that has acquired heat resistance and chemical resistance by using an organic material having photocrosslinkability (for example, photocrosslinkable resin). I thought that. The organic material having photocrosslinkability forms a three-dimensional crosslinked structure when irradiated with light. This three-dimensional crosslinked structure is resistant to heat and chemicals. Therefore, if a honeycomb structure is manufactured using a material having such characteristics, a honeycomb structure excellent in heat resistance and chemical resistance can be provided.

  If a honeycomb structure is provided with an organic material having photocrosslinkability using a manufacturing method using the above self-organization phenomenon, the above-described mold technology can be used without using a complicated manufacturing apparatus as described above. It was thought that a honeycomb structure excellent in heat resistance and chemical resistance could be provided with high accuracy without requiring a long time for the production as in the production method using. However, when the present inventors manufactured a honeycomb structure from an organic material having a photocrosslinkability by using the above-described manufacturing method utilizing a conventionally known self-organization phenomenon, the honeycomb structure was uniformly submicron to about 100 microns. A honeycomb structure having pores could not be provided stably.

  Therefore, as a result of earnestly examining the manufacturing method using the self-organization phenomenon, the inventors of the present application control the timing of exposure to an organic material having photocrosslinkability to form a three-dimensional crosslinked structure. Even when an organic material having photocrosslinkability is applied, the present invention has been completed by paying attention to the provision of a honeycomb structure having uniform pores of about submicron to 100 microns.

  That is, in the method for manufacturing a honeycomb structured body of the present invention, a solution in which a hydrophobic organic solvent, a photocrosslinkable material, and a curing agent are mixed is applied on the substrate, and the application process is performed. The hydrophobic organic solvent is evaporated from the solution, and a droplet forming step for generating droplets on the surface of the solution, and the photocrosslinkable material is crosslinked on the surface where the droplets are generated by the droplet forming step. A method for manufacturing a honeycomb structure including a light irradiation step of irradiating light, wherein in the light irradiation step, the hydrophobic organic solvent is completely evaporated and droplets are formed or It is characterized by irradiating the above-mentioned light to a solution in which the trace maintains its original shape.

  In the method for manufacturing the honeycomb structure, in the droplet forming step, it is preferable to blow a gas having a relative humidity of 50% to 95% onto the solution at a predetermined flow rate.

  In the above method for manufacturing a honeycomb structure, the photocrosslinkable material is preferably composed of a monomer, an oligomer, or a mixture thereof.

  In the above method for manufacturing a honeycomb structured body, the light is preferably ultraviolet light or visible light.

  In the above honeycomb structure manufacturing method, the solution preferably contains an amphiphilic compound.

  In the above method for manufacturing a honeycomb structure, it is preferable that the curing agent is contained at least 2% by weight with respect to the photocrosslinkable material.

  The above honeycomb structure manufacturing method may include a step of forming or loading a substance different from the honeycomb structure into the pores of the honeycomb structure manufactured by the above honeycomb structure manufacturing method. .

  The present invention also includes a honeycomb structure manufactured by the above manufacturing method.

  Other objects, features, and advantages of the present invention will be fully understood from the following description. The benefits of the present invention will become apparent from the following description with reference to the accompanying drawings.

FIG. 2 is a view showing a honeycomb structure manufactured by the manufacturing method according to the present invention, in which (a) is a plan view showing a surface structure of the honeycomb structure, and (b) is shown in (a). Fig. 3 is an enlarged perspective view of another honeycomb structure. BRIEF DESCRIPTION OF THE DRAWINGS The mechanism by which a honeycomb structure is formed using the manufacturing method of the present invention is schematically described. In the figure, (a) is an explanatory view of a solution applied on a substrate viewed from the liquid surface side. Middle (b) is explanatory drawing which looked at the solution apply | coated on the board | substrate from the side surface side. It is a figure which shows the structure of the manufacturing apparatus which enforces the manufacturing method which concerns on this invention. The chemical structural formula of the amphiphilic compound contained in the honeycomb structure manufactured by the manufacturing method according to the present invention is shown. The surface structure of the honeycomb structure manufactured by the manufacturing method according to the present invention is shown. (A) in the figure is 200 seconds after application, (b) is 400 seconds after, and (c) is (c) in the figure. After 500 seconds, (d) in the figure was 600 seconds, (e) in the figure was 700 seconds, (f) in the figure was 800 seconds, and (g) in FIG. The surface structure of the structure is shown. It is the graph which showed the weight change of the said solution after apply | coating a solution to a container using the manufacturing method which concerns on this invention. It is the microscope image which observed the surface structure of the honeycomb structure with the scanning electron microscope, (a) is a perspective view of the said surface structure in the figure, (b) is a surface structure shown to (a) in the figure. It is the expansion perspective view which expanded. 1 shows the appearance of a honeycomb structure manufactured by the manufacturing method according to the present invention and peeled from a container. It is an optical microscope image which showed the surface structure of the honeycomb structure manufactured by the manufacturing method of this invention, (a) and (b) in a figure is a case where the density | concentration of a photocrosslinkable material and a hardening | curing agent is changed. It is an optical microscope image which showed the surface structure of the honeycomb structure manufactured by the manufacturing method of this invention. It is an optical microscope image showing the surface structure of the honeycomb structure, in which (a) is the surface structure of the honeycomb structure after applying pure water, (b) is ethanol, (c) is acetone, ( d) is an optical microscope image showing the surface structure of the honeycomb structure after applying the chloroform solution. 3 is an optical microscope image showing a surface structure of a honeycomb structure.

  An embodiment of the present invention will be described below with reference to FIG.

<Honeycomb structure>
FIG. 1 shows the structure of a honeycomb structure in the present embodiment. (A) in FIG. 1 is a plan view showing the surface structure of the honeycomb structure, and (b) in FIG. FIG. 2 is an enlarged perspective view of the honeycomb structure shown in FIG. As shown in FIG. 1, the honeycomb structure refers to a structure in which pores having a fixed shape and a fixed size are continuously and regularly arranged. This regular arrangement is two-dimensional in the case of a single layer and regular in three dimensions in the case of a multilayer. This regularity is arranged so that a plurality of (for example, six) holes surround one hole in a two-dimensional manner, and three-dimensionally like a face-centered cubic or hexagonal crystal structure. However, depending on the manufacturing conditions, other regularity may be exhibited.

  The honeycomb structure of the present invention is manufactured using a photocrosslinkable material. The photo-crosslinkable material refers to a material having a characteristic of forming a three-dimensional crosslinked structure by light irradiation.

  The photocrosslinkable material can be crosslinked (cured) by irradiation with ultraviolet rays and visible light, and is a (meth) acrylate oligomer, (meth) acrylate monomer, or a mixture of these oligomers, monomers, or a mixture thereof. A main component of a photopolymerization initiator (a) in an amount sufficient to polymerize and cure, an epoxy group-containing compound, a vinyl compound, a compound having an oxetane ring, an alicyclic epoxy compound, or a mixture thereof; Those containing as a main component a photopolymerization initiator (b) in an amount sufficient to polymerize and cure these compounds and mixtures thereof are used. In addition, a half-ester compound, a (meth) acrylate monomer, an epoxy group-containing compound, a vinyl compound, a compound having an oxetane ring, an alicyclic epoxy compound, or a mixture thereof, and these compounds, monomers, and mixtures thereof are polymerized and cured. The main component of the photopolymerization initiator (a) and the photopolymerization initiator (b) in a sufficient amount can be used.

  The (meth) acrylate-based oligomer is an oligomer having at least one (meth) acrylate group at the molecular end or side chain. For example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, melamine (Meth) acrylate and the like. These can be used alone or in combination of two or more.

  The (meth) acrylate monomer is a monomer having one or more (meth) acrylate groups at the molecular end or side chain. For example, dicyclopentadiene mono (meth) acrylate, dicyclopentadieneethoxy (meth) acrylate, isobonyl There are (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, diethylene glycol di (meth) acrylate and the like. These can be used alone or in combination of two or more.

  The photopolymerization initiator (a) is a compound that generates an active radical by irradiating with ultraviolet light having a wavelength of 200 to 600 nm and light in the visible light region to cause the polymerization reaction to proceed. Examples thereof include benzoin photopolymerization initiators, acetophenone photopolymerization initiators such as diethoxyacetophenone, and thioxanthone photopolymerization initiators such as thioxanthone and diethylthioxanthone. These can be used alone or in combination of two or more. Moreover, these addition amount is 0.01-20 weight% with respect to 100 weight% of these oligomers, monomers, and mixtures thereof (meth) acrylate oligomer, (meth) acrylate monomer, or mixtures thereof. .

  The epoxy group-containing compound is an oligomer having one or more epoxy groups in one molecule. For example, bisphenol type epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, polyglycidyl ether, alicyclic epoxide, human dyne Type epoxy resin, glycidylamine type epoxy resin, dimer acid modified epoxy resin, NBR modified epoxy resin, CTBN modified epoxy resin and the like. These can be used alone or in combination of two or more.

  Examples of the vinyl compound include alkyl vinyl ethers, styrene, alkynyl vinyl ethers, aryl vinyl ethers, and alkyl divinyl ethers. These can be used alone or in combination of two or more.

  Examples of the compound having an oxetane ring include oxetane alcohol, xylylene oxetane, allyl oxetane, oxetanylsilsesoxane, triethoxysilylpropoxyoxetane, and the like. These can be used alone or in combination of two or more.

  The photopolymerization initiator (b) is one that generates an acid by irradiating ultraviolet light having a wavelength of 200 to 600 nm and light in a visible light region, and causes the polymerization reaction to proceed by using the generated acid as a catalyst. There are sulfonium salts, iodonium salts, diazonium salts, azide compounds, sulfonic acid ester compounds, and the like. Examples include triallylsulfonium hexafluoroantimony analogs, triallylsulfonium hexafluorophosphate analogues, P, P′dialkyldiallyliodonium salt hexafluoroantimony analogues, P, P′dialkyldiallyliodonium salt hexafluorophosphate analogues, and the like. . These can be used alone or in combination of two or more. Moreover, these addition amount is 0.01-20 weight% with respect to 100 weight% of these compounds and those mixtures, and these compounds, and those mixtures.

  The half ester compound is an epoxy resin (A) having two or more epoxy groups in one molecule as a starting material, and 0.5 to 0.9 equivalents with respect to 1 equivalent of the epoxy groups in the epoxy resin. A compound having an epoxy group, a hydroxyl group, and an unsaturated compound in one molecule, which is vinyl esterified by reacting the unsaturated monocarboxylic acid (B) or an unsaturated compound (C) having a carboxyl group. According to this synthesis method, it is possible to obtain a resin having a maximum of three types of functional groups in one molecule. These can be used alone or in combination of two or more.

  The component used as an essential raw material of the said half ester compound is demonstrated. As a starting material, an epoxy resin (A) having two or more epoxy groups in one molecule is used. Any known bifunctional epoxy resin can be used without particular limitation. Specifically, bisphenol type epoxy resin such as bisphenol A type, bisphenol S type, bisphenol F type, alicyclic epoxy resin, diglycidyl ether type epoxy resin, diglycidyl ester type epoxy resin, diglycidylamine type epoxy resin, etc. And bifunctional epoxy resins. These can be used alone or in combination of two or more. Examples of the trifunctional or higher functional epoxy resin include a phenol novolak resin, a cresol novolak resin, and a reactant of trisphenolmethane and epichlorohydrin. These can be used alone or in combination of two or more.

  Examples of the unsaturated carboxylic acid (B) include acrylic acid, methacrylic acid, furonic acid, and cinnamic acid. From the viewpoint of polymerization, acrylic acid and methacrylic acid are preferred.

  Examples of the unsaturated compound (C) include a half ester compound of a hydroxyl group-containing unsaturated compound and an acid anhydride. Specifically, a reactant of hydroxyethyl acrylate acrylate and succinic anhydride, methacryl And a reaction product of hydroxyethyl acid and phthalic anhydride. These can be used alone or in combination of two or more.

  Thus, in the honeycomb structure according to the present invention, a three-dimensional crosslinked structure is formed by light irradiation by using a photocrosslinkable material. This three-dimensional crosslinked structure is not easily affected by heat and chemicals. That is, the honeycomb structure in which the three-dimensional crosslinked structure is formed has characteristics excellent in heat resistance and chemical resistance.

  The lower limit of the concentration of the photocrosslinkable material (the concentration relative to the solution at the time of application to the substrate) is preferably 2.5 g / L or more, more preferably 5 g / L or more, and 10 g / L or more. Most preferably it is. The upper limit is preferably 150 g / L or less, more preferably 100 g / L or less, and most preferably 80 g / L or less. However, the present invention is not limited to this, and the concentration can be appropriately set so that a honeycomb structure that meets various application conditions can be manufactured.

  In producing the honeycomb structure of the present invention, since it is essential to form fine water droplet particles on the solution, the solvent to be used must be water-insoluble (hydrophobic). Therefore, for example, halogen-based organic solvents such as chloroform and methylene chloride, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, water-insoluble ketones such as methyl isobutyl ketone, diethyl ether And ethers such as carbon disulfide are used as the solvent. These organic solvents may be used alone or as a mixed solvent in which these solvents are combined.

  As a substrate used for manufacturing the honeycomb structure of the present invention, inorganic materials such as glass, metal, silicon wafer, organic materials excellent in organic solvent resistance such as polypropylene, polyethylene, polyetherketone, and polyfluorinated ethylene, water, Liquids such as liquid paraffin and liquid polyether can be used.

  A conventionally well-known hardening | curing agent can be used as a hardening | curing agent used for this invention. Examples of the curing agent used in the polymerization reaction by generating active radicals by irradiating with ultraviolet rays having a wavelength of 200 to 600 nm and visible light range include acetophenone, diethoxyacetophenone, 2,2-dimethoxy- 2-phenylacetophenone, 1-hydroxycyclohexylacetophenone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyltrichloroacetophenone, benzophenone compounds include benzophenone, benzophenone oxime, 4,4′- Tetra (t-butylperoxycarbonyl) benzophenone and benzoin ether compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether. As thioxanthone, diethylthioxanthone, and ketone compounds, 1-hydroxycyclohexyl phenyl ketone, 4- (2-acryloyloxy) phenyl (2-hydroxy-2-propyl) ketone, α-Hydroxyisobutylphenyl ketone and other compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzyldimethyl ketal, benzyl, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, methylisobutyroyl-methylphosphinate, methylisobutyroyl-phenylphosphinate, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, oligo [2-hydride Roxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and the like.

  Examples of the curing agent used for the polymerization reaction by generating an acid by irradiating ultraviolet light having a wavelength of 200 to 600 nm and light in the visible light region and using the generated acid as a catalyst include, for example, a sulfonium salt, an iodonium salt, a diazonium salt, Examples include azide compounds and sulfonic acid ester compounds. Examples include triallylsulfonium hexafluoroantimony analogs, triallylsulfonium hexafluorophosphate analogues, P, P′dialkyldiallyliodonium salt hexafluoroantimony analogues, P, P′dialkyldiallyliodonium salt hexafluorophosphate analogues, and the like. . If the concentration of the curing agent is at least 2% by weight with respect to the photocrosslinkable material, a good honeycomb pattern can be formed. However, the present invention is not limited to the above values, and the concentration can be appropriately set so that a honeycomb structure that meets various application conditions can be manufactured. In addition, the honeycomb structure manufactured using the manufacturing method of the present invention may be configured to be used as it is after being manufactured on the substrate by manufacturing it on the desired substrate from the beginning. It may be configured to be installed on a desired substrate after being peeled off from the substrate at the time. For example, by adjusting the concentration of the curing agent, the honeycomb structure of the present invention formed on the substrate can be peeled off from the substrate using tweezers as described in detail in a later example. Note that the peeling method is not limited to this, and the substrate may be placed on a desired substrate after being peeled off from the substrate at the time of manufacture after being immersed in an appropriate solvent such as ethanol. Also, when used after peeling, acrylic resin, urethane resin, epoxy resin, half ester compound, silane coupling agent, etc. that match the material and desired substrate material for the purpose of improving adhesion to a new substrate It is also possible to use an adhesive.

  In addition, the honeycomb structure of the present invention may be a honeycomb structure film having a stretched pore arrangement structure by stretching. The stretching method is not particularly limited, and can be performed, for example, by pinching two or more ends of the honeycomb structure with tweezers or hands and pulling in the extending direction. Alternatively, stretching can be performed using a micromanipulator.

  As the amphiphilic compound used in the present invention, an amphiphilic polymer can be used. Examples of the amphiphilic polymer include an amphiphilic polymer having polyacrylamide as a main chain skeleton, a dodecyl group as a hydrophobic side chain, and a carboxyl group as a hydrophilic side chain, and a polyethylene glycol / polypropylene glycol block copolymer. .

  Hydrophobic side chains are nonpolar linear groups such as methylene groups and phenylene groups, and branch off hydrophilic groups such as polar groups and ionic dissociation groups to the end, excluding linking groups such as ester groups and amide groups. It is preferable that the structure does not. For example, when a methylene group is used, it is preferably composed of 5 or more units.

  The hydrophilic side chain preferably has a structure having a polar part, an ionic dissociation group, or a hydrophilic part such as an oxyethylene group at the terminal via a linking part such as a methylene group.

  The ratio of the hydrophobic side chain to the hydrophilic side chain depends on the size, nonpolarity, polarity strength, and hydrophobicity of the hydrophobic organic solvent, but the unit ratio is 3/1 to 1/3. A range is desirable. In the case of a copolymer, a block copolymer in which a hydrophobic side chain and a hydrophilic side chain form a block as long as it does not affect the solubility in a hydrophobic solvent, rather than an alternating polymer of hydrophilic side chains of hydrophobic side chains. It is preferable that

  The honeycomb structure of the present invention can be used as, for example, a cell culture substrate in the biotechnology field. Therefore, it is preferable to use a non-toxic amphiphilic compound for such applications. Non-toxic amphiphilic compounds include, for example, polyethylene glycol / polypropylene glycol block copolymers and acrylamide polymers as the main chain skeleton, and both dodecyl groups as hydrophobic side chains and lactose groups or carboxyl groups as hydrophilic side chains Amphiphilic polymers, or ion complexes of anionic polymers such as heparin, dextran sulfate, and nucleic acids (DNA and RNA) with long-chain alkyl ammonium salts, and water-soluble proteins such as gelatin, collagen, and albumin have hydrophilic groups. It is desirable to use an amphiphilic polymer.

  In addition to air, an inert gas such as nitrogen gas or argon gas can be used as the gas whose humidity and flow rate are controlled when the honeycomb structure of the present invention is manufactured. These gases are preferably subjected to dust removal treatment such as passing through a filter in advance. Since dust in the atmosphere affects the honeycomb structure formed as condensation nuclei of water vapor, it is preferable to install dust removal equipment and the like at the manufacturing site.

  It is presumed that the mechanism for forming the honeycomb structure in the present invention is as shown in FIG. FIG. 2 schematically illustrates a mechanism by which the honeycomb structure 5 is formed by the manufacturing method of the present invention. FIG. 2 (a) shows the solution 2 applied on the substrate 1 from the liquid surface side. It is explanatory drawing seen, (b) in FIG. 2 is explanatory drawing which looked at the solution 2 apply | coated on the board | substrate 1 from the side surface side. As shown in FIG. 2, the solution 2 (coating step) applied on the substrate 1 has water on the surface of the solution 2 (ie, evaporative cooling) where the latent heat is removed and the temperature is lowered when the hydrophobic organic solvent evaporates. It condenses into minute water droplets (droplets) 3 and adheres to the surface of the solution 2 (droplet forming step). By the action of the hydrophilic portion of the amphiphilic compound 4 in the solution 2, the surface tension between the water droplet 3 and the hydrophobic organic solvent is reduced, and the water droplet 3 is prevented from aggregating and fusing into one lump. The water droplets 3 are transferred and collected by the flow of the solution 2 based on the solvent evaporation and the supplement from the surroundings, and are further closely packed by the transverse capillary force. As described above, since the honeycomb structure 5 forms a honeycomb pattern structure using the photocrosslinkable material, it is necessary to irradiate the light 6 with which the photocrosslinkable material forms a crosslinked structure. Therefore, in the production method of the present invention, as shown in FIG. 2, the hydrophobic organic solvent is completely evaporated and the water droplet 3 remains on the surface of the solution 2 or there is a trace of the water droplet 3. In the stage where the original shape is maintained, light 6 is irradiated (light irradiation process). By irradiating with light 6, the photocrosslinkable material forms a crosslinked structure, and finally, water completely evaporates and the polymer is left in the form of regularly arranged honeycombs, and the honeycomb structure 5 is completed.

  Examples of the light used for manufacturing the honeycomb structure of the present invention include ultraviolet light and visible light having a wavelength of 200 to 600 nm, and among these, depending on the type of the photocrosslinkable resin and the curing agent used in the present invention. Just choose. For example, in the case of using a curing agent having a characteristic of absorbing 250 nm ultraviolet visible light, ultraviolet (lamp) can be used.

  As described above, in the present invention, the honeycomb structure is formed by a method using the self-organization phenomenon. However, the inventors of the present invention use a manufacturing method using the above-described conventionally known self-organization phenomenon. Thus, when an attempt was made to manufacture a honeycomb structure from a photocrosslinkable material, it was not possible to stably provide a honeycomb structure having uniform pores of about submicron to 100 microns. Therefore, the inventors of the present invention have made extensive studies on a manufacturing method using a self-organization phenomenon, and as a result, by controlling the timing of exposure to an organic material having photocrosslinkability to form a three-dimensional crosslinked structure. As a result, a good honeycomb structure was formed. That is, as described above, in the production method of the present invention, the timing of exposure is determined based on whether the hydrophobic organic solvent is completely evaporated and the water droplet 3 remains on the surface of the solution 2 or the trace of the water droplet 3 is in its original form. By setting to a stage in which the above is maintained, a good honeycomb structure is formed. Although details will be described in an embodiment described later, when this timing is early, the trace of the template of water droplets on the solution surface disappears or collapses during exposure. This is presumably because the hydrophobic organic solvent in the solution is not completely evaporated and the solution surface is fluid, and water droplets are fused by heat from the light source and heat during the reaction. On the other hand, when the exposure timing is later than the above-described preferable exposure timing, the size of the pores of the honeycomb structure tends to be reduced, but the honeycomb-like pattern is similarly formed. There are two possible causes for the small holes. The first is that since the water droplets gradually evaporate and shrink, the structure itself shrinks and the hole diameter becomes smaller. Secondly, since the material is in a liquid state, it is considered that the structure flows over time when uncured.

  The exposure timing can be controlled by monitoring the weight of the solution applied on the substrate. That is, the weight of the solution decreases with a certain slope immediately after application on the substrate. Then, after a predetermined time, the inclination becomes gentle and finally becomes a constant value. This is because the hydrophobic organic solvent evaporates immediately after coating, and the water droplets that serve as the template evaporate after the hydrophobic organic solvent evaporates. After that, when the water droplets also evaporate and there is no other thing to evaporate, it is considered that the weight becomes constant. At the stage where the hydrophobic organic solvent still remains, since it is a dilute solution, the cross-linking reaction rate is very low, and it is difficult to immobilize the structure of the water droplet as a template. On the other hand, when the water droplets evaporate, the honeycomb structure is not fixed or the pore size is reduced even if the honeycomb structure is fixed. Therefore, it is possible to obtain a good honeycomb structure by performing exposure at a stage where the weight is monitored and the hydrophobic organic solvent evaporates and water droplets remain or the traces of the water droplets do not collapse. it can.

  As an environment for performing the manufacturing process of the honeycomb structure of the present invention, the relative humidity is preferably in the range of 50 to 95%. If it is less than 50%, water condensation on the solution surface tends to be insufficient. If it exceeds 95%, it is difficult to control the environment, and it tends to be difficult to maintain a uniform honeycomb structure.

  As an environment in which the production process of the present invention is performed, it is important to apply a steady wind having a constant air volume in addition to the relative humidity. The wind speed is preferably 0.05 m / second to 1 m / second. If it is less than 0.05 m / sec, it tends to be difficult to control the environment. Moreover, the wind speed exceeding 1 m / sec causes disturbance of the solvent surface, and tends to make it difficult to obtain a uniform honeycomb structure.

  The direction in which the steady air is applied can be produced in any direction from 0 ° to 90 ° with respect to the substrate surface, but is preferably 30 ° to 60 ° in order to improve the uniformity of the honeycomb structure. .

  It is desirable to strictly manage the environment in which the production process of the present invention is performed by using a commercially available constant dew point humidity generator or the like. It is desirable to control the air volume with a blower or the like and use a closed space in order to prevent the influence of outside air. In addition, it is desirable to set a gas introduction / extraction path and a film forming environment so that the gas is replaced by a laminar flow. Furthermore, it is desirable to monitor the temperature, humidity, flow rate, etc. with a measuring instrument in order to control the film forming quality. In order to control the hole diameter and film thickness of the honeycomb structure with high accuracy, it is essential to strictly control these parameters (particularly humidity and flow rate).

  The production method of the present invention is suitable for producing a honeycomb structure having a pore diameter of 0.1 μm to 100 μm. A preferable hole diameter is 0.3 μm to 20 μm, and more preferably 0.4 μm to 10 μm.

  When the pore diameter is less than 0.1 nm, the pores are not arranged in a honeycomb shape, and each pore diameter tends to vary. Further, when the pore diameter exceeds 100 μm, the shape of the pores collapses from a perfect circle, and there is a tendency that an isotropic film cannot be obtained.

  In the case of using nanometer-order fine particles or a fine structure, it is generally preferable that the pore diameter of the honeycomb structure of the present invention is small, because it has a high density. In order to reduce the pore diameter of the honeycomb structure using the manufacturing method of the present invention, it is effective to promote rapid drying. For example, it is effective to use a low-boiling point solvent as the solvent used, raise the support temperature, or shorten the initial developing solution thickness by increasing the developing speed.

  The thickness of the honeycomb structure of the present invention is approximately the pore diameter size to 1 mm, but a thick layer without pores can be provided on the substrate side. In this case, the thickness of the thick layer without voids can be controlled at 0 to 500 μm.

  The pores of the honeycomb structure obtained according to the above manufacturing method can be formed or filled with a substance different from the structure to form another honeycomb structure. For example, infrared absorbing particles can be filled. Further, after forming or filling a substance different from the honeycomb structure, the structure can be removed to obtain another honeycomb structure.

The different materials include metals such as Au, Ag, and Pt, organic polymer compounds such as polystyrene, polymethyl methacrylate, polycarbonate, and UV curable resin, and inorganic polymers such as polydimethylsiloxane and polyphenylmethylsiloxane. Examples thereof include inorganic oxides such as compounds, SiO ₂ , Al ₂ O ₃ , TiO ₂ , and ZrO ₂ .

  The different substances may be a single substance or a complex of a plurality of substances. Further, chemical modification such as physical adsorption of alkylbenzene sulfonate or carboxylic acid polymer on the surface or grafting of a compound having carboxylic acid may be performed.

  Further, as the different substance, a material that can maintain magnetism may be used. Thereby, a high-density magnetic storage medium can be provided. In addition, when using a magnetic material, since it is necessary to align the magnetic axis, it is preferable to use a material exhibiting crystal anisotropy. For the same reason, it is preferable to apply a magnetic field when creating the structure.

  In addition, as a method of forming or filling these different substances, a method of impregnating a solution prepared with a solvent that does not dissolve a molten state or honeycomb structure, a latex, a fine particle dispersion, a method of impregnating a monomer, and then heating or Examples thereof include a method of polymerizing by light, a method of impregnating tetraethoxysilane or metal alkoxide with a liquid obtained by adding an appropriate catalyst and water, and then dehydrating and condensing by heating or light (so-called sol-gel method).

  Furthermore, as a method of removing the honeycomb structure after forming or filling different substances, a method of immersing in a solvent that can dissolve only the structure without dissolving the different substances or a heat resistance such as an inorganic oxide of the different substances. In the case where there is, there can be exemplified a method in which the structure is thermally decomposed and removed by heating to 500 ° C. or higher. Specific examples include oxygen plasma treatment, ion milling, and laser ablation.

  As described above, in the present invention, the timing of light irradiation for crosslinking the photocrosslinkable material is set to a stage where the hydrophobic organic solvent of the solution applied on the substrate is completely evaporated and condensation occurs. Thus, even when the photocrosslinkable material is applied to the manufacturing method using the self-organization phenomenon, it is possible to provide a honeycomb structure having uniform pores of about submicron to 100 microns. A honeycomb structure manufactured using a photocrosslinkable material is excellent in heat resistance and chemical resistance.

  The honeycomb structure obtained by the present invention is a technology applicable to each field of optical / electronic engineering and biotechnology. A periodic honeycomb-like porous body is expected to be applied to a photonic crystal element. Further, in the field of electronics, it is possible to stably maintain a structure in heat or a solvent as a matrix material such as an electrode. In the field of biotechnology, the influence of the substrate pattern on the cell surface has been elucidated in recent years. However, since it has resistance to various solvents and the like, it can be provided as a stable patterned substrate.

〔Example〕
The features of the present invention will be described more specifically with reference to the following examples. Example 1 shows an experimental example in which the exposure timing is controlled, Example 2 shows an experimental example in which the concentrations of the photocrosslinkable material and the curing agent were examined, and Example 3 shows the present invention. The experimental result which investigated the tolerance with respect to various solvents of the honeycomb structure manufactured by this method is shown. A honeycomb structure manufactured using a photocrosslinkable material different from that in Example 1 is shown in Example 4.

<Example 1>
In this example, the honeycomb structure was manufactured using the manufacturing apparatus 10 shown in FIG. FIG. 3 is a configuration diagram of the honeycomb structure manufacturing apparatus 10. The manufacturing apparatus 10 includes a container (substrate) 11, a scale 12, a fiber type UV light source 13, a nitrogen injector 14, and a monitoring device 15.

  The installation angle θ with respect to the container 11 in the nitrogen injector 14 was set to θ = 30 °. The separation distance h between the nitrogen injector 14 and the container 11 was 85 mm. The separation distance H between the container 11 and the fiber type UV light source 13 was set to 100 mm. The scale 12 and the monitoring device 15 are connected, and the weight of the solution 2 in the container 11 measured by the scale 12 can be monitored by the monitoring device 15. By monitoring the weight of the solution 2 using the monitoring device 15, the exposure timing of the solution 2 by the fiber UV light source 13 can be set optimally.

  A bisphenol A type epoxy resin (Dainippon Ink & Chemicals, EXA-850CRP) was used as the photocrosslinkable material. As the curing agent, an iodonium salt cationic curing agent (manufactured by Rhodia, 2074) was used. Chloroform (Wako Pure Chemicals, grade 1) was used as the hydrophobic organic solvent. Cap was used as the amphiphilic compound. The chemical structural formula of the amphiphilic compound used in this example is shown in FIG.

  Next, the solution 2 (FIG. 3) will be described. First, a chloroform solution was prepared so that the concentration of the iodonium salt cationic curing agent was 10 g / L. Next, separately from this, a chloroform solution was prepared so that the concentration of the bisphenol A type epoxy resin was 100 g / L and the concentration of the amphiphilic compound was 1 g / L. 1 ml of each of the two prepared chloroform solutions was taken and mixed in a stoppered measuring cylinder.

  The manufacturing apparatus 10 shown in FIG. 3 was used for manufacturing the honeycomb structure. For the container 11, a lid (diameter: 36 mm) of a petri dish (TOKYO PETRI SCHALE, firing port 30) was used. Solution 2 (2 ml) mixed in a stoppered graduated cylinder was applied (cast) to the container 11, and humidified nitrogen gas was blown onto the lid through a washing bottle containing water. Nitrogen had a relative humidity of 70%, a temperature of 20 ° C., and a flow rate of 4 L / min. The nitrogen flow rate was measured using a flow meter (KOFLOC, MODEL RK1600R). In order to measure the weight change due to evaporation of chloroform and water, all experiments were performed on the balance 12 and the weight change was observed with the monitoring device 15.

  In this example, the timing of irradiation with UV light is 7 levels for the solution 2 from application to the container 11 until the chloroform and water droplets evaporate and the weight stabilizes (200 seconds after application, 400 seconds, 500 seconds after application). Seconds, 600 seconds, 700 seconds, 800 seconds, 1000 seconds). The preparation conditions of the solution 2 at each stage are shown in Table 1 below.

容器１１に塗布して窒素雰囲気下で所定の時間を経過した各溶液２には、ファイバー式ＵＶ光源（浜松ホトニクス株式会社 製）１３を用いてＵＶ光を２分間照射した。

Each solution 2 that was applied to the container 11 and passed a predetermined time under a nitrogen atmosphere was irradiated with UV light for 2 minutes using a fiber-type UV light source (manufactured by Hamamatsu Photonics) 13.

  The state in the container 11 after UV light irradiation was observed using an optical microscope (OM, Olympus BH-2), and was observed with a scanning electron microscope (SEM, Hitachi S-3500N) by sputtering with Pd / Pt. .

  As a result of observation, when nitrogen was applied after application, a part of the surface started to become cloudy in about 100 seconds, the range gradually expanded, and almost in 200 seconds. The cloudy surface disappeared from the edge after about 400 seconds, but it did not shrink after about 500 to 600 seconds. When the timing of exposure was early (less than 500 seconds after application), it was observed that the cloudiness formed on the surface during UV irradiation contracted. When observed with an optical microscope, the traces of the mold of water droplets disappeared or collapsed. This is presumably because the solution chloroform is fluid because the solvent chloroform is not overwhelmed, and the water droplets are fused by heat from the light source 13 and heat during the reaction. Further, when the exposure timing was late (after 500 seconds after coating), no change was observed in the white portion of the sample before and after UV irradiation. The result of observing the surface structure of the honeycomb structure with an optical microscope is shown in FIG. In FIG. 5, (a) is a solution exposed 200 seconds after coating, (b) is after 400 seconds, (c) is after 500 seconds, (d) is after 600 seconds, and (e) is after 700 seconds. (F) shows the surface structure of the solution (honeycomb structure) exposed after 800 seconds and (g) after 1000 seconds. From (a) and (b) of FIG. 5, the elapsed time after coating is almost changed to the surface structure up to 400 seconds, that is, no honeycomb pattern is seen, but as shown in (c) of FIG. After a second, the honeycomb-like pattern structure began to be fixed, and as shown in FIGS. 5E to 5G, a honeycomb-like pattern was seen after 700 seconds. When a longer time elapses, the size of the pores tends to be reduced, but a honeycomb-like pattern is similarly formed. There are two possible reasons why the holes become smaller as the elapsed time becomes longer. First, since the water droplets gradually evaporate and shrink, the structure itself shrinks and the pore diameter becomes small. Further, since the material is in a liquid state, it is considered that the structure flows over time when uncured. FIG. 6 shows the change in weight after application of each solution. FIG. 6 shows the weight of the solution along the vertical axis, and the elapsed time from the application along the horizontal axis. The change in weight of the seven types of solutions is represented by the exposure timing (in FIG. It is shown with an arrow. As shown in FIG. 6, the weight of each solution is uniformly reduced with a constant slope immediately after application, but the slope becomes gentle after 400 to 500 seconds and finally becomes a constant value. This is because chloroform as a solvent evaporates immediately after coating, but after chloroform completely evaporates, water droplets as a template evaporate. It is considered that the weight becomes constant when the water droplets also completely evaporate and then the evaporating substance disappears. Before 500 seconds have elapsed after coating (FIGS. 5A to 5C), chloroform still remains, and since it is a dilute solution, the crosslinking reaction rate is very low, and the structure of the template water droplet is immobilized. It ’s difficult. On the other hand, if the water droplets that serve as the mold evaporate, the pattern structure on the honeycomb is not fixed, or the pore size is reduced even if the pattern structure is fixed.

  The results of observing the honeycomb structure shown in FIG. 5 (e) with a scanning electron microscope are shown in FIGS. 7 (a) and 7 (b). FIG. 7A is a perspective view showing the surface structure of the honeycomb structure, and FIG. 7B is an enlarged perspective view in which the surface structure shown in FIG. 7A is enlarged. From the observation results shown in FIGS. 7A and 7B, it was revealed that a honeycomb structure having pores having a diameter of 3 microns and a height of about 1 micron was formed.

  From the above, it can be said that the exposure timing is most suitable when the solvent chloroform is evaporated and water droplets remain or the traces of the water droplets are not broken.

<Example 2>
In this example, the concentration of the photocrosslinkable material and the curing agent in the honeycomb structure manufactured according to the method of the present invention was examined. In this example, as in Example 1 above, a bisphenol A type epoxy resin (EXA-850CRP manufactured by Dainippon Ink & Chemicals, Inc.) was used as the photocrosslinkable material, and an iodonium salt cationic curing agent was used as the curing agent. , Cap was used for the amphiphilic compound, and a chloroform solution was used for the hydrophobic organic solvent.

  A chloroform solution A was prepared so that the concentration of the bisphenol A type epoxy resin was 100 g / L and 10 g / L, respectively. Next, separately from this, the chloroform solution B was prepared so that the density | concentration of an iodonium salt type | system | group cationic hardening | curing agent might be 10 g / L, 1 g / L, and 0.1 g / L. These chloroform solution A and chloroform solution B were mixed at a volume ratio of 1: 1 to prepare samples (1) to (5) shown in Table 2 below.

すなわち、各サンプルは体積比１：１で混合しているため、各サンプルのビスフェノールＡ型エポキシ樹脂およびヨードニウム塩系カチオン硬化剤の濃度は、上記の半分となる。

That is, since each sample is mixed at a volume ratio of 1: 1, the concentration of the bisphenol A type epoxy resin and the iodonium salt cationic curing agent in each sample is half of the above.

  Similarly to Example 1 above, a honeycomb structure was manufactured using the manufacturing apparatus 10 shown in FIG. 3 (each condition is the same as Example 1 above). 2 ml of each of the samples (1) to (5) shown in Table 2 was applied to the container 11, and nitrogen was sprayed at a relative humidity of 70%, a temperature of 20 ° C., and a flow rate of 4 L / min. 700 seconds after coating, UV light was irradiated from the light source 13 (FIG. 3) for 2 minutes to carry out photocrosslinking (photocuring). The surface and cross-sectional structure of the manufactured honeycomb structure were observed with an optical microscope (same as Example 1) and a scanning electron microscope (same as Example 1).

  All samples were cured by exposure to UV light for 2 minutes. Samples (1) and (4) had high toughness and could be peeled from the container 11 with tweezers as shown in FIG. On the other hand, the honeycomb structures of the samples (2), (3), and (5) were fragile and tended to be scraped when tweezers were applied. When visible light is applied to the honeycomb structures of samples (1) and (4), an interference color is observed, and the others tend to become cloudy. The result of having observed the honeycomb structure of sample (1)-(5) using the optical microscope is shown in FIG. 9A shows the surface structure of the honeycomb structures of the samples (1) and (4), and FIG. 9B shows the honeycomb structures of the samples (2), (3), and (5). The surface structure is shown. From (a) in FIG. 9, it can be seen that the honeycomb structures of Samples (1) and (4) have a good honeycomb structure. On the other hand, in the honeycomb structures of Samples (2), (3), and (5), a non-uniform structure was obtained as shown in (b) of FIG.

  From the above results, the method for manufacturing a honeycomb structure according to the present invention means that good results cannot be obtained unless a certain amount of the curing agent is mixed. Specifically, it is necessary that the solution to be applied contains a concentration of at least 5 g / L. However, this is the concentration when an iodonium salt cationic curing agent is used as the curing agent, and the concentration is preferably set as appropriate according to the type of curing agent used.

<Example 3>
In this example, experimental results obtained by examining resistance to various solvents in the honeycomb structure manufactured by the method of the present invention are shown.

  In order to evaluate solvent resistance, chloroform, acetone, pure water, and ethanol were used.

  Similar to Example 1 described above, a bisphenol A type epoxy resin (EXA-850CRP manufactured by Dainippon Ink & Chemicals, Inc.) is used as the photocrosslinkable material, an iodonium salt cationic curing agent is used as the curing agent, and a hydrophobic organic solvent. In this case, chloroform (Wako Pure Chemicals, grade 1) was used, and Cap was used as the amphiphilic compound. The chloroform solution prepared so that the concentration of the iodonium salt cationic curing agent was 10 g / L, the concentration of the bisphenol A type epoxy resin was 100 g / L, and the concentration of the amphiphilic compound was adjusted to 1 g / L. 1 ml each of the chloroform solution was taken and mixed in a stoppered graduated cylinder, and this solution (2 ml) was applied to the container 11 (FIG. 3). The honeycomb structure was manufactured using the manufacturing apparatus 10 shown in FIG. Nitrogen was blown at a relative humidity of 70%, a temperature of 20 ° C., and a flow rate of 4 L / min. 700 seconds after application, UV light was irradiated from the light source 13 (FIG. 3) for 2 minutes to carry out photocrosslinking.

  In order to investigate the resistance of the manufactured honeycomb structure to various solvents, the honeycomb structure is not peeled off from the container 11 (FIG. 3), and pure water, ethanol (Wako Pure Chemicals, Grade 1), acetone (Japanese) Optical pure drug, grade 1) and chloroform (Wako pure drug, grade 1) were applied so that the entire surface of the honeycomb structure was immersed. The surface structure of the honeycomb structure after applying each solvent and allowing to stand for 3 hours was observed with an optical microscope (same as in Example 1). The observation results are shown in FIG. In FIG. 10, (a) is the result of applying pure water, (b) is the result of applying ethanol, (c) is the result of applying acetone, and (d) is the result of applying a chloroform solution. It is a result. When the change in the surface structure was observed before and after applying each solvent, as shown in FIGS. 10A to 10D, a honeycomb pattern structure was formed when immersed in any solvent. It was confirmed that

  As described above, the method for manufacturing a honeycomb structure of the present invention includes a coating process in which a solution in which a hydrophobic organic solvent, a photocrosslinkable material, and a curing agent are mixed is applied on a substrate, and the above-described coating process. The hydrophobic organic solvent is evaporated from the applied solution and a droplet is formed on the surface of the solution, and the photocrosslinkability is formed on the surface on which the droplet is formed by the droplet forming step. A method of manufacturing a honeycomb structure including a light irradiation step of irradiating light for crosslinking the material, wherein the hydrophobic organic solvent is completely evaporated and droplets are formed in the light irradiation step, or It is characterized by irradiating the above-mentioned light onto a solution in which the traces of the droplets maintain the original shape.

  The timing of the light irradiation that crosslinks the photocrosslinkable material is determined so that the hydrophobic organic solvent of the solution applied on the substrate is completely evaporated and droplets are formed or the traces of the droplets remain intact. Even when the photocrosslinkable material is applied to the manufacturing method using the self-organization phenomenon, the honeycomb structure having uniform pores of about submicron to 100 microns can be obtained. Can be provided. That is, according to the method for manufacturing a honeycomb structure of the present invention, it is possible to manufacture a honeycomb structure very easily and quickly compared to nanoimprint in which application, transfer, and peeling are performed using a mold in a small area. It is possible to provide a stable honeycomb structure having resistance to heat and chemicals that cannot be produced with a honeycomb structure using water droplets as a mold.

  Therefore, the honeycomb structure manufactured from the photocrosslinkable material using the above-described manufacturing method can provide a honeycomb structure that is stable in various solvents and the like. Can be applied.

<Example 4>
In Example 1 described above, a bisphenol A type epoxy resin was used as the photocrosslinkable material. Therefore, in this example, a honeycomb structure was manufactured using another photocrosslinkable material.

  A solid epoxy base (manufactured by Dainippon Ink and Chemicals, HP-7200) was used as the photocrosslinkable material. The same curing agent, hydrophobic organic solvent, and amphiphilic compound as those used in Example 1 were used.

  Next, the solution 2 (FIG. 3) includes a chloroform solution prepared so that the concentration of the iodonium salt cationic curing agent is 10 g / L, and a solid epoxy base concentration of 100 g / L. The chloroform solution prepared so that the density | concentration of an ionic compound might be 1 g / L was produced. 1 ml of each of the two prepared chloroform solutions was taken and mixed in a stoppered measuring cylinder.

  For manufacturing the honeycomb structure, the manufacturing apparatus 10 shown in FIG. 3 described above was used. Various conditions in the manufacturing apparatus 10 were the same as those in Example 1.

  The container 11 was coated (cast) with the solution 2 (2 ml) mixed in the stoppered graduated cylinder using the lid (diameter 36 mm) of the petri dish (TOKYO PETRI SCHALE, firing port 30) as in Example 1. Then, humidified nitrogen gas was sprayed on the lid through a washing bottle containing water. Nitrogen had a relative humidity of 70%, a temperature of 20 ° C., and a flow rate of 4 L / min. The nitrogen flow rate was measured using a flow meter (KOFLOC, MODEL RK1600R). In order to measure the weight change due to evaporation of chloroform and water, all experiments were performed on the balance 12 and the weight change was observed with the monitoring device 15.

  In this example, after applying to the container 11 and evaporating the solvent (completely) in a nitrogen atmosphere, UV light was irradiated for 2 minutes using a fiber type UV light source (manufactured by Hamamatsu Photonics).

  The state in the container 11 after UV light irradiation was observed with an optical microscope (OM, Olympus BH-2). The observation results are shown in FIG.

  From the observation result of FIG. 11, it was shown that a honeycomb structure having pores having a diameter of 6 microns and a height of about 2 microns was formed.

  From the above, it was revealed that not only liquid epoxy resin but also solid epoxy resin can be formed in the same manner.

  The method for manufacturing a honeycomb structure according to the present invention has a honeycomb structure having uniform pores of about submicron to 100 microns even when a photocrosslinkable material is applied to a manufacturing method using a self-organization phenomenon. A honeycomb structure excellent in heat resistance and chemical resistance can be provided.

  Therefore, for example, it can be widely applied in the fields of optics and electronics such as high-functional composite materials, catalysts, nonlinear optical materials, and memory elements, and in various fields such as biotechnology.

Claims (8)

A coating process in which a solution in which a hydrophobic organic solvent, a photocrosslinkable material, and a curing agent are mixed is coated on a substrate;
A droplet forming step for evaporating the hydrophobic organic solvent from the solution applied by the application step and generating droplets on the surface of the solution;
A light irradiation step of irradiating light that crosslinks the photocrosslinkable material onto the surface where droplets are generated by the droplet formation step,
In the light irradiation step, the above-described light is irradiated to a solution in which the hydrophobic organic solvent is completely evaporated and droplets are formed or the traces of the droplets maintain the original shape. A method for manufacturing a honeycomb structured body.   2. The method for manufacturing a honeycomb structured body according to claim 1, wherein in the droplet forming step, a gas having a relative humidity of 50% to 95% is sprayed on the solution at a predetermined flow rate.   The method for manufacturing a honeycomb structure according to claim 1 or 2, wherein the photocrosslinkable material is composed of a monomer, an oligomer, or a mixture thereof.   The method for manufacturing a honeycomb structure according to any one of claims 1 to 3, wherein the light is ultraviolet light or visible light.   The method for manufacturing a honeycomb structured body according to any one of claims 1 to 4, wherein the solution contains an amphiphilic compound.   The method for manufacturing a honeycomb structure according to any one of claims 1 to 5, wherein the curing agent is contained in an amount of at least 2% by weight with respect to the photocrosslinkable material.   A honeycomb structure comprising a step of forming or loading a substance different from the honeycomb structure into pores of the honeycomb structure manufactured by the manufacturing method according to any one of claims 1 to 6. Body manufacturing method.   A honeycomb structure manufactured by the manufacturing method according to any one of claims 1 to 7.

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