WO2006090579A1

WO2006090579A1 - Process for producing honeycomb structure with isolated holes

Info

Publication number: WO2006090579A1
Application number: PCT/JP2006/302074
Authority: WO
Inventors: Masatsugu Shimomura; Masaru Tanaka; Hiroshi Yabu
Original assignee: National University Corporation Hokkaido University
Priority date: 2005-02-25
Filing date: 2006-02-07
Publication date: 2006-08-31
Also published as: JPWO2006090579A1; JP5050205B2

Abstract

A material solution comprising a hydrophobic organic solvent and a polymeric material dissolved or dispersed therein is applied to a substrate to form a liquid film of the material solution. A gas containing water vapor is blown against the surface of the liquid film to thereby form holes in a honeycomb arrangement while utilizing the resultant water droplets as a template. The resultant filmy object is heated or exposed to a good solvent for the polymeric material to partly deform or remove the hole-surrounding structure and thereby isolate the individual holes. By this technique, a honeycomb structure having isolated holes can be thus produced through self-organization using droplets as a template.

Description

Specification

Method for manufacturing honeycomb structure with isolated holes

Technical field

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a her cam structure, and more specifically, a her cam structure having excellent heat resistance and chemical resistance and having isolated pores. It relates to a method for manufacturing.

Background art

[0002] In recent years, Hercam structures are expected to be applied in the fields of optics, electronics, and biotechnology. In the field of optics and electronics, for example, application to high-performance composite materials, catalysts, nonlinear optical materials, memory elements and the like is expected. Biotechnology In one field, in a porous film having a Herkam structure, the Herkam pattern provides a cell adhesion surface, and the porous structure provides access to the cell support base and a nutrient supply route. Is shown.

[0003] As a method of obtaining a her cam structure having uniform pores of about submicron to 100 microns, there is a mold technology including nanoimprint. However, with this method, since the shape of the pores collapses when peeling the saddle, it is difficult in principle to accurately reflect the saddle structure.

[0004] Also, a method is known in which a colloidal fine particle dispersion is dried and a colloidal crystal that has been accumulated is used as a saddle shape to obtain a hammer-like porous film. After pouring, there was a problem that the saddle must be removed as described above.

[0005] In view of this, research has been conducted on a technique for manufacturing a Hercam structure using the self-organization phenomenon. This is a method in which a honeycomb structure can be produced by self-accumulation of droplets condensed from the air and the like and a polymer deposited at the solvent interface in the three-phase boundary region.

[0006] Specifically, the present inventors have applied (cast) a polymer solution onto a solid substrate and sprayed high-humidity air on a water droplet generated as a trapezoidal porous film in the form of a hard cam. Have been proposed [for example, Patent Document 1 (Japanese Patent Laid-Open No. 2003-80538) (See Patent Document 2 (Japanese Laid-Open Patent Publication No. 2003-128832 (published May 8, 2003)))]. The method using this self-organization phenomenon is a highly accurate honeycomb structure that does not require complicated manufacturing equipment and is long to manufacture and requires time as in the manufacturing method using the mold technology described above. The body can be manufactured.

[0007] However, in the technique for producing a polymer film having a heart cam structure by using the above water droplet as a bowl, it is difficult to make the formed hole in an isolated state. Have. Specifically, when the water droplets are bowl-shaped, it is possible to form a Hercam-like structure, but the formed holes are in communication with each other.

[0008] The above-described technique has been proposed by the present inventors and is a very excellent technique capable of easily producing a Hercam-like porous film. However, since the holes to be formed are communication holes, the use of the obtained porous film (her cam structure) is limited. Therefore, there is a need for the development of a technology that can isolate each hole to be formed and further expand the use of the her cam structure.

[0009] The present invention has been made in view of the above-mentioned problems, and the object thereof is to isolate the holes formed when manufacturing a her cam structure by self-organization using droplets as saddles. It is to provide technology that can be in a state.

Disclosure of the invention

[0010] As a result of intensive studies in view of the above problems, the present inventors have performed a proper post-treatment after producing a her cam structure having a droplet as a bowl and having a hole, whereby the her cam It has been found that it is possible to form a hole isolated from each other by fusing a part of the structure body at a fine level and closing a communication portion of a plurality of holes, thereby completing the present invention.

[0011] That is, a method for manufacturing a her cam structure according to the present invention is a method for manufacturing a honeycomb structure having a plurality of holes arranged in a honeycomb shape in order to solve the above-described problems. -A liquid film forming step of forming a liquid film of the material solution by laminating on the support a material solution in which the main body material to be the main body of the cam structure is dissolved or dispersed in the first solvent. While the first solvent is volatilized from the liquid film, a plurality of the droplets are formed in a bowl shape by the self-organization of the main body material accompanying the generation of the second solvent droplets that are not mixed with the first solvent. Forming a hole in the form of a hard cam. In addition, the film-like body obtained in the hole forming step includes a hole isolation step of isolating individual holes by partially deforming or removing the structure around the holes. It is said.

[0012] In the manufacturing method, in the hole isolation step, the body material is melted by heating the film body, or the film body is exposed to a solvent or a solution capable of dissolving the body material. The surrounding structure may be partially changed, or the surrounding structure of the hole may be partially removed by the adhesion and peeling of the adhesive to the surface of the film-like body. In this partial removal, for example, an adhesive tape can be used as an adhesive.

[0013] In the above production method, at least a polymer material or a monomer material that is polymerized by a polymerization reaction can be used as the main body material. When a monomer material is used as the main body material, the material solution can contain a catalyst that promotes the polymerization reaction of the monomer material.

[0014] In the above production method, a case where the first solvent is a hydrophobic organic solvent and the second solvent is water can be mentioned as a particularly preferable example. In this case, in the hole forming step, it is preferable to form droplets on the surface of the liquid film by blowing a gas containing the vapor of the second solvent onto the liquid film.

[0015] In the above production method, it is preferable that the liquid film is formed by casting the material solution onto the surface of the support in the liquid film forming step.

[0016] Furthermore, the present invention also includes a her cam structure manufactured by the above manufacturing method.

[0017] In the manufacturing method according to the present invention, it is not necessary to include all of the liquid film forming step, the hole forming step, and the hole isolating step. As an intermediate, it is possible to perform only a hole isolation process.

[0018] That is, another method for manufacturing a her cam structure that is useful in the present invention is a method for manufacturing a honeycomb structure having a plurality of holes arranged in a two-cam configuration, and having adjacent holes. Manufactured by self-organizing at least part of the main body material, which has at least part of the communicating part that communicates with the hole! In contrast to the pre-cam structure precursor, the structure around the hole is partially deformed or removed. Further, the present invention is characterized in that it includes a hole isolation process for isolating individual holes in the communication portion.

[0019] In the manufacturing method, in the hole isolation step, the body material is melted by heating the film body, or the film body is exposed to a solvent or solution that can dissolve the body material. The surrounding structure may be partially changed, or the surrounding structure of the hole may be partially removed by the adhesion and peeling of the adhesive to the surface of the film-like body. In this partial removal, for example, an adhesive tape can be used as an adhesive.

[0020] In the above production method, at least a polymer material or a monomer material that is polymerized by a polymerization reaction can be used as the main body material.

[0021] In the present invention, as described above, after forming a her-cam structure by self-organizing the main body material using a droplet as a bowl, the obtained cam-cam structure is used as a finished body. Instead, it is treated as an intermediate, and post-treatment such as heating, exposure to a solution, and physical processing is applied to the intermediate. This makes it possible to control the shape of the hole in the her cam structure, and it is possible to produce a no-cam structure in which individual holes are isolated (independent) only by the no-cam structure in which the holes communicate. it can. In addition, by appropriately setting the conditions of a series of manufacturing processes including the hole isolation process, it becomes possible to control the shape of the hard cam structure itself.

[0022] As a result, it is possible to obtain honeycomb structures having various structures according to various purposes and applications, and it is possible to expand the field of use of honeycomb structures and further improve their practicality. Monkey.

[0023] Other objects, features, and advantages of the present invention will be sufficiently enhanced by the following description. The benefits of the present invention will become apparent from the following description with reference to the accompanying drawings.

Brief Description of Drawings

[0024] FIG. 1 (a) is a view showing a scanning line electron microscope (SEM) photograph of the Hercam film obtained in Example 1.

Fig. 1 (b) is a view showing an SEM photograph of the honeycomb film obtained in Example 2.

FIG. 2 is a view showing an SEM photograph of the honeycomb film obtained in Example 3.

FIG. 3 (a) is a view showing an optical micrograph of the intermediate knob-cam film obtained in Example 4. is there.

FIG. 3 (b) is a view showing an SEM photograph of the knob-cam film (finished product) obtained in Example 4.

FIG. 4 is a view showing an SEM photograph of the honeycomb film obtained in Example 5.

BEST MODE FOR CARRYING OUT THE INVENTION

[0025] One embodiment of the present invention will be described as follows. The present invention is not limited to this.

[0026] In the Hercam structure according to the present invention, after the formation of the holes, the structure having the holes is heated or exposed to a solvent or the like. By these treatments, for example, the structure body around the hole can be fused up and down, so that an isolated partition wall can be formed around the hole, and an isolated hole can be formed. it can.

[0027] If the manufacturing method of the her cam structure according to the present invention is divided into steps, a step of preparing a solution of a material (main body material) that becomes a main body of the her cam structure (material solution preparation step), A step of forming a liquid film on the support using the obtained solution (liquid film forming step), a step of forming pores by self-organizing the main body material by evaporating the solvent from the obtained liquid film (Hole formation process) and a process of isolating the formed holes (hole isolation process). Hereinafter, the production method will be specifically described based on the above-mentioned division of each process.

[Material solution preparation step]

In the material solution preparation step, a material solution is prepared by dissolving or dispersing at least a main body material serving as a main body of the Hercam structure in an arbitrary solvent (referred to as a first solvent for convenience). The main body material used in the present invention is not particularly limited as long as it is a material capable of forming fine pores by a subsequent hole forming step! Specifically, for example, examples described later As shown in Fig. 5, various polymer materials (polymer or rosin) can be mentioned.

[0029] Specific examples of the polymer material include aliphatic polyesters such as polylactic acid, polyhydroxybutyric acid, polystrength prolatatone, polyethylene adipate, polybutylene adipate; polymethylmetatalylate, polytetrahydrofurol. Polyacrylic acid esters such as furylmetatalylate; Aliphatic polycarbonates such as polybutylene carbonate and polyethylene carbonate; Polyimides, polyamideimides, polyetherimides, polyesterimides, and other polymers Although riimides etc. can be mentioned, it is not specifically limited. As these polymer materials, an appropriate material can be selected according to the use of the Hercam structure. Moreover, only one kind of these polymer materials may be used, or a polymer blend obtained by combining two or more kinds may be used! /.

[0030] The main body material may be a monomer material that is polymerized by a polymerization reaction rather than a polymer material itself. The specific monomer material is not particularly limited. For example, the monomer compound used for the polymerization of the above-described polymer material can be appropriately selected and used. Furthermore, as the main body material, a polymer material may be combined with a monomer material, an oligomer material, or other crosslinking agent. Thus, after forming a liquid film, a monomer structure or oligomer material is subjected to a cross-linking reaction, thereby making it possible to produce a herm structure having a three-dimensional structure at the molecular level.

[0031] When a monomer material, an oligomer material, a cross-linking agent, or the like is used as the main body material, a catalyst can be added as necessary to promote a polymerization reaction or a cross-linking reaction. As the catalyst, a known appropriate substance can be selected and used according to the specific type of the monomer material or the like and the type of polymerization or crosslinking reaction.

[0032] Needless to say, it is possible to use materials other than polymer materials as the main body material used in the present invention. Any material can be used in the present invention as long as it can form a honeycomb structure in the hole forming step described later and can perform the hole isolation step.

[0033] The first solvent is not particularly limited as long as it can dissolve or disperse various substances used as the main body material. In the present invention, as described above, various polymer materials (or monomer materials used as raw materials thereof) can be suitably used as the main body material. Therefore, as the first solvent, these polymer materials can be dissolved or dispersed. Various organic solvents can be suitably used.

[0034] Specifically, for example, halogen-based organic solvents such as black mouth form and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; methyl isobutyl ketone and the like Water-insoluble ketones; ethers such as jetyl ether; and the like. It is also possible to use a solvent such as carbon dioxide. These solvents may be used alone or as a mixed solvent in which two or more kinds are combined as necessary.

In the hole forming step to be described later, it is preferable to form fine water droplet particles on the liquid film when forming the Hercam structure. Therefore, the first solvent used is preferably a solvent having as low an affinity as possible with water. In other words, it is preferably a water-insoluble (hydrophobic) solvent.

[0036] The method for preparing the material solution is not particularly limited, and a preferable preparation method may be appropriately selected and used depending on the type of the main body material to be used. In the case of a polymer material, it may be difficult to smoothly dissolve in a solvent because of its large molecular weight compared to a low-molecular compound or substance. Therefore, various treatments such as heating and application of ultrasonic waves may be performed during dissolution or dispersion. It is also possible to use a polymer polymerization solvent solution obtained by the polymerization reaction as it is as a material solution.

[0037] Further, in addition to the main body material, the above-mentioned material solution may contain known additives in a range that does not affect the formation of the hard cam structure and control of the shape.

[0038] Here, in the present invention, it is preferable to use an amphiphilic compound having an affinity for both the first solvent and the second solvent as the main body material in addition to the main material. . As a result, the surface tension between the second solvent droplet and the liquid solvent first solvent can be reduced in the pore formation process, so that the droplets aggregate and fuse into one lump. It can be effectively prevented. As a result, the hard cam structure can be manufactured even better.

[0039] The amphiphilic compound is not particularly limited. However, when a hydrophobic organic solvent is used as the first solvent and water is used as the second solvent, an amphiphilic polymer is used. Can be. 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 Z polypropylene glycol block copolymer. Is mentioned.

[0040] The hydrophobic side chain is a non-polar linear group such as a methylene group or a phenylene group, except for a linking group such as an ester group or an amide group. The hydrophilicity of It is preferable that the structure is not branched. For example, when using a methylene group, it is preferable that the unit consists of 5 or more units.

[0041] The hydrophilic side chain preferably has a structure having a hydrophilic part such as a polar group, an ionic dissociation group, or an oxyethylene group at the terminal via a linking part such as a methylene group.

[0042] The ratio of the hydrophobic side chain to the hydrophilic side chain depends on the size, nonpolarity, polarity strength, and hydrophobic organic solvent hydrophobicity. The unit ratio is in the range of 3Zl to lZ3. It is desirable that Also, 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 the solubility in a hydrophobic solvent is not affected, as compared with an alternating polymer of hydrophilic side chains of hydrophobic side chains. It is preferable that

[0043] As will be described later, the Hercam structure that is useful in the present invention can be used as a cell culture substrate in the biotechnology field, for example. Therefore, it is preferable to use a non-toxic amphiphilic compound for such applications. Non-toxic amphiphilic compounds such as polyethylene glycol z polypropylene glycol block copolymer, acrylamide polymer as the main chain skeleton, dodecyl group as hydrophobic side chain and ratato group as hydrophilic side chain, or Amphiphilic polymers that also have a carboxyl group, or ion complexes of heparin dextran sulfate, ionic polymers such as nucleic acids (DNA and RNA) and long chain alkyl ammonium salts, gelatin, collagen, It is desirable to use an amphiphilic polymer having a water-soluble protein such as albumin as a hydrophilic group.

[Liquid film forming step]

In the liquid film forming step, the material solution described above is laminated on a support to form a liquid film of the material solution. The term “liquid film” as used herein refers to a state in which the above-mentioned material solution is stably formed by spreading in the form of a film on the surface of the support in the solution state.

[0045] The material of the support does not affect the liquid film. On the other hand, the support is not altered or corroded by the first solvent, the main body material, or other additives contained in the liquid film. There is no particular limitation as long as it is made of a material. Specifically, for example, inorganic materials such as glass, metal and silicon wafers; organic materials excellent in organic solvent resistance such as polypropylene, polyethylene, polyetherketone and polyfluorinated styrene; water, liquid paraffin , Liquids such as liquid polyether, and the like can be used. In the embodiments to be described later, aluminum or glass is used.

[0046] The specific shape of the support is not particularly limited as long as the liquid film can be stably held on the surface thereof. Normally, a flat substrate (substrate) is preferably used. A curved substrate may be used according to the shape of the huck cam structure. Furthermore, when a large number of honeycomb structures are continuously produced, a rotating body such as a rotating drum or a rotating belt can be used.

[0047] The surface of the support may have a smoothness capable of holding a liquid film, but it should be peelable on the premise that the support is peeled off after the hole forming step described later. In order to improve it, a known surface treatment is applied!

[0048] The specific method for laminating the liquid film on the support is not particularly limited, and is a casting method in which a material solution is cast onto the support surface; a bar coater, a roll coater, a knife coater, etc. Examples thereof include a coating method using a known coating member; an extrusion coating method using various known dies; a dip method in which a support is immersed in a material solution; and the like. In the examples to be described later, the liquid film is formed by the casting method, but of course, the present invention is not limited to this, and an appropriate method is selected in consideration of the material solution, the type of support, the manufacturing scale, etc. Can be used.

[0049] In addition, the conditions in the liquid film lamination method (formation method) are not particularly limited, and the state of the liquid film formed on the support changes before it enters the hole forming step. Set the appropriate conditions according to the lamination method within the range that does not change the quality of the components!

[0050] [Hole forming step]

In the hole forming step, the first solvent is volatilized from the formed liquid film, and the self-organization of the body material accompanying the formation of droplets of the second solvent that does not mix with the first solvent results in the above-mentioned A plurality of holes are formed in a harcome shape with a droplet as a bowl.

[0051] The solvent used as the second solvent is not specifically limited. A known solvent that does not mix with the first solvent may be selected and used according to the type of the first solvent. . As described above, it is preferable to use water as the second solvent, but of course, it is not limited to this, and a hydrophilic organic solvent such as various lower alcohols is used in combination with water. Can also be used.

[0052] In a particularly preferred form of the pore forming process found by the present inventors, a gas containing water vapor is blown onto the liquid film to form droplets on the surface of the liquid film, and from the liquid film to hydrophobicity. The body material is self-assembled by evaporating the organic solvent.

[0053] More specifically, the liquid film formed on the support is deprived of latent heat when the hydrophobic organic solvent evaporates. Therefore, on the liquid film surface (that is, evaporative cooling) whose temperature has decreased, the water vapor contained in the gas condenses into minute water droplets (droplets) and adheres to the liquid film surface. Here, as described above, the surface tension between the water droplet and the hydrophobic organic solvent is reduced by the action of the hydrophilic portion of the amphiphilic compound contained in the liquid film. Aggregating and fusing into a single mass is effectively avoided. In this state, water droplets are transferred and accumulated by evaporation of the solvent and the flow of the material solution in the liquid film based on the compensation from the surroundings, and are further closely packed by the transverse capillary force. The main body material contained in the liquid film is self-organized using the filled water droplets as a bowl shape, and a hermetic pattern structure is formed.

[0054] Specifically, as the gas containing water vapor (spraying gas), for example, an inert gas such as air, nitrogen gas, or argon gas can be suitably used. Gases other than inert gas can be used depending on the type of liquid film components (main body material, first solvent, etc.) and the type of support. This blowing gas may be a single gas or a mixed gas such as air.

[0055] For the above gas, it is very preferable to control the humidity (in other words, the vapor pressure of the second solvent) and the flow rate in order to form a good Hercam structure. These humidity and flow rate control methods are not particularly limited, and may be controlled using known techniques related to gas flow and spraying. In addition, specific ranges of humidity and flow rate are not particularly limited, and appropriate conditions may be set in consideration of the material solution, the type of support, the manufacturing scale, and the like. For example, in the examples described later, the humidity is 70% and the spraying flow rate is 2 to 3 liters Z.

[0056] The blowing gas is desirably subjected to dust removal treatment such as passing through a filter before being blown onto the liquid film. In addition, since dust in the atmosphere affects the hard cam structure formed as condensation nuclei of water vapor, it is necessary to install dust removal equipment at the manufacturing site. preferable.

[0057] [Hole isolation process]

In the hole isolation step, individual holes are isolated by partially deforming or removing the structure around the holes from the film-like body obtained in the hole forming step. In other words, in the present invention, the nozzle-cam structure obtained in the hole forming step is used as an intermediate, and a process for isolating the holes from the intermediate is performed. Specifically, when the holes are in communication, the communication portion is closed, and if the trunk or pillar of the honeycomb structure has a certain thickness or width, the periphery of the communication portion is removed.

[0058] The method for closing the hole communication portion is not particularly limited, but a typical method is to heat the intermediate body (film-like body) of the Hercam structure obtained in the hole forming step. Then, the structure around the hole may be partially changed by thermally fusing the periphery of the hole or by partially dissolving the film-like body by exposure to various solutions or solvents.

[0059] The method for heating the film-like body is not particularly limited, and the type of the main body material to be the film-like body, that is, the honeycomb structure, the macro shape of the honeycomb structure (in the case of a film form, A suitable heating method may be selected according to various conditions such as film thickness, width, length, and the like. In the Example mentioned later, the film-form film-form body is heated using the hot stage.

[0060] The heating temperature for heating the film-like body is not particularly limited, and an appropriate temperature may be set according to the melting point or glass transition temperature (Tg) of the main body material. In the case of a polymer material, heating around Tg can soften and melt the periphery of the hole to effectively close the communication hole (see, for example, the heating temperatures of Examples 2 and 4). In addition, since the degree of softening and melting around the hole can be controlled by changing the heating temperature, the hole is not completely isolated, or the wall thickness of the isolated hole is changed. Can be used. In other words, in the present invention, the state of the honeycomb structure itself can also be controlled by controlling the heating temperature rather than simply isolating the communication holes.

[0061] When the membrane is exposed to a solution or a solvent, the type of the solution or solvent to be used is not particularly limited as long as it can dissolve the main body material. Usually, a good solvent for the main body material, an acidic solution, an alkaline solution, or the like can be used. In the examples described later, since the main body material is various polymers, for example, Black mouth form, which is a good solvent for the child material, is used (see Example 3). In addition, in the exposure treatment to a solution or a solvent, the degree of dissolution around the pores can be controlled by changing the exposure conditions or changing the type of solvent used, as in the case of the above heating (for example, In Example 3, it is possible to change the thickness of the stem of the Her-cam structure, the height of the pillar, etc.), so that the hole is not completely isolated or the wall of the isolated hole is The thickness can be changed. Therefore, in the present invention, the state of the Herckum structure itself can be controlled also by controlling the exposure conditions to the solution and the solvent.

[0062] The exposure conditions include, but are not particularly limited to, the exposure time of the film-like body to the solution or solvent, the exposure temperature, the concentration of the solution or solvent, and the like.

[0063] In the film state, a method for partially removing the structure around the hole is not particularly limited. For example, as shown in the examples described later, the surface of the film-like body An operation for adhering and peeling the pressure-sensitive adhesive can be mentioned (see Example 5). The adhesive body and its degree of adhesion may be selected appropriately depending on the strength of the main body material and the shape of the cam structure (the size of the trunk and pillars). In the examples described later, an adhesive tape is used as the pressure-sensitive adhesive body.

[Other steps]

The manufacturing method according to the present invention need not include all of the material solution preparation step, the liquid film formation step, the hole formation step, and the hole isolation step, but may include at least the hole isolation step. For example, as the material solution, an already prepared solution can be used. Therefore, the material solution can be omitted, and only the hole isolation step may be performed on the already manufactured Hercum structure. . In addition, after the hole forming step or the hole isolating step, a step of separating the formed two-cam structure from the support force may be included.

[Her cam structure that is useful in the present invention]

The her cam structure which is useful in the present invention is manufactured by the above manufacturing method and may have a plurality of holes arranged in a her cam shape. The hole is isolated. In other words, the independent holes are regularly arranged in a Harcam shape.

[0066] Here, the specific shape of the hard cam structure that is useful in the present invention, that is, the hard cam structure There is no particular limitation on the macro shape other than the micro shape. Since the manufacturing method described above is suitable for manufacturing a film, that is, a film-shaped her cam structure, the typical shape (primary shape) of the her cam structure according to the present invention is as follows. A flat-shaped her cam film may be a her cam film. These Hercam film Z films may have a quadratic secondary shape such as a square or a rectangle, a circular or elliptical secondary shape, or a more complicated secondary film. You may have the following shape. These secondary shapes are appropriately set according to the use of the honeycomb structure, and can be easily manufactured by performing secondary processing such as punching or cutting the manufactured honeycomb film Z film. (See Examples).

[0067] In addition, the Hercom structure that is useful in the present invention may be a honeycomb structure film having an array structure of stretched pores by stretching. The stretching method is not particularly limited. For example, the stretching can be performed by pinching two or more ends of the her cam structure with tweezers or hands and pulling in the extending direction. Alternatively, stretching can be carried out using a micro-manipulator. Further, a pair of rolling rollers or the like may be used.

[0068] The state of the hole formed in the hard cam structure that is useful in the present invention is not particularly limited, and may be a through hole or a non-through hole. Further, depending on the application in which all the holes do not need to be isolated, the holes may be partially or periodically communicated. Such a state can be achieved by controlling various conditions of the manufacturing method.

[Use of the present invention]

The application field of the honeycomb structure obtained by the present invention is not particularly limited, and can be used in a wide variety of known fields in which the honeycomb structure can be used. Specifically, for example, large-area 'flexible display devices, surface light emitters such as EL panels, display devices, and electronic devices such as memory elements; nonlinear optical materials such as photonic crystals and optical waveguides, and light energy conversion Examples include optical (and electronic) fields such as devices; chemical fields such as various catalysts and microreactors; biotechnology fields such as DNA chips, microarrays, macroarrays, protein chips, and cell culture substrates.

[0070] In particular, a nodular-cam-like porous body having periodic and isolated pores is expected to be applied to a photonic crystal element. In the field of electronics, matrix materials such as electrodes As a material, the structure can be stably maintained in heat or a solvent. In the field of biotechnology, the influence of substrate turnover on cell growth and separation has recently been elucidated, but it is also resistant to various solvents, so it can be used as a stable pattern base material. The use as a cell culture substrate is promising. In addition, the periodic shape of the cams with holes isolated from each other is very promising as a microreactor.

[Example]

The present invention will be described more specifically based on examples and FIGS. 1 to 4. The present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

Poly-force prolatatone (Aldrich) and amphiphilic polyacrylamide (CAP polymer) with the following structure as the main material

[0073] [Chemical 1]

[0074] In addition, a material solution was prepared using black mouth form as the first solvent. Poly (ε

-Strength prolatatone) and CAP polymer were dissolved in black mouth form so that the weight ratio was 10: 1, and the material solution was prepared so that the final concentration of the main body material was 4 mgZml.

[0075] As a support, a glass petri dish having an outer diameter of 9 cm, in which an aluminum substrate (5 cm square, 0.1 mm thick, manufactured by Niraco) was laid, was used. In the glass petri dish, 5 ml of the material solution was cast to form a liquid film. High-humidity air (humidity 70%) was blown onto this liquid film in an environment of temperature 25 ° C and humidity 30% (for 31itterZ). As a result, a hard cam structure (intermediate no-cam film) having a continuous hole was obtained as an intermediate. [0076] The intermediate knife-cam film formed on the aluminum substrate was punched into a circular shape having a diameter of 1 cm using a punching blade. Then, using the heater (trade name: RH6000, manufactured by Japan Hightech Co., Ltd.), heating at 100 ° C for 0 seconds, 5 seconds, and 40 seconds, respectively, the intermediate no-cam film Then, a her-cam structure (No. 2 cam Finolem) as a finished product was manufactured.

[0077] The obtained Hercam film was observed with a scanning electron microscope (SEM, trade name: S-3500 N, manufactured by Hitachi). The observation conditions were such that the magnification was X 2. Ok and 8. Ok, the voltage was 25 kv, and the substrate was tilted at 0 ° (front) and 45 °. The result is shown in Fig. 1 (a).

[0078] Note that 0s, 5s, and 40s in Fig. 1 (a) indicate the heating time at 100 ° C (0 seconds, 5 seconds, and 40 seconds). The Top view shows the front (0 °) force observed on the substrate, and the Ti It view shows the substrate observed by tilting 45 °.

[0079] As is apparent from the results shown in Fig. 1 (a), the longer the heating time, the narrower the trunk of the honeycomb structure, and it was found that the pillars were collapsed. In particular, the non-cam film heated for 40 seconds did not have a perfect dimple structure, but it was possible to produce a similar structure.

Under the same conditions as in Example 1, an intermediate no-cam film was prepared by an independent process, and the intermediate no-cam film was heated at 100 ° C. for 50 seconds, thereby completing the half-cam. A structure (Hercam film) was produced. Figure 1 (b) shows the result of observation of the resulting hard cam film by SEM. The observation conditions are the same as in Example 1.

[0081] As is apparent from the results shown in Fig. 1 (b), in the two-cam film heated for 50 seconds, a structure in which the polymer gathered at the columnar trunk portion was observed.

[0082] From the above results, it is clear that the shape of the trunk portion and the column portion of the honeycomb structure can be controlled by adjusting the heating time.

A material solution was prepared using polymethylmetatalylate (PMMA, Aldrich) and CAP polymer as the main material, and black mouth form as the first solvent. With PMMA The CAP polymer was dissolved in black mouth form so that the weight ratio was 10: 1, and the material solution was prepared so that the final concentration of the main body material was 4 mgZml.

[0084] As a support, a glass petri dish having an outer diameter of 9 cm, in which an aluminum substrate was spread, was used. In the glass petri dish, 7 ml of the material solution was cast to form a liquid film. High-humidity air (humidity 70%) was blown onto this liquid film in an environment of temperature 25 ° C and humidity 30% (for 31itterZ). As a result, a Hercam structure (intermediate nonicuminolem) having a continuous hole was obtained as an intermediate.

[0085] Since the edge portion inside the glass petri dish is slightly lower, cast about 1 ml of black mouth form on this part, and then cover the glass petri dish for several tens of seconds. Was dissolved to produce a finished her cam structure (no-cam film).

[0086] The completed Hercam film was observed by SEM. The observation condition is that the magnification is X

4. Ok times, voltage was 16. Okv, and substrate was tilted 55 °. The results are shown in Fig. 2.

[0087] As is apparent from the results shown in FIG. 2, in the melted no-cam film, the pillar portion of the two-cam structure is crushed, and the upper structure and the lower structure of the hard cam are connected. It was observed that it had a structure. Therefore, it can be seen that the shape of the Hercam structure can also be controlled by the dissolution treatment.

Polybutadiene (trade name: RB820, JSR) and CAP polymer were used as the main body material, and a material solution was prepared using black mouth form as the first solvent. Polybutadiene and CAP polymer were dissolved in black mouth form so that the weight ratio was 10: 1, and a material solution was prepared so that the final concentration of the main body material was 1.5 mg / ml.

[0089] As a support, a glass petri dish having an outer diameter of 9 cm and covered with a cover glass (18 mm X 18 mm, MATSUNAMI) was used. In the glass petri dish, 5 ml of the material solution was cast to form a liquid film. The liquid film was sprayed with nitrogen through an air-washing bottle containing 200 ml of deionized water in an environment of a temperature of 23 ° C. and a humidity of 53% (21itterZ). As a result, a hard cam structure (intermediate hard cam film) having a continuous hole is obtained as an intermediate. It was.

[0090] The obtained intermediate knot-cam film was cut out together with the cover glass, and observed with an optical microscope (trade name: BH-2, OLYMPUS). The result is shown in Fig. 3 (a). Also, the intermediate hard-cam film cut out from each cover glass is heated at 100 ° C for 1 minute with a heater (trade name: RH6000, manufactured by Japan High-Tech) to melt the intermediate hard-cam film. V. A finished Hercam structure (Harcam film) was manufactured.

[0091] The resulting Hercam film was observed by SEM. The observation conditions were a magnification of 100 to L000, a voltage of 10 to 25 kv, and a substrate tilted by 0 ° to 75 °. The result is shown in Fig. 3 (b).

[0092] Note that the upper two SEM images in Fig. 3 (b) show the state of the substrate before heating, and the left side is an observation of the front (0 °) of the substrate. The right side is observed with the substrate tilted 70 °. In addition, the two lower SEM images in Fig. 3 (b) show the state of the substrate after heating, and are observed with the substrate tilted 70 ° on both the left and right sides. Note that the lower left SEM image in FIG. 3B is a non-penetrating membrane, and the lower right SEM image is a penetrating membrane.

A material solution was prepared using polytetrahydrofurfuryl metatalylate (Aldrich) and CAP polymer as the main material, and black mouth form as the first solvent. Polytetrahydrofurfuryl metatalylate and CAP polymer were dissolved in chloroform so as to have a weight ratio of 10: 1, and a material solution was prepared so that the final concentration of the main body material was 4 mgZml.

[0094] A glass petri dish having an outer diameter of 9 cm was used as a support. In this glass petri dish, 5 ml of the above material solution was cast to form a liquid film. High-humidity air (humidity 70%) was blown onto this liquid film in an environment of temperature 25 ° C and humidity 30% (21itterZ). As a result, a honeycomb structure (intermediate honeycomb film) having a continuous hole was obtained as an intermediate.

[0095] An adhesive tape (Cellotape (registered trademark), -Chiban Co., Ltd.) was applied to the surface of the intermediate knob-cam film, and then the tape was peeled off. The operation was repeated once and twice. As a result, the structure around the hole is formed in the intermediate film-cam film. A partially removed Hercam structure (No., two cam film) was produced.

[0096] The finished Hercam film and intermediate Hercam film obtained were observed by SEM. The observation conditions were such that the magnification was X 1. Ok, the voltage was 25 kv, and the substrate was tilted 55 °. As a result, the original Hercam structure, the pillar structure on the glass petri dish, and the pillar structure on the adhesive tape were compared. The results are shown in Fig. 4.

[0097] As can be seen from the resultant force shown in Fig. 4, the dimple structure was produced on the surface of the glass petri dish by repeating the operation of pasting and peeling with an adhesive tape three times.

Note that the present invention is not limited to the configurations described above, and various modifications can be made within the scope shown in the claims, and the technical means disclosed in the different embodiments can be appropriately used. Embodiments obtained in combination are also included in the technical scope of the present invention.

Industrial applicability

[0099] As described above, according to the present invention, the shape of the Her-cam structure is obtained by performing post-processing on the No-cam structure obtained by self-organizing the main body material using a droplet as a bowl shape. Is controlling. For this reason, it is possible to obtain a microporous membrane with a Hercam structure having various structures according to various purposes and applications, and it is possible to expand the field of use of the Hercam structure. Therefore, the present invention can be used in the fields of a microreactor, a photonic crystal, a cell culture substrate, etc. using a Hercom structure having isolated holes.

Claims

The scope of the claims

[1] A method for manufacturing a honeycomb structure having a plurality of holes arranged in a honeycomb shape, which supports at least a material solution in which a main body material to be a main body of a her-cam structure is dissolved or dispersed in a first solvent A liquid film forming step of forming a liquid film of the material solution by laminating on the body;

While the first solvent is volatilized from the formed liquid film, the droplets are formed into a shape by the self-organization of the main body material accompanying the formation of a second solvent droplet that does not mix with the first solvent. And a hole forming step of forming a plurality of holes in the form of a saw-cam,

Further, the film-like body obtained in the hole forming step includes a hole isolation step of isolating individual holes by partially deforming or removing the structure around the holes. A method for manufacturing a honeycomb structure.

[2] In the hole isolation step, the structure around the hole is partially formed by melting the main body material by heating the film-like body or by exposing the film-like body to a solvent or solution capable of dissolving the main body material. 2. The method for manufacturing a honeycomb structured body according to claim 1, wherein

[3] The honeycomb according to claim 1, wherein in the hole isolation step, the structure around the hole is partially removed by the adhesion and peeling of the pressure-sensitive adhesive body to the surface of the film-like body. Manufacturing method of structure.

[4] The method for producing a Hercam structure according to [3], wherein an adhesive tape is used as the pressure-sensitive adhesive body.

[5] The manufacturing of the honeycomb structure according to any one of claims 1 to 4, wherein the main body material is at least a polymer material or a monomer material that is polymerized by a polymerization reaction. Method.

[6] The honeycomb structure according to claim 5, wherein when the monomer material is used as the main body material, the material solution contains a catalyst for promoting a polymerization reaction of the monomer material. Body manufacturing method.

7. The method for manufacturing a honeycomb structured body according to any one of claims 1 to 6, wherein the first solvent is a hydrophobic organic solvent and the second solvent is water.

[8] In the hole forming step, droplets are formed on the surface of the liquid film by blowing a gas containing the vapor of the second solvent onto the liquid film. The method for manufacturing a honeycomb structure according to any one of the above.

[9] The Hercam structure according to any one of [1] to [8], wherein in the liquid film forming step, a liquid film is formed by casting the material solution onto the support surface. Production method.

[10] A honeycomb structure manufactured by the manufacturing method according to any one of claims 1 to 9.

[11] A method for manufacturing a honeycomb structure having a plurality of holes arranged in a honeycomb shape, wherein adjacent holes and holes communicate with each other and have a communicating portion. The membrane material manufactured by self-organizing the main body material of the main body using droplets as a trapezoid is partially deformed or removed from the structure around the hole, so that the individual parts in the communication portion can be individually removed. A method for manufacturing a honeycomb structure, comprising a hole isolation step for isolating holes.

[12] In the hole isolation step, the structure surrounding the hole is partially formed by melting the body material by heating the film body or exposing the film body to a solvent or solution that can dissolve the body material. 12. The method of manufacturing a her-cam structure according to claim 11, wherein the structure is changed in a stepwise manner.

[13] The structure according to claim 11, wherein in the hole isolation step, the structure around the hole is partially removed by the adhesion and peeling of the adhesive to the surface of the film-like body. Manufacturing method of cam structure.

[14] The method for producing a ham- arm structure according to [13], wherein an adhesive tape is used as the pressure-sensitive adhesive body.

[15] The honeycomb structure according to any one of claims 11 and 14, wherein the main body material is at least a polymer material or a monomer material that is polymerized by a polymerization reaction. Manufacturing method.