WO2007007877A1

WO2007007877A1 - Process for producing porous structure and porous structure obtained by the process

Info

Publication number: WO2007007877A1
Application number: PCT/JP2006/314067
Authority: WO
Inventors: Yusuke Yamada
Original assignee: The Furukawa Electric Co., Ltd.
Priority date: 2005-07-14
Filing date: 2006-07-14
Publication date: 2007-01-18
Also published as: JP2007046042A

Abstract

A reversed-micelle template is used to form a porous structure comprising an organic polymer and an amphipathic substance. When the porous structure is produced, the state of pores evenly distributed in the structure, the state of open pores or through-pores, pore diameter (opening diameter), pore density, etc. can be regulated by controlling conditions including the proportion of water to the amphipathic substance and the proportion of the organic polymer to the amphipathic substance. Thus, a highly functional porous structure can be formed. The process for producing a porous structure in which a reversed-micelle template formed in a hydrophobic-organic-solvent solution is used for pore formation comprises: (i) a step in which a solution comprising an amphipathic substance, a hydrophobic organic polymer, a hydrophilic liquid, and a hydrophobic organic solvent which dissolves the organic polymer is mixed with stirring to obtain a hydrophobic-organic-solvent solution having reversed micelles formed therein (step (1)); (ii) a step in which the hydrophobic-organic-solvent solution is cast on a substrate (step (2)); and (iii) a step in which the hydrophobic organic solvent and the hydrophilic liquid are evaporated and removed from the hydrophobic-organic-solvent solution on the substrate to form a porous structure (step (3)).

Description

Technical field of manufacturing porous structure and porous structure obtained from the manufacturing method

[0001] The present invention relates to a method for producing a porous structure using a cage shape of a reverse micelle formed in a hydrophobic organic solvent solution using an amphiphilic substance for the formation of pores, and the production method. And a porous structure.

Background art

[0002] A method for forming a polymer porous membrane having fine pores having a diameter of 1 to 100 μm using self-organization is a method using condensation of water droplets, a method using micelle formation, or a block. A method using a copolymer is known. As a method of utilizing condensation of water droplets, a hydrophobic organic solvent solution of a polymer is cast on a substrate in a high-humidity atmosphere, and the organic solvent is gradually evaporated and simultaneously condensed on the cast liquid surface. There is known a method for producing a film having a Hercam structure by evaporating fine water droplets generated by condensation (see Patent Document 1 or Patent Document 2). The method using the formation of micelles is a method in which a reverse micelle solution containing a hydrophobic substance composed of an olefin monomer or the like, a hydrophilic liquid such as water, and a surfactant containing a polymerizable group is permeated onto the carrier. Thereafter, the liquid is polymerized to form a porous material coating on the support (see Patent Document 3). Examples of the method using a block copolymer include an example using a block copolymer block polystyrene having a hydrophilic block and a hydrophobic block force (see Non-Patent Document 1).

Patent Document 1: Japanese Patent Laid-Open No. 2001-157574

Patent Document 2: JP 2002-335949 A

Patent Document 3: Patent No. 3277233

Non-Patent Document 1: Science, 1999, No. 283, p. 372

Disclosure of the invention

Problems to be solved by the invention

[0004] In the above-described method using condensation, the formed film has self-supporting properties. However, in the method using dew condensation, minute water is formed by the formation of dew condensation under relatively high humidity conditions. It is difficult to control the density of the hole diameter of the droplet, and when the hole density increases, a phenomenon of communication between adjacent holes inevitably occurs, which may cause inconvenience depending on the purpose of use. In addition, when functional materials are introduced into the pores of the membrane in order to enhance the functionality of the membrane, these methods are used to introduce the functional material into the pores of the membrane that has been prepared in separate steps. And the process becomes more complex. Furthermore, if the hole diameter is small, it becomes difficult to selectively introduce the functional material into the hole.

On the other hand, in the method utilizing the formation of the micelles, the film to be formed has no self-supporting property and must be used integrally with the substrate. Therefore, the properties of the entire film depend on the properties of the substrate and are used. Applications were limited to filtration membranes and biosensors. In addition, when the block copolymer is used, there are many drawbacks such as inferior self-supporting property of the hard cam structure and the honeycomb structure with time.

Means for solving the problem

[0005] The present invention has been made in view of the above problems, and reverse micelles are formed in a solution comprising at least an amphiphile, a hydrophobic organic polymer, a hydrophilic liquid, and a hydrophobic organic solvent. Is formed on the substrate, and a hydrophobic organic solvent and a hydrophilic liquid are vaporized from the substrate. The present invention relates to the production of a porous body that is partitioned by a wall and communicates in a direction parallel to the surface of the structure.

That is, the present invention relates to (1) a porous structure using reverse micelle cages formed in a hydrophobic organic solvent solution for forming pores, comprising the steps described in the following (i) to (m): (Hereinafter sometimes referred to as “Embodiment 1”).

(i) A hydrophobic organic solvent in which reverse micelles are formed by stirring at least an amphiphile, a hydrophobic organic polymer, a hydrophilic liquid, and a hydrophobic organic solvent that dissolves the organic polymer. Step of obtaining a solution (Step 1)

(ii) A step of casting the hydrophobic organic solvent solution onto a substrate (Step 2)

(iii) A step of evaporating the hydrophobic organic solvent and the hydrophilic liquid from the hydrophobic organic solvent solution on the substrate to form a porous structure (step 3)

[0006] In the first embodiment, the following aspects (2) to (15) may be further provided. (2) Weight mixing ratio Rw (hydrophilic liquid Z both amphiphile) of hydrophilic liquid and amphiphile in step 1 is 0.1 to 15.

(3) Weight ratio Rp (organic polymer Z [organic polymer + amphiphile]) of organic polymer and amphiphile in step 1 is 0.1 to 0.9,

(4) The hydrophobic organic solvent is a normal pentane, normal hexane, cyclohexane, isooctane, normal heptane, normal decane, benzene, toluene, ethylbenzene, orthoxylene, meta-ethylene having a dielectric constant of 5 or less at 20 ° C. Xylene, para-xylene, mixed xylene, carbon tetrachloride, chloroform, and trans 1,2, -dichloroethylene, and butyl acetate, dichloromethane, 1,1,2,2- Tetrachloroluethane, cis 1,2-dichloroethane, and isobutyl methyl ketone

Power must be at least one selected,

(5) The amphiphile is bis (sodium 2-ethylhexylsulfosuccinate), sodium dioctylsulfosuccinate, sodium diisoptylsulfosuccinate, sodium dicyclohexylsulfosuccinate, sodium dihexylsulfosuccinate, dihexyl The polyion complex of xadecyldimethylammonium and polystyrene sulfonic acid, a block copolymer obtained from ethylene glycol and propylene glycol, and a block copolymer force capable of obtaining ethylene oxide and propylene oxide power are also at least one selected.

(6) The organic polymer is polyethylene, polypropylene, poly-4-methylpentene 1, cyclopolyolefin, polychlorinated butyl, polyvinylidene chloride, polystyrene, tali-tril-styrene resin (AS resin), acrylonitrile-butadiene-styrene Resin (ABS resin), Methacrylate ester resin, Acrylate ester resin, Ethylene butyl alcohol copolymer resin, Polyalkylene oxide, Polyamide, Polyacetal, Polycarbonate, Modified polyphenylene ether, Thermoplastic polyester At least one selected from the group consisting of polysulfone sulfide, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, and polyamideimide, (7) the substrate is made of glass, metal Ceramic, polypropylene, polyethylene, polyethylene terephthalate, polyether ketone, polyvinylidene modified styrene force chosen any one Or a substrate that is a combination of one or more of these,

(8) After forming a hydrophobic organic solvent solution containing reverse micelles in step 1, casting to a thickness of 0.01 to 5 mm on the substrate in step 2;

(9) Evaporating the hydrophobic organic solvent and hydrophilic liquid in step 3 under a dry gas flow,

(10) Use the hydrophobic organic solvent having a dielectric constant of 5 or less at 20 ° C in step 1 and a specific gravity of 0.65-0.90 at the same temperature, and the hydrophobic organic solvent in step 3 By evaporating, the negative force of the reverse micelle is a structure in which the holes formed are distributed almost uniformly in the structure, and the holes of the structure (excluding the openings and the through holes) An average value of the diameter of 0.1 to: forming a structure having L0 m,

(11) Using the organic polymer and Z or the hydrophobic organic solvent having a specific gravity greater than the specific gravity of the hydrophilic liquid in Step 1, and by the evaporation of the hydrophobic organic solvent in Step 3, perpendicular to the structure surface A structure in which the area ratio of holes (open holes) that are open (excluding through-holes) on the surface is 60% or more or the surface opening ratio is 5% or more in the total area of the holes in a simple cross section, Forming a structure having an average opening diameter of 0.1 to L00 μm,

(12) The Rw (hydrophilic liquid Z amphiphile) in step 1 is set to 3 to 15, and in step 2, the thickness of the multilayer structure after evaporation of the hydrophobic organic solvent in step 3 is set to ~ 50 m. The hydrophobic organic solvent solution is cast on a substrate, and the hole penetrating through the entire area of the hole in the cross section perpendicular to the structure surface due to evaporation of the hydrophobic organic solvent in step 3 (through hole) In which the surface area ratio is 60% or more or the surface opening ratio based on through holes is 7% or more, and the average hole diameter in the direction parallel to the structure surface of the through holes is 1 to 50 / zm, or the through holes Forming a structure with an average opening diameter of 1 to 50 m;

(13) The porous structure obtained by removing the substrate from the porous structure on the substrate formed in the step 3 has a self-supporting property,

(14) The hydrophobic organic solvent solution in Step 1 is an amphiphilic substance, a hydrophobic organic polymer, a hydrophobic organic solvent, a hydrophilic liquid, and a metal, alloy, or dispersion dispersed in the hydrophilic liquid phase. Is a metal compound fine particle force, and the metal, alloy or metal compound fine particles are contained in the pores of the porous structure obtained in step 3.

(15) The hydrophobic organic solvent solution in Step 1 is an amphiphilic substance, a hydrophobic organic polymer, a hydrophobic organic solvent, a hydrophilic liquid, and a functional material dispersed or dissolved in the hydrophilic liquid phase. And the functional material is contained in the pores of the porous structure obtained in step 3, and the functional material is Au, Ag, Cu, Pt, Fe, Ni, Co, Mn, Cr And at least one metal of Ti, semiconductor material, oxide, ceramic material, metal complex, ferroelectric material, ferromagnetic material, resistance change material, phase change material, optical functional material, and fluorescent functional material One functional material selected,

The present invention also relates to (16) a porous structure composed of an organic polymer having hydrophobicity, and an amphiphilic substance having an anionic group in a hydrophilic group having a molecular weight of 10,000 or less. The active substance constitutes the edge of the hole, and each hole is partitioned by a cutting wall made of the organic polymer, and communicates in a direction parallel to the surface of the structure. This is an invention relating to a porous structure (hereinafter referred to as “embodiment 2” t). In the second embodiment, the following aspects (17) to (28) can be further adopted.

(17) The amphiphile is composed of bis (sodium 2-ethylhexylsulfosuccinate), sodium dioctylsulfosuccinate, sodium diisoptylsulfosuccinate, sodium dicyclohexylsulfosuccinate, and sodium dihexylsulfosuccinate. Be at least one selected,

(18) The organic polymer is polyethylene, polypropylene, poly-4-methylpentene 1, cyclopolyolefin, polychlorinated buyl, poly (vinylidene chloride), polystyrene, tali-tril-styrene resin (AS resin), acrylonitrile-butadiene-styrene Resin (ABS resin), Methacrylate ester resin, Acrylate ester resin, Ethylene butyl alcohol copolymer resin, Polyalkylene oxide, Polyamide, Polyacetal, Polycarbonate, Modified polyphenylene ether, Thermoplastic polyester At least one selected from the group consisting of polysulfone sulfide, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, and polyamideimide,

(19) Weight mixing ratio of organic polymer and amphiphile in the porous structure (organic Limer Z (organic polymer + amphiphile)) is 0.1 to 0.9, (20) the porous structure is a porous film having self-supporting property,

[0010] (21) The pores of the structure are almost uniformly distributed in the structure, and the average pore diameter (excluding openings and through-holes) is 0.1 to LO / zm,

(22) Of the total area of the holes in the cross section perpendicular to the structure surface of the structure, the area ratio of holes (open holes) opened on the surface is 60% or more, or the surface opening ratio is 5% or more. And the average aperture diameter of the apertures is 0.1-100 μm,

(23) Of the total area of the holes in the cross section perpendicular to the structure surface of the structure, the area ratio of the through holes (through holes) is 60% or more, or the surface opening ratio based on the through holes is 7% or more. And the average hole diameter in the direction parallel to the surface of the structure of the through hole is 1 to 50 m, or the average opening diameter of the through hole is 1 to 50 μm,

(24) The porous structure is a film and has a thickness of 0.001 to lmm.

(25) The presence of metal, alloy or metal compound fine particles in the pores of the porous structure,

(26) In the pores of the porous structure, at least one metal selected from Au, Ag, Cu, Pt, Fe, Ni, Co, Mn, Cr and Ti, a semiconductor material, an oxide, a ceramic material, The presence of one functional material selected from metal complexes, ferroelectric materials, ferromagnetic materials, resistance change materials, phase change materials, optical functional materials, and fluorescent functional materials;

(27) the porous structure is formed on a substrate;

(28) The substrate has one of any force selected from glass, metal, ceramic substrate, polypropylene, polyethylene, polyethylene terephthalate, polyetherketone, and polyfluorinated styrene, which is a combination of at least one of these Being a substrate,

The invention's effect

[0011] According to the present invention, an organic polymer and an amphiphilic substance are formed by utilizing a reverse micelle cage formed in a hydrophobic organic solvent solution by a relatively easy operation for pore formation. A porous structure can be obtained.

At this time, by selecting the types of components such as hydrophobic organic solvent, amphiphile, hydrophilic liquid, organic polymer, and the blending ratio, the form of pores in the porous structure (the structure The pores are distributed almost uniformly, the pores are present on the surface of the structure, or the pores are present in the structure as through-holes), the size of the pores, the density of the pores, etc. It is possible to control.

A feature of the present invention is that most of the pores in the porous structure obtained by the present invention are partitioned by a partition wall that also has organic polymer power, and the pores communicate with each other.

In addition, since the formation of the porous structure and the embedding of the functional material in the pores of the structure can be performed at the same time, it is possible to form a porous structure having a high function at a low cost.

Brief Description of Drawings

FIG. 1 shows a time-dependent change in pore size distribution of reverse micelles in a hydrophobic organic solvent solution in Example 1.

FIG. 2 shows the change over time of the pore size distribution of reverse micelles in a hydrophobic organic solvent solution in Example 2.

FIG. 3 shows the change over time of the pore size distribution of reverse micelles in a hydrophobic organic solvent solution in Example 3.

FIG. 4 shows a cross-sectional view of the porous structure produced in Examples 4 and 5 when the Rw force is 25 (FIG. (A)) and the Rw force is .50 (FIG. (B)).

FIG. 5 shows a cross-sectional view of the porous structure produced in Examples 6 and 7 when the Rw force is 25 (FIG. (A)) and the Rw force is .50 (FIG. (B)).

FIG. 6 shows a cross-sectional view of the porous structure produced in Examples 8 and 9 when the Rw force is 25 (FIG. (A)) and the Rw force is .50 (FIG. (B)).

FIG. 7 shows an optical microscopic observation view of a porous film having an aperture hole produced in Example 13.

FIG. 8 is a perspective image of the porous film produced in Example 14 and observed with an optical microscope in which an oblique upward force of 45 degrees is also seen.

FIG. 9 shows the relationship between Rw and average opening diameter in the porous membranes obtained in Examples 13 and 23 to 25.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, Embodiments 1 and 2 of the present invention will be described. In addition, the observation, shape measurement, etc. of the hydrophobic organic solvent solution and the porous structure in the present invention are based on the following method.

(1) Measurement of micelle diameter of reverse micelle in hydrophobic organic solvent solution

By measurement using a laser diffractometer.

(2) Observation of surface and cross section of porous structure

By observation using a scanning electron microscope. The surface observation is performed as it is, and the cross-sectional observation is performed after cutting the surface perpendicularly to the surface to obtain a cross-section.

(3) Analysis of the concentration distribution of S (Io) component derived from polyion complex of dihexadecyldimethylammonium and polystyrenesulfonic acid

By observation using an energy dispersive X-ray fluorescence spectrometer.

(4) Measurement of parameters characterizing various forms of holes such as the following non-open holes, non-through holes, and through holes

Using a scanning electron microscope, the method described below is used.

(i) Non-opening holes (holes that are almost uniformly distributed in the structure and open)

Measurement of average hole diameter and cross-sectional porosity of non-open holes

(i 1) Measurement of average pore size

In the cross section of the porous structure, in consideration of the variation depending on the cutting position, five samples with large hole diameters corresponding to the approximate center cross section of the hole are extracted, and parallel to the surface of the structure of each hole. Measure the hole diameter (maximum length of holes in the parallel direction) and use the average value as the average hole diameter.

(i 2) Measurement of cross section porosity

In the cross section of the porous structure, the ratio of the pore area to the entire cross-sectional area is calculated and taken as the cross-sectional porosity.

(ii) Non-through hole (hole that is non-through and open)

Measurement of the area ratio of the non-through hole, the surface opening ratio, and the average opening diameter to the total area of the hole in the cross section

(ii-1) Area ratio of non-through holes to the total area of holes in the cross section

Area ratio of non-through-opening holes out of the total area of holes in any cross section of the porous structure Ask for.

(ii 2) Surface aperture ratio

Calculate the ratio of the area of non-through holes on the surface of the porous structure to the total surface area to obtain the surface area ratio.

(ii 3) Average opening diameter

Randomly extract 10 non-through holes on the surface of the porous structure, measure the opening diameter, and use the average value as the average opening diameter.

(iii) Negative hole

Out of the total area of holes in the cross section, the area ratio of through holes, surface opening ratio, average opening diameter, and average hole diameter in the direction parallel to the structure surface

(iii-1) Area ratio of through-hole to total area of hole in cross section

The area ratio of through-holes is determined from the total area of holes in an arbitrary cross section of the porous structure.

(iii 2) Surface aperture ratio

The ratio of the opening area of the through holes on the surface of the porous structure to the entire surface area is calculated to obtain the surface opening ratio.

(iii 3) Average opening diameter

Randomly extract 10 through-holes on the surface of the porous structure, measure the opening diameter, and use the average value as the average opening diameter.

(iii-1) Average hole diameter in the direction parallel to the surface of the through hole structure

Five holes with large hole dimensions corresponding to the approximate center cross section of the hole are extracted, and the hole diameter in the direction parallel to the surface of the structure of each hole (the maximum length of the holes in the parallel direction) is measured. The average value is the average pore diameter.

[1] Embodiment 1

The “method for producing a porous structure” according to Embodiment 1 includes:

A reverse micelle cage formed in a hydrophobic organic solvent solution including the steps described in the following (i) to (iii) is used for the formation of pores.

(i) at least amphiphile, hydrophobic organic polymer, hydrophilic liquid and the organic Step of obtaining a hydrophobic organic solvent solution in which reverse micelles are formed by mixing and stirring a solution consisting of a hydrophobic organic solvent that dissolves the polymer (Step 1)

Here, for example, in an aqueous solution in which the positive micelle is hydrophilic, the hydrophobic part of the amphiphile does not mix with water, so that the hydropower should be kept away and interact with the hydrophobic part. In contrast, a reverse micelle is a molecular assembly that has a structure opposite to that of a normal micelle in a hydrophobic organic solvent, and has a structure in which the hydrophobic portion protrudes into the solvent. is there

In the present invention, first, in Step 1, a solution comprising at least an amphiphile, a hydrophobic organic polymer, a hydrophilic liquid and a hydrophobic organic solvent is stirred to obtain a hydrophobic organic solvent. A relatively stable reverse micelle is formed therein. The reverse micelle distribution state (reverse micelles are uniformly distributed in the solution, relatively upwardly distributed or relatively downwardly distributed), reverse micelle diameter, density, etc. Organic solvents (dielectric constant, specific gravity, vapor pressure during evaporation, solubility of organic polymer, properties such as hydrophobicity), amphiphiles, hydrophilic liquids, organic polymers (physical properties such as specific gravity, hydrophobicity), etc. It can be controlled by the type of ingredients, the blending ratio, etc.

In addition, from the above conditions, the porous structure can be made into a thin film by using a hydrophobic organic solvent with a specific gravity larger than that of the hydrophilic liquid, a condition in which the reverse micelle diameter is relatively large, and a relatively small proportion of the organic polymer used. By evaporating the hydrophobic organic solvent in step 3, it is possible to form a structure with many holes on the surface of the structure and a structure with many through-holes. .

[0016] In step 2, the hydrophobic organic solvent solution is cast on the substrate, but after forming reverse micelles in the hydrophobic organic solvent solution, casting onto the substrate and further starting evaporation of the organic solvent. It is possible to control the thickness and the shape of the pores in the porous structure after evaporation of the hydrophobic organic solvent by selecting the time and the coating thickness of the hydrophobic organic solvent solution on the substrate. Next, in the first half of the step 3, the hydrophobic organic solvent solution on the substrate may be treated with a hydrophobic organic solvent (hereinafter referred to as “organic solvent” hereinafter), with conservative removal of the hydrophilic liquid (for example, water). ) Is removed by evaporation. In this case, as the organic solvent evaporates, the density of the reverse micelles in the hydrophobic organic solvent solution increases, but in the present invention, the holes formed by the organic solvent evaporation are partitioned by the partition wall made of the organic polymer cover. As a result, many unique holes are formed through communication.

The evaporation time of the organic solvent is about several minutes, but the pores formed in the structure can be made more three-dimensionally uniform by selecting the temperature and pressure conditions at which the organic solvent evaporates in a relatively short time. It becomes possible to distribute.

When reverse micelles are present uniformly in the porous structure, the hydrophilic liquid is confined in the reverse micelles and sealed in an organic solvent. Even if the vapor pressure of the solvent is lower than that of the hydrophilic liquid, the organic solvent evaporates selectively. However, it appears that the amount of hydrophilic liquid present in reverse micelles is extremely small and that the hydrophilic liquid will eventually evaporate through small amounts of dissolution in organic solvents and organic polymers.

When the pores in the porous structure formed during the evaporation of the organic solvent are formed as openings or through holes as a result, the hydrophilic liquid can be easily removed by evaporation. After evaporation of the organic solvent, an amphiphile is present at the edge of the pores formed in the porous structure.

Steps 1 to 3 will be described in detail below.

(A) Step of obtaining a hydrophobic organic solvent solution (Step 1)

In Embodiment 1, first, in Step 1, reverse micelles are formed in a hydrophobic organic solvent solution.

(A-1) Hydrophobic organic solvent solution components

In step 1, at least an amphiphile, a hydrophobic organic polymer, a hydrophilic liquid, and a component comprising the organic polymer are used. These components that can be used in Step 1 are exemplified below, but those that can be used in the present invention are not limited to these. (a) Organic polymer

The organic polymer that can be used in the present invention is hydrophobic and has an appropriate solubility in an organic solvent, and can maintain a cage structure based on reverse micelles that are self-assembled after the organic solvent is removed by evaporation in Step 3. Depending on the purpose of use, it is preferable that the porous film formed on the substrate has rigidity enough to have self-supporting properties. Specific examples of the organic polymer include olefin-based polymers such as polyethylene, polypropylene, poly-4-methylpentene-1, cyclopolyolefin, etc .; polychlorinated butyl, polysalt-bi-lidene chlorine-based polymer; polyalkylene oxide; Alcohol-based resins such as butyl alcohol and ethylene-bulb alcohol copolymerized resins; polystyrene, Atari mouth-tolyl-styrene resin (AS resin), styrenes such as acrylonitrile-butadiene-styrene resin (ABS resin) Acrylic resin such as methacrylic ester resin and acrylic ester resin; polyamide resin (polyamide 6, polyamide 46, polyamide 66, etc.), polyacetal, polycarbonate, modified polyphenylene ether, thermoplastic Polyester resin (polyethylene terephthalate, Do the phase separation occurs after re ethylene naphthalate, etc.), etc. one engineering selected from plastic, or having compatibility (hydrophobic organic solvent evaporated! /,) 2 or more organic polymers.

[0018] In addition, depending on the selection or use purpose of the organic solvent, thermoplastic resins such as polyvinylidene fluoride, polytetrafluoroethylene, polyacetate butyl, cellulosic plastic, and thermoplastic elastomer may be used as the organic polymer. Polyphenylene sulfide, polysulfone, amorphous polyarylate, polyether imide, polyether sulfone, polyether ketone, polyethylene ether ketone, liquid crystal polyester, polyamide imide, polyimide and the like can also be used.

Of these, polystyrene and acrylic resin are preferable in terms of cost, and polycarbonate, cyclopolyolefin, fluorine resin are also preferable in terms of transparency, and polyamide and polyimide are preferable from the viewpoint of heat resistance. Polystyrene, polycarbonate, and cyclopolyolefin are particularly preferred because they are soluble in organic solvents such as black mouth form and can easily obtain a membrane-like porous structure.

[0019] (b) Amphiphile The amphiphile used in Embodiment 1 is not particularly limited as long as it has a hydrophobic group and a hydrophilic group, and may be a polymer amphiphile or an amphiphile other than a polymer. Examples of anions constituting hydrophilic groups in ionic amphiphiles include —Coo_, —so—, etc., and cations such as dimethylammonium ion, trimethyl.

Four

Ruammo-mu ion, pyridi-mu ion, etc. In addition, the hydrophilic group in the nonionic amphiphile includes a hydroxyl group and an ether bond.

Specific examples of amphiphiles include bis (2-ethylhexylsulfosuccinate) (shown by the following chemical formula 1), sodium dioctylsulfosuccinate, sodium diisoptylsulfosuccinosuccinate, dicyclohexyl. Block copolymer from which sodium sulfosuccinate, dihexyl sodium sulfosuccinate, dihexadecyldimethylammonium and polystyrenesulfonic acid polyion complex (shown by the following chemical formula 2), ethylene glycol and propylene glycol can be obtained, ethylene oxide And propylene oxide strength At least one selected block copolymer strength can be mentioned.

[0020] [Chemical 1]

Chemical formula 1 Chemical formula 2

[0021] (c) Hydrophobic organic solvent

The organic solvent used in Embodiment 1 has a property of dissolving hydrophobic organic polymer to some extent, making reverse micelles small and stable to some extent with a micelle diameter, and step 3 The type is not particularly limited as long as it has the property of being relatively easy to evaporate. In selecting the hydrophobic organic solvent of the present invention, the desired reverse micelle form (uniform dispersion in the solution, micelle diameter, etc.), stability, evaporability in step 3, etc., the hydrophobicity of the organic solvent, It is desirable to consider dielectric constant, solubility of organic polymer, vapor pressure, specific gravity and the like.

[0022] In Step 1 of the present invention, reverse micelles are formed in the hydrophobic organic solvent solution, so the organic solvent to be used needs to be hydrophobic, and the water is a hydrophilic liquid. Hydrophilic organic solvents such as methyl acetate and tetrahydrofuran, which have a high solubility in, are suitable because they do not form good reverse micelles.

[0023] The reverse micelles in the hydrophobic organic solvent solution described in the above step 1 are cast until the casting of step 2 and the organic solvent of step 3 evaporate to form the basic skeleton of the porous structure. It is desirable that it is relatively stable. In general, reverse micelles are relatively stable in nonpolar organic solvents having a low dielectric constant.

Table 1 shows examples of relatively non-polar organic solvents having a dielectric constant (ε) of 5 or less at 20 ° C, and Table 2 shows relatively polar organic solvents having a dielectric constant of more than 5 at 20 ° C. It is.

In toluene (ε: 2.38), which has a low dielectric constant at 20 ° C, reverse micelles tend to exist relatively stably with small micelle diameters. For example, in the composition shown in Table 1, ε: 2.40 With the black mouth form (ε: 4.81), if the change in the micelle diameter over time can be grasped, it can be used to control the pore diameter of the porous structure.

In this way, the desired porous structure can be designed from the selection of the hydrophobic organic solvent by grasping the micelle diameter and distribution of reverse micelles in each hydrophobic organic solvent, and the change in the micelle diameter over time. Is possible.

[0024] The hydrophobic organic solvent is preferably a solvent in which an organic polymer is appropriately dissolved and the amphiphilic substance is excellent in uniform dispersibility. In particular, it is desirable that the hydrophobic organic solvent appropriately dissolves the used hydrophobic organic polymer and amphiphile. In this case, if the solubility of the organic polymer and the amphiphile in the hydrophobic organic solvent is too high, the organic polymer and the amphiphile in the organic solvent become porous at the stage where the organic polymer and the amphiphile in the organic solvent reach a high concentration in the evaporation step of Step 3. When the basic structure of the structure is formed, it may cause inconvenience to form pores uniformly, while the solubility of the organic polymer and amphiphile in hydrophobic organic solvent If it is low, it is necessary to use a relatively large amount of an organic solvent, which may not be preferable. It is desirable that the organic polymer and the amphiphilic substance in the hydrophobic organic solvent be in a concentration range of about 0.01 to LgZml, particularly 0.05 to 0.5 gZml, together with the hydrophobic organic solvent solution.

[0025] In step 3, when a porous structure is formed by evaporating the organic solvent and the hydrophilic liquid from the hydrophobic organic solvent solution, a large amount of the organic solvent is first evaporated, and then the hydrophilic liquid is evaporated. The porous structure can be surely formed by making it. For this purpose, the vapor pressure of the hydrophobic organic solvent at the evaporation temperature of the hydrophobic organic solvent and the hydrophilic liquid is preferably higher than the vapor pressure of the hydrophilic liquid.

As described above, since the hydrophilic liquid exists in a state of being sealed in the hydrophobic organic solvent solution by the amphiphilic substance, the vapor pressure of the organic solvent is determined at the evaporation temperature of the hydrophobic organic solvent in Step 3. As a result, when the organic solvent present in a relatively large amount evaporates to some extent, the viscosity of the solution increases to such an extent that the reverse micelle shape (or its bowl-shaped structure) can be maintained. If so, it is possible to form a porous structure. The vapor pressure of the hydrophobic organic solvent at the evaporation temperature in step 3 is preferably at least 0.3 times, more preferably at least 0.7 times, particularly preferably at least 1.0 times the vapor pressure of the hydrophilic liquid. In such a case, it is possible to use an organic solvent such as toluene or xylene having a boiling point higher than that of the hydrophilic liquid.

[0026] The specific gravity of the organic solvent can be used to control the vertical formation positions of the pores in the formed porous structure.

In general, it is desirable to use a nonpolar solvent when it is desired to uniformly distribute the pores in the porous structure. On the other hand, when water is used as the hydrophilic liquid, for example, if a specific gravity such as chloroform is larger than that of water, reverse micelles can be distributed more upward, while aliphatic carbonization is performed. If a specific gravity such as hydrogen or an aromatic hydrocarbon is smaller than that of water, a large number of reverse micelles can be distributed downward. When many reverse micelles are distributed upward, the specific gravity of the organic polymer is larger than the specific gravity of water except for some polyolefins such as polyethylene and polypropylene. It is also possible to use an organic solvent smaller than the specific gravity of water using the specific gravity of Is possible.

Specific examples of hydrophobic organic solvents with specific gravity greater than water include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1,2 dichloro. Examples of chlorinated solvents such as ethylene and trichloroethylene; disulfur carbon and the specific gravity of hydrophobic organic solvents that are lighter than water include normal pentane, normal hexane, cyclohexane, and benzene. , Toluene, xylene and the like. These organic solvents can be used alone, or a mixed solvent can be used when these solvents are combined to form a uniform solution.

[0027] As the hydrophobic organic solvent that can be used in the present invention, as shown in Table 1, normal pentane, normal hexane, cyclohexane, isooctane, normal heptane, normal decane, which are not more than the dielectric constant force at 20 ° C, Benzene, toluene, ethylbenzene, orthoxylene, metaxylene, paraxylene, mixed xylene, carbon tetrachloride, black form, and trans 1,2, -dichloroethylene,

And butyl acetate, dichloromethane, 1,1,2,2-tetrachloroethane, cis 1,2-dichloroethane, and isobutyl methyl ketone or mixtures thereof as shown in Table 2 and having a dielectric constant of greater than 5 at 20 ° C. However, the hydrophobic organic solvent that can be used in the present invention is not limited thereto.

It is preferable that the hydrophobic organic solvent has a high solubility of the organic polymer, a low solubility of water and a high vapor pressure. Further, it is preferable from the viewpoint of practicality. It is preferably chemically stable and low in toxicity. From these viewpoints, preferred examples of the solvent include toluene and black mouth form.

[0028] [Table 1] Nonpolar solvent

* Composition of mixed xylene (mass%)

To ethyl: ortho-xylene: meta-xylene: ba-xylene = 15: 22: 44: 19

[0029] [Table 2]

Polar solvent

[0030] (d) Hydrophilic liquid

Water is most preferably used as the hydrophilic liquid for forming reverse micelles. In the present invention, a hydrophobic organic solvent comprising an amphiphile, an organic polymer, a hydrophobic organic solvent, and a hydrophilic liquid. If a reverse micelle is formed in a hydrophobic organic solvent solution, a hydrophilic liquid other than water or a hydrophilic liquid other than water is added to water. Thus, the specific gravity, vapor pressure, solubility, etc. of the hydrophilic liquid can be adjusted. Examples of hydrophilic liquids other than water include ethylene glycol, propylene glycol, formic acid and the like.

[0031] (A-2) Mixing ratio of hydrophobic organic solvent solution component

The weight ratio Rw (hydrophilic liquid, amphiphile) between the hydrophilic liquid and the amphiphile in Step 1 is preferably 0.1 to 15 depending on the micelle diameter design of the reverse micelle. 2 to 15 is more preferred 0.5 to 10 is particularly preferred. By setting Rw to 0.1 or more, reverse micelles can be easily formed, and by setting the Rw to 15 or less, it is possible to effectively prevent reverse micelles from irreversibly aggregating.

Further, the size of the reverse micelle formed in the hydrophobic organic solvent solution can be controlled within the above range. That is, when Rw is increased, the diameter of the reverse micelle is increased. On the other hand, by decreasing Rw, the diameter of the reverse micelle can be decreased.

[0032] When the concentration of the organic polymer dissolved in the hydrophobic organic solvent solution is expressed as the concentration of the organic polymer in the organic solvent and the organic polymer, 0.01 to: LO mass% is more preferable. 0.05 to 5% by mass. In this concentration range, the pore diameter becomes uniform, and the pores tend to be more easily ordered.

Also, the weight blending ratio of organic polymer and amphiphile in step 1 (ratio of organic polymer to the sum of organic polymer and amphiphile: organic polymer Z [organic polymer + amphiphile]) (hereinafter referred to as Rp) 0.1 to 0.9 is preferred 0.1 or 0.6 is more preferred.

By setting Rp to the above blending ratio, the formation of reverse micelles can be ensured.

[0033] The density of the pores in the porous membrane, that is, the ratio of the pores per unit volume, can be controlled by the relative concentrations of the hydrophilic liquid, the organic polymer, and the amphiphile. That is, the weight ratio of the hydrophilic liquid to the entire solute (hydrophilic liquid + organic polymer + amphiphile) (hydrophilic liquid Z [hydrophilic liquid + organic polymer + amphiphile]) (hereinafter referred to as Rs The density of the holes increases relatively. At this time, if the concentration of the organic polymer and the amphiphile is constant, the pore size does not increase, and the density of the pores increases with the concentration of water S. On the other hand, the concentration of the amphiphile increases with the water concentration. If Rw is constant, the hole density is increased while the hole diameter remains constant.

In addition, the pore size can be controlled by Rw, and the film thickness can be controlled by the concentration of the organic polymer in the hydrophobic organic solvent solution and the thickness condition of the solution cast on the substrate. Can be controlled. That is, a through-hole can be formed by setting the film thickness to be equal to or smaller than the hole diameter, and a non-through hole can be formed by setting the film thickness to be equal to or larger than the hole diameter.

[0034] In step 1, the blending order of the amphiphile, organic polymer, hydrophilic liquid and organic solvent is not particularly limited. Agitating these components in a container to form reverse micelles. Magnetic stirring, which is widely used in experiments, is possible if sufficient agitation is possible without the need for special operations in the stirring method. · Examples include stirrers, rotating blades, and stirring using ultrasonic waves. Of these, a stirring method using ultrasonic waves is preferable from the viewpoint of finer and uniform pore diameter.

[0035] (B) Casting process (Process 2)

Step 2 is a step of casting the hydrophobic organic solvent solution formed in Step 1 onto a substrate.

A substrate on which such a hydrophobic organic solvent solution is cast is required to have durability such as solvent resistance to the organic solvent to be used, but is not particularly limited as long as this is satisfied. For example, the substrate is an inorganic substrate such as glass, a ceramic substrate such as a metal or silicon oxide, an organic substrate excellent in resistance to organic solvents such as polypropylene, polyethylene, polyethylene terephthalate, polyetherenoketone, or polyphenylene ethylene. One type of cocoon selected from can be a substrate that is a combination of one or more of these types.

The hydrophobic organic solvent solution can be applied on the substrate to a predetermined thickness using a blade coater or the like. In this case, the thickness of the solution is preferably about 0.01 to 5 mm, and more preferably 0.05 to lmm. In this thickness range, the organic solvent evaporates in a short time, and sufficient mechanical strength can be imparted to the obtained film-like multilayer structure. The thickness of the coating is important in controlling the density of pores formed in the porous structure and the arrangement of the pores together with the concentration of the organic polymer in the hydrophobic organic solvent solution.

[0036] (C) Evaporation process (process 3) Step 3 is a step of obtaining a porous film having reverse micelles in a bowl shape by evaporating the organic solvent and the hydrophilic liquid from the hydrophobic organic solvent solution on the substrate. Water is particularly preferable as the hydrophilic liquid.

(C-1) Evaporation operation of organic solvent

By using an organic solvent at a fumigation pressure higher than the vapor pressure of the hydrophilic liquid at a temperature at which the organic solvent and the hydrophilic liquid evaporate, a relatively large amount of the organic solvent evaporates, and then the hydrophilic solvent in the reverse micelle As a result of the evaporation of the conductive liquid, a porous film utilizing a reverse micelle cage is formed. However, as described above, when the organic solvent and the hydrophilic liquid are evaporated from the hydrophobic organic solvent solution, even if the vapor pressure of the organic solvent is lower than the vapor pressure of the hydrophilic liquid, the hydrophilic liquid is not mixed with the organic solvent and the amphiphile. When the hydrophobic organic solvent evaporates to some extent, if the viscosity of the solution increases to such an extent that the reverse micelle or its vertical structure can be maintained, a porous structure can be formed. It becomes.

In this solvent evaporation process, the reverse micelles are regularly arranged in a self-organized manner due to van der Waals force and electrostatic force acting between the reverse micelles, friction force between the reverse micelles and the substrate, capillary force, and the like. For this reason, the pores of the porous structure having the reverse micelles in a bowl shape are relatively regularly arranged.

In step 3, the arrangement regularity of the holes can be controlled by changing the ambient temperature, pressure, and the like. Lowering the temperature decreases the solvent evaporation rate and increases the time spent in the self-assembled arrangement of reverse micelles. Therefore, the arrangement regularity is improved. Increasing the pressure suppresses the evaporation of the solvent and also reduces the evaporation rate of the solvent, thus increasing the ordering regularity. Further, the arrangement regularity can also be improved by irradiating ultrasonic waves.

The method for evaporating the hydrophobic organic solvent solution and the hydrophilic liquid is not particularly limited. It is desirable that V ヽ be carried out under a dry inert gas flow while the hydrophobic organic solvent solution is allowed to stand. Examples of the dry inert gas include dry air and dry inert gas. The dry inert gas in this case is preferably air or an inert gas having a relative humidity of 70% or less, more preferably a relative humidity of 50% or less, and particularly preferably a relative humidity of 30% or less. This evaporation operation can be performed under reduced pressure, normal pressure, or increased pressure. It is desirable to increase the pressure under reduced pressure.

(C-2) Formation of porous structure

The porous structure formed on the substrate after evaporating and removing the hydrophobic organic solvent and the hydrophilic liquid is usually a film. In this case, the thickness of the film is preferably in the range of 0.001 to lmm, more preferably 0.005-0.1mm. In this thickness range, the porous structure has a sufficient mechanical strength, and it is relatively easy to control the penetration or non-penetration of the formed holes. The thickness of such a porous structure can be controlled by the concentration of the organic polymer in the hydrophobic organic solvent solution in Step 1 and the thickness of the hydrophobic organic solvent solution on the substrate in Step 2.

[0038] (i) Formation of a porous structure in which fine pores are uniformly distributed

In step 1, a hydrophobic organic solvent having a dielectric constant of 5 or less is used, and in step 3, evaporation of about 90% by mass of the hydrophobic organic solvent is preferably within 3 minutes, more preferably within 2 minutes. It is possible to form a structure in which the holes formed by the saddle force of the reverse micelles are distributed almost uniformly in the structure, particularly preferably by performing the temperature and pressure conditions that are completed within 1 minute. Become. The evaporation rate of the hydrophobic organic solvent can be controlled by the temperature and pressure conditions in the system, but it is desirable to control the degree of vacuum or partial pressure in the system. In this case, using a hydrophobic organic solvent having a specific gravity of 0.665-0.90 at 20 ° C improves the uniform distribution.

By the above operation, the average hole diameter of the holes can be set to 0.1 to L0 m.

[0039] (ii) Formation of porous structure having openings

In step 1, the specific gravity is greater than the specific gravity of the hydrophilic liquid, the organic polymer and the hydrophobic organic solvent are used, and in step 3, about 90% by mass of the hydrophobic organic solvent is evaporated. Is preferably performed for 1 minute or more, more preferably 3 minutes or more, and particularly preferably 5 minutes or more under the temperature and pressure conditions. A structure having a ratio of 60% or more or a surface opening ratio of 5% or more can be formed. The evaporation rate of the hydrophobic organic solvent can be controlled by the temperature and pressure conditions in the system, but it is desirable to control the degree of vacuum or partial pressure in the system. Regarding the surface opening ratio, as described above, the weight ratio of the hydrophilic liquid to the entire solute (hydrophilic liquid + organic polymer + amphiphile) (hydrophilic liquid Z [hydrophilic liquid + organic polymer] + Amphiphile]) (hereinafter sometimes referred to as Rs), it is possible to relatively increase the density of the pores, with constant concentrations of organic polymer and amphiphile. While increasing the pore size, the density of the pores can be increased. On the other hand, if the Rw is constant while increasing the concentration of the amphiphile as well as the concentration of water, the density of the pores can be increased while keeping the pore size constant. it can.

When water is used as the hydrophilic liquid, in this case, when the hydrophobic organic solvent having a specific gravity at 20 ° C of about 1.0 to 1.6 is used, the ratio of the open holes is improved. Can be raised.

In this case, the average opening diameter of the opening holes may be 0.1 to: LOO / zm.

[0040] (iii) Formation of porous structure having through-holes

The Rw (hydrophilic liquid water Z amphiphile) in step 1 is 3 to 15, and the thickness of the multilayer structure after evaporation of the hydrophobic organic solvent in step 3 is 1 to 50; ζ ΐη By casting the hydrophobic organic solvent solution on the substrate in step 2, the area ratio of the through holes is 60% or more of the total area of the holes in the cross section perpendicular to the structure surface, or the surface opening ratio based on the through holes It is possible to form a structure with a 7% or more. The surface opening ratio based on the through holes is the same as described for the surface opening ratio in the above-mentioned “formation of porous structure having openings”.

In this case, the average hole diameter in the direction parallel to the surface of the structure of the through hole can be set to 1 to 50 m, or the average opening diameter of the opening hole can be set to 1 to 50 m.

(iv) Formation of a porous structure having self-supporting properties

In addition, it is desirable that the porous structure obtained by removing the substrate from the porous structure on the substrate formed in step 3 has self-supporting properties from the viewpoint of workability. Self-supporting means that the structure itself is self-supporting, and it is possible to provide self-supporting by selecting an organic polymer and designing the thickness of the porous structure.

[0041] (D) Other

In the present invention, the hydrophobic organic solvent solution in Step 1 contains an amphiphilic substance and an organic polymer. , An organic solvent, a hydrophobic organic solvent, water, and a porous material obtained through the subsequent step 2 and step 3 when the metal, alloy or metal compound particles dispersed in the aqueous phase are contained. The metal, alloy or metal compound fine particles can be contained in the pores of the structure.

Similarly, if a functional material is contained in the hydrophobic organic solvent solution in step 1, the functional material is contained in the pores of the porous structure obtained through the subsequent steps 2 and 3. It becomes possible. That is, the hydrophobic organic solvent solution used in Step 1 is composed of an amphiphile, a hydrophobic organic polymer, a hydrophobic organic solvent, water, and a functional material dispersed or dissolved in the aqueous phase. The functional material is contained in the pores of the porous structure obtained in step 3. In this case, the functional material includes at least one metal selected from Au, Ag, Cu, Pt, Fe, Ni, Co, Mn, Cr and Ti, a semiconductor material, an oxide, a ceramic material, and a metal. Examples include at least one selected from complexes, ferroelectric materials, ferromagnetic materials, resistance change materials, phase change materials, optical functional materials, and fluorescent functional materials, but other functional materials are also available. It is possible to use. The oxides are not limited to metal oxides, and can include non-metal oxides such as silicon oxides as necessary.

[2] Embodiment 2

The porous structure according to Embodiment 2 (hereinafter “porous structure A” t ゝぅ) includes an organic polymer having hydrophobicity and an amphiphile having an anionic group in a hydrophilic group having a molecular weight of 10,000 or less. A porous structure composed of an organic substance, wherein the amphiphile constitutes the edge of the hole and each hole is partitioned by a partition wall made of the organic polymer. It is characterized in that it communicates in a direction parallel to the surface.

Such a porous structure A can be obtained by using an amphiphilic substance having an anionic group as a hydrophilic group in Step 1 of Embodiment 1 by using an electrostatic repulsive force between hydrophilic groups. The distance becomes larger. Furthermore, by using a low molecular weight amphiphile having a molecular weight of 10,000 or less, micelles are more easily dispersed by electrostatic repulsion than those having a high molecular weight. As a result, even in the portion where the distance between the formed holes is the smallest, it has a certain thickness, so that the holes do not communicate with each other in the direction parallel to the surface of the structure. The structure is such that each hole is partitioned by a partition wall that also has the organic polymer force.

[0043] The method for producing porous structure A is basically the same as the method described in Steps 1 to 3 of Embodiment 1, and the organic polymer used is the same as that described in Step 1 of Embodiment 1. Can be illustrated.

In an amphiphilic substance having an ionic group in a hydrophilic group having a molecular weight of 10,000 or less, examples of the anion constituting the hydrophilic group include -coo_, -so- and the like. Amphiphiles

Four

As a general rule, amphiphiles containing anions in hydrophilic groups are generally more stable in micelle dispersion than amphipathic lipids containing cations such as dimethylammonium, trimethylammonium and pyridinium ions in hydrophilic groups. It is more preferable for industrial applications because of its high heat resistance and high heat resistance.

Amphiphilic substances having an anionic group in the hydrophilic group with a molecular weight of 10,000 or less include bis (sodium 2-ethylhexylsulfosuccinate), sodium dioctylsulfosuccinate, sodium diisoptylsulfosuccinate, dicyclohexane. Sodium hexylsulfosuccinate

, And dihexylsulfosuccinate sodium power One or more selected can be exemplified, but the present invention is not limited thereto.

Examples of the porous structure obtained in Embodiment 4 include the following (i) to (iii). The formation of these is as described in the first embodiment.

(i) Porous structure in which the pores in the structure are almost uniformly distributed in the structure, and the average pore diameter is 0.1 to L0 m

(ii) Of the total area of the holes in the cross section perpendicular to the structure surface of the structure, the area ratio of the surface opening holes is 60% or more or the surface opening ratio is 5% or more, and the average opening of the opening holes is Porous structure having a diameter of 0.1-: LOO / zm

(iii) Of the total area of the holes in the cross section perpendicular to the structure surface of the structure, the area ratio of the through holes is 60% or more, or the surface opening ratio based on the through holes is 7% or more, and the through holes A porous structure having an average pore diameter of 1 to 50 m in a direction parallel to the surface of the structure, or an average opening diameter of the through holes of 1 to 50 m

In the porous structure A, as described in Embodiment 1, the porous structure is a self-supporting porous film, and the average opening diameter of the pores of the porous structure is 0.1-1 It is desirable that the thickness is 00 μm, and the porous structure is a film and has a thickness of 0.001-1 mm.

[0045] In the porous structure A, by using the filling method described in the second embodiment, it is possible to make metal, alloy, or metal compound fine particles exist in the pores of the porous structure. Similarly, at least one of metals such as Au, Ag, Cu, Pt, Fe, Ni, Co, Mn, Cr, and Ti, semiconductor materials, oxides, ceramics, metals in the pores of the porous structure Complex materials, ferroelectric materials, ferromagnetic materials, resistance change materials, phase change materials, optical functional materials, and fluorescent functional materials may exist in the form of fine particles or aqueous solutions. Although it is possible, functional materials other than these can also be used. The oxide is not limited to a metal oxide, but can include a non-metal oxide such as silicon oxide as necessary.

Further, in the porous structure B, as described in the first embodiment, the porous structure B may be formed on the substrate. The substrate may be an inorganic substrate such as glass, metal, silicon oxide. Ceramic substrates such as polypropylene, polyethylene, polyethylene terephthalate, polyetherketone, polyfluorinated styrene, etc., any one selected from these substrates, or a substrate that combines at least one of these may be used. it can.

[0046] The multilayer structure or porous structure A manufactured according to Embodiment 1 can be widely used in the fields of semiconductors, capacitors, magnetic memories, memories, DVDs, light-emitting devices, biochips, and the like. .

Example

[0047] The power of the present invention to be described below with reference to examples. The present invention is not limited to the following examples.

(1) The following evaluation methods were employed in the present examples and comparative examples.

(i) Measurement of micelle size of reverse micelle in hydrophobic organic solvent solution

Measurement was performed using a laser diffractometer (laser diffraction Z scattering type particle size distribution analyzer, model: LA-920, manufactured by Horiba, Ltd.).

(ii) Cross-sectional observation of porous structure

Using a scanning electron microscope (SEM) (model: JSM-6330F, manufactured by JEOL Ltd.) The structure cut out perpendicularly to the surface and cut out was observed.

(iii) Analysis of the concentration distribution of the S (io) component derived from the polyion complex of dihexadecyldimethylammonium and polystyrenesulfonic acid

S component concentration distribution was analyzed using an energy dispersive X-ray fluorescence spectrometer. (iv) Method for measuring the average pore size and cross-sectional porosity of pores in porous structures with pores distributed almost uniformly!

From the observation results of the cross-section of the membrane using a scanning electron microscope, arbitrarily extract five samples that are close to the central cross section of the hole, measure the hole diameter in the direction parallel to the surface of the structure of each hole, and average the average value. The pore size was used. Similarly, the ratio of the pore area to the entire membrane cross-sectional area was calculated from the results of membrane cross-sectional observation, and used as the cross-sectional porosity.

(V) Measuring method of area ratio of non-through-opening hole, average opening diameter, and surface opening ratio of cross-sectional area of structure whose opening is 60% or more among holes

The area ratio of the non-through hole was calculated out of the total area of the holes in an arbitrary cross section of the porous structure by a scanning electron microscope. From the film surface observation results, 10 non-through-holes were randomly extracted to measure the hole diameter, and the average value was taken as the average opening diameter. Similarly, the ratio of the area of the non-through holes to the entire surface area of the membrane was calculated from the results of observation of the membrane surface and used as the surface opening rate.

(vi) Measurement of the area ratio, surface opening ratio, average opening diameter, and average hole diameter in the direction parallel to the surface of the structure with respect to the total area of the holes in the cross section of the structure with 60% or more of the through holes Law

The area ratio of the through holes to the total area of the holes in the cross section is the area ratio of the through holes in the total area of the holes in any cross section of the porous structure. The surface opening ratio is obtained by calculating the ratio of the opening area of the through holes on the surface of the porous structure to the entire surface area. For the average opening diameter, 10 through-holes on the surface of the porous structure are randomly extracted and the opening diameter is measured, and the average value is taken as the average opening diameter. For the average hole diameter in the direction parallel to the structure surface of the through-hole, five holes with large hole sizes corresponding to the approximate center cross section of the hole are extracted, and the hole diameter in the direction parallel to the structure surface of each hole ( The maximum length of the holes in the parallel direction) is measured, and the average value is taken as the average hole diameter. [0049] (2) Samples used in Examples and Comparative Examples and their abbreviations are shown below.

(i) Polystyrene: Idemitsu Petrochemical Co., Ltd. (trade name: HH30) was used.

(ii) Bis (sodium 2-ethylhexylsulfosuccinate) (AOT): Aldrich (molecular weight: 444) was used.

(iii) Dihexadecyl dimethyl ammonium polystyrene complex (PIC): Dihexadecyl dimethyl ammonium bromide (Tokyo Kasei) 1.0 g of 2% ultrasonic dispersion and polystyrene sulfonic acid Sodium (manufactured by Aldrich) 0.24 g of 0.5% aqueous solution was stirred at 60 ° C., and the resulting white precipitate was collected by suction filtration and dissolved in chloroform. Anhydrous sodium sulfate was dried in the black mouth form solution, and the anhydrous sodium sulfate was removed by natural filtration, followed by reprecipitation by mixing with an excess amount of ethanol. By decantation, a colorless and transparent purified product of PIC (molecular weight: 10,000 or more) was obtained.

(iv) Mixed xylene: A mixed solution having ethylbenzene (15 wt%), orthoxylene (22 wt%), metaxylene (44 wt%), and paraxylene (19 wt%) was used.

[0050] [Examples 1 to 3]

In Examples 1 to 3, toluene (dielectric constant: 2.38), mixed xylene (dielectric constant: 2.40), and black mouth form (dielectric constant: 4.81) were used as hydrophobic organic solvents, respectively. Then, the following hydrophobic organic solvent solution was prepared, and the change with time of the average pore size of the reverse micelles present in the solution was measured.

In Example 1, polystyrene 1.OOg as an organic polymer and amphiphile AOT 1.OOg were mixed, this mixture was dissolved in 20.00 ml of 卜 Noren, and 0.50 ml of water was further added. Hydrophobic organic solvent in which reverse micelles were formed after ultrasonic dispersion for 1 minute (ultrasonic disperser used: Sharp Corporation, model: UT-204, the same ultrasonic disperser was used in the following examples) A solution was prepared. Weight ratio of organic polymer to amphiphile in this solution Rp ([Organic polymer] / ([Organic polymer] + [Amphiphile])) is 0.50, weight blend of water and amphiphile. The ratio Rw (water Z amphiphile) is 0.50. While stirring the resulting solution with a stir bar, the micelle size distribution was measured with a laser diffractometer every 5 minutes. Figure 1 shows the changes over time. The average micelle diameter in Figure 1 is 1.51 μm after 0 minutes, 1.50 μm after 5 minutes, 1.48 μm after 10 minutes, and 1.42 μm after 15 minutes. It was.

[0051] Similarly, in Examples 2 and 3, Example 1 except that mixed xylene was used in Example 2 and black mouth form was used in Example 3 instead of toluene in Example 1 as the hydrophobic organic solvent. A hydrophobic organic solvent solution was prepared in the same manner as described. The change over time of the average pore size of the reverse micelle was measured in the same manner as in Example 1 for the resulting solution. Figures 2 and 3 show the measurement results of the changes over time.

The average micelle diameter in FIG. 2 was 14.69 / ζ πι after 0 minutes, 8.38 / ζ πι after 5 minutes, and 3.19 / z m after 10 minutes. The average micelle diameter in FIG. 3 was 159.10 m after 0 minutes, 174.49 μm after 5 minutes, and 151.86 / z m after 10 minutes and 129.46 after 15 minutes.

From the measurement results, it was confirmed that the hydrophobic organic solvent had a lower dielectric constant, that is, the nonpolar solvent had a smaller average micelle diameter and a tendency to change with time with a smaller reverse micelle.

By measuring the change in the average pore diameter over time, it is possible to obtain a guide for the operation time of the process of evaporating the hydrophobic organic solvent and the hydrophilic liquid after forming the hydrophobic organic solvent solution containing reverse micelles.

[0052] [Examples 4 and 5]

In Example 4, the hydrophobic organic solvent solution formed with reverse micelles obtained in Example 1 was applied onto a polyethylene terephthalate (PET) substrate (10 cm × 10 cm) at a thickness of 300 / z m using a blade coater. After forming a hydrophobic organic solvent solution containing reverse micelles by stirring, a PET substrate coated with this solution after about 30 seconds passed was blown in dry air at a position 3 cm above the substrate in the evaporation container. Using a pipe (with four lmm φ holes inclined at an equal interval of 3cm and provided in the downward direction), the substrate is directed diagonally upward from one end of the substrate to a temperature of 26 ° The solvent is allowed to spontaneously evaporate in about 3 minutes while flowing dry air (relative humidity 17%) at C at a flow rate of KL / min (in the following example! The same evaporation method was adopted except changing the time.) A thin film with a thickness of 3.12 m was obtained on the PET substrate.

From observation with an optical microscope, micropores were distributed almost uniformly in the obtained thin film, the average pore diameter was 1.66 m, and the cross-sectional porosity was 22.2%. In Example 5, a hydrophobic organic solvent solution containing reverse micelles was formed in the same manner as in Example 4 except that the amount of water used was 0.25 ml, Rw was 0.25, and Rs was 0.11. After casting, the solvent was naturally evaporated to obtain a thin film having a thickness of 1.41 μm on the glass substrate. From observation with an optical microscope, the micropore distribution in the obtained thin film was almost the same as in Example 4, the average pore diameter was 1.15 m, and the cross-sectional porosity was 24.3%. These experimental conditions and results are summarized in Table 3.

In addition, cross-sectional views of the porous structures produced in Examples 4 and 5 when 1 ^ 0.25 and Rw are 0.50 are shown in FIGS. 4 (A) and 4 (B), respectively.

[0053] [Examples 6 and 7]

In Example 6, the hydrophobic organic solvent solution in which the reverse micelles obtained in Example 2 were formed was made into a polyethylene terephthalate (PET) substrate (10 cm × 10 cm) to a thickness of 300 m using a blade coater. ). After forming a hydrophobic organic solvent solution containing reverse micelles by agitation, a flow rate of L / min at a temperature of 26 ° C (dry air vs. humidity 17%) was applied to the PET substrate on which this solution was applied approximately 30 seconds later. ) Was allowed to evaporate naturally in about 7 minutes, and a thin film with a thickness of 2.90 m was obtained on the PET substrate.

From observation with an optical microscope, micropores were almost uniformly distributed in the obtained thin film, the average pore diameter was 1.63 m, and the cross-sectional porosity was 27.3%.

In Example 7, a hydrophobic organic solvent solution containing reverse micelles was formed in the same manner as in Example 6 except that the amount of water used was 0.25 ml, Rw was 0.25, and Rs was 0.11. After casting, the solvent was naturally evaporated to obtain a thin film having a thickness of 1.10 m on the glass substrate. From observation with an optical microscope, the micropore distribution of the obtained thin film was almost the same as in Example 6, the average pore diameter was 1.07 m, and the cross-sectional porosity was 24.2%. These experimental conditions and results are summarized in Table 3.

In addition, cross-sectional views of the porous structures produced in Examples 6 and 7 when 1 ^ 0.25 and Rw are 0.50 are shown in FIGS. 5 (A) and 5 (B), respectively.

[0054] [Table 3] Example No. Example 4 Example 5 Example 6 Example 7

Organic polymer (g) 1.00 1.00 1.00 1.00

Real Amphiphile ― A0T A0T A0T Α0Τ

(g) 1.00 1.00 1.00 1.00

Experimental Hydrophobic Organic Solvents 1 Tonorene Tonoylene Xylene Xylene

(ml) 20.00 20.00 20.00 20.00

Article Water (ml) 0.50 0.25 0.50 0.25

Rw ― 0.50 0.25 0.50 0.25

Rp 1 0.50 0.50 0.50 0.50

R s ― 0.20 0.11 0.20 0.11

Hole distribution-Uniform distribution Uniform distribution Uniform distribution Uniform distribution

Average pore size 1.66 1.15 1.63 1.07

Fruit cross section porosity (%) 22.2 24.3 27.3 24.2

Film thickness (μηι) 3.12 1.41 2.90 1.10

Rw: [Water] / [Amphiphile] (weight ratio)

R p: [Organic polymer] / ([Organic polymer] + [Amphiphile]) (weight ratio)

R s: [Water] / ([Organic polymer] + [Amphiphile] + [Water]) (weight ratio) [Examples 8 and 9]

In Example 8, the hydrophobic organic solvent solution in which the reverse micelles obtained in Example 3 were formed was made into a polyethylene terephthalate (PET) substrate (10 cm X) using a blade coater to a thickness of 300 μm. 10 cm). After forming a hydrophobic organic solvent solution containing reverse micelles by agitation, a flow rate of l (L) was applied to a PET substrate coated with this solution after 30 seconds at a temperature of 26 ° C and a humidity of 17%. / min), the solvent was naturally evaporated in about 1 minute, and a thin film with a thickness of 3.41 μm was obtained on the PET substrate.

From observation with an optical microscope, micropores were almost uniformly distributed in the obtained thin film, the average pore diameter was 1.41 / m, and the cross-sectional porosity was 19.6%.

In Example 9, a hydrophobic organic solvent solution containing reverse micelles was formed in the same manner as in Example 8 except that the amount of water used was 0.25 ml, Rw was 0.25, and Rs was 0.11. After casting, the solvent was naturally evaporated to obtain a thin film with a thickness of 4.88 m on the PET substrate. From observation with an optical microscope, the micropore distribution of the obtained thin film was almost the same as in Example 6, the average pore diameter was 1.00 m, and the cross-sectional porosity was 22.4%. These experimental conditions and results are summarized in Table 4.

Further, the porous structures produced in Examples 8 and 9 when Rw is 0.25 and Rw is 0.50 Sectional views are shown in Fig. 6 (A) and Fig. 6 (B), respectively.

[Examples 10, 11, 12]

An experiment was conducted to confirm that the cross-sectional porosity of the porous structure obtained from the hydrophobic organic solvent solution using toluene as the hydrophobic organic solvent can be controlled.

In Example 10, 0.54 g of polystyrene as an organic polymer and 0.06 g of the amphiphilic substance ATO are dissolved in 6.00 ml of toluene, and 0.03 ml of water is further added and ultrasonically dispersed for 3 minutes to form reverse micelles. A hydrophobic organic solvent solution was prepared. Weight ratio of organic polymer and amphiphile in this solution Rp ([Organic polymer] / ([Organic polymer] + [Amphiphile])) is 0.90, and weight ratio of water and amphiphile Rw (Water Z amphiphile) is 0.50.

The hydrophobic organic solvent solution containing reverse micelles obtained above was applied onto a polyethylene terephthalate (PET) substrate (10 cm × 10 cm) with a thickness of 300 μm using a blade coater. After forming a hydrophobic organic solvent solution containing reverse micelles by agitation, a flow rate of 1 (L / L) was applied to a PET substrate coated with this solution after 30 seconds at a temperature of 26 ° C and a humidity of 17%. The solvent was allowed to evaporate naturally in about 3 minutes, and a thin film with a thickness of 7.80 μm was obtained on the PET substrate. From observation with an optical microscope, micropores were almost uniformly distributed in the obtained thin film, the average pore diameter was 1.22 m, and the porosity was 4.32%.

In Examples 11 and 12, a thin film on the PET substrate was obtained in the same manner as described in Example 10 except that organic polymer, amphiphile AOT, toluene, and water were used in the amounts shown in Table 4. .

Regardless of the specific gravity of the organic solvent, when the evaporation time is relatively short, the solvent evaporates while the micelles are uniformly present in the entire solution. It is estimated that a porous film having a small aperture ratio and a large number of pores inside the film was obtained.

Table 4 summarizes the experimental conditions and results. From these experiments, it was confirmed that the cross-sectional porosity of the porous structure can be controlled by setting conditions.

[0057] [Table 4] Example No. Example 8 Example 9 Example 10 Example 11 Example 12 Organic polymer (g) 1.00 1.00 0.54 0.42 0.30 Actual amphiphile ― A0T A0T A0T Α0Τ A0T

(g) 1.00 1.00 0.06 0.18 0.30 Test Hydrophobic Organic Solvent-Chlomouth Form Chlorophore Tem Ton Teng

(ml) 20.00 20.00 6.00 6.00 6.00 Article Water (ml) 0.50 0.25 0.03 0.09 0.15

Rw 1 0.50 0.25 0.50 0.50 0.50 Case Rp ― 0.50 0.50 0.90 0.70 0.50

R s 1 0.20 0.11 0.05 0.13 0.20 Hole distribution-Uniform distribution Uniform distribution Uniform distribution Uniform distribution Uniform distribution Concentration average pore diameter (μπι) 1.41 1.00 1.22 2.44 1.32

Fruit cross section porosity (%) 19.6 22.4 4.3 20.2 27.8

Film thickness 3.41 4.88 7.80 5.85 1.58

Rw: [Water] [Amphiphile] (weight ratio)

Rp: [Organic Hom! / Mer] / ([Organic Homomer] + [Amphiphile]) (weight ratio)

R s: [Water] / ([Organic organic solvent Η + [Amphiphile] + [Water]) (Weight ratio) [Example 13]

Polystyrene (Idemitsu Petrochemical Co., Ltd., trade name: HH30) O.03g, dihexadecyldimethylammonium and 0.23g of polyion complex of polystyrene sulfonate (pic) were mixed, and this mixture was dissolved in 3ml of Kuroguchi Form. Then, 0.1 g of plain water was added and ultrasonically dispersed for about 5 minutes to prepare a hydrophobic organic solvent solution in which reverse micelles were formed. The weight ratio (Rw) of water and amphiphile was 0.43, and the weight ratio (Rp) of organic polymer and amphiphile was 0.1.

This solution was applied onto a glass substrate to a thickness of 100 m using a blade coater. Approximately 30 seconds after the preparation of the hydrophobic organic solvent solution, dry air (17% relative humidity) is allowed to flow at a flow rate of 3 (L / min) at a temperature of 26 ° C on the glass substrate coated with this solution. The solvent and water were naturally evaporated in about 1 minute, and a thin film with a thickness of 4 // m having an opening on the glass substrate was obtained.

From the results of film cross-sectional observation using a scanning electron microscope, the area ratio of the surface open holes in the cross section perpendicular to the structure surface was 60% or more.

The average opening diameter of the obtained film was 0.75 μm, and the surface opening ratio obtained using optical microscope observation was 6.7%. Figure 7 shows the microscopic view of the resulting porous membrane (the hole is black). Show). In addition, the analysis using an energy dispersive X-ray fluorescence analyzer confirmed that the concentration distribution of the s component derived from the polyion complex of dihexadecyldimethylammonium and polystyrenesulfonic acid was particularly high at the pore edge. These experimental conditions and results are summarized in Table 5.

[0059] [Example 14]

Polystyrene (made by Idemitsu Petrochemical Co., Ltd., trade name: HH30) O. 67g and bis (sodium 2-ethylhexylsulfosuccinate) 5. OOg are mixed, and this mixture is dissolved in 20 ml of black mouth form. Water 5. Og was added and ultrasonically dispersed for about 5 minutes to prepare a hydrophobic organic solvent solution in which reverse micelles were formed. Weight ratio of organic polymer and amphiphile in this solution Rp ([Organic polymer] / ([Organic polymer] + [Amphiphile])) is 0.12. Rw ([water Z amphiphile]) is 1.0.

This solution was applied onto a glass substrate with a thickness of 100 m using a blade coater. After preparing a hydrophobic organic solvent solution and applying a force of about 30 seconds, the solvent was flowed on a glass substrate coated with this solution at a temperature of 26 ° C (dry air vs. humidity 17%) at a flow rate of 3 (L / min). Was spontaneously evaporated in about 1 minute to obtain a thin film having a thickness of 1. having a through-hole on the glass substrate. From the observation with an optical microscope, the area ratio of the through-holes is 60% or more of the total area of the holes in the cross section perpendicular to the structure surface, and the obtained thin film has micropores with an average opening diameter of 10.89 m. The surface opening ratio was confirmed to be 36.6%. Table 5 summarizes the experimental conditions and results.

Figure 8 shows a perspective image of the obtained porous film observed with an optical microscope viewed at an oblique upward force of 45 degrees.

[0060] [Examples 15 to 18]

A thin film having many through-holes was formed by using black mouth form as an organic solvent and selecting conditions such that the mixing ratio Rw of water and amphiphile was 0.50, 1.0, 3.0, 5.0.

In Example 15, polystyrene (produced by Idemitsu Petrochemical Co., Ltd., trade name: HH30) O. 67 g and bis (2-ethylhexylsulfosuccinate sodium) lg were mixed, and this mixture was dissolved in 20 ml of chloroform. Further, 0.5 g of water was added and ultrasonically dispersed for about 5 minutes to prepare a hydrophobic organic solvent solution in which reverse micelles were formed. Organic polymer and amphiphile in this solution Weight ratio Rp ([Organic polymer] / ([Organic polymer] + [Amphiphile])) is 0.4, Mixing ratio of water and amphiphile Rw ([Water Z amphiphile ] Is 0.5).

This solution was applied onto a glass substrate with a thickness of 100 m using a blade coater. After preparing a hydrophobic organic solvent solution for about 30 seconds, dry air at a temperature of 26 ° C and a humidity of 17% at a flow rate of 3 (L / min) on a glass substrate coated with this solution. While the solvent was naturally evaporated for about 1 minute, a thin film with a film thickness of 9.1 μm was obtained on the glass substrate.

From the cross-sectional observation with an optical microscope, the area ratio of the through-holes in the cross-section perpendicular to the surface of the structure is 60% or more. It was confirmed that it had micropores with a pore size of 10.9 m and an average aperture size of 8.2 m, and a surface aperture ratio of 8.9%. In addition, analysis with an energy dispersive X-ray fluorescence spectrometer confirmed that the concentration distribution of S component derived from bis (2-ethylhexylsulfosulphate sodium) was particularly high at the edge of the hole.

[0061] In Examples 16 to 18, the amount of water added to the amphiphile is constant, and the amount of water added is l.OOg (Example 16), 3.00 g (Example 17), 5.00 g (Example) 18). The other conditions were the same as in Example 15 to produce a film. From the cross-sectional observation with the optical microscope, the area ratio of the through-holes is 60% or more of the total area of the holes in the cross-section perpendicular to the surface of the obtained structure. Asked.

Table 5 summarizes the reverse micelle solution preparation conditions (each component, Rw and Rp), and the average aperture diameter, surface aperture ratio, and film thickness measurement results.

[0062] [Table 5]

Example, Comparative Example No. Example 13 Example 14 Example 15 Example 16 Example 17 Example 18

Organic polymer (ε) 0.03 0.67 0.67 0.67 0.67 0.67 Real amphiphile PIC A0T A0T A0T A0T A0T

(g) 0.23 5, 00 1 1 1 1 Experimental hydrophobic organic solvent. Holm Kuro Holm Kuro Holm Kuroguchi Holm Kuro Holm

(ml) 3 20.00 20 20 20 20 Water (g) 0.1 5.00 0.50 1.00 3.00 5.00

R 1 0.43 1.00 0.50 1.00 3.00 5.00 cases p ― 0.12 0.12 0, 40 0.40 0.40 0.40

R s 1 0.28 0.47 0.23 0.37 0.64 0.75 Hole type-Opening Through-hole Through-hole Through-hole Through-hole Through-hole Average opening diameter m) 0, 75 10.89 8.2 22 43 50 Fruit surface opening ratio (%) 6.7 36.6 8.9 15.1 20.2 22.2

Film thickness (nm) m) 4.0 1.18 9.1 9.5 8.1 8.3

Rw: [Water] Z [| *) Amphiphile] (weight ratio)

R p ： [Organic organic '-] / ([Organic organic Ί?-] + [Amphiphile]) (weight ratio)

R s: [Water] / ([Organic polymer] + [Amphiphile «] + [Water]) (weight ratio)

[0063] [Comparative Example 1]

In Comparative Example 1, using the same components as used in Example 15, the mixing ratio of amphiphile 1.0 g, organic polymer 0.67 g, water 0.25 g, black mouth form 20 ml, magnetic 'stirrer was used. A membrane was prepared in the same manner as in Example 15 except that stirring was performed for about 30 seconds.

Rwi was 0.25 and Rpi was 0.4.

The obtained film was observed with an optical microscope. As a result, fine pores were not confirmed. Relatively large pore size ヽ Many reverse micelles exist, and Kuroguchi Form, which has a relatively large specific gravity, was used as the organic solvent. Unformed power.

[0064] [Examples 19 to 21]

In Examples 19 to 21, the blending ratio Rp ((organic polymer) / ((organic polymer) + [amphiphile])) of the organic polymer and the amphiphilic substance is constant with the blending amount other than the organic polymer being constant. A porous structure was produced under the condition of 0.1 to 0.6.

In Examples 19 to 21, the amount of water and amphiphile added is constant (Rw: 0.5), and the organic polymer has Rp of 0.1 (Example 19), 0.2 (Example 20), and 0.6 (Example 21). ) Was added. Other conditions were the same as in Example 15 to produce a porous membrane.

Holes in the cross section perpendicular to the surface of the structure obtained from cross-sectional observation with an optical microscope Of these total areas, the ratio of the area of the penetrating holes was 60% or more, and the average aperture diameter and the surface aperture ratio were obtained from observation with an optical microscope. From the surface observation, in Example 19, the average pore diameter in the direction parallel to the membrane surface of the through-hole was 13.6 m. Table 6 summarizes the conditions for preparing the reverse micelle solution (each component, Rw and Rp), and the average aperture diameter, surface aperture ratio, and film thickness measurement results.

[0065] [Table 6]

R w: [water] / [two amphiphiles] (weight ratio)

R p: [Organic Lima-] / ([Organic Lima] + [Amphiphile]) (Weight ratio)

R s: [Water] Z ([Organic polymer] + [Amphiphile] + [Water]) (weight ratio)

[0066] [Comparative Example 2]

In Comparative Example 2, the same components as those used in Example 19 were used, and the mixing ratio was 1.0 g of amphiphile, 9.0 g of organic polymer, 0.5 g of water, and 20 ml of black mouth form. A membrane was prepared in the same manner as in Example 19 except that stirring was performed for about 30 seconds.

Rw was 0.50 and Rp was 0.90.

In Comparative Example 2, no fine pores were observed. The agitation during the formation of reverse micelles is insufficient, and the ratio of reverse micelles in the entire membrane is reduced due to the relatively small amount of amphiphiles with a relatively large amount of organic polymer. It seems that it was confirmed power.

[0067] [Example 22]

An experiment was conducted in which copper fine particles were introduced into the porous structure as a functional material in the porous membrane. In Example 15, 0.5 mg of copper fine particles (average particle size 50 nm) was added to 0.5 g of water to be added. The resultant mixture was stirred and dispersed with a stirrer for about 5 minutes to prepare a hydrophobic organic solvent solution in which reverse micelles were formed. After applying this solution to a glass substrate with a thickness of 0.5 mm using a blade coater, the organic solvent and water were naturally evaporated in the same manner as in Example 15 to form a 6 μm-thick thin film with many through holes. Obtained. From observation with an optical microscope, it was confirmed that fine pores having an average opening diameter of 5 μm were present, and copper fine particles were selectively present in the pores.

[0068] [Examples 23 to 25]

Weight ratio of organic polymer and amphiphile Rp ((Organic polymer) / ((Organic polymer) + (Amphiphile))) is 0.12 ~ 0.6 An experiment was conducted to control the average aperture diameter under the range condition.

In the same manner as described in Example 13, in Examples 23 to 25, the amounts of polystyrene shown in Table 7 were mixed with dihexadecyldimethylammonium and polystyrene sulfonate polyion complex (PIC). Dissolved in 3 ml of mouth form, further added 0.1 lg of water and ultrasonically dispersed for 5 minutes to prepare a hydrophobic organic solvent solution in which reverse micelles were formed. Table 7 shows the composition ratio of each component. This solution was applied onto a glass substrate with a thickness of 100 m using a blade coater. About 30 seconds after the preparation of the hydrophobic organic solvent solution, dry air (relative humidity 17%) flows at a flow rate of 3 (L / min) at a temperature of 26 ° C on the glass substrate coated with this solution. The organic solvent and water were naturally evaporated to obtain a 4 m thin film on the glass substrate.

From the cross-sectional observation with the optical microscope, the area ratio of the through-holes is 60% or more of the total area of the holes in the cross section perpendicular to the surface of the obtained structure, and the optical microscope observation power average aperture diameter and surface aperture ratio are Asked.

Table 7 shows the conditions for preparing the reverse micelle solution (each component, Rw and Rp), and the average aperture diameter, surface aperture ratio, and film thickness.

[0069] [Table 7] Example No.Example 13 Example 23 Example 24 Example 25

Organic polymer (g) 0.03 0.08 0. 13 0. 15

Real Amphiphile I PIC PIC PIC PIC

(g) 0.23 0. 18 0.13 0. 10

Hydrophobic organic solvent

(ml) 3 3 3 3

Water (g) 0. 1 0. 1 0. 1 0.1

Rw 1 0.43 0.56 0.77 1.00

R p 1 0.12 0.31 0.50 0.60

R s 0.28 0.28 0.28 0.29

Form of hole 1 Through hole Through hole Through hole Through hole

(Average diameter m) 0.75 15 30 35

Fruit surface opening ratio (%) 6.7 14.9 12.4 8.4

Film thickness m) 4.0 5.0 4.4 4. 1

Rw: [Water] [Amphiphile] (weight ratio)

R p: [Organic web] [(Organic polymer] + [Amphiphile]) (weight ratio)

R s: [Water] / "([Organic polymer] + [Amphiphile] + [Water]) (weight ratio)

[0070] [Comparative Example 3]

In Example 15, a film was formed in exactly the same manner as Example 15 except that only water was not added to the hydrophobic organic solvent solution. Observation with an optical microscope revealed that the film surface was smooth and no pores were observed.

Industrial applicability

[0071] The multilayer structure obtained by the method of the present invention can be used as an optical filter, a diffractive element, or the like, and also includes a semiconductor, a capacitor, a magnetic memory, a memory, a DVD, a light emitting device, or a biochip. Can be widely used in the field of application.

Application No. 2005-205961 (Application date: July 14, 2005) and Application No. 2006-191742 (Application date: July 12, 2006) of the Japanese application that is the basic application of this application The contents of the specification, drawings, and claims disclosed are incorporated into the present invention.

Claims

The scope of the claims

[1] A method for producing a porous structure using the reverse micelle cage shape formed in a hydrophobic organic solvent solution for forming pores, comprising the following steps (i) and (iii):

[2] The method for producing a porous structure according to claim 1, wherein the weight mixing ratio Rw (hydrophilic liquid, amphiphile) of the hydrophilic liquid and the amphiphile in step 1 is 0.1 to 15. .

[3] The porous composition according to claim 1, wherein the weight mixing ratio Rp (organic polymer / [organic polymer + amphiphile]) of the organic polymer and the amphiphile in step 1 is 0.1 to 0.9. Manufacturing method of structure.

[4] The hydrophobic organic solvent is a normal pentane, normal hexane, cyclohexane, isooctane, normal heptane, normal decane, benzene, toluene, ethylbenzene, orthoxylene, having a dielectric constant at 20 ° C. of 5 or less. Meta-xylene, para-xylene, mixed xylene, carbon tetrachloride, chlorophenol, and trans 1,2, -dichloroethylene, and butyl acetate, dichloromethane, 1,1,2,2- Tetrachloroluethane, cis 1,2-dichloroethane, and isobutyl methyl ketone

2. The method for producing a porous structure according to claim 1, wherein at least one selected from force is used.

[5] The amphiphile is bis (2-ethylhexylsulfosuccinate sodium), dioctylsulfosuccinate sodium, diisoptylsulfosuccinate sodium, dicyclohexylsulfosuccinate sodium, dihexylsulfosuccinate sodium, dihexene A polyion complex of xadecyldimethylammonium and polystyrene sulfonic acid, a block copolymer obtained from ethylene glycol and propylene glycol, an ethylene oxide and propylene oxide force, a block copolymer force obtained, and one or more selected. The manufacturing method of the porous structure of description.

[6] The organic polymer is polyethylene, polypropylene, poly-4-methylpentene-1, cyclopolyolefin, polyvinyl chloride, polyvinyl chloride, polyvinylidene, polystyrene, acrylonitrile-styrene resin (AS resin), acrylonitrile— Butadiene-styrene resin (ABS resin), methacrylate ester resin, acrylate ester resin, ethylene butyl alcohol copolymer resin, polyalkylene oxide, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, thermoplastic polyester 2. The porous structure according to claim 1, wherein the porous structure is at least one selected from the group consisting of polyphenylene sulfide, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, and polyamideimide. Production method.

[7] The substrate is any one selected from glass, metal, ceramics, polypropylene, polyethylene, polyethylene terephthalate, polyether ketone, and polyfluorinated styrene power, or a composite of one or more of these displacement forces. The method for producing a porous structure according to claim 1.

[8] The method according to claim 1, wherein after forming the hydrophobic organic solvent solution containing reverse micelles in step 1, casting is performed on the substrate in step 2 so that the thickness of the hydrophobic organic solvent solution is 0.01 to 5 mm. The manufacturing method of the porous structure as described in above.

[9] The method for producing a porous structure according to [1], wherein the hydrophobic organic solvent and the hydrophilic liquid in step 3 are evaporated under a circulation of a dry gas.

[10] The hydrophobic organic solvent having a dielectric constant of 20 or less at 20 ° C. in step 1 and a specific gravity of 0.65 to 0.90 at the same temperature is used, and the hydrophobic organic solvent in step 3 is used. By evaporating the solvent, the holes in which reverse micelle cages are also formed are distributed almost uniformly in the structure, and the structure has holes (opening and penetrating! /, 2. The method for producing a porous structure according to claim 1, wherein a structure having an average diameter of 0.1 to L0 m is formed.

[11] The specific gravity in step 1 is larger than the specific gravity of the hydrophilic liquid, the organic polymer and Z or the hydrophobic organic solvent are used, and the hydrophobic organic solvent is evaporated in step 3 to the surface of the structure. Of the total area of holes in a vertical cross section, the area ratio of holes (open holes) that are open (excluding through holes) on the surface is 60% or more, or the surface opening ratio is 5% or more. 2. The method for producing a porous structure according to claim 1, wherein the structure is formed and a structure having an average opening diameter of 0.1 to 100 μm is formed.

[12] The Rw (hydrophilic liquid Z amphiphile) in step 1 is 3 to 15, and the thickness of the multilayer structure after evaporation of the hydrophobic organic solvent in step 3 is 1 to 50 m in step 2 The hydrophobic organic solvent solution is cast on a substrate so as to be, and by the evaporation of the hydrophobic organic solvent in step 3, a hole penetrating through the entire area of the hole in the cross section perpendicular to the structure surface ( The through hole has an area ratio of 60% or more, or a surface opening ratio force based on the through hole of 7% or more, and the average hole diameter force in the direction parallel to the structure surface of the through hole is ~ 50 m or the through The method for producing a porous structure according to claim 1, wherein a structure having an average opening diameter of pores of 1 to 50 m is formed.

13. The method for producing a porous structure according to claim 1, wherein the porous structure obtained by removing the substrate from the porous structure on the substrate formed in the step 3 has a self-supporting property. .

[14] The hydrophobic organic solvent solution in Step 1 is an amphiphilic substance, a hydrophobic organic polymer, a hydrophobic organic solvent, a hydrophilic liquid, and a metal, alloy, or metal compound dispersed in the hydrophilic liquid phase. The metal, alloy or metal compound fine particles are contained in the pores of the porous structure made of fine particles and obtained in step 3! The method for producing a porous structure according to claim 1.

[15] The hydrophobic organic solvent solution in Step 1 is an amphiphilic substance, a hydrophobic organic polymer, a hydrophobic organic solvent, a hydrophilic liquid, and a functional material dispersed or dissolved in the hydrophilic liquid phase. The functional material is contained in the pores of the porous structure obtained in step 3, and the functional material is Au, Ag, Cu, Pt, Fe, Ni, Co, Mn, Selected from metals consisting of Cr and Ti, semiconductor materials, oxides, ceramic materials, metal complexes, ferroelectric materials, ferromagnetic materials, resistance change materials, phase change materials, optical functional materials, and fluorescent functional materials The method for producing a porous structure according to claim 1, wherein the method is one or more functional materials.

[16] A porous structure composed of an organic polymer having hydrophobicity and an amphiphilic substance having an anionic group in a hydrophilic group having a molecular weight of 10,000 or less, wherein the amphiphile is a side of the pore. A porous structure comprising an edge and each hole being partitioned by a partition wall made of the organic polymer cover and communicating in a direction parallel to the surface of the structure.

[17] The amphiphile is selected from bis (sodium 2-ethylhexylsulfosuccinate), sodium dioctylsulfosuccinate, sodium diisoptylsulfosuccinate, sodium dicyclohexylsulfosuccinate, and sodium dihexylsulfosuccinate. The porous structure according to claim 16, which is at least one kind.

[18] The organic polymer is polyethylene, polypropylene, poly-4-methylpentene 1, cyclopolyolefin, polyvinyl chloride, polyvinyl chloride, vinylidene, polystyrene, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin. Fat (ABS resin), Methacrylate ester resin, Acrylate ester resin, Ethylene butyl alcohol copolymer resin, Polyalkylene oxide, Polyamide, Polyacetal, Polycarbonate, Modified polyphenylene ether, Thermoplastic polyester, Polyphenylene sulfide The porous structure according to claim 16, wherein the porous structure is at least one selected from the group consisting of polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, and polyamideimide. .

19. The weight blending ratio of organic polymer and amphiphile (organic polymer Z [organic polymer + amphiphile]) in the porous structure is 0.1 to 0.9. A porous structure according to 1.

20. The porous structure according to claim 16, wherein the porous structure is a porous film having self-supporting properties.

[21] The structure according to claim 16, wherein the pores in the structure are distributed substantially uniformly in the structure, and the average pore diameter (excluding openings and through-holes) is 0.1 to L0 m. The porous structure described.

[22] Of the total area of the holes in the cross section perpendicular to the structure surface of the structure, the area ratio of holes (open holes) opened on the surface is 60% or more, or the surface opening ratio is 5% or more. The porous structure according to claim 16, wherein the average opening diameter of the opening holes is 0.1 to L00 m.

[23] The hole penetrating out of the total area of the hole in a cross section perpendicular to the structure surface of the structure

The area ratio of (through hole) is 60% or more, or the surface opening ratio based on the through hole is 7% or more, and the average hole diameter in the direction parallel to the structure surface of the through hole is 1 to 50 m, or 17. The porous structure according to claim 16, wherein the average opening diameter of the through holes is 1 to 50 μm.

24. The porous structure according to claim 16, wherein the porous structure is a film and has a thickness of 0.001 to 1 mm.

25. The porous structure according to claim 16, wherein metal, alloy or metal compound fine particles are present in the pores of the porous structure.

[26] In the pores of the porous structure, at least one metal selected from Au, Ag, Cu, Pt, Fe, Ni, Co, Mn, Cr and Ti, a semiconductor material, an oxide, a ceramic material, 17. The functional material according to claim 16, wherein there is one functional material selected from a metal complex, a strong dielectric material, a ferromagnetic material, a resistance change material, a phase change material, an optical functional material, and a fluorescent functional material. Porous structure.

27. The porous structure according to claim 16, wherein the porous structure is formed on a substrate.

[28] The substrate is any one selected from glass, metal, ceramic substrate, polypropylene, polyethylene, polyethylene terephthalate, polyether ketone, and polyfluorinated styrene, or a composite of any one or more of these. 28. The porous structure according to claim 27.