WO2007007877A1 - Processus de fabrication de structure poreuse et structure poreuse obtenue grâce au processus - Google Patents

Processus de fabrication de structure poreuse et structure poreuse obtenue grâce au processus Download PDF

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Publication number
WO2007007877A1
WO2007007877A1 PCT/JP2006/314067 JP2006314067W WO2007007877A1 WO 2007007877 A1 WO2007007877 A1 WO 2007007877A1 JP 2006314067 W JP2006314067 W JP 2006314067W WO 2007007877 A1 WO2007007877 A1 WO 2007007877A1
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Prior art keywords
porous structure
organic solvent
hydrophobic organic
organic polymer
amphiphile
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PCT/JP2006/314067
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English (en)
Japanese (ja)
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Yusuke Yamada
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The Furukawa Electric Co., Ltd.
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Publication of WO2007007877A1 publication Critical patent/WO2007007877A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Definitions

  • 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.
  • a method for forming a polymer porous membrane having fine pores having a diameter of 1 to 100 ⁇ m 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.
  • 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.
  • Patent Document 1 or Patent Document 2 There is known a method for producing a film having a Hercam structure by evaporating fine water droplets generated by condensation.
  • 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).
  • a block copolymer examples 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
  • the formed film has self-supporting properties.
  • 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.
  • 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.
  • the hole diameter is small, it becomes difficult to selectively introduce the functional material into the hole.
  • 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.
  • 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.
  • 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”).
  • Step 1 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)
  • step 3 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)
  • Weight mixing ratio Rw (hydrophilic liquid Z both amphiphile) of hydrophilic liquid and amphiphile in step 1 is 0.1 to 15.
  • 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.
  • Power must be at least one selected
  • 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.
  • 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
  • step 2 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;
  • 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,
  • 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)
  • 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;
  • 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
  • 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.
  • 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, 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
  • 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).
  • the following aspects (17) to (28) can be further adopted.
  • the amphiphile is composed of bis (sodium 2-ethylhexylsulfosuccinate), sodium dioctylsulfosuccinate, sodium diisoptylsulfosuccinate, sodium dicyclohexylsulfosuccinate, and sodium dihexylsulfosuccinate. Be at least one selected,
  • 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,
  • 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 average aperture diameter of the apertures is 0.1-100 ⁇ m
  • 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.
  • 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 ⁇ m,
  • the porous structure is a film and has a thickness of 0.001 to lmm.
  • 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,
  • one functional material selected from metal complexes, ferroelectric materials, ferromagnetic materials, resistance change materials, phase change materials, optical functional materials, and fluorescent functional materials;
  • the porous structure is formed on a substrate
  • 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,
  • 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.
  • 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.
  • 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.
  • Embodiments 1 and 2 of the present invention will be described.
  • 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.
  • the ratio of the pore area to the entire cross-sectional area is calculated and taken as the cross-sectional porosity.
  • 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.
  • the area ratio of through-holes is determined from the total area of holes in an arbitrary cross section of the porous structure.
  • 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.
  • the average value is the average pore diameter.
  • 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.
  • step 3 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)
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • organic solvent hydrophobic organic solvent
  • 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.
  • 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.
  • Step 1 reverse micelles are formed in a hydrophobic organic solvent solution.
  • 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.
  • 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.
  • the porous film formed on the substrate has rigidity enough to have self-supporting properties.
  • organic polymer examples 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
  • 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.
  • polystyrene and acrylic resin are preferable in terms of cost
  • polycarbonate, cyclopolyolefin, fluorine resin are also preferable in terms of transparency
  • 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.
  • 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.
  • anions constituting hydrophilic groups in ionic amphiphiles include —Coo_, —so—, etc., and cations such as dimethylammonium ion, trimethyl.
  • the hydrophilic group in the nonionic amphiphile includes a hydroxyl group and an ether bond.
  • 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.
  • 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.
  • the desired reverse micelle form uniform dispersion in the solution, micelle diameter, etc.
  • stability 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.
  • 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.
  • 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 ( ⁇ ) of 5 or less at 20 ° C
  • Table 2 shows relatively polar organic solvents having a dielectric constant of more than 5 at 20 ° C. It is.
  • toluene which has a low dielectric constant at 20 ° C
  • reverse micelles tend to exist relatively stably with small micelle diameters.
  • black mouth form 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.
  • 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.
  • 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.
  • the hydrophobic organic solvent appropriately dissolves the used hydrophobic organic polymer and amphiphile.
  • 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.
  • 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.
  • 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.
  • 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.
  • the vapor pressure of the organic solvent is determined at the evaporation temperature of the hydrophobic organic solvent in Step 3.
  • 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.
  • the specific gravity of the organic solvent can be used to control the vertical formation positions of the pores in the formed porous structure.
  • a nonpolar solvent when it is desired to uniformly distribute the pores in the porous structure.
  • water used as the hydrophilic liquid
  • a specific gravity such as chloroform is larger than that of water
  • reverse micelles can be distributed more upward, while aliphatic carbonization is performed.
  • a specific gravity such as hydrogen or an aromatic hydrocarbon
  • a large number of reverse micelles can be distributed downward.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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.
  • Water is most preferably used as the hydrophilic liquid for forming reverse micelles.
  • 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.
  • hydrophilic liquids other than water include ethylene glycol, propylene glycol, formic acid and the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • the density of the pores in the porous membrane 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).
  • Rs 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
  • the pore size can be controlled by Rw
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ be carried out under a dry inert gas flow while the hydrophobic organic solvent solution is allowed to stand.
  • 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.
  • the porous structure formed on the substrate after evaporating and removing the hydrophobic organic solvent and the hydrophilic liquid is usually a film.
  • 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.
  • 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.
  • the average hole diameter of the holes can be set to 0.1 to L0 m.
  • 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.
  • 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)
  • Rs the weight ratio of the hydrophilic liquid to the entire solute
  • hydrophilic liquid Z [hydrophilic liquid + organic polymer] + Amphiphile] (hereinafter sometimes referred to as Rs)
  • the hydrophilic liquid 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.
  • the average opening diameter of the opening holes may be 0.1 to: LOO / zm.
  • 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; ⁇ ⁇
  • 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”.
  • 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.
  • 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.
  • the hydrophobic organic solvent solution in Step 1 contains an amphiphilic substance and an organic polymer.
  • the metal, alloy or metal compound fine particles can be contained in the pores of the structure.
  • 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.
  • 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.
  • porous structure A 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.
  • 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.
  • 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.
  • the structure is such that each hole is partitioned by a partition wall that also has the organic polymer force.
  • 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.
  • 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 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.
  • 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.
  • 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
  • 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
  • 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 ⁇ m, and the porous structure is a film and has a thickness of 0.001-1 mm.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • Measurement was performed using a laser diffractometer (laser diffraction Z scattering type particle size distribution analyzer, model: LA-920, manufactured by Horiba, Ltd.).
  • SEM scanning electron microscope
  • 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.
  • 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.
  • PIC Dihexadecyl dimethyl ammonium polystyrene complex
  • 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.
  • 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 ⁇ 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
  • Rw water Z amphiphile
  • 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 / ⁇ ⁇ after 0 minutes, 8.38 / ⁇ ⁇ 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 ⁇ m after 5 minutes, and 151.86 / z m after 10 minutes and 129.46 after 15 minutes.
  • 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.
  • 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.
  • PET polyethylene terephthalate
  • 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.
  • 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 ⁇ m 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%.
  • 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.
  • PET polyethylene terephthalate
  • 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%.
  • 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 ⁇ m. 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 ⁇ m was obtained on the PET substrate.
  • PET polyethylene terephthalate
  • 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%.
  • 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 ⁇ m 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 ⁇ 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 1.22 m, and the porosity was 4.32%.
  • PET polyethylene terephthalate
  • Example 11 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. .
  • 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.
  • Example 12 Organic polymer (g) 1.00 1.00 0.54 0.42 0.30 Actual amphiphile ⁇ A0T A0T A0T ⁇ 0 ⁇ A0T
  • 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.
  • 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 ⁇ m, 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).
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m was obtained on the glass substrate.
  • 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%.
  • 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.
  • Example 16 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.
  • Example 18 Comparative Example No. Example 13 Example 14 Example 15 Example 16 Example 17 Example 18
  • 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 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.
  • Example 19 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.
  • 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.
  • 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.
  • Example 15 An experiment was conducted in which copper fine particles were introduced into the porous structure as a functional material in the porous membrane.
  • 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.
  • the organic solvent and water were naturally evaporated in the same manner as in Example 15 to form a 6 ⁇ m-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 ⁇ m were present, and copper fine particles were selectively present in the pores.
  • 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.
  • 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.
  • 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.

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Abstract

L’invention concerne un gabarit à micelles inversées servant à constituer une structure poreuse comprenant un polymère organique et une substance amphipathique. La production de la structure poreuse permet de réguler l’état de pores répartis de manière uniforme dans la structure, l’état de pores ouverts ou de pores traversant, le diamètre de pore (diamètre d’ouverture), la densité de pore, etc. en jouant sur les conditions dont la proportion d’eau dans la substance amphipathique et la proportion du polymère organique dans la substance amphipathique. On peut ainsi obtenir une structure poreuse extrêmement fonctionnelle. Le processus de fabrication d'une structure poreuse dans laquelle un gabarit à micelles inversées formé dans une solution de solvant organique hydrophobe est utilisé pour la formation de pores comprend les phases suivantes : (i) une phase dans laquelle on mélange avec agitation une solution comprenant une substance amphipathique, un polymère organique hydrophobe, un liquide hydrophile et un solvant organique hydrophobe qui dissout le polymère organique pour obtenir une solution de solvant organique hydrophobe ayant des micelles inversées formées dans celle-ci (phase (1)); (ii) une phase dans laquelle la solution de solvant organique hydrophobe est coulée sur un substrat (phase (2)) ; et (iii) une phase dans laquelle le solvant organique hydrophobe et le liquide hydrophile s’évaporent et sont retirés de la solution de solvant organique hydrophobe sur le substrat pour constituer une structure poreuse (phase (3)).
PCT/JP2006/314067 2005-07-14 2006-07-14 Processus de fabrication de structure poreuse et structure poreuse obtenue grâce au processus WO2007007877A1 (fr)

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KR102159437B1 (ko) * 2018-11-09 2020-09-23 한양대학교 에리카산학협력단 다공성 탄성 구조체, 표면이 개질된 다공성 탄성 구조체, 및 그들의 제조 방법.
JP7465428B2 (ja) * 2020-02-27 2024-04-11 トヨタ自動車株式会社 樹脂多孔質体の製造方法
KR102630082B1 (ko) * 2020-11-30 2024-01-29 한국화학연구원 신축성 및 전도성을 갖는 다공성 전극 제조용 페이스트 조성물, 이를 이용한 다공성 전극 및 이의 제조방법
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