WO2006112358A1

WO2006112358A1 - Process for production of honeycomb-like porous material

Info

Publication number: WO2006112358A1
Application number: PCT/JP2006/307840
Authority: WO
Inventors: Masatsugu Shimomura; Masaru Tanaka; Hiroshi Yabu; Hidekazu Yamazaki; Hirohisa Hokazono; Yukako Fukuhira; Hiroaki Kaneko
Original assignee: National University Corporation Hokkaido University; Fujifilm Corporation; Teijin Limited
Priority date: 2005-04-13
Filing date: 2006-04-13
Publication date: 2006-10-26
Also published as: JP5041534B2; JPWO2006112358A1

Abstract

A process for the production of honeycomb-like porous material made of a water-nonsoluble polymer, which comprises the step of applying a solution obtained by dissolving a water-nonsoluble polymer and a surfactant in a water-insoluble organic solvent and having an interfacial tension of 10 to 20mN/m against water to a substrate made of a metal or glass to form a thin film of the solution and the step of evaporating the organic solvent from the thin film on the substrate. This process can give a high-quality honeycomb-like porous material exhibiting a standard deviation of pore diameter of 10% or below in an area 100μm square. Further, another high-quality honeycomb-like porous material having a pore diameter of as small as 1nm to 100μm and a standard deviation of pore diameter of 10% or below can be obtained by conducting the evaporation of the solvent under a specified air stream. The honeycomb-like porous materials are useful as optical films such as photonic crystal, antireflection coating, and light diffusing plate; electronic materials such as molds of patterned resists or electrodes; cell culture substrata; separation membranes with uniform pore diameters; and so on.

Description

Specification

A method for manufacturing a honeycomb-shaped porous body.

Technical field

[0001] The present invention relates to a method for manufacturing a honeycomb-shaped porous body having a fine periodic structure.

Background art

[0002] A structure having a fine periodic structure is a useful material in various fields such as electronics, optics, and biotechnology. In the field of electronic engineering, a process for producing electronic materials having a fine periodic structure of lOOnm or less has been put into practical use along with the channel miniaturization technology of electric field transistors (Non-patent Document 1). In the field of optics, structures having a fine periodic structure such as diffraction gratings and photonic crystals are attracting attention as next-generation optical functional elements (Non-patent Document 2). In addition, a thin film having a fine periodic structure having a periodic structure equal to or shorter than the wavelength of light is transparent in the visible light region, and is expected to have an effect of preventing light scattering and the like. In recent years, in the field of regenerative medicine, it has been reported that the fine structure of the surface of a structure having a fine periodic structure affects the proliferation of cultured cells (Non-patent Document 3).

[0003] Photolithography, soft lithography (Non-patent Document 4) and the like are known as conventional techniques for producing a structure having a fine periodic structure. Such a method is to produce a structure having a fine periodic structure by slicing the material used as a raw material, and is called a top-down production process. In general, top-down fabrication processes are based on breaking intermolecular bonds, and thus essentially require high energy. Therefore, this process is a high-cost process that requires multi-step processes, and there are many problems to be solved as a method of manufacturing a structure having a simple periodic structure such as a diffraction limit.

[0004] On the other hand, an attempt has been made to produce a structure having a fine periodic structure by accumulating materials at molecular level. For example, phase separation of a block copolymer is known as a process for producing a structure having an lOnm scale microstructure (Non-patent Document 5). Block copo that covalently connects the ends of two or more polymers with different compatibility The remer can change the period of the phase separation structure according to the compatibility and the length of each segment. However, this method also requires a complicated organic synthesis process, and the types of block copolymers that can be synthesized are limited.

[0005] In addition, a method of producing a structure having a two-dimensional or three-dimensional periodic structure by accumulating submicron colloidal fine particles (Non-patent Document 6), and by making this a saddle type, it is inverted. Although methods for producing a structure having an opal structure (Non-Patent Document 7) have been reported, fine particles having a single particle size must be prepared, and a mold is taken. After that, there are various process problems, such as cocoons that must be disassembled.

[0006] As a method based on a principle different from these methods, there has been reported a method for easily producing a structure having a honeycomb-like fine periodic structure (honeycomb-like porous body) using water droplets as a saddle type ( Patent Document 1). Specifically, water droplets are condensed on the surface of the polymer non-aqueous organic solvent solution, and a honeycomb-shaped porous body is prepared using the water droplets as a bowl shape. Non-Patent Document 1: Gelsinge et al., IEEE Spectrum, 1989, p. 89, p. 43.

Non-Patent Document 2: Noda et al., Nature, 2000, 407, 608.

Non-Patent Document 3: Chen et al., Science, 1997, 276, 1425 Non-Patent Document 4: White Size et al., Angew. Chem. Int. Ed., 1998, 37th, 550— 575 pages

Non-Patent Document 5: Albrecht et al., Macromolecules, 2002, 35th, 8106-8110

Non-Patent Document 6: Gu et al., Langmuir, 17th pp. 6751-6753.

Non-Patent Document 7: Carso et al., Langmuir, 1999, 15th, 8276-8

281 pages

Patent Document 1: Japanese Patent Laid-Open No. 8-311231

Disclosure of the invention

Problems to be solved by the invention

[0007] However, in any of the above methods, attention is paid to producing a structure having a fine periodic structure with high quality by making the pore diameter of the porous body uniform. Not.

[0008] An object of the present invention is to make a pore size of a porous body substantially uniform in a method for producing a Hercam-like porous body, which is a structure having a fine periodic structure with water droplets in a bowl shape. Is to provide the technology.

Means for solving the problem

[0009] The inventors of the present invention provide a method for producing a Hercam-like porous body having water droplets in a bowl shape! The present inventors have found that the presence of the agent can suppress the variation in the pore diameter of the porous body and produce a high-quality Hercam-like porous body, thereby completing the present invention.

The present invention provides the following manufacturing method.

[0011] 1) A water-insoluble organic solvent solution in which a water-insoluble polymer and a surfactant are dissolved in a water-insoluble organic solvent and having an interface tension with respect to water of 10 to 20 mNZm is applied to a glass or metal substrate. A method for producing a Hermacous porous material comprising a water-insoluble polymer substance, the method comprising: preparing a thin film of the solution; and evaporating an organic solvent from the thin film on the substrate.

[0012] 2) The production method according to 1), wherein the surfactant is one or more surfactants selected from compounds represented by formula (I) or formula (II).

[0013] Formula (I)

[Chemical 1]

(Where n: m is 1: 0 to: LO: 1)

[0014] Formula (II)

[Chemical 2] CH OCORi

CH ₂ OCOR ₂

CH2OPO3CH2CH2R3

(Π)

Wherein R and R are each independently selected from C to C aliphatic hydrocarbon groups.

1 2 11 17

, R is selected as N + (CH 3) or NH force).

3 3 3 3

[0015] 3) Surfactant power of formula (I) Copolymerization ratio = 1: 10 ~: L0: 1, molecular weight = 20,000 ~ 500,000 poly (dodecylacrylamide-co-6-,, -aminocapro 2). The production method according to 2).

[0016] 4) The production method according to 2), which is a surfactant power represented by the formula (II): dioleyl phosphatidylethanolamine, dipalmitoyl phosphatidylethanolamine or dimyristoyl phosphatidylcholine.

[0017] 5) Compound force in which the surfactant is represented by formula (III) or formula (IV) is selected one or more fields — \

The production method according to 1), which is a surfactant. , / 1

[0018] Formula (III)

[Chemical 3]

(UV)

[Chemical 4]

(In the above formula (III) and formula (IV), R represents R ′ or R ′ O, R ′ represents a hydrogen atom or an aliphatic hydrocarbon group having 4 to 22 carbon atoms, a halogen, a hydroxy group, Represents an alkoxy group or a haloalkoxy group, A represents an aliphatic divalent group having 1 to 50 carbon atoms, n represents an integer of 0 to 6, X represents —COOM, —SOM, — PO (OM) or its salt

3 2

Or a hydroxyl group, M represents a hydrogen atom or a cation or cation molecule capable of forming a salt, R represents a hydrogen atom or an aliphatic hydrocarbon group having 4 to 22 carbon atoms, and has the formula (o

The compound of formula (IV) may be a homopolymer consisting of a single monomer or a copolymer having the above-mentioned R, A, n and X which are different for each monomer unit. The compound of formula (IV) is the same or different for each monomer unit. (Random copolymer having R, A, n and X may be used)

6) The production method according to 1), wherein the surfactant is one or more surfactants selected from the compound force represented by formula (V).

[Chemical 5]

(In the formula (V), R represents an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 50 carbon atoms.

Four

X is —SO M, —COOM or — PO (OM)

3 2

Wherein M represents a hydrogen atom or a cation or cation molecule capable of forming a salt)

7) Flow rate having a relative humidity of 30% or more 0.1 to: The production method according to 1), wherein the solvent is evaporated by placing a thin film in an air stream of L00LZ.

[0019] 8) The method according to 1) or 7), wherein the thin film is prepared by applying a water-insoluble organic solvent solution to the substrate while moving the substrate in a uniaxial direction.

[0020] 9) The method according to 1), 7) or 8), wherein a substrate whose surface is modified with an alkyl silane coupling agent is used. Brief Description of Drawings

FIG. 1 shows an apparatus for continuously producing a honeycomb porous body of the present invention.

FIG. 2 shows an overall view of operations and apparatuses in Example 1.

FIG. 3 shows an optical microscope image of the honeycomb porous body of the present invention obtained in Example 1. The left is a honeycomb-like porous body obtained from the solution (A), and the right is a non-nicamic porous body obtained from the solution (B).

[4] An optical microscope image of the honeycomb-shaped porous material prepared from the solution (C) is shown.

FIG. 5 shows an optical microscope image of the honeycomb porous body of the present invention obtained in Example 2.

FIG. 6 shows an optical microscope image of the honeycomb porous body of the present invention obtained in Example 3.

FIG. 7 shows an optical microscope image of the honeycomb porous body of the present invention obtained in Example 4.

FIG. 8 shows an optical microscope image of the honeycomb porous body of the present invention obtained in Example 5. The bar in the figure is the scale bar (10 μm)

FIG. 9 shows an optical microscope image of the honeycomb porous body of the present invention obtained in Example 6. The bar at the bottom is the scale bar (10 ^ m).

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] In the method of the present invention, a water-insoluble organic solvent solution having a water-insoluble organic solvent and a surfactant dissolved in a water-insoluble organic solvent and having an interfacial tension with respect to water of 10 to 20 mNZm is made of glass or metal. Manufacturing a porous porous body made of a water-insoluble polymer substance, comprising a step of preparing a thin film of the solution by applying the thin film on a substrate and a step of evaporating an organic solvent from the thin film on the substrate Regarding the method. In this method, water droplets are condensed on the surface of a polymer non-aqueous organic solvent solution, and a honeycomb porous body is prepared using the water droplets as a bowl shape.

[0023] In addition, the Hercam's porous body (a two-cam structure or a Hercam's sheet) in the present invention is a porous thin film made of a water-insoluble polymer (polymer). Submicron-scale and micron-scale micropores (including dents) oriented in the vertical direction of the membrane are provided in the form of a honeycomb (in a huck shape) in the plane direction of the membrane. Say. The pores may penetrate the membrane in the vertical direction or may communicate with surrounding pores in the planar direction within the membrane. With such a hard cam-like shape! The porous thin film is understood as a structure that is completely different from a normal porous body having irregular pores with various pore diameters, shapes, or depths.

[0024] The shape of the Hercam's porous material in the present invention is such that the film thickness is 0.01 μm to 100 μm, preferably 0.1 μm to 50 μm, more preferably 1 μm. m ~ 20 μm, diameter diameter ^ Ο. 0 Ol ^ m ^ lOO ^ m, preferably ί or 0.1 ^ m to 50 ^ m, more preferably ί or 1 πι to 20; ζ m, especially Preferably, it is 5 m to 10 m.

[0025] The honeycomb-shaped porous body having such a structural feature condenses water droplets on the surface of a polymer non-aqueous organic solvent solution, and prepares a honeycomb-shaped porous body using the water droplets as a bowl shape. It can be prepared by a method, for example, a method described in Patent Document 1, JP-A-2001-157475, JP-A-2002-347107 or JP-A-2002-335949.

[0026] One of the steps constituting the production method of the present invention is a water-insoluble organic solvent solution in which a water-insoluble polymer and a surfactant are dissolved in a water-insoluble organic solvent and the interfacial tension with respect to water is 10 to 20 mNZm. Is applied to a glass or metal substrate to prepare a thin film of the solution.

[0027] The water-insoluble organic solvent that can be used in the present invention is water-insoluble enough to retain water droplets condensed on the solvent surface, and has a boiling point of 0 to 150 ° C under atmospheric pressure, preferably Any of 10 to 50 ° C. can be used. Specifically, halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, and chloroform, aromatic hydrocarbons such as benzene, toluene, and xylene, esters such as ethyl acetate and butyl acetate, and methylisobutyl ketone. Non-water-soluble ketones, carbon dioxide and so on.

[0028] Among these, it can be appropriately selected and used in consideration of solubility in a polymer to be specifically used (described in the next section).

[0029] The water-insoluble polymer used in the present invention is insoluble in water and soluble in the above water-insoluble organic solvent, or is dissolved in the same organic solvent in the presence of a surfactant used in the present invention described later. Any polymer that can be dissolved can be used, and a polymer that can give the function or characteristics expected of the honeycomb-shaped porous body to be produced can be appropriately selected and used.

[0030] For example, biodegradable polymers such as polylactic acid and polyhydroxybutyric acid, aliphatic polycarbonate Nate, amphiphilic polymer, photofunctional polymer, and electronic functional polymer.

[0031] Examples of specific combinations of the water-insoluble organic solvent and the water-insoluble polymer include, for example, polyalkyls such as polystyrene, polycarbonate, polysnolephone, polyetherenolenolephone, polyalkylsiloxane, and polymethylmethacrylate. For polymers that also have a group strength consisting of metatalylate or polyalkyl acrylate, polybutadiene, polyisoprene, poly (N-vinylcarbazole), polylactic acid, poly-one strength prolatatone), polyalkylacrylamide, and copolymers of these. On the other hand, organic solvents such as carbon tetrachloride, dichloromethane, chloroform, benzene, toluene, xylene, and carbon dioxide can be used in combination.

[0032] In the present invention, the water-insoluble polymer is dissolved in a water-insoluble organic solvent in an amount of 0.01 gZL to 50 g ZL, and preferably 0.1 gZL to 10 gZL. Can be appropriately determined according to the properties, physical properties, and solvent used for the honeycomb-like porous body to be produced.

[0033] The surfactant that can be used in the present invention is preferably one or more surfactants selected from compounds represented by formula (I) or formula (II).

[0034] Formula (I)

[Chemical 6]

(Where n: m is 1: 0 to: LO: 1)

[0035] Formula (Π)

[Chemical 7] CH OCORi

CH ₂ OCOR ₂

CH2OPO3CH2CH2R3

(Π)

1 2 11 17

, R is selected as N + (CH 3) or NH force).

3 3 3 3

[0036] For the compound of formula (I), it is preferable to use a compound of n: m = 1: 0, 4: 1 or 10: 1. Particularly, the copolymerization ratio = 1:10 to: L0: 1. It is preferable to use poly (dodecyl atalylamide-co-6-aminocaproic acrylamide) (Cap) having a molecular weight of 20,000 to 500,000. In addition, the compound of the formula (II) includes dimyristoylphosphine in which R, R = C H, R = N + (CH).

1 2 11 23 3 3 3

Dipalmitoy in Fatidylcholine (DMPC) where R, R = C H, R = N + (CH)

1 2 15 31 3 3

Ruphosphatidylcholine (DPPC) or dioley where R, R = C H and R = NH

1 2 17 33 3 3

Use of Ruphosphatidylethanolamine (DOPE) is preferred!

[0037] These surfactants are all known substances, and can be purchased from, for example, Aldrich, etc., and the method of Nishida et al. (Polymer Journal, 34, 166, 2002)

).

In the present invention, a surfactant represented by formula (III) or formula (IV) can also be used.

[0039] Formula (III)

[Chemical 8]

(m) Formula (IV)

In the formula (III) and formula (IV), R represents R ′ or R ′ O, R ′ represents a hydrogen atom or an aliphatic hydrocarbon group having 4 to 22 carbon atoms, halogen, hydroxy group, alkoxy Represents a group or a haloalkoxy group, A represents an aliphatic divalent group having 1 to 50 carbon atoms, n represents an integer of 0 to 6, X represents —COOM, —SO M, — PO (OM) or its salt

3 2

The compound of formula (IV) may be a homopolymer consisting of a single monomer or a copolymer having the above-mentioned R, A, n and X which are different for each monomer unit. The compound of formula (IV) is the same or different for each monomer unit. Random copolymers having the above R, A, n and X may also be used.

[0040] The aliphatic hydrocarbon group having 4 to 22 carbon atoms represented by R 'may be linear or branched, and may have an unsaturated bond. 2 or more types of aromatic hydrocarbon groups! /, May! /

[0041] The number of carbon atoms of the aliphatic hydrocarbon group represented by R 'is preferably 6 to 18. Examples thereof include alkyl groups such as butyl, amyl, hexyl, octyl, nonyl, dodecyl, or octadecyl, and alkenyl groups such as cis-octadecyl group. Halogen is Cl, Br, I, etc., and alkoxy groups are preferably 4-22 carbon atoms in the alkyl moiety, such as octyloxy group, hexyloxy group, dodecoxy group, β-hydroxyethoxy, etc. As the alkoxy group, 4 to 22 carbon atoms in the alkyl portion are preferred, and examples thereof include j8-chloroethoxy and / 3 bromoethoxy. R may be a hydroxy group.

[0042] Examples of the aliphatic divalent group having 1 to 50 carbon atoms represented by A include, for example, an anorylene group, an anorylene group, a polyanorylene group, and an anorylene group. -Divalent groups such as an alkylene group are exemplified, and specific examples include ethylene, trimethylene, otamethylene, ethyleneoxy, polyethyleneoxy, polypropyleneoxy, ethyleneoxy-trimethylene groups.

[0043] One COOM, one SO M, and one PO (OM) acidic group represented by X

3 2

The M in the salt thereof includes, for example, alkaline earth metal ions such as sodium ion, potassium ion and lithium ion, transition metal ions such as calcium ion, normium ion, ammonium ion, silver ion and cadmium ion, carbon number Examples thereof include 1 to 4 alkyl ammonium, quaternized ammonium ions or derivatives thereof.

[0044] Examples of the compound represented by the formula (IV), the formula (III) 5 to monomeric units represented by molar% to 95 molar ^_0/0 it is preferable to include equipment 10 mol% to 90 mol more preferably contains ^_0/0.

[0045] Examples of the monomer units in the formulas (III) and (IV) include the following.

[Chemical 10]

In the above formula, R represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. Molecular weight

0

ί is not particularly limited Repulsion 600-10, 000 force is preferred, 900-5,000 force ^ more preferred! / ,.

[0046] Specific examples of preferred polymers are shown below.

. く十 x $ -Οί- ^Α ' ^:

L = ^ + ^ L

ί = i-'Ol-· <

υ≡ "o-i-■ <

8L0 £ / 900Zd £ / 13d ZY 1/9001 OAV ; 0 i-)

^Ι: Ν¾ ^ Η :) ^? Η つ h ^c H;)

(6— M)

+ 卜. ^ 3

b ^l H ⁶ DI

"N ^c OS ^f ( ^r

: H H,

;: 8— ΛΛ) f above o

i = ■ · <-V: ^ £ Λ: \

g =. <+ (— = people '

!: 9— M)

SL0 £ / 900Zdr I13d 8SCZll / 900Z OAV m

; 'SI— Μ)

Ot one ΛΛ)

(ε 卜 M)

Aoi-, / Tente "?

01 = Λ + X (i: I Λ: V

II -ΛΛ)

0 8L0 £ / 900ZdT / 13d 8SCZll / 900Z OAV Formula (W— 1 6) '

\: Ί: 4 χ f = b

x = 6 Furthermore, in the present invention, it is possible to use one or more kinds of surfactants that can select the compound power represented by the formula (V).

Formula (V)

[Chemical 15]

X

R

Four

X is —SO M, —COOM or — PO (OM)

3 2

Wherein M represents a hydrogen atom or a cation or cation molecule capable of forming a salt.) O M is as described above.

The synthesis method of these compounds is not particularly limited, and a known synthesis method power can be appropriately selected according to the purpose. For example, a formalin polycondensate of alkylphenols. Examples of the synthesis of these include the methods described in Industrial Science Journal 66, 391 (1963), Oil Chemistry 12 625 (1963). For example, it is described in Industrial Science Journal 73-563 (1970), 59-221 (1956), J. Am • Chem. Soc. 77, 2496 (1955), etc. The method which is being done is mentioned.

[0049] The present invention uses a water-insoluble organic solvent solution in which the water-insoluble organic solvent and the surfactant are dissolved in a water-insoluble organic solvent and the interfacial tension with respect to water is 10 to 20 mNZm. The interfacial tension in the present invention means a surface tension measured by a method called a hanging drop method for measuring the interfacial tension of a liquid. In this method, as shown in general textbooks on surface tension, for example, Physics of Surface Tension (Yoshioka Shoten), page 57, by Dougène Brossier Louviare Kele, its principles and concrete The method is well known. More simply, it can be measured using PD-W, an interfacial tension measuring device manufactured by Kyowa Interface Science Co., Ltd. (http: 〃 www.face-kyowa.co.jp/j/interface_chemistry/005.html). The

[0050] With respect to the interfacial tension of the solution of the present invention, the water-insoluble polymer itself has little effect on the interfacial tension of the solution, and therefore the combination of the water-insoluble organic solvent and surfactant used, as well as in the solution. It can be set according to the concentration of the surfactant. The combination and concentration may be determined by dissolving a surfactant in a water-insoluble organic solvent to prepare a water-insoluble solution and measuring the interfacial tension by the hanging drop method. Preferable examples include use of DOPE or Cap for halogenated hydrocarbon solvents such as chloroform or dichloromethane or aromatic hydrocarbons such as toluene and benzene.

[0051] Examples of the substrate material that can be used in the present invention include glass and silicon. In this case, the wettability of the substrate itself with respect to the water-insoluble organic solvent used can affect the thickness of the thin film formed on the substrate.

[0052] Therefore, it is preferable to use a substrate having a high affinity with a water-insoluble organic solvent solution, or a substrate having a surface that has been processed to increase the affinity with a water-insoluble organic solvent solution. Such improvement in the wettability of the substrate can be achieved by a method known per se, such as a glass or metal substrate, in accordance with the combination of the substrate material and the water-insoluble organic solvent used. Alkyl silane coupling treatment can be used for monomolecular film formation treatment with thiol compound.

[0053] For example, as a substrate in the case of using a hydrophobic organic solvent such as black mouth form, it is preferable to use a sufficiently cleaned Si substrate or a glass substrate whose surface is modified with an alkyl silane coupling agent or the like. .

In the present invention, a water-insoluble organic solvent solution containing a water-insoluble polymer and a surfactant as exemplified above is applied to a substrate to form a thin film of the same solution. The coating thickness may be 10 m to 5 mm. If it is too thin, it may be a problem in terms of the strength of the hermetic porous material after production, and if it is too thick, it may be a problem in terms of the efficiency of pore formation.

[0055] As a method of applying a water-insoluble organic solvent solution to a substrate, in addition to the above-mentioned method of dropping the water-insoluble organic solvent solution onto a substrate, a bar coat, a dip coat, a spin coat method, and the like can be given. Either batch type or continuous type can be used.

[0056] In the present invention, from the viewpoint of producing a honeycomb porous body having fine pores, a method of preparing a thin film by applying a water-insoluble organic solvent solution to a movable substrate is preferable. For example, a powerful method can be implemented by using an apparatus as shown in FIG. The apparatus in FIG. 1 has a substrate 1 that can move from the right to the left in the figure at a predetermined speed, a metal plate 2 provided on the substrate 1, and a nozzle 3 that blows air having a predetermined relative humidity. is doing. Here, the metal plate 2 is placed on the substrate 1 with a gap corresponding to a desired thin film thickness.

In this apparatus, the thickness of the thin film applied to the substrate 1 is reduced by passing the substrate 1 on which the water-insoluble organic solvent solution has been applied in advance under the metal plate. The thickness can be adjusted to approximately the same as the gap between the two. It is desirable to adjust the moving speed of the substrate 1 to 0.1 l / z m˜: LOmmZ seconds, particularly 1 to 5 mmZ seconds.

[0058] When this apparatus principle is used, the Hercam-like porous body formed on the substrate can be continuously recovered from the substrate, so that the Hercam-like porous body of the present invention is industrially produced. The production method is also IJI.

[0059] By placing the water-insoluble organic solvent on the substrate in this manner and evaporating the water-insoluble organic solvent from the thin film, a Hercam's porous body made of a water-insoluble polymer can be produced. At that time, by adjusting the evaporation rate of the solvent, the pore size of the Hercam's porous material should be less than lOOnm. Can do. In particular, a flow rate having a relative humidity of 30% or more is 0.1 to: L00LZ, preferably 1.0 to 50LZ, by placing the thin film on the substrate and evaporating the water-insoluble organic solvent. 1 to: A high-quality Herkam-like porous body having a uniform pore diameter within the range of LOOnm can also be produced.

[0060] In this method, a thin film of a water-insoluble organic solvent solution is placed in an air stream having a relative humidity of 30% or more to quickly evaporate the solvent and to suppress the growth of water droplets condensing on the solvent surface. Holes smaller than lOOnm are provided in the Hercam-like porous body. The flow rate of the air flow in such a method may be appropriately adjusted according to the volatility of the solvent used and the thickness of the thin film on the substrate, but is generally 0.1 to: LOOLZ minutes, preferably 1.0 to 50 LZ minutes. And it is sufficient. In addition, as for the arrangement of the thin film relative to the airflow direction, if the thin film on the substrate is tilted upward, or if the vertical force is applied to the airflow, the thin film will be distorted or cracked by the air pressure of the airflow. It can happen. In such a case, it is preferable that the thin film is formed in parallel or upward with a thin film of the organic solvent solution on the substrate with respect to the air flow. In this case, the airflow may be generated by any positive pressure from the upstream side or negative pressure by the downstream force. For example, the nozzle force installed toward the substrate may be ejected from a predetermined air, or the air above the substrate may be sucked from one direction.

Industrial applicability

[0061] According to the present invention, it is possible to produce a high-quality Hercam-shaped porous body having a standard deviation of pore diameters of 10% or less in a 100 μm square Hercum-shaped porous body. Also, by evaporating the solvent under a constant air flow, Inn! It is possible to produce a high-quality hard-cam porous body having a fine pore diameter of ˜100 m and a standard deviation of the pore diameter of 10% or less. Such Hercam's porous materials include photonic crystals, antireflection films, optical films such as light diffusing plates, electronic materials such as patterned resists and electrode plates, cell culture substrates, uniform It can be used for separation membranes using various pore sizes.

[0062] Details of the present invention will be described below with reference to examples. However, these examples do not limit the present invention.

Example 1

[0063] Poly (ε-force prolatatatone) as a water-insoluble polymer (Wako Pure Chemical, molecular weight 70,000 to 100,000) As a surfactant, nZm is 4Zl, number average molecular weight = 29,000, molecular weight 210,000, compound 1 of general formula (I), and in formula (II), R, R = CH, R = NH

1 2 17 33 3 3 A honeycomb-like porous body was prepared using dioleylphosphatidylethanolamine (DOPE) as a water-insoluble organic solvent and chloroform.

[0064] A poly (ε-force prolatatone) concentration of 5 mg / mL and the above compound 1 is 3. Omg / mL of a closed form solution (A), a poly (ε-force prolatatone) concentration of 5 mg / mL and DOPE A 0.5 mg / mL black mouth form solution (B) was prepared. When the interfacial tension of both solutions to water was measured by the hanging drop method (PD-W, Kyowa Interface Chemistry), the solution (A) was 18.6 mNZm and the solution (13.3 mNZm).

[0065] 5 ml of the solution (A) and (B) were dropped onto each glass petri dish, and humidified air (relative humidity 80%, flow rate 2 L / min) was sprayed to evaporate the solvent to form a film (Fig. 2). . The surface structure of the prepared film was observed with an optical microscope, the porosity was calculated from the optical microscope image using image processing software (Image SX M, NIH, USA.), And the standard deviation of the pore diameter was calculated.

[0066] As a result, a high-quality honeycomb film having a standard deviation of the pore diameter of 10% or less was obtained from both solutions (A) and (B) (Fig. 3).

[0067] On the other hand, a solution (C) having the same composition as solution (B) except that the concentration of DOPE was 0.05 mg / mL was prepared, and the interfacial tension was measured. As a result, it was 25.8 mNZm. From this solution (C), a Hercam's porous material was formed by the same operation as described above, but the pore size of the resulting Hercam's porous material was clearly uneven (Fig. 4). .

Example 2

[0068] Polylactic acid (manufactured by SIGMA, molecular weight: 750,000 to 120,000) in a concentration of 5 mgZml and in formula (II) R, R = C H and R = NH

1 2 17 33 3 3

Cloform form solution with a DOPE concentration of 0.1 mgZml 5. Drop Oml onto a glass petri dish, spray humidified air (relative humidity 80%, flow rate 2 L / min) to evaporate the solvent, and form a film. (Figure 5). The surface structure of the fabricated film was observed with an optical microscope, the porosity was calculated from the optical microscope image using image processing software (Image SXM, NIH, USA.), And the standard deviation of the pore diameter was calculated. The standard deviation was less than 10%.

Example 3 [0069] Polystyrene (manufactured by Aldrich, molecular weight of about 280,000) concentration of 5 mgZml and dioleylphosphatidylethanolamine in which R, R = CH and R = NH in formula (II)

1 2 17 33 3 3

(DOPE) concentration of 0.1 mgZml of Kuroguchi form solution 5. Oml was dropped on a glass petri dish, and humidified air (relative humidity 80%, flow rate 2L / min) was sprayed to evaporate the solvent to form a film. (Figure 6). The surface structure of the fabricated film was observed with an optical microscope, the porosity was calculated from the optical microscope image using image processing software (Image SXM, NIH, USA.), And the standard deviation of the pore diameter was calculated. The standard deviation was less than 10%.

Example 4

[0070] Using a polyion complex as a surfactant, a Hercam's porous material was produced. Dimethyto dioctadecy to ammonium bromide (Mutual drug ENE-SOKU, hereinafter referred to as DDAB) 31 mg was dispersed in 200 mL of pure water by sonication. Polystyrene sulfonate potassium salt (Showa Denko) 917 mg was dissolved in 300 mL of pure water, and DDAB aqueous solution was added thereto. The resulting precipitate was extracted with toluene, sodium sulfate was added and dried, and then the solvent was removed by a rotary evaporator. Excess solvent was removed by drying under reduced pressure to obtain 858 mg of polyion complex represented by the following formula (VI) (yield: about 82%).

[0071] Formula (VI)

[Chemical 16]

The polyion complex was dissolved in black mouth form to prepare a 1.0 mg / mL solution. Using this solution, the interfacial tension with respect to water was measured by the hanging drop method, and it was about 17 m NZm.

[0072] Polyion complex concentration is 1. OmgZmL and polystyrene concentration is lOmgZm 4 ml of a solution obtained by dissolving polyion complex and polystyrene in black mouth form so as to be L was cast into a 9 cm petri dish, and humidified air (humidity 40-50%) was sprayed at a flow rate of 4 LZ. An optical microscope image of the obtained film is shown in FIG. A nodular-cam-like porous film in which pores of about 3 microns were arranged in hexagonal was obtained.

Example 5

[0073] Polylactic acid (manufactured by Aldrich, molecular weight 70,000 to 100,000) lOmgZml and dioleyl phosphatidylethanolamine (DOP) in which R, R = C H and R = NH in formula (II)

1 2 17 33 3 3

E) 20 ml of black mouth form solution containing 0.05 mg / ml at the same time was dropped into a glass petri dish and sprayed with humidified air (relative humidity 80%, flow rate 2 L / min) to evaporate the solvent and form a film (Fig. 8).

Example 6

[0074] The poly (ε-strength prolatatone) concentration is 5 mg / mL and the compound of formula (III) (W

A black mouth form solution containing 0.5 mg / mL of the compound of 1) was prepared. The interfacial tension of this solution with respect to water was measured by the hanging drop method (PD-W, Kyowa Interface Chemistry) and found to be 19. OmNZm.

[0075] 5 ml of the solution was dropped onto a glass petri dish, and humidified air (relative humidity 80%, flow rate 2 L / min) was sprayed to evaporate the solvent to form a film (FIG. 9). The surface structure of the fabricated film was observed with an optical microscope, the porosity was calculated from the optical microscope image using image processing software (Image SXM, NIH, USA), and the standard deviation of the pore diameter was calculated. The standard deviation of the hole diameter is less than 10%.

Claims

The scope of the claims

[1] A water-insoluble organic solvent solution in which a water-insoluble polymer and a surfactant are dissolved in a water-insoluble organic solvent and an interfacial tension with respect to water is 10 to 20 mNZm is applied to a glass or metal substrate and the solution is applied. A method for producing a Hermac porous material comprising a water-insoluble polymer substance, comprising a step of preparing a thin film of a solution and a step of evaporating an organic solvent from the thin film on the substrate.

[2] The production method according to claim 1, wherein the surfactant is one or more surfactants selected from compounds represented by formula (I) or formula (II).

Formula (I)

[Chemical 17]

(Where n: m is 1: 0 to: LO: 1)

Formula (Π)

[Chemical 18]

1 2 11 17

, R is selected as N + (CH 3) or NH force).

3 3 3 3

[3] Surfactant power of formula (I) Copolymerization ratio = 1: 0 to: LO: l, molecular weight = 20,000 to 500,000 poly (dodecylacrylamide—co-6-aminocaproic acrylamide) The manufacturing method according to claim 2, wherein:

[4] Surfactant power represented by formula (II) dioleyl phosphatidylethanolamine, dipal The production method according to claim 2, which is mitoyl phosphatidylethanolamine or dimyristoyl phosphatidylcholine.

2. The production method according to claim 1, wherein the surfactant is one or more surfactants selected from compounds represented by formula (III) or formula (IV).

Formula (ΠΙ)

[Chemical 19]

3 2

The compound of formula (IV) may be a homopolymer consisting of a single monomer or a copolymer having the above-mentioned R, A, n and X which are different for each monomer unit. The compound of formula (IV) is the same or different for each monomer unit. (Random copolymer having R, A, n and X may be used) [6] The production method according to claim 1, wherein the surfactant is one or more surfactants selected from the compound force represented by the formula (V).

[Chemical 21]

X

Four

X represents an acidic group represented by —SO M, —COOM or —PO (OM) or those

3 2

[7] The production method according to claim 1, wherein the solvent is evaporated by placing a thin film under an air flow of L00LZ for a flow rate having a relative humidity of 30% or more.

[8] The production method according to claim 1 or 7, wherein the thin film is prepared by applying a water-insoluble organic solvent solution to the substrate while moving the substrate in a uniaxial direction.

[9] The method according to claim 1, 7, or 8, wherein a substrate whose surface is modified with an alkyl silane coupling agent is used.