JP5131690B2 - Method for producing nanostructured material, nanostructured material and use thereof - Google Patents

Description

  The present invention relates to a method for producing a nanostructured material, a nanostructured material and use thereof, and more particularly to a method for producing a nanostructured material having a helical structure, nanostructured material and use thereof.

  The nano-helical structure, which is a nano-scale fine helical structure, can be used in a wide range of applications as an electromagnetic wave absorbing material, sensor, antenna, high-performance separation membrane, etc. in the ultra-high frequency region. Further, if the spiral pitch and the spiral diameter in such a nano-helical structure can be accurately controlled, the industrial impact is very large.

  An organic or inorganic material having optical activity is known as a polymer material that is conventionally considered to form a nano-helical structure.

  For example, Patent Document 1 discloses an optical activity for the purpose of efficiently transferring molecular level chiral information possessed by a polymer having an optically active chiral alignment structure such as a helical structure to a metal oxide such as silica. It has been reported to produce a helical structure composed of an organic / inorganic composite having a chiral orientation structure.

  Further, in Non-Patent Documents 1 and 2, even if the two-component block copolymer in which any of the components has optical activity has an intramolecular composition ratio that forms a cylinder structure or a gyroid structure, it is clockwise. It has been reported to form a helical structure.

  In general, in a two-component block copolymer in which each component does not have optical activity, the same kind of polymer chains gather together by covalently bonding incompatible polymer chains to each other, and each component is independent. As a result, a so-called microphase separation occurs. In general, in an AB block copolymer formed by covalently bonding a polymer block A and a polymer block B, various highly ordered nanoscale higher-order structures are expressed depending on the volume fraction of the A component and the B component. As the volume fraction of the A component increases, the A component has a spherical structure, the A component has a cylindrical shape, the A component has a gyroid-like structure, a lamellar structure, and the B component has a gyroid-like structure. A structure in which the B component is cylindrical and a structure in which the B component is spherical are observed.

  Non-Patent Document 1 discloses that a single helical structure is produced from a styrene-L-lactide block copolymer, and Non-Patent Document 2 discloses that a single helical structure is produced from a styrene-isocyanide block copolymer. ing.

  As polymers having no optical activity, Non-Patent Documents 3 and 4 disclose that a three-component block copolymer exhibits a helical structure. This helical structure is considered to be a structure in which four cylinders are spirally wound around a core cylinder.

  By the way, the block copolymer film having a vertically oriented cylinder structure or lamellar structure is expected to be applied to a wide range of fields such as a magnetic recording medium, a solar cell, a light emitting element, and a precision filter. However, various methods have been proposed because it is difficult to orient the cylinder structure or lamella structure vertically.

  For example, in Patent Document 2, a styrene-ethylenebutylene-styrene triblock copolymer is used, a spherical structure is formed by a solvent casting method using a poor solvent, and heat treatment is performed in a silicone oil bath to perform vertical alignment. A method of manufacturing a cylinder structure is disclosed.

  Patent Document 3 discloses a method for producing a lamellar structure in which a styrene-isoprene block copolymer is vertically aligned by zone heating.

  Further, Patent Document 4 discloses a method of manufacturing a lamellar structure that is vertically aligned by placing a block copolymer on a substrate (unevenness) having a characteristic surface roughness or more and performing heat treatment.

  Patent Document 5 discloses a method for producing a vertically oriented cylinder structure by using a block copolymer composed of a hydrophilic polymer and a hydrophobic polymer.

Non-Patent Document 5 discloses a method for manufacturing a vertically aligned cylinder structure by applying a direct current.
JP 2005-239863 A (published September 8, 2005) JP 2006-299106 A (published on November 2, 2006) JP 2005-060583 A (published March 10, 2005) JP 2004-099667 A (published April 2, 2004) JP 2004-124088 (released on April 22, 2004) Three-Dimensionally Packed Nanohelical Phase in Chiral Block Copolymers, Rong-Ming Ho, Yeo-Wan Chiang, Chi-Chun Tsai, Chu-Chieh Lin, Bao-Tsan Ko, and Bor-Han Huang, J. Am. Chem. Soc. , 126,2704 (2004) Helical Superstructures from Charged Poly (stylene) -Poly (isocyanodipeptide) Block Copolymers, Jerone JLMCornrlissen, Matthias Fischer, Nico AJMSommerdijk, Roeland JMNolte, Science, 280, 1427 (2007) Udo Kreppe, et al. Macromolecules 1995,28,4558 “Cylindrical morphologies in asymmetric ABC triblock copolymers”, Ulrike Breiner, Udo Krappe, Volker Abetz, and Reimund Stadler, Macromol. Chem. Phys. 198,1051-1083 (1997) Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates, T.Thurn-Albrecht, J.Schotter, GAKaestle, N.Emley, T.Shibauchi, L.Krusin-Elbaum, K.Guarini, CTBlack, MTTuominen, and TPRussell , Science Dec 15 2000: 2126-2129

  Conventionally, organic or inorganic materials having optical activity have been used as polymer materials that are supposed to form nano-helical structures. However, it is not practical to actually use an optically active material industrially. Therefore, there is a demand for a method for forming a nano-helical structure using a general-purpose material without using an optically active material.

  The present invention has been made in view of the above problems, and an object of the present invention is to produce a nanostructure material having a nanohelical structure using a general-purpose material without using a material having optical activity, and the method. The object is to realize a nanostructured material having a nanohelical structure.

  Conventionally, a two-component block copolymer has been used as the vertically oriented block copolymer, and the manifestation structure has been limited to a lamellar structure or a cylinder structure. If nanostructured materials with vertically aligned nano-helical structures can be obtained, magnetic recording media, solar cells, light-emitting devices, precision devices that can be expected to be applied to block copolymer films with vertically aligned cylinder structures and lamellar structures The possibility of application to a wide range of fields such as filters and new fields will expand.

  The present invention has been made in view of the above-mentioned viewpoints, and another object of the present invention is to realize a method for producing a film-like nanostructured material that forms a vertically oriented nanohelical structure and the nanostructured material. There is to do.

In order to solve the above problems, the method for producing a nanostructure material according to the present invention includes a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and the polymer block B. A nano-structured material comprising an ABC-triblock copolymer consisting of a third polymer block C covalently bonded to the polymer block C, wherein the phase consisting of the polymer block C is used as a matrix. A phase comprising a cylinder structure, and a phase comprising a polymer block B is a method for producing a nanostructured material having a helical structure around the cylinder structure as a core,
The weight fraction of polymer block A in the ABC-triblock copolymer is 17% or more and less than 26%, the weight fraction of polymer block B is 4% or more and less than 12%, and the weight fraction of polymer block C Is 63% or more and less than 79%, the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B is χ _AB , the repeating monomer constituting the polymer block B, and the polymer block When the interaction parameter with the repeating monomer constituting C is χ _BC , and the interaction parameter between the repeating monomer constituting polymer block A and the repeating monomer constituting polymer block C is χ _AC , χ _BC > satisfy χ _AB> χ _AC ABC- triblock copolymer , A film forming step of forming a film containing the block copolymer using the obtained solution of ABC-triblock copolymer, and microphase separation by removing the solvent from the film And a step of expressing the structure.

  According to said structure, the nanostructure material which has a very high regularity nanometer order helical structure can be simply manufactured using a general purpose substance. Further, according to the above configuration, the nanostructured material having a helical structure oriented in the direction perpendicular to the film surface can be obtained very easily and without any operation such as application of an electric field, application of a temperature gradient, or zone heating. It can be manufactured at a low cost.

In order to solve the above problems, the nanostructure material according to the present invention includes a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and a covalent bond to the polymer block B. A nanophase-separated nanostructured material comprising an ABC-triblock copolymer consisting of a third polymer block C, wherein the nanostructured material has the shape of a membrane, and the ABC-triblock copolymer The weight fraction of polymer block A in the polymer is 17% or more and less than 26%, the weight fraction of polymer block B is 4% or more and less than 12%, and the weight fraction of polymer block C is 63% or more and 79%. And the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B is χ _AB , The interaction parameter between the repeating monomer constituting the polymer block B and the repeating monomer constituting the polymer block C is χ _BC , and the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block C Χ _AC , where χ _BC > χ _AB > χ _AC is satisfied, the phase composed of the polymer block C is used as a matrix, the phase composed of the polymer block A has a cylinder structure, and the polymer block B The phase is characterized by having a spiral structure with the cylinder structure as a core and around it.

  According to said structure, the nanostructure material which has a very high regularity nanometer order helical structure can be simply manufactured using a general purpose substance. Further, according to the above configuration, the nanostructured material having a helical structure oriented in the direction perpendicular to the film surface can be obtained very easily and without any operation such as application of an electric field, application of a temperature gradient, or zone heating. It can be manufactured at a low cost.

  In the nanostructured material according to the present invention, the cylinder structure composed of the polymer block A penetrates from one surface of the membrane toward the opposite surface, and the end of the cylinder structure constituting a part of the membrane surface. It is preferable that at least a part of the cylinder structure including the portion is oriented perpendicular to the film surface, and the absolute value of the disorder of the orientation angle of the vertically oriented portion is less than 45 °.

  With the above configuration, when the cylindrical structure and / or helical structure is dissolved to form a hollow porous structure, a porous structure penetrating the film can be obtained, and the film can be used as a high-functional film, an electrolyte film, or the like. Is possible.

  The nanostructured material according to the present invention preferably has a film thickness of less than 1000 nm.

  Since the nanostructured material has a film thickness of less than 1000 nm, the film can be used for various applications such as a high-functional film and an electrolyte film.

  In the nanostructured material according to the present invention, the cylinder structure is oriented perpendicularly to the film surface throughout the entire surface from one surface of the film to the opposite surface, and the vertically oriented portion The absolute value of the disorder of the orientation angle is preferably less than 45 °.

  With the above configuration, when the cylindrical structure and / or helical structure is dissolved to form a hollow porous structure, a porous structure penetrating the film can be obtained, and the film can be used as a high-functional film, an electrolyte film, or the like. Is possible. Further, such a nanostructured material can be used as a material for producing a nanostamp or nanohelix.

  The nanostructured material according to the present invention preferably has a film thickness of 1 μm or more and 1000 μm or less.

  When the nanostructured material has a film thickness of 1 μm or more and 1000 μm or less, such a film can be used for various applications such as an electrolyte film of a fuel cell and an electromagnetic wave absorbing material in an ultrahigh frequency region.

  In the nanostructured material according to the present invention, the helical structure is preferably a double helical structure.

  The above helical structure is a double helical structure, so that two types of ABC-triblock polymers differing only in the weight fraction of the polymer block B in the ABC-triblock polymer are mixed and dissolved in a solvent to form a film. By doing so, it is possible to manufacture nanostructured materials in which the diameter of the phase composed of the polymer block B forming the double helix is different for each helix of the double helix. A nanoporous material prepared by a method described later using such a nanostructured material can be used as a separation membrane having bimodal pores, for example.

  In the nanostructured material according to the present invention, the polymer block A, the polymer block B, and the polymer block C are preferably achiral.

  Since the polymer block A, the polymer block B, and the polymer block C are achiral, the nanostructured material can be manufactured using a general-purpose polymer material.

  In the nanostructured material according to the present invention, the ABC-triblock copolymer preferably has a weight average molecular weight Mw of 10,000 or more and 1,000,000 or less.

  When the weight average molecular weight Mw of the ABC-triblock copolymer is within the above range, a nanostructure material having a helical structure with a nanometer order size can be produced, which is preferable.

In the nanostructured material according to the present invention, the cylinder structure is preferably arranged in a hexagonal lattice shape .

By the cylinder structure are arranged in a hexagonal lattice, the electromagnetic wave absorbing material of the nanostructured material ultra high frequency range, the sensor, the antenna, high-performance separation membrane and the electrolyte membrane or the like high film, polarizing plate protective film ( (Vertical alignment) and the like.

  In the nanostructured material according to the present invention, the distance between the centers of the cylinder structures is preferably 10 nm or more and 300 nm or less.

  When the distance between the centers of the cylinder structures is 10 nm or more and 300 nm or less, the nanostructure material can be suitably used for an electromagnetic wave absorbing material, a sensor, an antenna, a high-performance separation film, or the like in an ultrahigh frequency region.

  In the nanostructured material according to the present invention, the outer diameter of the helical structure is preferably 5 nm or more and 150 nm or less.

  The outer diameter of the helical structure is 5 nm or more and 150 nm or less, so that the nanostructured material can be used as an electromagnetic wave absorbing material in the ultra-high frequency region, a sensor, an antenna, a high-performance film such as a high-performance separation film or an electrolyte film, and polarizing plate protection. It can be suitably used for a film (vertical alignment) or the like.

  The nanostructured material according to the present invention may further include a substrate, and the film may be formed on the substrate.

  The nanoporous material according to the present invention is preferably one in which the phase composed of the polymer block B of the ABC-triblock copolymer in the nanostructure material is removed by decomposition or dissolution.

  Due to the above configuration, the nanoporous material has a nanometer-order helical structure oriented substantially perpendicular to the film surface, so that it can be used for high-frequency electromagnetic wave absorbing materials, sensors, antennas, highly functional separation membranes, electrolyte membranes, etc. It can be suitably used for a performance film, a polarizing plate protective film (vertical alignment) and the like.

  In the nanostamp according to the present invention, the nanoporous material is filled with a metal, a semiconductor, or an inorganic compound, and then the phase composed of the polymer block A and the phase composed of the polymer block C of the ABC-triblock copolymer are decomposed or dissolved. Is preferably obtained by

  With the above configuration, the nanostamp has a metal, semiconductor, and inorganic compound having a helical structure in the order of nanometers oriented substantially perpendicular to the film surface. It can be suitably used for high-performance membranes such as separation membranes and electrolyte membranes, polarizing plate protective films (vertical alignment), and the like.

  The nanohelix according to the present invention is preferably obtained by removing the phase composed of the polymer block A and the phase composed of the polymer block C of the ABC-triblock copolymer in the nanostructured material by decomposition or dissolution.

  With the above configuration, the nano-helix has a nanometer-order helical structure oriented substantially perpendicular to the film surface. It can be suitably used for a performance film, a polarizing plate protective film (vertical alignment) and the like.

  In the method for producing a nanostructure material according to the present invention, it is preferable to change the outer diameter and pitch of the helical structure by changing the weight fraction of the polymer block A.

  With the above configuration, a nanostructure material having a helical structure having a desired shape can be manufactured.

  In the method for producing a nanostructure material according to the present invention, it is preferable to change the diameter of the helical structure by changing the weight fraction of the polymer block B.

  With the above configuration, a nanostructure material having a helical structure having a desired shape can be manufactured.

As described above, in the method for producing a nanostructure material according to the present invention, the weight fraction of the polymer block A in the ABC-triblock copolymer is 17% or more and less than 26%, and the weight fraction of the polymer block B. Is 4% or more and less than 12%, and the weight fraction of the polymer block C is 63% or more and less than 79%, and the interaction between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B The parameter is χ _AB , the interaction parameter between the repeating monomer constituting the polymer block B and the repeating monomer constituting the polymer block C is χ _BC , the repeating monomer constituting the polymer block A, and the repeating monomer constituting the polymer block C When the interaction parameter with χ _AC is χ _BC A step of dissolving an ABC-triblock copolymer satisfying> χ _AB > χ _AC in a solvent, and forming a film containing the block copolymer using a solution of the obtained ABC-triblock copolymer Since it has a structure that includes a formation process and a process of removing the solvent from the membrane to develop a microphase-separated structure, a nanostructured material with a highly regular helical structure on the order of nanometers It can be easily produced using a substance. Further, according to the above configuration, the nanostructured material having a helical structure oriented in the direction perpendicular to the film surface can be obtained very easily and without any operation such as application of an electric field, application of a temperature gradient, or zone heating. It can be manufactured at a low cost.

As described above, the nanostructure material according to the present invention has a film shape in order to solve the above-described problems, and the weight fraction of the polymer block A in the ABC-triblock copolymer is as follows. 17% or more and less than 26%, the weight fraction of the polymer block B is 4% or more and less than 12%, the weight fraction of the polymer block C is 63% or more and less than 79%, and constitutes the polymer block A The interaction parameter between the repeating monomer and the repeating monomer constituting the polymer block B is χ _AB , and the interaction parameter between the repeating monomer constituting the polymer block B and the repeating monomer constituting the polymer block C is χ _BC , the polymer block A reciprocal monomer constituting A and a repetitive monomer constituting polymer block C The use parameter when chi _AC, and is provided with the structure satisfying _{χ BC> χ AB> χ AC} , the nanostructured material with a very high helical structure of nanometer order regularity, the general-purpose material And can be easily manufactured. Further, according to the above configuration, the nanostructured material having a helical structure oriented in the direction perpendicular to the film surface can be obtained very easily and without any operation such as application of an electric field, application of a temperature gradient, or zone heating. It can be manufactured at a low cost.

  In addition, a nanoscale coil (nanocoil) can be created. Examples of the use of the nanocoil include an electromagnetic wave absorbing material in a high frequency region.

  The present invention will be described below in the order of (I) nanostructured material, (II) method for producing nanostructured material, and (III) use of nanostructured material.

(I) Nanostructured material The nanostructured material according to the present invention includes a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and a covalent bond to the polymer block B. A microphase-separated nanostructured material comprising an ABC-triblock copolymer consisting of a third polymer block C, wherein the nanostructured material has a membrane shape, and the ABC-triblock copolymer The polymer block A has a weight fraction of 17% or more and less than 26%, the polymer block B has a weight fraction of 4% or more and less than 12%, and the polymer block C has a weight fraction of 63% or more and less than 79%. with some, and repeating monomer constituting the polymer block a, the interaction parameter chi _AB between the repeating monomer constituting the polymer block _B, poly Repeating monomers constituting the over block B, and interaction parameter chi _BC and repeating monomer constituting the polymer block _C, a repeating monomer constituting the polymer block A, the interaction parameters between repeating monomer constituting the polymer block C when chi _AC, and satisfies _{χ BC> χ AB> χ AC} , a phase consisting of polymer block C as the matrix phase is composed of a polymer block a, has a cylindrical structure, consisting of a polymer block B The phase has a spiral structure around the cylinder structure as a core and is wound around it.

(I-1) ABC-triblock copolymer The nanostructured material according to the present invention includes a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and the polymer block. A nanophase-separated nanostructured material comprising an ABC-triblock copolymer consisting of a third polymer block C covalently bonded to B.

In the nanostructured material of the present invention, as the ABC-triblock copolymer, the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B is χ _AB , and the polymer block B is The interaction parameter between the repeating monomer constituting the polymer block C and the repeating monomer constituting the polymer block C is χ _BC , and the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block C is χ _AC , The repeating monomer satisfying χ _BC > χ _AB > χ _AC is selected, and the weight fraction of the polymer block A, the polymer block B, and the polymer block C is set to a predetermined range. By using such an ABC-triblock copolymer, it is possible to obtain a nanostructured material that is microphase-separated so that the phase composed of the polymer block B forms a helical structure.

  Here, the ABC-triblock copolymer is a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and a second polymer block B covalently bonded to the polymer block B. 3 is a linear block copolymer composed of 3 polymer blocks C. Here, each of the polymer blocks A, B, and C is composed of different repeating monomers. In other words, the ABC-triblock copolymer is a polymer block A composed of repeating monomers, a polymer block B composed of repeating monomers different from the repeating monomers constituting the polymer block A, and a polymer block A. It is a linear block copolymer in which three types of polymer chains are combined with a polymer block C composed of a repetitive monomer different from the recurring monomer constituting B and B.

  In the ABC-triblock copolymer, the polymer block A has a weight fraction of 17% or more and less than 26%, and the polymer block B has a weight fraction of 4% or more and less than 12%. The weight fraction of C is preferably in the range of 63% or more and less than 79%. By obtaining a weight fraction of the polymer block A, the polymer block B, and the polymer block C within the above range, a nanostructured material that is microphase-separated so as to form a helical structure of the phase composed of the polymer block B is obtained. Can do.

  By obtaining a weight fraction of the polymer block A, the polymer block B, and the polymer block C within the above range, a nanostructured material that is microphase-separated so as to form a helical structure of the phase composed of the polymer block B is obtained. For example, the following reasons can be considered. That is, the phase consisting of the polymer block B having the smallest weight fraction is extremely stretched by forming a wound spiral structure around the cylinder structure of the phase consisting of the polymer block A having the next smallest weight fraction, It is thought that the molecular chain that shrinks is the smallest and the most stable in terms of energy.

  The weight fraction of the polymer block A is preferably from 17% to less than 26%, more preferably from 18% to 25%, and further preferably from 19% to 24%. The weight fraction of the polymer block B is preferably 4% or more and less than 12%, more preferably 5% or more and 11% or less, and further preferably 6% or more and 10% or less. The weight fraction of the polymer block C is preferably in the range from 63% to less than 79%, more preferably from 64% to 78%, and even more preferably from 65% to 77%.

In the ABC-triblock copolymer, the interaction parameter between the repeating monomers constituting the polymer block A, the polymer block B, and the polymer block C satisfies χ _BC > χ _AB > χ _AC. is there. Thereby, a nanostructured material that is microphase-separated so that the phase composed of the polymer block B forms a helical structure can be obtained.

Here, the interaction parameter χ refers to the interaction parameter of Flory-Huggins. For example, the interaction parameter χ _AB between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B is as follows. The value obtained by equation (1).
χ _AB = (v / RT) (δ _A −δ _B ) ² (1)
In the formula (1), v represents a molar volume, R represents a gas constant, T represents an absolute temperature, and δ represents a Hildebrand compatibility parameter.

The molar volume v is a value obtained by the following formula (2).
v = {(molecular weight of repeating monomer constituting polymer block A / density of polymer block A) + (molecular weight of repeating monomer constituting polymer block B / density of polymer block B)} / 2 (2)
In the present invention, the Hildebrand compatibility parameter δ used to calculate the interaction parameter χ is Polymer Handbook (Brandrup, J and Immergut, EH “Polymer Handbook”, 3. Ed., Wiley). , New York 1989).

The Hildebrand compatibility parameter δ is defined by the following equation considering the attractive force between molecules in the Hildebrand-Scatchard solution theory.
δ = (ΔE _V / V ₁ ) ^1/2
Here, ΔE _V represents evaporation energy, V ₁ represents molecular volume, and ΔE _V / V ₁ represents cohesive energy density. Also,
ΔE _V = ΔH _V -PdV
At 1 mole, ΔE _V = ΔH _V -RT
Wherein the molar heat of evaporation at an absolute temperature T is [Delta] H _V, P is the pressure, R represents shows the gas constant. Therefore, the following relationship is derived.
δ = (ΔH _V −RT / V ₁ ) ^1/2
Here, the relationship between χ _BC , χ _AB, and χ _AC may be χ _BC > χ _AB > χ _AC , but compared to χ _BC / χ _AB , χ _BC / χ _AC and χ _AB / χ _AC is big. Also, χ _BC , χ _AB and χ _AC are 0 <(χ _BC / χ _AB ) <3, 8 <(χ _BC / χ _AC ) <12 and 4 <(χ _AB / χ _AC ) <8 It is more preferable that they are in a relationship.

In the ABC-triblock copolymer used in the present invention, the interaction parameter between repeating monomers constituting the polymer block A, the polymer block B, and the polymer block C satisfies χ _BC > χ _AB > χ _AC If it is satisfied and the weight fraction of the polymer block A, the polymer block B, and the polymer block C is within the above range, it is not particularly limited, and any ABC-triblock copolymer may be used. Good.

  More specifically, examples of the ABC-triblock copolymer include polystyrene-polybutadiene-polymethyl methacrylate, polystyrene-polyethylene butylene-polymethyl methacrylate, polystyrene-poly-2-vinylpyridine-poly tert-butyl methacrylate, polystyrene- Examples thereof include polyferrocenylsilane-polymethyl methacrylate, polystyrene-polyisoprene-polymethyl methacrylate, and polystyrene-polyethylenepropylene-polymethyl methacrylate.

The polymer block A, polymer block B, and polymer block C used in the present invention are preferably achiral. In the present invention, unlike the conventional two-component block copolymer, the interaction parameter between repeating monomers constituting the polymer block A, the polymer block B, and the polymer block C is expressed as χ _BC > χ _AB > χ By using an ABC-triblock copolymer satisfying _AC and having a weight fraction of polymer block A, polymer block B, and polymer block C within the above range, a phase composed of polymer block B does not spiral. Since a microphase-separated structure having a structure is expressed, it is not necessary to use a chiral material, and a nanostructure material having a helical structure can be manufactured using a general-purpose polymer material.

  The weight average molecular weight Mw of the ABC-triblock copolymer is not particularly limited and may be selected according to the size of the target nanostructure material. For example, the weight average molecular weight Mw is 10,000 or more. It is preferably 1,000,000 or less, more preferably 20,000 or more and 750,000 or less, and further preferably 30,000 or more and 500,000 or less. When the weight average molecular weight Mw of the ABC-triblock copolymer is within the above range, a nanostructure material having a helical structure with a size of nanometer order to micrometer order can be produced.

  In addition, by changing the weight average molecular weight Mw of the ABC-triblock copolymer, the phase consisting of the polymer block C is used as a matrix, and the phase consisting of the polymer block A has a cylinder structure. The phase consisting of can be changed in size while maintaining the microphase separation structure having a spiral structure around the cylinder structure as a core. For example, if the weight average molecular weight Mw of the ABC-triblock copolymer is decreased, a smaller microphase separation structure can be expressed, and the weight average molecular weight Mw of the ABC-triblock copolymer can be increased. For example, the larger microphase separation structure can be developed.

  Here, the weight average molecular weight Mw means a value measured by gel permeation chromatography.

  Moreover, the molecular weight distribution (Mw / Mn) of the ABC-triblock copolymer is preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less. .

  When the molecular weight distribution is within the above range, a more uniform microphase separation structure can be expressed.

  Here, the molecular weight distribution (Mw / Mn) means a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography.

  The method for producing the ABC-triblock copolymer is not particularly limited, and a conventionally known method can be suitably used. As such a method, for example, living anionic polymerization can be suitably used. Living anionic polymerization is preferred from the viewpoint of reducing the molecular weight distribution.

(I-2) Higher-order structure of ABC-triblock copolymer A nanostructured material according to the present invention is a nanostructured material separated from a microphase containing the ABC-triblock copolymer, and the polymer block C The phase consisting of the polymer block A has a cylindrical structure, and the phase consisting of the polymer block B has a helical structure around the cylinder structure as a core. Yes.

  A nanostructured material according to the present invention will be described with reference to FIGS. FIG. 1 is a diagram schematically showing a nanostructure material according to the present invention. As shown in FIG. 1, in the nanostructured material according to the present invention, the phase composed of the polymer block A forms a cylinder structure. With such a cylinder structure as a core, a spiral structure is formed by winding a phase composed of the polymer block B around the periphery. The matrix that fills the gap in the cylinder structure in which the phase composed of the polymer block B is wound is constituted by the phase composed of the polymer block C. Each phase is constituted by aggregation of polymer blocks constituting the phase. FIG. 3 shows the results obtained by tilting the nanostructured material according to the present invention in a transmission electron microscope (TEM), acquiring transmission images at various angles, and performing three-dimensional reconstruction. FIG. In FIG. 3, the black spiral structure is a phase composed of the polymer block B, the gray portion in the spiral is a phase composed of the polymer block A, and the matrix portion is a phase composed of the polymer block C.

  Moreover, the winding direction of the helical structure wound around the cylinder structure as a core is not particularly limited, and may be the same direction or may be partially different in the winding direction.

  The size of each phase is not particularly limited, but the diameter of the phase composed of the polymer block A forming the cylinder structure, that is, the diameter of the cross section perpendicular to the longitudinal direction of the cylinder structure is usually 10 nm to 140 nm. Is more preferably 20 nm to 120 nm, and even more preferably 30 nm to 100 nm. Here, the shape of the cross section is more preferably circular, but is not limited to a circular shape, and may be an ellipse, a triangle, a quadrangle, a pentagon, or a polygon having more than that. Further, when the cross-sectional shape is not circular, the cross-sectional diameter can be defined by the diameter when the outer periphery of the cross-section is converted into the outer periphery of a circle. When the diameter of the cylinder structure is in the above range, it is suitably used for electromagnetic wave absorbing materials, sensors, antennas, high-performance membranes such as high-performance separation membranes and electrolyte membranes, polarizing plate protective films (vertical alignment), etc. be able to.

  The cylinder structure is regularly arranged at least partially on the surface of the nanostructured material film. More preferably, the cylinder structure is regularly arranged in more parts, more preferably all parts, on the surface of the film of nanostructured material. More specifically, the part where the cylinder structure is regularly arranged is 20% or more, more preferably 50% or more, and still more preferably 80% with respect to the entire surface area of the nanostructured material film. That's it.

The arrangement of the cylinder structures is not particularly limited as long as the cylinder structures are regularly arranged. For example, the cylinder structures are arranged in a hexagonal lattice shape or a cubic lattice shape .

  The distance between the centers of the cylinder structure, that is, the distance between the centers of the cross sections perpendicular to the longitudinal direction of the cylinder structure is usually 10 nm to 300 nm, more preferably 20 nm to 200 nm, more preferably 30 nm to More preferably, it is 150 nm. When the interval between the cylinder structures is in the above range, it can be suitably used for an electromagnetic wave absorbing material, a sensor, an antenna, a high-functional separation membrane, etc. in an ultrahigh frequency region.

  The helical structure may be a single helix, a double helix, a triple helix, or a higher helix structure. In addition, the present inventors narrowed the molecular weight distribution of the ABC-triblock copolymer so that the microphase-separated structure including the double helix structure has many parts, more preferably all parts of the nanostructure material. Has been found to be expressed in

  When the helical structure is doubled, for example, two types of ABC-triblock polymers differing only in the weight fraction of the polymer block B in the ABC-triblock polymer are mixed and dissolved in a solvent to form a film. In this way, nanostructured materials can be produced in which the phase of the polymer block B forming the double helix has a different diameter for each helix of the double helix. A nanoporous material prepared by a method described later using such a nanostructured material can be used as a separation membrane having bimodal pores, for example.

  The pitch of the helical structure indicated by a in FIG. 3 is not particularly limited, but is usually 20 nm to 100 nm, more preferably 40 nm to 80 nm, and further preferably 50 nm to 70 nm.

  Further, the inclination angle of the helix with respect to the cylinder phase shown by b in FIG. 3 is not particularly limited, but is preferably 20 ° to 60 °, more preferably 35 ° to 45 °.

  Also, the diameter of the phase constituting the helical structure indicated by c in FIG. 3 is not particularly limited, but is usually 9 nm to 17 nm, more preferably 11 nm to 15 nm, and more preferably 12 nm to 14 nm. More preferably.

  Further, the diameter of the phase constituting the cylinder structure is not particularly limited, but is usually 10 nm to 140 nm, more preferably 20 nm to 120 nm, and further preferably 30 nm to 100 nm.

  Further, the outer diameter of the helical structure indicated by d in FIG. 3 is usually 5 nm to 150 nm, more preferably 10 nm to 140 nm, and further preferably 20 nm to 120 nm. Here, the outer diameter of the helical structure refers to a value represented by (diameter of the phase constituting the cylinder structure + diameter of the phase constituting the helical structure × 2).

  Moreover, when the said helical structure is a double or more helical structure, the thickness of each helical structure may be the same and may differ.

(I-3) Nanostructured material The nanostructured material according to the present invention preferably has a film shape. The film thickness of the film made of the nanostructured material of the present invention is not particularly limited, but is preferably 5,000 μm or less, and more preferably 1,000 μm or less.

  Among these, a more preferred embodiment of the film made of the nanostructured material according to the present invention is a film having a film thickness of less than 1000 nm. Such a membrane can be used for various applications such as a high-performance membrane and an electrolyte membrane. The thickness of such a film may be greater than 0 and less than 1000 nm, more preferably 10 nm to 500 nm, and still more preferably 20 nm to 300 nm.

  Another more preferred embodiment of the film made of the nanostructured material according to the present invention is a film having a film thickness of 1 μm or more and 1000 μm or less. Such a membrane can be used for various applications such as an electrolyte membrane of a fuel cell and an electromagnetic wave absorbing material in an ultrahigh frequency region. The film thickness of such a film may be 1 μm or more and 1000 μm or less, more preferably 1 μm or more and 100 μm or less, and still more preferably 1 μm or more and 50 μm or less.

  The nanostructured material according to the present invention may further include a substrate, and the film may be formed on the substrate. In the present invention, regardless of whether the substrate is hydrophilic or hydrophobic, the cylinder structure (and the central axis of the helical structure) is at least from the film surface on both sides toward the inside of the film. Some can be oriented perpendicular to the film surface.

  Although it does not specifically limit as said board | substrate, For example, a silicon substrate, a mica, a glass substrate, an ITO board | substrate etc. can be used suitably.

  In the nanostructured material according to the present invention, the cylinder structure composed of the polymer block A penetrates from one surface of the membrane toward the opposite surface. In addition, the spiral structure formed by wrapping around the cylinder structure also penetrates from one surface of the membrane to the opposite surface, like the cylinder structure. Thus, when the cylindrical structure and / or the helical structure is dissolved to form a hollow porous structure, a porous structure penetrating the film can be obtained, and the film can be used as a high-functional film, an electrolyte film, or the like. It becomes possible.

  In addition, the block copolymer consisting of a hydrophilic phase and a hydrophobic phase usually having a cylinder structure has a problem that the hydrophobic phase covers the surface of the membrane, but the nanostructured material of the present invention Then there is no such problem.

  In the nanostructured material according to the present invention, at least a part of the cylinder structure including the end of the cylinder structure constituting a part of the film surface is oriented perpendicularly to the film surface, and is oriented vertically. The absolute value of the disorder of the orientation angle of the portion is preferably less than 45 °, more preferably less than 35 °, and still more preferably less than 20 °.

  That is, in the nanostructured material, the cylinder structure is oriented perpendicular to the film surface at least in the vicinity of the film surfaces on both sides. In addition, in the spiral structure formed by wrapping around the cylinder structure, the central axis of the spiral structure is oriented perpendicular to the film surface in the vicinity of the film surfaces on both sides, similarly to the cylinder structure. .

  Here, the cylinder structure (and the central axis of the spiral structure) may be oriented at least partially perpendicular to the film surface from the film surface on both sides toward the inside of the film. Preferably, at least 10 μm and more preferably at least 2 μm from the film surfaces on both sides should be oriented perpendicular to the film surface.

  When the nanostructured material according to the present invention is a film having a film thickness of less than 1000 nm, the cylinder structure is perpendicular to the film surface over the entire surface from one surface of the film to the opposite surface. It is preferable that the absolute value of the disorder of the orientation angle of the vertically oriented portion is less than 45 ° while being oriented. The absolute value of the disorder in the orientation angle of the vertically oriented portion is more preferably less than 35 °, and even more preferably less than 20 °. In such a case, the spiral structure formed by wrapping around the cylinder structure also has a central axis of the spiral structure extending from one surface of the film to the opposite surface. It is preferable that the absolute value of the disorder of the orientation angle of the portion oriented perpendicularly to the surface is less than 45 °.

  Thus, when the cylindrical structure and / or the helical structure is dissolved to form a hollow porous structure, a porous structure penetrating the film can be obtained, and the film can be used as a high-functional film, an electrolyte film, or the like. It becomes possible.

  Note that “the film is oriented perpendicularly to the film surface and the absolute value of the disorder of the orientation angle of the vertically oriented part is less than 45 °” means that the film is oriented perpendicularly to the film surface. The case and the case where there is a certain disorder in the orientation angle. Here, the “absolute value of orientation angle disturbance” refers to an absolute value of an angle formed with a line perpendicular to the film surface, such as the angle θ shown in FIG. 8, and a cross-sectional TEM image is observed. Can be measured.

(II) Method for Producing Nanostructured Material A method for producing a nanostructured material according to the present invention is a nanostructured material containing the above ABC-triblock copolymer and microphase-separated, and comprising a phase comprising a polymer block C. As a matrix, a nanostructure material in which a phase composed of a polymer block A has a cylinder structure, and a phase composed of a polymer block B has a helical structure that is wound around the cylinder structure as a core The weight fraction of polymer block A in the ABC-triblock copolymer is 17% or more and less than 26%, and the weight fraction of polymer block B is 4% or more and less than 12%. The polymer block C has a weight fraction of 63% or more and less than 79%, and a repeating monomer constituting the polymer block A; , The interaction parameter with the repeating monomer constituting the polymer block B is χ _AB , the interaction parameter between the repeating monomer constituting the polymer block B and the repeating monomer constituting the polymer block C is χ _BC , and the polymer block A is constituted repeating monomer, the step of dissolving _AC interaction parameters between repeating monomer constituting the polymer block C _chi, and was at the time, the χ _BC> χ _AB> χ satisfying the _AC ABC-triblock copolymer in a solvent And a film forming step of forming a film containing the block copolymer using the obtained ABC-triblock copolymer solution, and a step of removing a solvent from the film to develop a microphase separation structure. Should be included.

In the method for producing a nanostructure material according to the present invention, an interaction parameter between repeating monomers constituting the polymer block A, the polymer block B, and the polymer block C satisfies χ _BC > χ _AB > χ _AC , In addition, by using a specific ABC-triblock copolymer in which the weight fraction of the polymer block A, the polymer block B, and the polymer block C is within the above range, the ABC-triblock copolymer is removed from the solvent. In the simple method of dissolving in the solution, forming a film, and removing the solvent, the phase composed of the polymer block C is used as a matrix, the phase composed of the polymer block A has a cylinder structure, and consists of the polymer block B The phase has a spiral structure around the cylinder structure as a core. It is possible to produce nanostructured materials. In addition, at least a part of the cylinder structure including the end of the cylinder structure constituting a part of the film surface is oriented perpendicular to the film surface, and the orientation angle of the vertically oriented part Take measures such as the conventional zone heating of block copolymers and the use of (uneven) substrates with a characteristic surface roughness higher than that of nanostructured materials with an absolute value of disturbance of less than 45 °. And can be manufactured reliably.

  In the method for producing a nanostructure material according to the present invention, the outer diameter and pitch of the helical structure can be changed by changing the weight fraction of the polymer block A. Thereby, a nanostructure material having a helical structure having a desired shape can be manufactured.

  Further, the outer diameter and pitch of the helical structure are the same as those in the polymer block A in addition to or in place of the method for changing the weight fraction of the polymer block A. It can also be changed by blending homopolymers of structure.

  Further, in the method for producing a nanostructure material according to the present invention, the wire fraction of the helical structure, in other words, the helical structure shown by c in FIG. 3 is formed by changing the weight fraction of the polymer block B. The phase diameter can be varied. Thereby, the nanostructure material which has the wire diameter of a desired helical structure can be manufactured.

  Further, the wire diameter of the helical structure may be changed from the same chemical structure as that of the polymer block B to the ABC-triblock copolymer in addition to or instead of the method of changing the weight fraction of the polymer block B. It can also be changed by blending the homopolymers.

(II-1) Step of dissolving the ABC-triblock copolymer in a solvent The ABC-triblock copolymer used in this step is the same as that described in (I) above, and is not described here. To do.

  Moreover, the said solvent used at this process will be specifically limited if it is a solvent which is not a poor solvent with respect to all of the polymer block A, the polymer block B, and the polymer block C of the ABC-triblock copolymer to be used. Instead, it may be appropriately selected according to the type of ABC-triblock copolymer to be used.

  As such a solvent, for example, chloroform, tetrahydrofuran, dioxane, methyl isobutyl ketone, benzene, toluene, xylene, carbon tetrachloride, ethylbenzene, propylbenzene and the like can be suitably used. For example, when the ABC-triblock copolymer to be used is polystyrene-polybutadiene-polymethyl methacrylate, chloroform or the like can be suitably used.

  In addition, the concentration of the ABC-triblock copolymer, that is, the ratio of the weight of the dissolved ABC-triblock copolymer to the total weight of the dissolved ABC-triblock copolymer and the solvent is 0. 0.05 wt% to 20 wt% is preferable, and 0.1 wt% to 10 wt% is more preferable. It can use suitably for a film forming process because the density | concentration of the said ABC-triblock copolymer is the said range.

(II-2) Film Formation Step In the film formation step, a film containing the block copolymer is formed using the ABC-triblock copolymer solution obtained in the above step. The method for forming the film is not particularly limited, and a conventionally known method may be appropriately selected and used.

  Examples of the film forming method include a solvent casting method, a spin coating method, a dip coating method, and the like, but the film forming method is not limited to these, and may be performed by other methods. . The film thickness can be adjusted by appropriately selecting the concentration of the ABC-triblock copolymer, the number of revolutions and time in spin coating, the pulling rate in the dip coating method, and the like.

(II-3) Step of removing the solvent from the membrane to develop a microphase separation structure In this step, the solvent is removed from the membrane obtained in II-2 to develop a microphase separation structure. The method for removing the solvent is not particularly limited, and airless drying, hot air drying, or the like may be used.

  In the present invention, the microphase separation structure can be advanced even when heat treatment is not performed. However, heat treatment may be performed in order to sufficiently advance the microphase separation structure. The heat treatment temperature is usually 140 ° C. to 190 ° C., and the heating time is 12 hours to 48 hours.

  In the conventional method for producing a nanostructured material, various methods have been taken as disclosed in the above-mentioned patent documents and non-patent documents in order to orient the cylinder structure perpendicular to the film surface. Compared to Patent Document 2, the method for producing a nanostructured material according to the present invention is superior in that the sample is not heat-treated in a silicone oil bath, so that deterioration of the sample due to heat can be prevented. In addition, since the sample is not zone-heated with respect to the above-mentioned Patent Document 3, there is an advantage in that it can be easily vertically aligned without using a special apparatus. Moreover, it is superior to Patent Document 4 in that no special processing is performed on the substrate. In addition, Patent Document 5 has an advantage in that a general-purpose polymer material is used. Further, it has an advantage over Non-Patent Document 4 in that it does not require application of a direct current.

(III) Utilization of Nanostructured Material Since the nanostructured material according to the present invention has a spiral structure in which at least a part is vertically oriented from the surface of the film toward the inside of the film, the nanoporous material, nanostamp, nanotemplate, etc. By doing so, it can be used for a wide range of applications such as electromagnetic wave absorbing materials in the ultra-high frequency region, sensors, antennas, high-performance films such as highly functional separation membranes and electrolyte membranes, and polarizing plate protective films (vertical alignment).

  Therefore, the present invention also includes nanoporous materials, nanostamps, nanotemplates and the like that are produced using the nanostructured material.

  The nanoporous material according to the present invention is obtained by removing the phase composed of the polymer block B of the ABC-triblock copolymer in the nanostructured material by decomposition or dissolution.

  The method for decomposing the phase comprising the polymer block B is not particularly limited, and a conventionally known method can be suitably used. Examples thereof include ozone decomposition treatment, ion beam etching, and the like. it can. Further, the method for dissolving the phase composed of the polymer block B is not particularly limited, and a conventionally known method can be used. For example, the polymer block B is dissolved, but the polymer blocks A and C are not dissolved. Such solvents can be mentioned.

  As a result, the diameter of the helical structure, in other words, the diameter of the phase constituting the helical structure shown by c in FIG. 3 is 9 nm to 17 nm, and at least a part is vertically oriented from the surface of the film toward the inside of the film. A nanoporous material having a spiral through-hole can be obtained.

  Such a nanoporous material can be suitably used for an electromagnetic wave absorbing material, a sensor, an antenna, a high-performance film such as a highly functional separation film or an electrolyte film, a polarizing plate protective film (vertical alignment), and the like.

  The nanohelix according to the present invention is obtained by removing the phase composed of the polymer block A and the phase composed of the polymer block C of the ABC-triblock copolymer in the nanostructured material by decomposition or dissolution.

  The method for decomposing the phase composed of the polymer block A and the phase composed of the polymer block C is not particularly limited, and a conventionally known method can be suitably used. For example, as an example, ozonolysis treatment, ion Examples include beam etching. Further, the method for dissolving the phase composed of the polymer block A and the phase composed of the polymer block C is not particularly limited, and a conventionally known method can be used. For example, the phase composed of the polymer block A can be used. And a solvent that dissolves the phase composed of the polymer block C but does not dissolve the polymer block B.

  As a result, the diameter of the helical structure, in other words, the diameter of the phase constituting the helical structure shown by c in FIG. 3 is 9 nm to 17 nm, and at least a part is vertically oriented from the surface of the film toward the inside of the film. Nano-helix can be obtained.

  Such a nano helix can be suitably used for an electromagnetic wave absorbing material, a sensor, an antenna, a high-performance film such as a highly functional separation film or an electrolyte film, a polarizing plate protective film (vertical alignment), and the like.

  In the nanostamp according to the present invention, the nanoporous material is filled with a metal, a semiconductor, or an inorganic compound, and then the phase composed of the polymer block A and the phase composed of the polymer block C of the ABC-triblock copolymer are decomposed or dissolved. It is obtained by doing.

  Thereby, the diameter of the helical structure, in other words, the diameter of the phase constituting the helical structure shown by c in FIG. 3 is 9 nm to 17 nm, and at least a part is perpendicular from the surface of the film to the inside of the film. An oriented nano-helix composed of a metal, a semiconductor, or an inorganic compound can be obtained.

  Such nano stamps can be suitably used for electromagnetic wave absorbing materials in the ultra-high frequency region, sensors, antennas, high-performance films such as highly functional separation membranes and electrolyte membranes, polarizing plate protective films (vertical alignment), and the like.

[Example 1: Production of ABC-triblock copolymer]
Polystyrene (PS) -polybutadiene (PB) -polymethyl methacrylate (PMMA) was produced as an ABC-triblock copolymer by the method described in Clemens Auschra, Reimund Dtadler, Polymer Bulletin 30, 257-264 (1993). .

  20 ml of a 1.4M heptane solution of n-BuLi was added to 1200 ml of purified THF and left overnight at room temperature. The next day, styrene was introduced and cooled to -80 ° C. The reaction solution was stirred vigorously and polymerization was initiated with n-BuLi to obtain an orange living polystyrene solution. After 30 minutes, butadiene was condensed in a reaction vessel, and the colorless reaction solution was heated to −10 ° C. to polymerize butadiene over 4 to 6 hours. Under such conditions, most butadiene (> 90%) reacted. Subsequently, excess 1,1-diphenylethylene was added to the resulting solution. The solution turned red within a few minutes. After the solution was cooled to -60 ° C, methyl methacrylate was slowly added. The colorless solution was heated to −40 ° C. and stirred for 1 hour to complete the reaction. The resulting polystyrene-polybutadiene-polymethyl methacrylate was separated by precipitation in methanol.

  During the polymerization, the polystyrene block and a portion of the polystyrene-polybutadiene capped with 1,1-diphenylethylene were separated for analytical purposes.

  The obtained polystyrene-polybutadiene-polymethyl methacrylate has Mn (polystyrene block) = 34000, Mn (polybutadiene block) = 1900, Mn (polymethyl methacrylate block) = 124100, Mw / Mn = 1.06, Mn (polystyrene- Polybutadiene-polymethyl methacrylate) = 1700. From the above results, the weight fraction of polystyrene block (polymer block A) is 20%, the weight fraction of polybutadiene block (polymer block B) is 7%, and the weight fraction of polymethyl methacrylate block (polymer block C) is It was 73%.

In addition, the interaction parameter between each polymer block of polystyrene-polybutadiene-polymethyl methacrylate is χ _AB (χ _(PS-PB) ) = 0.098, χ _BC (χ _(PB-PMMA) ) = 0.168. , Χ _AC (χ _(PS−PMMA) ) = 0.016.

[Example 2: Production of a film having a thickness of micrometer order]
The polystyrene-polybutadiene-polymethyl methacrylate obtained in Example 1 was dissolved in chloroform so as to be 5 wt% to obtain a chloroform solution. This chloroform solution was dropped into a glass petri dish, and the solvent was evaporated at room temperature for 24 hours to obtain a film having a thickness of 1000 μm. From the obtained film, an ultrathin section with a membrane cross section was prepared using an ultramicrotome, and the PB phase was stained by exposure to vapor of an OsO ₄ solution.

  Stained ultrathin sections are tilted in a transmission electron microscope (Transmission Electron Microscopy, TEM: JEM-2200FS (acceleration voltage 200 kV), manufactured by JEOL Ltd.), and transmission images are acquired at various angles to reconstruct three-dimensionally. Went. From the obtained three-dimensional data, the pitch and winding angle of the helical structure were determined.

FIG. 2 is a diagram showing the results of TEM observation of the film obtained in this example. Since dyeing is performed with OsO ₄ , the black phase is the PB phase, the gray phase is the PS phase, and the whitest phase (matrix) is the PMMA phase. As shown in FIG. 2 (a), the can be observed are arranged in a hexagonal lattice (hexagonal to the packing) ¥ shaped gray phase (internal PS phase, circular black PB phase) Further, as shown in FIG. 2B, a parallel pattern composed of a gray phase (PS phase) including crossed PB phases could be observed. From this, it was found that the basic structure of the triblock copolymer used in this example was a cylinder structure.

  FIG. 3 is a diagram showing the result of three-dimensional reconstruction of the film obtained in this example. In FIG. 3, the phases indicated by x and y are both PB phases. It can be seen from FIG. 3 that the PB phase indicated by x and the PB phase indicated by y form a cylinder structure having a left-handed double helix that does not cross each other.

  The pitch of the helix was 60 nm, the inclination angle of the helix with respect to the cylinder phase was 40 °, the diameter of the PB phase was 13 nm, and the outer diameter of the helix structure was 40 nm. This double helix structure could be confirmed in all regions of this sample, and the quadruple helix structure reported in the past was not formed at all. Furthermore, not only the left-handed spiral structure, but also the right-handed spiral structure and the one in which the winding direction was changed in one spiral structure were confirmed.

  FIG. 5 is a cross-sectional view of the film surface of the film obtained in this example. The TEM image shown by (a) in the figure shows a cross section near the surface of the film formed in the glass petri dish on the side in contact with air (indicated as “Air surface” in the figure). As can be seen from the TEM image shown in (a) in the figure, on the surface in contact with air, the cylinder structure (and the central axis of the spiral structure) is directed from the film surface on the side in contact with air toward the inside of the film. It was observed that at least part of the film was oriented substantially perpendicular to the film surface. In addition, the TEM image shown in (b) in the drawing shows a cross section near the surface on the side in contact with the glass petri dish (labeled “Grass surface”) of the film formed in the glass petri dish. As can be seen from the TEM image shown in (b) in the figure, the cylinder structure (and the central axis of the spiral structure) also faces the inside of the film from the film surface on the side in contact with the glass petri dish even on the surface in contact with the glass petri dish. Thus, it was observed that at least part of the film was oriented substantially perpendicular to the film surface.

[Example 3: Production of a film having a thickness of nanometer order]
The polystyrene-polybutadiene-polymethyl methacrylate obtained in Example 1 was dissolved in chloroform so as to be 0.4 wt% to obtain a chloroform solution of a triblock copolymer. After the triblock copolymer solution is dropped on the mica substrate, the mica substrate is rotated by a spin coater at a rotation speed of 4000 rpm for 2 minutes, and the triblock copolymer solution is uniformly applied on the mica substrate. Chloroform was evaporated to form a thin film. The triblock copolymer was aligned by exposing this thin film to chloroform vapor at room temperature for 4 days, and the PB phase was stained by exposing it to the vapor of an OsO ₄ solution. The dyed thin film was peeled from the mica substrate using the water surface, transferred to a copper grid for TEM observation, and subjected to TEM observation in the same manner as in Example 2. In addition, the film thickness of the obtained thin film was 30 nm.

FIG. 4 is a diagram showing the results of TEM observation of the surface of the film obtained in this example. Since dyeing is performed with OsO ₄ , the black phase is the PB phase, the gray phase is the PS phase, and the white phase (matrix) is the PMMA phase. In FIG. 4, both the PB phase and the PS phase appear black. Yes. In FIG. 4, the scale bar indicates 2 μm. As shown in FIG. 4, it was confirmed that the microphase separation structure including the helical structure and the cylinder structure of the polystyrene-polybutadiene-polymethylmethacrylate film was arranged in a hexagonal lattice pattern in the entire observed region. Further, from the result of the three-dimensional reconstruction of the film obtained in this example, it was found that the PB phase formed a double helix.

  In the film obtained in this example, the cylinder structure (and the central axis of the helical structure) is oriented perpendicular to the film surface over the entire surface from one surface of the film to the opposite surface. In addition, it was confirmed that the absolute value of the disorder of the orientation angle of the vertically oriented portion was less than 20 °.

[Example 4: Production of a film having a thickness of nanometer order]
The polystyrene-polybutadiene-polymethyl methacrylate obtained in Example 1 was dissolved in chloroform at 0.8 wt% to obtain a chloroform solution of a triblock copolymer. After the triblock copolymer solution is dropped on the mica substrate, the mica substrate is rotated by a spin coater at a rotation speed of 4000 rpm for 2 minutes, and the triblock copolymer solution is uniformly applied on the mica substrate. Chloroform was evaporated to form a thin film. The triblock copolymer was aligned by exposing this thin film to chloroform vapor at room temperature for 4 days, and the PB phase was stained by exposing it to the vapor of an OsO ₄ solution. The dyed thin film was peeled from the mica substrate using the water surface, transferred to a copper grid for TEM observation, and subjected to TEM observation in the same manner as in Example 2. The obtained thin film had a thickness of about 80 nm.

  6 and 7 are diagrams showing the results of TEM observation of the surface of the film obtained in this example. The scale bar in FIG. 6 indicates 1 μm, and the scale bar in FIG. 7 indicates 2 μm. In FIG. 6, the black phase is the PB phase, the gray phase is the PS phase, and the white phase (matrix) is the PMMA phase. In FIG. 7, both the PB phase and the PS phase appear black. As shown in FIGS. 6 and 7, it was confirmed that the microphase separation structure including the helical structure and the cylinder structure of the polystyrene-polybutadiene-polymethyl methacrylate film was arranged in a hexagonal lattice pattern in the entire observed region. It was. Further, from the result of the three-dimensional reconstruction of the film obtained in this example, it was found that the PB phase formed a double helix.

  FIG. 9 is a cross-sectional view of the film obtained in this example. As shown in FIG. 9, in the film obtained in this example, the cylinder structure (and the central axis of the helical structure) is in relation to the film surface over the entire surface from one surface to the opposite surface of the film. It was confirmed that the absolute value of the disorder of the orientation angle of the vertically oriented portion was less than 20 ° while being vertically oriented.

[Example 5: Production of a film having a thickness of nanometer order]
The polystyrene-polybutadiene-polymethyl methacrylate obtained in Example 1 was dissolved in chloroform at 1.6 wt% to obtain a chloroform solution of a triblock copolymer. After the triblock copolymer solution is dropped on the mica substrate, the mica substrate is rotated by a spin coater at a rotation speed of 4000 rpm for 2 minutes, and the triblock copolymer solution is uniformly applied on the mica substrate. Chloroform was evaporated to form a thin film. The triblock copolymer was aligned by exposing this thin film to chloroform vapor at room temperature for 4 days, and the PB phase was stained by exposing it to the vapor of an OsO ₄ solution. The dyed thin film was peeled from the mica substrate using the water surface, transferred to a copper grid for TEM observation, and subjected to TEM observation in the same manner as in Example 2. The film thickness of the obtained thin film was 120 nm.

  FIG. 8 is a diagram showing the results of TEM observation of the surface of the film obtained in this example. In FIG. 8, the scale bar indicates 2 μm. In FIG. 8, the black phase is the PB phase, the gray phase is the PS phase, and the white phase (matrix) is the PMMA phase, but both the PB phase and the PS phase appear black. As shown in FIG. 8, it was confirmed that the microphase separation structure including the helical structure and the cylinder structure of the polystyrene-polybutadiene-polymethylmethacrylate film was arranged in a hexagonal lattice pattern in the entire observed region. Further, from the result of the three-dimensional reconstruction of the film obtained in this example, it was found that the PB phase formed a double helix.

  In the film obtained in this example, the cylinder structure (and the central axis of the helical structure) is oriented perpendicular to the film surface over the entire surface from one surface of the film to the opposite surface. In addition, it was confirmed that the absolute value of the disorder of the orientation angle of the vertically oriented portion was less than 20 °.

[Example 6: Control of outer diameter and pitch of helical structure by blending polymer block A]
Polystyrene (Mn = 8400, Mw / Mn = 1.03) was added to the polystyrene-polybutadiene-polymethyl methacrylate obtained in Example 1, and the polystyrene was added to the total amount of polystyrene-polybutadiene-polymethyl methacrylate and polystyrene. Blending was performed so that the weight fraction was 30%. In chloroform, polystyrene-polybutadiene-polymethylmethacrylate and polystyrene were dissolved so that the total amount was 5 wt% to obtain a chloroform solution. This chloroform solution was dropped into a glass petri dish, and the solvent was evaporated at room temperature for 24 hours to obtain a film having a thickness of 1000 μm. The prepared film was observed by TEM in the same manner as in Example 2.

  FIG. 11 shows the result of observing the film obtained in this example with TEM, together with the result of observing the film obtained in Example 2 with TEM. In FIG. 11, (a) shows the result of observing the film obtained in Example 2 by TEM, and (b) shows the film obtained by using a blend of polystyrene-polybutadiene-polymethyl methacrylate and polystyrene by TEM. The observation result is shown.

  As shown in FIG. 11, the helical pitch and the outer diameter of the helical structure in the film shown in (a) are 60 nm and 40 nm, respectively, whereas the helical pitch and the helical structure in the film shown in (b) are The outer diameter was 52 nm and 60 nm, respectively. From this example, it was found that by blending polystyrene with the polystyrene phase forming the cylinder structure that becomes the core of the helical structure, the helical pitch becomes narrower and the outer diameter of the helical structure becomes wider.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used in application fields such as a nanostructure material having a spiral structure, a nanoporous material, a nano stamp, a nano helix, and the like, and various processed products and devices using these. More specific application fields include electromagnetic wave absorbing materials in the ultra-high frequency region, sensors, antennas, high-performance membranes such as high-performance separation membranes and electrolyte membranes, and polarizing plate protective films (vertical alignment). It seems possible.

  Further, it can be applied to a microwave oven, a wireless LAN, a mobile phone using an electromagnetic wave absorbing material, and a fuel cell using an electrolyte membrane, which is very useful.

It is a figure which represents typically the nanostructure material concerning this invention. It is a figure which shows the result of the TEM observation of the film | membrane obtained in the Example. It is a figure which shows the result obtained by inclining the nanostructure material concerning this invention within a transmission electron microscope, acquiring a transmission image at various angles, and performing three-dimensional reconstruction. It is a figure which shows the result of the TEM observation of the film | membrane obtained in the Example. It is sectional drawing in the film | membrane surface of the film | membrane obtained in the Example. It is a figure which shows the result of having observed the surface of the film | membrane obtained in the Example by TEM. It is a figure which shows the result of having observed the surface of the film | membrane obtained in the Example by TEM. It is a figure which shows the result of having observed the surface of the film | membrane obtained in the Example by TEM. It is a figure which shows the result of having observed the cross section of the film | membrane obtained in the Example by TEM. It is a figure which shows "the absolute value of disorder of an orientation angle." It is a figure which shows the result of having observed the film | membrane obtained in the Example by TEM.

Claims (17)

An ABC-triblock copolymer comprising a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and a third polymer block C covalently bonded to the polymer block B. A nanostructured material containing a polymer and microphase-separated, wherein the phase consisting of polymer block C is a matrix, the phase consisting of polymer block A has a cylinder structure, and the phase consisting of polymer block B is A method for producing a nanostructured material having a helical structure around the cylinder structure as a core,
Polymer block A, polymer block B, and polymer block C are achiral,
The weight fraction of polymer block A in the ABC-triblock copolymer is 17% or more and less than 26%, the weight fraction of polymer block B is 4% or more and less than 12%, and the weight fraction of polymer block C Is 63% or more and less than 79%,
The interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B is χ _AB , and the interaction parameter between the repeating monomer constituting the polymer block B and the repeating monomer constituting the polymer block C Χ _BC , and the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block C is χ _AC , ABC-triblock satisfying χ _BC > χ _AB > χ _AC Dissolving the copolymer in a solvent;
A film forming step of forming a film containing the block copolymer using the obtained ABC-triblock copolymer solution;
Removing the solvent from the membrane to develop a microphase separation structure;
A method for producing a nanostructured material comprising: An ABC-triblock copolymer comprising a first polymer block A, a second polymer block B covalently bonded to the polymer block A, and a third polymer block C covalently bonded to the polymer block B. A microphase-separated nanostructured material comprising a polymer,
Polymer block A, polymer block B, and polymer block C are achiral,
The nanostructured material has a membrane shape;
The weight fraction of polymer block A in the ABC-triblock copolymer is 17% or more and less than 26%, the weight fraction of polymer block B is 4% or more and less than 12%, and the weight fraction of polymer block C is 63% or more and less than 79%,
The interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block B is χ _AB , and the interaction parameter between the repeating monomer constituting the polymer block B and the repeating monomer constituting the polymer block C Is χ _BC , and the interaction parameter between the repeating monomer constituting the polymer block A and the repeating monomer constituting the polymer block C is χ _AC , χ _BC > χ _AB > χ _AC is satisfied,
A phase consisting of polymer block C is used as a matrix, a phase consisting of polymer block A has a cylindrical structure, and a phase consisting of polymer block B has a helical structure around the cylinder structure as a core. Nanostructured material characterized by having.   The cylinder structure composed of the polymer block A penetrates from one surface of the membrane toward the opposite surface, and at least a part of the cylinder structure including an end portion of the cylinder structure constituting a part of the membrane surface is provided. The nanostructured material according to claim 2, wherein the nanostructured material is oriented perpendicularly to the film surface, and the absolute value of the disorder of the orientation angle of the vertically oriented part is less than 45 °.   The nanostructured material according to claim 2 or 3, wherein the nanostructured material has a film thickness of less than 1000 nm.   The cylinder structure is oriented perpendicular to the film surface over the entire surface from one surface to the opposite surface of the film, and the absolute value of the disorder of the orientation angle of the vertically oriented portion is 45. The nanostructured material according to claim 4, wherein the nanostructured material is less than 0 °.   The nanostructured material according to claim 2 or 3, wherein the nanostructured material has a film thickness of 1 µm or more and 1000 µm or less.   The nanostructured material according to any one of claims 2 to 6, wherein the helical structure is a double helical structure. The nanostructured material according to any one of claims 2 to 7 , wherein the ABC-triblock copolymer has a weight average molecular weight of 10,000 or more and 1,000,000 or less. The nanostructure material according to any one of claims 2 to 8 , wherein the cylinder structures are arranged in a hexagonal lattice pattern . The nanostructure material according to any one of claims 2 to 9 , wherein a distance between centers of the cylinder structures is 10 nm or more and 300 nm or less. The outer diameter of the helical structure, the nanostructured material according to any one of claims 2-10, characterized in that at 5nm or 150nm or less. The nanostructure material according to any one of claims 2 to 11 , further comprising a substrate, wherein the film is formed on the substrate. A nanoporous material obtained by removing the phase comprising the polymer block B of the ABC-triblock copolymer in the nanostructured material according to any one of claims 2 to 12 by decomposition or dissolution. The nanoporous material according to claim 13 is obtained by filling a metal, a semiconductor, or an inorganic compound, and then decomposing or dissolving the phase composed of the polymer block A and the phase composed of the polymer block C of the ABC-triblock copolymer. Nano stamp. A nanohelix in which the phase composed of the polymer block A and the phase composed of the polymer block C of the ABC-triblock copolymer in the nanostructured material according to any one of claims 2 to 12 is removed by decomposition or dissolution.   The method for producing a nanostructured material according to claim 1, wherein the outer diameter and pitch of the helical structure are changed by changing the weight fraction of the polymer block A. The method for producing a nanostructured material according to claim 1 or 16 , wherein the wire diameter of the helical structure is changed by changing the weight fraction of the polymer block B.