JP2010260994A - Metal-containing block copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a metal-containing block copolymer in which a significant amount of metal is contained at the nano level and regularly in a block copolymer. <P>SOLUTION: A mixed solution is prepared by dissolving a block copolymer including a polymer block phase A to which metal can perform coordinate linkage and a polymer block phase B to which the metal does not perform coordinate linkage, and a metal compound which is a compound of the metal, in a solvent in which the block copolymer and the metal compound can be dissolved and to which the metal can perform coordinate linkage, and then the solvent is removed. The solvation of the metal and the solvent can certainly prevent the metal from performing direct coordinate linkage to the polymer block phase A and aggregation. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a metal-containing block copolymer in which metal is regularly contained in a nanometer size and a method for producing the same.

  In recent years, composite materials containing metals at a nano level in a matrix such as polymer or glass have been developed, and their application to functional materials utilizing their unique optical properties, electrical and magnetic properties, or applications to catalysts and medicines. Is expected. For example, surface plasmon resonance (SPR) is generated by regularly including fine metal particles having a size equivalent to the wavelength of light in a matrix. Sensors, waveguides, optical devices, and the like using the surface plasmon resonance have been studied.

  In Phys. Rev. Lett. 95 (2005) 237401, silver or gold is processed into nano-rings with a diameter of several hundreds of nanometers, and a number of slits with a gap interval of about 10 nm are integrated into this, making it visible. It is described that an electric current flows by SPR in a wide frequency range covering the entire light, and an artificial magnetism can be expressed. Therefore, if a metamaterial in which such a fine metal integrated body is formed in a matrix is used, light can be bent freely and a negative refractive index can be realized.

  As one example of producing a composite material containing a metal at a nano level in a matrix such as polymer or glass, a method of mixing metal nanoparticles produced by PVD or CVD with a polymer solution or a molten polymer is known. ing. However, in this method, irreversible aggregates are easily formed when the metal nanoparticles are dispersed in the matrix, and the obtained product is not satisfactory as an optical functional material because light scattering occurs.

Therefore, in JP 2002-179931 A, a metal precursor such as AgBF ₄ salt is dissolved in a polymer solution and dispersed at a molecular level, and then the metal precursor is reduced by irradiation with light, A method for fixing metallic silver in a polymer at a nano level has been proposed. According to this production method, since the metal precursor can be dispersed at the nano level without agglomerating in the polymer matrix, the metal after reduction can also be dispersed at the nano level in the polymer matrix.

  However, this production method only provides a composite material in which metal particles are uniformly dispersed in the polymer matrix, and the metal particles cannot be regularly arranged in the polymer matrix. Therefore, there has been a problem that the field of use as a metal-containing nanostructure such as metamaterials and photonic crystals is restricted.

On the other hand, in Macromolecules, 2008, 41 (7), 2577-2583, a metal-containing block copolymer in which CdCl ₂ is regularly arranged at a nano level in a block copolymer composed of a polystyrene block and a polyvinylpyridine block. Is described. The manufacturing method is such that CdCl ₂ is mixed with a solution obtained by dissolving a block copolymer obtained by anionic polymerization in a mixed solvent of tetrahydrofuran / ethanol (8: 2), cast into a film, and then annealed. is there.

According to this metal-containing block copolymer, CdCl ₂ is immobilized at the nano level by coordinate bonding to the pyridine unit of the polyvinyl pyridine block. Therefore, CdCl ₂ is regularly arranged inside the block copolymer, such as a lamella structure, and the field of use as an optical functional material is greatly expanded.

JP 2002-179931 A

Phys. Rev. Lett. 95 (2005) 237401 Macromolecules, 2008,41 (7), 2577-2583

However in the non-patent document 2, when mixed with CdCl ₂ in excess of 0.2 mole with respect to pyridine units 1 mole of polyvinylpyridine block, it precipitates not uniformly coordinated to the block copolymer CdCl ₂ Is described. That is, it was difficult to complex CdCl ₂ exceeding 0.2 mol (4.4% by volume) with respect to 1 mol of pyridine unit while controlling the structure at the nano level. Therefore, since the metal-containing block copolymer obtained has a low metal content, there is a limit to the improvement of optical characteristics and other physical characteristics, and there is a limit to the expansion of the application field.

  This invention is made | formed in view of such a situation, and makes it the problem which should be solved to make a block copolymer contain a lot of metals regularly on a nano level.

  A feature of the method for producing a metal-containing block copolymer of the present invention that solves the above problems is that a block copolymer comprising a polymer block A phase in which a metal can be coordinated and a polymer block B phase in which a metal is not coordinated And a metal compound that is a compound of the metal, a dissolution step of preparing a mixed solution in which the block copolymer and the metal compound can be dissolved and in which the metal can coordinately bond, and from the mixed solution And a removing step for removing the solvent.

  The mixed solution preferably contains a metal compound in an amount of more than 0.2 mol and not more than 2.0 mol as a metal with respect to 1 mol of the coordinate-bondable unit of the polymer block A phase. Alternatively, it is desirable that the metal compound is contained in an amount of more than 4.4% by volume and not more than 33% by volume.

  The dissolving step is desirably performed by mixing a solution in which the block copolymer is dissolved in a solvent and a solution in which the metal compound is dissolved in the solvent. In the removing step, it is desirable to remove the solvent from the mixed solution at a rate of 10 ml / second or less. Further, at least one of an application step for adjusting the film thickness before the removal step, an annealing step for heating and holding the metal-containing block copolymer after the removal step, and a reduction step for reducing the metal-containing block copolymer is performed. Is desirable.

  A feature of the metal-containing block copolymer of the present invention is a metal-containing block copolymer produced by the production method of the present invention, in which a metal block coordinated with a polymer block A phase and the metal are coordinated. A block copolymer including a polymer block B phase that is not bonded, and a metal compound that is a compound of the metal selectively bonded to the polymer block A phase of the block copolymer. The metal compound is coordinated and bonded in an amount of more than 0.2 mol and less than 2.0 mol as a metal, or more than 4.4 vol% and less than 33 vol% as a metal compound per 1 mol of phase-coordinating units. There is to be.

  According to the production method of the present invention, a solvent in which the block copolymer and the metal compound can be dissolved and the metal can be coordinated is used. Accordingly, since the metal compound is first coordinated with the solvent molecule to be in a solvated state, the coordinated bond with the polymer block A phase is restricted in the mixed solution after the dissolution step. Therefore, even if the amount of the metal compound is large, a uniform mixed solution is obtained, and aggregation and precipitation do not occur.

  Thereafter, when the removal step is performed, it is considered that the solvent molecules in the mixed solution are released first, and then the solvent molecules coordinated to the metal compound are released. At this time, when one of the solvent molecules coordinated and bonded from the metal compound is released, the metal compound is coordinated and fixed to the polymer block A phase. Therefore, when the metal compound is 1 mol or less as a metal with respect to 1 mol of the unit capable of coordinate bonding of the polymer block A phase, the metal atom in the metal compound is respectively a unit capable of coordinate bonding of the polymer block A phase. Coordination bonds occur and the metal is contained in a nanometer size.

  In addition, when the metal compound exceeds 1 mol as a metal with respect to 1 mol of the coordination-bondable unit of the polymer block A phase, the excess metal compound is converted into a metal compound that is already coordinated by electrostatic interaction. It is considered that they are held close to each other, and no aggregation or precipitation occurs.

  Therefore, the metal compound is contained only in the polymer block A phase, and the block copolymer has a nanophase separation structure in which the polymer block A phase and the polymer block B phase are regularly arranged. A metal-containing block copolymer having a nanophase separation structure is obtained.

  That is, according to the production method of the present invention, a large amount of metal can be regularly contained in the block copolymer at a nano level. Therefore, in the obtained metal-containing block copolymer of the present invention, the metal compound is coordinated and bonded in an amount of more than 0.2 mol and not more than 2.0 mol as a metal with respect to 1 mol of the coordinate-bondable unit of the polymer block A phase. Moreover, since the metal compound is contained only in the polymer block A phase, the metal is regularly contained at the nano level. Therefore, the fields of use as metamaterials are greatly expanded.

In one Example of this invention, it is a chemical formula which shows the state in which the metal salt was solvated. It is a chemical formula which shows the composition of the mixed solution in one Example of this invention. It is a chemical formula which shows the stage in the middle of the removal process in one Example of this invention. 1 is a chemical formula showing a metal-containing block copolymer produced in one example of the present invention. The structure of the block copolymer containing no FeCl ₃ produced as a blank in one embodiment of the present invention is a TEM photograph showing. Is a TEM photograph showing the structure of an embodiment of FeCl ₃ 0.5 mole (11.2 vol%) prepared in Example-containing metal-containing block copolymer of the present invention. Is a TEM photograph showing the structure of a FeCl ₃ produced 2.0 mole (33% by volume) containing metal-containing block copolymer in Example 2 of the present invention. It is a DSC chart of the block copolymer which is a blank, and the metal containing block copolymer manufactured by one Example of this invention. It is a FT-IR chart of the block copolymer which is a blank, and the metal containing block copolymer manufactured by one Example of this invention. It is explanatory drawing which shows typically the reaction mechanism in the manufacturing method of this invention. It is explanatory drawing which shows the state of the metal containing block copolymer after the removal process in Example 1 and a comparative example.

  The block copolymer used in the production method of the present invention includes a polymer block A phase in which a metal can be coordinated and a polymer block B phase in which the metal is not coordinated. Other polymer blocks other than the polymer block A phase and B phase may be included. This block copolymer can be produced by a known polymerization method such as stepwise polymerization method, coupling method, living anion polymerization, living cation polymerization, living radical polymerization (RAFT polymerization, etc.).

  Here, the RAFT polymerization is a reversible addition-fragmentation chain transfer polymerization, and is abbreviated as a “reversible addition-fragmentation chain transfer agent” (hereinafter referred to as “RAFT agent”). ) Is used for polymerization. Examples of the RAFT agent include cumyl dithiobenzoate, S-1-dodecyl-S '(a, a "-dimethyl-a" -acetic acid) trithiocarbonate, 2-cyanoprop-2-yl dithiobenzoate, and the like.

  The polymer block A phase is a polymer in which a metal can be coordinated, and is preferably a polymer obtained by polymerizing a monomer containing an oxygen atom or a nitrogen atom having coordination ability. For example, polyvinyl pyridine, polyvinyl pyrrolidone, polyvinyl ether, polyethylene glycol, polypropylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid, polymethacrylic acid ester, polyvinyl acetate, polyvinylphenol, polyethylene terephthalate, polyamide, polyvinyl alcohol, polycarbonate And polyoxymethylene.

  The polymer block B phase is a polymer in which the metal does not coordinate bond, and is not particularly limited as long as it can be blocked with the polymer block A phase. For example, polystyrene, polyisoprene, polybutadiene, polyvinylidene fluoride, polyvinylidene chloride, polydimethylsiloxane, polyisobutylene, polyethylene, polypropylene, polyalkene and the like are exemplified. When the hardness of the metal-containing block copolymer is increased due to the coordinate bond of the metal, it is also preferable to use a soft polymer for the polymer block B phase.

  The composition ratio of the polymer block A phase and the polymer block B phase, the molecular weight of each, or the molecular weight of the block copolymer is not particularly limited, but when used as an optical functional material utilizing visible light, the structure of the block copolymer The period is preferably about 100 nm to 250 nm (1/4 to 1/3 times the visible light wavelength).

  The metal used in the present invention is capable of coordinating with at least a unit capable of coordinating bonding constituting the polymer block A phase. In general, a metal is likely to exist in an oxidized state in which electrons are lost, and since it can be coordinate-bonded, most metals, alloys, or intermetallic compounds can be used. When used as an optical functional material, it is preferable to contain Cu, Ag, Au, etc., for example.

Examples of the metal compound include acetylacetone salts, bromides, chlorides, iodides, oxides, nitrates, sulfates, carbonates, acetates, phosphates, and hydrides of the metals that are soluble in the solvent described below. Used. For example, in the case of FeCl ₃ , the mixed amount of the metal compound is in the range of more than 0.2 mol and less than 2.0 mol as Fe with respect to 1 mol of the coordination-bondable unit of the polymer block A phase, and the volume fraction is 4.8 volumes. % To 33% by volume is desirable. In the case of zinc bromide (ZnBr ₂ ), 0.2 to 2.0 mol corresponds to 4.5 vol% to 32 vol%, and in the case of copper bromide (CuBr), 0.2 to 2.0 mol is 2.6 vol% to 21 vol. Corresponds to volume%.

  The solvent used in the present invention is not particularly limited as long as the block copolymer and the metal compound can be dissolved and the metal can be coordinated, and can be removed in the removing step, particularly water, alcohol, Examples include pyridine, pyrrolidone, amines, aqueous ammonia and the like. These solvents may be used alone, or a mixed solvent in which a plurality of solvents are mixed may be used. The mixing amount of the solvent is not less than the amount in which the block copolymer and the metal compound are completely dissolved.

  In the dissolution step, a mixed solution in which the block copolymer and the metal compound are dissolved in a solvent is prepared. At this time, when the metal of the metal compound is coordinated to the polymer block A phase before the metal is coordinated to the solvent, the metal is coordinated to the other polymer block A phase to be in a crosslinked state, resulting in aggregation There is. Therefore, it is desirable to mix a solution in which the block copolymer is previously dissolved in a solvent and a solution in which the metal compound is previously dissolved in a solvent. By doing in this way, a metal compound and a solvent can be coordinate-bonded reliably and it can prevent reliably that aggregation arises.

  In addition, when the speed at which the metal coordinates to the polymer block A phase is different from the speed at which the metal coordinates to the solvent, the speed at which the metal coordinates to the solvent is greater than the speed at which the metal coordinates to the polymer block A phase. In addition, it is desirable to select the type of solvent or polymer block A phase.

  In the removal step, it is considered that the solvent molecules in the mixed solution are first released, and then the solvent molecules coordinated to the metal compound are released. At this time, when one of the solvent molecules coordinated and bonded from the metal compound is released, the metal compound is coordinated and fixed to the polymer block A phase. Therefore, when the metal compound is less than 1 mole of the metal as a metal with respect to 1 mole of the unit capable of coordination bonding in the polymer block A phase, each metal atom of the metal compound is coordinated with the unit capable of coordination bonding in the polymer block A phase. Coordinated, and the metal will be contained in a nanometer size.

  This removal step can be performed by a general drying method in which the mixed solution is heated to evaporate the solvent. It is also preferable to dry in a reduced pressure atmosphere. However, if the removal step is performed rapidly, the rate at which the solvent is released from the solvated metal compound and the rate at which the solvent in the mixed solution evaporate are close to each other, and the polymer block A phase may be crosslinked and aggregated by the metal compound. is there. Therefore, it is desirable to make the solvent removal rate as small as possible, and it is preferable to remove it at a rate of 10 ml / second or less.

  The obtained metal-containing block copolymer may be used as it is, but the coating step for adjusting the film thickness before the removing step, or the annealing step and the metal-containing block for heating and holding the metal-containing block copolymer after the removing step. It is desirable to perform at least one of a reduction process for reducing the copolymer. Using a bar coater, a spin coater or the like, the film thickness can be adjusted by appropriately adjusting the concentration of the mixed solution and performing the coating step. Moreover, the nanophase separation structure of the metal-containing block copolymer can be made more uniform by performing the annealing step. The heating temperature is preferably equal to or higher than the glass transition temperature of the polymer block B phase not containing metal. Further, by performing the reduction step, the metal compound can be reduced to metal, and the degree of freedom in the field of use is further increased.

  Hereinafter, the present invention will be described specifically by way of examples.

<Preparation of block copolymer>
The RAFT agent {S-1-dodecyl-S '(a, a "-dimethyl-a" -acetic acid) trithiocarbonate} shown in [Chemical Formula 1] is dissolved in styrene monomer and polymerized at 130 ° C for 6 hours. Thus, a polystyrene block was synthesized. Subsequently, 4-vinylpyridine monomer was added and polymerized at 70 ° C. for 1 hour to synthesize a block copolymer shown in [Chemical Formula 2].

This block copolymer is composed of a polyvinylpyridine block (hereinafter referred to as polymer block A phase) and a polystyrene block (hereinafter referred to as polymer block B phase). The number average molecular weight is 48,000, the molecular weight distribution is 1.30, and the volume fraction of the polymer block A phase is 0.60.

<Dissolution process>
Pyridine was added to the obtained block copolymer solution to prepare a polymer solution having a block copolymer concentration of 4% by mass. Commercially available FeCl ₃ was dissolved in pyridine to prepare a metal salt solution having a FeCl ₃ concentration of 2 mass%. Then, the polymer solution and the metal salt solution were mixed at a volume ratio of 1: 1 to prepare a mixed solution. The mixed solution was in a uniform solution state without causing aggregation or precipitation.

This mixed solution has a block copolymer: FeCl ₃ = 3: 1 by mass ratio, and contains 0.5 mol of FeCl ₃ with respect to 1 mol of pyridine units in the polymer block A phase. The volume fraction of FeCl ₃ is 11.2%.

<Removal process>
The mixed solution was transferred to a Teflon (trademark) container and kept at 50 ° C. for 36 hours to evaporate pyridine. The evaporation rate is 5 μl / min. The block copolymer film after the removal step was a uniform brown transparent body having no aggregation or separation as shown in FIG. In this removal step, it is assumed that the following reaction occurred.

In the FeCl ₃ pyridine solution, FeCl ₃ is in the solvated state shown in FIG. Even if this is mixed with the polymer solution, the state does not change, and the block copolymer 1 and the solvate 2 of FeCl ₃ are dissolved in pyridine 3 as shown in FIG.

Pyridine coordinated with FeCl ₃ is less likely to evaporate than pyridine as a solvent. Therefore, when pyridine is gradually evaporated from this solution, the solvent pyridine first evaporates. When the amount of pyridine as a solvent decreases, pyridine coordinated to FeCl ₃ solvate 2 also evaporates. However, when one of the three pyridines is released, the Fe atom from which the pyridine is released is coordinated with the pyridine unit of the polymer block A phase in the block copolymer 1, as shown in FIG. Thereafter, the remaining pyridine coordinated to Fe is released, so that a uniform metal-containing block copolymer having no aggregation or separation is generated as shown in FIG.

<Annealing process>
Subsequently, it was kept at 160 ° C. for 60 hours to obtain a uniform film-like metal-containing block copolymer.
[blank]
Pyridine was added to the block copolymer produced in Example 1 to prepare a polymer solution having a block copolymer concentration of 4% by mass. Only this polymer solution was transferred to a Teflon (trademark) container, and pyridine was evaporated and annealed in the same manner as in Example 1 to obtain a block copolymer film containing no FeCl ₃ as a blank.

<TEM observation>
The blank block copolymer film and the metal-containing block copolymer film of Example 1 were observed by TEM under the condition of an acceleration voltage of 100 kV. The results are shown in FIGS. The blank block copolymer film is dyed with iodine. FIG. 7 shows a TEM photograph of a metal-containing block copolymer film containing 2.0 mol (33% by volume) of FeCl _{3 according to} Example 2 described later.

  FIG. 5 shows that a dark gray portion exists in an island shape in a light gray sea, and the dark gray portion forms a nanophase separation structure of a cylinder structure. On the other hand, FIG. 6 shows a lamellar nanophase separation structure in which a light gray portion and a dark gray portion are formed in layers. FIG. 7 also shows that the light gray portion is a nanophase separation structure having a cylindrical structure.

That By containing FeCl _3, as further becomes large content of FeCl _3, 5, 6, morphology transition changes to 7 was observed to occur. The metal-containing block copolymer according to FIGS. 6 and 7 could clearly observe the lamella structure without being dyed.

<DSC measurement>
DSC measurement was performed on the blank block copolymer film and the metal-containing block copolymer film of Example 1 under the conditions of a temperature increase rate of 10 ° C./min and a temperature range of 20 to 250 ° C. It was. The results are shown in FIG. In FIG. 8, the endothermic peak near 108 to 109 ° C. is attributed to the polymer block B phase, and the endothermic peak near 152 ° C. is attributed to the polymer block A phase. The endothermic peak due to the polymer block A phase disappears from the metal-containing block copolymer, which indicates that Fe atoms are selectively dispersed only in the polymer block A phase.

<FT-IR measurement>
The blank block copolymer film and the metal-containing block copolymer film of Example 1 were each dissolved in pyridine, coated on a KBr plate, and vacuum-dried at 120 ° C. These were subjected to FT-IR measurement under atmospheric pressure, detector: TGS, resolution: 2 cm ⁻¹ . The results are shown in FIG. The film of the metal-containing block copolymer of Example 1 was completely dissolved in pyridine. This means that there are no irreversible aggregates in the film.

As shown in FIG. 9, the metal-containing block copolymer has an absorption peak at 1613 cm ⁻¹ , indicating that Fe is coordinated to the unpaired electron of the pyridine unit in the polymer block A phase. Yes.

<Discussion>
Therefore, it was observed that morphological transition occurred in TEM by containing FeCl _3, as schematically shown in FIG. 10, the Fe atom of FeCl ₃ was coordinated only to the polymer block A phase. This is considered to be due to the increase in the volume of the polymer block A phase. That is, in the blank block copolymer 1, the polymer block A phase 11 exists in a cylinder structure in the sea of the polymer block B phase 10 as shown in FIG. When FeCl ₃ is added thereto, Fe atoms are selectively coordinated to the polymer block A phase 11. Then, it is considered that the volume of the polymer block A phase 11 is increased and the polymer block A phases 11 adjacent to each other are connected to form a lamellar structure.

  In addition, since the lamellar structure was confirmed also by structural observation by small angle X-ray scattering (SAXS), the metal-containing block copolymer of Example 1 has a nanophase separation structure similar to that in FIG. It is clear that

That is, in the metal-containing block copolymer obtained in Example 1, FeCl ₃ is selectively coordinated to the pyridine unit of the polymer block A phase of the block copolymer, and a nanophase separation structure having a lamellar structure is formed. There is no. Moreover, even though FeCl ₃ is contained in a large amount of 0.5 mole per mole of pyridine unit in the polymer block A phase, it is a metal-containing block copolymer having a uniform composition without problems such as aggregation and separation. It was.

In the dissolution step, FeCl ₃ was added in an amount of 0.2 to 2.0 moles per mole of pyridine units in the polymer block A phase in the same manner as in Example 1 except that the mixing ratio of the polymer solution and the metal salt solution was variously changed. 4.8 vol% to 33 vol%) containing metal-containing block copolymers were prepared.

  When the obtained metal-containing block copolymer was observed by TEM in the same manner as in Example 1, the nanophase separation structures shown in Table 1 were observed. The mixed solution and film in each example had a uniform composition without aggregation and separation as in Example 1.

As shown in FIGS. 5 and 10, the cylinder structure of the polymer block A phase means a state in which the polymer block A phase is regularly arranged in an elongated cylindrical shape in the sea of the polymer block B phase. As shown in FIG. 7, the cylinder structure of the block B phase refers to a state in which the polymer block B phase is regularly arranged in an elongated cylindrical shape in the sea of the polymer block A phase. It can be seen that as the molar ratio of FeCl ₃ increases, the volume of the polymer block A phase increases, so that the transition from the cylinder structure to the lamellar structure and further to the cylinder structure of the polymer block B phase.

That is, according to the production method of the present invention, the FeCl ₃ against pyridine units 1 mole of the polymer block A phase can be coordinated in an amount greater than 0.2 mole (4.8 vol%), the FeCl ₃ 2.0 moles ( It is clear that a stable nanophase separation structure can be formed even if it is contained up to 33% by volume).

Instead of FeCl ₃ , acetylacetone nickel (II) {Ni (acac) ₂ }, zinc bromide {ZnBr ₂ }, silver nitrate (I) {AgNO ₃ }, iron oxide (III) {Fe ₂ O ₃ }, bromide A metal-containing block copolymer was produced in the same manner as in Example 1 (metal content 0.5 mol) except that copper (I) {CuBr} was used.

Uniform films were obtained with any of the metal compounds. When they were observed with a TEM, the same lamellar structure as in FIG. 6 was confirmed.
[Comparative example]
A polymer solution and a metal salt solution were prepared in the same manner as in Example 1 except that chloroform was used instead of pyridine. When the polymer solution and the metal salt solution were mixed, precipitation and separation due to aggregation occurred. Further, a removal step for removing chloroform was performed in the same manner as in Example 1. However, as shown in FIG. 10, a non-uniform lump was formed, and the subsequent experiment was canceled.

That is, since Fe atoms do not coordinate with chloroform, the Fe atoms coordinate to the polymer block A phase at the moment when the polymer solution and the metal salt solution are mixed, and FeCl ₃ passes between the other polymer block A phases. Aggregation is considered to have occurred due to crosslinking.

  The metal-containing block copolymer of the present invention includes surface enhanced Raman scattering, surface enhanced infrared absorption, biosensor, scanning near-field optical microscope, waveguide, surface plasmon excitation device, energy enhancement device, optical regular processing device, light In addition to being used for recording / reproducing devices, photonic crystal devices, etc., it is also expected to be used as various templates as they are, or by reducing metals or burning organic substances.

1: Block copolymer
10: Polystyrene block phase (polymer block B phase)
11: Polyvinylpyridine block phase (polymer block A phase)

Claims (7)

A block copolymer comprising a polymer block A phase capable of coordinate bonding with a metal and a polymer block B phase to which the metal does not coordinate bond, and a metal compound which is a compound of the metal, the block copolymer and the block copolymer A dissolution step of preparing a mixed solution in which a metal compound can be dissolved and the metal can be coordinated;
A removal step of removing the solvent from the mixed solution, and a method for producing a metal-containing block copolymer.   2. The metal according to claim 1, wherein the mixed solution contains the metal compound in an amount of more than 0.2 mol and not more than 2.0 mol as a metal with respect to 1 mol of the coordinate-bondable unit of the polymer block A phase. A method for producing a containing block copolymer.   The metal-containing block copolymer according to claim 1 or 2, wherein the dissolution step is performed by mixing a solution in which the block copolymer is dissolved in the solvent and a solution in which the metal compound is dissolved in the solvent. Manufacturing method of coalescence.   The method for producing a metal-containing block copolymer according to any one of claims 1 to 3, wherein the removing step removes the solvent from the mixed solution at a rate of 10 ml / second or less.   5. The metal-containing block copolymer according to claim 1, further comprising at least one of an annealing step for heating and holding the metal-containing block copolymer and a reduction step for reducing the metal-containing block copolymer after the removing step. A method for producing a polymer.   The method for producing a metal-containing block copolymer according to any one of claims 1 to 5, wherein the polymer block A phase includes a pyridine ring, and the solvent includes pyridine. A metal-containing block copolymer produced by the production method according to claim 1,
A block copolymer comprising a polymer block A phase in which a metal can be coordinated and a polymer block B phase in which the metal is not coordinated; and a coordinate bond selectively to the polymer block A phase of the block copolymer A metal compound that is a compound of the metal
The metal-containing block copolymer wherein the metal compound is coordinated and bonded in an amount of more than 0.2 mol and not more than 2.0 mol as a metal with respect to 1 mol of the coordinate-bondable unit of the polymer block A phase. .