KR20100032718A - Method for fabrication of nanostructured particles from block copolymers using emulsion droplets - Google Patents

Abstract

PURPOSE: A manufacturing method of nano-structured fine particles using droplet is provided to selectively control a shape of a particle and to control nanostructure of a copolymer which is assembled with surfactants. CONSTITUTION: A manufacturing method of nano-structured fine particles using droplet includes the following steps: preparing a block copolymer(S101); manufacturing a block copolymer dispersion solution(S102); forming the droplet of the block copolymer by agitating the block copolymer dispersion solution, a droplet guiding solution and surfactant(S103); forming fine particles by evaporating a solvent of the block copolymer droplet(S104); and attaching a compound and a metal nanoparticle on the surface of the fine particles.

Description

Method for fabrication of nanostructured particles from block copolymers using emulsion droplets}

The present invention relates to a method for producing nanostructured microparticles using droplets, and more particularly, by controlling a nanostructure of a block copolymer to be self-assembled by participating in a self-assembly process of a block copolymer. The present invention relates to a method for producing nanostructured microparticles using droplets capable of selectively implementing shapes.

A method of preparing a micrometer-sized particle having a nano structure, and a method of preparing the particle through self-assembly by evaporating a solvent in an aerosol containing a block copolymer and a silica precursor ( Nature 398, 223, 1999 ). However, it is not easy to control the evaporation rate and the reaction of the solvent, there is a difficulty in the operation of the aerosol, and also the nanostructure of the prepared particles is limited to a multilayer concentric form.

In addition, the emulsion polymerization method ( Langmuir, 23, 5978, 2007 ) in which the block copolymer is self-assembled by preparing an emulsion including a block copolymer and removing the solvent in the emulsion, and by modifying the emulsion polymerization method, a multi-layer surface coating Although a method of manufacturing polymer particles having a similar multilayer structure through advanced processes ( Advanced Functional Materials, 18, 1961, 2008 ) has been reported, these methods are also confined to concentric shapes of nanostructured particles.

On the other hand, when the block copolymer is dissolved in a mixed solution of water and THF (Tetrahydrofuran) and then THF is selectively removed, the block copolymer is spherically aggregated ( Advanced Materials, 17, 2062, 2005 ). It is difficult to control the size and structure.

The present invention has been made to solve the above problems, by controlling the nanostructure of the block copolymer to be self-assembled by participating in the self-assembly process of the block copolymer, the shape of the particles can be selectively implemented. It is an object of the present invention to provide a method for producing nanostructured microparticles using droplets.

In addition, the present invention is another object to enable the functional patterning of the microparticles by inducing a selective reaction on the surface of the microparticles by introducing a reactor to the surfactant. Along with this, another purpose is to prepare a fine particle having nano pores by selectively removing a part of the block copolymer.

Nanostructured microparticles manufacturing method using the droplets according to the present invention for achieving the above object comprises the steps of (a) preparing a block copolymer, (b) preparing a block copolymer dispersion solution, and the block (C) forming a block copolymer droplet by stirring the copolymer dispersion solution, the droplet inducing solution and the surfactant, and (d) evaporating the solvent of the block copolymer droplet to form fine particles. It features.

After the step (d), may further comprise the step of attaching the compound or metal nanoparticles on the surface of the microparticles, in this case the surfactant includes a surfactant comprising a specific reactor, the compound or metal The surface of the nanoparticles may be provided with a reactor that reacts with a specific reactor of the surfactant.

In addition, the metal nanoparticles are included in the block copolymer dispersion solution, and the same component as a specific component among a plurality of components constituting the block copolymer may be applied to the surface of the metal nanoparticles. In this case, the metal nanoparticles are self-assembled in the specific component of the microparticles, the specific component may be the same as the component applied to the surface of the metal nanoparticles.

Meanwhile, after the step (d), the method may further include mixing metal precursors reacting with specific components of the block copolymer with the microparticles so that the metals are self-assembled in the specific components of the microparticles.

The block copolymer may be any one or a combination of an organic block copolymer, an organic-inorganic copolymer, an inorganic-inorganic block copolymer, and the same component as each block of the different components constituting the block copolymer. At least one homopolymer having may be added to the block copolymer. On the other hand, the concentration of the block copolymer in the block copolymer dispersion solution is preferably in the range of 0.01 to 10wt%.

The solvent and the droplet inducing solution of the block copolymer dispersion solution are composed of water or oil, and when the solvent of the block copolymer dispersion solution is water, the droplet inducing solution is oil, and the solvent of the block copolymer dispersion solution is oil. The droplet inducing solution is water. In addition, the oil has a continuous phase or a dispersed phase and is any one of toluene, silicone oil, dodecane, hexadecane.

After the step (d), may further comprise the step (e) of removing the specific components constituting the microparticles to produce nanoporous microparticles, the specific components constituting the microparticles through ultraviolet irradiation Can be removed.

The block copolymer is a polystyrene-b-polybutadiene (PS-b-PB) double block copolymer, polystyrene-b-poly-4-vinylpyridine double block copolymer , Polystyrene-b-polymethylmethacrylate (polystyrene-b-polymethylmethacrylate) may be any one or a combination of the double block copolymer, a triple block copolymer composed of the components constituting the double block copolymer may also be used. .

Meanwhile, as the surfactant, an amphiphilic block copolymer including at least one or more of the components constituting the block copolymer may be used, and two or more amphiphilic block copolymers may be used as the surfactant. Such amphiphilic block copolymers for surfactants include polystyrene-b-polyethyeleneoxide, polybutadiene-b-polyethyeleneoxide block copolymers, and polyethylene oxide-polypropylene oxide-polyethylene oxide triple blocks. Ester-like polymeric surfactants with long-chain alkyl and OH-groups (polyethyleneoxide-polypropyleneoxide-polyethyleneoxide), sorbitan monooleate, long-chain alkyl, and OH-groups Any one or a combination thereof.

Nanostructured microparticles manufacturing method using the droplets according to the present invention has the following effects.

Self-assembled nanostructured microparticles can be prepared by evaporating the solvent from the block copolymer droplets, and upon forming the droplets, the nanostructure of the microparticles can be selectively selected by adding a surfactant having the same components as the specific block of the block copolymer. Can be controlled. In addition, the nanoporous microparticles may be easily prepared by removing specific components of the prepared microparticles through ultraviolet irradiation.

Such nanostructured microparticles can be used as a carrier for catalysts, materials for the production of photonic crystals, or sensors using surface plasmon properties, or electronic paper using anisotropic polarization properties.

The method for producing nanostructured microparticles using the droplets according to the present invention is characterized by preparing a fine particle having a nanostructure by removing a solvent from the droplet containing the block copolymer.

Specifically, the method for producing nanostructured microparticles using droplets according to the present invention includes preparing a block copolymer as shown in FIG. 1 (S101), preparing a block copolymer dispersion solution (S102), and a liquid. It comprises the step of forming an enemy (S103) and the fine particles are formed by self-assembly (S104). Each step will be described in detail as follows.

(a) preparing a block copolymer

The block copolymer is contained in the droplets, and finally, when the solvent constituting the droplets evaporates, the block copolymers self-assemble to form nanostructured microparticles.

As such a block copolymer, any one of organic block copolymers, organic-inorganic copolymers, inorganic-inorganic block copolymers, or a combination thereof may be used. In this case, the organic block copolymer, the organic-inorganic copolymer, the inorganic-inorganic block copolymer, and the like are multi-block copolymers composed of two or more different blocks, and at least one of the multi-block copolymers or a combination thereof. The above homopolymer may be added.

The homopolymer may be configured to be the same as any one of the blocks constituting the multi-block copolymer, thereby controlling the nanostructure of the finally formed microparticles from the lamellar phase to tubular or spherical can do. In addition, the inclusion of homopolymers having the same component as each block constituting the multi-block copolymer together in the droplets may increase the period of the nanostructure of the microparticles.

The block copolymer is preferably a polymer material having a controlled molecular weight distribution and having a low polydispersity index of 1.1 or less. For example, polystyrene-polybutadiene having a molecular weight of several hundred thousand to several million. (Polystyrene-b-Polybutadiene, PS-b-PB) double block copolymer, polystyrene-polyvinylpyridine double block copolymer, polystyrene-polybutadiene-polystyrene (PS-b-PB-b-PS) triple block copolymer This can be used. On the other hand, the block copolymer may be prepared by an anion polymerization method or RAFT (Reversible additional fragmentation chain transfer) polymerization method.

(b) preparing a block copolymer dispersion solution

The block copolymer dispersion solution may be prepared by dispersing the block copolymer in water or oil. At this time, the concentration of the block copolymer in the block copolymer dispersion solution may be adjusted to 0.01 to 10wt% range. Here, when the concentration of the block copolymer is 0.01wt% or less, the evaporation time of the droplets is long, and the self-assembly process of the microparticles is delayed, and when 10wt% or more, the microparticles may not self-assemble.

The concentration of the block copolymer directly affects the size of the droplets and the size of the finally formed fine particles. The higher the concentration of the block copolymer, the larger the size of the droplets and the size of the fine particles. Specifically, the size of the microparticles is directly proportional to the size of the droplets and is proportional to one third of the concentration of the block copolymer.

(c) forming droplets

Droplet refers to the change of a specific fluid in the form of droplets due to the difference in surface tension by applying mechanical force to two kinds of unmixed fluids. In the present invention, the block copolymer dispersion solution is a liquid induction solution such as water or oil. To form block copolymer droplets.

Specifically, an emulsion is formed when a block copolymer dispersion solution and a droplet induction solution are prepared and the two solutions are stirred using an emulsifier (homogenizer, colloid mill, high-speed turbine exchanger, etc.) to form an emulsion. The block copolymer droplets in which the solution is granulated are dispersed and formed. In this case, when the solvent of the block copolymer dispersion solution is water, the droplet induction solution should be oil. On the contrary, when the solvent of the block copolymer dispersion solution is oil, water is used as the droplet induction solution. When the droplet inducing solution is an oil, it may be selected from the group consisting of a material having a low solubility in water and high solubility of the block copolymer such as toluene, silicone oil, dodecane, hexadecane, and the like. In addition, in addition to the emulsifier, a droplet is formed through a micropipette or a microfluidic device, which is a method of using viscous stress in a coflowing stream, or a mixture of two liquids is shaken to shake a liquid of a polydispersion system. You can also form enemies.

Meanwhile, in forming the block copolymer droplets, in order to stabilize the droplets and control the nanostructure of the finally formed microparticles, the mixed solution of the two solutions, that is, the mixed solution of the block copolymer dispersion solution and the droplet induction solution, may be used. Add surfactant.

The surfactant interacts with the block copolymer in the process of evaporating the solvent of the droplet to self-assemble the block copolymer in the droplet to form microparticles, whereby the affinity of each component of the block copolymer with the surfactant The internal nanostructure of the block copolymer is changed.

In order to control the affinity with each component of such a block copolymer, when a block copolymer composed of two blocks of different components is used, the amphiphile in which one of the two components is included and the water or oil-friendly block is connected Block copolymers may be used alone or as a mixture. For example, when a block copolymer having a lamella phase is used, an emulsion is formed by using, as a surfactant, an amphiphilic block copolymer having a friendly group with a specific block constituting the block copolymer. Finally, when the solvent of the emulsion is removed, microparticles having an onion-like multilayer concentric nanostructure are formed, and at this time, a block copolymer phase having the same components as the amphiphilic block copolymer is formed at the outermost part of the microparticles. In addition, the thickness of the outermost layer of the microparticles can also be adjusted according to the block length of the amphiphilic block copolymer used as the surfactant.

In addition, the surfactant may be selected according to the droplet and the continuous phase of the droplet, when the oil droplet is formed in water amphiphilic block comprising at least one or more of the components constituting the block copolymer dissolved inside the droplet Copolymers or two or more amphiphilic block copolymers may be used as the surfactant.

For example, when polystyrene-polybutadiene is used as the block copolymer in the droplets, the amphiphilic block copolymer for the surfactant may be polystyrene-b-polyethyeleneoxide, polybutadiene-polyethyleneyeoxide (polybutadiene-b-polyethyeleneoxide). ) Block copolymers, polyethylene oxide-polypropylene oxide-polyethylene oxide triple block copolymers (polyesteroxide-polypropyleneoxide-polyethyleneoxide), sorbitan monooleate, long-chain alkyl, ester-like polymeric surfactants with OH-groups (ester-like polymeric surfactant with long-chain alkyl and OH-groups) or any combination thereof.

(d) forming fine particles by self-assembly

In the state where the block copolymer droplets are prepared, evaporation of the solvent constituting the block copolymer droplets causes the block copolymer droplets to gradually diffuse into the continuous phase, and the concentration of the block copolymer is gradually increased. Or evaporation-induced self-assembly with microparticles having a size of less than that (see FIG. 7). At this time, the self-assembled microparticles have a nanostructure, such as plate, tubular, spherical, depending on the molecular weight ratio of the block copolymer, the interaction force between the blocks and the affinity between the surfactant and the block. In addition, the self-assembled microparticles are directly proportional to the size of the block copolymer droplets as described above and are proportional to 1/3 square the concentration of the block copolymer. For reference, circular microparticles and elliptical microparticles are shown in FIG. 7, wherein the circular microparticles are used when a single surfactant is composed of one component, and the elliptic microparticles have two components ( This is the case where a mixed surfactant made of polystyrene (PS) and polybutadiene (PB) is used.

Meanwhile, nanoporous microparticles having nano-sized pores may be prepared by selectively removing specific blocks among a plurality of blocks constituting the block copolymer from the self-assembled microparticles having nanostructures through ultraviolet irradiation. have. In this case, in the case of the organic-inorganic block copolymer, the organic component may be removed to prepare nanoporous inorganic microparticles.

In addition, an additional process may be applied to impart specific functions to the self-assembled microparticles having nanostructures. That is, specific functions may be imparted to the microparticles through a method of functional patterning the surface of the microparticles and a selective reaction method in the microparticles.

First, a method of functional patterning the surface of the microparticles is as follows.

Certain reactors may attach certain compounds or metal nanoparticles to the surface of the microparticles by reacting the compound or metal nanoparticles with the microparticles. To this end, the surface of the microparticles should include a reactor capable of reacting with the reactor of the compound or metal nanoparticles, the reactor of the microparticles can be obtained from the surfactant.

Specifically, when the emulsion is formed, a surfactant having a reactor capable of reacting with the reactor of the compound or metal nanoparticles and a reactor-free surfactant are added together to form an emulsion, and fine particles are formed through self-assembly. A reactor is formed on the surface of the produced microparticles. For example, when a polystyrene-polyacrylic acid block copolymer and a polybutadiene-polyethylene oxide are used as a surfactant, a carboxyl group (COOH) in polyacrylic acid is provided on the surface of the microparticles.

In such a state, when the resulting fine particles, for example, microparticles having a carboxyl group (COOH) and a compound or metal nanoparticles having a reactor, for example, an amine group (NH ₂ ), are mixed with water, FIG. 8. The compound or metal nanoparticles are attached onto the surface of the microparticles through an amide bond reaction (amide) as shown in FIG. By applying such a reaction, when the end group of the DNA is substituted with an amine group, the DNA can be selectively attached to the surface of the microparticles through the amide bond reaction as described above.

Next, look at how to give a specific function to the microparticles through a selective reaction in the microparticles. As a first method for realizing this, a specific component of a plurality of components constituting the block copolymer is applied to the surface of the metal nanoparticle, and the metal nanoparticle is included in the block copolymer droplet through the block copolymer dispersion solution. Then, when the microparticles are formed through self-assembly, the <metal nanoparticles having the same components as the specific components of the block copolymer on the surface> may be selectively self-assembled only within the same component among the plurality of components constituting the block copolymer. Done. That is, the metal nanoparticles are provided only within specific components in the self-assembled microparticles. FIG. 9 shows that polystyrene (PS) is applied to the surface to stabilize gold nanoparticles contained within the block copolymer droplets and ultimately self-assemble into the polystyrene layer of microparticles.

As a second method for the selective reaction in the microparticles, a microparticle having a metal nanostructure is prepared by mixing a metal precursor reacting with a specific component of the block copolymer with the microparticle so that the metal self-assembles only within the specific component of the microparticle. can do. In this case, the unique phenomenon that the metal nanostructure combines with light, that is, the surface plasmon phenomenon can be realized in the microparticles, and the surface plasmon phenomenon can be freely controlled by controlling the nanostructure in the microparticles. In addition, if the biomaterial selectively adheres to the surface of the microparticles, it can be applied as a device that can be detected using light. 10 illustrates a case where the gold precursor (HAuCl ₄ ) reacts with a specific component of the block copolymer.

On the other hand, it is also possible to react the metal material to the dark portion of the fine particles, in this case it can be applied as a display device. Specifically, as shown in FIG. 11, when the metal plate made of the metal material in the microparticles is parallel to the direction of the electric field (see FIG. 11 (a)), the light is perpendicular to the case (see FIG. 11 (b)). A difference occurs in the degree of absorption, which can be applied to a polarizing plate or the like as shown in FIG.

Hereinafter, a method for producing nanostructured microparticles using droplets according to an embodiment of the present invention will be described in detail.

<Example 1>

A block copolymer dispersion solution was prepared by dispersing a polystyrene-polybutadiene double block copolymer (PS-b-PB) having a molecular weight of 300,000 and a polystyrene mass ratio of 46% in toluene at 0.2wt%. Then, the prepared block copolymer dispersion solution was mixed with water in which 1 wt% of a surfactant (polyethylene oxide-polypropylene oxide-polyethylene oxide, Pluronic F108) was dispersed to form a block copolymer droplet. At this time, droplet formation was performed using a homogenizer, the speed was 8500 rpm, and the stirring time was 1 minute.

The droplets thus produced were evaporated at a temperature of 95 ° C., and as a result, polystyrene-polybutadiene was self-assembled to form fine particles having spherical nanostructures as shown in FIG. 2. The formed microparticles are distributed with a size of 1 ~ 10㎛, the internal structure of the microparticles are in the form of onion and two kinds of polymers, that is, polystyrene and polybutadiene are alternately arranged, each layer is concentric circles Able to know.

<Example 2>

The experiment was conducted in the same manner as in Example 1 except for the surfactant, and polystyrene-b-polyethylene oxide (PS-b-PEO) and polybutadiene-polyethylene oxide (Polybutadiene) were used as the surfactant. -b- Polyethyleneoxide, PB-b-PEO) was used.

In PS-b-PEO, one component of the surfactant, the weight average molecular weight (MW) of polystyrene was 3600, the weight average molecular weight of polyethylene oxide was 16600, and the ratio of the number average molecular weight to the weight average molecular weight was 1.06. . In addition, the weight average molecular weight of polybutadiene in PB-b-PEO, which is another component of the surfactant, was 500, the weight average molecular weight of polyethylene oxide was 20000, and the ratio of the number average molecular weight to the weight average molecular weight was 1.01.

In the microparticles prepared in Example 2, the nanostructure of the microparticles was changed according to the weight ratio of PB-b-PEO and PS-b-PEO. Specifically, the weight ratio of PS-b-PEO is 0wt%. As shown in (a) of FIG. 3, the structure having an onion form and the outermost polybutadiene was obtained, and when the weight ratio of PS-b-PEO was 36wt%, as shown in FIG. The structure was created. In addition, when the weight ratio of PS-b-PEO is 46wt%, as shown in (c) of FIG. 3, it was possible to obtain fine particles embodied in the form of elliptical particles having a flat structure, which is illustrated in FIG. 3 (f). It can also be confirmed by scanning electron micrograph. On the other hand, when the weight ratio of PS-b-PEO is 77wt%, the reverse structure of FIG. 3 (b) is obtained, and when the weight ratio of PS-b-PEO is 100wt%, an onion structure can be obtained again, in this case, The outermost polystyrene is located.

<Example 3>

General process conditions are the same as those of Example 2, but the polystyrene-polybutadiene double block copolymer (PS-b-PB) was mixed with polystyrene having a weight average molecular weight of 10000 in a weight ratio of 41 wt% in preparing a block copolymer dispersion solution. Microparticles were prepared on the basis.

When PS-b-PEO constituting the surfactant is 0% and PB-b-PEO is 100%, fine particles having a structure as shown in FIG. 4A can be obtained, and the polybutadiene is located at the outermost part. It was. In addition, when the PS-b-PEO is 46% and the PB-b-PEO is 54%, a linear cylinder is arranged inside the disk-shaped particle as shown in FIG. Particles can be obtained. The cross-sectional structures of FIGS. 4A and 4B are as shown in FIGS. 4D and 4E, respectively. On the other hand, when PS-b-PEO is 100% and PB-b-PEO is 0%, it has a structure as shown in (c) of FIG. 4 and polystyrene is located at the outermost part.

<Example 4>

In the third embodiment, the polybutadiene was selectively irradiated with an ultraviolet lamp having a wavelength of 185 nm on the disk-shaped microparticles prepared using a surfactant having 46% PS-b-PEO and 54% PB-b-PEO. To remove the nanoporous microparticles were prepared. FIG. 5 (a) shows a scanning electron micrograph of the nanoporous microparticles prepared in Example 4, and FIG. 5 (b) shows a transmission electron micrograph of the nanoporous microparticles.

Example 5

General process conditions are the same as those of Example 2, but the polystyrene-polybutadiene double block copolymer (PS-b-PB) was mixed with polystyrene having a weight average molecular weight of 10000 in a weight ratio of 68 wt%. Microparticles were prepared on the basis.

When PS-b-PEO constituting the surfactant is 0% and PB-b-PEO is 100%, fine particles having a structure as shown in FIGS. 6A and 6D can be obtained. Polybutadiene was located. In addition, when the PS-b-PEO is 46% and the PB-b-PEO is 54%, as shown in (b) and (e) of FIG. 6, fine particles having a hemispherical polybutadiene phase outside the spherical particles are shown. Particles could be obtained. The cross-sectional structures of FIGS. 6B and 6E are as shown in FIGS. 6G and 6H, respectively. When PS-b-PEO is 100% and PB-b-PEO is 0%, it has a structure as shown in FIGS. 6C and 6F and polystyrene is located at the outermost part.

On the other hand, polybutadiene can be removed through ultraviolet irradiation as in Example 4, through which nanoporous microparticles as shown in FIG.

1 is a flow chart illustrating a method for producing nanostructured microparticles using droplets according to an embodiment of the present invention.

Figure 2 is a transmission electron micrograph of the microparticles prepared according to Example 1 of the present invention.

Figure 3 is a transmission electron micrograph of the fine particles prepared according to Example 2 of the present invention.

Figure 4 is a transmission electron micrograph of the fine particles prepared according to Example 3 of the present invention.

5 is a scanning electron micrograph of the microparticles prepared according to Example 4 of the present invention.

Figure 6 is a transmission electron micrograph of the microparticles prepared according to Example 5 of the present invention.

7 is a conceptual diagram of a method for producing nanostructured microparticles using droplets according to the present invention.

8 is a conceptual view illustrating a surface patterning method of microparticles according to an embodiment of the present invention.

9 is a conceptual diagram for a method for selectively placing metal nanoparticles inside microparticles according to an embodiment of the present invention.

10 is a conceptual diagram of a method for forming a selective metal material inside the microparticles according to an embodiment of the present invention.

11 is a conceptual diagram for the polarization characteristics of the fine particles according to an embodiment of the present invention.

12 is a conceptual view of the application of the display device of the fine particles according to an embodiment of the present invention.

Claims (17)

(A) preparing a block copolymer; (B) preparing a block copolymer dispersion solution; (C) stirring the block copolymer dispersion solution, the droplet inducing solution and the surfactant to form a block copolymer droplet; And (D) forming a fine particle by evaporating the solvent of the block copolymer droplets. The method of claim 1, wherein after step (d), Method for producing nanostructured microparticles using droplets further comprising the step of attaching the compound or metal nanoparticles on the surface of the microparticles. The method of claim 2, wherein the surfactant includes a surfactant including a specific reactor, and the surface of the compound or metal nanoparticles is provided with a reactor for reacting with the specific reactor of the surfactant Nanostructured microparticles manufacturing method. The method of claim 1, wherein the metal nanoparticles are included in the block copolymer dispersion solution, the same component as the specific component of the plurality of components constituting the block copolymer on the surface of the metal nanoparticles, characterized in that the coating Nanostructured microparticles manufacturing method using droplets. The nanostructured microparticles using droplets according to claim 4, wherein the metal nanoparticles are self-assembled in a specific component of the microparticle, and the specific component is the same as a component applied to the surface of the metal nanoparticle. Manufacturing method. The method of claim 1, wherein after step (d), Mixing a metal precursor reacts with a specific component of the block copolymer with the microparticles to allow the metal to self-assemble in the specific component of the microparticles, characterized in that the nanostructured microparticles manufacturing method using droplets. The method of claim 1, wherein the block copolymer is an organic block copolymer, an organic-inorganic copolymer, an inorganic-inorganic block copolymer, or a combination thereof. . 8. The nanostructured microparticles using droplets of claim 7, wherein at least one homopolymer having the same component as each block of different components constituting the block copolymer is added to the block copolymer. Manufacturing method. The method of claim 1, wherein the concentration of the block copolymer in the block copolymer dispersion solution is characterized in that the nanostructured microparticles manufacturing method using a droplet characterized in that 0.01 ~ 10wt%. According to claim 1, wherein the solvent and the droplet-inducing solution of the block copolymer dispersion solution is composed of water or oil, when the solvent of the block copolymer dispersion solution is water, the droplet induction solution is an oil, the block copolymer When the solvent of the dispersion solution is an oil, the droplet induction solution is nanostructured microparticles manufacturing method using a droplet, characterized in that the water. The method of claim 10, wherein the oil has a continuous phase or a dispersed phase and is any one of toluene, silicone oil, dodecane, and hexadecane. The method of claim 1, wherein after step (d), Removing the specific components constituting the microparticles to produce nanoporous microparticles further comprises the step of producing nanostructured microparticles using the droplets characterized in that it comprises. 13. The method of claim 12, wherein the specific component constituting the microparticles is removed by UV irradiation. The method of claim 1, wherein the block copolymer is a polystyrene-b-polybutadiene (PS-b-PB) double block copolymer, polystyrene-poly-4-vinylpyridine (polystyrene-b-poly-4- vinylpyridine) Double block copolymer, polystyrene-b-polymethylmethacrylate (polystyrene-b-polymethylmethacrylate) A method for producing nanostructured microparticles using droplets, characterized in that any one or a combination thereof. 15. The method of claim 14, wherein the block copolymer is a triple block copolymer composed of components constituting the double block copolymer or a combination thereof. According to claim 1, wherein the surfactant is a nanostructured fine using droplets, characterized in that the amphiphilic block copolymer comprising at least one or more of the components constituting the block copolymer or two or more amphiphilic block copolymer Particle preparation method. The method of claim 16, wherein the amphiphilic block copolymer is a polystyrene-b-polyethyeleneoxide, a polybutadiene-b-polyethyeleneoxide block copolymer, polyethylene oxide-polypropylene oxide-polyethylene oxide Ester-like polymeric surfactants with long-chain alkyl and OH- groups, polyethyleneoxide-polypropyleneoxide-polyethyleneoxide, sorbitan monooleate, long-chain alkyl, OH- A method for producing nanostructured microparticles using droplets, characterized in that any one or a combination thereof.

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