WO2016003212A1

WO2016003212A1 - Non-spherical amphiphilic polymer nanoparticles having interfacial properties which can be reversibly controlled by temperature, method for producing same, and composition comprising same

Info

Publication number: WO2016003212A1
Application number: PCT/KR2015/006806
Authority: WO
Inventors: 조은철; 박지훈; 임소라; 한누리
Original assignee: 한양대학교 산학협력단
Priority date: 2014-07-02
Filing date: 2015-07-02
Publication date: 2016-01-07

Abstract

The present invention relates to a non-spherical amphiphilic polymer nanoparticles having interfacial properties which can be reversibly controlled by temperature at the aqueous solution-to-oil and aqueous solution-to-solid interfaces, a method for producing the non-spherical amphiphilic polymer nanoparticles, and an emulsion composition or a nanopattern-forming composition comprising same, the hydrophilic and hydrophobic properties of the particle surface of the non-spherical amphiphilic polymer nanoparticles according to the present invention reversibly changing with temperature, thus allowing the interfacial properties between liquid-to-liquid or liquid-to-solid to be reversibly controlled by temperature. Accordingly, the emulsion composition comprising the non-spherical amphiphilic polymer nanoparticles according to the present invention can maximize the delivery of drugs, cosmetics and the like in the medical and cosmetic fields by controlling the size of the emulsion by means of temperature-based control of the interfacial properties. Additionally, the effectiveness of the lithographic process for semiconductor chip production can be maximized in the electronics industry as the wettability of the liquid for a solid substrate can be controlled by using the characteristic in which the interfacial properties can be reversibly controlled by temperature. Furthermore, the present invention can be used as a printer ink composition and the like in the printer ink and paint industries to maximize the coating effectiveness on the surface of printer paper and painting surfaces having diverse surface characteristics.

Description

Non-spherical amphiphilic dimer nanoparticles capable of reversibly controlling interfacial properties according to temperature, preparation method thereof and composition comprising same

The present invention relates to non-spherical amphiphilic dimer nanoparticles, a method for preparing the same, and a composition comprising the same. More specifically, the present invention relates to a non-spherical shape capable of reversibly adjusting interfacial properties according to temperature at an aqueous solution-oil and an aqueous-solid interface. Amphiphilic dimer nanoparticles, a method for preparing the same and an emulsion composition or composition for forming a nanopattern comprising the same.

In the field of medicine and cosmetics, various surfactants are used to stably disperse the oil composition of an emulsion system having a water-oil composition in an aqueous phase. When the emulsion system is applied to the skin, the oil is applied to the skin interface to have an occlusive effect that prevents the evaporation of water present in the skin and at the same time serves to deliver the bioactive ingredients and drugs mixed in the oil to the skin. . In addition to the purpose of delivering the oil stably to the water, the surfactant controls the size of the oil particles and the skin absorption of the oil by controlling the interfacial energy of the water and the oil. However, when an excessive amount of surfactant is used, the surfactant is also delivered to the skin, causing skin irritation and damage. In order to solve this problem, a surfactant made of polymer particles has been introduced, but a polymer surfactant made of a single chemical component has a high hydrophobicity or hydrophilicity, which is insufficient to stabilize the interface between water and oil, and is irreversible depending on temperature. If the denaturation of the particles, such as aggregation can no longer act as a surfactant there is a difficult management problem. Therefore, many techniques have been proposed to solve this problem, but more research is needed.

In addition, the lithography process, which is the first step in the manufacture of semiconductor chips in the electronics industry, is currently using photolithography technology based on photosensitizers capable of reacting to light stimuli such as ultraviolet rays. . Recently, a method of patterning a substrate using various methods has been applied, including soft lithography, a pattern using a block copolymer or nanoparticles, and for this purpose, various surfaces of the substrate are manufactured. have. However, when the substrate is patterned using an aqueous solution, when the surface property is hydrophobic, wetting is not secured, thus making it difficult to process.

Accordingly, there is a need for the development of nanoparticles that can deliver nanoparticles dispersed in an aqueous solution to a substrate while controlling the interfacial energy between the aqueous solution and the hydrophobic substrate. In addition, in the ink and paint industry for printers, there is a need for a technology that can effectively coat coating surfaces and print paper surfaces having various surface properties, and furthermore, particles and particles capable of reversibly controlling the surface properties of water and substrates according to temperature. It is an urgent need to develop a technology for controlling the wettability using the properties.

As a prior art, Non-Patent Document 1 (Jin-Woong Kim, Ryan J. Larsen, and David A. Weitz, J. Am. Chem. Soc., 2006, 128 (44), pp 1437414377) reacts with styrene. The present invention relates to non-spherical particles formed by phase separation by adding glycidyl methacrylate (GMA) different from styrene to polymerized seed particles. Non-Patent Document 2 (Jin-Woong Kim, Ryan J. Larsen, and David A. Weitz, Chem. Commun., 2012, 48, 90569058) relate to non-spherical particles functionalized by coating gold nanoparticles on only part of them using the amphiphilic affinities. These non-spherical particles form aggregates and are used to control interfacial energy or interfacial tension between liquid-liquid and liquid-solids, but there is a limit to use because the size of aggregated particles cannot be adjusted according to temperature.

Therefore, depending on the temperature, the size of the emulsion can be controlled by controlling the interfacial properties acting on the water-oil, and the wettability of the liquid on the solid substrate by controlling the interfacial properties between the solid substrate and the liquid having various surface properties. There is a need for the development of non-spherical particles that can control wettability.

Accordingly, the present invention is to provide a non-spherical amphiphilic dimer nanoparticles that can reversibly adjust the interface properties according to the temperature.

In addition, the present invention is to provide a method for producing non-spherical amphiphilic dimer nanoparticles that can reversibly adjust the interface properties according to the temperature.

In addition, the present invention is to provide an emulsion composition and a composition for forming a nanopattern comprising the non-spherical amphiphilic dimer nanoparticles.

Accordingly, the present invention provides a non-spherical amphiphilic dimer nanoparticles consisting of the first particles and the second particles, and reversibly adjust the interfacial energy with water according to the temperature in order to solve the above problems. The first particles may be hydrophilic in surface characteristics, and the second particles may be hydrophobic in surface characteristics.

In addition, the non-spherical amphiphilic dimer nanoparticles according to the present invention is characterized in that the interfacial energy between the surface of the first particle and water is reversibly increased or decreased with temperature.

In addition, in the non-spherical amphiphilic dimer nanoparticles according to the present invention, the first particle is characterized in that the core-shell structure comprising a core made of a hydrophobic polymer, and a shell made of a hydrophilic polymer surrounding the core The second particle may be formed by protruding a hydrophobic polymer constituting the core from one point of the first particle, and the second particle is partially in contact with the first particle.

According to one embodiment of the invention, the hydrophobic polymer is styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, glycidyl methacrylate Acrylates and polymers thereof.

According to another embodiment of the present invention, the hydrophilic polymer may be selected from N-isopropyl acrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate, and polymers thereof.

In addition, the present invention comprises the steps of (a) adding a hydrophobic monomer, an ionic initiator and a crosslinking agent to an aqueous solution containing cyclodextrin to prepare a solution in which seed particles are formed;

(b) adding a solution in which the seed particles are formed and an ionic initiator to an aqueous solution containing a hydrophilic monomer to prepare a solution in which the first particles having a core-shell structure are formed;

(c) further adding a hydrophobic monomer to the solution in which the first particles are formed, followed by stirring to swell the first particles;

(d) reswelling the first particles by heating and restirring to 25 to 100 ° C. after step (c); And

(e) adding a radical initiator after the reswelling to polymerize the hydrophobic monomer added in step (c); and

Method for producing non-spherical amphiphilic dimer nanoparticles reversibly controlled interfacial energy with water according to the temperature characterized in that the hydrophobic monomer is polymerized to form second particles protruding from one point of the first particles. to provide.

In addition, the first particle of the core-shell structure includes a core made of a hydrophobic polymer and a hydrophilic polymer surrounding the core, the surface property of the first particle is hydrophilic, and the surface property of the second particle is hydrophobic. It is characterized by. In addition, the interfacial energy between the surface of the first particle and water is reversibly increased or decreased depending on the temperature.

According to an embodiment of the present invention, step (c) may be performed at 10 to 40 ° C. for 10 to 30 hours.

According to another embodiment of the present invention, the size of the first particles increases and the size of the second particles decreases as the reswelling time of step (d) increases.

According to another embodiment of the present invention, the hydrophobic monomer is styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, glycy It may be at least one selected from dimethyl methacrylate.

According to another embodiment of the present invention, the hydrophilic monomer may be at least one selected from N-isopropyl acrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate.

According to another embodiment of the present invention, the cyclodextrin is methyl-β-cyclodextrin (methyl-β-cyclo dextrin), β-cyclodextrin (β-cyclodextrin), 2,6-dimethyl-β-cyclodextrin (2,6-dimethyl-β-cyclodextrin) and sulfobutyl ether-β-cyclodextrin may be one or more selected from sodium sulphobutyl ether-β-cyclodextrin.

According to another embodiment of the present invention, the ionic initiator may be at least one selected from potassium peroxodisulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS).

According to another embodiment of the present invention, the radical initiator is 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile), 2,2-azo Bis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxy Benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate and mixtures thereof.

In addition, the present invention provides an emulsion composition comprising the non-spherical amphiphilic dimer nanoparticles.

In the emulsion composition according to the present invention, the non-spherical amphiphilic dimer nanoparticles in the composition are arranged on an aqueous solution-oil interface to form an emulsion, and the interface between water and the first particle surface forming the non-spherical amphiphilic dimer nanoparticles The energy is reversibly changed with temperature.

In addition, the interfacial energy between the surface of the first particle and water is reversibly changed with temperature, so that the size of the emulsion is reversibly adjusted with temperature.

According to an embodiment of the present invention, the size of the emulsion may be 1 to 50 ㎛.

In addition, the present invention provides a composition for forming a nanopattern comprising the non-spherical amphiphilic dimer nanoparticles.

The composition for forming a nanopattern according to the present invention is characterized in that the non-spherical amphiphilic dimer nanoparticles in the composition are arranged on the interface of the nanopattern-forming solid substrate, and the surface of the first particle and the water forming the non-spherical amphiphilic dimer nanoparticle Is characterized in that the interfacial energy of reversibly changes with temperature.

In addition, as the interfacial energy between the surface of the first particle and water is reversibly changed with temperature, the interfacial energy between the aqueous dispersion including the nanoparticles and the solid substrate for forming the nanopattern is reversibly controlled. do.

Amphiphilic non-spherical dimer nanoparticles according to the present invention can reversibly adjust the liquid-liquid or liquid-solid interface characteristics with temperature as the hydrophilic and hydrophobic properties of the particle surface reversibly change with temperature. Therefore, the emulsion composition comprising an amphiphilic non-spherical dimer according to the present invention can maximize the delivery of drug cosmetics, such as by adjusting the size of the emulsion by adjusting the interfacial properties according to the temperature in the field of medicine, cosmetics.

In addition, in the electronics industry, the wettability of a liquid on a solid substrate may be controlled by using a property of reversibly adjusting interface characteristics according to temperature, thereby maximizing the efficiency of a lithography process for manufacturing a semiconductor chip. . In addition, it is possible to maximize the coating efficiency of the coating surface and the surface of the print paper having a variety of surface properties used in the printer ink and paint industry, such as the ink liquid composition for the printer.

1A is a cross-sectional view of non-spherical amphiphilic dimer nanoparticles prepared according to the present invention.

Figure 1b is a schematic diagram showing the characteristics of the production method and non-spherical amphiphilic dimer nanoparticles according to Example 1 of the present invention.

Figure 1c is a schematic diagram showing the characteristics of the production method and non-spherical amphiphilic dimeric nanoparticles according to Example 2 of the present invention.

FIG. 2A is a SEM image of polystyrene seed particles (PS), and FIG. 2B is a SEM image of Pnipaam-co-MA coated polystyrene nanoparticles (Core-shell).

FIG. 3A is a graph illustrating a change in hydrodynamic diameter of particles according to temperature change of polystyrene nanoparticles (PS) and polystyrene nanoparticles (core-shell) coated with a hydrophilic polymer, and FIG. 3B is zeta according to temperature change. It is a graph showing the change in potential (zeta potential).

FIG. 4 is an optical microscope illustrating a process of forming a pickling emulsion by adding a polystyrene monomer to a solution in which polystyrene nanoparticles (core-shell) coated with a hydrophilic polymer are formed and stirred according to Example 2 of the present invention. Image taken with microscope.

FIG. 5 is a cross-sectional view schematically illustrating a process of forming a pickling emulsion according to Example 2 of the present invention and a change in size of the pickling emulsion according to agitation time.

Figure 6 is a graph showing the size change with stirring time of the pickling emulsion formed according to Example 2 of the present invention.

7 is an image taken with an optical microscope to confirm the formation mechanism of the non-spherical amphiphilic dimer nanoparticles according to Example 2 of the present invention, ac is a polystyrene nanoparticles coated with a hydrophilic polymer (Core (shell) shows the emulsion change after injecting styrene monomer into the dispersion solution (a: after stirring for 11 hours at room temperature, b: heating to 80 ℃, re-stirring and 10 minutes after AIBN addition, c: heating to 80 ℃, re 20 minutes after stirring and AIBN addition), dg shows the emulsion change after injection of styrene monomer into distilled water and homogenization (d: immediately after homogenization at room temperature, e: after heating to 80 ° C, f: heating to 80 ° C, re 20 min after stirring and AIBN addition, g: heating to 80 ° C., restirring and 4 hours after AIBN addition).

8 is an SEM image of non-spherical amphiphilic dimer nanoparticles prepared according to the present invention.

9 is a swelling time (a: 0h, b: 1h, c: 2h, d: 6h, e: 18h, h in the process of re-swelling the first particles by re-stirring at 80 ℃ according to Example 2 of the present invention) SEM image showing changes in particle size and shape according to: 24h).

10 is a swelling time (a: 0h, b: 1h, c: 2h, d: 6h, e: 18h, h in the process of re-swelling the first particles by re-stirring at 80 ℃ according to Example 2 of the present invention) A graph showing the change in particle size according to: 24h).

11 is a non-spherical compound synthesized after adsorbing a fluorescent dye to the first particles of the core-shell structure in order to prove that the non-spherical amphiphilic dimer nanoparticles prepared according to Example 2 have amphiphilic properties SEM images of amphiphilic dimer nanoparticles, images taken with a confocal microscope, and images taken with a confocal microscope after re-adsorption of a fluorescent dye after synthesis are shown.

Figure 12a is a polystyrene nanoparticles (PS), hydrophilic polymer-coated polystyrene nanoparticles (Core-shell), non-spherical amphiphilic dimer nanoparticles according to Example 2 of the present invention prepared by varying the reswelling time (0h , 6h, 18h) and poly fluoride intensities (FL Intensity) of poly (N-isopropylacrylamide) hydrogel nanoparticles.

Figure 12b is a polystyrene nanoparticles (PS), hydrophilic polymer-coated polystyrene nanoparticles (Core-shell), non-spherical amphiphilic dimer nanoparticles according to Example 2 of the present invention prepared by varying the reswelling time (0h , 1h, 2h, 6h, 12h, 24h) is a graph showing the change in the diameter of the particles (hydrodynamic diameter) with the temperature change (diameter at room temperature (RT)-diameter at 50 ° C).

Figure 12c is a polystyrene nanoparticles (PS), polystyrene nanoparticles (Core-shell) coated with a hydrophilic polymer, non-spherical amphiphilic dimer nanoparticles according to Example 2 of the present invention prepared by varying the reswelling time (0h , 1h, 2h, 6h, 12h, 24h) is a graph showing the change in zeta potential (zeta potential at room temperature (RT)-zeta potential at 50 ° C.) with temperature changes.

Figure 13 is a schematic diagram showing the change in the size of the emulsion formed with temperature.

14 is a schematic diagram showing the contact angle of an aqueous solution containing non-spherical amphiphilic dimer nanoparticles with temperature.

15a to 15d is an image showing the change in emulsion size according to the temperature of the non-spherical amphiphilic dimer nanoparticle dispersion solution and coconut oil solution prepared according to Example 1 of the present invention using an optical microscope (Fig. 15A is room temperature, FIG. 15B is 50 ° C., and FIG. 15C is cooled again to room temperature) and a graph (FIG. 15D).

16A to 16C are images showing particle size changes according to the temperature of a solution of a polystyrene dispersion solution and coconut oil using an optical microscope (FIG. 16A is room temperature, FIG. 16B is 50 ° C, and FIG. 16C is again cooled to room temperature). In one case).

17 is a change in the size of the emulsion according to the temperature of the non-spherical amphiphilic dimer nanoparticle dispersion solution and silicon oil (DC 200) solution prepared according to Example 2 of the present invention (a: room temperature (RT), b: 30 ° C., c: 35 ° C., d: 40 ° C., e: 45 ° C., f: 50 ° C.) is an image taken with an optical microscope.

18 is a change in emulsion size according to the temperature of the non-spherical amphiphilic dimer nanoparticle dispersion solution prepared according to Example 2 of the present invention and a silicone oil (DC 200) solution (a: room temperature (RT), b : 30 degreeC, c: 35 degreeC, d: 40 degreeC, e: 45 degreeC f: 50 degreeC).

Figure 19 is the size of the emulsion while repeating cooling to room temperature and heating to 50 ° C solution of a non-spherical amphiphilic dimer nanoparticle dispersion solution prepared in Example 2 of the present invention and a silicone oil (DC 200) The change was taken with an optical microscope.

20 is the size of the emulsion while repeating cooling to room temperature and heating to 50 ℃ the solution of the non-spherical amphiphilic dimer nanoparticle dispersion solution prepared in Example 2 of the present invention and silicon oil (DC 200) It is a graph showing the change.

FIG. 21A is a surface of polystyrene film of water, polystyrene dispersion (PS) at room temperature (25 ° C.) and 50 ° C., and a non-spherical amphiphilic dimer dispersion solution prepared according to Example 1 of the present invention. Image showing contact angle for.

Figure 21b is a polydimethyl of water (water), polystyrene dispersion (PS) at room temperature (25 ℃) and 50 ℃ and non-spherical amphiphilic dimer (dimer) dispersion solution prepared according to Example 1 of the present invention Image showing contact angle with respect to siloxane film surface.

FIG. 21C is a surface of polystyrene film of water, polystyrene dispersion (PS) at room temperature (25 ° C.) and 50 ° C., and a non-spherical amphiphilic dimer dispersion solution prepared according to Example 1 of the present invention. And a contact angle with respect to the polydimethylsiloxane film surface, respectively.

Figure 22a shows the contact angle to the surface of the polystyrene film of water at room temperature (25 ℃) and 50 ℃, non-spherical amphiphilic dimer nanoparticles (Dimer) dispersion solution prepared according to Example 2 of the present invention Image.

22b is water prepared at room temperature (25 ° C.) and 50 ° C., polystyrene nanoparticles (PS), hydrophilic polymer-coated polystyrene nanoparticles (Core-shell, CS), and prepared according to Example 2 of the present invention. Is a graph showing the contact angle to the surface of the polystyrene film of the non-spherical amphiphilic dimer nanoparticles (Dimer) dispersion solution.

FIG. 23A is a polydimethylsiloxane (PDMS) film of water at room temperature (25 ° C.) and 50 ° C., a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution prepared according to Example 2 of the present invention. This image shows the contact angle to the surface.

23b is prepared according to Example 2 of the present invention and water, polystyrene nanoparticles (PS), hydrophilic polymer-coated polystyrene nanoparticles (Core-shell, CS) at room temperature (25 ° C.) and 50 ° C. Is a graph showing the contact angle of polydimethylsiloxane (PDMS) film surface of the prepared non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution.

Hereinafter, the present invention will be described in more detail.

In order to overcome various problems caused by the use of surfactants in emulsion systems with water-oil composition, attempts have been made to prepare emulsions using polymer particles. However, most polymer particles have hydrophobic properties so that water and oil There is a problem that the interfacial activity of is significantly lowered.

Therefore, recently, studies have been conducted to increase the interfacial force by preparing dimer particles and giving hydrophilicity to one particle and hydrophobicity to one particle. However, the production of particles that can control the size and function of the oil dispersed in water by reversibly controlling the interfacial force between water and oil according to the temperature has not been developed, and also has a variety of surface properties Above, the technology for controlling the wettability of the substrate or the pattern of patterning the particles on the substrate using the particles and the properties that can reversibly control the surface properties of the water and the substrate according to the temperature has not been developed.

Accordingly, the present inventors can effectively control the interface characteristics such as interfacial energy or interfacial tension between liquid-liquid and liquid-solid, and in particular, the interfacial characteristics between water and oil are reversibly adjusted according to temperature and dispersed in water. It is possible to control the size of the oil and the function of the oil, non-spherical, characterized in that it is possible to adjust the interface properties of the water and the substrate reversibly according to the temperature to control the wettability of the substrate or pattern of particles patterned on the substrate Amphiphilic dimeric nanoparticles, and methods for their preparation are provided.

Figure 1a is a cross-sectional view of the non-spherical amphiphilic dimer nanoparticles prepared in accordance with the present invention.

Non-spherical amphiphilic dimer nanoparticles according to the present invention is composed of the first particles and the second particles, it is characterized in that the reversible energy control with the water depending on the temperature. In addition, in the non-spherical amphiphilic dimer nanoparticles according to the present invention, the first particle is characterized in that the core-shell structure comprising a core made of a hydrophobic polymer, and a shell made of a hydrophilic polymer surrounding the core The second particle may be formed by protruding a hydrophobic polymer constituting the core from one point of the first particle, and the second particle is partially in contact with the first particle. In addition, the first particles in contact with the second particles are characterized in that the phase separation without mixing with each other.

In the non-spherical amphiphilic dimer nanoparticles according to the present invention, the first particle has a hydrophilic surface property, and the second particle has a hydrophobic surface property, thereby implementing amphiphilic properties. Here, the surface of the first particle has a hydrophilic property, but it is characterized by a change in hydrophobicity as the temperature increases, in particular, the change of the surface hydrophilicity and hydrophobic properties is characterized in that it is reversible with temperature changes.

As shown in Figure 1b and Figure 1c, the surface of the first particle of the non-spherical amphiphilic dimer nanoparticles according to the present invention at room temperature (RT) interfacial energy (γ _sw or γ _pw is low, but the interface energy with water (γ _sw or γ _pw ) increases, and this characteristic is due to the interfacial energy with water (γ _sw or γ _pw ) has a low reversibility. That is, the interfacial energy between the surface of the first particle and the water of the non-spherical amphiphilic dimer nanoparticles prepared according to the present invention is reversibly increased or decreased depending on the temperature.

According to an embodiment of the present invention, the hydrophobic polymer is styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, glycidyl methacryl The hydrophilic polymer may be selected from N-isopropylacrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate, and polymers thereof.

1B shows a method for preparing non-spherical amphiphilic dimer nanoparticles and a non-spherical amphiphilic dimer nanoparticle according to Example 1 of the present invention.

Briefly describing the preparation method according to Example 1, first, the hydrophilic polymer material having different phases is coated on the seed particles made of the hydrophobic polymer material to form seed particles surface-coated with the hydrophilic polymer. When an excessive amount of the monomer (first monomer) of the hydrophobic polymer is added thereto, the monomer penetrates into the coated seed particles and the coated seed particles swell. When the monomers are polymerized in the seed particles to form the core of the first particles, the hydrophobic polymer in the seed particles increases and protrudes out of the seed particle surface to form second particles.

The size of the second particles can be controlled by the amount of the first monomer added in excess to swell the seed particles. The amount of the first monomer to be added may be 5 to 15 times than the amount of the first monomer added to form the seed particles, and preferably 9 to 11 times. If it is less than the lower limit, it is insufficient to form the second particles, and if it is more than the upper limit, the second particles may grow too much to cover the first particles, thereby weakening the properties of the dimer.

Hereinafter, the manufacturing method according to Example 1 of the present invention will be described in more detail. The manufacturing method according to Example 1 of the present invention is characterized by including the following steps.

(a) adding a hydrophobic monomer, an ionic initiator and a crosslinking agent to an aqueous solution containing cyclodextrin to form seed particles,

(b) coating the seed particles by adding an aqueous solution containing a hydrophilic monomer,

(c) further adding a hydrophobic monomer to swell the coated seed particles,

(d) adding an aqueous solution containing an anionic surfactant and a radical initiator to polymerize the hydrophobic monomer added in step (c).

According to a preferred embodiment of the present invention, the hydrophobic monomer is styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, glycidyl methacrylate It is preferable that it is 1 or more types chosen from a acrylate and these polymers.

According to a preferred embodiment of the present invention, the hydrophilic monomer is preferably at least one selected from N-isopropyl acrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate and polymers thereof.

According to a preferred embodiment of the present invention, the cyclodextrin is methyl-β-cyclodextrin (methyl-β-cyclo dextrin), β-cyclodextrin (β-cyclodextrin), 2,6-dimethyl-β-cyclodextrin (2 It is preferable that it is at least one selected from, 6-dimethyl-β-cyclodextrin) and sodium sulphobutyl ether-β-cyclodextrin.

According to a preferred embodiment of the present invention, the ionic initiator is preferably at least one selected from potassium peroxodisulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS).

According to a preferred embodiment of the present invention, the anionic surfactant is sodium dodecyl sulfate (SDS), diisooctyl sodium sulfosuccinate (DSS), sodium tetratradecylsulfate, sodium hexadecyl sulfate (sodiumhexadecylsulfate), sodium Dodecylbenzenesulfonate, xylenesulfonate, sodium oleate, 4-n-decylbenzenesulfonate, sodium laurate, 4-dode 4-benzene-sulfonic acid, dodecylamine hydrochloride, dodecyltrimethylammonium chloride, 4-n-octylbenzenesulfonate, ethoxylatedsulfonate (Ethoxylatedsulfonate), Decylbenzenesulfonate, Potassium oleate, n-decylbenzenesulfonate, alkyl tree Methylammonium bromide (Alkyltrimethylammonium bromide), Dodecylamine, Tedecyltrimethylammonium chloride, Dodecylpolysaccharideglycoside, Cyclodextrins, Glycolipidid-glycolipidin It is preferably at least one selected from peptides (lipoproteinipopeptides), phospholipids, para-toluenesulfonicacid and trisiloxane.

According to a preferred embodiment of the present invention, the radical initiator is 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile), 2,2-azobis ( 2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl per It is preferable that it is at least 1 sort (s) chosen from an oxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy isobutyrate, and mixtures thereof.

When the excess first monomer is added to the coated seed particles in step (b), the polymerized polymer flows out of the seed particles while the first monomer polymerized into the seed particles is polymerized to form second particles, and the non-spherical particles as a whole. To form. The amount of the first monomer added may be 5 to 15 times based on the first monomer used in step (a), preferably 9 to 11 times.

According to a preferred embodiment of the present invention, step (c) may be carried out at 10 to 40 ℃, for 10 to 30 hours.

1C shows the method for preparing the non-spherical amphiphilic dimer nanoparticles according to Example 2 of the present invention and the characteristics of the non-spherical amphiphilic dimer nanoparticles, and the non-spherical amphiphilic dimer according to Example 2 of the present invention. The method for preparing sieve nanoparticles includes the following steps.

(a) adding a hydrophobic monomer, an ionic initiator and a crosslinking agent to an aqueous solution containing cyclodextrin to prepare a solution in which seed particles are formed;

(e) adding a radical initiator after the reswelling to polymerize the hydrophobic monomer added in step (c).

At this time, while the hydrophobic monomer added in step (c) is polymerized, the second particles protruding from one point of the first particles are formed, thereby forming non-spherical particles as a whole.

First, in step (a), a hydrophobic monomer, an ionic initiator and a crosslinking agent are added to an aqueous solution containing cyclodextrin to prepare a solution in which seed particles are formed. Thereafter, in step (b), a solution in which the seed particles are formed and an ionic initiator are added to an aqueous solution containing a hydrophilic monomer to prepare a solution in which the first particles having a core-shell structure are formed.

The prepared core-shell structured first particles include a core made of a hydrophobic polymer and a hydrophilic polymer surrounding the core, the surface properties of the first particles are hydrophilic, and the surface properties of the second particles are hydrophobic. It is characterized by. Figure 2a is a SEM image of the polystyrene seed particles (PS) prepared through the step (a) according to an embodiment of the present invention, Figure 2b is coated with Pnipaam-co-MA prepared through the step (b) SEM images of polystyrene nanoparticles (Core-shell) are shown. In addition, as can be seen through Figure 3a and 3b, the polystyrene seed particles (PS) prepared through the step (a) has little change in the diameter and zeta potential of the particles with temperature changes, the (b) Pnipaam-co-MA-coated polystyrene nanoparticles (Core-shell) prepared by the step) is reduced solubility with water when the temperature is increased due to the temperature sensitivity of Pnipaam-co-MA coated on the surface of the seed particles Phase separation occurs to reduce the particle size through shrinkage, zeta potential can also be seen that the negative (negative) properties are higher.

Next, in the step (c), the hydrophobic monomer is further added to the solution in which the first particles are formed, followed by stirring to swell the first particles. At this time, according to a preferred embodiment of the present invention, step (c) is preferably performed for 10 to 30 hours at 10 to 40 ℃. As shown in FIG. 5, when the hydrophobic monomer is added and stirred to swell the first particles, the core-shell structured first particles surround the added hydrophobic monomer to form a picking emulsion. As shown in Figure 4 and 6, it can be seen that the size of the pickling emulsion gradually decreases with the stirring time, which is the first hydrophobic monomer is added to the first hydrophobic monomer swelling It is implied that the pickling emulsion enters or breaks down to form a smaller size pickling emulsion. The amount of the hydrophobic monomer to be added may be 5 to 15 times based on the hydrophobic monomer used in step (a), preferably 7 to 11 times.

Next, in the step (d), after the step (c), the step of reswelling the first particles is performed by heating and restirring at 25 to 100 ° C. In this case, as the reswelling time of the first particles through the restirring increases, the size of the first particles of the core-shell structure of the prepared non-spherical amphiphilic dimer nanoparticles increases, while the size of the second particles decreases. It can be seen that the overall shape is close to the spherical shape (Figs. 9 and 10), in the present invention by adjusting the swelling time of the step (d) by controlling the size and shape of the particle surface The hydrophilic and hydrophobic properties of can be controlled. In addition, the higher the temperature within the above-described temperature range, the larger the size of the first particle of the core-shell structure within a short time, thereby reducing the reswelling time for adjusting to a spherical shape relatively shorter On the other hand, as the temperature is lowered, the size of the first particles of the core-shell structure is gradually increased, so that the reswelling time for adjusting to a shape close to a spherical shape is required.

Next, in step (e), a radical initiator is added to polymerize the hydrophobic monomer added through step (c), wherein the added hydrophobic monomer is polymerized, from one point of the first particle. Protruding second particles are formed, which form the non-spherical amphiphilic dimer particles according to the invention as a whole.

According to a preferred embodiment of the present invention, the hydrophobic monomer is styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, glycidyl methacrylate It is preferable that it is at least 1 sort (s) chosen from a acrylate.

According to a preferred embodiment of the present invention, the hydrophilic monomer is preferably at least one selected from N-isopropyl acrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate.

The non-spherical amphiphilic dimer nanoparticles according to the present invention prepared according to the production method of Examples 1 and 2 have both hydrophobicity and hydrophilicity and thus reversibly change the interfacial characteristics of liquid-liquid or solid-liquid according to temperature. The wettability to the solid surface may be adjusted, in particular depending on the temperature.

In particular, according to the manufacturing method according to the second embodiment of the present invention, it is possible to prepare non-spherical amphiphilic dimer nanoparticles without the use of a surfactant, which can greatly reduce human stimulation and toxicity, as well as swelling time (swelling) by controlling the size and shape of the particles to control the hydrophilicity and hydrophobicity of the particle surface.

The non-spherical amphiphilic dimer according to the present invention can form an emulsion in a water-soluble or fat-soluble solvent, the size of the emulsion can be reversibly changed with temperature by the interfacial properties that are reversibly controlled with temperature.

Figure 13 is a schematic diagram showing the size change of the emulsion with temperature.

The emulsion formed at room temperature (RT) is large in size due to the large number of non-spherical amphiphilic dimers of the present invention is formed, but at 50 ℃ a small number of dimers gather to form a large number of micelles of small size. Due to the change in the size of the emulsion with temperature, the contact angle between the aqueous solution containing the non-spherical amphiphilic dimer of the present invention and the surface also varies with temperature.

14 is a schematic view showing the contact angle of the non-spherical amphiphilic dimer aqueous solution on the hydrophobic surface.

The contact angle is large at room temperature (RT), the contact angle is small at 50 ℃ and the size of the contact angle can be reversibly changed depending on the temperature.

Since the non-spherical amphiphilic dimer according to the present invention can control the interfacial properties between liquid and liquid, it minimizes skin irritation, maximizes the feeling of use, and is included in the emulsion system of water-oil composition in medicine, cosmetics It is possible to maximize the skin delivery of the drug can be used in pharmaceutical or cosmetic compositions, such as ointments, lotions, creams, essences.

In addition, the non-spherical amphiphilic dimer according to the present invention can control the interfacial properties between the liquid and solid, and in particular, in the electronic industry, the interfacial energy with the hydrophobic surface is reduced in the process requiring a nanopattern based on an aqueous solution. (wetting) can be increased, and the shape of the nanopattern can be controlled when the nanopattern is formed by reversibly controlling the interfacial property between water and the solid surface, and thus can also be used for an ink liquid composition for a printer or a composition for a lithography nanopattern process. For example, it can be used as a template in the nano-pattern forming process based on an aqueous solution to increase the wetting by reducing the interfacial energy with the hydrophobic surface.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples and the like are intended to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

Example 1.

(1) Preparation of Polystyrene Seed Particle Dispersion Solution

The 250 ml flask was immersed in an oil reaction vessel at 80 ° C. and nitrogen was added thereto, added with a 1 wt% methyl-β-cyclodextrin (M-β-CD) aqueous solution and heated to 80 ° C., followed by potassium peroxodisulfate (KPS ) An initiator was added. 0.1 g of divinylbenzene (DVB), a crosslinking agent, and 9.9 g of styrene, a monomer, were mixed and stirred while adding to the flask at a constant rate for 2 hours through a syringe pump. After adding the crosslinking agent and the monomer, the mixture was stirred for 1 hour and then cooled to prepare a solution in which the polystyrene seed particles were dispersed.

(2) coating of NIPAAm-co-MA copolymer polymer material

The 250 ml flask was immersed in an oil reaction vessel at 80 ° C., nitrogen was added, 60 ml of the seed particle dispersion solution and 29 ml of distilled water were added, mixed, and heated to 80 ° C., followed by the addition of a potassium peroxide disulfide (KPS) initiator. It was. A solution containing 90: 10 mol% of N-isopropylacrylamide (NIPAAm) monomer and methacrylic acid (MA) monomer in distilled water 1 prepared in advance was added to the flask, followed by stirring for 4 hours to form NIPAAm and MA. A solution in which the copolymer-coated polystyrene seed particles was dispersed was prepared.

(3) Preparation of Non-Spherical Amphiphilic Dimers According to the Present Invention

25 ml of the coated polystyrene seed particle dispersion solution was placed in a beaker and 90 g of styrene monomer was added thereto, followed by reaction at room temperature for 20 hours. The beaker was immersed in an oil reaction vessel at 80 ° C., heated to 80 ° C. while nitrogen was added thereto, and then reacted for 1 hour by adding sodium dodecyl sulfate (SDS). An azobisisobutylonitrile (AIBN) initiator was added to the styrene monomer dispersion solution prepared in advance, followed by reaction for 4 hours to prepare a solution in which the non-spherical amphiphilic dimer was dispersed.

Example 2.

(1) Preparation of Polystyrene Seed Particle Dispersion Solution

The 250 ml flask was immersed in an oil reaction vessel at 80 ° C. and nitrogen was added thereto, added with a 1 wt% methyl-β-cyclodextrin (M-β-CD) aqueous solution and heated to 80 ° C., followed by potassium peroxodisulfate (KPS ) An initiator was added. 0.4 g of divinylbenzene (DVB), a crosslinking agent, and 5.6 g of styrene, a monomer, were mixed and stirred with a syringe pump at a constant rate for 2 hours. After adding the crosslinking agent and the monomer, the mixture was stirred for 1 hour and then cooled to prepare a solution in which the polystyrene seed particles were dispersed.

(2) coating of NIPAAm-co-MA copolymer polymer material

A 250 ml flask was immersed in an oil reaction vessel at 80 ° C., and nitrogen was added thereto. A solution containing 90: 10 mol% of N-isopropylacrylamide (NIPAAm) monomer and methacrylic acid (MA) monomer was added to 40 ml of distilled water. Put it. Next, after adding 15 ml of the solution in which the polystyrene smooth particles were dispersed and heating to 80 ° C., NIPAAm and MA having a core-shell structure were reacted for 2 hours and 30 minutes by adding a potassium peroxodisulfate (KPS) initiator. A solution in which a copolymer consisting of polystyrene seed particles (first particles) was dispersed was prepared.

(3) Preparation of Non-Spherical Amphiphilic Dimer Nanoparticles According to the Present Invention

3.5 ml of a solution in which the polystyrene seed particles (first particles) coated with a copolymer of NIPAAm and MA of the core-shell structure was dispersed and 4 ml of distilled water were added to a beaker, and 50.4 g of styrene monomer was added thereto. The polystyrene seed particles coated with the copolymer of NIPAAm and MA were swollen with stirring for an hour. The beaker was immersed in an oil reaction vessel at 80 ° C., heated to 80 ° C., and then coated with a copolymer of NIPAAm and MA while being restirred for 0 hours, 1 hour, 2 hours, 6 hours, 18 hours, and 24 hours, respectively. Polystyrene seed particles were reswelled. Thereafter, azobisisobutylonitrile (AIBN) initiator was added, followed by reaction for 4 hours and 30 minutes to polymerize the styrene monomer to prepare a solution in which the non-spherical amphiphilic dimer was dispersed.

Experimental Example

Experimental Example 1. Confirmation of the formation mechanism of non-spherical amphiphilic dimer nanoparticles

Experiments were conducted to confirm the formation mechanism of the non-spherical amphiphilic dimer nanoparticles prepared according to Example 2 of the present invention.

First, a change in the pickling emulsion after injecting a styrene monomer into a polystyrene seed particle (first particle) dispersion solution coated with a copolymer of NIPAAm and MA having a core-shell structure was observed by an optical microscope. The results are shown in ac of FIG. 7 (a: after stirring at room temperature for 11 hours, b: heating at 80 ° C., re-stirring and 10 minutes after AIBN addition, c: heating at 80 ° C., re-stirring and AIBN addition After 20 minutes). Referring to ac of FIG. 7, as the reaction proceeds, the injected styrene monomer enters the first particle of the swollen core-shell structure, or the pickling emulsion is split to form an emulsion of smaller size. It can be confirmed, thereby means that the non-spherical amphiphilic dimer nanoparticles are formed according to the present invention, which can be prepared according to the production method of the present invention without the use of surfactants Imply that there is.

Next, the styrene monomer was injected into distilled water and homogenized, and then the change of the emulsion was observed with an optical microscope, and the results are shown in dg of FIG. f: 20 minutes after heating to 80 ° C., restirring and adding AIBN, g: results after 4 hours after heating to 80 ° C., restirring and adding AIBN). Looking at the d-g of Figure 8 it can be seen that the size of the emulsion gradually decreases as the reaction proceeds, which suggests that the polystyrene nanoparticles can be synthesized without a surfactant.

Experimental Example 2 Amphipathic Confirmation of Non-Spherical Amphiphilic Dimer Particles

Polystyrene seed particles (first particles) coated with a copolymer of NIPAAm and MA having a core-shell structure to confirm the amphiphilic properties of non-spherical amphiphilic dimer nanoparticles prepared according to Example 2 of the present invention. After adsorbing the fluorescent dye on the styrene monomer, the reaction was carried out by adding styrene monomer to synthesize the non-spherical amphiphilic dimer nanoparticles, and then the SEM image, the image taken by confocal microscope, and the fluorescent dye after synthesis After the adsorption, the image taken by a confocal microscope was observed, and the results are shown in FIG. 11.

As shown in FIG. 11, it can be confirmed that non-spherical amphiphilic dimer nanoparticles were formed through SEM image after synthesis. In addition, confocal microscopy images showed a circular fluorescence immediately after synthesis, whereas non-spherical fluorescence was observed after fluorescence dye resorption, indicating that the copolymer consisting of coated NIPAAm and MA was only present on the surface of the first particle. The second particle is newly formed during the synthesis process, and as a result, the dimer nanoparticle according to the present invention is a core-shell structured first particle having a hydrophilic surface property and a second particle having a hydrophobic surface property. It can be confirmed that the particles, that is, amphipathic properties are measured.

Experimental Example 3. Observation of particle size and shape change by reswelling time control, fluorescence intensity measurement and change of particle size and zeta potential

(1) Observation of particle size and shape change with reswelling time

Swelling time (a: 0h, b: 1h, c: 2h, d: 6h, e: 18h, in the process of reswelling the first particles of the core-shell structure by restirring at 80 ° C according to Example 2 of the present invention) h: 24h) according to the change in the size and shape of the particles were measured, the results are shown in Figure 9 (SEM) and Figure 10 (graph).

As shown in FIGS. 9 and 10, as the reswelling time increases, the area of the first particle of the core-shell structure coated with the hydrophilic polymer increases, while the area of the second particle composed of the hydrophobic polymer decreases. It can be seen that the shape of the near to the sphere, which means that by controlling the size and shape of the particles by controlling the swelling time can control the hydrophilic and hydrophobic properties of the particle surface, that is, amphipathy.

(2) FL Intensity Measurement

In order to confirm the amphiphilic properties of the non-spherical amphiphilic dimer nanoparticles prepared according to Example 2 of the present invention, polystyrene nanoparticles (PS), core-shell first particles (Core-shell), reswelling time Methylene blue (MB) to non-spherical amphiphilic dimer nanoparticles (0h, 6h, 18h) and poly N-isopropylacrylamide (Poly (N-isopropylacrylamide)) hydrogel nanoparticles prepared according to the present invention After the adsorption, the fluorescence intensity (FL Intensity) at an excitation wavelength of 665 nm was measured, and the results are shown in FIG. 12A.

As shown in FIG. 12A, the peaks of the polystyrene nanoparticles are the highest, and the peaks of the poly N-isopropylacrylamide hydrogel gel nanoparticles are the lowest. This is due to the physical properties of polystyrene nanoparticles and poly N-isopropylacrylamide (Poly (N-isopropylacrylamide)). Polystyrene nanoparticles have relatively hard properties, so that dyes are adsorbed on the surface of particles. Poly N-isopropylacrylamide (Poly (N-isopropylacrylamide)) has soft properties because most of the light is reflected and high peaks appear. The peak will appear. It can be observed that the non-spherical amphiphilic dimer nanoparticles according to the present invention have a lower peak as the reswelling time increases, which is the first particle of the core-shell structure coated with a hydrophilic polymer as the reswelling time increases. While the area of is increased, the area of the second particles composed of hydrophobic polymers means that the reduced particle size is increased. As a result, the non-spherical amphiphilic dimer nanoparticles according to the present invention have amphiphilic properties, and the hydrophilicity and hydrophobicity of the surface of the particles can be controlled by controlling the size and shape of the particles by controlling the reswelling time. Means. It also implies that the amphipathic control can control the physicochemical properties of the particles, including the surface properties of the dimers, in particular the softness.

(3) Measurement of change in particle diameter and zeta potential with temperature change

In order to confirm the amphiphilic properties of the non-spherical amphiphilic dimer nanoparticles prepared according to Example 2 of the present invention, polystyrene nanoparticles (PS), core-shell first particles (Core-shell), reswelling time Changes in particle diameter (hydrodynamic diameter) of the non-spherical amphiphilic dimer nanoparticles (0h, 1h, 2h, 6h, 12h, 24h) according to the present invention prepared at different temperatures (at room temperature (RT) Diameter-diameter at 50 ° C.) and change in zeta potential (zeta potential at room temperature (RT) − zeta potential at 50 ° C.) were measured and the results are shown in FIGS. 12B and 12C below. .

As shown in FIG. 12A, polystyrene nanoparticles have almost no difference in diameter and zeta potential of the particles according to temperature change, whereas core-shell particles of the core-shell structure have the same characteristics. The difference in diameter and zeta potential was very large, and it can be seen that this is a result of the temperature sensitivity of the copolymer consisting of NIPAAm and MA, which are coated hydrophilic polymers. In addition, the non-spherical amphiphilic dimer nanoparticles according to the present invention has a medium value between the polystyrene nanoparticles and the core-shell, which means that the non-spherical amphiphilic dimer nanoparticles according to the present invention have amphiphilic properties. In addition, the size and shape can be changed according to the temperature, which means that the physical and chemical properties of the particles change.

Experimental Example 4. Determination of the size of the emulsion containing a non-spherical amphiphilic dimer and the reversibility of the temperature change

(1) Non-spherical amphiphilic dimer nanoparticles and polystyrene nanoparticles according to Example 1

15a to 15d is a non-spherical amphiphilic dimer dispersion prepared according to Example 1 of the present invention and coconut oil was cooled to 25 ℃, 50 ℃ and again 25 ℃ of a solution mixed in a 97.5: 2.5 volume ratio Emulsion size changes in the state are images and graphs shown using an optical microscope.

As shown in Figure 15a to 15d, when the temperature of the dimer dispersion solution is 25 ℃ room temperature (Fig. 15a), it can be seen that the size of the emulsion is 5 to 25 ㎛. The micelle size at 50 ° C. can be seen to be 1-10 μm, much smaller than 25 μm (FIG. 15B). This is because as the temperature increases, a small number of dimers form an emulsion, which results in many emulsions of small size. In addition, when the dimer dispersion solution temperature was cooled again at 50 ° C. to room temperature, the emulsion was reversibly increased again (FIG. 15C).

16A to 16C are comparative examples of the present invention, in which the particle size change according to the temperature of the solution of the polystyrene dispersion solution prepared in Example 1 (1) and the coconut oil in a 97.5: 2.5 volume ratio The image shown using.

As shown in FIGS. 16A to 16C, polystyrene polymers aggregate to form particles at room temperature (RT) (FIG. 16A), and when the temperature increases to 50 ° C., the particle size decreases (FIG. 16B). However, even when cooled to room temperature again, it can be confirmed that the smaller particles do not grow again (FIG. 16C). This is because unstable particles are destroyed with increasing temperature and phase separation can no longer form the particles.

(2) Non-Spherical Amphiphilic Dimer Nanoparticles According to Example 2

17 to 20 is a non-spherical amphiphilic dimer nanoparticle dispersion solution prepared according to Example 2 (reswelling time is 0 h) of the present invention and the silicone oil (DC 200) in a volume ratio of 9.9: 0.1 Changes in emulsion size with temperature of one solution are images and graphs using an optical microscope.

As shown in Figure 17 to 18, when the temperature is increased from 50 ℃ to room temperature it can be seen that the size of the emulsion is reduced from approximately 10 ㎛ to 4 ㎛, which means that as the temperature increases the number of dimers This means that many small emulsions are made.

In addition, as shown in FIGS. 19 to 20, when the temperature is cooled to room temperature and the heating is repeated at 50 ° C., the size of the emulsion may be reversibly increased and decreased, thereby making the non-spherical shape manufactured according to the present invention. Amphiphilic dimer nanoparticles change the physicochemical properties according to the temperature, and eventually can adjust the interface properties reversibly according to the temperature, it can be seen that the size of the emulsion can be reversibly changed according to the temperature.

Experimental Example 5 Contact Angle Measurement

(1) Non-Spherical Amphiphilic Dimer Nanoparticles According to Example 1

The contact angle according to the temperature at the hydrophobic surface of the non-spherical amphiphilic dimer dispersion solution prepared according to Example 1 of the present invention and the distilled water (poly) (PS) dispersion solution as a comparative example of Example 1 Each was measured.

Figure 21a is a polystyrene (PS) film of water (water), polystyrene dispersion (PS) and non-spherical amphiphilic dimer dispersion solution prepared according to an embodiment of the present invention at 25 ℃ and 50 ℃ Image showing the contact angle to the surface, Figure 21b is an image showing the contact angle to the surface of the poly-dimethylsiloxane (PDMS) film of each solution at 25 ℃ and 50 ℃. 21C is a graph showing each contact angle.

As can be seen in Figure 21a to 21c, the difference in contact angle with temperature can be seen that the largest in the non-spherical amphiphilic dimer dispersion solution of the present invention. This is because the dimer of the present invention forms an emulsion having a different size depending on the temperature than water molecules or polystyrene polymer particles of distilled water. At 25 ° C, a large number of dimers gather to form an emulsion, which increases the size of the emulsion, resulting in a large contact angle with the interface. On the other hand, at 50 ° C, a small number of dimers gather to form an emulsion, resulting in a small emulsion and a contact angle with the interface. Becomes smaller.

(2) non-spherical amphiphilic dimer nanoiba according to Example 2

Preparation of non-spherical dimer nanoparticle dispersion solution, water, polystyrene (PS) dispersion solution, core-shell structure prepared according to Example 2 (re-swelling time is 0 h) of the present invention The contact angle with temperature at the hydrophobic surface of 1 particle (CS) was measured.

22A is an image showing the contact angle to the surface of the polystyrene film of water at room temperature (25 ℃) and 50 ℃, non-spherical amphiphilic dimer nanoparticles (Dimer) dispersion solution prepared according to an embodiment of the present invention 22b shows water, polystyrene nanoparticles (PS), hydrophilic polymer-coated polystyrene nanoparticles (Core-shell, CS) at room temperature (25 ° C.) and 50 ° C., and Example 2 of the present invention. It is a graph showing the contact angle to the surface of the polystyrene film of the non-spherical amphiphilic dimer nanoparticles (Dimer) dispersion solution prepared according to.

FIG. 23A is a polydimethylsiloxane (PDMS) film of water at room temperature (25 ° C.) and 50 ° C., a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution prepared according to Example 2 of the present invention. Figure 23b shows the contact angle to the surface, Figure 23b is water (poly) nanoparticles (PS), hydrophilic polymer coated polystyrene nanoparticles (Core-shell, CS) and water at room temperature (25 ℃) and 50 ℃ It is a graph showing the contact angle of the polydimethylsiloxane (PDMS) film surface of the non-spherical amphiphilic dimer nanoparticles (Dimer) dispersion solution prepared according to Example 2 of the present invention.

As shown in Figures 22a to 23b, it can be seen that the difference in contact angle with temperature is large in the first particle (CS) of the core-shell structure and the non-spherical amphiphilic dimer nanoparticle dispersion solution according to the present invention. This is because, unlike water molecules, polystyrene, the core-shell structured first particles (CS) and non-spherical amphiphilic dimer nanoparticles according to the present invention have a hydrophilic polymer surface which is temperature sensitive, and the dimer of the present invention has a temperature This is because they form emulsions of different sizes. Specifically, at room temperature (RT), since a large number of dimers gather to form an emulsion, the size of the emulsion increases, and the contact angle with the interface appears large. On the other hand, at 50 ° C., a small number of dimers gather to form an emulsion, so the size of the emulsion is It turns out that it becomes small and the contact angle with an interface becomes small.

Through this, the non-spherical amphiphilic dimer nanoparticles prepared according to the present invention will change the physicochemical properties according to the temperature, and thus can reversibly adjust the interfacial properties according to the temperature. It can be seen that the interfacial energy of can be adjusted.

Amphiphilic non-spherical dimer nanoparticles according to the present invention can reversibly adjust the interfacial properties between the liquid-liquid or liquid-solid as the hydrophilic and hydrophobic properties of the particle surface reversibly change with temperature, In the field of medicine and cosmetics, by controlling the size of the emulsion by adjusting the interfacial properties according to the temperature, it is possible to maximize the delivery of drug cosmetics.

Claims

Non-spherical amphiphilic dimer nanoparticles consisting of the first particles and the second particles, it is possible to control the interfacial energy with water reversibly according to the temperature.
The method of claim 1,

Non-spherical amphiphilic dimer nanoparticles, characterized in that the first particles are hydrophilic in surface properties, the second particles are hydrophobic in surface properties.
The method of claim 1,

Non-spherical amphiphilic dimer nanoparticles, characterized in that the interfacial energy between the surface of the first particle and water is reversibly increased or lowered with temperature.
The method of claim 1,

The first particle has a core-shell structure including a core made of a hydrophobic polymer and a shell made of a hydrophilic polymer surrounding the core.

The second particles are formed by protruding a hydrophobic polymer forming the core from one point of the first particles,

Non-spherical amphiphilic dimer nanoparticles, characterized in that the second particles are partially in contact with the first particle at the one point.
The method of claim 4, wherein

The hydrophobic polymer is selected from styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, glycidyl methacrylate and polymers thereof Non-spherical amphiphilic dimer nanoparticles, characterized in that.
The method of claim 4, wherein

The hydrophilic polymer is a non-spherical amphiphilic dimer nanoparticles, characterized in that selected from N-isopropyl acrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate and polymers thereof.
(a) adding a hydrophobic monomer, an ionic initiator and a crosslinking agent to an aqueous solution containing cyclodextrin to prepare a solution in which seed particles are formed;

(b) adding a solution in which the seed particles are formed and an ionic initiator to an aqueous solution containing a hydrophilic monomer to prepare a solution in which the first particles having a core-shell structure are formed;

(c) further adding a hydrophobic monomer to the solution in which the first particles are formed, followed by stirring to swell the first particles;

(d) reswelling the first particles by heating and restirring to 25 to 100 ° C. after step (c); And

(e) adding a radical initiator after the reswelling to polymerize the hydrophobic monomer added in step (c); and

Method for producing non-spherical amphiphilic dimer nanoparticles reversibly controlled interfacial energy with water according to the temperature, characterized in that the hydrophobic monomer is polymerized to form second particles protruding from one point of the first particles.
The method of claim 7, wherein

The first particle of the core-shell structure includes a core made of hydrophobic polymer and a hydrophilic polymer surrounding the core,

The surface properties of the first particles are hydrophilic, the surface properties of the second particles is a method for producing non-spherical amphiphilic dimer nanoparticles, characterized in that hydrophobic.
The method of claim 7, wherein

Method for producing a non-spherical amphiphilic dimer nanoparticles characterized in that the interfacial energy between the surface of the first particle and water is reversibly increased or lowered with temperature.
The method of claim 7, wherein

The step (c) is a method for producing non-spherical amphiphilic dimer nanoparticles, characterized in that carried out for 10 to 30 hours at 10 to 40 ℃.
The method of claim 7, wherein

The method of manufacturing the non-spherical amphiphilic dimer nanoparticles characterized in that the size of the first particle increases, and the size of the second particle decreases as the reswelling time of step (d) increases.
The method of claim 7, wherein

The hydrophobic monomer may be at least one selected from styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate and glycidyl methacrylate. Method for producing a non-spherical amphiphilic dimer nanoparticles characterized in.
The method of claim 7, wherein

The hydrophilic monomer is N-isopropyl acrylamide, methacrylic acid, methacrylate, allylamine, ethylene glycol methacrylate production method of non-spherical amphiphilic dimer nanoparticles, characterized in that at least one.
The method of claim 7, wherein

The cyclodextrin is methyl-β-cyclodextrin, β-cyclodextrin, 2,6-dimethyl-β-cyclodextrin (2,6-dimethyl-β-cyclodextrin). And sodium sulphobutyl ether-β-cyclodextrin. The method for producing non-spherical amphiphilic dimer nanoparticles, characterized in that at least one selected from the group consisting of sodium sulphobutyl ether-β-cyclodextrin.
The method of claim 7, wherein

The ionic initiator is a method for producing non-spherical amphiphilic dimer nanoparticles, characterized in that at least one selected from potassium peroxulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS).
The method of claim 7, wherein

The radical initiator is 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile) , Benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t-butylperoxy-2 -A method for producing non-spherical amphiphilic dimer nanoparticles, characterized in that it is at least one selected from ethylhexanoate, t-butylperoxyisobutyrate and mixtures thereof.
An emulsion composition comprising the non-spherical amphiphilic dimer nanoparticles of claim 1.
The method of claim 17,

The non-spherical amphiphilic dimer nanoparticles are arranged on an aqueous solution-oil interface to form an emulsion,

Emulsion composition, characterized in that the interfacial energy between the surface of the first particle and water is reversibly changed with temperature.
The method of claim 18,

The interfacial energy between the surface of the first particle and water is reversibly changed with temperature, so that the size of the emulsion is reversibly adjusted with temperature.
The method of claim 17,

The emulsion composition is characterized in that the size of 1 to 50 ㎛.
Composition for forming a nanopattern comprising the non-spherical amphiphilic dimer nanoparticles according to claim 1.
The method of claim 21,

The non-spherical amphiphilic dimer nanoparticles are arranged on the interface of the nanopattern-forming solid substrate,

The interfacial energy between the surface of the first particle and water is reversibly changed in accordance with the temperature, the composition for forming a nanopattern.
The method of claim 22,

The interfacial energy between the surface of the first particle and water is reversibly changed with temperature, so that the interfacial energy with the solid substrate for nanopattern forming is reversibly controlled.