KR100870245B1 - Preparation of polymer microcapsule with semiconductor nano particles - Google Patents

Abstract

A manufacturing method of a semiconductor nanoparticle-containing microcapsule is provided to prevent the change and degradation of spectroscopic property and to suppress the elution even in the external circumstances change such as various solvent and pH change. A manufacturing method of a semiconductor nanoparticle-containing microcapsule comprises a first step for reforming the surface of a semiconductor nanoparticle with a C5-C20 fatty acid compound; a second step for mixing the surface-modified semiconductor nanoparticle, organic solvent and emulsion aqueous solution to manufacture droplet; and a third step for emulsion-polymerizing the droplet and the amine-based -aldehyde copolymer to microcapsule polymerized wit polymer on the surface of the droplet containing semiconductor nanoparticles. The semiconductor nanoparticle has the particle size of 1 ~ 100 nm.

Description

Manufacturing method of microcapsules containing semiconductor nanoparticles {Preparation of polymer microcapsule with semiconductor nano particles}

The present invention relates to a method of manufacturing a microcapsule containing particles in the form of a capsule containing semiconductor nanoparticles therein, wherein the semiconductor nanoparticles contain semiconductor nanoparticles on the inside of the capsule or the inner wall of the capsule, and thus are not easily dissolved. will be.

In general, a polymer particle including semiconductor nanoparticles is a form in which the semiconductor nanoparticles are embedded in the inside of the particle when the semiconductor nanoparticles physically adsorb on the surface of the polymer, chemical bonds, or polymer chains form a bead-shaped polymer particle. And the like are known.

As such, when the semiconductor nanoparticles are physically adsorbed on the surface of the polymer particles or attached by chemical bonds, they are greatly influenced by external conditions. That is, if the change in pH of the external environment, chemical change by reactive substances, elution by solvent, etc., the fluorescence characteristics of semiconductor nanoparticles are easily changed or lost. Only serves as a support of the nanoparticles.

In addition, the method in which the semiconductor nanoparticles are included in the swollen polymer particles by dispersing the fluorescent particles in the polymer beads forms a state in which the semiconductor nanoparticles are buried in the polymer chain, thereby maintaining stability against external environmental changes. However, its properties can be changed by various physical and chemical actions with the polymer chains forming the polymer particles. That is, since the semiconductor nanoparticles and the polymer chains are bonded at the molecular level, physical and chemical effects are greatly affected by the physical properties of the polymer chains. In addition, the content of the semiconductor nanoparticles varies depending on the size and morphology of the polymer particles, and in the case where the semiconductor nanoparticles have fluorescence, the position where the semiconductor nanoparticles are located is specifically located in the inner center layer of the polymer particles and near the surface. There was a problem in that particles having irregular spectroscopic properties were formed depending on the location.

The present invention is a spectroscopic characteristic when the conventional method of containing semiconductor nanoparticles in the polymer has sensitivity to external environmental changes, dissolution of the contained semiconductor nanoparticles due to a decrease in dispersibility of the semiconductor nanoparticles, and fluorescence among the semiconductor nanoparticles. The present invention proposes a method of manufacturing a microcapsule completely enclosed with semiconductor nanoparticles by improving problems such as change and degradation.

The present invention comprises the steps of modifying the surface of the semiconductor nanoparticles with a fatty acid compound having 1 to 20 carbon atoms; Preparing a droplet by mixing the surface-modified semiconductor nanoparticles, an organic solvent, and an aqueous solution of an emulsifier; And preparing a microcapsule in which the polymer is polymerized on the surface of the droplet containing the semiconductor nanoparticle by emulsion-polymerizing the droplet and the amine-aldehyde copolymer. The method has its features.

The present invention is to prepare a microcapsule containing the semiconductor nanoparticles therein by a method through emulsion interfacial polymerization, the semiconductor nanoparticles are stably encapsulated inside the capsule, such as various solvents such as polar or nonpolar solvents, pH change, etc. In the case of eluting external environmental changes or having fluorescence in the semiconductor nanoparticles, the spectroscopic characteristics are not changed or deteriorated, so micro processes such as labeling materials of the sensor are required and its utilization is expected in the field of biosensors exposed to various environments.

The present invention forms a droplet by mixing an aqueous solution of an emulsifier and an organic solution containing semiconductor nanoparticles whose surface is modified with a fatty acid compound, and the polymer is polymerized on the surface of the droplet by emulsion polymerization of the droplet and the amine-aldehyde copolymer. To a method for producing a microcapsule. In the prepared microcapsules, the semiconductor nanoparticles are encapsulated inside the capsule and stacked on the capsule wall, so that the microcapsules are hardly eluted even in external environment changes such as specific solvent conditions and pH changes. In particular, in the case where the contained semiconductor nanoparticles have fluorescence, they have a characteristic of changing spectroscopic characteristics and not deteriorating.

The microcapsules containing the semiconductor nanoparticles of the present invention are a series of processes for surface modification, droplet formation, and emulsion polymerization at the droplet interface, in which fluorescent particles are physically adsorbed, chemically bonded to polymer chains, and polymer chains. It is not a state, but is encapsulated inside the capsule and stacked on the inner wall. The emulsion interfacial polymerization is generally a method for preparing capsules in the art, but a technique for successfully encapsulating semiconductor nanoparticles using the same has not been reported, and conventional conditions are prepared under acidic conditions and oxidized. The process of encapsulating highly sensitive semiconductor nanoparticles into capsules has been limited.

Thus, the present invention is applied to a process for producing a microcapsule containing the semiconductor nanoparticles by improving the manufacturing process under conditions that minimize the influence of the semiconductor nanoparticles in the manufacturing process. In other words, this is not simply preparing a microcapsule containing the semiconductor nanoparticles by introducing a known method, but is carried out under the optimized conditions for encapsulating the semiconductor nanoparticles inside the capsule and laminated on the inner wall. Specifically, there is a feature in the technical configuration of the semiconductor nanoparticles with the optimum coating material applied to minimize the effect of the manufacturing process and minimize the possibility of exposure to acid condensation conditions.

Hereinafter, a method of manufacturing a semiconductor nanoparticle-containing microcapsules according to the present invention will be described in detail.

First, the surface of a semiconductor nanoparticle is modified with a C1-C20 fatty acid compound. The semiconductor nanoparticles are generally used in the art and use nanocrystals having a size in the range of 1 to 100 nm. If the size of the particles is less than 1 nm, the original characteristics of the semiconductor nanoparticles are lost. In case of exceeding the size distribution of each nanoparticle is uneven, so that the problem occurs that the characteristic distribution is very wide, it is good to maintain the above range. In particular, the semiconductor nanoparticles may be a particle represented by the following formula (1).

M _m X _n

In Formula 1, M is an element selected from Zn, Cd, Ga, Ge, In, Tl, Si, Ge, Sn, and Pb, X is O, S, Se, Te, N, P, As, Sb and Bi M and n are integers of 1-4, respectively, in order to match oxidation number.

The inorganic fluorescent particles represented by Chemical Formula 1 correspond to quantum dots called semiconductor nanocrystals, and have a single wavelength by allowing a narrow range of fluorescence wavelengths through bandgap adjustment. Application to lasers, light-emitting sensors, in vivo labeling materials has been studied, which can be applied to the present invention. In the case of such inorganic fluorescent particles, a core-shell structure of two or more components may be formed, and the surface of the particles may be lipophilic in order to improve affinity for an organic solvent. Inorganic fluorescent particles show high dispersion ability in nonpolar solvents through lipophilizing, but in order to realize spectroscopic characteristics as fluorescent particles as materials, stability of external environment and dispersion of medium are controlled, binding and aggregation of support Sedimentation, etc. must be resolved.

The semiconductor nanoparticles are subjected to a hydrophobic process so as to be contained in the droplets, and at this time, the surface is subjected to a reforming reaction using a fatty acid compound having 1 to 20 carbon atoms. The fatty acid compound is selected from saturated or unsaturated fatty acids having 1 to 20 carbon atoms, specifically, oleic acid, palmitic acid, ethylhexanoic acid, linolenic acid, or the like may be used. The fatty acid compound is contained in the range of 0.5 to 10% by weight with respect to the semiconductor nanoparticles, when the content is less than 0.5% by weight, the effect of coating is lowered. It is desirable to maintain this range because there is a problem of losing.

Next, droplets containing semiconductor nanoparticles are prepared by mixing semiconductor nanoparticles whose surface is modified with fatty acid compounds, an aqueous solution of an emulsifier in the range of pH 6.5 to 7.5, and an organic solvent. At this time, the mixture is stirred at 50 to 100 ° C. in a range of 500 to 4000 rpm to disperse to a size in a range of 100 to 10000 nm to prepare droplets. When the stirring speed is less than 500 rpm, the size of the droplets is large and uneven, and if it exceeds 4000 rpm, it is preferable to maintain the above range because a separate device for high speed agitation occurs. In addition, in this case, when the pH range of the solution is out of the range, it may be a problem that oxidation of the semiconductor nanoparticles may proceed, so it is preferable to maintain the range.

The emulsifier is generally used in the art, but is not particularly limited, and specifically, a single compound or a mixture of two or more selected from poly (styrene-maleic acid) copolymer, polyvinyl alcohol, and sodium dodecyl sulfate may be used. have. Such emulsifiers are used in the range of 0.1 to 10 weight ratios with respect to the aqueous solution. If the amount is less than 0.1 weight ratio, there is no effect of keeping the droplets stable, and if the amount exceeds 10 weight ratios, it becomes difficult to remove them. It is good to keep it.

The semiconductor nanoparticles are used by dissolving them in an organic solvent, and the organic solvent may not be mixed with water generally used in the art, but aromatic or aliphatic hydrocarbons may be used, but specifically, decane and dodecane in the present invention. , Octadecane, hexylbenzene and the like are preferably used. The organic solvent is used in the range of 5 to 80 weight ratio with respect to the aqueous solution containing an emulsifier. When the amount of the organic solvent is less than 5 weight ratio, the number of capsule particles obtained in one reaction is small, so that the reaction efficiency is lowered and exceeds 80 weight ratio. In this case, it is preferable to maintain the above range because the concentration of the droplets increases, making it difficult to obtain a spherical constant size capsule.

Next, the droplet containing the fluorescent particles and the amine-aldehyde copolymer are interfacially polymerized to prepare a capsule in which a polymer is polymerized on the surface of the droplet. In this case, the emulsion interfacial polymerization is carried out in the range of pH 3 to 5 under the conditions of 50 ~ 100 ℃, if the polymerization temperature is less than 50 ℃ the polymerization reaction is very slow, when the temperature exceeds 100 ℃ boiling phenomenon occurs It is preferable to maintain the above range because a problem of unstable droplets occurs. In addition, the pH is set to neutral for the protection of the semiconductor nanoparticles at the time of droplet formation, the temperature is increased when the emulsion interfacial polymerization is performed, and then gradually lowered the pH after 1 hour to maintain the pH range of 3 to 5 The nanoparticles form a condition that is separated as much as possible from the aqueous solution, and the emulsion interfacial polymerization proceeds under acidic conditions. If it is out of the range, the condensation reaction tends to be slow, so it is preferable to occupy the range.

The amine-aldehyde copolymer is generally used in the art, but is not particularly limited. The amine compound is a copolymer of an amine compound and an aldehyde compound, and the amine compound is melamine, urea, alkylene having 1 to 10 carbon atoms. One single compound or a mixture of two or more selected from diamine, alkylenetriamine having 1 to 10 carbon atoms, triaminobenzene and diaminobenzene can be used. In addition, the aldehyde-based compound may use a single compound or a mixture of two or more species selected from formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, benzaldehyde and paraformaldehyde.

The copolymer contains an aldehyde-based compound in the range of 30 to 200 mol% with respect to the amine-based compound. When the content is less than 30%, the bond of the polymer is not sufficient, and the unreacted aldehyde is more than 200 mol%. The problem is that a large amount remains.

The amine-aldehyde copolymer is used in the range of 5 to 20 weight ratios with respect to the droplets. If the amount is less than 5 weight ratios, a sufficient polymer outer layer is not formed to surround all the droplets. It is preferable to maintain the above range because a problem occurs that polymer particles other than the capsule outer layer are formed irrespective of the enemy.

Thereafter, purification is performed by a repeated process of centrifugation and washing, and dried at 150 ° C. or lower, specifically, below 150 ° C. to prepare microcapsules containing fluorescent particles. If the drying temperature exceeds 150 ℃ it is good to maintain the above range because the problem occurs that the properties of the encapsulated semiconductor nanoparticles are altered.

In the above process, the present invention can produce a fluorescent particle-containing microcapsules, the fluorescent particles are contained in the form of dispersion or laminated on the inner wall of the microcapsule, the microcapsules are in the range of 100 nm ~ 1 mm, organic solvent The elution amount of the fluorescent particles in the range of 1 ppm or less, the dissolution rate is maintained in the range of 0 to 50%, and shows the relative luminescence intensity of 40 to 90% of the fluorescence emission intensity of the semiconductor nanoparticles in solution before encapsulation.

On the other hand, it can be seen that the fluorescent particles containing the microcapsules prepared according to the present invention hardly dissolve the fluorescent substance contained therein even when dispersed in a solvent having high solubility in the fluorescent particles. At this time, the solvent used for the dispersion may be water, alcohol, chloroform, dichloromethane, dichloroethane, tetrachloromethane and tetrahydrofuran. At this time, the concentration of the fluorescent particles in the solvent portion is in the range of about 1 ppm or less, it can be confirmed that the elution does not appear at all as a result of the concentration of the fluorescent particles contained in the microcapsules does not change.

For example, if the spectroscopic characteristics of the microcapsules including fluorescent particles were checked, the average particle size of 8 nm semiconductor nanocrystals composed of CdSe / ZnS was used as fluorescence particles, and octadecane was used as an inner core, and melamine-formaldehyde resin was used. In the case of the outer polymer shell layer, a fluorescence emission spectrum of λ _max 600 nm was observed, indicating that the spectroscopic characteristics of the fluorescent particles were well preserved even after encapsulation.

In addition, in the case of aliphatic and aromatic hydrocarbons, such as octadecane, in the case of using such a dispersion solvent, the internal core material elutes to the outside over 5 minutes to 1 hour. This phenomenon is thought to be caused by the low density of the outer wall and the penetration of the solvent and the dissolution of the internal material by the solvent in which the polymer shell layer formed at about 50 nm can be swollen. Even in the elution of the internal material, the fluorescent nanoparticles encapsulated inside the capsule were trapped in the polymer shell layer and showed no results out of the capsule. The microcapsules containing the fluorescent particles of the present invention are fluorescence on the inner surface of the melamine-formaldehyde resin outer layer formed 50 nm thick in microcapsules when observed using an electron microscope and a laser confocal fluorescence microscope. It can be seen that the particles are attached and prepared.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1

After diluting 1.32 g of poly (styrene-maleic acid) copolymer sodium salt (molecular weight: 120,000, viscosity; 24,000 cps, 30% aqueous solution, maleic acid content: 50 mol%) as an emulsifier to 9 g of ion-purified water The pH was adjusted to 4.5 using 20 wt% NaOH and 20 wt% H ₂ SO ₄ with rapid stirring at 600 rpm. To 6 g of octadecane, 45 mg of CdSe / ZnS fluorescent particles (particle size 8 nm) whose particle surface was modified with 2% by weight of oleic acid were dispersed, added to an aqueous solution of the emulsifier prepared above, for 10 minutes in a thermostat set at 70 ° C. Dispersion was carried out using a homogenizer.

In a three-necked round bottom flask, 0.396 g of melamine powder, 0.764 g of formaldehyde, and 1.32 g of ionic purified water were heated, and the temperature was raised to 70 ° C. under a nitrogen atmosphere and stirred at 200 rpm for 10 minutes to melamine prepolymer. , Hereinafter referred to as 'MF'. Droplets containing CdSe / ZnS fluorescent particles were added thereto, followed by reaction at 70 ° C. for 3 hours to prepare MF-capsules. The MF-capsules containing the prepared fluorescent particles were separated from an aqueous solution by centrifugation, washed with hexane and ethanol, and centrifuged three times, and dried in powder form using a lyophilizer. At this time, the size of the prepared MF-capsules showed a 400 nm range (± 100 nm).

Figure 1 shows a laser confocal fluorescence micrograph of the prepared MF-capsules, it was confirmed that the fluorescent particles are attached along the inner wall of the capsule.

Example 2

MF-capsules were prepared in the same manner as in Example 1, except that 200 mg of TiO ₂ (particle size 5 nm) whose surface was modified with 4% by weight of palmitic acid instead of CdSe / ZnS. At this time, the size of the prepared MF-capsules showed a 400 nm range (± 100 nm).

Comparative Example 1

1 g of polystyrene (molecular weight: 30000) was added to 10 mL of tetrahydrofuran, and heated and stirred at 70 ° C. for 1 hour to prepare a homogeneous solution. 45 mg of CdSe / ZnS fluorescent particles (coated with 2% by weight of oleic acid per particle, particle size of 8 nm) were added to the solution cooled to room temperature and stirred for 10 minutes. 800 mg of sodium dodesylsulfonate was dissolved in 100 mL of ethanol, and the prepared polystyrene-fluorescent particle solution was slowly added dropwise for 30 minutes while rapidly stirring at 800 rpm using a homogenizer. After the stirring was completed, the polymer particles were separated by a centrifuge and washed with ethanol, hexane and water. The process was repeated three times and dried to prepare polystyrene polymer particles including CdSe / ZnS fluorescent particles. At this time, the size of the polymer particles prepared above showed a 300 nm range (± 200 nm).

Comparative Example 2

In the same manner as in Comparative Example 1, coumarin 314-polystyrene polymer particles were prepared using 40 mg of coumarin 314 (manufactured by Aldrich) instead of CdSe / ZnS as fluorescent particles. At this time, the size of the polymer particles prepared above showed a 350 nm (± 100 nm) range.

Comparative Example 3

In the same manner as in Comparative Example 1, instead of CdSe / ZnS as a fluorescent particle to prepare a TiO ₂ -polystyrene polymer particles using 200 mg of hydrophobic TiO ₂ (coated 4% by weight of palmitic acid, particle size 5 nm) 200 mg. It was. At this time, the size of the polymer particles prepared above showed a 300 nm range (± 200 nm).

Comparative Example 4

In the same manner as in Example 1, coumarin 314 (Aldrich) 40 mg instead of CdSe / ZnS was used to prepare a polymer particle containing coumarin 314. At this time, the size of the polymer particles prepared above was in the range of 4000 nm (± 100 nm).

Comparative Example 5

     The polymer particles were prepared in the same manner as in Example 1, but using 45 mg of CdSe / ZnS fluorescent particles (particle size 8 nm) whose surface was modified with 2% by weight of trioctylphosphine oxide (TOPO) instead of oleic acid. . At this time, the size of the polymer particles prepared above showed a 350 nm (± 100 nm) range.

Experimental Example 1

Experiments were carried out to confirm the dissolution ability of the fluorescent particles contained in the particles prepared in Examples 1 and 2 and Comparative Examples 1 to 5. First, the amount of fluorescent material contained in the particles was quantified by using ICP-AES (Inductive coupled plasma-atomic emission spectroscopy) or by concentration calculation through UV-Vis spectroscopy. Next, the particles prepared in Examples 1 to 2 and Comparative Examples 1 to 5 were dispersed in chloroform and sonicated for 1 hour to elute the fluorescent material contained in the particles, and then treated with particles. The solution was analyzed by the above method to quantify the amount of fluorescent material contained in the particles.

division Ingredients Content when manufacturing particles (% by weight) Content after dissolution evaluation (% by weight) Elution amount (dissolution rate) (wt%) Example 1 CdSe / ZnS nanoparticles (oleic acid coating, particle size 8 nm) 0.39 0.39 0 (0%) Example 2 Hydrophobic TiO ₂ (coated with palmitic acid, particle size 5 nm) 0.22 0.22 0 (0%) Comparative Example 1 CdSe / ZnS nanoparticles (oleic acid coating, particle size 8 nm) 0.17 0.01 0.16 (94%) Comparative Example 2 Coumarin 314 (Aldrich) 0.07 0 0.07 (100%) Comparative Example 3 Hydrophobic TiO ₂ (coated with palmitic acid, particle size 5 nm) 0.28 0.01 0.27 (96%) Comparative Example 4 Coumarin 314 (Aldrich) 0.12 0.05 0.07 (58%) Comparative Example 5 CdSe / ZnS nanoparticles (trioctylphosphine oxide coating, particle size 8 nm) 0.33 0.24 0 (0%)

As shown in Table 1, the particles of Examples 1 to 2 according to the present invention was confirmed that no phenomenon that the fluorescent particles are completely encapsulated inside the capsule and escaped to the outside of the capsule.

Specifically, it was confirmed that the CdSe / ZnS nanoparticles used in Example 1 were well encapsulated inside the capsule and did not escape out of the capsule as shown in FIG. The TiO ₂ particles used in Example 3 had a smaller 4 nm average size than the nanoparticles of Example 1 but were also encapsulated inside the capsule and did not escape out of the capsule.

Comparative Examples 1 to 3 were manufactured in a form in which fluorescent particles are buried in polymer particles aggregated into a generally known spherical shape, and almost all of the fluorescent particles contained therein were eluted. This can be seen that most of the nanoparticles and compounds contained in the form trapped inside as the polymer chain is released in the solvent conditions of high solubility to the polymer is largely escaped to the outside. In Comparative Example 4, coumarin coumarin (314) was used as an organic fluorescent substance, and the content contained in the capsule was decreased after the dissolution experiment. It is understood that it is completely dissolved in the solution penetrating into the capsule as a monomolecular compound and penetrates the melamine-formaldehyde polymer shell layer.

2 and 3 show the same results as in Table 1 above, even if the core material that was inside the capsule, that is, oil droplets during manufacture, was used as the oil droplets during manufacture, and all materials forming the inside of the capsule were eluted out to be deformed. It can be seen that the nanoparticles encapsulated inside the capsule are present in the capsule as it is.

Experimental Example 2

The relative luminescence fluorescence intensity of the fluorescent particles contained in the particles prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was measured. In this case, the relative luminescence fluorescence intensity is measured by measuring the intensity of luminescence generated by absorbing the relative luminescence intensity of the semiconductor nanoparticles in the solution state before the fluorescence emission intensity at λ = 420 nm by fluorescence spectrometer.

division Ingredients Relative fluorescence intensity% (relative to the luminescence intensity of the same amount of fluorescence component before encapsulation) Example 1 CdSe / ZnS nanoparticles (oleic acid coating, particle size 8 nm) 67 Comparative Example 1 CdSe / ZnS nanoparticles (oleic acid coating, particle size 8 nm) 21 Comparative Example 2 Coumarin 314 (Aldrich) 5 Comparative Example 4 Coumarin 314 (Aldrich) 43 Comparative Example 5 CdSe / ZnS nanoparticles (trioctylphosphine oxide coating, particle size 8 nm) 5

As shown in Table 2, the microcapsules prepared according to the present invention maintain the luminous effect well as a relative value of the luminous intensity of the fluorescent material included in the polymer particles (relative value of the luminous intensity before encapsulation). You can check it. This can be said that the fluorescent material present in the inside of the particles can be excited to the external light by being present in the inner wall just below the polymer shell layer, as shown in Figure 1, it can be said that the emission of fluorescence can also effectively radiate to the outside.

In the results of Comparative Examples 1 and 2 it can be seen that it is difficult to show the spectroscopic characteristics of the fluorescent material reacting to the external light due to the state in which the fluorescent material is embedded in the polymer particles.

In Comparative Example 4, the coumarin 314 contained in the microcapsules may exhibit fluorescence characteristics relatively well, but as shown in Experimental Example 1, it shows a tendency to elute.

The results of Comparative Example 5 shows the importance of the coating material of the semiconductor nanoparticles, when coated with trioctylphosphine oxide, most of the fluorescence properties are lost in the manufacturing process encapsulated into capsules and the emission intensity is very weak. Can be seen. From the results in Table 1, the content of the semiconductor nanoparticles is not significantly different from the case of Example 1 coated with oleic acid, but it can be seen that the result of the emission intensity shown in Table 2 is very low.

Figure 1 shows a laser confocal micrograph of the microcapsules prepared in Example 1 according to the present invention.

Figure 3 shows a transmission electron microscope (TEM) photograph after the microcapsules prepared in Example 1 according to the present invention in the same conditions as in Experiment 1.

4 shows a transmission electron microscope (TEM) photograph after the microcapsules prepared in Example 2 according to the present invention are treated under the same conditions as in Experimental Example 1. FIG.

Claims (8)

A first step of modifying the surface of the semiconductor nanoparticles with a fatty acid compound having 5 to 20 carbon atoms; Preparing a droplet by mixing the surface-modified semiconductor nanoparticles, an organic solvent, and an aqueous solution of an emulsifier in a range of pH 6.5 to 7.5; And Interfacial polymerization of the droplet and the amine-aldehyde copolymer to prepare a microcapsule polymerized with polymer on the surface of the droplet containing the semiconductor nanoparticles Method for producing a semiconductor nanoparticle-containing microcapsule comprising a. The method of claim 1, wherein the semiconductor nanoparticles are 1-100 nm in size. The method of claim 2, wherein the semiconductor nanoparticles are inorganic fluorescent particles represented by Formula 1 below: [Formula 1] M _m X _n In Formula 1, M is an element selected from Zn, Cd, Ga, Ge, In, Tl, Si, Ge, Sn, and Pb, X is O, S, Se, Te, N, P, As, Sb and Bi M and n are integers of 1-4, respectively, in order to match oxidation number. The method of claim 1, wherein the amine-aldehyde copolymer is selected from melamine, urea, alkylenediamine having 1 to 10 carbon atoms, alkylenetriamine having 1 to 10 carbon atoms, triaminobenzene and diaminobenzene. It is a copolymer of the amine type compound of a single compound or 2 or more types of mixtures, and an aldehyde type compound. The method according to claim 1, wherein the fatty acid compound is a saturated or unsaturated fatty acid compound having 1 to 20 carbon atoms. The method of claim 1, wherein the size of the microcapsules is in the range of 100 nm to 1 mm. delete delete

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