KR101677102B1 - Fabrication Method for 3D Microarchitectures Having Microparticles with Different Height Connected Each Other - Google Patents
Fabrication Method for 3D Microarchitectures Having Microparticles with Different Height Connected Each Other Download PDFInfo
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- KR101677102B1 KR101677102B1 KR1020150060343A KR20150060343A KR101677102B1 KR 101677102 B1 KR101677102 B1 KR 101677102B1 KR 1020150060343 A KR1020150060343 A KR 1020150060343A KR 20150060343 A KR20150060343 A KR 20150060343A KR 101677102 B1 KR101677102 B1 KR 101677102B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/124—Treatment for improving the free-flowing characteristics
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/10—Investigating individual particles
- G01N15/14—Electro-optical investigation, e.g. flow cytometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
Abstract
The present invention relates to a method for producing monodisperse microparticles having a three-dimensional structure of a more complex structure using a replica mold, and more particularly, to a method for producing a monodisperse microparticle having a structure in which micro- ≪ / RTI > More particularly, the present invention relates to a method for producing microparticles using a solvent which is not mixed with a polymer monomer and a polymer monomer, the method comprising the steps of: A) connecting two or more shapes having different widths by bridges, Preparing a duplicate mold having a cross-sectional structure in which the ratio of the width of the bridge to the width of the figure having a width larger than or equal to the width of the figure having a small width among the connected figures is 0.4 or less; B) filling the micro mold of the replica mold with the polymer monomer; C) a solvent having a swelling coefficient of 1.1 or more with respect to the replica mold, while satisfying the condition that the wettability to the replica mold is larger than that of the polymer monomer and the density is lower than that of the polymer monomer, is applied to the upper surface of the micro- Swelling the replica mold; And D) polymerizing the polymeric monomer. The present invention also relates to a method for producing microstructures of different height connected with each other.
Description
The present invention relates to a method for producing monodisperse microparticles having a three-dimensional structure of a more complex structure using a replica mold, and more particularly, to a method for producing a monodisperse microparticle having a structure in which micro- ≪ / RTI >
Microparticles are characterized by their ability to control various parameters and to impart new functionality through control of shape such as particle size, shape, surface charge, internal structure with small volume, large surface area, high maneuverability. This feature has high potential as a tool for high-speed mass screening and immunoassay such as chromatography in bio-industry, supports for flow cell analysis, detection and isolation of DNA and proteins.
According to the prior art, microparticles were prepared by suspending polymerization in which a small amount of a continuous phase, a dispersed phase, and a polymerization initiator, which do not mix with each other in a large-sized reactor, was added to give a mechanical force. Such suspension polymerization has an advantage that mass production can be performed. However, because of the polydispersity of the obtained particles, a separate separation step is required and the particle size distribution is also limited. In order to solve such a problem, emulsion polymerization which produces monodisperse microparticles having a certain shape by forming micelles through emulsification with hydrophobic monomers by a water-soluble surfactant contained in the continuous phase and polymerizing them with a water-soluble initiator emulsion polymerization was introduced. However, it is difficult to clean the used surfactant, the selection of materials is limited, and the size distribution of particles that can be formed does not exceed a certain range as in suspension polymerization.
In recent years, studies have been made to solve and improve the problems of the prior art by fabricating a device capable of dynamic / static microfluid control through a micro electro mechanical systems (MEMS) based nano or micro structure forming technique.
The dynamic method is a method of producing microparticles by using microfluidics, and has a common characteristic that droplets are formed by using a desired material and then crosslinked to produce particles. According to this method, monodisperse particles can be simply produced, but the washing process is very important because the produced microparticles are present in a mixed state with unreacted monomer or continuous phase solvent. In addition, expensive equipment is required, the experimental conditions such as flow rate must be precisely controlled, and the selection of materials is also affected by hydrodynamic or thermodynamic factors. Also, since the shape of the particles can not be largely deviated from the spherical shape or is limited to the two-dimensional structure, the application field is limited.
The static method can easily and easily manufacture monodisperse particles of a desired size by injecting a fluid into a replica mold having a micro sized engraved pattern and polymerizing it. Through the introduction of the microparticle production method using the replica mold, it is possible to easily manufacture the three-dimensional shape control and the multi-functional particles which were difficult to realize in microfluidics. In particular, it is possible to manufacture anisotropic particles having a more complicated shape or system in a conventional isotropic spherical shape, so that it is possible to easily control the shape serving as the greatest variable for determining the functionality of the particle, . ≪ / RTI >
The inventors of the present invention have found that it is possible to use a chemical treatment method which changes the surface and interfacial energy beyond the limit of the conventional clone molding which is dependent on the engraving pattern and the physical treatment for controlling the pattern and aspect ratio of the clone mold used and the stretching or compression by the external stimulus A method of controlling the shape of the microparticles by using the above-described method is disclosed in, for example, Patent Documents 10-1221332, 10-1399013, 10-1408704, and 10-2015-0053226. It becomes possible to control the three-dimensional shape of the microparticles in various forms by the above methods. However, the shape of the microparticles is limited to a structure in which curvature is formed on a sphere or a surface, and there are still many limitations in the production of monodisperse microparticles having a more complex three-dimensional structure.
Disclosure of the Invention In order to solve the problems of the conventional techniques described above, the present invention provides a method of manufacturing a monodisperse three-dimensional microstructure having a complicated structure in which particles having different heights are connected to each other, And a method for producing the same.
According to an aspect of the present invention, there is provided a method of producing microparticles using a solvent that is not mixed with a polymer monomer and a polymer monomer, the method comprising: A) one or more shapes having different diameters are connected by bridges, Is less than or equal to the width of the figure having a small width among the figures connected by the bridge and the ratio of the width of the bridge to the width of the figure having a large width is 0.4 or less, Preparing; B) filling the micro mold of the replica mold with the polymer monomer; C) a solvent having a swelling coefficient of not less than 10% with respect to the replica mold while satisfying the condition that the wettability to the replica mold is larger than that of the polymer monomer and the density is lower than that of the polymer monomer, is applied to the upper surface of the micro- Thereby swelling the replica mold; And D) polymerizing the polymeric monomer. The present invention also relates to a method for producing microstructures of different height connected with each other.
FIG. 1 is a schematic view illustrating a process of forming a microstructure according to an embodiment of the present invention. Referring to FIG. To this end, the micro mold of the replica mold according to the present invention includes two or more shapes whose cross-sectional structures are connected by bridges so that two or more microparticles to be produced can be connected to each other.
When a solvent is filled in the micro mold of the replica mold and a solvent satisfying the condition that the wettability of the replica mold with respect to the replica mold is larger than that of the polymer monomer and the density is lower than that of the polymer monomer is added, If they are different from each other, a difference in Laplace pressure occurs because the Laplace pressure acting on the polymer monomer and the solvent is not uniform depending on the position in the micro-mold. Since the polymer monomer has low wettability with respect to the replica mold, the Laplace pressure on the side having a smaller width of the micro-mold becomes larger than the side having a larger width. Therefore, the polymer monomer in the narrow bridge region is moved toward the mold formed by the wide shape, and as the bridge region is decompressed, the polymer monomer on the mold side formed by the narrow shape additionally moves to the bridge region, The polymer monomer moves toward the wide shape in the narrow shape.
In addition, if the solvent has a property of swelling the replica mold, the effect of shrinking the micro-mold is obtained, and the effect of squeezing the polymer monomer onto the upper surface of the micro-mold is generated. Thus, the horizontal movement of the polymer monomer by the Laplace pressure difference The polymer monomer moves to the vertical side. Therefore, the height of the polymer monomer in the area formed by the graphic pattern having a larger width becomes higher than the area formed by the graphic pattern with the narrower width, and when this polymer is polymerized, a microstructure in which particles having different heights are connected to each other is constructed . As a result of a preliminary experiment in which various solvents were tested for the replica mold, the microstructure according to the present invention can be effectively produced when the flatness factor (S) indicating the degree of swelling of the replica mold is 1.1 or more. The swelling coefficient (S) is expressed by the following equation.
Swelling coefficient (S) = D / D o
At this time, D is the length of the material constituting the replica mold, and D o is the length of the dried state before applying the solvent.
Depending on the material of the replica mold, those skilled in the art will be able to select a suitable solvent if it satisfies the above condition, and it will be meaningless to limit the kind thereof.
In addition, as a result of preliminary experiments on various shapes of micro molds, regardless of the shape of the micro mold, when the width of the bridge is 0.4 or less with respect to the width of the graphic having a large width, the Laplace pressure It was confirmed that tea was formed. In order for the two particles to be connected by a bridge, it is natural that the width of the bridge should be smaller than or equal to the width of the figure having a small width among the figures connected by the bridge.
If the width of the bridge is too narrow, the width of the bridge is too narrow due to the swelling of the replica mold to restrict the movement of the solvent. If the bridge is too wide, the capillary force is lowered and the Laplace pressure The movement of the solvent by the tea was not efficient.
As described above, since the difference in the width of the figure is closely related to the Laplace pressure difference, the height difference of the microparticles constituting the microstructure can be controlled by the ratio of the width of the figure connected by the bridge. That is, the greater the difference in the width of the figure, the greater the height difference.
Also, since the difference in height of the microparticles constituting the microstructure is proportional to the degree of swelling of the replica mold, and it takes a certain time for the solvent to swell the replica mold to reach the equilibrium state (see FIG. 3) It is possible to control the difference in height of the microparticles constituting the microstructure by a period of time after the solvent is applied to the upper surface of the micro mold and then left to stand.
In the present invention, the polymer monomer is a polymer capable of forming a polymer by a polymerization reaction. The polymerization reaction may be thermal polymerization, polymerization by a catalyst, photopolymerization or a sol-gel reaction. Also, when a catalyst is required in the polymerization, the catalyst may be included in the polymer monomer in consideration of the nature of the catalytic reaction, or may be included in the solvent to cause a polymerization reaction. The core of the present invention is to produce a microstructure in which particles having different heights are connected using swelling of a replica mold and Laplace pressure difference in a replica mold. Any kind of the polymer monomer may be used as long as it is known from the prior art And it is meaningless to limit its concrete kind.
In the following examples, it is described that PDMS is used as the material of the replica mold. However, it is easy for a person skilled in the art to select the polymer monomer and the solvent satisfying the above-mentioned conditions according to the prior art. According to a preliminary experiment, the PDMS was found to be a mixture of pentane, PDMS oil, diisopropylamine, hexane, heptane, triethylamine, ether, cyclohexane, trichlorethylene, dimethoxyethane, xylene, toluene, ethyl acetate, benzene, , A swelling coefficient of 1.1 or more, and thus an effective microstructure is produced. The microstructure of the microstructure of the present invention is not particularly limited, and examples of the microstructure of the microstructure may include, but are not limited to, polypropylene, polystyrene, Could. Therefore, a polymer which meets the density or wettability can be selected depending on the kind of the polymer monomer used.
As described above, the conventional microparticles of the present invention merely form a curvature on the surface, whereas the microparticles of the present invention can be produced by a simple method of a monodisperse three-dimensional microstructure having a complicated structure in which particles having completely different heights are connected to each other have. Since microparticles can impart functionality by size, shape, and structure of the particles, the microstructure manufacturing method of the present invention can be advantageously used for realizing a three-dimensional structure suitable for the use of the microparticles to be used.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a process of forming a microstructure according to the present invention; FIG.
2 is an optical image showing the shape of a microstructure fabricated by an embodiment of the present invention.
Figure 3 is an optical image showing the shape of microparticles due to solvent and swelling of the replica mold over time.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are merely examples for explaining the content and scope of the technical idea of the present invention, and thus the technical scope of the present invention is not limited or changed. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.
Example
Example 1: Fabrication of a replication mold
A negative photoresist (SU-8, Microchem Co., USA) was uniformly coated on a silicon wafer and coated with a photoresist at a height of 70 μm by spin coating at 2700 rpm. The mask was fabricated using an AutoCAD program to place a specific pattern, including the bridges, as shown in the left column of FIG. The photoresist coating layer coated on the silicon wafer was irradiated with UV through the mask to prepare a master mold having the pattern formed in an embossed shape. A mixture (10: 1, v / v) of PDMS (Polydimethylsiloxane) (Sylgard 184; Dow Corning, Midland, MI) and a crosslinking agent (10: 1, v / v) was poured into the prepared master mold and cured at 65 ° C for 48 hours.
Example 2: Preparation of microparticles
1) Preparation of microparticles by photopolymerization
Microparticles were prepared using the replica mold prepared in Example 1.
First, 1 vol% of PEG-DA (poly (ethylene glycol) diacrylate, Mn = 700) and 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173) Lt; / RTI > The excess PEG-DA and photoinitiator mixture remaining after filling the micro-mold was recovered using a capillary bite by tilting the replica mold or using a pipette tip.
Then, paraffin oil (Sigma-Aldrich) or PDMS oil (20 cP, Sylgard 184) was added to the upper surface of the replica mold and left for 5 minutes. Then, a 100 W HBO mercury lamp equipped with a UV-2A filter (Nikon, Japan) Was irradiated for 30 seconds to be photopolymerized. The microparticles formed by photopolymerization were recovered by immersing the replica mold in IPA (isopropyl alcohol).
FIG. 3 is an image showing the degree of swelling of the replica mold by the paraffin oil and the PDMS oil. In the replica mold in which the micro-mold having the square cross section is formed by the paraffin oil, swelling of the replica mold hardly occurs even after a lapse of time, It is confirmed that only the curvature is formed on the surface of the substrate (FIG. 3A). On the other hand, PDMS oil shows shrinkage of the micro mold due to swelling of the replica mold with time, and the shape of the polymer monomer is disturbed (FIG. 3B).
The second column of FIG. 2 is photographs of paraffin oil, the third column is photographs of microparticles (TE2000, Nikon, Japan) of microparticles produced by PDMS oil, and the rightmost column is photographs of microparticles (SEM, JEOL, JSM-7000F, Japan).
In Fig. 2, the paraffin oil formed a slight curvature on the upper surface of the produced particles, but the height of the particles connected by the bridge was the same. On the other hand, in the case of PDMS oil swelling the replica mold, as the diameter of the graphic object connected by the bridge is increased, the height of the generated particles is increased, so that microstructures having different height are formed.
2) Preparation of microparticles by sol-gel reaction
At room temperature, 5 ml of TEOS (tetraethylorthosilicate, Sigma-Aldrich Chemicals) was added to a mixture of 2.5 ml of ethanol and 2.5 ml of 1N hydrochloric acid, and the mixture was stirred for 10 minutes to prepare a silica precursor. Instead of PEG-DA, the precursor was mixed with polyethylene glycol (Mn = 400) in a 7: 3 volume ratio to fill the micro mold of the replica mold. When the mineral oil was applied onto the replica mold, the precursor mixture quickly polymerized to form microparticles similar in shape to 1).
Claims (7)
A) two or more graphic shapes having different widths are connected by bridges, and the width of the bridges is smaller than or equal to the width of the graphic form having a small width among the graphic objects connected by the bridge, Preparing a duplicate mold of a PDMS (Polydimethylsiloxane) material having a cross-sectional structure in which the width ratio of the bridge to the target is 0.4 or less;
B) filling the micro mold of the replica mold with the polymer monomer;
C) pentane, PDMS oil, diisopropylamine, hexane, heptane, triethylamine, ether, cyclohexane, trichlorethylene, dimethoxyethane, xylene, toluene, ethyl acetate, benzene, The wettability to the replica mold in at least one solvent selected from the group consisting of tetrahydrofuran, dimethyl carbonate, chlorobenzene, methylene chloride, acetone, dioxane, pyridine, N-methylpyrrolidone, Swelling the replica mold by adding a solvent that is larger than the polymer monomer and satisfying the density lower than that of the polymer monomer to the upper surface of the micro-mold filled with the polymer monomer; And
D) polymerizing the polymeric monomer;
Wherein the microstructures have different heights. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the width of the bridge is 5 to 50 占 퐉.
Wherein a height difference of micro-particles constituting the micro-structure is controlled by a ratio of a width of a figure connected by a bridge among the micro-molds.
Wherein the height difference of the microparticles constituting the microstructure is controlled according to a time period during which the solvent is applied to the top surface of the micro mold in the step C) Way.
Wherein the polymerization of the polymer monomer in step D) is carried out by photopolymerization, thermal polymerization or catalytic reaction.
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| KR101171738B1 (en) * | 2010-06-07 | 2012-08-07 | 터프츠 유니버시티 | Fabrication of DNA-conjugated hydrogel microparticles via replica molding and DNA hybridization assay using the microparticles |
| KR101221332B1 (en) * | 2011-01-20 | 2013-01-14 | 충남대학교산학협력단 | Fabrication Method of Monodisperse Polymer Microparticle with Three-Dimensional Structure |
| KR101408704B1 (en) * | 2012-03-15 | 2014-06-17 | 충남대학교산학협력단 | Fabrication of microspheres using replica mold |
| KR101399013B1 (en) * | 2012-03-22 | 2014-06-19 | 충남대학교산학협력단 | Fabrication of microparticles by swelling of replica mold |
| US9287726B2 (en) | 2013-11-06 | 2016-03-15 | The Boeing Company | Virtual cell for battery thermal management |
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