KR101763317B1 - Core-shell structure nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof - Google Patents
Core-shell structure nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof Download PDFInfo
- Publication number
- KR101763317B1 KR101763317B1 KR1020150125018A KR20150125018A KR101763317B1 KR 101763317 B1 KR101763317 B1 KR 101763317B1 KR 1020150125018 A KR1020150125018 A KR 1020150125018A KR 20150125018 A KR20150125018 A KR 20150125018A KR 101763317 B1 KR101763317 B1 KR 101763317B1
- Authority
- KR
- South Korea
- Prior art keywords
- core
- nanoparticles
- water
- silver
- group
- Prior art date
Links
Images
Classifications
-
- C09D7/12—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
Abstract
The present invention relates to a core-shell structure nanoparticle having water repellency and antimicrobial function simultaneously. More specifically, the present invention relates to a core layer formed of silver nanoparticles having antibacterial properties and a fluorine- Silane and a shell layer comprising a crosslinking compound, a coating composition prepared using the core-shell structure nanoparticles, and a process for producing the same, and to provide antibacterial And a water repellent function at the same time, and to improve the durability of the material.
Description
The present invention relates to a core-shell nanoparticle having both water repellent and antibacterial functions and a coating composition using the nanoparticle. More particularly, the present invention relates to a core layer comprising silver having antibacterial function and an outer layer And a shell layer formed of a fluorine-based compound having a water-repellent function, a composition for coating using the composite particle, and a method of manufacturing the same.
The antifouling coating generally refers to the function of preventing surface contamination of the surface of the coating layer by a surface coating technique that prevents contamination by human fingerprints and external foreign objects on the surface of the product. The antimicrobial function is to kill or inhibit various viruses, bacteria, fungi Which is a surface coating material composed of a material having resistance and which is applied to various products requiring a clean and harmless use environment.
Fingerprints on the surface of the product are mainly caused by residual organic matter on the surface of the product, which is a technique that significantly reduces surface adsorption to organic materials. The remaining organic components are degraded over time Or bacteria may occur. Therefore, the anti-pollution technology and the antibacterial technology are complementary to each other in function.
Recently, the use of various display products such as smart phones, PDAs, PMPs, and tablet PCs equipped with a touch function has been exploding and consumers are increasingly demanding an interface that provides a clean and harmless use environment. In accordance with this trend, there is an increasing demand for the contamination and antimicrobial function of housings of home appliances including a refrigerator, a washing machine and an air conditioner, housings of IT products and automobiles as well as electronic products having touch functions.
In this regard, Korea Patent Publication No. 2006-0107089 entitled "Antibacterial-super water-repellent coating composition, a method for producing the same, and a coating method using the same" hereinafter referred to as Prior Art 1) In the water-repellent coating solution, silver nanoparticles, composite particles in the form of silver nanoparticles adsorbed on the SiO 2 surface of a spherical or expanded microstructure, and dispersion solution in which silver component particles such as silver-containing compounds are dispersed are mixed, Water-repellent coating composition by dissolving the compound and then reducing it to silver, thereby coating the substrate.
In the
Further, there is also a problem in that the process steps are complicated and the manufacturing cost is limited by manufacturing the coating composition by dispersing and mixing the materials having the respective properties.
Accordingly, it is an object of the present invention to provide nanoparticles having water repellency and antibacterial properties at the same time in order to maximize water repellency and antibacterial properties, and to reduce processing time and cost in the preparation of coating compositions and films.
In addition, the present invention provides a core-shell structure particle having water repellency and antibacterial function simultaneously, which further comprises a crosslinking compound in the shell part, thereby improving the durability of the film through crosslinking with the binder material .
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.
According to an aspect of the present invention, there is provided a core-shell nanoparticle comprising a core layer having an antibacterial function and a shell layer formed on the outer layer thereof and having a water-repellent function, to provide.
In addition, in the present invention, the core layer has an antibacterial property and is formed to have an average particle diameter of 1 to 300 nm including silver nanoparticles surface-modified with a silanol group, and the shell layer contains fluorosilane having a water repellency and a chain length of C1 to C20 And may be formed to a thickness of 1 to 100 nm.
The nanoparticles according to the present invention may further comprise a crosslinkable compound in the shell layer. The crosslinkable compound may be an acrylic functional group, an epoxy functional group, a vinyl functional group, or the like capable of forming a crosslinking with a photocurable binder or a thermosetting binder May be included.
The present invention also provides a silver nanoparticle modified silver nanoparticle comprising a silver nanoparticle modified with a silane coupling agent by reacting a silver precursor with a silane coupling agent under a solvent, a silver nanoparticle modified with a silane coupling agent, Forming a nanoparticle core layer, and introducing a fluorine-based compound into the core layer to form a shell layer, wherein the water-repellent and antibacterial functions are simultaneously provided.
In addition, the present invention is a precursor AgNO 3, AgClO 4, AgBF 4 , AgPF 6,
Also, the present invention provides a coating composition comprising 2.5 to 50 parts by weight of core-shell nanoparticles having water repellency and antibacterial function simultaneously with 100 parts by weight of an organic vehicle.
The present invention also provides a film comprising nanoparticles of core-shell structure having both water repellency and antibacterial function. The film material according to the present invention has a super water-repellent property with a water contact angle of 100 to 140 ° . ≪ / RTI >
It is a first object of the present invention to provide a silver-fluorine core-shell particle having both water repellency and antibacterial function to provide a functional material having a water repellent and antibacterial property maximized, It has a second effect that it is possible to shorten the manufacturing process and to reduce the manufacturing cost when manufacturing a film or a coating composition containing the same, which has two functions at the same time.
Regarding the first effect, unlike the prior art in which a compound having antimicrobial activity and water repellency are mixed to produce a functional material, water-repellent and antimicrobial properties including particles having higher water content and antimicrobial function It can be improved. In addition, the antimicrobial material and the water-repellent material have a polarity different from that of the water-repellent material, thereby limiting the antimicrobial function on the surface of the water-repellent and antibacterial film. However, the present invention provides a silver- Can maximize water repellency and antibacterial properties at the same time.
With respect to the second effect, particles and water-repellent and antimicrobial functions are simultaneously dispersed in an organic vehicle to prepare a coating composition and a film. As shown in FIG. 1, It is possible to shorten the process steps and the process time compared to the conventional technology and to reduce the manufacturing cost.
It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.
1 is a schematic view of a film material having water repellency and antimicrobial function simultaneously according to the prior art.
2 is a schematic view of a silver-fluorine core-shell particle having water repellency and antibacterial function according to an embodiment of the present invention.
FIG. 3 is a schematic view of a film material including silver-fluorine core-shell particles having water repellency and antibacterial function simultaneously according to an embodiment of the present invention.
4 is a UV / vis absorption spectrum of Ag-SiOMe powder and Ag-Si-OH powder according to an embodiment of the present invention.
5 is a graph illustrating particle size analysis results of Ag-Si-OH particles according to an embodiment of the present invention.
6 is a SEM photograph of Ag-Si-OH according to an embodiment of the present invention.
7 is a SEM photograph of Ag-Si-F according to an embodiment of the present invention.
8 is a view showing SEM / EDS measurement results of Ag-Si-OH according to an embodiment of the present invention.
9 is a view showing SEM / EDS measurement results of Ag-Si-F according to an embodiment of the present invention.
10 is an XPS spectrum of Ag-Si-OH powder according to an embodiment of the present invention.
11 is an XPS spectrum of Ag-Si-F powder according to an embodiment of the present invention.
12 is a photograph showing the results of measurement of the water contact angle of a film made of Ag-Si-F particles according to an embodiment of the present invention.
13 is an XPS spectrum of Ag-Si-F-MA powder according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.
Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Fig. 2 shows a schematic view of a silver-fluorine core-shell particle according to the present invention. The present invention provides a core-
First, in the present invention, the core layer that provides the antibacterial function may include silver nanoparticles having antibacterial properties, but the present invention is not limited thereto, and metal nanoparticles and metal oxide nanoparticles, which are usually applied to antibacterial functional products, . It is well known that metal materials such as copper, platinum, gold, germanium, and zinc, including silver, act to catalyze oxidation to suppress or kill microbial propagation. The silver nanoparticles having excellent antimicrobial properties can be selected as an antimicrobial substance. The silver nanoparticles of the present invention can be easily incorporated into a water-repellent layer, have sufficient oxidation stability, and have excellent antibacterial properties. Respectively. The core layer may be made of only silver nanoparticles, but may be made of the metal or metal oxide. Alternatively, a low-cost metal such as copper may be encapsulated with silver to form a core layer. It can contribute to reduce the unit price. In preparing the silver-fluorine core-shell structure according to the present invention, the surface of the silver nanoparticles can be modified in order to facilitate the introduction of the shell layer, Modified silver nanoparticles. This will be described later. In the present invention, the core layer may have an average particle diameter of 1 to 300 nm. The average particle diameter of the core layer having an antibacterial function is closely related to the antibacterial property. When the average particle diameter is less than 1 nm, the agglomeration effect of the silver nanoparticles increases in the preparation of the silver-fluorine core- It may not be easy to introduce the water repellent layer around the layer. When the average particle diameter of the core layer exceeds 300 nm, the energy value according to the surface area decreases, and even if the same amount of the silver nanoparticles is contained, the antibacterial property may be lowered compared to the core layer having a smaller particle diameter. In order to minimize the above-described problems, the present invention specifies the size of the core layer as 1 to 300 nm. However, the present invention is not limited to this, and a coating composition or film having both water- It can be varied depending on the content of the particles.
Next, in the present invention, the shell layer providing the water-repellent function may comprise a fluorine-based compound. In one embodiment of the present invention, the fluorine-based compound may be a fluorine-based silane. The fluorine-based silane is a compound comprising a combination of a fluoroalkyl group and an alkoxysilane containing a functional group such as a methoxy group or an ethoxy group. The fluoroalkyl group is a representative hydrophobic group and provides a water repellent property, and the alkoxysilane is a reactive functional group that provides reactivity with organic matter. In the present invention, the fluorine-based silane may include fluoroalkyl groups having a chain length of C1 to C20. When the fluorine-based silane is less than C1, it may be difficult to secure the minimum water repellency. When the fluorine- It may not be easy to introduce a shell layer on the surface of the surface-modified silver nanoparticles. Non-limiting examples of fluorine-based silanes include tridecafluorooctyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluoro But are not limited to, heptadecafluorodecyltriisopropoxysilane. In the present invention, the shell layer may be formed to a thickness of 1 to 100 nm, and if it is less than 1 nm, the water repellent layer may not be sufficiently secured and it may be difficult to ensure the minimum water repellency. The energy value according to the surface area decreases, and the water repellency characteristic of the shell layer having a thinner thickness may be lowered even if the same amount of the fluorine compound is included.
The silver-fluorine core-shell particles according to the present invention may have an average particle diameter of 2 to 400 nm. When the average particle diameter is less than 2 nm, water-repellency and antibacterial properties may be improved by increasing the surface area. There is a problem in that the coagulation effect between the particles is large during the production of the coating composition and film, which makes it difficult to disperse the particles, gives a larger mechanical agitation force, and increases the content of the dispersant. When the particle diameter of the core-shell particles exceeds 400 nm, it may be difficult to maximize water repellency and antibacterial properties by energy reduction depending on the surface area as described above.
In addition, the nanoparticles of the core-shell structure according to the present invention may further comprise a crosslinkable compound in the shell layer. The crosslinkable compound according to the present invention may be characterized by being bonded to the surface of the core layer and containing at least one functional group capable of forming a crosslinking with a photocurable binder or a thermosetting binder. Examples of the functional group contained in the crosslinkable compound include an acrylic functional group, an epoxy functional group, a vinyl functional group, and an ally functional functional group, but are not limited thereto. The crosslinkable compound may include a silane group that is easily bonded to the silver nanoparticle surface-modified at one end, and the other end may include the above-mentioned crosslinkable functional group. Concretely, the vinyl silane, acrylic silane, epoxy Based silane, methacrylic based silane, and allyl based silane. The silane group of such a compound is bonded to the surface of the core layer of the present invention and the functional group at the end is located on the surface of the particle to form a crosslinking reaction with a photocurable binder or a thermosetting binder in the production of a film including core- The durability of the water repellent and antibacterial functional film can be improved.
Hereinafter, a method for producing the silver-fluorine core-shell particle of the present invention will be described.
First, it is a step of preparing a solution containing a silver precursor stabilized with a dispersant. The silver precursor may be at least one compound selected from the group consisting of AgNO 3 , AgClO 4 , AgBF 4 , AgPF 6 , CH 3 COOAg, AgCF 3 SO 3 , Ag 2 SO 4 , CH 3 COCH═COCH 3 Ag, Reduced silver nanoparticles are formed. The dispersant minimizes the aggregation of particles during the preparation of silver nanoparticles, thereby enabling the formation of silver nanoparticles of uniform particle size. A water-soluble polymer such as PVP or PVA can be used as a surfactant conventionally used in the production of silver nanoparticles.
In one embodiment of the present invention, a solution comprising a silver precursor stabilized with a dispersant may be prepared under a two phase solution system. More specifically, the method includes the steps of preparing a first solution by mixing a first solvent and a dispersant, preparing a second solution by completely dissolving the silver precursor in a second solvent phase-separated with respect to the first solvent, 2 solution is mixed with a predetermined agitation force to stabilize the silver precursor dissolved in the second solution with a dispersant to transfer it to the first solution and then removing the second solution to prepare a solution containing the silver precursor stabilized with the dispersant can do. The second solution may contain a silver precursor that is not stabilized with a dispersant and some ions dissociated from the dispersant, and silver nanoparticles of even grain size can be prepared by removing such a substance. In a preferred embodiment of the present invention, the first solvent may be a nonpolar solvent such as toluene, chloroform, xylene, ether, or benzene, and the dispersing agent may be a quaternary ammonium salt-based surfactant. Further, the second solvent may be an aqueous solvent which is phase-separated from the first solvent, preferably water. The solution containing the silver precursor stabilized with the dispersant is not limited to the above-mentioned method, and it is specified that the solvent can be prepared even in one solvent system.
Second, a step of dispersing a silane coupling agent in a solution containing a silver precursor stabilized with a dispersant to prepare a dispersion solution. The silane coupling agent has a functional group that binds to the surface of the silver nanoparticles to improve the dispersibility and to provide reactivity with the organic material, so that the introduction of the fluorine-based compound can be facilitated. The silane coupling agent is a compound having two or more functional groups, and comprises a first functional group capable of hydrolysis and a second functional group reactive with a surface of the core layer, wherein the first functional group is a methoxy group, an alkoxy group And the second functional group may be at least one functional group selected from the group consisting of a thiol group, a hydroxyl group, and an amide group. Preferably, the second functional group may be a thiol group having a strong bonding force with the metal nanoparticle surface.
Third, a silver nanoparticle stabilized with a silane coupling agent is prepared by performing a reaction of reducing a silver precursor by adding a reducing agent to a dispersion in which a silane coupling agent is dispersed. Silver nanoparticles having a narrow particle size distribution can be produced by performing the reduction reaction of the silver precursor in a state where the silane coupling agent is dispersed. As described above, the silane coupling agent is a compound containing a second functional group and a first functional group. In one embodiment, the second functional group contained in the silane coupling agent may be a thiol group, and the thiol group may bond to the surface of the silver nanoparticle And the first functional moiety is formed around the silver nanoparticles to facilitate the introduction of the fluorine-based compound.
Fourth, silver nanoparticles stabilized with a silane coupling agent are formed by a sol-gel method to form a silver nanoparticle core layer modified with a silanol group. The sol-gel method is a reaction in which a three-dimensional crosslinking is formed through hydrolysis and condensation reaction of a silane coupling agent. Specifically, the alkoxysilane contained in the silane coupling agent is hydrolyzed into a silanol group by adding water, When the condensation and polycondensation reaction between the silanol groups is carried out, three-dimensional crosslinking can be formed. As described above, when the three-dimensional crosslinking between the silanol groups provided on the surface of the silver nanoparticles is formed, the thermal stability can be secured. The silanol groups which do not form crosslinks provide reactivity with organic functional groups, You can do it. Further, in one embodiment of the present invention, in order to improve the purity of the product to produce high-quality particles, the method may further include, after the fourth step, washing, drying and purifying the liquid surface-modified silver nanoparticles.
Fifth, a step of forming a shell layer by introducing a fluorine-based compound having a water-repellent property into the core layer. In the present invention, the fluorine-based compound may include fluorine-based silane. The fluorine-based silane may be a compound comprising a combination of a fluoroalkyl group and an alkoxy silane such as a methoxy group or an ethoxy group as described above, and the fluoroalkyl group provides water repellency, and the alkoxy silane is a surface- It is a reactive functional group that provides reactivity with nanoparticles. The silanol group formed on the surface of the core layer under a polar solvent or catalyst and the alkoxysilane formed on the fluorine silane compound easily react to form a siloxane bond so that the core layer having an antibacterial function is hydrophobically modified to have water repellent and antibacterial properties Concurrent functional multi-functional core-shell particles can be prepared. In an embodiment of the present invention, the fifth step may further include a crosslinking compound to form a shell layer. The crosslinking compound is the same as that described above and will be omitted.
In addition, after the fifth step, washing may be performed several times to obtain a high-purity product to obtain a solid, followed by drying for a predetermined period of time.
In one embodiment of the present invention, the silver-fluorine core-shell particles having water repellency and antibacterial function simultaneously can be prepared by modifying the surface of silver nanoparticles having antibacterial properties with a silane coupling agent and bonding fluorine silane But is not limited to. However, the silane compound such as the silane coupling agent and the fluorine silane can facilitate the bonding of the core layer and the shell layer even under the low-temperature reaction condition, and the siloxane group formed by the bonding can improve the water repellent effect by the hydrophobic bonding. In addition, by encapsulating silver nanoparticles with silica, it is possible to secure human affinity, and it is preferable to use a silane coupling agent and a fluorine-based silane compound in order to maximize process efficiency and function. In addition, it should be noted that the method of manufacturing the silver-fluorine core-shell particles is not limited to the above-described manufacturing process, but may be modified and carried out by omitting the steps described in this specification or adding other processes.
Further, the present invention provides a coating composition and film-related technology comprising nanoparticles of a core-shell structure having water repellency and antibacterial function at the same time. In one embodiment of the present invention, the composition for coating may include 2.5 to 50 parts by weight of core-shell nanoparticles having water repellency and antibacterial function simultaneously with 100 parts by weight of the organic vehicle.
In addition, in one embodiment of the present invention, the organic vehicle may comprise a solvent and a binder resin in a predetermined ratio. The binder resin may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Acrylate-based or methacrylate-based monomers, low-density polyethylene, polypropylene, polyethylene terephthalate, polycarbonate and polymethyl (meth) acrylate including 2-hydroxyethyl An epoxy-based binder, a urethane-based binder, and a silicon-based binder, but the present invention is not limited thereto It is noted that any known binder resin may be possible. In order to control the viscosity of the coating solution and facilitate the dispersion of the core-shell nanoparticles, a coating composition may be prepared by mixing a solvent. Examples of the solvent include an alcohol-based solvent, a polyol- Any solvent which is generally used in the production can be used. In addition, when the core-shell structure nanoparticles are mixed at less than 2.5 parts by weight in the coating composition, the minimum water repellency and antimicrobial function can not be secured. When the amount exceeds 50 parts by weight, It may be difficult to coat it, and the transmittance may be lowered so that application to products requiring transparency may be limited. In addition, the coating composition according to the present invention may further contain at least one kind of additives such as a dispersant, a photoinitiator, a thermal initiator and a stabilizer. The dispersant may be added to minimize aggregation between the nanoparticles of the core-shell structure, and the long-term dispersion stability of the composition can be secured by adding it. In addition, the curing initiator plays a role of initiating a reaction in which a photo-curable binder or a thermosetting binder forms a three-dimensional network structure by heat or light. As the curing initiator, UV initiators and thermal initiators known in the art can be used as compounds capable of initiating the reaction by dissociating heat or light when formed by non-uniform decomposition to form radicals. For example, commercially available Irgacure 184, Irgacure 819, Iragacure 907 and
The present invention also provides a film comprising nanoparticles of a core-shell structure having both water repellency and antibacterial function, wherein the film is formed by applying the above-mentioned composition for coating onto a substrate, But is not limited thereto. Methods for applying the coating composition to the substrate may include, but are not limited to, spin coating, bar coating, doctor blade coating, spray coating and the like. 1 is a schematic view showing a material having water repellency and antibacterial properties simultaneously according to the prior art. Referring to FIG. 1, a
In addition, the film prepared by including the silver-fluorine core-shell particles according to the present invention may have a water contact angle of 100 to 140 °, and the antibacterial property and water repellency of the film according to an embodiment of the present invention The present invention will be described in more detail with reference to the following Examples and Experimental Examples.
The particles having water repellency and antibacterial function according to the present invention can be applied in various forms such as powder, sol, solution and film, and are applied to a housing of a display, an electronic appliance and an electric appliance, And can be easily applied to various fields ranging from food packaging materials, medical supplies, and architectural paints.
Hereinafter, examples and experimental examples of the present invention will be described.
[Example 1] Preparation of silver-fluorine core-shell particles
≪ Preparation of silver nanoparticles (Ag-SiOMe) stabilized with a silane coupling agent >
4.9 mmol of tetrabutylammonium bromide (TBAB) as a dispersant is mixed with chloroform to prepare a 35 wt% solution. Next, an aqueous solution of 40 wt% silver nitrate (AgNO 3 ) is prepared, mixed with the dispersant solution, and stirred vigorously for 1 hour. After stirring for 1 hour, when the two solutions are phase-separated, remove the aqueous solution layer and add 0.04 mmol of (3-mercaptopropyl) trimethoxysilane as a silane coupling agent to the chloroform layer. Silane coupling agent is added and stirring is carried out for 6 hours. While continuing the stirring, an aqueous solution of sodium borohydride (NaBH 4 ) prepared in advance of 60 wt% is slowly injected. The mixture was vigorously stirred for 6 hours to perform a reduction reaction. Thus, an Ag-SiOMe mixed solution was prepared. (See
[Reaction Scheme 1]
≪ Preparation of Silver Nanoparticles Modified with Silanol Group (Ag-Si-OH)
The Ag-SiOMe mixed solution was mixed with 200 ml of anhydrous ethanol and 15 ml of 28% ammonia water at 25 ° C with stirring, and then heated to 60 ° C to conduct a sol-gel reaction for 24 hours. After completion of the reaction, the solution in the upper layer was removed by ultracentrifugation at 10,000 rpm for 30 minutes, washed several times with an ethanol / toluene mixed solvent, and filtered to obtain a solid component. Then, it was vacuum-dried at 40 DEG C for 24 hours to obtain powdered Ag-Si-OH particles. (See Scheme 2 below).
[Reaction Scheme 2]
<Preparation of water-repellent and antibacterial functional core-shell particles (Ag-Si-F)
0.25 g of the powder of Ag-Si-OH particles and 2.55 g of perfluorooctyltriethoxysilane were mixed with 100 ml of ethanol and reacted at 60 DEG C for 24 hours under a nitrogen atmosphere. After the reaction was completed, the solution was ultracentrifuged at 10,000 rpm for 30 minutes to remove the upper layer solution, washed several times with an ethanol / toluene mixed solvent, and filtered to obtain a solid component. And then vacuum-dried at 40 DEG C for 24 hours to obtain a powder of silver-fluorine core-shell particles (Ag-Si-F). (See
[Reaction Scheme 3]
≪ Production of a film containing Ag-Si-F particles >
An Ag-Si-F powder was mixed in a proportion of 10 wt% to a photo-curable acrylic binder using an ethanol solvent, followed by stirring to prepare a coating composition. This was applied to the PET substrate by spin coating (1000 rpm, 20 seconds) and dried in a drying oven at 120 ° for 1 minute. The dried substrate was irradiated with UV at an intensity of 400 mJ / cm < 2 > to produce a film.
[Experimental Example 1]
1. Confirmation of the formation of silver nanoparticles
UV / vis spectroscopic analysis (SHIMADAZU, UV-2550) of Ag-SiOMe and Ag-Si-OH solutions was performed to confirm the reduction of the silver precursor by the method according to Example 1. The resulting absorption spectrum is shown in Fig. Referring to this, in the solution containing Ag-SiOMe particles, an absorption peak was observed at 390 nm, which is close to the absorption peak of conventional silver nanoparticles, and an absorption peak of the solution containing Ag-Si-OH particles was observed at 550 nm. As a result, it can be confirmed that silver nano-particles are formed by the manufacturing method according to the first embodiment. In addition, Ag-Si-OH particles subjected to hydrolysis and polycondensation by the sol-gel method have a larger particle size than Ag-SiOMe and more agglomeration among particles because the absorption peaks shift to a longer wavelength region Respectively.
2. Particle size analysis of the core layer (Ag-Si-OH)
Particle size analysis of Ag-SiOH particles prepared according to Example 1 was carried out using an electrophoresis light scattering method (Photal, ELS-Z). In order to carry out particle size analysis, Ag-SiOH was dispersed in chloroform to prepare a sample, and measurement was carried out at 25 ° C. The results are shown in Fig. 5 is a graph showing the number particle size distribution. Referring to FIG. 5, it can be seen that the Ag-Si-OH particles prepared according to Example 1 have an average size of about 20 nm.
3. SEM analysis of core layer (Ag-Si-OH) and core-shell particles (Ag-Si-F)
SEM measurement was performed to analyze the size and shape of Ag-Si-OH particles and Ag-Si-F particles prepared according to Example 1, and the results are shown in FIG. 6 and FIG. FIG. 6 is an SEM photograph of Ag-Si-OH particles, and FIG. 7 is a SEM photograph of Ag-Si-F particles. It can be seen from the results that Ag-Si-OH and Ag-Si-F particles have a size of 100 nm or less, Ag-Si-OH particles mean 20 nm, Ag- It was confirmed that the shell layer was formed to have an average size of about 100 nm.
4. SEM / EDS analysis of core layer (Ag-Si-OH) and core-shell particles (Ag-Si-F)
SEM / EDS measurements were carried out to analyze the constituent elements of the Ag-Si-OH particles and Ag-Si-F particles prepared according to Example 1. The results are shown in Fig. 8 and Fig. FIG. 8A is a SEM photograph of Ag-Si-OH, and FIG. 8B is an EDS result graph for the area shown in the SEM photograph. Referring to this, it is confirmed that Ag (La1) and Si (Ka1) are distributed over the entire area shown in the SEM photograph. 9A is a SEM photograph of Ag-Si-F, and FIG. 9B is an EDS result graph for an area shown in an SEM photograph. Referring to this, it can be confirmed that Ag (La1) and Si (Ka1) are contained in the whole region shown in the SEM photograph, and F (Ka1) is also detected, indicating that the fluorine compound is introduced.
5. XPS analysis of core layer (Ag-Si-OH) and core-shell particles (Ag-Si-F)
XPS measurement was performed to confirm the synthesis of the Ag-Si-OH particles and Ag-Si-F particles according to Example 1. 10 to 11 show the results. 10 is a graph showing XPS results of Ag-Si-OH particles. Referring to FIG. 10, peaks corresponding to O (1s), Ag (3d), (C1s), S (2p) and Si (2p) , And a silanol group is formed on the outer layer of the thiol group and the silver nanoparticle bonded to the surface of the silver nanoparticle. FIG. 11 is a graph showing XPS results of Ag-Si-F particles. Referring to FIG. 11, Ag (3d), (C1s), S (2p) , And a peak of F (1s) was confirmed in the vicinity of 700 eV in addition to that, it can be confirmed that a shell layer composed of fluorine-based silane was formed.
6. Measurement of contact angle of films prepared with Ag-Si-F particles
A static water contact angle (KSL 2110) measurement was performed to evaluate the water repellency characteristics of the film produced according to Example 1. 12 shows the static water contact angle measurement result. As a result of the measurement, it was confirmed that the water contact angle of the film prepared according to Example 1 was repeatedly measured and found to have a contact angle of 130 ° to 140 °.
7. Evaluation of antibacterial properties of films prepared with Ag-Si-F particles
Antibacterial assays (ISO 22196) were performed to evaluate the antimicrobial effect of the films prepared according to Example 2, and the results are given in Table 1.
Strain
sample
Bacterial killed after 24h [%]
Log [CFU / ml] After 24h
S.Aureus
Example 4
99.99
5.34
Control
0
-
E. coli
Example 4
99.99
5.77
control
0
-
Referring to Table 1, when the culture broth of the strain was plated on the film according to Example 1 and cultured for 24 hours, it was confirmed that there was almost no viable cell count. In addition, it has been confirmed that the antimicrobial activity against two strains can provide an industrially suitable antimicrobial property with a value of 5 or more.
Hereinafter, examples of core-shell structure nanoparticles that can improve the durability of the film by cross-linking with the binder material when the film is prepared by further including a compound capable of crosslinking with the binder material in the shell layer are described .
[Example 2]
<Preparation of silver-fluorine core-shell particle (Ag-Si-F-MA) into which methacryl group was introduced>
0.25 g of the powder of Ag-Si-OH particles, 2.55 g of excessive amount of perfluorooctyltriethoxysilane and 100 g of 3- (trimethoxysilyl) propyl (meth) acrylate as a crosslinking compound were added to 100 ml of ethanol. Methacrylate) were mixed, and the fluorine compound and the crosslinkable compound were mixed at a molar ratio of 7: 3. The mixture was reacted under stirring at 60 DEG C for 24 hours under a nitrogen atmosphere. After the reaction was completed, the solution was ultracentrifuged at 10,000 rpm for 30 minutes to remove the upper layer solution, washed several times with an ethanol / toluene mixed solvent, and filtered to obtain a solid component. Subsequently, vacuum drying was performed at 40 캜 for 24 hours to obtain a powder of silver-fluorine core-shell particles (Ag-Si-F-MA) into which a methacryl group was introduced. (See Scheme 4 below for this.)
[Reaction Scheme 4]
≪ Production of a film containing Ag-Si-F-MA particles >
A film was produced under the same conditions as in the film production method according to Example 1, except that Ag-Si-F-MA powder was used.
[Experimental Example 2]
≪ XPS analysis of silver-fluorine core-shell particle (Ag-Si-F-MA)
XPS measurements were performed to confirm the synthesis of the Ag-Si-F-MA particles according to Example 2, and the results are shown in FIG. 13 is a graph showing the XPS results of Ag-Si-F-MA particles. Referring to FIG. 13, peaks corresponding to O (1s), Ag (3d), (C1s) and Si (2p) can be confirmed. Further, when compared with the XPS analysis results of the Ag-Si-F particles prepared by mixing the same amount of Ag-Si-OH powder and the perfluorooctyltriethoxysilane as in Example 2, the oxygen peak was greatly increased And it can be seen that 3- (trimethoxysilyl) propyl methacrylate, which is a crosslinking compound, was introduced into the nanoparticles.
[Example 3]
≪ Preparation of silver-fluorine core-shell particles (Ag-Si-F-A)
The silver-fluorine core-shell particle (1) having an acryl group introduced in the same manner and under the same conditions as in Example 2 except that 3- (trimethoxysilyl) propyl acrylate was used as the crosslinkable compound (Ag-Si-FA). (See Scheme 5 below).
[Reaction Scheme 5]
≪ Production of a film containing Ag-Si-F-A particles >
A film was produced under the same conditions as the film production method according to Example 1, except that Ag-Si-F-A powder was used.
[Example 4]
<Preparation of silver-fluorine core-shell particles (Ag-Si-F-E) into which an epoxy group was introduced>
(3-Glycidyloxypropyl) trimethoxysilane was used as the crosslinking compound in the same manner as in Example 2, except that 3- (trimethoxysilyl) propyl acrylate (3-glycidyloxypropyl) trimethoxysilane was used as the crosslinking compound To prepare silver-fluorine core-shell particles (Ag-Si-FE) having an epoxy group introduced therein. (See Scheme 6 below for this.)
[Reaction Scheme 6]
≪ Production of a film containing Ag-Si-F-E particles >
An Ag-Si-F-E powder was mixed with a thermosetting acrylic binder using an ethanol solvent at a ratio of 10 wt%, followed by stirring to prepare a coating composition. The composition for coating was applied to a PET substrate by spin coating (1000 rpm, 20 seconds) and dried in a drying oven at 120 ° for 2 minutes to prepare a film.
[Comparative Example 1]
A thermosetting acrylic binder using an ethanol solvent was applied to the PET substrate by spin coating (1000 rpm, 20 seconds) and dried in a drying oven at 120 ° for 2 minutes to prepare a film.
[Comparative Example 2]
A photo-curable acrylic binder using an ethanol solvent was applied to the PET substrate by spin coating (1000 rpm, 20 seconds) and dried in a drying oven at 120 ° for 1 minute. The dried substrate was irradiated with UV at an intensity of 400 mJ / cm < 2 > to produce a film.
[Experimental Example 3]
<Durability Evaluation of Ag-Si-F Particles Prepared with a Crosslinkable Compound>
When the core-shell structure nanoparticles further contain a crosslinkable compound, the abrasion test of the films according to Examples 1, 2, 3 and 4 was carried out in order to confirm whether the durability was improved. The abrasion test was carried out by applying a load of 500 g to the eraser, placing it on the film surface, and then reciprocating at a speed of 40 reciprocations / minute. The abrasion resistance was evaluated by measuring the number of times that the contact angle changed more than 15 degrees from the initial value by measuring the water contact angle after reciprocation. See Table 2 for the results.
Comparative Example 1
Comparative Example 2
Example 1
Example 2
Example 3
Example 4
Abrasion resistance
[Number of round trips]
> 500
> 500
> 2000
> 3000
> 3000
> 3000
Referring to Table 2, it can be seen that the films of Comparative Example 1 and Comparative Example 2, which were manufactured without the nanoparticles of the core-shell structure, were deformed while the number of reciprocations exceeded 500 times. On the other hand, it can be seen that the films of Examples 1 to 4 prepared by using the nanoparticles of the core-shell structure according to the present invention are four times or more superior to those of Comparative Example 1 and Comparative Example 2. In particular, it can be confirmed that the films of Examples 2 to 4, which were further prepared by further containing a crosslinking compound, were more than 6 times more abrasion-resistant than Comparative Examples 1 and 2. Therefore, when a functional film including nanoparticles having both water repellency and antibacterial function according to the present invention is prepared, the water repellency and antibacterial property of the film can be improved simultaneously, and excellent durability as compared with the prior art can be secured.
It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
100: core-shell particle
110: core layer
150: shell layer
200: Film material (water repellent and antimicrobial function simultaneously)
210: substrate
220: Coating layer
221: Foot importer
225: Antimicrobial compound
θ: contact angle
Claims (24)
i) preparing a solution comprising a silver precursor stabilized with a dispersant;
ii) dispersing the silane coupling agent in the solution to prepare a dispersion;
iii) adding a reducing agent to the dispersion to reduce the silver precursor to produce silver nanoparticles stabilized with a silane coupling agent;
iv) forming the silver nanoparticle core layer modified with a silanol group by a sol-gel method; And
v) introducing a fluorine-based compound into the core layer to form a shell layer;
Wherein the nanoparticles have a water repellent function and an antibacterial function at the same time.
The step i)
Wherein the silver nanoparticles are carried out under a two-phase solution system to control the particle size distribution of the nanoparticles.
Wherein the precursor containing AgNO 3, AgClO 4, AgBF 4 , AgPF 6, CH 3 COOAg, AgCF 3 SO 3, Ag 2 SO 4, CH 3 COCH = at least one compound selected from COCH the group consisting of 3 Ag Wherein the water-repellent and antimicrobial functions of the core-shell structure are simultaneously provided.
Wherein the silane coupling agent comprises a first functional group capable of hydrolysis and a second functional group reactive with a surface of the core layer.
Wherein the bifunctional group comprises at least one functional group selected from the group consisting of a thiol group, an amino group, and a hydroxyl group.
Wherein the fluorine-based compound comprises a fluorine-based silane, wherein the water-repellent and antibacterial functions are simultaneously provided.
A method for producing nanoparticles of core-shell structure having both water repellency and antibacterial function, characterized in that in step (v), a shell layer is formed by further adding a crosslinking compound.
Wherein the organic vehicle comprises a solvent and a binder resin, wherein the organic vehicle comprises a core-shell structure nanoparticle having water repellency and antibacterial function at the same time.
Wherein the coating composition further comprises at least one additive selected from the group consisting of a dispersing agent, a photoinitiator and a heat initiator, and a coating comprising nanoparticles of core-shell structure simultaneously having water repellent and antibacterial functions / RTI >
Wherein the film has a water contact angle of 100 to 140 DEG, wherein the film has a water-repellent and antibacterial function.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150125018A KR101763317B1 (en) | 2015-09-03 | 2015-09-03 | Core-shell structure nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150125018A KR101763317B1 (en) | 2015-09-03 | 2015-09-03 | Core-shell structure nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170028505A KR20170028505A (en) | 2017-03-14 |
| KR101763317B1 true KR101763317B1 (en) | 2017-08-02 |
Family
ID=58460131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150125018A KR101763317B1 (en) | 2015-09-03 | 2015-09-03 | Core-shell structure nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101763317B1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10287386B2 (en) * | 2017-07-28 | 2019-05-14 | Eternal Materials Co., Ltd. | Core-shell particle, method of manufacturing the same and applications thereof |
| KR102112057B1 (en) * | 2018-07-13 | 2020-05-18 | (주)유니드 | Antibacterial, antifungal and high functional coating composition and products using this |
| KR102145351B1 (en) * | 2018-11-26 | 2020-08-19 | 한국생산기술연구원 | Resin composition comprising nanoparticles and method for preparing the same |
| KR102244177B1 (en) * | 2019-12-31 | 2021-04-23 | 한가람화학 주식회사 | Water-Soluble Nano-Ceramic Coating Composition for Parts of an Automobile |
| KR102405654B1 (en) * | 2020-10-05 | 2022-06-07 | 주식회사 오지피테크 | Polyvinyl chloride based anti-microbial film, mater batch for the same, and method for preparing anti-microbial film |
| KR102339843B1 (en) * | 2021-04-15 | 2021-12-14 | 데코민 주식회사 | Bio antibacterial handle with excellent antibacterial properties, and method for manufacturing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090238889A1 (en) | 2006-09-27 | 2009-09-24 | Henkel Ag & Co. Kgaa | Hyper-Branched Polymers for the Provision of Hygienic Characteristics |
| US8337923B2 (en) | 2003-08-22 | 2012-12-25 | Dupont Nutrition Biosciences Aps | Encapsulated antimicrobial material |
| WO2014075956A1 (en) | 2012-11-19 | 2014-05-22 | Unilever Plc | Improvements relating to encapsulated benefit agents |
| JP2014519504A (en) * | 2011-05-24 | 2014-08-14 | アジエニック，インコーポレイテッド | Composition and method of antibacterial metal nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060107089A (en) | 2005-04-07 | 2006-10-13 | 엘지전자 주식회사 | Coating composition having antibiotic and ultra water-repellent property, preparation method thereof and coating method using the coating composition |
-
2015
- 2015-09-03 KR KR1020150125018A patent/KR101763317B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8337923B2 (en) | 2003-08-22 | 2012-12-25 | Dupont Nutrition Biosciences Aps | Encapsulated antimicrobial material |
| US20090238889A1 (en) | 2006-09-27 | 2009-09-24 | Henkel Ag & Co. Kgaa | Hyper-Branched Polymers for the Provision of Hygienic Characteristics |
| JP2014519504A (en) * | 2011-05-24 | 2014-08-14 | アジエニック，インコーポレイテッド | Composition and method of antibacterial metal nanoparticles |
| WO2014075956A1 (en) | 2012-11-19 | 2014-05-22 | Unilever Plc | Improvements relating to encapsulated benefit agents |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170028505A (en) | 2017-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101763317B1 (en) | Core-shell structure nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof | |
| Aziz et al. | Recent progress in silane coupling agent with its emerging applications | |
| Bressy et al. | New insights into the adsorption of 3-(trimethoxysilyl) propylmethacrylate on hydroxylated ZnO nanopowders | |
| MX2007008425A (en) | Composite materials containing carbon nanoparticles. | |
| CN105149612A (en) | Method for preparing SiO2-coated Au@Ag core-shell nanorod | |
| JP5673895B1 (en) | Core-shell type nanoparticles and method for producing the same | |
| CN101230208A (en) | Method for preparing gold nano-rod particles coated with silica layer | |
| JP2008291109A (en) | Infrared shielding microparticle, its manufacturing method, infrared shielding microparticle dispersion, infrared shielding element, and infrared shielding base material | |
| CN110713746A (en) | High-refractive-index wear-resistant hardened coating composition and preparation method of hardened film thereof | |
| Yan et al. | Hydrophobic modification on the surface of SiO2 nanoparticle: wettability control | |
| KR20080083249A (en) | Substrate for hard coating film and coating solution for hard coating film | |
| KR101864767B1 (en) | Preparation method of hollow silica nano powder with high purity and low reflection coating membrane comprising the powder | |
| CN109280389B (en) | Preparation method of silver nanoparticle composite organic silicon resin | |
| CN110499044A (en) | A kind of preparation and its application in polymer composites of organically-modified black phosphorus nanometer sheet | |
| CN105435651A (en) | Method for preparing strong-hydrophilicity PET membrane | |
| JP5621950B2 (en) | Organic-inorganic composite silica nanoparticles, dispersion having the same, and production method thereof | |
| JP5162879B2 (en) | METAL OXIDE PARTICLE-SILICONE RESIN COMPOSITION, OPTICAL MEMBER AND LIGHT EMITTING DEVICE PROVIDED WITH THE SAME, AND METHOD FOR PRODUCING METAL OXIDE PARTICLE-SILICONE RESIN COMPOSITION | |
| Tiwari et al. | Polyacrylate/silica hybrid materials: A step towards multifunctional properties | |
| Hao et al. | Emerging applications of silica nanoparticles as multifunctional modifiers for high performance polyester composites | |
| Zhou et al. | A novel method for preparing silver/poly (siloxane‐b‐methyl methacrylate) nanocomposites with multiple properties in the DMF‐toluene mixture solvent | |
| US20070060693A1 (en) | Paint composition and method for manufacturing the same | |
| KR102568474B1 (en) | Liquid composition for forming an infrared shielding film, method for manufacturing an infrared shielding film using the same, and infrared shielding film | |
| KR101818650B1 (en) | Organic-inorganic composite particle material having water repellent and antibiotic, and preparation method thereof | |
| KR101818649B1 (en) | High durable nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof | |
| KR101132347B1 (en) | Nanofiller for enameled wire, nanocomposite including the same, and preparing method of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |