WO2020032519A1 - Method for preparing plasmonics implementation layer, and plasmonic antibacterial/sterilization filter using same - Google Patents

Abstract

The present invention provides a method for preparing a plasmonics implementation layer which has improved abilities in sterilizing/fighting/disintegrating harmful substances such as SOx/NOx, bacteria, and viruses, in the visible light region, and which is mass-producible and thus increases productivity. More specifically, the method comprises: a first step in which a nano-core shell and a binder composition containing a silane-based oligomer are prepared, the nano-core shell being prepared by mixing a first base solution containing a titanium alkoxide compound with a second base solution containing a metal nitride; a second step in which the binder composition is coated on the surface of a coating target and semi-cured in a preset temperature range, thereby forming an adhesive binder layer; and a third step in which the nano core-shell is coated and cured on the outer surface of the adhesive binder layer, thereby forming a plasmonics implementation layer. Thus, antibacterial and sterilization effects can be exhibited through plasmonics phenomena in the visible light region.

Description

Manufacturing method of plasmonics expression layer and plasmonics antimicrobial / sterilization filter applied thereto

The present invention relates to a plasmonic expression layer, and more particularly, to a method for preparing a plasmonic expression layer with improved productivity while improving sterilization / antibacterial / resolution in the visible light region and to a plasmonic antibacterial / sterilization filter applied thereto. It is about.

Recently, due to the rapidly developing social environment, air pollution is getting serious, and the demand for improving the air quality of the indoor space is increasing as the time to stay in the indoor space increases. In particular, respiratory, eye and skin diseases caused by fine dust and ultrafine dust containing harmful heavy metals are increasing rapidly along with yellow dust, and the risk of diseases due to the emergence of highly infectious bacteria and viruses is increasing.

Accordingly, technologies for adsorbing and sterilizing / decomposing organic and inorganic contaminants in the air have been researched and developed, among which photocatalysts are particularly attracting attention for economical and environmentally friendly reasons.

In detail, the photocatalyst is a kind of catalyst, and light is used as a main energy source, and when light having energy above the bandgap is incident, an electron / hole pair is generated and an oxidation / reduction reaction is performed. Through this, contaminants adsorbed on the surface of the photocatalyst, in particular, it is possible to purify the contaminated air by decomposing organic pollutants such as bacteria.

Here, various semiconductor materials have been studied as the photocatalyst material, and in particular, titanium-based oxides (TiOx) are mainly used. These titanium oxides are not corrosive by light and are biologically and chemically harmless and do not affect the human body. In addition, it is most used because it is economically inexpensive because it is stable and rich in acid, base and organic solvent used as a solvent of the photocatalyst.

However, such a titanium oxide has a limitation in that it has a wide bandgap and absorbs light in the ultraviolet region, which is about 4% of the total light, thereby exhibiting photocatalytic activity. For this reason, there is a problem in that the manufacturing cost of products such as air cleaners, water purifiers and the like increases due to the use of ultraviolet light sources of high cost.

In addition, the ultraviolet light source reacts with the surrounding oxygen to generate ozone harmful to the human body. Therefore, since a separate component for removing or filtering ozone is required, the manufacturing cost of the product is further increased, and as the size of the product is increased, there is a problem that space utilization is lowered.

On the other hand, the plasmonics phenomenon is a phenomenon having a different principle from the oxidation / reduction reaction by the electron hole pair of the photocatalyst and has sterilization / antibacterial / degradation ability. That is, when visible light enters the plasmonic structure, partial activation occurs between the metal and the dielectric, and the generated electrons move to the surface to generate active oxygen species. Then, decomposition of harmful substances (eg, S0x, organic substances including NOx, etc.) by the generated reactive oxygen species occurs and bactericidal action of bacteria and viruses occurs.

Some techniques have been disclosed in which the plasmonic structure is applied to various structures having a substrate or flexibility to have an antibacterial and sterilization function through the plasmonic phenomenon in the visible light region. The plasmonic structure is applied by depositing a plasmon-forming material on the surface of the substrate.

However, since the method of applying the conventional plasmonic structure has to be generally made through vacuum equipment and high temperature heat treatment method, there are many limitations in the selection of the material to be deposited. As a result, mass production or continuous production is difficult, which leads to a problem in that the productivity is reduced. there was.

In addition, it is difficult to form a plasmonic structure on the outer surface of a flexible substrate, a mesh, a bead, etc. structure, and it is difficult to provide plasmonics visible light antibacterial / sterilization function with a certain performance through the formed plasmonic structure. there was.

In order to solve the above problems, the present invention is capable of mass production while improving the sterilization / antibacterial / resolution for harmful substances such as S Ox / NOx and bacteria, viruses in the visible light range, the productivity is improved plasmonics expression The problem is to provide a method for producing a layer and a plasmonic antimicrobial / sterilization filter applied thereto.

In order to solve the above problems, the present invention is prepared by mixing a first base solution containing a titanium alkoxide compound and a second base solution containing a metal nitride so that antibacterial and bactericidal functions are exhibited in visible light by the plasmonic phenomenon. A first step of preparing a binder composition each comprising the prepared nanocore shell and a silane oligomer; A second step in which the binder composition is coated on the surface of the coating object and semi-cured at a predetermined temperature range to form an adhesive binder layer; And a third step of coating and curing the nanocore shell on the outer surface of the adhesive binder layer to form a plasmonic expression layer.

In addition, the present invention is an adhesive binder layer formed by separating and mixing the first agent and the second agent comprising silane oligomers of different weight percent mutually, and titanium alkoxide so that antibacterial and bactericidal functions are exhibited in visible light by the plasmonic phenomenon. A plasmonic expression layer comprising a nanocore shell prepared by mixing a first base solution containing a compound and a second base solution containing a metal nitride is sequentially laminated and coated on the outer surface of each of the plurality of glass beads. A plurality of plasmonic functional beads; And an accommodating space in which a plurality of the plasmonic functional beads are filled between the inner partition and the outer partition, so that light in the visible region is irradiated therein to activate the plasmonic phenomenon through the plasmonic functional beads. The plasmonic expression layer is applied to the inner partition and the outer partition including a filter body having a projection having an opening gap less than the diameter of the plasmonic functional beads. Provides plasmonic antimicrobial / sterilization filters.

Through the above solution, the manufacturing method of the plasmonic expression layer according to the present invention and the plasmonic antimicrobial / sterilization filter applied thereto provides the following effects.

First, as titanium dioxide is combined into a nanocore shell structure surrounding nano-sized nano-metal particles of gold and silver, a plasmonic expression layer having strong antibacterial / sterilizing ability is formed even in visible light. Therefore, the plasmonics phenomenon is activated even in a low-cost visible light lamp or natural light, and thus economical and excellent antibacterial / sterilizing ability can significantly improve the hygiene of the product and the surroundings of the plasmonic expression layer.

Second, the binder composition to be pre-coated on the surface of the coating object is based on the silane-based, but separate mixing of the two formulations with different composition ratios to control the adhesion and curing rate, so that the nanocore shell is attached / before the binder is completely cured As combined, the coating power is improved. At the same time, as the nanocore shell is washed in IPA and then injected into the surface, the adhesion binder layer is dissolved and re-cured by IPA remaining on the surface, thereby providing more firm adhesion, thereby significantly improving the coating power of the plasmonic expression layer. Can be.

Third, since the nanocore shell is manufactured by mixing and treating the dielectric material and the nanometal particle solution to express the plasmonic phenomenon, mass production is possible. In addition, the process is simplified by continuously coating each coating in the liquid and ultra-fine state without heat treatment at high temperature / high pressure, thereby minimizing restrictions on the shape, material bending and heat resistance of the product. It can be applied to a variety of industries that require visible light antibacterial / sterilization function through the surface plasmon phenomenon can be significantly improved utilization.

1 is a flow chart showing a method for producing a plasmonic expression layer according to an embodiment of the present invention.

Figure 2 is a flow chart showing a method of manufacturing a nanocore shell in the method for producing a plasmonic expression layer according to an embodiment of the present invention.

Figure 3 is an exemplary view showing a state in which the nanocore shell is bonded to the adhesive binder layer in the method for producing a plasmonic expression layer according to an embodiment of the present invention.

Figure 4 is an exemplary view showing a coating process through a rotary stirring in the manufacturing method of the plasmonic expression layer according to an embodiment of the present invention.

Figure 5 is a photograph showing the results of the bactericidal evaluation for the plasmonic expression layer prepared according to each example.

Figure 6 is a cross-sectional view showing a sterilization process using a plasmonic antibacterial / sterilization filter applied plasmonic expression layer prepared according to an embodiment of the present invention.

Best Modes for Carrying Out the Invention The best embodiments of the invention will be described in more detail below with reference to the accompanying drawings.

Hereinafter, with reference to the accompanying drawings will be described in detail a method for producing a plasmonic expression layer according to a preferred embodiment of the present invention and a plasmonic antibacterial / sterilization filter applied thereto.

1 is a flowchart illustrating a method of manufacturing a plasmonic expression layer according to an embodiment of the present invention, Figure 2 is a method of manufacturing a nanocore shell in the method of manufacturing a plasmonic expression layer according to an embodiment of the present invention. 3 is an exemplary view showing a state in which a nanocore shell is bonded to an adhesive binder layer in a method of manufacturing a plasmonic expression layer according to an embodiment of the present invention.

On the other hand, the manufacturing method of the plasmonic expression layer may be applied to the coating, which has the substrate, beads, mesh or flexibility, but need to sterilize and antibacterial of harmful organic substances. In addition, the coating object, such as a substrate, beads, mesh, etc., on which the plasmonic expression layer is formed, may be applied to products such as various machines, parts, or articles that must maintain an antimicrobial state or a filter that decomposes and sterilizes organic substances in the surrounding environment. .

That is, as the plasmonic expression layer is formed on the coating object, it can be maintained in a clean and hygienic state by antibacterial and sterilization through the plasmonic phenomenon in the visible light region. For example, the plasmonic expression layer may be applied to a filter provided in an air purifier or a water purification device. Hereinafter, a plasmonic antibacterial / sterilization filter in which the plasmonic expression layer is formed will be described as an example.

As shown in Figures 1 to 3, the method for producing a plasmonic expression layer according to the present invention is prepared through a series of steps as follows.

First, a first base solution containing a titanium alkoxide compound and a second base solution containing a metal nitride are mixed, heat treated and refluxed to prepare a nanocore shell structure in which a plasmonic phenomenon is expressed. In addition, a binder composition including a silane oligomer is prepared (s10).

Then, the binder composition is semi-cured in the coating and a predetermined temperature range on the surface of the coating object to form an adhesive binder layer (s20). At this time, the predetermined temperature range is preferably set to 60 ~ 150 ℃, more preferably, may be set to a temperature of less than 120 ℃.

Subsequently, as the nanocore shell is coated and cured on the outer surface of the adhesive binder layer, a plasmonic expression expression layer is formed on the outer surface of the coating object (s30).

In detail, the titanium alkoxide compound is oxidized and provided to surround the outer surface of the nano metal particles in the second base solution in the form of titanium dioxide (TiO ₂ ) dielectric. At this time, the titanium dioxide is Under the influence of light irradiated from the light source, a plasmonic phenomenon occurs between the surface of the nanometal particle and the dielectric, and locally strong electrons are generated. The electrons thus generated migrate to the surface of the dielectric and generate reactive oxygen species on the surface of the nanocore shell.

Then, the generated active oxygen species and ionized particles cause microorganisms to be sterilized or to oxidatively decompose organic compounds having toxic and volatile properties such as formaldehyde, phenol, TCE, and the like.

In addition, the metal nitride is nano-sized in solution and the surface is surrounded by the titanium dioxide. At this time, the plasmonic phenomenon is expressed in visible light by the surface of the nano metal particles and the titanium dioxide dielectric covering the nano metal particles. Therefore, the light source may be provided with a visible light lamp which is inexpensive and does not generate ozone when reacting with oxygen, thereby significantly improving economic efficiency and safety.

In this case, the first base solution is one selected from the group consisting of titanium ethoxide, titanium methoxide, titanium butoxide, titanium isopropoxide, and mixtures thereof. It is preferred to be provided. More preferably, it may be provided with titanium tetra isopropoxide (hereinafter TTIP). Such a titanium alkoxide compound is included to supply the titanium dioxide dielectric to be coated on the surface of the coating object (C) to exhibit a plasmonic phenomenon.

The second base solution is selected from the group consisting of gold nitrate, silver nitrate, copper nitrate, nickel nitrate, cobalt nitrate, and a mixture thereof. It is preferred to be provided. Such metal nitrides are included to supply nanometal particles (or noble metal nanoparticles) to which titanium dioxide is bonded to the surface to generate plasmonic phenomenon in visible light as described above.

In addition, the alcohol solvent is methyl alcohol, ethyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, pentyl alcohol, benzyl alcohol, and the like. It is preferably provided with one selected from the group consisting of a mixture thereof. Here, the nano-core shell (14a) is formed through the following process.

First, the first base solution, that is, the titanium alkoxide compound is added to an alcohol solvent and mixed for 13 to 17 minutes at a temperature range of 27 to 33 ° C. to form a primary solution (s11). Then, the second base solution, ie, metal nitride, is added to the primary solution and mixed for 13 to 17 minutes at a temperature range of 27 to 33 ° C. to form a secondary solution (s12).

Subsequently, dimethylformamide (hereinafter referred to as DMF) was added to the secondary solution, followed by heat treatment and reflux for 100 to 200 minutes at a temperature range of 80 to 120 ° C. to form a tertiary solution including the nanocore shell 14a. To form (s13). Here, the reflux is preferably understood as an operation of condensing the vapor generated by heating to return to the liquid phase.

At this time, the nanocore shell 14a is 1.2-2.2 wt% of the first base solution, 1.7-2.4 wt% of the second base solution, 73-80 wt% of the alcohol solvent, 17- Preferably, 23 wt% of DMF is included.

Herein, the first base solution and the second base solution are added to supply dielectric and nano metal particles in which plasmonic phenomenon is expressed. Preferably, the weight percent range of the first base solution and the second base solution is It is preferable that they are 1: 1.05-1.18. Accordingly, the outer surface of the metal nanoparticles may be uniformly wrapped with titanium dioxide and formed as the nanocore shell 14a.

In addition, when the alcoholic solvent is more than 80% by weight, the input amount of each base solution is reduced, and if less than 73% by weight, the mixing uniformity is lowered, so it is preferably included in 73 to 80% by weight. In addition, as the DMF is contained in 17 to 23% by weight, the base solution may be stably mixed and the nanocore shell 14a may be formed.

In addition, the nanocore shell 14a is formed by heat-treating for 100 to 200 minutes in a temperature range of 80 to 120 ° C. while maintaining a solution state through a reflux process. At this time, the nanocore shell 14a is separated from the tertiary solution and washed with isopropyl alcohol (hereinafter referred to as IPA) (s14). Herein, the nanocore shell 14a and the isopropyl alcohol preferably have a weight range of 1:99 to 5:95.

In detail, the third solution is centrifuged to separate only the nanocore shell 14a. In addition, when the IPA in the above weight% range is mixed with the separated nanocore shell 14a, the surface of the nanocore shell 14a is washed, and the nanocoreshell 14a is present on the IPA solution. do.

Accordingly, when the nanocore shell 14a is introduced in the state in which the binder composition described later is pre-coated to the coating object C, the surface of the adhesive binder layer 13 of the silane base is partially formed by the IPA. Dissolves. Through this, the nanocore shell 14a may be more firmly attached / bonded to the adhesive binder layer 13, so that the coating power of the plasmonic expression layer 14 may be significantly improved.

For example, 1.8 wt% of the TTIP is added to 77 wt% of 2-propyl alcohol and mixed to form the primary solution. In addition, 1.96% by weight of silver nitrate is added to the primary solution and mixed to form the secondary solution. Subsequently, 19.24% by weight of the DMF was added to the secondary solution, followed by heat treatment and reflux at the above-mentioned temperature. Through this, the TTIP and the silver nitrate may be formed as a reaction structure of the nanocore shell 14a in which the titanium dioxide 14b is wrapped on the outer surface of the silver particles 14c through mutual reactions.

The nanocore shell 14a manufactured as described above may be formed to have a particle diameter of 50 to 150 nm. At this time, the silver particles 14c are provided at the central side of the nanocore shell 14a so that the outer surface is wrapped in the titanium dioxide 14b, and the silver particles 14c are formed to have a particle diameter of 10 to 50 nm. Can be. Alternatively, the silver particles 14c may have a particle diameter of 10 to 20 nm, but may be embedded in a plurality of one inside the nanocore shell 14a, and the titanium dioxide 14b may be entirely wrapped around the plurality of silver particles 14c. And may be provided in one shell form.

In addition, the nanocore shell 14a may be added to be coated on the outer surface of the adhesive binder layer 13 in the form of the above-described tertiary solution, but may further improve adhesion to the adhesive binder layer 13. The IPA is washed and added in powder or solution form.

On the other hand, the binder composition is preferably prepared by separating and mixing a first agent comprising a silane oligomer and a second agent comprising a weight percent silane oligomer different from the first agent. In this case, the first agent and the second agent is separated and mixed, the first agent and the second agent is provided separately as a separate composition, which is mixed as a single composition before coating the surface of the coating object It is preferable to understand that.

In detail, the first agent includes 45 to 80 wt% of a siloxane oligomer, 15 to 50 wt% of a diluent solvent, and 2 to 8 wt% of a reaction additive based on the total weight of the first agent. Is preferred. The second agent is preferably 40 to 65% by weight of the siloxane oligomer, 30 to 55% by weight of the diluent solvent, and 2 to 6% by weight of the reaction additive, based on the total weight of the second agent. .

Here, the first agent and the second agent preferably include one selected from the group consisting of siloxane trimers, siloxane tetramers, and mixtures thereof as the siloxane oligomer.

The diluent solvent included in the first agent and the second agent may be an alcohol solvent selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, pentyl alcohol, benzyl alcohol, and mixtures thereof. It is preferable to include. In addition, the reaction additive included in the first agent and the second agent may include at least one or more of an antifoaming agent, a dispersant, a coupling agent. In this way, the individual composition of the first agent and the second agent or the separation and mixing of the first agent and the second agent to reduce the generation of bubbles and each compound can be mixed uniformly.

Accordingly, the adhesive binder layer 13 may be firmly coated with a uniform thickness on the surface of the coating object (C). At this time, it is preferable that the adhesive provider layer 13 is firmly coated because it is excellent in adhesion with the surface of the coating object (C). Through this, since the plasmonic expression layer 14 coated on the outer surface of the adhesive binder layer 13 is firmly attached, sterilization and resolution of microorganisms and organic compounds in the air through the plasmonic phenomenon can be significantly improved. have.

In addition, as the adhesive binder layer 13 is formed to be transparent, the nanocore shell 14a is stably attached / bonded while visible light is incident on the coating object C on which the plasmonic expression layer 14 is formed. It can have an attachment ability that can be.

In this case, the first agent and the second agent is a mixture of the same kind of compound is composed, but the weight ratio of each compound is provided is set differently. Moreover, it is preferable that the weight% of the siloxane oligomers contained in the first agent is set at a ratio greater than the weight% of the siloxane oligomers contained in the second agent.

For example, the first agent may include 65% by weight of the siloxane oligomer, 30% by weight of isopropyl alcohol, and 5% by weight of the reaction additive. In addition, the second agent may include 55% by weight of the siloxane oligomer, 40% by weight of isopropyl alcohol, and 5% by weight of the reaction additive. Here, the first agent is included as an adhesive for firmly coating the plasmonic expression layer 14 on the surface of the coating object (C). And, the second agent is included as a curing agent for adjusting the curing rate of the adhesive binder layer (13).

That is, the present invention is based on the siloxane oligomer, but is composed of a different mixing ratio of the binder composition which is separated and mixed with a formulation having adhesion and curing ability is coated on the surface of the coating object (C). Therefore, the outer surface of the adhesive binder layer 13 The coating rate of the plasmonic expression layer 14 that is continuously coated is improved, through which the expression of the plasmonic phenomenon can be significantly improved.

At this time, the first agent and the second agent is preferably mixed in a ratio of 8 to 10: 1 by weight ratio. In detail, when the first agent is mixed at less than 8 wt% with respect to the first wt% of the second agent, cracks of the adhesive binder layer 13 due to a rapid curing reaction occur while increasing the ratio of the curing agent in the binder composition. In addition, the outer surface of the adhesive binder layer 13 is cured before the nanocore shell 14a included in the plasmonic expression layer 14 is attached.

As a result, the plasmonic expression layer 14 may not be formed to a uniform thickness, or the adhesion may be degraded, thereby degrading coating performance. In addition, the coating performance is reduced, so that the plasmonic expression layer 14 is unevenly formed on the surface of the coating object (C), and the adhesion range of the nanocore shell 14a is reduced, so that the expression of plasmonic phenomenon is reduced. Is lowered. For this reason, harmful substances such as SOx / NOx, bacteria and viruses are not substantially decomposed or sterilized, and when applied to an air purifier, the air cleaning efficiency of the space to be purified is reduced.

On the other hand, when the first agent is mixed in excess of 10% by weight relative to the first weight% of the second agent, the binder composition becomes excessively sticky and the curing time increases. Thus, the binder coating is bonded between the coating object (C) in the step of coating, or is bonded to the inner surface of the rotary stirrer is a coating. This causes peeling or cracking of the adhesive binder layer 13 in the process of separating the coating object (C).

In addition, as the curing of the binder composition is delayed, the nanocore shell 14a included in the plasmonic expression layer 14 is excessively settled into the adhesive binder layer 13. As a result, even though the adhesive binder layer 13 is coated on the surface of the coating object C to have a predetermined thickness, an area in which the air contaminated by the organic material is contaminated with the nanocore shell 14a is reduced. Therefore, the bactericidal and resolution of microorganisms and organic compounds are lowered due to the lower expression of plasmonic phenomenon.

Accordingly, the first agent and the second agent are mixed in a ratio of 8 to 10: 1 by weight so that the adhesive binder layer 13 is uniformly coated on the surface of the coating object C, and each layer is firmly coated. desirable.

Furthermore, it is preferable that the binder composition is composed of a mixing ratio at which the first agent as an adhesive is larger than the second agent as a curing agent. Therefore, not only the flat substrate but also the surface of the coating object having the structure and the flexible structure in which the mesh, the beads and the irregular / irregular irregularities are formed can be uniformly coated.

In addition, the nanocore shell 14a is mixed with a powder or a solvent and coated on the outer surface of the adhesive binder layer 13 in a liquid phase, but before the binder composition is completely cured to form a thin film, that is, the adhesive binder layer ( It is preferable to add in the semi-cured state of 13).

Furthermore, the nanocore shell 14a is bonded / attached to the adhesive binder layer 13 in an ultrafine state of tens to hundreds of nano units. Therefore, the plasmonic expression layer 14 may be formed on the surface of the curved or minute gap regardless of the surface shape and deformation of the coating object (C). Through this, it can be applied to a variety of products requiring plasmonics visible light antibacterial / sterilization functionality can be significantly improved utilization.

Meanwhile, as the first agent and the second agent are separated and prepared before coating the surface of the coating object (C), the adhesive force of the first agent and the curing induction reaction of the second agent may buffer each other. .

That is, while maintaining the adhesion based on the first agent, the curing and drying speed of the adhesive binder layer 13 may be controlled through the second agent. Through this, the adhesive binder layer 13 is uniformly formed on the surface of the coating object C, and the nanocore shell 14a is continuously added while the adhesive binder layer 13 is semi-cured. The plasmonic expression layer 14 to be formed may be firmly attached.

On the other hand, the manufacturing process of the above-described nanocore shell 14a, the process of coating the adhesive binder layer 13 and finally the process of manufacturing the plasmonic expression layer 14 is substantially a heat treatment process of 120 ℃ or less Go through

Accordingly, Si—O—Si bonds formed on the surface of the adhesive binder layer 13 based on silane are mixed with Ti—O—Ti bonds formed on the surface of the nanocore shell 14a, and thus, -Si -O-Ti-O- bond is formed. That is, the unstable bonding structure of the nanocore shell 14a may be coupled and attached in a stable state through the reaction with the adhesive binder layer 13 and the adhesive performance. Through this, the plasmonic expression layer 14 may be firmly coated on the outer surface of the adhesive binder layer 13 through physical and chemical bonding.

In addition, since the temperature applied in the heat treatment process is set to 120 ° C lower than the prior art, the present invention can be minimized deformation of the coating object (C) due to heat, unlike the prior art had a material limitation according to the heat resistance. Accordingly, the restriction of the use of the material to which the plasmonic expression layer 14 can be applied can be significantly reduced. Through this, since the range of the industrial field to which the plasmonic expression layer 14 is applicable increases significantly, the usability and economic efficiency may be significantly improved.

Meanwhile, Figure 4 is an exemplary view showing a coating process through a rotary stirring in the manufacturing method of the plasmonic expression layer according to an embodiment of the present invention. Hereinafter, the coating object is prepared and illustrated as an example of the glass beads 12.

As shown in FIG. 4, the adhesive binder layer 13 is formed by inserting a plurality of the glass beads 12 and the binder composition b into a rotary stirrer s and rotating stirring. At this time, the glass beads 12 are preferably provided in a transparent sphere shape having a predetermined diameter.

In detail, when the plurality of glass beads 12 and the binder composition b are mixed while rotating in the rotary stirrer s, the binder composition b is laminated on the outer surface of each of the glass beads 12. .

At this time, when the binder composition (b) is coated, the rotary stirrer (s) is rotated and stirred for 4 to 9 minutes at a speed of 10 to 60 rpm to form an adhesive binder layer on the outer surface of each of the plurality of glass beads 12 ( 13). Here, the rotation speed of the rotary stirrer (s) is more preferably set to 22 ~ 27 rpm, moreover, the rotary stirrer (s) is rotated at a speed of 25 rpm, the drying time may be set to 5 minutes. .

In addition, the adhesive binder layer 13 is formed into the plasmonic expression layer 14 as it is continuously stirred and rotated into the naconoshell solution or powder state in the rotary stirrer s in a semi-cured state. do.

In detail, the nanocore shell is sequentially introduced into the rotary stirrer s containing the glass beads 12 coated with the adhesive binder layer 13 in a semi-cured state, and rotated while the adhesive binder layer 13 is rotated. The nanocore shell is laminated on the outer surface.

At this time, when coating the nanocore shell, the rotary stirrer (s) is set to correspond to the rotational speed when coating the binder composition (b), a plurality of the glass beads (80 to 100 minutes by drying while rotating stirring) 12) The plasmonic expression layer is formed on the outer surface of the adhesive binder layer 13 formed on each outer surface. Further, in order to form the plasmonic expression layer on the outer surface of the adhesive binder layer 13 formed on the outer surface of each of the plurality of glass beads 12, more preferably, the rotary stirrer s of 25 rpm Rotated at speed, the drying time can be set to 90 minutes.

As a result, the binder composition (b) and the nanocore shell are sequentially coated with a solution or powder on the outer surface of each of the plurality of glass beads 12 to have plasmonic antimicrobial / sterilization function in the visible region. It may be formed of a plurality of plasmonic functional beads. At this time, the plasmonic functionalities are preferably understood to mean having antibacterial / sterilizing function in visible light through the plasmonic phenomenon.

Here, it is preferable to set the rotation speed of the rotary stirrer s as the amount of the glass beads 12 to coat the plasmonic expression layer is increased. That is, by adjusting the rotation speed of the rotary stirrer (s) according to the production amount of the product coated with the plasmonics expression layer can be adjusted the coating thickness and coating performance of the coating layer to be continuously laminated. Through this, the coating quality of the plasmonic expression layer can always be kept constant, the quality of the product to which it is applied can be significantly improved.

In this case, the binder composition (b) is preferably coated with 17 to 23 parts by weight based on 1000 parts by weight of the plurality of glass beads 12.

Here, when the binder composition (b) is added to less than 17 parts by weight, the thickness of the adhesive binder layer 13 is formed to a thickness that does not satisfy the adhesive strength enough to be firmly attached to the plasmonic expression layer. . On the other hand, when the binder composition (b) is added in excess of 23 parts by weight, the economic efficiency is lowered due to the generation of surplus and the adhesion occurs between the glass beads 12 due to the surplus.

Accordingly, the binder composition (b) may be coated with a thickness such that the adhesive binder layer 13 may firmly attach the nanocore shell, while preventing the adhesion between the glass beads 12. (12) It is preferable to add 17-23 weight part with respect to 1000 weight part.

In addition, the nanocore shell, 17 to 23 parts by weight based on 1000 parts by weight of the plurality of glass beads 12 is preferably coated on the outer surface of the adhesive binder layer 13 in a semi-cured state. In this case, the nanocore shell may be added in a solution state.

Here, when the nanocore shell is less than 17 parts by weight, the thickness of the plasmonic expression layer is formed to be thin and the plasmonics developability is lowered because it is not coated on the outer surface of the glass beads 12 as a whole. On the other hand, if the nanocore shell is added in excess of 23 parts by weight, the economic efficiency is reduced due to the generation of excess.

Therefore, the nanocore shell is 17 to 23 parts by weight based on 1000 parts by weight of the plurality of glass beads 12 so as to satisfy the antimicrobial / sterilization characteristics through the expression of the plasmonic phenomenon to reduce the manufacturing cost. This is preferred.

Here, when forming each coating layer, the rotary stirrer (s) is preferably rotated in a state arranged inclined in a predetermined angle range (Θ). At this time, the predetermined angle range Θ is preferably set to 15 ~ 20 °. In addition, each of the coating layer is preferably understood as the adhesive binder layer 13 and the plasmonic expression layer.

In detail, when the rotary stirrer s is rotated and stirred in an inclined state in an angle range of 15 to 20 °, the plurality of glass beads 12 introduced therein are rotated and pulled to the inclined upper side of the rotary stirrer s. .

Then, the glass bead 12 rotated and pulled to the inclined upper side of the rotary stirrer s automatically slides or falls to the lower side of the rotary stirrer s by its own weight. The binder composition (b) may be uniformly coated on the outer surface of each of the plurality of glass beads 12 while the rotational traction and automatic slide movement / fall of the glass beads 12 are repeated.

Here, the rotation of the rotary stirrer s in the process of coating the binder composition (b) on the outer surface of each of the plurality of glass beads 12, the position of the glass beads 12 is automatically changed rotation do. Accordingly, while the binder composition (b) is uniformly coated on the outer surface of each of the plurality of glass beads 12, the adhesion between the glass beads 12 or between the glass beads 12 and the inner surface of the rotary stirrer s. Adhesion is prevented.

That is, in the present invention, the plurality of glass beads 12 may be stirred and rotated individually through the rotation of the rotary stirrer s. Through this, while the individual coating is made on the outer surface of each of the glass beads 12, it is possible to prevent the adhesion between the glass beads 12 or the adhesion between the glass beads 12 and the inner surface of the rotary stirrer (s).

Therefore, each of the coating layers such as the adhesive binder layer 13 and the plasmonic expression layer may be uniformly and firmly coated with a predetermined thickness. In addition, as the rotary stirrer s is rotated, each of the coating layers may be automatically laminated and coated, thereby improving productivity.

Further, the plasmonic expression layer through the simple process of rotating and stirring the glass beads 12, the binder composition (b) and the nanocore shell into the solution or powder with a time difference in the rotary stirrer (s). Can be formed.

That is, it does not require expensive heat treatment equipment or vacuum equipment for the production of the plasmonic expression layer can be formed in a compact workspace and manufacturing cost is reduced. In addition, it is possible to manufacture continuously without moving the working position in each process. Moreover, since the continuous production and the mass production are possible by a simple method of increasing the size or number of the rotary stirrer (s), productivity and manufacturability can be significantly improved.

At this time, when the rotary stirrer s is disposed at an inclination angle of less than 15 °, the adhesive force of the binder composition (b) is greater than the load of the glass beads 12 so that rotational traction and slide movement / fall are not automatically performed. . This causes adhesion between the plurality of glass beads 12 or adhesion between the glass beads 12 and the inner surface of the rotary stirrer s.

Alternatively, when the rotary stirrer s is disposed at an inclination angle exceeding 20 °, due to the automatic slide movement / falling impact of the glass bead 12 rotated and towed to the inclined upper side of the rotary stirrer s. Cracks are generated in the glass beads 12 or the adhesive binder layer 12. In addition, the glass beads 12 are separated to the outside of the rotary stirrer s by the reaction of the drop impact.

Accordingly, the rotary stirrer (s) is 15 to 20 so that a plurality of the glass beads 12 are freely rotated to the viscosity of the binder composition (b) and the cracks due to impacts are individually coated while being automatically moved / falling. It is preferably arranged obliquely in the angle range.

Of course, in some cases, the rotary stirrer s may be rotated and stirred in a state where the inclination angle is 0 °, that is, disposed horizontally with the ground.

On the other hand, in the step of forming the adhesive binder layer 13 or the plasmonic expression layer, a heating unit for maintaining the internal temperature of the rotary stirrer (s) above a predetermined temperature may be further provided.

For example, the heating unit is provided as a heating means, such as a heating bulb disposed on the open upper side of the rotary stirrer s to provide radiant heat, a hot air fan, or an induction heating device such as a water heater disposed below the rotary stirrer s. do. When the heating means is driven, heat of at least room temperature, preferably 60 to 150 ° C., and more preferably 120 ° C. or less, may be applied to the inside of the rotary stirrer s.

Through this, the adhesive binder layer 13 may be semi-cured in a state having a predetermined adhesiveness without being completely cured. In addition, the nanocore shell solution continuously injected in a state in which the adhesive binder layer 13 is coated in a semi-cured state may be rapidly cured while being coated in a thin thin film form.

In addition, unlike the prior art, which requires a high temperature / high pressure heat treatment apparatus or a vacuum apparatus, the present invention is continuously coated through a relatively low temperature heat treatment to simplify the process steps and equipment required for the process. In addition, since the restrictions on the shape, material bending and heat resistance of the product applicable to the process can be minimized, it can be used in various industrial fields requiring plasmonics visible light antimicrobial / sterilization function, which can significantly improve utilization.

In this case, the adhesive binder layer 13 formed based on the siloxane oligomer forms a thin silica film on the outer surface of each of the plurality of glass beads 12, so that the plasmonic expression layer is firmly attached. In addition, since the light transmittance of the adhesive binder layer 13 is high, light irradiated from the light source may be transmitted while passing through the plurality of plasmonic functional beads as a whole.

On the other hand, Figure 5 is a photograph showing the results of the bactericidal evaluation of the plasmonic expression layer prepared according to each embodiment.

As shown in Figure 5 and Tables 1 to 3 to be described later, the sterilization evaluation results of the plasmonic functional beads including the plasmonic expression layer prepared according to the present invention is as follows.

	Mixing ratio		Coating Evaluation
	The first	Second	Initial weight (g)	Coating weight (g)	Washing weight (g)	Peel Amount (g)	Sterilization Rate (%)
Example 1	6	One	100	102	100.6	1.4	93.6
Example 2	12	One	100	102.9	102.1	0.8	97.2
Example 3	9	One	100	103.1	102.2	0.9	99.4

Table 1 is a table showing the coating evaluation according to the mixing ratio of the first agent and the second agent. In each embodiment according to Table 1, the coating method except for the mixing ratio of the first agent and the second agent is as follows. Each example prepares the same amount of glass beads and measures the initial weight. In addition, the nanocoreshell solution in each example is prepared in a 1: 1 ratio with the binder composition prepared according to the mixing ratio of each example. In addition, the binder composition prepared according to the mixing ratio of each example is coated on the glass beads once for 1 minute and then the nanocore shell solution is coated for 3 minutes. Then, the binder composition and the nanocore shell solution prepared according to each embodiment are then coated. After sequentially measuring the weight of the glass beads immediately after coating and drying and washing them. In addition, the coating performance was evaluated by calculating the peeling amount by comparing the initial weight of each example with the weight immediately after coating and the weight after washing, and it is preferable that the smaller the peeling amount, the higher the coating rate.

In addition, the sterilization rate of the plasmonic functional beads prepared according to each example is evaluated together. The sterilization rate evaluation method of the plasmonic functional beads prepared according to each example is as follows.

In detail, the experiment uses E. coli DH5α as the experimental strain, the OD value is set to 1 and the basic bacterial count is set to 10 ⁴ . Then, 50 g of the plasmonic functional beads prepared according to each example were mixed and directly dispensed with the experimental strain in 150 ml of distilled water, respectively. Subsequently, after 5 minutes by irradiating light in the visible region, the test bacteria were treated in the order of separation / washing / dilution, and each plate was plated in a medium and incubated at 35 ° C. for 24 hours to measure the number of bacteria.

As shown in Table 1, the mixing ratio of the first agent and the second agent can be confirmed that the excellent coating performance and sterilization rate in Example 3 satisfying the range of 8 ~ 10: 1 by weight ratio.

On the other hand, in Example 1, where the mixing ratio of the second agent, which is a curing agent, is relatively high, the coating weight is lower than that of other examples, and thus, the sterilization rate is low. In addition, in the case of Example 2 having a relatively high mixing ratio of the first agent as an adhesive, it can be confirmed that the coating performance is high but the sterilization rate is lower than that of Example 3.

	Coating method	Coating time
Example 4	Individual coating	4 minutes (1 minute / 3 minutes)
Example 5	1: 1 mix, once	4 minutes
Example 6	1: 1 mixing, 2 coatings	4 minutes
Example 7	1: 1 mixing, one coating / one additional nanocore shell coating	4 minutes (20 seconds / 3 minutes 30 seconds)

ingredient	Example 4	Example 5
C	34.89	33.12
O	31.41	33.28
Si	27.46	30.68
Ti	6.24	2.92

Table 2 is a table showing the coating method of the plasmonic functional beads according to each embodiment, Table 3 is a table showing the surface composition of the plasmonic functional beads prepared according to Example 4 and Example 5 of Table 2 The content of the surface composition was expressed in weight percent through EDAX analysis. At this time, in Example 4, the binder composition was coated on the outer surface of the glass beads once for 1 minute and then laminated coating the nanocore shell solution once for 3 minutes. In Example 5, the binder composition and the nanocore shell solution were mixed 1: 1 to coat the outer surface of the glass beads once for 4 minutes. In Example 6, the binder composition and the nanocore shell solution were mixed 1: 1 to coat the outer surface of the glass bead once for 4 minutes, and then the same mixture was further coated once more. In Example 7, the binder composition and the nanocoreshell solution were mixed 1: 1 to coat the outer surface of the glass bead once for 20 seconds, and then separately prepared for the nanocoreshell solution to be further coated for 3 minutes and 30 seconds. .

At this time, the composition method of each composition except the coating method and the coating time in each embodiment according to Table 2 is the same as in Example 3 of Table 1.

In addition, the sterilization experiment using the plasmonic functional beads prepared according to the Examples of Table 2 was performed in the same manner as in Table 1 above. On the other hand, the comparative example shown in Figure 4 is to directly dispense the experimental strain to 200ml of distilled water not mixed with plasmonic functional beads to measure the number of bacteria in the above method.

In detail, referring to Table 3, the titanium component is coated on the surface of Example 4 to coat the binder composition and sequentially coat the nanocoreshell solution, rather than Example 5, wherein the binder composition and the nanocoreshell solution are mixed and coated. It was confirmed that much of this was detected. Accordingly, as shown in FIG. 5, Example 4, in which many titanium components were detected on the surface, that is, the plasmonic functional beads prepared according to the present invention exhibited high sterilization rate of 99.9% through excellent plasmonic development. I could confirm it. At this time, in the case of Example 6 and Example 7, the titanium component is detected by a lower weight ratio than Example 5, and the display is omitted from Table 3.

6 is a cross-sectional view illustrating a sterilization process using a plasmonic antibacterial / sterilization filter to which a plasmonic expression layer prepared according to an embodiment of the present invention is applied.

As shown in FIG. 6, the plasmonic functional beads 11 to which the plasmonic expression layer 14 is applied to the surface are filled in the filter body portion 15 in which an accommodating space is formed. It may be provided as / sterilization filter (10). In addition, the air purification apparatus 100 provided with the plasmonic antibacterial / sterilization filter 10 may sterilize / decompose organic matters contained in the air in the purification target space and keep them clean.

These plasmonic functional beads 11 may be expressed plasmonic phenomenon on each outer surface. In addition, since each of the plasmonic functional beads 11 is formed as a sphere, and the contact area between each other is minimized, the area where the contaminated air sucked from the outside corresponds to each of the plasmonic functional beads 11 is greatly increased. Can be set. Therefore, since the plasmonics reactivity is significantly improved relative to the volume of the plasmonic antibacterial / sterilization filter 10, the air purifier 100 may be provided with a compact and excellent air cleaning effect.

In detail, the filter body 15 may have a hollow cylindrical inner partition 16 having a predetermined first diameter and a second diameter spaced apart from the outer surface of the inner partition 16 by a predetermined interval. A hollow cylindrical outer partition 17 is included. Here, the first diameter and the second diameter are preferably standardized according to the size of the air purification device including the plasmonic antibacterial / sterilization filter 10.

At this time, the inner partition 16 and the outer partition 17 is preferably formed in a cylindrical shape having the same center. In addition, an upper end side between the inner partition 16 and the outer partition 17 may be opened, and each lower end may be connected to a donut-shaped bottom surface. Through this, the interval at which the light irradiated from the lamp unit 20 reaches can be formed uniformly.

Of course, the filter body portion 15 may be formed in various shapes such as square, pentagonal, hexagonal or elliptical in cross-section, and may be formed in a plate shape in which the inner partition is provided on one side and the outer partition is provided on the other side. It may be.

Here, the inner partition 16 and the outer partition 17 is preferably formed with projections 16a, 17a having an opening gap less than the diameter of the plasmonic functional beads 11. In detail, the projections 16a and 17a are formed in plural through the entire surfaces of the inner partition 16 and the outer partition 17.

That is, light in the visible light region irradiated from the lamp unit 20 may be transmitted to the plurality of plasmonic functional beads 11 through the projection unit 16a formed in the inner partition 16. In addition, the contaminated air a1 of the indoor space is sucked through the inlet hole 31h formed in the housing part 30 in which the plasmonic antimicrobial / sterilization filter 10 is accommodated, and then into the outer partition 17. It is transmitted to the inside of the accommodation space through the formed projection portion 17a.

In addition, the air may be purified while the microorganisms and organic compounds contained in the air (a1) contaminated by the plasmonic phenomenon through the plasmonic functional beads 11 are sterilized and decomposed. In this case, the purified air a2 may be discharged into the indoor space through the upper side of the air purifier 100 through the projection 16a formed in the inner partition 16.

That is, in the entire outer surface of the plurality of plasmonic functional beads 11 through light (v) directly irradiated through the lamp unit 20 and light (r) reflected indirectly through the nanocore shell. Plasmonix phenomena may be manifested. Through this, light in the visible region may also be transmitted to the plasmonic functional beads 11 filled in portions covered by the body except for the projections 16a and 17a formed in the filter body 15. Therefore, the air purification efficiency through the plasmonic phenomenon of the plasmonic antibacterial / sterilizing filter 10 can be significantly improved.

Here, the opening gap w of the projections 16a and 17a formed in the inner partition 16 and the outer partition 17 is smaller than the diameter d of the plasmonic functional beads 11. desirable.

Therefore, the area that can pass through the projections 16a and 17a to be irradiated to the plurality of plasmonic functional beads 11 filled in the accommodation space is set to the maximum. At the same time, the plasmonic functional beads 11 can be prevented from being separated into the inner partition 16 or the outer partition 17 through the projections 16a and 17a.

On the other hand, in the central portion of the filter body 15, the lamp unit 20 passing through the projections (16a, 17a) to the plurality of plasmonic functional beads 11 irradiating light in the visible light region is It is preferred to be provided.

In detail, the inner partition 16 and the outer partition 17 are each provided in a hollow cylindrical shape and have the same center, and the lamp unit 20 is disposed at the same center of each of the partitions 16 and 17. do. Therefore, since the amount of light irradiated to the plurality of plasmonic functional beads 11 filled in the accommodation space is uniformly transmitted, sterilization and resolution of microorganisms and organic compounds can be further improved.

Accordingly, harmful substances such as microorganisms or volatile organic compounds (VOCs) in the air sucked from the indoor space in which the air purifier 100 including the plasmonic antibacterial / sterilization filter 10 is disposed are sterilized and decomposed. . In addition, indoor air may be kept clean and comfortable as the harmful substances are sterilized and decomposed to re-release the purified air.

In this case, the base filter 50 including the HEPA filter 51 and the deodorizing filter 52 may be provided to surround the circumference of the plasmonic antibacterial / sterilization filter 10.

That is, when the blowing means 40 is driven, the contaminated air a1 introduced through the inlet part 31 is moved to the hollow 53 side in the base filter 50. At this time, while the contaminated air a1 passes through the HEPA filter 51, foreign substances having a relatively large size are physically filtered first. Subsequently, primary filtered air is continuously filtered through the deodorizing filter 52 stacked inside the HEPA filter 51 while adsorbing an odor component in the air.

In addition, the plasmonic antimicrobial / sterilization filter 10 is provided inside the hollow 53 of the base filter 50, and a purification space 10a is formed at the center thereof. In addition, the lamp unit 20 is disposed at the center of the plasmonic antibacterial / sterilizing filter 10 to irradiate light in the visible region.

Therefore, the plasmonic antibacterial / sterilizing filter 10 is organic in air passing through the base filter 50 through the plasmonic phenomenon which is activated by the light in the visible ray region irradiated from the lamp unit 20. The material can be sterilized and purified.

That is, the contaminants in the air blown through the HEPA filter 51, the deodorization filter 52, and the plasmonics antibacterial / sterilization filter 10, which are multi-layered in and outward, are sequentially purified through physical and chemical reactions. Therefore, the cleanliness of the air can be significantly improved.

As described above, the present invention is not limited to the above-described embodiments, but may be modified and implemented by those skilled in the art without departing from the scope of the claims of the present invention. Such modifications are within the scope of the present invention.

The present invention can be applied to the industry for the manufacture and use of antimicrobial / sterilization filter by providing a plasmonic antimicrobial / sterilization filter to which the plasmonics expression layer with improved productivity while improving the sterilization / antibacterial / resolution in the visible region. .

Claims (10)

1. Nano-core shell prepared by mixing a first base solution containing a titanium alkoxide compound and a second base solution containing a metal nitride so as to exhibit antibacterial and bactericidal properties in visible light by the plasmonic phenomenon, and comprising a silane oligomer A first step in which each binder composition is prepared;

   A second step in which the binder composition is coated on the surface of the coating object and semi-cured at a predetermined temperature range to form an adhesive binder layer; And

   And a third step of coating and curing the nanocore shell on an outer surface of the adhesive binder layer to form a plasmonic expression layer.
2. The method of claim 1,

   In the first step,

   The first base solution is provided with one selected from the group consisting of titanium ethoxide, titanium methoxide, titanium butoxide, titanium isopropoxide and mixtures thereof,

   The second base solution is gold nitrate, silver nitrate, copper nitrate, nickel nitrate, cobalt nitrate and a method for producing a plasmonic expression layer characterized in that it is provided with one selected from the group consisting of a mixture thereof.
3. The method of claim 1,

   In the first step, the nanocore shell is

   Adding and mixing the first base solution in an alcohol solvent to form a primary solution;

   Adding and mixing the second base solution to the primary solution to form a secondary solution;

   Dimethylformamide was added to the secondary solution, followed by heat treatment and reflux to prepare a tertiary solution including the nanocore shell;

    Separating the nanocore shell from the tertiary solution and washing with isopropyl alcohol method of producing a plasmonic expression layer characterized in that it is formed.
4. The method of claim 3, wherein

   In the first step, preparing the tertiary solution 100 to 200 minutes are carried out in the temperature range of 80 ~ 120 ℃,

   The nanocore shell includes 1.2 to 2.2 wt% of the first base solution, 1.7 to 2.4 wt% of the second base solution, 73 to 80 wt% of the alcohol solvent, and 17 to 23 wt% of dimethyl. Method for producing a plasmonic expression layer characterized in that it comprises a formamide.
5. The method of claim 1,

   In the second step, the binder composition is prepared by separating and mixing a first agent comprising a siloxane oligomer and a second agent comprising a siloxane oligomer different from the first agent by weight. Manufacturing method.
6. The method of claim 5, wherein

   In the first step, the first agent comprises 45 to 80% by weight of the siloxane oligomer, 15 to 50% by weight of the diluent solvent, and 2 to 8% by weight of the reaction additive, based on the total weight of the first agent. The second agent includes 40 to 65% by weight of the siloxane oligomer, 30 to 55% by weight of the diluent solvent, and 2 to 6% by weight of the reaction additive, based on the total weight of the second agent.

   In the first step, the first agent and the second agent is a method of producing a plasmonic expression layer, characterized in that mixed in a ratio of 8 to 10: 1 by weight.
7. The method of claim 1,

   In the second step, the coating object is provided with glass beads having a predetermined diameter, the adhesive binder layer is a 4 ~ at a speed of 22 ~ 27 rpm by putting a plurality of the glass beads and the binder composition in a rotary stirrer It is formed to be semi-cured by rotating stirring for 9 minutes,

   In the third step, the plasmonic expression layer is added to the nanocore shell in the rotary stirrer by rotating stirring for 80 to 100 minutes at a speed of 22 ~ 27 rpm and the adhesion binder layer and Si-O-Ti bond and Method for producing a plasmonic expression layer characterized in that cured.
8. The method of claim 7, wherein

   In the second step, the binder composition is coated with 17 to 23 parts by weight based on 1000 parts by weight of the plurality of glass beads,

   In the third step, the nanocore shell is a method of manufacturing a plasmonic expression layer, characterized in that 17 to 20 parts by weight based on 1000 parts by weight of the glass bead is coated.
9. An adhesive binder layer formed by separating and mixing a first agent and a second agent comprising silane oligomers having different weight percents from each other, and a agent containing a titanium alkoxide compound such that antibacterial and bactericidal functions are exhibited in visible light by plasmonic development. A plurality of plasmonics in which a plasmonic expression layer comprising a nanocore shell prepared by mixing a first base solution and a second base solution including a metal nitride are sequentially laminated and coated on the outer surface of each of the plurality of glass beads. Functional beads; And

   An accommodation space in which a plurality of the plasmonic functional beads are filled is formed between the inner partition and the outer partition, and the light of visible light is irradiated to the inside to activate the plasmonic phenomenon through the plasmonic functional beads. The plasmonic expression layer is applied to the inner partition and the outer partition including a filter body having a projection having an opening gap less than the diameter of the plasmonic functional beads. Plasmonics antibacterial / sterilization filter.
10. The method of claim 9,

    The nanocore shell comprises 1.2 to 2.2 wt% of the first base solution, 1.7 to 2.4 wt% of the second base solution, 73 to 80 wt% of an alcohol solvent, and 17 to 23 wt% of dimethylformamide. A plasmonic antimicrobial / sterilization filter applied with a plasmonic expression layer, characterized in that the composition, including, but is washed with isopropyl alcohol and attached to the outer surface of the adhesive binder layer.

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