KR102074698B1 - Sheet with antibacterium and sterilization function and a process for preparing it - Google Patents

Abstract

The present invention relates to a mesh structure sheet having an antibacterial and bactericidal function and a method of manufacturing the same. More specifically, the nanospheres having antimicrobial and bactericidal function by plasmonics can be firmly bonded on the flexible sheet or the sheet of the mesh structure, and the block (holes) of the mesh structure can be prevented from clogging during the coating process. In order to enable continuous production of such a sheet, the method of manufacturing the primer coating step (S1) of forming a primer layer 21 by spraying or dipping a primer coating 20 on a flexible sheet 10 of a mesh structure. ); A primary air blowing step of injecting air onto the sheet on which the primer layer is formed; An antimicrobial agent coating step (S3) of forming a antimicrobial layer on the primer layer by spraying or dipping the nanospheres 31 dispersion having an antimicrobial coating layer 32 formed on the sheet; A secondary air spray step (S4) of spraying air on the sheet on which the antimicrobial layer is formed; And a heat treatment step of drying the sheet on which the primer layer and the antimicrobial layer are formed. It relates to a method for producing a mesh structure sheet having an antibacterial and bactericidal function.

Description

Sheet having antibacterial and sterilizing function and its manufacturing method {SHEET WITH ANTIBACTERIUM AND STERILIZATION FUNCTION AND A PROCESS FOR PREPARING IT}

The present invention relates to a sheet having an antibacterial and bactericidal function and a method of manufacturing the same, and more specifically, to effectively combine nanospheres having a plasmonic antibacterial / sterilizing function on a flexible sheet or a sheet having a mesh structure. It relates to a method for producing a sheet having an antibacterial and sterilizing function capable of continuous production.

In general, silver (Ag) is known to be excellent in antibacterial, sterilization, deodorization, electromagnetic shielding and kill more than 650 bacteria. In addition, the nano-sized silver has a UV protection function and heat insulation, and also has an excellent effect on antistatic due to its high electrical conductivity.

Particularly, if silver is controlled in nano size, the antibacterial activity is more maximized and it is safe because it is several times stronger than chlorine disinfectant and harmless to human body. Especially, it is possible to mass-produce nano silver. Since silver particles are dispersed in nano size and the effect is much better, the utility of the technology related to nano silver is very large.

As an example of this in the Republic of Korea Patent Registration No. 10-0592365 (Patent Document 1), the step of diluting the nano-silver colloidal solution to 5 to 5000ppm; Applying the diluted nano silver colloidal solution onto the sheet; Predrying at 40 to 120 ° C. such that the applied sheet has a water content of 20 to 25%; Curing the pre-dried sheet at a temperature of 100 to 170 ° C; Soaping and washing with alkaline liquid; And it has been proposed a method of antibacterial treatment of the sheet comprising the step of drying at 80 to 150 ℃.

However, since the nano silver colloid coating method such as Patent Document 1 is simply coated on the sheet, the adhesion or bonding strength is weak, so that if the flexible sheet is repeatedly refracted or continuously rubbed in an unspecified direction, There is a problem in that the antimicrobial or bactericidal deterioration.

Moreover, when nano silver colloid solution is applied and dried on a sheet having a mesh structure, the space (hole) of the mesh structure is clogged, which lowers the flexibility, thereby reducing the air permeability, antibacterial and bactericidal properties, and also makes mass production or continuous production difficult. There are also disadvantages.

Due to these problems, a method of adhering nanospheres to a flexible substrate or a mesh structure sheet has not been commercialized.

Korean Patent Registration No. 10-0592365 Patent Registration

The problem to be solved in the prior art is to firmly bond nanospheres having antibacterial and bactericidal functions by plasmonics on a flexible sheet or a sheet of mesh structure, and also a space (hole) on the mesh structure in the coating process. It is to produce a sheet having an antibacterial and bactericidal function capable of preventing this clogging and capable of continuously producing such a sheet.

In order to solve the above problems, the inventors of the present invention, by spraying or immersing a primer coating on a flexible sheet of the mesh structure to form a primer layer, the primary air spray on the sheet on which the primer layer is formed, the antimicrobial coating layer on the surface The formed nanosphere dispersion is sprayed or immersed on the sheet to form an antimicrobial layer on the primer layer, and after the secondary air spray on the sheet on which the antimicrobial layer is formed, the primer layer and the sheet on which the antimicrobial layer are formed are dried. It was found that the above problems can be solved through a heat treatment process to make the present invention completed.

According to the sheet having an antimicrobial and bactericidal function according to the present invention and a method for manufacturing the same, the sheet is first coated with a primer on a flexible sheet or a mesh structure, and then coated by spraying or dipping a nanosphere dispersion coated with titanium dioxide. It can improve the adhesion between nanospheres.

In addition, when using a nano-sphere coated with a silica-based primer and titanium dioxide, it is possible to maximize the bonding force by the physicochemical bonding between the primer layer and the coating layer, thereby preventing the nanospheres from being detached or separated. Has antibacterial performance.

In addition, by spraying air onto the sheet after the primer coating and after the nanosphere dispersion coating, it is possible to prevent the formation of holes formed on the sheet of the mesh structure, thereby preventing antibacterial and sterilization performance without sacrificing flexibility. There is an advantage to maximize.

1 is a block diagram sequentially showing the manufacturing process of the sheet having an antibacterial and sterilizing function according to the present invention.
2 is a process chart for continuously producing a sheet having an antibacterial and sterilizing function according to the present invention.
3 is an enlarged photograph of a portion of the sheet in a state in which the primer is coated and primary air sprayed during the manufacturing process of the sheet having the antibacterial and sterilizing function according to the present invention.
Figure 4 is an enlarged photograph of a portion of the sheet in the state of completing the manufacturing process of the sheet having an antibacterial and sterilizing function according to the present invention.
Figure 5 is a block diagram showing the bonding state of the nanospheres and the sheet of the plasmonic antibacterial and sterilizing function by the method of producing a sheet having an antibacterial and sterilizing function according to the present invention.
Figure 6 shows the molecular binding relationship between the nanospheres of the plasmonic antibacterial and sterilizing function and the bonding portion of the sheet made by the method for producing a sheet having an antibacterial and sterilizing function according to the present invention.

The present invention may be modified in various ways and may have various embodiments. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, this is not intended to limit the present invention to only the illustrated form, and the spirit and scope of the present invention include the conventional modifications and equivalents or substitutes of the illustrated forms.

1 is a block diagram sequentially showing a manufacturing process of a sheet having an antibacterial and sterilizing function according to the present invention, Figure 2 is a process chart for continuously producing a sheet having an antibacterial and sterilizing function according to the present invention, Figure 3 is Coating of the primer during the manufacturing process of the sheet having an antimicrobial and sterilizing function according to the present invention, a photograph of a portion of the sheet enlarged in the first air spraying state, Figure 4 has an antibacterial and sterilizing function according to the present invention 5 is an enlarged photograph of a part of a sheet in a state in which a sheet manufacturing process is completed, and FIG. 5 illustrates nanospheres and sheets of plasmonic antibacterial and sterilizing function by a method of manufacturing a sheet having antibacterial and sterilizing function according to the present invention. Figure 6 is a block diagram showing a combined state, Figure 6 is a plasmonic antimicrobial and sterilization function made by a method for producing a sheet having an antibacterial and sterilization function according to the present invention Shows an binding molecule binding between parts of the furnace with a spear sheet.

As shown in Figure 1, 2 and 5, the method for producing a sheet having an antibacterial and sterilizing function according to the present invention, the primer coating step (S1), the first air spraying step (S2), antimicrobial coating for adhesion A step S3, a secondary air injection step S4 and a heat treatment step S5 are included.

The primer coating step (S1), by spraying or dipping the primer coating agent 20 having an adhesive performance on the flexible sheet 10 of the mesh structure primer layer 21 on the surface of the flexible sheet (10) ) Is the process of forming.

The primer coating 20 may be an organic-inorganic coating including silica nanoparticles, for example, may be an organic-inorganic hybrid coating.

The organic-inorganic hybrid coating agent, as a coating agent based on the silica network structure may be one that R _x Si (OR) _y of the organic silicon alkoxide (organoalkoxysilane) to which the organic material is attached. In the alkoxide precursor, an alkoxy group forms an oxide network structure by the following sol-gel reaction of hydrolysis and condensation reaction.

Hydrolysis ： ≡Si-OR + H ₂ O → ≡Si-OH + ROH

Condensation reaction: ≡Si-OH + ≡Si-OH → ≡Si-O-Si≡ + H ₂ O

           ≡Si-OH + ≡Si-OR → ≡Si-O-Si≡ + ROH

Such organic-inorganic hybrid coating agent, for example, may be prepared by the manufacturing method described in Republic of Korea Patent No. 10-1081431, the primer coating agent 20 applied to the present invention is not limited to those illustrated in the above patent document. If the organic-inorganic coating agent containing silica nanoparticles can improve the adhesion, other known commercially available coatings or coatings prepared by known manufacturing methods can be applied.

The primary air spraying step (S2) is a process of spraying air onto the flexible sheet 10 on which the primer layer 21 is formed.

As shown in FIG. 3, the flexible sheet 10 of the mesh structure has a fine space (hole) formed between the mesh structures because the structure is formed in a lattice form, and spray or immerse the primer coating 20 therein. Spaces (holes) on the lower surface sheet 10 may be blocked by the primer coating 20.

Therefore, before the primer coating 20 is cured, the high pressure air is blown to separate the coating 20 penetrating into the space (hole) on the sheet 10, so that the flexible sheet 10 takes the form of the mesh structure. While maintaining, the primer layer 21 may be formed only on the surface of the mesh structure.

The antimicrobial coating step (S3), by spraying or dipping the silver (Ag) nanosphere dispersion 30 is formed on the surface with an antimicrobial and bactericidal coating layer on the flexible sheet 10 (primer) It is a process of forming an antimicrobial layer on the layer 21.

The nanosphere dispersion 30 is prepared by using silver nitrate (AgNO ₃ ) and titanium tetra-isopropoxide (TTIP), that is, isopropyl alcohol (2-propanol) and titanium tetra-isopropoxide (TTIP) in a predetermined ratio. After mixing, the silver nitrate (AgNO ₃ ) and dimethylformamide (DMF) with a time difference can be prepared by sequentially adding and heating while stirring.

An antimicrobial agent having an Ag-TiO ₂ core shell structure in which a titanium dioxide (TiO ₂ ) film layer 32 is formed on the surface of the silver (Ag) nanospheres 31 is manufactured by the above-described manufacturing method. can do.

The secondary air injection step (S4) is a step of injecting air to the flexible sheet 10 coated with the nanosphere dispersion 30, the flexibility of the mesh structure as in the above-described primary air injection step (S2) It is a process for preventing the minute space (hole) of the sheet 10 from being blocked by the nanosphere dispersion 30.

The heat treatment step (S5) is a process of drying at 80 ° C. to 150 ° C. using a heat treatment apparatus 40 such as an induction heating apparatus or a hot air apparatus, wherein Ag of the primer layer 21 and the nanosphere dispersion 30 is used. The TiO ₂ core shells may be physicochemically bonded to each other, such that the primer layer 21 and the coating layer 32 are mutually physicochemically, as shown in the surface photograph of FIG. 4 and the cross-sectional structure of FIG. 5. Coupled to the coupling portion 33 is formed.

5 and 6, since the primer layer 21 is based on silica nanoparticles, and the antimicrobial layer includes a titanium dioxide (TiO ₂ ) coating layer 32, heat treatment in the state where they are attached After the process, the Si-O-Si structure of the primer layer 21 is combined with the Ti-O-Ti structure of the antimicrobial layer so that the coating layer 32 of the antimicrobial layer is a primer layer 21 by Si-O-Ti bonding. It can be connected to the physicochemically to form the coupling portion 33, thereby increasing the bonding strength, that is, the adhesion can be improved durability and adhesion of the antimicrobial layer.

A series of processes from the primer coating step (S1) to the heat treatment step (S5) is a transfer process for transferring the flexible sheet 10 of the mesh structure by a plurality of rollers 11 as shown in FIG. In the primer coating step (S1), the first air injection step (S2), the antimicrobial agent coating step (S3), the second air injection step (S4) and the heat treatment step (S5) to be made in sequence to the antibacterial and sterilization function The sheet having can be produced continuously.

[Antibacterial and Sterilization Test Example]

Prepare two test specimens (mesh sheet of Table 1) in which the sheets having antibacterial and bactericidal functions according to the present invention were cut into 5 cm horizontally and vertically, and each test specimen was Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538. After inoculation, and after irradiating light (visible light) for 30 minutes at a distance of 2.5 cm from the LED lamp, the bacterial reduction rate was measured.

In addition, as a control, two test pieces (blanks in Table 1) obtained by cutting non-microbial sheets before performing antibacterial and bactericidal coating at 5 cm in width and length were prepared, and Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538 were prepared for each test piece. After inoculating the phosphorus test strain, and then irradiated with light (visible light) for 30 minutes at a distance of 2.5 cm from the LED lamp, the bacterial reduction rate was measured, the test results are shown in Table 1 below.

Test Items Test result Test environment Initial concentration
(CHU / mL) Concentration after 30 minutes
(CHU / mL) Bacterial reduction rate
(%)


(37.0 ± 0.1) ℃
(31.9 ± 0.2)% RH Escherichia coli
On by
Antibacterial test Blank 1.5 × 10 ⁴ 1.5 × 10 ⁴ - Mesh sheet 1.5 × 10 ⁴ 2.5 × 10 ³ 83.3 Staphylococcus aureus
On by
Antibacterial test Blank 1.0 × 10 ⁴ 1.0 × 10 ⁴ - Mesh sheet 1.0 × 10 ⁴ 1.2 × 10 ³ 88.0

* CFU: Colony Forming Unit

* Strain used: Escherichia coli ATCC 25922

Staphylococcus aureus ATCC 6538

* Read the inoculation method and result: KCL-FIR-1003: 2011

As shown in Table 1 above, the blank specimen without the antimicrobial and antiseptic coating had no bacterial reduction after 30 minutes, whereas the nanospheres with the plasmonic antibacterial and antiseptic function were combined as the present invention. (Mech Sheet) reduced E. coli by 83.3% and Staphylococcus aureus by 88.0%, confirming the excellent antibacterial and bactericidal properties.

In the above description, the technical idea of the present invention has been described with reference to the accompanying drawings, but the present invention has been described by way of example only, and is not intended to limit the present invention. Anyone can make various modifications and imitations without departing from the scope of the technical idea of the present invention, and such modifications and imitations are included in the scope of the technical idea of the present invention.

10... Flexible sheet
11... Roller
20... Primer coatings
21... Primer layer
30... Nanosphere Dispersion
31... Nanospheres
32... Film layer
33... Joint
40... Heat treatment device

Claims (6)

A primer coating step of spraying or dipping the primer coating on a flexible sheet of a mesh structure to form a primer layer; A primary air blowing step of injecting air onto the sheet on which the primer layer is formed; An antimicrobial agent coating step of forming an antimicrobial layer on the primer layer by spraying or immersing the nanosphere dispersion having an antimicrobial coating layer formed on the surface of the sheet; A secondary air jet step of injecting air onto the sheet on which the antimicrobial layer is formed; A heat treatment step of drying the sheet on which the primer layer and the antimicrobial layer are formed; Including,
The primer coating agent is an organic-inorganic coating agent containing silica nanoparticles, the antimicrobial agent is an Ag-TiO ₂ core shell structure in which a titanium dioxide (TiO ₂ ) coating layer is formed on the surface of silver (Ag) nanospheres, In the heat treatment step, the Si-O-Si structure of the primer layer is combined with the Ti-O-Ti structure, which is a coating layer of the antimicrobial layer, and the coating layer of the antimicrobial layer is connected to the primer layer by Si-O-Ti bonding. Method for producing a sheet having an antibacterial and antiseptic function, characterized in that formed. The method according to claim 1,
The flexible sheet of the mesh structure may be continuously produced by sequentially performing the primer coating step, the first air injection step, the antimicrobial agent coating step, the second air injection step and the heat treatment step in the process of being transported by a plurality of rollers. Method for producing a sheet having an antibacterial and sterilizing function characterized in. delete delete The method according to claim 1,
The temperature in the heat treatment step is a method for producing a sheet having an antibacterial and sterilizing function, characterized in that 80 ~ 150 ℃. After spraying or immersing an organic-inorganic primer coating agent containing silica nanoparticles onto a flexible sheet of a mesh structure to form a primer layer, and after primary air spraying on the sheet on which the primer layer is formed, silver (Ag) nanospheres of An antimicrobial agent having an Ag-TiO ₂ core shell structure having a titanium dioxide (TiO ₂ ) film layer formed on the surface thereof is sprayed or immersed on the sheet on which the primer layer is formed to form an antimicrobial layer on the primer layer. By secondary air spraying on the layered sheet and heat-drying the sheet on which the primer layer and the antimicrobial layer were formed, the Si-O-Si structure of the primer layer was combined with the Ti-O-Ti structure of the antimicrobial layer to form Si- A sheet having an antimicrobial and bactericidal function, characterized in that the coating layer of the antimicrobial layer is connected to the primer layer by O-Ti bonding to form a bond.

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