KR20210078774A - Manufacturing method of barrier film coated by spray layer-by-layer self-assembly and property evaluation method thereof - Google Patents

Abstract

The present invention relates to a manufacturing method of a barrier film coated by a spray-type layer-by-layer self-assembly and a property evaluation method thereof. The manufacturing method of a barrier film of the present invention performs the layer-by-layer self-assembled coating of the spraying scheme including one cycle composed of: a first step of spraying a cationic solution on a specimen; a second step of washing with deionized water; a third step of spraying the anionic solution; and a fourth step of washing with deionized water, so that the thickness of the desired layered structure is easily controlled by repeating the coating, and various specimens are coated rapidly and uniformly. Further, the present invention provides the property evaluation method according to the cyclic voltammetry performed with three electrodes for the barrier film manufactured by the spray-type layer-by-layer self-assembly coating, so that mass transfer is controlled and corrosion is suppressed.

Description

A method for manufacturing a barrier film coated by spray-type layered self-assembly and a method for evaluating its properties

The present invention relates to a method for manufacturing a barrier film coated by spray-type layered self-assembly and a method for evaluating its properties, and more particularly, a first step of spraying a cationic solution on a specimen, a first step of washing with deionized water The second step, the third step of spraying the anionic solution, and the fourth step of washing with deionized water are one cycle of the spray method layered self-assembly coating is performed, and the thickness of the desired layered structure is controlled by repeating the coating operation It is easy and relates to a method for manufacturing a barrier film coated by layered self-assembly of a spraying method capable of rapid and uniform coating on various specimens, and a method for evaluating its properties.

The layer-by layer self-assembly method enables nano-level thickness control through precise coating and is excellent in terms of environmental friendliness as it is based on an aqueous solution.

In addition, it is known that it can be coated on various substrates and base materials, so it is being applied in various fields.

More specifically, the multilayer ultra-thin film using the layered self-assembly method is structurally very stable because it is connected by electrostatic interaction, hydrogen bonding, or covalent bonding between each layer. Since a multilayer ultra-thin film can be implemented regardless of the size or shape of the substrate, if materials with desired properties are inserted into each layer, it can be widely applied to various types of electrical and electronic devices, optical devices, displays, or bio devices.

As an example thereof, Patent Document 1 discloses an invention related to a method for manufacturing a transparent graphene thin film using a layered self-assembly method, and uses an electrostatic interaction between nanosheets of oppositely charged graphene oxide or reduced graphene oxide, respectively, for layered self-assembly By doing so, a graphene sheet multilayer thin film can be manufactured simply and easily, and the thickness, light transmittance, and sheet resistance of the obtained graphene thin film can be controlled, so it is reported to be useful as a transparent electrode in an OLED device.

In addition, Patent Document 2 discloses a barrier film including at least two substrates each including a first surface and a second surface, wherein the first surface and the second surface are disposed to face each other; the second surfaces of each substrate are in direct contact with each other; wherein the second surface is not in direct contact with the barrier coating; and the barrier coating comprises alternating layers of cationic material and anionic material; wherein the barrier coating is adhesively bonded to the first surface of each substrate. At this time, the barrier coating utilizes a PET substrate and reports a technology for preventing air from passing into the package as a structure coated with PEI/PAA/PEI/MMT.

However, the invention has a limitation in that the manufacturing speed is slow due to the coating by the self-assembly of the layer by the dipping method.

1 is a schematic diagram of a conventional immersion-type layered self-assembly method coating, using a hydraulic system, placing a beaker on a mold, and moving the mold up and down due to hydraulic pressure to immerse the specimen in the dispersion. Specifically, it is immersed in a negatively charged solution for 10 minutes, washed in deionized water 3 times for 1 minute, and then dried for 1 minute. Similarly, after being immersed in a positively charged solution for 10 minutes, washed in deionized water 3 times for 1 minute, and dried for 1 minute, the positively or negatively charged materials are alternately stacked. This immersion-type layered self-assembly method coating requires a long time-consuming problem to be compensated.

Republic of Korea Patent Publication No. 2011-0115539 (published on October 21, 2011) Republic of Korea Patent Publication No. 2017-0026478 (published on Mar. 08, 2017)

It is an object of the present invention to provide a method for manufacturing a barrier film coated by a spray-type layered self-assembly.

Another object of the present invention is to provide a method for evaluating the physical properties of the barrier film.

In order to achieve the above object, the present invention provides a first step of spraying a cationic solution on the specimen, a second step of washing with deionized water, a third step of spraying an anionic solution, and a fourth step of washing with deionized water A layered self-assembly coating of a spraying method consisting of one cycle is performed, and a thin film made of a cationic-anionic composite material is coated by vacuum suction on the opposite side of the specimen during the washing step after the solution spraying, and the coating process is Provided is a method of manufacturing a barrier film that is repeatedly performed n times and arranged in n layers on a specimen to control the thickness of the thin film.

The specimen used in the present invention includes a conductive substrate selected from the group consisting of gold, copper, aluminum, nickel and zinc; Alternatively, a material having a flat surface such as a polymer substrate selected from PDMS or PET is preferable.

In addition, as the specimen of the present invention, a fiber selected from the group consisting of wool, cotton, polyester and glass fiber may be applied, and more preferably after a precursor layer of LPEI/PAA (linear polyethylenimine/polyacrylic acid) is formed on the fiber. The layered self-assembled coating of the spray method is performed.

The cationic solution applied to the layered self-assembly coating in the present invention is branched polyethyleneimine, linear polyethyleneimine, polydiallyldimethyl ammonium chloride, polyallylamine hydrochloride, poly-L-lysine, poly(amidoamine), poly (amino-co-ester), poly(2-N,N-dimethylaminoethyl methacrylate) and poly(ethylene glycol-co-2-N,N-dimethylaminoethyl methacrylate) at least selected from the group consisting of A solution containing one or more polymers.

In addition, as the anionic solution, a solution containing at least one selected from the group consisting of montmorillonite, laponite, saponite, beidellite, vermiculite, nontronite, hectorite and fluorohectorite may be used.

Furthermore, the present invention provides a method for evaluating the properties of a barrier film according to the cyclic voltammetry method in which the barrier film obtained by the spray-type layer self-assembly coating is used as a three-electrode.

According to the present invention, the spray-type layer self-assembly coating method can be completed at a significantly faster coating speed compared to the conventional immersion method, and it is possible to provide a method of manufacturing a barrier film capable of rapid and uniform coating on various specimens.

It is possible to provide a property evaluation method that can be utilized for controlling mass transfer and inhibiting corrosion according to the cyclic voltammetry method performed with three electrodes of the barrier film manufactured by the spray-type layered self-assembly coating of the present invention.

Therefore, the barrier film produced by the spray-type self-assembled coating of the present invention can be applied to metal parts requiring corrosion inhibition or filters requiring mass transfer control.

1 is a schematic diagram of a conventional immersion method layered self-assembly method coating,
Figure 2 is a schematic diagram for the self-assembled coating layer of the spraying method of the present invention,
3 is a diagram of the present invention; After 10 layers of MMT-PEI coating on Au specimen by spray-type layered self-assembly coating, it is a photograph of the surface before and after using a centrifuge,
4 is a diagram of the present invention. After coating MMT-PEI on Au specimen by spray-type layered self-assembly coating, it is the result of measurement by cyclic voltammetry in electrolyte,
5 is a diagram of the present invention. It is the result of MMT-PEI coating on Cu substrate by spray method layer self-assembly coating and then measured by cyclic voltammetry in electrolyte,
6 is a diagram of the present invention. This is a surface photo of MMT/PEI coating after 60 layers of MMT-PEI coating and LPEI/PAA coating on wool fibers by spraying layer self-assembly method coating,
7 is a surface element component analysis result for the coating for each condition of FIG. 6,
8 is a result of measuring the change in humidity in the air with respect to the coating for each condition of FIG. 6 .

Hereinafter, the present invention will be described in detail.

In the present invention, the spray-type layered self-assembly coating is performed, the thickness of the desired layered structure can be easily controlled by repeating the coating operation, and the spray-type layered self-assembly coating enables rapid and uniform coating on various specimens. Provided is a method for manufacturing a barrier film.

Figure 2 is a schematic diagram for the layer self-assembled coating of the spraying method of the present invention, specifically, on the specimen, the first step of spraying the cationic solution,

a second step of washing with deionized water;

A third step of spraying the anionic solution and

The fourth step of washing with deionized water is a spray-type layered self-assembled coating consisting of one cycle, and after spraying the solution, vacuum suction is performed on the opposite side of the specimen during the washing step to make a thin film made of a cationic-anionic composite material is coated, and the coating process is repeated n times to arrange n layers on the specimen to provide a method of manufacturing a barrier film capable of controlling the thickness of the thin film.

3 is a diagram of the present invention; After 10 layers of MMT-PEI were coated on the Au specimen by the spray-type layered self-assembly coating, it is possible to confirm the coating of the 10-layer laminate structure as a photograph of the surface before and after using the centrifuge.

On the other hand, the coating result of the laminated structure can be checked even in the case of the conventional immersion-type layered self-assembly method coating [not shown], but the time required to complete the same laminated structure is reduced in the conventional immersion-type layered self-assembly method coating , if within 1 day, in the case of the spraying method of the present invention, it is completed within 2 to 3 hours.

The specimen used in the present invention may be a flat metal, a flat polymer, a porous fiber, a filter, or the like.

Specifically, a conductive substrate selected from the group consisting of gold, copper, aluminum, nickel and zinc; or a polymer substrate selected from PDMS or PET.

In addition, as the specimen of the present invention, a fiber selected from the group consisting of wool, cotton, polyester and glass fiber may be applied, and after a precursor layer of LPEI/PAA (linear polyethylenimine/polyacrylic acid) is formed on the fiber, a spray-type layered layer When self-assembled coating is performed, it can be coated more evenly, which is preferable.

In an embodiment of the present invention, gold (Au), copper (Cu) and wool fibers are preferably selected as specimens, but the present invention is not limited thereto.

The method for producing a barrier film by the spray-type layer self-assembly coating of the present invention is not particularly limited as long as it is used as a cationic solution and an anionic solution that are usually applied to the layer self-assembly coating It can be applied.

Specifically, the cationic solution is branched polyethyleneimine, linear polyethyleneimine, polydiallyldimethyl ammonium chloride, polyallylamine hydrochloride, poly-L-lysine, poly(amidoamine), poly(amino-co-ester) , poly(2-N,N-dimethylaminoethyl methacrylate) and poly(ethylene glycol-co-2-N,N-dimethylaminoethyl methacrylate) containing at least one polymer selected from the group consisting of is a solution

In addition, as the anionic solution, a solution containing at least one selected from the group consisting of montmorillonite, laponite, saponite, beidellite, vermiculite, nontronite, hectorite and fluorohectorite may be used.

In an embodiment of the present invention, using a polyethyleneimine (PEI)-containing solution as a cationic solution and a montmorillonite (MMT)-containing solution as an anionic solution, it is coated with a thin film composed of MMT/PEI on the specimen.

The MMT is one of the clay materials, and it is easy to disperse in water and has high strength and thermal stability, so it can be applied as an eco-friendly coating technology. It can be used for penetration, etc.

Accordingly, in the embodiment of the present invention, the thin film coating composed of MMT/PEI (bi-layer) has excellent thermal stability and fire resistance. In addition, as a flat plate structure, there is an advantage that it can be replaced with a plate-shaped micro material such as graphene.

In addition, the thin film coating composed of MMT/PEI obtained by the spray-type layer self-assembled coating of the present invention can easily change the film properties according to the experimental conditions, and by using this, the strength and adhesion to the substrate are improved by ion diffusion. It can be used for control.

Furthermore, the present invention provides a method for evaluating physical properties according to cyclic voltammetry in which the barrier film obtained by the spray-type layered self-assembly coating is used as a three-electrode.

4 is a diagram of the present invention. Using an Au specimen coated with 10, 15 and 20 layers of MMT-PEI by spray-type layer self-assembly coating, and cyclic voltammetry in an electrolyte in which 0.25 mM indigo carmine was added to 0.2 M HCl solution. As a result of the measurement, the amount of penetrating ions can be adjusted according to the number of MMT-PEI coating layers formed on the Au specimen.

Specifically, a conductor electrode was placed on the back of the MMT-PEI-coated Au specimen in Examples 1 to 3 in an electrolyte containing indigo carmine, a molecule capable of reversible oxidation-reduction in solution, and electrochemical method ( As a result of quantitative analysis using the potential scanning method), the current value decreases as the MMT-PEI coating layer increases based on the current value measured with the Au specimen, so it can be evaluated as the amount of material transferred through the porous surface to the conductor. .

5 is a diagram of the present invention. 15 and 30 layer MMT-PEI coated Cu substrates by spray-type layer self-assembly coating were prepared, and the results were measured by cyclic voltammetry in 0.1 mol/L NaCl electrolyte solution, and oxidation reaction of metal As the number of MMT-PEI coating layers increases, the current value decreases as the number of MMT-PEI coating layers increases. From the above, by confirming the electrochemical behavior of the MMT-PEI coating layer on the Cu substrate, the degree of corrosion of the Cu substrate can be confirmed.

The barrier film produced by the spray-type layer self-assembly coating of the present invention can provide a property evaluation method that can be utilized to control mass transfer and suppress corrosion according to the cyclic voltammetry performed with three electrodes.

Therefore, the barrier film produced by the spray-type self-assembled coating of the present invention can be applied to metal parts requiring corrosion inhibition or filters requiring mass transfer control.

In addition, the barrier film produced by the spray-type self-assembled coating of the present invention has an effect on the movement of moisture in the air and can control the humidity in the equilibrium state. Therefore, the thicker the MMT is, the more it impedes the movement of water vapor in the air.

The experimental results supporting it are shown in FIG. 6 of the present invention. It shows a photograph of the surface when MMT/PEI was coated after 60 layers of MMT-PEI coating and LPEI/PAA were coated on wool fibers by spray-type layered self-assembly method coating. That is, the LPEI/PAA is a precursor layer first applied to non-flat wool fibers, and when MMT-PEI is coated after the precursor layer is formed, it can be seen that the LPEI/PAA is coated more evenly.

7 is a result of surface element component analysis for the coating for each condition. Silicon, one of the constituent elements of MMT, increased as the number of coating layers increased, and sulfur, a component of wool fibers, decreased.

In addition, Figure 8 is a result of measuring the change in humidity in the air for the coating for each condition, the barrier film by the spray-type layer self-assembled coating of the present invention affects the movement of moisture in the air and adjusts the humidity in the equilibrium state can [ FIG. 8 ].

Hereinafter, the present invention will be described in more detail through examples.

These examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

<Example 1 >

1, an Au specimen was used as a conductive substrate, the distance between the substrate and the nozzle was fixed to 25 cm, and a cation (PEI) solution was sprayed to the specimen at 0.2 ml/s for 5 seconds, and It was washed for 10 seconds with deionized water at a spray rate of 0.2 ml/s. After washing, an anion (MMT) solution was sprayed at 0.2 ml/s for 5 seconds, and washed with deionized water for 10 seconds to form a first layer. During the process of spraying and washing the solution, a vacuum pump was used to suck air from the opposite side of the spraying direction to the specimen so that it was laminated by a layered self-assembly method.

The above process was repeated to form a 10-layer MMT-PEI coating layer on the Au specimen.

<Example 2 >

Except for forming a 15-layer MMT-PEI coating layer on the Au specimen, the same procedure as in Example 1 was performed.

<Example 3 >

Except for forming a 20-layer MMT-PEI coating layer on the Au specimen, the same procedure as in Example 1 was performed.

<Example 4 >

1, except that a Cu substrate was used as a conductive substrate and MMT-PEI was coated in a 15-layer laminate structure, the same procedure as in Example 1 was performed.

<Example 5 >

The same procedure as in Example 1 was performed, except that a Cu substrate was used as the conductive substrate and MMT-PEI was coated in a 30-layer stacked structure.

<Examples 6-7 >

1, MMT-PEI coating was performed on wool fibers, (A) MMT-PEI was coated in 5 layers, (B) MMT-PEI was coated in 10 layers.

<Examples 8-9 >

As the specimen of Example 6, after forming a precursor layer of LPEI/PAA (linear polyethylenimine/polyacrylic acid) on the wool fiber, MMT-PEI coating, (C) 60 layers of LPEI/PAA coating on the wool fiber After that, 5 layers of MMT/PEI were coated, and (D) 60 layers of LPEI/PAA were coated on the wool fiber, and then 10 layers of MMT/PEI were coated.

At this time, the LPEI (linear polyethylenimine, Mw = 25,000 g/mol) and PAA (polyacrylic acid, Mw = 250,000 g/mol, 35w%) were used, and for deposition, lPEI solution (0.5 g/L) and PAA solution, respectively. (0.5 g/L) was adjusted to pH concentration using 1M HCl aqueous solution and 1M KOH. In addition, a pH 4 MMT solution (1 wt. %) and a PEI solution (0.1 wt. %) were used for deposition.

<Experimental Example 1> Physical property evaluation 1

For the 10-layer MMT-PEI coating on the Au specimen prepared by the spray layer self-assembly method in Example 1, the thickness and roughness were measured using the equipment (Veeco's Dectak 150), and a field emission scanning microscope (FE) -SEM, Hitachi High Technology's S-4800) was used to observe the deposition and shape.

3 is a diagram of the present invention; 10 layers of MMT-PEI were coated on the Au specimen by the spray-type layered self-assembly coating, and the surface photographs before and after using the centrifuge are shown.

As a result, it was confirmed that the layered structure in which 10 layers of MMT-PEI coating were laminated on the Au specimen was smoothly formed by the spray-type layered self-assembly coating of the present invention.

On the other hand, although the laminated structure was checked even by the conventional immersion-type layered self-assembly method coating, the time required to complete the same laminated structure is within one day in the case of the conventional immersion-type layered self-assembly method coating, the present invention In the case of the spray method, it is completed within 2-3 hours.

<Experimental Example 2> Electrochemical evaluation 1

In Examples 1 to 3, 10, 15, and 20 layer MMT-PEI coated Au specimens were prepared by the spray layer self-assembly method, and the current potential curve was measured by cyclic voltammetry (CV). analyzed. Through this cyclic voltammetry, information on the electrochemical activity of the thin film, the amount of stored charge, and oxidation-reduction can be obtained.

CV measurement is performed using the three-electrode method, but the MMT-PEI-coated specimen is inserted by the spray layer self-assembly method in Examples 1 to 3, which is the above specimen, on a platinum substrate for the working electrode and a gold substrate for the counter electrode. did. As the electrolyte, 0.2 mol HCl aqueous solution was used, and 0.25 mM indigo carmine was added to check the ion permeability. In addition, it was measured in a voltage range of 0.3 to 0.3 [V] at a scan rate of 10 mV/s. The area of the electrode used was 1.2 cm2, and the value of the y-axis in the graph was expressed as the value of the current per unit area.

The indigo carmine is an oxidation-reduction indicator. When a voltage is applied to the reference electrode, a redox reaction occurs under the working electrode, and the current flowing at this time is read from the counter electrode. The redox peak refers to the point at which the current generated by changing the voltage becomes the maximum. The metal substrate reacts with the indigo carmine ion to generate a reduction peak at 1.8 [V] potential and an oxidation peak at 1.2 [V] occurs Although the redox reaction of indigo carmine is a reversible reaction, there is a slight difference in the size of the oxidation peak and the reduction peak because the reactants remain on the electrode surface and the analyte decreases.

The results are described in Table 1 below and shown in FIG. 4 .

If the indigo carmine ions do not penetrate into the thin film by layer self-assembly (LBL) coating, they cannot access the metal substrate, which is the working electrode, so that the redox reaction does not occur.

As a result of Table 1 and FIG. 4, it can be seen that the redox current is different depending on the number of layers. In particular, as the number of layers increases, it is difficult for indigo carmine ions to penetrate into the layered self-assembly (LBL) coating, thereby lowering the ion permeability. Therefore, it was confirmed that the size of the redox peak gradually decreased as the number of ions reacting on the metal substrate decreased.

In particular, it was confirmed that oxidation-reduction reaction hardly occurred in the coating of 20 or more layers.

In addition, in order to evaluate the stability of the coating when subjected to repeated electrochemical stimulation in a highly acidic electrolyte, the change trend of the curve up to the 50th layer was investigated. As a result, the reaction potential and the reaction current almost changed after the 30th layer. It was stabilized without any change, and the size of the redox peak appeared in micro units, and almost no current flowed.

Through these experimental results, it can be determined that the MMT-PEI coating can control the ion permeability according to the number of layers and has electrochemically stable performance.

From the above, it was confirmed that the amount of penetrating ions can be adjusted according to the number of MMT-PEI coating layers formed on the Au specimen from the results of analyzing the current potential curve by measuring by the cyclic voltammetry.

Therefore, the mass transfer evaluation of the MMT coating laminated on a flat surface can be evaluated through the same electrochemical analysis method as above using a metal substrate.

<Experimental Example 3> Electrochemical evaluation 2

After 15 and 30 MMT-PEI coatings were formed on the Cu substrates prepared in Examples 4 to 5, the current potential curve was analyzed by measuring by cyclic voltammetry. At this time, in order to investigate the permeation of ions smaller in size than indigo carmine ions, the degree of corrosion of the copper substrate according to the number of layers in 0.1 mol/L NaCl solution was examined.

The results are described in Table 2 below and shown in FIG. 5 .

As a result, it was confirmed that the more active the oxidation reaction of the metal, the more active the reduction reaction in which the positive ions of the electrolyte approach the working electrode to obtain electrons. Therefore, as the number of layers increases, the current peak decreases.

In terms of corrosion of metal, it was confirmed that the current value increased as the number of cycles increased, and the current value decreased as the number of layers increased. By quantifying this, it is possible to control ion permeation according to experimental conditions.

These results are the effects confirmed by the conventional immersion-type layer-by-layer self-assembly coating, and the same effect can be expected through the spray-type layer-by-layer self-assembly coating.

<Experimental Example 4> Physical property evaluation 2

1. Morphology Observation

For the MMT-PEI coating layer formed on the Au specimen by the spray-type layered self-assembly method in Example 6, the thickness and roughness were measured using equipment (Veeco's Dectak 150), and a field emission scanning microscope (FE-SEM) , Hitachi High Technology's S-4800) was used to observe the deposition, shape, etc.

As a result, it was confirmed that the MMT-PEI coating was laminated in a layered structure on the Au specimen in FIG. 6 , and a coating with a wide film-like appearance was formed due to the plate-shaped structure of MMT. In particular, when coating MMT/PEI after coating 60 layers of LPEI/PAA, it was confirmed that the coating was more even.

2. Component Change Analysis

Elemental components were analyzed on the surfaces prepared in Example 6 for each condition (A), (B), (C), and (D).

As a result, it was confirmed that silicon, one of the constituent elements of MMT, increased as the number of layers increased, while sulfur, a component of wool fibers, decreased.

3. Measure changes in humidity in the air

Changes in humidity in the air were measured according to the passage of time for each condition (A), (B), (C), and (D) prepared in Example 6.

Specifically, in order to measure the moisture transfer control ability of each specimen, two sealed chambers of 3L size were made, each chamber was connected with a tube, humidity was set to 100% in one chamber, and the specimen was inserted in the center of the tube. Then, a vacuum pump was connected to the opposite chamber to allow water vapor to move through the tube. The humidity change of the chamber set to 100% was measured at 20 second intervals.

Comparing the humidity after 200 seconds from the start of the humidity change, the pure wool fiber is 57.8%, which is close to the equilibrium humidity, and in the case of the specimen coated with MMT-PEI 5 layers in (A) and (C), 66.5% and 73.6%, respectively. showed a difference with the equilibrium humidity.

In addition, in (B) and (D), the specimens coated with 10 layers of MMT-PEI were 76% and 78.5%, respectively, showing a significant difference from the equilibrium humidity.

From the above results, the layered self-assembly method coating made using MMT and PEI affected the moisture movement in the air and can control the humidity in the equilibrium state. Therefore, it can be said that the thicker the MMT is, the more it hinders the movement of water vapor in the air.

In the above, the present invention has been described in detail only with respect to the described embodiments, but it is obvious to those skilled in the art that various modifications and variations are possible within the scope of the technical spirit of the present invention, and it is natural that such variations and modifications belong to the appended claims.

Claims (7)

A first step of spraying a cationic solution on the specimen,
a second step of washing with deionized water;
A third step of spraying the anionic solution and
The fourth step of washing with deionized water is a spray-type layered self-assembled coating consisting of one cycle, and after spraying the solution, vacuum suction is performed on the opposite side of the specimen during the washing step to make a thin film made of a cationic-anionic composite material is coated,
A method of manufacturing a barrier film in which the coating is arranged in n layers on the specimen by repeating n times to control the thickness of the thin film. According to claim 1, wherein the specimen is a conductive substrate selected from the group consisting of gold, copper, aluminum, nickel and zinc; or a polymer substrate selected from PDMS or PET. The method of claim 1, wherein the specimen is a fiber selected from the group consisting of wool, cotton, polyester and glass fiber. The method of claim 3, wherein a precursor layer of LPEI/PAA (linear polyethylenimine/polyacrylic acid) is formed on the fiber. 2. The method of claim 1, wherein the cationic solution is branched polyethyleneimine, linear polyethyleneimine, polydiallyldimethyl ammonium chloride, polyallylamine hydrochloride, poly-L-lysine, poly(amidoamine), poly(amino- At least one selected from the group consisting of co-ester), poly(2-N,N-dimethylaminoethyl methacrylate) and poly(ethylene glycol-co-2-N,N-dimethylaminoethyl methacrylate) A method for producing a barrier film, characterized in that it is a solution containing a polymer. The method according to claim 1, wherein the anionic solution is a solution containing at least one selected from the group consisting of montmorillonite, laponite, saponite, beidellite, vermiculite, nontronite, hectorite, and fluorohectorite. Method for producing a barrier film, characterized in that. A method for evaluating the properties of a barrier film according to the cyclic voltammetry method in which the barrier film obtained by the spray-type layered self-assembly coating of claim 1 is used as a three-electrode.

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