KR101499291B1 - Method for preparing an anti-fingerprint layer and an anti-fingerprint layer prepared by using the same - Google Patents

Abstract

The present invention relates to an inner fingerprint coating method and an inner fingerprint coating layer produced using the same, which comprises: coating a composition for forming a lower coating layer containing silicon dioxide on a substrate to form a lower coating layer; Wherein the composition for forming a lower coating layer, the composition for forming an upper coating layer, and a combination thereof is used for forming the upper coating layer. The composition for forming the lower coating layer, the composition for forming the upper coating layer, And an organic acid composition in which ions are dispersed.
The inner fingerprint coating method can produce an inner fingerprint coating layer excellent in stain resistance and transparency and also excellent in antibacterial activity.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fingerprint coating method and an inner fingerprint coating layer using the same,

FIELD OF THE INVENTION The present invention relates to an inner fingerprint coating method and an inner fingerprint coating layer produced using the inner fingerprint coating method, and more particularly, to an inner fingerprint coating method having excellent stain resistance and anti- will be.

Cell phones are the stuff most people use, and they can be a hotbed of bacteria and bacteria because they are always carried around.

On the other hand, in recent years, in order to solve the problem of hygiene, a technique using nano metal particles having an antibacterial and sterilizing function has been widely spread. That is, a method is known in which a predetermined amount of nano metal particles are mixed with a master batch in the manufacture of articles, and a method in which nano metal particles are coated on the surface of an article is known.

However, when an article produced by mixing metal nanoparticles in a master batch is directly in contact with bacteria, the metal nanoparticles having an antibacterial and sterilizing function are located inside the article, so that the antibacterial and sterilizing functions are less directly or completely invalid .

When metal nanoparticles are coated on the surface of an article, they are mixed with an organic coating agent such as LACKER, or mixed with an inorganic coating agent such as a ceramic coating agent (CERAMIC GLAZE), and coated by spraying or sputtering , Organic coatings have a disadvantage in that they are simple in manufacturing process and high in transparency but they are weak in heat resistance and easily dissolve in solvents. Inorganic coatings have good heat resistance and high UV shielding properties. They are not easily soluble in solvents but have a complicated manufacturing process, There are easy disadvantages.

In addition, when the metal nanoparticles are coated, if the thickness of the metal nanoparticles is coated more than necessary, the manufacturing cost increases, regardless of the effect, and the metal nanoparticles aggregate, resulting in a higher failure rate of the product. .

On the other hand, in the case of various displays such as a mobile phone, the image is easily distorted by the fingerprint or the quality of the appearance is poor. In addition, when a conventional general surface treatment agent is used, the contamination such as a fingerprint is not easily removed, but rather the property of spreading causes a serious problem.

In addition, due to continuous use and impact, scratches are generated due to stress on the surface, and germs such as Escherichia coli, Staphylococcus aureus, and Super bacteria (MRSA), which are not only general bacteria but also pathogenic bacteria, progress.

Japanese Patent Laid-Open No. 2003-301273 Japanese Patent Application Laid-Open No. 2003-310411 Japanese Patent Application Laid-Open No. 2002-277604

It is an object of the present invention to provide an inner fingerprint coating method capable of producing an inner fingerprint coating layer excellent in stain resistance and transparency and also excellent in antibacterial activity.

Another object of the present invention is to provide an inner fingerprint coating layer produced by the inner fingerprint coating method.

According to an embodiment of the present invention, there is provided an inner fingerprint coating method comprising: forming a lower coating layer by coating a composition for forming a lower coating layer containing silicon dioxide on a substrate; and forming a coating composition for forming an upper coating layer containing a fluorine- Wherein the composition for forming a lower coating layer, the composition for forming an upper coating layer, and a combination thereof is prepared by coating an organic acid composition having nanometer metal ions dispersed therein, .

The composition for forming the lower coating layer or the composition for forming the upper coating layer may include 1 to 40% by weight of the organic acid composition in which the nano metal ions are dispersed in the composition for forming the lower coating layer or the composition for forming the upper coating layer .

The nano metal ion may be an ion of any metal selected from the group consisting of copper, silver, gold, zinc, platinum, cobalt, and combinations thereof.

The organic acid may be any one selected from the group consisting of citric acid, lactic acid, sorbic acid, and combinations thereof.

The organic acid composition in which the nano metal ions are dispersed is prepared by adding an organic acid to a solvent and heating and concentrating the mixture at 50 to 70 ° C to prepare a concentrated solution, adding a guanidine salt to the concentrated solution, And adding a strong acid salt of the metal to the organic acid composition to disperse the nano metal ions.

In the step of preparing the concentrated solution, ethylene oxide may be further added to the solvent together with the organic acid.

In the step of preparing the organic acid composition, titanium dioxide may be further added to the concentrated solution together with the guanidine salt.

After the step of dispersing the nano metal ions, the method may further include mixing the organic acid composition in which the nano metal ions are dispersed, with the alkoxysilane.

The alkoxysilane may be at least one selected from the group consisting of methyltrimethoxy silane, tetramethoxy silane, 3-methacryloxypropyltrimethoxysilane, and combinations thereof. Lt; / RTI >

According to another embodiment of the present invention, an inner fingerprint coating layer is coated on a substrate and includes a lower coating layer containing silicon dioxide, and an upper coating layer coated on the lower coating layer and including a fluorine-containing resin, The top coating layer includes an organic acid composition in which nano metal ions are dispersed.

The lower coating layer or the upper coating layer may contain 1 to 40% by weight of the organic acid composition in which the nano metal ions are dispersed throughout the lower coating layer or the upper coating layer.

Wherein the nano metal ion dispersed organic acid composition comprises 1 to 10% by weight of nano-metal ions, 1 to 10% by weight of organic acids, 0.5 to 5% by weight of ethylene oxide, 1 to 10% by weight of guanidine salts, 0.1 to 5% And may contain the remaining amount of solvent.

The inner fingerprint coating method of the present invention can produce an inner fingerprint coating layer excellent in stain resistance and transparency and excellent in antibacterial activity.

1 is a photograph showing a glass substrate on which an inner fingerprint coating layer prepared in Example 1 is formed.
2 to 5 are photographs showing results of antibacterial test of the inner fingerprint coating layer prepared in Example 1. Fig.

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

According to an embodiment of the present invention, there is provided an inner fingerprint coating method comprising: forming a lower coating layer by coating a composition for forming a lower coating layer containing silicon dioxide on a substrate; and forming a coating composition for forming an upper coating layer containing a fluorine- To form an upper coating layer.

First, a composition for forming a lower coating layer containing silicon dioxide is coated on a substrate to form a lower coating layer.

The substrate is not particularly limited in the present invention and may be glass, glass ceramics, ceramics, plastics or metal, for example.

The step of coating the composition for forming a lower coating layer containing silicon dioxide to form a lower coating layer may include preparing a composition for forming a lower coating layer including a silicon dioxide precursor capable of generating silicon dioxide or silicon dioxide, And coating a composition for forming a lower coating layer on the substrate.

Examples of the silicon dioxide precursor capable of generating silicon dioxide include tetramethoxysilane and tetraethoxysilane.

The composition for forming the lower coating layer may be prepared by adding the silicon dioxide or the silicon dioxide precursor to a solvent. In the present invention, the solvent may be any solvent capable of dissolving the silicon dioxide or the silicon dioxide precursor. Examples of the solvent include ethanol, methanol, propanol, isopropanol, butanol, acetone, pentane, toluene, (DMF), dimethyl acetamide (DMAC), dimethylsulfoxide (DMSO), carbon tetrachloride, dichloromethane, dichloroethane, dichloromethane and the like. , Any one selected from the group consisting of trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, trichlorobenzene, cyclohexane, cyclopentanone, cyclohexanone, dioxane, terpineol, methyletherketone and combinations thereof And preferably isopropanol can be used.

The method of coating the composition for forming the lower coating layer is not particularly limited in the present invention and may be carried out by a wet method such as dipping, spin coat, roll coat, spray coat, Or a dry method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) such as a vacuum deposition method, a reactive deposition method, an ion beam assist method, a sputtering method, or an ion plating method.

Next, a coating composition for forming an upper coating layer containing a fluorine-containing resin is coated on the lower coating layer to form an upper coating layer.

The step of coating the composition for forming an upper coating layer containing the fluorine-containing resin to form an upper coating layer may include the steps of preparing a composition for forming an upper coating layer comprising a fluorine-containing resin or a fluorine-containing resin precursor capable of producing a fluorine- , And coating the prepared composition for forming an upper coating layer on the lower coating layer.

As the fluorine-containing resin, not only a fluorine resin but also a resin in which a polyester resin, an epoxy resin, a polyolefin resin, a polyurethane resin, a fluorine resin, a phenol resin, an acrylic resin, a polycarbonate resin or the like is modified to fluorine can be used.

The fluorine-containing resin may be a water-repellent (lipophilic) resin containing fluorine such as a polyfluoroalkyl group or a polyfluoroether group having 4 to 12 carbon atoms.

Examples of the fluorine-containing silane is _{CF 3 (CH 2) 2 Si} , (OCH 3) 3, CF 3 CF 2 (CH 2) 2 Si (OCH 3 more specifically containing resin The fluorine may be in the containing silane fluoride, _{) 3, CF 3 (CF 2} ) 2 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 3 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 4 (CH _{2) 2 Si (OCH 3)} 3, CF 3 (CF 2) 5 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 6 (CH 2) 2 Si (OCH 3) 3, CF 3 _{(CF 2) 7 (CH 2} ) 2 Si (OCH 3) 3, CF 3 (CF 2) 8 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 9 (CH 2) 2 Si ( _{OCH 3) 3, CF 3 (} CH 2) 2 Si (OC 2 H 5) 3, CF 3 CF 2 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 2 (CH 2) _{2 Si (OC 2 H 5)} 3, CF 3 (CF 2) 3 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 4 (CH 2) 2 Si (OC 2 H 5) _{3, CF 3 (CF 2)} 5 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 6 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) _{7 (CH 2) 2 Si (} OC 2 H 5) 3, CF 3 (CF 2) 8 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 9 (CH 2) 2 Si ( OC ₂ H _{5) 3,} etc. can be exemplified, these alone or two or a The can also be used together.

As the fluorine-containing resin, commercially available KY-164 and KY-108 of Shin-Etsu, or DSX OPTOOL of Daikin Co., Ltd. may be used.

The composition for forming the upper coating layer may be prepared by adding the fluorine-containing resin or the fluorine-containing resin precursor to a solvent. In the present invention, any solvent may be used as long as it can dissolve the fluorine-containing resin or the fluorine-containing resin precursor. Examples of the solvent include ethanol, methanol, propanol, isopropanol, butanol, acetone, pentane, toluene, (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), carbon tetrachloride, dichloromethane, tetrahydrofuran, and the like. The solvent is selected from the group consisting of dichloroethane, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, trichlorobenzene, cyclohexane, cyclopentanone, cyclohexanone, dioxane, terpineol, methyletherketone, And preferably, isopropanol can be used.

The method for coating the composition for forming the upper coating layer is not particularly limited in the present invention and may be carried out by a wet method such as dipping, spin coat, roll coat, spray coat, Or a dry method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) such as a vacuum deposition method, a reactive deposition method, an ion beam assist method, a sputtering method, or an ion plating method. Specifically, the upper coating layer may be formed by preparing the composition for forming the upper coating layer in the form of a tablet and then sparking in a vacuum chamber.

At this time, any composition selected from the group consisting of the composition for forming the lower coating layer, the composition for forming the upper coating layer, and the combination thereof further includes an organic acid composition in which the nano metal ions are dispersed. The inner fingerprint coating method can produce an inner fingerprint coating layer having improved antibacterial activity through the organic acid composition in which the nano metal ions are dispersed.

The composition for forming a lower coating layer or the composition for forming an upper coating layer may contain 1 to 40% by weight, preferably 1 to 40% by weight, of an organic acid composition in which the nano metal ions are dispersed, with respect to the composition for forming a lower coating layer or the composition for forming an upper coating layer. By weight to 10% by weight. If the content of the organic acid composition in which the nano metal ions are dispersed is less than 1% by weight, the formed fingerprint coating layer may not have antibacterial property. If the content of the organic acid composition is more than 40% by weight, .

The nano metal ion may be an ion of any one metal selected from the group consisting of copper, silver, gold, zinc, platinum, cobalt, and combinations thereof. In particular, copper or silver has excellent antibacterial activity and can be preferably used .

The lower coating layer or the upper coating layer may be exposed to ultraviolet rays while being exposed to ultraviolet rays. The nano metal may be oxidized and changed in color upon irradiation with ultraviolet rays. Therefore, in order to prevent oxidation of the nano metal, Includes nanometals in the form of ions.

The method of introducing the organic acid composition in which the nano metal ions are dispersed into the composition for the lower coating or the composition for the upper coating is not limited to the present invention, and a conventionally used method can be used. For example, when the composition for the lower coating or the composition for the upper coating is a wet composition, the organic acid composition in which the nano-ions are dispersed may be mixed with the composition for the lower coating or the composition for the upper coating, When the composition for the upper coating or the composition for the upper coating is a dry composition, the composition for the lower coating or the composition for the upper coating is immersed in the organic acid composition in which the nano-ions are dispersed, The organic acid composition in which the nano-ions are dispersed may be injected.

The organic acid composition in which the nano metal ions are dispersed is one in which the nano metal ions are dispersed in any one of organic acids selected from the group consisting of citric acid, lactic acid, sorbic acid, , Can be prepared through the following steps.

First, an organic acid is added to a solvent, followed by heating and dissolution to prepare a concentrated solution. A guanidine salt is added to the concentrated solution and stirred to prepare the organic acid composition.

In the step of preparing the concentrated solution, the organic acid is added to the solvent, and the solution is heated and dissolved at 50 to 70 ° C to concentrate the organic acid to a content of 3 to 30% by weight.

The solvent may be any of those used for the lower coating composition or the composition for forming the upper coating layer, and preferably ethanol or ether may be used.

In the step of preparing the concentrated solution, ethylene oxide may be further added to the solvent together with the organic acid. The ethylene oxide may react with the water-based or alcohol-based solvent, ≪ / RTI >

The guanidine salt may be a salt of a guanidine such as a phosphate, a nitrate, a hydrochloride or a sulfate.

At this time, titanium dioxide may be further added to the concentrated solution together with the guanidine salt or after the guanidine salt is added. The titanium dioxide can improve the surface slip property of the composition for the lower coating or the composition for the upper coating and improve the stain resistance, and an anatase type can be preferably used.

When the strong acid salt of the metal is added to the prepared organic acid composition to disperse the nano metal ions, an organic acid composition in which nano metal ions are dispersed can be prepared. The strong acid salt of the metal may be a sulfate, a nitrate or a hydrochloride, preferably a nitrate. When the metal is added to the organic acid composition in the form of a strong acid salt, a composition in which nanometals are dispersed can be obtained.

After the step of dispersing the nano metal ions, the method may further include mixing the organic acid composition in which the nano metal ions are dispersed, with the alkoxysilane. When the organic acid composition in which the nano metal ions are dispersed is mixed with the alkoxysilane, an alkoxy group is introduced into the organic acid composition in which the nano metal ions are dispersed, and the organic acid composition in which the nano metal ions are dispersed is mixed with the fluorine- .

The alkoxysilane may be at least one selected from the group consisting of methyltrimethoxy silane, tetramethoxy silane, 3-methacryloxypropyltrimethoxysilane, and combinations thereof. Lt; / RTI >

The organic acid composition in which the nano metal ions are dispersed and the alkoxysilane may be mixed at a weight ratio of 10:90 to 30:70. When the weight ratio of the organic acid composition in which the nano metal ions are dispersed is less than 10, the antibacterial ability may be lowered, and when the weight ratio is more than 30, abrasion resistance may be deteriorated.

The inner fingerprint coating layer according to another embodiment of the present invention can be formed by the inner fingerprint coating method and is coated on the substrate and includes a lower coating layer containing silicon dioxide and a fluororesin coated on the lower coating layer Wherein the lower coating layer or the upper coating layer comprises an organic acid composition in which nano metal ions are dispersed.

Since the upper coating layer is a portion directly contacting the hand, when the organic acid composition containing the nano metal ion is dispersed, the inner fingerprint coating layer may have antibacterial properties. However, since the upper coating layer contains a fluorine-containing resin, there is a limit to the content of the organic acid composition in which the nano metal ions are dispersed. In addition, even when the undercoat layer includes an organic acid composition in which the nano metal ions are dispersed, the inner fingerprint coating layer may have antibacterial property because the nano metal ions included in the undercoat layer partially migrate .

The lower coating layer or the upper coating layer may contain 1 to 40% by weight, preferably 1 to 10% by weight, of the organic acid composition in which the nano metal ions are dispersed in the whole of the lower coating layer or the upper coating layer. If the content of the organic acid composition in which the nano metal ions are dispersed is less than 1% by weight, the formed fingerprint coating layer may not have antibacterial property. If the content of the organic acid composition is more than 40% by weight, .

Wherein the nano metal ion dispersed organic acid composition comprises 1 to 10% by weight of nano-metal ions, 1 to 10% by weight of organic acids, 0.5 to 5% by weight of ethylene oxide, 1 to 10% by weight of guanidine salts, 0.1 to 5% And may contain the remaining amount of solvent. In the method for preparing an organic acid composition in which the nano metal ions are dispersed, the addition amount of each component can be appropriately adjusted according to a desired final content in the organic acid composition in which the nano metal ions are dispersed.

If the content of the nano metal ions is less than 1% by weight, the antibacterial activity may be lowered. If the content is more than 10% by weight, the adhesive strength and transparency may be lowered.

If the content of the organic acid is less than 1% by weight, the antibacterial activity may be lowered. If the content is more than 10% by weight, the bonding strength may be lowered and precipitation may occur.

If the content of ethylene oxide is less than 0.5% by weight, unreacted materials may occur in a large amount. If the content of ethylene oxide is more than 5% by weight, dilution of other components may occur.

If the content of the guanidine salt is less than 1% by weight, the reaction may not take place, and if it exceeds 10% by weight, precipitation may occur.

If the content of the titanium dioxide is less than 0.1% by weight, the photocatalytic effect may not be generated. If the content of the titanium dioxide exceeds 5% by weight, transparency may be lowered.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Manufacturing example : My fingerprint  Preparation of coating layer]

( Example  One)

10 g of citric acid and 80 g of ethylene oxide were added to ethenol and dissolved by heating at 70 DEG C to concentrate the citric acid to 20 wt%. 10 g of a guanidine salt (a phosphate of guanidine) was added to the concentrated solution and stirred. To the concentrated solution, 1 g of titanium dioxide nanoparticle (anatase) was added, and the mixture was stirred at a high rotation speed of 10,000 rpm to prepare an organic acid composition. 1 g of copper nitrate was added to the organic acid composition to prepare an organic acid composition in which nano metal ions were dispersed.

80 parts by weight of methyltrimethoxysilane was added to 20 parts by weight of the organic acid composition in which the nano metal ions were dispersed, followed by mixing for 10 hours.

On the other hand, a composition for forming a lower coating layer was prepared by mixing 15% by weight of tetramethoxysilane precursor, 80% by weight of isopropyl alcohol as a solvent, and 5% by weight of an organic acid composition in which the nano metal ions were dispersed. The composition for forming a lower coating layer was coated on a glass substrate by a spin coat method to form a lower coating layer.

Further, an organic acid composition in which the nanometer metal ions were dispersed was injected into KY-164 of Shin-Etsu Co., Ltd., a fluorine-containing resin in the form of a tablet, to prepare a composition for forming an upper coating layer. At this time, the composition for forming the upper coating layer was injected so that the content of the organic acid composition in which the metal ions were dispersed was 5 wt%. The upper coating layer was formed on the lower coating layer by sparking the prepared composition for forming an upper coating layer in a vacuum chamber.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing a glass substrate on which the inner fingerprint coating layer prepared above is formed.

[ Experimental Example : Antibacterial test]

The bacterial counts of Staphylococcus aureus ATCC 6538P and Escherichia coli ATCC 8739 were cultured for 24 hours at 35 ± 1 ° C and RH 90 ± 5% in 25 cm 2 of the inner fingerprint coating layer prepared in Example 1, And the results are shown in Tables 1 to 2 and 2 to 5 below.

Table 1, FIG. 2 (experimental group) and FIG. 3 (control group) show the results of the experiment on Staphylococci. Table 2, FIG. 4 (experimental group) and FIG. 5 (control group) show the results of experiments on E. coli.

Strain 1: Staphylococcus aureus ATCC 6538P Inoculum concentration (CFU / ml) 2.1 × 10 ⁵ The proliferation value (F) 1.7 M _a 2.1 × 10 ⁵ M _b 1.0 x 10 ⁷ M _c <10 Antibacterial activity (S) - Reduction rate (%) (6.0) 99.9

Strain 2: Escherichia coli ATCC 8739 Inoculum concentration (CFU / ml) 2.4 × 10 ⁵ The proliferation value (F) 1.6 M _a 2.4 × 10 ⁵ M _b 1.2 × 10 ⁷ M _c <10 Antibacterial activity (S) - Reduction rate (%) (6.1) 99.9

- CFU: Colony Forming Unit

- Antibacterial activity (S): log (M _b / M _c )

- Antibacterial activity (S): log (Mb / Mc)

- reduction rate (%): [(Mb-Mc) / Mb] x 100

- Proliferation value (F): log (Mb / Ma) (1.5 or more)

- Ma: Average number of viable cells immediately after inoculation of test sample of standard sample (3 samples)

- Mb: Average number of viable cells (3 samples) after incubation of standard sample (24 hours)

- Mc: Average number of viable cells (3 samples) after incubation for a certain period of time (24 hours)

Referring to Tables 1 to 2 and 2 to 5, it can be confirmed that the inner fingerprint coating layer is excellent in antibacterial activity.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (12)

Coating a substrate with a composition for forming a lower coating layer comprising a silicon dioxide or silicon dioxide precursor and a solvent on the substrate to form a lower coating layer; and
Forming an upper coating layer by coating a composition for forming an upper coating layer prepared by adding a fluorine-containing resin to an organic acid composition in which nano metal ions are dispersed on the lower coating layer;
/ RTI &gt;
Wherein the composition for forming an upper coating layer comprises 1 to 40% by weight of an organic acid composition in which the nano metal ions are dispersed in the composition for forming an upper coating layer,
The organic acid composition in which the nano metal ions are dispersed comprises 1 to 10% by weight of nano-copper ions, 1 to 10% by weight of citric acid, 0.5 to 5% by weight of ethylene oxide, 1 to 10% by weight of salt, 0.1 to 5% by weight of titanium dioxide and the balance of the solvent. The method according to claim 1,
The composition for forming a lower coating layer may further comprise an organic acid composition in which nano metal ions are dispersed,
Wherein the composition for forming a lower coating layer comprises 1 to 40% by weight of an organic acid composition in which the nano metal ions are dispersed in the entire composition for forming a lower coating layer. delete delete The method according to claim 1,
The organic acid composition in which the nano metal ions are dispersed
Adding citric acid to the solvent and heating to 50 to 70 캜 to prepare a concentrated solution,
Adding a guanidine salt to the concentrated solution and stirring to prepare the organic acid composition, and
Adding the strong acid salt of copper to the organic acid composition to disperse the nano metal ions
&Lt; / RTI &gt; 6. The method of claim 5,
Wherein in the step of preparing the concentrated solution, ethylene oxide is further added to the solvent together with the citric acid. 6. The method of claim 5,
Wherein in the step of preparing the organic acid composition, titanium dioxide is further added to the concentrated solution together with the guanidine salt. 6. The method of claim 5,
Further comprising the step of mixing the nanocomposite-dispersed organic acid composition with the alkoxysilane after the step of dispersing the nano-metal ions. 9. The method of claim 8,
The alkoxysilane may be at least one selected from the group consisting of methyltrimethoxy silane, tetramethoxy silane, 3-methacryloxypropyltrimethoxysilane, and combinations thereof. By weight. A lower coating layer coated on the substrate and comprising silicon dioxide, and
And an upper coating layer coated on the lower coating layer and comprising an organic acid composition in which a fluorine-containing resin and nano metal ions are dispersed,
Wherein the upper coating layer comprises 1 to 40% by weight of an organic acid composition in which the nano metal ions are dispersed in the entire upper coating layer,
The organic acid composition in which the nano metal ions are dispersed comprises 1 to 10% by weight of nano-copper ions, 1 to 10% by weight of citric acid, 0.5 to 5% by weight of ethylene oxide, 1 to 10% by weight of salt, 0.1 to 5% by weight of titanium dioxide, and the balance of the solvent. 11. The method of claim 10,
Wherein the lower coating layer further comprises an organic acid composition in which nano metal ions are dispersed,
Wherein the lower coating layer comprises 1 to 40% by weight of an organic acid composition in which the nano metal ions are dispersed in the entire lower coating layer. delete

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