KR20130077630A - Method for preparing glass coating composition and composition for coating glass - Google Patents

Abstract

PURPOSE: A manufacturing method of a glass coating composition is provided to use an organic acid composition with nano metal ions dispersed inside for improving staining resistance, anti-finger printing property, and antibacterial activity. CONSTITUTION: A manufacturing method of a glass coating composition comprises the following steps: adding silicate into a solution to obtain a first mixture solution; adding silicon into the first mixture solution to obtain a first binding composition; and adding a nano metal ion dispersed organic acid composition to the first binding composition to obtain a second binding composition. The glass coating composition contains 10-35wt% of silica, 10-30wt% of silicon, 1-10wt% of a nano metal ion dispersed organic acid composition, 1-5wt% of an additive, and the solution. The nano metal ion dispersed organic acid composition contains 1-10wt% of nano metal ions, 1-10wt% of organic acid, 0.5-5wt% of ethylene oxide, 1-10wt% of guanidine salt, 0.1-5wt% of titanium dioxide, and a solvent.

Description

The manufacturing method of the composition for glass coatings, and the composition for glass coatings {METHOD FOR PREPARING GLASS COATING COMPOSITION AND COMPOSITION FOR COATING GLASS}

The present invention relates to a method for producing a composition for glass coating and a composition for glass coating, and more particularly, to a method for producing a composition for glass coating and a composition for glass coating which is excellent in stain resistance and anti-fingerprint resistance and also excellent in antibacterial activity. .

Mobile phones are objects used by most people and are always carried with them and can be a breeding ground for bacteria and bacteria.

On the other hand, in recent years, if you want to improve the hygiene problems, the technology using nano metal particles having an antibacterial and sterilization function is widely used. 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, an article manufactured by mixing metal nanoparticles in a master batch has a problem in that metal nanoparticles having antimicrobial and sterilizing functions are placed inside the article so that the antimicrobial and sterilizing functions have little or no direct effect. .

In addition, in the case of coating the metal nanoparticles on the surface of the article is mixed with an organic coating such as lacquer (LACKER), or mixed with an inorganic coating such as ceramic coating (CERAMIC GLAZE) to coat by spraying, sputtering, etc. In the case of organic coatings, the manufacturing process is simple and the transparency is high, but the heat resistance is weak and easily soluble in the solvent.In the case of the inorganic coating, the heat resistance is good, the UV blocking property is not easily soluble in the solvent, but the manufacturing process is complicated, the transparency is low and fragile. There is an easy disadvantage.

In addition, in the case of coating the metal nanoparticles with a thickness of more than necessary, the manufacturing cost increases and the aggregation of metal nanoparticles occurs regardless of the effect, resulting in a high incidence of product defects, thereby reducing the antibacterial and deodorizing effect. Can be.

On the other hand, in the case of various displays such as mobile phones, there is a problem in that the image is easily distorted by the fingerprint or the appearance quality is poor. In addition, when the conventional surface treatment agent is used, contamination such as fingerprints is not easily removed, but rather has a bleeding characteristic, the severity becomes greater.

Conventionally, a method of implementing a surface treatment to impart wear resistance and stain resistance has been proposed as follows.

The first method is to introduce a hydrophobic fluorine-based or silicone-based surfactant into the wear-resistant coating liquid, and after coating and curing, a hydrophobic surfactant is placed on the film surface to impart stain resistance to the film. In this case, since the hydrophobic surfactant is not bonded to the binder of the coating layer, the surface is rubbed several hundred times with a cloth, and then the stain resistance is measured. In addition, in order to secure a satisfactory level of pollution resistance, an excessive amount of surfactant must be added, and in this case, wear resistance is deteriorated.

The second method is to form a coating layer that imparts contamination resistance on the wear-resistant coating layer by two coating methods. Japanese Patent Laid-Open Publication No. 1995-016940 describes a method of separately coating a copolymer of acrylate and silica having a perfluoro group on a low reflection layer composed mainly of silica. Such a method has the effect that the fouling resistance property persists even when rubbing the film surface, but for this purpose, there is a restriction that a bond group capable of reacting with the material of the fouling resistant layer is required in the wear-resistant coating layer, and is produced by a double coating method. There is a problem that the manufacturing cost rises. In addition, when oil components, such as fingerprints, etc. are continuously contacted, the problem that oil penetrates into a membrane and the membrane characteristic falls rapidly cannot be improved.

Therefore, there is a great demand for a composition for coating metal nanoparticles having excellent wear resistance and stain resistance and excellent antibacterial performance which can be applied to a mobile phone.

Korean Patent Registration No. 0671982 (Registration date: January 15, 2007) Korean Patent Registration No. 0787544 (Registration date: December 21, 2007) Japanese Patent Publication No. 1995-016940 (published: January 20, 1995)

An object of the present invention is to provide a method for producing a composition for glass coating which is excellent in stain resistance and anti-fingerprint resistance and also excellent in antibacterial activity.

Another object of the present invention to provide a composition for glass coating prepared using the method for producing a composition for glass coating.

According to one or more exemplary embodiments, a method for preparing a glass coating composition may include adding silicates to a solvent to prepare a first mixed solution, and adding silicon to the first mixed solution to prepare a first binding composition. And adding an organic acid composition in which nano metal ions are dispersed in the primary binding composition to prepare a secondary binding composition.

The preparing of the first mixed solution may be performed by stirring at 100 to 150 ° C. to 300 to 400 rpm.

The preparing of the primary binding composition may be performed by mixing at 0 to 50 ° C. at 100 to 150 rpm for 1 to 3 hours and then stirring at 250 to 300 rpm for 4 to 8 hours.

The step of preparing the secondary binding composition may be made by stirring at 300 to 400 rpm at 0 to 50 ℃.

The nano metal ions may be ions of any one 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 concentrating by heating to 50 to 70 ° C. to prepare a concentrated solution, adding the guanidine salt to the concentrated solution and stirring to prepare the organic acid composition. And it can be prepared through the step of dispersing nano metal ions by adding a strong acid salt of the metal to the organic acid composition.

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

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

Glass coating composition according to another embodiment of the present invention is 10 to 35% by weight of silica, 10 to 30% by weight of silicon (silicone), 1 to 10% by weight of the organic acid composition in which the nano-metal ions are dispersed, 1 to 5% by weight of the additive % And the rest of the solvent.

The organic acid composition in which the nano metal ions are dispersed includes 1 to 10 wt% of nano metal ions, 1 to 10 wt% of organic acid, 0.5 to 5 wt% of ethylene oxide, 1 to 10 wt% of guanidine salt, 0.1 to 5 wt% of titanium dioxide, and The remaining content of solvent may be included.

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

Method for preparing a composition for glass coating according to an embodiment of the present invention comprises the steps of preparing a first mixed solution by adding a silicate to the solvent and stirring, adding a silicon to the first mixed solution and stirred to form a primary binding composition Preparing, and preparing a secondary binding composition by adding and stirring an organic acid composition in which nano metal ions are dispersed in the primary binding composition.

First, a silicate is added to the solvent and stirred to prepare a first mixed solution.

The silicate may be preferably used as a precursor for producing silica, preferably potassium silicate or sodium silicate.

The solvent serves as a diluent to preserve the transparency of the glass coating composition and maintain the viscosity. If the viscosity is high in the process of coating the glass coating composition on the glass surface may be difficult to coat.

The solvent can be used as long as it can dissolve the silicate, specifically, ethanol, methanol, propanol, isopropanol, butanol, acetone, pentane, toluene, benzene, diethyl ether, methyl butyl ether, N-methylpyro Lyddon (NMP), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), carbon tetrachloride, dichloromethane, dichloroethane, trichloroethylene, chloroform, chloro Benzene, dichlorobenzene, trichlorobenzene, cyclohexane, cyclopentanone, cyclohexanone, dioxane, terpineol, methyl ether ketone and combinations thereof, and any combination thereof, preferably isopropanol Can be used.

The preparing of the first mixed solution may be performed by stirring at 100 to 150 ° C. to 300 to 400 rpm. When the stirring conditions are within the above range, it may be easy to control the content of silicate by preventing evaporation of the liquid component.

Next, silicon is added to the prepared first mixed solution and stirred to prepare a primary bonding composition. The silicon is a polymer in which silicon containing an organic group (organosilicone) and oxygen are connected to each other by a chemical bond. The silicone may be silicone oil, silicone rubber or silicone resin, all of which can be used in the present invention.

The silicon serves to help the adhesion between the silica and the glass surface, and push the contaminants to the outside to increase the stain resistance.

The step of preparing the primary binding composition may be mixed at 100 to 150 rpm for 1 to 3 hours at 0 to 50 ° C., preferably at room temperature, and then to 250 to 300 rpm for 4 to 8 hours. In the case of stirring under the above conditions, the silicate and the silicon are easily mixed.

Finally, the secondary binding composition may be prepared by adding and stirring an organic acid composition in which nano metal ions are dispersed in the primary binding composition.

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, and particularly, copper or silver may be preferably used because of excellent antibacterial activity. .

The glass coating composition is applied to the glass surface is exposed to ultraviolet rays when used, since the nano metal can be oxidized to change color when irradiated with ultraviolet light, the glass coating composition is nano metal to prevent oxidation of the nano metal. In the form of ions.

The step of preparing the secondary binding composition may be made by stirring at 300 to 400rpm at 0 to 50 ℃, preferably room temperature. When stirring under the above conditions, the nano metal ions may be well dispersed in the silicate and silicon in the state of ions.

The organic acid composition in which the nano metal ions are dispersed is obtained by dispersing the nano metal ions in one organic acid selected from the group consisting of citric acid, lactic acid, sorbic acid, and a combination thereof. It can be prepared through the following steps.

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

In preparing the concentrated solution, the organic acid is added to the solvent and dissolved by heating at 50 to 70 ° C. until the content of the organic acid is 3 to 30 wt%.

The solvent may use all of the solvents used in the preparation of the first mixed solution, preferably ethanol or ether.

In the preparing of the concentrated solution, ethylene oxide may be further added to the solvent together with the organic acid, and the ethylene oxide is added to make the glass coating composition react well with water or an alcohol solvent.

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

At this time, after the addition of the guanidine salt or the guanidine salt to the concentrated solution, titanium dioxide may be further added. The titanium dioxide is to improve the surface slip properties of the glass coating composition and to improve the stain resistance, and the anatase type can be preferably used.

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

The prepared glass coating composition may be selectively annealed. The annealing may be made at 15 to 30 ℃. When the annealing is carried out at a temperature exceeding 30 ° C components of the glass coating composition may be volatilized.

The glass coating composition prepared by the method for preparing the glass coating composition finally has 10 to 35% by weight of silica, 10 to 30% by weight of silicon, 1 to 10% by weight of an organic acid composition in which nano metal ions are dispersed, and additives 1 to 1. 5% by weight, and the remainder of the solvent. That is, the addition amount of each component in the manufacturing method of the glass coating composition can be appropriately adjusted according to the desired final content in the glass coating composition.

If the content of the silica is less than 10% by weight there may be a surface unreacted problem, if it exceeds 35% by weight there may be a problem in long-term storage.

Hardness may be a problem after vitrification when the content of the silicon is less than 10% by weight, and curing rate may be too slow when it exceeds 30% by weight.

When the content of the organic acid composition in which the nano-metal ions are dispersed is less than 1% by weight, the increase of the antimicrobial activity is insignificant, and when the content of the organic acid composition exceeds 10% by weight, the adhesive strength and transparency may be reduced.

The organic acid composition in which the nano metal ions are dispersed includes 1 to 10 wt% of nano metal ions, 1 to 10 wt% of organic acid, 0.5 to 5 wt% of ethylene oxide, 1 to 10 wt% of guanidine salt, 0.1 to 5 wt% of titanium dioxide, and The remaining content of solvent may be included. Even in the method of preparing the organic acid composition in which the nano metal ions are dispersed, the amount of each component may be appropriately adjusted to the desired final content in the organic acid composition in which the nano metal ions are dispersed.

When the content of the nano-metal ions is less than 1% by weight, the antimicrobial activity may be lowered. When the content of the nanometal ions is greater than 10% by weight, the adhesive strength and transparency may be reduced.

When the content of the organic acid is less than 1% by weight, the antimicrobial activity may be lowered, and when it exceeds 10% by weight, the adhesive strength may be lowered and precipitation may occur.

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

When the content of the guanidine salt is less than 1% by weight, the reaction may not occur, and when it exceeds 10% by weight, precipitation may occur.

When the content of the titanium dioxide is less than 0.1% by weight, the photocatalytic effect may not occur, and when it exceeds 5% by weight, transparency may be reduced.

The glass coating composition may be coated on the glass by a conventionally known coating method, and the two-roll reverse coating, three-roll reverse coating, gravure coating, micro gravure coating, die coating, curtain coating, bar coating, dip Coatings and flow coatings. The glass coating composition is coated on the substrate and cured at 60 to 80 ° C.

The coating thickness is preferably 0.5 to 300um, more preferably 10 to 30um. The thicker the coating thickness, the better the wear resistance, but may cause curling or cracking of the film due to curing shrinkage.

The glass coating composition of the present invention is excellent in stain resistance and fingerprint resistance, and also excellent in antibacterial activity.

1 to 4 are photographs showing the antimicrobial test results of the coated glass prepared in Example 1 of the present invention.

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.

Preparation Example: Preparation of Composition for Glass Coating

(Example 1)

10 g of citric acid and 80 g of ethylene oxide were added to ethinol, and then dissolved by heating at 70 DEG C to 20% by weight of citric acid. To the concentrated solution, 10 g of guanidine salt (phosphate of guanidine) was added and stirred. An organic acid composition was prepared by adding 1 g of nano titanium dioxide (Anatase) to the concentrated solution and rotating at a high speed of 10,000 rpm. Copper nitrate 1g was added to the organic acid composition to prepare an organic acid composition in which nano metal ions were dispersed.

Meanwhile, 10 g of sodium silicate was added to 100 g of isopropanol, and stirred at 350 rpm for 3 hours at 70 ° C. After the stirred mixed solution was stabilized, 10 g of silicon was added, the mixture was stirred for 2 hours while maintaining 100 rpm at 50 ° C., and then stirred at 300 rpm for 10 hours to prepare a primary binding composition.

10 g of the organic acid composition in which the prepared nano metal ions were dispersed was added to the primary binding composition, and stirred at 300 rpm for 3 hours at 55 ° C. to prepare a glass coating composition.

Experimental Example: Antibacterial Test

The glass coating composition prepared in Example 1 was gravure coated on the glass surface, and cured in an oven at 60 to 80 ° C. for about 30 to 60 minutes.

The bacterial counts of Staphylococcus aureus (MRSA) ATCC 33591 and Escherichia coli ATCC 8739 were measured at 35 ± 1 ° C. and RH 90 ± 5% on a 25 cm 2 coated glass for 24 hours. The results are shown in Tables 1 to 2 and FIGS. 1 to 4.

Table 1, Figure 1 (experimental group) and Figure 2 (control) are the experimental results for Staphylococcus aureus, Table 2, Figure 3 (experimental group) and Figure 4 (control group) are the experimental results for E. coli.

Strain 1: Staphylococcus aureus (MRSA) ATCC 33591 Inoculum concentration (CFU / ml) 2.2 × 10 ⁵ The proliferation value (F) 1.7 M _a 2.2 × 10 ⁵ M _b 1.1 × 10 ⁷ M _c <10 Antibacterial activity (S) - Reduction rate (%) (6.0) 99.9

Strain 2: Escherichia coli ATCC 8739 Inoculum concentration (CFU / ml) 2.3 × 10 ⁵ The proliferation value (F) 1.7 M _a 2.3 × 10 ⁵ M _b 1.2 × 10 ⁷ M _c <10 Antibacterial activity (S) - Reduction rate (%) (6.1) 99.9

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

% Reduction: [(M _b -M _c ) / M _b ] × 100

Proliferation (F): log (Mb / Ma) (more than 1.5)

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

-M _b : Average number of viable cells after incubation for 24 hours with standard sample (3 samples)

-M _c : The average number of viable cells after incubation for a certain time (24 hours) of antimicrobial processed samples (3 samples)

Referring to Tables 1 to 2 and FIGS. 1 to 4, the glass coated with the glass coating composition may be confirmed to have improved antibacterial activity.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (9)

Adding silicate to a solvent to prepare a first mixed solution,
Preparing a first binding composition by adding silicone to the first mixed solution, and
Preparing a second binding composition by adding an organic acid composition in which nano metal ions are dispersed to the first binding composition.
Method for producing a composition for glass coating comprising a. The method of claim 1,
The step of preparing the first mixed solution is made by stirring at 100 to 150 ℃ 300 to 400rpm,
The step of preparing the primary binding composition is made by stirring at 100 to 150rpm for 1 to 3 hours at 0 to 50 ℃, then to 250 to 300rpm for 4 to 8 hours,
The step of preparing the secondary bonding composition is a method for producing a composition for glass coating which is made by stirring at 300 to 400 rpm at 0 to 50 ℃. The method of claim 1,
The nano metal ion is a method for producing a composition for glass coating, which is an ion of any one metal selected from the group consisting of copper, silver, gold, zinc, platinum, cobalt and combinations thereof. The method of claim 1,
The organic acid is any one selected from the group consisting of citric acid (citric acid), lactic acid (lactic acid), sorbic acid (sorbic acid) and combinations thereof. The method of claim 1,
The organic acid composition in which the nano metal ions are dispersed
Adding an organic acid to the solvent and heating and concentrating the solution at 50 to 70 DEG C to prepare a concentrated solution,
Adding the guanidine salt to the concentrated solution and stirring to prepare the organic acid composition, and
Adding a strong acid salt of the metal to the organic acid composition to disperse the nano metal ions
Method for producing a composition for glass coating that is prepared through. The method of claim 5,
In the step of preparing the concentrated solution, the method for producing a composition for coating a glass is further added to the solvent ethylene oxide with the organic acid. The method of claim 5,
In the step of preparing the organic acid composition, a method for producing a composition for glass coating is further added to the concentrated solution with the guanidine salt titanium dioxide. Composition for glass coating comprising 10 to 35% by weight of silica, 10 to 30% by weight of silicon, 1 to 10% by weight of organic acid composition in which nano metal ions are dispersed, 1 to 5% by weight of additive, and remaining amount of solvent . 9. The method of claim 8,
The organic acid composition in which the nano metal ions are dispersed includes 1 to 10 wt% of nano metal ions, 1 to 10 wt% of organic acid, 0.5 to 5 wt% of ethylene oxide, 1 to 10 wt% of guanidine salt, 0.1 to 5 wt% of titanium dioxide, and The composition for a glass coating comprising the remaining amount of the solvent.

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