KR101733449B1 - Manufacturing method of ceramic coating agents having antibiosis and strength with alkali metal ion - Google Patents

Abstract

The present invention relates to a method for preparing a ceramic coating agent having a strong antibacterial function against an alkali metal ion. The method comprises: a raw material mixing step of mixing distilled water and hydrochloric acid in a hydrophobic silica compound; a silica sol preparing step of hydrolyzing a mixture by emitting ultrasound to the mixture prepared through the raw material mixing step; a silver precursor mixing step of preparing a silica sol mixture by mixing a silica sol prepared through the silica sol preparing step with a silver precursor and a reducing agent; a gelling step of mixing a zirconia compound, a chelate compound and ammonia water with the silica sol mixture prepared through the silver precursor mixing step to be gelled; an acetone washing step of washing, with acetone, a gelled product prepared through the gelling step to remove ammonium chloride produced in the gelling step; and a heating step of heating the gelled product washed with the acetone through the acetone washing step to remove the acetone and moisture. The ceramic coating agent prepared through the above process exhibits excellent heat-resistance, corrosion resistance, adhesive properties and antibacterial performance.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a ceramic coating agent having a strong antibacterial function against an alkali metal ion,

The present invention relates to a method for producing a ceramic coating agent having a strong antibacterial function against alkaline metal ions, and more particularly to a method for producing a ceramic coating agent having excellent heat resistance, corrosion resistance, adhesion and antibacterial activity, It has a strong antimicrobial function against alkali metal ions which can be useful in the fields of daily necessities such as household appliances, gas ranges, heaters, electric fans, refrigerators and irons, buildings and building materials, health aids, vehicles and ships To a process for producing an added ceramic coating agent.

Ceramic coating methods on metal substrates include chemical vapor deposition, physical vapor deposition, plasma spraying, electrochemical deposition, and sol-gel processes.

Among them, a sol-gel process coating method has been studied actively with a ceramic coating agent which is lower in facility cost, lower reaction temperature, uniformity and impurities than other coating methods, and is resistant to corrosion resistance and heat resistance. However, ceramic materials are known to be resistant to corrosion, but they are weak against alkali resistance, so strong materials must be added to alkali metals to maintain the inherent properties of ceramic materials.

Therefore, research is continuing to develop coatings optimized for specific applications, or multifunctional ceramic coatings with improved performance, using a variety of ceramic and metallic materials.

Korean Patent Registration No. 10-0963224 discloses a ceramic coating heater capable of being used in both water and air. The coating heater is a ceramic coating agent having high heat resistance and corrosion resistance, and is made of nano-silica sol and expensive nano-zirconia powder, There is a problem in that it is not economical compared with the conventional ceramic coating agent.

Korean Patent Registration No. 10-585992 discloses an Al ₂ O ₃ -ZrO ₃ composite ceramic powder produced by a sol-gel method. However, in the above patent, a porous body obtained by foaming a composite ceramic powder has homogeneous pores However, it has been disclosed that these properties can be suitably used for various filter materials, and no improvement in the performance of the composite ceramic powder for use as a coating agent has been disclosed.

Korean Patent Registration No. 10-1214173 discloses that a lanthanum-strontium-cobalt-iron metal compound using a sol-gel method can be used for manufacturing a fuel cell electrolyte, a microsensor, and a porous ceramic thin film. However, And is a coating agent other than the electroconductivity, which is independent of other functional enhancement.

 Korean Patent Registration No. 10-1424082 discloses a composite ceramic produced by using a sol-gel method, a thin film coating agent having an ultra-high temperature resistance and a high corrosion resistance and a method for producing the same, but since the surface is made of a hydrophilic material, There was a problem that when the ceramic coating was applied to the surface, there was a large amount of -OH residues, and as the time passed, it reacted with hardness ions (Mg 2+, Fe 2+, Na +, K +) in the water to generate rust.

On the other hand, in the fields of various liquid crystal display devices such as TVs, computer monitors and mobile phones, various industrial products such as household appliances such as gas ranges, heaters, fans, refrigerators and irons, building materials and health aids, A variety of coating agents have been developed and applied. Especially, in the case of heat-resistant glass used for bezel, induction and gas stove in glass and display devices of various industrial display device panels including mobile phones, high heat resistance is required , Safety and environment friendliness are demanded from the human-friendly viewpoint.

In accordance with this demand, various techniques of ceramic coating materials have been developed in which ceramic powder is added as a coating component in order to impart environment-friendliness such as antibacterial properties and deodorization properties.

However, the ceramic coating composition conventionally used contains an organic resin such as epoxy, urethane and acrylic as a binder, and thus harmful components such as volatile organic compounds are essentially generated and adversely affect the human body and the environment. There is a problem that heat resistance is poor.

In addition, when organic resin is used as building interior and exterior materials, pollutants in the air are easily adhered to deteriorate aesthetics. In the case of a heating cooker or a heating device for a kitchen, There is a problem that washing is difficult.

In addition, there is a problem in that a building exterior material that directly or indirectly receives heat causes discoloration, discoloration, and carbonization over time, and discoloration and discoloration occur even when exposed to sunlight or strong illumination for a long period of time.

In order to overcome the above problems, organic and inorganic materials can be applied together as an organic / inorganic composite coating agent. However, in this case, the stability of the coating material is lowered and heat resistance and corrosion resistance after coating are lowered.

It is an object of the present invention to provide a liquid crystal display device which is excellent in heat resistance, corrosion resistance, adhesion property and antibacterial property and can be applied to various liquid crystal display devices such as TV, computer monitor and cellular phone, and household goods, such as gas range, heater, electric fan, refrigerator and iron, The present invention provides a method for producing a ceramic coating agent having a strong antibacterial function against alkali metal ions, which can be usefully used in various industrial products such as materials, health aids, vehicles and ships.

Another object of the present invention is to provide a method for producing a ceramic coating agent having a strong antimicrobial function on alkali metal ions showing uniform coating film thickness and surface roughness after application.

The object of the present invention is to provide a method for producing a silica sol which comprises a raw material mixing step of mixing distilled water and hydrochloric acid into a hydrophobic silica compound, a silica sol preparation step of hydrolyzing the mixture by irradiating ultrasonic waves to the mixture prepared through the raw material mixing step, A silver sulfide mixture in which a silica sol mixture is prepared by mixing a silver sulfone and a reducing agent to the prepared silica sol; a gelation step of mixing a zirconia compound, a chelate compound, and ammonia water with the silica sol mixture prepared through the silver- , Washing the gelled product obtained through the gelling step with acetone to remove ammonium chloride produced in the gelling step, and heating the gelled product washed with acetone through the acetone washing step to remove acetone and moisture And a heating step in which the alkali metal The strong antimicrobial ions is accomplished by providing an additional ceramic coating method.

According to a preferred aspect of the present invention, the raw material mixing step comprises mixing 100 parts by weight of the hydrophobic silica compound with 40 to 50 parts by weight of distilled water and 0.01 to 0.02 parts by weight of hydrochloric acid.

According to a more preferred feature of the present invention, the hydrophobic silica compound is at least one selected from the group consisting of water glass, tetraethyl orthosilicate, tetramethyl orthosilicate, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane and dimethyldiethoxysilane.

According to a further preferred feature of the present invention, the hydrophobic silica compound is a mixture of methyltriethoxysilane and dimethyldiethoxysilane.

According to a further preferred feature of the present invention, the hydrophobic silica compound is prepared by mixing methyltriethoxysilane and dimethyldiethoxysilane in a weight ratio of 1.2: 1.

According to a still further preferred feature of the present invention, the silver spherically spherical compounding step comprises mixing 0.3 to 0.4 parts by weight of a silver bulb and 0.03 to 0.04 part by weight of a reducing agent in 100 parts by weight of silica sol prepared through the silica sol preparation step .

According to a further preferred feature of the invention, the of silver sphere is _{AgNO 3, AgBF 4, AgPF 3} , Ag 2 O, CH 3 COOAg, AgCF 3 SO 3, AgCl, Ag 2 SO 4 and CH ₃ COCH-COCH ₃ Ag As shown in FIG.

According to a further preferred feature of the present invention, the reducing agent is sodium borohydride.

According to a further preferred feature of the present invention, the reducing agent is made of hydrazine.

According to a further preferred feature of the present invention, the gelling step comprises mixing 13 to 15 parts by weight of a zirconia compound, 40 to 45 parts by weight of a chelate compound and 4 to 4.5 parts by weight of ammonia water in 100 parts by weight of the mixture prepared through the silver- Are mixed.

According to a further preferred feature of the present invention, the zirconia compound is made of zirconium propoxide.

According to a further preferred feature of the present invention, the chelating compound is made of acetyl acetone.

According to an even more preferred feature of the present invention, the heating step comprises heating the gelled material washed with acetone through the acetone cleaning step to a temperature of 65 to 75 ° C to remove acetone, and then removing the acetone- To remove moisture.

The method of manufacturing a ceramic coating agent having a strong antibacterial function according to the present invention has excellent heat resistance, corrosion resistance, adhesion and antibacterial performance, and can be applied to various liquid crystal display devices such as a TV, a computer monitor, Exhibits an excellent effect of providing a ceramic coating agent having antimicrobial activity which can be usefully used in the fields of daily necessities such as household appliances such as electric appliances, electric fans, refrigerators and irons, buildings and building materials, health aids, vehicles and ships.

In addition, it exhibits an excellent effect of providing a ceramic coating agent having antimicrobial performance showing uniform film thickness and surface roughness after application.

1 is a flowchart showing a method of manufacturing a ceramic coating agent having an antibacterial function added to an alkali metal ion according to the present invention.
2 is a photograph showing a surface of a coating layer formed by coating a ceramic substrate with a ceramic coating agent prepared in Examples 1 to 4 on a metal substrate and then photographing the surface of the coating layer with a scanning electron microscope (SEM).

Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.

The method for producing a ceramic coating agent having a strong antibacterial function on alkali metal ions according to the present invention comprises a raw material mixing step (S101) of mixing distilled water and hydrochloric acid into a hydrophobic silica compound, a step of mixing ultrasound (S103) to produce a silica sol mixture by mixing the silver sol and the reducing agent with the silica sol prepared in the step (S103) to produce a silica sol mixture (S105 A step S107 of mixing the zirconia compound, the chelate compound and the ammonia water into the silica sol mixture prepared through the silver-containing spherical mixing step S105, and the gelation step S107, (S109) for removing the ammonium chloride produced in the gelling step (S107) and the acetone washing step (S109) Heating the gelled washed with a tone composed of a heating step (S111) of removing the acetone and water.

The raw material mixing step (S101) is a step of mixing distilled water and hydrochloric acid into the hydrophobic silica compound, which comprises mixing 40 to 50 parts by weight of distilled water and 0.01 to 0.02 parts by weight of hydrochloric acid in 100 parts by weight of the hydrophobic silica compound.

The hydrophobic silacar compound is at least one selected from the group consisting of water glass, tetraethyl orthosilicate, tetramethyl orthosilicate, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, and dimethyldiethoxysilane. Methyltriethoxysilane and dimethyldiethoxysilane are mixed in a weight ratio of 1.2: 1 More preferably methyltriethoxysilane and dimethyldiethoxysilane, and most preferably methyltriethoxysilane and dimethyldiethoxysilane in a ratio of 1.2: 1.

When the hydrophobic silica compound comprising methyltriethoxysilane and dimethyldiethoxysilane in a weight ratio of 12: 1 is used, the hardness, adhesion and contact angle of the ceramic coating film having antimicrobial activity formed through the present invention are significantly improved.

The silica sol preparation step (S103) is a step of hydrolyzing the mixture by irradiating ultrasound to the mixture prepared through the raw material mixing step (S101). The mixture prepared by the raw material mixing step (S101) Ultrasonic waves are irradiated for 2 to 4 hours to hydrolyze the mixture to produce silica sol.

In this case, if the hydrophobic silica compound contained in the mixture prepared through the raw material mixing step (S101) is composed of two or more substances, one substance is mixed with distilled water and hydrochloric acid, then the ultrasonic wave is irradiated, Drop size, and then proceeding to a step of irradiating ultrasonic waves again. The above process is performed, and the efficiency of the hydrolysis process is improved, thereby improving the efficiency of the silica sol manufacturing process.

The silver sulfide spherical mixing step (S105) is a step of preparing a silica sol mixture by mixing the silver sol and the reducing agent with the silica sol prepared through the step (S103) of preparing the silica sol. The silica sol preparation step (S103) To 100 parts by weight of the silica sol thus prepared, 0.3 to 0.4 parts by weight of a silver bulb and 0.03 to 0.04 part by weight of a reducing agent are mixed and stirred at a speed of 400 to 600 rpm for 10 to 30 minutes.

The silica sol mixture prepared through the above-described silver powder spherical mixing step (S105) exhibits excellent antibacterial performance due to the generation and dispersion of silver nanoparticles having excellent antimicrobial performance by containing silver silver spheres and a reducing agent.

If the content of the silver precursor is less than 0.3 parts by weight, the antibacterial performance of the silica sol mixture may be deteriorated. If the content of the silver spherulite exceeds 0.4 parts by weight, the antibacterial performance of the silica sol mixture is not greatly improved, .

If the content of the reducing agent is less than 0.03 parts by weight, the efficiency of conversion of silver spheres to silver nano powders decreases. When the content of the reducing agent exceeds 0.04 parts by weight, silver silver spheres are converted into silver nano powders Is not desirable.

The silver spheres may be selected from the group consisting of AgNO ₃ , AgBF ₄ , AgPF ₃ , Ag ₂ O, CH ₃ COOAg, AgCF ₃ SO ₃ , AgCl, Ag ₂ SO ₄ and CH ₃ COCH-COCH ₃ Ag And the reducing agent is preferably composed of sodium borohydride or hydrazine.

The gelation step (S107) is a step of mixing the zirconia compound, the chelate compound and the aqueous ammonia into the silica sol mixture prepared through the silver-containing spherical mixing step (S105) and gelling the mixture. 13 to 15 parts by weight of a zirconia compound, 40 to 45 parts by weight of a chelate compound and 4 to 4.5 parts by weight of ammonia water are mixed with 100 parts by weight of the mixture and gelled for 1 to 4 hours.

The zirconia compound mixed in the gelling step (S107) serves to protect the hydrophobic silica particles weak in alkali ion resistance, and the chelate compound serves to keep the zirconia compound in a stable state. The gelated gelled product not only improves the alkali ion resistance but also improves the viscosity and gives excellent adhesion performance.

Preferably, the ammonia water has a molar concentration of 0.5 to 2 M, and the zirconia compound is preferably composed of zirconium propoxide. The zirconium propoxide has an advantage of being easily hydrolyzed.

In addition, the chelate compound is preferably composed of acetyl acetone.

The acetone washing step (S109) is a step of washing the gelled substance produced through the gelling step (S107) with acetone to remove the ammonium chloride produced in the gelling step (S107). The gelling step (S107) The gelled product is washed with an acetone solution for 30 to 60 minutes to remove the ammonium chloride produced in the gelation step (S107). The acetone applied to the gelation in the acetone washing step is heated in the heating step (S111) The process is eliminated.

The heating step S111 is a step of heating the gelled material washed with acetone through the acetone cleaning step S109 to remove acetone and moisture, and the gelled material washed with acetone through the acetone cleaning step S109 Heating the solution to a temperature of 65 to 75 DEG C to remove acetone applied to the gelation, and then heating the gelation from which the acetone has been removed to a temperature of 110 DEG C to remove moisture.

When the heating step S111 is carried out, the production of a ceramic coating agent having an antibacterial activity is completed. A ceramic coating agent having a strong antibacterial function on the alkali metal ion produced through the above process is obtained by synthesizing a hydrophobic silica compound and zirconia It was confirmed that the hydrophobic group (-CH ₃ ) remained intact and exhibited excellent physical properties as a coating agent such as heat resistance, corrosion resistance, hardness and salt water resistance as well as antimicrobial activity, and particularly excellent in ultrahigh temperature resistance and corrosion resistance.

Also, it is preferable that the ceramic coating agent having antimicrobial activity prepared as described above is preheated for 20 to 40 minutes at a temperature of 100 to 120 ° C.

Hereinafter, the method for producing a ceramic coating agent having a strong antibacterial function against alkali metal ions according to the present invention and the physical properties of a ceramic coating agent having an antibacterial function prepared through the method will be described.

≪ Example 1 >

methyltrimethoxysilane, 14.2 g of distilled water and 0.004 g of hydrochloric acid were mixed to prepare a mixture. The resulting mixture was ultrasonicated using an ultrasonic disperser for 3 hours to hydrolyze methyltrimethoxysilane, and then dimethyldiethoxysilane compound was dropped in hydrolyzed methyltrimethoxysilane size to prepare a hydrophobic silica sol. The resulting hydrophobic silica sol was stirred at 500 rpm for 20 minutes while 0.16 g of AgNO ₃ and 0.016 g of sodium borohydride were injected into the drop size to prepare a silver nanoparticle powder 6.54 g of zirconium propoxide and 20.0 g of acetyl acetone were mixed with the prepared hydrophobic silica sol mixture, and 2 ml of 0.5 M ammonia water was added to the mixture to gel the mixture for 2 hours. After washing the ammonium chloride with acetone to remove the gel, Column to remove the acetone, and the acetone was prepared in a the removed gelled by heating to a temperature of 110 ℃ to remove the moisture contained in the gelled adding a strong antibacterial function to an alkali metal ion ceramic coating.

≪ Example 2 >

Proceeding in the same manner as in Example 1, 21.36 g of methyltrimethoxysilane and 11.84 g of dimethyldiethoxysilane were used to prepare a ceramic coating agent having a strong antibacterial function against alkali metal ions.

≪ Example 3 >

Proceeding in the same manner as in Example 1, 23.14 g of methyltrimethoxysilane and 10.36 g of dimethyldiethoxysilane were used to prepare a ceramic coating agent having a strong antibacterial function against alkali metal ions.

<Example 4>

Proceeding in the same manner as in Example 1, 24.92 g of methyltrimethoxysilane and 8.88 g of dimethyldiethoxysilane were used to prepare a ceramic coating agent having a strong antibacterial function against alkali metal ions.

A ceramic coating agent having a strong antibacterial function against the alkali metal ions prepared in Examples 1 to 4 was heated and melted at a temperature of 110 ° C. for 30 minutes, and then a metal substrate (AlSI 304 stainless 5 cm × 7 cm × 0.2 cm ), And then heat-treated at a temperature of 160 캜 for 24 hours. The antibacterial properties, pencil hardness, adhesion, heat resistance, acid resistance, alkali resistance, flame resistance and contact angle were measured and shown in Table 1 below .

(However, antimicrobial activity was evaluated by applying two test strains (Escherichia coli, Staphylococcus aureus) to film specimens 5 cm × 5 cm × 1 cm thick, and the pencil hardness was measured with an MIT-UNIT pencil , And the adhesion was measured by peeling evaluation after taping with 1.5 mm cross-cut. The heat resistance was evaluated by evaluating change of film after 3 hours at 300 ° C., and acid resistance was evaluated after immersion in 5% acetic acid solution for 8 hours, The alkali resistance was evaluated after immersing in 1% sodium hydroxide solution and after 1 hour. The salting resistance was evaluated after 16 hours from immersion in a 5% NaCl solution at 35 ° C. for 8 hours. The contact angle was measured by dropping the liquid on the sample The contact angle formed between the surface of the sample and the liquid drop was measured and shown.

<Table 1>

As shown in Table 1 above, the ceramic coatings prepared by Examples 1 to 4 of the present invention having a strong antimicrobial function have antibacterial properties, pencil hardness, adhesiveness, heat resistance, acid resistance, alkali resistance, Contact angle and the like, and it can be seen that the ceramic coating agent added with the antibacterial function prepared in Example 1 is the most excellent in physical properties.

A ceramic coating agent having a strong antibacterial function against the alkali metal ions prepared in Examples 1 to 4 was heated and melted at a temperature of 110 ° C. for 30 minutes, and then a metal substrate (AlSI 304 stainless 5 cm × 7 cm × 0.2 cm ) At a thickness of 0.6 mm, and the state of the coated film heat-treated for 24 hours at a temperature of 160 캜 was measured by a scanning electron microscope (SEM) and is shown in FIG. 2 below.

Example 4 (b) Example 2 (c) Example 3 (d) Example 4)

As shown in FIG. 2, a coating film made of a ceramic coating agent having a strong antibacterial function against alkali metal ions prepared according to Examples 1 to 4 of the present invention exhibited a uniform film thickness and surface roughness, 1 shows the best state of the coating film formed.

S101; Raw material mixing step
S103; Silica sol preparation step
S105; Silver spherical mixing step
S107; Gelling step
S109; Acetone washing step
S111; Heating step

Claims (13)

A raw material mixing step of mixing distilled water and hydrochloric acid into the hydrophobic silica compound;
A step of preparing silica sol by hydrolyzing the mixture by irradiating ultrasound to the mixture prepared through the raw material mixing step;
Mixing the silver sol prepared through the silica sol preparation step with a silver salt and a reducing agent to prepare a silica sol mixture;
A gelation step of mixing the zirconia compound, the chelate compound and the ammonia water with the silica sol mixture prepared through the silver / silver spherical mixing step to gel;
An acetone washing step of washing the gelled product produced through the gelation step with acetone to remove the ammonium chloride produced in the gelation step; And
Heating the gelled material washed with acetone through the acetone washing step to remove acetone and moisture,
Wherein the hydrophobic silica compound is a mixture of methyltriethoxysilane and dimethyldiethoxysilane in a ratio of 1.2: 1 by weight, wherein the antimicrobial function is added to the alkali metal ion.
The method according to claim 1,
Wherein the raw material mixing step comprises mixing 100 parts by weight of the hydrophobic silica compound with 40 to 50 parts by weight of distilled water and 0.01 to 0.02 parts by weight of hydrochloric acid, and adding an antibacterial function to the alkali metal ion.
delete delete delete The method according to claim 1,
Wherein the silver sulfide spherical mixing step comprises mixing 0.3 to 0.4 part by weight of the silver bulb and 0.03 to 0.04 part by weight of a reducing agent in 100 parts by weight of the silica sol prepared through the silica sol preparation step. Lt; / RTI &gt;
The method according to claim 1 or 6,
Wherein the silver spheres are formed of one selected from the group consisting of AgNO ₃ , AgBF ₄ , AgPF ₃ , Ag ₂ O, CH ₃ COOAg, AgCF ₃ SO ₃ , AgCl, Ag ₂ SO ₄ and CH ₃ COCH-COCH ₃ Ag Wherein a strong antibacterial function is added to the alkali metal ion.
The method according to claim 1 or 6,
Wherein the reducing agent is sodium borohydride. The method of claim 1, wherein the reducing agent is sodium borohydride.
The method according to claim 1 or 6,
Wherein the reducing agent is made of hydrazine, wherein a strong antimicrobial function is added to the alkali metal ion.
The method according to claim 1,
Wherein the gelation step comprises mixing 13 to 15 parts by weight of a zirconia compound, 40 to 45 parts by weight of a chelate compound and 4 to 4.5 parts by weight of ammonia water with 100 parts by weight of the mixture prepared through the silver / A method for producing a ceramic coating agent having a strong antibacterial function against ions.
The method according to claim 1 or 10,
Wherein the zirconia compound is composed of zirconium propoxide. 11. The method of claim 9, wherein the zirconia compound is zirconium propoxide.
The method according to claim 1 or 10,
Wherein the chelate compound is composed of acetyl acetone, wherein the antibacterial function is added to the alkali metal ion.
The method according to claim 1,
In the heating step, the gelled material washed with acetone through the acetone washing step is heated to a temperature of 65 to 75 ° C to remove acetone, and then the gelled material from which the acetone is removed is heated to a temperature of 110 ° C to remove moisture Wherein the antimicrobial function is added to the alkali metal ion.

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