KR102247698B1 - Method for manufacturing an antimicrobacterial and antidiscoloring copper dish - Google Patents

Abstract

The present invention relates to a method for manufacturing a copper dish with excellent anti-microbacterial and anti-chromic properties. A dish comprises a ceramic coating layer formed on both surfaces of a copper plate to prevent discoloration and maintain an own anti-microbacterial property of a copper material, so that the dish can be used for a dish for food requiring the anti-microbacterial property, a ripening degree, and a freshness degree.

Description

Manufacturing method of copper plate with excellent antibacterial and anti-discoloration properties {METHOD FOR MANUFACTURING AN ANTIMICROBACTERIAL AND ANTIDISCOLORING COPPER DISH}

The present invention relates to a method of manufacturing a plate made of copper with excellent antibacterial and anti-discoloration properties, wherein the copper includes pure copper, brass, phosphor bronze, nickel silver, and the like, and the plate includes a plate, a bowl, a cup, and the like.

Copper (Cu) has excellent antibacterial properties and is used as a material for dishes to hold foods that require freshness, warmth, and cold storage. In addition, copper is steadily favored as a material for dishes due to its beautiful color.

However, copper has a property of being easily oxidized and discolored when contacted with water and the like, and as the discoloration proceeds, aesthetics deteriorates, and there is a problem that harmful substances may be leaked.

Accordingly, a product coated with a plate made of the same material was developed.

The plate made of the copper material coated as described above has a problem of discoloration, and its antimicrobial property is deteriorated, and thus it is not suitable for use as a plate for containing food requiring freshness.

Accordingly, there is a need to develop a dish that can be commercially used to hold foods requiring freshness and warmth and cold storage by securing antimicrobial properties and discoloration at the same time.

Korean Patent Publication No. 2013-0096852

The present inventors have conducted various studies to solve the above problem, and as a result, it has been confirmed that when a ceramic coating layer is formed on a copper plate, discoloration of the copper plate can be prevented and the antimicrobial properties of the copper itself can be maintained.

Accordingly, an object of the present invention is to provide a method for manufacturing a plate made of copper having excellent antibacterial and anti-discoloration properties.

Another object of the present invention is to provide a plate made of copper having excellent antibacterial properties and anti-discoloration properties.

In order to achieve the above object, the present invention,

(S1) preheating the copper plate;

(S2) coating a ceramic coating layer forming agent on one surface of the preheated copper plate;

(S3) forming a first ceramic coating layer by drying the copper plate coated with the ceramic coating layer former in step (S2);

(S4) preheating the copper plate on which the first ceramic coating layer is formed;

(S5) coating a ceramic coating layer forming agent on the other surface of the preheated copper plate;

(S6) forming a second ceramic coating layer by drying the copper plate coated with the ceramic coating layer former in step (S5);

(S7) curing the copper plate on both sides of the first and second ceramic coating layers;

(S8) cooling the cured copper plate at 40°C to 80°C; And

(S9) firing the cooled copper plate; containing, it provides a method of manufacturing a copper plate excellent in antibacterial properties and anti-discoloration properties.

The present invention is also a copper plate; And ceramic coating layers formed on both sides of the copper plate; including, antibacterial and anti-discoloration properties, and provides a copper plate.

The copper plate having excellent antibacterial and anti-discoloration properties according to the present invention can prevent discoloration of the copper plate because the copper does not directly contact the external environment due to the structure in which the ceramic coating layer is formed on the surface of the copper plate.

In addition, the copper plate with excellent antimicrobial properties can be maintained without being blocked by the ceramic coating due to the structure in which copper ions can pass through the air holes formed through the curing step. .

In addition, the plate made of copper having excellent antimicrobial and anti-discoloration properties is suitable for use in containing foods that are particularly required for freshness and thermal insulation.

1 is a product photograph of a plate made of copper having excellent antibacterial properties and anti-discoloration properties according to the present invention.
2 is a photograph showing a specimen used in the antimicrobial test of Experimental Example 1.
Figure 3a is E. coli in Experimental Example 1 ( Escherichia coli ) is a photograph showing the results of an antimicrobial experiment, and FIG. 3B is a photograph showing the results of an antimicrobial experiment against Staphylococcus aureus in Experimental Example 1. FIG.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The term "copper" as used herein means including pure copper, brass, phosphor bronze and nickel silver.

The term "dish" as used herein means including all of a plate, a bowl, a cup, and the like.

Copper plate with excellent antibacterial and anti-discoloration properties

The present invention relates to a copper plate with excellent antibacterial and anti-discoloration properties, wherein the copper plate includes a copper plate; And a ceramic coating layer formed on both surfaces of the copper plate; including, a ceramic coating layer.

1 is a product photograph of a plate made of copper having excellent antibacterial properties and anti-discoloration properties according to the present invention.

In the present invention, the copper plate includes copper (Cu) having excellent antimicrobial properties by itself including an antimicrobial component.

In the present invention, the shape of the copper plate is not particularly limited, and may be, for example, a plate that can generally hold food.

In the present invention, the ceramic coating layer may be formed on the surface of the copper plate, specifically on both sides of the copper plate. The ceramic coating layers formed on both sides of the copper plate may be classified into first and second ceramic coating layers, respectively, and the composition of the first and second ceramic coating layers may be the same, and the thickness may be different or the same, respectively.

The ceramic coating layer of the present invention may be made of known silica (SiO ₂ ), inorganic oxide and organic components.

Since the ceramic coating layer includes a composition as described later, it may be formed to include an air hole having a diameter of 0.5 μm to 1.5 μm therein. Since the air hole is particularly suitable for passing the antimicrobial component contained in the copper material itself, even if the ceramic coating layer is formed on the copper plate, a plate having antimicrobial properties can be manufactured without being blocked.

The silica (SiO ₂ ) may be included in an amount of 30% to 70% by weight based on the total weight of the ceramic coating layer, and in this case, contamination resistance and solvent resistance of the ceramic coating layer may be enhanced due to the silica.

If the content of the silica is less than 30% by weight, the adhesion to the copper plate decreases, and the stain resistance or solvent resistance of the ceramic coating layer may be reduced, and if it exceeds 70% by weight, cracking and peeling of the ceramic coating layer may occur, resulting in stability. It can be degraded.

In addition, the inorganic oxide may include at least one selected from the group consisting of inorganic fillers and inorganic pigments.

The inorganic filler may enhance the hardness and scratch resistance of the ceramic coating layer. The inorganic filler is not particularly limited as long as it is an inorganic filler commonly used in the art, and examples thereof include alumina (Al ₂ O ₃ ) and zirconia (ZrO ₂ ).

The inorganic pigment may impart various colors having heat resistance or weather resistance to the ceramic coating layer. The inorganic pigment is not particularly limited as long as it is an inorganic pigment commonly used in the art, and examples thereof include transition metal oxides.

The inorganic oxide may be included in an amount of 20% to 75% by weight based on the total weight of the ceramic coating layer, and in this case, the hardness and scratch resistance of the ceramic coating layer may be enhanced due to the inorganic oxide.

If the content of the inorganic oxide is less than 20% by weight, the hardness of the ceramic coating layer decreases, so scratches or cracks may easily occur, and if it exceeds 75% by weight, the adhesion to the copper plate may decrease, and the density of the ceramic coating layer decreases, resulting in durability. This can be degraded.

In addition, the organic component may be included in an amount greater than 0% by weight and less than 5% by weight based on the total weight of the ceramic coating layer, and in this case, the heat resistance and weather resistance of the ceramic coating layer may be enhanced due to the organic component.

The organic component may include at least one selected from the group consisting of organic groups, alkoxy groups, and alcohols contained in organoalkoxysilane.

The organic groups of the organoalkoxysilane are methyl, ethyl, n-propyl, i-propyl, n-propyl, γ-chloropropyl, vinyl, 3.3.3-trifluoropropyl, and γ-greed. And a chisipropyl group, a γ-methacoxypropyl group, a γ-mecaftpropyl group, a phenyl group, a γ-aminopropyl group, and a 3.4-epoxycyclohexylethyl group.

The alkoxy group includes a methoxy group and an ethoxy group.

Examples of the alcohols include methanol, ethanol, and isopropyl.

If the content of the organic component is more than 5% by weight, gloss reduction, discoloration, and staining may occur due to partial decomposition of the organic component when exposed to light of the ceramic coating layer, and when exposed to heat, the ceramic coating layer may be discolored.

In addition, the thickness of the ceramic coating layer may be 7 μm to 25 μm, and due to such a thickness range and the ceramic coating layer formed in the curing step, antibacterial properties and anti-discoloration properties of a dish including a copper plate can be secured at the same time. In this case, the thickness may mean the dry thickness of the ceramic coating layer.

If the thickness of the ceramic coating layer is less than 7 μm, the function of protecting the copper plate from external environmental factors such as water decreases, which may lead to discoloration of the copper plate. If it exceeds 25 μm, the efficiency of the manufacturing process decreases, and the ceramic coating layer It is easy to crack due to excessive thickness.

Manufacturing method of copper plate with excellent antibacterial and anti-discoloration properties

The present invention relates to a method of manufacturing a dish comprising a ceramic coating layer, the manufacturing method includes the following steps (S1) to (S9):

(S1) preheating the copper plate;

(S2) coating a ceramic coating layer forming agent on one surface of the preheated copper plate;

(S3) forming a first ceramic coating layer by drying the copper plate coated with the ceramic coating layer former in step (S2);

(S4) preheating the copper plate on which the first ceramic coating layer is formed;

(S5) coating a ceramic coating layer forming agent on the other surface of the preheated copper plate;

(S6) forming a second ceramic coating layer by drying the copper plate coated with the ceramic coating layer former in step (S5);

(S7) curing the copper plate on both sides of the first and second ceramic coating layers;

(S8) cooling the cured copper plate at 40°C to 80°C; And

(S9) firing the cooled copper plate.

In the present invention, in the step (S1), the copper plate may be preheated so that the process of coating the ceramic coating layer forming agent on the copper plate can be smoothly performed.

The preheating temperature may be 40° C. to 60° C. In this case, the surface of the copper plate may be heat-treated so that the ceramic coating process can be performed well on the surface of the copper plate while preventing deformation of the copper plate.

In the present invention, in the step (S2), a ceramic coating layer forming agent may be coated on one surface of the preheated copper plate.

In this case, the ceramic coating layer forming agent may include silica, inorganic oxides, and organic components included in the ceramic coating layer as described above, and may further include a solvent and other additives. The solvent and other additives are not particularly limited as long as they are used in the coating slurry in the art. For example, the solvent may be trichloroethylene, methyl ethyl ketone, acetone, dimethylformamide, and the like, and the other additives may be catalysts, thickeners, dispersants, binders, and the like.

In addition, a coating method for coating the ceramic coating layer forming agent is also not particularly limited, and may be, for example, spray coating, roll coating, dip coating, floor coating, and the like, preferably spray coating.

In addition, the thickness of coating the ceramic coating layer forming agent may be appropriately adjusted so that the thickness of the finally prepared first ceramic coating layer after firing is 7 μm to 25 μm.

In the present invention, in the step (S3), the ceramic coating layer former coated on the copper plate may be dried to form a coating layer.

The drying temperature may be 120° C. to 180° C., and the drying time may be 5 minutes to 15 minutes, and in this case, a ceramic coating layer in a state well attached to the copper plate may be formed without cracking. During drying, a separate drying furnace may be used, but is not limited thereto.

In the present invention, in the step (S4), the copper plate may be preheated so that the process of coating the ceramic coating layer forming agent on the other surface of the copper plate can be smoothly performed. In this case, the preheating process may be performed in the same manner as in step (S1).

In the present invention, in the step (S5), a ceramic coating layer forming agent may be coated on the other surface of the preheated copper plate. In this case, the coating process may be performed in the same manner as in step (S2).

In the present invention, in the step (S6), the second ceramic coating layer may be formed by drying the copper plate coated with the ceramic coating layer former in the step (S5). In this case, the drying process may be performed in the same manner as in step (S3).

In the present invention, in the step (S7), the copper plate on which the first and second ceramic coating layers are formed on both sides may be cured.

Through the curing, the first and second ceramic coating layers formed on both sides of the copper plate can be hardened, thereby improving strength and durability.

The curing process may be performed by heat treatment at a temperature of 210°C to 280°C. When the curing temperature is less than 210° C., curing is not sufficiently performed, and when the curing temperature exceeds 280° C., cracks may occur in the ceramic coating layer.

In the present invention, in the step (S8), the shape of the dried coating layer is cooled by cooling the copper plate with the first and second ceramic coating layers formed on both sides of the cured in the step (S7) to a temperature of 40°C to 80°C. You can make sure it is well maintained. The cooling may be natural cooling in air, but is not limited thereto.

In the present invention, in the step (S9), the copper plate having the first and second ceramic coating layers formed on both sides is sintered, so that the copper plate having the ceramic coating layer formed on both sides can be changed to maintain antibacterial and anti-discoloration properties at the same time. have.

The sintering may be performed at 210° C. to 280° C. for 5 minutes to 20 minutes. If the sintering temperature is out of the range, the copper plate on which the ceramic coating layer is formed cannot simultaneously exhibit antibacterial and anti-discoloration properties. In addition, when the firing time is also outside the above range, any one or more of antimicrobial and anti-discoloration properties cannot be exhibited.

Hereinafter, preferred embodiments are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that changes and modifications fall within the scope of the appended claims.

Preparation Example 1: Preparation of ceramic coating layer former

A ceramic coating layer forming agent was prepared by mixing 55% by weight of silica, 25% by weight of an inorganic oxide, 3% by weight of an organic component, and 17% by weight of acetone as a solvent. As the inorganic oxide, alumina, which is an inorganic filler, was used, and an organoalkoxysilane was used as an organic component.

Example 1: Preparation of a dish containing a ceramic coating layer

After the concave dish-shaped copper plate was preheated at 50° C., the ceramic coating layer former obtained in Preparation Example 1 was spray-coated on one surface of the preheated copper plate. The copper plate coated with the ceramic coating layer forming agent on one side was dried in a drying furnace at 150° C. for 10 minutes to obtain a copper plate having a ceramic coating layer formed on one side.

Thereafter, the copper plate was preheated again at 50° C., and the ceramic coating layer former obtained in Preparation Example 1 was spray-coated on the other side of the preheated copper plate. The copper plate coated with the ceramic coating layer forming agent on the other side was dried for 10 minutes in a drying furnace at 150° C. to obtain a copper plate having ceramic coating layers formed on both sides.

The copper plate on which the ceramic coating layer was formed on both sides was cured at 230° C., naturally cooled with air at 60° C., and then fired at 230° C. for 10 minutes to prepare a gray plate including the ceramic coating layer on both sides. At this time, the thickness of the ceramic coating layers formed on both sides is 13 μm, respectively.

Comparative Example 1

A copper plate on which a ceramic coating layer was not formed was prepared as a plate.

Experimental Example 1: Antibacterial test

For the sashimi dish of Example 1 and Comparative Example 1, according to the JIS Z 2801:2010E method, Escherichia coli) and Staphylococcus aureus (were tested exemplary on the antimicrobial activity of the Staphylococcus aureus), as a result, showed a value of bacteriostatic reduction rate (actibacterial rate) and the eradication rate in Table 1 below (Korea SGS (primary), SGS in Korea) . At this time, the bacteriostatic reduction rate represents the ratio of the growth of bacteria in the sample being suppressed compared to the control group by comparing the sample with the control group without antibacterial activity, and the sterilization rate is the ratio of the number of bacteria remaining in the sample after the sterilization treatment compared to the initial number of bacteria in the sample. Means.

As a sample, the plate prepared in Example 1 was prepared as a film-type specimen having a width x length of 50 mm x 50 mm (Fig. 2), and the control plate of Comparative Example 1 was prepared as a specimen of the same shape. I did. The test was performed three times (1st, 2nd, 3rd).

Test strain is Escherichia coli ATCC 8739 and Staphylococcus aureus ATCC 6538p were used, respectively. Inoculation and cultivation of the test strains were performed according to the Pour plate method according to the JIS Z 2801:2010E method. The concentration of the inoculum is Escherichia coli 2.1 x 10 ⁵ CFU/film and Staphylococcus aureus 1.8 x 10 ⁵ CFU/film. 1/500 Nutrient broth (BD) was used as the culture medium, and inoculation was performed at 35°C for 24 hours and cultured at 35°C for 48 hours.

result Concentration of inoculum
(CFU/film) Control
(CFU/film) Sample (CFU/film) Antibacterial activity Bacteriostatic reduction rate (R, %) ^{Note 1 )} Sanitization rate (%) ^{Note 2 )} Escherichia coli ATCC 8739 2.1 x 10 ⁵ 6.9 x 10 ⁷ 1st <25 6.4 >99.9% 2nd <25 6.4 >99.9% 3nd <25 6.4 >99.9% Staphylococcus aureus ATCC 6538p 1.8 x 10 ⁵ 2.2 x 10 ⁷ 1st <25 5.9 >99.9% 2nd <25 5.9 >99.9% 3nd <25 5.9 >99.9% Note 1) The actibacterial rate (%) is calculated by comparing the control and the sample without antimicrobial activity to determine what% of the growth of bacteria was inhibited compared to the control group, and is calculated by the following formula 1.
[Equation 1]
{(Number of bacteria in control group)-(Number of bacteria in sample)}/(Number of bacteria in control group)x100(%)

Note 2) The remove rate of bacteria (%) is calculated by calculating the number of bacteria remaining in the sample 24 hours after the start of the test, and is calculated by Equation 2 below.
[Equation 2]
{(Number of initial bacteria)-(Number of bacteria 24 hours after test start)}/(Number of initial bacteria)x100(%)

As a result, as shown in Table 1, since the bacteriostatic reduction rate of the sample (Example 1) is a small value of 6.4% and 5.9%, the antibacterial activity is excellent compared to the control (Comparative Example 1), and the bacteriostatic rate is also excellent at 99.9% or more. It was confirmed (Figs. 3a and 3b).

From these results, it was found that in the case of the porcelain plate in which the ceramic coating layer was formed on both sides of the copper plate, the ability to suppress and remove bacteria growth was excellent.

Experimental Example 2: Anti-discoloration test

For the gray dishes of Example 1 and Comparative Example 1, water was sprayed on the surface for 48 hours on an hourly basis, and then allowed to stand at room temperature, and then, whether or not the surface of the gray plate was discolored was observed with the naked eye.

As a result, the surface of the gray dish on which the ceramic coating layer was formed was not observed at all, but the surface of the gray dish of Comparative Example 1 was uneven.

From these results, it was found that the case of the gray plate in which the ceramic coating layer was formed on both sides of the copper plate exhibited strong characteristics against discoloration due to external substances or the environment.

In the above, although the present invention has been described by limited embodiments and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following description by those of ordinary skill in the art to which the present invention pertains. It goes without saying that various modifications and variations are possible within the equivalent range of the claims to be made.

Claims (8)

(S1) preheating the copper plate;
(S2) coating a ceramic coating layer forming agent on one surface of the preheated copper plate;
(S3) forming a first ceramic coating layer by drying the copper plate coated with the ceramic coating layer forming agent in the step (S2) at 120 to 180°C;
(S4) preheating the copper plate on which the first ceramic coating layer is formed;
(S5) coating a ceramic coating layer forming agent on the other surface of the preheated copper plate;
(S6) forming a second ceramic coating layer by drying the copper plate coated with the ceramic coating layer forming agent in the step (S5) at 120 to 180°C;
(S7) curing the copper plate on both sides of the first and second ceramic coating layers at 210°C to 280°C;
(S8) cooling the cured copper plate at 40°C to 80°C; And
(S9) calcining the cooled copper plate at 210° C. to 280° C. for 5 minutes to 20 minutes; containing, a method of manufacturing a copper plate having excellent antibacterial and anti-discoloration properties. The method of claim 1,
The ceramic coating layer is a method of manufacturing a plate made of copper having excellent antibacterial properties and anti-discoloration properties, characterized in that it contains _{silica (SiO 2 ), inorganic oxides and organic components.} The method of claim 1,
The preheating temperature of the steps (S1) and (S4) is 40 ~ 60 ℃, characterized in that, antibacterial and anti-discoloration properties excellent copper plate manufacturing method. The method of claim 1,
The thickness of the ceramic coating layer is 7 ㎛ ~ 25 ㎛, characterized in that, antibacterial and anti-discoloration properties excellent copper plate manufacturing method.
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