KR102741536B1 - Antibacterial glass composition and method of manufactruing antibacterial glass powder using the same and domestic appliance including the same - Google Patents

Abstract

Disclosed are an antimicrobial glass composition made of ingredients harmless to the human body, which has high durability and chemical resistance and can maintain an antimicrobial function for a long period of time by controlling the ingredients and their ratios, a method for producing the antimicrobial glass powder, and a home appliance including the same.
In addition, the antibacterial glass composition according to the present invention is a permanent and economical antibacterial agent that can be used as an additive to plastic injection moldings, which has low solubility compared to organic antibacterial agents, high durability and chemical resistance, and can maintain antibacterial function for a long period of time.
As a result, the antimicrobial glass composition according to the present invention has no added Ag series metal ions, and thus is free from toxicity to the environment and human body, and has the advantage of being inexpensive compared to conventional organic and inorganic antimicrobial agents.

Description

ANTIBACTERIAL GLASS COMPOSITION AND METHOD OF MANUFACTRUING ANTIBACTERIAL GLASS POWDER USING THE SAME AND DOMESTIC APPLIANCE INCLUDING THE SAME

The present invention relates to an antibacterial glass composition and a method for producing an antibacterial glass powder thereof, and to home appliances comprising the same.

Microorganisms such as germs, fungi, and bacteria are ubiquitous in our living spaces such as refrigerators, ovens, and washing machines. If microorganisms enter the human body, they can cause life-threatening infections. Therefore, an antimicrobial glass composition that can control the spread of microorganisms in home appliances such as refrigerators, ovens, and washing machines is required.

In these home appliances, bacteria and mold can grow in parts that are exposed to moisture and use plastic injection molding, causing problems with appearance or the user environment.

The types of bacteria that live on home appliances are very diverse, and the main strains may differ depending on the part, but parts exposed to moisture are generally more likely to harbor Pseudomonas aeruginosa.

Therefore, antimicrobial agents must have antimicrobial performance against these strains. In addition, antimicrobial agents must be strictly selected from materials with low toxicity to the human body and the environment and high temperature resistance.

Antibacterial agents can be broadly divided into inorganic and organic. Organic antibacterial agents exhibit excellent antibacterial performance by dissolving antibacterial materials toward the surface with water, thereby exhibiting antibacterial power against bacteria. However, durability may be reduced when applied to washing machines. In addition, organic antibacterial agents have recently been raised as a problem of human and environmental hazards of the dissolved materials. In addition, there is a risk of decomposition during the injection process due to the low decomposition temperature.

Inorganic antibacterial agents have considerably lower solubility than organic antibacterial agents and can secure high-temperature durability, but they can cause interfacial wetting problems with plastic injection molded products and, since Ag is mostly used as the antibacterial material, their price is high, limiting their application.

KR Publication of Patent Publication No. 10-2005-0022510 (Published on March 8, 2005)

The purpose of the present invention is to provide an antibacterial glass composition comprising components harmless to the human body, which has high durability and chemical resistance and can maintain an antibacterial function for a long period of time by controlling the components and their ratios, and a method for producing the antibacterial glass powder thereof, and a home appliance comprising the same.

In addition, the purpose of the present invention is to provide an antimicrobial glass composition and a method for producing an antimicrobial glass powder, which have the advantages of being free from toxicity to the environment and human body and being inexpensive compared to conventional organic and inorganic antimicrobial agents because no Ag series metal ions are added, and home appliances including the same.

The purposes of the present invention are not limited to the purposes mentioned above, and other purposes and advantages of the present invention which are not mentioned can be understood by the following description, and will be more clearly understood by the embodiments of the present invention. In addition, it will be easily understood that the purposes and advantages of the present invention can be realized by the means and combinations thereof indicated in the claims.

The antibacterial glass composition according to the present invention is composed of components harmless to the human body, and by controlling the components and their ratios, it has high durability and chemical resistance and can maintain an antibacterial function for a long period of time.

In addition, the antibacterial glass composition according to the present invention is a permanent and economical antibacterial agent that can be used as an additive to plastic injection moldings, which has low solubility compared to organic antibacterial agents, high durability and chemical resistance, and can maintain antibacterial function for a long period of time.

To this end, the antimicrobial glass composition according to an embodiment of the present invention includes 40 to 50 wt% of a sum of SiO ₂ and B ₂ O ₃ ; 15 to 30 wt% of at least one of Na ₂ O and K ₂ O; 10 to 30 wt% of ZnO; 5 to 15 wt% of CaO; and 1 to 15 wt% of at least one of CuO and Fe ₂ O ₃ .

In this way, the antimicrobial glass composition according to the present invention and the method for producing the antimicrobial glass powder thereof, and the home appliances including the same, do not contain any Ag series metal ions, and thus are free from toxicity to the environment and human body compared to conventional organic and inorganic antimicrobial agents, and have the advantage of being inexpensive.

The antibacterial glass composition according to the present invention and the method for producing the antibacterial glass powder thereof, and the home appliance including the same, are composed of components harmless to the human body, and by controlling the components and their ratios, have high durability and chemical resistance and can maintain an antibacterial function for a long period of time.

In addition, the antibacterial glass composition according to the present invention is a permanent and economical antibacterial agent that can be used as an additive to plastic injection moldings, which has low solubility compared to organic antibacterial agents, high durability and chemical resistance, and can maintain antibacterial function for a long period of time.

As a result, the antimicrobial glass composition according to the present invention has no added Ag series metal ions, and thus is free from toxicity to the environment and human body, and has the advantage of being inexpensive compared to conventional organic and inorganic antimicrobial agents.

In addition to the effects described above, specific effects of the present invention are described below together with specific matters for carrying out the invention.

Figure 1 is a process flow diagram showing a method for manufacturing antibacterial glass powder according to an embodiment of the present invention.
Figure 2 is a photograph showing the results of measuring the antibacterial activity against Pseudomonas aeruginosa for an injection molded product manufactured according to Example 1.
Figure 3 is a photograph showing the results of measuring the antibacterial activity against Pseudomonas aeruginosa after immersion of an injection-molded product manufactured according to Example 2.

The above-mentioned objects, features and advantages will be described in detail below with reference to the attached drawings, so that those with ordinary skill in the art to which the present invention pertains can easily practice the technical idea of the present invention. In describing the present invention, if it is judged that a detailed description of a known technology related to the present invention may unnecessarily obscure the gist of the present invention, a detailed description thereof will be omitted. Hereinafter, a preferred embodiment according to the present invention will be described in detail with reference to the attached drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

As used herein, the singular expressions include the plural expressions unless the context clearly indicates otherwise. In this application, the terms "consisting of" or "comprising" should not be construed as necessarily including all of the various components or various steps described in the specification, and should be construed as not including some of the components or some of the steps, or may include additional components or steps.

Hereinafter, an antimicrobial glass composition and a method for producing an antimicrobial glass powder according to some embodiments of the present invention, and a home appliance including the same, will be described.

An antibacterial glass composition according to an embodiment of the present invention is composed of components harmless to the human body, and by controlling the components and their ratios, it has high durability and chemical resistance and can maintain an antibacterial function for a long period of time.

In addition, the antimicrobial glass composition according to an embodiment of the present invention is a permanent and economical antimicrobial agent that can be used as an additive to a plastic injection molded product, which has low solubility compared to organic antimicrobial agents, high durability and chemical resistance, and can maintain an antimicrobial function for a long period of time.

To this end, the antimicrobial glass composition according to an embodiment of the present invention includes 40 to 50 wt% of a sum of SiO ₂ and B ₂ O ₃ ; 15 to 30 wt% of at least one of Na ₂ O and K ₂ O; 10 to 30 wt% of ZnO; 5 to 15 wt% of CaO; and 1 to 15 wt% of at least one of CuO and Fe ₂ O ₃ .

In this way, the antimicrobial glass composition according to the embodiment of the present invention does not have any Ag series metal ions added, and thus is free from toxicity to the environment and human body, and has the advantage of being inexpensive compared to conventional organic and inorganic antimicrobial agents.

Below, the role and content of each component of the antimicrobial glass composition according to an embodiment of the present invention will be described in detail.

SiO ₂ and B ₂ O ₃ are glass formers that enable vitrification and are key components that serve as the structural framework of glass. In addition, SiO ₂ does not act as a direct component that exhibits antibacterial properties, but compared to P ₂ O _5, a representative glass former, it forms fewer OH groups on the glass surface, which is advantageous in making the glass surface positively charged by metal ions within the glass.

In addition, _B2O3 is _a component that lowers the eutectic point of the melt because it has a low melting point, and also helps the glass composition to be easily vitrified.

It is preferable that these SiO ₂ and B ₂ O ₃ are added in a total content of 40 to 50 wt% of the total weight of the antibacterial glass composition according to the present invention, and a more preferable range is 42 to 45 wt%. If the total content of SiO ₂ and B ₂ O ₃ exceeds 50 wt%, there is a problem that the workability and yield are reduced during the cooling process as the viscosity increases when the glass is melted. Conversely, if the total content of SiO ₂ and B ₂ O ₃ is less than 40 wt%, there is a problem that the structure of the glass is weakened and the water resistance is reduced.

In the present invention, it is preferable that SiO ₂ be added in a higher amount than the amount of B ₂ O ₃ , because it is advantageous for securing water resistance when the amount of SiO ₂ added is higher than the amount of B ₂ O ₃ added.

Therefore, it is more preferable that SiO ₂ is added in an amount of 30 to 40 wt% of the total weight of the antimicrobial glass composition according to the present invention, and that B ₂ O ₃ is added in an amount of 5 to 10 wt% of the total weight of the antimicrobial glass composition according to the present invention.

Alkali oxides such as _Na2O and _K2O are oxides that act as network modifiers that form non-crosslinking bonds within the glass composition. These components cannot be vitrified on their own, but when mixed with network-forming agents such as _SiO2 and _B2O3 in a certain ratio, vitrification becomes possible. If only one of the above components is included in the glass composition, the durability of the glass may be weakened within the vitrifiable region. However, if two or _more components are included in the glass composition, the durability of the glass may be improved again depending on the ratio. This is called the mixed alkali effect.

Therefore, it is preferable that at least one of Na ₂ O and K ₂ O is added in a content ratio of 15 to 30 wt% of the total weight of the antibacterial glass composition according to the present invention. If at least one of Na ₂ O and K ₂ O is added in a large amount exceeding 30 wt%, the thermal properties of the glass composition may deteriorate. Conversely, if at least one of Na ₂ O and K ₂ O is added in a content of less than 15 wt%, it is difficult to control the hydration of components such as ZnO, which may deteriorate the antibacterial properties.

ZnO is a component that performs both the role of a network former and a network modifier in terms of the structural aspect of glass. It is also one of the important components that express the antibacterial properties of the glass composition.

It is preferable that ZnO be added in a content ratio of 10 to 30 wt% of the total weight of the antibacterial glass composition according to the present invention. If ZnO is added in an amount less than 10 wt%, it is difficult to develop antibacterial properties of the glass composition. On the other hand, if ZnO is added in a large amount exceeding 30 wt%, the durability or thermal properties of the glass composition may deteriorate.

CaO is a component that, together with ZnO, plays the role of both a network former and a network modifier in terms of the structural aspect of glass. It is also one of the important components that expresses the antibacterial properties of the glass composition.

It is preferable that CaO be added in a content ratio of 5 to 15 wt% of the total weight of the antibacterial glass composition according to the present invention. If CaO is added in an amount less than 5 wt%, it is difficult to develop antibacterial properties of the glass composition. On the other hand, if CaO is added in a large amount exceeding 15 wt%, the durability or thermal properties of the glass composition may deteriorate.

CuO and Fe ₂ O ₃ are components that enable glass to exhibit antibacterial effects on its own. In addition, CuO and Fe ₂ O ₃ play a role in enhancing the adhesion of the glass coating layer by inducing chemical bonding between the substrate and the glass when glass is used as a material for coating a low-carbon steel substrate.

It is preferable that at least one of CuO and Fe ₂ O ₃ is added in a content ratio of 1 to 15 wt% of the total weight of the antibacterial glass composition according to the present invention. If at least one of CuO and Fe ₂ O ₃ is added in an amount of less than 1 wt%, the antibacterial properties of the glass may be reduced. Conversely, if at least one of CuO and Fe ₂ O ₃ is added in an amount exceeding 15 wt%, the durability of the glass may be reduced.

If the amount of CuO added is less than 1 wt%, there is a concern that the antibacterial activity may not be properly expressed. Therefore, in order to express the antibacterial activity, it is more preferable that CuO be included in an amount of 3 wt% or more, more specifically, 3 to 7 wt% of the total weight of the antibacterial glass composition.

Hereinafter, a method for manufacturing antibacterial glass powder according to an embodiment of the present invention will be described with reference to the attached drawings.

Figure 1 is a process flow diagram showing a method for manufacturing antibacterial glass powder according to an embodiment of the present invention.

As illustrated in FIG. 1, a method for manufacturing antibacterial glass powder according to an embodiment of the present invention includes a mixing step (S110), a melting step (S120), a cooling step (S130), and a crushing step (S140).

mix

In the mixing step (S110), 40 to 50 wt% of SiO ₂ and B ₂ O ₃ are mixed, 15 to 30 wt% of at least one of Na ₂ O and K ₂ O, 10 to 30 wt% of ZnO, 5 to 15 wt% of CaO, and 1 to 15 wt% of at least one of CuO and Fe ₂ O ₃ are mixed and stirred to form an antibacterial glass composition.

Here, it is preferable to add SiO ₂ in a higher content than that of B ₂ O ₃ .

More preferably, SiO ₂ is added at 30 to 40 wt% and B ₂ O ₃ is added at 5 to 10 wt%.

Additionally, it is more preferable to add CuO at 3 to 7 wt%.

Melting

In the melting step (S120), the antibacterial glass composition is melted.

In this step, it is preferable that the melting be performed at 1,200 to 1,300°C for 1 to 60 minutes. If the melting temperature is lower than 1,200°C or the melting time is lower than 1 minute, there is a problem that the antibacterial glass composition is not completely dissolved, causing inmiscibility of the glass melt. On the contrary, if the melting temperature exceeds 1,300°C or the melting time exceeds 60 minutes, it is not economical because excessive energy and time are required.

cooling

In the cooling step (S130), the molten antibacterial glass composition is cooled to room temperature.

At this stage, it is preferable that cooling be performed in a furnace. If air cooling or water cooling is applied, internal stress of the antibacterial glass may be severely formed, which may cause cracks in some cases. Therefore, cooling in a furnace is preferable.

smash

In the crushing step (S140), the cooled antibacterial glass is crushed. At this time, any of the commonly known ball mills, jet mills, and planetary mills can be applied for crushing.

By this grinding, the antibacterial glass is finely ground to produce antibacterial glass powder. It is preferable that the antibacterial glass powder has an average diameter of 30 ㎛ or less, and a more preferable range can be an average diameter of 1 to 10 ㎛.

Meanwhile, a home appliance according to an embodiment of the present invention includes a plastic injection molded product to which an antibacterial glass powder manufactured by the method described above is added to a resin material. In the present invention, the home appliance includes a washing machine, a stand air conditioner, a system air conditioner, and the like, and can be interpreted to mean an electronic product.

Here, the plastic injection molded product contains 95.0 to 99.0 wt% of resin material and 1.0 to 5.0 wt% of antibacterial glass powder.

If the amount of antibacterial glass powder added is less than 1.0 wt% of the total weight of the plastic injection molding, the antibacterial activity against Pseudomonas aeruginosa may not be sufficient. Conversely, if the amount of antibacterial glass powder added is excessive, exceeding 5.0 wt% of the total weight of the plastic injection molding, the mechanical properties may deteriorate.

The resin material contains at least one of PP (polypropylene), PC (polycarbonate), EPDM (ethylene propylene rubber), ABS (acrylonitrile-buradiene-styrene), and HIPS (high impact polystyrene).

At this time, the antibacterial glass powder contains 40 to 50 wt% of a combination of SiO ₂ and B ₂ O ₃ , 15 to 30 wt% of at least one of Na ₂ O and K ₂ O, 10 to 30 wt% of ZnO, 5 to 15 wt% of CaO, and 1 to 15 wt% of at least one of CuO and Fe ₂ O ₃ .

In addition, the plastic injection molded product may contain functional additives in addition to the antibacterial glass powder. At this time, the functional additives may include at least one selected from an antioxidant, a foaming agent, an impact modifier, a nucleating agent, a coupling agent, etc.

Accordingly, the home appliance according to the embodiment of the present invention is applied to the surface of a part that is vulnerable to bacterial growth and has a lot of contact with moisture, and has an antibacterial effect that can prevent the habitation and growth of various microorganisms.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and cannot be interpreted as limiting the present invention in any way.

Anything not described here is technically inferable enough to be understood by those skilled in the art, so its description will be omitted.

1. Manufacturing of injection molded products

Example 1

An antibacterial glass composition having the composition described in Table 1 was melted in an electric furnace at a temperature of 1,260°C, and then cooled in the form of a glass bulk on a stainless steel plate by air cooling to obtain an antibacterial glass in the form of a cullet. Thereafter, the antibacterial glass was pulverized in a dry grinder (ball mill) and passed through a 400 mesh sieve to produce an antibacterial glass powder having a D90 average particle size of 7 μm.

Next, 3 wt% of antibacterial glass powder and 97 wt% of PP (polypropylene) resin were mixed and injection-molded using an injection molding machine to produce an injection-molded product of 200 mm (width), 100 mm (height), and 3 mm (thickness).

Example 2

An antimicrobial glass powder having a D90 average particle size of 5 μm was manufactured in the same manner as in Example 1, except that the antimicrobial glass composition having the composition described in Table 1 was melted in an electric furnace at a temperature of 1,220°C.

Next, 4 wt% of antibacterial glass powder and 96 wt% of polypropylene (PP) resin were mixed and injection-molded using an injection molding machine to produce an injection-molded product of 200 mm (width), 100 mm (height), and 3 mm (thickness).

[Table 1] (Unit: weight%)

2. Antibacterial power measurement

Table 2 shows the results of antibacterial activity measurement for injection molded products manufactured according to Examples 1 and 2. At this time, in order to confirm the antibacterial activity for each injection molded product, the antibacterial activity values for Staphylococcus aureus, Escherichia coli, Streptococcus pneumoniae, and Pseudomonas aeruginosa were measured using the film adhesion method of JIS Z 2801, an antibacterial standard test method. Here, in Example 1, the antibacterial evaluation was conducted immediately after manufacturing the injection molded product without immersion, and in Example 2, the antibacterial evaluation was conducted after immersion at 90°C for 96 hours after manufacturing the injection molded product.

Stomacher 400 POLY-BAG was used as the standard film, and the test conditions were to measure the number of bacteria after culturing the test bacterial solution at 35 ± 1℃ and RH 90% for 24 hours.

[Table 2]

As shown in Tables 1 and 2, in the case of the injection-molded products manufactured according to Examples 1 and 2, it can be confirmed that the bacterial counts in all strains (Staphylococcus aureus, Escherichia coli, Streptococcus pneumoniae, and Pseudomonas aeruginosa) decreased rapidly after 24 hours.

In addition, it was confirmed that the injection-molded products manufactured according to Examples 1 and 2 had an antibacterial activity value of 2.0 log or higher, indicating an antibacterial power of 99% or higher.

Meanwhile, FIG. 2 is a photograph showing the results of measuring the antibacterial activity against Pseudomonas aeruginosa for an injection molded product manufactured according to Example 1, and FIG. 3 is a photograph showing the results of measuring the antibacterial activity against Pseudomonas aeruginosa after immersion for an injection molded product manufactured according to Example 2.

As shown in FIGS. 2 and 3, in the case of the injection molded products manufactured according to Examples 1 and 2, it can be confirmed from the results of measuring the antibacterial activity against Pseudomonas aeruginosa that Pseudomonas aeruginosa was significantly reduced after 24 hours.

As a result, it was confirmed that the injection-molded products manufactured according to Examples 1 and 2 exhibited excellent antibacterial activity against Pseudomonas aeruginosa.

Although the present invention has been described with reference to the drawings as examples, it is obvious that the present invention is not limited to the embodiments and drawings disclosed in this specification, and that various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. In addition, even if the effects according to the configuration of the present invention were not explicitly described while describing the embodiments of the present invention, it is natural that the effects predictable by the corresponding configuration should also be recognized.

S110 : Mixing stage
S120: Melting stage
S130: Cooling stage
S140: Crushing stage

Claims (10)

40 to 50 wt% of SiO ₂ and B ₂ O ₃ combined;
15 to 30 wt% of at least one of _Na2O and _K2O ;
ZnO 10 to 30 wt%;
CaO 5 to 15 wt%; and
An antibacterial glass composition comprising 1 to 15 wt% of CuO and Fe ₂ O ₃ in total;
An antimicrobial glass composition in which the addition of Ag series metal ions is excluded, and the antimicrobial glass composition is added as an additive in an amount of 1.0 to 5.0 wt% of the total weight of the plastic injection molded product.
In the first paragraph,
The above SiO ₂ is
An antibacterial glass composition added in a higher amount than the above B ₂ O ₃ content.
In the second paragraph,
The above SiO ₂ is added in an amount of 30 to 40 wt%,
_The above _B2O3 is an antibacterial glass composition added at 5 to 10 wt%.
In the first paragraph,
The above CuO is
An antimicrobial glass composition added at 3 to 7 wt%.
(a) a step of forming an antibacterial glass composition by mixing and stirring 40 to 50 wt% of a combination of SiO ₂ and B ₂ O ₃ , 15 to 30 wt% of at least one of Na ₂ O and K ₂ O, 10 to 30 wt% of ZnO, 5 to 15 wt% of CaO, and 1 to 15 wt% of a combination of CuO and Fe ₂ O ₃ ;
(b) a step of melting the antibacterial glass composition;
(c) a step of cooling the molten antimicrobial glass composition; and
(d) a step of crushing the cooled antibacterial glass to obtain antibacterial glass powder;
A method for manufacturing an antibacterial glass powder, wherein the addition of Ag series metal ions is excluded, and the antibacterial glass powder is added as an additive in an amount of 1.0 to 5.0 wt% of the total weight of a plastic injection molded product.
In paragraph 5,
In step (a) above,
The above SiO ₂ is
A method for producing antibacterial glass powder by adding a higher amount than the above B ₂ O ₃ amount.
In Article 6,
The above SiO ₂ is added in an amount of 30 to 40 wt%,
A method for producing antibacterial glass powder, _{wherein the above B2O3 is} added in an amount of 5 to 10 wt%.
In paragraph 5,
In step (a) above,
The above CuO is
A method for producing an antibacterial glass powder by adding 3 to 7 wt%.
A home appliance comprising a plastic injection molded product with antibacterial glass powder added to the resin material,
The above plastic injection molded product
95.0 to 99.0 wt% of the above resin material; and
Containing 1.0 to 5.0 wt% of the above antibacterial glass powder;
The above antibacterial glass powder contains 40 to 50 wt% of SiO ₂ and B ₂ O ₃ combined, 15 to 30 wt% of at least one of Na ₂ O and K ₂ O, 10 to 30 wt% of ZnO, 5 to 15 wt% of CaO, and 1 to 15 wt% of CuO and Fe ₂ O ₃ combined.
The above antibacterial glass powder is for home appliances that exclude the addition of Ag series metal ions.
In Article 9,
The above resin material
Home appliances containing at least one of PP (polypropylene), PC (polycarbonate), EPDM (ethylene propylene rubber), ABS (acrylonitrile-buradiene-styrene), and HIPS (high impact polystyrene).

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