Antimicrobial glass composition comprising mixture of two types of glass, method for producing antimicrobial glass powder thereof, and home appliances comprising same

Abstract

Disclosed in the present invention are an antimicrobial glass composition comprising a mixture of two types of glass, an antimicrobial glass powder thereof, and a method for producing same. The dual-type antimicrobial glass composition is prepared by mixing an Ag-containing borate glass and a Zn-containing phosphate glass to appropriately utilize two antimicrobial active substances. The dual-type antimicrobial glass composition is designed such that the Ag-containing borate glass and the Zn-containing phosphate glass have different elution rates when exposed to moisture or the like, thereby forming a crystalline phase in which an elution of Ag does not manifest as discoloration and thus suppressing discoloration caused by reduction of Ag.

Description

Antibacterial glass composition mixing two types of glass and a method for manufacturing the antibacterial glass powder thereof, and home appliances including the same

[0001] The present invention relates to a two-type glass mixture antibacterial glass composition and a method for manufacturing the antibacterial glass powder, and to a home appliance containing the same.

[0002]

[0003] Generally, antimicrobial glass utilizes performance trade-offs by optimizing a single type of glass composition. However, the technology of mixing two types of glass has limitations in that it utilizes the glass composition and the environment in which it is applied as variables, diversifying design parameters according to the purpose of application, and creating new products for different applications and environments each time.

[0004] In addition, conventionally, a technique of mixing two types of glass was used as a means to control leaching. By maximizing leaching to enhance antibacterial activity, the aim was to resolve the difficulties in achieving a compositional range.

[0005] However, in the case of glass containing Ag, the chronic problem of discoloration caused by the reduction of Ag could not be prevented, and glass containing Zn had the problem of not being able to achieve the same immediate performance as glass containing Ag.

[0006]

[0007] [Prior Art Literature]

[0008] [Patent Literature]

[0009] (Patent Document 1) KR Published Patent Application No. 10-2022-0129279 (Published Sep. 23, 2022)

[0010]

[0011] The objective of the present invention is to provide a two-type glass mixture antibacterial glass composition designed such that the leaching rates of Ag-containing borate glass and Zn-containing phosphate glass differ when exposed to moisture, etc., by appropriately utilizing two antibacterial active substances by mixing Ag-containing borate glass with Zn-containing phosphate glass, and to provide a method for manufacturing the antibacterial glass powder and the same, and a home appliance including the same.

[0012] In addition, the objective of the present invention is to provide a two-type glass mixture antibacterial glass composition capable of suppressing discoloration caused by the reduction of Ag by forming a crystalline phase in which the leaching of Ag does not appear as discoloration, a method for manufacturing the antibacterial glass powder, and a home appliance including the same.

[0013] In addition, the objective of the present invention is to provide a two-type glass mixed antibacterial glass composition capable of suppressing discoloration caused by reduction, which is a chronic problem of Ag, by forming a colorless crystalline phase according to the elution order to prevent discoloration caused by reduction of Ag, which is a chronic problem of antibacterial agents containing Ag, and a method for manufacturing the antibacterial glass powder thereof, and a home appliance including the same.

[0014] The objects of the present invention are not limited to those mentioned above, and other unmentioned objects and advantages of the present invention may be understood from the following description and will be more clearly understood by the embodiments of the present invention. Furthermore, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0015]

[0016] The antibacterial glass composition of two types of glass mixed according to the present invention and the method for manufacturing the antibacterial glass powder thereof, and the home appliance including the same are designed such that the leaching rates of Ag-containing borate glass and Zn-containing phosphate glass are different when exposed to moisture, etc. by appropriately utilizing two antibacterial active substances by mixing Zn-containing phosphate glass with Ag-containing borate glass.

[0017] As a result, the antibacterial glass composition mixed with two types of glass according to the present invention, the method for manufacturing the antibacterial glass powder, and the home appliance containing the same can suppress discoloration caused by the reduction of Ag by forming a crystalline phase in which the leaching of Ag does not appear as discoloration.

[0018] In this way, the antibacterial glass composition mixed with two types of glass according to the present invention, the method for manufacturing the antibacterial glass powder, and the home appliance containing the same secure immediate antibacterial power and long-term antibacterial power by mixing Ag-containing borate glass and Zn-containing phosphate glass.

[0019] In addition, the antibacterial glass composition mixed with two types of glass according to the present invention, the method for manufacturing the antibacterial glass powder, and the home appliance containing the same can prevent discoloration caused by reduction of Ag, which is a chronic problem of antibacterial agents containing Ag, by forming a colorless crystalline phase according to the order of elution, thereby suppressing discoloration caused by reduction of Ag, which is a chronic problem of Ag.

[0020] To this end, the antibacterial glass composition of two types of glass mixed according to an embodiment of the present invention comprises: Ag-containing borate glass; and Zn-containing phosphate glass mixed in the Ag-containing borate glass; wherein Ag is supported on the borate glass and, when exposed to moisture, the Ag supported on the borate glass is leached at a first rate, and Zn-containing phosphate glass is supported on the phosphate glass and, when exposed to moisture, the Zn supported on the phosphate glass is leached at a second rate slower than the first rate.

[0021] At this time, the antibacterial glass composition of the two types of glass mixture according to an embodiment of the present invention comprises 5 to 30 weight% of Ag-containing borate glass; and 70 to 95 weight% of Zn-containing phosphate glass.

[0022] Here, it is more preferable to include 10 to 25 weight% of Ag-containing borate glass; and 75 to 90 weight% of Zn-containing phosphate glass.

[0023] In addition, the Ag-containing borate glass comprises B2O3: 60 to 90 wt%; MgO: 5 to 35 wt%; and Ag2O: 2 to 10 wt%.

[0024] Here, it is more preferable to include 3 to 8 weight percent of Ag2O.

[0025] In addition, the Zn-containing phosphate glass contains P2O5: 50 to 75 wt%; MgO: 10 to 30 wt%; and ZnO: 12 to 36 wt%.

[0026] It is more preferable to include 15 to 30 weight percent of ZnO.

[0027]

[0028] According to the present invention, by mixing Ag-containing borate glass with Zn-containing phosphate glass and appropriately utilizing the two antimicrobial active substances, the leaching rates of Ag-containing borate glass and Zn-containing phosphate glass are designed to be different when exposed to moisture, etc.

[0029] As a result, according to the present invention, discoloration caused by the reduction of Ag can be suppressed by forming a crystalline phase in which the elution of Ag does not appear as discoloration.

[0030] In this way, according to the present invention, by mixing Ag-containing borate glass and Zn-containing phosphate glass, immediate antibacterial power and long-term antibacterial power can be secured.

[0031] Therefore, when applying and using the present invention as an antimicrobial agent, it is possible to optimize its use according to the environment by varying not only the additive content but also the ratio of the two types of glass mixed antimicrobial glass compositions depending on the application environment of the product.

[0032] As a result, the antibacterial glass powder mixed with two types of glass according to the present invention is suitable for semi-permanent use as at least one of a coating agent for glass shelves, an additive for plastic injection molding, an additive for paint, and an additive for powder coating.

[0033] In addition to the effects described above, the specific effects of the present invention are described together with the specific details for implementing the invention below.

[0034]

[0035] FIG. 1 is a process flowchart showing a method for manufacturing antibacterial glass powder mixed with two types of glass according to an embodiment of the present invention.

[0036]

[0037] The aforementioned objectives, features, and advantages are described in detail below with reference to the attached drawings, thereby enabling those skilled in the art to easily implement the technical concept of the present invention. In describing the present invention, detailed descriptions of known technologies related to the present invention are omitted if it is determined that such descriptions would unnecessarily obscure the essence of the invention. Hereinafter, preferred embodiments 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.

[0038] Singular expressions used in this specification include plural expressions unless the context clearly indicates otherwise. In this application, terms such as "composed of" or "comprising" should not be interpreted as necessarily including all of the various components or steps described in the specification, and should be interpreted as meaning that some of the components or steps may be omitted or additional components or steps may be included.

[0039] Hereinafter, a two-type glass mixed antibacterial glass composition according to some embodiments of the present invention, a method for manufacturing the antibacterial glass powder, and a home appliance including the same will be described.

[0040]

[0041] The antibacterial glass composition of two types of glass mixed according to an embodiment of the present invention is designed such that the leaching rates of Ag-containing borate glass and Zn-containing phosphate glass are different when exposed to moisture, etc., by appropriately utilizing two antibacterial active substances by mixing Ag-containing borate glass with Zn-containing phosphate glass.

[0042] As a result, the antibacterial glass composition of the two types of glass mixture according to the embodiment of the present invention suppressed discoloration caused by the reduction of Ag by forming a crystalline phase in which the leaching of Ag does not appear as discoloration.

[0043] As such, the antibacterial glass composition of the two types of glass mixture according to the embodiment of the present invention secures immediate antibacterial power and long-term antibacterial power by mixing Ag-containing borate glass and Zn-containing phosphate glass.

[0044] In this case, Ag exhibits immediate performance with a small amount because it exerts antibacterial activity by destroying cell walls. On the other hand, Zn is involved in cell metabolism and causes cell death due to metabolic dysfunction caused by an excess of ions, so it requires time for performance to manifest. Accordingly, the present invention implements the utilization of both effects.

[0045] In this invention, discoloration caused by the reduction of Ag, which is a chronic problem associated with antimicrobial agents containing Ag, can be prevented. Specifically, by forming a colorless crystalline phase according to the elution sequence, the discoloration caused by reduction, a chronic problem of Ag, is suppressed.

[0046]

[0047] To this end, the antibacterial glass composition of two types of glass mixed according to an embodiment of the present invention comprises: Ag-containing borate glass; and Zn-containing phosphate glass mixed in the Ag-containing borate glass; wherein Ag is supported on the borate glass and, when exposed to moisture, the Ag supported on the borate glass is leached at a first rate, and Zn-containing phosphate glass is supported on the phosphate glass and, when exposed to moisture, the Zn supported on the phosphate glass is leached at a second rate slower than the first rate.

[0048] At this time, the antibacterial glass composition of the two types of glass mixture according to an embodiment of the present invention comprises 5 to 30 weight% of Ag-containing borate glass; and 70 to 95 weight% of Zn-containing phosphate glass.

[0049] Here, it is more preferable to include 10 to 25 weight% of Ag-containing borate glass; and 75 to 90 weight% of Zn-containing phosphate glass.

[0050] If the content of Ag-containing borate glass is added at less than 5% by weight of the total weight of the antibacterial glass composition mixed with two types of glass, there is a high risk that the leaching concentration of Ag, which has an immediate antibacterial effect, will be low, and rapid antibacterial activity will not be exhibited. Conversely, if the content of Al-containing borate glass is added in large quantities exceeding 30% by weight of the total weight of the antibacterial glass composition mixed with two types of glass, the effect of preventing discoloration by silver borate, which has a transparent or white crystalline phase formed on the surface, is negligible, and there is a problem that yellowing of Ag occurs.

[0051] In addition, the Ag-containing borate glass comprises B2O3: 60 to 90 wt%; MgO: 5 to 35 wt%; and Ag2O: 2 to 10 wt%.

[0052] Here, it is more preferable to include 3 to 8 weight percent of Ag2O.

[0053] In addition, the Zn-containing phosphate glass contains P2O5: 50 to 75 wt%; MgO: 10 to 30 wt%; and ZnO: 12 to 36 wt%.

[0054] It is more preferable to include 15 to 30 weight percent of ZnO.

[0055]

[0056] Generally, phosphates and borates are widely known as glass-forming oxides for vitrifying Ag.

[0057] Since Ag is expensive, there is no difference in the degree of vitrification between phosphate and borate when the content is less than 2.0 wt%; however, when Ag is contained in high concentrations of 2.0 wt% or more, among the two glass-forming oxides, phosphate exhibits inferior characteristics compared to those containing relatively large amounts of Ag because it contains non-crosslinked oxygen. Furthermore, in cases where Ag discolors due to moisture (UV), Ag + The reduction of to Ag to become yellow or yellow, and Ag + There are cases where it reacts with phosphoric acid to form the yellow crystal color of Ag3PO4.

[0058] However, silver borate crystals are characterized by being transparent or white and having little change in color, but borate-based glass has poor durability because it is susceptible to moisture even if the structure is strengthened by including hard components.

[0059] Zn-containing phosphate glass has antioxidant properties. In addition, Zn-containing phosphate glass is Zn 2+It can exhibit antimicrobial properties because it can leach out. However, since Ag expresses antimicrobial activity by destroying cell walls, it demonstrates immediate performance with a small amount. Zn, on the other hand, is involved in cell metabolism and causes cell death due to metabolic dysfunction caused by an excess of ions; therefore, it requires time for performance to manifest, resulting in a lack of immediate efficacy. The crystalline phase of zinc phosphate has the property of absorbing UV light, and zinc phosphate glass also contains Zn within its glass structure 2+ , Since Zn-O bonds are mixed, it has antioxidant properties that absorb UV.

[0060]

[0061] Accordingly, in the present invention, by mixing Ag-containing borate glass with Zn-containing phosphate glass and appropriately utilizing the two antimicrobial active substances, the leaching rates of Ag-containing borate glass and Zn-containing phosphate glass are designed to be different when exposed to moisture, etc.

[0062] As a result, the antibacterial glass composition of the two types of glass mixture according to the embodiment of the present invention suppressed discoloration caused by the reduction of Ag by forming a crystalline phase in which the leaching of Ag does not appear as discoloration.

[0063] As such, the antibacterial glass composition of the two types of glass mixture according to the embodiment of the present invention secures immediate antibacterial power and long-term antibacterial power by mixing Ag-containing borate glass and Zn-containing phosphate glass.

[0064]

[0065] In the present invention, the Ag-containing borate glass comprises B2O3: 60 to 90 wt%; MgO: 5 to 35 wt%; and Ag2O: 2 to 10 wt%.

[0066] B2O3 is a representative network-forming oxide and, together with SiO2, is a key component that enables sufficient vitrification. This is attributed to its low melting point, which lowers the eutectic point of the melt. Additionally, B2O3 helps to form a homogeneous glass by increasing the solubility of hard components during vitrification melting. At this time, B2O3 possesses the characteristic of enabling vitrification with a high content of Ag.

[0067] It is preferable that B2O3 be added in a content ratio of 60 to 90 weight percent of the total weight of the Ag-containing borate glass, and more preferable that it be added in a content ratio of 65 to 85 weight percent. If the amount of B2O3 added is less than 60 weight percent of the total weight of the Ag-containing borate glass, there is a risk that Ag will not be sufficiently dissolved in the glass in ionic form and will be reduced to the metallic Ag form. Conversely, if the amount of B2O3 added exceeds 90 weight percent of the total weight of the Ag-containing borate glass, the durability of the glass is reduced and it becomes very susceptible to moisture.

[0068]

[0069] Although MgO is an alkaline earth metal, it is known to enhance the durability and raise the melting point of borate-based glasses, unlike CaO, due to the influence of single bond strength with oxygen and ionic size. In this invention, MgO was utilized as a component to strengthen the glass structure by excluding the use of Na2O, K2O, and CaO, which cause oxidation problems. Although MgO exists as a modifying oxide in the glass and plays a role in increasing non-crosslinked oxygen, the strong Mg-O bond strength and Mg + The size of the ion is Na + , K + , Ca + Because the ratio is small, the leaching characteristics caused by water ion exchange are reduced, resulting in improved durability. The core mechanism of water leaching is H3O +H3O in the initial reaction by the substitution of ions and glass ionic compounds + and Ag + It has the characteristic of being easy to elute by substitution because its ion size is similar.

[0070] It is preferable that MgO be added in a content ratio of 5 to 35 weight percent of the total weight of the Ag-containing borate glass, and more preferable that it be added in a content ratio of 15 to 30 weight percent. If the amount of MgO added is less than 5 weight percent of the total weight of the Ag-containing borate glass, the glass structure is not sufficiently strengthened and becomes very susceptible to moisture. Conversely, if the amount of MgO added exceeds 35 weight percent of the total weight of the Ag-containing borate glass, alkaline earth elements, which are substances that melt at high temperatures, are not sufficiently melted, so a phenomenon may occur in which unmelted material is formed outside the vitrification region.

[0071]

[0072] Ag2O is a component that exhibits representative antibacterial activity, and within glass, Ag + It exists in the form of a modified oxide. When Ag is added to glass, it is introduced through stoichiometric calculations in the form of Ag3PO4, AgNO3, Ag2O, and Ag metal powder, and the final form is Ag + Of course, adding a large amount of Ag has the advantage of strong antibacterial power, but it cannot be added in large quantities to the matrix that guarantees durability, and it is not practical due to issues such as discoloration and cost.

[0073] It is preferable that Ag2O be added in a content ratio of 2 to 10 weight percent of the total weight of the Ag-containing borate glass, and more preferable that it be added in a content ratio of 3 to 8 weight percent. If the amount of Ag2O added is less than 2 weight percent of the total weight of the Ag-containing borate glass, there is a concern that the antibacterial power may not be sufficiently exerted due to the low Ag content in the two-type mixed antibacterial glass composition. Conversely, if the amount of Ag2O added exceeds 10 weight percent of the total weight of the Ag-containing borate glass, there is a problem in that Ag is not sufficiently incorporated into the glass in ionic form and is reduced to the metallic Ag form.

[0074]

[0075] Meanwhile, in the present invention, the Zn-containing phosphate glass comprises P2O5: 50 to 75 wt%; MgO: 10 to 30 wt%; and ZnO: 12 to 36 wt%.

[0076] P2O5 is a representative network-forming oxide and, together with SiO2, is a key component that enables sufficient vitrification. This is due to its low melting point, which lowers the eutectic point of the melt. Additionally, P2O5 helps to form a homogeneous glass by increasing the solubility of hard components during vitrification melting.

[0077] It is preferable that P2O5 be added in a content ratio of 50 to 75 weight percent of the total weight of the Zn-containing phosphate glass, and more preferable that it be added in a content ratio of 50 to 65 weight percent. If the amount of P2O5 added is less than 50 weight percent of the total weight of the Zn-containing phosphate glass, there is a risk that the vitrification range may be exceeded due to a lack of network-forming oxides. Conversely, if the amount of P2O5 added exceeds 75 weight percent of the total weight of the Zn-containing phosphate glass, the durability of the glass is reduced and it becomes very susceptible to moisture.

[0078] Although MgO is an alkaline earth metal, it is known to enhance the durability and raise the melting point of borate-based glasses, unlike CaO, due to the influence of single bond strength with oxygen and ionic size. In this invention, MgO is utilized as a component that strengthens the glass structure by excluding the use of Na2O, K2O, and CaO, which cause oxidation problems. MgO exists as a modifying oxide within the glass and plays a role in increasing non-crosslinked oxygen. However, MgO is characterized by the strong Mg-O bond strength and Mg + The size of the ion is Na + , K + , Ca + Because the ratio is small, the leaching characteristics caused by water ion exchange are reduced, resulting in improved durability. The core mechanism of water leaching is H3O + H3O in the initial reaction by the substitution of ions and glass ionic compounds + and Ag + It has the characteristic of being easy to elute by substitution because its ion size is similar.

[0079] It is preferable to add MgO in a content ratio of 10 to 30 weight percent of the total weight of the Zn-containing phosphate glass. If the amount of MgO added is less than 10 weight percent of the total weight of the Zn-containing phosphate glass, the glass structure is not sufficiently strengthened and becomes very susceptible to moisture. Conversely, if the amount of MgO added exceeds 30 weight percent of the total weight of the Zn-containing phosphate glass, alkaline earth elements, which are substances that melt at high temperatures, are not sufficiently melted, so a phenomenon may occur in which unmelted material is formed outside the vitrification region.

[0080]

[0081] In terms of glass structure, ZnO is a component that performs both the roles of a network-forming agent and a modifying oxide. Furthermore, in the present invention, ZnO is a key component that exhibits an antibacterial effect. In a composition free of alkali oxides, the structure of ZnO is determined by P2O5, forming O-Zn-O covalent bonds and Zn 2+ Ionic bonds are also mixed in. This structure creates a local positive charge that differs from the negative charge of the normal state of the bacteria, and by adding the ROS produced by this structure, the bacteria undergo oxidative stress, thereby performing an antibacterial function. In the present invention, although ZnO does not exhibit primary antibacterial properties, it is utilized as an auxiliary material to complement the antibacterial properties of Ag.

[0082] In addition, O-Zn-O covalent bonds and Zn 2+ A state in which ionic bonds are mixed produces an effect similar to ZnO exhibiting ionic characteristics despite being a ceramic material. This state exhibits UV absorption performance and, in a localized state where alkali oxides are absent, absorbs UV energy directed toward Ag ions to prevent discoloration.

[0083] It is preferable that ZnO be added in a content ratio of 12 to 36 weight percent of the total weight of the Zn-containing phosphate glass, and more preferable that it be added in a content ratio of 15 to 30 weight percent. If the amount of ZnO added is less than 12 weight percent of the total weight of the Zn-containing phosphate glass, the glass structure is not sufficiently strengthened, making it susceptible to moisture, and the amount of Zn ion leaching decreases, which may reduce the properties that assist antibacterial power in the antibacterial glass composition of the two types of glass mixture. Conversely, if the amount of ZnO added exceeds 36 weight percent of the total weight of the Zn-containing phosphate glass, the density of the glass increases, resulting in a significant difference in density from borate glass, which may cause non-uniform separation during physical mixing.

[0084]

[0085] A method for manufacturing a two-type glass mixture antibacterial glass powder according to an embodiment of the present invention will be described below with reference to the attached drawings.

[0086] FIG. 1 is a process flowchart showing a method for manufacturing antibacterial glass powder mixed with two types of glass according to an embodiment of the present invention.

[0087] As illustrated in FIG. 1, a method for manufacturing antibacterial glass powder mixed with two types of glass according to an embodiment of the present invention includes a mixing step (S110), a melting step (S120), a cooling step (S130), and a grinding step (S140).

[0088]

[0089] mix

[0090] In the mixing step (S110), Zn-containing phosphate glass is mixed with Ag-containing borate glass and stirred to form a two-glass mixed antibacterial glass composition.

[0091] In this step, it is preferable to mix 5 to 30 weight% of Ag-containing borate glass and 70 to 95 weight% of Zn-containing phosphate glass, and more preferable to include 10 to 25 weight% of Ag-containing borate glass and 75 to 90 weight% of Zn-containing phosphate glass.

[0092] If the content of Ag-containing borate glass is added at less than 5% by weight of the total weight of the antibacterial glass composition mixed with two types of glass, there is a high risk that the leaching concentration of Ag, which has an immediate antibacterial effect, will be low, and rapid antibacterial activity will not be exhibited. Conversely, if the content of Ag-containing borate glass is added in large quantities exceeding 30% by weight of the total weight of the antibacterial glass composition mixed with two types of glass, there is a problem in that the effect of preventing discoloration by silver borate, which has a transparent or white crystalline phase formed on the surface, is negligible, and the yellowing of Ag occurs.

[0093] In addition, the Ag-containing borate glass comprises B2O3: 60 to 90 wt%; MgO: 5 to 35 wt%; and Ag2O: 2 to 10 wt%.

[0094] Here, it is more preferable to include 3 to 8 weight percent of Ag2O.

[0095] In addition, the Zn-containing phosphate glass contains P2O5: 50 to 75 wt%; MgO: 10 to 30 wt%; and ZnO: 12 to 36 wt%.

[0096] It is more preferable to include 15 to 30 weight percent of ZnO.

[0097]

[0098] melting

[0099] In the melting step (S120), the antibacterial glass composition of the two types of glass mixture is melted.

[0100] In this step, it is preferable to perform melting at 800 to 1,300°C for 30 to 90 minutes. If the melting temperature is below 800°C or the melting time is less than 30 minutes, the antibacterial glass composition mixed with two types of glass cannot be completely melted, which causes a problem of miscibility of the melted glass. Conversely, if the melting temperature exceeds 1,300°C or the melting time exceeds 90 minutes, it is not economical because excessive energy and time are required.

[0101]

[0102] cooling

[0103] In the cooling step (S130), the molten antibacterial glass composition of the two types of glass mixture is cooled.

[0104] At this stage, it is preferable to perform cooling in a furnace. Since applying air or water cooling can cause severe internal stress in the glass and potentially lead to cracking, furnace cooling is preferred.

[0105]

[0106] smash

[0107] In the grinding step (S140), the cooled antibacterial glass mixed with two types of glass is ground to obtain antibacterial glass powder mixed with two types of glass.

[0108] At this time, grinding can be performed using any one of the commonly known ball mills, jet mills, and planetary mills.

[0109] By this grinding, the glass is finely ground to produce a two-type glass mixture antibacterial glass powder. It is preferable that this two-type glass mixture antibacterial glass powder have an average diameter of 50 μm or less, and a more preferable range may be an average diameter of 1 to 15 μm.

[0110] By the above process (S110 ~ S140), a two-type glass mixed antibacterial glass powder according to an embodiment of the present invention can be manufactured.

[0111]

[0112] The method for manufacturing a two-type glass mixture antibacterial glass powder according to the embodiment of the present invention described above is designed such that the leaching rates of the Ag-containing borate glass and the Zn-containing phosphate glass are different when exposed to moisture, etc., by appropriately utilizing the two antibacterial active substances by mixing Zn-containing phosphate glass with Ag-containing borate glass.

[0113] As a result, the method for manufacturing antibacterial glass powder mixed with two types of glass according to the embodiment of the present invention suppressed discoloration caused by the reduction of Ag by forming a crystalline phase in which the leaching of Ag does not appear as discoloration.

[0114] As such, the method for manufacturing antibacterial glass powder mixed with two types of glass according to an embodiment of the present invention secures immediate antibacterial power and long-term antibacterial power by mixing Ag-containing borate glass and Zn-containing phosphate glass.

[0115] Accordingly, when the antibacterial glass powder mixed with two types of glass produced by the method according to the embodiment of the present invention is applied and used as an antibacterial agent, it is possible to optimize its use according to the environment by varying not only the added content but also the ratio of the antibacterial glass composition mixed with two types of glass depending on the application environment of the product.

[0116] As a result, the antibacterial glass powder mixed with two types of glass according to the embodiment of the present invention is suitable for semi-permanent use as at least one of a coating agent for glass shelves, an additive for plastic injection molding, an additive for paint, and an additive for powder coating.

[0117]

[0118] Meanwhile, a home appliance according to an embodiment of the present invention comprises a resin material and a plastic injection molded product to which antibacterial glass powder manufactured by the method described above is added to the resin material. The home appliance used in the present invention may include, but is not limited to, water purifiers, washing machines, stand air conditioners, system air conditioners, refrigerators, etc.

[0119] Here, the plastic injection molded product comprises 97.0 to 99.7 weight% of resin material and 0.3 to 3.0 weight% of a two-type glass mixed antibacterial glass powder.

[0120] If the amount of antibacterial glass powder mixed with two types of glass is less than 0.3% by weight of the total weight of the plastic injection molded product, the antibacterial agent is not homogeneously mixed, and performance variation may occur. Conversely, if the amount of antibacterial glass powder mixed with two types of glass is more than 3.0% by weight of the total weight of the plastic injection molded product, the proportion of expensive antibacterial agents increases, which increases costs and may lead to a deterioration in the physical properties of the plastic injection molded product.

[0121] The resin material may include at least one of PP (polypropylene), PC (polycarbonate), EPDM (ethylene propylene rubber), ABS (acrylonitrile-buradiene-styrene) and HIPS (high impact polystyrene), but is not limited thereto.

[0122] The antibacterial glass powder of the two types of glass mixture comprises: Ag-containing borate glass; and Zn-containing phosphate glass mixed with Ag-containing borate glass; wherein Ag is supported on the borate glass and, when exposed to moisture, the Ag supported on the borate glass is leached out at a first rate, and Zn-containing phosphate glass has Zn supported on the phosphate glass and, when exposed to moisture, the Zn supported on the phosphate glass is leached out at a second rate slower than the first rate.

[0123]

[0124] In addition, the plastic injection molded product may contain functional additives in addition to antibacterial glass powder. In this case, the functional additives may include one or more selected from antioxidants, foaming agents, impact modifiers, nucleating agents, coupling agents, etc.

[0125] Accordingly, the home appliance according to the embodiment of the present invention is applied to the surface of a part that is susceptible to bacterial proliferation and has frequent contact with moisture, thereby possessing antibacterial power capable of preventing the habitation and growth of various microorganisms.

[0126]

[0127] Examples

[0128] Hereinafter, the structure and operation of the present invention will be explained in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and should not be interpreted in any way as limiting the present invention.

[0129] Details not listed here can be sufficiently technically inferred by a person skilled in this field, so their explanation will be omitted.

[0130]

[0131] 1. Preparation of glass powder samples

[0132] Table 1 shows the candidate compositions for Ag-containing borate glass, and Table 2 shows the candidate compositions for Zn-containing phosphate glass. Additionally, Table 3 shows the mixing ratios of the two types of antibacterial glass compositions according to Examples 1 to 8. At this time, the Ag-containing borate glass mixed with the composition and ratios listed in Table 1 and the Zn-containing phosphate glass mixed with the composition and ratios listed in Table 2 were mixed and stirred according to the mixing ratios of Examples 1 to 8 listed in Table 3. The resulting two-type glass mixed antibacterial glass compositions were each melted in an electric furnace at a temperature of 1,200°C, then quenched on a stainless steel plate by air cooling (in the form of glass bulk) and quenched using a twin roll to obtain cullet-shaped glass. Subsequently, the glass was ground using a ball mill and passed through a mesh sieve to D 50 Glass powder with a particle size of 12㎛ or less was prepared.

[0133] Here, one of AgNO3, Ag3PO4, Ag2O, or Ag (metal powder) was used as the raw material for Ag2O by calculating the stoichiometry, and the remaining components were used as those listed in Tables 1 and 2. At this time, vitrification was classified based on the case where a homogeneous glassy state was observed and the phenomenon of milky whitening and unmelted material occurring.

[0134]

[0135] [Table 1] (Unit: weight%)

[0136]

[0137]

[0138] [Table 2] (Unit: weight%)

[0139]

[0140]

[0141] [Table 3] (Unit: weight%)

[0142]

[0143]

[0144] 2. Evaluation of Glass Powder Physical Properties

[0145] Table 4 shows the results of the physical property evaluation for the two types of glass mixed antibacterial glass powder samples prepared according to Examples 1 to 8.

[0146]

[0147] 1) Measurement of antibacterial activity

[0148] For Examples 1 to 8, in which homogeneous vitrification was performed, viable cell count analysis was conducted after exposure to two bacteria (Staphylococcus aureus, Escherichia coli, K) for 30 minutes and 1 hour according to the shaking flask method (ASTM E2149-13a).

[0149]

[0150] 2) Evaluation of discoloration characteristics

[0151] To evaluate the discoloration characteristics of the antibacterial glass powder mixed with two types of glass prepared according to Examples 1 to 8, the changes in color difference L, a, and b before and after 2 weeks of exposure under UV 30W, 5cm conditions were measured.

[0152]

[0153] [Table 4]

[0154]

[0155] As shown in Tables 1 to 4, the maximum antibacterial activity of the shaking flask method is 99.9%. At this time, excluding Example 7, it was confirmed that the two types of glass mixed antibacterial glass powders prepared according to Examples 1 to 6 and 8 exhibited excellent antibacterial activity of 99% or more.

[0156] In addition, it was confirmed that the antibacterial glass powders mixed with two types of glass prepared according to Examples 1 to 8 did not show significant changes in the color difference L, a, and b (ΔL, Δa, Δb). In particular, it was confirmed that the antibacterial glass powders mixed with two types of glass prepared according to Examples 1 to 5 and 7 showed almost no change in color.

[0157]

[0158] As can be seen from the experimental results above, in the case of the two types of glass mixed antibacterial glass powders prepared according to Examples 1 to 8, Ag is rapidly leached by being supported on borate glass with low durability, and zinc, which is subsequently leached from phosphate glass designed to have a relatively slower leaching rate, exhibits medium- and long-term antibacterial properties.

[0159] Accordingly, it was confirmed that discoloration caused by Ag reduction, a chronic problem associated with antimicrobial agents containing Ag, can be prevented. Furthermore, in cases where Ag discolors due to moisture (UV), Ag + The reduction of to Ag to become yellow or black, and Ag + There are cases where Ag3PO4 turns yellow when it comes into contact with phosphoric acid. However, when Ag-containing borate glass and Zn-containing phosphate glass are mixed, Ag and borate are leached first to form a silver borate crystal phase, and it was confirmed that the crystal phase is transparent and white with little change in color.

[0160]

[0161] 3. Manufacturing of plastic injection molded products

[0162] Table 5 shows the results of evaluating the antibacterial effect of injection-molded products manufactured according to Examples 1 to 8. At this time, the plastic injection-molded products were manufactured to dimensions of 200 mm (width), 100 mm (length), and 3 mm (thickness) respectively by mixing 1.5 wt% of each of the two types of glass mixed antibacterial glass manufactured according to Examples 1 to 8 and 98 wt% of PP (Polypropylene) resin, and then injection-molding using an injection molding machine. The antibacterial performance of the manufactured plastic injection-molded products against two bacteria (Staphylococcus aureus and Escherichia coli) was confirmed by the film adhesion method (JIS Z 2801).

[0163]

[0164] [Table 5]

[0165]

[0166] As shown in Table 5, the maximum antibacterial activity of the film adhesion method is 99.99%. At this time, it was confirmed that the plastic injection molded products prepared according to Examples 1 to 6 and 8, excluding Example 7, exhibited excellent antibacterial activity of 99% or more.

[0167]

[0168] Although the present invention has been described above with reference to the illustrated drawings, the present invention is not limited by the embodiments and drawings disclosed in this specification, and it is obvious that various modifications can be made by a person skilled in the art within the scope of the technical concept of the present invention. Furthermore, even if the effects of the configuration of the present invention were not explicitly described while explaining the embodiments of the present invention above, it is natural to acknowledge that the effects predictable by said configuration should also be recognized.

[0169]

[0170] [Explanation of the symbol]

[0171] S110: Mixing step

[0172] S120: Melting stage

[0173] S130: Cooling stage

[0174] S140: Grinding step

Claims

1. Ag-containing borate glass; and Zn-containing phosphate glass mixed in the above Ag-containing borate glass; comprising The above Ag-containing borate glass has Ag supported on the borate glass, and when exposed to moisture, the Ag supported on the borate glass is leached out at a first rate, and The above Zn-containing phosphate glass comprises Zn supported on the phosphate glass, and upon exposure to moisture, the Zn supported on the phosphate glass is leached out at a second rate slower than the first rate. Antibacterial glass composition of a mixture of two types of glass.

2. In Paragraph 1, 5 to 30 weight% of the above Ag-containing borate glass; and Comprising 70 to 95 weight% of the above Zn-containing phosphate glass, Antibacterial glass composition of a mixture of two types of glass.

3. In Paragraph 2, 10 to 25 weight% of the above Ag-containing borate glass; and Comprising 75 to 90 weight% of the above Zn-containing phosphate glass, Antibacterial glass composition of a mixture of two types of glass.

4. In Paragraph 2, The above Ag-containing borate glass is B2O3: 60 ~ 90 wt%; MgO: 5 ~ 35 wt%; and Ag2O: 2 to 10 wt%; comprising, Antibacterial glass composition of a mixture of two types of glass.

5. In Paragraph 4, The above Ag2O contains 3 to 8 weight percent. Antibacterial glass composition of a mixture of two types of glass.

6. In Paragraph 2, The above Zn-containing phosphate glass is P2O5: 50 ~ 75 wt%; MgO: 10 to 30 wt%; and Containing ZnO: 12 to 36 wt%; Antibacterial glass composition of a mixture of two types of glass.

7. In Paragraph 6, The above ZnO comprises 15 to 30 weight%. Antibacterial glass composition of a mixture of two types of glass. 8.(a) A step of mixing Zn-containing phosphate glass with Ag-containing borate glass and stirring to form a two-glass mixed antibacterial glass composition; (b) a step of melting the above two types of glass mixed antibacterial glass composition; (c) a step of cooling the molten two-type glass mixture antibacterial glass composition; and (d) a step of crushing the cooled antibacterial glass of the two-glass mixture to obtain antibacterial glass powder of the two-glass mixture; comprising, The above Ag-containing borate glass has Ag supported on the borate glass, and when exposed to moisture, the Ag supported on the borate glass is leached out at a first rate, and The above Zn-containing phosphate glass comprises Zn supported on the phosphate glass, and upon exposure to moisture, the Zn supported on the phosphate glass is leached out at a second rate slower than the first rate. Method for manufacturing antibacterial glass powder mixed with two types of glass.

9. In Paragraph 8, In step (a) above, 5 to 30 weight% of the above Ag-containing borate glass; and Mixing with 70 to 95 weight% of the above Zn-containing phosphate glass, Method for manufacturing antibacterial glass powder mixed with two types of glass.

10. In Paragraph 9, 10 to 25 weight% of the above Ag-containing borate glass; and Mixed with 75 to 90 weight% of the above Zn-containing phosphate glass, Method for manufacturing antibacterial glass powder mixed with two types of glass.

11. In Paragraph 9, The above Ag-containing borate glass is B2O3: 60 ~ 90 wt%; MgO: 5 ~ 35 wt%; and Ag2O: 2 to 10 wt%; comprising, Method for manufacturing antibacterial glass powder mixed with two types of glass.

12. In Paragraph 11, The above Ag2O contains 3 to 8 weight percent. Method for manufacturing antibacterial glass powder mixed with two types of glass.

13. In Paragraph 9, The above Zn-containing phosphate glass is P2O5: 50 ~ 75 wt%; MgO: 10 to 30 wt%; and Containing ZnO: 12 to 36 wt%; Method for manufacturing antibacterial glass powder mixed with two types of glass.

14. In Paragraph 13, The above ZnO comprises 15 to 30 weight%. Method for manufacturing antibacterial glass powder mixed with two types of glass.

15. In Paragraph 8, In step (b) above, The above melting Performed at 800 to 1,300℃ for 30 to 90 minutes, Method for manufacturing antibacterial glass powder mixed with two types of glass.

16. In Paragraph 8, In step (d) above, The above-mentioned two-type glass mixture antibacterial glass powder is having an average diameter of 50㎛ or less, Method for manufacturing antibacterial glass powder mixed with two types of glass.

17. In Paragraph 8, After step (d) above, The above-mentioned two-type glass mixture antibacterial glass powder is Used as at least one of a coating agent for glass shelves, an additive for plastic injection molding, an additive for paint, and an additive for powder coating, Method for manufacturing antibacterial glass powder mixed with two types of glass.

18. A home appliance comprising a plastic injection molded product in which two types of glass mixed antibacterial glass powder is added to a resin material, The above plastic injection molded product comprises 97.0 to 99.7 weight% of the resin material and 0.3 to 3.0 weight% of the above two-type glass mixed antibacterial glass powder, and The above-mentioned two-type glass mixture antibacterial glass powder comprises Ag-containing borate glass; and Zn-containing phosphate glass mixed with the Ag-containing borate glass; and The above Ag-containing borate glass has Ag supported on the borate glass, and when exposed to moisture, the Ag supported on the borate glass is leached out at a first rate, and The above Zn-containing phosphate glass comprises Zn supported on the phosphate glass, and upon exposure to moisture, the Zn supported on the phosphate glass is leached out at a second rate slower than the first rate. Home appliances.

19. In Paragraph 18, The above resin material is Comprising at least one of PP (polypropylene), PC (polycarbonate), EPDM (ethylene propylene rubber), ABS (acrylonitrile-buradiene-styrene), and HIPS (high impact polystyrene), Home appliances.

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