Phosphate-based antibacterial glass composition, antibacterial glass powder thereof and preparation method therefor

Abstract

The present invention provides a phosphate-based antibacterial glass composition, an antibacterial glass powder thereof and a preparation method therefor, which solve the problems of antibacterial persistence and discoloration, which are chronic problems of a phosphate-based glass containing Ag, by optimizing the mixing ratio of MgO, ZnO and TiO2 components in consideration of light absorption characteristics and ionization tendency without adding Na2O, K2O, CaO and Al2O3. To this end, the phosphate-based antibacterial glass composition according to the present invention comprises: 30-40 mol% of P2O5; 5-15 mol% of B2O3; 15-50 mol% of MgO; 10-40 mol% of ZnO; 0.2-1.5 mol% of TiO2; and 0.2-1.0 mol% of Ag2O.

Description

Phosphate-based antimicrobial glass composition, antimicrobial glass powder thereof, and method for manufacturing the same

[0001] The present invention relates to a phosphate-based antibacterial glass composition, the antibacterial glass powder thereof, and a method for manufacturing the same.

[0002]

[0003] Generally, glass compositions containing Ag utilize phosphate-based materials. Since phosphate-based glass is hygroscopic and dissolves easily in water, it is necessary to improve its durability.

[0004] Typically, commercial antimicrobial agents utilize Al2O3 or ZrO2 to improve the durability of phosphate-based glass. The glass structure is strengthened with PO-Al, which reduces non-crosslinked oxygen and strengthens the glass, but this results in a problem where the melting point increases.

[0005] In addition, the glass composition containing Ag is Ag + → Ag 0 A method of adding ZnO is also utilized to prevent discoloration due to reduction. When a small amount of ZnO is added to phosphate glass, it does not affect the melting point, but a large amount of ZnO is added to ensure sufficient discoloration prevention, which raises the melting point of the glass.

[0006] The increase in the melting point of phosphate glass containing Ag is caused by the volatilization of Ag and P2O5, which are relatively low-melting point materials, so alkali metals (Na2O, K2O) and alkaline earth metals (CaO) are used to lower the melting point.

[0007] The presence of these alkali metals or alkaline earth metals causes Ag discoloration. + → Ag 0 Because it promotes the reaction, reduction of Ag occurs due to the ionization tendency during the precipitation of Ag in the vitrification process or during the process in which Ag is leached with alkali metals or alkaline earth metals upon contact with moisture when using antimicrobial agents.

[0008] For this reason, when using Na2O, K2O, or CaO, discoloration of Ag occurs, or when the melting point is controlled by increasing the P2O5 content, there is a problem of insufficient durability.

[0009] As a way to overcome this, MgO, an alkaline earth metal, is added to phosphate glass containing Ag, but there are limitations to its use alone due to the technical differences between CaO and MgO. Although MgO is an alkaline earth metal, it is known to enhance the durability and raise the melting point of phosphate glass, unlike CaO, due to the influence of single bond strength with oxygen and ionic size, so it is used in combination with alkali metals or CaO.

[0010]

[0011] [Prior Art Literature]

[0012] [Patent Literature]

[0013] (Patent Document 1) KR Published Patent Application No. 10-2022-0129279 (Published Sep. 23, 2022)

[0014]

[0015] The objective of the present invention is to provide a phosphate-based antibacterial glass composition, an antibacterial glass powder, and a method for manufacturing the same, which solves the chronic problems of antibacterial persistence and discoloration of Ag-containing phosphate-based glass by optimizing the mixing ratio of MgO, ZnO, and TiO2 components considering light absorption characteristics and ionization tendencies without adding Na2O, K2O, CaO, and Al2O3.

[0016] Furthermore, the objective of the present invention is to provide a phosphate-based antibacterial glass composition, an antibacterial glass powder, and a method for manufacturing the same, which not only enables the vitrification of Ag into an ionic state without the adverse effect of causing discoloration of the utilized TiO2 instead of excluding the addition of alkali components, but also inhibits the reduction of Ag by leaching together when Ag ions leach out in the usage environment to perform antibacterial action.

[0017] As such, the present invention utilizes other components without adding melting point lowering (Na2O, K2O, CaO) components and structural strengthening (Al2O3) components.

[0018] In other words, since the present invention stabilizes Ag in terms of its ionization tendency, which is sensitive to vitrification and discoloration, it achieves an improvement in performance regarding antibacterial persistence (durability)—addressing aesthetic issues such as discoloration to yellow or black caused by the reduction of Ag—and the formation of a crystalline phase upon reduction, which is easily isolated from the amorphous glass material.

[0019] 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.

[0020]

[0021] The present invention is characterized by providing a phosphate-based antibacterial glass composition that improves upon the chronic problems of discoloration of Ag and poor durability due to reduced durability in the design of Ag-containing phosphate-based glass compositions, the antibacterial glass powder thereof, and a method for manufacturing the same.

[0022] The phosphate-based antibacterial glass composition, the antibacterial glass powder, and the method for manufacturing the same according to an embodiment of the present invention utilize high content of MgO and ZnO to form a highly durable glass.

[0023] In addition, the phosphate-based antibacterial glass composition, the antibacterial glass powder, and the method for manufacturing the same according to the embodiment of the present invention can form glass without using alkali, CaO, etc. by adding ZnO, which has a high melting point, in an appropriate molar ratio through a eutectic phenomenon.

[0024] In addition, since the phosphate-based antibacterial glass composition, the antibacterial glass powder, and the method for manufacturing the same according to the embodiment of the present invention are glasses free of alkali and CaO, sufficiently effective discoloration inhibition properties were achieved with intentionally low content to prevent the TiO2 from changing to red (purple) or becoming excessively crystallin upon reduction.

[0025]

[0026] To this end, the phosphate-based antibacterial glass composition according to an embodiment of the present invention comprises P2O5 30 ~ 40 mol%; B2O3 5 ~ 15 mol%; MgO 15 ~ 50 mol%; ZnO 10 ~ 40 mol%; TiO2 0.2 ~ 1.5 mol%; and Ag2O 0.2 ~ 1.0 mol%.

[0027] The phosphate-based antibacterial glass composition according to an embodiment of the present invention excludes the addition of Na2O, K2O, CaO, and Al2O3.

[0028] Here, it is more preferable that the P2O5 be added in an amount of 30.1 to 38.9 mol%, and the B2O3 be added in an amount of 5.5 to 12 mol%.

[0029] In addition, it is more preferable that the MgO be added in an amount of 30 to 49 mol%, and the ZnO be added in an amount of 10 to 30 mol%.

[0030]

[0031] According to the present invention, the chronic problems of antibacterial persistence and discoloration of Ag-containing phosphate glass were solved by optimizing the mixing ratio of MgO, ZnO, and TiO2 components considering light absorption characteristics and ionization tendencies without adding Na2O, K2O, CaO, and Al2O3.

[0032] In particular, according to the present invention, instead of excluding the addition of alkali components, the utilized TiO2 can be vitrified into the ionic state of Ag without the adverse effect of causing discoloration, and furthermore, when Ag ions are leached out in the usage environment to perform an antibacterial action, they are leached out together to inhibit the reduction of Ag.

[0033] As such, the present invention utilizes other components without adding melting point lowering (Na2O, K2O, CaO) components and structural strengthening (Al2O3) components.

[0034] Accordingly, according to the present invention, the problems of the prior art are solved by approaching Ag, which is sensitive to vitrification and discoloration, from a conceptual principle and utilizing the concept of ionization tendency to use a material having the reduction inhibition effect and light absorption properties of Ag.

[0035] In other words, the phosphate-based antibacterial glass powder and the method for manufacturing the same according to the embodiment of the present invention have been stabilized in terms of the ionization tendency of Ag, which is sensitive to vitrification and discoloration. Therefore, they have achieved an improvement in performance regarding antibacterial persistence (durability) by addressing aesthetic issues such as discoloration to yellow or black caused by the reduction of Ag, and by forming a crystalline phase upon reduction to easily isolate from the amorphous glass material.

[0036] Therefore, the phosphate-based antibacterial glass powder according to the present invention prevents the discoloration of Ag when applied to and used as an antibacterial agent in a product, and also has antioxidant performance, enabling efficient long-term use.

[0037] As a result, the phosphate-based antibacterial glass powder 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.

[0038] 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.

[0039]

[0040] FIG. 1 is a process flowchart showing a method for manufacturing phosphate-based antibacterial glass powder according to an embodiment of the present invention.

[0041]

[0042] 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.

[0043] 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.

[0044] Hereinafter, a phosphate-based antibacterial glass composition, the antibacterial glass powder, and a method for manufacturing the same according to some embodiments of the present invention will be described.

[0045]

[0046] The phosphate-based antibacterial glass composition according to an embodiment of the present invention can solve the chronic problems of antibacterial persistence and discoloration of Ag-containing phosphate glass by optimizing the mixing ratio of MgO, ZnO, and TiO2 components considering light absorption characteristics and ionization tendencies without adding Na2O, K2O, CaO, and Al2O3.

[0047] In particular, the phosphate-based antibacterial glass composition according to the embodiment of the present invention excludes the addition of alkali components and, instead, enables the utilized TiO2 to vitrify Ag into an ionic state without the adverse effect of causing discoloration. Furthermore, when Ag ions are leached out in the usage environment to perform antibacterial action, they are leached out together, thereby inhibiting the reduction of Ag.

[0048] As such, the phosphate-based antibacterial glass composition according to the embodiment of the present invention utilizes other components without adding melting point lowering (Na2O, K2O, CaO) components or structural strengthening (Al2O3) components. In the present invention, the problems of the prior art are solved by approaching Ag, which is sensitive to vitrification and discoloration, from a conceptual principle and utilizing the concept of ionization tendency to utilize a material having an Ag reduction inhibition effect and light absorption properties.

[0049] In other words, since the present invention stabilizes Ag in terms of its ionization tendency, which is sensitive to vitrification and discoloration, it achieves an improvement in performance regarding antibacterial persistence (durability)—addressing aesthetic issues such as discoloration to yellow or black caused by the reduction of Ag—and the formation of a crystalline phase upon reduction, which is easily isolated from the amorphous glass material.

[0050]

[0051] To this end, the phosphate-based antibacterial glass composition according to an embodiment of the present invention comprises P2O5 30 ~ 40 mol%; B2O3 5 ~ 15 mol%; MgO 15 ~ 50 mol%; ZnO 10 ~ 40 mol%; TiO2 0.2 ~ 1.5 mol%; and Ag2O 0.2 ~ 1.0 mol%.

[0052] The phosphate-based antibacterial glass composition according to an embodiment of the present invention excludes the addition of Na2O, K2O, CaO, and Al2O3.

[0053] Here, it is more preferable that the P2O5 be added in an amount of 30.1 to 38.9 mol%, and the B2O3 be added in an amount of 5.5 to 12 mol%.

[0054] In addition, it is more preferable that the MgO be added in an amount of 30 to 49 mol%, and the ZnO be added in an amount of 10 to 30 mol%.

[0055]

[0056] The phosphate-based antimicrobial glass composition according to an embodiment of the present invention contains Ag and has a matrix composition with excellent durability. The phosphate-based antimicrobial glass composition is a glass matrix that determines durability by forming a glass structure. It performs a role similar to that of a carrier for conventional inorganic antimicrobial agents (dispersing a material exhibiting antimicrobial properties on the surface).

[0057] While conventional inorganic carriers support antimicrobial components on their surfaces, glass matrices allow metal materials exhibiting antimicrobial properties to exist within their structure in ionic form. Since Ag exhibits high reducibility during manufacturing and use and demonstrates antimicrobial activity through leaching, its antimicrobial persistence (maintaining antimicrobial properties over a long period) is influenced by the control of glass durability. Consequently, the selection and proportion of appropriate network-forming oxides, intermediate oxides, and modifying oxides become critical.

[0058] The present invention is characterized by providing a phosphate-based antibacterial glass composition that improves upon the chronic problems of discoloration of Ag and poor durability caused by reduced durability in the design of Ag-containing phosphate-based glass compositions.

[0059] The phosphate-based antibacterial glass composition according to an embodiment of the present invention utilizes high amounts of MgO and ZnO to form a highly durable glass. Furthermore, by adding ZnO, which has a high melting point, in an appropriate molar ratio, the phosphate-based antibacterial glass composition according to an embodiment of the present invention can form a glass without using alkali, CaO, etc., through a eutectic phenomenon.

[0060] Since the phosphate-based antibacterial glass composition according to the embodiment of the present invention is a glass free of alkali and CaO, sufficiently effective discoloration inhibition properties were achieved with a deliberately low content to prevent the TiO2 from changing to red (purple) or becoming excessively crystallin.

[0061] Furthermore, in the phosphate-based antibacterial glass composition according to the embodiment of the present invention, ZnO, MgO, and TiO2 exhibit an effect of inhibiting discoloration, but the principle by which each component prevents the discoloration of Ag is different. MgO exists as a modifying oxide in the glass and plays a role in increasing non-crosslinked oxygen, but due to the strong bonding strength of Mg-O and Mg + The size of the ion is Na + , K + , Ca + Due to its smaller size, it has a closed structure with reduced leaching characteristics to water, resulting in improved durability. The key mechanism for leaching into water is H3O + H3O in the initial reaction by the substitution of ions and glass ionic compounds + and Ca + , Na + , K + , Ag +It is characterized by easy elution via substitution due to similar ionic sizes. While ZnO possesses the ability to inhibit elution through structural reinforcement, the O-Zn-O covalent bond and Zn 2+ The state in which ionic bonds are mixed produces an effect similar to ZnO exhibiting ionic characteristics despite being a ceramic material.

[0062] This state exhibits UV absorption performance, and in the absence of locally occurring alkali oxides, it absorbs UV energy directed toward Ag ions to achieve anti-discoloration performance. TiO2 is Ti 4+ The ions possess light absorption characteristics and absorb light energy directed toward the Ag ions, thereby enabling anti-discoloration performance.

[0063] Furthermore, regarding ionization tendency, Ti is an electrophilic material, so Ag is Ag + By maintaining the state, it prevents the reduction of Ag whether within the glass or in an leached state. Due to these compositional and structural characteristics, it is resistant to discoloration and deterioration compared to conventional Ag-based glass, and has the effect of improving the duration of antibacterial activity.

[0064]

[0065] Below, the role and content of each component of the phosphate-based antibacterial glass composition according to an embodiment of the present invention will be explained in detail.

[0066]

[0067] Network-forming oxides

[0068] Network-forming oxides form the framework structure of glass and are components that determine vitrification through covalent bonding.

[0069] The selection of a matrix containing Ag must consider electrochemical properties and the structural aspects of the glass. Since Ag has a high reducing tendency in terms of ionization tendency, the selection of glass-forming oxides and modifying oxides affects vitrification. Generally, known ionization tendencies are discussed primarily in the nucleophilic region, focusing on alkali-alkali earth elements. Here, Ag is known as an element with a low ionization tendency and high reducing tendency. However, in the present invention, which forms the glass, the tendency in the electrophilic region, rather than the nucleophilic region, plays an important role.

[0070] In the ionization tendency region following the sequence Ag - Pt - Au - Si - Ti - Ta - C - W - Mo - V - P, SiO2 glass is at a disadvantage for containing Ag because its ionization tendency is similar to that of Ag and it has relatively little non-crosslinked oxygen.

[0071] Therefore, the P2O5- (B2O3) matrix is ​​advantageous for stably vitrifying Ag into an ionic form.

[0072] P2O5 and B2O3 are representative network-forming oxides that enable vitrification, serving as the structural framework of the glass. Both components exhibit good vitrification capabilities when used individually, but they are characterized by low durability due to their hygroscopic nature. In particular, when the two components are used together, the glass structure becomes denser, which can slightly increase durability. Since P2O5 is a metal-based intermediate oxide and B2O3 is a water-modifying oxide such as alkali-alkali earth oxide, using them in appropriate proportions offers the advantage of expanding the range of desired composition designs.

[0073] The content of network-forming oxides is determined by the cross-linking oxygen and non-cross-linking oxygen formed according to the type and content of modifying oxides and intermediate oxides in the overall composition. Since the present invention contains high amounts of MgO and ZnO, an appropriate content of glass former is required.

[0074] To this end, it is preferable that P2O5 be added in an amount of 30 to 40 mol% of the total molar ratio of the phosphate-based antibacterial glass composition, and more preferable that it be added in an amount of 30.1 to 38.9 mol%. If the amount of P2O5 added is less than 30 mol%, the vitrification range is exceeded due to a lack of network-forming oxides, and if the amount of P2O5 added exceeds 40 mol%, the durability of the glass is reduced, the leaching of ionic components increases, discoloration intensifies, and there are limitations to continuous use.

[0075] In addition, it is preferable to add B2O3 in an amount of 5 to 15 mol% of the total molar ratio of the phosphate-based antibacterial glass composition, and more preferable to add it in an amount of 5.5 to 12 mol%. If the amount of B2O3 added is less than 5 mol%, the structural bonding effect due to the strengthening of the bond between the two components of the glass former is reduced, resulting in reduced durability. If the amount of B2O3 added exceeds 15 mol%, durability is reduced, the leaching of ionic components increases, discoloration intensifies, and there are limitations to continuous use.

[0076]

[0077] Modifying Oxide

[0078] Modifying oxides cannot vitrify on their own; instead, they are components that ionically bond by entering between the covalent bonds that form the glass, thereby influencing its properties.

[0079] In the present invention, it is important to select a structural reinforcing material, a melting point lowering material, and an antimicrobial active material as the modifying oxide.

[0080] When selecting components for phosphate-based antimicrobial glass containing Ag, the ionization tendency is an important factor. In the nucleophilic region of K - Ca - Na - Mg - Al - Zn - Fe - Ni - Sn - Pb - (H) - Cu - Hg - Ag - Pt, K, Na, and Ca have high ionization tendencies and reduce Ag either within the glass or in the leached state; therefore, in this invention, MgO was used instead of fundamentally excluding the use of K2O, Na2O, and CaO.

[0081] Although MgO is an alkaline earth metal, it is known to enhance the durability and increase the melting point of phosphate-based antimicrobial glass due to the influence of single bond strength with oxygen and ionic size, unlike CaO, so it is used in combination with alkali metals or CaO.

[0082] However, in the present invention, the use of Na2O, K2O, and CaO was excluded by utilizing other solutions for melting point reduction, and MgO was utilized for structural reinforcement of phosphate-based antimicrobial glass. Although MgO exists as a modifying oxide in the glass and plays a role in increasing non-crosslinked oxygen, the strong bonding strength of Mg-O 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 Ca + , Na + , K + , Ag + It has the characteristic of being easy to elute by substitution because the ion size is similar.

[0083] It is preferable to add MgO in an amount of 15 to 50 mol% of the total molar ratio of the phosphate-based antimicrobial glass composition, and more preferable to add it in an amount of 30 to 49 mol%. If the amount of MgO added is less than 15 mol%, the durability enhancement effect obtained by the Mg-O bond strength is not observed, resulting in reduced antimicrobial persistence; if the amount of MgO added exceeds 50 mol%, the melting point of the glass increases significantly, exceeding the vitrification range where unmelted material occurs. Generally, when alkaline earth metals are used in small amounts, their melting point may decrease due to eutectic reactions, but when added in large amounts, they exhibit their inherently high melting point characteristics.

[0084]

[0085] Ag2O is a component that exhibits representative antibacterial activity, and in glass, Ag + It exists in the form of a modified oxide. When added to glass, it is input 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 amounts to the matrix that guarantees durability, and it reduces practicality due to discoloration, cost, etc.

[0086] It is preferable to add Ag2O in an amount of 0.2 to 1.0 mol% of the total molar ratio of the phosphate-based antibacterial glass composition, and more preferable to add it in an amount of 0.4 to 0.9 mol%. If the amount of Ag2O added is less than 0.2 mol%, the leached Ag + Due to a lack of ions, sufficient antibacterial activity is not exhibited, and if the amount of Ag2O added exceeds 1.0 mol%, the effect of inhibiting discoloration by the glass composition is exceeded, so silver is easily reduced and yellowing occurs, thus limiting the ability to inhibit the discoloration of Ag.

[0087]

[0088] Intermediate oxide

[0089] The intermediate oxide is a component that can substitute for and covalently bond with a portion of the network-forming oxide, thereby enabling it to function as both a network-forming oxide and a modifying oxide. In the present invention, it is preferable to select an intermediate oxide that strengthens the structure and prevents discoloration, and for this purpose, ZnO and TiO2 were selected.

[0090] 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 and B2O3, forming O-Zn-O covalent bonds and Zn 2+ Ionic bonds are also present. This structure creates a local positive charge that differs from the negative charge of the bacteria's normal state, and by adding the ROS produced by this structure, it causes the bacteria to undergo oxidative stress, thereby providing an antimicrobial function.

[0091] In the present invention, although ZnO does not exhibit primary antibacterial properties, it complements the antibacterial properties of Ag and enhances antibacterial activity in terms of antibacterial persistence; therefore, unlike conventional technology where Ag is added in high amounts to suppress discoloration in order to exhibit antibacterial persistence, it enables the appropriate use of Ag.

[0092] In addition, O-Zn-O covalent bonds and Zn 2+ In a state where ionic bonds are mixed, ZnO exhibits an effect similar to ionic characteristics, even though it is a ceramic material. This state exhibits UV absorption performance, and in a state where there are no local alkali oxides, it absorbs UV energy directed toward Ag ions to achieve anti-discoloration performance.

[0093] ZnO must be added at a concentration of 10 mol% or more of the total molar ratio of the phosphate-based antibacterial glass composition so that a melting point lowering effect occurs due to the eutectic phenomenon, allowing the glass to be formed without the use of R2O and CaO. To this end, it is preferable to add ZnO at a concentration of 10 to 40 mol% of the total molar ratio of the phosphate-based antibacterial glass composition, and it is more preferable to add it at a concentration of 10 to 30 mol%. If the amount of ZnO added is less than 10 mol%, durability is reduced, and although initial antibacterial power is achieved, there are limitations to continuous use. If the amount of ZnO added exceeds 40 mol%, the melting point of the glass increases significantly, exceeding the vitrification range, which may result in a milky white phenomenon.

[0094]

[0095] Although TiO2 is an intermediate oxide, its high single bond strength with oxygen makes it similar to glass-forming oxides, and it improves the durability of glass through the coordination bonding of Ti. In addition, Ti 4+ The ions have light absorption properties, so they absorb light energy directed toward the Ag ions to achieve anti-discoloration performance.

[0096] Furthermore, regarding ionization tendency, Ti is an electrophilic material, so Ag is Ag + By maintaining the state, it prevents the reduction of Ag whether inside the glass or in an leached state. This means that it can exhibit antioxidant performance.

[0097] In the phosphate-based antibacterial glass composition of the present invention, since a glass-forming agent is added in a low amount and ZnO and MgO are added in a high amount, if TiO2 exceeds only 1.5 mol% of the total molar ratio of the phosphate-based antibacterial glass composition, it may exceed the vitrification range and result in crystalline devitrification and unmelted products.

[0098] Therefore, it is preferable to add TiO2 in an amount of 0.2 to 1.5 mol% of the total molar ratio of the phosphate-based antibacterial glass composition. If the amount of TiO2 added is less than 0.2 mol%, the durability enhancement and light absorption ability are reduced, resulting in insufficient effectiveness in improving the discoloration characteristics of silver-containing glass. If the amount of TiO2 added exceeds 1.5 mol%, the melting point of the glass increases significantly, exceeding the vitrification range, which may lead to crystalline devitrification and unmelted products.

[0099]

[0100] A method for manufacturing phosphate-based antibacterial glass powder according to an embodiment of the present invention will be described below with reference to the attached drawings.

[0101] FIG. 1 is a process flowchart showing a method for manufacturing phosphate-based antibacterial glass powder according to an embodiment of the present invention.

[0102] As illustrated in FIG. 1, a method for manufacturing phosphate-based 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 grinding step (S140).

[0103]

[0104] mix

[0105] In the mixing step (S110), P2O5 30 ~ 40 mol%, B2O3 5 ~ 15 mol%, MgO 15 ~ 50 mol%, ZnO 10 ~ 40 mol%, TiO2 0.2 ~ 1.5 mol%, and Ag2O 0.2 ~ 1.0 mol% are mixed and stirred to form a phosphate-based antibacterial glass composition.

[0106] Here, the addition of Na2O, K2O, CaO, and Al2O3 is excluded from the phosphate-based antimicrobial glass composition.

[0107] In addition, it is more preferable to add P2O5 in an amount of 30.1 to 38.9 mol%, and it is more preferable to add B2O3 in an amount of 5.5 to 12 mol%.

[0108] In addition, it is more preferable to add MgO in an amount of 30 to 49 mol%, and it is more preferable to add ZnO in an amount of 10 to 30 mol%.

[0109]

[0110] melting

[0111] In the melting step (S120), the phosphate-based antibacterial glass composition is melted.

[0112] In this step, it is preferable to perform melting at 1,000 to 1,400°C for 30 to 90 minutes. If the melting temperature is below 1,000°C or the melting time is less than 30 minutes, the phosphate-based antibacterial glass composition is not completely melted, which causes a problem of miscibility in the melted glass. Conversely, if the melting temperature exceeds 1,400°C or the melting time exceeds 90 minutes, it is not economical because excessive energy and time are required.

[0113]

[0114] cooling

[0115] In the cooling step (S130), the molten phosphate-based antibacterial glass composition is cooled.

[0116] 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.

[0117]

[0118] smash

[0119] In the grinding step (S140), the cooled phosphate-based antibacterial glass is ground to obtain phosphate-based antibacterial glass powder.

[0120] At this time, grinding can be performed using any one of the commonly known ball mills, jet mills, and planetary mills.

[0121] By this grinding, the glass is finely ground to produce phosphate-based antibacterial glass powder. It is preferable that this phosphate-based 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 20 μm.

[0122] By the above process (S110 ~ S140), a phosphate-based antibacterial glass powder according to an embodiment of the present invention can be manufactured.

[0123]

[0124] The phosphate-based antibacterial glass powder and the method for manufacturing the same according to the aforementioned embodiment of the present invention solved the chronic problems of antibacterial persistence and discoloration of Ag-containing phosphate-based glass by optimizing the mixing ratio of MgO, ZnO, and TiO2 components considering light absorption characteristics and ionization tendencies without adding Na2O, K2O, CaO, and Al2O3.

[0125] In particular, the phosphate-based antibacterial glass powder and the method for manufacturing the same according to the embodiment of the present invention not only enable the vitrification of Ag into an ionic state without the adverse effect of causing discoloration of the utilized TiO2, instead of excluding the addition of alkali components, but also inhibit the reduction of Ag by leaching together when Ag ions are released to perform antibacterial action in the usage environment.

[0126] As such, the phosphate-based antibacterial glass powder and the method for manufacturing the same according to the embodiment of the present invention utilize other components without adding melting point lowering (Na2O, K2O, CaO) components and structural strengthening (Al2O3) components. In the present invention, the problems of the prior art are solved by approaching Ag, which is sensitive to vitrification and discoloration, from a conceptual principle and utilizing the concept of ionization tendency to utilize a material having an Ag reduction inhibition effect and light absorption properties.

[0127] In other words, the phosphate-based antibacterial glass powder and the method for manufacturing the same according to the embodiment of the present invention have been stabilized in terms of the ionization tendency of Ag, which is sensitive to vitrification and discoloration. Therefore, they have achieved an improvement in performance regarding antibacterial persistence (durability) by addressing aesthetic issues such as discoloration to yellow or black caused by the reduction of Ag, and by forming a crystalline phase upon reduction to easily isolate from the amorphous glass material.

[0128] Accordingly, the phosphate-based antibacterial glass powder prepared by the method according to the embodiment of the present invention comprises P2O5 30 ~ 40 mol%, B2O3 5 ~ 15 mol%, MgO 15 ~ 50 mol%, ZnO 10 ~ 40 mol%, TiO2 0.2 ~ 1.5 mol%, and Ag2O 0.2 ~ 1.0 mol%, and the addition of Na2O, K2O, CaO, and Al2O3 is excluded.

[0129] Accordingly, the phosphate-based antibacterial glass powder prepared by the method according to the embodiment of the present invention prevents the discoloration of Ag when applied to and used as an antibacterial agent in a product, and also exhibits antioxidant performance, enabling efficient long-term use.

[0130] As a result, the phosphate-based antibacterial glass powder 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.

[0131]

[0132] Examples

[0133] 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.

[0134] Details not listed here can be sufficiently technically inferred by a person skilled in this field, so their explanation will be omitted.

[0135]

[0136] 1. Preparation of glass powder samples

[0137] Table 1 shows the composition and composition ratio of phosphate-based antibacterial glass powders according to Examples 1 to 5 and Comparative Examples 1 to 3. At this time, the phosphate-based antibacterial glass compositions mixed according to the composition and composition ratios listed in Table 1 were each melted in an electric furnace at a temperature of 1,200°C, and then quenched on a stainless steel plate by air cooling (glass bulk form) and quenched using a twin roll to obtain cullet-shaped glass. Subsequently, the material 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.

[0138] 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 the same as those listed in Table 1. 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.

[0139]

[0140] [Table 1] (Unit: mol%)

[0141]

[0142]

[0143] 2. Evaluation of Glass Powder Physical Properties

[0144] Table 2 shows the results of the physical property evaluation for phosphate-based antibacterial glass powder samples prepared according to Examples 1 to 5 and Comparative Examples 1 to 3.

[0145]

[0146] 1) Measurement of antibacterial activity

[0147] For Examples 1 to 5 and Comparative Examples 1 to 2, in which homogeneous vitrification was performed, the number of viable cells was measured after 1 hour of exposure to two bacteria (Staphylococcus aureus, Escherichia coli, K) according to the shaking flask method (ASTM E2149-13a).

[0148]

[0149] 2) Durability evaluation (antimicrobial persistence)

[0150] To evaluate the durability (antibacterial persistence) of the antibacterial glass powder prepared according to Examples 1 to 5 and Comparative Examples 1 to 2, an additional antibacterial activity test was conducted by exposing the antibacterial glass powder to distilled water and drying it, then leaching it at 50°C for 32 hours, in accordance with ASTM C1285 - 14 (Glat and glass ceramic durability evaluation method).

[0151]

[0152] 3) Evaluation of discoloration characteristics

[0153] To evaluate the discoloration characteristics of the antibacterial glass powder prepared according to Examples 1 to 5 and Comparative Examples 1 to 2, the changes in color difference L, a, and b before and after 2 weeks of exposure under UV 30W, 5cm conditions were measured.

[0154]

[0155] [Table 2]

[0156]

[0157] As shown in Tables 1 and 2, the maximum antibacterial activity of the shaking flask method is 99.9%. At this time, it was confirmed that the phosphate-based antibacterial glass powders prepared according to Examples 1 to 5 exhibited excellent antibacterial activity of over 99% and antibacterial persistence (antibacterial activity after durability evaluation).

[0158] On the other hand, it was confirmed that the phosphate-based antibacterial glass powders prepared according to Comparative Examples 1 and 2 had excellent antibacterial activity of over 99%, but poor antibacterial persistence (antibacterial activity after durability evaluation).

[0159]

[0160] In addition, it was confirmed that the phosphate-based antibacterial glass powders prepared according to Examples 1 to 5 did not show significant changes in the color difference L, a, and b (ΔL, Δa, Δb). In particular, it was confirmed that the phosphate-based antibacterial glass powder prepared according to Example 3 showed almost no change in color.

[0161] On the other hand, it was confirmed that the phosphate-based antibacterial glass powders prepared according to Comparative Examples 1 and 2 showed discoloration with a large deviation in the change amounts (ΔL, Δa, Δb) of color difference L, a, and b.

[0162]

[0163] As can be seen from the experimental results above, it was confirmed that the phosphate-based antibacterial glass powders prepared according to Examples 1 to 5 suppressed the chronic problems of Ag-containing phosphate glass, namely antibacterial persistence and discoloration, by optimizing the mixing ratio of MgO, ZnO, and TiO2 components considering light absorption characteristics and ionization tendency without adding Na2O, K2O, CaO, and Al2O3.

[0164] In addition, the phosphate-based antibacterial glass powders prepared according to Examples 1 to 5 are capable of vitrifying Ag into an ionic state without the adverse effect of causing discoloration of the utilized TiO2, instead of excluding the addition of alkali components. Furthermore, it is determined that when Ag ions are leached out in the usage environment to perform antibacterial action, they are leached out together to inhibit the reduction of Ag.

[0165]

[0166] 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.

[0167]

[0168] [Explanation of the symbol]

[0169] S110: Mixing step

[0170] S120: Melting stage

[0171] S130: Cooling stage

[0172] S140: Grinding step

Claims

1. P2O530 ~ 40 mol%; B2O35 ~ 15 mol%; MgO 15 ~ 50 mol%; ZnO 10 ~ 40 mol%; TiO2 0.2 ~ 1.5 mol%; and Ag2O 0.2 ~ 1.0 mol%; including, Phosphate-based antibacterial glass composition.

2. In Paragraph 1, Excluding the addition of Na2O, K2O, CaO, and Al2O3, Phosphate-based antibacterial glass composition.

3. In Paragraph 1, The above P2O5 is added in an amount of 30.1 to 38.9 mol%, Phosphate-based antibacterial glass composition.

4. In Paragraph 1, The above B2O3 is added in an amount of 5.5 to 12 mol%, Phosphate-based antibacterial glass composition.

5. In Paragraph 1, The above MgO is added in an amount of 30 to 49 mol%, Phosphate-based antibacterial glass composition.

6. In Paragraph 1, The above ZnO is added in an amount of 10 to 30 mol%, Phosphate-based antibacterial glass composition.

7. (a) A step of forming a phosphate-based antibacterial glass composition by mixing and stirring P2O530 ~ 40 mol%, B2O35 ~ 15 mol%, MgO 15 ~ 50 mol%, ZnO 10 ~ 40 mol%, TiO20.2 ~ 1.5 mol%, and Ag2O 0.2 ~ 1.0 mol%; (b) a step of melting the above phosphate-based antibacterial glass composition; (c) a step of cooling the molten phosphate-based antibacterial glass composition; and (d) a step of crushing the cooled phosphate-based antibacterial glass to obtain phosphate-based antibacterial glass powder; comprising, Method for manufacturing phosphate-based antibacterial glass powder.

8. In Paragraph 7, In the above (a) step, Excluding the addition of Na2O, K2O, CaO, and Al2O3, Method for manufacturing phosphate-based antibacterial glass powder.

9. In Paragraph 7, In the above (a) step, The above P2O5 is added in an amount of 30.1 to 38.9 mol%, Method for manufacturing phosphate-based antibacterial glass powder.

10. In Paragraph 7, In the above (a) step, The above B2O3 is added in an amount of 5.5 to 12 mol%, Method for manufacturing phosphate-based antibacterial glass powder.

11. In Paragraph 7, In the above (a) step, The above MgO is added in an amount of 30 to 49 mol%, Method for manufacturing phosphate-based antibacterial glass powder.

12. In Paragraph 7, In the above (a) step, The above ZnO is added in an amount of 10 to 30 mol%, Method for manufacturing phosphate-based antibacterial glass powder.

13. In Paragraph 7, In step (b) above, The above melting Performed at 1,000 ~ 1,400℃ for 30 ~ 90 minutes, Method for manufacturing phosphate-based antibacterial glass powder.

14. In Paragraph 7, In step (d) above, The above phosphate-based antibacterial glass powder is having an average diameter of 50㎛ or less, Method for manufacturing phosphate-based antibacterial glass powder.

15. A phosphate-based antibacterial glass powder manufactured by a manufacturing method according to any one of claims 7 to 14, It contains P2O530 ~ 40 mol%, B2O35 ~ 15 mol%, MgO 15 ~ 50 mol%, ZnO 10 ~ 40 mol%, TiO2 0.2 ~ 1.5 mol%, and Ag2O 0.2 ~ 1.0 mol%, and Excluding the addition of Na2O, K2O, CaO, and Al2O3, Phosphate-based antibacterial glass powder.

16. In Paragraph 15, The above phosphate-based 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, Phosphate-based antibacterial glass powder.

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