WO2022145821A1 - Composite glass composition, preparation method therefor, and cooking apparatus comprising same - Google Patents

Composite glass composition, preparation method therefor, and cooking apparatus comprising same Download PDF

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Publication number
WO2022145821A1
WO2022145821A1 PCT/KR2021/019100 KR2021019100W WO2022145821A1 WO 2022145821 A1 WO2022145821 A1 WO 2022145821A1 KR 2021019100 W KR2021019100 W KR 2021019100W WO 2022145821 A1 WO2022145821 A1 WO 2022145821A1
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weight
composition
antibacterial
glass composition
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PCT/KR2021/019100
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French (fr)
Korean (ko)
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박선영
손제구
김영석
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엘지전자 주식회사
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Publication of WO2022145821A1 publication Critical patent/WO2022145821A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/024—Chemical treatment of cullet or glass fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
    • C03C2207/02—Compositions specially applicable for the manufacture of vitreous enamels containing ingredients for securing a good bond between the vitrified enamel and the metal

Definitions

  • the present invention relates to a composite glass composition, a method for manufacturing the same, and a cooking appliance including the same.
  • Enamel is a glassy glaze applied to the surface of a metal plate. Common enamel is used in cooking appliances such as microwave ovens and ovens. BACKGROUND ART Cooking appliances such as electric ovens and gas ovens are appliances that cook food using a heating source.
  • the enamel is coated on the surface of the inner wall of the cavity of the cooking device to facilitate the removal of contaminants attached to the cooking device.
  • Bacteria inhabiting these cooking appliances are very diverse, and main strains may be different for each part.
  • Patent Document 1 KR Patent Publication No. 10-2008-0110144 (published on December 18, 2008)
  • An object of the present invention is to provide a composite glass composition that is harmless to the human body and exhibits excellent antibacterial performance by simply adding an antibacterial glass powder without changing the performance and appearance of the enamel composition, thereby permanently maintaining the antibacterial function, and a method for manufacturing the same, including the same
  • an object of the present invention is a composite glass composition that secures excellent antibacterial performance by adding an antibacterial glass powder using Zn and Sn to an enamel composition in an optimal content ratio without using Ag, which is widely used in the past, and a method for manufacturing the same And to provide a cooking appliance including the same.
  • SiO 2 -B 2 O 3 having excellent durability in a network structure, to maintain or improve durability, and to interact with ZnO and SnO, which are components that exhibit antibacterial performance, so that two or more kinds of alkali oxides ( Na 2 O, K 2 O) and alkaline earth oxides (CaO, MgO) are added in an optimal content ratio to provide a composite glass composition with improved durability and antibacterial properties, a method for manufacturing the same, and a cooking appliance including the same will be.
  • alkali oxides Na 2 O, K 2 O
  • CaO, MgO alkaline earth oxides
  • the composite glass composition according to the present invention prevent the growth of microorganisms in areas in contact with food or various contaminants in advance by adding an antibacterial glass powder having excellent durability to the enamel composition be able to do
  • the composite glass composition according to the present invention, the manufacturing method thereof, and the cooking appliance including the same are environmentally friendly because Ag, Cu, etc., which were used to implement antibacterial performance, are not used and are made of only ingredients that are harmless to the environment and the human body. Rather, it can be applied to various fields due to its excellent price competitiveness.
  • the composite glass composition according to the present invention a method for manufacturing the same, and a cooking appliance including the same have SiO 2 -B 2 O 3 having excellent durability in a network structure, maintain or improve durability, and contain ZnO, an antibacterial performance component, and By adding two or more kinds of alkali oxides (Na 2 O, K 2 O) and alkaline earth oxides (CaO, MgO) in an optimal content ratio to interact with SnO, durability and antibacterial properties can be improved.
  • alkali oxides Na 2 O, K 2 O
  • CaO, MgO alkaline earth oxides
  • the composite glass composition according to the present invention includes an enamel composition and an antibacterial glass powder mixed with the enamel composition, and the antibacterial glass powder is SiO 2 26 to 50 wt%, B 2 O 3 and P 2 O 5 One kind 0.5 to 4 wt% or more, 15 to 27 wt% of at least one of Na 2 O and K 2 O, 3 to 20 wt% of at least one of CaO, MgO and WO 3 , and 22 to 44 wt% of at least one of ZnO and SnO % by weight.
  • Na 2 O is preferably added in an amount of 5 to 18% by weight
  • K 2 O is preferably added in an amount of 5 to 13% by weight.
  • the composite glass composition according to an embodiment of the present invention is preferably mixed in 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder.
  • the enamel composition is P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1-20 wt%, Li 2 O 1-10 wt%, NaF 5 wt% or less, B 2 O 3 1-20 wt%, TiO 2 5 wt% or less and V 2 O 5 10 wt% or less can do.
  • the present invention it is possible to maintain the antibacterial function permanently by exhibiting excellent antibacterial performance while harmless to the human body by simply adding antibacterial glass powder without changing the performance and appearance of the enamel composition.
  • the antibacterial glass powder having excellent durability to the enamel composition, it is possible to suppress in advance the growth of microorganisms in the portion in contact with food or various contaminants.
  • FIG. 1 is a process flow chart showing a method for manufacturing a composite glass composition according to an embodiment of the present invention.
  • the composite glass composition according to an embodiment of the present invention is harmless to the human body and exhibits excellent antibacterial performance by simply adding antibacterial glass powder without any change in the performance and appearance of the enamel composition, thereby permanently maintaining the antibacterial function.
  • the composite glass composition according to an embodiment of the present invention secured excellent antibacterial performance by adding an antibacterial glass powder using Zn and Sn to the enamel composition in an optimal content ratio without using Ag, which is widely used in the past.
  • the composite glass composition according to an embodiment of the present invention has a highly durable SiO 2 -B 2 O 3 network structure, maintains or improves durability, and enables interaction between ZnO and SnO, which are components that exhibit antibacterial performance.
  • Two or more kinds of alkali oxides (Na 2 O, K 2 O) and alkaline earth oxides (CaO, MgO) were added in an optimal content ratio.
  • the composite glass composition according to an embodiment of the present invention includes an enamel composition and an antibacterial glass powder mixed in the enamel composition, and the antibacterial glass powder is SiO 2 26 to 50 wt%, B 2 O 3 and P 2 O 5 at least 0.5 to 4% by weight, at least one of Na 2 O and K 2 O at least 15 to 27% by weight, at least 3 to 20% by weight of at least one of CaO, MgO and WO 3 , and at least one of ZnO and SnO 22 to 44% by weight.
  • the antibacterial glass powder is SiO 2 26 to 50 wt%, B 2 O 3 and P 2 O 5 at least 0.5 to 4% by weight, at least one of Na 2 O and K 2 O at least 15 to 27% by weight, at least 3 to 20% by weight of at least one of CaO, MgO and WO 3 , and at least one of ZnO and SnO 22 to 44% by weight.
  • Na 2 O is preferably added in an amount of 5 to 18 wt%
  • K 2 O is preferably added in an amount of 5 to 13 wt%.
  • Na 2 O and K 2 O are more preferably added in a range satisfying the following formula (1).
  • Equation 1 0.5 ⁇ [Na 2 O] / [K 2 O] ⁇ 1.5
  • [] represents the content ratio of each component.
  • the antibacterial glass powder may further include 0.1 wt% or less of one or more of Ag 2 O, Ag 3 PO 4 and AgNO 3 .
  • the composite glass composition according to an embodiment of the present invention is preferably mixed with 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder, and more preferably 90 to 99% by weight of the enamel composition; and 1 to 10% by weight of antibacterial glass powder.
  • the antibacterial glass powder is added in an amount of less than 0.5% by weight of the total weight of the composite glass composition, it may be difficult to improve durability and antibacterial properties. Conversely, when the antibacterial glass powder exceeds 20% by weight of the total weight of the composite glass composition, the antibacterial performance is improved, but there is a risk of deterioration in appearance and performance, which is not preferable.
  • the antibacterial glass powder is mixed with the enamel composition, but this is exemplary and it is also possible to add the same ingredients and ratios to the glaze in addition to the enamel.
  • the enamel composition may be applied without particular limitation, as long as it is coated and used for cooking devices such as microwave ovens, ovens, gas ranges, and the like.
  • the enamel composition is P 2 O 5 10 to 35% by weight, SiO 2 10 to 45% by weight, Al 2 O 3 5 to 20% by weight, ZrO 2 10% by weight or less, Na 2 O 1 to 15% by weight, 1 to 20 wt% of K 2 O, 1 to 10 wt% of Li 2 O, 5 wt% or less of NaF, 1 to 20 wt% of B 2 O 3 , 5 wt% or less of TiO 2 and 10 wt% or less of V 2 O 5 may include
  • the enamel composition may further include 5 wt% or less of at least one of Co 3 O 4 , MnO 2 , NiO and Fe 2 O 3 .
  • the composite glass composition according to the above-described embodiment of the present invention is harmless to the human body and exhibits excellent antibacterial performance by simply adding antibacterial glass powder without changing the performance and appearance of the enamel composition, thereby maintaining the antibacterial function permanently.
  • the antibacterial glass powder having excellent durability is added to the enamel composition, it is possible to suppress the growth of microorganisms in advance in the portion in contact with food or various contaminants.
  • the composite glass composition according to an embodiment of the present invention does not use Ag, Cu, etc., which were used to implement antibacterial performance, and is made of only ingredients that are harmless to the environment and human body, it is not only eco-friendly but also has excellent price competitiveness in various fields It may be possible to apply to
  • SiO 2 , B 2 O 3 , and P 2 O 5 are network-forming oxides, which form the skeletal structure of glass and are key components that enable vitrification by covalent bonding.
  • SiO 2 is a glass former that enables vitrification, and in terms of the structure of the glass, it is a key component that serves as a framework. When such SiO 2 is contained in an appropriate amount or more, the viscosity increases when the glass is melted, and thus workability and yield are deteriorated in the cooling process. In addition, SiO 2 does not act as a direct component that exhibits antibacterial activity, but forms less OH - groups on the glass surface compared to P 2 O 5 , which is a typical network-forming oxide, so that the glass surface caused by metal ions in the glass is positively charged. It is advantageous to make
  • SiO 2 is preferably added in a content ratio of 26 to 50% by weight of the total weight of the antimicrobial glass composition according to the present invention.
  • the amount of SiO 2 added is less than 26% by weight, opacification may occur or a heterogeneity phenomenon in which transparent glass is mixed may occur due to a lack of network-forming oxides and leaving the vitrification region.
  • the amount of SiO 2 added exceeds 50% by weight, it is difficult to control the surface charge of the glass to a positive value, so that the antibacterial activity may be reduced.
  • B 2 O 3 and P 2 O 5 are key components that enable sufficient vitrification together with SiO 2 as representative network-forming oxides.
  • B 2 O 3 and P 2 O 5 have a low melting point and are used for lowering the eutectic point of the melt.
  • B 2 O 3 and P 2 O 5 When melting (melting) for vitrification, a homogeneous glass by performing an action of increasing the solubility of rigid components (Al 2 O 3 , CuO, etc.) help to become
  • B 2 O 3 and P 2 O 5 are added in a certain amount or more, a problem of weakening the bonding structure of the glass to reduce water resistance, etc. may occur.
  • B 2 O 3 and P 2 O 5 are preferably used in trace amounts only for lowering the melting point in order to implement water-insoluble antibacterial glass.
  • At least one of B 2 O 3 and P 2 O 5 is preferably added in a content ratio of 0.5 to 4% by weight of the total weight of the antimicrobial glass composition according to the present invention.
  • B 2 O 3 and P 2 O 5 is added in an amount of less than 0.5% by weight, the flux is insufficient, and thus it leaves the vitrification region, which may cause unmelting.
  • B 2 O 3 and P 2 O 5 exceeds 4% by weight, a decrease in water resistance may occur due to structural problems of B and P in the network-forming structure due to the properties of the element itself.
  • SiO 2 is preferably added in an amount higher than the content of B 2 O 3 , because it is advantageous to ensure water resistance when the amount of SiO 2 is higher than the amount of B 2 O 3 added.
  • Alkali oxides such as Na 2 O and K 2 O
  • Na 2 O and K 2 O are oxides that serve as a network modifier for non-crosslinking in the glass composition. Although these components cannot be vitrified alone, vitrification is possible when mixed with a network former such as SiO 2 and B 2 O 3 in a certain ratio. If only one component of Na 2 O and K 2 O is included in the glass composition, the durability of the glass may be weakened in the area where vitrification is possible. However, when two or more components are included in the glass composition, the durability of the glass is improved again according to the ratio. This is called the mixed alkali effect.
  • alkali oxides such as Na 2 O and K 2 O improve the antimicrobial activity by using the point that first occupies the modification oxide site in the glass.
  • alkali oxides such as Na 2 O and K 2 O contribute to the formation of a network of intermediate oxides such as ZnO and SnO, thereby enhancing durability, contributing to antibacterial activity due to water-insoluble properties and surface charge. do.
  • At least one of Na 2 O and K 2 O is preferably added in a content ratio of 15 to 27% by weight of the total weight of the antimicrobial glass composition according to the present invention.
  • a phenomenon in which an unmelted product is formed may occur due to leaving the vitrification region because the flux is insufficient.
  • alkali ions are easily replaced with H 3 O + ions of water according to the basic elution mechanism of the glass and water resistance that elution is intensified degradation may occur.
  • Na 2 O is added in an amount of 5 to 18% by weight
  • K 2 O is more preferably added in an amount of 5 to 13% by weight.
  • Na 2 O and K 2 O are preferably added in a range satisfying the following formula (1).
  • Equation 1 0.5 ⁇ [Na 2 O] / [K 2 O] ⁇ 1.5
  • [] represents the content ratio of each component.
  • Alkaline earth oxides such as CaO, MgO, and WO 3 are basically oxides that play the role of modifying oxides that are non-crosslinked in glass. Vitrification is impossible by itself, but vitrification is possible when mixed with a network former such as SiO 2 and B 2 O 3 in a certain ratio.
  • alkaline earth oxides such as CaO, MgO, and WO 3 have a +2 charge and have to be substituted with two water molecule ions, so ion exchange is relatively difficult, so it is used as a durability enhancing element. It is also used Therefore, alkaline earth oxides such as CaO, MgO, and WO 3 have strong durability among modified oxides and occupy a modified oxide site, which structurally indirectly contributes to the expression of water insolubility and antibacterial properties. oxide) for the same purpose.
  • At least one of CaO, MgO and WO 3 is preferably added in a content ratio of 3 to 20% by weight based on the total weight of the antimicrobial glass composition according to the present invention.
  • at least one of CaO, MgO, and WO 3 is less than 3 wt%, since the structure cannot be strengthened at the modified oxide site, a water resistance deterioration phenomenon that cannot prevent alkali elution may occur.
  • the alkaline earth oxide which is a material that melts at a high temperature, does not melt sufficiently, and thus leaves the vitrification region, resulting in the formation of an unmelted product. can occur
  • ZnO and SnO are components that are substituted with a part of the network-forming oxide and form a covalent bond to perform both the role of the network-forming oxide and the modifying oxide.
  • ZnO and SnO are components that greatly contribute to the expression of the antibacterial effect.
  • ZnO and SnO are intermediate oxides, and in order to participate in the network-forming structure in glass, the atomic radius is small and the electronegativity is large, so the difference from oxygen must be small. These intermediate oxides have a larger atomic radius and lower electronegativity than conventional network-forming oxides, such as Si, P, and B, making it difficult to form glass alone. say ingredients. These ZnO and SnO act only as modified oxides below a certain content, but above a certain content, they form a covalent bond, and the durability is radically improved.
  • the predetermined content is determined by the content of the network-forming oxide and the modifying oxide.
  • ZnO and at least one SnO is preferably added in a content ratio of 22 to 44% by weight of the total weight of the antimicrobial glass composition according to the present invention.
  • ZnO and SnO is added in an amount of less than 22% by weight, there is a problem in that sufficient antibacterial activity cannot be expressed because the absolute amount of the material exhibiting antibacterial performance is insufficient.
  • at least one of ZnO and SnO is added in excess of 44 wt%, opacification occurs due to the fact that it does not exist as an ionic state in the glass under homogeneity, and partially forms crystals to escape the vitrification region, resulting in opacification and transparent glass A heterogeneity phenomenon in which the are mixed may occur.
  • Ag 2 O, Ag 3 PO 4 and AgNO 3 are present in an ionic state in the glass, and are effective components for expressing antibacterial activity.
  • Ag 2 O, Ag 3 PO 4 and AgNO 3 serves to lower the melting point.
  • at least one of Ag 2 O, Ag 3 PO 4 and AgNO 3 is added in excess of 0.1 wt%, there is a risk of destabilizing vitrification due to precipitation of silver metal. Accordingly, at least one of Ag 2 O, Ag 3 PO 4 and AgNO 3 is preferably added in a strictly limited amount of 0.1 wt% or less of the total weight of the antimicrobial glass composition according to the present invention.
  • FIG. 1 is a process flow chart showing a method for manufacturing a composite glass composition according to an embodiment of the present invention.
  • the method for manufacturing a composite glass composition includes a primary mixing step (S110), a melting step (S120), a cooling step (S130), a grinding step (S140), and the secondary mixing.
  • Step S150 is included.
  • SiO 2 26-50 wt%, B 2 O 3 and P 2 O 5 one or more 0.5-4 wt%, Na 2 O and K 2 O one or more 15-27 wt%, CaO, MgO, and 3 to 20% by weight of at least one of WO 3 , and 22 to 44% by weight of at least one of ZnO and SnO are mixed and stirred to form an antibacterial glass composition.
  • Na 2 O is added in an amount of 5 to 18% by weight
  • K 2 O is preferably added in an amount of 5 to 13% by weight.
  • Equation 1 0.5 ⁇ [Na 2 O] / [K 2 O] ⁇ 1.5
  • [] represents the content ratio of each component.
  • the antimicrobial glass composition may further include 0.1 wt% or less of at least one of Ag 2 O, Ag 3 PO 4 and AgNO 3 .
  • the antimicrobial glass composition is melted.
  • the melting is preferably carried out at 1,100 ⁇ 1,400 °C for 1 ⁇ 60 minutes. If the melting temperature is less than 1,100° C. or the melting time is less than 1 minute, the antibacterial glass composition cannot completely melt, thereby causing an immiscibility of the glass melt. Conversely, when the melting temperature exceeds 1,400° C. or the melting time exceeds 60 minutes, it is not economical because excessive energy and time are required.
  • the molten antibacterial glass composition is cooled to room temperature.
  • the cooling is preferably performed in a cooling in furnace method.
  • furnace cooling is preferable.
  • the cooled antibacterial glass is crushed.
  • any one of a commonly known ball mill, jet mill, and planetary mill may be applied for the pulverization.
  • the antibacterial glass is finely pulverized to produce an antibacterial glass powder.
  • the antibacterial glass powder preferably has an average diameter of 80 ⁇ m or less, and can present an average diameter of 10 to 30 ⁇ m as a more preferable range.
  • the pulverized antibacterial glass powder is mixed with the enamel composition to form a composite glass composition.
  • the composite glass composition is preferably mixed in 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder, more preferably 90 to 99% by weight, and 1 to 10% by weight of the antibacterial glass powder can be presented
  • the antibacterial glass powder is added in an amount of less than 0.5% by weight of the total weight of the composite glass composition, it may be difficult to improve durability and antibacterial properties. Conversely, when the antibacterial glass powder exceeds 20% by weight of the total weight of the composite glass composition, the antibacterial performance is improved, but there is a risk of deterioration in appearance and performance, which is not preferable.
  • the enamel composition may be applied without particular limitation as long as it is used by coating on cooking devices such as microwave ovens, ovens, gas ranges, and the like.
  • the enamel composition is P 2 O 5 10 to 35% by weight, SiO 2 10 to 45% by weight, Al 2 O 3 5 to 20% by weight, ZrO 2 10% by weight or less, Na 2 O 1 to 15% by weight, 1 to 20 wt% of K 2 O, 1 to 10 wt% of Li 2 O, 5 wt% or less of NaF, 1 to 20 wt% of B 2 O 3 , 5 wt% or less of TiO 2 and 10 wt% or less of V 2 O 5 may include
  • the enamel composition may further include 5 wt% or less of at least one of Co 3 O 4 , MnO 2 , NiO and Fe 2 O 3 .
  • the composite glass composition according to the embodiment of the present invention may be manufactured.
  • the cooking appliance according to an embodiment of the present invention includes an injection molded product in which the composite glass composition is added to the base material or the composite glass composition is coated on the surface of the base material.
  • the cooking appliance may include a microwave oven, an oven, and the like, but is not limited thereto.
  • the base material may be a polymer resin or a metal material.
  • the composite glass composition includes an enamel composition and an antibacterial glass powder mixed in the enamel composition.
  • the antibacterial glass powder is SiO 2 26 to 50% by weight, B 2 O 3 and P 2 O 5 at least 0.5 to 4% by weight, Na 2 O and K 2 O at least 15 to 27% by weight, CaO, 3-20 wt% of at least one of MgO and WO 3 , and 22-44 wt% of at least one of ZnO and SnO.
  • the composite glass composition is mixed with 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder.
  • the enamel composition is P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1-20 wt%, Li 2 O 1-10 wt%, NaF 5 wt% or less, B 2 O 3 1-20 wt%, TiO 2 5 wt% or less and V 2 O 5 10 wt% or less do.
  • the enamel composition may further include 5 wt% or less of at least one of Co 3 O 4 , MnO 2 , NiO and Fe 2 O 3 .
  • Table 1 shows the compositions of the antibacterial glass compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 and their composition ratios. At this time, each of the antibacterial glass compositions having the compositions described in Examples 1 to 5 and Comparative Examples 1 to 3 were melted in an electric furnace at a temperature of 1,200 ° C. (cullet) form of antibacterial glass was obtained. Thereafter, the antibacterial glass was pulverized with a dry grinder (ball mill), and then passed through a 400 mesh sieve to prepare an antibacterial glass powder.
  • a dry grinder ball mill
  • the raw materials of the components Na 2 O, K 2 O, and CaO were Na 2 CO 3 , K 2 CO 3 , and CaCO 3 , respectively, and the remaining components were the same as those described in Table 1 were used.
  • vitrification was classified based on a case in which a homogeneous glassy appearance and a phenomenon in which opacification and unmelted matter occurred.
  • the antibacterial glass compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 prepared by the above method were added to the enamel composition in the content ratio shown in Table 1, and mixed using a 3D powder mixer to form a composite.
  • a glass composition was prepared.
  • 0.05 parts by weight of a silane coupling agent was further mixed with respect to 100 parts by weight of the composite glass compositions according to Examples 1 to 3 and Comparative Examples 1 to 2 to prepare enamel in the dry method.
  • the composite glass compositions according to Examples 4 to 5 and Comparative Example 3 were mixed with water in a weight ratio of 1:1, and clay aluminum oxide, based on 100 parts by weight of the composite glass composition, An additional 0.05 parts by weight of the sum of borax and bentonite was added and mixed for 10 hours.
  • the composite glass compositions according to Examples 1 to 3 and Comparative Examples 1 to 2 prepared in a dry method were sprayed on a low-carbon steel sheet using a corona discharge gun to form an enamel coating layer, and after spraying, a low-carbon steel sheet with an enamel coating layer was applied to 850
  • An enamel specimen was prepared by calcination at a temperature of °C for 7 minutes.
  • the voltage of the discharge gun was controlled to 60 kV.
  • the wet-prepared composite glass compositions according to Examples 4 to 5 and Comparative Example 3 were sprayed onto a low-carbon steel sheet using an air spray gun, and after spraying, the low-carbon steel sheet with an enamel coating layer was applied to a temperature condition of 860°C. Enameled specimens were prepared by firing for 8 minutes.
  • An enamel composition comprising wt%, B 2 O 3 10.5 wt%, TiO 2 1.0 wt%, V 2 O 5 6.2 wt%, MnO 2 1.1 wt%, and Fe 2 O 3 1.0 wt% was prepared.
  • 0.05 parts by weight of a silane coupling agent was further mixed, and then sprayed on a low-carbon steel sheet using a corona discharge gun to form an enamel coating layer. After spraying, the enamel coating layer The formed low-carbon steel sheet was fired at a temperature of 850° C. for 7 minutes to prepare an enamel specimen.
  • the voltage of the discharge gun was controlled to 60 kV.
  • Table 2 shows the antibacterial performance evaluation results for the specimens prepared according to Examples 1 to 5 and Comparative Examples 1 to 3.
  • the antibacterial standard test JIS Z 2801, film adhesion method
  • Staphylococcus aureus and Escherichia coil Antibacterial against The activity level was confirmed, and the antibacterial activity level against Klebsiella pneumonia and Pseudomonas aeruginosa was additionally evaluated.
  • the specimens prepared according to Examples 1 to 5 exhibited excellent antibacterial activity of 99.99% or more in all four bacteria.
  • Comparative Example 1 On the other hand, the sample prepared according to Comparative Example 1 exhibited an antibacterial activity of 99.9% on all four bacteria, and Comparative Examples 2 and 3 showed an antibacterial activity of 80% or less on all four bacteria.
  • Table 3 shows the enamel appearance evaluation results for the specimens prepared according to Examples 3 and 5 and Comparative Example 4. At this time, in order to evaluate the enamel appearance of the specimens prepared according to Examples 3 and 5 and Comparative Example 4, measurements were made using a colorimeter (Minolta CR-400) and a glossmeter (BYK AG-4446).

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Abstract

Disclosed are: a composite glass composition designed to exhibit, by the simple addition of an antibacterial glass powder without a change in the performance and appearance of an enamel composition, excellent antibacterial performance while being harmless to the human body, so as to be capable of permanently maintaining an antibacterial function; a method for preparing the composite glass powder; and a cooling apparatus comprising same.

Description

복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기Composite glass composition, method for manufacturing same, and cooking appliance comprising same
본 발명은 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기에 관한 것이다.The present invention relates to a composite glass composition, a method for manufacturing the same, and a cooking appliance including the same.
법랑(enamel)은 금속판의 표면에 유리질 유약을 도포시킨 것이다. 일반적인 법랑은 전자레인지와 오븐과 같은 조리기기 등에 사용된다. 전기오븐, 가스 오븐 등의 조리기기는 가열원을 이용하여 음식물을 조리하는 기기이다.Enamel is a glassy glaze applied to the surface of a metal plate. Common enamel is used in cooking appliances such as microwave ovens and ovens. BACKGROUND ART Cooking appliances such as electric ovens and gas ovens are appliances that cook food using a heating source.
조리과정에서 발생한 오염물질 등이 조리기기의 캐비티(cavity) 내벽에 들러붙게 되므로, 캐비티 내벽을 청소할 필요가 있다. 또한, 법랑은 조리기기의 캐비티 내벽 표면 등에 코팅되어 조리기기에 묻은 오염물의 제거를 용이하게끔 한다.Since contaminants generated during the cooking process adhere to the inner wall of the cavity of the cooking appliance, it is necessary to clean the inner wall of the cavity. In addition, the enamel is coated on the surface of the inner wall of the cavity of the cooking device to facilitate the removal of contaminants attached to the cooking device.
이러한 조리기기에 서식하는 균은 매우 다양하고, 부품 별로 주요 균주가 상이할 수 있다.Bacteria inhabiting these cooking appliances are very diverse, and main strains may be different for each part.
최근에는 법랑에 대한 항균 성능을 높이기 위해 법랑에 무기 항균제를 첨가하려는 시도가 있었다. 그러나, 법랑에 무기 항균제를 첨가할 시 항균 성능은 향상시킬 수 있으나, 외관 변화와 더불어 내열성, 내화학성 등의 물성이 저하되는 문제가 있었다.Recently, an attempt has been made to add inorganic antibacterial agents to enamel in order to increase the antibacterial performance of the enamel. However, when an inorganic antibacterial agent is added to the enamel, the antibacterial performance can be improved, but there is a problem in that physical properties such as heat resistance and chemical resistance are deteriorated along with a change in appearance.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 1) KR 공개특허공보 제10-2008-0110144호(2008.12.18. 공개)(Patent Document 1) KR Patent Publication No. 10-2008-0110144 (published on December 18, 2008)
본 발명의 목적은 법랑 조성물의 성능 및 외관에 대한 변화 없이 항균 유리 분말의 단순 첨가만으로 인체에 무해하면서도 우수한 항균 성능을 나타내어 영구적으로 항균 기능을 유지할 수 있는 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기를 제공하는 것이다.An object of the present invention is to provide a composite glass composition that is harmless to the human body and exhibits excellent antibacterial performance by simply adding an antibacterial glass powder without changing the performance and appearance of the enamel composition, thereby permanently maintaining the antibacterial function, and a method for manufacturing the same, including the same To provide cooking equipment for
또한, 본 발명의 목적은 기존에 널리 사용하는 Ag를 사용하지 않고 Zn과 Sn을 사용한 항균 유리 분말을 법랑 조성물에 최적의 함량비로 첨가하는 것에 의해 우수한 항균 성능을 확보한 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기를 제공하는 것이다.In addition, an object of the present invention is a composite glass composition that secures excellent antibacterial performance by adding an antibacterial glass powder using Zn and Sn to an enamel composition in an optimal content ratio without using Ag, which is widely used in the past, and a method for manufacturing the same And to provide a cooking appliance including the same.
아울러, 본 발명의 목적은 내구성이 뛰어난 SiO2-B2O3를 망목구조로 가지며, 내구성을 유지 또는 향상시키며 항균 성능 발현 성분인 ZnO와 SnO와의 상호작용을 할 수 있도록 2 종 이상의 알칼리 산화물(Na2O, K2O)와 알칼리 토류 산화물(CaO, MgO)을 최적의 함량비로 첨가하는 것에 의해, 내구성 및 항균성을 향상시킨 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기를 제공하는 것이다.In addition, it is an object of the present invention to have SiO 2 -B 2 O 3 having excellent durability in a network structure, to maintain or improve durability, and to interact with ZnO and SnO, which are components that exhibit antibacterial performance, so that two or more kinds of alkali oxides ( Na 2 O, K 2 O) and alkaline earth oxides (CaO, MgO) are added in an optimal content ratio to provide a composite glass composition with improved durability and antibacterial properties, a method for manufacturing the same, and a cooking appliance including the same will be.
본 발명의 목적들은 이상에서 언급한 목적으로 제한되지 않으며, 언급되지 않은 본 발명의 다른 목적 및 장점들은 하기의 설명에 의해서 이해될 수 있고, 본 발명의 실시예에 의해 보다 분명하게 이해될 것이다. 또한, 본 발명의 목적 및 장점들은 특허 청구 범위에 나타낸 수단 및 그 조합에 의해 실현될 수 있음을 쉽게 알 수 있을 것이다.The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned may be understood by the following description, and will be more clearly understood by the examples of the present invention. It will also be readily apparent that the objects and advantages of the present invention may be realized by the means and combinations thereof indicated in the appended claims.
본 발명에 따른 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기는 내구성이 우수한 항균 유리 분말이 법랑 조성물에 첨가되는 것에 의해, 식품이나 각종 오염물이 닿는 부분에서 미생물들이 성장하는 것을 미연에 억제할 수 있게 된다.The composite glass composition according to the present invention, a method for manufacturing the same, and a cooking appliance including the same prevent the growth of microorganisms in areas in contact with food or various contaminants in advance by adding an antibacterial glass powder having excellent durability to the enamel composition be able to do
또한, 본 발명에 따른 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기는 항균 성능을 구현하기 위해 사용되던 Ag, Cu 등이 사용되지 않고, 환경 및 인체에 무해한 성분들로만 이루어지므로 친환경적일 뿐만 아니라, 가격 경쟁력이 뛰어나 다양한 분야에 적용하는 것이 가능해질 수 있다.In addition, the composite glass composition according to the present invention, the manufacturing method thereof, and the cooking appliance including the same are environmentally friendly because Ag, Cu, etc., which were used to implement antibacterial performance, are not used and are made of only ingredients that are harmless to the environment and the human body. Rather, it can be applied to various fields due to its excellent price competitiveness.
아울러, 본 발명에 따른 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기는 내구성이 뛰어난 SiO2-B2O3를 망목구조로 가지며, 내구성을 유지 또는 향상시키며 항균 성능 발현 성분인 ZnO와 SnO와의 상호작용을 할 수 있도록 2 종 이상의 알칼리 산화물(Na2O, K2O)와 알칼리 토류 산화물(CaO, MgO)을 최적의 함량비로 첨가하는 것에 의해, 내구성 및 항균성을 향상시킬 수 있다.In addition, the composite glass composition according to the present invention, a method for manufacturing the same, and a cooking appliance including the same have SiO 2 -B 2 O 3 having excellent durability in a network structure, maintain or improve durability, and contain ZnO, an antibacterial performance component, and By adding two or more kinds of alkali oxides (Na 2 O, K 2 O) and alkaline earth oxides (CaO, MgO) in an optimal content ratio to interact with SnO, durability and antibacterial properties can be improved.
이를 위해, 본 발명에 따른 복합 유리 조성물은 법랑 조성물, 및 법랑 조성물에 혼합된 항균 유리 분말을 포함하며, 항균 유리 분말은 SiO2 26 ~ 50 중량%, B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%, Na2O 및 K2O 1종 이상 15 ~ 27 중량%, CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%, 및 ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%를 포함한다.To this end, the composite glass composition according to the present invention includes an enamel composition and an antibacterial glass powder mixed with the enamel composition, and the antibacterial glass powder is SiO 2 26 to 50 wt%, B 2 O 3 and P 2 O 5 One kind 0.5 to 4 wt% or more, 15 to 27 wt% of at least one of Na 2 O and K 2 O, 3 to 20 wt% of at least one of CaO, MgO and WO 3 , and 22 to 44 wt% of at least one of ZnO and SnO % by weight.
여기서, Na2O는 5 ~ 18 중량%로 첨가되는 것이 바람직하고, K2O는 5 ~ 13 중량%로 첨가되는 것이 바람직하다.Here, Na 2 O is preferably added in an amount of 5 to 18% by weight, and K 2 O is preferably added in an amount of 5 to 13% by weight.
아울러, 본 발명의 실시예에 따른 복합 유리 조성물은 법랑 조성물 80 ~ 99.5 중량%, 및 항균 유리 분말 0.5 ~ 20 중량%로 혼합되는 것이 바람직하다.In addition, the composite glass composition according to an embodiment of the present invention is preferably mixed in 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder.
여기서, 법랑 조성물은 P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함할 수 있다.Here, the enamel composition is P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1-20 wt%, Li 2 O 1-10 wt%, NaF 5 wt% or less, B 2 O 3 1-20 wt%, TiO 2 5 wt% or less and V 2 O 5 10 wt% or less can do.
본 발명에 따르면, 법랑 조성물의 성능 및 외관에 대한 변화 없이 항균 유리 분말의 단순 첨가만으로도 인체에 무해하면서 우수한 항균 성능을 나타내어 영구적으로 항균 기능을 유지할 수 있게 된다.According to the present invention, it is possible to maintain the antibacterial function permanently by exhibiting excellent antibacterial performance while harmless to the human body by simply adding antibacterial glass powder without changing the performance and appearance of the enamel composition.
아울러, 본 발명에 따르면, 내구성이 우수한 항균 유리 분말이 법랑 조성물에 첨가되는 것에 의해, 식품이나 각종 오염물이 닿는 부분에서 미생물들이 성장하는 것을 미연에 억제할 수 있게 된다.In addition, according to the present invention, by adding the antibacterial glass powder having excellent durability to the enamel composition, it is possible to suppress in advance the growth of microorganisms in the portion in contact with food or various contaminants.
또한, 본 발명에 따르면, 항균 성능을 구현하기 위해 사용되던 Ag, Cu 등이 사용되지 않고, 환경 및 인체에 무해한 성분들로만 이루어지므로 친환경적일 뿐만 아니라, 가격 경쟁력이 뛰어나 다양한 분야에 적용하는 것이 가능해질 수 있다.In addition, according to the present invention, since Ag, Cu, etc., which were used to implement antibacterial performance, are not used, and it is made of only ingredients that are harmless to the environment and human body, it is not only eco-friendly, but also has excellent price competitiveness, so that it can be applied to various fields. can
상술한 효과와 더불어 본 발명의 구체적인 효과는 이하 발명을 실시하기 위한 구체적인 사항을 설명하면서 함께 기술한다.In addition to the above-described effects, the specific effects of the present invention will be described together while describing specific details for carrying out the invention below.
도 1은 본 발명의 실시예에 따른 복합 유리 조성물 제조 방법을 나타낸 공정 순서도이다.1 is a process flow chart showing a method for manufacturing a composite glass composition according to an embodiment of the present invention.
전술한 목적, 특징 및 장점은 첨부된 도면을 참조하여 상세하게 후술되며, 이에 따라 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 용이하게 실시할 수 있을 것이다. 본 발명을 설명함에 있어서 본 발명과 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 상세한 설명을 생략한다. 이하, 첨부된 도면을 참조하여 본 발명에 따른 바람직한 실시예를 상세히 설명하기로 한다. 도면에서 동일한 참조부호는 동일 또는 유사한 구성요소를 가리키는 것으로 사용된다.The above-described objects, features and advantages will be described below in detail with reference to the accompanying drawings, and accordingly, those of ordinary skill in the art to which the present invention pertains will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of a known technology related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.
본 명세서에서 사용되는 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "구성된다" 또는 "포함한다" 등의 용어는 명세서 상에 기재된 여러 구성 요소들, 또는 여러 단계들을 반드시 모두 포함하는 것으로 해석되지 않아야 하며, 그 중 일부 구성 요소들 또는 일부 단계들은 포함되지 않을 수도 있고, 또는 추가적인 구성 요소 또는 단계들을 더 포함할 수 있는 것으로 해석되어야 한다.As used herein, the singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “consisting of” or “comprising” should not be construed as necessarily including all of the various components or various steps described in the specification, some of which components or some steps are It should be construed that it may not include, or may further include additional components or steps.
이하에서는, 본 발명의 몇몇 실시예에 따른 복합 유리 조성물 및 그 제조 방법과, 이를 포함하는 조리기기를 설명하도록 한다.Hereinafter, a composite glass composition according to some embodiments of the present invention, a method for manufacturing the same, and a cooking appliance including the same will be described.
본 발명의 실시예에 따른 복합 유리 조성물은 법랑 조성물의 성능 및 외관에 대한 변화 없이 항균 유리 분말의 단순 첨가만으로 인체에 무해하면서도 우수한 항균 성능을 나타내어 영구적으로 항균 기능을 유지할 수 있게 된다.The composite glass composition according to an embodiment of the present invention is harmless to the human body and exhibits excellent antibacterial performance by simply adding antibacterial glass powder without any change in the performance and appearance of the enamel composition, thereby permanently maintaining the antibacterial function.
또한, 본 발명의 실시예에 따른 복합 유리 조성물은 기존에 널리 사용하는 Ag를 사용하지 않고 Zn과 Sn을 사용한 항균 유리 분말을 법랑 조성물에 최적의 함량비로 첨가하는 것에 의해 우수한 항균 성능을 확보하였다.In addition, the composite glass composition according to an embodiment of the present invention secured excellent antibacterial performance by adding an antibacterial glass powder using Zn and Sn to the enamel composition in an optimal content ratio without using Ag, which is widely used in the past.
아울러, 본 발명의 실시예에 따른 복합 유리 조성물은 내구성이 뛰어난 SiO2-B2O3를 망목구조로 가지며, 내구성을 유지 또는 향상시키며 항균 성능 발현 성분인 ZnO와 SnO와의 상호작용을 할 수 있도록 2 종 이상의 알칼리 산화물(Na2O, K2O)와 알칼리 토류 산화물(CaO, MgO)을 최적의 함량비로 첨가하였다.In addition, the composite glass composition according to an embodiment of the present invention has a highly durable SiO 2 -B 2 O 3 network structure, maintains or improves durability, and enables interaction between ZnO and SnO, which are components that exhibit antibacterial performance. Two or more kinds of alkali oxides (Na 2 O, K 2 O) and alkaline earth oxides (CaO, MgO) were added in an optimal content ratio.
이때, 항균 성능 발현 성분인 ZnO 및 SnO는 소량 첨가 시 유리 구조를 약화시키며, 내구성이 떨어지게 되고 항균성능도 구현하지 못하나, 본 발명에서는 ZnO 및 SnO 중 1종 이상을 22 ~ 44 중량%의 함량비로 첨가하는 것에 의해 내구성 및 항균성을 향상시켰다.At this time, ZnO and SnO, which are components that exhibit antibacterial performance, weaken the glass structure when added in a small amount, and the durability is lowered and antibacterial performance cannot be realized. By adding, durability and antibacterial property were improved.
이를 위해, 본 발명의 실시예에 따른 복합 유리 조성물은 법랑 조성물, 및 법랑 조성물에 혼합된 항균 유리 분말을 포함하며, 항균 유리 분말은 SiO2 26 ~ 50 중량%, B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%, Na2O 및 K2O 1종 이상 15 ~ 27 중량%, CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%, 및 ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%를 포함한다.To this end, the composite glass composition according to an embodiment of the present invention includes an enamel composition and an antibacterial glass powder mixed in the enamel composition, and the antibacterial glass powder is SiO 2 26 to 50 wt%, B 2 O 3 and P 2 O 5 at least 0.5 to 4% by weight, at least one of Na 2 O and K 2 O at least 15 to 27% by weight, at least 3 to 20% by weight of at least one of CaO, MgO and WO 3 , and at least one of ZnO and SnO 22 to 44% by weight.
여기서, Na2O는 5 ~ 18 중량%로 첨가되는 것이 바람직하고, K2O는 5 ~ 13 중량%로 첨가되는 것이 바람직하다.Here, Na 2 O is preferably added in an amount of 5 to 18 wt%, and K 2 O is preferably added in an amount of 5 to 13 wt%.
아울러, Na2O 및 K2O는 하기 식 1을 만족하는 범위로 첨가되는 것이 보다 바람직하다.In addition, Na 2 O and K 2 O are more preferably added in a range satisfying the following formula (1).
식 1 : 0.5 ≤ [Na2O] / [K2O] ≤ 1.5Equation 1: 0.5 ≤ [Na 2 O] / [K 2 O] ≤ 1.5
여기서, []는 각 성분의 함량비를 나타낸다.Here, [] represents the content ratio of each component.
또한, 항균 유리 분말은 Ag2O, Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함할 수 있다.In addition, the antibacterial glass powder may further include 0.1 wt% or less of one or more of Ag 2 O, Ag 3 PO 4 and AgNO 3 .
아울러, 본 발명의 실시예에 따른 복합 유리 조성물은 법랑 조성물 80 ~ 99.5 중량%, 및 항균 유리 분말 0.5 ~ 20 중량%로 혼합되는 것이 바람직하고, 보다 바람직한 범위로는 법랑 조성물 90 ~ 99 중량%, 및 항균 유리 분말 1 ~ 10 중량%를 제시할 수 있다.In addition, the composite glass composition according to an embodiment of the present invention is preferably mixed with 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder, and more preferably 90 to 99% by weight of the enamel composition; and 1 to 10% by weight of antibacterial glass powder.
만일, 항균 유리 분말이 복합 유리 조성물 전체 중량의 0.5 중량% 미만으로 첨가될 경우에는 내구성 및 항균성을 향상시키는데 어려움이 따를 수 있다. 반대로, 항균 유리 분말이 복합 유리 조성물 전체 중량의 20 중량%를 초과할 경우에는 항균 성능은 향상되나, 외관 및 성능이 저하될 우려가 있으므로, 바람직하지 못하다.If the antibacterial glass powder is added in an amount of less than 0.5% by weight of the total weight of the composite glass composition, it may be difficult to improve durability and antibacterial properties. Conversely, when the antibacterial glass powder exceeds 20% by weight of the total weight of the composite glass composition, the antibacterial performance is improved, but there is a risk of deterioration in appearance and performance, which is not preferable.
본 발명의 실시예에서는, 법랑 조성물에 항균 유리 분말이 혼합되는 것으로 설명하였으나, 이는 예시적인 것으로 법랑 외에도 유약에도 동일한 성분 및 성분비로 첨가하는 것도 가능하다.In the embodiment of the present invention, it has been described that the antibacterial glass powder is mixed with the enamel composition, but this is exemplary and it is also possible to add the same ingredients and ratios to the glaze in addition to the enamel.
여기서, 법랑 조성물은 전자레인지, 오븐, 가스레인지 등과 같은 조리기기에 코팅하여 사용되는 것이라면, 특별히 제한 없이 적용될 수 있다.Here, the enamel composition may be applied without particular limitation, as long as it is coated and used for cooking devices such as microwave ovens, ovens, gas ranges, and the like.
이를 위해, 법랑 조성물은 P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함할 수 있다.To this end, the enamel composition is P 2 O 5 10 to 35% by weight, SiO 2 10 to 45% by weight, Al 2 O 3 5 to 20% by weight, ZrO 2 10% by weight or less, Na 2 O 1 to 15% by weight, 1 to 20 wt% of K 2 O, 1 to 10 wt% of Li 2 O, 5 wt% or less of NaF, 1 to 20 wt% of B 2 O 3 , 5 wt% or less of TiO 2 and 10 wt% or less of V 2 O 5 may include
아울러, 법랑 조성물은 Co3O4, MnO2, NiO 및 Fe2O3 중 1종 이상 5 중량% 이하를 더 포함할 수도 있다.In addition, the enamel composition may further include 5 wt% or less of at least one of Co 3 O 4 , MnO 2 , NiO and Fe 2 O 3 .
전술한 본 발명의 실시예에 따른 복합 유리 조성물은 법랑 조성물의 성능 및 외관에 대한 변화 없이 항균 유리 분말의 단순 첨가만으로도 인체에 무해하면서 우수한 항균 성능을 나타내어 영구적으로 항균 기능을 유지할 수 있게 된다.The composite glass composition according to the above-described embodiment of the present invention is harmless to the human body and exhibits excellent antibacterial performance by simply adding antibacterial glass powder without changing the performance and appearance of the enamel composition, thereby maintaining the antibacterial function permanently.
아울러, 본 발명의 실시예에 따른 복합 유리 조성물은 내구성이 우수한 항균 유리 분말이 법랑 조성물에 첨가되는 것에 의해, 식품이나 각종 오염물이 닿는 부분에서 미생물들이 성장하는 것을 미연에 억제할 수 있게 된다.In addition, in the composite glass composition according to an embodiment of the present invention, since the antibacterial glass powder having excellent durability is added to the enamel composition, it is possible to suppress the growth of microorganisms in advance in the portion in contact with food or various contaminants.
또한, 본 발명의 실시예에 따른 복합 유리 조성물은 항균 성능을 구현하기 위해 사용되던 Ag, Cu 등이 사용되지 않고, 환경 및 인체에 무해한 성분들로만 이루어지므로 친환경적일 뿐만 아니라, 가격 경쟁력이 뛰어나 다양한 분야에 적용하는 것이 가능해질 수 있다.In addition, since the composite glass composition according to an embodiment of the present invention does not use Ag, Cu, etc., which were used to implement antibacterial performance, and is made of only ingredients that are harmless to the environment and human body, it is not only eco-friendly but also has excellent price competitiveness in various fields It may be possible to apply to
이하에서는 본 발명의 실시예에 따른 항균 유리 분말의 원료인 항균 유리 조성물의 각 성분의 역할 및 그 함량에 대하여 상세히 설명하도록 한다.Hereinafter, the role and content of each component of the antimicrobial glass composition, which is a raw material of the antimicrobial glass powder according to an embodiment of the present invention, will be described in detail.
SiO2, B2O3 및 P2O5는 망목형성 산화물로서, 유리의 뼈대 구조를 형성하며, 공유결합하여 유리화를 가능하게 하는 핵심적인 성분이다.SiO 2 , B 2 O 3 , and P 2 O 5 are network-forming oxides, which form the skeletal structure of glass and are key components that enable vitrification by covalent bonding.
SiO2는 유리화가 가능하게 하는 유리형성제로서, 유리의 구조적인 측면에서는 뼈대의 역할을 하는 핵심적인 성분이 된다. 이러한 SiO2는 적정량 이상을 포함하게 되면 유리 용융시 점도가 높아져 냉각 과정에서 작업성 및 수율이 떨어지게 된다. 아울러, SiO2는 항균력을 발현하는 직접적인 성분으로 작용하지는 않으나, 대표적인 망목형성 산화물인 P2O5 대비 유리 표면에 OH- 기를 덜 형성시켜, 유리 내 금속 이온으로 야기되는 유리 표면을 양의 전하로 띠게 하는데 유리하다.SiO 2 is a glass former that enables vitrification, and in terms of the structure of the glass, it is a key component that serves as a framework. When such SiO 2 is contained in an appropriate amount or more, the viscosity increases when the glass is melted, and thus workability and yield are deteriorated in the cooling process. In addition, SiO 2 does not act as a direct component that exhibits antibacterial activity, but forms less OH - groups on the glass surface compared to P 2 O 5 , which is a typical network-forming oxide, so that the glass surface caused by metal ions in the glass is positively charged. It is advantageous to make
따라서, SiO2는 본 발명에 따른 항균 유리 조성물 전체 중량의 26 ~ 50 중량%의 함량비로 첨가되는 것이 바람직하다. SiO2의 첨가량이 26 중량% 미만일 시에는 망목형성 산화물가 부족하여 유리화 영역을 벗어나는데 기인하여 유백화가 나타나거나, 투명한 유리가 혼재하는 불균질화 현상이 발생할 수 있다. 반대로, SiO2의 첨가량이 50 중량%를 초과할 경우에는 유리의 표면 전하를 양의 값으로 제어하기 어렵기 때문에 항균력이 저하되는 현상이 발생할 수 있다.Therefore, SiO 2 is preferably added in a content ratio of 26 to 50% by weight of the total weight of the antimicrobial glass composition according to the present invention. When the amount of SiO 2 added is less than 26% by weight, opacification may occur or a heterogeneity phenomenon in which transparent glass is mixed may occur due to a lack of network-forming oxides and leaving the vitrification region. Conversely, when the amount of SiO 2 added exceeds 50% by weight, it is difficult to control the surface charge of the glass to a positive value, so that the antibacterial activity may be reduced.
B2O3 및 P2O5는 대표적인 망목형성 산화물로써 SiO2와 함께 충분한 유리화가 가능하게 하는 핵심적인 성분이다. B2O3 및 P2O5는 녹는점이 낮아 용융물의 공융점(eutectic point)을 낮추는 용도로 사용된다. 또한, B2O3 및 P2O5는 유리화를 위한 용융(melting)시, 단단(rigid)한 성분(Al2O3, CuO 등)들의 용해도(solubility)를 높이는 작용을 수행함으로써 균질한 유리가 되도록 돕는다. 하지만, B2O3 및 P2O5가 일정 함량 이상으로 첨가되면, 유리의 결합 구조를 약화시켜 내수성 등을 저하시키는 문제가 발생할 수 있다.B 2 O 3 and P 2 O 5 are key components that enable sufficient vitrification together with SiO 2 as representative network-forming oxides. B 2 O 3 and P 2 O 5 have a low melting point and are used for lowering the eutectic point of the melt. In addition, B 2 O 3 and P 2 O 5 When melting (melting) for vitrification, a homogeneous glass by performing an action of increasing the solubility of rigid components (Al 2 O 3 , CuO, etc.) help to become However, when B 2 O 3 and P 2 O 5 are added in a certain amount or more, a problem of weakening the bonding structure of the glass to reduce water resistance, etc. may occur.
따라서, B2O3 및 P2O5는 수불용성 항균 유리를 구현하기 위해 녹는점을 낮추는 용도 만으로 미량 사용하는 것이 바람직하다.Therefore, B 2 O 3 and P 2 O 5 are preferably used in trace amounts only for lowering the melting point in order to implement water-insoluble antibacterial glass.
이를 위해, B2O3 및 P2O5 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 0.5 ~ 4 중량%의 함량비로 첨가되는 것이 바람직하다. B2O3 및 P2O5 1종 이상이 0.5 중량% 미만으로 첨가될 경우에는 융제가 부족하기 때문에 유리화 영역을 벗어나게 되어, 미용융 현상이 발생할 수 있다. 반대로, B2O3 및 P2O5 1종 이상이 4 중량%를 초과할 경우에는 망목형성 구조 내에서 B, P의 구조적인 문제로 원소의 자체 성질에 의해 내수성 저하 현상이 발생할 수 있다.To this end, at least one of B 2 O 3 and P 2 O 5 is preferably added in a content ratio of 0.5 to 4% by weight of the total weight of the antimicrobial glass composition according to the present invention. When one or more of B 2 O 3 and P 2 O 5 is added in an amount of less than 0.5% by weight, the flux is insufficient, and thus it leaves the vitrification region, which may cause unmelting. Conversely, when one or more of B 2 O 3 and P 2 O 5 exceeds 4% by weight, a decrease in water resistance may occur due to structural problems of B and P in the network-forming structure due to the properties of the element itself.
본 발명에서, SiO2는 B2O3의 함량보다 높은 함량으로 첨가되는 것이 바람직한데, 이는 SiO2의 첨가량이 B2O3의 첨가량보다는 높아야 내수성 확보에 유리하기 때문이다.In the present invention, SiO 2 is preferably added in an amount higher than the content of B 2 O 3 , because it is advantageous to ensure water resistance when the amount of SiO 2 is higher than the amount of B 2 O 3 added.
Na2O, K2O와 같은 알칼리 산화물(alkali oxide)은 유리 조성 내에서 비가교 결합을 하는 망목수식제의 역할을 하는 산화물이다. 이러한 성분들은 단독으로는 유리화가 불가능하지만, SiO2 및 B2O3 등과 같은 망목형성제와 일정한 비율로 혼합하면 유리화가 가능해진다. Na2O 및 K2O 가운데 한가지 성분만이 유리 조성물에 포함되면, 유리화가 가능한 영역 내에서는 유리의 내구성을 약화시킬 수 있다. 하지만, 2가지 이상의 성분이 유리 조성에 포함되면 그 비율에 따라 유리의 내구성이 다시 향상되기도 한다. 이를 혼합된 알칼리 효과(mixed alkali effect)라 한다.Alkali oxides, such as Na 2 O and K 2 O, are oxides that serve as a network modifier for non-crosslinking in the glass composition. Although these components cannot be vitrified alone, vitrification is possible when mixed with a network former such as SiO 2 and B 2 O 3 in a certain ratio. If only one component of Na 2 O and K 2 O is included in the glass composition, the durability of the glass may be weakened in the area where vitrification is possible. However, when two or more components are included in the glass composition, the durability of the glass is improved again according to the ratio. This is called the mixed alkali effect.
따라서, Na2O, K2O와 같은 알칼리 산화물(alkali oxide)은 유리 내에서 가장 먼저 수식산화물 사이트(site)를 차지하는 점을 이용하여 항균력을 향상시키게 된다. 아울러, Na2O, K2O와 같은 알칼리 산화물(alkali oxide)은 중간산화물인 ZnO 및 SnO를 망목형성에 기여하도록 하여 내구도가 강화되어 수불용 특성 및 표면전하에 의한 항균력 발현에 기여하는 역할도 한다.Therefore, alkali oxides such as Na 2 O and K 2 O improve the antimicrobial activity by using the point that first occupies the modification oxide site in the glass. In addition, alkali oxides such as Na 2 O and K 2 O contribute to the formation of a network of intermediate oxides such as ZnO and SnO, thereby enhancing durability, contributing to antibacterial activity due to water-insoluble properties and surface charge. do.
Na2O 및 K2O 중 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 15 ~ 27 중량%의 함량비로 첨가되는 것이 바람직하다. Na2O 및 K2O 중 1종 이상이 15 중량% 미만으로 첨가될 경우에는 융제가 부족하기 때문에 유리화 영역을 벗어나는데 기인하여 미용융물이 형성되는 현상이 발생할 수 있다. 반대로, Na2O 및 K2O 중 1종 이상이 27 중량%를 초과하여 다량 첨가되면, 유리의 기본 용출 기작에 따라 알칼리 이온이 쉽게 물의 H3O+ 이온과 치환이 일어나고 용출이 심화되는 내수성 저하 현상이 발생할 수 있다.At least one of Na 2 O and K 2 O is preferably added in a content ratio of 15 to 27% by weight of the total weight of the antimicrobial glass composition according to the present invention. When at least one of Na 2 O and K 2 O is added in an amount of less than 15% by weight, a phenomenon in which an unmelted product is formed may occur due to leaving the vitrification region because the flux is insufficient. Conversely, when one or more of Na 2 O and K 2 O is added in a large amount exceeding 27% by weight, alkali ions are easily replaced with H 3 O + ions of water according to the basic elution mechanism of the glass and water resistance that elution is intensified degradation may occur.
여기서, Na2O는 5 ~ 18 중량%로 첨가되고, K2O는 5 ~ 13 중량%로 첨가되는 것이 보다 바람직하다.Here, Na 2 O is added in an amount of 5 to 18% by weight, and K 2 O is more preferably added in an amount of 5 to 13% by weight.
아울러, Na2O 및 K2O는 하기 식 1을 만족하는 범위로 첨가되는 것이 바람직하다.In addition, Na 2 O and K 2 O are preferably added in a range satisfying the following formula (1).
식 1 : 0.5 ≤ [Na2O] / [K2O] ≤ 1.5Equation 1: 0.5 ≤ [Na 2 O] / [K 2 O] ≤ 1.5
여기서, []는 각 성분의 함량비를 나타낸다.Here, [] represents the content ratio of each component.
만일, 위의 식 1의 범위를 벗어나게 되면, Na2O-K2O의 공융점을 통한 융점 저하 효과가 떨어져 유리화를 벗어날 수 있기 때문이다.If, outside the range of Equation 1 above, the effect of lowering the melting point through the eutectic point of Na 2 OK 2 O may be reduced and vitrification may be escaped.
CaO, MgO, WO3와 같은 알칼리 토류 산화물(alkaline earth oxide)은 기본적으로 유리 내에서 비가교결합을 하는 수식 산화물의 역할을 하는 산화물이다. 단독으로는 유리화가 불가능 하지만, SiO2 및 B2O3 등과 같은 망목형성제와 일정한 비율로 혼합하면 유리화가 가능해진다.Alkaline earth oxides such as CaO, MgO, and WO 3 are basically oxides that play the role of modifying oxides that are non-crosslinked in glass. Vitrification is impossible by itself, but vitrification is possible when mixed with a network former such as SiO 2 and B 2 O 3 in a certain ratio.
CaO, MgO, WO3와 같은 알칼리 토류 산화물(alkaline earth oxide)은 알칼리 산화물(alkali oxide)과 달리 +2가 전하를 띠어 물분자 이온 2개와 치환되어야 하기 때문에 상대적으로 이온교환이 어려워 내구성 강화 요소로 사용 되기도 한다. 따라서, CaO, MgO, WO3와 같은 알칼리 토류 산화물(alkaline earth oxide)은 수식 산화물 중 내구성이 강건한 점과 수식산화물 사이트를 차지하여 수불용성 및 항균특성을 발현하는데 구조적으로 간접 기여하는 알칼리 산화물(alkali oxide)과 같은 목적으로 사용한다.Unlike alkali oxides, alkaline earth oxides such as CaO, MgO, and WO 3 have a +2 charge and have to be substituted with two water molecule ions, so ion exchange is relatively difficult, so it is used as a durability enhancing element. It is also used Therefore, alkaline earth oxides such as CaO, MgO, and WO 3 have strong durability among modified oxides and occupy a modified oxide site, which structurally indirectly contributes to the expression of water insolubility and antibacterial properties. oxide) for the same purpose.
CaO, MgO 및 WO3 중 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 3 ~ 20 중량%의 함량비로 첨가되는 것이 바람직하다. CaO, MgO 및 WO3 중 1종 이상이 3 중량% 미만일 경우에는 수식산화물 사이트(site)에서 구조를 강건하게 하지 못하기 때문에 알칼리 용출을 막지 못하는 내수성 저하 현상이 발생할 수 있다. 반대로, CaO, MgO 및 WO3 중 1종 이상이 20 중량%를 초과할 경우에는 고온에 녹는 물질인 알칼리 토류 산화물이 충분히 용융되지 못하기 때문에 유리화 영역을 벗어나게 되는데 기인하여 미용융물이 형성되는 현상이 발생할 수 있다.At least one of CaO, MgO and WO 3 is preferably added in a content ratio of 3 to 20% by weight based on the total weight of the antimicrobial glass composition according to the present invention. When at least one of CaO, MgO, and WO 3 is less than 3 wt%, since the structure cannot be strengthened at the modified oxide site, a water resistance deterioration phenomenon that cannot prevent alkali elution may occur. Conversely, when at least one of CaO, MgO, and WO 3 exceeds 20% by weight, the alkaline earth oxide, which is a material that melts at a high temperature, does not melt sufficiently, and thus leaves the vitrification region, resulting in the formation of an unmelted product. can occur
ZnO 및 SnO는 망목형성 산화물의 일부와 치환되어 공유결합하여 망목형선 산화물의 역할 및 수식산화물 역할을 모두 수행하는 성분이다. 아울러, ZnO 및 SnO은 항균 효과를 발현하는데 크게 기여하는 성분이다.ZnO and SnO are components that are substituted with a part of the network-forming oxide and form a covalent bond to perform both the role of the network-forming oxide and the modifying oxide. In addition, ZnO and SnO are components that greatly contribute to the expression of the antibacterial effect.
이러한 ZnO 및 SnO는 중간산화물로서, 유리에서 망목형성 구조에 참여하기 위해서는 원자 반경이 작고, 전기음성도가 커서 산소와의 차이가 작아야 한다. 이러한 중간산화물은 통상적인 망목형성 산화물인 Si, P, B보다 원자 반경이 크고, 전기음성도가 낮아 단독으로 유리 형성은 어려우나 망목형성 산화물이 존재하는 상황에서 망목형성 산화물과 치환되어 그 역할을 하는 성분을 말한다. 이러한 ZnO 및 SnO는 일정 함량 이하에서는 수식산화물로만 역할 하게 되나, 일정 함량 이상에서는 공유결합을 형성하여 내구도가 급진적으로 향상된다. 여기서, 일정 함량은 망목형성 산화물과 수식산화물의 함량에 의하여 결정된다.These ZnO and SnO are intermediate oxides, and in order to participate in the network-forming structure in glass, the atomic radius is small and the electronegativity is large, so the difference from oxygen must be small. These intermediate oxides have a larger atomic radius and lower electronegativity than conventional network-forming oxides, such as Si, P, and B, making it difficult to form glass alone. say ingredients. These ZnO and SnO act only as modified oxides below a certain content, but above a certain content, they form a covalent bond, and the durability is radically improved. Here, the predetermined content is determined by the content of the network-forming oxide and the modifying oxide.
따라서, ZnO 및 SnO 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 22 ~ 44 중량%의 함량비로 첨가되는 것이 바람직하다. ZnO 및 SnO 1종 이상이 22 중량% 미만으로 첨가될 경우에는 항균성능을 발현하는 물질의 절대량이 부족하기 때문에 충분한 항균력을 발현하지 못하는 문제가 있다. 반대로, ZnO 및 SnO 1종 이상이 44 중량%를 초과하여 과다 첨가될 경우에는 균질하에 유리 내에 이온 상태로 존재하지 못하고, 부분적으로 결정을 형성시켜 유리화 영역을 벗어나게 되는데 기인하여 유백화가 나타나고, 투명한 유리가 혼재하는 불균질화 현상이 발생할 수 있다.Accordingly, ZnO and at least one SnO is preferably added in a content ratio of 22 to 44% by weight of the total weight of the antimicrobial glass composition according to the present invention. When one or more of ZnO and SnO is added in an amount of less than 22% by weight, there is a problem in that sufficient antibacterial activity cannot be expressed because the absolute amount of the material exhibiting antibacterial performance is insufficient. Conversely, when at least one of ZnO and SnO is added in excess of 44 wt%, opacification occurs due to the fact that it does not exist as an ionic state in the glass under homogeneity, and partially forms crystals to escape the vitrification region, resulting in opacification and transparent glass A heterogeneity phenomenon in which the are mixed may occur.
Ag2O, Ag3PO4 및 AgNO3는 유리 내에 이온 상태로 존재하며, 항균력을 발현하는데 효과적인 성분이다. 아울러, Ag2O, Ag3PO4 및 AgNO3는 용점을 낮추는 역할을 한다. 다만, Ag2O, Ag3PO4 및 AgNO3 중 1종 이상이 0.1 중량%를 초과하여 과다 첨가할 시 은 금속의 석출로 유리화를 불안정하게 할 우려가 있다. 따라서, Ag2O, Ag3PO4 및 AgNO3 중 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 0.1 중량% 이하로 엄격히 제한적으로 첨가되는 것이 바람직하다.Ag 2 O, Ag 3 PO 4 and AgNO 3 are present in an ionic state in the glass, and are effective components for expressing antibacterial activity. In addition, Ag 2 O, Ag 3 PO 4 and AgNO 3 serves to lower the melting point. However, when at least one of Ag 2 O, Ag 3 PO 4 and AgNO 3 is added in excess of 0.1 wt%, there is a risk of destabilizing vitrification due to precipitation of silver metal. Accordingly, at least one of Ag 2 O, Ag 3 PO 4 and AgNO 3 is preferably added in a strictly limited amount of 0.1 wt% or less of the total weight of the antimicrobial glass composition according to the present invention.
이하 첨부된 도면을 참조하여 본 발명의 실시예에 따른 복합 유리 조성물 제조 방법에 대하여 설명하도록 한다.Hereinafter, a method for manufacturing a composite glass composition according to an embodiment of the present invention will be described with reference to the accompanying drawings.
도 1은 본 발명의 실시예에 따른 복합 유리 조성물 제조 방법을 나타낸 공정 순서도이다.1 is a process flow chart showing a method for manufacturing a composite glass composition according to an embodiment of the present invention.
도 1에 도시된 바와 같이, 본 발명의 실시예에 따른 복합 유리 조성물 제조 방법은 1차 혼합 단계(S110), 용융 단계(S120), 냉각 단계(S130), 분쇄 단계(S140) 및 2차 혼합 단계(S150)를 포함한다.As shown in FIG. 1 , the method for manufacturing a composite glass composition according to an embodiment of the present invention includes a primary mixing step (S110), a melting step (S120), a cooling step (S130), a grinding step (S140), and the secondary mixing. Step S150 is included.
1차 혼합primary mix
1차 혼합 단계(S110)에서 SiO2 26 ~ 50 중량%, B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%, Na2O 및 K2O 1종 이상 15 ~ 27 중량%, CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%, 및 ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%로 혼합하고 교반하여 항균 유리 조성물을 형성한다.In the first mixing step (S110), SiO 2 26-50 wt%, B 2 O 3 and P 2 O 5 one or more 0.5-4 wt%, Na 2 O and K 2 O one or more 15-27 wt%, CaO, MgO, and 3 to 20% by weight of at least one of WO 3 , and 22 to 44% by weight of at least one of ZnO and SnO are mixed and stirred to form an antibacterial glass composition.
여기서, Na2O는 5 ~ 18 중량%로 첨가하고, K2O는 5 ~ 13 중량%로 첨가하는 것이 바람직하다.Here, Na 2 O is added in an amount of 5 to 18% by weight, and K 2 O is preferably added in an amount of 5 to 13% by weight.
아울러, Na2O 및 K2O는 하기 식 1을 만족하는 범위로 첨가하는 것이 보다 바람직하다.In addition, it is more preferable to add Na 2 O and K 2 O in a range satisfying the following formula (1).
식 1 : 0.5 ≤ [Na2O] / [K2O] ≤ 1.5Equation 1: 0.5 ≤ [Na 2 O] / [K 2 O] ≤ 1.5
여기서, []는 각 성분의 함량비를 나타낸다.Here, [] represents the content ratio of each component.
만일, 위의 식 1의 범위를 벗어나게 되면, Na2O-K2O의 공융점을 통한 융점 저하 효과가 떨어져 유리화를 벗어날 수 있기 때문이다.If, outside the range of Equation 1 above, the effect of lowering the melting point through the eutectic point of Na 2 OK 2 O may be reduced and vitrification may be escaped.
또한, 항균 유리 조성물은 Ag2O, Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함할 수 있다.In addition, the antimicrobial glass composition may further include 0.1 wt% or less of at least one of Ag 2 O, Ag 3 PO 4 and AgNO 3 .
용융melt
용융 단계(S120)에서는 항균 유리 조성물을 용융시킨다.In the melting step (S120), the antimicrobial glass composition is melted.
본 단계에서, 용융은 1,100 ~ 1,400℃에서 1 ~ 60분 동안 실시하는 것이 바람직하다. 용융 온도가 1,100℃ 미만이거나, 용융 시간이 1분 미만일 경우에는 항균 유리 조성물이 완전히 용융되지 못하여 유리 용융물의 불혼화를 발생시키는 문제가 있다. 반대로, 용융 온도가 1,400℃를 초과하거나, 용융 시간이 60분을 초과할 경우에는 과도한 에너지 및 시간이 필요하므로 경제적이지 못하다.In this step, the melting is preferably carried out at 1,100 ~ 1,400 ℃ for 1 ~ 60 minutes. If the melting temperature is less than 1,100° C. or the melting time is less than 1 minute, the antibacterial glass composition cannot completely melt, thereby causing an immiscibility of the glass melt. Conversely, when the melting temperature exceeds 1,400° C. or the melting time exceeds 60 minutes, it is not economical because excessive energy and time are required.
냉각Cooling
냉각 단계(S130)에서는 용융된 항균 유리 조성물을 상온까지 냉각한다.In the cooling step (S130), the molten antibacterial glass composition is cooled to room temperature.
본 단계에서, 냉각은 노냉(cooling in furnace) 방식으로 수행되는 것이 바람직하다. 공냉 또는 수냉을 적용할 경우에는 항균 유리의 내부응력이 심하게 형성되어 경우에 따라서는 크랙이 발생할 수 있는 바, 냉각은 노냉이 바람직하다.In this step, the cooling is preferably performed in a cooling in furnace method. When air cooling or water cooling is applied, the internal stress of the antibacterial glass is severely formed, and cracks may occur in some cases. Therefore, furnace cooling is preferable.
분쇄smash
분쇄 단계(S140)에서는 냉각된 항균 유리를 분쇄한다. 이때, 분쇄는 통상적으로 널리 알려진 볼밀, 제트밀, 유성 밀 중 어느 하나가 적용될 수 있다.In the crushing step (S140), the cooled antibacterial glass is crushed. In this case, any one of a commonly known ball mill, jet mill, and planetary mill may be applied for the pulverization.
이러한 분쇄에 의해, 항균 유리가 미세하게 분쇄되어 항균 유리 분말이 제조된다. 이러한 항균 유리 분말은 80㎛ 이하의 평균 직경을 갖는 것이 바람직하며, 보다 바람직한 범위로는 10 ~ 30㎛의 평균 직경을 제시할 수 있다.By this pulverization, the antibacterial glass is finely pulverized to produce an antibacterial glass powder. The antibacterial glass powder preferably has an average diameter of 80 μm or less, and can present an average diameter of 10 to 30 μm as a more preferable range.
2차 혼합secondary mixing
2차 혼합 단계(S150)에서는 분쇄된 항균 유리 분말을 법랑 조성물에 혼합하여 복합 유리 조성물을 형성한다.In the secondary mixing step (S150), the pulverized antibacterial glass powder is mixed with the enamel composition to form a composite glass composition.
여기서, 복합 유리 조성물은 법랑 조성물 80 ~ 99.5 중량%, 및 항균 유리 분말 0.5 ~ 20 중량%로 혼합되는 것이 바람직하고, 보다 바람직한 범위로는 90 ~ 99 중량%, 및 항균 유리 분말 1 ~ 10 중량%를 제시할 수 있다.Here, the composite glass composition is preferably mixed in 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder, more preferably 90 to 99% by weight, and 1 to 10% by weight of the antibacterial glass powder can be presented
만일, 항균 유리 분말이 복합 유리 조성물 전체 중량의 0.5 중량% 미만으로 첨가될 경우에는 내구성 및 항균성을 향상시키는데 어려움이 따를 수 있다. 반대로, 항균 유리 분말이 복합 유리 조성물 전체 중량의 20 중량%를 초과할 경우에는 항균 성능은 향상되나, 외관 및 성능이 저하될 우려가 있으므로, 바람직하지 못하다.If the antibacterial glass powder is added in an amount of less than 0.5% by weight of the total weight of the composite glass composition, it may be difficult to improve durability and antibacterial properties. Conversely, when the antibacterial glass powder exceeds 20% by weight of the total weight of the composite glass composition, the antibacterial performance is improved, but there is a risk of deterioration in appearance and performance, which is not preferable.
이때, 법랑 조성물은 전자레인지, 오븐, 가스레인지 등과 같은 조리기기에 코팅하여 사용되는 것이라면, 특별히 제한 없이 적용될 수 있다.In this case, the enamel composition may be applied without particular limitation as long as it is used by coating on cooking devices such as microwave ovens, ovens, gas ranges, and the like.
이를 위해, 법랑 조성물은 P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함할 수 있다.To this end, the enamel composition is P 2 O 5 10 to 35% by weight, SiO 2 10 to 45% by weight, Al 2 O 3 5 to 20% by weight, ZrO 2 10% by weight or less, Na 2 O 1 to 15% by weight, 1 to 20 wt% of K 2 O, 1 to 10 wt% of Li 2 O, 5 wt% or less of NaF, 1 to 20 wt% of B 2 O 3 , 5 wt% or less of TiO 2 and 10 wt% or less of V 2 O 5 may include
아울러, 법랑 조성물은 Co3O4, MnO2, NiO 및 Fe2O3 중 1종 이상 5 중량% 이하를 더 포함할 수도 있다.In addition, the enamel composition may further include 5 wt% or less of at least one of Co 3 O 4 , MnO 2 , NiO and Fe 2 O 3 .
상기의 과정(S110 ~ S150)에 의해, 본 발명의 실시예에 따른 복합 유리 조성물이 제조될 수 있다.By the above processes (S110 to S150), the composite glass composition according to the embodiment of the present invention may be manufactured.
한편, 본 발명의 실시예에 따른 조리기기는 모재 내에 복합 유리 조성물이 첨가되거나, 모재의 표면에 복합 유리 조성물이 코팅된 사출물을 포함한다. 여기서, 조리기기는 전자레인지, 오븐 등을 포함할 수 있으나, 이에 제한되는 것은 아니다.On the other hand, the cooking appliance according to an embodiment of the present invention includes an injection molded product in which the composite glass composition is added to the base material or the composite glass composition is coated on the surface of the base material. Here, the cooking appliance may include a microwave oven, an oven, and the like, but is not limited thereto.
여기서, 모재는 고분자 수지 또는 금속 재질이 이용될 수 있다.Here, the base material may be a polymer resin or a metal material.
아울러, 복합 유리 조성물은 법랑 조성물과, 법랑 조성물에 혼합된 항균 유리 분말을 포함한다.In addition, the composite glass composition includes an enamel composition and an antibacterial glass powder mixed in the enamel composition.
이때, 항균 유리 분말은 SiO2 26 ~ 50 중량%, B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%, Na2O 및 K2O 1종 이상 15 ~ 27 중량%, CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%, 및 ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%를 포함한다.At this time, the antibacterial glass powder is SiO 2 26 to 50% by weight, B 2 O 3 and P 2 O 5 at least 0.5 to 4% by weight, Na 2 O and K 2 O at least 15 to 27% by weight, CaO, 3-20 wt% of at least one of MgO and WO 3 , and 22-44 wt% of at least one of ZnO and SnO.
아울러, 복합 유리 조성물은 법랑 조성물 80 ~ 99.5 중량%, 및 항균 유리 분말 0.5 ~ 20 중량%로 혼합된다.In addition, the composite glass composition is mixed with 80 to 99.5% by weight of the enamel composition, and 0.5 to 20% by weight of the antibacterial glass powder.
여기서, 법랑 조성물은 P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함한다.Here, the enamel composition is P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1-20 wt%, Li 2 O 1-10 wt%, NaF 5 wt% or less, B 2 O 3 1-20 wt%, TiO 2 5 wt% or less and V 2 O 5 10 wt% or less do.
아울러, 법랑 조성물은 Co3O4, MnO2, NiO 및 Fe2O3 중 1종 이상 5 중량% 이하를 더 포함할 수도 있다.In addition, the enamel composition may further include 5 wt% or less of at least one of Co 3 O 4 , MnO 2 , NiO and Fe 2 O 3 .
실시예Example
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.
여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.Content not described here will be omitted because it can be technically inferred sufficiently by a person skilled in the art.
1. 시편 제조1. Specimen Preparation
실시예 1 ~ 5, 비교예 1 ~ 3Examples 1 to 5, Comparative Examples 1 to 3
항균 유리 조성물 제조Antibacterial glass composition preparation
표 1은 실시예 1 ~ 5 및 비교예 1 ~ 3에 따른 항균 유리 조성물에 대한 조성 및 이의 조성비를 나타낸 것이다. 이때, 실시예 1 ~ 5 및 비교예 1 ~ 3에 기재된 조성을 갖는 항균 유리 조성물을 전기로에서 1,200℃의 온도로 각각 용융시킨 후, 스테인리스(stainless steel) 강판에 공냉 방식으로 글래스 벌크 형태로 냉각하여 컬릿(cullet) 형태의 항균 유리를 얻었다. 이후, 항균 유리를 건식분쇄기(ball mill)로 분쇄한 후, 400메쉬 시브에 통과시켜 항균 유리 분말을 제조하였다.Table 1 shows the compositions of the antibacterial glass compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 and their composition ratios. At this time, each of the antibacterial glass compositions having the compositions described in Examples 1 to 5 and Comparative Examples 1 to 3 were melted in an electric furnace at a temperature of 1,200 ° C. (cullet) form of antibacterial glass was obtained. Thereafter, the antibacterial glass was pulverized with a dry grinder (ball mill), and then passed through a 400 mesh sieve to prepare an antibacterial glass powder.
여기서, 성분 Na2O, K2O, CaO의 원재료는 각각 Na2CO3, K2CO3, CaCO3를 사용하였고, 나머지 성분은 표 1에 기재된 것과 동일한 것을 사용하였다. 이때, 유리화는 균질하게 유리성상을 보이는 경우와 유백화 및 미용융물이 발생하는 현상을 기준으로 구분하였다.Here, the raw materials of the components Na 2 O, K 2 O, and CaO were Na 2 CO 3 , K 2 CO 3 , and CaCO 3 , respectively, and the remaining components were the same as those described in Table 1 were used. At this time, vitrification was classified based on a case in which a homogeneous glassy appearance and a phenomenon in which opacification and unmelted matter occurred.
복합 유리 조성물 제조Composite Glass Composition Manufacturing
위의 방법으로 제조된 실시예 1 ~ 5 및 비교예 1 ~ 3에 따른 항균 유리 조성물을 표 1에 기재된 함량비로 법랑 조성물에 첨가하고, 3차원 파우더 믹서(3D powder mixer)를 사용하여 혼합하여 복합 유리 조성물을 제조하였다.The antibacterial glass compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 prepared by the above method were added to the enamel composition in the content ratio shown in Table 1, and mixed using a 3D powder mixer to form a composite. A glass composition was prepared.
이때, 법랑 조성물로는 P2O5 18.5wt%, SiO2 32.3%, Al2O3 6.5wt%, ZrO2 5.0wt%, Na2O 4.1wt%, K2O 9.6wt%, Li2O 3.0wt%, NaF 1.2wt%, B2O3 10.5wt%, TiO2 1.0wt%, V2O5 6.2wt%, MnO2 1.1wt% 및 Fe2O3 1.0wt%로 조성된 것을 이용하였다.At this time, as the enamel composition, P 2 O 5 18.5 wt%, SiO 2 32.3%, Al 2 O 3 6.5 wt%, ZrO 2 5.0 wt%, Na 2 O 4.1 wt%, K 2 O 9.6 wt%, Li 2 O 3.0wt%, NaF 1.2wt%, B 2 O 3 10.5wt%, TiO 2 1.0wt%, V 2 O 5 6.2wt%, MnO 2 1.1wt% and Fe 2 O 3 1.0wt% was used. .
여기서, 건식 방식으로 법랑을 제작하기 위해, 실시예 1 ~ 3 및 비교예 1 ~ 2에 따른 복합 유리 조성물 100 중량부에 대하여, 실란커플링제(Silane coupling agent)를 0.05 중량부를 더 혼합하였다.Here, 0.05 parts by weight of a silane coupling agent was further mixed with respect to 100 parts by weight of the composite glass compositions according to Examples 1 to 3 and Comparative Examples 1 to 2 to prepare enamel in the dry method.
한편, 습식 방식으로 법랑을 제작하기 위해, 실시예 4 ~ 5 및 비교예 3에 따른 복합 유리 조성물을 물과 1 : 1의 중량비로 혼합하고, 복합 유리 조성물 100 중량부에 대하여, 클레이 산화알루미늄, 붕사 및 벤토나이트 합산으로 0.05 중량부를 더 첨가하여 10시간 동안 혼합하였다.Meanwhile, in order to produce enamel by a wet method, the composite glass compositions according to Examples 4 to 5 and Comparative Example 3 were mixed with water in a weight ratio of 1:1, and clay aluminum oxide, based on 100 parts by weight of the composite glass composition, An additional 0.05 parts by weight of the sum of borax and bentonite was added and mixed for 10 hours.
법랑 시편 제조Preparation of enamel specimens
건식으로 제조한 실시예 1 ~ 3 및 비교예 1 ~ 2에 따른 복합 유리 조성물을 코로나 방전 건을 이용하여 저탄소강 시트에 분사하여 법랑 코팅층을 형성하였으며, 분사 후 법랑 코팅층이 형성된 저탄소강 시트를 850℃의 온도 조건으로 7분 동안 소성하여 법랑 시편을 제조하였다. 여기서, 방전 건의 전압은 60kV로 제어하였다.The composite glass compositions according to Examples 1 to 3 and Comparative Examples 1 to 2 prepared in a dry method were sprayed on a low-carbon steel sheet using a corona discharge gun to form an enamel coating layer, and after spraying, a low-carbon steel sheet with an enamel coating layer was applied to 850 An enamel specimen was prepared by calcination at a temperature of ℃ for 7 minutes. Here, the voltage of the discharge gun was controlled to 60 kV.
한편, 습식으로 제조한 실시예 4 ~ 5 및 비교예 3에 따른 복합 유리 조성물을 에어 스프레이 건을 이용하여 저탄소강 시트에 분사하였으며, 분사 후 법랑 코팅층이 형성된 저탄소강 시트를 860℃의 온도 조건으로 8분 동안 소성하여 법랑 시편을 제조하였다.Meanwhile, the wet-prepared composite glass compositions according to Examples 4 to 5 and Comparative Example 3 were sprayed onto a low-carbon steel sheet using an air spray gun, and after spraying, the low-carbon steel sheet with an enamel coating layer was applied to a temperature condition of 860°C. Enameled specimens were prepared by firing for 8 minutes.
비교예 4Comparative Example 4
P2O5 18.5wt%, SiO2 32.3%, Al2O3 6.5wt%, ZrO2 5.0wt%, Na2O 4.1wt%, K2O 9.6wt%, Li2O 3.0wt%, NaF 1.2wt%, B2O3 10.5wt%, TiO2 1.0wt%, V2O5 6.2wt%, MnO2 1.1wt% 및 Fe2O3 1.0wt%로 조성된 법랑 조성물을 준비하였다.P 2 O 5 18.5 wt%, SiO 2 32.3%, Al 2 O 3 6.5 wt%, ZrO 2 5.0 wt%, Na 2 O 4.1 wt%, K 2 O 9.6 wt%, Li 2 O 3.0 wt%, NaF 1.2 An enamel composition comprising wt%, B 2 O 3 10.5 wt%, TiO 2 1.0 wt%, V 2 O 5 6.2 wt%, MnO 2 1.1 wt%, and Fe 2 O 3 1.0 wt% was prepared.
다음으로, 법랑 조성물 100 중량부에 대하여, 실란커플링제(Silane coupling agent)를 0.05 중량부를 더 혼합한 후, 코로나 방전 건을 이용하여 저탄소강 시트에 분사하여 법랑 코팅층을 형성하였으며, 분사 후 법랑 코팅층이 형성된 저탄소강 시트를 850℃의 온도 조건으로 7분 동안 소성하여 법랑 시편을 제조하였다. 여기서, 방전 건의 전압은 60kV로 제어하였다.Next, with respect to 100 parts by weight of the enamel composition, 0.05 parts by weight of a silane coupling agent was further mixed, and then sprayed on a low-carbon steel sheet using a corona discharge gun to form an enamel coating layer. After spraying, the enamel coating layer The formed low-carbon steel sheet was fired at a temperature of 850° C. for 7 minutes to prepare an enamel specimen. Here, the voltage of the discharge gun was controlled to 60 kV.
[표 1] (단위 : 중량%)[Table 1] (Unit: wt%)
Figure PCTKR2021019100-appb-img-000001
Figure PCTKR2021019100-appb-img-000001
2. 항균 성능 평가2. Antibacterial performance evaluation
표 2는 실시예 1 ~ 5 및 비교예 1 ~ 3에 따라 제조된 시편들에 대한 항균 성능 평가 결과를 나타낸 것이다. 이때, 실시예 1 ~ 5 및 비교예 1 ~ 3에 따라 제조된 시편들에 대하여, 항균 규격 시험(JIS Z 2801, 필름 부착법)으로 황색포도상구균(Staphylococcus aureus) 및 대장균(Escherichia coil)에 대한 항균활성치를 확인하였으며, 폐렴균(Klebsiella pneumonia) 및 녹농균(Pseudomonas aeruginosa)에 대한 항균활성치도 추가 평가하였다.Table 2 shows the antibacterial performance evaluation results for the specimens prepared according to Examples 1 to 5 and Comparative Examples 1 to 3. At this time, with respect to the specimens prepared according to Examples 1 to 5 and Comparative Examples 1 to 3, the antibacterial standard test (JIS Z 2801, film adhesion method) Staphylococcus aureus and Escherichia coil Antibacterial against The activity level was confirmed, and the antibacterial activity level against Klebsiella pneumonia and Pseudomonas aeruginosa was additionally evaluated.
[표 2][Table 2]
Figure PCTKR2021019100-appb-img-000002
Figure PCTKR2021019100-appb-img-000002
표 1 및 표 2에 도시된 바와 같이, 실시예 1 ~ 5 및 비교예 1 ~ 3에 따라 제조된 시편들은 모두 유리화가 이루어진 것을 확인하였다.As shown in Tables 1 and 2, it was confirmed that all of the specimens prepared according to Examples 1 to 5 and Comparative Examples 1 to 3 were vitrified.
이때, 실시예 1 ~ 5에 따라 제조된 시편들은 4개의 균 모두에서 99.99% 이상의 우수한 항균력을 나타내었다.At this time, the specimens prepared according to Examples 1 to 5 exhibited excellent antibacterial activity of 99.99% or more in all four bacteria.
반면, 비교예 1에 따라 제조된 시료는 4개의 균 모두에서 99.9%의 항균력을 나타내었고, 비교예 2 및 3은 4개의 균 모두에서 80% 이하의 항균력을 나타내었다.On the other hand, the sample prepared according to Comparative Example 1 exhibited an antibacterial activity of 99.9% on all four bacteria, and Comparative Examples 2 and 3 showed an antibacterial activity of 80% or less on all four bacteria.
3. 법랑 외관 평가3. Enamel Appearance Evaluation
표 3은 실시예 3 및 5와 비교예 4에 따라 제조된 시편들에 대한 법랑 외관 평가 결과를 나타낸 것이다. 이때, 실시예 3 및 5와 비교예 4에 따라 제조된 시편들에 대한 법랑 외관을 평가하기 위해, 색차계(Minolta CR-400)와 광택도계(BYK AG-4446)을 사용하여 측정하였다.Table 3 shows the enamel appearance evaluation results for the specimens prepared according to Examples 3 and 5 and Comparative Example 4. At this time, in order to evaluate the enamel appearance of the specimens prepared according to Examples 3 and 5 and Comparative Example 4, measurements were made using a colorimeter (Minolta CR-400) and a glossmeter (BYK AG-4446).
[표 3][Table 3]
Figure PCTKR2021019100-appb-img-000003
Figure PCTKR2021019100-appb-img-000003
표 3에 도시된 바와 같이, 법랑 조성물에 항균 유리 조성물이 1wt% 및 10wt%로 각각 첨가된 실시예 3 및 5와 법랑 조성물에 항균 유리 조성물이 첨가되지 않은 비교예 4와 비교해 본 결과, 색차 값 및 광택도 값에서 상호 유사한 수준을 나타내는 것을 확인하였다.As shown in Table 3, the color difference values were compared with Examples 3 and 5, in which the antimicrobial glass composition was added to the enamel composition at 1 wt% and 10 wt%, respectively, and Comparative Example 4, in which the antibacterial glass composition was not added to the enamel composition. and it was confirmed that they exhibited similar levels to each other in gloss values.
위의 실험 결과로부터 알 수 있듯이, 실시예 3 및 5에 따라 제조된 법랑 시편들의 경우, 외관의 변화 및 성능의 변화가 발생하지 않은 것을 확인하였다.As can be seen from the above experimental results, in the case of the enamel specimens prepared according to Examples 3 and 5, it was confirmed that there was no change in appearance or performance.
이상과 같이 본 발명에 대해서 예시한 도면을 참조로 하여 설명하였으나, 본 명세서에 개시된 실시 예와 도면에 의해 본 발명이 한정되는 것은 아니며, 본 발명의 기술사상의 범위 내에서 통상의 기술자에 의해 다양한 변형이 이루어질 수 있음은 자명하다. 아울러 앞서 본 발명의 실시 예를 설명하면서 본 발명의 구성에 따른 작용 효과를 명시적으로 기재하여 설명하지 않았을 지라도, 해당 구성에 의해 예측 가능한 효과 또한 인정되어야 함은 당연하다.As described above, the present invention has been described with reference to the illustrated drawings, but the present invention is not limited by the embodiments and drawings disclosed in the present specification. It is obvious that variations can be made. In addition, although the effects according to the configuration of the present invention have not been explicitly described and described while describing the embodiments of the present invention, it is natural that the effects predictable by the configuration should also be recognized.
[부호의 설명][Explanation of code]
S110 : 1차 혼합 단계S110: first mixing step
S120 : 용융 단계S120: melting stage
S130 : 냉각 단계S130: cooling stage
S140 : 분쇄 단계S140: crushing step
S150 : 2차 혼합 단계S150: Second mixing step

Claims (16)

  1. 법랑 조성물; 및 enamel composition; and
    상기 법랑 조성물에 혼합된 항균 유리 분말;을 포함하며, Including; antibacterial glass powder mixed in the enamel composition,
    상기 항균 유리 분말은 The antibacterial glass powder is
    SiO2 26 ~ 50 중량%; SiO 2 26 to 50% by weight;
    B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%; 0.5 to 4 wt% of at least one B 2 O 3 and P 2 O 5 ;
    Na2O 및 K2O 1종 이상 15 ~ 27 중량%; 15 to 27 wt% of at least one Na 2 O and K 2 O;
    CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%; 및 3 to 20% by weight of at least one of CaO, MgO and WO 3 ; and
    ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%; 22 to 44 wt% of at least one of ZnO and SnO;
    를 포함하는 복합 유리 조성물.A composite glass composition comprising a.
  2. 제1항에 있어서,According to claim 1,
    상기 Na2O는 5 ~ 18 중량%로 첨가되고, The Na 2 O is added in an amount of 5 to 18% by weight,
    상기 K2O는 5 ~ 13 중량%로 첨가된 복합 유리 조성물.The K 2 O is added in an amount of 5 to 13% by weight of the composite glass composition.
  3. 제2항에 있어서,3. The method of claim 2,
    상기 Na2O 및 K2O는 The Na 2 O and K 2 O are
    하기 식 1을 만족하는 범위로 첨가된 복합 유리 조성물.A composite glass composition added in a range satisfying Equation 1 below.
    식 1 : 0.5 ≤ [Na2O] / [K2O] ≤ 1.5Equation 1: 0.5 ≤ [Na 2 O] / [K 2 O] ≤ 1.5
    (여기서, []는 각 성분의 함량비를 나타냄.)(Here, [] indicates the content ratio of each component.)
  4. 제1항에 있어서,According to claim 1,
    상기 항균 유리 분말은 The antibacterial glass powder is
    Ag2O, Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함하는 포함하는 복합 유리 조성물.Ag 2 O, Ag 3 PO 4 , and AgNO 3 Composite glass composition further comprising 0.1% by weight or less of one or more.
  5. 제1항에 있어서,According to claim 1,
    상기 복합 유리 조성물은 The composite glass composition is
    상기 법랑 조성물 80 ~ 99.5 중량%; 및 80 to 99.5% by weight of the enamel composition; and
    상기 항균 유리 분말 0.5 ~ 20 중량%로 혼합된 복합 유리 조성물.A composite glass composition mixed with the antibacterial glass powder in an amount of 0.5 to 20% by weight.
  6. 제5항에 있어서,6. The method of claim 5,
    상기 법랑 조성물은 The enamel composition is
    P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함하는 복합 유리 조성물.P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1 to 20 % by weight, Li 2 O 1 to 10% by weight, NaF 5% by weight or less, B 2 O 3 1 to 20% by weight, TiO 2 5% by weight or less, and V 2 O 5 10% by weight or less.
  7. SiO2 26 ~ 50 중량%, B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%, Na2O 및 K2O 1종 이상 15 ~ 27 중량%, CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%, 및 ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%로 혼합하고 교반하여 항균 유리 조성물을 형성하는 단계; SiO 2 26-50 wt%, B 2 O 3 and P 2 O 5 at least one kind 0.5-4 wt%, Na 2 O and K 2 O at least one kind 15-27 wt%, CaO, MgO and 1 of WO 3 Forming an antibacterial glass composition by mixing and stirring 3 to 20% by weight of at least one species, and 22 to 44% by weight of at least one of ZnO and SnO;
    상기 항균 유리 조성물을 용융시키는 단계; melting the antimicrobial glass composition;
    상기 용융된 항균 유리 조성물을 냉각하는 단계; cooling the molten antimicrobial glass composition;
    상기 냉각된 항균 유리를 분쇄하는 단계; 및 crushing the cooled antibacterial glass; and
    상기 분쇄된 항균 유리 분말을 법랑 조성물에 혼합하는 단계; mixing the pulverized antibacterial glass powder into an enamel composition;
    를 포함하는 복합 유리 조성물 제조 방법.A method for manufacturing a composite glass composition comprising a.
  8. 제7항에 있어서,8. The method of claim 7,
    상기 Na2O는 5 ~ 18 중량%로 첨가하고, The Na 2 O is added in an amount of 5 to 18% by weight,
    상기 K2O는 5 ~ 13 중량%로 첨가하는 복합 유리 조성물 제조 방법.The method for producing a composite glass composition in which K 2 O is added in an amount of 5 to 13% by weight.
  9. 제8항에 있어서,9. The method of claim 8,
    상기 Na2O 및 K2O는 The Na 2 O and K 2 O are
    하기 식 1을 만족하는 범위로 첨가하는 복합 유리 조성물 제조 방법.A method for producing a composite glass composition, which is added in a range satisfying the following formula (1).
    식 1 : 0.5 ≤ [Na2O] / [K2O] ≤ 1.5Equation 1: 0.5 ≤ [Na 2 O] / [K 2 O] ≤ 1.5
    (여기서, []는 각 성분의 함량비를 나타냄.)(Here, [] indicates the content ratio of each component.)
  10. 제7항에 있어서,8. The method of claim 7,
    상기 항균 유리 분말은 The antibacterial glass powder is
    Ag2O, Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함하는 복합 유리 조성물 제조 방법.Ag 2 O, Ag 3 PO 4 A method of manufacturing a composite glass composition further comprising 0.1 wt% or less of at least one of AgNO 3 .
  11. 제7항에 있어서,8. The method of claim 7,
    상기 복합 유리 조성물은 The composite glass composition is
    상기 법랑 조성물 80 ~ 99.5 중량%; 및 80 to 99.5% by weight of the enamel composition; and
    상기 항균 유리 분말 0.5 ~ 20 중량%로 혼합된 복합 유리 조성물 제조 방법.A method for producing a composite glass composition in which the antibacterial glass powder is mixed in an amount of 0.5 to 20% by weight.
  12. 제11항에 있어서,12. The method of claim 11,
    상기 법랑 조성물은 The enamel composition is
    P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함하는 복합 유리 조성물 제조 방법.P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1 to 20 % by weight, Li 2 O 1-10 wt%, NaF 5 wt% or less, B 2 O 3 1-20 wt%, TiO 2 5 wt% or less, and V 2 O 5 10 wt% or less Way.
  13. 제7항에 있어서,8. The method of claim 7,
    상기 용융은 The melting is
    1,100 ~ 1,400℃에서 1 ~ 60분 동안 실시하는 복합 유리 조성물 제조 방법.A method for manufacturing a composite glass composition carried out at 1,100 to 1,400° C. for 1 to 60 minutes.
  14. 모재 내에 복합 유리 조성물이 첨가되거나, 모재의 표면에 복합 유리 조성물이 코팅된 사출물을 포함하는 조리기기로서, A cooking appliance comprising an injection molded product in which a composite glass composition is added to a base material or coated with a composite glass composition on a surface of a base material,
    상기 모재는 고분자 수지 또는 금속 재질이고, The base material is a polymer resin or a metal material,
    상기 복합 유리 조성물은 법랑 조성물과, 상기 법랑 조성물에 혼합된 항균 유리 분말을 포함하며, The composite glass composition includes an enamel composition and an antibacterial glass powder mixed with the enamel composition,
    상기 항균 유리 분말은 SiO2 26 ~ 50 중량%, B2O3 및 P2O5 1종 이상 0.5 ~ 4 중량%, Na2O 및 K2O 1종 이상 15 ~ 27 중량%, CaO, MgO 및 WO3 중 1종 이상 3 ~ 20 중량%, 및 ZnO 및 SnO 중 1종 이상 22 ~ 44 중량%를 포함하는 조리기기.The antibacterial glass powder is SiO 2 26-50 wt%, B 2 O 3 and P 2 O 5 one or more 0.5-4 wt%, Na 2 O and K 2 O one or more 15-27 wt%, CaO, MgO and 3 to 20% by weight of at least one of WO 3 and 22 to 44% by weight of at least one of ZnO and SnO.
  15. 제14항에 있어서,15. The method of claim 14,
    상기 복합 유리 조성물은 The composite glass composition is
    상기 법랑 조성물 80 ~ 99.5 중량%; 및 80 to 99.5% by weight of the enamel composition; and
    상기 항균 유리 분말 0.5 ~ 20 중량%로 혼합된 포함하는 조리기기.A cooking appliance comprising 0.5 to 20% by weight of the antibacterial glass powder.
  16. 제15항에 있어서,16. The method of claim 15,
    상기 법랑 조성물은 The enamel composition is
    P2O5 10 ~ 35 중량%, SiO2 10 ~ 45 중량%, Al2O3 5 ~ 20 중량%, ZrO2 10 중량% 이하, Na2O 1 ~ 15 중량%, K2O 1 ~ 20 중량%, Li2O 1 ~ 10 중량%, NaF 5 중량% 이하, B2O3 1 ~ 20 중량%, TiO2 5 중량% 이하 및 V2O5 10 중량% 이하를 포함하는 조리기기.P 2 O 5 10 to 35 wt%, SiO 2 10 to 45 wt%, Al 2 O 3 5 to 20 wt%, ZrO 2 10 wt% or less, Na 2 O 1 to 15 wt%, K 2 O 1 to 20 Weight %, Li 2 O 1 ~ 10% by weight, NaF 5% by weight or less, B 2 O 3 1 ~ 20% by weight, TiO 2 5% by weight or less, and V 2 O 5 Cooking appliance comprising 10% by weight or less.
PCT/KR2021/019100 2021-01-04 2021-12-15 Composite glass composition, preparation method therefor, and cooking apparatus comprising same WO2022145821A1 (en)

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