WO2022265405A1 - Antibacterial glass composition, method for preparing antibacterial glass powder thereof, and household electronic appliance comprising same - Google Patents
Antibacterial glass composition, method for preparing antibacterial glass powder thereof, and household electronic appliance comprising same Download PDFInfo
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- WO2022265405A1 WO2022265405A1 PCT/KR2022/008496 KR2022008496W WO2022265405A1 WO 2022265405 A1 WO2022265405 A1 WO 2022265405A1 KR 2022008496 W KR2022008496 W KR 2022008496W WO 2022265405 A1 WO2022265405 A1 WO 2022265405A1
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- 239000011521 glass Substances 0.000 title claims abstract description 151
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 136
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- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title abstract description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 23
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- 238000002844 melting Methods 0.000 claims description 19
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- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 13
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- 239000004599 antimicrobial Substances 0.000 abstract description 5
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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Images
Classifications
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- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/1005—Forming solid beads
- C03B19/102—Forming solid beads by blowing a gas onto a stream of molten glass or onto particulate materials, e.g. pulverising
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- 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
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- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
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- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- 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
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- 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
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- 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
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- 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
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- C03C3/111—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing nitrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L25/08—Copolymers of styrene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Definitions
- the present invention relates to an antibacterial glass composition, a method for manufacturing the antibacterial glass powder, and home appliances including the same.
- Bacteria and fungi propagate in parts exposed to moisture among parts in which plastic injection molding is used in such home appliances, causing problems in appearance or use environment.
- antibacterial agents must have antibacterial performance against these strains.
- the antibacterial agent must be strictly selected as a material with low toxicity to the human body and the environment and a material with durability against high temperatures.
- Antimicrobial agents can be largely divided into inorganic and organic types.
- the organic antibacterial agent exhibits excellent antibacterial performance because the material having antibacterial performance is eluted toward the surface by water to express antimicrobial activity against bacteria, but durability may be deteriorated when applied to a washing machine.
- organic antibacterial agents have been recently eluted to human health and environmental hazards have been raised.
- Inorganic antibacterial agents have significantly lower solubility than organic antimicrobial agents and can secure high-temperature durability, but problems may arise in interfacial wettability with plastic injection products, and since Ag is used as an antibacterial material in most cases, the price is high, so the application is limited. .
- non-eluting antibacterial glass does not mean that the entire glass is non-eluting, and a glass composed of a water-insoluble glass substrate and ions or crystalline components eluted for antibacterial purposes is called non-eluting.
- an object of the present invention is to form a strong glass structure that is not eluted in water by strictly controlling each component of the glass composition and its component ratio so that Zn and Ca ions, which are components that exhibit antibacterial performance, participate in the network-forming structure,
- An antibacterial glass composition that exhibits antibacterial properties without elution in water by controlling the surface charge of glass, a method for manufacturing the antibacterial glass powder, and home appliances including the same are provided.
- an object of the present invention is to exhibit non-emission characteristics by strictly controlling each component of the glass composition and its component ratio, and thus have an excellent effect in preventing contamination by bacteria and mold when used as a coating agent for parts that come into contact with drinking water. It is to provide an antibacterial glass composition capable of exhibiting antibacterial glass powder, a method for manufacturing the antibacterial glass powder, and home appliances including the same.
- the antibacterial glass powder manufacturing method thereof, and home appliances including the same metal ions in the glass cause the surface charge of the glass, that is, zeta potential, to be positively charged. It attracts negatively charged bacteria and creates a charged atmosphere in which bacteria cannot grow, thereby killing the bacteria.
- the antibacterial glass composition according to the present invention is an antibacterial agent exhibiting non-elution characteristics, when used as a coating agent for parts that come into contact with drinking water, it exhibits an excellent effect in preventing contamination by bacteria and fungi.
- the antibacterial glass composition according to the present invention contains 25 to 45% by weight of SiO 2 , 3 to 20% by weight of one or more types of B 2 O 3 and P 2 O 5 , 10 to 30% by weight of one or more types of Na 2 O and K 2 O . 10 to 30 wt% of at least one of ZnO and CaO, and 0.1 to 3 wt% of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 .
- the present invention since it is a water-insoluble antibacterial agent composed of multi-purpose antimicrobial components, it can be used permanently when used as a coating material for glass shelves and an additive for plastic injection molding products.
- the present invention since it is an antibacterial agent exhibiting non-elimination characteristics, when used as a coating agent for a group of parts that come into contact with drinking water, it exhibits an excellent effect in preventing contamination by bacteria and fungi.
- FIG. 1 is a process flow chart showing a method for manufacturing an antibacterial glass powder according to an embodiment of the present invention.
- an antibacterial glass composition according to some embodiments of the present invention, a method for manufacturing the antibacterial glass powder, and home appliances including the same will be described.
- the antibacterial glass composition according to the embodiment of the present invention has an antibacterial effect that is permanently effective even when the glass does not react with water at all even in water.
- the intermediate oxide in order to take advantage of the fact that the intermediate oxide can serve as both a modifying oxide and a network forming oxide during glass formation, components exhibiting antibacterial performance by controlling each component and its component ratio.
- Phosphorus Zn and Ca ions participate in the network structure to form a strong glass structure that is not eluted in water, and by controlling the surface charge of the glass, it is possible to exhibit antibacterial properties without eluted in water.
- the antibacterial glass composition according to an embodiment of the present invention controls antibacterial activity and water resistance by controlling the netting to be achieved by using the content ratio of the modifying oxide and the netting oxide to elute Zn and Ca ions to implement the antibacterial function. secured at the same time.
- elements for manufacturing an antibacterial glass composition having excellent durability may be largely divided into two types.
- the conventional carrier is a type in which an antibacterial component is supported on the surface of an inorganic antimicrobial agent, but in the present invention, a metal material expressing antibacterial properties is present in the glass substrate in the form of an ion.
- a metal material expressing antibacterial properties is present in the glass substrate in the form of an ion.
- the content ratio of glass formers such as SiO 2 and B 2 O 3 is important, but also the mixed alkali effect in glass (mixed alkali effect in glass: mechanical properties of glass depend on the ratio of alkali components). may change nonlinearly) is also a very important factor.
- the antibacterial glass composition according to the embodiment of the present invention is an antibacterial agent exhibiting non-elution characteristics, when used as a coating agent for parts that come into contact with drinking water, it exhibits an excellent effect in preventing contamination by bacteria and fungi.
- SiO 2 , B 2 O 3 and P 2 O 5 are network-forming oxides, which form a framework structure of glass and are key components enabling vitrification by covalent bonding.
- SiO 2 is a glass forming agent that enables vitrification and is a key component that serves as a framework in terms of glass structure. When such SiO 2 is included in an appropriate amount or more, viscosity increases during melting of the glass, resulting in reduced workability and yield during the cooling process. In addition, SiO 2 does not act as a direct component that expresses antibacterial activity, but forms less OH - groups on the glass surface compared to P 2 O 5 , which is a representative network-forming oxide, and thus causes the glass surface caused by metal ions in the glass to be positively charged. It is advantageous to wear
- SiO 2 is preferably added in a content ratio of 25 to 45% by weight of the total weight of the antimicrobial glass composition according to the present invention.
- the added amount of SiO 2 is less than 25% by weight, opacification may occur due to the lack of network-forming oxides and thus escape from the vitrification region, or heterogeneity in which transparent glass may coexist.
- the amount of SiO 2 added exceeds 45% by weight, it is difficult to control the surface charge of the glass to a positive value, so the antibacterial activity may decrease.
- B 2 O 3 and P 2 O 5 are representative network-forming oxides and, together with SiO 2 , are key components enabling sufficient vitrification.
- B 2 O 3 and P 2 O 5 have low melting points and are used for lowering the eutectic point of a melt.
- B 2 O 3 and P 2 O 5 act to increase the solubility of rigid components (Al 2 O 3 , CuO, etc.) during melting for vitrification, resulting in a homogeneous glass. help to become
- B 2 O 3 and P 2 O 5 are added in a certain amount, a problem of deteriorating water resistance by weakening the bonding structure of glass may occur.
- B 2 O 3 and P 2 O 5 are preferably used in small amounts only for lowering the melting point in order to realize water-insoluble antibacterial glass.
- one or more of B 2 O 3 and P 2 O 5 is preferably added in a content ratio of 3 to 20% by weight of the total weight of the antibacterial glass composition according to the present invention.
- the melting agent is insufficient, so that the vitrification region is not reached, and thus, a non-melting phenomenon may occur.
- one or more of B 2 O 3 and P 2 O 5 exceeds 20% by weight, a decrease in water resistance may occur due to the nature of the elements due to structural problems of B and P in the network-forming structure.
- Alkali oxides such as Na 2 O and K 2 O are oxides that act as network modifiers for non-crosslinking in the glass composition. Although these components cannot be vitrified alone, they can be vitrified when mixed with network forming agents such as SiO 2 and B 2 O 3 in a certain ratio. If only one of the components is included in the glass composition, the durability of the glass may be weakened in a vitrifiable region. However, when two or more components are included in the glass composition, the durability of the glass is improved again depending on the ratio. This is called the mixed alkali effect.
- alkali oxides such as Na 2 O and K 2 O improve antibacterial activity by using the fact that alkali oxides first occupy a modified oxide site in glass.
- alkali oxides such as Na 2 O and K 2 O contribute to the formation of a network by making the intermediate oxides ZnO and CaO to contribute to the formation of a network, thereby enhancing durability and contributing to the expression of antimicrobial activity by water insolubility and surface charge. do.
- Na 2 O is added at 4 to 20% by weight
- K 2 O is more preferably added at 6 to 20% by weight.
- ZnO and CaO are components that play both roles as network-forming oxides and modifier oxides by substituting and covalently bonding with some of the network-forming oxides.
- ZnO and CaO are components that greatly contribute to the expression of antibacterial effects.
- ZnO and CaO are intermediate oxides, and in order to participate in the network formation structure in glass, they must have a small atomic radius and a large electronegativity to have a small difference with oxygen. These intermediate oxides have a larger atomic radius than typical network-forming oxides, such as Si, P, and B, and have low electronegativity, making it difficult to form a glass alone. say the ingredients. These ZnO and CaO serve only as modified oxides below a certain content, but above a certain content, they form covalent bonds to rapidly improve durability.
- the predetermined content is determined by the content of the network-forming oxide and the modifier oxide.
- At least one of ZnO and CaO is preferably added in a content ratio of 10 to 30% by weight of the total weight of the antimicrobial glass composition according to the present invention.
- ZnO and CaO is added in an amount of less than 10% by weight, there is a problem in that sufficient antibacterial activity is not expressed because the absolute amount of the substance exhibiting antibacterial activity is insufficient.
- ZnO and CaO are added in excess of more than 30% by weight, they do not exist in the ionic state in the glass in a homogeneous manner, and opacification occurs due to partial crystal formation and leaving the vitrification region, resulting in transparent glass Mixed heterogeneity may occur.
- the composition of the present invention includes 0.1 to 3% by weight of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 .
- the composition of the present invention does not exhibit sufficient antibacterial activity.
- one or more of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 is included in an amount exceeding 3% by weight, there is a problem in that metal precipitation occurs due to a reduction reaction and vitrification does not occur. can
- Ag 3 PO 4 and AgNO 3 exist in an ionic state in glass and are effective components for expressing antibacterial activity.
- Ag 3 PO 4 and AgNO 3 serve to lower the melting point.
- at least one of Ag 3 PO 4 and AgNO 3 is preferably added in a strictly limited amount of 0.1% by weight or less based on the total weight of the antimicrobial glass composition according to the present invention.
- each of the above-described materials such as Silver Oxide, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 exists in a covalent bond state.
- the component exists in an ion-bound state, and when in an ionic state, it is active and exhibits antibacterial properties. In order to exhibit antibacterial activity by using the component alone in the glass, it needs to be included in a high content.
- the base matrix should be Borate or Phosphate Glass, R 2 O (Alkali Oxide)/RO (Alkaline-earth Oxide) with relatively high ionization tendency, and low structural complexity.
- FIG. 1 is a process flow chart showing a method for manufacturing an antibacterial glass powder according to an embodiment of the present invention.
- the antibacterial glass powder manufacturing method includes a mixing step (S110), a melting step (S120), a cooling step (S130), and a grinding step (S140).
- the mixing step (S110) 25 to 45 wt% of SiO 2 , 3 to 20 wt% of at least one B 2 O 3 and P 2 O 5 , 10 to 30 wt% of at least one Na 2 O and K 2 O, ZnO and 10 to 30% by weight of one or more of CaO and 0.1 to 3% by weight of one or more of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 are mixed and stirred to form an antibacterial glass composition .
- SiO 2 is preferably added in an amount higher than that of B 2 O 3 .
- Na 2 O is added at 4 to 20% by weight
- K 2 O is added at 6 to 20% by weight
- the antibacterial glass composition may further include 0.1% by weight or less of at least one of Ag 3 PO 4 and AgNO 3 .
- the molten antibacterial glass composition is cooled to room temperature.
- the plastic injection product includes 95.0 to 99.0% by weight of the resin material and 1.0 to 5.0% by weight of the antibacterial glass powder.
- the antibacterial glass powder When the antibacterial glass powder is added in a small amount of less than 1.0% by weight of the total weight of the plastic injection molding, the antibacterial activity against Pseudomonas aeruginosa may not be sufficient. Conversely, when the antibacterial glass powder is added in excess of 5.0% by weight of the total weight of the plastic injection molding product, mechanical properties may be deteriorated.
- the resin material includes at least one of polypropylene (PP), polycarbonate (PC), ethylene propylene rubber (EPDM), acrylonitrile-buradiene-styrene (ABS), and high impact polystyrene (HIPS).
- PP polypropylene
- PC polycarbonate
- EPDM ethylene propylene rubber
- ABS acrylonitrile-buradiene-styrene
- HIPS high impact polystyrene
- Na 2 O is added at 4 to 20% by weight
- K 2 O is added at 6 to 20% by weight
- a functional additive may be further included in the plastic injection molding product in addition to the antibacterial glass powder.
- the functional additive may include at least one selected from antioxidants, foaming agents, impact modifiers, nucleating agents, coupling agents, and the like.
- the home appliance according to the embodiment of the present invention is applied to the surface of a part that is vulnerable to bacterial propagation and has a lot of contact with moisture, and has antibacterial activity capable of preventing the habitat and growth of various microorganisms.
- Na 2 CO 3 , K 2 CO 3 , and CaCO 3 were used as raw materials for the components Na 2 O, K 2 O, and CaO, respectively, and the other components were the same as those described in Tables 1 and 2.
- vitrification was classified based on the case of homogeneously showing glass properties and the phenomenon of opacification and minor melting.
- the WHO guide and domestic drinking water standards were used through the ASTM C1285-14 (glass and glass ceramic durability evaluation method) test method in Table 5 below. Elution levels for the listed elements were evaluated for pass or fail.
- the chemical durability was expressed as O when the elution amount for each element listed in Table 3 at 50 ° C. for 32 hours was less than the reference value, and was expressed as X when it was more than the reference value.
- Example 2 Comparative Example 1 Comparative Example 2 Staphylococcus aureus 99.99% 99.99% 71.0% 38.4% Escherichia coil 99.99% 99.99% 62.7% 55.5% Klebsiella pneumoniae 99.99% 99.99% 50.5% 67.9% Pseudomonas aeruginosa 99.9% 99.9% 48.0% 21.4%
- the injection products manufactured according to the comparative example were measured as less than 2.0 in antibacterial activity and showed an antibacterial activity of 80% or less.
Abstract
Disclosed are: an antibacterial glass composition; a method for preparing an antibacterial glass powder thereof; and a household electronic appliance comprising same, wherein antibacterial activity and water resistance are achieved by controlling Zn and Ca ions, which are eluted in order to bring about antibacterial functions, to achieve network formation by using the content ratio of a modified oxide and a network-forming oxide. As a result, the antibacterial glass composition, the method for preparing an antibacterial glass powder thereof, and the household electronic appliance comprising same according to the present invention use antimicrobials which have non-eluting characteristics and can thus exhibit remarkable effects in preventing bacterial or mold contamination when used as a coating agent on components that come into contact with drinking water.
Description
본 발명은 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품에 관한 것이다.The present invention relates to an antibacterial glass composition, a method for manufacturing the antibacterial glass powder, and home appliances including the same.
세균, 균류, 박테리아와 같은 미생물은 정수기, 냉장고, 오븐, 세탁기 등과 같은 우리의 생활 공간에 편재해 있다. 만일, 미생물이 인체에 들어가게 되면, 이들은 생명을 위협하는 감염의 원인이 될 수 있다. 따라서, 정수기, 냉장고, 오븐, 세탁기 등과 같은 가전제품에 미생물의 확산을 제어할 수 있는 항균 유리 조성물이 요구된다. Microorganisms such as germs, fungi, and bacteria are ubiquitous in our living spaces, such as water purifiers, refrigerators, ovens, and washing machines. If microorganisms enter the human body, they can cause life-threatening infections. Therefore, there is a need for an antibacterial glass composition capable of controlling the spread of microorganisms in home appliances such as water purifiers, refrigerators, ovens, and washing machines.
이러한 가전제품에서 플라스틱 사출물이 사용되는 부품 중 수분에 노출되는 부품에서 세균 및 곰팡이가 번식하여 외관상 혹은 사용 환경에 문제를 일으킨다.Bacteria and fungi propagate in parts exposed to moisture among parts in which plastic injection molding is used in such home appliances, causing problems in appearance or use environment.
가전제품에 서식하는 균은 매우 다양하고, 부품 별로 주요 균주가 상이할 수 있으나, 수분에 노출되는 부품에는 일반적으로 녹농균이 서식할 가능성이 높다.Bacteria inhabiting home appliances are very diverse, and major strains may be different for each part, but there is a high possibility that Pseudomonas aeruginosa inhabits in general on parts exposed to moisture.
따라서, 항균제는 이러한 균주에 대한 항균 성능이 확보되어야 한다. 또한, 항균제는 인체 및 환경에 대한 독성이 낮은 재료, 고온에 대한 내구성이 확보된 재료로 엄격히 선정되어야 한다.Therefore, antibacterial agents must have antibacterial performance against these strains. In addition, the antibacterial agent must be strictly selected as a material with low toxicity to the human body and the environment and a material with durability against high temperatures.
항균제는 크게 무기계 및 유기계로 나눌 수 있다. 유기 항균제는 항균 성능을 가지는 소재를 물에 의해 표면 쪽으로 용출시켜 균에 대한 항균력을 발현하므로 뛰어난 항균 성능을 보이나, 세탁기에 적용 시 내구성이 저하될 수 있다. 또한, 유기 항균제는 최근 용출된 소재의 인체 및 환경 유해성 문제가 제기되고 있다. 또한, 낮은 분해 온도로 사출 공정 시 분해될 위험이 있다.Antimicrobial agents can be largely divided into inorganic and organic types. The organic antibacterial agent exhibits excellent antibacterial performance because the material having antibacterial performance is eluted toward the surface by water to express antimicrobial activity against bacteria, but durability may be deteriorated when applied to a washing machine. In addition, organic antibacterial agents have been recently eluted to human health and environmental hazards have been raised. In addition, there is a risk of decomposition during the injection process due to the low decomposition temperature.
무기 항균제는 용출성이 유기 항균제에 비해 상당히 낮고 고온 내구성을 확보할 수 있지만, 플라스틱 사출물과의 계면 젖음성 문제가 발생할 수 있고 항균 소재로 Ag를 사용하는 경우가 대부분이므로 가격이 높아 적용에 한계가 있다.Inorganic antibacterial agents have significantly lower solubility than organic antimicrobial agents and can secure high-temperature durability, but problems may arise in interfacial wettability with plastic injection products, and since Ag is used as an antibacterial material in most cases, the price is high, so the application is limited. .
종래의 비용출성 항균 유리는 유리 전체가 비용출성을 의미하는 것은 아니고, 수불용성인 유리 기질과 항균성을 목적으로 용출되는 이온 또는 결정상 성분으로 구성된 유리를 비용출성으로 명명하고 있다.Conventional non-eluting antibacterial glass does not mean that the entire glass is non-eluting, and a glass composed of a water-insoluble glass substrate and ions or crystalline components eluted for antibacterial purposes is called non-eluting.
결과적으로, 항균력을 발현하기 위해서는 항균성능을 발현하는 이온 혹은 결정상이 용출되어야 한다. 그러나, 종래의 용출성 항균 유리는 장기 지속성을 발휘하기 어려우며, 식음수에 닿는 부품에 적용하는데 안전성에 한계가 있었다.As a result, in order to express antibacterial activity, ions or crystal phases exhibiting antibacterial activity must be eluted. However, it is difficult for the conventional eluting antibacterial glass to exhibit long-term sustainability, and there is a limit in safety when applied to parts that come into contact with drinking water.
(특허문헌 1) KR 공개특허공보 제10-2005-0022510호(2005.03.08. 공개)(Patent Document 1) KR Unexamined Patent Publication No. 10-2005-0022510 (published on March 8, 2005)
본 발명의 목적은 기존의 용출 메커니즘과 달리 유리가 물속에서도 전혀 물과 반응하지 않아도 영구적으로 효과가 지속되는 항균 작용을 발휘하는 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품을 제공하는 것이다.An object of the present invention is to provide an antibacterial glass composition that exhibits an antibacterial effect that is permanently effective even when the glass does not react with water at all, unlike conventional elution mechanisms, a method for manufacturing antibacterial glass powder, and home appliances including the same. is to provide
아울러, 본 발명의 목적은 유리 조성물의 각 성분 및 이의 성분비를 엄격히 제어하여 항균 성능을 발현하는 성분인 Zn, Ca 이온이 망목형성 구조에 참여하도록 하여 물에 용출되지 않는 강건한 유리 구조를 형성함으로써, 유리의 표면 전하를 제어하여 물에서 용출되는 것 없이 항균성을 발휘하는 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품을 제공하는 것이다.In addition, an object of the present invention is to form a strong glass structure that is not eluted in water by strictly controlling each component of the glass composition and its component ratio so that Zn and Ca ions, which are components that exhibit antibacterial performance, participate in the network-forming structure, An antibacterial glass composition that exhibits antibacterial properties without elution in water by controlling the surface charge of glass, a method for manufacturing the antibacterial glass powder, and home appliances including the same are provided.
또한, 본 발명의 목적은 유리 조성물의 각 성분 및 이의 성분비를 엄격히 제어하는 것에 의해 비용출 특성을 나타내어, 식음수에 닿는 부품군에 코팅제로 사용할 시, 세균, 곰팡이 등의 오염을 막는데 탁월한 효과를 발휘할 수 있는 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품을 제공하는 것이다.In addition, an object of the present invention is to exhibit non-emission characteristics by strictly controlling each component of the glass composition and its component ratio, and thus have an excellent effect in preventing contamination by bacteria and mold when used as a coating agent for parts that come into contact with drinking water. It is to provide an antibacterial glass composition capable of exhibiting antibacterial glass powder, a method for manufacturing the antibacterial glass powder, and home appliances including the same.
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 above can 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 means of the instrumentalities and combinations indicated in the claims.
본 발명에 따른 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품은 항균 기능을 구현하기 위하여 용출시키는 Zn, Ca 이온을 수식산화물과 망목형성 산화물의 함량비를 이용하여 망목형성이 이루어지도록 제어하여 항균력과 내수성을 동시에 확보하였다.The antibacterial glass composition according to the present invention, the method for manufacturing the antibacterial glass powder, and home appliances including the same can form a mesh by using the content ratio of the modified oxide and the mesh-forming oxide to elute Zn and Ca ions to realize antibacterial function. It was controlled to ensure antibacterial activity and water resistance at the same time.
아울러, 본 발명에 따른 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품은 유리 내 금속이온이 유리의 표면 전하, 즉 제타 포텐셜(zeta potential)을 양의 전하를 띠게 해, 통상적으로 음의 전하를 띠는 세균을 끌어당기고 세균이 성장할 수 없는 전하 분위기를 조성해 균을 사멸시키게 된다.In addition, in the antibacterial glass composition according to the present invention, the antibacterial glass powder manufacturing method thereof, and home appliances including the same, metal ions in the glass cause the surface charge of the glass, that is, zeta potential, to be positively charged. It attracts negatively charged bacteria and creates a charged atmosphere in which bacteria cannot grow, thereby killing the bacteria.
이 결과, 본 발명에 따른 항균 유리 조성물은 비용출 특성을 나타내는 항균제이므로, 식음수에 닿는 부품군에 코팅제로 사용할 시, 세균, 곰팡이 등의 오염을 막는데 탁월한 효과를 발휘하게 된다.As a result, since the antibacterial glass composition according to the present invention is an antibacterial agent exhibiting non-elution characteristics, when used as a coating agent for parts that come into contact with drinking water, it exhibits an excellent effect in preventing contamination by bacteria and fungi.
이를 위해, 본 발명에 따른 항균 유리 조성물은 SiO2 25 ~ 45 중량%, B2O3 및 P2O5 1종 이상 3 ~ 20 중량%, Na2O 및 K2O 1종 이상 10 ~ 30 중량%, ZnO 및 CaO 중 1종 이상 10 ~ 30 중량% 및 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%를 포함한다.To this end, the antibacterial glass composition according to the present invention contains 25 to 45% by weight of SiO 2 , 3 to 20% by weight of one or more types of B 2 O 3 and P 2 O 5 , 10 to 30% by weight of one or more types of Na 2 O and K 2 O . 10 to 30 wt% of at least one of ZnO and CaO, and 0.1 to 3 wt% of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 .
또한, 본 발명에 따른 항균 유리 조성물은 Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함할 수 있다.In addition, the antibacterial glass composition according to the present invention may further include 0.1% by weight or less of at least one of Ag 3 PO 4 and AgNO 3 .
본 발명에 따르면, 유리 조성물의 각 성분 및 이의 성분비를 엄격히 제어하여 항균 성능을 발현하는 성분인 Zn, Ca 이온이 망목형성 구조에 참여하도록 하여 물에 용출되지 않는 강건한 유리 구조를 형성함으로써, 유리의 표면 전하를 제어하여 물에서 용출되는 것 없이 항균성을 발휘할 수 있게 된다.According to the present invention, each component of the glass composition and its component ratio are strictly controlled to allow Zn and Ca ions, which are components that exhibit antibacterial performance, to participate in the network-forming structure to form a strong glass structure that is not eluted in water. By controlling the surface charge, it is possible to exhibit antibacterial properties without eluting from water.
또한, 본 발명에 따르면, 다목적 항균성 성분으로 이루어지는 수불용성 항균제이므로, 유리 선반의 코팅 재료 및 플라스틱 사출품의 첨가제로 활용할 시, 영구적으로 사용할 수 있게 된다.In addition, according to the present invention, since it is a water-insoluble antibacterial agent composed of multi-purpose antimicrobial components, it can be used permanently when used as a coating material for glass shelves and an additive for plastic injection molding products.
아울러, 본 발명에 따르면, 비용출 특성을 나타내는 항균제이므로, 식음수에 닿는 부품군에 코팅제로 사용할 시, 세균, 곰팡이 등의 오염을 막는데 탁월한 효과를 발휘하게 된다.In addition, according to the present invention, since it is an antibacterial agent exhibiting non-elimination characteristics, when used as a coating agent for a group of parts that come into contact with drinking water, it exhibits an excellent effect in preventing contamination by bacteria and fungi.
상술한 효과와 더불어 본 발명의 구체적인 효과는 이하 발명을 실시하기 위한 구체적인 사항을 설명하면서 함께 기술한다.In addition to the effects described above, specific effects of the present invention will be described together while explaining specific details for carrying out the present invention.
도 1은 본 발명의 실시예에 따른 항균 유리 분말 제조 방법을 나타낸 공정 순서도이다.1 is a process flow chart showing a method for manufacturing an antibacterial glass powder 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 objects, features and advantages will be described later in detail with reference to the accompanying drawings, and accordingly, those skilled in the art to which the present invention belongs will be able to easily implement the technical spirit of the present invention. In describing the present invention, if it is determined that the detailed description of the known technology related to the present invention may unnecessarily obscure the subject matter 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.Singular expressions used herein include plural expressions unless the context clearly dictates otherwise. In this application, terms such as "consisting of" or "comprising" should not be construed as necessarily including all of the various components or steps described in the specification, and some of the components or some of the steps It should be construed that it may not be included, or may further include additional components or steps.
이하에서는, 본 발명의 몇몇 실시예에 따른 항균 유리 조성물 및 그 항균 유리 분말 제조 방법과, 이를 포함하는 가전제품을 설명하도록 한다.Hereinafter, an antibacterial glass composition according to some embodiments of the present invention, a method for manufacturing the antibacterial glass powder, and home appliances including the same will be described.
항균 유리 조성물antibacterial glass composition
본 발명의 실시예에 따른 항균 유리 조성물은 기존의 용출 메커니즘과 달리 유리가 물속에서도 전혀 물과 반응하지 않아도 영구적으로 효과가 지속되는 항균 작용을 한다.Unlike the conventional elution mechanism, the antibacterial glass composition according to the embodiment of the present invention has an antibacterial effect that is permanently effective even when the glass does not react with water at all even in water.
이를 위해, 본 발명의 실시예에 따른 항균 유리 조성물은 유리 형성 시 중간산화물이 수식산화물 또는 망목형성 산화물 역할이 모두 가능한 점을 활용 하기 위해, 각 성분 및 이의 성분비를 제어하여 항균 성능을 발현하는 성분인 Zn, Ca 이온이 망목형성 구조에 참여하도록 하여 물에 용출되지 않는 강건한 유리 구조를 형성하며, 유리의 표면 전하를 제어하여 물에서 용출되는 것 없이 항균성을 발휘할 수 있게 된다.To this end, in the antibacterial glass composition according to an embodiment of the present invention, in order to take advantage of the fact that the intermediate oxide can serve as both a modifying oxide and a network forming oxide during glass formation, components exhibiting antibacterial performance by controlling each component and its component ratio. Phosphorus Zn and Ca ions participate in the network structure to form a strong glass structure that is not eluted in water, and by controlling the surface charge of the glass, it is possible to exhibit antibacterial properties without eluted in water.
이와 같이, 본 발명의 실시예에 따른 항균 유리 조성물은 항균 기능을 구현하기 위하여 용출시키는 Zn, Ca 이온을 수식산화물과 망목형성 산화물의 함량비를 이용하여 망목형성이 이루어지도록 제어하여 항균력과 내수성을 동시에 확보하였다.As such, the antibacterial glass composition according to an embodiment of the present invention controls antibacterial activity and water resistance by controlling the netting to be achieved by using the content ratio of the modifying oxide and the netting oxide to elute Zn and Ca ions to implement the antibacterial function. secured at the same time.
아울러, 본 발명에서 항균성이 발현되는 메커니즘은 유리 내 금속이온이 유리의 표면 전하, 즉 제타 포텐셜(zeta potential)을 양의 전하를 띠게 해, 통상적으로 음의 전하를 띠는 세균을 끌어당기고 세균이 성장할 수 없는 전하 분위기를 조성해 균을 사멸시킨다.In addition, the mechanism by which antibacterial properties are expressed in the present invention is that metal ions in the glass make the surface charge of the glass, that is, zeta potential, positively charged, attracting bacteria that are usually negatively charged, and bacteria It creates an charged atmosphere that cannot grow and kills germs.
이때, 내구성이 우수한 항균성 유리 조성물을 제조하기 위한 요소로는 크게 두 가지로 구분될 수 있다.At this time, elements for manufacturing an antibacterial glass composition having excellent durability may be largely divided into two types.
첫째로는 유리 구조를 형성시켜 화학적 내구성을 결정하는 유리 기질(glass matrix)이다. 이는 기존 무기항균제의 담체와 유사한 역할(항균 특성을 발현하는 재료를 표면에 분산시킴)을 수행한다.First, it is a glass matrix that determines chemical durability by forming a glass structure. This plays a role similar to that of the existing inorganic antimicrobial carrier (dispersing the material exhibiting antimicrobial properties on the surface).
차이가 있다면, 기존 담체는 무기항균제의 표면에 항균 성분을 담지시킨 형태이지만, 본 발명에서는 항균 특성을 발현하는 금속 재료를 이온 형태로 유리 기질 내에 존재하도록 한 것이다. 이렇게 내구성이 우수한 유리 기질을 만들기 위해서는 SiO2 및 B2O3와 같은 유리형성제의 함량비가 중요할 뿐만 아니라, 알칼리 성분간의 조합비(mixed alkali effect in glass : 알칼리성분의 비율에 따라 유리의 기계적 특성 등이 비선형적으로 변화할 수 있음)도 매우 중요한 요소이다.If there is a difference, the conventional carrier is a type in which an antibacterial component is supported on the surface of an inorganic antimicrobial agent, but in the present invention, a metal material expressing antibacterial properties is present in the glass substrate in the form of an ion. In order to make such a durable glass substrate, not only the content ratio of glass formers such as SiO 2 and B 2 O 3 is important, but also the mixed alkali effect in glass (mixed alkali effect in glass: mechanical properties of glass depend on the ratio of alkali components). may change nonlinearly) is also a very important factor.
둘째로는 유리 내에 포함되는 금속 성분의 효과이다. 즉, 금속 성분이 항균 성능을 발휘하게 하는 주요 인자라고 할 수 있는데 성분마다 그 항균 특성의 차이는 크다. 또한, 유리 기질 내의 성분과의 상호작용에 의해 이온결합 및 공유결합 상태에 따라 내구성에 차이가 나타날 수 있기 때문에 항균 유리 조성비의 최적화 설계가 중요하다.The second is the effect of the metal component included in the glass. In other words, it can be said that the metal component is a major factor that exerts antibacterial performance, but the difference in antibacterial properties for each component is large. In addition, since a difference in durability may appear depending on the state of ionic and covalent bonds due to interaction with components in the glass substrate, it is important to optimize the antibacterial glass composition ratio.
이를 위해, 본 발명의 실시예에 따른 항균 유리 조성물은 SiO2 25 ~ 45 중량%, B2O3 및 P2O5 1종 이상 3 ~ 20 중량%, Na2O 및 K2O 1종 이상 10 ~ 30 중량%, ZnO 및 CaO 중 1종 이상 10 ~ 30 중량% 및 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%를 포함한다.To this end, the antibacterial glass composition according to an embodiment of the present invention contains 25 to 45% by weight of SiO 2 , 3 to 20% by weight of one or more kinds of B 2 O 3 and P 2 O 5 , and one or more kinds of Na 2 O and K 2 O 10 to 30% by weight, 10 to 30% by weight of one or more of ZnO and CaO, and 0.1 to 3% by weight of one or more of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 .
또한, 본 발명의 실시예에 따른 항균 유리 조성물은 Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함할 수 있다.In addition, the antibacterial glass composition according to an embodiment of the present invention may further include 0.1% by weight or less of at least one of Ag 3 PO 4 and AgNO 3 .
전술한 본 발명의 실시예에 따른 항균 유리 조성물은 다목적 항균성 성분으로 이루어지는 수불용성 항균제이므로, 유리 선반의 코팅 재료 및 플라스틱 사출품의 첨가제로 활용할 시, 영구적으로 사용할 수 있게 된다.Since the antimicrobial glass composition according to the embodiment of the present invention described above is a water-insoluble antimicrobial agent composed of multipurpose antimicrobial components, it can be used permanently when used as a coating material for glass shelves and an additive for plastic injection molding products.
아울러, 본 발명의 실시예에 따른 항균 유리 조성물은 비용출 특성을 나타내는 항균제이므로, 식음수에 닿는 부품군에 코팅제로 사용할 시, 세균, 곰팡이 등의 오염을 막는데 탁월한 효과를 발휘하게 된다.In addition, since the antibacterial glass composition according to the embodiment of the present invention is an antibacterial agent exhibiting non-elution characteristics, when used as a coating agent for parts that come into contact with drinking water, it exhibits an excellent effect in preventing contamination by bacteria and fungi.
이하에서는 본 발명의 실시예에 따른 항균 유리 조성물의 각 성분의 역할 및 그 함량에 대하여 상세히 설명하도록 한다.Hereinafter, the role and content of each component of the antibacterial glass composition 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 a framework structure of glass and are key components enabling 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 forming agent that enables vitrification and is a key component that serves as a framework in terms of glass structure. When such SiO 2 is included in an appropriate amount or more, viscosity increases during melting of the glass, resulting in reduced workability and yield during the cooling process. In addition, SiO 2 does not act as a direct component that expresses antibacterial activity, but forms less OH - groups on the glass surface compared to P 2 O 5 , which is a representative network-forming oxide, and thus causes the glass surface caused by metal ions in the glass to be positively charged. It is advantageous to wear
따라서, SiO2는 본 발명에 따른 항균 유리 조성물 전체 중량의 25 ~ 45 중량%의 함량비로 첨가되는 것이 바람직하다. SiO2의 첨가량이 25 중량% 미만일 시에는 망목형성 산화물가 부족하여 유리화 영역을 벗어나는데 기인하여 유백화가 나타나거나, 투명한 유리가 혼재하는 불균질화 현상이 발생할 수 있다. 반대로, SiO2의 첨가량이 45 중량%를 초과할 경우에는 유리의 표면 전하를 양의 값으로 제어하기 어렵기 때문에 항균력이 저하 현상이 발생할 수 있다.Therefore, SiO 2 is preferably added in a content ratio of 25 to 45% by weight of the total weight of the antimicrobial glass composition according to the present invention. When the added amount of SiO 2 is less than 25% by weight, opacification may occur due to the lack of network-forming oxides and thus escape from the vitrification region, or heterogeneity in which transparent glass may coexist. Conversely, when the amount of SiO 2 added exceeds 45% by weight, it is difficult to control the surface charge of the glass to a positive value, so the antibacterial activity may decrease.
B2O3 및 P2O5는 대표적인 망목형성 산화물로써 SiO2와 함께 충분한 유리화가 가능하게 하는 핵심적인 성분이다. B2O3 및 P2O5는 녹는점이 낮아 용융물의 공융점(eutectic point)을 낮추는데 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 이상으로 첨가되면, 유리의 결합 구조를 약화시켜 내수성 등을 저하시키는 문제가 발생할 수 있다.B 2 O 3 and P 2 O 5 are representative network-forming oxides and, together with SiO 2 , are key components enabling sufficient vitrification. B 2 O 3 and P 2 O 5 have low melting points and are used for lowering the eutectic point of a melt. In addition, B 2 O 3 and P 2 O 5 act to increase the solubility of rigid components (Al 2 O 3 , CuO, etc.) during melting for vitrification, resulting in a homogeneous glass. help to become However, if B 2 O 3 and P 2 O 5 are added in a certain amount, a problem of deteriorating water resistance by weakening the bonding structure of glass 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 small amounts only for lowering the melting point in order to realize water-insoluble antibacterial glass.
이를 위해, B2O3 및 P2O5 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 3 ~ 20 중량%의 함량비로 첨가되는 것이 바람직하다. B2O3 및 P2O5 1종 이상이 3 중량% 미만으로 첨가될 경우에는 융제가 부족하기 때문에 유리화 영역을 벗어나게 되어, 미용융 현상이 발생할 수 있다. 반대로, B2O3 및 P2O5 1종 이상이 20 중량%를 초과할 경우에는 망목형성 구조 내에서 B, P의 구조적인 문제로 원소의 자체 성질에 의해 내수성 저하 현상이 발생할 수 있다.To this end, one or more of B 2 O 3 and P 2 O 5 is preferably added in a content ratio of 3 to 20% by weight of the total weight of the antibacterial 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 3% by weight, the melting agent is insufficient, so that the vitrification region is not reached, and thus, a non-melting phenomenon may occur. Conversely, when one or more of B 2 O 3 and P 2 O 5 exceeds 20% by weight, a decrease in water resistance may occur due to the nature of the elements due to structural problems of B and P in the network-forming structure.
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 that of B 2 O 3 , because it is advantageous to secure water resistance when the amount of SiO 2 added is higher than that of B 2 O 3 .
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. 상기 성분들 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 act as network modifiers for non-crosslinking in the glass composition. Although these components cannot be vitrified alone, they can be vitrified when mixed with network forming agents such as SiO 2 and B 2 O 3 in a certain ratio. If only one of the components is included in the glass composition, the durability of the glass may be weakened in a vitrifiable region. However, when two or more components are included in the glass composition, the durability of the glass is improved again depending on 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 CaO를 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 antibacterial activity by using the fact that alkali oxides first occupy a modified oxide site in glass. In addition, alkali oxides such as Na 2 O and K 2 O contribute to the formation of a network by making the intermediate oxides ZnO and CaO to contribute to the formation of a network, thereby enhancing durability and contributing to the expression of antimicrobial activity by water insolubility and surface charge. do.
Na2O 및 K2O 중 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 10 ~ 30 중량%의 함량비로 첨가되는 것이 바람직하다. Na2O 및 K2O 중 1종 이상이 10 중량% 미만으로 첨가될 경우에는 융제가 부족하기 때문에 유리화 영역을 벗어나는데 기인하여 미용융물이 형성되는 현상이 발생할 수 있다. 반대로, Na2O 및 K2O 중 1종 이상이 30 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 10 to 30% by weight of the total weight of the antibacterial glass composition according to the present invention. When one or more of Na 2 O and K 2 O is added in an amount of less than 10% by weight, a phenomenon in which a non-melt is formed due to leaving the vitrification region may occur because the melting agent is insufficient. Conversely, when one or more of Na 2 O and K 2 O is added in excess of 30% by weight, alkali ions are easily replaced with H 3 O + ions of water according to the basic elution mechanism of glass, and the elution intensifies. degradation may occur.
여기서, Na2O는 4 ~ 20 중량%로 첨가되고, K2O는 6 ~ 20 중량%로 첨가되는 것이 보다 바람직하다.Here, Na 2 O is added at 4 to 20% by weight, and K 2 O is more preferably added at 6 to 20% by weight.
본 발명에서 ZnO 및 CaO은 망목형성 산화물의 일부와 치환되어 공유결합하여 망목형성 산화물의 역할 및 수식산화물 역할을 모두 수행하는 성분이다. 아울러, ZnO 및 CaO은 항균 효과를 발현하는데 크게 기여하는 성분이다.In the present invention, ZnO and CaO are components that play both roles as network-forming oxides and modifier oxides by substituting and covalently bonding with some of the network-forming oxides. In addition, ZnO and CaO are components that greatly contribute to the expression of antibacterial effects.
이러한 ZnO 및 CaO는 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 CaO는 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 CaO are intermediate oxides, and in order to participate in the network formation structure in glass, they must have a small atomic radius and a large electronegativity to have a small difference with oxygen. These intermediate oxides have a larger atomic radius than typical network-forming oxides, such as Si, P, and B, and have low electronegativity, making it difficult to form a glass alone. say the ingredients. These ZnO and CaO serve only as modified oxides below a certain content, but above a certain content, they form covalent bonds to rapidly improve durability. Here, the predetermined content is determined by the content of the network-forming oxide and the modifier oxide.
따라서, ZnO 및 CaO 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 10 ~ 30 중량%의 함량비로 첨가되는 것이 바람직하다. ZnO 및 CaO 1종 이상이 10 중량% 미만으로 첨가될 경우에는 항균성능을 발현하는 물질의 절대량이 부족하기 때문에 충분한 항균력을 발현하지 못하는 문제가 있다. 반대로, ZnO 및 CaO 1종 이상이 30 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. Therefore, at least one of ZnO and CaO is preferably added in a content ratio of 10 to 30% by weight of the total weight of the antimicrobial glass composition according to the present invention. When one or more of ZnO and CaO is added in an amount of less than 10% by weight, there is a problem in that sufficient antibacterial activity is not expressed because the absolute amount of the substance exhibiting antibacterial activity is insufficient. Conversely, when one or more of ZnO and CaO are added in excess of more than 30% by weight, they do not exist in the ionic state in the glass in a homogeneous manner, and opacification occurs due to partial crystal formation and leaving the vitrification region, resulting in transparent glass Mixed heterogeneity may occur.
또한 본 발명의 조성물은 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%를 포함한다. Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 중량% 미만으로 첨가되면 본 발명의 조성물은 충분한 항균력을 발현하지 못한다. 반대로 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 3 중량%를 초과하여 포함되면, 환원반응에 의해 금속 석출 현상이 발생되고 유리화가 되지 않는 문제가 있을 수 있다.In addition, the composition of the present invention includes 0.1 to 3% by weight of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 . When at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 is added at less than 0.1% by weight, the composition of the present invention does not exhibit sufficient antibacterial activity. Conversely, when one or more of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 is included in an amount exceeding 3% by weight, there is a problem in that metal precipitation occurs due to a reduction reaction and vitrification does not occur. can
Ag3PO4 및 AgNO3는 유리 내에 이온 상태로 존재하며, 항균력을 발현하는데 효과적인 성분이다. 아울러, Ag3PO4 및 AgNO3는 용점을 낮추는 역할을 한다. 다만, Ag3PO4 및 AgNO3 중 1종 이상이 0.1 중량%를 초과하여 과다 첨가할 시 은 금속의 석출로 유리화를 불안정하게 할 우려가 있다. 따라서, Ag3PO4 및 AgNO3 중 1종 이상은 본 발명에 따른 항균 유리 조성물 전체 중량의 0.1 중량% 이하로 엄격히 제한적으로 첨가되는 것이 바람직하다.Ag 3 PO 4 and AgNO 3 exist in an ionic state in glass and are effective components for expressing antibacterial activity. In addition, Ag 3 PO 4 and AgNO 3 serve to lower the melting point. However, when one or more of Ag 3 PO 4 and AgNO 3 is added in excess of 0.1% by weight, there is a risk of destabilizing vitrification due to precipitation of silver metal. Therefore, at least one of Ag 3 PO 4 and AgNO 3 is preferably added in a strictly limited amount of 0.1% by weight or less based on the total weight of the antimicrobial glass composition according to the present invention.
상술한, Silver Oxide, MnO2, Ga2O3, TeO2 및 La2O3 와 같은 각 물질은 공유결합 상태로 존재한다. 유리 내에서는 해당 성분은 이온 결합 상태로 존재하며, 이온 상태일 때 활성을 띄며 항균 특성을 발현한다. 유리 내에서 해당 성분을 단독 활용하여 항균력을 나타내기 위해서는 고함량으로 포함될 필요성이 있다. 위 성분들이 고함량으로 포함하기 위해서는 베이스 매트릭스(Base Matrix)가 Borate 또는 Phosphate Glass, 이온화 경향이 상대적으로 높은 R2O(Alkali Oxide)/RO(Alkaline-earth Oxide)의 함량이 낮은 구조적 복합성이 낮은 조성이 되어야 하며, 이러한 조성의 유리는 내구성이 낮기 때문에 용출에 의한 항균특성을 발현하도록 설계가 된다. 그러나, 본 발명에서는 항균 특성과 더불어 내구성이 높은 유리 조성계를 구현하기 위해 위 성분들의 함량을 적게 포함하였다. 본 발명은 위 성분들을 적게 포함하면서도 타 성분과의 비율에 의해서 전위교란 및 산화성 스트레스를 부여하여 균을 약화 시킨다. 이에 따라, 본 발명은 위 성분들의 함량이 낮음에도 불구하고 충분한 항균력을 발현 할 수 있다.Each of the above-described materials such as Silver Oxide, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 exists in a covalent bond state. In glass, the component exists in an ion-bound state, and when in an ionic state, it is active and exhibits antibacterial properties. In order to exhibit antibacterial activity by using the component alone in the glass, it needs to be included in a high content. In order to include the above components in high content, the base matrix should be Borate or Phosphate Glass, R 2 O (Alkali Oxide)/RO (Alkaline-earth Oxide) with relatively high ionization tendency, and low structural complexity. It should be composed, and since the glass of this composition has low durability, it is designed to express antibacterial properties by elution. However, in the present invention, a small amount of the above components was included in order to realize a glass composition system having antibacterial properties and high durability. The present invention weakens bacteria by imparting potential disturbance and oxidative stress by the ratio with other components while containing a small amount of the above components. Accordingly, the present invention can express sufficient antibacterial activity despite the low content of the above components.
항균 유리 분말의 제조 방법Manufacturing method of antibacterial glass powder
이하 첨부된 도면을 참조하여 본 발명의 실시예에 따른 항균 유리 분말 제조 방법에 대하여 설명하도록 한다.Hereinafter, a method for manufacturing an antibacterial glass powder according to an embodiment of the present invention will be described with reference to the accompanying drawings.
도 1은 본 발명의 실시예에 따른 항균 유리 분말 제조 방법을 나타낸 공정 순서도이다.1 is a process flow chart showing a method for manufacturing an antibacterial glass powder according to an embodiment of the present invention.
도 1에 도시된 바와 같이, 본 발명의 실시예에 따른 항균 유리 분말 제조 방법은 혼합 단계(S110), 용융 단계(S120), 냉각 단계(S130) 및 분쇄 단계(S140)를 포함한다.As shown in FIG. 1 , the antibacterial glass powder manufacturing method according to an embodiment of the present invention includes a mixing step (S110), a melting step (S120), a cooling step (S130), and a grinding step (S140).
혼합mix
혼합 단계(S110)에서 SiO2 25 ~ 45 중량%, B2O3 및 P2O5 1종 이상 3 ~ 20 중량%, Na2O 및 K2O 1종 이상 10 ~ 30 중량%, ZnO 및 CaO 중 1종 이상 10 ~ 30 중량% 및 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%로 혼합하고 교반하여 항균 유리 조성물을 형성한다.In the mixing step (S110), 25 to 45 wt% of SiO 2 , 3 to 20 wt% of at least one B 2 O 3 and P 2 O 5 , 10 to 30 wt% of at least one Na 2 O and K 2 O, ZnO and 10 to 30% by weight of one or more of CaO and 0.1 to 3% by weight of one or more of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 are mixed and stirred to form an antibacterial glass composition .
여기서, SiO2는 B2O3의 함량보다 높은 함량으로 첨가하는 것이 바람직하다.Here, SiO 2 is preferably added in an amount higher than that of B 2 O 3 .
아울러, Na2O는 4 ~ 20 중량%로 첨가하고, K2O는 6 ~ 20 중량%로 첨가한다.In addition, Na 2 O is added at 4 to 20% by weight, and K 2 O is added at 6 to 20% by weight.
또한, 항균 유리 조성물은 Ag3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함할 수 있다.In addition, the antibacterial glass composition may further include 0.1% by weight or less of at least one of Ag 3 PO 4 and AgNO 3 .
용융melting
용융 단계(S120)에서는 항균 유리 조성물을 용융시킨다.In the melting step (S120), the antibacterial 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, melting is preferably performed at 1,100 to 1,400 ° C for 1 to 60 minutes. When the melting temperature is less than 1,100° C. or the melting time is less than 1 minute, the antibacterial glass composition is not completely melted, causing 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, cooling is preferably performed by 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 for cooling.
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 pulverization step (S140), the cooled antibacterial glass is pulverized. At this time, any one of a ball mill, a jet mill, and a planetary mill commonly known for grinding may be applied.
이러한 분쇄에 의해, 항균 유리가 미세하게 분쇄되어 항균 유리 분말이 제조된다. 이러한 항균 유리 분말은 30㎛ 이하의 평균 직경을 갖는 것이 바람직하며, 보다 바람직한 범위로는 5 ~ 15㎛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 30 μm or less, and an average diameter of 5 to 15 μm may be suggested as a more preferable range.
한편, 본 발명의 실시예에 따른 가전제품은 수지재와, 수지재에 상술한 방법에 의해 제조된 항균 유리 분말이 첨가된 플라스틱 사출물을 포함한다. 본 발명에서 사용한 가전제품은 정수기, 세탁기, 스탠드 에어컨, 시스템 에어컨, 냉장고 등을 포함할 수 있으나, 이에 제한되는 것은 아니다.Meanwhile, the home appliance according to an embodiment of the present invention includes a resin material and an injection-molded plastic product in which the antibacterial glass powder manufactured by the above-described method is added to the resin material. Home appliances used in the present invention may include, but are not limited to, water purifiers, washing machines, stand air conditioners, system air conditioners, and refrigerators.
여기서, 플라스틱 사출물은 수지재 95.0 ~ 99.0 중량% 및 항균 유리 분말 1.0 ~ 5.0 중량%을 포함한다.Here, the plastic injection product includes 95.0 to 99.0% by weight of the resin material and 1.0 to 5.0% by weight of the antibacterial glass powder.
항균 유리 분말의 첨가량이 플라스틱 사출물 전체 중량의 1.0 중량% 미만으로 미량 첨가될 경우에는 녹농균에 대한 항균력이 충분하지 않을 수 있다. 반대로, 항균 유리 분말의 첨가량이 플라스틱 사출물 전체 중량의 5.0 중량%를 초과하여 과량 첨가될 경우에는 기계적 물성이 저하될 가능성이 있다. When the antibacterial glass powder is added in a small amount of less than 1.0% by weight of the total weight of the plastic injection molding, the antibacterial activity against Pseudomonas aeruginosa may not be sufficient. Conversely, when the antibacterial glass powder is added in excess of 5.0% by weight of the total weight of the plastic injection molding product, mechanical properties may be deteriorated.
수지재는 PP(polypropylene), PC(polycarbonate), EPDM(ethylene propylene rubber), ABS(acrylonitrile-buradiene-styrene) 및 HIPS(high impact polystyrene) 중 적어도 하나 이상을 포함한다.The resin material includes at least one of polypropylene (PP), polycarbonate (PC), ethylene propylene rubber (EPDM), acrylonitrile-buradiene-styrene (ABS), and high impact polystyrene (HIPS).
이때, 항균 유리 분말은 SiO2 25 ~ 45 중량%, B2O3 및 P2O5 1종 이상 3 ~ 20 중량%, Na2O 및 K2O 1종 이상 10 ~ 30 중량%, ZnO 및 CaO 중 1종 이상 10 ~ 30 중량% 및 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%을 포함한다.At this time, the antibacterial glass powder contains 25 to 45% by weight of SiO 2 , 3 to 20% by weight of one or more types of B 2 O 3 and P 2 O 5 , 10 to 30% by weight of one or more types of Na 2 O and K 2 O, ZnO and 10 to 30% by weight of one or more of CaO and 0.1 to 3% by weight of one or more of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 .
여기서, Na2O는 4 ~ 20 중량%로 첨가하고, K2O는 6 ~ 20 중량%로 첨가한다.Here, Na 2 O is added at 4 to 20% by weight, and K 2 O is added at 6 to 20% by weight.
또한, 플라스틱 사출물에는 항균 유리 분말 외에 기능성 첨가제가 더 포함되어 있을 수 있다. 이때, 기능성 첨가제로는 산화방지제, 발포제, 충격보강제, 핵제, 커플링제 등에서 선택된 1종이 이상을 포함할 수 있다.In addition, a functional additive may be further included in the plastic injection molding product in addition to the antibacterial glass powder. At this time, the functional additive may include at least one selected from antioxidants, foaming agents, impact modifiers, nucleating agents, coupling agents, and the like.
이에 따라, 본 발명의 실시예에 따른 가전제품은 세균 번식에 취약하고, 수분과의 접촉이 많은 부품의 표면에 적용되어 각종 미생물의 서식 및 성장을 방지할 수 있는 항균력을 갖게 된다.Accordingly, the home appliance according to the embodiment of the present invention is applied to the surface of a part that is vulnerable to bacterial propagation and has a lot of contact with moisture, and has antibacterial activity capable of preventing the habitat and growth of various microorganisms.
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 by this in any sense.
여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.Contents not described herein can be technically inferred by those skilled in the art, so descriptions thereof will be omitted.
1. 항균 유리 분말 시료 제조1. Antibacterial glass powder sample preparation
표 1은 실시예 및 비교예의 항균 유리 조성물에 대한 조성 및 이의 조성비를 나타낸 것이다.Table 1 shows the compositions and composition ratios of the antibacterial glass compositions of Examples and Comparative Examples.
상기 실시예 및 비교예에 기재된 조성을 갖는 항균 유리 조성물을 전기로에서 1,200℃의 온도로 각각 용융시킨 후, 스테인리스(stainless steel) 강판에 공냉 방식으로 글래스 벌크 형태로 냉각하였다. 이후, 수득한 유리를 건식분쇄기(ball mill)로 분쇄한 후, 400메쉬 시브에 통과시켜 항균 유리 분말 시료를 제조하였다.The antibacterial glass compositions having the compositions described in Examples and Comparative Examples were melted in an electric furnace at a temperature of 1,200° C., and then cooled in a glass bulk form on a stainless steel sheet by an air cooling method. Thereafter, the obtained glass was pulverized with a ball mill and passed through a 400 mesh sieve to prepare an antibacterial glass powder sample.
여기서, 성분 Na2O, K2O, CaO의 원재료는 각각 Na2CO3, K2CO3, CaCO3를 사용하였고, 나머지 성분은 표 1 및 표 2에 기재된 것과 동일한 것을 사용하였다. 아울러, 유리화는 균질하게 유리 성상을 보이는 경우와 유백화 및 미용융물이 발생하는 현상을 기준으로 구분하였다.Here, Na 2 CO 3 , K 2 CO 3 , and CaCO 3 were used as raw materials for the components Na 2 O, K 2 O, and CaO, respectively, and the other components were the same as those described in Tables 1 and 2. In addition, vitrification was classified based on the case of homogeneously showing glass properties and the phenomenon of opacification and minor melting.
| 구분division | 실시예Example | 비교예comparative example | |||||||
| 1One | 22 | 33 | 44 | 55 | 1One | 22 | 33 | 44 | |
| SiO2 SiO 2 | 44.644.6 | 26.226.2 | 44.644.6 | 37.237.2 | 38.238.2 | 15.215.2 | 44.644.6 | 15.115.1 | 48.248.2 |
| P2O5 P 2 O 5 | - - | 1.31.3 | 44 | - - | 1.31.3 | 11.711.7 | 44 | 34.834.8 | 1.11.1 |
| B2O3 B 2 O 3 | 1414 | 17.4 17.4 | 1010 | 44 | 18.7 18.7 | 19.319.3 | 1010 | 1.21.2 | 0.70.7 |
| Na2ONa 2 O | 5.65.6 | 4.64.6 | 19.619.6 | 19.619.6 | 4.64.6 | 15.515.5 | 19.619.6 | 0.80.8 | 7.87.8 |
| K2O K2O | 9.69.6 | 19.6 19.6 | 9.69.6 | 9.69.6 | 6.66.6 | 15.515.5 | 9.69.6 | 1.31.3 | 8.28.2 |
| CaOCaO | 3.33.3 | 8.88.8 | - - | 8.88.8 | 8.88.8 | - - | 0.70.7 | 1.41.4 | - - |
| ZnOZnO | 22.422.4 | 19.319.3 | 11.511.5 | 19.319.3 | 19.319.3 | 22.822.8 | 11.511.5 | 41.241.2 | 3434 |
| Ag2OAg 2 O | 0.50.5 | 0.30.3 | 0.70.7 | 0.30.3 | - - | - - | - - | 0.70.7 | - - |
| MnO2 MnO 2 | - - | 1One | - - | - - | - - | - - | - - | 1One | - - |
| Ga2O3 Ga 2 O 3 | - - | 1.51.5 | - - | - - | 0.40.4 | - - | - - | 1One | - - |
| TeO2 TeO 2 | - - | - - | - - | 1.21.2 | 0.40.4 | - - | - - | - - | - - |
| La2O3 La 2 O 3 | - - | - - | 22 | - - | 1.71.7 | - - | - - | 1.51.5 | - - |
| TotalTotal | 100100 | 100100 | 100100 | 100100 | 100100 | 100100 | 100100 | 100100 | 100100 |
(단위 : 중량%)(Unit: % by weight)
2. 항균 유리 분말 물성 평가2. Evaluation of antibacterial glass powder properties
표 2는 실시예 및 비교예에 따라 제조된 시료에 대한 물성 평가 결과를 나타낸 것이다.Table 2 shows the results of evaluating the physical properties of samples prepared according to Examples and Comparative Examples.
1) 항균력 측정1) Measurement of antibacterial activity
균질하게 유리화가 진행된 실시예 및 비교예에 대하여, 진탕플라스크법(ASTM E2149-13a)에 의거하여 4개 균(Staphylococcus aureus, Escherichia coil, Klebsiella pneumoniae, Pseudomonas aeruginosa)에 대하여 항균 평가를 실시하였다.For Examples and Comparative Examples in which vitrification was performed homogeneously, antimicrobial activity was evaluated against four bacteria (Staphylococcus aureus, Escherichia coil, Klebsiella pneumoniae, and Pseudomonas aeruginosa) according to the shake flask method (ASTM E2149-13a).
2) 화학적 내구성 평가2) Evaluation of chemical durability
균질하게 유리화가 진행된 실시예 및 비교예에 대한 내구성을 평가하기 위하여 ASTM C1285-14(glass 및 glass ceramic 내구성 평가법)시험법을 통하여 WHO 가이드(guide) 및 국내 음용수 기준을 사용하여 하기의 표 5에 기재된 원소에 대한 용출 수준에 대한 통과 여부를 평가하였다. 여기서, 화학적 내구성은 50℃, 32시간에서 표 3에 기재된 각 원소에 대한 용출량이 기준치 미만일 시에는 O로 표시하였고, 기준치 이상에서는 X로 표시하였다.In order to evaluate the durability of the homogeneously vitrified examples and comparative examples, the WHO guide and domestic drinking water standards were used through the ASTM C1285-14 (glass and glass ceramic durability evaluation method) test method in Table 5 below. Elution levels for the listed elements were evaluated for pass or fail. Here, the chemical durability was expressed as O when the elution amount for each element listed in Table 3 at 50 ° C. for 32 hours was less than the reference value, and was expressed as X when it was more than the reference value.
| 구분division | 실시예Example | 비교예comparative example | ||||||||
| 1One | 22 | 33 | 44 | 55 | 1One | 22 | 33 | 44 | ||
|
유리화 (O, X)vitrification (O, X) |
OO | OO | OO | OO | OO | OO | OO | XX | XX | |
| 항균력antibacterial power | Staphylococcus aureusStaphylococcus aureus | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 77.0%77.0% | 38.4%38.4% | -- | -- |
| Escherichia coilEscherichia coil | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 54.7%54.7% | 55.5%55.5% | -- | -- | |
| Klebsiella pneumoniaeKlebsiella pneumoniae | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 47.5%47.5% | 67.9%67.9% | -- | -- | |
| Pseudomonas aeruginosaPseudomonas aeruginosa | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 99.9%99.9% | 44.0%44.0% | 21.4%21.4% | -- | -- | |
| 화학적 내구성 평가Chemical durability evaluation | OO | OO | OO | OO | OO | OO | XX | -- | -- | |
| 용출량(ppm)Elution amount (ppm) | BB | ZnZn | MnMn |
| WHO guideWHO guide | 2.42.4 | -- | -- |
| 국내 음용수domestic drinking water | 1.01.0 | 33 | 0.050.05 |
표 1에 도시된 바와 같이, 실시예 1 ~ 5에 따라 제조된 시료들은 4개의 균 모두에서 99% 이상의 항균력을 나타내었다.As shown in Table 1, the samples prepared according to Examples 1 to 5 exhibited antibacterial activity of 99% or more in all four bacteria.
반면, 비교예의 경우에는 비교예 1 ~ 2를 제외하고는 균질하게 유리화가 진행되지 않았다.On the other hand, in the case of Comparative Examples, vitrification did not proceed homogeneously except for Comparative Examples 1 and 2.
아울러, 비교예 1 내지 2에 따라 제조된 시료는 4개의 균 모두에서 좋은 항균력을 발휘한 경우가 없었다.In addition, samples prepared according to Comparative Examples 1 and 2 did not exhibit good antibacterial activity in all four bacteria.
아울러, 내구성 측정 결과, 실시예 1 ~ 5에 따라 제조된 시료를 이용했을 시, B, Zn 및 Mn 원소에 대한 용출이 일어나지 않아 우수한 화학적 내구성을 나타내는 것을 확인하였다.In addition, as a result of durability measurement, it was confirmed that when samples prepared according to Examples 1 to 5 were used, elution of B, Zn, and Mn elements did not occur, indicating excellent chemical durability.
반면, 비교예 1에 따라 제조된 시료는 용출이 일어나지 않았으나, 비교예 2에 따라 제조된 시료에서 용출이 일어나 화학적 내구성이 좋지 않은 것을 확인하였다.On the other hand, it was confirmed that elution did not occur in the sample prepared according to Comparative Example 1, but elution occurred in the sample prepared according to Comparative Example 2, resulting in poor chemical durability.
3. 사출품 제조3. Manufacture of injection parts
하기 표에 기재된 것처럼, 각각 제조된 항균 유리 분말 2 중량% 및 PP(Polypropylene) 수지 98 중량%를 혼합한 후 사출 성형기를 이용하여 사출 성형하여 200mm(가로), 100mm(세로) 및 3mm(두께)의 사출품을 각각 제조하였다. 이때, 각 사출품의 항균도를 확인하기 위해 ASTM E2149-13a, 진탕플라스크법으로 황색포도상구균 및 대장균에 대한 항균활성치를 측정하였다. 또한, 폐렴균 및 녹농균에 대한 항균력도 추가 평가하였다.As shown in the table below, after mixing 2% by weight of antibacterial glass powder and 98% by weight of PP (Polypropylene) resin, respectively prepared by injection molding using an injection molding machine, 200mm (width), 100mm (length) and 3mm (thickness) Each of the injection products were manufactured. At this time, in order to confirm the antibacterial activity of each injection product, the antibacterial activity against Staphylococcus aureus and Escherichia coli was measured by ASTM E2149-13a, the shake flask method. In addition, the antibacterial activity against Pneumococcus and Pseudomonas aeruginosa was further evaluated.
|
항균력 (JIS Z 2801, 필름부착법)antibacterial power (JIS Z 2801, film adhesion method) |
실시예 1Example 1 | 실시예 2Example 2 | 비교예 1Comparative Example 1 | 비교예 2Comparative Example 2 |
| Staphylococcus aureusStaphylococcus aureus | 99.99 %99.99% | 99.99 %99.99% | 71.0%71.0% | 38.4%38.4% |
| Escherichia coilEscherichia coil | 99.99 %99.99% | 99.99 %99.99% | 62.7%62.7% | 55.5%55.5% |
| Klebsiella pneumoniaeKlebsiella pneumoniae | 99.99 %99.99% | 99.99 %99.99% | 50.5%50.5% | 67.9%67.9% |
| Pseudomonas aeruginosaPseudomonas aeruginosa | 99.9 %99.9% | 99.9 %99.9% | 48.0%48.0% | 21.4%21.4% |
표 4에 도시된 바와 같이, 실시예에 따라 제조된 사출품들은 모두 항균활성치 2.0 이상으로 측정되어, 항균력 99% 이상을 나타내는 것을 확인하였다.As shown in Table 4, it was confirmed that the injection products manufactured according to the examples were all measured with an antibacterial activity value of 2.0 or more, and exhibited an antibacterial activity of 99% or more.
반면, 비교예에 따라 제조된 사출품들은 항균활성치가 2.0 미만으로 측정되어 항균력 80% 이하를 나타내었다.On the other hand, the injection products manufactured according to the comparative example were measured as less than 2.0 in antibacterial activity and showed an antibacterial activity of 80% or less.
위의 실험 결과를 토대로 알 수 있듯이, 실시예에 따라 제조된 사출품들이 비교예에 따라 제조된 사출품들에 비하여 우수한 항균력을 나타내는 것을 확인하였다.As can be seen based on the above experimental results, it was confirmed that the injection-molded products manufactured according to the Examples exhibit excellent antibacterial activity compared to the injection-molded products manufactured according to the Comparative Example.
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 drawings illustrated, but the present invention is not limited by the embodiments and drawings disclosed in this specification, and various modifications are made by those skilled in the art within the scope of the technical idea of the present invention. It is obvious that variations can be made. In addition, although the operational 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 corresponding configuration should also be recognized.
[부호의 설명][Description of code]
S110 : 혼합 단계S110: mixing step
S120 : 용융 단계S120: melting step
S130 : 냉각 단계S130: cooling step
S140 : 분쇄 단계S140: crushing step
Claims (15)
- SiO2 25 ~ 45 중량%; 25 to 45% by weight of SiO 2 ;B2O3 및 P2O5 1종 이상 3 ~ 20 중량%; 3 to 20% by weight of one or more of B 2 O 3 and P 2 O 5 ;Na2O 및 K2O 1종 이상 10 ~ 30 중량%; 10 to 30% by weight of at least one of Na 2 O and K 2 O;ZnO 및 CaO 중 1종 이상 10 ~ 30 중량%;및10 to 30% by weight of at least one of ZnO and CaO; andAg2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%를 포함하는Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 containing 0.1 to 3% by weight of one or more species항균 유리 조성물. Antibacterial glass composition.
- 제1항에 있어서,According to claim 1,상기 SiO2는 The SiO 2 is상기 B2O3의 함량보다 높은 함량으로 첨가된 항균 유리 조성물.An antibacterial glass composition added in a higher content than the content of B 2 O 3 .
- 제1항에 있어서,According to claim 1,상기 Na2O는 4 ~ 20 중량%로 첨가되고, The Na 2 O is added in an amount of 4 to 20% by weight,상기 K2O는 6 ~ 20 중량%로 첨가된 항균 유리 조성물.The K 2 O is added in an amount of 6 to 20% by weight of the antimicrobial glass composition.
- 제1항에 있어서,According to claim 1,상기 ZnO는 The ZnO is상기 CaO의 함량보다 높은 함량으로 첨가된added in a higher content than the CaO content항균 유리 조성물.Antibacterial glass composition.
- 제1항에 있어서,According to claim 1,상기 항균 유리 조성물은 The antibacterial glass compositionAg3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함하는 항균 유리 조성물.An antibacterial glass composition further comprising 0.1% by weight or less of at least one of Ag 3 PO 4 and AgNO 3 .
- (a) SiO2 25 ~ 45 중량%, B2O3 및 P2O5 1종 이상 3 ~ 20 중량%, Na2O 및 K2O 1종 이상 10 ~ 30 중량%, ZnO 및 CaO 중 1종 이상 10 ~ 30 중량% 및 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%로 혼합하고 교반하여 항균 유리 조성물을 형성하는 단계; (a) 25 to 45% by weight of SiO 2 , 3 to 20% by weight of at least one of B 2 O 3 and P 2 O 5 , 10 to 30% by weight of at least one of Na 2 O and K 2 O, 1 of ZnO and CaO 10 to 30% by weight of at least one species and 0.1 to 3% by weight of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 and stirring to form an antibacterial glass composition;(b) 상기 항균 유리 조성물을 용융시키는 단계; (b) melting the antimicrobial glass composition;(c) 상기 용융된 항균 유리 조성물을 냉각하는 단계; 및 (c) cooling the molten antimicrobial glass composition; and(d) 상기 냉각된 항균 유리를 분쇄하는 단계; (d) grinding the cooled antibacterial glass;를 포함하는 항균 유리 분말 제조 방법.Antibacterial glass powder manufacturing method comprising a.
- 제6항에 있어서,According to claim 6,상기 (a) 단계에서, In step (a),상기 SiO2는 The SiO 2 is상기 B2O3의 함량보다 높은 함량으로 첨가하는 항균 유리 분말 제조 방법.Antibacterial glass powder manufacturing method of adding a higher content than the content of the B 2 O 3 .
- 제6항에 있어서,According to claim 6,상기 (a) 단계에서, In step (a),상기 Na2O를 4 ~ 20 중량%로 첨가하고, The Na 2 O is added in an amount of 4 to 20% by weight,상기 K2O를 6 ~ 20 중량%로 첨가하는,Adding 6 to 20% by weight of the K 2 O,항균 유리 분말 제조 방법.Antibacterial glass powder manufacturing method.
- 제8항에 있어서,According to claim 8,상기 (a) 단계에서,In step (a),상기 ZnO는 The ZnO is상기 CaO의 함량보다 높은 함량으로 첨가하는Added at a higher content than the CaO content항균 유리 분말 제조 방법.Antibacterial glass powder manufacturing method.
- 제6항에 있어서,According to claim 6,상기 (a) 단계에서, In step (a),상기 항균 유리 조성물은 The antibacterial glass compositionAg3PO4 및 AgNO3 중 1종 이상 0.1 중량% 이하를 더 포함하는 항균 유리 분말 제조 방법.Ag 3 PO 4 And AgNO 3 Antibacterial glass powder manufacturing method further comprising at least 0.1% by weight or less of at least one of.
- 제6항에 있어서,According to claim 6,상기 (b) 단계에서,In step (b),상기 용융은 The melt is1,100 ~ 1,400℃에서 1 ~ 60분 동안 실시하는 항균 유리 분말 제조 방법.Antibacterial glass powder manufacturing method carried out at 1,100 ~ 1,400 ℃ for 1 ~ 60 minutes.
- 수지재에 항균 유리 분말이 첨가된 플라스틱 사출물을 포함하는 가전제품으로서, As a home appliance including a plastic injection product in which antibacterial glass powder is added to a resin material,상기 플라스틱 사출물은 The plastic extrusion상기 수지재 95.0 ~ 99.0 중량%; 및 95.0 to 99.0% by weight of the resin material; and상기 항균 유리 분말 1.0 ~ 5.0 중량%;를 포함하며, 1.0 to 5.0% by weight of the antimicrobial glass powder;상기 항균 유리 분말은 SiO2 25 ~ 45 중량%, B2O3 및 P2O5 1종 이상 3 ~ 20 중량%, Na2O 및 K2O 1종 이상 10 ~ 30 중량%, ZnO 및 CaO 중 1종 이상 10 ~ 30 중량% 및 Ag2O, MnO2, Ga2O3, TeO2 및 La2O3 가운데 1종 이상 0.1 ~ 3 중량%를 포함하는 가전제품.The antimicrobial glass powder contains 25 to 45% by weight of SiO 2 , 3 to 20% by weight of one or more of B 2 O 3 and P 2 O 5 , 10 to 30% by weight of one or more of Na 2 O and K 2 O, ZnO and CaO 10 to 30% by weight of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 , TeO 2 and La 2 O 3 0.1 to 3% by weight of at least one of Ag 2 O, MnO 2 , Ga 2 O 3 .
- 제12항에 있어서,According to claim 12,상기 수지재는 The resin materialPP(polypropylene), PC(polycarbonate), EPDM(ethylene propylene rubber), ABS(acrylonitrile-buradiene-styrene) 및 HIPS(high impact polystyrene) 중 적어도 하나 이상을 포함하는 가전제품.Home appliances containing at least one of PP (polypropylene), PC (polycarbonate), EPDM (ethylene propylene rubber), ABS (acrylonitrile-buradiene-styrene), and HIPS (high impact polystyrene).
- 제12항에 있어서,According to claim 12,상기 Na2O는 4 ~ 20 중량%로 첨가되고, The Na 2 O is added in an amount of 4 to 20% by weight,상기 K2O는 6 ~ 20 중량%로 첨가된 The K 2 O is added at 6 to 20% by weight가전제품.home appliances.
- 제12항에 있어서,According to claim 12,상기 ZnO는 The ZnO is상기 CaO의 함량보다 높은 함량으로 첨가된 added in a higher content than the CaO content가전제품.home appliances.
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| KR1020210078074A KR102549222B1 (en) | 2021-06-16 | 2021-06-16 | Antibacterial glass composition and method of manufactruing antibacterial glass powder using the same and domestic appliance including the same |
| KR10-2021-0078074 | 2021-06-16 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000203876A (en) * | 1998-12-28 | 2000-07-25 | Nippon Sheet Glass Co Ltd | Antimicrobial glass and resin composition containing the glass |
| JP2007507408A (en) * | 2003-09-30 | 2007-03-29 | ショット アクチエンゲゼルシャフト | Antibacterial glass surface of glass powder |
| JP2014005194A (en) * | 2012-06-01 | 2014-01-16 | Ishizuka Glass Co Ltd | Antibacterial glass and manufacturing method of the same |
| KR20210026838A (en) * | 2019-09-02 | 2021-03-10 | 엘지전자 주식회사 | Antibacterial glass composite and manufacturing method of antibacterial glass |
| KR20210063092A (en) * | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Antibacterial glass composition and method of manufactruing antibacterial glass powder using the same |
-
2021
- 2021-06-16 KR KR1020210078074A patent/KR102549222B1/en active IP Right Grant
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- 2022-06-15 WO PCT/KR2022/008496 patent/WO2022265405A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000203876A (en) * | 1998-12-28 | 2000-07-25 | Nippon Sheet Glass Co Ltd | Antimicrobial glass and resin composition containing the glass |
| JP2007507408A (en) * | 2003-09-30 | 2007-03-29 | ショット アクチエンゲゼルシャフト | Antibacterial glass surface of glass powder |
| JP2014005194A (en) * | 2012-06-01 | 2014-01-16 | Ishizuka Glass Co Ltd | Antibacterial glass and manufacturing method of the same |
| KR20210026838A (en) * | 2019-09-02 | 2021-03-10 | 엘지전자 주식회사 | Antibacterial glass composite and manufacturing method of antibacterial glass |
| KR20210063092A (en) * | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Antibacterial glass composition and method of manufactruing antibacterial glass powder using the same |
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