KR20020009963A - Preparation of a Composite for a Glass Ceramics having far-infrared Radiation and Antibacterial Properties - Google Patents

Preparation of a Composite for a Glass Ceramics having far-infrared Radiation and Antibacterial Properties Download PDF

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KR20020009963A
KR20020009963A KR1020000043663A KR20000043663A KR20020009963A KR 20020009963 A KR20020009963 A KR 20020009963A KR 1020000043663 A KR1020000043663 A KR 1020000043663A KR 20000043663 A KR20000043663 A KR 20000043663A KR 20020009963 A KR20020009963 A KR 20020009963A
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infrared radiation
glass ceramics
cuo
temperature
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KR100388281B1 (en
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강원호
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강원호
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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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

PURPOSE: Provided is an antibacterial glass ceramic composition with high porosity and surface area, and high far-infrared emission efficiency at room temperature so that it is used for bowls, sanitary fixture and food storage cases. CONSTITUTION: The preparation method comprises the steps of: reacting Ag2O Li2CO3, CaCO3, TiO2(anatase) with H3PO4 to be the composition of 0-5Ag2O, 0-5LiO2, 30-40CaO, 10-25TiO2, 20-30P2O5 in a molar ratio; adding 0.3-1.5wt.% of CuO to give a far-infrared emission effect with water for a slurry, and drying; grinding to powders less than 300mesh; heating at 700-900deg.C for 1hr. and melting 1250-1350deg.C; quenching by pouring the melt on a heated graphite plate to get a mother glass; forming nuclei by heating at 600-620deg.C for 5-20hrs.; crystallizing at 720-740deg.C for 10-20hrs.; soaking in an acidic solution for 1-5hrs. to elute crystalline Ca3(PO4)2.

Description

원적외선 방사 항균성 글라스 세라믹스 조성물의 제조방법{Preparation of a Composite for a Glass Ceramics having far-infrared Radiation and Antibacterial Properties}Preparation of a Composite for a Glass Ceramics having far-infrared Radiation and Antibacterial Properties

본 발명은 글라스 세라믹스 조성물의 제조방법에 관한 것으로, 보다 상세하게는 항균성을 가짐과 동시에 생체에 유익한 작용을 하는 원적외선을 방사하는 글라스 세라믹스 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing a glass ceramic composition, and more particularly, to a method for producing a glass ceramic composition that emits far-infrared rays which have antibacterial properties and have a beneficial effect on a living body.

본 발명자에 의하여 항균성이 우수한 다공성 글라스 세라믹스의 제조방법에 관한 특허출원이 있었다(한국 특허출원 제2000-5702호). 상기 출원에 의한 글라스 세라믹스는 결정화 온도가 낮고 기공율과 비표면적이 매우 높으며, 항균성 또한 우수하여 식기, 위생도기 등과 같은 도자기 분야 및 가습기, 식품보관용기 등과 같은 합성수지 분야와 정수필터 재료 등에 효과적으로 적용될 수 있다. 그러나 상기 기술에 의한 글라스 세라믹스는 상기 장점에도 불구하고, 최근 선도유지 효과가 있는 것으로 판명된 원적외선 방사효과가 부족하여 고급 식품보관용기에 적용이 어려운 문제점이 있다.There is a patent application regarding the method for producing porous glass ceramics having excellent antimicrobial properties by the present inventors (Korean Patent Application No. 2000-5702). Glass ceramics according to the application is low crystallization temperature, porosity and specific surface area is very high, and also excellent antibacterial, it can be effectively applied to ceramics field such as tableware, sanitary ware, and synthetic resin field such as humidifier, food storage container and water filter material. . However, despite the above advantages, the glass ceramics according to the above technology have a problem of being difficult to apply to high-quality food storage containers due to a lack of far-infrared radiation effect that has recently been found to have a leading maintenance effect.

본 발명은 상기 기술을 개량한 것으로, 상기 기술이 가진 장점을 그대로 살리되 생체에 유익한 효과를 주는 원적외선을 상온에서 고효율로 방사할 수 있는 글라스 세라믹스를 제공하는 것을 목적으로 한다.The present invention is an improvement of the above-described technology, and it is an object of the present invention to provide glass ceramics that can radiate far-infrared rays at room temperature with high efficiency while maintaining the advantages of the above technology.

도1은 본 발명의 실시예 1에 의한 글라스 세라믹스의 항균성 측정 결과를 나타낸 도표이고,1 is a chart showing the antimicrobial measurement results of the glass ceramics according to Example 1 of the present invention,

도2는 본 발명의 실시예 1에 의한 글라스 세라믹스의 원적외선 방사율을 측정한 도표이고,FIG. 2 is a chart measuring far-infrared emissivity of glass ceramics according to Example 1 of the present invention.

도3은 본 발명의 실시예 1에 의한 글라스 세라믹스의 원적외선 방사에너지를 측정한 도표이고,3 is a diagram measuring far-infrared radiation energy of glass ceramics according to Example 1 of the present invention;

도4는 본 발명의 실시예 2에 의한 글라스 세라믹스의 원적외선 방사율을 측정한 도표이고,4 is a chart measuring far-infrared emissivity of glass ceramics according to Example 2 of the present invention.

도5는 본 발명의 실시예 2에 의한 글라스 세라믹스의 원적외선 방사에너지를 측정한 도표이고,5 is a diagram measuring far-infrared radiation energy of glass ceramics according to Example 2 of the present invention.

도6은 본 발명의 실시예 3에 의한 글라스 세라믹스의 원적외선 방사율을 측정한 도표이고,FIG. 6 is a chart of measuring far-infrared emissivity of glass ceramics according to Example 3 of the present invention;

도7은 본 발명의 실시예 3에 의한 글라스 세라믹스의 원적외선 방사율에너지를 측정한 도표이다.Fig. 7 is a chart measuring far-infrared emissivity energy of glass ceramics according to the third embodiment of the present invention.

본 발명은 0-5 Ag2O, 0-5 Li2O, 30-40 CaO, 10-25 TiO2, 20-30 P2O5(mole ratio) 의 조성이 되도록 LiCO3, CaCO3, TiO2(anantase)와 H3PO4용액을 처방하고, 여기에 0.3 - 1.5 wt%의 CuO를 첨가하여 물을 가하면서 혼합하여 슬러리 상태로 만든 다음 건조시키고, 건조된 슬러리를 300메쉬 이하의 분말상태로 분쇄한 후, 700-900℃의 온도에서 1시간 내외 유지시킨 다음, 1250-1350℃의 온도에서 용융시키고 가열된 흑연판 위에 부어 급냉시켜 모유리를 제조하고, 얻어진 모유리를 600-620℃의 온도에서 5-20시간동안 가열하여 핵생성 시킨 다음, 720-740℃의 온도에서 10-20시간동안 결정화시킨 후, 산용액에 1-5시간동안 담지시키는 것을 특징으로 한다.The present invention provides a composition of LiCO 3 , CaCO 3 , TiO such that 0-5 Ag 2 O, 0-5 Li 2 O, 30-40 CaO, 10-25 TiO 2 , and 20-30 P 2 O 5 (mole ratio). 2 (anantase) and H 3 PO 4 solution is prescribed, 0.3-1.5 wt% of CuO is added thereto, mixed with water to make a slurry, and then dried, and the dried slurry is powdered up to 300 mesh. After pulverization, and maintained at a temperature of 700-900 ° C for about 1 hour, then melted at a temperature of 1250-1350 ° C and poured on a heated graphite plate to quench the mother glass to prepare a mother glass, and obtained mother glass 600-620 ° C After nucleation by heating for 5-20 hours at the temperature of the crystallization, and then crystallized for 10-20 hours at a temperature of 720-740 ℃, it is characterized in that it is supported for 1-5 hours in an acid solution.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

일반적으로 원적외선은 4 - 1000㎛의 파장을 가지는 적외선을 말하며, 이것은 지구상에 존재하는 생명체의 고유 진동운동과 공명현상을 일으킬 수 있으므로 생명체에 좋은 영향을 주는 것이 확인됨에 따라 최근에는 여러 분야에 적용되고 있다.In general, far infrared rays are infrared rays having a wavelength of 4-1000㎛, which can cause natural vibration and resonance of living things on earth, so it has been applied to various fields recently. have.

특히, 도자기나 식품보관용기의 경우에는 식품의 선도유지와 맛과 영양분의 장기간 유지를 위하여 원적외선 방사재료의 적용이 집중되고 있다.In particular, in the case of ceramics or food storage containers, the application of far-infrared radiation materials is concentrated in order to maintain the freshness of food and to maintain the taste and nutrients for a long time.

지금까지 잘 알려진 원적외선 방사물질은 Al2O3, SiO2, ZrO2, Y2O3, La2O3,CeO2, Fe2O3, MgO, BaO, SnO2, Sb2O5, TiO2등이다. 그러나 이러한 물질들을 글라스 세라믹스에 적용시킬 경우, 방사효율이 저하하거나 글라스 세라믹스 조성물과의 상용성 부족으로 물성이 저하되는 문제점과 아울러, 재료 자체가 고가이어서 일반적인 식품용기에는 적용이 어려운 경우가 많았다.Far-infrared emitters well known so far are Al 2 O 3 , SiO 2 , ZrO 2 , Y 2 O 3 , La 2 O 3 , CeO 2 , Fe 2 O 3 , MgO, BaO, SnO 2 , Sb 2 O 5 , TiO 2 and so on. However, when these materials are applied to glass ceramics, in addition to the problem of lowering the radiation efficiency or physical properties due to lack of compatibility with the glass ceramic composition, the material itself is expensive, so it is often difficult to apply to the general food container.

본 발명자는 다공성 글라스 세라믹스에 원적외선 방사효능을 부여하기 위하여 다양한 실험을 한 결과, CuO가 가장 효과적임을 밝혀 내게 되었다. 비교적 저가의 CuO는 다공성 글라스 세라믹스에 아무런 물성 저하를 야기시키지 아니하면서 상온에서 높은 효율의 원적외선을 방사효과를 부여하였다.The present inventors have conducted various experiments to impart far-infrared radiation efficacy to porous glass ceramics. As a result, it has been found that CuO is most effective. Relatively inexpensive CuO gave high efficiency far-infrared radiation at room temperature without causing any degradation in the properties of porous glass ceramics.

즉, CuO의 첨가에 의하여 항균성과 다공성을 그대로 유지하면서 원적외선까지 고효율로 방사할 수 있게 되었으며, 이러한 재료는 식품용기의 첨가제로 가장 이상적인 것이다. CuO의 적절한 첨가량은 0.3-1.5 wt%로, 이 범위 미만의 경우에는 원적외선 방사효과가 부족하고, 이 범위를 초과하더라도 더 이상의 원적외선 방사효과의 상승이 없다. 상기 범위의 CuO를 첨가하였을 경우, 원적외선 방사에너지는 369.4 내지 370.8(w/m2) 이며, 원적외선 방사율은 91.6 내지 92.6%이다. 원적외선 방사체로 널리 사용되고 있는 맥반석의 원적외선 방사에너지가 373.0(w/m2)이고 원적외선 방사율이 92.5%인 점을 감안할 때 본 발명에 의한 글라스 세라믹스는 매우 높은 효율로 원적외선을 방사함을 알 수 있다.In other words, by adding CuO, it is possible to radiate far infrared rays with high efficiency while maintaining antimicrobial properties and porosity, and such a material is an ideal additive for food containers. The proper addition amount of CuO is 0.3-1.5 wt%, and far below this range there is a lack of far-infrared radiation effect, and even if it exceeds this range, there is no further increase in far-infrared radiation effect. When CuO is added in the above range, the far infrared radiation energy is 369.4 to 370.8 (w / m 2 ), and the far infrared radiation rate is 91.6 to 92.6%. Considering that far-infrared radiation energy of elvan is widely used as far-infrared radiator is 373.0 (w / m 2 ) and far-infrared emissivity is 92.5%, the glass ceramics according to the present invention emit far-infrared rays with very high efficiency.

본 발명의 실시예는 아래와 같다.An embodiment of the present invention is as follows.

(실시예 1-3)(Example 1-3)

Ag2O 3, Li2O 2, CaO 36, TiO220, P2O527 (몰비)의 조성이 되도록 Ag2O, Li2CO3, CaCO3, TiO2(anatase)와 H3PO4(85%) 용액을 처방하고, 여기에 CuO를 0.3-1.5 wt% 첨가하여 혼합한 후 물을 가하면서 저어주어서 슬러리 상태로 만든 다음, 이를 건조시키고 건조된 덩어리를 300메쉬 이하의 분말상태로 분쇄하였다. Ag 2 O 3, Li 2 O 2, CaO 36, TiO 2 20, P 2 O 5 27 Ag 2 O, so that a composition of (mole ratio) Li 2 CO 3, CaCO 3 , TiO 2 (anatase) and H 3 PO Prescribe 4 (85%) solution, add 0.3-1.5 wt% of CuO, mix, stir with water and make slurry, and dry it and make the dried mass less than 300 mesh Pulverized.

분쇄된 분말을 800℃에서 1시간동안 유지시켜 탈포시킨 후, 1300℃에서 1시간동안 용융시켰다. 용융된 유리를 흑연판에 부어 급냉시켜 모유리를 제조하였고, 얻어진 모유리를 615℃에서 20시간동안 유지시켜 핵생성시켰으며, 이를 730℃에서 20시간동안 유지시켜 결정화시켰다.The ground powder was degassed by holding at 800 ° C. for 1 hour and then melted at 1300 ° C. for 1 hour. The molten glass was poured into a graphite plate and quenched to prepare a mother glass, and the obtained mother glass was nucleated by holding at 615 ° C. for 20 hours, which was crystallized by holding at 730 ° C. for 20 hours.

얻어진 글라스 세라믹스를 1N HCl 용액에 3일간 침지시켜 가용성분인 Ca3(PO4)2결정상을 용출시켜 다공성을 부여하였다.The obtained glass ceramics were immersed in 1N HCl solution for 3 days to elute the Ca 3 (PO 4 ) 2 crystalline phase as a soluble component to impart porosity.

얻어진 글라스 세라믹스의 기공율과 비표면적을 측정한 결과는 46.8(%) 및 15.4(m2/g) 이었으며, 항균성은 도1과 같았다. 원적외선 방사율과 방사에너지는 아래의 표1 및 도2 내지 도7과 같았다.The porosity and specific surface area of the obtained glass ceramics were measured as 46.8 (%) and 15.4 (m 2 / g). Far-infrared emissivity and radiation energy were as shown in Table 1 below and FIGS. 2 to 7.

*항균성 측정방법* Antibacterial method

1. 세균의 전배양1. Preculture of Bacteria

그람 양성균인 포도상 구균(Staphylococcus aureus)과 그람 음성균인 장티프스(Salmonella typhi)는 영양배지에서 18시간 배양한 후 phosphate buffer 용액으로 104cfu/ml이 되게 희석한 후 사용.Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Salmonella typhi were incubated in nutrient media for 18 hours and diluted to 10 4 cfu / ml with phosphate buffer solution.

2. 항균효과 측정2. Antibacterial effect measurement

글라스 세라믹스 샘플을 121℃에서 15분간 습윤멸균한 다음, 각각의 샘플 2.5㎎을 세균(104cfu/ml) 또는 진균 포자현탁액(104spores/ml)이 첨가된 PBS(phosphate buffer solution) 5ml에 첨가 후, 25℃에서 배양하며 시간별로 샘플 0.1ml 씩을 취하여 적정배수로 희석한 후 세균은 nutrient agar에서 진균은 sabouraud dextrose agar에서 배양한 후 생성된 colony를 세고 희석배수를 곱하여 C.F.U(Colony Forming Unit, 생균수/ml)를 계산함으로써 살균효과를 측정.The glass ceramics samples were wet sterilized at 121 ° C. for 15 minutes, and 2.5 mg of each sample was added to 5 ml of PBS (phosphate buffer solution) added with bacteria (10 4 cfu / ml) or fungal spore suspension (10 4 spores / ml). After addition, incubate at 25 ℃ and take 0.1ml of sample every hour and dilute it with proper drainage.Bacterium is cultured in nutrient agar and fungus is incubated in sabouraud dextrose agar. Water / ml) to determine the bactericidal effect.

*원적외선 방사율 측정방법* Far infrared emissivity measuring method

3-20㎛ 의 파장을 대상으로 40℃에서 측정하였음.Measured at 40 ° C. with a wavelength of 3-20 μm.

(비교예 1)(Comparative Example 1)

실시예와 동일하게 시행하되, CuO를 첨가하지 아니하였다. 기공율과 비표면적을 측정한 결과는 실시예와 동일하였으며, 원적외선 방사율과 방사에너지는 아래의 표1과 같았다.In the same manner as in Example, CuO was not added. The results of measuring porosity and specific surface area were the same as in Example, and far-infrared emissivity and radiation energy were shown in Table 1 below.

(비교예 2)(Comparative Example 2)

실시예와 동일하게 시행하되 CuO를 2.0 wt%를 첨가하였다. 기공율과 비표면적을 측정한 결과는 실시예와 같았으며, 원적외선 방사율과 방사에너지는 아래의 표1과 같았다.In the same manner as in Example, but added 2.0 wt% CuO. The results of measuring porosity and specific surface area were the same as in Example, and far-infrared emissivity and emission energy were shown in Table 1 below.

표1)Table 1

구 분division 방사율(%)Emissivity (%) 방사에너지(w/㎡)Radiation energy (w / ㎡) 실시예1(CuO 0.3wt%)실시예 2(CuO 1.0wt%)실시예 3(CuO 1.5wt%)비교예 1(CuO 0)비교예 2(CuO 2.0wt%)Example 1 (CuO 0.3 wt%) Example 2 (CuO 1.0 wt%) Example 3 (CuO 1.5 wt%) Comparative Example 1 (CuO 0) Comparative Example 2 (CuO 2.0 wt%) 91.691.892.090.592.091.691.892.090.592.0 369.39370.29370.80365.23370.82369.39370.29370.80365.23370.82

이상의 실시예 및 비교예를 통하여 알 수 있는 바와 같이, 본 발명에 의한 글라스 세라믹스는 항균성과 아울러, 높은 기공율과 비표면적을 가짐과 동시에, 상온에서 높은 효율로 원적외선을 방사함으로써 식기, 위생도기 등과 같은 도자기 분야 및 식품보관용기 등과 정수재료등에 효과적으로 적용될 수 있다.As can be seen through the above examples and comparative examples, the glass ceramics according to the present invention have antimicrobial properties, high porosity and specific surface area, and emit far infrared rays with high efficiency at room temperature, such as tableware, sanitary ware, etc. It can be effectively applied to ceramics field, food storage container, and water purification material.

Claims (2)

본 발명은 0-5 Ag2O, 0-5 Li2O, 30-40 CaO, 10-25 TiO2, 20-30 P2O5(mole ratio) 의 조성이 되도록 LiCO3, CaCO3, TiO2(anantase)와 H3PO4용액을 처방하고, 여기에 0.3 - 1.5 wt%의 CuO를 첨가하여 물을 가하면서 혼합하여 슬러리 상태로 만든 다음 건조시키고, 건조된 슬러리를 300메쉬 이하의 분말상태로 분쇄한 후, 700-900℃의 온도에서 1시간 내외 유지시킨 다음, 1250-1350℃의 온도에서 용융시키고 가열된 흑연판 위에 부어 급냉시켜 모유리를 제조하고, 얻어진 모유리를 600-620℃의 온도에서 5-20시간동안 가열하여 핵생성 시킨 다음, 720-740℃의 온도에서 10-20시간동안 결정화시킨 후, 산용액에 1-5시간동안 담지시키는 것을 특징으로 하는 원적외선 방사 항균성 글라스 세라믹스 조성물의 제조방법.The present invention provides a composition of LiCO 3 , CaCO 3 , TiO such that 0-5 Ag 2 O, 0-5 Li 2 O, 30-40 CaO, 10-25 TiO 2 , and 20-30 P 2 O 5 (mole ratio). 2 (anantase) and H 3 PO 4 solution is prescribed, 0.3-1.5 wt% of CuO is added thereto, mixed with water to make a slurry, and then dried, and the dried slurry is powdered up to 300 mesh. After pulverization, and maintained at a temperature of 700-900 ° C for about 1 hour, then melted at a temperature of 1250-1350 ° C and poured on a heated graphite plate to quench the mother glass to prepare a mother glass, and obtained mother glass 600-620 ° C After nucleation by heating at a temperature of 5-20 hours, and then crystallized for 10-20 hours at a temperature of 720-740 ℃, the far-infrared radiation antibacterial glass ceramics, characterized in that it is immersed in an acid solution for 1-5 hours Method of Preparation of the Composition. 제1항에 있어서, 결정화시켜 얻어진 결정상 중 Ca3(PO4)2의 결정상이 산용액에 용해되어 용출되는 것을 특징으로 하는 원적외선 방사 항균성 글라스 세라믹스 조성물의 제조방법.The method for producing a far-infrared radiation antimicrobial glass ceramic composition according to claim 1, wherein a Ca 3 (PO 4 ) 2 crystal phase is dissolved in an acid solution and eluted in the crystal phase obtained by crystallization.
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WO2012135194A1 (en) * 2011-03-28 2012-10-04 Corning Incorporated Antimicrobial action of copper in glass
KR20220168393A (en) * 2021-06-16 2022-12-23 엘지전자 주식회사 Antibacterial glass composition and method of manufactruing antibacterial glass powder using the same and domestic appliance including the same

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KR20030083848A (en) * 2002-04-22 2003-11-01 김금복 Production method of mat and glass composition with an air cleaning effect

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JPH06183780A (en) * 1992-03-16 1994-07-05 Hideo Hosono Porous glass ceramic and its production
JP3486951B2 (en) * 1994-05-09 2004-01-13 日本板硝子株式会社 Antibacterial glass composition
KR970042406A (en) * 1995-12-29 1997-07-24 김익명 Antimicrobial Ceramics and Manufacturing Method Thereof
KR970042405A (en) * 1995-12-29 1997-07-24 김익명 Antimicrobial Ceramics and Manufacturing Method Thereof
KR100255111B1 (en) * 1997-02-04 2000-05-01 박찬영 Anti-bacterial ceramic composition maintaining freshment and the manufacture method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012135194A1 (en) * 2011-03-28 2012-10-04 Corning Incorporated Antimicrobial action of copper in glass
CN103459338A (en) * 2011-03-28 2013-12-18 康宁股份有限公司 Antimicrobial action of copper in glass
KR20220168393A (en) * 2021-06-16 2022-12-23 엘지전자 주식회사 Antibacterial glass composition and method of manufactruing antibacterial glass powder using the same and domestic appliance including the same

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