JPH0714825B2 - Antibacterial / sterilizing glass - Google Patents
Antibacterial / sterilizing glassInfo
- Publication number
- JPH0714825B2 JPH0714825B2 JP1283068A JP28306889A JPH0714825B2 JP H0714825 B2 JPH0714825 B2 JP H0714825B2 JP 1283068 A JP1283068 A JP 1283068A JP 28306889 A JP28306889 A JP 28306889A JP H0714825 B2 JPH0714825 B2 JP H0714825B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- antibacterial
- silver
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims description 47
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 30
- 230000001954 sterilising effect Effects 0.000 title claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 description 20
- 238000002844 melting Methods 0.000 description 19
- 230000008018 melting Effects 0.000 description 19
- 239000004332 silver Substances 0.000 description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 239000003242 anti bacterial agent Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- -1 silver ions Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 244000063299 Bacillus subtilis Species 0.000 description 2
- 235000014469 Bacillus subtilis Nutrition 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 239000003619 algicide Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229940023064 escherichia coli Drugs 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008223 sterile water Substances 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000201788 Staphylococcus aureus subsp. aureus Species 0.000 description 1
- NGDDCFINDCHPTF-UHFFFAOYSA-N [Br].[Ag] Chemical compound [Br].[Ag] NGDDCFINDCHPTF-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Classifications
-
- 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
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、抗菌・殺菌用ガラス（失透状態のガラスすな
わち結晶化ガラスをも包含する）に関するものである。TECHNICAL FIELD The present invention relates to antibacterial / sterilizing glass (including devitrified glass, that is, crystallized glass).
従来の技術 従来の抗菌性ガラスは重金属を含み、それらは一価の銀
イオンおよび銅イオンを含む場合が多い。その抗菌効果
は、水溶性の該ガラスによりその表面から前記イオンが
溶出することによってあらわれ、抗菌剤および殺菌剤と
して使用される。BACKGROUND OF THE INVENTION Conventional antimicrobial glasses contain heavy metals, which often contain monovalent silver and copper ions. The antibacterial effect is exhibited by elution of the ions from the surface of the water-soluble glass and is used as an antibacterial agent and a bactericidal agent.
これらの製造方法としては、重油、ガス、電気などを用
いる熔解炉や熔解るつぼを使用して1200−1400℃で熔解
する場合と、ゾルゲル法などの方法によって熔解する場
合とがある。As a method for producing these, there are a case of melting at 1200-1400 ° C. using a melting furnace or a melting crucible that uses heavy oil, gas, electricity, and a case of melting by a method such as a sol-gel method.
抗菌性ガラスは、水処理剤として、または殺藻、防藻用
に使用される場合が多い。また、殺菌、抗菌の用途以外
にも、銀イオン含有ガラスは光可変ガラス（すなわちフ
オトクロミックガラス）としても使用され、たとえばサ
ングラス等に使用され、この場合は調光ガラスとも言わ
れる。ただしこのような光可変ガラスの銀含量は酸化物
換算で0.2％以下にとどまる場合がほとんどである。Antibacterial glass is often used as a water treatment agent, or for algae killing and controlling. In addition to sterilization and antibacterial applications, the silver ion-containing glass is also used as light variable glass (that is, photochromic glass), for example, sunglasses, and in this case, it is also called dimming glass. However, in most cases, the silver content of such light-variable glass is less than 0.2% in terms of oxide.
発明が解決しようとする問題点 上述の従来の抗菌剤ガラスは一般に一価の銀を多量に含
み、酸化物換算で約１−５％である。また、ゾルゲル法
においては銀を数十％も多量に含んでいる。そこで銀を
使用した場合、経済的および資源的な見地からも難しい
問題点が多い。また、一価または二価の銅イオンを使用
する場合は、ガラスの銅含量は約１−35％である。Problems to be Solved by the Invention The above-mentioned conventional antibacterial agent glass generally contains a large amount of monovalent silver, and its content is about 1-5% in terms of oxide. Further, the sol-gel method contains a large amount of silver of several tens of percent. Therefore, when using silver, there are many difficult problems from an economical and resource standpoint. Also, when monovalent or divalent copper ions are used, the copper content of the glass is about 1-35%.
また、熔解炉法で熔解した場合、殺菌および抗菌効果を
上げようと銀含量を増加すれば熔解中に還元され、溶解
炉の底部に金属銀として残り、ガラス中に熔解しない欠
点がある。Further, in the case of melting by a melting furnace method, if the silver content is increased in order to enhance the sterilization and antibacterial effects, it is reduced during the melting, remains as metallic silver at the bottom of the melting furnace, and does not melt in the glass.
そこで本発明は、一価の銀イオンや銅イオンがガラス中
に熔解が難しいという問題点を解決し、かつ、さらに強
力な殺菌力を付与するためにハロゲン族イオン（たとえ
ばCl、Br、Ｉイオン）を積極的に添加することを包含す
る。この場合には、熔解炉で熔かしたときでも銀や銅イ
オンは容易にガラス中にコロイドとして分散し、銀イオ
ンのガラス中残存率が高い。Therefore, the present invention solves the problem that monovalent silver ions and copper ions are difficult to melt in glass, and further imparts a stronger sterilizing power to halogen group ions (for example, Cl, Br, I ions). ) Is added positively. In this case, silver and copper ions are easily dispersed in the glass as a colloid even when melted in a melting furnace, and the residual ratio of silver ions in the glass is high.
また、銀を多量含む場合は、従来のガラスでは黒色化が
生じ、粉砕してもその着色はあり、用途によっては使用
できない場合がある。Further, when a large amount of silver is contained, conventional glass is blackened, and even if it is crushed, it is colored and may not be used depending on the application.
AgイオンおよびCuイオンが殺菌および抗菌作用を有する
ことは既に知られており、本発明ではこれに、ガラス中
に強力な殺菌および抗菌力を発揮するハロゲン族元素で
あるたとえば塩素（Cl）、ブロム（Br）、ヨウ素（Ｉ）
を積極的に添加し、両方の効果を期待しつつ相乗効果を
ねらい、安価な抗菌、殺菌剤を供給するものである。It is already known that Ag ions and Cu ions have a bactericidal and antibacterial action, and in the present invention, the halogen group elements such as chlorine (Cl) and bromine which exert a strong bactericidal and antibacterial action in the present invention are added to this. (Br), iodine (I)
In order to achieve a synergistic effect while expecting both effects, an inexpensive antibacterial and bactericidal agent is supplied.
また、通常の熔解炉法では銀コロイド（原料はほとんど
の場合硝酸銀を使用）としてガラス中になかなか熔解が
難しく、熔解操作の後に金属銀が熔解炉の底部に残り、
上述の効果がなかなか出しにくい。Also, in the usual melting furnace method, it is quite difficult to melt in the glass as silver colloid (mostly silver nitrate is used as a raw material), and metallic silver remains at the bottom of the melting furnace after the melting operation.
It is difficult to obtain the above effects.
本発明によれば、銀コロイドおよび／または銅コロイド
を残し、さらに、ハロゲン族イオンの添加により、ガラ
ス中にそれらの残存率が非常に高くなることが見出され
た。According to the present invention, it was found that the silver colloid and / or the copper colloid are left, and the addition of the halogen group ion makes the residual ratio thereof very high in the glass.
また、本発明では、容易に水に溶解するB2O3の量を多く
し、かつ溶出速度を早めるアルカリ金属の含有量の多い
組成としたので、従来は効果が少ないとされていた、重
金属含量が低いときでも、本発明の抗菌性ガラスは充分
な殺菌および抗菌効果を発揮する。Further, in the present invention, the amount of B 2 O 3 that is easily dissolved in water is increased, and the composition is high in the content of alkali metal that accelerates the elution rate. Even when the content is low, the antibacterial glass of the present invention exerts sufficient bactericidal and antibacterial effects.
発明の構成 本発明は、SiO2 30〜80重量％、B2O3 8〜40重量％、Ag2
O 1〜５重量％またはCuO 1〜30重量％、Cl,BrおよびＩ
からなる群から選ばれたハロゲン 0.05〜２重量％、Na2
O 3〜15重量％を基本構成とする抗菌・殺菌用ガラスで
ある。Composition of the Invention The present invention relates to SiO 2 30 to 80 wt%, B 2 O 3 8 to 40 wt%, Ag 2
1-5 wt% O or 1-30 wt% CuO, Cl, Br and I
Halogen selected from the group consisting of 0.05-2% by weight, Na 2
It is an antibacterial / sterilizing glass with a basic composition of O 3-15% by weight.
上記組成には、さらにK2O 0.1〜10重量％を添加するこ
とができ、また、さらにAl2O3 5重量％以下及び／また
はZr2O 3重量％以下を添加することもできる。To the above composition, 0.1 to 10% by weight of K 2 O can be further added, and 5% by weight or less of Al 2 O 3 and / or 3% by weight or less of Zr 2 O 3 can be further added.
特に好ましい組成は、SiO2 68.0重量％、Al2O3 3.0重量
％、B2O3 12.0重量％、Ag2O 3.0重量％またはCuO 20.0
重量％、Cl,BrおよびＩからなる群から選ばれたハロゲ
ン 0.4重量％、Na2O 8.6重量％、K2O 3.0重量％、ZrO2
2.0重量％である。Particularly preferable compositions are SiO 2 68.0 wt%, Al 2 O 3 3.0 wt%, B 2 O 3 12.0 wt%, Ag 2 O 3.0 wt% or CuO 20.0.
% By weight, halogen selected from the group consisting of Cl, Br and I 0.4% by weight, Na 2 O 8.6% by weight, K 2 O 3.0% by weight, ZrO 2
2.0% by weight.
本発明の抗菌・殺菌用ガラスは、普通のほうけい酸塩系
ガラスの場合と実質的に同様な製法によって製造でき
る。The antibacterial / sterilizing glass of the present invention can be manufactured by a manufacturing method substantially similar to the case of ordinary borosilicate glass.
本発明のガラスはほうけい酸塩系ガラスを主体としてい
るので、その原料は、シリカ（SiO2）、ほう砂（Na2B4O
7）、酸化ほう素（B2O3）、ほう酸（H3BO4）、さらに硝
酸銀（AgNO3）、塩化銀（AgCl）、ブロム銀（AgBr）、
ヨウ化銀（AgI）、塩化ナトリウム（NaCl）等である。Since the glass of the present invention is mainly composed of borosilicate glass, its raw materials are silica (SiO 2 ) and borax (Na 2 B 4 O
7 ), boron oxide (B 2 O 3 ), boric acid (H 3 BO 4 ), silver nitrate (AgNO 3 ), silver chloride (AgCl), bromine silver (AgBr),
Examples include silver iodide (AgI) and sodium chloride (NaCl).
また、銅の化合物、酸化物も同様である。The same applies to copper compounds and oxides.
所定の原料を混合してるつぼまたは熔解炉に入れ、1200
−1400℃程度の高温で熔解し、次いで冷却してガラスを
得る。既述の従来の含銀ガラスの場合と異なり、本発明
のガラスの熔融操作の場合には、銀や銅は容易にガラス
中にコロイドとして分散し、これらの重金属イオンのガ
ラス中残存率が高い。このことは、既に述べたように本
発明の重要な特長の１つである。Mix the prescribed materials and put them in a crucible or melting furnace.
Melt at a high temperature of about -1400 ° C, and then cool to obtain glass. Unlike the case of the conventional silver-containing glass described above, in the glass melting operation of the present invention, silver and copper are easily dispersed as a colloid in the glass, and the residual ratio of these heavy metal ions in the glass is high. . This is one of the important features of the present invention as described above.
本発明のガラスは、従来の抗菌性ガラスの場合と同様
に、水処理剤、殺藻、防藻剤、および殺菌、抗菌剤とし
て、種々の分野で有利に使用できる。使用量は、当該技
術分野の技術者であれば容易に決定できるであろう。こ
の抗菌性ガラスの使用方法の若干の具体例は、後記の実
施例中に記載されている。Like the conventional antibacterial glass, the glass of the present invention can be advantageously used in various fields as a water treatment agent, an algaecide, an algaecide, and a bactericidal or antibacterial agent. The amount used can be easily determined by those skilled in the art. Some specific examples of how to use this antibacterial glass are described in the examples below.
次に本発明の実施例を示す。しかしながら本発明の範囲
は決して実施例に記載の範囲内のみに限定されるもので
はない。Next, examples of the present invention will be described. However, the scope of the invention is in no way limited to the scope described in the examples.
実施例１ SiO2 68.0、Al2O3 3.0、B2O3 12.0、Ag2O 3.0、ハロゲ
ン 0.4、Na2O 8.6、K2O 3.0、NrO2 2.0（wt％）の基本
組成をもつガラスを熔解した。ガラス原料は炭酸塩、水
酸化物、およびハロゲン化物を利用した。熔解条件はガ
ラス量で200kg、熔解温度1350℃、熔解時間3hr、そして
ハロゲンガスを熔解しルツボに充填しながら行った。途
中、30分毎にステンレス棒で撹拌を行ない、Ag2Oおよび
ハロゲンが均一にガラス中に分散するようにした。熔解
後、ルツボよりガラスを取り出し、水中で急冷乾燥後、
ボールミルにて20μｍ以下になるよう粉砕を行なった。
なお、金属銀の析出（ルツボ底部）は、ほとんどなし。
色調は白色、乳濁、銀はコロイド状に分散していた。Example 1 Glass having a basic composition of SiO 2 68.0, Al 2 O 3 3.0, B 2 O 3 12.0, Ag 2 O 3.0, halogen 0.4, Na 2 O 8.6, K 2 O 3.0, and NrO 2 2.0 (wt%). Melted. Carbonates, hydroxides, and halides were used as glass raw materials. The melting conditions were glass amount of 200 kg, melting temperature of 1350 ° C., melting time of 3 hours, and melting with a halogen gas and filling the crucible. On the way, stirring was performed with a stainless steel bar every 30 minutes so that Ag 2 O and halogen were uniformly dispersed in the glass. After melting, take out the glass from the crucible, quench and dry in water,
It was crushed by a ball mill so that the particle size became 20 μm or less.
Almost no metal silver deposition (bottom of crucible).
The color tone was white, milky, and silver was colloidally dispersed.
このガラスを、抗菌剤としての効果を見るために、菌数
測定法にて測定した。This glass was measured by the bacterial count method in order to see the effect as an antibacterial agent.
ウレタン樹脂（溶剤分 70％、固形分 30％）93％に対
し、このガラス７％を添加した。転写紙にコーテイング
し、それを紳士用靴下に転写した。それらを、無加工試
料と菌数測定法によって比較した。（抗菌防臭加工製品
の加工効果評価試験マニュアル・菌数測定法：繊維製品
衛生加工協議会 昭和63年）なお、試験菌は、黄色ぶど
う状球菌〔Staphylococcus aureus,ATCC 6538P（IFO 12
732）〕を用いた。7% of this glass was added to 93% of urethane resin (solvent content 70%, solid content 30%). It was coated on transfer paper and transferred to men's socks. They were compared to the unprocessed sample by a densitometry method. (Processing effect evaluation test manual for antibacterial and deodorant processed products, bacterial count measurement method: Textile Product Hygiene Processing Council, 1988) The test bacteria are Staphylococcus aureus, ATCC 6538P (IFO 12
732)] was used.
上表の結果より、オリジナル1.0×102に対し、洗濯後10
回で3.2×10-1と大幅に減少、黄色ぶどう状球菌に対し
て非常な効果があった。 From the results in the above table, after washing 10 against the original 1.0 × 10 2.
It was greatly reduced to 3.2 × 10 -1, and it was very effective against Staphylococcus aureus.
洗濯後、優秀な結果が得られたのは、表面樹脂が洗濯ご
とに取れ、抗菌剤が溶出し、抗菌結果に対して良い効果
が出たためである。After washing, excellent results were obtained because the surface resin was removed with each washing and the antibacterial agent was eluted, which had a good effect on the antibacterial results.
なお、転写の形状は、ベタ塗りでなく、高さ2mm、丸さ3
mmのドットの水玉状転写であり、空間率50％である。し
たがって、空間率が０％の場合は２倍の効果が出ると確
信できる。The shape of the transfer is 2 mm high and 3 round, not solid.
It is a dot-shaped transfer of mm dots and has a porosity of 50%. Therefore, when the porosity is 0%, it can be convinced that the effect is doubled.
実施例２ 第３表に記載のガラス組成物を熔解した。原料は実施例
１の場合と同様で、条件は第３表の通りである。６種類
の抗菌剤を同様に転写紙にコーテイングし、その後、紳
士用肌着に転写し、比較した。供試菌は、大腸菌（Esch
erichia coli）、黄色ぶどう状球菌（Staphy lococcus
aureus）、枯草菌（Bacillus suntilis）である。試験
方法は、あらかじめ前培養を行った細菌を減菌水で懸濁
させ、ハートインヒュージョン寒天培地15mlに対し、0.
2mlの割合で混釈し、平板に固める。この上から、直径2
cmの大きさに切り取った試料をのせ、30℃24時間培養
後、生じたハロー（生育阻止帯）の有無を観察した。Example 2 The glass composition shown in Table 3 was melted. The raw materials are the same as in Example 1, and the conditions are as shown in Table 3. Six types of antibacterial agents were similarly coated on a transfer paper, and then transferred to men's underwear for comparison. The test bacteria are Escherichia coli (Esch
erichia coli), Staphylococcus aureus
aureus), Bacillus subtilis (Bacillus suntilis). The test method is to suspend the pre-cultured bacteria in sterile water, and for 0.5 ml of heart-infusion agar, 0.
Pour at a rate of 2 ml and solidify on a flat plate. From above, diameter 2
A sample cut into a size of cm was put on the plate, and after culturing at 30 ° C. for 24 hours, the presence or absence of the generated halo (growth arrest zone) was observed.
また、あらかじめ前培養した細菌を減菌水に懸濁させ、
試験管に5mlずつ分散し、これに１×2cmの試料片を２枚
入れ、振盪培養し、直後の菌数と24時間置後の菌数の変
化を測定した。Also, suspend the pre-cultured bacteria in sterile water,
5 ml each was dispersed in a test tube, two 1 × 2 cm sample pieces were put into this, and shake culture was carried out, and changes in the number of bacteria immediately after and after 24 hours of standing were measured.
第３表の結果より、試料No.1,2,3の水への溶解速度の早
いガラスは、SiO2が少なく約70％以下で、また、容易に
水に溶解するB2O3の量の高い組成および、また溶出速度
を早めるアルカリ金属の含有量の多いものが、菌数の抗
菌に効果があったと認められる。また試料No.4,5,6も、
抗菌力は前記の試料より多少劣るが、しかし、かなりの
抗菌効果を上げている。また、Ag2Oの含有量が、公知の
ガラスより少量であるにもかかわらず、ハロゲンの添加
により、さらに抗菌の効果が著しい。 From the results shown in Table 3, the glasses of Samples Nos. 1, 2, and 3 that have a fast dissolution rate in water have a low SiO 2 content of approximately 70% or less, and the amount of B 2 O 3 that dissolves easily in water. It is considered that the composition having a high content and a high content of alkali metal which accelerates the dissolution rate were effective in the antibacterial effect of the bacterial count. Sample Nos. 4, 5 and 6 are also
The antibacterial activity is slightly inferior to that of the above sample, however, the antibacterial effect is considerably increased. Further, although the content of Ag 2 O is smaller than that of known glass, the addition of halogen makes the antibacterial effect more remarkable.
実施例３ 第４表に記載のガラス組成物を熔解した。原料は、実施
例1,2の場合と同様で、条件も同様である。また、抗菌
剤としての試験も同様である。その結果を第４表にまと
めた。Example 3 The glass composition shown in Table 4 was melted. The raw materials are the same as in Examples 1 and 2, and the conditions are also the same. The same applies to tests as antibacterial agents. The results are summarized in Table 4.
実施例３より、CuOおよびAg2O、さらには、試料No.2、N
o.7のハロゲンの添加をしない組成を検討した結果、CuO
とハロゲンの入った抗菌剤は、黄色ぶどう状球菌に対し
ては非常に良い効果を表している。また、大腸菌および
枯草菌に対しても効果がある。なお、公知のAg2O入り抗
菌剤と、それにハロゲンの入った本発明の抗菌剤とで
は、やはりハロゲン入りの方が結果が非常に良い、ま
た、CuOにハロゲンの入った抗菌剤も良い効果があり、
本発明が経済的な見地からも、また、抗菌効果も、従来
の物よりはるかに優れていることが確信できた。 From Example 3, CuO and Ag 2 O, as well as sample No. 2 and N
As a result of examining the composition of o.7 without adding halogen, it was found that CuO
The antibacterial agents containing and halogen show very good effect against Staphylococcus aureus. It is also effective against E. coli and Bacillus subtilis. In addition, in the case of the known Ag 2 O-containing antibacterial agent and the halogen-containing antibacterial agent of the present invention, the halogen-containing antibacterial agent gives a very good result, and the CuO halogen-containing antibacterial agent also has a good effect. There is
It was convinced that the present invention is far superior to the conventional ones from the economical point of view and the antibacterial effect.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1283068A JPH0714825B2 (en) | 1989-11-01 | 1989-11-01 | Antibacterial / sterilizing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1283068A JPH0714825B2 (en) | 1989-11-01 | 1989-11-01 | Antibacterial / sterilizing glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03146436A JPH03146436A (en) | 1991-06-21 |
| JPH0714825B2 true JPH0714825B2 (en) | 1995-02-22 |
Family
ID=17660789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1283068A Expired - Fee Related JPH0714825B2 (en) | 1989-11-01 | 1989-11-01 | Antibacterial / sterilizing glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0714825B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021145724A1 (en) * | 2020-01-17 | 2021-07-22 | 엘지전자 주식회사 | Antibacterial glass composition and method for preparing same |
| WO2022211156A1 (en) * | 2021-04-01 | 2022-10-06 | 엘지전자 주식회사 | Non-elutable antimicrobial glass composition, and method for preparing antimicrobial glass powder using same |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994027442A1 (en) * | 1993-05-31 | 1994-12-08 | Sumitomo Osaka Cenent Co., Ltd. | Antibacterial mildewproof glaze composition for ceramic products |
| JPH07196385A (en) * | 1993-11-25 | 1995-08-01 | Sumitomo Osaka Cement Co Ltd | Method for producing ceramic product and ceramic product |
| GB9502253D0 (en) * | 1995-02-06 | 1995-03-29 | Giltech Ltd | The effects of antibacterial agents on the behaviour of mouse fibroblasts in vitro |
| JP3697540B2 (en) * | 2000-01-31 | 2005-09-21 | 株式会社トーエー | Bacteria growth-inhibiting sand manufacturing apparatus and method |
| DE10141117A1 (en) * | 2001-08-22 | 2003-03-13 | Schott Glas | Antimicrobial silicate glass and its use |
| DE10156577A1 (en) * | 2001-11-20 | 2003-05-28 | Schott Glas | Anti-inflammatory, wound-healing glass powder has specified composition |
| DE10141230A1 (en) * | 2001-08-22 | 2003-03-13 | Schott Glas | Color additive including a glass with an antimicrobial effect |
| WO2003018496A1 (en) * | 2001-08-22 | 2003-03-06 | Schott Glas | Antimicrobial, anti-inflammatory, wound-healing glass powder and use thereof |
| WO2003018498A1 (en) | 2001-08-22 | 2003-03-06 | Schott Glas | Antimicrobial, anti-inflammatory, wound-healing and disinfecting glass and use thereof |
| DE10293768B4 (en) * | 2001-08-22 | 2011-05-12 | Schott Ag | Antimicrobial glass powder, its use and process for its preparation |
| DE10214273A1 (en) * | 2002-03-28 | 2003-10-23 | Schott Glas | Use of glass and/or glass ceramic powder and/or fiber for time- and quantity-controlled ion release is useful cosmetic or medicinal formulation as skin care cream and for healing or covering wound and treating chronic wound |
| JP4602320B2 (en) | 2003-02-25 | 2010-12-22 | ショット アクチエンゲゼルシャフト | Antimicrobial action phosphate glass |
| JP2006520311A (en) * | 2003-02-25 | 2006-09-07 | ショット アクチエンゲゼルシャフト | Antimicrobial action borosilicate glass |
| DE10345625A1 (en) * | 2003-09-29 | 2005-04-28 | Schott Ag | Making glass powder with time-release antimicrobial action, for use in widely-diverse consumables, employs purely inorganic solutions and nanoparticle suspensions in sol-gel process |
| KR100655152B1 (en) * | 2003-10-22 | 2006-12-08 | 광덕신약 주식회사 | Composition for sterilizing and product using the same |
| KR100657123B1 (en) * | 2004-03-15 | 2006-12-13 | 코아 가라스 가부시키가이샤 | Antibacterial glass and method for producing antibacterial glass |
| DE102005004790A1 (en) * | 2005-02-01 | 2006-08-31 | Seleon Gmbh | Glass frit, open-pored foamed glass, disinfection device, water tank, air conditioning, use and method |
| WO2010140515A1 (en) | 2009-06-03 | 2010-12-09 | コニカミノルタオプト株式会社 | Image pickup lens, image pickup device having image pickup lens, and portable terminal having image pickup device |
| CN101606537B (en) | 2009-06-23 | 2011-12-21 | 哈尔滨工业大学 | Preparation method of SiO2-AgCl composite antibacterial thin films |
| US20140079807A1 (en) * | 2011-03-28 | 2014-03-20 | Corning | Antimicrobial action of copper in glass |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
| WO2015123077A1 (en) | 2014-02-13 | 2015-08-20 | Corning Incorporated | Glass with enhanced strength and antimicrobial properties, and method of making same |
| US11039621B2 (en) | 2014-02-19 | 2021-06-22 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| US9622483B2 (en) * | 2014-02-19 | 2017-04-18 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| US11039620B2 (en) | 2014-02-19 | 2021-06-22 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
| JP5784848B1 (en) * | 2014-07-10 | 2015-09-24 | 石塚硝子株式会社 | Deodorants |
| JP6472727B2 (en) * | 2015-07-23 | 2019-02-20 | 石塚硝子株式会社 | Absorbent pad |
| JP6441182B2 (en) * | 2015-08-05 | 2018-12-19 | 石塚硝子株式会社 | Masterbatch and method for producing deodorant resin composition |
| JP6670055B2 (en) * | 2015-08-13 | 2020-03-18 | 石塚硝子株式会社 | Glass film forming material and glass coated product using the same |
| WO2017070280A1 (en) | 2015-10-21 | 2017-04-27 | Corning Incorporated | Antimicrobial phase-separable glass/polymer composite articles and methods for making the same |
| JP6388888B2 (en) * | 2016-02-05 | 2018-09-12 | 国立大学法人徳島大学 | Coating composition |
| WO2017185341A1 (en) * | 2016-04-29 | 2017-11-02 | Kornerstone Materials Technology Company, Ltd. | Antimicrobial chemically strengthened glass and optimization method for the manufacture thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168339A (en) | 1978-07-26 | 1979-09-18 | Corning Glass Works | Photochromic microsheet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4222781A (en) * | 1979-08-16 | 1980-09-16 | Corning Glass Works | Optically clear copper halide photochromic glass articles |
| US4284686A (en) * | 1980-06-09 | 1981-08-18 | Corning Glass Works | Spectacle lenses to reduce discomfort from aphakia and certain eye diseases |
| US4358542A (en) * | 1981-04-08 | 1982-11-09 | Corning Glass Works | Photochromic glass suitable for microsheet and simultaneous heat treatment and shaping |
| US4374931A (en) * | 1982-01-08 | 1983-02-22 | Corning Glass Works | Photochromic glass suitable for ophthalmic applications |
-
1989
- 1989-11-01 JP JP1283068A patent/JPH0714825B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168339A (en) | 1978-07-26 | 1979-09-18 | Corning Glass Works | Photochromic microsheet |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021145724A1 (en) * | 2020-01-17 | 2021-07-22 | 엘지전자 주식회사 | Antibacterial glass composition and method for preparing same |
| KR20210093120A (en) * | 2020-01-17 | 2021-07-27 | 엘지전자 주식회사 | Antibacterial glass composite, manufacturing method thereof |
| WO2022211156A1 (en) * | 2021-04-01 | 2022-10-06 | 엘지전자 주식회사 | Non-elutable antimicrobial glass composition, and method for preparing antimicrobial glass powder using same |
| EP4317093A4 (en) * | 2021-04-01 | 2025-03-05 | LG Electronics Inc. | NON-ELUTABLE ANTIMICROBIAL GLASS COMPOSITION, AND METHOD FOR PREPARING ANTIMICROBIAL GLASS POWDER USING SAME |
| AU2021437878B2 (en) * | 2021-04-01 | 2025-09-11 | Lg Electronics Inc. | Non-elutable antimicrobial glass composition, and method for preparing antimicrobial glass powder using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03146436A (en) | 1991-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH03146436A (en) | Antimicrobial glass | |
| US8080490B2 (en) | Antimicrobial phosphate glass | |
| US7192602B2 (en) | Water-insoluble, antimicrobial silicate glass and use thereof | |
| EP1667941B1 (en) | Antimicrobial glass surfaces of glass powders | |
| US20050233888A1 (en) | Antimicrobial phosphate glass with adapted refractive index | |
| WO2003018498A1 (en) | Antimicrobial, anti-inflammatory, wound-healing and disinfecting glass and use thereof | |
| US20060166806A1 (en) | Antimicrobial sulfophosphate glass | |
| JPS62210098A (en) | Glass water treating agent | |
| TW201309614A (en) | Antimicrobial action of copper in glass | |
| EP0809506A2 (en) | Antimicrobial composition composed of controlled release glasses | |
| JPH07300339A (en) | Antifungal glass composition | |
| CN114847279A (en) | A kind of inorganic antibacterial agent and preparation method thereof | |
| JPH0848539A (en) | Antibacterial glass composition | |
| KR20230024947A (en) | Antibacterial glass powder and manufacturing method of antibacterial glass powder | |
| JPH01317133A (en) | Water-treating agent made from glass | |
| CN116947314A (en) | Ultra-white antibacterial glass and preparation method thereof | |
| JPH1160268A (en) | Antimicrobial glass and resin composition | |
| JP2628014B2 (en) | Polarized glass | |
| JP3248279B2 (en) | Composition for antibacterial glass | |
| JPH0269334A (en) | Highly refractive low density phototropic glass | |
| JP3110963B2 (en) | Durable antimicrobial agent | |
| JPH07291654A (en) | Antimicrobial glass powder | |
| JP2000302478A (en) | Microbicidal glass and polystyrene resin composition containing the same | |
| US3957498A (en) | Boron-free silver halide photochromic glasses | |
| JPH0748142A (en) | Production of glass containing silver ion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |