JPH11228186A - Glass, production of glass and composition for tempered anti-bacterial gass - Google Patents
Glass, production of glass and composition for tempered anti-bacterial gassInfo
- Publication number
- JPH11228186A JPH11228186A JP2681898A JP2681898A JPH11228186A JP H11228186 A JPH11228186 A JP H11228186A JP 2681898 A JP2681898 A JP 2681898A JP 2681898 A JP2681898 A JP 2681898A JP H11228186 A JPH11228186 A JP H11228186A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- antibacterial
- silver
- potassium
- surface layer
- 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.)
- Pending
Links
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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス、特に抗菌
性を有する強化ガラス、及びその製造方法、並びにその
製造に用いる組成物に関する。The present invention relates to a glass, especially a tempered glass having antibacterial properties, a method for producing the same, and a composition used for producing the same.
【０００２】[0002]
【従来の技術】アルカリ成分としてナトリウムイオンを
含有するガラスをカリウムイオンを含有する溶融塩に接
触させ、ガラス中のナトリウムイオンと溶融塩中のカリ
ウムイオンとの間でのイオン交換により強度を向上させ
たガラスが知られている。しかし、この強化ガラスでも
耐久性に問題があるとされ、ガラス中のナトリウムイオ
ンと溶融塩中のカリウムイオンとの間でのイオン交換に
よりガラス板表面に圧縮層を形成した後、ガラス板表面
をリチウム塩水溶液に接触させることが提案（特開平７
−２２３８４５号公報）されている。2. Description of the Related Art Glass containing sodium ions as an alkali component is brought into contact with a molten salt containing potassium ions, and the strength is improved by ion exchange between sodium ions in the glass and potassium ions in the molten salt. Glass is known. However, even with this tempered glass, it is said that there is a problem in durability, and after forming a compression layer on the surface of the glass plate by ion exchange between sodium ions in the glass and potassium ions in the molten salt, the surface of the glass plate is removed. Proposal to contact with lithium salt aqueous solution
223845).
【０００３】ところで、現在、我々が生活している環境
中には、様々な菌が生息している。菌の存在は、健康な
人にとって余り問題ないものの、病人、子供、高齢者の
ような抵抗力の低い人にとっては問題がある。特に、最
近、医療施設においては院内感染が問題となっており、
この対策として抗菌剤による抗菌作用（殺菌作用、滅菌
作用、細菌増殖抑止作用）が注目されている。At present, various bacteria inhabit the environment where we live. Although the presence of the bacterium is less problematic for healthy people, it is problematic for people with low resistance, such as the sick, children, and the elderly. In particular, hospital-acquired infections have recently become a problem in medical facilities,
As a countermeasure against this, attention has been paid to the antibacterial action (bactericidal action, sterilizing action, and bacterial growth inhibiting action) of the antibacterial agent.
【０００４】例えば、銀、銅、亜鉛、及びこれら金属の
イオンが抗菌作用を持つことが知られている。そして、
これらの金属や金属イオンを含む商品は歴史的にも実績
が有り、かつ、地球環境に優しい安全性が高いと言われ
ている。最近では、特開平４−３３８１３８号公報で、
ガラスを硝酸銀水溶液に浸漬し、熱処理を加え、ガラス
に含まれるナトリウムイオンを殺菌作用を呈する銀イオ
ンと置換した殺菌性ガラスが提案されている。For example, it is known that silver, copper, zinc and ions of these metals have an antibacterial effect. And
Products containing these metals and metal ions have a track record in history and are said to have high environmentally friendly safety. Recently, Japanese Patent Application Laid-Open No. 4-338138 discloses that
A germicidal glass in which glass is immersed in an aqueous solution of silver nitrate and subjected to heat treatment to replace sodium ions contained in the glass with silver ions having a bactericidal action has been proposed.
【０００５】特開平９−６７１４３号公報では、金属銀
または銀化合物を蒸発させ、銀の蒸発雰囲気下でガラス
組成物中に銀を拡散させた抗菌ガラスが提案されてい
る。Japanese Patent Application Laid-Open No. 9-67143 proposes an antibacterial glass obtained by evaporating metallic silver or a silver compound and diffusing silver into a glass composition under an atmosphere of evaporating silver.
【０００６】[0006]
【発明が解決しようとする課題】前記ガラスに含まれる
ナトリウムイオンを銀イオンで置換したガラスは、銀イ
オンに起因して抗菌性が優れているものの、強度的な問
題が残されている。更には、透明性も悪い。一方、ガラ
スに含まれるナトリウムイオンをカリウムイオンで置換
したガラスは、強度的に優れているものの、抗菌性が無
い。The glass in which the sodium ion contained in the glass is replaced with silver ion has excellent antibacterial properties due to silver ion, but has a problem in strength. Furthermore, transparency is poor. On the other hand, glass in which sodium ions contained in glass are replaced with potassium ions is excellent in strength but does not have antibacterial properties.
【０００７】従って、本発明が解決しようとする第１の
課題は、抗菌性に優れ、かつ、強度的にも優れたガラス
を提供することである。又、本発明が解決しようとする
第２の課題は、抗菌性に優れ、かつ、強度的に優れ、更
には透明性にも優れたガラスを提供することである。Accordingly, a first object of the present invention is to provide a glass having excellent antibacterial properties and excellent strength. A second problem to be solved by the present invention is to provide a glass having excellent antibacterial properties, excellent strength, and excellent transparency.
【０００８】[0008]
【課題を解決するための手段】ガラスに含まれるナトリ
ウムイオンをカリウムイオンで置換した場合には、強度
向上が図れるものの、抗菌性が得られず、又、ガラスに
含まれるナトリウムイオンを銀イオンで置換した場合に
は、抗菌性が得られるものの、強度向上が小さく、更に
はガラス特有の透明感が損なわれる。When sodium ions contained in glass are replaced with potassium ions, strength can be improved, but antibacterial properties cannot be obtained, and sodium ions contained in glass are replaced with silver ions. When substituted, antibacterial properties are obtained, but the improvement in strength is small, and further, the transparency unique to glass is impaired.
【０００９】そこで、ガラスに含まれるナトリウムイオ
ンをカリウムイオン及び銀イオンの双方で置換したなら
ばと考えたものの、これでは、ガラスに含まれるナトリ
ウムイオンに対するカリウムイオンの置換量や銀イオン
の置換量は中途半端なものとなり、抗菌性や強度が共に
満足できないであろうと予想された。つまり、一定量の
ナトリウムイオンをカリウムイオンと銀イオンとの両者
で置換したならば、カリウムイオンだけの場合、又、銀
イオンだけの場合に比べて、各々の置換量は減少するこ
とになり、各々の効果（強度向上、抗菌性）が共に弱く
なってしまうであろうと考えられた。Therefore, although it was considered that the sodium ions contained in the glass were replaced by both potassium ions and silver ions, in this case, the replacement amount of potassium ions and the replacement amount of silver ions with respect to the sodium ions contained in the glass were considered. Was half-finished, and it was expected that both antibacterial properties and strength would not be satisfactory. In other words, if a certain amount of sodium ions are replaced by both potassium ions and silver ions, the respective replacement amounts will be reduced as compared with the case of only potassium ions or the case of only silver ions, It was thought that each effect (strength improvement, antibacterial property) would be weakened together.
【００１０】しかし、本発明者による研究開発が鋭意押
し進められて行くうちに、意外な結果に遭遇した。すな
わち、硝酸銀と硝酸カリウムとの溶融塩を用いてナトリ
ウムを含むガラスを処理した場合、硝酸銀を含まない硝
酸カリウムのみの溶融塩で処理した場合よりも、ガラス
の曲げ強度が一層向上することを見出したのである。こ
の現象について本発明者は次のように考えた。銀イオン
とカリウムイオンとがガラス中に熱拡散すると、ナトリ
ウムイオンと置換したカリウムイオンはイオン状態で存
在するものの、銀イオンは金属銀に還元され、ガラス中
の酸素イオンが余剰になり、電気的平衡が保たれなくな
る。そこで、電気的平衡を保とうとする作用が働き、処
理浴中のカリウムイオンが更にガラス中に拡散し、カリ
ウムイオンが増加し、表面での圧縮応力が増して曲げ強
度が一層向上したと考えたのである。[0010] However, as the research and development by the inventor proceeded intensively, unexpected results were encountered. That is, when the glass containing sodium was treated using the molten salt of silver nitrate and potassium nitrate, the bending strength of the glass was further improved as compared with the case where the glass was treated with the molten salt containing only potassium nitrate containing no silver nitrate. is there. The present inventor considered this phenomenon as follows. When silver ions and potassium ions are thermally diffused into the glass, potassium ions replaced with sodium ions exist in an ionic state, but silver ions are reduced to metallic silver, oxygen ions in the glass become excessive, and electrical The balance will not be maintained. Therefore, it was thought that the action of maintaining electrical equilibrium worked, potassium ions in the treatment bath were further diffused into the glass, potassium ions increased, compressive stress on the surface increased, and bending strength was further improved. It is.
【００１１】又、銀イオンは短時間のうちにガラス中に
拡散しており、これに対してカリウムイオンのガラス中
への拡散は遅く、従って上記のことから銀イオンが侵入
・拡散し、還元されて銀となり、ガラス中の酸素イオン
が余剰になると、電気的平衡が保たれなくなることか
ら、カリウムイオンのガラス中への拡散も早くなり、従
って短時間での処理で済むから、カリウムイオンは内部
深い箇所まで拡散し難く、この為表面での圧縮応力が増
し、曲げ強度が一層向上したと考えたのである。The silver ions diffuse into the glass in a short time, whereas the diffusion of potassium ions into the glass is slow. When silver ions become excessive and oxygen ions in the glass become excessive, electrical equilibrium is no longer maintained, and the diffusion of potassium ions into the glass also becomes faster, so that processing in a short time can be completed. It was thought that it was difficult to diffuse deeply into the inside, so that the compressive stress on the surface increased, and the bending strength was further improved.
【００１２】又、銀イオンがガラス中に拡散して行った
ならば、カリウムイオンも一層拡散して行く結果とな
り、曲げ強度が一層向上するだけでなく、ガラス中への
銀イオンの拡散がカリウムイオンの拡散によって阻害さ
れるものでもなく、銀による抗菌性が損なわれるもので
無いことも判って来た。このような知見に沿って本発明
が達成されたものであり、前記の課題は、ガラス表面層
のＮａ+ がＭ+ （ＭはＮａよりイオン半径が大きなアル
カリ金属原子）で置換されると共に、ガラス表面層に抗
菌性物質が設けられてなることを特徴とするガラスによ
って解決される。If silver ions are diffused into the glass, potassium ions are further diffused, which not only improves the bending strength but also enhances the diffusion of silver ions into the glass. It has also been found that the antibacterial property of silver is not impaired by the diffusion of ions, nor is it impaired. The present invention has been achieved based on such findings, and the above-described problem is caused by the fact that Na + in the glass surface layer is replaced by M + (M is an alkali metal atom having an ionic radius larger than that of Na), The problem is solved by glass characterized in that an antibacterial substance is provided on a glass surface layer.
【００１３】又、ガラス表面層のＮａ+ がＭ+ （ＭはＮ
ａよりイオン半径が大きなアルカリ金属原子）で置換さ
れると共に、ガラス表面層に抗菌性物質が侵入・拡散し
てなることを特徴とするガラスによって解決される。
又、Ｍ+ （ＭはＮａよりイオン半径が大きなアルカリ金
属原子）を提供できる化合物と抗菌性物質とを含む溶融
塩で処理されてなることを特徴とするガラスによって解
決される。Further, Na + of the glass surface layer is M + (M is N
This is solved by a glass characterized by being replaced by an alkali metal atom having an ionic radius larger than a) and having an antibacterial substance penetrating and diffusing into the glass surface layer.
Further, the problem is solved by a glass characterized by being treated with a molten salt containing a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance.
【００１４】又、Ｍ+ （ＭはＮａよりイオン半径が大き
なアルカリ金属原子）を提供できる化合物と抗菌性物質
とを含むことを特徴とする強化抗菌ガラス用組成物によ
って解決される。又、Ｍ+ （ＭはＮａよりイオン半径が
大きなアルカリ金属原子）を提供できる化合物と抗菌性
物質とを含む溶融塩からなることを特徴とする強化抗菌
ガラス用組成物によって解決される。[0014] The present invention is also achieved by a composition for a strengthened antibacterial glass, which comprises a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance. Further, the present invention is solved by a composition for a strengthened antibacterial glass, comprising a molten salt containing a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance.
【００１５】又、上記の強化抗菌ガラス用組成物でガラ
スを処理することを特徴とする強化抗菌ガラスの製造方
法によって解決される。又、ナトリウムを含むガラスを
１００〜５００℃に加熱する工程と、上記の強化抗菌ガ
ラス用組成物を含む３３０〜５００℃の処理浴で前記ガ
ラスを処理する工程とを具備することを特徴とする強化
抗菌ガラスの製造方法によって解決される。Further, the present invention solves the above problem by a method for producing a strengthened antibacterial glass, which comprises treating the glass with the above composition for a strengthened antibacterial glass. Further, the method includes a step of heating the glass containing sodium to 100 to 500 ° C., and a step of treating the glass in a treatment bath at 330 to 500 ° C. containing the composition for strengthened antibacterial glass. The problem is solved by a method of manufacturing a tempered antibacterial glass.
【００１６】上記本発明におけるガラス表面層のＮａ+
が置換されるＭ+ は、カリウムイオン、ルビジウムイオ
ン、セシウムイオンが挙げられるが、カリウムイオンが
最も好ましい。従って、Ｍ+ を提供できる化合物はカリ
ウム塩が最も好ましく、このような化合物として、例え
ば硝酸カリウム、塩化カリウム、硫酸カリウム、水酸化
カリウム、硫化カリウム等が挙げられる。In the present invention, Na + of the glass surface layer is used .
There is M + is substituted, potassium ions, rubidium ions, cesium ions include potassium ions are most preferred. Therefore, the compound capable of providing M + is most preferably a potassium salt, and examples of such a compound include potassium nitrate, potassium chloride, potassium sulfate, potassium hydroxide, potassium sulfide and the like.
【００１７】本発明においては、ガラス、特にガラス表
面層には抗菌性物質が侵入・拡散している。この抗菌性
物質は、例えば銀、銀化合物、銅、銅化合物、亜鉛、亜
鉛化合物の群の中から選ばれる一種以上のものである。
Ｍ+ を提供できる化合物と抗菌性物質とを含む溶融塩に
おける抗菌性物質は、還元性を有するものが、特に、好
ましい。すなわち、ガラス中に侵入・拡散した抗菌性物
質は、還元されて安定化し、この安定化状態で抗菌性を
呈する物質であるものが好ましい。このようなことか
ら、抗菌性物質は銀塩、銅塩、亜鉛塩の群の中から選ば
れるものが、特に、好ましい。例えば、硝酸銀、塩化
銀、硝酸銅、塩化銅、硫酸銅、硝酸亜鉛、塩化亜鉛、硫
酸亜鉛などが挙げられる。In the present invention, an antibacterial substance has penetrated and diffused into the glass, particularly into the glass surface layer. The antibacterial substance is, for example, at least one selected from the group consisting of silver, silver compounds, copper, copper compounds, zinc, and zinc compounds.
As the antibacterial substance in the molten salt containing the compound capable of providing M + and the antibacterial substance, those having a reducing property are particularly preferable. That is, the antibacterial substance that has penetrated and diffused into the glass is preferably a substance that is reduced and stabilized and exhibits antibacterial properties in this stabilized state. For this reason, the antibacterial substance is particularly preferably selected from the group consisting of silver salts, copper salts and zinc salts. Examples include silver nitrate, silver chloride, copper nitrate, copper chloride, copper sulfate, zinc nitrate, zinc chloride, zinc sulfate, and the like.
【００１８】処理に用いる強化抗菌ガラス用組成物中に
おけるＭ+ を提供できる化合物／抗菌性物質の割合（重
量比）は４／１〜１００００／１、特に１００／１〜２
０００／１であるのが好ましい。すなわち、例えば銀塩
の割合が少な過ぎた場合には、強度向上度合いが低く、
又、抗菌性も低く、逆に、銀塩の割合が多すぎた場合に
は、ガラスの透明感が損なわれ、ガラスとしての利用が
狭まるからによる。The ratio (weight ratio) of the compound capable of providing M + to the antibacterial substance in the composition for strengthened antibacterial glass used in the treatment is from 4/1 to 10000/1, particularly 100/1 to 2/1.
It is preferably 000/1. That is, for example, when the proportion of the silver salt is too small, the strength improvement degree is low,
On the other hand, when the antibacterial property is low and the proportion of the silver salt is too large, the transparency of the glass is impaired and the use as the glass is narrowed.
【００１９】ガラスを上記溶融塩で処理する場合、ガラ
スを予め１００〜５００℃（より好ましくは、２００〜
４５０℃）に加熱（予熱）しておくことが好ましい。こ
れは、予め、ガラスを加熱しておくと、次工程でのガラ
ス中へのＭ+ 、例えばカリウムイオンの拡散が効果的な
ものとなるからである。この後、上記溶融塩でガラスが
処理される。この処理時におけ溶融塩の温度は３３０〜
５００℃（より好ましくは、３８０〜４６０℃）が好ま
しい。すなわち、温度が低すぎた場合には、ガラス中へ
の銀イオンやカリウムイオンの拡散が不十分であり、逆
に、高すぎた場合には、ガラスの軟化などによる変形の
恐れがあるからである。処理（浸漬）時間は、１０分以
上、好ましくは３０分以上、更には１時間以上、特に６
時間以上が好ましい。又、４８時間以内が好ましい。更
には、２４時間以内が好ましい。すなわち、浸漬時間が
短すぎると、ガラス中への銀イオンやカリウムイオンの
拡散が不十分であり、逆に、浸漬時間が長すぎると、表
面層だけでなく、内部深くまでカリウムイオンが拡散
し、表面強度の向上が得られ難くなるからである。When the glass is treated with the above-mentioned molten salt, the glass is previously heated to 100 to 500 ° C. (more preferably, 200 to 500 ° C.).
(450 ° C.). This is because if the glass is heated in advance, the diffusion of M + , for example, potassium ions into the glass in the next step becomes effective. Thereafter, the glass is treated with the molten salt. During this treatment, the temperature of the molten salt is 330-
500 ° C (more preferably, 380 to 460 ° C) is preferable. That is, if the temperature is too low, the diffusion of silver ions and potassium ions into the glass is insufficient, and if the temperature is too high, there is a risk of deformation due to softening of the glass and the like. is there. The treatment (immersion) time is 10 minutes or more, preferably 30 minutes or more, further 1 hour or more, especially 6 hours.
The time is preferably longer than an hour. Also, it is preferable that the time is within 48 hours. Further, the time is preferably within 24 hours. That is, if the immersion time is too short, the diffusion of silver ions and potassium ions into the glass is insufficient, and if the immersion time is too long, potassium ions diffuse not only into the surface layer but also deep inside. This is because it is difficult to improve the surface strength.
【００２０】本発明は、特に、ナトリウムを含むガラス
に適用される。特に、ナトリウムを０．７ｗｔ％以上、
特に１ｗｔ％以上であって、２０ｗｔ％以下、特に１０
ｗｔ％以下含むガラスに適用される。例えば、ＪＩＳ
Ｒ３２０１，ＪＩＳ Ｒ ３２０２，ＪＩＳ Ｒ ３５
２２，ＪＩＳ Ｓ ２０４３，ＪＩＳ Ｔ ３２０１ガ
ラス等のガラスに適用される。特に好ましいのは、ＪＩ
Ｓ Ｒ ３２０２のフロートガラスや磨きガラスであ
る。尚、ナトリウムを含まない、或いは０．５ｗｔ％以
下しか含まない場合には、本発明の強化ガラス用組成物
で処理しても、強度向上は認められず、かつ、抗菌性が
得られない。The invention applies in particular to glasses containing sodium. In particular, at least 0.7 wt% of sodium,
In particular, it is not less than 1 wt% and not more than 20 wt%, especially 10 wt%.
Applies to glass containing less than wt%. For example, JIS
R3201, JIS R 3202, JIS R 35
22, JIS S 2043 and JIS T 3201 glass. Particularly preferred is JI
SR 3202 float glass or polished glass. When sodium is not contained or contains only 0.5 wt% or less, no improvement in strength is observed and no antibacterial property is obtained even when treated with the composition for tempered glass of the present invention.
【００２１】[0021]
【発明の実施の形態】本発明のガラスは、ガラス表面層
のＮａ+ がＭ+ （ＭはＮａよりイオン半径が大きなアル
カリ金属原子）で置換されると共に、ガラス表面層に抗
菌性物質が設けられたものである。或いは、ガラス表面
層のＮａ+ がＭ+ （ＭはＮａよりイオン半径が大きなア
ルカリ金属原子）で置換されると共に、ガラス表面層に
抗菌性物質（特に、抗菌性を有する金属のイオン）が侵
入・拡散したものである。又は、Ｍ+ （ＭはＮａよりイ
オン半径が大きなアルカリ金属原子）を提供できる化合
物と抗菌性物質（特に、抗菌性を有する金属の塩）とを
含む溶融塩で処理されたものである。抗菌性物質は、例
えば銀、銀化合物、銅、銅化合物、亜鉛、亜鉛化合物の
群の中から選ばれる一種以上のものである。BEST MODE FOR CARRYING OUT THE INVENTION In the glass of the present invention, Na + in the glass surface layer is replaced by M + (M is an alkali metal atom having a larger ionic radius than Na), and an antibacterial substance is provided on the glass surface layer. It was done. Alternatively, Na + in the glass surface layer is replaced by M + (M is an alkali metal atom having a larger ionic radius than Na), and an antibacterial substance (in particular, an ion of a metal having antibacterial properties) penetrates the glass surface layer.・ It is diffused. Alternatively, it is treated with a molten salt containing a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance (particularly, a salt of a metal having antibacterial properties). The antibacterial substance is, for example, one or more selected from the group consisting of silver, silver compounds, copper, copper compounds, zinc, and zinc compounds.
【００２２】本発明の強化ガラス用組成物は、Ｍ+ （Ｍ
はＮａよりイオン半径が大きなアルカリ金属原子）を提
供できる化合物と抗菌性物質（特に、抗菌性を有する金
属の塩）とを含むものである。特に、Ｍ+ （ＭはＮａよ
りイオン半径が大きなアルカリ金属原子）を提供できる
化合物と抗菌性物質（特に、抗菌性を有する金属の塩）
とを含む溶融塩からなる。Ｍ+ を提供できる化合物／抗
菌性物質との割合（重量比）は、４／１〜１００００／
１、特に１００／１〜２０００／１である。強化ガラス
用組成物における抗菌性物質は、ガラス中に侵入・拡散
した抗菌性物質が、還元されて安定化し、この安定化状
態で抗菌性を呈する物質である。例えば、硝酸銀、塩化
銀などの銀塩、硝酸銅、塩化銅、硫酸銅などの銅塩、硝
酸亜鉛、塩化亜鉛、硫酸亜鉛などの亜鉛塩のような金属
塩である。Ｍ+ を提供できる化合物としては、硝酸カリ
ウム、塩化カリウム、硫酸カリウム、水酸化カリウム等
である。本発明の強化ガラス用組成物が銀塩とカリウム
塩とからなる場合、その割合は、Ａｇ／Ｋが０．０００
１以上、特に０．０００５以上であり、０．２５以下、
特に０．０１以下であるのが好ましい。一番好ましいの
は、Ａｇ／Ｋが０．０００５〜０．０１の割合の銀塩と
カリウム塩との溶融塩である。The composition for a tempered glass according to the present invention comprises M + (M
Contains a compound capable of providing an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance (particularly, a salt of a metal having antibacterial properties). In particular, compounds capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and antibacterial substances (especially salts of antibacterial metals)
And a molten salt containing: The ratio (weight ratio) of the compound capable of providing M + to the antibacterial substance is 4/1 to 10,000 /
1, especially 100/1 to 2000/1. The antibacterial substance in the composition for tempered glass is a substance in which the antibacterial substance that has entered and diffused into the glass is reduced and stabilized, and exhibits antibacterial properties in this stabilized state. Examples thereof include silver salts such as silver nitrate and silver chloride, copper salts such as copper nitrate, copper chloride and copper sulfate, and metal salts such as zinc salts such as zinc nitrate, zinc chloride and zinc sulfate. Compounds that can provide M + include potassium nitrate, potassium chloride, potassium sulfate, potassium hydroxide and the like. When the tempered glass composition of the present invention comprises a silver salt and a potassium salt, the ratio is such that Ag / K is 0.000.
1 or more, especially 0.0005 or more, 0.25 or less,
In particular, it is preferably 0.01 or less. Most preferred is a molten salt of a silver salt and a potassium salt having an Ag / K ratio of 0.0005 to 0.01.
【００２３】本発明のガラスの製造方法は、上記の強化
抗菌ガラス用組成物でガラスを処理する方法である。特
に、ナトリウムを含むガラスを１００〜５００℃（特
に、２００〜４５０℃）に加熱する工程と、上記の強化
抗菌ガラス用組成物を含む３３０〜５００℃（特に、３
８０〜４６０℃）の処理浴で前記ガラスを処理する工程
とを有する方法である。The method for producing glass of the present invention is a method of treating glass with the above composition for strengthened antibacterial glass. In particular, a step of heating the glass containing sodium to 100 to 500 ° C (particularly 200 to 450 ° C), and a step of heating the glass containing sodium to 330 to 500 ° C (particularly 3
(80 to 460 ° C.) in a treatment bath.
【００２４】以下、更に詳しく説明する。例えば、ナト
リウムを１ｗｔ％以上含むＪＩＳ Ｒ ３２０２ガラス
を１００〜５００℃に加熱する。この後、Ａｇ／Ｋ＝
０．０００１〜０．２５の範囲内にある硝酸銀−硝酸カ
リウムの３３０〜５００℃の溶融塩中に、前記予熱され
たガラスを１〜４８時間浸漬する。The details will be described below. For example, JIS R 3202 glass containing 1 wt% or more of sodium is heated to 100 to 500 ° C. Thereafter, Ag / K =
The preheated glass is immersed in a molten salt of silver nitrate-potassium nitrate in the range of 0.0001 to 0.25 at 330 to 500 ° C for 1 to 48 hours.
【００２５】これにより、ガラス表面層のＮａ+ がＫ+
で置換され、表面における圧縮応力が増して曲げ強度が
一層向上する。かつ、拡散したＡｇ+ が還元されてＡｇ
としてガラス表面層に存在しており、抗菌性を持ってい
る。そして、本発明になるガラスは、強度に優れ、か
つ、抗菌性に優れていることから、例えば薬品容器など
の医療用途におけるガラス製品、例えば飲料用ガラス
瓶、ガラスコップなどの食品や飲料用途におけるガラス
製品、食器棚の仕切り板や食品用ショーケース等のガラ
ス製品、その他にも手や口にする可能性が有る玩具など
に好適である。As a result, Na + of the glass surface layer becomes K +
And the compressive stress on the surface is increased to further improve the bending strength. In addition, the diffused Ag + is reduced to Ag
As it exists in the glass surface layer and has antibacterial properties. The glass according to the present invention is excellent in strength and excellent in antibacterial properties.For example, glass products in medical applications such as medicine containers, for example, glass bottles for beverages, glass in food and beverage applications such as glass cups, and the like. It is suitable for products, glass products such as cupboard partition boards and food showcases, and other toys that may be used in hands and mouth.
【００２６】以下、具体的実施例を挙げて本発明を説明
するが、本発明はこれに限定されるものではない。Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited to these examples.
【００２７】[0027]
【実施例１】ＳｉＯ2 を７３．０ｗｔ％、Ｎａ2 Ｏを１
６．０ｗｔ％、Ａｌ2 Ｏ3 を２．０ｗｔ％、ＭｇＯを
３．５ｗｔ％、ＣａＯを５．５ｗｔ％含む板厚が１ｍｍ
で７０ｍｍ×１５０ｍｍの大きさのソーダ石灰ガラスＡ
を用意した。このガラスＡを４００℃に予熱した。EXAMPLE 1 73.0 wt% of SiO 2 and 1 of Na 2 O
6.0wt%, Al 2 O 3 and 2.0 wt%, MgO and 3.5 wt%, thickness containing 5.5 wt% of CaO is 1mm
Soda-lime glass A with a size of 70 mm x 150 mm
Was prepared. This glass A was preheated to 400 ° C.
【００２８】この予熱されたガラスＡを、Ａｇ／Ｋ＝
０．０５の硝酸銀−硝酸カリウムの５００℃の溶融塩中
に２４時間浸漬した。この後、ガラスＡを引き上げ、６
０℃まで徐々に冷却し、そして脱イオン水によって充分
に水洗し、室温で乾燥した。The preheated glass A was converted to Ag / K =
It was immersed in a molten salt of 0.05 ° C silver nitrate-potassium nitrate at 500 ° C for 24 hours. Thereafter, the glass A is pulled up, and 6
Cooled slowly to 0 ° C. and washed thoroughly with deionized water and dried at room temperature.
【００２９】[0029]
【実施例２】実施例１において、Ａｇ／Ｋ＝０．００７
の硝酸銀−硝酸カリウムを用い、この溶融塩の処理浴温
度を４６０℃、浸漬時間を０．５時間とした以外は同様
に行った。Example 2 In Example 1, Ag / K = 0.007
Of silver nitrate-potassium nitrate, and the treatment temperature of the molten salt was 460 ° C., and the immersion time was 0.5 hour.
【００３０】[0030]
【実施例３】実施例１において、Ａｇ／Ｋ＝０．００７
の硝酸銀−硝酸カリウムを用い、この溶融塩の処理浴温
度を４６０℃、浸漬時間を４８時間とした以外は同様に
行った。Embodiment 3 In Embodiment 1, Ag / K = 0.007
Of silver nitrate-potassium nitrate was used, except that the treatment bath temperature of the molten salt was 460 ° C. and the immersion time was 48 hours.
【００３１】[0031]
【実施例４】実施例１において、Ａｇ／Ｋ＝０．００１
の硝酸銀−硝酸カリウムを用い、この溶融塩の処理浴温
度を４６０℃、浸漬時間を１時間とした以外は同様に行
った。Embodiment 4 In Embodiment 1, Ag / K = 0.001
Of silver nitrate-potassium nitrate was used, except that the treatment bath temperature of the molten salt was 460 ° C. and the immersion time was 1 hour.
【００３２】[0032]
【実施例５】実施例１において、Ａｇ／Ｋ＝０．００１
の塩化銀−硝酸カリウムを用い、この溶融塩の処理浴温
度を４６０℃、浸漬時間を２４時間とした以外は同様に
行った。Embodiment 5 In Embodiment 1, Ag / K = 0.001
Was performed in the same manner as above except that the bath temperature of the molten salt was 460 ° C. and the immersion time was 24 hours.
【００３３】[0033]
【実施例６】実施例１において、Ａｇ／Ｋ＝０．００１
の塩化銀−硝酸カリウムを用い、この溶融塩の処理浴温
度を３３０℃、浸漬時間を２４時間とした以外は同様に
行った。Embodiment 6 In Embodiment 1, Ag / K = 0.001
Of silver chloride-potassium nitrate, and the treatment bath temperature of the molten salt was 330 ° C., and the immersion time was 24 hours.
【００３４】[0034]
【実施例７】実施例１において、Ａｇ／Ｋ＝０．００１
の塩化銀−硝酸カリウムを用い、この溶融塩の処理浴温
度を４６０℃、浸漬時間を１６時間とした以外は同様に
行った。Embodiment 7 In Embodiment 1, Ag / K = 0.001
Was performed in the same manner except that the bath temperature of the molten salt was 460 ° C. and the immersion time was 16 hours.
【００３５】[0035]
【実施例８】実施例１において、Ａｇ／Ｋ＝０．２の硝
酸銀−硝酸カリウムを用い、この溶融塩の処理浴温度を
４６０℃、浸漬時間を２４時間とした以外は同様に行っ
た。Example 8 The procedure of Example 1 was repeated, except that Ag / K = 0.2 silver nitrate-potassium nitrate was used, the treatment bath temperature of the molten salt was 460 ° C., and the immersion time was 24 hours.
【００３６】[0036]
【実施例９】実施例１において、Ａｇ／Ｋ＝０．０００
２の硝酸銀−硝酸カリウムを用い、この溶融塩の処理浴
温度を４６０℃、浸漬時間を２４時間とした以外は同様
に行った。Embodiment 9 In Embodiment 1, Ag / K = 0.000
The same operation was performed except that silver nitrate-potassium nitrate No. 2 was used, the treatment bath temperature of the molten salt was 460 ° C., and the immersion time was 24 hours.
【００３７】[0037]
【比較例１】実施例１において、硝酸銀−硝酸カリウム
の代わりに硝酸カリウム（硝酸銀を含まない）を用い、
この溶融塩の処理浴温度を４６０℃、浸漬時間を２４時
間とした以外は同様に行った。Comparative Example 1 In Example 1, potassium nitrate (containing no silver nitrate) was used instead of silver nitrate-potassium nitrate.
The procedure was the same except that the bath temperature of the molten salt was 460 ° C. and the immersion time was 24 hours.
【００３８】[0038]
【比較例２】実施例１において、硝酸銀−硝酸カリウム
の代わりに硝酸銀（硝酸カリウムを含まない）を用い、
この溶融塩の処理浴温度を４６０℃、浸漬時間を２４時
間とした以外は同様に行った。Comparative Example 2 In Example 1, silver nitrate (containing no potassium nitrate) was used instead of silver nitrate-potassium nitrate.
The procedure was the same except that the bath temperature of the molten salt was 460 ° C. and the immersion time was 24 hours.
【００３９】[0039]
【特性】上記各例で得たガラスについて、その抗菌性、
曲げ強度、及び透明性を調べたので、その結果を表−１
に示す。 表−１ 抗菌性（滅菌率） 曲げ強度（ｋｇｆ／ｍｍ2 ） 透明性 実施例１ ９９．９％以上 ３５ ◎ 実施例２ ９９．９％以上 ２５ ◎ 実施例３ ９９．９％以上 ３８ ◎ 実施例４ ９９．９％以上 ３１ ◎ 実施例５ ９９．９％以上 ４４ ◎ 実施例６ ９９．９％以上 ３６ ◎ 実施例７ ９９．９％以上 ４１ ◎ 実施例８ ９９．９％以上 ２７ ○ 実施例９ ９２％ ３０ ◎ 比較例１ ０％ ２４ ◎ 比較例２ ９９．９％以上 １９ × 抗菌性（滅菌率）は、５０ｍｍ×５０ｍｍの検体上に大
腸菌が１０5 個／ｍｌとなるよう調整した後、ポリエチ
レンフィルムを密着させ、３０℃で保存し、そして２４
時間後に菌を洗い出し、検体上の生菌数をＳＣＤＬＰ培
地を使用して混釈平板培地法により測定し、１ｍｌ中の
菌数を算出し、（１０5 個−算出菌数）／１０5 個×１
００の式により求めた。[Properties] The antibacterial properties of the glass obtained in each of the above examples,
The bending strength and the transparency were examined.
Shown in Table 1 Antibacterial property (sterilization rate) Flexural strength (kgf / mm 2 ) Transparency Example 1 99.9% or more 35 ◎ Example 2 99.9% or more 25 ◎ Example 3 99.9% or more 38 ◎ Execution Example 4 99.9% or more 31 ◎ Example 5 99.9% or more 44 ◎ Example 6 99.9% or more 36 ◎ Example 7 99.9% or more 41 ◎ Example 8 99.9% or more 27 ○ Example 9 92% 30 ◎ Comparative Example 10 0% 24 ◎ Comparative Example 2 99.9% or more 19 × Antibacterial property (sterilization rate) was adjusted so that Escherichia coli was 10 5 cells / ml on a 50 mm × 50 mm specimen. Afterwards, a polyethylene film is adhered, stored at 30 ° C., and
After an hour, the bacteria are washed out, and the number of viable bacteria on the specimen is measured by the pour plate method using the SCDLP medium, and the number of bacteria in 1 ml is calculated, and (10 5 cells−calculated number of cells) / 10 5 cells × 1
00 was obtained.
【００４０】曲げ強度は、板厚１ｍｍで７０ｍｍ×１５
ｍｍの大きさのサンプルを用意し、中点荷重を受ける曲
げ強度試験方法により行い、３Ｐ・ａ／ｂ・ｄ2 （Ｐ＝
曲げ荷重、ａ＝破壊断面とこれに近い方の支点までの距
離（ｍｍ）、ｂ＝サンプルの断面幅（ｍｍ）、ｄ＝サン
プルの高さ（ｍｍ））により求めた。透明性は、反射・
透過率計を使用して可視光線透過率を測定し、透過率が
３０％以上を◎で、透過率が５〜２９％を○で、透過率
が４％以下を×で表示した。The bending strength is 70 mm × 15 at a plate thickness of 1 mm.
A sample having a size of 2 mm is prepared and subjected to a bending strength test method under a midpoint load, and 3P · a / b · d 2 (P =
Bending load, a = distance between fractured section and fulcrum closer thereto (mm), b = cross section width of sample (mm), d = height of sample (mm)). Transparency is reflective
The visible light transmittance was measured using a transmittance meter, and the transmittance was indicated by ◎ when the transmittance was 30% or more, by ○ when the transmittance was 5 to 29%, and by X when the transmittance was 4% or less.
【００４１】これによれば、本発明になるものは、抗菌
性、曲げ強度、透明性に優れていることが判る。すなわ
ち、カリウム塩のみの溶融塩で処理した比較例１の場合
には、抗菌性が全くなく、かつ、曲げ強度も２４ｋｇｆ
／ｍｍ2 程度であり、又、銀塩のみの溶融塩で処理した
比較例２の場合には、抗菌性が有るものの、曲げ強度が
１９ｋｇｆ／ｍｍ2 程度であり、かつ、透明性も悪いの
に対して、本発明のものは、抗菌性を有すると共に、曲
げ強度にも優れ、更には透明性にも優れている。According to this, it can be seen that the composition according to the present invention is excellent in antibacterial properties, bending strength and transparency. That is, in the case of Comparative Example 1 which was treated with a molten salt containing only a potassium salt, there was no antibacterial property and the bending strength was 24 kgf.
/ Mm 2 , and in the case of Comparative Example 2 treated with a molten salt of only a silver salt, it has antibacterial properties, but has a bending strength of about 19 kgf / mm 2 and poor transparency. On the other hand, the thing of the present invention has not only antibacterial property but also excellent bending strength and further excellent transparency.
【００４２】特に、Ａｇ／Ｋが０．０００５〜０．０１
の割合の銀塩−カリウム塩の溶融塩で処理した場合、抗
菌性は銀塩のみの溶融塩で処理した場合と同等の特長を
奏し、又、曲げ強度はカリウム塩のみの溶融塩で処理し
た場合よりも優れた特長を奏している。Particularly, Ag / K is 0.0005 to 0.01.
When treated with a molten salt of a silver salt-potassium salt in the proportion of, the antibacterial properties exhibited the same characteristics as when treated with a molten salt of only a silver salt, and the bending strength was treated with a molten salt of only a potassium salt. It has better features than the case.
【００４３】[0043]
【発明の効果】本発明によれば、強度に優れ、かつ、抗
菌性に富み、更には透明性に優れたガラスが得られる。According to the present invention, it is possible to obtain a glass having excellent strength, high antibacterial properties and excellent transparency.
Claims (10)
よりイオン半径が大きなアルカリ金属原子）で置換され
ると共に、ガラス表面層に抗菌性物質が設けられてなる
ことを特徴とするガラス。1. The method according to claim 1, wherein Na + of the glass surface layer is M + (M is Na
A glass characterized by being replaced by an alkali metal atom having a larger ionic radius) and having an antibacterial substance provided on a glass surface layer.
よりイオン半径が大きなアルカリ金属原子）で置換され
ると共に、ガラス表面層に抗菌性物質が侵入・拡散して
なることを特徴とするガラス。2. The method according to claim 1, wherein Na + of the glass surface layer is M + (M is Na
A glass characterized by being replaced by an alkali metal atom having a larger ionic radius) and having an antibacterial substance penetrating and diffusing into the glass surface layer.
アルカリ金属原子）を提供できる化合物と抗菌性物質と
を含む溶融塩で処理されてなることを特徴とするガラ
ス。3. A glass which is treated with a molten salt containing a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance.
物、亜鉛、亜鉛化合物の群の中から選ばれる一種以上の
ものである請求項１〜請求項３いずれかのガラス。4. The glass according to claim 1, wherein the antibacterial substance is at least one selected from the group consisting of silver, silver compounds, copper, copper compounds, zinc, and zinc compounds.
アルカリ金属原子）を提供できる化合物と抗菌性物質と
を含むことを特徴とする強化抗菌ガラス用組成物。5. A composition for strengthened antibacterial glass, comprising a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance.
アルカリ金属原子）を提供できる化合物と抗菌性物質と
を含む溶融塩からなることを特徴とする強化抗菌ガラス
用組成物。6. A composition for a strengthened antibacterial glass, comprising a molten salt containing a compound capable of providing M + (M is an alkali metal atom having a larger ionic radius than Na) and an antibacterial substance.
４／１〜１００００／１（重量比）の割合でＭ+ を提供
できる化合物と抗菌性物質とを含む請求項５又は請求項
６の強化抗菌ガラス用組成物。7. A compound capable of providing M + / an antibacterial substance =
The composition for a strengthened antibacterial glass according to claim 5 or 6, comprising a compound capable of providing M + at a ratio of 4/1 to 10,000 / 1 (weight ratio) and an antibacterial substance.
物、亜鉛、亜鉛化合物の群の中から選ばれる一種以上の
ものである請求項５〜請求項７いずれかの強化抗菌ガラ
ス用組成物。8. The tempered antibacterial glass according to claim 5, wherein the antibacterial substance is at least one selected from the group consisting of silver, silver compounds, copper, copper compounds, zinc, and zinc compounds. Composition.
ガラス用組成物でガラスを処理することを特徴とする強
化抗菌ガラスの製造方法。9. A method for producing a strengthened antibacterial glass, comprising treating the glass with the composition for a strengthened antibacterial glass according to any one of claims 5 to 8.
００℃に加熱する工程と、請求項５〜請求項８いずれか
の強化抗菌ガラス用組成物を含む３３０〜５００℃の処
理浴で前記ガラスを処理する工程とを具備することを特
徴とする強化抗菌ガラスの製造方法。10. A glass containing sodium, which is 100 to 5%.
9. Tempering comprising a step of heating to 00C and a step of treating the glass in a treatment bath at 330 to 500C containing the composition for strengthened antibacterial glass according to any one of claims 5 to 8. Manufacturing method of antibacterial glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2681898A JPH11228186A (en) | 1998-02-09 | 1998-02-09 | Glass, production of glass and composition for tempered anti-bacterial gass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2681898A JPH11228186A (en) | 1998-02-09 | 1998-02-09 | Glass, production of glass and composition for tempered anti-bacterial gass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11228186A true JPH11228186A (en) | 1999-08-24 |
Family
ID=12203868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2681898A Pending JPH11228186A (en) | 1998-02-09 | 1998-02-09 | Glass, production of glass and composition for tempered anti-bacterial gass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11228186A (en) |
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