JPH06219771A - Composition for antibacterial glass - Google Patents

Abstract

PURPOSE:To provide a composition capable of giving glass low in the deposition of colloidal or metallic Ag and containing Ag<+> ions with powerful antibacterial activity, and also capable of giving glass suitable for being made into fibers without affecting platinum equipment and useful for fibers containing antibacterial Ag<+> ions. CONSTITUTION:The objective composition having the following composition: (A) 25-60wt.% or SiO2, (B) 18-60wt.% or B2O3, (C) 0-20wt.% of Al2O3, (D) 8-30wt.% of R2O (R is Li, Na or K), (E) 0-20wt.% of R'O (R' is Ca, Mg, Zn or Ba), (F) 0.05-2.0 of Ag2O, (G) 0.01-0.1wt.% of SO3, and (H) 0-0.1wt.% of iron oxide(s) (in terms of Fe2O3).

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は抗菌性ガラス用組成物、
特に塊状、粉末状、または繊維状でそのまま水処理剤な
どとして、あるいは粉末または繊維状のものを樹脂など
と混合使用するに適した抗菌、抗カビ性に優れたガラス
用組成物およびガラス繊維用組成物に関する。The present invention relates to an antibacterial composition for glass,
Particularly, a composition for glass and a glass fiber having excellent antibacterial and antifungal properties suitable for use as a water treatment agent as it is in a lump, powder, or fiber form, or by mixing the powder or fiber form with a resin or the like. It relates to a composition.

【０００２】[0002]

【従来の技術】一価の銀イオン（Ａｇ⁺）および銅イオ
ン（Ｃｕ⁺）が微生物などの下等生物に対して毒性を示
すことは良く知られている。本明細書で微生物とは、狭
義の微生物である細菌、菌類、ウイルスおよび、広義の
微生物である原生動物、藻類などを含めて定義する。ま
た前記の微生物などに対して毒性作用（抗菌作用を含
む。）を示すことを、単に抗菌性があるということにす
る。BACKGROUND OF THE INVENTION It is well known that monovalent silver ions (Ag ⁺ ) and copper ions (Cu ⁺ ) are toxic to lower organisms such as microorganisms. In the present specification, the microorganism is defined to include bacteria, fungi, and viruses that are microorganisms in a narrow sense, and protozoa and algae that are microorganisms in a broad sense. In addition, having a toxic effect (including an antibacterial effect) on the aforementioned microorganisms and the like is simply referred to as having antibacterial properties.

【０００３】Ａｇ⁺イオンを溶解性ガラスに含有させて
抗菌性を付与する方法が数多く提案されている。このよ
うな溶解性ガラスとしては、ＳｉＯ2とＢ2Ｏ3を主成分
とするほう珪酸塩系ガラス、およびＰ2Ｏ5を主成分とす
るりん酸塩系ガラスが知られている。例えばほう珪酸塩
系の溶解性ガラスにＡｇ⁺イオンを含有させた抗菌性の
ある水処理剤（特公平４−５０８７８）、Ａｇ⁺イオン
を溶出しうる化合物を配合した溶解性ガラスの粒子を分
散した層を有するフィルム（特開平２−２５８２５
６）、Ａｇ⁺イオンを溶出させる溶解性ガラスを粉末、
ビーズ、あるいは繊維状にして石膏や珪酸カルシウムの
中に混合すること（特開平２ー３０２３５４、特開平２
−３０２３５５）が知られている。Many methods have been proposed for incorporating anti-bacterial properties by incorporating Ag ⁺ ions into a soluble glass. As such a soluble glass, borosilicate glass containing SiO2 and B2O3 as main components and phosphate glass containing P2O5 as main components are known. For example, disperse particles of soluble glass in which a borosilicate-based soluble glass contains Ag ⁺ ions and has an antibacterial water treatment agent (Japanese Patent Publication No. 4-50878) and a compound capable of eluting Ag ⁺ ions. A film having a layer (JP-A-2-25825)
6), powdered soluble glass that elutes Ag ⁺ ions,
Mixing in beads or fibrous form in gypsum or calcium silicate (JP-A-2-302354, JP-A-2-3023)
-302355) is known.

【０００４】[0004]

【発明が解決しようとする課題】上記のＡｇ⁺イオン含
有ほう珪酸塩系ガラスにおいては、コロイド状Ａｇや金
属Ａｇの析出が認められる。すなわち特公平４ー５０８
７８ではＢ2Ｏ3を２０〜７０モル％含有するほう珪酸塩
系の溶解性ガラスが開示され、特開平２ー３０２３５５
では、実施例で２０モル％のＢ2Ｏ3、５０モル％のＳｉ
Ｏ2、３０モル％のＮａ2Ｏをあげているが、これらの組
成物はいずれも金属Ａｇが析出しやすく、以下に述べる
欠点を有する。In the above-mentioned borosilicate glass containing Ag ⁺ ions, precipitation of colloidal Ag and metallic Ag is recognized. That is, Japanese Patent Publication 4-508
No. 78 discloses a borosilicate-based soluble glass containing 20 to 70 mol% of B2 O3, and disclosed in JP-A-2-302355.
In the examples, 20 mol% B2O3 and 50 mol% Si
Although O2 and Na2O of 30 mol% are listed, all of these compositions have the drawbacks described below because metal Ag easily precipitates.

【０００５】抗菌作用があるのはガラス中のＡｇ⁺イオ
ンで、ガラス中にコロイド状や金属状態で存在するＡｇ
は抗菌作用はあまり期待できない。そのため銀の大部分
をＡｇ⁺イオンの状態にすれば少量の銀で抗菌作用を発
揮することになり、高価な銀の使用料を少なくすること
ができる。更にコロイド状のＡｇは黄色い着色となり、
金属Ａｇもガラスが繊維状になったり、粉砕されると褐
色に着色しやすくなる。黄色や褐色に変色したガラス粉
末やガラス繊維はその商品価値を減ずることになる。ガ
ラス中にＡｇ⁺イオンを安定に含有させる方法として、
酸化性雰囲気での溶融（特開平１−３１７１３３）が提
案されている。しかしながら、この方法ではコロイド状
あるいは金属Ａｇの析出抑制が十分ではなく、また溶解
に掛かる費用が増加して経済的ではない。It is Ag ⁺ ions in glass that have an antibacterial action, and Ag that exists in the glass in a colloidal or metallic state
Can not expect much antibacterial action. Therefore, if most of the silver is made into the state of Ag ⁺ ions, a small amount of silver exhibits an antibacterial action, and the expensive silver usage fee can be reduced. Furthermore, colloidal Ag turns yellow,
Metal Ag also tends to be colored brown when the glass becomes fibrous or crushed. Glass powder and glass fibers that have turned yellow or brown will reduce their commercial value. As a method of stably containing Ag ⁺ ions in the glass,
Melting in an oxidizing atmosphere (JP-A-1-317133) has been proposed. However, this method is not economical because the precipitation of colloidal or metallic Ag is not sufficiently suppressed and the cost for dissolution increases.

【０００６】また、特開平２ー３０２３５５では同じく
繊維状の溶解性ガラスを提案し、実施例で２２．３重量
％のＢ2Ｏ3、４８．０重量％のＳｉＯ2、２９．７重量
％のＮａ2Ｏをあげている。この場合も、粘性が低すぎ
て効率よく繊維を製造するには不適であり、また金属Ａ
ｇの析出を完全には防止できず、以下に述べる欠点を有
する。Further, in Japanese Patent Laid-Open No. 302302/1990, a fibrous soluble glass is also proposed, and in the examples, 22.3% by weight of B2O3, 48.0% by weight of SiO2 and 29.7% by weight of Na2O are mentioned. ing. In this case, too, the viscosity is too low to be suitable for efficient fiber production, and the metal A
The precipitation of g cannot be completely prevented and has the drawbacks described below.

【０００７】ガラス繊維の製造工程では白金類が繊維化
装置の壁、電気加熱体などの設備に多用されている。銀
がＡｇ⁺イオンとして存在すればよいがコロイド状や金
属Ａｇになると白金類と低融点の合金を作って、白金設
備のトラブルに成り易い。ガラス原料からガラス繊維ま
で連続生産せず、一度ガラスとした後、再溶融してガラ
ス繊維を生産する場合には、上記連続生産に比べて更に
コロイド状あるいは金属Ａｇが析出し易い。ガラスを塊
や粉末で使用する場合はコロイド状あるいは金属Ａｇに
ついてそれほど考慮する必要はないが、繊維化について
はコロイド状または金属状Ａｇの析出の防止に細心の注
意が必要である。また上述のように銀の大部分をＡｇ⁺
イオンの状態にすることにより、高価な銀の使用料を少
なくすることができる。更に金属Ａｇは、ガラス短繊維
製造においてはショットと呼ばれる非繊維状の大きな異
物を繊維の製品中に混入させる原因になり、ガラス長繊
維製造にあっては繊維切断の原因になっていずれも生産
性および品質低下を引き起こす。[0007] In the glass fiber manufacturing process, platinums are frequently used for equipment such as walls of fiberizing devices and electric heating elements. It suffices if silver exists as Ag ⁺ ions, but if it becomes colloidal or metallic Ag, it forms an alloy with a low melting point with platinums, which easily causes troubles in platinum equipment. In the case where the glass raw material and the glass fiber are not continuously produced but once made into glass and then remelted to produce the glass fiber, colloidal or metallic Ag is more likely to be deposited than in the above continuous production. When glass is used in the form of a lump or powder, it is not necessary to consider colloidal or metallic Ag so much, but fibrosis requires careful attention to prevent precipitation of colloidal or metallic Ag. Also, as mentioned above, most of silver is Ag ⁺
The ionic state makes it possible to reduce the amount of expensive silver used. Further, metal Ag causes a large amount of non-fibrous foreign substances called shots to be mixed into the fiber product in the production of short glass fibers, and in the production of long glass fibers, it causes fiber breakage, and both are produced. Cause deterioration of sex and quality.

【０００８】本発明は上記の問題点を解決するためにコ
ロイド状あるいは金属Ａｇの析出が少なくて、原料とし
て用いた銀の大部分を抗菌作用の強いＡｇ⁺イオンとし
て含むガラス組成物を提供するものである。さらに本発
明は、繊維化に適し、白金設備に悪影響を与えることな
くガラスの溶出を適度に制御した抗菌性を示すＡｇ⁺イ
オンを含む繊維用のガラス組成を提供するものである。In order to solve the above problems, the present invention provides a glass composition containing little colloidal or metallic Ag precipitation and containing most of silver used as a raw material as Ag ⁺ ions having a strong antibacterial action. It is a thing. Further, the present invention provides a glass composition for fibers containing Ag ⁺ ions, which is suitable for fiberization and has an antibacterial property in which elution of glass is appropriately controlled without adversely affecting platinum equipment.

【課題を解決するための手段】すなわち、本発明は、重
量％で表示して、 ＳｉＯ2 ２５〜６０ Ｂ2Ｏ3 １８〜６０ Ａｌ2Ｏ3 ０〜２０ Ｒ2Ｏ ８〜３０ （Ｒ＝Ｌｉ、Ｎａ、Ｋ） Ｒ’Ｏ ０〜２０ （Ｒ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ） Ａｇ2Ｏ ０．０５〜２．０ ＳＯ3 ０．０１〜０．１ 鉄酸化物（Ｆｅ2Ｏ3に換算） ０〜０．１ を含有することを特徴とする抗菌性ガラス用組成物であ
る。[Means for Solving the Problems] That is, the present invention, expressed in% by weight, comprises: SiO2 25-60 B2O3 18-60 Al2O3 0-20 R2O 8-30 (R = Li, Na, K) R'O 0-20 (R '= Ca, Mg, Zn, Ba) Ag2O 0.05-2.0 SO3 0.01-0.1 Iron oxide (converted to Fe2O3) 0-0.1 It is a composition for antibacterial glass.

【０００９】また本発明は、重量％で表示して、 ＳｉＯ2 ３５〜６０ Ａｌ2Ｏ3 ０〜２０ ただしＳｉＯ2＋Ａｌ2Ｏ3 ４０〜６５ Ｂ2Ｏ3 １８〜５０ Ｒ2Ｏ ８〜２５ （Ｒ＝Ｌｉ、Ｎａ、Ｋ） Ｒ’Ｏ ０〜２０ （Ｒ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ） ただしＲ2Ｏ＋Ｒ'Ｏ ８〜３５ ＳＯ3 ０．０１〜０．１ 鉄酸化物（Ｆｅ2Ｏ3に換算） ０〜０．０５ Ａｇ2Ｏ ０．０５〜１．５ を含有することを特徴とする抗菌性ガラス繊維用組成物
である。In the present invention, the weight percentage is expressed as: SiO2 35-60 Al2O3 0-20 where SiO2 + Al2O3 40-65 B2O3 18-50 R2O 8-25 (R = Li, Na, K) R'O 0- 20 (R '= Ca, Mg, Zn, Ba) However, R2O + R'O 8 to 35 SO3 0.01 to 0.1 Iron oxide (converted to Fe2O3) 0 to 0.05 Ag2O 0.05 to 1.5 It is an antibacterial composition for glass fibers which is characterized by containing.

【００１０】本発明において、ＳｉＯ2成分はガラスの
骨格をなすものであって、その含有量は２５〜６０重量
％、好ましくは３０〜５５重量％である。２５重量％未
満ではＡｇイオンおよびガラス成分の溶出量が多すぎて
抗菌性ガラス用組成物としての寿命（または耐久性）が
極度に短かくなる。逆に６０重量％を越えると粘性が増
大してガラスの溶融が困難になるとともに、Ａｇイオン
の溶出量が少なすぎて抗菌性が十分でない。繊維化用に
おいてはＳｉＯ2成分の含有量は３５〜６０重量％、好
ましくは４０〜５８重量％である。３５重量％未満では
繊維化が困難となり、６０重量％を越えると上記のよう
に抗菌性が弱くなりガラスの溶融が困難になるるととも
に、ガラス繊維化が困難になる。In the present invention, the SiO2 component forms the skeleton of glass, and its content is 25 to 60% by weight, preferably 30 to 55% by weight. If it is less than 25% by weight, the amount of Ag ions and glass components eluted is too large, and the life (or durability) of the composition for antibacterial glass becomes extremely short. On the other hand, if it exceeds 60% by weight, the viscosity is increased and it becomes difficult to melt the glass, and the elution amount of Ag ions is too small, and the antibacterial property is not sufficient. For fiberizing, the content of the SiO2 component is 35 to 60% by weight, preferably 40 to 58% by weight. If it is less than 35% by weight, it becomes difficult to make it into fibers, and if it exceeds 60% by weight, the antibacterial property becomes weak as described above, and it becomes difficult to melt the glass and it becomes difficult to make it into glass fibers.

【００１１】Ｂ2Ｏ3はガラスの溶出を促進し、Ａｇ⁺イ
オン安定化に寄与するもので、１８〜６０重量％、好ま
しくは２０〜５５重量％である。１８重量％未満ではＡ
ｇ⁺イオンの溶出量が少なすぎて、抗菌性が弱く、か
つ、金属Ａｇが析出しやすい。６０重量％を越えるとガ
ラスの溶出量が多すぎて寿命が極度に短かくなるととも
に、これ以上含有させてもＡｇ⁺イオン安定化にはあま
り効果がない。繊維化用のガラスではＢ2Ｏ3量は１８〜
５０重量％、好ましくは２０〜４０重量％である。Ｂ2
Ｏ3の含有量が５０重量％を越えると粘性が低下し、繊
維化が困難になる。B2O3 promotes the elution of glass and contributes to the stabilization of Ag ⁺ ions, and is 18 to 60% by weight, preferably 20 to 55% by weight. A less than 18% by weight
Since the amount of g ⁺ ions eluted is too small, the antibacterial property is weak and metal Ag is likely to precipitate. If it exceeds 60% by weight, the glass elution amount becomes too large and the life becomes extremely short. Further, if it is contained in a larger amount, it is not so effective in stabilizing Ag ⁺ ions. The amount of B2O3 in glass for fiberization is 18-
It is 50% by weight, preferably 20-40% by weight. B2
If the content of O3 exceeds 50% by weight, the viscosity decreases and it becomes difficult to form fibers.

【００１２】Ａｌ2Ｏ3は必須成分ではないがガラスの溶
出を抑制し、Ａｇ⁺イオン安定化に寄与するもので、０
〜２０重量％、好ましくは１〜１０重量％である。２０
重量％を越えるとガラスの溶出量が少なくて抗菌性が弱
くなり、粘性が増大してガラスも溶融しにくい。繊維化
用ガラスでは、Ａｌ2Ｏ3は０〜２０重量％、好ましくは
２〜１５重量％である。２０重量％を越えると上記の抗
菌性弱化およびガラスの溶融の困難に加えて繊維化も困
難になる。繊維化用ガラスでは、ＳｉＯ2とＡｌ2Ｏ3の
合計量は４０〜６５重量％、好ましくは４２〜６３重量
％である。この合計量が４０重量％未満では耐水性が悪
くなるとともに、粘性が低下して繊維化が困難になり、
６５重量％を越えると抗菌性が弱くなるとともにガラス
の溶融および繊維化が困難になる。Although Al2O3 is not an essential component, it suppresses the elution of glass and contributes to the stabilization of Ag ⁺ ions.
-20% by weight, preferably 1-10% by weight. 20
If it exceeds 5% by weight, the elution amount of the glass is small, the antibacterial property is weakened, the viscosity is increased, and the glass is difficult to melt. In the glass for fiberizing, Al2O3 is 0 to 20% by weight, preferably 2 to 15% by weight. If it exceeds 20% by weight, in addition to the above-mentioned weakening of antibacterial property and the difficulty of melting the glass, fiberization becomes difficult. In the fiberizing glass, the total amount of SiO2 and Al2O3 is 40 to 65% by weight, preferably 42 to 63% by weight. If this total amount is less than 40% by weight, the water resistance will be poor and the viscosity will be low, making it difficult to form fibers.
If it exceeds 65% by weight, the antibacterial property becomes weak and it becomes difficult to melt and fiberize the glass.

【００１３】Ｒ2Ｏ（ここでＲはＬｉ、Ｎａ、Ｋ）はガ
ラスの溶融と溶出を促進するもので、Ｌｉ2Ｏ、Ｎａ2
Ｏ、およびＫ2Ｏの合計の含有量は８〜３０重量％、好
ましくは１０〜２０重量％である。８重量％未満では溶
融促進の効果が少なく、またＡｇ⁺イオンの溶出も抑制
されて抗菌性が少なく、３０重量％以上ではガラスの溶
出量が多すぎて、耐久性に乏しい。繊維化用ガラスでは
Ｒ2Ｏの合計は８〜２５重量％、好ましくは１０〜２０
重量％である。２５重量％を越えると、粘性が低くなっ
て繊維化が困難になる。R2O (where R is Li, Na, K) promotes melting and elution of glass. Li2O, Na2
The total content of O and K2O is 8 to 30% by weight, preferably 10 to 20% by weight. If it is less than 8% by weight, the effect of accelerating the melting is small, and the elution of Ag ⁺ ions is suppressed, so that the antibacterial property is low. In the glass for fiberizing, the total amount of R2O is 8 to 25% by weight, preferably 10 to 20%.
% By weight. If it exceeds 25% by weight, the viscosity becomes low and it becomes difficult to form fibers.

【００１４】Ｒ'Ｏ（ここでＲ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂ
ａ）は必須成分ではないがＲ2Ｏと同じく、ガラスの溶
融と溶出を促進するものであり、ＣａＯ、ＭｇＯ、Ｚｎ
Ｏ、およびＢａＯの合計量は０〜２０重量％、好ましく
は０〜１０重量％である。２０重量％を越えると、Ｒ2
Ｏとの併用でガラスの溶出量が多くなりすぎて耐久性に
乏しくなり、また繊維化用としては失透しやすくなり繊
維化が困難になる。更に繊維化用としては、Ｒ2Ｏ成分
合計とＲ'Ｏ成分合計との和（Ｒ2Ｏ＋Ｒ'Ｏ）は８〜３
５重量％、好ましくは１０〜３０重量％である。８重量
％未満では溶融促進の効果が少なく、耐水性が良くなり
過ぎて抗菌性が弱くなる。３５重量％を越えると、粘性
が低下して繊維化が困難になり、耐水性も低下する。R'O (where R '= Ca, Mg, Zn, B
Although a) is not an essential component, it promotes melting and elution of glass like R2O, and CaO, MgO, Zn
The total amount of O and BaO is 0 to 20% by weight, preferably 0 to 10% by weight. If it exceeds 20% by weight, R2
When it is used in combination with O, the amount of glass eluted becomes too large and the durability becomes poor, and when used for fiberizing, devitrification is likely to occur and fiberizing becomes difficult. Furthermore, for fiberization, the sum of the total R2O component and the total R'O component (R2O + R'O) is 8 to 3
It is 5% by weight, preferably 10 to 30% by weight. If it is less than 8% by weight, the effect of promoting melting is small, the water resistance becomes too good, and the antibacterial property becomes weak. If it exceeds 35% by weight, the viscosity is lowered and it becomes difficult to form fibers and the water resistance is lowered.

【００１５】Ａｇ2Ｏはガラス中でＡｇ⁺イオンとなる抗
菌性に必須の成分で、０．０５〜２．０重量％、好まし
くは０．１〜１．０重量％である。０．０５重量％未満
ではＡｇ⁺イオンの溶出が抑制されて抗菌性に乏しく、
２．０重量％を越えて含有させると抗菌性の少ない金属
Ａｇの析出がかなり多くなり、銀は高価でもあるため
２．０重量％を上限とする。繊維化用としてはＡｇ2Ｏ
は０．０５〜１．５重量％、好ましくは０．１〜１．０
重量％である。１．５重量％を越えて含有させると前述
のコロイド状あるいは金属Ａｇ析出による白金設備への
悪影響を無視できなくなる。Ag2O is an essential component for antibacterial properties which becomes Ag ⁺ ions in glass, and is 0.05 to 2.0% by weight, preferably 0.1 to 1.0% by weight. If it is less than 0.05% by weight, elution of Ag ⁺ ions is suppressed and the antibacterial property is poor,
If the content exceeds 2.0% by weight, the precipitation of metal Ag having low antibacterial properties is considerably increased, and silver is also expensive, so the upper limit is 2.0% by weight. Ag2O for fiberizing
Is 0.05 to 1.5% by weight, preferably 0.1 to 1.0
% By weight. If the content exceeds 1.5% by weight, the above-mentioned adverse effects on platinum equipment due to colloidal or metallic Ag deposition cannot be ignored.

【００１６】Ｆｅ2Ｏ3は０〜０．１重量、好ましくは
０．０５重量％以下である。Ｆｅ2Ｏ3 は原料中の不純
物としてガラス中に含有されるが、多すぎるとコロイド
状あるいは金属Ａｇが析出しやすくなる。金属Ａｇの析
出許容限度から鉄分含有量は０．１重量％を上限とす
る。繊維化用としてはＦｅ2Ｏ3は０．０５重量％以下、
好ましくは０．０１重量％以下である。０．０５重量％
を越えて含有させると前述のコロイド状Ａｇまたは金属
Ａｇの析出による白金設備への悪影響を無視できなくな
る。Fe2O3 is 0 to 0.1% by weight, preferably 0.05% by weight or less. Fe2O3 is contained in the glass as an impurity in the raw material, but if it is too much, colloidal or metallic Ag tends to precipitate. The upper limit of the iron content is 0.1% by weight from the permissible precipitation limit of Ag metal. Fe2O3 is 0.05 wt% or less for fiberization,
It is preferably 0.01% by weight or less. 0.05% by weight
If it is contained in an amount exceeding the above range, the adverse effect on the platinum equipment due to the above-mentioned precipitation of colloidal Ag or metallic Ag cannot be ignored.

【００１７】ＳＯ3は０．０１〜０．１重量％、好まし
くは０．０１〜０．０３重量％である。ＳＯ3は溶融時
または再溶融時の昇温で高温になるまでのガラスを酸化
状態に保持してコロイド状あるいは金属Ａｇの析出を防
止する効果がある。特にガラスを再溶融して繊維化する
場合には効果が著しい。本組成範囲においてはガラス原
料中に一定量の硫酸塩を添加してもガラス中に残留する
ＳＯ3は極く一部にすぎず、その大部分は上記のように
ガラスを高温まで酸化状態に保持しつつ、溶融雰囲気中
に硫黄酸化物として離脱していく。０．０１重量％未満
になるような硫酸塩添加量ではその効果が期待できず、
また残留ＳＯ3を０．１重量％を越えて含有させても効
果は横ばいであり、ＳＯ3を多量、含有させることは、
作業環境や大気汚染対策上の問題があり、０．１重量％
を上限とする。SO3 is 0.01 to 0.1% by weight, preferably 0.01 to 0.03% by weight. SO3 has the effect of holding the glass in an oxidized state until the temperature rises to a high temperature during melting or remelting, and prevents colloidal or metallic Ag precipitation. In particular, the effect is remarkable when the glass is remelted to form fibers. In this composition range, even if a certain amount of sulfate is added to the glass raw material, only a small amount of SO3 remains in the glass, and most of it retains the glass in an oxidized state up to a high temperature as described above. At the same time, they are released as sulfur oxides in the molten atmosphere. The effect cannot be expected if the amount of sulfate added is less than 0.01% by weight.
Further, the effect remains flat even if the residual SO3 is contained in an amount of more than 0.1% by weight.
0.1% by weight due to work environment and air pollution control issues
Is the upper limit.

【００１８】本発明の抗菌性ガラス繊維用組成物は容易
に繊維化できる粘性範囲にあることが必要である。ロー
タリー法、火炎吹き飛ばし法、ロータリーガスジェット
法などの各種短繊維繊維製造法および長繊維製造法に対
応する粘性として１０³ポイズになる粘性がある温度範
囲にあることが好ましい。すなわち、本発明の抗菌性ガ
ラス繊維用組成物は、粘性が１０³ポイズになる温度が
８００℃〜１２５０℃の範囲内にある特性温度を有する
ことが好ましい。より好ましくは８００〜１１５０℃で
ある。８００℃未満では粘性が低すぎて繊維化困難であ
ると同時に繊維化したときに欠点が発生しやすく、１２
５０℃を越えると紡糸温度が高くなりすぎて、生産性が
悪くなるため１２５０℃を上限とする。The composition for antibacterial glass fiber of the present invention needs to be in a viscosity range where it can be easily fiberized. It is preferable that the viscosity is 10 ³ poise as a viscosity corresponding to various short fiber manufacturing methods and long fiber manufacturing methods such as the rotary method, the flame blowing method and the rotary gas jet method. That is, the antibacterial glass fiber composition of the present invention preferably has a characteristic temperature at which the temperature at which the viscosity becomes 10 ³ poise is in the range of 800 ° C to 1250 ° C. More preferably, it is 800-1150 degreeC. If it is less than 800 ° C, the viscosity is too low and it is difficult to fiberize, and at the same time, defects are likely to occur when fiberizing.
If it exceeds 50 ° C, the spinning temperature becomes too high and the productivity deteriorates. Therefore, the upper limit is 1250 ° C.

【００１９】更に本発明による抗菌性ガラス繊維用組成
物において抗菌性を発揮させるにはＡｇ⁺イオンの溶出
が必要である。ただし水溶性が限度以上になって、耐久
性に乏しいのは避けるべきである。ガラスの水溶性測定
法として日本光学硝子工業会規格（ＪＯＧＩＳ）の『光
学ガラスの化学的耐久性の測定方法（粉末法）０６ー１
９７５』がある。この方法で測定したガラスの減量率が
８０．０重量％以下であることが好ましい。８０．０重
量％を越えると抗菌性は十分あるがガラスの溶出速度が
速くて耐久性に劣るため、８０．０重量％を上限とす
る。また本発明による抗菌性ガラス繊維用組成物により
製造される抗菌性ガラス繊維の好ましい繊維直径は０．
３〜５μｍ、更に好ましくは０．５〜２．０μｍであ
る。これらのガラス繊維は綿状、織布状、不織布状等の
形態で使用される。Further, in order to exert antibacterial properties in the antibacterial glass fiber composition according to the present invention, elution of Ag ⁺ ions is necessary. However, it should be avoided that its water solubility exceeds its limit and its durability is poor. As a method for measuring the water solubility of glass, the method for measuring the chemical durability of optical glass (powder method) 06-1 of the Japan Optical Glass Industry Standard (JOGIS) is used.
975 ”. The weight loss rate of glass measured by this method is preferably 80.0% by weight or less. If it exceeds 80.0% by weight, the antibacterial property is sufficient, but the glass elution rate is high and the durability is poor, so the upper limit is 80.0% by weight. The preferred fiber diameter of the antibacterial glass fiber produced by the composition for antibacterial glass fiber according to the present invention is 0.
It is 3 to 5 μm, more preferably 0.5 to 2.0 μm. These glass fibers are used in the form of cotton, woven fabric, non-woven fabric and the like.

【００２０】[0020]

【作用】前述の通り、本発明の抗菌性ガラス用組成物は
ガラスを構成する各種酸化物の組成を適切な範囲に調整
することにより、コロイドＡｇによる着色や金属Ａｇの
析出を抑制しつつ、Ａｇ⁺イオンによる抗菌作用のある
ガラスを、コスト上、品質上、有利に製造可能としたも
のである。また、本発明の抗菌性ガラス繊維用組成物は
ガラスを構成する各種酸化物の組成、粘性、水溶性を適
切な範囲に調整することにより、Ａｇ⁺イオンによる抗
菌作用のあるガラス繊維を、設備に使用されている白金
類を損傷することなく、水溶性を調節しつつ、コストの
安いガラス繊維を容易に製造可能としたものである。As described above, the composition for antibacterial glass of the present invention adjusts the composition of various oxides constituting the glass in an appropriate range to suppress coloring by colloid Ag and precipitation of metal Ag, The glass having an antibacterial action by Ag ⁺ ions can be advantageously manufactured in terms of cost and quality. Further, the composition for antibacterial glass fiber of the present invention is provided with glass fiber having antibacterial action by Ag ⁺ ion by adjusting the composition, viscosity and water solubility of various oxides constituting glass to an appropriate range. The present invention makes it possible to easily manufacture low-cost glass fibers while controlling the water solubility without damaging the platinums used in.

【００２１】[0021]

【実施例】【Example】

実施例１〜１０、比較例１〜６ 表１および表２に示す目標組成になるように調合したけ
い砂、ほう酸、ほう砂、酸化アルミ、炭酸リチウム、炭
酸ナトリウム、炭酸カリウム、炭酸カルシウム、塩基性
炭酸マグネシウム、亜鉛華、炭酸バリウム、硝酸銀から
なるバッチを調整した。ＳＯ3成分として、上記原料中
に含まれる分で不足する場合には、硫酸ナトリウムを添
加使用した。通常原料中のＦｅ2Ｏ3は約５０ｐｐｍであ
り、Ｆｅ2Ｏ3を多く含ませるガラスの原料には酸化鉄を
添加した。このバッチを、金属Ａｇの析出が多いと予測
される場合はアルミナ坩堝に入れ、それ以外の場合は白
金坩堝に入れて、電気炉の中で１３００〜１５００℃、
２時間加熱して溶融した。溶融したガラスをステンレス
板の上に流し出し、板状に成形後、徐冷した。Examples 1 to 10 and Comparative Examples 1 to 6 Silica sand, boric acid, borax, aluminum oxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, base prepared to have the target compositions shown in Table 1 and Table 2. A batch of acidic magnesium carbonate, zinc white, barium carbonate and silver nitrate was prepared. As the SO3 component, sodium sulphate was added and used when the amount contained in the above raw material was insufficient. Usually, Fe2O3 in the raw material was about 50 ppm, and iron oxide was added to the raw material of the glass containing a large amount of Fe2O3. This batch was put in an alumina crucible if it was predicted that a large amount of metal Ag was precipitated, otherwise put in a platinum crucible and placed in an electric furnace at 1300 to 1500 ° C.
It was melted by heating for 2 hours. The molten glass was poured onto a stainless plate, shaped into a plate, and then gradually cooled.

【００２２】この試料について、金属Ａｇの析出、ガラ
スの着色状態、抗菌性および水溶性を次に示す方法によ
り測定した。With respect to this sample, the deposition of metal Ag, the coloring state of glass, the antibacterial property and the water solubility were measured by the following methods.

【００２３】金属Ａｇの析出状況；上述のようにして溶
融、流し出した板状のガラスにハロゲンランプを照射し
て、長径が１０μｍ以上の金属Ａｇを４０倍の倍率のル
ーペを用いてカウントし、ガラス１００ｇ当たりの個数
で表わし、全く検出されない場合（個数ゼロ）に◎、１
００個以下の場合に○、１００個を越える場合において
はΧで示した。金属Ａｇの大きさ（長径）は大部分が５
０μｍ以下のため、１００個以下の場合には着色は全く
認められず品質に与える影響は小さくて、製品の品種に
よっては無視できる程度である。Precipitation of metal Ag: The plate glass melted and poured out as described above was irradiated with a halogen lamp, and the metal Ag having a major axis of 10 μm or more was counted using a magnifier with a magnification of 40 times. It is expressed as the number per 100 g of glass, and when none is detected (zero number), ◎, 1
When the number is less than 00, it is indicated by ◯, and when it exceeds 100, it is indicated by Χ. Most of the size (major axis) of metal Ag is 5
Since it is 0 μm or less, when 100 or less, coloring is not recognized at all and the influence on the quality is small, and it is negligible depending on the product type.

【００２４】着色；上のサンプルで褐色や黄色いコロイ
ド着色がない場合を○とし、上記着色がある場合をＸと
した。Coloring: The case where there was no brown or yellow colloidal coloring in the above sample was marked with ◯, and the above coloring was marked with X.

【００２５】抗菌性；まず１０５〜２５０μｍの粒度に
粉砕したガラス試料１０ｇを１００ｃｃのビーカーに入
れ、この中に市販のプロセスチーズの塊（約２ｃｍｘ２
ｃｍｘ１ｃｍ）を１個を置いた後、蒸留水６０ｃｃを入
れる。これを約２０℃の室内に放置して、水やチーズの
腐敗とカビの発生状況を肉眼で観察した。３０日間放置
でもチーズの腐敗がなく、カビの発生がない場合につい
て抗菌性強いとし○で示し、カビの発生が認められる場
合を抗菌性弱いとしＸで示した。Antibacterial property: First, 10 g of a glass sample crushed to a particle size of 105 to 250 μm was placed in a 100 cc beaker, in which a block of commercially available processed cheese (about 2 cm × 2) was placed.
cm × 1 cm), put 60 cc of distilled water. This was left to stand in a room at about 20 ° C., and the state of water and cheese rot and the occurrence of mold were observed with the naked eye. When the cheese was not spoiled even after being left for 30 days and no mold was generated, the antibacterial property was judged to be strong, and it is indicated by ◯, and when mold was found, the antibacterial property was judged to be weak and indicated by X.

【００２６】水溶性；日本光学硝子工業会規格（ＪＯＧ
ＩＳ）の『光学ガラスの化学的耐久性の測定方法（粉末
法）０６ー１９７５』により減量率を測定して、これが
８０．０重量％以下であれば○とし、８０重量％を越え
る場合は耐久性に乏しいとしてΧとした。Water solubility: Japan Optical Glass Industry Standard (JOG)
The weight loss rate is measured according to IS) “Method for measuring chemical durability of optical glass (powder method) 06-1975”. If the weight loss rate is 80.0% by weight or less, it is indicated as ◯, and if it exceeds 80% by weight. Χ was used because of poor durability.

【００２７】溶融性；上記板状ガラス試料を再び溶融し
てその粘性が１０の２乗ポイズになる温度を白金球引き
上げ法により測定し、この温度が１５００℃以下の場合
に溶融性が良好であるとして○で示し、１５００℃を越
える場合においては溶融困難としてＸで示した。Meltability: The temperature at which the above-mentioned plate glass sample was melted again and its viscosity became 10 2 poise was measured by a platinum ball pulling method, and when the temperature was 1500 ° C. or less, the meltability was good. It is shown as ◯, and when it exceeds 1500 ° C., it is indicated as X because it is difficult to melt.

【００２８】表１に、実施例のガラス組成、溶融性、金
属Ａｇの析出、ガラスの着色状態、抗菌性および水溶性
を示した。表２に、比較例のガラス組成、溶融性、金属
Ａｇの析出、抗菌性および水溶性を示した。Table 1 shows the glass composition, meltability, deposition of metal Ag, coloring state of glass, antibacterial property and water solubility of Examples. Table 2 shows the glass composition, meltability, precipitation of metal Ag, antibacterial property, and water solubility of Comparative Examples.

【表１】 表１ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 実施例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ １ ２ ３ ４ ５ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 27.8 33.2 33.4 36.5 34.5 Ａｌ2Ｏ3 16.9 1.5 1.2 2.1 3.3 Ｂ2Ｏ3 44.7 37.6 54.1 41.2 34.3 Ｌｉ2Ｏ 0 0 0 0.4 0 Ｎａ2Ｏ 10.5 10.2 10.8 10.2 24.2 Ｋ2Ｏ 0 0 0 1.8 3.5 ＣａＯ 0 13.2 0 4.1 0 ＭｇＯ 0 4.1 0 1.5 0 ＺｎＯ 0 0 0 0.8 0 Ｂａ０ 0 0 0 0.6 0 Ｆｅ2Ｏ3 0.03 0.06 0.10 0.005 0.01 ＳＯ3 0.02 0.05 0.02 0.03 0.02 Ａｇ2Ｏ 0.1 0.05 0.4 0.8 0.2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ◎ ○ ○ ◎ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ガラスの着色 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ○ ○ ○ ○ ○ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝[Table 1] Table 1 ================================== Example ---------- −−−−−−−−−−−−−−−−−−−−−−−− No 1 2 3 4 5 −−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−− Composition wt% SiO2 27.8 33.2 33.4 36.5 34.5 Al2O3 16.9 1.5 1.2 2.1 3.3 B2O3 44.7 37.6 54.1 41.2 34.3 Li2O 0 0 0 0.4 0 Na2O 10.5 10.2 10.8 10.2 24.2 K2O 0 0 0 1.8 3.5 CaO 0 13.2 0 4.1 0 MgO 0 4.1 0 1.5 0 ZnO 0 0 0 0.8 0 Ba0 0 0 0 0.6 0 Fe2O3 0.03 0.06 0.10 0.005 0.01 SO3 0.02 0.05 0.02 0.03 0.02 Ag2O 0.1 0.05 0.4 0.8 0.2 −−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− Metal Ag precipitation ◎ ○ ○ ◎ ◎ −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−− glass Coloring ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Antibacterial property ○ ○ ○ ○ ○ --- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Water solubility ○ ○ ○ ○ ○ −−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−− Meltness ○ ○ ○ ○ ○ ======================= ===========

【表２】 表１（つづき） ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 実施例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ ６ ７ ８ ９ １０ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 40.1 52.1 53.5 56.2 59.3 Ａｌ2Ｏ3 1.8 3.6 0 6.9 0 Ｂ2Ｏ3 44.6 26.9 30.4 18.4 26.9 Ｌｉ2Ｏ 0 0 0 0 0 Ｎａ2Ｏ 11.5 12.3 8.3 10.9 13.2 Ｋ2Ｏ 0 0.8 0 2.7 0 ＣａＯ 0 2.8 5.3 3.2 0 ＭｇＯ 0 1.0 2.1 1.4 0 ＺｎＯ 0 0 0 0 0 Ｂａ０ 0 0 0 0 0 Ｆｅ2Ｏ3 0.005 0.005 0.005 0.005 0.005 ＳＯ3 0.01 0.03 0.03 0.02 0.02 Ａｇ2Ｏ 2.0 0.5 0.4 0.3 0.5 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ○ ◎ ◎ ○ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ガラスの着色 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ○ ○ ○ ○ ○ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝[Table 2] Table 1 (continued) ======================================== Example --- −−−−−−−−−−−−−−−−−−−−−−−−−−− No 6 7 8 9 10 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−− Composition wt% SiO2 40.1 52.1 53.5 56.2 59.3 Al2O3 1.8 3.6 0 6.9 0 B2O3 44.6 26.9 30.4 18.4 26.9 Li2O 0 0 0 0 0 Na2O 11.5 12.3 8.3 10.9 13.2 K2O 0 0.8 0 2.7 0 CaO 0 2.8 5.3 3.2 0 MgO 0 1.0 2.1 1.4 0 ZnO 0 0 0 0 0 Ba0 0 0 0 0 0 Fe2O3 0.005 0.005 0.005 0.005 0.005 SO3 0.01 0.03 0.03 0.02 0.02 Ag2O 2.0 0.5 0.4 0.3 0.5 --- −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Precipitation of metal Ag ○ ◎ ◎ ○ ◎ −−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−− Coloring of glass ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Antibacterial property ○ ○ ○ ○ ○ − − −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Water solubility ○ ○ ○ ○ ○ −−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−− Meltness ○ ○ ○ ○ ○ ======================= ============

【表３】 表２ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 比較例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ １ ２ ３ ４ ５ ６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 21.1 23.7 54.2 57.1 45.9 66.3 Ａｌ2Ｏ3 0 0 0 4.5 8.0 5.1 Ｂ2Ｏ3 63.9 40.7 23.3 14.6 24.9 20.8 Ｌｉ2Ｏ 0 0 0 0 0 0 Ｎａ2Ｏ 14.5 32.8 13.5 18.1 17.8 7.5 Ｋ2Ｏ 0 0 3.1 1.2 0 0 ＣａＯ 0 0 3.7 2.9 3.4 0 ＭｇＯ 0 0 1.2 1.0 0 0 ＺｎＯ 0 0 0 0 0 0 Ｂａ０ 0 0 0 0 0 0 Ｆｅ2Ｏ3 0.01 0.01 0.15 0.03 0.005 0.005 ＳＯ3 0.01 0.01 0 0.01 0.02 0.02 Ａｇ2Ｏ 0.5 2.8 0.8 0.6 0.01 0.3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ー Χ Χ Χ ー ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ー ー ー ー Χ Χ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 Χ Χ ー ー ー ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ー ー ー ー ー Χ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 表１から明かなように、実施例のいずれのガラスも抗菌
作用が優れ、ガラスの着色はなく、金属Ａｇの析出は全
くないか、無視できる程度に少ない。以上のことから表
１にあるガラス組成物から生産性、品質で優れた抗菌性
ガラスの製造が可能であることが分かる。 表２の比較
例１は耐水性に劣り、比較例２、３、４は金属Ａｇの析
出が多く、そのうち比較例２は水溶性が限度を越えてい
る。比較例５はＡｇ⁺イオンが少なくて、比較例６は溶
融性に劣るとともにガラスの溶出が少なすぎて、抗菌性
に劣るガラス組成物である。[Table 3] Table 2 ==================================== Comparative Example -------- −−−−−−−−−−−−−−−−−−−−−−−−−− No 1 2 3 4 5 6 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− Composition wt% SiO2 21.1 23.7 54.2 57.1 45.9 66.3 Al2O3 0 0 0 4.5 8.0 5.1 B2O3 63.9 40.7 23.3 14.6 24.9 20.8 Li2O 0 0 0 0 0 0 Na2O 14.5 32.8 13.5 18.1 17.8 7.5 K2O 0 0 3.1 1.2 0 0 CaO 0 0 3.7 2.9 3.4 0 MgO 0 0 1.2 1.0 0 0 ZnO 0 0 0 0 0 0 Ba0 0 0 0 0 0 0 Fe2O3 0.01 0.01 0.15 0.03 0.005 0.005 SO3 0.01 0.01 0 0.01 0.02 0.02 Ag2O 0.5 2.8 0.8 0.6 0.01 0.3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Metal Ag precipitationー Χ Χ Χ ー −−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−− Antibacterial property ー Χ Χ −−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−− Water-soluble Χ Χ ー ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− − Meltability ―――― ＝ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ As shown in Table 1. In addition, all the glasses of Examples have excellent antibacterial action, there is no coloring of the glass, and there is no or no metal Ag precipitation, which is negligible. From the above, it is understood that it is possible to produce antibacterial glass excellent in productivity and quality from the glass composition shown in Table 1. Comparative Example 1 in Table 2 is inferior in water resistance, Comparative Examples 2, 3 and 4 have a large amount of metal Ag precipitation, and Comparative Example 2 has a water solubility exceeding the limit. Comparative Example 5 is a glass composition having a small amount of Ag ⁺ ions, and Comparative Example 6 having a poor meltability and an excessively small amount of glass elution, and thus a poor antibacterial property.

【００２９】実施例１１〜２５、比較例７〜１５ 上記実施例１〜１０と同様に、表３の実施例および表４
の比較例に示す目標組成になるように、調合、溶融、成
形、徐冷をおこなった板状ガラス試料を、高温粘性およ
びガラスの減量率の各測定用と金属Ａｇの析出検査用サ
ンプルした。抗菌性簡易検査用には上記ガラス試料を再
溶融してガラス短繊維製造法の一つであるいわゆるロー
タリーガスジェット法（例えば特公昭５８−５７３７４
参照）により約１μｍ直径で長さが０．５ｍｍ〜２ｍｍ
のガラス繊維の綿状としたものを使用した。Examples 11 to 25, Comparative Examples 7 to 15 Similar to the above Examples 1 to 10, Examples of Table 3 and Table 4 are shown.
The plate-like glass sample prepared, melted, molded, and gradually cooled so as to have the target composition shown in Comparative Example 1 above was used as a sample for measuring each of high-temperature viscosity and glass weight loss rate and a sample for inspecting metal Ag precipitation. For simple antibacterial inspection, the so-called rotary gas jet method (for example, Japanese Patent Publication No. 58-57374) is one of the methods for producing short glass fibers by remelting the above glass sample.
Refer to) and have a diameter of about 1 μm and a length of 0.5 mm to 2 mm
The glass fiber of cotton was used.

【００３０】上記板状ガラス試料およびガラス繊維試料
について、溶融性、繊維化の良否、金属Ａｇの析出、ガ
ラスの着色状態、抗菌性および耐水性を次に示す方法に
より測定した。なお溶融性は上記と同じ方法である。With respect to the above-mentioned plate glass sample and glass fiber sample, meltability, quality of fiberization, deposition of metal Ag, coloring state of glass, antibacterial property and water resistance were measured by the following methods. The meltability is the same as above.

【００３１】繊維化の良否；上記板状ガラス試料を再び
溶融してその粘性が１０³ポイズになる温度を白金球引
き上げ法により測定し、この温度が８００℃〜１１５０
℃以下の場合に繊維化に非常に好適であるので◎で示
し、１１５０℃を越えて１２５０℃以下の場合には比較
的良好に繊維化できるので○で示し、８００℃未満ある
いは１２５０℃を越える場合においては、繊維化困難で
ありまた欠点が発生しやすいのでΧで示した。Whether the fiberization is good or not; the temperature at which the above-mentioned plate glass sample was melted again and the viscosity became 10 ³ poise was measured by a platinum ball pulling method, and this temperature was 800 ° C to 1150.
When the temperature is lower than ℃, it is very suitable for fiberization, and is indicated by ⊚. In some cases, it is difficult to form fibers and defects are likely to occur.

【００３２】金属Ａｇの析出状況；上述板状のガラスに
ハロゲンランプを照射して、長径が１０μｍ以上の金属
Ａｇを４０倍の倍率のルーペを用いてカウントし、ガラ
ス１００ｇ当たりの個数で表わし、全く検出されない場
合（個数ゼロ）に◎、１０個以下の場合に○、１０個を
越える場合においてはΧで示した。金属Ａｇの大きさ
（長径）は大部分が５０μｍ以下のため、１０個以下の
場合には白金類や品質に与える影響は小さくて、製品の
品種によっては無視できる程度である。Precipitation state of metal Ag: The above-mentioned plate-shaped glass was irradiated with a halogen lamp, metal Ag having a major axis of 10 μm or more was counted using a loupe having a magnification of 40 times, and expressed as the number per 100 g of glass. When not detected at all (zero number), ⊚ when 10 or less, ◯ when more than 10 Since most of the size (major axis) of the metal Ag is 50 μm or less, when it is 10 or less, the influence on platinum and quality is small, and it is negligible depending on the product type.

【００３３】着色；上のサンプルで褐色や黄色いコロイ
ド着色がない場合を○とし、上記着色がある場合をＸと
した。Coloring: The case where there was no brown or yellow colloidal coloring in the above sample was marked with ◯, and the case where there was the above coloring was marked with X.

【００３４】抗菌性；まずガラス繊維試料約５ｇをほぐ
して３００ｃｃのビーカーに入れ、この中に市販のプロ
セスチーズの塊（約２ｃｍｘ２ｃｍｘ１ｃｍ）を１個置
いた後、蒸留水１５０ｃｃを入れる。これを約２０℃の
室内に放置して、水やチーズの腐敗とカビの発生状況を
肉眼で観察した。３０日間放置でもチーズの腐敗がな
く、カビの発生がない場合について抗菌性強いとし○で
示し、カビの発生が認められる場合を抗菌性弱いとしＸ
で示した。Antibacterial property: First, about 5 g of a glass fiber sample is unraveled and placed in a 300 cc beaker, one commercial processed cheese mass (about 2 cm x 2 cm x 1 cm) is placed therein, and then 150 cc of distilled water is put therein. This was left to stand in a room at about 20 ° C., and the state of water and cheese rot and the occurrence of mold were observed with the naked eye. If the cheese does not rot even after being left for 30 days and no mold is generated, the antibacterial property is indicated as ○, and if mold is found, the antibacterial property is indicated as X.
Indicated by.

【００３５】表３の実施例にはガラス組成の他にガラス
の溶融性、繊維化の良否、沸騰水中での溶解によるガラ
スの減量率、金属Ａｇの析出状況、抗菌性を示した。表
４の比較例にはガラス組成と必要な項目の結果のみ示し
た。In addition to the glass composition, the examples in Table 3 show the meltability of the glass, the quality of the fiber formation, the weight loss rate of the glass due to dissolution in boiling water, the deposition state of metal Ag, and the antibacterial property. In the comparative example of Table 4, only the glass composition and the results of necessary items are shown.

【表４】 表３ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 実施例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ １１ １２ １３ １４ １５ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 35.8 40.3 40.1 38.6 39.1 Ａｌ2Ｏ3 5.5 4.2 14.0 2.3 2.7 Ｂ2Ｏ3 38.6 39.1 25.3 48.6 49.4 Ｌｉ2Ｏ 0 0 0 0 0 Ｎａ2Ｏ 10.5 11.3 17.2 10.2 8.2 Ｋ2Ｏ 0 0 0 0 0 ＣａＯ 7.4 3.1 2.2 0 0 ＭｇＯ 2.1 1.9 0.9 0 0 ＺｎＯ 0 0 0 0 0 Ｂａ０ 0 0 0 0 0 Ｆｅ2Ｏ3 0.005 0.005 0.005 0.05 0.03 ＳＯ3 0.02 0.02 0.03 0.02 0.01 Ａｇ2Ｏ 0.05 0.1 0.3 0.3 0.6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 繊維化の良否 ◎ ◎ ◎ ◎ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ◎ ◎ ◎ ○ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ガラスの着色 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ○ ○ ○ ○ ○ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝Table 3 Table 3 ================================== Example ---------- −−−−−−−−−−−−−−−−−−−−−−−− No 11 12 13 14 15 −−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−− Composition wt% SiO2 35.8 40.3 40.1 38.6 39.1 Al2O3 5.5 4.2 14.0 2.3 2.7 B2O3 38.6 39.1 25.3 48.6 49.4 Li2O 0 0 0 0 0 Na2O 10.5 11.3 17.2 10.2 8.2 K2O 0 0 0 0 0 CaO 7.4 3.1 2.2 0 0 MgO 2.1 1.9 0.9 0 0 ZnO 0 0 0 0 0 Ba0 0 0 0 0 0 Fe2O3 0.005 0.005 0.005 0.05 0.03 SO3 0.02 0.02 0.03 0.02 0.01 Ag2O 0.05 0.1 0.3 0.3 0.6 -------- −−−−−−−−−−−−−−−−−−−−−−−−−−− Goodness of fiberization ◎ ◎ ◎ ◎ ◎ ---------- −−−−−−−−−−−−−−−−−−− Water Properties ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Precipitation of metal Ag ◎ ◎ ◎ ○ ◎ −− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Glass coloring ○ ○ ○ ○ ○ −−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−− Antibacterial property ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−− Meltness ○ ○ ○ ○ ○ ================================ ==

【表５】 表３（つづき） ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 実施例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ １６ １７ １８ １９ ２０ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 40.3 42.1 45.5 47.0 51.3 Ａｌ2Ｏ3 2.1 2.5 4.1 19.6 3.4 Ｂ2Ｏ3 46.9 23.6 20.8 22.5 26.0 Ｌｉ2Ｏ 0 0 1.2 0 0 Ｎａ2Ｏ 9.2 10.1 13.7 10.5 19.2 Ｋ2Ｏ 0 2.1 4.8 0 0 ＣａＯ 0 9.8 7.1 0 0 ＭｇＯ 0 4.5 2.7 0 0 ＺｎＯ 0 2.7 0 0 0 Ｂａ０ 0 2.5 0 0 0 Ｆｅ2Ｏ3 0.005 0.005 0.005 0.005 0.005 ＳＯ3 0.01 0.02 0.05 0.02 0.03 Ａｇ2Ｏ 1.5 0.1 0.06 0.4 0.08 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 繊維化の良否 ◎ ◎ ◎ ◎ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ○ ○ ○ ◎ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ガラスの着色 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ○ ○ ○ ○ ○ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝Table 3 (continued) ======================================== Example ----- ------------------------------------ No 16 17 18 19 20 ------------------- −−−−−−−−−−−−−−−− Composition wt% SiO2 40.3 42.1 45.5 47.0 51.3 Al2O3 2.1 2.5 4.1 19.6 3.4 B2O3 46.9 23.6 20.8 22.5 26.0 Li2O 0 0 1.2 0 0 Na2O 9.2 10.1 13.7 10.5 19.2 K2O 0 2.1 4.8 0 0 CaO 0 9.8 7.1 0 0 MgO 0 4.5 2.7 0 0 ZnO 0 2.7 0 0 0 Ba0 0 2.5 0 0 0 Fe2O3 0.005 0.005 0.005 0.005 0.005 SO3 0.01 0.02 0.05 0.02 0.03 Ag2O 1.5 0.1 0.06 0.4 0.08 --- −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Goodness of fiberization ◎ ◎ ◎ ◎ ◎ ◎ -------- −−−−−−−−−−−−−−− −−−−−− Water solubility ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Metal Ag precipitation ○ ○ ○ ◎ ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Glass coloring ○ ○ ○ ○ ○ −−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Antibacterial property ○ ○ ○ ○ ○ −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Meltness ○ ○ ○ ○ ○ ======================== ==========

【表６】 表３（つづき） ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 実施例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ ２１ ２２ ２３ ２４ ２５ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 52.1 53.5 55.4 58.1 59.3 Ａｌ2Ｏ3 3.1 9.1 8.8 2.2 2.1 Ｂ2Ｏ3 21.3 26.3 18.5 22.3 28.3 Ｌｉ2Ｏ 0 0 0 0 1.3 Ｎａ2Ｏ 14.7 10.7 17.1 17.0 8.6 Ｋ2Ｏ 8.6 0 0 0 0 ＣａＯ 0 0 0 0 0 ＭｇＯ 0 0 0 0 0 ＺｎＯ 0 0 0 0 0 Ｂａ０ 0 0 0 0 0 Ｆｅ2Ｏ3 0.005 0.005 0.005 0.005 0.005 ＳＯ3 0.03 0.01 0.02 0.02 0.02 Ａｇ2Ｏ 0.1 0.4 0.06 0.4 0.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 繊維化の良否 ◎ ◎ ◎ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ○ ◎ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ガラスの着色 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ○ ○ ○ ○ ○ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝Table 6 (Continued) ======================================= Example −−−−−−−−−−−−−−−−−−−−−−−−−−− No 21 22 23 24 25 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−− Composition wt% SiO2 52.1 53.5 55.4 58.1 59.3 Al2O3 3.1 9.1 8.8 2.2 2.1 B2O3 21.3 26.3 18.5 22.3 28.3 Li2O 0 0 0 0 1.3 Na2O 14.7 10.7 17.1 17.0 8.6 K2O 8.6 0 0 0 0 CaO 0 0 0 0 0 MgO 0 0 0 0 0 ZnO 0 0 0 0 0 Ba0 0 0 0 0 0 Fe2O3 0.005 0.005 0.005 0.005 0.005 SO3 0.03 0.01 0.02 0.02 0.02 Ag2O 0.1 0.4 0.06 0.4 0.4 --- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Fairness of fiberization −−−−−−−−−−−−−−−−−−−−−− − Water solubility ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Precipitation of metal Ag ○ ◎ ○ ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Coloring of glass ○ ○ ○ ○ ○ −−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−− Antibacterial property ○ ○ ○ ○ ○ −−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−− Meltability ○ ○ ○ ○ ○ ============================== ====

【表７】 表４ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 比較例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ ７ ８ ９ １０ １１ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 23.5 53.7 52.3 50.7 25.5 Ａｌ2Ｏ3 0 9.6 14.0 8.3 0.6 Ｂ2Ｏ3 54.7 25.0 14.6 28.2 35.3 Ｌｉ2Ｏ 0 0 0 0 0 Ｎａ2Ｏ 20.9 11.2 18.6 10.6 38.2 Ｋ2Ｏ 0 0 0 0 0 ＣａＯ 0 0 0 0 0 ＭｇＯ 0 0 0 0 0 ＺｎＯ 0 0 0 0 0 Ｂａ０ 0 0 0 0 0 Ｆｅ2Ｏ3 0.03 0.12 0.005 0.005 0.005 ＳＯ3 (*) 0.007以下 0.02 0.03 0.02 0.02 Ａｇ2Ｏ 0.9 0.4 0.5 2.2 0.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 繊維化の良否 Χ ー ー ー Χ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 Χ Χ Χ Χ ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 Ｘ ー ー ー Ｘ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ー ー ー ー ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ー ー ー ー ー ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ (*)は検出限界以下を示す。[Table 7] Table 4 ==================================== Comparative Example -------- −−−−−−−−−−−−−−−−−−−−−−−−− No 7 8 9 10 11 −−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−− Composition wt% SiO2 23.5 53.7 52.3 50.7 25.5 Al2O3 0 9.6 14.0 8.3 0.6 B2O3 54.7 25.0 14.6 28.2 35.3 Li2O 0 0 0 0 0 Na2O 20.9 11.2 18.6 10.6 38.2 K2O 0 0 0 0 0 CaO 0 0 0 0 0 MgO 0 0 0 0 0 ZnO 0 0 0 0 0 Ba 0 0 0 0 0 0 Fe2O3 0.03 0.12 0.005 0.005 0.005 SO3 (*) 0.007 or less 0.02 0.03 0.02 0.02 Ag2O 0.9 0.4 0.5 2.2 0.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Fairness of fiberization Χ ー ー Χ ---- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Precipitation of Ag metal Χ Χ Χ Χ --------------------------------------------------- Water-soluble X-- X -------------------------------------------- Antibacterial property -------- −−−−−−−−−−−−−−−−−−−−−−−−−−−− Meltability −− ============== ==================== (*) indicates below the detection limit.

【００３６】[0036]

【表８】 表４（つづき） ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 比較例 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Ｎｏ １２ １３ １４ １５ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 組成 wt% ＳｉＯ2 21.1 65.3 50.3 52.3 Ａｌ2Ｏ3 2.3 5.7 21.7 8.7 Ｂ2Ｏ3 28.6 22.1 19.3 29.2 Ｌｉ2Ｏ 0 0 0 0 Ｎａ2Ｏ 19.2 6.6 8.5 9.8 Ｋ2Ｏ 0 0 0 0 ＣａＯ 27.1 0 0 0 ＭｇＯ 1.3 0 0 0 ＺｎＯ 0 0 0 0 Ｂａ０ 0 0 0 0 Ｆｅ2Ｏ3 0.005 0.01 0.005 0.02 ＳＯ3 0.03 0.01 0.03 0.01 Ａｇ2Ｏ 0.4 0.3 0.2 0.02 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 繊維化の良否 Χ Χ Ｘ ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属Ａｇの析出 ー ー ー ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 水溶性 Ｘ ー ー ー −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 抗菌性 ー Χ Χ Χ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 溶融性 ー Χ Χ ー ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 表３から明かなように、実施例のいずれのガラスも抗菌
作用が強く、金属Ａｇの析出は全くないか、無視できる
程度に少なく、着色もなく、容易に溶融および繊維化で
きる粘性を有し、水溶性も適当で耐久性に劣ることはな
い。以上のことから実施例のガラス組成からは生産性、
品質で優れた抗菌性ガラス繊維を製造することができ
る。[Table 8] Table 4 (continued) ================================== Comparative Example -------- −−−−−−−−−−−−−−−−−−−−−−−−− No 12 13 14 15 −−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−− Composition wt% SiO2 21.1 65.3 50.3 52.3 Al2O3 2.3 5.7 21.7 8.7 B2O3 28.6 22.1 19.3 29.2 Li2O 0 0 0 0 Na 2 O 19.2 6.6 8.5 9.8 K 2 O 0 0 0 0 CaO 27.1 0 0 0 MgO 1.30 0 0 ZnO 0 0 0 0 Ba0 0 0 0 0 Fe2O3 0.005 0.01 0.005 0.02 SO3 0.03 0.01 0.03 0.01 Ag2O 0.4 0.3 0.2 0.02 ------------------------ −−−−−−−−−−−− Quality of fiber formation Χ X − −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− --- Precipitation of metal Ag --- ---------------- −−−−−−−−−−−−−−−−−−−− Water-soluble X −−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−− Antibacterial property Χ Χ Χ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Meltness ================================= As is clear from Table 3, any of the glasses of Examples is antibacterial. It has a strong action, has no or no precipitation of metallic Ag, is negligible, has no coloring, has a viscosity capable of being easily melted and made into fibers, and has suitable water solubility and is not inferior in durability. From the above, productivity from the glass composition of the example,
It is possible to produce an antibacterial glass fiber excellent in quality.

【００３７】表４から明かなように比較例のガラス組成
は以下に述べる欠点を持つ。まずＮｏ.７〜１０は金属
Ａｇの析出が多く、うちＮｏ.７は粘性が低くて繊維化
が困難でかつ水溶性も限度を越えて大きすぎる。Ｎｏ.
１１、１２は水溶性が限度以上で、かつ粘性が低すぎて
繊維化しにくい。またＮｏ.１３、１４は溶融困難で繊
維化もしにくく、抗菌性が弱い。最後にＮｏ.１５はＡ
ｇ2Ｏの含有量が少なくて、抗菌性が弱い。As is clear from Table 4, the glass compositions of Comparative Examples have the following drawbacks. First, Nos. 7 to 10 have a large amount of metal Ag precipitates, of which No. 7 has a low viscosity and is difficult to fibrillate, and its water solubility is too large, exceeding its limit. No.
Nos. 11 and 12 have water-solubility higher than the limit, and have too low a viscosity to easily form fibers. In addition, Nos. 13 and 14 are difficult to melt and difficult to fibrillize, and have weak antibacterial properties. Finally, No. 15 is A
Low g2O content and weak antibacterial properties.

【００３８】[0038]

【発明の効果】以上のように本発明の抗菌性ガラス組成
物は、ＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、Ｒ2Ｏ（Ｒ＝Ｌｉ、
Ｎａ、Ｋ）、Ｒ'Ｏ（Ｒ＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ）、
Ａｇ2 Ｏ、ＳＯ3、Ｆｅ2Ｏ3の割合を適切に調節するこ
とによって、コスト的に有利で品質に優れた抗菌性のあ
るガラスの製造を可能にするものである。また本発明の
抗菌性ガラス繊維用組成物は各成分を適切に調節するこ
とによって白金類からなるガラス繊維製造装置を損傷さ
せることなく、また生産性と品質に優れた抗菌作用のあ
るガラス繊維の製造を可能にするものである。As described above, the antibacterial glass composition of the present invention has the following properties: SiO2, B2O3, Al2O3, R2O (R = Li,
Na, K), R'O (R = Ca, Mg, Zn, Ba),
By appropriately adjusting the proportions of Ag2O, SO3, and Fe2O3, it becomes possible to manufacture a glass having antibacterial properties which is cost-effective and excellent in quality. Further, the composition for antibacterial glass fiber of the present invention is a glass fiber having antibacterial action excellent in productivity and quality without damaging a glass fiber manufacturing apparatus comprising platinum by appropriately adjusting each component. It enables manufacturing.

【００３９】[0039]

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 重量％で表示して、 ＳｉＯ2 ２５〜６０ Ｂ2Ｏ3 １８〜６０ Ａｌ2Ｏ3 ０〜２０ Ｒ2Ｏ ８〜３０ （Ｒ＝Ｌｉ、Ｎａ、Ｋ） Ｒ'Ｏ ０〜２０ （Ｒ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ） Ａｇ2Ｏ ０．０５〜２．０ ＳＯ3 ０．０１〜０．１ 鉄酸化物（Ｆｅ2Ｏ3に換算） ０〜０．１ を含有することを特徴とする抗菌性ガラス用組成物。Claims 1. SiO2 25-60 B2O3 18-60 Al2O3 0-20 R2O 8-30 (R = Li, Na, K) R'O 0-20 (R '= Ca, Mg) , Zn, Ba) Ag2O 0.05-2.0 SO3 0.01-0.1 Iron oxide (converted to Fe2O3) 0-0.1 is contained, The composition for antibacterial glass characterized by the above-mentioned. 【請求項２】 重量％で表示して、 ＳｉＯ2 ３０〜５５ Ｂ2Ｏ3 ２０〜５５ Ａｌ2Ｏ3 １〜１０ Ｒ2Ｏ １０〜２０ （Ｒ＝Ｌｉ、Ｎａ、Ｋ） Ｒ'Ｏ ０〜１０ （Ｒ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ） Ａｇ2Ｏ ０．１〜１．０ ＳＯ3 ０．０１〜０．０３ 鉄酸化物（Ｆｅ2Ｏ3に換算） ０〜０．０５ を含有する請求項１記載の抗菌性ガラス用組成物。2. SiO2 30-55 B2O3 20-55 Al2O3 1-10 R2O 10-20 (R = Li, Na, K) R'O 0-10 (R '= Ca, Mg) , Zn, Ba) Ag2O 0.1-1.0 SO3 0.01-0.03 Iron oxide (converted to Fe2O3) 0-0.05, The antibacterial glass composition according to claim 1. 【請求項３】 重量％で表示して、 ＳｉＯ2 ３５〜６０ Ａｌ2Ｏ3 ０〜２０ ただしＳｉＯ2＋Ａｌ2Ｏ3 ４０〜６５ Ｂ2Ｏ3 １８〜５０ Ｒ2Ｏ ８〜２５ （Ｒ＝Ｌｉ、Ｎａ、Ｋ） Ｒ'Ｏ ０〜２０ （Ｒ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ） ただしＲ2Ｏ＋Ｒ'Ｏ ８〜３５ ＳＯ3 ０．０１〜０．１ 鉄酸化物（Ｆｅ2Ｏ3に換算） ０〜０．０５ Ａｇ2Ｏ ０．０５〜１．５ を含有することを特徴とする抗菌性ガラス繊維用組成
物。3. SiO2 35-60 Al2O3 0-20 where SiO2 + Al2O3 40-65 B2O3 18-50 R2O 8-25 (R = Li, Na, K) R'O 0-20 (R) '= Ca, Mg, Zn, Ba) However, R2O + R'O 8 to 35 SO3 0.01 to 0.1 Iron oxide (converted to Fe2O3) 0 to 0.05 Ag2O 0.05 to 1.5 should be contained. A composition for antibacterial glass fiber, characterized by: 【請求項４】 重量％で表示して、 ＳｉＯ2 ４０〜５８ Ａｌ2Ｏ3 ２〜１５ ただしＳｉＯ2＋Ａｌ2Ｏ3 ４２〜６３ Ｂ2Ｏ3 ２０〜４０ Ｒ2Ｏ １０〜２０ （Ｒ＝Ｌｉ、Ｎａ、Ｋ） Ｒ'Ｏ ０〜１０ （Ｒ'＝Ｃａ、Ｍｇ、Ｚｎ、Ｂａ） ただしＲ2Ｏ＋Ｒ'Ｏ １０〜３０ ＳＯ3 ０．０１〜０．０３ 鉄酸化物（Ｆｅ2Ｏ3に換算） ０〜０．０１ Ａｇ2Ｏ ０．１〜１．０ を含有する請求項３記載の抗菌性ガラス繊維用組成物。4. SiO2 40-58 Al2O3 2-15 where SiO2 + Al2O3 42-63 B2O3 20-40 R2O 10-20 (R = Li, Na, K) R'O 0-10 (R) '= Ca, Mg, Zn, Ba) However, R2O + R'O 10-30 SO3 0.01-0.03 Iron oxide (converted to Fe2O3) 0-0.01 Ag2O 0.1-1.0 is contained. Item 3. The antibacterial glass fiber composition according to Item 3. 【請求項５】前記抗菌性ガラス繊維用組成物が、粘性が
１０³ポイズになる温度が８００〜１２５０℃である特
性温度を有する請求項３記載の抗菌性ガラス繊維用組成
物。5. The antibacterial glass fiber composition according to claim 3, wherein the antibacterial glass fiber composition has a characteristic temperature such that the temperature at which the viscosity reaches 10 ³ poise is 800 to 1250 ° C. 【請求項６】前記抗菌性ガラス繊維用組成物が、日本光
学硝子工業会規格（ＪＯＧＩＳ）の『光学ガラスの化学
的耐久性の測定方法（粉末法）０６ー１９７５』で測定
したとき、その減量率が８０．０重量％以下にある請求
項３記載の抗菌性ガラス繊維用組成物。6. When the composition for antibacterial glass fiber is measured by "Method for measuring chemical durability of optical glass (powder method) 06-1975" of the Japan Optical Glass Industry Association (JOGIS), The antibacterial glass fiber composition according to claim 3, wherein the weight loss rate is 80.0% by weight or less.