JP3486951B2 - Antibacterial glass composition - Google Patents
Antibacterial glass compositionInfo
- Publication number
- JP3486951B2 JP3486951B2 JP09478694A JP9478694A JP3486951B2 JP 3486951 B2 JP3486951 B2 JP 3486951B2 JP 09478694 A JP09478694 A JP 09478694A JP 9478694 A JP9478694 A JP 9478694A JP 3486951 B2 JP3486951 B2 JP 3486951B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- cao
- antibacterial
- composition
- zno
- 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
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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- 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
- 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)
- Glass Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌および抗カビ性に
優れたガラス組成物に関する。TECHNICAL FIELD The present invention relates to a glass composition having excellent antibacterial and antifungal properties.
【０００２】[0002]
【従来の技術】一価の銀イオン（ Ａｇ+）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。ここで微生物とは、狭義には細菌，菌類，ウィルス
を言い、広義には更に原生動物，藻類などを含める。本
明細書では、前記の微生物などに毒性作用（抗菌作用を
含む）を示すことを、簡単に抗菌性があると言うことに
する。It is well known that monovalent silver ion (Ag + ) is toxic to lower organisms such as microorganisms. Here, the microorganisms mean bacteria, fungi, and viruses in a narrow sense, and further include protozoa, algae, and the like in a broad sense. In the present specification, showing toxic effects (including antibacterial effects) to the above-mentioned microorganisms is simply referred to as having antibacterial properties.
【０００３】銀イオンを溶解性ガラスに含有することで
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，Ｂ2Ｏ3を主成分
とするホウケイ酸系とＰ2Ｏ5を主成分とするリン酸系が
知られている。例えばホウケイ酸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）、リン酸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樹脂添加用ガラス組成
物（特開平４−３３８１２９）などがある。Many methods for imparting antibacterial properties by incorporating silver ions into a soluble glass have been proposed. As such a soluble glass, a borosilicate type glass containing SiO 2 , B 2 O 3 as a main component and a phosphoric acid type glass containing P 2 O 5 as a main component are known. For example, for borosilicate soluble glass
An antibacterial water treatment agent containing Ag + ions (Japanese Patent Publication No. 4-50878), a phosphoric acid-based soluble glass containing Ag +
There is an antibacterial resin-added glass composition containing an ion (JP-A-4-338129).
【０００４】[0004]
【発明が解決しようとする課題】銀含有ガラスの抗菌性
は、主に Ａｇ+イオンによって示されるので、そのガラ
ス組成としては銀がイオンとして安定に存在し得る組成
が望ましい。ガラス中での Ａｇ+イオンの安定性は、ガ
ラスネットワークを形成するカチオンと酸素の間の結合
の酸性度が高い程、すなわちＳｉ−Ｏ＜Ｂ−Ｏ＜Ｐ−Ｏ
の順に高くなるので、ケイ酸系＜ホウケイ酸系＜リン酸
系の順にＡｇ+ イオンを多量かつ安定に含有することが
できる（例えば、窯業協会誌,88[8],459(1980)）。Since the antibacterial property of the silver-containing glass is mainly represented by Ag + ions, the glass composition is preferably a composition in which silver can stably exist as ions. The stability of Ag + ions in glass is determined by the higher acidity of the bond between the cation forming the glass network and oxygen, that is, Si-O <B-O <P-O.
Therefore, a large amount of Ag + ions can be stably contained in the order of silicic acid type <borosilicate type <phosphoric acid type (for example, Ceramic Industry Association, 88 [8], 459 (1980)).
【０００５】しかし、ホウケイ酸系ガラスはケイ酸系ガ
ラスより多量のＡｇ+ イオンを含有することができるも
のの、その中におけるＡｇ+イオン安定性は余り高くは
なく、有機材料と複合化させる場合、あるいは塗料に混
合して他物品の表面に塗布して使用する場合において、
加熱処理や紫外線照射によってガラス中のＡｇ+ イオン
が容易に還元されて着色を起こす。また、ホウケイ酸系
ガラス中に銀をイオンとして含有することができる量は
せいぜい ０.５モル％程度に過ぎず、粉末状や繊維状で
他素材に添加して使用される場合には材料全体で見ると
Ａｇ+イオン含有量が少なくなって抗菌作用が十分でな
い場合がある。However, although the borosilicate glass can contain a larger amount of Ag + ions than the silicate glass, the Ag + ion stability in the glass is not so high, and when it is combined with an organic material, Or when mixed with paint and applied to the surface of other articles for use,
Ag + ions in the glass are easily reduced by heat treatment or UV irradiation to cause coloring. Further, the amount of silver that can be contained as ions in the borosilicate glass is at most about 0.5 mol%, and when it is used in the form of powder or fiber added to other materials, the whole material is used. Looking at, the content of Ag + ions may be low and the antibacterial action may not be sufficient.
【０００６】これに対して、リン酸系ガラス中では Ａ
ｇ+イオンは非常に安定で、数モル％以上含有すること
が可能であり、また有機材料と複合化させる時の加熱処
理によって、あるいは紫外線照射によっても還元されに
くく変色を起こしにくい。上記特開平４−３３８１２９
にはこのような現象に着目し、合成樹脂に添加した時に
変色を起こしにくいガラス組成物として、
Ｐ2０5 ４５〜７５モル％
ＣａＯ＋ＭｇＯ ３５〜５５モル％
Ｎａ2Ｏ＋Ｋ2Ｏ ０〜 ５モル％
ＳｉＯ2＋Ａｌ2Ｏ3 ５〜２０モル％
Ａｇ2Ｏ ０．１〜５重量％
で表されるリン酸系ガラス組成物が開示されている。し
かし、ここに開示されているアルカリ土類のリン酸塩を
主成分とするガラス組成物は、（１）その溶融に比較的
高温を必要とし、また（２）水分への溶解速度が比較的
小さく銀イオンの溶出速度が小さいために、銀イオンを
多量に含有できるにもかかわらず抗菌性を十分に発現で
きず、さらに（３）用途に応じて水分への溶解速度を調
整することが可能な範囲が狭いという問題点がある。On the other hand, in phosphoric acid type glass, A
The g + ion is very stable and can be contained in an amount of several mol% or more. Further, it is hard to be reduced and discolored even by a heat treatment for forming a composite with an organic material or by irradiation with ultraviolet rays. JP-A-4-338129
Paying attention to such a phenomenon, as a glass composition which hardly causes discoloration when added to a synthetic resin, P 2 0 5 45 to 75 mol% CaO + MgO 35 to 55 mol% Na 2 O + K 2 O 0 to 5 mol% A phosphoric acid-based glass composition represented by SiO 2 + Al 2 O 3 5 to 20 mol% Ag 2 O 0.1 to 5 wt% is disclosed. However, the glass composition containing an alkaline earth phosphate as a main component disclosed herein (1) requires a relatively high temperature for melting, and (2) has a relatively low dissolution rate in water. Since the elution rate of silver ions is small, silver ions can be contained in a large amount, but the antibacterial properties cannot be sufficiently expressed. (3) It is possible to adjust the dissolution rate in water according to the application. There is a problem that the range is narrow.
【０００７】本発明は、上記従来技術の問題点に基づ
き、多量の Ａｇ+イオンを安定に含有することができ、
その製造が比較的容易で、なおかつ水分への溶解速度を
調整することによって用途に応じて十分な抗菌性を発現
できる範囲が広いガラス組成物を提供とする事を目的と
するものである。The present invention is capable of stably containing a large amount of Ag + ions based on the above problems of the prior art,
It is an object of the present invention to provide a glass composition which is relatively easy to produce and has a wide range in which sufficient antibacterial properties can be exhibited depending on the application by adjusting the rate of dissolution in water.
【０００８】[0008]
【課題を解決するための手段】すなわち本発明は、樹脂
にＡｇ含有抗菌性ガラスを混入させてなる抗菌性樹脂
の、加熱処理または紫外線照射によるＡｇ+ イオン還元
に起因する変色を防止するための前記Ａｇ含有抗菌性ガ
ラスとして、モル％で表示して、
Ｐ2０5 ４４．０〜５２．５％、
ＣａＯ＋Ｍｇ０ ３０〜６０％、ただしモル比で表してＣａＯ／（ＣａＯ＋Ｍｇ０）は７
０％以上、
ＳｉＯ2＋Ａｌ2Ｏ3 ０〜 ４％、
Ｌｉ2Ｏ＋Ｂ2Ｏ3 ０〜１５％、
Ｎａ2Ｏ＋Ｋ2Ｏ ０〜 ５％、
ＺｎＯ＋ＢａＯ ０〜３０％、
ただし（ＣａＯ＋Ｍｇ０＋ＺｎＯ＋ＢａＯ）の合計 ３
０〜６０％、
ＰｂＯ ０〜 ５％、
Ａｇ2Ｏ ０．０３〜５％からなる組成を有し、かつ日
本光学硝子工業会規格（ＪＯＧＩＳ）『光学ガラスの化
学的耐久性の測定方法（粉末法）０６−１９７５』に基
づいて測定した溶解性で定義した耐水性が１．０〜４０
％であるものを使用する方法である。また本発明は、樹
脂にＡｇ含有抗菌性ガラスの粉末または繊維を混入させ
てなる抗菌性樹脂のＡｇ含有抗菌性ガラスの粉末または
繊維として、モル％で表示して、
Ｐ2０5 ４４．０〜５２．５％、
ＣａＯ＋Ｍｇ０ ３０〜６０％、ただしモル比で表してＣａＯ／（ＣａＯ＋Ｍｇ０）は７
０％以上、
ＳｉＯ2＋Ａｌ2Ｏ3 ０〜 ４％、
Ｌｉ2Ｏ＋Ｂ2Ｏ3 ０〜１５％、
Ｎａ2Ｏ＋Ｋ2Ｏ ０〜 ５％、
ＺｎＯ＋ＢａＯ ０〜３０％、
ただし（ＣａＯ＋Ｍｇ０＋ＺｎＯ＋ＢａＯ）の合計 ３
０〜６０％、
ＰｂＯ ０〜 ５％、
Ａｇ2Ｏ ０．０３〜５％からなる組成を有し、かつ日
本光学硝子工業会規格（ＪＯＧＩＳ）『光学ガラスの化
学的耐久性の測定方法（粉末法）０６−１９７５』に基
づいて測定した溶解性で定義した耐水性が１．０〜４０
％であるものを使用することを特徴とする加熱処理また
は紫外線照射によるＡｇ+ イオン還元に起因する抗菌性
樹脂の変色を防止する方法である。Means for Solving the Problems That is, the present invention is for preventing discoloration of an antibacterial resin obtained by mixing Ag-containing antibacterial glass in a resin due to Ag + ion reduction by heat treatment or ultraviolet irradiation. as the Ag-containing antimicrobial glass, and displayed in a mole%, P 2 0 5 44.0~52.5% , CaO + Mg0 30~60%, but expressed as molar ratios CaO / (CaO + Mg0) 7
0% or more, SiO 2 + Al 2 O 3 0 to 4%, Li 2 O + B 2 O 3 0 to 15%, Na 2 O + K 2 O 0 to 5%, ZnO + BaO 0 to 30%, but (CaO + Mg0 + ZnO + BaO) total 3
0~60%, PbO 0~ 5%, has a composition consisting of Ag 2 O 0.03~5%, and date
This optical glass industry association standard (JOGIS)
Method for measuring mechanical durability (powder method) 06-1975 ”
The water resistance defined by the solubility measured based on 1.0 to 40
% Is the method to use. The present invention, the Ag-containing antimicrobial glass antimicrobial resin obtained by mixing a powder or fibers of Ag-containing antimicrobial glass to resin powder or
As a fiber , expressed in mol %, P 2 0 5 44.0 to 52.5 %, CaO + Mg0 30 to 60%, but CaO / (CaO + Mg0) is 7 in terms of molar ratio.
0% or more, SiO 2 + Al 2 O 3 0 to 4%, Li 2 O + B 2 O 3 0 to 15%, Na 2 O + K 2 O 0 to 5%, ZnO + BaO 0 to 30%, but (CaO + Mg0 + ZnO + BaO) total 3
0~60%, PbO 0~ 5%, has a composition consisting of Ag 2 O 0.03~5%, and date
This optical glass industry association standard (JOGIS)
Method for measuring mechanical durability (powder method) 06-1975 ”
The water resistance defined by the solubility measured based on 1.0 to 40
% Is used to prevent discoloration of the antibacterial resin due to Ag + ion reduction due to heat treatment or ultraviolet irradiation.
【０００９】本発明の抗菌性ガラス組成物は、ガラスネ
ットワークを形成するカチオンと酸素の間の結合の酸性
度が高く Ａｇ+イオンが安定に存在し得るリン酸系を主
成分としているために、多量の Ａｇ+イオンを安定に含
有することが可能である。また、リン酸系ガラスの溶融
性を悪化させる ＳｉＯ2、Ａｌ2Ｏ3の含有量を少量に抑
えることによって、比較的容易に溶融が可能である。Since the antibacterial glass composition of the present invention is mainly composed of a phosphoric acid system in which the acidity of the bond between the cation forming the glass network and oxygen is high and Ag + ions can exist stably, It is possible to stably contain a large amount of Ag + ions. Further, by controlling the contents of SiO 2 and Al 2 O 3 which deteriorate the meltability of the phosphoric acid type glass to a small amount, it is possible to relatively easily melt the glass.
【００１０】また、本発明の抗菌性ガラス組成物は、リ
ン酸系ガラスの水に対する溶解速度を小さくする成分で
あるＡｌ2Ｏ3の含有量を少量に抑えているので、それ自
身の少量の範囲での含有量の調整、あるいはそれ以外の
成分、例えばＰ2Ｏ5、ＭｇＯ、ＣａＯ、ＢａＯ、ＺｎＯ
などの含有量を調整することによって、水分への溶解速
度を制御することが可能であり、用途に応じた抗菌性の
発現を調節することが可能である。さらに、本発明の抗
菌性ガラス組成物は、原料の混合，溶融が容易で安価に
製品を供給することができるよう、その組成がガラス原
料として安価な粉末状のリン酸塩原料の組み合わせで実
現できる範囲にある。Further, the antibacterial glass composition of the present invention suppresses the content of Al 2 O 3 which is a component for reducing the dissolution rate of phosphoric acid glass in water to a small amount, so that the small amount of itself can be used. Adjustment of the content in the range or other components such as P 2 O 5 , MgO, CaO, BaO, ZnO
The rate of dissolution in water can be controlled by adjusting the content of such as, and the expression of antibacterial properties can be adjusted according to the application. Further, the antibacterial glass composition of the present invention is realized by a combination of powdery phosphate raw materials whose composition is inexpensive as a glass raw material so that the raw materials can be easily mixed and melted and the product can be supplied at a low cost. It is within the range.
【００１１】上記組成範囲における各成分の限定理由は
以下の通りである。即ち、Ｐ2Ｏ5は４０モル％より少な
いとガラスが失透し易くなり、５５モル％より多いと粉
末状のリン酸塩原料のみの組み合わせではＰ2Ｏ5分が足
りなくなり、混合，溶融が困難となり製品のコスト上昇
を招く液体状のリン酸や非常に吸湿性の強いＰ2Ｏ5を原
料として使用せざるを得なくなる。The reasons for limiting each component in the above composition range are as follows. That is, if P 2 O 5 is less than 40 mol%, the glass tends to be devitrified, and if it is more than 55 mol%, P 2 O 5 is insufficient in the combination of only powdery phosphate raw materials, and the mixture and melting are caused. However, liquid phosphoric acid or P 2 O 5 having a very high hygroscopic property is inevitably used as a raw material.
【００１２】 ＣａＯ＋Ｍｇ０の含有量は、３０モル％
より少ないと粉末状のリン酸塩原料のみの組み合わせ組
成を実現することが困難となり、６０モル％より多いと
Ｐ2Ｏ5分が４０モル％より少なくなりガラスが失透し易
くなる。なお、ＣａＯ＋Ｍｇ０の成分の内、ＭｇＯのみ
を使用する場合には、ＣａＯのみの使用の場合に比べて
ガラスの水に対する溶解速度が小さくなり、他の成分の
含有量の調整で耐水性を制御可能な範囲が狭くなるの
で、ＣａＯのみを使用するかあるいはＣａＯの割合を多
くして、モル比でＣａＯ／（ＣａＯ＋Ｍｇ０）を７０％
以上とする。 The content of CaO + Mg0 is 30 mol%
If it is less, it becomes difficult to realize a combined composition of only powdery phosphate raw materials, and if it is more than 60 mol%, the content of P 2 O 5 is less than 40 mol%, and the glass tends to devitrify. In addition, when only MgO is used among the components of CaO + Mg0, the dissolution rate of glass in water becomes smaller than when only CaO is used, and the water resistance can be controlled by adjusting the content of other components. Since the range is narrow, use only CaO or increase the ratio of CaO, and the molar ratio of CaO / (CaO + Mg0) is 70%.
That is all.
【００１３】Ａｌ2Ｏ3は、上記のようにガラスの溶融性
を悪化させると共に、多量に入れ過ぎるとガラスの水に
対する溶解速度を小さくなり過ぎるので必須成分ではな
いが、少量の添加でガラスの水に対する溶解速度の調整
が可能な成分である。ＳｉＯ2もＡｌ2Ｏ3と同様の働き
をするので、（ＳｉＯ2＋Ａｌ2Ｏ3）の合計の上限量は
４モル％望ましくは３モル％である。Al 2 O 3 is not an essential component because it deteriorates the melting property of glass as described above, and if too much is added, the dissolution rate of glass in water becomes too small. It is a component whose dissolution rate in water can be adjusted. Because the same function as SiO 2 also Al 2 O 3, the upper limit of the sum of (SiO 2 + Al 2 O 3 ) is 4 mol% desirably 3 mol%.
【００１４】Ｌｉ2ＯおよびＢ2Ｏ3は必須成分ではない
が、 いずれも銀イオンの安定性を悪化させること無
く、ガラスの溶融性を向上させることができる成分であ
り、Ｌｉ2ＯおよびＢ2Ｏ3の合計で １５モル％以下の範
囲で加えることができる。これらの成分は、ガラスの水
に対する溶解速度を減少させるので、１５モル％を越え
ると水分に対する溶解性が低くなり過ぎる。また、これ
らの原料は高価なため、その量が多くなると製品のコス
トが上昇する。またＺｎＯおよびＢａＯはいずれも必須
成分ではないが、銀イオンの安定性を悪化させることな
くガラスの溶融を向上させる成分であり、ＺｎＯおよび
ＢａＯの合計で３０モル％以下の範囲で加えることがで
きる。また、Ｚｎ2+はＡｇ2+には劣るものの同様に抗菌
性を示す成分であってガラスの抗菌力を向上させる効果
もある。さらに（ＣａＯ＋Ｍｇ０＋ＺｎＯ＋ＢａＯ）の
合計量があまり大きすぎると、Ｐ2Ｏ5分が４０モル％よ
り少なくなりガラスが失透し易くなるのでこれら合計量
は６０モル％以下にする必要がある。またＰｂＯは５モ
ル％以下含有していても差し支えない。 Ａｇ2Ｏは、
０．０３モル％未満では抗菌性が弱くなり、５モル％を
越えると抗菌性に寄与しない金属状の銀が生じ易くなる
と共に、銀は高価であるため製品のコストを上昇させ
る。Li 2 O and B 2 O 3 are not essential components, but both are components capable of improving the meltability of glass without deteriorating the stability of silver ions. Li 2 O and B 2 The total amount of 2 O 3 can be added in the range of 15 mol% or less. Since these components reduce the dissolution rate of glass in water, the solubility in water becomes too low when the content exceeds 15 mol%. Further, since these raw materials are expensive, the cost of the product increases when the amount thereof increases. Although ZnO and BaO are not essential components, they are components that improve the melting of the glass without deteriorating the stability of silver ions, and the total amount of ZnO and BaO can be added in the range of 30 mol% or less. . Further, Zn 2+ is a component which is inferior to Ag 2+ but similarly exhibits antibacterial properties and has an effect of improving the antibacterial activity of glass. Further, if the total amount of (CaO + Mg0 + ZnO + BaO) is too large, the P 2 O 5 content will be less than 40 mol% and the glass will be easily devitrified, so these total amounts must be 60 mol% or less. Further, PbO may be contained in an amount of 5 mol% or less. Ag 2 O is
If it is less than 0.03 mol%, the antibacterial property is weakened, and if it exceeds 5 mol%, metallic silver that does not contribute to the antibacterial property is likely to be produced, and the cost of the product is increased because silver is expensive.
【００１５】[0015]
【実施例】表１に示した実施例および表２に示した比較
例の組成になるよう、Ｃａ，Ｍｇのリン酸塩あるいは場
合により炭酸塩、Ｌｉ、Ｎａのリン酸塩化合物あるいは
炭酸塩、ＳｉＯ2、Ａｌ2Ｏ3、アルミニウムのリン酸
塩、Ｈ3ＢＯ3、ＢａＣＯ3、ＺｎＯ、メタリン酸亜鉛、
ＡｇＮＯ3を原料として用いバッチを調合した。 このバ
ッチをＰｔるつぼに入れ、１３００℃で２時間溶融した
後、ステンレス板上に流し出し板状に成形後徐冷した。
本実施例の組成になるバッチは、粉末状の原料のみで構
成可能で、通常のケイ酸系あるいはホウケイ酸系ガラス
の場合と同様に混合，溶融が可能であった。次に、得ら
れたガラスについて、金属銀の析出状況、耐水性、抗菌
性、樹脂混合時の変色を調べた。結果を表１および表２
下段に示す。表２に示した比較例の内、１，２はホウケ
イ酸系抗菌ガラスの代表的組成、３〜５は前述の特開平
４−３３８１２９の特許請求範囲に含まれる組成、６〜
１０は本発明の特許請求範囲を外れた組成である。EXAMPLES The compositions of the examples shown in Table 1 and the comparative examples shown in Table 2 were adjusted so that Ca, Mg phosphates or carbonates, and optionally Li, Na phosphate compounds or carbonates, SiO 2 , Al 2 O 3 , aluminum phosphate, H 3 BO 3 , BaCO 3 , ZnO, zinc metaphosphate,
A batch was prepared using AgNO 3 as a raw material. This batch was placed in a Pt crucible, melted at 1300 ° C. for 2 hours, cast on a stainless steel plate, shaped into a plate, and then gradually cooled.
The batch having the composition of this example could be composed only of powdery raw materials, and could be mixed and melted as in the case of ordinary silicic acid-based or borosilicate-based glass. Next, the obtained glass was examined for metal silver deposition, water resistance, antibacterial properties, and discoloration during resin mixing. The results are shown in Table 1 and Table 2.
Shown in the lower row. Among the comparative examples shown in Table 2, 1 and 2 are typical compositions of antibacterial borosilicate glass, 3 to 5 are compositions included in the claims of the above-mentioned JP-A-4-338129, and 6 to
10 is a composition outside the scope of the claims of the present invention.
【００１６】金属銀の析出状況は、得られた板状ガラス
にハロゲンランプを照射して１０μｍ以上の金属銀につ
いてそのガラス１００ｇ当たりの数を数え、検出されな
い場合に◎、１００個以下の場合に○、１００個以上の
場合に×で示した。The deposition state of metallic silver was measured by irradiating a halogen lamp on the obtained plate-shaped glass, counting the number of metallic silver of 10 μm or more per 100 g of the glass. ◯, x when 100 or more
【００１７】 耐水性は、日本光学硝子工業会規格（Ｊ
ＯＧＩＳ）『光学ガラスの化学的耐久性の測定方法（粉
末法）０６−１９７５』を用いて評価した。この方法
は、粉砕したガラスから４２０〜５９０μｍの粒度の粉
末を採取し、これをアセトンで洗浄して微粉を除去した
後、その中から比重ｇ分を１００ｍｌの沸騰水中に１時
間浸漬し、乾燥後重量減を測定する方法である。銀入り
ガラスが抗菌性を示すためには、ガラスが水分にある程
度溶解し、銀イオンが溶出する必要があり、また余り溶
解速度が速過ぎると耐久性あるいは抗菌性の持続性が乏
しくなるので、本試験法による重量減で１．０〜４０％
の水に対する溶解性が必要である。なおこの溶解性の数
値は後の実施例および比較例では「耐水性」の数値とし
て表している。 Water resistance is defined by the Japan Optical Glass Industry Association standard (J
OGIS) “Method for measuring chemical durability of optical glass (powder method) 06-1975” was used for evaluation. In this method, powder having a particle size of 420 to 590 μm is collected from crushed glass, washed with acetone to remove fine powder, and then specific gravity g is immersed in 100 ml of boiling water for 1 hour and dried. It is a method of measuring the rear weight loss. In order for silver-containing glass to exhibit antibacterial properties, the glass must be dissolved in water to some extent and silver ions must be eluted, and if the dissolution rate is too fast, durability or antibacterial durability will be poor, 1.0-40% in weight loss according to this test method
Is required to be soluble in water. The number of this solubility
The value is the numerical value of "water resistance" in Examples and Comparative Examples described later.
Is represented.
【００１８】抗菌性は、以下のようにして簡易的に評価
した。１０５μｍ以下に粉砕したガラスをオルガノポリ
シロキサン系バインダーに重量で１０％添加し、これを
スプレーで５ｃｍ角で厚さが１ｍｍのガラス板表面に吹
き付け、乾燥して試料とした。この試料を寒天培地上に
置き、その上からカビの一種であるアスペルギウステレ
ウスの胞子を約１×１０5個／ｍｌ 含有する胞子懸濁液
を散布した後蓋をし、３０℃の恒温槽中で１週間培養
し、カビの生育状況を観察した。評価は、ガラス表面上
にアスペルギウステレウスの生育が全く観察されなかっ
た場合に◎、アスペルギウステレウスの生育範囲がガラ
ス表面の１／３以下の場合に○、ガラス表面の１／３以
上にアスペルギウステレウスが生育した場合に×で示し
た。The antibacterial property was evaluated simply as follows. 10% by weight of glass pulverized to 105 μm or less was added to an organopolysiloxane-based binder, and this was sprayed onto a glass plate surface of 5 cm square and 1 mm thick, and dried to obtain a sample. This sample was placed on an agar medium, and a spore suspension containing about 1 × 10 5 spores of Aspergius terreus, which is a mold, was sprayed on the sample, which was then covered with a constant temperature of 30 ° C. After culturing in the tank for 1 week, the growth of mold was observed. The evaluation was ⊚ when no growth of Aspergius terreus was observed on the glass surface, ◯ when the growth range of Aspergius terreus was 1/3 or less of the glass surface, and 1/3 or more of the glass surface. When Aspergius terreus was grown in, it was shown as x.
【００１９】樹脂混合時の変色は、重量で同量の粉末状
ポリエチレンと１０５μｍ以下のガラス粉末を混合し、
これを２００℃に保持したオーブン中に入れ、３０分間
加熱した後炉外に取り出して冷却し、溶融したポリエチ
レンが変色するかどうかによって評価した。評価は、変
色が全く認められない場合に◎、変色がわずかな場合に
○、変色が顕著な場合に×で示した。The discoloration at the time of resin mixing is to mix the same amount of powdery polyethylene by weight and glass powder of 105 μm or less,
This was placed in an oven maintained at 200 ° C., heated for 30 minutes, taken out of the furnace and cooled, and it was evaluated by whether or not the melted polyethylene was discolored. The evaluation was indicated by ⊚ when no discoloration was observed, ∘ when the discoloration was slight, and × when the discoloration was remarkable.
【００２０】[0020]
【表１】 [Table 1]
【００２１】 実施例（mol%） ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ ９ １０ １１ １２ １３ １４ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− P2O5 48.0 44.5 49.5 49.5 49.5 48.5 CaO 48.0 44.5 39.5 46.5 46.5 48.5 BaO 0 10.0 0 0 0 0 ZnO 0 0 10.0 0 0 0 SiO2 3.0 0 0 0 0 0 Na2O 0 0 0 3.0 0 0 K2O 0 0 0 0 3.0 0 PbO 0 0 0 0 0 2.0 Ag2O 1.0 1.0 1.0 1.0 1.0 1.0 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属銀析出 ◎ ◎ ◎ ◎ ◎ ◎ 耐水性（％） 9.5 21.7 15.1 24.8 31.2 18.5 抗菌性 ◎ ◎ ◎ ◎ ◎ ◎ 樹脂着色 ◎ ◎ ◎ ○ ○ ◎ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝Example (mol%) ========================================== 9 10 11 12 12 13 14 − −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− P 2 O 5 48.0 44.5 49.5 49.5 49.5 48.5 CaO 48.0 44.5 39.5 46.5 46.5 48.5 BaO 0 10.0 0 0 0 0 ZnO 0 0 10.0 0 0 0 SiO 2 3.0 0 0 0 0 0 Na 2 O 0 0 0 3.0 0 0 K 2 O 0 0 0 0 3.0 0 PbO 0 0 0 0 0 2.0 Ag 2 O 1.0 1.0 1.0 1.0 1.0 1.0 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Metallic silver deposition ◎ ◎ ◎ ◎ ◎ ◎ ◎ Water resistance (%) 9.5 21.7 15.1 24.8 31.2 18.5 Antibacterial property ◎ ◎ ◎ ◎ ◎ ◎ ◎ Resin coloring ◎ ◎ ◎ ○ ○ ◎ ======================= ============
【００２２】[0022]
【表２】 比較例（mol%） ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ 1 2 3 4 5 6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− SiO2 37.5 36.8 0 0 10.0 0 P2O5 0 0 49.5 50.0 50.0 35.0 MgO 0 0 43.5 39.0 0 0 CaO 0 0 0 0 39.0 50.0 Al2O3 0 0 6.0 10.0 0 0 B2O3 47.0 46.8 0 0 0 10.0 Li2O 0 0 0 0 0 0 Na2O 15.0 14.9 0 0 0 4.0 Ag2O 0.5 1.0 1.0 1.0 1.0 1.0 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 金属銀析出 ○ × ◎ - - - 耐水性（％） 35.0 - 0.5 - - - 抗菌性 ◎ - ○ - - - 樹脂着色 × - ○ - - - ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝[Table 2] Comparative example (mol%) =================================== 1 2 3 4 5 6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− SiO 2 37.5 36.8 0 0 10.0 0 P 2 O 5 0 0 49.5 50.0 50.0 35.0 MgO 0 0 43.5 39.0 0 0 CaO 0 0 0 0 39.0 50.0 Al 2 O 3 0 0 6.0 10.0 0 0 B 2 O 3 47.0 46.8 0 0 0 10.0 Li 2 O 0 0 0 0 0 0 Na 2 O 15.0 14.9 0 0 0 4.0 Ag 2 O 0.5 1.0 1.0 1.0 1.0 1.0 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− × ◎---Water resistance (%) 35.0-0.5---Antibacterial property ◎-○---Resin coloring ×-○---================== ================
【００２３】 ４〜５：１３００℃，２時間では完全に溶融せず。 ５、７：粉末状のリン酸塩原料のみでの調合不可。 ６、８：失透してガラス化しない。[0023] 4-5: Not completely melted at 1300 ° C for 2 hours. 5, 7: Cannot be prepared only with powdered phosphate raw material. 6, 8: devitrification and no vitrification.
【００２４】 表１に示した実施例から明らかなよう
に、本発明の範囲にある組成のガラスについては、金属
銀の析出は認められず、樹脂着色もほとんど認められな
かった。着色が認められたものも、それはわずかで実用
上問題無いレベルと推定された。また、耐水性も組成の
調整により、 1.5％から数10％程度までの広い範囲で調
整可能であり、組成によっては多少弱い物もあるが抗菌
性が観察された。この抗菌性の違いは、銀イオン含有量
および耐水性の違いによる、ガラスからの銀イオンの溶
出速度の違いに起因すると思われる。また、表２の比較
例１０および前述の特開平４−３３８１２９に記載のよ
うに、銀イオンの安定性が高く、樹脂に混合した時に着
色を起こしにくいリン酸系ガラスであっても、Ｎａ2Ｏ
あるいはＫ2Ｏなどのアルカリ金属酸化物を５ｍｏｌ％
を越えて含有すると、ガラス中の銀イオン安定性が低下
し、樹脂に混合した時に着色を起こし易くなる。 As is clear from the examples shown in Table 1, with respect to the glass having the composition within the range of the present invention, deposition of metallic silver was not observed, and resin coloring was hardly observed. It was estimated that coloring was slight and there was no problem in practical use. In addition, the water resistance can be adjusted in a wide range from 1.5 % to several tens of% by adjusting the composition, and antibacterial properties were observed although there are some weak materials depending on the composition. This difference in antibacterial property is considered to be due to the difference in the elution rate of silver ions from the glass due to the difference in silver ion content and water resistance. Further, as described in Comparative Example 10 in Table 2 and Japanese Patent Application Laid-Open No. 4-338129 mentioned above, even if the phosphoric acid-based glass has a high stability of silver ions and hardly causes coloring when mixed with a resin, Na 2 O
Or 5 mol% of alkali metal oxide such as K 2 O
When content exceeds, reduces the silver ion stability in the glass, that a susceptible to coloration when mixed with the resin.
【００２５】一方、表２に示した比較例の中では、１お
よび２のホウケイ酸系組成については、銀含有量が少な
いと金属銀の析出はなく抗菌性も強いが、樹脂に混合す
ると顕著な変色を起こし、銀含有量を増加させると金属
銀の析出が起こった。また、３〜５の特開平４−３３８
１２９の特許請求範囲に含まれる組成の中では、３につ
いては金属銀の析出はなく樹脂の着色もわずかであった
が、耐水性が良く銀イオンの溶出速度が小さいため抗菌
性がやや弱く、４，５の組成についてはバッチの溶解性
が悪く１３００℃では完全に溶融しなかった。また、５
組成のバッチについては粉末状のリン酸塩原料のみでの
調合が不可能であり、液体状のリン酸あるいは吸湿性が
非常に強い無水リン酸を使用する必要があった。さら
に、本発明の特許請求の範囲を外れた６〜８の組成につ
いては失透してガラスが得られなかったり、あるいは粉
末状のリン酸原料のみでの調合が不可能であり、また
９、１０の組成については、抗菌性が弱かったり、ある
いは樹脂に混合すると顕著な着色を起こした。On the other hand, among the comparative examples shown in Table 2, for the borosilicate type compositions 1 and 2, when the silver content is small, metallic silver does not precipitate and the antibacterial property is strong, but when mixed with the resin, it is remarkable. When the silver content was increased, metallic silver was precipitated. Further, JP-A-4-338 of 3 to 5
In the composition included in the scope of claims of 129, for 3 there was no precipitation of metallic silver and a slight coloring of the resin, but the antibacterial property was slightly weak because of good water resistance and a low silver ion elution rate, Regarding the compositions of Nos. 4 and 5, the solubility of the batch was poor and it did not completely melt at 1300 ° C. Also, 5
With respect to the batch of composition, it was impossible to prepare only the powdery phosphate raw material, and it was necessary to use liquid phosphoric acid or phosphoric anhydride having a very strong hygroscopic property. Further, regarding the compositions of 6 to 8 that deviate from the claims of the present invention, glass cannot be obtained by devitrification, or it is impossible to prepare only with a powdery phosphoric acid raw material. Regarding composition No. 10, the antibacterial property was weak, or when it was mixed with resin, remarkable coloring occurred.
【００２６】[0026]
【発明の効果】 以上の通り、本発明によれば、多量の
銀イオンを含有可能で、比較的製造が容易な抗菌性ガラ
ス組成物を得ることができる。また、本発明による抗菌
性ガラス組成物は、水分に対する溶解性を調整すること
によって銀イオンの溶出性を抗菌性が発現される比較的
広い範囲で調整することが可能で、用途に応じて抗菌性
を比較的広い範囲で調整することが可能である。この抗
菌性ガラス組成物を樹脂に混合して得られる抗菌性樹脂
は変色を起こすことがほとんどない。 As described above, according to the present invention, it is possible to obtain an antibacterial glass composition which can contain a large amount of silver ions and is relatively easy to manufacture. Further, the antibacterial glass composition according to the present invention can adjust the elution of silver ions in a relatively wide range in which the antibacterial property is expressed by adjusting the solubility in water, and the antibacterial glass composition according to the application can be used. Ru can der to adjust the sexual a relatively wide range. This anti
Antibacterial resin obtained by mixing fungal glass composition with resin
There is little to cause a strange color.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 1/00 - 14/00 A01N 1/00 - 65/02 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) C03C 1/00-14/00 A01N 1/00-65/02
Claims (2)
は繊維を混入させてなる抗菌性樹脂の、加熱処理または
紫外線照射によるＡｇ+ イオン還元に起因する変色を防
止するための前記Ａｇ含有抗菌性ガラスとして、モル％
で表示して、 Ｐ2０5 ４４．０〜５２．５％、 ＣａＯ＋Ｍｇ０ ３０〜６０％、ただしモル比で表してＣａＯ／（ＣａＯ＋Ｍｇ０）は７
０％以上、 ＳｉＯ2＋Ａｌ2Ｏ3 ０〜 ４％、 Ｌｉ2Ｏ＋Ｂ2Ｏ3 ０〜１５％、 Ｎａ2Ｏ＋Ｋ2Ｏ ０〜 ５％、 ＺｎＯ＋ＢａＯ ０〜３０％、 ただし（ＣａＯ＋Ｍｇ０＋ＺｎＯ＋ＢａＯ）の合計 ３
０〜６０％、 ＰｂＯ ０〜 ５％、 Ａｇ2Ｏ ０．０３〜５％ からなる組成を有し、かつ日本光学硝子工業会規格（Ｊ
ＯＧＩＳ）『光学ガラスの化学的耐久性の測定方法（粉
末法）０６−１９７５』に基づいて測定した溶解性で定
義した耐水性が１．０〜４０％であるものを使用する方
法。1. A resin containing Ag-containing antibacterial glass powder or
Is the above-mentioned Ag-containing antibacterial glass for preventing discoloration of the antibacterial resin containing fibers by heat treatment or UV irradiation to reduce discoloration due to Ag + ion reduction.
Is expressed as P 2 0 5 44.0 to 52.5 %, CaO + Mg 0 30 to 60%, but CaO / (CaO + Mg0) is 7 in terms of molar ratio.
0% or more, SiO 2 + Al 2 O 3 0 to 4%, Li 2 O + B 2 O 3 0 to 15%, Na 2 O + K 2 O 0 to 5%, ZnO + BaO 0 to 30%, but (CaO + Mg0 + ZnO + BaO) total 3
0 to 60%, PbO 0 to 5%, and Ag 2 O 0.03 to 5%, and has a composition of Japan Optical Glass Industry Standard (J.
OGIS) “Method of measuring chemical durability of optical glass (powder
End method) 06-1975 ”
A method using a material having a defined water resistance of 1.0 to 40% .
繊維を混入させてなる抗菌性樹脂のＡｇ含有抗菌性ガラ
スの粉末または繊維として、モル％で表示して、 Ｐ2０5 ４４．０〜５２．５％、 ＣａＯ＋Ｍｇ０ ３０〜６０％、ただしモル比で表してＣａＯ／（ＣａＯ＋Ｍｇ０）は７
０％以上、 ＳｉＯ2＋Ａｌ2Ｏ3 ０〜 ４％、 Ｌｉ2Ｏ＋Ｂ2Ｏ3 ０〜１５％、 Ｎａ2Ｏ＋Ｋ2Ｏ ０〜 ５％、 ＺｎＯ＋ＢａＯ ０〜３０％、 ただし（ＣａＯ＋Ｍｇ０＋ＺｎＯ＋ＢａＯ）の合計 ３
０〜６０％、 ＰｂＯ ０〜 ５％、 Ａｇ2Ｏ ０．０３〜５％ からなる組成を有し、かつ日本光学硝子工業会規格（Ｊ
ＯＧＩＳ）『光学ガラスの化学的耐久性の測定方法（粉
末法）０６−１９７５』に基づいて測定した溶解性で定
義した耐水性が１．０〜４０％であるものを使用するこ
とを特徴とする加熱処理または紫外線照射によるＡｇ+
イオン還元に起因する抗菌性樹脂の変色を防止する方
法。2. A resin containing Ag-containing antibacterial glass powder or
As a powder or fibers of Ag-containing antimicrobial glass antimicrobial resin obtained by mixing the fibers, and displayed in mol%, P 2 0 5 44.0~52.5% , CaO + Mg0 30~60%, provided that the molar ratio CaO / (CaO + Mg0) is 7
0% or more, SiO 2 + Al 2 O 3 0 to 4%, Li 2 O + B 2 O 3 0 to 15%, Na 2 O + K 2 O 0 to 5%, ZnO + BaO 0 to 30%, but (CaO + Mg0 + ZnO + BaO) total 3
0 to 60%, PbO 0 to 5%, and Ag 2 O 0.03 to 5%, and has a composition of Japan Optical Glass Industry Standard (J.
OGIS) “Method of measuring chemical durability of optical glass (powder
End method) 06-1975 ”
Ag + by heat treatment or ultraviolet irradiation characterized by using a water resistance of 1.0-40% as defined
A method for preventing discoloration of an antibacterial resin due to ion reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09478694A JP3486951B2 (en) | 1994-05-09 | 1994-05-09 | Antibacterial glass composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09478694A JP3486951B2 (en) | 1994-05-09 | 1994-05-09 | Antibacterial glass composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07300339A JPH07300339A (en) | 1995-11-14 |
| JP3486951B2 true JP3486951B2 (en) | 2004-01-13 |
Family
ID=14119768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09478694A Expired - Fee Related JP3486951B2 (en) | 1994-05-09 | 1994-05-09 | Antibacterial glass composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3486951B2 (en) |
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| DE102004011520A1 (en) * | 2004-03-08 | 2005-10-06 | Schott Ag | Antimicrobial refractive index adapted phosphate glass |
| JP5171569B2 (en) | 2008-11-19 | 2013-03-27 | 浜松ホトニクス株式会社 | Fiber optic plate and manufacturing method thereof |
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| US10676394B2 (en) | 2013-06-17 | 2020-06-09 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH07300339A (en) | 1995-11-14 |
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| LAPS | Cancellation because of no payment of annual fees |