JP3212903B2 - Antibacterial agent for adding synthetic resin - Google Patents
Antibacterial agent for adding synthetic resinInfo
- Publication number
- JP3212903B2 JP3212903B2 JP04002297A JP4002297A JP3212903B2 JP 3212903 B2 JP3212903 B2 JP 3212903B2 JP 04002297 A JP04002297 A JP 04002297A JP 4002297 A JP4002297 A JP 4002297A JP 3212903 B2 JP3212903 B2 JP 3212903B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- glass
- synthetic resin
- antibacterial agent
- resin
- 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 - Lifetime
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、無色透明性が要求され
る樹脂製品（例えば、内容物が有姿のままよく見えるも
の、文房具のファイルシートやボールペン、密封容器
等）の性能を損なわないで、これらの製品に抗菌性を付
与するための合成樹脂添加用抗菌剤に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention does not impair the performance of resin products which are required to be colorless and transparent (for example, those whose contents can be seen as they are, stationery file sheets, ballpoint pens, sealed containers, etc.). The present invention relates to an antibacterial agent for adding a synthetic resin for imparting antibacterial properties to these products.
【０００２】[0002]
【従来の技術】一般家庭あるいは業務用の合成樹脂とし
ては、様々な用途で使用されている。その中の多くの場
合には、デザイン上、制約を受ける、或いは外観上の見
栄えのよさを理由に製品に対して無色透明性が要求され
ている。そして、これらの製品は、日常生活の中で人間
と直接接触、あるいは直接目に触れることも多いため、
清潔感が要求されると共に、加工時、使用時においても
変色しないことが求められている。2. Description of the Related Art Synthetic resins for general household or business use are used for various purposes. In many cases, products are required to be colorless and transparent due to design restrictions, or because of their good appearance. And because these products often come into direct contact with humans or even directly in daily life,
It is required to have a clean feeling and not to be discolored during processing and use.
【０００３】そこで、合成樹脂添加用抗菌剤として抗菌
作用を有する銀イオン含有ゼオライト粒子に代表される
珪酸塩化合物のような無機系抗菌剤が提案されている
が、ゼオライト粒子からの銀イオンの溶出量が少なく抗
菌効果が十分に発揮されなかったり、ゼオライト粒子自
体の吸湿性が大きいためにその取扱いが容易でなく製
造、加工が困難であるという欠点があった。また、銀が
移動しやすい構造になったものであるため、少量で抗菌
効果を示すものの、光学的異方性結晶質でもあるため、
光散乱で不透明化したり、銀の溶出が激しい環境下（人
間の汗及び光）ではＡｇ+ →Ａｇ0 の還元が起こりやす
く、製品が変色するおそれがあった。Therefore, inorganic antibacterial agents such as silicate compounds typified by silver ion-containing zeolite particles having an antibacterial effect have been proposed as antibacterial agents for adding synthetic resins. However, elution of silver ions from zeolite particles has been proposed. There were drawbacks that the antibacterial effect was not sufficiently exhibited due to the small amount, and that the zeolite particles themselves were not easily handled due to their high hygroscopicity, and were difficult to manufacture and process. In addition, because it has a structure in which silver can easily move, it shows antibacterial effect in a small amount, but because it is also optically anisotropic crystalline,
In an environment where light scattering makes the material opaque or silver elutes violently (human sweat and light), reduction of Ag + → Ag 0 is likely to occur, and the product may be discolored.
【０００４】また他には、銀錯体担持シリカゲルやリン
酸ジルコニウム等のリン酸塩化合物を使用するものがあ
るが、上記のものと同様に１価の銀イオンが金属銀に還
元しやすく加工時、又は使用時の汗と光により変色する
おそれがあり、これら抗菌剤自体が高価で、コスト的に
も見合うものではなかった。[0004] Others use a phosphate compound such as silica gel supporting silver complex or zirconium phosphate. However, similarly to the above, monovalent silver ions are easily reduced to metallic silver, and processing is difficult. Or, there is a risk of discoloration due to sweat and light during use, and these antibacterial agents themselves are expensive and not worth the cost.
【０００５】銀を担持したリン酸カルシウムを使用する
ものもあるが、銀がイオンとしてほとんど遊離しないの
で、変色の可能性はないものの、抗菌効果が低く、十分
な効果が得られなかった。そこで、確実に抗菌性を付与
するためには、含有量がどうしても多くなってしまうこ
とと、また、樹脂との屈折率差が０．４程度であるこ
と、更に光学的異方性であることも加わって透明性が極
度に低下するものであった。また、銀錯塩担持珪酸塩化
合物及び銀担持硼珪酸系ガラスも用いられることがある
が、無変色性、透明性の面で満足しえるものではなかっ
た。[0005] Some of them use calcium phosphate carrying silver, but since silver is hardly released as ions, there is no possibility of discoloration, but the antibacterial effect is low and a sufficient effect cannot be obtained. Therefore, in order to reliably impart antibacterial properties, the content must be increased by all means, and the difference in refractive index from the resin must be about 0.4, and the optical anisotropy must also be achieved. In addition, the transparency was extremely reduced. Further, a silicate compound supporting silver complex salt and a borosilicate glass supporting silver are sometimes used, but they are not satisfactory in terms of non-discoloration and transparency.
【０００６】これらのように、樹脂の無色透明性を維持
しつつ、抗菌性を満たす無機系抗菌剤は存在していなか
った。As described above, there has been no inorganic antibacterial agent satisfying the antibacterial property while maintaining the colorless and transparent properties of the resin.
【０００７】一方、上記の銀イオンの変色の可能性の問
題を回避するために、万が一変色しても外観的に変化の
ないように樹脂の原料に着色剤を混合させて変色をカモ
フラージュさせる対応を実施しており、樹脂の製造コス
ト増加の一因となっていると共に、無色透明性の要求に
対しては、満足させることができていなかった。On the other hand, in order to avoid the above-mentioned problem of the possibility of discoloration of silver ions, a colorant is mixed with a resin material so that the discoloration does not change even if the discoloration occurs. This has been one of the causes of an increase in the production cost of the resin, and has not been able to satisfy the demand for colorless transparency.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記した従来
の問題点を解決して、優れた抗菌機能を長期間にわたっ
て安定して発揮することができ、樹脂の持つ特性を損な
わないで無色透明性を維持できるようにすることであ
る。さらに、取扱いが容易で製造や加工性にも優れると
ともに、いかなる製造、加工条件や使用条件下において
も着色変化することがなく、製造コストの低減もできう
る合成樹脂添加用抗菌剤を提供しようとするものであ
る。また、合成樹脂添加用抗菌剤自体の低コスト化も見
込まれるものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems and can exhibit an excellent antibacterial function stably over a long period of time, and is colorless and transparent without impairing the properties of the resin. To be able to maintain sex. Furthermore, it is intended to provide an antibacterial agent for adding a synthetic resin which is easy to handle, excellent in production and processability, does not change color under any production, processing conditions and use conditions, and can reduce the production cost. Is what you do. Further, cost reduction of the antibacterial agent for adding the synthetic resin itself is expected.
【０００９】[0009]
【課題を解決するための手段】上記の課題を解決するた
めになされた本発明の無色透明合成樹脂添加用抗菌剤
は、Ｂ2Ｏ3 ：４０〜６０モル％、ＭｇＯ：３０〜５０
モル％、Ｎａ2 Ｏ：１〜１０モル％、Ｐ2 Ｏ5 ：１〜１
０モル％の基本組成に、Ａｇ2 Ｏを０．０５〜３重量％
含有した溶解性ガラスを粒子径１μｍ〜５０μｍに粉砕
したことを特徴とするものである。 Colorless and transparent synthetic resin additive for antibacterial agent of the present invention has been made to solve the above problems BRIEF SUMMARY OF THE INVENTION may, B 2 O 3: 40~60 mol%, MgO: 30 to 50
Mol%, Na 2 O: 1~10 mol%, P 2 O 5: 1~1
The basic composition of 0 mol%, the Ag 2 O 0.05 to 3 wt%
It is characterized in that the contained soluble glass is ground to a particle diameter of 1 μm to 50 μm.
【００１０】本発明で使用される溶解性ガラスとは、制
御された溶解速度を持つようにガラスの物理的、化学的
特性を考慮して組成を調整したガラスの総称であり、抗
菌成分とは、銀イオンであり、それらを含有させた徐放
性のガラスは数時間から数年間の任意の期間にわたって
定められた速度で銀イオンを溶出させることができる。
そして溶出した上記金属イオンは細菌や微生物の細胞壁
に吸着したり細胞膜内に凝縮していわゆるオリゴジナミ
ー作用により細菌や微生物の生育を阻害し、抗菌機能を
発揮するものである。[0010] The melting glass used in the present invention is a generic name of glass whose composition is adjusted in consideration of physical and chemical properties of the glass so as to have a controlled melting rate. , Silver ions, and a sustained-release glass containing them can elute silver ions at a predetermined rate over an arbitrary period of several hours to several years.
The eluted metal ions are adsorbed on the cell walls of bacteria and microorganisms or condensed in the cell membrane, and inhibit the growth of bacteria and microorganisms by the so-called oligodynamic action, thereby exhibiting an antibacterial function.
【００１１】本発明で用いられる溶解性ガラスは、Ｐ2
Ｏ5 ，Ｂ2 Ｏ3 ，Ｎａ2 Ｏ，ＭｇＯ，等のうち特定成分
を含むガラス組成物の他に、抗菌成分である銀イオンを
含んだものである。加えて言えば、組成が無限大の数あ
る抗菌性ガラスを鋭意研究により、見極めることにより
達成することができたものであり、さらに粒径を数μｍ
とすること、非晶質（光学的等方性）のものであるこ
と、屈折率の近似化をなすこと及び銀の含有量、溶出速
度を安定に保持することの全てを兼ね備えたガラスとす
ることにより解決することができるものである。The melting glass used in the present invention is P 2
O 5, B 2 O 3, Na 2 O, MgO, in addition to the glass composition containing a specific component of the like, are those that contain silver ions are antimicrobial component. In addition, it was possible to achieve the antimicrobial glass having an infinite number of compositions through intense research and to identify the antimicrobial glass.
Glass that has all of the following characteristics: being amorphous (optically isotropic), approximating the refractive index, and stably maintaining the silver content and the elution rate. This can be solved by doing so.
【００１２】ここで、銀イオンを所定の速度で溶出させ
るためには、溶解性ガラスの組成中にＡｇ2 Ｏを０．０
５〜３重量％含有しておく必要がある。０．０５重量％
未満では、十分な抗菌機能が期待できないためである。
逆に３重量％を超えると、必要以上にＡｇの量が多くな
ることにより、練り込み変色又は経時変色を引き起こす
ことにつながってしまうからである。基本ガラス組成
中、Ｂ2 Ｏ3 は４０〜６０モル％である必要がある。４
０％未満では、結晶化して透明性が低下するためであ
り、６０％を超えると、Ａｇ+ の溶出速度が上昇し、経
時変色を招くためである。またＭｇＯが３０〜５０モル
％である必要があるのは、３０％未満では、Ａｇ+ の溶
出速度が上昇し、経時変色を招くためであり、５０％を
超えると、非晶質ガラスが得にくくそのため、透明性が
大きく損なわれるためである。さらにＮａ2 Ｏが１〜１
０モル％であるのは、１％未満では非晶質ガラスが得に
くくそのため、上記同様透明性が大きく損なわれるため
であり、１０％を超えると、アルカリ性が強くなり、銀
の変色が目立つようになってしまうからである。Ｐ2 Ｏ
5 は１〜１０モル％である必要がある。これは、１％未
満及び１０％超のいずれでも非晶質ガラスが得にくくそ
の結果として、透明性が大きく損なわれるためである。In order to elute silver ions at a predetermined rate, Ag 2 O is added to the composition of the melting glass in an amount of 0.02.
It is necessary to contain 5 to 3% by weight. 0.05% by weight
If it is less than 30, sufficient antibacterial function cannot be expected.
On the other hand, if it exceeds 3% by weight, the amount of Ag is increased more than necessary, which leads to discoloration during kneading or discoloration with time. In the basic glass composition, B 2 O 3 should be 40 to 60 mol%. 4
If it is less than 0%, the crystallinity is reduced, and if it is more than 60%, the dissolution rate of Ag + is increased, which causes discoloration with time. The reason why MgO is required to be 30 to 50 mol% is that if it is less than 30%, the dissolution rate of Ag + increases, causing discoloration with time. If it exceeds 50%, amorphous glass is obtained. This is because the transparency is greatly impaired. Further, Na 2 O is 1 to 1
The reason why the content is 0 mol% is that if it is less than 1%, it is difficult to obtain an amorphous glass, so that the transparency is greatly impaired as described above. It is because it becomes. P 2 O
5 needs to be 1 to 10 mol%. This is because it is difficult to obtain an amorphous glass at any of less than 1% and more than 10%, and as a result, transparency is greatly impaired.
【００１３】溶解性ガラスを粒子径１μｍ〜５０μｍに
粉砕したものを使用する。５０μｍを超えると、異物感
が生じてきたり、樹脂本来の物性低下を招いてしまうか
らであり、逆に１μｍ未満であると光散乱が著しくな
り、透明性が劣り、さらに０．１μｍ未満では、透明性
は向上するが、ガラスの２次凝集が起こってしまうこと
と、コスト高で現実的には、良くなかった。そして、よ
り好ましくは２μｍ〜２０μｍがよい。このガラスを樹
脂に０．０５〜０．５重量％の割合で含有させなければ
ならない。０．０５％未満では、抗菌効果が不足してし
まうからであり、０．５％超では、透明性が劣ってしま
うからである。より好ましくは、０．１〜０．２％がよ
い。[0013] A glass obtained by pulverizing a soluble glass to a particle diameter of 1 to 50 µm is used. If it exceeds 50 μm, a foreign-body sensation occurs or the physical properties of the resin are deteriorated. Conversely, if it is less than 1 μm, light scattering becomes remarkable, transparency is poor, and if it is less than 0.1 μm, Although the transparency is improved, secondary aggregation of the glass occurs and the cost is high, which is not good in practice. And more preferably, it is 2 μm to 20 μm. The glass must be contained in the resin at a rate of 0.05 to 0.5% by weight. If it is less than 0.05%, the antibacterial effect will be insufficient, and if it exceeds 0.5%, the transparency will be poor. More preferably, 0.1 to 0.2% is good.
【００１４】この組成のガラスは、粒径５００μｍにお
いて２０℃の水にＡｇ+ を０．０１１ｍｇ／ｇ／Ｈｒの
スピードで溶出し、適正な粒径と少量の添加率で樹脂に
無色透明性と抗菌性を付与することができるものであ
る。The glass of this composition elutes Ag + into water at 20 ° C. at a speed of 0.011 mg / g / Hr at a particle size of 500 μm and has a colorless and transparent resin with an appropriate particle size and a small addition ratio. It can provide antibacterial properties.
【００１５】本発明において、用いる樹脂の材質は特に
限定するものではないが、例えば、ＰＳ（ポリスチレ
ン）、ＡＳ（アクリルスチレン）、ＡＢＳ（アクリルブ
タジエンスチレン）、ＰＰ（ポリプロピレン）、ＰＥ
（ポリエチレン）、ＰＶＣ（塩化ビニル）、ＰＣ（ポリ
カーボネート）、ＰＥＴ（ポリエステル）、ＰＭＭＡ
（ポリメチルメタアクリレート）、尿素樹脂、ナイロン
等を挙げることができる。In the present invention, the material of the resin used is not particularly limited. For example, PS (polystyrene), AS (acryl styrene), ABS (acryl butadiene styrene), PP (polypropylene), PE
(Polyethylene), PVC (vinyl chloride), PC (polycarbonate), PET (polyester), PMMA
(Polymethyl methacrylate), urea resin, nylon and the like.
【００１６】[0016]
【作用】このように構成された本発明の合成樹脂添加用
抗菌剤は、使用時あるいは使用後における水分との接触
の際に樹脂等が持つ僅かな透水性、透湿性によって水分
が合成樹脂添加用抗菌剤本体の内部に浸透し、この水分
によって溶解性ガラスが微量ずつ溶解し、抗菌性能を有
する銀イオンを溶出することとなる。銀イオンの溶出量
は一定期間中ほぼ一定量であり、この結果、銀イオンの
抗菌作用によって合成樹脂添加用抗菌剤の表面上におけ
る細菌の繁殖、あるいはそれらによる変色等を完全に防
止することが可能になる。また、本発明の溶解性ガラス
によれば、抗菌剤の屈折率と種々の樹脂の屈折率の差が
０．１０未満であり、しかも材料特性として光学的等方
性を有するため、適正な含有量範囲であれば樹脂の特性
を損なうことなく、無色透明性も維持されることとな
る。The antibacterial agent for adding a synthetic resin according to the present invention thus constituted is characterized in that the moisture is added to the synthetic resin due to the slight water permeability and moisture permeability of the resin at the time of use or after contact with the water after use. The water penetrates into the antibacterial agent main body, and the water dissolves the dissolvable glass in small amounts, thereby eluting silver ions having antibacterial performance. The amount of silver ion eluted is almost constant for a certain period of time, and as a result, the antibacterial action of silver ion can completely prevent the growth of bacteria on the surface of the antibacterial agent for adding synthetic resin or the discoloration due to them. Will be possible. Further, according to the melting glass of the present invention, the difference between the refractive index of the antibacterial agent and the refractive index of various resins is less than 0.10, and the material has optical isotropy as a material property. When the amount is within the range, the colorless and transparent property is maintained without impairing the properties of the resin.
【００１７】[0017]
【実施例】本発明の合成樹脂添加用抗菌剤を実施例によ
り詳細に説明する。抗菌剤としてＢ2 Ｏ3 、ＭｇＯ、Ｎ
ａ2 Ｏ、Ｐ2 Ｏ5 、Ａｇ2 Ｏを表１に示す組成比となる
ようにＢ2 Ｏ3 塩、Ｐ2 Ｏ5 塩、Ａｇ塩化合物を調合
し、１２００〜１４００℃で１時間溶融して、ガラス化
したものを用いた。これをロールクラッシャージェット
ミル粉砕により、各々の粒径とした。EXAMPLES The antibacterial agent for adding a synthetic resin of the present invention will be described in more detail with reference to examples. B 2 O 3 , MgO, N as antibacterial agents
B 2 O 3 salt, P 2 O 5 salt, and Ag salt compound were prepared so that a 2 O, P 2 O 5 , and Ag 2 O had the composition ratios shown in Table 1, and melted at 1200 to 1400 ° C. for 1 hour. Then, a vitrified material was used. This was made into each particle size by roll crusher jet mill pulverization.
【００１８】[0018]
【表１】 [Table 1]
【００１９】これらについて、それぞれ硝子化（結晶
化の有無により○、×で表示），練込変色（ポリプロ
ピレンに０．２重量％練込んで変色の有無を目視により
判断して○、×で表示。なお、これ以下の試験はいずれ
も本試験で作成したプレートによるテスト），耐光変
色（キセノンランプ４５０ｗ／ｍ2 に２００時間照射後
の色差ΔＥの値），ＮａＣｌＯ水浸漬（１％ＮａＣｌ
Ｏ水溶液中に２週間浸漬後の色差ΔＥの値），Ｎａ2
Ｓ水浸漬（１％Ｎａ2 Ｓ水溶液中に２週間浸漬後の色差
ΔＥの値），透明性（６００ｎｍの光透過率差％），
抗菌性（黄色ブドウ球菌を含む１／５０普通ブイヨン
をプレートに滴下、フィルムを密着させ、３５℃、２４
Ｈｒ放置後に、洗い出し、培養して生菌数を計数するこ
とによって行った。）について調べた結果を表２に示
す。For each of these, vitrification (indicated by ○ or × depending on the presence or absence of crystallization) and discoloration (kneading in 0.2% by weight in polypropylene to visually judge the presence or absence of discoloration, indicated by 、 and ×) The tests below were all performed using the plate prepared in this test), lightfastness (color difference ΔE after irradiation with a xenon lamp 450 w / m 2 for 200 hours), immersion in NaClO water (1% NaCl).
O) for 2 weeks after immersion in an aqueous O solution), Na 2
S water immersion (color difference ΔE value after immersion in 1% Na 2 S aqueous solution for 2 weeks), transparency (light transmittance difference% at 600 nm),
Antibacterial (1/50 normal broth containing Staphylococcus aureus is dropped on the plate, the film is adhered,
After leaving for hrs, the cells were washed out, cultured, and the number of viable cells was counted. ) Are shown in Table 2.
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【発明の効果】以上説明したように、本発明の合成樹脂
添加用抗菌剤は、優れた抗菌機能を長期間にわたって安
定して発揮することができ、樹脂の持つ特性を損なわな
いで無色透明性を維持できるようにすることである。さ
らに、取扱いが容易で製造や加工性にも優れるととも
に、いかなる製造、加工条件や使用条件下においても着
色変化することがなく、製造コストの低減もできるもの
である。従って、抗菌と美観が両立することができると
いう効果を有している。よって本発明は従来の問題点を
一掃した合成樹脂添加用抗菌剤として極めて大きい意義
がある。As described above, the antibacterial agent for adding a synthetic resin of the present invention can exhibit an excellent antibacterial function stably over a long period of time, and is colorless and transparent without impairing the properties of the resin. Is to be able to maintain. Furthermore, it is easy to handle and excellent in production and processability, and does not change color under any production, processing or use conditions, and can reduce production costs. Therefore, there is an effect that both antibacterial and aesthetic appearance can be compatible. Therefore, the present invention is of great significance as an antibacterial agent for adding a synthetic resin that has eliminated the conventional problems.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｋ 7/20 Ｃ０８Ｋ 7/20 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C08K 7/20 C08K 7/20
Claims (1)
３０〜５０モル％、Ｎａ2 Ｏ：１〜１０モル％、Ｐ2 Ｏ
5 ：１〜１０モル％の基本組成に、Ａｇ2Ｏを０．０５
〜３重量％含有した溶解性ガラスを粒子径１μｍ〜５０
μｍに粉砕したことを特徴とする無色透明合成樹脂添加
用抗菌剤。1. A B 2 O 3: 40~60 mol%, MgO:
30-50 mol%, Na 2 O: 1~10 mol%, P 2 O
5 : 1 to 10 mol% of basic composition, 0.05% of Ag 2 O
Melting glass containing 1 to 3% by weight.
An antimicrobial agent for adding a colorless and transparent synthetic resin, which is pulverized to a size of μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04002297A JP3212903B2 (en) | 1997-02-07 | 1997-02-07 | Antibacterial agent for adding synthetic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04002297A JP3212903B2 (en) | 1997-02-07 | 1997-02-07 | Antibacterial agent for adding synthetic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10218712A JPH10218712A (en) | 1998-08-18 |
| JP3212903B2 true JP3212903B2 (en) | 2001-09-25 |
Family
ID=12569287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04002297A Expired - Lifetime JP3212903B2 (en) | 1997-02-07 | 1997-02-07 | Antibacterial agent for adding synthetic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3212903B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160040A (en) * | 1998-11-27 | 2000-06-13 | Kamaya Kagaku Kogyo Co Ltd | Biodegradable resin molded product |
| JP4689019B2 (en) * | 1999-12-28 | 2011-05-25 | 石塚硝子株式会社 | Antibacterial imparting glass composition, antibacterial polymer composite material using the same, and antibacterial polymer composite material |
| AU2002349533A1 (en) * | 2002-03-29 | 2003-10-13 | Koa Glass Co., Ltd. | Antimicrobial glass and process for producing the same |
-
1997
- 1997-02-07 JP JP04002297A patent/JP3212903B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10218712A (en) | 1998-08-18 |
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