JPH08133918A - Inorganic antimicrobial agent - Google Patents
Inorganic antimicrobial agentInfo
- Publication number
- JPH08133918A JPH08133918A JP30323494A JP30323494A JPH08133918A JP H08133918 A JPH08133918 A JP H08133918A JP 30323494 A JP30323494 A JP 30323494A JP 30323494 A JP30323494 A JP 30323494A JP H08133918 A JPH08133918 A JP H08133918A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- inorganic
- zinc oxide
- inorganic powder
- sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【産業上の利用分野】本発明は、主に細菌の繁殖を抑制
させる無機系抗菌剤に関し、より詳しくは合成樹脂、塗
料、ゴム等の各種素材に添加する用途に用いる無機系抗
菌剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic antibacterial agent which mainly suppresses the growth of bacteria, and more particularly to an inorganic antibacterial agent for use in various materials such as synthetic resins, paints and rubbers.
【従来の技術】従来これら無機系抗菌剤としては、例え
ば特開昭６０−１８１００２に示される様に、ゼオライ
トに代表される無機系粉（多くの場合担体もしくは担持
体と言われる）に銀、銅及び亜鉛をイオン交換させるこ
とにより担持させる構成を有していた。Conventionally, as these inorganic antibacterial agents, for example, as shown in JP-A-60-181002, an inorganic powder represented by zeolite (often called a carrier or a carrier) and silver, It had a configuration in which copper and zinc were carried by ion exchange.
【発明が解決しようとする課題】しかしながらこれら従
来の無機系抗菌剤は、銀、銅及び亜鉛のうち最も多様な
細菌に抗菌力を示し、且つ抗菌力の最も強い銀の溶解度
（以下ここで言う溶解度とは、無機系抗菌剤から水中で
溶解する金属イオンの溶解度を表すものとする）が低い
ため、特に合成樹脂、塗料、ゴム等に混練、混合等の手
法により添加した際、これら合成樹脂、塗料、ゴム等の
表面に付着する細菌を抑制するに十分な銀イオンを供給
することができず、結果として抗菌力が不十分であると
いう課題があった。本発明はこれら従来の課題を解決す
るものであり、合成樹脂、塗料、ゴム等の各種素材に添
加しても十分な抗菌力を示す無機系抗菌剤を提供するこ
とを目的とする。However, these conventional inorganic antibacterial agents show antibacterial activity against most diverse bacteria among silver, copper and zinc, and the solubility of silver having the strongest antibacterial activity (hereinafter referred to as "herein"). Solubility refers to the solubility of metal ions that are dissolved in water from an inorganic antibacterial agent), so when these synthetic resins are added to synthetic resins, paints, rubbers, etc. by a method such as kneading and mixing, However, there is a problem in that it is not possible to supply sufficient silver ions to suppress bacteria adhering to the surface of paint, rubber, etc., and as a result, the antibacterial activity is insufficient. The present invention solves these conventional problems, and an object of the present invention is to provide an inorganic antibacterial agent which exhibits sufficient antibacterial activity even when added to various materials such as synthetic resins, paints and rubbers.
【課題を解決するための手段】これら従来の課題を解決
するために本発明の無機系抗菌剤は、硫酸銀を担持させ
た無機系粉末と酸化亜鉛からなるものである。In order to solve these conventional problems, the inorganic antibacterial agent of the present invention comprises an inorganic powder supporting silver sulfate and zinc oxide.
【作用】これらの構成によって、いかに本発明の目的が
達成されるかについて、以下順を追って説明する。本発
明で用いる硫酸銀は（化１）に示す。How the objects of the present invention are achieved by these configurations will be described step by step below. The silver sulfate used in the present invention is shown in Chemical formula 1.
【化１】 この硫酸銀は、硝酸銀と硫酸塩（例えば硫酸ナトリウ
ム）との反応により水系で容易に合成できる。さらに硫
酸銀は水に対する飽和溶解度が２０℃において、０．７
９重量％と高く、細菌の繁殖を抑制するに十分な銀イオ
ンを供給することができる。この硫酸銀を担持させる無
機系粉末としては、水に不要な無機系化合物であればよ
く、耐熱性、安定性の点から好ましくはリン酸カルシウ
ム、シリカゲル、硫酸バリウム、酸化チタンであり、よ
り好ましくはシリカゲル、硫酸バリウムである。さらに
これら無機系粉末の平均１次粒子径は、合成樹脂等の素
材に均一に分散させ、且つ広い表面積を得るために１０
μｍ以下が好ましく、より好ましくは５μｍ以下であ
る。本発明で用いる酸化亜鉛とは通常亜鉛華と称され、
白色顔料、塗料、薬用として広く用いられる粒子状無機
物であり、抗菌剤助剤としても他の抗菌力を有する金
属、特に銀と併用することによって抗菌効果を著しく強
化せしめることが公知の事実である。ここで本発明の最
大の特徴は、酸化亜鉛として酸化亜鉛ウイスカを用いる
ことであり、他に類をみない独特のテトラポット形状の
単結晶体であるため通常の亜鉛華にくらべ抗菌活性が強
く、特に硫酸銀との併用により優れた抗菌力を発現させ
るものである。図１は本発明で用いる酸化亜鉛ウイスカ
の結晶構造を示す電子顕微鏡写真であり、その形状特異
性が容易に確認できる。本発明に用いる硫酸銀の無機系
粉末に対する担持量は０．０４％以上５．０％未満が好
ましく、より好ましくは０．３％以上１．８％未満であ
る。硫酸銀の無機系粉末に対する担持量がこれより多い
とコスト的に著しく不利になるばかりか、銀特有の黒変
色を生じ好ましくなく、これより少ないと抗菌力が不十
分である。本発明に用いる酸化亜鉛もしくは酸化亜鉛ウ
イスカと硫酸銀を担持させた無機系粉末との比率は、
０．２対９９．８から３０対７０の間で選択されること
が好ましく、より好ましくは３対９７から１０対９０の
間である。酸化亜鉛もしくは酸化亜鉛ウイスカと硫酸銀
を担持させた無機系粉末との比率がこれ以外の場合、例
えば酸化亜鉛もしくは酸化亜鉛ウイスカが硫酸銀を担持
させた無機系粉末に比して多いとイオン化傾向の相違か
ら硫酸銀の溶解度を減少させ、逆に少ないと硫酸銀と酸
化亜鉛もしくは酸化亜鉛ウイスカとの併用効果が十分に
発揮されず、好ましくない。Embedded image This silver sulfate can be easily synthesized in an aqueous system by a reaction between silver nitrate and a sulfate (for example, sodium sulfate). Further, silver sulfate has a saturated solubility in water of 20 ° C. of 0.7.
It is as high as 9% by weight, and it is possible to supply sufficient silver ions to suppress bacterial growth. The inorganic powder for supporting silver sulfate may be any inorganic compound that is unnecessary for water, and in view of heat resistance and stability, calcium phosphate, silica gel, barium sulfate, and titanium oxide are preferable, and silica gel is more preferable. , Barium sulfate. Furthermore, the average primary particle size of these inorganic powders is 10 in order to uniformly disperse them in materials such as synthetic resins and to obtain a large surface area.
It is preferably at most 5 μm, more preferably at most 5 μm. Zinc oxide used in the present invention is usually called zinc white,
It is a well-known fact that the antibacterial effect can be remarkably enhanced by using it in combination with other antibacterial metal, especially silver, which is a particulate inorganic substance widely used for white pigments, paints and medicinal purposes. . Here, the greatest feature of the present invention is that zinc oxide whiskers are used as zinc oxide, and since it is a unique tetrapot-shaped single crystal, it has stronger antibacterial activity than ordinary zinc white. , Particularly when used in combination with silver sulfate, it exhibits excellent antibacterial activity. FIG. 1 is an electron micrograph showing the crystal structure of zinc oxide whiskers used in the present invention, and its shape specificity can be easily confirmed. The amount of silver sulfate used in the present invention supported on the inorganic powder is preferably 0.04% or more and less than 5.0%, more preferably 0.3% or more and less than 1.8%. If the amount of silver sulfate supported on the inorganic powder is larger than this, not only the cost becomes significantly disadvantageous, but also black discoloration peculiar to silver occurs, which is not preferable, and if less than this, the antibacterial activity is insufficient. The ratio of zinc oxide or zinc oxide whiskers used in the present invention to the inorganic powder supporting silver sulfate is
It is preferably selected between 0.2: 99.8 and 30:70, more preferably between 3:97 and 10:90. When the ratio of zinc oxide or zinc oxide whiskers to the inorganic powder supporting silver sulfate is other than this, for example, when the proportion of zinc oxide or zinc oxide whiskers is higher than that of the inorganic powder supporting silver sulfate, the ionization tendency tends to occur. On the contrary, if the solubility of silver sulfate is decreased, and if it is too small, the combined effect of silver sulfate and zinc oxide or zinc oxide whiskers is not sufficiently exhibited, which is not preferable.
【実施例】以下本発明の実施例について説明するが本発
明はこれら実施例に限定されるものではない。 （実施例１）平均１次粒子径２．３μｍのシリカゲル８
００ｇをイオン交換水３．１ｌ中に加え攪拌した後、
０．３ｍｏｌ／ｌの硝酸銀水溶液１ｌと０．１５ｍｏｌ
／ｌの硫酸ナトリウム水溶液１ｌを加え、さらに硝酸水
溶液を用いてＰＨを５．９に調整し緩速回転にて攪拌し
ながら１２時間放置した。その後固形分を濾過し減圧下
において乾燥させた後、粉砕することにより硫酸銀を担
持したシリカゲル粉末（以下ＳＩ／Ａｇとする）を得
た。得られたＳＩ／Ａｇの銀担持量を調べるため、硝酸
中で溶解させ原子吸光度法により測定した結果、銀換算
で１．２％であった。さらに得られたＳＩ／ＡｇのＸ線
回折パターンからは、硫酸銀の明確なピークとケイ酸銀
の弱いピークが確認された。得られたＳＩ／Ａｇを０．
４％イオン交換水中に分散させ２４時間放置した後、遠
心分離により上澄液中の銀濃度を定量した結果１２２ｐ
ｐｍであった。又従来技術に相当する公知の方法（たと
えば特開昭６０−１８１００２）により得られたゼオラ
イトに銀を１．４％イオン交換法により担持させた試料
を用いて同様の試験を行なった結果銀濃度は２３ｐｐｍ
であり、本発明の無機系抗菌剤の銀溶解度が従来技術に
よる無機系抗菌剤に比して著しく高いことが分かる。次
に得られたＳＩ／Ａｇ０．９％と酸化亜鉛ウイスカ０．
１％を、アクリルニトリル−ブタジエン−スチレン樹脂
（以下ＡＢＳとする）、アクリル系エマルジョン塗料、
ＳＢＲゴムにそれぞれ添加し、ＡＢＳ，ＳＢＲゴムの場
合は加圧成形により、アクリル系エマルジョン塗料の場
合は約１０μｍの塗膜をスレート板上に形成し試験片を
得た。さらに得られた各種試験片上に初期濃度１０5／c
cオーダーの大腸菌液、及び黄色ブドウ球菌液を１ccず
つ滴下し２４時間後の生菌数を平板混釈培養法により求
めた。比較として公知の方法により得られたゼオライト
に銀を１．４％イオン交換法により担持させた試料を前
記各種素材に１％添加したもの、及び抗菌剤を添加しな
い前記各種素材の抗菌力も同様に評価した。結果はすべ
て（表１）に示す。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. (Example 1) Silica gel 8 having an average primary particle diameter of 2.3 μm
After adding 00 g to 3.1 l of ion-exchanged water and stirring,
1 mol of 0.3 mol / l silver nitrate aqueous solution and 0.15 mol
1 l of an aqueous solution of sodium sulfate of 1 / l was added, and the pH was adjusted to 5.9 using an aqueous solution of nitric acid, and the mixture was allowed to stand for 12 hours while stirring at slow rotation. Then, the solid content was filtered, dried under reduced pressure, and then pulverized to obtain a silica gel powder supporting silver sulfate (hereinafter referred to as SI / Ag). In order to examine the amount of silver supported on the obtained SI / Ag, it was dissolved in nitric acid and measured by an atomic absorption method. As a result, it was 1.2% in terms of silver. Further, from the obtained SI / Ag X-ray diffraction pattern, a clear peak of silver sulfate and a weak peak of silver silicate were confirmed. The obtained SI / Ag was 0.
The dispersion was dispersed in 4% ion-exchanged water, left standing for 24 hours, and then the concentration of silver in the supernatant was quantified by centrifugation.
pm. Further, a similar test was conducted using a sample obtained by carrying out a 1.4% ion exchange method on a zeolite obtained by a known method corresponding to the prior art (for example, JP-A-60-181002). As a result, the silver concentration was determined. Is 23 ppm
It can be seen that the silver solubility of the inorganic antibacterial agent of the present invention is remarkably higher than that of the inorganic antibacterial agents of the prior art. Next, obtained SI / Ag 0.9% and zinc oxide whisker 0.
1% of acrylonitrile-butadiene-styrene resin (hereinafter referred to as ABS), acrylic emulsion paint,
SBR rubber was added to each, and in the case of ABS and SBR rubber, pressure molding was performed, and in the case of acrylic emulsion paint, a coating film of about 10 μm was formed on a slate plate to obtain a test piece. Furthermore, an initial concentration of 10 5 / c was applied on the various test pieces obtained.
C-order Escherichia coli solution and Staphylococcus aureus solution were added dropwise by 1 cc and the viable cell count after 24 hours was determined by the plate pour culture method. As a comparison, the antibacterial activity of the various materials obtained by adding 1% to the various materials prepared by loading the zeolite obtained by the known method with 1.4% silver by the ion exchange method and the antibacterial activity of the various materials without the addition of the antibacterial agent are also the same. evaluated. All results are shown in (Table 1).
【表１】 （表１）から明らかなように、本発明の無機系抗菌剤は
その銀溶解度が高いため、従来技術による無機系抗菌剤
に比して、抗菌力に優れていることがわかる。 （実施例２）実施例１で得られたＳＩ／Ａｇ０．９％と
酸化亜鉛として亜鉛華特号０．１％を、ＡＢＳに添加し
加圧成形により試験片を得た。さらに得られた各種試験
片上に初期濃度１０5／ccオーダーの大腸菌液、及び黄
色ブドウ球菌液を１ccずつ滴下し２４時間後の生菌数を
平板混釈培養法により求めた。比較として公知の方法に
より得られたゼオライトに銀を１．４％イオン交換法に
より担持させた試料をＡＢＳに１％添加したもの、及び
抗菌剤を添加しないＡＢＳの抗菌力も同様に評価した。
結果はすべて（表２）に示す。[Table 1] As is clear from (Table 1), the inorganic antibacterial agent of the present invention has a high silver solubility, and is therefore superior in antibacterial activity to the inorganic antibacterial agents of the prior art. (Example 2) SI / Ag 0.9% obtained in Example 1 and zinc white special feature 0.1% as zinc oxide were added to ABS to obtain a test piece by pressure molding. Further, 1 cc of the initial concentration of 10 5 / cc order Escherichia coli solution and 1 cc of Staphylococcus aureus solution were dropped on each of the various test pieces obtained, and the viable cell count after 24 hours was determined by the plate pour culture method. For comparison, the antibacterial activity of the zeolite obtained by a known method and having 1% of ABS loaded with a sample in which silver was loaded by 1.4% by the ion exchange method and ABS without the addition of the antibacterial agent were similarly evaluated.
All results are shown in (Table 2).
【表２】 （表２）から明らかなように、酸化亜鉛のみを亜鉛華特
号に変更することにより、実施例１と比較して抗菌力は
劣化方向にあるものの、依然として従来技術による無機
系抗菌剤に比し優れた抗菌力を有していることがわか
る。 （実施例３）平均１次粒子径３．４μｍのリン酸カルシ
ウム８００ｇをイオン交換水３．１ｌ中に加え攪拌した
後、０．３ｍｏｌ／ｌの硝酸銀水溶液１ｌと０．１５ｍ
ｏｌ／ｌの硫酸ナトリウム水溶液１ｌを加え、さらに硝
酸水溶液を用いてＰＨを５．９に調整し緩速回転にて攪
拌しながら１２時間放置した。その後固形分を濾過し減
圧下において乾燥させた後、粉砕することにより硫酸銀
を担持したリン酸カルシウム粉末（以下ＣＡＰＯ／Ａｇ
とする）を得た。得られたＣＡＰＯ／Ａｇの銀担持量を
調べるため、硝酸中で溶解させ原子吸光度法により測定
した結果、銀換算で１．４％であった。さらに得られた
ＣＡＰＯ／ＡｇのＸ線回折パターンからは、硫酸銀の明
確なピークとリン酸銀の弱いピークが確認された。得ら
れたＣＡＰＯ／Ａｇを０．４％イオン交換水中に分散さ
せ２４時間放置した後、遠心分離により上澄液中の銀濃
度を定量した結果１０５ｐｐｍであった。又従来技術に
相当する公知の方法（たとえば特開昭６０−１８１００
２）により得られたゼオライトに銀を１．４％イオン交
換法により担持させた試料を用いて同様の試験を行なっ
た結果銀濃度は２２ｐｐｍであり、本発明の無機系抗菌
剤の銀溶解度が従来技術による無機系抗菌剤に比して、
著しく高いことが分かる。次に得られたＣＡＰＯ／Ａｇ
０．９％と酸化亜鉛ウイスカ０．１％を、ＡＢＳに添加
し加圧成形により試験片を得た。さらに得られた試験片
上に初期濃度１０5／ccオーダーの大腸菌液、及び黄色
ブドウ球菌液を１ccずつ滴下し２４時間後の生菌数を平
板混釈培養法により求めた。比較として公知の方法によ
り得られたゼオライトに銀を１．４％イオン交換法によ
り担持させた試料を前記各種素材に１％添加したもの、
及び抗菌剤を添加しない前記各種素材の抗菌力も同様に
評価した。結果はすべて（表３）に示す。[Table 2] As is clear from (Table 2), by changing only zinc oxide to Zinc Hua Special Feature, the antibacterial activity tends to deteriorate as compared with Example 1, but it is still higher than that of the inorganic antibacterial agent according to the prior art. It can be seen that it has excellent antibacterial activity. (Example 3) 800 g of calcium phosphate having an average primary particle diameter of 3.4 μm was added to 3.1 l of ion-exchanged water and stirred, and then 1 l of a 0.3 mol / l silver nitrate aqueous solution and 0.15 m
1 l of an aqueous solution of sodium sulfate of ol / l was added, the pH was adjusted to 5.9 with an aqueous solution of nitric acid, and the mixture was allowed to stand for 12 hours while stirring at a slow rotation. Then, the solid content is filtered, dried under reduced pressure, and then pulverized to carry out calcium sulfate-supported calcium phosphate powder (hereinafter referred to as CAPO / Ag).
I got). In order to examine the amount of CAPO / Ag thus obtained supported on silver, it was dissolved in nitric acid and measured by an atomic absorption method. As a result, it was 1.4% in terms of silver. Further, from the obtained CAPO / Ag X-ray diffraction pattern, a clear peak of silver sulfate and a weak peak of silver phosphate were confirmed. The obtained CAPO / Ag was dispersed in 0.4% ion-exchanged water, allowed to stand for 24 hours, and then the silver concentration in the supernatant was quantified by centrifugation, resulting in 105 ppm. In addition, a known method corresponding to the prior art (for example, JP-A-60-18100).
A similar test was conducted using a sample in which the zeolite obtained in 2) was loaded with silver by the 1.4% ion exchange method. As a result, the silver concentration was 22 ppm, and the silver solubility of the inorganic antibacterial agent of the present invention was Compared with inorganic antibacterial agents by conventional technology,
It turns out that it is extremely high. Next obtained CAPO / Ag
0.9% and zinc oxide whiskers 0.1% were added to ABS to obtain a test piece by pressure molding. Further, 1 cc of an initial concentration of 10 5 / cc order Escherichia coli solution and 1 cc of Staphylococcus aureus solution were dropped on each of the obtained test pieces, and the viable cell count after 24 hours was determined by the plate pour culture method. For comparison, a sample obtained by supporting silver by a 1.4% ion-exchange method on a zeolite obtained by a known method and adding 1% to the above-mentioned various materials,
Also, the antibacterial activity of the above-mentioned various materials to which no antibacterial agent was added was evaluated in the same manner. All results are shown in (Table 3).
【表３】 （表３）から明らかなように、本発明の無機系抗菌剤は
その銀溶解度が高いため、従来技術による無機系抗菌剤
に比して、抗菌力に優れていることがわかる。 （実施例４）平均１次粒子径３．４μｍの硫酸バリウム
８００ｇをイオン交換水３．１ｌ中に加え攪拌した後、
０．３ｍｏｌ／ｌの硝酸銀水溶液１ｌと０．１５ｍｏｌ
／ｌの硫酸ナトリウム水溶液１ｌを加え、さらに硝酸水
溶液を用いてＰＨを５．９に調整し緩速回転にて攪拌し
ながら１２時間放置した。その後固形分を濾過し減圧下
において乾燥させた後、粉砕することにより硫酸銀を担
持した硫酸バリウム粉末（以下ＢＡＳ／Ａｇとする）を
得た。得られたＢＡＳ／Ａｇの銀担持量を調べるため、
硝酸中で溶解させ原子吸光度法により測定した結果、銀
換算で１．２％であった。さらに得られたＢＡＳ／Ａｇ
のＸ線回折パターンからは、硫酸銀の明確なピークのみ
が確認された。得られたＢＡＳ／Ａｇを０．４％イオン
交換水中に分散させ２４時間放置した後、遠心分離によ
り上澄液中の銀濃度を定量した結果１３９ｐｐｍであっ
た。又従来技術に相当する公知の方法（たとえば特開昭
６０−１８１００２）により得られたゼオライトに銀を
１．４％イオン交換法により担持させた試料を用いて同
様の試験を行なった結果銀濃度は２２ｐｐｍであり、本
発明の無機系抗菌剤の銀溶解度が従来技術による無機系
抗菌剤に比して著しく高いことが分かる。次に得られた
ＢＡＳ／Ａｇ０．９％と酸化亜鉛ウイスカ０．１％を、
ＡＢＳに添加し加圧成形により試験片を得た。さらに得
られた試験片上に初期濃度１０5／ccオーダーの大腸菌
液、及び黄色ブドウ球菌液を１ccずつ滴下し２４時間後
の生菌数を平板混釈培養法により求めた。比較として公
知の方法により得られたゼオライトに銀を１．４％イオ
ン交換法により担持させた試料を前記各種素材に１％添
加したもの、及び抗菌剤を添加しない前記各種素材の抗
菌力も同様に評価した。結果はすべて（表４）に示す。[Table 3] As is clear from (Table 3), the inorganic antibacterial agent of the present invention has a high silver solubility, and thus is superior in antibacterial activity to the inorganic antibacterial agents of the prior art. Example 4 After adding 800 g of barium sulfate having an average primary particle size of 3.4 μm to 3.1 l of ion-exchanged water and stirring,
1 mol of 0.3 mol / l silver nitrate aqueous solution and 0.15 mol
1 l of an aqueous solution of sodium sulfate of 1 / l was added, and the pH was adjusted to 5.9 using an aqueous solution of nitric acid, and the mixture was allowed to stand for 12 hours while stirring at slow rotation. After that, the solid content was filtered, dried under reduced pressure, and then pulverized to obtain barium sulfate powder supporting silver sulfate (hereinafter referred to as BAS / Ag). In order to check the amount of silver supported on the obtained BAS / Ag,
As a result of dissolving in nitric acid and measuring by an atomic absorption method, it was 1.2% in terms of silver. Further obtained BAS / Ag
From the X-ray diffraction pattern of, only a clear peak of silver sulfate was confirmed. The obtained BAS / Ag was dispersed in 0.4% ion-exchanged water, allowed to stand for 24 hours, and then the silver concentration in the supernatant was quantified by centrifugation, resulting in 139 ppm. Further, a similar test was conducted using a sample obtained by carrying out a 1.4% ion exchange method on a zeolite obtained by a known method corresponding to the prior art (for example, JP-A-60-181002). As a result, the silver concentration was determined. Is 22 ppm, which indicates that the silver solubility of the inorganic antibacterial agent of the present invention is remarkably higher than that of the inorganic antibacterial agents of the prior art. Next, the obtained BAS / Ag 0.9% and zinc oxide whisker 0.1%,
A test piece was obtained by adding to ABS and pressure molding. Further, 1 cc of an initial concentration of 10 5 / cc order Escherichia coli solution and 1 cc of Staphylococcus aureus solution were dropped on each of the obtained test pieces, and the viable cell count after 24 hours was determined by the plate pour culture method. As a comparison, the antibacterial activity of the various materials obtained by adding 1% to the various materials prepared by loading the zeolite obtained by the known method with 1.4% silver by the ion exchange method and the antibacterial activity of the various materials without the addition of the antibacterial agent are also the same. evaluated. All results are shown in (Table 4).
【表４】 （表４）から明らかなように、本発明の無機系抗菌剤は
その銀溶解度が高い為、従来技術による無機系抗菌剤に
比して、抗菌力に優れていることがわかる。 （実施例５）平均１次粒子径１．８μｍの酸化チタン８
００ｇをイオン交換水３．１ｌ中に加え攪拌した後、
０．３ｍｏｌ／ｌの硝酸銀水溶液１ｌと０．１５ｍｏｌ
／ｌの硫酸ナトリウム水溶液１ｌを加え、さらに硝酸水
溶液を用いてＰＨを５．９に調整し緩速回転にて攪拌し
ながら１２時間放置した。その後固形分を濾過し減圧下
において乾燥させた後、粉砕することにより硫酸銀を担
持した酸化チタン粉末（以下ＴＩＯ／Ａｇとする）を得
た。得られたＴＩＯ／Ａｇの銀担持量を調べるため、硝
酸中で溶解させ原子吸光度法により測定した結果、銀換
算で１．２％であった。さらに得られたＴＩＯ／Ａｇの
Ｘ線回折パターンからは、硫酸銀の明確なピークのみが
確認された。得られたＴＩＯ／Ａｇを０．４％イオン交
換水中に分散させ２４時間放置した後、遠心分離により
上澄液中の銀濃度を定量した結果１１６ｐｐｍであっ
た。又従来技術に相当する公知の方法（たとえば特開昭
６０−１８１００２）により得られたゼオライトに銀を
１．４％イオン交換法により担持させた試料を用いて同
様の試験を行なった結果銀濃度は２６ｐｐｍであり、本
発明の無機系抗菌剤の銀溶解度が従来技術による無機系
抗菌剤に比して著しく高いことが分かる。次に得られた
ＴＩＯ／Ａｇ０．９％と酸化亜鉛ウイスカ０．１％を、
ＡＢＳに添加し加圧成形により試験片を得た。さらに得
られた試験片上に初期濃度１０5／ccオーダーの大腸菌
液、及び黄色ブドウ球菌液を１ccずつ滴下し２４時間後
の生菌数を平板混釈培養法により求めた。比較として公
知の方法により得られたゼオライトに銀を１．４％イオ
ン交換法により担持させた試料を前記各種素材に１％添
加したもの、及び抗菌剤を添加しない前記各種素材の抗
菌力も同様に評価した。結果はすべて（表５）に示す。[Table 4] As is clear from Table 4, since the inorganic antibacterial agent of the present invention has a high silver solubility, it has a superior antibacterial activity as compared with the conventional inorganic antibacterial agents. (Example 5) Titanium oxide 8 having an average primary particle diameter of 1.8 μm
After adding 00 g to 3.1 l of ion-exchanged water and stirring,
1 mol of 0.3 mol / l silver nitrate aqueous solution and 0.15 mol
1 l of an aqueous solution of sodium sulfate of 1 / l was added, and the pH was adjusted to 5.9 using an aqueous solution of nitric acid, and the mixture was allowed to stand for 12 hours while stirring at slow rotation. Thereafter, the solid content was filtered, dried under reduced pressure, and then pulverized to obtain a titanium oxide powder supporting silver sulfate (hereinafter referred to as TIO / Ag). In order to investigate the amount of silver supported on the obtained TIO / Ag, it was dissolved in nitric acid and measured by an atomic absorption method. As a result, it was 1.2% in terms of silver. Further, from the obtained X-ray diffraction pattern of TIO / Ag, only a clear peak of silver sulfate was confirmed. The obtained TIO / Ag was dispersed in 0.4% ion-exchanged water, allowed to stand for 24 hours, and then the concentration of silver in the supernatant was quantified by centrifugation to find that it was 116 ppm. Further, a similar test was conducted using a sample obtained by carrying out a 1.4% ion exchange method on a zeolite obtained by a known method corresponding to the prior art (for example, JP-A-60-181002). As a result, the silver concentration was determined. Is 26 ppm, which indicates that the silver solubility of the inorganic antibacterial agent of the present invention is remarkably higher than that of the conventional inorganic antibacterial agents. Next, 0.9% of the obtained TIO / Ag and 0.1% of zinc oxide whiskers,
A test piece was obtained by adding to ABS and pressure molding. Further, 1 cc of an initial concentration of 10 5 / cc order Escherichia coli solution and 1 cc of Staphylococcus aureus solution were dropped on each of the obtained test pieces, and the viable cell count after 24 hours was determined by the plate pour culture method. As a comparison, the antibacterial activity of the various materials obtained by adding 1% to the various materials prepared by loading the zeolite obtained by the known method with 1.4% silver by the ion exchange method and the antibacterial activity of the various materials without the addition of the antibacterial agent are also the same. evaluated. All results are shown in (Table 5).
【表５】 （表５）から明らかなように、本発明の無機系抗菌剤は
その銀溶解度が高いため、従来技術による無機系抗菌剤
に比して、抗菌力に優れていることがわかる。なお本実
施例で示した硫酸銀の各種担体への添加量、及び本発明
の無機系抗菌剤の各種素材への添加量はこれに限定する
ものではなく、用途や抗菌力の寿命等に応じて本発明の
主目的を損なわない範囲で任意になしうることは言うま
でもない。又本発明の無機系抗菌剤の銀溶解度をさらに
高める目的で、銀と錯化合物を形成するチオ硫酸ナトリ
ウム、アンモニウム塩等との併用も本発明の目的を損な
わない範囲で任意になしうることは言うまでもない。[Table 5] As is clear from (Table 5), the inorganic antibacterial agent of the present invention has a high silver solubility, and thus is superior in antibacterial activity to the inorganic antibacterial agents of the prior art. Note that the addition amount of silver sulfate to various carriers shown in this example, and the addition amount to various materials of the inorganic antibacterial agent of the present invention are not limited to this, depending on the application, the life of antibacterial activity, etc. It goes without saying that the present invention can be arbitrarily made within a range that does not impair the main purpose of the present invention. Further, for the purpose of further increasing the silver solubility of the inorganic antibacterial agent of the present invention, the combined use with sodium thiosulfate, an ammonium salt or the like which forms a complex compound with silver can be arbitrarily performed within the range not impairing the object of the present invention. Needless to say.
【発明の効果】以上のように本発明の無機系抗菌剤は、
酸化亜鉛と硫酸銀を担持させた無機系粉末からなるもの
で、合成樹脂、塗料、ゴム等の各種素材に添加した場合
でも優れた抗菌力を示す優れた効果を奏するものであ
る。As described above, the inorganic antibacterial agent of the present invention is
It is composed of an inorganic powder supporting zinc oxide and silver sulfate, and exhibits excellent antibacterial activity even when added to various materials such as synthetic resins, paints and rubbers.
【図１】酸化亜鉛ウイスカの結晶構造を示す電子顕微鏡
写真FIG. 1 is an electron micrograph showing the crystal structure of zinc oxide whiskers.
Claims (3)
鉛からなる無機系抗菌剤。1. An inorganic antibacterial agent comprising an inorganic powder supporting silver sulfate and zinc oxide.
造の単結晶酸化亜鉛であることを特徴とする請求項１記
載の無機系抗菌剤。2. The inorganic antibacterial agent according to claim 1, wherein the zinc oxide is a single crystal zinc oxide having a tetrapod-like three-dimensional crystal structure.
下であり、且つリン酸カルシウム、シリカゲル、硫酸バ
リウム、酸化チタンのうちから選ばれたことを特徴とす
る請求項１記載の無機系抗菌剤。3. The inorganic antibacterial agent according to claim 1, wherein the inorganic powder has an average primary particle size of 10 μm or less and is selected from calcium phosphate, silica gel, barium sulfate and titanium oxide. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30323494A JPH08133918A (en) | 1994-11-11 | 1994-11-11 | Inorganic antimicrobial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30323494A JPH08133918A (en) | 1994-11-11 | 1994-11-11 | Inorganic antimicrobial agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08133918A true JPH08133918A (en) | 1996-05-28 |
Family
ID=17918498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30323494A Pending JPH08133918A (en) | 1994-11-11 | 1994-11-11 | Inorganic antimicrobial agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08133918A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006133857A1 (en) * | 2005-06-16 | 2006-12-21 | Imperial Chemical Industries Plc | Anti-microbial paint films |
| EP1747723A1 (en) | 2005-07-29 | 2007-01-31 | Southwest Jiaotong University | An inorganic antimicrobial agent comprising zinc oxides and silver ions loaded in crystal lattices of the said zinc oxides and preparing method thereof |
| US7261867B1 (en) | 2006-04-07 | 2007-08-28 | Eastman Kodak Company | Production of silver sulfate grains using organo-sulfate or organo-sulfonate additives |
| WO2008089822A2 (en) * | 2007-01-23 | 2008-07-31 | Merck Patent Gmbh | Antimicrobial composition comprising zinc oxide, barium sulphate and silver ions |
| JP2009526822A (en) * | 2006-02-16 | 2009-07-23 | ザッハトレーベン ヒェミー ゲゼルシヤフト ミット ベシュレンクテル ハフツング | Biocidal composition |
| US7655212B2 (en) | 2008-04-11 | 2010-02-02 | Eastman Kodak Company | Production of silver sulfate grains using a fluorinated additive |
| US8062615B2 (en) | 2008-04-11 | 2011-11-22 | Eastman Kodak Company | Production of silver sulfate grains using carboxylic acid additives |
| CN102578148A (en) * | 2012-01-03 | 2012-07-18 | 西南交通大学 | Method for improving antibacterial property of tetrapod-like zinc oxide whisker |
| CN104047114A (en) * | 2014-06-17 | 2014-09-17 | 李文博 | Nano-silver antibacterial melt-blown non-woven fabric and production method thereof |
| JP2016522802A (en) * | 2013-04-16 | 2016-08-04 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Liquid soap with improved antibacterial activity |
| US10370622B2 (en) | 2013-04-16 | 2019-08-06 | Conopco, Inc. | Soap bar having enhanced antibacterial activity |
| CN114854259A (en) * | 2022-05-18 | 2022-08-05 | 来斯奥集成家居股份有限公司 | Water-based art coating with antibacterial function and preparation method thereof |
-
1994
- 1994-11-11 JP JP30323494A patent/JPH08133918A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006133857A1 (en) * | 2005-06-16 | 2006-12-21 | Imperial Chemical Industries Plc | Anti-microbial paint films |
| EP1747723A1 (en) | 2005-07-29 | 2007-01-31 | Southwest Jiaotong University | An inorganic antimicrobial agent comprising zinc oxides and silver ions loaded in crystal lattices of the said zinc oxides and preparing method thereof |
| JP2009526822A (en) * | 2006-02-16 | 2009-07-23 | ザッハトレーベン ヒェミー ゲゼルシヤフト ミット ベシュレンクテル ハフツング | Biocidal composition |
| US7261867B1 (en) | 2006-04-07 | 2007-08-28 | Eastman Kodak Company | Production of silver sulfate grains using organo-sulfate or organo-sulfonate additives |
| WO2008089822A2 (en) * | 2007-01-23 | 2008-07-31 | Merck Patent Gmbh | Antimicrobial composition comprising zinc oxide, barium sulphate and silver ions |
| WO2008089822A3 (en) * | 2007-01-23 | 2009-04-09 | Merck Patent Gmbh | Antimicrobial composition comprising zinc oxide, barium sulphate and silver ions |
| US7655212B2 (en) | 2008-04-11 | 2010-02-02 | Eastman Kodak Company | Production of silver sulfate grains using a fluorinated additive |
| US8062615B2 (en) | 2008-04-11 | 2011-11-22 | Eastman Kodak Company | Production of silver sulfate grains using carboxylic acid additives |
| CN102578148A (en) * | 2012-01-03 | 2012-07-18 | 西南交通大学 | Method for improving antibacterial property of tetrapod-like zinc oxide whisker |
| JP2016522802A (en) * | 2013-04-16 | 2016-08-04 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Liquid soap with improved antibacterial activity |
| US10370622B2 (en) | 2013-04-16 | 2019-08-06 | Conopco, Inc. | Soap bar having enhanced antibacterial activity |
| CN104047114A (en) * | 2014-06-17 | 2014-09-17 | 李文博 | Nano-silver antibacterial melt-blown non-woven fabric and production method thereof |
| CN114854259A (en) * | 2022-05-18 | 2022-08-05 | 来斯奥集成家居股份有限公司 | Water-based art coating with antibacterial function and preparation method thereof |
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