JP4203572B2 - Method for producing silver antibacterial agent - Google Patents
Method for producing silver antibacterial agent Download PDFInfo
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- JP4203572B2 JP4203572B2 JP05751898A JP5751898A JP4203572B2 JP 4203572 B2 JP4203572 B2 JP 4203572B2 JP 05751898 A JP05751898 A JP 05751898A JP 5751898 A JP5751898 A JP 5751898A JP 4203572 B2 JP4203572 B2 JP 4203572B2
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- Prior art keywords
- silver
- antibacterial agent
- inorganic particles
- nitrate
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Description
【０００１】
【発明の属する技術分野】
本発明は、無機物粒子上に銀を担持させる抗菌剤製造方法に関し、特には、銀を有効成分とする抗菌力の持続性に優れる抗菌剤の製造に関する。
【０００２】
【従来の技術】
銀が優れた抗菌作用を有することは知られている。この銀を利用して抗菌剤を製造することも知られている。このような銀系抗菌剤の製造においては、通常、硝酸銀水溶液を用いてイオン交換作用によりゼオライト等無機物粒子上に銀を担持させ、得られた銀担持無機物粒子を水洗し、加熱乾燥して抗菌剤としている（特開昭６３−２６５８０９号公報）。
【０００３】
【発明が解決しようとする課題】
しかしながら、このようにゼオライト等無機物粒子を硝酸銀水溶液に浸漬し、イオン交換反応を利用して前記無機物粒子に銀を担持させる場合、浸漬処理を行い通常の水洗を行った後のゼオライト等無機物粒子即ち成品の表面になお硝酸イオンが残留し、また硝酸銀が付着しているという現象が見られた。
【０００４】
硝酸イオンまた特に硝酸銀はタンパク質凝固作用や腐食性を有し、酸化力も強いため、得られる抗菌剤における硝酸イオンの残留や硝酸銀の付着は、樹脂や繊維等の有機物質と複合化させる場合、この抗菌剤の残留硝酸イオンや硝酸銀が樹脂等有機物質と反応してこれらを変色させあるいは劣化させるという問題があった。
【０００５】
このような問題に鑑み、本発明は、硝酸銀水溶液に無機物粒子を浸漬させて銀を担持させる銀系抗菌剤の製造において、浸漬処理後の銀担持無機物粒子における硝酸イオンの残留や硝酸銀の付着状態の解消を目的とする。
【０００６】
【課題を解決するための手段】
本発明者等は、上記問題を解決するために鋭意研究を進めた結果、上記硝酸銀の付着は、無機物粒子表面に銀担持処理液の硝酸イオンが残留し、この硝酸イオンが浸漬処理後の水洗によっても十分に除去しきれず、さらに担持された銀と反応し、硝酸銀を再生成することによることを見いだし、この硝酸イオンの残留および硝酸銀の再結晶化を防ぐために、アンモニア水による洗浄を行い、前記無機物粒子２ｇを１００ｃｍ3 の蒸留水中に添加し、１時間撹拌後の溶液中に溶出する硝酸イオン濃度が少なくとも１００重量ｐｐｍ以下になるまで無機物粒子上に残留する硝酸イオン濃度を低減する必要があることを見いだしたものである。
【０００７】
即ち、本発明は、第１に、銀が被覆されてなる無機物粒子であって、前記無機物粒子２ｇを１００ｃｍ3 の蒸留水中に添加し、１時間撹拌後の溶液中に溶出する硝酸イオン濃度が１００重量ｐｐｍ以下である無機物粒子からなることを特徴とする銀系抗菌剤；第２に、前記無機物粒子は粒径が１〜５０μｍであることを特徴とする上記第１記載の銀系抗菌剤；第３に、前記無機物粒子は本質的にゼオライトとリン酸カルシウムとリン酸ジルコニウムと珪酸カルシウムのうちから一種又は二種以上選択されたものからなることを特徴とする上記第１または２記載の銀系抗菌剤；第４に、無機物粒子を硝酸銀水溶液に浸漬し、無機物粒子表面に銀を担持させた後水洗浄する銀担持抗菌剤の製造方法において、前記水洗浄に先立ち３〜１０重量％アンモニア水による洗浄を行うことにより、前記無機物粒子２ｇを１００ｃｍ3 の蒸留水中に添加し、１時間撹拌後の溶液中に溶出する硝酸イオン濃度を１００重量ｐｐｍ以下に低減させるところの銀系抗菌剤の製造方法；第５に、前記無機物粒子は粒径１〜５０μｍで且つ本質的にゼオライトとリン酸カルシウムとリン酸ジルコニウムと珪酸カルシウムのうちから選択された一種又は二種以上のものからなり、前記硝酸銀水溶液における硝酸銀の濃度は０．０１〜１０ｍｏｌ／ｄｍ3 であるところの銀系抗菌剤の製造方法を提供するものである。
【０００８】
【発明の実施の形態】
銀担持用の無機物粒子としては、イオン交換反応性が高い理由からゼオライトとリン酸カルシウムとリン酸ジルコニウムと珪酸カルシウムのうちから一種又は二種以上選択された無機物粒子からなることが好ましい。さらに、この無機物粒子は、銀イオンの担持容量の点と抗菌剤として樹脂等有機物へ混練する際の分散性及び作業性の点から、１〜５０μｍの粒径のものが望ましい。また、１μｍ未満の粒径では無機物粒子そのものの調製にも手間がかかり、経済的に不利である。
【０００９】
前記粒径の無機物粒子に対する硝酸銀濃度については０．０１〜１０ｍｏｌ／ｄｍ3 とすることが好ましい。０．０１ｍｏｌ／ｄｍ3 未満では銀を担持する反応効率が著しく低く、また、１０ｍｏｌ／ｄｍ3 を超えると反応効率がこれ以上あがらず、特にまた、銀担持無機物粒子上への硝酸イオンの残留を増大させるという問題を生じる。
【００１０】
無機物粒子の硝酸銀溶液への浸漬処理後、銀担持無機物粒子は３〜１０重量％アンモニア水で洗浄することにより、前記無機物粒子２ｇを１００ｃｍ3 の蒸留水中に添加し、１時間撹拌後の溶液中に溶出する硝酸イオン濃度を１００重量ｐｐｍ以下にすることができ、これは即ち、無機物粒子上に残存する硝酸イオン濃度を中和分離で低減することができ、引き続く水洗浄により、銀担持無機物粒子を清浄化することができる。従って、アンモニア水洗浄により無機粒子上に残留する硝酸イオン濃度が前記条件を満たせば、得られた銀担持無機物粒子即ち抗菌剤上に硝酸銀が再生成することがなくなり、安全性の面でもより好ましく、また樹脂等有機物質との反応性の低い銀系抗菌剤を得ることができる。なお、このアンモニア水による洗浄手段は非常に有効であり、アンモニア水の濃度が３重量％未満では効果にばらつきがあるが、１０重量％を超えて添加しても不経済である。
【００１１】
【実施例】
〔実施例１〕
平均粒径３μｍのゼオライト粒子１００ｇを硝酸銀濃度１ｍｏｌ／ｄｍ3 の硝酸銀溶液１ｄｍ3 に３０分間浸漬した後、５重量％アンモニア水２０ｄｍ3 で洗浄し、その後、さらに１０ｄｍ3 の水で洗浄し、ヌッチェで濾過、乾燥して銀担持粒子に調製した。前記ゼオライト粒子２ｇを１００ｃｍ3 の蒸留水中に添加し、１時間撹拌後の溶液中に溶出する硝酸イオン濃度をアルカリで中和滴定して算出したが、硝酸イオンは２９．０重量ｐｐｍであった。
【００１２】
この銀担持粒子を酸溶解し、濾過液の銀濃度を誘導結合プラスマ（ＩＣＰ）発光分析法で測定した結果から、銀担持粒子の銀含有量を算出すると３重量％であった。なお、この銀担持粒子についてＸ線回折測定を行った結果においても、水のみで洗浄した従来品の場合は、硝酸銀の存在が認められたのに対し、アンモニア水で洗浄した本発明による成品の場合は、硝酸銀の存在は認められなかった。抗菌性評価は大腸菌および黄色ぶどう球菌に対する最小発育阻止濃度を測定して評価した。両数値はそれぞれ２００μｇ／ｃｍ3 および３００μｇ／ｃｍ3 であった。即ち、安全かつ安定な抗菌性を持つ抗菌剤が生成したことが確認された。
【００１３】
〔実施例２〕
平均粒径５μｍのリン酸ジルコニウム粒子５０ｇを１ｍｏｌ／ｄｍ3 の硝酸銀溶液１ｄｍ3 に３０分間浸漬した後、５重量％アンモニア水２０ｄｍ3 で洗浄し、その後、さらに１０ｄｍ3 の水で洗浄し、ヌッチェで濾過、乾燥して銀担持粒子に調製した。なお、前記リン酸ジルコニウム２ｇを１００ｃｍ3 の蒸留水中に添加し、１時間撹拌後の溶液中に溶出する硝酸イオン濃度をアルカリで中和滴定して算定したが、硝酸イオンは２１．０重量ｐｐｍであった。
【００１４】
この銀担持粒子を酸溶解し、濾過液の銀濃度をＩＣＰ発光分析法で測定した結果から銀担持粒子の銀含有量を算出すると２重量％であった。また、銀担持粒子についてＸ線回折測定を行った結果においても、水のみで洗浄した場合は、硝酸銀の存在が認められたが、アンモニア水で洗浄した場合は、硝酸銀の存在は認められなかった。抗菌性評価は大腸菌および黄色ブドウ球菌に対する最小発育阻止濃度を測定して評価した。両数値は１００μｇ／ｃｍ3 および２００μｇ／ｃｍ3 であった。即ち、安全性があり且つ安定な抗菌性を持つ抗菌剤が生成したことが確認された。
【００１５】
【発明の効果】
本発明によれば、無機物粒子上に銀を担持させた後、銀担持粒子をアンモニア水で洗浄するようにしたことにより、着実に銀担持無機物粒子への硝酸イオンの残留を防止でき、従ってこの硝酸イオンによる硝酸銀の再生成を抑止でき、従ってまた、この銀担持無機物粒子により安全且つ安定した銀系抗菌剤を得ることができるという効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an antibacterial agent in which silver is supported on inorganic particles, and particularly relates to the production of an antibacterial agent having silver as an active ingredient and having excellent antibacterial activity.
[0002]
[Prior art]
It is known that silver has an excellent antibacterial action. It is also known to produce an antibacterial agent using this silver. In the production of such a silver-based antibacterial agent, silver is usually supported on inorganic particles such as zeolite by ion exchange using an aqueous silver nitrate solution, and the resulting silver-supported inorganic particles are washed with water, dried by heating and antibacterial. (Japanese Unexamined Patent Publication No. 63-265809).
[0003]
[Problems to be solved by the invention]
However, when inorganic particles such as zeolite are soaked in an aqueous silver nitrate solution and silver is supported on the inorganic particles using an ion exchange reaction, the inorganic particles such as zeolite after immersion treatment and normal water washing, There was a phenomenon in which nitrate ions still remained on the surface of the product and silver nitrate adhered.
[0004]
Nitrate ions, especially silver nitrate, have protein coagulation and corrosive properties, and have strong oxidizing power. Therefore, residual nitrate ions and adhesion of silver nitrate in the resulting antibacterial agent are not effective when combined with organic substances such as resins and fibers. There is a problem that the residual nitrate ions and silver nitrate of the antibacterial agent react with organic substances such as resins to discolor or deteriorate them.
[0005]
In view of such problems, the present invention provides a silver-based antibacterial agent in which inorganic particles are immersed in an aqueous silver nitrate solution to support silver, and the remaining nitrate ions and the adhesion state of silver nitrate in the silver-supported inorganic particles after the immersion treatment The purpose is to eliminate.
[0006]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the inventors of the present invention have found that the silver nitrate adheres to the surface of the inorganic particles so that the nitrate ions of the silver-supported treatment liquid remain on the surface of the inorganic particles. In order to prevent the remaining nitrate ions and recrystallization of the silver nitrate, it was washed with ammonia water. It is necessary to add 2 g of the inorganic particles to 100 cm 3 of distilled water and reduce the concentration of nitrate ions remaining on the inorganic particles until the concentration of nitrate ions eluted in the solution after stirring for 1 hour is at least 100 ppm by weight or less. I found something.
[0007]
That is, the present invention is firstly inorganic particles coated with silver, wherein 2 g of the inorganic particles are added to 100 cm 3 of distilled water, and the concentration of nitrate ions eluted in the solution after stirring for 1 hour is A silver-based antibacterial agent comprising inorganic particles of 100 ppm by weight or less; second, the silver-based antibacterial agent according to the first item, wherein the inorganic particles have a particle size of 1 to 50 μm 3rdly, the said inorganic substance particle consists of what was essentially chosen from 1 type, or 2 or more types from zeolite, calcium phosphate, zirconium phosphate, and calcium silicate, The silver type | system | group of said 1 or 2 characterized by the above-mentioned Antibacterial agent; fourthly, in the method for producing a silver-carrying antibacterial agent in which inorganic particles are immersed in a silver nitrate aqueous solution and silver is supported on the surface of the inorganic particles and then washed with water; A silver-based antibacterial agent in which 2 g of the inorganic particles are added to 100 cm 3 of distilled water by washing with monia water and the nitrate ion concentration eluted in the solution after stirring for 1 hour is reduced to 100 ppm by weight or less. Fifth, the inorganic particles have a particle size of 1 to 50 μm and consist essentially of one or more selected from zeolite, calcium phosphate, zirconium phosphate and calcium silicate, and the silver nitrate The present invention provides a method for producing a silver-based antibacterial agent, wherein the concentration of silver nitrate in the aqueous solution is 0.01 to 10 mol / dm 3 .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The inorganic particles for supporting silver are preferably composed of one or more inorganic particles selected from zeolite, calcium phosphate, zirconium phosphate and calcium silicate because of high ion exchange reactivity. Further, the inorganic particles preferably have a particle diameter of 1 to 50 μm from the viewpoint of the silver ion carrying capacity and the dispersibility and workability when kneading into an organic substance such as a resin as an antibacterial agent. In addition, when the particle diameter is less than 1 μm, it takes time to prepare the inorganic particles themselves, which is economically disadvantageous.
[0009]
The silver nitrate concentration with respect to the inorganic particles having the particle diameter is preferably 0.01 to 10 mol / dm 3 . If it is less than 0.01 mol / dm 3 , the reaction efficiency for supporting silver is remarkably low, and if it exceeds 10 mol / dm 3 , the reaction efficiency does not increase any more, and in particular, nitrate ions remain on the silver-supported inorganic particles. The problem of increasing.
[0010]
After the immersion treatment of the inorganic particles in the silver nitrate solution, the silver-supported inorganic particles are washed with 3 to 10% by weight ammonia water to add 2 g of the inorganic particles to 100 cm 3 of distilled water, and in the solution after stirring for 1 hour. The concentration of nitrate ions eluted on the inorganic particles can be reduced to 100 ppm by weight or less, that is, the concentration of nitrate ions remaining on the inorganic particles can be reduced by neutralization separation, and the silver-supported inorganic particles can be reduced by subsequent water washing. Can be cleaned. Therefore, if the concentration of nitrate ions remaining on the inorganic particles by washing with aqueous ammonia satisfies the above conditions, silver nitrate is not regenerated on the obtained silver-supported inorganic particles, that is, the antibacterial agent, which is more preferable in terms of safety. In addition, a silver antibacterial agent having low reactivity with an organic substance such as a resin can be obtained. The cleaning means using aqueous ammonia is very effective, and the effect varies when the concentration of aqueous ammonia is less than 3% by weight, but it is uneconomical to add over 10% by weight.
[0011]
【Example】
[Example 1]
After immersing average particle zeolite particles 100g diameter 3μm silver nitrate solution 1 dm 3 of silver nitrate concentration 1mol / dm 3 30 minutes, washed with 5 wt% aqueous ammonia 20 dm 3, then washed further with water 10 dm 3, Nutsche And then dried to prepare silver-supported particles. 2 g of the zeolite particles were added to 100 cm 3 of distilled water, and the nitrate ion concentration eluted in the solution after stirring for 1 hour was calculated by neutralization titration with alkali. The nitrate ion was 29.0 ppm by weight. .
[0012]
The silver-supported particles were acid-dissolved, and the silver content of the silver-supported particles was calculated from the result of measuring the silver concentration of the filtrate by an inductively coupled plasma (ICP) emission analysis method. In the results of X-ray diffraction measurement of these silver-supported particles, the presence of silver nitrate was recognized in the case of the conventional product washed with water alone, whereas the product according to the present invention washed with ammonia water was used. In the case, the presence of silver nitrate was not observed. Antibacterial evaluation was performed by measuring the minimum inhibitory concentration against Escherichia coli and Staphylococcus aureus. Both numerical values were 200 μg / cm 3 and 300 μg / cm 3 , respectively. That is, it was confirmed that an antibacterial agent having safe and stable antibacterial properties was produced.
[0013]
[Example 2]
After immersing average particle zirconium phosphate particles 50g diameter 5μm silver nitrate solution 1 dm 3 of 1 mol / dm 3 30 minutes, washed with 5 wt% aqueous ammonia 20 dm 3, then washed further with water 10 dm 3, Nutsche And then dried to prepare silver-supported particles. In addition, 2 g of the above-mentioned zirconium phosphate was added to 100 cm 3 of distilled water, and the nitrate ion concentration eluted in the solution after stirring for 1 hour was calculated by neutralization titration with alkali. Met.
[0014]
The silver-supported particles were acid-dissolved, and the silver content of the silver-supported particles was calculated from the result of measuring the silver concentration of the filtrate by ICP emission spectrometry. Further, in the result of X-ray diffraction measurement of the silver-supported particles, the presence of silver nitrate was observed when washed with water alone, but the presence of silver nitrate was not observed when washed with aqueous ammonia. . Antibacterial evaluation was performed by measuring the minimum inhibitory concentration against Escherichia coli and Staphylococcus aureus. Both numerical values were 100 μg / cm 3 and 200 μg / cm 3 . That is, it was confirmed that an antibacterial agent having safety and stable antibacterial properties was produced.
[0015]
【The invention's effect】
According to the present invention, after silver is supported on the inorganic particles, the silver-supported particles are washed with aqueous ammonia, so that it is possible to steadily prevent nitrate ions from remaining on the silver-supported inorganic particles. Reproduction of silver nitrate due to nitrate ions can be suppressed, and therefore, a safe and stable silver-based antibacterial agent can be obtained with the silver-supporting inorganic particles.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05751898A JP4203572B2 (en) | 1998-02-23 | 1998-02-23 | Method for producing silver antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05751898A JP4203572B2 (en) | 1998-02-23 | 1998-02-23 | Method for producing silver antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11240812A JPH11240812A (en) | 1999-09-07 |
| JP4203572B2 true JP4203572B2 (en) | 2009-01-07 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05751898A Expired - Fee Related JP4203572B2 (en) | 1998-02-23 | 1998-02-23 | Method for producing silver antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4203572B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040007190A (en) * | 2002-07-15 | 2004-01-24 | 배향수 | Antibiotic agent comprising a colloidal silver and breeding method of a poultry using the same |
| JP4987235B2 (en) * | 2005-02-14 | 2012-07-25 | 日揮触媒化成株式会社 | Zeolite compact |
| JP2009221119A (en) * | 2008-03-14 | 2009-10-01 | Antimicrobial Technology Co Ltd | Silver-based liquid inorganic antibacterial agent |
| KR102576256B1 (en) * | 2021-01-08 | 2023-09-11 | 주식회사 에스폴리텍 | Disinfectant with silver inorganic microbicide and manufacturing method thereof |
| CN113773049B (en) * | 2021-10-08 | 2023-05-12 | 江苏脒诺甫纳米材料有限公司 | Zircon sand whitening emulsion and preparation process thereof |
-
1998
- 1998-02-23 JP JP05751898A patent/JP4203572B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11240812A (en) | 1999-09-07 |
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