JP3085682B2 - Antimicrobial composition - Google Patents
Antimicrobial compositionInfo
- Publication number
- JP3085682B2 JP3085682B2 JP02074088A JP7408890A JP3085682B2 JP 3085682 B2 JP3085682 B2 JP 3085682B2 JP 02074088 A JP02074088 A JP 02074088A JP 7408890 A JP7408890 A JP 7408890A JP 3085682 B2 JP3085682 B2 JP 3085682B2
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- Japan
- Prior art keywords
- antibacterial
- composition
- antibacterial composition
- ion
- metal ions
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は抗菌性組成物に関し、特に、抗菌力が高く各
種の工業材料、工業製品に利用可能な抗菌性組成物に関
する。The present invention relates to an antibacterial composition, and more particularly to an antibacterial composition having a high antibacterial activity and usable for various industrial materials and products.
銀イオンや銅イオンが細菌や黴などに対する抗菌力を
有することは周知である。そして、抗菌効果の持続性お
よび抗菌物質の安定性を改善する目的で、抗菌性の金属
イオンをゼオライトまたは無定形のアルミノ珪酸塩に担
持した抗菌性組成物が知られている。It is well known that silver ions and copper ions have antibacterial activity against bacteria, molds and the like. An antibacterial composition in which an antibacterial metal ion is supported on zeolite or amorphous aluminosilicate for the purpose of improving the durability of the antibacterial effect and the stability of the antibacterial substance is known.
しかしながら、上記公知の抗菌性組成物と言えども、
抗菌力や抗菌効果の持続性の点で、必ずしも満足のゆく
ものではなかった。However, even with the above known antimicrobial composition,
In terms of antibacterial activity and sustainability of antibacterial effects, it was not always satisfactory.
また、これらの抗菌性組成物の粒状体は分散性が良く
ないので、これら粒状体を各種の樹脂と混合して所望の
形状に成型する場合、成型性が悪いために、成型物の抗
菌力が粒状体の抗菌力と比較して著しく低下するという
問題点があった。In addition, since the particles of these antibacterial compositions have poor dispersibility, when these particles are mixed with various resins and molded into a desired shape, the moldability is poor. However, there is a problem that the antibacterial activity is significantly reduced as compared with the antibacterial activity of the granular material.
本発明は前記問題点を解決するためのもので、その目
的は、抗菌力に優れ、しかも、長期間に亘り抗菌効果を
持続することができて、変色が少なく、耐熱性、耐薬品
性に優れた抗菌性組成物を提供することにある。The present invention is intended to solve the above-mentioned problems, and its object is to excel in antibacterial activity, and also to maintain the antibacterial effect for a long period of time, reduce discoloration, and improve heat resistance and chemical resistance. It is to provide an excellent antibacterial composition.
さらに、本発明は分散性の良い粒状体の抗菌性組成物
を提供することにより、成型物としての抗菌力の低下が
少ない抗菌性組成物提供することにある。Another object of the present invention is to provide a particulate antibacterial composition having good dispersibility, so as to provide an antibacterial composition having a small decrease in antibacterial activity as a molded product.
本発明は、メタ珪酸アルミン酸マグネシウムの金属イ
オンを、抗菌性を有する金属イオンでイオン交換してな
る抗菌性組成物によって上記目的を達成するものであ
る。The present invention achieves the above object by an antibacterial composition obtained by ion-exchanging metal ions of magnesium metasilicate aluminate with metal ions having antibacterial properties.
以下に本発明に係る抗菌性組成物について具体的に説
明する。Hereinafter, the antibacterial composition according to the present invention will be specifically described.
本発明では、抗菌性組成物の母材として、メタ珪酸ア
ルミン酸マグネシウムを用いる。メタ珪酸アルミン酸マ
グネシウムは水に不溶性であり、樹脂中に分散させて使
用するとき等、抗菌性組成物が溶出しにくく、抗菌力が
持続する。また、メタ珪酸アルミン酸マグネシウムは安
全性の点からも好ましい。In the present invention, magnesium aluminate metasilicate is used as a base material of the antibacterial composition. Magnesium metasilicate aluminate is insoluble in water, and when used in a state of being dispersed in a resin, the antibacterial composition is hardly eluted and the antibacterial activity is maintained. Magnesium aluminate metasilicate is also preferred from the viewpoint of safety.
上記無機のオキソ酸の塩は、予め成型したものであっ
ても、粒状のものであってもよい。本発明の抗菌性組成
物を樹脂に添加して所望の形状に成型する場合には、粒
子間の凝集を抑制して、成型体中の分散性を高め、以
て、抗菌性を均一に発現させるために、粒子径は２μｍ
以下、特に、0.5μｍ以下が好ましい。The inorganic oxo acid salt may be preformed or granular. When the antibacterial composition of the present invention is added to a resin and molded into a desired shape, aggregation between particles is suppressed, dispersibility in the molded body is increased, and thus, antibacterial properties are uniformly exhibited. Particle size is 2 μm
The thickness is particularly preferably 0.5 μm or less.
イオン交換される抗菌性を有する金属イオンとして
は、通常、抗菌剤、殺菌剤として使用される金属イオ
ン、例えば、Ag、Cu、Zn、Sn、Hg、Pb、Cdなどの金属イ
オンを用いることができる。特に、Ag、Cu、Zn、Snの金
属イオンは人体に対する安全性の面で望ましい。As the metal ion having antibacterial properties to be ion-exchanged, usually, an antibacterial agent, a metal ion used as a bactericide, for example, a metal ion such as Ag, Cu, Zn, Sn, Hg, Pb, Cd may be used. it can. In particular, metal ions of Ag, Cu, Zn, and Sn are desirable in terms of safety for the human body.
これらの金属イオンは、通常の方法で、前記メタ珪酸
アルミン酸マグネシウムの金属イオンとイオン交換され
る。These metal ions are ion-exchanged with the metal ions of the magnesium metasilicate aluminate in a usual manner.
例えば、Ag、Cu、Zn、Snなどのイオン交換は、水酸化
物を生成するpH値より低く、しかも、メタ珪酸アルミン
酸マグネシウムが溶解しない領域で行われる。即ち、Ag
の場合はpH9〜４、Cuの場合はpH6〜４、Znの場合はpH9
〜４の範囲であって、60℃以上の温度領域が望ましい。For example, ion exchange of Ag, Cu, Zn, Sn and the like is performed in a region lower than the pH value at which hydroxide is formed and in which magnesium metasilicate aluminate is not dissolved. That is, Ag
PH 9-4 for Cu, pH 6-4 for Cu, pH 9 for Zn
And a temperature range of 60 ° C. or more.
上記金属イオンは、塩化物や硫酸塩の形で利用するこ
ともできるが、陰イオンが残りにくい硝酸塩を利用する
のが好ましい。The metal ions can be used in the form of chlorides or sulfates, but it is preferable to use nitrates in which anions hardly remain.
メタ珪酸アルミン酸マグネシウムは、その金属イオン
の一部が抗菌性を有する金属イオンによってイオン交換
されるが、イオン交換される抗菌性の金属イオンの割合
は、メタ珪酸アルミン酸マグネシウムが保有するイオン
交換容量の0.1〜90モル％であることが適当である。さ
らに、抗菌性組成物中のイオン交換された金属イオンは
抗菌性組成物の0.01〜40重量％であることが好ましい。
金属イオンの割合が、上記最小値に満たない場合には、
抗菌性が十分に発揮されず、他方、最大値を越える場合
には、金属イオンが不安定となり、抗菌効果の安定性と
持続性を欠くことになる。In magnesium metasilicate aluminate, some of the metal ions are ion-exchanged by metal ions having antibacterial properties, but the ratio of antibacterial metal ions to be ion-exchanged depends on the ion exchange rate possessed by magnesium metasilicate aluminate. Suitably, it is between 0.1 and 90 mol% of the volume. Further, the ion-exchanged metal ion in the antibacterial composition is preferably 0.01 to 40% by weight of the antibacterial composition.
If the ratio of metal ions is less than the above minimum value,
If the antibacterial properties are not sufficiently exhibited, and if the maximum value is exceeded, the metal ions become unstable, and the antibacterial effect lacks stability and persistence.
イオン交換操作後は、常法に従い、洗浄、乾燥して所
望の抗菌性組成物を得る。なお、乾燥しただけでは抗菌
性の金属イオンが強固に固定されず、溶出し易いので、
乾燥後、300℃以上の温度で焼成することが望ましい。
本発明の抗菌性組成物は、このようにして調製するの
で、自由状態の金属イオンが少なく、加熱や光による酸
化作用を受けにくい。従って、変色を起こさない。After the ion exchange operation, the desired antibacterial composition is obtained by washing and drying according to a conventional method. In addition, antibacterial metal ions are not firmly fixed and are easily eluted only by drying.
After drying, it is desirable to bake at a temperature of 300 ° C. or higher.
Since the antibacterial composition of the present invention is prepared in this manner, the free metal ions are small, and the composition is less susceptible to oxidizing action due to heating or light. Therefore, no discoloration occurs.
本発明の抗菌性組成物はポリエチレン、ポリプロピレ
ンなどの樹脂に混合してその抗菌性を利用することもで
きるが、その場合、メタ珪酸アルミン酸マグネシウムは
ゼオライトのようにはダイラタンシー性を保有しないの
で、成型が容易である。The antibacterial composition of the present invention can also be used by mixing it with a resin such as polyethylene or polypropylene to use the antibacterial property.In that case, magnesium aluminosilicate does not have dilatancy like zeolite, It is easy to mold.
本発明の抗菌性組成物の用途としては、浄水器の濾過
材、人工培地、農業用薬剤、化粧品および医療材料など
が挙げられる。また、塗料、インク顔料などに添加した
り、ポリエチレン、ポリプロピレンなどの非ハロゲン
系、または、ポリ塩化ビニルなどのハロゲン系などのあ
らゆる樹脂に添加して繊維、家庭用品、紙、台所用品、
サニタリー、フィルム、シート、レザー、発泡体等一般
樹脂製品およびパイプ内装材、接着剤、コーキング剤等
の工業、建築材料等に利用可能である。Applications of the antimicrobial composition of the present invention include filtration materials for water purifiers, artificial media, agricultural chemicals, cosmetics, medical materials, and the like. In addition, it can be added to paints, ink pigments, etc., or to any resin such as non-halogens such as polyethylene and polypropylene, or to any resin such as halogens such as polyvinyl chloride.
It can be used for general resin products such as sanitary, film, sheet, leather and foam, and for industrial and building materials such as pipe interior materials, adhesives and caulks.
実施例１ ５の純水に、硝酸銀（AgNO3）3.2gと硝酸銅（Cu（N
O3）２・3H3O）5.7gを溶解し、pHを5.0に調整した。こ
の水溶液にメタ珪酸アルミン酸マグネシウム（Al2O3・M
gO・2SiO2・7H2O、平均粒径0.02μｍ、水分量20重量
％）125gを添加し、再度、pHを5.0に調整し、60℃で１
時間攪拌した。その後、５当量の温水で洗浄し、乾燥
（110℃、４時間）および焼成（600℃、２時間）して、
抗菌性組成物（Ａ）を得た。この抗菌性組成物（Ａ）の
性状を第１表に示す。Example 15 3.2 g of silver nitrate (AgNO 3 ) and copper nitrate (Cu (N
O 3) was dissolved 2 · 3H 3 O) 5.7g, and the pH was adjusted to 5.0. This aqueous solution contains magnesium metasilicate aluminate (Al 2 O 3 · M
gO · 2SiO 2 · 7H 2 O, average particle size 0.02 μm, water content 20% by weight) 125 g, and adjust the pH to 5.0 again.
Stirred for hours. Then, it was washed with 5 equivalents of warm water, dried (110 ° C, 4 hours) and calcined (600 ° C, 2 hours),
An antibacterial composition (A) was obtained. Table 1 shows the properties of the antibacterial composition (A).
参考例１ ５の純水に、硝酸銀（AgNO3）3.2gと硝酸銅（Cu（N
O3）２・3H3O）5.7gを溶解し、pHを5.0に調整した。こ
の水溶液に水酸アパタイト（Ca10（PO4）６（OH）２、
平均粒径0.1μｍ、水分量0.5重量％）100.5gを添加し、
再度、pHを5.0に調整し、60℃で１時間攪拌した。その
後、５当量の温水で洗浄し、乾燥（110℃、４時間）お
よび焼成（600℃、２時間）して、抗菌性組成物（Ｂ）
を得た。この抗菌性組成物（Ｂ）の性状を第１表に示
す。In the pure water of Reference Example 15, 3.2 g of silver nitrate (AgNO 3 ) and copper nitrate (Cu (N
O 3) was dissolved 2 · 3H 3 O) 5.7g, and the pH was adjusted to 5.0. Hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ,
100.5g of average particle size 0.1μm, water content 0.5% by weight)
Again, the pH was adjusted to 5.0 and stirred at 60 ° C. for 1 hour. Thereafter, the composition is washed with 5 equivalents of warm water, dried (110 ° C., 4 hours) and calcined (600 ° C., 2 hours) to obtain the antibacterial composition (B)
I got Table 1 shows the properties of the antibacterial composition (B).
比較例１ ５の純水に、硝酸銀（AgNO3）3.2gと硝酸銅（Cu（N
O3）２・3H3O）5.7gを溶解し、pHを5.0に調整した。こ
の水溶液にＡ型ゼオライト（平均粒径2.0μｍ、水分量2
3重量％）130gを添加し、再度、pHを5.0に調整し、60℃
で１時間攪拌した。その後、５当量の温水で洗浄し、乾
燥（110℃、４時間）および焼成（600℃、２時間）し
て、抗菌性組成物（Ｃ）を得た。この抗菌性組成物
（Ｃ）の性状を第１表に示す。Comparative Example 15 3.2 g of silver nitrate (AgNO 3 ) and copper nitrate (Cu (N
O 3) was dissolved 2 · 3H 3 O) 5.7g, and the pH was adjusted to 5.0. A type zeolite (average particle size 2.0 μm, water content 2
3% by weight), and the pH was adjusted to 5.0 again, and the temperature was adjusted to 60 ° C.
For 1 hour. Thereafter, the resultant was washed with 5 equivalents of warm water, dried (110 ° C., 4 hours) and fired (600 ° C., 2 hours) to obtain an antibacterial composition (C). Table 1 shows the properties of the antibacterial composition (C).
樹脂成型物の成形 上記実施例１、参考例１および比較例１の抗菌性組成
物（Ａ）、（Ｂ）、（Ｃ）を、それぞれ0.5重量％の濃
度となるようにポリエチレンに混合し、溶融延伸して1m
m厚の板に形成した。それぞれの板を（AP）、（BP）、
（CP）とする。 Molding of Resin Molded Product The antimicrobial compositions (A), (B) and (C) of Example 1, Reference Example 1 and Comparative Example 1 were mixed with polyethylene so as to have a concentration of 0.5% by weight, respectively. 1m by melt drawing
It was formed into an m-thick plate. Each board is (AP), (BP),
(CP).
抗菌性組成物の評価 上記実施例１、参考例１および比較例１の抗菌性組成
物を次の方法により評価した。Evaluation of antibacterial composition The antibacterial compositions of Example 1, Reference Example 1 and Comparative Example 1 were evaluated by the following methods.
（１）細菌に対する抗菌力（Halo Test） 無菌水中に抗菌性組成物を5.0重量％含有させて調製
した懸濁液に、直径8mmの濾紙を60分間浸漬し、その
後、懸濁液から濾紙を取り出し風乾した。(1) Antibacterial activity against bacteria (Halo Test) A filter paper having a diameter of 8 mm is immersed in a suspension prepared by containing 5.0% by weight of an antibacterial composition in sterile water for 60 minutes, and then the filter paper is removed from the suspension. Removed and air dried.
生理食塩水中に被検菌を109個/ml懸濁した液を、寒天
培地を入れたシャーレに0.1ml入れ、コンラージ棒で塗
布した。その後、前記濾紙をシャーレの上に置き、32℃
で24時間培養し、阻止帯を測定した。10 nine test bacteria in saline / ml, suspended liquid, placed 0.1ml in a Petri dish containing the agar medium, was applied with a Conradi rod. After that, place the filter paper on a petri dish and set at 32 ° C.
For 24 hours, and the inhibition zone was measured.
被検菌として、エッシェリヒア・コリ（Escherichia
coli）、シュードモナス・エルギノーサ（Pseudomonas
aeruginosa）、スタフィロコッカス・オーレウス（Stap
hylococcus aureuss）の３種を用い、菌の培地は一般細
菌用寒天培地を用いた。Escherichia coli (Escherichia)
coli), Pseudomonas aeruginosa (Pseudomonas)
aeruginosa), Staphylococcus aureus (Stap
hylococcus aureuss), and an agar medium for general bacteria was used as a bacterial medium.
なお、前記樹脂の成型物については、成型物を直径8m
mの円形に切断したものを濾紙の代わりに用いて評価し
た。In addition, regarding the molded article of the resin, the molded article was 8 m in diameter.
The product cut into a circular shape of m was evaluated in place of the filter paper.
（２）真菌の死滅率 無菌生理食塩水に抗菌性組成物を懸濁させて、0.05重
量％濃度の懸濁液を調製し、この懸濁液9mlと被検菌ア
スペルギルス・ニガー（Aspergillus niger）を108個/m
l懸濁した液1mlとを混合して、28℃で24時間接触させ、
生菌数測定法に準じて生菌数を測定した。(2) Death rate of fungus The antibacterial composition was suspended in sterile physiological saline to prepare a suspension having a concentration of 0.05% by weight, and 9 ml of the suspension was combined with the test microorganism Aspergillus niger. 10 8 pieces / m
1 ml of the suspended liquid is mixed and contacted at 28 ° C. for 24 hours,
The viable cell count was measured according to the viable cell count method.
なお、前記樹脂の成型物については、成型物を1mm×2
mm×5mmに切断したもの1gを9mlの無菌生理食塩水に添加
した液を用いて評価した。In addition, regarding the molded article of the resin, the molded article was 1 mm × 2 mm.
Evaluation was performed using a solution obtained by adding 1 g of a piece cut into a size of 5 mm to 9 ml of sterile physiological saline.
（３）耐薬品性テスト 抗菌性組成物を多量の酢酸水溶液（濃度、３重量％）
に室温で５時間浸した後、洗浄、乾燥したものを用い
て、前記（１）細菌に対する抗菌力（Halo Test）を行
い、耐薬品性の評価をした。(3) Chemical resistance test A large amount of acetic acid aqueous solution (concentration: 3% by weight)
After immersion for 5 hours at room temperature, the washed and dried one was subjected to the (1) antibacterial activity against bacteria (Halo Test) to evaluate the chemical resistance.
（４）変色テスト 抗菌性組成物を300℃で２時間空気中で焼成して変色
の程度を観察した。(4) Discoloration test The antibacterial composition was fired in air at 300 ° C. for 2 hours to observe the degree of discoloration.
以上のテストの評価結果を第２表にまとめて示す。な
お、メタ珪酸アルミン酸マグネシウム、水酸アパタイト
およびＡ型ゼオライト自体については、上記テスト
（１）（２）（３）の評価結果は、全て陰性であった。Table 2 summarizes the evaluation results of the above tests. The evaluation results of the above tests (1), (2) and (3) were all negative for magnesium metasilicate aluminate, hydroxyapatite and A-type zeolite itself.
〔発明の効果〕 本発明の抗菌性組成物は従来公知の抗菌性組成物と比
較して、抗菌力が優れている。 [Effect of the Invention] The antibacterial composition of the present invention is superior in antibacterial activity to conventionally known antibacterial compositions.
また、本発明の抗菌性組成物は樹脂と混合した場合に
おいても、抗菌力は僅かしか低下しない。Further, even when the antibacterial composition of the present invention is mixed with a resin, the antibacterial activity is only slightly reduced.
さらに、変色が少なく、耐熱性、耐薬品性に優れてい
るという顕著な結果を有する。Furthermore, there is a remarkable result that the discoloration is small and the heat resistance and the chemical resistance are excellent.
フロントページの続き (56)参考文献 特開 平１−257124（ＪＰ，Ａ) 特開 平２−19308（ＪＰ，Ａ) 特開 平１−238508（ＪＰ，Ａ) 特開 昭63−88109（ＪＰ，Ａ) 特開 平３−193707（ＪＰ，Ａ) 特開 平３−120204（ＪＰ，Ａ) 特開 平２−268104（ＪＰ，Ａ) 特開 平３−271209（ＪＰ，Ａ) 特開 平３−90007（ＪＰ，Ａ) 特開 平３−43457（ＪＰ，Ａ) 特開 平２−180270（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) A01N 59/16 A01N 25/08 A01N 25/12 A01N 59/20 A01N 61/00 A61K 33/24 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (56) References JP-A-1-257124 (JP, A) JP-A-2-19308 (JP, A) JP-A-1-238508 (JP, A) JP-A-63-88109 (JP) JP-A-3-193707 (JP, A) JP-A-3-120204 (JP, A) JP-A-2-268104 (JP, A) JP-A-3-271209 (JP, A) 3-90007 (JP, A) JP-A-3-43457 (JP, A) JP-A-2-180270 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) A01N 59/16 A01N 25/08 A01N 25/12 A01N 59/20 A01N 61/00 A61K 33/24 CA (STN) REGISTRY (STN)
Claims (1)
オンを、抗菌性を有する金属イオンでイオン交換をして
なることを特徴とする抗菌性組成物。1. An antibacterial composition comprising a metal ion of magnesium aluminate metasilicate ion-exchanged with a metal ion having antibacterial properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02074088A JP3085682B2 (en) | 1990-03-24 | 1990-03-24 | Antimicrobial composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02074088A JP3085682B2 (en) | 1990-03-24 | 1990-03-24 | Antimicrobial composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03275627A JPH03275627A (en) | 1991-12-06 |
| JP3085682B2 true JP3085682B2 (en) | 2000-09-11 |
Family
ID=13537077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02074088A Expired - Lifetime JP3085682B2 (en) | 1990-03-24 | 1990-03-24 | Antimicrobial composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3085682B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3448896B2 (en) * | 1992-05-21 | 2003-09-22 | 東亞合成株式会社 | Manufacturing method of antibacterial agent |
| US8486433B2 (en) | 2004-05-07 | 2013-07-16 | Jgc Catalysts And Chemicals Ltd. | Antibacterial deodorant |
| WO2008082007A1 (en) * | 2006-12-29 | 2008-07-10 | Kyowa Chemical Industry Co., Ltd. | Antibacterial particle, method for producing the same and antibacterial composition |
-
1990
- 1990-03-24 JP JP02074088A patent/JP3085682B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03275627A (en) | 1991-12-06 |
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