JP3054926B2 - How to make silver dispersed carbon material - Google Patents
How to make silver dispersed carbon materialInfo
- Publication number
- JP3054926B2 JP3054926B2 JP8060601A JP6060196A JP3054926B2 JP 3054926 B2 JP3054926 B2 JP 3054926B2 JP 8060601 A JP8060601 A JP 8060601A JP 6060196 A JP6060196 A JP 6060196A JP 3054926 B2 JP3054926 B2 JP 3054926B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- pitch
- carbon material
- quinoline
- activated carbon
- 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
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属銀が均一に分
散した炭素材料の製造方法に関する。The present invention relates to a method for producing a carbon material in which metallic silver is uniformly dispersed.
【０００２】[0002]
【従来技術とその問題点】石炭系ピッチ、石油系ピッ
チ、高分子化合物などに銀、コバルト、ルテニウム、銅
などの金属成分を添加して、金属を含有する炭素複合体
を製造する方法は、例えば、特開平4-124105号公報に記
載されている。しかしながら、この方法では、金属成分
として、非常に高価な有機金属を用いているので、経済
的に実用性に欠けるという問題点がある。2. Description of the Related Art A method for producing a metal-containing carbon composite by adding a metal component such as silver, cobalt, ruthenium, or copper to coal-based pitch, petroleum-based pitch, or a polymer compound, For example, it is described in JP-A-4-124105. However, this method has a problem that it is not economically practical because an extremely expensive organic metal is used as the metal component.
【０００３】銀などを含む炭素複合体を活性炭として用
いることも提案されている。例えば、特開昭59-193134
号公報に記載された方法では、活性炭表面に銀を添着さ
せており、また、特開平1-278408号公報に記載された方
法においては、銀を合成ゼオライト表面に添着させ、こ
れを活性炭と混合して使用している。しかしながら、こ
れらの方法では、活性炭の表面に銀を均一に添着するこ
とができないので、炭素複合体を抗菌材として使用する
場合には、銀イオンの溶出量が一定とならず、長期にわ
たって抗菌性の効果を一定に保持することができない。
また、銀を含有する抗菌材を使用する場合には、溶出す
る銀濃度は、米国公衆衛生局（NIH）による飲料水中の
銀濃度規制値（50ppb）を超えてはならないので、添着
する銀の濃度は、自ずから制限を受けることになり、殺
菌性効果の持続時間が短くなるという問題を生じてい
る。It has also been proposed to use a carbon composite containing silver or the like as activated carbon. For example, JP-A-59-193134
In the method described in Japanese Unexamined Patent Application Publication No. H07-189, silver is impregnated on the surface of activated carbon. And use it. However, these methods do not allow silver to be uniformly impregnated on the surface of activated carbon, so that when the carbon composite is used as an antibacterial material, the amount of silver ions eluted is not constant, and the antibacterial properties are not long-term. Cannot be kept constant.
When using silver-containing antibacterial materials, the concentration of silver eluted must not exceed the regulated value of silver (50 ppb) in drinking water by the United States Public Health Service (NIH). Concentrations are naturally limited, giving rise to the problem that the duration of the bactericidal effect is reduced.
【０００４】また、先述の特開平4-124105号公報には、
抗菌性金属超微粒子−炭素複合体に特定の形状を付与す
る技術は、開示されていない。[0004] Also, in the above-mentioned Japanese Patent Application Laid-Open No. 4-124105,
A technique for imparting a specific shape to the antibacterial metal ultrafine particle-carbon composite is not disclosed.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明は、長
期にわたり規制値未満の一定の濃度で銀イオンを溶出さ
せることができるとともに、賦形性に優れた抗菌性炭素
材料を提供することを主な目的とする。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antibacterial carbon material which can elute silver ions at a constant concentration below the regulation value for a long period of time and is excellent in shapeability. Main purpose.
【０００６】[0006]
【課題を解決する手段】本発明者は、上記の様な技術の
現状に鑑み、研究を重ねた結果、炭素材料の出発原料で
ある有機物に酢酸銀を添加し、よく混合した後、炭素化
することにより、金属銀が均一に分散し、抗菌性に優れ
た炭素材料が得られることを見出した。Means for Solving the Problems In view of the above-mentioned state of the art, the present inventor has conducted extensive research and has found that silver acetate is added to an organic substance as a starting material of a carbon material, mixed well, and then carbonized. By doing so, it has been found that metallic silver is uniformly dispersed and a carbon material having excellent antibacterial properties can be obtained.
【０００７】また、有機物に対する酢酸銀の添加方法
は、酢酸銀粉末を製造原料となる有機物に直接添加し、
熱処理を行っても良いが、酢酸銀をキノリン或いはキノ
リンと酢酸の混合溶液に溶解した後、有機物に添加し、
熱処理を行うことにより、銀がより均一に分散した炭素
材料が得られることも、見出した。[0007] In addition, a method of adding silver acetate to an organic substance is that silver acetate powder is directly added to an organic substance as a production raw material,
Although heat treatment may be performed, silver acetate is dissolved in quinoline or a mixed solution of quinoline and acetic acid, and then added to organic matter,
It has also been found that by performing the heat treatment, a carbon material in which silver is more uniformly dispersed can be obtained.
【０００８】すなわち、本発明は、下記の銀分散型炭素
材料の製造方法を提供する； １．銀分散型炭素材料の製造方法において、製造原料で
ある有機物と酢酸銀とを混合した後、混合物を熱処理す
ることを特徴とする銀分散型炭素材料の製造方法。That is, the present invention provides the following method for producing a silver-dispersed carbon material; What is claimed is: 1. A method for producing a silver-dispersed carbon material, comprising: mixing an organic material, which is a production raw material, with silver acetate; and heat-treating the mixture.
【０００９】２．混合物の熱処理を蒸留、重縮合、不融
化、炭素化および賦活化により行う上記項１に記載の銀
分散型炭素材料の製造方法。[0009] 2. Item 2. The method for producing a silver-dispersed carbon material according to Item 1, wherein the heat treatment of the mixture is performed by distillation, polycondensation, infusibility, carbonization, and activation.
【００１０】３．銀分散型炭素材料の製造において、酢
酸銀をキノリンまたはキノリンと酢酸との混合溶液に溶
解し、製造原料である有機物と混合した後、混合物を熱
処理することを特徴とする銀分散型炭素材料の製造方
法。[0010] 3. In the production of a silver-dispersed carbon material, silver acetate is dissolved in quinoline or a mixed solution of quinoline and acetic acid, mixed with an organic material as a raw material, and then heat-treated. Production method.
【００１１】４．混合物の熱処理を蒸留、重縮合、不融
化、炭素化および賦活化により行う上記項３に記載の銀
分散型炭素材料の製造方法。4. Item 4. The method for producing a silver-dispersed carbon material according to Item 3, wherein the heat treatment of the mixture is performed by distillation, polycondensation, infusibility, carbonization, and activation.
【００１２】[0012]
【発明の実施の形態】本発明における炭素材料の製造原
料となる有機物としては、特に制限されず、石炭系重質
油、石油系重質油、溶融性ポリマ−など液状物質のほか
に、木屑、ヤシ殻などの固体物質も挙げられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The organic substance used as a raw material for producing a carbon material in the present invention is not particularly limited, and in addition to liquid substances such as coal-based heavy oil, petroleum-based heavy oil and fusible polymer, wood chips And solid substances such as coconut shells.
【００１３】有機物に対する酢酸銀の混合に際しては、
酢酸銀の粉末を直接有機物に添加し、混合しても良く、
或いは酢酸銀をキノリンまたはキノリンと酢酸との混合
溶液に溶解した後、有機物に加えて混合しても良い。こ
の際、キノリン単独よりも、キノリン−酢酸混合液を使
用することにより、より容易に酢酸銀を溶解させること
ができる。酢酸銀を溶液状態で有機物に添加し、混合す
る場合には、有機物中に酢酸銀をより一層均一に混合す
ることができるので、最終的に得られる銀分散型炭素材
料における銀の分散が均一となり、抗菌材としての性能
が改善できる。When mixing silver acetate with an organic substance,
Silver acetate powder may be added directly to the organic matter and mixed,
Alternatively, silver acetate may be dissolved in quinoline or a mixed solution of quinoline and acetic acid, and then added to an organic substance and mixed. At this time, silver acetate can be more easily dissolved by using a quinoline-acetic acid mixture than quinoline alone. When silver acetate is added to an organic substance in a solution state and mixed, silver acetate can be mixed more uniformly in the organic substance, so that the silver dispersion in the finally obtained silver-dispersed carbon material is uniform. And the performance as an antibacterial material can be improved.
【００１４】酢酸銀をキノリンに溶解させるに際しての
キノリンの温度は、特に限定されるものではないが、操
作上からは常温乃至その近傍の温度が好ましい。溶解温
度が高くなると、会合により再結晶する場合があるが、
抗菌性能などには、何ら影響はない。The temperature of the quinoline in dissolving silver acetate in the quinoline is not particularly limited, but is preferably room temperature or a temperature close to the room temperature in terms of operation. When the dissolution temperature increases, recrystallization may occur due to association,
There is no effect on antibacterial performance.
【００１５】キノリンに酢酸を添加した溶液に酢酸銀を
溶解しておく場合には、加温しても会合による再結晶を
抑えることが出来る。キノリン−酢酸混合溶液中の酢酸
濃度は、特に限定されるものではないが、過剰量を添加
してもより一層の効果の改善が得られることがないの
で、通常0.01〜10wt％程度とする。When silver acetate is dissolved in a solution obtained by adding acetic acid to quinoline, recrystallization due to association can be suppressed even when heated. The concentration of acetic acid in the quinoline-acetic acid mixed solution is not particularly limited. However, even if an excessive amount is added, no further improvement in the effect is obtained, so that the concentration is usually about 0.01 to 10 wt%.
【００１６】酢酸銀をキノリン溶液或いはキノリン−酢
酸混合溶液として使用する場合の溶液中の酢酸銀の濃度
は、特に限定されないが、通常50wt％以下程度である。When silver acetate is used as a quinoline solution or a quinoline-acetic acid mixed solution, the concentration of silver acetate in the solution is not particularly limited, but is usually about 50% by weight or less.
【００１７】炭素材料としての有機物に対する酢酸銀の
添加量は、特に限定されるものではなく、原料である有
機物の炭素化歩留、製品である銀分散型炭素材料の用途
などによって大きく異なり得るため、一般的には炭素材
料中の銀の濃度が通常0.01〜10wt％程度、より好ましく
は0.1〜5wt％程度となる様にすれば良い。The amount of silver acetate to be added to the organic material as the carbon material is not particularly limited, and may vary greatly depending on the carbonization yield of the organic material as the raw material, the use of the silver dispersed carbon material as the product, and the like. Generally, the concentration of silver in the carbon material may be generally about 0.01 to 10% by weight, more preferably about 0.1 to 5% by weight.
【００１８】炭素材料の原料となる有機物への酢酸銀の
混合方法は、特に制限されず、常法に従って、前者に後
者を添加し、均一に混合すればよい。加熱により液状を
呈する有機物の場合には、加熱された液状の有機物に酢
酸銀を添加し、混合することが好ましい。この場合の混
合温度は、有機物の分解を生じない限り、特に限定され
ない。There is no particular limitation on the method of mixing silver acetate with the organic substance used as the raw material of the carbon material, and the latter may be added to the former and uniformly mixed according to a conventional method. In the case of an organic substance which becomes liquid by heating, it is preferable to add silver acetate to the heated liquid organic substance and mix them. The mixing temperature in this case is not particularly limited as long as the organic substance does not decompose.
【００１９】また、有機物に対する酢酸銀含有キノリン
溶液或いは酢酸銀含有キノリン−酢酸溶液の混合方法
も、特に限定されるものでもなく、液体または加熱すれ
ば液体となる有機物原料に対しては、液体状態の原料に
酢酸銀含有溶液を加え、混合すればよい。この時の混合
温度も、原料が分解されない限り、特に限定されるもの
ではない。The method of mixing a silver acetate-containing quinoline solution or a silver acetate-containing quinoline-acetic acid solution with an organic substance is not particularly limited, either. The silver acetate-containing solution may be added to and mixed with the raw materials of the above. The mixing temperature at this time is not particularly limited as long as the raw material is not decomposed.
【００２０】次いで、上記の様にして得られた酢酸銀を
分散含有する有機物は、一般的に知られている熱処理方
法により処理される。この様な熱処理方法としては、蒸
留方法；酸素、オゾンなどの活性ガスを吹き込みながら
熱処理して、重縮合させる方法：窒素、アルゴンなどの
不活性ガスを吹き込みながら熱処理して、重縮合させる
方法など例示される。Next, the organic matter containing silver acetate dispersed therein obtained as described above is treated by a generally known heat treatment method. Examples of such a heat treatment method include a distillation method; a heat treatment while blowing an active gas such as oxygen and ozone; and a polycondensation method: a heat treatment while blowing an inert gas such as nitrogen and argon to perform a polycondensation. Is exemplified.
【００２１】上記で得られた熱処理生成物を原料とし
て、公知の方法により繊維状、粒状、粉末状などの任意
の形状に加工した後、公知の方法により不融化処理また
は／および炭素化または／および賦活処理を行うことに
より、金属銀が均一に分散した繊維状、粒状、粉末状な
どの炭素材料を得ることが出来る。The heat-treated product obtained above is used as a raw material, processed into an arbitrary shape such as fibrous, granular, powdery or the like by a known method, and then infusibilized or / and / or carbonized or / and / or processed by a known method. By performing the activation treatment, it is possible to obtain a fibrous, granular, or powdery carbon material in which metallic silver is uniformly dispersed.
【００２２】或いは、金属銀を分散含有した液状有機物
（例えば、金属銀を分散含有するピッチ）をバインダー
として木屑、ヤシ殻などの固体物質と混合し、成形し、
炭素化または／および賦活処理しても良い。或いは、酢
酸銀を溶解したキノリン溶液に木屑、ヤシ殻などの固体
物質を含浸した後、これを公知の方法で炭素化または／
および賦活処理を行うことにより、金属銀の分散した炭
素材料を製造することが出来る。Alternatively, a liquid organic material containing dispersed metallic silver (for example, a pitch containing dispersed metallic silver) is mixed with a solid substance such as wood chips and coconut shell as a binder, and molded.
It may be carbonized and / or activated. Alternatively, a solid material such as wood chips and coconut shells is impregnated with a quinoline solution in which silver acetate is dissolved and then carbonized by a known method.
By performing the activation treatment, a carbon material in which metallic silver is dispersed can be produced.
【００２３】[0023]
【発明の効果】本発明によれば、金属銀が分散した粉末
状、粒状、繊維状などの任意の形態の炭素材料を容易に
製造することができる。According to the present invention, it is possible to easily produce a powdery, granular, fibrous, or other arbitrary carbon material in which metallic silver is dispersed.
【００２４】また、酢酸銀を予めキノリンまたはキノリ
ン−酢酸混合物に溶解させた状態で原料である有機物に
添加混合する場合には、金属銀がより均一に分散した炭
素材料を得ることができる。When silver acetate is previously dissolved in quinoline or a quinoline-acetic acid mixture and added to and mixed with an organic material as a raw material, a carbon material in which metallic silver is more uniformly dispersed can be obtained.
【００２５】本発明による炭素材料は、抗菌性材料とし
て、従来品に比して、抗菌性効果およびその持続性に優
れており、また、使用時の銀の溶出量をNIHによる規制
値以下に抑制することができる。The carbon material according to the present invention, as an antibacterial material, has an excellent antibacterial effect and its sustainability as compared with conventional products, and the amount of silver eluted during use is less than the value regulated by NIH. Can be suppressed.
【００２６】[0026]
【実施例】以下に実施例および比較例を示し、本発明の
特徴とするところをより一層明らかにする。EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention.
【００２７】実施例１粉末状酢酸銀を有機物に直接添加する実施例 キノリン不溶分3.1wt％を含むコ−ルタ−ルを加熱し、
水分を除去した後、150℃で濾紙を用いて濾過を行い、
キノリン不溶成分を完全に除去した。Example 1 Example in which powdery silver acetate was directly added to an organic substance A coal tar containing 3.1% by weight of a quinoline-insoluble matter was heated,
After removing water, perform filtration using filter paper at 150 ° C,
Quinoline insoluble components were completely removed.
【００２８】次いで、このコ−ルタ−ルを蒸留して、キ
ノリン不溶成分を含まない、軟化点68.2℃のピッチをコ
−ルタ−ル当り72.5wt％の収率で得た。Then, the coal tar was distilled to obtain a pitch having a softening point of 68.2 ° C., containing no quinoline-insoluble component, in a yield of 72.5% by weight per col tar.
【００２９】次いで、得られたピッチ500gを容量１リッ
トルの小型反応器に仕込み、250℃で溶解した後、撹拌
しつつ、粉末の酢酸銀2.0gを徐々に添加し、添加終了後
さらに0.5時間撹拌を行った。Next, 500 g of the obtained pitch was charged into a small reactor having a capacity of 1 liter, and after dissolving at 250 ° C., 2.0 g of powdered silver acetate was gradually added thereto with stirring. Stirring was performed.
【００３０】次いで、上記の小型反応器内のピッチの温
度を330℃まで昇温させた後、常圧撹拌下で５リットル
／分の空気を吹き込みつつ240分間ピッチを重縮合させ
た。Next, after the temperature of the pitch in the small reactor was raised to 330 ° C., the pitch was polycondensed for 240 minutes while blowing air at 5 liters / minute under normal pressure stirring.
【００３１】取得したピッチの軟化点をメトラ−法で測
定したところ、283.2℃であり、ピッチ中の銀の濃度
は、0.39％であった。ピッチの取得量は、306gであつ
た。次いで、上記のピッチをバッチ式のモノホ−ル紡糸
器に仕込み、335℃の溶融温度で、ノズル径0.3mm、巻取
速度300m/の速度で紡糸を行い、ピッチ繊維を得た。When the softening point of the obtained pitch was measured by the Metra method, it was 283.2 ° C., and the silver concentration in the pitch was 0.39%. The amount of the pitch obtained was 306 g. Subsequently, the pitch was charged into a batch type mono-hole spinner, and spun at a melting temperature of 335 ° C. at a nozzle diameter of 0.3 mm and a winding speed of 300 m / to obtain pitch fibers.
【００３２】次いで、上記のピッチ繊維を空気中で常温
から300℃まで昇温速度2.0℃／分の速度で昇温を行い、
さらに300℃で180分間保持して、不融化処理した。Next, the pitch fiber is heated in the air from room temperature to 300 ° C. at a rate of 2.0 ° C./min.
Further, it was kept at 300 ° C. for 180 minutes to perform infusibility treatment.
【００３３】次いで、不融化処理したピッチ繊維を窒素
雰囲気中で常温から850℃まで10℃／分の速度で昇温し
た後、850℃で60分間蒸気と窒素の混合気体により賦活
処理を行い、不融化繊維に対し39.1wt％の収率で活性炭
素繊維を得た。Next, the infusibilized pitch fiber is heated from room temperature to 850 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere, and then activated by a mixed gas of steam and nitrogen at 850 ° C. for 60 minutes. Activated carbon fibers were obtained in a yield of 39.1 wt% based on the infusibilized fibers.
【００３４】得られた活性炭素繊維の平均細孔半径は8.
1Å、比表面積は1306m2/g、Agの含有率は0.88％であ
り、繊維の断面をEPMAで観察したところ、繊維断面全体
にAgが観察された。またESCAでこのAgの電子状態を測定
した結果、金属銀であることが確認された。The average pore radius of the obtained activated carbon fiber is 8.
1 mm, the specific surface area was 1306 m 2 / g, and the Ag content was 0.88%. When the cross section of the fiber was observed by EPMA, Ag was observed over the entire fiber cross section. The electronic state of the Ag was measured by ESCA, and it was confirmed that the Ag was metallic silver.
【００３５】実施例２予めキノリンに溶解した酢酸銀をコ−ルタ−ルに添加す
る実施例 実施例１で用いたと同様のコ−ルタ−ルを実施例１と同
様にして熱処理し、水分とキノリン不溶成分をと除去し
た。Example 2 Silver acetate previously dissolved in quinoline was added to the coal tar.
The same cold tar as used in Example 1 was heat-treated in the same manner as in Example 1 to remove water and quinoline insoluble components.
【００３６】次いで、濾過処理後のコ−ルタ−ル1000g
を蒸留フラスコに入れ、フラスコ内を窒素雰囲気とした
後、コ−ルタ−ルを50〜70℃に加温した。Next, 1000 g of the coal tar after the filtration treatment
Was placed in a distillation flask, and the inside of the flask was set to a nitrogen atmosphere, and then the coal tar was heated to 50 to 70 ° C.
【００３７】次いで、別途にビ−カ−中の100mlのキノ
リンに酢酸銀3.0gを添加し、常温で溶解させた後、フラ
スコ内で加温してあるコ−ルタ−ルに徐々に滴下し、約
0.5時間にわたり撹拌混合を行った。引続き、減圧下で
蒸留を行って、キノリンとコ−ルタ−ル中の軽質分を除
去し、軟化点82.6℃のピッチをコ−ルタ−ル当り60.8wt
％の収率で取得した。Next, 3.0 g of silver acetate was separately added to 100 ml of quinoline in a beaker, dissolved at room temperature, and then gradually dropped into a cold tar heated in the flask. ,about
Stir mixing was performed for 0.5 hour. Subsequently, distillation was carried out under reduced pressure to remove quinoline and light components in the coal tar, and a pitch having a softening point of 82.6 ° C. was added to 60.8 wt.
% Yield.
【００３８】次いで、この軟化点82.6℃のピッチ500gを
容量１リットルの小型の反応容器に仕込み、反応温度33
0℃、反応圧力常圧で撹拌下に5リットル／分の空気を吹
き込みながら、240分間反応を行ったところ、軟化点27
8.1℃のピッチ315gを取得した。このピッチには、銀が
0.46wt％が含まれていた。Next, 500 g of the pitch having a softening point of 82.6 ° C. was charged into a small reaction vessel having a capacity of 1 liter, and the reaction temperature was set at 33 ° C.
The reaction was carried out for 240 minutes while blowing air at 5 ° C./min under stirring at 0 ° C. and reaction pressure of normal pressure.
A pitch of 315 g at 8.1 ° C was obtained. Silver on this pitch
0.46 wt% was contained.
【００３９】次いで、このピッチを使用して実施例１と
同じ方法で紡糸を行った後、さらに実施例１と同じ条件
で不融化および賦活処理を行うことにより、不融化処理
繊維に対し40.2wt％の収率で活性炭素繊維を取得した。Next, spinning is performed in the same manner as in Example 1 using this pitch, and further infused and activated under the same conditions as in Example 1, whereby 40.2 wt. % Of the activated carbon fiber was obtained.
【００４０】得られた繊維状活性炭の平均細孔半径は8.
2Åであり、比表面積は1320m2/g、金属銀の含有率は1.0
2wt％であった。The average pore radius of the obtained fibrous activated carbon was 8.
2Å, specific surface area 1320 m 2 / g, metal silver content 1.0
2 wt%.
【００４１】実施例３予め酢酸−キノリン混合物に溶解した酢酸銀をピッチに
添加する実施例 実施例１で取得した軟化点68.2℃のピッチ500gを容量１
リットルの小型反応容器に仕込み、温度を150〜170℃に
調整して、ピッチを溶解した。Example 3 Silver acetate previously dissolved in an acetic acid-quinoline mixture was used as a pitch.
Example of adding 500 g of pitch having a softening point of 68.2 ° C. obtained in Example 1 to a capacity of 1
A small reaction vessel of 1 liter was charged, and the temperature was adjusted to 150 to 170 ° C. to dissolve the pitch.
【００４２】別途にビ−カ−に0.1wt％の酢酸を含むキ
ノリン50mlに酢酸銀4.60gを添加し、70〜80℃で溶解し
た後、上記の150〜170℃で溶融したピッチに徐々に添加
し、同温度で0.5時間撹拌混合した後、実施例１と同じ
方法で240分間反応を行い、軟化点280.3℃のピッチ310g
を取得した。得られたピッチ中の銀の含有量は0.89wt％
であった。Separately, 4.60 g of silver acetate was added to 50 ml of quinoline containing 0.1% by weight of acetic acid in a beaker, dissolved at 70 to 80 ° C., and gradually added to the pitch melted at 150 to 170 ° C. After adding, stirring and mixing at the same temperature for 0.5 hour, a reaction was carried out for 240 minutes in the same manner as in Example 1, and a 310 g pitch having a softening point of 280.3 ° C.
I got The content of silver in the obtained pitch is 0.89wt%
Met.
【００４３】次いで、このピッチを原料として実施例１
と同じ方法で紡糸を行った後、実施例１と同じ条件で不
融化および賦活処理を行うことにより、不融化処理繊維
に対し40.6wt％の収率で活性炭素繊維を取得した。Next, using this pitch as a raw material,
After spinning in the same manner as described above, infusibilization and activation treatment were performed under the same conditions as in Example 1 to obtain an activated carbon fiber at a yield of 40.6 wt% based on the infusibilized fiber.
【００４４】得られた繊維状活性炭の平均細孔半径は8.
5Åであり、比表面積は1367m2/g、金属銀の含有率は1.9
1wt％であった。The average pore radius of the obtained fibrous activated carbon was 8.
5Å, specific surface area 1367 m 2 / g, metal silver content 1.9
1 wt%.
【００４５】比較例１ 実施例１で取得した軟化点が68.2℃のピッチ600gを容量
１リットルの小型反応器に仕込み、実施例１と同様にし
て反応器を徐々に加温し、反応器内のピッチの温度が15
0℃になった時点から撹拌と減圧を開始し、反応温度が3
30℃になった時点で、常圧下で撹拌を行いながら5リッ
トル／分の空気を吹き込みつつ、240分間の反応を行っ
た。その結果、軟化点282.7℃のピッチ301gを取得し
た。ピッチ中の銀の含有量は１ppm以下であった。Comparative Example 1 A small reactor having a capacity of 1 liter was charged with 600 g of the pitch having a softening point of 68.2 ° C. obtained in Example 1, and the reactor was gradually heated in the same manner as in Example 1. Pitch temperature of 15
When the temperature reached 0 ° C, stirring and decompression were started, and the reaction temperature was reduced to 3 ° C.
When the temperature reached 30 ° C., the reaction was carried out for 240 minutes while blowing air at 5 L / min while stirring under normal pressure. As a result, 301 g of a pitch having a softening point of 282.7 ° C. was obtained. The silver content in the pitch was 1 ppm or less.
【００４６】このピッチを原料として実施例１と同じ方
法で紡糸を行い、ピッチ繊維を得た後、得られたピッチ
繊維を実施例１と同じ条件で不融化処理および賦活処理
して繊維状の活性炭を得た。Using this pitch as a raw material, spinning is performed in the same manner as in Example 1 to obtain pitch fibers, and the obtained pitch fibers are infusibilized and activated under the same conditions as in Example 1 to obtain a fibrous material. Activated carbon was obtained.
【００４７】得られた活性炭素繊維は、ピッチ繊維当り
の収率38.6wt％、平均細孔半径7.8Å比表面積1318m2/
g、Agの含有率は５ppm以下であった。The obtained activated carbon fiber had a yield per pitch fiber of 38.6 wt%, an average pore radius of 7.8 and a specific surface area of 1318 m 2 /
The contents of g and Ag were 5 ppm or less.
【００４８】実施例４ 実施例１、実施例２、実施例３および比較例１で取得し
たそれぞれの繊維状活性炭について、抗菌性を試験し
た。抗菌力試験は、以下の様にして行った。Example 4 Each of the fibrous activated carbons obtained in Example 1, Example 2, Example 3, and Comparative Example 1 was tested for antibacterial properties. The antibacterial test was performed as follows.
【００４９】イ．試験菌株 大腸菌；Escherichia coli IFO 3301 黄色ブドウ球菌；Staphylococcus aureus IFO 12732 ロ．試験菌液の調製 試験菌株をBrain Heart Infusion Agarに接種し、35℃
で24時間培養し、その１白金耳を0.2％肉エキス加普通
ブイヨン培地で37℃で16〜24時間振とう培養した後、減
菌リン酸緩衝液を用いて1000倍に希釈し、減菌リン酸緩
衝液50mlを収容する容積200mlの三角フラスコにこの希
釈菌液1mlを加えて、1ml当りの生菌数が104個となるよ
うに調整した。なお、使用した減菌リン酸緩衝液は、リ
ン酸二水素カリウム34gを精製水5000mlに溶かし、これ
に4wt％の水酸化ナトリウム溶液約175mlを加え、次い
で、pH7.2に調整した後、精製水を加えて全量を1000ml
とし、さらにこの溶液を精製水で800倍に希釈して、調
製した。 ハ．試験方法と試験結果 実施例および比較例で取得した繊維状活性炭、粉末活性
炭および成形活性炭を粉砕し、先に調製した試験菌液に
0.1gを加えて試験液とした。これを25℃で振とうし、1
時間後、2時間後、6時間後および24時間後に試験液中の
生菌数を菌数測定用培地を用いた混釈平板培養法により
測定を行った。B. Test strain E. coli; Escherichia coli IFO 3301 Staphylococcus aureus; Staphylococcus aureus IFO 12732 b. Preparation of test bacterial solution Inoculate the test strain into Brain Heart Infusion Agar,
After 24 hours of shaking culture at 37 ° C in a normal broth medium containing 0.2% meat extract for 16 to 24 hours, dilute 1000 times with sterile phosphate buffer to sterilize in addition the diluted bacterial solution 1ml Erlenmeyer flask volume 200ml housing the phosphate buffer 50 ml, was adjusted so that the number of viable cells per 1ml of 10 4. The sterilized phosphate buffer used was prepared by dissolving 34 g of potassium dihydrogen phosphate in 5000 ml of purified water, adding about 175 ml of a 4 wt% sodium hydroxide solution, adjusting the pH to 7.2, and then purifying the solution. Add water to make 1000ml
The solution was further diluted 800 times with purified water to prepare. C. Test method and test results The fibrous activated carbon, powdered activated carbon and molded activated carbon obtained in the examples and comparative examples were pulverized and mixed with the previously prepared test bacterial solution.
0.1 g was added to prepare a test solution. Shake this at 25 ° C and add 1
After hours, 2 hours, 6 hours, and 24 hours, the number of viable bacteria in the test solution was measured by a pour plate culture method using a culture medium for measuring the number of bacteria.
【００５０】なお、対照として活性炭を添加していない
試験菌液のみについても、同様の試験を行った。As a control, the same test was carried out only for the test bacterial solution to which no activated carbon was added.
【００５１】試験結果について表１および表２に示す。Tables 1 and 2 show the test results.
【００５２】[0052]
【表１】 [Table 1]
【００５３】表１に示す結果から、本発明による銀分散
型の炭素材料が、大腸菌に対して優れた抗菌性を発揮す
ることが明らかである。From the results shown in Table 1, it is clear that the silver-dispersed carbon material according to the present invention exhibits excellent antibacterial properties against Escherichia coli.
【００５４】[0054]
【表２】 [Table 2]
【００５５】表２に示す結果から、本発明による銀分散
型の炭素材料が、黄色ブドウ球菌に対しても優れた抗菌
性を発揮することが明らかである。From the results shown in Table 2, it is clear that the silver-dispersed carbon material according to the present invention exhibits excellent antibacterial properties against Staphylococcus aureus.
【００５６】実施例５ 実施例２で取得した繊維状活性炭と市販の銀添着活性炭
（武田薬品工業（株）製：粒状白鷺WHA 銀の添着量0.7
6wt％）とについて、銀の溶出量の比較試験を行った。Example 5 Fibrous activated carbon obtained in Example 2 and commercially available silver-impregnated activated carbon (manufactured by Takeda Pharmaceutical Co., Ltd .: granular Shirasagi WHA silver impregnation amount 0.7)
6 wt%) and a comparative test of the amount of silver eluted was performed.
【００５７】試験は、サンプル1gを秤取り、300mlの丸
底フラスコに投入し、純水100mlを加え、丸底フラスコ
に還流冷却器を取り付けた後、所定時間沸騰を行い、室
温まで冷却し、濾紙を用いて濾過を行い、濾液中の銀の
溶出量を測定することにより、行った。In the test, 1 g of a sample was weighed, put into a 300 ml round bottom flask, 100 ml of pure water was added, a reflux condenser was attached to the round bottom flask, the mixture was boiled for a predetermined time, and cooled to room temperature. Filtration was performed using filter paper, and the elution amount of silver in the filtrate was measured.
【００５８】試験結果を表３に示す。Table 3 shows the test results.
【００５９】[0059]
【表３】 [Table 3]
【００６０】表３に示す結果から、本発明による銀分散
型炭素材料は、水との接触状態で銀の溶出量が少なく、
飲料水用の抗菌材としてNIHの銀濃度規制（50ppb）を超
えないことが明らかである。From the results shown in Table 3, the silver-dispersed carbon material according to the present invention has a small amount of silver eluted in contact with water,
It is clear that the antibacterial material for drinking water does not exceed the silver concentration regulation of NIH (50 ppb).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松井 久次 大阪府大阪市中央区平野町四丁目１番２ 号 大阪瓦斯株式会社内 (72)発明者 山田 啓明 大阪府大阪市中央区平野町四丁目１番２ 号 大阪瓦斯株式会社内 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hisashi Matsui 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Inside Osaka Gas Co., Ltd. (72) Inventor Hiroaki Yamada Hirano-cho, Chuo-ku, Osaka-shi, Osaka Chome 1-2 Osaka Gas Co., Ltd.
Claims (3)
において、酢酸銀をキノリンまたはキノリンと酢酸とのIn the above, silver acetate is converted to quinoline or quinoline and acetic acid.
混合溶液に溶解し、ピッチ製造原料有機物と混合した後After dissolving in the mixed solution and mixing with the organic material for pitch production
に、該混合物を重縮合反応させて金属銀が均一に分散しThen, the mixture is subjected to a polycondensation reaction to uniformly disperse metallic silver.
たピッチを得、該ピッチを不融化し、炭素化し、賦活すThe pitch, infusibilize, carbonize and activate the pitch
ることを特徴とする銀分散型活性炭素材料の製造方法。A method for producing a silver-dispersed activated carbon material, comprising:
抗菌性銀分散型活性炭素材料。Antibacterial silver dispersed activated carbon material.
素材料が、繊維状、粒状或いは粉末状である活性炭素材Activated carbon material whose material is fibrous, granular or powdered
料。Fees.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8060601A JP3054926B2 (en) | 1996-03-18 | 1996-03-18 | How to make silver dispersed carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8060601A JP3054926B2 (en) | 1996-03-18 | 1996-03-18 | How to make silver dispersed carbon material |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10001899A Division JP3148892B2 (en) | 1999-04-07 | 1999-04-07 | Method for producing silver-dispersed carbon material |
| JP10001999A Division JP3148893B2 (en) | 1999-04-07 | 1999-04-07 | Method for producing silver-dispersed carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09249885A JPH09249885A (en) | 1997-09-22 |
| JP3054926B2 true JP3054926B2 (en) | 2000-06-19 |
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