JPH09100474A - Production of silver dispersed type carbon material - Google Patents
Production of silver dispersed type carbon materialInfo
- Publication number
- JPH09100474A JPH09100474A JP7258578A JP25857895A JPH09100474A JP H09100474 A JPH09100474 A JP H09100474A JP 7258578 A JP7258578 A JP 7258578A JP 25857895 A JP25857895 A JP 25857895A JP H09100474 A JPH09100474 A JP H09100474A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- softening point
- pitch
- heavy oil
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銀の化合物ある
いは銀を含有する重質油およびピッチの新しい製造方
法、ならびに銀の化合物あるいは銀を含有する重質油
およびピッチを原料として用いる、抗菌性に優れた炭素
繊維、活性炭などの新しい炭素材料の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a novel method for producing a silver compound or a heavy oil and pitch containing silver, and an antibacterial property using a heavy oil and pitch containing a silver compound or silver as a raw material. The present invention relates to a method for producing a new carbon material such as excellent carbon fiber and activated carbon.
【０００２】[0002]
＊重質油…石油系および石炭系の重質油を総称し、石油
蒸留残渣、ナフサ熱分解残渣、エチレンボトム油、石炭
液化油、コールタールなどが例示される， ＊低軟化点ピッチ…上記重質油を蒸留することにより低
沸点成分を除去した、メトラー法（ＡＳＴＭ）による軟
化点が４０〜１５０℃のピッチをいう。* Heavy oil: A generic name for petroleum-based and coal-based heavy oils, and examples include petroleum distillation residue, naphtha pyrolysis residue, ethylene bottom oil, coal liquefied oil, coal tar, etc. * Low softening point pitch ... Above A pitch having a low boiling point component removed by distilling heavy oil and having a softening point of 40 to 150 ° C. according to the METTLER method (ASTM).
【０００３】＊高軟化点ピッチ…上記の重質油または低
軟化点ピッチを（イ）蒸留、（ロ）熱処理または（ハ）
熱処理後蒸留することにより中沸点成分を除去した、メ
トラー法（ＡＳＴＭ）による軟化点が１５０℃以上のピ
ッチをいう。* High softening point pitch: The above heavy oil or low softening point pitch is (a) distilled, (b) heat treated or (c)
A pitch having a softening point of 150 ° C. or higher as measured by the METTLER method (ASTM), in which a medium boiling point component is removed by distillation after heat treatment.
【０００４】＊等方性…偏光顕微鏡により観察した場合
に、光学的組織が等方性を示すことを恵味する。* Isotropic: It is advantageous that the optical structure exhibits isotropicity when observed by a polarization microscope.
【０００５】＊異方性…扁光顕鎌鏡により観察した場合
に、光学的組織が異方性を示すことを意味する。* Anisotropy: It means that the optical structure exhibits anisotropy when observed with a flat microscope.
【０００６】＊炭素繊維…ピッチを紡糸し、不融化処理
した繊維を、（イ）炭化処理したもの、（ロ）賦活処理
したもの、および（ハ）炭化処理し、賦活処理したもの
を包含する。このうち、（ロ）および（ハ）は、賦式活
処理により多孔質化しており、活性炭素繊維ともいう。* Carbon fiber ... Includes (a) carbonized, (b) activated, and (c) carbonized and activated fibers made of pitch-spun and infusibilized fibers. . Of these, (b) and (c) are made porous by the activation treatment and are also called activated carbon fibers.
【０００７】＊活性炭…粉末状または粒状であって、賦
活処理により多孔質化したもの、および上記の活性炭素
繊維をいう。* Activated carbon: Powder or granules which are made porous by activation treatment, and the above-mentioned activated carbon fibers.
【０００８】[0008]
【従来の技術】石炭系ピッチ、石油系ピッチ、高分子化
合物などに対し、銀、コバルト、ルテニウム、銅などの
金属成分源を添加することにより、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４−１２４１
０５号公報に記載されている。しかしながら、この方法
では、金属成分源は、無機金属に比べ非常に高価である
有機金属の形態で使用されているため、経済性の点で実
用的でないという欠点がある。2. Description of the Related Art A method for producing a carbon-containing carbon composite by adding a metal component source such as silver, cobalt, ruthenium or copper to coal-based pitch, petroleum-based pitch, polymer compound, etc. , For example, JP-A-4-1241
No. 05 publication. However, in this method, since the metal component source is used in the form of an organic metal, which is much more expensive than an inorganic metal, it has a drawback that it is not practical in terms of economy.
【０００９】銀などを含む金属−炭素複合体を活性炭と
して用いることも行われている。例えば、特開昭５９−
１９３１３４号公報は、活性炭表面に銀を添着させる方
法を開示しており、特開平−２７８４０８号公報は、銀
を合成ゼオライト表面に添着させ、活性炭と混合して使
用する方法を開示している。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させることがで
きないので、銀イオンの溶出量は、一定とならなず、一
定の抗菌性効果を持続的に発揮させることができない。
また、溶出する銀濃度として、米国公衆衛生局（ＮＩ
Ｈ）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、添加する銀の濃度は、自ずから制
限を受けることになり、活性炭の殺菌性持続時間が短く
なるという問題点を有している。A metal-carbon composite containing silver or the like has also been used as activated carbon. For example, JP-A-59-
Japanese Patent No. 193134 discloses a method of impregnating silver on the surface of activated carbon, and Japanese Patent Laid-Open No. 278408/1994 discloses a method of impregnating silver on the surface of synthetic zeolite and mixing it with activated carbon. However, with these methods, silver cannot be uniformly attached to the surface of the activated carbon, so the amount of silver ions eluted is not constant, and a constant antibacterial effect cannot be exerted continuously.
In addition, as the concentration of silver to be eluted,
The concentration of silver added to drinking water according to (H) must not exceed the regulated value (50 ppb) in drinking water, so the concentration of added silver is naturally limited, and there is a problem that the sterilization duration of activated carbon is shortened. ing.
【００１０】また、上記の特開平４−１２４１０５号公
報には、繊維状活性炭の製造方法については、全く触れ
られていない。Further, the above-mentioned Japanese Patent Application Laid-Open No. 4-124105 does not mention the method for producing fibrous activated carbon at all.
【００１１】[0011]
【発明が解決しようとする課題】従って、本発明は、抗
菌性に優れ、使用時に銀の溶出量が規制値よりも低く、
抗菌性作用を長期にわたり発揮する活性炭の製造方法を
提供することを主な目的とする。Therefore, according to the present invention, the antibacterial property is excellent, and the amount of silver eluted at the time of use is lower than the regulated value.
The main object is to provide a method for producing activated carbon that exhibits an antibacterial action for a long period of time.
【００１２】[0012]
【課題を解決するための手段】本発明者は、上記の様な
技術の現状に鑑みて研究を重ねた結果、活性炭の出発原
料となる重質油または低軟化点ピッチに銀の無機化合物
を配合し、銀の化合物の融点以上または分解点以上の温
度で混合する場合には、均一に分散された銀または銀の
化合物を含有する重質油または低軟化点ピッチが得られ
ること、またこの様な重質油またはピッチをそのまま用
いて、或いはこの様な重質油またはピッチを蒸留するこ
とにより得られる低軟化点ピッチを用いて、或いはこれ
らの重質油、ピッチまたは低軟化点ピッチを用いて、或
いはさらにこれらの重質油または低軟化点ピッチを熱処
理することにより得られる高軟化点ピッチを用いて、炭
素材料を製造する場合には、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 As a result of repeated studies in view of the current state of the art as described above, the present inventor has found that a heavy oil as a starting material of activated carbon or a silver inorganic compound is added to a low softening point pitch. When blended and mixed at a temperature above the melting point or above the decomposition point of the silver compound, a heavy oil or a low softening point pitch containing uniformly dispersed silver or the compound of silver can be obtained. Such a heavy oil or pitch as it is, or a low softening point pitch obtained by distilling such a heavy oil or pitch, or these heavy oil, pitch or low softening point pitch A carbon material having excellent antibacterial properties can be obtained when a carbon material is produced by using or using a high softening point pitch obtained by heat-treating these heavy oils or a low softening point pitch. see It was.
【００１３】すなわち、本発明は、下記の方法を提供す
るものである。That is, the present invention provides the following method.
【００１４】１．重質油に銀化合物を添加し、銀化合物
の融点または分解点以上の温度で混合することを特徴と
する、銀または銀化合物を分散含有する重質油の製造方
法。1. A method for producing a heavy oil containing silver or a silver compound dispersed therein, comprising adding a silver compound to the heavy oil and mixing at a temperature equal to or higher than a melting point or a decomposition point of the silver compound.
【００１５】２．低軟化点ピッチに銀化合物を添加し、
銀化合物の融点または分解点以上の温度で混合すること
を特徴とする、銀または銀化合物を分散含有する低軟化
点ピッチの製造方法。2. Add a silver compound to the low softening point pitch,
A method for producing a low softening point pitch containing silver or a silver compound dispersed therein, which comprises mixing at a temperature equal to or higher than the melting point or the decomposition point of the silver compound.
【００１６】３．上記項１または２に記載の方法で得ら
れた銀または銀化合物を分散含有する重質油または低軟
化点ピッチに酸素またはオゾンを含有する気体を吹き込
みつつ２５０〜４５０℃で熱処理した後、蒸留すること
により、光学的に等方性組織を示し、銀または銀化合物
を分散含有する高軟化点ピッチを得ることを特徴とする
ピッチの製造方法。3. After heat treatment at 250 to 450 ° C. while blowing a gas containing oxygen or ozone into a heavy oil containing a dispersion of silver or a silver compound or a low softening point pitch obtained by the method according to the above item 1 or 2, distillation is performed. By so doing, a pitch having a high softening point that optically exhibits an isotropic structure and contains silver or a silver compound dispersed therein is obtained.
【００１７】４．上記項１または２に記載の方法で得ら
れた銀または銀化合物を分散含有する重質油または低軟
化点ピッチに不活性ガスを吹き込みつつ３５０〜５００
℃で熱処理した後、蒸留することにより、光学的に異方
性の組織を２０％以上含み、銀または銀化合物を分散含
有する高軟化点ピッチを得ることを特徴とするピッチの
製造方法。4. 350 to 500 while blowing an inert gas into a heavy oil or a low softening point pitch containing silver or a silver compound dispersed therein obtained by the method according to the above 1 or 2.
A method for producing a pitch, characterized by obtaining a high softening point pitch containing 20% or more of an optically anisotropic structure and containing silver or a silver compound dispersed therein, by performing a heat treatment at 0 ° C. and then distilling.
【００１８】５．上記項１〜４のいずれかに記載された
方法により製造された銀または銀化合物を分散含有する
重質油、低軟化点ピッチまたは高軟化点ピッチを炭素材
料の製造原料として使用することを特徴とする、銀また
は銀化合物を分散含有する抗菌性に優れた炭素材料の製
造方法。5. A heavy oil containing silver or a silver compound produced by the method according to any one of the above items 1 to 4, a low softening point pitch or a high softening point pitch is used as a raw material for producing a carbon material. A method for producing a carbon material containing silver or a silver compound dispersed therein and having excellent antibacterial properties.
【００１９】６．炭素材料が、活性炭である上記項５に
記載の方法。6. Item 6. The method according to Item 5, wherein the carbon material is activated carbon.
【００２０】７．活性炭が、活性炭素繊維、粒状活性炭
または粉末状活性炭である上記項６に記載の方法。[7] FIG. Item 7. The method according to Item 6, wherein the activated carbon is activated carbon fiber, granular activated carbon or powdered activated carbon.
【００２１】８．炭素材料が、炭素繊維である上記項５
に記載の方法。8. The above item 5 in which the carbon material is carbon fiber
The method described in.
【００２２】９．グリセリンまたはエタノールに溶解し
た硝酸銀を重質油に添加し、混合分散させることを特徴
とする、硝酸銀を分散含有する重質油の製造方法。9. A method for producing a heavy oil containing silver nitrate dispersed therein, comprising adding silver nitrate dissolved in glycerin or ethanol to the heavy oil and mixing and dispersing.
【００２３】１０．グリセリンまたはエタノールに溶解
した硝酸銀を低軟化点ピッチに添加し、混合分散させる
ことを特徴とする、硝酸銀を分散含有する低軟化点ピッ
チの製造方法。10. A method for producing a low softening point pitch containing silver nitrate dispersed therein, which comprises adding silver nitrate dissolved in glycerin or ethanol to the low softening point pitch and mixing and dispersing.
【００２４】１１．上記項９または１０に記載の方法で
得られた硝酸銀を分散含有する重質油または低軟化点ピ
ッチに酸素またはオゾンを含有する気体を吹き込みつつ
２５０〜４５０℃で熱処理した後、蒸留することによ
り、光学的に等方性組織を示し、硝酸銀または銀を分散
含有する高軟化点ピッチを得ることを特徴とするピッチ
の製造方法。11. By heat treating at 250 to 450 ° C. while blowing a gas containing oxygen or ozone into a heavy oil containing silver nitrate dispersed therein or a low softening point pitch obtained by the method according to Item 9 or 10, by distillation, A method for producing a pitch, which is characterized by obtaining a high softening point pitch that shows an optically isotropic structure and contains silver nitrate or silver dispersed therein.
【００２５】１２．上記項９または１０に記載の方法で
得られた硝酸銀を分散含有する重質油または低軟化点ピ
ッチに不活性ガスを吹き込みつつ３５０〜５００℃で熱
処理した後、蒸留することにより、光学的に異方性の組
織を２０％以上含み、硝酸銀または銀を分散含有する高
軟化点ピッチを得ることを特徴とするピッチの製造方
法。12. The heat treatment is performed at 350 to 500 ° C. while blowing an inert gas into the heavy oil containing silver nitrate dispersed therein or the low softening point pitch obtained by the method according to the above item 9 or 10, and then optically distilled. A method for producing a pitch, comprising obtaining a high softening point pitch containing 20% or more of an anisotropic structure and containing silver nitrate or silver dispersed therein.
【００２６】１３．上記項９〜１２のいずれかに記載さ
れた方法により製造された硝酸銀または銀を分散含有す
る重質油、ピッチ、低軟化点ピッチまたは高軟化点ピッ
チを炭素材料の製造原料として使用することを特徴とす
る、硝酸銀または銀を分散含有する抗菌性に優れた活性
炭の製造方法。13. Use of heavy oil containing silver nitrate or silver dispersed therein produced by the method described in any one of the above items 9 to 12, pitch, low softening point pitch or high softening point pitch as a raw material for producing a carbon material. A method for producing activated carbon containing silver nitrate or silver dispersed therein and having excellent antibacterial properties.
【００２７】１４．炭素材料が、活性炭である上記項１
３に記載の方法。14. Item 1 in which the carbon material is activated carbon
3. The method according to 3.
【００２８】１５．活性炭が、活性炭素繊維、粒状活性
炭または粉末状活性炭である上記項１４に記載の方法。15. Item 15. The method according to Item 14, wherein the activated carbon is activated carbon fiber, granular activated carbon or powdered activated carbon.
【００２９】１６．炭素材料が、炭素繊維である上記項
１３に記載の方法。16. Item 14. The method according to Item 13, wherein the carbon material is carbon fiber.
【００３０】[0030]
【発明の実施の態様】本発明においては、前記の用語の
定義で示した様に、石油系および石炭系の全ての重質油
が使用可能である。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as shown in the above definition of terms, all heavy oils of petroleum type and coal type can be used.
【００３１】重質油に添加する銀の化合物としたは、硝
酸銀、亜硝酸銀、酸化銀、塩化銀、臭化銀などの一般的
な銀の無機化合物が挙げられる。これらの化合物を重質
油に直接添加した後、これらの化合物の融点以上または
分解点以上の温度で攪拌下に混合を行うことにより、銀
化合物或いは銀化合物の分解により生成した金属銀が均
一に分散した重質油を製造することができる。Examples of the silver compound added to the heavy oil include general silver inorganic compounds such as silver nitrate, silver nitrite, silver oxide, silver chloride and silver bromide. After directly adding these compounds to heavy oil, by mixing with stirring at a temperature above the melting point or above the decomposition point of these compounds, the silver compound or metallic silver produced by the decomposition of the silver compound is made uniform. A dispersed heavy oil can be produced.
【００３２】また、硝酸銀を使用する場合には、グリセ
リンまたはエタノールに硝酸銀をグリセリンまたはエタ
ノールの沸点未満の温度で溶解し、使用した溶剤の沸点
未満の温度で重質油に添加する。或いは、主溶媒として
のグリセリンまたはエタノールと重質油との相溶性を高
めるために、硝酸銀を含むグリセリンまたはエタノール
にあらかじめキノリン、トルエン、テトラヒドロフラン
などの助溶媒を加えた後、これを重質油に添加し、用い
た主溶媒および助溶媒の沸点未満の温度で全体を混合し
た後、主溶媒および助溶媒を蒸留により除去しても良
い。この場合、重質油中の硝酸銀の分散状態をより一層
向上させることが出来る。When silver nitrate is used, silver nitrate is dissolved in glycerin or ethanol at a temperature lower than the boiling point of glycerin or ethanol and added to heavy oil at a temperature lower than the boiling point of the solvent used. Alternatively, in order to increase the compatibility of glycerin or ethanol as a main solvent with heavy oil, quinoline, toluene, or a cosolvent such as tetrahydrofuran is previously added to glycerin or ethanol containing silver nitrate, which is then added to heavy oil. After adding and mixing the whole at a temperature lower than the boiling points of the main solvent and auxiliary solvent used, the main solvent and auxiliary solvent may be removed by distillation. In this case, the dispersion state of silver nitrate in heavy oil can be further improved.
【００３３】重質油に硝酸銀を添加する場合に用いるグ
リセリンまたはエタノールの量は、特に限定されるもの
ではなく、硝酸銀が溶解する量であればよい。キノリ
ン、トルエンなどの助溶媒についても、特に量的な限定
はない。The amount of glycerin or ethanol used in the case of adding silver nitrate to heavy oil is not particularly limited as long as it dissolves silver nitrate. There is no particular limitation as to the amount of cosolvent such as quinoline and toluene.
【００３４】重質油に対する硝酸銀などの銀化合物の添
加量は、重質油を原料とする所望の炭素材料に応じて、
必要とされる量を添加すれば良い。例えば、銀または銀
化合物を含む重質油または低融点ピッチに空気を吹き込
みながら熱処理を行い、軟化点１５０℃以上の高軟化点
ピッチを取得し、この高軟化点ピッチを微粉砕した後、
不融化処理および賦活処理を行って、粉末活性炭を製造
する場合には、粉末活性炭が所定の抗菌性能（抗菌効果
の程度、持続時間など）を発揮するのに必要な銀の濃度
を担持する様にすれば良い。重質油に対する銀化合物の
添加量は、特に限定されるものではないが、通常０．０
１〜１０重量％（以下単に％とする）程度である。The amount of silver compounds such as silver nitrate added to the heavy oil depends on the desired carbon material made from the heavy oil.
The necessary amount may be added. For example, heat treatment is performed while blowing air into heavy oil or a low melting point pitch containing silver or a silver compound to obtain a high softening point pitch having a softening point of 150 ° C. or higher, and after finely pulverizing the high softening point pitch,
When producing powdered activated carbon by infusibilizing treatment and activation treatment, it is necessary that the powdered activated carbon carry the concentration of silver necessary for exhibiting predetermined antibacterial performance (degree of antibacterial effect, duration, etc.). You can do it. The amount of the silver compound added to the heavy oil is not particularly limited, but is usually 0.0
It is about 1 to 10% by weight (hereinafter simply referred to as%).
【００３５】銀または銀化合物を含む高軟化点ピッチを
紡糸し、不融化し、炭化処理し若しくは炭化処理するこ
となく、賦活して、抗菌性に優れた活性炭素繊維を製造
する場合には、重質油に添加する銀化合物として、硝酸
銀が最も好ましい。添加量は特に限定されるものではな
いが、抗菌性を発揮するに必要な０．０１％を下限と
し、且つピッチの紡糸性を損なわない量、すなわち紡糸
ピッチ中の硝酸銀濃度が１０％以下、より好ましくは５
％以下となる様に、添加することが好ましい。When a high softening point pitch containing silver or a silver compound is spun, infusibilized, carbonized or activated without carbonization to produce activated carbon fibers having excellent antibacterial properties, Silver nitrate is most preferred as the silver compound added to the heavy oil. The addition amount is not particularly limited, but the lower limit is 0.01% necessary for exhibiting antibacterial properties, and an amount that does not impair the spinnability of the pitch, that is, the silver nitrate concentration in the spinning pitch is 10% or less, More preferably 5
It is preferable to add it so that the content becomes less than or equal to%.
【００３６】以下、銀を分散含有する重質油の製造方法
から銀含有炭素材料の製造方法までを順次説明する。Hereinafter, a method for producing a heavy oil containing silver dispersed therein to a method for producing a silver-containing carbon material will be sequentially described.
【００３７】Ｉ．銀含有重質油の製造方法 上述の様に、重質油に銀または銀化合物を加えた混合物
を銀化合物の融点以上または銀化合物の分解点以上の温
度で攪拌混合することにより、銀または銀化合物を含有
する重質油を得る。I. Method for producing silver-containing heavy oil As described above, by stirring and mixing a mixture obtained by adding silver or a silver compound to heavy oil at a temperature not lower than the melting point of the silver compound or not lower than the decomposition point of the silver compound, silver or silver is obtained. A heavy oil containing the compound is obtained.
【００３８】銀化合物として硝酸銀を使用する場合に
は、硝酸銀をグリセリンまたはエタノールに予め溶解さ
せ、これを重質油に加え、全体を攪拌混合することによ
り、銀または銀化合物を含有する重質油を得る。When silver nitrate is used as the silver compound, the silver nitrate is dissolved in advance in glycerin or ethanol, and this is added to the heavy oil, and the whole is stirred and mixed to obtain a heavy oil containing silver or the silver compound. To get
【００３９】また、主溶媒であるグリセリンまたはエタ
ノールと重質油との相溶性を改善して、重質油に対する
硝酸銀の分散状態をより良好ならしめるためには、硝酸
銀を含むグリセリンまたはエタノールにさらにキノリ
ン、トルエン、テトラヒドロフランなどの助溶媒を加え
ておき、これを重質油に加え、全体を攪拌混合すること
により、銀または銀化合物を含有する重質油を得る。Further, in order to improve the compatibility of the heavy oil with glycerin or ethanol as the main solvent and to improve the dispersion state of silver nitrate in the heavy oil, glycerin or ethanol containing silver nitrate is further added. A co-solvent such as quinoline, toluene or tetrahydrofuran is added in advance, this is added to the heavy oil, and the whole is stirred and mixed to obtain a heavy oil containing silver or a silver compound.
【００４０】銀または銀化合物含有重質油が、その後の
工程で熱処理される場合（例えば、熱処理により高軟化
点ピッチとされる場合など）には、重質油から主溶媒ま
たは主溶媒／助溶媒の除去を予め行う必要はない。勿
論、後述の様に、この様な銀または銀化合物含有重質油
を蒸留して低軟化点ピッチを得る際に、重質油中の軽質
分ともに主溶媒または主溶媒／助溶媒を除去しても差し
支えない。When a heavy oil containing silver or a silver compound is heat-treated in a subsequent step (for example, when a high softening point pitch is obtained by heat treatment), the heavy oil is used as a main solvent or a main solvent / auxiliary solvent. It is not necessary to remove the solvent beforehand. Of course, as described later, when such a heavy oil containing silver or a silver compound is distilled to obtain a low softening point pitch, the main solvent or main solvent / cosolvent is removed together with the light components in the heavy oil. It doesn't matter.
【００４１】ＩＩ．銀含有低軟化点ピッチの製造方法 上記で得られた銀または銀化合物を含有する重質油を次
いで蒸留して、低沸点成分を（場合によっては、主溶媒
または主溶媒／助溶媒をも）除去することにより、メト
ラー法（ＡＳＴＭ）による軟化点が４０〜１５０℃程度
の低軟化点ピッチを得る。II. Method for Producing Silver-Containing Low Softening Point Pitch The heavy oil containing silver or silver compound obtained above is then distilled to remove low-boiling components (in some cases, main solvent or main solvent / cosolvent). By removing, a low softening point pitch having a softening point of about 40 to 150 ° C. according to the METTLER method (ASTM) is obtained.
【００４２】或いは、予め調製した低軟化点ピッチに銀
化合物を添加し、銀化合物の融点または分解点以上の温
度で混合することによっても、同様の銀または銀化合物
含有低軟化点ピッチが得られる。Alternatively, a similar low-softening-point pitch containing silver or a silver compound can be obtained by adding a silver compound to a low-softening-point pitch prepared in advance and mixing them at a temperature above the melting point or decomposition point of the silver compound. .
【００４３】ＩＩＩ．高軟化点ピッチの製造方法（１） 上記のＩ．の方法またはＩＩ．の方法で得られた銀また
は銀化合物を含有する重質油または低軟化点ピッチを、
２５０〜４５０℃程度（より好ましくは３００〜４００
℃程度）の温度で、常圧下または減圧下において、酸素
またはオゾンを含む気体を重質油またはピッチ１ｋｇ当
り空気として０．１〜１０ｌ／分程度（より好ましくは
０．２〜５ｌ／分程度）の割合で吹き込みつつ熱処理す
ることにより、光学的組織が等方性であり、メトラー法
（ＡＳＴＭ）による軟化点が１５０〜３５０℃程度で銀
または銀化合物を含む高軟化点ピッチが製造される。III. High softening point pitch manufacturing method (1) Method or II. Heavy oil or low softening point pitch containing silver or a silver compound obtained by the method of
250 to 450 ° C (more preferably 300 to 400)
C.) at atmospheric pressure or under reduced pressure, a gas containing oxygen or ozone is used as heavy oil or air per kg of pitch of about 0.1 to 10 l / min (more preferably about 0.2 to 5 l / min). ), The optical structure is isotropic, and a high softening point pitch containing silver or a silver compound is produced at a softening point of about 150 to 350 ° C. according to the Mettler method (ASTM). .
【００４４】なお、上記Ｉ．の方法において、原料であ
る重質油中のキノリン不溶成分を公知の遠心分離法、濾
過処理法などにより予め除去しておくとともに、銀化合
物として硝酸銀を用いて得られた硝酸銀含有重質油を本
熱処理方法に供する場合には、ピッチの繊維化、球状化
などの賦形性に特に優れた高軟化点ピッチを製造するこ
とができる。The above I. In the method, the quinoline-insoluble component in the heavy oil that is the raw material is previously removed by a known centrifugation method, filtration method, etc., and the silver nitrate-containing heavy oil obtained by using silver nitrate as a silver compound is When subjected to the present heat treatment method, it is possible to produce a high softening point pitch which is particularly excellent in shapeability such as fiberization and spheroidization of pitch.
【００４５】この場合には、高軟化点ピッチの軟化点
は、硝酸銀の融点以上で紡糸ができる様に調整する必要
があり、２００℃〜３００℃程度であることが好まし
い。In this case, the softening point of the high softening point pitch needs to be adjusted so that spinning can be performed at a temperature not lower than the melting point of silver nitrate, and it is preferably about 200 ° C to 300 ° C.
【００４６】また、この場合に、熱処理を硝酸銀の分解
温度である４４４℃以上で行う場合には、銀含有高軟化
点ピッチが得られるのに対し、熱処理を硝酸銀の分解温
度未満で行う場合には、硝酸銀含有高軟化点ピッチが得
られる。Further, in this case, when the heat treatment is carried out at 444 ° C. or higher which is the decomposition temperature of silver nitrate, a high softening point pitch containing silver can be obtained, whereas when the heat treatment is carried out below the decomposition temperature of silver nitrate. Gives a high softening point pitch containing silver nitrate.
【００４７】ＩＶ．高軟化点ピッチの製造方法（２） 或いは、上記のＩ．の方法またはＩＩ．の方法で得られ
た銀または銀化合物を含有する重質油または低軟化点ピ
ッチを、３００〜５００℃程度（より好ましくは３５０
〜４５０℃程度）の温度で、窒素、アルゴンなどの不活
性気体を重質油またはピッチ１ｋｇ当り０．５〜１０リ
ットル／分程度（より好ましくは１〜５リットル／分程
度）の割合で吹き込みつつ熱処理することにより、光学
的異方性組織の割合が２０％以上であり、硝酸銀を含む
高軟化点ピッチが製造される。このピッチのメトラー法
（ＡＳＴＭ）による軟化点も、１５０〜３５０℃程度で
ある。IV. High softening point pitch manufacturing method (2) Method or II. The heavy oil or the low softening point pitch containing silver or a silver compound obtained by the above method is about 300 to 500 ° C. (more preferably 350 ° C.).
At a temperature of about 450 ° C), an inert gas such as nitrogen or argon is blown at a rate of about 0.5 to 10 liters / minute (more preferably about 1 to 5 liters / minute) per kg of heavy oil or pitch. By heat treatment while making it, the ratio of the optically anisotropic structure is 20% or more, and the high softening point pitch containing silver nitrate is produced. The softening point of this pitch by the Mettler method (ASTM) is also about 150 to 350 ° C.
【００４８】なお、上記Ｉ．の方法において、原料であ
る重質油中のキノリン不溶成分を公知の遠心分離法、濾
過処理法などにより予め除去しておくとともに、銀化合
物として硝酸銀を用いて得られた硝酸銀含有重質油を本
熱処理方法に供する場合には、やはりピッチの繊維化、
球状化などの賦形性に特に優れた高軟化点ピッチを製造
することができる。The above I. In the method, the quinoline-insoluble component in the heavy oil that is the raw material is previously removed by a known centrifugation method, filtration method, etc., and the silver nitrate-containing heavy oil obtained by using silver nitrate as a silver compound is When subjected to the present heat treatment method, pitch fiberization,
It is possible to produce a high softening point pitch that is particularly excellent in shapeability such as spheroidization.
【００４９】この場合にも、高軟化点ピッチの軟化点
は、硝酸銀の融点以上で紡糸ができる様に調整する必要
があり、２００℃〜３００℃程度であることが好まし
い。Also in this case, the softening point of the high softening point pitch needs to be adjusted so that spinning can be performed at a temperature equal to or higher than the melting point of silver nitrate, and it is preferably about 200 ° C to 300 ° C.
【００５０】また、この場合にも、熱処理を硝酸銀の分
解温度である４４４℃以上で行う場合には、銀含有高軟
化点ピッチが得られるのに対し、熱処理を硝酸銀の分解
温度未満で行う場合には、硝酸銀含有高軟化点ピッチが
得られる。Also in this case, when the heat treatment is carried out at 444 ° C. or higher, which is the decomposition temperature of silver nitrate, a high softening point pitch containing silver can be obtained, whereas when the heat treatment is carried out below the decomposition temperature of silver nitrate. A high softening point pitch containing silver nitrate can be obtained.
【００５１】Ｖ．抗菌性に優れた炭素材料の製造方法 上記Ｉ．乃至ＩＩＩ．の方法により製造した銀または銀
化合物を含有する重質油、低軟化点ピッチ或いは高軟化
点ピッチを使用して、抗菌性に優れた各種の炭素材料を
製造する。V. Method for producing carbon material having excellent antibacterial property To III. Using the heavy oil containing silver or a silver compound, the low softening point pitch or the high softening point pitch produced by the method described above, various carbon materials having excellent antibacterial properties are produced.
【００５２】（ａ）例えば、銀または銀化合物を含む重
質油または低軟化点ピッチを粒状活性炭を製造する際の
バインダーとして使用することにより、抗菌性に優れた
銀含有粒状活性炭を製造することができる。(A) Production of silver-containing granular activated carbon having excellent antibacterial properties by using, for example, heavy oil containing silver or a silver compound or low softening point pitch as a binder in producing granular activated carbon. You can
【００５３】粒状活性炭は、銀化合物を含む重質油また
は低軟化点ピッチをバインダーとして用いる以外は、常
法とほぼ同様にして実施することができ、銀化合物の分
解温度を上回る温度において、炭素化処理または賦活処
理すればよい。なお、銀化合物の分解温度を超える温度
で調製されたピッチにおいて、すでに金属銀として存在
している場合には、炭素化処理および賦活処理の温度に
制約はない。Granular activated carbon can be prepared in the same manner as in the conventional method, except that heavy oil containing a silver compound or low softening point pitch is used as a binder. Carbon is used at a temperature above the decomposition temperature of the silver compound. It may be activated or activated. In the pitch prepared at a temperature higher than the decomposition temperature of the silver compound, if it is already present as metallic silver, there is no restriction on the temperature of the carbonization treatment and the activation treatment.
【００５４】この様にして製造した粒状活性炭は金属銀
を均一に分散含有しているので、抗菌性に優れている。Since the granular activated carbon thus produced contains metallic silver uniformly dispersed therein, it has excellent antibacterial properties.
【００５５】（ｂ）また、硝酸銀などの銀化合物を含む
高軟化点ピッチから炭素繊維を得る方法としても、常法
を採用すれば良い。(B) Further, as a method for obtaining carbon fibers from a high softening point pitch containing a silver compound such as silver nitrate, a conventional method may be adopted.
【００５６】すなわち、まず、高軟化点ピッチを軟化点
以上の温度で溶融紡糸し、ピッチ繊維を得る。紡糸に際
しては、硝酸銀はピッチ中に均一に分散しており且つ溶
融状態にあるため、支障なく紡糸することができる，次
いで、得られたピッチ繊維を常法に従って不融化処理
し、炭素化処理することにより、金属銀を含む炭素繊維
を容易に製造できる。That is, first, pitch having a high softening point is melt-spun at a temperature equal to or higher than the softening point to obtain a pitch fiber. During spinning, silver nitrate is uniformly dispersed in the pitch and is in a molten state, so spinning can be performed without any problems. Next, the obtained pitch fiber is infusibilized and carbonized by a conventional method. Thereby, the carbon fiber containing metallic silver can be easily manufactured.
【００５７】ピッチ繊維の不融化は、特に限定されるも
のではないが、例えばピッチ繊維を空気、酸素、オゾン
などの活性ガス雰囲気中において、軟化点以下の温度か
ら昇温し、４００℃までの必要な温度で保持することに
より行う。The infusibilization of the pitch fiber is not particularly limited, but for example, the pitch fiber is heated from a temperature below the softening point to 400 ° C. in an atmosphere of an active gas such as air, oxygen or ozone. It is carried out by holding at the required temperature.
【００５８】次いで、不融化したピッチ繊維をアルゴ
ン、窒素などの不活性ガス雰囲気下に７００〜１５００
℃の所定の温度で炭素化することにより、金属銀を含む
炭素繊維を容易に製造できる。Next, the infusibilized pitch fiber is heated to 700 to 1500 in an atmosphere of an inert gas such as argon or nitrogen.
Carbon fiber containing metallic silver can be easily produced by carbonizing at a predetermined temperature of ° C.
【００５９】（ｃ）活性炭素繊維は、上記と同様にして
得た不融化繊維または炭素繊維を公知の方法で賦活処理
することにより、得られる。The activated carbon fiber (c) can be obtained by subjecting the infusible fiber or carbon fiber obtained in the same manner as above to activation treatment by a known method.
【００６０】すなわち、不融化処理した繊維または炭化
処理した繊維を水蒸気、二酸化炭素、酸素、これらの混
合ガス、或いはこれらのガスを窒素などの不活性ガスで
希釈したガスなどの雰囲気下において、６００〜１２０
０℃程度の温度で賦活処理を行うことにより、金属銀を
含む多孔質の炭素繊維を容易に製造できる。That is, the infusibilized fiber or the carbonized fiber is heated in an atmosphere of steam, carbon dioxide, oxygen, a mixed gas of these, or a gas obtained by diluting these gases with an inert gas such as nitrogen. ~ 120
By carrying out the activation treatment at a temperature of about 0 ° C., porous carbon fibers containing metallic silver can be easily manufactured.
【００６１】（ｄ）また、上記のＩＩ．の方法またはＩ
ＩＩ．の方法で得られた銀または銀化合物を含有する低
軟化点ピッチまたは高軟化点ピッチを粉砕して微粉末と
した後、上記（ｂ）および（ｃ）と同様にして、不融化
処理し、炭素化処理することにより、金属銀を含む炭素
粉末が得られる。(D) In addition, the above II. Method or I
II. After pulverizing the low softening point pitch or the high softening point pitch containing silver or a silver compound obtained by the method of (1) to a fine powder, infusibilizing treatment is carried out in the same manner as in the above (b) and (c), A carbon powder containing metallic silver is obtained by the carbonization treatment.
【００６２】また、この金属銀を含有する炭素粉末を賦
活処理することにより、金属銀を含む抗菌性に優れた粉
末状の活性炭が製造できる。By activating the carbon powder containing the metallic silver, powdered activated carbon containing metallic silver and having excellent antibacterial properties can be produced.
【００６３】[0063]
【発明の効果】本発明によれば、金属銀が分散した粉末
炭素、粒状炭素および繊維状炭素を容易に製造すること
ができる。また、これらの炭素材料を賦活して、活性炭
として用いる場合には、従来よりも抗菌効果および抗菌
持続性に優れ、しかも使用時の銀の過度の溶出を抑制し
た活性炭が得られる。According to the present invention, powder carbon, granular carbon and fibrous carbon in which metallic silver is dispersed can be easily produced. Further, when these carbon materials are activated and used as activated carbon, it is possible to obtain activated carbon which is more excellent in antibacterial effect and antibacterial durability than before, and which suppresses excessive elution of silver during use.
【００６４】[0064]
【実施例】以下に実施例および比較例ならびに試験例を
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, comparative examples and test examples will be shown below to further clarify the features of the present invention.
【００６５】実施例１ キノリン不溶分８．１％およびトルエン不溶分７．３％
を含むコールタールを加熱して水分を除去した後、１５
０℃の温度で濾紙を用いて濾過を行い、キノリン不溶成
分を除去した。Example 1 Quinoline insoluble matter 8.1% and toluene insoluble matter 7.3%
After heating coal tar containing water to remove water,
The quinoline-insoluble component was removed by filtration using filter paper at a temperature of 0 ° C.
【００６６】次いで、濾過処理後のコールタール１００
０ｇを蒸留フラスコに入れ、コールタール中の軽質分を
蒸留で除去して、軟化点７０．８℃の低軟化点ピッチを
コールタール当り７０．４％の収率で得た。Then, coal tar 100 after the filtration treatment
0 g was placed in a distillation flask, and light components in coal tar were removed by distillation to obtain a low softening point pitch having a softening point of 70.8 ° C. in a yield of 70.4% based on the coal tar.
【００６７】得られた低軟化点ピッチ６００ｇを容量１
リットルの反応器に仕込み、さらに硝酸銀５ｇを添加
し、窒素雰囲気中圧力１．０ｋｇ／ｃｍ2・Ｇの加圧下
において２５０℃の温度で３時間攪拌混合した。次い
で、反応器内の圧力を常圧に戻し、さらに３３０℃まで
昇温を行いながら、反応圧力を１００ｔｏｒｒまで下
げ、同温度と同圧力下で攪拌を行いながら、空気を４ｌ
／分の速度で吹き込み、１３５分間反応を行なうことに
より、軟化点２７４．２℃、キノリン不溶成分１１．４
％、トルエン不溶成分６９．１％、銀としての含有量
１．０１％の高軟化点ピッチを低軟化点ピッチ当り５
０．４％の収率で得た。600 g of the obtained low softening point pitch was used as the capacity 1
A reactor of 1 liter was charged, 5 g of silver nitrate was further added, and the mixture was stirred and mixed at a temperature of 250 ° C. for 3 hours under a pressure of 1.0 kg / cm 2 · G in a nitrogen atmosphere. Then, the pressure inside the reactor was returned to normal pressure, the reaction pressure was lowered to 100 torr while further raising the temperature to 330 ° C., and while stirring at the same temperature and pressure, 4 l of air was added.
It is blown at a rate of / min and the reaction is carried out for 135 minutes to give a softening point of 274.2 ° C and a quinoline-insoluble component of 11.4.
%, Toluene insoluble component 69.1%, content of silver as 1.01% high softening point pitch per low softening point pitch 5
Obtained in a yield of 0.4%.
【００６８】この高軟化点ピッチをバッチ式のモノホー
ル紡糸器に仕込み、ピッチの溶融温度３２５℃、ノズル
径０．３ｍｍ、巻取速度３００ｍ／分で紡糸を行い、ピ
ッチ繊維を得た。This high softening point pitch was charged into a batch type monohole spinning machine and spun at a pitch melting temperature of 325 ° C., a nozzle diameter of 0.3 mm and a winding speed of 300 m / min to obtain pitch fibers.
【００６９】得られたピッチ繊維を空気中常温から３０
０℃までを２℃／分の速度で昇温し、３００℃で２時間
保持して、不融化処理を行った。The obtained pitch fiber was heated in air from room temperature to 30
The temperature was raised to 0 ° C. at a rate of 2 ° C./min, and the temperature was maintained at 300 ° C. for 2 hours to perform infusibilization treatment.
【００７０】次いで、不融化処理したピッチ繊維を、窒
素雰囲気中常温から１０００℃まで１０℃／分の速度で
昇温し、１０００℃で１０分間保持して、炭素繊維を得
た。Next, the infusibilized pitch fiber was heated in a nitrogen atmosphere from room temperature to 1000 ° C. at a rate of 10 ° C./min and held at 1000 ° C. for 10 minutes to obtain a carbon fiber.
【００７１】得られた炭素繊維の物性は、繊維径１６μ
ｍ、引張強度９８ｋｇ／ｍｍ2、伸び２％、金属銀の合
有量１．１１％であった。The physical properties of the obtained carbon fiber are 16 μm in diameter.
m, the tensile strength was 98 kg / mm 2 , the elongation was 2%, and the content of metallic silver was 1.11%.
【００７２】さらに、この炭素繊維を水蒸気と窒素の混
合ガスの存在下において８００℃で３５分間賦活処理を
行ったところ、比表面積が１３０８ｍ2／ｇ、平均細孔
径８．６Åの繊維状の活性炭を炭素繊維当り３６．３１
％の収率で取得した。繊維状活性炭中の銀の濃度は、
３．０２％であった。Further, when this carbon fiber was subjected to activation treatment at 800 ° C. for 35 minutes in the presence of a mixed gas of steam and nitrogen, a fibrous activated carbon having a specific surface area of 1308 m 2 / g and an average pore diameter of 8.6Å was obtained. 36.31 per carbon fiber
Obtained in% yield. The concentration of silver in fibrous activated carbon is
It was 3.02%.
【００７３】実施例２ 実施例１と同様のコールタールを使用して実施例１と同
様の方法で水分の除去と濾過とを行い、キノリン不溶成
分を除去した。Example 2 Using the same coal tar as in Example 1, water was removed and filtration was carried out in the same manner as in Example 1 to remove the quinoline-insoluble component.
【００７４】得られたコールタールを蒸留して、軟化点
６９．８℃で、キノリン不溶成分を含まない低軟化点ピ
ッチをコールタール当り７３．２％の収率で得た。The obtained coal tar was distilled to obtain a low softening point pitch having a softening point of 69.8 ° C. and containing no quinoline-insoluble component in a yield of 73.2% based on the coal tar.
【００７５】次いで、低軟化点ピッチ６００ｇ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、１５
０〜１７０℃に加温した。Next, 600 g of the low softening point pitch was put in a distillation flask and the inside of the flask was made into a nitrogen atmosphere.
Warmed to 0-170 ° C.
【００７６】別にビーカーにグリセリン６０ｍｌを入
れ、８０〜ｌ００℃に加温を行った後、硝酸銀２ｇを加
え、硝酸銀をグリセリンに溶解させ、さらにキノリン６
０ｍｌを加え、混合を行った。Separately, 60 ml of glycerin was placed in a beaker, heated to 80 to 100 ° C., 2 g of silver nitrate was added, the silver nitrate was dissolved in glycerin, and quinoline 6 was added.
0 ml was added and mixed.
【００７７】次いで、硝酸銀を溶解させたグリセリンと
キノリンとの混合溶液を、予めフラスコ内で加温してあ
る低軟化点ピッチに徐々に滴下し、２時間攪拌混合を行
った。Then, a mixed solution of glycerin and quinoline in which silver nitrate was dissolved was gradually added dropwise to the low softening point pitch which had been heated in the flask in advance, and the mixture was stirred and mixed for 2 hours.
【００７８】次いで、硝酸銀を溶解したグリセリン−キ
ノリン混合物を含む低軟化点ピッチを容量１リットルの
反応器内に仕込み、反応器を徐々に加温し、反応器内の
ピッチの温度が１００℃になった時点で攪拌と減圧を開
始し、反応温度が３３０℃になった時点で、反応圧力を
１５０torrに調整し、攪拌下に５１／分の空気を吹き込
みながら、１５０分間の反応を行った。Next, a low softening point pitch containing a glycerin-quinoline mixture in which silver nitrate was dissolved was charged into a reactor having a capacity of 1 liter, and the reactor was gradually heated to bring the pitch temperature in the reactor to 100 ° C. When the reaction temperature reached 330 ° C., the reaction pressure was adjusted to 150 torr and the reaction was carried out for 150 minutes while blowing 51 / min of air under stirring.
【００７９】得られた高軟化点ピッチの性状は、軟化点
＝２６４．８℃、キノリン不溶成分＝９．０％、トルエ
ン不溶成分＝６８．５％、銀としての含有量＝０．３７
％であった。The properties of the obtained high softening point pitch are as follows: softening point = 264.8 ° C., quinoline insoluble component = 9.0%, toluene insoluble component = 68.5%, silver content = 0.37.
%Met.
【００８０】高軟化点ピッチの収率は、低軟化点ピッチ
当り５５．４％であった。The yield of high softening point pitch was 55.4% per low softening point pitch.
【００８１】次いで、このピッチを実施例１と同じパッ
チ式のモノホール紡糸器に仕込み、ピッチの溶融温度３
１５℃、ノズル径０．３ｍｍ、巻取速度８００ｍ／分で
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に供した。Next, this pitch was charged into the same patch type monohole spinning machine as in Example 1, and the melting temperature of the pitch was 3
Spinning was performed at 15 ° C., a nozzle diameter of 0.3 mm, and a winding speed of 800 m / min to obtain pitch fibers, and the obtained pitch fibers were subjected to infusibilization treatment under the same conditions as in Example 1.
【００８２】次いで、不融化処理したピッチ繊維を窒素
雰囲気中常温から８００℃まで１０℃／分の速度で昇温
し、８００℃で水蒸気と窒素との混合気体により３０分
間賦活処理を行い、ピッチ繊維当り３５．２％の収率で
活性炭素繊維を得た。Then, the infusibilized pitch fiber is heated in a nitrogen atmosphere from room temperature to 800 ° C. at a rate of 10 ° C./min, and activated at 800 ° C. for 30 minutes with a mixed gas of steam and nitrogen to give a pitch. Activated carbon fiber was obtained in a yield of 35.2% per fiber.
【００８３】得られた活性炭素繊維の平均細孔半径は、
８．３Å、比表面積は１２７２ｍ2／ｇ、銀の含有率は
０．９８％であった。活性炭素繊維の断面を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
It had a specific surface area of 1272 m 2 / g and a silver content of 0.98%. When the cross section of the activated carbon fiber was observed by EPMA, Ag was observed over the entire cross section of the fiber. In addition, as a result of measuring the electronic state of this Ag by ESCA, it was confirmed to be metallic silver.
【００８４】実施例３ 実施例１と同様のコールタールを使用して実施例１と同
様の方法で水分の除去と濾過を行い、キノリン不溶成分
を除去した。Example 3 Using the same coal tar as in Example 1, water was removed and filtration was performed in the same manner as in Example 1 to remove the quinoline-insoluble component.
【００８５】次いで、濾過処理後のコールタール１００
０ｇ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、コールタールを８０〜１００℃に加温した。Then, coal tar 100 after filtration treatment
0 g was put in a distillation flask, the inside of the flask was made a nitrogen atmosphere, and then coal tar was heated to 80 to 100 ° C.
【００８６】別に、ビーカーにグリセリン５０ｍｌを秤
取り、８０〜１００℃に加温し、硝酸銀１．６５ｇを加
え、硝酸銀をグリセリンに溶解させた後、硝酸銀を溶解
したグリセリンを先にフラスコ内で加温しておいたコー
ルタールに徐々に滴下し、３時間攪拌混合した。Separately, 50 ml of glycerin was weighed in a beaker, heated to 80 to 100 ° C., 1.65 g of silver nitrate was added, silver nitrate was dissolved in glycerin, and glycerin in which silver nitrate was dissolved was first added in the flask. The mixture was gradually added dropwise to warm coal tar, and mixed by stirring for 3 hours.
【００８７】次いで、硝酸銀を溶解したグリセリンを含
むコールタールを蒸留し、グリセリンとコール夕一ル中
の軽質分を除去して、軟化点８３．６℃の低軟化点ピッ
チをコールタール当り６０．５％の収率で得た。Then, the coal tar containing glycerin in which silver nitrate was dissolved was distilled to remove light components in the glycerin and the coal batch, and a low softening point pitch with a softening point of 83.6 ° C. was set to 60.60 per coal tar. Obtained in a yield of 5%.
【００８８】得られた低軟化点ピッチ６００ｇを更に容
量１リットルの反応器に仕込み、反応温度３３０℃、反
応圧力常圧で攪拌下に５ｌ／分の空気を吹き込みなが
ら、２８０分間反応を行ったところ、軟化点＝２７６．
１℃、キノリン不溶成分３１．４％、トルエン不溶成分
６７．８％、銀としての含有量＝０．２５％の高軟化点
ピッチが、低軟化点ピッチ当り６９．０％の収率で得ら
れた。600 g of the obtained low softening point pitch was further charged into a reactor having a capacity of 1 liter, and the reaction was carried out for 280 minutes at a reaction temperature of 330 ° C. and at a reaction pressure and atmospheric pressure while blowing 5 l / min of air with stirring. However, softening point = 276.
A high softening point pitch of 11.4 ° C., a quinoline insoluble component 31.4%, a toluene insoluble component 67.8%, and a silver content = 0.25% was obtained at a yield of 69.0% per low softening point pitch. Was given.
【００８９】次いで、この高軟化点ピッチを実施例１と
同じ紡糸器を用い、３２５．８℃の温度で紡糸を行った
後、実施例１と同様にしてピッチ繊維の不融化処理を行
い、不融化処理したピッチ繊維を窒素雰囲気中で常温か
ら７５０℃まで１０℃／分の速度で昇温し、７５０℃で
蒸気と窒素の混合気体により６０分間賦活処理を行うこ
とにより、不融化繊維に対し４３％の収率で活性炭素繊
維を得た。Next, this high softening point pitch was spun at the temperature of 325.8 ° C. using the same spinning machine as in Example 1, and then the pitch fibers were infusibilized in the same manner as in Example 1, By heating the infusibilized pitch fiber in a nitrogen atmosphere from room temperature to 750 ° C. at a rate of 10 ° C./min, and activating the mixed gas of steam and nitrogen at 750 ° C. for 60 minutes, an infusible fiber is obtained. Activated carbon fiber was obtained in a yield of 43%.
【００９０】得られた活性炭素繊維の平均細孔半径は
７．１Å、比表面積は１１１２ｍ2／ｇ、金属銀の含有
率は０．５８％であった。この繊維断面をＥＳＣＡで観
察したところ、実施例２と同じように金属銀が観察され
た。The activated carbon fiber thus obtained had an average pore radius of 7.1Å, a specific surface area of 1112 m 2 / g and a metal silver content of 0.58%. When the cross section of this fiber was observed by ESCA, metallic silver was observed as in Example 2.
【００９１】実施例４ 実施例１で用いたと同様のキノリン不溶分８．１％およ
びトルエン不溶分７．３％を含むコールタール２０００
ｇを濾過処理を行うことなく、蒸留フラスコに入れ、フ
ラスコ内を窒棄雰囲気とした後、８０〜ｌ００℃に加温
し、酸化銀の微粉末１０ｇを加え、同温度で３時間攪拌
混合を行った。Example 4 Coal tar 2000 containing the same quinoline insoluble matter 8.1% and toluene insoluble matter 7.3% as used in Example 1.
g was put into a distillation flask without performing a filtration treatment, and after the inside of the flask was made into a scrubbing atmosphere, it was heated to 80 to 100 ° C., 10 g of silver oxide fine powder was added, and the mixture was stirred and mixed at the same temperature for 3 hours. went.
【００９２】上記で得た銀含有コールタールを攪拌を行
いつつ蒸留し、コールタール中の軽質分を除去して、コ
ールタール当り６８．４％の収率で軟化点７３．４℃の
低軟化点ピッチを得た。この低軟化点ピッチの軟化点以
外の物性は、キノリン不溶成分＝５．６％、トルエン不
溶成分＝１４．３％、銀濃度＝０．６６％であった。次
いで、この低軟化点ピッチ５００ｇを容量１リットルの
反応器に仕込み、反応温度３３０℃、反応圧力常圧で攪
拌下に５ｌ／分の空気を吹き込みつつ、２８０分間反応
を行ったところ、軟化点＝３０３．２℃、キノリン不溶
成分＝４６．５％、トルエン不溶成分＝７４．８％、銀
としての含有量＝１．２０％の高軟化点ピッチが、低軟
化点ピッチ当り５３．６％の収率で得られた。The silver-containing coal tar obtained above was distilled with stirring to remove light components in the coal tar, and the softening point was lowered to 73.4 ° C. at a softening point of 68.4% based on the coal tar. Got the point pitch. The physical properties of the low softening point pitch other than the softening point were quinoline insoluble component = 5.6%, toluene insoluble component = 14.3%, and silver concentration = 0.66%. Next, 500 g of this low softening point pitch was charged into a reactor having a capacity of 1 liter, and a reaction was carried out for 280 minutes while blowing air at 5 l / min with stirring at a reaction temperature of 330 ° C. and a normal reaction pressure, and the reaction was carried out for 280 minutes. = 303.2 ° C., quinoline insoluble component = 46.5%, toluene insoluble component = 74.8%, content as silver = 1.20%, high softening point pitch is 53.6% per low softening point pitch. It was obtained with a yield of.
【００９３】次いで、得られた高軟化点ピッチを微粉砕
し、平均粒径８μｍの粉末ピッチを得た後、その５０ｇ
を小型のローターリーキルンに仕込み、空気を通しなが
ら、常温から３３０℃まで徐々に昇温して不融化処理を
行った。Then, the obtained high softening point pitch was finely pulverized to obtain a powder pitch having an average particle size of 8 μm, and then 50 g thereof
Was charged in a small rotary kiln, and the temperature was gradually raised from room temperature to 330 ° C. while passing air through the infusibilizing treatment.
【００９４】次いで、不蝕化処理したピッチ粉末を不融
化処理に用いたローターリーキルン中窒素雰囲気下で３
００℃まで昇温した後、雰囲気を蒸気と窒素との混合気
体に切り替え、４５分間賦活処理を行い、高軟化点ピッ
チ粉末を基準として、３２％の収率で活性炭粉末を得
た。Next, the pitch powder subjected to the non-corrosion treatment was used in the rotory kiln used for the non-corrosion treatment in a nitrogen atmosphere at 3
After the temperature was raised to 00 ° C., the atmosphere was switched to a mixed gas of steam and nitrogen, and activation treatment was performed for 45 minutes to obtain activated carbon powder in a yield of 32% based on the high softening point pitch powder.
【００９５】得られた活性炭の平均細孔半径は９．８
Å、比表面積は１８２３ｍ2／ｇ、金属銀の含有率は
３．６５％であった。The average pore radius of the obtained activated carbon is 9.8.
Å The specific surface area was 1823 m 2 / g, and the content ratio of metallic silver was 3.65%.
【００９６】実施例５ 実施例４と同様にして得た軟化点７８．４℃の低軟化点
ピッチ５００ｇを容量１リットルの反応器に仕込み、反
応温度４３０℃、反応圧力常圧で攪拌下に５ｌ／分の窒
素ガスを吹き込みながら、３８０分間反応を行った。そ
の結果、軟化点３１６．２℃、キノリン不溶成分８６．
２％、トルエン不溶成分９４．８％、偏光顕微鏡観察に
よる光学的異方性組織が８０％、銀含有量が１．９０％
である高軟化点ピッチが、低軟化点ピッチ当り３３．４
％の収率で得られた。Example 5 500 g of a low softening point pitch having a softening point of 78.4 ° C. obtained in the same manner as in Example 4 was charged into a reactor having a capacity of 1 liter, and the reaction temperature was 430 ° C. and the reaction pressure was normal pressure with stirring. The reaction was performed for 380 minutes while blowing nitrogen gas at 5 l / min. As a result, the softening point was 316.2 ° C. and the quinoline-insoluble component was 86.
2%, toluene insoluble component 94.8%, optically anisotropic structure by polarization microscope observation 80%, silver content 1.90%
The high softening point pitch is 33.4 per low softening point pitch.
% Yield.
【００９７】次いで、高軟化点ピッチを微粉砕し、平均
粒径９μｍの粉末ピッチを得た後、この粉末ピッチ５０
ｇを実施例４と同様にして小型のローターリーキルンに
仕込み、空気を通しながら常温から３５０℃まで徐々に
昇温して、不融化処理を行った。Next, the high softening point pitch was finely pulverized to obtain a powder pitch having an average particle size of 9 μm, and the powder pitch 50
In the same manner as in Example 4, g was charged into a small rotary kiln, and the temperature was gradually raised from room temperature to 350 ° C. while passing air through the infusibilizing treatment.
【００９８】次いで、不融化処理したピッチ粉末を不融
化処理に用いたと同じローターリーキルン中で窒素雰囲
気下８００℃まで昇温した後、雰囲気を蒸気と窒素との
混合気体に切り替え、７５分問賦活処理を行い、ピッチ
粉末に対し４１％の収率で活性炭粉末を得た。Then, the infusibilized pitch powder was heated to 800 ° C. in a nitrogen atmosphere in the same rotory kiln as used for the infusibilization, and then the atmosphere was changed to a mixed gas of steam and nitrogen for 75 minutes. An activation treatment was performed to obtain an activated carbon powder in a yield of 41% with respect to the pitch powder.
【００９９】得られた活性炭の平均細孔半径は１３．３
Å、比表面積は９２３ｍ2／ｇ、金属銀含有率は４．６
０％であった。The activated carbon thus obtained has an average pore radius of 13.3.
Å, specific surface area is 923 m 2 / g, metallic silver content is 4.6
It was 0%.
【０１００】比較例１ 実施例２と同様にして取得した軟化点６９，８℃の低軟
化点ヒッチ６００ｇを１リットルの反応器に仕込み、実
施例２と同様に反応器を徐々に加温し、反応器内のピッ
チの温度が１００℃になった時点から攪拌と減圧を開始
し、反応温度が３３０℃になった時点で、反応圧力を１
５０torrに調整し、攪拌下に５ｌ／分の空気を吹き込み
ながら、１４５分問反応を行った。Comparative Example 1 600 g of a low softening point hitch having a softening point of 69,8 ° C. obtained in the same manner as in Example 2 was charged into a 1-liter reactor, and the reactor was gradually heated in the same manner as in Example 2. The stirring and depressurization were started when the pitch temperature in the reactor reached 100 ° C, and the reaction pressure was adjusted to 1 when the reaction temperature reached 330 ° C.
The reaction was adjusted to 50 torr and the reaction was carried out for 145 minutes while blowing 5 l / min of air with stirring.
【０１０１】得られたピッチの軟化点は２６５．７℃、
キノリン不溶成分１６．４％、トルエン不溶成分６８．
８％であり、銀の含有貴は２ｐｐｍ以下であった。The softening point of the obtained pitch is 265.7 ° C.,
Quinoline insoluble component 16.4%, toluene insoluble component 68.
8%, and the content of silver was 2 ppm or less.
【０１０２】また、得られた高軟化点ピッチの収率は、
低軟化点ピッチ当り？ ％であった。The yield of the obtained high softening point pitch is
Low softening point per pitch? %Met.
【０１０３】このピッチを実施例１と同じバッチ式のモ
ノホール紡糸器に仕込み、ピッチの溶融温度３１６℃、
ノズル径０．３ｍｍ、巻取速度８００ｍ／分で紡糸を行
い、ピッチ繊維を得た。This pitch was charged in the same batch type monohole spinning machine as in Example 1, and the melting temperature of the pitch was 316 ° C.
Spinning was performed at a nozzle diameter of 0.3 mm and a winding speed of 800 m / min to obtain pitch fibers.
【０１０４】次いで、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に供した後、不融化処理したピッ
チ繊維を実施例２と同じ条件で賦活処理に供して、活性
炭素繊維を得た。Next, the obtained pitch fiber was subjected to infusibilization treatment under the same conditions as in Example 1, and then the infusibilization-treated pitch fiber was subjected to activation treatment under the same conditions as in Example 2 to obtain activated carbon fiber. Obtained.
【０１０５】得られた活性炭素繊維は、ピッチ繊維当り
の収率＝３３．６％、平均細孔半径＝８．８Å、比表面
積＝１３０２ｍ2／ｇ、Ａｇ含有率＝５ｐｐｍ以下であ
った。The obtained activated carbon fiber had a yield per pitch fiber = 33.6%, an average pore radius = 8.8Å, a specific surface area = 1302 m 2 / g, and an Ag content = 5 ppm or less.
【０１０６】比較例２ 実施例１で用いたと同様のキノリン不溶分８．１％およ
びトルエン不溶分７．３％を含むコールタール１０００
ｇを濾過処理することなく蒸留フラスコに入れ、蒸留を
行ない、コールタール中の軽質分を除去して、コールタ
ール当り６６．９％の収率で軟化点７１．２℃の低軟化
点ピッチを得た。このピッチの軟化点以外の物性は、キ
ノリン不溶成分５．３％、トルエン不溶成分１４．０
％、銀の濃度２ｐｐｍ以下であった。Comparative Example 2 Coal tar 1000 containing the same quinoline insoluble matter 8.1% and toluene insoluble matter 7.3% as used in Example 1.
g was placed in a distillation flask without filtering and distilled to remove light components in the coal tar, and a softening point pitch of 71.2 ° C. was obtained at a yield of 66.9% per coal tar. Obtained. The physical properties of the pitch other than the softening point were 5.3% of the quinoline-insoluble component and 14.0 of the toluene-insoluble component.
%, And the silver concentration was 2 ppm or less.
【０１０７】この低軟化点ピッチ６００ｇを容量１リッ
トルの反応器に仕込み、反応温度３８０℃、反応圧力常
圧で攪拌下で、５ｌ／分の空気を吹き込みながら、２８
０分間反応を行ったところ、軟化点２９９．８℃、キノ
リン不溶成分４４．８％、トルエン不溶成分７２．８
％、銀含有量５ｐｐｍ以下の高軟化点ピッチが得られ
た。高軟化点ピッチの収率は、低軟化点ピッチ当り５
４．９％であった。600 g of this low softening point pitch was charged into a reactor having a capacity of 1 liter, and while stirring at a reaction temperature of 380 ° C. and a reaction pressure and atmospheric pressure while blowing 5 l / min of air, 28
When the reaction was carried out for 0 minutes, the softening point was 299.8 ° C., the quinoline insoluble component was 44.8%, and the toluene insoluble component was 72.8.
%, A high softening point pitch having a silver content of 5 ppm or less was obtained. The yield of high softening point pitch is 5 per low softening point pitch.
It was 4.9%.
【０１０８】この高軟化点ピッチを実施例４と同様にし
て微粉砕し、平均粒径９μｍの微粉末ピッチを得た後、
さらに実施例４と同様にして小型のローターリーキルン
に１００ｇ仕込み、空気を通しながら、常温から３００
℃まで徐々に昇温して不融化処理し、同じローターリ一
キルン中で窒素雰囲気下８００℃まで昇温し、次いで雰
囲気を蒸気と窒素の混合気体に切り替え、６０分間賦活
処理を行い、ピッチ粉末に対し３８％の収率で活性炭粉
末を得た。This high softening point pitch was pulverized in the same manner as in Example 4 to obtain a fine powder pitch having an average particle size of 9 μm.
Further, in the same manner as in Example 4, 100 g was charged in a small rotary kiln, and air was passed through the mixture at room temperature to 300 g.
Gradually raise the temperature to ℃ to infusibilize, raise the temperature to 800 ℃ under nitrogen atmosphere in the same rotary kiln, then switch the atmosphere to a mixed gas of steam and nitrogen, perform activation treatment for 60 minutes, and pitch powder. Activated carbon powder was obtained in a yield of 38%.
【０１０９】得られた活性炭の平均細孔半径は８．７
Å、比表面積は１２８０ｍ2／ｇ、銀含有率は５ｐｐｍ
以下であった。The average pore radius of the obtained activated carbon is 8.7.
Å, specific surface area is 1280m 2 / g, silver content is 5ppm
It was below.
【０１１０】実施例６ 実施例１で用いたと同様のコールタールを濾過処理する
ことなく蒸留フラスコに１００ｇ秤取り、フラスコ内を
窒素雰囲気とした後、８０〜１００℃に加温した。Example 6 100 g of the same coal tar as that used in Example 1 was weighed in a distillation flask without filtering, and the inside of the flask was made a nitrogen atmosphere, and then heated to 80 to 100 ° C.
【０１１１】別にビーカーにエタノール１００ｍｌを秤
取り、８０〜１００℃に加温を行った後、エタノール中
に硝酸銀ｌ０ｇを加え、加えた硝酸銀を溶解した。Separately, 100 ml of ethanol was weighed in a beaker, heated to 80 to 100 ° C., 10 g of silver nitrate was added to ethanol, and the added silver nitrate was dissolved.
【０１１２】硝酸銀を溶解したエタノールを予めフラス
コ内で加温してあるコールタールに徐々に滴下し、約１
時間攪拌混合を行った。Ethanol in which silver nitrate was dissolved was gradually added dropwise to the coal tar which had been heated in the flask in advance, and about 1
Stir-mixing was carried out for an hour.
【０１１３】次いで、上記で得た硝酸銀とエタノールを
含むコールタールを蒸留し、エタノールとコールタール
中の軽質分を除去して、軟化点３６．４℃の重質油を９
８ｇを取得した。この重質油の物性は、キノリン不溶成
分１３．１％、トルエン不溶成分１９．２％、銀濃度
６．１％であった。Next, the coal tar containing silver nitrate and ethanol obtained above was distilled to remove the light components in the ethanol and coal tar, and 9 parts of heavy oil having a softening point of 36.4 ° C. was removed.
Obtained 8 g. The physical properties of this heavy oil were: quinoline insoluble component 13.1%, toluene insoluble component 19.2%, and silver concentration 6.1%.
【０１１４】上記で取得した重質油５ｇに比較例２で取
得した粉末状の活性炭４５ｇを加え、約８０℃に加温し
ながら混合を行った後、混合物を約５０℃まで冷却し、
直径５ｍｍ、長さ１０ｍｍの成形体を作製した。この成
形体の平均密度は、１．３６ｇ／ｃｍ3であった。45 g of the powdered activated carbon obtained in Comparative Example 2 was added to 5 g of the heavy oil obtained above and mixed while heating to about 80 ° C., then the mixture was cooled to about 50 ° C.,
A molded body having a diameter of 5 mm and a length of 10 mm was produced. The average density of this molded body was 1.36 g / cm 3 .
【０１１５】次いで、得られた成形体を金網上に並べた
後、熱風循環式乾燥器内において空気雰囲気中で不融化
処理を行った。不融化条件としての昇温速度は、常温か
ら１００℃までを０．２℃／分、１００℃から３００℃
までを０．７℃／分とし、３００℃で３時間保持した。Next, the obtained molded bodies were arranged on a wire mesh and then subjected to infusibilization treatment in an air atmosphere in a hot air circulation dryer. The temperature rising rate as the infusibilizing condition is from room temperature to 100 ° C at 0.2 ° C / min, from 100 ° C to 300 ° C.
Was maintained at 300 ° C. for 3 hours.
【０１１６】次いで、不融化処理した成形体を窒素雰囲
気下８００℃まで昇温し、８００℃に達した時点で雰囲
気を蒸気と窒素の混合気体に切り替え、１５分間賦活処
理を行った。Next, the infusibilized molded body was heated to 800 ° C. in a nitrogen atmosphere, and when the temperature reached 800 ° C., the atmosphere was changed to a mixed gas of steam and nitrogen, and activation treatment was performed for 15 minutes.
【０１１７】得られた活性炭成形体の平均細孔半径は
９．６Å、比表面積は１３２１ｍ2／ｇ、銀含有率は
６．６％であった。The activated carbon molded body thus obtained had an average pore radius of 9.6Å, a specific surface area of 1321 m 2 / g and a silver content of 6.6%.
【０１１８】試験例１ 実施例２、実施例３、実施例４、実施例５、比較例１お
よび比較例２で取得した繊維状活性炭、粉末活性炭およ
び成形活性炭について、抗菌性の比較を行った。抗菌力
試験は、下記の様にして行った。Test Example 1 The antibacterial properties of the fibrous activated carbon, powdered activated carbon and molded activated carbon obtained in Example 2, Example 3, Example 4, Example 5, Comparative Example 1 and Comparative Example 2 were compared. . The antibacterial activity test was conducted as follows.
【０１１９】Ｉ．試験菌株 ＊大腸菌 Escherichia coli IF03301 ＊黄色ブドウ球菌 Staphylococcus aureus IFOl2782 ＩＩ．試験菌液 試験菌液は、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％肉エキス加普通プイヨン培地で３７℃で１６〜２４
時間振とう培養した後、減薗リン酸緩衝液を用いて１０
００倍に希釈し、５０ｍ１の減菌リン酸緩衝液の入った
２００ｍ１容積の三角フラスコにこの薗液１ｍｌを加え
て、１ｍｌ当りの生菌数が１０4個となるように調整
し、これを試験菌液とした。I. Test strain * Escherichia coli IF03301 * Staphylococcus aureus IFOl2782 II. Test bacterial solution As a test bacterial solution, the test bacterial strain was inoculated into Brain Heart Infusion Agar and cultured at 35 ° C. for 24 hours.
16-24 at 37 ℃ in normal broth medium with 2% meat extract
After culturing with shaking for 10 hours,
Dilute to 00 times, add 1 ml of this Sono liquid to a 200 ml Erlenmeyer flask containing 50 ml of sterile phosphate buffer, and adjust so that the number of viable bacteria per ml is 10 4. The test bacterial solution was used.
【０１２０】滅菌リン酸緩衝夜の調製は、リン酸二水素
カリウム３４ｇを精製水５００ｍ１に溶かし、これに水
酸化ナトリウム４％水溶液１７５ｍｌを加え、次にｐＨ
７．２に調整した後、精製水を加えて全量を１０００ｍ
１とし、さらにこの溶液を精製水で８００倍に希釈して
用いた。To prepare the sterile phosphate buffer night, 34 g of potassium dihydrogen phosphate was dissolved in 500 ml of purified water, 175 ml of a 4% aqueous solution of sodium hydroxide was added thereto, and then pH was adjusted.
After adjusting to 7.2, add purified water to make the total volume 1000m.
It was set to 1, and this solution was diluted 800 times with purified water before use.
【０１２１】ＩＩＩ．試験方法 実施例および比較例で取得した繊維状活性炭、粉末活性
炭或いは成形活性炭を粉砕し、先に調製した試験菌液に
その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時問
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した。III. Test Method Fibrous activated carbon, powdered activated carbon or molded activated carbon obtained in Examples and Comparative Examples were crushed, and 0.1 g thereof was added to the test bacterial solution prepared above to prepare a test solution. This was shaken at 25 ° C., and after 1 hour, 2 hours, 6 hours and 24 hours, the viable cell count in the test solution was measured by the pour plate culture method using a cell count measuring medium.
【０１２２】なお、対照として活性炭を添加しない試験
菌液についても、同様の試験を行った。As a control, the same test was carried out on a test bacterial solution to which activated carbon was not added.
【０１２３】ＩＶ．試験結果 表１に大腸菌に対する抗菌力試験の結果を示し、表２に
黄色ブドウ球菌に対する抗菌力試験の結果を示す。IV. Test Results Table 1 shows the results of the antibacterial activity test against Escherichia coli, and Table 2 shows the results of the antibacterial activity test against Staphylococcus aureus.
【０１２４】[0124]
【表１】 [Table 1]
【０１２５】[0125]
【表２】 [Table 2]
【０１２６】試験例２ 実施例２で取得した活性炭素繊維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０．７６％）について銀の溶出量の比較試験を行っ
た。Test Example 2 Activated carbon fiber obtained in Example 2 and commercially available silver-impregnated activated carbon ("Granular Shirasagi WHA" manufactured by Takeda Pharmaceutical Co., Ltd., impregnated amount of silver 0.76%), silver elution amount The comparison test was performed.
【０１２７】試験は、サンプルをｌｇ秤取り、３００ｍ
ｌの丸底フラスコに投入し、さらに純水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（ｐｐｂ）を測定することによ
り、行った。結果を表３に示す。For the test, 1 g of the sample was weighed and 300 m
Into a 1-liter round-bottomed flask, 100 ml of pure water was further added, the reflux condenser was attached to the round-bottomed flask, and the mixture was boiled for a predetermined time, cooled to room temperature, filtered using a filter paper, and This was done by measuring the amount of silver eluted (ppb). Table 3 shows the results.
【０１２８】[0128]
【表３】 [Table 3]
【０１２９】表３に示す結果から、本発明による活性炭
からの銀溶出量は、ＮＩＨによる飲料水中の銀濃度規制
値以下であることが明らかである。From the results shown in Table 3, it is clear that the amount of silver eluted from the activated carbon according to the present invention is equal to or less than the regulation value of silver concentration in drinking water by NIH.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｃ 3/00 Ｃ１０Ｃ 3/00 Ｄ０１Ｆ 9/145 Ｄ０１Ｆ 9/145 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display area C10C 3/00 C10C 3/00 D01F 9/145 D01F 9/145
Claims (16)
点または分解点以上の温度で混合することを特徴とす
る、銀または銀化合物を分散含有する重質油の製造方
法。1. A method for producing a heavy oil containing silver or a silver compound dispersed therein, which comprises adding a silver compound to the heavy oil and mixing them at a temperature not lower than a melting point or a decomposition point of the silver compound.
合物の融点または分解点以上の温度で混合することを特
徴とする、銀または銀化合物を分散含有する低軟化点ピ
ッチの製造方法。2. A method for producing a low softening point pitch containing silver or a silver compound dispersed therein, which comprises adding a silver compound to the low softening point pitch and mixing at a temperature above the melting point or decomposition point of the silver compound. .
銀または銀化合物を分散含有する重質油または低軟化点
ピッチに酸素またはオゾンを含有する気体を吹き込みつ
つ２５０〜４５０℃で熱処理した後、蒸留することによ
り、光学的に等方性組織を示し、銀または銀化合物を分
散含有する高軟化点ピッチを得ることを特徴とするピッ
チの製造方法。3. A heavy oil containing a dispersion of silver or a silver compound obtained by the method according to claim 1 or a low softening point pitch at 250 to 450 ° C. while being blown with a gas containing oxygen or ozone. A method for producing a pitch, characterized by obtaining a high softening point pitch which exhibits an optically isotropic structure and which contains silver or a silver compound dispersed therein, by performing a heat treatment and then distilling.
銀または銀化合物を分散含有する重質油または低軟化点
ピッチに不活性ガスを吹き込みつつ３５０〜５００℃で
熱処理した後、蒸留することにより、光学的に異方性の
組織を２０％以上含み、銀または銀化合物を分散含有す
る高軟化点ピッチを得ることを特徴とするピッチの製造
方法。4. Heat treatment at 350 to 500 ° C. while blowing an inert gas into a heavy oil or a low softening point pitch containing silver or a silver compound dispersed therein obtained by the method according to claim 1 or 2. A method for producing a pitch, characterized in that a high softening point pitch containing 20% or more of an optically anisotropic structure and containing silver or a silver compound dispersed therein is obtained by distillation.
により製造された銀または銀化合物を分散含有する重質
油、低軟化点ピッチまたは高軟化点ピッチを炭素材料の
製造原料として使用することを特徴とする、銀または銀
化合物を分散含有する抗菌性に優れた炭素材料の製造方
法。5. A heavy oil containing silver or a silver compound dispersed therein produced by the method according to any one of claims 1 to 4, a low softening point pitch or a high softening point pitch as a raw material for producing a carbon material. A method for producing a carbon material containing silver or a silver compound dispersed therein and having excellent antibacterial properties, which is used.
の方法。6. The method according to claim 5, wherein the carbon material is activated carbon.
は粉末状活性炭である請求項６に記載の方法。7. The method according to claim 6, wherein the activated carbon is activated carbon fiber, granular activated carbon or powdered activated carbon.
載の方法。8. The method according to claim 5, wherein the carbon material is carbon fiber.
酸銀を重質油に添加し、混合分散させることを特徴とす
る、硝酸銀を分散含有する重質油の製造方法。9. A method for producing a heavy oil containing silver nitrate dispersed therein, wherein silver nitrate dissolved in glycerin or ethanol is added to the heavy oil and mixed and dispersed.
硝酸銀を低軟化点ピッチにに添加し、混合分散させるこ
とを特徴とする、硝酸銀を分散含有する低軟化点ピッチ
の製造方法。10. A method for producing a low softening point pitch containing silver nitrate dispersed therein, which comprises adding silver nitrate dissolved in glycerin or ethanol to the low softening point pitch and mixing and dispersing.
れた硝酸銀を分散含有する重質油または低軟化点ピッチ
に酸素またはオゾンを含有する気体を吹き込みつつ２５
０〜４５０℃で熱処理した後、蒸留することにより、光
学的に等方性組織を示し、硝酸銀または銀を分散含有す
る高軟化点ピッチを得ることを特徴とするピッチの製造
方法。11. A heavy oil containing silver nitrate dispersed therein or obtained by the method according to claim 9 or 10 while blowing a gas containing oxygen or ozone into the low softening point pitch.
A method for producing a pitch, characterized by obtaining a high softening point pitch which exhibits an optically isotropic structure and which contains silver nitrate or silver in a dispersed state by performing a heat treatment at 0 to 450 ° C. and then distilling.
れた硝酸銀を分散含有する重質油または低軟化点ピッチ
に不活性ガスを吹き込みつつ３５０〜５００℃で熱処理
した後、蒸留することにより、光学的に異方性の組織を
２０％以上含み、硝酸銀または銀を分散含有する高軟化
点ピッチを得ることを特徴とするピッチの製造方法。12. Heat treatment at 350 to 500 ° C. while blowing an inert gas into a heavy oil containing silver nitrate dispersed therein or a low softening point pitch obtained by the method according to claim 9 or 10, and then distilling. According to the above method, a high softening point pitch containing 20% or more of an optically anisotropic structure and containing silver nitrate or silver dispersed therein is obtained.
方法により製造された硝酸銀または銀を分散含有する重
質油、ピッチ、低軟化点ピッチまたは高軟化点ピッチを
炭素材料の製造原料として使用することを特徴とする、
硝酸銀または銀を分散含有する抗菌性に優れた活性炭の
製造方法。13. A raw material for producing a carbon material using a heavy oil containing silver nitrate or silver dispersed therein produced by the method according to any one of claims 9 to 12, pitch, a low softening point pitch or a high softening point pitch. Characterized by using as,
A method for producing activated carbon containing silver nitrate or silver dispersed therein and having excellent antibacterial properties.
記載の方法。14. The method according to claim 13, wherein the carbon material is activated carbon.
たは粉末状活性炭である請求項１４に記載の方法。15. The method according to claim 14, wherein the activated carbon is activated carbon fiber, granular activated carbon or powdered activated carbon.
に記載の方法。16. The carbon material is carbon fiber.
The method described in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7258578A JPH09100474A (en) | 1995-10-05 | 1995-10-05 | Production of silver dispersed type carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7258578A JPH09100474A (en) | 1995-10-05 | 1995-10-05 | Production of silver dispersed type carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09100474A true JPH09100474A (en) | 1997-04-15 |
Family
ID=17322202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7258578A Pending JPH09100474A (en) | 1995-10-05 | 1995-10-05 | Production of silver dispersed type carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09100474A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11278823A (en) * | 1998-03-25 | 1999-10-12 | Kuraray Chem Corp | Antibacterial activated carbon and its production |
| KR100455664B1 (en) * | 2001-12-10 | 2004-11-06 | 한국화학연구원 | Activated carbon fiber having silver particles on the surface thereof, and preparation process therefor |
| KR100458488B1 (en) * | 1998-11-10 | 2005-01-24 | 안정오 | Method for producing charcoal containing silver |
| JP2006188393A (en) * | 2005-01-06 | 2006-07-20 | Japan Science & Technology Agency | Method of processing carbon material |
| JP2017505839A (en) * | 2014-01-29 | 2017-02-23 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Detergent composition containing stable silver |
| CN110499033A (en) * | 2019-07-06 | 2019-11-26 | 胡赛辉 | A kind of preparation method of visible light catalytic type vehicle exhaust asphalt pavement material |
-
1995
- 1995-10-05 JP JP7258578A patent/JPH09100474A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11278823A (en) * | 1998-03-25 | 1999-10-12 | Kuraray Chem Corp | Antibacterial activated carbon and its production |
| KR100458488B1 (en) * | 1998-11-10 | 2005-01-24 | 안정오 | Method for producing charcoal containing silver |
| KR100455664B1 (en) * | 2001-12-10 | 2004-11-06 | 한국화학연구원 | Activated carbon fiber having silver particles on the surface thereof, and preparation process therefor |
| JP2006188393A (en) * | 2005-01-06 | 2006-07-20 | Japan Science & Technology Agency | Method of processing carbon material |
| JP2017505839A (en) * | 2014-01-29 | 2017-02-23 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Detergent composition containing stable silver |
| CN110499033A (en) * | 2019-07-06 | 2019-11-26 | 胡赛辉 | A kind of preparation method of visible light catalytic type vehicle exhaust asphalt pavement material |
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