JP2005154174A - Functional metal and/or functional metal compound-containing porous carbon material, and its manufacture method - Google Patents

Functional metal and/or functional metal compound-containing porous carbon material, and its manufacture method Download PDF

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JP2005154174A
JP2005154174A JP2003392762A JP2003392762A JP2005154174A JP 2005154174 A JP2005154174 A JP 2005154174A JP 2003392762 A JP2003392762 A JP 2003392762A JP 2003392762 A JP2003392762 A JP 2003392762A JP 2005154174 A JP2005154174 A JP 2005154174A
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functional metal
porous carbon
carbon material
functional
metal compound
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JP4467961B2 (en
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Michihide Yokoyama
理英 横山
Satoshi Hayashi
聡 林
Hitoshi Kawasaki
仁士 川崎
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Nisshoku Corp
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<P>PROBLEM TO BE SOLVED: To provide a functional metal and/or functional metal compound-containing poroous carbon material which is harmless to a human body, fishes, and water plants, exhibits high antimicrobial properties, antialgae properties, etc., having excellent usability, and can be manufactured at a low cost. <P>SOLUTION: The functional metal and/or functional metal compound 2 is held in a vegetable porous material prepared by carbonizing a vegetable material 1. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

この発明は、機能性金属及び/又は機能性金属化合物含有多孔質炭素材料およびその製造方法に関する。   The present invention relates to a functional metal and / or a porous metal material containing a functional metal compound and a method for producing the same.

例えば、多孔質炭素材料の代表である活性炭は、空気浄化、上下水道処理、排水処理などに広く利用され、また、木炭も、調湿材や河川浄化、土壌改良材として広く普及しており、例えば排ガス中の塩素系ガスや硫黄酸化物などの除去にも利用されている。
特開2000−319011号公報
For example, activated carbon, which is representative of porous carbon materials, is widely used for air purification, water and sewage treatment, wastewater treatment, etc., and charcoal is also widely used as a humidity control material, river purification, soil improvement material, For example, it is also used for removing chlorine-based gases and sulfur oxides in exhaust gas.
JP 2000-319011 A

しかし、上記の利用はいずれも、前記活性炭・木炭(多孔質炭素材料)の内部の微細な細孔の吸着特性のみを活用するものに過ぎなかった。   However, all of the above uses only utilize the adsorption characteristics of fine pores inside the activated carbon / charcoal (porous carbon material).

ところで、鑑賞魚を収容したガラス水槽や鑑賞池などでは、水中に発生する藻類やアオコが美観を損ね、また、水のBODを高めたり、水中の細菌を増加させたりする。これらを防ぐために、水の交換・掃除や、防藻剤の添加などの作業を定期的に行っているが、これらの作業を行うには手間がかかり、また、添加した防藻剤が水中や水底に浮遊、沈殿したりして美観を損なうおそれがある。さらに、防藻剤として強力な薬剤を使用すると、水草を死滅させたり、魚類の成長を害する危険性がある。   By the way, in a glass aquarium or an appreciation pond in which appreciation fish are housed, algae and blue sea urchins generated in the water lose their beauty, increase the BOD of water, and increase the bacteria in the water. In order to prevent these problems, work such as water exchange / cleaning and the addition of an algae-proofing agent is performed regularly, but it takes time and effort to perform these operations. There is a risk of losing aesthetics by floating or settling on the bottom of the water. In addition, the use of powerful agents as an algae killer has the risk of killing aquatic plants and harming fish growth.

さらに、近年、食中毒や院内感染の事件が多発し、細菌汚染等に関する認識が高まり、抗菌剤(例えば無機系としては銀、酸化チタン等、有機系としては塩素、次亜塩素酸ナトリウム等の抗菌剤)が広く使用されるようになった。しかし、いずれの抗菌剤も材料が高値であったり、人体に有害であったり、酸化チタンであると光の照射が不可欠であり、使用可能な環境・条件が限られるという問題があった。   Furthermore, in recent years, food poisoning and nosocomial infections have frequently occurred, and awareness of bacterial contamination has increased. Antibacterial agents (for example, silver and titanium oxide for inorganic systems, chlorine and sodium hypochlorite for organic systems, etc.) Agent) has been widely used. However, any antibacterial agent has a problem that the material is expensive, harmful to the human body, or if it is titanium oxide, light irradiation is indispensable and the usable environment and conditions are limited.

この発明は上述の事柄に留意してなされたもので、その目的は、人体や魚類、水草類には無害でありつつ、高い抗菌性・防藻性等を発揮し、使用性に優れ、低コストで製造することができる機能性金属及び/又は機能性金属化合物含有多孔質炭素材料およびその製造方法を提供することである。   The present invention has been made in consideration of the above-mentioned matters, and its purpose is harmless to the human body, fish and aquatic plants, while exhibiting high antibacterial / algaeproofing properties, etc., excellent usability, and low A functional metal and / or a functional metal compound-containing porous carbon material that can be produced at a low cost and a method for producing the same are provided.

上記目的を達成するために、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料は、植物性材料を炭化してなる植物性多孔質材料に機能性金属及び/又は機能性金属化合物を保持させた(請求項1)。   In order to achieve the above object, the functional metal and / or functional metal compound-containing porous carbon material of the present invention is obtained by adding a functional metal and / or functionality to a plant porous material obtained by carbonizing a plant material. A metal compound was retained (claim 1).

詳しくは、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料は、機能性金属及び/又は機能性金属化合物を1〜40重量%含む(請求項2)。   Specifically, the functional metal and / or functional metal compound-containing porous carbon material of the present invention contains 1 to 40% by weight of the functional metal and / or the functional metal compound (claim 2).

また、保持させる機能性金属及び/又は機能性金属化合物の結晶が10μm以下であることが好ましい(請求項3)。   Moreover, it is preferable that the crystal | crystallization of the functional metal and / or functional metal compound to hold | maintain is 10 micrometers or less (Claim 3).

一方、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の製造方法は、機能性金属を含むアルカリ溶液に植物性材料を浸漬後、400〜900℃で炭化させる(請求項4)。   On the other hand, in the method for producing a functional metal and / or porous metal material containing a functional metal compound according to the present invention, the plant material is immersed in an alkaline solution containing the functional metal and then carbonized at 400 to 900 ° C. 4).

また、前記アルカリ溶液が、アルミニウムアルカリ溶液であることが望ましい(請求項5)。   The alkali solution is preferably an aluminum alkali solution.

上記の構成からなる発明では、人体や魚類、水草類には無害でありつつ、高い抗菌性・防藻性等を発揮し、使用性に優れ、低コストで製造することができる機能性金属及び/又は機能性金属化合物含有多孔質炭素材料およびその製造方法を提供することができる。   In the invention having the above-described structure, a functional metal that is harmless to human body, fish, aquatic plants, exhibits high antibacterial and algal control properties, is excellent in usability and can be manufactured at low cost, and A functional metal compound-containing porous carbon material and a method for producing the same can be provided.

詳しくは、例えば導管や仮導管を有する一般の木材、あるいはヤシ繊維、ジュート、麻、ビンロウジュ等の連続気孔を有する植物繊維、あるいはその他、藁や籾殻、竹などの植物性材料は、炭化させることにより、膨大な表面積を有する多孔質の炭素材料(植物性多孔質材料)と化す。すなわち、例えば木材では導管、仮導管を形成している組織の微細な孔が多孔質化し、ヤシ繊維などの植物繊維では連続気孔を形成している組織が多孔質化し、さらに、藁や籾殻、竹などでは繊維組織が多孔質化する。   Specifically, for example, general wood having conduits or temporary conduits, or plant fibers having continuous pores such as palm fiber, jute, hemp, areca, or other plant materials such as straw, rice husk, bamboo, etc. should be carbonized. Thus, a porous carbon material (plant-type porous material) having a huge surface area is obtained. That is, for example, in wood, the fine pores of the tissue forming the conduit and the temporary conduit are made porous, and in the plant fiber such as palm fiber, the tissue forming the continuous pores is made porous. In bamboo and the like, the fiber structure becomes porous.

一方、これらの植物性材料を炭化させる前に、機能性金属及び/又は機能性金属化合物の溶液に浸漬させると、具体的には、ヤシ繊維、ジュート、麻、ビンロウジュ等の連続気孔を有する植物繊維や藁や籾殻などの植物性材料については、これをそのまま用いて、機能性金属及び/又は機能性金属化合物の溶液に浸漬させると、その植物組織内に機能性金属及び/又は機能性金属化合物を取り込むことができる。なお、機能性金属とは、防藻性・抗菌性・ガス除去性などの少なくとも一以上の機能をもつ金属(例えば亜鉛・銀・チタンなど)のことであり、機能性金属化合物とは上記金属の化合物である。   On the other hand, before carbonizing these plant materials, when immersed in a solution of a functional metal and / or functional metal compound, specifically, plants having continuous pores such as palm fiber, jute, hemp, areca With regard to plant materials such as fibers, straw and rice husks, if they are used as they are and immersed in a solution of functional metals and / or functional metal compounds, functional metals and / or functional metals in the plant tissue. Compounds can be incorporated. The functional metal is a metal having at least one function (eg, zinc, silver, titanium, etc.) such as antialgae, antibacterial, and gas removability, and the functional metal compound is the above metal. It is a compound of this.

また、木材や竹などの植物性材料についても、チップ化したり木毛に加工したり、おが屑を利用したりして、これを機能性金属及び/又は機能性金属化合物の溶液に浸漬させると、導管や仮導管を形成している組織内の微細な細孔に機能性金属及び/又は機能性金属化合物を取り込むことができる。   Also, for plant materials such as wood and bamboo, when chipped or processed into wood hair, sawdust is used, and this is immersed in a solution of a functional metal and / or functional metal compound, A functional metal and / or a functional metal compound can be taken into the fine pores in the tissue forming the conduit or temporary conduit.

そして、上記のようにして植物性材料に取り込まれた機能性金属及び/又は機能性金属化合物は、植物性材料内に浸透し、植物性材料のもつ水酸基と結合したり、植物性材料の孔表面に付着した状態となる。   The functional metal and / or functional metal compound incorporated into the plant material as described above penetrates into the plant material and binds to the hydroxyl group of the plant material or pores of the plant material. It will be in the state which adhered to the surface.

続いて、前記機能性金属及び/又は機能性金属化合物を上記のように取り込んだ植物性材料を例えば400〜900℃で炭化させると、孔が発達して広がると共に、水酸基と結合した機能性金属及び/又は機能性金属化合物が孔表面に析出し、最終的に、水酸基は蒸発して機能性金属及び/又は機能性金属化合物が孔表面に残り、これにより、機能性金属及び/又は機能性金属化合物含有多孔質炭素材料が完成する。このように完成した多孔質炭素材料は、細孔が良好に発達した状態の植物性多孔質材料の炭化組織内に機能性金属及び/又は機能性金属化合物が微細(結晶の大きさが10μm以下)に高分散した(より満遍なく均一に分散した)ものとなる。   Subsequently, when the plant material incorporating the functional metal and / or functional metal compound as described above is carbonized at 400 to 900 ° C., for example, the pores develop and expand, and the functional metal bonded to the hydroxyl group. And / or the functional metal compound precipitates on the pore surface, and finally the hydroxyl group evaporates and the functional metal and / or functional metal compound remains on the pore surface, whereby the functional metal and / or functionality A metal compound-containing porous carbon material is completed. In the porous carbon material thus completed, the functional metal and / or the functional metal compound is fine (the crystal size is 10 μm or less) in the carbonized structure of the plant porous material in which the pores are well developed. ) Highly dispersed (more evenly and uniformly dispersed).

ここで、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料が、機能性金属及び/又は機能性金属化合物系化合物を1〜40重量%保持するように構成することにより、機能性金属及び/又は機能性金属化合物の反応性が十分に高まり、また、機能性金属及び/又は機能性金属化合物が水中等に溶出しやすい状態となる。   Here, the functional metal and / or functional metal compound-containing porous carbon material of the present invention is configured to hold 1 to 40% by weight of the functional metal and / or functional metal compound-based compound, The reactivity of the functional metal and / or the functional metal compound is sufficiently increased, and the functional metal and / or the functional metal compound is likely to elute into water or the like.

また、前記植物性材料を浸漬する機能性金属及び/又は機能性金属化合物を含むアルカリ溶液の濃度を1〜3Nとすれば、前記アルカリ溶液において機能性金属及び/又は機能性金属化合物が容易に溶解し、また、溶液によって植物性材料(木質)に変質が大きく起こることもないため、植物性材料への機能性金属及び/又は機能性金属化合物の導入を良好に行うことが可能となる。   Moreover, if the density | concentration of the alkaline solution containing the functional metal and / or functional metal compound which immerses the said plant material shall be 1-3N, a functional metal and / or a functional metal compound will be easily in the said alkaline solution. Since it dissolves and the plant material (woody material) is not greatly altered by the solution, it is possible to satisfactorily introduce the functional metal and / or functional metal compound into the plant material.

そして、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料において、植物性多孔質材料の炭化組織には、その内部の微細な細孔の吸着特性によって、微生物(細菌類)、藻類が多く付着する。一方、機能性金属及び/又は機能性金属化合物としての例えば酸化亜鉛などは、抗菌性、防藻性を有し、細菌類、藻類の発生を抑制する効果がある。なお、機能性金属及び/又は機能性金属化合物の上記の効果(抗菌性、防藻性)は、前記細菌類、藻類までの距離が長くなるほど弱まるが、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料では、前記植物性多孔質材料の炭化組織の吸着特性によって細菌類、藻類を集め、細菌類、藻類を機能性金属及び/又は機能性金属化合物に近づけることができ、また、機能性金属及び/又は機能性金属化合物は植物性多孔質材料の炭化組織内に微細に高分散していることからも、前記機能性金属及び/又は機能性金属化合物により細菌類、藻類を効果的に減少させることが可能となり、この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料は非常に高い抗菌性、防藻性を発揮することになる。   In the functional metal and / or functional metal compound-containing porous carbon material of the present invention, the carbonized tissue of the plant porous material has microorganisms (bacteria) due to the adsorption characteristics of the fine pores therein. A lot of algae are attached. On the other hand, for example, zinc oxide as a functional metal and / or a functional metal compound has antibacterial and antialgal properties, and has an effect of suppressing the generation of bacteria and algae. In addition, although the said effect (antibacterial property, anti-algae property) of a functional metal and / or a functional metal compound becomes so weak that the distance to the said bacteria and algae becomes long, the functional metal and / or function of this invention In the porous carbon material containing a functional metal compound, bacteria and algae can be collected by the adsorption characteristics of the carbonized tissue of the plant porous material, and the bacteria and algae can be brought close to the functional metal and / or the functional metal compound. In addition, since the functional metal and / or functional metal compound is finely and highly dispersed in the carbonized tissue of the plant porous material, bacteria, Algae can be effectively reduced, and the functional metal and / or functional metal compound-containing porous carbon material of the present invention will exhibit extremely high antibacterial and algal resistance.

また、亜鉛には脱硫作用があるので、例えば石炭ガスに、機能性金属及び/又は機能性金属化合物として亜鉛を用いたこの発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料を接触させれば、前記脱硫作用と吸着特性とにより、石炭ガス中の硫黄化合物濃度を効果的に下げることが可能となる。   Further, since zinc has a desulfurization action, for example, the functional metal and / or the functional metal compound-containing porous carbon material of the present invention using zinc as a functional metal and / or functional metal compound for coal gas is used. If contacted, the sulfur compound concentration in the coal gas can be effectively reduced by the desulfurization action and the adsorption characteristics.

さらに、前記機能性金属及び/又は機能性金属化合物が酸化亜鉛である場合、酸化亜鉛は電子(e- )と正孔(h+ )の対を生じ、この正孔が大気中等に存在する酸素や水と反応することによって酸化力の強いスーパーオキサイドイオン(O2-)や水酸化ラジカル(−OH)を生成する。そして、この活性酸素は非常に不安定であり、安定した状態になるために、大気中等に存在するNOX やSOX 等を分解し、例えば分解されたNOX は無害なHNO3 などになる。従って、酸化亜鉛を用いたこの発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料を、例えば、NOX やSOX 等を含む排ガスなどに接触させれば、前記NOX やSOX を分解し、その排ガスを浄化することができる。また、前記活性酸素は酸化力が強く、殺菌効果も有するため、前記排ガス等の殺菌をも行うことが可能となる。 Further, when the functional metal and / or the functional metal compound is zinc oxide, the zinc oxide generates a pair of an electron (e ) and a hole (h + ), and this hole exists in the atmosphere or the like. It reacts with water to produce superoxide ions (O 2− ) and hydroxyl radicals (—OH) with strong oxidizing power. Since this active oxygen is very unstable and becomes stable, it decomposes NO x , SO x, etc. present in the atmosphere, for example, the decomposed NO x becomes harmless HNO 3, etc. . Accordingly, when the functional metal and / or functional metal compound-containing porous carbon material of the present invention using zinc oxide is brought into contact with, for example, exhaust gas containing NO x , SO x, etc., the NO x or SO X can be decomposed and the exhaust gas can be purified. In addition, since the active oxygen has a strong oxidizing power and a sterilizing effect, the exhaust gas and the like can be sterilized.

また、前記アルカリ溶液を、機能性金属を含む1〜3Nのアルミニウムアルカリ溶液とすることが望ましい。すなわち、通常のアルカリ溶液に植物性材料(植物性多孔質材料)を浸漬させて機能性金属及び/又は機能性金属化合物含有多孔質炭素材料を製造した場合よりも、前記アルカリ溶液としてアルミニウムアルカリ溶液を用い、このアルミニウムアルカリ溶液に植物性材料(植物性多孔質材料)を浸漬させて機能性金属及び/又は機能性金属化合物含有多孔質炭素材料を製造した場合のほうが、機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の機能性金属及び/又は機能性金属化合物の含有量が増加し、また、植物性多孔質材料の炭化組織内に析出する機能性金属及び/又は機能性金属化合物の結晶がより小さく(1μm以下)なり、表面積が増加するため、その反応性がより高まり、ひいては機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の上記の効果がより高まることとなる。   Moreover, it is desirable that the alkali solution is a 1 to 3N aluminum alkali solution containing a functional metal. That is, an aluminum alkali solution is used as the alkali solution, compared with the case where a functional metal and / or a functional metal compound-containing porous carbon material is produced by immersing a plant material (plant porous material) in a normal alkali solution. When a functional material and / or a functional metal compound-containing porous carbon material is produced by immersing a plant material (plant porous material) in this aluminum alkali solution, the functional metal and / or Functional metal and / or functional metal in which content of functional metal and / or functional metal compound of porous carbon material containing functional metal compound is increased and precipitated in carbonized structure of plant porous material Since the crystal of the compound is smaller (less than 1 μm) and the surface area is increased, its reactivity is further enhanced, and consequently functional metal and / or functional metallization Additional advantages of the object containing the porous carbon material becomes more enhanced it.

以下、この発明の詳細を、図を参照しながら説明する。図1は、本発明の一実施例に係る機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の製造方法を概略的に示す説明図である。   Hereinafter, the details of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view schematically showing a method for producing a functional metal and / or a functional metal compound-containing porous carbon material according to an embodiment of the present invention.

この発明の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の製造方法は、植物性材料1に機能性金属及び/又は機能性金属化合物(以下、機能性金属物質という)2を含浸する工程(以下、含浸工程という)と、植物性材料1を炭化させて植物性多孔質材料を形成する工程(以下、炭化工程という)とをこの順に有し、植物性材料1を炭化してなる植物性多孔質材料に機能性金属物質2を保持させてなる機能性金属物質含有多孔質炭素材料Dを形成する。   In the method for producing a functional metal and / or porous metal material containing a functional metal compound according to the present invention, the plant material 1 is impregnated with a functional metal and / or a functional metal compound (hereinafter referred to as a functional metal substance) 2. A process (hereinafter referred to as an impregnation process) and a process of carbonizing the plant material 1 to form a plant porous material (hereinafter referred to as a carbonization process) in this order, and carbonizing the plant material 1 A functional metallic substance-containing porous carbon material D is formed by holding the functional metallic substance 2 in the plant porous material.

前記植物性材料1は、セルロース、ヘミセルロース、リグニンなどの成分を有するもので、例えば、ヤシ繊維やジュート、麻、ビンロウジュ、竹や木材(間伐材、伐採木、廃木材等)、中でも好ましくは、吸水性の高い針葉樹をチップ化したものや木毛に加工したもの、おが屑、藁、籾殻などを選択することができる。   The plant material 1 has components such as cellulose, hemicellulose, and lignin. For example, palm fiber, jute, hemp, areca, bamboo and wood (thinned wood, felled wood, waste wood, etc.), preferably, It is possible to select coniferous trees with high water absorption as chips, those processed into wood wool, sawdust, straw, and rice husks.

前記機能性金属物質2としては、防藻性・抗菌性・ガス除去性などの少なくとも一以上の機能をもつ様々な金属(例えば亜鉛・銀・銅・チタンなど)およびそれらの化合物を用いることができ、この実施例では、亜鉛及び/又は亜鉛化合物(酸化亜鉛や水酸化亜鉛など)である。   As the functional metal substance 2, various metals (for example, zinc, silver, copper, titanium, etc.) having at least one function such as an algae-proofing property, an antibacterial property, and a gas removal property and their compounds are used. In this embodiment, it is zinc and / or a zinc compound (such as zinc oxide or zinc hydroxide).

前記含浸工程では、機能性金属物質2としての亜鉛を含むアルカリ溶液3に植物性材料1を所定時間浸漬する。ここで、前記アルカリ溶液3の濃度は1〜3Nであることが望ましい。これは、前記アルカリ溶液3の濃度が1N未満では亜鉛2が溶解しにくく、3Nより高いと植物性多孔質材料1(木質)に変質が大きく起こるためである。   In the impregnation step, the plant material 1 is immersed in an alkaline solution 3 containing zinc as the functional metal substance 2 for a predetermined time. Here, the concentration of the alkaline solution 3 is preferably 1 to 3N. This is because if the concentration of the alkaline solution 3 is less than 1N, the zinc 2 is difficult to dissolve, and if it is higher than 3N, the plant porous material 1 (wood) is greatly altered.

また、前記アルカリ溶液3には、亜鉛2を0.1〜5.0重量%、好ましくは1〜3重量%含有させることが好適である。ここで、前記溶液3が中性の溶液である場合、亜鉛2が溶解しにくく、また、酸性の溶液である場合には、植物性多孔質材料1の細孔4内に亜鉛2が残るだけで前記植物性多孔質材料1の成分と亜鉛2とは反応せず(アルカリ性でないと反応が起こらない)、炭化の際に酸性ガスが発生し、環境に良くない上、炭化工程で用いる炭化装置5を劣化させてしまうという不都合が生じることから、前記溶液3をアルカリ性としてある。   Further, it is preferable that the alkaline solution 3 contains zinc 2 in an amount of 0.1 to 5.0% by weight, preferably 1 to 3% by weight. Here, when the solution 3 is a neutral solution, the zinc 2 is difficult to dissolve, and when the solution 3 is an acidic solution, only the zinc 2 remains in the pores 4 of the plant porous material 1. The component of the plant porous material 1 and the zinc 2 do not react (the reaction does not occur unless it is alkaline), an acid gas is generated during carbonization, and is not good for the environment. Therefore, the solution 3 is made alkaline.

上記の構成からなる含浸工程では、まず、機能性金属物質(亜鉛)2がアルカリ溶液3に一旦溶解し、続いて、亜鉛2が植物性材料1の内部に浸透する。その後、前記植物性材料1中の成分の水酸基等に亜鉛イオンが結合する。このとき、植物性材料1の内部に浸透せず、植物性材料1の孔の表面に付着する亜鉛2も有ると考えられる。   In the impregnation step having the above-described configuration, first, the functional metal substance (zinc) 2 is once dissolved in the alkaline solution 3, and then the zinc 2 penetrates into the plant material 1. Thereafter, zinc ions are bonded to the hydroxyl group or the like of the component in the plant material 1. At this time, it is considered that there is also zinc 2 that does not penetrate into the inside of the plant material 1 and adheres to the surface of the hole of the plant material 1.

前記炭化工程では、炭化装置5を用いて、前記機能性金属物質2を取り込んだ状態の植物性材料1を400〜900℃、好ましくは650〜750℃で炭化させる。上記の温度(高温)で植物性材料1を炭化させると、植物性材料1は細孔4が良好に発達した(多孔質化した)状態の炭化組織からなる植物性多孔質材料となる。そして、上記炭化に伴って、植物性材料1の孔4が発達して広がると共に、水酸基と結合した亜鉛が孔4表面に析出する。なお、植物性材料1を炭化させるための温度を400℃未満とすると、植物性多孔質材料内における細孔4は発達が不十分のままとなり、また、900℃より高くすると、機能性金属物質(亜鉛化合物)2が昇華してしまう。   In the carbonization step, the plant material 1 in which the functional metal substance 2 is incorporated is carbonized at 400 to 900 ° C., preferably 650 to 750 ° C., using the carbonization device 5. When the plant material 1 is carbonized at the above temperature (high temperature), the plant material 1 becomes a plant porous material composed of carbonized tissue in which the pores 4 are well developed (made porous). And with the said carbonization, while the hole 4 of the plant material 1 develops and spreads, the zinc couple | bonded with the hydroxyl group precipitates on the hole 4 surface. If the temperature for carbonizing the plant material 1 is less than 400 ° C., the pores 4 in the plant porous material remain underdeveloped, and if it is higher than 900 ° C., the functional metal substance (Zinc compound) 2 is sublimated.

そして、植物性材料1の上記高温での炭化時に、前記細孔4内に析出していた機能性金属物質(亜鉛化合物)2のうちの水酸化亜鉛の水酸基などは全て蒸発し、亜鉛はそのほとんどが酸化して酸化亜鉛となる。従って、植物性材料1の炭化後には、機能性金属物質2としての酸化亜鉛が孔4の表面に残り、これにより、機能性金属物質含有多孔質炭素材料が完成する。   Then, during the carbonization of the plant material 1 at the high temperature, all the hydroxyl groups of zinc hydroxide in the functional metal substance (zinc compound) 2 deposited in the pores 4 are evaporated, Most of them are oxidized to zinc oxide. Therefore, after carbonization of the plant material 1, zinc oxide as the functional metal substance 2 remains on the surface of the pores 4, thereby completing the functional metal substance-containing porous carbon material.

上記のようにして形成される機能性金属物質含有多孔質炭素材料Dは、前記機能性金属物質2を1〜40重量%保持していることが望ましい。機能性金属物質2を1重量%より少なく保持させると、反応性が十分に高まらず、機能性金属物質2を40重量%より多く保持させると、機能性金属物質(亜鉛化合物)2が溶出しにくくなり、水質浄化等の機能が低下するためである。   The functional metal substance-containing porous carbon material D formed as described above preferably holds 1 to 40% by weight of the functional metal substance 2. If the functional metal substance 2 is held less than 1% by weight, the reactivity is not sufficiently increased, and if the functional metal substance 2 is held more than 40% by weight, the functional metal substance (zinc compound) 2 is eluted. This is because it becomes difficult and functions such as water purification are reduced.

ここで、前記含浸工程において、前記アルカリ溶液3を、機能性金属物質(亜鉛)2を含む1〜3Nのアルミニウムアルカリ溶液(アルミニウムを含むアルカリ溶液)とすることが望ましい。すなわち、通常のアルカリ溶液3に植物性材料1を浸漬させることで前記含浸工程を行うと、完成した機能性金属物質含有多孔質炭素材料Dに含まれる機能性金属物質(亜鉛)2の含有量は10〜15重量%となるのに対し、前記アルカリ溶液3としてのアルミニウムアルカリ溶液に植物性材料1を浸漬させることで前記含浸工程を行うと、完成した機能性金属物質含有多孔質炭素材料Dに含まれる機能性金属物質(亜鉛)2の含有量は20〜30重量%となる。これは、アルミニウムのもつ触媒的な作用により植物性材料1の含有成分と亜鉛との反応が促進されるためである。   Here, in the impregnation step, the alkaline solution 3 is preferably a 1 to 3 N aluminum alkaline solution (an alkaline solution containing aluminum) containing a functional metal substance (zinc) 2. That is, when the impregnation step is performed by immersing the plant material 1 in a normal alkaline solution 3, the content of the functional metal substance (zinc) 2 contained in the completed functional metal substance-containing porous carbon material D When the impregnation step is performed by immersing the plant material 1 in the aluminum alkali solution as the alkali solution 3, the porous carbon material D containing the functional metal substance is completed. The content of the functional metal substance (zinc) 2 contained in is 20 to 30% by weight. This is because the reaction between the components of the plant material 1 and zinc is promoted by the catalytic action of aluminum.

上記のことを確認するために、前記アルカリ溶液3として、通常のアルカリ溶液(アルミニウムを含まないアルカリ溶液)と、アルミニウムアルカリ溶液(アルミニウムを含むアルカリ溶液)とを作成し、それぞれを用いて機能性金属物質含有多孔質炭素材料Dの製造を行い、各機能性金属物質含有多孔質炭素材料Dに含まれる機能性金属物質2の量を測定するとともに、各機能性金属物質含有多孔質炭素材料Dの細孔4内の状態を顕微鏡で観察した。   In order to confirm the above, as the alkali solution 3, a normal alkali solution (an alkali solution not containing aluminum) and an aluminum alkali solution (an alkali solution containing aluminum) are prepared, and each is used for functionality. The metal material-containing porous carbon material D is manufactured, the amount of the functional metal material 2 contained in each functional metal substance-containing porous carbon material D is measured, and each functional metal substance-containing porous carbon material D is measured. The state in the pores 4 was observed with a microscope.

詳しくは、前記植物性材料1としては木材チップを用いた。また、前記通常のアルカリ溶液は、水酸化ナトリウム40gを含むイオン交換水としての蒸留水(H2 O)500mLからなる1〜3N(好ましくは2N)の溶液に機能性金属物質2としての酸化亜鉛10gを溶解させて形成し、前記アルミニウムアルカリ溶液は、水酸化ナトリウム40gおよび水酸化アルミニウム10を含むイオン交換水としての蒸留水(H2 O)500mLからなる1〜3N(好ましくは2N)の溶液に機能性金属物質2としての酸化亜鉛10gを溶解させて形成した。なお、機能性金属物質2として酸化亜鉛を選択したのは、安価で且つ取り扱い上安全であるためである。 Specifically, wood chips were used as the plant material 1. The normal alkaline solution is zinc oxide as the functional metal substance 2 in a 1 to 3N (preferably 2N) solution composed of 500 mL of distilled water (H 2 O) as ion exchange water containing 40 g of sodium hydroxide. The aluminum alkali solution is formed by dissolving 500 g of distilled water (H 2 O) as ion-exchanged water containing 40 g of sodium hydroxide and aluminum hydroxide 10 to form a 1 to 3 N (preferably 2 N) solution. 10 g of zinc oxide as the functional metal substance 2 was dissolved in The reason why zinc oxide is selected as the functional metal material 2 is that it is inexpensive and safe to handle.

そして、前記通常のアルカリ溶液およびアルミニウムアルカリ溶液にそれぞれ木材チップを浸漬した後、400〜900℃(好ましくは700℃)でそれぞれの液に浸漬した木材チップを炭化させて、機能性金属物質含有多孔質炭素材料Dを製造し、各機能性金属物質含有多孔質炭素材料Dに含まれる機能性金属物質(亜鉛)2の量を測定した。この機能性金属物質2の量の測定は、製造した機能性金属物質含有多孔質炭素材料Dを灰化させた後に硝酸で溶解した後、ICP(Inductively Coupled Plasma:誘導結合プラズマ)発光分析により行った。   Then, after immersing the wood chips in the normal alkali solution and the aluminum alkali solution, respectively, the wood chips immersed in the respective liquids are carbonized at 400 to 900 ° C. (preferably 700 ° C.) to obtain a porous material containing a functional metal substance. The carbonaceous material D was manufactured, and the amount of the functional metal substance (zinc) 2 contained in each functional metal substance-containing porous carbon material D was measured. The amount of the functional metal substance 2 is measured by ashing the produced functional metal substance-containing porous carbon material D, dissolving it with nitric acid, and then performing ICP (Inductively Coupled Plasma) emission analysis. It was.

その結果、通常のアルカリ溶液を用いて機能性金属物質含有多孔質炭素材料Dを製造した場合には、機能性金属物質含有多孔質炭素材料D100g中の機能性金属物質(亜鉛)2の量は10〜15gとなり、アルミニウムアルカリ溶液を用いて機能性金属物質含有多孔質炭素材料Dを製造した場合には、機能性金属物質含有多孔質炭素材料D100g中の機能性金属物質(亜鉛)2の量は20〜30gとなった。なお、アルミニウムアルカリ溶液を用いた場合でも、分析ではアルミニウムはほとんど検出されなかったため、析出しているのは全て機能性金属物質(亜鉛化合物)2であると考えられる。   As a result, when the functional metal substance-containing porous carbon material D is manufactured using a normal alkaline solution, the amount of the functional metal substance (zinc) 2 in 100 g of the functional metal substance-containing porous carbon material D is When the functional metal substance-containing porous carbon material D is produced using an aluminum alkaline solution, the amount of the functional metal substance (zinc) 2 in 100 g of the functional metal substance-containing porous carbon material D Became 20-30 g. Even when an aluminum alkali solution was used, aluminum was hardly detected in the analysis, so it is considered that all of the precipitated metal is the functional metal substance (zinc compound) 2.

また、通常のアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dの細孔4(仮導管)内の状態が撮影された顕微鏡写真およびその拡大図を図2(A)および(B)に、また、アルミニウムアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dの細孔4(仮導管)内の状態が撮影された顕微鏡写真およびその拡大図を図2(C)および(D)にそれぞれ示す。通常のアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dの細孔4(仮導管)内に析出した機能性金属物質2(酸化亜鉛)の結晶の大きさは、1〜7μm程度であったのに対して、アルミニウムアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dの細孔4(仮導管)内に析出した機能性金属物質2(酸化亜鉛)の結晶の大きさは、200〜400nm程度であった。   Moreover, the micrograph and the enlarged view in which the state in the pore 4 (temporary conduit | pipe) of the functional metal substance containing porous carbon material D manufactured using the normal alkaline solution was image | photographed and its enlarged view are shown to FIG. FIG. 2 (C) shows a micrograph and an enlarged view of the state in the pore 4 (temporary conduit) of the porous carbon material D containing the functional metal substance produced using the aluminum alkaline solution. ) And (D), respectively. The size of the crystal of the functional metal substance 2 (zinc oxide) deposited in the pores 4 (temporary conduit) of the functional carbon substance-containing porous carbon material D produced using a normal alkaline solution is 1 to 7 μm. The crystal of the functional metal substance 2 (zinc oxide) deposited in the pores 4 (temporary conduit) of the functional metal substance-containing porous carbon material D produced using the aluminum alkali solution. The size of was about 200 to 400 nm.

上記の結果から明らかなように、通常のアルカリ溶液を用いて機能性金属物質含有多孔質炭素材料Dを製造するよりもアルミニウムアルカリ溶液を用いて機能性金属物質含有多孔質炭素材料Dを製造するほうが、細孔4内に析出する機能性金属物質2(亜鉛)の量が増え、かつ析出した機能性金属物質2の結晶がより小さく(細かく)なるため、その反応性がより高まり、ひいては機能性金属物質含有多孔質炭素材料Dの効果が高まることとなる。   As is apparent from the above results, the functional metal substance-containing porous carbon material D is produced using an aluminum alkali solution rather than the functional metal substance-containing porous carbon material D produced using a normal alkali solution. However, since the amount of the functional metal substance 2 (zinc) deposited in the pores 4 is increased and the crystals of the precipitated functional metal substance 2 are smaller (finer), the reactivity is further increased, and consequently the function The effect of the porous carbon material D containing the conductive metal substance is enhanced.

また、前記機能性金属物質含有多孔質炭素材料Dが有する防藻性(水中における藻の発生を防止する性質)を確認するための実験を行った。詳しくは、それぞれ10Lの水道水を収容した水槽を複数用意し、これらの水槽を、フィルタ(水質浄化手段)として市販品の活性炭を用いた第1の水槽と、フィルタとして木炭を用いた第2の水槽と、フィルタとして本実施例の機能性金属物質含有多孔質炭素材料D(アルミニウムアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料D)を用いた第3の水槽との3種類に分けて、各水槽における藻の発生の様子を観察した。   In addition, an experiment was conducted to confirm the algae-proofing property (property for preventing the generation of algae in water) possessed by the functional metal substance-containing porous carbon material D. Specifically, a plurality of water tanks each containing 10 L of tap water are prepared, and these water tanks are a first water tank using commercially available activated carbon as a filter (water purification means), and a second using charcoal as a filter. And a third water tank using the functional metal substance-containing porous carbon material D (functional metal substance-containing porous carbon material D manufactured using an aluminum alkali solution) of this example as a filter. The state of algae in each aquarium was observed by dividing into types.

その結果、第1の水槽(市販品の活性炭を用いた水槽)および第2の水槽(木炭を用いた水槽)では3週間後に藻が大量に発生したが、第3の水槽(本実施例の機能性金属物質含有多孔質炭素材料Dを用いた水槽)では、3か月経過後も藻は発生せず、また、その後、藻が発生したが水槽のガラス壁面への付着は見られなかった。この結果から、前記機能性金属物質含有多孔質炭素材料Dが高い防藻性を有することが明らかとなった。   As a result, in the first aquarium (aquarium using commercially available activated carbon) and the second aquarium (aquarium using charcoal), a large amount of algae was generated after 3 weeks, but the third aquarium (in this example) In the water tank using the functional metal substance-containing porous carbon material D), algae did not occur even after the elapse of 3 months, and then algae were generated, but adhesion to the glass wall of the water tank was not observed. . From this result, it became clear that the functional metal substance-containing porous carbon material D has a high algaeproofing property.

また、前記機能性金属物質含有多孔質炭素材料Dが有する抗菌性を確認するための実験を行った。詳しくは、それぞれ内部で大腸菌を液体培養してある容器を複数用意し、木炭を収容した第1の容器と、前記通常のアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dを収容した第2の容器と、アルミニウムアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dを収容した第3の容器との3種類に分けて、各容器における大腸菌の増殖率をコロニー数で比較した。   In addition, an experiment for confirming the antibacterial property of the functional metal substance-containing porous carbon material D was performed. Specifically, a plurality of containers in which Escherichia coli is liquid-cultured are prepared, and a first container containing charcoal and a porous carbon material D containing a functional metal substance manufactured using the normal alkaline solution are provided. The growth rate of Escherichia coli in each container is divided into three types, the second container accommodated and the third container containing the functional metal substance-containing porous carbon material D produced using an aluminum alkaline solution. Compared by number.

その結果、第1の容器(木炭を収容した容器)では前記コロニー数が平均143であったのに対して、第2の容器(通常のアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dを収容した容器)ではコロニー数の平均が5、第3の容器(アルミニウムアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料Dを収容した容器)ではコロニー数の平均が3という低い値となった。この結果から、前記機能性金属物質含有多孔質炭素材料Dが高い抗菌性を有することが明らかとなった。   As a result, the average number of colonies in the first container (contained charcoal) was 143, whereas the second container (functional metal material-containing porous material manufactured using a normal alkaline solution) was used. In the container containing the carbon material D), the average number of colonies is 5, and in the third container (the container containing the functional metal substance-containing porous carbon material D manufactured using the aluminum alkaline solution), the average number of colonies is The value was as low as 3. From this result, it became clear that the functional metal substance-containing porous carbon material D has high antibacterial properties.

この発明の一実施例に係る機能性金属物質含有多孔質炭素材料の製造方法を概略的に示す説明図である。It is explanatory drawing which shows roughly the manufacturing method of the functional metal substance containing porous carbon material which concerns on one Example of this invention. (A)および(B)は、通常のアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料の細孔(仮導管)内の状態が撮影された顕微鏡写真およびその拡大図であり、(C)および(D)は、アルミニウムアルカリ溶液を用いて製造した機能性金属物質含有多孔質炭素材料の細孔(仮導管)内の状態が撮影された顕微鏡写真およびその拡大図である。(A) and (B) are a micrograph and an enlarged view of a state in which pores (temporary conduit) of a functional metal substance-containing porous carbon material produced using a normal alkaline solution are photographed, (C) And (D) is the microscope picture and the enlarged view by which the state in the pore (temporary conduit | pipe) of the functional metal substance containing porous carbon material manufactured using the aluminum alkaline solution was image | photographed.

符号の説明Explanation of symbols

1 植物性材料
2 機能性金属物質
D 機能性金属物質含有多孔質炭素材料
DESCRIPTION OF SYMBOLS 1 Plant material 2 Functional metal substance D Porous carbon material containing functional metal substance

Claims (5)

植物性材料を炭化してなる植物性多孔質材料に機能性金属及び/又は機能性金属化合物を保持させたことを特徴とする機能性金属及び/又は機能性金属化合物含有多孔質炭素材料。   A functional metal and / or a functional metal compound-containing porous carbon material, wherein a functional metal and / or a functional metal compound is held in a plant porous material obtained by carbonizing a plant material. 機能性金属及び/又は機能性金属化合物を1〜40重量%含む請求項1に記載の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料。   The functional metal and / or functional metal compound-containing porous carbon material according to claim 1, comprising 1 to 40% by weight of the functional metal and / or the functional metal compound. 保持させる機能性金属及び/又は機能性金属化合物の結晶が10μm以下である請求項1または2に記載の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の製造方法。   The functional metal and / or functional metal compound-containing porous carbon material according to claim 1 or 2, wherein the functional metal and / or functional metal compound crystals to be retained are 10 µm or less. 機能性金属を含むアルカリ溶液に植物性材料を浸漬後、400〜900℃で炭化させることを特徴とする機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の製造方法。   A method for producing a functional metal and / or a porous carbon material containing a functional metal compound, wherein the plant material is immersed in an alkaline solution containing a functional metal and then carbonized at 400 to 900 ° C. 前記アルカリ溶液が、アルミニウムアルカリ溶液である請求項4に記載の機能性金属及び/又は機能性金属化合物含有多孔質炭素材料の製造方法。   The method for producing a porous carbon material containing a functional metal and / or a functional metal compound according to claim 4, wherein the alkali solution is an aluminum alkali solution.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7421608B1 (en) 2022-08-01 2024-01-24 星和電機株式会社 Metal particle-supported porous carbon material and its manufacturing method, precursor of metal particle-supported porous carbon material, and catalyst material and electrode material using metal particle-supported porous carbon material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7421608B1 (en) 2022-08-01 2024-01-24 星和電機株式会社 Metal particle-supported porous carbon material and its manufacturing method, precursor of metal particle-supported porous carbon material, and catalyst material and electrode material using metal particle-supported porous carbon material

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