JPH09215735A - Deodorant and deodorizing member - Google Patents
Deodorant and deodorizing memberInfo
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- JPH09215735A JPH09215735A JP8026885A JP2688596A JPH09215735A JP H09215735 A JPH09215735 A JP H09215735A JP 8026885 A JP8026885 A JP 8026885A JP 2688596 A JP2688596 A JP 2688596A JP H09215735 A JPH09215735 A JP H09215735A
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- deodorant
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は冷蔵庫等に使用さ
れ、冷蔵庫内の悪臭の原因となる硫化水素、硫化メチル
類、有機アミン及びアンモニア等の除去又は雑菌の繁殖
の防止に使用される脱臭剤及び脱臭部材に関する。TECHNICAL FIELD The present invention relates to a deodorant used for refrigerators and the like, which is used for removing hydrogen sulfide, methyl sulfides, organic amines, ammonia and the like, which cause malodor in the refrigerator, or for preventing the growth of various bacteria. And a deodorizing member.
【０００２】[0002]
【従来の技術】従来、冷蔵庫等の中の脱臭剤として活性
炭が使用されていることは公知である。しかしながら、
活性炭は脱臭剤としての寿命が短く、交換の頻度が高い
ので、脱臭剤の長寿命化に対する要求が高くなってきて
いた。2. Description of the Related Art Conventionally, it is known that activated carbon is used as a deodorant in refrigerators and the like. However,
Since activated carbon has a short life as a deodorant and is frequently replaced, there has been an increasing demand for extending the life of the deodorant.
【０００３】そこで、オゾンを利用した脱臭方法が提案
されている（特公平５−８６２５３、特公平５−２８１
４８）。このオゾン脱臭法は、オゾン発生器によってオ
ゾンを発生させ、オゾンの存在下において触媒を使用し
て悪臭成分を接触分解させるものである。Therefore, a deodorizing method using ozone has been proposed (Japanese Patent Publication No. 5-86253, Japanese Patent Publication No. 5-281).
48). In this ozone deodorization method, ozone is generated by an ozone generator, and a malodorous component is catalytically decomposed using a catalyst in the presence of ozone.
【０００４】また、白金触媒を使用した熱分解脱臭法も
提案されている。熱分解脱臭法は、吸着材に白金等の熱
分解触媒を付与し、一定時間において冷蔵庫内の臭気を
吸着させた後、ヒータで加熱することにより臭気物質を
分解させる方法である。A thermal decomposition deodorizing method using a platinum catalyst has also been proposed. The thermal decomposition deodorization method is a method in which a thermal decomposition catalyst such as platinum is applied to an adsorbent to adsorb the odor in the refrigerator for a certain period of time and then heated by a heater to decompose the odorous substance.
【０００５】これらのオゾン脱臭法及び熱分解脱臭法
は、活性炭を使用する脱臭剤と比較して脱臭能力を長く
維持することができる。The ozone deodorizing method and the thermal decomposition deodorizing method can maintain the deodorizing ability for a long time as compared with the deodorizing agent using activated carbon.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、オゾン
脱臭法はオゾン発生器が必要であり、熱分解脱臭法は加
熱用ヒータが必要であるので、脱臭装置の製造コストが
高くなると共に、装置が大規模になるという問題点があ
る。However, since the ozone deodorizing method requires an ozone generator and the thermal decomposition deodorizing method requires a heater for heating, the manufacturing cost of the deodorizing apparatus is high and the apparatus is large. There is a problem that it becomes a scale.
【０００７】本発明はかかる問題点に鑑みてなされたも
のであって、長寿命で低コストであると共に、悪臭成分
を効率的に除去することができ、抗菌性能が優れた脱臭
剤及び脱臭部材を提供することを目的とする。The present invention has been made in view of the above problems, and has a long service life and a low cost, can efficiently remove a malodorous component, and has an excellent antibacterial property, and a deodorant and a deodorant member. The purpose is to provide.
【０００８】[0008]
【課題を解決するための手段】本発明に係る脱臭剤は、
Ａｌ2Ｏ3、ＳｉＯ2 、マンガン酸化物、銅酸化物及びマ
グネシウム酸化物からなる群から選択された少なくとも
１種の酸化物と、活性炭とを含有し、更に、Ｎａ化合物
をＮａ換算値で０．０１乃至５．００重量％、Ｋ化合物
をＫ換算値で０．０１乃至５．００重量％含有すること
を特徴とする。Means for Solving the Problems The deodorant according to the present invention is
It contains at least one oxide selected from the group consisting of Al 2 O 3 , SiO 2 , manganese oxide, copper oxide and magnesium oxide, and activated carbon, and further contains a Na compound in Na conversion value of 0. 0.01 to 5.00% by weight, and a K compound is contained in an amount of 0.01 to 5.00% by weight in terms of K value.
【０００９】また、８０℃で１時間乾燥された後に測定
された強熱減量（Ｉｇ．ｌｏｓｓ）が０．１乃至１５．
０重量％であることが好ましい。更に、含有される活性
炭は１０乃至５０重量％であることが好ましい。The loss on ignition (Ig.loss) measured after drying at 80 ° C. for 1 hour is 0.1 to 15.
It is preferably 0% by weight. Further, it is preferable that the contained activated carbon is 10 to 50% by weight.
【００１０】更にまた、Ａｌ2Ｏ3含有量は１０乃至５０
重量％、ＳｉＯ2 含有量は１０乃至５０重量％、マンガ
ン酸化物はＭｎＯ換算値で５乃至３０重量％、銅酸化物
はＣｕＯ換算値で１乃至１０重量％、マグネシウム酸化
物はＭｇＯ換算値で０．０１乃至３．００重量％である
ことが好ましい。Furthermore, the Al 2 O 3 content is 10 to 50.
% By weight, SiO 2 content is 10 to 50% by weight, manganese oxide is 5 to 30% by weight in terms of MnO, copper oxide is 1 to 10% by weight in terms of CuO, and magnesium oxide is in terms of MgO. It is preferably 0.01 to 3.00% by weight.
【００１１】更にまた、ＳｉＯ2 の一部又は全部がＳｉ
Ｏ2 ／Ａｌ2Ｏ3モル比が５以上であるハイシリカゼオラ
イトとして添加されていることが好ましい。Furthermore, part or all of SiO 2 is Si
It is preferably added as high silica zeolite having an O 2 / Al 2 O 3 molar ratio of 5 or more.
【００１２】更にまた、銀又は銀化合物をＡｇ換算値で
０．００１乃至１５重量％含有することが好ましい。Further, it is preferable to contain silver or a silver compound in an amount of 0.001 to 15% by weight in terms of Ag.
【００１３】本発明に係る脱臭部材は、前記脱臭剤を担
持体に被着して構成されていることを特徴とする。The deodorizing member according to the present invention is characterized in that the deodorizing agent is adhered to a carrier.
【００１４】[0014]
【発明の実施の形態】本願発明者等が前記課題を解決す
るために鋭意実験研究を重ねた結果、脱臭剤中にＳｉＯ
2 、マンガン酸化物、銅酸化物及びマグネシウム酸化物
からなる群から少なくとも１種と活性炭とを含有し、Ｎ
ａ化合物及びＫ化合物の含有量を適正量に調整すると、
脱臭性能が向上すると共に長寿命の脱臭剤を得ることが
できることを見い出した。また、含有成分中の結晶水
（Ig.loss ）量を規定し、前記種々の酸化物を適正量に
規制すると、更に一層脱臭効率が向上する。BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive experiments and researches conducted by the inventors of the present application to solve the above-mentioned problems, SiO 2 was contained in the deodorant.
2 , containing at least one selected from the group consisting of manganese oxide, copper oxide and magnesium oxide, and activated carbon, N
When the contents of the a compound and the K compound are adjusted to appropriate amounts,
It has been found that the deodorizing performance is improved and a long-life deodorant can be obtained. Further, if the amount of water of crystallization (Ig.loss) in the contained components is regulated and the various oxides are regulated to proper amounts, the deodorizing efficiency is further improved.
【００１５】本発明の脱臭剤は粉状のまま使用すること
ができるが、ペレット状又はハニカム状等の成形体にし
て使用することが好適である。また、本発明において
は、含有成分及び組成を適正量に規定した脱臭剤を担持
体に被着させることによって脱臭部材を構成することも
できる。従って、本発明においては脱臭剤全重量に対す
る脱臭剤中の化学成分及び組成を規定するものとする。The deodorant of the present invention can be used in a powder form as it is, but it is preferable to use it as a pellet-shaped or honeycomb-shaped molded body. Further, in the present invention, the deodorizing member can also be constituted by applying a deodorizing agent in which the components and the composition are regulated to proper amounts to the carrier. Therefore, in the present invention, the chemical components and composition in the deodorant based on the total weight of the deodorant are defined.
【００１６】以下、本発明に係る脱臭剤に含有される化
学成分及びその組成限定理由について説明する。但し、
化学組成においては、試料を８０℃で１時間乾燥させた
後に測定した値とする。The chemical components contained in the deodorant according to the present invention and the reasons for limiting the composition thereof will be described below. However,
The chemical composition is a value measured after the sample was dried at 80 ° C. for 1 hour.
【００１７】Ｎａ化合物（Ｎａ換算値）：０．０１乃至
５．００重量％ Ｎａは脱臭性能を向上させる成分である。脱臭剤中のＮ
ａ化合物がＮａ換算値で０．０１重量％未満であると、
特に、硫化水素等の酸性物質に対する脱臭効果が低下す
る。一方、脱臭剤中のＮａ化合物がＮａ換算値で５．０
０重量％を超えると、触媒成分と反応して非活性な物質
に変化するので、脱臭性能が低下する。従って、脱臭剤
全重量に対するＮａ化合物はＮａ換算値で０．０１乃至
５．００重量％とする。なお、Ｎａ化合物としては、酸
化ナトリウム、過酸化ナトリウム、炭酸ナトリウム、リ
ン酸ナトリウム、塩化ナトリウム、硫酸ナトリウム、水
酸化ナトリウム及び過塩素酸ナトリウム等の無機化合物
並びにクエン酸ナトリウム、酢酸ナトリウム及びシュウ
酸ナトリウム等の有機化合物がある。 Na compound (Na conversion value): 0.01 to
5.00 wt% Na is a component that improves the deodorizing performance. N in deodorant
When the compound a is less than 0.01 wt% in terms of Na,
In particular, the deodorizing effect on acidic substances such as hydrogen sulfide decreases. On the other hand, the Na compound in the deodorant is 5.0 in Na conversion value.
When it exceeds 0% by weight, it reacts with the catalyst component and changes into an inactive substance, so that the deodorizing performance is deteriorated. Therefore, the Na compound content relative to the total weight of the deodorant is 0.01 to 5.00% by weight in terms of Na. The Na compounds include inorganic compounds such as sodium oxide, sodium peroxide, sodium carbonate, sodium phosphate, sodium chloride, sodium sulfate, sodium hydroxide and sodium perchlorate, and sodium citrate, sodium acetate and sodium oxalate. There are organic compounds such as.
【００１８】Ｋ化合物（Ｋ換算値）：０．０１乃至５．
００重量％ Ｋは、Ｎａと同様に、脱臭性能を向上させる成分であ
る。脱臭剤中のＫ化合物がＫ換算値で０．０１重量％未
満であると、特に、硫化水素等の酸性物質に対する脱臭
効果が低下する。一方、脱臭剤中のＫ化合物がＫ換算値
で５．００重量％を超えると、触媒成分と反応して非活
性な物質に変化するので、脱臭性能が低下する。従っ
て、脱臭剤全重量に対するＫ化合物はＫ換算値で０．０
１乃至５．００重量％とする。なお、Ｋ化合物として
は、酸化カリウム、過酸化カリウム、炭酸カリウム、リ
ン酸カリウム、塩化カリウム、硫酸カリウム、水酸化カ
リウム及び過塩素酸カリウム等の無機化合物並びにクエ
ン酸カリウム、酢酸カリウム及びシュウ酸カリウム等の
有機化合物がある。 K compound (K conversion value): 0.01 to 5.
00 wt% K, like Na, is a component that improves deodorizing performance. When the K compound in the deodorant is less than 0.01% by weight in terms of K value, the deodorizing effect on acidic substances such as hydrogen sulfide is particularly deteriorated. On the other hand, if the K compound in the deodorant exceeds 5.00% by weight in terms of K value, it reacts with the catalyst component and changes to an inactive substance, so that the deodorizing performance deteriorates. Therefore, the K compound based on the total weight of the deodorant is 0.0 in terms of K.
1 to 5.00% by weight. Examples of the K compound include inorganic compounds such as potassium oxide, potassium peroxide, potassium carbonate, potassium phosphate, potassium chloride, potassium sulfate, potassium hydroxide and potassium perchlorate, and potassium citrate, potassium acetate and potassium oxalate. There are organic compounds such as.
【００１９】強熱減量（Ig.loss ）：０．１乃至１５．
０重量％ 強熱減量は鉱物中の結晶水の量を判断することができる
ものであり、この結晶水は、特に、水溶性の硫化水素及
びトリメチルアミンに対する脱臭性能を向上させる効果
を有する。強熱減量が０．１重量％未満であると、硫化
水素及びトリメチルアミンに対する脱臭性能が低下す
る。一方、強熱減量が１５．０重量％を超えると、成形
体にした場合に必要とされる強度が低下する。従って、
脱臭剤全重量に対する強熱減量（Ig.loss ）は０．１乃
至１５．０重量％とすることが好ましい。 Ignition loss (Ig.loss): 0.1 to 15.
The 0% by weight loss on ignition can determine the amount of water of crystallization in minerals, and this water of crystallization has an effect of improving the deodorizing performance especially for water-soluble hydrogen sulfide and trimethylamine. When the loss on ignition is less than 0.1% by weight, the deodorizing performance with respect to hydrogen sulfide and trimethylamine deteriorates. On the other hand, when the loss on ignition exceeds 15.0% by weight, the strength required for forming a molded product decreases. Therefore,
The loss on ignition (Ig.loss) relative to the total weight of the deodorant is preferably 0.1 to 15.0% by weight.
【００２０】なお、強熱減量（Ig.loss ）とは、ＪＩＳ
Ｍ８８５３の長石分析方法に示すように、乾燥処理が
施された試料を１０００℃で恒量になるまで強熱したと
きの減量をいうが、本発明においては活性炭を含有する
ので、Ｃ（炭素）の燃焼を防止するために、窒素雰囲気
中において強熱するものとする。The ignition loss (Ig.loss) is defined by JIS
As shown in the feldspar analysis method of M8853, it refers to the weight loss when a dried sample is ignited at 1000 ° C. until it becomes a constant weight. However, in the present invention, since activated carbon is contained, C (carbon) In order to prevent combustion, it shall be ignited in a nitrogen atmosphere.
【００２１】活性炭：１０乃至５０重量％ 活性炭は脱臭性能を向上させる成分である。脱臭剤中の
活性炭が１０重量％未満であると、十分な脱臭効果を得
ることができない。一方、脱臭剤中の活性炭が５０重量
％を超えると、成形体にした場合に必要とされる強度が
不足すると共に、粉化しやすくなる。従って、脱臭剤全
重量に対する活性炭の含有量は１０乃至５０重量％とす
ることが好ましい。 Activated carbon: 10 to 50% by weight Activated carbon is a component for improving deodorizing performance. If the activated carbon in the deodorant is less than 10% by weight, a sufficient deodorizing effect cannot be obtained. On the other hand, when the activated carbon in the deodorant exceeds 50% by weight, the strength required for forming a molded body is insufficient and the powder tends to be pulverized. Therefore, the content of activated carbon is preferably 10 to 50% by weight based on the total weight of the deodorant.
【００２２】Ａｌ2Ｏ3：１０乃至５０重量％ Ａｌ2Ｏ3は成形体にした場合に必要とされる強度を確保
するための成分である。脱臭剤中のＡｌ2Ｏ3が１０重量
％未満であると、その効果が十分に得られないので、成
形体の強度が不足すると共に、粉化しやすくなる。一
方、脱臭剤中のＡｌ2Ｏ3が５０重量％を超えると、脱臭
効果を有する成分の含有量が相対的に低下するので、脱
臭性能が低下する。従って、脱臭剤中にＡｌ2Ｏ3を含有
させる場合、脱臭剤全重量に対するＡｌ2Ｏ3含有量は１
０乃至５０重量％とすることが好ましい。 Al 2 O 3 : 10 to 50 wt% Al 2 O 3 is a component for ensuring the strength required when forming a molded body. If Al 2 O 3 in the deodorant is less than 10% by weight, the effect cannot be sufficiently obtained, so that the strength of the molded body is insufficient and the powder is easily pulverized. On the other hand, when Al 2 O 3 in the deodorant exceeds 50% by weight, the content of the component having the deodorizing effect is relatively decreased, and the deodorizing performance is deteriorated. Therefore, when Al 2 O 3 is contained in the deodorant, the Al 2 O 3 content based on the total weight of the deodorant is 1
It is preferably 0 to 50% by weight.
【００２３】ＳｉＯ2 ：１０乃至５０重量％ ＳｉＯ2 は脱臭性能を向上させる成分である。脱臭剤中
のＳｉＯ2 が１０重量％未満であると、特に、硫化メチ
ル及びトリメチルアミンに対する脱臭性能が低下する。
一方、脱臭剤中のＳｉＯ2 が５０重量％を超えると、成
形体にした場合に必要とされる強度が不足すると共に、
粉化しやすくなる。従って、脱臭剤中にＳｉＯ2 を含有
させる場合、脱臭剤全重量に対するＳｉＯ2 含有量は１
０乃至５０重量％とすることが好ましい。 SiO 2 : 10 to 50 wt% SiO 2 is a component that improves the deodorizing performance. If the amount of SiO 2 in the deodorant is less than 10% by weight, the deodorizing performance especially against methyl sulfide and trimethylamine deteriorates.
On the other hand, when the SiO 2 content in the deodorant exceeds 50% by weight, the strength required for forming a molded article becomes insufficient, and
It becomes easy to powder. Therefore, when SiO 2 is contained in the deodorant, the SiO 2 content is 1 based on the total weight of the deodorant.
It is preferably 0 to 50% by weight.
【００２４】また、このＳｉＯ2 の一部又は全部の供給
源であるハイシリカゼオライトは硫化メチルに対する脱
臭性能を向上させる効果がある。従って、ＳｉＯ2 の一
部又は全部がＳｉＯ2 ／Ａｌ2Ｏ3モル比が５以上である
ハイシリカゼオライトして添加されていることが望まし
い。The high-silica zeolite, which is a source of a part or all of this SiO 2 , has the effect of improving the deodorizing performance for methyl sulfide. Therefore, it is desirable that a part of SiO 2 or the whole is added to the high-silica zeolite is SiO 2 / Al 2 O 3 molar ratio of 5 or more.
【００２５】Ｍｎ酸化物（ＭｎＯ換算値）：５乃至３０
重量％ Ｍｎ酸化物は脱臭性能を向上させる成分であり、特に、
Ｍｎ酸化物を銅酸化物と共存させることにより、脱臭性
能が著しく向上する。脱臭剤中のＭｎ酸化物がＭｎＯ換
算値で５重量％未満であると、十分な脱臭効果を得るこ
とができない。一方、Ｍｎ酸化物がＭｎＯ換算値で３０
重量％を超えると、成形体にした場合に必要とされる強
度が低下すると共に、粉化しやすくなる。従って、脱臭
剤中にＭｎ酸化物を含有させる場合、脱臭剤全重量に対
するＭｎ酸化物はＭｎＯ換算値で５乃至３０重量％とす
ることが好ましい。 Mn oxide (MnO conversion value): 5 to 30
The wt% Mn oxide is a component that improves the deodorizing performance.
The coexistence of the Mn oxide and the copper oxide significantly improves the deodorizing performance. If the Mn oxide content in the deodorant is less than 5% by weight in terms of MnO, a sufficient deodorizing effect cannot be obtained. On the other hand, the Mn oxide content is 30 in terms of MnO.
When the content is more than weight%, the strength required for forming a molded product is lowered and the powder is easily pulverized. Therefore, when the Mn oxide is contained in the deodorant, the Mn oxide is preferably 5 to 30 wt% in terms of MnO based on the total weight of the deodorant.
【００２６】銅酸化物（ＣｕＯ換算値）：１乃至１０重
量％ 銅酸化物は脱臭性能及び抗菌性能を向上させる成分であ
り、前述の如く、銅酸化物をＭｎ酸化物と共存させるこ
とにより、脱臭性能が著しく向上する。脱臭剤中の銅酸
化物がＣｕＯ換算値で１重量％未満であると、十分な脱
臭及び抗菌効果を得ることができない。一方、Ｃｕ酸化
物がＣｕＯ換算値で１０重量％を超えると、成形体にし
た場合に必要とされる強度が低下し、粉化しやすくな
る。従って、脱臭剤中に銅酸化物を含有させる場合、脱
臭剤全重量に対するＣｕ酸化物はＣｕＯ換算値で１乃至
１０重量％とすることが好ましい。 Copper oxide (CuO conversion value): 1 to 10 layers
The amount% copper oxide is a component that improves deodorizing performance and antibacterial performance, and as described above, the coexistence of copper oxide and Mn oxide significantly improves the deodorizing performance. When the copper oxide content in the deodorant is less than 1% by weight in terms of CuO, sufficient deodorizing and antibacterial effects cannot be obtained. On the other hand, when the Cu oxide content exceeds 10% by weight in terms of CuO, the strength required for forming a molded body is lowered and the powder is easily pulverized. Therefore, when the copper oxide is contained in the deodorant, the Cu oxide content relative to the total weight of the deodorant is preferably 1 to 10% by weight in terms of CuO.
【００２７】Ｍｇ酸化物（ＭｇＯ換算値）：０．０１乃
至３．００重量％ Ｍｇ酸化物は抗菌性能を向上させる成分である。脱臭剤
中のＭｇ酸化物がＭｇＯ換算値で０．０１重量％未満で
あると、十分な抗菌効果を得ることができない。一方、
Ｍｇ酸化物がＭｇＯ換算値で３．００重量％を超える
と、成形体にした場合に必要とされる強度が低下し、粉
化しやすくなる。従って、脱臭剤中にＭｇ酸化物を含有
させる場合、脱臭剤全重量に対するＭｇ酸化物はＭｇＯ
換算値で０．０１乃至３．００重量％とすることが好ま
しい。 Mg oxide (MgO conversion value): 0.01
To 3.00 wt% Mg oxide is a component that improves antibacterial performance. If the Mg oxide content in the deodorant is less than 0.01% by weight in terms of MgO, a sufficient antibacterial effect cannot be obtained. on the other hand,
If the Mg oxide content exceeds 3.00% by weight in terms of MgO, the strength required for forming a molded product decreases and the powder tends to be pulverized. Therefore, when the Mg oxide is contained in the deodorant, the Mg oxide is MgO based on the total weight of the deodorant.
The converted value is preferably 0.01 to 3.00% by weight.
【００２８】銀又は銀化合物（Ａｇ換算値）：０．００
１乃至１５重量％ 銀又は銀化合物はＭｇ酸化物と同時に添加すると、両者
の相互作用により、抗菌性能を向上させることができ
る。脱臭剤中の銀又は銀化合物がＡｇ換算値で０．００
１重量％未満であると、十分な抗菌効果を得ることがで
きない。一方、銀又は銀化合物がＡｇ換算値で１５重量
％を超えると、成形体にした場合に必要とされる強度が
低下し、粉化しやすくなる。従って、脱臭剤全重量に対
する銀又は銀化合物はＡｇ換算値で０．００１乃至１５
重量％とすることが好ましい。なお、脱臭剤中のＡｇと
して、Ａｇ及びＡｇ化合物の他にＡｇ含有物がある。こ
のＡｇ含有物とは、ゼオライト及びヒドロキシルアパタ
イト等のようなイオン交換体中のイオンをＡｇに交換し
てＡｇを含有するようにした物質をいう。 Silver or silver compound (Ag conversion value): 0.00
If 1 to 15% by weight of silver or a silver compound is added at the same time as Mg oxide, the interaction between the two can improve the antibacterial performance. The silver or silver compound in the deodorant is 0.00 in terms of Ag.
If it is less than 1% by weight, a sufficient antibacterial effect cannot be obtained. On the other hand, if the silver or silver compound exceeds 15% by weight in terms of Ag, the strength required for forming a molded article decreases and the powder is easily pulverized. Therefore, the silver or silver compound relative to the total weight of the deodorant is 0.001 to 15 in terms of Ag.
It is preferable to set the weight%. As Ag in the deodorant, there are Ag-containing substances in addition to Ag and Ag compounds. The term "Ag-containing material" refers to a material obtained by exchanging ions in an ion exchanger such as zeolite and hydroxylapatite for Ag so as to contain Ag.
【００２９】[0029]
【実施例】以下、本発明に係る脱臭剤の実施例について
その比較例と比較して具体的に説明する。EXAMPLES Examples of the deodorant according to the present invention will be specifically described below in comparison with its comparative example.
【００３０】先ず、脱臭剤を種々の成分で配合し、各脱
臭剤についての化学組成を分析した。各化学成分の分析
に際しては、前処理として試料を８０℃で１時間の乾燥
処理を実施した後に、下記表１に示す方法で分析した。First, a deodorant was mixed with various components, and the chemical composition of each deodorant was analyzed. In the analysis of each chemical component, the sample was subjected to a drying treatment at 80 ° C. for 1 hour as a pretreatment and then analyzed by the method shown in Table 1 below.
【００３１】[0031]
【表１】 [Table 1]
【００３２】また、強熱減量（Ig.loss ）については、
前述の如く、ＪＩＳ Ｍ８８５３の長石分析方法に準じ
て、前記乾燥処理が施された試料を１０００℃で恒量に
なるまで強熱したときの減量を測定した。但し、本発明
においては、脱臭剤中に活性炭を含有しているので、Ｃ
の燃焼を防止するために、窒素雰囲気中で強熱した。Regarding the loss on ignition (Ig.loss),
As described above, in accordance with the feldspar analysis method of JIS M8853, the weight loss of the dried sample was measured when it was ignited at 1000 ° C. to a constant weight. However, in the present invention, since the deodorant contains activated carbon,
It was ignited in a nitrogen atmosphere in order to prevent the combustion.
【００３３】次いで、各脱臭剤について、脱臭性能、圧
縮強度及び抗菌性能を評価した。これらの評価方法は以
下の通りである。Next, each deodorant was evaluated for deodorizing performance, compressive strength and antibacterial performance. These evaluation methods are as follows.
【００３４】脱臭性能については、ハニカム成形した脱
臭剤をサンプルとして、図１に示す脱臭性能評価装置を
使用して評価した。図１に示すように、エアボンベ８及
び悪臭ガスボンベ７から供給されるガスは、ガス混合器
６によって混合された後、その混合ガスが流量計５を介
して恒温恒湿装置２内に供給されるように配置されてい
る。恒温恒湿装置２内には、入口濃度測定器３及び出口
濃度測定器４が配置され、測定器３と４との間にはサン
プル１が配置されるようになっている。The deodorizing performance was evaluated using the deodorizing performance evaluation apparatus shown in FIG. 1 using the honeycomb-molded deodorizing agent as a sample. As shown in FIG. 1, the gas supplied from the air cylinder 8 and the malodorous gas cylinder 7 is mixed by the gas mixer 6, and then the mixed gas is supplied into the constant temperature and humidity apparatus 2 via the flow meter 5. Are arranged as follows. An inlet concentration measuring device 3 and an outlet concentration measuring device 4 are arranged in the constant temperature and humidity device 2, and a sample 1 is arranged between the measuring devices 3 and 4.
【００３５】このように構成された脱臭性能評価装置を
使用して、恒温恒湿装置２内の入口濃度測定器３と出口
濃度測定器４との間にサンプル１を配置し、入口濃度測
定器側から混合ガスを供給して、入口濃度測定器３によ
り入口悪臭濃度Ｃｉ（ｐｐｍ）を測定すると共に、出口
濃度測定器４により出口悪臭濃度Ｃｏ（ｐｐｍ）を測定
した。但し、入口悪臭濃度Ｃｉは１００ｐｐｍ、ＳＶ
（Space Velocity；空間速度）は９００００ｈｒ-1、装
置２内の温度は２５℃、湿度は６０％とした。このＳＶ
とは、単位触媒体積に対して、単位時間に通過する悪臭
気体の容積のことであり、脱臭性能の評価条件の１つで
あって、下記数式１によって算出することができる。Using the deodorizing performance evaluation device thus constructed, the sample 1 is placed between the inlet concentration measuring device 3 and the outlet concentration measuring device 4 in the constant temperature and humidity device 2, and the inlet concentration measuring device is arranged. A mixed gas was supplied from the side, and the inlet malodor concentration Ci (ppm) was measured by the inlet concentration measuring device 3 and the outlet malodor concentration Co (ppm) was measured by the outlet concentration measuring device 4. However, the inlet malodor concentration Ci is 100 ppm, SV
(Space Velocity) was 90,000 hr −1 , the temperature inside the apparatus 2 was 25 ° C., and the humidity was 60%. This SV
Is the volume of the malodorous gas that passes per unit time with respect to the unit catalyst volume, which is one of the evaluation conditions of the deodorizing performance, and can be calculated by the following mathematical formula 1.
【００３６】[0036]
【数１】 ＳＶ（hr-1）＝処理ガス量（m3／hr）／触媒量（m3）[Formula 1] SV (hr -1 ) = treatment gas amount (m 3 / hr) / catalyst amount (m 3 )
【００３７】本実施例においては、直径が１２ｍｍで厚
さが１０ｍｍのサイズの触媒に対して、１．７リットル／分
の悪臭ガスを流して、サンプル１の脱臭性能を下記数式
２により算出した。In this example, 1.7 liters / minute of a malodorous gas was flowed to a catalyst having a diameter of 12 mm and a thickness of 10 mm, and the deodorizing performance of Sample 1 was calculated by the following mathematical formula 2. .
【００３８】[0038]
【数２】脱臭性能＝（１−Ｃｏ／Ｃｉ）×１００（％）[Equation 2] Deodorizing performance = (1-Co / Ci) × 100 (%)
【００３９】なお、混合ガスの悪臭源としては、ＣＨ3
ＳＨ、Ｈ2Ｓ、（ＣＨ3）2Ｓ及び（ＣＨ3）3Ｎが含まれ
ており、ＣＨ3ＳＨ、Ｈ2Ｓ及び（ＣＨ3）3Ｎについては
脱臭性能が８０％以上を良好として、（ＣＨ3）2Ｓにつ
いては７０％以上を良好、８０％以上を最良とした。CH 3 is used as a source of the malodor of the mixed gas.
SH, H 2 S, (CH 3 ) 2 S and (CH 3 ) 3 N are contained. For CH 3 SH, H 2 S and (CH 3 ) 3 N, deodorization performance of 80% or more is considered good. , (CH 3 ) 2 S, 70% or more was good, and 80% or more was the best.
【００４０】また、圧縮強度については、図２に示すよ
うに、ハニカム成形された２０ｍｍ×２０ｍｍ×２０ｍ
ｍのサイズのサンプル１を使用し、通気方向に荷重を印
加して、サンプル１が破壊するときのサンプルの断面積
Ａ（ｍ2 ）に対する最大荷重Ｐ（Ｎ）を測定した。そし
て、サンプル１の圧縮強度σを下記数式３により算出し
た。Regarding the compressive strength, as shown in FIG. 2, honeycomb-formed 20 mm × 20 mm × 20 m
A sample 1 having a size of m was used, a load was applied in the ventilation direction, and the maximum load P (N) with respect to the cross-sectional area A (m 2 ) of the sample when the sample 1 broke was measured. Then, the compressive strength σ of Sample 1 was calculated by the following mathematical formula 3.
【００４１】[0041]
【数３】圧縮強度σ＝Ｐ／Ａ （ＭＰａ）(3) Compressive strength σ = P / A (MPa)
【００４２】更に抗菌性能については、抗菌性能の評価
培養温度条件を６乃至１０℃として、ＪＩＳ Ｚ２９１
１に準じて菌糸の発育を肉眼によって評価した。この抗
菌性能試験に使用したカビを下記表２に示す。Further, regarding the antibacterial performance, JIS Z291 was used under the condition that the culture temperature condition for evaluating the antibacterial performance was 6 to 10 ° C.
According to 1, the development of hyphae was visually evaluated. The molds used in this antibacterial performance test are shown in Table 2 below.
【００４３】[0043]
【表２】 [Table 2]
【００４４】なお、本実施例においては、サンプルに菌
糸を接種して、その部分に菌糸の発育が認められないも
のを抗菌性能が良好（○）であるとし、その他のものを
不良（×）とした。In this example, the sample was inoculated with hyphae, and if the growth of hyphae was not observed in that part, the antibacterial performance was good (○), and the others were bad (x). And
【００４５】このようにして脱臭剤の化学成分を分析
し、全ての項目が本発明の範囲内であるものを実施例と
して、この分析結果を下記表３〜４に示し、評価結果を
下記表５に示す。但し、表４中のハイシリカゼオライト
のＳｉＯ2 ／Ａｌ2Ｏ3モル比欄において、−はハイシリ
カゼオライトを使用していないことを示し、（ ）内の
値は脱臭剤全重量に対するハイシリカゼオライトの含有
量を示す。In this way, the chemical components of the deodorant were analyzed, and the results of this analysis are shown in Tables 3 to 4 below, with all items falling within the scope of the present invention as examples. 5 shows. However, in the SiO 2 / Al 2 O 3 molar ratio column of high silica zeolite in Table 4, − indicates that high silica zeolite is not used, and the value in parentheses is the high silica zeolite based on the total weight of the deodorant. The content of is shown.
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【表４】 [Table 4]
【００４８】[0048]
【表５】 [Table 5]
【００４９】上記表３乃至５に示すように、実施例Ｎ
ｏ．１〜１６は脱臭剤中の全ての化学成分及びＩｇ．ｌ
ｏｓｓが本発明の範囲内であるので、全ての悪臭成分に
対する脱臭性能が高く、強度及び抗菌性能が優れてい
た。また、実施例Ｎｏ．１乃至３、５、６、８、１０、
１４及び１６はＳｉＯ2 ／Ａｌ2Ｏ3モル比が５以上であ
るハイシリカゼオライトを使用しているので、硫化メチ
ルに対する脱臭性能が更に一層向上した。As shown in Tables 3 to 5 above, Example N
o. 1 to 16 are all chemical components in the deodorant and Ig. l
Since the oss was within the range of the present invention, the deodorizing performance for all malodorous components was high, and the strength and antibacterial performance were excellent. In addition, Example No. 1 to 3, 5, 6, 8, 10,
Since 14 and 16 used high silica zeolite having a SiO 2 / Al 2 O 3 molar ratio of 5 or more, the deodorizing performance for methyl sulfide was further improved.
【００５０】次いで、脱臭剤中の化学成分の内、Ｎａ及
びＫ含有量が本発明の範囲から外れている比較例につい
て、その分析結果及び評価結果を下記表６乃至８に示
す。Next, the analysis results and evaluation results of Comparative Examples in which the Na and K contents are out of the range of the present invention among the chemical components in the deodorant are shown in Tables 6 to 8 below.
【００５１】[0051]
【表６】 [Table 6]
【００５２】[0052]
【表７】 [Table 7]
【００５３】[0053]
【表８】 [Table 8]
【００５４】上記表３乃至８に示すように、比較例Ｎ
ｏ．１７及び１９はＮａ及びＫ含有量が本発明の範囲未
満であるので、実施例と比較して、硫化水素に対する脱
臭性能が低下した。また、比較例Ｎｏ．１８及び２０に
ついては、Ｎａ及びＫ含有量が本発明の範囲を超えてい
るため、全ての悪臭成分に対して脱臭性能が低下した。As shown in Tables 3 to 8 above, Comparative Example N
o. Since Nos. 17 and 19 had Na and K contents below the range of the present invention, the deodorizing performance for hydrogen sulfide was lower than that of the Examples. Also, in Comparative Example No. Regarding Nos. 18 and 20, since the Na and K contents exceeded the range of the present invention, the deodorizing performance was lowered for all malodorous components.
【００５５】次に、脱臭剤中のＩｇ．ｌｏｓｓが本発明
の範囲から外れている比較例、即ち、請求項２を満足し
ない比較例について、その分析結果及び評価結果を下記
表９乃至１１に示す。Next, Ig. Tables 9 to 11 below show the analysis results and evaluation results of comparative examples whose loss is outside the range of the present invention, that is, comparative examples not satisfying claim 2.
【００５６】[0056]
【表９】 [Table 9]
【００５７】[0057]
【表１０】 [Table 10]
【００５８】[0058]
【表１１】 [Table 11]
【００５９】上記表３乃至５及び９乃至１１に示すよう
に、比較例Ｎｏ．２１はＩｇ．ｌｏｓｓが本発明の範囲
未満であるので、実施例と比較して、水溶性である硫化
水素及びトリメチルアミンに対する脱臭性能が低下し
た。また、比較例Ｎｏ．２２については、Ｉｇ．ｌｏｓ
ｓが本発明の範囲を超えているため、圧縮強度が低下し
た。As shown in Tables 3 to 5 and 9 to 11, Comparative Example Nos. 21 is Ig. Since the loss was less than the range of the present invention, the deodorizing performance for water-soluble hydrogen sulfide and trimethylamine was decreased as compared with the examples. Also, in Comparative Example No. No. 22, Ig. los
Since s exceeds the range of the present invention, the compressive strength was lowered.
【００６０】また、脱臭剤中の必須成分である活性炭が
本発明の範囲から外れている比較例、即ち、請求項３を
満足しない比較例について、その分析結果及び評価結果
を下記表１２乃至１４に示す。Further, the analysis results and evaluation results of the comparative examples in which the activated carbon which is an essential component in the deodorant is out of the scope of the present invention, that is, the comparative example which does not satisfy claim 3, are shown in Tables 12 to 14 below. Shown in.
【００６１】[0061]
【表１２】 [Table 12]
【００６２】[0062]
【表１３】 [Table 13]
【００６３】[0063]
【表１４】 [Table 14]
【００６４】上記表３乃至５及び１２乃至１４に示すよ
うに、比較例Ｎｏ．２３は活性炭の含有量が本発明の範
囲未満であるので、実施例と比較して、全ての悪臭成分
に対して脱臭性能が低下した。比較例Ｎｏ．２４は活性
炭の含有量が本発明の範囲を超えているので、圧縮強度
が低下した。As shown in Tables 3 to 5 and 12 to 14, Comparative Example Nos. In No. 23, the content of activated carbon was less than the range of the present invention, so that the deodorizing performance was reduced for all the malodorous components as compared with the examples. Comparative Example No. In No. 24, since the content of activated carbon exceeds the range of the present invention, the compressive strength is lowered.
【００６５】更に、脱臭剤中に必須成分として含有され
る酸化物の内、少なくとも１種の酸化物（Ａｌ2Ｏ3、Ｓ
ｉＯ2 、ＭｎＯ、ＣｕＯ、ＭｇＯ及びＣａＯ）の含有量
が本発明の範囲から外れている比較例、即ち、請求項４
乃至８の少なくとも１項を満足しない比較例について、
その分析結果及び評価結果を下記表１５乃至１７に示
す。Further, among the oxides contained as an essential component in the deodorant, at least one oxide (Al 2 O 3 , S
A comparative example in which the content of iO 2 , MnO, CuO, MgO and CaO is outside the range of the present invention, that is,
Comparative Examples not satisfying at least one item of
The analysis results and evaluation results are shown in Tables 15 to 17 below.
【００６６】[0066]
【表１５】 [Table 15]
【００６７】[0067]
【表１６】 [Table 16]
【００６８】[0068]
【表１７】 [Table 17]
【００６９】上記表３乃至５及び１５乃至１７に示すよ
うに、比較例Ｎｏ．２５はＡｌ2Ｏ3の含有量が本発明の
範囲未満であるので、実施例と比較して、圧縮強度が低
下した。比較例Ｎｏ．２６はＡｌ2Ｏ3含有量が本発明の
範囲を超えているので、全ての悪臭成分に対して脱臭性
能が低下した。比較例Ｎｏ．２７はＳｉＯ2 含有量が本
発明の範囲未満であるので、硫化メチル及びトリメチル
アミンに対する脱臭性能が低下した。As shown in Tables 3 to 5 and 15 to 17, Comparative Example Nos. In No. 25, since the content of Al 2 O 3 was less than the range of the present invention, the compressive strength was lowered as compared with the examples. Comparative Example No. In No. 26, since the Al 2 O 3 content exceeds the range of the present invention, the deodorizing performance was deteriorated with respect to all the malodorous components. Comparative Example No. In No. 27, since the SiO 2 content was less than the range of the present invention, the deodorizing performance for methyl sulfide and trimethylamine was lowered.
【００７０】また、比較例Ｎｏ．２８、３０、３２及び
３４はＳｉＯ2 、ＭｎＯ、ＣｕＯ又はＭｇＯ含有量が本
発明の範囲未満であるので、圧縮強度が低下した。更
に、比較例Ｎｏ．２９はＭｎＯの含有量が本発明の範囲
未満であるので、実施例と比較して、脱臭性能が低下
し、比較例Ｎｏ．３１はＣｕＯ含有量が本発明の範囲未
満であるので、脱臭性能及び抗菌性能が低下した。ま
た、比較例Ｎｏ．３３はＭｇＯ含有量が本発明の範囲未
満であるので、抗菌性能が低下した。Further, in Comparative Example No. Nos. 28, 30, 32, and 34 had a SiO 2 , MnO, CuO, or MgO content below the range of the present invention, so the compressive strength decreased. Further, in Comparative Example No. No. 29 has a MnO content less than the range of the present invention, so the deodorizing performance is lower than in the Examples, and Comparative Example No. Since No. 31 had a CuO content less than the range of the present invention, the deodorizing performance and the antibacterial performance were deteriorated. Also, in Comparative Example No. In No. 33, since the MgO content was less than the range of the present invention, the antibacterial performance was lowered.
【００７１】更にまた、脱臭剤中の化学成分の内、Ａｇ
含有量が本発明の範囲から外れている比較例、即ち、請
求項１０を満足しない比較例について、その分析結果及
び評価結果を下記表１８乃至２０に示す。Furthermore, among the chemical components in the deodorant, Ag is
Tables 18 to 20 show the analysis results and evaluation results of Comparative Examples in which the content is outside the range of the present invention, that is, Comparative Examples not satisfying claim 10.
【００７２】[0072]
【表１８】 [Table 18]
【００７３】[0073]
【表１９】 [Table 19]
【００７４】[0074]
【表２０】 [Table 20]
【００７５】上記表３乃至５及び１８乃至２０に示すよ
うに、比較例Ｎｏ．３５はＡｇ含有量が本発明の範囲未
満であるので、抗菌性能が低下した。また、比較例Ｎ
ｏ．３６については、Ａｇ含有量が本発明の範囲を超え
ているため、圧縮強度が低下した。As shown in Tables 3 to 5 and 18 to 20 above, Comparative Example No. In No. 35, since the Ag content was less than the range of the present invention, the antibacterial performance was lowered. Comparative Example N
o. Regarding No. 36, the Ag content exceeded the range of the present invention, so the compressive strength decreased.
【００７６】[0076]
【発明の効果】以上詳述したように、本発明によれば、
脱臭剤中に酸化物と活性炭とを含有し、特に、Ｎａ及び
Ｋ含有量を適正量に規定しているので、脱臭剤以外の付
属装置を使用することなく悪臭成分を効率的に除去する
ことができ、長寿命で低コストであると共に、抗菌性能
が優れた脱臭剤及び脱臭部材を得ることができる。ま
た、脱臭剤中のＩｇ．ｌｏｓｓ及びその他の化学成分の
含有量を適正量に規制すると、更に一層、脱臭性能、強
度及び抗菌性能が向上する。As described in detail above, according to the present invention,
Since the deodorant contains oxides and activated carbon, and particularly the Na and K contents are regulated to proper amounts, it is possible to efficiently remove the malodorous components without using an auxiliary device other than the deodorant. It is possible to obtain a deodorant and a deodorant member having a long life and low cost, and excellent antibacterial performance. In addition, Ig. When the content of loss and other chemical components is regulated to an appropriate amount, deodorizing performance, strength and antibacterial performance are further improved.
【図１】脱臭性能評価装置の構造を示す模式図である。FIG. 1 is a schematic diagram showing a structure of a deodorizing performance evaluation device.
【図２】圧縮強度σの測定方法を示す模式図である。FIG. 2 is a schematic diagram showing a method for measuring compressive strength σ.
１；サンプル ２；恒温恒湿装置 ３、４；濃度測定器 ５；流量計 ６；ガス混合器 ７；悪臭ガスボンベ ８；エアボンベ 1; Sample 2; Constant temperature and humidity device 3, 4; Concentration measuring device 5; Flow meter 6; Gas mixer 7; Malodorous gas cylinder 8; Air cylinder
Claims (11)
銅酸化物及びマグネシウム酸化物からなる群から選択さ
れた少なくとも１種の酸化物と、活性炭とを含有し、更
に、Ｎａ化合物をＮａ換算値で０．０１乃至５．００重
量％、Ｋ化合物をＫ換算値で０．０１乃至５．００重量
％含有することを特徴とする脱臭剤。1. Al 2 O 3 , SiO 2 , manganese oxide,
It contains at least one oxide selected from the group consisting of copper oxides and magnesium oxides and activated carbon, and further contains 0.01 to 5.00% by weight of Na compound in terms of Na and K compound. A deodorant characterized by being contained in an amount of 0.01 to 5.00% by weight in terms of K.
定された強熱減量（Ｉｇ．ｌｏｓｓ）が０．１乃至１
５．０重量％であることを特徴とする請求項１に記載の
脱臭剤。2. The loss on ignition (Ig.loss) measured after drying at 80 ° C. for 1 hour is 0.1 to 1.
The deodorant according to claim 1, which is 5.0% by weight.
ことを特徴とする請求項１又は２に記載の脱臭剤。3. The deodorant according to claim 1, wherein the activated carbon is 10 to 50% by weight.
ることを特徴とする請求項１乃至３のいずれか１項に記
載の脱臭剤。4. The deodorant according to any one of claims 1 to 3, wherein the Al 2 O 3 is 10 to 50% by weight.
ることを特徴とする請求項１乃至４のいずれか１項に記
載の脱臭剤。5. The deodorant according to any one of claims 1 to 4, wherein the SiO 2 is 10 to 50% by weight.
乃至３０重量％であることを特徴とする請求項１乃至５
のいずれか１項に記載の脱臭剤。6. The MnO converted value of the manganese oxide is 5
% To 30% by weight.
The deodorant according to any one of 1.
０重量％であることを特徴とする請求項１乃至６のいず
れか１項に記載の脱臭剤。7. The copper oxide has a CuO conversion value of 1 to 1.
The deodorant according to any one of claims 1 to 6, which is 0% by weight.
で０．０１乃至３．００重量％であることを特徴とする
請求項１乃至７のいずれか１項に記載の脱臭剤。8. The deodorant according to any one of claims 1 to 7, wherein the magnesium oxide is 0.01 to 3.00 wt% in terms of MgO.
／Ａｌ2Ｏ3モル比が５以上であるハイシリカゼオライト
として添加されていることを特徴とする請求項１乃至８
のいずれか１項に記載の脱臭剤。9. some or all of the SiO 2 is SiO 2
9. A high silica zeolite having a molar ratio of / Al 2 O 3 of 5 or more is added as a high silica zeolite.
The deodorant according to any one of 1.
０．００１乃至１５重量％含有することを特徴とする請
求項１乃至９のいずれか１項に記載の脱臭剤。10. The deodorant according to any one of claims 1 to 9, further comprising 0.001 to 15% by weight of Ag or a silver compound in terms of Ag.
載の脱臭剤を担持体に被着して構成されたことを特徴と
する脱臭部材。11. A deodorizing member, characterized in that the deodorizing agent according to any one of claims 1 to 10 is applied to a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02688596A JP3576302B2 (en) | 1996-02-14 | 1996-02-14 | Deodorizer and deodorizing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02688596A JP3576302B2 (en) | 1996-02-14 | 1996-02-14 | Deodorizer and deodorizing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09215735A true JPH09215735A (en) | 1997-08-19 |
| JP3576302B2 JP3576302B2 (en) | 2004-10-13 |
Family
ID=12205732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02688596A Expired - Fee Related JP3576302B2 (en) | 1996-02-14 | 1996-02-14 | Deodorizer and deodorizing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3576302B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4837828B2 (en) * | 1998-09-15 | 2011-12-14 | ナノスケール コーポレーション | Reactive nanoparticles as adsorption and removal agents for biological and chemical pollutants |
-
1996
- 1996-02-14 JP JP02688596A patent/JP3576302B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4837828B2 (en) * | 1998-09-15 | 2011-12-14 | ナノスケール コーポレーション | Reactive nanoparticles as adsorption and removal agents for biological and chemical pollutants |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3576302B2 (en) | 2004-10-13 |
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