JP7141089B2 - Deodorizing material and deodorizing sheet - Google Patents
Deodorizing material and deodorizing sheet Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、脱臭材及び脱臭シートに関する。 The present invention relates to a deodorizing material and a deodorizing sheet.
近年、空気浄化に関する関心が高まっており、室内等において、より悪臭の少ない環境が求められている。また、シックハウス症候群の問題を発端として、住環境における揮発性有機化合物（ＶＯＣ）への対策も求められている。 2. Description of the Related Art In recent years, there has been a growing interest in air purification, and there has been a demand for an environment with less offensive odors, such as indoors. In addition, due to the problem of sick house syndrome, measures against volatile organic compounds (VOC) in the living environment are also required.
例えば、自動車などの車室内においては、シートパッド、インストルメント・パネル、ドアトリムなどの内装樹脂部品、塗料、接着剤などからの揮発性有機化合物の悪臭、さらに、排気ガス、燃料臭、タバコ、人体、食品の腐敗物などの多くの悪臭が発生し得る。また、車室内は、住宅に比して空間が狭いため、密閉すると特に悪臭が充満しやすいという問題を有する。 For example, in the interior of a car, the odor of volatile organic compounds from interior resin parts such as seat pads, instrument panels, and door trims, paints, and adhesives, as well as exhaust gas, fuel odor, cigarette smoke, and human body. , food spoilage and many other odors can occur. In addition, since the space inside the vehicle is narrower than that of a house, there is a problem that a bad odor tends to fill the vehicle when the vehicle is closed.
特許文献１は、繊維状活性炭と芳香族アミノ酸と硫酸とを含んだ繊維状脱臭材であって、以下の工程を含む方法によって製造された繊維状脱臭材を開示している。
芳香族アミノ酸と硫酸とを含有した水溶液中に繊維状活性炭を浸漬させて繊維状活性炭に芳香族アミノ酸と硫酸とを担持させる工程であって、繊維状活性炭に対する芳香族アミノ酸の質量比を１０質量％乃至２０質量％の範囲内とし、繊維状活性炭に対する硫酸の質量比を５質量％乃至２５質量％の範囲内とする工程と、
芳香族アミノ酸及び硫酸を担持させた繊維状活性炭から水溶液を除去する工程と、
水溶液を除去した繊維状活性炭を乾燥させる工程。
Patent Document 1 discloses a fibrous deodorizing material containing fibrous activated carbon, aromatic amino acids and sulfuric acid, which is produced by a method including the following steps.
A step of immersing a fibrous activated carbon in an aqueous solution containing an aromatic amino acid and sulfuric acid to support the aromatic amino acid and sulfuric acid on the fibrous activated carbon, wherein the mass ratio of the aromatic amino acid to the fibrous activated carbon is 10 mass. % to 20% by mass, and the mass ratio of sulfuric acid to fibrous activated carbon is in the range of 5% to 25% by mass;
removing the aqueous solution from the fibrous activated carbon supporting the aromatic amino acid and sulfuric acid;
A step of drying the fibrous activated carbon from which the aqueous solution has been removed.
特許文献１に開示された脱臭材によれば、アセトアルデヒドを高い効率で除去し且つ優れた貯蔵安定性を達成することが可能となる。しかしながら、本発明者が検討したところ、特許文献１に開示された脱臭材は、アセトアルデヒドを吸着した後に高温雰囲気下に置くと、吸着したアセトアルデヒドの脱臭材からの脱離が比較的多くなる場合があることを知得した。 According to the deodorizing material disclosed in Patent Document 1, it is possible to remove acetaldehyde with high efficiency and achieve excellent storage stability. However, when the deodorizing material disclosed in Patent Document 1 is placed in a high-temperature atmosphere after having adsorbed acetaldehyde, the deodorizing material disclosed in Patent Document 1 may release a relatively large amount of the adsorbed acetaldehyde from the deodorizing material. I learned something.
そこで、本発明は、上記問題を解決し、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率の小さい脱臭材、及び該脱臭材を用いた脱臭シートを提供することを主な課題とする。 Therefore, the present invention solves the above problems and provides a deodorizing material with a small desorption rate of adsorbed acetaldehyde when placed in a high-temperature atmosphere after adsorbing acetaldehyde, and a deodorizing sheet using the deodorizing material. The main task is to
本発明者は、このような課題を解決するために鋭意検討を行った。その結果、活性炭と、前記活性炭に担持された、（Ａ）「芳香族アミン及び該芳香族アミンの硫酸塩」、又は、（Ｂ）「芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸」とを含む、脱臭材であって、前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部である脱臭材とすることにより、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができることを見出した。本発明は、これらの知見に基づいて、さらに検討を重ねることにより完成された発明である。 The inventor of the present invention has made intensive studies to solve such problems. As a result, activated carbon and (A) "aromatic amine and sulfate of said aromatic amine" or (B) "aromatic amine, sulfate of said aromatic amine and sulfuric acid supported on said activated carbon ", wherein the total pore volume of the activated carbon is 0.45 cc/g or more, and the sum of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon The deodorizing material has a supported amount of 20 to 32 parts by mass, and a total supported amount of the sulfate salt of the aromatic amine and the sulfuric acid with respect to 100 parts by mass of the activated carbon is 1.8 to 3.5 parts by mass. Therefore, it was found that the desorption rate of the adsorbed acetaldehyde can be reduced when placed in a high-temperature atmosphere after adsorbing acetaldehyde. The present invention is an invention completed by further studies based on these findings.
すなわち、本発明は、下記に掲げる態様の発明を提供する。
項１． 活性炭と、前記活性炭に担持された、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とを含む、脱臭材であって、
前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、
前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、
前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部である、
脱臭材。
項２． 前記活性炭にｐ－アミノ安息香酸とｐ－アミノ安息香酸の硫酸塩が担持されている、項１に記載の脱臭材。
項３． アセトアルデヒドの脱離率が１５％以下である、項１又は２に記載の脱臭材。
項４． 項１～３のいずれか１項に記載の脱臭材を含む、脱臭シート。
That is, the present invention provides inventions in the following aspects.
Section 1. A deodorizing material comprising activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid supported on the activated carbon. and
The activated carbon has a total pore volume of 0.45 cc/g or more,
The total supported amount of the aromatic amine and the sulfate salt of the aromatic amine is 20 to 32 parts by mass with respect to 100 parts by mass of the activated carbon,
The total supported amount of the aromatic amine sulfate and the sulfuric acid is 1.8 to 3.5 parts by mass with respect to 100 parts by mass of the activated carbon.
Deodorizing material.
Section 2. Item 2. The deodorizing material according to Item 1, wherein p-aminobenzoic acid and p-aminobenzoic acid sulfate are supported on the activated carbon.
Item 3. Item 3. The deodorizing material according to Item 1 or 2, wherein the desorption rate of acetaldehyde is 15% or less.
Section 4. A deodorizing sheet comprising the deodorizing material according to any one of items 1 to 3.
本発明の脱臭材によれば、活性炭と、前記活性炭に担持された、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とを含む、脱臭材であって、前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部であることから、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができる。 According to the deodorizing material of the present invention, activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine and a sulfate of the aromatic amine supported on the activated carbon and sulfuric acid, wherein the activated carbon has a total pore volume of 0.45 cc/g or more, and the aromatic amine and the sulfate of the aromatic amine are added to 100 parts by mass of the activated carbon. is 20 to 32 parts by mass, and the total amount of the sulfate of the aromatic amine and the sulfuric acid is 1.8 to 3.5 parts by mass with respect to 100 parts by mass of the activated carbon. The desorption rate of the adsorbed acetaldehyde can be reduced when placed in a high-temperature atmosphere after adsorbing acetaldehyde.
本発明の脱臭材は、活性炭と、前記活性炭に担持された、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とを含む、脱臭材であって、前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部であることを特徴とする。以下、本発明の脱臭材及びこれを用いた脱臭シートについて詳述する。 The deodorizing material of the present invention comprises activated carbon, (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and and sulfuric acid, wherein the activated carbon has a total pore volume of 0.45 cc/g or more, and the sum of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon. The amount supported is 20 to 32 parts by mass, and the total supported amount of the sulfate of the aromatic amine and the sulfuric acid is 1.8 to 3.5 parts by mass with respect to 100 parts by mass of the activated carbon. . Hereinafter, the deodorizing material of the present invention and the deodorizing sheet using the same will be described in detail.
以下において、細孔容積とは、ＱＳＤＦＴ法（急冷固体密度汎関数法）によって算出される細孔容積をいう。ＱＳＤＦＴ法とは、幾何学的・化学的に不規則なミクロポーラス・メソポーラスな炭素の細孔径解析を対象とした、約０．５ｎｍ～約４０ｎｍまでの細孔径分布の計算ができる解析手法である。ＱＳＤＦＴ法では、細孔表面の粗さと不均一性による影響が明瞭に考慮されているため、細孔径分布解析の正確さが大幅に向上した手法である。本発明においては、Ｑｕａｎｔａｃｈｒｏｍｅ社製「ＡＵＴＯＳＯＲＢ－１－ＭＰ」を用いて窒素吸着等温線の測定、及びＱＳＤＦＴ法による細孔径分布解析をおこなう。７７Ｋの温度において測定した窒素の脱着等温線に対し、Ｃａｌｃｕｌａｔｉｏｎ ｍｏｄｅｌとしてＮ２ ａｔ ７７Ｋ ｏｎ ｃａｒｂｏｎ［ｓｌｉｔ ｐｏｒｅ，ＱＳＤＦＴ ｅｑｕｉｌｉｂｒｉｕｍ ｍｏｄｅｌ］を適用して細孔径分布を計算することで、特定の細孔径範囲の細孔容積を算出することができる。 Hereinafter, the pore volume refers to the pore volume calculated by the QSDFT method (quenched solid density functional theory). The QSDFT method is an analysis method that can calculate the pore size distribution from about 0.5 nm to about 40 nm for the pore size analysis of geometrically and chemically irregular microporous and mesoporous carbon. . The QSDFT method clearly takes into account the effects of pore surface roughness and non-uniformity, and is therefore a technique that greatly improves the accuracy of pore size distribution analysis. In the present invention, "AUTOSORB-1-MP" manufactured by Quantachrome is used to measure the nitrogen adsorption isotherm and analyze the pore size distribution by the QSDFT method. By applying N2 at 77K on carbon [slit pore, QSDFT equilibrium model] as a calculation model to the desorption isotherm of nitrogen measured at a temperature of 77 K to calculate the pore size distribution, the fineness of a specific pore size range can be obtained. Pore volume can be calculated.
本発明の脱臭材は、活性炭と、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とを含む。本発明の脱臭材において、活性炭と、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩とが含まれる場合には、芳香族アミン及び該芳香族アミンの硫酸塩が、当該活性炭に担持されている。また、本発明の脱臭材において、活性炭と、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とが含まれる場合には、芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸が、当該活性炭に担持されている。 The deodorizing material of the present invention contains activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid. When the deodorizing material of the present invention contains activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, the aromatic amine and the sulfate of the aromatic amine are carried on the activated carbon. ing. When the deodorizing material of the present invention contains activated carbon, (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid, the aromatic amine, the sulfate of the aromatic amine, and Sulfuric acid is supported on the activated carbon.
本発明において、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸（以下、総称して「本発明の脱臭材に含まれる薬剤」と略することがある。）を担持させる、活性炭は、全細孔容積が０．４５ｃｃ／ｇ以上である。なお、本明細書において、活性炭の説明については、別途説明の無い限り、本発明の脱臭材に含まれる薬剤を担持する前のものを示す。 In the present invention, (A) an aromatic amine and a sulfate salt of the aromatic amine, or (B) an aromatic amine, a sulfate salt of the aromatic amine, and sulfuric acid (hereinafter collectively referred to as the "deodorizing material of the present invention The activated carbon on which the "drug contained in" is supported has a total pore volume of 0.45 cc/g or more. In this specification, unless otherwise specified, the description of activated carbon refers to the carbon before carrying the chemical contained in the deodorizing material of the present invention.
本発明において、活性炭を上記前細孔容積とすることにより、後述する本発明の脱臭材に含まれる薬剤の担持量とすることができる。上記全細孔容積としては、０．７ｃｃ／ｇ以上がより好ましい。上記全細孔容積の上限値としては特に制限されないが、例えば、１．３ｃｃ／ｇ以下とすることが挙げられる。 In the present invention, by setting the activated carbon to the above-described front pore volume, it is possible to obtain the amount of drug contained in the deodorizing material of the present invention, which will be described later. More preferably, the total pore volume is 0.7 cc/g or more. Although the upper limit of the total pore volume is not particularly limited, it may be, for example, 1.3 cc/g or less.
本発明において、活性炭の比表面積としては、例えば、０．４５ｃｃ／ｇ以上の全細孔容積を確保しつつ、アセトアルデヒド吸着性能をより向上させる観点から、１０００ｍ2／ｇ以上が好ましく、１５００ｍ2／ｇ以上がより好ましい。上限値としては特に制限されないが、例えば、３０００ｍ2／ｇ以下が挙げられ、２５００ｍ2／ｇ以下が好ましく挙げられる。なお、活性炭の比表面積は、ＪＩＳ Ｋ１４７７に記載されたＢＥＴ法（１点法）により求めた値である。 In the present invention, the specific surface area of the activated carbon is preferably 1000 m 2 /g or more, more preferably 1500 m 2 /g, from the viewpoint of further improving the acetaldehyde adsorption performance while ensuring a total pore volume of 0.45 cc/g or more. g or more is more preferable. Although the upper limit is not particularly limited, it is, for example, 3000 m 2 /g or less, preferably 2500 m 2 /g or less. The specific surface area of activated carbon is a value determined by the BET method (one-point method) described in JIS K1477.
本発明において、活性炭の平均細孔径としては、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率をより一層小さいものとする観点から、１．５～２．３ｎｍが好ましく挙げられ、１．５～１．８ｎｍがより好ましく挙げられ、１．７～１．８ｎｍがさらに好ましく挙げられる。なお、活性炭の平均細孔径としては、下記式（１）により算出されるものである。
平均細孔直径（ｎｍ）
＝４×全細孔容積（ｃｃ／ｇ）／比表面積（ｍ2／ｇ）×１０3 ・・・（１）
In the present invention, the average pore diameter of the activated carbon is 1.5 to 2.5 to 1.5 to 2.0, from the viewpoint of further reducing the desorption rate of adsorbed acetaldehyde when placed in a high-temperature atmosphere after adsorbing acetaldehyde. 3 nm is preferred, 1.5 to 1.8 nm is more preferred, and 1.7 to 1.8 nm is even more preferred. The average pore diameter of activated carbon is calculated by the following formula (1).
Average pore diameter (nm)
= 4 x total pore volume (cc/g)/specific surface area (m 2 /g) x 10 3 (1)
本発明において、活性炭の、０．６５ｎｍ以上２ｎｍ以下の細孔径の細孔容積としては、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率をより一層小さいものとする観点から、０．２～０．７ｃｃ／ｇが好ましく挙げられ、０．６～０．７ｃｃ／ｇがより好ましく挙げられる。 In the present invention, the pore volume of the activated carbon with a pore diameter of 0.65 nm or more and 2 nm or less is one that further reduces the desorption rate of the adsorbed acetaldehyde when placed in a high-temperature atmosphere after acetaldehyde is adsorbed. 0.2 to 0.7 cc/g is preferred, and 0.6 to 0.7 cc/g is more preferred.
本発明の脱臭材において、活性炭の形態は特に限定されないが、例えば、粒状活性炭、粉末状活性炭、繊維状活性炭等が挙げられる。アセトアルデヒドの吸着速度が比較的速いという観点からは、繊維状である繊維状活性炭とすることがより好ましい。なお、繊維状活性炭の平均繊維径としては、好ましくは３０μｍ以下、より好ましくは５～２０μｍ程度が挙げられる。なお、本発明における平均繊維径は、画像処理繊維径測定装置（ＪＩＳ Ｋ １４７７に準拠）により測定した値である。また、粒状活性炭及び粉末状活性炭の粒径としては、レーザー回折／散乱式法で測定した積算体積百分率Ｄ５０が０．０１～５ｍｍが挙げられる。 In the deodorizing material of the present invention, the form of activated carbon is not particularly limited, but examples thereof include granular activated carbon, powdered activated carbon, and fibrous activated carbon. From the viewpoint that the adsorption speed of acetaldehyde is relatively high, it is more preferable to use a fibrous activated carbon. The average fiber diameter of fibrous activated carbon is preferably 30 μm or less, more preferably about 5 to 20 μm. In addition, the average fiber diameter in the present invention is a value measured by an image processing fiber diameter measuring device (based on JIS K 1477). Further, as the particle size of granular activated carbon and powdered activated carbon, an integrated volume percentage D50 measured by a laser diffraction/scattering method is 0.01 to 5 mm.
活性炭前駆体の原料種及び形態としては特に制限されるものではない。活性炭前駆体の原料種の例としては、不融化或いは炭素化した有機質材料、フェノール樹脂等の硬化性樹脂等が挙げられ、該有機質材料としては、例えば、ポリアクリロニトリル、ピッチ、ポリビニルアルコール、セルロース等が挙げられる。また、オガ屑、木材チップ、木材、ピート、木炭、ヤシ殻、石炭、オイル、炭素質物質（石油コークス、石炭コークス、石油ピッチ、石炭ピッチ、コールタールピッチ、及びこれらの複合物など）、合成樹脂（フェノール樹脂、ポリアクリロニトリル（ＰＡＮ）、ポリイミド、フラン樹脂など）、セルロース系繊維（紙、綿繊維など）、及びこれらの複合物（紙－フェノール樹脂積層板など）、フラーレンなどが挙げられる。これらの中でも、炭素化時の理論炭素化収率の点で、ピッチであることが好ましく、石炭ピッチであることがより好ましい。活性炭前駆体の形態の例としては、粒状、粉末状、繊維状等が挙げられる。 The raw material species and form of the activated carbon precursor are not particularly limited. Examples of raw materials for activated carbon precursors include infusibilized or carbonized organic materials, curable resins such as phenolic resins, etc. Examples of the organic materials include polyacrylonitrile, pitch, polyvinyl alcohol, cellulose, and the like. is mentioned. Also sawdust, wood chips, wood, peat, charcoal, coconut shells, coal, oil, carbonaceous materials (such as petroleum coke, coal coke, petroleum pitch, coal pitch, coal tar pitch, and combinations thereof), synthetic Examples include resins (phenolic resin, polyacrylonitrile (PAN), polyimide, furan resin, etc.), cellulosic fibers (paper, cotton fiber, etc.), composites thereof (paper-phenolic resin laminates, etc.), and fullerenes. Among these, pitch is preferable, and coal pitch is more preferable, from the viewpoint of the theoretical carbonization yield during carbonization. Examples of the form of the activated carbon precursor include granular, powdery, fibrous and the like.
本発明の脱臭材に用いる活性炭を得る方法としては、特に制限されないが、例えば、上記活性炭前駆体を、水蒸気を用いて、所定の全細孔容積となるよう、賦活温度、賦活時間を調整して得る方法が挙げられる。 The method for obtaining the activated carbon used in the deodorizing material of the present invention is not particularly limited, but for example, the activated carbon precursor is adjusted with water vapor to obtain a predetermined total pore volume at an activation temperature and an activation time. can be obtained by
本発明の脱臭材において、芳香族アミンとしては特に制限されないがアセトアルデヒドに対する脱臭能をより効果的に高めるため、また製造上の取り扱い易さや安全上の観点から、ハロゲン、スルホ基、アセトアミド基、又はカルボニル基がベンゼン環に結合した芳香族アミンが好ましい。ハロゲン、スルホ基、アセトアミド基、又はカルボニル基がベンゼン環に結合した芳香族アミンとしては、アミノ安息香酸、アミノアセトアニリド、アミノサリチル酸、アミノスルファニル酸等が好ましく挙げられる。中でも、芳香族アミンと該芳香族アミンの硫酸塩としてはアミノ安息香酸及びその硫酸塩が好ましい。すなわち、本発明の脱臭材においては、繊維状活性炭にアミノ安息香酸及びその硫酸塩が担持されていることが好ましい。本発明の脱臭材中において、芳香族アミンの少なくとも一部は、後述の硫酸と共に硫酸塩を形成する。芳香族アミンと該芳香族アミンの硫酸塩は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 In the deodorizing material of the present invention, the aromatic amine is not particularly limited, but in order to more effectively enhance the deodorizing ability against acetaldehyde, and from the viewpoint of ease of handling in production and safety, halogen, sulfo group, acetamide group, or Aromatic amines in which the carbonyl group is attached to the benzene ring are preferred. Aminobenzoic acid, aminoacetanilide, aminosalicylic acid, aminosulfanilic acid and the like are preferred as the aromatic amine having a halogen, sulfo group, acetamide group or carbonyl group bonded to the benzene ring. Among them, aminobenzoic acid and its sulfate are preferable as the aromatic amine and the sulfate of the aromatic amine. That is, in the deodorizing material of the present invention, it is preferable that aminobenzoic acid and its sulfate are supported on the fibrous activated carbon. At least part of the aromatic amine in the deodorizing material of the present invention forms a sulfate with sulfuric acid, which will be described later. The aromatic amine and the sulfate of the aromatic amine may be used singly or in combination of two or more.
アミノ安息香酸としては、特に制限されず、ｐ－アミノ安息香酸、ｍ－アミノ安息香酸、及びｏ－アミノ安息香酸のうち少なくとも１種を用いることができる。アセトアルデヒドに対する脱臭能をより効果的に高める観点からは、本発明の脱臭材においては、ｐ－アミノ安息香酸が担持されていることが特に好ましい。 Aminobenzoic acid is not particularly limited, and at least one of p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid can be used. From the viewpoint of more effectively enhancing the deodorizing ability against acetaldehyde, it is particularly preferable that the deodorizing material of the present invention supports p-aminobenzoic acid.
本発明の脱臭材においては、上記の芳香族アミンと該芳香族アミンの硫酸塩と共に、硫酸が担持されていてもよい。すなわち、本発明の脱臭材は、（Ａ）芳香族アミンと該芳香族アミンの硫酸塩が担持された活性炭（硫酸が担持されていなくてもよい）、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸とが担持された活性炭を備えている。 In the deodorizing material of the present invention, sulfuric acid may be supported together with the aromatic amine and the sulfate of the aromatic amine. That is, the deodorizing material of the present invention includes (A) activated carbon supporting an aromatic amine and a sulfate salt of the aromatic amine (sulfuric acid may not be supported), or (B) an aromatic amine and the It comprises activated carbon on which a sulfate salt of an aromatic amine and sulfuric acid are supported.
硫酸は、沸点が比較的高く、揮発し難い。硫酸は、水へのアミノ安息香酸の溶解を促進するため、後述するような脱臭材の製造過程において、活性炭に芳香族アミンと該芳香族アミンの硫酸塩を均一に担持させることを可能とする。さらに、硫酸は、脱臭材において、芳香族アミン、芳香族アミンの硫酸塩同士が互いに重合することを抑制する効果を発揮する。 Sulfuric acid has a relatively high boiling point and is difficult to volatilize. Since sulfuric acid promotes the dissolution of aminobenzoic acid in water, it enables the aromatic amine and the sulfate of the aromatic amine to be uniformly supported on the activated carbon in the process of manufacturing a deodorizing material as described later. . Furthermore, sulfuric acid exhibits the effect of suppressing mutual polymerization of aromatic amines and sulfates of aromatic amines in the deodorant.
前述のとおり、特許文献１に開示された繊維状脱臭材においては、繊維状活性炭に対する配合量が特定の範囲に設定された芳香族アミノ酸と硫酸とを含有した水溶液を用い、この水溶液中に、繊維状活性炭を浸漬することによって繊維状脱臭材を得ているが、アセトアルデヒドを吸着した後高温雰囲気下に置くと、吸着したアセトアルデヒドの脱臭材からの脱離が比較的多くなる場合がある。 As described above, in the fibrous deodorizing material disclosed in Patent Document 1, an aqueous solution containing an aromatic amino acid and sulfuric acid in which the blending amount with respect to the fibrous activated carbon is set within a specific range is used, and in this aqueous solution, A fibrous deodorizing material is obtained by immersing fibrous activated carbon, but if the material is placed in a high-temperature atmosphere after adsorbing acetaldehyde, a relatively large amount of the adsorbed acetaldehyde may be released from the deodorizing material.
これに対して、本発明の脱臭材においては、（Ａ）芳香族アミンと該芳香族アミンの硫酸塩が担持された活性炭、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸とが担持された活性炭を備える脱臭材とし、該活性炭の全細孔容積を０．４５ｃｃ／ｇ以上とした上で、該活性炭１００質量部に対する、担持される芳香族アミン及び前記芳香族アミンの硫酸塩の合計担持量を２０～３２質量部とし、担持される芳香族アミンの硫酸塩と前記硫酸との合計担持量を１．８～３．５質量部に設定することにより、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができる。 On the other hand, in the deodorizing material of the present invention, (A) activated carbon on which an aromatic amine and a sulfate salt of the aromatic amine are supported, or (B) an aromatic amine and a sulfate salt of the aromatic amine A deodorizing material comprising activated carbon on which sulfuric acid is supported, and the total pore volume of the activated carbon is 0.45 cc/g or more, and the aromatic amine supported and the aromatic amine are added to 100 parts by mass of the activated carbon. The total supported amount of the sulfate is 20 to 32 parts by mass, and the total supported amount of the supported aromatic amine sulfate and the sulfuric acid is set to 1.8 to 3.5 parts by mass. The desorption rate of the adsorbed acetaldehyde can be reduced when placed in a high-temperature atmosphere after adsorption.
活性炭１００質量部に対する、担持される芳香族アミン及び前記芳香族アミンの硫酸塩の合計担持量は２８～３２質量部がより好ましい。また、活性炭１００質量部に対する、担持される芳香族アミンの硫酸塩と前記硫酸との合計担持量は２．０～３．０質量部がより好ましい。 The total supported amount of the aromatic amine and the sulfate salt of the aromatic amine to be supported with respect to 100 parts by weight of the activated carbon is more preferably 28 to 32 parts by weight. Further, the total amount of supported aromatic amine sulfate and sulfuric acid is more preferably 2.0 to 3.0 parts by mass with respect to 100 parts by mass of activated carbon.
本発明の脱臭材において、このような特定の構成を採用することによってアセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができる機構の詳細は明らかではないが、例えば、次のような要因が関連しているものと考えられる。脱臭材に接触したアセトアルデヒドは、芳香族アミン等と化学吸着するか、活性炭の細孔に物理吸着すると考えられる。アルデヒドを吸着した脱臭材を高温環境に置くと、不可逆に化学吸着したアセトアルデヒドは脱離しないが、物理吸着したアセトアルデヒドは一部が細孔から脱離する。脱臭材における芳香族アミン等の担持量が十分でないと、物理吸着の寄与が比較的大きくなり、脱着するアセトアルデヒド量が多くなるため、結果脱離率が増加する。また、芳香族アミン等を所定の担持量となるように担持させるためには、担持する活性炭は細孔容積が一定以上必要であり、所定の細孔容積を有する活性炭に芳香族アミン等を担持させることで、上記効果を奏することが可能となる。 In the deodorizing material of the present invention, the details of the mechanism that can reduce the desorption rate of the adsorbed acetaldehyde when placed in a high-temperature atmosphere after adsorbing acetaldehyde by adopting such a specific configuration are as follows. Although it is not clear, for example, the following factors are thought to be related. Acetaldehyde coming into contact with the deodorizing material is considered to chemically adsorb to aromatic amines or the like, or to physically adsorb to pores of activated carbon. When a deodorizing material that has adsorbed aldehyde is placed in a high-temperature environment, the irreversibly chemically adsorbed acetaldehyde is not desorbed, but part of the physically adsorbed acetaldehyde is desorbed from the pores. If the amount of aromatic amine or the like supported in the deodorizing material is insufficient, the contribution of physical adsorption becomes relatively large, and the amount of desorbed acetaldehyde increases, resulting in an increased desorption rate. In addition, in order to support a predetermined amount of aromatic amine, etc., the activated carbon to be supported must have a certain pore volume or more. It is possible to achieve the above effect by making the
なお、本発明の脱臭材中における芳香族アミンと芳香族アミンの硫酸塩の合計担持量、及び、芳香族アミンの硫酸塩と硫酸の合計担持量は、例えば、以下のように測定することができる。 The total supported amount of aromatic amine and aromatic amine sulfate and the total supported amount of aromatic amine sulfate and sulfuric acid in the deodorizing material of the present invention can be measured, for example, as follows. can.
活性炭１００質量部に対する芳香族アミンと該芳香族アミンの硫酸塩の合計担持量（質量部）の測定
活性炭に担持された芳香族アミンと該芳香族アミンの硫酸塩の合計担持量については、薬剤溶液の、活性炭を浸漬する前の液と活性炭を浸漬した後の液の有機物濃度を、それぞれ全有機物濃度（ＴＯＣ）計を用いて測定し、浸漬操作前後の有機物濃度の差から、合計担持量を測定する。具体的には、まず全有機物濃度（ＴＯＣ）計（株式会社島津製作所製ＴＯＣ－５０００）を用いて、浸漬操作前後の薬剤溶液について、炭素（Ｃ）に換算された有機物濃度（ｍｇＣ／Ｌ）を測定し、操作前後の濃度の差を求める。別途、秤量して調製した既知濃度の芳香族アミン水溶液について同様に全有機物濃度を測定し、有機物濃度（ｍｇＣ／Ｌ）と芳香族アミン濃度（ｍｇ芳香族アミン／Ｌ）の対応を表す検量線を作成する。作成した検量線を用いて、添着操作前後の有機物濃度の差（ｍｇＣ／Ｌ）を芳香族アミン濃度の差（ｍｇ芳香族アミン／Ｌ）に換算する。求めた濃度の差に処理液量（Ｌ）を乗じて芳香族アミン質量の差を算出する。算出された値を、薬剤溶液に浸漬する前の活性炭１００質量部あたりの質量部に換算し、得られた質量部を、活性炭１００質量部に対する芳香族アミンと該芳香族アミンの硫酸塩の合計担持量（質量部）とする。
Measurement of the total amount (parts by mass) of aromatic amine and the sulfate of the aromatic amine supported on 100 parts by mass of activated carbon. The concentration of organic substances in the solution before immersion in activated carbon and in the solution after immersion in activated carbon were each measured using a total organic concentration (TOC) meter, and from the difference in the concentration of organic substances before and after the immersion operation, the total supported amount was obtained. to measure. Specifically, first, using a total organic matter concentration (TOC) meter (TOC-5000 manufactured by Shimadzu Corporation), the organic matter concentration (mgC / L) converted to carbon (C) for the chemical solution before and after the immersion operation. and determine the difference in concentration before and after the operation. Separately, the total organic substance concentration was similarly measured for an aqueous aromatic amine solution of known concentration prepared by weighing, and a calibration curve representing the correspondence between the organic substance concentration (mgC/L) and the aromatic amine concentration (mg aromatic amine/L) was prepared. to create Using the prepared calibration curve, the difference in organic substance concentration before and after the impregnation operation (mgC/L) is converted into the difference in aromatic amine concentration (mg aromatic amine/L). The difference in aromatic amine mass is calculated by multiplying the obtained difference in concentration by the amount of treatment liquid (L). The calculated value is converted to parts by mass per 100 parts by mass of activated carbon before being immersed in the chemical solution, and the obtained parts by mass are the sum of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of activated carbon. It is defined as the supported amount (parts by mass).
活性炭１００質量部に対する芳香族アミンの硫酸塩と硫酸の合計担持量（質量部）の測定
活性炭に担持された芳香族アミンの硫酸塩と硫酸の合計物質量についても同様に、活性炭を浸漬する前の薬剤溶液と、活性炭を浸漬した後の薬剤溶液について、ＪＩＳ Ｋ ０１０１：１９９８ ４２．４に規定のイオンクロマトグラフ法に準じ硫酸イオンの濃度（ｍｇ／Ｌ）を測定することで、これらの合計担持量を計算する。具体的には浸漬操作前後の薬剤溶液の硫酸イオンの濃度（ｍｇ／Ｌ）を、検量線を用いてそれぞれ測定し、操作前後の硫酸イオン濃度の差（ｍｇ／Ｌ）を求める。求めた操作前後の硫酸イオン濃度の差（ｍｇ／Ｌ）に、硫酸の分子量（９８．０８ｇ／ｍｏｌ）と硫酸イオンの分子量（９６．０６ｇ／ｍｏｌ）の比を乗じて硫酸濃度の差に換算する。硫酸濃度の差に処理液量（Ｌ）を乗じて操作前後の硫酸の差を算出する。算出した操作前後の硫酸の差を、薬剤溶液に浸漬する前の活性炭１００質量部あたりの質量部に換算し、得られた質量部を、活性炭１００質量部に対する芳香族アミンの硫酸塩と硫酸の合計担持量（質量部）とする。
Measurement of total amount (parts by mass) of aromatic amine sulfate and sulfuric acid supported on 100 parts by mass of activated carbon and the drug solution after immersion in activated carbon, the concentration of sulfate ions (mg / L) was measured according to the ion chromatography method specified in JIS K 0101: 1998 42.4. Calculate the loading. Specifically, the sulfate ion concentration (mg/L) of the chemical solution before and after the immersion operation is measured using a calibration curve, and the difference in sulfate ion concentration (mg/L) before and after the operation is determined. The difference in sulfate ion concentration before and after the operation (mg/L) obtained is multiplied by the ratio of the molecular weight of sulfuric acid (98.08 g/mol) and the molecular weight of sulfate ion (96.06 g/mol) to convert to the difference in sulfuric acid concentration. do. The difference in sulfuric acid concentration before and after the operation is calculated by multiplying the difference in sulfuric acid concentration by the amount of treated liquid (L). The calculated difference in sulfuric acid before and after the operation was converted to parts by mass per 100 parts by mass of activated carbon before being immersed in the chemical solution, and the obtained parts by mass were added to 100 parts by mass of the aromatic amine sulfate and sulfuric acid relative to 100 parts by mass of activated carbon. The total supported amount (parts by mass).
本発明の脱臭材の比表面積（本発明の脱臭材に含まれる薬剤を担持後の比表面積）としては、特に制限されないが、例えば、５０～１０００ｍ2／ｇが好ましく挙げられ、５００～１０００ｍ2／ｇがより好ましく挙げられる。 The specific surface area of the deodorizing material of the present invention (the specific surface area after carrying the drug contained in the deodorizing material of the present invention) is not particularly limited, but for example, 50 to 1000 m 2 /g is preferable, and 500 to 1000 m 2 is preferred. /g is more preferred.
本発明の脱臭材において、本発明の脱臭材に含まれる薬剤の担持により減少する比表面積（＝担持前の活性炭の比表面積－担持後の脱臭材の比表面積）としては、例えば、５００～１３００ｍ2／ｇが挙げられ、９００～１２００ｍ2／ｇが挙げられる。また、本発明の脱臭材において、活性炭の比表面積の、本発明の脱臭材に含まれる薬剤の担持による減少率（＝担持後の脱臭材の比表面積／担持前の活性炭の比表面積×１００（％））としては、例えば、３０～９５％が挙げられ、４０～７０％が好ましく挙げられる。 In the deodorizing material of the present invention, the specific surface area (=the specific surface area of the activated carbon before carrying - the specific surface area of the deodorizing material after carrying) that decreases due to carrying the drug contained in the deodorizing material of the present invention is, for example, 500 to 1300 m. 2 /g, and 900-1200 m 2 /g. In addition, in the deodorizing material of the present invention, the reduction rate of the specific surface area of the activated carbon due to the loading of the drug contained in the deodorizing material of the present invention (=specific surface area of deodorizing material after loading/specific surface area of activated carbon before loading x 100 ( %)) is, for example, 30 to 95%, preferably 40 to 70%.
本発明の脱臭材は、活性炭と、前記活性炭に担持された、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とを含む、脱臭材であって、前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部であることから、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができる。本発明の脱臭材の、下記測定方法における脱離率としては、１５％以下が挙げられ、１２％以下が挙げられる。当該脱離率の下限値としては、特に制限されないが、例えば、１％以上又は３％以上が挙げられる。 The deodorizing material of the present invention comprises activated carbon, (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and and sulfuric acid, wherein the activated carbon has a total pore volume of 0.45 cc/g or more, and the sum of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon. The supported amount is 20 to 32 parts by mass, and the total supported amount of the aromatic amine sulfate and the sulfuric acid is 1.8 to 3.5 parts by mass with respect to 100 parts by mass of the activated carbon. The desorption rate of the adsorbed acetaldehyde can be reduced when placed in a high-temperature atmosphere after adsorption. The desorption rate of the deodorizing material of the present invention in the following measurement method is 15% or less, and 12% or less. Although the lower limit of the desorption rate is not particularly limited, examples thereof include 1% or more and 3% or more.
（アセトアルデヒド脱離率測定方法）
脱臭材０．０１ｇと、４５０ｐｐｍのアセトアルデヒドガス３Ｌとをガスバッグに封入し、２０℃の環境下において静置し、脱臭材にアセトアルデヒドを吸着させる。２４時間経過後、ガスバッグ内のアセトアルデヒド濃度を測定し、脱臭材１ｇあたりのアセトアルデヒド吸着量を算出する。次に、アセトアルデヒドを吸着した脱臭材をガスバッグから取り出し、該脱臭材を窒素ガス３Ｌとともにガスバッグに封入し、７０℃の環境下において静置する。２４時間経過後、ガスバッグ内のアセトアルデヒド濃度を測定し、脱臭材１ｇあたりのアセトアルデヒド脱離量を算出する。そして、得られたアセトアルデヒド吸着量とアセトアルデヒド脱離量を下記式（２）に代入し、得られる値をアセトアルデヒド脱離率（％）とする。
アセトアルデヒド脱離率（％）
＝アセトアルデヒド脱離量／アセトアルデヒド吸着量×１００（％） ・・・（２）
(Method for measuring acetaldehyde elimination rate)
0.01 g of the deodorizing material and 3 L of 450 ppm acetaldehyde gas are sealed in a gas bag and allowed to stand in an environment of 20° C. to allow the deodorizing material to adsorb acetaldehyde. After 24 hours, the acetaldehyde concentration in the gas bag is measured, and the amount of acetaldehyde adsorbed per 1 g of the deodorizing material is calculated. Next, the deodorizing material that has adsorbed acetaldehyde is taken out from the gas bag, the deodorizing material is sealed in the gas bag together with 3 L of nitrogen gas, and left to stand in an environment of 70°C. After 24 hours have passed, the acetaldehyde concentration in the gas bag is measured, and the amount of acetaldehyde eliminated per 1 g of the deodorizing material is calculated. Then, the obtained acetaldehyde adsorption amount and acetaldehyde desorption amount are substituted into the following formula (2), and the resulting value is defined as the acetaldehyde desorption rate (%).
Acetaldehyde elimination rate (%)
= Acetaldehyde desorption amount/acetaldehyde adsorption amount x 100 (%) (2)
本発明の脱臭材は、例えば、次のようにして製造することができる。まず、全細孔容積が０．４５ｃｃ／ｇ以上である活性炭を準備する。当該活性炭を得る方法としては、前述のとおりである。次に、芳香族アミンおよび／またはその塩と、硫酸および／またはその塩と、水とを含有した処理液を調製する。芳香族アミンおよび／またはその塩は、水で十分に希釈した硫酸および／またはその塩の水溶液中に溶解させてもよく、硫酸および／またはその塩を比較的高い濃度で含んだ水溶液中に溶解させた後にこれを水で希釈して処理液としてもよい。硫酸としては、濃硫酸を用いてもよいし、希硫酸を用いてもよい。また、芳香族アミンおよび／またはその塩を水に溶解させるために、硫酸および／またはその塩の水溶液を、例えば５０～８０℃の範囲内の温度に加熱し、ここに芳香族アミンおよび／またはその塩を混合してもよい。また、芳香族アミンとしては、前述のものを用いる。芳香族アミンの塩としては、特に制限されないが、例えば、当該芳香族アミンの硫酸塩などが挙げられる。 The deodorizing material of the present invention can be produced, for example, as follows. First, activated carbon having a total pore volume of 0.45 cc/g or more is prepared. The method for obtaining the activated carbon is as described above. Next, a treatment liquid containing aromatic amine and/or its salt, sulfuric acid and/or its salt, and water is prepared. The aromatic amine and/or its salt may be dissolved in an aqueous solution of sulfuric acid and/or its salt sufficiently diluted with water, or dissolved in an aqueous solution containing a relatively high concentration of sulfuric acid and/or its salt. This may be diluted with water to prepare a treatment solution. As the sulfuric acid, concentrated sulfuric acid may be used, or dilute sulfuric acid may be used. Also, in order to dissolve the aromatic amine and/or its salt in water, an aqueous solution of sulfuric acid and/or its salt is heated, for example, to a temperature within the range of 50 to 80° C., and the aromatic amine and/or The salt may be mixed. As the aromatic amine, those mentioned above are used. Salts of aromatic amines are not particularly limited, and examples thereof include sulfates of the aromatic amines.
処理液における芳香族アミンおよび／またはその塩の仕込み量としては、本発明の脱臭材における芳香族アミンおよび／またはその塩の担持量が所望の範囲となるように設定すれば、特に制限されず、例えば、後に浸漬する活性炭１００質量部に対して、２０～４０質量部程度とすればよい。また、処理液における硫酸および／またはその塩の仕込み量としては、本発明の脱臭材における芳香族アミンと該芳香族アミンの硫酸塩、又は、芳香族アミンと該芳香族アミンの硫酸塩と硫酸の含有量が所望の範囲となるように設定すれば、特に制限されず、後に浸漬する活性炭１００質量部に対して、２０～４０質量部程度とすればよい。 The amount of the aromatic amine and/or salt thereof charged in the treatment liquid is not particularly limited as long as the amount of the aromatic amine and/or salt thereof carried in the deodorizing material of the present invention falls within the desired range. For example, it may be about 20 to 40 parts by mass with respect to 100 parts by mass of activated carbon to be immersed later. The amounts of sulfuric acid and/or salts thereof to be charged in the treatment liquid are the aromatic amine and the sulfate of the aromatic amine, or is not particularly limited as long as it is set within a desired range.
次に、この処理液中に準備した活性炭を浸漬して、該活性炭に（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸を担持させる。例えば、活性炭を処理液中に均一に分散させ、その後、十分な時間に亘ってこの分散液を静置する。活性炭を処理液中に浸漬させる時間は、例えば約１時間以上とする。活性炭の質量と処理液の体積との比は、例えば５～５０ｇ／Ｌの範囲内とする。この比が小さすぎる場合、（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸を活性炭に担持させるためにより長い時間を要する。一方、この比が大きすぎる場合、（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸を活性炭に均一に担持させることが難しくなる。なお、活性炭を水溶液と接触させている時間が十分に長ければ、この比が活性炭に担持される（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸の量に及ぼす影響は無視することができる。なお、活性炭を浸漬する処理液は、上記の芳香族アミンおよび／またはその塩の仕込みの際に加熱された状態で使用してもよく、加熱した処理液を冷却した後に使用してもよい。 Next, the prepared activated carbon is immersed in this treatment solution, and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine and a sulfate of the aromatic amine are applied to the activated carbon. and sulfuric acid. For example, activated carbon is uniformly dispersed in the treatment liquid, and then the dispersion is allowed to stand for a sufficient period of time. The time for which the activated carbon is immersed in the treatment liquid is, for example, about 1 hour or more. The ratio of the mass of activated carbon to the volume of the treatment liquid is, for example, within the range of 5 to 50 g/L. If this ratio is too small, a longer time is required to load (A) the aromatic amine and the sulfate of the aromatic amine, or (B) the aromatic amine, the sulfate of the aromatic amine, and the sulfuric acid onto the activated carbon. need. On the other hand, if this ratio is too large, (A) the aromatic amine and the sulfate of the aromatic amine, or (B) the aromatic amine, the sulfate of the aromatic amine, and sulfuric acid should be uniformly supported on the activated carbon. becomes difficult. If the time of contacting the activated carbon with the aqueous solution is sufficiently long, the ratio of (A) the aromatic amine and the sulfate of the aromatic amine supported on the activated carbon, or (B) the aromatic amine and the The effect on the amount of aromatic amine sulfate and sulfuric acid is negligible. The treatment liquid in which the activated carbon is immersed may be used in a heated state during the charging of the aromatic amine and/or its salt, or may be used after cooling the heated treatment liquid.
次いで、（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸とを担持させた活性炭から処理液を除去する。処理液を除去する方法としては、特に制限されず、例えば、活性炭を処理液から引き上げることにより行うことができる。（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸とを担持させた活性炭からの処理液の除去に先立って、処理液を水で希釈してもよい。 Next, the treating solution is removed from (A) the aromatic amine and the sulfate of the aromatic amine, or (B) the activated carbon supporting the aromatic amine, the sulfate of the aromatic amine, and sulfuric acid. A method for removing the treatment liquid is not particularly limited, and for example, it can be carried out by pulling up the activated carbon from the treatment liquid. (A) aromatic amine and the sulfate of the aromatic amine, or (B) the aromatic amine, the sulfate of the aromatic amine, and sulfuric acid are supported on the activated carbon prior to the removal of the treatment liquid from the activated carbon. The liquid may be diluted with water.
その後、処理液を除去した活性炭を乾燥させる。この乾燥には、例えば、自然乾燥、通風乾燥、熱風乾燥、マイクロ波加熱乾燥、間接加熱乾燥などを利用することができる。乾燥は、活性炭の温度が、例えば１３０℃以下、好ましくは８０℃以下に維持されるように行う。以上のようにして、本発明の脱臭材を製造することができる。 After that, the activated carbon from which the treatment liquid has been removed is dried. For this drying, for example, natural drying, air drying, hot air drying, microwave heating drying, indirect heating drying, or the like can be used. Drying is carried out so that the temperature of the activated carbon is maintained at, for example, 130° C. or lower, preferably 80° C. or lower. The deodorizing material of the present invention can be produced as described above.
次に、本発明の脱臭シートについて詳述する。本発明の脱臭シートは、上記の本発明の脱臭材を用いたものであり、本発明の脱臭材を含む。具体的には、本発明の脱臭シートは、例えば、上記の脱臭材がシート状に成形されたものである。シートの形態としては、特に限定されないが、不織布が好ましく挙げられる。本発明の脱臭シートは、上記の脱臭材をシート状に成形することなどを目的として、必要に応じてバインダーを含んでいてもよい。バインダーとしては、脱臭材を構成する活性炭同士を接着できるものであれば特に制限されず、例えば、（繊維状バインダーが挙げられ、繊維状バインダーの市販品としてはユニチカ株式会社製商品名メルティ）などを使用することができる。 Next, the deodorant sheet of the present invention will be described in detail. The deodorizing sheet of the present invention uses the deodorizing material of the present invention and includes the deodorizing material of the present invention. Specifically, the deodorizing sheet of the present invention is, for example, formed by molding the above-described deodorizing material into a sheet. The form of the sheet is not particularly limited, but a nonwoven fabric is preferred. The deodorizing sheet of the present invention may optionally contain a binder for the purpose of forming the deodorizing material into a sheet. The binder is not particularly limited as long as it can bond the activated carbons constituting the deodorizing material together. can be used.
本発明の脱臭シートがバインダーを含む場合、バインダーと、（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸が担持された活性炭との質量比（バインダー／活性炭）としては、好ましくは７５／２５～２５／７５程度が挙げられる。 When the deodorizing sheet of the present invention contains a binder, the binder and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine and sulfuric acid are supported. The mass ratio (binder/activated carbon) to activated carbon is preferably about 75/25 to 25/75.
本発明の脱臭シートの密度は、特に限定されるものではないが、アセトアルデヒドに対する脱臭能をより一層優れたものとする観点から、例えば、０．０５～０．３ｇ／ｃｍ3が好ましく、０．０５～０．２０ｇ／ｃｍ3がより好ましく、０．０８～０．１２ｇ／ｃｍ3が特に好ましい。また、本発明の脱臭シートの厚さとしては、例えば、０．１５～０．８０ｍｍ、０．１５～０．５０ｍｍ、好ましくは０．１５～０．２５ｍｍとすると、上記脱臭能に優れつつ、車室内の座席のカバー内に収容できやすくなる。上記のような密度が低い、および／または薄いシートを得る方法としては、例えば、目付け１～８ｇ／ｍ2程度の薄い不織布を製造し、該不織布を複数層重ねてニードルパンチ加工を施して一体化させることにより得ることができる。 The density of the deodorizing sheet of the present invention is not particularly limited, but is preferably 0.05 to 0.3 g/cm 3 and 0.05 to 0.3 g/cm 3 from the viewpoint of further improving the deodorizing ability against acetaldehyde. 05 to 0.20 g/cm 3 is more preferred, and 0.08 to 0.12 g/cm 3 is particularly preferred. The thickness of the deodorizing sheet of the present invention is, for example, 0.15 to 0.80 mm, 0.15 to 0.50 mm, preferably 0.15 to 0.25 mm. It becomes easy to accommodate in the cover of the seat in the passenger compartment. As a method for obtaining a sheet having a low density and/or thinness as described above, for example, a thin nonwoven fabric with a basis weight of about 1 to 8 g/m 2 is produced, and a plurality of layers of the nonwoven fabric are piled up and needle-punched to integrate them. It can be obtained by
本発明の脱臭シートは、例えば、上記の脱臭材をシート状に成形することにより製造することもできるし、繊維状活性炭に（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸を担持させる前の繊維状活性炭をシート状に成形した後、当該シートを上記と同様にして処理液に浸漬して、繊維状活性炭に（Ａ）芳香族アミンと該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミンと該芳香族アミンの硫酸塩と硫酸を担持させることによっても製造することができる。 The deodorizing sheet of the present invention can be produced, for example, by molding the above deodorizing material into a sheet, or by adding (A) an aromatic amine and a sulfate salt of the aromatic amine to fibrous activated carbon, or ( B) After the fibrous activated carbon before supporting the aromatic amine, the sulfate salt of the aromatic amine, and the sulfuric acid is formed into a sheet, the sheet is immersed in the treatment liquid in the same manner as described above to form a fibrous activated carbon. It can also be produced by supporting (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid.
本発明の脱臭シートを空気浄化用シートとして用いる場合は、エレクトレット化された不織布シート、ＨＥＰＡ（ｈｉｇｈ ｅｆｆｉｃｉｅｎｃｙ ｐａｒｔｉｃｕｌａｔｅ ａｉｒ）フィルタ、ＵＬＰＡ（ｕｌｔｒａ ｌｏｗ ｐｅｎｅｔｒａｔｉｏｎ ａｉｒ）フィルタなどの除塵シートを脱臭シートに貼り合せることによって、除塵効果を付与した積層体とすることも可能である。そのような積層体は、空気浄化と除塵とを行う空気清浄器などにおいて好適に使用され得る。 When the deodorizing sheet of the present invention is used as an air purification sheet, a dust removing sheet such as an electret nonwoven fabric sheet, a HEPA (high efficiency particulate air) filter, or an ULPA (ultra low penetration air) filter is attached to the deodorizing sheet. It is also possible to obtain a laminate having a dust removing effect. Such a laminate can be suitably used in an air purifier for air purification and dust removal.
本発明の脱臭シートは、上記した本発明の脱臭材を含んでいるため、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができ、自動車、電車、船舶、飛行機などの内装材にも好適に使用できる。中でも、本発明の脱臭シートは、自動車内装材として、車室内の座席のカバー内に収容して用いることができる。すなわち、本発明の脱臭シートを含む、車室内用座席とすることができる。また、本発明の脱臭材は、アセトアルデヒド以外にも、ホルムアルデヒド等の低級アルデヒドに対しても、脱離率を小さくすることができる。 Since the deodorizing sheet of the present invention contains the deodorizing material of the present invention described above, it is possible to reduce the desorption rate of the adsorbed acetaldehyde when placed in a high-temperature atmosphere after adsorbing acetaldehyde. , trains, ships, airplanes and the like. Among others, the deodorizing sheet of the present invention can be used as an automobile interior material by being housed in the cover of the seat in the passenger compartment. That is, it can be a vehicle interior seat including the deodorizing sheet of the present invention. Moreover, the deodorizing material of the present invention can reduce the desorption rate of not only acetaldehyde but also lower aldehydes such as formaldehyde.
以下に、実施例及び比較例を示して本発明を詳細に説明する。ただし、本発明は、実施例に限定されない。 EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. However, the invention is not limited to the examples.
＜実施例１＞
活性炭の準備
粒状石炭ピッチを、溶融押出機に供給し、溶融温度３２０℃で溶融混合し、吐出量２０ｇ／ｍｉｎで紡糸することによりピッチ繊維を得た。得られたピッチ繊維を空気中常温から３５４℃まで１～３０℃／分の割合で５４分間昇温することにより不融化処理をおこない、不融化されたピッチ繊維である活性炭前駆体を得た。得られた活性炭前駆体を、Ｈ2Ｏ濃度が１００容量％のガスを賦活炉内に連続的に導入し、雰囲気温度８７５℃で４０分間熱処理することにより賦活をおこない、繊維状活性炭を得た。得られた繊維状活性炭の全細孔容積は０．４７６ｃｃ／ｇ、比表面積は１２３２ｍ2／ｇ、平均細孔径は１．５５ｎｍ、０．６５ｎｍ以上２ｎｍ以下の細孔径の細孔容積は０．２５５ｃｃ／ｇであった。
<Example 1>
Preparation of activated charcoal
Granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320° C., and spun at a discharge rate of 20 g/min to obtain pitch fibers. The obtained pitch fibers were heated in the air from room temperature to 354° C. at a rate of 1 to 30° C./min for 54 minutes to perform an infusibilization treatment, thereby obtaining an activated carbon precursor as infusible pitch fibers. The obtained activated carbon precursor was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into an activation furnace and heat-treating it at an atmospheric temperature of 875° C. for 40 minutes to obtain fibrous activated carbon. . The obtained fibrous activated carbon had a total pore volume of 0.476 cc/g, a specific surface area of 1232 m 2 /g, an average pore diameter of 1.55 nm, and a pore volume of 0.65 nm or more and 2 nm or less. It was 255 cc/g.
薬剤溶液の調製
まず、７５質量％の濃度で硫酸を含有した硫酸水溶液を調製した。この硫酸水溶液を６５℃以上の温度で撹拌して、芳香族アミンとしてｐ－アミノ安息香酸を水溶液に加え、完全に溶解させたのち、活性炭の質量と処理液の体積との比が２０ｇ／Ｌとなるように水を加え、処理液を得た。なお、芳香族アミン及び硫酸の仕込み量は、活性炭１００質量部に対して２２．５質量部となるようにした。なお、硫酸の当該仕込み量（質量部）は、７５硫酸水溶液中の、純水を除いた硫酸のみの量（質量部）を示す。
Preparation of Chemical Solution First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75 mass % was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65° C. or higher, and p-aminobenzoic acid as an aromatic amine is added to the aqueous solution and completely dissolved. Water was added so as to obtain a treatment liquid. The amounts of the aromatic amine and sulfuric acid charged were set to 22.5 parts by mass with respect to 100 parts by mass of the activated carbon. The amount (parts by mass) of sulfuric acid charged indicates the amount (parts by mass) of only sulfuric acid excluding pure water in the aqueous solution of 75 sulfuric acid.
活性炭への薬剤の担持
次に、薬剤溶液に、上記得られた活性炭１００質量部を浸漬した。続いて、この溶液を１０分間に亘って撹拌して、活性炭を溶液中に均一に分散させた。その後、この分散液を静置した。８時間以上静置した後、活性炭を溶液から引き上げ、乾燥機を用いて８０℃で３時間に亘って乾燥させ、実施例１の脱臭材を得た。なお、脱臭材における、活性炭１００質量部に対する芳香族アミンと該芳香族アミンの硫酸塩の合計担持量（質量部）、及び活性炭１００質量部に対する芳香族アミンの硫酸塩と硫酸の合計担持量（質量部）は、前述の方法で測定した。
Carrying Agent on Activated Carbon Next, 100 parts by mass of the activated carbon obtained above was immersed in the chemical solution. The solution was then stirred for 10 minutes to evenly disperse the activated carbon in the solution. This dispersion was then allowed to stand. After standing still for 8 hours or more, the activated carbon was pulled out of the solution and dried at 80° C. for 3 hours using a dryer to obtain the deodorant of Example 1. In the deodorizing material, the total amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine per 100 parts by mass of the activated carbon, and the total amount of the sulfate of the aromatic amine and the sulfuric acid per 100 parts by mass of the activated carbon ( parts by mass) was measured by the method described above.
＜実施例２＞
活性炭の準備
実施例１で得た活性炭を準備した。
<Example 2>
Preparation of activated charcoal
Activated carbon obtained in Example 1 was prepared.
薬剤溶液の調製
まず、７５質量％の濃度で硫酸を含有した硫酸水溶液を調製した。この硫酸水溶液を６５℃以上の温度で撹拌して、芳香族アミンとしてｐ－アミノ安息香酸を水溶液に加え、完全に溶解させたのち、活性炭の質量と処理液の体積との比が２０ｇ／Ｌとなるように水を加え、処理液を得た。なお、芳香族アミン及び硫酸の仕込み量は、活性炭１００質量部に対して３０．０質量部となるようにした。なお、硫酸の当該仕込み量（質量部）は、７５硫酸水溶液中の、純水を除いた硫酸のみの量（質量部）を示す。
Preparation of Chemical Solution First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75 mass % was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65° C. or higher, and p-aminobenzoic acid as an aromatic amine is added to the aqueous solution and completely dissolved. Water was added so as to obtain a treatment liquid. The amounts of the aromatic amine and sulfuric acid charged were set to 30.0 parts by mass with respect to 100 parts by mass of the activated carbon. The amount (parts by mass) of sulfuric acid charged indicates the amount (parts by mass) of only sulfuric acid excluding pure water in the aqueous solution of 75 sulfuric acid.
活性炭への薬剤の担持
次に、薬剤溶液に、上記得られた活性炭１００質量部を浸漬した。続いて、この溶液を１０分間に亘って撹拌して、活性炭を溶液中に均一に分散させた。その後、この分散液を静置した。８時間以上静置した後、活性炭を溶液から引き上げ、乾燥機を用いて８０℃で３時間に亘って乾燥させ、実施例２の脱臭材を得た。
Carrying Agent on Activated Carbon Next, 100 parts by mass of the activated carbon obtained above was immersed in the chemical solution. The solution was then stirred for 10 minutes to evenly disperse the activated carbon in the solution. This dispersion was then allowed to stand. After standing still for 8 hours or longer, the activated carbon was pulled out of the solution and dried at 80° C. for 3 hours using a dryer to obtain a deodorizing material of Example 2.
＜実施例３＞
活性炭の準備
粒状石炭ピッチを、溶融押出機に供給し、溶融温度３２０℃で溶融混合し、吐出量２０ｇ／ｍｉｎで紡糸することによりピッチ繊維を得た。得られたピッチ繊維を空気中常温から３５４℃まで１～３０℃／分の割合で５４分間昇温することにより不融化処理をおこない、不融化されたピッチ繊維である活性炭前駆体を得た。得られた活性炭前駆体を、Ｈ2Ｏ濃度が１００容量％のガスを賦活炉内に連続的に導入し、雰囲気温度８７５℃で５０分間熱処理することにより賦活をおこない、繊維状活性炭を得た。得られた繊維状活性炭の、全細孔容積は０．７５３ｃｃ／ｇ、比表面積は１７３１ｍ2／ｇ、平均細孔径は１．７４ｎｍ、０．６５ｎｍ以上２ｎｍ以下の細孔径の細孔容積は０．６２２ｃｃ／ｇであった。
<Example 3>
Preparation of activated charcoal
Granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320° C., and spun at a discharge rate of 20 g/min to obtain pitch fibers. The obtained pitch fibers were heated in the air from room temperature to 354° C. at a rate of 1 to 30° C./min for 54 minutes to perform an infusibilization treatment, thereby obtaining an activated carbon precursor as infusible pitch fibers. The obtained activated carbon precursor was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 875° C. for 50 minutes to obtain fibrous activated carbon. . The obtained fibrous activated carbon had a total pore volume of 0.753 cc/g, a specific surface area of 1731 m 2 /g, an average pore diameter of 1.74 nm, and a pore volume of 0.65 nm or more and 2 nm or less. .622 cc/g.
薬剤溶液の調製
まず、７５質量％の濃度で硫酸を含有した硫酸水溶液を調製した。この硫酸水溶液を６５℃以上の温度で撹拌して、芳香族アミンとしてｐ－アミノ安息香酸を水溶液に加え、完全に溶解させたのち、活性炭の質量と処理液の体積との比が２０ｇ／Ｌとなるように水を加え、処理液を得た。なお、芳香族アミン及び硫酸の仕込み量は、活性炭１００質量部に対して２２．５質量部となるようにした。なお、硫酸の当該仕込み量（質量部）は、７５硫酸水溶液中の、純水を除いた硫酸のみの量（質量部）を示す
Preparation of Chemical Solution First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75 mass % was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65° C. or higher, and p-aminobenzoic acid as an aromatic amine is added to the aqueous solution and completely dissolved. Water was added so as to obtain a treatment liquid. The amounts of the aromatic amine and sulfuric acid charged were set to 22.5 parts by mass with respect to 100 parts by mass of the activated carbon. The amount of sulfuric acid charged (parts by mass) indicates the amount (parts by mass) of only sulfuric acid excluding pure water in the 75 sulfuric acid aqueous solution.
活性炭への薬剤の担持
次に、薬剤溶液に、上記得られた活性炭１００質量部を浸漬した。続いて、この溶液を１０分間に亘って撹拌して、活性炭を溶液中に均一に分散させた。その後、この分散液を静置した。８時間以上静置した後、活性炭を溶液から引き上げ、乾燥機を用いて８０℃で３時間に亘って乾燥させ、実施例３の脱臭材を得た。
Carrying Agent on Activated Carbon Next, 100 parts by mass of the activated carbon obtained above was immersed in the chemical solution. The solution was then stirred for 10 minutes to evenly disperse the activated carbon in the solution. This dispersion was then allowed to stand. After standing still for 8 hours or more, the activated carbon was pulled out of the solution and dried at 80° C. for 3 hours using a dryer to obtain a deodorizing material of Example 3.
＜実施例４＞
活性炭の準備
実施例３で得た活性炭を準備した。
<Example 4>
Preparation of activated charcoal
Activated carbon obtained in Example 3 was prepared.
薬剤溶液の調製
まず、７５質量％の濃度で硫酸を含有した硫酸水溶液を調製した。この硫酸水溶液を６５℃以上の温度で撹拌して、芳香族アミンとしてｐ－アミノ安息香酸を水溶液に加え、完全に溶解させたのち、活性炭の質量と処理液の体積との比が２０ｇ／Ｌとなるように水を加え、処理液を得た。なお、芳香族アミン及び硫酸の仕込み量は、活性炭１００質量部に対して３０．０質量部となるようにした。なお、硫酸の当該仕込み量（質量部）は、７５硫酸水溶液中の、純水を除いた硫酸のみの量（質量部）を示す。
Preparation of Chemical Solution First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75 mass % was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65° C. or higher, and p-aminobenzoic acid as an aromatic amine is added to the aqueous solution and completely dissolved. Water was added so as to obtain a treatment liquid. The amounts of the aromatic amine and sulfuric acid charged were set to 30.0 parts by mass with respect to 100 parts by mass of the activated carbon. The amount (parts by mass) of sulfuric acid charged indicates the amount (parts by mass) of only sulfuric acid excluding pure water in the aqueous solution of 75 sulfuric acid.
活性炭への薬剤の担持
次に、薬剤溶液に、上記得られた活性炭１００質量部を浸漬した。続いて、この溶液を１０分間に亘って撹拌して、活性炭を溶液中に均一に分散させた。その後、この分散液を静置した。８時間以上静置した後、活性炭を溶液から引き上げ、乾燥機を用いて８０℃で３時間に亘って乾燥させ、実施例４の脱臭材を得た。
Carrying Agent on Activated Carbon Next, 100 parts by mass of the activated carbon obtained above was immersed in the chemical solution. The solution was then stirred for 10 minutes to evenly disperse the activated carbon in the solution. This dispersion was then allowed to stand. After standing still for 8 hours or longer, the activated carbon was pulled out of the solution and dried at 80° C. for 3 hours using a dryer to obtain a deodorizing material of Example 4.
＜比較例１＞
実施例１で得た活性炭を準備した。
<Comparative Example 1>
Activated carbon obtained in Example 1 was prepared.
薬剤溶液の調製
まず、７５質量％の濃度で硫酸を含有した硫酸水溶液を調製した。この硫酸水溶液を６５℃以上の温度で撹拌して、芳香族アミンとしてｐ－アミノ安息香酸を水溶液に加え、完全に溶解させたのち、活性炭の質量と処理液の体積との比が２０ｇ／Ｌとなるように水を加え、処理液を得た。なお、芳香族アミン及び硫酸の仕込み量は、活性炭１００質量部に対して１５．０質量部となるようにした。なお、硫酸の当該仕込み量（質量部）は、７５硫酸水溶液中の、純水を除いた硫酸のみの量（質量部）を示す。
Preparation of Chemical Solution First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75 mass % was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65° C. or higher, and p-aminobenzoic acid as an aromatic amine is added to the aqueous solution and completely dissolved. Water was added so as to obtain a treatment liquid. The amounts of the aromatic amine and sulfuric acid charged were set to 15.0 parts by mass with respect to 100 parts by mass of the activated carbon. The amount (parts by mass) of sulfuric acid charged indicates the amount (parts by mass) of only sulfuric acid excluding pure water in the aqueous solution of 75 sulfuric acid.
活性炭への薬剤の担持
次に、薬剤溶液に、上記得られた活性炭１００質量部を浸漬した。続いて、この溶液を１０分間に亘って撹拌して、活性炭を溶液中に均一に分散させた。その後、この分散液を静置した。８時間以上静置した後、活性炭を溶液から引き上げ、乾燥機を用いて８０℃で３時間に亘って乾燥させ、比較例１の脱臭材を得た。
Carrying Agent on Activated Carbon Next, 100 parts by mass of the activated carbon obtained above was immersed in the chemical solution. The solution was then stirred for 10 minutes to evenly disperse the activated carbon in the solution. This dispersion was then allowed to stand. After standing still for 8 hours or more, the activated carbon was pulled out of the solution and dried at 80° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1.
＜比較例２＞
活性炭の準備
粒状石炭ピッチを、溶融押出機に供給し、溶融温度３２０℃で溶融混合し、吐出量２０ｇ／ｍｉｎで紡糸することによりピッチ繊維を得た。得られたピッチ繊維を空気中常温から３５４℃まで１～３０℃／分の割合で５４分間昇温することにより不融化処理をおこない、不融化されたピッチ繊維である活性炭前駆体を得た。得られた活性炭前駆体を、Ｈ2Ｏ濃度が１００容量％のガスを賦活炉内に連続的に導入し、雰囲気温度８７５℃で３０分間熱処理することにより賦活をおこない、繊維状活性炭を得た。得られた繊維状活性炭の、全細孔容積は０．３１５ｃｃ／ｇ、比表面積は８２５ｍ2／ｇ、平均細孔径は１．５３ｎｍ、０．６５ｎｍ以上２ｎｍ以下の細孔径の細孔容積は０．１１６ｃｃ／ｇであった。
<Comparative Example 2>
Preparation of activated charcoal
Granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320° C., and spun at a discharge rate of 20 g/min to obtain pitch fibers. The obtained pitch fibers were heated in the air from room temperature to 354° C. at a rate of 1 to 30° C./min for 54 minutes to perform an infusibilization treatment, thereby obtaining an activated carbon precursor as infusible pitch fibers. The obtained activated carbon precursor was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into an activation furnace and heat-treating it at an atmospheric temperature of 875° C. for 30 minutes to obtain fibrous activated carbon. . The obtained fibrous activated carbon had a total pore volume of 0.315 cc/g, a specific surface area of 825 m 2 /g, an average pore diameter of 1.53 nm, and a pore volume of 0.65 nm or more and 2 nm or less. .116 cc/g.
薬剤溶液の調製
まず、７５質量％の濃度で硫酸を含有した硫酸水溶液を調製した。この硫酸水溶液を６５℃以上の温度で撹拌して、芳香族アミンとしてｐ－アミノ安息香酸を水溶液に加え、完全に溶解させたのち、活性炭の質量と処理液の体積との比が２０ｇ／Ｌとなるように水を加え、処理液を得た。なお、芳香族アミン及び硫酸の仕込み量は、活性炭１００質量部に対して３０．０質量部となるようにした。なお、硫酸の当該仕込み量（質量部）は、７５硫酸水溶液中の、純水を除いた硫酸のみの量（質量部）を示す。
Preparation of Chemical Solution First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75 mass % was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65° C. or higher, and p-aminobenzoic acid as an aromatic amine is added to the aqueous solution and completely dissolved. Water was added so as to obtain a treatment liquid. The amounts of the aromatic amine and sulfuric acid charged were set to 30.0 parts by mass with respect to 100 parts by mass of the activated carbon. The amount (parts by mass) of sulfuric acid charged indicates the amount (parts by mass) of only sulfuric acid excluding pure water in the aqueous solution of 75 sulfuric acid.
活性炭への薬剤の担持
次に、薬剤溶液に、上記得られた活性炭１００質量部を浸漬した。続いて、この溶液を１０分間に亘って撹拌して、活性炭を溶液中に均一に分散させた。その後、この分散液を静置した。８時間以上静置した後、活性炭を溶液から引き上げ、乾燥機を用いて８０℃で３時間に亘って乾燥させ、比較例２の脱臭材を得た。
Carrying Agent on Activated Carbon Next, 100 parts by mass of the activated carbon obtained above was immersed in the chemical solution. The solution was then stirred for 10 minutes to evenly disperse the activated carbon in the solution. This dispersion was then allowed to stand. After standing for 8 hours or longer, the activated carbon was pulled out of the solution and dried at 80° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2.
実施例１～４、比較例１及び２で得た脱臭材を用い、比表面積、アセトアルデヒド脱離率を前述の方法に従い、測定した。また、得られた脱臭材の比表面積から活性炭の比表面積を減じ、芳香族アミン及び硫酸の担持により減少した比表面積を算出した。結果を表１に示す。 Using the deodorizing materials obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the specific surface areas and acetaldehyde elimination rates were measured according to the methods described above. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorizing material, and the specific surface area decreased by supporting the aromatic amine and sulfuric acid was calculated. Table 1 shows the results.
表１から、実施例１～４の脱臭材は、活性炭と、前記活性炭に担持された、（Ａ）芳香族アミン及び該芳香族アミンの硫酸塩、又は、（Ｂ）芳香族アミン、該芳香族アミンの硫酸塩、及び硫酸とを含む、脱臭材であって、前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部であることから、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率を小さくすることができるものであった。 From Table 1, the deodorizing materials of Examples 1 to 4 consisted of activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine supported on the activated carbon, or (B) an aromatic amine and the aromatic A deodorizing material containing a sulfate salt of a group amine and sulfuric acid, wherein the activated carbon has a total pore volume of 0.45 cc/g or more, and the aromatic amine and the aromatic The total supported amount of the amine sulfate and the amine sulfate is 20 to 32 parts by mass, and the total supported amount of the aromatic amine sulfate and the sulfuric acid is 1.8 to 3.5 parts by mass with respect to 100 parts by mass of the activated carbon. Therefore, the desorption rate of the adsorbed acetaldehyde can be reduced when placed in a high-temperature atmosphere after adsorbing acetaldehyde.
一方、比較例１の脱臭材は、活性炭１００質量部に対する、芳香族アミンと芳香族アミンの硫酸塩との合計担持量が２０質量部未満、及び、活性炭１００質量部に対する、芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８質量部未満であったことから、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率が高かった。また、比較例２の脱臭材は、活性炭の全細孔容積が０．４５ｃｃ／ｇ未満であり、芳香族アミンと芳香族アミンの硫酸塩との合計担持量が２０質量部未満、及び、活性炭１００質量部に対する、芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８質量部未満であったことから、アセトアルデヒドを吸着させた後に高温雰囲気下に置いたときの、吸着したアセトアルデヒドの脱離率が高かった。 On the other hand, in the deodorizing material of Comparative Example 1, the total supported amount of the aromatic amine and the sulfate salt of the aromatic amine is less than 20 parts by mass with respect to 100 parts by mass of the activated carbon, and the sulfuric acid of the aromatic amine is less than 20 parts by mass with respect to 100 parts by mass of the activated carbon. Since the total amount of salt and sulfuric acid supported was less than 1.8 parts by mass, the desorption rate of adsorbed acetaldehyde was high when placed in a high-temperature atmosphere after adsorbing acetaldehyde. In the deodorizing material of Comparative Example 2, the total pore volume of activated carbon is less than 0.45 cc/g, the total amount of aromatic amine and sulfate of aromatic amine supported is less than 20 parts by mass, and the activated carbon Since the total supported amount of the aromatic amine sulfate and the sulfuric acid was less than 1.8 parts by mass with respect to 100 parts by mass, when placed in a high-temperature atmosphere after adsorbing acetaldehyde, the adsorbed acetaldehyde had a high detachment rate.
Claims (4)
前記活性炭の全細孔容積が０．４５ｃｃ／ｇ以上であり、
以下の方法によって測定される、前記活性炭１００質量部に対する、前記芳香族アミンと前記芳香族アミンの硫酸塩との合計担持量が２０～３２質量部であり、
以下の方法によって測定される、前記活性炭１００質量部に対する、前記芳香族アミンの硫酸塩と前記硫酸との合計担持量が１．８～３．５質量部である、
脱臭材。
（活性炭１００質量部に対する芳香族アミンと該芳香族アミンの硫酸塩の合計担持量（質量部）の測定）
活性炭に担持された芳香族アミンと該芳香族アミンの硫酸塩の合計担持量については、薬剤溶液の、活性炭を浸漬する前の液と活性炭を浸漬した後の液の有機物濃度を、それぞれ全有機物濃度（ＴＯＣ）計を用いて測定し、浸漬操作前後の有機物濃度の差から、合計担持量を測定するまず全有機物濃度（ＴＯＣ）計を用いて、浸漬操作前後の薬剤溶液について、炭素（Ｃ）に換算された有機物濃度（ｍｇＣ／Ｌ）を測定し、操作前後の濃度の差を求める。別途、秤量して調製した既知濃度の芳香族アミン水溶液について同様に全有機物濃度を測定し、有機物濃度（ｍｇＣ／Ｌ）と芳香族アミン濃度（ｍｇ芳香族アミン／Ｌ）の対応を表す検量線を作成する。作成した検量線を用いて、添着操作前後の有機物濃度の差（ｍｇＣ／Ｌ）を芳香族アミン濃度の差（ｍｇ芳香族アミン／Ｌ）に換算する。求めた濃度の差に処理液量（Ｌ）を乗じて芳香族アミン質量の差を算出する。算出された値を、薬剤溶液に浸漬する前の活性炭１００質量部あたりの質量部に換算し、得られた質量部を、活性炭１００質量部に対する芳香族アミンと該芳香族アミンの硫酸塩の合計担持量（質量部）とする。
（活性炭１００質量部に対する芳香族アミンの硫酸塩と硫酸の合計担持量（質量部）の測定）
活性炭に担持された芳香族アミンの硫酸塩と硫酸の合計物質量は、活性炭を浸漬する前の薬剤溶液と、活性炭を浸漬した後の薬剤溶液について、ＪＩＳ Ｋ ０１０１：１９９８ ４２．４に規定のイオンクロマトグラフ法に準じ硫酸イオンの濃度（ｍｇ／Ｌ）を測定することで、これらの合計担持量を計算する。浸漬操作前後の薬剤溶液の硫酸イオンの濃度（ｍｇ／Ｌ）を、検量線を用いてそれぞれ測定し、操作前後の硫酸イオン濃度の差（ｍｇ／Ｌ）を求める。求めた操作前後の硫酸イオン濃度の差（ｍｇ／Ｌ）に、硫酸の分子量（９８．０８ｇ／ｍｏｌ）と硫酸イオンの分子量（９６．０６ｇ／ｍｏｌ）の比を乗じて硫酸濃度の差に換算する。硫酸濃度の差に処理液量（Ｌ）を乗じて操作前後の硫酸の差を算出する。算出した操作前後の硫酸の差を、薬剤溶液に浸漬する前の活性炭１００質量部あたりの質量部に換算し、得られた質量部を、活性炭１００質量部に対する芳香族アミンの硫酸塩と硫酸の合計担持量（質量部）とする。 A deodorizing material comprising activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid supported on the activated carbon. and
The activated carbon has a total pore volume of 0.45 cc/g or more,
The total supported amount of the aromatic amine and the sulfate salt of the aromatic amine with respect to 100 parts by mass of the activated carbon measured by the following method is 20 to 32 parts by mass,
The total supported amount of the sulfate salt of the aromatic amine and the sulfuric acid is 1.8 to 3.5 parts by mass with respect to 100 parts by mass of the activated carbon , which is measured by the following method .
Deodorizing material.
(Measurement of the total supported amount (parts by mass) of the aromatic amine and the sulfate salt of the aromatic amine with respect to 100 parts by mass of activated carbon)
Regarding the total amount of aromatic amine supported on activated carbon and the sulfate salt of the aromatic amine, the concentration of organic matter in the chemical solution before and after immersion in activated carbon was calculated as total organic matter. Measure using a concentration (TOC) meter, and measure the total supported amount from the difference in the concentration of organic substances before and after the immersion operation. ) is measured, and the difference in concentration before and after the operation is determined. Separately, the total organic substance concentration was similarly measured for an aqueous aromatic amine solution of known concentration prepared by weighing, and a calibration curve representing the correspondence between the organic substance concentration (mgC/L) and the aromatic amine concentration (mg aromatic amine/L) was prepared. to create Using the prepared calibration curve, the difference in organic substance concentration before and after the impregnation operation (mgC/L) is converted into the difference in aromatic amine concentration (mg aromatic amine/L). The difference in aromatic amine mass is calculated by multiplying the obtained difference in concentration by the amount of treatment liquid (L). The calculated value is converted to parts by mass per 100 parts by mass of activated carbon before being immersed in the chemical solution, and the obtained parts by mass are the sum of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of activated carbon. It is defined as the supported amount (parts by mass).
(Measurement of total supported amount (parts by mass) of aromatic amine sulfate and sulfuric acid per 100 parts by mass of activated carbon)
The total substance amount of the aromatic amine sulfate and sulfuric acid supported on the activated carbon is defined in JIS K 0101: 1998 42.4 for the chemical solution before the activated carbon is immersed and the chemical solution after the activated carbon is immersed. By measuring the concentration (mg/L) of sulfate ions according to the ion chromatography method, the total supported amount is calculated. The sulfate ion concentration (mg/L) of the chemical solution before and after the immersion operation is measured using a calibration curve, and the difference in sulfate ion concentration (mg/L) before and after the operation is determined. The difference in sulfate ion concentration before and after the operation (mg/L) obtained is multiplied by the ratio of the molecular weight of sulfuric acid (98.08 g/mol) and the molecular weight of sulfate ion (96.06 g/mol) to convert to the difference in sulfuric acid concentration. do. The difference in sulfuric acid concentration before and after the operation is calculated by multiplying the difference in sulfuric acid concentration by the amount of treated liquid (L). The calculated difference in sulfuric acid before and after the operation was converted to parts by mass per 100 parts by mass of activated carbon before being immersed in the chemical solution, and the obtained parts by mass were added to 100 parts by mass of the aromatic amine sulfate and sulfuric acid relative to 100 parts by mass of activated carbon. The total supported amount (parts by mass).
A deodorizing sheet comprising the deodorizing material according to any one of claims 1 to 3.
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| JP2005152033A (en) | 2003-11-20 | 2005-06-16 | Cataler Corp | Deodorant for composite offensive odor |
| US20090029853A1 (en) | 2005-07-06 | 2009-01-29 | Toyo Boseki Kabushiki Kaisha | Adsorbent and Process for Producing the Same |
| WO2011040577A1 (en) | 2009-09-30 | 2011-04-07 | 株式会社 キャタラー | Adsorbent material and method for producing same |
| JP2011072603A (en) | 2009-09-30 | 2011-04-14 | Cataler Corp | Fibrous deodorant and deodorizing sheet |
| JP2017165936A (en) | 2016-03-15 | 2017-09-21 | 東ソー株式会社 | Aldehyde scavenger |
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| JP2721509B2 (en) * | 1988-05-13 | 1998-03-04 | 日本たばこ産業株式会社 | Adsorbent for aldehydes |
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| JP2005152033A (en) | 2003-11-20 | 2005-06-16 | Cataler Corp | Deodorant for composite offensive odor |
| US20090029853A1 (en) | 2005-07-06 | 2009-01-29 | Toyo Boseki Kabushiki Kaisha | Adsorbent and Process for Producing the Same |
| WO2011040577A1 (en) | 2009-09-30 | 2011-04-07 | 株式会社 キャタラー | Adsorbent material and method for producing same |
| JP2011072603A (en) | 2009-09-30 | 2011-04-14 | Cataler Corp | Fibrous deodorant and deodorizing sheet |
| JP2017165936A (en) | 2016-03-15 | 2017-09-21 | 東ソー株式会社 | Aldehyde scavenger |
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