JP5935354B2 - Adsorption sheet and adsorption element using the same - Google Patents
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Description
本発明は、空気中の水分、有機溶剤、および、悪臭成分を効率的に分離・回収、もしくは、吸着・除去する吸着シート、および、それを用いた吸着エレメントに関する。 The present invention relates to an adsorption sheet that efficiently separates, collects, adsorbs and removes moisture, organic solvents, and malodorous components in the air, and an adsorption element using the same.
活性炭やシリカゲル、ゼオライト等といった多孔質材料は、脱臭、空気や水の浄化、ガスの分離・精製といった様々な用途に利用されており、現代の生活に必要不可欠な材料となっている。近年、種々の配位形態を取り得る金属イオンと、２座以上の配位座を有する架橋配位子とを組み合わせて自己集合させた多孔質材料、すなわち、多孔性金属錯体（ＭＯＦ）、もしくは、多孔性配位高分子（ＰＣＰ）と呼ばれる新しい多孔質材料が見出された。これら多孔性金属錯体は、活性炭やシリカゲル、ゼオライト等の従来の多孔質材料にはない特徴、すなわち、高比表面積、シャープな細孔分布、および、高い構造設計性という特徴を有しており、注目されている。 Porous materials such as activated carbon, silica gel, and zeolite are used for various purposes such as deodorization, purification of air and water, and separation and purification of gas, and are indispensable materials for modern life. In recent years, a porous material self-assembled by combining a metal ion capable of various coordination forms and a bridging ligand having two or more coordination sites, that is, a porous metal complex (MOF), or A new porous material called a porous coordination polymer (PCP) has been found. These porous metal complexes have characteristics not found in conventional porous materials such as activated carbon, silica gel, and zeolite, that is, high specific surface area, sharp pore distribution, and high structural design. Attention has been paid.
これら多孔性金属錯体として、例えば、特許文献１には、特定のジカルボン酸金属錯体がガス吸蔵材、特にメタンを主成分とするガスの吸蔵材として好適であることが開示されている。また、特許文献２には、銅イオンとトリメシン酸類から合成された多孔質錯体が開示されており、吸着材がその用途の一例として開示されている。さらに、特許文献３には、金属クロムまたはクロム塩と、トリメシン酸類から得られる多孔性配位高分子が、特に水蒸気吸着材として優れていることが開示されており、また、多孔性配位高分子を種々の物質の吸着材として使用するためには、減圧下で加熱することによって脱溶媒することが好ましいことが開示されている。しかしながら、特許文献１〜３には、これら多孔性金属錯体からなる吸着シート、および、それを用いた吸着エレメントについての製造方法等の具体的な記載はない。 As these porous metal complexes, for example, Patent Document 1 discloses that a specific dicarboxylic acid metal complex is suitable as a gas occlusion material, particularly a gas occlusion material mainly composed of methane. Patent Document 2 discloses a porous complex synthesized from copper ions and trimesic acids, and an adsorbent is disclosed as an example of its use. Furthermore, Patent Document 3 discloses that a porous coordination polymer obtained from metal chromium or a chromium salt and trimesic acid is particularly excellent as a water vapor adsorbent, and has a high porous coordination polymer. It is disclosed that in order to use molecules as adsorbents for various substances, it is preferable to remove the solvent by heating under reduced pressure. However, Patent Documents 1 to 3 do not have specific descriptions such as an adsorption sheet made of these porous metal complexes and a production method for an adsorption element using the same.
従来、粉末活性炭やゼオライトを含有するシートとして、粉末活性炭やゼオライトと繊維成分を混合抄造してなるシートが知られている。例えば、特許文献４には、粉末活性炭を混合抄造したシートとして、粉末活性炭と自己固結性を有する繊維状の粘土鉱物、および、耐熱性人造繊維を主成分として含有することを特徴とするコルゲート加工可能な吸着性シートが開示されている。しかしながら、この吸着性シートは、耐熱性人造繊維を含有するため、耐熱性には優れているものの、有機バインダーを含有しないため、吸着材の担持性に劣り、吸着材が容易に脱落してしまうという問題があり、また、吸着材の脱落を抑制するために、シート中に含有される吸着材量を低減すると、吸着性能が低下してしまうという問題があった。さらに、上記吸着シートは、吸着シート中に有機バインダーを含有しないため、シートが柔軟性に乏しく、折り曲げ加工等の加工性が悪いという問題、加えて、粉末活性炭を吸着材として用いるものであるため、吸着性能が十分でないという問題もあった。 Conventionally, as a sheet containing powdered activated carbon or zeolite, a sheet obtained by mixing and making powder activated carbon or zeolite and a fiber component is known. For example, Patent Document 4 discloses a corrugated sheet containing powdered activated carbon and a self-consolidating fibrous clay mineral and heat-resistant artificial fibers as a main component as a mixed paper sheet. A processable adsorbent sheet is disclosed. However, since this adsorbent sheet contains heat-resistant man-made fibers and is excellent in heat resistance, it does not contain an organic binder, so the adsorbent is inferior in carrying ability and the adsorbent easily falls off. In addition, if the amount of the adsorbent contained in the sheet is reduced in order to suppress the adsorbent from falling off, there is a problem that the adsorption performance is deteriorated. Furthermore, since the adsorbent sheet does not contain an organic binder in the adsorbent sheet, the sheet is poor in flexibility and has poor workability such as bending, and in addition, powdered activated carbon is used as the adsorbent. There was also a problem that the adsorption performance was not sufficient.
また、ゼオライトを混合抄造したシートとして、例えば、特許文献５には、ゼオライトと水分吸着性・自己固結性を有する粘土鉱物繊維、及びガラス繊維、並びに有機バインダーを含有する吸着シートが開示されている。この吸着シートは、粘土鉱物繊維、及び、ガラス繊維を含有するため、耐熱性に優れており、また、有機バインダーを含有するため、吸着材の担持性、および、シートの柔軟性には優れている。しかしながら、吸着材であるゼオライトの細孔内に有機バインダーの側鎖等が吸着してしまい、十分な吸着性能が得られないという問題があった。なお、吸着材（ゼオライト）の細孔内に吸着した有機バインダーは、温度４００℃〜８００℃で３０分以上焼成することにより除去することは可能であるが、有機バインダーを除去したとしても、吸着材がゼオライトであるため、吸着性能が十分とはいえず、また、ゼオライトに代えて多孔性金属錯体を吸着材として用いた場合、前記条件で焼成すると、多孔性金属錯体の細孔構造が破壊されてしまい、十分な吸着性能が得られないという問題があった。 Further, as a sheet made by mixing and making zeolite, for example, Patent Document 5 discloses an adsorption sheet containing clay mineral fiber having water adsorption property / self-consolidation property and glass fiber, and an organic binder. Yes. Since this adsorbing sheet contains clay mineral fibers and glass fibers, it has excellent heat resistance, and since it contains an organic binder, it has excellent adsorbent supportability and sheet flexibility. Yes. However, there has been a problem that the side chains of the organic binder are adsorbed in the pores of the zeolite, which is the adsorbent, and sufficient adsorption performance cannot be obtained. The organic binder adsorbed in the pores of the adsorbent (zeolite) can be removed by baking at a temperature of 400 ° C. to 800 ° C. for 30 minutes or more. However, even if the organic binder is removed, the adsorption takes place. Since the material is zeolite, the adsorption performance is not sufficient, and when a porous metal complex is used as the adsorbent instead of zeolite, the pore structure of the porous metal complex is destroyed when fired under the above conditions. As a result, there is a problem that sufficient adsorption performance cannot be obtained.
上述のとおり、耐熱性、吸着材（多孔性金属錯体）の担持性、および、シートの柔軟性に優れており、十分な吸着性能を有する吸着シート、および、それを用いた吸着エレメントは見当たらないというのが現状である。ここでいう耐熱性とは、８０℃以上の温度条件下で、吸着シート、および、それを用いた吸着エレメントにおいて、その強度が著しく低下しないことを指す。 As described above, there is no adsorbing sheet that has excellent heat resistance, adsorbent (porous metal complex) supportability, and sheet flexibility and has sufficient adsorbing performance, and an adsorbing element using the adsorbing element. That is the current situation. The term “heat resistance” as used herein means that the strength is not significantly reduced in the adsorption sheet and the adsorption element using the same under a temperature condition of 80 ° C. or higher.
本発明は上記従来技術の課題を背景になされたものであり、耐熱性、多孔性金属錯体の担持性、および、シートの柔軟性に優れており、且つ、十分な吸着性能を有する吸着シート、および、それを用いた吸着エレメントを提供することを目的とする。 The present invention has been made against the background of the above-mentioned prior art, and has excellent heat resistance, supportability of a porous metal complex, and flexibility of the sheet, and an adsorption sheet having sufficient adsorption performance, And it aims at providing the adsorption element using the same.
本発明者らは上記課題を解決するため、鋭意研究した結果、遂に本発明を完成するに到った。すなわち本発明は、以下の通りである。
１．多孔性金属錯体、および、耐熱性繊維を含有することを特徴とする吸着シート、
２．前記吸着シートが自己固結性を有する粘土鉱物繊維を含有する上記１の吸着シート、
３．前記吸着シートが有機バインダーを含有する上記１又は２の吸着シート、および、
４．上記１〜３のいずれかの吸着シートを用いた吸着エレメントである。
As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention is as follows.
1. A porous metal complex, and an adsorbent sheet characterized by containing a heat-resistant fiber,
2. 1 said adsorption sheet containing the clay mineral fiber in which the said adsorption sheet has self-consolidating property,
3. 1 or 2 of the adsorption sheet, wherein the adsorption sheet contains an organic binder, and
4). It is an adsorption | suction element using the adsorption sheet in any one of said 1-3.
なお、本明細書でいう有機溶剤とは、物質を溶解する性質をもつ有機化合物のことを指し、具体的には、トルエン、キシレン、スチレン等の芳香族炭化水素類；クロロベンゼン等の塩化芳香族炭化水素類；ジクロロメタン、クロロエチレン等の塩化脂肪族炭化水素類；メタノール、エタノール、イソプロパノール等のアルコール類；酢酸エチル等のエステル類、１，４−ジオキサン等のエーテル類；メチルエチルケトン等のケトン類；メチルセロソルブ等のグリコールエーテル類；シクロヘキサノン等の脂環式炭化水素類；ノルマルヘキサン等の脂肪族炭化水素類；トリメチルシラノール、ヘキサメチルジシラザン、環状シロキサン（オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等）等の含ケイ素化合物；その他、クレゾール、二硫化炭素、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等；が挙げられる。 In addition, the organic solvent as used in this specification refers to the organic compound which has the property to melt | dissolve a substance, specifically, aromatic hydrocarbons, such as toluene, xylene, and styrene; Chlorinated aromatics, such as chlorobenzene Hydrocarbons; chlorinated aliphatic hydrocarbons such as dichloromethane and chloroethylene; alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate; ethers such as 1,4-dioxane; ketones such as methyl ethyl ketone; Glycol ethers such as methyl cellosolve; alicyclic hydrocarbons such as cyclohexanone; aliphatic hydrocarbons such as normal hexane; trimethylsilanol, hexamethyldisilazane, cyclic siloxane (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane Silicon-containing compounds such as , Cresol, carbon disulfide, N, N- dimethylformamide, N- methylpyrrolidone and the like; and the like.
また、本明細書でいう悪臭成分としては、具体的には、ホルムアルデヒド、アセトアルデヒド等のアルデヒド類；酢酸、イソ吉草酸などのカルボン酸類；アンモニア等の含窒素化合物；硫化水素、二硫化メチル、メチルメルカプタン等の含硫黄化合物；等が挙げられる。 Further, the malodorous component referred to in this specification includes, specifically, aldehydes such as formaldehyde and acetaldehyde; carboxylic acids such as acetic acid and isovaleric acid; nitrogen-containing compounds such as ammonia; hydrogen sulfide, methyl disulfide, methyl And sulfur-containing compounds such as mercaptans.
本発明の吸着シート、および、それを用いた吸着エレメントは、多孔性金属錯体、および、耐熱性繊維を含有しており、さらに、必要に応じて、自己固結性を有する粘土鉱物繊維、および、有機バインダーを含有するため、耐熱性、多孔性金属錯体の担持性、シートの柔軟性、および、吸着性能に優れるという利点を有する。 The adsorbing sheet of the present invention and the adsorbing element using the same contain a porous metal complex and a heat-resistant fiber, and if necessary, a clay mineral fiber having self-consolidating properties, and Since it contains an organic binder, it has advantages of excellent heat resistance, porous metal complex support, sheet flexibility, and adsorption performance.
以下、本発明を詳細に説明する。本発明における吸着シートは、多孔性金属錯体、および、耐熱性繊維を含有する。多孔性金属錯体を含有することにより、十分な吸着性能が得られ、また、耐熱性繊維を含有することにより、８０℃以上の温度条件下においても著しい強度の低下を生じ難く、十分な耐熱性が得られるからである。吸着シートが多孔性金属錯体を含有していない場合は、吸着性能が不十分となる。また、吸着シートが耐熱性繊維を含有していなければ、十分な耐熱性が得られず、８０℃以上の温度条件下において、吸着シートに著しい強度の低下が起こる。 Hereinafter, the present invention will be described in detail. The adsorption sheet in the present invention contains a porous metal complex and heat-resistant fibers. By containing a porous metal complex, sufficient adsorption performance can be obtained, and by containing a heat-resistant fiber, it is difficult to cause a significant decrease in strength even under temperature conditions of 80 ° C. or higher, and sufficient heat resistance. This is because When the adsorption sheet does not contain a porous metal complex, the adsorption performance becomes insufficient. Further, if the adsorbing sheet does not contain heat resistant fibers, sufficient heat resistance cannot be obtained, and the strength of the adsorbing sheet is significantly reduced under a temperature condition of 80 ° C. or higher.
本発明に係る多孔性金属錯体は、金属イオンと、配位子を有する化合物とからなる多孔性材料である。本発明で使用可能な多孔性金属錯体の形態には特に定めがなく、粉末状、もしくは、粒状のものを用いることができる。好ましくは、平均粒子径が０．１μｍ〜２００μｍの多孔性金属錯体である。平均粒子径が０．１μｍ未満では、取り扱いが困難であり、また、平均粒子径が２００μｍを超えると、吸着シートに、多孔性金属錯体を十分に担持させ難くなり、多孔性金属錯体の脱落が多くなる場合がある。 The porous metal complex according to the present invention is a porous material composed of a metal ion and a compound having a ligand. The form of the porous metal complex that can be used in the present invention is not particularly limited, and a powdered or granular form can be used. Preferably, it is a porous metal complex having an average particle size of 0.1 μm to 200 μm. If the average particle size is less than 0.1 μm, it is difficult to handle, and if the average particle size exceeds 200 μm, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the porous metal complex may fall off. May increase.
多孔性金属錯体の７７Ｋ窒素吸着法によるＢＥＴ比表面積は、特に限定されないが、例えば５００ｍ2／ｇ以上であることが好ましい。ＢＥＴ比表面積が５００ｍ2／ｇより小さいと、十分な吸着性能を得難い場合がある。ＢＥＴ比表面積は、１０００ｍ2／ｇ以上であるのがより好ましい。ＢＥＴ比表面積の上限は特に限定されないが、６０００ｍ2／ｇ以下であることが好ましい。この範囲を超えると、多孔性金属錯体の製造が非常に困難になるという不都合が生じるからである。
なお、平均粒子径及びＢＥＴ比表面積は、実施例に記載の方法により測定することができる。
The BET specific surface area of the porous metal complex by the 77K nitrogen adsorption method is not particularly limited, but is preferably 500 m 2 / g or more, for example. If the BET specific surface area is smaller than 500 m 2 / g, it may be difficult to obtain sufficient adsorption performance. The BET specific surface area is more preferably 1000 m 2 / g or more. The upper limit of the BET specific surface area is not particularly limited, but is preferably 6000 m 2 / g or less. If this range is exceeded, the production of the porous metal complex becomes very difficult.
In addition, an average particle diameter and a BET specific surface area can be measured by the method as described in an Example.
前記多孔性金属錯体を構成する金属イオンとしては、特に限定されないが、例えば、アルミニウムイオン等の典型金属元素、鉄イオン、銅イオン及び亜鉛イオン等の遷移金属元素が挙げられる。一方、配位子を有する化合物としては、例えば、２−メチルイミダゾール、テレフタル酸及びトリメシン酸等が挙げられる。具体的な多孔性金属錯体としては、例えば、亜鉛イオンと２−メチルイミダゾールから構成される多孔性金属錯体（ＢＡＳＦ社製、Ｂａｓｏｌｉｔｅ（登録商標、以下同様） Ｚ１２００）、アルミニウムイオンとテレフタル酸から構成される多孔性金属錯体（ＢＡＳＦ社製、Ｂａｓｏｌｉｔｅ Ａ１００）、銅イオンとトリメシン酸から構成される多孔性金属錯体（ＢＡＳＦ社製、Ｂａｓｏｌｉｔｅ Ｃ３００）、鉄イオンとトリメシン酸から構成される多孔性金属錯体（ＢＡＳＦ社製、Ｂａｓｏｌｉｔｅ Ｆ３００）等が挙げられる。吸着シートの使用目的が、水分を含むガスから有機溶剤、および、悪臭成分の効率的な分離・回収、もしくは、吸着・除去である場合は、疎水性の高い多孔性金属錯体を採用するのが好ましい。疎水性の高い多孔性金属錯体とは、真空条件下、温度２００℃で４８時間以上の真空加熱処理を施した後の多孔性金属錯体を、３０℃、相対湿度６０％ＲＨの窒素雰囲気下に３日以上静置したときの質量増加を、上記真空加熱処理直後の多孔性金属錯体の質量で割った質量増加率が１０質量％未満である多孔性金属錯体のことを指す。具体的な疎水性の高い多孔性金属錯体としては、亜鉛イオンと２−メチルイミダゾールから構成される多孔性金属錯体（ＢＡＳＦ社製、Ｂａｓｏｌｉｔｅ Ｚ１２００）等が挙げられる。 Although it does not specifically limit as a metal ion which comprises the said porous metal complex, For example, transition metal elements, such as typical metal elements, such as an aluminum ion, an iron ion, a copper ion, and a zinc ion, are mentioned. On the other hand, examples of the compound having a ligand include 2-methylimidazole, terephthalic acid, and trimesic acid. As a specific porous metal complex, for example, a porous metal complex composed of zinc ion and 2-methylimidazole (BASF, Basolite (registered trademark, hereinafter the same) Z1200), composed of aluminum ion and terephthalic acid Porous metal complex (BASF, Basolite A100), porous metal complex composed of copper ion and trimesic acid (BASF, Basolite C300), porous metal complex composed of iron ion and trimesic acid (Basolite F300, manufactured by BASF). If the purpose of using the adsorbent sheet is to efficiently separate / recover, or adsorb / remove organic solvents and malodorous components from moisture-containing gases, a highly hydrophobic porous metal complex should be used. preferable. A highly hydrophobic porous metal complex is a porous metal complex that has been subjected to a vacuum heat treatment at a temperature of 200 ° C. for 48 hours or more under vacuum conditions in a nitrogen atmosphere at 30 ° C. and a relative humidity of 60% RH. It refers to a porous metal complex having a mass increase rate of less than 10% by mass obtained by dividing the mass increase when left standing for 3 days or more by the mass of the porous metal complex immediately after the vacuum heat treatment. Specific examples of a highly hydrophobic porous metal complex include a porous metal complex composed of zinc ions and 2-methylimidazole (BASF Corp., Basolite Z1200).
本発明の吸着シートにおける、多孔性金属錯体の含有量は、５０質量％〜８５質量％であるのが好ましく、より好ましくは６０質量％〜８０質量％である。含有量が５０質量％未満では十分な吸着性能を得ることが難しい場合がある。一方、含有量が８５質量％を超えると、吸着シートに多孔性金属錯体を十分に担持することが困難になり、脱落量が多くなる。また、シート強度も著しく低下する虞がある。 The content of the porous metal complex in the adsorption sheet of the present invention is preferably 50% by mass to 85% by mass, and more preferably 60% by mass to 80% by mass. If the content is less than 50% by mass, it may be difficult to obtain sufficient adsorption performance. On the other hand, when the content exceeds 85% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the amount of dropping off increases. In addition, the sheet strength may be significantly reduced.
本発明の吸着シートに含まれる耐熱性繊維は、吸着シートの耐熱性を確保する成分である。ここで、耐熱性繊維とは、あらかじめ１５０℃、真空下で１２時間乾燥させたサンプル３０ｍｇを、熱量計測測定装置（Ｑ５０、ティー・エイ・インスツルメント・ジャパン株式会社製）を使用し、空気流量６０ｍＬ／ｍｉｎ、昇温速度２０℃／ｍｉｎで常温から３００℃まで昇温させたときの重量減少率が５％以下の繊維を意味する。斯かる耐熱性繊維は、８０℃以上の温度条件下において強度の著しい低下を生じ難く、吸着シートに耐熱性を付与する成分として好ましい。なお、強度の著しい低下を生じ難いとは、８０℃以上の加熱雰囲気下において、本発明の吸着シートを９０度に折り曲げた際に、吸着シートに割れや亀裂等が生じ難いことをいう。 The heat resistant fiber contained in the adsorption sheet of the present invention is a component that ensures the heat resistance of the adsorption sheet. Here, the heat resistant fiber is a sample of 30 mg dried in advance at 150 ° C. under vacuum for 12 hours using a calorimeter (Q50, manufactured by TA Instruments Japan Co., Ltd.), and air It means a fiber having a weight reduction rate of 5% or less when the temperature is raised from normal temperature to 300 ° C. at a flow rate of 60 mL / min and a temperature increase rate of 20 ° C./min. Such a heat-resistant fiber hardly causes a significant decrease in strength under a temperature condition of 80 ° C. or higher, and is preferable as a component that imparts heat resistance to the adsorption sheet. In addition, it means that it is hard to produce a crack, a crack, etc. to an adsorption sheet when the adsorption sheet of this invention is bend | folded at 90 degree | times in a heating atmosphere of 80 degreeC or more that it is hard to produce the remarkable fall of intensity | strength.
具体的な耐熱性繊維としては、ガラス繊維、セラミック繊維、ロックウール繊維等の無機繊維；アラミド繊維、メタアラミド繊維、ポリベンズイミダゾール繊維、ポリベンズオキサゾール繊維、ポリイミド繊維、ポリアミド繊維、ポリアミドイミド繊維、ポリエーテルケトン繊維等の有機繊維；および、これらをフィブリル化した繊維；等が挙げられ、これらの中の１種又は２種以上を用いることが好ましい。耐熱性繊維の繊維径は１μｍ〜１５μｍであるのが好ましく、１μｍ〜１０μｍであるのがより好ましい。また、繊維長は１ｍｍ〜１０ｍｍであるのが好ましく、２ｍｍ〜５ｍｍであるのがより好ましい。吸着シートの強度および柔軟性の両方を向上させる観点から、耐熱性繊維には、繊維径１μｍ〜１０μｍであり、且つ、繊維長２ｍｍ〜５ｍｍのガラス繊維が含まれているのが好ましい。 Specific heat-resistant fibers include glass fibers, ceramic fibers, rock wool fibers, and the like; aramid fibers, meta-aramid fibers, polybenzimidazole fibers, polybenzoxazole fibers, polyimide fibers, polyamide fibers, polyamideimide fibers, poly And organic fibers such as ether ketone fibers; and fibers obtained by fibrillating them; and one or more of these are preferably used. The fiber diameter of the heat resistant fiber is preferably 1 μm to 15 μm, more preferably 1 μm to 10 μm. The fiber length is preferably 1 mm to 10 mm, and more preferably 2 mm to 5 mm. From the viewpoint of improving both the strength and flexibility of the adsorption sheet, the heat-resistant fiber preferably contains glass fibers having a fiber diameter of 1 μm to 10 μm and a fiber length of 2 mm to 5 mm.
本発明における吸着シートは自己固結性を有する粘土鉱物繊維を含有することが好ましい。ここで、自己固結性とは、それ自身のみで固結する特性のことを表す。したがって、自己固結性を有する粘土鉱物繊維を使用することで、吸着シートの耐熱性、および、多孔性金属錯体の担持性を向上させることができ、さらに、粘土鉱物繊維の自己固結性により吸着シート強度を一層向上させることができる。前記粘土鉱物繊維の種類については特に限定されないが、入手が容易であることから、珪酸マグネシウム繊維、もしくは、珪酸カルシウム繊維が好ましい。前記粘土鉱物繊維の繊維径と繊維長については特に限定されないが、繊維径は、好ましくは０．１μｍ〜０．５μｍであり、より好ましくは０．１μｍ〜０．２μｍであり、繊維長は、好ましくは１μｍ〜５０μｍであり、より好ましくは１μｍ〜３０μｍである。繊維径が０．１μｍ未満で、繊維長が１μｍ未満の場合、繊維が微細すぎるため、多孔性金属錯体の担持性が低下する傾向があるだけでなく、吸着シートの強度も低下し、さらにシート作製時等の粘土鉱物繊維の取り扱いが困難になることがある。一方、繊維径が０．５μｍより大きく、また、繊維長が５０μｍより長くなると、十分な自己固結性を発現させるために高温で長時間の加熱が必要となり、多孔性金属錯体の細孔構造が壊れてしまう虞がある。 The adsorbing sheet in the present invention preferably contains clay mineral fibers having self-consolidating properties. Here, the self-consolidating property represents a property of consolidating only by itself. Therefore, by using clay mineral fibers having self-consolidating properties, it is possible to improve the heat resistance of the adsorption sheet and the supportability of the porous metal complex, and further, due to the self-consolidating properties of the clay mineral fibers. The strength of the adsorption sheet can be further improved. Although it does not specifically limit about the kind of said clay mineral fiber, Since it is easy to acquire, a magnesium silicate fiber or a calcium silicate fiber is preferable. The fiber diameter and fiber length of the clay mineral fiber are not particularly limited, but the fiber diameter is preferably 0.1 μm to 0.5 μm, more preferably 0.1 μm to 0.2 μm, and the fiber length is Preferably they are 1 micrometer-50 micrometers, More preferably, they are 1 micrometer-30 micrometers. When the fiber diameter is less than 0.1 μm and the fiber length is less than 1 μm, the fiber is too fine, so that not only the support property of the porous metal complex tends to be lowered but also the strength of the adsorbing sheet is lowered, and the sheet It may be difficult to handle clay mineral fibers during production. On the other hand, if the fiber diameter is larger than 0.5 μm and the fiber length is longer than 50 μm, heating at a high temperature for a long time is required to develop sufficient self-consolidation, and the porous structure of the porous metal complex. May break.
吸着シートにおける粘土鉱物繊維の含有率は、５質量％〜３５質量％が好ましく、より好ましくは５質量％〜２５質量％である。粘土鉱物繊維の含有率が５質量％未満では、多孔性金属錯体の担持性が不足し、一方、３５質量％を超えると、多孔性金属錯体が粘土鉱物繊維により被覆されてしまい、十分な吸着性能を得難い場合がある。 5 mass%-35 mass% are preferable, and, as for the content rate of the clay mineral fiber in an adsorption sheet, More preferably, they are 5 mass%-25 mass%. If the content of the clay mineral fiber is less than 5% by mass, the supportability of the porous metal complex is insufficient. On the other hand, if the content exceeds 35% by mass, the porous metal complex is covered with the clay mineral fiber and sufficient adsorption is achieved. It may be difficult to obtain performance.
本発明における吸着シートは、有機バインダーを含むことが好ましい。吸着シートの柔軟性や強度を向上させられるからである。有機バインダーとしては、多孔性金属錯体（吸着材）と耐熱性繊維とを接合できるものであれば特に限定されない。例えば、ポリビニルアルコール系ポリマー、ポリアクリロニトリル系ポリマー、ポリエチレン系ポリマー、ポリエステル系ポリマー等を用いることができる。取り扱い性の面からは、ポリビニルアルコール系ポリマーが好ましい。有機バインダーの使用態様は特に限定されないが、繊維状のものを使用すると、吸着シートが簡便に作製できるため好ましい。吸着シートにおける有機バインダーの含有率は、５質量％〜１５質量％が好ましく、５質量％〜１０質量％がより好ましい。５質量％未満では多孔性金属錯体の担持性が不足し、１５質量％を超えると多孔性金属錯体が有機バインダーにより被覆されてしまい、十分な吸着性能が得られ難くなる傾向がある。 The adsorbing sheet in the present invention preferably contains an organic binder. This is because the flexibility and strength of the adsorption sheet can be improved. The organic binder is not particularly limited as long as it can join the porous metal complex (adsorbent) and the heat-resistant fiber. For example, a polyvinyl alcohol polymer, a polyacrylonitrile polymer, a polyethylene polymer, a polyester polymer, or the like can be used. From the viewpoint of handleability, polyvinyl alcohol polymers are preferred. The use mode of the organic binder is not particularly limited, but it is preferable to use a fibrous material because an adsorption sheet can be easily produced. 5 mass%-15 mass% are preferable, and, as for the content rate of the organic binder in an adsorption sheet, 5 mass%-10 mass% are more preferable. If it is less than 5% by mass, the supportability of the porous metal complex is insufficient, and if it exceeds 15% by mass, the porous metal complex is covered with an organic binder, and sufficient adsorption performance tends to be difficult to obtain.
本発明の吸着シートは、前記多孔性金属錯体以外の多孔質材料を含んでいてもよく、本発明の吸着シートに含有される多孔質材料については特に限定されないが、例えば、活性炭、ゼオライト、シリカゲル、活性アルミナ、粘土鉱物（前述の粘土鉱物繊維を除く）、アルミノリン酸塩、シリコアルミノリン酸、スチレン−ジビニルベンゼン共重合体等の有機高分子多孔質体、等が挙げられる。好ましくは、安価に入手できる活性炭、ゼオライト、シリカゲル、活性アルミナである。 The adsorbent sheet of the present invention may contain a porous material other than the porous metal complex, and the porous material contained in the adsorbent sheet of the present invention is not particularly limited. For example, activated carbon, zeolite, silica gel , Activated alumina, clay minerals (excluding the aforementioned clay mineral fibers), aluminophosphates, silicoaluminophosphoric acid, organic polymer porous materials such as styrene-divinylbenzene copolymer, and the like. Preferred are activated carbon, zeolite, silica gel and activated alumina, which can be obtained at low cost.
本発明の吸着シートの厚みは、０．１ｍｍ〜０．６ｍｍであることが好ましく、より好ましくは０．１ｍｍ〜０．５ｍｍである。厚みが０．１ｍｍ未満であればシート強度が著しく低下するため、後加工においてハニカム状等の吸着エレメントに加工することが困難になる場合がある。また、厚みが０．６ｍｍより大きければ、吸着シートをハニカム状等に加工した時の吸着エレメントの圧損が高くなる傾向がある。 The thickness of the suction sheet of the present invention is preferably 0.1 mm to 0.6 mm, more preferably 0.1 mm to 0.5 mm. If the thickness is less than 0.1 mm, the sheet strength is remarkably reduced, so that it may be difficult to process into a honeycomb-like adsorption element in post-processing. Further, if the thickness is larger than 0.6 mm, the pressure loss of the adsorbing element tends to increase when the adsorbing sheet is processed into a honeycomb shape or the like.
本発明の吸着シートの坪量は、２５ｇ／ｍ2〜２００ｇ／ｍ2が好ましい。より好ましくは４０ｇ／ｍ2〜１５０ｇ／ｍ2である。坪量が２５ｇ／ｍ2未満であれば、シートの厚みが薄くなり、シート強度が著しく低下する虞があり、後加工においてハニカム状等の吸着エレメントへの加工が困難になる場合がある。また、坪量が２００ｇ／ｍ2を超えると、シートの厚みが大きくなり過ぎ、ハニカム状等に加工した時の吸着エレメントの圧損が高くなる場合がある。 The basis weight of the adsorption sheet of the present invention, 25g / m 2 ~200g / m 2 is preferred. More preferably from 40g / m 2 ~150g / m 2 . If the basis weight is less than 25 g / m 2 , the thickness of the sheet may be reduced, and the sheet strength may be significantly reduced, which may make it difficult to process the honeycomb-shaped adsorption element in post-processing. On the other hand, if the basis weight exceeds 200 g / m 2 , the thickness of the sheet becomes too large, and the pressure loss of the adsorption element when processed into a honeycomb or the like may increase.
本発明の吸着シートを製造する方法としては、特に制限されず、従来公知の加工方法を用いることができる。好ましくは、多孔性金属錯体と、耐熱性繊維、必要により用いられる粘土鉱物繊維、及び、有機バインダー等のシート構成材料とを、水、有機溶媒又はこれらの混合物中に分散させ、成形、脱水、乾燥することにより得られる湿式シート化法が挙げられる。 It does not restrict | limit especially as a method of manufacturing the adsorption sheet of this invention, A conventionally well-known processing method can be used. Preferably, a porous metal complex, a heat-resistant fiber, a clay mineral fiber used if necessary, and a sheet constituent material such as an organic binder are dispersed in water, an organic solvent or a mixture thereof, and molded, dehydrated, The wet sheeting method obtained by drying is mentioned.
なお、上記多孔性金属錯体は、その細孔内に溶媒分子を有する状態で、上記シート構成材料と混合し、シート化工程に供するのが好ましい。多孔性金属錯体が細孔内に溶媒分子を有していない場合、吸着シートを構成する有機バインダーが、当該細孔内に吸着されてしまう虞がある。この場合、シート化後、後述する脱溶媒処理を実施しても多孔性金属錯体細孔内に捕捉された有機バインダーを除去することは難しく、吸着シートの吸着性能が劣る結果となる。すなわち、本発明では、多孔性金属錯体の細孔に溶媒分子を吸着させておくことにより、シート化工程における有機バインダー等の細孔への吸着を防止し、シート化工程後、後述する脱溶媒処理により細孔内から溶媒分子を除去することにより、吸着シートの吸着性能を確保している。通常は、多孔性金属錯体を合成する段階で、当該多孔性金属錯体の細孔内に溶媒分子が吸着するが、多孔性金属錯体が細孔内に溶媒分子を有していない場合又は溶媒分子の吸着量が不十分である場合は、後述する実施例に記載の方法により細孔内に有機溶媒を吸着させることができる。尚、ここでいう溶媒分子とは、水や一般的な有機溶媒分子を指す。 In addition, it is preferable that the said porous metal complex is mixed with the said sheet constituent material in the state which has a solvent molecule in the pore, and uses for a sheet forming process. When the porous metal complex does not have solvent molecules in the pores, the organic binder constituting the adsorption sheet may be adsorbed in the pores. In this case, it is difficult to remove the organic binder trapped in the pores of the porous metal complex even after the solvent removal treatment described later is carried out after sheet formation, resulting in poor adsorption performance of the adsorption sheet. That is, in the present invention, by adsorbing solvent molecules to the pores of the porous metal complex, adsorption to the pores of the organic binder or the like in the sheeting step is prevented. By removing the solvent molecules from the pores by the treatment, the adsorption performance of the adsorption sheet is ensured. Usually, at the stage of synthesizing a porous metal complex, solvent molecules are adsorbed in the pores of the porous metal complex, but the porous metal complex does not have solvent molecules in the pores or the solvent molecules When the amount of adsorbed is insufficient, the organic solvent can be adsorbed in the pores by the method described in Examples described later. In addition, the solvent molecule | numerator here refers to water and a general organic solvent molecule.
本発明の吸着シートの製造では、シート化工程後に、吸着シート内に含まれる溶媒を除去する脱溶媒処理工程を実施する。上述の様に、前記多孔性金属錯体は、その細孔内に溶媒分子を有する状態でシート化されている。したがって、多孔性金属錯体がその細孔内に溶媒分子を有する状態では、十分な吸着性能が得られ難い。よって、吸着性能を発現させるため、シート化工程後に脱溶媒処理を実施する。尚、脱溶媒処理の実施時期はシート化工程以降であれば特に限定されない。 In manufacture of the adsorption sheet of this invention, the desolvation process process which removes the solvent contained in an adsorption sheet is implemented after a sheeting process. As described above, the porous metal complex is formed into a sheet with solvent molecules in the pores. Therefore, in a state where the porous metal complex has solvent molecules in the pores, it is difficult to obtain sufficient adsorption performance. Therefore, in order to develop the adsorption performance, the solvent removal treatment is performed after the sheet forming step. In addition, if the implementation time of a solvent removal process is after the sheet forming process, it will not be specifically limited.
脱溶媒処理の条件は特に定めないが、温度は８０℃〜３００℃であることが好ましい。８０℃未満では、溶媒の除去が不完全となる虞があり、十分な吸着性能が得られ難い場合がある。一方、３００℃を超えると、多孔性金属錯体の細孔構造が壊れてしまう虞があり、この場合も十分な吸着性能が得られ難くなる。より好ましくは１００℃〜２００℃である。また、脱溶媒処理は、減圧下で実施することで一層効率よく溶媒を除去できる。この際、圧力は特に限定されず、多孔性金属錯体の物性や配合量に応じて適宜調整すればよいが、例えば、１０3Ｐａ〜１０-5Ｐａが好ましく、１０-1Ｐａ〜１０-5Ｐａであるのがより好ましい。脱溶媒処理時間も特に限定されないが、例えば１時間〜１００時間とするのが好ましく、より好ましくは３時間〜４８時間であり、さらに好ましくは３時間〜２４時間である。尚、最も好ましい脱溶媒処理の条件は、真空条件下で１００℃〜２００℃、３時間〜２４時間である。 The conditions for the solvent removal treatment are not particularly defined, but the temperature is preferably 80 ° C to 300 ° C. If it is less than 80 degreeC, there exists a possibility that the removal of a solvent may become incomplete and sufficient adsorption | suction performance may be difficult to be obtained. On the other hand, when it exceeds 300 ° C., the pore structure of the porous metal complex may be broken, and in this case, it is difficult to obtain sufficient adsorption performance. More preferably, it is 100 degreeC-200 degreeC. Moreover, the solvent removal can be more efficiently removed by carrying out the solvent removal treatment under reduced pressure. At this time, the pressure is not particularly limited, may be suitably adjusted depending on the physical properties and amount of the porous metal complex, but for example, preferably 10 3 Pa~10 -5 Pa, 10 -1 Pa~10 -5 More preferably, it is Pa. Although the solvent removal treatment time is not particularly limited, it is preferably, for example, 1 hour to 100 hours, more preferably 3 hours to 48 hours, and further preferably 3 hours to 24 hours. The most preferable conditions for the solvent removal treatment are 100 ° C. to 200 ° C. for 3 hours to 24 hours under vacuum conditions.
本発明の吸着シートは、平面状で使用してもよく、また、適宜、プリーツ加工、ハニカム加工、又は、コルゲート加工等を施して、所望の形状として用いてもよい。 The adsorption sheet of the present invention may be used in a planar shape, or may be used in a desired shape by appropriately performing pleating, honeycomb processing, corrugating, or the like.
本発明の吸着エレメントは、上記本発明の吸着シートを備えているところに特徴を有する。本発明に係る吸着エレメントの型式は特に限定されず、従来公知の型式はいずれも採用でき、用途や目的に応じて適宜選択すればよい。また、本発明の吸着エレメントに備えられる吸着シートの形状には特に定めはないが、例えば、吸着シートを平面状、プリーツ状、ハニカム状等に加工したものを用いることができる。例えば、プリーツ状に加工された吸着シートは直交流型吸着エレメントとしての使用において、また、ハニカム状に加工された吸着シートは平行流型吸着エレメントとしての使用において、それぞれ、処理する気体との接触面積を大きくして除去効率の向上と、吸着エレメントの低圧損化とを同時に図ることができる。平行流型吸着エレメントは、直交流型吸着エレメントと比較して、ミストやゴミによる目詰まりの防止、低圧損化、軽量化の点で優れているため、当該吸着エレメントに備えられる吸着シートはハニカム状であることが好ましい。 The adsorption element of the present invention is characterized in that the adsorption sheet of the present invention is provided. The type of the adsorbing element according to the present invention is not particularly limited, and any conventionally known type can be adopted and may be appropriately selected according to the application and purpose. Further, the shape of the suction sheet provided in the suction element of the present invention is not particularly limited, but for example, a suction sheet processed into a flat shape, a pleat shape, a honeycomb shape, or the like can be used. For example, when the adsorption sheet processed into a pleat is used as a cross-flow type adsorption element, and when the adsorption sheet processed into a honeycomb is used as a parallel flow type adsorption element, contact with the gas to be treated respectively. By increasing the area, it is possible to improve the removal efficiency and reduce the pressure loss of the adsorption element at the same time. The parallel flow type adsorption element is superior to the cross flow type adsorption element in terms of prevention of clogging due to mist and dust, low pressure loss, and weight reduction. Therefore, the adsorption sheet provided in the adsorption element is a honeycomb. It is preferable that it is a shape.
本発明の吸着シート、および、それを用いた吸着エレメントは、屋内、乗り物内、壁紙、家具、内装材、樹脂成形体、電気機器等で、悪臭成分等を低減する目的や、工場等から排出される空気中の有機溶剤の分離・回収、もしくは、吸着・除去の目的で広く用いることができる。 The adsorbing sheet of the present invention and the adsorbing element using the same are discharged indoors, in vehicles, wallpaper, furniture, interior materials, resin moldings, electrical equipment, etc., for the purpose of reducing malodorous components, etc. It can be widely used for the purpose of separation / recovery or adsorption / removal of organic solvents in the air.
以下、実施例によって本発明の作用効果をより具体的に示す。下記実施例は本発明を限定する性質のものではなく、前・後記の趣旨に沿って設計変更することはいずれも本発明の技術的範囲に含まれるものである。なお、実施例中で測定した特性値の評価方法を以下に示す。 Hereinafter, the effects of the present invention will be described more specifically by way of examples. The following examples are not intended to limit the present invention, and any design changes that fall within the spirit of the preceding and following descriptions are within the technical scope of the present invention. In addition, the evaluation method of the characteristic value measured in the Example is shown below.
［ＢＥＴ比表面積の測定方法］
実施例、比較例で使用した多孔性金属錯体サンプル（有機溶媒処理前）約１００ｍｇを採取し、１２０℃で１２時間真空乾燥した後、秤量した。自動比表面積測定装置（ジェミニ２３７５、マイクロメリティックス社製）を使用し、液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を、相対圧を０．０２〜０．９５の範囲で徐々に高めながら４０点測定し、前記サンプルの吸着等温線を作成した。自動比表面積測定装置に付属の解析ソフト（ＧＥＭＩＮＩ−ＰＣＷ ｖｅｒｓｉｏｎ１．０１）にて、ＢＥＴ条件で、表面積解析範囲を０．０１〜０．１５に設定して、ＢＥＴ比表面積［ｍ2／ｇ］を求めた。
[Measurement method of BET specific surface area]
About 100 mg of a porous metal complex sample (before treatment with an organic solvent) used in Examples and Comparative Examples was collected, vacuum-dried at 120 ° C. for 12 hours, and weighed. Using an automatic specific surface area measuring device (Gemini 2375, manufactured by Micromeritics), the amount of nitrogen gas adsorbed at the boiling point of liquid nitrogen (-195.8 ° C.), the relative pressure of 0.02 to 0.95. 40 points were measured while gradually increasing in the range, and an adsorption isotherm of the sample was created. With the analysis software (GEMINI-PCW version 1.01) attached to the automatic specific surface area measuring device, the surface area analysis range is set to 0.01 to 0.15 under the BET conditions, and the BET specific surface area [m 2 / g] Asked.
［平均粒子径の測定方法］
走査型電子顕微鏡（株式会社日立製作所製、Ｓ−３５００）を使用して、下記実施例及び比較例で用いた多孔性金属錯体の直径を１００点測定し、それを相加平均して、多孔性金属錯体の平均粒子径［μｍ］を求めた。
[Measurement method of average particle size]
Using a scanning electron microscope (manufactured by Hitachi, Ltd., S-3500), the diameters of the porous metal complexes used in the following examples and comparative examples were measured at 100 points, and the results were arithmetically averaged. The average particle size [μm] of the conductive metal complex was determined.
［繊維径、繊維長の測定方法］
走査型電子顕微鏡（株式会社日立製作所製、Ｓ−３５００）により、下記実施例及び比較例で用いた耐熱性繊維、粘土鉱物繊維、有機バインダーの１００点分の繊維直径［μｍ］、繊維長［ｍｍ］を測定した。１００点分の繊維直径を相加平均して、サンプルの繊維径［μｍ］を求めた。また、１００点分の繊維長を相加平均して、サンプルの繊維長［ｍｍ］を求めた。
[Measurement method of fiber diameter and fiber length]
Using a scanning electron microscope (S-3500, manufactured by Hitachi, Ltd.), the fiber diameter [μm], fiber length [100 points of heat-resistant fiber, clay mineral fiber, and organic binder used in the following Examples and Comparative Examples] mm]. The fiber diameter [μm] of the sample was obtained by arithmetically averaging the fiber diameters of 100 points. Moreover, the fiber length [mm] of the sample was calculated by averaging the fiber lengths of 100 points.
［耐熱性の測定方法］
実施例、比較例で製造した吸着シートから切り出した１０ｃｍ×１０ｃｍの試験片について、空気雰囲気下２５０℃で１０時間処理を行った後、処理後の試験片の両端を持ち、９０度に折り曲げた。この時、シートが割れなかったものを○、亀裂が生じたものを△、割れてしまったものを×として評価した。
[Measurement method of heat resistance]
About the test piece of 10 cm x 10 cm cut out from the adsorption sheet manufactured by the Example and the comparative example, after processing at 250 degreeC by air atmosphere for 10 hours, it has both ends of the test piece after a process, and it bent at 90 degree | times. . At this time, the case where the sheet was not broken was evaluated as ◯, the case where the crack was generated was evaluated as Δ, and the case where the sheet was broken was evaluated as ×.
［担持性の測定方法］
実施例、比較例で製造した吸着シートから切り出した１０ｃｍ×１０ｃｍの試験片に、直径２．４ｃｍ、質量２０ｇの球体（素材：アルミニウム）を、１０ｃｍ/ｓの速度で１０回衝突させ、脱落した多孔性金属錯体の量が、０．１ｍｇより少ない場合を○、１０ｍｇより多い場合を×、０．１ｍｇ〜１０ｍｇの場合を△とした。
[Measurement method of supportability]
A sphere (material: aluminum) having a diameter of 2.4 cm and a mass of 20 g was collided 10 times at a speed of 10 cm / s on a 10 cm × 10 cm test piece cut out from the adsorption sheet manufactured in Example and Comparative Example, and dropped off. The case where the amount of the porous metal complex was less than 0.1 mg was evaluated as ◯, the case where the amount was more than 10 mg as x, and the case where the amount was 0.1 mg to 10 mg as Δ.
［柔軟性の測定方法］
実施例、比較例で製造した吸着シートから切り出した１０ｃｍ×１０ｃｍの試験片の両端を持ち、９０度に折り曲げた。この時、シートが割れなかったものを○、亀裂が生じたものを△、割れてしまったものを×として評価した。
[Measurement method of flexibility]
The test piece of 10 cm x 10 cm cut out from the adsorption sheet manufactured in the Example and the comparative example was held, and it bent at 90 degree | times. At this time, the case where the sheet was not broken was evaluated as ◯, the case where the crack was generated was evaluated as Δ, and the case where the sheet was broken was evaluated as ×.
［吸着性能の測定方法］
バインダーとして無機接着剤（水ガラス）を使用し、吸着シートを定法によりコルゲート化し、さらに、得られたコルゲートボードを、無機接着剤（水ガラス）を使用して積層することにより、ハニカム化し、３００セル／ｉｎｃｈ2のハニカムサンプルを作製した。６０ｍｍφのガラス製カラムにハニカムサンプル（６０ｍｍφ、厚み２０ｍｍ）をセットし、そのカラム中にトルエン５ｐｐｍを含む温度２５℃の乾燥空気を２ｍ／ｓの速度で通過させた。ＦＩＤ付きガスクロマトグラフ（株式会社島津製作所製、ＧＣ−２０１４）にて、ハニカムサンプル通過前後のトルエン濃度を１分毎に測定し、その通過前後の濃度変化からトルエンの除去率を算出した。除去率が２０％になるまで測定を続け、その経過時間、除去率よりトルエンの総除去質量［ｇ］を算出し、それをハニカムサンプルの体積で割ることによりトルエン除去量［ｇ／Ｌ］を算出した。
[Measurement method of adsorption performance]
An inorganic adhesive (water glass) is used as a binder, the adsorbing sheet is corrugated by a regular method, and the obtained corrugated board is laminated by using an inorganic adhesive (water glass) to form a honeycomb, 300 A cell / inch 2 honeycomb sample was prepared. A honeycomb sample (60 mmφ, thickness 20 mm) was set in a 60 mmφ glass column, and dry air containing 5 ppm of toluene at a temperature of 25 ° C. was passed through the column at a speed of 2 m / s. Using a gas chromatograph with FID (Shimadzu Corporation, GC-2014), the toluene concentration before and after passing through the honeycomb sample was measured every minute, and the toluene removal rate was calculated from the change in concentration before and after the passage. The measurement is continued until the removal rate reaches 20%, and the total removal mass [g] of toluene is calculated from the elapsed time and the removal rate, and the toluene removal amount [g / L] is calculated by dividing it by the volume of the honeycomb sample. Calculated.
（実施例１）
Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％（溶媒分子を除く）、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置（東洋紡エンジニアリング株式会社製、以下同様。）を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルについて、耐熱性、担持性、柔軟性、吸着性能を測定した。
Example 1
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (excluding solvent molecules), 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0) as clay mineral fiber 0.1 μm, fiber length 1 μm) as an organic binder, polyvinyl alcohol (PVA) fibers (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) are mixed at a ratio of 10% by mass, and the basis weight An adsorption sheet was prepared using a wet papermaking apparatus (manufactured by Toyobo Engineering Co., Ltd., the same applies hereinafter) at a mass of 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained sample was measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例２）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ａ１００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 2)
As a porous metal complex, Basolite A100 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample, 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例３）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｃ３００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをエタノール中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 3)
As a porous metal complex, Basolite C300 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in ethanol for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample, 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例４）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｆ３００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
Example 4
As a porous metal complex, Basolite F300 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample, 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例５）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを６０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．２μｍ、繊維長３０μｍ）を１５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、１５０℃、１気圧条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 5)
As a porous metal complex, Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 60% by mass of the porous metal complex sample, 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.2 μm, fiber length 30 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Further, the solvent removal treatment was performed at 150 ° C. and 1 atm for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例６）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを６０質量％、耐熱性繊維として、フィブリル化されたアラミド繊維（帝人製、トワロン（登録商標）、繊維径１２μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を１５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、１５０℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 6)
As a porous metal complex, Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 60% by mass of the porous metal complex sample as heat-resistant fiber, 15% by mass of fibrillated aramid fiber (Teijin, Twaron (registered trademark), fiber diameter 12 μm, fiber length 3 mm), clay mineral fiber, 15% by mass of magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm), and 10% by mass of polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) as an organic binder An adsorbent sheet was prepared using a wet papermaking apparatus at a mass of 70 g / m 2 basis weight. Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例７）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を篩いにかけ、平均粒子径が１０μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを６０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を１５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、１５０℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 7)
As a porous metal complex, Basolite Z1200 (manufactured by BASF) was sieved to prepare an average particle size of 10 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 60% by mass of the porous metal complex sample, 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例８）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を１０ｋｇｆ／ｃｍ2の圧力で軽く押し固め、篩いにかけ、平均粒子径が１５０μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを６０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を１５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、１５０℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 8)
As a porous metal complex, Basolite Z1200 (manufactured by BASF) was lightly pressed and hardened at a pressure of 10 kgf / cm 2 and sieved to prepare an average particle size of 150 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 60% by mass of the porous metal complex sample, 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例９）
多孔性金属錯体として、Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを８０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１０質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を５質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
Example 9
As a porous metal complex, Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 80% by mass of the porous metal complex sample, 10% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) As an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 5% by mass, resulting in a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine by mass. Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例１０）
Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を２０質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 10)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample, 20% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, An adsorbing sheet was prepared using a wet papermaking machine at a mass of 70 g / m 2 on a basis weight, and a fiber diameter of 11 μm and a fiber length of 3 mm). Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（実施例１１）
Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を２０質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Example 11)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample, 20% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber, and magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber ) Was mixed at a ratio of 10% by mass, and an adsorbent sheet was prepared using a wet papermaking machine at a mass of basis weight 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（比較例１）
ＨＳＺ−３９０ＨＵＡ（東ソー社製、Ｙ型ゼオライト）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。得られたゼオライトサンプルを７０質量％、耐熱性繊維として、ガラス繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Comparative Example 1)
HSZ-390HUA (manufactured by Tosoh Corporation, Y-type zeolite) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. 70% by mass of the obtained zeolite sample, heat-resistant fiber, glass fiber (fiber diameter 6 μm, fiber length 3 mm) 15% by mass, clay mineral fiber, magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5% by weight, as an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10% by weight, and the weight becomes a basis weight of 70 g / m 2. Adsorption sheets were prepared using a wet papermaking machine. Furthermore, it processed in 200 degreeC and vacuum conditions for 24 hours, and the adsorption sheet sample was obtained. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（比較例２）
Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルをＮ，Ｎ−ジメチルホルムアミド中に２４時間浸漬させた後に、ろ過し、細孔内に溶媒分子が吸着された多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維の代わりにポリブチレンテレフタレート繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Comparative Example 2)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample, 15% by mass of polybutylene terephthalate fiber (fiber diameter 6 μm, fiber length 3 mm) instead of heat-resistant fiber, magnesium silicate fiber (fiber diameter 0.1 μm, 5 mass% of fiber length (1 μm) is used as an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10 mass%, and the basis weight is 70 g / m Adsorption sheets were prepared using a wet papermaking machine with a mass of 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（比較例３）
Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルを２００℃、真空条件下、２４時間で脱溶媒処理を行い、多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、ポリブチレンテレフタレート繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率で混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Comparative Example 3)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was desolvated in a vacuum condition at 200 ° C. for 24 hours to obtain a porous metal complex sample. 70% by mass of the porous metal complex sample, 15% by mass of polybutylene terephthalate fiber (fiber diameter 6 μm, fiber length 3 mm), and 5 mg of magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) as clay mineral fiber. As a mass% organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10 mass%, and the mass becomes a basis weight of 70 g / m 2 . Adsorption sheets were prepared using a wet papermaking machine. Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
（比較例４）
Ｂａｓｏｌｉｔｅ Ｚ１２００（ＢＡＳＦ社製）を乳鉢で粉砕した後に篩いにかけ、平均粒子径が１μｍになるように調製した。さらに、そのサンプルを２００℃、真空条件下、２４時間で脱溶媒処理を行い、多孔性金属錯体サンプルを得た。その多孔性金属錯体サンプルを７０質量％、耐熱性繊維の代わりに、ポリブチレンテレフタレート繊維（繊維径６μｍ、繊維長３ｍｍ）を１５質量％、粘土鉱物繊維として、珪酸マグネシウム繊維（繊維径０．１μｍ、繊維長１μｍ）を５質量％、有機バインダーとして、ポリビニルアルコール（ＰＶＡ）繊維（株式会社クラレ製、ＶＰＢ１０５、繊維径１１μｍ、繊維長３ｍｍ）を１０質量％の比率でで混合し、坪量７０ｇ／ｍ2となる質量にて湿式抄紙装置を使い吸着シートを作製した。さらに、２００℃、真空条件下、２４時間で脱溶媒処理を行い、吸着シートサンプルを得た。得られたサンプルに対して、耐熱性、担持性、柔軟性、吸着性能を測定した。
(Comparative Example 4)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was desolvated in a vacuum condition at 200 ° C. for 24 hours to obtain a porous metal complex sample. 70% by mass of the porous metal complex sample, 15% by mass of polybutylene terephthalate fiber (fiber diameter 6 μm, fiber length 3 mm) instead of heat-resistant fiber, magnesium silicate fiber (fiber diameter 0.1 μm) as clay mineral fiber , Fiber length 1 μm) as an organic binder, polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) is mixed at a ratio of 10 mass%, and the basis weight is 70 g. An adsorbent sheet was prepared using a wet papermaking machine at a mass of / m 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
実施例１〜１１、比較例１〜４のサンプルに関して、耐熱性、担持性、柔軟性、吸着性能を測定した結果を表１又は２に示す。表１、２より明らかなように、本発明例である実施例１〜１１は、吸着材が多孔性金属錯体ではない場合（比較例１）、耐熱性繊維を含まない場合（比較例２、３、４）と比較して、耐熱性、担持性、柔軟性、吸着性能の面で優れていることが分かる。また、粘土鉱物繊維を含まない場合（実施例１０）、有機バインダーを含まない場合（実施例１１）は、これらを含む実施例に比べて、耐熱性、担持性、又は柔軟性にやや劣る傾向が見られた。 Tables 1 and 2 show the results of measuring heat resistance, supportability, flexibility, and adsorption performance for the samples of Examples 1 to 11 and Comparative Examples 1 to 4. As is clear from Tables 1 and 2, Examples 1 to 11, which are examples of the present invention, have a case where the adsorbent is not a porous metal complex (Comparative Example 1), or a case where no heat-resistant fiber is contained (Comparative Example 2, Compared with 3, 4), it can be seen that heat resistance, supportability, flexibility, and adsorption performance are superior. Moreover, when it does not contain a clay mineral fiber (Example 10) and when it does not contain an organic binder (Example 11), it tends to be slightly inferior in heat resistance, supportability, or flexibility as compared with Examples containing these. It was observed.
本発明の吸着シート又は吸着エレメントによれば、空気中の水分、有機溶剤、および、悪臭成分を効率的に分離・回収、もしくは、吸着・除去するができるようになり、産業界に大きく寄与することが期待できる。
According to the adsorbing sheet or adsorbing element of the present invention, it becomes possible to efficiently separate / recover or adsorb / remove moisture, organic solvents, and malodorous components in the air, which greatly contributes to the industry. I can expect that.
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