JP2002177716A - Hydrogen sulfide removing material, its manufacturing method and filter using the same - Google Patents
Hydrogen sulfide removing material, its manufacturing method and filter using the sameInfo
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- JP2002177716A JP2002177716A JP2000378580A JP2000378580A JP2002177716A JP 2002177716 A JP2002177716 A JP 2002177716A JP 2000378580 A JP2000378580 A JP 2000378580A JP 2000378580 A JP2000378580 A JP 2000378580A JP 2002177716 A JP2002177716 A JP 2002177716A
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- Prior art keywords
- hydrogen sulfide
- filter
- monomer
- nonwoven fabric
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Ventilation (AREA)
- Separation Of Gases By Adsorption (AREA)
- Filtering Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、硫化水素除去材に
係り、特に空気中に存在する極微量の硫化水素を除去す
ることができる硫化水素除去材とその製造方法及びそれ
を用いたフィルタに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen sulfide removing material, and more particularly to a hydrogen sulfide removing material capable of removing a trace amount of hydrogen sulfide present in air, a method for producing the same, and a filter using the same. Things.
【０００２】[0002]
【従来の技術】硫化水素は、極微量でも悪臭が強いの
で、一般家庭のみならず公共の場においても、硫化水素
除去に対する関心が強い。また、半導体産業等の精密産
業では、空気中の硫黄成分が半導体の性能や歩留まりに
影響を与えており、製造環境の硫化水素濃度を極低濃度
にする必要がある。半導体業界向けのケミカルフィルタ
は、空気中のアンモニア、二酸化硫黄、ホウ素などに対
し、良好な除去性能を示すが、硫化水素に対するもので
は、除去性能で満足なフィルタはなかった。イオン交換
体ケミカルフィルタでは、４級アンモニウム基を有する
強塩基性アニオン交換体が、硫化水素に対する除去性能
があるが、しかし、空気中には、炭酸ガスが３００ｐｐ
ｍ以上存在するので、短時間のうちに炭酸ガスが吸着
し、イオン交換基が飽和する。その状態では、さらに弱
い酸である硫化水素の除去が十分でない。さらに、硫化
水素を吸着した吸着材から、強い硫化水素臭が発生する
といった問題、また空気中の湿度が低い場合（５０％以
下）に、除去率が低下するという問題点があった。従っ
て、空気中の低濃度硫化水素に対する効率の良い除去材
が待望されていた。2. Description of the Related Art Since hydrogen sulfide has a strong odor even in a very small amount, there is a strong interest not only in ordinary households but also in public places. In the precision industry such as the semiconductor industry, sulfur components in the air affect the performance and yield of semiconductors, and it is necessary to make the concentration of hydrogen sulfide in the production environment extremely low. Chemical filters for the semiconductor industry show good removal performance for ammonia, sulfur dioxide, boron and the like in the air, but none of the filters for hydrogen sulfide have satisfactory removal performance. In the ion exchanger chemical filter, a strongly basic anion exchanger having a quaternary ammonium group has a performance of removing hydrogen sulfide. However, in the air, 300 pp of carbon dioxide gas is present.
m or more, carbon dioxide gas is adsorbed within a short time, and the ion exchange group is saturated. In that state, the removal of hydrogen sulfide, which is a weaker acid, is not sufficient. Further, there is a problem that a strong hydrogen sulfide odor is generated from the adsorbent that has adsorbed hydrogen sulfide, and a problem that the removal rate is reduced when the humidity in the air is low (50% or less). Therefore, an efficient removal material for low-concentration hydrogen sulfide in air has been desired.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題点を解消し、空気中に存在する極微量の硫化水
素のみを効率良く除去し、硫化水素臭の発生、除去率の
低下等のない硫化水素除去材とその製造方法及びそれを
用いた硫化水素除去フィルタを提供することを課題とす
る。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, efficiently removes only a trace amount of hydrogen sulfide present in the air, generates hydrogen sulfide odor, and reduces the removal rate. It is an object of the present invention to provide a hydrogen sulfide removing material without any other factors, a method for producing the same, and a hydrogen sulfide removing filter using the same.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に、本発明では、銀型のカチオン交換基及び／又はキレ
ート基を有する側鎖が、繊維径３０μｍ以下のポリオレ
フィン系繊維、その集合体である織布又は不織布、又は
それらの加工品に、化学的に導入されていることを特徴
とする硫化水素除去材としたものである。前記硫化水素
除去材において、側鎖の化学的な導入は、放射線グラフ
ト重合法で行うことができる。また、本発明では、繊維
径３０μｍ以下のポリオレフィン系繊維、その集合体で
ある織布又は不織布、又はそれらの加工品に、２００ｋ
Ｇｙ以下の放射線を照射した後、カチオン交換基を有す
るモノマー、カチオン交換基に転換可能なモノマー、キ
レート基を有するモノマー及びキレート基に転換可能な
モノマーより選ばれた一種以上のモノマーをグラフト重
合し、次いで銀イオンを担持させることを特徴とする硫
化水素除去材の製造方法としたものである。さらに、本
発明では、前記の硫化水素除去材において、前記織布又
は不織布の目付が２５ｇ／ｍ2以上であり、通気度３０
ｍｌ／ｃｍ2・秒以上であることを特徴とする硫化水素
除去フィルタとしたものである。前記硫化水素除去フィ
ルタは、フィルタの寿命を予測するための上流側と下流
側との色調比較をする手段を具備することができる。According to the present invention, there is provided a polyolefin-based fiber having a silver-type cation exchange group and / or a chelate group having a fiber diameter of 30 μm or less, and an aggregate thereof. The hydrogen sulfide removing material is characterized by being chemically introduced into a woven or non-woven fabric or a processed product thereof. In the hydrogen sulfide removing material, the side chains can be chemically introduced by a radiation graft polymerization method. Further, in the present invention, a polyolefin-based fiber having a fiber diameter of 30 μm or less, a woven or non-woven fabric as an aggregate thereof, or a processed product thereof,
After irradiation with radiation of Gy or less, graft polymerization of one or more monomers selected from a monomer having a cation exchange group, a monomer convertible to a cation exchange group, a monomer having a chelate group and a monomer convertible to a chelate group is performed. And a method for producing a hydrogen sulfide removing material characterized by supporting silver ions. Furthermore, in the present invention, in the hydrogen sulfide removing material, the basis weight of the woven or nonwoven fabric is 25 g / m 2 or more, and the air permeability is 30%.
This is a hydrogen sulfide removal filter characterized by being at least ml / cm 2 · second. The hydrogen sulfide removal filter may include means for comparing the color tone between the upstream side and the downstream side for estimating the life of the filter.
【０００５】[0005]
【発明の実施の形態】本発明は、次のような知見に基づ
いてなされたものである。銀イオンは、硫化水素と極め
て反応しやすく硫化銀を生成する。従って、吸着材に高
密度に銀イオンを固定化すれば、硫化水素に対して優れ
た吸着能を示す材料ができる。グラフト側鎖は、特にイ
オン交換基やキレート基が導入された状態でモビリティ
が大きいので、銀型への変換効率、銀型へ調整後の硫化
水素除去性能が大きい。カチオン交換基やキレート基を
官能基として有する繊維は、硝酸銀などの水溶液に接触
させることにより、容易に銀イオンを繊維に化学吸着さ
せることができる。繊維などの高分子材料を製造する
際、硝酸銀等を練り込むことにより、銀イオンを含有す
る繊維を製造可能であるが、銀イオンの密度が小さいこ
とや硫化水素の繊維内部への溶解拡散速度が小さいため
除去性能が悪い。架橋構造を有するイオン交換繊維は、
銀型への変換効率や硫化水素の繊維内部への拡散速度が
小さく、除去性能が十分ではない。反応生成物である硫
化銀は、繊維内部に保持されるので、外に微粒子となっ
て放出されることはない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention has been made based on the following findings. Silver ions readily react with hydrogen sulfide to produce silver sulfide. Therefore, if silver ions are immobilized on the adsorbent at high density, a material exhibiting excellent adsorption ability to hydrogen sulfide can be obtained. Since the graft side chain has high mobility, particularly in a state where an ion exchange group or a chelate group is introduced, the conversion efficiency to a silver form and the hydrogen sulfide removal performance after adjustment to a silver form are large. The fiber having a cation exchange group or a chelate group as a functional group can easily chemically adsorb silver ions to the fiber by contact with an aqueous solution such as silver nitrate. When producing high molecular materials such as fibers, fibers containing silver ions can be produced by kneading silver nitrate, etc., but the density of silver ions is low and the rate of dissolution and diffusion of hydrogen sulfide into the fibers is low. Is small, so the removal performance is poor. Ion exchange fibers having a crosslinked structure
The conversion efficiency to silver mold and the diffusion rate of hydrogen sulfide into the fiber are small, and the removal performance is not sufficient. Silver sulfide, which is a reaction product, is retained inside the fiber, and is not emitted as fine particles to the outside.
【０００６】次に、本発明の構成について説明する。本
発明で側鎖を導入する基材は、直径３０μｍ以下の単繊
維、繊維の集合体である織布や不織布、さらにそれらの
加工品であり、それらは成形加工が容易であり、本発明
の用途への使用形態であるフィルタ状にも、容易に加工
できるばかりでなく、表面積が大きいので、低濃度の硫
化水素の除去性能が大である。直径３０μｍを超える
と、圧力損失が小さくなるが、除去性能が悪くなる。ま
た、ポリオレフィン系の繊維は、耐薬品性が大きく、ま
た不織布化の段階で熱融着しやすい等の利点があるばか
りでなく、後述の放射線グラフト重合しやすい材料であ
るため、本発明に最適の素材である。本発明で側鎖とし
て導入するカチオン交換基としては、スルホン酸基、カ
ルボキシル基、りん酸基、などが一般的であり、いずれ
も本発明に利用できるが、この範囲に限定される訳では
ない。キレート基としては、イミノジ酢酸基、アミドキ
シム基、アミノりん酸基などいずれも利用できるが、こ
の範囲に限定される訳ではない。イオン交換基やキレー
ト基は、いずれも強い親水基であるため、周囲に水を吸
着している。これらが有効に働くので、空気中の湿度が
低い場合にも、硫化水素の除去性能に大きく影響与える
ことは少ない。Next, the configuration of the present invention will be described. The base material into which the side chains are introduced in the present invention is a single fiber having a diameter of 30 μm or less, a woven fabric or a nonwoven fabric which is an aggregate of fibers, and further processed products thereof. Not only can it be easily processed into a filter form which is a use form for the purpose, but also the surface area is large, so that the performance of removing low-concentration hydrogen sulfide is great. When the diameter exceeds 30 μm, the pressure loss is reduced, but the removal performance is deteriorated. In addition, polyolefin-based fibers are not only advantageous in that they have high chemical resistance and are easy to be heat-fused at the stage of non-woven fabric formation, and are also easy to be subjected to radiation graft polymerization as described later. Material. As the cation exchange group introduced as a side chain in the present invention, a sulfonic acid group, a carboxyl group, a phosphate group, and the like are generally used, and any of them can be used in the present invention, but is not limited to this range. . As the chelate group, any of an iminodiacetic acid group, an amidoxime group, an aminophosphate group and the like can be used, but it is not limited to this range. Since both the ion exchange group and the chelate group are strong hydrophilic groups, they adsorb water around. Since these work effectively, even when the humidity in the air is low, there is little influence on the performance of removing hydrogen sulfide.
【０００７】次に、本発明で用いる放射線グラフト重合
法について説明する。グラフト鎖は、架橋構造がないの
で、カチオン交換基やキレート基等の電荷を有する官能
基を導入させた場合、同電荷の反発及び吸着した水によ
り、膨潤する。放射線グラフト重合は、複雑な形状の繊
維にも均一に内部までラジカルを生成でき、グラフト鎖
を導入できる。放射線グラフト重合法には、照射方法に
よって前照射グラフト重合法と同時照射グラフト重合法
がある。前者は、予め高分子基材に放射線を照射した
後、モノマー（重合性単量体）と接触させる方法であ
り、後者は、高分子基材とモノマーが両方存在するとこ
ろで、放射線を照射する方法であるが、どちらの方法も
利用できる。また、モノマーと高分子基材との接触方法
によって、液相グラフト、気相グラフト、含浸気相グラ
フトなどがある。本発明の効果を最も発揮する繊維状基
材の場合、含浸気相グラフト重合がモノマーの利用効率
が大きく、且つ均一にグラフト重合できるので好まし
い。Next, the radiation graft polymerization method used in the present invention will be described. Since the graft chain has no cross-linking structure, when a charged functional group such as a cation exchange group or a chelate group is introduced, the graft chain swells due to repulsion of the same charge and absorbed water. Radiation graft polymerization can uniformly generate radicals even in fibers having a complicated shape to the inside, and can introduce a graft chain. The radiation graft polymerization method includes a pre-irradiation graft polymerization method and a simultaneous irradiation graft polymerization method depending on the irradiation method. The former is a method of irradiating a polymer substrate in advance with radiation and then contacting it with a monomer (polymerizable monomer), and the latter is a method of irradiating radiation where both the polymer substrate and the monomer are present. However, either method can be used. Further, there are a liquid phase graft, a gas phase graft, an impregnated gas phase graft, and the like, depending on the method of contact between the monomer and the polymer substrate. In the case of a fibrous substrate exhibiting the effects of the present invention most, the impregnated gas-phase graft polymerization is preferable because the utilization efficiency of the monomer is large and the graft polymerization can be performed uniformly.
【０００８】放射線グラフト重合に利用する放射線は、
ガンマ線、α線、β線、電子線、紫外線などがあるが、
実用的には、ガンマ線、電子線、紫外線などが適してい
る。吸収線量としては、２００ｋＧｙ以下が好ましい。
本発明の硫化水素除去材は、繊維表面が主な反応の場と
なるので、繊維の表面付近にグラフト側鎖を高密度に導
入できればよい。したがって、エネルギーの小さな紫外
線も利用できる。放射線グラフト重合に使用できるモノ
マーには、カチオン交換基を有するものとしてアクリル
酸、メタクリル酸、スチレンスルホン酸ナトリウム、ビ
ニルスルホン酸ナトリウムなどがあり、いずれも使用可
能であるが、この範囲に限定される訳ではない。カチオ
ン交換基に変換できるモノマーとしては、メタクリル酸
グリシジル、スチレン、アクリロニトリルなどがある
が、この範囲に限定される訳ではない。これらをグラフ
ト重合した後、公知の方法で２次処理を行ない、カチオ
ン交換基を導入できる。例えば、メタクリル酸グリシジ
ルをグラフト重合した後、亜硫酸ナトリウム水溶液でス
ルホン化することが可能である。カルボキシル基を有す
るアクリル酸やメタクリル酸は、単独で容易にグラフト
でき、低グラフト率で交換容量が大きく、銀型で除去率
が高く、コストも低いなどの利点があり、本発明に好適
である。The radiation used for the radiation graft polymerization is
There are gamma rays, α rays, β rays, electron beams, ultraviolet rays, etc.
Practically, gamma rays, electron beams, ultraviolet rays and the like are suitable. The absorbed dose is preferably 200 kGy or less.
In the hydrogen sulfide removing material of the present invention, since the fiber surface is the main reaction site, it is sufficient that the graft side chain can be introduced at a high density near the fiber surface. Therefore, ultraviolet rays having low energy can be used. Monomers that can be used for radiation graft polymerization include acrylic acid, methacrylic acid, sodium styrenesulfonate, sodium vinylsulfonate, and the like having a cation exchange group, and any of them can be used, but is limited to this range. Not in translation. Monomers that can be converted to a cation exchange group include glycidyl methacrylate, styrene, acrylonitrile, and the like, but are not limited to this range. After these are graft-polymerized, a secondary treatment is performed by a known method to introduce a cation exchange group. For example, after graft polymerization of glycidyl methacrylate, sulfonation with an aqueous sodium sulfite solution is possible. Acrylic acid or methacrylic acid having a carboxyl group can be easily grafted alone, has a low grafting rate, a large exchange capacity, a silver type with a high removal rate, and low costs, and is suitable for the present invention. .
【０００９】また、これらのモノマーを複数併用するこ
とも可能である。例えば、スチレンスルホン酸ナトリウ
ムは、ポリオレフィン系繊維に単独でグラフト重合する
ことが難しいので、アクリル酸やメタクリル酸と併用す
ることもできる。キレート基を導入するには、メタクリ
ル酸グリシジルやクロロメチルスチレンなどをグラフト
重合した後、イミノジ酢酸ナトリウム水溶液などで処理
するなど、公知の方法でイミノジ酢酸基を導入できる。
アミドキシム基は、アクリロニトリルをグラフト重合し
た後、塩酸ヒドロキシルアミン水溶液などにより、アミ
ドキシム化を行ない導入できる。銀型への変換は、カル
ボキシル基を有する場合、ナトリウム型へ変換後、硝酸
銀水溶液に接触させることによって、容易に変換でき
る。スルホン酸基の場合は、ナトリウム型に変換するこ
となく、Ｈ型のままで硝酸銀水溶液に接触させても良
い。ここで、ハロゲンイオンが存在すると、ハロゲン化
銀が生成し、光によって黒変するなど品質の劣化がある
ので、特に塩素イオンなどは水から除去しておく必要が
ある。It is also possible to use a plurality of these monomers in combination. For example, sodium styrenesulfonate is difficult to graft-polymerize alone to polyolefin-based fibers, and thus can be used in combination with acrylic acid or methacrylic acid. In order to introduce a chelate group, an iminodiacetic acid group can be introduced by a known method such as graft polymerization of glycidyl methacrylate or chloromethylstyrene, followed by treatment with an aqueous solution of sodium iminodiacetic acid.
The amidoxime group can be introduced by graft polymerization of acrylonitrile, followed by amidoximation with an aqueous solution of hydroxylamine hydrochloride or the like. When the compound has a carboxyl group, it can be easily converted to the silver form by contacting it with an aqueous solution of silver nitrate after conversion to the sodium form. In the case of a sulfonic acid group, it may be brought into contact with an aqueous solution of silver nitrate as it is in the H form without conversion to the sodium form. Here, if halogen ions are present, silver halide is formed and the quality is deteriorated such as blackening by light. Therefore, it is necessary to remove chlorine ions and the like from water in particular.
【００１０】次に、硫化水素除去フィルタについて説明
する。繊維の集合体である織布や不織布は、フィルタヘ
の成形加工が容易であり、本発明に好適である。また、
目付が２５ｇ／ｍ2以上でないと、フィルタ全体での銀
イオンの担持量が小さくなり、十分な寿命が得られな
い。２５ｇ／ｍ2以下の場合、放射線グラフト重合やそ
の後の２次処理での物理的・化学的にハードな環境で十
分な強度を保持し得ないし、プリーツ型への成形も難し
い。また、通気度３０ｍl／ｃｍ2・秒以上でないと、フ
ィルタ加工した場合の圧力損失が大きくなりすぎ、流量
が所定量に達しないという場合もある。銀イオンが硫化
水素と接触すると、黒色の硫化銀が生成する。接触する
前は薄茶色であるため、上流側から下流側に黒色の変色
域が拡大する。フィルタの下流側全体に黒色が移行する
前に交換すれば、所定濃度以上の硫化水素が下流側に流
出することはない。このように、前記フィルタの上流側
と下流側との色調比較をすることにより、フィルタの寿
命を予測できる。また、硫化水素フィルタは、使用環境
やフィルタ稼動状況などにより、色調の変化はまちまち
と思われるので、使用前と使用後の色見本を作成してお
けば、便利である。Next, the hydrogen sulfide removal filter will be described. A woven or nonwoven fabric, which is an aggregate of fibers, can be easily formed into a filter and is suitable for the present invention. Also,
If the basis weight is not more than 25 g / m 2 , the silver ion carrying amount in the whole filter becomes small, and a sufficient life cannot be obtained. When it is 25 g / m 2 or less, sufficient strength cannot be maintained in a physically and chemically hard environment in radiation graft polymerization and subsequent secondary treatment, and it is difficult to form a pleated mold. If the air permeability is not more than 30 ml / cm 2 · sec, the pressure loss when the filter is processed becomes too large, and the flow rate may not reach the predetermined amount. When silver ions come into contact with hydrogen sulfide, black silver sulfide is formed. Before contact, the color is light brown, so the black discoloration area expands from upstream to downstream. If replaced before the black color is transferred to the entire downstream side of the filter, hydrogen sulfide having a predetermined concentration or more will not flow downstream. As described above, by comparing the color tone between the upstream side and the downstream side of the filter, the life of the filter can be predicted. Further, the color tone of the hydrogen sulfide filter is considered to vary depending on the use environment and the operating condition of the filter, so it is convenient to prepare color samples before and after use.
【００１１】次に、本発明の硫化水素除去フィルタの設
置例を図面を用いて説明する。図１〜図３に、本発明の
フィルタを設置した断面の概略構成図を示す。本発明の
フィルタは、図に示すように、クリーンルーム１の外気
取入口２、循環系３、３’、半導体製造装置、ファンフ
ィルタユニット５又はウエハ搬送用などに使われるクリ
ーンボックス６のファン７の出口８に取りつけ、各製造
環境中の硫化水素を低減できる。図３で、１０はウエハ
収納枠である。図４に、本発明のフィルタを組込んだ有
害ガス除去用のフィルタ９の構成図を示す。該フィルタ
９は、粗塵フィルタ９ａ、本発明フィルタ９ｂ、アンモ
ニア除去用フィルタ９ｃ、ＨＥＰＡフィルタ９ｄよりな
り、このように、本発明に付加して微粒子除去用のフィ
ルタ素材や他のガス成分を除去できる素材を一つのフィ
ルタ構造の中に積層し、複数の機能を有するフィルタ構
造に適用することもできる。Next, an example of installation of the hydrogen sulfide removal filter of the present invention will be described with reference to the drawings. 1 to 3 show schematic configuration diagrams of cross sections in which the filter of the present invention is installed. As shown in the figure, the filter of the present invention includes a fan 7 of a clean box 6 used for an outside air inlet 2, a circulation system 3, 3 ', a semiconductor manufacturing apparatus, a fan filter unit 5, or a wafer transfer or the like in a clean room 1. At the outlet 8, hydrogen sulfide in each production environment can be reduced. In FIG. 3, reference numeral 10 denotes a wafer storage frame. FIG. 4 shows a configuration diagram of a filter 9 for removing harmful gas, incorporating the filter of the present invention. The filter 9 comprises a coarse dust filter 9a, a filter 9b of the present invention, a filter 9c for removing ammonia, and a HEPA filter 9d. Thus, a filter material for removing fine particles and other gas components in addition to the present invention are removed. The materials that can be formed can be stacked in one filter structure, and applied to a filter structure having a plurality of functions.
【００１２】[0012]
【実施例】以下、本発明を実施例により具体的に説明す
る。 実施例１ （ａ）銀型不織布の調整 繊維径１７μｍのポリエチレン（鞘）／ポリププロピレ
ン（芯）の複合繊維よりなる目付５５ｇ／ｍ2、厚み
０．３５ｍｍの熱融着不織布に、窒素雰囲気で電子線を
１５０ｋＧｙ照射した。この照射済不織布に、アクリル
酸を重量で基材の約５０％となるよう浸漬し、真空容器
に入れ、４０℃で３時間反応させた。取出した不織布
を、水酸化ナトリウム５％水溶液に浸漬し、５０℃で１
時間処理し、ホモポリマーを除去した。この不織布は、
イオン交換容量が４．４ｍｅｑ／ｇであった。次に、硝
酸銀１％水溶液にこの不織布を入れ、３０分撹拌し、銀
型に調整した。The present invention will be described below in more detail with reference to examples. Example 1 (a) Preparation of silver-type nonwoven fabric A heat-sealed nonwoven fabric having a basis weight of 55 g / m 2 and a thickness of 0.35 mm made of a composite fiber of polyethylene (sheath) / polypropylene (core) having a fiber diameter of 17 μm was applied in a nitrogen atmosphere. An electron beam was irradiated at 150 kGy. Acrylic acid was immersed in the irradiated non-woven fabric so as to be about 50% by weight of the substrate, placed in a vacuum vessel, and reacted at 40 ° C. for 3 hours. The taken out non-woven fabric is immersed in a 5% aqueous solution of sodium hydroxide,
Time treatment removed homopolymer. This non-woven fabric
The ion exchange capacity was 4.4 meq / g. Next, this nonwoven fabric was put into a 1% aqueous solution of silver nitrate, stirred for 30 minutes, and adjusted to a silver mold.
【００１３】（ｂ）硫化水素除去試験 不織布（再生型）を５ｃｍΦの塩ビ製のカラムに装着
し、図５に示す評価装置で硫化水素ガス除去試験を行な
った。図５において、１１はカラム、１２は不織布試
料、１３は入口濃度測定用サンプリング口、１４は出口
濃度測定用サンプリング口、１５はポンプ、１６はパー
ミエータ、１７はフィルタホルダーである。入口硫化水
素ガス濃度は、１ｐｐｍとなるようパーミエータ１６を
調整し、風量１５Ｌ／ｍｉｎで通ガスした。上流側の不
織布表面の色は、徐々に黒化し下流側に移行した。不織
布の下流側（裏側）の色がやや濃くなった時点で、硫化
水素濃度を測定したところ０．１ｐｐｍであった。それ
までの通ガス時間は、７時間であった。(B) Hydrogen Sulfide Removal Test A nonwoven fabric (recycled type) was mounted on a 5 cmΦ polyvinyl chloride column, and a hydrogen sulfide gas removal test was performed using an evaluation device shown in FIG. In FIG. 5, 11 is a column, 12 is a nonwoven fabric sample, 13 is an inlet concentration measurement sampling port, 14 is an outlet concentration measurement sampling port, 15 is a pump, 16 is a permeator, and 17 is a filter holder. The permeator 16 was adjusted so that the concentration of hydrogen sulfide gas at the inlet became 1 ppm, and gas was passed at an air flow rate of 15 L / min. The color of the surface of the nonwoven fabric on the upstream side gradually turned black and shifted to the downstream side. When the color of the downstream side (back side) of the nonwoven fabric became slightly dark, the hydrogen sulfide concentration was measured and found to be 0.1 ppm. The gas passing time up to that time was 7 hours.
【００１４】実施例２ （ａ）銀型不織布の調整 実施例１と同様の熱融着不織布にガンマ線を１６０ｋＧ
ｙ照射した。この照射済不織布に、メタクリル酸グリシ
ジルを基材の１５５％となるよう浸漬した。この不織布
を真空容器に入れ、真空ポンプで減圧にした後、５０℃
で３時間反応させた。取出した不織布は乾燥していた。
ジメチルホルムアミド溶液に入れ７０℃で３時間処理
し、ホモポリマー除去した。しかし、重量減少は０．２
％であり、ほぼ完全にグラフト重合してしていた。この
不織布を、亜硫酸ナトリウム／イソプロピルアルコール
／水＝１５／１０／７５の溶液に浸漬し、８０℃で９時
間反応を行なってスルホン化した。取出した不織布を十
分洗浄した後、中性塩分解容量を測定したところ、２．
６５ｍｅｑ／ｇの強酸性カチオン交換不織布が得られ
た。この不織布を硝酸銀１％水溶液に１時間浸漬し、３
０分撹拌して銀型に調整した。Example 2 (a) Preparation of Silver-Type Nonwoven Fabric 160 g of gamma rays were applied to the same heat-sealed nonwoven fabric as in Example 1.
y irradiation. Glycidyl methacrylate was immersed in the irradiated nonwoven fabric so that 155% of the base material was obtained. This nonwoven fabric is put in a vacuum container, and the pressure is reduced by a vacuum pump.
For 3 hours. The removed nonwoven fabric was dry.
It was placed in a dimethylformamide solution and treated at 70 ° C. for 3 hours to remove a homopolymer. However, the weight loss is 0.2
%, And the graft polymerization was almost complete. This nonwoven fabric was immersed in a solution of sodium sulfite / isopropyl alcohol / water = 15/10/75 and reacted at 80 ° C. for 9 hours for sulfonation. After the taken-out nonwoven fabric was sufficiently washed, the neutral salt decomposition capacity was measured.
A strongly acidic cation exchange nonwoven fabric of 65 meq / g was obtained. This nonwoven fabric is immersed in a 1% aqueous solution of silver nitrate for 1 hour,
The mixture was stirred for 0 minutes and adjusted to a silver mold.
【００１５】（ｂ）硫化水素除去試験 この不織布を５ｃｍΦの塩ビ製のカラム１１に装着し、
図５に示す評価装置で硫化水素ガス除去試験を行なっ
た。入口硫化水素ガス濃度は、１ｐｐｍとなるようパー
ミエータ１６を調整し、風量１５Ｌ／ｍｉｎで通ガスし
た。上流側の不織布表面の色は徐々に黒化し下流側に移
行した。不織布の下流側（裏側）の色がやや濃くなった
時点で、硫化水素濃度をガス検知管出口で測定したとこ
ろ、０．１ｐｐｍであった。それまでの通ガス時間は
４．５時間であった。(B) Hydrogen sulfide removal test This non-woven fabric was mounted on a PVC column 11 having a diameter of 5 cm.
A hydrogen sulfide gas removal test was performed using the evaluation device shown in FIG. The permeator 16 was adjusted so that the concentration of hydrogen sulfide gas at the inlet became 1 ppm, and gas was passed at an air flow rate of 15 L / min. The color of the surface of the nonwoven fabric on the upstream side gradually turned black and shifted to the downstream side. When the color of the downstream side (back side) of the nonwoven fabric became slightly dark, the concentration of hydrogen sulfide was measured at the outlet of the gas detection tube and found to be 0.1 ppm. The gas passing time up to that was 4.5 hours.
【００１６】実施例３ （ａ）銀型不織布の調整 実施例２のメタクリル酸グリシジルグラフト不織布を、
イミノジ酢酸ナトリウム／イソプロピルアルコール／水
＝１０／１０／８０の溶液に浸漬し、８０℃で５時間反
応を行なって取出した。取出した不織布を十分洗浄した
後、重量増加よりイミノジ酢酸ナトリウム基の導入量を
測定したところ、２．４５ｍｍｏｌ／ｇであった。中性
塩分解容量を測定したところ、２．６５ｍｅｑ／ｇの強
酸性カチオン交換不織布が得られた。この不織布を硝酸
銀１％水溶液に１時間浸漬し、３０分撹拌して銀型に調
整した。Example 3 (a) Preparation of Silver-Type Nonwoven Fabric The glycidyl methacrylate-grafted nonwoven fabric of Example 2 was
It was immersed in a solution of sodium iminodiacetate / isopropyl alcohol / water = 10/10/80, reacted at 80 ° C. for 5 hours, and taken out. After the taken-out nonwoven fabric was sufficiently washed, the amount of sodium iminodiacetate group introduced was measured from the increase in weight, and was found to be 2.45 mmol / g. When the neutral salt decomposition capacity was measured, a strongly acidic cation exchange nonwoven fabric of 2.65 meq / g was obtained. This nonwoven fabric was immersed in a 1% aqueous solution of silver nitrate for 1 hour and stirred for 30 minutes to prepare a silver mold.
【００１７】（ｂ）硫化水素除去試験 この不織布を５ｃｍΦの塩ビ製のカラム１１に装着し、
図５に示す評価装置で硫化水素ガス除去試験を行なっ
た。入口硫化水素ガス濃度は０．１ｐｐｍとなるようパ
ーミエータ１６を調整し、風量１５Ｌ／ｍｉｎで通ガス
した。上流側の不織布表面の色は、徐々に黒化し下流側
に移行した。不織布の下流側（裏側）の色がやや濃くな
った時点で、硫化水素濃度をガスクロで測定したとこ
ろ、０．０２ｐｐｍであった。それまでの通ガス時間
は、７８時間であった。(B) Hydrogen sulfide removal test This nonwoven fabric was mounted on a PVC column 11 having a diameter of 5 cm.
A hydrogen sulfide gas removal test was performed using the evaluation device shown in FIG. The permeator 16 was adjusted so that the inlet hydrogen sulfide gas concentration was 0.1 ppm, and gas was passed at an air volume of 15 L / min. The color of the surface of the nonwoven fabric on the upstream side gradually turned black and shifted to the downstream side. When the color of the downstream side (back side) of the nonwoven fabric became slightly dark, the concentration of hydrogen sulfide was measured by gas chromatography and found to be 0.02 ppm. The gas passing time up to that time was 78 hours.
【００１８】実施例４ （ａ）銀型不織布の調整 繊維径１０μｍのポリエチレン単独繊維よりなり、スポ
ット融着（エンボス加工）により不織布にした目付４０
ｇ／ｍ2、厚み０．２８ｍｍの熱融着不織布に、ガンマ
線で１５０ｋＧｙ照射した。この照射済不織布に、スチ
レンスルホン酸／アクリル酸／水＝２５／２５／５０を
重量で基材の約１３０％となるよう浸漬し、真空容器に
入れ４０℃で３時間反応させた。取出した不織布を水酸
化ナトリウム５％水溶液に浸漬し、５０℃で１時間処理
し、ホモポリマーを除去した。この不織布は、イオン交
換容量が中性塩分解容量２．３５ｍｅｑ／ｇであった。
次に、硝酸銀１％水溶液にこの不織布を入れ、３０分撹
拌し、銀型に調整した。Example 4 (a) Preparation of silver-type nonwoven fabric A nonwoven fabric made of polyethylene single fiber having a fiber diameter of 10 μm and formed into a nonwoven fabric by spot fusion (embossing) 40
A heat-fused nonwoven fabric having a g / m 2 and a thickness of 0.28 mm was irradiated with gamma rays at 150 kGy. In the irradiated nonwoven fabric, styrenesulfonic acid / acrylic acid / water = 25/25/50 was immersed so as to be about 130% by weight of the base material, put in a vacuum vessel, and reacted at 40 ° C. for 3 hours. The removed nonwoven fabric was immersed in a 5% aqueous solution of sodium hydroxide and treated at 50 ° C. for 1 hour to remove the homopolymer. This nonwoven fabric had an ion exchange capacity of a neutral salt decomposition capacity of 2.35 meq / g.
Next, this nonwoven fabric was put into a 1% aqueous solution of silver nitrate, stirred for 30 minutes, and adjusted to a silver mold.
【００１９】（ｂ）硫化水素除去試験 不織布（再生型）を５ｃｍΦの塩ビ製のカラム１１に装
着し、図５に示す評価装置で硫化水素ガス除去試験を行
なった。入口硫化水素ガス濃度は、１ｐｐｍとなるよう
パーミエータ１６を調整し、風量１５Ｌ／ｍｉｎで通ガ
スした。上流側の不織布表面の色は、徐々に黒化し下流
側に移行した。不織布の下流側（裏側）の色がやや濃く
なった時点で、硫化水素濃度を測定したところ、０．１
ｐｐｍであった。それまでの通ガス時間は、７時間であ
った。(B) Hydrogen Sulfide Removal Test A nonwoven fabric (regenerated type) was mounted on a vinyl chloride column 11 having a diameter of 5 cmΦ, and a hydrogen sulfide gas removal test was performed using an evaluation device shown in FIG. The permeator 16 was adjusted so that the concentration of hydrogen sulfide gas at the inlet became 1 ppm, and gas was passed at an air flow rate of 15 L / min. The color of the surface of the nonwoven fabric on the upstream side gradually turned black and shifted to the downstream side. When the color of the downstream side (back side) of the nonwoven fabric became slightly dark, the hydrogen sulfide concentration was measured.
ppm. The gas passing time up to that time was 7 hours.
【００２０】[0020]
【発明の効果】本発明によれば、空気中に存在する極微
量の硫化水素を効率よく除去すると共に、硫化水素臭の
発生がなく、得られたフィルタの寿命を容易に予測でき
る硫化水素除去材とそれを用いたフィルタを提供するこ
とができた。According to the present invention, a very small amount of hydrogen sulfide present in the air can be efficiently removed, and no hydrogen sulfide odor is generated, and the life of the obtained filter can be easily predicted. The material and the filter using it could be provided.
【図１】本発明のフィルタを設置したクリーンルームの
断面の概略構成図。FIG. 1 is a schematic configuration diagram of a cross section of a clean room in which a filter of the present invention is installed.
【図２】本発明のフィルタを設置したフィルタユニット
の断面の概略構成図。FIG. 2 is a schematic configuration diagram of a cross section of a filter unit provided with a filter of the present invention.
【図３】本発明のフィルタを設置したクリーンボックス
の断面の概略構成図。FIG. 3 is a schematic configuration diagram of a cross section of a clean box provided with a filter of the present invention.
【図４】本発明のフィルタを組込んだ有害ガス除去用フ
ィルタの構成図。FIG. 4 is a configuration diagram of a filter for removing harmful gas incorporating the filter of the present invention.
【図５】本発明の実施例の硫化水素除去試験に用いた評
価装置の概略構成図。FIG. 5 is a schematic configuration diagram of an evaluation device used in a hydrogen sulfide removal test according to an example of the present invention.
１：クリーンルーム、２：外気取入口フィルタ、３、
３’：循環系フィルタ、４：半導体製造装置フィルタ、
５：ファンフィルタユニット、６：クリーンボックス、
７：ファン、８：出口フィルタ、９：有害ガス除去フィ
ルタ、９ａ：粗塵フィルタ、９ｂ：本発明のフィルタ、
９ｃ：アンモニア除去用フィルタ、９ｄ：ＨＥＰＡフィ
ルタ、１０：ウエハ収納枠、１１：カラム、１２：不織
布試料、１３：入口濃度測定用サンプリング口、１４：
出口濃度測定用サンプリング口、１５：ポンプ、１６：
パーミエータ、１７：フィルタホルダー1: clean room, 2: outside air intake filter, 3,
3 ': circulation system filter, 4: semiconductor manufacturing equipment filter,
5: fan filter unit, 6: clean box,
7: fan, 8: outlet filter, 9: harmful gas removal filter, 9a: coarse dust filter, 9b: filter of the present invention,
9c: Ammonia removal filter, 9d: HEPA filter, 10: Wafer storage frame, 11: Column, 12: Nonwoven fabric sample, 13: Inlet concentration measurement sampling port, 14:
Outlet concentration measurement sampling port, 15: pump, 16:
Permeator, 17: filter holder
フロントページの続き (72)発明者 勝峰 万理 東京都大田区羽田旭町11番１号株式会社荏 原製作所内 Ｆターム(参考） 3L058 BE02 BF09 4D012 BA01 4D019 BA13 BB02 BB03 BC04 BD01Continued on the front page (72) Inventor Mari Katsumine 11-1 Haneda Asahimachi, Ota-ku, Tokyo EBARA CORPORATION F-term (reference) 3L058 BE02 BF09 4D012 BA01 4D019 BA13 BB02 BB03 BC04 BD01
Claims (5)
ト基を有する側鎖が、繊維径３０μｍ以下のポリオレフ
ィン系繊維、その集合体である織布又は不織布、又はそ
れらの加工品に、化学的に導入されていることを特徴と
する硫化水素除去材。1. A method according to claim 1, wherein the side chain having a silver-type cation exchange group and / or a chelate group has a polyolefin fiber having a fiber diameter of 30 μm or less, a woven or nonwoven fabric as an aggregate thereof, or a processed product thereof. A material for removing hydrogen sulfide, which is introduced into a material.
フト重合法で行うことを特徴とする請求項１記載の硫化
水素除去材。2. The hydrogen sulfide removing material according to claim 1, wherein the chemical introduction of the side chain is performed by a radiation graft polymerization method.
繊維、その集合体である織布又は不織布、又はそれらの
加工品に、２００ｋＧｙ以下の放射線を照射した後、カ
チオン交換基を有するモノマー、カチオン交換基に転換
可能なモノマー、キレート基を有するモノマー及びキレ
ート基に転換可能なモノマーより選ばれた一種以上のモ
ノマーをグラフト重合し、次いで銀イオンを担持させる
ことを特徴とする硫化水素除去材の製造方法。3. A monomer having a cation exchange group and a cation exchange group after irradiating a polyolefin fiber having a fiber diameter of 30 μm or less, a woven or nonwoven fabric as an aggregate thereof, or a processed product thereof to a radiation of 200 kGy or less. A method for producing a hydrogen sulfide removing material, comprising graft-polymerizing one or more monomers selected from a monomer convertible into a monomer, a monomer having a chelate group and a monomer convertible into a chelate group, and then supporting silver ions. .
おいて、前記織布又は不織布の目付が２５ｇ／ｍ2以上
であり、通気度３０ｍｌ／ｃｍ2・秒以上であることを
特徴とする硫化水素除去フィルタ。4. The material for removing hydrogen sulfide according to claim 1, wherein the woven or nonwoven fabric has a basis weight of 25 g / m 2 or more and an air permeability of 30 ml / cm 2 · second or more. Hydrogen sulfide removal filter.
するための上流側と下流側との色調比較をする手段を具
備したことを特徴とする請求項４記載の硫化水素除去フ
ィルタ。5. The hydrogen sulfide removal filter according to claim 4, wherein the filter includes means for comparing the color tone between the upstream side and the downstream side for estimating the life of the filter.
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|---|---|---|---|
| JP2000378580A JP3960408B2 (en) | 2000-12-13 | 2000-12-13 | Hydrogen sulfide removing material, manufacturing method thereof, and filter using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000378580A JP3960408B2 (en) | 2000-12-13 | 2000-12-13 | Hydrogen sulfide removing material, manufacturing method thereof, and filter using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2002177716A true JP2002177716A (en) | 2002-06-25 |
| JP3960408B2 JP3960408B2 (en) | 2007-08-15 |
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Cited By (1)
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|---|---|---|---|---|
| EP1869370A2 (en) * | 2005-03-21 | 2007-12-26 | Camfil Farr, Inc. | An exhaust filter module, and a method and apparatus for efficiency testing the same |
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|---|---|---|---|---|
| KR101970499B1 (en) * | 2018-08-14 | 2019-04-19 | (주)한길산업 | An odor removing apparatus for removing odor, a method for manufacturing the same, and an odor removing apparatus using the manufactured adsorption deodorizer |
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2000
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1869370A2 (en) * | 2005-03-21 | 2007-12-26 | Camfil Farr, Inc. | An exhaust filter module, and a method and apparatus for efficiency testing the same |
| EP1869370A4 (en) * | 2005-03-21 | 2014-06-04 | Camfil Farr Inc | An exhaust filter module, and a method and apparatus for efficiency testing the same |
| US9976770B2 (en) | 2005-03-21 | 2018-05-22 | Camfil Usa, Inc. | Exhaust filter module, and a method and apparatus for efficiency testing the same |
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| JP3960408B2 (en) | 2007-08-15 |
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