JP3953717B2 - Pleated fold air purification filter consisting of flat encapsulated deodorizing sheet - Google Patents
Pleated fold air purification filter consisting of flat encapsulated deodorizing sheet Download PDFInfo
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- JP3953717B2 JP3953717B2 JP2000235412A JP2000235412A JP3953717B2 JP 3953717 B2 JP3953717 B2 JP 3953717B2 JP 2000235412 A JP2000235412 A JP 2000235412A JP 2000235412 A JP2000235412 A JP 2000235412A JP 3953717 B2 JP3953717 B2 JP 3953717B2
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- deodorizing
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- Filtering Materials (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
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Description
【0001】
【発明の属する技術分野】
本発明は、空気清浄化フィルターに関する。
【0002】
【従来の技術】
従来、脱臭剤を使用した空気清浄化フィルターは、通気性を有するウレタンの多孔質基材上に、粒状或いは粉体状活性炭を接着させたものや、不織布に活性炭を塗りつけたり、活性炭素を含浸させたものにエレクトレットを貼り合わせたものがあった。また、ハニカム状の六角柱の部分の中にぺレット状活性炭を詰めたもの、あるいは、波状の不織布と平面状の不織布を組み合わせてできる三角柱の部分に同じくぺレット状活性炭を詰めたもの等があった。
【0003】
特開昭61−119269号公報では2枚の基材シート間に活性炭などの脱臭剤を挟み込む脱臭シートの製造方法が開示されている。
この2枚のシート間に脱臭剤を挟み込む脱臭シートの製造方法は、脱臭剤が基材から剥落することがなく、脱臭剤表面が樹脂で覆われることなく脱臭効果の低下が少ない脱臭シートを提供するものであり、更に、所望に応じて脱臭剤を多くすることができて脱臭寿命を長くできるなどの利点を有し、脱臭機能に関しては実用性が特に優れたものであった。
【0004】
しかしながら、この従来法においては、脱臭剤の上にシート又は熱によりシートを形成し得る材料を積層し全面を加熱するため、シートにかかる熱の影響が多大となり、加熱によって性能が低下する基材シートを用いることができず、多機能性の空気清浄化フィルターが得難いという問題があった。
【0005】
さらに重要な問題は、上記のような2枚の基材シートに脱臭剤を挟み込む方法では、出来上がった脱臭シートの全面に脱臭剤があり、例えば断裁した場合にはその断裁面から脱臭剤が抜け落ちたり、あるいはプリーツ折り(襞折り)した場合はその折り部において内部の脱臭剤が基材シートを突き破ってしまうなどの構造上の問題があった。
【0006】
【発明が解決しようとする課題】
本発明の課題は、2枚の基材シートに脱臭剤が封入された平面状封入脱臭シートにおいて、内部の脱臭剤が切断面や襞折り面から脱落することのない、粉落ち性の改良された平面状封入脱臭シートからなる空気清浄化フィルターを提供するものである。
【0007】
【課題を解決するための手段】
本発明者らは、上記課題を解決するため鋭意検討を重ねた結果、本発明に到達したものである。
【0008】
(i)基材A、基材Bとその間に封入された脱臭剤よりなる脱臭シートにおいて、基材Aおよび基材Bが、不織布、エレクレットフィルター、HEPAフィルターのいずれかであり、
(1)基材を走行させた状態で一定間隔でホッパーからの脱臭剤の落下を継続及び中断する方法、
(2)グラビアロールなどの凹部を有するロールに規則的に凹部を設けない場所を作って脱臭剤を規則的に基材上に供給する方法、
(1)、(2)のいずれかの方法・手段により、脱臭シートの内側の面に一定間隔ごとに脱臭剤が配置されるとともに脱臭剤が配置されない領域を設けた事を特徴とする平面状封入脱臭シートからなるプリーツ折り空気清浄化フィルター。
【0009】
(ii)請求項1記載の平面状封入脱臭シートにおいて、脱臭剤が配置されない領域において基材Aと基材Bが接着されていることを特徴とする請求項1記載の平面状封入脱臭シートからなるプリーツ折り空気清浄化フィルター。
【0010】
(iii)請求項1記載の平面状封入脱臭シートにおいて、脱臭剤が配置されない領域にバインダーが配置され、このバインダーにより基材Aと基材Bが接着されていることを特徴とする請求項1記載の平面状封入脱臭シートからなるプリーツ折り空気清浄化フィルター。
【0013】
【発明の実施の形態】
本発明は、2枚の基材シートに脱臭剤が封入された脱臭シートにおいて、内部の脱臭剤が切断面や襞折り面から脱落することのない、粉落ち性の改良された脱臭シートからなるプリーツ折り空気清浄化フィルターを提供する。
【0014】
本発明に係わる基材Aあるいは基材Bとしては、織布、不織布、ネット、及びスポンジ等の他、ポリエチレンフィルム、ポリプロピレンフィルム、及びポリエステルフィルムの様な汎用の熱可塑性フィルムや薄板等が挙げられる。これらの内、フィルムや薄板等の通気性に乏しいシートは、微細な穴をあけて通気性を向上させ、通気性フィルターとしても良い。その中でも、特に不織布等を用いれば、比較的均一な通気性を確保することができるばかりか、封入加工も容易であるため、優位に使用される。基材Aと基材Bは同じであっても差し支えなく、また異なる基材であっても差し支えない。
【0015】
本発明に係わる基材Aあるいは基材Bには、必要に応じて抗菌、防黴、抗ウイルス、防虫、害虫忌避、脱臭、消臭、粗塵除去などの機能を有するものを用いても良い。中でも、抗菌、防黴、抗ウイルス機能を有する基材を用いることが好ましく、基材Aあるいは基材Bはエレクトレットや光触媒担持のフィルターであっても良い。
【0016】
不織布は、ポリアミド系繊維、ポリエステル系繊維、ポリアルキレンパラオキシベンゾエート系繊維、ポリウレタン系繊維、ポリビニルアルコール系繊維、ポリ塩化ビニリデン系繊維、ポリ塩化ビニル系繊維、ポリアクリロニトリル系繊維、ポリオレフィン系繊維、フェノール系繊維などの合成繊維、ガラス繊維、金属繊維、アルミナ繊維、活性炭素繊維などの無機繊維、木材パルプ、麻パルプ、コットンリンターパルプなどの天然繊維、再生繊維、あるいはこれらの繊維に親水性、難燃性、脱臭性、吸着性、抗菌性などの機能を付与した繊維などを使用し、各種方法によって製造したものである。
【0017】
不織布の製造方法については特に制限はなく、目的・用途に応じて、乾式法、湿式抄造法、メルトブローン法、スパンボンド法などで得られたウェブを水流交絡法、ニードルパンチ法、ステッチボンド法などの物理的方法、サーマルボンド法などの熱による接着方法、レジンボンドなどの接着剤による接着方法で強度を発現させる方法を適宜組み合わせて製造することができる。
【0018】
本発明に係わる基材としてエレクトレットフィルター、HEPAフィルター、芳香剤を担持したフィルター、吸着剤や触媒が熱可塑性樹脂に練り込み担持されながらその一部が表面に露出しているフィルター、酵素系などの脱臭剤を担持したフィルター、あるいは消臭剤や抗菌剤などを担持したフィルターを用いることが出来る。
【0019】
本発明に係わるエレクトレットフィルターとは、半永久的に電気分極を保持し、外部に対して電気力を及ぼすフィルターであり、その静電気力によって粒子を捕捉するものである。帯電方法としては、エレクトロエレクトレット、熱エレクトレット、ラジオエレクトレット、メカノエレクトレット、フォトエレクトレット、マグネットエレクトレットなどが挙げられるが、工業的に不織布フィルターで用いられているものは、主にエレクトロエレクトレットおよび熱エレクトレットであり、フィルター材料としてはポリプロピレンまたはプロピレン主体の共重合体が用いられることが多い。
【0020】
不織布は嵩高で3次元空隙が存在するため、コロナ放電などによる帯電処理では安定した帯電効果を得ることが難しい。しかしながら、コロナ放電などで帯電処理を施したフィルムを繊維状に断裁、それを不織布化したスプリットファイバーエレクトレットフィルターや、メルトブロー紡糸時および溶融紡糸時に高電圧を印加して熱エレクトレット的に繊維を帯電させたメルトブロー不織布式エレクトレットフィルターおよびスパンボンド不織布式エレクトレットフィルターなどは、安定した分極電荷を得ることができる。なお、メルトブロー不織布式エレクトレットフィルターは単体では力学的強度が小さいため、乾式不織布やスパンボンドなどを貼り合わせて使用される場合がある。
【0021】
本発明に係わるHEPAフィルターとは、超高性能の集塵フィルターであり、0.3μmの粒子に対して99.97%以上の集塵効率を有するものである。従来は、軍事用、放射性廃棄物用、クリーンルーム用などの特殊用途で用いられたものであるが、近年では家庭用空気清浄機などの民生用にもHEPAフィルターの使用が拡大する傾向がある。
【0022】
本発明に係わる脱臭剤とは主に悪臭を除去する目的で用いられる薬剤の総称であり、具体的には、活性炭、添着活性炭、ゼオライト、活性アルミナ、活性白土、イオン交換樹脂、鉄アスコルビン酸、鉄フタロシアニン誘導体などの吸着脱臭剤、マンガン系酸化物やペロブスカイト型触媒などの低温酸化触媒、酸化チタンや酸化亜鉛などの光触媒、植物抽出成分に含まれる化合物であるカテキン、タンニン、フラボノイド等を用いた消臭剤などを挙げることができる。これらの脱臭剤は必要に応じて複数のものを併用しても良く、また、これらの脱臭剤を複合化したハイブリット脱臭剤としても良い。
【0023】
本発明に係わるバインダーは熱可塑性樹脂、熱硬化性樹脂、ホットメルト、ヒートシール、2液硬化型接着剤、湿気硬化型型接着剤、紫外線あるいは電子線硬化型接着剤などであり、その中でも優位に使用される熱可塑性樹脂として、エチレン酢酸ビニル共重合体またはこの変性物、エチレンアクリレート共重合体、アイオノマー、ポリアミド、ナイロン、ポリエステル、ポリエチレン、ポリプロピレン、ポリウレタン系などの樹脂を挙げることができる。
【0024】
本発明に係わるバインダーの軟化点または融点は特に制限されるものではなく、フィルターの後加工条件や使用環境温度、基材または脱臭剤の耐熱性などを考慮して適宜選択すれば良い。
【0025】
本発明に係わる脱臭剤の形状は、粉体状、粒状、ウイスカー状、短繊維状、長繊維状であることが好ましい。
本発明に係わる脱臭剤または熱可塑性接着剤の粒径は、10〜100メッシュであることが好ましい。粒径が10メッシュ未満では活性炭が加圧時に割れたり、基材同士の接着点が不均一になるなどの問題があり、一方、粒径が100メッシュを越えると基材の目から離脱するなどの問題がある。同様な理由で本発明に係わるバインダーの形状も粉体状、粒状、ウイスカー状、短繊維状、長繊維状など各種の形態をとることができるが、さらに液状、半固形状、シート状などの形態をとることも可能である。
【0026】
本発明に係わる脱臭剤の封入量は、特に制限されるものではないが、800g/m2以下であることが好ましい。封入量が800g/m2を越えると基材間の接着強度が低くなり、また、厚さが大きくなってプリーツ加工が困難となるため、実用性が低下する。
【0027】
本発明に係わる基材の上に脱臭剤と熱可塑性接着剤を散布する場合には、両者を個別に散布しても良いが、脱臭性などに特に影響がなければ予め混合したものを散布することが好ましい。散布の方法としては、ホッパー下部からの自由落下による散布、グラビアロールなどの凹部を有するロールに連続供給して基材上に供給する方法、空気中に分散した送風による散布、水系分散してのスプレー塗工やダイ塗工などを挙げることができる。
【0028】
本発明において、平面状封入脱臭シートの内側の面に脱臭剤を一定間隔で配置する部分と、脱臭剤を配置しない部分を設けて平面状封入脱臭シートを貼合せる必要がある。脱臭剤を一定間隔で配置するには基材を走行させた状態で一定間隔でホッパーからの脱臭剤の落下を継続及び中断する方法、グラビアロールなどの凹部を有するロールに規則的に凹部を設けない場所を作って脱臭剤を規則的に基材上に供給する方法、空気中に分散した送風による散布において規則的に送風を中断することにより脱臭剤の供給を制御する手段、水系分散してのスプレー塗工やダイ塗工などで機械的に脱臭剤の供給を制御する手段などを挙げることができる。
【0029】
本発明において、平面状封入脱臭シートの内側の面に脱臭剤を配置しない部分において、その部分にバインダーのみを供給する必要がある。方法は大きくわけて2方法あり、第一には脱臭剤の有無にかかわらず基材全面にバインダーを散布する方法であり、バインダーの散布は脱臭剤の散布の前、後のどちらでも差し支えない。第二には脱臭剤を配置しなかった部分にのみバインダーを配置する方法であり、これは基材を走行させた状態で脱臭剤の供給の断続と全く逆になるようにホッパーからバインダーの落下を継続及び中断する方法、同じく脱臭剤を供給したグラビアロールの非供給部分のみに凹部を有する別のグラビアロールによりバインダーを規則的(すなわち脱臭剤の配置されない部分にのみ)に基材上に供給する方法など、脱臭剤を断続的に供給する技術を応用して使用することができる。この際、脱臭剤の有無をタイミングマークなどにより検知し、バインダー供給のタイミングを図ることは何ら問題ない。
【0030】
本発明において2枚の基材を貼合せる場合には、加熱あるいは加圧、もしくはその両方により達成することができる。加熱方法は、特に限定されるものではないが、バインダーが熱可塑性樹脂である場合には散布した側から加熱することが好ましい。熱可塑性樹脂を散布した側から加熱する場合には、接触式の熱伝導による加熱は困難であるため、熱風などの非接触式の加熱手段を採ることが好ましく、中でも赤外線ヒーターやガスバーナーヒーターのような放射熱による手段が特に好ましい。
【0031】
本発明に係わる基材を重ね合わせた後の加圧は、例えば加圧したロール間を通す方法などを採用できる。加圧の程度は、接着強度、脱臭剤の潰れ、通気性への影響などを考慮して、適宜設定すればよい。
【0032】
本発明は、2枚の基材に脱臭剤を挟み込んだ平面状封入脱臭シートにおいて、その断裁面から脱臭剤が抜け落ちたり、あるいはプリーツ折り(襞折り)した場合はその折り部において内部の脱臭剤が基材シートを突き破るなどの問題を解消するものであるが、平面状封入脱臭シートの内側の面に一定間隔ごとに脱臭剤が配置されるとともに脱臭剤が配置されない領域を設ける事により、脱臭剤が配置されない領域を断裁あるいはプリーツの折り部にすることにより脱臭剤の抜け落ちや基材シートの破れを回避するものである。
【0033】
さらに本発明においては、平面状封入脱臭シートの内側の面に一定間隔ごとに脱臭剤が配置されるとともに脱臭剤が配置されない領域を設け、かつその脱臭剤が配置されない領域にバインダーのみを設けることにより貼合せた状況での強度を増大させることが可能となり、このバインダーのみを設けた領域を断裁あるいはプリーツの折り部にすることにより脱臭剤の抜け落ちや基材シートの破れを回避するものである。
【0034】
【実施例】
以下、本発明を実施例により説明するが、本発明の趣旨を逸脱しない限り、実施例に限定されるものではない。
【0035】
調製例1
ポリプロピレン繊維(4d、38mm、50w%)、ポリエチレン繊維(6d、51mm、30w%)とビスコースレーヨン繊維(3d、51mm、20w%)とを混合し、乾式法により空気中でウエッブを形成し、次に、熱可塑性のバインダーであるアクリルのラテックス中に含浸し、繊維を接着して形成し、不織布を得た。次いで、ピリジンチオール亜鉛塩の微粒子からなる抗菌・防黴剤を含む塗液にこの不織布を含浸させてピリジンチオール亜鉛塩を1g/m2担持し、抗菌・防黴性の 基材Bを調製した。
【0036】
調製例2
脱臭剤として、粒状活性炭50重量部と粒状ゼオライト吸着剤50重量部の混合物を用い、その混合物合計100部に対して、脱臭剤用のバインダーとして熱可塑性接着剤であり軟化点100℃のエチレン酢酸ビニル樹脂粉体50重量部を混合し、脱臭混合粉体を調製した。
【0037】
調整例3
脱臭剤を含まないバインダーとして、熱可塑性接着剤であり軟化点90℃のエチレン酢酸ビニル樹脂粉体を用いた。
【0038】
調製例4
極細ガラス繊維(平均繊維径0.6μm)を12重量%と、ポリエステル繊維(繊維径18μm、繊維長は5mm)を38重量%と、バインダー繊維として芯鞘型熱融着性ポリエステル繊維(繊維径14μm、繊維長5mm、鞘部融点110℃)を50重量%とを混合して水性スラリーを調製し、これらのスラリーから円網抄紙機にて坪量40g/m2のHEPAフィルターを作製し、これを基材Aとした。
【0039】
調製例5
ポリエステル繊維(テトロン、3d、38mm、50w%/6d、51mm、30w%)とビスコースレーヨン繊維(3d、51mm、20w%)とを混合し、乾式法により空気中でウエッブを形成し、次に、熱可塑性のバインダーであるアクリルのラテックス中に含浸し、繊維を接着して形成し、不織布を得た。次いで、シリカゲル担体に柿カテキンを担持させた抗菌剤を含む塗液にこの不織布を含浸させて抗菌剤塗液を20g/m2担持し、抗菌剤を担持した基材(A’)を調製した。
【0040】
実施例1
調製例1の基材Bの上に24cm角の四角形の面積上に調製例2の脱臭混合粉体を50g/m2の割合で散布した。脱臭混合粉体が散布された四角形は四辺から2cmずつの割合で脱臭混合粉体(脱臭剤)が設けられていない部分を介して隣の脱臭混合粉体が散布された四角形と並んでいる。製造においてはグラビア式の回転ロールを用い、脱臭混合粉体の供給と非供給をグラビアロールの凹部の配置により決定した。混合粉体を散布した側から表面温度150℃の遠赤外線ヒーターを用いて加熱した。熱可塑性のバインダーが可塑化した後に加熱を止め、速やかに基材Bの脱臭剤散布側に基材Aとして市販のエレクトレットフィルター(東燃タピルス製、PO−20ALOG)を重ね合わせて2本の回転ロール間に挟んで加圧一体化し、平面状封入脱臭シートを製造した。これを実施例1の平面状封入脱臭シートとした。
【0041】
実施例2
実施例1において、市販のエレクトレットフィルターに代えてHEPAフィルターとして調製例4の基材Aとする以外は、全て実施例1と同一の方法で平面状封入脱臭シートを製造した。これを実施例2の平面状封入脱臭シートとした。
【0042】
実施例3
実施例1において、市販のエレクトレットフィルターに代えて調製例5の抗菌剤を担持した基材A’とする以外は、全て実施例1と同一の方法で平面状封入脱臭シートを製造した。これを実施例3の平面状封入脱臭シートとした。
【0043】
実施例4
調製例1の基材Bの上に24cm角の四角形の面積上に調製例2の脱臭混合粉体を50g/m2の割合で散布した。脱臭混合粉体が散布された四角形は四辺から2cmずつの割合で脱臭混合粉体(脱臭剤)が設けられていない部分をを介して隣の脱臭混合粉体が散布された四角形と並んでいる。該2cmの幅の脱臭混合粉体(脱臭剤)が設けられていない部分には、調整例3のバインダーのみを50g/m2の割合で散布した。製造においてはグラビア式の回転ロールを2機用い、脱臭混合粉体の供給と非供給をグラビアロールの凹部の配置により決定し、それと同調させてバインダーの非供給と供給をグラビアロールの凹部の配置により決定した。混合粉体を散布した側から表面温度150℃の遠赤外線ヒーターを用いて加熱した。熱可塑性のバインダーが可塑化した後に加熱を止め、速やかに基材Bの脱臭剤散布側に基材Aとして市販のエレクトレットフィルター(東燃タピルス製、PO−20ALOG)を重ね合わせて2本の回転ロール間に挟んで加圧一体化し、平面状封入脱臭シートを製造した。これを実施例4の平面状封入脱臭シートとした。
【0044】
比較例1
調製例1の基材Bの上全面に調製例2の脱臭混合粉体を50g/m2の割合で散布した。製造においてはグラビア式の回転ロールを用い、脱臭混合粉体を連続して供給した。混合粉体を散布した側から表面温度150℃の遠赤外線ヒーターを用いて加熱した。熱可塑性のバインダーが可塑化した後に加熱を止め、速やかに基材Bの脱臭剤散布側に基材Aとして市販のエレクトレットフィルター(東燃タピルス製、PO−20ALOG)を重ね合わせて2本の回転ロール間に挟んで加圧一体化し、平面状封入脱臭シートを製造した。これを比較例1の平面状封入脱臭シートとした。
【0045】
比較例2
比較例1において、市販のエレクトレットフィルターに代えてHEPAフィルターとして調製例4の基材Aとする以外は、全て比較例1と同一の方法で平面状封入脱臭シートを製造した。これを比較例2の平面状封入脱臭シートとした。
【0046】
比較例3
比較例1において、市販のエレクトレットフィルターに代えて調製例5の抗菌剤を担持した基材A’とする以外は、全て比較例1と同一の方法で平面状封入脱臭シートを製造した。これを比較例3の平面状封入脱臭シートとした。
【0047】
以上、実施例および比較例で得られた平面状封入脱臭シートは以下の方法で粉落ち試験、プリーツ加工試験を行い、その結果を表1に示した。
【0048】
[粉落ち試験]
実施例および比較例の平面状封入脱臭シートを25cm角の大きさに断裁した。25cm角に断裁した平面状封入脱臭シートを10枚重ね、箱の中で5分間激しく振った。箱の中に落ちた脱臭剤を集めて重量を測定した。粉落ちは皆無ということは有り得ないのでこの測定条件で10mg以下を優、10mgより重く20mg以下を良、20mgより重く50mg以下を並、50mgを超える場合を劣として評価した。
【0049】
[プリーツ折り試験]
実施例および比較例の平面状封入脱臭シートを25cmのピッチでプリーツ折りした。100山折った状態で再度広げて平面状に戻し、折り面の表裏の状況を確認した。この測定条件で折り面に内部の脱臭剤がはみ出しているなどの破断箇所が全くないものを優、1個以上で10個以下を並、10個よりも多い場合を劣として評価した。当然ながらこのような破断箇所があるとそこから脱臭剤の脱落の危険性があるばかりでなく、空気が漏れるため除塵性能を低下させるという問題を生じる。
【0050】
[除塵性能]
平面状封入脱臭シートをプリーツ折りしたフィルターエレメントを用いてその除塵性能を、脱臭剤を含んでいない元の基材シートのみからなるフィルターエレメントの除塵性能と比較した。除塵性能はパーティクルカウンターを用いて測定した10cm/秒の線風速で上流と下流の大気塵(0.3〜0.5μmφ)の数より除去率を算定して比較した。脱臭剤を含まない元の基材のみからなるフィルターエレメントの除去率よりも良好な場合を優、比較して98%以上の除去率である場合を並、90%以上で98%未満を可、90%未満を不可とした。
【0051】
[接着性試験]
実施例、比較例の平面状封入脱臭シートを25cm角に切断し、そのエッジ面から基材A、基材Bの剥離を行い接着性を判定した。テンシロンで測定した基材A〜B間の剥離強度が100gf/25mm以上の場合を剥離しがたいとして接着性が優。50gf/25mmより大きく100gf/25mmより小さい場合を接着性が並、50gf/25mmより小さい場合を接着性が劣とした。
【0052】
【表1】
【0053】
表1の結果から、実施例の平面状封入脱臭シートは、同じ基材を用いた比較例の平面状封入脱臭シートに比べて粉落ち防止性能が非常に高く、また破断箇所がないことから破断面からの脱臭剤の脱落もないばかりか除塵性能も良好であることが判明した。
【0054】
【発明の効果】
本発明により、2枚の基材シートに脱臭剤が封入された平面状封入脱臭シートにおいて、内部の脱臭剤が切断面や襞折り面から脱落することのない、粉落ち性の改良された平面状封入脱臭シートからなるプリーツ折り空気清浄化フィルターを提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an air cleaning filter.
[0002]
[Prior art]
Conventionally, air purification filters using deodorizers are made by adhering granular or powdered activated carbon on a porous urethane porous substrate, applying activated carbon to nonwoven fabric, or impregnating activated carbon. There was a thing which stuck the electret to what was made to do. In addition, a honeycomb-shaped hexagonal column portion filled with pellet-like activated carbon, or a triangular prism portion formed by combining a wave-like nonwoven fabric and a planar nonwoven fabric, and a pellet-like activated carbon portion, etc. there were.
[0003]
Japanese Patent Application Laid-Open No. 61-119269 discloses a method for producing a deodorizing sheet in which a deodorizing agent such as activated carbon is sandwiched between two substrate sheets.
The deodorizing sheet manufacturing method in which the deodorizing agent is sandwiched between the two sheets provides a deodorizing sheet in which the deodorizing agent is not peeled off from the base material and the surface of the deodorizing agent is not covered with a resin, and the deodorizing effect is less deteriorated. In addition, it has the advantage that the deodorizing agent can be increased as desired and the deodorizing life can be extended, and the practicality of the deodorizing function is particularly excellent.
[0004]
However, in this conventional method, a sheet or a material capable of forming a sheet by heating is laminated on the deodorizer and the entire surface is heated, so that the influence of the heat applied to the sheet is great, and the performance is deteriorated by heating. There was a problem that a sheet could not be used and it was difficult to obtain a multifunctional air cleaning filter.
[0005]
More importantly, in the method of sandwiching the deodorant between the two base sheets as described above, there is a deodorant on the entire surface of the completed deodorant sheet. For example, when the sheet is cut, the deodorant is dropped from the cut surface. Or when the pleats are folded (folded), there is a structural problem such that the internal deodorant breaks through the base sheet at the folded portion.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to improve the powder fall-off property in a flat encapsulated deodorizing sheet in which a deodorizing agent is encapsulated in two base sheet sheets so that the internal deodorizing agent does not fall off from the cut surface or the folded surface. An air purification filter comprising a flat encapsulated deodorizing sheet is provided.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
[0008]
( I ) In the deodorization sheet which consists of the base material A and the base material B, and the deodorizing agent enclosed between them, the base material A and the base material B are any of a nonwoven fabric, an electret filter, and a HEPA filter,
(1) A method of continuing and interrupting the dropping of the deodorant from the hopper at regular intervals while the substrate is running,
(2) A method of regularly supplying a deodorizing agent on a base material by creating a place where a concave portion is not provided on a roll having a concave portion such as a gravure roll ,
(1) A planar shape characterized in that a deodorizer is disposed at regular intervals on the inner surface of the deodorization sheet and a region where no deodorant is disposed is provided by any one of the methods / means of (2) Pleated folded air purification filter consisting of an enclosed deodorizing sheet.
[0009]
( Ii ) The planar encapsulated deodorizing sheet according to claim 1, wherein the base material A and the base material B are adhered in a region where the deodorizing agent is not disposed. A pleated fold air cleaning filter.
[0010]
(Iii) In a planar inclusion deodorizing sheet of claim 1, wherein the binder is disposed in a region deodorants is not disposed, according to claim 1, by the binder base material A and the substrate B, characterized in that it is bonded serial mounting planar inclusion deodorizing pleat folding air freshening filter consist of a sheet of.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a deodorizing sheet deodorant is sealed on two of the base sheet, not to the interior of the deodorizing agent from falling off from the cut surface and pleated surfaces, consisting of deodorant sheet having improved the powder falling property A pleated folded air cleaning filter is provided.
[0014]
Examples of the substrate A or the substrate B according to the present invention include general-purpose thermoplastic films and thin plates such as polyethylene films, polypropylene films, and polyester films, as well as woven fabrics, nonwoven fabrics, nets, and sponges. . Among these, a sheet with poor air permeability such as a film or a thin plate may be formed as a breathable filter by making fine holes to improve air permeability. Among them, the use of non-woven fabrics and the like is advantageous because not only can relatively uniform air permeability be ensured but also the encapsulation process is easy. The substrate A and the substrate B may be the same, or may be different substrates.
[0015]
As the substrate A or the substrate B according to the present invention, those having functions such as antibacterial, antifungal, antiviral, insecticidal, pest repellent, deodorization, deodorization, and coarse dust removal may be used as necessary. . Among them, it is preferable to use a base material having antibacterial, antifungal, and antiviral functions, and the base material A or the base material B may be an electret or a filter supporting a photocatalyst.
[0016]
Non-woven fabric is polyamide fiber, polyester fiber, polyalkylene paraoxybenzoate fiber, polyurethane fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyvinyl chloride fiber, polyacrylonitrile fiber, polyolefin fiber, phenol fiber. Synthetic fibers such as fibers, inorganic fibers such as glass fibers, metal fibers, alumina fibers and activated carbon fibers, natural fibers such as wood pulp, hemp pulp, and cotton linter pulp, recycled fibers, or hydrophilicity and flame resistance to these fibers It is manufactured by various methods using fibers having functions such as property, deodorizing property, adsorptive property and antibacterial property.
[0017]
There are no particular restrictions on the method of manufacturing the nonwoven fabric, and the web obtained by the dry method, wet papermaking method, meltblown method, spunbond method, etc., hydroentangled method, needle punch method, stitch bond method, etc., depending on the purpose and application It is possible to manufacture by appropriately combining the physical method, the heat bonding method such as the thermal bond method, and the method of developing the strength with the adhesive method such as the resin bond.
[0018]
As a base material according to the present invention, an electret filter, a HEPA filter, a filter carrying a fragrance, a filter in which an adsorbent or a catalyst is kneaded and supported in a thermoplastic resin, a part of which is exposed on the surface, an enzyme system, etc. A filter carrying a deodorant or a filter carrying a deodorant or an antibacterial agent can be used.
[0019]
The electret filter according to the present invention is a filter that retains electric polarization semipermanently and applies an electric force to the outside, and captures particles by the electrostatic force. Examples of charging methods include electroelectrets, thermal electrets, radio electrets, mechano electrets, photo electrets, and magnet electrets, but industrially used non-woven fabric filters are mainly electroelectrets and thermal electrets. In many cases, polypropylene or propylene-based copolymers are used as filter materials.
[0020]
Since the nonwoven fabric is bulky and has three-dimensional voids, it is difficult to obtain a stable charging effect by charging treatment using corona discharge or the like. However, a film that has been charged by corona discharge or the like is cut into a fiber, and a non-woven split fiber electret filter or a high voltage is applied during melt blow spinning and melt spinning to charge the fiber like a heat electret. The melt blown nonwoven fabric electret filter and the spunbond nonwoven fabric electret filter can obtain a stable polarization charge. The melt blown nonwoven fabric electret filter has a small mechanical strength, and may be used by bonding a dry nonwoven fabric or a spunbond.
[0021]
The HEPA filter according to the present invention is an ultra-high performance dust collection filter, and has a dust collection efficiency of 99.97% or more with respect to 0.3 μm particles. Conventionally, it has been used for special purposes such as military use, radioactive waste use, and clean room use. In recent years, however, the use of HEPA filters has been increasing for consumer use such as household air purifiers.
[0022]
The deodorizer according to the present invention is a general term for agents mainly used for the purpose of removing malodor, specifically, activated carbon, impregnated activated carbon, zeolite, activated alumina, activated clay, ion exchange resin, iron ascorbic acid, Adsorption deodorizers such as iron phthalocyanine derivatives, low-temperature oxidation catalysts such as manganese-based oxides and perovskite-type catalysts, photocatalysts such as titanium oxide and zinc oxide, catechins, tannins, and flavonoids that are compounds contained in plant extracts A deodorant etc. can be mentioned. A plurality of these deodorizers may be used in combination as necessary, or may be a hybrid deodorizer obtained by combining these deodorizers.
[0023]
The binder according to the present invention is a thermoplastic resin, a thermosetting resin, a hot melt, a heat seal, a two-component curable adhesive, a moisture curable adhesive, an ultraviolet ray or an electron beam curable adhesive, etc. Examples of the thermoplastic resin used in the resin include ethylene vinyl acetate copolymer or a modified product thereof, ethylene acrylate copolymer, ionomer, polyamide, nylon, polyester, polyethylene, polypropylene, polyurethane resin and the like.
[0024]
The softening point or melting point of the binder according to the present invention is not particularly limited, and may be appropriately selected in consideration of the post-processing conditions of the filter, the use environment temperature, the heat resistance of the base material or the deodorizing agent, and the like.
[0025]
The shape of the deodorizer according to the present invention is preferably powder, granular, whisker, short fiber, or long fiber.
The particle size of the deodorizer or thermoplastic adhesive according to the present invention is preferably 10 to 100 mesh. If the particle size is less than 10 mesh, there is a problem that the activated carbon is cracked when pressed or the adhesion points between the substrates are non-uniform. On the other hand, if the particle size exceeds 100 mesh, it is detached from the eyes of the substrate. There is a problem. For the same reason, the shape of the binder according to the present invention can take various forms such as powder, granular, whisker, short fiber, long fiber, etc., but also liquid, semi-solid, sheet, etc. It can also take a form.
[0026]
The amount of the deodorizing agent according to the present invention is not particularly limited, but is preferably 800 g / m 2 or less. When the amount of encapsulation exceeds 800 g / m 2 , the adhesive strength between the substrates becomes low, and the thickness becomes large and pleating becomes difficult.
[0027]
When the deodorizing agent and the thermoplastic adhesive are sprayed on the substrate according to the present invention, both may be sprayed separately, but if there is no particular influence on the deodorizing property, a premixed one is sprayed. It is preferable. As a method of spraying, spraying by free fall from the lower part of the hopper, a method of continuously supplying to a roll having a concave portion such as a gravure roll and supplying it on a base material, spraying by air blown dispersed in the air, Examples include spray coating and die coating.
[0028]
In this invention, it is necessary to provide the part which arrange | positions a deodorizing agent at a fixed space | interval on the inner surface of a planar enclosure deodorizing sheet, and the part which does not arrange | position a deodorizing agent, and to bond a planar enclosure deodorizing sheet. In order to arrange the deodorant at regular intervals, a method of continuing and interrupting the dropping of the deodorant from the hopper at regular intervals while the base material is running, a roll having a concave portion such as a gravure roll is regularly provided A method of supplying a deodorant regularly on a substrate by creating a place where there is no space, a means for controlling the supply of a deodorant by discontinuing air blowing regularly in spraying by air blowing dispersed in air, A means for mechanically controlling the supply of the deodorizer by spray coating or die coating.
[0029]
In the present invention, it is necessary to supply only the binder to the portion where the deodorizing agent is not disposed on the inner surface of the flat encapsulated deodorizing sheet. There are roughly two methods. First, the binder is sprayed over the entire surface of the substrate regardless of the presence or absence of the deodorant. The binder can be sprayed before or after the deodorant is sprayed. The second method is to place the binder only on the part where the deodorant is not placed. This means that the binder is dropped from the hopper so that it is completely opposite to the intermittent supply of the deodorant while the substrate is running. The binder is regularly supplied to the substrate by another gravure roll having a recess only in the non-feeding part of the gravure roll which is also supplied with the deodorizer (that is, only in the part where no deodorant is arranged). The technique which supplies a deodorizing agent intermittently, such as a method to perform, can be used. At this time, there is no problem in detecting the presence or absence of the deodorizing agent with a timing mark or the like and timing the binder supply.
[0030]
In the present invention, when two substrates are bonded, this can be achieved by heating or pressurization, or both. The heating method is not particularly limited, but when the binder is a thermoplastic resin, it is preferable to heat from the sprayed side. When heating from the sprayed side of the thermoplastic resin, it is difficult to heat by contact-type heat conduction, so it is preferable to employ non-contact heating means such as hot air, among which infrared heaters and gas burner heaters are used. Such radiant heat means is particularly preferred.
[0031]
For example, a method of passing between the pressurized rolls can be adopted as the pressurization after the substrates according to the present invention are superposed. The degree of pressurization may be appropriately set in consideration of the adhesive strength, the deodorizing agent crushing, the influence on air permeability, and the like.
[0032]
The present invention relates to a flat encapsulated deodorizing sheet in which a deodorizing agent is sandwiched between two substrates, and when the deodorizing agent falls off from the cut surface or is folded in a pleat (folded), the internal deodorizing agent is in the folded portion. However, the deodorizing agent is placed on the inner surface of the flat encapsulated deodorizing sheet at regular intervals and areas where the deodorizing agent is not arranged are provided. The region where the agent is not disposed is cut or formed into a fold portion of the pleats to prevent the deodorant from falling off and the base sheet from being torn.
[0033]
Further, in the present invention, a region where the deodorizer is arranged at regular intervals and a region where the deodorant is not disposed is provided on the inner surface of the flat encapsulated deodorant sheet, and only a binder is provided in a region where the deodorant is not disposed. It is possible to increase the strength in the situation where they are bonded together, and it is possible to avoid dropping of the deodorant and tearing of the base sheet by cutting the region provided only with this binder or by folding the pleat. .
[0034]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, unless it deviates from the meaning of this invention, it is not limited to an Example.
[0035]
Preparation Example 1
Polypropylene fiber (4d, 38mm, 50w%), polyethylene fiber (6d, 51mm, 30w%) and viscose rayon fiber (3d, 51mm, 20w%) are mixed, and a web is formed in the air by a dry method. Next, it was impregnated in an acrylic latex, which is a thermoplastic binder, and the fibers were bonded to form a nonwoven fabric. Next, an antibacterial / antifungal base material B was prepared by impregnating the nonwoven fabric with a coating solution containing antibacterial / antifungal agents composed of fine particles of pyridinethiol zinc salt to carry 1 g / m 2 of pyridinethiol zinc salt. .
[0036]
Preparation Example 2
As a deodorizer, a mixture of 50 parts by weight of granular activated carbon and 50 parts by weight of a granular zeolite adsorbent was used, and a total of 100 parts of the mixture was a thermoplastic adhesive as a deodorizer binder and ethylene acetate having a softening point of 100 ° C. 50 parts by weight of vinyl resin powder was mixed to prepare a deodorized mixed powder.
[0037]
Adjustment example 3
As a binder not containing a deodorant, an ethylene vinyl acetate resin powder having a softening point of 90 ° C., which is a thermoplastic adhesive, was used.
[0038]
Preparation Example 4
12% by weight of ultrafine glass fiber (average fiber diameter 0.6 μm), 38% by weight of polyester fiber (fiber diameter 18 μm, fiber length 5 mm), core-sheath type heat-fusible polyester fiber (fiber diameter) as binder fiber 14 μm, fiber length 5 mm, sheath melting point 110 ° C.) were mixed with 50% by weight to prepare an aqueous slurry, and a HEPA filter having a basis weight of 40 g / m 2 was produced from these slurries with a circular paper machine, This was designated as substrate A.
[0039]
Preparation Example 5
Polyester fiber (Tetron, 3d, 38mm, 50w% / 6d, 51mm, 30w%) and viscose rayon fiber (3d, 51mm, 20w%) are mixed, and a web is formed in the air by a dry method. It was impregnated into an acrylic latex, which is a thermoplastic binder, and the fibers were bonded to form a nonwoven fabric. Next, a non-woven fabric was impregnated with a coating liquid containing an antibacterial agent having a silica gel carrier supporting cocoon catechin, and the antibacterial coating liquid was supported at 20 g / m 2 to prepare a base material (A ′) supporting the antibacterial agent. .
[0040]
Example 1
On the base material B of Preparation Example 1, the deodorized mixed powder of Preparation Example 2 was sprayed at a rate of 50 g / m 2 on a 24 cm square area. The quadrangle in which the deodorized mixed powder is dispersed is aligned with the quadrangle in which the adjacent deodorized mixed powder is dispersed through a portion where the deodorized mixed powder (deodorant) is not provided at a rate of 2 cm from the four sides. In production, a gravure-type rotating roll was used, and the supply and non-supply of the deodorized mixed powder was determined by the arrangement of the concave portions of the gravure roll. It heated using the far-infrared heater with a surface temperature of 150 degreeC from the side which spread mixed powder. After the thermoplastic binder has been plasticized, the heating is stopped, and two rotating rolls are quickly formed by superimposing a commercially available electret filter (PO-20ALOG, manufactured by Tonen Tapirs) as the base material A on the side of the base material B where the deodorant is applied. A flat encapsulated deodorizing sheet was produced by pressing and interposing them. This was used as the flat encapsulated deodorizing sheet of Example 1.
[0041]
Example 2
In Example 1, a flat encapsulated deodorizing sheet was produced in the same manner as in Example 1 except that instead of the commercially available electret filter, the substrate A of Preparation Example 4 was used as the HEPA filter. This was used as the flat encapsulated deodorizing sheet of Example 2.
[0042]
Example 3
In Example 1, a planar encapsulated deodorizing sheet was produced in the same manner as in Example 1 except that the substrate A ′ carrying the antibacterial agent of Preparation Example 5 was used instead of the commercially available electret filter. This was used as the flat encapsulated deodorizing sheet of Example 3.
[0043]
Example 4
On the base material B of Preparation Example 1, the deodorized mixed powder of Preparation Example 2 was sprayed at a rate of 50 g / m 2 on a 24 cm square area. The quadrangle on which the deodorized mixed powder is dispersed is arranged at a rate of 2 cm from the four sides along with the quadrangle on which the adjacent deodorized mixed powder is dispersed through a portion where the deodorized mixed powder (deodorant) is not provided. . Only the binder of Preparation Example 3 was sprayed at a rate of 50 g / m 2 on the portion where the deodorized mixed powder (deodorant) having a width of 2 cm was not provided. In production, two gravure-type rotating rolls are used, and the supply and non-supply of deodorized mixed powder is determined by the arrangement of the concave portions of the gravure roll, and the non-supply and supply of the binder is arranged in synchronization with the arrangement of the concave portions of the gravure roll Determined by. It heated using the far-infrared heater with a surface temperature of 150 degreeC from the side which spread mixed powder. After the thermoplastic binder has been plasticized, the heating is stopped, and two rotating rolls are quickly formed by superimposing a commercially available electret filter (PO-20ALOG, manufactured by Tonen Tapirs) as the base material A on the side of the base material B where the deodorant is applied. A flat encapsulated deodorizing sheet was produced by pressing and interposing them. This was used as the flat encapsulated deodorizing sheet of Example 4.
[0044]
Comparative Example 1
The deodorized mixed powder of Preparation Example 2 was sprayed on the entire upper surface of the base material B of Preparation Example 1 at a rate of 50 g / m 2 . In production, a gravure-type rotating roll was used, and the deodorized mixed powder was continuously supplied. It heated using the far-infrared heater with a surface temperature of 150 degreeC from the side which spread mixed powder. After the thermoplastic binder has been plasticized, the heating is stopped, and two rotating rolls are quickly formed by superimposing a commercially available electret filter (PO-20ALOG, manufactured by Tonen Tapirs) as the base material A on the side of the base material B where the deodorant is applied. A flat encapsulated deodorizing sheet was produced by pressing and interposing them. This was used as the flat encapsulated deodorizing sheet of Comparative Example 1.
[0045]
Comparative Example 2
In Comparative Example 1, a flat encapsulated deodorizing sheet was produced by the same method as Comparative Example 1 except that the substrate A of Preparation Example 4 was used instead of the commercially available electret filter as a HEPA filter. This was used as the flat encapsulated deodorizing sheet of Comparative Example 2.
[0046]
Comparative Example 3
In Comparative Example 1, a flat encapsulated deodorizing sheet was produced in the same manner as Comparative Example 1 except that the substrate A ′ carrying the antibacterial agent of Preparation Example 5 was used instead of the commercially available electret filter. This was used as the flat encapsulated deodorizing sheet of Comparative Example 3.
[0047]
As described above, the flat encapsulated deodorizing sheets obtained in Examples and Comparative Examples were subjected to a powder falling test and a pleating process test by the following methods, and the results are shown in Table 1.
[0048]
[Powder falling test]
The flat encapsulated deodorizing sheets of Examples and Comparative Examples were cut to a size of 25 cm square. Ten flat encapsulated deodorizing sheets cut to 25 cm square were stacked and shaken vigorously in the box for 5 minutes. The deodorizer that fell in the box was collected and weighed. Since there is no possibility of powder falling off, 10 mg or less was excellent under this measurement condition, 20 mg or less was heavier than 10 mg, 50 mg or less was heavier than 20 mg, and the case of exceeding 50 mg was evaluated as inferior.
[0049]
[Pleated folding test]
The flat encapsulated deodorizing sheets of Examples and Comparative Examples were pleated at a pitch of 25 cm. In the state where 100 mountains were folded, it was spread again and returned to a flat shape, and the state of the front and back of the folded surface was confirmed. Under these measurement conditions, the case where there was no fracture portion such as the internal deodorant protruding on the folded surface was evaluated as excellent, and the number of 1 or more and 10 or less was evaluated, and the case of more than 10 was evaluated as inferior. Of course, if there is such a broken part, there is a risk that the deodorizer will drop off, and there will be a problem that the dust removal performance is lowered due to air leakage.
[0050]
[Dust removal performance]
Using a filter element obtained by pleat-folding a flat encapsulated deodorizing sheet, the dust removing performance was compared with the dust removing performance of a filter element consisting only of the original base material sheet not containing a deodorizing agent. The dust removal performance was compared by calculating the removal rate from the number of upstream and downstream atmospheric dust (0.3 to 0.5 μmφ) at a linear wind speed of 10 cm / second measured using a particle counter. It is superior to the removal rate of the filter element consisting only of the original base material not containing the deodorant, and in the case of a removal rate of 98% or more in comparison, 90% or more and less than 98% is possible. Less than 90% was regarded as impossible.
[0051]
[Adhesion test]
The flat encapsulated deodorizing sheets of Examples and Comparative Examples were cut into 25 cm squares, and the base material A and base material B were peeled from the edge surfaces to determine the adhesiveness. Adhesiveness is excellent because it is difficult to peel off when the peel strength between the substrates A and B measured with Tensilon is 100 gf / 25 mm or more. The case where the adhesiveness was larger than 50 gf / 25 mm and smaller than 100 gf / 25 mm was considered as poor, and the case where it was smaller than 50 gf / 25 mm was considered as poor.
[0052]
[Table 1]
[0053]
From the results in Table 1, the flat encapsulated deodorizing sheet of the example has a very high powder fall prevention performance compared with the flat encapsulated deodorizing sheet of the comparative example using the same base material, and there is no breakage. It was found that the deodorizing agent did not fall off from the cross section and the dust removal performance was good.
[0054]
【The invention's effect】
According to the present invention, in a flat encapsulated deodorizing sheet in which a deodorizing agent is encapsulated in two base sheet sheets, the internal deodorizing agent does not fall off from the cut surface or the folded surface, and is a flat surface with improved powder removal properties. A pleated folded air purification filter comprising a sealed encapsulated deodorizing sheet can be provided.
Claims (3)
(1)基材を走行させた状態で一定間隔でホッパーからの脱臭剤の落下を継続及び中断する方法、
(2)グラビアロールなどの凹部を有するロールに規則的に凹部を設けない場所を作って脱臭剤を規則的に基材上に供給する方法、
(1)、(2)のいずれかの方法・手段により、脱臭シートの内側の面に一定間隔ごとに脱臭剤が配置されるとともに脱臭剤が配置されない領域を設けた事を特徴とする平面状封入脱臭シートからなるプリーツ折り空気清浄化フィルター。In the planar encapsulated deodorizing sheet composed of the base material A and the base material B and the deodorizing agent enclosed therebetween, the base material A and the base material B are any of a nonwoven fabric, an electret filter, and a HEPA filter,
(1) A method of continuing and interrupting the dropping of the deodorant from the hopper at regular intervals while the substrate is running,
(2) A method of regularly supplying a deodorizing agent on a base material by creating a place where a concave portion is not provided on a roll having a concave portion such as a gravure roll,
(1) By the method or means of (2), a planar shape characterized in that a deodorizing agent is disposed at regular intervals on the inner surface of the deodorizing sheet and a region where the deodorizing agent is not disposed is provided. Pleated folded air purification filter consisting of an enclosed deodorizing sheet.
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JP2000235412A JP3953717B2 (en) | 2000-08-03 | 2000-08-03 | Pleated fold air purification filter consisting of flat encapsulated deodorizing sheet |
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Cited By (1)
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JP2009179921A (en) * | 2008-02-01 | 2009-08-13 | Taiyo Kagaku Co Ltd | Polymerization type catechin nanofiber |
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US8057567B2 (en) | 2004-11-05 | 2011-11-15 | Donaldson Company, Inc. | Filter medium and breather filter structure |
KR20070085812A (en) * | 2004-11-05 | 2007-08-27 | 도날드슨 캄파니 인코포레이티드 | Filter medium and structure |
JP6257547B2 (en) * | 2015-03-17 | 2018-01-10 | 三菱製紙株式会社 | Deodorant-filled filter media |
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JP2009179921A (en) * | 2008-02-01 | 2009-08-13 | Taiyo Kagaku Co Ltd | Polymerization type catechin nanofiber |
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