JP2004270064A - Structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain functional structure in which a technique of easy water removal required for forming a sheet comprising a bacterial cellulosic substance, especially a cellulosic substance as a main component produced by acetic acid bacteria is searched and the characteristics of the cellulosic substance produced by a bacterium is exhibited to maximum. <P>SOLUTION: The sheetlike structure comprises a cellulosic minute fibrillable substance produced by a bacterium and a hydrophilic solvent and/or a hydrophobic solvent. The cellulosic minute fibrillable substance is produced by a bacterium belonging to the genus Enterobacter or Kluyvera and is independent bodies or connected bodies constituting a macrofibril radially from a central section. In the sheetlike structure, the independent bodies or the connected bodies are connected mutually in microfibril in a circular pore state described in phase separation structure. Another material is arranged on at least one side of the sheetlike structure and both the material and the sheetlike structure are integrated to give bonded structure. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００２５】
【実施例３】
〈他材料との接合その１〉
実施例２−１〜２シート（親水性媒体（水）／疎水性媒体（トルエン）含有）と実施例１−１〜２シート（親水性媒体（水分）含有シート）に対し、三菱エンジニアリングプラステック社製、芳香族共重合ポリアミドＰＡ（ＮｏｖａｍｉｄＸ２１）、エーアンドエム社製ポリスチレンＰＳ（ＧＰ６８５）、旭化成社製ポリオキシメチレンＰＯＭ、東レ社製ポリブチレンテレフタレートＰＢＴ（トレコン）を、表２（他材料はＰＡ、ＰＳ、ＰＢＴ、ＰＯＭと略記）の所定温度（圧力１．８２ＭＰｓ）で熱圧着させた。
次いで、各々の接合構造体の接着性をピーリング性試験で判定した。
なお、ピーリング性試験は、ＪＩＳ Ｃ６４８１（引きはがし強さ）で行い、判定は、◎（優秀）、○（良好）、△（やや弱い）、×（剥がれる）とした。
【００２６】
【比較例３】
〈他材料との接合その１〉
実施例２−１〜２シート、実施例１−１〜２シートに代えて、それらの絶乾シートである比較例２−１〜２シート、比較例１−１〜２シート（表１）を使用した以外は実施例３と同様にして他材料と熱圧着させた。
次いで、各々の接合構造体の接着性を同上ピーリング性試験で判定した。
実施例３と比較例３のピーリング性試験の判定結果を表２に示した。
表２から明らかなように、親水性ポリマー（ＰＯＭ）は、水分が残留しているシート（実施例１−１〜２シート）との接合性が良好で、疎水性ポリマー（ＰＳ、ＰＢＴ）は疎水性媒体が残留しているシート（実施例２−１〜２シート）と良好な接着性を示した。
ＰＡでは、芳香族が共重合されており、いずれの場合も、ほぼ良好な結果を得た。
【００２７】
【表２】

【００２８】
【実施例４】
〈他材料との接合その２〉
実施例２−１スラリー（水、トルエン含有）４０ｗｔ％と、別途作成した平均繊維径１μｍのアラミドパルプ（東レ・デュポン社製、シート材料）の０．０５ｗｔ％分散液６０ｗｔ％を混合分散し、これを、通常の抄造装置で、Ａ４版（約２１×３０ｃｍ）のシートを作成し、風乾した。風乾後のシートの水分率は約２０％、トルエン含有率１０％であった。
このシートに、実施例３で使用したＰＡを、１３０℃、１．８２ＭＰａで熱圧着した。
この接合構造体のピーリング性試験をしたところ、剥がれなく、評価は表２に準拠すると◎であった。
【比較例４】
〈他材料との接合その２〉
実施例４の風乾後のシートに代えて、それを熱風乾燥した絶乾シートを使用した以外は実施例４と同様にしてＰＡと熱圧着させた。その接合構造体のピーリング性試験をしたところ、剥離する部分が多数存在し、評価は表２に準拠すると×であった。
【００２９】
【実施例５】
〈電子材料基板〉
実施例２−１〜２シート（親水性媒体（水）／疎水性媒体（トルエン）含有）に、再度トルエンを噴霧した後、このシートにメチルエチルケトンに溶解したエポキシ樹脂（アミン系触媒含有）を含浸し、余剰分をロール操作で除去した。
次いで、これを風乾、予備乾燥後、シートの両面に、銅箔（古河サーキットフォイル社製、厚さ；１０μｍ）を１８０℃、２ＭＰａ条件で１時間、熱圧着して、電子材料基板用銅箔シートを得た。
次いで、この銅箔シートの切片を電子顕微鏡観察した結果、エポキシ樹脂が、きわめて均一にセルロース内表面に入っていた。
また、この銅箔シートの１５０℃での熱処理で収縮は７ｐｐｍ以下であり、電子材料の配線基板として良好であった。エポキシ樹脂の代わりに、イソシアネート系樹脂、ヒンダードフェノール系樹脂を使用しても、同様の結果が得られた。
【比較例５】
〈電子材料基板〉
実施例２−１〜２シート（親水性媒体（水）／疎水性媒体（トルエン）含有）に代えて、実施例１−１〜２シート（親水性媒体（水分）含有シート）を用いた以外は、実施例５と同様に操作し、電子材料基板用銅箔シートを得た。
得られた銅箔シートには、所々、セルロースとエポキシ樹脂間にボイド状の剥離が有った。
【００３０】
【実施例６】
〈酸素濃縮用構造体〉
実施例２−１スラリー（水、トルエン含有）８５ｗｔ％と、平均繊維径０．１８μｍのポリエステル微細繊維（旭化成社製）の０．０５ｗｔ％水分散液１５ｗｔ％を混合分散し、これを、通常の抄造装置で、Ａ４版（約２１ｘ３０ｃｍ）のシートを作成し、風乾した。風乾後のシートの水分率は約２０％、トルエン含有率１０％であった。このシートの通気性をＫＥＳ方式で測定したところ、３−４ＫＰａ ／ｓ・ｍであった。
このシートを、ポリオキシメチルシランの５ｗｔ％トルエン溶液１０００ｇに１０ｇの水を加えよく混合して調製した、極めてわずかに白化した半透明状原液にデイップし、その後一定圧のロールで余剰ポリマー溶液を除去後、風乾、熱乾燥させシート状構造体を得た。
そして、このシート状構造体を小円状に切り出し、その１０枚を重ね合わせ、軽く圧をかけて平坦化し、ミリポア社製円筒ろ過装置に装着後、空気を流し、酸素、窒素の溶解拡散による透過性（Ｐ：ｃｍ^３ ・ｃｍ／ｃｍ^２ ・ｓ・Ｐａ）を評価した。
通常可塑剤・フィラーを１０ｗｔ％含むポリオキシメチレン膜の酸素、窒素に対する透過性（Ｐ：ｃｍ^３ ・ｃｍ／ｃｍ^２ ・ｓ・Ｐａ））はそれぞれ、３６７、１７０であるが、実施例６のシート状構造体では、分離効率は低下するものの、透過性（Ｐ：ｃｍ^３ ・ｃｍ／ｃｍ^２ ・ｓ・Ｐａ））はそれぞれ、７２０、４００であった。
【比較例６】
〈酸素濃縮用構造体〉
実施例６のシート状構造体に代えて、それを熱風乾燥して殆ど溶媒を除去して調製したシート状構造体を用いる以外は実施例６と同様に行った。
このシート状構造体の通気性をＫＥＳ方式で測定したところ、６−７ＫＰａ ／ｓ・ｍであり、圧力を高くしないと、空気は流れにくかった。
【００３１】
【実施例７】
〈インク吸収用または湿度自己調節用構造体〉
実施例２−１シート（水／トルエン含有）と実施例１−１シート（水含有）に、特願２００１−１２７６９９号明細書に記載の方法に従って調製した透明なナノポーラスシリカ水ゲル（シリカ濃度；３０％）を、ドクターナイフ（１μｍ厚）で、コーテイング、風乾後、熱風乾燥した。
得られたシート状構造体はいずれも均一なシートで、特に、前者は、フレキシビリテイ性が良好であった。
得られたシート状構造体は、インクなどの吸収性（速度、量とも）が良好で、インクジェット印刷に好適であった。
また、得られたシート状構造体は、湿度／温度環境の違いで、吸放湿する性質があった。さらに、触媒を担持する材料としても好適であった。
【比較例７】
〈インク吸収用または湿度自己調節用構造体〉
実施例２−１シート（水／トルエン含有）と実施例１−１シート（水含有）に代えて、前出の比較例１−１シート（実施例１−１シートの絶乾シート）を用いる以外は実施例７と同様に行った。
得られたシート状構造体は、シリカポリマーが硬く、剥離が目立った。
【００３２】
【実施例８】
〈光触媒用構造体〉
実施例２−１シート（水／トルエン含有）と実施例１−１シート（水含有）に、微量の燐酸を含むアルコキシチタンの１５％ブタンール／エタノール混合液を含浸させ、徐々に、乾燥、熱乾燥した。
得られたシート状構造体はいずれも均一なシートで、特に、前者は、フレキシビリテイ性が良好であった。これらは３３０ｎｍの光で触媒作用を有していた。
【比較例８】
〈光触媒用構造体〉
実施例２−１シート（水／トルエン含有）と実施例１−１シート（水含有）に代えて、前出の比較例１−１シート（実施例１−１シートの絶乾シート）を用いる以外は実施例８と同様に行った。
得られたシート状構造体は、チタンが硬く、剥離が目立った。
【００３３】
【実施例９】
〈オプトエレクトロニクス用構造体〉
実施例２−１シート（水／トルエン含有）と実施例１−１シート（水含有）に、微量の酢酸を含むバリウムとチタンのアルコキシド３０％を含むブタンール／エタノール混合液を含浸し、徐々に、乾燥、９０℃にて熱乾燥した。
得られたシート状構造体は、やや褐色だが透明なチタン酸バリウムが均一に配されたシートで、特に、前者は、フレキシビリテイ性が良好であった。
得られたシート状構造体は、チタン酸バリウムの強誘電体作用、微生物産生セルロース（フィブリル径は、５０ｎｍと小さい）の高透明性を有することから、機械強度のあるオプトエレクトロニックス素材として有用である。
【比較例９】
〈オプトエレクトロニクス用構造体〉
実施例２−１シート（水／トルエン含有）と実施例１−１シート（水含有）に代えて、前出の比較例１−１シート（実施例１−１シートの絶乾シート）を用いる以外は実施例９と同様に行った。
得られたシート状構造体は、チタン酸バリウムを微生物セルロース上に、見かけ上コーテイングしたような形態だが、ひび割れた表面となった。
【００３４】
【実施例１０】
〈ＨＥＰＡフィルター用構造体〉
実施例１−１スラリー３０ｗｔ％と、実施例６で使用した、平均繊維径０．１８μｍのポリエステル微細繊維の０．０５ｗｔ％水分散液７０ｗｔ％とを混合分散し、これを、通常の抄造装置で、Ａ４版（約２１ｘ３０ｃｍ）の厚さ約３ｍｍのシート状物を作成し、風乾した。
風乾後のシートの水分率は約３０％であった。
得られたシート状構造体の通気性をＫＥＳ方式で、測定したところ、１−１．５ＫＰａ ／ｓ・ｍであった。
得られたシート状構造体に対し、脱アセチル化度４２％のキトサン酸性溶液（キトサン濃度１ｗｔ％、溶媒０．６Ｎ塩酸水溶液）を含浸させロールで簡単に絞り、急激に熱風乾燥操作後、苛性ソーダ水溶液にて、中和後、風乾、熱乾燥させた。次いで、このシートをＨＥＰＡフィルターとして装着した除塵装置を用い、０．０３５μｍの塵を発生させた空気の塵捕集率を求めたところ、９９．９９％であったが、圧損がより小さく、通気量が稼げる結果となった。
また、上記ＨＥＰＡフィルター用シート状構造体を用いて、微生物を扱う部屋に存在する空気を通過させた。この通過空気と元の空気の存在下に、普通寒天培地にて、細菌の検出を行った結果、元の空気では細菌が検出されたが、通過空気では、生菌の検出は、大きく減じた。
【００３５】
【比較例１０】
〈ＨＥＰＡフィルター用構造体〉
実施例８の絶乾シート（ＫＥＳ方式での通気性：３−４ＫＰａ ／ｓ・ｍ）に対し、実施例１０と同様に、脱アセチル化度４２％のキトサン酸性溶液（キトサン濃度１ｗｔ％、溶媒０．６Ｎ塩酸水溶液）を含浸させロールで簡単に絞り、急激に熱風乾燥操作後、苛性ソーダ水溶液にて、中和後、風乾、熱乾燥させた。次いで、このシートをＨＥＰＡフィルターとして装着した除塵装置を用い、０．０３５μｍの塵を発生させた空気の塵捕集率を求めたところ、実施例１０と同様９９．９９％であったが、圧損がより大きかった。
【００３６】
【実施例１１】
〈研磨用構造体、インク吸収用構造体、同左用塗装液〉
実施例１−１で得たセルロース固形濃度１０％の水含有体１００ｇを、水で５倍に希釈、強分散し、セルロース固形濃度２ｗｔ％の水分散体を得た。これに対し、分散操作をしながら、シクロヘキサン５０ｇを、徐々に加え、乳白でやや透明性のあるスラリーを得た。
このスラリーを水で希釈、分散し、セルロース固形濃度０．０５ｗｔ％のスラリーを得た。
このスラリー中のセルロース２５重量部に対し、γ−アルミナ（研磨用）７２重量部、ＳＢラテックス３重量部（固形換算）を加え、分散させ抄造用スラリーた。
この抄造用スラリーを、通常の抄造装置で、Ａ４版（約２１×３０ｃｍ）の厚さ約３ｍｍのシート状構造物を作成した。
得られたシート状構造物の抄造過程でのアルミナ補足率は、９７％であった。
また、得られたシート状構造物は、フレキシビリテイが高かった。
そして、得られたシート状構造物でスリガラスを磨くことにより、スリガラスが透明になり、インク吸収性も良好であった。
さらに、上記抄造用スラリーはそのまま、塗装液としても有用である。
加えて、得られたシート状構造物の上に、同様のシクロヘキサン含有セルロース分散液（ただし、セルロース／アルミナ／ＳＢラテックス＝３０／６７／３、重量比）を抄造後、風乾、熱乾燥、真空乾燥を繰り返したが、水は抜けるものの、シクロヘキサンは３％程度残留していた。このシートは水中での寸法安定性は良好であった。
【００３７】
【比較例１１】
〈研磨用構造体、インク吸収用構造体、同左用塗装液〉
実施例１１のセルロース固形濃度２ｗｔ％の水分散体に、シクロヘキサンを加えない以外は実施例１１と同様の操作をし、厚さ３ｍｍのシート状構造物を得た。得られたシート状構造物の抄造過程でのアルミナ補足率は９０％で、フレキシビリテイは実施例１１のシート状構造物より低かった。
さらに、得られたシート状構造物に同組成の分散液（シクロヘキサンを含まず）を抄造後、風乾、熱乾燥、真空乾燥を繰返えしたシートは、高度に硬いが、水中での寸法安定性は、若干劣っていた。
以上の実施例１１及び比較例１１から明らかなように、水と疎水性溶媒の共存下の方が、親水性の無機酸化物の均一分散性が良好なのは、水が微生物セルロースの水素結合面を開き、かつ、それに垂直方向に当たる疎水面を疎水性溶媒が、開いている結果、スムースな分散が実現（以後の実施例の無機物含浸系においては、この効果を基本としている。）されることによるものと思われる。（なお、このことは、実施例２に記載の比表面積の増大現象とは、パラレルな関係にある。）
【００３８】
【実施例１２】
〈光触媒用構造体〉
実施例１１のセルロース固形濃度０．０５ｗｔ％のスラリー（シクロヘキサン含有）中のセルロース４０重量部に対し、アナターゼ型酸化チタン（粒径５μｍ以下）５７重量部、ＳＢラテックス３重量部（固形換算）を加え、分散させ、塗装・含浸用スラリーを得た。
このスラリーを用い、市販のガラス繊維製ＨＥＰＡ（厚み１．５ｍｍ）フィルタ−に、０．１ｍｍ厚みで、積層後、乾燥させた。
得られたシートの積層抄造過程での、酸化チタン補足率は、実施例で９８％であった。
光触媒効果の促進判定として、得られたシート（改質ＨＥＰＡフィルタ）に、３３０ｎｍのＵＶを照射しつつ、塵と細菌を含む空気を流しつづけた。
【比較例１２】
〈光触媒用構造体〉
実施例１１の塗装・含浸用スラリーにおいて、シクロヘキサンを加えないで塗装・含浸用スラリーを調製した。このスラリーを用い、市販のガラス繊維製ＨＥＰＡ（厚み１．５ｍｍ）フィルタ−に、０．１ｍｍ厚みで、積層後、乾燥させた。
得られたシートの積層抄造過程での、酸化チタン補足率は、実施例で９２％であった。
光触媒効果の促進判定においては、実施例１２よりも、比較例１２の場合が汚染が若干早かった。
【００３９】
【実施例１３】
実施例２−１（水／トルエン含有）シートに、０．１ｗｔ％の熱硬化型液状フェノール樹脂（カネボウ社製）をトルエンに分散させ、これに１０倍容の水を徐々に加えて分散させたものを、ローラーにて含浸した。こうして得られたフェノール樹脂含浸シートを、乾燥後、１００℃で１時間加温したところ、シートの形状に変化は認められず平板状を保った。
得られたフェノール樹脂を含浸したシートは、熱変形温度が２４０℃というフェノール樹脂の特性を付与することができ、コンデンサー用などの絶縁材料に適した構造体となり得る。
【比較例１３】
実施例１−１シート（水含有）に、実施例１３と同様にフェノール樹脂を含浸し、乾燥、加温処理した。
得られたシートは、フェノール樹脂の含浸が不安定で、乾燥時の収縮の違いから片面に反りのある形状になった。
【００４０】
【実施例１４】
実施例１１のセルロース固形濃度０．０５ｗｔ％のスラリー（シクロヘキサン含有）６０ｗｔ％と、平均繊維径１μｍのポリプロピレン短繊維（三菱レイヨン社製）の０．０５ｗｔ％分散液４０ｗｔ％を混合分散し、これを、通常の抄造装置で、Ａ４版（約２１×３０ｃｍ）、厚さ約２ｍｍのシート（水３０％、シクロヘキサン１５％残留）作成した。
このシートの上に、先に作成したセルロース／ポリプロピレン分散液（全繊維濃度０．０５ｗｔ％）に、対繊維３０ｗｔ％の粉末活性炭を混合分散した分散液を、厚さ約２ｍｍで積層抄造し、風乾しシート状構造体を得た。
このシート状構造体に対し、２０ｐｐｍのクロロホルムを含む水を、通過させ、通過水中の、クロロホルム量を、ガスクロマトグラフィーにて測定した。測定結果は、ｐｐｂレベルであった。
【００４１】
【比較例１４】
シクロヘキサンを含有させない以外は、実施例１４と同様に操作をして、同組成、同構造（セルロース／ポリプロピレンシート上に、セルロース／ポリプロピレン／活性炭シートを積層）のシート状構造体を得た。
このシート状構造体に対し、２０ｐｐｍのクロロホルムを含む水を、実施例１４と同速度で通過させ、通過水中のクロロホルム量を、ガスクロマトグラフィーにて測定した。測定結果は、６ｐｐｍ以上であった。
この実施例１４と比較例１４との差異は、シクロヘキサンを含むシートは、水のみを含むシートに比し、実施例２で記載した様に、セルロースの比表面積が大きいことと、シクロヘキサンの一時的な存在が、セルロースの面配向を阻害し、ハロゲンなどの非水系溶媒を取り込む能力が向上していることに起因していると思われる。
また、ハロゲン含有水を同じ速度で通過させる場合の圧損は、実施例１４の方が比較例１４より相当小さく、大量処理にも有効であることが判明した。
【００４２】
【実施例１５】
実施例１−１で得たセルロース固形濃度１０％の水含有体を、水で希釈、分散し、セルロース固形濃度０．０５ｗｔ％の水分散体を得た。
他方、平均繊維径０．１８μｍのポリエステル微細繊維（旭化成社製）の０．０５ｗｔ％水分散液を作成した。
次いで、上記セルロース水分散体５０ｗｔ％とポリエステル繊維水分散体５０ｗｔ％を混合分散し、これから通常の抄造装置を用いて、Ａ４版（約２１ｘ３０ｃｍ）の厚さ約３ｍｍ、水分率２０ｗｔ％（対セルロース４０ｗｔ％）のシート状物を作成した（第１工程）。
このシートに脱アセチル化度４２％のキトサン酸性溶液（キトサン濃度１ｗｔ％、溶媒０．６Ｎ塩酸水溶液）を含浸させ、ロールで簡単に絞った後、急激に熱風乾燥し、苛性ソーダ水溶液にて中和し、風乾させて、水分率２０ｗｔ％のシートを得た（第２工程）。
このキトサン含浸シートを、０．１％の酸化銅の希酸溶液に含浸させ、ローラーで絞り乾燥して、キトサン／イオン化酸化銅含浸シートを作成した（第３工程）。シートは、全体に極薄の青色を示した。
得られたシートに対し、殺菌灯で紫外線を照射しながら、重油燃焼排煙を通過させ、排煙中の酸化窒素ＮＯ_Ｘ を定法（ガスクロマトグラフィー法）により測定した。上記シート通過前のＮＯ_Ｘ は９００ｐｐｍ、通過後ではｐｐｂレベルであった。
得られたシートにおいて、酸化銅の代わりに水酸化亜鉛水溶液を用いれば、ＳＯ_Ｘ 吸着にも有効である。
また、実施例１５の微生物産生セルロース／キトサン構造体は、銅、亜鉛以外に、パラヂウム、白金、ルテニウムなど他の金属を担持させ得るので、不斉水添反応などの金属触媒用構造体ともなり得る。
【００４３】
【比較例１５】
実施例１５の第１〜３工程で、水分の殆どないシート状物（セルロース／ポリエステル繊維含有）を用いて、実施例１５と同様に操作し、キトサン／イオン化酸化銅含浸シートを作成した。シートは、青色はまだらであった。
得られたシートを用い、実施例１５と同様に測定したＮＯ_Ｘ は１００ｐｐｍ程度であった。
実施例１５と比較例１５の効果の差異は、実施例１５が、すべて水分存在下に、キトサン、銅イオンを、含浸させており、セルロース／キトサンが比較的一に分散・吸着され、銅イオンもキトサンのＮ−アセチル基、および、微生物産生セルロースのＣ２、Ｃ３位のＯＨ基へ均一に配位したため、効率的な触媒作用が実現されたと考えられる。
【００４４】
【実施例１６】
実施例１−１で得たセルロース固形濃度１０％の水含有体１００ｇを、水で５倍に希釈、強分散し、セルロース固形濃度２ｗｔ％の水分散体を得た。
これに対し、分散操作をしながら、シクロヘキサン５０ｇを、徐々に加え、乳白でやや透明性のある水分散体を得た。
次いで、この水分散体を水で希釈、分散し、セルロース固形濃度０．０５ｗｔ％の水分散体を調製し、この水分散体から通常の抄造装置を用いて、Ａ４版（約２１ｘ３０ｃｍ）の厚さ約１ｍｍ、水分率約３０ｗｔ％、シクロヘキサン含有率約１５ｗｔ％のシート状物を得た（第１工程）。
他方、上記の操作法に従って、水の希釈率を変えて調製したシクロヘキサン含有、セルロース固形濃度１ｗｔ％水分散体２５重量部に対し、炭酸バリウム固形濃度１ｗｔ％水分散体７２重量部、ＳＢラテックス固形濃度１ｗｔ％水分散体３重量部を加え、ブレンダーで分散させ粘性状物を得た。
これを、上記第１工程て作成したシート状物の両面に、コーテイングし、一定厚みとなるようにローラー操作を行い、風乾し、厚さ約３ｍｍのシート状物を作成し、続いてこれを熱風乾燥して、炭酸バリウム含有積層構造体を得た。
この積層構造体は、基材のセルロースシートとの接合強度が確保された積層構造体であり、既存の方法で電気容量を測定した結果、２ｎＦ の電気容量を示した。
また、この積層構造体の２００℃での線膨張率は基材のセルロースシートと同意程度の数ｐｐｍと低く、寸法安定性があった。これは、基材セルロースシートに残存するシクロヘキサン及び水と、コーテイング材にも存在するシクロヘキサン及び水の影響で、コーテイング材に存在するラテックス粒子の一部がセルロース基材へ拡散し、基材とコーテイング材のセルロース繊維間の絡み合いが促進された結果といえる。
上記炭酸バリウムに代えて、他の無機物、例えば、酸化亜鉛、ルチル形酸化チタン、クレー、炭酸カルシウム、炭酸マグネシウム、カオリン、石膏、珪酸カルシウムなどの難溶性無機物も採用でき、機械強度を維持した機能性積層構造体を提供できる。
勿論、出来た構造体を更に、二次的に、実施例８や１２の様に、機能補填できる。
【００４５】
【比較例１６】
実施例１６の第１工程において、一切シクロヘキサンを使用せず、かつ、水分も殆ど含まないセルロース繊維シートを調製した。
また、コーティング材用粘性状物の調製においても一切シクロヘキサンを使用しかった。
以上のこと以外は、実施例１６と同様に操作し、炭酸バリウム含有積層構造体を得た。
得られた積層構造体は、基材とコーテイング材の接合が不調で、一体の構造体とはならなかった。
【実施例１７】
実施例１−１で得たセルロース固形濃度１０％の水含有体１００ｇを、水で５倍に希釈、強分散し、セルロース固形濃度２ｗｔ％の水分散体を得た。
これに対し、分散操作をしながら、シクロヘキサン５０ｇを、徐々に加え、乳白でやや透明性のある水分散体を得た。
次いで、この水分散体を水で希釈、分散し、セルロース固形濃度０．０５ｗｔ％の水分散体を得た。
続いて、この水分散体中のセルロース２５重量部に対し、酸化ジルコニウム７２重量部、ＳＢラテックス３重量部（固形換算）を加え、分散させた。
この水分散体から通常の抄造装置で、Ａ４版（約２１ｘ３０ｃｍ）の厚さ約３ｍｍのシート状物を作成した。
このようにして得られた酸化ジルコニウム含有シート状物を乾燥後、その片面を２００℃に加熱し、該シート状物の反対側の表面温度を測定した結果、該表面温度は変化しなかった。
実施例１７の酸化ジルコニウム含有シートは、酸化ジルコニウムの低熱伝性が付与され、低熱伝体としての構造体となり得る。
酸化ジルコニウムに代えて、他の無機物、例えば、酸化亜鉛、ルチル形酸化チタン、クレー、炭酸カルシウム、炭酸マグネシウム、カオリン、石膏、珪酸カルシウムなどの難溶性無機物をも採用でき、機械強度を維持した機能性積層構造体を提供できる。
勿論、得られたシート状物を更に、二次的に、実施例８や１２の様に、機能補填できる。
【００４６】
【比較例１７】
シクロヘキサンを加えない以外は実施例１７と同様に操作して酸化ジルコニウム含有シート状物を得た。
このようにして得られた酸化ジルコニウム含有シート状物を乾燥後、その片面を２００℃に加熱し、該シート状物の反対側の表面温度を測定した結果、該表面温度は７０℃まで上昇した。
【実施例１８】
実施例１−１で得たセルロース固形濃度１０％の水含有体１００ｇを、水で５倍に希釈、強分散し、セルロース固形濃度２ｗｔ％の水分散体を得た。
これに対し、分散操作をしながら、シクロヘキサン５０ｇを、徐々に加え、乳白でやや透明性のある水分散体を得た。
次いで、この水分散体を水で希釈、分散し、セルロース固形濃度０．０５ｗｔ％の水分散体を得た。
この水分散体中のセルロース２５重量部に対し、酸化亜鉛７２重量部、ＳＢラテックス３重量部（固形換算）を加え、分散させた。
この水分散体より通常の抄造装置で、Ａ４版（約２１ｘ３０ｃｍ）の厚さ約３ｍｍのシート状物を作成した（第１工程）。
このようにして得られたシートを風乾後、０．１％のルテノセン色素溶液に０．００５％のＳＢラテックスを分散させたものをローラーにより含浸させた。
この含浸シートを乾燥後、太陽光を照射し、発生する電流を測定した。その結果、毎秒４００ｍＡの電流が発生した。
このことは、実施例１−１から得られた比表面積の大きいセルロースシートは、ローラー操作で、ルテノセン色素の光増感性と亜鉛の感光性が付与され、感光体基材としての構造体となり得ることを示している。
【００４７】
【比較例１８】
実施例１８の第１工程において、絶乾した状態としてセルロース繊維シートを調製した。
以上のこと以外は、実施例１８と同様に操作し、亜鉛／ルテノセン色素含有シートを得た。
得られたシートは、電流の発生は毎秒２００ｍＡであった。
【実施例１９】
実施例２で得た風乾したＡ４版（約２１×３０ｃｍ）トルエン含有シート（実施例２−１シート）に、１ｇのγ−フェライトを１０ｍｌの３０％ニトロセルロース溶液（窒素含量１０．９〜１１．２％；イソプロピルアルコール溶液）に分散したものをスプレーコーティングした。
得られたγ−フェライトをコーティングしたシートは、γ−フェライトがむらなく一様にコーティングされ、ピーリングテストで剥がれなかった。
このγ−フェライトをコーティングしたシートは良好な強磁性体としての構造体となり得る。
【００４８】
【比較例１９】
実施例２で得た風乾したＡ４版（約２１×３０ｃｍ）トルエン含有シート（実施例２−１シート）を絶乾したシートに、実施例１９と同様にγ−フェライトをコーティングした。
得られたγ−フェライトをコーティングしたシートは、コーティングにむらがあり、多くの部分で剥がれた。
【実施例２０】
実施例２で得た風乾したＡ４版（約２１×３０ｃｍ）トルエン含有シート（実施例２−１シート）に、１％の酸化コバルト水溶液に１％（ｗ／ｖ）の液状シリコーンを徐々に加えて分散させ、さらに１／１０容のトルエンを加えて分散させたものをローラーにて含浸した。
このようにして得られた酸化コバルト含浸シートを、乾燥後、電気容量を測定した結果、１０ｐＦの電気容量が認められた。
この酸化コバルト含浸シートは、酸化コバルトの低電気伝導性が付与され、低電気伝導体としての構造体となり得る。
【００４９】
【比較例２０】
実施例２で得た風乾したＡ４版（約２１×３０ｃｍ）トルエン含有シート（実施例２−１シート）を絶乾したシートを、実施例２０と同様に処理して酸化コバルト含浸シートを得た。
得られた酸化コバルト含浸シートでは電気容量は５０ｐＦであった。
【実施例２１】
シアノエチル化ヒロドキシエチルセルロース（ＣＥＨＥＣ）を、Ｊｏｕｎａｌｏｆ Ｗｏｏｄ Ｓｃｉｅｎｃｅ，４４：３５−３９（１９９８）記載の方法により合成した。
その０．５ｗｔ％のアセトン溶液に、水を徐々に濁り点近傍まで加え、さらにＣＥＨＥＣと同量のチタン酸バリウムを加えて分散させた。
この分散液を、実施例２で得た風乾したＡ４版（約２１×３０ｃｍ）トルエン含有シート（実施例２−１シート）に含浸し、ローラー圧搾し、風乾、乾燥した後、１２０℃で熱圧着処理した。堅固で、熱安定性の良いシート状構造体が得られた。
上記構造体は、ＣＥＨＥＣの持つ最高レベルの圧電係数（ｄ_２５＝１０^−１１ Ｃ／Ｎ）とチタン酸バリウムの持つ１２００Ｆ／ｍという高い誘電率が付与されるとともに、微生物産生セルロースの持つ面配向構造（構造異方性）との相乗効果により、例えば、動的電気トランスデューサーなどの高誘電材用構造体となり得る。
【比較例２１】
実施例２−１シートから溶媒を殆ど除去したシートに対し、実施例２１と同様の処理加工を加えてシート状構造体を得た。
このシート状構造体は、熱圧着処理時、接合不良部が散見された。
【００５０】
【発明の効果】
本発明によれば、特殊な微生物産生セルロース系物質が提供されるとともに、該セルロース系物質と他材料との接合・分散等の加工条件が確立され、かつ、相乗効果の期待できる機能構造体が提供され、これにより、従来の微生物産生セルロースが達し得なかった、新たな工業的価値を付加することに成功した。
【図面の簡単な説明】
【図１】本発明のセルロース系物質の光学顕微鏡写真。
【図２】本発明のセルロース系物質の走査型電子顕微鏡写真。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention solves the problem of high energy consumption due to high water content (for example, the problem of consuming a large amount of energy for disaggregation, dehydration, and drying) required to produce a sheet-like material of a microbial cellulosic material. And a technology for providing a microorganism-producing cellulosic material having an appropriate and novel morphology for the purpose of disclosing a highly functional technology that is truly industrially acceptable.
[0002]
[Prior art]
Conventionally, cellulosic substances produced by microorganisms, especially acetic acid bacteria, are well known as a food material “Nata de coco”. As other industrial uses, utilizing its characteristic functions, for example, nano-level fibrillation, high water content, high crystallinity, high elasticity, high energy loss, high capacity inorganic material support, high transparency Many uses have been proposed.
For example, an acoustic diaphragm (Patent Document 2), a high mechanical sheet (Patent Document 3), a wound covering material (Patent Document 4), a reinforcing material of polyacetal or rubber (Patent Document 5, Patent Document 6), a living tissue replacement material ( Patent Document 7), food material (Patent Document 8), anti-counterfeit paper (Patent Document 9), transparent transfer paper for electrophotography (Patent Document 10), paper made of colloidal silica / amphoteric starch / pulp / bacterial cellulose (Patent Document 11), a functional sheet containing 50% or more of fine particles (Patent Document 12), an artificial soil composition (Patent Document 13), a carrier for immobilizing enzymes and microorganisms (Patent Document 14), a filtration membrane (Patent Document 15), activated carbon Materials (Patent Document 16), Concrete Mixture (Patent Document 17), Support for Thermal Recording Paper (Patent Document 18), Filter Containing Activated Carbon (Patent Document 19), Low Density Smooth Paper (Patent Document 20) The thermal transfer-receiving sheet (Patent Document 21), but support for photographic paper (Patent Document 22) have been proposed, they are all the acetic acid bacterium producing microbial cellulose as a starting material. In addition, it can be said that most of the proposed uses other than the acoustic diaphragm are fields in which there is little necessity of being cellulose produced by microorganisms.
[0003]
Furthermore, in addition to the reason that the production cost is high, in many application areas, low wet compressibility derived from its high water content (here, wet compressibility means water leakage when compressed under pressure) Becomes a bottleneck, and a great deal of energy is required for disaggregation, dehydration, and drying in the process of microbial production, and also in the production of paper and sheet materials as secondary products. Process defects such as poor drainage.
In addition, even after the secondary product, in terms of water resistance, it is not much different from celluloses such as pulp and cotton that are usually used, and there is a problem in product stability. At present, solid industrial uses have not been established. For this reason, many attempts have been made to solve the cellulosic substances produced by acetic acid bacteria using a disintegration technique, but at present, no drastic solution has been found.
On the other hand, other characteristics of the cellulosic material derived from microorganisms, such as ultra-low thermal expansion, light weight, barrier properties, high surface hydroxyl group density, controllability of its orientation characteristics, and structures derived from them Applications to high-performance applications utilizing anisotropic properties, adsorbing properties of organic impurities such as halogen, auxiliary properties of optical activity, and the like have not been known.
[0004]
[Patent Document 1]
Japanese Patent No. 2873927
[Patent Document 2]
JP-A-6-233691
[Patent Document 3]
Japanese Patent Publication No. 5-27653
[Patent Document 4]
U.S. Pat. No. 4,588,400
[Patent Document 5]
U.S. Pat. No. 5,086,096
[Patent Document 6]
U.S. Pat. No. 5,290,830
[Patent Document 7]
JP-A-3-165774
[Patent Document 8]
JP-A-3-157402
[Patent Document 9]
JP-A-6-313297
[Patent Document 10]
JP-A-6-250431
[Patent Document 11]
JP-A-6-287888
[Patent Document 12]
JP-A-1-156600
[Patent Document 13]
JP-A-7-298777
[Patent Document 14]
JP-A-8-35155
[Patent Document 15]
JP-A-1-199604
[Patent Document 16]
JP-A-10-94728
[Patent Document 17]
JP-A-5-330888
[Patent Document 18]
JP-A-6-297840
[Patent Document 19]
JP-A-5-237326
[Patent Document 20]
JP-A-6-248594
[Patent Document 21]
JP-A-8-142528
[Patent Document 22]
JP-A-6-242548
[0005]
[Problems to be solved by the invention]
The object of the present invention is to
{Circle around (1)} Searching for a technology that facilitates water drainage required for producing a sheet containing a conventional so-called bacterial cellulosic, particularly a cellulosic substance produced by acetic acid bacteria as a main component,
(2) Searching for a microbial cellulosic substance having a morphology that facilitates water drainage, and
(3) After solving the above problems, establish a technology capable of providing a functional structure capable of maximizing the characteristics of the microbial cellulosic material, especially ultra-low thermal expansion, light weight, barrier properties, and surface properties. An object of the present invention is to create a high-performance application such as a structure utilizing a large hydroxyl group density (adhesiveness) and controllability of its orientation characteristics, for example, an electronic material substrate.
[0006]
[Means for Solving the Problems]
The present inventors have proposed sheet-forming conditions (including selection of materials to be mixed) of microorganism-produced cellulosic materials to solve the above-mentioned problems, and joining conditions after sheeting (polymer materials, metal foils and the like). ) And the special form (independent or connected body that constitutes macrofibrils radially from the central region), and they are connected to each other by microfibrils in a circular pore shape called phase separation. The present invention has been completed by finding a microorganism-produced cellulosic substance having high wet compressibility, low slurry viscosity, and advantageous in bonding with other materials.
[0007]
That is, the present invention has the following configuration.
(1) A sheet-like structure comprising a cellulosic microfibrillar substance produced by a microorganism and a hydrophilic solvent and / or a hydrophobic solvent.
(2) The hydrophilic solvent is water and / or glycols, and the hydrophobic solvent is at least one selected from aromatic hydrocarbons, alicyclic hydrocarbons, and derivatives having these as a skeleton. The sheet-like structure according to the above (1), wherein:
(3) The sheet according to the above (1) or (2), wherein the microbial cellulosic substance produced by the microorganism is a cellulosic microfibrillar substance produced by an acetic acid bacterium (genus Acetobacter). Shaped structure.
(4) The cellulosic microfibrillar substance produced by the microorganism is a cellulosic microfibril substance produced by a microorganism belonging to the genus Enterobacter or the genus Cluvella, wherein the independent substance comprises macrofibrils radially from a central region, Alternatively, the sheet according to the above (1) or (2), wherein the sheet is a connected body, and they are connected to each other by microfibrils in a circular pore shape as referred to by a phase separation structure. Shaped structure.
(5) A method for manufacturing a joined structure, comprising disposing another material on at least one surface of the sheet-like structure according to any one of the above (1) to (4), and integrating them.
(6) A joint structure manufactured by the manufacturing method according to (5).
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The sheet-like structure of the present invention is composed mainly of nano-level microfibrous microbial microorganism-producing cellulose-based material, and, if necessary, is composed of a combination of a polymer fiber, an inorganic fiber, an inorganic filler, and the like, and It is formed into a sheet containing a hydrophilic solvent and / or a hydrophobic solvent.
The sheet-like material is impregnated with a polymer solution or the like, coated, and has a structure in which one surface of the sheet-like material or another material is arranged on both surfaces.For example, a substrate material for an electronic material, a separator for a capacitor, It is used in a wide variety of application areas such as battery separators, oxygen-enriched thin films, catalyst-carrying thin films, abrasive sheets, super-ink-absorbing sheets, HEPA filters, microfiltration materials, optical split sheets, and humidity self-regulating materials.
Cellulose-based substances produced on a nano-level microfibrous microorganism which can be used in the present invention include Acetobacter xylinum subspecies schlofermenta (BPR2001 strain). Acetobacter xylinum subsp. sucrofermentans ), Acetobacter xylinum ( Acetobacter xylinum ) ATCC 23768, Acetobacter xylinum ATCC 23770, Acetobacter pasteurianus ( A. pasteurianus ) Acetobacter (Acetobacter) such as ATCC 10245, Acetobacter xylinum ATCC 14851, Acetobacter xylinum ATCC 11142 and Acetobacter xylinum ATCC 10821, Agrobacterium, Rhizobium, Sarsina, Pseudomonas, Achromobacter, Alcaligenes Genus, Aerobacterium, Azotobacter and Zooglare, Enterobacter or Kluvera, and various mutant strains created by mutating them by a known method using NTG (nitrosoguanidine) or the like. Is what is done.
[0009]
In particular, a strain belonging to the genus Enterobacter or the genus Krubera, for example, CJF002 strain (Patent Microorganism Depositary Center, Research Institute of Biotechnology, Institute of Industrial Science and Technology, Ministry of International Trade and Industry, designation of microorganism "Enterobactersp. 17799 ", hereinafter simply referred to as Enterobacter CJF002 or CJF002.) The cellulosic microfibrillar substance produced is an independent body or a linked body constituting macrofibrils radially from the central region (see FIG. 1). Further, they are characterized in that they are connected to each other by microfibrils in a circular pore shape referred to as phase separation (see FIG. 2).
And the cellulosic microfibrillar substances produced by the microorganisms belonging to the genus Enterobacter or Clubella are much higher in wet compressibility, lower in slurry viscosity, and more effective in adhesion to other substances than those of acetic acid bacteria. It is particularly preferably used in the present invention in that it may have a component (eg, galactose, mannose, etc.).
[0010]
The above-mentioned nano-level microfibrous microorganism-producing cellulosic material can be mixed, cultivated, separated, sterilized, sterilized, purified, or afterwards, by a mixer, polytron, self-excited ultrasonic pulverizer, ultrasonic oscillator, various bead mills. The dispersion can be prepared using a high-pressure shearing machine represented by a microfluidizer.
In particular, in the case of the cellulosic microfibrillar substances produced by the CJF002 strain, the dispersing operation is extremely easy and the energy consumption is small as compared with those produced by acetic acid bacteria.
On the other hand, as described in the section of "prior art", nano-level fine fibrous cellulosic material derived from acetic acid bacteria, when the dispersion medium is water, low wet compressibility, and sheet Since the viscosity of the slurry during the formation is extremely high, the viscosity may be reduced in some cases by mixing and dispersing a water-soluble organic solvent such as alcohols in addition to water.
If necessary, a polymer fiber, an inorganic fiber, and an inorganic filler are mixed and dispersed in these dispersion liquids, whereby the viscosity of the slurry can be further reduced, and the water drainage property can be improved.
A sheet is obtained by using the above dispersion liquid and making a paper on a mesh by an ordinary method such as suction, pressurization, or natural flow.
[0011]
In the next step of impregnation or joining of other substances, in order to improve insufficient joining and uniform impregnation, the sheet-like material is provided with a hydrophobic organic solvent, in particular, an aromatic hydrocarbon or an alicyclic hydrocarbon. It may be advantageous for one or more selected from hydrogen and their derivatives to be present.
In particular, the presence of the hydrophobic organic solvent can improve the low wet compressibility, which is a drawback of the nano-level fibrous cellulosic material derived from acetic acid bacteria, by controlling the orientation characteristics of OH groups.
Of course, the present invention can also be applied to the case of a nano-level fine fibrous cellulosic material derived from the genus Enterobacter or the genus Krübela.
Microbial cellulosic substances with high plane orientation have the property of easily incorporating aromatic hydrocarbons and alicyclic hydrocarbons into intermolecular regions different from water and alcohols, and the dispersion is prepared. At the same time. Depending on the case, the obtained sheet may be impregnated and sprayed, or may be supplied as a solvent for impregnation and bonding of another substance in the next step.
[0012]
When preparing the sheet-like structure of the present invention, in some cases, fine fibers derived from natural cellulose fibers or regenerated cellulose fibers, polyolefin fine fibers, polyester fine fibers, polyamide fine fibers, aramid fine fibers. At least one of fiber, polyacrylic fine fiber, carbon fiber, glass fiber, alumina fiber, asbestos, and various inorganic whiskers may be mixed and dispersed.
If necessary, for example, calcium carbonate, clay, talc, glass fine powder, carbon powder, kaolin, calcined kaolin, delamikaolin, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, hydroxide Inorganic fillers such as zinc, magnesium hydroxide, calcium hydroxide, magnesium silicate, calcium silicate, calcium sulfate, aluminosilicate, silica, sericite, celite, bentonite, and smectite may also be mixed and dispersed.
Similarly, functional inorganic substances, for example, barium carbonate as an X-ray shield / ferroelectric, zirconium oxide as a low heat conductor / high refractive index material, zinc oxide as a catalyst material / photoreceptor substrate, Γ-ferrite as ferromagnetic, barium titanate as ferroelectric, cobalt oxide as paramagnetic / low electric conductor, tin oxide, alumina, silicon oxide as catalyst / polishing material, UV absorber / photocatalyst May be mixed and dispersed.
[0013]
The amount of these additives is not limited, and can be determined by a person skilled in the art from the viewpoint of cost and performance in consideration of the end use. From the viewpoint of exhibiting the performance of the nano-level fibrous microorganism-producing cellulose-based material of the present invention, the content of other materials is 90% or less, preferably 80% or less. In particular, in the case of a hydrophobic fiber material or a fine particle-based material, the sheet form cannot be maintained unless it is 80% or less. Further, in the electronic material substrate and the condenser separator, the content should be 60% or less in order to utilize characteristics such as low thermal expansion property and high elasticity of the microorganism-produced cellulose.
Further, for the purpose of lowering the apparent density of the sheet, a so-called bulking agent can be used. A bulking agent is, for example, a surfactant described in Paper and Paper Technology Times, July 2000, P14-17, for example, for improving the electrolyte retention and ion permeability of a capacitor separator or a battery separator. It is especially effective. The amount to be added is not limited depending on the type of bulking agent and the like. It is preferable to add 1% or more and less than 15%.
Although the thickness of the sheet-like structure of the present invention is not limited, the thickness of an electronic material substrate or a separator for a capacitor, which is required to be lightweight and thin, is 60 μm or less, preferably 30 μm or less.
[0014]
The sheet-like structure of the present invention is required to contain a hydrophilic solvent and / or a hydrophobic solvent, which means that it facilitates impregnation and bonding of other substances in the next step. An important factor is that it facilitates the movement of the whole molecule of microbial cellulose. Hydrophilic solvents move the hydrogen bonding surface (region), and hydrophobic solvents move the van der Waals surface (region). In particular, the hydrophobic solvent can control the orientation of the OH group and control the wettability of the sheet surface with water as described above. The hydrophilic solvent may be water, alcohols, polyhydric alcohols, amides, sulfoxides, etc., as long as the solvent has an inherent hydrogen bonding property. It gives the mobility of the plane (area). In terms of quantity, 2% or more is sufficient for the constituent cellulose component, but in practice, it is about 2% to 30%. The upper limit is not limited and needs to be suppressed to an amount sufficient to maintain the sheet state. The upper limit may be determined empirically in relation to the impregnation and bonding of other substances in the next step. As the hydrophobic solvent, aliphatic hydrocarbons, aliphatic halides, aromatic hydrocarbons, alicyclic hydrocarbons, and ester derivatives thereof are used. Hydrocarbons, alicyclic hydrocarbons, and derivatives having them as a skeleton most promote the mobility of cellulose. Quantitatively, the amount by which the microorganism-produced cellulosic substance can take up the hydrophobic solvent is sufficient, and is usually about 1 to 20%, but the upper limit is not limited.
[0015]
Other material solutions that can be impregnated into the sheet-like structure of the present invention are organic or inorganic sols or gels. The organic substance generally refers to various solutions or gels of macromolecules as long as they are soluble or gel-forming in any of a hydrophilic solvent, a hydrophobic solvent, and an amphoteric solvent. Either may be used. Examples of natural polymers include natural rubber, various proteins, polyglucosamine, polysaccharides represented by curdlan, mucopolysaccharides, chitin, chitosan, polylactic acid, polybutyric acid, and the like. Many of these can form gels with water. Synthetic polymers include condensation polymers typified by nylon and polyester, polyvinyl compounds, addition polymers typified by polyacrylates and various copolymers, so-called living polymers contained in addition polymers, nylon 6 and synthetic polymers. There are ring-opening polymers represented by proteins (NCA method) and polyaddition polymers represented by polyurethane. As the inorganic gel, there is a polysiloxane water gel.
The material that can be coated is basically a concentrated solution of the aforementioned polymer.
[0016]
The thermocompression-bondable material is not limited. For example, general-purpose hydrophobic / thermoplastic polymers such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), and polyalkylene oxides (PAO) And super engineering plastics such as polysulfones (PSu), polyamides (PA), polyesters (PET), polycarbonates, polyimides (PI), and polyphenylene ethers (PPE). .
The metal foil can also be press-bonded, and may be any of aluminum, copper, silver, gold, tin, and alloys thereof as long as they are extensible. For example, copper and alloys such as zinc, tin, aluminum and nickel, and aluminum and alloys such as manganese, magnesium, silica and zinc are also used. Copper is preferably used as the wiring board material for the electrical material.
[0017]
The structure obtained by impregnating the material of the present invention into the sheet of the present invention, coating and thermocompression bonding improves the morphological stabilization of the material group by the effect of the low coefficient of thermal expansion of the microorganism-produced cellulose. It is desirable to impregnate, coat, and thermocompression-bond a substance that exhibits more functions when combined with the produced cellulosic substance.
For example, when a solution of polymethylpentene-1 or γ-benzyl-L-glutamate is thinly impregnated into a microorganism-produced cellulosic material sheet having a thickness of about 6 μm and the solvent is removed, oxygen selective permeability based on the dissolution diffusion mechanism increases. I do.
In addition, when the polyaniline is impregnated with a dimethylformamide solution and the solvent is removed, the shape is stabilized and the range of use as a polymer electrolyte is expanded.
When impregnated with a toluene solution of PPE, a super engineering plastic sheet having extremely high thermal stability can be obtained.
[0018]
When a nanoporous silica gel obtained from TEOS or the like is rolled and impregnated with a roller or the like, a structure having high transparency and high ink absorption can be obtained.
In addition, after impregnating with an epoxy resin solution containing a catalyst, removing the solvent, pre-curing, and pressing the copper foil on both sides, it is highly dimensionally stable as an electronic material substrate with a copper foil surface insulated with cellulose / epoxy resin. , The material having.
If, for example, toluene is mixed as a solvent at the time of impregnation with the epoxy resin, it is possible to prevent a decrease in physical properties that is concerned under a water atmosphere after processing.
In addition, since cellulose has a high ability to adsorb hydrophobic toxic organic substances in drinking water such as halogen, stacking a layer of cellulosic fibers having higher water permeability can provide an effective adsorbent having high water permeability.
Cellulose itself is an optically active substance. If chitosan or the like having another optical activity is arranged and complexed with Pd or Rh, a highly selective hydrogenation catalyst sheet can be obtained.
[0019]
On the other hand, among the sheet-like structures of the present invention, when other fine fibers or inorganic fillers are maintained by a microorganism-produced cellulosic material, or when used as a high-dispersion material, the sheet is impregnated and coated. The material to be thermocompression-bonded should be selected with consideration given to improving the functions of the fine fibers and inorganic fillers already blended as constituent elements.
For example, a microbial cellulose sheet containing 50% of polyester fine fibers is useful as a HEPA filter by itself, but impregnating and cross-linking with polyglucosamine increases the effect of ionically removing fine dust.
In addition, the microorganism-produced cellulosic sheet in which titanium oxide is finely dispersed has a UV absorbing property and a photocatalytic effect. Therefore, it is impregnated with other highly transparent materials, such as PMMA, polycarbonate, PVA, etc., coated, and thermocompressed. Is desirable.
The microorganism-produced cellulosic sheet on which barium carbonate as an X-ray shield / ferroelectric substance is disposed is desirably impregnated, coated, and thermocompressed with another material having high strength.
Similarly, zirconium oxide as a low heat conductor / high refractive index material, zinc oxide as a catalyst material / photosensitive material base, γ ferrite as a ferromagnetic material, barium titanate as a ferroelectric, paramagnetic / low electric Examples of such a structure include cobalt oxide as a conductor, tin oxide, alumina, and silicon oxide as catalysts and abrasives.
[0020]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples.
Embodiment 1
<Preparation of microbial microfibrous cellulose material, slurry, and sheet>
(Example 1-1)
Polysaccharide production medium (Polysaccharide-production-medium, Akihiko Shimada, Viva Origino, 23, 1, 52-53, 1995) supplemented with 2.0% glucose was subjected to high-pressure steam sterilization, and 1000 ml of the resulting mixture was subjected to a 3000 ml content. Put the CJF-002 strain in a fermenter ⁴ CFU / ml was inoculated, and agitated culture with aeration was performed at 30 ° C. for 1 day under aeration.
As a result of the culturing, a cellulose substance in a special form (independent or linked bodies constituting macrofibrils radially from the central region) as shown in FIG. 1 was obtained.
This was filtered off with a screen mesh, washed with water, pressed, immersed in a 1% NaOH solution, sterilized, neutralized again, washed with water and pressed again to easily obtain a water-containing substance (cellulose solid concentration: 10 wt%).
Incidentally, the viscosity of a slurry (hereinafter, referred to as Example 1-1 slurry) in which the obtained microbial microbial fibrous cellulosic material obtained was dispersed in water with a normal blender so that the concentration was 0.05%. Was about 200 cp.
Next, an A4 plate (about 21 × 30 cm) and a sheet having a thickness of about 40 μm were prepared from the slurry of Example 1-1 using a usual papermaking apparatus, and air-dried (hereinafter referred to as “Example 1-1 sheet”).
The moisture content of the air-dried sheet was about 30%.
[0021]
(Example 1-2)
On the other hand, using acetic acid bacterium ATCC 10245, 4% fructose was used as a carbon source, and a small jar fermenter (total volume 2000 ml) was used to obtain cellulose fine fibers in accordance with the method described in JP-A-10-195713. A water-containing material having a cellulose solid concentration of 10% was obtained using Polytron, which is recommended in the publication.
The shape of the obtained cellulose was such that microfibrils of bacterial cellulose crossed, and were completely different from the circular pore shape referred to by phase separation as in Example 1-1.
Incidentally, the viscosity of the slurry (hereinafter, referred to as a slurry in Example 1-2) in which the obtained microbial microbial cellulosic material produced was dispersed in water with a normal blender so that the concentration was 0.05%. Was about 1000 cp.
Next, a sheet having a size of A4 (about 21 × 30 cm) and a thickness of about 40 μm was prepared from the slurry of Example 1-2 using a usual papermaking apparatus, and air-dried (hereinafter, referred to as a sheet of Example 1-2).
The moisture content of the air-dried sheet was about 30%.
The slurry of Example 1-2 was slightly more difficult to handle in forming a sheet than the slurry of Example 1-1.
Hereinafter, the numerical value 1 after the hyphen indicates that it is derived from Enterobacter (CJF002) and 2 is derived from Acetobacter (ATCC10245).
[0022]
[Comparative Example 1]
<Preparation of absolutely dry sheet>
The Example 1-1 sheet and the Example 1-2 sheet were dried with hot air to obtain their absolutely dry sheets (hereinafter referred to as Comparative Example 1-1 sheet and Comparative Example 1-2 sheet).
Embodiment 2
<Preparation of slurry containing hydrophilic medium and hydrophobic medium, and sheet>
10 g of the water-containing material having a cellulose solid concentration of 10% described in Example 1-1 or Example 1-2 was diluted 5-fold with water and strongly dispersed to obtain an aqueous dispersion having a cellulose solid concentration of 2 wt%. . On the other hand, 5 g of toluene was gradually added while performing a dispersion operation under shearing, and finally the mixture was passed through a microfluidizer to obtain a milky-white and slightly transparent dispersion. In the case of microbial cellulose produced by acetic acid bacteria, the viscosity was high and required a considerable time. These were further diluted and dispersed with water to obtain a slurry having a cellulose solid content of 0.05 wt% (hereinafter, referred to as Example 2-1 and Example 2-2 slurries).
Next, an A4 plate (about 21 × 30 cm) and a sheet having a thickness of about 40 μm were prepared using the slurry of Example 2-1 and an ordinary papermaking apparatus using a usual papermaking apparatus, and air-dried (hereinafter, Example 2). -1 sheet, Example 2-2 sheet).
The moisture content of each sheet after air drying was about 30%, and toluene was 15%.
The Example 2-1 sheet was easier to drain than the Example 2-2 sheet.
[0023]
[Comparative Example 2]
<Preparation of absolutely dry sheet>
The Example 2-1 sheet and the Example 2-2 sheet were dried with hot air to obtain their absolutely dry sheets (hereinafter referred to as Comparative Example 2-1 sheets and Comparative Example 2-2 sheets).
Next, the specific surface areas of Comparative Examples 1-1 and 2 and Comparative Examples 2-1 and 2 were ₂ The measurement was performed according to the gas adsorption method (BET method).
The results are shown in Table 1 below.
In view of the results in Table 1, in each case of the CJF bacteria or the microorganism-produced cellulose fibrils derived from acetic acid bacteria, the sheets prepared from the aqueous dispersion containing toluene (Comparative Examples 2-1 and 2) were: The specific surface area is large as compared with a sheet prepared from an aqueous dispersion containing no toluene (Comparative Examples 1-1 to 2), and physical bonding and physical bonding are performed in the process of forming various bonding structures of the present invention. When utilizing the absorption action, it can be said that it is preferable that the hydrophilic medium and the hydrophobic medium coexist.
On the other hand, in Examples 1-1 to 2 sheets and Example 2-1 to 2 sheets (water content of 30 wt%) in which moisture was left, any sheet obtained from any of the microorganisms was obtained from X-ray diffraction (11-0). ) The orientation of the surface is 40-60% of the sheets (Comparative Examples 1-1 and 2 and Comparative Examples 2-1 and 2) obtained by absolutely drying these sheets, and high hydrogen bond formation is inhibited. Therefore, it is considered that preparing a sheet in which moisture is left is advantageous for bonding with a hydrophilic substance.
[0024]
[Table 1]

[0025]
Embodiment 3
<Joining with other materials # 1>
Example 2 sheets (hydrophilic medium (water) / hydrophobic medium (toluene) -containing) and Example 1-1 sheets (hydrophilic medium (water) -containing sheet) were compared with Mitsubishi Engineering Plus Tech. Aromatic copolymer polyamide PA (Novamid X21), A & M Corporation polystyrene PS (GP685), Asahi Kasei Corporation polyoxymethylene POM, Toray polybutylene terephthalate PBT (Trecon), Table 2 (other materials: PA, Thermocompression bonding was performed at a predetermined temperature (pressure 1.82MPs) of PS, PBT, and POM.
Next, the adhesiveness of each bonded structure was determined by a peeling test.
The peeling test was performed according to JIS C6481 (peeling strength), and the evaluation was ◎ (excellent), （(good), Δ (slightly weak), and × (peeling).
[0026]
[Comparative Example 3]
<Joining with other materials # 1>
Instead of the Example 2-1 and Example 2 sheets and the Example 1-1 and Example 2 sheets, Comparative Example 2-1 and Example 2 and Comparative Example 1-1 and Example 2 sheets (Table 1), which are absolutely dry sheets thereof, A thermocompression bonding with another material was carried out in the same manner as in Example 3 except that it was used.
Next, the adhesiveness of each bonded structure was determined by the same peeling test.
Table 2 shows the results of the peeling test of Example 3 and Comparative Example 3.
As is clear from Table 2, the hydrophilic polymer (POM) has good bonding properties with the sheet in which moisture remains (Examples 1-1 to 2), and the hydrophobic polymer (PS, PBT) has a good bonding property. It showed good adhesiveness with the sheet (Example 2-1 to 2 sheets) in which the hydrophobic medium remained.
In PA, aromatics were copolymerized, and in each case, almost satisfactory results were obtained.
[0027]
[Table 2]

[0028]
Embodiment 4
<Joint with other materials # 2>
Example 2-1 A mixture of 40 wt% of a slurry (containing water and toluene) and 60 wt% of a separately prepared 0.05 wt% dispersion liquid of aramid pulp having an average fiber diameter of 1 μm (manufactured by Du Pont-Toray Co., Ltd., sheet material) was prepared. An A4 size (about 21 × 30 cm) sheet was prepared from the resulting sheet using an ordinary papermaking apparatus and air-dried. The moisture content of the air-dried sheet was about 20%, and the toluene content was 10%.
The PA used in Example 3 was thermocompression-bonded to this sheet at 130 ° C. and 1.82 MPa.
When the peeling property test was performed on the joined structure, no peeling was observed, and the evaluation was ◎ according to Table 2.
[Comparative Example 4]
<Joint with other materials # 2>
The sheet was thermocompressed with PA in the same manner as in Example 4 except that the air-dried sheet of Example 4 was replaced with a completely dried sheet which was hot-air dried. When the peeling property test was performed on the joined structure, there were many peeling portions, and the evaluation was x based on Table 2.
[0029]
Embodiment 5
<Electronic material substrate>
Example 2-1 Toluene was sprayed again on a sheet (containing a hydrophilic medium (water) / hydrophobic medium (toluene)) and then impregnated with an epoxy resin (containing an amine-based catalyst) dissolved in methyl ethyl ketone. Then, the surplus was removed by a roll operation.
Then, after air drying and preliminary drying, copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., thickness: 10 μm) is thermocompression-bonded at 180 ° C. and 2 MPa for 1 hour on both sides of the sheet to obtain a copper foil for an electronic material substrate. I got a sheet.
Next, the section of this copper foil sheet was observed with an electron microscope, and as a result, the epoxy resin was found to enter the cellulose inner surface extremely uniformly.
Further, the heat treatment at 150 ° C. of this copper foil sheet showed a shrinkage of 7 ppm or less, which was good as a wiring board for electronic materials. Similar results were obtained when an isocyanate-based resin or a hindered phenol-based resin was used instead of the epoxy resin.
[Comparative Example 5]
<Electronic material substrate>
Instead of using the sheets of Examples 2-1 and 2 (containing a hydrophilic medium (water) / hydrophobic medium (toluene)) and using the sheets of Examples 1-1 and 2 (a sheet containing a hydrophilic medium (water)) Was operated in the same manner as in Example 5 to obtain a copper foil sheet for an electronic material substrate.
The obtained copper foil sheet had void-like peeling between cellulose and epoxy resin in some places.
[0030]
Embodiment 6
<Structure for oxygen concentration>
Example 2-1 85 wt% of a slurry (containing water and toluene) and 15 wt% of a 0.05 wt% aqueous dispersion of polyester fine fibers (manufactured by Asahi Kasei Corporation) having an average fiber diameter of 0.18 μm were mixed and dispersed. A4 sheet (approximately 21 × 30 cm) was prepared using the papermaking apparatus described above and air-dried. The moisture content of the air-dried sheet was about 20%, and the toluene content was 10%. The air permeability of this sheet measured by the KES method was 3-4 KPa / s · m.
This sheet is dipped into a very slightly whitened translucent stock solution prepared by adding 10 g of water to 1000 g of a 5 wt% toluene solution of polyoxymethylsilane and mixing well, and then the excess polymer solution is rolled with a constant pressure roll. After removal, the sheet was air-dried and heat-dried to obtain a sheet-like structure.
Then, the sheet-shaped structure is cut into small circles, the ten sheets are superimposed, flattened by applying light pressure, and mounted on a Millipore cylindrical filtration device, air is flowed, and oxygen and nitrogen are dissolved and diffused. Permeability (P: cm ³ ・ Cm / cm ² .S · Pa) was evaluated.
Permeability to oxygen and nitrogen of a polyoxymethylene film containing 10 wt% of a plasticizer / filler (P: cm ³ ・ Cm / cm ² S · Pa)) are 367 and 170, respectively. In the sheet-like structure of Example 6, although the separation efficiency is reduced, the permeability (P: cm ³ ・ Cm / cm ² S · Pa)) were 720 and 400, respectively.
[Comparative Example 6]
<Structure for oxygen concentration>
Example 6 was carried out in the same manner as in Example 6 except that the sheet-like structure prepared in Example 6 was dried by hot air to remove most of the solvent.
When the air permeability of this sheet-like structure was measured by the KES method, it was 6-7 KPa / s · m. If the pressure was not increased, air was difficult to flow.
[0031]
Embodiment 7
<Structure for ink absorption or humidity self-regulation>
In Example 2-1 sheet (containing water / toluene) and Example 1-1 sheet (containing water), a transparent nanoporous silica water gel (silica concentration; prepared in accordance with the method described in Japanese Patent Application No. 2001-127699) was added. 30%) was coated with a doctor knife (1 μm thick), air-dried, and then dried with hot air.
Each of the obtained sheet-like structures was a uniform sheet, and in particular, the former had good flexibility.
The obtained sheet-like structure had good absorbability (both speed and amount) of ink and the like, and was suitable for inkjet printing.
Further, the obtained sheet-like structure had a property of absorbing and releasing moisture depending on the difference in humidity / temperature environment. Furthermore, it was also suitable as a material for supporting a catalyst.
[Comparative Example 7]
<Structure for ink absorption or humidity self-regulation>
Instead of the Example 2-1 sheet (containing water / toluene) and the Example 1-1 sheet (containing water), the above Comparative Example 1-1 sheet (absolutely dried sheet of Example 1-1 sheet) is used. Other than that, it carried out similarly to Example 7.
In the obtained sheet-like structure, the silica polymer was hard and peeling was conspicuous.
[0032]
Embodiment 8
<Photocatalyst structure>
Example 2-1 Sheet (containing water / toluene) and Example 1-1 sheet (containing water) are impregnated with a 15% butanel / ethanol mixed solution of alkoxytitanium containing a small amount of phosphoric acid, and gradually dried and heated. Dried.
Each of the obtained sheet-like structures was a uniform sheet, and in particular, the former had good flexibility. These had a catalytic action with light of 330 nm.
[Comparative Example 8]
<Photocatalyst structure>
Instead of the Example 2-1 sheet (containing water / toluene) and the Example 1-1 sheet (containing water), the above Comparative Example 1-1 sheet (absolutely dried sheet of Example 1-1 sheet) is used. Except for the above, the same procedure was performed as in Example 8.
In the obtained sheet-like structure, titanium was hard and peeling was conspicuous.
[0033]
Embodiment 9
<Structures for optoelectronics>
Example 2-1 Sheet (containing water / toluene) and Example 1-1 sheet (containing water) are impregnated with a butane / ethanol mixed solution containing 30% of alkoxide of barium and titanium containing a small amount of acetic acid, and gradually. , Drying and heat drying at 90 ° C.
The obtained sheet-like structure was a sheet on which barium titanate, which was slightly brown but transparent, was evenly distributed. In particular, the former had good flexibility.
The obtained sheet-like structure has a ferroelectric effect of barium titanate and high transparency of cellulose produced by microorganisms (the fibril diameter is as small as 50 nm), so that it is useful as an optoelectronic material having mechanical strength. is there.
[Comparative Example 9]
<Structures for optoelectronics>
Instead of the Example 2-1 sheet (containing water / toluene) and the Example 1-1 sheet (containing water), the above Comparative Example 1-1 sheet (absolutely dried sheet of Example 1-1 sheet) is used. Other than that, it carried out similarly to Example 9.
The obtained sheet-like structure had a form in which barium titanate was apparently coated on microbial cellulose, but had a cracked surface.
[0034]
Embodiment 10
<Structure for HEPA filter>
Example 1-1 30% by weight of a slurry and 70% by weight of an aqueous dispersion of 0.05% by weight of a polyester fine fiber having an average fiber diameter of 0.18 μm used in Example 6 were mixed and dispersed. Then, an A4 plate (about 21 × 30 cm) having a thickness of about 3 mm was prepared and air-dried.
The moisture content of the air-dried sheet was about 30%.
When the air permeability of the obtained sheet-like structure was measured by the KES method, it was 1-1.5 KPa / s · m.
The obtained sheet-like structure is impregnated with a chitosan acidic solution having a deacetylation degree of 42% (chitosan concentration of 1 wt%, solvent of 0.6N hydrochloric acid aqueous solution), squeezed easily with a roll, rapidly dried with hot air, and then treated with caustic soda. After neutralization with an aqueous solution, air drying and heat drying were performed. Next, the dust collection rate of the air that generated 0.035 μm of dust was determined using a dust remover equipped with the sheet as a HEPA filter, and was found to be 99.99%. The result is that you can earn a lot.
In addition, the air existing in the room handling microorganisms was passed using the above-mentioned HEPA filter sheet-like structure. In the presence of this passing air and the original air, bacteria were detected on the ordinary agar medium.As a result, bacteria were detected in the original air, but in the passing air, the detection of live bacteria was greatly reduced. .
[0035]
[Comparative Example 10]
<Structure for HEPA filter>
In the same manner as in Example 10, a chitosan acidic solution having a degree of deacetylation of 42% (chitosan concentration of 1 wt%, solvent) was applied to the absolutely dried sheet of Example 8 (air permeability by KES method: 3-4 KPa / s · m). (0.6N hydrochloric acid aqueous solution), squeezed easily with a roll, rapidly dried with hot air, neutralized with caustic soda aqueous solution, air-dried, and heat-dried. Next, the dust collection rate of the air that generated 0.035 μm of dust was determined using a dust remover equipped with the sheet as a HEPA filter. The result was 99.99% as in Example 10, but the pressure loss was found. Was bigger.
[0036]
Embodiment 11
<Polishing structure, ink absorbing structure, left-hand coating liquid>
100 g of the water-containing material having a cellulose solid concentration of 10% obtained in Example 1-1 was diluted 5-fold with water and strongly dispersed to obtain an aqueous dispersion having a cellulose solid concentration of 2 wt%. On the other hand, 50 g of cyclohexane was gradually added while performing a dispersion operation to obtain a milky, slightly transparent slurry.
This slurry was diluted and dispersed with water to obtain a slurry having a cellulose solid concentration of 0.05% by weight.
To 25 parts by weight of cellulose in this slurry, 72 parts by weight of γ-alumina (for polishing) and 3 parts by weight of SB latex (in terms of solids) were added and dispersed to obtain a slurry for papermaking.
Using this papermaking slurry, an A4 plate (about 21 × 30 cm) sheet-like structure having a thickness of about 3 mm was prepared using a usual papermaking apparatus.
The alumina capture ratio of the obtained sheet-like structure in the papermaking process was 97%.
Moreover, the obtained sheet-like structure had high flexibility.
Then, by polishing the ground glass with the obtained sheet-like structure, the ground glass became transparent and the ink absorbability was good.
Further, the above slurry for papermaking is useful as it is as a coating liquid.
In addition, the same cyclohexane-containing cellulose dispersion (cellulose / alumina / SB latex = 30/67/3, weight ratio) is formed on the obtained sheet-like structure, and then air-dried, heat-dried, and vacuum-dried. The drying was repeated, but about 3% of cyclohexane remained although water was removed. This sheet had good dimensional stability in water.
[0037]
[Comparative Example 11]
<Polishing structure, ink absorbing structure, left-hand coating liquid>
The same operation as in Example 11 was carried out except that cyclohexane was not added to the aqueous dispersion having a cellulose solid concentration of 2 wt% in Example 11, to obtain a sheet-like structure having a thickness of 3 mm. The obtained sheet-like structure had an alumina capture ratio of 90% during the papermaking process, and the flexibility was lower than that of the sheet-like structure of Example 11.
Furthermore, after the dispersion (without cyclohexane) of the same composition is formed on the obtained sheet-like structure, the sheet is repeatedly air-dried, heat-dried, and vacuum-dried. The sheet is highly hard, but is dimensionally stable in water. The sex was slightly inferior.
As is clear from the above Example 11 and Comparative Example 11, the better uniform dispersibility of the hydrophilic inorganic oxide in the coexistence of water and the hydrophobic solvent is due to the fact that water forms the hydrogen bonding surface of the microbial cellulose. As a result of the hydrophobic solvent being opened and the hydrophobic surface that is perpendicular to it being opened by the hydrophobic solvent, smooth dispersion is realized (this effect is based on the inorganic impregnation system of the following examples). It seems to be. (Note that this is in parallel with the phenomenon of increasing the specific surface area described in Example 2.)
[0038]
Embodiment 12
<Photocatalyst structure>
57 parts by weight of anatase-type titanium oxide (particle size: 5 μm or less) and 3 parts by weight of SB latex (solid basis) were added to 40 parts by weight of cellulose in the slurry (containing cyclohexane) having a cellulose solid concentration of 0.05 wt% in Example 11. In addition, the mixture was dispersed to obtain a slurry for coating and impregnation.
This slurry was laminated on a commercially available glass fiber HEPA (1.5 mm thick) filter to a thickness of 0.1 mm, and then dried.
The titanium oxide capture rate in the laminating process of the obtained sheet was 98% in the examples.
To determine the promotion of the photocatalytic effect, the obtained sheet (modified HEPA filter) was continuously irradiated with dust and bacteria while irradiating UV at 330 nm.
[Comparative Example 12]
<Photocatalyst structure>
The coating / impregnating slurry of Example 11 was prepared without adding cyclohexane. This slurry was laminated on a commercially available glass fiber HEPA (1.5 mm thick) filter to a thickness of 0.1 mm, and then dried.
The titanium oxide capture rate in the laminating papermaking process of the obtained sheet was 92% in the examples.
In the determination of the promotion of the photocatalytic effect, the contamination in Comparative Example 12 was slightly earlier than that in Example 12.
[0039]
Embodiment 13
Example 2-1 A 0.1% by weight thermosetting liquid phenol resin (manufactured by Kanebo Co., Ltd.) was dispersed in toluene on a sheet (containing water / toluene), and a 10-fold volume of water was gradually added thereto and dispersed. Was impregnated with a roller. The phenolic resin-impregnated sheet thus obtained was dried and heated at 100 ° C. for 1 hour. As a result, no change was observed in the shape of the sheet, and the sheet remained flat.
The sheet impregnated with the obtained phenolic resin can have the property of a phenolic resin having a heat distortion temperature of 240 ° C., and can be a structure suitable for an insulating material for capacitors and the like.
[Comparative Example 13]
Example 1-1 A sheet (containing water) was impregnated with a phenol resin in the same manner as in Example 13, dried and heated.
The resulting sheet was unstable in impregnation with the phenolic resin, and had a shape with one side warped due to differences in shrinkage during drying.
[0040]
Embodiment 14
60% by weight of the slurry (containing cyclohexane) having a cellulose solid concentration of 0.05% by weight in Example 11 and 40% by weight of a dispersion of 0.05% by weight of a polypropylene short fiber having an average fiber diameter of 1 μm (manufactured by Mitsubishi Rayon Co., Ltd.) were mixed and dispersed. Was prepared using an ordinary papermaking apparatus to form an A4 plate (about 21 × 30 cm) and a sheet having a thickness of about 2 mm (water 30%, cyclohexane 15% remaining).
On this sheet, a dispersion obtained by mixing and dispersing a previously prepared cellulose / polypropylene dispersion (total fiber concentration: 0.05 wt%) with powdered activated carbon having a fiber content of 30 wt% was laminated and formed to a thickness of about 2 mm. The sheet was air-dried to obtain a sheet-like structure.
Water containing 20 ppm of chloroform was passed through the sheet-like structure, and the amount of chloroform in the passing water was measured by gas chromatography. The measurement result was at the ppb level.
[0041]
[Comparative Example 14]
A sheet-like structure having the same composition and the same structure (cellulose / polypropylene / activated carbon sheet laminated on cellulose / polypropylene sheet) was obtained in the same manner as in Example 14 except that cyclohexane was not contained.
Water containing 20 ppm of chloroform was passed through the sheet-like structure at the same speed as in Example 14, and the amount of chloroform in the passing water was measured by gas chromatography. The measurement result was 6 ppm or more.
The difference between Example 14 and Comparative Example 14 is that, as described in Example 2, the sheet containing cyclohexane had a larger specific surface area of cellulose, and the sheet containing It is considered that the presence of a non-aqueous solvent inhibits the plane orientation of cellulose and improves the ability to take in a non-aqueous solvent such as halogen.
Further, it was found that the pressure loss when passing the halogen-containing water at the same speed was much smaller in Example 14 than in Comparative Example 14, and it was found that the pressure loss was also effective for mass processing.
[0042]
Embodiment 15
The water-containing material having a cellulose solid concentration of 10% obtained in Example 1-1 was diluted and dispersed with water to obtain an aqueous dispersion having a cellulose solid concentration of 0.05 wt%.
On the other hand, a 0.05 wt% aqueous dispersion of polyester fine fiber (manufactured by Asahi Kasei Corporation) having an average fiber diameter of 0.18 μm was prepared.
Then, 50 wt% of the above aqueous cellulose dispersion and 50 wt% of an aqueous polyester fiber dispersion were mixed and dispersed, and the thickness of an A4 plate (about 21 × 30 cm) was about 3 mm and the water content was 20 wt% (based on cellulose) using a normal papermaking apparatus. (40 wt%) sheet material (first step).
The sheet is impregnated with a chitosan acidic solution having a degree of deacetylation of 42% (chitosan concentration: 1 wt%, solvent: 0.6N hydrochloric acid aqueous solution), squeezed easily with a roll, rapidly dried with hot air, and neutralized with a sodium hydroxide aqueous solution. Then, the sheet was air-dried to obtain a sheet having a water content of 20 wt% (second step).
The chitosan-impregnated sheet was impregnated with a 0.1% copper oxide dilute acid solution and squeezed and dried with a roller to prepare a chitosan / ionized copper oxide impregnated sheet (third step). The sheet showed a very thin blue color throughout.
The resulting sheet is irradiated with ultraviolet light by a germicidal lamp while passing heavy oil combustion flue gas, and nitric oxide NO in the flue gas is discharged. _X Was measured by a conventional method (gas chromatography method). NO before passing through the sheet _X Was 900 ppm and ppb level after passing.
In the obtained sheet, if an aqueous zinc hydroxide solution is used instead of copper oxide, SO _X It is also effective for adsorption.
Further, since the microorganism-produced cellulose / chitosan structure of Example 15 can carry other metals such as palladium, platinum, and ruthenium in addition to copper and zinc, it also serves as a structure for a metal catalyst such as an asymmetric hydrogenation reaction. obtain.
[0043]
[Comparative Example 15]
In the first to third steps of Example 15, the same operation as in Example 15 was carried out using a sheet-like material (containing cellulose / polyester fibers) having almost no moisture to prepare a chitosan / ionized copper oxide-impregnated sheet. The sheet was mottled blue.
Using the obtained sheet, NO was measured in the same manner as in Example 15. _X Was about 100 ppm.
The difference between the effects of Example 15 and Comparative Example 15 is that Example 15 is impregnated with chitosan and copper ions in the presence of moisture, and cellulose / chitosan is dispersed and adsorbed relatively uniformly. It is thought that efficient catalytic action was realized because N was uniformly coordinated to the N-acetyl group of chitosan and the OH group at C2 and C3 positions of cellulose produced by microorganisms.
[0044]
Embodiment 16
100 g of the water-containing material having a cellulose solid concentration of 10% obtained in Example 1-1 was diluted 5-fold with water and strongly dispersed to obtain an aqueous dispersion having a cellulose solid concentration of 2 wt%.
On the other hand, while performing the dispersion operation, 50 g of cyclohexane was gradually added to obtain a milky white, slightly transparent aqueous dispersion.
Next, this aqueous dispersion was diluted and dispersed with water to prepare an aqueous dispersion having a cellulose solid concentration of 0.05 wt%, and the thickness of an A4 plate (about 21 × 30 cm) was prepared from the aqueous dispersion using a normal papermaking apparatus. A sheet having a thickness of about 1 mm, a water content of about 30 wt%, and a cyclohexane content of about 15 wt% was obtained (first step).
On the other hand, with respect to 25 parts by weight of an aqueous dispersion containing 1% by weight of cellulose and containing 1% by weight of solid cellulose, 72 parts by weight of an aqueous dispersion containing 1% by weight of barium carbonate and SB latex solid were prepared by changing the dilution ratio of water according to the above-mentioned operation method. 3 parts by weight of a 1 wt% aqueous dispersion was added, and the mixture was dispersed with a blender to obtain a viscous substance.
This is coated on both sides of the sheet-like material prepared in the first step, a roller operation is performed so as to have a constant thickness, and air-dried to form a sheet-like material having a thickness of about 3 mm. Hot air drying was performed to obtain a barium carbonate-containing laminated structure.
This laminated structure was a laminated structure in which the bonding strength with the cellulose sheet as the base material was ensured. The capacitance was measured by an existing method, and as a result, the capacitance was 2 nF.
The coefficient of linear expansion at 200 ° C. of this laminated structure was as low as several ppm, which is almost the same as that of the cellulose sheet as the base material, and had dimensional stability. This is because some of the latex particles present in the coating material diffuse into the cellulose base material due to the effects of cyclohexane and water remaining in the base material cellulose sheet and cyclohexane and water also present in the coating material, and the base material and the coating material are diffused. It can be said that the entanglement between the cellulose fibers of the material was promoted.
In place of the above barium carbonate, other inorganic substances, for example, zinc oxide, rutile titanium oxide, clay, calcium carbonate, magnesium carbonate, kaolin, gypsum, a poorly soluble inorganic substance such as calcium silicate can be adopted, and the function of maintaining mechanical strength The laminated structure can be provided.
Needless to say, the function of the resulting structure can be further supplemented as in Embodiments 8 and 12.
[0045]
[Comparative Example 16]
In the first step of Example 16, a cellulose fiber sheet containing no cyclohexane and containing almost no water was prepared.
Also, cyclohexane has been used at all in preparing the viscous material for a coating material.
Except for the above, the same operation as in Example 16 was performed to obtain a barium carbonate-containing laminated structure.
In the obtained laminated structure, the bonding between the base material and the coating material was unsatisfactory, and the laminated structure did not become an integrated structure.
Embodiment 17
100 g of the water-containing material having a cellulose solid concentration of 10% obtained in Example 1-1 was diluted 5-fold with water and strongly dispersed to obtain an aqueous dispersion having a cellulose solid concentration of 2 wt%.
On the other hand, while performing the dispersion operation, 50 g of cyclohexane was gradually added to obtain a milky white, slightly transparent aqueous dispersion.
Next, this aqueous dispersion was diluted and dispersed with water to obtain an aqueous dispersion having a cellulose solid concentration of 0.05 wt%.
Subsequently, 72 parts by weight of zirconium oxide and 3 parts by weight of SB latex (in terms of solids) were added to 25 parts by weight of cellulose in the aqueous dispersion and dispersed.
An A4 plate (about 21 × 30 cm) sheet having a thickness of about 3 mm was prepared from this aqueous dispersion using a usual papermaking apparatus.
After drying the zirconium oxide-containing sheet thus obtained, one surface thereof was heated to 200 ° C., and the surface temperature on the opposite side of the sheet was measured. As a result, the surface temperature did not change.
The zirconium oxide-containing sheet of Example 17 has low thermal conductivity of zirconium oxide, and can be a structure as a low thermal conductor.
Instead of zirconium oxide, other inorganic substances, for example, zinc oxide, rutile-type titanium oxide, clay, calcium carbonate, magnesium carbonate, kaolin, gypsum, a poorly soluble inorganic substance such as calcium silicate can be used, and the function of maintaining mechanical strength The laminated structure can be provided.
Needless to say, the function of the obtained sheet-like material can be further supplemented as in Examples 8 and 12.
[0046]
[Comparative Example 17]
A zirconium oxide-containing sheet was obtained in the same manner as in Example 17 except that cyclohexane was not added.
After drying the zirconium oxide-containing sheet thus obtained, one surface thereof was heated to 200 ° C., and the surface temperature on the opposite side of the sheet was measured. As a result, the surface temperature rose to 70 ° C. .
Embodiment 18
100 g of the water-containing material having a cellulose solid concentration of 10% obtained in Example 1-1 was diluted 5-fold with water and strongly dispersed to obtain an aqueous dispersion having a cellulose solid concentration of 2 wt%.
On the other hand, while performing the dispersion operation, 50 g of cyclohexane was gradually added to obtain a milky white, slightly transparent aqueous dispersion.
Next, this aqueous dispersion was diluted and dispersed with water to obtain an aqueous dispersion having a cellulose solid concentration of 0.05 wt%.
To 25 parts by weight of cellulose in this aqueous dispersion, 72 parts by weight of zinc oxide and 3 parts by weight of SB latex (in terms of solids) were added and dispersed.
From this aqueous dispersion, an A4 plate (about 21 × 30 cm) having a thickness of about 3 mm was prepared using a conventional papermaking apparatus (first step).
The sheet thus obtained was air-dried and impregnated with a roller in which a 0.005% SB latex was dispersed in a 0.1% ruthenocene dye solution.
After drying the impregnated sheet, the sheet was irradiated with sunlight and the generated current was measured. As a result, a current of 400 mA per second was generated.
This means that the cellulose sheet having a large specific surface area obtained from Example 1-1 is provided with the photosensitivity of the ruthenocene dye and the photosensitivity of zinc by a roller operation, and can be a structure as a photoconductor substrate. It is shown that.
[0047]
[Comparative Example 18]
In the first step of Example 18, a cellulose fiber sheet was prepared in a completely dried state.
Except for the above, the same procedure as in Example 18 was carried out to obtain a zinc / ruthenocene dye-containing sheet.
The resulting sheet generated 200 mA per second.
Embodiment 19
To the air-dried A4 plate (about 21 × 30 cm) toluene-containing sheet (Example 2-1 sheet) obtained in Example 2, 1 g of γ-ferrite was added to 10 ml of a 30% nitrocellulose solution (nitrogen content: 10.9 to 11). .2%; isopropyl alcohol solution).
The obtained sheet coated with γ-ferrite was uniformly coated with γ-ferrite, and did not peel off in the peeling test.
The sheet coated with this γ-ferrite can be a good ferromagnetic structure.
[0048]
[Comparative Example 19]
A sheet obtained by drying the air-dried A4-sized (about 21 × 30 cm) toluene-containing sheet obtained in Example 2 (Example 2-1 sheet) was coated with γ-ferrite in the same manner as in Example 19.
The obtained sheet coated with γ-ferrite had uneven coating and peeled off in many parts.
Embodiment 20
To the air-dried A4 plate (about 21 × 30 cm) toluene-containing sheet (Example 2-1 sheet) obtained in Example 2, 1% (w / v) liquid silicone was gradually added to a 1% aqueous cobalt oxide solution. And 1/10 volume of toluene was added and dispersed, and impregnated with a roller.
After the thus obtained cobalt oxide-impregnated sheet was dried, the electric capacity was measured. As a result, an electric capacity of 10 pF was recognized.
This cobalt oxide impregnated sheet is given the low electrical conductivity of cobalt oxide and can be a structure as a low electrical conductor.
[0049]
[Comparative Example 20]
A sheet obtained by completely drying the air-dried A4 plate (about 21 × 30 cm) toluene-containing sheet (Example 2-1 sheet) obtained in Example 2 was treated in the same manner as in Example 20 to obtain a cobalt oxide impregnated sheet. .
The electric capacity of the obtained cobalt oxide impregnated sheet was 50 pF.
Embodiment 21
Cyanoethylated hydroxyethylcellulose (CEHEC) was synthesized according to the method described in Jounalf Wood Science, 44: 35-39 (1998).
Water was gradually added to the 0.5 wt% acetone solution to near the cloud point, and barium titanate in the same amount as CEHEC was added and dispersed.
This dispersion was impregnated into the air-dried A4-size (about 21 × 30 cm) toluene-containing sheet (Example 2-1 sheet) obtained in Example 2, pressed with a roller, air-dried, and dried. It was crimped. A rigid and heat-stable sheet-like structure was obtained.
The above structure has the highest level of piezoelectric coefficient (d ₂₅ = 10 ^-11 C / N) and the high dielectric constant of 1200 F / m of barium titanate, and the synergistic effect of the plane orientation structure (structural anisotropy) of the microbial cellulose, for example, a dynamic electric transducer And the like for a high dielectric material.
[Comparative Example 21]
Example 2-1 A sheet-like structure was obtained by performing the same processing as in Example 21 on a sheet from which the solvent was almost completely removed.
In the sheet-shaped structure, defective bonding portions were found during the thermocompression bonding process.
[0050]
【The invention's effect】
According to the present invention, a special microorganism-produced cellulosic material is provided, and processing conditions such as bonding and dispersion of the cellulosic material and other materials are established, and a functional structure that can be expected to have a synergistic effect is provided. The present invention has succeeded in adding a new industrial value, which cannot be achieved by conventional microorganism-produced cellulose.
[Brief description of the drawings]
FIG. 1 is an optical micrograph of a cellulosic material of the present invention.
FIG. 2 is a scanning electron micrograph of the cellulosic material of the present invention.

Claims (6)

A sheet-like structure comprising a cellulosic microfibrillar substance produced by a microorganism and a hydrophilic solvent and / or a hydrophobic solvent. The hydrophilic solvent is water and / or glycols, and the hydrophobic solvent is at least one selected from aromatic hydrocarbons, alicyclic hydrocarbons, and derivatives having them as a skeleton. The sheet-like structure according to claim 1, wherein: 3. The sheet-like structure according to claim 1, wherein the cellulosic microfibrillar substance produced by the microorganism is a cellulosic microfibril substance produced by an acetic acid bacterium (genus Acetobacter). Cellulosic microfibrillar substances produced by microorganisms are cellulose microfibrillar substances produced by microorganisms belonging to the genus Enterobacter or Kluvera, independent of macrofibrils radiating from the central region, or linked. The sheet-like structure according to claim 1 or 2, wherein the sheet-like structure is a body, and they are connected to each other by microfibrils in a circular pore shape in a phase-separated structure. A method for manufacturing a joined structure, comprising disposing another material on at least one surface of the sheet-shaped structure according to any one of claims 1 to 4, and integrating the two materials. A joint structure manufactured by the manufacturing method according to claim 5.

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