JP4229421B2 - Method for modifying polymer material and use thereof - Google Patents

Description

【００５２】
（２）歯列矯正用ブラケット：
サイズ２．２３×３．０×３．８ｍｍ、重量約３１ｍｇ／個、アルミニウム金具で補強されたポリプロピレン成形物。
【００５３】
（Ｂ）試薬類
（１）ポリビニルアルコール（ＰＶＡ）：和光純薬（株）製、製品番号１６０−１１４８５（平均重合度=１５００〜１８００）
（２）カルボキシメチルセルロースナトリウム（ＣＭＣ）：和光純薬（株）製、製品番号０３９−０１３５５
（３）アクリル酸：和光純薬（株）製、製品番号０１１−００７７６
（４）メタクリル酸：和光純薬（株）製、製品番号１３８−１０８０５
（５）メタクリル酸メチル：和光純薬（株）製、製品番号１３９−０２７２６
（６）過硫酸ナトリウム（ＳＰＳ）：和光純薬（株）製、製品番号１９５−０４９８５
（７）過硫酸カリウム（ＫＰＳ）：和光純薬（株）製、製品番号１６２−０４２３５
（８）２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）：和光純薬（株）製、製品番号０１９−０４９３２
（９）硝酸二セリウムアンモニウム（IV）（ＣＡＮ）：和光純薬（株）製、製品番号０３６−０１７４２
（１０）ベンゾフェノン：和光純薬（株）製、製品番号０２３−０１０７２
（１１）メタノール：和光純薬（株）製、製品番号１３６−０９４７５
（１２）水酸化ナトリウム：和光純薬（株）製、製品番号１９４−０２１３５
（１３）塩酸：和光純薬（株）製、製品番号０８０−０１０６６
（１４）トルエン：和光純薬（株）製、製品番号２０４−０１８６６、この液体そのものを用いた（含浸剤Ａ）。
（１５）ドデシルベンゼンスルホン酸ナトリウム（ＤＢＳ）：東京化成工業（株）、製品番号Ｄ１２３８、界面活性剤として使用した。
（１６）デカヒドロナフタレン（シス、トランス混合物）：和光純薬（株）製、製品番号０４８−O００６６、この液体そのものを用いた（含浸剤Ｂ）。
（１７）オルトヒドロキシビフェニール（ＯＨＢ）：和光純薬（株）製、製品Ｂ番号０８０-O１４０２、オルトヒドロキシビフェニール１ｇと水酸化ナトリウム０．２ｇ、界面活性剤（ドデシルベンゼンスルホン酸ナトリウム）０．２ｇを水２００ｍｌに混合して得た溶液をして用いた（含浸剤Ｃ）。
またはオルトヒドロキシビフェニール０．５ｇをメタノール３００ｍｌに溶解して得た溶液をキャリヤーとして用いた水に分散させて用いた（キャリヤーＤ）。
（１８）サリチル酸ナトリウム（ＳＳ）：和光純薬（株）製、製品番号１９５−O３１４５（含浸剤Ｄ）
サリチル酸ナトリウム１ｇを水２００ｍｌに溶解し、１０％塩酸０．５ｍｌを混合して得た溶液を用いた水に分散させて用いた（含浸剤Ｅ）。
（１９）ジフェニル（ＤＰ）：和光純薬（株）製、製品番号０４０−１８４１２。ジフェニル２．５ｇと界面活性剤（ドデシルベンゼンスルホン酸ナトリウム）０．２ｇを水２００ｍｌに混合して得た溶液を用いた（含浸剤Ｆ）。
（２０）キャリアント（商品名、東邦化学（株）製）：ポリエステル系合成繊維染色用キャリヤー、芳香族エーテル系アニオン活性剤配合品。水に分散させて用いた（キャリヤー１）。
（２１）キャリヤーTW２００（商品名、日華化学（株）製）：ポリエステル・羊毛混紡用系合成繊維染色用キャリヤー、メチルナフタレンその他の配合品、水に分散させて用いた（キャリヤー２）。
【００５４】
（Ｃ）オゾン処理：
試験片を容積２Ｌまたは１０Ｌの硬質ガラス製容器（ガスの導入口と出口付き）に入れ、オゾン発生機（三菱電機（株）製ＯＳ−１Ｎ）より、オゾン発生量１ｇ／ｈ、濃度２０ｇ／ｍ^３のオゾンを含む酸素を８００ｍｌ／分の流量で２０〜１２０分間吹き込んだ。次に、オゾンを含まない酸素を１０分間吹き込んだ。オゾンの濃度はヨウ素滴定により求めた。酸化の程度は処理試験片の表面部材を削り、赤外線吸収スペクトルを測定して、１７１０ｃｍ^−１付近の吸収ピーク（カルボニル基の吸収）の吸光度の変化および、この吸光度と９７３ｃｍ^−１の吸光度の比より判断した。
【００５５】
（Ｄ）プラズマ処理：
プラズマ処理装置（ヤマトＰＲ５００）の反応槽内の電極間に試験片（布、フィルムなど）を置いた。反応槽内の圧力が０．２７Ｐａになるまで減圧した後、アルゴンガスと酸素ガスの混合物（体積比１：１）を圧力５．６Ｐａになるまで導入した。供給電力を４０Ｗから１００Ｗの間の値として、発振周波数１３．５６ＭＨｚで、主に３０秒から３分間グロー放電した。放電後、ガス導入を中止して、圧力を常圧に戻してから、処理試験片をとりだした。処理の程度は、フィルムに対する水の接触角の低下により判断した。
【００５６】
（Ｅ）紫外線照射処理：
活性化処理の場合は、試料そのものに対して、高圧水銀ランプ（東芝高圧水銀灯Ｈ４００Ｐ）を１０ｃｍの距離から直接照射した。
グラフト化の場合は、反応混合物をパイレックスガラス製の反応容器に入れて、温度１０〜７０℃にして、高圧水銀ランプ（東芝高圧水銀灯Ｈ４００Ｐ）を２０ｃｍの距離から照射した。光が均一に照射されるように、反応管は、自転しながら、ランプの周りを公転させた。
【００５７】
（Ｆ）吸水性の評価：
不織布、織布、繊維束、フィルム、板、多孔性フイルムの吸水率の測定：
（１）吸水率：試験片（サイズ１０ｃｍ×１０ｃｍ）を水を入れたビーカーに入れて、ガラス棒で穏やかに、約１分間撹拌する。次に、試験片を取り出し、３分間つるす（水滴が落ちなくなる）。吸水した試験片の重量から乾燥試験片の重量を引いて増加重量（吸水量）を求め、乾燥試験片の重量に対する百分率を吸水率（％）とした。
吸水率（％）＝（吸水量／乾燥時の試験片重量）×１００
【００５８】
（２）吸水速度：幅１．５ｃｍの試験片の下端１ｃｍを水に浸け、1分間に水が上昇した距離（単位ｃｍ／分）を測定した。
なお本実施例に用いた全ての未処理試料の吸水速度は０ｃｍ／分であった。 なお本実施例に用いた全ての未処理試料の水吸上げ速度は０ｃｍ/分であった。
【００５９】
（Ｇ）水の接触角の測定：
接触角測定装置（協和界面科学（株）製ＣＡ−Ｘ）を用いた。２０℃において、注射器から直径１ｍｍ程度の水滴を試験片の表面に滴下したものを、ビデオカメラで拡大した像のサイズから計算によって求めた。
【００６０】
（Ｈ）耐洗濯性試験：
試験片を弱アルカリ性の脂肪酸ナトリウム石鹸（商品名：ライオン（株）製ライオン粉石鹸）０．４％水溶液に、浴比１：２５０で入れ、撹拌しながら５分間、沸騰洗浄を行った。その後、十分に水洗後、乾燥した。吸水率、水吸上げ速度、および引張強度を測定し洗濯前と比較した。
【００６１】
（Ｉ）引張強度試験：
試験片を１．５ｃｍ×７ｃｍの長方形に切り、両端から１ｃｍの部分を引張試験機（今田製作所社製ＳＶ５５−０−２０Ｍ）のクランプに固定し、つかみ間隔を５ｃｍとして、引張速度１００ｍｍ／分で引っ張った。縦目と横目の各方向について測定した。各実施例においては縦目方向のみを示した。
【００６２】
（Ｊ）接着剥離強度試験：
（１）フィルムの場合：
試験片を３０ｍｍ（縦目方向）×５ｍｍの大きさに切り、一端の５ｍｍ×５ｍｍの部分に接着剤０．１ｇをつけ、ベニヤ板（厚さ２ｍｍ、サイズ２０ｍｍ×１０ｍｍ）または付箋紙（（厚さ0.2ｍｍ、サイズ２０ｍｍ×１０ｍｍ）につけて、ポリエチレンフィルムにはさんで５００ｇの分銅を１２時間のせておく。ベニヤ板の接着していない部分１０ｍｍとフィルムの接着していない一端１０ｍｍを引張試験機（島津製作所製ＡＧＳ−Ｈ）のクランプにはさみ、引張速度３０ｍｍ／分で引っ張り、接着部分の剥離に要したエネルギー（接着剥離エネルギー）を求めた。接着条件を規格化するために、同様に行った未処理の材料の接着剥離エネルギーを１．０として相対値を求めた。
用いた接着剤は、ベニヤ板の場合は、ポリシアノアクリレート系（アロンアルファ：東亜合成（株）製）と付箋紙の場合は、文具用の紙用途接着剤（商品名：コクヨ（株）製、プリット）である。
【００６３】
（２）ブラケットの場合：
処理または未処理ブラケットの接着面に接着剤を約０．０１ｇをつけ、セラミック製プレート（サイズ２０ｍｍ×１０ｍｍ）につけて、ループ状の針金をひっかけて、セラミック製プレートの接着していない部分を引張試験機（島津製作所製、ＳＶ５５−０−２０Ｍ）の下部クランプにはさみ固定し、針金を上部クランプに固定して、引張速度１１０ｍｍ／分で引っ張り、接着部分の剥離までに加えた荷重を求める。接着条件を規格化するために、同時に行った未処理の材料の剥離強度を１．０として相対値を求めた。重合性メタクリル樹脂系接着剤（メタクリル酸メチルモノマー、ポリマーおよび重合触媒等を混合して用いる）：商品名スーパーボンド（サンメディカル（株））、または自家製品を用いた。
【００６４】
請求項１、２、３に該当する処理をそれぞれ発明１、２、３として、以下に、ポリプロピレン、ポリエステル、ポリエチレンからなる各種不織布または織布の処理例を示す。これらの結果、得られた処理または未処理試料の吸水率、吸水高さ、洗浄後の吸水率を表２に示す。全ての実施例において、高分子材料に含まれる酸化防止剤、安定剤、その他の添加剤を除く操作はしなかった。
【００６５】
(実施例１) 発明１によるポリプロピレン不織布の親水化
含浸剤処理として、トルエン１００ｍｌを５０℃としてから、ＰＰ不織布１の１．０ｇ（サイズ２０ｃｍ×２０ｃｍ）を１５分間漬けた。次に、メタノールで濯いでから、遠心分離器（８００回転/分）に１分間かけた。試料の重量増加は４％程度であった。
次に、活性化処理として、３０分間のオゾン処理をした(オゾン発生速度：１．０ｇ／ｈ)。赤外線吸収スペクトルを測定して、１７１０ｃｍ^−１付近の吸収ピーク（カルボニル基の吸収）の吸光度の比は、０．０２であった。
次に、パイレックス製のガラス管に、水２００ml、硝酸二セリウムアンモニウム(IV)２０ｍｇ、アクリル酸０．６ｍｌを入れて作られた溶液に、処理材料を入れ、４００ワットの高圧水銀灯を２０ｃｍの距離から、３０℃に保ちながら、１２０分間照射した。処理後、材料は６０℃の洗剤水溶液にて１０分間、煮沸洗浄した後、水洗して、乾燥させた。処理試料の吸水性試験による吸水は３１０％であった。吸水高さは２．０ｃｍ／分であった。未処理の同不織布の吸水率は０％、吸水高さは０ｃｍ／分であった。
特に、吸水性、電解液の保持率に優れていた。耐アルカリ性、耐酸性、耐酸化剤性にも優れており、電池セパレータの製造法として有効である。
【００６６】
(実施例２)
含浸剤処理として、デカヒドロナフタレン（含浸剤Ｂ）、活性化処理として、３０秒のプラズマ処理、モノマーにメタクリル酸を用いること以外は、全て実施例１と同様である。
【００６７】
(実施例３)
含浸剤処理として、オルトヒドロキシビフェニール（ＯＨＢ）水分散液（含浸剤Ｃ）を用いること以外は、全て実施例１と同様である。
(実施例４)
含浸剤処理として、オルトヒドロキシビフェニールのメタノール溶液（含浸剤Ｄ）を用いることこと以外は、全て実施例１と同様である。
【００６８】
（実施例５）
含浸剤処理としてサリチル酸ナトリウム水分散液（含浸剤Ｅ）を用いること、活性化処理として、６０分間の紫外線照射処理を行うこと以外は、全て実施例１と同様である。
【００６９】
（実施例６）
含浸剤処理としてジフェニル溶液（含浸剤Ｆ）を用いること以外は、活性化処理として、６０分間の紫外線照射処理を行うこと以外は、全て実施例１と同様である。
（比較例１〜５）
比較例１は実施例１で用いたPP試料の未処理のものを用いた結果である。
比較例２は、実施例１の工程で、含浸剤処理工程を省いたこと以外は実施例１と同様である。
比較例３は、実施例１の工程で、含浸剤処理工程と活性化工程を省いたこと以外は実施例１と同様である。比較例４は、実施例１の工程で、含浸剤処理工程とグラフト化工程を省いたこと以外は実施例１と同様である。比較例５は、実施例１の工程で、活性化処理工程を省いたこと以外は実施例１と同様である。
【００７０】
（実施例７）
ＰＰ試料として、ＰＰ平織布を用い、含浸剤処理として、オルトヒドロキシビフェニール（ＯＨＢ）溶液（含浸剤Ｃ）、および活性化処理として、２時間の紫外線照射を行った。その他の方法および手順は実施例１と同様である。グラフト化は実施例１と同様であった。
【００７１】
（比較例６）未処理のＰＰ平織布の結果である。
【００７２】
（比較例７）ＰＰ平織布を試料として、含浸剤処理を省いたこと以外は、実施例２と同様の処理である。実施例３より、吸水率の耐久性が、少し落ちた。
【００７３】
(実施例８)
ＰＥＴ不織布（サイズ１０ｃｍ×１０ｃｍ）を用い、キャリヤー１（商品名：キャリアント）の水分散液（試薬５ｇを水２００ｍｌに混合した）を用い、開始剤としてＣＡＮの代わりにＡＩＢＮ２０ｍｇを用いて、実施例１と同法で行った。
【００７４】
(実施例９)
ＰＥＴ不織布（サイズ１０ｃｍ×１０ｃｍ）を用い、キャリヤー２（商品名：キャリヤーTW２００）の水分散液（試薬５ｇを水２００ｍｌに混合した）を用い、活性化はオゾン処理、グラフト化は開始剤としてＣＡＮの代わりにＡＩＢＮ２０ｍｇを用いて、７０℃で４時間の熱重合を行った（実施例と手順は同様であるが、紫外線を照射しなかった）。
実施例１と同法で行った。
【００７５】
（実施例１０)
ＰＥＴ不織布（サイズ１０ｃｍ×１０ｃｍ）について、実施例１と同法で行った。
【００７６】
（比較例８〜１２）
ＰＥＴ不織布について、比較例８は未処理、比較例９は実施例１から含浸剤処理を省き、比較例１０は実施例１から含浸剤処理と活性化処理を省き、比較例１１は実施例４から含浸剤処理とグラフト化処理を省いた処理である。比較例１２は実施例１から活性化処理を省いたものである。
【００７７】
（実施例１１〜１２）
実施例１１は、ＰＰ不織布２とオルトヒドロキシビフェニール（ＯＨＢ）溶液（含浸剤Ｃ）を用いて、実施例１と同様に、また実施例１２はＰＰ不織布２と含浸剤Ｃを用いて、実施例２と同様に行った。
【００７８】
（比較例１３〜１７）
いずれもＰＰ不織布２を用いた。比較例１３は、未処理ＰＰ不織布２、比較例１４は含浸剤処理を省いた以外は実施例１と同様、比較例１５は含浸剤処理と活性化処理を省いた以外は実施例１と同様、比較例１６は活性化処理としてのオゾン処理のみ、比較例１７は活性化処理を省いた以外は、実施例１と同様である。
【００７９】
（実施例１３）
Ｐ／Ｅ不織布を試料とし、含浸剤処理としてオルトヒドロキシビフェニール（ＯＨＢ）の水分散液（含浸剤Ｃ）を用い、活性化はオゾン処理、開始剤に硝酸二セリウムアンモニウム（IV）を用い、メタクリル酸をモノマーとして、８０℃で３時間の熱グラフト化を行った。
【００８０】
（実施例１４）Ｐ／Ｅ不織布を試料とし、硝酸二セリウムアンモニウム（IV）の代りに、加硫酸カリウムを用いて、実施例２と同様に行った。
【００８１】
（比較例１８）未処理のＰ／Ｅ不織布の結果である。
【００８２】
表２に結果をまとめた。
なお、吸水率は、処理後、洗剤洗浄して乾燥後の値、３回洗浄後の吸水率は、煮沸洗剤溶液による洗浄、乾燥を３回行った後の吸水率である
【００８３】
【表２】

【００８４】
以下に、ポリエチレンテレフタレートフィルム、超高分子量ポリエチレン板、ポリプロピレンフィルムの処理の実施例と、未処理および本発明の方法から１ないし２工程を省いた比較例を示す。結果は、表３にまとめて示す。
【００８５】
(実施例１５)
ポリエチレンテレフタレートフィルムの処理
含浸剤処理として、トルエン１００ｍｌ（含浸剤Ａ）を８０℃としてから、ＰＥＴフィルム１．６２ｇ（サイズ１５ｃｍ×１５ｃｍ）を１５分間漬けた。次に、メタノールで濯いでから、余分なキャリヤーを紙でふき取り、５分間、室温で乾燥させた。
次に、活性化処理として、３０分間のオゾン処理をした(オゾン発生速度：１．０ｇ／ｈ)。
次に、グラフト化を、パイレックス製のガラス管に、水２００ｍｌ、ＡＩＢＮ２０ｍｇ、アクリル酸１．２ｍｌを入れて作られた溶液に、処理材料を入れ、８０℃に保ちながら、４時間放置した。処理後、材料は６０℃の洗剤水溶液にて１分間、煮沸洗浄した後、水洗して、乾燥させた。処理試料の吸水性試験による吸水は９０%で、水の接触角は６３°であった。文具用糊（プリット）による、付箋紙の接着剥離強度は、未処理の接着剥離強度を１とした場合、４．０であった。
【００８６】
（実施例１６）
オルトヒドロキシビフェニールの水分散液（含浸剤Ｃ）１００ｍｌを７０℃としてから、ＰＥＴフィルム１．６２ｇ（サイズ１５ｃｍ×１５ｃｍ）を１５分間漬けた。次に、メタノールで濯いでから、余分な紙でふき取り、５分間、室温で乾燥させた。
次に、実施例１と同様のオゾン処理をした後、紫外線照射グラフト化を、水１８０ｍｌ、過硫酸カリウム２０ｍｇ、メタクリル酸１．２ｍｌを用いて行った。
【００８７】
（実施例１７）
オルトヒドロキシビフェニールのメタノール溶液（含浸剤Ｄ）を用いた以外は、実施例１６と同様に行った。
【００８８】
（実施例１８）
サリチル酸ナトリウム１ｇの水分散液（含浸剤Ｅ）を用いた以外は、実施例１６と同様に行った。
【００８９】
（比較例１９）
未処理ＰＥＴフィルムの結果である。
（比較例２０）
実施例１６から含浸剤処理を省いた処理を行った。
（比較例２１）
実施例１６から含浸剤処理と活性化処理を省いた処理を行った。
（比較例２２）
実施例１６から含浸剤処理とグラフト化処理を省いた処理を行った。
（比較例２３）
実施例１６から活性化処理を省いた処理を行った。
【００９０】
（実施例１９）
超高分子量ポリエチレン板３．８４ｇ（サイズ１０ｃｍ×１０ｃｍ）を
含浸剤処理として、トルエンの１００ｍｌ（含浸剤Ａ）に７０℃で１５分間漬けた。次に、メタノールで濯いでから、余分な含浸剤を紙でふき取り、５分間、室温で乾燥させた。
次に、活性化は、オゾン処理を１２０分行った。次に、実施例２と同様の紫外線照射グラフト化を、水１８０ｍｌ、硝酸二セリウムアンモニウム（IV）２０mg、アクリル酸１.０mlを用いて行った。
【００９１】
（実施例２０）
含浸剤処理としてデカヒドロナフタレン（含浸剤Ｂ）を用いた以外は、実施例１９と同様に行った。
【００９２】
（実施例２１）
オルトヒドロキシビフェニール（ＯＨＢ）（含浸剤Ｃ）を用いたこと、グラフト化の際に開始剤を加えなかったこと以外は、実施例１９と同様に行った。
【００９３】
（比較例２４）
未処理の超高分子量ポリエチレン板の結果である。
（比較例２５）
実施例１９から含浸剤処理を省いた処理を行った。
（比較例２６）
実施例１９から含浸剤処理と活性化処理を省いた処理を行った。
（比較例２７）
実施例１９から含浸剤処理とグラフト化処理を省いた処理を行った。
（比較例２８）
実施例１９から活性化処理を省いた処理を行った。
【００９４】
（実施例２２）
ポリプロピレンフィルム０．３８ｇ（サイズ１５ｃｍ×１５ｃｍ）を
オルトヒドロキシビフェニールの水分散液（含浸剤Ｃ）（７０℃、１００ｍｌ）に１０分間漬けた。次に、メタノールで濯いでから、余分な含浸剤を紙でふき取り、５分間、室温で乾燥させた。
次に、活性化は、オゾン処理を４５分行った。次に、実施例１と同様の紫外線照射グラフト化を、水１８０ｍｌ、ＡＩＢＮ２０ｍｇ、アクリル酸１.０ｍｌを用いて行った。
【００９５】
（実施例２３）
オルトヒドロキシビフェニールのメタノール溶液（含浸剤Ｄ）を用いた以外は、実施例１７と同様に行った。
【００９６】
（実施例２４）
サリチル酸ナトリウム（含浸剤Ｅ）を用い、活性化処理として３０秒のプラズマ処理を行い、モノマーにアクリル酸とメタクリル酸の混合物を用い、その他は実施例１７と同様である。
【００９７】
（比較例２９）
未処理ポリプロピレンフィルムの結果である。
（比較例３０）
実施例２２から含浸剤処理を省いた処理を行った。
（比較例３１）
実施例２２から含浸剤処理と活性化処理を省いた処理を行った。
（比較例３２）
実施例２２から含浸剤処理とグラフト化処理を省いた処理を行った。
（比較例３３）
実施例２２から活性化処理を省いた処理を行った。
以上の結果を表３にまとめて示した。
【表３】

【００９８】
（実施例２５）
炭素繊維の親水化と複合材料用途：
炭素繊維６．０ｇを、含浸剤処理として、５０℃のメタノールに３０分浸けた。次に、遠心分離器（８００回転／分）に１分間かけた。次に、活性化処理として、厚さ１．５ｍｍの硬質ガラス製容器に入れ、オゾン発生機に流量１００ｍｌ／分の酸素を導入し、４０ｍｇ／Ｌの濃度のオゾンを発生させ、これを容器に導入し、３０分間吹き込んだ。次に、オゾンを含まない酸素を１０分間吹き込んだ。次に、グラフト化として、処理繊維に、アクリル酸１．２ｍｌ 、水２００ｍｌ、メタノール５ｍｌを加えて、反応容器を窒素雰囲気にした。高圧水銀ランプ（東芝高圧水銀灯Ｈ４００Ｐ）を反応容器まで１５．５ｃｍの距離から３時間照射した。温度は４５℃とした。次に容器の内容物を大量の水中に投入した。ポリマーの付着した炭素繊維を取り出し、洗剤よる煮沸洗浄を３回行った。グラフト率は１５％であった。処理後、沸騰洗剤水溶液で３回洗浄した（１回、５００ｍｌの水を使用）。乾燥後、吸水率は２００％（未処理は１２０％）と上昇した。
【００９９】
（比較例３４）なお、含浸剤処理を除いて、活性化処理と紫外線グラフト化した場合、グラフト率は４．２％であった。
（比較例３５）含浸剤処理と紫外線グラフト化処理を行った場合、グラフト率は３．０％であった。
（比較例３６）紫外線グラフト化のみを行った場合、グラフト率は１．０％であった。
【０１００】
（実施例２６）実施例２５で得られた炭素繊維を、エポキシ樹脂接着剤と混合して、乾燥して、５ｍｍ×５ｍｍ×１００ｍｍの棒を作った。比較のために、親水化未処理の炭素繊維を混合したエポキシ樹脂棒を作った。親水化炭素繊維強化エポキシ樹脂棒の引張強度は、親水化未処理の炭素繊維を混合したエポキシ樹脂棒の４０倍の引張強度を示した。
【０１０１】
（実施例２７）
羊毛繊維布の親水化：
羊毛繊維（織布）１．０２ｇを、含浸剤処理として、５０℃の無水炭酸ナトリウム１０ｍｇとメタノール１０容と水９０容からなる溶液に３０分浸けた。次に、遠心分離器（８００回転／分）に１分間かけた。次に、活性化処理として、オゾン発生機に流量１００ｍｌ／分の酸素を導入し、４０ｍｇ／Ｌの濃度のオゾンを発生させ、これを容器に導入し、３０分間接触させた。次に、オゾンを含まない酸素を１０分間吹き込んだ。次に、グラフト化として、処理繊維に、アクリル酸１．２ｍｌ 、水２００ｍｌ、メタノール５ｍｌを加えて、反応容器を窒素雰囲気にした。高圧水銀ランプ（東芝高圧水銀灯Ｈ４００Ｐ）を反応容器まで２０ｃｍの距離から３時間照射した。温度は４５℃とした。次に容器の内容物を大量の水中に投入した。ポリマーの付着した炭素繊維を取り出し、洗剤よる煮沸洗浄を３回行った。グラフト率は１８％であった。
【０１０２】
（比較例３７）なお、含浸剤処理を除いて、活性化処理と紫外線グラフト化した場合、グラフト率は４．２％であった。
（比較例３８）紫外線グラフト化のみを行った場合、グラフト率は１．５％であった。
（比較例３９）含浸剤処理と紫外線グラフト化した場合、グラフト率は１．６％であった。
【０１０３】
（吸水性のテスト）
処理および未処理の羊毛繊維布を水面に平行に浮かべて、吸水して沈むまでの時間を計測した。未処理羊毛布は６０分、実施例２７の処理羊毛布は１秒、比較例３７、３８、３９はそれぞれ、１５秒、２８秒、３０秒であった。
【０１０４】
（実施例２８）
ポリプロピレン製合成紙の親水化：
合成紙用の多孔性ポリプロピレンフィルムについて、実施例２と同様の処理を行い、親水性を付与できた。処理合成紙は、水溶性インクでの筆記が可能となり、水溶性の糊料（デンプン、ＣＭＣ、ＰＶＡ糊など）で、付せん紙を接着できた。付せん紙は破断するために剥離できなかった。
【０１０５】
（実施例２９）
多孔性ポリエチレンフィルムの親水化及びフィルター用途：
多孔性ポリエチレンフィルム０．３ｇ（サイズ１０ｃｍ×１０ｃｍ）について、実施例１７と同様の処理を行った。処理フィルムは、沸騰洗剤水溶液で洗浄し、よく水洗した。乾燥後、吸水率は２００％（未処理多孔性ポリエチレンフィルムは５％）であった。水の接触角は、吸水性のため、測定不可能であった（０°とみなされる、未処理多孔性ポリエチレンフィルムは１２０°）。また親水化処理による試料の重量増加は２％であった。この親水化多孔性ポリエチレンフィルムは、耐アルカリ性と耐酸性があり、水溶液中の成分を、ろ過するのに有効であった。
【０１０６】
（実施例３０）多孔性ポリエチレンフィルムについて、含浸剤処理（７０℃のトルエンで１５分間）、活性化処理（プラズマ処理０．５分間）、紫外線グラフト化（メタクリル酸と過硫酸カリウム使用）によって、実施例２６と同様の結果が得られた。
【０１０７】
（実施例３１）
多孔性ポリサルホンフィルムの親水化及びフィルター用途：
多孔性ポリサルホンフィルム０．５ｇ（サイズ１０ｃｍ×１０ｃｍ）について、含浸剤処理として、メタノール１０体積％水溶液に室温で１分間浸けた。活性化処理としてオゾン処理を５分行った。実施例１７と同様の処理を行った。処理フィルムは、沸騰洗剤水溶液で洗浄し、よく水洗した。乾燥後、吸水率は２００％（未処理多孔性ポリエチレンフィルムは５％）であった。水の接触角は、吸水性のため、測定不可能であった（未処理多孔性ポリエチレンフィルムは１２０°）。また親水化処理による試料の質量増加は２％であった。この親水化多孔性ポリエチレンフィルムは、耐アルカリ性と耐酸性、耐熱性（120℃のオートクレーブで３０分間の加熱処理を３回繰り返した）があり、水溶液中の成分を、ろ過するのに有効であった。
【０１０８】
（実施例３２）
ポリプロピレン不織布２の親水化（ポリビニルアルコール使用）：
ポリプロピレン不織布２の１．０ｇ（サイズ：約１５ｃｍ×１５ｃｍ）を含浸処理として、ジフェニル２．５ｇと界面活性剤（ドデシルベンゼンスルホン酸ナトリウム）０．２ｇを水２００ｍｌに混合して得た溶液に、５０℃で５分間浸けた。次に、遠心分離器（回転数１０００回／分）で脱液した。重量増加４％となったら、活性化処理として２０℃で３０分間のオゾン処理をした。次に、高分子処理として、処理不織布を反応容器に入れ、水２００ｍｌ、過硫酸カリウム６０ｍｇ、ポリビニルアルコール０．３ｇ、メタノール６ｍｌの混合物を加えて、８０℃で２時間処理した。処理後、水洗し、洗剤洗濯を行った。吸水率は８００〜１１００％でり、親水化処理による試料の質量の増減は０．１ｍｇの精度では測定できなかった。結果を表１に示す。６回の洗剤洗濯の後でも吸水率８１０％以上を保った。本処理試料は、吸水性用途の材料として最適であった。
【０１０９】
（実施例３３）発明２によるポリプロピレン不織布２の処理（カルボキシメチルセルロースナトリウム使用）：
ポリプロピレン不織布２の処理を、ポリビニルアルコールの代わりに、カルボキシメチルセルロースナトリウムを用い実施例３２と同様に行った。吸水率は６００〜９００％で、耐久性があった。
【０１１０】
（実施例３４）
微生物培地の用途：実施例３２に基づいて製造した吸水性不織布をそれぞれ各２枚づつ２ｃｍ×２ｃｍに切り、直径８ｃｍ、深さ２ｃｍのシャーレに重ならないように並べた。１重量％肉エキス、１重量％ポリペプトン、０．５重量％塩化ナトリウム、１．５重量％寒天を含む水溶液からなるブイヨン寒天溶液１００mlをつくり、電子レンジで寒天を融解させた後、このブイヨン寒天溶液５０mlを前記不織布にしみ込ませた後、室温に戻した。こうして得られたブイヨン寒天溶液をしみ込ませた不織布（培地不織布とする）を１２０℃、１５分間オートクレーブ滅菌した試験管に入れた。この試験官を立てた状態で３７℃で一晩保温し、翌日、無菌状態を確認した後、培養する微生物株（大腸菌Ｋ−１２株、サルモネラタイヒムリウムＬＴ−２株、枯草菌マールブルグ株など）を植株し、これを恒温器で３０〜３７℃で一晩静置培養した。植株した各種菌の生育状態を顕微鏡で観察したところ各種菌は順調に生育していた。
【０１１１】
（比較例４０）
ポリプロピレン不織布２について実施例３２の含浸処理の工程を除いた処理を行った。処理試料の吸水性は、洗剤洗浄を３回行った後、７８０％から４００％まで低下した。
【０１１２】
（実施例３５）発明３による試料６の親水化と拭き取り清掃用布の用途：
試料６はポリエステルを芯、ポリエチレンを鞘とする芯鞘型繊維の不織布である。
ポリエチレン／ポリエステル芯鞘型複合繊維の不織布２．４ｇを、室温で、含浸処理として、１０ｍｌのオルトヒドロキシビフェニール０．５ｇをメタノール３００ｍｌに溶解して得た溶液（含浸剤Ｄ）に７０℃で１０分間浸けた。
次に遠心脱水器（回転数１０００／分）にかけ、見掛け上、表面が乾いた状態にした。質量増加は４％程度であった。次に、３０分間のオゾン処理をした。次に、オゾン処理した不織布を三角フラスコに入れ、メタノール５ｍｌ、水１００ｍｌ、ポリビニルアルコール０．５ｇ、過硫酸カリウム０．１ｇを加え、８０℃で２時間処理した。処理後、６０℃の水で充分に洗浄した。処理不織布の水を絞り（吸水率３００％程度に）、容器に入れ、水４００ｍｌ、硝酸二セリウムアンモニウム（IV）１００ｍｇ、アクリル酸５ｍｌを加えて、窒素雰囲気として、８０℃で２時間放置した。処理不織布は、処理後、６０℃の洗剤液で３回洗浄した（１回、５００ｍｌの水を使用）。乾燥後、吸水率（吸水性試験１による）は２３１０％であり、また未処理の同不織布は３５０％であった。また親水化処理による試料の重量増加は４％であった。発明１の方法よりもさらに、吸水率が高く、（発明１の方法で処理すると、吸水率１４００％程度）、かつ吸水速度および吸水性の耐久力に優れ、拭き取り清掃用のワイパー（雑巾の代替物）として最適であった。親水化処理不織布に吸水させて（吸水率２０００％程度）、１０枚重ねとして、清掃用モップにとりつけ、木製床の拭き取りに使用した。使用後、水で濯ぎ、１０回以上の繰返し使用が可能であった。
【０１１３】
（実施例３６）
親水化ポリプロピレン不織布2と使い捨て衛生用品の材料用途：
実施例１１の方法で得られた親水化ポリプロピレン不織布２を内側布として、水分保持剤（吸水性高分子：パルプ、デンプンまたはポリアクリル酸改質物等）と、外部用未処理ポリプロピレン不織布を用いて、使い捨てオムツのモデルを製造した。即ち、最も下に、未処理の撥水性ポリプロピレン不織布を置き、その上に吸水性ポリマーを敷き、さらにその上に、本発明の吸水性ポリオレフィン不織布を置いた。上から水をかけると、水は迅速に吸水性ポリオレフィン不織布を透過して、水分保持剤に吸収された。このように、本発明による吸水性不織布は、使い捨てオムツや衛生・生理用品の素材として最適である。
【０１１４】
（実施例３７）
歯列矯正用ポリプロピレン製ブラケットの接着性改良：
歯列矯正用ポリプロピレン製ブラケット２０個（０．６２２ｇ）について、実施例１４と同様の方法で、メタクリル酸メチルをグラフト化させた。メタクリル酸メチルの重合抑制剤は除いて用いた。処理物は重合性アクリル樹脂接着剤によるセラミックス歯科材料との接着性が改良され、引張試験により歯列矯正用ポリプロピレン製ブラケットの材料破壊が起こった。
【０１１５】
（比較例４１）
公知の界面活性剤により親水化されたポリプロピレン／ポリエチレン不織布（日本バイリーン（株）製に界面活性剤を含浸させたもの：目付け等は表１の試料４と同様）を用意し、実施例１と同様の評価を行った。結果は以下のとおりであった。
１）耐アルカリ性試験：乾燥後、吸水性は元の５％に低下した。
２）耐硫酸試験：十分に水洗して、乾燥後、吸水性は元の５％に低下した。
３）耐酸化剤試験：乾燥後、吸水率は元の５％に低下した。
【０１１６】
（比較例４２）公知の紫外線照射による不織布１へのアクリル酸のグラフト化：ポリプロピレンからなる表１記載の不織布１の１．２ｇ（サイズ７．７ｃｍ×１０ｃｍ）を、アクリル酸モノマー２０．０％、水７８．８％、ベンゾフェノン０．２％およびメタノール１．０％（いずれも重量％）の組成を有する反応溶液に浸けて、４００ワットの高圧水銀灯を１２ｃｍの距離から、１２０分間照射した。反応後の不織布は重合物で固まっていたが、脂肪酸ナトリウム石鹸水溶液（濃度２重量％、浴比１／２０）で１０分間煮沸洗浄後、水洗した結果、重合物は溶解し、分離した。得られた不織布の吸水率は１００％であった（未処理の不織布は４８％）。グラフト率は１％であった。即ち、紫外線照射によるグラフト化は、本不織布の場合、困難であり。洗剤による煮沸洗浄にて、生成したアクリル酸のみからなる単独ポリマーは溶解して不織布から外れるとみられた。酸およびアルカリ処理用によって、親水性が低下した。
【０１１７】
【発明の効果】
以上に説明したとおり、本発明の高分子材料の改質方法により得られた各種高分子材料は強度低下を伴うことなしに優れた吸水性、接着剤による接着性等の性質改善効果を示した。改質により付与された性質は耐久性に優れている。また、ポリオレフィン製の濾過材の親水化により、水溶液の濾過用途が開発された。合成紙に吸水性を付与し、接着性も向上でき、印刷性能の改良が期待できる。炭素繊維を含む多くの高分子材料の接着剤による接着性が向上するため、複合材料の強化繊維として有用な親水化処理物を与える。各種高分子成形物についても、親水性を改良でき、従来不可能であったポリオレフィン製の筆記具用部品について、水溶性インクの吸収性等を改良できる。各種医療・衛生・化粧用品、衣料用繊維製品の用途や、歯列矯正用ポリプロピレン製ブラケットの接着性の改良、高分子製医療用材料の水濡れ性を改善できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for modifying a polymer material. In particular, the present invention relates to a modification method that improves water absorption and adhesion without reducing the strength of the polymer material. The present invention also relates to a polymer material obtained by such a modification method and its use.
[0002]
[Prior art]
Polyolefin materials such as polypropylene and polyethylene are excellent in lightness, strength, chemical resistance, and the like, and are widely used for molded products such as films, nonwoven fabrics, automobile parts and electrical equipment parts. However, the polyolefin material has characteristics that it has low polarity due to its chemical structure and high crystallinity, so that it is poor in hydrophilicity and hardly undergoes chemical modification. Conventionally, ozone treatment, plasma treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, corona discharge treatment, sandblast treatment, solvent etching treatment, chromium mixed acid treatment, flame treatment, etc. have been performed to improve the hydrophilicity and adhesion of these materials. Attempts have been made to perform various surface activation treatments. However, even if these surface treatments are performed, water absorption enough to absorb water several times its own weight is not provided.
For example, a method for improving the plating property, paintability, and adhesiveness by applying an ozone oxidation treatment was examined (Japanese Patent Publication No. 3-103448). However, if the desired surface characteristics are to be imparted only by the ozone treatment, the ozone treatment must be severe, and there is a problem that the strength of the object to be treated is remarkably lowered and it cannot be put into practical use. Further, water absorption cannot be sufficiently imparted only by ozone oxidation treatment. Any of the other treatment methods described above has problems such as difficulty in high activation without a decrease in strength, increased equipment costs, and waste disposal burden.
[0003]
In addition to the method of directly activating the surface of the polymer material as described above, a method of forming a layer made of a highly active component on the surface of the polymer material has been proposed. For example, a method has been proposed in which a vinyl monomer having an ester bond is graft-polymerized on a nonwoven fabric of polyolefin fiber, and then the ester bond is hydrolyzed to generate an acid group to thereby have hydrophilicity and ion exchange capacity ( JP-A-11-7937). However, there is a problem that it is not easy to graft a sufficient amount for imparting hydrophilicity even when a vinyl monomer is grafted onto a polyolefin fiber or film by the disclosed method. Moreover, it is necessary to further hydrolyze after the graft polymerization, which is troublesome.
[0004]
On the other hand, a method for imparting hydrophilicity by treating a nonwoven fabric made of polyolefin fibers with a hydrophilic resin in the presence of a persulfate has been proposed (Japanese Patent Laid-Open No. 11-67183). In this method, the nonwoven fabric could be given hydrophilicity to a practical level, but the hydrophilic durability was not always sufficient. For example, when heated with a detergent, the hydrophilicity is considerably lost. Further, when a film or a molded product other than the nonwoven fabric is processed, sufficient hydrophilicity cannot be imparted, or the adhesiveness due to the adhesive cannot be improved.
A method of coating a nonwoven fabric with polyvinyl alcohol to impart hydrophilicity is also known (Japanese Patent Application Laid-Open No. 1-248460). However, although the obtained coating is highly hydrophilic, there is a problem that hydrophilic durability is not sufficient because it is a simple coating.
[0005]
In addition, the inventor first activated the surface of the polymer material, and then graft-polymerized monomers such as acrylamide, or further transferred the amide group of the grafted compound to the Hoffmann transition, thereby achieving particularly high dyeability. An improved surface modification method for polymer materials has been proposed (Japanese Patent Laid-Open No. 8-109228). Based on this method, a polymer material imparted with hydrophilicity can be produced. However, this method has a limit in the types of polymer material to be treated.
Further, the present inventor treats the polymer material in the order of (1) an activation treatment and (2) a treatment with a hydrophilic polymer. Alternatively, the polymer material is treated in the order of (1) an activation treatment step (2) a hydrophilic polymer treatment step and (3) a monomer grafting step, or the polymer material is Proposed a method for modifying a polymer material characterized by (1) a solvent treatment step, (2) an activation treatment step, and (3) a treatment step with a hydrophilic polymer. Hei 11-375055, PCT / JP00 / 090420).
According to these methods, a polymer material imparted with excellent hydrophilicity can be easily produced at low cost. However, these additives reduce the effect of the activation treatment when processing molded articles of polymeric materials containing additives such as stabilizers and antioxidants to determine powerful and durable hydrophilic properties. There is a case.
[0006]
The technical demands as described above exist not only for polyolefins but also for other polymer materials having superior surface activity. For example, it may be required to modify the original surface properties of the polymer to give the desired surface properties.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for modifying the surface of a polymer material which is not accompanied by a decrease in the strength of the material and has excellent durability.
In addition, the present invention is for medical / hygiene / cosmetic products made of such modified materials, that is, disposable diapers, sanitary products, bandages, gauze, disinfecting adhesive cloths, various cleansing applications / face-wash packs, napkins, etc. Water-absorbing materials, water-retaining materials such as agricultural and dry land greening materials, microbial medium materials, synthetic paper, filter media, wiping and cleaning materials, orthodontic brackets, medical equipment materials (artificial organs, joints, various tubulars) It is an object of the present invention to provide a polymer material with improved adhesiveness, a composite material with the polymer material, and the like.
[0008]
[Means for Solving the Problems]
As a result of intensive studies on surface modification methods for various polymer materials in order to achieve the above-mentioned object, the present inventor has conducted impregnation treatment, activation treatment, grafting of vinyl monomer, and treatment with a hydrophilic polymer. The present invention has been completed by finding that it is effective to combine the two. That is, the present invention is to contact the surface of the polymer material with (1) a compound impregnated with the polymer material, Within 1000 microns from the surface Impregnation treatment step in which the impregnation amount is in the range of 0.1 to 40% by weight (with respect to the polymer material) and the shape of the material is not substantially changed, (2) A carbonyl group is introduced on the surface of the polymer material And (3) a step of grafting the monomer in the presence of at least one of a catalyst, an initiator, heating, and ultraviolet irradiation. It is about quality methods.
[0009]
Alternatively, in the present invention, the surface of the polymer material is brought into contact with (1) a compound impregnated with the polymer material, Within 1000 microns from the surface An impregnation treatment step in which the impregnation amount is in the range of 0.1 to 40% by weight (with respect to the polymer material) and the shape of the material is not substantially changed, (2) a carbonyl group is introduced on the surface of the polymer material Activation treatment step, (3) in the presence of catalyst or initiator Or in the absence The present invention relates to a method for modifying a polymer material, characterized in that the treatment is performed in this order by the step of treating with a hydrophilic polymer solution.
[0010]
Alternatively, in the present invention, the surface of the polymer material is brought into contact with (1) a compound impregnated with the polymer material, Within 1000 microns from the surface An impregnation treatment step in which the impregnation amount is in the range of 0.1 to 40% by weight (with respect to the polymer material) and the shape of the material is not substantially changed, (2) a carbonyl group is introduced on the surface of the polymer material Activation treatment step, (3) in the presence of catalyst or initiator Or in the absence And (4) a step of grafting the monomer in the presence of at least one of a catalyst, an initiator, heating, and ultraviolet irradiation. The present invention relates to a method for modifying a polymer material.
[0011]
Alternatively, the present invention provides a polymer material having a modified surface obtained by such a modification method, a water-absorbing material using the same, a water retention material, a microorganism medium material, a synthetic paper, a filter material, a wipe cleaning cloth, Disposable medical / hygiene / cosmetic products (diapers, sanitary products, bandages, gauze, napkins, tapes, other medical / hygiene products, cosmetic products such as various cleansing / facial cleansing packs, etc.), adhesive improvement materials, orthodontics It relates to brackets, medical device materials (artificial organs, tubes, threads, plate-like molded products) and the like.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is described in detail below.
(Polymer material)
The polymer material used in the present invention is a material obtained by mixing or combining a polymer single material, a mixed material or a modified material thereof, or a polymer, a glass, a metal, a carbon material, or the like. Means the polymeric material involved. As the synthetic polymer, any of a thermoplastic polymer and a thermosetting polymer can be used. Although various methods are illustrated as a synthesis method, the polymer material of the present invention includes a synthetic polymer obtained by any of these methods. For example, (1) addition polymer: homopolymer or copolymer of a monomer selected from the group consisting of olefins, vinyl compounds other than olefins, vinylidene compounds and other compounds having a carbon-carbon double bond, or Mixtures or modifications of these homopolymers or copolymers, (2) polycondensates: polyesters, polyamides, etc., or mixtures or modifications of these polymers, (3) addition condensates: phenol resins (Kinol: (Including trade name, manufactured by Nippon Kainol Co., Ltd.), urea resin, melamine resin, xylene resin, etc., or a mixture or modified product of these polymers, (4) polyaddition product: polyurethane, polyurea, etc. (5) Ring-opening polymer: cyclopropane, ethylene oxide, propylene Homopolymers or copolymers of oxides, lactones, lactams, etc., or mixtures or modifications of these homopolymers or copolymers, (6) cyclized polymers: divinyl compounds (eg, 1,4-pentadiene) Or homopolymers such as diyne compounds (eg, 1,6-heptadiyne), or mixtures or modifications of these homopolymers or copolymers, (7) isomerized polymers: eg ethylene and isobutene (8) Electrolytic polymer: Homopolymer or copolymer of pyrrole, aniline, acetylene, etc., or a mixture or modified product of these homopolymers or copolymers, (9) Aldehyde or Examples include ketone polymers, (10) polyethersulfone, (11) polypeptide, and the like. Examples of the natural polymer include cellulose, protein, polysaccharide and the like alone or as a mixture, and modified products thereof.
[0013]
In the present invention, the above addition polymer is particularly preferably used. Although the monomer which comprises an addition polymer is not specifically limited, As olefin, arbitrary things, such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, etc. An α-olefin homopolymer or a copolymer of two or more of these, or a mixture of these homopolymers and / or copolymers can be appropriately used.
In the present invention, the vinyl compound other than olefin is a compound having a vinyl group, such as vinyl chloride, styrene, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid ester, vinyl acetate, vinyl ethers, vinyl carbazole, acrylonitrile. Etc. A vinylidene compound other than olefin is a compound containing a vinylidene group, and examples thereof include vinylidene chloride, vinylidene fluoride, and isobutylene.
Examples of compounds having carbon-carbon double bonds other than olefins, vinyl compounds and vinylidene compounds include maleic anhydride, pyromellitic anhydride, 2-butenoic acid, ethylene tetrafluoride, ethylene trifluoride chloride and the like and double bonds Examples of the compound include two or more, such as butadiene, isoprene, chloroprene and the like.
[0014]
As a preferable addition polymer, a homopolymer of these monomers, a copolymer of two or more monomers, or a mixture of these polymers can be appropriately used. Particularly preferred are polyethylene, copolymers of ethylene and other α-olefins, and copolymers of polypropylene, propylene and other α-olefins. The copolymer includes a random copolymer and a block copolymer.
In the present invention, polyolefin is preferably used as the polymer material because it is particularly effective for imparting hydrophilicity to polyolefin, which is said to be difficult to treat.
[0015]
The polymer material other than polyolefin is a homopolymer or copolymer of at least one monomer selected from the group consisting of vinyl compounds other than olefins, vinylidene compounds, and other compounds having a carbon-carbon double bond. , For example, polymethacrylate resin, polyacrylate resin, polystyrene, polytetrafluoroethylene, acrylonitrile copolymer (acrylic fibers and their moldings, ABS resin, etc.), copolymer containing butadiene (synthetic rubber) ), Etc., and polyamides (including aliphatic polyamides and aromatic polyamides including nylon), polyesters (including polyethylene terephthalate and aliphatic and wholly aromatic polyesters), polycarbonates, polyurethanes, polybenzoates, polyether sulfones Poloacetal, various synthetic rubbers and the like are preferably used.
[0016]
Examples of the polymer compound other than the above include, for example, polyacetal, polyphenol, polyphenylene ether, polyalkyl paraoxybenzoate, polyimide, polybenzimidazole, poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole, polybenzothiazole. Examples include polybenzoxazole, acetate fiber, regenerated cellulose fiber (rayon, cupra, polynosic, etc.), vinylon, fiber of vinyl alcohol and vinyl chloride copolymer (polyclar, trade name: corderan, etc.), etc. it can. Furthermore, natural fibers such as carbon fibers, cotton, hemp and other plant fibers, and animal fibers such as silk and wool can also be used. Also, a mixture or composite of a plurality of these polymer materials can be preferably used.
The polymer material used in the present invention is not limited to those described above, and can be applied to all polymer compounds.
[0017]
The polymer material may contain an antioxidant, a stabilizer, a nucleating agent, a flame retardant, a filler, a foaming agent, an antistatic agent, and other additives that are usually added to other polymer materials. In general, stabilizers such as antioxidants obstruct surface activation, and thus their presence is considered to be undesirable, and measures such as preparing additive-free materials or removing stabilizers are desirable. ing. On the other hand, the present invention can achieve effective surface modification even when the polymer material contains an additive such as a stabilizer. Therefore, a molded product obtained by a normal production method can be used as it is as a polymer material.
[0018]
In the present invention, there is no particular limitation on the form of the molded article of the polymer material subjected to the modification treatment. For example, any form of fiber, woven fabric, non-woven fabric, cloth, plate, film, sheet, tube, rod, hollow container, box, foam, and laminate can be used. In particular, from the viewpoint of improving water absorption, molded articles such as fibers, woven fabrics, nonwoven fabrics, cloths, films, and sheets can be easily treated. In particular, porous films and sheets produced for filters and synthetic papers can be subjected to durable and effective hydrophilic treatment. Further, by applying the processing method of the present invention to a molded body for a member or part that has been previously molded into a predetermined shape, a polymer material that could not be used conventionally can be used. Various plastic products (bolts, nuts, chains, parts of electric appliances, caps, covers, etc.) are also made hydrophilic by the present invention, so that wettability and adhesion are improved, and chargeability is reduced. .
As fibers and fiber products, various fibers, woven fabrics and nonwoven fabrics can be preferably used. The form of the fiber may be any of a single component fiber, a mixture of a plurality of types of fibers, a blended fiber, and a composite fiber (core-sheath type, parallel type, multicore type, archipelago type, radial type, etc.) Good.
[0019]
In performing surface modification of the polymer material, it is preferable to remove impurities by washing the surface of the polymer material with an appropriate liquid. For example, polyolefin, polyvinyl chloride, polyvinylidene chloride and the like are preferably washed with alcohol or toluene. Acetate, nylon, polyester, polystyrene, acrylic resin, polyvinyl acetate, polycarbonate, polyurethane and the like are preferably washed with alcohol. Cellulosic materials such as rayon and cupra are preferably washed with alcohol after washing with a detergent.
[0020]
(Impregnation treatment)
The impregnation treatment is a method in which a compound having an affinity for a polymer material is used as it is or as a solution or dispersion, and the compound is contacted at a temperature below its softening point to impregnate the compound from the surface. . At this time, the polymer material is not substantially deformed. A compound used for this purpose is called an impregnating agent. This impregnation treatment step can be said to be a step in which the impregnating agent soaks into the amorphous region of the polymer compound and creates a gap inside the material. There exists an effect | action which makes the activation process and grafting process etc. which are performed next easy. The impregnated impregnating agent is removed by washing after subsequent processing steps.
A preferable range of the impregnating amount of the impregnating agent with respect to the polymer material is expressed by a weight increase rate. When the thickness of the polymer material is less than 1000 microns, it is 0.1 to 40% by weight, and the material thickness is 1000 microns In the above case, it is 0.1 to 40% by weight with respect to the material portion within a depth of 1000 microns from the surface of the material. In the case of a polymer material having a thickness and a diameter of about 20 mm or less, the amount of impregnation is preferably about 0.1 to 10% by weight for simplicity.
[0021]
The compound that can be used as the impregnating agent may be any of organic, inorganic, gas, liquid, and solid as long as the compound has an affinity for the polymer material. The liquid impregnating agent can be used as it is or as a mixture such as a solution or dispersion with another liquid, as long as it is solid, as a solution or dispersion or emulsion, or as a gas. The impregnating agent in the present invention includes a so-called solvent, but is not limited thereto.
The impregnating agent is selected according to the type of the polymer material to be treated. Compounds used for carrier dyeing of synthetic fibers, particularly polyester-based synthetic fibers, and commercially available assistants for carrier dyeing can be preferably used. In addition, various compounds corresponding thereto can be used. These can be applied to a wide range of polymer materials such as polyolefin, polystyrene, polyacrylic resin, and polyurethane in addition to polyester. Examples of this include diphenyl, ortho or parahydroxybiphenyl, other diphenyl derivatives, or sodium salicylate or derivatives thereof, halogenated aromatic compounds (eg mono, di or trichlorobenzene), etc. It can be used as an organic liquid solution as a solvent, an aqueous dispersion, or an emulsion using a surfactant.
Alternatively, an organic liquid having an affinity for the polymer material can be used as the impregnating agent. In this case, the standard of selection of the organic liquid is a single liquid or a mixture of a plurality of liquids close to the solubility parameter (SP value) of the polymer material to be processed. It is preferable to treat with a solvent having a difference of about +2 or −2 from the solubility parameter of the polymer. Solvents with differences within this range can be used if they are processed at a low temperature in a short time. Just soak into the surface of the polymer, do not dissolve. Even organic solvents that are soluble at high temperatures can be used if they are treated in a short time at low temperatures that do not exhibit solubility.
Examples of liquid impregnating agents include polypropylene, toluene, xylene, decalin, tetralin, cyclohexane, a mixture of 1 volume of dichloroethane and 4 volumes of ethanol, and polyethylene includes 1 volume of toluene, xylene, α-chloronaphthalene, dichlorobenzene. A mixture of 1 volume of toluene and 10 volumes of methanol can be used for polystyrene, and a mixture of 1 volume of phenol and 10 volumes of hexane can be used for polyethylene terephthalate.
[0022]
Conditions such as temperature and time of the impregnation treatment are appropriately selected depending on the shape of the material. For example, in the case of a non-woven fabric made of polyolefin fibers having a fiber diameter of about 5 to 10 μm, the impregnating agent is immersed in a room-temperature impregnating agent (for example, toluene) for 2 minutes and subjected to a centrifugal dehydrator (number of rotations 500 to 2000 times / min) Shake off and finish when the surface impregnating agent is apparently dry. In the case of a polyolefin film, plate and molded product (thickness of about 2 to 5 mm), it is immersed in an impregnating agent at room temperature to 70 ° C. for about 5 to 30 minutes and then drained as described above. The impregnation weight ratio in these cases is about 1 to 10% by weight.
In the case of wool, it is immersed in a mixture of an aqueous sodium carbonate solution and methanol at room temperature for 1 to 10 minutes, rinsed with methanol, and drained with a centrifuge.
This impregnation treatment is effective in the case of a material having a large surface area such as a film or a plate, or a material containing many antioxidants and other additives.
[0023]
(Activation process)
The step of activating the polymer material in the present invention means a treatment for introducing a carbonyl group on the surface of the material. In addition to the carbonyl group, it also includes introducing a functional group containing oxygen or nitrogen, an unsaturated bond, or the like. A preferable method for the activation treatment is various treatments such as plasma treatment, ozone treatment, ultraviolet irradiation treatment, corona discharge treatment, and high-pressure discharge treatment. For the purpose of the present invention, any known equipment can be used. The degree of the activation treatment is appropriately adjusted according to the purpose of the modification, but in the present invention, the minimum activation treatment that can confirm the introduction of the carbonyl group is preferable. Conventionally proposed activation treatment methods are often excessive treatments for the purpose of the present invention. As a criterion for judgment, it is effective to measure the infrared absorption spectrum of the processed polymer material. For example, the ratio of the absorbance of the absorption based on the introduced carbonyl group and the absorbance of the absorption based on the structure of the unchanged crystal part can be determined by the baseline method to know the degree of oxidation. For example, in the case of polypropylene, 1710 cm based on the introduced carbonyl group ^-1 Absorption near 973 cm based on the absorbance in the vicinity and the unchanged crystalline partial methyl group ^-1 The ratio of the absorbance at is preferably about 0.2 or less.
A preferable method for setting the activation treatment conditions is to obtain a relationship between the treatment time and the carbonyl absorption in advance for the target polymer material, and based on this relational expression, the activation treatment to the extent that the material strength is not reduced. Define the conditions. Even if there is a minimum amount of carbonyl group that can be detected by infrared absorption spectroscopy, if intensity decreases, it is appropriate to interpolate to the time corresponding to the absorbance that cannot be measured by infrared absorption based on this relational expression. The correct processing time. By doing so, an effective surface activation treatment can be achieved without reducing the material strength.
[0024]
(Ozone treatment)
The purpose of the ozone treatment is to perform a reforming reaction mainly including an oxidation reaction by bringing the surface of the polymer material into contact with ozone molecules. The ozone treatment is performed by exposing the polymer material to ozone. The exposure method can be performed by an appropriate method such as a method of holding in an atmosphere in which ozone exists for a predetermined time, a method of exposing in an ozone stream for a predetermined time. Ozone can be generated by supplying an oxygen-containing gas such as air, oxygen gas or oxygen-added air to an ozone generator. The obtained ozone-containing gas can be introduced into a container, tank, or the like that holds the material to perform ozone treatment. Various conditions such as the ozone concentration in the ozone-containing gas, the exposure time, and the exposure temperature can be appropriately determined according to the type and shape of the polymer material and the purpose of the surface modification. Usually, oxygen or air flow is used, and the flow rate is 20 ml to 10 L / min, and 10 to 200 g / m. ³ Can be processed at a temperature of 10 to 80 ° C. for 1 minute to 10 hours. For example, in the case of polypropylene or polyvinyl chloride fiber, the ozone concentration is 10 to 40 g / m. ³ Thus, treatment at room temperature for about 10 to 30 minutes is appropriate. In the case of a film shape, the ozone concentration is 10 to 80 g / m. ³ The treatment for about 20 minutes to 3 hours at room temperature is appropriate. The generated ozone concentration when air is used is about 50% when oxygen is used.
It is estimated that hydroperoxy groups (--O-OH), etc. are introduced into the surface of polymer materials by ozone treatment due to ozone treatment, and some of them are converted to functional groups such as hydroxyl groups and carbonyl groups. The
[0025]
(Plasma treatment)
In the plasma treatment, a polymer material is placed in a container containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen, air, etc., exposed to plasma generated by glow discharge, and a functional group containing oxygen, nitrogen, etc. on the surface of the material. The purpose is to introduce. When an inert gas such as argon or neon is present at a low pressure, it is considered that the surface of the polymer material is attacked by the generated plasma and radicals are generated on the surface. Then, it is considered that radicals are combined with oxygen by being exposed to air, and a carboxylic acid group, a carbonyl group, an amino group, or the like is introduced into the surface of the polymer material. In addition, it is thought that a functional group is directly introduced by a plasma treatment in a small amount of nitrogen, carbon dioxide, oxygen or air. Discharge forms of plasma generation are classified into (1) DC discharge and low frequency discharge, (2) radio wave discharge, (3) microwave discharge, and the like.
[0026]
(UV irradiation treatment)
The ultraviolet irradiation treatment is a method of irradiating the surface of the polymer material with ultraviolet rays in the air. As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. The surface of the polymer material may be treated with an ultraviolet absorbing solvent before irradiation. Although the wavelength of ultraviolet rays can be selected as appropriate, in order to reduce deterioration of the material, it is preferably around 360 nm or less. When the polymer material is irradiated with ultraviolet rays, the ultraviolet rays are absorbed by chemical structures such as double bonds in the surface region of the molded product, the chemical bonds are broken by the absorbed energy, and oxygen in the air is generated in the generated radicals. It is considered that a carbonyl group, a carboxyl group, and the like are generated by bonding and via a peroxide structure in the middle.
[0027]
(High pressure discharge treatment)
In the high-pressure discharge treatment, a belt conveyor for moving the polymer material to be processed is installed in the tunnel-shaped processing device, and a large number of electrodes are attached to the inner wall surface of the processing device while moving the polymer material. In this method, a high voltage of hundreds of thousands of volts is applied to and discharged in the air. It is considered that oxygen in the air and the surface of the object to be processed are activated by the discharge, oxygen is taken into the surface of the polymer material, and polar groups are generated.
[0028]
(Corona discharge treatment)
In the corona discharge treatment, a corona discharge is generated by applying a high voltage of several thousand volts between a grounded metal roll and a knife-like electrode placed at a distance of several millimeters, and between the electrode and the roll during this discharge. Is passed through the polymer material to be treated. This method is suitable for the processing of films or laminae.
[0029]
Methods other than ozone treatment activate the surface by irradiating the material, and it is necessary to devise a shadowed portion that is not exposed to radiation. Accordingly, ozone treatment is preferable for treating a fiber aggregate such as a non-woven fabric or the entire material having a shadow portion depending on the form of the material. In addition, ozone treatment is preferable because it is inexpensive in terms of equipment costs.
[0030]
(Monomer grafting process)
In the present invention, the monomer to be grafted is not limited as long as it can be grafted, but is preferably a compound having at least one carbon-carbon double bond, such as a vinyl compound or a similar compound. Of the monomers, hydrophilic monomers are preferred. Hydrophilic monomers include acrylic acid, methacrylic acid, vinyl acetic acid, 2-butenoic acid, ethylene sulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, maleic anhydride, anhydrous Preference is given to at least one monomer selected from the group consisting of pyromellitic acid or a mixture with at least one monomer selected from these groups. In the present invention, it is particularly preferable to use acrylic acid or methacrylic acid from the viewpoint of chemical resistance and water absorption.
[0031]
Furthermore, vinyl monomers such as acrylic acid esters, methacrylic acid esters, vinyl acetate, and styrene, which are less hydrophilic than hydrophilic monomers, can also be used. It is preferable to use only a hydrophilic monomer, but by using a mixture of a hydrophilic monomer and a poorly hydrophilic monomer, the grafting rate increases and the hydrophilicity contained in the graft polymer. The monomer may be able to impart the hydrophilicity of the material.
[0032]
Monomer grafting is (1) a method in which a catalyst or an initiator (hereinafter collectively referred to as “initiator”) is present, and (2) a method in which heating is performed in the presence or absence of an initiator. Or (3) Any method in which ultraviolet irradiation is carried out in the presence or absence of a catalyst or an initiator is preferred. Initiators include peroxides (benzoyl peroxide, t-butylhydroxyperoxide, di-t-butylhydroxyperoxide, etc.), ceric ammonium nitrate (IV), persulfates (potassium persulfate, ammonium persulfate, etc.), Redox initiator (oxidizer: persulfate, hydrogen peroxide, hydroperoxide, etc., inorganic reducer: copper salt, iron salt, sodium bisulfite, sodium thiosulfate, etc., or organic reducer: alcohol, amine, Combination with oxalic acid and the like, and oxidizing agent: hydroperoxide and the like and inorganic reducing agent: copper salt, iron salt, sodium bisulfite, sodium thiosulfate and the like, or organic reducing agent: dialkyl peroxide, diacyl peroxide and the like and reducing agent : Tertiary amine, naphthenate, mercaptan, organometallic compound (triethylaluminum Combination of triethyl like element)), and other known radical polymerization initiator and the like.
When acrylic acid is used as a monomer, a water-soluble polymerization initiator such as dicerium ammonium nitrate (IV) or potassium persulfate is preferably used, but benzoyl peroxide, N, N-azobisisobutyronitrile, etc. The water-insoluble initiator can be used by dissolving in methanol or acetone and mixing with water. In the case of ultraviolet irradiation, a photosensitizer such as benzophenone or hydrogen peroxide may be added as a catalyst in addition to these polymerization initiators.
[0033]
For grafting of the monomer, a general grafting method can be used. Specific examples are shown below.
In the case of a water-soluble initiator, the required amount is dissolved in water. In the case of a water-insoluble initiator, it is dissolved in an organic solvent (for example, acetone, methanol, etc.) mixed with water such as alcohol or acetone, and then mixed with water so that the initiator does not precipitate. A material subjected to an activation treatment or a hydrophilic polymer treatment described later is added to the initiator solution, and a monomer is added to perform grafting. The inside of the processing container is purged with nitrogen as necessary. In the case of heat grafting, the reaction mixture is heated at an appropriate temperature for an appropriate time. Alternatively, when grafting is performed under ultraviolet irradiation, ultraviolet irradiation is performed at an appropriate temperature and time. Although the ultraviolet lamp is not particularly limited, a high-pressure mercury lamp (for example, trade name: H400P manufactured by Toshiba Corporation) can be used. Although the wavelength may extract ultraviolet rays around 360 nm with a filter, it may irradiate light of all wavelengths.
[0034]
A method in which a vinyl monomer having an amide group is used as the monomer and the amide group is Hoffmann-transferred from the method described in JP-A-8-109228 by the present inventor can also be preferably used.
[0035]
(Hydrophilic polymer)
In the present invention, the hydrophilic polymer means a water-soluble polymer or a polymer that is not readily water-soluble but has hydrophilicity. Specific examples include polyvinyl alcohol, carboxymethyl cellulose, ethylene-vinyl alcohol copolymer, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, poly-α-hydroxyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, Examples include polyalkylene glycols such as polypropylene glycol. These sulfonated products can also be used. Other examples include sodium alginate, starch, silk fibroin, silk sericin, gelatin, various proteins, and polysaccharides.
[0036]
(Treatment with hydrophilic polymer)
When the hydrophilic polymer treatment is performed on the activated polymer material, it is preferably performed in the presence of a catalyst or an initiator. As the catalyst and the initiator, the same ones as in the case of grafting with a monomer can be used.
In the treatment step with the hydrophilic polymer, the hydrophilic polymer is preferably used in a solution state. Any water-soluble polymer can be used as an aqueous solution. If it is poor in water solubility, dissolve it in a suitable solvent. The case where a water-soluble polymer is used will be described below.
When the treatment with the water-soluble polymer is performed in the absence of the initiator, the polymer material subjected to the activation treatment is placed in an aqueous solution of a hydrophilic polymer.
When the treatment with the water-soluble polymer is performed in the presence of the initiator, an aqueous solution of the water-soluble polymer is first prepared, and in the case of the water-soluble initiator, a necessary amount is dissolved therein. In the case of a water-insoluble initiator, it is dissolved in an organic solvent mixed with water, such as alcohol or acetone, and then added to an aqueous solution of a water-soluble polymer. A polymer material subjected to an activation treatment is placed in a solution of a water-soluble polymer to which an initiator has been added for treatment. It is desirable to replace the inside of the processing container with nitrogen. However, in a simple manner, a practical process can be performed without nitrogen substitution.
The temperature of the treatment with the water-soluble polymer and the initiator is not particularly limited, and is usually 10 to 80 ° C., preferably 60 to 90 ° C. In order to improve hydrophilic durability, a treatment at a high temperature for a long time (for example, about 12 hours) is also performed.
[0037]
(Use)
The polymer material modified by the method of the present invention is greatly improved in hydrophilicity, water absorption, water retention, adhesiveness, and the like, and has excellent durability. It can be applied to various uses by utilizing the above. Moreover, since it is excellent also in adhesiveness, it can adhere | attach to paper, wood, a metal, etc. with a general adhesive agent, for example, starch, polyvinyl acetate, polyvinyl alcohol, an epoxy resin system, polycyanoacrylate, etc. It can be applied to various materials that require adhesiveness. Furthermore, the modification method of the present invention can be applied to many polymer materials including polyolefins such as polypropylene and polyethylene, which are particularly difficult to modify. Polyolefin non-woven fabric or mixed non-woven fabric made of polyolefin and other polymers can give water absorption of 7 to 10 times its own weight, and further to adhesiveness, alkali resistance, acid resistance and oxidation resistance. Excellent. Although each use is demonstrated below, the use of this invention is not limited to the following.
[0038]
(1) Wiping cleaning materials:
At present, mainly based on polyester fiber, polyolefin fiber, and synthetic fiber composite fiber, blended with rayon to make it hydrophilic, and then impregnated with an aqueous solution containing a surfactant. Are commercially available as disposable cleaning materials or wipers. When this disposable cleaning material is manufactured with the fiber of the modified water-absorbing polymer material of the present invention, it is lightweight, high-strength, excellent in water-absorbing property and surfactant-absorbing property, and thus has increased durability. Is obtained. After use, it can be reused by washing with water several times.
[0039]
(2) Water absorption material:
It means a polymer material having water absorption produced according to the present invention.
[0040]
(3) Water retention material:
The hydrophilic polyolefin nonwoven fabric produced by the present invention is useful as a water retention material for supplying water to plants. The material shape as a water retention material for this purpose may be a woven fabric, a nonwoven fabric, or a fiber having no cloth shape, or a cut fibrous waste. About 10-500 micrometers is easy to use the diameter of a constituent fiber.
[0041]
(4) Medical, hygiene and cosmetic products:
Means various disposable items. Illustrative examples include diapers, sanitary products, bandages, gauze, sanitary napkins, disinfecting affixing cloths and tapes, other medical supplies, and various cosmetics such as cleansing applications, face-wash packs, and pads.
Disposable diapers or sanitary products contain a water-absorbing material made from pulp, starch, acrylic polymer, etc. inside, and the outside is covered with a water-repellent polyolefin non-woven fabric so as not to pass urine, moisture, blood, etc. It has been broken. Moisture discharged from the body permeates the inner hydrophilic nonwoven fabric and is absorbed by the inner water-absorbing material. Hydrophilic polyolefin nonwoven fabric is the most desirable material as a material that is resistant to moisture and difficult to tear. However, the hydrophilization of the hydrophilized non-woven fabric used on the inside is only impregnated with a surfactant or water-soluble treatment agent that easily drops with water. For this reason, the hydrophilicity is not durable and is easily washed away with water. The effect of surfactants on the skin is also a problem. Therefore, a cheap, easy and durable hydrophilization technology is desired. The water-absorbing / water-retaining polyolefin material obtained by the hydrophilization technique of the present invention is an optimal material as a disposable diaper or a cloth for inner sewing of a sanitary product. Further, the polymer material having high water absorption according to the present invention is also used as a water-absorbing material in disposable diapers or sanitary products. Light weight, high strength, safety and withstand repeated use. The hydrophilic or water-absorbing material obtained by the present invention is lightweight and high in strength and can be impregnated with detergents, chemicals, adhesives, etc., so gauze, wiping textiles, pasting disinfecting cloth / tape, etc. Suitable for cosmetic materials. When used as a disposable medical / hygiene / cosmetic article, the material shape is preferably woven fabric or non-woven fabric, and the basis weight and thickness may be appropriately selected. However, the diameter of the constituent fiber of the woven or non-woven fabric is easy to use about 1 to 500 μm.
[0042]
(5) Internal materials such as clothing, beds and futons:
The hydrophilic or water-absorbing polymer material obtained by the present invention is lightweight and has high strength, and is suitable for internal materials such as textiles for clothes, beds, and futons by controlling water absorption.
[0043]
(6) Filter material:
Filter media made of a porous film made of a hydrophobic material such as polyolefin, polysulfone, or polyester has higher strength than paper filter media, but is poor in hydrophilicity, so it is not suitable for aqueous solution filtration. Is appropriate. Currently, surfactants and water-soluble polymers are applied to cope with these problems, but these hydrophilized parts are eluted during filtration and lack durability. A durable, water-absorbing filter medium can be obtained by subjecting the filter medium made of such a hydrophobic material to the hydrophilization treatment of the present invention.
[0044]
(7) Materials for microbial medium:
The water-absorbing material obtained by the present invention is excellent in water-absorbing property, strength, and microbial propagation, and is optimal as a material for a microbial medium. The shape of the material for the microbial medium may be a woven fabric, a non-woven fabric, a fiber having no cloth shape, or a cut fibrous waste. About 10-500 micrometers is easy to use the diameter of a constituent fiber.
[0045]
(8) Orthodontic bracket:
By the treatment method according to the present invention, the adhesion of the polymer material can be improved. Since it can be utilized for various materials that require adhesiveness, composite materials, and reinforcing fibers blended in fiber-reinforced plastics, the adhesiveness between the orthodontic bracket made of plastic and the teeth can be improved.
[0046]
(9) Medical device material parts:
Means artificial blood vessels, artificial organs, artificial joints, tubular, thread-like, plate-like polymer material parts. The hydrophilicity of these materials can be improved to improve medical compatibility. Examples thereof include those used in contact with the human body or human tissue (catheter, drainage device), body fluid absorbing materials, contact lenses, synthetic fiber bandages, gauze infusion devices, and the like.
[0047]
(10) Polymer material composite material:
The adhesive property of the reinforcing fiber blended in the composite material and the fiber reinforced plastic can be improved and used for a polymer material composite material having excellent strength.
[0048]
(11) Synthetic paper:
Synthetic paper made of a polymer material such as polyethylene or polyolefin such as polypropylene or polyester is added with air bubbles or a filler to give whiteness, and is used as a substitute for paper. By making the surface hydrophilic according to the present invention, it is possible to improve adhesion and printability.
[0049]
(12) Material with improved adhesion:
In addition to improving the adhesiveness of the orthodontic bracket and the reinforcing fiber for composite material, the adhesiveness of various polymer films and molded products can be improved to improve the adhesiveness with the same or different materials.
[0050]
(13) Other uses of hydrophilic film:
According to the present invention, high hydrophilicity can be imparted to a polymer film such as polyolefin or polyester. For example, a water-absorbing polyester film is excellent in adhesiveness and easily wetted with water, so that an anti-fogging effect can be obtained by sticking to glass or a mirror.
[0051]
(Example)
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention should not be construed as being limited to these examples.
The materials, reagents, and test / evaluation methods used are shown below.
(A) Materials including polymer materials
(1) Table 1 shows the characteristics of the nonwoven fabrics, woven fabrics, fiber bundles, films, plates, and porous films used in Examples and Comparative Examples. Note that PP: polypropylene, PE: polyethylene, PET: polyethylene terephthalate, PSU: polysulfone, P / E: a mixed sample of PP and PE.
[Table 1]

[0052]
(2) Orthodontic bracket:
A polypropylene molded product sized 2.23 × 3.0 × 3.8 mm, weight of about 31 mg / piece, and reinforced with an aluminum fitting.
[0053]
(B) Reagents
(1) Polyvinyl alcohol (PVA): Wako Pure Chemical Industries, Ltd., product number 160-11485 (average degree of polymerization = 1500-1800)
(2) Sodium carboxymethyl cellulose (CMC): Wako Pure Chemical Industries, Ltd., product number 039-01355
(3) Acrylic acid: Wako Pure Chemical Industries, Ltd., product number 011-00776
(4) Methacrylic acid: Wako Pure Chemical Industries, Ltd., product number 138-10805
(5) Methyl methacrylate: manufactured by Wako Pure Chemical Industries, Ltd., product number 139-02726
(6) Sodium persulfate (SPS): Wako Pure Chemical Industries, Ltd., product number 195-04985
(7) Potassium persulfate (KPS): Wako Pure Chemical Industries, Ltd., product number 162-04235
(8) 2,2′-azobisisobutyronitrile (AIBN): manufactured by Wako Pure Chemical Industries, Ltd., product number 019-04932
(9) Dicerium ammonium nitrate (IV) (CAN): Wako Pure Chemical Industries, Ltd., product number 036-01742
(10) Benzophenone: manufactured by Wako Pure Chemical Industries, Ltd., product number 023-01072
(11) Methanol: Wako Pure Chemical Industries, Ltd., product number 136-09475
(12) Sodium hydroxide: manufactured by Wako Pure Chemical Industries, Ltd., product number 194-02135
(13) Hydrochloric acid: Wako Pure Chemical Industries, Ltd., product number 080-01066
(14) Toluene: Wako Pure Chemical Industries, Ltd., product number 204-01866, this liquid itself was used (impregnating agent A).
(15) Sodium dodecylbenzenesulfonate (DBS): Tokyo Chemical Industry Co., Ltd., product number D1238, used as a surfactant.
(16) Decahydronaphthalene (cis, trans mixture): Wako Pure Chemical Industries, Ltd., product number 048-O0066, this liquid itself was used (impregnating agent B).
(17) Orthohydroxybiphenyl (OHB): Wako Pure Chemical Industries, Ltd., product B number 080-O1402, 1 g of orthohydroxybiphenyl and sodium hydroxide 0.2 g, surfactant (sodium dodecylbenzenesulfonate) 0.2 g Was used as a solution obtained by mixing 200 ml of water (impregnating agent C).
Alternatively, a solution obtained by dissolving 0.5 g of orthohydroxybiphenyl in 300 ml of methanol was used by dispersing in water used as a carrier (carrier D).
(18) Sodium salicylate (SS): Wako Pure Chemical Industries, Ltd., product number 195-O3145 (impregnating agent D)
1 g of sodium salicylate was dissolved in 200 ml of water and mixed with 0.5 ml of 10% hydrochloric acid and dispersed in water for use (impregnating agent E).
(19) Diphenyl (DP): Wako Pure Chemical Industries, Ltd., product number 040-18412. A solution obtained by mixing 2.5 g of diphenyl and 0.2 g of a surfactant (sodium dodecylbenzenesulfonate) in 200 ml of water was used (impregnating agent F).
(20) Carnant (trade name, manufactured by Toho Chemical Co., Ltd.): Carrier for dyeing polyester-based synthetic fibers, blended product of aromatic ether-based anionic activator. Used by dispersing in water (carrier 1).
(21) Carrier TW200 (trade name, manufactured by Nikka Chemical Co., Ltd.): A carrier for dyeing synthetic fibers for polyester / wool blends, methylnaphthalene and other blended products, used by dispersing in water (carrier 2).
[0054]
(C) Ozone treatment:
The test piece is put in a 2 L or 10 L hard glass container (with gas inlet and outlet), and from an ozone generator (OS-1N manufactured by Mitsubishi Electric Corporation), the amount of ozone generated is 1 g / h and the concentration is 20 g / h. m ³ Oxygen containing ozone was blown for 20 to 120 minutes at a flow rate of 800 ml / min. Next, oxygen not containing ozone was blown for 10 minutes. The concentration of ozone was determined by iodometric titration. The degree of oxidation is determined by scraping the surface member of the treated test piece and measuring the infrared absorption spectrum. ^-1 Change in absorbance of absorption peak in the vicinity (absorption of carbonyl group), and this absorbance and 973 cm ^-1 It was judged from the ratio of the absorbance.
[0055]
(D) Plasma treatment:
A test piece (cloth, film, etc.) was placed between the electrodes in the reaction vessel of the plasma processing apparatus (Yamato PR500). After reducing the pressure in the reaction vessel to 0.27 Pa, a mixture of argon gas and oxygen gas (volume ratio 1: 1) was introduced until the pressure reached 5.6 Pa. Glow discharge was performed mainly for 30 seconds to 3 minutes at an oscillation frequency of 13.56 MHz with a supplied power value between 40 W and 100 W. After discharge, gas introduction was stopped and the pressure was returned to normal pressure, and then the treated test piece was taken out. The degree of treatment was judged by the decrease in the contact angle of water with the film.
[0056]
(E) UV irradiation treatment:
In the case of activation treatment, the sample itself was directly irradiated with a high-pressure mercury lamp (Toshiba high-pressure mercury lamp H400P) from a distance of 10 cm.
In the case of grafting, the reaction mixture was placed in a Pyrex glass reaction vessel, brought to a temperature of 10 to 70 ° C., and irradiated with a high pressure mercury lamp (Toshiba high pressure mercury lamp H400P) from a distance of 20 cm. The reaction tube revolved around the lamp while rotating so that the light was uniformly irradiated.
[0057]
(F) Evaluation of water absorption:
Measurement of water absorption rate of nonwoven fabric, woven fabric, fiber bundle, film, board, porous film:
(1) Water absorption: Put a test piece (size 10 cm × 10 cm) in a beaker containing water and gently agitate with a glass rod for about 1 minute. Next, the test piece is taken out and hung for 3 minutes (water drops do not drop). The weight of the dried test piece was subtracted from the weight of the water-absorbed test piece to obtain an increased weight (water absorption amount), and the percentage with respect to the weight of the dry test piece was defined as the water absorption rate (%).
Water absorption rate (%) = (Water absorption amount / weight of test piece when dried) × 100
[0058]
(2) Water absorption rate: 1 cm of the lower end of a test piece having a width of 1.5 cm was immersed in water, and the distance (unit: cm / min) of the rise of water per minute was measured.
All the untreated samples used in this example had a water absorption rate of 0 cm / min. In addition, the water uptake speed of all the untreated samples used in this example was 0 cm / min.
[0059]
(G) Measurement of water contact angle:
A contact angle measuring device (CA-X manufactured by Kyowa Interface Science Co., Ltd.) was used. At 20 ° C., a drop of water having a diameter of about 1 mm from the syringe was dropped onto the surface of the test piece, and was calculated from the size of the image magnified by the video camera.
[0060]
(H) Washing resistance test:
The test piece was placed in a weakly alkaline fatty acid sodium soap (trade name: Lion Powder Soap manufactured by Lion Corporation) 0.4% aqueous solution at a bath ratio of 1: 250, and boiling washed for 5 minutes with stirring. Thereafter, it was sufficiently washed with water and dried. The water absorption rate, water uptake speed, and tensile strength were measured and compared with those before washing.
[0061]
(I) Tensile strength test:
The test piece is cut into a 1.5 cm × 7 cm rectangle, and 1 cm from both ends are fixed to the clamp of a tensile tester (SV55-0-20M, Imada Seisakusho Co., Ltd.), the holding interval is 5 cm, and the pulling speed is 100 mm / min. Pulled on. Measurements were made in each direction of the vertical and horizontal eyes. In each example, only the longitudinal direction was shown.
[0062]
(J) Adhesive peel strength test:
(1) For film:
The test piece is cut into a size of 30 mm (longitudinal direction) × 5 mm, 0.1 g of adhesive is applied to a 5 mm × 5 mm portion at one end, and a plywood (thickness 2 mm, size 20 mm × 10 mm) or sticky note ((thickness) A 500 g weight is put on a polyethylene film for 12 hours, and a tensile tester (10 mm of the unbonded part of the plywood and 10 mm of the unbonded end of the film are attached). It was sandwiched between Shimadzu AGS-H) clamps and pulled at a pulling speed of 30 mm / min to determine the energy required to peel off the bonded part (adhesive peel energy). The relative value was determined by setting the adhesion release energy of the untreated material to 1.0.
In the case of plywood, the adhesive used was polycyanoacrylate (Aron Alpha: manufactured by Toa Gosei Co., Ltd.) and in the case of sticky notes, paper adhesive for stationery (trade name: manufactured by KOKUYO Co., Ltd., Plit) ).
[0063]
(2) For bracket:
Apply approximately 0.01 g of adhesive to the adhesive surface of the treated or untreated bracket, attach it to a ceramic plate (size 20 mm x 10 mm), hook a loop wire, and pull the unadhered part of the ceramic plate The test machine (Shimadzu Corporation, SV55-0-20M) is clamped with the lower clamp, the wire is fixed to the upper clamp, pulled at a pulling speed of 110 mm / min, and the load applied until the bonded portion is peeled is determined. In order to standardize the bonding conditions, the relative value was determined with the peel strength of the untreated material performed at the same time being 1.0. Polymerizable methacrylic resin-based adhesive (used by mixing methyl methacrylate monomer, polymer, polymerization catalyst, etc.): Trade name Superbond (Sun Medical Co., Ltd.) or homemade product was used.
[0064]
The treatments corresponding to claims 1, 2, and 3 are referred to as inventions 1, 2, and 3, respectively, and examples of treatment of various nonwoven fabrics or woven fabrics made of polypropylene, polyester, and polyethylene are shown below. Table 2 shows the water absorption rate, water absorption height, and water absorption rate after washing of the obtained treated or untreated samples. In all the examples, the operation of removing the antioxidant, stabilizer and other additives contained in the polymer material was not performed.
[0065]
(Example 1) Hydrophilization of polypropylene nonwoven fabric according to Invention 1
As the impregnating treatment, 100 ml of toluene was set to 50 ° C., and then 1.0 g (size 20 cm × 20 cm) of PP nonwoven fabric 1 was soaked for 15 minutes. Next, it was rinsed with methanol and then placed in a centrifuge (800 rpm) for 1 minute. The weight increase of the sample was about 4%.
Next, as an activation treatment, ozone treatment was performed for 30 minutes (ozone generation rate: 1.0 g / h). Measured infrared absorption spectrum, 1710cm ^-1 The absorbance ratio of the absorption peak in the vicinity (absorption of carbonyl group) was 0.02.
Next, the treatment material is put into a solution made by adding 200 ml of water, 20 mg of dicerium ammonium nitrate (IV), and 0.6 ml of acrylic acid to a Pyrex glass tube, and a 400 watt high-pressure mercury lamp is placed at a distance of 20 cm. Then, irradiation was carried out for 120 minutes while maintaining at 30 ° C. After the treatment, the material was boiled and washed in a 60 ° C. detergent aqueous solution for 10 minutes, then washed with water and dried. Water absorption by the water absorption test of the treated sample was 310%. The water absorption height was 2.0 cm / min. The untreated nonwoven fabric had a water absorption rate of 0% and a water absorption height of 0 cm / min.
In particular, it was excellent in water absorption and electrolyte retention. It is also excellent in alkali resistance, acid resistance, and oxidation resistance, and is effective as a battery separator manufacturing method.
[0066]
(Example 2)
Except for using decahydronaphthalene (impregnating agent B) as the impregnation treatment, plasma treatment for 30 seconds as the activation treatment, and using methacrylic acid as the monomer, all are the same as in Example 1.
[0067]
Example 3
Except for using an orthohydroxy biphenyl (OHB) aqueous dispersion (impregnating agent C) as the impregnating treatment, everything is the same as in Example 1.
Example 4
Except for using a methanol solution of orthohydroxy biphenyl (impregnating agent D) as the impregnating agent treatment, everything is the same as in Example 1.
[0068]
(Example 5)
Example 1 is the same as Example 1 except that a sodium salicylate aqueous dispersion (impregnant E) is used as the impregnating treatment, and an ultraviolet irradiation treatment for 60 minutes is performed as the activation treatment.
[0069]
(Example 6)
Except for using a diphenyl solution (impregnating agent F) as the impregnating agent treatment, everything is the same as in Example 1 except for performing an ultraviolet irradiation treatment for 60 minutes as the activation treatment.
(Comparative Examples 1-5)
Comparative Example 1 is a result of using an untreated PP sample used in Example 1.
Comparative Example 2 is the same as Example 1 except that the impregnating treatment process is omitted in the process of Example 1.
Comparative Example 3 is the same as Example 1 except that the impregnating agent treatment process and the activation process are omitted in the process of Example 1. Comparative Example 4 is the same as Example 1 except that the impregnating agent treatment step and the grafting step are omitted in the step of Example 1. Comparative Example 5 is the same as Example 1 except that the activation process is omitted in the process of Example 1.
[0070]
(Example 7)
A PP plain woven fabric was used as a PP sample, and an orthohydroxy biphenyl (OHB) solution (impregnating agent C) was used as an impregnation treatment, and ultraviolet irradiation was performed for 2 hours as an activation treatment. Other methods and procedures are the same as those in the first embodiment. Grafting was similar to Example 1.
[0071]
(Comparative example 6) It is a result of untreated PP plain woven fabric.
[0072]
(Comparative Example 7) The same treatment as in Example 2 except that the plain plain cloth was used as a sample and the impregnation treatment was omitted. From Example 3, the durability of water absorption decreased a little.
[0073]
(Example 8)
Using PET non-woven fabric (size: 10cm x 10cm), carrier 1 (trade name: Carnant) in water dispersion (5g reagent mixed in 200ml water), using AIBN 20mg instead of CAN as an initiator Performed in the same manner as Example 1.
[0074]
Example 9
Using PET non-woven fabric (size 10cm x 10cm), carrier 2 (trade name: carrier TW200) in water dispersion (5g reagent mixed in 200ml water), activated by ozone treatment, grafting by CAN as initiator Instead of, 20 mg of AIBN was used, and thermal polymerization was carried out at 70 ° C. for 4 hours (the procedure was the same as in the examples, but no ultraviolet light was irradiated).
The same method as in Example 1 was performed.
[0075]
(Example 10)
A PET non-woven fabric (size 10 cm × 10 cm) was performed in the same manner as in Example 1.
[0076]
(Comparative Examples 8-12)
For the PET nonwoven fabric, Comparative Example 8 was untreated, Comparative Example 9 was omitted from the impregnating treatment from Example 1, Comparative Example 10 was omitted from the impregnating treatment and activation treatment from Example 1, and Comparative Example 11 was Example 4. In this process, the impregnating treatment and the grafting treatment are omitted. In Comparative Example 12, the activation process was omitted from Example 1.
[0077]
(Examples 11 to 12)
Example 11 uses PP nonwoven fabric 2 and ortho-hydroxybiphenyl (OHB) solution (impregnating agent C), as in Example 1, and Example 12 uses PP nonwoven fabric 2 and impregnating agent C. Same as 2.
[0078]
(Comparative Examples 13-17)
In either case, PP nonwoven fabric 2 was used. Comparative Example 13 is untreated PP nonwoven fabric 2, Comparative Example 14 is the same as Example 1 except that the impregnating treatment is omitted, and Comparative Example 15 is the same as Example 1 except that the impregnating treatment and activation treatment are omitted. Comparative Example 16 is the same as Example 1 except that only the ozone treatment as the activation treatment is performed, and Comparative Example 17 is omitted.
[0079]
(Example 13)
Using a P / E non-woven fabric as a sample, an aqueous dispersion of orthohydroxy biphenyl (OHB) (impregnating agent C) as an impregnating agent treatment, activation using ozone treatment, ceric ammonium nitrate (IV) as an initiator, methacrylic acid Thermal grafting was performed at 80 ° C. for 3 hours using an acid as a monomer.
[0080]
(Example 14) A P / E nonwoven fabric was used as a sample, and potassium sulfate was used in place of dicerium ammonium nitrate (IV).
[0081]
(Comparative example 18) It is a result of an untreated P / E nonwoven fabric.
[0082]
Table 2 summarizes the results.
The water absorption is the value after treatment, washing with detergent and drying, and the water absorption after washing three times is the water absorption after washing with a boiling detergent solution and drying three times.
[0083]
[Table 2]

[0084]
Examples of the treatment of polyethylene terephthalate film, ultrahigh molecular weight polyethylene plate, and polypropylene film, and comparative examples in which one or two steps are omitted from the untreated and the method of the present invention are shown below. The results are summarized in Table 3.
[0085]
(Example 15)
Processing of polyethylene terephthalate film
As the impregnating treatment, 100 ml of toluene (impregnating agent A) was brought to 80 ° C., and 1.62 g (size 15 cm × 15 cm) of a PET film was soaked for 15 minutes. Next, after rinsing with methanol, excess carrier was wiped off with paper and dried for 5 minutes at room temperature.
Next, as an activation treatment, ozone treatment was performed for 30 minutes (ozone generation rate: 1.0 g / h).
Next, grafting was carried out for 4 hours while keeping the treatment material in a solution prepared by adding 200 ml of water, 20 mg of AIBN, and 1.2 ml of acrylic acid to a glass tube made of Pyrex. After the treatment, the material was boiled and washed with a 60 ° C. aqueous detergent solution for 1 minute, then washed with water and dried. The water absorption by the water absorption test of the treated sample was 90%, and the contact angle of water was 63 °. The adhesive peel strength of the sticky note by the stationery paste (plit) was 4.0 when the untreated adhesive peel strength was 1.
[0086]
(Example 16)
After 100 ml of an aqueous dispersion of orthohydroxy biphenyl (impregnating agent C) was brought to 70 ° C., 1.62 g (size 15 cm × 15 cm) of a PET film was soaked for 15 minutes. Next, it was rinsed with methanol and then wiped off with excess paper and dried at room temperature for 5 minutes.
Next, after the same ozone treatment as in Example 1, UV irradiation grafting was performed using 180 ml of water, 20 mg of potassium persulfate, and 1.2 ml of methacrylic acid.
[0087]
(Example 17)
The same procedure as in Example 16 was performed except that a methanol solution of orthohydroxybiphenyl (impregnating agent D) was used.
[0088]
(Example 18)
The same procedure as in Example 16 was performed except that 1 g of an aqueous dispersion of sodium salicylate (impregnating agent E) was used.
[0089]
(Comparative Example 19)
It is a result of an untreated PET film.
(Comparative Example 20)
The treatment without the impregnating agent treatment from Example 16 was performed.
(Comparative Example 21)
From Example 16, the treatment without the impregnating treatment and the activation treatment was performed.
(Comparative Example 22)
From Example 16, the treatment without the impregnating treatment and the grafting treatment was performed.
(Comparative Example 23)
The process which carried out the activation process from Example 16 was performed.
[0090]
Example 19
3.84 g of ultra high molecular weight polyethylene plate (size 10 cm x 10 cm)
As the impregnating treatment, it was immersed in 100 ml of toluene (impregnating agent A) at 70 ° C. for 15 minutes. Next, after rinsing with methanol, excess impregnating agent was wiped off with paper and dried at room temperature for 5 minutes.
Next, for activation, ozone treatment was performed for 120 minutes. Next, the same UV irradiation grafting as in Example 2 was performed using 180 ml of water, 20 mg of ceric ammonium nitrate (IV), and 1.0 ml of acrylic acid.
[0091]
(Example 20)
The same procedure as in Example 19 was performed except that decahydronaphthalene (impregnating agent B) was used as the impregnating treatment.
[0092]
(Example 21)
Example 19 was repeated except that ortho-hydroxybiphenyl (OHB) (impregnating agent C) was used and no initiator was added during grafting.
[0093]
(Comparative Example 24)
It is a result of an untreated ultra high molecular weight polyethylene board.
(Comparative Example 25)
The treatment without the impregnating agent treatment was carried out from Example 19.
(Comparative Example 26)
From Example 19, the treatment without the impregnating treatment and the activation treatment was performed.
(Comparative Example 27)
From Example 19, the treatment without the impregnating treatment and the grafting treatment was performed.
(Comparative Example 28)
The process which carried out the activation process from Example 19 was performed.
[0094]
(Example 22)
0.38g of polypropylene film (size 15cm x 15cm)
It was immersed in an aqueous dispersion of orthohydroxy biphenyl (impregnating agent C) (70 ° C., 100 ml) for 10 minutes. Next, after rinsing with methanol, excess impregnating agent was wiped off with paper and dried at room temperature for 5 minutes.
Next, activation performed ozone treatment for 45 minutes. Next, the same UV irradiation grafting as in Example 1 was performed using 180 ml of water, 20 mg of AIBN, and 1.0 ml of acrylic acid.
[0095]
(Example 23)
The same procedure as in Example 17 was performed, except that a methanol solution of orthohydroxy biphenyl (impregnating agent D) was used.
[0096]
(Example 24)
Sodium salicylate (impregnant E) was used, plasma treatment was performed for 30 seconds as the activation treatment, a mixture of acrylic acid and methacrylic acid was used as the monomer, and the others were the same as in Example 17.
[0097]
(Comparative Example 29)
It is a result of an untreated polypropylene film.
(Comparative Example 30)
The treatment from Example 22 was carried out without the impregnating agent treatment.
(Comparative Example 31)
The treatment in Example 22 was carried out without the impregnating treatment and the activation treatment.
(Comparative Example 32)
From Example 22, the treatment without the impregnating treatment and the grafting treatment was performed.
(Comparative Example 33)
The process which carried out the activation process from Example 22 was performed.
The above results are summarized in Table 3.
[Table 3]

[0098]
(Example 25)
Carbon fiber hydrophilization and composite materials:
Carbon fiber 6.0 g was immersed in methanol at 50 ° C. for 30 minutes as an impregnation treatment. The centrifuge (800 rpm) was then applied for 1 minute. Next, as an activation treatment, it is put in a hard glass container having a thickness of 1.5 mm, oxygen is introduced into the ozone generator at a flow rate of 100 ml / min, and ozone having a concentration of 40 mg / L is generated. Introduced and blown for 30 minutes. Next, oxygen not containing ozone was blown for 10 minutes. Next, as grafting, 1.2 ml of acrylic acid, 200 ml of water, and 5 ml of methanol were added to the treated fiber to bring the reaction vessel into a nitrogen atmosphere. A high pressure mercury lamp (Toshiba high pressure mercury lamp H400P) was irradiated to the reaction vessel from a distance of 15.5 cm for 3 hours. The temperature was 45 ° C. Next, the contents of the container were poured into a large amount of water. The carbon fiber to which the polymer was adhered was taken out and boiled and washed with a detergent three times. The graft rate was 15%. After the treatment, it was washed three times with a boiling detergent aqueous solution (once, using 500 ml of water). After drying, the water absorption increased to 200% (untreated 120%).
[0099]
(Comparative Example 34) The graft ratio was 4.2% when the activation treatment and the ultraviolet ray grafting were carried out except for the impregnation treatment.
(Comparative Example 35) When the impregnating treatment and the ultraviolet grafting treatment were performed, the graft ratio was 3.0%.
(Comparative Example 36) When only ultraviolet grafting was performed, the graft ratio was 1.0%.
[0100]
(Example 26) The carbon fiber obtained in Example 25 was mixed with an epoxy resin adhesive and dried to produce a 5 mm x 5 mm x 100 mm bar. For comparison, an epoxy resin rod mixed with untreated hydrophilized carbon fiber was prepared. The tensile strength of the hydrophilic carbon fiber reinforced epoxy resin rod showed 40 times the tensile strength of the epoxy resin rod mixed with the untreated hydrophilic carbon fiber.
[0101]
(Example 27)
Hydrophilization of wool fiber cloth:
As an impregnating agent treatment, 1.02 g of wool fiber (woven fabric) was immersed in a solution composed of 10 mg of anhydrous sodium carbonate, 10 parts of methanol and 90 parts of water for 30 minutes. The centrifuge (800 rpm) was then applied for 1 minute. Next, as an activation treatment, oxygen at a flow rate of 100 ml / min was introduced into an ozone generator to generate ozone having a concentration of 40 mg / L, which was introduced into a container and contacted for 30 minutes. Next, oxygen not containing ozone was blown for 10 minutes. Next, as grafting, 1.2 ml of acrylic acid, 200 ml of water, and 5 ml of methanol were added to the treated fiber to bring the reaction vessel into a nitrogen atmosphere. A high pressure mercury lamp (Toshiba high pressure mercury lamp H400P) was irradiated to the reaction vessel from a distance of 20 cm for 3 hours. The temperature was 45 ° C. Next, the contents of the container were poured into a large amount of water. The carbon fiber to which the polymer was adhered was taken out and boiled and washed with a detergent three times. The graft rate was 18%.
[0102]
(Comparative Example 37) The grafting rate was 4.2% when the activation treatment and the UV grafting were carried out except for the impregnation treatment.
(Comparative Example 38) When only ultraviolet grafting was performed, the graft ratio was 1.5%.
(Comparative Example 39) When the impregnating treatment and ultraviolet ray grafting were carried out, the graft ratio was 1.6%.
[0103]
(Water absorption test)
A treated and untreated wool fiber cloth was floated in parallel to the water surface, and the time taken to absorb water and sink was measured. The untreated wool cloth was 60 minutes, the treated wool cloth of Example 27 was 1 second, and Comparative Examples 37, 38, and 39 were 15 seconds, 28 seconds, and 30 seconds, respectively.
[0104]
(Example 28)
Hydrophilization of polypropylene synthetic paper:
The porous polypropylene film for synthetic paper was treated in the same manner as in Example 2 to impart hydrophilicity. The treated synthetic paper can be written with water-soluble ink, and the sticky paper can be adhered with a water-soluble paste (starch, CMC, PVA glue, etc.). The sticky paper could not be peeled because it broke.
[0105]
(Example 29)
Hydrophilization of porous polyethylene film and filter application:
About the porous polyethylene film 0.3g (size 10cm x 10cm), the process similar to Example 17 was performed. The treated film was washed with a boiling detergent aqueous solution and thoroughly washed with water. After drying, the water absorption was 200% (5% for the untreated porous polyethylene film). The contact angle of water was not measurable due to water absorption (considered as 0 °, 120 ° for untreated porous polyethylene film). The weight increase of the sample due to the hydrophilization treatment was 2%. This hydrophilized porous polyethylene film had alkali resistance and acid resistance, and was effective in filtering components in an aqueous solution.
[0106]
(Example 30) For a porous polyethylene film, by impregnating treatment (15 minutes with toluene at 70 ° C), activation treatment (plasma treatment 0.5 minutes), UV grafting (using methacrylic acid and potassium persulfate), The same results as in Example 26 were obtained.
[0107]
(Example 31)
Hydrophilization of porous polysulfone film and filter application:
As a saturant treatment, 0.5 g of a porous polysulfone film (size 10 cm × 10 cm) was immersed in a 10% by volume aqueous methanol solution at room temperature for 1 minute. Ozone treatment was performed for 5 minutes as the activation treatment. The same treatment as in Example 17 was performed. The treated film was washed with a boiling detergent aqueous solution and thoroughly washed with water. After drying, the water absorption was 200% (5% for the untreated porous polyethylene film). The contact angle of water could not be measured due to water absorption (120 ° for an untreated porous polyethylene film). The increase in the mass of the sample due to the hydrophilization treatment was 2%. This hydrophilized porous polyethylene film has alkali resistance, acid resistance, and heat resistance (heat treatment for 30 minutes in a 120 ° C. autoclave was repeated three times), and was effective in filtering components in an aqueous solution. It was.
[0108]
(Example 32)
Hydrophilization of polypropylene nonwoven fabric 2 (using polyvinyl alcohol):
As an impregnation treatment, 1.0 g (size: about 15 cm × 15 cm) of the polypropylene nonwoven fabric 2, and 2.5 g of diphenyl and 0.2 g of a surfactant (sodium dodecylbenzenesulfonate) mixed with 200 ml of water, Soaked at 50 ° C. for 5 minutes. Next, the liquid was removed with a centrifuge (rotation speed 1000 times / min). When the weight increase reached 4%, ozone treatment was performed at 20 ° C. for 30 minutes as an activation treatment. Next, as a polymer treatment, the treated nonwoven fabric was put in a reaction vessel, and a mixture of 200 ml of water, 60 mg of potassium persulfate, 0.3 g of polyvinyl alcohol, and 6 ml of methanol was added and treated at 80 ° C. for 2 hours. After the treatment, it was washed with water and washed with detergent. The water absorption is 800 to 1100%, and the water absorption rate of the sample is quality The increase or decrease in amount could not be measured with an accuracy of 0.1 mg. The results are shown in Table 1. The water absorption rate was maintained at 810% or more even after six washings with detergent. This treated sample was optimal as a material for water absorption applications.
[0109]
(Example 33) Treatment of polypropylene nonwoven fabric 2 according to Invention 2 (using sodium carboxymethyl cellulose):
The polypropylene nonwoven fabric 2 was treated in the same manner as in Example 32 using sodium carboxymethyl cellulose instead of polyvinyl alcohol. The water absorption was 600 to 900% and was durable.
[0110]
(Example 34)
Use of microorganism culture medium: Each of the two water-absorbing nonwoven fabrics produced according to Example 32 was cut into 2 cm × 2 cm pieces and arranged so as not to overlap a petri dish having a diameter of 8 cm and a depth of 2 cm. After making 100 ml of bouillon agar solution consisting of an aqueous solution containing 1 wt% meat extract, 1 wt% polypeptone, 0.5 wt% sodium chloride and 1.5 wt% agar, the agar was melted in a microwave oven, and then the bouillon agar After 50 ml of the solution was soaked into the nonwoven fabric, the temperature was returned to room temperature. The nonwoven fabric impregnated with the bouillon agar solution thus obtained (referred to as a medium nonwoven fabric) was placed in a test tube autoclaved at 120 ° C. for 15 minutes. Incubate this tester overnight at 37 ° C., and confirm the aseptic condition the next day, then culture the microorganism strain (E. coli K-12 strain, Salmonella typhimurium LT-2 strain, Bacillus subtilis Marburg strain, etc. ) Was planted, and this was statically cultured overnight at 30-37 ° C. with a thermostat. When the growth state of the various inoculated bacteria was observed with a microscope, the various bacteria were growing smoothly.
[0111]
(Comparative Example 40)
The polypropylene nonwoven fabric 2 was subjected to the treatment excluding the impregnation treatment step of Example 32. The water absorption of the treated sample decreased from 780% to 400% after three detergent cleanings.
[0112]
(Example 35) Hydrophilization of sample 6 according to Invention 3 and use of wipe cleaning cloth:
Sample 6 is a non-woven fabric of core-sheath fiber having polyester as a core and polyethylene as a sheath.
2.4 g of a nonwoven fabric of polyethylene / polyester core-sheath composite fiber was impregnated at room temperature, and 10 ml of a solution (impregnant D) obtained by dissolving 0.5 g of 10 ml of orthohydroxybiphenyl in 300 ml of methanol at 70 ° C. Soaked for a minute.
Next, it was subjected to a centrifugal dehydrator (rotation speed 1000 / min), and the surface was apparently dried. The increase in mass was about 4%. Next, ozone treatment was performed for 30 minutes. Next, the ozone-treated non-woven fabric was placed in an Erlenmeyer flask, and 5 ml of methanol, 100 ml of water, 0.5 g of polyvinyl alcohol, and 0.1 g of potassium persulfate were added and treated at 80 ° C. for 2 hours. After the treatment, it was thoroughly washed with 60 ° C. water. The treated nonwoven fabric was squeezed (with a water absorption rate of about 300%), placed in a container, 400 ml of water, 100 mg of dicerium ammonium nitrate (IV) and 5 ml of acrylic acid were added, and the mixture was allowed to stand at 80 ° C. for 2 hours. The treated nonwoven fabric was washed three times with a detergent solution at 60 ° C. after treatment (uses 500 ml of water once). After drying, the water absorption (according to the water absorption test 1) was 2310%, and the untreated nonwoven fabric was 350%. The weight increase of the sample due to the hydrophilization treatment was 4%. Further, the water absorption rate is higher than that of the method of the invention 1 (the water absorption rate is about 1400% when treated by the method of the invention 1), and the water absorption speed and water absorption durability are excellent. It was optimal as a product. The hydrophilic nonwoven fabric was made to absorb water (water absorption rate of about 2000%), and 10 sheets were attached to a cleaning mop and used to wipe the wooden floor. After use, it was rinsed with water and could be used over 10 times.
[0113]
(Example 36)
Hydrophilic polypropylene nonwoven fabric 2 and disposable sanitary materials:
Using the hydrophilized polypropylene nonwoven fabric 2 obtained by the method of Example 11 as an inner fabric, using a moisture retention agent (water-absorbing polymer: pulp, starch, polyacrylic acid modified product, etc.) and external untreated polypropylene nonwoven fabric. Manufactured a model of disposable diapers. That is, an untreated water-repellent polypropylene nonwoven fabric was placed at the bottom, a water-absorbing polymer was laid thereon, and the water-absorbing polyolefin nonwoven fabric of the present invention was further placed thereon. When water was applied from above, the water quickly permeated the water-absorbing polyolefin nonwoven fabric and was absorbed by the moisture retention agent. Thus, the water-absorbing nonwoven fabric according to the present invention is optimal as a material for disposable diapers and sanitary and sanitary products.
[0114]
(Example 37)
Improved adhesion of orthodontic polypropylene brackets:
About 20 orthodontic brackets made of polypropylene (0.622 g), methyl methacrylate was grafted in the same manner as in Example 14. The polymerization inhibitor for methyl methacrylate was used except. The treated product was improved in adhesion to ceramic dental material by the polymerizable acrylic resin adhesive, and the material failure of the orthodontic polypropylene bracket was caused by the tensile test.
[0115]
(Comparative Example 41)
A polypropylene / polyethylene non-woven fabric hydrophilized with a known surfactant (Nippon Vilene Co., Ltd. impregnated with a surfactant: the basis weight is the same as Sample 4 in Table 1) was prepared. Similar evaluations were made. The results were as follows.
1) Alkali resistance test: After drying, the water absorption decreased to the original 5%.
2) Sulfuric acid resistance test: After sufficiently washing with water and drying, the water absorption decreased to the original 5%.
3) Antioxidant test: After drying, the water absorption decreased to the original 5%.
[0116]
(Comparative Example 42) Grafting of acrylic acid onto nonwoven fabric 1 by known ultraviolet irradiation: 1.2 g (size 7.7 cm × 10 cm) of nonwoven fabric 1 described in Table 1 made of polypropylene was added to acrylic acid monomer 20.0% The sample was immersed in a reaction solution having a composition of 78.8% water, 0.2% benzophenone and 1.0% methanol (all by weight), and irradiated with a 400 watt high-pressure mercury lamp from a distance of 12 cm for 120 minutes. The non-woven fabric after the reaction was solidified with the polymer, but the polymer was dissolved and separated as a result of washing with boiling water for 10 minutes with an aqueous solution of fatty acid sodium soap (concentration 2% by weight, bath ratio 1/20). The water absorption of the obtained nonwoven fabric was 100% (48% for the untreated nonwoven fabric). The graft ratio was 1%. That is, grafting by ultraviolet irradiation is difficult in the case of the present nonwoven fabric. By boiling washing with a detergent, it was considered that the single polymer consisting only of the generated acrylic acid was dissolved and removed from the nonwoven fabric. The hydrophilicity was lowered by the acid and alkali treatment.
[0117]
【The invention's effect】
As described above, various polymer materials obtained by the method for modifying a polymer material according to the present invention showed excellent properties such as water absorption and adhesive property improvement without causing a decrease in strength. . The property imparted by the modification is excellent in durability. In addition, applications for aqueous solution filtration have been developed by hydrophilizing polyolefin filter media. It is possible to give water absorption to the synthetic paper, improve adhesiveness, and improve printing performance. Since the adhesiveness of many polymer materials including carbon fibers with adhesives is improved, a hydrophilized product useful as a reinforcing fiber for composite materials is provided. The hydrophilicity of various polymer molded products can be improved, and the absorbability of water-soluble ink can be improved for polyolefin writing instrument parts, which has been impossible in the past. It can improve the application of various medical / hygiene / cosmetic products and textile products for clothing, the adhesion of orthodontic polypropylene brackets, and the wettability of polymeric medical materials.

Claims (24)

The surface of the polymer material is contacted with (1) a compound impregnating the polymer material, and the impregnation amount within 1000 microns from the surface is in the range of 0.1 to 40% by weight (with respect to the polymer material). Impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group to the surface of the polymer material, and (3) catalyst, initiator, heating, ultraviolet irradiation A method for modifying a polymer material, characterized by treating in this order by a step of grafting a monomer in the presence of at least one of the above. The surface of the polymer material is contacted with (1) a compound impregnating the polymer material, and the impregnation amount within 1000 microns from the surface is in the range of 0.1 to 40% by weight (with respect to the polymer material). Impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group to the polymer material surface, (3) in the presence or absence of a catalyst or initiator A method for modifying a polymer material, wherein the treatment is performed in this order by a step of treating with a hydrophilic polymer solution below . The surface of the polymer material is contacted with (1) a compound impregnating the polymer material, and the impregnation amount within 1000 microns from the surface is in the range of 0.1 to 40% by weight (with respect to the polymer material). Impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group to the polymer material surface, (3) in the presence or absence of a catalyst or initiator It is characterized in that it is treated in this order by a step of treating with a solution of a hydrophilic polymer below and (4) a step of grafting a monomer in the presence of at least one of a catalyst, an initiator, heating and ultraviolet irradiation. A method for modifying a polymer material.   The polymer material is a molded body or other material selected from the group consisting of fibers, woven fabrics, knitted fabrics, nonwoven fabrics, plates, bars, films, sheets, porous films and sheets, and members or products molded into a predetermined shape. 4. The method for modifying a polymer material according to claim 1, wherein the polymer material is a composite material.   4. The method for modifying a polymer material according to claim 1, wherein the polymer material contains at least one of an antioxidant and a stabilizer.   The method for modifying a polymer material according to any one of claims 1 to 3, wherein the impregnation treatment is performed at a temperature below the melting point or the softening point of the polymer material.   4. The activation process according to claim 1, wherein the activation process is at least one process selected from the group consisting of an ozone process, a plasma process, an ultraviolet irradiation process, a corona discharge process, and a high-pressure discharge process. A method for modifying a polymer material as described.   The method for modifying a polymer material according to any one of claims 1 to 3, wherein the monomer is a compound having a carbon-carbon double bond.   The monomer is acrylic acid, methacrylic acid, vinyl acetic acid, 2-butenoic acid, ethylene sulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, maleic anhydride, pyromellitic anhydride The mixture of at least one monomer selected from the group consisting of at least one monomer selected from these groups and another vinyl monomer. A method for surface modification of a polymer material according to claim 1.   The hydrophilic polymer is polyvinyl alcohol, carboxymethyl cellulose, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyalkylene glycol, starch, glucomannan, fibroin, sericin, The method for modifying a surface of a polymer material according to claim 2 or 3, wherein the polymer material is at least one polymer compound selected from the group consisting of agar, protein in egg white, and sodium alginate.   The method of grafting the monomer comprises (1) a method performed in the presence of a catalyst or an initiator, (2) a method of heating in the presence or absence of a catalyst or an initiator, (3) a catalyst or The polymer material according to any one of claims 1 and 2, wherein the method is a method of irradiating ultraviolet rays in the presence or absence of an initiator or a photosensitizer, either alone or by a plurality of methods. Reforming method.   The method for modifying a surface of a polymer material according to any one of claims 2 to 3, wherein in the step of treating with the hydrophilic polymer, these steps are carried out in the presence of a catalyst or an initiator.   The initiator is at least one compound selected from the group consisting of peroxides, ceric ammonium nitrate (IV), persulfates, redox initiators and other radical polymerization initiators. The method for modifying a polymer material according to claim 11.   A polymer material modified by the polymer material modification method according to claim 1.   A wiping and cleaning material comprising a polymer material modified by the polymer material modification method according to claim 1.   A filter medium comprising a polymer material modified by the polymer material modification method according to claim 1.   A water-absorbing material comprising a polymer material modified by the polymer material modification method according to claim 1.   A water retention material comprising a polymer material modified by the polymer material modification method according to claim 1.   A member for a writing instrument using a polymer material modified by the method for modifying a polymer material according to claim 1.   A material for a microbial medium comprising a polymer material modified by the method for modifying a polymer material according to any one of claims 1 to 13.   A medical / hygiene / cosmetic article comprising a polymer material modified by the polymer material modification method according to claim 1.   A synthetic paper made of a polymer material modified by the method for modifying a polymer material according to any one of claims 1 to 13.   An orthodontic bracket containing a polymer material modified by the polymer material modification method according to claim 1.   A medical device material comprising a polymer material modified by the method for modifying a polymer material according to claim 1.