JP4050801B2 - Method for modifying polymer material by gas phase photochemical reaction, modified polymer material and dyeing method - Google Patents

Description

【００１３】
しかしながら、このような光化学的な反応機構による方法では、主として低分子化合物の反応を実施しているため、液相中でも分子の拡散又は混合は充分に起こるが、高分子材料との反応では固体中での分子の拡散を充分に起こさせるためには、固体−液体よりは固体−気体の状態の方が拡散速度も速く、表面ばかりでなく、高分子材料内部の改質も効率よく実施できる。さらに、液体中では活性種と改質すべき材料との衝突確率も低くなり、従来、液体中の処理では充分に目的を達成することは困難であった。
【００１４】
一方、高分子材料の染色技術についての従来技術と問題点について述べると、次の通りである。
合成繊維は天然繊維に比べて一般的に染色性に乏しいといわれている。これは天然高分子に比べて、合成高分子はその構造に染料分子が結合する足掛かりになる官能基の数が極めて少ない事に由来しているといえる。また、官能基の種類により染色するための染料を使い分ける必要があり、すべての材料を同一染料により染色し染着することはできない。例えば、ナイロンはカチオン、アニオン、反応性染料で染色可能であり、この時に染料分子が結合する足掛かりとなる官能基は重合末端のアミノ基もしくはカルボキシル基でありその数は極めて少なく、充分な染色性を具備しているとは言えない。
【００１５】
さらに、他の合成高分子材料のポリエチレンテレフタレート，ポリプロピレン，アラミド等においては官能基はさらに少なくカチオン，アニオン，反応性染料に対してはほとんど染色性を示さず、実際的には紡糸前に分散染料を練り込むか高温高圧下で分散染料を昇華させて材料のガラス転移温度以上で染料分子を不定形部分に拡散させることで染色するのが唯一の染色法である。そのために天然繊維と合成繊維もしくは異種の合成繊維による混紡による材料は同一染料では染色できなかった。そのために木綿とポリエステルの混紡の染色には反応性染料と分散染料の混合染料により染色したり工夫がされているが染色条件が違い、染着率が充分とはいえなかった。
【００１６】
また木綿等の天然セルロース系繊維は極性基である−ＯＨ基を多数有するため反応性染料分子を結合する官能基は充分であるが低温での反応性は低く、染色には強アルカリの存在下で高温蒸気により反応性を高めねば充分な染色ができないといった問題点があった。これらの問題を解決するために布帛表面にアクリル系樹脂を塗布して表面樹脂を染色したり、顔料をラテックス樹脂で分散させて印捺する等の技術が工夫されたが、この方法では布帛の風合いを阻害するため満足のいく染色方法ではなかった。
【００１７】
【発明が解決しようとする課題】
高分子材料の機能性付与のための改質を充分に高分子量で機械的特性を維持した状態で、もしくは使用時の形態を維持した状態で、反応性もしくは極性官能基を導入することが、本発明の課題である。
【００１８】
さらに導入すべき官能基量も表面のみならず内部、裏面にも従来技術より多く導入し、その効果の持続性が長い高分子材料とその製造処理方法を提供することが、本発明の課題である。
【００１９】
本発明の別の課題は、高分子材料の染料分子と結合する足掛かりとなる官能基を導入し、染色性を向上させると共に異種材料のブレンドもしくは混紡等の混合使用された材料に同一染料で染色することにあり、その時にも布帛であればその風合いを維持した状態で染色し、その染色条件も温和である染色方法を提供することにある。
【００２０】
上記課題を解決するために鋭意検討した結果、本発明においては高分子材料の表面または内部の改質を特定化合物の気相中で活性反応種を反応させることで種々の反応性もしくは極性官能基を導入すること、さらに導入した官能基と反応する化合物により高分子材料の性質を変えること、及び染色する高分子材料に染料分子と強固に結合するための反応性官能基を積極的に導入した材料を使用することが有効であることを、本発明者らは見出した。
【００２１】
【課題を解決するための手段及び作用】
本発明の上記課題は、下記構成によって解決される。
１．天然もしくは合成高分子からなる材料である高分子材料に官能基を導入する改質方法であり、活性エネルギー線により励起することで反応性活性種を発生する第１の化合物の気相中で高分子材料を活性エネルギー線照射下で処理する高分子材料の改質方法において、前記高分子材料は飽和もしくは不飽和の炭化水素構造を有し、Ｃ−Ｈ活性化反応を利用できるものであり、前記第１の化合物が二塩化オキザリルであることを特徴とする高分子材料の改質方法。
【００２２】
２．前記１により得られた改質された高分子材料に反応性もしくは極性官能基を有する第２の化合物を反応させ官能基を変更させる工程を有することを特徴とする高分子材料の改質方法。
【００２３】
３．前記反応性もしくは極性官能基が−ＣＯＣｌ，−ＣＯＯＨ，−ＯＨ，−ＳＨ，−ＮＨ_２，Ｒ_１ＮＨ（Ｒ _１ は−ＣＨ _２ ＣＨ _２ ＯＨを表す。）を末端に有することを特徴とする前記２に記載の高分子材料の改質方法。
【００２４】
４．前記活性エネルギー線が紫外光であることを特徴とする前記１に記載の高分子材料の改質方法。
【００２５】
５．前記２の官能基を変更させる反応を有機溶媒中で行うことを特徴とする前記２又は３に記載の高分子材料の改質方法。
【００２６】
６．前記２の官能基を変更させる工程を前記第２の化合物の気相中で行うことを特徴とする前記２又は３に記載の高分子材料の改質方法。
【００２７】
７．前記第２の化合物が分子構造中に２種以上の反応性もしくは極性官能基を有することを特徴とする前記２又は３に記載の高分子材料の改質方法。
【００２８】
８．天然もしくは合成高分子からなる材料である高分子材料に官能基を導入して得られる改質高分子材料であり、活性エネルギー線により励起することで反応性活性種を発生する第１の化合物の気相中で高分子材料を活性エネルギー線照射下で処理して得られる、反応性もしくは極性官能基を導入した高分子材料において、前記高分子材料は飽和もしくは不飽和の炭化水素構造を有し、Ｃ−Ｈ活性化反応を利用できるものであり、前記活性エネルギー線が紫外光であり、かつ前記第１の化合物が二塩化オキザリルであることを特徴とする改質高分子材料。
【００２９】
９．前記８により得られた改質された高分子材料に反応性もしくは極性官能基を有する第２の化合物を反応させ官能基を変更させて得られることを特徴とする高分子材料。
【００３０】
１０．前記反応性もしくは極性官能基が−ＣＯＣｌ，−ＣＯＯＨ，−ＯＨ，−ＳＨ，−ＮＨ_２，Ｒ_１ＮＨ（Ｒ _１ は−ＣＨ _２ ＣＨ _２ ＯＨを表す。）を末端に有することを特徴とする前記９に記載の改質高分子材料。
【００３２】
１１．前記９の官能基を変更させる反応を有機溶媒中で行うことを特徴とする前記９又は１０に記載の改質高分子材料。
【００３３】
１２．前記９の官能基を変更させる反応を前記第２の化合物の気相中で行うことを特徴とする前記９又は１０に記載の改質高分子材料。
【００３４】
１３．前記第２の化合物が分子構造中に２種以上の反応性もしくは極性官能基を有することを特徴とする前記９又は１０に記載の改質高分子材料。
【００３５】
１４．天然もしくは合成高分子からなる材料である高分子材料の染色方法であり、該高分子材料に予め活性エネルギー線により励起することで反応性活性種を発生する第１の化合物の気相中で高分子材料を活性エネルギー線照射下で処理して得られた反応性もしくは極性官能基を導入した高分子材料を使用する染色方法において、前記高分子材料は飽和もしくは不飽和の炭化水素構造を有し、Ｃ−Ｈ活性化反応を利用できるものであり、前記第１の化合物が二塩化オキザリルであることを特徴とする染色方法。
【００３６】
１５．前記反応性もしくは極性官能基が−ＣＯＣｌ，−ＣＯＯＨ，−ＯＨ，−ＳＨ，−ＮＨ_２，Ｒ_１ＮＨ（Ｒ _１ は−ＣＨ _２ ＣＨ _２ ＯＨを表す。）であることを特徴とする前記１４記載の染色方法。
【００３７】
１６．前記活性エネルギー線が紫外光であることを特徴とする前記１４記載の染色方法。
【００３８】
１７．前記高分子材料が異種材料からなるブレンドもしくは混紡による繊維，フィルムであり、且つ前記高分子材料が有する飽和もしくは不飽和の炭化水素構造のＣ−Ｈ活性化反応を利用する染色方法で用いる染料が同一染料であることを特徴とする前記１４〜１６のいずれかに記載の染色方法。
【００３９】
１８．前記高分子材料が有する飽和もしくは不飽和の炭化水素構造のＣ−Ｈ活性化反応を利用する染色方法で用いる染料が反応性染料であって、これにより中性染色することを特徴とする前記１４〜１６のいずれかに記載の染色方法。
【００４０】
１９．前記高分子材料が有する飽和もしくは不飽和の炭化水素構造のＣ−Ｈ活性化反応を利用する染色方法が、５０℃以下の低温で行われることを特徴とする前記１４〜１６のいずれかに記載の染色方法。
【００４１】
２０．前記高分子材料が有する飽和もしくは不飽和の炭化水素構造のＣ−Ｈ活性化反応を利用する染色方法が、気相中での染色であることを特徴とする請求項１４〜１６のいずれかに記載の染色方法。
【００４５】
【発明の実施の態様】
上記の課題を解決する手段を以下に具体的に述べる。
本発明者らは高分子材料の改質に関する前記課題を解決するために 鋭意検討をした結果、高分子材料の多くには飽和もしくは不飽和の炭化水素構造を有するため、Ｃ−Ｈ活性化反応を利用することで課題を解決することができることを見出した。
そして、光Ｃ−Ｈ活性化により繊維分子を官能基化し、その特性を改質するために光化学反応を気相で行うようにすることにより、高分子材料すなわち紡糸、織布、フィルム等の形状を維持した状態でも処理することを可能とした。
【００４６】
以下、本発明の実施の形態では、特に二塩化オキザリルの光化学反応による、Ｃ−Ｈのクロロカルボニル化反応を用いた例を示す。この反応は、光化学的に発生する、反応性活性種（ラジカル種）を経る反応であり、化学量論的には（式２）に示すとおりである。
【００４７】
【化２】

【００４８】
この反応は、各種の炭化水素基のクロロカルボニル化反応に有効であり、例えば、ポリエチレンテレフタレートの基本構造を有する化合物では、メチレン鎖の各部位がクロロカルボニル化された生成物が得られる。
【００４９】
【化３】

【００５０】
一般にＣ−Ｈ活性化に使用される光としては、化合物を励起して、反応活性種（ラジカル種）を発生させる活性エネルギー線であれば使用可能である。例えば、γ線，β線，Ｘ線などの電子線や放射線や紫外線等の活性エネルギー線が使用できる。その中でも、紫外線からなる紫外光を利用することが、使用場所の制限を受けず、小型化でき、安全性からも好ましい。
また、反応性活性種を発生する第１の化合物としては、前述の活性エネルギー線により励起され反応性活性種を発生する化合物であればよいが、実施例に示す以外にも種々の化合物が使用可能であり、本発明は例示化合物以外にも効果があることはいうまでもなく、発明の範囲は実施例に限定されるものではない。
第１の化合物としては例えば、ニトロシルクロライド等があげられる。
【００５１】
導入後の官能基を利用して特性を変えるためには、特に二塩化オキザリルが第１の化合物として用いられる。二塩化オキザリルは常温で液体であり、適度な蒸気圧（約１００ｍｍＨｇ）を有するため、特に加熱等の処理操作をせずに反応処理容器に導入することで気相での処理が可能となる。気相中とは、化合物のみを気化した雰囲気中、若しくはこれに他の気体を加えた雰囲気中であってもよい。
【００５２】
例えば、オゾン等の気体も使用可能だが、オゾン発生装置を必要とし導入量の制御も困難であり、以下に例示したものが好ましい。
また、気相反応の際のその他の気体としては、空気でも可能であるが安定に処理するためには、湿度及び酸素含有量を制御するために窒素，ヘリウム，アルゴン等の不活性気体が好ましい。また、取り扱いの容易さからは乾燥窒素が好ましい。
処理時の気体圧力は特に問題とはならないが、常圧処理で充分な効果が得られる。また装置の簡便さの点でも常圧処理が好ましい。
【００５３】
改質処理する高分子材料としては、布帛の状態としては植物繊維，動物繊維，人造繊維等からなる織布や編布等が使用できる。植物繊維としては、綿花，麻よりなる布帛、動物繊維としては絹，羊毛よりなる布帛、人造繊維としては再生人造繊維と分類される繊維素系のビスコースレーヨン，ポリノジックレーヨン，銅アンモニウムレーヨン，蛋白質系等の布帛が挙げられる。
また、人造繊維中合成繊維に分類されるポリアミド，ポリイミド，ポリウレタン，ポリビニルアルコール，ポリアクリル，ポリエステル，ポリプロピレン，塩化ビニル，塩化ビニリデン等からなる繊維よりなる布帛が挙げられる。これらの布帛はいずれも繊維状でも織物状並びに編物状の形態のいずれでも使用できる。これらを構成する繊維糸はフィラメント，ステープルの形態のいずれの形態でも構わない。
またこれらの繊維は単独あるいは２種以上の混紡，混織，混編のいずれでも使用可能である。すなわち、これら繊維を構成する高分子材料の分子構造中にＣ−Ｈ結合を有していればいずれの場合にも使用可能である。
【００５４】
また、高分子材料の形態としては繊維ばかりでなく、フィルムもしくは板状の材料にも適応できる。これらを形成する材料としては、ポリエチレンテレフタレート（ＰＥＴ），ポリエチレンナフタレート（ＰＥＮ），ポリエチレン，ポリプロピレン，ポリイミド，ポリアミド，塩化ビニル，塩化ビニリデン等が挙げられる。またこれらの高分子材料のブレンドや 貼り合わせ等の複合材料にも使用することができる。これら複合材料としては、各々の材料を混合してキャストしたフィルム，板やこれらフィルム，板を貼り合わせた表裏の材料が異なるもの、もしくはＰＥＴ表面にポリウレタン樹脂等を塗布したフィルム等が挙げられる。
【００５５】
さらに、本発明では改質された高分子材料の表面官能基を変更することで、使用する用途及び高分子材料に対して使用できる化合物の範囲を拡大できることも特徴である。すなわち、始めに導入された官能基と反応により共有結合を形成する化合物を使用することで、表面の官能基を変更することが可能である。
例えば、式２で示した酸クロライド残基はさらにアミン類もしくはアルコール類，チオール類の化合物もしくは水と反応し、残基を変更することができる。そのとき塩基性化合物の存在下で反応させると導入率を向上させることもできる。
【００５６】
さらに、この時反応性もしくは極性基を分子構造中に２個以上有する化合物を使用すると表面の官能基を所望の残基とすることができるので好ましい。複数の官能基もしくは極性基は同じであっても異なっていても良いが、表面状態を同種官能基とするには同じ官能基であることが好ましい。
【００５７】
表面の官能基を変更するための第２の化合物としてはエチレンジアミン，トリエチレンジアミン等のアミン類やエチレングリコール，ジエチレングリコール，ブタンジオール等のグリコール類やジエタノールアミン，ヒドロキシエチルアミン等の異種の官能基を有する化合物が挙げられる。本発明は必ずしも例示した化合物ばかりでなく反応する官能基ならばいずれも使用することが可能である。
【００５８】
官能基を変更する反応は有機溶媒中、例えばベンゼン，トルエン，キシレン，ヘキサン，ヘプタン等の石油系炭化水素溶媒や塩化メチレン，クロロホルム四塩化炭素等のハロゲン化炭化水素等の溶剤中に第２の化合物を溶解して、改質されて酸クロライド残基を有する高分子材料表面に浸漬することで処理することができる。またこの時に脱塩化水素のためにトリエチルアミンやピリジン等の三級アミン類や水酸化ナトリウム、ナトリウムアルコキシド等のアルカリ性試薬を共存させて反応させた後水洗して副成物を除去しても良い。
【００５９】
また、本反応は第２の化合物をガス状として導入した気相中でも達成できる。このような第２の化合物としては沸点が低く蒸気圧が比較的高いものか、もしくは加熱することで容易にガス状にできるものであれば可能であり洗浄等の処理を必要としないなどの利点を有する。
このような第２の化合物の中でもガス状にして気相中で反応可能なものとしてはエチレンジアミン等の化合物が使用できる。
反応模式図で示すと式４の様に表せる。
【００６０】
【化４】

【００６１】
次に、本発明に係る改質高分子材料からなる繊維、布帛、フィルム、板状体等の染色方法について補充説明する。
本発明における布帛は織物でも編物でも、不織布でもよく、布帛に用いる繊維素材としては、任意の合成繊維（ポリエステル、ポリアミド、アクリル繊維など）、半合成繊維（アセテート、レーヨンなど）、天然繊維（綿、絹、羊毛など）、これらの混合品（混紡品、交撚品、交編繊品）などすべての繊維素材を適用することができる。
【００６２】
本発明における染料インクとしては布帛に対して染着可能な染料を含有するものが必要であり、この染料としては酸性染料、直接染料、反応性染料、カチオン染料、分散染料などがあげられる。
【００６３】
従来の染色方法では、染料液を構成する染料は使用する繊維素材に対応して変更させなければならない。例えば、布帛を構成する繊維素材がポリエステル、アセテート繊維である場合は染料液は分散染料を用いて構成される。
布帛を構成する素材が羊毛、絹、ポリアミド、綿、レーヨンなどアニオン性染料可染素材の場合は染料として、直接染料、酸性染料、反応染料などのアニオン性染料が適用される。また、アクリル繊維やカチオン可染ポリエステル系繊維などのカチオン性染料可染素材の場合は染料としてカチオン性染料が適用される。
【００６４】
本発明に使用される染料としては、素材に対応して変更させる必要はなく、導入した官能基と共有結合もしくはイオン結合をする染料が使用できる。一般的な染料としては、次のようなものが挙げられる。
分散染料としては、アゾ系、アントラキノン系、ニトロジフェニルアミン系、ナフタルイミド系、ナフトキノンイミド系、メチン系などがあげられる。具体的には新版染料便覧（発行所；丸善株式会社）第７２５〜８１６頁記載の染料があげられる。
直接染料としては、アゾ系、スチルベン系、チアゾール系、ジオキサジン系、フタロシアニン系などがあげられる。具体的には同染料便覧第３１７〜３９６頁記載の染料があげられる。
酸性染料としては、アゾ系、アントラキノン系、トリフェニルメタン系、キサンチン系などがあげられる。具体的には同染料便覧第３９３〜５２６頁記載の染料があげられる。
反応染料としては、アゾ系、アントラキノン系、フタロシアニン系染料などがあげられる。具体的には同染料便覧第８８１〜９３４頁記載の染料があげられる。
カチオン染料としては、具体的には同染料便覧第５２９〜５６２頁記載の染料があげられる。
【００６５】
尚、布帛に付与された染料を加熱発色させるために蒸熱または乾熱処理してもよい。熱固着条件は使用される染料の種類や布帛類の種類によって異なるが、蒸熱の場合、１００〜１３０℃で１０〜３０分、乾熱の場合、１８０〜２１０℃で１〜５分処理する。最後に未染着染料および該水不溶性吸水性樹脂を除去するためにソーピングまたは還元洗浄を行う。
【００６６】
【実施例】
以下に実施例を含めて具体的効果を説明する。
実施例１−１
予め真空乾燥器中で５０度で１時間、減圧下で乾燥させた厚み１１０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを５ｃｍ×５ｃｍの形状にして、３０Ｗの低圧水銀灯を取り付けた容器に吊るし、二塩化オキザリルガスと窒素ガスとがそれぞれ分圧１００ｍｍＨｇ，６６０ｍｍＨｇとなるようにして２０分間光照射して処理した。容器からＰＥＴフィルムを取り出し乾燥空気で１時間風乾した。
【００６７】
実施例１−２
ＰＥＴフィルムを厚さ２００μｍのポリプロピレン布帛に変えた以外は実施例１−１と同様に処理した。
【００６８】
実施例１−３
ＰＥＴフィルムを厚さ１２０μｍのアラミド繊維からなる布帛に変えた以外は実施例１−１と同様に処理した。
【００６９】
比較例１−１
二塩化オキザリルガスの替わりに窒素ガスとして実施例１−１と同様に処理した。
【００７０】
比較例１−２
低圧水銀灯の照射をせずに実施例１−１と同条件で処理した。
【００７１】
以上の実施例１−１，２，３および比較例１−１，２の試料を反射ＦＴ−ＩＲにより表面の赤外スペクトルにより塩化カルボニルの特性吸収を測定した。さらに、それぞれの試料を５０℃で１００ｍｌの水に３０分間浸漬し、試料を引き上げた残液の特性をリトマス試験紙で測定した。結果を表１に示す。
【００７２】
【表１】

【００７３】
いずれの例においても処理前と後での形状変化はなく、触感等の風合いにも変化を与えなかった。
以上の結果から材料に塩化カルボニル基が導入され、反応性を有するために水により加水分解され残液が酸性を呈することがわかる。
さらに、塩化カルボニル基ばかりでなく他の官能基にも変換できる例を示す。
実施例１−４
実施例１−１で処理したＰＥＴフィルムを１％のエチレンジアミンを含むベンゼン溶液１００ｍｌに１０分間室温で浸して引き上げ、その後真空乾燥器中で減圧としてベンゼンとエチレンジアミンを留去した。
【００７４】
実施例１−５
実施例１−１で処理したＰＥＴフィルムを１％のエチレングリコールと等量のトリエチルアミンを含むベンゼン溶液１００ｍｌに１０分間室温で撹拌しながら浸して引き上げ、水洗後真空乾燥器中で乾燥した。
実施例１−４，５の試料を反射ＦＴ−ＩＲにより表面の赤外分光吸収スペクトルを測定した結果、塩化カルボニルの特性吸収が消失し、水酸基およびアミノ基と同定されるブロードな特性吸収を得た。
【００７５】
次にこれらの官能基が変化したことを確認するための例を示す。
実施例１−６
実施例１−１および４の試料および比較Ａとして処理を施さないＰＥＴフィルムをメチレンブルーおよびオレンジ２で染色した。結果を表２に示す。
【００７６】
【表２】

【００７７】
以上の結果からＰＥＴの改質がされ官能基が導入されており、さらに導入された官能基が変換されていることがわかる。
以上の結果から本発明は天然及び合成高分子材料に官能基を導入することによりその特性を改質できることがわかる。
【００７８】
以下に本発明に係る染色方法の実施例を含めて具体的効果を説明する。
実施例２−１
予め真空乾燥器中で５０度で１時間、減圧下で乾燥させた厚み１８０μｍのポリエチレンテレフタレート（ＰＥＴ）布帛を５ｃｍ×５ｃｍの形状にして、３０Ｗの低圧水銀灯を取り付けた容器に吊るし、二塩化オキザリルガスと窒素ガスとがそれぞれ分圧１００ｍｍＨｇ，６６０ｍｍＨｇとなるようにして２０分間光照射して処理した。容器からＰＥＴフィルムを取り出し乾燥空気で１時間風乾した。
【００７９】
実施例２−２
ＰＥＴ布帛を２２０μｍのポリプロピレン布帛に変えた以外は実施例２−１と同様に処理した。
【００８０】
実施例２−３
ＰＥＴ布帛を２００μｍのアラミド布帛に変えた以外は実施例２−１と同様に処理した。
【００８１】
実施例２−４
ＰＥＴ布帛を２５０μｍのナイロン布帛に変えた以外は実施例２−１と同様に処理した。
【００８２】
比較例２−１
実施例２−１の処理をしないＰＥＴ布帛
比較例２−２
実施例２−１の処理をしないポリプロピレン布帛
比較例２−３
実施例２−１の処理をしないアラミド布帛
比較例２−４
実施例２−１の処理をしないナイロン布帛
【００８３】
実施例２−１，２，３，４及び比較例２−１，２，３，４の布帛をＰＨ＝８の水中でカチオン染料であるメチレンブルーで染色した。結果を表３に示す。
【００８４】
【表３】

【００８５】
以上の例からもわかるように異種材料の染色が同一染料で可能となり、さらには従来では染色できない材料も本染色方法により染色可能となることがわかる。
【００８６】
さらに本発明による官能基の変更に関して実施例により説明する。
実施例２−５
実施例２−１で処理したＰＥＴ布帛を１％のエチレンジアミンを含むベンゼン溶液に１０分間室温で浸して引き上げ、その後真空乾燥器中で減圧としてベンゼンとエチレンジアミンを留去した。
【００８７】
実施例２−６
実施例２−４で処理したナイロン布帛を実施例２−５と同様に処理した。
【００８８】
実施例２−７
実施例２−３で処理したアラミド布帛を実施例２−５と同様に処理した。
【００８９】
比較例２−５
実施例２−１で処理したＰＥＴ布帛
【００９０】
実施例２−５，６，７及び比較例２−５の処理布帛をｐＨ＝３．５の水中でアニオン染料であるオレンジ２で染色した結果、ナイロンで染色性の大幅な改善が認められ濃色に染色された。またＰＥＴではまったく染色されないものが良好に染色された。アラミドでも染色性良好であった。結果を表４に示す。
【００９１】
【表４】

【００９２】
以上の結果からも異種材料の染色が同一染料で染色できることを示している。また実施例２−１，５及び比較例２−５からもわかるように、処理の違いによりメチレンブルーとオレンジ２による染色性が変化しており、このことは処理により官能基の変換がされていることを示唆している。
【００９３】
さらに反応性染料による染色例を説明する。
実施例２−８
実施例２−５のポリエステル布帛を中性の水中で反応性染料であるＰｒｉｃｉｏｎ Ｒｅｄ ＭＸ−５Ｂで染色した。
【００９４】
比較例２−６
実施例２−１の処理に使用したポリエステル布帛を何も処理せずに実施例２−８と同様に染色した。結果を表５に示す
【００９５】
【表５】

【００９６】
この結果から反応性染料では全く染色されないポリエステル布帛が本発明の 染色方法により染色されることがわかる。またその染色条件も中性であり、強アルカリを使用せずに室温程度の低温染色で染色されることがわかる。実施例２−８で染色された布帛を家庭用洗剤（商品名モノゲン）水溶液で約１時間煮たが脱色等の変化はなく強固に染着されていることを確認した。
【００９７】
【発明の効果】
本発明の改質方法及び改質高分子材料によれば、高分子材料に対し、材料の機械的強度や使用時の形態を維持した状態で反応性若しくは極性官能基を導入できる。そして、この基の導入により高分子材料の特性を改質できる。
【００９８】
また、本発明の染色方法によれば、異種の材料を同一染料により染色することが可能であり、布帛の風合いを維持した優れた染色方法である。また反応性染料の染色においても特に強アルカリを必要とせず、しかも温和な条件で強固な染色ができる。尚、混紡系についても、本発明の効果が得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for modifying and dyeing materials made of natural or synthetic polymers. Specifically, a method for modifying a polymer material that introduces a reactive or polar functional group for imparting functionality to a material composed of a polymer, a modified polymer material, and a fiber, a fabric composed of the modified polymer material, The present invention relates to a method for dyeing films, plates and the like.
[0002]
[Prior art and problems]
Conventionally, in order to introduce a reactive or polar functional group to give functionality to a polymer material, in the case of a synthetic polymer, a functional group is previously introduced into a polymerizable monomer (monomer) which becomes a repeating unit. Thereafter, there are a polymerization method and a method in which a polymer material is dissolved in a solvent and introduced by a reaction between a compound having a functional group to be introduced and a polymer. Functionality includes wettability (hydrophilicity, water repellency), polarity and the like. Regarding the modification of polymer materials by introducing functional groups into these polymer materials and the method, for example, a book on functional polymers (Kyoritsu Publishing Co., Ltd.) edited by the Society of Polymer Science, Japan It is stated in.
[0003]
However, in the method of introducing the monomer into the polymerizable monomer (monomer) in advance, the introduced functional group inhibits the polymerization reaction, the degree of polymerization does not increase, or the introduced functional group reacts during the polymerization. There are problems such as reducing the amount of solvent, lowering the solvent solubility of the polymer material to which the corner function is added by creating a crosslinked structure by reaction, and making it difficult to change the shape such as molding in order to increase the thermal softening temperature. there were.
[0004]
Furthermore, depending on the polymerization reaction, there is a problem that the functional group to be introduced does not exhibit a sufficient function because it is present in the material as a non-uniform block. Further, this method cannot be used for modifying materials such as natural fibers.
[0005]
In addition, the method of introducing a functional group by dissolving a polymer material in a solvent and reacting with a low molecular compound having a functional functional group can be used only for a material that dissolves in the solvent, and has a functional group to be introduced. If the low molecular weight compound is not dissolved in the same solvent as the polymer material, the reaction will not proceed well, and even if the functional group introduction reaction proceeds, the solubility in the reaction solvent will decrease with the progress of the reaction, resulting in precipitation, etc. There is also a problem that a sufficient amount of functional groups cannot be introduced.
[0006]
In addition to the above, a method of surface modification after forming a polymer material into a structure such as a film, a fiber or a fabric woven by spinning using fibers, or a knitted fabric is also widely used in various fields. ing. As the method, there is a method in which polar groups are generated on the surface of a polymer structure (polymer material) by treatment such as electron beam, plasma, corona discharge in the presence of a gas such as nitrogen, oxygen, helium and argon. For example, methods for improving the wettability of an aqueous dye solution during printing by plasma treatment of the surface of the fabric are described in JP-A-2-47378, JP-A-4-153811, and the like.
[0007]
This method is effective in improving the wettability of the fabric surface with the aqueous dye solution, but a sufficient amount of functional groups for imparting a function cannot be introduced. Furthermore, there is a problem that desired reactivity or polar functional groups cannot be introduced.
[0008]
Also disclosed is a method for improving the adhesion by a method in which the surface of a film made of polyethylene terephthalate is subjected to corona discharge treatment in air and a coating film is formed on the treated surface. In this method, the film surface is modified and the adhesiveness is improved by the interaction with the coating film, but a desired functional group cannot be introduced.
[0009]
In addition, these conventional methods sometimes have a problem that foreign matters such as dust are easily attracted due to charging during processing, and the surface is contaminated. Furthermore, the sustainability of the effect was short and it had to be used in the next step immediately after treatment. Further, the modification was only on the polymer surface, and the effect could not be exerted on the inside or the back side of the material.
[0010]
In addition, a technology that efficiently improves and uses the polarity of the surface by actively irradiating the fabric surface with ultraviolet rays in the presence of ozone has been disclosed, but a sufficient amount of polar groups has not been introduced, and its effect There is a problem with the sustainability of the product, and a desired functional group cannot be introduced.
[0011]
In addition, photo-CH activation will be described.
C—H activation is a means for directly introducing a functional group by cleaving an inactive C—H bond such as a saturated hydrocarbon, such as chlorine substitution into natural gas. It hits.
Usually, a metal catalyst or the like is used, but there is a method based on a photochemical reaction mechanism. Although these reactions are well known as organic synthetic chemistry reactions, they are not widely used industrially because of the difficulty in controlling the reaction position. However, examples of use include photonitrosation of cyclohexane (formula 1) in Toray's caprolactam synthesis.
[0012]
[Chemical 1]

[0013]
However, in such a method based on a photochemical reaction mechanism, a reaction of a low-molecular compound is mainly carried out, so that diffusion or mixing of molecules occurs sufficiently even in a liquid phase. In order to sufficiently cause molecular diffusion in the solid-liquid state, the solid-gas state has a higher diffusion rate than the solid-liquid state, and not only the surface but also the inside of the polymer material can be efficiently modified. Furthermore, the collision probability between the active species and the material to be modified is low in the liquid, and conventionally, it has been difficult to achieve the object sufficiently by the treatment in the liquid.
[0014]
On the other hand, conventional techniques and problems regarding dyeing techniques for polymer materials are described as follows.
Synthetic fibers are generally said to have poor dyeability compared to natural fibers. It can be said that the synthetic polymer is derived from the fact that the number of functional groups that serve as a foothold for the dye molecule to bind to the structure is extremely small compared to the natural polymer. Moreover, it is necessary to use different dyes for dyeing depending on the type of functional group, and all materials cannot be dyed and dyed with the same dye. For example, nylon can be dyed with a cation, anion, or reactive dye, and the functional group that serves as a starting point to which the dye molecule binds at this time is an amino group or carboxyl group at the polymerization end, and its number is extremely small, and sufficient dyeability It cannot be said that it is equipped.
[0015]
In addition, other synthetic polymer materials such as polyethylene terephthalate, polypropylene, and aramid have few functional groups, and hardly exhibit dyeability with respect to cation, anion, and reactive dyes. The only dyeing method is dyeing by kneading the dye or by sublimating the disperse dye under high temperature and high pressure and diffusing the dye molecules into the amorphous part above the glass transition temperature of the material. For this reason, materials made by blending natural and synthetic fibers or different types of synthetic fibers could not be dyed with the same dye. For this reason, dyeing of cotton and polyester blends is done with a mixed dye of reactive dyes and disperse dyes, and it has been devised, but the dyeing conditions are different and the dyeing rate is not sufficient.
[0016]
In addition, natural cellulosic fibers such as cotton have many -OH groups, which are polar groups, so the functional groups that bind reactive dye molecules are sufficient, but the reactivity at low temperatures is low, and in the presence of strong alkali for dyeing. However, there is a problem that sufficient dyeing cannot be performed unless the reactivity is increased by high-temperature steam. In order to solve these problems, techniques such as dyeing the surface resin by applying an acrylic resin to the fabric surface, or dispersing and printing a pigment with a latex resin have been devised. It was not a satisfactory dyeing method because it interfered with the texture.
[0017]
[Problems to be solved by the invention]
Introducing a reactive or polar functional group in a state in which the modification for imparting the functionality of the polymer material is sufficiently high molecular weight and the mechanical properties are maintained, or the form at the time of use is maintained, It is the subject of the present invention.
[0018]
Further, it is an object of the present invention to provide a polymer material having a long lasting effect and a method for producing the same, by introducing a larger amount of functional groups to be introduced not only on the surface but also on the inside and on the back as compared with the prior art. is there.
[0019]
  Another object of the present invention is to introduce a functional group that serves as a starting point for bonding with a dye molecule of a polymer material, thereby improving dyeability.WhenA dyeing method in which both materials blended or mixed materials such as blended materials are dyed with the same dye, and even if it is a fabric, it is dyed while maintaining its texture, and the dyeing conditions are mild. Is to provide.
[0020]
As a result of intensive studies to solve the above problems, in the present invention, various reactive or polar functional groups are obtained by reacting active reactive species in the gas phase of a specific compound to modify the surface or the interior of the polymer material. In addition, the property of the polymer material is changed by the compound that reacts with the introduced functional group, and the reactive functional group for positively binding the dye molecule to the dyed polymer material is positively introduced. The inventors have found that the use of materials is effective.
[0021]
[Means and Actions for Solving the Problems]
  The above-described problems of the present invention are solved by the following configuration.
1.A material made of natural or synthetic polymersThis is a modification method for introducing a functional group into a polymer material, and the polymer material is treated under irradiation of active energy rays in the gas phase of the first compound that generates reactive active species by being excited by active energy rays. In a method for modifying a polymer material,The polymer material has a saturated or unsaturated hydrocarbon structure and can utilize a C—H activation reaction,A method for modifying a polymer material, wherein the first compound is oxalyl dichloride.
[0022]
2. A method for modifying a polymer material comprising the step of reacting a modified polymer material obtained in 1 with a second compound having a reactive or polar functional group to change the functional group.
[0023]
3.SaidReactive or polar functional groups are -COCl, -COOH, -OH, -SH, -NH₂, R₁NH(R ₁ Is -CH ₂ CH ₂ Represents OH. )At the end2 aboveA method for modifying a polymer material as described.
[0024]
4). 2. The method for modifying a polymer material as described in 1 above, wherein the active energy ray is ultraviolet light.
[0025]
5). The reaction for changing the functional group of 2 is carried out in an organic solvent.Or 32. A method for modifying a polymer material according to 1.
[0026]
6). The step 2 for changing the functional group of 2 is performed in the gas phase of the second compound.Or 32. A method for modifying a polymer material according to 1.
[0027]
7). The second compound, wherein the second compound has two or more reactive or polar functional groups in the molecular structure.Or 32. A method for modifying a polymer material according to 1.
[0028]
8).A material made of natural or synthetic polymersA modified polymer material obtained by introducing a functional group into a polymer material, wherein the polymer material is activated energy in the gas phase of the first compound that generates reactive active species when excited by active energy rays. In polymer materials introduced with reactive or polar functional groups, obtained by treatment under irradiation with radiation,The polymer material has a saturated or unsaturated hydrocarbon structure, can utilize a C—H activation reaction, the active energy ray is ultraviolet light, andA modified polymer material, wherein the first compound is oxalyl dichloride.
[0029]
9. Said8A polymer material obtained by reacting a modified polymer material obtained by the above with a second compound having a reactive or polar functional group to change the functional group.
[0030]
10.SaidReactive or polar functional groups are -COCl, -COOH, -OH, -SH, -NH₂, R₁NH(R ₁ Is -CH ₂ CH ₂ Represents OH. )At the end9The modified polymer material described.
[0032]
11.The reaction for changing the functional group of 9 is performed in an organic solvent.Or 10Modified polymer material described in 1.
[0033]
12The reaction for changing the functional group of 9 is performed in the gas phase of the second compound.Or 10Modified polymer material described in 1.
[0034]
13.The second compound is characterized in that the second compound has two or more types of reactive or polar functional groups in the molecular structure.Or 10Modified polymer material described in 1.
[0035]
14 A material made of natural or synthetic polymersA method of dyeing a polymer material, wherein the polymer material is treated under active energy ray irradiation in the gas phase of a first compound that generates a reactive active species by exciting the polymer material with active energy rays in advance. In a dyeing method using a polymer material into which a reactive or polar functional group is obtained,The polymer material has a saturated or unsaturated hydrocarbon structure and can utilize a C—H activation reaction,The dyeing method, wherein the first compound is oxalyl dichloride.
[0036]
15.SaidReactive or polar functional groups are -COCl, -COOH, -OH, -SH, -NH₂, R₁NH(R ₁ Is -CH ₂ CH ₂ Represents OH. )15. The staining method as described in 14 above, wherein
[0037]
16.The active energy ray is ultraviolet light,14The dyeing | staining method as described.
[0038]
17.SaidFibers and films made from blends or blends of different polymer materialsAnd the dye used in the dyeing method using the C—H activation reaction of the saturated or unsaturated hydrocarbon structure of the polymer material is the same dyeThe dyeing | staining method in any one of said 14-16 characterized by these.
[0039]
18.A dye used in a dyeing method using a C—H activation reaction of a saturated or unsaturated hydrocarbon structure of the polymer materialReactive dyeAnd thisNeutral dyeing | staining is carried out, The dyeing | staining method in any one of said 14-16 characterized by the above-mentioned.
[0040]
19.A dyeing method using a C—H activation reaction of a saturated or unsaturated hydrocarbon structure possessed by the polymer material,At low temperature below 50 ℃DoneThe dyeing method according to any one of 14 to 16, wherein:
[0041]
20.A dyeing method using a C—H activation reaction of a saturated or unsaturated hydrocarbon structure possessed by the polymer material,In the gas phaseIt is dyeing inThe dyeing | staining method in any one of Claims 14-16 characterized by the above-mentioned.
[0045]
BEST MODE FOR CARRYING OUT THE INVENTION
Means for solving the above problems will be specifically described below.
As a result of intensive studies to solve the above-mentioned problems related to the modification of polymer materials, the present inventors have found that many of the polymer materials have a saturated or unsaturated hydrocarbon structure. We found that the problem can be solved by using.
And by functionalizing fiber molecules by photo-CH activation and performing a photochemical reaction in the gas phase in order to modify its properties, the shape of polymer materials, such as spinning, woven fabrics, films, etc. It was possible to process even in a state of maintaining.
[0046]
Hereinafter, in the embodiment of the present invention, an example using a chlorocarbonylation reaction of C—H by a photochemical reaction of oxalyl dichloride will be described. This reaction is a reaction that occurs through a reactive active species (radical species) generated photochemically, and stoichiometrically as shown in (Formula 2).
[0047]
[Chemical formula 2]

[0048]
This reaction is effective for chlorocarbonylation reaction of various hydrocarbon groups. For example, in the case of a compound having a basic structure of polyethylene terephthalate, a product in which each site of the methylene chain is chlorocarbonylated is obtained.
[0049]
[Chemical 3]

[0050]
In general, light used for C—H activation can be any active energy ray that excites a compound to generate a reactive species (radical species). For example, electron beams such as γ rays, β rays, and X rays, and active energy rays such as radiation and ultraviolet rays can be used. Among these, use of ultraviolet light composed of ultraviolet rays is preferable from the standpoint of safety and miniaturization without being restricted by the place of use.
The first compound that generates the reactive active species may be any compound that generates the reactive active species by being excited by the above-described active energy rays, but various compounds other than those shown in the examples are used. It goes without saying that the present invention is effective in addition to the exemplified compounds, and the scope of the invention is not limited to the examples.
Examples of the first compound include nitrosilkyl chloride.
[0051]
  In order to change the characteristics by using the functional group after introduction, oxalyl dichloride is used as the first compound.Used. Oxalyl dichloride is a liquid at room temperature and has an appropriate vapor pressure (about 100 mmHg), so that it can be processed in the gas phase by introducing it into the reaction processing vessel without any processing operation such as heating. The gas phase may be an atmosphere in which only the compound is vaporized or an atmosphere in which another gas is added thereto.
[0052]
For example, a gas such as ozone can be used, but an ozone generator is required and the amount of introduction is difficult to control, and those exemplified below are preferable.
Further, as other gas in the gas phase reaction, air can be used, but in order to process stably, an inert gas such as nitrogen, helium, argon or the like is preferable in order to control humidity and oxygen content. . Moreover, dry nitrogen is preferable from the ease of handling.
The gas pressure during the treatment is not particularly problematic, but a sufficient effect can be obtained by the normal pressure treatment. In view of simplicity of the apparatus, atmospheric pressure treatment is preferable.
[0053]
As the polymer material to be modified, a woven or knitted fabric made of vegetable fiber, animal fiber, artificial fiber, or the like can be used as the state of the fabric. Plant fibers are cotton, hemp fabric, animal fibers are silk, wool fabric, artificial fibers are classified as regenerated artificial fibers, viscose rayon, polynosic rayon, copper ammonium rayon, protein Examples thereof include fabrics such as series.
Moreover, the cloth which consists of a fiber which consists of polyamide, a polyimide, a polyurethane, a polyvinyl alcohol, polyacryl, polyester, a polypropylene, a vinyl chloride, vinylidene chloride etc. which are classified into a synthetic fiber in an artificial fiber is mentioned. Any of these fabrics can be used in the form of fibers, woven fabrics and knitted fabrics. The fiber yarns constituting them may be in the form of filaments or staples.
These fibers can be used singly or in combination of two or more kinds of blends, woven fabrics, and knitted fabrics. That is, it can be used in any case as long as it has a C—H bond in the molecular structure of the polymer material constituting these fibers.
[0054]
The polymer material can be applied not only to fibers but also to film or plate-like materials. Examples of the material for forming these include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polyimide, polyamide, vinyl chloride, and vinylidene chloride. It can also be used for composite materials such as blends and bonding of these polymer materials. Examples of these composite materials include films and plates cast by mixing the respective materials, those having different materials for the front and back surfaces to which these films and plates are bonded, or films obtained by applying a polyurethane resin or the like to the PET surface.
[0055]
Further, the present invention is characterized in that the range of compounds that can be used for the polymer material can be expanded by changing the surface functional group of the modified polymer material. That is, it is possible to change the functional group on the surface by using a compound that forms a covalent bond by reaction with the first introduced functional group.
For example, the acid chloride residue represented by Formula 2 can be further reacted with amines, alcohols, thiol compounds or water to change the residue. At that time, when the reaction is carried out in the presence of a basic compound, the introduction rate can be improved.
[0056]
Further, at this time, it is preferable to use a compound having two or more reactive or polar groups in the molecular structure because the functional group on the surface can be a desired residue. A plurality of functional groups or polar groups may be the same or different, but the same functional group is preferable in order to make the surface state the same functional group.
[0057]
Examples of the second compound for changing the functional group on the surface include amines such as ethylenediamine and triethylenediamine, glycols such as ethylene glycol, diethylene glycol and butanediol, and compounds having different functional groups such as diethanolamine and hydroxyethylamine. Can be mentioned. In the present invention, not only the exemplified compounds but also any functional group capable of reacting can be used.
[0058]
The reaction for changing the functional group is carried out in an organic solvent such as a petroleum hydrocarbon solvent such as benzene, toluene, xylene, hexane or heptane, or a halogenated hydrocarbon such as methylene chloride or chloroform tetrachloride. It can be treated by dissolving the compound and immersing it in the surface of a polymer material that has been modified and has an acid chloride residue. At this time, for dehydrochlorination, tertiary amines such as triethylamine and pyridine and alkaline reagents such as sodium hydroxide and sodium alkoxide may be allowed to coexist and then washed with water to remove by-products.
[0059]
Further, this reaction can be achieved even in a gas phase in which the second compound is introduced as a gas. Such a second compound can be used as long as it has a low boiling point and a relatively high vapor pressure, or can be easily converted into a gaseous state by heating, and does not require a treatment such as washing. Have
Among such second compounds, compounds that can be reacted in the gas phase in a gaseous state can be compounds such as ethylenediamine.
If it shows with a reaction schematic diagram, it can express like Formula 4.
[0060]
[Formula 4]

[0061]
Next, supplementary explanation will be given for a method for dyeing fibers, fabrics, films, plates and the like made of the modified polymer material according to the present invention.
The fabric in the present invention may be a woven fabric, a knitted fabric, or a non-woven fabric. As a fiber material used for the fabric, any synthetic fiber (polyester, polyamide, acrylic fiber, etc.), semi-synthetic fiber (acetate, rayon, etc.), natural fiber (cotton) , Silk, wool, etc.), and mixed materials (mixed products, knitted products, knitted fabric products), and all other fiber materials can be applied.
[0062]
The dye ink in the present invention needs to contain a dye that can be dyed on a fabric, and examples of the dye include acid dyes, direct dyes, reactive dyes, cationic dyes, and disperse dyes.
[0063]
In the conventional dyeing method, the dye constituting the dye solution must be changed according to the fiber material to be used. For example, when the fiber material constituting the fabric is polyester or acetate fiber, the dye solution is configured using a disperse dye.
When the material constituting the fabric is an anionic dye-dyeable material such as wool, silk, polyamide, cotton, or rayon, an anionic dye such as a direct dye, an acid dye, or a reactive dye is applied as the dye. In the case of cationic dyeable materials such as acrylic fibers and cationic dyeable polyester fibers, cationic dyes are used as the dyes.
[0064]
The dye used in the present invention does not need to be changed according to the material, and a dye having a covalent bond or an ionic bond with the introduced functional group can be used. Common dyes include the following.
Examples of the disperse dye include azo series, anthraquinone series, nitrodiphenylamine series, naphthalimide series, naphthoquinoneimide series, and methine series. Specifically, dyes described in pages 725 to 816 of the new edition dye manual (publishing office; Maruzen Co., Ltd.) can be mentioned.
Examples of the direct dye include azo series, stilbene series, thiazole series, dioxazine series, and phthalocyanine series. Specifically, the dyes described in pages 317 to 396 of the same dye manual are listed.
Examples of the acid dye include azo series, anthraquinone series, triphenylmethane series, and xanthine series. Specific examples include the dyes described in pages 393 to 526 of the same handbook of dyes.
Examples of reactive dyes include azo dyes, anthraquinone dyes, and phthalocyanine dyes. Specific examples include the dyes described on pages 881-934 of the same dye manual.
Specific examples of the cationic dye include dyes described in pages 529 to 562 of the same Handbook of Dyes.
[0065]
In addition, in order to heat and color the dye provided to the fabric, steaming or dry heat treatment may be performed. The heat fixing condition varies depending on the type of dye used and the type of fabric, but in the case of steaming, it is treated at 100 to 130 ° C. for 10 to 30 minutes, and in the case of dry heat, it is treated at 180 to 210 ° C. for 1 to 5 minutes. Finally, soaping or reduction cleaning is performed to remove the undyed dye and the water-insoluble water-absorbent resin.
[0066]
【Example】
Specific effects including examples will be described below.
Example 1-1
A 110 μm thick polyethylene terephthalate (PET) film, previously dried under vacuum at 50 ° C. for 1 hour in a vacuum drier, is suspended in a container equipped with a 30 W low-pressure mercury lamp and oxalyl dichloride gas. And nitrogen gas were treated with light irradiation for 20 minutes such that the partial pressures were 100 mmHg and 660 mmHg, respectively. The PET film was taken out from the container and air-dried with dry air for 1 hour.
[0067]
Example 1-2
The same treatment as in Example 1-1 was performed except that the PET film was changed to a polypropylene fabric having a thickness of 200 μm.
[0068]
Example 1-3
The same treatment as in Example 1-1 was performed except that the PET film was changed to a fabric made of aramid fibers having a thickness of 120 μm.
[0069]
Comparative Example 1-1
It processed like Example 1-1 as nitrogen gas instead of oxalyl dichloride gas.
[0070]
Comparative Example 1-2
It processed on the same conditions as Example 1-1, without irradiating a low pressure mercury lamp.
[0071]
The characteristic absorption of carbonyl chloride was measured for the samples of Examples 1-1, 2, and 3 and Comparative Examples 1-1 and 2 by reflection FT-IR using the surface infrared spectrum. Furthermore, each sample was immersed in 100 ml of water at 50 ° C. for 30 minutes, and the characteristics of the residual liquid obtained by pulling up the sample were measured with a litmus paper. The results are shown in Table 1.
[0072]
[Table 1]

[0073]
In any of the examples, there was no change in shape before and after the treatment, and the texture such as touch was not changed.
From the above results, it can be seen that a carbonyl chloride group is introduced into the material, and because it has reactivity, it is hydrolyzed with water and the residual liquid becomes acidic.
Furthermore, examples that can be converted not only to the carbonyl chloride group but also to other functional groups are shown.
Example 1-4
The PET film treated in Example 1-1 was dipped in 100 ml of a benzene solution containing 1% ethylenediamine for 10 minutes at room temperature, and then benzene and ethylenediamine were distilled off under reduced pressure in a vacuum dryer.
[0074]
Example 1-5
The PET film treated in Example 1-1 was immersed in 100 ml of a benzene solution containing 1% ethylene glycol and an equal amount of triethylamine while stirring at room temperature for 10 minutes, washed with water, and dried in a vacuum dryer.
As a result of measuring the infrared spectral absorption spectrum of the samples of Examples 1-4 and 5 by reflection FT-IR, the characteristic absorption of carbonyl chloride disappeared and broad characteristic absorption identified as a hydroxyl group and an amino group was obtained. It was.
[0075]
Next, an example for confirming that these functional groups have changed will be shown.
Example 1-6
Samples of Examples 1-1 and 4 and untreated PET film as Comparative A were stained with methylene blue and orange 2. The results are shown in Table 2.
[0076]
[Table 2]

[0077]
From the above results, it can be seen that PET has been modified to introduce functional groups, and the introduced functional groups have been converted.
From the above results, it can be seen that the present invention can be modified by introducing functional groups into natural and synthetic polymer materials.
[0078]
Specific effects will be described below including examples of the staining method according to the present invention.
Example 2-1
A 180 μm thick polyethylene terephthalate (PET) fabric previously dried in a vacuum dryer at 50 ° C. for 1 hour in a 5 cm × 5 cm shape is suspended in a container equipped with a 30 W low-pressure mercury lamp, and oxalyl dichloride gas And nitrogen gas were treated with light irradiation for 20 minutes such that the partial pressures were 100 mmHg and 660 mmHg, respectively. The PET film was taken out from the container and air-dried with dry air for 1 hour.
[0079]
Example 2-2
The same treatment as in Example 2-1 was performed except that the PET fabric was changed to a 220 μm polypropylene fabric.
[0080]
Example 2-3
The same treatment as in Example 2-1 was performed except that the PET fabric was changed to a 200 μm aramid fabric.
[0081]
Example 2-4
The same treatment as in Example 2-1 was performed except that the PET fabric was changed to a 250 μm nylon fabric.
[0082]
Comparative Example 2-1
PET fabric not treated in Example 2-1
Comparative Example 2-2
Polypropylene fabric not treated in Example 2-1
Comparative Example 2-3
Aramid fabric not treated in Example 2-1
Comparative Example 2-4
Nylon fabric not treated in Example 2-1
[0083]
The fabrics of Examples 2-1, 2, 3, and 4 and Comparative Examples 2-1, 2, 3, and 4 were dyed with methylene blue, which is a cationic dye, in water at PH = 8. The results are shown in Table 3.
[0084]
[Table 3]

[0085]
As can be seen from the above examples, different materials can be dyed with the same dye, and materials that cannot be dyed conventionally can also be dyed by this dyeing method.
[0086]
Further, examples of the modification of the functional group according to the present invention will be described.
Example 2-5
The PET fabric treated in Example 2-1 was dipped in a benzene solution containing 1% ethylenediamine at room temperature for 10 minutes and then pulled up, and then benzene and ethylenediamine were distilled off as reduced pressure in a vacuum dryer.
[0087]
Example 2-6
The nylon fabric treated in Example 2-4 was treated in the same manner as in Example 2-5.
[0088]
Example 2-7
The aramid fabric treated in Example 2-3 was treated in the same manner as in Example 2-5.
[0089]
Comparative Example 2-5
PET fabric treated in Example 2-1.
[0090]
As a result of dyeing the treated fabrics of Examples 2-5, 6, 7 and Comparative Example 2-5 with orange 2, which is an anionic dye, in water at pH = 3.5, a significant improvement in dyeability was observed with nylon. Stained in color. Moreover, what was not dye | stained at all by PET was dye | stained favorably. Aramid also showed good dyeability. The results are shown in Table 4.
[0091]
[Table 4]

[0092]
The above results also show that different materials can be dyed with the same dye. Further, as can be seen from Examples 2-1 and 5 and Comparative Example 2-5, the dyeability by methylene blue and orange 2 changes due to the difference in the treatment, which means that the functional group is converted by the treatment. Suggests that.
[0093]
Further, an example of dyeing with a reactive dye will be described.
Example 2-8
The polyester fabric of Example 2-5 was dyed with Prition Red MX-5B, which is a reactive dye, in neutral water.
[0094]
Comparative Example 2-6
The polyester fabric used for the treatment of Example 2-1 was dyed in the same manner as in Example 2-8 without any treatment. The results are shown in Table 5.
[0095]
[Table 5]

[0096]
From this result, it can be seen that the polyester fabric that is not dyed at all by the reactive dye is dyed by the dyeing method of the present invention. The dyeing conditions are also neutral, and it can be seen that dyeing is performed by low-temperature dyeing at about room temperature without using a strong alkali. The fabric dyed in Example 2-8 was boiled for about 1 hour in a household detergent (trade name monogen) aqueous solution, but it was confirmed that the fabric was strongly dyed without change in decolorization or the like.
[0097]
【The invention's effect】
According to the modification method and the modified polymer material of the present invention, a reactive or polar functional group can be introduced into the polymer material while maintaining the mechanical strength of the material and the form during use. And by introducing this group, the characteristics of the polymer material can be modified.
[0098]
Further, according to the dyeing method of the present invention, different materials can be dyed with the same dye, which is an excellent dyeing method that maintains the texture of the fabric. Also, in the dyeing of reactive dyes, strong alkali is not particularly required, and strong dyeing can be performed under mild conditions. The effects of the present invention were also obtained for the mixed spinning system.

Claims (20)

This is a modification method that introduces a functional group into a polymer material that is a material made of natural or synthetic polymer, and it is highly modified in the gas phase of the first compound that generates reactive active species when excited by active energy rays. In the modification method of the polymer material in which the molecular material is treated under irradiation with active energy rays, the polymer material has a saturated or unsaturated hydrocarbon structure and can utilize a C—H activation reaction. A method for modifying a polymer material, wherein the first compound is oxalyl dichloride. A method for modifying a polymeric material comprising the step of reacting a modified or polymeric material obtained according to claim 1 with a second compound having a reactive or polar functional group to change the functional group. . The reactive or polar functional group has —COCl, —COOH, —OH, —SH, —NH ₂ , R ₁ NH (R ₁ represents —CH ₂ CH ₂ OH) at the terminal . The method for modifying a polymer material according to claim 2 . The method for modifying a polymer material according to claim 1, wherein the active energy ray is ultraviolet light. The method for modifying a polymer material according to claim 2 or 3, wherein the reaction for changing the functional group according to claim 2 is carried out in an organic solvent. The method for modifying a polymer material according to claim 2 or 3, wherein the step of changing the functional group according to claim 2 is performed in a gas phase of the second compound. 4. The method for modifying a polymer material according to claim 2, wherein the second compound has two or more types of reactive or polar functional groups in the molecular structure. A modified polymer material obtained by introducing a functional group into a polymer material that is a material made of natural or synthetic polymer, and is a first compound that generates reactive active species when excited by active energy rays. In a polymer material into which a reactive or polar functional group is introduced, obtained by treating a polymer material in the gas phase under irradiation with active energy rays, the polymer material has a saturated or unsaturated hydrocarbon structure. A modified polymer material which can utilize a C—H activation reaction, wherein the active energy ray is ultraviolet light, and the first compound is oxalyl dichloride. A polymer material obtained by reacting a modified polymer material obtained according to claim 8 with a second compound having a reactive or polar functional group to change the functional group. The reactive or polar functional group has —COCl, —COOH, —OH, —SH, —NH ₂ , R ₁ NH (R ₁ represents —CH ₂ CH ₂ OH) at the terminal . The modified polymer material according to claim 9 . The modified polymer material according to claim 9 or 10, wherein the reaction for changing the functional group according to claim 9 is performed in an organic solvent. The modified polymer material according to claim 9 or 10, wherein the reaction for changing a functional group according to claim 9 is performed in a gas phase of the second compound. The modified polymer material according to claim 9 or 10, wherein the second compound has two or more types of reactive or polar functional groups in the molecular structure. A method for dyeing a polymer material, which is a material made of a natural or synthetic polymer, which is highly excited in the gas phase of a first compound that generates a reactive active species by exciting the polymer material with active energy rays in advance. In a dyeing method using a polymer material introduced with a reactive or polar functional group obtained by treating a molecular material under irradiation of active energy rays, the polymer material has a saturated or unsaturated hydrocarbon structure. A staining method characterized in that a C—H activation reaction can be used, and the first compound is oxalyl dichloride. The reactive or polar functional group is —COCl, —COOH, —OH, —SH, —NH ₂ , R ₁ NH (R ₁ represents —CH ₂ CH ₂ OH). 14. The staining method according to 14. The dyeing method according to claim 14, wherein the active energy ray is ultraviolet light. A dye used in a dyeing method using a C—H activation reaction of a saturated or unsaturated hydrocarbon structure of the polymer material, wherein the polymer material is a fiber or film by blending or blending of different materials , and the polymer material has The dyeing method according to any one of claims 14 to 16, wherein the dyes are the same . The dye used in the dyeing method using the C—H activation reaction of a saturated or unsaturated hydrocarbon structure of the polymer material is a reactive dye , and thereby neutral dyeing. The dyeing | staining method in any one of 14-16. The dyeing method using a C—H activation reaction of a saturated or unsaturated hydrocarbon structure of the polymer material is performed at a low temperature of 50 ° C. or lower. The dyeing | staining method as described. Dyeing method using C-H activation reaction of hydrocarbon structures of a saturated or unsaturated wherein the polymeric material has found to claim 14 to 16, characterized in that the staining in the gas phase The dyeing | staining method as described.