JP3603645B2 - Polyphenyleneethynylene having dendron side chain, resin composition containing the same, luminescent paint, and luminescent sheet-like molded product - Google Patents
Polyphenyleneethynylene having dendron side chain, resin composition containing the same, luminescent paint, and luminescent sheet-like molded product Download PDFInfo
- Publication number
- JP3603645B2 JP3603645B2 JP04424799A JP4424799A JP3603645B2 JP 3603645 B2 JP3603645 B2 JP 3603645B2 JP 04424799 A JP04424799 A JP 04424799A JP 4424799 A JP4424799 A JP 4424799A JP 3603645 B2 JP3603645 B2 JP 3603645B2
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- JP
- Japan
- Prior art keywords
- dendron
- polyphenyleneethynylene
- luminescent
- side chain
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 Polyphenyleneethynylene Polymers 0.000 title claims description 61
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- Compositions Of Macromolecular Compounds (AREA)
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Description
【０００１】
【発明の属する技術分野】
本発明は、デンドロン側鎖を有するポリフェニレンエチニレン、並びにこれを含有する樹脂組成物、発光性塗料、及び発光性シート状成形体に関する。詳しくは、高い発光能、優れた溶剤溶解性、及び優れた塗膜形成性を有するため、溶液塗布可能な発光材料として非常に有用な新規材料に関するものである。
【０００２】
【従来の技術】
ポリフェニレンエチニレンは、その長いπ電子共役系のため、光の吸収と発光、導電性等の性質を有するため、発光体やナノエレクトロニクスにおける配線手段等としての応用が考えられるだけでなく、その剛直な化学構造から液晶性等の特異な物理的性質が期待される材料である。例えば、Ｄｅｖａｄｏｓｓ，Ｃ．ら；Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．、１１８巻、９６３５頁（１９９６）、あるいは池田剛ら；Ｐｏｌｙｍ．Ｐｒｅｐｒ．，Ｊａｐａｎ、４７巻３号、４０３頁（１９９８）には、この構造の光物性の利用についての記述がある。
【０００３】
一方、π電子共役系の側鎖として立体的に込み合ったデンドロン（樹枝状規則分岐を有するデンドリマー構造を持つ分子構築部品という意味で用いられる術語；例えば、Ｇ．Ｒ．Ｎｅｗｋｏｍｅら著の成書；Ｄｅｎｄｒｉｔｉｃ Ｍｏｌｅｃｕｌｅｓ，Ｃｏｎｃｅｐｔｓ・Ｓｙｎｔｈｅｓｉｓ・Ｐｅｒｓｐｅｃｔｉｖｅｓ（ＶＣＨ Ｖｅｒｌａｇｓｇｅｓｅｌｌｓｃｈａｆｔ ｍｂＨ；Ｗｅｉｎｈｅｉｍ，Ｇｅｒｍａｎｙ；１９９６、ＩＳＢＮ：３−５２７−２９３２５−６）を参照）を導入することで、「分子配線（Ｍｏｌｅｃｕｌａｒ ｗｉｒｅ）」を被覆する試みが、Ｓｃｈｅｎｎｉｎｇ，Ａ．Ｐ．Ｈ．Ｊ．ら；Ｃｈｅｍ．Ｃｏｍｍｕｎ．、１０１３頁（１９９８）に報告されている。しかし、ここで報告されている物質のπ電子共役系はポリエチニレン構造であり、繰り返し単位の数は高々５と小さく、塗膜性に優れた材料とは言えなかった。また、使用した芳香族デンドロンによる発光の増強効果は知られていなかった。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、高い発光能、優れた溶剤溶解性、及び優れた塗膜形成性を有し、溶液塗布可能な発光材料を提供し、これを利用した塗料と発光性シート状成形体を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは上記の目的を達成すべく鋭意検討を重ねた結果、デンドロン側鎖とポリフェニレンエチニレンとから構成される新規材料が、デンドロン側鎖の発光能増強機能とポリフェニレンエチニレンの優れた溶剤溶解性と塗膜性を兼備し、発光材料として極めて有益に利用できることに知見し、特にデンドロンを結合したビスエチニル化合物の合成とその重縮合反応をについて系統的な検討を行った結果、本発明を完成するに至った。
【０００６】
即ち、本発明の要旨は、下記の９項目に存する。
１．ポリフェニレンエチニレンに、芳香環を含む繰り返し単位を有するデンドロンがそのフォーカルポイントで結合されてなることを特徴とするデンドロン側鎖を有するポリフェニレンエチニレン。
２．化学構造が下記一般式（１）（式（１）中、Ｌは互いに異なっていても良いデンドロンを表す）で表されるものであるデンドロン側鎖を有するポリフェニレンエチニレン。
【０００７】
【化３】
３．前記デンドロンがポリベンジルエーテル構造を有するものであるデンドロン側鎖を有するポリフェニレンエチニレン。
４．前記ポリベンジルエーテル構造が、下記一般式（２）で表される３，５−ジオキシベンジル基を繰り返し単位とするものであるデンドロン側鎖を有するポリフェニレンエチニレン。
【０００９】
【化４】
５．上記１〜４のいずれかに記載のデンドロン側鎖を有するポリフェニレンエチニレンと非晶性樹脂とを含有することを特徴とする樹脂組成物。
６．上記５に記載の非晶性樹脂が、スチレン系樹脂、アクリル系樹脂、及び芳香族ポリカーボネート樹脂のいずれかである樹脂組成物。
７．上記１〜４のいずれかに記載のデンドロン側鎖を有するポリフェニレンエチニレンを含有することを特徴とする発光性塗料。
８．上記５または６に記載の樹脂組成物を含有することを特徴とする発光性塗料。
９．上記７または８に記載の発光性塗料を塗布乾燥して得られることを特徴とする発光性シート状成形体。
【００１１】
【発明の実施の形態】
以下、本発明につきさらに詳細に説明する。
＜デンドロン＞
本発明におけるデンドロン（Ｄｅｎｄｒｏｎ）とは、近年非常に盛んになってきているデンドリマー（Ｄｅｎｄｒｉｍｅｒ：樹枝状規則分岐を有する高分子構造の総称）の研究において、かかる構造単位を持つ分子構築部品という意味で広く用いられる術語であり、例えば、前掲のＮｅｗｋｏｍｅら著の成書等にて用いられている。そして、該分岐構造の開始点（デンドロンを模式的に扇型と見なした場合の扇の要に相当）をフォーカルポイントと称し、分岐の次数を「世代（Ｇｅｎｅｒａｔｉｏｎ）」と称する（図１を参照）。本発明におけるデンドロンの分岐点における分岐の本数には制限はないが、通常２本（図１の場合）又は３本であり、好ましくは２本である。なお、本発明においては、分岐点が１つの構造（即ち第１世代）もデンドロンと見なす。
【００１２】
本発明に用いられるデンドロンは、その化学構造の繰り返し単位に芳香環を有する必要がある。これは、該デンドロンが紫外光あるいは可視光を吸収することにより本発明のポリフェニレンエチニレンをより強く発光させるためである。ここで芳香環とは、例えば、ベンゼン環、ナフタレン環、アントラセン環等の炭化水素芳香環、ピリジン環、キノリン環等の含窒素芳香環等を意味する。本発明に好適なデンドロンの構造例として、具体的には、ポリベンジルエーテル等の芳香族ポリエーテル、ポリヒドロキシ安息香酸等の芳香族ポリエステル、芳香族又は半芳香族ポリアミド、芳香族ポリカーボネート、芳香族ポリエステルカーボネート、ポリフェニレンスルフィド等の芳香族ポリスルフィド、芳香族ポリイミド、芳香族ポリアミドイミド等の炭素以外の元素を高分子主鎖に含む芳香族系高分子構造、ポリフェニレン、ポリフェニレンエチニレン、ポリフェニレンエチレン等の炭素−炭素結合で主鎖が構成されている芳香族系共役高分子構造等が挙げられ、このうちポリベンジルエーテル等の芳香族ポリエーテル、ポリヒドロキシ安息香酸等の芳香族ポリエステル等が好ましく、中でもポリベンジルエーテル等の芳香族ポリエーテルがより好ましく、下記一般式（２）で表される３，５−ジオキシベンジル基を繰り返し単位とする構造（Ｃ．Ｊ．Ｈａｗｋｅｒら；Ｊ．Ｃｈｅｍ．Ｓｏｃ．，Ｃｈｅｍ．Ｃｏｍｍｕｎ．、１０１０−１０１３頁（１９９０）を参照）が最適である。なお、これらの複数種の構造が１つのデンドロン残基中に共存していても差し支えなく、また、複数種のデンドロン残基が１つのポリフェニレンエチニレン鎖に結合していても差し支えない。
【００１３】
【化５】
本発明に用いられるデンドロンの世代に特に制限はないが、通常１〜６、合成の容易性から好ましくは１〜４、発光効果の点でより好ましくは２〜４、最も好ましくは３または４とする。
本発明に用いられるデンドロンは、そのフォーカルポイントにおいてポリフェニレンエチニレンに結合する必要がある。その結合様式には特に制限はないが、具体的な結合構造として、例えばエーテル結合、エステル結合、アミド結合、炭素−炭素結合、炭素−窒素結合等が挙げられる。
ポリフェニレンエチニレン主鎖へ結合するデンドロンの数に特に制限はなく、所望の発光挙動により変動するが、該主鎖の１つの繰り返し単位中のデンドロン数とフェニレン環数の比は、通常２：１〜１：１０、発光効率と溶剤溶解性の点で好ましくは２：１〜１：８、更に好ましくは２：１〜１：６、最も好ましくは２：１〜１：４とする。
【００１５】
＜ポリフェニレンエチニレン＞
本発明におけるポリフェニレンエチニレンとは、具体的には、下記一般式（３）〜（５）で表されるフェニレンエチニレン単位のいずれかから構成され、これらを任意の共重合比で含む重合体である。但し、一般式（３）〜（５）においてＲ１ 、Ｒ２ 、Ｒ３ 、及びＲ４ は、それぞれ独立に、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、イソブチル基、ヘキシル基、オクチル基、デシル基等の炭素数１０以下の炭化水素基、メトキシ基、エトキシ基、ｎ−プロピルオキシ基、イソプロピルオキシ基、ｎ−ブチルオキシ基、ｓｅｃ−ブチルオキシ基、イソブチルオキシ基、ヘキシルオキシ基等の炭素数６以下のアルコキシ基、及び前記のデンドロンからなる群から任意に選ばれる構造を意味する。
【００１６】
【化６】
【化７】
【化８】
特に好適なポリフェニレンエチニレンの構造として、下記一般式（１）の一般式（式（１）中、Ｌは互いに異なっていても良い前記のデンドロンを表す）で表されるものが挙げられる。
【００２０】
【化９】
本発明のポリフェニレンエチニレンにおいて、上記一般式（３）〜（５）のいずれかの一般式で表されるフェニレンエチニレン単位の繰り返し数（重合度）には特に制限はないが、重量平均重合度として、通常５〜１０００、塗膜性と溶剤溶解性の観点から好ましくは１０〜７００、更に好ましくは１５〜５００、最も好ましくは２０〜４００とする。この時の分子量分布にも特に制限はないが、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定される重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比Ｍｗ／Ｍｎとして、通常２．０〜２０、塗膜性と溶剤溶解性の観点から好ましくは２．２〜１５、更に好ましくは２．３〜１３、最も好ましくは２．３〜１０とする。
【００２２】
＜樹脂組成物＞
本発明は、前記のデンドロンを側鎖として結合したポリフェニレンエチニレンと非晶性樹脂とからなる樹脂組成物を提供する。ここで言う非晶性樹脂とは、樹脂成形産業において汎用的に行われている溶融成形手段により可視領域で透明な非晶性成形体を与える重合体であり、例えば、ポリスチレン、スチレン／α−メチルスチレン共重合体、スチレン／無水マレイン酸共重合体、スチレン／メチルメタクリレート共重合体、スチレングリシジルメタクリレート共重合体等のスチレン系樹脂、ポリメチルメタクリレート、ポリメチルアクリレート、ポリエチルメタクリレート、ポリエチルアクリレート、ポリｔｅｒｔ−ブチルメタクリレート、ポリフェニルメタクリレート、ポリベンジルメタクリレート、ポリアダマンチルアクリレート、ポリメタクリル酸、ポリアクリル酸、ポリアクリルアミド、メチルメタクリレート／メタクリル酸共重合体等のアクリル系樹脂、２，２−ビス（４−ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）を原料とするポリカーボネート、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン（通称ビスフェノールＣ）を原料とするポリカーボネート、２，２−ビス（４−ヒドロキシフェニル）フェニルエタン（通称ビスフェノールＰ）を原料とするポリカーボネート等の芳香族ポリカーボネート樹脂、水素添加ポリスチレン、ポリ（３−メチルブテン−１）等の非晶性ポリオレフィン等が例示でき、これらのうち光線透過率や成形温度の点で好適なのは、ポリスチレン、スチレン／α−メチルスチレン共重合体、スチレン／無水マレイン酸共重合体、スチレングリシジルメタクリレート共重合体等のスチレン系樹脂、ポリメチルメタクリレート、ポリメチルアクリレート、ポリエチルメタクリレート、ポリエチルアクリレート、ポリアダマンチルアクリレート、ポリメタクリル酸、メチルメタクリレート／メタクリル酸共重合体等のアクリル系樹脂、及びビスフェノールＡポリカーボネート、ビスフェノールＣポリカーボネート、ビスフェノールＰポリカーボネート等の芳香族ポリカーボネート樹脂であり、中でもポリスチレン等のスチレン系樹脂、ポリメチルメタクリレート、ポリメチルアクリレート、メチルメタクリレート／メタクリル酸共重合体等のアクリル系樹脂、及びビスフェノールＡポリカーボネート、ビスフェノールＰポリカーボネート等の芳香族ポリカーボネート樹脂が更に好適である。
【００２３】
かかる樹脂組成物を製造する方法には特に制限はなく、例えば、テトラヒドロフラン（ＴＨＦ）、トルエン、塩化メチレン、クロロホルム等の溶剤中での溶液混合、あるいは単軸押出機、二軸押出機、ブラベンダー、ロールミキサー等による溶融混合等の汎用的手段が可能である。
本発明の樹脂組成物において、本発明のデンドロン側鎖を有するポリフェニレンエチニレンの重量百分率は、通常、０．１％〜９５％、樹脂組成物の発光能から好ましくは１％〜９５％、より好ましくは３％〜９５％、樹脂組成物の機械的強度の観点から更に好ましくは３％〜８０％、最も好ましくは５％〜７０％とする。なお、かかる樹脂組成物には、その効果を著しく損なわない限りにおいてガラス繊維、ガラスフレーク、ガラスビーズ、マイカ、タルク、モンモリロナイト、スメクタイト、合成マイカ、合成スメクタイト等の無機フィラー、ポリエチレン、ポリプロピレン、ポリエステル、ポリアミド等の熱可塑性樹脂、スチレン系熱可塑性エラストマーやアクリルゴム等のゴム成分、樹脂ビーズ、中空ビーズ、熱安定剤、酸化防止剤、紫外線吸収剤、難燃剤、ワセリンやグリセリンエステル等の可塑剤や滑剤、金属粉、半導体粉、黒鉛、樹脂粉、色素、染料、蛍光染料、顔料、相溶化剤等、任意の添加剤を加えても構わない。
【００２４】
＜発光性塗料と発光性シート状成形体＞
本発明は、本発明のデンドロン側鎖を有するポリフェニレンエチニレン、または本発明の上記樹脂組成物を含有する発光性塗料と、これを塗布乾燥して得られる発光性シート状成形体を提供する。かかる塗料は、本発明のポリフェニレンエチニレン、または本発明の樹脂組成物を適当な溶剤に溶解して得られる。使用される溶剤には、必要な溶解性を有する限りにおいて特に制限はないが、例えば、テトラヒドロフラン（ＴＨＦ）、トルエン、塩化メチレン、クロロホルム等が挙げられ、本発明の効果を著しく損なわない範囲で、前記の任意の添加剤を加えても構わない。
【００２５】
本発明の発光性塗料において、使用される溶剤１００重量部に対する本発明のポリフェニレンエチニレンの使用量は、通常、０．１〜８０重量部、発光能の観点から好ましくは１〜８０重量部、より好ましくは５〜８０重量部、溶液の取り扱い性の観点から更に好ましくは５〜６０重量部、最も好ましくは５〜５０重量部とする。本発明の樹脂組成物を使用する場合には、使用される溶剤１００重量部に対する該組成物の使用量として、通常、１〜７０重量部、発光能の観点から好ましくは５〜７０重量部、より好ましくは７〜７０重量部、溶液の取り扱い性の観点から更に好ましくは７〜６０重量部、最も好ましくは１０〜５０重量部とする。
【００２６】
本発明の発光性塗料を塗布乾燥して得られる発光性シート状成形体は、粒子状、膜状、フィルム状、シート状、その他任意形状の立体的構造物として得ることができるが、特に膜あるいはフィルム状として成形された場合に実用的価値が高い。
かような成形体を得る方法に特に制限はないが、例えば、本発明の発光性塗料を基材上に塗布及び乾燥するような汎用的な方法（必要に応じ加熱・変形等任意の工程を付加する）により好適に製造できる。
【００２７】
用いられる基材には特に制限はないが、例えば、金属、金属酸化物、セラッミックス、化合物半導体などの無機物質、及び各種ポリマーや紙などの有機物質等が挙げられ、更に、水やアルコール類等の液体表面を使用して例えばＬＢ膜を得ることもできる。基材への塗布方法としては、スピンコーティング法、ディップコーティング法、ウェッティングフィルム法、スプレーコーティング法等の一般的な方法を用いることができる。
【００２８】
上述したような方法の他、本発明のポリフェニレンエチニレン、または本発明の樹脂組成物が熱可塑性を有する場合には、加熱押し出し製膜のような汎用的な方法も可能である。
このようにして得られる成形体の厚み、大きさ、形状、面の性質（例えば平面、球面、曲面、凹面、凸面、多孔質の面、平滑性、あるいは厚さの分布等の属性）には特に制限はないが、例えば厚みは、通常、１〜１００，０００ｎｍ、好ましくは１〜１０，０００ｎｍ、より好ましくは１〜１，０００ｎｍ程度である。
【００２９】
さらに、得られる成形体に、任意の添加剤、例えば酸化防止剤、熱安定剤、あるいは光安定剤等の各種安定剤、ガラス繊維、ガラスビーズ、マイカ、タルク、カオリン、粘土鉱物、炭素繊維、カーボンブラック、黒鉛、金属繊維、金属粉等の各種フィラー、帯電防止剤、離型剤、可塑剤、顔料や染料、ゴムやエラストマー類、熱可塑性樹脂等、必要に応じて任意の添加物を混合することも可能である。
【００３０】
＜発光方法とその原理＞
本発明のポリフェニレンエチニレン、樹脂組成物、発光性塗料、および発光性シート状成形体のいずれかを発光させる方法に制限はないが、例えば、デンドロン側鎖やポリフェニレンエチニレン主鎖の吸収する紫外光や可視光の照射により可能である。
【００３１】
ポリフェニレンエチニレン構造自体が発光することは公知であるが、本発明の完成に必要であった自然現象の１つとして、デンドロン側鎖の吸収する光の照射によりデンドロン自体は実質的に発光せずにポリフェニレンエチニレン主鎖が強く発光することが挙げられる。これは、Ｍ．Ｋａｗａら；Ｃｈｅｍ．Ｍａｔｅｒ．、１０巻、２８６−２９６頁（１９９８）において公知の芳香族デンドロンのランタノイド陽イオン発光の増感効果（アンテナ効果）が有機発光体においても起こるという新事実の発見に他ならない。本発明者らは、デンドロン側鎖の化学構造の制御により、該デンドロンからポリフェニレンエチニレン主鎖へのエネルギー移動がほぼ１００％の効率で起こることを既に実証しているので、従来のポリフェニレンエチニレンを発光させる技術では達成不可能な非常に強い発光がかかるデンドロンの化学構造の制御により初めて可能となったのであり、分子構造の最適化により更に発光特性が改良される可能性が指摘される。
【００３２】
【実施例】
以下に実施例により本発明の具体的態様を更に詳細に説明するが、本発明は、その要旨を越えない限り、これらの実施例によって限定されるものではない。
なお、実施例において使用した試薬や樹脂は、特に記載のないかぎりＡｌｄｒｉｃｈ社から供給されるものを使用した。
【００３３】
［測定装置と条件等］
（１） １Ｈ−ＮＭＲ
ＪＥＯＬ社製ＧＳＸ−２７０型ＦＴ−ＮＭＲ（２７０ＭＨｚ）、溶媒：ＣＤＣｌ３ 。室温測定。基準は、ＣＤＣｌ３ の７．２８ｐｐｍのシグナルとした。
（２）マススペクトル：Ｂｒｕｋｅｒ社製ＰｒｏｔｅｉｎＴｏｆ型ＭＡＬＤＩ−ＴＯＦ−ＭＳを使用した。マトリックス物質として、９−ニトロアントラセンを使用した。
（３）ＧＰＣ：東ソー社製ＨＬＣ−８０２０を使用し、溶媒はテトラヒドロフラン（ＴＨＦ）、Ｉｎｌｅｔ温度３５℃、オーブン温度４０℃、流速：１ｍＬ／ｍｉｎ １ｍＬ／分、圧力７６ｋｇｆ／ｃｍ２ 、検出４３２ｎｍの吸収で測定した。分子量は、分子量既知の複数種の単分散ポリスチレンによる検量線により決定した。
（４）吸収スペクトル：ＪＡＳＣＯ社製Ｖ５６０吸光光度計（１ｃｍ水晶セル使用）。室温測定。
（５）発光スペクトル：ＪＡＳＣＯ社製ＦＰ−７７７Ｗ蛍光光度計（１ｃｍ水晶セル使用）。室温測定。
【００３４】
１．デンドロンの合成
Ｊｉａｎｇ，Ｄ．−Ｌ．ら；Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．、１２０巻、１０８９５頁に記載の方法に準じ、３，５−ジメトキシベンジル基を有し、３，５−ジオキシベンジル構造の繰り返し単位を有し、フォーカルポイントにベンジルブロミド構造を有するデンドロンを得た（以下、このデンドロンを［Ｇ−ｎ］Ｂｒと略称する。ここでｎは自然数でデンドロンの世代数を表す。但し、該文献中の表示では［Ｇ−ｎ］はＬ（ｎ−１）に相当する。）。構造と純度は、 １Ｈ−ＮＭＲにおける３．７ｐｐｍのメトキシ基のシグナルとベンジル位プロトンとの積分値の比、およびマススペクトルで理論分子量に相当するシグナルを得たことから確認した。
【００３５】
２．デンドロンを結合したジエチニレンベンゼン［Ｇ−ｎ］２Ｅ２の合成
１，４−ジヒドロキシ−２，５−ジヨードベンゼン（図２中の化合物１：１．０当量）に、攪拌しながら塩化第一銅（０．０５当量）とジクロロビス（トリフェニルフォスフィン）パラジウム（ＩＩ）（０．０５当量）を室温で順次加え、容器内の真空引きと窒素置換を繰り返した。ここにトリメチルシリルアセチレン（３．０当量）とジイソプロピルアミン（３．０当量）を順次加え、６０℃で４時間反応させた後、トルエンで希釈し濾過して固体を除去した。これをシリカゲルカラムクロマトグラフィで精製して１，４−ジヒドロキシ−２，５−ビス（トリメチルシリルエチニル）ベンゼンを得た（図２中の化合物２）。次いで、これを過剰量の無水炭酸カリウムとともにメタノール中で室温にて１昼夜攪拌し、メタノール／塩化メチレンを流出溶剤とするシリカゲルカラムクロマトグラフィで精製して１，４−ジヒドロキシ−２，５−ジエチニルベンゼンを得た（図２中の化合物３）。これらの生成物の化学構造は、 １Ｈ−ＮＭＲにて確認した。更に、前記で合成したフォーカルポイントにベンジルブロミド構造を有するデンドロン［Ｇ−ｎ］Ｂｒ（２．１当量）と１，４−ジヒドロキシ−２，５−ジエチニルベンゼン（図２中の化合物３：１．０当量）、無水炭酸カリウム（５．０当量）を混合した容器内の真空引きと窒素置換を繰り返し、ここに乾燥したＮ，Ｎ−ジメチルフォルムアミド（ＤＭＦ）を加え６０℃で６．５時間攪拌した。反応液を大過剰の水に攪拌しながら注ぎ、生成した固体を濾別し、シリカゲルカラムクロマトグラフィで精製して目的とするデンドロンを結合したジエチニレンベンゼン［Ｇ−ｎ］２Ｅ２を得た（図２中の最終生成物）。このものの構造は、 １Ｈ−ＮＭＲにてデンドロン由来（メトキシ基、ベンジル位、及びベンゼン環）、エチニル基、及びエチニル基が結合するベンゼン環にそれぞれ帰属されるシグナルが明瞭に観測されたことと、それらの積分値比から確認した。
３．デンドロンを側鎖に結合したポリフェニレンエチニレンの合成と評価
【００３６】
実施例１
前記で合成した第３世代のデンドロンを結合したジエチニレンベンゼン［Ｇ−３］２Ｅ２（９６．８ｍｇ；１．０当量）、ｐ−ジヨードベンゼン（１５．２７ｍｇ；１．０当量）、テトラキス（トリフェニルフォスフィン）パラジウム（０）（２．６８ｍｇ；０．０５当量）を混合し、容器内の真空引きと窒素置換を繰り返した後、乾燥テトラヒドロフラン（ＴＨＦ）３ｍＬを溶媒として加え、更に、ヨウ化第一銅２．７５ミリモルを１０００ｍＬのジイソプロピルアミンに溶解したものをヨウ化第一銅として０．０５当量となるよう攪拌しながら加えた。これを５０℃で２６時間攪拌後、エチニルベンゼンを２滴加え更に１３時間反応を継続した。反応液は減圧下濃縮し、クロロホルム可溶分をメタノール中に投入する再沈殿法で精製した。この生成物はＧＰＣで数平均分子量（Ｍｎ）４３９００、重量平均分子量（Ｍｗ）２７７６００、ピークトップ分子量として１５００００（図３に示す予想構造に基づき約７０量体に相当）を与えた。この生成物はテトラヒドロフランに可溶であり、この溶液の吸収スペクトル測定で、２８０ｎｍ付近にデンドロン由来の吸収帯を、４３２ｎｍ付近にポリフェニレンエチニレン主鎖由来の吸収帯をそれぞれ観測した。そこで、デンドロン構造を励起すべく２８０ｎｍの紫外光を照射したところ、該デンドロン由来の発光帯（３１０ｎｍ付近）は観測されずポリフェニレンエチニレン主鎖由来の発光帯（４５４ｎｍ付近）のみが観測されたことから、デンドロン側鎖からポリフェニレンエチニレン主鎖へのエネルギー移動により発光していることが確認された。更に、吸収スペクトルと励起スペクトルの比較から、このエネルギー移動はほぼ１００％の効率で起こっていることが確認された。また、この溶液のスピンキャストにより良好なフィルムが得られ、２８０ｎｍの紫外光の照射により前記の溶液系と同じ発光帯を与えたことから、この物質のフィルムも優れた発光能を持つことが確認された。
【００３７】
実施例２
実施例１の［Ｇ−３］２Ｅ２の代わりに第２世代デンドロンを結合した相当化合物である［Ｇ−２］２Ｅ２を用いて同様の操作を行い、ＧＰＣによりポフェニレンエチニレンの生成を確認した。
実施例３
実施例１の［Ｇ−３］２Ｅ２の代わりに第４世代デンドロンを結合した相当化合物である［Ｇ−４］２Ｅ２を用いて同様の操作を行い、ＧＰＣによりポフェニレンエチニレンの生成を確認した。
４．デンドロンを側鎖に結合したポリフェニレンエチニレンと非晶性樹脂との組成物の製造と評価
【００３８】
実施例４
実施例１で合成した第３世代デンドロンを側鎖に結合したポリフェニレンエチニレンのテトラヒドロフラン溶液にポリスチレン（重量平均分子量は約３５０００）を加えた。該ポリフェニレンエチニレンとポリスチレンの配合比は１０：９０重量比とした。この溶液のスピンキャストにより良好なフィルムが得られ、２８０ｎｍの紫外光の照射により実施例１に記載の発光帯と同じ発光を与えたことから、このポリスチレン樹脂組成物フィルムも優れた発光能を持つことが確認された。
【００３９】
実施例５
実施例４において、第３世代デンドロンを側鎖に結合したポリフェニレンエチニレンとポリスチレンの配合比を８０：２０重量比とした以外、同様の操作を行ったところ良好なフィルムが得られ、２８０ｎｍの紫外光の照射により実施例１に記載の発光帯と同じ発光を与えたことから、このポリスチレン樹脂組成物フィルムも優れた発光能を持つことが確認された。
【００４０】
実施例６
実施例１で合成した第３世代デンドロンを側鎖に結合したポリフェニレンエチニレンのテトラヒドロフラン溶液にポリメチルメタクリレート（重量平均分子量は約１５０００）を加えた。該ポリフェニレンエチニレンとポリメチルメタクリレートの配合比は１０：９０重量比とした。この溶液のスピンキャストにより良好なフィルムが得られ、２８０ｎｍの紫外光の照射により実施例１に記載の発光帯と同じ発光を与えたことから、このポリメチルメタクリレート樹脂組成物フィルムも優れた発光能を持つことが確認された。
【００４１】
実施例７
実施例４において、第３世代デンドロンを側鎖に結合したポリフェニレンエチニレンとポリメチルメタクリレートの配合比を８０：２０重量比とした以外、同様の操作を行ったところ良好なフィルムが得られ、２８０ｎｍの紫外光の照射により実施例１に記載の発光帯と同じ発光を与えたことから、このポリメチルメタクリレート樹脂組成物フィルムも優れた発光能を持つことが確認された。
【００４２】
実施例８
実施例１で合成した第３世代デンドロンを側鎖に結合したポリフェニレンエチニレンのテトラヒドロフラン溶液にビスフェノールＡポリカーボネート（ＡＳＴＭ−Ｄ１２３８規格の３００℃／１．２ｋｇ荷重でのメルトインデックスが８−１０ｇ／１０分）を加えた。該ポリフェニレンエチニレンとビスフェノールＡポリカーボネートの配合比は１０：９０重量比とした。この溶液のスピンキャストにより良好なフィルムが得られ、２８０ｎｍの紫外光の照射により実施例１に記載の発光帯と同じ発光を与えたことから、このビスフェノールＡポリカーボネート樹脂組成物フィルムも優れた発光能を持つことが確認された。
【００４３】
実施例９
実施例４において、第３世代デンドロンを側鎖に結合したポリフェニレンエチニレンとビスフェノールＡポリカーボネートの配合比を８０：２０重量比とした以外、同様の操作を行ったところ良好なフィルムが得られ、２８０ｎｍの紫外光の照射により実施例１に記載の発光帯と同じ発光を与えたことから、このビスフェノールＡポリカーボネート樹脂組成物フィルムも優れた発光能を持つことが確認された。
【００４４】
【発明の効果】
本発明で新規に見出された繰り返し単位に芳香環を有するデンドロンを側鎖に有するポリフェニレンエチニレンは、優れた溶剤溶解性と塗膜形成性、並びに高い発光能を有するので、発光性塗料や該塗料をフィルム等に塗布した発光性シート状成形体として利用できる。また、スチレン系樹脂、アクリル系樹脂、あるいは芳香族ポリカーボネート樹脂等の非晶性樹脂への相溶性を有するため前記樹脂との組成物として使用でき、かかる樹脂組成物も前記同様の特徴と用途を有する。
【図面の簡単な説明】
【図１】デンドリマーの世代とフォーカルポイントを示す模式図である。
【図２】本発明のデンドロンを側鎖に有するポリフェニレンエチニレンの合成経路を示す説明図である。
【図３】実施例１で得られた生成物の化学構造を示す略図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyphenyleneethynylene having a dendron side chain, and a resin composition, a luminescent paint, and a luminescent sheet-like molded article containing the same. More specifically, the present invention relates to a novel material which has high light-emitting ability, excellent solvent solubility, and excellent film-forming property, and thus is very useful as a light-emitting material that can be applied in a solution.
[0002]
[Prior art]
Since polyphenyleneethynylene has properties such as light absorption, light emission, and conductivity due to its long π-electron conjugated system, it can be applied not only to light emitters and wiring means in nanoelectronics, but also to its rigidity. It is a material that is expected to have unique physical properties such as liquid crystallinity due to its unique chemical structure. For example, Devadoss, C.A. J. et al. Am. Chem. Soc. 118, 9635 (1996) or Tsuyoshi Ikeda et al .; Polym. Prepr. , Japan, Vol. 47, No. 3, p. 403 (1998) describes the use of optical properties of this structure.
[0003]
On the other hand, dendrons sterically crowded as side chains of a π-electron conjugated system (a term used in the meaning of a molecular building part having a dendrimer structure having dendritic regular branches; for example, a written book of GR Newkome et al .; See Dendritic Molecules, Concepts, Synthesis, Perspectives (VCH Verlagsgesellschaft mbH; Weinheim, Germany; 1996, ISBN: 3-527-29325-6). In Schening, A .; P. H. J. Chem. Commun. 1013 (1998). However, the π-electron conjugated system of the substance reported here has a polyethynylene structure, the number of repeating units is as small as 5 at most, and it cannot be said that the material has excellent coating properties. Further, the effect of enhancing the light emission by the aromatic dendron used was not known.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a light-emitting material having high light-emitting ability, excellent solvent solubility, and excellent film-forming property and capable of being applied in a solution, and to provide a paint and a light-emitting sheet-like molded product using the same. To provide.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, a novel material composed of a dendron side chain and polyphenyleneethynylene, a light emitting ability enhancement function of the dendron side chain and an excellent polyphenyleneethynylene The present inventors have found that they have both solvent solubility and coating properties and can be used extremely usefully as a luminescent material, and as a result of systematically studying the synthesis and polycondensation reaction of a bisethynyl compound bound with a dendron, the present invention Was completed.
[0006]
That is, the gist of the present invention resides in the following nine items.
1. A polyphenylene ethynylene having a dendron side chain, wherein a dendron having a repeating unit containing an aromatic ring is bonded to polyphenylene ethynylene at its focal point.
2. A polyphenyleneethynylene having a dendron side chain, whose chemical structure is represented by the following general formula (1) (in the formula (1), L represents a dendron which may be different from each other).
[0007]
Embedded image
3. A polyphenyleneethynylene having a dendron side chain, wherein the dendron has a polybenzyl ether structure.
4. A polyphenyleneethynylene having a dendron side chain, wherein the polybenzyl ether structure has a repeating unit of a 3,5-dioxybenzyl group represented by the following general formula (2).
[0009]
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5. A resin composition comprising the polyphenyleneethynylene having a dendron side chain according to any one of the above 1 to 4, and an amorphous resin.
6. A resin composition wherein the amorphous resin according to the above 5 is any one of a styrene resin, an acrylic resin, and an aromatic polycarbonate resin.
7. 5. A luminescent coating comprising the polyphenyleneethynylene having a dendron side chain according to any one of the above 1 to 4.
8. 7. A luminescent coating, comprising the resin composition according to 5 or 6 above.
9. A luminescent sheet-like molded product obtained by applying and drying the luminescent paint according to the above item 7 or 8.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
<Dendron>
The term “Dendron” in the present invention means a molecular building part having such a structural unit in the research on dendrimers (Dendrimer: a generic name of polymer structures having dendritic regular branches), which has become very popular in recent years. It is a term that is widely used, and is used, for example, in the books written by Newcome et al. Then, the starting point of the branch structure (corresponding to the key of a fan when the dendron is schematically considered to be a sector) is referred to as a focal point, and the order of the branch is referred to as a "generation" (see FIG. 1). reference). The number of branches at the branch point of the dendron in the present invention is not limited, but is usually two (in the case of FIG. 1) or three, and preferably two. In the present invention, a structure having one branch point (that is, the first generation) is also regarded as a dendron.
[0012]
The dendron used in the present invention needs to have an aromatic ring in the repeating unit of its chemical structure. This is because the dendron absorbs ultraviolet light or visible light to cause the polyphenyleneethynylene of the present invention to emit light more strongly. Here, the aromatic ring means, for example, a hydrocarbon aromatic ring such as a benzene ring, a naphthalene ring and an anthracene ring, and a nitrogen-containing aromatic ring such as a pyridine ring and a quinoline ring. Specific examples of the structure of the dendron suitable for the present invention include, specifically, aromatic polyethers such as polybenzyl ether, aromatic polyesters such as polyhydroxybenzoic acid, aromatic or semi-aromatic polyamides, aromatic polycarbonates, and aromatic polycarbonates. Polyester carbonate, aromatic polysulfide such as polyphenylene sulfide, aromatic polyimide including aromatic polyimide, aromatic polyamide imide and other elements other than carbon in the polymer main chain, aromatic polymer structure containing polyphenylene, polyphenylene ethynylene, carbon such as polyphenylene ethylene -An aromatic conjugated polymer structure in which the main chain is composed of carbon bonds, among which aromatic polyethers such as polybenzyl ether, aromatic polyesters such as polyhydroxybenzoic acid, and the like are preferable, and Aromatic polyethers such as benzyl ether Ter is more preferable, and a structure having a 3,5-dioxybenzyl group represented by the following general formula (2) as a repeating unit (CJ Hawker et al .; J. Chem. Soc., Chem. Commun., 1010) -1013 (1990)). It is to be noted that these plural kinds of structures may coexist in one dendron residue, and plural kinds of dendron residues may be bonded to one polyphenyleneethynylene chain.
[0013]
Embedded image
The generation of the dendron used in the present invention is not particularly limited, but is usually 1 to 6, preferably 1 to 4 from the viewpoint of easiness of synthesis, more preferably 2 to 4 in terms of luminous effect, and most preferably 3 or 4. I do.
The dendron used in the present invention needs to bind to polyphenyleneethynylene at its focal point. The bonding mode is not particularly limited, but specific bonding structures include, for example, an ether bond, an ester bond, an amide bond, a carbon-carbon bond, and a carbon-nitrogen bond.
The number of dendrons bonded to the polyphenyleneethynylene main chain is not particularly limited, and varies depending on the desired light emission behavior. The ratio of the number of dendrons to the number of phenylene rings in one repeating unit of the main chain is usually 2: 1. The ratio is preferably from 2: 1 to 1: 8, more preferably from 2: 1 to 1: 6, most preferably from 2: 1 to 1: 4 from the viewpoint of luminous efficiency and solvent solubility.
[0015]
<Polyphenylene ethinylene>
The polyphenyleneethynylene in the present invention is specifically a polymer composed of any of the phenyleneethynylene units represented by the following general formulas (3) to (5) and containing these at an arbitrary copolymerization ratio. It is. However, in general formulas (3) to (5), R 1 , R 2 , R 3 , And R 4 Independently represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a hexyl group, an octyl group, a decyl group, etc. Having 6 or less carbon atoms such as a hydrocarbon group having 10 or less carbon atoms, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a sec-butyloxy group, an isobutyloxy group, and a hexyloxy group. It means a structure arbitrarily selected from the group consisting of an alkoxy group and the above-mentioned dendron.
[0016]
Embedded image
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As a particularly preferable structure of polyphenyleneethynylene, a structure represented by the following general formula (1) (in the formula (1), L represents the above-mentioned dendron which may be different from each other) is exemplified.
[0020]
Embedded image
In the polyphenyleneethynylene of the present invention, the number of repetitions (degree of polymerization) of the phenyleneethynylene units represented by any of the general formulas (3) to (5) is not particularly limited; The degree is usually from 5 to 1000, preferably from 10 to 700, more preferably from 15 to 500, and most preferably from 20 to 400 from the viewpoints of coating properties and solvent solubility. There is no particular limitation on the molecular weight distribution at this time, but the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is usually 2.0 to 2.0. 20, preferably from 2.2 to 15, more preferably from 2.3 to 13, and most preferably from 2.3 to 10, from the viewpoints of coating properties and solvent solubility.
[0022]
<Resin composition>
The present invention provides a resin composition comprising polyphenyleneethynylene and a non-crystalline resin each having the above-mentioned dendron bonded as a side chain. The amorphous resin referred to here is a polymer that gives a transparent amorphous molded body in the visible region by a melt molding means generally used in the resin molding industry, and includes, for example, polystyrene, styrene / α- Styrene resins such as methyl styrene copolymer, styrene / maleic anhydride copolymer, styrene / methyl methacrylate copolymer, styrene glycidyl methacrylate copolymer, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyethyl acrylate Acrylic resins such as polytert-butyl methacrylate, polyphenyl methacrylate, polybenzyl methacrylate, polyadamantyl acrylate, polymethacrylic acid, polyacrylic acid, polyacrylamide, methyl methacrylate / methacrylic acid copolymer, Polycarbonate starting from 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A); polycarbonate starting from 2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly known as bisphenol C); Examples thereof include aromatic polycarbonate resins such as polycarbonate using 2,2-bis (4-hydroxyphenyl) phenylethane (commonly known as bisphenol P) as a raw material, and amorphous polyolefins such as hydrogenated polystyrene and poly (3-methylbutene-1). Among these, preferred in terms of light transmittance and molding temperature are styrene resins such as polystyrene, styrene / α-methylstyrene copolymer, styrene / maleic anhydride copolymer, and styrene glycidyl methacrylate copolymer; Polymethyl methacrylate, polymethyl Acrylic resin such as acrylate, polyethyl methacrylate, polyethyl acrylate, polyadamantyl acrylate, polymethacrylic acid, methyl methacrylate / methacrylic acid copolymer, and aromatic polycarbonate resin such as bisphenol A polycarbonate, bisphenol C polycarbonate, bisphenol P polycarbonate Among them, styrene resins such as polystyrene, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, methyl methacrylate / methacrylic acid copolymer, and aromatic polycarbonate resins such as bisphenol A polycarbonate and bisphenol P polycarbonate are more preferable. It is.
[0023]
The method for producing such a resin composition is not particularly limited. For example, a solution is mixed in a solvent such as tetrahydrofuran (THF), toluene, methylene chloride, chloroform, or a single-screw extruder, a twin-screw extruder, or a Brabender. General-purpose means such as melt mixing with a roll mixer or the like are possible.
In the resin composition of the present invention, the weight percentage of the polyphenylene ethynylene having a dendron side chain of the present invention is usually 0.1% to 95%, preferably 1% to 95% from the luminous ability of the resin composition. It is preferably from 3% to 95%, more preferably from 3% to 80%, most preferably from 5% to 70% from the viewpoint of the mechanical strength of the resin composition. Incidentally, such a resin composition, as long as the effect is not significantly impaired, glass fibers, glass flakes, glass beads, mica, talc, montmorillonite, smectite, synthetic mica, inorganic fillers such as synthetic smectite, polyethylene, polypropylene, polyester, Thermoplastic resins such as polyamide, rubber components such as styrene-based thermoplastic elastomers and acrylic rubber, resin beads, hollow beads, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, plasticizers such as petrolatum and glycerin esters, Arbitrary additives such as a lubricant, metal powder, semiconductor powder, graphite, resin powder, pigment, dye, fluorescent dye, pigment, compatibilizer and the like may be added.
[0024]
<Luminescent paint and luminous sheet-like molded body>
The present invention provides a luminescent paint containing the polyphenyleneethynylene having a dendron side chain of the present invention or the resin composition of the present invention, and a luminescent sheet-like molded product obtained by applying and drying the luminescent paint. Such a paint can be obtained by dissolving the polyphenyleneethynylene of the present invention or the resin composition of the present invention in a suitable solvent. The solvent used is not particularly limited as long as it has a necessary solubility. Examples thereof include tetrahydrofuran (THF), toluene, methylene chloride, chloroform and the like, as long as the effects of the present invention are not significantly impaired. The above-mentioned optional additives may be added.
[0025]
In the luminescent coating material of the present invention, the amount of the polyphenylene ethynylene of the present invention relative to 100 parts by weight of the solvent used is usually 0.1 to 80 parts by weight, preferably 1 to 80 parts by weight from the viewpoint of luminous ability, The amount is more preferably 5 to 80 parts by weight, still more preferably 5 to 60 parts by weight, and most preferably 5 to 50 parts by weight from the viewpoint of solution handling properties. When the resin composition of the present invention is used, the amount of the composition relative to 100 parts by weight of the solvent used is usually 1 to 70 parts by weight, preferably 5 to 70 parts by weight from the viewpoint of luminous ability, The amount is more preferably 7 to 70 parts by weight, still more preferably 7 to 60 parts by weight, most preferably 10 to 50 parts by weight from the viewpoint of handleability of the solution.
[0026]
The luminescent sheet-like molded product obtained by applying and drying the luminescent paint of the present invention can be obtained as a three-dimensional structure of any shape, such as particles, a film, a film, a sheet, and the like. Or, when it is molded as a film, the practical value is high.
There is no particular limitation on the method for obtaining such a molded body, and for example, a general-purpose method such as applying and drying the luminescent coating material of the present invention on a substrate (optionally performing any steps such as heating and deformation if necessary). ) Can be suitably manufactured.
[0027]
The substrate used is not particularly limited, but includes, for example, inorganic substances such as metals, metal oxides, ceramics, and compound semiconductors, and organic substances such as various polymers and paper, and further, water and alcohols. For example, an LB film can be obtained using the liquid surface described above. As a method for applying to the substrate, a general method such as a spin coating method, a dip coating method, a wetting film method, and a spray coating method can be used.
[0028]
In addition to the above-mentioned method, when the polyphenyleneethynylene of the present invention or the resin composition of the present invention has thermoplasticity, a general-purpose method such as heat extrusion film formation is also possible.
The thickness, size, shape, and surface properties (for example, attributes such as flat surface, spherical surface, curved surface, concave surface, convex surface, porous surface, smoothness, and thickness distribution) of the molded body obtained in this manner are described below. Although not particularly limited, for example, the thickness is usually about 1 to 100,000 nm, preferably about 1 to 10,000 nm, and more preferably about 1 to 1,000 nm.
[0029]
Further, in the obtained molded body, optional additives, for example, various stabilizers such as an antioxidant, a heat stabilizer, or a light stabilizer, glass fiber, glass beads, mica, talc, kaolin, clay mineral, carbon fiber, Various additives such as carbon black, graphite, metal fiber, metal powder, etc., antistatic agent, release agent, plasticizer, pigment and dye, rubber and elastomers, thermoplastic resin, etc. It is also possible.
[0030]
<Light-emitting method and principle>
The method of causing any of the polyphenyleneethynylene, the resin composition, the luminescent coating, and the luminescent sheet-shaped molded article of the present invention to emit light is not limited, but, for example, ultraviolet rays absorbed by a dendron side chain or a polyphenyleneethynylene main chain. It is possible by irradiation of light or visible light.
[0031]
Although it is known that the polyphenyleneethynylene structure itself emits light, one of the natural phenomena necessary for the completion of the present invention is that the irradiation of light absorbed by the dendron side chain causes the dendron itself to emit substantially no light. And that the polyphenyleneethynylene main chain emits strong light. This is the Kawa et al .; Chem. Mater. 10, pp. 286-296 (1998), is the discovery of the new fact that the sensitizing effect (antenna effect) of lanthanoid cation emission of aromatic dendrons also occurs in organic luminescent materials. The present inventors have already demonstrated that by controlling the chemical structure of the dendron side chain, energy transfer from the dendron to the polyphenyleneethynylene main chain occurs with almost 100% efficiency. It was possible for the first time to control the chemical structure of such dendrons, and it was pointed out that the luminescence characteristics could be further improved by optimizing the molecular structure.
[0032]
【Example】
Hereinafter, specific embodiments of the present invention will be described in more detail with reference to Examples. However, the present invention is not intended to be limited by these Examples as long as the gist of the present invention is not exceeded.
The reagents and resins used in the examples were supplied from Aldrich unless otherwise noted.
[0033]
[Measuring equipment and conditions, etc.]
(1) 1 H-NMR
GSX-270 FT-NMR (270 MHz) manufactured by JEOL, solvent: CDCl 3 . Room temperature measurement. The standard is CDCl 3 At 7.28 ppm.
(2) Mass spectrum: ProteinTof type MALDI-TOF-MS manufactured by Bruker was used. 9-Nitroanthracene was used as matrix material.
(3) GPC: HLC-8020 manufactured by Tosoh Corporation was used, the solvent was tetrahydrofuran (THF), the inlet temperature was 35 ° C, the oven temperature was 40 ° C, the flow rate was 1 mL / min 1 mL / min, and the pressure was 76 kgf / cm. 2 , Detected by absorption at 432 nm. The molecular weight was determined by a calibration curve using a plurality of types of monodisperse polystyrene having known molecular weights.
(4) Absorption spectrum: V560 absorption spectrophotometer manufactured by JASCO (using 1 cm quartz cell). Room temperature measurement.
(5) Emission spectrum: JASCO FP-777W fluorimeter (using 1 cm quartz cell). Room temperature measurement.
[0034]
1. Dendron synthesis
Jiang, D .; -L. J. et al. Am. Chem. Soc. 120, 10895, a dendron having a 3,5-dimethoxybenzyl group, having a 3,5-dioxybenzyl structure repeating unit, and having a benzyl bromide structure at the focal point. (Hereinafter, this dendron is abbreviated as [G-n] Br. Here, n is a natural number and represents the generation number of the dendron. However, in the display in the document, [G-n] is L (n-1). .). Structure and purity 1 It was confirmed from the ratio of the integrated value of the 3.7 ppm methoxy group signal and the benzylic proton in H-NMR, and the fact that a signal corresponding to the theoretical molecular weight was obtained in the mass spectrum.
[0035]
2. Synthesis of diethylene benzene [Gn] 2E2 bound to dendron
Cuprous chloride (0.05 equivalent) and dichlorobis (triphenylphosphine) palladium were added to 1,4-dihydroxy-2,5-diiodobenzene (compound 1: 1.0 equivalent in FIG. 2) while stirring. (II) (0.05 equivalent) was sequentially added at room temperature, and vacuum evacuation and nitrogen replacement in the vessel were repeated. Trimethylsilylacetylene (3.0 equivalents) and diisopropylamine (3.0 equivalents) were sequentially added thereto, reacted at 60 ° C. for 4 hours, diluted with toluene and filtered to remove solids. This was purified by silica gel column chromatography to obtain 1,4-dihydroxy-2,5-bis (trimethylsilylethynyl) benzene (compound 2 in FIG. 2). Then, this was stirred in methanol at room temperature for 24 hours with an excess amount of anhydrous potassium carbonate, and purified by silica gel column chromatography using methanol / methylene chloride as an eluent to give 1,4-dihydroxy-2,5-diethynyl. Benzene was obtained (
3. Synthesis and evaluation of polyphenyleneethynylene with dendron attached to side chain
[0036]
Example 1
Diethynylenebenzene [G-3] 2E2 (96.8 mg; 1.0 equiv.), P-diiodobenzene (15.27 mg; 1.0 equiv.), Bound to the third-generation dendron synthesized above, tetrakis (Triphenylphosphine) palladium (0) (2.68 mg; 0.05 equivalent) was mixed, and the inside of the vessel was repeatedly evacuated and replaced with nitrogen. Then, 3 mL of dry tetrahydrofuran (THF) was added as a solvent. A solution obtained by dissolving 2.75 mmol of cuprous iodide in 1000 mL of diisopropylamine was added thereto while stirring so that 0.05 equivalent of cuprous iodide was obtained. After stirring at 50 ° C. for 26 hours, 2 drops of ethynylbenzene were added, and the reaction was continued for further 13 hours. The reaction solution was concentrated under reduced pressure, and purified by a reprecipitation method in which a chloroform-soluble matter was poured into methanol. The product gave a number average molecular weight (Mn) of 43900 by GPC, a weight average molecular weight (Mw) of 277600 and a peak top molecular weight of 150,000 (corresponding to about 70-mer based on the predicted structure shown in FIG. 3). This product was soluble in tetrahydrofuran. In the absorption spectrum measurement of this solution, an absorption band derived from dendron was observed around 280 nm, and an absorption band derived from polyphenyleneethynylene main chain was observed around 432 nm. Then, when ultraviolet light of 280 nm was irradiated to excite the dendron structure, the emission band derived from the dendron (around 310 nm) was not observed, and only the emission band derived from the polyphenyleneethynylene main chain (around 454 nm) was observed. From this, it was confirmed that light was emitted by energy transfer from the dendron side chain to the polyphenyleneethynylene main chain. Furthermore, a comparison of the absorption spectrum and the excitation spectrum confirmed that this energy transfer occurred at an efficiency of almost 100%. In addition, a good film was obtained by spin casting of this solution, and the same emission band as that of the above solution system was given by irradiation with 280 nm ultraviolet light. Therefore, it was confirmed that the film of this substance also had excellent luminescence ability. Was done.
[0037]
Example 2
The same operation was performed using [G-2] 2E2, which is a corresponding compound to which a second-generation dendron was bound instead of [G-3] 2E2 in Example 1, and the formation of pophenyleneethynylene was confirmed by GPC. .
Example 3
The same operation was performed using [G-4] 2E2, which is a corresponding compound to which a fourth-generation dendron was bound instead of [G-3] 2E2 in Example 1, and the formation of pophenyleneethynylene was confirmed by GPC. .
4. Preparation and evaluation of composition of polyphenyleneethynylene with dendron attached to side chain and amorphous resin
[0038]
Example 4
Polystyrene (weight-average molecular weight: about 35,000) was added to a solution of polyphenyleneethynylene in tetrahydrofuran in which the third-generation dendron synthesized in Example 1 was bonded to the side chain. The mixing ratio of the polyphenylene ethynylene and the polystyrene was 10:90 by weight. A good film was obtained by spin-casting this solution, and the irradiation with ultraviolet light of 280 nm gave the same light emission as the light-emitting band described in Example 1. Thus, this polystyrene resin composition film also has excellent light-emitting ability. It was confirmed that.
[0039]
Example 5
A similar film was obtained in the same manner as in Example 4 except that the mixing ratio of polyphenyleneethynylene in which the third-generation dendron was bonded to the side chain and polystyrene was 80:20 by weight, and a good film was obtained. The light emission gave the same light emission as the light emission band described in Example 1, confirming that this polystyrene resin composition film also had excellent light emission ability.
[0040]
Example 6
Polymethyl methacrylate (weight average molecular weight: about 15,000) was added to a solution of polyphenylene ethynylene in tetrahydrofuran in which the third-generation dendron synthesized in Example 1 was bonded to the side chain. The mixing ratio of the polyphenyleneethynylene and the polymethyl methacrylate was 10:90 by weight. A good film was obtained by spin casting of this solution, and the same emission as the emission band described in Example 1 was given by irradiation with ultraviolet light of 280 nm. Therefore, this polymethyl methacrylate resin composition film also has excellent light emission ability. Was confirmed to have.
[0041]
Example 7
A good film was obtained by performing the same operation as in Example 4 except that the mixing ratio of polyphenyleneethynylene in which the third generation dendron was bonded to the side chain and polymethyl methacrylate was set to 80:20 by weight. Gave the same light emission as the emission band described in Example 1 from the irradiation of the ultraviolet light, and it was confirmed that this polymethyl methacrylate resin composition film also had excellent light emission ability.
[0042]
Example 8
A bisphenol A polycarbonate (ASTM-D1238 standard melt index under a 300 ° C / 1.2 kg load of 8-10 g / 10 min. ) Was added. The mixing ratio of the polyphenyleneethynylene and the bisphenol A polycarbonate was 10:90 by weight. A good film was obtained by spin casting of this solution, and the same emission as the emission band described in Example 1 was given by irradiation with ultraviolet light of 280 nm. Therefore, this bisphenol A polycarbonate resin composition film also has excellent light emission ability. Was confirmed to have.
[0043]
Example 9
A similar film was obtained in the same manner as in Example 4 except that the mixing ratio of polyphenyleneethynylene in which the third-generation dendron was bonded to the side chain and bisphenol A polycarbonate was changed to 80:20 by weight, whereby a good film was obtained. Gave the same light emission as the emission band described in Example 1 from the ultraviolet light irradiation, and it was confirmed that this bisphenol A polycarbonate resin composition film also had excellent light emission ability.
[0044]
【The invention's effect】
Polyphenyleneethynylene having a dendron having an aromatic ring in the repeating unit newly found in the present invention in the side chain has excellent solvent solubility and film forming properties, and has high luminous ability, so that luminescent paints and The coating material can be used as a luminescent sheet-like molded product applied to a film or the like. Further, since it has compatibility with an amorphous resin such as a styrene-based resin, an acrylic-based resin, or an aromatic polycarbonate resin, it can be used as a composition with the resin, and such a resin composition also has the same characteristics and uses as described above. Have.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing dendrimer generations and focal points.
FIG. 2 is an explanatory diagram showing a synthetic route of polyphenyleneethynylene having a dendron of the present invention in a side chain.
FIG. 3 is a schematic diagram showing the chemical structure of the product obtained in Example 1.
Claims (8)
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