JP4419484B2

JP4419484B2 - Π-conjugated polymer having dendritic branch in side chain and organic thin film device using the same

Info

Publication number: JP4419484B2
Application number: JP2003317593A
Authority: JP
Inventors: 汪芳白井; 睦木村; 江美子神戸
Original assignee: TDK Corp
Current assignee: TDK Corp
Priority date: 2003-09-09
Filing date: 2003-09-09
Publication date: 2010-02-24
Anticipated expiration: 2023-09-09
Also published as: JP2005082730A

Description

本発明は、側鎖に樹状分岐を有するπ共役系高分子及びそれを用いた有機薄膜素子に関する。 The present invention relates to a π-conjugated polymer having a dendritic branch in a side chain and an organic thin film element using the same.

導電性高分子は、一般的に不溶不融の物質である。このような導電性高分子を可溶化できれば塗布により容易に薄膜を形成でき、発光素子、太陽電池、有機ＦＥＴ素子、光電変換素子等に応用できるため、置換基導入等によって骨格を調整し可溶化を図る試みがなされている。 The conductive polymer is generally an insoluble and infusible substance. If such a conductive polymer can be solubilized, a thin film can be easily formed by coating, and can be applied to light-emitting elements, solar cells, organic FET elements, photoelectric conversion elements, etc., so that the skeleton can be adjusted and solubilized by introducing substituents, etc. Attempts have been made.

このような試みとして、有機ＥＬ素子においては、可溶性の前駆体高分子を電極上にコーティングして薄膜化した後、加熱処理を施すことによって共役系高分子に転換させて素子を形成する方法が報告されている（特許文献１）。また、可溶化のために、ポリパラフェニレンビニレン、ポリチオフェン、ポリフルオレン等のπ共役系高分子の側鎖に、長鎖アルキル基、アルコキシ基、フェノキシ基等を導入することも検討されている。 As such an attempt, in organic EL devices, a method of forming a device by coating a soluble precursor polymer on an electrode to form a thin film and then converting it to a conjugated polymer by heat treatment is reported. (Patent Document 1). In addition, for solubilization, introduction of a long-chain alkyl group, an alkoxy group, a phenoxy group, or the like into a side chain of a π-conjugated polymer such as polyparaphenylene vinylene, polythiophene, or polyfluorene has been studied.

電子材料としてはまた、デンドリマー骨格を有したものが知られている。このような電子材料は、下記特許文献２や特許文献３に開示されているが、開示された材料はいずれも低分子量であるモノマー中心に対し非共役系のデンドロン骨格を有する超分岐高分子である。なお、太陽電池においても、吸光性高分子として長鎖アルコキシ基を側鎖に導入したポリパラフェニレンビニレン誘導体が適用されている（特許文献４）。
特許第３２４９９７１号公報特開２００３−１６１９７２号公報特開２００３−０７８１８８号公報特表２００１−５２６４６６号公報 An electronic material having a dendrimer skeleton is also known. Such electronic materials are disclosed in the following Patent Document 2 and Patent Document 3, but all disclosed materials are hyperbranched polymers having a non-conjugated dendron skeleton with respect to a monomer center having a low molecular weight. is there. Note that a polyparaphenylene vinylene derivative in which a long-chain alkoxy group is introduced into a side chain as a light-absorbing polymer is also applied to solar cells (Patent Document 4).
Japanese Patent No. 3249971 JP 2003-161972 A Japanese Patent Laid-Open No. 2003-078188 JP-T-2001-526466

しかしながら、上述のような溶解性付与のための側鎖の導入により、導電性高分子の柔軟性が高くなりガラス転移温度が低下してしまい、有機薄膜素子に適用した場合に高温耐久性が低下する。また、ミクロブラウン運動によるサーモクロミズム発生の問題や高分子同士の凝集の問題もある。また発光層ホストとして用いる場合には、発光ドーパントへのエネルギー移動あるいは電荷移動が起こりにくく、ドーパントからの発光が効率よく取り出せないため、高効率化又は高輝度化が比較的容易に行うことができるドーピング添加による手法を施しても効果が得られないといった問題が生じていた。このように、従来の側鎖導入法によれば、種々の物性上の問題点が発生し、素子に適用した場合の特性を不安定化させていた。 However, the introduction of the side chain for imparting solubility as described above increases the flexibility of the conductive polymer and lowers the glass transition temperature, resulting in reduced high-temperature durability when applied to an organic thin film element. To do. There is also a problem of thermochromism due to micro Brownian motion and a problem of aggregation between polymers. In addition, when used as a light emitting layer host, energy transfer or charge transfer to the light emitting dopant hardly occurs, and light emission from the dopant cannot be taken out efficiently, so that high efficiency or high luminance can be performed relatively easily. There has been a problem that the effect cannot be obtained even when the doping method is applied. Thus, according to the conventional side chain introduction method, various problems in physical properties occur, and the characteristics when applied to the device are destabilized.

そこで、本発明の目的は、側鎖が導入されたπ共役系高分子であって、有機溶媒で溶解可能であり、側鎖の存在によっても高分子全体としてのガラス転移温度の低下が見られず、有機薄膜素子へ適用した場合に優れた電荷移動性やエネルギー移動性を発揮し、高温耐久性にも優れる、π共役系高分子を提供することにある。本発明の目的はまた、このようなπ共役系高分子を用いた有機薄膜素子を提供することにある。 Therefore, an object of the present invention is a π-conjugated polymer into which side chains are introduced, which can be dissolved in an organic solvent, and the glass transition temperature as a whole of the polymer is lowered by the presence of side chains. First, it is to provide a π-conjugated polymer that exhibits excellent charge mobility and energy mobility when applied to an organic thin film element and is excellent in high-temperature durability. Another object of the present invention is to provide an organic thin film element using such a π-conjugated polymer.

上記課題を解決するために、本発明は、π共役系高分子からなる主鎖と該主鎖に結合した少なくとも１つの側鎖化合物とから構成され、上記側鎖化合物の少なくとも１つは、コアユニットを中心に第１〜第ｎ世代枝ユニットが世代順に順次樹状に分岐するように結合して成長したπ共役系樹状分岐化合物（ｎは１又は２以上の整数であり、末端枝ユニットの世代数を表す。）である、側鎖に樹状分岐を有するπ共役系高分子を提供するものである。 In order to solve the above problems, the present invention comprises a main chain composed of a π-conjugated polymer and at least one side chain compound bonded to the main chain, wherein at least one of the side chain compounds is a core A π-conjugated dendritic compound (n is an integer of 1 or 2 and a terminal branch unit) in which the 1st to n-th generation branch units are connected to each other so that the first to n-th generation branch units are sequentially branched in the order of generation. The π-conjugated polymer having a dendritic branch in the side chain is provided.

本発明のπ共役系高分子は、側鎖にπ共役系樹状分岐化合物を有するため分子全体の剛直性が増し、側鎖導入に伴うガラス転移温度の低下が防止される。また、側鎖の樹状分岐化合物がπ共役系であるために、有機薄膜素子へ適用した場合に高分子全体として電荷移動性やエネルギー移動性に優れるようになる。また、側鎖の樹状分岐化合物の末端枝ユニットには官能基を導入でき、高分子全体としての反応性や有機溶媒への溶解性及び電荷移動性を制御できる。 Since the π-conjugated polymer of the present invention has a π-conjugated dendritic compound in the side chain, the rigidity of the whole molecule is increased and the glass transition temperature is not lowered due to the introduction of the side chain. In addition, since the dendritic compound of the side chain is a π-conjugated system, when applied to an organic thin film element, the entire polymer is excellent in charge mobility and energy mobility. Moreover, a functional group can be introduced into the terminal branch unit of the dendritic compound of the side chain, and the reactivity of the polymer as a whole, the solubility in an organic solvent, and the charge mobility can be controlled.

合成の容易性及び側鎖の対称性の観点からは、π共役系樹状分岐化合物は、コアユニットにおいて主鎖と結合していることが好ましい。また、ｎを２以上の整数とすることで、有機薄膜素子へ適用した場合の電荷移動性等の諸特性を向上できる。 From the viewpoint of ease of synthesis and side chain symmetry, the π-conjugated dendritic compound is preferably bonded to the main chain in the core unit. Further, by setting n to an integer of 2 or more, various characteristics such as charge mobility when applied to an organic thin film element can be improved.

なお、末端枝ユニットを除く枝ユニット及びコアユニットは、芳香環又は芳香族性複素環から導かれる多価の基であり、末端枝ユニットは芳香環又は芳香族性複素環から導かれる１価の基であり、コアユニットと枝ユニットの結合並びに枝ユニット同士の結合は単結合であることが好ましい。このような化合物はπ電子共役性に優れ、また対称性よく精密に合成できるため、有機薄膜素子へ適用した場合の特性を向上できる。また、分子の剛直性を向上させる点においても有利である。 The branch unit and the core unit excluding the terminal branch unit are polyvalent groups derived from an aromatic ring or an aromatic heterocyclic ring, and the terminal branch unit is a monovalent group derived from an aromatic ring or an aromatic heterocyclic ring. It is preferable that the bond between the core unit and the branch unit and the bond between the branch units are a single bond. Such a compound is excellent in π-electron conjugation and can be synthesized precisely with good symmetry, so that the characteristics when applied to an organic thin film element can be improved. It is also advantageous in terms of improving molecular rigidity.

有機溶剤への溶解性の制御の点からは、末端枝ユニットは、水素原子、アルキル基、置換又は未置換のアミノ基、アルコキシ基及びアルキルチオ基からなる群より選ばれる少なくとも１つの基を有するのがよく、電荷輸送性向上の点からは、主鎖であるπ共役系高分子は、ポリフェニレンビニレン系高分子、ポリフェニレンエチニレン系高分子、ポリフルオレン系高分子、ポリチオフェン系高分子、ポリチアジアゾール系高分子又はポリフェニレン系高分子であるのがよい。 From the viewpoint of controlling solubility in an organic solvent, the terminal branch unit has at least one group selected from the group consisting of a hydrogen atom, an alkyl group, a substituted or unsubstituted amino group, an alkoxy group, and an alkylthio group. From the point of charge transport improvement, the main chain π-conjugated polymer is polyphenylene vinylene polymer, polyphenylene ethynylene polymer, polyfluorene polymer, polythiophene polymer, polythiadiazole polymer It may be a polymer or a polyphenylene polymer.

上述した、側鎖に樹状分岐を有するπ共役系高分子としては、下記一般式（１）で表される繰返し単位を含むものが挙げられる。
［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、アルキル基、１価の複素環基又はシアノ基、Ａｒは、芳香環又は芳香族性複素環から導かれる（２＋ｑ）価の基、ｐは０又は１、ｑは１〜６の整数、をそれぞれ表す。また、Ｇは、コアユニットを中心に第１〜第ｎ世代枝ユニットが世代順に順次樹状に分岐するように結合して成長したπ共役系樹状分岐化合物（ｎは１又は２以上の整数であり、末端枝ユニットの世代数を表す。）から導かれる１価の基を表す。但し、前記末端枝ユニットを除く枝ユニット及び前記コアユニットは、芳香環又は芳香族性複素環から導かれる多価の基であり、前記末端枝ユニットは芳香環又は芳香族性複素環から導かれる１価の基であり、前記コアユニットと前記枝ユニットの結合並びに前記枝ユニット同士の結合は単結合であり、更に、前記末端枝ユニットは、水素原子、アルキル基、置換又は未置換のアミノ基、アルコキシ基及びアルキルチオ基からなる群より選ばれる少なくとも１つの基を有する。］ Examples of the π-conjugated polymer having a dendritic branch in the side chain described above include those containing a repeating unit represented by the following general formula (1).
[Wherein, R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a monovalent heterocyclic group or a cyano group, and Ar is a (2 + q) -valent group derived from an aromatic ring or an aromatic heterocyclic ring. , P represents 0 or 1, and q represents an integer of 1 to 6, respectively. G is a π-conjugated dendritic branch compound in which the 1st to n-th generation branch units are coupled so as to be branched in a tree-like manner in order of generation around the core unit (n is an integer of 1 or 2 or more) And represents the number of generations of the terminal branch unit). However, the branch unit excluding the terminal branch unit and the core unit are polyvalent groups derived from an aromatic ring or an aromatic heterocyclic ring, and the terminal branch unit is derived from an aromatic ring or an aromatic heterocyclic ring. A monovalent group, a bond between the core unit and the branch unit and a bond between the branch units are a single bond, and the terminal branch unit is a hydrogen atom, an alkyl group, a substituted or unsubstituted amino group; , At least one group selected from the group consisting of an alkoxy group and an alkylthio group. ]

この場合においても、π共役系樹状分岐化合物は、コアユニットにおいてＡｒと結合していることが好ましく、ｎは２以上が好ましく、末端枝ユニットを除く枝ユニット及びコアユニットは、置換又は未置換ベンゼンから導かれる３価の基であり、末端枝ユニットは、水素原子、アルキル基、置換又は未置換のアミノ基、アルコキシ基及びアルキルチオ基からなる群より選ばれる少なくとも１つの基を有するフェニル基が好ましい。 Also in this case, the π-conjugated dendritic compound is preferably bonded to Ar in the core unit, n is preferably 2 or more, and the branch unit and core unit excluding the terminal branch unit are substituted or unsubstituted. A trivalent group derived from benzene, wherein the terminal branch unit is a phenyl group having at least one group selected from the group consisting of a hydrogen atom, an alkyl group, a substituted or unsubstituted amino group, an alkoxy group and an alkylthio group; preferable.

また、側鎖に樹状分岐を有するπ共役系高分子のポリスチレン換算の重量平均分子量（Ｍｗ）は、３０００〜５００００００が好ましい。Ｍｗが３０００未満であると、塗膜性が悪く、また電界が作用した際には高分子鎖の凝集が発生する場合がある。凝集した部分は低エネルギー状態であるので、たとえば有機ＥＬ素子に応用した場合は、励起エネルギーが凝集部分に集中し長波長の発光になってしまい、相互作用の無い本来の発光に比べ電流効率が低く、寿命の劣化といった問題が生じる。一方、Ｍｗが５００００００を超すと溶媒に溶解しずらくなるので、適用可能な用途が制限されてしまう。 Moreover, as for the weight average molecular weight (Mw) of polystyrene conversion of (pi) conjugated polymer which has a dendritic branch in a side chain, 3000-5 million are preferable. When Mw is less than 3000, the coating properties are poor, and when an electric field is applied, polymer chains may be aggregated. Since the agglomerated part is in a low energy state, for example, when applied to an organic EL element, the excitation energy is concentrated on the agglomerated part and light emission has a long wavelength, and the current efficiency is higher than that of original light emission without interaction. The problem is low and the life is deteriorated. On the other hand, if Mw exceeds 5000000, it is difficult to dissolve in a solvent, and therefore, applicable applications are limited.

このような、側鎖に樹状分岐を有するπ共役系高分子を用いることにより、当該π共役系高分子を含む層を備える有機薄膜素子及び太陽電池が提供される。また電荷輸送層又は発光層として、当該π共役系高分子を含む層或いは当該π共役系高分子を含む母材にドーパントが添加された層を備える有機ＥＬ素子が提供される。 By using such a π-conjugated polymer having a dendritic branch in the side chain, an organic thin film element and a solar cell including a layer containing the π-conjugated polymer are provided. In addition, an organic EL element including a layer containing the π-conjugated polymer or a layer in which a dopant is added to a base material containing the π-conjugated polymer is provided as the charge transport layer or the light-emitting layer.

本発明によれば、側鎖が導入されたπ共役系高分子であって、有機溶媒で溶解可能であり、側鎖の存在によっても高分子全体としてのガラス転移温度の低下が見られず、有機薄膜素子へ適用した場合に優れた電荷移動性を発揮し、高温耐久性にも優れる、π共役系高分子が提供される。また、このようなπ共役系高分子を用いた有機薄膜素子が提供される。特に、上記π共役系高分子を有機ＥＬ素子の発光層ホストとして用いる場合には、発光ドーパントへのエネルギー移動或いは電荷移動が生じて、ドーパントからの発光を効率よく取り出すことができ、高効率化又は高輝度化が容易となる。 According to the present invention, a π-conjugated polymer having side chains introduced therein, which can be dissolved in an organic solvent, and the glass transition temperature as a whole polymer is not lowered even by the presence of side chains, Provided is a π-conjugated polymer that exhibits excellent charge mobility when applied to an organic thin film element and is excellent in high-temperature durability. In addition, an organic thin film element using such a π-conjugated polymer is provided. In particular, when the above π-conjugated polymer is used as a light-emitting layer host of an organic EL device, energy transfer or charge transfer to the light-emitting dopant occurs, and light emission from the dopant can be efficiently taken out, thereby improving efficiency. Alternatively, it is easy to increase the brightness.

図１は、π共役系高分子からなる主鎖に結合する側鎖化合物を模式的に示すものである。図１に示す側鎖化合物１００は、コアユニット１０を中心に第１世代枝ユニット１、第２世代枝ユニット２、第３世代枝ユニット３が世代順に順次樹状に分岐するように、結合６により成長したπ共役系樹状分岐化合物である。ここで、第３世代枝ユニット３は末端枝ユニットに相当する。なお、本発明において、側鎖化合物の世代数は（末端枝ユニットの世代−１）で表すこととし、図１の側鎖化合物１００の世代数は２である。したがって、コアユニット１０と第１世代枝ユニット１のみからなる側鎖化合物は世代数は０であり、コアユニット１０と第１世代枝ユニット１と第２世代枝ユニット２とからなる側鎖化合物は世代数は１である。側鎖化合物１００は主鎖であるπ共役系高分子と結合している必要があり、その結合箇所はコアユニットであっても枝ユニットであってもよい。但し、合成の容易性や側鎖の対称性の点から側鎖化合物はそのコアユニットにおいて主鎖のπ共役系高分子と結合しているのがよい。 FIG. 1 schematically shows a side chain compound bonded to a main chain composed of a π-conjugated polymer. The side chain compound 100 shown in FIG. 1 has a bond 6 so that the first generation branch unit 1, the second generation branch unit 2, and the third generation branch unit 3 are sequentially branched in the order of generation around the core unit 10. It is a π-conjugated dendritic compound grown by Here, the third generation branch unit 3 corresponds to a terminal branch unit. In the present invention, the number of generations of the side chain compound is represented by (generation of terminal branch unit-1), and the number of generations of the side chain compound 100 in FIG. Therefore, the side chain compound consisting only of the core unit 10 and the first generation branch unit 1 has 0 generations, and the side chain compound consisting of the core unit 10, the first generation branch unit 1 and the second generation branch unit 2 is The number of generations is 1. The side chain compound 100 needs to be bonded to the π-conjugated polymer as the main chain, and the bonding site may be a core unit or a branch unit. However, from the viewpoint of ease of synthesis and side chain symmetry, the side chain compound is preferably bonded to the π-conjugated polymer of the main chain in its core unit.

図２は、主鎖と結合するための官能基をコアユニットに有した側鎖化合物を模式的に示すものである。図２に示す側鎖化合物１００は、コアユニット１０を中心に第１世代枝ユニット１、第２世代枝ユニット２、第３世代枝ユニット３が世代順に順次樹状に分岐するように、結合６により成長したπ共役系樹状分岐化合物であり、コアユニット１０は主鎖と結合するための側鎖官能基１２を有している。 FIG. 2 schematically shows a side chain compound having a functional group for binding to the main chain in the core unit. The side chain compound 100 shown in FIG. 2 has a bond 6 so that the first generation branch unit 1, the second generation branch unit 2, and the third generation branch unit 3 are sequentially branched in the order of generation around the core unit 10. The core unit 10 has a side chain functional group 12 for bonding to the main chain.

図３は、主鎖と結合するための官能基をコアユニットに有した側鎖化合物と、側鎖化合物と結合するための官能基を有した主鎖を模式的に示すものである。すなわち、図３には、図２と同様の構成を有した側鎖化合物１００と、側鎖化合物と結合するための主鎖官能基２２とπ共役系高分子２０とから構成される主鎖２００とが模式的に表されている。ここで、側鎖官能基１２と主鎖官能基２２とが結合することにより、主鎖２００に側鎖化合物１００が導入される。 FIG. 3 schematically shows a side chain compound having a functional group for binding to the main chain in the core unit and a main chain having a functional group for binding to the side chain compound. That is, FIG. 3 shows a main chain 200 composed of a side chain compound 100 having the same configuration as FIG. 2, a main chain functional group 22 for binding to the side chain compound, and a π-conjugated polymer 20. Is schematically represented. Here, the side chain compound 100 is introduced into the main chain 200 by bonding the side chain functional group 12 and the main chain functional group 22.

図４は、側鎖に樹状分岐を有するπ共役系高分子を模式的に示すものである。図４に示す、側鎖に樹状分岐を有するπ共役系高分子３００は、側鎖化合物１００の側鎖官能基１２と主鎖２００の主鎖官能基２２とが反応して結合３０が形成され、側鎖化合物１００が主鎖２００に導入されたものである。形成される結合３０の種類は任意であるがπ共役系高分子３００全体としてπ電子が共役できる結合であることが好ましい。 FIG. 4 schematically shows a π-conjugated polymer having a dendritic branch in the side chain. In the π-conjugated polymer 300 having a dendritic branch in the side chain shown in FIG. 4, the side chain functional group 12 of the side chain compound 100 and the main chain functional group 22 of the main chain 200 react to form a bond 30. The side chain compound 100 is introduced into the main chain 200. The type of bond 30 to be formed is arbitrary, but it is preferable that the π-conjugated polymer 300 as a whole is a bond capable of conjugating π electrons.

本発明において好適なπ共役系樹状分岐化合物は、例えば、以下の一般式（Ｓ１）及び（Ｓ２）で表される構造を有するものである。一般式（Ｓ１）において、Ｒ^１０、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に水素原子、アルキル基、置換又は未置換のアミノ基、アルコキシ基又はアルキルチオ基を表し、一般式（Ｓ２）において、Ｒ^２０及びＲ^２１はそれぞれ独立にアルキル基、置換又は未置換のアミノ基、アルコキシ基又はアルキルチオ基を表す。本発明において、末端枝ユニットの世代数は２以上が好ましいことから、π共役系樹状分岐化合物としては、一般式（Ｓ１）で表されるものがより好ましい。また、コアユニットにおいて主鎖と結合することが好ましいことから、一般式（Ｓ１）及び（Ｓ２）における＋が付された炭素において主鎖と結合（好ましくは単結合により結合）することが好ましい。なお、一般式（Ｓ１）及び（Ｓ２）で表される化合物は、＋で表される位置に図２に示されるような側鎖官能基を有していてもよい。また、置換アミノ基の置換基としては炭素数１〜３のアルキル基、フェニル基が挙げられる。 The π-conjugated dendritic compound suitable in the present invention has, for example, a structure represented by the following general formulas (S1) and (S2). In the general formula (S1), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, a substituted or unsubstituted amino group, an alkoxy group or an alkylthio group, and in the general formula (S2) , R ²⁰ and R ²¹ each independently represents an alkyl group, a substituted or unsubstituted amino group, an alkoxy group or an alkylthio group. In the present invention, since the number of generations of terminal branch units is preferably 2 or more, the π-conjugated dendritic compound is more preferably represented by the general formula (S1). Moreover, since it is preferable to couple | bond with a principal chain in a core unit, it is preferable to couple | bond with a principal chain (preferably couple | bonded by a single bond) in carbon attached | subjected + in general formula (S1) and (S2). In addition, the compound represented by general formula (S1) and (S2) may have a side chain functional group as shown in FIG. 2 in the position represented by +. Moreover, as a substituent of a substituted amino group, a C1-C3 alkyl group and a phenyl group are mentioned.

一般式（Ｓ１）で表されるπ共役系樹状分岐化合物として好適なものとしては、以下の化学式（Ｓ１−１）、（Ｓ１−２）、（Ｓ１−３）及び（Ｓ１−４）で表される化合物が挙げられる。なお＋は上記と同義である。 As a suitable π-conjugated dendritic compound represented by the general formula (S1), the following chemical formulas (S1-1), (S1-2), (S1-3) and (S1-4) And the compounds represented. In addition, + is synonymous with the above.

上述した側鎖が結合する主鎖の骨格としては、以下の一般式（２ａ）又は（２ｂ）で表される繰り返し単位を含むπ共役系高分子が好ましい。
As the skeleton of the main chain to which the side chain is bonded, a π-conjugated polymer containing a repeating unit represented by the following general formula (2a) or (2b) is preferable.

上記式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、アルキル基、１価の複素環基又はシアノ基、Ａｒ及びＡｒ’は、それぞれ独立に芳香環又は芳香族性複素環から導かれる２価の基、ｐ、ｐ１及びｐ２は、それぞれ独立に０又は１を表す。なお、芳香環及び芳香族性複素環には縮合環が含まれ（以下同様）、側鎖化合物との結合は一般式（２ａ）又は（２ｂ）で表される繰り返し単位のうちのＡｒ又はＡｒ’の箇所で生じることが好ましい。 In the above formula, R ¹ and R ² are each independently a hydrogen atom, alkyl group, monovalent heterocyclic group or cyano group, and Ar and Ar ′ are each independently derived from an aromatic ring or aromatic heterocyclic ring. The divalent groups, p, p1 and p2 each independently represent 0 or 1. The aromatic ring and the aromatic heterocyclic ring include a condensed ring (hereinafter the same), and the bond with the side chain compound is Ar or Ar in the repeating unit represented by the general formula (2a) or (2b) It is preferable to occur at the point of '.

一般式（２ａ）又は（２ｂ）で表される繰り返し単位を含むπ共役系高分子としては、以下の（２−１）〜（２−１０）の一般式で表されるものが挙げられ（Ａｒ、Ａｒ’、Ｒ^１及びＲ^２については上記と同義であり、ｔ及びｕはそれぞれ独立に１以上の整数である。）、更に詳しくは、下記式（２−１ａ）、（２−３ａ）、（２−５ａ）、（２−６ａ）及び（２−７ａ）で表されるものが挙げられる。 Examples of the π-conjugated polymer containing the repeating unit represented by the general formula (2a) or (2b) include those represented by the following general formulas (2-1) to (2-10) ( Ar, Ar ′, R ¹ and R ² are as defined above, and t and u are each independently an integer of 1 or more.) More specifically, the following formulas (2-1a) and (2-3a) ), (2-5a), (2-6a) and (2-7a).

本発明に係る、側鎖に樹状分岐を有するπ共役系高分子は、好ましくは以下の一般式（１ａ）又は（１ｂ）で表される繰り返し単位を含む。なお、これらの式中、Ｒ^１、Ｒ^２、ｐ、ｐ１及びｐ２は上記と同義であり、Ａｒは、芳香環又は芳香族性複素環から導かれる（２＋ｑ）価の基、Ａｒ’は、芳香環又は芳香族性複素環から導かれる２価の基、ｑは１〜６の整数（１〜４の整数が好ましく、１〜２の整数がより好ましい。）、をそれぞれ表す。また、Ｇは上述したπ共役系分岐化合物から導かれる１価の基である。
The π-conjugated polymer having a dendritic branch in the side chain according to the present invention preferably contains a repeating unit represented by the following general formula (1a) or (1b). In these formulas, R ¹ , R ² , p, p1 and p2 are as defined above, Ar is a (2 + q) -valent group derived from an aromatic ring or aromatic heterocyclic ring, and Ar ′ is A divalent group derived from an aromatic ring or an aromatic heterocyclic ring, q represents an integer of 1 to 6 (an integer of 1 to 4 is preferable, and an integer of 1 to 2 is more preferable). G is a monovalent group derived from the above-described π-conjugated branched compound.

側鎖に樹状分岐を有するπ共役系高分子としては、以下の（ｐ−１）〜（ｐ−１７）の繰り返し単位を有するものが具体例として挙げられる。なお、式中のｔ及びｕは上記と同義であり、側鎖に樹状分岐を有するπ共役系高分子は、以下の各化学式における＊と＊の間の構造が繰り返していることを意味する（以下同様）。
Specific examples of the π-conjugated polymer having a dendritic branch in the side chain include those having the following repeating units (p-1) to (p-17). Note that t and u in the formula are as defined above, and a π-conjugated polymer having a dendritic branch in the side chain means that the structure between * and * in the following chemical formulas is repeated. (The same applies hereinafter).

側鎖に樹状分岐を有するπ共役系高分子は、主鎖を形成する単量体に側鎖であるπ共役系樹状分岐化合物を結合させた後、当該単量体を重合することにより合成でき、主鎖であるπ共役系高分子を重合した後に、側鎖であるπ共役系樹状分岐化合物を結合させることによっても合成することができる。 A π-conjugated polymer having a dendritic branch in the side chain is obtained by bonding the π-conjugated dendritic compound, which is a side chain, to the monomer that forms the main chain, and then polymerizing the monomer. It can also be synthesized by polymerizing a π-conjugated polymer that is a main chain and then bonding a π-conjugated dendritic compound that is a side chain.

この場合に適用できる合成法としては、以下の（１）〜（６）の合成法が代表的である（Ｇ、ｑ、Ａｒ、Ａｒ’については一般式（２ａ）及び（２ｂ）におけるのと同様である。）。なお、（１）〜（６）の合成法における単量体のＡｒ又はＡｒ’にはあらかじめＧがｑ個結合していてもよく、重合後のＡｒ又はＡｒ’にＧをｑ個結合させてもよい。
（１）ハロゲン化メチル基を２以上有する化合物の脱ハロゲン化水素法による重縮合
Typical synthetic methods applicable in this case are the following synthetic methods (1) to (6) (G, q, Ar, and Ar ′ are the same as those in the general formulas (2a) and (2b)). The same). In addition, q G may be bonded in advance to the monomer Ar or Ar ′ in the synthesis methods (1) to (6), and q G is bonded to Ar or Ar ′ after polymerization. Also good.
(1) Polycondensation of compounds having two or more halogenated methyl groups by the dehydrohalogenation method

（２）アルデヒド基を有する化合物とホスホニウム基を有する化合物とのWittig反応による重合
(2) Polymerization by Wittig reaction of a compound having an aldehyde group and a compound having a phosphonium group

（３）アルデヒド基を有する化合物とアセトニトリル基を有する化合物とのKnoevenagel反応による重合
(3) Polymerization of a compound having an aldehyde group and a compound having an acetonitrile group by the Knoevenagel reaction

（４）Suzukiカップリング反応により重合する方法
(4) Polymerization method by Suzuki coupling reaction

（５）酸化剤により重合する方法
(5) Method of polymerizing with an oxidizing agent

（６）Ｎｉ触媒により重合する方法
(6) Method of polymerizing with Ni catalyst

上述した、側鎖に樹状分岐を有するπ共役系高分子は、有機薄膜素子に用いることができる。例えば、互いに対向して配置されている２つの電極間に、１又は２以上の有機層を備える有機ＥＬ素子において、有機層の少なくとも１つとして、このπ共役系高分子からなる層を適用できる。この有機ＥＬ素子においては、π共役系高分子からなる層が発光層又は電荷輸送層として機能する。有機ＥＬ素子と同様の構成は、太陽電池にも採用可能である。 The above-described π-conjugated polymer having a dendritic branch in the side chain can be used for an organic thin film element. For example, in an organic EL device having one or more organic layers between two electrodes arranged opposite to each other, a layer made of this π-conjugated polymer can be applied as at least one of the organic layers. . In this organic EL element, a layer made of a π-conjugated polymer functions as a light emitting layer or a charge transport layer. A configuration similar to that of the organic EL element can also be adopted for a solar cell.

以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、化学式中のｒ及びｓは１以上の整数を意味する。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In the chemical formula, r and s mean an integer of 1 or more.

［側鎖化合物の合成］
（合成例１−１）
以下の反応スキームに従って側鎖化合物（ａ１−１）を合成した。
側鎖化合物（ａ１−１）：FT-IR(KBr) : 1347cm^-1(-B-)。
[Synthesis of side chain compounds]
(Synthesis Example 1-1)
A side chain compound (a1-1) was synthesized according to the following reaction scheme.
Side chain compound (a1-1): FT-IR (KBr): 1347 cm ^-1 (-B-).

（合成例１−２）
合成例１−１で得た側鎖化合物（ａ１−１）を用いて、以下の反応スキームに従って側鎖化合物（ａ１−２）を合成した。
側鎖化合物（ａ１−２）：FT-IR(KBr) : 1358cm^-1(-B-)。
(Synthesis Example 1-2)
Using the side chain compound (a1-1) obtained in Synthesis Example 1-1, a side chain compound (a1-2) was synthesized according to the following reaction scheme.
Side chain compound (a1-2): FT-IR (KBr): 1358 cm ^-1 (-B-).

（合成例１−３）
合成例１−２で得た側鎖化合物（ａ１−２）を用いて、以下の反応スキームに従って、中間体（ｂ１）を経由して、側鎖化合物（ａ１−３）を合成した。
中間体（ｂ１）：¹H NMR : δ= 7.92 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.77 (s, 7H, ArH), 7.60 (d, 8H, ArH), 7.28 (d, 8H, ArH), 7.28 (d, 8H, ArH), 2.42 (s, 12H,CH₃), 0.37 (s, 9,CH₃),
側鎖化合物（ａ１−３）：FT-IR(KBr) : 1376cm^-1(-B-)。 (Synthesis Example 1-3)
Using the side chain compound (a1-2) obtained in Synthesis Example 1-2, a side chain compound (a1-3) was synthesized via an intermediate (b1) according to the following reaction scheme.
Intermediate (b1): ¹ H NMR: δ = 7.92 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.77 (s, 7H, ArH), 7.60 (d, 8H, ArH), 7.28 ( d, 8H, ArH), 7.28 (d, 8H, ArH), 2.42 (s, 12H, CH ₃ ), 0.37 (s, 9, CH ₃ ),
Side chain compound (a1-3): FT-IR (KBr): 1376 cm ^-1 (-B-).

（合成例２−１）
以下の反応スキームに従って側鎖化合物（ａ２−１）を合成した。
側鎖化合物（ａ２−１）：FT-IR(KBr) : 1347cm^-1(-B-)。
(Synthesis Example 2-1)
A side chain compound (a2-1) was synthesized according to the following reaction scheme.
Side chain compound (a2-1): FT-IR (KBr): 1347 cm ^-1 (-B-).

（合成例２−２）
合成例２−１で得た側鎖化合物（ａ２−１）を用いて、以下の反応スキームに従って側鎖化合物（ａ２−２）を合成した。
側鎖化合物（ａ２−２）：FT-IR(KBr) : 1358cm^-1(-B-)。
(Synthesis Example 2-2)
The side chain compound (a2-2) was synthesized according to the following reaction scheme using the side chain compound (a2-1) obtained in Synthesis Example 2-1.
Side chain compound (a2-2): FT-IR (KBr): 1358 cm ^-1 (-B-).

（合成例２−３）
合成例２−２で得た側鎖化合物（ａ２−２）を用いて、以下の反応スキームに従って、中間体（ｂ２）を経由して、側鎖化合物（ａ２−３）を合成した。
中間体（ｂ２）：¹H NMR : δ= 7.92 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.77 (s, 7H, ArH), 7.60 (d, 8H, ArH), 7.28 (d, 8H, ArH), 7.28 (d, 8H, ArH), 2.23 (s, 8H,CH₂), 1.24-1.50 (m, 80H, CH₂), 0.86 (t, 12H, CH₃) 0.37 (s, 9,CH₃),
側鎖化合物（ａ２−３）：FT-IR(KBr) : 1376cm^-1(-B-)。 (Synthesis Example 2-3)
Using the side chain compound (a2-2) obtained in Synthesis Example 2-2, a side chain compound (a2-3) was synthesized via an intermediate (b2) according to the following reaction scheme.
Intermediate (b2): ¹ H NMR: δ = 7.92 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.77 (s, 7H, ArH), 7.60 (d, 8H, ArH), 7.28 ( d, 8H, ArH), 7.28 (d, 8H, ArH), 2.23 (s, 8H, CH ₂ ), 1.24-1.50 (m, 80H, CH ₂ ), 0.86 (t, 12H, CH ₃ ) 0.37 (s , 9, CH ₃ ),
Side chain compound (a2-3): FT-IR (KBr): 1376 cm ^-1 (-B-).

（合成例３−１）
以下の反応スキームに従って側鎖化合物（ａ３−１）を合成した。
側鎖化合物（ａ３−１）：FT-IR(KBr) : 1347cm^-1(-B-)。
(Synthesis Example 3-1)
A side chain compound (a3-1) was synthesized according to the following reaction scheme.
Side chain compound (a3-1): FT-IR (KBr): 1347 cm ^-1 (-B-).

（合成例３−２）
合成例３−１で得た側鎖化合物（ａ３−１）を用いて、以下の反応スキームに従って側鎖化合物（ａ３−２）を合成した。
側鎖化合物（ａ３−２）：FT-IR(KBr) : 1358cm^-1(-B-)。
(Synthesis Example 3-2)
The side chain compound (a3-2) was synthesized according to the following reaction scheme using the side chain compound (a3-1) obtained in Synthesis Example 3-1.
Side chain compound (a3-2): FT-IR (KBr): 1358 cm ^-1 (-B-).

（合成例３−３）
合成例３−２で得た側鎖化合物（ａ３−２）を用いて、以下の反応スキームに従って、中間体（ｂ３）を経由して、側鎖化合物（ａ３−３）を合成した。
中間体（ｂ３）：¹H NMR : δ= 7.92 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.77 (s, 7H, ArH), 7.60 (d, 8H, ArH), 7.28 (d, 8H, ArH), 7.28 (d, 8H, ArH), 1.58 (s, 36H,CH₃), 0.37 (s, 9,CH₃),
側鎖化合物（ａ３−３）：FT-IR(KBr) : 1376cm^-1(-B-)。 (Synthesis Example 3-3)
Using the side chain compound (a3-2) obtained in Synthesis Example 3-2, a side chain compound (a3-3) was synthesized via an intermediate (b3) according to the following reaction scheme.
Intermediate (b3): ¹ H NMR: δ = 7.92 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.77 (s, 7H, ArH), 7.60 (d, 8H, ArH), 7.28 ( d, 8H, ArH), 7.28 (d, 8H, ArH), 1.58 (s, 36H, CH ₃ ), 0.37 (s, 9, CH ₃ ),
Side chain compound (a3-3): FT-IR (KBr): 1376 cm ^-1 (-B-).

［π共役系高分子の合成］
（比較例１−１）
合成例１−１で合成した側鎖化合物（ａ１−１）を用いて、以下の反応スキームに従って、中間体（ｃ１−１）、（ｄ１−１）を経由して、第０世代樹状分岐化合物（樹状分岐化合物のコアユニットのみからなる化合物）を側鎖に有したπ共役系高分子（ＰＰＶ０−１）を合成した。なお、中間体（ｄ１−１）からπ共役系高分子（ＰＰＶ０−１）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ１−１）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ０−１）を得た。
中間体（ｃ１−１）： ¹H NMR : δ= 8.03 (d, 2H, ArH), 7.22 (s, 4H, ArH), 3.93 (s, 3H, COOCH₃) 3.68 (s, 3H, COOCH₃), 2.40 (s, 3H, CH₃); ¹³C NMR : δ= 168.7 , 166.3 , 142.4 , 137.5 , 137.3 , 134.9 , 132.4 , 131.8 , 129.7 , 130.0 , 129.0 , 128.2 , 127.9 , 52.4 , 52.2 , 21.2。
中間体（ｄ１−１）： ¹H NMR: δ= 7.53 (d, 1H, ArH), 7.40 (d, 1H, ArH), 7.30 (d, 3H, ArH), 7.25 (d, 1H, ArH), 7.24 (s, 1H, ArH), 4.59 (s, 2H, -CH₂-), 4.52 (s, 2H, -CH₂-), 2.41 (s, 3H, CH₃); ¹³C NMR : δ=142.5 , 137.7 , 137.5 , 136.7 , 135.2 , 131.0 , 130.5 , 129.1 , 129.0 , 127.8 , 45.7 , 44.0 , 21.2。
π共役系高分子（ＰＰＶ０−１）：溶媒に不溶であったため、NMRやGPCによる分析は行わなかった。 [Synthesis of π-conjugated polymers]
(Comparative Example 1-1)
Using the side chain compound (a1-1) synthesized in Synthesis Example 1-1, the 0th generation dendritic branch via intermediates (c1-1) and (d1-1) according to the following reaction scheme A π-conjugated polymer (PPV0-1) having a compound (compound consisting only of a core unit of a dendritic branched compound) in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV0-1) from the intermediate (d1-1) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d1-1) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV0-1).
Intermediate (c1-1): ¹ H NMR: δ = 8.03 (d, 2H, ArH), 7.22 (s, 4H, ArH), 3.93 (s, 3H, COOCH ₃ ) 3.68 (s, 3H, COOCH ₃ ) , 2.40 (s, 3H, CH ₃ ); ¹³ C NMR: δ = 168.7, 166.3, 142.4, 137.5, 137.3, 134.9, 132.4, 131.8, 129.7, 130.0, 129.0, 128.2, 127.9, 52.4, 52.2, 21.2.
Intermediate (d1-1): ¹ H NMR: δ = 7.53 (d, 1H, ArH), 7.40 (d, 1H, ArH), 7.30 (d, 3H, ArH), 7.25 (d, 1H, ArH), 7.24 (s, 1H, ArH), 4.59 (s, 2H, -CH _2- ), 4.52 (s, 2H, -CH _2- ), 2.41 (s, 3H, CH ₃ ); ¹³ C NMR: δ = 142.5 , 137.7, 137.5, 136.7, 135.2, 131.0, 130.5, 129.1, 129.0, 127.8, 45.7, 44.0, 21.2.
π-conjugated polymer (PPV0-1): Since it was insoluble in the solvent, analysis by NMR or GPC was not performed.

（実施例１−１）
合成例１−２で合成した側鎖化合物（ａ１−２）を用いて、以下の反応スキームに従って、中間体（ｃ１−２）、（ｄ１−２）を経由して、第１世代樹状分岐化合物を側鎖に有したπ共役系高分子（ＰＰＶ１−１）を合成した。なお、中間体（ｄ１−２）からπ共役系高分子（ＰＰＶ１−１）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ１−２）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ１−１）を得た。
中間体（ｃ１−２）： FT-IR(KBr) : 1725cm^-1(-COOCH₃); ¹H NMR: δ=8.17 (s, 1H, ArH), 8.15 (d, 1H, ArH), 7.88 (d , 1H, ArH), 7.80 (s, 1H, ArH), 7.57 (d, 4H, ArH), 7.50 (s, 2H, ArH), 7.28 (d, 4H, ArH), 3.95 (s, 3H, -COOCH₃), 3.66 (s, 3H, -COOCH₃), 2.41 (s, 6H, CH₃)。
中間体（ｄ１−２）： ¹H NMR: δ= 7.82 (s, 1H, ArH), 7.59 (d, 4H, ArH), 7.58 (s, 2H, ArH), 7.57 (s, 1H, ArH), 7.41 (d , 2H, ArH), 7.27 (d, 4H, ArH), 4.62 (s, 1H, -CH₂-), 4.61 (s, 1H, -CH₂-), 2.41 (s, 6H, CH₃); ¹³C NMR: δ=141.8 , 140.5 , 137.9 , 137.5 , 135.3 , 131.1 , 130.4 , 129.6 , 128.2 , 127.2 , 126.4 , 125.0 , 45.6 , 44.1 , 21.1。
π共役系高分子（ＰＰＶ１−１）： ¹H NMR: δ= 7.48~7.76 (m, 9H, ArH), 7.13~7.18 (m, 8H, ArH), 2.35 (s, 6H, CH₃); ¹³C NMR: δ=129.5 , 127.1 , 77.3 , 77.0 , 76.7 , 21.1; GPC (THF): Mw39000 , PDI=4.00; DSC: Tg = 187^oC. UV-Vis (CH₂Cl₂): 260 and 423nm。 (Example 1-1)
Using the side chain compound (a1-2) synthesized in Synthesis Example 1-2, the first generation dendritic branch via intermediates (c1-2) and (d1-2) according to the following reaction scheme A π-conjugated polymer (PPV1-1) having a compound in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV1-1) from the intermediate (d1-2) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d1-2) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV1-1).
Intermediate (c1-2): FT-IR (KBr): 1725 cm ⁻¹ (—COOCH ₃ ); ¹ H NMR: δ = 8.17 (s, 1H, ArH), 8.15 (d, 1H, ArH), 7.88 ( d, 1H, ArH), 7.80 (s, 1H, ArH), 7.57 (d, 4H, ArH), 7.50 (s, 2H, ArH), 7.28 (d, 4H, ArH), 3.95 (s, 3H,- COOCH ₃ ), 3.66 (s, 3H, -COOCH ₃ ), 2.41 (s, 6H, CH ₃ ).
Intermediate (d1-2): ¹ H NMR: δ = 7.82 (s, 1H, ArH), 7.59 (d, 4H, ArH), 7.58 (s, 2H, ArH), 7.57 (s, 1H, ArH), 7.41 (d, 2H, ArH), 7.27 (d, 4H, ArH), 4.62 (s, 1H, -CH _2- ), 4.61 (s, 1H, -CH _2- ), 2.41 (s, 6H, CH ₃ ); ¹³ C NMR: δ = 141.8, 140.5, 137.9, 137.5, 135.3, 131.1, 130.4, 129.6, 128.2, 127.2, 126.4, 125.0, 45.6, 44.1, 21.1.
π-conjugated polymer (PPV1-1): ¹ H NMR: δ = 7.48-7.76 (m, 9H, ArH), 7.13-7.18 (m, 8H, ArH), 2.35 (s, 6H, CH ₃ ); ¹³ C NMR: δ = 129.5, 127.1, 77.3, 77.0, 76.7, 21.1; GPC (THF): Mw39000, PDI = 4.00; DSC: Tg = 187 ^° C. UV-Vis (CH ₂ Cl ₂ ): 260 and 423 nm.

（実施例１−２）
合成例１−３で合成した側鎖化合物（ａ１−３）を用いて、以下の反応スキームに従って、中間体（ｃ１−３）、（ｄ１−３）を経由して、第２世代樹状分岐化合物を側鎖に有したπ共役系高分子（ＰＰＶ２−１）を合成した。なお、中間体（ｄ１−３）からπ共役系高分子（ＰＰＶ２−１）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ１−３）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ２−１）を得た。
中間体（ｃ１−３）： FT-IR(KBr) : 1727cm^-1(-COOCH₃); ¹H NMR: δ= 8.20 (s, 1H, ArH), 8.17 (d, 1H, ArH), 8.00 (s, 1H, ArH), 7.92 (d, 1H, ArH), 7.83 (s, 4H, ArH), 7.79 (s, 2H, ArH), 7.66 (s, 2H, ArH), 7.60 (d, 8H, ArH), 7.28 (d, 8H, ArH), 3.94 (s, 3H, -COOCH₃), 3.70(s, 3H, -COOCH₃), 2.41 (s, 12H, CH₃)。
中間体（ｄ１−３）： ¹H NMR: δ= 7.96 (s, 1H, ArH), 7.78 (s, 4H, ArH), 7.71 (s, 2H, ArH), 7.70 (d, 2H, ArH), 7.52 (d, 8H, ArH), 7.83 (s, 2H, ArH), 7.18 (d, 8H, ArH), 6.89 (s, 1H, ArH), 4.56 (s, 1H, -CH₂-), 4.53 (s, 1H, -CH₂-), 2.31 (s, 12H, CH₃)。
π共役系高分子（ＰＰＶ２−１）： ¹H NMR: δ= 7.37~7.74 (m, 18H, ArH), 7.11 (m, 10H, ArH), 2.26 (s, 12H, CH₃); GPC(THF): Mw160000 , PDI=3.21; DSC: Tg = 223 ^oC. UV-Vis (CH₂Cl₂): 260 and 420nm。 (Example 1-2)
Using the side chain compound (a1-3) synthesized in Synthesis Example 1-3, the second generation dendritic branch via intermediates (c1-3) and (d1-3) according to the following reaction scheme A π-conjugated polymer (PPV2-1) having a compound in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV2-1) from the intermediate (d1-3) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d1-3) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV2-1).
Intermediate (c1-3): FT-IR (KBr): 1727 cm ^-1 (-COOCH ₃ ); ¹ H NMR: δ = 8.20 (s, 1H, ArH), 8.17 (d, 1H, ArH), 8.00 ( s, 1H, ArH), 7.92 (d, 1H, ArH), 7.83 (s, 4H, ArH), 7.79 (s, 2H, ArH), 7.66 (s, 2H, ArH), 7.60 (d, 8H, ArH ), 7.28 (d, 8H, ArH), 3.94 (s, 3H, -COOCH ₃ ), 3.70 (s, 3H, -COOCH ₃ ), 2.41 (s, 12H, CH ₃ ).
Intermediate (d1-3): ¹ H NMR: δ = 7.96 (s, 1H, ArH), 7.78 (s, 4H, ArH), 7.71 (s, 2H, ArH), 7.70 (d, 2H, ArH), 7.52 (d, 8H, ArH), 7.83 (s, 2H, ArH), 7.18 (d, 8H, ArH), 6.89 (s, 1H, ArH), 4.56 (s, 1H, -CH _2- ), 4.53 ( s, 1H, -CH _2- ), 2.31 (s, 12H, CH ₃ ).
π-conjugated polymer (PPV2-1): ¹ H NMR: δ = 7.37-7.74 (m, 18H, ArH), 7.11 (m, 10H, ArH), 2.26 (s, 12H, CH ₃ ); GPC (THF ): Mw160000, PDI = 3.21; DSC: Tg = 223 ^° C. UV-Vis (CH ₂ Cl ₂ ): 260 and 420 nm.

（比較例１−２）
合成例２−１で合成した側鎖化合物（ａ２−１）を用いて、以下の反応スキームに従って、中間体（ｃ２−１）、（ｄ２−１）を経由して、第０世代樹状分岐化合物（樹状分岐化合物のコアユニットのみからなる化合物）を側鎖に有したπ共役系高分子（ＰＰＶ０−２）を合成した。なお、中間体（ｄ２−１）からπ共役系高分子（ＰＰＶ０−２）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ２−１）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ０−２）を得た。
中間体（ｃ２−１）： ¹H NMR : δ= 8.03 (d, 2H, ArH), 7.22 (s, 4H, ArH), 3.93 (s, 3H, COOCH₃) 3.68 (s, 3H, COOCH₃), 2.24 (m, 2H, CH₂), 1.24-1.45 (m, 20H, CH₂), 0.98 (t, 3H, CH₃); ¹³C NMR : δ= 168.7 , 166.3 , 142.4 , 137.5 , 137.3 , 134.9 , 132.4 , 131.8 , 129.7 , 130.0 , 129.0 , 128.2 , 127.9 , 52.4 , 52.2 , 21.2。
中間体（ｄ２−１）： ¹H NMR: δ= 7.53 (d, 1H, ArH), 7.40 (d, 1H, ArH), 7.30 (d, 3H, ArH), 7.25 (d, 1H, ArH), 7.24 (s, 1H, ArH), 4.59 (s, 2H, -CH₂-), 4.52 (s, 2H, -CH₂-), 2.25 (m, 2H, CH₂), 1.24-1.48 (m, 20H, CH₂), 0.98 (t, 3H, CH₃); ¹³C NMR : δ=142.5 , 137.7 , 137.5 , 136.7 , 135.2 , 131.0 , 130.5 , 129.1 , 129.0 , 127.8 , 45.7 , 44.0 , 21.2。
π共役系高分子（ＰＰＶ0−2）： ¹H NMR: δ= 7.48~7.76 (m, 5H, ArH), 7.13~7.18 (m, 4H, ArH), 2.22 (b, 2H, CH₂), 1.20-1.40 (b, 20H, CH₂), 0.98 (b, 3H, CH₃); ¹³C NMR: δ=129.5 , 127.1 , 77.3 , 77.0 , 76.7 , 21.1; GPC (THF): Mw40000 , PDI=4.00; DSC: Tg = 50^oC. UV-Vis (CH₂Cl₂): 260 and 423nm。
(Comparative Example 1-2)
Using the side chain compound (a2-1) synthesized in Synthesis Example 2-1, the 0th generation dendritic branch via intermediates (c2-1) and (d2-1) according to the following reaction scheme A π-conjugated polymer (PPV0-2) having a compound (comprising only a core unit of a dendritic branched compound) in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV0-2) from the intermediate (d2-1) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d2-1) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained the (pi) conjugated polymer (PPV0-2).
Intermediate (c2-1): ¹ H NMR: δ = 8.03 (d, 2H, ArH), 7.22 (s, 4H, ArH), 3.93 (s, 3H, COOCH ₃ ) 3.68 (s, 3H, COOCH ₃ ) , 2.24 (m, 2H, CH ₂ ), 1.24-1.45 (m, 20H, CH ₂ ), 0.98 (t, 3H, CH ₃ ); ¹³ C NMR: δ = 168.7, 166.3, 142.4, 137.5, 137.3, 134.9 , 132.4, 131.8, 129.7, 130.0, 129.0, 128.2, 127.9, 52.4, 52.2, 21.2.
Intermediate (d2-1): ¹ H NMR: δ = 7.53 (d, 1H, ArH), 7.40 (d, 1H, ArH), 7.30 (d, 3H, ArH), 7.25 (d, 1H, ArH), 7.24 (s, 1H, ArH), 4.59 (s, 2H, -CH _2- ), 4.52 (s, 2H, -CH _2- ), 2.25 (m, 2H, CH ₂ ), 1.24-1.48 (m, 20H , CH ₂ ), 0.98 (t, 3H, CH ₃ ); ¹³ C NMR: δ = 142.5, 137.7, 137.5, 136.7, 135.2, 131.0, 130.5, 129.1, 129.0, 127.8, 45.7, 44.0, 21.2.
π-conjugated polymer (PPV0-2): ¹ H NMR: δ = 7.48-7.76 (m, 5H, ArH), 7.13-7.18 (m, 4H, ArH), 2.22 (b, 2H, CH ₂ ), 1.20 -1.40 (b, 20H, CH ₂ ), 0.98 (b, 3H, CH ₃ ); ¹³ C NMR: δ = 129.5, 127.1, 77.3, 77.0, 76.7, 21.1; GPC (THF): Mw40000, PDI = 4.00; DSC: Tg = 50 ^° C. UV-Vis (CH ₂ Cl ₂ ): 260 and 423 nm.

（実施例１−３）
合成例２−２で合成した側鎖化合物（ａ２−２）を用いて、以下の反応スキームに従って、中間体（ｃ２−２）、（ｄ２−２）を経由して、第１世代樹状分岐化合物を側鎖に有したπ共役系高分子（ＰＰＶ１−２）を合成した。なお、中間体（ｄ２−２）からπ共役系高分子（ＰＰＶ１−２）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ２−２）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ１−２）を得た。
中間体（ｃ２−２）： FT-IR(KBr) : 1725cm^-1(-COOCH₃); ¹H NMR: δ=8.17 (s, 1H, ArH), 8.15 (d, 1H, ArH), 7.88 (d , 1H, ArH), 7.80 (s, 1H, ArH), 7.57 (d, 4H, ArH), 7.50 (s, 2H, ArH), 7.28 (d, 4H, ArH), 3.95 (s, 3H, -COOCH₃), 3.66 (s, 3H, -COOCH₃), 2.25 (m, 4H, CH₂), 1.22-1.54 (m, 40H, CH₂), 0.99 (t, 6H, CH₃)。
中間体（ｄ２−２）： ¹H NMR: δ= 7.82 (s, 1H, ArH), 7.59 (d, 4H, ArH), 7.58 (s, 2H, ArH), 7.57 (s, 1H, ArH), 7.41 (d , 2H, ArH), 7.27 (d, 4H, ArH), 4.62 (s, 1H, -CH₂-), 4.61 (s, 1H, -CH₂-), 2.24 (m, 4H, CH₂), 1.24-1.48 (m, 40H, CH₂), 0.98 (t, 12H, CH₃); ¹³C NMR: δ=141.8 , 140.5 , 137.9 , 137.5 , 135.3 , 131.1 , 130.4 , 129.6 , 128.2 , 127.2 , 126.4 , 125.0 , 45.6 , 44.1 , 21.1。
π共役系高分子（ＰＰＶ１−２）： ¹H NMR: δ= 7.48〜7.76 (m, 9H, ArH), 7.13~7.18 (m, 8H, ArH), 2.22 (b, 4H, CH₂), 1.22-1.50 (m, 40H, CH₂), 0.95 (t, 12H, CH₃); ¹³C NMR: δ=129.5 , 127.1 , 77.3 , 77.0 , 76.7 , 21.1; GPC (THF): Mw80000。 (Example 1-3)
Using the side chain compound (a2-2) synthesized in Synthesis Example 2-2, the first generation dendritic branch via intermediates (c2-2) and (d2-2) according to the following reaction scheme A π-conjugated polymer (PPV1-2) having a compound in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV1-2) from the intermediate (d2-2) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d2-2) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV1-2).
Intermediate (c2-2): FT-IR (KBr): 1725 cm ⁻¹ (—COOCH ₃ ); ¹ H NMR: δ = 8.17 (s, 1H, ArH), 8.15 (d, 1H, ArH), 7.88 ( d, 1H, ArH), 7.80 (s, 1H, ArH), 7.57 (d, 4H, ArH), 7.50 (s, 2H, ArH), 7.28 (d, 4H, ArH), 3.95 (s, 3H,- _{COOCH 3), 3.66 (s,} 3H, -COOCH 3), 2.25 (m, 4H, CH 2), 1.22-1.54 (m, 40H, CH 2), 0.99 (t, 6H, CH 3).
Intermediate (d2-2): ¹ H NMR: δ = 7.82 (s, 1H, ArH), 7.59 (d, 4H, ArH), 7.58 (s, 2H, ArH), 7.57 (s, 1H, ArH), 7.41 (d, 2H, ArH), 7.27 (d, 4H, ArH), 4.62 (s, 1H, -CH _2- ), 4.61 (s, 1H, -CH _2- ), 2.24 (m, 4H, CH ₂ ), 1.24-1.48 (m, 40H, CH ₂ ), 0.98 (t, 12H, CH ₃ ); ¹³ C NMR: δ = 141.8, 140.5, 137.9, 137.5, 135.3, 131.1, 130.4, 129.6, 128.2, 127.2, 126.4, 125.0, 45.6, 44.1, 21.1.
π-conjugated polymer (PPV1-2): ¹ H NMR: δ = 7.48-7.76 (m, 9H, ArH), 7.13-7.18 (m, 8H, ArH), 2.22 (b, 4H, CH ₂ ), 1.22 -1.50 (m, 40H, CH ₂ ), 0.95 (t, 12H, CH ₃ ); ¹³ C NMR: δ = 129.5, 127.1, 77.3, 77.0, 76.7, 21.1; GPC (THF): Mw80000.

（実施例１−４）
合成例２−３で合成した側鎖化合物（ａ２−３）を用いて、以下の反応スキームに従って、中間体（ｃ２−３）、（ｄ２−３）を経由して、第２世代樹状分岐化合物を側鎖に有したπ共役系高分子（ＰＰＶ２−２）を合成した。なお、中間体（ｄ２−３）からπ共役系高分子（ＰＰＶ２−２）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ２−３）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ２−２）を得た。
中間体（ｃ２−３）： FT-IR(KBr) : 1727cm^-1(-COOCH₃); ¹H NMR: δ= 8.20 (s, 1H, ArH), 8.17 (d, 1H, ArH), 8.00 (s, 1H, ArH), 7.92 (d, 1H, ArH), 7.83 (s, 4H, ArH), 7.79 (s, 2H, ArH), 7.66 (s, 2H, ArH), 7.60 (d, 8H, ArH), 7.28 (d, 8H, ArH), 3.94 (s, 3H, -COOCH₃), 3.70(s, 3H, -COOCH₃), 2.25 (m, 8H, CH₂), 1.24-1.48 (m, 80H, CH₂), 0.98 (t, 12H, CH₃)。
中間体（ｄ２−３）： ¹H NMR: δ= 7.96 (s, 1H, ArH), 7.78 (s, 4H, ArH), 7.71 (s, 2H, ArH), 7.70 (d, 2H, ArH), 7.52 (d, 8H, ArH), 7.83 (s, 2H, ArH), 7.18 (d, 8H, ArH), 6.89 (s, 1H, ArH), 4.56 (s, 1H, -CH₂-), 4.53 (s, 1H, -CH₂-), 2.24 (m, 8H, CH₂), 1.22-1.45 (m, 80H, CH₂), 0.98 (t, 12H, CH₃)。
π共役系高分子（ＰＰＶ２−２）： ¹H NMR: δ= 7.37〜7.74 (m, 18H, ArH), 7.11 (m, 10H, ArH), 2.24 (b, 8H, CH₂), 1.22-1.45 (m, 80H, CH₂), 0.98 (b, 12H, CH₃) ; GPC (THF): Mw120000。 (Example 1-4)
Using the side chain compound (a2-3) synthesized in Synthesis Example 2-3, the second generation dendritic branch via intermediates (c2-3) and (d2-3) according to the following reaction scheme A π-conjugated polymer (PPV2-2) having a compound in the side chain was synthesized. The polymerization of the intermediate (d2-3) to the π-conjugated polymer (PPV2-2) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d2-3) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV2-2).
Intermediate (c2-3): FT-IR (KBr): 1727 cm ^-1 (-COOCH ₃ ); ¹ H NMR: δ = 8.20 (s, 1H, ArH), 8.17 (d, 1H, ArH), 8.00 ( s, 1H, ArH), 7.92 (d, 1H, ArH), 7.83 (s, 4H, ArH), 7.79 (s, 2H, ArH), 7.66 (s, 2H, ArH), 7.60 (d, 8H, ArH ), 7.28 (d, 8H, ArH), 3.94 (s, 3H, -COOCH ₃ ), 3.70 (s, 3H, -COOCH ₃ ), 2.25 (m, 8H, CH ₂ ), 1.24-1.48 (m, 80H , CH ₂ ), 0.98 (t, 12H, CH ₃ ).
Intermediate (d2-3): ¹ H NMR: δ = 7.96 (s, 1H, ArH), 7.78 (s, 4H, ArH), 7.71 (s, 2H, ArH), 7.70 (d, 2H, ArH), 7.52 (d, 8H, ArH), 7.83 (s, 2H, ArH), 7.18 (d, 8H, ArH), 6.89 (s, 1H, ArH), 4.56 (s, 1H, -CH _2- ), 4.53 ( _{s, 1H, -CH 2 -)} , 2.24 (m, 8H, CH 2), 1.22-1.45 (m, 80H, CH 2), 0.98 (t, 12H, CH 3).
π-conjugated polymer (PPV2-2): ¹ H NMR: δ = 7.37-7.74 (m, 18H, ArH), 7.11 (m, 10H, ArH), 2.24 (b, 8H, CH ₂ ), 1.22-1.45 _{(m, 80H, CH 2)} , 0.98 (b, 12H, CH 3); GPC (THF): Mw120000.

（実施例１−５）
合成例３−３で合成した側鎖化合物（ａ３−３）を用いて、以下の反応スキームに従って、中間体（ｃ３−３）、（ｄ３−３）を経由して、第２世代樹状分岐化合物を側鎖に有したπ共役系高分子（ＰＰＶ２−３）を合成した。なお、中間体（ｄ３−３）からπ共役系高分子（ＰＰＶ２−３）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ３−３）をゆっくり滴下し、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ２−３）を得た。
中間体（ｃ３−３）： FT-IR(KBr) : 1727cm^-1(-COOCH₃); ¹H NMR: δ= 8.20 (s, 1H, ArH), 8.17 (d, 1H, ArH), 8.00 (s, 1H, ArH), 7.92 (d, 1H, ArH), 7.83 (s, 4H, ArH), 7.79 (s, 2H, ArH), 7.66 (s, 2H, ArH), 7.60 (d, 8H, ArH), 7.28 (d, 8H, ArH), 3.94 (s, 3H, -COOCH₃), 3.70(s, 3H, -COOCH₃), 1.58 (m, 36H, CH₃)。
中間体（ｄ３−３）： ¹H NMR: δ= 7.96 (s, 1H, ArH), 7.78 (s, 4H, ArH), 7.71 (s, 2H, ArH), 7.70 (d, 2H, ArH), 7.52 (d, 8H, ArH), 7.83 (s, 2H, ArH), 7.18 (d, 8H, ArH), 6.89 (s, 1H, ArH), 4.56 (s, 1H, -CH₂-), 4.53 (s, 1H, -CH₂-), 1.58 (m, 36H, CH₃)。
π共役系高分子（ＰＰＶ２−３）： ¹H NMR: δ= 7.37〜7.74 (m, 18H, ArH), 7.11 (m, 10H, ArH), 1.56 (br, 36H, CH₃); GPC (THF): Mw160000。 (Example 1-5)
Using the side chain compound (a3-3) synthesized in Synthesis Example 3-3, the second generation dendritic branch via intermediates (c3-3) and (d3-3) according to the following reaction scheme A π-conjugated polymer (PPV2-3) having a compound in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV2-3) from the intermediate (d3-3) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d3-3) dissolved in toluene was slowly added dropwise thereto, followed by stirring and refluxing under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV2-3).
Intermediate (c3-3): FT-IR (KBr): 1727 cm ^-1 (-COOCH ₃ ); ¹ H NMR: δ = 8.20 (s, 1H, ArH), 8.17 (d, 1H, ArH), 8.00 ( s, 1H, ArH), 7.92 (d, 1H, ArH), 7.83 (s, 4H, ArH), 7.79 (s, 2H, ArH), 7.66 (s, 2H, ArH), 7.60 (d, 8H, ArH ), 7.28 (d, 8H, ArH), 3.94 (s, 3H, -COOCH ₃ ), 3.70 (s, 3H, -COOCH ₃ ), 1.58 (m, 36H, CH ₃ ).
Intermediate (d3-3): ¹ H NMR: δ = 7.96 (s, 1H, ArH), 7.78 (s, 4H, ArH), 7.71 (s, 2H, ArH), 7.70 (d, 2H, ArH), 7.52 (d, 8H, ArH), 7.83 (s, 2H, ArH), 7.18 (d, 8H, ArH), 6.89 (s, 1H, ArH), 4.56 (s, 1H, -CH _2- ), 4.53 ( _{s, 1H, -CH 2 -)} , 1.58 (m, 36H, CH 3).
π-conjugated polymer (PPV2-3): ¹ H NMR: δ = 7.37-7.74 (m, 18H, ArH), 7.11 (m, 10H, ArH), 1.56 (br, 36H, CH ₃ ); GPC (THF ): Mw160000.

（実施例１−６）
合成例１−３で合成した側鎖化合物（ａ１−３）を用いて、以下の反応スキームに従って、中間体（ｃ１−３）、（ｄ１−３）を経由して、第２世代樹状分岐化合物を側鎖に有したπ共役系高分子（ＰＰＶ’２−１）を合成した。なお、中間体（ｄ１−３）からπ共役系高分子（ＰＰＶ’２−１）の重合は以下に従った。すなわち、KO-tBuと18-クラウン-6-エーテルをトルエンに溶解し、そこへトルエンに溶解させた中間体（ｄ１−３）及び下記反応スキームにおいて示す（ｄ’１−３）とをゆっくり滴下し（前者：後者は、モル比で１：１）、N₂下３時間攪拌還流した。そして、反応液をメタノールへ投入し、沈殿物をメタノールで洗浄し、乾燥しπ共役系高分子（ＰＰＶ’２−１）を得た。
中間体（ｃ１−３）： FT-IR(KBr)及び¹H NMRの結果は、実施例１−２と同様であった。
中間体（ｄ１−３）： ¹H NMRの結果は、実施例１−２と同様であった。
π共役系高分子（ＰＰＶ’２−１）： ¹H NMR: δ= 7.37〜7.74 (m, 22H, ArH), 7.11 (m, 10H, ArH), 3.48 (s, 6H, OCH₃), 2.26 (s, 12H, CH₃)GPC (THF): Mw80000。 (Example 1-6)
Using the side chain compound (a1-3) synthesized in Synthesis Example 1-3, the second generation dendritic branch via intermediates (c1-3) and (d1-3) according to the following reaction scheme A π-conjugated polymer (PPV′2-1) having a compound in the side chain was synthesized. The polymerization of the π-conjugated polymer (PPV′2-1) from the intermediate (d1-3) was as follows. That is, KO-tBu and 18-crown-6-ether were dissolved in toluene, and the intermediate (d1-3) dissolved in toluene and (d′ 1-3) shown in the following reaction scheme were slowly added dropwise. (The former: the latter was 1: 1 in molar ratio), and the mixture was stirred and refluxed under N _{2 for} 3 hours. And the reaction liquid was thrown into methanol, the deposit was wash | cleaned with methanol, and it dried and obtained (pi) conjugated polymer (PPV'2-1).
Intermediate (c1-3): The results of FT-IR (KBr) and ¹ H NMR were the same as in Example 1-2.
Intermediate (d1-3): The result of ¹ H NMR was the same as that of Example 1-2.
π-conjugated polymer (PPV′2-1): ¹ H NMR: δ = 7.37-7.74 (m, 22H, ArH), 7.11 (m, 10H, ArH), 3.48 (s, 6H, OCH ₃ ), 2.26 (s, 12H, CH ₃ ) GPC (THF): Mw80000.

［π共役系高分子の評価］
実施例１−２で得たＰＰＶ１−１と、実施例１−２で得たＰＰＶ２−１とについて、紫外／可視吸収スペクトル（ＵＶ／ＶＩＳ吸収スペクトル）を測定し、また、λex＝２８０ｎｍにおけるＰＬスペクトルを測定した。その結果を図５に示す。図５より、ＰＰＶ特有の４２３ｎｍ付近の吸収ピークとπ共役系樹状分岐化合物（デンドロン）由来の２８０ｎｍの吸収ピークが得られた。また、世代の上昇に伴って、２８０ｎｍにおけるデンドロン由来の吸収ピーク強度が増大している。このことから、ＰＰＶ側鎖にポリフェニレンデンドロンの導入を確認した。また、デンドロンの吸収ピークにおいて励起したところ、３８０ｎｍ付近のデンドロンの蛍光は見られずＰＰＶ主鎖からの蛍光しか観察されなかった。これは、デンドロンからＰＰＶへの高効率な分子内エネルギー移動によると考えられる。 [Evaluation of π-conjugated polymers]
An ultraviolet / visible absorption spectrum (UV / VIS absorption spectrum) was measured for PPV1-1 obtained in Example 1-2 and PPV2-1 obtained in Example 1-2, and PL at λex = 280 nm was measured. The spectrum was measured. The result is shown in FIG. From FIG. 5, an absorption peak near 423 nm peculiar to PPV and an absorption peak at 280 nm derived from the π-conjugated dendritic compound (dendron) were obtained. In addition, with the increase in generation, the absorption peak intensity derived from dendron at 280 nm increases. This confirmed the introduction of polyphenylene dendron into the PPV side chain. When excited at the absorption peak of dendron, no fluorescence of dendron near 380 nm was observed, and only fluorescence from the PPV main chain was observed. This is thought to be due to highly efficient intramolecular energy transfer from dendron to PPV.

また、ＰＰＶ１−１及びＰＰＶ２−１について、溶液（クロロホルム溶剤の１重量％溶液）及びフィルムの場合のλex＝２８０ｎｍにおけるＰＬスペクトルをそれぞれ比較した。ＰＰＶ１−１については図６にＰＰＶ２−１については図７にその結果を示す。 Moreover, about PPV1-1 and PPV2-1, the PL spectrum in (lambda) ex = 280nm in the case of a solution (1 weight% solution of chloroform solvent) and a film was compared, respectively. FIG. 6 shows the results for PPV1-1 and FIG. 7 shows the results for PPV2-1.

次に、比較例１−２で得たＰＰＶ０−２と、実施例１−３で得たＰＰＶ１−２と、実施例１−４で得たＰＰＶ２−２について、溶液（クロロホルム溶剤の１重量％溶液）及びフィルムの場合のＵＶ／ＶＩＳ吸収スペクトルを測定した。なお、ＰＰＶ０−２については合成後においてクロロホルムに対し可溶な部分のみを採取し、ＵＶ／ＶＩＳ吸収スペクトルを測定した。ＰＰＶ０−２とＰＰＶ１−２の結果を図８に、ＰＰＶ０−２とＰＰＶ２−２の結果を図９にそれぞれ示す。これらの図より、π共役系樹状分岐化合物（デンドロン）を持つＰＰＶ１−２及びＰＰＶ２−２は溶液内とほぼ同じ吸収スペクトルを示した。 Next, for PPV0-2 obtained in Comparative Example 1-2, PPV1-2 obtained in Example 1-3, and PPV2-2 obtained in Example 1-4, a solution (1 wt% of chloroform solvent) was used. UV / VIS absorption spectra for solution) and film were measured. For PPV0-2, only a portion soluble in chloroform after the synthesis was collected, and a UV / VIS absorption spectrum was measured. The results of PPV0-2 and PPV1-2 are shown in FIG. 8, and the results of PPV0-2 and PPV2-2 are shown in FIG. From these figures, PPV1-2 and PPV2-2 having a π-conjugated dendritic compound (dendron) showed almost the same absorption spectrum as in the solution.

また、ＰＰＶ０−２、ＰＰＶ１−２及びＰＰＶ２−２について、溶液（クロロホルム溶剤の１重量％溶液）及びフィルムの場合のλex＝２８０ｎｍにおけるＰＬスペクトルをそれぞれ比較した。ＰＰＶ０−２とＰＰＶ１−２については図１０に、ＰＰＶ０−２とＰＰＶ２−２については図１１にその結果を示す。これらの図より、世代の小さいＰＰＶ１−２では、溶液内でのピーク位置から約２０ｎｍ程度のシフトが見られるのに対し、２世代デンドロンを持つＰＰＶ２−２ではほとんどピークのシフトは見られなかった。このことから、立体障害の大きなデンドロンの導入によりフィルム内において主鎖間の相互作用が抑制されることが明らかとなった。また、デンドロンからの蛍光はフィルム内でも全く見られないことから、フィルム内においてもデンドロンからＰＰＶへのエネルギー移動が起こっていることがわかった。 Further, for PPV 0-2, PPV 1-2, and PPV 2-2, PL spectra at λex = 280 nm in the case of a solution (1 wt% solution of chloroform solvent) and a film were compared, respectively. The results are shown in FIG. 10 for PPV0-2 and PPV1-2, and in FIG. 11 for PPV0-2 and PPV2-2. From these figures, the PPV 1-2 with a small generation shows a shift of about 20 nm from the peak position in the solution, whereas the PPV 2-2 with the second generation dendron hardly shows a peak shift. . From this, it has been clarified that the introduction of dendron having a large steric hindrance suppresses the interaction between main chains in the film. Further, since no fluorescence from the dendron was observed in the film, it was found that energy transfer from the dendron to the PPV occurred in the film.

更に、ＰＰＶ１−２及びＰＰＶ２−２について、溶液（クロロホルム溶剤の１重量％溶液）及びフィルムの場合のλex＝４２０ｎｍにおけるＰＬスペクトルをそれぞれ比較した。ＰＰＶ１−２については図１２に、ＰＰＶ２−２については図１３にその結果を示す。これらの図より、デンドロンで励起した場合とほぼ同じスペクトルを与えたことから、ＰＰＶ主鎖間の相互作用は世代の高いデンドロンを導入することによって抑制されることがわかった。 Furthermore, for PPV1-2 and PPV2-2, the PL spectra at λex = 420 nm in the case of a solution (a 1% by weight solution of chloroform solvent) and a film were compared, respectively. The results are shown in FIG. 12 for PPV1-2 and in FIG. 13 for PPV2-2. From these figures, it was found that the interaction between PPV main chains was suppressed by introducing a high-generation dendron, since the spectrum was almost the same as that obtained when excited with dendron.

［溶解性及びＴｇ］
未置換ＰＰＶ（未置換のポリフェニレンビニレン）、ＭＥＨ−ＰＰＶ、比較例１−１で得られたＰＰＶ０−１、実施例１−１で得られたＰＰＶ１−１、実施例１−２で得られたＰＰＶ２−１について、これらの２重量％トルエン溶液を作製し、溶解性を評価した。また、これらのＴｇ（ガラス転移温度）をＤＳＣにより測定した。この結果を以下の表１に示す。なお、表１において、○は溶解性が良好であることを意味し、×は溶解性が悪いことを意味する。 [Solubility and Tg]
Unsubstituted PPV (unsubstituted polyphenylene vinylene), MEH-PPV, PPV 0-1 obtained in Comparative Example 1-1, PPV 1-1 obtained in Example 1-1, obtained in Example 1-2 About PPV2-1, these 2 weight% toluene solutions were produced and solubility was evaluated. Moreover, these Tg (glass transition temperature) was measured by DSC. The results are shown in Table 1 below. In Table 1, o means that the solubility is good, and x means that the solubility is poor.

［有機ＥＬ素子の作製］
（実施例２−１）
ガラス基板上にシート抵抗１５Ω／□のＩＴＯが形成されている基盤の上に、ＰＥＤＯＴ／ＰＳＳ（ポリエチレンジオキシチオフェン／ポリスチレンスルホン酸（商品名：バイトロンＰ、（株）バイエル社製））からなるホール注入層をスピンコートにより形成した（なお、シート抵抗（Ω／□）とは、「薄膜ハンドブック（オーム社刊）」p.896に記載の「表面抵抗」と同義であり、面状の抵抗体を正方形に切り出して対向する２辺間の抵抗で表したものを示す。この表面抵抗は、抵抗分布が一様ならば正方形の寸法に無関係である。以下同様）。得られたホール注入層の膜厚は４０ｎｍであった。次いで、ホール注入層の上に、実施例１−４で得たπ共役系高分子（ＰＰＶ２−２）からなる発光層をスピンコートにより形成した。スピンコートは、π共役系高分子（ＰＰＶ２−２）を２重量％含むトルエン溶液を用いて行い、得られた発光層の膜厚は７０ｎｍであった。次に、発光層の上に、陰極としてＣａを６ｎｍ、Ａｌを２５０ｎｍそれぞれ蒸着し、有機ＥＬ素子を得た。 [Production of organic EL element]
(Example 2-1)
It is made of PEDOT / PSS (polyethylenedioxythiophene / polystyrene sulfonic acid (trade name: Vitron P, manufactured by Bayer Co., Ltd.)) on a substrate on which ITO having a sheet resistance of 15Ω / □ is formed on a glass substrate. The hole injection layer was formed by spin coating (note that the sheet resistance (Ω / □) is synonymous with the “surface resistance” described in “Thin Film Handbook (Ohm Publishing Co., Ltd.)” p.896. The body is cut out into a square and represented by the resistance between two opposing sides, and the surface resistance is irrelevant to the dimensions of the square if the resistance distribution is uniform. The film thickness of the obtained hole injection layer was 40 nm. Next, a light emitting layer made of the π-conjugated polymer (PPV2-2) obtained in Example 1-4 was formed on the hole injection layer by spin coating. The spin coating was performed using a toluene solution containing 2% by weight of π-conjugated polymer (PPV2-2), and the resulting light emitting layer had a thickness of 70 nm. Next, 6 nm of Ca and 250 nm of Al were vapor-deposited as a cathode on the light emitting layer, respectively, and the organic EL element was obtained.

この有機ＥＬ素子の、電流密度１０ｍＡ／ｃｍ^２の輝度は４１３ｃｄ／ｍ^２であり、駆動電圧は３．８６Ｖであった。また、電流密度１０ｍＡ／ｃｍ^２の定電流駆動におけるこの輝度半減寿命は５００時間であった。 This organic EL device had a luminance of 413 cd / m ² at a current density of 10 mA / cm ² and a driving voltage of 3.86 V. In addition, the luminance half life in constant current driving at a current density of 10 mA / cm ² was 500 hours.

（比較例２−１）
発光層に比較例１−２で得たπ共役系高分子（ＰＰＶ０−２）を用いた他は、実施例２−１と同様にして、有機ＥＬ素子を作製した。この有機ＥＬ素子の、電流密度１０ｍＡ／ｃｍ^２の輝度は１８ｃｄ／ｍ^２であり、駆動電圧は５．５Ｖであった。また、電流密度１０ｍＡ／ｃｍ^２の定電流駆動におけるこの輝度半減寿命は２０時間であった。 (Comparative Example 2-1)
An organic EL device was produced in the same manner as in Example 2-1, except that the π-conjugated polymer (PPV0-2) obtained in Comparative Example 1-2 was used for the light emitting layer. This organic EL element had a luminance of 18 cd / m ² at a current density of 10 mA / cm ² and a drive voltage of 5.5V. The luminance half life in constant current driving at a current density of 10 mA / cm ² was 20 hours.

（比較例２−２）
発光層にＭＥＨ−ＰＰＶ（下記構造の化合物、Ｍｗ＝４０００００）を用いた他は、実施例２−１と同様にして、有機ＥＬ素子を作製した。この有機ＥＬ素子の、電流密度１０ｍＡ／ｃｍ^２の輝度は２００ｃｄ／ｍ^２であり、駆動電圧は４．５Ｖであった。また、電流密度１０ｍＡ／ｃｍ^２の定電流駆動におけるこの輝度半減寿命は２０時間であった。
(Comparative Example 2-2)
An organic EL device was produced in the same manner as in Example 2-1, except that MEH-PPV (compound having the following structure, Mw = 400000) was used for the light emitting layer. This organic EL element had a luminance of 200 cd / m ² at a current density of 10 mA / cm ² and a drive voltage of 4.5V. The luminance half life in constant current driving at a current density of 10 mA / cm ² was 20 hours.

（実施例２−２）
発光層として、π共役系高分子（ＰＰＶ２−２）に代えて実施例１−５で得たπ共役系高分子（ＰＰＶ２−３）を用い、ルブレンをπ共役系高分子（ＰＰＶ２−３）に対し５重量％添加した他は、実施例２−１と同様にして有機ＥＬ素子を作製した。この有機ＥＬ素子の、電流密度１０ｍＡ／ｃｍ^２の輝度は７００ｃｄ／ｍ^２であり、駆動電圧は４．２Ｖであった。また、電流密度１０ｍＡ／ｃｍ^２の定電流駆動におけるこの輝度半減寿命は８００時間であった。 (Example 2-2)
As the light emitting layer, the π-conjugated polymer (PPV2-3) obtained in Example 1-5 was used instead of the π-conjugated polymer (PPV2-2), and rubrene was replaced with the π-conjugated polymer (PPV2-3). An organic EL device was produced in the same manner as in Example 2-1, except that 5% by weight was added. The luminance of the organic EL element at a current density of 10 mA / cm ² was 700 cd / m ² and the driving voltage was 4.2V. The luminance half life in constant current driving at a current density of 10 mA / cm ² was 800 hours.

（比較例２−３）
発光層として、π共役系高分子（ＰＰＶ２−３）に代えて上記ＭＥＨ−ＰＰＶを用いた他は、実施例２−２と同様にして有機ＥＬ素子を作製した。この有機ＥＬ素子の、電流密度１０ｍＡ／ｃｍ^２の輝度は８０ｃｄ／ｍ^２であり、駆動電圧は４．５Ｖであった。また、電流密度１０ｍＡ／ｃｍ^２の定電流駆動におけるこの輝度半減寿命は２０時間であった。 (Comparative Example 2-3)
An organic EL device was produced in the same manner as in Example 2-2 except that the MEH-PPV was used instead of the π-conjugated polymer (PPV2-3) as the light emitting layer. This organic EL device had a luminance of 80 cd / m ² at a current density of 10 mA / cm ² and a drive voltage of 4.5V. The luminance half life in constant current driving at a current density of 10 mA / cm ² was 20 hours.

実施例２−２と比較例２−３の結果より、ＭＥＨ−ＰＰＶのように側鎖が単に長鎖アルコキシ基であると主鎖から発光ドーパントへのエネルギー移動又は電荷移動が妨げられてしまうが、側鎖が本発明のπ共役系樹状分岐化合物であると発光ドーパントへのエネルギー移動が充分に行えることが判明した。 From the results of Example 2-2 and Comparative Example 2-3, energy transfer or charge transfer from the main chain to the light-emitting dopant is hindered when the side chain is simply a long-chain alkoxy group like MEH-PPV. It has been found that the energy transfer to the light-emitting dopant can be sufficiently performed when the side chain is the π-conjugated dendritic compound of the present invention.

（実施例２−３）
発光層として、π共役系高分子（ＰＰＶ２−２）に代えて実施例１−６で得たπ共役系高分子（ＰＰＶ’２−１）を用いた他は、実施例２−１と同様にして有機ＥＬ素子を作製した。この有機ＥＬ素子の、電流密度１０ｍＡ／ｃｍ^２の輝度は４００ｃｄ／ｍ^２であり、駆動電圧は４．２Ｖであった。また、電流密度１０ｍＡ／ｃｍ^２の定電流駆動におけるこの輝度半減寿命は４００時間であった。 (Example 2-3)
Except for using the π-conjugated polymer (PPV′2-1) obtained in Example 1-6 in place of the π-conjugated polymer (PPV2-2) as the light emitting layer, the same as in Example 2-1. Thus, an organic EL element was produced. This organic EL element had a luminance of 400 cd / m ² at a current density of 10 mA / cm ² and a driving voltage of 4.2 V. Further, the luminance half life in constant current driving at a current density of 10 mA / cm ² was 400 hours.

（実施例２−４）
発光層に実施例１−５で得たπ共役系高分子（ＰＰＶ２−３）を用いた他は、実施例２−１と同様にして、有機ＥＬ素子を作製した。この有機ＥＬ素子を８５℃にて保存し、３００時間後の発光面積を確認したところ初期面積と比較し９７％であった。 (Example 2-4)
An organic EL device was produced in the same manner as in Example 2-1, except that the π-conjugated polymer (PPV2-3) obtained in Example 1-5 was used for the light emitting layer. The organic EL device was stored at 85 ° C. and the emission area after 300 hours was confirmed to be 97% compared with the initial area.

（比較例２−４）
比較例２−１で作製した有機ＥＬ素子を実施例２−４と同様にして、８５℃にて保存したところダークスポットの発生が見られ１００時間後の発光面積は初期面積と比較し５０％以下になった。 (Comparative Example 2-4)
When the organic EL device produced in Comparative Example 2-1 was stored at 85 ° C. in the same manner as in Example 2-4, dark spots were observed, and the light emitting area after 100 hours was 50% compared to the initial area. It became the following.

実施例２−４と比較例２−４の結果より、ＭＥＨ−ＰＰＶはＴｇが大変低いため、高温保存時に結晶化しダークスポットの多量発生が生じるのに対して、側鎖が本発明のπ共役系樹状分岐化合物である本発明のπ共役系高分子は高Ｔｇであるため高温保存によっても安定であることが判明した。 From the results of Example 2-4 and Comparative Example 2-4, MEH-PPV has a very low Tg, so that it crystallizes during high-temperature storage and a large amount of dark spots are generated, whereas the side chain is the π conjugate of the present invention. Since the π-conjugated polymer of the present invention, which is a dendritic compound, has a high Tg, it has been found to be stable even at high temperature storage.

［太陽電池の作製］
（実施例３−１）
ガラス基板上にシート抵抗１５Ω／□のＩＴＯが形成されている基盤の上に、バイトロンＰからなる薄膜をスピンコートにより形成した。得られた薄膜の膜厚は４０ｎｍであった。次いで、この薄膜上に、実施例１−４で得たπ共役系高分子（ＰＰＶ２−２）とフラーレン誘導体（ＰＣＢＭ、［６，６］−フェニル−Ｃ６１−ブチル酸メチルエステル）の１重量％クロロベンゼン溶液をスピンコートすることにより、高分子化合物層を形成した。得られた高分子化合物層の膜厚は５０ｎｍであった。なお、ＰＰＶ２−２とＰＣＢＭとの混合比率は１：４（重量比）とした。高分子化合物層上に更にＣａを６ｎｍ、Ａｌを２５０ｎｍそれぞれ蒸着して陰極を形成した。この場合において、太陽電池の実効面積は０．２５ｃｍ^２（０．５×０．５ｃｍ）であった。 [Production of solar cells]
(Example 3-1)
A thin film made of Vitron P was formed by spin coating on a substrate on which ITO having a sheet resistance of 15Ω / □ was formed on a glass substrate. The film thickness of the obtained thin film was 40 nm. Next, on this thin film, 1% by weight of the π-conjugated polymer (PPV2-2) and fullerene derivative (PCBM, [6,6] -phenyl-C61-butyric acid methyl ester) obtained in Example 1-4. A polymer compound layer was formed by spin coating a chlorobenzene solution. The film thickness of the obtained polymer compound layer was 50 nm. The mixing ratio of PPV2-2 and PCBM was 1: 4 (weight ratio). On the polymer compound layer, 6 nm of Ca and 250 nm of Al were further evaporated to form a cathode. In this case, the effective area of the solar cell was 0.25 cm ² (0.5 × 0.5 cm).

（比較例３−１）
π共役系高分子（ＰＰＶ２−２）に代えて、ＭＥＨ−ＰＰＶを用いた他は実施例３−１と同様にして、太陽電池を作製した。 (Comparative Example 3-1)
A solar cell was produced in the same manner as in Example 3-1, except that MEH-PPV was used instead of the π-conjugated polymer (PPV2-2).

実施例３−１及び比較例３−１で得られた太陽電池について、ＡＭ１．５（１０００Ｗ／ｍ^２）のソーラーシミュレーターを用いて、開放電圧（Ｖｏｃ）、光電流密度（Ｊｓｃ）、形状因子（ＦＦ）、光電変換効率（η）の測定を行い、電池特性を評価した。この結果を以下の表２に示す。 For the solar cells obtained in Example 3-1 and Comparative Example 3-1, an open circuit voltage (Voc), a photocurrent density (Jsc), and a form factor were used using an AM1.5 (1000 W / m ² ) solar simulator. (FF) and photoelectric conversion efficiency (η) were measured to evaluate battery characteristics. The results are shown in Table 2 below.

π共役系高分子からなる主鎖に結合する側鎖化合物を模式的に示す図である。It is a figure which shows typically the side chain compound couple | bonded with the principal chain which consists of (pi) conjugated polymer. 主鎖と結合するための官能基をコアユニットに有した側鎖化合物を模式的に示す図である。It is a figure which shows typically the side chain compound which has the functional group for couple | bonding with a principal chain in a core unit. 主鎖と結合するための官能基をコアユニットに有した側鎖化合物と、側鎖化合物と結合するための官能基を有した主鎖（π共役系高分子）を模式的に示す図である。It is a figure which shows typically the side chain compound which has the functional group for couple | bonding with a principal chain in a core unit, and the principal chain ((pi-conjugated polymer) which has a functional group for couple | bonding with a side chain compound. . 側鎖に樹状分岐を有するπ共役系高分子を模式的に示す図である。It is a figure which shows typically the (pi) conjugated polymer which has a dendritic branch in a side chain. ＰＰＶ１−１とＰＰＶ２−１のＵＶ／ＶＩＳ吸収スペクトルである。It is a UV / VIS absorption spectrum of PPV1-1 and PPV2-1. ＰＰＶ１−１のＰＬスペクトルを示す図である。It is a figure which shows PL spectrum of PPV1-1. ＰＰＶ２−１のＰＬスペクトルを示す図である。It is a figure which shows PL spectrum of PPV2-1. ＰＰＶ０−２とＰＰＶ１−２のＵＶ／ＶＩＳ吸収スペクトルである。It is UV / VIS absorption spectrum of PPV0-2 and PPV1-2. ＰＰＶ０−２とＰＰＶ２−２のＵＶ／ＶＩＳ吸収スペクトルである。It is a UV / VIS absorption spectrum of PPV0-2 and PPV2-2. ＰＰＶ０−２とＰＰＶ１−２のＰＬスペクトルを示す図である。It is a figure which shows PL spectrum of PPV0-2 and PPV1-2. ＰＰＶ０−２とＰＰＶ２−２のＰＬスペクトルを示す図である。It is a figure which shows PL spectrum of PPV0-2 and PPV2-2. ＰＰＶ１−２のＰＬスペクトルを示す図である。It is a figure which shows PL spectrum of PPV1-2. ＰＰＶ２−２のＰＬスペクトルを示す図である。It is a figure which shows PL spectrum of PPV2-2.

Explanation of symbols

１・・・第１世代枝ユニット、２・・・第２世代枝ユニット、３・・・第３世代枝ユニット、１０・・・コアユニット、６，３０・・・結合、１２・・・側鎖官能基、２２・・・主鎖官能基、１００・・・側鎖化合物、２００・・・主鎖、３００・・・側鎖に樹状分岐を有するπ共役系高分子。

DESCRIPTION OF SYMBOLS 1 ... 1st generation branch unit, 2 ... 2nd generation branch unit, 3 ... 3rd generation branch unit, 10 ... Core unit, 6,30 ... Connection, 12 ... side Chain functional group, 22 ... main chain functional group, 100 ... side chain compound, 200 ... main chain, 300 ... π-conjugated polymer having a dendritic branch in the side chain.

Claims

A π-conjugated polymer containing a repeating unit represented by the following general formula (1) and having a dendritic branch in the side chain.
[Wherein, R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a monovalent heterocyclic group or a cyano group, and Ar is a (2 + q) -valent group derived from an aromatic ring or an aromatic heterocyclic ring. , P represents 0 or 1, and q represents an integer of 1 to 6, respectively. G is a π-conjugated dendritic branch compound in which the 1st to n-th generation branch units are coupled so as to be branched in a tree-like manner in order of generation around the core unit (n is an integer of 1 or 2 or more) And represents the number of generations of the terminal branch unit). However, the branch unit excluding the terminal branch unit and the core unit are polyvalent groups derived from an aromatic ring or an aromatic heterocyclic ring, and the terminal branch unit is derived from an aromatic ring or an aromatic heterocyclic ring. A monovalent group, a bond between the core unit and the branch unit and a bond between the branch units are a single bond, and the terminal branch unit is a hydrogen atom, an alkyl group, a substituted or unsubstituted amino group; , At least one group selected from the group consisting of an alkoxy group and an alkylthio group. ]

The [pi-conjugated dendritic compound is coupled to the said Ar in the core unit, [pi-conjugated polymer having a dendritic branch to the side chain of claim 1, wherein.

The π-conjugated polymer having a dendritic branch in the side chain according to claim 1 or 2 , wherein n is an integer of 2 or more.

The branch unit excluding the terminal branch unit and the core unit are trivalent groups derived from substituted or unsubstituted benzene, and the terminal branch unit includes a hydrogen atom, an alkyl group, a substituted or unsubstituted amino group, an alkoxy group. The π-conjugated polymer having a dendritic branch in a side chain according to any one of claims 1 to 3 , which is a phenyl group having at least one group selected from the group consisting of a group and an alkylthio group.

The π-conjugated polymer having a dendritic branch in the side chain according to any one of claims 1 to 4 , having a polystyrene-equivalent weight average molecular weight of 3000 to 5000000.

An organic thin film element provided with the layer containing (pi) conjugated polymer which has a dendritic branch in the side chain as described in any one of Claims 1-5 .

An organic EL device comprising a layer containing a π-conjugated polymer having a dendritic branch in the side chain according to any one of claims 1 to 5 as a charge transport layer.

An organic EL device comprising a layer containing a π-conjugated polymer having a dendritic branch in the side chain according to any one of claims 1 to 5 as a light emitting layer.

An organic EL device comprising, as a light emitting layer, a layer in which a dopant is added to a base material containing a π-conjugated polymer having a dendritic branch in the side chain according to any one of claims 1 to 5 .

A solar cell provided with the layer containing (pi) conjugated polymer which has a dendritic branch in the side chain as described in any one of Claims 1-5 .