JP2011153269A - White light emitting polymer composite material and method of production thereof - Google Patents
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本発明は、白色発光性高分子複合材料およびその製造方法に関するものである。 The present invention relates to a white light-emitting polymer composite material and a method for producing the same.
白色発光性材料については、液晶ディスプレイのバックライトや照明装置等への利用拡大が期待されることから、近年活発に開発が行われている。 White light-emitting materials have been actively developed in recent years because they are expected to expand their use in backlights and lighting devices for liquid crystal displays.
中でも有機系の白色発光性材料は、無機系の白色発光性材料に比べ、ディスプレイの薄膜化や軽量化が可能である点、高効率な発光による省エネ対策に寄与することができる点、機能性の付与が容易である点等において優れている。さらに、有機高分子系の白色発光性材料は、溶液の塗布により大型の素子が作製できることから、大画面フラットパネルディスプレイへの応用が期待される。 In particular, organic white light-emitting materials can make displays thinner and lighter than inorganic white light-emitting materials, and can contribute to energy-saving measures through highly efficient light emission. It is excellent in that it is easy to give. Furthermore, organic polymer-based white light-emitting materials are expected to be applied to large-screen flat panel displays because large elements can be produced by applying a solution.
かかる有機高分子系の白色発光性材料としては、青色発光性高分子化合物に、緑色発光性の構造単位及び赤色発光性の構造単位が組み込まれた共重合体を用いるのが主流である（例えば、非特許文献１等参照）。 As such an organic polymer-based white light-emitting material, a copolymer in which a green light-emitting structural unit and a red light-emitting structural unit are incorporated in a blue light-emitting polymer compound is mainly used (for example, And non-patent document 1).
また、有機高分子系の白色発光性材料を実現する他の技術として、フェルスター型のエネルギー移動を利用するポリマーブレンドが報告されている（例えば、非特許文献２等参照）。非特許文献２では、ポリ（９−ビニルカルバゾール）（ＰＶＫ）、ポリ（９,９´−ジヘキシルフルオレン−２,７−ジビニレン−ｍ−フェニレンビニレン−ｓｔａｔ−ｐ−フェニレンビニレン）（ＣＰＤＨＦＰＶ）、及びポリ[２−メトキシ−５−（２´−エチル−ヘキシロキシ）−１,４−フェニレンビニレン]（ＭＥＨ−ＰＰＶ）を、重量比で１９：１：１の割合で溶解した溶液をＩＴＯ−被覆ガラス基板にスピンキャストして得られたＬＥＤから白色発光が得られることが報告されている。かかるポリマーブレンドでは、ＰＶＫからのエネルギー移動により青色発光が発現されると同時に、ＰＶＫ及びＣＰＤＨＦＰＶとＭＥＨ−ＰＰＶとの低い混和性により部分的なフェルスター型エネルギー移動が起こっていることが記載されている。 As another technique for realizing an organic polymer-based white light-emitting material, a polymer blend using Forster-type energy transfer has been reported (see, for example, Non-Patent Document 2). In Non-Patent Document 2, poly (9-vinylcarbazole) (PVK), poly (9,9′-dihexylfluorene-2,7-divinylene-m-phenylene vinylene-stat-p-phenylene vinylene) (CPDHFPV), and A solution in which poly [2-methoxy-5- (2′-ethyl-hexyloxy) -1,4-phenylenevinylene] (MEH-PPV) was dissolved at a weight ratio of 19: 1: 1 was used as an ITO-coated glass. It has been reported that white light emission can be obtained from an LED obtained by spin casting on a substrate. In such polymer blends, it is described that blue light emission is developed by energy transfer from PVK, and at the same time, partial forster energy transfer occurs due to low miscibility of PVK and CPDHFPV with MEH-PPV. Yes.
しかしながら、色調制御が容易で、相溶性が良く、且つ、簡便に製造できる白色発光性材料は未だ得られていない。 However, a white light-emitting material that can be easily controlled in color tone, has good compatibility, and can be easily produced has not yet been obtained.
すなわち、青色発光性高分子化合物に、緑色発光性の構造単位及び赤色発光性の構造単位が組み込まれた共重合体は単一化合物であるという利点はあるが、その製造は、メタ位、パラ位等の結合位置や組成の制御が困難である。そのため、多段階で精密な合成手法の確立が求められ、精密設計された高純度かつ高価な触媒や合成条件の最適化が必要である。また、組成を精密に制御することができないため、色調制御が困難である。 That is, a copolymer in which a green light-emitting structural unit and a red light-emitting structural unit are incorporated in a blue light-emitting polymer compound has an advantage that it is a single compound, but its production is performed at the meta position, It is difficult to control the bonding position such as the position and the composition. Therefore, it is required to establish a precise synthesis method in multiple stages, and it is necessary to optimize a high-purity and expensive catalyst and synthesis conditions that are precisely designed. In addition, since the composition cannot be precisely controlled, color tone control is difficult.
また、非特許文献２に記載の、フェルスター型のエネルギー移動を利用するポリマーブレンドでは、ＰＶＫ及びＣＰＤＨＦＰＶとＭＥＨ−ＰＰＶとの混和性が低いため、相分離が起こっている。そのため、エネルギー移動は、フェルスターの有効半径内で、相の境界をまたいで部分的に起こっており、これにより２つの色が同時に発光して白色発光が実現されている。しかしながら、かかる方法では、各ポリマーの構造が少しでも変わると、相分離の構造が変化するため、ポリマーの選択や組成により相分離を制御するのが非常に困難である。さらに、製造ロットごとの共重合体（コポリマー、ターポリマー）の構造や分子量のばらつきにより、相分離構造の制御性が悪くなるという欠点がある。 Further, in the polymer blend using the Forster type energy transfer described in Non-Patent Document 2, phase miscibility occurs because the miscibility of PVK and CPDHFPV with MEH-PPV is low. Therefore, the energy transfer partially occurs across the phase boundary within the effective radius of the Förster, whereby two colors emit light simultaneously to realize white light emission. However, in such a method, if the structure of each polymer changes even slightly, the structure of phase separation changes. Therefore, it is very difficult to control the phase separation by the selection and composition of the polymer. Furthermore, there is a drawback in that the controllability of the phase separation structure is deteriorated due to variations in the structure and molecular weight of the copolymer (copolymer, terpolymer) for each production lot.
入手容易で安価な単独重合体（ホモポリマー）からなる発光性高分子化合物から、白色発光性材料が簡便に構築できたならば産業上大きな利点をもたらす。 If a white light-emitting material can be easily constructed from a light-emitting polymer compound consisting of a readily available and inexpensive homopolymer (homopolymer), it provides a great industrial advantage.
また、非特許文献２に記載の、フェルスター型のエネルギー移動を利用するポリマーブレンドでは、相分離が起こっているため、ポリマー同士がフェルスターの有効半径内に存在する割合が限られる。そのため、エネルギー移動の効率が悪いという問題点がある。 Further, in the polymer blend using the Förster type energy transfer described in Non-Patent Document 2, since the phase separation occurs, the ratio of the polymers existing within the effective radius of Förster is limited. Therefore, there exists a problem that the efficiency of energy transfer is bad.
本発明は、上記問題点に鑑みてなされたものであり、その目的は、色調制御が容易で、相溶性が良く、且つ、簡便に製造できる白色発光性材料およびその製造方法を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a white light-emitting material that is easy to control the color tone, has good compatibility, and can be easily manufactured, and a method for manufacturing the white light-emitting material. is there.
本発明に係る白色発光性共役高分子複合材料は、上記課題を解決するために、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有する青色発光性共役高分子化合物と、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、を含む共役高分子化合物混合溶液に、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加して得られる凝集体を含むことを特徴としている。 In order to solve the above problems, the white light-emitting conjugated polymer composite material according to the present invention includes a blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm, and the blue light-emitting property. A green light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength of the conjugated polymer compound, and a red light-emitting conjugated polymer having an absorption wavelength partially overlapping with the light emission wavelength of the green light-emitting conjugated polymer compound A poor solvent for the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound. It is characterized by including a collection.
上記の構成によれば、入手容易で安価な発光性高分子化合物から、白色発光性材料が簡便に構築できるとともに、色調制御が容易で、相溶性が良い白色発光性材料を実現することができる。 According to the above configuration, a white light-emitting material can be easily constructed from a readily available and inexpensive light-emitting polymer compound, and a white light-emitting material that is easy to control color tone and has good compatibility can be realized. .
本発明に係る白色発光性共役高分子複合材料では、上記緑色発光性共役高分子化合物は、４７０〜６００ｎｍの波長領域にフォトルミネセンスの発光ピークを有することが好ましい。 In the white light-emitting conjugated polymer composite material according to the present invention, the green light-emitting conjugated polymer compound preferably has a photoluminescence emission peak in a wavelength region of 470 to 600 nm.
上記の構成によれば、青色、緑色及び赤色がさらにバランスよく発光して白色発光が実現されるというさらなる効果を奏する。 According to said structure, there exists the further effect that white light emission is implement | achieved by further light-emitting blue, green, and red.
本発明に係る白色発光性共役高分子複合材料では、上記赤色発光性共役高分子化合物は、５２０〜７５０ｎｍの波長領域にフォトルミネセンスの発光ピークを有することが好ましい。 In the white light-emitting conjugated polymer composite material according to the present invention, the red light-emitting conjugated polymer compound preferably has a photoluminescence emission peak in a wavelength region of 520 to 750 nm.
上記の構成によれば、青色、緑色及び赤色がさらにバランスよく発光して白色発光が実現されるというさらなる効果を奏する。 According to said structure, there exists the further effect that white light emission is implement | achieved by further light-emitting blue, green, and red.
本発明に係る白色発光性共役高分子複合材料では、上記緑色発光性共役高分子化合物は、フォトルミネセンスの吸収波長が３６０〜５２０ｎｍの波長領域に含まれることが好ましい。 In the white light-emitting conjugated polymer composite material according to the present invention, it is preferable that the green light-emitting conjugated polymer compound has a photoluminescence absorption wavelength in a wavelength region of 360 to 520 nm.
上記の構成によれば、上記緑色発光性共役高分子化合物は上記青色発光性共役高分子化合物の青色発光のエネルギーを吸収して、緑色の発光が起こる。 According to said structure, the said green light emission conjugated polymer compound absorbs the blue emission energy of the said blue light emission conjugated polymer compound, and green light emission occurs.
本発明に係る白色発光性共役高分子複合材料では、上記赤色発光性共役高分子化合物は、フォトルミネセンスの吸収波長が３７０〜６１０ｎｍの波長領域に含まれることが好ましい。 In the white light-emitting conjugated polymer composite material according to the present invention, the red light-emitting conjugated polymer compound is preferably included in a wavelength region of 370 to 610 nm in photoluminescence absorption wavelength.
上記の構成によれば、上記赤色発光性共役高分子化合物は上記緑又は青色発光性共役高分子化合物の発光のエネルギーを吸収して、赤色の発光が起こる。 According to said structure, the said red light emission conjugated polymer compound absorbs the light emission energy of the said green or blue light emission conjugated polymer compound, and red light emission occurs.
本発明に係る白色発光性共役高分子複合材料では、上記青色発光性共役高分子化合物に対する上記緑色発光性共役高分子化合物の割合は、１〜１２０モル％であり、上記青色発光性共役高分子化合物に対する上記赤色発光性共役高分子化合物の割合は、０．０００３〜１モル％であることが好ましい。 In the white light-emitting conjugated polymer composite material according to the present invention, the ratio of the green light-emitting conjugated polymer compound to the blue light-emitting conjugated polymer compound is 1 to 120 mol%, and the blue light-emitting conjugated polymer is The ratio of the red light-emitting conjugated polymer compound to the compound is preferably 0.0003 to 1 mol%.
上記の構成によれば、青色、緑色及び赤色がさらにバランスよく発光して白色発光が実現されるというさらなる効果を奏する。 According to said structure, there exists the further effect that white light emission is implement | achieved by further light-emitting blue, green, and red.
本発明に係る白色発光性共役高分子複合材料は、上記共役高分子化合物混合溶液に対し、上記貧溶媒を５０〜２５０体積％添加して得られる凝集体を含むことが好ましい。 The white light-emitting conjugated polymer composite material according to the present invention preferably contains an aggregate obtained by adding 50 to 250% by volume of the poor solvent to the conjugated polymer compound mixed solution.
上記の構成によれば、さらに好適に凝集体を得ることができるというさらなる効果を奏する。 According to said structure, there exists the further effect that an aggregate can be obtained more suitably.
本発明に係る白色発光性共役高分子複合材料では、上記青色発光性共役高分子化合物は、下記一般式（１） In the white light-emitting conjugated polymer composite material according to the present invention, the blue light-emitting conjugated polymer compound has the following general formula (1):
（一般式（１）中、Ｒ１及びＲ２はそれぞれ独立して、炭素数４〜１８のアルキル基を示し、ｎは１０〜１０００の整数を示す。）で表される構造を有することが好ましい。 (In General Formula (1), R 1 and R 2 each independently represents an alkyl group having 4 to 18 carbon atoms, and n represents an integer of 10 to 1000). preferable.
本発明に係る白色発光性共役高分子複合材料では、上記緑色発光性共役高分子化合物は、下記一般式（２） In the white light-emitting conjugated polymer composite material according to the present invention, the green light-emitting conjugated polymer compound has the following general formula (2):
（一般式（２）中、Ｒ３及びＲ４はそれぞれ独立して、炭素数４〜１８のアルキル基を示し、ｎは１０〜１０００の整数を示す。）で表される構造を有することが好ましい。 (In General Formula (2), R 3 and R 4 each independently represents an alkyl group having 4 to 18 carbon atoms, and n represents an integer of 10 to 1000). preferable.
本発明に係る白色発光性共役高分子複合材料では、上記赤色発光性共役高分子化合物は、下記一般式（３） In the white light-emitting conjugated polymer composite material according to the present invention, the red light-emitting conjugated polymer compound has the following general formula (3):
（一般式（３）中、Ｒ５及びＲ６はそれぞれ独立して、炭素数１〜１８のアルキル基を示し、ｎは１０〜１０００の整数を示す。）で表される構造を有することが好ましい。 (In General Formula (3), R 5 and R 6 each independently represent an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 10 to 1000). preferable.
本発明に係る白色発光性共役高分子複合材料の製造方法は、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有する青色発光性共役高分子化合物と、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、を含む共役高分子化合物混合溶液を調製する混合溶液調製工程と、当該共役高分子化合物混合溶液に貧溶媒を添加して白色発光性共役高分子複合材料を、凝集体として得る貧溶媒添加工程と、を含むことを特徴としている。 A method for producing a white light-emitting conjugated polymer composite material according to the present invention includes a blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm, and the blue light-emitting conjugated polymer compound. A green light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength, and a red light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength of the green light-emitting conjugated polymer compound. A mixed solution preparation step of preparing a conjugated polymer compound mixed solution containing, a poor solvent addition step of adding a poor solvent to the conjugated polymer compound mixed solution to obtain a white light-emitting conjugated polymer composite material as an aggregate, It is characterized by including.
上記の構成によれば、入手容易で安価な発光性高分子化合物から、白色発光性材料が簡便に構築できるとともに、色調制御が容易で、相溶性が良い白色発光性材料を実現することができる。 According to the above configuration, a white light-emitting material can be easily constructed from a readily available and inexpensive light-emitting polymer compound, and a white light-emitting material that is easy to control color tone and has good compatibility can be realized. .
本発明に係る白色発光性共役高分子複合材料は、以上のように、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有する青色発光性共役高分子化合物と、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、を含む共役高分子化合物混合溶液に、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加して得られる凝集体を含む構成を備えているので、入手容易で安価な発光性高分子化合物から、白色発光性材料が簡便に構築できるとともに、色調制御が容易で、相溶性が良い白色発光性材料を実現することができるという効果を奏する。 As described above, the white light-emitting conjugated polymer composite material according to the present invention includes a blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm and the blue light-emitting conjugated polymer. A green light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength of the compound, and a red light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength of the green light-emitting conjugated polymer compound; And an aggregate obtained by adding a poor solvent for the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound to a conjugated polymer compound mixed solution containing Since it has a configuration, it is easy to build a white light-emitting material from easily available and inexpensive light-emitting polymer compounds, and it is easy to control color tone and has good compatibility. An effect that it is possible to realize a white light emitting material.
また、本発明に係る白色発光性共役高分子複合材料の製造方法は、以上のように、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有する青色発光性共役高分子化合物と、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、を含む共役高分子化合物混合溶液を調製する混合溶液調製工程と、当該共役高分子化合物混合溶液に貧溶媒を添加して白色発光性共役高分子複合材料を、凝集体として得る貧溶媒添加工程と、を含む構成を備えているので、入手容易で安価な発光性高分子化合物から、白色発光性材料が簡便に構築できるとともに、色調制御が容易で、相溶性が良い白色発光性材料を実現することができるという効果を奏する。 In addition, as described above, the method for producing a white light-emitting conjugated polymer composite material according to the present invention includes a blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm and the blue color. A green light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength of the light-emitting conjugated polymer compound, and a red light-emitting property having an absorption wavelength partially overlapping with the light emission wavelength of the green light-emitting conjugated polymer compound A mixed solution preparation step of preparing a conjugated polymer compound mixed solution including a conjugated polymer compound, and adding a poor solvent to the conjugated polymer compound mixed solution to form a white light-emitting conjugated polymer composite material as an aggregate And a poor solvent addition step to obtain a white light-emitting material from a readily available and inexpensive light-emitting polymer compound, and color tone control Easy, there is an effect that it is possible to realize a good compatibility white luminous material.
本発明の一実施形態について図１ないし図５に基づいて説明すると以下の通りである。なお、本明細書では、範囲を示す「Ａ〜Ｂ」は、特に断りのない限り、Ａ以上Ｂ以下であることを示す。 An embodiment of the present invention will be described below with reference to FIGS. In the present specification, “A to B” indicating a range indicates A or more and B or less unless otherwise specified.
（Ｉ）白色発光性共役高分子複合材料
本発明者らは、上記課題を解決するために鋭意検討した結果、第１の発光性共役高分子化合物の発光波長と、第２の発光性共役高分子化合物の吸収波長とが重なる２種類の発光性共役高分子化合物を溶解した溶液中では、殆どエネルギー移動が起こらない場合でも、当該溶液にこれらの発光性共役高分子化合物に対する貧溶媒を加えることにより発現する凝集体では、高効率なエネルギー移動が起こることを見出した。そこで、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有する青色発光性共役高分子化合物と、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物とを含む共役高分子化合物混合溶液に、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加したところ、白色発光性の凝集体が得られることを見出した。そして、かかる凝集体を蛍光顕微鏡により観察した結果、３種類の発光性共役高分子化合物が別々に発光しているのではなく、１つの凝集体系から発光していることが判った。また、得られた凝集体のフォトルミネセンス（ＰＬ）スペクトルから、可視域の全波長をカバーするように青、緑及び赤を発光させることができたことを確認した。
(I) White light-emitting conjugated polymer composite material As a result of intensive studies to solve the above problems, the present inventors have found that the emission wavelength of the first light-emitting conjugated polymer compound and the second light-emitting conjugated polymer compound are high. Even in the case where almost no energy transfer occurs in a solution in which two kinds of light-emitting conjugated polymer compounds overlapping with the absorption wavelength of the molecular compound are dissolved, a poor solvent for these light-emitting conjugated polymer compounds should be added to the solution. It was found that high-efficiency energy transfer occurs in the aggregates expressed by. Therefore, a blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm, and a green light-emitting conjugate having an absorption wavelength partially overlapping with the light emission wavelength of the blue light-emitting conjugated polymer compound. The blue light-emitting conjugated polymer is added to a conjugated polymer compound mixed solution comprising a polymer compound and a red light-emitting conjugated polymer compound having an absorption wavelength that partially overlaps the light emission wavelength of the green light-emitting conjugated polymer compound. It was found that when a poor solvent for the compound, the green light-emitting conjugated polymer compound and the red light-emitting conjugated polymer compound was added, a white light-emitting aggregate was obtained. As a result of observing the aggregates with a fluorescence microscope, it was found that the three types of light-emitting conjugated polymer compounds did not emit light separately, but emitted light from one aggregate system. Moreover, it was confirmed from the photoluminescence (PL) spectrum of the obtained aggregate that blue, green and red could be emitted so as to cover all wavelengths in the visible range.
本発明にかかる白色発光性共役高分子複合材料は、上記共役高分子化合物混合溶液に、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加して得られる凝集体を含む。本発明に係る白色発光性共役高分子複合材料における白色発光は以下に示す機構により起こっていると考えられる。 The white light-emitting conjugated polymer composite material according to the present invention is prepared by adding the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound to the conjugated polymer compound mixed solution. It contains aggregates obtained by adding a poor solvent. It is considered that white light emission in the white light-emitting conjugated polymer composite material according to the present invention is caused by the following mechanism.
図１は、本発明で用いられる青色発光性共役高分子化合物、緑色発光性共役高分子化合物及び赤色発光性共役高分子化合物の一例の紫外可視吸収スペクトルとフォトルミネセンス（ＰＬ）スペクトルとを示す図である。なお、図１に示されるＰＦ８は青色発光性共役高分子化合物の一例、Ｆ８Ｔ２は緑色発光性共役高分子化合物の一例、ＭＥＨ−ＰＰＶは赤色発光性共役高分子化合物の一例である。また図１中、太線の実線は青色発光性共役高分子化合物の紫外可視吸収スペクトルを、細線の実線は青色発光性共役高分子化合物のフォトルミネセンススペクトルを、太線の破線は緑色発光性共役高分子化合物の紫外可視吸収スペクトルを、細線の破線は緑色発光性共役高分子化合物のフォトルミネセンススペクトルを、太線の二点鎖線は赤色発光性共役高分子化合物の紫外可視吸収スペクトルを、細線の二点鎖線は赤色発光性共役高分子化合物のフォトルミネセンススペクトルを示す。 FIG. 1 shows an ultraviolet-visible absorption spectrum and a photoluminescence (PL) spectrum of an example of a blue light-emitting conjugated polymer compound, a green light-emitting conjugated polymer compound, and a red light-emitting conjugated polymer compound used in the present invention. FIG. 1 is an example of a blue light-emitting conjugated polymer compound, F8T2 is an example of a green light-emitting conjugated polymer compound, and MEH-PPV is an example of a red light-emitting conjugated polymer compound. In FIG. 1, the bold solid line shows the UV-visible absorption spectrum of the blue light-emitting conjugated polymer compound, the thin solid line shows the photoluminescence spectrum of the blue light-emitting conjugated polymer compound, and the thick broken line shows the green light-emitting conjugate high molecular weight. The ultraviolet-visible absorption spectrum of the molecular compound, the thin broken line the photoluminescence spectrum of the green light-emitting conjugated polymer compound, the bold two-dot chain line the ultraviolet-visible absorption spectrum of the red light-emitting conjugated polymer compound, The dotted line indicates the photoluminescence spectrum of the red light-emitting conjugated polymer compound.
図１に示されるように、上記青色発光性共役高分子化合物の発光波長と緑色発光性共役高分子化合物の吸収波長は部分的に重なっており、上記緑色発光性共役高分子化合物の発光波長と赤色発光性共役高分子化合物の吸収波長とは部分的に重なっている。これにより、エネルギードナー（以下、本明細書において単にドナーと称することがある。）である青色発光性共役高分子化合物及び緑色発光性共役高分子化合物の発光波長と、エネルギーアクセプター（以下、本明細書において単にアクセプターと称することがある。）である、それぞれ緑色発光性共役高分子化合物及び赤色発光性共役高分子化合物の吸収波長とが重なるという、フェルスター型エネルギー移動の条件を満たしている。したがって、ドナーと、アクセプターとが、相互にフェルスターの有効半径内に存在する場合には、フェルスター型のエネルギー移動が起こる。なお、フェルスターの有効半径は、通常、１〜１０ｎｍである。 As shown in FIG. 1, the emission wavelength of the blue light-emitting conjugated polymer compound and the absorption wavelength of the green light-emitting conjugated polymer compound partially overlap, and the emission wavelength of the green light-emitting conjugated polymer compound and It partially overlaps with the absorption wavelength of the red light emitting conjugated polymer compound. As a result, the emission wavelength of the blue light-emitting conjugated polymer compound and the green light-emitting conjugated polymer compound, which are energy donors (hereinafter sometimes simply referred to as donors in the present specification), and the energy acceptor (hereinafter referred to as the present invention). In the specification, it may be simply referred to as an acceptor.), Which satisfies the conditions of Forster energy transfer, in which the absorption wavelengths of the green light-emitting conjugated polymer compound and the red light-emitting conjugated polymer compound overlap each other. . Therefore, when the donor and the acceptor are within the effective radius of the Förster, a Förster-type energy transfer occurs. The effective radius of Forster is usually 1 to 10 nm.
なお、本発明では、青色発光性共役高分子化合物の発光波長と赤色発光性共役高分子化合物の吸収波長も部分的に重なっていてもよい。かかる場合は、青色発光性共役高分子化合物と、赤色発光性共役高分子化合物との関係では、青色発光性共役高分子化合物はフェルスター型のエネルギー移動のドナー、赤色発光性共役高分子化合物がアクセプターとなる。 In the present invention, the emission wavelength of the blue light-emitting conjugated polymer compound and the absorption wavelength of the red light-emitting conjugated polymer compound may partially overlap. In such a case, in the relationship between the blue light-emitting conjugated polymer compound and the red light-emitting conjugated polymer compound, the blue light-emitting conjugated polymer compound is a Forster energy transfer donor, and the red light-emitting conjugated polymer compound is Become an acceptor.
したがって、エネルギードナーである青色発光性共役高分子化合物のフォトルミネセンスの発光ピークが３８０〜５００ｎｍの波長領域にある場合には、エネルギーアクセプターである緑色発光性共役高分子化合物の紫外可視吸収波長は３６０〜５２０ｎｍであることが好ましい。同様に、エネルギードナーである青色発光性共役高分子化合物及び／又は緑色発光性共役高分子化合物のフォトルミネセンスの発光ピークが３８０〜６００ｎｍの波長領域にある場合には、エネルギーアクセプターである赤色発光性共役高分子化合物の紫外可視吸収波長は３７０〜６１０ｎｍであることが好ましい。 Therefore, when the emission peak of photoluminescence of the blue light-emitting conjugated polymer compound as an energy donor is in the wavelength region of 380 to 500 nm, the ultraviolet-visible absorption wavelength of the green light-emitting conjugated polymer compound as an energy acceptor Is preferably 360 to 520 nm. Similarly, when the photoluminescence emission peak of the blue light-emitting conjugated polymer compound and / or the green light-emitting conjugated polymer compound that is an energy donor is in the wavelength region of 380 to 600 nm, the red color that is the energy acceptor. The UV-visible absorption wavelength of the luminescent conjugated polymer compound is preferably 370 to 610 nm.
本発明に係る白色発光性共役高分子複合材料では、上記共役高分子化合物混合溶液に、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加することにより凝集体が得られる。かかる凝集体では、巨視的には各共役高分子化合物の相分離は起こらず、相溶性が良い。これにより、フェルスター型のエネルギー移動のドナーとアクセプターとがフェルスターの有効半径内に存在するという条件が満たされエネルギー移動が起こる。それゆえ、高効率なエネルギー移動を起こしやすくなると考えられる。 In the white light-emitting conjugated polymer composite material according to the present invention, the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound are added to the conjugated polymer compound mixed solution. Aggregates are obtained by adding a poor solvent. Macroscopically, the conjugated polymer compound does not undergo phase separation macroscopically and has good compatibility. This satisfies the condition that the Forster-type energy transfer donor and acceptor are within the effective radius of the Forster and energy transfer occurs. Therefore, it is considered that highly efficient energy transfer is likely to occur.
また、本発明に係る白色発光性共役高分子複合材料では、ドナーの発光波長と、アクセプターの吸収波長とが、完全には重ならないように、厳密に部分的に重なるようにすることにより、部分的なフェルスター型エネルギー移動を起こさせる。すなわち、ドナーである青色発光性共役高分子化合物の吸収波長、より好ましくは吸収極大波長で、本発明に係る白色発光性共役高分子複合材料を励起すると青色発光が起こる。このとき、ドナーの発光波長と、アクセプターの吸収波長とが、完全に重ならないことにより、青色発光を残しながら、青色発光のエネルギーをアクセプターが吸収して、緑色及び赤色の発光が起こる。
これにより青色、緑色及び赤色がバランスよく発光して白色発光が実現されると考えられる。
In the white light-emitting conjugated polymer composite material according to the present invention, the emission wavelength of the donor and the absorption wavelength of the acceptor are strictly overlapped so that they do not overlap completely. Cause typical Forster energy transfer. That is, when the white light-emitting conjugated polymer composite material according to the present invention is excited at the absorption wavelength of the blue light-emitting conjugated polymer compound as a donor, more preferably, the absorption maximum wavelength, blue light emission occurs. At this time, since the emission wavelength of the donor and the absorption wavelength of the acceptor do not completely overlap, the acceptor absorbs the energy of blue emission while leaving blue emission, and green and red emission occurs.
Thereby, it is considered that blue, green, and red light are emitted in a balanced manner to realize white light emission.
本発明に係る白色発光性共役高分子複合材料では、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物はホモポリマーであることがより好ましい。これにより、共重合体を用いる場合のように、製造ロットごとに構造が異なることによる、相分離構造の制御が困難であるという問題がないため好ましい。 In the white light-emitting conjugated polymer composite material according to the present invention, the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound are more preferably homopolymers. This is preferable because there is no problem that it is difficult to control the phase separation structure due to the structure being different for each production lot as in the case of using a copolymer.
また、本発明に係る白色発光性共役高分子複合材料では、白色発光性高分子の蛍光量子収率が５０％以上である高量子収率の白色発光性共役高分子複合材料を実現することができる。なお、本発明において蛍光量子収率とは発光体に対して光を照射した際に、発光体がその光エネルギーを何％吸収して何％の蛍光を放出しているかを示した値をいう。 The white light-emitting conjugated polymer composite material according to the present invention can realize a white light-emitting conjugated polymer composite material having a high quantum yield in which the fluorescence quantum yield of the white light-emitting polymer is 50% or more. it can. In the present invention, the fluorescence quantum yield means a value indicating what percentage of light energy is absorbed by the light emitter and what percentage of fluorescence is emitted when the light emitter is irradiated with light. .
＜青色発光性共役高分子化合物＞
本発明で用いられる青色発光性共役高分子化合物は、上述したように、エネルギー移動のドナーとなるものであり、青色発光性であれば特に限定されるものではない。本発明で用いられる青色発光性共役高分子化合物は、好ましくは３８０〜５００ｎｍの波長領域、より好ましくは、４１０〜４８０ｎｍの波長領域にフォトルミネセンスの発光ピークを有するものである。さらに好ましくは、本発明で用いられる青色発光性共役高分子化合物は、フォトルミネセンスの発光波長が、３８０〜５００ｎｍの波長領域、特に好ましくは４１０〜４８０ｎｍの波長領域に含まれるものである。
<Blue light-emitting conjugated polymer compound>
As described above, the blue light-emitting conjugated polymer compound used in the present invention serves as an energy transfer donor, and is not particularly limited as long as it emits blue light. The blue light-emitting conjugated polymer compound used in the present invention preferably has a photoluminescence emission peak in a wavelength region of 380 to 500 nm, more preferably in a wavelength region of 410 to 480 nm. More preferably, the blue light-emitting conjugated polymer compound used in the present invention has a photoluminescence emission wavelength in the wavelength region of 380 to 500 nm, particularly preferably in the wavelength region of 410 to 480 nm.
なお、本発明において、共役高分子化合物とは、紫外、可視または近赤外域のいずれかに吸収および発光を示す高分子化合物をいう。 In the present invention, the conjugated polymer compound refers to a polymer compound that absorbs and emits light in any of the ultraviolet, visible, and near infrared regions.
また、本発明で用いられる青色発光性共役高分子化合物は、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有するものであれば、励起は如何なる方法で行ってもよいが、例えば、３５０〜４３０ｎｍの光によって励起されうる。 The blue light-emitting conjugated polymer compound used in the present invention may be excited by any method as long as it has a photoluminescence emission peak in the wavelength region of 380 to 500 nm. It can be excited by light of ˜430 nm.
上記青色発光性共役高分子化合物としては、特に限定されるものではないが、例えばポリフルオレン系化合物、ポリカルバゾール等を好適に用いることができる。 Although it does not specifically limit as said blue light emission conjugated polymer compound, For example, a polyfluorene type compound, polycarbazole, etc. can be used suitably.
上記青色発光性共役高分子化合物のより具体的な一例としては、例えば、下記一般式（１） As a more specific example of the blue light-emitting conjugated polymer compound, for example, the following general formula (1)
で表される構造を有するポリフルオレン系化合物を挙げることができる。一般式（１）中、Ｒ１及びＲ２はそれぞれ独立して、炭素数４〜１８のアルキル基を示し、ｎは１０〜１０００の整数を示す。 The polyfluorene type compound which has a structure represented by these can be mentioned. In General Formula (1), R 1 and R 2 each independently represent an alkyl group having 4 to 18 carbon atoms, and n represents an integer of 10 to 1000.
Ｒ１及びＲ２としては、炭素数４〜１８のアルキル基であれば特に限定されるものではなく、直鎖状であっても、分岐状であってもよい。 R 1 and R 2 are not particularly limited as long as they are alkyl groups having 4 to 18 carbon atoms, and may be linear or branched.
Ｒ１及びＲ２としては、より具体的には、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等を挙げることができる。 More specifically, examples of R 1 and R 2 include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like. Group, hexadecyl group, heptadecyl group, octadecyl group and the like.
＜緑色発光性共役高分子化合物＞
本発明で用いられる緑色発光性共役高分子化合物は、上述したように、上記青色発光性共役高分子化合物に対してエネルギー移動のアクセプターとなるものであり、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有するものであれば特に限定されるものではない。
<Green light-emitting conjugated polymer compound>
As described above, the green light-emitting conjugated polymer compound used in the present invention serves as an energy transfer acceptor for the blue light-emitting conjugated polymer compound. There is no particular limitation as long as it has an absorption wavelength that partially overlaps the wavelength.
なお、本発明において部分的に重なるとは、励起エネルギーのドナーである発光帯のプロファイルと、励起エネルギーのアクセプターである吸収帯のプロファイルの部分一致として定義される。本発明で用いられる緑色発光性共役高分子化合物の吸収波長が、上記青色発光性共役高分子化合物の発光波長と完全に重ならないで、部分的に重なるようにすることにより、部分的なフェルスター型エネルギー移動を起こさせることができる。 In the present invention, “partially overlapping” is defined as a partial coincidence between a profile of an emission band that is an excitation energy donor and a profile of an absorption band that is an acceptor of excitation energy. By making the absorption wavelength of the green light-emitting conjugated polymer compound used in the present invention partially overlap with the light emission wavelength of the blue light-emitting conjugated polymer compound, a partial forster is obtained. Mold energy transfer can occur.
上記緑色発光性共役高分子化合物の吸収波長は、青色発光性共役高分子化合物のフォトルミネセンスの発光波長の範囲の全部と重ならないことが好ましく、３６０〜５２０ｎｍの波長領域に含まれることがより好ましい。 The absorption wavelength of the green light-emitting conjugated polymer compound preferably does not overlap the entire photoluminescence emission wavelength range of the blue light-emitting conjugated polymer compound, and is more preferably included in the wavelength range of 360 to 520 nm. preferable.
これにより、上記緑色発光性共役高分子化合物は上記青色発光性共役高分子化合物の青色発光のエネルギーを吸収して、緑色の発光が起こる。 Accordingly, the green light-emitting conjugated polymer compound absorbs the blue light emission energy of the blue light-emitting conjugated polymer compound, and green light emission occurs.
また、上記緑色発光性共役高分子化合物は、好ましくは４７０〜６００ｎｍの波長領域、より好ましくは、４９０〜５６０ｎｍの波長領域にフォトルミネセンスの発光ピークを有するものである。さらに好ましくは、本発明で用いられる緑色発光性共役高分子化合物は、フォトルミネセンスの発光波長が、４７０〜６００ｎｍの波長領域、特に好ましくは４９０〜５６０ｎｍの波長領域に含まれるものである。 The green light-emitting conjugated polymer compound preferably has a photoluminescence emission peak in a wavelength region of 470 to 600 nm, more preferably in a wavelength region of 490 to 560 nm. More preferably, the green light-emitting conjugated polymer compound used in the present invention has a photoluminescence emission wavelength in the wavelength region of 470 to 600 nm, particularly preferably in the wavelength region of 490 to 560 nm.
また、上記緑色発光性共役高分子化合物は、４７０〜６００ｎｍの波長領域にフォトルミネセンスの発光ピークを有し、かつ吸収波長が３６０〜５２０ｎｍであることが好ましい。これにより、青色発光性共役高分子化合物からの部分的なフェルスター型エネルギー移動を受けることができ、かつバランスのよい白色発光を実現することができる。 The green light-emitting conjugated polymer compound preferably has a photoluminescence emission peak in a wavelength region of 470 to 600 nm and an absorption wavelength of 360 to 520 nm. Thereby, partial Forster energy transfer from the blue light-emitting conjugated polymer compound can be received, and balanced white light emission can be realized.
上記緑色発光性共役高分子化合物としては、特に限定されるものではないが、例えばポリフルオレンチオフェン系化合物等を好適に用いることができる。 Although it does not specifically limit as said green light emission conjugated polymer compound, For example, a polyfluorene thiophene type compound etc. can be used conveniently.
上記緑色発光性共役高分子化合物のより具体的な一例としては、例えば、下記一般式（２） As a more specific example of the green light-emitting conjugated polymer compound, for example, the following general formula (2)
で表される構造を有するポリフルオレンチオフェン系化合物を挙げることができる。一般式（２）中、Ｒ３及びＲ４はそれぞれ独立して、炭素数４〜１８のアルキル基を示し、ｎは１０〜１０００の整数を示す。 The polyfluorene thiophene type compound which has a structure represented by these can be mentioned. In General Formula (2), R 3 and R 4 each independently represent an alkyl group having 4 to 18 carbon atoms, and n represents an integer of 10 to 1000.
Ｒ３及びＲ４としては、炭素数４〜１８のアルキル基であれば特に限定されるものではなく、直鎖状であっても、分岐状であってもよい。 R 3 and R 4 are not particularly limited as long as they are alkyl groups having 4 to 18 carbon atoms, and may be linear or branched.
Ｒ３及びＲ４としては、より具体的には、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等を挙げることができる。 More specifically, as R 3 and R 4 , for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group Group, hexadecyl group, heptadecyl group, octadecyl group and the like.
＜赤色発光性共役高分子化合物＞
本発明で用いられる赤色発光性共役高分子化合物は、上述したように、エネルギー移動のアクセプターとなるものであり、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有するものであれば特に限定されるものではない。さらに、上述したように、本発明で用いられる赤色発光性共役高分子化合物は、上記青色発光性共役高分子化合物の発光波長とも部分的に重なる吸収波長を有していてもよい。
<Red light emitting conjugated polymer compound>
As described above, the red light-emitting conjugated polymer compound used in the present invention serves as an energy transfer acceptor, and has an absorption wavelength that partially overlaps the light emission wavelength of the green light-emitting conjugated polymer compound. If it is, it will not specifically limit. Furthermore, as described above, the red light-emitting conjugated polymer compound used in the present invention may have an absorption wavelength that partially overlaps with the light emission wavelength of the blue light-emitting conjugated polymer compound.
上記赤色発光性共役高分子化合物の吸収波長は、緑色発光性共役高分子化合物、又は青色発光性共役高分子化合物と緑色発光性共役高分子化合物との両方のフォトルミネセンスの発光波長の範囲の全部と重ならないことが好ましく、３７０〜６１０ｎｍの範囲に含まれることがより好ましい。これにより、上記赤色発光性共役高分子化合物は上記緑又は青色発光性共役高分子化合物の発光のエネルギーを吸収して、赤色の発光が起こる。 The absorption wavelength of the red light emitting conjugated polymer compound is in the range of the emission wavelength of the photoluminescence of both the green light emitting conjugated polymer compound or the blue light emitting conjugated polymer compound and the green light emitting conjugated polymer compound. It is preferable that it does not overlap all, and it is more preferable that it is included in the range of 370 to 610 nm. Accordingly, the red light-emitting conjugated polymer compound absorbs the light emission energy of the green or blue light-emitting conjugated polymer compound, and red light emission occurs.
また、上記赤色発光性共役高分子化合物は、好ましくは５２０〜７５０ｎｍの波長領域、より好ましくは、５４０〜７２０ｎｍの波長領域にフォトルミネセンスの発光ピークを有するものである。さらに好ましくは、本発明で用いられる赤色発光性共役高分子化合物は、フォトルミネセンスの発光波長が、５２０〜７５０ｎｍの波長領域、特に好ましくは５４０〜７２０ｎｍの波長領域に含まれるものである。 The red light-emitting conjugated polymer compound preferably has a photoluminescence emission peak in a wavelength region of 520 to 750 nm, more preferably in a wavelength region of 540 to 720 nm. More preferably, the red light-emitting conjugated polymer compound used in the present invention has a photoluminescence emission wavelength in the wavelength region of 520 to 750 nm, particularly preferably in the wavelength region of 540 to 720 nm.
また、上記赤色発光性共役高分子化合物は、５２０〜７５０ｎｍの波長領域にフォトルミネセンスの発光ピークを有し、かつ吸収波長が３７０〜６１０ｎｍであることが好ましい。これにより、青及び／又は緑色発光性共役高分子化合物からの部分的なフェルスター型エネルギー移動を受けることができ、かつバランスのよい白色発光を実現することができる。
上記赤色発光性共役高分子化合物としては、特に限定されるものではないが、例えばポリフェニレンビニレン系化合物、ポリチオフェン等を好適に用いることができる。
The red light-emitting conjugated polymer compound preferably has a photoluminescence emission peak in a wavelength region of 520 to 750 nm and an absorption wavelength of 370 to 610 nm. Thereby, it is possible to receive partial Forster energy transfer from the blue and / or green light-emitting conjugated polymer compound, and to realize balanced white light emission.
Although it does not specifically limit as said red light emission conjugated polymer compound, For example, a polyphenylene vinylene type compound, polythiophene, etc. can be used suitably.
上記赤色発光性共役高分子化合物のより具体的な一例としては、例えば、下記一般式（３） As a more specific example of the red light-emitting conjugated polymer compound, for example, the following general formula (3)
で表される構造を有するポリフェニレンビニレン系化合物を挙げることができる。一般式（３）中、Ｒ５及びＲ６はそれぞれ独立して、炭素数１〜１８のアルキル基を示し、ｎは１０〜１０００の整数を示す。 The polyphenylene vinylene type compound which has a structure represented by these can be mentioned. In General Formula (3), R 5 and R 6 each independently represent an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 10 to 1000.
Ｒ５及びＲ６としては、炭素数１〜１８のアルキル基であれば特に限定されるものではなく、直鎖状であっても、分岐状であってもよい。例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等を挙げることができる。 R 5 and R 6 are not particularly limited as long as they are alkyl groups having 1 to 18 carbon atoms, and may be linear or branched. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, A heptadecyl group, an octadecyl group, etc. can be mentioned.
また、Ｒ５とＲ６とは、対称すなわち同一であってもよいし、非対称すなわち相違していてもよい。中でも、Ｒ５とＲ６とは、非対称であることがより好ましい。これにより、青色及び緑色発光性共役高分子化合物との相溶性が向上するため好ましい。Ｒ５とＲ６とが非対称であることにより相溶性が向上する理由は明らかではないが、以下の理由が考えられる。すなわち、異種ポリマーの混合では必ず相分離は起こる。しかし対称置換基だと結晶性が向上し、融点上昇、ガラス転移温度の上昇を招き、結果的に相分離の程度は強くなる。それゆえ、非対称置換基の場合に相溶性が増すと考えられる。 R 5 and R 6 may be symmetric, that is, the same, or asymmetric, that is, different. Among these, R 5 and R 6 are more preferably asymmetric. This is preferable because the compatibility with the blue and green light-emitting conjugated polymer compounds is improved. The reason why the compatibility is improved by the asymmetry of R 5 and R 6 is not clear, but the following reasons are considered. That is, phase separation always occurs when different polymers are mixed. However, symmetric substituents improve crystallinity, increase the melting point and increase the glass transition temperature, and as a result, the degree of phase separation increases. Therefore, it is believed that compatibility is increased in the case of asymmetric substituents.
Ｒ５とＲ６とが、非対称である場合には、例えば、Ｒ５は炭素数１、２、３、４、５又は６のアルキル基であり、Ｒ６は炭素数４〜１８のアルキル基である。また、Ｒ６が炭素数１、２、３、４、５又は６のアルキル基であり、Ｒ５が炭素数４〜１８のアルキル基であってもよい。 When R 5 and R 6 are asymmetric, for example, R 5 is an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms, and R 6 is an alkyl group having 4 to 18 carbon atoms. It is. R 6 may be an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms, and R 5 may be an alkyl group having 4 to 18 carbon atoms.
また、Ｒ５とＲ６とは、分岐状のアルキル基であることがより好ましい。これにより、青色及び緑色発光性共役高分子化合物との相溶性が向上するため好ましい。 R 5 and R 6 are more preferably branched alkyl groups. This is preferable because the compatibility with the blue and green light-emitting conjugated polymer compounds is improved.
上記分岐状のアルキル基としても特に限定されるものではなく、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘプチル基、またはこれらの組み合わせを、分岐鎖として１個以上有する炭素数２〜１７のアルキル基を挙げることができる。 The branched alkyl group is not particularly limited. For example, carbon having one or more methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, heptyl groups, or combinations thereof as a branched chain. Examples of the alkyl group include 2 to 17.
＜共役高分子化合物混合溶液＞
上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物を含む共役高分子化合物混合溶液は、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物をこれらに対する良溶媒に溶解した溶液であればよい。かかる共役高分子化合物混合溶液は、例えば、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物をそれぞれ良溶媒に溶解した溶液を調製し、これらの各溶液を混合することによって調製することができる。各溶液を混合するために添加する順序は特に限定されるものではなく、どのような順であってもよい。
<Conjugated polymer compound mixed solution>
The conjugated polymer compound mixed solution including the blue luminescent conjugated polymer compound, the green luminescent conjugated polymer compound, and the red luminescent conjugated polymer compound includes the blue luminescent conjugated polymer compound and the green luminescent conjugate. Any solution may be used as long as the polymer compound and the red light-emitting conjugated polymer compound are dissolved in a good solvent for them. Such a conjugated polymer compound mixed solution is prepared by, for example, preparing a solution in which the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound and the red light-emitting conjugated polymer compound are dissolved in a good solvent. Can be prepared by mixing each solution. The order in which the solutions are added for mixing is not particularly limited, and may be in any order.
また、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物をそれぞれ良溶媒に溶解した溶液中における各共役高分子化合物の濃度は特に限定されるものではないが、例えば、２×１０−４〜５×１０−７Ｍである。なお、ここで、単位「Ｍ」は、溶液１Ｌ中に含まれるポリマーの繰返し単位で規格化したモル濃度を意味する。）
また、共役高分子化合物混合溶液中の上記青色発光性共役高分子化合物の濃度は１０−３〜１０−５Ｍであることが好ましい。
Further, the concentration of each conjugated polymer compound in a solution obtained by dissolving the blue luminescent conjugated polymer compound, the green luminescent conjugated polymer compound, and the red luminescent conjugated polymer compound in a good solvent is particularly limited. Although it is not a thing, it is 2 * 10 < -4 > -5 * 10 <-7> M, for example. Here, the unit “M” means the molar concentration normalized with the repeating unit of the polymer contained in 1 L of the solution. )
The concentration of the blue light-emitting conjugated polymer compound in the conjugated polymer compound mixed solution is preferably 10 −3 to 10 −5 M.
また、共役高分子化合物混合溶液中の上記緑色発光性共役高分子化合物の濃度は１０−３〜１０−５Ｍであることが好ましい。 The concentration of the green light-emitting conjugated polymer compound in the conjugated polymer compound mixed solution is preferably 10 −3 to 10 −5 M.
また、共役高分子化合物混合溶液中の上記赤色発光性共役高分子化合物の濃度は１０−５〜１０−７Ｍであることが好ましい。 Further, the concentration of the red light-emitting conjugated polymer compound in the conjugated polymer compound mixed solution is preferably 10 −5 to 10 −7 M.
ここで、上記良溶媒とは、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物と、−１０〜５０℃において、無制限に混合する溶媒であれば特に限定されるものではない。 Here, the good solvent is a solvent that is mixed indefinitely with the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound at −10 to 50 ° C. There is no particular limitation as long as it is present.
上記良溶媒は、用いる共役高分子化合物に応じて適宜選択すればよいが、例えば、クロロホルム、テトラヒドロフラン、トルエン、キシレン等を挙げることができる。 The good solvent may be appropriately selected according to the conjugated polymer compound to be used, and examples thereof include chloroform, tetrahydrofuran, toluene, xylene and the like.
また、上記共役高分子化合物混合溶液中に含まれる青色発光性共役高分子化合物、緑色発光性共役高分子化合物、赤色発光性共役高分子化合物の割合は、上記青色発光性共役高分子化合物に対する上記緑色発光性共役高分子化合物の割合が、好ましくは１〜１２０モル％、より好ましくは５〜１００モル％、さらに好ましくは１０〜１００モル％であり、上記青色発光性共役高分子化合物に対する上記赤色発光性共役高分子化合物の割合が、０．０００３〜１モル％、より好ましくは０．０１〜１モル％、さらに好ましくは０．０１〜０．１モル％である。なお、ここで、単位「モル％」は、ポリマーの繰返し単位で規格化したモル比率を意味する。 The ratio of the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound contained in the conjugated polymer compound mixed solution is the same as the ratio of the blue light-emitting conjugated polymer compound to the blue light-emitting conjugated polymer compound. The ratio of the green light-emitting conjugated polymer compound is preferably 1 to 120 mol%, more preferably 5 to 100 mol%, still more preferably 10 to 100 mol%, and the red color relative to the blue light-emitting conjugated polymer compound The ratio of the luminescent conjugated polymer compound is 0.0003 to 1 mol%, more preferably 0.01 to 1 mol%, and still more preferably 0.01 to 0.1 mol%. Here, the unit “mol%” means a molar ratio normalized by the repeating unit of the polymer.
＜白色発光性共役高分子複合材料＞
本発明に係る白色発光性共役高分子複合材料は、上記共役高分子化合物混合溶液に、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加して得られる凝集体を含んでいるものである。
<White light emitting conjugated polymer composite material>
The white light-emitting conjugated polymer composite material according to the present invention is prepared by adding the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound to the conjugated polymer compound mixed solution. It contains aggregates obtained by adding a poor solvent.
ここで、上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒とは、溶質を溶かす能力はあるが、溶解度に限界がある溶媒であれば特に限定されるものではない。 Here, the poor solvent for the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound is a solvent that has the ability to dissolve solutes but has limited solubility. There is no particular limitation as long as it is present.
上記貧溶媒は、用いる共役高分子化合物に応じて適宜選択すればよいが、例えば、メタノール、エタノール、イソプロパノール等を用いることができる。 The poor solvent may be appropriately selected according to the conjugated polymer compound to be used. For example, methanol, ethanol, isopropanol, or the like can be used.
上記共役高分子化合物混合溶液に、貧溶媒を添加すると、上記共役高分子化合物混合溶液に溶解していた上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物が凝集して凝集体が得られる。このとき、上記共役高分子化合物混合溶液に添加する貧溶媒の量も特に限定されるものではないが、上記共役高分子化合物混合溶液に対して、５０〜２５０体積％であることがより好ましく、６０〜２３０体積％であることがさらに好ましい。 When a poor solvent is added to the conjugated polymer compound mixed solution, the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugate dissolved in the conjugated polymer compound mixed solution. The polymer compound aggregates to obtain an aggregate. At this time, the amount of the poor solvent added to the conjugated polymer compound mixed solution is not particularly limited, but is more preferably 50 to 250% by volume with respect to the conjugated polymer compound mixed solution, More preferably, it is 60-230 volume%.
本発明に係る白色発光性共役高分子複合材料は、得られた上記凝集体を含むものであればよい。したがって、上記凝集体その物であってもよいし、上記凝集体の乾燥物であってもよいし、他の成分を含んでいてもよい。 The white light-emitting conjugated polymer composite material according to the present invention only needs to contain the obtained aggregate. Accordingly, the aggregate itself may be a dried product of the aggregate, or may contain other components.
本発明に係る白色発光性共役高分子複合材料に、白色発光を起こさせるためには、例えば、白色発光性共役高分子複合材料を、上記青色発光性共役高分子化合物の吸収波長である３５０〜４３０ｎｍの光によって励起すればよい。なお、本発明の白色発光性共役高分子複合材料は、電圧を印加することによっても、白色発光を発現させることができると考えられる。 In order to cause the white light-emitting conjugated polymer composite material according to the present invention to emit white light, for example, the white light-emitting conjugated polymer composite material is 350 to 350 which is the absorption wavelength of the blue light-emitting conjugated polymer compound. What is necessary is just to excite by the light of 430 nm. In addition, it is thought that the white light emitting conjugated polymer composite material of this invention can express white light emission also by applying a voltage.
（ＩＩ）白色発光性共役高分子複合材料の製造方法
また、本発明にかかる白色発光性共役高分子複合材料の製造方法は、３８０〜５００ｎｍの波長領域にフォトルミネセンスの発光ピークを有する青色発光性共役高分子化合物と、上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、を含む共役高分子化合物混合溶液を調製する、混合溶液調製工程と、当該共役高分子化合物混合溶液に貧溶媒を添加して白色発光性共役高分子複合材料を、凝集体として得る貧溶媒添加工程とを含んでいる。
(II) Method for Producing White Light-Emitting Conjugated Polymer Composite Material The method for producing a white light-emitting conjugated polymer composite material according to the present invention comprises blue light emission having a photoluminescence emission peak in a wavelength region of 380 to 500 nm. Light-emitting conjugated polymer compound, green light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the light emission wavelength of the blue light-emitting conjugated polymer compound, and light emission wavelength and partial of the green light-emitting conjugated polymer compound A conjugated polymer compound mixed solution containing a red luminescent conjugated polymer compound having an absorption wavelength overlapping with the mixed solution preparation step, and adding a poor solvent to the conjugated polymer compound mixed solution to emit white light And a poor solvent addition step for obtaining a conjugated polymer composite material as an aggregate.
ここで、上記混合溶液調製工程、及び、貧溶媒添加工程については、上記（Ｉ）で説明したとおりであるのでここでは説明を省略する。 Here, since the mixed solution preparation step and the poor solvent addition step are as described in the above (I), the description thereof is omitted here.
また、上記貧溶媒添加工程においては、貧溶媒を添加した後攪拌を行ってもよい。攪拌を行う時間は特に限定されるものではなく、０秒〜１０分程度である。 Moreover, in the said poor solvent addition process, after adding a poor solvent, you may stir. The time for stirring is not particularly limited, and is about 0 second to 10 minutes.
本発明にかかる白色発光性共役高分子複合材料の製造方法を用いれば、青色発光性共役高分子化合物、緑色発光性共役高分子化合物及び赤色発光性共役高分子化合物の割合や溶媒組成を変化させることにより、白色発光の色調を容易に制御することができる。 If the method for producing a white light-emitting conjugated polymer composite material according to the present invention is used, the ratio and the solvent composition of the blue light-emitting conjugated polymer compound, the green light-emitting conjugated polymer compound, and the red light-emitting conjugated polymer compound are changed. This makes it possible to easily control the color tone of white light emission.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.
〔青色発光性共役高分子化合物溶液の調製〕
青色発光性共役高分子化合物として、ポリ（９,９−ｎ−ジオクチル−２,７−フルオレン）（ＰＦ８、Aldrich社製、Ｍｗ：74000、Ｍｗ／Ｍｎ：4.4）３．８８ｍｇを秤量し、サンプル管に入れた。秤量したＰＦ８を、クロロホルム スペクトロゾール（登録商標）（同仁化学研究所製）１０ｍＬに溶解し、１．０×１０−３Ｍのストック溶液を調製した。当該ストック溶液に、クロロホルム スペクトロゾール（登録商標）を加えることで希釈し、目的の濃度の青色発光性共役高分子化合物溶液とした。
(Preparation of blue light-emitting conjugated polymer compound solution)
As a blue light-emitting conjugated polymer compound, 3.88 mg of poly (9,9-n-dioctyl-2,7-fluorene) (PF8, manufactured by Aldrich, Mw: 74000, Mw / Mn: 4.4) was weighed and sampled Put in a tube. The weighed PF8 was dissolved in 10 mL of chloroform Spectrozol (registered trademark) (manufactured by Dojindo Laboratories) to prepare a 1.0 × 10 −3 M stock solution. The stock solution was diluted by adding chloroform Spectrozol (registered trademark) to obtain a blue light-emitting conjugated polymer compound solution having a target concentration.
〔緑色発光性共役高分子化合物溶液の調製〕
緑色発光性共役高分子化合物として、ポリ[(９,９−ジオクチルフルオレニル−２,７−ジイル)−コ−ビチオフェン]（Ｆ８Ｔ２、Aldrich社製、Ｍｗ：23000、Ｍｗ／Ｍｎ：2.5、蛍光量子収率φ＝89％）５．５２ｇを秤量し、サンプル管に入れた。秤量したＦ８Ｔ２を、クロロホルム スペクトロゾール（登録商標）（同仁化学研究所製）１０ｍＬに溶解し、１．０×１０−３Ｍのストック溶液を調製した。当該ストック溶液に、クロロホルム スペクトロゾール（登録商標）を加えることで希釈し、目的の濃度の緑色発光性共役高分子化合物溶液とした。
[Preparation of green light-emitting conjugated polymer compound solution]
As a green light-emitting conjugated polymer compound, poly [(9,9-dioctylfluorenyl-2,7-diyl) -co-bithiophene] (F8T2, manufactured by Aldrich, Mw: 23000, Mw / Mn: 2.5, fluorescence (Quantum yield φ = 89%) 5.52 g was weighed and placed in a sample tube. Weighed F8T2 was dissolved in 10 mL of chloroform Spectrozole (registered trademark) (manufactured by Dojindo Laboratories) to prepare a 1.0 × 10 −3 M stock solution. The stock solution was diluted by adding chloroform Spectrozole (registered trademark) to obtain a green light-emitting conjugated polymer compound solution having a target concentration.
〔赤色発光性共役高分子化合物溶液の調製〕
赤色発光性共役高分子化合物として、ポリ[２−メトキシ−５−（２−エチルヘキシロキシ）−１,４−フェニレンビニレン]（ＭＥＨ−ＰＰＶ、Aldrich社製、Ｍｗ：304000、Ｍｗ／Ｍｎ：4.5）２．６０ｇを秤量し、サンプル管に入れた。秤量したＭＥＨ−ＰＰＶを、クロロホルム スペクトロゾール（登録商標）（同仁化学研究所製）１０ｍＬに溶解して１．０×１０−３Ｍのストック溶液を調製した。当該ストック溶液に、クロロホルム スペクトロゾール（登録商標）を加えることで希釈し、目的の濃度の赤色発光性共役高分子化合物溶液とした。
[Preparation of red light-emitting conjugated polymer compound solution]
As a red light emitting conjugated polymer compound, poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene] (MEH-PPV, manufactured by Aldrich, Mw: 304000, Mw / Mn: 4.5 ) 2.60 g was weighed and placed in a sample tube. The weighed MEH-PPV was dissolved in 10 mL of chloroform Spectrozole (registered trademark) (manufactured by Dojindo Laboratories) to prepare a 1.0 × 10 −3 M stock solution. The stock solution was diluted by adding chloroform Spectrozol (registered trademark) to obtain a red light-emitting conjugated polymer compound solution having a target concentration.
〔実施例１〕
１０ｍｍ×１０ｍｍ角セル内で、１．０×１０−４Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．９ｍＬに、５．０×１０−６Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、２．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．９ｍＬを加えて共役高分子化合物混合溶液を調製した。
[Example 1]
In a 10 mm × 10 mm square cell, 1.0 × 10 −4 M of the green light-emitting conjugated polymer compound solution (F8T2 solution) 0.9 mL, 5.0 × 10 −6 M of the red light-emitting conjugate high A molecular compound solution (MEH-PPV solution) 20 μL and 2.0 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.9 mL were added to prepare a conjugated polymer compound mixed solution.
この共役高分子化合物混合溶液に、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）１．２ｍＬを加え、スターラーを用いて５分間撹拌することにより凝集体を得た。凝集体が発現した後、凝集体を含むセル内の液をスターラーで３０秒間攪拌し、凝集体を均一に拡散させて各種光学測定を行った。得られた凝集体から、３６５ｎｍ付近の励起光により白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。 To this conjugated polymer compound mixed solution, 1.2 mL of methanol Spectrozol (registered trademark) (manufactured by Dojindo Laboratories), which is a poor solvent, was added and stirred for 5 minutes using a stirrer to obtain an aggregate. After the aggregate was developed, the liquid in the cell containing the aggregate was stirred for 30 seconds with a stirrer to uniformly diffuse the aggregate, and various optical measurements were performed. From the obtained aggregate, white light emission was observed by excitation light around 365 nm. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
得られた凝集体のフォトルミネセンス（ＰＬ）スペクトルを図３に示す。３種類の共役高分子化合物を良溶媒であるクロロホルム中で混和させ、さらに貧溶媒であるメタノールで凝集体を発現させ、ポリマー鎖間を近接させることで、共役高分子化合物間のエネルギー移動が効率よく起こり、可視域の全波長をカバーするように青、緑及び赤を発光させることができたことが判る。結果として白色発光性共役高分子複合材料が簡単に構築できた。 The photoluminescence (PL) spectrum of the obtained aggregate is shown in FIG. Efficient energy transfer between conjugated polymer compounds by mixing three types of conjugated polymer compounds in chloroform as a good solvent, expressing aggregates in methanol as a poor solvent, and bringing the polymer chains close together It is common to see that blue, green, and red could be emitted to cover all visible wavelengths. As a result, a white light-emitting conjugated polymer composite material was easily constructed.
また、得られた凝集体の蛍光顕微鏡による観察結果を図４に示す。蛍光顕微鏡観察により得られた凝集体は３種類の共役高分子化合物が別々に発光しているのではなく、１つの凝集体系から発光していることが判る。 Moreover, the observation result by the fluorescence microscope of the obtained aggregate is shown in FIG. It can be seen that the aggregate obtained by the fluorescence microscope observation emits light from one aggregate system, rather than the three conjugated polymer compounds emitting light separately.
また、得られた凝集体の蛍光スペクトルを図５に示す。図５より、単一凝集体からの部分的エネルギー移動の結果、可視域の全波長をカバーするように青、緑及び赤を発光させることができたことが判る。 Moreover, the fluorescence spectrum of the obtained aggregate is shown in FIG. From FIG. 5, it can be seen that as a result of partial energy transfer from a single aggregate, blue, green and red could be emitted so as to cover all wavelengths in the visible range.
なお、各実施例において用いた各共役高分子化合物溶液の濃度及び量並びに添加した貧溶媒の量を下表１に示す。 The concentration and amount of each conjugated polymer compound solution used in each example and the amount of the poor solvent added are shown in Table 1 below.
〔比較例１〕
１０ｍｍ×１０ｍｍ角セル内で、１．０×１０−４Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．９ｍＬに、２．１ｍＬのメタノール スペクトロゾール（登録商標）（同仁化学研究所製）を加え、スターラーを用いて５分間撹拌して凝集体を得た。
[Comparative Example 1]
In a 10 mm × 10 mm square cell, 2.1 × 10 −4 M of the above green light-emitting conjugated polymer compound solution (F8T2 solution) 0.9 mL, 2.1 mL of methanol Spectrozole (registered trademark) (Dojindo Laboratories) And agitation was obtained using a stirrer for 5 minutes.
１０ｍｍ×１０ｍｍ角セル内で、５．０×１０−６Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬに、２．９ｍＬのメタノール スペクトロゾール（登録商標）（同仁化学研究所製）を加え、スターラーを用いて５分間撹拌して凝集体を得た。 In a 10 mm × 10 mm square cell, 2.9 mL of methanol Spectrozol (registered trademark) (Dojindo Laboratories) was added to 20 μL of the above red light emitting conjugated polymer compound solution (MEH-PPV solution) of 5.0 × 10 −6 M. And agitation was obtained using a stirrer for 5 minutes.
１０ｍｍ×１０ｍｍ角セル内で、２．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．９ｍＬに、２．１ｍＬのメタノール スペクトロゾール（登録商標）（同仁化学研究所製）を加え、スターラーを用いて５分間撹拌して凝集体を得た。 In a 10 mm × 10 mm square cell, 2.1 mL of methanol Spectrozol (registered trademark) (manufactured by Dojindo Laboratories) was added to 0.9 mL of the 2.0 × 10 −4 M blue light-emitting conjugated polymer compound solution. In addition, the mixture was stirred for 5 minutes using a stirrer to obtain an aggregate.
凝集体を含む各発光性共役高分子化合物溶液を混合し、スターラーを用いて５分間攪拌し、蛍光顕微鏡観察を行ったが白色発光は観察されなかった。 Each luminescent conjugated polymer compound solution containing an aggregate was mixed, stirred for 5 minutes using a stirrer, and observed with a fluorescence microscope, but no white light emission was observed.
〔実施例２〕
２．０×１０−５の上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．９ｍＬに、５．０×１０−６Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、２．０×１０−５Ｍの上記青色発光性共役高分子化合物溶液０．９ｍＬを加えた以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
[Example 2]
To 0.9 mL of the green light-emitting conjugated polymer compound solution (F8T2 solution) of 2.0 × 10 −5 , 5.0 × 10 −6 M of the red light-emitting conjugated polymer compound solution (MEH-PPV solution) Aggregates were obtained in the same manner as in Example 1 except that 0.9 mL of the blue light-emitting conjugated polymer compound solution of 20 μL and 2.0 × 10 −5 M was added. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例３〕
２．０×１０−４Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．９ｍＬに、５．０×１０−５Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、２．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液１．３ｍＬを加えた以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 3
To 0.9 mL of 2.0 × 10 −4 M of the green luminescent conjugated polymer compound solution (F8T2 solution), 5.0 × 10 −5 M of the red luminescent conjugated polymer compound solution (MEH-PPV solution). ) Aggregates were obtained in the same manner as in Example 1 except that 1.3 mL of the blue light-emitting conjugated polymer compound solution of 20 μL and 2.0 × 10 −4 M was added. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例４〕
２．０×１０−５Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．３ｍＬに、５．０×１０−７Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）０．１ｍＬ、及び、１．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．８ｍＬを加え、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）の添加量を１．７ｍＬとした以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 4
To 0.3 mL of 2.0 × 10 −5 M green light-emitting conjugated polymer compound solution (F8T2 solution), 5.0 × 10 −7 M red light-emitting conjugated polymer compound solution (MEH-PPV solution) ) Add 0.1 mL and 0.8 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.8 mL, and use methanol spectrozole (registered trademark) (manufactured by Dojindo Laboratories) as a poor solvent. Aggregates were obtained in the same manner as in Example 1 except that the addition amount was 1.7 mL. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例５〕
２．０×１０−５Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．３ｍＬに、５．０×１０−７Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）０．１５ｍＬ、及び、１．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．９ｍＬを加え、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）の添加量を１．７ｍＬとした以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 5
To 0.3 mL of 2.0 × 10 −5 M green light-emitting conjugated polymer compound solution (F8T2 solution), 5.0 × 10 −7 M red light-emitting conjugated polymer compound solution (MEH-PPV solution) ) 0.15 mL and 1.0 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.9 mL were added, and methanol Spectrosol (registered trademark) (manufactured by Dojindo Laboratories), which is a poor solvent, was added. Aggregates were obtained in the same manner as in Example 1 except that the addition amount was 1.7 mL. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例６〕
２．０×１０−５Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．３ｍＬに、５．０×１０−７Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、１．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．６ｍＬを加え、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）の添加量を１．８ｍＬとした以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 6
To 0.3 mL of 2.0 × 10 −5 M green light-emitting conjugated polymer compound solution (F8T2 solution), 5.0 × 10 −7 M red light-emitting conjugated polymer compound solution (MEH-PPV solution) ) 20 μL and 1.0 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.6 mL are added, and the amount of methanol spectrosol (registered trademark) (manufactured by Dojindo Laboratories), which is a poor solvent, is added. An agglomerate was obtained in the same manner as in Example 1 except that the amount was 1.8 mL. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例７〕
２．０×１０−５Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．６ｍＬに、５．０×１０−５Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、２．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．９ｍＬを加え、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）の添加量を１．８ｍＬとした以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 7
To 0.6 mL of 2.0 × 10 −5 M of the green light-emitting conjugated polymer compound solution (F8T2 solution), 5.0 × 10 −5 M of the red light-emitting conjugated polymer compound solution (MEH-PPV solution). ) 20 μL and 2.0 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.9 mL are added, and the amount of methanol spectrosol (registered trademark) (manufactured by Dojindo Laboratories) as a poor solvent is added. An agglomerate was obtained in the same manner as in Example 1 except that the amount was 1.8 mL. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例８〕
２．０×１０−５Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．６ｍＬに、５．０×１０−７Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、１．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．５ｍＬを加え、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）の添加量を１．９ｍＬとした以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 8
To 0.6 mL of the green light-emitting conjugated polymer compound solution (F8T2 solution) of 2.0 × 10 −5 M, 5.0 × 10 −7 M of the red light-emitting conjugated polymer compound solution (MEH-PPV solution) ) 20 μL and 1.0 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.5 mL are added, and the amount of methanol spectrosol (registered trademark) (manufactured by Dojindo Laboratories) as a poor solvent is added. An agglomerate was obtained in the same manner as in Example 1 except that was changed to 1.9 mL. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
〔実施例９〕
２．０×１０−５Ｍの上記緑色発光性共役高分子化合物溶液（Ｆ８Ｔ２溶液）０．３ｍＬに、５．０×１０−７Ｍの上記赤色発光性共役高分子化合物溶液（ＭＥＨ−ＰＰＶ溶液）２０μＬ、及び、１．０×１０−４Ｍの上記青色発光性共役高分子化合物溶液０．６ｍＬを加え、貧溶媒であるメタノール スペクトロゾール（登録商標）（同仁化学研究所製）の添加量を２．１ｍＬとした以外は実施例１と同様にして凝集体を得た。得られた凝集体から白色発光が観察された。また、得られた凝集体においては巨視的には相分離は確認されなかった。
Example 9
To 0.3 mL of 2.0 × 10 −5 M green light-emitting conjugated polymer compound solution (F8T2 solution), 5.0 × 10 −7 M red light-emitting conjugated polymer compound solution (MEH-PPV solution) ) 20 μL and 1.0 × 10 −4 M of the blue light-emitting conjugated polymer compound solution 0.6 mL are added, and the amount of methanol spectrosol (registered trademark) (manufactured by Dojindo Laboratories), which is a poor solvent, is added. An aggregate was obtained in the same manner as in Example 1 except that the amount was 2.1 mL. White luminescence was observed from the resulting aggregate. Further, in the obtained aggregate, no phase separation was confirmed macroscopically.
実施例１−９では得られた凝集体からいずれも白色発光が観察された。また、各共役高分子化合物溶液の濃度及び量並びに添加した貧溶媒の量を変化させることにより、色調制御及び相対発光強度を制御することができることが判った。 In Example 1-9, white luminescence was observed from any of the obtained aggregates. It was also found that the color tone control and the relative light emission intensity can be controlled by changing the concentration and amount of each conjugated polymer compound solution and the amount of the poor solvent added.
本発明にかかる白色発光性共役高分子複合材料及びその製造方法を用いれば、液晶ディスプレイ、フルカラーディスプレイのバックライト、照明装置、大画面フラットパネルディスプレイ等に利用できる白色発光性材料を、入手容易で安価な発光性高分子化合物から、簡便に構築できるとともに、色調制御が容易で、相溶性が良い白色発光性材料を実現することができる。 By using the white light-emitting conjugated polymer composite material and the manufacturing method thereof according to the present invention, a white light-emitting material that can be used for a liquid crystal display, a backlight of a full-color display, a lighting device, a large screen flat panel display, etc. A white light-emitting material that can be easily constructed from an inexpensive light-emitting polymer compound, can be easily controlled in color tone, and has good compatibility can be realized.
それゆえ、本発明は、白色発光性材料の製造を行う化学工業において利用可能であるのみならず、さらにはこれを利用する液晶ディスプレイ、フルカラーディスプレイのバックライト、照明装置、大画面フラットパネルディスプレイ等を製造する工業においても利用可能であり、しかも非常に有用であると考えられる。 Therefore, the present invention can be used not only in the chemical industry for producing white light emitting materials, but also in liquid crystal displays, full color display backlights, lighting devices, large screen flat panel displays, etc. It can also be used in the industry for manufacturing, and is considered to be very useful.
Claims (11)
上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、
上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、
を含む共役高分子化合物混合溶液に、
上記青色発光性共役高分子化合物、上記緑色発光性共役高分子化合物及び上記赤色発光性共役高分子化合物に対する貧溶媒を添加して得られる凝集体を含むことを特徴とする白色発光性共役高分子複合材料。 A blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm;
A green light-emitting conjugated polymer compound having an absorption wavelength that partially overlaps the emission wavelength of the blue light-emitting conjugated polymer compound;
A red light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the emission wavelength of the green light-emitting conjugated polymer compound;
In a conjugated polymer compound mixed solution containing
A white light emitting conjugated polymer comprising an aggregate obtained by adding a poor solvent for the blue light emitting conjugated polymer compound, the green light emitting conjugated polymer compound, and the red light emitting conjugated polymer compound. Composite material.
上記青色発光性共役高分子化合物に対する上記赤色発光性共役高分子化合物の割合は、０．０００３〜１モル％であることを特徴とする請求項１〜５のいずれか１項に記載の白色発光性共役高分子複合材料。 The ratio of the green light-emitting conjugated polymer compound to the blue light-emitting conjugated polymer compound is 1 to 120 mol%,
The ratio of the said red light emission conjugated polymer compound with respect to the said blue light emission conjugated polymer compound is 0.0003-1 mol%, The white light emission of any one of Claims 1-5 characterized by the above-mentioned. Conjugated polymer composite material.
で表される構造を有することを特徴とする請求項１〜７のいずれか１項に記載の白色発光性共役高分子複合材料。 The blue light-emitting conjugated polymer compound has the following general formula (1)
The white light-emitting conjugated polymer composite material according to claim 1, wherein the white light-emitting conjugated polymer composite material has a structure represented by:
で表される構造を有することを特徴とする請求項１〜８のいずれか１項に記載の白色発光性共役高分子複合材料。 The green light-emitting conjugated polymer compound has the following general formula (2)
The white light-emitting conjugated polymer composite material according to claim 1, wherein the white light-emitting conjugated polymer composite material has a structure represented by:
で表される構造を有することを特徴とする請求項１〜９のいずれか１項に記載の白色発光性共役高分子複合材料。 The red light-emitting conjugated polymer compound has the following general formula (3)
The white light-emitting conjugated polymer composite material according to claim 1, wherein the white light-emitting conjugated polymer composite material has a structure represented by:
上記青色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する緑色発光性共役高分子化合物と、
上記緑色発光性共役高分子化合物の発光波長と部分的に重なる吸収波長を有する赤色発光性共役高分子化合物と、
を含む共役高分子化合物混合溶液を調製する混合溶液調製工程と、
当該共役高分子化合物混合溶液に貧溶媒を添加して白色発光性共役高分子複合材料を、凝集体として得る貧溶媒添加工程と、
を含むことを特徴とする白色発光性共役高分子複合材料の製造方法。 A blue light-emitting conjugated polymer compound having a photoluminescence emission peak in a wavelength region of 380 to 500 nm;
A green light-emitting conjugated polymer compound having an absorption wavelength that partially overlaps the emission wavelength of the blue light-emitting conjugated polymer compound;
A red light-emitting conjugated polymer compound having an absorption wavelength partially overlapping with the emission wavelength of the green light-emitting conjugated polymer compound;
A mixed solution preparation step of preparing a conjugated polymer compound mixed solution containing:
A poor solvent addition step of adding a poor solvent to the conjugated polymer compound mixed solution to obtain a white light-emitting conjugated polymer composite material as an aggregate;
A method for producing a white light-emitting conjugated polymer composite material comprising:
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