JP7177001B2 - Dibenzopyromethene boron chelate compound, near-infrared light absorbing dye, photoelectric conversion device, near-infrared light sensor and imaging device - Google Patents
Dibenzopyromethene boron chelate compound, near-infrared light absorbing dye, photoelectric conversion device, near-infrared light sensor and imaging device Download PDFInfo
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- JP7177001B2 JP7177001B2 JP2019096458A JP2019096458A JP7177001B2 JP 7177001 B2 JP7177001 B2 JP 7177001B2 JP 2019096458 A JP2019096458 A JP 2019096458A JP 2019096458 A JP2019096458 A JP 2019096458A JP 7177001 B2 JP7177001 B2 JP 7177001B2
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- aromatic
- heterocyclic
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- -1 boron chelate compound Chemical class 0.000 title claims description 121
- 238000006243 chemical reaction Methods 0.000 title claims description 92
- 238000003384 imaging method Methods 0.000 title claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 239000010409 thin film Substances 0.000 claims description 32
- 125000000623 heterocyclic group Chemical group 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 125000001931 aliphatic group Chemical group 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000005647 linker group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
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- 239000000758 substrate Substances 0.000 description 9
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- 125000000335 thiazolyl group Chemical group 0.000 description 9
- 125000001544 thienyl group Chemical group 0.000 description 9
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
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Description
本発明は、ジベンゾピロメテンホウ素キレート構造を有する新規な化合物、光電変換素子、光センサー、撮像素子に関する。特に、近赤外領域に主たる吸収帯を有する光電変換素子及びその利用に関する。 TECHNICAL FIELD The present invention relates to a novel compound having a dibenzopyromethene boron chelate structure, a photoelectric conversion device, a photosensor, and an imaging device. In particular, it relates to a photoelectric conversion element having a main absorption band in the near-infrared region and its use.
７８０乃至２０００ｎｍの近赤外領域（国際電気標準会議規格ＩＥＣ６００５０－８４１；１９８３）に吸収帯を有する近赤外光吸収色素は、従来から産業上の様々な用途への応用が検討されている。例を挙げると、近赤外光吸収色素は、ＣＤ－Ｒ（Ｃｏｍｐａｃｔ Ｄｉｓｋ－Ｒｅｃｏｒｄａｂｌｅ）等の光情報記録媒体；サーマルＣＴＰ（Ｃｏｍｐｕｔｅｒ Ｔｏ Ｐｌａｔｅ）、フラッシュトナー定着、レーザー感熱記録等の印刷用途；熱遮断フィルム等の用途に利用されている。さらには、近赤外光吸収色素は、選択的に特定波長域の光を吸収するというその特性を用いて、ＰＤＰ（プラズマ・ディスプレイ・パネル）のフィルター等に用いられる近赤外線カットフィルターや、植物成長調整用フィルム等にも使用されている。また、近赤外光吸収色素は、溶媒に溶解又は分散させることにより、近赤外光吸収インクとして使用することも可能である。該近赤外光吸収インクによる印字物は、目視では認識が困難であり、近赤外光検出器等でのみ読み取りが可能であることから、例えば偽造防止等を目的とした印字等に使用される。 Near-infrared light-absorbing dyes having an absorption band in the near-infrared region of 780 to 2000 nm (International Electrotechnical Commission standard IEC60050-841; 1983) have been studied for various industrial applications. Examples of near-infrared light absorbing dyes include optical information recording media such as CD-R (Compact Disk-Recordable); printing applications such as thermal CTP (Computer To Plate), flash toner fixing, and laser thermal recording; It is used for applications such as shielding films. Furthermore, near-infrared light-absorbing pigments can be used for near-infrared cut filters used in PDP (plasma display panel) filters, etc., and plants It is also used for growth control films. Also, the near-infrared light-absorbing dye can be used as a near-infrared light-absorbing ink by dissolving or dispersing it in a solvent. Printed matter using the near-infrared light absorbing ink is difficult to recognize visually and can be read only with a near-infrared light detector or the like. be.
このような不可視画像形成用の近赤外光吸収材料としては、無機系の近赤外光吸収材料と、有機系の近赤外光吸収材料とが既に知られている。このうち、無機系の近赤外光吸収材料としては、イッテルビウム等の希土類金属や、銅リン酸結晶化ガラス等が知られている。しかしながら、無機系の近赤外光吸収材料は、近赤外領域の光の吸収性が十分でないために、不可視画像の単位面積あたりに多量の近赤外光吸収材料が必要となる。そのため、無機系の近赤外光吸収材料によって不可視画像を形成した場合、その表面上にさらに可視画像を形成すると、下側の不可視画像の凹凸が表面側の可視画像に影響を与えてしまう。 As near-infrared light absorbing materials for such invisible image formation, inorganic near-infrared light absorbing materials and organic near-infrared light absorbing materials are already known. Among them, rare earth metals such as ytterbium, copper phosphate crystallized glass, and the like are known as inorganic near-infrared light absorbing materials. However, since inorganic near-infrared light absorbing materials do not sufficiently absorb light in the near-infrared region, a large amount of near-infrared light absorbing material is required per unit area of the invisible image. Therefore, when an invisible image is formed using an inorganic near-infrared light absorbing material, if a visible image is further formed on the surface, the unevenness of the invisible image on the lower side affects the visible image on the surface side.
それに対し、有機系の近赤外光吸収材料は、近赤外領域の光の吸収性が十分であるために、不可視画像の単位面積あたりの使用量が少なくてすむので、無機系の近赤外光吸収材料を使用した場合のような不都合は生じない。そのため、現在に至るまで多くの有機系近赤外光吸収材料の開発が進められている。 On the other hand, organic near-infrared light-absorbing materials have sufficient light absorptivity in the near-infrared region. Inconveniences such as those in the case of using an external light absorbing material do not occur. Therefore, many organic near-infrared light absorbing materials have been developed up to now.
例えば、特許文献１には、有機系の近赤外光吸収材料として、ナフタロシアニン系化合物が開示されている。しかしながら、ナフタロシアニン系化合物は、製造方法の煩雑さ、及び溶解性の調整の困難さがあることから、一般の工業的には、対イオン性色素化合物を近赤外光吸収材料として用いることが通常となっている。
また、さらに特許文献２には、近赤外領域に蛍光波長を有する近赤外蛍光色素の例として、ナフトフルオレセイン化合物が開示されている。
For example,
Furthermore,
一方、有機エレクトロニクスデバイスは、原材料に希少金属などを含まず，安定した供給が可能であるのみならず、無機材料には無い屈曲性や湿式成膜法による製造が可能な点から、近年非常に関心が高まっている。有機エレクトロニクスデバイスの具体例としては有機ＥＬ素子、有機太陽電池素子、有機光電変換素子及び有機トランジスタ素子等が挙げられ、デバイスとしての性能は勿論のこと、有機材料の特色を活かした用途が検討されている。 On the other hand, organic electronic devices, which do not contain rare metals as raw materials, can be stably supplied, have flexibility that inorganic materials do not have, and can be manufactured by a wet film-forming method. Interest is growing. Specific examples of organic electronic devices include organic EL elements, organic solar cell elements, organic photoelectric conversion elements, organic transistor elements, and the like, and not only performance as devices but also applications that take advantage of the characteristics of organic materials are being studied. ing.
非特許文献１では、赤色又は近赤外光領域に吸収帯から蛍光帯を示し、堅牢性の優れた色素としてボロンジピロメテン色素（ｂｏｒｏｎ－ｄｉｐｙｒｒｏｍｅｔｈｅｎｅ、以下「ＢＯＤＩＰＹ」と称す。）に関する報告がなされている。
また、特許文献３乃至５には、ＢＯＤＩＰＹ骨格を有する化合物をＢ－Ｏキレート化することにより、化合物の光に対する堅牢性が更に向上すると共に、吸収波長を長波長側にシフトさせることができることが記載されている。しかしながら、ＢＯＤＩＰＹ骨格を有する化合物はＢ－Ｏキレート化することにより分子の剛直性が高くなるため、溶解性が著しく低下するのが一般的である。
Non-Patent
Further,
現在用いられている近赤外光吸収色素には、更なる耐久性の向上が求められている。しかも工業的に用いるための加工容易性を考慮すると、溶剤に対する高い溶解性を有しつつ、近赤外光吸収特性を維持することが必要である。 Near-infrared light absorbing dyes currently used are required to have further improved durability. Moreover, considering ease of processing for industrial use, it is necessary to maintain near-infrared light absorption properties while maintaining high solubility in solvents.
本発明の目的は、近赤外領域帯に吸収特性を有すると共に、溶剤に対する高い溶解性を示すことによって溶液プロセスで薄膜を形成し得る近赤外光吸収材料、該近赤外光吸収材料を含む有機薄膜、該有機薄膜を含む有機エレクトロデバイス及び該有機薄膜を含む有機光電変換素子を提供することにある。 An object of the present invention is to provide a near-infrared light-absorbing material that has absorption characteristics in the near-infrared region and exhibits high solubility in a solvent, thereby forming a thin film in a solution process, and the near-infrared light-absorbing material. It is an object of the present invention to provide an organic thin film containing the organic thin film, an organic electronic device containing the organic thin film, and an organic photoelectric conversion element containing the organic thin film.
本発明者らは前記諸課題を解決するべく考究した結果、分子内にアゾメチン骨格を導入したジベンゾピロメテンホウ素キレート化合物を用いることにより上記の課題が解決することを見出し、本発明を完成するに至った。
即ち、本発明は、
[１]下記一般式（１）
As a result of investigations aimed at solving the above problems, the present inventors found that the above problems can be solved by using a dibenzopyrromethene boron chelate compound having an azomethine skeleton introduced into the molecule, and have completed the present invention. Arrived.
That is, the present invention
[1] General formula (1) below
（式中、Ｒ１乃至Ｒ８はそれぞれ独立に水素原子、脂肪族炭化水素基、アルコキシ基、アルキルチオ基、芳香族基、複素環基、ハロゲン原子、水酸基、メルカプト基、ニトロ基、置換アミノ基、非置換アミノ基、シアノ基、スルホ基、又はアシル基を表す。Ｒ９及びＲ１０はそれぞれ独立に水素原子、脂肪族炭化水素基、芳香族基、又は複素環基を表す。Ｒ１１及びＲ１２はそれぞれ独立に脂肪族炭化水素基、芳香族基、又は複素環基を表す。Ｚ１及びＺ２はそれぞれ独立に芳香族化合物の芳香環から水素原子を二つ除いた二価の連結基、又は複素環化合物の複素環から水素原子を二つ除いた二価の連結基を表す。ｎはそれぞれ独立に０以上の整数を表す。）で表されるジベンゾピロメテンホウ素キレート化合物、
［２］ｎが１である前項［１］に記載のジベンゾピロメテンホウ素キレート化合物、
［３］Ｒ９及びＲ１０が水素原子である前項［１］又は［２］に記載のジベンゾピロメテンホウ素キレート化合物、
［４］Ｒ１１及びＲ１２が芳香族基、又は複素環基である前項［１］乃至［３］のいずれか一項に記載のジベンゾピロメテンホウ素キレート化合物、
［５］前項［１］乃至［４］のいずれか一項に記載のジベンゾピロメテンホウ素キレート化合物含む近赤外吸収色素、
［６］前項［１］乃至［４］のいずれか一項に記載のジベンゾピロメテンホウ素キレート化合物含む有機薄膜、
［７］前項［１］乃至［４］のいずれか一項に記載のジベンゾピロメテンホウ素キレート化合物を含む光電変換素子、
［８］前項［７］に記載の光電変換素子を備える近赤外光センサー、及び
［９］前項［７］に記載の光電変換素子を備える撮像素子、
に関する。
(wherein R 1 to R 8 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group, , an unsubstituted amino group, a cyano group, a sulfo group, or an acyl group, R 9 and R 10 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic group, or a heterocyclic group, R 11 and R 12 each independently represents an aliphatic hydrocarbon group, an aromatic group, or a heterocyclic group Z 1 and Z 2 each independently represent a divalent linkage obtained by removing two hydrogen atoms from an aromatic ring of an aromatic compound group, or a divalent linking group obtained by removing two hydrogen atoms from the heterocyclic ring of the heterocyclic compound.n represents an integer of 0 or more.),
[2] The dibenzopyrromethene boron chelate compound according to [1] above, wherein n is 1;
[3] The dibenzopyromethene boron chelate compound according to [1] or [2] above, wherein R 9 and R 10 are hydrogen atoms;
[4] The dibenzopyromethene boron chelate compound according to any one of [1] to [3] above, wherein R 11 and R 12 are an aromatic group or a heterocyclic group;
[5] A near-infrared absorbing dye containing the dibenzopyrromethene boron chelate compound according to any one of [1] to [4] above,
[6] An organic thin film containing the dibenzopyromethene boron chelate compound according to any one of [1] to [4] above,
[7] A photoelectric conversion device containing the dibenzopyromethene boron chelate compound according to any one of [1] to [4] above,
[8] A near-infrared light sensor comprising the photoelectric conversion element according to [7] above, and [9] An imaging device comprising the photoelectric conversion element according to [7] above,
Regarding.
本発明のジベンゾピロメテンホウ素キレート化合物は、近赤外領域に吸収特性を有し、高い溶解性を有することで溶液塗布による成膜が可能なことから、ウェットプロセスによる光電素子の作製及びそれを含む有機撮像素子、光センサー、赤外センサー等のデバイスやそれらを用いたカメラ、ビデオカメラ、赤外線カメラ等の分野へ応用することができる。 The dibenzopyromethene boron chelate compound of the present invention has absorption properties in the near-infrared region and has high solubility, so that film formation by solution coating is possible. It can be applied to fields such as devices such as organic imaging devices, optical sensors, and infrared sensors, and cameras, video cameras, and infrared cameras using them.
以下、本発明の内容について詳細に説明する。ここに記載する構成要件の説明については、本発明の代表的な実施態様や具体例に基づくものである一方、本発明はそのような実施態様や具体例に限定されない。なお、本発明において近赤外領域とは、７８０乃至２０００ｎｍの範囲内にある波長領域をいい、近赤外光吸収材料（色素）とは近赤外光領域に主たる吸収波長をもつ材料をいい、近赤外発光材料（色素）とは近赤外光領域において発光する材料をいう。 The contents of the present invention will be described in detail below. While the descriptions of the constituent elements described herein are based on representative embodiments and examples of the invention, the invention is not limited to such embodiments and examples. In the present invention, the near-infrared region refers to a wavelength region within the range of 780 to 2000 nm, and the near-infrared light absorbing material (dye) refers to a material having an absorption wavelength mainly in the near-infrared region. A near-infrared light-emitting material (dye) means a material that emits light in the near-infrared region.
本発明のジベンゾピロメテンホウ素キレート化合物は上記式（１）で表される。尚、上記の式（１）は共鳴構造の一つを示したものにすぎず、本発明の化合物は図示した共鳴構造に限定されるものではない。
式（１）中のＲ１乃至Ｒ８はそれぞれ独立に水素原子、脂肪族炭化水素基、アルコキシ基、アルキルチオ基、芳香族基、複素環基、ハロゲン原子、水酸基、メルカプト基、ニトロ基、置換アミノ基、非置換アミノ基、シアノ基、スルホ基、又はアシル基を表す。
The dibenzopyromethene boron chelate compound of the present invention is represented by the above formula (1). The above formula (1) merely shows one resonance structure, and the compound of the present invention is not limited to the illustrated resonance structure.
R 1 to R 8 in formula (1) each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, or a substituted represents an amino group, an unsubstituted amino group, a cyano group, a sulfo group, or an acyl group;
上記式（１）中のＲ１乃至Ｒ８が表す脂肪族炭化水素基は、飽和又は不飽和の直鎖状、分岐状又は環状のいずれにも限定されず、その炭素数は１乃至３０が好ましく、１乃至２０がより好ましい。ここで、飽和又は不飽和の直鎖、分岐又は環状の脂肪族炭化水素基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、アリル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－セチル基、ｎ－ヘプタデシル基、ｎ－ブテニル基、２－エチルへキシル基、３－エチルヘプチル基、４－エチルオクチル基、２－ブチルオクチル基、３－ブチルノニル基、４－ブチルデシル基、２－ヘキシルデシル基、３－オクチルウンデシル基、４－オクチルドデシル基、２－オクチルドデシル基、２－デシルテトラデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
式（１）中のＲ１乃至Ｒ８が表す脂肪族炭化水素基としては、直鎖状又は分岐状の脂肪族炭化水素基であることが好ましく、飽和の直鎖状又は分岐状のアルキル基であることがより好ましく、ｎ－ブチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ドデシル基、２－エチルへキシル基、２－メチルプロピル基又は２－ブチルオクチル基であることが更に好ましく、ｎ－ヘキシル基、ｎ－オクチル基又は２－メチルプロピル基であることが特に好ましい。
The aliphatic hydrocarbon group represented by R 1 to R 8 in the above formula (1) is not limited to any of saturated or unsaturated linear, branched or cyclic, and has 1 to 30 carbon atoms. Preferably, 1 to 20 are more preferable. Here, specific examples of saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group and allyl group. , t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-cetyl group, n-heptadecyl group , n-butenyl group, 2-ethylhexyl group, 3-ethylheptyl group, 4-ethyloctyl group, 2-butyloctyl group, 3-butylnonyl group, 4-butyldecyl group, 2-hexyldecyl group, 3-octyl undecyl group, 4-octyldodecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
The aliphatic hydrocarbon group represented by R 1 to R 8 in formula (1) is preferably a linear or branched aliphatic hydrocarbon group, and a saturated linear or branched alkyl group More preferably, n-butyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 2-methylpropyl group or 2-butyloctyl group is more preferred, and n-hexyl group, n-octyl group or 2-methylpropyl group is particularly preferred.
上記式（１）中のＲ１乃至Ｒ８が表すアルコキシ基とは、酸素原子とアルキル基が結合した置換基であり、アルコキシ基が有するアルキル基としては、例えば式（１）中のＲ１乃至Ｒ８が表す脂肪族炭化水素基の項に具体例として記載したアルキル基が挙げられる。
式（１）中のＲ１乃至Ｒ８が表すアルコキシ基は、例えばアルコキシ基等の置換基を有していてもよい。
上記式（１）中のＲ１乃至Ｒ８が表すアルキルチオ基とは、硫黄原子とアルキル基が結合した置換基であり、アルキルチオ基が有するアルキル基としては、例えば式（１）中のＲ１乃至Ｒ８が表す脂肪族炭化水素基の項に具体例として記載したアルキル基が挙げられる。
式（１）中のＲ１乃至Ｒ８が表すアルキルチオ基は、例えばアルキルチオ基等の置換基を有していてもよい。
The alkoxy group represented by R 1 to R 8 in the above formula ( 1 ) is a substituent in which an oxygen atom and an alkyl group are bonded. Specific examples thereof include the alkyl groups described in the section on the aliphatic hydrocarbon group represented by R 8 to R 8 .
The alkoxy group represented by R 1 to R 8 in formula (1) may have a substituent such as an alkoxy group.
The alkylthio group represented by R 1 to R 8 in the above formula ( 1 ) is a substituent in which a sulfur atom and an alkyl group are bonded. Specific examples thereof include the alkyl groups described in the section on the aliphatic hydrocarbon group represented by R 8 to R 8 .
The alkylthio groups represented by R 1 to R 8 in formula (1) may have a substituent such as an alkylthio group.
上記式（１）中のＲ１乃至Ｒ８が表す芳香族基とは、芳香族化合物の芳香環から水素原子を一つ除いた残基である。式（１）のＲ１乃至Ｒ８が表す芳香族基としては、例えばフェニル基、ビフェニル基、トリル基、インデニル基、ナフチル基、アントリル基、フルオレニル基、ピレニル基、フェナンスニル基又はメシチル基等が挙げられるが、フェニル基、ビフェニル基、トリル基、ナフチル基又はメシチル基が好ましく、フェニル基、トリル基又はメシチル基がより好ましい。
尚、芳香族基と成り得る芳香族化合物は置換基を有していてもよく、該有していてもよい置換基は特に限定されない。
The aromatic group represented by R 1 to R 8 in the above formula (1) is a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound. Examples of aromatic groups represented by R 1 to R 8 in formula (1) include phenyl group, biphenyl group, tolyl group, indenyl group, naphthyl group, anthryl group, fluorenyl group, pyrenyl group, phenanthyl group and mesityl group. Among them, phenyl group, biphenyl group, tolyl group, naphthyl group or mesityl group is preferred, and phenyl group, tolyl group or mesityl group is more preferred.
In addition, the aromatic compound that can be an aromatic group may have a substituent, and the substituent that may have is not particularly limited.
上記式（１）中のＲ１乃至Ｒ８が表す複素環基とは、複素環化合物の複素環から水素原子を一つ除いた残基である。式（１）のＲ１乃至Ｒ８が表す複素環基としては、例えばフラニル基、チエニル基、チエノチエニル基、ピロリル基、イミダゾリル基、Ｎ－メチルイミダゾリル基、チアゾリル基、オキサゾリル基、ピリジル基、ピラジル基、ピリミジル基、キノリル基、インドリル基、ベンゾピラジル基、ベンゾピリミジル基、ベンゾチエニル基、ベンゾチアゾリル基、ピリジノチアゾリル基、ベンゾイミダゾリル基、ピリジノイミダゾリル基、Ｎ－メチルベンゾイミダゾリル基、ピリジノ－Ｎ－メチルイミダゾリル基、ベンゾオキサゾリル基、ピリジノオキサゾリル基、ベンゾチアジアゾリル基、ピリジノチアジアゾリル基、ベンゾオキサジアゾリル基、ピリジノオキサジアゾリル基、カルバゾリル基、フェノキサジニル基又はフェノチアジニル基等が挙げられ、チエニル基、チエノチエニル基、チアゾリル基、ピリジル基、ベンゾチアゾリル基、ベンゾチアジアゾリル基又はピリジノチアジアゾリル基が好ましく、チエニル基、チアゾリル基、ピリジル基がより好ましい。
尚、複素環基と成り得る複素環化合物は置換基を有していてもよく、該有していても良い置換基は特に限定されない。
The heterocyclic group represented by R 1 to R 8 in the above formula (1) is a residue obtained by removing one hydrogen atom from the heterocyclic ring of the heterocyclic compound. Examples of heterocyclic groups represented by R 1 to R 8 in formula (1) include furanyl, thienyl, thienotienyl, pyrrolyl, imidazolyl, N-methylimidazolyl, thiazolyl, oxazolyl, pyridyl, and pyrazyl. group, pyrimidyl group, quinolyl group, indolyl group, benzopyrazyl group, benzopyrimidyl group, benzothienyl group, benzothiazolyl group, pyridinothiazolyl group, benzimidazolyl group, pyridinoimidazolyl group, N-methylbenzimidazolyl group, pyridino-N-methyl imidazolyl group, benzoxazolyl group, pyridinooxazolyl group, benzothiadiazolyl group, pyridinothiadiazolyl group, benzoxadiazolyl group, pyridinooxadiazolyl group, carbazolyl group, phenoxazinyl group, or phenothiazinyl A thienyl group, a thienothienyl group, a thiazolyl group, a pyridyl group, a benzothiazolyl group, a benzothiadiazolyl group or a pyridinothiadiazolyl group is preferable, and a thienyl group, a thiazolyl group and a pyridyl group are more preferable.
In addition, the heterocyclic compound that can be a heterocyclic group may have a substituent, and the substituent that may have is not particularly limited.
上記式（１）中のＲ１乃至Ｒ８が表すハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、フッ素原子又は塩素原子が好ましく、フッ素原子がさらに好ましい。 Halogen atoms represented by R 1 to R 8 in formula (1) include fluorine, chlorine, bromine and iodine atoms, preferably fluorine or chlorine, more preferably fluorine.
上記式（１）中のＲ１乃至Ｒ８が表す置換アミノ基は、アミノ基の水素原子が一つ又は二つ置換基で置換された置換基である。置換アミノ基の有する置換基としては、アルキル基又は芳香族基が好ましく、芳香族基がより好ましい。これら置換基の具体例としては、式（１）中のＲ１乃至Ｒ８が表す脂肪族炭化水素基の項に記載したアルキル基及び式（１）中のＲ１乃至Ｒ８が表す芳香族基と同じものが挙げられる。
上記式（１）中のＲ１乃至Ｒ８が表すアシル基とは、カルボニル基と芳香族基又はアルキル基が結合した置換基であり、アシル基の有するアルキル基及び芳香族基としては、式（１）中のＲ１乃至Ｒ８が表す脂肪族炭化水素基の項に記載したアルキル基、及び式（１）中のＲ１乃至Ｒ８が表す芳香族基と同じものが挙げられる。
The substituted amino group represented by R 1 to R 8 in the above formula (1) is a substituent in which one or two hydrogen atoms of the amino group are substituted with one or two substituents. The substituent of the substituted amino group is preferably an alkyl group or an aromatic group, more preferably an aromatic group. Specific examples of these substituents include the alkyl groups described in the section on the aliphatic hydrocarbon groups represented by R 1 to R 8 in formula (1) and the aromatic groups represented by R 1 to R 8 in formula (1). The same as the group can be mentioned.
The acyl group represented by R 1 to R 8 in the above formula (1) is a substituent in which a carbonyl group and an aromatic group or an alkyl group are bonded. Examples thereof include the same alkyl groups described in the section of the aliphatic hydrocarbon groups represented by R 1 to R 8 in (1) and the aromatic groups represented by R 1 to R 8 in formula (1).
式（１）におけるＲ１乃至Ｒ８としてはそれぞれ独立に水素原子、芳香族基、複素環基又はハロゲン原子が好ましく、それぞれ独立に水素原子、芳香族基又はハロゲン原子がより好ましい。
また、Ｒ１とＲ８が同一であることが好ましく、Ｒ２とＲ７が同一であることが好ましく、Ｒ３とＲ６が同一であることが好ましく、Ｒ４とＲ５が同一であることが好ましい。
R 1 to R 8 in formula (1) are each independently preferably a hydrogen atom, an aromatic group, a heterocyclic group or a halogen atom, and more preferably each independently a hydrogen atom, an aromatic group or a halogen atom.
R 1 and R 8 are preferably the same, R 2 and R 7 are preferably the same, R 3 and R 6 are preferably the same, R 4 and R 5 are the same is preferred.
式（１）中のＲ９及びＲ１０はそれぞれ独立に水素原子、脂肪族炭化水素基、芳香族基、又は複素環基を表す。
上記式（１）中のＲ９及びＲ１０が表す脂肪族炭化水素基は、飽和又は不飽和の直鎖状、分岐状又は環状のいずれにも限定されず、その炭素数は１乃至１０が好ましく、１乃至６がより好ましい。ここで、飽和又は不飽和の直鎖、分岐又は環状の脂肪族炭化水素基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、アリル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－セチル基、ｎ－ヘプタデシル基、ｎ－ブテニル基、２－エチルへキシル基、３－エチルヘプチル基、４－エチルオクチル基、２－ブチルオクチル基、３－ブチルノニル基、４－ブチルデシル基、２－ヘキシルデシル基、３－オクチルウンデシル基、４－オクチルドデシル基、２－オクチルドデシル基、２－デシルテトラデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
式（１）中のＲ９及びＲ１０が表す脂肪族炭化水素基としては、直鎖状又は分岐状の脂肪族炭化水素基であることが好ましく、飽和の直鎖状又は分岐状のアルキル基であることがより好ましく、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基又は２－ヘキシル基であることが更に好ましく、ｎメチル基、エチル基又はｎ－プロピル基であることが特に好ましい。
R 9 and R 10 in formula (1) each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic group, or a heterocyclic group.
The aliphatic hydrocarbon group represented by R 9 and R 10 in the above formula (1) is not limited to a saturated or unsaturated linear, branched or cyclic group, and has 1 to 10 carbon atoms. Preferably, 1 to 6 are more preferable. Here, specific examples of saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group and allyl group. , t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-cetyl group, n-heptadecyl group , n-butenyl group, 2-ethylhexyl group, 3-ethylheptyl group, 4-ethyloctyl group, 2-butyloctyl group, 3-butylnonyl group, 4-butyldecyl group, 2-hexyldecyl group, 3-octyl undecyl group, 4-octyldodecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
The aliphatic hydrocarbon group represented by R 9 and R 10 in formula (1) is preferably a linear or branched aliphatic hydrocarbon group, a saturated linear or branched alkyl group more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group or a 2-hexyl group, an n-methyl group, an ethyl group or an n-propyl group is particularly preferred.
上記式（１）中のＲ９及びＲ１０が表す芳香族基とは、芳香族化合物の芳香環から水素原子を一つ除いた残基である。式（１）のＲ９乃至Ｒ１０が表す芳香族基としては、例えばフェニル基、ビフェニル基、トリル基、インデニル基、ナフチル基、アントリル基、フルオレニル基、ピレニル基、フェナンスニル基及びメシチル基等が挙げられるが、フェニル基、ビフェニル基、トリル基、ナフチル基又はメシチル基が好ましく、フェニル基、トリル基又はメシチル基がより好ましい。
尚、芳香族基と成り得る芳香族化合物は置換基を有していてもよく、該有していてもよい置換基は特に限定されない。
The aromatic group represented by R 9 and R 10 in the above formula (1) is a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound. Examples of aromatic groups represented by R 9 to R 10 in formula (1) include phenyl, biphenyl, tolyl, indenyl, naphthyl, anthryl, fluorenyl, pyrenyl, phenanthyl and mesityl groups. Among them, phenyl group, biphenyl group, tolyl group, naphthyl group or mesityl group is preferred, and phenyl group, tolyl group or mesityl group is more preferred.
In addition, the aromatic compound that can be an aromatic group may have a substituent, and the substituent that may have is not particularly limited.
上記式（１）中のＲ９及びＲ１０が表す複素環基とは、複素環化合物の複素環から水素原子を一つ除いた残基である。式（１）のＲ９乃至Ｒ１０が表す複素環基としては、例えばフラニル基、チエニル基、チエノチエニル基、ピロリル基、イミダゾリル基、Ｎ－メチルイミダゾリル基、チアゾリル基、オキサゾリル基、ピリジル基、ピラジル基、ピリミジル基、キノリル基、インドリル基、ベンゾピラジル基、ベンゾピリミジル基、ベンゾチエニル基、ベンゾチアゾリル基、ピリジノチアゾリル基、ベンゾイミダゾリル基、ピリジノイミダゾリル基、Ｎ－メチルベンゾイミダゾリル基、ピリジノ－Ｎ－メチルイミダゾリル基、ベンゾオキサゾリル基、ピリジノオキサゾリル基、ベンゾチアジアゾリル基、ピリジノチアジアゾリル基、ベンゾオキサジアゾリル基、ピリジノオキサジアゾリル基、カルバゾリル基、フェノキサジニル基及びフェノチアジニル基等が挙げられ、チエニル基、チエノチエニル基、チアゾリル基、ピリジル基又はベンゾチアゾリル基が好ましく、チエニル基、チアゾリル基又はピリジル基がより好ましい。
尚、複素環基と成り得る複素環化合物は置換基を有していてもよく、該有していても良い置換基は特に限定されない。
The heterocyclic group represented by R 9 and R 10 in the above formula (1) is a residue obtained by removing one hydrogen atom from the heterocyclic ring of the heterocyclic compound. Examples of heterocyclic groups represented by R 9 to R 10 in formula (1) include furanyl, thienyl, thienotienyl, pyrrolyl, imidazolyl, N-methylimidazolyl, thiazolyl, oxazolyl, pyridyl and pyrazyl. group, pyrimidyl group, quinolyl group, indolyl group, benzopyrazyl group, benzopyrimidyl group, benzothienyl group, benzothiazolyl group, pyridinothiazolyl group, benzimidazolyl group, pyridinoimidazolyl group, N-methylbenzimidazolyl group, pyridino-N-methyl imidazolyl group, benzoxazolyl group, pyridinooxazolyl group, benzothiadiazolyl group, pyridinothiadiazolyl group, benzoxadiazolyl group, pyridinooxadiazolyl group, carbazolyl group, phenoxazinyl group and phenothiazinyl group A thienyl group, a thienothienyl group, a thiazolyl group, a pyridyl group or a benzothiazolyl group is preferred, and a thienyl group, a thiazolyl group or a pyridyl group is more preferred.
In addition, the heterocyclic compound that can be a heterocyclic group may have a substituent, and the substituent that may have is not particularly limited.
式（１）におけるＲ９及びＲ１０としては、それぞれ独立に水素原子、脂肪族炭化水素基、芳香族基又は複素環基が好ましく、それぞれ独立に水素原子、脂肪族炭化水素基又は芳香族基がより好ましく、水素原子が更に好ましい。 R 9 and R 10 in formula (1) are each independently preferably a hydrogen atom, an aliphatic hydrocarbon group, an aromatic group or a heterocyclic group, and each independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic group is more preferred, and a hydrogen atom is even more preferred.
式（１）中のＲ１１及びＲ１２はそれぞれ独立に脂肪族炭化水素基、芳香族基、複素環基を表す。
上記式（１）中のＲ１１及びＲ１２が表す脂肪族炭化水素基は、飽和又は不飽和の直鎖状、分岐状又は環状のいずれにも限定されず、その炭素数は１乃至１０が好ましく、１乃至６がより好ましい。ここで、飽和又は不飽和の直鎖、分岐又は環状の脂肪族炭化水素基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、アリル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－セチル基、ｎ－ヘプタデシル基、ｎ－ブテニル基、２－エチルへキシル基、３－エチルヘプチル基、４－エチルオクチル基、２－ブチルオクチル基、３－ブチルノニル基、４－ブチルデシル基、２－ヘキシルデシル基、３－オクチルウンデシル基、４－オクチルドデシル基、２－オクチルドデシル基、２－デシルテトラデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
R 11 and R 12 in formula (1) each independently represent an aliphatic hydrocarbon group, an aromatic group or a heterocyclic group.
The aliphatic hydrocarbon group represented by R 11 and R 12 in the above formula (1) is not limited to any of saturated or unsaturated linear, branched or cyclic, and has 1 to 10 carbon atoms. Preferably, 1 to 6 are more preferable. Here, specific examples of saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group and allyl group. , t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-cetyl group, n-heptadecyl group , n-butenyl group, 2-ethylhexyl group, 3-ethylheptyl group, 4-ethyloctyl group, 2-butyloctyl group, 3-butylnonyl group, 4-butyldecyl group, 2-hexyldecyl group, 3-octyl undecyl group, 4-octyldodecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
上記式（１）中のＲ１１及びＲ１２が表す芳香族基とは、芳香族化合物の芳香環から水素原子を一つ除いた残基である。式（１）のＲ１１乃至Ｒ１２が表す芳香族基としては、例えばフェニル基、ビフェニル基、トリル基、フルオロフェニル基、インデニル基、ナフチル基、アントリル基、フルオレニル基、ピレニル基、フェナンスニル基及びメシチル基等が挙げられるが、フェニル基、ビフェニル基、トリル基又はメシチル基が好ましく、フェニル基、トリル基、フルオロフェニル基又はメシチル基がより好ましい。
尚、芳香族基と成り得る芳香族化合物は置換基を有していてもよく、該有していてもよい置換基は特に限定されない。
The aromatic group represented by R 11 and R 12 in the above formula (1) is a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound. Examples of aromatic groups represented by R 11 to R 12 in formula (1) include phenyl, biphenyl, tolyl, fluorophenyl, indenyl, naphthyl, anthryl, fluorenyl, pyrenyl, phenanthyl and A phenyl group, a biphenyl group, a tolyl group or a mesityl group is preferred, and a phenyl group, a tolyl group, a fluorophenyl group or a mesityl group is more preferred.
In addition, the aromatic compound that can be an aromatic group may have a substituent, and the substituent that may have is not particularly limited.
上記式（１）中のＲ１１及びＲ１２が表す複素環基とは、複素環化合物の複素環から水素原子を一つ除いた残基である。式（１）のＲ１１乃至Ｒ１２が表す複素環基としては、例えばフラニル基、チエニル基、チエノチエニル基、ピロリル基、イミダゾリル基、Ｎ－メチルイミダゾリル基、チアゾリル基、オキサゾリル基、ピリジル基、ピラジル基、ピリミジル基、キノリル基、インドリル基、ベンゾピラジル基、ベンゾピリミジル基、ベンゾチエニル基、ベンゾチアゾリル基、ピリジノチアゾリル基、ベンゾイミダゾリル基、ピリジノイミダゾリル基、Ｎ－メチルベンゾイミダゾリル基、ピリジノ－Ｎ－メチルイミダゾリル基、ベンゾオキサゾリル基、ピリジノオキサゾリル基、ベンゾチアジアゾリル基、ピリジノチアジアゾリル基、ベンゾオキサジアゾリル基、ピリジノオキサジアゾリル基、カルバゾリル基、フェノキサジニル基及びフェノチアジニル基等が挙げられ、チエニル基、チエノチエニル基、チアゾリル基、ピリジル基、オキサゾリル基又はベンゾチアゾリル基が好ましく、チエニル基、チアゾリル基又はベンゾチアゾリル基がより好ましい。
尚、複素環基と成り得る複素環化合物は置換基を有していてもよく、該有していても良い置換基は特に限定されない。
The heterocyclic group represented by R 11 and R 12 in the above formula (1) is a residue obtained by removing one hydrogen atom from the heterocyclic ring of the heterocyclic compound. Examples of heterocyclic groups represented by R 11 to R 12 in formula (1) include furanyl, thienyl, thienotienyl, pyrrolyl, imidazolyl, N-methylimidazolyl, thiazolyl, oxazolyl, pyridyl and pyrazyl. group, pyrimidyl group, quinolyl group, indolyl group, benzopyrazyl group, benzopyrimidyl group, benzothienyl group, benzothiazolyl group, pyridinothiazolyl group, benzimidazolyl group, pyridinoimidazolyl group, N-methylbenzimidazolyl group, pyridino-N-methyl imidazolyl group, benzoxazolyl group, pyridinooxazolyl group, benzothiadiazolyl group, pyridinothiadiazolyl group, benzoxadiazolyl group, pyridinooxadiazolyl group, carbazolyl group, phenoxazinyl group and phenothiazinyl group A thienyl group, a thienothienyl group, a thiazolyl group, a pyridyl group, an oxazolyl group or a benzothiazolyl group is preferred, and a thienyl group, a thiazolyl group or a benzothiazolyl group is more preferred.
In addition, the heterocyclic compound that can be a heterocyclic group may have a substituent, and the substituent that may have is not particularly limited.
式（１）におけるＲ１１及びＲ１２としては、それぞれ独立に芳香族基又は複素環基が好ましく、芳香族基がより好ましい。 R 11 and R 12 in formula (1) are each independently preferably an aromatic group or a heterocyclic group, more preferably an aromatic group.
式（１）中のＺ１及びＺ２はそれぞれ独立に芳香族化合物の芳香環から水素原子を二つ除いた二価の連結基、又は複素環化合物の複素環から水素原子を二つ除いた二価の連結基を表す。
上記式（１）中のＺ１及びＺ２が表す芳香族化合物の芳香環から水素原子を一つ除いた二価の連結基となり得る芳香族化合物としては、例えばベンゼン、ナフタレン、アントラセン、ピレン、フルオレン及びフェナントレン等が挙げられ、ベンゼン又はナフタレンが好ましく、ベンゼンがより好ましい。
尚、二価の連結基と成り得る芳香族化合物は置換基を有していてもよく、該有していてもよい置換基は特に限定されない。
Z 1 and Z 2 in formula (1) are each independently a divalent linking group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic compound, or a heterocyclic compound obtained by removing two hydrogen atoms from a heterocyclic ring. represents a divalent linking group.
Examples of the aromatic compound that can be a divalent linking group obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound represented by Z 1 and Z 2 in the above formula (1) include benzene, naphthalene, anthracene, pyrene, Fluorene, phenanthrene and the like can be mentioned, with benzene or naphthalene being preferred, and benzene being more preferred.
In addition, the aromatic compound that can be a divalent linking group may have a substituent, and the substituent that may have is not particularly limited.
上記式（１）中のＺ１及びＺ２が表す複素環化合物の複素環から水素原子を一つ除いた二価の連結基となり得る芳香族化合物としては、例えばチオフェン、フラン、ピロール、チアゾール、イミダゾール、オキサゾール、ピリジン、ピラジン、ピリミジン及びキノリン等が挙げられ、チオフェン、チアゾール又はピリジンが好ましく、チオフェンがより好ましい。
尚、二価の連結基と成り得る複素環化合物は置換基を有していてもよく、該有していてもよい置換基は特に限定されない。
Examples of the aromatic compound that can be a divalent linking group obtained by removing one hydrogen atom from the heterocyclic ring of the heterocyclic compound represented by Z 1 and Z 2 in the above formula (1) include thiophene, furan, pyrrole, thiazole, Examples include imidazole, oxazole, pyridine, pyrazine, pyrimidine and quinoline, preferably thiophene, thiazole or pyridine, more preferably thiophene.
In addition, the heterocyclic compound that can be a divalent linking group may have a substituent, and the substituent that may have is not particularly limited.
式（１）中、二価の連結基Ｚ１及びＺ２の数を意味するｎはそれぞれ独立に０以上の整数を表し、それぞれ独立に０又は１が好ましく、１がより好ましい。 In formula (1), each n, which means the number of divalent linking groups Z1 and Z2, independently represents an integer of 0 or more, preferably 0 or 1 , more preferably 1.
次に、本発明の一般式（１）で表される化合物の合成方法について詳細に説明する。
前記式（１）で表される化合物は例えば以下の示す合成スキームにより合成することができる。化合物（ａ）は、公知の方法（特許文献５）を参考に合成可能であり、得られた化合物（ａ）を２級アミン誘導体と反応させて、化合物（ｂ）とした後に、三臭化ホウ素を反応させることでＢ－Ｏキレート化することにより式（１）で表される化合物が得られる。これらの化合物の精製方法は特に限定されず、例えば洗浄、再結晶、カラムクロマトグラフィー、真空昇華等が採用でき、必要に応じてこれらの方法を組み合わせることができる。
Next, a method for synthesizing the compound represented by formula (1) of the present invention will be described in detail.
The compound represented by the formula (1) can be synthesized, for example, by the synthesis scheme shown below. Compound (a) can be synthesized with reference to a known method (Patent Document 5), and the resulting compound (a) is reacted with a secondary amine derivative to form compound (b), followed by tribromide. A compound represented by formula (1) is obtained by BO chelation by reacting boron. Methods for purifying these compounds are not particularly limited, and for example, washing, recrystallization, column chromatography, vacuum sublimation, etc. can be employed, and these methods can be combined if necessary.
前記式（１）で表される化合物の具体例として、式（１－１）乃至（１－１２８）で表される化合物を以下に示すが、本発明はこれに限定されない。なお、具体例として示した構造式は共鳴構造の一つを表したものにすぎず、図示した共鳴構造に限定されない。 As specific examples of the compound represented by formula (1), compounds represented by formulas (1-1) to (1-128) are shown below, but the present invention is not limited thereto. It should be noted that the structural formula shown as a specific example merely represents one resonance structure, and is not limited to the illustrated resonance structure.
本発明の近赤外光吸収色素は、上記式（１）で表される化合物を含有する。
本発明の近赤外光吸収色素中の式（１）で表される化合物の含有量は、近赤外光吸収色素を用いる用途において必要とされる近赤外光の吸収能力が発現する限り特に限定されないが、通常は５０質量％以上であり、８０質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が更に好ましい。
本発明の近赤外光吸収色素には、式（１）で表される化合物以外の化合物（例えば式（１）で表される化合物以外の近赤外光吸収色素等）や添加剤等を併用してもよい。併用し得る化合物や添加剤等は、近赤外光吸収材料を用いる用途において必要とされる近赤外光の吸収能力が発現する限り特に限定されない。
The near-infrared light absorbing dye of the present invention contains the compound represented by the above formula (1).
The content of the compound represented by formula (1) in the near-infrared light-absorbing dye of the present invention is as long as the near-infrared light absorption ability required in the application using the near-infrared light-absorbing dye is expressed. Although not particularly limited, it is usually 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
The near-infrared light-absorbing dye of the present invention contains compounds other than the compound represented by formula (1) (for example, near-infrared light-absorbing dyes other than the compound represented by formula (1), etc.) and additives. They may be used together. The compounds, additives, and the like that can be used in combination are not particularly limited as long as they exhibit the near-infrared light absorbing ability required in the application using the near-infrared light absorbing material.
本発明の化合物を用いて、薄膜を作製することができる。当該薄膜は本発明の化合物のみで構成されていてもよいが、別途公知の近赤外光吸収色素を含んでいてもよい。 Thin films can be prepared using the compounds of the present invention. The thin film may be composed only of the compound of the present invention, or may separately contain a known near-infrared light absorbing dye.
本発明の薄膜の形成方法には、一般的な乾式成膜法や湿式成膜法が挙げられる。具体的には真空プロセスである抵抗加熱蒸着、電子ビーム蒸着、スパッタリング、分子積層法、溶液プロセスであるキャスティング、スピンコーティング、ディップコーティング、ブレードコーティング、ワイヤバーコーティング、スプレーコーティング等のコーティング法、インクジェット印刷、スクリーン印刷、オフセット印刷、凸版印刷等の印刷法、マイクロコンタクトプリンティング法等のソフトリソグラフィーの手法等が挙げられる。
一般的な近赤外光吸収色素は、加工の容易性という観点からは化合物を溶液状態で塗布するようなプロセスが望まれているが、有機膜を積層するような有機エレクトロニクスデバイスの場合、塗布溶液が下層の有機膜を侵す恐れがあることから不向きである。
Methods for forming the thin film of the present invention include general dry film forming methods and wet film forming methods. Specifically, vacuum processes such as resistance heating deposition, electron beam deposition, sputtering, molecular lamination, solution processes such as casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, and inkjet printing. , printing methods such as screen printing, offset printing, letterpress printing, and soft lithography techniques such as microcontact printing.
For general near-infrared light absorbing dyes, from the viewpoint of ease of processing, the process of coating the compound in a solution state is desired. It is not suitable because the solution may damage the underlying organic film.
この様な多層積層構造を実現するためには、乾式成膜法、例えば抵抗加熱蒸着の様な蒸着可能な材料を用いることが適切である。したがって、近赤外領域に主たる吸収波長を有し、且つ蒸着可能な近赤外光吸収色素が近赤外光電変換材料として好ましい。 In order to realize such a multi-layer laminated structure, it is appropriate to use materials that can be vapor-deposited by a dry film-forming method, such as resistance heating vapor deposition. Therefore, a near-infrared light-absorbing dye that has a main absorption wavelength in the near-infrared region and can be vapor-deposited is preferable as a near-infrared photoelectric conversion material.
各層の成膜には上記の手法を複数組み合わせた方法を採用してもよい。各層の厚みは、それぞれの物質の抵抗値・電荷移動度にもよるので限定することはできないが、通常は０．５乃至５０００ｎｍの範囲であり、好ましくは１乃至１０００ｎｍの範囲、より好ましくは５乃至５００ｎｍの範囲である。 A method in which a plurality of the above methods are combined may be employed for forming each layer. The thickness of each layer cannot be limited because it depends on the resistance value and charge mobility of each substance, but it is usually in the range of 0.5 to 5000 nm, preferably in the range of 1 to 1000 nm, more preferably 5 nm. to 500 nm.
〔有機エレクトロニクスデバイス〕
本発明の化合物、近赤外光吸収材料或いは近赤外発光材料又はこれらを用いた有機薄膜を含む有機エレクトロニクスデバイスを作製することができる。有機エレクトロニクスデバイスとしては、例えば、薄膜トランジスタ、有機光電変換素子、有機太陽電池素子、有機エレクトロルミネッセンス素子（以下、「有機ＥＬ素子」又は「有機発光素子」と表す。）、有機発光トランジスタ素子、有機半導体レーザー素子などが挙げられる。本発明では、特に近赤外用途の展開が期待される有機光電変換素子、有機ＥＬ素子に着目する。ここでは本発明の実施形態の一つである近赤外光吸収材料として用いた近赤外有機光電変換素子、近赤外発光特性を利用した有機ＥＬ素子、有機半導体レーザー素子について説明する。
なお、ここでは詳細に説明しないが、７００ｎｍを超える近赤外光は、生体組織に対する透過性が高い。従って、生体内組織の観測のため利用も可能であるため、近赤外蛍光プローブ等、医療分野での病理解明、診断等において、その目的に応じて、いろいろな態様での適用が可能である。
[Organic electronic devices]
An organic electronic device containing the compound of the present invention, a near-infrared light absorbing material, a near-infrared light emitting material, or an organic thin film using these can be produced. Examples of organic electronic devices include thin film transistors, organic photoelectric conversion elements, organic solar cell elements, organic electroluminescence elements (hereinafter referred to as "organic EL elements" or "organic light emitting elements"), organic light emitting transistor elements, and organic semiconductors. A laser element etc. are mentioned. In the present invention, attention is paid to organic photoelectric conversion devices and organic EL devices, which are expected to be developed especially for near-infrared applications. Here, a near-infrared organic photoelectric conversion device, an organic EL device utilizing near-infrared light emission characteristics, and an organic semiconductor laser device, which are used as a near-infrared light absorbing material, which are one embodiment of the present invention, will be described.
Although not described in detail here, near-infrared light exceeding 700 nm has high permeability to living tissue. Therefore, since it can be used for observation of in vivo tissues, it can be applied in various aspects according to the purpose in the medical field, such as near-infrared fluorescent probes, in clarifying pathologies, diagnosing, etc. .
〔有機光電変換素子〕
上記式（１）で表される化合物は近赤外光吸収特性を有する化合物であることから、近赤外有機光電変換素子としての利用が期待される。特に、本発明の有機光電変換素子に於ける光電変換層に用いることができる。当該素子に於いては、光に対する応答波長光の吸収帯の極大吸収が７８０ｎｍ以上２５００ｎｍ以下であることが好ましい。ここで、近赤外有機光電変換素子としては近赤外光センサ、有機撮像素子、近赤外光イメージセンサ等が挙げられる。
[Organic photoelectric conversion element]
Since the compound represented by the above formula (1) is a compound having near-infrared light absorption properties, it is expected to be used as a near-infrared organic photoelectric conversion device. In particular, it can be used for the photoelectric conversion layer in the organic photoelectric conversion element of the present invention. In the element, it is preferable that the maximum absorption of the absorption band of the response wavelength light for light is 780 nm or more and 2500 nm or less. Here, examples of near-infrared organic photoelectric conversion elements include near-infrared photosensors, organic imaging elements, and near-infrared image sensors.
有機光電変換素子は、対向する一対の電極膜間に光電変換部（膜）を配置した素子であって、電極膜の上方から光が光電変換部に入射されるものである。光電変換部は前記の入射光に応じて電子と正孔を発生するものであり、半導体により前記電荷に応じた信号が読み出され、光電変換膜部の吸収波長に応じた入射光量を示す素子である。光が入射しない側の電極膜には読み出しのためのトランジスタが接続される場合もある。光電変換素子は、アレイ状に多数配置されている場合、入射光量に加え入射位置情報をも示すため、撮像素子となる。又、より光源近くに配置された光電変換素子が、光源側から見てその背後に配置された光電変換素子の吸収波長を遮蔽しない（透過する）場合は、複数の光電変換素子を積層して用いてもよい。 An organic photoelectric conversion element is an element in which a photoelectric conversion portion (film) is arranged between a pair of opposing electrode films, and light is incident on the photoelectric conversion portion from above the electrode films. The photoelectric conversion portion generates electrons and holes in response to the incident light, and a semiconductor device reads out a signal corresponding to the charge and indicates the amount of incident light corresponding to the absorption wavelength of the photoelectric conversion film portion. is. A readout transistor may be connected to the electrode film on the side where light does not enter. When a large number of photoelectric conversion elements are arranged in an array, they serve as an imaging element because they indicate incident position information in addition to the amount of incident light. Further, when a photoelectric conversion element placed closer to the light source does not block (transmits) the absorption wavelength of the photoelectric conversion element placed behind it when viewed from the light source side, a plurality of photoelectric conversion elements are stacked. may be used.
本発明の有機光電変換素子は、前記式（１）で表される化合物を上記光電変換部の構成材料として用いることができる。
光電変換部は、光電変換層と、電子輸送層、正孔輸送層、電子ブロック層、正孔ブロック層、結晶化防止層及び層間接触改良層等から成る群より選択される一種又は複数種の光電変換層以外の有機薄膜層とから成ることが多い。本発明の化合物は光電変換層以外にも用いることもできるが、光電変換層の有機薄膜層として用いることが好ましい。光電変換層は前記式（１）で表される化合物のみで構成されていてもよいが、前記式（１）で表される化合物以外に、公知の近赤外光吸収材料やその他を含んでいてもよい。
The organic photoelectric conversion element of the present invention can use the compound represented by the formula (1) as a constituent material of the photoelectric conversion part.
The photoelectric conversion part includes one or more selected from the group consisting of a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an anti-crystallization layer, an interlayer contact improving layer, and the like. It is often composed of an organic thin film layer other than the photoelectric conversion layer. Although the compound of the present invention can be used in a layer other than the photoelectric conversion layer, it is preferably used as an organic thin film layer of the photoelectric conversion layer. The photoelectric conversion layer may be composed only of the compound represented by the formula (1), but in addition to the compound represented by the formula (1), it may contain a known near-infrared light absorbing material or others. You can
本発明の有機光電変換素子で用いられる電極膜は、後述する光電変換部に含まれる光電変換層が、正孔輸送性を有する場合や光電変換層以外の有機薄膜層が正孔輸送性を有する正孔輸送層である場合は、該光電変換層やその他の有機薄膜層から正孔を取り出してこれを捕集する役割を果たし、又光電変換部に含まれる光電変換層が電子輸送性を有する場合や、有機薄膜層が電子輸送性を有する電子輸送層である場合は、該光電変換層やその他の有機薄膜層から電子を取り出して、これを吐出する役割を果たすものである。よって、電極膜として用い得る材料は、ある程度の導電性を有するものであれば特に限定されないが、隣接する光電変換層やその他の有機薄膜層との密着性や電子親和力、イオン化ポテンシャル、安定性等を考慮して選択することが好ましい。電極膜として用い得る材料としては、例えば、酸化錫（ＮＥＳＡ）、酸化インジウム、酸化錫インジウム（ＩＴＯ）及び酸化亜鉛インジウム（ＩＺＯ）等の導電性金属酸化物；金、銀、白金、クロム、アルミニウム、鉄、コバルト、ニッケル及びタングステン等の金属：ヨウ化銅及び硫化銅等の無機導電性物質：ポリチオフェン、ポリピロール及びポリアニリン等の導電性ポリマー：炭素等が挙げられる。これらの材料は、必要により複数を混合して用いてもよいし、複数を２層以上に積層して用いてもよい。電極膜に用いる材料の導電性も、光電変換素子の受光を必要以上に妨げなければ特に限定されないが、光電変換素子の信号強度や、消費電力の観点からできるだけ高いことが好ましい。例えばシート抵抗値が３００Ω／□以下の導電性を有するＩＴＯ膜であれば、電極膜として充分機能するが、数Ω／□程度の導電性を有するＩＴＯ膜を備えた基板の市販品も入手可能となっていることから、この様な高い導電性を有する基板を使用することが望ましい。ＩＴＯ膜（電極膜）の厚さは導電性を考慮して任意に選択することができるが、通常５乃至５００ｎｍ、好ましくは１０乃至３００ｎｍ程度である。ＩＴＯなどの膜を形成する方法としては、従来公知の蒸着法、電子線ビーム法、スパッタリング法、化学反応法及び塗布法等が挙げられる。基板上に設けられたＩＴＯ膜には必要に応じＵＶ－オゾン処理やプラズマ処理等を施してもよい。 In the electrode film used in the organic photoelectric conversion element of the present invention, the photoelectric conversion layer contained in the photoelectric conversion part described later has a hole-transport property, or the organic thin film layer other than the photoelectric conversion layer has a hole-transport property. When it is a hole transport layer, it plays a role of extracting and collecting holes from the photoelectric conversion layer and other organic thin film layers, and the photoelectric conversion layer contained in the photoelectric conversion part has electron transport properties. In some cases, or when the organic thin film layer is an electron transport layer having electron transport properties, it plays a role of extracting electrons from the photoelectric conversion layer or other organic thin film layers and ejecting them. Therefore, the material that can be used as the electrode film is not particularly limited as long as it has a certain degree of conductivity. is preferably selected in consideration of Examples of materials that can be used as electrode films include conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); gold, silver, platinum, chromium, and aluminum. , metals such as iron, cobalt, nickel and tungsten; inorganic conductive substances such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole and polyaniline; and carbon. A plurality of these materials may be mixed and used if necessary, or a plurality of these materials may be used by laminating two or more layers. The conductivity of the material used for the electrode film is also not particularly limited as long as it does not interfere with the light reception of the photoelectric conversion element more than necessary. For example, a conductive ITO film with a sheet resistance value of 300 Ω/□ or less functions well as an electrode film, but substrates with an ITO film having a conductivity of several Ω/□ are also available on the market. Therefore, it is desirable to use a substrate having such high conductivity. Although the thickness of the ITO film (electrode film) can be arbitrarily selected in consideration of conductivity, it is usually about 5 to 500 nm, preferably about 10 to 300 nm. Methods for forming a film such as ITO include conventionally known vapor deposition methods, electron beam methods, sputtering methods, chemical reaction methods, coating methods, and the like. If necessary, the ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment, or the like.
電極膜のうち、少なくとも光が入射する側の何れか一方に用いられる透明電極膜の材料としては、ＩＴＯ、ＩＺＯ、ＳｎＯ２、ＡＴＯ（アンチモンドープ酸化スズ）、ＺｎＯ、ＡＺＯ（Ａｌドープ酸化亜鉛）、ＧＺＯ（ガリウムドープ酸化亜鉛）、ＴｉＯ２、ＦＴＯ（フッ素ドープ酸化スズ）等が挙げられる。光電変換層の吸収ピーク波長における透明電極膜を介して入射した光の透過率は、６０％以上であることが好ましく、８０％以上であることがより好ましく、９５％以上であることが特に好ましい。 Materials for the transparent electrode film used for at least one of the light incident sides of the electrode film include ITO, IZO, SnO 2 , ATO (antimony-doped tin oxide), ZnO, and AZO (Al-doped zinc oxide). , GZO (gallium-doped zinc oxide), TiO 2 , FTO (fluorine-doped tin oxide), and the like. The transmittance of light incident through the transparent electrode film at the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, and particularly preferably 95% or more. .
又、検出する波長の異なる光電変換層を複数積層する場合、それぞれの光電変換層の間に用いられる電極膜（これは上記記載の一対の電極膜以外の電極膜である）は、それぞれの光電変換層が検出する光以外の波長の光を透過させる必要があり、該電極膜には入射光の９０％以上を透過する材料を用いることが好ましく、９５％以上の光を透過する材料を用いることがより好ましい。 Further, in the case of stacking a plurality of photoelectric conversion layers that detect different wavelengths, the electrode film (this is an electrode film other than the pair of electrode films described above) used between the respective photoelectric conversion layers is It is necessary to transmit light of a wavelength other than the light detected by the conversion layer, and it is preferable to use a material that transmits 90% or more of the incident light for the electrode film, and a material that transmits 95% or more of the light is used. is more preferable.
電極膜はプラズマフリーで作製することが好ましい。プラズマフリーでこれらの電極膜を作成することにより、電極膜が設けられる基板にプラズマが与える影響が低減され、光電変換素子の光電変換特性を良好にすることができる。ここで、プラズマフリーとは、電極膜の成膜時にプラズマが発生しないか、又はプラズマ発生源から基板までの距離が２ｃｍ以上、好ましくは１０ｃｍ以上、更に好ましくは２０ｃｍ以上であり、基板に到達するプラズマが減ぜられるような状態を意味する。 The electrode film is preferably produced plasma-free. By forming these electrode films in a plasma-free manner, the influence of plasma on the substrate on which the electrode films are provided is reduced, and the photoelectric conversion characteristics of the photoelectric conversion element can be improved. Here, "plasma-free" means that no plasma is generated during the deposition of the electrode film, or that the distance from the plasma generation source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and the plasma reaches the substrate. Denotes the state in which the plasma is reduced.
電極膜の成膜時にプラズマが発生しない装置としては、例えば、電子線蒸着装置（ＥＢ蒸着装置）やパルスレーザー蒸着装置等が挙げられる。ＥＢ蒸着装置を用いて透明電極膜の成膜を行う方法をＥＢ蒸着法と称し、パルスレーザー蒸着装置を用いて透明電極膜の成膜を行う方法をパルスレーザー蒸着法と称する。 Examples of apparatuses that do not generate plasma when forming an electrode film include an electron beam vapor deposition apparatus (EB vapor deposition apparatus) and a pulse laser vapor deposition apparatus. A method of forming a transparent electrode film using an EB vapor deposition device is called an EB vapor deposition method, and a method of forming a transparent electrode film using a pulse laser vapor deposition device is called a pulse laser vapor deposition method.
成膜中プラズマを減ずることができるような状態を実現できる装置（以下、プラズマフリーである成膜装置という）としては、例えば、対向ターゲット式スパッタ装置やアークプラズマ蒸着装置等が考えられる。 As an apparatus capable of realizing a state in which plasma can be reduced during film formation (hereinafter referred to as a plasma-free film formation apparatus), for example, a facing target type sputtering apparatus, an arc plasma vapor deposition apparatus, and the like can be considered.
透明導電膜を電極膜（例えば第一の導電膜）とした場合、ＤＣショート、あるいはリーク電流の増大が生じる場合がある。この原因の一つは、光電変換層に発生する微細なクラックがＴＣＯ（Ｔｒａｎｓｐａｒｅｎｔ Ｃｏｎｄｕｃｔｉｖｅ Ｏｘｉｄｅ）などの緻密な膜によって被覆され、透明導電膜とは反対側の電極膜との間の導通が増すためと考えられる。そのため、Ａｌなど膜質が比較して劣る材料を電極に用いた場合、リーク電流の増大は生じにくい。電極膜の膜厚を、光電変換層の膜厚（クラックの深さ）に応じて制御することにより、リーク電流の増大を抑制することができる。 When a transparent conductive film is used as an electrode film (for example, a first conductive film), a DC short circuit or an increase in leakage current may occur. One of the reasons for this is that fine cracks generated in the photoelectric conversion layer are covered with a dense film such as TCO (Transparent Conductive Oxide), and the conduction between the transparent conductive film and the electrode film on the opposite side increases. it is conceivable that. Therefore, when a material such as Al having a relatively inferior film quality is used for the electrode, an increase in leakage current is less likely to occur. By controlling the film thickness of the electrode film according to the film thickness (crack depth) of the photoelectric conversion layer, an increase in leakage current can be suppressed.
通常、導電膜を所定の値より薄くすると、急激な抵抗値の増加が起こる。本実施形態の光センサ用光電変換素子における導電膜のシート抵抗は、通常１００乃至１００００Ω／□であり、膜厚の自由度が大きい。又、透明導電膜が薄いほど吸収する光の量が少なくなり、一般に光透過率が高くなる。光透過率が高くなると、光電変換層で吸収される光が増加して光電変換能が向上するため非常に好ましい。 Generally, when the conductive film is made thinner than a predetermined value, a rapid increase in resistance value occurs. The sheet resistance of the conductive film in the photoelectric conversion element for optical sensors of this embodiment is usually 100 to 10000 Ω/□, and the film thickness has a large degree of freedom. Also, the thinner the transparent conductive film, the less light it absorbs, and generally the higher the light transmittance. When the light transmittance is high, the amount of light absorbed by the photoelectric conversion layer is increased and the photoelectric conversion performance is improved, which is very preferable.
本発明の有機光電変換素子が有する光電変換部は、光電変換層及び光電変換層以外の有機薄膜層を含む場合もある。光電変換部を構成する光電変換層には一般的に有機半導体膜が用いられるが、その有機半導体膜は一層若しくは複数の層であってもよく、一層の場合は、ｐ型有機半導体膜、ｎ型有機半導体膜、又はそれらの混合膜（バルクヘテロ構造）が用いられる。一方、複数の層である場合は、２乃至１０層程度であり、ｐ型有機半導体膜、ｎ型有機半導体膜、又はそれらの混合膜（バルクヘテロ構造）の何れかを積層した構造であり、層間にバッファ層が挿入されていてもよい。なお、上記の混合膜により光電変換層を形成する場合、本発明の一般式（１）で表される化合物をｐ型半導体材料として用い、ｎ型半導体材料としては一般的なフラーレンや、その誘導体を用いることが好ましい。 The photoelectric conversion part of the organic photoelectric conversion element of the present invention may include a photoelectric conversion layer and an organic thin film layer other than the photoelectric conversion layer. An organic semiconductor film is generally used for the photoelectric conversion layer that constitutes the photoelectric conversion part, and the organic semiconductor film may be a single layer or a plurality of layers. type organic semiconductor films, or mixed films thereof (bulk heterostructures) are used. On the other hand, in the case of a plurality of layers, it is about 2 to 10 layers, and is a structure in which either a p-type organic semiconductor film, an n-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is laminated. A buffer layer may be inserted in the . When the photoelectric conversion layer is formed from the above mixed film, the compound represented by the general formula (1) of the present invention is used as the p-type semiconductor material, and the n-type semiconductor material is a general fullerene or a derivative thereof. is preferably used.
本発明の有機光電変換素子において、光電変換部を構成する光電変換層以外の有機薄膜層は、光電変換層以外の層、例えば、電子輸送層、正孔輸送層、電子ブロック層、正孔ブロック層、結晶化防止層又は層間接触改良層等としても用いられる。特に電子輸送層、正孔輸送層、電子ブロック層及び正孔ブロック層（以下「キャリアブロック層」とも表す。）から成る群より選択される一種以上の薄膜層として用いることにより、弱い光エネルギーでも効率よく電気信号に変換する素子が得られるため好ましい。 In the organic photoelectric conversion device of the present invention, the organic thin film layer other than the photoelectric conversion layer constituting the photoelectric conversion part is a layer other than the photoelectric conversion layer, such as an electron transport layer, a hole transport layer, an electron blocking layer, and a hole blocking layer. It can also be used as a layer, an anti-crystallization layer, an interlayer contact improving layer, or the like. In particular, by using one or more thin film layers selected from the group consisting of an electron transport layer, a hole transport layer, an electron block layer and a hole block layer (hereinafter also referred to as "carrier block layers"), even weak light energy It is preferable because an element that efficiently converts into an electric signal can be obtained.
加えて、例えば有機撮像素子は、一般的には高コントラスト化や省電力化を目的として、暗電流の低減により性能向上を目指すと考えられため、層構造内にキャリアブロック層を挿入する手法が好ましい。これらのキャリアブロック層は、有機エレクトロニクスデバイス分野では一般に用いられており、其々デバイスの構成膜中において正孔若しくは電子の逆移動を制御する機能を有する。 In addition, for example, organic image sensors are generally considered to aim for performance improvement by reducing dark current for the purpose of high contrast and power saving, so a method of inserting a carrier block layer in the layer structure is proposed. preferable. These carrier block layers are generally used in the field of organic electronic devices, and each have a function of controlling the reverse transfer of holes or electrons in the constituent films of the device.
電子輸送層は、光電変換層で発生した電子を電極膜へ輸送する役割と、電子輸送先の電極膜から光電変換層に正孔が移動するのをブロックする役割とを果たす。正孔輸送層は、発生した正孔を光電変換層から電極膜へ輸送する役割と、正孔輸送先の電極膜から光電変換層に電子が移動するのをブロックする役割とを果たす。電子ブロック層は、電極膜から光電変換層への電子の移動を妨げ、光電変換層内での再結合を防ぎ、暗電流を低減する役割を果たす。正孔ブロック層は、電極膜から光電変換層への正孔の移動を妨げ、光電変換層内での再結合を防ぎ、暗電流を低減する機能を有する。 The electron transport layer plays a role of transporting electrons generated in the photoelectric conversion layer to the electrode film and a role of blocking the movement of holes from the electrode film to which the electrons are transported to the photoelectric conversion layer. The hole transport layer plays a role of transporting generated holes from the photoelectric conversion layer to the electrode film and a role of blocking the movement of electrons from the electrode film to which the holes are transported to the photoelectric conversion layer. The electron blocking layer plays a role of preventing movement of electrons from the electrode film to the photoelectric conversion layer, preventing recombination within the photoelectric conversion layer, and reducing dark current. The hole blocking layer has a function of preventing holes from moving from the electrode film to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
図１に本発明の有機光電変換素子の代表的な素子構造を示すが、本発明はこの構造に限定されるものではない。図１の態様例においては、１が絶縁部、２が一方の電極膜、３が電子ブロック層、４が光電変換層、５が正孔ブロック層、６が他方の電極膜、７が絶縁基材又は他の有機光電変換素子をそれぞれ表す。図中には読み出し用のトランジスタを記載していないが、２又は６の電極膜と接続されていればよく、更には光電変換層４が透明であれば、光が入射する側とは反対側の電極膜の外側に成膜されていてもよい。有機光電変換素子への光の入射は、光電変換層４を除く構成要素が、光電変換層の主たる吸収波長の光を入射することを極度に阻害することがなければ、上部若しくは下部からの何れからでもよい。
Although FIG. 1 shows a typical device structure of the organic photoelectric conversion device of the present invention, the present invention is not limited to this structure. In the example of FIG. 1, 1 is an insulating part, 2 is one electrode film, 3 is an electron blocking layer, 4 is a photoelectric conversion layer, 5 is a hole blocking layer, 6 is the other electrode film, and 7 is an insulating base. material or other organic photoelectric conversion element, respectively. Although a readout transistor is not shown in the figure, it may be connected to two or six electrode films. may be formed outside the electrode film. Light is incident on the organic photoelectric conversion element from either the top or the bottom, provided that the components other than the
［有機半導体レーザー素子について］
上記一般式（１）で表される化合物は近赤外発光特性を有する化合物であることから、有機半導体レーザー素子としての利用が期待される。すなわち、上記一般式（１）で表される化合物を含有する有機半導体レーザー素子に共振器構造を組み込み、効率的にキャリアを注入して励起状態の密度を十分に高めることができれば、光が増幅されレーザー発振に至る事が期待される。従来、光励起によるレーザー発振が観測されるのみで、電気励起によるレーザー発振に必要とされる、高密度のキャリアを有機半導体素子に注入し、高密度の励起状態を発生させるのは非常に困難と提唱されているが、上記一般式（１）で表される化合物を含有する有機半導体素子を用いることで、高効率な発光（電界発光）が起こる可能性が期待される。
[Regarding the organic semiconductor laser element]
Since the compound represented by the above general formula (1) is a compound having near-infrared emission properties, it is expected to be used as an organic semiconductor laser device. That is, if a resonator structure can be incorporated into an organic semiconductor laser device containing the compound represented by the general formula (1), and carriers can be efficiently injected to sufficiently increase the density of the excited state, light will be amplified. is expected to lead to laser oscillation. Conventionally, only laser oscillation by photoexcitation has been observed, and it is extremely difficult to inject the high-density carriers required for laser oscillation by electrical excitation into an organic semiconductor device to generate a high-density excited state. Although proposed, the possibility of highly efficient light emission (electroluminescence) is expected by using an organic semiconductor device containing the compound represented by the general formula (1).
以下に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの例に限定されるものではない。合成例に記載の化合物は、必要に応じて質量分析スペクトル、核磁気共鳴スペクトル（ＮＭＲ）により構造を決定した。実施例における１Ｈ ＮＭＲの測定は、ＪＮＭ－ＥＣＳ４００（ＪＥＯＬ社製）を用いて、分子量の測定はＩＳＱ ＬＴ ＧＣ－ＭＳ（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製）を用いて、また吸収スペクトルのλｍａｘの値はＵＶ－１７００（島津製作所製）を用いてそれぞれ行った。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The structures of the compounds described in Synthesis Examples were determined by mass spectrometry and nuclear magnetic resonance spectroscopy (NMR) as necessary. In the examples, 1 H NMR was measured using JNM-ECS400 (manufactured by JEOL), molecular weight was measured using ISQ LT GC-MS (manufactured by Thermo Fisher Scientific), and the λmax value of the absorption spectrum was Each was carried out using UV-1700 (manufactured by Shimadzu Corporation).
実施例１（本発明の化合物の合成）
下記のスキームにより式（１－６８）で表される本発明の化合物を合成した。
Example 1 (synthesis of compounds of the present invention)
A compound of the present invention represented by formula (1-68) was synthesized according to the following scheme.
（工程１）上記スキーム中、式（２－２）で表される中間体化合物の合成
フラスコ中で、上記式（２－１）で表される化合物（０．５５ｍｍｏｌ）とアニリン（５．４ｍｍｏｌ）をトルエン（３６ｍＬ）に溶解し、９５℃に加熱して４時間撹拌した。反応液を放冷して、溶媒を濃縮乾燥した後に、エタノールで懸濁ろ過することにより、式（２－２）で表される中間体化合物を得た（０．３４ｍｍｏｌ、収率６２質量％）。式（２－２）で表される化合物の分子量の測定結果は以下のとおりであった。
ＥＩ－ＭＳ（ｍ／ｚ）：９１０［Ｍ］＋
(Step 1) In the above scheme, in a synthesis flask of the intermediate compound represented by formula (2-2), the compound represented by the above formula (2-1) (0.55 mmol) and aniline (5.4 mmol) ) was dissolved in toluene (36 mL), heated to 95° C. and stirred for 4 hours. The reaction solution was allowed to cool, the solvent was concentrated to dryness, and the suspension was filtered with ethanol to obtain an intermediate compound represented by formula (2-2) (0.34 mmol, yield 62% by mass. ). The measurement results of the molecular weight of the compound represented by formula (2-2) were as follows.
EI-MS (m/z): 910 [M] +
（工程２）上記具体例の式（１－６８）で表される化合物の合成
フラスコ中で、工程１で得られた式（２－２）で表される中間体化合物（０．２９ｍｍｏｌ）をジクロロメタン（２５ｍＬ）に溶解させた。次いで、三臭化ホウ素（５．７ｍＬ）を反応系に加え、１８時間攪拌した。反応液を飽和炭酸水素ナトリウム水溶液に加えることで中和したのち、有機層を濃縮乾燥した。メタノールを加えて、懸濁ろ過することにより式（１－６８）で表される本発明の化合物を得た。（０．１２ｍｍｏｌ、収率：４１質量％）。
式（１－６８）で表される化合物の分子量の測定結果は以下のとおりであった。
ＥＩ－ＭＳ（ｍ／ｚ）：８４２［Ｍ］＋
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ（ｐｐｍ）＝８．４６（ｓ、２Ｈ）、７．９２（ｍ、６Ｈ）、７．７８（ｄ、４Ｈ）、７．７１（ｄ、２Ｈ）、７．４８（ｓ、１Ｈ）、７．４０（ｔ、４Ｈ）、７．３０－７．２１（ｍ、１０Ｈ）
(Step 2) Synthesis of the compound represented by the formula (1-68) in the above specific example In a flask, the intermediate compound (0.29 mmol) represented by the formula (2-2) obtained in
The measurement results of the molecular weight of the compound represented by formula (1-68) were as follows.
EI-MS (m/z): 842 [M] +
1 H NMR (CDCl 3 ) δ (ppm) = 8.46 (s, 2H), 7.92 (m, 6H), 7.78 (d, 4H), 7.71 (d, 2H), 7.71 (d, 2H); 48 (s, 1H), 7.40 (t, 4H), 7.30-7.21 (m, 10H)
実施例２（本発明の化合物の合成）
（工程３）上記具体例の式（１－１０１）で表される本発明の化合物の合成
フラスコ中で、ジ（（ホルミルチエニル）－メトキシチエニル）ジフルオロジベンゾピロメテンーＢＦ２錯体（０．０３３ｍｍｏｌ）と３，５―ジメチルアニリン（０．３０ｍｍｏｌ）をトルエン（２ｍＬ）に溶解し、９５℃に加熱して３時間撹拌した。反応液を放冷して、溶媒を濃縮乾燥した後に、エタノールで懸濁ろ過することにより、中間体化合物を得た（０．０２０ｍｍｏｌ）。前記で得られた中間体化合物をフラスコ中でジクロロメタン（２ｍＬ）に溶解させた。次いで、三臭化ホウ素（０．５ｍＬ）を反応系に加え、７時間攪拌した。反応液を飽和炭酸水素ナトリウム水溶液に加えることで中和したのち、有機層を濃縮乾燥した。メタノールを加えて、懸濁ろ過することにより式（１－１０１）で表される本発明の化合物を得た。（０．１１ｍｍｏｌ、収率：３３質量％）。
式（１－１０１）で表される化合物の分子量の測定結果は以下のとおりであった。
ＥＩ－ＭＳ（ｍ／ｚ）：９１０［Ｍ］＋
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ（ｐｐｍ）＝８．５２（ｓ、２Ｈ）、７．９３（ｄｄ、２Ｈ）、７．６５（ｄ、２Ｈ）、７．４５（ｓ、１Ｈ）、７．４０（ｄ、２Ｈ）、７．３４（ｄ、２Ｈ）、７．２８（ｄ、２Ｈ）、７．０８（ｓ、２Ｈ）、６．８９（ｓ、２Ｈ）、６．８７（ｓ、４Ｈ）、２．３４（ｓ、１２Ｈ）
Example 2 (Synthesis of compounds of the present invention)
(Step 3) Synthesis of the compound of the present invention represented by formula (1-101) of the above specific example In a flask, di((formylthienyl)-methoxythienyl)difluorodibenzopyromethene-BF 2 complex (0.033 mmol) ) and 3,5-dimethylaniline (0.30 mmol) were dissolved in toluene (2 mL), heated to 95° C. and stirred for 3 hours. The reaction solution was allowed to cool, the solvent was concentrated to dryness, and the intermediate compound was obtained by suspension filtration with ethanol (0.020 mmol). The intermediate compound obtained above was dissolved in dichloromethane (2 mL) in a flask. Boron tribromide (0.5 mL) was then added to the reaction and stirred for 7 hours. After the reaction solution was neutralized by adding a saturated aqueous solution of sodium hydrogencarbonate, the organic layer was concentrated and dried. Methanol was added and suspension filtration was performed to obtain the compound of the present invention represented by formula (1-101). (0.11 mmol, yield: 33% by mass).
The measurement results of the molecular weight of the compound represented by formula (1-101) were as follows.
EI-MS (m/z): 910 [M] +
1 H NMR (CDCl 3 ) δ (ppm) = 8.52 (s, 2H), 7.93 (dd, 2H), 7.65 (d, 2H), 7.45 (s, 1H), 7. 40 (d, 2H), 7.34 (d, 2H), 7.28 (d, 2H), 7.08 (s, 2H), 6.89 (s, 2H), 6.87 (s, 4H) ), 2.34(s, 12H)
比較例１（比較用の化合物の合成）
特許文献５に記載の方法に準じて、下記式（３－１）で表される比較用の化合物を得た。
Comparative Example 1 (Synthesis of compound for comparison)
According to the method described in
（本発明の化合物及び比較用の化合物のクロロホルムに対する溶解度測定）
実施例１、２及び比較例１で得られた本発明の化合物及び比較用の化合物のクロロホルムへの溶解度を測定し、結果を表１に示した。
(Measurement of solubility of compounds of the present invention and comparative compounds in chloroform)
The solubility in chloroform of the compound of the present invention and the comparative compound obtained in Examples 1 and 2 and Comparative Example 1 was measured, and the results are shown in Table 1.
実施例１及び２で得られた本発明の化合物（式（１－６８）、（１－１０１））はいずれも１０ｍｇ／ｍＬ以上の溶解度を示したのに対して。比較例１で得られた比較用の化合物（式（３－１））は２ｍｇ／ｍＬ以下の溶解度であった。この結果より、本発明の化合物が比較用の化合物よりも高い溶解度を有する事は明らかである。 The compounds of the present invention (formulas (1-68) and (1-101)) obtained in Examples 1 and 2 all exhibited a solubility of 10 mg/mL or more. The comparative compound (formula (3-1)) obtained in Comparative Example 1 had a solubility of 2 mg/mL or less. From this result, it is clear that the compounds of the invention have higher solubility than the comparative compounds.
（本発明の化合物及び比較用の化合物のクロロホルム溶液の吸収スペクトルのλｍａｘの測定）
実施例１、２及び比較例１で得られた化合物のクロロホルム溶液（濃度１．０×１０－５ｍｏｌ／Ｌ）を調製し、吸収スペクトルの測定結果に基づいて求めたλｍａｘの値を表２に示した。
(Measurement of λmax of absorption spectra of chloroform solutions of compounds of the present invention and comparative compounds)
Chloroform solutions (concentration 1.0×10 −5 mol/L) of the compounds obtained in Examples 1 and 2 and Comparative Example 1 were prepared, and the values of λmax determined based on the results of absorption spectrum measurement are shown in Table 2. It was shown to.
表２の結果より、実施例１及び２で得られた本発明の化合物（式（１－６８）、（１－１０１））は比較用の化合物（式（３－１））よりも長波長領域にλｍａｘを有しており、近赤外光をより効率的に吸収できることは明らかである。 From the results in Table 2, the compounds of the present invention (formulas (1-68) and (1-101)) obtained in Examples 1 and 2 have a longer wavelength than the comparative compound (formula (3-1)). It is clear that it has λmax in the region and can absorb near-infrared light more efficiently.
実施例３（本発明の化合物を含む有機薄膜の作成と評価）
実施例１で得られた式（１－６８）で表される化合物を用いて、０．５ｗｔ％のクロロホルム溶液を調製した後、石英基板上に１００μＬ塗布し、１０００ｒｐｍ、３０秒の条件でスピンコーティングをすることで本発明の有機薄膜を得た。得られた有機薄膜について吸収スペクトルを測定し、結果を図２に示した。実施例３の有機薄膜のλｍａｘは８９７ｎｍであった。
Example 3 (Preparation and evaluation of an organic thin film containing the compound of the present invention)
Using the compound represented by the formula (1-68) obtained in Example 1, a 0.5 wt% chloroform solution was prepared, then 100 μL was applied on a quartz substrate and spun at 1000 rpm for 30 seconds. The organic thin film of the present invention was obtained by coating. An absorption spectrum was measured for the obtained organic thin film, and the results are shown in FIG. The λmax of the organic thin film of Example 3 was 897 nm.
実施例４（本発明の化合物を含む有機薄膜の作成と評価）
実施例２で得られた式（１－１０１）で表される化合物を用いて、０．５ｗｔ％のクロロホルム溶液を調製した後、石英基板上に１００μＬ塗布し、１０００ｒｐｍ、３０秒間の条件でスピンコーティングをすることで本発明の有機薄膜を得た。得られた有機薄膜について吸収スペクトルを測定し、結果を図３に示した。実施例４の有機薄膜のλｍａｘは９３３ｎｍであった。
Example 4 (Preparation and evaluation of organic thin film containing the compound of the present invention)
Using the compound represented by the formula (1-101) obtained in Example 2, a 0.5 wt% chloroform solution was prepared, then 100 μL was applied on a quartz substrate and spun at 1000 rpm for 30 seconds. The organic thin film of the present invention was obtained by coating. An absorption spectrum was measured for the obtained organic thin film, and the results are shown in FIG. The λmax of the organic thin film of Example 4 was 933 nm.
図３及び４の結果より、本発明の化合物を含む有機薄膜が、近赤外光領域でも良好な光吸収特性を示すことは明らかである。 From the results of FIGS. 3 and 4, it is clear that the organic thin film containing the compound of the present invention exhibits good light absorption properties even in the near-infrared region.
本発明の化合物は、合成上の簡便さと、溶媒に対する高い溶解性、溶液プロセスによる成膜性、近赤外領域における吸収特性を兼ね備えており、近赤外領域における光吸収色素として非常に有用である。 The compounds of the present invention are very useful as light-absorbing dyes in the near-infrared region because of their ease of synthesis, high solubility in solvents, film-forming properties by solution processes, and absorption properties in the near-infrared region. be.
（図１）
１ 絶縁部
２ 上部電極
３ 電子ブロック層
４ 光電変換層
５ 正孔ブロック層
６ 下部電極
７ 絶縁基材若しくは他光電変換素子
(Fig. 1)
1 Insulating
Claims (9)
An imaging device comprising the photoelectric conversion device according to claim 7 .
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