JP3972097B2 - Phthalocyanine-based near infrared dye and thin film - Google Patents
Phthalocyanine-based near infrared dye and thin film Download PDFInfo
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- JP3972097B2 JP3972097B2 JP2003038060A JP2003038060A JP3972097B2 JP 3972097 B2 JP3972097 B2 JP 3972097B2 JP 2003038060 A JP2003038060 A JP 2003038060A JP 2003038060 A JP2003038060 A JP 2003038060A JP 3972097 B2 JP3972097 B2 JP 3972097B2
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- phthalocyanine
- infrared dye
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- infrared
- thin film
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims description 22
- 239000010409 thin film Substances 0.000 title claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical compound I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 125000004429 atom Chemical group 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000000975 dye Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000010408 film Substances 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 4
- 229920006391 phthalonitrile polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LOTMIRVNJTVTSU-UHFFFAOYSA-N 4-tert-butylbenzene-1,2-dicarbonitrile Chemical compound CC(C)(C)C1=CC=C(C#N)C(C#N)=C1 LOTMIRVNJTVTSU-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 phthalocyanine compound Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Landscapes
- Optical Filters (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、フタロシアン系近赤外色素およびその薄膜とその製造方法に関するものである。さらに詳しくは、この出願の発明は、半導体レーザー用感光色素、プラズマディスプレー（ＰＤＰ）やシリコン受光素子（ＳＤＰ）用の近赤外線カットフィルター等として有用な、フタロシアニン系近赤外色素およびその薄膜とその製造方法に関するものである。
【０００２】
【従来の技術とその課題】
ＣＣＤ（電荷結合素子）やフォトダイオードに使用されるＳＰＤの感度は可視域から近赤外線まで及ぶが、その感度を人間の視感度に合わせるために７００〜１０００ｎｍの近赤外線を遮断する目的で、またＰＤＰが放つ無用の近赤外域の雑音の悪影響からＳＰＤを用いた機器（リモコン付家電等）を保護する必要性等から近赤外吸収材の重要性が高まっている。一方で、光コピー、レーザープリンター、そして光ディスク（ＣＤ−Ｒ）等、半導体レーザーを用いる産業においては、近赤外光を積極的に利用するために、レーザー光の波長に応じた感度を持つ安定した感光色素が必要であり、これらの波長域に感度を持つ色素としてフタロシアニン系の化合物が頻繁に用いられている。そして、一般にフタロシアニンの光吸収極大波長は可視域（典型的には６６０〜６９０ｎｍ）に存在しているために上記の波長域から離れていることから、この波長の差を克服するために、従来は、フタロシアニンの結晶系を制御することにより吸収を広幅化させて対応する方法や分子骨格に特殊な置換基を導入することによる吸収極大波長を長波長シフトさせる方法、フタロシアニンのπ電子系を拡張したナフタロシアニンの誘導体を用いて近赤外に吸収を持たせる方法などが採用されている。しかしながら、これら従来の方法はいずれも多大な労力を必要とする他、薄膜化が困難であることや、高価な試薬を用いて数段階の反応経路を必要とする等の欠点を有している。また、薄膜化した場合に会合の影響による短波長シフトのために十分な吸収強度を持てない等の問題点がある。
【０００３】
このような状況において、この出願の発明者らは、五価のアンチモンのフタロシアニン系錯体に注目して近赤外色素とすることを検討してきた（文献１〜３）。また、この検討の過程において特許出願も行っている（特願２００２−１７２４５１号）。
【０００４】
だが、上記のような課題についての解決策としては必ずしも実用的に満足できないでいた。
【０００５】
【文献】
１：Y.Kagaya, H.Isago, Chem.Lett., 1994,1957-1960
２：H.Isago, Y.Kagaya, S.Nakajima, Chem.Lett., 32,112-113(2003)
３：Y.Kagaya, H.Isago, Bull.Chem.Soc.Jpn., 70,2179-2185(1997)
そこで、この出願の発明は、上記のとおりの問題点を解消し、合成、精製、そして製膜が容易で、近赤外吸収特性に優れた、新しい近赤外色素とその薄膜、並びにその製造方法を提供することを課題としている。
【０００６】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、第１には、
次式；
【０００７】
【化２】
（式中のＲは、各々のベンゼン環に結合する１以上の置換基であって、同一または別異であってよく、炭化水素基および異種原子を有する置換炭化水素基から選択されたものを示す）
で表わされる陽イオンと対陰イオンとによって構成される錯体であって、軸配位子を有しないフタロシアニン系近赤外色素を提供し、また、第２には、上記炭化水素基が直鎖または分枝鎖状のアルキル基であるフタロシアニン系近赤外色素を、そして、第３には上記色素が成膜されたものであることを特徴とするフタロシアニン系近赤外色素薄膜を、そして、この出願の発明は、第４には、ベンゼン環に、同一または別異の、１以上の、炭化水素基および異種原子を有する置換炭化水素基から選択された置換基を結合するフタロニトリルとヨウ化アンチモン（ＳｂＩ ３ ）との混合物を加熱する上記フタロシアニン系近赤外色素の製造方法を提供する。
【０００９】
【発明の実施の形態】
そこで、以下に発明の実施の形態について説明する。
【００１０】
この出願の発明においては、フタロシアニン骨格上の置換基としては、比較的炭素数の少ない炭化水素を含む置換基が立体構造学的に安定性が良く、このような炭化水素としてはアルキル基等が特に好ましいが、アルキル基だけでなくアルコキシ基、アルキルチオ基等も考慮されてよい。また、炭化水素部分は直鎖炭化水素だけでなく、tert−ブチル基のような枝分かれした炭化水素も対象になることは言うまでもない。
【００１１】
また、この出願の発明における対陰イオンは化合物の物性にほとんど関係がないので、それ自身が安定であり、かつアンチモン−フタロシアニンの陽イオン部分と反応さえしなければどのようなものでも使用可能である。
【００１２】
この出願の発明を、ベンゼン環の１個をtert−ブチル基で置換されたフタロニトリルと三価のヨウ化アンチモンを例に説明すると、フタロニトリルの４モルと三価のヨウ化アンチモンの１モルとの混合物（モル比４：１）を６時間から８時間程度加熱することにより、テトラ−tert−ブチルフタロシアニナト）アンチモン(III)（〔Ｓｂ（ｔｂｐｃ）〕+；ｔｂｐｃ＝Ｃ48Ｈ48Ｎ8 2-）の三ヨウ化物（Ｉ3 -）を単離することができる。
【００１３】
この単離された緑色の粘性の高い融液をジクロロメタン、ベンゼン、ヘキサンを用いて精製する。そして、精製された化合物をスピンコート法に用いられる一般的な溶媒に容易に溶解すると、その溶液は近赤外領域に強い光吸収を示し（ジクロロメタン中で７６３ｎｍ：溶媒によって異なる）、高濃度では分子会合によりさらに長波長側に（８６０ｎｍ）にも吸収を示すものであり、その溶液から製造される溶媒キャスト膜は６００−１０００ｎｍに及ぶ領域に強い光吸収を示すことも確認することができる。
【００１４】
この出願の発明による化合物においては、フタロシアニンとアンチモン(III)との相互作用により吸収極大波長が近赤外まで達しているので、フタロシアニン分子骨格に導入する置換基は、化合物の溶解度さえ向上できればtert−ブチル基の様な単純なものでも差し支えない。また当該発明品の場合、分子会合の影響により、吸収帯が長波長シフトするため、薄膜化した場合に、より広範囲の近赤外域に感度を持つ特徴がある。さらに市販の安価な置換フタロニトリルとヨウ化アンチモンの混合物をある適当な条件で加熱するだけであるので合成が容易であり、収率も高く、また溶解度が高いので精製も容易であるため、生産コストを大変低く抑えることができる。また、この方法は一般の有機溶媒に高い溶解性を持つためスピンコート法や溶媒キャスト法による製膜が容易である。
【００１５】
なお、三価のアンチモンのフタロシアニン錯体そのものについてはその溶液中のスペクトルが報告されている（文献４）が、この場合には単離されていないために組成は判明していない。また、結晶構造も報告されている（文献５）が、この報告では色素としての性質やスペクトルデータは何一つ明らかにされていない。
【００１６】
【文献】
４：G.Knoer, Inorg.Chem., 35,7916-7917(1996)
５：R.Kubiak, J.Janczak, M.Razik, Inorg.Chim.Acta, 293, 155-159(1999)そこで以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって発明が限定されることはない。
【００１７】
【実施例】
１．４９ｇのtert−ブチルフタロニトリルと１．００ｇの無水ヨウ化アンチモンの混合物を１６５℃で攪拌しながら７時間加熱して生じた緑色の粘性の高い融液を室温まで放冷し、２００ｍｌのジクロロメタンに溶解し、不溶物を除去した後、溶媒を除去する。得られた緑色の固体をベンゼン（約２００ｍｌ）に縣濁させ、３倍の体積のヘキサンを加えて固体を析出させ、紫色の母液は捨てる。この操作を母液がほとんど無色になるまで（本実施例では３回）繰り返す。さらにジクロロメタン（約２０ｍｌ）に縣濁させ、上と同様に３倍の体積のヘキサンを加えて固体を析出させ、母液がほとんど無色になるまで（本実施例では２回）繰り返す。析出した固体を集めて６０℃で１時間乾燥させて、１．１７ｇの当該発明品の粗生成物を得る。２１０ｍｇの粗生成物を５５ｍｌのジクロロメタンに溶解し、不溶性の黄色固体をろ別した後、溶媒をロータリーエバポレーターを用いて除去する。得られた固体を６０ｍｌのジクロロメタンに再度溶解し、３倍の体積のヘキサンを加えて緑色の固体を析出させる（この操作を２回繰り返す）。遠心分離で固体を集めて８０℃で２時間乾燥させ、１５５ｍｇ（原料の置換フタロニトリルに対し、収率３５％）の当該発明品を得る。元素分析結果；Ｃ：４６．６９％、Ｈ：３．７７％、Ｎ：８．７４％（理論値；Ｃ：４６．５２％、Ｈ：３．９０％、Ｎ：９．０４％；Ｃ48Ｈ48Ｎ8ＳｂＩ3として）。色素部分の組成が〔Ｃ48Ｈ48Ｎ8Ｓｂ〕+であることを質量分析（図１）から、対陰イオンＩ3 -の存在はラマンスペクトルにおける特徴的な散乱ピーク（１１４ｃｍ-1）によって確認した。ジクロロメタン、ベンゼン、アセトン、アセトニトリル、テトラヒドロフラン、ジメチルスルホキシド等の溶媒に良く溶け、ヘキサンには全く溶けない。ジクロロメタン希薄溶液中で７６３ｎｍに光吸収極大（モル吸光係数１．３×１０5Ｍ-1ｃｍ-1）を示し、また高濃度では会合体を生じ、８５９ｎｍを新たな吸収帯を示す。この化合物をジクロロメタンに溶解して約２×１０-4Ｍ程度の溶液を調整し、約５０℃に加熱した石英板上に塗布することにより、溶媒キャスト膜を得た。
【００１８】
図２に示すように、この膜は７７０ｎｍおよび８９０ｎｍにそれぞれ非会合体および会合体による光吸収帯があり、膜自体としては６００−１０００ｎｍの範囲に光吸収を示すことが確認された。
【００１９】
【発明の効果】
この出願の発明によって、合成、精製、製膜が容易であるため、近赤外吸収色素およびその薄膜が安価に製造でき、しかも、高性能な半導体レーザー用感光色素、プラズマディスプレー（ＰＤＰ）やシリコン受光素子（ＳＤＰ）用の近赤外線カットフィルター等に有用な色素とその薄膜を提供することができる。
【図面の簡単な説明】
【図１】フタロシアニン系赤外色素の質量分析結果と安定同位体分布に基づいた理論値との比較図である。
【図２】フタロシアニン系赤外色素のジクロロメタン溶液中および溶媒キャスト膜の光吸収スペクトルならびに濃度依存性を示す図である。[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a phthalocyanine-based near-infrared dye, a thin film thereof, and a production method thereof. More specifically, the invention of this application relates to a phthalocyanine-based near-infrared dye, its thin film, and its thin film, which are useful as a photosensitive dye for a semiconductor laser, a near-infrared cut filter for a plasma display (PDP), a silicon light-receiving element (SDP), etc. It relates to a manufacturing method.
[0002]
[Prior art and its problems]
The sensitivity of SPDs used in CCDs (Charge Coupled Devices) and photodiodes extends from the visible range to the near infrared, but for the purpose of blocking the near infrared of 700 to 1000 nm in order to match the sensitivity with human visual sensitivity, The importance of near-infrared absorbers is increasing due to the need to protect devices (such as home appliances with remote controls) using SPD from the adverse effects of unwanted near-infrared noise emitted by PDP. On the other hand, in industries that use semiconductor lasers, such as optical copying, laser printers, and optical discs (CD-R), in order to actively use near-infrared light, stable with sensitivity according to the wavelength of the laser light. A phthalocyanine compound is frequently used as a dye having sensitivity in these wavelength ranges. In general, since the light absorption maximum wavelength of phthalocyanine exists in the visible region (typically 660 to 690 nm) and is far from the above wavelength region, in order to overcome this wavelength difference, Expands the π-electron system of phthalocyanine, a method that broadens absorption by controlling the crystal system of phthalocyanine, a method that shifts the absorption maximum wavelength by introducing a special substituent into the molecular skeleton, and a long wavelength shift For example, a method of giving absorption in the near infrared using a naphthalocyanine derivative has been adopted. However, each of these conventional methods requires a great deal of labor, and also has drawbacks that it is difficult to reduce the thickness of the film and that several reaction paths are required using an expensive reagent. . In addition, when the film is thinned, there is a problem that a sufficient absorption intensity cannot be obtained due to a short wavelength shift due to the influence of the association.
[0003]
Under such circumstances, the inventors of this application have studied to make a near-infrared dye by paying attention to a phthalocyanine-based complex of pentavalent antimony (
[0004]
However, it was not always satisfactory practically as a solution to the above problems.
[0005]
[Literature]
1: Y. Kagaya, H. Isago, Chem. Lett., 1994, 1957-1960
2: H. Isago, Y. Kagaya, S. Nakajima, Chem. Lett., 32, 112-113 (2003)
3: Y. Kagaya, H. Isago, Bull. Chem. Soc. Jpn., 70, 2179-2185 (1997)
Therefore, the invention of this application eliminates the problems as described above, is easy to synthesize, purify and form a film, and has a new near-infrared dye excellent in near-infrared absorption characteristics, its thin film, and its production The challenge is to provide a method.
[0006]
[Means for Solving the Problems]
As the invention of this application solves the above-mentioned problems, first,
The following formula:
[0007]
[Chemical 2]
(In the formula, R represents one or more substituents bonded to each benzene ring, which may be the same or different, and are selected from a hydrocarbon group and a substituted hydrocarbon group having a hetero atom. Show)
And a phthalocyanine-based near-infrared dye having no axial ligand, and secondly, the hydrocarbon group is a straight chain. Or a phthalocyanine-based near-infrared dye, which is a branched alkyl group, and thirdly, a phthalocyanine-based near-infrared dye thin film characterized in that the dye is formed into a film, and the invention of this application, the fourth, the benzene ring, the same or different, one or more, and the lid nitrile to combine a substituent selected from substituted hydrocarbon group having a hydrocarbon group and a heteroatom Provided is a method for producing the above phthalocyanine-based near infrared dye, in which a mixture with antimony iodide (SbI 3 ) is heated.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Therefore, embodiments of the invention will be described below.
[0010]
In the invention of this application, as a substituent on the phthalocyanine skeleton, a substituent containing a hydrocarbon having a relatively small number of carbon atoms has good steric structural stability, and such a hydrocarbon includes an alkyl group and the like. Although particularly preferable, not only an alkyl group but also an alkoxy group, an alkylthio group, and the like may be considered. Needless to say, the hydrocarbon portion is not only a straight chain hydrocarbon but also a branched hydrocarbon such as a tert-butyl group.
[0011]
In addition, since the counter anion in the invention of this application has little relation to the physical properties of the compound, anything can be used as long as it is stable and does not react with the cationic part of antimony-phthalocyanine. is there.
[0012]
The invention of this application will be described with reference to phthalonitrile in which one of the benzene rings is substituted with a tert-butyl group and trivalent antimony iodide as an example. 4 moles of phthalonitrile and 1 mole of trivalent antimony iodide Is heated for about 6 to 8 hours to give tetra-tert-butylphthalocyaninato) antimony (III) ([Sb (tbpc)] + ; tbpc = C 48 H 48 N 8 2- ) triiodide (I 3 − ) can be isolated.
[0013]
The isolated green viscous melt is purified using dichloromethane, benzene and hexane. When the purified compound is easily dissolved in a general solvent used in the spin coating method, the solution shows strong light absorption in the near infrared region (763 nm in dichloromethane: different depending on the solvent). It can also be confirmed that the solvent cast film produced from the solution exhibits strong light absorption in the region extending from 600 to 1000 nm due to the molecular association, which also absorbs on the longer wavelength side (860 nm).
[0014]
In the compound according to the invention of this application, since the absorption maximum wavelength reaches the near infrared due to the interaction between phthalocyanine and antimony (III), the substituent introduced into the phthalocyanine molecular skeleton can be tert if it can improve the solubility of the compound. -It can be as simple as a butyl group. Further, in the case of the invention product, the absorption band shifts by a long wavelength due to the influence of molecular association. Therefore, when it is thinned, it has a characteristic of having sensitivity in a wider range of near infrared region. In addition, a commercially available mixture of inexpensive substituted phthalonitrile and antimony iodide can be heated only under appropriate conditions, so that the synthesis is easy, the yield is high, and the solubility is high. Cost can be kept very low. Further, since this method has high solubility in a general organic solvent, film formation by a spin coating method or a solvent casting method is easy.
[0015]
The trivalent antimony phthalocyanine complex itself has been reported to have a spectrum in the solution (Reference 4), but in this case, since it has not been isolated, its composition is not known. A crystal structure has also been reported (Reference 5), but this report does not reveal any properties or spectral data as a dye.
[0016]
[Literature]
4: G. Knoe, Inorg. Chem., 35, 7916-7917 (1996)
5: R. Kubiak, J. Janczak, M. Razik, Inorg. Chim. Acta, 293, 155-159 (1999) Then, an Example is shown below and it demonstrates in detail. Of course, the invention is not limited by the following examples.
[0017]
【Example】
A green viscous melt formed by heating a mixture of 1.49 g of tert-butylphthalonitrile and 1.00 g of anhydrous antimony iodide with stirring at 165 ° C. for 7 hours was allowed to cool to room temperature. After dissolving in dichloromethane and removing insolubles, the solvent is removed. The obtained green solid is suspended in benzene (about 200 ml), three times the volume of hexane is added to precipitate the solid, and the purple mother liquor is discarded. This operation is repeated until the mother liquor is almost colorless (three times in this example). Further, suspend in dichloromethane (about 20 ml), add 3 times the volume of hexane in the same manner as above to precipitate a solid, and repeat until the mother liquor is almost colorless (twice in this example). The precipitated solid is collected and dried at 60 ° C. for 1 hour to obtain 1.17 g of the crude product of the present invention. 210 mg of the crude product is dissolved in 55 ml of dichloromethane, the insoluble yellow solid is filtered off and the solvent is then removed using a rotary evaporator. The obtained solid is dissolved again in 60 ml of dichloromethane, and 3 times volume of hexane is added to precipitate a green solid (this operation is repeated twice). The solid is collected by centrifugation and dried at 80 ° C. for 2 hours to obtain 155 mg (35% yield with respect to the raw material substituted phthalonitrile) of the invention. Elemental analysis results: C: 46.69%, H: 3.77%, N: 8.74% (theoretical value; C: 46.52%, H: 3.90%, N: 9.04%; C as 48 H 48 N 8 SbI 3) . From the mass analysis (FIG. 1) that the composition of the dye moiety is [C 48 H 48 N 8 Sb] + , the presence of the counter anion I 3 − is caused by a characteristic scattering peak (114 cm −1 ) in the Raman spectrum. confirmed. It dissolves well in solvents such as dichloromethane, benzene, acetone, acetonitrile, tetrahydrofuran, and dimethyl sulfoxide, but does not dissolve in hexane at all. It shows a light absorption maximum (molar extinction coefficient 1.3 × 10 5 M −1 cm −1 ) at 763 nm in a dilute solution of dichloromethane, and an association is formed at a high concentration, and a new absorption band is shown at 859 nm. This compound was dissolved in dichloromethane to prepare a solution of about 2 × 10 −4 M and coated on a quartz plate heated to about 50 ° C. to obtain a solvent cast film.
[0018]
As shown in FIG. 2, this film has light absorption bands due to non-aggregates and aggregates at 770 nm and 890 nm, respectively, and the film itself was confirmed to exhibit light absorption in the range of 600 to 1000 nm.
[0019]
【The invention's effect】
According to the invention of this application, since synthesis, purification, and film formation are easy, a near-infrared absorbing dye and its thin film can be manufactured at low cost, and a high-performance photosensitive dye for semiconductor laser, plasma display (PDP) and silicon It is possible to provide a dye useful for a near infrared cut filter for a light receiving element (SDP) and a thin film thereof.
[Brief description of the drawings]
FIG. 1 is a comparison diagram between the results of mass spectrometry analysis of phthalocyanine-based infrared dyes and theoretical values based on stable isotope distributions.
FIG. 2 is a diagram showing the light absorption spectrum and concentration dependency of a phthalocyanine-based infrared dye in a dichloromethane solution and a solvent cast film.
Claims (4)
で表わされる陽イオンと対陰イオンとによって構成される錯体であって、軸配位子を有しないことを特徴とするフタロシアニン系近赤外色素。The following formula:
A phthalocyanine-based near-infrared dye, which is a complex composed of a cation and an anion represented by formula (1) and has no axial ligand .
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| JP5360534B2 (en) * | 2008-08-01 | 2013-12-04 | 独立行政法人物質・材料研究機構 | Photosensitive element |
| WO2010098359A1 (en) * | 2009-02-24 | 2010-09-02 | 独立行政法人物質・材料研究機構 | Water-soluble phthalocyanine dye |
| JP5586010B2 (en) * | 2010-01-26 | 2014-09-10 | 独立行政法人物質・材料研究機構 | Water-soluble phthalocyanine |
| JP5383755B2 (en) * | 2010-12-17 | 2014-01-08 | 株式会社日本触媒 | Light selective transmission filter, resin sheet, and solid-state image sensor |
| TWI588192B (en) | 2011-10-14 | 2017-06-21 | Jsr Corp | Optical filter, solid-state imaging device and camera module using the optical filter |
| JP2013103911A (en) * | 2011-11-14 | 2013-05-30 | Kaneka Corp | Infrared absorption phthalocyanine |
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