JP2015074754A - Organic dye - Google Patents
Organic dye Download PDFInfo
- Publication number
- JP2015074754A JP2015074754A JP2013213265A JP2013213265A JP2015074754A JP 2015074754 A JP2015074754 A JP 2015074754A JP 2013213265 A JP2013213265 A JP 2013213265A JP 2013213265 A JP2013213265 A JP 2013213265A JP 2015074754 A JP2015074754 A JP 2015074754A
- Authority
- JP
- Japan
- Prior art keywords
- group
- organic dye
- represent
- organic
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(C(C(C1=CC2)=CC2=C)=C(C)C)*1=C Chemical compound CC(C(C(C1=CC2)=CC2=C)=C(C)C)*1=C 0.000 description 4
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
本発明は、光吸収材料として有用な有機色素に関するものである。 The present invention relates to an organic dye useful as a light absorbing material.
光吸収材料として使用されている色素は、銀塩写真感光材料、感熱記録材料、光学用フィルター、CD−RやDVD−R等の光学記録媒体、光感光性樹脂用の増感剤、医療用蛍光性センサー、衣料用染色剤等、広範囲な分野に用途を有する。また、近年では、太陽電池の分野においても、色素の利用が検討されている。 Dyes used as light absorbing materials include silver salt photographic light-sensitive materials, heat-sensitive recording materials, optical filters, optical recording media such as CD-R and DVD-R, sensitizers for photosensitive resins, and medical use It has applications in a wide range of fields, such as fluorescent sensors and clothing dyes. In recent years, the use of dyes has been studied also in the field of solar cells.
光吸収材料として使用されている色素は、無機色素、有機金属色素(錯体系色素)、有機色素に大別される。このうち、有機色素は、種類が多い、色の自由度が多い、安価である等の利点を有していて、上述した用途において、有用な色素として使用されている(例えば、特許文献1〜9参照)。しかしながら、無機色素や有機金属色素と比較して、有機色素の耐久性は低く、特に、光照射によって劣化するという問題を有していた。 The dyes used as the light absorbing material are roughly classified into inorganic dyes, organometallic dyes (complex dyes), and organic dyes. Among these, organic dyes have advantages such as many types, many degrees of freedom in color, and low cost, and are used as useful dyes in the above-described applications (for example, Patent Documents 1 to 3). 9). However, compared to inorganic dyes and organometallic dyes, the durability of organic dyes is low, and in particular, there is a problem that they deteriorate due to light irradiation.
本発明の課題は、優れた耐光性を有する有機色素を提供することである。 The subject of this invention is providing the organic pigment | dye which has the outstanding light resistance.
上記課題を達成すべく鋭意検討した結果、下記発明によって、上記課題を解決した。 As a result of intensive studies to achieve the above-mentioned problems, the following problems have been solved by the following invention.
(1)一般式[I]で示される有機色素。 (1) An organic dye represented by the general formula [I].
(一般式[I]において、Ar1とAr2は芳香族炭化水素残基を示し、R1とR2、R3とR4は水素原子またはアルキル基を示し、両者が連結してシクロペンタン環またはシクロヘキサン環を形成しても良い。Q1とQ2は、二価の電子吸引性有機残基を示す。L1とL2は、アルキレン基を示す。X−は対アニオンを示す。) (In the general formula [I], Ar 1 and Ar 2 represent aromatic hydrocarbon residues, R 1 and R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group, and both are linked to form cyclopentane. A ring or a cyclohexane ring may be formed, Q 1 and Q 2 represent a divalent electron-withdrawing organic residue, L 1 and L 2 represent an alkylene group, and X − represents a counter anion. )
(2)Q1とQ2が、一般式[II]、[III]、[IV]、[V]、[VI]で示される二価の電子吸引性有機残基から選択されるいずれかである上記(1)記載の有機色素。 (2) Q 1 and Q 2 are any one selected from divalent electron-withdrawing organic residues represented by the general formulas [II], [III], [IV], [V], and [VI] The organic dye according to (1) above.
(R5、R7、R10、R12、R15は、水素原子またはアルキル基である。R6、R9、R11、R14は、アルキレン基である。R8、R13、R16、R17は、アルキル基、アラルキル基またはアリール基である。) (R 5 , R 7 , R 10 , R 12 , R 15 are hydrogen atoms or alkyl groups. R 6 , R 9 , R 11 , R 14 are alkylene groups. R 8 , R 13 , R 15 16 and R 17 are an alkyl group, an aralkyl group or an aryl group.)
(3)R5、R7、R10、R12、R15が、水素原子または炭素数1以上4以下のアルキル基であり、R6、R9、R11、R14が、炭素数1以上3以下のアルキレン基であり、R8、R13、R16、R17が、炭素数1以上14以下のアルキル基、炭素数7以上14以下のアラルキル基または炭素数6以上14以下のアリール基である上記(2)記載の有機色素。 (3) R 5 , R 7 , R 10 , R 12 , and R 15 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 6 , R 9 , R 11 , and R 14 are 1 carbon atom. It is an alkylene group having 3 or less and R 8 , R 13 , R 16 and R 17 are alkyl groups having 1 to 14 carbon atoms, aralkyl groups having 7 to 14 carbon atoms or aryl having 6 to 14 carbon atoms The organic dye according to (2), which is a group.
(4)L1とL2が、炭素数2以上10以下のアルキレン基である上記(1)〜(3)のいずれか記載の有機色素。 (4) The organic dye according to any one of (1) to (3), wherein L 1 and L 2 are alkylene groups having 2 to 10 carbon atoms.
一般式[I]で示される有機色素は、電子吸引性物質である、4,4′−ビピリジニウム残基に対して、メロシアニン色素に分類される色素の残基が2個連結された化合物であり、優れた耐光性を達成することができる。 The organic dye represented by the general formula [I] is a compound in which two dye residues classified as merocyanine dyes are linked to a 4,4′-bipyridinium residue which is an electron-withdrawing substance. Excellent light resistance can be achieved.
一般式[I]で示される有機色素について説明する。一般式[I]において、Ar1とAr2は芳香族炭化水素残基を示す。好ましい例としては、以下に示すAR−1〜AR−22が挙げられるが、これらに限定されるものではない。Ar1とAr2において、これら芳香族炭化水素残基が、置換基としてpKaが6未満の酸性基をさらに有しても良い。pKaが6未満の酸性基の具体例としては、カルボキシ基、スルホ基、スルフィノ基、スルフェノ基、フォスフォノ基、フォスフィニコ基などが挙げられる。この中でも、カルボキシ基が特に好ましい。 The organic dye represented by the general formula [I] will be described. In the general formula [I], Ar 1 and Ar 2 represent an aromatic hydrocarbon residue. Preferred examples include AR-1 to AR-22 shown below, but are not limited thereto. In Ar 1 and Ar 2 , these aromatic hydrocarbon residues may further have an acidic group having a pKa of less than 6 as a substituent. Specific examples of the acidic group having a pKa of less than 6 include a carboxy group, a sulfo group, a sulfino group, a sulfeno group, a phosphono group, and a phosphinico group. Among these, a carboxy group is particularly preferable.
R1とR2、R3とR4は水素原子またはアルキル基を示す。アルキル基の具体例としては、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、n−ヘキシル基、n−オクチル基等の直鎖のアルキル基、イソプロピル基、イソブチル基、イソペンチル基、イソヘキシル基等の側鎖を有するアルキル基が挙げられる。R1とR2、R3とR4は、それぞれ、同一炭素数のアルキル基であっても良いし、異なる炭素数のアルキル基であっても良い。また、R1とR2、R3とR4は、両者で結合してシクロペンタン環またはシクロヘキサン環を形成しても良い。特に好ましいのは、両者で結合してシクロペンタン環またはシクロヘキサン環を形成しているものである。 R 1 and R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group. Specific examples of the alkyl group include a straight chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group, an isopropyl group, and an isobutyl group. And an alkyl group having a side chain such as a group, an isopentyl group, and an isohexyl group. R 1 and R 2 , R 3 and R 4 may each be an alkyl group having the same carbon number, or may be an alkyl group having a different carbon number. R 1 and R 2 , R 3 and R 4 may be bonded together to form a cyclopentane ring or a cyclohexane ring. Particularly preferred are those in which they are combined to form a cyclopentane ring or a cyclohexane ring.
Q1とQ2は、二価の電子吸引性有機残基を示す。二価の電子吸引性有機残基の具体例については、「高機能フォトケミカルズ−構造機能と応用展望−」((株)シーエムシー、1986年発行)の第101ページに記載されている活性ケトメチレン化合物を構造内に有する二価の有機残基が挙げられるが、もちろん、これらに限定されるものではない。活性ケトメチレン化合物の具体例を下記に示す。 Q 1 and Q 2 represent a divalent electron-withdrawing organic residue. For specific examples of divalent electron-withdrawing organic residues, active ketomethylene described in page 101 of "Highly functional photochemicals-Structural function and application prospects" (CMC, 1986). A divalent organic residue having a compound in the structure may be mentioned, but of course, the present invention is not limited thereto. Specific examples of the active ketomethylene compound are shown below.
好ましいQ1とQ2としては、一般式[II]、[III]、[IV]、[V]、[VI]で示される二価の電子吸引性有機残基が挙げられる。 Preferred examples of Q 1 and Q 2 include divalent electron-withdrawing organic residues represented by the general formulas [II], [III], [IV], [V], and [VI].
R5、R7、R10、R12、R15は、水素原子またはアルキル基である。アルキル基としては、メチル基、エチル基、n−プロピル基、n−ブチル基等が挙げられ、好ましくは炭素数1以上4以下のアルキル基である。また、R6、R9、R11、R14は、メチレン基、エチレン基、トリメチレン基、テトラメチレン基等のアルキレン基であり、好ましくは炭素数1以上3以下のアルキレン基である。 R 5 , R 7 , R 10 , R 12 and R 15 are a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and an alkyl group having 1 to 4 carbon atoms is preferable. R 6 , R 9 , R 11 , and R 14 are alkylene groups such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group, and preferably an alkylene group having 1 to 3 carbon atoms.
R8、R13、R16、R17は、アルキル基、アラルキル基またはアリール基である。アルキル基としては、メチル基、エチル基、n−プロピル基、n−ブチル基、n−ヘキシル基、n−オクチル基等の直鎖のアルキル基、イソプロピル基、イソブチル基、イソペンチル基、イソヘキシル基等の側鎖を有するアルキル基が挙げられ、好ましくは炭素数1以上14以下のアルキル基である。アラルキル基としては、ベンジル基、ヘネチル基、4−フェニルブチル基等が挙げられ、好ましくは炭素数7以上14以下のアラルキル基である。アリール基としては、フェニル基、2−ナフチル基等が挙げられ、好ましくは炭素数6以上14以下のアリール基である。 R 8 , R 13 , R 16 and R 17 are an alkyl group, an aralkyl group or an aryl group. Examples of the alkyl group include a straight chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, and an n-octyl group, an isopropyl group, an isobutyl group, an isopentyl group, and an isohexyl group. And an alkyl group having 1 to 14 carbon atoms is preferable. Examples of the aralkyl group include a benzyl group, a henethyl group, and a 4-phenylbutyl group, and an aralkyl group having 7 to 14 carbon atoms is preferable. Examples of the aryl group include a phenyl group and a 2-naphthyl group, and an aryl group having 6 to 14 carbon atoms is preferable.
X−は対アニオンである。具体的には、ハロゲンアニオン、アルキル硫酸アニオン(例えば、メタンスルホン酸アニオン)、有機スルホン酸アニオン(例えばp−トルエンスルホン酸)、硫酸アニオン、テトラフルオロホウ酸アニオン、ヘキサフルオロリン酸アニオン、ヘキサフルオロケイ酸アニオン等が挙げられる。 X − is a counter anion. Specifically, halogen anion, alkyl sulfate anion (for example, methanesulfonate anion), organic sulfonate anion (for example, p-toluenesulfonic acid), sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, hexafluoro Examples include silicate anion.
次に、一般式[I]で示される有機色素の具体例を挙げるが、これらに限定されるものではない。 Next, specific examples of the organic dye represented by the general formula [I] will be given, but it should not be construed that the invention is limited thereto.
本発明の有機色素の代表的な合成方法を説明する。例えば、化合物a)を出発原料として、以下の合成スキームにしたがって合成できる。化合物a)は、例えば特開2004−200068号公報などに記載の合成方法を参考にして合成することができる。 A typical synthesis method of the organic dye of the present invention will be described. For example, it can be synthesized according to the following synthesis scheme using compound a) as a starting material. Compound a) can be synthesized with reference to a synthesis method described in, for example, JP-A No. 2004-200068.
上記合成スキームにおいて、R、R′は水素原子またはアルキル基を示す。Q3、Q4は電子吸引性有機残基を示す。Xは、置換反応によってX−(ハロゲンアニオン、アルキル硫酸アニオン、有機スルホン酸アニオン等)を生じる基を示し、Yはハロゲン原子を示す。色素の合成及び単離後、化学的にアニオン交換処理することによって、X−を硫酸アニオン、テトラフルオロホウ酸アニオン、ヘキサフルオロリン酸アニオン、ヘキサフルオロケイ酸アニオン等に変換することができる。 In the above synthetic scheme, R and R ′ represent a hydrogen atom or an alkyl group. Q 3 and Q 4 represent electron-withdrawing organic residues. X represents a group that generates X − (halogen anion, alkyl sulfate anion, organic sulfonate anion, etc.) by a substitution reaction, and Y represents a halogen atom. After synthesis and isolation of the dye, chemically by anion exchange treatment, X - can be converted sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, a hexafluorosilicate anion.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらに何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these at all.
(合成例1:有機色素D−9の合成)
化合物A、化合物B及び2−ブロモエチルアミン・臭化水素酸塩を用いて、上記合成スキームにしたがって、本発明の有機色素D−9を合成した。図1は、有機色素D−9の吸収スペクトル(DMF(ジメチルホルムアミド)溶液)である。図2は、有機色素D−9の1H−NMRスペクトル(DMSO(ジメチルスルホキシド)−d6溶液)である。有機色素D−9の吸収スペクトルの吸収極大値:λmax=541nm、463nm、397nm(DMF溶液)。
(Synthesis Example 1: Synthesis of organic dye D-9)
Using Compound A, Compound B and 2-bromoethylamine / hydrobromide, the organic dye D-9 of the present invention was synthesized according to the above synthesis scheme. FIG. 1 is an absorption spectrum (DMF (dimethylformamide) solution) of the organic dye D-9. FIG. 2 is a 1 H-NMR spectrum (DMSO (dimethyl sulfoxide) -d 6 solution) of the organic dye D-9. Absorption maximum values of absorption spectrum of organic dye D-9: λmax = 541 nm, 463 nm, 397 nm (DMF solution).
(合成例2:有機色素D−14の合成)
化合物A、化合物C及び2−ブロモエチルアミン・臭化水素酸塩を用いて、合成スキームにしたがって、本発明の有機色素D−14を合成した。図3は、有機色素D−14の吸収スペクトル(DMF溶液)であり、図4は、有機色素D−14の1H−NMRスペクトル(DMSO−d6溶液)である。有機色素D−14の吸収スペクトルの吸収極大値:λmax=468nm(DMF溶液)。
(Synthesis Example 2: Synthesis of Organic Dye D-14)
Using Compound A, Compound C and 2-bromoethylamine / hydrobromide, the organic dye D-14 of the present invention was synthesized according to the synthesis scheme. 3 is an absorption spectrum (DMF solution) of the organic dye D-14, and FIG. 4 is a 1 H-NMR spectrum (DMSO-d 6 solution) of the organic dye D-14. Absorption maximum of absorption spectrum of organic dye D-14: λmax = 468 nm (DMF solution).
(合成例3:有機色素D−13の合成)
化合物D、化合物E及び2−ブロモエチルアミン・臭化水素酸塩を用いて、合成スキームにしたがって、本発明の有機色素D−13を合成した。図5は、有機色素D−13の吸収スペクトル(DMF溶液)である。図6は、有機色素D−13の1H−NMRスペクトル(DMSO−d6溶液)である。有機色素D−13の吸収スペクトルの吸収極大値:λmax=532nm、389nm(DMF溶液)。
(Synthesis Example 3: Synthesis of Organic Dye D-13)
Using Compound D, Compound E, and 2-bromoethylamine / hydrobromide, the organic dye D-13 of the present invention was synthesized according to the synthesis scheme. FIG. 5 is an absorption spectrum (DMF solution) of the organic dye D-13. FIG. 6 is a 1 H-NMR spectrum (DMSO-d 6 solution) of the organic dye D-13. Absorption maximum value of absorption spectrum of organic dye D-13: λmax = 532 nm, 389 nm (DMF solution).
(合成例4:有機色素D−42の合成)
化合物F、化合物G及び2−ブロモエチルアミン・臭化水素酸塩を用いて、合成スキームにしたがって、本発明の有機色素D−42を合成した。図7は、有機色素D−42の吸収スペクトル(DMF溶液)である。図8は、有機色素D−42の1H−NMRスペクトル(DMSO−d6溶液)である。有機色素D−42の吸収スペクトルの吸収極大値:λmax=513nm、393nm(DMF溶液)。
(Synthesis Example 4: Synthesis of Organic Dye D-42)
Using Compound F, Compound G, and 2-bromoethylamine / hydrobromide, the organic dye D-42 of the present invention was synthesized according to the synthesis scheme. FIG. 7 is an absorption spectrum (DMF solution) of the organic dye D-42. FIG. 8 is a 1 H-NMR spectrum (DMSO-d 6 solution) of the organic dye D-42. Absorption maximum of absorption spectrum of organic dye D-42: λmax = 513 nm, 393 nm (DMF solution).
(評価)
有機色素20mgをTHF/クロロホルム=1g/1gの混合溶液に溶解した。バインダー樹脂としてポリエステル樹脂(商品名:エリーテル(登録商標)UE3300、ユニチカ製)の40質量%トルエン/MEK(メチルエチルケトン)溶液を0.3g加えて撹拌して均一な溶液とした。この溶液を透明PET(ポリエチレンテレフタレート)フィルム上にワイヤーバーでコートし、ドライヤーで加熱乾燥して膜厚20ミクロンの有機色素膜を形成した。この有機色素膜を晴天下の日光に3時間暴露した後、日光に未暴露の有機色素膜と目視で比較し、有機色素の耐光性を下記判定基準で評価した。結果を表1に示す。なお、有機色素D−1〜D−42は、実施例となる本発明の有機色素であり、有機色素E−1〜E−3は、比較例となる本発明外の有機色素である。
(Evaluation)
20 mg of organic dye was dissolved in a mixed solution of THF / chloroform = 1 g / 1 g. As a binder resin, 0.3 g of a 40% by mass toluene / MEK (methyl ethyl ketone) solution of a polyester resin (trade name: Elitel (registered trademark) UE3300, manufactured by Unitika) was added and stirred to obtain a uniform solution. This solution was coated on a transparent PET (polyethylene terephthalate) film with a wire bar and heated and dried with a dryer to form an organic dye film having a thickness of 20 microns. The organic dye film was exposed to sunlight under fine weather for 3 hours and then visually compared with an organic dye film not exposed to sunlight, and the light resistance of the organic dye was evaluated according to the following criteria. The results are shown in Table 1. The organic dyes D-1 to D-42 are organic dyes of the present invention as examples, and the organic dyes E-1 to E-3 are organic dyes other than the present invention as comparative examples.
判定基準
○:有機色素の退色なし。
△:有機色素の退色あり。
Judgment criteria ○: No organic dye fading.
Δ: Organic dye fading
表1から明らかなように、本発明の有機色素は、比較例の有機色素に比べて耐光性に優れていることがわかる。 As is clear from Table 1, it can be seen that the organic dye of the present invention is superior in light resistance to the organic dye of the comparative example.
本発明の有機色素は、銀塩写真感光材料、感熱記録材料、光学用フィルター、CD−RやDVD−R等の光学記録媒体、光感光性樹脂用の増感剤、医療用蛍光性センサー、衣料用染色剤、太陽電池、光センサー、表示用インク等の用途において利用することができる。 The organic dye of the present invention is a silver salt photographic light-sensitive material, a heat-sensitive recording material, an optical filter, an optical recording medium such as CD-R or DVD-R, a sensitizer for a photosensitive resin, a medical fluorescent sensor, It can be used in applications such as clothing stains, solar cells, photosensors, and display inks.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013213265A JP6239338B2 (en) | 2013-10-11 | 2013-10-11 | Organic dye |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013213265A JP6239338B2 (en) | 2013-10-11 | 2013-10-11 | Organic dye |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2015074754A true JP2015074754A (en) | 2015-04-20 |
JP6239338B2 JP6239338B2 (en) | 2017-11-29 |
Family
ID=52999871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013213265A Active JP6239338B2 (en) | 2013-10-11 | 2013-10-11 | Organic dye |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6239338B2 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007066690A (en) * | 2005-08-31 | 2007-03-15 | Mitsubishi Paper Mills Ltd | Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using it |
JP2008016383A (en) * | 2006-07-07 | 2008-01-24 | Mitsubishi Paper Mills Ltd | Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using it |
WO2010134607A1 (en) * | 2009-05-22 | 2010-11-25 | パナソニック電工株式会社 | Light-absorbing material and photoelectric conversion element |
-
2013
- 2013-10-11 JP JP2013213265A patent/JP6239338B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007066690A (en) * | 2005-08-31 | 2007-03-15 | Mitsubishi Paper Mills Ltd | Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using it |
JP2008016383A (en) * | 2006-07-07 | 2008-01-24 | Mitsubishi Paper Mills Ltd | Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using it |
WO2010134607A1 (en) * | 2009-05-22 | 2010-11-25 | パナソニック電工株式会社 | Light-absorbing material and photoelectric conversion element |
Also Published As
Publication number | Publication date |
---|---|
JP6239338B2 (en) | 2017-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101836274B (en) | A dye including an anchoring group in its molecular structure | |
JP2010111750A (en) | Light-absorbing composition | |
CN101437902B (en) | Methylene dye and use thereof | |
JP2009263614A (en) | Infrared absorptive compound and fine particles comprising the compound | |
JP6139681B2 (en) | Diketopyrrolopyrrole (DPP) -based sensitizers for electrochemical or optoelectronic devices | |
JP2010204132A5 (en) | ||
WO2018186489A1 (en) | Phthalocyanine compound and use of same | |
KR20120087485A (en) | Novel organic dye and preparation thereof | |
JP2012514063A (en) | Copper phthalocyanine compound and near infrared absorption filter using the same | |
CN103764768B (en) | Pigment and its manufacture method, photo-electric conversion element and photoelectrochemical cell and terpyridyl compounds and its manufacture method | |
JP5898725B2 (en) | Photosensitizer and photoelectric conversion element | |
US4122261A (en) | Polycyclic iminoisoindoline chelates | |
CN103620864B (en) | Photo-electric conversion element, photoelectrochemical cell and these pigments used | |
JPWO2020071470A1 (en) | Phthalocyanine compounds and their uses | |
JP4274403B2 (en) | Fluorescent dye material | |
JP2008520782A5 (en) | ||
JP6239338B2 (en) | Organic dye | |
JP2010018688A (en) | Light absorbing composition | |
TW200821285A (en) | Bridged cyanine compounds and optical recording materials containing the same | |
JP5941844B2 (en) | Near-infrared absorbing cyanine dyes and their applications | |
KR101677574B1 (en) | Phthalocyanine compound and near infrared ray absorption filter using the same | |
JP4466940B2 (en) | Red fluorescent material and composition containing the same | |
Jaung et al. | Dicyanopyrazine studies. Syntheses and characterization of new bis-styryl fluorescent dyes from DAMN. Part III | |
JP7470357B2 (en) | Pyrene fluorescent dye | |
WO2015037676A1 (en) | Methine dye and dye-sensitized photoelectric conversion element |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160831 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170427 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170502 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170613 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170711 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170814 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171010 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171101 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6239338 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |