JPH07107030B2 - Novel squarylium compound and method for producing the same - Google Patents
Novel squarylium compound and method for producing the sameInfo
- Publication number
- JPH07107030B2 JPH07107030B2 JP62305860A JP30586087A JPH07107030B2 JP H07107030 B2 JPH07107030 B2 JP H07107030B2 JP 62305860 A JP62305860 A JP 62305860A JP 30586087 A JP30586087 A JP 30586087A JP H07107030 B2 JPH07107030 B2 JP H07107030B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- represented
- following general
- squarylium compound
- 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.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
- G03G5/0611—Squaric acid
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、新規なスクアリリウム化合物及びその製造方
法に関する。TECHNICAL FIELD The present invention relates to a novel squarylium compound and a method for producing the same.
従来の技術 従来、電子写真感光体に使用する感光材料については種
々のものが知られているが、近年有機系感光材料を用い
た電子写真感光体が注目され、種々検討されている。有
機系の光導電材料としては、ビスアゾ系顔料、トリスア
ゾ系顔料、フタロシアニン系顔料、シアニン類、ピリリ
ウム類等が知られており、又、近年ある種のスクアリリ
ウム化合物が優れた光導電特性を示し、電子写真感光材
料として使用できることが報告されている（例えば特開
昭60−136542号公報、同60−142946号公報、同60−1429
47号公報、同61−10540号公報、同62−450号公報参
照）。2. Description of the Related Art Conventionally, various photosensitive materials used for electrophotographic photosensitive members have been known, but in recent years, electrophotographic photosensitive members using an organic photosensitive material have attracted attention and various studies have been made. As the organic photoconductive material, bisazo-based pigments, trisazo-based pigments, phthalocyanine-based pigments, cyanines, pyryliums and the like are known, and in recent years, some squarylium compounds exhibit excellent photoconductive properties, It has been reported that it can be used as an electrophotographic light-sensitive material (for example, JP-A-60-136542, JP-A-60-142946, and JP-A-60-1429).
47, 61-10540, 62-450).
発明が解決しようとする問題点 従来提案されている種々の有機化合物は、電子写真感光
体において、電荷発生剤として利用できるが、更に他の
優れた電荷発生剤を提供することが望まれている。Problems to be Solved by the Invention Various conventionally proposed organic compounds can be used as charge generating agents in electrophotographic photoreceptors, but it is desired to provide further excellent charge generating agents. .
本発明者等は、一群のスクアリリウム化合物について検
討した結果、以下に示す新規なスクアリリウム化合物が
電荷発生剤として有用であることを見出だし、本発明を
完成するに至った。As a result of examining a group of squarylium compounds, the present inventors have found that the following novel squarylium compounds are useful as a charge generating agent, and have completed the present invention.
したがって、本発明の目的は、電子写真感光体の電荷発
生剤として有用な新規なスクアリリウム化合物及びその
製造方法を提供することにある。Therefore, an object of the present invention is to provide a novel squarylium compound useful as a charge generating agent for an electrophotographic photoreceptor and a method for producing the same.
問題点を解決するための手段 本発明の新規なスクアリリウム化合物は、下記一般式
（Ｉ）で示される。Means for Solving Problems The novel squarylium compound of the present invention is represented by the following general formula (I).
（式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わす） 上記一般式（Ｉ）で示されるスクアリリウム化合物は、
次のようにして製造される。 (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group.) The squarylium compound represented by the general formula (I) is
It is manufactured as follows.
まず、下記構造式（II） で示される3,4−ジクロロ−３−シクロブテン−1,2−ジ
オンと、下記一般式（III） （式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わす） で示されるアニリン誘導体とを反応させて、下記一般式
（IV） （式中、Ｘは前記と同じ意味を表わす） で示されるクロロシクロブテンジオン誘導体を合成し、
次いで該クロロシクロブテンジオン誘導体を加水分解し
て、下記一般式（Ｖ） （式中、Ｘは前記と同じ意味を表わす） で示されるヒロドキシシクロブテンジオン誘導体を合成
し、該ヒロドキシシクロブテンジオン誘導体を下記構造
式（VI） で示されるアニリン誘導体と反応させることによって製
造することができる。First, the following structural formula (II) 3,4-dichloro-3-cyclobutene-1,2-dione represented by the following general formula (III) (Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group), and then reacted with an aniline derivative represented by the following general formula (IV) (Wherein X represents the same meaning as described above), and a chlorocyclobutenedione derivative represented by the following formula is synthesized:
Then, the chlorocyclobutenedione derivative is hydrolyzed to give the following general formula (V): (Wherein, X represents the same meaning as described above), and a hydroxycyclobutenedione derivative represented by the following formula (VI) is prepared. It can be produced by reacting with an aniline derivative represented by
上記の製造法において、各工程の反応は、公知の類似の
反応に準じて実施することができる。In the above production method, the reaction in each step can be carried out according to a known similar reaction.
即ち、まず、3,4−ジクロロ−３−シクロブテン1,2−ジ
オンを前記一般式（III）で示されるアニリン誘導体と
反応させるが、アニリン誘導体としては、N,N−ジメチ
ルアニリン、３−メチル−N,N−ジメチルアニリン、３
−フルオロ−N,N−ジメチルアニリン及び３−ヒドロキ
シ−N,N−ジメチルアニリンを使用することができる。That is, first, 3,4-dichloro-3-cyclobutene 1,2-dione is reacted with the aniline derivative represented by the general formula (III), and the aniline derivative is N, N-dimethylaniline or 3-methylaniline. -N, N-dimethylaniline, 3
-Fluoro-N, N-dimethylaniline and 3-hydroxy-N, N-dimethylaniline can be used.
この反応は、それ等を、適当な溶剤、例えば塩化メチレ
ン、四塩化炭素、クロロホルム等のハロゲン化炭化水
素、ニトロベンゼン、エチルエーテル、アセトニトリル
等の通常のフリーデルクラフツ反応溶媒に溶解し、所望
ならば触媒、例えば三フッ化硼素エチルエーテル錯体、
塩化アルミニウム、塩化アンチモン、塩化鉄（II）又は
（III）、塩化チタン（IV）、塩化錫（IV）、塩化ビス
マス（IV）、塩化亜鉛（II）、塩化水銀等の存在下、０
〜40℃において撹拌することによって行なうことができ
る。This reaction is carried out by dissolving them in a suitable solvent, for example, a halogenated hydrocarbon such as methylene chloride, carbon tetrachloride and chloroform, a conventional Friedel-Crafts reaction solvent such as nitrobenzene, ethyl ether and acetonitrile, and if desired. A catalyst such as boron trifluoride ethyl ether complex,
0 in the presence of aluminum chloride, antimony chloride, iron (II) or (III) chloride, titanium (IV) chloride, tin (IV) chloride, bismuth (IV) chloride, zinc (II) chloride, mercury chloride, etc.
This can be done by stirring at -40 ° C.
合成されたクロロシクロブテンジオン誘導体は、続いて
加水分解されるが、加水分解は、適当な酸、例えば酢酸
を含む水中で、加熱することによって実施される。The synthesized chlorocyclobutenedione derivative is subsequently hydrolyzed, the hydrolysis being carried out by heating in water with a suitable acid, for example acetic acid.
続いて、加水分解によって得られたヒドロキシシクロブ
テンジオン誘導体を前記構造式（VI）で示されるアニリ
ン誘導体と反応させるが、その反応は、これ等の化合物
を適当な溶剤、例えば、ｎ−ブチルアルコール、ｎ−ヘ
プチルアルコール等の炭素数４〜８の脂肪族アルコー
ル、またはこれとベンゼン、トルエン等の芳香族炭化水
素との混合溶媒中で加熱することによって行なうことが
できる。Subsequently, the hydroxycyclobutenedione derivative obtained by hydrolysis is reacted with the aniline derivative represented by the above structural formula (VI) by the reaction of these compounds with a suitable solvent such as n-butyl alcohol. , N-heptyl alcohol and other aliphatic alcohols having 4 to 8 carbon atoms, or a mixed solvent thereof with an aromatic hydrocarbon such as benzene and toluene.
本発明のスクアリリウム化合物は、電子写真感光体の電
荷発生剤として有用である。例えば、感光層が電荷発生
層と電荷輸送層とに機能分離された積層構造を有する場
合において、上記スクアリリウム化合物を成膜性の樹脂
と共に用いて電荷発生層を形成することができる。The squarylium compound of the present invention is useful as a charge generating agent for an electrophotographic photoreceptor. For example, when the photosensitive layer has a laminated structure in which the charge generation layer and the charge transport layer are functionally separated, the squarylium compound can be used together with a film-forming resin to form the charge generation layer.
実施例 以下、本発明の実施例を示す。Examples Examples of the present invention will be shown below.
実施例１ 3,4−ジクロロ−３−シクロブテン−1,2−ジオン7.5g
（0.051モル）及び三フッ化硼素エチルエーテル錯体6.5
ml（0.05モル）を塩化メチレン30mlに溶解し、これに３
−フルオロ−ジメチルアニリン35g（0.25モル）を加え
て混合し、室温で16時間撹拌して反応を行なった。反応
終了後、反応混合物を希塩酸、次いで水で洗浄し、カラ
ムクロマトグラフィーを用いて分離精製を行ない、下記
構造式で示されるクロロシクロブテンジオン誘導体9.1g
（収率72％）を得た。Example 1 3,4-dichloro-3-cyclobutene-1,2-dione 7.5 g
(0.051 mol) and boron trifluoride ethyl ether complex 6.5
ml (0.05 mol) is dissolved in 30 ml of methylene chloride and added to
35 g (0.25 mol) of -fluoro-dimethylaniline was added and mixed, and the reaction was carried out by stirring at room temperature for 16 hours. After the reaction was completed, the reaction mixture was washed with dilute hydrochloric acid and then with water, and separated and purified by column chromatography to give 9.1 g of the chlorocyclobutenedione derivative represented by the following structural formula.
(Yield 72%) was obtained.
得られたクロロシクロブテンジオン誘導体7.60g（0.030
モル）に酢酸120ml及び水30mlを加え、２時間加熱還流
させた後、放冷し、析出する沈澱物を濾別し、下記構造
式で示されるヒドロキシシクロブテンジオン誘導体6.32
g（収率90％）を得た。 The obtained chlorocyclobutenedione derivative 7.60 g (0.030
Mol)) and 120 ml of acetic acid and 30 ml of water were added, and the mixture was heated under reflux for 2 hours, allowed to cool, and the precipitated precipitate was filtered off to give the hydroxycyclobutenedione derivative 6.32 represented by the following structural formula.
g (90% yield) was obtained.
得られたヒドロキシシクロブテンジオン誘導体2.01g
（8.55ミリモル）と３−ヒドロキシ−N,N−ジフェニル
アニリン2.53g（9.86ミリモル）をブタノール100mlとト
ルエン50mlの混合溶媒中で５時間加熱撹拌した後、カラ
ムクロマトグラフィーを用いて分離精製し、下記構造式
で示されるスクアリリウム化合物1.01g（収率25％）を
得た。融点m.p.＝235℃（分解）。 2.01 g of the obtained hydroxycyclobutenedione derivative
(8.55 mmol) and 3-hydroxy-N, N-diphenylaniline 2.53 g (9.86 mmol) were heated and stirred in a mixed solvent of 100 ml butanol and 50 ml toluene for 5 hours, and then separated and purified by column chromatography. 1.01 g (yield 25%) of the squarylium compound represented by the structural formula was obtained. Melting point mp = 235 ° C (decomposition).
この化合物の赤外吸収スペクトルは第１図に示す通りで
あり、紫外吸収スペクトル（最大）は、UV（CH2Cl2）:6
50nmであった。又、元素分析値は、C30H23FN2O3とし
て、次の通りであった。 The infrared absorption spectrum of this compound is as shown in FIG. 1, and the ultraviolet absorption spectrum (maximum) is UV (CH 2 Cl 2 ): 6.
It was 50 nm. Moreover, the elemental analysis values were as follows as C 30 H 23 FN 2 O 3 .
計算値（％） 実測値（％） Ｃ 75.30 75.11 Ｈ 4.84 5.08 Ｎ 5.85 5.68 実施例２〜４ 目的化合物に対応する適当な原料物質を選択し、実施例
１におけると同様な方法で処理して、第１表に示すヒド
ロキシシクロブテンジオン誘導体を、続いて第１表に示
す目的化合物を製造した。それらの化合物の赤外吸収ス
ペクトル（最大）を第１表に示す。Calculated value (%) Measured value (%) C 75.30 75.11 H 4.84 5.08 N 5.85 5.68 Examples 2 to 4 Appropriate starting materials corresponding to the target compound were selected and treated in the same manner as in Example 1, The hydroxycyclobutenedione derivatives shown in Table 1 were prepared, and subsequently the target compounds shown in Table 1 were prepared. The infrared absorption spectra (maximum) of these compounds are shown in Table 1.
発明の効果 本発明のスクアリリウム化合物は、新規な化合物であ
り、電子写真感光体における電荷発生剤として有用な物
質であって、可視領域から近赤外領域までの広い範囲に
わたって感度を有する電子写真感光体を得ることができ
る。特に、電荷発生層と電荷輸送層とに機能分離された
積層構造を有する電子写真感光体において電荷発生在中
に含有させると、良好な感度のものが得られる。 EFFECTS OF THE INVENTION The squarylium compound of the present invention is a novel compound, is a substance useful as a charge generating agent in an electrophotographic photosensitive member, and has sensitivity in a wide range from the visible region to the near infrared region. You can get the body. In particular, in an electrophotographic photosensitive member having a laminated structure in which a charge generating layer and a charge transporting layer are functionally separated, when contained in a charge generating layer, excellent sensitivity can be obtained.
第１図は実施例１におけるスクアリリウム化合物の赤外
吸収スペクトル図である。FIG. 1 is an infrared absorption spectrum diagram of the squarylium compound in Example 1.
Claims (2)
基を表わす） で示されるスクアリリウム化合物。1. The following general formula (I): (In the formula, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group).
オンと、下記一般式（III） （式中、Ｘは水素原子、メチル基、フッ素原子又は水酸
基を表わす） で示されるアニリン誘導体とを反応させて、下記一般式
（IV） （式中、Ｘは前記と同じ意味を表わす） で示されるクロロシクロブテンジオン誘導体を合成し、
次いで該クロロシクロブテンジオン誘導体を加水分解し
て、下記一般式（Ｖ） （式中、Ｘは前記と同じ意味を表わす） で示されるヒロドキシシクロブテンジオン誘導体を合成
し、該ヒロドキシシクロブテンジオン誘導体を下記構造
式（VI） で示されるアニリン誘導体と反応させることを特徴とす
る下記一般式（Ｉ） （式中、Ｘは前記と同じ意味を表わす） で示されるスクアリリウム化合物の製造方法。2. The following structural formula (II) 3,4-dichloro-3-cyclobutene-1,2-dione represented by the following general formula (III) (Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom or a hydroxyl group), and then reacted with an aniline derivative represented by the following general formula (IV) (Wherein X represents the same meaning as described above), and a chlorocyclobutenedione derivative represented by the following formula is synthesized:
Then, the chlorocyclobutenedione derivative is hydrolyzed to give the following general formula (V): (Wherein, X represents the same meaning as described above), and a hydroxycyclobutenedione derivative represented by the following formula (VI) is prepared. Represented by the following general formula (I) characterized by reacting with an aniline derivative (In the formula, X has the same meaning as described above.) A method for producing a squarylium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305860A JPH07107030B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62305860A JPH07107030B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01146846A JPH01146846A (en) | 1989-06-08 |
| JPH07107030B2 true JPH07107030B2 (en) | 1995-11-15 |
Family
ID=17950232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62305860A Expired - Fee Related JPH07107030B2 (en) | 1987-12-04 | 1987-12-04 | Novel squarylium compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07107030B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2871181B2 (en) * | 1991-07-09 | 1999-03-17 | ブラザー工業株式会社 | Photocurable composition |
| JP3141517B2 (en) | 1992-05-14 | 2001-03-05 | ブラザー工業株式会社 | Photocurable composition |
| DE69330060T2 (en) * | 1992-10-26 | 2001-11-15 | Dainippon Printing Co Ltd | Photoelectric sensor, information recording system and method for information recording |
| JP3362745B2 (en) * | 1993-07-28 | 2003-01-07 | ブラザー工業株式会社 | Photosensitive microcapsule type toner |
| US20100065112A1 (en) | 2008-09-15 | 2010-03-18 | Thompson Mark E | Organic Photosensitive Devices Comprising a Squaraine Containing Organoheterojunction and Methods of Making Same |
| EP2673321A2 (en) | 2011-02-09 | 2013-12-18 | Stephen R. Forrest | Organic photosensitive devices comprising aryl squaraines and methods of making the same |
| KR101969612B1 (en) | 2011-10-14 | 2019-04-16 | 제이에스알 가부시끼가이샤 | Optical filter, solid state image-capturing device using same, and camera module using same |
| WO2014002864A1 (en) | 2012-06-25 | 2014-01-03 | Jsr株式会社 | Solid-state image capture element optical filter and application thereof |
| JP6281975B2 (en) * | 2013-02-07 | 2018-02-21 | 国立大学法人山形大学 | Asymmetric squarylium derivative, donor material comprising the same, and organic thin film solar cell using the same |
| KR101661088B1 (en) | 2013-10-17 | 2016-09-28 | 제이에스알 가부시끼가이샤 | Optical filter, solid-state image pickup device, and camera module |
| JP6536589B2 (en) | 2014-12-04 | 2019-07-03 | Jsr株式会社 | Solid-state imaging device |
| TWI675907B (en) | 2015-01-21 | 2019-11-01 | 日商Ｊｓｒ股份有限公司 | Solid imaging device |
| WO2017018419A1 (en) | 2015-07-28 | 2017-02-02 | Jsr株式会社 | Optical filter and environment light sensor provided with optical filter |
| WO2017213047A1 (en) | 2016-06-08 | 2017-12-14 | Jsr株式会社 | Optical filter and optical sensor device |
| US11261374B2 (en) * | 2018-09-14 | 2022-03-01 | Konica Minolta, Inc. | Squarylium compound, light-emitting composition, and light-emitting film |
-
1987
- 1987-12-04 JP JP62305860A patent/JPH07107030B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01146846A (en) | 1989-06-08 |
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