JPH0368906B2 - - Google Patents
Info
- Publication number
- JPH0368906B2 JPH0368906B2 JP59104777A JP10477784A JPH0368906B2 JP H0368906 B2 JPH0368906 B2 JP H0368906B2 JP 59104777 A JP59104777 A JP 59104777A JP 10477784 A JP10477784 A JP 10477784A JP H0368906 B2 JPH0368906 B2 JP H0368906B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- fluorine
- squarium
- general formula
- 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 8
- 230000036211 photosensitivity Effects 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- 108091008695 photoreceptors Proteins 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class 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 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
産業上の利用分野
本発明は電子写真用感光体の電荷初生物質とし
て可視域から近赤外の波長域にわたつてフラツト
な光感度を有する新規なスクエアリウム化合物及
びその製造方法に関する。
従来技術
従来、電子写真用感光体材料として数多くの物
質が知られている。中でも、長波長域に光感度を
示すものとしてSe／Te、Se／As、CdSe、フタ
ロシアニン化合物などがある。このうち、Se／
Teなどの無機化合物は可視域から近赤外域にわ
たつてフラツトな光感度を有する感光体を得るこ
とが難しく、また可撓性がないためベルト状に加
工することが困難であるなど多くの問題点があ
る。また、有機化合物のフタロシアニン化合物は
550nｍ以下での光感度が低いことと精製が困難
であることが問題であり、可視域から近赤外域に
わたつてフラツトな光感度を示す実用的な物質は
みつかつていない。
発明の目的
本発明の目的は可視域から近赤外の波長域の全
体にわたつてフラツトな光感度を有する新規なス
クエアリウム化合物を提供することにある。
発明の構成
本発明者等は鋭意検討の結果、前記の目的にか
なつた新規なスクエアリウム化合物及びその製造
方法を見出し、本発明を完成した。
すなわち、本発明の第１の対象は下記一般式
（）で示されるスクエアリウム化合物である。
上記の式中、X1は水素、フツ素又は臭素を表
わし、X2〜X5は水素、フツ素又は塩素を表わす。
本発明の第２の対象は式（）
で示される３，４−ジヒドロキシ−３−シクロブ
テン−１，２−ジオン（以下、スクエアリツクア
シツドと呼ぶ。）と一般式（）
一般式（）
（式中、X1〜X5は前記と同じ意味を表わす。）
で示されるアニリン誘導体とを反応させることを
特徴とする前記一般式（）で示される新規なス
クエアリウム化合物の製造方法である。
前記の新規スクエアリウム化合物は、スクエア
リン酸とアニリン誘導体を溶媒（例えば、ｎ−ブ
チルアルコールあるいはアミルアルコール）中
で、120〜140℃にて３時間から５時間反応させる
ことによつて得られる。得られた化合物は、洗浄
後さらに適当な溶媒で再結晶することによつて精
製される。
この様にして得られる本発明の新規なスクエア
リウム化合物の具体例を構造式で以下の表１に示
す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a novel squarium compound having flat photosensitivity over the visible to near-infrared wavelength range as a charge starter material for electrophotographic photoreceptors, and a method for producing the same. BACKGROUND OF THE INVENTION Conventionally, many substances have been known as electrophotographic photoreceptor materials. Among these, compounds that exhibit photosensitivity in the long wavelength range include Se/Te, Se/As, CdSe, and phthalocyanine compounds. Of these, Se/
Inorganic compounds such as Te have many problems such as it is difficult to obtain a photoreceptor with flat photosensitivity from the visible region to the near-infrared region, and it is difficult to process them into a belt shape due to their lack of flexibility. There is a point. In addition, phthalocyanine compounds, which are organic compounds,
Problems include low photosensitivity below 550 nm and difficulty in purification, and no practical substance has yet been found that exhibits flat photosensitivity from the visible region to the near-infrared region. OBJECTS OF THE INVENTION An object of the present invention is to provide a novel squarium compound having a flat photosensitivity over the entire visible to near-infrared wavelength range. Structure of the Invention As a result of extensive studies, the present inventors have discovered a novel squarium compound and a method for producing the same that meet the above objectives, and have completed the present invention. That is, the first object of the present invention is a squarium compound represented by the following general formula (). In the above formula, X 1 represents hydrogen, fluorine or bromine, and X 2 to X 5 represent hydrogen, fluorine or chlorine. The second object of the present invention is the expression () 3,4-dihydroxy-3-cyclobutene-1,2-dione (hereinafter referred to as square acid) represented by the general formula () and the general formula () (In the formula, X 1 to X 5 have the same meanings as above.) A method for producing a novel squarium compound represented by the general formula (), characterized by reacting it with an aniline derivative represented by the formula (). . The novel squarium compound described above can be obtained by reacting squaric acid and an aniline derivative in a solvent (for example, n-butyl alcohol or amyl alcohol) at 120 to 140°C for 3 to 5 hours. After washing, the obtained compound is further purified by recrystallization from a suitable solvent. Specific examples of the novel squarium compounds of the present invention obtained in this manner are shown in Table 1 below in terms of structural formulas.
【表】
この様にして製造される新規なスクエアリウム
化合物は積層型感光体の電荷発生物質として有効
である。
また、分光感度は400〜850nｍの範囲にわたつ
てフラツトな光感度を示し、全可視域及び近赤外
域において充分な光感度を有する。
発明の効果
従つて本発明のスクエアリウム化合物は通常の
電子写真様複写機のみならず、半導体レーザー用
プリンターとしての応用が可能で、インテリジエ
ントコピアとして広く用いることができる。また
電子写真分野以外にも、レーザーデイスクなどの
光学記録媒体として有機大陽電池などの様々な応
用が可能である。
次に本発明の実施例を説明する。
実施例 １
化合物(1)の製造
Ｎ−Ｐ−ブロモベンジル−Ｎ−メチル−アニリ
ン4.8ｇとスクエアリン酸１ｇをｎ−ブチルアル
コール60ml中に加え、撹拌しながら120〜130℃で
３時間加熱した。冷却後、析出した緑色の結晶を
過し、メタノールで洗浄後クロロホルムで再結
晶を行ない、目的物のスクエアリウム色素を1.4
ｇ（26％）得た。
分解点：269.5〜270.5℃。
赤外線吸収スペクトル（KBγ錠剤法）：νC=0＝
1610cm-1。
可視吸収スペクトル
λnax＝631nmm（ジクロロメタン溶液中）。
元素分析 実測値 理論値
Ｃ 61.03％ 61.97％
Ｈ 4.08％ 4.13％
Ｎ 4.51％ 4.45％
実施例 ２〜５
化合物(2)〜(5)の製造
アニリン誘導体を相当する化合物に代えて、実
施例１と同様にして化合物(2)〜(5)を得た。表２に
生成した各化合物の分解点、赤外吸収スペクトル
及び可視吸収スペクトルの値を示し、表３の元素
分析の結果を示した。[Table] The novel squarium compound produced in this manner is effective as a charge-generating material for laminated photoreceptors. Further, the spectral sensitivity shows flat photosensitivity over the range of 400 to 850 nm, and has sufficient photosensitivity in the entire visible region and near-infrared region. Effects of the Invention Therefore, the squarium compound of the present invention can be applied not only to ordinary electrophotographic copying machines but also to semiconductor laser printers, and can be widely used as intelligent copiers. In addition to the field of electrophotography, various applications such as organic solar cells and optical recording media such as laser disks are possible. Next, examples of the present invention will be described. Example 1 Production of compound (1) 4.8 g of N-P-bromobenzyl-N-methyl-aniline and 1 g of squaric acid were added to 60 ml of n-butyl alcohol, and heated at 120 to 130°C for 3 hours with stirring. . After cooling, the precipitated green crystals were filtered, washed with methanol, and recrystallized with chloroform to obtain 1.4% of the target squarium pigment.
g (26%) was obtained. Decomposition point: 269.5-270.5℃. Infrared absorption spectrum (KBγ tablet method): ν C=0 =
1610cm -1 . Visible absorption spectrum λ nax = 631 nm (in dichloromethane solution). Elemental analysis Actual value Theoretical value C 61.03% 61.97% H 4.08% 4.13% N 4.51% 4.45% Examples 2 to 5 Production of compounds (2) to (5) Example 1 was carried out by replacing the aniline derivative with the corresponding compound. Compounds (2) to (5) were obtained in the same manner. Table 2 shows the decomposition point, infrared absorption spectrum, and visible absorption spectrum values of each compound produced, and Table 3 shows the results of elemental analysis.
【表】
＊ 塩化メチレン溶液
[Table] * Methylene chloride solution
【表】【table】
Claims (1)
X2〜X5は水素、フツ素又は塩素を表わす。） で示されるスクエアリウム化合物。 ２ 式（） で示される３，４−ジヒドロキシ−３−シクロブ
テン−１，２−ジオンと一般式（） （式中、X1は水素、フツ素又は臭素を表わし、
X2〜X5は水素、フツ素又は塩素を表わす。） で示されるアニリン誘導体とを反応させることを
特徴とする一般式（） （式中X1〜X5は前記と同じ意味を表わす。） で示されるスクエアリウム化合物の製造方法。[Claims] 1 General formula () (In the formula, X 1 represents hydrogen, fluorine or bromine,
X2 to X5 represent hydrogen, fluorine or chlorine. ) is a squarium compound. 2 formula () 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the general formula () (In the formula, X 1 represents hydrogen, fluorine or bromine,
X2 to X5 represent hydrogen, fluorine or chlorine. ) General formula () characterized by reacting with an aniline derivative represented by (In the formula, X 1 to X 5 have the same meanings as above.) A method for producing a squarium compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59104777A JPS60248653A (en) | 1984-05-25 | 1984-05-25 | Novel squarium compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59104777A JPS60248653A (en) | 1984-05-25 | 1984-05-25 | Novel squarium compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60248653A JPS60248653A (en) | 1985-12-09 |
| JPH0368906B2 true JPH0368906B2 (en) | 1991-10-30 |
Family
ID=14389905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59104777A Granted JPS60248653A (en) | 1984-05-25 | 1984-05-25 | Novel squarium compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60248653A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62267750A (en) * | 1986-05-16 | 1987-11-20 | Fuji Xerox Co Ltd | Electrophotographic sensitive body |
| JPS62267752A (en) * | 1986-05-16 | 1987-11-20 | Fuji Xerox Co Ltd | Electrophotographic sensitive body |
-
1984
- 1984-05-25 JP JP59104777A patent/JPS60248653A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60248653A (en) | 1985-12-09 |
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