JPH0475262B2 - - Google Patents
Info
- Publication number
- JPH0475262B2 JPH0475262B2 JP58236201A JP23620183A JPH0475262B2 JP H0475262 B2 JPH0475262 B2 JP H0475262B2 JP 58236201 A JP58236201 A JP 58236201A JP 23620183 A JP23620183 A JP 23620183A JP H0475262 B2 JPH0475262 B2 JP H0475262B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- squarium
- compound
- photosensitivity
- represented
- 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 10
- 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 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 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 7
- 230000036211 photosensitivity Effects 0.000 description 7
- 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 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- -1 Se/Te Chemical class 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
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PPHQUIPUBYPZLD-UHFFFAOYSA-N n-ethyl-n-methylaniline Chemical compound CCN(C)C1=CC=CC=C1 PPHQUIPUBYPZLD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 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 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 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
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Light Receiving Elements (AREA)
- Photoreceptors In Electrophotography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は電子写真感光体の電荷発生物質とし
て、可視域から近赤外の波長域にわたつて光感度
を有する新規なスクエアリウム化合物の製造方法
に関する。
従来、電子写真用感光体用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な
どの無機化合物がある。これら無機化合物の多く
は毒物、劇物あるいは特定化学物質に指定され、
その取扱い、特に廃棄には注意を要するとともに
製造が難かしく、製造コストが高いという欠点が
ある。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ことなど多くの問題点があ
る。
一方、有機化合物としてはフタロシアニン化合
物が毒性がなく安価であるが、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。
本発明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
リウム化合物の製造方法を提供したものである。
すなわち本発明は、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）と式（）
（式中、Ｒはエチル基、ｎ−プロピル基または
ｎ−ブチル基を表わす。）
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、Ｒは前記と同じ意味を表わす。）
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
ツクアシツドとアニリン誘導体を、溶媒（例えば
ｎ−ブタノールあるいはアミルアルコール）中で
120〜140℃で、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り、精製さ
れる。
この様にして得られる本発明の新規スクエアリ
ウム化合物の具体例を構造式で次に示す。
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400〜850mmの範囲にわたつ
て、フラツトな光感度を示し、全可視域および近
赤外域において充分な光感度を有する。
従つて通常の電子写真複写機のみならず、半導
体レーザープリンターとしての応用が可能で、イ
ンテリジエント複写機として広く用いられる。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も有機太陽電池など様々な
応用が可能である。
次に実施例により本発明を説明する。
実施例１ 化合物（）の製造
Ｎ−エチル−Ｎ−メチルアニリン2.37ｇと３，
４−ジヒドロキシ−３−シクロブテン−１，２−
ジオン１ｇをｎ−ブタノール70mlとベンゼン10ml
の混合溶液中に加え、攪拌しながら、120〜130℃
で４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、乾燥することに
よつて目的のスクエアリウム色素が1.2ｇ（39.1
％）得られた。
分解点：219℃。
赤外線吸収スペクトル（KBr錠剤法）；
ｃ＝ｏ＝1580cm-1 0
元素分析： 実測値 計算値
Ｃ 75.86％ 75.83％
Ｈ 7.00％ 6.94％
Ｎ 8.21％ 8.04％
可視吸収スペクトル：
λmax＝634nm（ジクロロメタン溶液中）。
実施例 ２−３
アニリンの誘導体をかえて、実施例１と同様に
して３，４−ジヒドロキシ−３−シクロブテン
１，２−ジオンとアニリン誘導体を反応させた。
The present invention relates to a method for producing a novel squarium compound, which has photosensitivity over a wavelength range from the visible region to the near-infrared region, as a charge generating material for electrophotographic photoreceptors. Conventionally, many substances have been known as materials for electrophotographic photoreceptors. Among them, there are inorganic compounds such as Se/Te, Se/As, and CdSe that exhibit photosensitivity in the long wavelength range. Many of these inorganic compounds are designated as poisonous, deleterious substances, or specified chemical substances.
It has disadvantages in that it requires careful handling, especially disposal, and is difficult to manufacture and expensive. Furthermore, there are many problems such as the fact that it is difficult to process it into a belt shape due to its lack of flexibility. On the other hand, among organic compounds, phthalocyanine compounds are non-toxic and inexpensive, but they suffer from low photosensitivity at wavelengths below 550 nm and difficulty in purification. No practical substance that exhibits photosensitivity has yet been found. The present invention provides a novel method for producing a squarium compound having a flat photosensitivity over the entire wavelength range from the visible region to the near-infrared region. That is, the present invention is based on the formula () 3,4-dihydroxy-3-cyclobutene-1,2-dione (hereinafter referred to as square acid) represented by the formula () (In the formula, R represents an ethyl group, n-propyl group or n-butyl group.) General formula () characterized by reacting with an aniline derivative represented by (In the formula, R represents the same meaning as above.) This is a method for producing a novel squarium compound represented by the following formula. The novel squarium compound is prepared by combining squarium acid and an aniline derivative in a solvent (e.g. n-butanol or amyl alcohol).
It is obtained by reacting at 120 to 140°C for 3 to 5 hours. After washing, the obtained compound is further purified by recrystallization from an appropriate solvent. A specific example of the novel squarium compound of the present invention obtained in this manner is shown below in terms of its structural formula. The novel squarium compound produced in this manner is effective as a charge-generating material for laminated photoreceptors. Moreover, the spectral sensitivity shows flat photosensitivity over the range of 400 to 850 mm, and has sufficient photosensitivity in the entire visible region and near-infrared region. Therefore, it can be applied not only as a normal electrophotographic copying machine but also as a semiconductor laser printer, and is widely used as an intelligent copying machine. In addition to the field of electrophotography, various applications are possible, such as optical recording media such as laser disks and organic solar cells. Next, the present invention will be explained with reference to examples. Example 1 Production of compound () 2.37 g of N-ethyl-N-methylaniline and 3,
4-dihydroxy-3-cyclobutene-1,2-
1g of dione, 70ml of n-butanol and 10ml of benzene
Add to the mixed solution of and heat to 120-130℃ while stirring.
It was heated for 4 hours. After cooling, the precipitated green crystals were filtered, washed with methanol, and dried to obtain 1.2 g (39.1 g) of the desired squarium pigment.
%) obtained. Decomposition point: 219℃. Infrared absorption spectrum (KBr tablet method); c = o = 1580 cm -1 0 Elemental analysis: Actual value Calculated value C 75.86% 75.83% H 7.00% 6.94% N 8.21% 8.04% Visible absorption spectrum: λmax = 634 nm (in dichloromethane solution) ). Example 2-3 3,4-dihydroxy-3-cyclobutene 1,2-dione and the aniline derivative were reacted in the same manner as in Example 1, except that the aniline derivative was changed.
【表】
＊ジクロルメタン溶液中
[Table] *In dichloromethane solution
【表】
表１に生成した各化合物の分解点、赤外吸収ス
ペクトル、および可視吸収スペクトルの数値を示
し、表２に元素分析の結果を示した。[Table] Table 1 shows the decomposition point, infrared absorption spectrum, and visible absorption spectrum of each compound produced, and Table 2 shows the results of elemental analysis.
Claims (1)
テン−１，２−ジオンと一般式（） （式中、Ｒはエチル基、ｎ−プロピル基または
ｎ−ブチル基を表わす。） 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（１） （式中、Ｒ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 1 Formula () 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the general formula () (In the formula, R represents an ethyl group, n-propyl group or n-butyl group.) General formula (1) characterized by reacting with an aniline derivative represented by (In the formula, R represents the same meaning as above.) A method for producing a squarium compound represented by the following.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236201A JPS60130557A (en) | 1983-12-16 | 1983-12-16 | Novel squarium compound and its preparation |
| US06/682,211 US4700001A (en) | 1983-12-16 | 1984-12-17 | Novel squarylium compound and photoreceptor containing same |
| US06/946,641 US4707427A (en) | 1983-12-16 | 1986-12-29 | Squarylium compound in an electrophotographic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236201A JPS60130557A (en) | 1983-12-16 | 1983-12-16 | Novel squarium compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60130557A JPS60130557A (en) | 1985-07-12 |
| JPH0475262B2 true JPH0475262B2 (en) | 1992-11-30 |
Family
ID=16997276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58236201A Granted JPS60130557A (en) | 1983-12-16 | 1983-12-16 | Novel squarium compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60130557A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61103155A (en) * | 1984-10-26 | 1986-05-21 | Fuji Xerox Co Ltd | Electrophotographic sensitive body |
| JPS62267754A (en) * | 1986-05-16 | 1987-11-20 | Fuji Xerox Co Ltd | Electrophotographic sensitive material and its production |
| JPS63113465A (en) * | 1986-10-30 | 1988-05-18 | Fuji Xerox Co Ltd | Electrophotographic sensitive body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5236760A (en) * | 1975-09-17 | 1977-03-22 | Matsushita Electric Ind Co Ltd | Deteriorated flux identifying piece |
| JPS5255643A (en) * | 1975-09-15 | 1977-05-07 | Ibm | Method of producing electrophotographic image forming element |
| JPS5553335A (en) * | 1978-10-16 | 1980-04-18 | Hitachi Ltd | Composite type electrophotographic plate |
| JPS6045253A (en) * | 1983-04-11 | 1985-03-11 | リコ− システムズ インコ−ポレ−テツド | Photosensitive electrophotographic plate containing squaric acid methine dye dispersing in binder |
-
1983
- 1983-12-16 JP JP58236201A patent/JPS60130557A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5255643A (en) * | 1975-09-15 | 1977-05-07 | Ibm | Method of producing electrophotographic image forming element |
| JPS5236760A (en) * | 1975-09-17 | 1977-03-22 | Matsushita Electric Ind Co Ltd | Deteriorated flux identifying piece |
| JPS5553335A (en) * | 1978-10-16 | 1980-04-18 | Hitachi Ltd | Composite type electrophotographic plate |
| JPS6045253A (en) * | 1983-04-11 | 1985-03-11 | リコ− システムズ インコ−ポレ−テツド | Photosensitive electrophotographic plate containing squaric acid methine dye dispersing in binder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60130557A (en) | 1985-07-12 |
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