JPS6364471B2 - - Google Patents

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Publication number
JPS6364471B2
JPS6364471B2 JP16939180A JP16939180A JPS6364471B2 JP S6364471 B2 JPS6364471 B2 JP S6364471B2 JP 16939180 A JP16939180 A JP 16939180A JP 16939180 A JP16939180 A JP 16939180A JP S6364471 B2 JPS6364471 B2 JP S6364471B2
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JP
Japan
Prior art keywords
photoreceptor
disazo
present
disazo compound
charge
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
Application number
JP16939180A
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Japanese (ja)
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JPS5792052A (en
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed filed Critical
Priority to JP16939180A priority Critical patent/JPS5792052A/en
Priority to US06/256,162 priority patent/US4618672A/en
Priority to DE3117076A priority patent/DE3117076C2/en
Priority to GB8113374A priority patent/GB2076007B/en
Publication of JPS5792052A publication Critical patent/JPS5792052A/en
Publication of JPS6364471B2 publication Critical patent/JPS6364471B2/ja
Granted legal-status Critical Current

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Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は新規なジスアゾ化合物に関する。 従来からジスアゾ化合物は、電子写真方式にお
いて使用される感光体の一つの形態である積層型
感光体の、電荷発生層に用いられる電荷発生顔料
として有効であることが知られている。ここでい
う積層型感光体とは、導電性支持体上に、光によ
つて電荷担体を生成する能力を有する電荷発生顔
料を適切な方法、例えば真空蒸着、顔料溶液の塗
布あるいは樹脂溶液に、顔料の微細粒子を分散し
た分散液の塗布などにより薄層として電荷発生層
を形成せしめ、その上に電荷発生層で生成した電
荷担体を効率よく注入することが可能で、しかも
その移動を行うところの電荷移動層(通常この電
荷移動層は、電荷移動物質と結着樹脂とからな
る。)を形成せしめた感光体である。従来、この
種の感光体に使用されるジスアゾ化合物として、
例えば特開昭47−37543号公報、あるいは特開昭
52−55643号公報、などに開示されているベンジ
ジン系ジスアゾ顔料あるいは、特開昭54−22834
号公報に開示されているフルオレノン系ジスアゾ
顔料などが公知である。しかしながら、従来のジ
スアゾ顔料を用いた積層型の感光体は感度が比較
的低く、高速複写機の感光体としては適切でない
などの欠点を有している。 本発明の目的は、先に述べた積層型の感光体に
おいて有効な新規なジスアゾ化合物を提供するこ
とにあり、本発明のジスアゾ化合物を用いた積層
型感光体は感度が高く、高速複写機用の感光体と
して適している。 すなわち、本発明の新規なジスアゾ化合物は、
式() で表わされるジスアゾ化合物である。この新規な
ジスアゾ化合物は、常温において紫黒色の結晶体
である。第1図には()の赤外線吸収スペクト
ル(KBr錠剤法)を、第2図には熱分析図(TG
−DSC)を、また第3図にはX線回析図を示し
た。 上記の本発明のジスアゾ化合物は、下記のよう
な手段によつて製造することが出来る。すなわ
ち、本発明の新規なジスアゾ化合物は式()で
表わされる2,7−ジアミノ−9−フルオレノン をジアゾ化して、一般式()で表わされるテト
ラゾニウム塩とし、 (但し、Xはアニオン官能基を表わす。) これと式()で表わされる2−ヒドロキシ−3
−(2−フルオロフエニルカルバモイル)ナフタ
レン とを反応されることによつて製造することができ
る。 この製造方法においては、2,7−ジアミノ−
9−フルオレノンのジアゾ化は、これを希塩酸あ
るいは希硫酸のような希薄無機酸中で亜硝酸ナト
リウム水溶液を−10℃ないし、10℃にて添加する
ことにより行なわれる。このジアゾ化反応は、お
よそ30分間から3時間で完結する。さらに反応混
合物に、例えばホウフツ化水素酸あるいはホウフ
ツ化ナトリウム水溶液などを加えてテトラゾニウ
ム塩として沈殿させ、結晶を取してから次の反
応に用いることが望ましい。次いで、このテトラ
ゾニウム塩に式の2−ヒドロキシ−3−(2−
フルオロフエニルカルバモイル)ナフタレンを作
用して、カツプリング反応を起させることにより
行われる。実際にはこの反応は、N,N−ジメチ
ルホルムアミド(DMF)やジメチルスルホキシ
ドなどの有機溶媒にテトラゾニウム塩およびカツ
プラーを混合溶解しておき、これに−10℃ないし
40℃にて酢酸ナトリウム水溶液などのアルカリ水
溶液を滴下することにより行なわれる。この反応
はおよそ5分間ないし3時間で完結する。反応終
了後、析出している結晶を取し、適切な方法に
より精製(例えば水あるいは/および有機溶剤に
よる洗浄、再結晶法など)することにより上記ジ
スアゾ化合物の製造は完了する。 このようにして製造される本発明のジスアゾ化
合物の製造例を示せば次の通りである。 製造例 2,7−ジアミノ−9−フルオレノン
〔Schmidt,Retzlaff,Haid;Ann.390 225
(1912)〕63.07gと6規定塩酸1.2の混合物に、
亜硫酸ナトリウム44.81gを水180mlに溶解した溶
液を0℃にて約1時間で滴下した。滴下終了後、
同温度で更に30分間撹拌したのち少量の未反応物
を別し、液に42%ホウフツ化水素酸400mlを
加えた。析出して来た結晶を取し、冷水で洗浄
後乾燥して黄橙色の結晶として、9−フルオレノ
ン−2,7−ビスジアゾニウムビステトラフルオ
ロボレート108.2g(88.4%)を得た。 分解点 約155℃ 赤外線吸収スペクトル(KBr錠剤法) νN2 2300cm-1 νCO 1745cm-1 次に上記のようにして得たテトラゾニウム塩
2.04gおよび2−ヒドロキシ−3−(2−フルオ
ロフエニルカルバモイル)ナフタレン2.81gを
DMF300mlに溶解し、これに酢酸ナトリウム1.64
gを水14mlに溶解した溶液を室温にて約15分間で
滴下した。滴下終了後、同温度で更に2時間撹拌
したのち析出している結晶を取した。得られた
粗結晶ケーキをDMF300mlに分散し、80℃で2時
間撹拌したのち再び結晶を取し、更にこの操作
を2回くり返した。その後結晶を水洗して乾燥
し、本発明のジスアゾ化合物2.67g(67.3%)を
得た。 紫黒色結晶 分解点 300℃以上 元素分析値 実測値 計算値 C% 70.92 71.03 H% 3.80 3.55 N% 10.31 10.58 赤外線吸収スペクトル(KBr錠剤法) νCO(フルオレノン) 1720cm-1 νCO(第2アミド) 1675cm-1 本発明のジスアゾ化合物は前述のとおり積層型
感光体の電荷発生顔料として有効であり、その点
を明らかにするために以下に具体的な用途例を示
す。また本発明の進歩性を明らかにするために従
来からのジスアゾ化合物との比較結果も示す。 用途例 (1) 本発明のジスアゾ化合物76重量部、ポリエステ
ル樹脂(バイロン200、東洋紡績株式会社製)の
テトラヒドロフラン溶液(固形分濃度2%)1260
重量部、およびテトラヒドロフラン3700重量部を
ボールミル中で粉砕混合し、得られた分散液をア
ルミニウム蒸着したポリエステルベース(導電性
支持体)のアルミ面上にドクターブレートを用い
て塗布し、自然乾燥して、厚さ約1μmの電荷発
生層を形成した。一方、9−エチルカルバゾール
−3−カルボキシアルデヒド1−メチル−1−フ
エニルヒドラゾン2重量部、ポリカーボネート樹
脂(パンライトK1300、帝人化成株式会社製)2
重量部およびテトラヒドロフラン16重量部混合溶
解して溶液としたのち、これを前記電荷発生層上
にドクターブレードで塗布し80℃で2分間次いで
100℃で5分間乾燥して厚さ約20μmの電荷移動
層を形成せしめ、第4図に示した積層型の感光体
(A)を作成した。 また、比較のために、上記の感光体作成手順に
従い、本発明のジスアゾ化合物のかわりに前述し
た特開昭47−37543号公報あるいは特開昭52−
55643に開示されているベンジジン系ジスアゾ顔
料である。4,4′−ビス(2−ヒドロキシ−3−
フエニルカルバモイル−1−ナフチルアゾ)−3,
3′−ジクロルジフエニル〔比較顔料(1)〕、特開昭
54−22834号公報に開示されているフルオレノン
系ジスアゾ顔料である2,7−ビス〔2−ヒドロ
キシ−3−(4−クロルフエニルカルバモイル)−
1−ナフチルアゾ〕−9−フルオレノン〔比較顔
料(2)〕および2,7−ビス〔2−ヒドロキシ−3
−(2−メチル−5−クロルフエニルカルバモイ
ル)−1−ナフチルアゾ〕−9−フルオレノン〔比
較顔料(3)〕を用いた以外は、全く同様に感光体を
作成し、それぞれ比較用感光体として感光体(B),
(C),(D)を得た。 次に上記のようにして作成した4種の感光体す
なわち、 1 本発明のジスアゾ化合物を用いた積層型感光
体 ……感光体(A) 2 比較顔料(1)を用いた積層型感光体
……感光体(B) 3 比較顔料(2)を用いた積層型感光体
……感光体(C) 4 比較顔料(3)を用いた積層型感光体
……感光体(D) について市販の静電複写紙試験装置(川口電機製
作所製SP−428型)を用いてその静電特性を測定
した。 すなわち、まず感光体に−6KVのコロナ放電
を20秒間行なつて負帯電させ、その時の表面電位
を測定してVdo(ボルト)を求めそのまま20秒間
暗所で暗減衰させて、その時の表面電位を測定し
てVpo(ボルト)とした。ついでタングステンラ
ンプから、その表面が照度20ルツクスになるよう
感光層に光照射を施し、その表面電位がVpoの1/
2になる迄の時間(秒)を求めて露光量E1/2(ル
ツクス・秒)とした。同様に、Vpoの1/5及び1/1
0になる迄の時間(秒)を求めて露光量E1/5(ル
ツクス・秒)及びE1/10(ルツクス・秒)を求め
た。 表1に、感光体(A)〜(D)の測定結果を示した。
The present invention relates to novel disazo compounds. It has been known that disazo compounds are effective as charge-generating pigments used in charge-generating layers of laminated photoreceptors, which are one type of photoreceptor used in electrophotography. The laminated photoreceptor referred to herein means that a charge-generating pigment having the ability to generate charge carriers by light is deposited on a conductive support by an appropriate method, such as vacuum deposition, coating with a pigment solution, or coating with a resin solution. It is possible to form a charge generation layer as a thin layer by coating a dispersion liquid containing fine pigment particles, and to efficiently inject the charge carriers generated in the charge generation layer onto the charge generation layer, and also to move the charge carriers. This is a photoreceptor on which a charge transfer layer (generally, this charge transfer layer consists of a charge transfer substance and a binder resin) is formed. Conventionally, disazo compounds used in this type of photoreceptor include:
For example, JP-A-47-37543, or JP-A-Sho.
Benzidine-based disazo pigments disclosed in Publication No. 52-55643, etc., or JP-A No. 54-22834
Fluorenone-based disazo pigments disclosed in Japanese Patent Publication No. 1, No. 1, and the like are known. However, conventional laminated photoreceptors using disazo pigments have relatively low sensitivity and are not suitable as photoreceptors for high-speed copying machines. An object of the present invention is to provide a new disazo compound that is effective in the above-mentioned laminated photoreceptor, and the laminated photoreceptor using the disazo compound of the present invention has high sensitivity and is suitable for high-speed copying machines. It is suitable as a photoreceptor. That is, the novel disazo compound of the present invention is
formula() It is a disazo compound represented by This novel disazo compound is a purple-black crystalline substance at room temperature. Figure 1 shows the infrared absorption spectrum (KBr tablet method) of (), and Figure 2 shows the thermal analysis diagram (TG
-DSC) and an X-ray diffraction diagram is shown in FIG. The disazo compound of the present invention described above can be produced by the following method. That is, the novel disazo compound of the present invention is 2,7-diamino-9-fluorenone represented by the formula (). is diazotized to obtain a tetrazonium salt represented by the general formula (), (However, X represents an anionic functional group.) This and 2-hydroxy-3 represented by the formula ()
-(2-fluorophenylcarbamoyl)naphthalene It can be produced by reacting with. In this production method, 2,7-diamino-
Diazotization of 9-fluorenone is carried out by adding an aqueous solution of sodium nitrite in a dilute inorganic acid such as dilute hydrochloric acid or dilute sulfuric acid at -10°C to 10°C. This diazotization reaction is completed in approximately 30 minutes to 3 hours. Furthermore, it is desirable to add, for example, hydroborofluoric acid or an aqueous sodium borofluoride solution to the reaction mixture to precipitate the tetrazonium salt, and then use it in the next reaction after crystallizing it. This tetrazonium salt is then converted to 2-hydroxy-3-(2-
This is accomplished by reacting with (fluorophenylcarbamoyl)naphthalene to cause a coupling reaction. In reality, this reaction is carried out by dissolving a tetrazonium salt and a coupler in an organic solvent such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide, and then heating the solution at -10°C or
This is carried out by dropping an aqueous alkaline solution such as an aqueous sodium acetate solution at 40°C. This reaction is complete in approximately 5 minutes to 3 hours. After completion of the reaction, the precipitated crystals are collected and purified by an appropriate method (for example, washing with water and/or an organic solvent, recrystallization method, etc.) to complete the production of the disazo compound. Examples of the production of the disazo compound of the present invention produced in this manner are as follows. Production example 2,7-diamino-9-fluorenone [Schmidt, Retzlaff, Haid; Ann. 390 225
(1912)] into a mixture of 63.07 g and 1.2 g of 6N hydrochloric acid,
A solution of 44.81 g of sodium sulfite dissolved in 180 ml of water was added dropwise at 0° C. over about 1 hour. After finishing dropping,
After stirring for an additional 30 minutes at the same temperature, a small amount of unreacted material was separated, and 400 ml of 42% hydroborofluoric acid was added to the liquid. The precipitated crystals were collected, washed with cold water, and dried to obtain 108.2 g (88.4%) of 9-fluorenone-2,7-bisdiazonium bistetrafluoroborate as yellow-orange crystals. Decomposition point: approximately 155℃ Infrared absorption spectrum (KBr tablet method) νN 2 2300cm -1 νCO 1745cm -1 Next, the tetrazonium salt obtained as above
2.04 g and 2.81 g of 2-hydroxy-3-(2-fluorophenylcarbamoyl)naphthalene.
Dissolve in 300ml of DMF and add 1.64ml of sodium acetate to this.
A solution prepared by dissolving g in 14 ml of water was added dropwise at room temperature over about 15 minutes. After the addition was completed, the mixture was further stirred at the same temperature for 2 hours, and then the precipitated crystals were collected. The resulting crude crystal cake was dispersed in 300 ml of DMF, stirred at 80°C for 2 hours, then crystals were collected again, and this operation was repeated twice. Thereafter, the crystals were washed with water and dried to obtain 2.67 g (67.3%) of the disazo compound of the present invention. Purple-black crystal decomposition point 300℃ or higher Elemental analysis value Actual value Calculated value C% 70.92 71.03 H% 3.80 3.55 N% 10.31 10.58 Infrared absorption spectrum (KBr tablet method) νCO (fluorenone) 1720cm -1 νCO (secondary amide) 1675cm - 1 As mentioned above, the disazo compound of the present invention is effective as a charge-generating pigment for a laminated photoreceptor, and in order to clarify this point, specific application examples are shown below. Furthermore, in order to clarify the inventive step of the present invention, comparison results with conventional disazo compounds are also shown. Application examples (1) 76 parts by weight of the disazo compound of the present invention and a tetrahydrofuran solution (solid content concentration 2%) of polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) 1260
parts by weight and 3,700 parts by weight of tetrahydrofuran were pulverized and mixed in a ball mill, and the resulting dispersion was applied onto the aluminum surface of an aluminum-deposited polyester base (conductive support) using a doctor blade, and air-dried. , a charge generation layer having a thickness of about 1 μm was formed. On the other hand, 2 parts by weight of 9-ethylcarbazole-3-carboxaldehyde 1-methyl-1-phenylhydrazone, 2 parts by weight of polycarbonate resin (Panlite K1300, manufactured by Teijin Kasei Ltd.)
After mixing and dissolving 16 parts by weight of Tetrahydrofuran and 16 parts by weight to form a solution, this was applied onto the charge generation layer using a doctor blade and then heated at 80°C for 2 minutes.
The layered photoreceptor shown in Figure 4 was dried at 100°C for 5 minutes to form a charge transfer layer with a thickness of about 20 μm.
(A) was created. For comparison, the above-mentioned JP-A No. 47-37543 or JP-A No. 52-Sho.
55643 is a benzidine-based disazo pigment. 4,4'-bis(2-hydroxy-3-
Phenylcarbamoyl-1-naphthylazo)-3,
3'-Dichlorodiphenyl [Comparative pigment (1)], JP-A-Sho
2,7-bis[2-hydroxy-3-(4-chlorophenylcarbamoyl)-, which is a fluorenone disazo pigment disclosed in Japanese Patent No. 54-22834
1-naphthylazo]-9-fluorenone [comparative pigment (2)] and 2,7-bis[2-hydroxy-3
Photoreceptors were prepared in exactly the same manner except that -(2-methyl-5-chlorophenylcarbamoyl)-1-naphthylazo]-9-fluorenone [comparative pigment (3)] was used, and each photoreceptor was used as a comparative photoreceptor. Photoreceptor (B),
Obtained (C) and (D). Next, four types of photoreceptors were prepared as described above, namely: 1. A laminated photoreceptor using the disazo compound of the present invention...Photoreceptor (A) 2. A laminated photoreceptor using the comparative pigment (1)
...Photoreceptor (B) 3 Laminated photoreceptor using comparative pigment (2)
...Photoreceptor (C) 4 Laminated photoreceptor using comparative pigment (3)
...The electrostatic properties of the photoreceptor (D) were measured using a commercially available electrostatic copying paper testing device (Model SP-428 manufactured by Kawaguchi Electric Seisakusho). That is, first, the photoreceptor is negatively charged by applying a -6KV corona discharge for 20 seconds, and the surface potential at that time is measured to find Vdo (volts). was measured and defined as Vpo (volts). Next, the photosensitive layer is irradiated with light from a tungsten lamp so that the surface has an illuminance of 20 lux, and the surface potential becomes 1/1 of Vpo.
The time (seconds) until the value becomes 2 was determined and defined as the exposure amount E1/2 (lux seconds). Similarly, 1/5 and 1/1 of Vpo
The time (seconds) until the value reached 0 was determined, and the exposure amount E1/5 (lux/second) and E1/10 (lux/second) were determined. Table 1 shows the measurement results for photoreceptors (A) to (D).

【表】 表1の結果より明らかなように、本発明にかか
わる感光体(A)は、比較感光体である感光体(B)およ
び(C)と比較すると、その感度は高く、また、その
暗減衰は(C)及び(D)の感光体と比較し、小さく、こ
のことから、本発明のジスアゾ化合物がきわめて
すぐれた化合物であることが理解されよう。 以上述べて来たように、本発明のジスアゾ化合
物は電子写真感光体用の素材料として、きわめて
有用な材料であり、また有機物であるがゆえの軽
量低コストなどの多くの利点を兼ね備えており、
本発明のジスアゾ化合物がきわめてすぐれた材料
であることが良く理解出来るであろう。
[Table] As is clear from the results in Table 1, the photoreceptor (A) according to the present invention has higher sensitivity than the comparative photoreceptors (B) and (C). The dark decay was smaller than that of the photoreceptors (C) and (D), and from this fact it can be understood that the disazo compound of the present invention is an extremely excellent compound. As mentioned above, the disazo compound of the present invention is an extremely useful material for electrophotographic photoreceptors, and because it is an organic material, it has many advantages such as being lightweight and low cost. ,
It will be clearly understood that the disazo compound of the present invention is an extremely excellent material.

【図面の簡単な説明】[Brief explanation of drawings]

第1図は本発明のジスアゾ化合物の赤外線吸収
スペクトル、第2図は熱分析図、第3図はX線回
析図を示す。第4図は、本発明のジスアゾ化合物
の用途例の感光体例である。 1…導電性支持体、2…ポリエステルベース、
3…アルミニウム蒸着膜、4…電荷発生層、5…
電荷移動層。
FIG. 1 shows an infrared absorption spectrum of the disazo compound of the present invention, FIG. 2 shows a thermal analysis diagram, and FIG. 3 shows an X-ray diffraction diagram. FIG. 4 is an example of a photoreceptor in which the disazo compound of the present invention is used. 1... Conductive support, 2... Polyester base,
3... Aluminum vapor deposited film, 4... Charge generation layer, 5...
Charge transfer layer.

Claims (1)

【特許請求の範囲】 1 式()で表わされるジスアゾ化合物。 [Claims] 1. A disazo compound represented by formula ().
JP16939180A 1980-04-30 1980-12-01 Novel disazo compound and its preparation Granted JPS5792052A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP16939180A JPS5792052A (en) 1980-12-01 1980-12-01 Novel disazo compound and its preparation
US06/256,162 US4618672A (en) 1980-04-30 1981-04-21 Bisazo compounds useful as charge generating pigments in electrophotography
DE3117076A DE3117076C2 (en) 1980-04-30 1981-04-29 New bisazo connections
GB8113374A GB2076007B (en) 1980-04-30 1981-04-30 Disazo compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP16939180A JPS5792052A (en) 1980-12-01 1980-12-01 Novel disazo compound and its preparation

Publications (2)

Publication Number Publication Date
JPS5792052A JPS5792052A (en) 1982-06-08
JPS6364471B2 true JPS6364471B2 (en) 1988-12-12

Family

ID=15885723

Family Applications (1)

Application Number Title Priority Date Filing Date
JP16939180A Granted JPS5792052A (en) 1980-04-30 1980-12-01 Novel disazo compound and its preparation

Country Status (1)

Country Link
JP (1) JPS5792052A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH027969U (en) * 1988-06-30 1990-01-18

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH027969U (en) * 1988-06-30 1990-01-18

Also Published As

Publication number Publication date
JPS5792052A (en) 1982-06-08

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