JPH07287408A - Electrophotographic photoreceptor using novel diamino compound - Google Patents
Electrophotographic photoreceptor using novel diamino compoundInfo
- Publication number
- JPH07287408A JPH07287408A JP6081594A JP8159494A JPH07287408A JP H07287408 A JPH07287408 A JP H07287408A JP 6081594 A JP6081594 A JP 6081594A JP 8159494 A JP8159494 A JP 8159494A JP H07287408 A JPH07287408 A JP H07287408A
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- weight
- resin
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- Plural Heterocyclic Compounds (AREA)
- Indole Compounds (AREA)
- Photoreceptors In Electrophotography (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Furan Compounds (AREA)
- Pyrane Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規ジアミノ化合物を
感光材料、輸送材料として使用する電子写真感光体に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor using a novel diamino compound as a photosensitive material or a transport material.
【０００２】[0002]
【従来の技術】感光材料、電荷輸送材料として使用可能
な有機化合物は、従来より、アントラセン誘導体、アン
トラキノン誘導体、イミダゾール誘導体、カルバゾール
誘導体、スチリル誘導体等種々知られており、例えば、
特開昭６２−２８０８５０号公報には、下記一般式で表
されるようなジアミノ化合物を含有する感光体が開示さ
れている。2. Description of the Related Art Conventionally, various organic compounds usable as a light-sensitive material and a charge transport material are known such as anthracene derivative, anthraquinone derivative, imidazole derivative, carbazole derivative and styryl derivative.
JP-A-62-280850 discloses a photoreceptor containing a diamino compound represented by the following general formula.
【０００３】[0003]
【化２】 [Chemical 2]
【０００４】[式中、Ｒ1〜Ｒ4およびＸは上記公報中に
記載のものを表わす。] また、特開昭６２−２８３３４１号公報には下記一般式
で表わされるようなジアミノ化合物を含有する感光体が
開示されている。[In the formula, R 1 to R 4 and X represent those described in the above publication. Further, JP-A-62-283341 discloses a photoreceptor containing a diamino compound represented by the following general formula.
【０００５】[0005]
【化３】 [Chemical 3]
【０００６】[式中、Ｒ1〜Ｒ5は上記公報中に記載のも
のを表わす。][In the formula, R 1 to R 5 represent those described in the above publication. ]
【０００７】[0007]
【発明が解決しようとする課題】しかし、従来の感光体
では、感度、繰り返し安定性、耐久性等の電子写真特性
全般にわたって満足するものは殆どないのが現状であ
る。したがって、本発明の目的は、既に公知のいずれの
構造とも異なり、電荷輸送能、あるいは他の材料との適
合性、耐久性に優れた新規ジアミノ化合物を感光体の電
荷輸送材料として用いることにより、電子写真特性全般
に優れ、特に高感度の感光体を提供することを目的とす
る。However, under the present circumstances, most of the conventional photoconductors do not satisfy all the electrophotographic characteristics such as sensitivity, repetitive stability and durability. Therefore, the object of the present invention is different from any already known structure, by using a novel diamino compound excellent in charge transporting ability or compatibility with other materials, durability as a charge transporting material of a photoreceptor, It is an object of the present invention to provide a photoconductor having excellent electrophotographic properties and particularly high sensitivity.
【０００８】[0008]
【課題を解決するための手段】即ち本発明は、導電性支
持体上に下記一般式[Ｉ]で表わされるジアミノ化合物含
有する感光層を有することを特徴とする電子写真感光
体。That is, the present invention is an electrophotographic photoreceptor having a photosensitive layer containing a diamino compound represented by the following general formula [I] on a conductive support.
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】[式中、Ａr1およびＡr2は、アルキル基、
アラルキル基、アリール基または複素環式基を示す。Ｒ
1、Ｒ2、Ｒ3およびＲ4はそれぞれ水素原子、アルキル
基、アルコキシ基またはハロゲン原子を表す。Ｘは−Ｏ
−、−Ｓ−、−(Ｒ5)Ｃ(Ｒ6)−、−Ｎ(Ｒ7)−、−Ｎ＝
Ｎ−、−Ｃ2Ｈ4−または−ＣＨ＝ＣＨ−を表わす。但
し、Ｒ5、Ｒ6およびＲ7はそれぞれ水素原子、それぞれ
置換基を有してもよいアルキル基またはアリール基を表
わす。Ｙは−ＣＨ2−、−Ｃ2Ｈ4−または−ＣＨ＝ＣＨ
−を表わす。] 一般式[Ｉ]中、Ａr1およびＡr2は、それぞれ置換基を有
してもよいアルキル基、例えばメチル基、エチル基ある
いはプロピル基等；アラルキル基、例えばベンジル基あ
るいはフェネチル基等；アリール基、例えばフェニル基
等；または複素環式基、例えばチエニル基、フリル基、
ピロリル基あるいはピリジル基等を表わす。これらの基
は、アルキル基(メチル基、エチル基、プロピル基、ブ
チル基等)またはアルコキシ基(メトキシ基等)等の置換
基を有していてもよい。好ましいＡr1およびＡr2はフェ
ニル基、ナフチル基、特にフェニル基であり、樹脂相溶
性の点から、より立体障害の大きいアルキル基やアルコ
キシ基を有することが好ましい。Ｒ1、Ｒ2、Ｒ3および
Ｒ4は、それぞれ水素原子、アルキル基、例えばメチル
基、エチル基あるいはプロピル基等；アルコキシ基、例
えばメトキシ基、エトキシ基あるいはプロポキシ基等；
ハロゲン原子(フッ素原子、塩素原子、臭素原子等)を表
わす。樹脂との相溶性の点からはアルキル基が好まし
い。Ｘは、−Ｏ−、−Ｓ−、−(Ｒ5)Ｃ(Ｒ6)−、−Ｎ
(Ｒ7)−、−Ｎ＝Ｎ−、−Ｃ2Ｈ5−また−ＣＨ＝ＣＨ−
を表わし、式中のＲ5、Ｒ6およびＲ7は、それぞれ水素
原子、アルキル基例えばメチル基、エチル基あるいはプ
ロピル基等；アリール基、例えばフェニル基あるいはナ
フチル基等を表わす。[Wherein Ar 1 and Ar 2 are alkyl groups,
An aralkyl group, an aryl group or a heterocyclic group is shown. R
1 , R 2 , R 3 and R 4 each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. X is -O
-, - S -, - ( R 5) C (R 6) -, - N (R 7) -, - N =
N -, - C 2 H 4 - or represents a -CH = CH-. However, R 5 , R 6 and R 7 each represent a hydrogen atom or an alkyl group or aryl group which may have a substituent. Y is -CH 2 -, - C 2 H 4 - or -CH = CH
Represents-. In the general formula [I], Ar 1 and Ar 2 are each an alkyl group which may have a substituent, such as a methyl group, an ethyl group or a propyl group; an aralkyl group, such as a benzyl group or a phenethyl group; A group such as a phenyl group; or a heterocyclic group such as a thienyl group, a furyl group,
It represents a pyrrolyl group or a pyridyl group. These groups may have a substituent such as an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.) or an alkoxy group (methoxy group, etc.). Preferable Ar 1 and Ar 2 are a phenyl group and a naphthyl group, especially a phenyl group, and from the viewpoint of resin compatibility, it is preferable to have an alkyl group or an alkoxy group having a larger steric hindrance. R 1 , R 2 , R 3 and R 4 are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group;
Represents a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.). An alkyl group is preferred from the viewpoint of compatibility with the resin. X is, -O -, - S -, - (R 5) C (R 6) -, - N
(R 7) -, - N = N -, - C 2 H 5 - Further -CH = CH-
Wherein R 5 , R 6 and R 7 each represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group; an aryl group such as a phenyl group or a naphthyl group.
【００１１】本発明の一般式[Ｉ]で表されるジアミノ化
合物は、例えば下記の方法により合成することができ
る。例えば、下記一般式[II]:The diamino compound represented by the general formula [I] of the present invention can be synthesized, for example, by the following method. For example, the following general formula [II]:
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】[式中、Ｘ及びＹは一般式[Ｉ]のそれと同
意義。]で表わされるヨード化合物と、下記一般式[III]
および[IV]:[In the formula, X and Y have the same meanings as those in the general formula [I]. ] And an iodine compound represented by the following general formula [III]
And [IV]:
【００１４】[0014]
【化６】 [Chemical 6]
【００１５】[式中、Ｒ1、Ｒ4、Ａr1およびＡr2は一般
式[Ｉ]のそれと同意義。]で表わされるアミノ化合物をU
llmann反応により順次縮合させることにより得られる。
また、下上記一般式[Ｖ］：[In the formula, R 1 , R 4 , Ar 1 and Ar 2 have the same meanings as those in formula [I]. ] The amino compound represented by
It is obtained by sequentially condensing by the llmann reaction.
In addition, the above general formula [V]:
【００１６】[0016]
【化７】 [Chemical 7]
【００１７】［式中、Ｘ及びＹは一般式[Ｉ]中のそれと
同意義。]で表わされるアミノ化合物と、一般式[VI]、
[VII]、[VIII]あるいは[IX]で表されるヨード化合物と
を塩基性化合物又は遷移金属化合物触媒の存在下で適当
なよう液中でUllmann反応により合成することもでき
る。[In the formula, X and Y have the same meanings as those in formula [I]. ] With an amino compound represented by the general formula [VI],
It is also possible to synthesize the iodo compound represented by [VII], [VIII] or [IX] by an Ullmann reaction in an appropriate liquid in the presence of a basic compound or a transition metal compound catalyst.
【００１８】[0018]
【化８】 [Chemical 8]
【００１９】また反応は、一般的に常圧下１００〜２５
０℃での温度で行なわれるが、加圧下で行なってもよ
い。反応終了後、反応液中に折出した固形物を除去した
後、溶媒を除去し生成物を得ることができる。The reaction is generally 100 to 25 under normal pressure.
It is carried out at a temperature of 0 ° C., but it may be carried out under pressure. After the completion of the reaction, the solid matter that has broken out into the reaction solution can be removed, and then the solvent can be removed to obtain the product.
【００２０】上記方法における塩基性化合物としては、
アルカリ金属の水酸化物、炭酸塩、炭酸水素塩、アルコ
ラートなどが一般的に用いられるが、第４級アンモニウ
ム化合物や脂肪族アミンや芳香族アミンのような有機塩
基を用いることも可能である。このなかでアルカリ金属
や第４級アンモニウムの炭酸塩や炭酸水素塩が好ましい
ものとして用いられる。更に、反応速度及び熱安定性と
いう観点からアルカリ金属の炭酸塩や炭酸水素塩が最も
好ましい。As the basic compound in the above method,
Alkali metal hydroxides, carbonates, hydrogen carbonates, alcoholates and the like are generally used, but it is also possible to use quaternary ammonium compounds and organic bases such as aliphatic amines and aromatic amines. Of these, alkali metal and quaternary ammonium carbonates and hydrogen carbonates are preferably used. Furthermore, from the viewpoint of reaction rate and thermal stability, carbonates and hydrogen carbonates of alkali metals are most preferable.
【００２１】本発明のジアミノ化合物の合成に用いられ
る遷移金属又は遷移金属化合物としては、例えばＣu、
Ｆe、Ｃo、Ｎi、Ｃr、Ｖ、Ｐd、Ｐt、Ａg等の金属及び
それらの化合物が用いられるが、収率の点から銅及びパ
ラジウムとそれらの化合物が好ましい。銅化合物として
は特に限定はなく、ほとんどの銅化合物が用いられる
が、ヨウ化第一銅、塩化第一銅、酸化第一銅、臭化第一
銅、シアン化第一銅、硫酸第一銅、硫酸第二銅、塩化第
二銅、水酸化第二銅、酸化第二銅、臭化第二銅、リン酸
第二銅、硝酸第一銅、硝酸第二銅、炭酸銅、酢酸第一
銅、酢酸第二銅などが好ましい。その中でも特にＣuＣ
l、ＣuＣl2、ＣuＢr、ＣuＢr2、ＣuＩ、ＣuＯ、Ｃu
2Ｏ、ＣuＳＯ4、Ｃu(ＯＣＯＣＨ3)2は容易に入手可能で
ある点で好適である。パラジウム化合物としても、ハロ
ゲン化物、硫酸塩、硝酸塩、有機酸塩などを用いること
ができる。遷移金属及びその化合物の使用量は、反応さ
せるヨード化合物の０．５〜５００モル％とするのが望
ましい。Examples of the transition metal or transition metal compound used in the synthesis of the diamino compound of the present invention include Cu,
Metals such as Fe, Co, Ni, Cr, V, Pd, Pt and Ag and their compounds are used, but copper and palladium and their compounds are preferable in terms of yield. The copper compound is not particularly limited, and most copper compounds are used, but cuprous iodide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous cyanide, cuprous sulfate. , Cupric sulfate, cupric chloride, cupric hydroxide, cupric oxide, cupric bromide, cupric phosphate, cuprous nitrate, cupric nitrate, copper carbonate, acetic acid first Copper, cupric acetate, etc. are preferred. Among them, especially CuC
l, CuCl 2 , CuBr, CuBr 2 , CuI, CuO, Cu
2 O, CuSO 4 , and Cu (OCOCH 3 ) 2 are preferable because they are easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts and the like can be used. The amount of the transition metal and its compound used is preferably 0.5 to 500 mol% of the iodine compound to be reacted.
【００２２】合成で用いられる溶媒は、一般的に用いら
れる溶媒であれば良いが、ニトロベンゼン、ジメチルホ
ルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリ
ドン等の非プロトン性極性溶媒が好ましく用いられる。The solvent used in the synthesis may be a commonly used solvent, but an aprotic polar solvent such as nitrobenzene, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone is preferably used.
【００２３】上記一般式[Ｉ]で表されるジアミノ化合物
はいずれも側鎖の特定の位置に２つのビフェニル基を有
する点に構造的特徴を有するものである。このビフェニ
ル基の立体構造により結着樹脂中における結晶化を抑え
ることができ、樹脂への良好な相溶性を示す。尚、側鎖
にビフェニル基が３つ以上結合すると、相溶性は向上す
るものの、輸送能が低下したり成膜性が悪くなるといっ
た弊害が生じる。The diamino compounds represented by the above general formula [I] are structurally characterized in that they have two biphenyl groups at specific positions on their side chains. Due to this three-dimensional structure of the biphenyl group, crystallization in the binder resin can be suppressed, and good compatibility with the resin is exhibited. Incidentally, when three or more biphenyl groups are bonded to the side chain, the compatibility is improved, but the transportability is lowered and the film forming property is deteriorated.
【００２４】以下に、一般式[Ｉ]で表される本発明のジ
アミノ化合物を具体的に示すが、これに限定されるもの
ではない。Specific examples of the diamino compound of the present invention represented by the general formula [I] are shown below, but the invention is not limited thereto.
【００２５】[0025]
【化９】 [Chemical 9]
【００２６】[0026]
【化１０】 [Chemical 10]
【００２７】[0027]
【化１１】 [Chemical 11]
【００２８】[0028]
【化１２】 [Chemical 12]
【００２９】[0029]
【化１３】 [Chemical 13]
【００３０】[0030]
【化１４】 [Chemical 14]
【００３１】[0031]
【化１５】 [Chemical 15]
【００３２】[0032]
【化１６】 [Chemical 16]
【００３３】[0033]
【化１７】 [Chemical 17]
【００３４】[0034]
【化１８】 [Chemical 18]
【００３５】[0035]
【化１９】 [Chemical 19]
【００３６】[0036]
【化２０】 [Chemical 20]
【００３７】[0037]
【化２１】 [Chemical 21]
【００３８】[0038]
【化２２】 [Chemical formula 22]
【００３９】[0039]
【化２３】 [Chemical formula 23]
【００４０】[0040]
【化２４】 [Chemical formula 24]
【００４１】[0041]
【化２５】 [Chemical 25]
【００４２】[0042]
【化２６】 [Chemical formula 26]
【００４３】[0043]
【化２７】 [Chemical 27]
【００４４】[0044]
【化２８】 [Chemical 28]
【００４５】本発明においては、感度、樹脂との相溶性
の点から、化合物の構造式中にアルキル基、アルコキシ
基等の置換基を有するものが良好である。具体的には、
上記化合物例中において、[２]、[３]、[４]、[７]、
[８]、[９]、[１０]、[１２]、[１３]、[１４]、[１
６]、[１９]、[２２]、[２４]、[２５]、[２6]、[２
７]、[２８]、[３２]、[３８]、[３９]、[４０]、[４
３]、[４４]、[５２]、[５３]、[５４]、[５５]、[５
８]、[５９]、[６０]、[６３]、[６４]、[６５]、[６
６]、[６７]、[６８]、[６９]、[７２]、[７３]、[７
４]、[７５]、[８３]、[８４]、[８５]、[８６]、[９
０]、[９１]、[９２]、[９３]、[９４]、[９６]、[９
７]、[９８]および[９９]が特に好ましい。In the present invention, those having a substituent such as an alkyl group or an alkoxy group in the structural formula of the compound are preferable from the viewpoint of sensitivity and compatibility with the resin. In particular,
In the above compound examples, [2], [3], [4], [7],
[8], [9], [10], [12], [13], [14], [1
6], [19], [22], [24], [25], [26], [2]
7], [28], [32], [38], [39], [40], [4]
3], [44], [52], [53], [54], [55], [5]
8], [59], [60], [63], [64], [65], [6]
6], [67], [68], [69], [72], [73], [7]
4], [75], [83], [84], [85], [86], [9
0], [91], [92], [93], [94], [96], [9
7], [98] and [99] are particularly preferable.
【００４６】上記ジアミノ化合物は光導電性化合物であ
るが、光感度、電荷の輸送性に優れており、特に電荷輸
送材料として作用する。また上記ジアミノ化合物は、１
種あるいは２種以上混合してもよく、他の電荷輸送物
質、例えばヒドラゾン化合物と混合して使用することも
可能である。Although the above-mentioned diamino compound is a photoconductive compound, it is excellent in photosensitivity and charge transport property, and particularly acts as a charge transport material. The diamino compound is 1
One kind or a mixture of two or more kinds may be used, and it is also possible to use it by mixing with another charge transporting material such as a hydrazone compound.
【００４７】本発明の一般式[Ｉ]で表されるジアミノ化
合物は、感光体の感光材料、特に電荷輸送材料として利
用することができ、光を吸収することにより発生した電
荷担体を、極めて効率よく輸送することで、電荷移動
度、および高速応答性に優れた感光体を提供することが
できる。The diamino compound represented by the general formula [I] of the present invention can be used as a light-sensitive material for a photoconductor, particularly a charge-transporting material, and is extremely efficient in absorbing charge carriers generated by absorbing light. By transporting well, a photoreceptor having excellent charge mobility and high-speed response can be provided.
【００４８】導電性支持体上に、少なくとも一般式[Ｉ]
で表されるジアミノ化合物を１種あるいは２種以上含有
する感光層を形成することによって、高感度で結着樹脂
との相溶性に優れた感光体を提供することができ、その
形態としては、例えば図１から図５に示すようなものが
挙げられる。On a conductive support, at least the compound of the general formula [I]
By forming a photosensitive layer containing one or more diamino compounds represented by, it is possible to provide a photoreceptor having high sensitivity and excellent compatibility with a binder resin. For example, the ones shown in FIGS. 1 to 5 can be cited.
【００４９】例えば、図１に示すような導電性支持体上
１に電荷発生材料２を含有する電荷発生層５と電荷輸送
材料３を含有する電荷輸送層６とがこの順序で積層され
て成る機能分離型の積層感光体、あるいは図２に示すよ
うな導電性支持体１上に電荷輸送材料３を含有する電荷
輸送層６と電荷発生材料２を含有する電荷発生層５とが
順に積層されてなる機能分離型の感光体である。図３に
示すような導電性支持体１上に形成される感光層が電荷
発生材料２と電荷輸送材料３とを結着剤とともに配合さ
せて感光層４を形成した単層型の感光体、また図４に示
すように、図１の感光体表面に表面保護層７を設けたも
のや、図５に示すように導電性支持体１と感光層４との
間に中間層８を設けたものであってもよい。For example, a charge generating layer 5 containing a charge generating material 2 and a charge transporting layer 6 containing a charge transporting material 3 are laminated in this order on a conductive support 1 as shown in FIG. A function-separated type laminated photoreceptor or a charge transport layer 6 containing a charge transport material 3 and a charge generation layer 5 containing a charge generation material 2 are sequentially laminated on a conductive support 1 as shown in FIG. It is a function-separated type photoreceptor. A single-layer type photoreceptor in which the photosensitive layer formed on the conductive support 1 as shown in FIG. 3 is formed by mixing the charge generating material 2 and the charge transporting material 3 with a binder to form the photosensitive layer 4. Further, as shown in FIG. 4, a surface protective layer 7 is provided on the surface of the photoreceptor of FIG. 1, and an intermediate layer 8 is provided between the conductive support 1 and the photosensitive layer 4 as shown in FIG. It may be one.
【００５０】まず本発明の感光体として図１に示すよう
な積層感光体を作製する場合について説明する。この場
合、導電性支持体上に、電荷発生材料を真空蒸着する
か、あるいは電荷輸送材料を適当な溶剤もしくは必要が
あれば結着樹脂を溶解させた溶液中に分散させて作製し
た塗布液を塗布乾燥した後、その上に電荷輸送材料およ
び結着樹脂を含む溶液を塗布乾燥して電荷輸送層を形成
する。電荷発生層の膜厚は４μm以下、好ましくは２μm
以下とする。電荷輸送層は一般式[Ｉ]で表される本発明
のジアミノ化合物および結着樹脂を含む溶液を塗布、乾
燥することによって作製される。このとき電荷輸送層中
のジアミノ化合物の割合は、少な過ぎると感度が悪く、
多過ぎると帯電性が悪くなったり、感光層の機械的強度
が弱くなったりするため、結着樹脂１重量部に対して
０.２〜２重量部、好ましくは０.３〜１.３重量部と
し、電荷輸送層の膜厚は３〜５０μm、好ましくは５〜
４０μmとするのが望ましい。感光体の高速化あるいは
長寿命化に対応するためには、電荷輸送層の膜厚を３０
〜５０μｍと厚く構成することが望ましい。First, the case of producing a laminated photoreceptor as shown in FIG. 1 as the photoreceptor of the present invention will be described. In this case, a coating solution prepared by vacuum-depositing the charge-generating material on the conductive support or dispersing the charge-transporting material in a suitable solvent or a solution in which a binder resin is dissolved if necessary is prepared. After coating and drying, a solution containing a charge transporting material and a binder resin is coated and dried thereon to form a charge transporting layer. The thickness of the charge generation layer is 4 μm or less, preferably 2 μm
Below. The charge transport layer is prepared by applying a solution containing the diamino compound of the present invention represented by the general formula [I] and a binder resin and drying the solution. At this time, if the ratio of the diamino compound in the charge transport layer is too small, the sensitivity is poor,
If the amount is too large, the chargeability may be deteriorated or the mechanical strength of the photosensitive layer may be weakened, so 0.2 to 2 parts by weight, preferably 0.3 to 1.3 parts by weight, relative to 1 part by weight of the binder resin. And the charge transport layer has a thickness of 3 to 50 μm, preferably 5 to
It is desirable to set it to 40 μm. The film thickness of the charge transport layer is set to 30 in order to cope with the speeding up and the long life of the photoconductor.
It is desirable that the thickness is as thick as ˜50 μm.
【００５１】このような機能分離型の積層型感光体は、
材料の選択範囲が広く、帯電特性、残留電位、繰り返し
特性、耐久性等の電子写真特性において、最良の物質を
組み合わさせることができ、これによって高性能な感光
体を提供する利点がある。さらに膜厚の調整により、感
光体の長寿命化を図ることも容易である。Such a function-separated laminated type photoreceptor is
There is an advantage that a wide range of materials can be selected, and the best substances can be combined in terms of electrophotographic characteristics such as charging characteristics, residual potential, repetitive characteristics and durability, thereby providing a high performance photoreceptor. It is also easy to extend the life of the photoconductor by adjusting the film thickness.
【００５２】本発明における感光体として、図３に示す
ような単層型感光体を作製する場合について説明する。
この場合、電荷発生材料の微粒子を本発明のジアミノ化
合物と樹脂を溶解した溶液中に分散せしめ、これを導電
性支持体上に塗布乾燥して感光体を作製する。このと
き、感光層中の電荷発生材料の量は、結着樹脂１重量部
に対して０.０１〜２重量部、好ましくは、０.２〜１.
２重量部が望ましい。一般式[Ｉ]で表わされるジアミノ
化合物の量については、少ない場合は充分な感度が得ら
れず、多い場合は成膜性が悪い、感光層の機械的強度が
弱い等の問題点を生じるため、感光層中の結着樹脂１重
量部に対して０.０１〜２重量部、好ましくは０.１〜
１.５重量部、より好ましくは０.２〜１.２重量部配合
するのがよい。また、通常、感光層の膜厚は３〜５０μ
m、好ましくは５〜４０μmとするのがよい。A case of producing a single-layer type photosensitive member as shown in FIG. 3 as the photosensitive member in the present invention will be described.
In this case, fine particles of the charge generating material are dispersed in a solution in which the diamino compound of the present invention and a resin are dissolved, and this is coated on a conductive support and dried to prepare a photoreceptor. At this time, the amount of the charge generating material in the photosensitive layer is 0.01 to 2 parts by weight, preferably 0.2 to 1 part by weight with respect to 1 part by weight of the binder resin.
2 parts by weight is desirable. When the amount of the diamino compound represented by the general formula [I] is small, sufficient sensitivity cannot be obtained, and when it is large, problems such as poor film-forming property and weak mechanical strength of the photosensitive layer occur. 0.01 to 2 parts by weight, preferably 0.1 to 2 parts by weight, relative to 1 part by weight of the binder resin in the photosensitive layer.
The amount is preferably 1.5 parts by weight, more preferably 0.2 to 1.2 parts by weight. The thickness of the photosensitive layer is usually 3 to 50 μm.
m, preferably 5 to 40 μm.
【００５３】上記のような単層型感光体は、オゾン発生
に対して有効である正帯電用感光体として使用可能であ
る。また、両極性感光体としても使用可能であり、種々
の画像システムと組み合わせて使用することができる。The single-layer type photoconductor as described above can be used as a positive charging photoconductor which is effective for ozone generation. It can also be used as a bipolar photoreceptor and can be used in combination with various image systems.
【００５４】また本発明の感光体は、図５に示すように
中間層を設けたものであってもよく、これによって接着
性の改良、塗工性の向上、支持体の保護、支持体側から
の感光層への電荷注入性の抑制を図ることができる。The photoreceptor of the present invention may be provided with an intermediate layer as shown in FIG. 5, whereby the adhesion is improved, the coatability is improved, the support is protected, and the support side is provided. It is possible to suppress the charge injection property of the above into the photosensitive layer.
【００５５】中間層に用いられる材料としてはポリイミ
ド、ポリアミド、ニトロセルロースポリビニルブチラー
ル、ポリビニルアルコール、酸化アルミニウム等が適当
で、また膜厚は１μｍ以下が望ましい。Polyimide, polyamide, nitrocellulose polyvinyl butyral, polyvinyl alcohol, aluminum oxide and the like are suitable as the material used for the intermediate layer, and the film thickness is preferably 1 μm or less.
【００５６】さらに本発明の感光体は表面保護層を設け
たものであってもよい。表面保護層に用いられる材料と
しては、アクリル樹脂、ポリアリール樹脂、ポリカーボ
ネート樹脂、ウレタン樹脂などのポリマーをそのまま、
または酸化スズや酸化インジウムなどの低抵抗化合物を
分散させたものなどが適当である。Further, the photoreceptor of the present invention may be provided with a surface protective layer. As a material used for the surface protective layer, a polymer such as an acrylic resin, a polyaryl resin, a polycarbonate resin, or a urethane resin is directly used,
Alternatively, a material in which a low resistance compound such as tin oxide or indium oxide is dispersed is suitable.
【００５７】また有機プラズマ重合膜を使用することが
できる。有機プラズマ重合膜は必要に応じて適宜酸素、
窒素、ハロゲン、周期律表の第３族、第５族原子を含ん
でいてもよい。It is also possible to use organic plasma polymerized membranes. The organic plasma polymerized film is appropriately oxygen,
It may contain nitrogen, halogen, and atoms of Group 3 and Group 5 of the periodic table.
【００５８】本発明の感光体に用いられる導電性支持体
としては、銅、アルミニウム、鉄、ニッケル等の泊ある
いは板を、シート状またはドラム状にしたものが使用さ
れ、る。またこれらの金属を、プラスチックフィルム等
に真空蒸着、無電解メッキしたもの、あるいは導電性ポ
リマー、酸化インジュウム、酸化スズ等の導電性化合物
の層を同様に、紙あるいはプラスチックフィルムなどの
支持体上に塗布もしくは蒸着によって設けたものであ
る。As the conductive support used in the photoreceptor of the present invention, a sheet or drum of copper, aluminum, iron, nickel or the like is used. Further, these metals are vacuum-deposited or electroless plated on a plastic film, or a layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide is similarly formed on a support such as paper or a plastic film. It is provided by coating or vapor deposition.
【００５９】電荷発生材料としては、ビスアゾ系顔料、
トリアリールメタン系染料、チアジン系染料、オキサジ
ン系染料、キサンテン系染料、シアニン系色素、スチリ
ル色素、ピリリウム系染料、アゾ系顔料、キナクリドン
系顔料、インジゴ系顔料、ペリレン系顔料、多環キノン
系顔料、ビスベンズイミダゾール系顔料、インダスロン
系顔料、スクアリウム塩系顔料、アズレン系色素、フタ
ロシアニン系顔料等の有機物質や、セレン、セレン・テ
ルル、セレン・砒素などのセレン合金、硫化カドミウ
ム、セレン化カドミウム、酸化亜鉛、アモルアァスシリ
コン等の無機物質が挙げられる。これ以外でも、光を吸
収し極めて高い確率で電荷担体を発生する材料であれ
ば、いずれの材料であっても使用することができる。As the charge generating material, a bisazo pigment,
Triarylmethane dye, thiazine dye, oxazine dye, xanthene dye, cyanine dye, styryl dye, pyrylium dye, azo pigment, quinacridone pigment, indigo pigment, perylene pigment, polycyclic quinone pigment , Bisbenzimidazole-based pigments, indathlon-based pigments, squalium salt-based pigments, azulene-based pigments, phthalocyanine-based pigments, and other organic substances, selenium, selenium / tellurium, selenium / arsenic, and other selenium alloys, cadmium sulfide, cadmium selenide Inorganic substances such as zinc oxide, and amorphous silicon. Other than this, any material can be used as long as it absorbs light and generates charge carriers with an extremely high probability.
【００６０】上記のような感光体の製造に使用される結
着樹脂は電気絶縁性であり、単独で測定して１×１０12
Ω・cm以上の体積抵抗を有することが望ましい。例え
ば、それ自体公知の熱可塑性樹脂、熱硬化性樹脂、光硬
化性樹脂、光導電性樹脂等の結着剤を使用することがで
きる。具体的には、飽和ポリエステル樹脂、ポリアミド
樹脂、アクリル樹脂、エチレン−酢酸ビニル樹脂、イオ
ン架橋オレフィン共重合体(アイオノマー)、スチレン−
ブタジエンブロック共重合体、ポリカーボネート、塩化
ビニル−酢酸ビニル共重合体、セルロースエステル、ポ
リイミド、スチロール樹脂等の熱可塑性樹脂;エポキシ
樹脂、ウレタン樹脂、シリコーン樹脂、フェノール樹
脂、メラミン樹脂、キシレン樹脂、アルキッド樹脂、熱
硬化アクリル樹脂等の熱硬化性樹脂;光硬化性樹脂;ポリ
ビニルカルバゾール、ポリビニルピレン、ポリビニルア
ントラセン、ポリビニルピロール等の光導電性樹脂が挙
げられ、これらの結着樹脂は単独もしくは２種以上組み
合わせて使用する。尚、本願発明においては、電荷輸送
層に使用する結着樹脂として、感度、耐久性の面でポリ
カーボネート樹脂、ポリアリール樹脂が特に好ましい。The binder resin used in the production of the above-mentioned photoreceptor is electrically insulating, and is measured by itself to be 1 × 10 12
It is desirable to have a volume resistance of Ω · cm or more. For example, a binder such as a thermoplastic resin, a thermosetting resin, a photocurable resin, or a photoconductive resin known per se can be used. Specifically, saturated polyester resin, polyamide resin, acrylic resin, ethylene-vinyl acetate resin, ion-crosslinked olefin copolymer (ionomer), styrene-
Thermoplastic resins such as butadiene block copolymer, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin, urethane resin, silicone resin, phenol resin, melamine resin, xylene resin, alkyd resin , Thermosetting resins such as thermosetting acrylic resins; photocurable resins; photoconductive resins such as polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, and polyvinylpyrrole. These binder resins may be used alone or in combination of two or more. To use. In the present invention, as the binder resin used for the charge transport layer, a polycarbonate resin and a polyaryl resin are particularly preferable in terms of sensitivity and durability.
【００６１】本発明の感光体は結着樹脂とともに、ハロ
ゲン化パラフイン、ポリ塩化ビフエニル、ジメチルナフ
タレン、ジブチルフタレート、Ｏ−ターフエニルなどの
可塑剤やクロラニル、テトラシアノエチレン、２,４,７
−トリニトロフルオレノン、５,６−ジシアノベンゾキ
ノン、テトラシアノキノジメタン、テトラクロル無水フ
タル酸、３,５−ジニトロ安息香酸等の電子吸引性増感
剤、メチルバイオレット、ローダミンＢ、シアニン染
料、ピリリウム塩、チアピリリウム塩等の増感剤を使用
してもよい。The photoconductor of the present invention comprises a binder resin, a plasticizer such as halogenated paraffin, polychlorinated biphenyls, dimethylnaphthalene, dibutylphthalate and O-terphenyl, chloranil, tetracyanoethylene, 2,4,7.
-Trinitrofluorenone, 5,6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, electron-withdrawing sensitizer such as 3,5-dinitrobenzoic acid, methyl violet, rhodamine B, cyanine dye, pyrylium salt A sensitizer such as thiapyrylium salt may be used.
【００６２】[0062]
【合成例】以下に化合物例[２]で表されるジアミノ化合
物の合成方法を示す。[Synthesis Example] The synthesis method of the diamino compound represented by Compound Example [2] is shown below.
【００６３】下記式で示されるジヨード化合物４１.８
ｇ(０.１０モル)と、The diiodo compound 41.8 represented by the following formula:
g (0.10 mol),
【００６４】[0064]
【化２９】 [Chemical 29]
【００６５】Ｎ−ビフェニル−Ｎ−ｐトリルアミン６
２.２ｇ(０.２４モル)、炭酸カリウム３５ｇ(０.３０モ
ル)、銅粉１０ｇ(０.１６モル)及びニトロベンゼン４０
０ｇを１リットルの還流冷却器付き４つ口フラスコに装
入し、窒素気流下に２００℃で１８時間攪拌反応させ
た。反応終了後、水蒸気蒸留によりニトロベンゼンを留
去させた後、テトラヒドロフラン(ＴＨＦ)３００ｇを加
え、次いで固型物を濾過した。濾液をシリカゲルカラム
クロマトで分離した後、分離物をトルエン−エタノール
混合溶媒中で再結晶して精製し、５２ｇの白色結晶を得
た。元素分析の結果は下記表１の通りである(Ｃ51Ｈ40
Ｎ2として) 。N-biphenyl-N-p-tolylamine 6
2.2 g (0.24 mol), potassium carbonate 35 g (0.30 mol), copper powder 10 g (0.16 mol) and nitrobenzene 40
0 g was placed in a 1-liter four-necked flask equipped with a reflux condenser, and the mixture was stirred and reacted at 200 ° C. for 18 hours under a nitrogen stream. After completion of the reaction, nitrobenzene was distilled off by steam distillation, 300 g of tetrahydrofuran (THF) was added, and then the solid product was filtered. The filtrate was separated by silica gel column chromatography, and the separated product was recrystallized in a toluene-ethanol mixed solvent for purification to obtain 52 g of white crystals. The results of elemental analysis are shown in Table 1 below (C 51 H 40
As N 2).
【００６６】 また、ＦＤ−マススペクトル測定にて目的物の親ピーク
を検出したところ、[0066] When the parent peak of the target substance was detected by FD-mass spectrum measurement,
【００６７】[0067]
【数１】 [Equation 1]
【００６８】であった。It was
【００６９】次に、化合物例[８]で表されるジアミノ化
合物の合成方法を示す。Next, a method for synthesizing the diamino compound represented by Compound Example [8] is shown.
【００７０】下記式で示されるジヨード化合物４４.６
ｇ(０.１０モル)と、A diiodo compound represented by the following formula: 44.6
g (0.10 mol),
【００７１】[0071]
【化３０】 [Chemical 30]
【００７２】Ｎ−ビフェニル−Ｎ−２,４−キシリルア
ミン６５.６ｇ(０.２４モル)、炭酸カリウム３５ｇ(０.
３０モル)、銅粉１０ｇ(０.１６モル)及びニトロベンゼ
ン４００ｇを１リットルの還流冷却器付き４つ口フラス
コに装入し、窒素気流下に２００℃で１８時間攪拌反応
させた。反応終了後、水蒸気蒸留によりニトロベンゼン
を留去させた後、テトラヒドロフラン(ＴＨＦ)３００ｇ
を加え、次いで固型物を濾過した。濾液をシリカゲルカ
ラムクロマトで分離した後、分離物をトルエン−エタノ
ール混合溶媒中で再結晶して精製し、５２ｇの白色結晶
を得た。元素分析の結果は下記表２の通りである(Ｃ55
Ｈ48Ｎ2として)。N-biphenyl-N-2,4-xylylamine 65.6 g (0.24 mol) and potassium carbonate 35 g (0.2 mol).
30 mol), 10 g (0.16 mol) of copper powder, and 400 g of nitrobenzene were charged into a 1-liter four-necked flask equipped with a reflux condenser, and reacted with stirring at 200 ° C. for 18 hours under a nitrogen stream. After completion of the reaction, nitrobenzene was distilled off by steam distillation, and then tetrahydrofuran (THF) 300 g
Was added and then the solid was filtered. The filtrate was separated by silica gel column chromatography, and the separated product was recrystallized in a toluene-ethanol mixed solvent for purification to obtain 52 g of white crystals. The results of elemental analysis are shown in Table 2 below (C 55
H 48 N 2 ).
【００７３】 また、ＦＤ−マススペクトル測定にて目的物の親ピーク
を検出したところ、[0073] When the parent peak of the target substance was detected by FD-mass spectrum measurement,
【００７４】[0074]
【数２】 [Equation 2]
【００７５】であった。It was
【００７６】[0076]
【実施例】以下、具体的実施例を挙げながら本発明を説
明する。以後の実施例に用いられる本発明のジアミノ化
合物は前記合成例またはこれと類似の方法により合成を
行ったものである。EXAMPLES The present invention will be described below with reference to specific examples. The diamino compounds of the present invention used in the following Examples are those synthesized by the above-mentioned Synthesis Example or a method similar thereto.
【００７７】実施例１ 下記一般式[Ａ]で表されるビスアゾ化合物： Example 1 Bisazo compound represented by the following general formula [A]:
【００７８】[0078]
【化３１】 [Chemical 31]
【００７９】０.４５重量部、ポリエステル樹脂(バイロ
ン２００；東洋紡績社製)０.４５重量部をシクロヘキサ
ノン５０重量部とともにサンドグラインダーにより分散
させた。得られたビスアゾ化合物の分散物を厚さ１００
μmのアルミ化マイラー上にフィルムアプリケーターを
用いて、乾燥膜厚が０.３g／m2となる様に塗布した後乾
燥し、電荷発生層を形成した。この上にジアミノ化合物
[２]７０重量部およびポリカーボネート樹脂(パンライ
トＫ−１３００;帝人化成社製)７０重量部とを１,４−
ジオキサン４００部に溶解した溶液を乾燥膜厚が２０μ
mになるように塗布し、乾燥させて電荷輸送層を形成し
て、２層からなる感光層を有する電子写真感光体を作製
した。0.45 parts by weight of polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) of 0.45 parts by weight were dispersed with a sand grinder together with 50 parts by weight of cyclohexanone. The dispersion of the obtained bisazo compound was made to have a thickness of 100.
A film applicator was used to apply a dry film thickness of 0.3 g / m 2 on μm aluminized mylar and then dried to form a charge generation layer. Diamino compound on this
[2] 70 parts by weight of polycarbonate resin (Panlite K-1300; Teijin Chemicals Co., Ltd.)
The solution dissolved in 400 parts of dioxane has a dry film thickness of 20μ.
It was coated so as to have a thickness of m, and dried to form a charge transport layer, thereby preparing an electrophotographic photoreceptor having a photosensitive layer composed of two layers.
【００８０】実施例２〜４ 実施例１で用いたジアミノ化合物[２]の変わりにトリア
ミノ化合物[５]、[８]、[９]を用いた以外は実施例１と
同様の方法で３種類の積層感光体を作製した。 Examples 2 to 4 Three kinds were prepared in the same manner as in Example 1 except that the diamino compound [2] used in Example 1 was replaced with the triamino compounds [5], [8] and [9]. To prepare a laminated photoconductor.
【００８１】実施例５ 下記一般式[Ｂ]で表されるビスアゾ化合物： Example 5 Bisazo compound represented by the following general formula [B]:
【００８２】[0082]
【化３２】 [Chemical 32]
【００８３】０.４５重量部、ポリスチレン樹脂(分子量
４００００)０.４５重量部をシクロヘキサノン５０重量
部とともにサンドグラインダーにより分散させた。0.45 parts by weight and 0.45 parts by weight of polystyrene resin (molecular weight 40,000) were dispersed together with 50 parts by weight of cyclohexanone by a sand grinder.
【００８４】得られたビスアゾ化合物の分散液を厚さ１
００μmのアルミ化マイラー上にフィルムアプリケータ
ーを用いて、乾燥膜厚が０．３g／m2となる様に塗布し
た後乾燥し電荷発生層を形成した。この上にトリアミノ
化合物[７]７０重量部およびポリアリレート樹脂(Ｕ−
１００；ユニチカ社製)７０重量部を１,４−ジオキサン
４００重量部に溶解した溶液を乾燥膜厚が２０μmにな
るように塗布し、乾燥させて電荷輸送層を形成して、２
層からなる感光層を有する電子写真感光体を作製した。The dispersion liquid of the obtained bisazo compound was made to have a thickness of 1
A charge applicator layer was formed by applying a dry film thickness of 0.3 g / m 2 on a 00 μm aluminized mylar using a film applicator and then drying. On top of this, 70 parts by weight of a triamino compound [7] and a polyarylate resin (U-
100: Unitika Ltd.) 70 parts by weight dissolved in 400 parts by weight of 1,4-dioxane is applied to a dry film thickness of 20 μm and dried to form a charge transport layer.
An electrophotographic photoreceptor having a photosensitive layer composed of layers was produced.
【００８５】実施例６〜８ 実施例５で用いたジアミノ化合物[７]の代わりにジアミ
ノ化合物[１０]、[１２]、[１３]を用いた以外は実施例
５と同様の方法で３種類の積層感光体を作製した。 Examples 6 to 8 Three kinds were prepared in the same manner as in Example 5 except that the diamino compounds [10], [12] and [13] were used instead of the diamino compound [7] used in Example 5. To prepare a laminated photoconductor.
【００８６】実施例９ 下記一般式[Ｃ]で表される多環キノン系顔料： Example 9 Polycyclic quinone pigment represented by the following general formula [C]:
【００８７】[0087]
【化３３】 [Chemical 33]
【００８８】０.４５重量部、ポリカーボネート樹脂(パ
ンライトＫ−１３０００:帝人化成社製)０.４５重量部
をジクロルエタン５０重量部とともにサンドミルにより
分散させた。得られた多環キノン系顔料の分散液を厚さ
１００μmのアルミ化マイラー上にフィルムアプリケー
ターを用いて、乾燥膜厚が０.４g／m2となる様に塗布し
電荷発生層を形成した。この上にジアミノ化合物[１４]
６０重量部およびポリアリレート樹脂(Ｕ−１００;ユニ
チカ社製)５０重量部を１,４−ジオキサン４００重量部
に溶解した溶液を乾燥膜厚が１８μmになるように塗布
し、乾燥させて電荷輸送層を形成して、２層からなる感
光層を有する電子写真感光体を作製した。0.45 part by weight and 0.45 part by weight of a polycarbonate resin (Panlite K-13000, manufactured by Teijin Chemicals) were dispersed in a sand mill together with 50 parts by weight of dichloroethane. The resulting polycyclic quinone pigment dispersion was applied onto a 100 μm thick aluminized mylar using a film applicator so that the dry film thickness was 0.4 g / m 2 to form a charge generation layer. Diamino compound on this [14]
A solution prepared by dissolving 60 parts by weight and 50 parts by weight of polyarylate resin (U-100; manufactured by Unitika Ltd.) in 400 parts by weight of 1,4-dioxane was applied to a dry film thickness of 18 μm, and dried to charge transport. Layers were formed to prepare an electrophotographic photoreceptor having a photosensitive layer composed of two layers.
【００８９】実施例１０〜１１ 実施例９で用いたジアミノ化合物[１４]の代わりにジア
ミノ化合物[１５]、[１９]を用いた以外は実施例９と同
様の方法で３種類の感光体を作製した。 Examples 10 to 11 Three kinds of photoconductors were prepared in the same manner as in Example 9 except that the diamino compounds [15] and [19] were used in place of the diamino compound [14] used in Example 9. It was made.
【００９０】実施例１２ 下記一般式[Ｄ]で表されるペリレン系顔料： Example 12 Perylene pigment represented by the following general formula [D]:
【００９１】[0091]
【化３４】 [Chemical 34]
【００９２】０.４５重量部、ブチラール樹脂(ＢＸ−
１;積水化学工業社製)０.４５重量部をジクロルエタン
５０重量部とともにサンドミルにより分散させた。得ら
れたペリレン系顔料の分散液を厚さ１００μmのアルミ
化マイラー上にフィルムアプリケーターを用いて、乾燥
膜厚が０.４g／m2となる様に塗布した後乾燥させ、電荷
発生層を形成した。この上にジアミノ化合物[２２]５０
重量部およびポリカーボネート樹脂(ＰＣ−Ｚ;三菱ガス
化学社製)５０重量部を１,４−ジオキサン４００重量部
に溶解した溶液を乾燥膜厚が２３μmになるように塗布
し、電荷輸送層を形成して、２層からなる感光層を有す
る電子写真感光体を作製した。0.45 parts by weight of butyral resin (BX-
(1; manufactured by Sekisui Chemical Co., Ltd.) (0.45 parts by weight) was dispersed in a sand mill together with 50 parts by weight of dichloroethane. The resulting dispersion of perylene pigment was applied on aluminized mylar having a thickness of 100 μm using a film applicator so that the dry film thickness was 0.4 g / m 2, and then dried to form a charge generation layer. did. Diamino compound [22] 50 on top of this
A solution of 50 parts by weight and 50 parts by weight of a polycarbonate resin (PC-Z; manufactured by Mitsubishi Gas Chemical Co., Inc.) in 400 parts by weight of 1,4-dioxane is applied to a dry film thickness of 23 μm to form a charge transport layer. Then, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.
【００９３】実施例１３〜１４ 実施例１２で用いたジアミノ化合物[２２]の代わりにジ
アミノ化合物[２５]、[２６]を用いた以外は実施例１２
と同様の方法で２種類の感光体を作製した。 Examples 13 to 14 Example 12 except that diamino compounds [25] and [26] were used instead of the diamino compound [22] used in Example 12.
Two types of photoconductors were produced by the same method as described above.
【００９４】実施例１５ チタニルフタロシアニン０.４５重量部、ブチラール樹
脂(ＢＸ−１;積水化学工業社製)０.４５重量部をジクロ
ルエタン５０重量部とともにサンドミルにより分散させ
た。得られたフタロシアニン顔料の分散液を厚さ１００
μmのアルミ化マイラー上にフィルムアプリケーターを
用いて、乾燥膜厚が０.３g／m2となる様に塗布した後乾
燥させ電荷発生層を形成した。この上にジアミノ化合物
[３８]５０重量部およびポリカーボネート樹脂(ＰＣ−
Ｚ;三菱ガス化学社製)５０重量部を１,４−ジオキサン
４００重量部に溶解した溶液を乾燥膜厚が２５μmにな
るように塗布し電荷輸送層を形成して、２層からなる感
光層を有する電子写真感光体を作製した。 Example 15 0.45 parts by weight of titanyl phthalocyanine and 0.45 parts by weight of butyral resin (BX-1; manufactured by Sekisui Chemical Co., Ltd.) were dispersed in a sand mill together with 50 parts by weight of dichloroethane. The dispersion liquid of the obtained phthalocyanine pigment was made to have a thickness of 100.
A film applicator was used to apply a dry film thickness of 0.3 g / m 2 on μm aluminized mylar, and then dried to form a charge generation layer. Diamino compound on this
[38] 50 parts by weight and polycarbonate resin (PC-
(Z; manufactured by Mitsubishi Gas Chemical Co., Inc.) 50 parts by weight dissolved in 400 parts by weight of 1,4-dioxane is applied to a dry film thickness of 25 μm to form a charge transport layer, and a photosensitive layer composed of two layers. Was prepared.
【００９５】実施例１６〜１７ 実施例１５で用いたジアミノ化合物[３８]の代わりにジ
アミノ化合物[３９]、[４６]を用いた以外は実施例１５
と同様の方法で２種類の感光体を作製した。。 Examples 16 to 17 Example 15 except that diamino compounds [39] and [46] were used instead of the diamino compound [38] used in Example 15.
Two types of photoconductors were produced by the same method as described above. .
【００９６】実施例１８ 銅フタロシアニン５０重量部とテトラニトロ銅フタロシ
アニン０.２重量部を９８％濃硫酸５００重量部に充分
撹拌しながら溶解させ、これを水５０００重量部と混合
し、銅フタロシアニンとテトラニトロ銅フタロシアニン
の光導電性材料組成物を析出させた後、濾過、水洗し、
減圧下１２０℃で乾燥させた。こうして得られた光導電
性組成物１０重量部を熱硬化性アクリル樹脂(アクリデ
ィクＡ４０５;大日本インク社製)２２.５重量部、メラ
ミン樹脂(スーパーベッカミンＪ８２０;大日本インク社
製)７.５重量部、ジアミノ化合物[５３]１５重量部を、
メチルエチルケトンとキシレンを同量に混合した混合溶
剤１００重量部とともにボールミルポットに入れて４８
時間分散して感光性塗液を調製し、この塗液をアルミニ
ウムドラム基体上に塗布、乾燥して厚さ約２５μmの感
光層を形成し単層型感光体を作製した。 Example 18 50 parts by weight of copper phthalocyanine and 0.2 parts by weight of tetranitrocopper phthalocyanine were dissolved in 500 parts by weight of 98% concentrated sulfuric acid with sufficient stirring, and this was mixed with 5000 parts by weight of water to give copper phthalocyanine and tetranitro. After depositing a photoconductive material composition of copper phthalocyanine, filtered, washed with water,
It was dried under reduced pressure at 120 ° C. 10 parts by weight of the photoconductive composition thus obtained were used in an amount of 22.5 parts by weight of a thermosetting acrylic resin (Acridic A405; manufactured by Dainippon Ink and Chemicals), and a melamine resin (Super Beckamine J820; manufactured by Dainippon Ink and Chemicals) 7. 5 parts by weight, 15 parts by weight of diamino compound [53],
48 in a ball mill pot together with 100 parts by weight of a mixed solvent in which methyl ethyl ketone and xylene are mixed in the same amount.
A photosensitive coating liquid was prepared by dispersing for a time, and the coating liquid was applied onto an aluminum drum substrate and dried to form a photosensitive layer having a thickness of about 25 μm to prepare a single-layer type photoreceptor.
【００９７】実施例１９〜２１ 実施例１８で用いたジアミノ化合物[５３]の代わりにジ
アミノ化合物[５４]、[６５]、[９８]を用いた以外は実
施例１８と同様の方法で３種類の感光体を作製した。 Examples 19 to 21 Three kinds of compounds were prepared in the same manner as in Example 18 except that diamino compounds [54], [65] and [98] were used instead of the diamino compound [53] used in Example 18. A photoconductor was manufactured.
【００９８】比較例１〜４ 実施例１８で用いたジアミノ化合物[５３]の代わりに下
記に示すアミノ化合物[Ｅ]、[Ｆ]、[Ｇ]、[Ｈ]を用いた
以外は実施例１８と同様の方法で４種類の感光体を作製
した。 Comparative Examples 1 to 4 Example 18 except that the amino compounds [E], [F], [G] and [H] shown below were used in place of the diamino compound [53] used in Example 18 Four types of photoconductors were prepared in the same manner as in.
【００９９】[0099]
【化３５】 [Chemical 35]
【０１００】比較例５〜９ 実施例１８で用いたジアミノ化合物[５３]の代わりに下
記に示すアミノ化合物[Ｉ]、[Ｊ]、[Ｋ]、[Ｌ]または
[Ｍ]を各々用いた以外は実施例１８と全く同様にして５
種類の感光体を作製した。 Comparative Examples 5-9 Instead of the diamino compound [53] used in Example 18, the following amino compounds [I], [J], [K], [L] or
5 was carried out in the same manner as in Example 18 except that each [M] was used.
A variety of photoreceptors were made.
【０１０１】[0101]
【化３６】 [Chemical 36]
【０１０２】こうして得られた実施例１〜１７の感光体
を市販の電子写真複写機(ミノルタカメラ社製；ＥＰ−
５４００)に組み込み、−６Ｋvでコロナ帯電させ、初期
表面電位Ｖ0(Ｖ)、初期電位を１／２にするために要し
た露光量Ｅ1/2(lux・sec)、１秒間暗中に放置したとき
の初期電位の減衰率ＤＤＲ1(％)を測定した。さらに実
施例１８〜２１、比較例１〜９の感光体については、市
販の電子写真複写機(ミノルタカメラ社製;ＥＰ−３５０
Ｚ)による正帯電時の繰り返し実写テストを行ない、
Ｖ0、Ｅ1/2、ＤＤＲ1を測定した。結果を表３および表
４に示す。The photoconductors of Examples 1 to 17 thus obtained were put on the market in an electrophotographic copying machine (manufactured by Minolta Camera Co .; EP-
5400), corona charged at −6 Kv, and exposed to an initial surface potential V 0 (V) and an exposure amount E 1/2 (lux · sec) required to reduce the initial potential to 1/2, and left in the dark for 1 second. The initial potential decay rate DDR 1 (%) was measured. Further, regarding the photoconductors of Examples 18 to 21 and Comparative Examples 1 to 9, a commercially available electrophotographic copying machine (manufactured by Minolta Camera Co .; EP-350) was used.
Repeated live-action test with positive charge by Z),
V 0 , E 1/2 and DDR 1 were measured. The results are shown in Tables 3 and 4.
【０１０３】尚、実施例１〜２１においては、各実施例
で使用した感光性塗液は感光層塗布時に結晶化せず、良
好な塗膜が得られた。さらに上記感光性塗液を常温で１
週間放置しても結晶は析出しなかった。一方、比較例１
〜９においては、化合物[Ｇ]、[Ｈ]、[Ｊ]および[Ｌ]を
用いた感光性塗液は、感光層塗布時に一部結晶が析出し
た。これにより、本発明の新規ジアミノ化合物は結着樹
脂に対する相溶性が優れていることが確認された。In Examples 1 to 21, the photosensitive coating liquids used in each Example were not crystallized at the time of coating the photosensitive layer, and good coating films were obtained. Further, the above-mentioned photosensitive coating solution is applied at room temperature for 1
No crystals were deposited even if left for a week. On the other hand, Comparative Example 1
In Nos. 9 to 9, in the photosensitive coating liquids using the compounds [G], [H], [J] and [L], some crystals were precipitated during the coating of the photosensitive layer. From this, it was confirmed that the novel diamino compound of the present invention has excellent compatibility with the binder resin.
【０１０４】[0104]
【表３】 [Table 3]
【０１０５】[0105]
【表４】 [Table 4]
【０１０６】表３及び表４から明らかなように、本発明
の感光体は積層型でも単層型でも電荷保持能が充分あ
り、暗減衰率も感光体としては充分使用可能な程度に小
さく、また感度においても優れている。As is clear from Tables 3 and 4, the photoconductor of the present invention has a sufficient charge holding ability regardless of whether it is a laminated type or a single layer type, and the dark decay rate is small enough to be used as a photoconductor. It is also excellent in sensitivity.
【０１０７】さらに、実施例１８の感光体については、
市販の電子写真複写機(ミノルタカメラ社製;ＥＰ−３５
０Ｚ)による正帯電時の繰り返し実写テストを行った
が、１０００枚の実写の後も、初期画像と同様階調性に
優れ、感度変化がなく、鮮明な画像が得られ、本発明の
感光体は繰り返し特性についても安定していることが確
認された。Furthermore, regarding the photoconductor of Example 18,
Commercially available electrophotographic copying machine (Minolta Camera Co .; EP-35
(0Z), a repeated real-image test was performed at the time of positive charging. Even after 1,000 actual images were taken, excellent gradation was obtained as with the initial image, and there was no change in sensitivity, and a clear image was obtained. It was confirmed that the repeating characteristics were stable.
【０１０８】[0108]
【発明の効果】上述した様に、本発明においては、上記
ジアミノ化合物は樹脂との相溶性がよく、これを感光層
中含有させることにより、電荷輸送性、繰り返し使用に
対する光疲労が少なく、高感度な感光体を提供すること
ができた。As described above, in the present invention, the above-mentioned diamino compound has good compatibility with the resin, and by containing this in the photosensitive layer, the charge transporting property and the light fatigue due to repeated use are small, and high. It was possible to provide a sensitive photoreceptor.
【図１】 導電性支持体上に電荷発生層および電荷輸送
層を積層してなる機能分離型感光体の概略断面図であ
る。FIG. 1 is a schematic cross-sectional view of a function-separated type photoreceptor in which a charge generation layer and a charge transport layer are laminated on a conductive support.
【図２】 導電性支持体上に電荷輸送層および電荷発生
層を積層してなる機能分離型感光体の概略断面図であ
る。FIG. 2 is a schematic cross-sectional view of a function-separated type photoconductor in which a charge transport layer and a charge generation layer are laminated on a conductive support.
【図３】 導電性支持体上に感光層を積層してなる分散
型感光体の概略断面図である。FIG. 3 is a schematic cross-sectional view of a dispersion type photoconductor in which a photosensitive layer is laminated on a conductive support.
【図４】 導電性支持体上に感光層および表面保護層を
形成した感光体の概略断面図である。FIG. 4 is a schematic cross-sectional view of a photoconductor in which a photoconductive layer and a surface protective layer are formed on a conductive support.
【図５】 導電性支持体上に中間層および感光層を形成
した感光体の概略断面図である。FIG. 5 is a schematic sectional view of a photoconductor in which an intermediate layer and a photoconductive layer are formed on a conductive support.
１ 導電性支持体 ２ 電荷発生材料 ３ 電荷輸送材料 ４ 感光層 ５ 電荷発生層 ６ 電荷輸送層 ７ 表面保護層 ８ 中間層 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Charge generating material 3 Charge transporting material 4 Photosensitive layer 5 Charge generating layer 6 Charge transporting layer 7 Surface protective layer 8 Intermediate layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 237/36 307/52 307/91 311/82 313/14 333/20 333/36 333/76 409/14 ２３７ ３０７ 521/00 Ｃ０９Ｂ 17/00 57/00 Ｎ Ｐ Ｚ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07D 237/36 307/52 307/91 311/82 313/14 333/20 333/36 333/76 409/14 237 307 521/00 C09B 17/00 57/00 N P Z
Claims (1)
されるジアミノ化合物含有する感光層を有する電子写真
感光体。 【化１】 [式中、Ａr1およびＡr2は、それぞれ置換基を有しても
よいアルキル基、アラルキル基、アリール基または複素
環式基を示す。Ｒ1、Ｒ2、Ｒ3およびＲ4はそれぞれ水素
原子、アルキル基、アルコキシ基またはハロゲン原子を
表す。Ｘは−Ｏ−、−Ｓ−、−(Ｒ5)Ｃ(Ｒ6)−、−Ｎ
(Ｒ7)−、−Ｎ＝Ｎ−、−Ｃ2Ｈ4−または−ＣＨ＝ＣＨ
−を表わす。但し、Ｒ5、Ｒ6およびＲ7はそれぞれ水素
原子、それぞれ置換基を有してもよいアルキル基または
アリール基を表わす。Ｙは−ＣＨ2−、−Ｃ2Ｈ4−また
は−ＣＨ＝ＣＨ−を表わす。]1. An electrophotographic photoreceptor having a photosensitive layer containing a diamino compound represented by the following general formula [I] on a conductive support. [Chemical 1] [In the formula, Ar 1 and Ar 2 each represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group which may have a substituent. R 1 , R 2 , R 3 and R 4 each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. X is -O -, - S -, - (R 5) C (R 6) -, - N
(R 7) -, - N = N -, - C 2 H 4 - or -CH = CH
Represents-. However, R 5 , R 6 and R 7 each represent a hydrogen atom or an alkyl group or aryl group which may have a substituent. Y is -CH 2 -, - C 2 H 4 - or represents a -CH = CH-. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6081594A JPH07287408A (en) | 1994-04-20 | 1994-04-20 | Electrophotographic photoreceptor using novel diamino compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6081594A JPH07287408A (en) | 1994-04-20 | 1994-04-20 | Electrophotographic photoreceptor using novel diamino compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07287408A true JPH07287408A (en) | 1995-10-31 |
Family
ID=13750650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6081594A Pending JPH07287408A (en) | 1994-04-20 | 1994-04-20 | Electrophotographic photoreceptor using novel diamino compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07287408A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10310574A (en) * | 1997-05-09 | 1998-11-24 | Minolta Co Ltd | Novel amino compound, its production and use |
| WO2002020460A1 (en) * | 2000-09-05 | 2002-03-14 | Idemitsu Kosan Co., Ltd. | Novel arylamine compounds and organic electroluminescent devices |
| WO2007125714A1 (en) | 2006-04-26 | 2007-11-08 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative, and organic electroluminescence element using the same |
| WO2008023549A1 (en) | 2006-08-23 | 2008-02-28 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivatives and organic electroluminescent devices made by using the same |
| WO2009020095A1 (en) | 2007-08-06 | 2009-02-12 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescent device using the same |
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-
1994
- 1994-04-20 JP JP6081594A patent/JPH07287408A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10310574A (en) * | 1997-05-09 | 1998-11-24 | Minolta Co Ltd | Novel amino compound, its production and use |
| KR100831510B1 (en) * | 2000-09-05 | 2008-05-22 | 이데미쓰 고산 가부시키가이샤 | Novel arylamine compounds and organic electroluminescent devices |
| US6657084B2 (en) * | 2000-09-05 | 2003-12-02 | Idemitsu Kosan Co., Ltd. | Arylamine compound and organic electroluminescence device |
| EP1219590A4 (en) * | 2000-09-05 | 2006-03-29 | Idemitsu Kosan Co | Novel arylamine compounds and organic electroluminescent devices |
| US7081550B2 (en) | 2000-09-05 | 2006-07-25 | Idemitsu Kosan Co., Ltd. | Arylamine compound and organic electroluminescence device |
| WO2002020460A1 (en) * | 2000-09-05 | 2002-03-14 | Idemitsu Kosan Co., Ltd. | Novel arylamine compounds and organic electroluminescent devices |
| WO2007125714A1 (en) | 2006-04-26 | 2007-11-08 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative, and organic electroluminescence element using the same |
| US8044222B2 (en) | 2006-08-23 | 2011-10-25 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivatives and organic electroluminescent device using same |
| WO2008023759A1 (en) | 2006-08-23 | 2008-02-28 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivatives and organic electroluminescence devices using the same |
| WO2008023549A1 (en) | 2006-08-23 | 2008-02-28 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivatives and organic electroluminescent devices made by using the same |
| WO2009020095A1 (en) | 2007-08-06 | 2009-02-12 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescent device using the same |
| WO2010016405A1 (en) * | 2008-08-07 | 2010-02-11 | 出光興産株式会社 | Novel aromatic amine derivative and organic electroluminescence element using the same |
| WO2011136484A1 (en) * | 2010-04-30 | 2011-11-03 | Rohm And Haas Electronic Materials Korea Ltd. | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| US8475984B1 (en) * | 2011-12-22 | 2013-07-02 | Fuji Xerox Co., Ltd. | Image holding member for image forming apparatus, process cartridge, and image forming apparatus |
| WO2018061409A1 (en) * | 2016-09-27 | 2018-04-05 | 保土谷化学工業株式会社 | Sensitizing dye, sensitizing dye for photoelectric conversion and photoelectric transducer using same, and dye-sensitized solar cell |
| JPWO2018061409A1 (en) * | 2016-09-27 | 2019-07-04 | 保土谷化学工業株式会社 | Sensitizing dye, sensitizing dye for photoelectric conversion, photoelectric conversion device using the same, and dye-sensitized solar cell |
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