JP2852464B2 - Electrophotographic photoreceptor - Google Patents

Electrophotographic photoreceptor

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Publication number
JP2852464B2
JP2852464B2 JP25472490A JP25472490A JP2852464B2 JP 2852464 B2 JP2852464 B2 JP 2852464B2 JP 25472490 A JP25472490 A JP 25472490A JP 25472490 A JP25472490 A JP 25472490A JP 2852464 B2 JP2852464 B2 JP 2852464B2
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JP
Japan
Prior art keywords
carrier
layer
present
pigments
polymer compound
Prior art date
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JP25472490A
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Japanese (ja)
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JPH04133066A (en
Inventor
平野  明
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Konica Minolta Inc
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Konica Minolta Inc
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  • Photoreceptors In Electrophotography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は電子写真感光体に関し、更に詳しくはキャリ
ア輸送物質として光導電性高分子化合物を含有する電子
写真感光体に関する。
Description: TECHNICAL FIELD The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member containing a photoconductive polymer compound as a carrier transporting substance.

[従来の技術] 従来、電子写真感光体としては、セレン、酸化亜鉛、
硫化カドミウム、シリコン等の無機光導電性化合物を主
成分とする感光層を有する無機感光体が、広く用いられ
てきた。しかし、これらは感度、熱安定性、耐湿性、耐
久性等において必ずしも満足し得るものではない。例え
ば、セレンは結晶化すると感光体としての特性が劣化し
てしまうため製造上も難しく、また熱や指紋等が原因と
なり結晶化し、感光体としての性能が劣化してしまう。
また硫化カドミウムでは耐湿性や耐久性について、酸化
亜鉛では耐久性等に問題がある。
[Prior Art] Conventionally, selenium, zinc oxide,
Inorganic photoreceptors having a photosensitive layer containing an inorganic photoconductive compound such as cadmium sulfide or silicon as a main component have been widely used. However, these are not always satisfactory in sensitivity, thermal stability, moisture resistance, durability and the like. For example, when selenium is crystallized, its characteristics as a photoreceptor are deteriorated, so that it is difficult to manufacture, and selenium is crystallized due to heat, fingerprints and the like, and the performance as a photoreceptor is deteriorated.
Cadmium sulfide has a problem in moisture resistance and durability, and zinc oxide has a problem in durability and the like.

これら無機感光体の持つ欠点を克服する目的で様々な
有機光導電性化合物を主成分とする感光層を有する有機
感光体の研究・開発が近年盛んに行われている。
In recent years, research and development of organic photoconductors having a photosensitive layer containing various organic photoconductive compounds as main components have been actively conducted in order to overcome the disadvantages of the inorganic photoconductors.

このような有機感光体は、焼却が可能であり、無公害
の利点を有し、更に多くのものは塗工により薄膜形成が
可能で大量生産が容易である。それ故にコストが大幅に
低下でき、又、用途に応じて様々な形状に加工する事が
できるという長所を有している。しかしながら、有機感
光体においては、その感度、耐久性に問題が残されてお
り、高感度、高耐久性の有機感光体の出現が強く望まれ
ている。このような点を改良するため、キャリア発生機
能とキャリア輸送機能とを異なる物質にそれぞれ分担さ
せ、より高性能の有機感光体を開発する試みがなされて
いる。このようないわゆる機能分離型の感光体の形態と
しては単層型と積層型の2種類があり、両者ともそれぞ
れの材料を広い範囲から選択することができ、任意の性
能を有する感光体を比較的容易に作成し得ることから多
くの研究がなされてきた。このような機能分離型感光
体、特に積層型感光体において、キャリヤー輸送層に用
いられるキャリヤー輸送物質としては、キャリヤー発生
層からの電荷の注入効率が大きく、更にキャリヤー輸送
層内で電荷の移動度が大である化合物を選定する必要が
ある。そのためには、イオン化ポテンシャルが小さい化
合物、ラジカルカチオンが発生しやすい化合物が選ばれ
るが、中でもトリアリールアミン誘導体(特開昭53−47
260号公報)、ヒドラゾン誘導体(特開昭57−101844号
公報)、オキサジアゾール誘導体(特公昭34−5466号公
報)、ピラゾリン誘導体(特公昭52−4188号公報)、ス
チルベン誘導体(特開昭58−198043号公報)、トリフェ
ニルメタン誘導体(特公昭45−555号公報)等の低分子
化合物が従来よく用いられている。
Such organic photoreceptors can be incinerated and have no pollution, and many of them can be formed into a thin film by coating and are easily mass-produced. Therefore, it has the advantages that the cost can be greatly reduced and that it can be processed into various shapes depending on the application. However, the sensitivity and durability of the organic photoreceptor still have problems, and the appearance of an organic photoreceptor having high sensitivity and high durability has been strongly desired. In order to improve such a point, an attempt has been made to develop a higher performance organic photoreceptor by assigning a carrier generation function and a carrier transport function to different substances, respectively. There are two types of photoreceptors of such a so-called function-separated type, a single-layer type and a laminated type. Both types can select a material from a wide range, and compare photoreceptors having arbitrary performance. Much research has been done because they can be easily created. In such a function-separated type photoreceptor, in particular, a stacked type photoreceptor, the carrier transporting material used in the carrier transporting layer has a high charge injection efficiency from the carrier generating layer, and further has a charge mobility in the carrier transporting layer. Needs to be selected. For this purpose, a compound having a small ionization potential and a compound in which a radical cation is easily generated are selected.
No. 260), hydrazone derivatives (JP-A-57-101844), oxadiazole derivatives (JP-B-34-5466), pyrazoline derivatives (JP-B-52-4188), and stilbene derivatives (JP-A-52-4188). Low molecular weight compounds such as 58-198043) and triphenylmethane derivatives (Japanese Patent Publication No. 45-555) have been conventionally used.

このようなキャリヤー輸送層は多くの場合、ポリカー
ボネート、ポリエステル等の高分子フィルム形成性バイ
ンダー中に分散または溶解された前記の如き低分子化合
物を含む。一般に、輸送層内の高分子フィルム形成性バ
インダーはそれ自体電気的に不活性であり、キャリヤー
輸送物質を含有したときに電気的に活性となる。
Such carrier transport layers often include such low molecular weight compounds dispersed or dissolved in a polymeric film forming binder such as polycarbonate, polyester, and the like. Generally, the polymeric film-forming binder in the transport layer is itself electrically inactive and becomes electrically active when it contains a carrier transport material.

[発明が解決しようとする課題] しかしながら、上記の如き低分子化合物の添加はポリ
マー系のガラス転移温度を著しく低下させ、種々の電子
写真プロセスにおける感光層の傷や感光体自体の変形等
機械的強度低下の原因となるのみならず、電荷輸送性能
の向上を目的として低分子化合物の添加量増大をはかっ
た場合、該低分子化合物のポリマー中での結晶化による
析出、相分離等を引きおこし、この結果、更に感光体の
機械的強度や感度が低下する等の問題を有していた。
[Problems to be Solved by the Invention] However, the addition of the low-molecular compound as described above significantly lowers the glass transition temperature of the polymer system, and causes mechanical damage such as damage to the photosensitive layer and deformation of the photosensitive member itself in various electrophotographic processes. Not only does this cause a decrease in strength, but when the amount of the low-molecular compound is increased for the purpose of improving the charge transport performance, precipitation of the low-molecular compound by crystallization in the polymer, phase separation, etc. are caused. As a result, there is a problem that the mechanical strength and sensitivity of the photoreceptor are further reduced.

従って本発明の目的は、結晶析出や相分離がなく、優
れた機械的強度及び光導電性を有する電子写真感光体を
提供することにある。
Accordingly, it is an object of the present invention to provide an electrophotographic photoreceptor having excellent mechanical strength and photoconductivity without crystal precipitation or phase separation.

[課題を解決するための手段] 本発明者等は前記課題に鑑みて、鋭意研究の結果、本
発明の上記目的は、下記構造単位(I),(II)及び
(III)の少なくとも1つを含む繰り返し単位を少なく
とも1種有する高分子化合物を含有する電子写真感光体
を提供することにより達成されることを見出した。
[Means for Solving the Problems] In view of the above problems, the present inventors have conducted intensive studies and as a result, have found that the above object of the present invention is at least one of the following structural units (I), (II) and (III) It has been found that this is achieved by providing an electrophotographic photosensitive member containing a polymer compound having at least one repeating unit containing

[式中、R1,R2,R3,R4及びR5は各々アルキル基又はアル
コキシ基を表わし、n1及びn3は各々1〜5の整数を、
n2,n4及びn5は各々1〜4の整数を表わす。また、l,m及
びpはそれぞれ0より大きく、1以下の数を表わす。] 以下に本発明を更編に詳細に説明する。
[Wherein, R 1 , R 2 , R 3 , R 4 and R 5 each represent an alkyl group or an alkoxy group, and n 1 and n 3 each represent an integer of 1 to 5,
n 2 , n 4 and n 5 each represent an integer of 1 to 4. Further, l, m and p each represent a number greater than 0 and 1 or less. Hereinafter, the present invention will be described in further detail.

本発明に用いられる上記構造単位の少なくとも1つを
含む繰り返し単位を少なくとも1種有する高分子化合物
(以下、本発明の高分子化合物と称す)は、単一の繰り
返し単位からなるホモポリマーも、上記構造単位(I)
〜(III)の少なくとも1つを含み、かつお互いに異な
る二種以上の繰り返し単位からなる共重合体も好ましく
包含しうる。更に、これらの繰返し単位と他の重合可能
なモノマーとの共重合体も含まれる。これらは二次元的
あるいは三次元網目構造を有するものも含む。
The polymer compound having at least one repeating unit containing at least one of the structural units used in the present invention (hereinafter, referred to as the polymer compound of the present invention) may be a homopolymer composed of a single repeating unit, Structural unit (I)
A copolymer containing at least one of (III) to (III) and comprising two or more kinds of repeating units different from each other can also be preferably included. Furthermore, copolymers of these repeating units and other polymerizable monomers are also included. These include those having a two-dimensional or three-dimensional network structure.

本発明の高分子化合物としては、構造単位(II)を含
むものが好ましく用いられる。
As the polymer compound of the present invention, those containing the structural unit (II) are preferably used.

本発明の高分子化合物中には上記構造単位(I)〜
(III)の少なくとも一つが50〜100モル%含まれること
が好ましい。
In the polymer compound of the present invention, the above structural units (I) to (I)
It is preferable that at least one of (III) is contained in 50 to 100 mol%.

また、本発明の高分子化合物は分子量として、数平均
分子量で3,000〜3,000,000、更に10,000〜1,000,000で
あることが好ましい。
Further, the polymer compound of the present invention preferably has a number average molecular weight of 3,000 to 3,000,000, and more preferably 10,000 to 1,000,000, in terms of molecular weight.

本発明において前記構造単位(I)〜(III)の各々
において、N原子に結合する三つのフェニル基はいずれ
も置換基R1〜R5のいずれかを有することができる。この
ような置換基としてはメチル基等のアルキル基、メトキ
シ基等のアルコキシ基が挙げられる。また、n1個のR1
n2個のR2、n3個のR3、n4個のR4及びn5個のR5はそれぞれ
同一でも異なっていてもよい。
In the present invention, in each of the structural units (I) to (III), any of the three phenyl groups bonded to the N atom can have any of the substituents R 1 to R 5 . Examples of such a substituent include an alkyl group such as a methyl group and an alkoxy group such as a methoxy group. Also, n 1 R 1 ,
n 2 R 2 , n 3 R 3 , n 4 R 4 and n 5 R 5 may be the same or different.

本発明の高分子化合物は更に前述の如く他の重合可能
なモノマーとの共重合体も含むが、このような重合可能
なモノマーとしては、例えばメタクリ酸メチル、メタク
リル酸エチル、メタクリル酸ブチル等のメタクリル酸エ
ステルモノマー、アクリル酸メチル、アクリル酸ブチル
等のアクリル酸エステルモノマー、スチレン系モノマ
ー、アクリロニトリル等が挙げられる。
The polymer compound of the present invention further includes a copolymer with another polymerizable monomer as described above. Examples of such a polymerizable monomer include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Examples include methacrylate monomers, acrylate monomers such as methyl acrylate and butyl acrylate, styrene monomers, and acrylonitrile.

本発明の高分子化合物としては構造単位(I)とメタ
クリル酸メチルを好ましくは1:1の割合で含有するもの
が好ましく用いられる。
As the polymer compound of the present invention, those containing the structural unit (I) and methyl methacrylate preferably in a ratio of 1: 1 are preferably used.

以下に本発明の高分子化合物の具体例を例示する。 Hereinafter, specific examples of the polymer compound of the present invention will be described.

以下に上記本発明の高分子化合物の合成例を挙げる
が、他の本発明の高分子化合物もこれら合成例に準じて
合成することができる。
The synthesis examples of the polymer compound of the present invention are described below, but other polymer compounds of the present invention can also be synthesized according to these synthesis examples.

合成例1:本発明の高分子化合物(2−1)の合成 4−ヒドロキシトリフェニルアミン2g(7.7ミリモ
ル)を100ml4つロフラスコに入れ、脱水したDMF40mlを
加え溶解させた。水素化ナトリウム0.37g(7.7ミリモ
ル)を加え固形物がなくなるまで撹拌した。反応容器を
氷浴上に移しい5℃まで冷却し、クロロメチルスチレン
1.18g(7.7ミリモル)を滴下した。5℃で2時間反応さ
せた後、室温で一晩反応させた。反応液を200mlのイオ
ン交換水中に注ぎトルエンで抽出した。トルエン溶液
は、イオン交換水で水層が中性になるまで洗浄した。減
圧下でトルエンを除去し得られた赤褐色オイル状物質を
トルエン/ヘキサン=2/1混合溶媒に溶解させシリカゲ
ルを用いて精製した。溶媒を除去いて黄色オイル状物質
を得た。(収量2g,収率70%) メチルスチリル4−(N,N−ジフェニルアミノ)−フ
ェニルエーテル11.72g(0.031モル)、メタクリル酸メ
チル3.11g(0.031モル)、AIBN0.31g(0.0019モル)を
重合用アンプルに入れトルエンで50mlとした後、脱気
し、封管した。重合温度60℃、反応時間2時間で重合し
た。重合終了後、直ちに冷水中でアンプルを冷やし、開
封してクロロホルムを加え、20倍量のメタノール中に滴
下した。再沈澱を2度行って目的物を得た。(乾燥重量
3.1g,収率20.9%) 得られたポリマー中におけるトリフェニルアミンの割
合は75重量%であった。また、分子量は1×105であっ
た。
Synthesis Example 1: Synthesis of Polymer Compound (2-1) of the Present Invention 2-hydroxytriphenylamine (2 g, 7.7 mmol) was placed in a 100 ml four-necked flask, and 40 ml of dehydrated DMF was added and dissolved. 0.37 g (7.7 mmol) of sodium hydride was added and the mixture was stirred until there was no solid matter. Transfer the reaction vessel to an ice bath and cool to 5 ° C.
1.18 g (7.7 mmol) were added dropwise. After reacting at 5 ° C. for 2 hours, the reaction was carried out at room temperature overnight. The reaction solution was poured into 200 ml of deionized water and extracted with toluene. The toluene solution was washed with ion-exchanged water until the aqueous layer became neutral. The reddish brown oily substance obtained by removing toluene under reduced pressure was dissolved in a mixed solvent of toluene / hexane = 2/1 and purified using silica gel. Removal of the solvent gave a yellow oil. (2 g, 70% yield) Polymerization of methylstyryl 4- (N, N-diphenylamino) -phenyl ether 11.72 g (0.031 mol), methyl methacrylate 3.11 g (0.031 mol), AIBN 0.31 g (0.0019 mol) The mixture was placed in an ampoule for use, adjusted to 50 ml with toluene, degassed, and sealed. Polymerization was performed at a polymerization temperature of 60 ° C. and a reaction time of 2 hours. Immediately after the polymerization was completed, the ampoule was cooled in cold water, opened, added with chloroform, and added dropwise to a 20-fold amount of methanol. Reprecipitation was performed twice to obtain the desired product. (Dry weight
(3.1 g, yield: 20.9%) The proportion of triphenylamine in the obtained polymer was 75% by weight. The molecular weight was 1 × 10 5 .

合成例2:本発明の高分子化合物(3−1)の合成 4,4′−ジヒドロキシトリフェニルアミン10g(0.036
モル)をDMSO300mlに溶解し、水素化ナトリウム(50%
ミリモル)1.9gを添加し、撹拌した。反応容器を5%ま
で冷却し、クロロメチルスチレン11.95g(0.079モル)
を滴下した。5℃で2時間反応させた後、室温で一晩反
応させた。反応液を200mlのイオン交換水中に注ぎ、オ
イル分をトルエンで抽出した。トルエンを除去して得ら
れた赤褐色オイル成分をトルエン/ヘキサン=2/1溶媒
を用いて精製し、目的モノマーを得た。(収量12.8g,収
率70%) ビス{(メチルスチリル)4−(N,N−ジフェニルア
ミノ)}フェニルエーテル10g(0.02モル)、AIBN0.2g
(0.0012モル)をアンプルに入れトルエンで50mlとした
後、脱気し、封管した。
Synthesis Example 2: Synthesis of polymer compound (3-1) of the present invention 10 g of 4,4'-dihydroxytriphenylamine (0.036
Mol) dissolved in 300 ml of DMSO and sodium hydride (50%
(Mmol) was added and stirred. The reaction vessel was cooled to 5% and chloromethylstyrene 11.95 g (0.079 mol)
Was added dropwise. After reacting at 5 ° C. for 2 hours, the reaction was carried out at room temperature overnight. The reaction solution was poured into 200 ml of deionized water, and the oil was extracted with toluene. The reddish-brown oil component obtained by removing toluene was purified using a toluene / hexane = 2/1 solvent to obtain a target monomer. (Yield 12.8 g, 70% yield) Bis {(methylstyryl) 4- (N, N-diphenylamino)} phenyl ether 10 g (0.02 mol), AIBN 0.2 g
(0.0012 mol) was placed in an ampoule, made up to 50 ml with toluene, degassed, and sealed.

合成例1と同様の方法で重合を行ない目的物を得た。
(収量2.0g,収率20%) 得られたポリマー中におけるトリフェニルアミンの割
合は47.7重量%であり、分子量は2×105であった。
Polymerization was carried out in the same manner as in Synthesis Example 1 to obtain the desired product.
(Yield 2.0 g, yield 20%) The ratio of triphenylamine in the obtained polymer was 47.7% by weight, and the molecular weight was 2 × 10 5 .

合成例3:本発明の高分子化合物(5−1)の合成 4,4′,4″−トリヒドロキシトリフェニルアミン5gを1
00ml4つロフラスコに入れ、脱水DMF40mlを加え溶解させ
た。水素化ナトリウム1.47gを加え撹拌した。5℃まで
冷却し、クロロメチルスチレン9.37gを加え2時間反応
させ、その後一晩室温で反応させた。
Synthesis Example 3: Synthesis of polymer compound (5-1) of the present invention 5 g of 4,4 ', 4 "-trihydroxytriphenylamine was added to 1 g of
The flask was placed in a 00 ml four-necked flask, and 40 ml of dehydrated DMF was added to dissolve. 1.47 g of sodium hydride was added and stirred. After cooling to 5 ° C., 9.37 g of chloromethylstyrene was added and reacted for 2 hours, and then reacted overnight at room temperature.

反応液を200mlイオン交換水に注ぎ、トルエンで抽出
した。トルエン溶液を水洗し、その後トルエンを除去し
た。オイル状物質を精製し、目的のモノマーを得た。
(収率60%) 得られたモノマー5gとAIBN3.05gをトルエン溶液に溶
解し、100℃で反応させた。得られたポリマーをさらに
トルエンに溶解し、AIBN0.92gを加えて、Al基体上にジ
ブロモアンスアンソロン(2Y)を蒸着した基板上に塗布
し、90℃で反応させ目的ポリマーを得た。
The reaction solution was poured into 200 ml of ion-exchanged water and extracted with toluene. The toluene solution was washed with water, and then the toluene was removed. The oily substance was purified to obtain the desired monomer.
(Yield: 60%) 5 g of the obtained monomer and 3.05 g of AIBN were dissolved in a toluene solution and reacted at 100 ° C. The obtained polymer was further dissolved in toluene, 0.92 g of AIBN was added, and the solution was applied on a substrate on which dibromoanthanelone (2Y) was deposited on an Al substrate, and reacted at 90 ° C. to obtain a target polymer.

上記本発明の高分子化合物は感光層中に好ましくは40
〜100重量%、更に好ましくは60〜100重量%含有され
る。
The polymer compound of the present invention is preferably present in the photosensitive layer in an amount of 40.
-100% by weight, more preferably 60-100% by weight.

本発明の電子写真感光体において、使用可能なキャリ
ヤー発生物質としては、例えば電磁波を吸収してフリー
キャリアを発生するものであれば、無機顔料及び有機顔
料の何れも用いることができる。
In the electrophotographic photoreceptor of the present invention, any of inorganic pigments and organic pigments can be used as a usable carrier-generating substance, as long as the substance generates free carriers by absorbing electromagnetic waves.

このようなキャリヤー発生物質(CGM)としては以下
のものが例示される。
Examples of such a carrier generating substance (CGM) include the following.

(1)無定型セレン、三方晶系セレン、セレン−砒素合
金、セレン−テルル合金、硫化カドミウム、セレン化カ
ドミウム、硫セレン化カドミウム、硫化水銀、硫化鉛、
酸化亜鉛、酸化チタン無定型シリコン等の無機顔料 (2)モノアゾ顔料、ポリアゾ顔料、金属錯塩アゾ顔
料、ピラゾロンアゾ顔料、スチルベンアゾ及びチアゾー
ルアゾ顔料等のアゾ系顔料 (3)アントラキノン誘導体、アントアントロン誘導
体、ジベンズピレンキノン誘導体、ビラントロン誘導
体、ビオラントロン誘導体及びイソビオラントロン誘導
体等のアントラキノン系又は多環キノン系顔料 (4)インジゴ誘導体及びチオインジゴ誘導体等のイン
ジゴイド系顔料 (5)チタニルフタロシアニン、バナジルフタオロシア
ニン等の各種金属フタロシアニン、及びα型、β型、γ
型、τ型、τ′型、η型、η′型等の無金属フタロシア
ニン等のフタロシアニン系顔料 (6)ジフェニルメタン系顔料、トリフェニルメタン顔
料、キサンテン顔料及びアクリジン顔料等のカルボニウ
ム系顔料 (7)アジン顔料、オキサジン顔料及びチアジン顔料等
のキノンイミン系顔料 (8)シアニン顔料及びアゾメチン顔料等のメチン系顔
料 (9)キノリン系顔料 (10)ニトロ系顔料 (11)ニトロソ系顔料 (12)ベンゾキノン及びナフトキノン系顔料 (13)ナフタルイミド系顔料 (14)ビスベンズイミダゾール誘導体等のペリノン系顔
料 (15)フルオレノン系顔料 (16)スクアリリウム顔料 (17)アズレニウム化合物 更に、好ましいアゾ化合物、多環キノン系顔料の例に
ついて示す。これら化合物の具体例については特願昭60
−298013号明細書等に詳細に記載されている。
(1) amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium sulfate selenide, mercury sulfide, lead sulfide,
Inorganic pigments such as zinc oxide and titanium oxide amorphous silicon (2) Azo pigments such as monoazo pigments, polyazo pigments, metal complex azo pigments, pyrazolone azo pigments, stilbene azo and thiazole azo pigments (3) Anthraquinone derivatives, anthantrone derivatives , Anthraquinone-based or polycyclic quinone-based pigments such as dibenzpyrenequinone derivatives, vilanthrone derivatives, biolanthrone derivatives and isobiolanthrone derivatives; (4) indigoid-based pigments such as indigo derivatives and thioindigo derivatives; (5) titanyl phthalocyanine, vanadyl phthalocyanine Various metal phthalocyanines such as nin, and α-type, β-type, γ
-Type, τ-type, τ'-type, η-type, η'-type, etc., phthalocyanine-based pigments such as non-metallic phthalocyanine (6) diphenylmethane-based pigments, triphenylmethane-based pigments, xanthene pigments, and acridine-based pigments (7) Quinone imine pigments such as azine pigments, oxazine pigments and thiazine pigments (8) Methine pigments such as cyanine pigments and azomethine pigments (9) Quinoline pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and naphthoquinone (13) Naphthalimide pigments (14) Perinone pigments such as bisbenzimidazole derivatives (15) Fluorenone pigments (16) Squarylium pigments (17) Azurenium compounds Further preferred examples of azo compounds and polycyclic quinone pigments It shows about. For specific examples of these compounds, see
-298013 and the like.

[但し、上記各一般式中、 Ar1,Ar2及びAr3:それぞれ、置換若しくは未置換の炭
素環式芳香環基、 R1,R2,R3及びR4:それぞれ、電子吸引性基又は水素原
子であって、R1〜R4の少なくとも1つはシアノ基等の電
子吸引性基、 (Xは、ヒドロキシ基、 −NHSO2+−R8(但し、R6及びR7はそれぞれ、水素原子
又は置換若しくは未置換のアルキル基、R8は置換若しく
は未置換のアルキル基または置換若しくは未置換のアリ
ール基)、 Yは、水素原子、ハロゲン原子、置換若しくは未置換
のアルキル基、アルコキシ基、カルボキシル基、スルホ
基、置換若しくは未置換のカルバモイル基または置換若
しくは未置換のスルファモイル基(但し、mが2以上の
ときは、互いに異なる基であってもよい。)、 Zは、置換若しくは未置換の炭素環式芳香族環または
置換若しくは未置換の複素環式芳香族環を構成するのに
必要な原子群、 R5は、水素原子、置換若しくは未置換のアミノ基、置
換若しくは未置換のカルバモイル基、カルボキシル基ま
たはそのエステル基、 Ar4は、置換若しくは未置換のアリール基、 nは、1または2の整数、 mは、0〜4の整数である。)] また、次の一般式[II]群の多環キノン顔料もCGMと
して使用できる。
[However, in each of the above general formulas, Ar 1 , Ar 2 and Ar 3 : a substituted or unsubstituted carbocyclic aromatic ring group, R 1 , R 2 , R 3 and R 4 : an electron withdrawing group, respectively Or a hydrogen atom, and at least one of R 1 to R 4 is an electron-withdrawing group such as a cyano group; (X is a hydroxy group, —NHSO 2 + −R 8 (where R 6 and R 7 are each a hydrogen atom or a substituted or unsubstituted alkyl group, R 8 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group), Y Is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxyl group, a sulfo group, a substituted or unsubstituted carbamoyl group or a substituted or unsubstituted sulfamoyl group (provided that when m is 2 or more, , may be different from each other group.), Z is atomic group necessary to configure a substituted or unsubstituted carbocyclic aromatic ring or a substituted or unsubstituted heterocyclic aromatic ring, R 5 Is a hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a carboxyl group or its ester group, and Ar 4 is a substituted or unsubstituted aryl A group, n is an integer of 1 or 2, and m is an integer of 0-4. )] Further, polycyclic quinone pigments of the following general formula [II] group can also be used as CGM.

(但し、この一般式中、X′はハロゲン原子、ニトロ
基、シアノ基、アシル基又はカルボキシル基を表わし、
pは0〜4の整数、qは0〜6の整数を表わす。
(However, in this general formula, X ′ represents a halogen atom, a nitro group, a cyano group, an acyl group or a carboxyl group;
p represents an integer of 0 to 4, and q represents an integer of 0 to 6.

スクアリリウム顔料については特開昭60−258550号公
報等に記載がある。
The squarylium pigment is described in JP-A-60-258550.

チタニルフアロシアニンについては特願昭62−241983
号明細書に記載がある。
Japanese Patent Application No. 62-241983 for titanyl phthalocyanine
There is a description in the specification.

アズレニウム化合物については、特願昭62−251188号
明細書に記載がある。
The azurenium compound is described in Japanese Patent Application No. 62-251188.

更に、特殊な無金属フタロシアニンについて、特願昭
61−295784号明細書等に記載がある。
Furthermore, regarding special metal-free phthalocyanine,
It is described in the specification of 61-295784 and the like.

本発明の高分子化合物は優れた光導電性を有し、これ
を含む感光層を導電性支持体上に設けることにより本発
明の電子写真感光体を製造するこができる。本発明の高
分子化合物は、その優れたキャリア輸送能を利用して、
これをキャリア輸送物質として用い、これと組み合わせ
て有効に作用し得る前記の如きキャリア発生物質を共に
用いることにより、いわゆる機能分離型の感光体とする
ことができる。前記機能分離型感光体は前記両物質の混
合分散型のものであってもよいが、キャリア発生層と、
キャリア輸送層とを積層した積層型感光体とすることが
より好ましい。
The polymer compound of the present invention has excellent photoconductivity, and the electrophotographic photoreceptor of the present invention can be produced by providing a photosensitive layer containing the same on a conductive support. The polymer compound of the present invention utilizes its excellent carrier transport ability,
A so-called function-separated type photoreceptor can be obtained by using this as a carrier transporting substance and using the above-mentioned carrier generating substance which can work effectively in combination with this. The function-separated type photoreceptor may be a mixed dispersion type of the two substances, but a carrier generation layer,
It is more preferable to form a laminated photoconductor in which a carrier transport layer is laminated.

尚、積層構成の感光層の場合キャリア発生層は入射光
量の大部分が電荷発生層で吸収されて多くの電荷発生キ
ャリアを生成すると共に発生した電荷キャリアを再結合
や捕獲(トラップ)により失活することなくキャリア輸
送層に注入するために光キャリアを生成するのに十分な
膜厚の範囲でできる限り薄膜層とすることが好ましい。
In the case of a laminated photosensitive layer, most of the incident light is absorbed by the charge generation layer to generate a large amount of charge generation carriers, and the generated charge carriers are deactivated by recombination or trapping. It is preferable to use a thin film layer as far as possible within a range of a film thickness sufficient to generate photocarriers for injecting into the carrier transport layer without performing.

またキャリア輸送層は前述のキャリア発生層と電気的
に接合されており、電界の存在下で電荷発生層から注入
された電荷キャリアを表面まで輸送できる機能を有して
いる。
The carrier transport layer is electrically connected to the above-described carrier generation layer, and has a function of transporting charge carriers injected from the charge generation layer to the surface in the presence of an electric field.

また単層構成の機能分離型感光体においては、単層で
光キャリアの発生及び輸送を行うもので層内でキャリア
発生物質とキャリア輸送物質が電気的に結合されている
か、かつ/またはキャリア発生物質もキャリアの輸送に
寄与するものである。
In a single-layer function-separated type photoreceptor, photocarriers are generated and transported in a single layer, and the carrier-generating substance and the carrier-transporting substance are electrically coupled in the layer, and / or the carrier is generated. Substances also contribute to carrier transport.

また、キャリア発生層にキャリア発生物質とキャリア
輸送物質の一部の両方が含有されていてもよい。いずれ
の層構成においても、感光層の上に保護層を設けても良
く、また支持体と感光層の間にバリア機能と接着性を持
つ下引層(中間層)を設けても良い。
Further, the carrier generation layer may contain both the carrier generation material and a part of the carrier transport material. In any of the layer configurations, a protective layer may be provided on the photosensitive layer, or an undercoat layer (intermediate layer) having a barrier function and adhesiveness may be provided between the support and the photosensitive layer.

感光層、保護層、下引層に使用可能なバインダー樹脂
としては、例えばポリスチレン、ポリエチレン、ポリプ
ロピレン、アクリル樹脂、メタクリル樹脂、塩化ビニル
樹脂、酢酸ビニル樹脂、ポリビニルブチラール樹脂、エ
ポキシ樹脂、ポリウレタン樹脂、フェノール樹脂、ポリ
エステル樹脂、アルキッド樹脂、ポリカーボネート樹
脂、シリコン樹脂、メラミン樹脂、等の付加重合型樹
脂、重付加型樹脂、重縮合型樹脂、並びにこれらの樹脂
の繰り返し単位のうち2つ以上を含む共重合体樹脂等が
挙げられる。またこれらの絶縁性樹脂の他、ポリ−N−
ビニルカルバゾール等の高分子有機半導体が挙げられ
る。
Examples of the binder resin usable for the photosensitive layer, the protective layer, and the undercoat layer include polystyrene, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, and phenol. Resins, polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, etc., addition polymerization type resins, polyaddition type resins, polycondensation type resins, and copolymers containing two or more of the repeating units of these resins Coalescing resin and the like. In addition to these insulating resins, poly-N-
High molecular organic semiconductors such as vinyl carbazole are exemplified.

又、感光層中にはキャリア発生物質のキャリア発生機
能を改善する目的で有機アミン類を添加することがで
き、特に2級アミンを添加するのが好ましい。かかる有
機アミンの添加量としては、キャリア発生物質に対して
該キャリア発生物質の1倍以下、好ましくは0.2倍〜0.0
05倍の範囲のモル数とするのがよい。
Organic amines can be added to the photosensitive layer for the purpose of improving the carrier generation function of the carrier generation substance, and it is particularly preferable to add a secondary amine. The amount of the organic amine to be added is 1 time or less of the carrier generating substance, preferably 0.2 to 0.0 times the carrier generating substance.
The number of moles should be in the range of 05 times.

又、上記感光層においては、オゾン劣化防止の目的で
ヒンダードフェノール類、ヒンダードアミン類、パラフ
ェニレンジアミン類、ハイドロキノン類、有機燐化合物
類等の酸化防止剤を添加することができる。
In the above-mentioned photosensitive layer, antioxidants such as hindered phenols, hindered amines, paraphenylenediamines, hydroquinones and organic phosphorus compounds can be added for the purpose of preventing ozone deterioration.

これらの化合物はゴム、プラスチック、油脂類等の酸
化防止剤として知られており、市販品を容易に入手でき
る。
These compounds are known as antioxidants for rubbers, plastics, oils and the like, and commercially available products can be easily obtained.

これらの酸化防止剤はキャリア発生層、キャリア輸送
層、又は保護層のいずれに添加されてもよいが、好まし
くはキャリア輸送層に添加される。その場合の酸化防止
剤の添加量はキャリア輸送物質100重量部に対して0.1〜
100重量部、好ましくは1〜50重量部、特に好ましくは
5〜25重量部である。
These antioxidants may be added to any of the carrier generation layer, the carrier transport layer, and the protective layer, but are preferably added to the carrier transport layer. In this case, the amount of the antioxidant to be added is 0.1 to 100 parts by weight of the carrier transporting substance.
100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 5 to 25 parts by weight.

次に前記感光層を支持する導電性支持体としては、ア
ルミニュウム、ニッケルなどの金属板、金属ドラム又は
金属箔をラミネートした、或はアルミニュウム、酸化
錫、酸化インジュウムなどを蒸着したプラスチックフィ
ルムあるいは導電性物質を塗布した紙、プラスチックな
どのフィルム又はドラムを使用することができる。
Next, as the conductive support for supporting the photosensitive layer, a metal plate of aluminum, nickel, or the like, a metal drum or a metal foil laminated, or a plastic film on which aluminum, tin oxide, indium oxide, or the like is deposited, or a conductive film. Films or drums, such as paper, plastic, etc. coated with a substance can be used.

本発明において、キャリア発生層は代表的には前述の
キャリア発生物質を適当な分散媒に単独もしくは適当な
バインダ樹脂と共に分散せしめた分散液を例えばディッ
プ塗布、スプレイ塗布、ブレード塗布、ロール塗布等に
よって支持体若しくは下引層上又はキャリア輸送層上に
塗布して乾燥させる方法により設けることができる。ま
たキャリア発生物質の分散にはボールミル、ホモミキ
サ、サンドミル、超音波分散機、アトライタ等が用いら
れる。
In the present invention, the carrier-generating layer is typically prepared by dispersing the above-mentioned carrier-generating substance alone or in an appropriate dispersion medium together with an appropriate binder resin, for example, by dip coating, spray coating, blade coating, roll coating, or the like. It can be provided by a method of coating and drying on a support, an undercoat layer or a carrier transport layer. A ball mill, a homomixer, a sand mill, an ultrasonic disperser, an attritor, or the like is used for dispersing the carrier generating substance.

キャリア発生物質の分散媒としては、例えばヘキサ
ン、ベンゼン、トルエン、キシレン等の炭化水素類;メ
チレンクロライド、1,2−ジクロルエタン、sym−テトラ
クロルエタン、1,1,2−トリクロルエタン、クロロホル
ム等のハロゲン化炭化水素;アセトン、メチルエチルケ
トン、シクロヘキサノン等のケトン類;酢酸エチル、酢
酸ブチル等のエステル類;メタノール、エタノール、プ
ロパノール、ブタノール、シクロヘキサノール、ヘプタ
ノール、エチレングリコール、メチルセルソルブ、エチ
ルセルソルブ、酢酸セルソルブ等のアルコール類及びこ
の誘導体;テトラヒドロフラン、1,4−ジオキサン、フ
ラン、フルフラール等のエーテル、アセラール類;ピリ
ジンやブチルアミン、ジエチルアミン、エチレンジアミ
ン、イソプロパノールアミン等のアミン類; N,N−ジメチルホルムアミド等のアミド類等の窒素化
合物、その他脂肪酸及びフェノール類、二硫化炭素や燐
酸トリエチル等の硫黄、燐化合物等の1種又は2種以上
を用いることができる。
Examples of the dispersion medium of the carrier-generating substance include hydrocarbons such as hexane, benzene, toluene, and xylene; methylene chloride, 1,2-dichloroethane, sym-tetrachloroethane, 1,1,2-trichloroethane, and chloroform. Halogenated hydrocarbons; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; methanol, ethanol, propanol, butanol, cyclohexanol, heptanol, ethylene glycol, methyl cellosolve, ethyl cellosolve and acetic acid Alcohols such as cellosolve and derivatives thereof; ethers such as tetrahydrofuran, 1,4-dioxane, furan and furfural, acerals; pyridine, butylamine, diethylamine, ethylenediamine, isopropanolamine Nitrogen compounds such as amides such as N, N-dimethylformamide; and one or more kinds of sulfur and phosphorus compounds such as fatty acids and phenols, carbon disulfide and triethyl phosphate, and the like. .

本発明の感光体が積層型構成の場合、キャリア発生層
中のバインダ:キャリア発生物質:キャリア輸送物質の
重量比は0〜100:1〜500:0〜500が好ましい。
When the photoreceptor of the present invention has a laminated structure, the weight ratio of binder: carrier generating substance: carrier transporting substance in the carrier generating layer is preferably from 0 to 100: 1 to 500: 0 to 500.

キャリア発生物質の含有割合がこれより少ないと感度
が低く、残留電位の増加を招き、またこれより多いと暗
減衰及び受容電位が低下する。
If the content of the carrier-generating substance is less than this, the sensitivity is low and the residual potential is increased, and if it is more than this, the dark decay and the receiving potential are reduced.

以上のようにして形成されるキャリア発生層の膜厚
は、好ましくは0.01〜10μm、特に好ましくは0.1〜5
μmである。
The thickness of the carrier generation layer formed as described above is preferably 0.01 to 10 μm, particularly preferably 0.1 to 5 μm.
μm.

本発明においてキャリア輸送層は、本発明の高分子化
合物からなるキャリア輸送物質を単独であるいは上述の
バインダ樹脂と共に溶解分散せしめたものを塗布、乾燥
して形成することができる。用いられる分散媒としては
前記キャリア発生物質の分散において用いた分散媒を用
いることができる。
In the present invention, the carrier transporting layer can be formed by applying and drying a carrier transporting substance comprising the polymer compound of the present invention alone or in a state of being dissolved and dispersed together with the binder resin described above. As the dispersion medium to be used, the dispersion medium used in dispersion of the carrier generating substance can be used.

本発明においては本発明の高分子化合物と共に他のキ
ャリア輸送物質を本発明の目的を損わない範囲で使用す
ることができる。使用可能なキャリア輸送物質として
は、特に制限はないが、例えばオキサゾール誘導体、オ
キサジアゾール誘導体、チアゾール誘導体、チアジアゾ
ール誘導体、トリアゾール誘導体、イミダゾール誘導
体、イミダゾロン誘導体、イミダゾリジン誘導体、ビス
イミダゾリジン誘導体、スチリル化合物、ヒドラゾン化
合物、ピラゾリン化合物、アミン誘導体、オキサゾロン
誘導体、ベンゾチアゾール誘導体、ベンズイミダゾール
誘導体、キナゾリン誘導体、ベンゾフラン誘導体、アク
リジン誘導体、フェナジン誘導体、アミノスチルベン誘
導体、ポリ−N−ビニルカルバゾール、ポリ−1−ビニ
ルピレン、ポリ−9−ビニルアントラセン等である。
In the present invention, other carrier transporting substances can be used together with the polymer compound of the present invention as long as the object of the present invention is not impaired. Although there is no particular limitation on the carrier transporting substance that can be used, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds Hydrazone compound, pyrazoline compound, amine derivative, oxazolone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, poly-N-vinylcarbazole, poly-1-vinylpyrene, And poly-9-vinylanthracene.

本発明においてキャリア輸送物質の添加量は、キャリ
ア輸送層中のバインダ樹脂100重量部に対してキャリア
輸送物質20〜200重量部が好ましく、特に好ましくは30
〜150重量部である。
In the present invention, the added amount of the carrier transporting substance is preferably 20 to 200 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the binder resin in the carrier transporting layer.
~ 150 parts by weight.

形成されるキャリア輸送層の膜厚は、好ましくは5〜
50μm、特に好ましくは5〜30μmである。
The thickness of the formed carrier transport layer is preferably 5 to 5.
It is 50 μm, particularly preferably 5 to 30 μm.

また、単層機能分離型の電子写真感光体の場合は、バ
インダ:キャリア発生物質:キャリア輸送物質の割合は
0〜100:1〜500:0〜500が好ましく、形成される感光層
の膜厚は5〜50μmが好ましく、特に好ましくは5〜30
μmである。
In the case of a single-layer function-separated electrophotographic photoreceptor, the ratio of binder: carrier generating substance: carrier transporting substance is preferably 0 to 100: 1 to 500: 0 to 500, and the thickness of the formed photosensitive layer Is preferably 5 to 50 μm, particularly preferably 5 to 30 μm.
μm.

本発明においてキャリア発生層には感度の向上、残留
電位乃至反復使用時の疲労低減等を目的として、一種又
は二種以上の電子受容性物質を含有せしめることができ
る。電子受容性物質の添加割合は重量比で、本発明に係
るキャリア発生物質:電子受容性物質=100:0.01〜200
が好ましく、更に好ましくは100:0.1〜100である。
In the present invention, one or two or more kinds of electron accepting substances can be contained in the carrier generating layer for the purpose of improving sensitivity, reducing residual potential or reducing fatigue upon repeated use. The addition ratio of the electron accepting substance is a weight ratio, and the carrier generating substance according to the present invention: the electron accepting substance = 100: 0.01 to 200
And more preferably 100: 0.1 to 100.

電子受容性物質はキャリア輸送層に添加してもよく、
この場合の電子受容性物質の添加割合は重量比で、全キ
ャリア輸送物質:電子受容性物質=100:0.01〜100が好
ましく、更に好ましくは100:0.1〜50である。
The electron accepting substance may be added to the carrier transport layer,
In this case, the addition ratio of the electron-accepting substance is preferably 100: 0.01 to 100, more preferably 100: 0.1 to 50, in terms of weight ratio.

また本発明の感光体にはその他、必要により感光層を
保護する目的で紫外線吸収剤、酸化防止剤等を含有して
もよく、また、感色性補正の染料を含有してもよい。
The photoreceptor of the present invention may further contain, if necessary, an ultraviolet absorber, an antioxidant or the like for the purpose of protecting the photosensitive layer, or may contain a dye for correcting color sensitivity.

[実施例] 以下、本発明を実施例によって具体的に説明するが、
本発明はこれらによって限定されるものではない。
EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by these.

実施例1 Alを蒸着したPETフィルム上に、塩化ビニル−酢酸ビ
ニル−マレイン酸共重合体「エスレックMF−10」(積水
化学工業社製)より成る厚さ約0.1μmの中間層を設け
た。次に、ジブロモアンスアンソロン40gをボールミル
で24時間粉砕し、これにビスフェノールA型ポリカーボ
ネート「パンライトL−1250」(帝人化成社製)20gを
1,2−ジクロロエタン1300mlに溶解した溶液を加えて更
に24時間分散し、得られた分散液を前記中間層上にワイ
ヤーバーで塗布し、厚さ約0.5μmのキャリア発生層を
形成した。
Example 1 An intermediate layer having a thickness of about 0.1 μm and made of a vinyl chloride-vinyl acetate-maleic acid copolymer “ESREC MF-10” (manufactured by Sekisui Chemical Co., Ltd.) was provided on a PET film on which Al was deposited. Next, 40 g of dibromoanthanesolone was pulverized by a ball mill for 24 hours, and 20 g of bisphenol A-type polycarbonate “PANLITE L-1250” (manufactured by Teijin Chemicals Ltd.) was added thereto.
A solution dissolved in 1300 ml of 1,2-dichloroethane was added and dispersed for another 24 hours, and the resulting dispersion was applied on the intermediate layer with a wire bar to form a carrier generating layer having a thickness of about 0.5 μm.

次に、合成例1で合成した本発明の高分子化合物(2
−1)20gを1,2−ジクロロエタン200mlに溶解した溶液
を上記キャリア発生層上にドクターブレードを用いて塗
布し、温度90℃にて1時間乾燥させ、キャリヤ輸送層
(厚さ約10μm)とし、感光体試料を作成した。
Next, the polymer compound of the present invention (2
-1) A solution prepared by dissolving 20 g in 200 ml of 1,2-dichloroethane is applied to the carrier generating layer using a doctor blade, and dried at a temperature of 90 ° C. for 1 hour to form a carrier transporting layer (about 10 μm thick). A photoreceptor sample was prepared.

得られた試料について、受容電位(Va)、残留電位
(Vr)、感度(E1/2)及び析出性を評価した。
The obtained sample was evaluated for accepting potential (V a ), residual potential (V r ), sensitivity (E 1/2 ), and deposition property.

感光体試料の評価には、感光体試験機を用いた。 A photoconductor tester was used for evaluation of the photoconductor sample.

結果を表1に示す。 Table 1 shows the results.

実施例2 実施例1において、キャリア輸送層における本発明の
高分子化合物(2−1)を合成例2で合成した本発明の
高分子化合物(3−1)に変更した以外は、実施例1と
同様にして、感光体試料を作製し、同様に評価した。結
果を表1に示す。
Example 2 Example 1 was the same as Example 1 except that the polymer compound (2-1) of the present invention in the carrier transport layer was changed to the polymer compound (3-1) of the present invention synthesized in Synthesis Example 2. In the same manner as in the above, a photoreceptor sample was prepared and evaluated in the same manner. Table 1 shows the results.

実施例3 実施例1において、キャリア輸送層における本発明の
高分子化合物(3−1)を合成例3で合成した本発明の
高分子化合物(5−1)に変更した以外は、実施例1と
同様にして、感光体試料を作製し、同様に評価した。結
果を表1に示す。
Example 3 Example 1 was the same as Example 1 except that the polymer compound (3-1) of the present invention in the carrier transport layer was changed to the polymer compound (5-1) of the present invention synthesized in Synthesis Example 3. In the same manner as in the above, a photoreceptor sample was prepared and evaluated in the same manner. Table 1 shows the results.

比較例1 下記構造式で表わすキャリア輸送物質80gとアクリル
樹脂ダイヤナールBR−80(三菱レイヨン製)160gとを1,
2−ジクロロエタン1070mlに溶解して得た溶液をキャリ
ヤ発生層上にドクターブレードを用いて塗布し、キャリ
ア輸送層(膜厚10μm)を形成した以外は実施例1と同
様にして比較感光体試料を作製し、同様に評価した。結
果を表1に示す。
Comparative Example 1 80 g of a carrier transporting material represented by the following structural formula and 160 g of an acrylic resin dial BR-80 (manufactured by Mitsubishi Rayon) were mixed with 1,
A comparative photoreceptor sample was prepared in the same manner as in Example 1 except that a solution obtained by dissolving in 1070 ml of 2-dichloroethane was applied on the carrier generating layer using a doctor blade to form a carrier transporting layer (film thickness: 10 μm). It was prepared and evaluated similarly. Table 1 shows the results.

比較例2 実施例1において、本発明の高分子化合物(2−1)
にかえてポリビニルカルバゾール(阿南香料製ツビコー
ル210)を用いた以外は実施例1と同様にして比較感光
体試料を作製し、同様に評価した。結果を表1に示す。
Comparative Example 2 In Example 1, the polymer compound (2-1) of the present invention was used.
A comparative photoreceptor sample was prepared and evaluated in the same manner as in Example 1 except that polyvinyl carbazole (Tubicol 210 manufactured by Anan Koshiro) was used instead. Table 1 shows the results.

比較例3 トリフェニルアミン60gとポリカーボネート100gを1,2
−ジクロロエタン1000mlに溶解した溶液を塗布してキャ
リア輸送層とした以外は実施例1と同様にして比較感光
体試料を作製し、同様に評価した。感光層にトリフェニ
ルアミンの析出が発生した。他の結果も含め表1に示
す。
Comparative Example 3 60 g of triphenylamine and 100 g of polycarbonate were mixed in 1,2
A comparative photoreceptor sample was prepared and evaluated in the same manner as in Example 1 except that a solution dissolved in 1000 ml of dichloroethane was applied to form a carrier transport layer. Triphenylamine was deposited on the photosensitive layer. Table 1 includes other results.

表1より明らかなように、本発明の高分子化合物をキ
ャリア輸送物質として用いた実施例1〜3はいずれも、
本発明外のキャリア輸送物質を用いた比較例1〜3の各
々に比較してすべての特性において優れている。
As is clear from Table 1, all of Examples 1 to 3 using the polymer compound of the present invention as a carrier transporting substance,
It is superior in all characteristics as compared with each of Comparative Examples 1 to 3 using a carrier transporting substance outside the present invention.

[発明の効果] 以上詳細に述べたように、本発明の高分子化合物によ
り、結晶析出や相分離がなく、優れた機械的強度及び光
導電性を有する電子写真感光体を提供することができ
る。
[Effects of the Invention] As described in detail above, the polymer compound of the present invention can provide an electrophotographic photoreceptor having excellent mechanical strength and photoconductivity without crystal precipitation or phase separation. .

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】下記構造単位(I),(II)及び(III)
の少なくとも1つを含む繰り返し単位を少なくとも1種
有する高分子化合物を含有する電子写真感光体。 [式中、R1,R2,R3,R4及びR5は各々アルキル基又はアル
コキシ基を表わし、n1及びn3は各々1〜5の整数を、
n2,n4及びn5は各々1〜4の整数を表わす。また、l,m及
びpはそれぞれ0より大きく、1以下の数を表わす。]
1. The following structural units (I), (II) and (III)
An electrophotographic photoreceptor containing a polymer compound having at least one repeating unit containing at least one of the following. [Wherein, R 1 , R 2 , R 3 , R 4 and R 5 each represent an alkyl group or an alkoxy group, and n 1 and n 3 each represent an integer of 1 to 5,
n 2 , n 4 and n 5 each represent an integer of 1 to 4. Further, l, m and p each represent a number greater than 0 and 1 or less. ]
JP25472490A 1990-09-25 1990-09-25 Electrophotographic photoreceptor Expired - Lifetime JP2852464B2 (en)

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