JPH075715A - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
- Publication number
- JPH075715A JPH075715A JP16976693A JP16976693A JPH075715A JP H075715 A JPH075715 A JP H075715A JP 16976693 A JP16976693 A JP 16976693A JP 16976693 A JP16976693 A JP 16976693A JP H075715 A JPH075715 A JP H075715A
- Authority
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- Japan
- Prior art keywords
- charge
- layer
- formula
- electrophotographic
- generating substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電子写真感光体に関し、
詳しくはその電荷発生物質として無金属フタロシアニン
顔料と特定の構造のペリレンテトラカルボン酸誘導体顔
料とを同時に含有する電子写真感光体に関する。FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic photoconductor that simultaneously contains a metal-free phthalocyanine pigment and a perylene tetracarboxylic acid derivative pigment having a specific structure as its charge generating substance.
【０００２】[0002]
【従来の技術】電子写真プロセスは静電力による潜像の
可視化を原理として用いたものであるため、そのプロセ
スに用いられる電子写真感光体には良好な帯電性と光照
射による迅速な表面電位の減衰が必要となる。これらプ
ロセス上必要な特性は、固体物性値である暗抵抗の高さ
と良好な量子効率、高い電荷移動度に還元される。これ
らの物性値を満足するものとして、従来、セレン、セレ
ン−テルル合金、砒素セレン等の無機化合物から構成さ
れた電子写真感光体が知られている。一方、２，４，７
−トリニトロ−９−フルオレノン（ＴＮＦ）とポリ−Ｎ
−ビニルカルバゾール（ＰＶＫ）との電荷移動錯体を用
いた電子写真感光体が光導電性を示すことが発見されて
から、数多くの有機光導電体が開発されてきた。2. Description of the Related Art Since the electrophotographic process uses the visualization of a latent image by electrostatic force as a principle, the electrophotographic photosensitive member used in the process has a good charging property and a rapid surface potential due to light irradiation. Attenuation is needed. The properties required for these processes are reduced to high dark resistance, which is a physical property value, good quantum efficiency, and high charge mobility. As those satisfying these physical property values, an electrophotographic photoreceptor composed of an inorganic compound such as selenium, a selenium-tellurium alloy, or arsenic selenium has been conventionally known. On the other hand, 2, 4, 7
-Trinitro-9-fluorenone (TNF) and poly-N
A number of organic photoconductors have been developed since it was discovered that electrophotographic photoreceptors using a charge transfer complex with -vinylcarbazole (PVK) exhibit photoconductivity.
【０００３】例えば、ペリレン系顔料を用いたもの（Ｕ
ＳＰ ３８７１８８２参照）、フタロシアニン系顔料を
用いたもの（特公昭４９−４３３８号、特開昭５８−１
８２６３９号、特開昭６０−１９１５１号参照）、アゾ
顔料を用いたもの（特公昭５５−４２３８０号、特開昭
５５−８４９４３号参照）、スクアリウム系染料、多環
キノン系顔料等を用いたものがある。これらの電荷発生
物質のうちペリレン系顔料を用いた感光体は、高速の複
写機用としては感度が低く、また顔料の吸収が６００ｎ
ｍより短波長側に限られているため赤色光には感度がな
くカラー複写機用感光体としては不適当である。一方、
フタロシアニン系顔料は電子写真感度が異なる様々な結
晶型を有するが、高感度結晶型を用いたものでも５００
ｎｍ付近の光に対して感度が低く、また帯電性等の特性
が温度、湿度などの環境変動、帯電、露光などの使用サ
イクルにより変化しやすい。またアゾ顔料を用いたもの
は電荷発生層製造時に安定な分散性を有する塗布液を作
製するのが難しく、加えて顔料の光安定性が悪く且つ顔
料の高純度化が困難であるなどの欠点を持つている。For example, one using a perylene pigment (U
SP 3718882), using a phthalocyanine pigment (Japanese Patent Publication No. 49-4338, JP-A-58-1).
No. 82639, JP-A-60-19151), those using azo pigments (see JP-B-55-42380, JP-A-55-89443), squarylium dyes, polycyclic quinone pigments, etc. There is something. Among these charge generating substances, the photoreceptor using a perylene pigment has low sensitivity for a high-speed copying machine and has a pigment absorption of 600 n.
Since it is limited to the wavelength side shorter than m, it has no sensitivity to red light and is unsuitable as a photoconductor for a color copying machine. on the other hand,
Phthalocyanine pigments have various crystal types with different electrophotographic sensitivities.
The sensitivity to light in the vicinity of nm is low, and the characteristics such as chargeability are likely to change due to environmental changes such as temperature and humidity, and usage cycles such as charging and exposure. Further, those using an azo pigment have drawbacks that it is difficult to prepare a coating liquid having stable dispersibility during the production of the charge generation layer, and in addition, the light stability of the pigment is poor and it is difficult to highly purify the pigment. Have
【０００４】このように、単一顔料を電荷発生物質に用
いた場合、十分な感度、可視域から赤外域までの幅広い
分光感度域が得られないという問題点があった。可視域
から赤外域までの幅広い分光感度域を得る方法としては
従来から、２種以上の電荷発生物質を併用することが提
案され、現在も開発されている。たとえば、横山等は、
電子受容性（ｎ型）顔料と電子供与性（ｐ型）顔料を共
蒸着することで量子効率が向上することを報告している
（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５８，１０６２
（１９９１））。しかし、バルク層の抵抗が小さいた
め、直接これを電子写真感光体に適用することはできな
い。また、電荷発生物質にペリレンテトラカルボン酸ジ
イミドとＸ型メタルフリーフタロシアニンとを含有する
電子写真感光体（特開平２−２２８６７１）や、アンサ
ンスロン系化合物とオキソチタニルフタロシアニンとを
含有する電子写真感光体（特開平２−２２２９６２）等
が提案されているが、未だ十分な感度が得られていな
い。As described above, when a single pigment is used as a charge generating substance, there is a problem that sufficient sensitivity and a wide spectral sensitivity range from the visible region to the infrared region cannot be obtained. As a method for obtaining a wide spectral sensitivity range from the visible range to the infrared range, it has been conventionally proposed to use two or more kinds of charge generating substances in combination and is still being developed. For example, Yokoyama
It has been reported that the quantum efficiency is improved by co-evaporating an electron-accepting (n-type) pigment and an electron-donating (p-type) pigment (Appl. Phys. Lett., 58, 1062).
(1991)). However, since the bulk layer has a low resistance, it cannot be directly applied to an electrophotographic photoreceptor. Further, an electrophotographic photoreceptor containing perylene tetracarboxylic acid diimide and X-type metal-free phthalocyanine as a charge generating substance (JP-A-2-228671), and an electrophotographic photoreceptor containing an anthanthrone compound and oxotitanyl phthalocyanine. (Japanese Patent Laid-Open No. 2-222962) has been proposed, but sufficient sensitivity has not been obtained yet.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は上記問
題点を解消し、高感度で、電子写真特性の優れた電子写
真感光体を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide an electrophotographic photoreceptor having high sensitivity and excellent electrophotographic characteristics.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記目的
を達成するため鋭意検討した結果、導電性基体上に、少
なくとも電荷発生物質及び電荷輸送物質の双方が含有さ
れてなる積層又は単層感光層を持つ電子写真感光体にお
いて、電荷発生物質として特定な電子受容性（ｎ型）顔
料と特定な電子供与性（ｐ型）顔料を一旦均一な溶解状
態とし、その後貧溶媒で粒子化した混合物を用いること
により上記目的が達成されることを見い出した。すなわ
ち、本発明によれば、導電性基体上に少なくとも電荷発
生物質と電荷輸送物質とが同一層中に含有されている単
層感光層、又は両物質が別々の層に含有されている積層
感光層を有する電子写真感光体において、該電荷発生物
質として無金属フタロシアニンと下記一般式（Ｉ）（化
１）で表わされるペリレンテトラカルボン酸ジイミド化
合物とを一旦均一な溶解状態とし、その後貧溶媒で粒子
化した混合物を用いることを特徴とする電子写真感光体
が提供される。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a laminated or monolayer structure in which at least both a charge generating substance and a charge transporting substance are contained on a conductive substrate. In an electrophotographic photoreceptor having a layer photosensitive layer, a specific electron-accepting (n-type) pigment and a specific electron-donating (p-type) pigment as charge generating substances are once made into a uniform dissolved state, and then granulated with a poor solvent. It has been found that the above object is achieved by using the above mixture. That is, according to the present invention, a single-layer photosensitive layer in which at least a charge generating substance and a charge transporting substance are contained in the same layer on a conductive substrate, or a laminated photosensitive layer in which both substances are contained in separate layers. In an electrophotographic photoreceptor having a layer, a metal-free phthalocyanine as the charge generating substance and a perylenetetracarboxylic acid diimide compound represented by the following general formula (I) (formula 1) are once brought into a uniform dissolved state, and then a poor solvent is used. There is provided an electrophotographic photosensitive member characterized by using a mixture which is made into particles.
【化１】 （式中、Ｒ1、Ｒ2は水素、置換もしくは無置換のアルキ
ル基又は置換もしくは無置換のアリール基を表す。） また、本発明によれば、導電性基体上に少なくとも電荷
発生物質と電荷輸送物質とが同一層中に含有されている
単層感光層、又は両物質が別々の層に含有されている積
層感光層を有する電子写真感光体において、該電荷発生
物質として無金属フタロシアニンと下記一般式（ＩＩ）
（化２）で表わされるペリレンテトラカルボン酸ジイミ
ダゾール化合物とを一旦均一な溶解状態とし、その後貧
溶媒で粒子化した混合物を用いることを特徴とする電子
写真感光体が提供される。[Chemical 1] (In the formula, R 1 and R 2 represent hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) Further, according to the present invention, at least the charge generating substance and the charge are formed on the conductive substrate. In an electrophotographic photoreceptor having a single-layer photosensitive layer in which a transport substance is contained in the same layer, or a laminated photosensitive layer in which both substances are contained in separate layers, metal-free phthalocyanine and General formula (II)
There is provided an electrophotographic photosensitive member characterized by using a mixture of the perylene tetracarboxylic acid diimidazole compound represented by (Chemical Formula 2) once in a uniform dissolved state and then granulating the mixture with a poor solvent.
【化２】 （式中、Ｘ1、Ｘ2は、置換もしくは無置換の縮合多環又
はヘテロ環の２価基を表す。） 前記一般式（Ｉ）において、Ｒ1、Ｒ2の置換基として
は、置換基を有していてもよいベンゼン環、ハロゲン原
子、アルコキシ基が挙げられ、また上記アリール基とし
てはフェニル基、ナフチル基などの縮合多環類、ピリジ
ル基などのヘテロ環類が、その置換基としてはアルキル
基、アルコキシ基、ハロゲン原子等が挙げられる。また
一般式（ＩＩ）において、Ｘ1、Ｘ2の置換基としては、
アルキル基、アルコキシ基、ハロゲン原子等が挙げられ
る。[Chemical 2] (In the formula, X 1 and X 2 represent a substituted or unsubstituted divalent group of a fused polycyclic or heterocyclic ring.) In the general formula (I), the substituents of R 1 and R 2 are substituted. A benzene ring which may have a group, a halogen atom, an alkoxy group, and examples of the aryl group include a condensed polycycle such as a phenyl group and a naphthyl group, and a heterocycle such as a pyridyl group, and the substituents thereof. Examples thereof include an alkyl group, an alkoxy group and a halogen atom. Further, in the general formula (II), as the substituents of X 1 and X 2 ,
Examples thereof include an alkyl group, an alkoxy group and a halogen atom.
【０００７】本発明は、電荷発生物質として無金属フタ
ロシアニンとペリレンテトラカルボン酸ジイミド化合物
又はペリレンテトラカルボン酸ジイミダゾール化合物と
を一旦均一な溶解状態とし、その後貧溶媒で粒子化した
混合物を用いることを特徴とする。本発明は無金属フタ
ロシアニンとペリレンテトラカルボン酸ジイミド化合物
又はペリレンテトラカルボン酸ジイミダゾール化合物と
を一旦均一な溶解状態とし、その後貧溶媒で粒子化した
混合物を電荷発生物質として用いたことから、高感度で
電子写真特性に優れた電子写真感光体が得られる。In the present invention, as a charge generating substance, a metal-free phthalocyanine and a perylene tetracarboxylic acid diimide compound or a perylene tetracarboxylic acid diimidazole compound are once made into a uniform dissolved state and then a mixture obtained by granulating with a poor solvent is used. Characterize. In the present invention, a metal-free phthalocyanine and a perylene tetracarboxylic acid diimide compound or a perylene tetracarboxylic acid diimidazole compound are once brought into a uniform dissolved state, and then a mixture obtained by granulating with a poor solvent is used as a charge generating substance. Thus, an electrophotographic photoreceptor having excellent electrophotographic characteristics can be obtained.
【０００８】電荷発生物質として、フタロシアニン顔料
を単独で使用した場合には、後記比較例から明らかなよ
うに、帯電性が悪く、また十分に高い感度を有するもの
が得られず、本発明の目的を達成することができない。When the phthalocyanine pigment is used alone as the charge generating substance, as will be apparent from the comparative example described below, a substance having a poor charging property and a sufficiently high sensitivity cannot be obtained. Can not be achieved.
【０００９】また、電荷発生物質として、ペリレンテト
ラカルボン酸誘導体を単独で使用した場合にも、後記比
較例から明らかなように、感度が悪く、本発明の所期の
目的を達成することができない。Also, when a perylene tetracarboxylic acid derivative is used alone as the charge generating substance, the sensitivity is poor and the intended object of the present invention cannot be achieved, as will be apparent from the comparative examples described later. .
【００１０】無金属フタロシアニンと特定の構造のペリ
レンテトラカルボン酸誘導体の使用割合は１／９〜９９
／１、好ましくは５／９５〜９５／５である。本発明に
おける上記２種顔料の溶解方法としては、濃硫酸、ジク
ロル酢酸、トリフルオロ酢酸等の強酸、あるいはトリエ
チルアミン、トリエタノールアミン等の強塩基に溶解さ
せ、一旦均一な溶解状態とする。続いて、上記溶液を貧
溶媒に注入することにより粒子化がなされる。使用でき
る貧溶媒としては、水、メタノール、エタノール、ヘキ
サン、シクロヘキサン、エーテル、酢酸エチル、１，２
−ジクロルエタン、クロロホルム、ベンゼン、トルエ
ン、テトラヒドロフラン、シクロヘキサノン、クロルベ
ンゼン、ニトロベンゼン、アセトニトリル、ジメチルホ
ルムアミド、ジメチルスルホキサイド等が挙げられる。
これらは単独あるいは２種以上が混合されていてもよ
い。これらの貧溶媒で粒子化後、更に同種、あるいは別
種の貧溶媒で処理してもよい。これらのうち、好ましい
混合粒子化方法としては、所定量比の無金属フタロシア
ニンと特定の構造のペリレンテトラカルボン酸誘導体の
合計１ｇを濃硫酸１００ｇに溶解（アシッドペースト処
理）後、１リットルの水中に注入し、析出させ、さらに
水で十分に洗浄後テトラヒドロフランで処理する方法が
挙げられる。このような方法で得られた化合物を電荷発
生物質として用いた電子写真感光体は、従来のものと比
べて高感度で電子写真特性に優れる。これは、本発明で
用いる前記２種顔料の接触面積が増大したことによると
考えられる。The usage ratio of the metal-free phthalocyanine and the perylene tetracarboxylic acid derivative having a specific structure is 1/9 to 99.
/ 1, preferably 5/95 to 95/5. As a method for dissolving the above two kinds of pigments in the present invention, they are dissolved in a strong acid such as concentrated sulfuric acid, dichloroacetic acid, trifluoroacetic acid, or a strong base such as triethylamine, triethanolamine, and once brought into a uniform dissolved state. Subsequently, the solution is injected into a poor solvent to form particles. As the poor solvent that can be used, water, methanol, ethanol, hexane, cyclohexane, ether, ethyl acetate, 1, 2
-Dichloroethane, chloroform, benzene, toluene, tetrahydrofuran, cyclohexanone, chlorobenzene, nitrobenzene, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like.
These may be used alone or in combination of two or more. After forming particles with these poor solvents, they may be further treated with the same or different poor solvent. Among these, the preferred method for forming mixed particles is to dissolve a total of 1 g of a metal-free phthalocyanine in a predetermined amount ratio and a perylenetetracarboxylic acid derivative having a specific structure in 100 g of concentrated sulfuric acid (acid paste treatment), and then dissolve in 1 liter of water. A method of injecting, precipitating, further thoroughly washing with water and treating with tetrahydrofuran can be mentioned. The electrophotographic photosensitive member using the compound obtained by such a method as a charge generating substance has higher sensitivity and excellent electrophotographic characteristics as compared with the conventional one. It is considered that this is because the contact area of the two pigments used in the present invention was increased.
【００１１】次に、本発明で用いられる一般式（Ｉ）で
表わされるペリレンテトラカルボン酸ジイミド及び一般
式（ＩＩ）で表わされるペリレンテトラカルボン酸ジイ
ミダゾールの具体例を例示する。Next, specific examples of the perylenetetracarboxylic acid diimide represented by the general formula (I) and the perylenetetracarboxylic acid diimidazole represented by the general formula (II) used in the present invention will be illustrated.
【表１−（１）】[Table 1- (1)]
【化１】 [Chemical 1]
【表１−（２）】 [Table 1- (2)]
【化２】 [Chemical 2]
【００１２】本発明の電子写真感光体の代表的な層構成
を図１及び図２に示す。図１は感光層が単一層からな
り、感光層が電荷発生物質２と結着剤中に電荷輸送物質
とが分子状に分散されたマトリックス３を表わしてい
る。なお、１は導電性基体である。図２は感光層が電荷
発生層４と、電荷輸送層５の積層構造をとっており、電
荷発生物質２を含有している。A typical layer structure of the electrophotographic photosensitive member of the present invention is shown in FIGS. FIG. 1 shows a matrix 3 in which the photosensitive layer is composed of a single layer, and the photosensitive layer has a charge generating substance 2 and a charge transporting substance dispersed in a binder in a molecular form. In addition, 1 is a conductive substrate. In FIG. 2, the photosensitive layer has a laminated structure of a charge generation layer 4 and a charge transport layer 5, and contains a charge generation substance 2.
【００１３】本発明で用いることができる導電性基体と
しては、アルミニウム、ニッケル、銅、ステンレス等の
金属板、金属ドラムまたは金属箔、アルミニウム、酸化
錫、ヨウ化銅の薄膜を塗布したプラスチックフィルムあ
るいはガラス等が挙げられる。本発明の感光体では帯電
性を改良する目的で感光層と導電性基体の間に下引き層
を設けることができる。これらの材料としては後で記載
する結着剤樹脂の他に、ポリアミド樹脂、ポリビニルア
ルコール、カゼイン、ポリビニルピロリドン等を用いる
ことができる。下引き層の厚さは０．０１〜１０μｍ好
ましくは０．１〜５μｍくらいが適当である。As the conductive substrate which can be used in the present invention, a metal plate such as aluminum, nickel, copper or stainless steel, a metal drum or a metal foil, a plastic film coated with a thin film of aluminum, tin oxide or copper iodide, or Examples thereof include glass. In the photoreceptor of the present invention, an undercoat layer may be provided between the photosensitive layer and the conductive substrate for the purpose of improving charging property. As these materials, in addition to the binder resin described later, polyamide resin, polyvinyl alcohol, casein, polyvinylpyrrolidone and the like can be used. The thickness of the undercoat layer is 0.01 to 10 μm, preferably 0.1 to 5 μm.
【００１４】図１に示すような単一層からなる感光層
は、たとえば、前記無金属フタロシアニン顔料とペリレ
ンテトラカルボン酸誘導体を混合した電荷発生物質と電
荷輸送物質（正孔移動物質及びアクセプタ化合物）を適
当な結着剤樹脂溶液中に混合し塗布乾燥することにより
得られる。図２に示すような積層構造からなる感光層の
電荷発生層の形成方法としては、本発明に係る前記顔料
を混合した電荷発生物質を適当な結着剤樹脂溶液ととも
に分散し、塗布・乾燥することによって得られる。The photosensitive layer composed of a single layer as shown in FIG. 1 comprises, for example, a charge-generating substance and a charge-transporting substance (hole-transporting substance and acceptor compound) obtained by mixing the metal-free phthalocyanine pigment and the perylenetetracarboxylic acid derivative. It is obtained by mixing in a suitable binder resin solution, coating and drying. As a method for forming the charge generating layer of the photosensitive layer having a laminated structure as shown in FIG. 2, the charge generating substance mixed with the pigment according to the present invention is dispersed with a suitable binder resin solution, and then coated and dried. Obtained by
【００１５】本発明で用いることができる結着剤樹脂と
しては、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、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、シリコーン樹脂、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
繰り返し単位のうち２つ以上を含む共重合体樹脂、例え
ば塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸
ビニル−無水マレイン酸共重合体樹脂を挙げることがで
きる。The binder resin usable in the present invention includes polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, Addition polymerization type resins such as polycarbonate resins, silicone resins, melamine resins, polyaddition type resins, polycondensation type resins, and copolymer resins containing two or more of these repeating units, for example vinyl chloride-vinyl acetate copolymer Mention may be made of vinyl chloride-vinyl acetate-maleic anhydride copolymer resins.
【００１６】電荷輸送層は主として電荷輸送物質（有機
正孔移動物質）と結着剤樹脂とを溶剤中に溶解させた塗
料を塗工乾燥して形成する。電荷輸送物質には正孔輸送
物質と電子輸送物質がある。The charge transport layer is mainly formed by coating and drying a paint in which a charge transport substance (organic hole transport substance) and a binder resin are dissolved in a solvent. The charge transport material includes a hole transport material and an electron transport material.
【００１７】正孔輸送物質としては、９−エチルカルバ
ゾール−３−アルデビド１−メチル−１−フェニルヒド
ラゾン、９−エチルカルバゾール−３−アルデヒド１，
１−ジフェニルヒドラゾン、４−ジエチルアミノスチレ
ン−β−アルデヒド１−メチル−１−フェニルヒドラゾ
ン、４−メトキシナフタレン−１−アルデヒド１−ベン
ジル−１−フェニルヒドラゾン、４−メトキシベンズア
ルデヒド１−メチル−１−フェニルヒドラゾン、２，４
−ジメトキシベンズアルデヒド１−ベンジル−１−フェ
ニルヒドラゾン、４−ジエチルアミノベンズアルデヒド
１，１−ジフェニルヒドラゾン、４−メトキシベンズア
ルデヒド１−ベンジル−１−（４−メトキシフェニル）
ヒドラゾン、４−ジフェニルアミノベンズアルデヒド１
−ベンジル−１−フェニルヒドラゾン、４−ジベンジル
アミノベンズアルデヒド１，１−ジフェニルヒドラゾン
等のヒドラゾン化合物、１，１−ビス（４−ジベンジル
アミノフェニル）プロパン、トリス（４−ジエチルアミ
ノフェニル）メタン、２，２’−ジメチル−４，４’−
ビス（ジエチルアミノ）−トリフェニルメタン等のトリ
フェニルメタン化合物、またはジフェニルメタン化合
物、９−（４−ジエチルアミノスチリル）アントラセ
ン、９−ブロム−１０−（４−ジエチルアミノスチリ
ル）アントラセン、９−（４−ジメチルアミノスチリ
ル）フルオレン、３−（９−フルオレニリデン）−９−
エチルカルバゾール、１，２−ビス（２，４−ジエチル
アミノスチリル）ベンゼン、１，２−ビス（２，４−ジ
メトキシスチリル）ベンゼン、３−スチリル−９−エチ
ルカルバゾール、３−（４−メトキシスチリル）−９−
エチルカルバゾール、４−ジフェニルアミノスチルベ
ン、４−ジベンジルアミノスチルベン、４−ジトリルア
ミノスチルベン、１−（４−ジフェニルアミノスチリ
ル）ナフタレン、１−（４−ジエチルアミノスチリル）
ナフタレン、４’−ジフェニルアミノ−α−フェニルス
チルベン、４’−メチルフェニルアミノ−α−フェニル
スチルベン等のスチルベン化合物、またはアリールビニ
ル化合物、１−フェニル−３−（４−ジエチルアミノス
チリル）−５−（４−ジエチルアミノフェニル）ピラゾ
リン、１−フェニル−３−（４−ジメチルアミノスチリ
ル）−５−（４−ジメチルアミノフェニル）ピラゾリン
等のピラゾリン化合物、２，５−ビス（４−ジエチルア
ミノフェニル）−１，３，４−オキサジアゾール、２，
５−ビス〔４−（４−ジエチルアミノスチリル）フェニ
ル〕−１，３，４−オキサジアゾール、２−（９−エチ
ルカルバゾリル−３−）−５−（４−ジエチルアミノフ
ェニル）−１，３，４−オキサジアゾール、２−ビニル
−４−（２−クロロフェニル）−５−（４−ジエチルア
ミノフェニル）オキサゾール、２−（４−ジエチルアミ
ノフェニル）−４−フェニルオキサゾール等の複素環化
合物、トリフェニルアミン、トリ−ｐ−トリルアミン、
４，４’−ジメトキシトリフェニルアミン、Ｎ，Ｎ’−
ビス（３−メチルフェニル）−Ｎ，Ｎ’−ジフェニルベ
ンジジン、１，１−ビス（４−ジ−ｐ−トリフェニルア
ミノフェニル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’−
テトラ（ｐ−トリル）ベンジジン、Ｎ，Ｎ，Ｎ’，Ｎ’
−テトラ（ｐ−トリル）−ｏ−フェニレンジアミン、
Ｎ，Ｎ’−ビス（４−メトキシフェニル）−１−アミノ
ピレン等のトリフェニルアミン化合物、またはトリアリ
ールアミン化合物、などの低分子化合物がある。また、
ポリ−Ｎ−ビニルカルバゾール、ハロゲン化ポリ−Ｎ−
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、ピレンホルムアルデヒド樹脂、エチルカル
バゾールホルムアルデヒド樹脂、などの高分子化合物も
使用できる。As the hole-transporting substance, 9-ethylcarbazole-3-aldevid 1-methyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde 1,
1-diphenylhydrazone, 4-diethylaminostyrene-β-aldehyde 1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde 1-benzyl-1-phenylhydrazone, 4-methoxybenzaldehyde 1-methyl-1-phenyl Hydrazone, 2,4
-Dimethoxybenzaldehyde 1-benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde 1,1-diphenylhydrazone, 4-methoxybenzaldehyde 1-benzyl-1- (4-methoxyphenyl)
Hydrazone, 4-diphenylaminobenzaldehyde 1
Hydrazone compounds such as -benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde 1,1-diphenylhydrazone, 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 2 , 2'-dimethyl-4,4'-
Triphenylmethane compounds such as bis (diethylamino) -triphenylmethane, or diphenylmethane compounds, 9- (4-diethylaminostyryl) anthracene, 9-bromo-10- (4-diethylaminostyryl) anthracene, 9- (4-dimethylamino) Styryl) fluorene, 3- (9-fluorenylidene) -9-
Ethylcarbazole, 1,2-bis (2,4-diethylaminostyryl) benzene, 1,2-bis (2,4-dimethoxystyryl) benzene, 3-styryl-9-ethylcarbazole, 3- (4-methoxystyryl) -9-
Ethylcarbazole, 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4-diethylaminostyryl)
Naphthalene, stilbene compounds such as 4′-diphenylamino-α-phenylstilbene, 4′-methylphenylamino-α-phenylstilbene, or aryl vinyl compounds, 1-phenyl-3- (4-diethylaminostyryl) -5- ( Pyrazoline compounds such as 4-diethylaminophenyl) pyrazolin, 1-phenyl-3- (4-dimethylaminostyryl) -5- (4-dimethylaminophenyl) pyrazolin, 2,5-bis (4-diethylaminophenyl) -1, 3,4-oxadiazole, 2,
5-bis [4- (4-diethylaminostyryl) phenyl] -1,3,4-oxadiazole, 2- (9-ethylcarbazolyl-3-)-5- (4-diethylaminophenyl) -1, Heterocyclic compounds such as 3,4-oxadiazole, 2-vinyl-4- (2-chlorophenyl) -5- (4-diethylaminophenyl) oxazole, 2- (4-diethylaminophenyl) -4-phenyloxazole, tri Phenylamine, tri-p-tolylamine,
4,4'-dimethoxytriphenylamine, N, N'-
Bis (3-methylphenyl) -N, N'-diphenylbenzidine, 1,1-bis (4-di-p-triphenylaminophenyl) cyclohexane, N, N, N ', N'-
Tetra (p-tolyl) benzidine, N, N, N ', N'
-Tetra (p-tolyl) -o-phenylenediamine,
There are low molecular weight compounds such as triphenylamine compounds such as N, N′-bis (4-methoxyphenyl) -1-aminopyrene, or triarylamine compounds. Also,
Poly-N-vinylcarbazole, halogenated poly-N-
Polymer compounds such as vinylcarbazole, polyvinylpyrene, polyvinylanthracene, pyreneformaldehyde resin, ethylcarbazoleformaldehyde resin can also be used.
【００１８】電荷輸送物質としては、例えば、クロルア
ニル、ブロムアニル、テトラシアノエチレン、テトラシ
アノキノジメタン、２，４，７−トリニトロ−９−フル
オレノン、２，４，５，７−テトラニトロ−９−フルオ
レノン、ジフェノキノン、２，４，５，７−テトラニト
ロキサントン、２，４，８−トリニトロチオキサント
ン、２，６，８−トリニトロ−４Ｈ−インデノ〔１，２
−ｂ〕チオフェン−４−オン、１，３，７−トリニトロ
ジベンゾチオフェン−５，５−ジオキサイド、無水コハ
ク酸、無水マレイン酸、フタル酸、テトラクロル無水フ
タル酸、テトラブロム無水フタル酸、４−ニトロ無水フ
タル酸、３−ニトロ無水フタル酸、無水ピロメリット
酸、ピクリン酸、ｏ−ニトロ安息香酸、３，５−ジニト
ロ安息香酸、ペンタフルオロ安息香酸、５−ニトロサリ
チル酸、３，５−ジニトロサリチル酸、ｏ−ジニトロベ
ンゼン、ｍ−ジニトロベンゼン、１，３，５−トリニト
ロベンゼン、ｐ−ニトロベンゾニトリル、ピクリルクロ
ライド、ジクロロジシアノ−ｐ−ベンゾキノン、アント
ラキノン、クロロアントラキノン、ジクロロアントラキ
ノン、ジニトロアントラキノン、９−フルオレニリデン
〔ジシアノメチレンマロノジニトリル〕、２，４，７−
トリニトロ−フルオレニリデンアニリン等、電子親和力
が大きい化合物が挙げられる。Examples of the charge transport material include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone. , Diphenoquinone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2]
-B] thiophen-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, succinic anhydride, maleic anhydride, phthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 4- Nitrophthalic anhydride, 3-nitrophthalic anhydride, pyromellitic anhydride, picric acid, o-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid , O-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, dichlorodicyano-p-benzoquinone, anthraquinone, chloroanthraquinone, dichloroanthraquinone, dinitroanthraquinone, 9- Fluorenylidene (dicyanomethylene Ronojinitoriru], 2,4,7
Examples thereof include compounds having a large electron affinity such as trinitro-fluorenylideneaniline.
【００１９】これらの電荷輸送物質は、単独または２種
以上混合して用いられる。感光層が単一の場合、膜厚は
５〜１００μｍ、好ましくは１０〜４０μｍくらいが適
当である。５μｍより薄いと帯電性が低下し、逆に、１
００μｍより厚いと感度の低下をもたらす。また感光層
が積層構造の場合、電荷発生層の膜厚は０．０１〜１０
μｍ、好ましくは０．０５〜５μｍの範囲であり、電荷
輸送層の膜厚は５〜４０μｍ、好ましくは１０〜３０μ
ｍの範囲にある。These charge transport materials may be used alone or in admixture of two or more. When the photosensitive layer is single, the film thickness is 5 to 100 μm, preferably 10 to 40 μm. If the thickness is less than 5 μm, the charging property will decrease, and conversely, 1
If it is thicker than 00 μm, the sensitivity is lowered. When the photosensitive layer has a laminated structure, the thickness of the charge generation layer is 0.01 to 10
μm, preferably 0.05 to 5 μm, and the thickness of the charge transport layer is 5 to 40 μm, preferably 10 to 30 μm.
It is in the range of m.
【００２０】[0020]
【実施例】次に本発明を実施例により、さらに具体的に
説明するが、これにより本発明の態様が限定されるもの
ではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the embodiments of the present invention are not limited thereby.
【００２１】実施例１ 無金属フタロシアニン０．３ｇと前記構造式〔Ａ−１〕
０．１ｇ（混合比：７５／２５）とを硫酸に溶解した
後、水中にあけて析出させることによって電荷発生物質
を調製した。この電荷発生物質０．２５ｇをポリカーボ
ネートＺ（ＰＣ−Ｚ）溶液６．２５ｇ（テトラヒドロフ
ラン中に２ｗｔ％に溶解したもの）とともにボールミリ
ングした後、顔料組成２ｗｔ％、ＰＣ−Ｚ組成が５０ｗ
ｔ％、下記のアクセプタ化合物（化３）が１８ｗｔ％、
下記の正孔移動物質（化４）が３０ｗｔ％となるよう１
０ｗｔ％のＰＣ−Ｚ溶液、アクセプタ化合物、正孔移動
物質を加え感光体の塗布液を作製した。この液をアルミ
ニウム基体上に塗布し加熱乾燥して約１８μｍの単層型
感光体を作製した。Example 1 0.3 g of metal-free phthalocyanine and the above structural formula [A-1]
A charge generating substance was prepared by dissolving 0.1 g (mixing ratio: 75/25) in sulfuric acid, and then pouring the mixture into water for precipitation. After 0.25 g of this charge generating substance was ball-milled with 6.25 g of a polycarbonate Z (PC-Z) solution (dissolved in tetrahydrofuran at 2 wt%), the pigment composition was 2 wt%, and the PC-Z composition was 50 w.
t%, 18 wt% of the following acceptor compound (Chemical Formula 3),
The following hole transfer material (Chemical formula 4) should be 30 wt% 1
A 0 wt% PC-Z solution, an acceptor compound, and a hole transfer substance were added to prepare a photoconductor coating solution. This solution was applied onto an aluminum substrate and dried by heating to prepare a single layer type photoreceptor having a thickness of about 18 μm.
【化３】 [Chemical 3]
【化４】 [Chemical 4]
【００２２】実施例２〜３ 無金属フタロシアニンと前記構造式〔Ａ−１〕との混合
比を各々５０／５０、２５／７５とした以外は実施例１
と同様にして実施例２及び実施例３の感光体を作成し
た。Examples 2 to 3 Example 1 except that the metal-free phthalocyanine and the structural formula [A-1] were mixed at the mixing ratios of 50/50 and 25/75, respectively.
In the same manner as above, the photoconductors of Examples 2 and 3 were prepared.
【００２３】比較例１ 無金属フタロシアニン０．４ｇを硫酸に溶解した後、水
中にあけて析出させた化合物を電荷発生物質として用い
る以外は実施例１と同様にして比較例１の感光体を作成
した。Comparative Example 1 A photoconductor of Comparative Example 1 was prepared in the same manner as in Example 1 except that 0.4 g of a metal-free phthalocyanine was dissolved in sulfuric acid and then the compound was poured into water and deposited as a charge generating substance. did.
【００２４】比較例２ 前記構造式〔Ａ−１〕０．４ｇを硫酸に溶解した後、水
中にあけて析出させた化合物を電荷発生物質として用い
る以外は実施例１と同様にして比較例２の感光体を作成
した。Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1 except that 0.4 g of the above structural formula [A-1] was dissolved in sulfuric acid and then the compound was poured into water and precipitated to use as a charge generating substance. The photoconductor was created.
【００２５】実施例１〜３及び比較例１〜２に従って作
成した電子写真感光体を静電試験装置（ＳＰ−４２８：
川口電気社製）を用いて評価した。評価は初めに＋１６
μＡの条件で２０秒間のコロナ帯電を行い、２０秒間放
置後の表面電位Ｖｏを求めた。続いて表面照度が２０ｌ
ｕｘとなるような露光（タングステンランプ）を行い、
表面電位が１／２に減衰するのに必要な露光量（Ｅ１／
２）を測定した。その結果を表３に示す。また、＋６Ｋ
Ｖのコロナ放電を行い感光体表面を帯電させ、その後暗
所にて表面電位を＋５００Ｖまで減衰させ、ついで単色
光を照射し感光体の表面電位を光減衰させる。この時、
感光体の表面電位が＋５００Ｖから＋２５０Ｖまで減衰
させるのに要した光のエネルギー、半減露光エネルギー
Ｅ１／２（ｃｍ2／μＪ）を測定した。その結果を表３
に示す。また４６０〜７６０ｎｍの範囲での分光感度を
図３に示す。The electrophotographic photosensitive members prepared according to Examples 1 to 3 and Comparative Examples 1 and 2 were subjected to an electrostatic testing device (SP-428:
It was evaluated by using Kawaguchi Electric Co., Ltd.). Evaluation is +16 at the beginning
Corona charging was performed for 20 seconds under the condition of μA, and the surface potential Vo after standing for 20 seconds was obtained. Then the surface illuminance is 20 l
Do the exposure (tungsten lamp) to get ux,
The amount of exposure required to reduce the surface potential to 1/2 (E1 /
2) was measured. The results are shown in Table 3. Also, + 6K
The surface of the photoconductor is charged by performing corona discharge of V, and then the surface potential is attenuated to +500 V in a dark place, and then monochromatic light is irradiated to optically attenuate the surface potential of the photoconductor. At this time,
The energy of light required to attenuate the surface potential of the photoconductor from +500 V to +250 V, and the half-exposure energy E1 / 2 (cm 2 / μJ) were measured. The results are shown in Table 3.
Shown in. Further, FIG. 3 shows the spectral sensitivity in the range of 460 to 760 nm.
【表３】 [Table 3]
【００２６】実施例４ 無金属フタロシアニン０．３ｇと前記構造式〔Ａ−１〕
０．１ｇ（混合比：７５／２５）とを硫酸に溶解した
後、水中にあけて析出させることによって電荷発生物質
を調製した。この電荷発生物質０．２５ｇをポリカーボ
ネートＺ（ＰＣ−Ｚ）溶液６．２５ｇ（テトラヒドロフ
ラン中に２ｗｔ％に溶解したもの）とともにボールミリ
ングし、顔料／ＰＣ−Ｚ＝２／１となるようテトラヒド
ロフランを加えてアルミニウム基体上に塗布し、乾燥後
膜厚が０．１５μｍの電荷発生層を形成した。次に実施
例１で用いた正孔移動剤０．５ｇを１０ｗｔ％ＰＣ−Ｚ
溶液５ｇとテトラヒドロフラン０．１１ｇとに溶解した
溶液を作成し、電荷発生層状に塗布した。乾燥後膜厚１
８μｍの電荷輸送層を形成し、積層型感光体を作製し
た。Example 4 0.3 g of metal-free phthalocyanine and the above structural formula [A-1]
A charge generating substance was prepared by dissolving 0.1 g (mixing ratio: 75/25) in sulfuric acid, and then pouring the mixture into water for precipitation. 0.25 g of this charge generating substance was ball-milled with 6.25 g of a polycarbonate Z (PC-Z) solution (dissolved in tetrahydrofuran at 2 wt%), and tetrahydrofuran was added so that pigment / PC-Z = 2/1. And applied on an aluminum substrate to form a charge generation layer having a thickness of 0.15 μm after drying. Next, 0.5 g of the hole transfer agent used in Example 1 was added to 10 wt% PC-Z.
A solution prepared by dissolving 5 g of the solution and 0.11 g of tetrahydrofuran was prepared and applied on the charge generation layer. Film thickness after drying 1
A charge transporting layer having a thickness of 8 μm was formed to prepare a laminated photoreceptor.
【００２７】実施例５〜６ 無金属フタロシアニンと前記構造式〔Ａ−１〕との混合
比を各々５０／５０、２５／７５とした以外は実施例４
と同様にして、実施例５および実施例６の感光体を作成
した。Examples 5 to 6 Example 4 except that the metal-free phthalocyanine and the structural formula [A-1] were mixed at the mixing ratios of 50/50 and 25/75, respectively.
In the same manner as in, the photoconductors of Example 5 and Example 6 were prepared.
【００２８】比較例３ 無金属フタロシアニン０．４ｇを硫酸に溶解した後、水
中にあけて析出させた化合物を電荷発生物質として用い
る以外は実施例４と同様にして、比較例３の感光体を作
成した。Comparative Example 3 A photoconductor of Comparative Example 3 was prepared in the same manner as in Example 4 except that 0.4 g of a metal-free phthalocyanine was dissolved in sulfuric acid and then the compound was poured into water and precipitated to use as a charge generating substance. Created.
【００２９】比較例４ 前記構造式〔Ａ−１〕０．４ｇを硫酸に溶解した後、水
中にあけて析出させた化合物を電荷発生物質として用い
る以外は実施例４と同様にして、比較例４の感光体を作
成した。Comparative Example 4 Comparative Example 4 was carried out in the same manner as in Example 4 except that 0.4 g of the above structural formula [A-1] was dissolved in sulfuric acid and then poured into water and precipitated as a charge generating substance. 4 was prepared.
【００３０】実施例４〜６及び比較例３〜４に従って作
成した電子写真感光体を静電試験装置（ＳＰ−４２８：
川口電気社製）を用いて評価した。評価は初めに＋２４
μＡの条件で２０秒間のコロナ帯電を行い、２０秒間放
置後の表面電位Ｖｏを求めた。続いて表面照度が２０ｌ
ｕｘとなるような露光（タングステンランプ）を行い、
表面電位が１／２に減衰するのに必要な露光量（Ｅ１／
２）を測定した。その結果を表４に示す。また、−６Ｋ
Ｖのコロナ放電を行い感光体表面を帯電させ、その後暗
所にて表面電位を−４００Ｖまで減衰させ、ついで単色
光を照射し感光体の表面電位を光減衰させる。この時、
感光体の表面電位が−４００Ｖから＋２００Ｖまで減衰
させるのに要した光エネルギー、半減露光エネルギーＥ
１／２（ｃｍ2／μＪ）を測定した。その結果を表４に
示す。４６０〜７６０ｎｍの範囲での分光感度を図４に
示す。The electrophotographic photosensitive members prepared according to Examples 4 to 6 and Comparative Examples 3 to 4 were subjected to an electrostatic testing device (SP-428:
It was evaluated by using Kawaguchi Electric Co., Ltd.). Evaluation is +24 at the beginning
Corona charging was performed for 20 seconds under the condition of μA, and the surface potential Vo after standing for 20 seconds was obtained. Then the surface illuminance is 20 l
Do the exposure (tungsten lamp) to get ux,
The amount of exposure required to reduce the surface potential to 1/2 (E1 /
2) was measured. The results are shown in Table 4. Also, -6K
The surface of the photoconductor is charged by performing corona discharge of V, and then the surface potential is attenuated to -400 V in a dark place, and then monochromatic light is irradiated to optically attenuate the surface potential of the photoconductor. At this time,
Light energy required to attenuate the surface potential of the photoconductor from -400V to + 200V, half-exposure energy E
1/2 (cm 2 / μJ) was measured. The results are shown in Table 4. The spectral sensitivity in the range of 460 to 760 nm is shown in FIG.
【表４】 [Table 4]
【００３１】実施例７ 無金属フタロシアニン０．３ｇと前記構造式〔Ｂ−１〕
０．１ｇ（混合比：７５／２５）とを硫酸に溶解した
後、水中にあけて析出させることによって電荷発生物質
を調製した。この電荷発生物質０．２５ｇをポリカーボ
ネートＺ（ＰＣ−Ｚ）溶液６．２５ｇ（テトラヒドロフ
ラン中に２ｗｔ％に溶解したもの）とともにボールミリ
ングした後、顔料組成２ｗｔ％、ＰＣ−Ｚ組成が５０ｗ
ｔ％、実施例１で用いたアクセプタ化合物が１８ｗｔ
％、実施例１で用いた正孔移動材料が３０ｗｔ％となる
よう１０ｗｔ％のＰＣ−Ｚ溶液、アクセプタ化合物、正
孔移動剤を加え感光体の塗布液を作成した。この液をア
ルミニウム基体上に塗布し加熱乾燥して約１８μｍの単
層型感光体を作製した。Example 7 0.3 g of metal-free phthalocyanine and the above structural formula [B-1]
A charge generating substance was prepared by dissolving 0.1 g (mixing ratio: 75/25) in sulfuric acid, and then pouring the mixture into water for precipitation. After 0.25 g of this charge generating substance was ball-milled with 6.25 g of a polycarbonate Z (PC-Z) solution (dissolved in tetrahydrofuran at 2 wt%), the pigment composition was 2 wt%, and the PC-Z composition was 50 w.
t%, 18 wt% of the acceptor compound used in Example 1
%, A 10 wt% PC-Z solution, an acceptor compound, and a hole transfer agent were added so that the hole transfer material used in Example 1 would be 30 wt%, to prepare a coating solution for a photoreceptor. This solution was applied onto an aluminum substrate and dried by heating to prepare a single layer type photoreceptor having a thickness of about 18 μm.
【００３２】実施例８〜９ 無金属フタロシアニンと前記構造式〔Ｂ−１〕との混合
比を各々５０／５０、２５／７５とした以外は実施例１
と同様にして実施例８および実施例９の感光体を作成し
た。Examples 8 to 9 Example 1 was repeated except that the mixing ratios of the metal-free phthalocyanine and the structural formula [B-1] were 50/50 and 25/75, respectively.
Photoconductors of Examples 8 and 9 were prepared in the same manner as in.
【００３３】比較例５ 前記構造式〔Ｂ−１〕０．４ｇを硫酸に溶解した後、水
中にあけて析出させた化合物を電荷発生物質として用い
る以外は実施例１と同様にして、比較例５の感光体を作
成した。Comparative Example 5 A comparative example was carried out in the same manner as in Example 1 except that 0.4 g of the above structural formula [B-1] was dissolved in sulfuric acid and then poured into water and precipitated to use as a charge generating substance. 5 was prepared.
【００３４】実施例７〜９及び比較例５に従って作成し
た電子写真感光体を静電試験装置（ＳＰ−４２８：川口
電気社製）を用いて評価した。評価は初めに＋１６μＡ
の条件で２０秒間のコロナ帯電を行い、２０秒間放置後
の表面電位Ｖｏを求めた。続いて表面照度が２０ｌｕｘ
となるような露光（タングステンランプ）を行い、表面
電位が１／２に減衰するのに必要な露光量（Ｅ１／２）
を測定した。その結果を表５に示す。また、＋６ＫＶの
コロナ放電を行い感光体表面を帯電させ、その後暗所に
て表面電位を＋５００Ｖまで減衰させ、ついで単色光を
照射し感光体の表面電位を光減衰させる。この時、感光
体の表面電位が＋５００Ｖから＋２５０Ｖまで減衰させ
るのに要した光のエネルギー、半減露光エネルギーＥ１
／２（ｃｍ２／μＪ）を測定した。その結果を表５に示
す。４６０〜８４０ｎｍの範囲での分光感度を図５に示
す。The electrophotographic photoreceptors produced according to Examples 7 to 9 and Comparative Example 5 were evaluated using an electrostatic tester (SP-428: manufactured by Kawaguchi Electric Co., Ltd.). Evaluation is + 16μA at the beginning
Under these conditions, corona charging was performed for 20 seconds, and the surface potential Vo after standing for 20 seconds was obtained. Then the surface illuminance is 20lux
Exposure (Tungsten lamp) to achieve the following, and the amount of exposure required to reduce the surface potential to 1/2 (E1 / 2)
Was measured. The results are shown in Table 5. Further, the surface of the photoconductor is charged by performing corona discharge of +6 KV, and then the surface potential is attenuated to +500 V in a dark place, and then monochromatic light is irradiated to optically attenuate the surface potential of the photoconductor. At this time, the light energy required to attenuate the surface potential of the photoconductor from +500 V to +250 V, the half-exposure energy E1
/ 2 (cm2 / μJ) was measured. The results are shown in Table 5. The spectral sensitivity in the range of 460 to 840 nm is shown in FIG.
【表５】 [Table 5]
【００３５】実施例１０ 電荷発生物質は、無金属フタロシアニン０．３ｇと前記
構造式〔Ｂ−１〕０．１ｇ（混合比：７５／２５）とを
硫酸に溶解した後、水中にあけて析出させることによっ
て電荷発生物質を調製した。この電荷発生物質０．２５
ｇをポリカーボネートＺ（ＰＣ−Ｚ）溶液６．２５ｇ
（テトラヒドロフラン中に２ｗｔ％に溶解したもの）と
ともにボールミリングし、顔料／ＰＣ−Ｚ＝２／１とな
るようテトラヒドロフランを加えてアルミニウム基体上
に塗布し、乾燥後膜厚が０．１５μｍの電荷発生層を形
成した。次に実施例１で用いた正孔移動剤０．５ｇを１
０ｗｔ％ＰＣ−Ｚ溶液５ｇとテトラヒドロフラン０．１
１ｇとに溶解した溶液を作成し、電荷発生層状に塗布し
た。乾燥後膜厚１８μｍの電荷輸送層を形成し、積層型
電子写真感光体を作成した。Example 10 As the charge generating substance, 0.3 g of metal-free phthalocyanine and 0.1 g of the above-mentioned structural formula [B-1] (mixing ratio: 75/25) were dissolved in sulfuric acid and then poured into water to precipitate. To prepare a charge generating material. This charge generation material 0.25
6.25 g of polycarbonate Z (PC-Z) solution
Ball milling with (dissolved in tetrahydrofuran at 2 wt%), tetrahydrofuran was added so that the pigment / PC-Z = 2/1, and the mixture was coated on an aluminum substrate. After drying, a charge with a film thickness of 0.15 μm was generated. Layers were formed. Next, 0.5 g of the hole transfer agent used in Example 1 was added to 1
0 wt% PC-Z solution 5 g and tetrahydrofuran 0.1
A solution dissolved in 1 g was prepared and applied as a charge generation layer. After drying, a charge transport layer having a film thickness of 18 μm was formed to prepare a laminated electrophotographic photosensitive member.
【００３６】実施例１１〜１２ 無金属フタロシアニンと前記構造式〔Ｂ−１〕との混合
比を各々５０／５０、２５／７５とした以外は実施例１
０と同様にして、実施例１１と実施例１２の感光体を作
成した。Examples 11 to 12 Example 1 except that the metal-free phthalocyanine and the structural formula [B-1] were mixed at the mixing ratios of 50/50 and 25/75, respectively.
Photoconductors of Example 11 and Example 12 were prepared in the same manner as in Example 1.
【００３７】比較例６ 前記構造式〔Ｂ−１〕０．４ｇを硫酸に溶解した後、水
中にあけて析出させた化合物を電荷発生物質として用い
る以外は実施例１０と同様にして、比較例６の感光体を
作成した。Comparative Example 6 A comparative example was carried out in the same manner as in Example 10 except that 0.4 g of the above structural formula [B-1] was dissolved in sulfuric acid and then poured into water and precipitated to use as a charge generating substance. A photoconductor of No. 6 was prepared.
【００３８】実施例１０〜１２及び比較例６に従って作
成した電子写真感光体を静電試験装置（ＳＰ−４２８：
川口電気社製）を用いて評価した。評価は初めに−２４
μＡの条件で２０秒間のコロナ帯電を行い、２０秒間放
置後の表面電位Ｖｏを求めた。続いて表面照度が２０ｌ
ｕｘとなるような露光（タングステンランプ）を行い、
表面電位が１／２に減衰するのに必要な露光量（Ｅ１／
２）を測定した。その結果を表６に示す。また、−６Ｋ
Ｖのコロナ放電を行い感光体表面を帯電させ、その後暗
所にて表面電位を−４００Ｖまで減衰させる。ここで単
色光を照射し感光体の表面電位を光減衰させる。この
時、感光体の表面電位が−４００Ｖから＋２００Ｖまで
減衰させるのに要した光エネルギー、半減露光エネルギ
ーＥ１／２（ｃｍ２／μＪ）を測定した。その結果を表
６に示す。また４６０〜８４０ｎｍの範囲での分光感度
を図６に示す。The electrophotographic photosensitive members produced according to Examples 10 to 12 and Comparative Example 6 were subjected to an electrostatic testing device (SP-428:
It was evaluated by using Kawaguchi Electric Co., Ltd.). Evaluation is -24
Corona charging was performed for 20 seconds under the condition of μA, and the surface potential Vo after standing for 20 seconds was obtained. Then the surface illuminance is 20 l
Do the exposure (tungsten lamp) to get ux,
The amount of exposure required to reduce the surface potential to 1/2 (E1 /
2) was measured. The results are shown in Table 6. Also, -6K
A V corona discharge is performed to charge the surface of the photoconductor, and then the surface potential is attenuated to −400 V in a dark place. Here, monochromatic light is irradiated to attenuate the surface potential of the photoconductor. At this time, the light energy required to attenuate the surface potential of the photoconductor from -400 V to +200 V and the half-exposure energy E1 / 2 (cm2 / μJ) were measured. The results are shown in Table 6. Further, the spectral sensitivity in the range of 460 to 840 nm is shown in FIG.
【表６】 [Table 6]
【００３９】[0039]
【発明の効果】以上の結果から明らかなように、本発明
の電子写真感光体は無金属フタロシアニンとペリレンテ
トラカルボン酸ジイミド化合物又は、ペリレンテトラカ
ルボン酸ジイミダゾール化合物とを一旦均一な溶解状態
とし、その後貧溶媒で粒子化した混合物を電荷発生物質
として用いたことから、高感度で電子写真特性に優れた
ものである。As is apparent from the above results, the electrophotographic photosensitive member of the present invention is a uniform dissolution state of the metal-free phthalocyanine and perylene tetracarboxylic acid diimide compound or perylene tetracarboxylic acid diimidazole compound, After that, the mixture, which was made into particles with a poor solvent, was used as the charge generating substance, so that it has high sensitivity and excellent electrophotographic characteristics.
【図１】本発明に係る単層型電子写真感光体の模式断面
図。FIG. 1 is a schematic cross-sectional view of a single-layer type electrophotographic photosensitive member according to the present invention.
【図２】本発明に係る積層型電子写真感光体の模式断面
図。FIG. 2 is a schematic sectional view of a laminated electrophotographic photosensitive member according to the present invention.
【図３】実施例２〜３及び比較例１〜２で得られた電子
写真感光体の分光感度曲線。FIG. 3 is a spectral sensitivity curve of the electrophotographic photoconductors obtained in Examples 2-3 and Comparative Examples 1-2.
【図４】実施例５〜６及び比較例３〜４で得られた電子
写真感光体の分光感度曲線。FIG. 4 is a spectral sensitivity curve of the electrophotographic photoconductors obtained in Examples 5-6 and Comparative Examples 3-4.
【図５】実施例８〜９及び比較例５で得られた電子写真
感光体の分光感度曲線。5 is a spectral sensitivity curve of the electrophotographic photoconductors obtained in Examples 8 to 9 and Comparative Example 5. FIG.
【図６】実施例１１〜１２及び比較例６で得られた電子
写真感光体の分光感度曲線。6 is a spectral sensitivity curve of the electrophotographic photoconductors obtained in Examples 11 to 12 and Comparative Example 6. FIG.
１ 導電性基体 ２ 電荷発生物質 ３ 結着剤中に電荷輸送物質が分子状に分散されたマト
リックス ４ 電荷発生層 ５ 電荷輸送層DESCRIPTION OF SYMBOLS 1 Conductive substrate 2 Charge generating substance 3 Matrix in which charge transporting substance is molecularly dispersed in a binder 4 Charge generating layer 5 Charge transporting layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小島 明夫 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Kojima 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.
Claims (2)
と電荷輸送物質とが同一層中に含有されている単層感光
層、又は両物質が別々の層に含有されている積層感光層
を有する電子写真感光体において、該電荷発生物質とし
て無金属フタロシアニンと下記一般式（Ｉ）（化１）で
表わされるペリレンテトラカルボン酸ジイミド化合物と
を一旦均一な溶解状態とし、その後貧溶媒で粒子化した
混合物を用いることを特徴とする電子写真感光体。 【化１】 （式中、Ｒ1、Ｒ2は水素、置換もしくは無置換のアルキ
ル基又は置換もしくは無置換のアリール基を表す。）1. A single-layer photosensitive layer in which at least a charge-generating substance and a charge-transporting substance are contained in the same layer, or a laminated photosensitive layer in which both substances are contained in separate layers, on a conductive substrate. In the electrophotographic photosensitive member, a metal-free phthalocyanine as the charge generating substance and a perylenetetracarboxylic acid diimide compound represented by the following general formula (I) (formula 1) are once brought into a uniform dissolved state, and then granulated with a poor solvent. An electrophotographic photoreceptor comprising a mixture. [Chemical 1] (In the formula, R 1 and R 2 represent hydrogen, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
と電荷輸送物質とが同一層中に含有されている単層感光
層、又は両物質が別々の層に含有されている積層感光層
を有する電子写真感光体において、該電荷発生物質とし
て無金属フタロシアニンと下記一般式（ＩＩ）（化２）
で表わされるペリレンテトラカルボン酸ジイミダゾール
化合物とを一旦均一な溶解状態とし、その後貧溶媒で粒
子化した混合物を用いることを特徴とする電子写真感光
体。 【化２】 （式中、Ｘ1、Ｘ2は、置換もしくは無置換の縮合多環又
はヘテロ環の２価基を表す。）2. A single-layer photosensitive layer in which at least a charge-generating substance and a charge-transporting substance are contained in the same layer, or a laminated photosensitive layer in which both substances are contained in separate layers, on a conductive substrate. In an electrophotographic photoreceptor, a metal-free phthalocyanine and the following general formula (II)
An electrophotographic photosensitive member comprising a mixture of the perylene tetracarboxylic acid diimidazole compound represented by the formula (1) in a uniformly dissolved state and then granulating with a poor solvent. [Chemical 2] (In the formula, X 1 and X 2 each represents a substituted or unsubstituted fused polycyclic or heterocyclic divalent group.)
Priority Applications (1)
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|---|---|---|---|
| JP16976693A JP3230548B2 (en) | 1993-06-16 | 1993-06-16 | Electrophotographic photoreceptor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16976693A JP3230548B2 (en) | 1993-06-16 | 1993-06-16 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH075715A true JPH075715A (en) | 1995-01-10 |
| JP3230548B2 JP3230548B2 (en) | 2001-11-19 |
Family
ID=15892462
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08320584A (en) * | 1995-05-24 | 1996-12-03 | Nec Corp | Electrophotographic photoreceptor |
| US6391505B1 (en) * | 1999-07-28 | 2002-05-21 | Kyocera Mita Corporation | Phthalocyanine crystal and its production, and electrophotosensitive material using the same |
| US6514651B1 (en) | 1999-05-31 | 2003-02-04 | Konica Corporation | Metal phthalocyanine crystal particles, production method thereof, and electrophotographic photoreceptor as well as electrophotographic process using the same |
| JP2003101060A (en) * | 2001-09-20 | 2003-04-04 | National Institute Of Advanced Industrial & Technology | Organic photocurrent amplifier element and manufacturing method therefor |
| JP2005309292A (en) * | 2004-04-26 | 2005-11-04 | Kyocera Mita Corp | Electrophotographic photoreceptor for wet development and image forming apparatus for wet development |
| JP2007024917A (en) * | 2005-07-12 | 2007-02-01 | Ricoh Co Ltd | Image forming apparatus and image forming method |
| USRE45758E1 (en) | 2000-12-06 | 2015-10-13 | Panasonic Intellectual Property Management Co., Ltd. | OFDM signal transmission system, portable terminal and E-commerce system |
| JP2016142929A (en) * | 2015-02-02 | 2016-08-08 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photoreceptor, manufacturing method of electrophotographic photoreceptor, image forming apparatus, and process cartridge |
-
1993
- 1993-06-16 JP JP16976693A patent/JP3230548B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08320584A (en) * | 1995-05-24 | 1996-12-03 | Nec Corp | Electrophotographic photoreceptor |
| US6514651B1 (en) | 1999-05-31 | 2003-02-04 | Konica Corporation | Metal phthalocyanine crystal particles, production method thereof, and electrophotographic photoreceptor as well as electrophotographic process using the same |
| US6391505B1 (en) * | 1999-07-28 | 2002-05-21 | Kyocera Mita Corporation | Phthalocyanine crystal and its production, and electrophotosensitive material using the same |
| USRE45758E1 (en) | 2000-12-06 | 2015-10-13 | Panasonic Intellectual Property Management Co., Ltd. | OFDM signal transmission system, portable terminal and E-commerce system |
| JP2003101060A (en) * | 2001-09-20 | 2003-04-04 | National Institute Of Advanced Industrial & Technology | Organic photocurrent amplifier element and manufacturing method therefor |
| JP2005309292A (en) * | 2004-04-26 | 2005-11-04 | Kyocera Mita Corp | Electrophotographic photoreceptor for wet development and image forming apparatus for wet development |
| JP2007024917A (en) * | 2005-07-12 | 2007-02-01 | Ricoh Co Ltd | Image forming apparatus and image forming method |
| JP4523503B2 (en) * | 2005-07-12 | 2010-08-11 | 株式会社リコー | Image forming apparatus and image forming method |
| JP2016142929A (en) * | 2015-02-02 | 2016-08-08 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photoreceptor, manufacturing method of electrophotographic photoreceptor, image forming apparatus, and process cartridge |
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|---|---|
| JP3230548B2 (en) | 2001-11-19 |
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