JP3473207B2 - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
- Publication number
- JP3473207B2 JP3473207B2 JP22196795A JP22196795A JP3473207B2 JP 3473207 B2 JP3473207 B2 JP 3473207B2 JP 22196795 A JP22196795 A JP 22196795A JP 22196795 A JP22196795 A JP 22196795A JP 3473207 B2 JP3473207 B2 JP 3473207B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive layer
- electrophotographic
- layer
- photoreceptor
- photoconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Photoreceptors In Electrophotography (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、電子写真感光体に
関するものである。特に、感光層の特異な光電流の流れ
方を応用し、現在次第に隆盛になってきているデジタル
記録に関する諸要求に応え得る感光体に関する。TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor. In particular, the present invention relates to a photoconductor that can respond to various demands for digital recording, which are becoming more and more prominent at present, by applying a peculiar flow of photocurrent in the photoconductive layer.
【0002】[0002]
【従来の技術】カールソン法をはじめとする電子写真法
は、原稿像をアナログ的に描写することを主眼点におい
て開発されてきた。入力光の明暗を忠実にトナー像の明
暗として再現するために、そこで用いられる感光体とし
ては、入力光量(又はその対数値)に対して線形に相似
する光電流が流れる特性(以下、「低γ特性」とい
う。)を有することが求められてきた。従って、このよ
うな低γ特性を有する感光剤を感光体の材料として選択
することが原則的として行なわれてきた。そのため、電
子写真法の初期段階における単純な光導電体に近いもの
からはじまり、セレン(Se)系のアモルファス状態の
感光層や、シリコン(Si)のアモルファス層や、Se
のアモルファス層と類似すべく作られたZnOの結着層
等が、感光体として使用されてきた。さらに、特に有機
光導電体を使用したいわゆる機能分離型の感光層が感光
体として使用されるまでに展開してきている。ところ
が、近年、電子写真技術とコンピュータ・通信が結合
し、プリンターやファクシミリの情報出力方式が電子写
真記録方式に急激に移行し、また、通常のコピーマシー
ンであっても、反転、切りとり、白抜き等の画像処理を
可能とする方式になりつつある。そのため、電子写真の
記録方式も、従来の普通紙複写機用アナログ記録形式か
らデジタル記録形式への変更が望まれている。2. Description of the Related Art Electrophotographic methods such as the Carlson method have been developed with a focus on rendering an original image in an analog manner. In order to faithfully reproduce the brightness of the input light as the brightness of the toner image, the photoconductor used therein has a characteristic that a photocurrent that is linearly similar to the input light amount (or its logarithmic value) flows (hereinafter referred to as “low It has been sought to have “gamma characteristics”). Therefore, it has been a general rule to select a photosensitizer having such a low γ characteristic as a material for a photoconductor. Therefore, starting from a material close to a simple photoconductor in the initial stage of electrophotography, a photosensitive layer in a selenium (Se) -based amorphous state, an amorphous layer of silicon (Si), and Se.
A ZnO tie layer made to resemble the amorphous layer of 1) has been used as a photoreceptor. Furthermore, a so-called function-separated type photosensitive layer using an organic photoconductor has been developed until it is used as a photosensitive body. However, in recent years, electrophotographic technology has been combined with computers and communications, and the information output method of printers and facsimiles has rapidly changed to the electrophotographic recording method. It is becoming a system that enables image processing such as. Therefore, it is desired to change the recording method for electrophotography from the conventional analog recording format for plain paper copying machines to the digital recording format.
【0003】しかしながら、前記したように、アナログ
概念に基づく伝統的な電子写真法に用いられている感光
体は、低γ特性を有しており、その特性上、コンピュー
ターのデータ出力用のプリンター、または画像をデジタ
ル処理するデジタルコピー等、入力されたデジタル光信
号をデジタル像として描写する必要がある電子写真には
不向きである。即ち、コンピューターや画像処理装置か
ら当該電子写真装置に達するまでの信号路におけるデジ
タル信号の劣化や、書き込み用の光ビームを集光させ、
または、原稿像を結像させるための光学系による収差ま
でをも、これらの感光剤を用いた感光体は忠実に描写し
てしまい、本来のデジタル画像を再現し得ないからであ
る。従って、この分野に利用できる入力光量に対する光
電流の応答がしきい値(スレッシュ・ホールド)を有す
る、いわゆる高γ特性を有した感光体の提供が強く渇望
されている。However, as described above, the photoconductor used in the traditional electrophotographic method based on the analog concept has a low γ characteristic, and due to the characteristic, a printer for outputting data of a computer, Alternatively, it is not suitable for an electronic photograph such as a digital copy in which an image is digitally processed, or the like, in which an input digital optical signal needs to be described as a digital image. That is, the deterioration of the digital signal in the signal path from the computer or the image processing device to the electrophotographic device, or the light beam for writing is focused,
Alternatively, even with the aberration caused by the optical system for forming the original image, the photoconductor using these photosensitizers faithfully renders the original digital image. Therefore, it is strongly desired to provide a photoconductor having a so-called high γ characteristic, in which the response of the photocurrent to the input light amount applicable to this field has a threshold value (threshold).
【0004】[0004]
【発明が解決しようとする課題】この様な状況下、特開
平1−169454号公報には、デジタル光入力用感光
体の概念が開示されている。しかしながらその電子写真
感光体特性は感度、暗減衰時間、残留電位のバランスに
おいて十分なものではなく実用上大きな問題があった。
本発明は、この現状に鑑みなされたもので、高感度、低
残留電位のデジタル光入力用感光体を提供することを目
的とするものである。Under such circumstances, Japanese Patent Application Laid-Open No. 1-169454 discloses the concept of a photoreceptor for digital optical input. However, the characteristics of the electrophotographic photosensitive member are not sufficient in the balance of sensitivity, dark decay time, and residual potential, which poses a serious problem in practical use.
The present invention has been made in view of this situation, and an object of the present invention is to provide a high-sensitivity, low residual potential digital photoinput photosensitive member.
【0005】[0005]
【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意検討した結果、特に感光層の構成を
特定の積層構造とすることにより、従来の材料系を用い
ても感度、暗減衰時間、残留電位の最適化が出来ること
を見いだし、本発明を完成するに至った。本発明の要旨
は、電荷発生剤として、フタロシアニン顔料と結着剤樹
脂を含む感光層を導電性支持体上に有する電子写真感光
体において、該感光層が各層に電荷発生剤を含む2層以
上からなり、各感光層中の電荷発生剤の量子効率は、導
電性支持体側の感光層の方が小さいことを特徴とする、
デジタル光入力電子写真感光体にある。電荷発生剤の量
子効率は、感光体中に入射する光子数と発生するキャリ
ア数との比で表され、理想的に光子1個に対しキャリア
1個が発生するとき、量子効率は1となる。この量子効
率は、電子写真的に感光体が用いられる波長の光を用い
て得た光減衰曲線より求められる。As a result of intensive studies for solving the above-mentioned problems, the inventors of the present invention have found that the sensitivity of the conventional material system can be improved even if the conventional material system is used, in particular, by forming the photosensitive layer into a specific laminated structure. The inventors have found that the dark decay time and the residual potential can be optimized, and have completed the present invention. The gist of the present invention is to provide an electrophotographic photoreceptor having a photosensitive layer containing a phthalocyanine pigment and a binder resin as a charge generating agent on a conductive support, wherein the photosensitive layer comprises two or more layers each containing a charge generating agent. The quantum efficiency of the charge generating agent in each photosensitive layer is characterized in that the photosensitive layer on the side of the conductive support is smaller .
Digital light input electrophotographic photoreceptor. The quantum efficiency of the charge generating agent is represented by the ratio of the number of photons incident on the photoconductor to the number of carriers generated. When one carrier is generated ideally for one photon, the quantum efficiency is 1. . This quantum efficiency is obtained from a light attenuation curve obtained by using light of a wavelength at which the photoconductor is electrophotographically used.
【0006】[0006]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明に用いられる電荷発生剤は結着剤樹脂に分散さ
せ、光導電性を示すものであればよく、ピリリウム系染
料、チオピリリウム系染料、シアニン系染料、フタロシ
アニン系顔料、アントアントロン系顔料、ジベンズピレ
ンキノン顔料、ピラントロン顔料、トリスアゾ顔料、ジ
スアゾ顔料、アゾ顔料、インジゴ染料、キナクリドン系
顔料、非対称キノシアニン、キノシアニン顔料、酸化亜
鉛、硫化カドミウム、シリコン、セレン等が例として挙
げられる。必要に応じて、電荷発生剤の混合物を使用し
てもよい。混合物の場合の量子効率は、各々単体の量子
効率の重量平均値を用いる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The charge generating agent used in the present invention is dispersed in a binder resin and may be any one that exhibits photoconductivity, and may be a pyrylium dye, a thiopyrylium dye, a cyanine dye, a phthalocyanine pigment, an anthranthone pigment, Examples thereof include benzpyrenequinone pigment, pyranthrone pigment, trisazo pigment, disazo pigment, azo pigment, indigo dye, quinacridone pigment, asymmetric quinocyanine, quinocyanine pigment, zinc oxide, cadmium sulfide, silicon and selenium. Mixtures of charge generating agents may be used if desired. As the quantum efficiency in the case of a mixture, the weight average value of the quantum efficiency of each simple substance is used.
【0007】電荷発生剤として好ましくは、フタロシア
ニン系顔料、トリスアゾ顔料、ジスアゾ顔料、アゾ顔
料、酸化亜鉛、硫化カドミウム、シリコン、セレンが用
いられ、さらに好ましくはフタロシアニン系顔料が用い
られる。感光層が2層構造をとる場合の電荷発生剤の量
子効率は導電性支持体側の感光層より、上層の感光層の
方が大きければ良いが、その比率は、好ましくは1.2
倍以上、さらに好ましくは2倍以上である。The charge generating agent is preferably a phthalocyanine pigment, a trisazo pigment, a disazo pigment, an azo pigment, zinc oxide, cadmium sulfide, silicon or selenium, and more preferably a phthalocyanine pigment. When the photosensitive layer has a two-layer structure, the quantum efficiency of the charge generating agent may be higher in the upper photosensitive layer than in the photosensitive layer on the conductive support side, but the ratio is preferably 1.2.
It is twice or more, more preferably twice or more.
【0008】具体的な電荷発生剤の組み合わせとしては
導電支持体側の感光層から順にアゾ顔料とフタロシアニ
ン顔料、アゾ顔料とトリスアゾ顔料、酸化亜鉛とフタロ
シアニン顔料、等がある。フタロシアニン顔料を用いた
系では中心金属、結晶型によっても量子効率が異なり、
メタルフリーフタロシアニンとチタニルフタロシアニ
ン、銅フタロシアニンとメタルフリーフタロシアニン、
メタルフリーフタロシアニンと混晶型フタロシアニン等
の組み合わせが考えられる。Specific examples of the combination of the charge generating agents include an azo pigment and a phthalocyanine pigment, an azo pigment and a trisazo pigment, a zinc oxide and a phthalocyanine pigment in this order from the photosensitive layer on the conductive support side. In the system using the phthalocyanine pigment, the quantum efficiency differs depending on the central metal and crystal type,
Metal-free phthalocyanine and titanyl phthalocyanine, copper phthalocyanine and metal-free phthalocyanine,
Combinations of metal-free phthalocyanine and mixed crystal phthalocyanine are possible.
【0009】3層以上の構造を取る場合も量子効率は導
電性支持体側の感光層より、上層の感光層の方が大きけ
れば良く、各層間の量子効率の比率は1.2倍以上離れ
ていることが好ましい。本発明の感光体は電荷発生剤を
適当な溶媒中に結着剤樹脂と共に分散させ導電性支持体
上に塗布、乾燥することにより製膜される。結着剤樹脂
としては、通常、電子写真感光体に使用されるものであ
れば特に限定されず、ポリカーボネート、ポリエステ
ル、メタクリル樹脂、アクリル樹脂、ポリ塩化ビニル、
ポリ塩化ビニリデン、ポリスチレン、ポリビニルアセテ
ート、スチレン−ブタジエン共重合体、塩化ビニリデン
−アクリロニトリル共重合体、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、シリコン樹脂、シリコン−アルキッド樹脂、フ
ェノール−ホルムアルデヒド樹脂、スチレン−アルキッ
ド樹脂、ポリ−N−ビニルカルバゾール、ポリビニルブ
チラール、フッ素樹脂、ウレタン樹脂、アルキッド樹
脂、エポキシ樹脂、メラミン樹脂、等の絶縁性樹脂、ま
たはポリビニルカルバゾール、ポリシラン等の半導電性
樹脂を用いることが出来る。また、熱及び/又は光によ
って架橋される熱硬化性樹脂及び光硬化性樹脂も使用で
きる。Even in the case of a structure having three or more layers, the quantum efficiency may be higher in the upper photosensitive layer than in the photosensitive layer on the side of the conductive support, and the quantum efficiency ratio between the layers is 1.2 times or more. Is preferred. The photoreceptor of the present invention is formed into a film by dispersing a charge generating agent together with a binder resin in a suitable solvent, coating the conductive support on the conductive support, and drying. The binder resin is not particularly limited as long as it is usually used for electrophotographic photoreceptors, and includes polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride,
Polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone -Insulating resin such as alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, fluororesin, urethane resin, alkyd resin, epoxy resin, melamine resin, or polyvinylcarbazole, polysilane. It is possible to use a semiconductive resin such as. Further, a thermosetting resin and a photocurable resin which are crosslinked by heat and / or light can also be used.
【0010】これらの結合剤を使用する場合、さらに、
可塑剤、流動性付与剤、ピンホール抑制剤等の添加剤を
必要に応じて添加することができる。感光層には、感光
特性を改良する目的で電荷輸送物質を添加させることも
可能である。電荷輸送物質としては、例えばトリニトロ
フルオレノン、テトラニトロフルオレノンなどの電子受
容性物質、或いは、例えばポリ−N−ビニルカルバゾー
ルに代表されるような複素環化合物を側鎖に有する重合
体、トリアゾール誘導体、オキサジアゾール誘導体、イ
ミダゾール誘導体、ピラゾリン誘導体、ポリアリールア
ルカン誘導体、フェニレンジアミン誘導体、ヒドラゾン
誘導体、アミノ置換カルコン誘導体、トリアリールアミ
ノ誘導体、カルバゾール誘導体、スチルベン誘導体など
の正電荷輸送性の電子供与性物質が挙げられるが、本発
明において用いられる電荷輸送物質がこれらに限定され
るものではない。When using these binders,
Additives such as a plasticizer, a fluidity imparting agent, and a pinhole inhibitor can be added as necessary. A charge transport material may be added to the photosensitive layer for the purpose of improving photosensitive characteristics. Examples of the charge-transporting substance include electron-accepting substances such as trinitrofluorenone and tetranitrofluorenone, or polymers having a heterocyclic compound represented by poly-N-vinylcarbazole in the side chain, triazole derivatives, and the like. Positive charge transporting electron-donating substances such as oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, polyarylalkane derivatives, phenylenediamine derivatives, hydrazone derivatives, amino-substituted chalcone derivatives, triarylamino derivatives, carbazole derivatives, and stilbene derivatives are available. However, the charge transport material used in the present invention is not limited to these.
【0011】本発明で用いられる導電性支持体として
は、金属板、金属ドラム、または導電性ポリマー、酸化
インジウム等の導電性化合物、若しくはアルミニウム、
パラジウム、金等の金属よりなる導電性薄層を塗布、蒸
着、ラミネート等の手段により、紙、セラミック、プラ
スチック、フィルム等の基体に設けてなるもの等が用い
られる。これらの形態はシート状、ドラム状、ベルト
状、シームレスベルト状等のいずれの形態をとっても良
い。The conductive support used in the present invention includes a metal plate, a metal drum, a conductive polymer, a conductive compound such as indium oxide, or aluminum.
A conductive thin layer made of a metal such as palladium or gold is provided on a substrate such as paper, ceramic, plastic or film by means of coating, vapor deposition, laminating and the like. These forms may take any form such as a sheet form, a drum form, a belt form and a seamless belt form.
【0012】本発明の電子写真感光体は電荷発生剤、結
着剤街脂、溶剤及び必要に応じその他の成分などを、ボ
ールミル、アトライター、超音波分散器、ホモミキサ
ー、ペイントミキサー、サンドミル、アトライター、デ
ィスパーザー、超音波分散等などの混練分散機で均一に
分散させ、エアードクターコーター、ブレードコータ
ー、ロッドコーター、リバースロールコーター、スプレ
ーコーター、ホットコーター、スクゥイーズコーター、
グラビアコーターなどの塗布方式で感光体組成物を導電
性基体上に塗布して、感光層を形成することができる。The electrophotographic photoreceptor of the present invention comprises a ball mill, an attritor, an ultrasonic disperser, a homomixer, a paint mixer, a sand mill, a charge-generating agent, a binder, a street fat, a solvent and, if necessary, other components. Distribute evenly with a kneading disperser such as an attritor, disperser, ultrasonic disperser, etc., air doctor coater, blade coater, rod coater, reverse roll coater, spray coater, hot coater, squeeze coater,
The photosensitive composition can be applied to the conductive substrate by a coating method such as a gravure coater to form a photosensitive layer.
【0013】塗布後、感光層として十分な帯電電位をも
つことができるように適当に乾燥を行う。また、結着剤
樹脂の種類によっては硬化反応を行うこともできる。上
記した溶剤の例としては、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系溶剤、テトラヒドロ
フラン等のエーテル系溶剤、トルエン、キシレン等の芳
香族系溶剤、塩化メチレン、四塩化炭素等のハロゲン化
炭化水素系溶剤、メタノール、エタノール、プロパノー
ル等のアルコール系溶剤が挙げられる。After coating, appropriate drying is carried out so that the photosensitive layer can have a sufficient charging potential. Further, depending on the type of binder resin, a curing reaction can be performed. Examples of the above-mentioned solvent, acetone, methyl ethyl ketone, ketone solvents such as cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride. , Alcoholic solvents such as methanol, ethanol and propanol.
【0014】本発明の電子写真感光体は2層以上の電荷
発生層を導電性支持体上に積層して形成されるが、1層
の膜厚は、通常、0.1〜20μmであり、好ましくは
0.1〜10μmの範囲である。感光層全体の膜厚は、
通常、3〜50μmであり、さらに好ましくは5〜30
μmである。電荷発生剤の含有割合([電荷発生剤]/
[電荷発生層全体の重量])は10〜50重量%の範囲
が好ましく、各層で異なっていてもよい。The electrophotographic photoreceptor of the present invention is formed by laminating two or more charge generation layers on a conductive support, and the thickness of one layer is usually 0.1 to 20 μm. The range is preferably 0.1 to 10 μm. The film thickness of the entire photosensitive layer is
Usually, it is 3 to 50 μm, and more preferably 5 to 30 μm.
μm. Content ratio of charge generation agent ([charge generation agent] /
The [weight of the entire charge generation layer] is preferably in the range of 10 to 50% by weight, and may be different in each layer.
【0015】また、本発明の電子写真感光体は、上記の
様にして得られる導電性基体上に直接、感光層を積層し
た構造の電子写真感光体の他に、導電性基体、感光層間
の接着性の改良やキャリア注入を阻止する目的で、ポリ
アミド樹脂、ポリビニルアルコール、セルロースなどの
有機高分子や、酸化アルミニウム等からなる下引き層を
導電性基体と感光層の間に有する電子写真感光体、物理
的、化学的に感光層表面を保護する目的で、アクリル樹
脂、ポリエステル樹脂、ウレタン樹脂、フッ素樹脂、シ
リコン樹脂等からなる保護層を感光層表面に有する電子
写真感光体、上記下引き層、保護層の両者を有する電子
写真感光体等であってもよい。Further, the electrophotographic photosensitive member of the present invention is not limited to the electrophotographic photosensitive member having a structure in which a photosensitive layer is directly laminated on the conductive substrate obtained as described above, as well as between the conductive substrate and the photosensitive layer. An electrophotographic photoreceptor having an undercoating layer made of an organic polymer such as polyamide resin, polyvinyl alcohol, or cellulose, or aluminum oxide or the like between a conductive substrate and a photosensitive layer for the purpose of improving adhesiveness or preventing carrier injection. , An electrophotographic photoreceptor having a protective layer made of an acrylic resin, a polyester resin, a urethane resin, a fluororesin, a silicone resin or the like on the surface of the photosensitive layer for the purpose of physically and chemically protecting the surface of the photosensitive layer; Alternatively, an electrophotographic photoreceptor having both the protective layer and the like may be used.
【0016】上記の様にして得られる本発明の電子写真
感光体は、従来の電子写真感光体に比べ、特異的な光電
流の流れ方をするため、デジタル光入力用感光体として
通常、正帯電を行なって用いることができる。すなわ
ち、従来の感光体は、上述したように、入力光量(また
はその対数値)に対して線形に対応した量の光電流が流
れるのに対して、本発明の感光体は、ある入力光量まで
は光電流が流れず、あるいは流れても極く少量であり、
前記のようにある入力光量を越えた直後から急激に光電
流が流れ出す。これは、画像階調をドット面積によって
表現するようなデジタル記録方式の電子写真感光体に要
求される光感度特性と一致するものである。Since the electrophotographic photosensitive member of the present invention obtained as described above has a specific flow of photocurrent as compared with the conventional electrophotographic photosensitive member, it is usually a positive photosensitive member for digital light input. It can be charged and used. That is, in the conventional photoconductor, as described above, the photocurrent of an amount linearly corresponding to the input light amount (or its logarithmic value) flows, whereas in the photoconductor of the present invention, up to a certain input light amount. Does not flow photocurrent, or even if it flows, it is a very small amount,
As described above, the photocurrent suddenly starts to flow immediately after the amount of input light exceeds a certain value. This is in agreement with the photosensitivity characteristic required for a digital recording type electrophotographic photosensitive member in which image gradation is expressed by a dot area.
【0017】なぜなら、レーザースポットを光学系で正
確に変調したとしても、高度な収差補正をしない限り、
光学系は必然的に収差を伴う。従って、光学系のスポッ
トそのものに光量の分布が生じること、及びハローが生
じること等は、原理的に避けられない。そのため、光エ
ネルギー(入力光量)の変化を段階的にひろう従来の電
子写真感光体では光量変化によってドットパターンの濃
度が変化し、また、わずかなスポットのにじみによって
もドットパターンの外縁が変化する。以上のドットパタ
ーンの変化が、ノイズとしてカブリの原因になるのであ
る。本発明の電子写真感光体は、この様なドットパター
ンの変化をキャンセルすることができるので、有効なデ
ジタル光入力感光体である。また、上記の様にして製造
される本発明の電子写真感光体は、感光層と導電性基体
との接着性が大きく、耐湿性が良好であり、経時変化が
少なく、毒性上の問題も少なく、製造が容易であり、安
価である等の実用上優れた特徴を有するものである。This is because even if the laser spot is accurately modulated by the optical system, unless a high degree aberration correction is performed,
The optical system inevitably involves aberrations. Therefore, in principle, it is inevitable that a light amount distribution occurs in the spot itself of the optical system and that a halo occurs. Therefore, in the conventional electrophotographic photosensitive member that changes the light energy (input light amount) stepwise, the density of the dot pattern changes due to the change in the light amount, and the outer edge of the dot pattern also changes due to slight spot bleeding. The above change in the dot pattern causes fogging as noise. The electrophotographic photoconductor of the present invention is an effective digital light input photoconductor since it can cancel such a change in the dot pattern. Further, the electrophotographic photoreceptor of the present invention produced as described above has a large adhesiveness between the photosensitive layer and the conductive substrate, good moisture resistance, little change over time, and little toxicity problem. In addition, it has practically excellent characteristics such as easy manufacture and low cost.
【0018】[0018]
【実施例】以下、実施例により本発明を更に詳細に説明
する。
実施例1
X型無金属フタロシアニン(量子効率0.2)1.0
g、硬化型フッ素樹脂(「セフラルコートA−202
B」、セントラル硝子(株)製)6.4g、メラミン
(「ニカラックMW−30」、(株)三和ケミカル製)
0.8g、シクロヘキサノン20.0gをガラスビーズ
(直径2mm)24gと共にガラス容器中に密閉し、ペ
イントシェーカーにより、4時間分散させ、分散後ガラ
スビーズを分離し第一感光体塗布液を得た。この第一感
光体塗布液を厚さ90μmの脱脂したアルミニウムシー
ト上にワイヤーバー法により塗布し、室温で予備乾燥
後、オーブン中で100℃、1時間の乾燥硬化処理を行
うことにより膜厚12μmの第一感光層を得た。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 X-type metal-free phthalocyanine (quantum efficiency 0.2) 1.0
g, curable fluororesin (“Sephral coat A-202
B ", Central Glass Co., Ltd., 6.4 g, melamine (" Nikarac MW-30 ", Sanwa Chemical Co., Ltd.)
0.8 g of cyclohexanone and 20.0 g of cyclohexanone were sealed in a glass container together with 24 g of glass beads (diameter: 2 mm) and dispersed for 4 hours with a paint shaker. After dispersion, the glass beads were separated to obtain a first photoreceptor coating liquid. This first photoreceptor coating liquid is applied on a degreased aluminum sheet having a thickness of 90 μm by a wire bar method, preliminarily dried at room temperature, and then dried and cured at 100 ° C. for 1 hour in an oven to give a film thickness of 12 μm. To obtain a first photosensitive layer of.
【0019】さらに、粉末X線回折スペクトルにおいて
ブラッグ角(2θ±0.2°)が9.5°,24.1
°,27.3°に大きいピークを有する結晶型のチタニ
ルフタロシアニン(量子効率0.7)1.0g、硬化型
フッ素樹脂(「セフラルコートA−202B」、セント
ラル硝子(株)製)6.7g、イソシアネート(「コロ
ネートHX」、日本ポリウレタン工業(株)製)0.7
g、ジブチルチンジラウレート0.1mg、シクロヘキ
サノン20.0gをガラスビーズ(直径2mm)24g
と共にガラス容器中に密閉し、ペイントシェーカーによ
り、4時間分散させ、分散後ガラスビーズを分離し第二
感光体塗布液を得た。この塗布液を第一感光体層の上に
ワイヤーバー法で塗布し、室温で予備乾燥後、オーブン
中で100℃、1時間の乾燥硬化処理を行うことにより
膜厚4μmの第二感光層を積層し、第一層と合わせて膜
厚16μmの感光層を有する二層積層感光体を得た。Further, in the powder X-ray diffraction spectrum, the Bragg angles (2θ ± 0.2 °) are 9.5 ° and 24.1.
1.0 g of crystalline titanyl phthalocyanine (quantum efficiency 0.7) having a large peak at 60 °, 27.3 °, 6.7 g of curable fluororesin (“Sephralcoat A-202B”, manufactured by Central Glass Co., Ltd.), Isocyanate (“Coronate HX”, manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.7
g, dibutyltin dilaurate 0.1 mg, cyclohexanone 20.0 g, glass beads (diameter 2 mm) 24 g
Along with this, it was sealed in a glass container and dispersed by a paint shaker for 4 hours. After dispersion, the glass beads were separated to obtain a second photoreceptor coating liquid. This coating solution is applied onto the first photosensitive layer by a wire bar method, pre-dried at room temperature, and then dried and cured at 100 ° C. for 1 hour in an oven to form a second photosensitive layer having a thickness of 4 μm. By laminating, a two-layer laminated photoreceptor having a photosensitive layer having a film thickness of 16 μm together with the first layer was obtained.
【0020】実施例2
実施例1においてX型無金属フタロシアニンをα型銅フ
タロシアニン(量子効率0.03)に、チタニルフタロ
シアニンをX型無金属フタロシアニンにそれぞれ代えた
以外は同じ条件で二層積層感光体を得た。Example 2 A two-layer laminated photoconductor under the same conditions as in Example 1 except that the X-type metal-free phthalocyanine was replaced with α-type copper phthalocyanine (quantum efficiency 0.03) and the titanyl phthalocyanine was replaced with X-type metal-free phthalocyanine. Got the body
【0021】実施例3
粉末X線回折スペクトルにおいてブラッグ角(2θ±
0.2°)6.8°,7.4°,15.0°,24.7
°,26.2°,27.2°にピークを有するチタニル
フタロシアニンと無金属フタロシアニンの混晶体(チタ
ニルフタロシアニンと無金属フタロシアニンのモル比が
8:2、量子効率0.6)を実施例1におけるX型無金
属フタロシアニンの代わりに用いた以外は実施例1と同
じ条件で二層積層感光体を得た。Example 3 In the powder X-ray diffraction spectrum, the Bragg angle (2θ ±
0.2 °) 6.8 °, 7.4 °, 15.0 °, 24.7
A mixed crystal of titanyl phthalocyanine and metal-free phthalocyanine having peaks at °, 26.2 °, and 27.2 ° (the molar ratio of titanyl phthalocyanine and metal-free phthalocyanine is 8: 2, quantum efficiency is 0.6) in Example 1. A two-layer laminated photoreceptor was obtained under the same conditions as in Example 1, except that the X-type metal-free phthalocyanine was used instead.
【0022】比較例1
実施例1の第一感光層のみの感光層を得た。すなわち、
実施例1の第一感光体塗布液と同様にして得た感光体塗
布液を厚さ90μmの脱脂したアルミニウムシート上に
ワイヤーバー法により塗布し、室温で予備乾燥後、オー
ブン中で100℃、1時間、その後200℃、10分間
の乾燥硬化処理を行うことにより膜厚16μmの感光体
を得た。Comparative Example 1 A photosensitive layer having only the first photosensitive layer of Example 1 was obtained. That is,
The photoreceptor coating liquid obtained in the same manner as the first photoreceptor coating liquid of Example 1 was applied on a degreased aluminum sheet having a thickness of 90 μm by the wire bar method, pre-dried at room temperature, and then 100 ° C. in an oven, A photoconductor having a film thickness of 16 μm was obtained by performing a dry curing treatment at 200 ° C. for 10 minutes and then at 200 ° C.
【0023】比較例2
実施例1の第二感光層のみの感光層を得た。すなわち、
実施例1の第二感光体塗布液と同様にして得た塗布液を
第一感光体層の上にワイヤーバー法で塗布し、室温で予
備乾燥後、オーブン中で100℃、1時間の乾燥硬化処
理を行うことにより膜厚16μmの感光体を得た。Comparative Example 2 A photosensitive layer having only the second photosensitive layer of Example 1 was obtained. That is,
A coating liquid obtained in the same manner as the second photosensitive liquid coating liquid of Example 1 was applied on the first photosensitive member layer by a wire bar method, pre-dried at room temperature, and then dried in an oven at 100 ° C. for 1 hour. By carrying out curing treatment, a photoreceptor having a film thickness of 16 μm was obtained.
【0024】比較例3
実施例1の感光層構成を上下逆構造にして感光体を作成
した。すなわち、実施例1の第二感光体塗布液と同様に
して得た塗布液を厚さ90μmの脱脂したアルミニウム
シート上にワイヤーバー法で塗布し、室温で予備乾燥
後、オーブン中で100℃、1時間の乾燥硬化処理を行
うことにより膜厚12μmの第一層の感光層を得た。Comparative Example 3 A photosensitive member was prepared by reversing the structure of the photosensitive layer of Example 1 upside down. That is, the coating solution obtained in the same manner as the second photoreceptor coating solution of Example 1 was applied on a degreased aluminum sheet having a thickness of 90 μm by the wire bar method, preliminarily dried at room temperature, and then 100 ° C. in an oven, By performing a dry curing treatment for 1 hour, a photosensitive layer of a first layer having a film thickness of 12 μm was obtained.
【0025】次に、実施例1の第一感光体塗布液と同様
にして得た塗布液を第一感光体層の上にワイヤーバー法
により塗布し、室温で予備乾燥後、オーブン中で100
℃、1時間の乾燥硬化処理を行うことにより膜厚4μm
の第二感光層を積層し第一層と合わせて膜厚16μmの
二層積層感光体を得た。Next, a coating solution obtained in the same manner as the coating solution for the first photoconductor of Example 1 was applied on the first photoconductor layer by the wire bar method, pre-dried at room temperature, and then dried in an oven at 100 ° C.
Film thickness 4μm by performing dry hardening treatment at ℃ for 1 hour
The second photosensitive layer of was laminated and combined with the first layer to obtain a two-layer laminated photoreceptor having a film thickness of 16 μm.
【0026】<電子写真感光体の評価>上記で得られた
各実施例及び各比較例の電子写真感光体について、光感
度特性及び繰り返し特性を感光体評価装置(シンシア−
55、ジェンテック社製)を用いて評価した。
(1)感光体特性
上記各電子写真感光体を+6.0kVの電圧でコロナ帯
電させ、これに光強度が異なった780nmの単色光を
照射し、各光強度に対する光減衰時間曲線(照射時間に
対する表面電位の特性曲線)を各々測定し、その曲線か
ら得られた一定時間照射(ここでは0.075秒)後に
おける表面電位を、図1に例示した様に各々光エネルギ
ーに対してプロットした。これをγカーブと称する。<Evaluation of Electrophotographic Photoreceptor> The photosensitivity and repetitive characteristics of the electrophotographic photoreceptors of Examples and Comparative Examples obtained above were evaluated by a photoreceptor evaluation device (Cynthia
55, manufactured by Gentec). (1) Characteristics of photoconductor Each of the electrophotographic photoconductors described above is corona-charged at a voltage of +6.0 kV, and monochromatic light of 780 nm having different light intensity is irradiated onto the electrophotographic photoconductor, and a light decay time curve (with respect to irradiation time) for each light intensity is obtained. Each surface potential curve was measured, and the surface potential after irradiation for a certain period of time (here, 0.075 seconds) obtained from the curve was plotted against the light energy as illustrated in FIG. This is called a γ curve.
【0027】表面電位を初期電位(帯電直後の電位)と
ほぼ同じ程度に維持できる光エネルギーのうち最大の光
エネルギーをE1(γカーブにおける立ち下がり点の光
エネルギー)、表面電位を残留電位程度までに低下させ
ることのできる光エネルギーのうち最小の光エネルギー
をE2(γカーブにおける立ち上がり点の光エネルギ
ー)とし、E2/E1の値を以下の評価基準でデジタル
記録可能の目途とした。
0<E2/E1<5:デジタル記録可能
5<E2/E1 :アナログ記録
また、0<E2/E1<5であるもののうちでも、E1
が小さい程、光感度がよく電子写真感光体として優れて
いるといえる。Among the light energies that can maintain the surface potential at almost the same level as the initial potential (potential immediately after charging), the maximum light energy is E1 (light energy at the falling point in the γ curve), and the surface potential is up to the residual potential. The minimum light energy among the light energies that can be reduced to E2 is E2 (light energy at the rising point in the γ curve), and the value of E2 / E1 is set as a target for digital recording according to the following evaluation criteria. 0 <E2 / E1 <5: Digitally recordable 5 <E2 / E1: Analog record Also, even if 0 <E2 / E1 <5, E1
It can be said that the smaller the value, the better the photosensitivity and the better the electrophotographic photoreceptor.
【0028】(2)繰り返し特性
評価プロセスは、各電子写真感光体について、プラス
帯電(+6.0kV)、露光(波長780nm、20
μJ/cm2 )、マイナス帯電(−5.3kV)、
イレース光(200 lux、タングステンランプ)の
繰り返しで行い、プラス帯電直後の表面電位Vo を各繰
り返し回数毎に測定し、Vo が10%以上変動するまで
の回数Nを記録した。上記評価の結果を表1に示す。(2) The repeating characteristic evaluation process was carried out by using positive charging (+6.0 kV), exposure (wavelength 780 nm, 20) for each electrophotographic photosensitive member.
μJ / cm 2 ), negative charge (-5.3 kV),
Erase light (200 lux, a tungsten lamp) is performed by repeating, the surface potential V o immediately positively charged was measured for each repetition count was recorded the number N to V o varies more than 10%. The results of the above evaluations are shown in Table 1.
【0029】[0029]
【表1】 [Table 1]
【0030】[0030]
【発明の効果】本発明によれば、高感度で低残留電位の
デジタル光入力に適した電子写真感光体を提供できる。
更に、本発明の電子写真感光体は、感光層と導電性基体
との接着性が大きく、耐湿性が良好であり、経時変化が
少なく、毒性上の問題も少なく、製造が容易であり、安
価である等の実用上優れた特徴を有する。According to the present invention, it is possible to provide an electrophotographic photoreceptor having high sensitivity and low residual potential, which is suitable for digital light input.
Further, the electrophotographic photoreceptor of the present invention has a large adhesiveness between the photosensitive layer and the conductive substrate, good moisture resistance, little change over time, little toxicity problem, easy production, and low cost. It has practically excellent features such as
【図1】電子写真感光体の表面電位と露光エネルギーと
の関係を例示する図。FIG. 1 is a diagram illustrating a relationship between a surface potential of an electrophotographic photosensitive member and exposure energy.
フロントページの続き (56)参考文献 特開 昭63−151954(JP,A) 特開 昭63−38942(JP,A) 特開 平7−64303(JP,A) 特開 平6−289641(JP,A) 特開 平6−289636(JP,A) 特開 平6−118676(JP,A) 特開 平4−296369(JP,A) 特開 平4−217263(JP,A) 特開 平1−267551(JP,A) 特開 平1−136157(JP,A) (58)調査した分野(Int.Cl.7,DB名) G03G 5/00 Continuation of the front page (56) Reference JP-A-63-151954 (JP, A) JP-A-63-38942 (JP, A) JP-A-7-64303 (JP, A) JP-A-6-289641 (JP , A) JP 6-289636 (JP, A) JP 6-118676 (JP, A) JP 4-296369 (JP, A) JP 4-217263 (JP, A) JP 1-267551 (JP, A) JP-A-1-136157 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) G03G 5/00
Claims (2)
と結着剤樹脂を含む感光層を導電性支持体上に有する電
子写真感光体において、該感光層が各層に電荷発生剤を
含む2層以上からなり、各感光層中の電荷発生剤の量子
効率は、導電性支持体側の感光層の方が小さいことを特
徴とする、デジタル光入力電子写真感光体。1. An electrophotographic photoreceptor having a photosensitive layer containing a phthalocyanine pigment and a binder resin as a charge generating agent on a conductive support, wherein the photosensitive layer contains a charge generating agent in each layer. A digital optical input electrophotographic photosensitive member comprising two or more layers, wherein the quantum efficiency of the charge generating agent in each photosensitive layer is smaller in the photosensitive layer on the side of the conductive support.
荷発生剤を用いることを特徴とする請求項1記載の電子
写真感光体。2. The electrophotographic photosensitive member according to claim 1, wherein a charge generating agent having a quantum efficiency ratio of at least twice as much is used.
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JP22196795A JP3473207B2 (en) | 1995-08-30 | 1995-08-30 | Electrophotographic photoreceptor |
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JP22196795A JP3473207B2 (en) | 1995-08-30 | 1995-08-30 | Electrophotographic photoreceptor |
Publications (2)
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JPH0968816A JPH0968816A (en) | 1997-03-11 |
JP3473207B2 true JP3473207B2 (en) | 2003-12-02 |
Family
ID=16774979
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