JPH0693125B2 - Photoconductor - Google Patents

Photoconductor

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Publication number
JPH0693125B2
JPH0693125B2 JP11591686A JP11591686A JPH0693125B2 JP H0693125 B2 JPH0693125 B2 JP H0693125B2 JP 11591686 A JP11591686 A JP 11591686A JP 11591686 A JP11591686 A JP 11591686A JP H0693125 B2 JPH0693125 B2 JP H0693125B2
Authority
JP
Japan
Prior art keywords
weight
group
layer
photoreceptor
binder
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 - Fee Related
Application number
JP11591686A
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Japanese (ja)
Other versions
JPS62272268A (en
Inventor
秀昭 植田
Original Assignee
ミノルタ株式会社
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Filing date
Publication date
Application filed by ミノルタ株式会社 filed Critical ミノルタ株式会社
Priority to JP11591686A priority Critical patent/JPH0693125B2/en
Priority to US07/035,183 priority patent/US4808505A/en
Priority to DE19873711795 priority patent/DE3711795A1/en
Publication of JPS62272268A publication Critical patent/JPS62272268A/en
Publication of JPH0693125B2 publication Critical patent/JPH0693125B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0698—Compounds of unspecified structure characterised by a substituent only

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Description

【発明の詳細な説明】 産業上の利用分野 本発明は低分子量の有機化合物を含有する感光体に関す
る。Description: FIELD OF THE INVENTION The present invention relates to a photoreceptor containing a low molecular weight organic compound.

従来の技術 一般に電子写真においては、感光体の感光層表面に帯
電，露光を行なって静電潜像を形成し、これを現像剤で
現像して可視化させ、その可視像をそのまま直接感光体
上に定着させて複写像を得る直接方式、また感光体上の
可視像を紙などの転写紙上に転写し、その転写像を定着
させて複写像を得る粉像転写方式あるいは感光体上の静
電潜像を転写紙上に転写し、転写紙上の静電潜像を現像
・定着する潜像転写方式等が知られている。2. Description of the Related Art Generally, in electrophotography, the surface of a photosensitive layer of a photoconductor is charged and exposed to form an electrostatic latent image, which is developed with a developer to be visualized. Direct method of fixing on top to obtain a copy image, or powder image transfer method of transferring a visible image on a photoreceptor onto a transfer paper such as paper and fixing the transferred image to obtain a copy image or on a photoreceptor There is known a latent image transfer system in which an electrostatic latent image is transferred onto a transfer paper, and the electrostatic latent image on the transfer paper is developed and fixed.

従来この種の電子写真法に使用される感光体の感光層を
形成するのに、光導電性材料として、セレン、硫化カド
ミウム、酸化亜鉛等の無機光導電性材料を用いることが
知られている。これらの光導電性材料は、暗所で適当な
電位に帯電できること、暗所で電荷の逸散が少ないこ
と、あるいは光照射によって速かに電荷を逸散できるこ
となどの数多くの利点をもっている反面、次のような各
種の欠点を有している。例えば、セレン系感光体では、
製造コストが高く、また熱や機械的な衝撃に弱いため取
扱いに注意を要する。また、硫化カドミウム系感光体や
酸化亜鉛感光体では、多湿の環境下で安定した感度が得
られない点や、増感剤として添加した色素がコロナ帯電
による帯電劣化や露光による光退色を生じるため長期に
わたって安定した特性を与えることができない欠点を有
している。Conventionally, it has been known to use an inorganic photoconductive material such as selenium, cadmium sulfide, or zinc oxide as a photoconductive material for forming a photosensitive layer of a photoconductor used in this type of electrophotography. . These photoconductive materials have many advantages such as being capable of being charged to an appropriate electric potential in the dark, having little dissipation of charges in the dark, and being capable of rapidly dissipating charges by light irradiation. It has the following various drawbacks. For example, with selenium-based photoreceptors,
The manufacturing cost is high, and it is vulnerable to heat and mechanical shocks, so it requires careful handling. In addition, with cadmium sulfide-based photoreceptors and zinc oxide photoreceptors, stable sensitivity cannot be obtained in humid environments, and the dye added as a sensitizer causes charge deterioration due to corona charging and photobleaching due to exposure. It has a drawback that it cannot provide stable characteristics for a long period of time.

一方、ポリビニルカルバゾールをはじめとする各種の有
機光導電性ポリマーが提案されてきたが、これらのポリ
マーは、前述の無機系光導電材料に比べて成膜性、軽量
性などの点で優れているが、未だ十分な感度，耐久性お
よび環境変化による安定性の点で無機系光導電材料に比
べ劣っている。On the other hand, various organic photoconductive polymers such as polyvinylcarbazole have been proposed, but these polymers are superior in film forming property and lightness to the above-mentioned inorganic photoconductive materials. However, it is still inferior to inorganic photoconductive materials in terms of sufficient sensitivity, durability and stability due to environmental changes.

また低分子量の有機光導電性化合物は、併用する結着剤
の種類、組成比等を選択することにより、被膜の物性あ
るいは電子写真特性を制御することができる点では好ま
しいものであるが、結着剤と併用されるため、結着剤に
対する高い相溶性が要求される。A low molecular weight organic photoconductive compound is preferable in that the physical properties or electrophotographic properties of the coating film can be controlled by selecting the type and composition ratio of the binder used in combination. Since it is used in combination with a binder, high compatibility with the binder is required.

これらの高分子量及び低分子量の有機光導電性化合物を
結着剤樹脂中に分散させた感光体は、キャリアのトラッ
プが多いため残留電位が大きく、感度が低い等の欠点を
有する。そのため有機光導電性化合物に電荷輸送材料を
配合して前記の欠点を解決することが提案されている。The photoconductor in which these high-molecular weight and low-molecular weight organic photoconductive compounds are dispersed in the binder resin has drawbacks such as a large residual potential because of many carrier traps and low sensitivity. Therefore, it has been proposed to blend an organic photoconductive compound with a charge transport material to solve the above drawbacks.

電荷輸送材料としては多くの有機化合物があげられてい
るが実際には種々の問題点がある。例えば米国特許第3,
189,447号公報に記載されている2,5−ビス（Ｐ−ジエチ
ルアミノフエニル）−1,3,4−オキサジアゾールは、結
着剤に対する相溶性が低く、結晶が析出しやすい。米国
特許第3,820,989号公報に記載されているジアリールア
ルカン誘導体は結着剤に対する相溶性は良好であるが、
繰り返し使用した場合に感度変化が生じる。また特開昭
54−59143号公報に記載されているヒドラゾン化合物
は、残留電位特性は比較的良好であるが、感度、帯電能
及び繰り返し特性が劣るという欠点を有する。Although many organic compounds are mentioned as charge transport materials, there are various problems in practice. For example, U.S. Pat.
The 2,5-bis (P-diethylaminophenyl) -1,3,4-oxadiazole described in Japanese Patent No. 189,447 has low compatibility with a binder and crystals are likely to precipitate. Although the diarylalkane derivative described in U.S. Pat.No. 3,820,989 has good compatibility with a binder,
When used repeatedly, sensitivity changes. In addition,
The hydrazone compound described in Japanese Patent Laid-Open No. 54-59143 has relatively good residual potential characteristics, but has the disadvantage of poor sensitivity, chargeability and repetitive characteristics.

このように感光体を作成する上で実用的に好ましい特性
を有する低分子量の有機化合物はほとんどないのが実状
である。As described above, there are almost no low-molecular-weight organic compounds having practically preferable properties for producing a photoreceptor.

本発明の目的は、結着剤に対する相溶性及び電荷輸送能
に優れたエナミン化合物を含有し、高感度で帯電能に優
れ、繰り返し使用による疲労劣化が少なく、電子写真特
性の安定している感光体を提供することを目的とする。An object of the present invention is to include an enamine compound having excellent compatibility with a binder and excellent charge transporting ability, high sensitivity and excellent charging ability, less fatigue deterioration due to repeated use, and stable electrophotographic characteristics. Intended to provide the body.

問題点を解決するための手段 本発明は特定のエナミン化合物を含有することによって
上記の欠点を解決する。Means for Solving the Problems The present invention solves the above-mentioned drawbacks by containing a specific enamine compound.

本発明は下記一般式〔Ｉ〕で表わされるエナミン化合物
を含有する感光体を特徴とする。The present invention features a photoreceptor containing an enamine compound represented by the following general formula [I].

一般式： 〔式中R1は水素、アルキル基、アリール基を示し、アリ
ール基は置換基を有していてもよい。R2はアリール基、
複素環式基を示し、アリール基、複素環式基は置換基を
有していてもよい。R3はジ置換アミノ基、R4は水素、ア
ルキル基、アルコキシ基、フェノキシ基、アラルキルオ
キシ基、ジ置換アミノ基を示す。〕 本発明の一般式〔Ｉ〕で表わされるエナミン化合物の好
ましい具体例としては、例えば次の構造式を有するもの
があげられるが、これらに限定されるものではない。General formula: [In the formula, R 1 represents hydrogen, an alkyl group, or an aryl group, and the aryl group may have a substituent. R 2 is an aryl group,
A heterocyclic group is shown, and the aryl group and the heterocyclic group may have a substituent. R 3 represents a di-substituted amino group, R 4 represents hydrogen, an alkyl group, an alkoxy group, a phenoxy group, an aralkyloxy group or a di-substituted amino group. Preferred specific examples of the enamine compound represented by the general formula [I] of the present invention include, but are not limited to, those having the following structural formulas.

本発明の一般式〔Ｉ〕で表わされるエナミン化合物は公
知の方法により容易に製造することができる。 The enamine compound represented by the general formula [I] of the present invention can be easily produced by a known method.

例えば下記一般式〔II〕 一般式： 〔式中R1、R2は〔Ｉ〕と同意義〕 で表わされるアルデヒド化合物と下記一般式〔III〕 一般式： 〔式中R3、R4は〔Ｉ〕と同意義〕 で表わされるアミン化合物を脱水縮合反応させることに
より合成することができる。For example, the following general formula [II] general formula: [Wherein R 1 and R 2 have the same meaning as in [I]] and the following general formula [III]: [Wherein R 3 and R 4 have the same meaning as in [I]] can be synthesized by subjecting an amine compound represented by the formula to a dehydration condensation reaction.

反応は一般にベンゼン、トルエン、あるいはキシレンな
どの溶媒を用いて生成した水を共沸によって除いたり、
炭酸カリウム、Ｐ−トルエンスルホン酸、酢酸Dowex5
0、あるいはMontmorillonite触媒KIOなどの触媒を用い
て行なわれる。In the reaction, water produced using a solvent such as benzene, toluene, or xylene is generally removed azeotropically,
Potassium carbonate, P-toluenesulfonic acid, Acetic acid Dowex5
0, or using a catalyst such as Montmorillonite catalyst KIO.

本発明のエナミン化合物を用いた感光体の構成例を第１
図から第５図に模式的に示す。First Example of Structure of Photoreceptor Using Enamine Compound of the Present Invention
It is schematically shown in FIGS.

第１図は、基体（１）上に光導電性材料（３）と電荷輸
送材料（２）を結着剤に配合した感光層（４）が形成さ
れた感光体であり、電荷輸送材料として本発明のエナミ
ン化合物が用いられている。FIG. 1 shows a photoreceptor in which a photoconductive layer (4) in which a photoconductive material (3) and a charge transport material (2) are mixed with a binder is formed on a substrate (1). The enamine compound of the present invention is used.

第２図は、感光層として電荷発生層（６）と電荷輸送層
（５）を有する機能分離型感光体であり、電荷発生層
（６）の表面に電荷輸送層（５）が形成されている。電
荷輸送層（５）中に本発明のエナミン化合物が配合され
ている。FIG. 2 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5) as a photosensitive layer. The charge transport layer (5) is formed on the surface of the charge generation layer (6). There is. The enamine compound of the present invention is blended in the charge transport layer (5).

第３図は、第２図と同様電荷発生層（６）と電荷輸送層
（５）を有する機能分離型感光体であるが、第２図とは
逆に電荷輸送層（５）の表面に電荷発生層が形成されて
いる。Similar to FIG. 2, FIG. 3 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5). On the contrary to FIG. A charge generation layer is formed.

第４図は、第１図の感光体の表面にさらに表面保護層
（７）を設けたものであり、感光層（４）は電荷発生層
（６）と電荷輸送層（５）に分離した機能分離型として
もよい。FIG. 4 shows the surface of the photoreceptor of FIG. 1 further provided with a surface protective layer (7). The photosensitive layer (4) is separated into a charge generation layer (6) and a charge transport layer (5). It may be a function separation type.

第５図は、基体（１）と感光層（４）の間に中間層
（８）を設けたものであり、中間層（８）は接着性の改
善、塗工性の向上、基体の保護、基体からの光導電層へ
の電荷注入性改善のために設けることができる。中間層
としては、ポリイミド樹脂、ポリエステル樹脂、ポリビ
ニルチラール樹脂、カゼイン等を用いるとよい。この態
様の感光体も感光層を機能分離型としてもよい。FIG. 5 shows an intermediate layer (8) provided between the substrate (1) and the photosensitive layer (4). The intermediate layer (8) has improved adhesion, improved coatability, and substrate protection. , Can be provided to improve the charge injection property from the substrate to the photoconductive layer. As the intermediate layer, polyimide resin, polyester resin, polyvinyl chiral resin, casein or the like may be used. In the photoreceptor of this aspect, the photosensitive layer may have a function-separated type.

本発明の感光体は、一般式〔Ｉ〕で表わされるエナミン
化合物をバインダーと共に適当な溶剤中に溶解あるいは
分散し、必要に応じ光導電性材料と電子吸引性化合物、
あるいは増感染料、その他の顔料を添加して得られる塗
布液を導電性基体上に塗布、乾燥し、通常５〜30μｍ、
好ましくは６〜20μｍの膜厚の感光層を形成させること
により製造することができる。The photoconductor of the present invention comprises an enamine compound represented by the general formula [I] dissolved or dispersed in a suitable solvent together with a binder, and if necessary, a photoconductive material and an electron-withdrawing compound,
Alternatively, a coating solution obtained by adding a sensitizing dye and other pigments is coated on a conductive substrate and dried, usually 5 to 30 μm,
Preferably, it can be produced by forming a photosensitive layer having a film thickness of 6 to 20 μm.

導電性支持体上に感光層を積層してなり前述した第１図
の感光体と同様の構成である分散型感光体は、光導電性
材料の微粒子をエナミン化合物と樹脂を溶解した溶液中
に分散させ、これを導電性支持体上に塗布、乾燥して感
光層を形成して得られる。このときの感光層の厚さは、
３〜30μｍ、好ましくは５〜20μｍがよい。使用する光
導電性材料の量が少なすぎると感度が悪く、多すぎると
帯電性が悪くなったり、感光層の強度が弱くなったり
し、感光層中の光導電性材料の量は、樹脂１重量部に対
して0.01〜２重量部、好ましくは0.05〜１重量部がよ
く、エナミン化合物の割合は樹脂１重量部に対し、0.01
〜２重量部、好ましくは0.02〜1.2重量部が好適であ
る。また、それ自身バインダーとして使用できるポリビ
ニルカルバゾールなどの高分子光導電体と併用してもよ
い。また、他の電荷輸送材料、たとえばヒドラゾン化合
物と組み合わせてもよい。A dispersion type photoconductor having a photosensitive layer laminated on a conductive support and having the same structure as the photoconductor of FIG. 1 described above is prepared by dissolving fine particles of a photoconductive material in a solution in which an enamine compound and a resin are dissolved. It is obtained by dispersing, coating this on a conductive support, and drying to form a photosensitive layer. The thickness of the photosensitive layer at this time is
The thickness is 3 to 30 μm, preferably 5 to 20 μm. If the amount of the photoconductive material used is too small, the sensitivity is poor, and if it is too large, the charging property is deteriorated or the strength of the photosensitive layer is weakened. 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, is preferable, and the ratio of the enamine compound is 0.01 to 1 part by weight of the resin.
˜2 parts by weight, preferably 0.02 to 1.2 parts by weight. It may also be used in combination with a polymer photoconductor such as polyvinyl carbazole which itself can be used as a binder. It may also be combined with other charge transport materials such as hydrazone compounds.

具体的には導電性支持体上に電荷発生層と電荷輸送層を
積層してなり前述した第２図と同じ構成である機能分離
型感光体は、導電性支持体上に光導電性材料を真空蒸着
するか、適当な溶剤もしくは必要があれば、バインダー
樹脂を溶解させた溶液中に分散させて作製した塗布液を
塗布、乾燥して電荷発生層を形成し、その上にエナミン
化合物とバインダーを適当な溶剤に溶解させた溶液を塗
布、乾燥して電荷輸送層を形成して得られる。このとき
の電荷発生層の厚みは４μｍ以下、好ましくは２μｍ以
下であり、電荷輸送層の厚みは３〜30μｍ、好ましくは
５〜20μｍがよい。電荷輸送層中のエナミン化合物の割
はバインダー１重量部に対し0.02〜２重量部、好ましく
は0.03〜1.3重量部とするのが好適である。また、他の
電荷輸送材を組み合わせてもよい。それ自身バインダー
として使用できる高分子電荷輸送材料の場合は、他のバ
インダーを使用しなくてもよい。尚感光体の構成は前述
した第３図の感光体と同様に導電性支持体上に電荷輸送
層を形成し、その上に電荷発生層を積層した構成でもよ
い。Specifically, a function-separated type photoreceptor having the same structure as that shown in FIG. 2 which is obtained by stacking a charge generation layer and a charge transport layer on a conductive support has a photoconductive material on the conductive support. Vacuum evaporation, or an appropriate solvent or, if necessary, dispersed in a solution in which a binder resin is dissolved, is applied and dried to form a charge generating layer, on which an enamine compound and a binder are formed. It is obtained by applying a solution in which is dissolved in a suitable solvent and drying it to form a charge transport layer. At this time, the thickness of the charge generation layer is 4 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer is 3 to 30 μm, preferably 5 to 20 μm. The proportion of the enamine compound in the charge transport layer is 0.02 to 2 parts by weight, preferably 0.03 to 1.3 parts by weight, based on 1 part by weight of the binder. Also, other charge transport materials may be combined. In the case of the polymer charge transport material which itself can be used as a binder, other binder may not be used. The photosensitive member may have a structure in which a charge transport layer is formed on a conductive support and a charge generating layer is laminated on the conductive support, as in the photosensitive member shown in FIG.

本発明の感光体の光導電性材料に用いられるものとして
は、ビスアゾ系顔料、トリアリールメタン系染料、チア
ジン系染料、オキサジン系染料、キサンテン系染料、シ
アニン系色素、スチリル系色素、ピリリウム系染料、ア
ゾ系顔料、キアクリドン系顔料、インジゴ系顔料、ベリ
レン系顔料、多環キノン系顔料、ビスベンズイミダゾー
ル系顔料、インダスロン系顔料、スクアリリウム系顔
料、フタロシアニン系顔料等の有機物質やセレン、セレ
ン・テルル、セレン・ヒ素、硫化カドミウム、アモルフ
ァスシリコン等の無機物質があげられる。これ以外も、
光を吸収し極めて高い効率で電荷担体を発生する材料で
あれば、いずれの材料であっても使用することができ
る。Examples of materials used for the photoconductive material of the photoreceptor of the present invention include bisazo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes. , Azo pigments, quiacridone pigments, indigo pigments, berylylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indathlon pigments, squarylium pigments, phthalocyanine pigments, and other organic substances, selenium, selenium, Inorganic substances such as tellurium, selenium / arsenic, cadmium sulfide, and amorphous silicon can be given. Other than this,
Any material can be used as long as it absorbs light and generates charge carriers with extremely high efficiency.

本発明におけるバインダーとして使用できるものは、電
気絶縁性であるそれ自体公知の熱可塑性樹脂あるいは熱
硬化性樹脂や光硬化性樹脂、また、光導電性樹脂も全て
使用することができる。As the binder that can be used in the present invention, all known electrically insulating thermoplastic resins, thermosetting resins and photocurable resins, and also photoconductive resins can be used.

適当なバインダー樹脂の例は、これに限定されるもので
はないが、飽和ポリエステル樹脂、ポリアミド樹脂、ア
クリル樹脂、エチレン−酢酸ビニル共重合体、イオン架
橋オレフィン共重合体（アイオノマー）、スチレン−ブ
タジエンブロック共重合体、ポリアリレート、ポリカー
ボネート、塩化ビニル−酢酸ビニル共重合体、セルロー
スエステル、ポリイミド、スチロール樹脂等の熱可塑性
結着剤；エポキシ樹脂、ウレタン樹脂、シリコーン樹
脂、フェノール樹脂、メラミン樹脂、キシレン樹脂、ア
ルキッド樹脂、熱硬化性アクリル樹脂等の熱硬化結着
剤；光硬化性樹脂；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等の光導電性
樹脂等である。これらは単独で、または組み合わせて使
用することができる。Examples of suitable binder resins include, but are not limited to, saturated polyester resins, polyamide resins, acrylic resins, ethylene-vinyl acetate copolymers, ionically cross-linked olefin copolymers (ionomers), styrene-butadiene blocks. Thermoplastic binder such as copolymer, polyarylate, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin, urethane resin, silicone resin, phenol resin, melamine resin, xylene resin Thermosetting binders such as alkyd resins and thermosetting acrylic resins; photocurable resins; photoconductive resins such as poly-N-vinylcarbazole, polyvinylpyrene, and polyvinylanthracene. These can be used alone or in combination.

これら電気絶縁性樹脂は単独で測定して１×1012Ω・cm
以上の体積抵抗を有することが望ましい。より好ましい
ものとしてはポリエステル樹脂、ポリカーボネート、ア
クリル樹脂である。These electrically insulating resins are individually measured 1 × 10 12 Ω · cm
It is desirable to have the above volume resistance. More preferred are polyester resin, polycarbonate and acrylic resin.

本発明の感光体はバインダーとともに、ハロゲン化パラ
フィン、ポリ塩化ビフェニル、ジメチルナフタレン、ジ
ブチルフタレート、０−ターフエニルなどの可塑剤や、
クロラニル、テトラシアノエチレン、2,4,7−トリニト
ロ−９−フルオレノン、5,6−ジシアノベンゾキノン、
テトラシアノキノジメタン、テトラクロル無水フタル
酸、3,5−ジニトロ安息香酸等の電気吸引性増感剤、メ
チルバイオレット、ローダミンＢ、シアニン染料、ピリ
リウム塩、チアピリリウム塩等の増感剤を使用してもよ
い。The photoreceptor of the present invention, together with a binder, a plasticizer such as halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate, and 0-terphenyl,
Chloranil, tetracyanoethylene, 2,4,7-trinitro-9-fluorenone, 5,6-dicyanobenzoquinone,
Using an electro-attractive sensitizer such as tetracyanoquinodimethane, tetrachlorophthalic anhydride, 3,5-dinitrobenzoic acid, sensitizer such as methyl violet, rhodamine B, cyanine dye, pyrylium salt, thiapyrylium salt Good.

この様にして形成される感光体は前述した第４図及び第
５図のように必要に応じて接着層、中間層（８）、表面
保護層（７）を有していてもよい。The photoreceptor thus formed may have an adhesive layer, an intermediate layer (8) and a surface protective layer (7) as required as shown in FIGS. 4 and 5 described above.

発明の効果 本発明の感光体は、上述のエナミン化合物を含有してい
ることにより、電荷輸送能に優れ、初期表面電位が安定
しており、暗減衰率も十分に小さく、良好な帯電能を有
する。またキャリアのトラップも少なく高感度である。EFFECT OF THE INVENTION The photoreceptor of the present invention contains the above-mentioned enamine compound, and thus has excellent charge transportability, stable initial surface potential, sufficiently low dark decay rate, and good chargeability. Have. In addition, there are few carrier traps and high sensitivity.

実施例１ Ｅ型銅フタロシアニン（東洋インキ（株）製）１重量
部、ポリエステル樹脂（バイロン200東洋紡（株）製）
１重量部及びテトラヒドロフラン50重量部をボールミル
ポットに入れて24時間分散し、感光塗液を得た。これを
アルミニウム基体上に塗布、乾燥し、厚さ１μの電荷発
生層を形成させた。Example 1 1 part by weight of E-type copper phthalocyanine (manufactured by Toyo Ink Co., Ltd.), polyester resin (manufactured by Byron 200 Toyobo Co., Ltd.)
1 part by weight and 50 parts by weight of tetrahydrofuran were placed in a ball mill pot and dispersed for 24 hours to obtain a photosensitive coating solution. This was applied onto an aluminum substrate and dried to form a charge generation layer having a thickness of 1 μm.

この電荷発生層上に前述したエナミン化合物（３）を10
重量部、ポリカーボネート樹脂（パンライトK1300帝人
化成（株）製）10重量部を、テトラヒドロフラン100重
量部からなる溶媒中に溶解させた塗液を塗布、乾燥して
厚さ15μの電荷輸送層を形成し、感光体を作成した。On the charge generation layer, the above-mentioned enamine compound (3) 10
Parts by weight, 10 parts by weight of a polycarbonate resin (manufactured by Panlite K1300, Teijin Kasei Co., Ltd.) are dissolved in a solvent consisting of 100 parts by weight of tetrahydrofuran, and dried to form a charge transport layer having a thickness of 15μ. Then, a photoconductor was prepared.

こうして得られた感光体を市販の電子写真複写機（ミノ
ルタカメラ（株）製EP450Z）を用い、−6KVでコロナ帯
電させ、初期電位Vo（ｖ）、初期電位を1/2にするため
に要した露光量Ｅ1/2（lux・sec）、５秒間暗所に放置
した時の初期電位の減衰率DDR5（％）を測定した。The photoreceptor thus obtained was corona-charged at -6 KV by using a commercially available electrophotographic copying machine (EP450Z manufactured by Minolta Camera Co., Ltd.) to obtain the initial potential Vo (v) and the initial potential of 1/2. The exposure amount E 1/2 (lux · sec) was measured, and the initial potential decay rate DDR 5 (%) when left in the dark for 5 seconds was measured.

実施例２〜４ 実施例１と同様の方法で同一の構成のもの、但し実施例
１で用いたエナミン化合物（３）の代わりにエナミン化
合物（４）、（５）、（６）を夫々用いる感光体を作製
した。Examples 2 to 4 have the same constitution as in Example 1 except that the enamine compounds (4), (5) and (6) are used instead of the enamine compound (3) used in Example 1. A photoconductor was prepared.

こうして得られた感光体について、実施例１と同様の方
法でVo、Ｅ1/2、DDR5を測定した。Vo, E 1/2 , and DDR 5 of the photoreceptor thus obtained were measured in the same manner as in Example 1.

実施例５ 銅フタロシアニン50重量部とテトラニトロ銅フタロシア
ニン0.2重量部を98％濃硫酸500重量部に十分撹拌しなが
ら溶解させ、これを水5000重量部にあけ、銅フタロシア
ニンとテトラニトロ銅フタロシアニンの光導電性材料組
成物を折出させた後、濾過、水洗し減圧下120℃で乾燥
した。Example 5 50 parts by weight of copper phthalocyanine and 0.2 parts by weight of tetranitrocopper phthalocyanine were dissolved in 500 parts by weight of 98% concentrated sulfuric acid with sufficient stirring, and this was poured into 5,000 parts by weight of water to obtain photoconductivity of copper phthalocyanine and tetranitrocopper phthalocyanine. After the material composition was projected, it was filtered, washed with water, and dried at 120 ° C. under reduced pressure.

こうして得られた光導電性組成物10重量部を熱硬化性ア
クリル樹脂（アクリディックA405大日本インキ（株）
製）22.5重量部、メラミン樹脂（スーパーベッカミンJ8
20大日本インキ（株）製）7.5重量部前述したエナミン
化合物（８）15重量部をメチルエチルケトンとキシレン
を同量に混合した混合溶剤100重量部とともにボールミ
ルポットに入れて48時間分散して光導電性塗液を調整
し、この塗液をアルミニウム基体上に塗布、乾燥して厚
さ約15μの感光層を形成させ感光体を作製した。10 parts by weight of the photoconductive composition thus obtained was used as a thermosetting acrylic resin (Acridic A405 Dainippon Ink and Chemicals, Inc.)
22.5 parts by weight, melamine resin (Super Beckamine J8)
20 Dainippon Ink and Co., Ltd. 7.5 parts by weight 15 parts by weight of the above-mentioned enamine compound (8) are placed in a ball mill pot together with 100 parts by weight of a mixed solvent in which methyl ethyl ketone and xylene are mixed in the same amount, and dispersed for 48 hours for photoconduction A photosensitive coating liquid was prepared, and the coating liquid was applied onto an aluminum substrate and dried to form a photosensitive layer having a thickness of about 15 μm to prepare a photoconductor.

こうして得られた感光体について実施例１と同様の方
法、但しコロナ帯電を＋6KVで行ってVo、Ｅ1/2、DDR5を
測定した。Vo, E 1/2 , and DDR 5 of the thus obtained photoreceptor were measured in the same manner as in Example 1 except that corona charging was performed at +6 KV.

実施例６〜８ 実施例５と同様の方法で同一の構成のもの、但し実施例
５で用いたエナミン化合物（８）の代わりにエナミン化
合物（９）、（11）、（13）を夫々用いた感光体を作製
した。Examples 6 to 8 The same method as in Example 5 was used, but the enamine compounds (9), (11), and (13) were used instead of the enamine compound (8) used in Example 5, respectively. Was prepared.

こうして得られた感光体について実施例５と同様の方法
でVo、Ｅ1/2、DDR5を測定した。Vo, E 1/2 , and DDR 5 of the photoreceptor thus obtained were measured in the same manner as in Example 5.

実施例９ 下記一般式〔Ａ〕で表わされるジスアゾ顔料２重量部、
ポリエステル樹脂（バイロン200東洋紡（株）製）１重
量部、メチルエチルケトン100重量部をボールミルポッ
トに入れて24時間分散し感光塗液を得た。これをアルミ
ニウム基体上に塗布、乾燥し、厚さ１μの電荷発生層を
形成させた。Example 9 2 parts by weight of a disazo pigment represented by the following general formula [A],
1 part by weight of a polyester resin (Vylon 200 Toyobo Co., Ltd.) and 100 parts by weight of methyl ethyl ketone were placed in a ball mill pot and dispersed for 24 hours to obtain a photosensitive coating solution. This was applied onto an aluminum substrate and dried to form a charge generation layer having a thickness of 1 μm.

一般式： この電荷発生層上に前述したエナミン化合物（14）を10
重量部、ポリアリレート樹脂（Ｕ−100ユニチカ社製）1
0重量部、クロルベンゼン100重量部からなる溶媒中に溶
解させた塗液を塗布、乾燥して厚さ15μの電荷輸送層を
形成し、感光体を作製した。General formula: On the charge generation layer, the above-mentioned enamine compound (14) 10
Parts by weight, polyarylate resin (U-100 Unitika) 1
A coating liquid dissolved in a solvent consisting of 0 part by weight and 100 parts by weight of chlorobenzene was applied and dried to form a charge transport layer having a thickness of 15 μm, and a photoconductor was prepared.

こうして得られた感光体について実施例１と同様の方法
でVo、Ｅ1/2、DDR5を測定した。Vo, E 1/2 , and DDR 5 of the photoreceptor thus obtained were measured in the same manner as in Example 1.

実施例10〜11 実施例９と同様の方法で同一の構成のもの、但し実施例
９で用いたエナミン化合物（14）の代わりにエナミン化
合物（15）、（17）を夫々用いる感光体を作製した。Examples 10 to 11 Photoreceptors having the same constitution as in Example 9 but using the enamine compounds (15) and (17) instead of the enamine compound (14) used in Example 9 were prepared. did.

こうして作製した感光体について実施例１と同様の方法
でVo、Ｅ1/2、DDR5を測定した。Vo, E 1/2 , and DDR 5 of the photoconductor thus prepared were measured in the same manner as in Example 1.

実施例１〜11で得られた感光体のVo、Ｅ1/2、DDR5の測
定結果を第１表にまとめて示す。Table 1 summarizes the measurement results of Vo, E 1/2 , and DDR 5 of the photoconductors obtained in Examples 1 to 11.

第１表からわかるように、本発明の感光体は積層型でも
単層型でも600V以上の初期表面電位があり、暗減衰率も
感光体としては十分使用可能な程度に小さく、良好な帯
電能を有する。また感度においても優れていることがデ
ーターより明らかである。更に、市販の電子写真複写機
（ミノルタカメラ（株）製EP350Z）による正帯電の繰り
返し実写テストを実施例５及び６の感光体において行っ
たが、10000枚のコピーを行っても初期、最終画像にお
いて階調性が優れ、感度変化がなく、鮮明な画像が得ら
れ、本発明の感光体は繰り返し特性にも安定しているこ
とがわかる。 As can be seen from Table 1, the photoconductor of the present invention has an initial surface potential of 600 V or more regardless of whether it is a laminated type or a single layer type, and the dark decay rate is small enough to be used as a photoconductor, and the chargeability is good. Have. It is also clear from the data that the sensitivity is also excellent. Furthermore, a repeated positive actual charging test using a commercially available electrophotographic copying machine (EP350Z manufactured by Minolta Camera Co., Ltd.) was conducted on the photoconductors of Examples 5 and 6, but the initial and final images were obtained even after copying 10,000 sheets. It is understood that in (1), the gradation is excellent, there is no change in sensitivity and a clear image is obtained, and the photoconductor of the present invention is stable in repeatability.

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

第１図〜第５図は本発明に係る感光体の模式図であって
第１図、第４図、第５図は導電性支持体上に感光層を積
層してなる分散型感光体の構造を示し、第２図、第３図
は導電性支持体上に電荷発生層と電荷輸送層を積層して
なる機能分離型感光体の構造を示す。 １……導電性支持体、２……電荷輸送材料 ３……光導電性材料、４……感光層 ５……電荷輸送層、６……光導電層 ７……表面保護層、８……中間層1 to 5 are schematic views of a photosensitive member according to the present invention, and FIGS. 1, 4, and 5 show a dispersion type photosensitive member obtained by laminating a photosensitive layer on a conductive support. The structure is shown in FIGS. 2 and 3 which shows the structure of a function-separated type photoreceptor in which a charge generation layer and a charge transport layer are laminated on a conductive support. DESCRIPTION OF SYMBOLS 1 ... Conductive support, 2 ... Charge transport material 3 ... Photoconductive material, 4 ... Photosensitive layer 5 ... Charge transport layer, 6 ... Photoconductive layer 7 ... Surface protective layer, 8 ... Middle class

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】下記一般式〔Ｉ〕で表わされるエナミン化
合物を含有することを特徴とする感光体。 一般式： 〔式中R1は水素、アルキル基、アリール基を示し、アリ
ール基は置換基を有してもよい。R2はアリール基、複素
環式基を示し、アリール基、複素環式基は置換基を有し
ていてもよい。R3はジ置換アミノ基、R4は水素、アルキ
ル基、アルコキシ基、フェノキシ基、アラルアルキルオ
キシ基、ジ置換アミノ基を示す。〕1. A photoconductor containing an enamine compound represented by the following general formula [I]. General formula: [In the formula, R 1 represents hydrogen, an alkyl group or an aryl group, and the aryl group may have a substituent. R 2 represents an aryl group or a heterocyclic group, and the aryl group or the heterocyclic group may have a substituent. R 3 represents a di-substituted amino group, R 4 represents hydrogen, an alkyl group, an alkoxy group, a phenoxy group, an aralkylalkyl group or a di-substituted amino group. ]
JP11591686A 1986-04-08 1986-05-20 Photoconductor Expired - Fee Related JPH0693125B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP11591686A JPH0693125B2 (en) 1986-05-20 1986-05-20 Photoconductor
US07/035,183 US4808505A (en) 1986-04-08 1987-04-07 Photosensitive member with enamine charge transport material
DE19873711795 DE3711795A1 (en) 1986-04-08 1987-04-08 LIGHT SENSITIVE ELEMENT

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP11591686A JPH0693125B2 (en) 1986-05-20 1986-05-20 Photoconductor

Publications (2)

Publication Number Publication Date
JPS62272268A JPS62272268A (en) 1987-11-26
JPH0693125B2 true JPH0693125B2 (en) 1994-11-16

Family

ID=14674386

Family Applications (1)

Application Number Title Priority Date Filing Date
JP11591686A Expired - Fee Related JPH0693125B2 (en) 1986-04-08 1986-05-20 Photoconductor

Country Status (1)

Country Link
JP (1) JPH0693125B2 (en)

Also Published As

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JPS62272268A (en) 1987-11-26

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LAPS Cancellation because of no payment of annual fees