JPH0772801B2 - Photoconductor - Google Patents

Photoconductor

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Publication number
JPH0772801B2
JPH0772801B2 JP61108050A JP10805086A JPH0772801B2 JP H0772801 B2 JPH0772801 B2 JP H0772801B2 JP 61108050 A JP61108050 A JP 61108050A JP 10805086 A JP10805086 A JP 10805086A JP H0772801 B2 JPH0772801 B2 JP H0772801B2
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JP
Japan
Prior art keywords
weight
layer
parts
photoreceptor
group
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
JP61108050A
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Japanese (ja)
Other versions
JPS62264057A (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 JP61108050A priority Critical patent/JPH0772801B2/en
Priority to US07/035,183 priority patent/US4808505A/en
Priority to DE19873711795 priority patent/DE3711795A1/en
Publication of JPS62264057A publication Critical patent/JPS62264057A/en
Publication of JPH0772801B2 publication Critical patent/JPH0772801B2/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線感光体
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,
Since the manufacturing cost is high and it is vulnerable to heat and mechanical impact, it needs to be handled with care.In addition, with the cadmium sulfide-based photoconductor and the zinc oxide photoconductor, stable sensitivity cannot be obtained in a humid environment. The dye added as a sensitizer has a drawback that stable characteristics cannot be provided for a long period of time because it causes charge deterioration due to corona charging and photobleaching due to exposure.

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。Further, 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.

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挙げられてお
り、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−ジエチルアミノフェニル）−1,3,4−
オキサジアゾール、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、特開昭54−59
143号公報に記載さらているヒドラゾン化合物等が知ら
れている。As the charge transport material, many organic compounds have been mentioned, for example, 2,5-bis (p-diethylaminophenyl) -1,3,4-described in U.S. Pat. No. 3,189,447.
Oxadiazoles and diarylalkane derivatives described in U.S. Pat.No. 3,820,989 are disclosed in JP-A-54-59.
The hydrazone compounds described in Japanese Patent No. 143 are known.

本発明の目的は、電荷輸送能に優れた新規なエナミン化
合物を含有した感光体を提供することにある。An object of the present invention is to provide a photoconductor containing a novel enamine compound having excellent charge transporting ability.

また、本願発明の他の目的は、感度及び帯電能の良好な
感光体を提供することにある。Another object of the present invention is to provide a photoreceptor having good sensitivity and chargeability.

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
上記の目的を達成する。Means for Solving the Problems The present invention achieves the above object by containing a specific enamine compound.

本発明の感光体は、下記一般式［Ｉ］あるいは［II］で
表されるエナミン化合物を含有することを特徴とする。The photoreceptor of the present invention is characterized by containing an enamine compound represented by the following general formula [I] or [II].

一般式： ［式中R1は水素、アルコキシ基、アルキル基を表わす。
R2は水素、それぞれ置換基を有してもよいアルキル基、
アルコキシ基、ジ置換アミノ基を表わす。R3はそれぞれ
置換基を有してもよいアリール基、複素環式基を表わ
す。R4は水素、置換基を有してもよいアリール基を表わ
し、R3が複素環式基の時R4は水素をとる。ただし、R1お
よびR2が水素、かつ、R3およびR4がアルコキシフェニル
基で表わされる化合物を除く。］ ［式中R5は水素、それぞれ置換基を有してもよいアルキ
ル基、アルコキシ基、ジ置換アミノ基を表わす。R6、R7
はそれぞれ置換基を有してもよいアリール基を表わ
す。］ 本発明に係る一般式〔Ｉ〕あるいは〔II〕で表わされる
エナミン化合物の具体例としては、例えば次の構造を有
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, R1 represents hydrogen, an alkoxy group, or an alkyl group.
R2 is hydrogen, an alkyl group which may have a substituent,
It represents an alkoxy group or a di-substituted amino group. R3 represents an aryl group or a heterocyclic group which may have a substituent. R4 represents hydrogen or an aryl group which may have a substituent, and when R3 is a heterocyclic group, R4 takes hydrogen. However, a compound in which R1 and R2 are hydrogen and R3 and R4 are alkoxyphenyl groups is excluded. ] [In the formula, R5 represents hydrogen, an alkyl group which may have a substituent, an alkoxy group, or a disubstituted amino group. R6, R7
Each represents an aryl group which may have a substituent. Specific examples of the enamine compound represented by the general formula [I] or [II] according to the present invention include, but are not limited to, those having the following structures.

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.

例えば一般式［IV］ 一般式： ［式中R3、R4は［Ｉ］と同意義］ で表されるアルデヒド化合物と一般式［Ｖ］ 一般式： ［式中R1、R2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, general formula [IV] general formula: [Wherein R 3 and R 4 have the same meanings as [I]] and the general formula [V]: [Wherein R 1 and R 2 have the same meaning as [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、あるいはキシレン等
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、Dowex50
あるいはMontmorillonite触媒KIO等の触媒を用いて行な
われる。In the reaction, water produced by using a solvent such as benzene, toluene, or xylene is generally removed by azeotropic distillation, potassium carbonate, P-toluenesulfonic acid, acetic acid, Dowex50
Alternatively, it is carried out 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 compounds of the invention have been 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）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 charge transport layer (5) contains the enamine compound of the present invention.

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〕あるいは〔II〕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
に溶解あるいは分離し、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 photoreceptor of the present invention is prepared by dissolving or separating an enamine compound represented by the general formula [I] or [II] together with a binder in a suitable solvent, and if necessary, a photoconductive material and an electron-withdrawing compound, or hyperinfection. It can be produced by coating a coating solution obtained by adding a pigment and other pigments on a conductive substrate and drying it to form a photosensitive layer having a thickness of usually 5 to 30 μm, preferably 6 to 20 μm. .

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
合はバインダー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.

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.

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
ゾ系染料、キアクリドン系顔料、インジゴ系顔料、ペリ
レン系顔料、多環キノン系顔料、ビスベンズイミダゾー
ル系顔料、インダスロン系顔料、スクアリリウム系顔
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 dyes, quinacridone pigments, indigo pigments, perylene 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、エチレン一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、
フエノール樹脂、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 monovinyl acetate copolymers, ionically crosslinked olefin copolymers (ionomers), styrene-butadiene blocks. Thermoplastic binders such as copolymers, polyarylate, polycarbonate, vinyl chloride / vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin, urethane resin, silicone resin,
Thermosetting binder such as phenol resin, melamine resin, xylene resin, alkyd resin, thermosetting acrylic resin; photocurable resin; photoconductive resin such as poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, etc. is there. 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、ポリ塩化ビフエニル、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子吸引性増感剤、メ
チルバイオレット、ローダミンＢ、シアニン染料、ピリ
リウム塩、チアピリリウム塩等の増感剤を使用してもよ
い。The photoreceptor of the present invention, together with a binder, a plasticizer such as halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutylphthalate, 0-terphenyl,
Chloranil, tetracyanoethylene, 2,4,7-trinitro-9-fluorenone, 5,6-dicyanobenzoquinone,
Using electron-withdrawing sensitizers such as tetracyanoquinodimethane, tetrachlorophthalic anhydride and 3,5-dinitrobenzoic acid, sensitizers such as methyl violet, rhodamine B, cyanine dyes, pyrylium salts and thiapyrylium salts 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、上述したエナミン化合物を含有して
いることにより、電荷輸送能が著しく優れたものであ
り、初期表面電位が安定しており、暗減衰率も感光体に
十分使用可能な程度に小さく、良好な帯電能を有してい
る。また本発明の感光体は電荷輸送能に優れていること
から、キャリアのトラップも少なく高感度である。EFFECTS OF THE INVENTION The photoconductor of the present invention, which contains the above-mentioned enamine compound, has a remarkably excellent charge transporting ability, the initial surface potential is stable, and the dark decay rate is sufficient for the photoconductor. It is small enough to be used and has good charging ability. Further, since the photoreceptor of the present invention is excellent in charge transporting ability, it has few carriers traps and high sensitivity.

実施例１ 下記一般式〔Ａ〕で表わされるジスアゾ顔料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、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0.5μの電荷発生層を形
成させた。Example 1 1 part 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 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 coated on an aluminum substrate and dried to form a charge generation layer having a thickness of 0.5 μm.

一般式： この電荷発生層の上に前述したエナミン化合物（１）10
重量部、ポリカーボネート樹脂（パンライトＫ−1300帝
人化成（株）製）10重量部をテトラヒドロフラン80重量
部に溶解させた塗布液を塗布、乾燥し厚さ15μの電荷輸
送層を形成させ感光体を作製した。General formula: The above-mentioned enamine compound (1) 10 is formed on this charge generation layer.
Parts by weight, 10 parts by weight of a polycarbonate resin (manufactured by Panlite K-1300 Teijin Kasei Co., Ltd.) in 80 parts by weight of tetrahydrofuran are applied and dried to form a charge transporting layer having a thickness of 15 μm to form a photoreceptor. It was made.

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Ep 360Z）を用い−6.0KV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。Principal thus obtained photosensitive member commercially available electrophotographic copying machine was corona charged at -6.0KV using (Minolta Camera Co., Ltd. Ep 360Z) initial potential Vo (v), the initial potential to the 1/2 the exposure amount E 1/2 (lux · sec ), attenuation rate DDR 5 (%) of the initial potential when allowed to stand at 5 seconds dark was measured.

実施例２〜３ 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（１）の代わりにエナミン化
合物（２），（４）を夫々用いる感光体を作製した。Examples 2 to 3 Photoreceptors having the same structure as in Example 1 but having the same constitution, except that the enamine compounds (2) and (4) were used instead of the enamine compound (1) used in Example 1, were prepared. did.

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, the E 1/2, DDR 5 was measured in the same manner as in Example 1 for the thus obtained photosensitive member.

実施例４ 下記一般式〔Ｂ〕で表わされるトリスアゾ顔料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 4 2 parts by weight of a trisazo pigment represented by the following general formula [B], a polyester resin (manufactured by Byron 200 Toyobo Co., Ltd.)
1 part by weight 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（５）10重
量部、ポリアリレート樹脂（Ｕ−100ユニチカ製）10重
量部をクロルベンゼン100重量部に溶解させた塗布液を
塗布、乾燥し厚さ15μの電荷輸送層を形成させた感光体
を作製した。General formula: A coating solution prepared by dissolving 10 parts by weight of the above-mentioned enamine compound (5) and 10 parts by weight of a polyarylate resin (manufactured by U-100 Unitika) in 100 parts by weight of chlorobenzene was applied onto the charge generation layer and dried to a thickness of 15 μm. A photoconductor having the above charge transport layer formed thereon was produced.

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, the E 1/2, DDR 5 was measured in the same manner as in Example 1 for the thus obtained photosensitive member.

実施例５〜６ 実施例４と同様の方法で同一の構成のもの、但し実施例
４で用いたエナミン化合物（５）の代わりにエナミン化
合物（６）、（７）を夫々用いる感光体を作製した。Examples 5 to 6 Photoconductors having the same constitution as in Example 4 except that the enamine compounds (6) and (7) were used instead of the enamine compound (5) used in Example 4 were prepared. did.

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, the E 1/2, DDR 5 was measured in the same manner as in Example 1 for the thus obtained photosensitive member.

実施例８ 下記一般式〔Ｃ〕で表わされるスクワリン酸系顔料２重
量部、ポリエステル樹脂（バイロン200東洋紡（株）
製）５重量部をメチルエチルケトン100重量部と共にボ
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 8 2 parts by weight of a squalic acid pigment represented by the following general formula [C], a polyester resin (Vylon 200 Toyobo Co., Ltd.)
5 parts by weight) 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： この電荷発生層の上にエナミン化合物（12）を10重量
部、ポリカーボネート樹脂（パンライトＫ−1300帝人化
成（株）製）10重量部をテトラヒドロフラン80重量部に
溶解させた塗布液を乾燥後の膜厚が約15μになるように
塗布して電荷輸送層を形成させ感光体を作成した。General formula: On the charge generation layer, 10 parts by weight of the enamine compound (12) and 10 parts by weight of a polycarbonate resin (manufactured by Panlite K-1300 Teijin Kasei Co., Ltd.) were dissolved in 80 parts by weight of tetrahydrofuran to form a coating solution, which was dried. A photoconductor was prepared by forming a charge transport layer by coating so as to have a film thickness of about 15 μm.

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, the E 1/2, DDR 5 was measured in the same manner as in Example 1 for the thus obtained photosensitive member.

実施例７ 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
成物を析出させた後、濾過、水洗し減圧下120℃で乾燥
した。Example 7 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 5000 parts by weight of water to obtain photoconductivity of copper phthalocyanine and tetranitrocopper phthalocyanine. After depositing the material composition, 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（10）10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 Co., Ltd. 7.5 parts by weight 10 parts by weight of the above-mentioned enamine compound (10) are placed in a ball mill pot together with 100 parts by weight of a mixture of methyl ethyl ketone and xylene in the same amount and dispersed for 48 hours for photoconductivity. Adjust the coating liquid,
Apply this coating solution on an aluminum substrate and dry it to a thickness of approximately
A 15 μm photosensitive layer was formed to prepare a photoreceptor.

こうして得られた感光体について実施例と同様の方法、
但しコロナ帯電を＋6KVで行ってVo、E1/2、DDR5を測定
した。For the photoreceptor thus obtained, the same method as in Example,
However was measured Vo, the E 1/2, DDR 5 performs corona charging at + 6KV.

実施例８〜９ 実施例７と同様の方法で同一の構成のもの、但し実施例
７で用いたエナミン化合物（10）の代わりにエナミン化
合物（12）、（15）を夫々用いた感光体を作製した。Examples 8 to 9 A photoreceptor having the same structure as in Example 7 except that the enamine compounds (12) and (15) were used instead of the enamine compound (10) used in Example 7 was used. It was made.

こうして得られた感光体について実施例７と同様の方法
でVo、E1/2、DDR5を測定した。Vo, the E 1/2, DDR 5 was measured in the same manner as in Example 7 for the thus obtained photosensitive member.

実施例１〜９の感光体のVo、E1/2、DDR5の測定結果を第
１表に示す。Vo of the photosensitive member of Example 1-9, the measurement results of the E 1/2, DDR 5 shown in Table 1.

第１表からわかるように本発明の感光体はいずれの場合
も初期表面電位が600V以上で安定しており、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、帯電能が
良好である。また感度もほぼどの感光体においても安定
しており、高感度であることがわかる。 As can be seen from Table 1, in all cases, the photoreceptor of the present invention had an initial surface potential of 600 V or more and was stable, the dark decay rate was small enough to be used as a photoreceptor, and the chargeability was good. is there. Further, it can be seen that the sensitivity is stable in almost all the photoconductors, and the sensitivity is high.

【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 photoreceptor according to the present invention, and FIGS. 1, 4, and 5 are dispersion type photoreceptors in which a photosensitive layer is laminated on a conductive support. 2 and 3 show 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］あるいは［II］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、アルコキシ基、アルキル基を表わす。
R2は水素、それぞれ置換基を有してもよいアルキル基、
アルコキシ基、ジ置換アミノ基を表わす。R3はそれぞれ
置換基を有してもよいアリール基、複素環式基を表わ
す。R4は水素、置換基を有してもよいアリール基を表わ
し、R3が複素環式基の時R4は水素をとる。ただし、R1お
よびR2が水素、かつ、R3およびR4がアルコキシフェニル
基で表わされる化合物を除く。］ ［式中R5は水素、それぞれ置換基を有してもよいアルキ
ル基、アルコキシ基、ジ置換アミノ基を表わす。R6、R7
はそれぞれ置換基を有してもよいアリール基を表わ
す。］1. A photoconductor containing an enamine compound represented by the following general formula [I] or [II]. General formula: [In the formula, R1 represents hydrogen, an alkoxy group, or an alkyl group.
R2 is hydrogen, an alkyl group which may have a substituent,
It represents an alkoxy group or a di-substituted amino group. R3 represents an aryl group or a heterocyclic group which may have a substituent. R4 represents hydrogen or an aryl group which may have a substituent, and when R3 is a heterocyclic group, R4 takes hydrogen. However, a compound in which R1 and R2 are hydrogen and R3 and R4 are alkoxyphenyl groups is excluded. ] [In the formula, R5 represents hydrogen, an alkyl group which may have a substituent, an alkoxy group, or a disubstituted amino group. R6, R7
Each represents an aryl group which may have a substituent. ]
JP61108050A 1986-04-08 1986-05-12 Photoconductor Expired - Fee Related JPH0772801B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP61108050A JPH0772801B2 (en) 1986-05-12 1986-05-12 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
JP61108050A JPH0772801B2 (en) 1986-05-12 1986-05-12 Photoconductor

Publications (2)

Publication Number Publication Date
JPS62264057A JPS62264057A (en) 1987-11-17
JPH0772801B2 true JPH0772801B2 (en) 1995-08-02

Family

ID=14474653

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61108050A Expired - Fee Related JPH0772801B2 (en) 1986-04-08 1986-05-12 Photoconductor

Country Status (1)

Country Link
JP (1) JPH0772801B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5663835B2 (en) * 2008-12-03 2015-02-04 三菱化学株式会社 Electrophotographic photosensitive member, electrophotographic cartridge, and image forming apparatus
JP5590202B2 (en) * 2013-08-23 2014-09-17 三菱化学株式会社 Electrophotographic photosensitive member, novel enamine compound, electrophotographic photosensitive member cartridge, and image forming apparatus

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0789222B2 (en) * 1986-04-08 1995-09-27 ミノルタ株式会社 Photoconductor
JPH0789224B2 (en) * 1986-04-16 1995-09-27 ミノルタ株式会社 Photoconductor

Also Published As

Publication number Publication date
JPS62264057A (en) 1987-11-17

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