JPS60213953A - Electrophotographic sensitive body - Google Patents

Electrophotographic sensitive body

Info

Publication number
JPS60213953A
JPS60213953A JP7014284A JP7014284A JPS60213953A JP S60213953 A JPS60213953 A JP S60213953A JP 7014284 A JP7014284 A JP 7014284A JP 7014284 A JP7014284 A JP 7014284A JP S60213953 A JPS60213953 A JP S60213953A
Authority
JP
Japan
Prior art keywords
group
charge transport
coating
formula
transport layer
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.)
Pending
Application number
JP7014284A
Other languages
Japanese (ja)
Inventor
Akio Kojima
小島　明夫
Junichiro Hashimoto
準一郎 橋本
Hiroshi Tamura
宏 田村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Priority to JP7014284A priority Critical patent/JPS60213953A/en
Publication of JPS60213953A publication Critical patent/JPS60213953A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • G03G5/0629—Heterocyclic compounds containing one hetero ring being five-membered containing one hetero atom
    • 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
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0564—Polycarbonates

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

PURPOSE:To obtain superior electrophotographic characteristics long and stable in pot life, capable of controlling concn. in a wide range, free from restriction of the coating method to be used, by using a combination of a specified electrostatic charge transfer material, a binder, and a solvent for forming a charge transfer layer. CONSTITUTION:The charge transfer layer of a laminate type photosensitive layer formed on a conductive substrate is formed with a coating fluid contg. a hydrazone compd. represented by formula I (R1 is methyl, ethyl, 2-hydroxyethyl or the like; R2 is methyl, ethyl, phenyl, or the like; and R3 is Cl, Br, 1-4C alkyl or alkoxy), and a polycarbonate resin having repeating units represented by formula IIIobtained from phosgen and 4,4'-dihydroxyphenyl-1,1-cyclohexane represented by formula II. The use of such a compsn. of specified combination permits a coating fluid long and stable in pot life, controllable in a wide range of concn. and adaptable to various restriction conditions required from the coating methods to be obtained.

Description

【発明の詳細な説明】 技術分野 本発明は電子写真用の感光体に関し、更に詳しくは導電
性支持体上に電荷発生層及び電荷搬送層を設けた電子写
真用感光体に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a charge generation layer and a charge transport layer provided on a conductive support.

従来技術 従来よりＳ電性支持体上に、光吸収により電荷担体を生
成することの出来る、いわゆる電荷発生層を設け、更に
その上に生成した電荷担体を電場の力により移動させる
ことができる、いわゆる電荷搬送層を設Ｇプだ積層型の
電子写真用感光体が数多く提案されている。Prior Art Conventionally, a so-called charge generation layer, which can generate charge carriers by light absorption, is provided on an S-electrode support, and furthermore, the charge carriers generated thereon can be moved by the force of an electric field. Many laminated type electrophotographic photoreceptors having a so-called charge transport layer have been proposed.

これらの積層型電子写真用感光体において、電荷発生層
は、一般的には１）３ｅ　、’３ｅ３ｅ、ａ−３ｔ、有
機顔料等の電荷発生物質を真空蒸着、グｌ」−放電等に
より設ける（例えば特開昭４８−４７８３８、周４９−
４８３３４　＞、２）　Ｓｅ　。In these laminated electrophotographic photoreceptors, the charge generation layer is generally formed by 1) providing a charge generation substance such as 3e, '3e3e, a-3t, or organic pigment by vacuum evaporation, glue discharge, or the like; (For example, JP-A-48-47838, Shu 49-
48334 >, 2) Se.

Ｓｅ合金、Ｚｎ　Ｏ，Ｔｉ　０２　、Ｃｄ　Ｓ等の無機
顔料、及び有機顔料等の電荷発生物質を、必要ならば結
着剤を加えて分散した分散液を塗布する（例えば特開昭
４７−１８５４３、同５５−７９４４９）、３）有機顔
料の電荷発生物質を有機アミン中に溶解した溶液を塗布
する（例えば特開昭５２−５５６４３　）等の方法が行
なわれている。A dispersion of Se alloy, inorganic pigments such as Zn O, Ti 02 , Cd S, etc., and charge generating substances such as organic pigments, with the addition of a binder if necessary, is applied (for example, as described in JP-A-47-18543). , 55-79449) and 3) applying a solution of an organic pigment charge-generating substance dissolved in an organic amine (for example, JP-A-52-55643).

一方、電荷搬送層は、一般的には電荷搬送物質を結着剤
と共に溶剤に溶解し、適当な塗工法により塗布すること
によって設けている。On the other hand, the charge transport layer is generally provided by dissolving a charge transport substance together with a binder in a solvent and applying the resulting solution by a suitable coating method.

電荷搬送層に要求される機能としては、良好な電子写真
特性（帯電性、感度、少ない残留電位等）を提供するこ
とは言うまでもなく、さらに使用中に受ける電気的、熱
的、光学的ハザード等に対して劣化が少なく、また雰囲
気による特性変化、保存中での特性変化が極力少ないこ
とである。Needless to say, the functions required of the charge transport layer include providing good electrophotographic properties (charging properties, sensitivity, low residual potential, etc.), as well as electrical, thermal, and optical hazards encountered during use. There is little deterioration compared to other materials, and changes in characteristics due to atmosphere and during storage are as small as possible.

また電荷搬送層形成用の塗布液はボッ１〜ライフが永く
、安定であり、広い範囲でのｍ度コントロールが可能で
あり、塗工法から要求される種々の制約条件を満足し、
かつ塗工装置に対する制約が少ないことが要求される。In addition, the coating liquid for forming the charge transport layer is stable, has a long life, and can be controlled over a wide range, and satisfies various constraints required by the coating method.
In addition, it is required that there are few restrictions on the coating equipment.

従来より電荷搬送層を形成する為に種々の材料が検討さ
れている。電荷搬送層は基本的には電荷搬送物質、結着
剤及び必要に応じて加える可塑剤、レベリング剤等の添
加剤とから成り、それらを溶剤に溶解し、各種の塗工法
により形成されている。Various materials have been considered for forming charge transport layers. The charge transport layer basically consists of a charge transport substance, a binder, and optional additives such as a plasticizer and a leveling agent, and is formed by dissolving them in a solvent and using various coating methods. .

電荷搬送物質としては例えば、ポリ−Ｎ−ビニルカルバ
ゾール及びその誘導体、ポリーγ−カルバゾリルエチル
グルタメート及びその誘導体、ピレン−ホルムアルデヒ
ド縮合物及びその誘導体、ポリビニルピレン、ポリビニ
ルフェナントレン、オキサゾール誘導体、オキサジノ７
ゾール誘導体、イミダゾール誘導体、９−（ｐ−ジエチ
ルアミノスチリル）アントラセン、１，１−ビス（４−
ジベンジルアミノフェニル）プロパン、スチリルアント
ラセン、スチリルピラゾリン、フェニルヒドラゾン類、
α−フェニルスチルベン誘導体等の電子供与性物質、或
いはフルオレノン誘導体、ジベンゾチオフェン誘導体、
インデノチオフェン誘導体、フェナンスレンキノン誘導
体、インデノピリジン誘導体、チオキサントン誘導体、
ベンゾ［ε］シンノリン誘導体、フェナジンオキサイド
誘導体、テトラシアノエチレン、テトラシアノキノジメ
タン、プロマニル、クロラニル、ベンゾキノン等の電子
受容性が検問されている。Examples of the charge transport substance include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, and oxazino-7.
zole derivatives, imidazole derivatives, 9-(p-diethylaminostyryl)anthracene, 1,1-bis(4-
dibenzylaminophenyl) propane, styryl anthracene, styryl pyrazoline, phenylhydrazones,
Electron-donating substances such as α-phenylstilbene derivatives, fluorenone derivatives, dibenzothiophene derivatives,
indenothiophene derivatives, phenanthrenequinone derivatives, indenopyridine derivatives, thioxanthone derivatives,
The electron acceptability of benzo[ε]cinnoline derivatives, phenazine oxide derivatives, tetracyanoethylene, tetracyanoquinodimethane, promanil, chloranil, benzoquinone, etc. has been examined.

結着剤としては、種々の高分子材料、例えばポリスチレ
ン、スチレン−アクリロニトリル共重合体、スチレン−
ブタジェン共重合体、スチレン−無水マレイン酸共重合
体、ポリエステル、ポリ塩化ビニル、塩化ビニル−酢酸
ビニル共重合体、ポリ酢酸ビニル、ボリアリレー１〜樹
脂、ポリ塩化ビニリデン、西１酸セルロース、エチルセ
ルロース、ポリビニルブチラール、ポリビニルホルマー
ル、ポリアミド、ポリ−Ｎ−ビニルカルバゾール、ポリ
ビニルトルエン、アクリル樹脂、ポリカーボネート、シ
リコン樹脂、エポキシ樹脂、メラミン樹脂、ウレタン樹
脂、フェノール樹脂、アルキッド樹脂等の熱可塑性樹脂
、熱硬化性樹脂、デンプン、ニカワ、カゼイン等の天然
物等の単独もしくは混合での使用が検問され−Ｃいる。As the binder, various polymer materials such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile copolymer, etc.
Butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyaryl 1~resin, polyvinylidene chloride, cellulose nitrate, ethyl cellulose, polyvinyl Thermoplastic resins, thermosetting resins such as butyral, polyvinyl formal, polyamide, poly-N-vinylcarbazole, polyvinyltoluene, acrylic resin, polycarbonate, silicone resin, epoxy resin, melamine resin, urethane resin, phenolic resin, alkyd resin, The use of natural products such as starch, glue, casein, etc. alone or in combination is examined.

また溶剤としては一般的にはベンゼン、１−ルエン、キ
シレン等の炭化水素類、アセトン、メチルエチルケトン
、メチルイソブチルケトン、シクロヘキサノン等のケ１
〜ン類、テ１−ラヒドロフラン、ジオキサン等のエーテ
ル類、酢酸エチル、酢酸プロピル、酢酸ブチル等のエス
テル類、塩化メチレン、ジ塩化エチレン、１．１．２−
　トリクロルエタン、四塩化炭素、モノクロルベンゼン
、０−ジクロルベンゼン等の塩化炭化水素類、ｎ−プロ
ピルアルコール、イソプロピルアルコール、０−ブチル
アルコール、イソブチルアルコール等のアルコール類の
使用が検討されている。In addition, the solvents generally include hydrocarbons such as benzene, 1-toluene, and xylene;
1.1.2-
The use of chlorinated hydrocarbons such as trichloroethane, carbon tetrachloride, monochlorobenzene, and 0-dichlorobenzene, and alcohols such as n-propyl alcohol, isopropyl alcohol, 0-butyl alcohol, and isobutyl alcohol is being considered.

目　的 本発明の目的は、積層型電子写真用感光体の電荷搬送層
に関するものであり、前述した如くの機能を全て満足す
る電荷搬送層及びそれを具体的に可能にする電荷搬送層
形成用塗布液を提供することにある。Object The object of the present invention is to provide a charge transport layer for a laminated electrophotographic photoreceptor, and a charge transport layer that satisfies all of the above-mentioned functions, and a charge transport layer forming material that specifically enables the above-mentioned functions. The purpose of the present invention is to provide a coating liquid.

構　成 本発明者らは種々の材料を検討し、電荷搬送物質、結着
剤、溶剤の特定の組合せにより、前述した様な要求機能
、すなわちポットライフが永く、安定であり、広い範囲
での８度コントロールが可能であり、塗工法から要求さ
れる種々の制約条件を満足し、かつ塗工装置に対する制
約が少ない電荷搬送層形成用の塗布液が１９られ、それ
を塗布覆ることにより、極めて良好な電子写真特性が得
られる電子写真用感光体を提供出来ることを見出した。Composition The present inventors studied various materials, and by using a specific combination of a charge transport substance, a binder, and a solvent, the required functions as described above, namely, a long pot life, stability, and a wide range of A coating liquid for forming a charge transport layer that can be controlled, satisfies various constraints required by the coating method, and has few restrictions on coating equipment has been created. We have discovered that it is possible to provide an electrophotographic photoreceptor that provides excellent electrophotographic characteristics.

従来より電荷搬送層を形成する為に、前述した様な材料
が検討されていると述べたが、本発明者らの検討では、
それらの電荷搬送物質は一般的には溶剤に対する溶解性
が悪く、結着剤との相溶性も悪い。従ってその様な電荷
搬送層形成用の塗布液より得られる電荷搬送層は経時変
化し、電荷搬送物質が表面に析出し、電子写真特性に大
きな影響を及ばず。As mentioned above, materials such as those mentioned above have been considered for forming the charge transport layer, but in the study of the present inventors,
These charge transport materials generally have poor solubility in solvents and poor compatibility with binders. Therefore, the charge transport layer obtained from such a coating solution for forming a charge transport layer changes over time, and the charge transport substance precipitates on the surface without significantly affecting the electrophotographic properties.

また電荷搬送物質と結着剤との物質比にも制約が生じ、
好ましい物質比を選択するのが難しい。さらに塗布液の
濃度にも低いレベルで限界が有り、塗膜形成コントロー
ル上支障をきたす。その為に各種の溶剤が検討されてい
るが、前述した溶剤の中では、炭化水素類、エーテル類
、塩化炭化水素類の使用が一般的にはとられている。本
発明者らの検討では、塩化炭化水素類を使用すると電荷
搬送物質、結着剤を相溶さｕ１安定な塗布液を提供する
という点では優れているが、電荷搬送物質として電子供
与性物質を使用した場合、塩化炭化水素類の遊離の塩素
と反応し、電荷移動錯体を形成し、電子写真特性に悪影
響を及ぼすこと、ｌｉ離の塩素が装置を腐食させること
が生じＩこ。また炭化水素類を使用した場合は溶解性が
悪く、膜厚のコントロール、塗膜の均一性に支障をきた
すことが判った。そこで本発明者らは多くの物質に対す
る溶解性が優れている溶剤であるエーテル類のテ１へラ
ヒドロフランに注目し、種々の電荷搬送物質、結着剤の
検討を行なつｌ〔。There are also restrictions on the material ratio between the charge transport material and the binder.
Difficult to select preferred material ratios. Furthermore, there is a limit to the concentration of the coating solution at a low level, which poses a problem in controlling coating film formation. Various solvents have been studied for this purpose, but among the above-mentioned solvents, hydrocarbons, ethers, and chlorinated hydrocarbons are generally used. According to the studies conducted by the present inventors, the use of chlorinated hydrocarbons is superior in terms of dissolving the charge transporting substance and the binder and providing a stable coating solution; If chlorine is used, it will react with the free chlorine of chlorinated hydrocarbons, forming a charge transfer complex, which will have an adverse effect on the electrophotographic properties, and the free chlorine may corrode the equipment. It has also been found that when hydrocarbons are used, they have poor solubility, which impedes control of film thickness and uniformity of the coating film. Therefore, the present inventors focused on the ether hydrofuran, which is a solvent with excellent solubility for many substances, and investigated various charge transport substances and binders.

まず電荷搬送物質として下記一般式（Ｔ）で示されるヒ
ドラゾン化合物を用いる。First, a hydrazone compound represented by the following general formula (T) is used as a charge transporting substance.

（式中、Ｒ１はメチル基、エチル基、２−ヒドロキシエ
チル基、２−クロルエチル基を表わし、Ｒ２はメチル基
、エチル基、ベンジル基、フェニル基を表わし、Ｒ３は
塩素、臭素、炭素＠１〜４のアルキル基、炭素数１〜４
のアルコキシ基、ジアルキルアミノ基、ニトロ基を表わ
び。） また、結着剤として、４．４−−ジヒドロキシフェニル
−１，１−シクロヘキサノン及びホスゲンより得られる
繰返し単位、 のポリカーボネート樹脂（ビス７１ノール２タイプポリ
カーボネート）を使用する。(In the formula, R1 represents a methyl group, ethyl group, 2-hydroxyethyl group, or 2-chloroethyl group, R2 represents a methyl group, ethyl group, benzyl group, or phenyl group, and R3 represents chlorine, bromine, or carbon@1 ~4 alkyl group, carbon number 1-4
represents an alkoxy group, a dialkylamino group, and a nitro group. ) Also, as a binder, a polycarbonate resin (bis71nol 2 type polycarbonate) having repeating units obtained from 4,4-dihydroxyphenyl-1,1-cyclohexanone and phosgene is used.

本発明では、これらを用いることによって、ことにより
、極めて安定で、塗工性の擾れ１＝電荷搬送層形成用塗
布液が得られ、それを塗布することにより極めて良好な
電子写真特性が得られる電子写真用感光体を提供出来る
ことを見出した。何故にその様に（曇れｌζ特性が得ら
れるのかについては詳細は判らないが、比較検討した例
えば飽和ポリエステル樹脂を結着剤として用いた場合は
、塗布液の安定性は優れているが、機械的強度が劣る、
Ｔ（Ｉが低い為に保存中に経時変化し、電荷搬送物質が
表面に析出してくる、ま／、：Ｉ械的強麿が優れ°Ｃい
るビスフェノールΔタイプポリカーボネート、ボリアリ
レート樹脂を使用した場合は塗布液が経時変化を起し、
刻々粘度が変化し、ゲル化してくる等の事実より、恐ら
くビスフェノールＺタイプポリカーボネート樹脂は構造
的に機械的強度が優れ、Ｔ（Ｉが高く（１７０〜１８０
℃）、さらに非晶質である為ではないかと推定している
。In the present invention, by using these, it is possible to obtain a coating liquid for forming a charge transport layer that is extremely stable and has poor coating properties, and by coating it, extremely good electrophotographic properties can be obtained. It has been found that it is possible to provide an electrophotographic photoreceptor that can be used. Although we do not know the details of why such a characteristic (cloudy lζ) is obtained, for example, when saturated polyester resin is used as a binder, the stability of the coating solution is excellent, but the mechanical target strength is poor,
Bisphenol Δ type polycarbonate and polyarylate resin, which has excellent mechanical strength, are used. If the coating solution changes over time,
Bisphenol Z type polycarbonate resin probably has superior structural mechanical strength and has a high T(I) (170-180
℃), and it is presumed that this is due to the fact that it is amorphous.

従って塗布液は長期間において使用が可能であり、生産
性、コスト面で非常に有利となり、テトラヒトＤフラン
を使用する為、設備面で特別の配線は必要としなくてす
む。Therefore, the coating liquid can be used for a long period of time, which is very advantageous in terms of productivity and cost, and since tetrahydrofuran is used, no special wiring is required in terms of equipment.

本発明の電荷搬送層は、電荷搬送物質のヒドラゾン化合
物と結着剤であるビスフェノールＺポリカーボネートと
から基本的に成るが、その物質比は極めて広い範囲で使
用可能だが、１０：１〜１：１０、好ましくは２：１〜
１：２が適当であり、厚さは感光体の使用条件により異
なるが、５〜１００μ位が適当である。またさらに必要
ならば公知の可塑剤、レベリング剤を加えることも出来
る。The charge transport layer of the present invention basically consists of a hydrazone compound as a charge transport substance and bisphenol Z polycarbonate as a binder, and the ratio of these substances can be used in a very wide range, but it is 10:1 to 1:10. , preferably 2:1~
A ratio of 1:2 is suitable, and the thickness varies depending on the usage conditions of the photoreceptor, but a thickness of about 5 to 100 μm is suitable. Furthermore, if necessary, known plasticizers and leveling agents can be added.

本発明の積層型電子写真用感光体は、基本的にはアルミ
ニウム、ニッケル、クロム、酸化スズ、酸化インジウム
等をポリエステルフィルム、ポリプロピレンフィルム、
酢酸セルロースフィルム等のプラスチックフィルムに蒸
着し導電処理したもの、或いはアルミニウム、ニッケル
、鉄等の金属板、金属管を導電性支持体どし、その上に
電荷発生層を設け、さらに電荷搬送層を積層することに
より得られる。The laminated electrophotographic photoreceptor of the present invention basically contains aluminum, nickel, chromium, tin oxide, indium oxide, etc., in polyester film, polypropylene film,
A conductive support is made of a plastic film such as cellulose acetate film that has been vapor-deposited and conductively treated, or a metal plate or tube made of aluminum, nickel, iron, etc., and a charge generation layer is provided thereon, followed by a charge transport layer. Obtained by laminating.

本発明において用いられる電荷発生層は、５ｅＳＳｅ合
金、ａ−８ｉ等の無機半導体、フタロシアニン顔料、ペ
リレン顔料、インジゴ顔料等の光導電性有機顔料を蒸着
、スパッタリング、グロー放電等により設（）たり、光
導電性有機顔料例えば、シーアイピグメントブル−２５
（カラーインデックス（ＣＩ）２１１８０）、シーアイ
ピグメントレッド４１（ＣＩ２１２００）　、シーアイ
ジッドレッド５２（Ｃｌ　４５１００）、シーアイベー
シックレッド３（ＣＩ　４５２１０）の他に、カルバゾ
ール骨格を有するアゾ顔料（特開昭５３−９５０３３号
公報に記載）、スヂリルスヂルベン骨格を有するアゾ顔
料（特開昭５３−１３３２２９号公報に記載）、１ヘリ
フにルアミン骨格を有するアゾ顔料（特開昭５３−１３
２５４７号公報に記載）、ジベンゾチオフェン骨格を有
するアゾ顔料（特Ｕロ昭５４−２１７２８号公報に記載
）、オキサジアゾール骨格を有するアゾ顔料（特開昭５
４−１２７４２号公報に記載）、フルオレノン骨格を有
するアゾ顔料（特開昭５４−２２８３４号公報に記載）
、ビススチルベン骨格を有するアゾ顔料（特開昭５４−
１７７３３号公報に記載）、ジスチリルオキサジアゾー
ル骨格を有するアゾ顔料（特開昭５４−２１２９号公報
に記載）、ジスチリルカルバゾール骨格を有するアゾ顔
料（特開昭５４−１７７３４号公報に記載）、カルバゾ
ール骨格を有するトリスアゾ顔料（特開昭５７−１９５
７６７、特開昭５７−１９５７６８号に記載）など、更
には、シーアイピグメントブルー１６　（ＣＩ　７４１
００）などのフタロシアニン系顔料、シーアイバットブ
ラウン５（Ｃｆ　７３４１０）　、シーアイバットダイ
（Ｃ１７３０３０）などのインジゴ系顔料、アルゴスカ
ーレットＢ（バイエル社製）、インダンスレンスカーレ
ットＢ（バイエル社製）などのペリレン系顔料などを単
独、もしくは数種類使用し、必要ならば結着剤とともに
溶剤に分散し、塗布等により設【プることが出来る。結
着剤としてはポリビニルブチラール樹脂、ポリビニルホ
ルマール樹脂、ポリエステル樹脂、ポリカーボネート樹
脂、ポリスチレン、ポリ酢酸ビ二ル、ポリ塩化ビニル、
ポリアミド、ポリウレタン、各種ヒルロース等を使用す
ることが出来る。The charge generation layer used in the present invention is formed by depositing a 5eSSe alloy, an inorganic semiconductor such as a-8i, a photoconductive organic pigment such as a phthalocyanine pigment, a perylene pigment, an indigo pigment, etc. by vapor deposition, sputtering, glow discharge, etc. Photoconductive organic pigments such as CI Pigment Blue-25
(Color Index (CI) 21180), CI Pigment Red 41 (CI21200), CI Gid Red 52 (Cl 45100), CI Basic Red 3 (CI 45210), as well as azo pigments with a carbazole skeleton (JP-A-53- 95033), an azo pigment having a styrylsdirbene skeleton (described in JP-A-53-133229), an azo pigment having a luamine skeleton in one heliph (JP-A-53-13)
No. 2547), azo pigments having a dibenzothiophene skeleton (described in Japanese Patent Application Publication No. 1972-21728), azo pigments having an oxadiazole skeleton (described in Japanese Patent Application Laid-Open No. 1983-21728),
4-12742), azo pigments having a fluorenone skeleton (described in JP-A-54-22834)
, an azo pigment having a bisstilbene skeleton (Japanese Unexamined Patent Publication No. 1983-
17733), an azo pigment having a distyryloxadiazole skeleton (described in JP-A-54-2129), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-17734) , a trisazo pigment having a carbazole skeleton (JP-A-57-195
767, described in JP-A-57-195768), and CI Pigment Blue 16 (CI 741
00), indigo pigments such as C.I. Butt Brown 5 (Cf 73410) and C.I. Butt Dye (C173030), Argo Scarlet B (manufactured by Bayer), Indanthrene Scarlet B (manufactured by Bayer), etc. Perylene pigments can be used alone or in combination, and if necessary, they can be dispersed in a solvent together with a binder and applied by coating. As a binder, polyvinyl butyral resin, polyvinyl formal resin, polyester resin, polycarbonate resin, polystyrene, polyvinyl acetate, polyvinyl chloride,
Polyamide, polyurethane, various types of hirulose, etc. can be used.

また、溶剤としてはベンゼン、トルエン、キシレン、塩
化メチレン、ジクロルエタン、モノクロルベンゼン、ジ
クロルベンゼン、酢酸メチル、酢酸ブチル、メチルエチ
ルケトン、ジオキサン、テトラヒドロフラン、ジメチル
ホルムアミド、シクロヘンサノン、メチルセルソルブ、
エチルセルソルブ等及びこれらの混合物が挙げられる。In addition, solvents include benzene, toluene, xylene, methylene chloride, dichloroethane, monochlorobenzene, dichlorobenzene, methyl acetate, butyl acetate, methyl ethyl ketone, dioxane, tetrahydrofuran, dimethylformamide, cyclohensanone, methyl cellosolve,
Examples include ethyl cellosolve and mixtures thereof.

これらの方法で形成される電荷発生層の厚さは０．０５
〜２０μ、好ましくは０．１〜２μ程度が適当である。The thickness of the charge generation layer formed by these methods is 0.05
~20μ, preferably about 0.1~2μ is appropriate.

なお本発明において、感光体の層間後盾性及び帯電特性
を改良するために、電荷発生層を形成する前に、導電性
支持体上にポリアミド、ポリ酢酸ビニル、ポリウレタン
等の接着層、中間層、或いは酸化アルミニウム等の薄層
を塗布、蒸着等の常法により０．０１〜２．０μ厚程度
設けることが出来る。In the present invention, in order to improve the interlayer shielding properties and charging characteristics of the photoreceptor, before forming the charge generation layer, an adhesive layer of polyamide, polyvinyl acetate, polyurethane, etc., an intermediate layer, Alternatively, a thin layer of aluminum oxide or the like can be provided with a thickness of about 0.01 to 2.0 μm by a conventional method such as coating or vapor deposition.

以下に実施例を示す。Examples are shown below.

実施例１ 光導電性有機顔料として、下記のジアゾ顔料を使用し、
以下の手順で電荷発生層形成塗布液を調整した。Example 1 The following diazo pigment was used as a photoconductive organic pigment,
A charge generation layer forming coating solution was prepared according to the following procedure.

ポリエステル樹脂（バイロン２００、東洋紡０勾製）の
５重量％テトラヒドロフラン溶液１３．６ｇ テトラヒドロフラン　４４．２ｇ をボールミルで４８時間分散した後、ざらにテトラヒド
ロフラン２２．３（］　、エチルセルソルブ３７．２ｇ
を加え１時間分散した。分散後ミルベースを容器に取り
出し、テトラヒドロフラン、エチルセルソルブが重量比
で４＝６、固形分濃度が１重量％になる様に希釈攪拌し
、塗布用の分散液を調製した。After dispersing 13.6 g of a 5% by weight tetrahydrofuran solution of polyester resin (Vylon 200, manufactured by Toyobo 0 Co., Ltd.) and 44.2 g of tetrahydrofuran for 48 hours in a ball mill, 22.3 g of tetrahydrofuran (22.3 g) and 37.2 g of ethyl cellosolve were dispersed in a ball mill.
was added and dispersed for 1 hour. After dispersion, the mill base was taken out into a container and diluted and stirred so that the weight ratio of tetrahydrofuran and ethyl cellosolve was 4=6 and the solid content concentration was 1% by weight to prepare a dispersion for coating.

次にこの分散液を、浸漬塗工法で、０．５ｍｍ厚アルミ
ニウム板（ＪＩ　Ｓ　１０７０）上に塗布し、乾燥して
厚さ０．５μｍの電荷発生層を設けた。Next, this dispersion was applied by dip coating onto a 0.5 mm thick aluminum plate (JIS 1070) and dried to form a charge generation layer with a thickness of 0.5 μm.

次に下記組成の電荷搬送層形成用の塗布液を用意し、浸
漬塗工法により塗布し、乾燥後の膜厚が２０μｍの電荷
搬送層を設けて、積層型電子写真用感光体を作成した。Next, a coating solution for forming a charge transport layer having the following composition was prepared and applied by dip coating to provide a charge transport layer having a thickness of 20 μm after drying, thereby producing a laminated electrophotographic photoreceptor.

下記構造式のヒドラゾン化合物 ビスフェノールＺポリカーボネート　２０ｇシリコンオ
イル＜ＫＦ５０　信越化学（体製）０．００２ｇ テトラヒドロフラン　１６０ｇ 比較例１ 電荷搬送層形成用塗布液として、ビスフェノールＺポリ
カーボネートの代りに、ポリアクリレート樹脂（Ｕ−１
００：ユニチカ製）を用いた以外は実施例１と全く同様
の条件で積層型電子写真用感光体を作成した。Hydrazone compound bisphenol Z polycarbonate with the following structural formula 20 g Silicone oil < KF50 Shin-Etsu Chemical (manufactured by Taiyo) 0.002 g Tetrahydrofuran 160 g Comparative Example 1 As a coating liquid for forming a charge transport layer, polyacrylate resin (U- 1
A laminated electrophotographic photoreceptor was produced under exactly the same conditions as in Example 1, except that a photoreceptor (manufactured by Unitika Co., Ltd.) was used.

実施例２ ０．５ｍｍ厚さのアルミニウム板（Ｊ　Ｉ　Ｓ　１０７
０）ポリアミド樹脂（共重合ナイロン、 Ｅ　ｌｖａｍｉｄｅ　８０６１　［Ｊ　ｕｐｏｎｔ製＞
　１００エチルアルコール　１９０（］ より成る塗布液を用意し、浸漬塗工により塗布し、乾燥
後の膜厚的０．２μの中間層を設けｌこ　。Example 2 0.5 mm thick aluminum plate (JIS 107
0) Polyamide resin (copolymerized nylon, Elvamide 8061 [manufactured by Jupont]
A coating solution consisting of 100% ethyl alcohol and 190% ethyl alcohol was prepared and applied by dip coating to provide an intermediate layer having a thickness of 0.2 μm after drying.

次に光導電性顔料として下記のジスアゾ顔料を使用し、
以下の手順により電荷発生層形成用塗布液を調製した。Next, use the following disazo pigment as a photoconductive pigment,
A coating solution for forming a charge generation layer was prepared according to the following procedure.

ジスアゾ顔料 シクロヘキサノン　５７ｇ をボールミルで４８時間分散した後、さらにシクロヘキ
サノンを９０ｇ加え、さらに１時間分散した。分散後ミ
ルベースを容器に取り出し、シクロヘキサノンを加え、
固形分ｍ度が１重量％になる様に希釈攪拌し、塗布用の
分散液を調製した。次にこの分散液を浸漬塗工法で中間
層上に塗布し、乾燥後の厚さ０．５μＩＩＩの電荷発生
層を設けた。次に下記組成の電荷搬送層形成用塗布液を
用意し、浸漬塗工法により電荷発生層上に塗布し、乾燥
後の膜厚が２０μｍの電荷搬送層を設けて、導電層−中
間層−電荷発生層−電荷搬送層より成る積層型電子写真
用感光体を作成した。After 57 g of the disazo pigment cyclohexanone was dispersed in a ball mill for 48 hours, 90 g of cyclohexanone was added and further dispersed for 1 hour. After dispersion, take out the mill base into a container, add cyclohexanone,
The mixture was diluted and stirred so that the solid content was 1% by weight to prepare a dispersion for coating. Next, this dispersion was applied onto the intermediate layer by dip coating to provide a charge generation layer having a dry thickness of 0.5 μm. Next, a coating solution for forming a charge transport layer having the following composition was prepared, and applied onto the charge generation layer by dip coating to form a charge transport layer with a dry film thickness of 20 μm. A laminated electrophotographic photoreceptor consisting of a generation layer and a charge transport layer was prepared.

下記構造式のヒドラゾン化合物 ビスフェノールＡポリカーボネート　２０ｇシリコンオ
イル（Ｋ、Ｆ５０信越化学■製）ｏ、ｏｏ２ｇ テトラヒドロフラン　１６０ｇ 比較例２ 電荷搬送層形成用塗布液として、ビスフェノールＺポリ
カーボネートの代りに、ビスフェノールＡポリカーボネ
ート（Ｋ−１３００：帝人化成■製）を用いた以外は実
施例２と全く同様の材料、条件で積層型電子写真用感光
体を作成しｌζ。Hydrazone compound with the following structural formula Bisphenol A polycarbonate 20 g Silicone oil (K, F50 manufactured by Shin-Etsu Chemical ■) o, oo 2 g Tetrahydrofuran 160 g Comparative Example 2 As a coating liquid for forming a charge transport layer, bisphenol A polycarbonate (K A laminated electrophotographic photoreceptor was prepared using the same materials and conditions as in Example 2, except that 1300 (manufactured by Teijin Kasei ■) was used.

次に各実施例及び比較例で調製した電荷搬送層形成用塗
布液を容器に入れ密封し、回転粘度δＩ（Ｅ型粘度計、
タイプＥＬ；東機産業（（３）製）を使用し、粘度の経
時変化を測定した。Next, the charge transport layer forming coating solution prepared in each Example and Comparative Example was placed in a container and sealed, and the rotational viscosity δI (E-type viscometer,
Type EL: Toki Sangyo (manufactured by (3)) was used to measure the change in viscosity over time.

測定結果を表１に示す。The measurement results are shown in Table 1.

また以上の様にして作成した各々の電子写真用感光体は
静電複写紙試験装置（■川口電機製作所製５Ｐ４２８型
）を用いて、以下の条件で電子写真特性を評価した。Further, the electrophotographic properties of each of the electrophotographic photoreceptors prepared as described above were evaluated using an electrostatic copying paper tester (model 5P428 manufactured by Kawaguchi Denki Seisakusho) under the following conditions.

コロナ放電を２０秒間行なって帯電せしめ、その時の表
面電位Ｖｓ　（ボルト）を測定し、更に２０秒間暗所に
放置し、その時の表面電位Ｖｏ　（ボルト）を測定し、
ついで２０ルツクスの白色タングステン光を照射した後
、ｖＯが１／１０に減衰するのに要する露光量Ｅ　１／
１０（ルックス・秒）、及び照射３０秒後の表面電位Ｖ
　を測定した。Conduct corona discharge for 20 seconds to charge it, measure the surface potential Vs (volts) at that time, leave it in a dark place for another 20 seconds, measure the surface potential Vo (volts) at that time,
Then, after irradiating white tungsten light of 20 lux, the exposure amount E required for vO to attenuate to 1/10 is 1/
10 (lux seconds), and surface potential V after 30 seconds of irradiation.
was measured.

結果を表２に示す。The results are shown in Table 2.

表−１粘度の経時変化（測定温度　２０℃）表−２電子
写真特性 効　果 以上の例で判る様に、基本的に本弁明のヒドラゾン化合
物、ビスフェノールＺポリカーボネート、テトラヒドロ
フランより成る電荷搬送層形成用の塗布液は経時変化す
ることなく極めて安定Ｃあり、それを使用づることによ
り、極めて高品位な積層型電子写真用感光体が得られる
。Table 1 Change in viscosity over time (measurement temperature 20°C) Table 2 Effects on electrophotographic properties As can be seen from the above examples, for forming a charge transport layer basically consisting of the hydrazone compound of the present invention, bisphenol Z polycarbonate, and tetrahydrofuran. The coating liquid C is extremely stable without changing over time, and by using it, a laminated electrophotographic photoreceptor of extremely high quality can be obtained.

特ム′［出願人　株式会社リ　コ　− 代理人　弁理士　小　松　秀　岳 代理人　弁理士　旭　宏Special feature [Applicant: Rico Co., Ltd.] Agent Patent Attorney Hidetake Komatsu Agent Patent Attorney Hiroshi Asahi

Claims (1)

【特許請求の範囲】[Claims] （１）導電性支持体上に電荷発生層及び電荷搬送層を設
けた積層型の電子写真用感光体において、電荷搬送層が
、少なくとも下記一般式（Ｉ＞で示されるヒドラゾン化
合物と （式中、１（１はメチル基、エチル基、２−ヒドロキシ
エチル基、２−クロルエチル基を表わし、Ｒ２はメチル
基、エチル基、ベンジル基、フェニル阜を表わし、Ｒ３
は塩素、臭素、炭素数１〜４のアルキル基、炭素数１〜
４の７アルコキシ基、ジアルキルアミノ基、ニトロ基を
表ねず。〉 構造式 ％式％ 及びホスゲンより得られる繰返し単位 のポリカーボネート樹脂を含むことを特徴とする電子写
真用感光体。(1) In a laminated electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are provided on a conductive support, the charge transport layer contains at least a hydrazone compound represented by the following general formula (I>) and (in the formula , 1 (1 represents a methyl group, ethyl group, 2-hydroxyethyl group, 2-chloroethyl group, R2 represents a methyl group, ethyl group, benzyl group, phenyl group, R3
is chlorine, bromine, alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4-7 does not represent an alkoxy group, dialkylamino group, or nitro group. 〉 An electrophotographic photoreceptor comprising a polycarbonate resin having the structural formula % and a repeating unit obtained from phosgene.
JP7014284A 1984-04-10 1984-04-10 Electrophotographic sensitive body Pending JPS60213953A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7014284A JPS60213953A (en) 1984-04-10 1984-04-10 Electrophotographic sensitive body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7014284A JPS60213953A (en) 1984-04-10 1984-04-10 Electrophotographic sensitive body

Publications (1)

Publication Number Publication Date
JPS60213953A true JPS60213953A (en) 1985-10-26

Family

ID=13423021

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7014284A Pending JPS60213953A (en) 1984-04-10 1984-04-10 Electrophotographic sensitive body

Country Status (1)

Country Link
JP (1) JPS60213953A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6214160A (en) * 1985-07-11 1987-01-22 Canon Inc Electrophotographic sensitive body
JPS6214159A (en) * 1985-07-11 1987-01-22 Canon Inc Electrophotographic sensitive body
JPS6278563A (en) * 1985-10-02 1987-04-10 Canon Inc Electrophotographic sensitive body
JPS62187353A (en) * 1986-02-14 1987-08-15 Fuji Xerox Co Ltd Electrophotographic sensitive body
US4851314A (en) * 1986-01-09 1989-07-25 Canon Kabushiki Kaisha Electrophotographic photosensitive member with combined polycarbonate resins
EP1143302A1 (en) * 2000-04-05 2001-10-10 Ricoh Company, Ltd. Electrophotographic photoreceptor and image forming method and apparatus using the photoreceptor

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6214160A (en) * 1985-07-11 1987-01-22 Canon Inc Electrophotographic sensitive body
JPS6214159A (en) * 1985-07-11 1987-01-22 Canon Inc Electrophotographic sensitive body
JPS6278563A (en) * 1985-10-02 1987-04-10 Canon Inc Electrophotographic sensitive body
JPH0549101B2 (en) * 1985-10-02 1993-07-23 Canon Kk
US4851314A (en) * 1986-01-09 1989-07-25 Canon Kabushiki Kaisha Electrophotographic photosensitive member with combined polycarbonate resins
JPS62187353A (en) * 1986-02-14 1987-08-15 Fuji Xerox Co Ltd Electrophotographic sensitive body
JPH0473944B2 (en) * 1986-02-14 1992-11-25
EP1143302A1 (en) * 2000-04-05 2001-10-10 Ricoh Company, Ltd. Electrophotographic photoreceptor and image forming method and apparatus using the photoreceptor
US6432596B2 (en) 2000-04-05 2002-08-13 Ricoh Company Limited Electrophotographic photoreceptor and image forming method and apparatus using the photoreceptor

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